TWI295314B - Polymerizable liquid crystal material - Google Patents

Description

Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed 1295314 A7 __ B7 V. INSTRUCTIONS (i) Scope of the Invention The present invention relates to a polymerizable liquid crystal material containing at least one polymerizable surface active compound for preparing anisotropy thereof Uses of polymer films' and the use of liquid crystal materials and polymer films in optical and electrooptical devices for decorative and security applications. BACKGROUND OF THE INVENTION AND PRIOR ART A polymerizable liquid crystal material for preparing an anisotropic polymer film having a uniform orientation is known in the prior art. These films are often prepared by coating a thin layer of a polymerizable liquid crystal mixture on a substrate, arranging the mixture into a uniform orientation, and polymerizing the mixture. It is necessary to induce a planar arrangement in the liquid crystal layer for a particular application, even if the liquid crystal molecules are substantially oriented parallel to the layers. The cells are then blocked in a polymerized liquid crystal mixture. For example, an oriented film or layer of a polymeric nematic liquid crystal material arranged in a plane is used as a useful A-plate compensator or polarizer. Another important application is an oriented film or layer of a polymeric cholesteric liquid crystal material having a twisted molecular structure. If the cholesterol material has a planar arrangement, these films exhibit a selective reflection of light, where the reflected color is dependent on the viewing angle. It can be used, for example, as a circular polarizer, a color filter or an effective pigment for the preparation of decorative or security applications. The planar alignment can be achieved, for example, by treating a substrate coated with a liquid crystal material (e.g., honing or coating an alignment layer) or applying a liquid crystal material with a shearing force (e.g., during or after coating). > It is also known in the prior art to add a surface active compound to a liquid crystal material. This paper scale is applicable to China National Standard (CNS) A4 specification (210X297 mm). Please read the notes on the back and fill out this page. -4- 1295314 齐 眢 眢 眢 时 苟 Employees 泎 消费 泎 泎 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 A liquid crystal material arranged in a plane on a single substrate. For example, 'W0 99/45082 describes a photoresist film obtained by planarizing a layer of polymerizable liquid crystal material containing one or more fluorocarbon surfactants. US 5,9 9 5, 1 8 4 proposes a method for producing a phase retardation plate in a planar array of polymerizable liquid crystal material layers, wherein a surface active material such as, for example, polyacrylate, polyfluorenone or organodecane is added to the liquid crystal material to reduce The angle of inclination at the liquid crystal/air interface of the liquid crystal layer. However, the method of achieving planar alignment as described in the above document has many disadvantages. Therefore, the surfactant tends to be phase-to-liquid during or after polymerization. Separation of materials. If another layer is also provided on the polymeric liquid crystal film containing the surfactant, the surfactant tends to move into the second layer. For example, in special applications, such as cholesteric color filters A polymerized cholesteric liquid crystal material film is a part of a composite LC battery in which other layers must be added to the cholesteric film, such as other liquid crystal layers, retardation layers or cap layers, etc., but are not limited thereto. During the subsequent addition of layers, etc., the well-known surfactant molecules are filtered from the bottom layer and moved to the air interface. This causes the sample/air interface region to gradually concentrate more surfactants. The subsequent layers have different layers. Surface energy, and may no longer be considered to be the same. The movement of the surfactant may also be where it is desired to configure the top layer that does not include the surfactant or where the surfactant may also cause other species to move from one layer to the next. This poses a problem. Therefore, the object of the present invention is to provide a layout for preparation (please read the back of the note first and then fill out this page) - This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) -5- Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1295314 V. Invention description () 3 polymer film polymerizable liquid crystal material, It does not have the disadvantages described above. Other objects of the present invention will be immediately apparent to those skilled in the art from the following detailed description. The inventors of the present invention have discovered that it is possible to provide a polymerizable compound containing one or more polymerizable surface-active compounds. The liquid crystal mixture can achieve the above object. The present invention proposes to use a polymerizable surfactant in a mixture of polymerizable liquid crystal generating materials. The polymerizable surfactant can be easily polymerized into a liquid crystal film, and thus is completely hindered. Any surfactant is moved to a subsequent layer or the like. The present invention further demonstrates how it is possible to create different layer stacks' wherein one or more layers comprise low surface energy surfactants, such as fluorination-based surfactants, while maintaining the desired physical properties of subsequent layers and the like. An object of the present invention is a polymerizable liquid crystal material containing at least one polymerizable surface-active compound. Another object of the present invention is a method of preparing an anisotropic polymer film having a low inclination angle in a planar arrangement, which is coated on a substrate with a polymerizable liquid crystal material containing one or more polymerizable surface-active compounds. The materials are arranged in a planar orientation and the materials are polymerized. Another object of the present invention is a planarly arranged anisotropic polymer film having a low tilt angle obtained from a polymerizable liquid crystal material containing one or more polymerizable surface-active compounds. Another object of the present invention is to apply the Chinese National Standard (CNS) A4 specification (210 X 29*7 public) II to the standard of the polymerizable liquid crystal paper according to the present invention. II-line (please read the back first) Note: Please fill out this page again) -6 - 1295314 A7 B7 V. INSTRUCTIONS (4) Materials and polymer films are used as optical films for optical devices, decoration or preservation purposes, such as alignment layers, polarizers, compensators , color filters, laser photographic elements, hot stamping foils, colored images, decorative or security imprints, and optical films for the preparation of liquid crystal pigments for decorative or security applications. Another object of the invention is an alignment layer obtained from a polymerizable liquid crystal material containing one or more polymerizable surface-active compounds. Another object of the present invention is a cholesteric color filter obtained by polymerizable cholesteric liquid crystal material containing one or more polymerizable surface-active compounds. Macro Meaning of Terms As used in this application, the film/term includes a self-supporting (ie unsupported) film that exhibits more or less significant mechanical stability and flexibility, on a support substrate or on two substrates. Between the coating or layer. The 'liquid crystal generating compound/terminology used in the context should have a liquid crystal forming group which is in the form of a rod, a strip, or a disc, and the good P has a group capable of inducing a mesophase behavior. It is not necessary for these compounds to exhibit the mesophase behavior by themselves. It is also possible for these compounds to exhibit mesophase behavior only in a mixture of other compounds or in a polymerized liquid crystal forming compound or a mixture thereof. In particular, a liquid crystal forming group in the form of a rod or a strip is preferred. For the sake of simplification, the liquid crystal material is used for both the liquid crystal material and the liquid crystal generating material, and is used for the liquid crystal generating group of the material in the liquid crystal formability/terminology. This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) (please read the note on the back and fill out this page) Γ Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1295314 A7 A7 B7 V. Invention Description ( c) 5 Anisotropic or liquid crystal layer or film, angle of inclination / average angle of inclination of the entire film, unless otherwise stated. DETAILED DESCRIPTION OF THE INVENTION The polymerizable liquid crystal mixture according to the present invention comprises a polymerizable surfactant component comprising one or more polymerizable liquid crystal forming compounds and one or more surface active compounds. When the liquid crystal mixture is coated on the substrate, the surface active compound lowers the tilt angle of the liquid crystal molecules in the coating layer and thus enhances the planar alignment of the liquid crystal mixture. The surfactant is copolymerized with the monomer of the liquid crystal mixture and thus chemically bound into a shaped polymer film. To avoid the movement or separation of the surfactant. The arrangement of the polymerizable liquid crystal material can be further controlled by the choice of polymerizable liquid crystal generating or liquid crystalline compound. Therefore, it has been found that if the mixture includes only a small amount of a polymerizable liquid crystal forming compound having a nonpolar terminal group (and preferably consists of a compound having a polar terminal group), a plane having a small inclination angle can be achieved. arrangement. 'Polar group / special representative is selected from halogen, CN, N 0 2, Ο Η, 〇CH3, 〇CN, SCN, vinyloxy, propenyl, methacryl, chloropropenyl, epoxy, with up to a carbonyl or carboxyl group of 4 C atoms, or a mono-, oligo- or polyfluorinated alkyl or alkoxy group having 1 to 5 C atoms. The halogen is preferably F or C 1 . <Apolar group/particularly an aliphatic or aromatic alkyl group having 1 or more C atoms or an alkenyl group or alkoxy group having 2 or more C atoms, which is not a polar group. This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) -----------Installation-- (Please read the note on the back and fill in this page), ?τ line Zou & 曰 时 时 员工 Employee Employees Consuming Society Printing -8-1295314 A7 B7 V. Description of Invention (6) Ethyleneoxy, propenyl, methacryl, epoxy, F, C 1 , 〇H, CN, 〇CH3, C〇CH3, COC2H5, C00CH3' COOC2H5' CF3, C2F5, 〇CF3, 〇CHF 2 and 0 C 2 F 5 are particularly preferred polar groups, especially ethyl ethoxide, propylene , methacryl, epoxy, F, C 1 , CN, 〇C Η 3 and 〇CF 3 . A particularly preferred embodiment relates to a polymerizable liquid crystal material comprising: less than 40% by weight of a polymerizable liquid crystal forming compound having a nonpolar terminal group, preferably less than 20%, preferably less than 1% by weight. , in particular, less than 5%, • the ratio of the polymerizable liquid crystal forming compound having at least one polar terminal group to the polymerizable liquid crystal generating compound having a nonpolar terminal group is at least 2:1 to at least 3:1 Preferably, especially at least 5:1, • does not include any polymerizable liquid crystal forming compound having a nonpolar group, • consists essentially of a polymerizable liquid crystal forming compound having at least one polar terminal group, Included from 0. 01 to 15% by weight of the polymerizable surface-active compound, preferably from 0.1 to 5%, • comprising one or more surface-active compounds selected from polymerizable fluorocarbon surfactants, in particular fluorocarbon Acrylate or fluorocarbon methacrylate, • Contains one or more surface active compounds with a surface tension of 15 to 5 OmNm_1. This paper scale applies to Chinese national standards. CNS ) A4 Specification (210><297 mm) I-----------^ —— (Please read the notes on the back and fill out this page) Order -9 - Ministry of Economics Intellectual Property Bureau employee consumption cooperative printing 1295314 A7 B7 V. Description of invention (7) • Contains one or more surface active compounds having a surface tension of less than 2 5 mNm·1, • In addition to the polymerizable surfactant, only Two or more (two preferred) polymerizable polymerizable liquid crystal forming compounds • comprising at least 20% by weight of one or more polymerizable single reactivitys containing one polymerizable group and one polar terminal group Liquid crystal forming compounds • Contains less than 5% of non-polymerizable components, • Contains one or more palmitic compounds, • Contains less than 15% of the palmitic component. The surface active compound contains at least one polymerizable group (preferably one or two). It may also be liquid crystal forming or liquid crystal. Suitable surface-active compounds are, for example, those comprising one or more polymerizable groups selected from the group consisting of propenyl, methylpropyl, epoxy, vinyl, vinyloxy, styrene or propylene ether groups, in particular propylene groups. , methacryl, epoxy and vinyloxy. The polymerizable surface-active compound is preferably a polymerizable group polymerized under the same conditions as those of at least one of the polymerizable liquid crystal compounds of the mixture. It is particularly preferable that the polymerizable group of the surface active compound is the same as the polymerizable group of the liquid crystal mixture. The average tilt angle of the polymerizable liquid crystal material according to the present invention on a single substrate having a surface exposed to air may be between the tilt angles of the liquid crystal material typically on the substrate of from about 2 〇 - 30 ° to about 〇 °. sort out. This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) -----------Install ------1T------ line (please read the back of the note first) Matters refill this page) -10 - 1295314 A7 B7__ V. INSTRUCTIONS (.) 8 It is preferable to use short-chain and mixed fluorocarbon/hydrocarbon surfactants because the lower surface energy enables a given concentration of interfacial activity. The surface tension of the mixture of the agent is more reduced. For example, hydrocarbons, anthrones, and fluorochemical surfactants typically have surface tensions of 225, 20-35, and 16-20 m N m .1, such as L. Gehlhoff, Fluorosurfactants for Paint and Coatings, and 3 M products. Information report (St. Paul, Minnesota, USA). The low tension of these fluorine chemical interfacial agents has been utilized in the prior art, for example, in leveling agents for coatings (L. Gehlhoff, VN Fluorosurfactants for Paint and Coatings, 3 M Product Information). Molecules with low surface energy can easily accumulate at the CLC/air interface to promote alignment effects. It is particularly preferable to use an acrylic monomer having a perfluoroalkyl group or a mixture thereof, such as, for example, Fluorad FX-13® and FX-14® (St. Paul, Minnesota, USA) commercially available from 3 ,, which has the following structure

CnF2n + iS〇2N(C2H5)CH2CH2〇COCH = CH2 IX(FX-13)

CnF2n + iS〇2N(C2H5)CH2CH2〇COC(CH3) = CH2 X(FX-14) wherein n is an integer from 4 to 8, and the perfluoroalkyl group may be straight or branched. Once these surfactants are used, it is possible to produce an anisotropic polymer film having a planar arrangement with a low tilt angle ranging from 0 to 3 degrees (especially 0 to 1.5). In the ideal case, the tilt angle is about 0 degrees. Preferred embodiments are directed to a planar array of polymeric films comprising polymeric nematic liquid crystal materials in accordance with the present invention. This paper scale applies to the Chinese National Standard (CNS) A4 specification (210Χ297 mm) ' -11 - -----------^------1Τ------^ (please Read the notes on the back and fill out this page.) Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperatives Ministry of Printing and Economy Ministry Intellectual Property Bureau Staff Consumer Cooperatives Print 1295314 A7 B7 V. Invention Description (9) Another preferred embodiment is about A polymer film in a planar arrangement containing a polymeric cholesteric liquid crystal material according to the present invention. In a preferred embodiment, the polymerizable liquid crystal material comprises at least one polymerizable compound having two or more polymerizable functional groups (two or more reactive or di- or polyfunctional compounds), It may be a liquid crystal forming compound or a surface active compound. Once polymerized in this mixture, a three-phase polymer network is formed. Polymer films made from such networks are self-supporting and exhibit high mechanical and thermal stability and low temperature dependence of their liquid crystal properties. In an ideal case, the liquid crystal properties of the polymer film are temperature dependent. The crosslink density of the resulting polymer film can be easily adjusted by different polyfunctional liquid crystal generating or non-liquid crystal generating compound concentrations, and thus the physical and chemical properties such as the glass transition temperature (which is optically variable to the film) can be easily adjusted. Temperature dependence is also important), thermal and mechanical stability or solvent resistance. The polymerizable material is particularly preferably a polyreactive liquid crystal-forming compound containing 5 to 100% by weight, particularly 25 to 80%, and preferably 4 to 70%. A di-reactive liquid crystal-forming compound is particularly preferred. The polymerizable liquid crystal generating compound of the liquid crystal material is preferably selected from the group consisting of Formula I

P-(Sp-X)n.MG-R I wherein P is a polymerizable group, s P has a spacer of 1 to 25 C atoms, and the paper scale is applicable to China National Standard (CNS) A4 specification (210X297 public) PCT) -----------Install ------Set ------ line (please read the note on the back and fill out this page) •12- 1295314 A7 ___B7 _ V. DESCRIPTION OF THE INVENTION (1〇) X is one, one s —, one c 〇 one, one c 〇〇 one, one 〇 C 〇 one, one CO — NH — , one NH — C〇 one, —CH 2 CH 2 —, One CH2 — , one CH 2 ◦ —, one SCH2 —, one CH 2 S —, one CH=CH — , one CH=CH—C〇〇, —〇C〇—CH=CH—, one CeC—or one-button , η 〇 or 1, MG liquid crystal generating group, and R system Η, CN, NO", halogen or a linear or branched alkyl group having up to 25 C atoms, the alkyl group may not be substituted Or mono- or poly-substituted with halogen or C ,, it is also possible that in each case one or more non-contiguous CH2 groups are independent of each other by a 0-, an S-, - ΝΗ-, a N (CH3) —, one C〇 one, one COO—one one C〇 one, one〇 c〇 one One, one S - c 〇 one, one c 〇 s - or - C E C - is replaced by a way that the oxygen atoms are not directly connected to each other, or R represents P - ( s p - X ) η -. The MG in Formula I is preferably selected from Formula I I.

II wherein Ζ1 and Ζ2 are each independently a C0 0—, a 〇c〇1, a CH2CH2—, a 〇ch2—, a CH2〇1, a CH=CH—, a CH=CH—C〇〇1, A C〇CH=CH—, a CEC—or a single bond, A1, A2, and A3 are each independently 1,4-phenylene, and the paper size is applicable to the Chinese National Standard (CNS) Μ specification (210X297 PCT 1 ^ (Please read the notes on the back and fill out this page) Loading - Customizing the Ministry of Commerce, Intellectual Property Office, Staff Consumer Cooperatives Printing - 13- 1295314 A7 B7 V. One or more of the invention instructions (u) The CH group is replaced by N, 1, 4 cyclohexene. In addition, one or two uncontiguous CH 2 groups may be fluorene and/or S, 1 ' 4 -cyclohexene, 1,4-bicyclo (2, 2, 2) octyl, pyridin-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6- Dihydrogen substitution, all of these groups may not be substituted or have an alkyl, alkoxy or alkane group having 1 to 7 C atoms in F, C1, 0H, CN, N〇2_ (where one or more A Η atom is taken in F or C1 ), And the Department of square m, 1, or 2. Formula I I preferred a small part of the liquid crystal display substrate generated as follows. For simplicity reasons, P in these groups is based h e 1, 4-phenylene one,

PheL is an alkyl, alkoxy or alkyl fluorenyl group which is fluorinated or chlorinated as needed, with 1 to 4 lines of F, C1, 01^, 〇11, 1^〇2 or 1 to 7 C atoms. L-substituted 1,4-phenylene, and Cyc 1,4-cyclohexene. The following list of preferred liquid crystal generating groups includes the sub-forms II-1 to II-25 and the mirror image of the other. --------------Please read the notes on the back This buy) Ordering economy Lang wisdom when producing 3⁄4 members X consumption combined with fi printing-Phe-Z-Phe- II-l -Phe-Z-Cyc- II-2 -Cyc-Z-Cyc- II-3 - PheL-Z-Phe- II-4 -PheL-Z-Cyc- II-5 -PheL-Z-PheL- II-6 -Phe-Z-Phe-Z-Phe- II-7 -Phe-Z-Phe- Z-Cyc- II-8 This paper scale applies to Chinese National Standard (CNS) A4 size (2H) X29: 7 mm) -14 - 1295314 λ7 Β7 V. Invention description (12) -Phe-Z-Cyc-Z -Phe- II-9 -Cyc-Z-Phe-Z-Cyc- IMO -Phe-Z-Cyc-Z-Cyc- IM 1 -Cyc-Z-Cy cZ-Cy c- 11-12 -Phe-Z- Phe-Z-PheL-IM3 -Phe-Z-PheL-Z-Phe· 11-14 -PheL-Z-Phe-Z-Phe- 11-15 -PheL-Z-Phe-Z-PheL- 11-16 - PheL-Z-PheL-Z-Phe- 11-17 -PheL-Z-PheL-Z-PheL- 11-18 -Phe-Z-PheL-Z-Cyc- 11-19 -Phe-Z-Cyc-Z- PheL- 11-20 -Cyc-Z-Phe-Z-PheL 11-21 -PheL-Z-Cyc-Z-PheL 11-22 -PheL-Z-PheL-Z-Cyc- 11-23 -PheL-Z- Cyc-Z-Cyc- 11-24 -Cyc-Z-PheL-Z-Cyc- 11-25 ------------^------1Τ------# (Please read the note on the back first) Item re-filled this page) Economy Zou Wisdom, 苟 Employees' consumption 阼 ii printed with sub-type II — 1, II - 2, II — 4, II — 6, I 1-7, I 1—8, II 11. I 1 - 13, II - 1 4, II - 1 5 and II - 1 6 are particularly good. In each case, these preferred Z groups independently have one of the meanings of Z 1 provided by Formula I. The Z series is preferably a C 〇〇 , - 〇 C 〇 , a CH 2 CH 2 -, a CeC - or a single bond. The liquid crystal generating group M G is selected from the following chemical formula and the mirror image of the paper. The Chinese National Standard (CNS) A4 specification (210×297 mm) -15-1295314

1 Binding I line (please read the note on the back and then fill out this page) This paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm) -16-1295314 A7 B7 V. Invention description 14 7 (L) r (L)r coo^_^_ llh

(L)r Uycoo^y^y(L)r (u (μ 卜0〇 〇〇c

Hi

Ilk ^ (u (μ llm

(L)r (U ^ch2ch2^Q^ch2ch2 lln (L)r (L)r (L)r llo ^ Batching order (please read the notes on the back and fill out this page) Ministry of Economic Affairs Intellectual Property Office staff The consumer cooperative prints that L has the meaning provided above and the r system 0, 1 or 2J^r represents in these preferred chemical formulas.

Base

L is very good, even more than one of the L series has more than one of the meaning provided. The paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -17- 1295314 λ7 _Β7_ V. DESCRIPTION OF THE INVENTION (15) The subtypes II d, II g, II h, II i , II k and II o are particularly preferred, especially the secondary II d and II k. L is preferably F, C1, CN, 〇H, N〇2, CH3, C2H5' OCH3' OC2H5' COCHa' COC2H5, c〇〇ch3, C〇〇C2H5, CF3, 〇CF3, 〇CHF2, OC2F5, In particular, F, C 1 , CN, CH3, C2H5, 〇CH3, C〇CH3 and 〇CF3 are optimal for F, C 1 , CH3, 〇CH3 and C〇CH3. In another preferred embodiment, the polymerizable mixture comprises at least one palmitic polymerizable compound of formula I comprising a liquid crystal forming group having at least one pair of palmitic centers. Among these compounds, M1 and/or Μ 2 are preferably selected according to the following chemical formula: -(A1-Z)a-G1-II*-1 -(A1-Z)a-G2-(Z-A2)b. II *.2 where A1, A2 and Z have the meanings set forth in Formula II, a and b are independent of each other, 〇, 1 or 2, and G 1 and R together form a terminal-to-palm group in Formula I, and G 2 It is a divalent pair of palmity groups. Preferred palmitoyl groups G 1 - R are, for example, cholesterol decyl alkenyl groups (for example, as disclosed in W096/17901), selected from the group consisting of a capping group, a neodecyl group, a canrenyl group, a pine base group, and a terpineyl group. Iso-leaf base, cover base, carreyl, myrthenyl, nodecyl, geranyl, linaloyl, neroli, fragrant paper scale applicable to China National Standard (CNS) A4 specification (210X297 mm) " ~ -18- II » I Pack III Order - ~ Line (please read the notes on the back and fill out this page) 16 -〇

Rf

1295314 at B7 V. DESCRIPTION OF THE INVENTION (Thomal and dihydrocitronellol groups are preferred, especially for capping or anthrone derivatives or terminal pairs of mono- or bicyclic groups containing pyranose or furanose rings Palmitic sugar derivatives, such as those derived from palmitic sugars disclosed, for example, by W〇9 5 / 1 0 0 07. Preferred palmitoyl G 2 systems such as cholesteryl or derived from saccharides a dinaphthyl derivative or an optically active ethylene glycol', especially an ethane-1,2-diol substituted with an alkyl group or an aryl group at the 1- and/or 2-position. In the case of a glycosyl group These are preferably selected from mono- and bicyclic groups containing pentose or hexose rings. The following G 2 is particularly preferred - 〇, 尸一Ο, 一 0 Phe, 〇-Phe O- Phe 〇 One Phe 0-

Wherein p h e has the meaning set forth above, R 4 is F or an optionally fluorinated alkyl group having 1 to 4 C atoms, and Y 1 , Y 2, Y 3 and Y 4 have one of the meanings of R1 in formula I. G 2 is a sorbitan, substituted ethane glycol (such as the paper size applicable to China National Standard (CNS) A4 specification (210X297 mm) ------------ ------tr------0 (Please read the notes on the back and then fill out this page) Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperative Printed -19- _ _ _ _ _ _ _ _ _ Fi print dry 1295314 A7 B7 five, invention description (17)

Among them, Y1, Y2, Y3 and Y4 are H, F or an optionally fluorinated alkyl group having 1 to 8 c atoms). One (A1 - Z) ^ one and one (Z - A2) b in the formulae II 1 * and II 2 * - is selected from the above-mentioned preferred formula II - 1 to II - 25 and II a to II Preferably, b is the most preferred of the formulae II 1 to I 16 and II a to II f. In the polymerizable liquid crystal forming compound @^ having a nonpolar group, R is preferably an alkyl group of up to 15 C atoms or an alkoxy group having 2 to 15 ίθ<: atoms. If R is an alkyl or alkoxy group (i.e., at the end of a 0-substituted terminal c Η 2 ^ ), it may be straight or branched. It is preferred to have a linear chain of 2, 3, 4, 5'6, 7 or 8 carbon atoms, and therefore apply to the Chinese National Standard (CNS) A4 specification (210X297 mm) on an ethyl, vapor-based basis. )

Ii IIII Pack - III Order - Line III (please read the notes on the back and fill out this page) -20- Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1295314 A7 __B7_ V. Invention Description (18) Base, E More preferably, a hexyl group, a heptyl group, a heptyl group, an octyl group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group or an octyloxy group, Base, fluorene-fluorenyl, 12-yard, tridecyl, tetradecyl, pentadecyl, decyloxy, nonyloxy, undecyloxy, dodecyloxy, tridecane Oxy or tetradecyloxy. An oxoalkyl group (ie, a C 2 group substituted with 〇-) is, for example, a linear 2- propyl propyl group (=methoxymethyl group), a 2-ethoxymethyl group, or a 3-oxobutyl group. (=2 - methoxyethyl), 2 -, 3 ~ or 4 -β-pentyl, 2 -, 3 -, 4 - or 5-octyl, 2 -, 3 -, 4 -, 5 - or 6-β-heptyl, 2-, 3-, 4-, 5-, 6- or 7-π, oxayl, 2-, 3-, 4-, 5-, 6-, 7- or 8-chew Mercapto or 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxime is preferred. In the case of a polymerizable liquid crystal forming compound having a terminal polar group, R is selected from CN, Ν〇2, halogen, 〇CH3, OCN, SCN, COR1, COOR1 or a single having 1 to 4 C atoms, Oligo- or polyfluorinated alkyl or alkoxy. R4 is an alkyl group having 1 to 4 C atoms (preferably 1 to 3 C atoms) which is optionally fluorinated. The halogen is preferably F or C 1 . Among these compounds, R is particularly preferably selected from the group consisting of F, C 1 ^ CN'NOs'OCHs' COCH3> COC2H5, C〇〇CH3, COOC2H5, CF3, C2F5, 〇CF3, OCHF2 and 〇C2F5, especially F, c. 1, cn, 〇ch3&〇cf3. In the compounds of formula I, R can be a non-pivoling or a pair of palmitic groups. This paper scale applies to China National Standard (CNS) A4 specification (21〇χ: 297 mm) 1 Gutter (please read the note on the back and fill out this page) -21 - 绖齐郎Smart Time 苟 Employees' Consumption泎Ti printing 1295314 λ7 __Β7 V. Description of the invention (19) In the case of the palm base, the base is preferably selected according to the following formula III

11*2 -X-Q -CH-Q

Q3 HI wherein the lanthanum is one to one, one s-, one C 〇 one, one c 〇〇 one, - 〇c 〇 one, one 〇 c 〇〇 one or one bond, Q1 has 1 to 10 C atoms Alkyl or alkoxy or a single bond, Q2 is an alkyl or alkoxy group having 1 to 10 C atoms, which may be unsubstituted or mono- or polysubstituted by halogen or CN, and possibly each In the case, one or more unadjacent c H2 groups are independent of each other by a C Ξ c -, a 〇 -, -S -, an NH -, a N (CH3) -, a c 〇 one, a c 〇〇 One, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one An alkyl or alkoxy group having 1 to 4 C atoms different from Q2. If Q 1 in the formula I I is an alkoxy group, it is preferred to have a ruthenium atom adjacent to the palmitic C atom. Preferred palmitic groups R are, for example, 2-butyl (==1-propylpropyl), 2-methylbutyl, 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-two Amyl, 2-octyl, especially for example 2-methylbutyl, 2----- This paper scales the wealth of the family (10) (1) 槻 丨 献 献 献 献 献 献 献 献 献 献 献 献 献 献 献 献 ( ( ( ( ( ( ( ( ( Precautions on the back side of this page) -22- 1295314 A7 B7 V. Description of invention (2()) Sleeping Qilang t Hui Shi production 3⁄4 member X consumption 阼 ii printing base butoxy, 2-methyl pentane Oxy, 3-methylpentyloxy, 2-ethylhexyloxy, 1-methylhexyloxy, 2-octyloxy, 2-oxo-3-methylbutyl, 3-oxyl-4 Monomethylpentyl, 4-methylhexyl, 2-indenyl, 2-indenyl, 2-dodecyl, 6-methoxyoctyloxy, 6-methyloctyloxy, 6-methyloctyl Oxy, 5-methylheptyloxycarbonyl, 2-methylbutanoxy, 3-methylpentyloxy, 4-methylhexyloxy, 2-chloropropyloxy, 2-chloro 3-methyl-butoxycarbonyl, 2-chloro-4-methylpentyloxy, 2-chloro-3-methylpenta Oxyl, 2-methyl-3-oxopentyl, 2-methyl-3-oxohexyl, 1-methoxyprop-2-oxo' 1 -ethoxypropan-2-oxyl, 1 Propoxy-2-methoxy, 1-butoxyprop-2-oxy, 2-fluorooctyloxy, 2-fluorodecyloxy. Furthermore, for example, a compound of formula I containing a non-p-branched branched chain r is occasionally important because it reduces the tendency to crystallize. Branched groups of this type typically do not include more than one branch. Preferred non-p-branched branched groups are isopropyl, isobutyl (=methylpropyl), isopentyl (=3-methylbutyl), isopropoxy, 2-methylpropoxy and 3-methylbutoxy group. Another preferred embodiment of the invention is directed to a compound of the formula wherein R represents P - (Sp - X) n -. In Formula I, the polymerizable group P is selected from the group consisting of 0 w2Mn-CH2=CW1~C〇〇- W2HC — CH - w2 I I I I — I I I I I line (please read the back note before filling in this page)

C H c w

H 〇 a C W 2 W o

(ch2v〇- 〇 I, CHs — CH=CH — 〇一

H S c w 2 w

HW 2 N This paper scale applies to China National Standard (CNS) M specification (2丨〇χ297 mm) -23- Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1295314 λ, Β7 5, invention description (21) h〇- Cw2w3-nh - ^ ch2=cw1-~co-nh- , C Η 2 = C Η — (C〇〇) ki—Phe — (〇)k2 —, Phe-CH=CH-, H〇〇C I. 〇CN—and W4W5W6Si—preferably, W1 is H, C1, CN, phenyl or an alkyl group having 1 to 5 C atoms, particularly H, C 1 or CH 3 , and the W 2 and W 3 systems are independent of each other. An anthracene or an alkyl group having 1 to 5 C atoms, particularly a methyl group, an ethyl group or a n-propyl group, and the W4, W5 and W6 systems are each independently an anthracene, an alkyl group having 1 to 5 C atoms or an oxocarbonyl group. The alkyl group, P he is 1,4 - phenylene, and the ki and k 2 systems are independently 〇 or 1. The oxime is preferably an acrylate group, a methacrylate, a vinyloxy group or an epoxy group, particularly an acrylate group or an epoxy group. As for the spacer S ρ in the formula I, all groups known to those skilled in the art for this purpose can be used. The spacer S ρ is preferably a linear or branched alkyl group having 1 to 20 C atoms, particularly 1 to 12 C atoms, and further, one of them may be -, - S -, - - , one N ( C Η 3 ) one, one C 0 one, one one C 0 —, one S—C〇 one, one one C〇〇, one C〇一 S—, one C〇 one, one One CH (halogen) one, one CH (CN) — , one CH = C Η — or —C three C — replaces one or more non-contiguous C Η 2 groups. Typical spacers are, for example, ethylene, propylene, butadiene, pentylene, hexamethylene, hexamethylene, octylene, yttrium, yttrium, undecylene, dodecane, octadecanene, ethylene Oxyethylene, methylene oxybutyl, ethylene thioethylene, ethylene oxime - methyl iminoethylene, 1-methyl alkyl, vinyl, and propylene paper scales applicable to China Standard (CNS) Α4 size (210χ297 mm) II —.· Binding II I line (please read the note on the back and fill out this page) -24- 1295314 A7 B7 V. INSTRUCTIONS (22) Alkene and butene support. The compound of the formula I of the present invention in which s p represents an alkyl group or alkoxy group having 2 to 8 C atoms is particularly preferred. It is especially preferred to use a linear alkyl group or an alkoxy group. In another preferred embodiment of the invention, the palm-forming compound of Formula I comprises at least one spacer s p, which is a pair of palms of the formula IV: Yu-Q, CH-Q4-

I

Q3 IV wherein Q1 and Q3 have an alkylene or alkoxy group or a single bond having 1 to 1 C atom different from that proposed in Formula II, and Q4 is different from Q1. In this case, R represents P - S p - X, and the two spacers Sp in the compound of formula I may be the same or different. Among the above preferred compounds, those wherein n is 1 are particularly preferred. To include η where η is 〇—(Sp — X) η — and its in! 1 is a group of 1 P - (Sp - X) „ - two compounds are more preferred. The compound of formula I can be synthesized according to methods known in the art or similar to those described in standard organic chemistry, for example, Houben-Weby ,

Methoden der organischen Chemie, Thieme-Verlag, Stuttgart. Particular preparation methods can be employed by way of example. This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) ------------f-- (Please read the note on the back and fill out this page) Property Bureau employee consumption cooperative printing - 25 - Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 1295314 at B7_ V. Invention description (23) In, for example, W〇93/22397, EP 0,261,712, DE 195,04, Examples of suitable polymerizable liquid crystal forming compounds which can be used as a component of a polymerizable CLC material are described in 224, W〇95/22586 and W〇97/00600. However, only the compounds disclosed in these documents are to be considered as examples, and should not be construed as limiting the scope of the invention. The polymerizable C L C mixture is preferably a polymerizable liquid crystal-forming compound containing at least one polymerizable functional group and at least one polymerizable liquid crystal-forming compound having two or more polymerizable functional groups. Examples of particularly useful single-reactive and palm-free polymerizable liquid crystal-forming compounds are shown in the following list of compounds, but are merely illustrative of their use and are not intended to limit the invention in any way. However, the invention is explained by its generation: P-(CH2)x〇000 Y (Va) ρ,2)χ〇Ό^00^Ο^Ό"Υ(Vb) ρ·2)χ〇^3^οο 〇(vc) ρ-(〇Η2)χ〇Όε〇〇+ΟΧ5^. (vd) (Ve) This paper scale applies to the Chinese National Standard (CNS) Α 4 specification (210x297 mm) ----------- Participate ------? τ------- --I (Please read the note on the back and fill out this page) -26- 1295314 A7 B7 V. Inventions (24

P-(CH2)〇 coo

Coo COO-Ter ο CH2CH(CH3)C2H5

P-(ch2)xo P-(CH2)xO -o-~Qr P-(CH2) coo COO-Chol

(Vf)(Vg) (Vh) (Vi) (Vk) (Vm) Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumer Cooperatives, where P has one of the meanings of Formula I, and is better defined as above, X is from An integer from 1 to 12, A is 1,4-phenylene or 1,4-cyclohexene, v-system or 1,Y is a polar group as defined above, and RQ is a non-polar alkyl group as defined above or Alkoxy, Terenyl terpenyl, such as Mendocyl, Cho 1 cholesteryl, and L1 and L2 are each independently Η, F, C 1 , 0 Η, CN, N 0 2 or optionally halogenated An alkyl group, an alkoxy group or a carbonyl group having 1 to 7 C atoms. Examples of useful two-reactive and palm-free polymerizable liquid crystal-forming compounds are shown in the following list of compounds, but are merely exemplified by their actions, and are not intended to limit the present invention in any way. I line (please read the note on the back and then fill out this page) This paper scale applies to Chinese National Standard (CNS) Α4 specification (21〇Χ297 mm) -27- A7 B7 25 1295314 V. Invention description (but with its generation For the purpose of explaining the invention

P(CH2)x〇· coo oco 0(°ΗΛΡ (Via) P(CH2)x〇 ch2ch2

CHXH.

Or

〇(CH2)yP (Vlb) L2 (Vic) P(CH2)x〇 a H CH=CHCOO. I 〇

H 〇〇CCH=CH〇W (v 丨(1) P(CH2)x〇

〇(CH2)vP (Vie) I II _I II Installation - Set II ~" Line (please read the note on the back and fill out this page) The Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, printed P, x, D, The L 1 and L 2 systems have one of the above-mentioned meanings, and the y-system is the same or different from x. The integer from 1 to 12 includes, according to a preferred embodiment of the present invention, the polymerizable liquid crystal material comprises one or more A palm-forming polymerizable liquid crystal forming compound. These compounds are preferably selected from formula I wherein M G, Sp and/or R comprise a palmitic moiety. The palm powder compound selected from the above formulas V a to V m is particularly suitable for the Chinese National Standard (CNS) A4 specification (210X297 mm) -28 - Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1295314 A7 __B7__ V. INSTRUCTION DESCRIPTION (26) In another preferred embodiment of the invention, the polymerizable liquid crystal material comprises one or more non-polymerizable pairs of palmitic dopants. It is especially preferred to have a palm-shaped dopant having a high helical twist energy (Η Τ , ), especially those disclosed in W 0 9 8 / 0 0 4 2 8 . More typically used palmitic dopants such as the commercially available S 1 0 1 1 , 尺 8 11 or 〇 6 15 (taken from 1^1^^[〇3八,〇31*11^&(^ Germany).

Selected from the formula V I I

The palmitic dopants are particularly preferred, including (R'R), (R, S), (S, R) and (S, S) mirror isomers, each of which is not shown. Is a 1,4-phenylene or trans-1,4-1,4-cyclohexene, ν-system or 1 , Ζ °-C 0 0 —, a 〇C〇, a C Η 2 which may be substituted by L as defined above. C Η 2 - or a single bond, and R is an alkyl or alkano group having 1 to 12 C atoms. This paper scale applies to China National Standard (CNS) Α4 specifications (210Χ297 mm) ----------- pain ------, order ------ ^ (please read the back first Note: Please fill out this page again) -29- 1295314 A7 ____ B7 V. Inventions (27) (Please read the notes on the back and fill out this page) In W〇9 8 / Ο Ο 4 2 8 II compounds and their synthesis. The compound of formula V I I I and its synthesis are illustrated in GB 2 '328,207. The palm-forming compounds of the above formulas V I I and V I I I exhibit very high helical twist energy (Η T P ) and are therefore particularly useful for the purposes of the present invention. The first preferred polymerizable liquid crystal material comprises a) 5 to 80% by weight of up to five (one, two or three very preferred) monoreactive liquid crystal forming compounds having a polar terminal group, to 1 0 to 6 5 % is very good, b) 10 to 90% by weight of up to four (one or two very good) one reactive polymerizable liquid crystal-forming compound, preferably from 25 to 75 % , c) 0 · 1 to 1 5 wt% of up to three (one or two very good) non-polymerizable palmitic dopants, preferably 2 to 9 %, d) 0 · 5 to 10% by weight of the polymerization initiator, preferably from 1 to 7%, printed by the Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, e) 0 · 〇1 to 6% by weight of one or more polymerizable surface-active compounds, 〇· 1 to 3% is very good. The second preferred polymerizable liquid crystal material comprises a) from 0 to 30% by weight of up to five (one, two or three very preferred) monoreactive liquid crystal forming compounds having a polar terminal group, Up to 5% is very good, b) up to four of 90% by weight or more (with one or two very good paper scales applicable to China National Standard (CNS) A4 specification (210X297 public) ---*- -30- 1295314 λ7 Β7

Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperatives, Printing 5, Inventions (28) II) Two reactive polymerizable liquid crystal-forming compounds, with 90 to II 9 9 • 5 % Very good, IIC ) 0 • I to I Up to three of 5% by weight (one or two, please I first). Non-polymerizable pair of palmitic dopants, from 0 to 2 to 9% very good, read I back d) 0 • 5 to I 0% by weight of polymerization initiator, I to 7 % Sr I Note I is very good • Refill I e ) 0 • 0 1 to 6 wt% of one or more polymerizable surface active II compounds at 0 · I to 3% is very good. Written in this page I. A particularly preferred mixture of the second embodiment is a mixture of mono-reactive polymerizable compounds which do not contain component I I I a ). III. The first preferred polymerizable liquid crystal material comprises II a) up to five of 80% by weight or more (very good in one, two or three order) single reactive liquid crystal generation having polar terminal groups The compound is preferably II 9 0 to 9 9 • 5 %, III b ) 0 to 20% by weight up to four (very good one or two) II line I direactive polymerizable liquid crystal formability Compounds, preferably from 0 to: 5%, C) 0 • I to I 5% by weight of up to three (in one or two very I | preferred) non-polymerizable pair of palmitic dopants, 0. 2 Up to 9% very good, II d ) 0 • 5 to I 0% by weight of a polymerization initiator, from 1 to 7% II Very good II e ) 0 • 0 I to 6% by weight of one or more polymerizable surface activities The II compound is preferably from 0.1% to 3%. I I A particularly preferred mixture of the second embodiment is a mixture of mono-reactive polymerizable binders which do not contain the component snow I I b ). III sheets of paper are allowed to be used in the country of the country. Wanted public 97 2 31 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1295314 A7 ____________ B7______ V. Invention description (..) The compound of component a) is selected from the above formula V a and V b are preferred. The compound of component b) is preferably selected from the formulae V I a and V I b above. The compound of the component c) is preferably a compound of the formula V I I and V I I I selected from the above. The compound of component e) is preferably selected from the group I X and X selected from the above. According to the method of the present invention, the polymerizable liquid crystal material is coated on the substrate and arranged in a uniform orientation. It can then be polymerized to permanently immobilize the orientation of the cholesterol material. As the substrate, for example, a glass or quartz or plastic film or sheet can be used. In the case of polymerizable materials, the substrate may or may not be removed after polymerization. In the case where the substrate is not taken out from the polymer film after the polymerization, it is preferred to use an isotropic substrate. The substrate may also be a plastic substrate, such as a film of polyester (such as polyethylene terephthalate (PET)), polyvinyl alcohol (PVA), polycarbonate (PC) or triethyl fluorenyl cellulose ( The film of TAC) is particularly preferred as a PET film or a TAC film. A uniaxially stretched plastic film can be used as the birefringent substrate. For example, commercially available I C I is a P E butyl film under the trademark Melinex. Glass substrates are particularly preferred, especially those which are covered with honed polyimine. The polymerizable liquid crystal material can also be dissolved in a solvent, preferably an organic solvent. The solution is then coated onto the substrate by, for example, spin coating or other known techniques, and the solvent is evaporated. In most cases, it is suitable to use the Chinese National Standard (CNS) A4 specification (210X297 mm) for the mixed paper scale ------------^------1T-- --- — Line, (please read the notes on the back and fill out this page) -32- Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1295314 A7 _____B7____ V. Invention Description (3〇) Compound heating to accelerate solvent Evaporation. In addition to the above methods, the shearing of the material in the form of, for example, a doctor blade can further enhance the planar arrangement in the coating layer of the polymerizable liquid crystal material. It is also possible to apply an alignment layer on the top end of the substrate, for example, a honed polyimine layer or a sputtered Si x Ο X layer, or directly honing the substrate, i.e., without coating another alignment layer. For example, honing can be achieved in the form of a honing cloth (such as a velvet cloth) or a flat rod covered with a honing. In a preferred embodiment of the invention, the friction is achieved in at least one honing drum (such as, for example, a fast rotating drum that is brushed across the substrate) or by placing the substrate between at least two rollers in each case. Wherein at least one of the rollers is covered with a honing cloth as desired. In another preferred embodiment of the invention, honing is achieved by shielding at least a portion of the substrate at a specified angle around the drum, preferably by wrapping the drum in a honing cloth. The polymerization of the polymerizable liquid crystal material is achieved, for example, by exposure to heat and actinic radiation. The actinic radiation represents either radiation (such as U V light, IR light or visible light), X-ray or r-ray irradiation or high-energy particles (such as ions or electrons). It is preferred to carry out the polymerization by U V irradiation. For example, a single U V lamp or a U V lamp set can be used as the source of actinic radiation. When using high energy lamps, the curing time can be reduced. Another possible source of actinic radiation is a laser such as, for example, a U V laser, an I R laser or a visible light laser. Aggregation in the presence of an absorbing agent at the wavelength of actinic radiation. This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) _. —I Binding I line (please read the notes on the back and fill in the form) This page) -33- Jing Qilang Zeng Huishi 苟 苟 Employees 汴 汴 12 12 1295314 at __Β7 _____ V. Invention Description (31). For example, when polymerizing in the form of u V light, a photoinitiator which decomposes under irradiation of u V can be used to generate radicals or ions which start the polymerization reaction. In the case of curing a polymerizable liquid crystal-producing substance having an acrylate or methacrylate group, it is preferred to use a photo-based initiator to cure a polymerizable liquid crystal-forming substance having a vinyl group and an epoxy group. It is preferred to use a cationic photoinitiator. It is also possible to use a polymerization initiator which decomposes upon heating to generate radicals or ions which initiate polymerization. For example, commercially available Irgacure 651, Irgacure 184, Darocure 1173 or Darocure 4205 (all from Ciba Geigy AG) can be used as the photoinitiator for the base polymerization, however, in the case of cationic photopolymerization, commercially available ones can be used. UVI 6 9 7 4 ( Union

Carbide). The polymerizable liquid crystal material contains from 0. 01 to 10% of a polymerization initiator, and is preferably from 0.5 to 5%, particularly from 0 to 1 to 3%. Preferably, a U V photoinitiator, especially a based U V photoinitiator. The curing time depends on, for example, the reactivity of the polymerizable liquid crystal generating material, the thickness of the coating layer, the type of the polymerization initiator, and the U V lamp energy. The curing time according to the present invention is preferably not more than 10 minutes, particularly preferably not more than 5 minutes, and even more preferably not more than 2 minutes. For a large amount of production, a short curing time of 3 minutes or less is preferred, and 1 minute or less is excellent, especially 30 seconds or less. In addition to the polymerization initiator, the polymerizable material may also contain one or the paper scale applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -~ -34-

In 装~~ 订. 11 I line (please read the note on the back and then fill out this page) 1295314 Α7 Β7 V. Description of invention (32) A variety of other suitable components, such as catalysts, stabilizers, chain transfer agents Or co-reacting monomers. It is especially preferred to add a stabilizer to avoid undesired spontaneous polymerization of, for example, materials which are polymerizable during storage. In principle, all compounds known to the person skilled in the art for this purpose can be used as stabilizers. These compounds are a wide variety of commercially available products. Typical examples of stabilizers are 4-ethoxyphenol or butylated hydroxytoluene (Β Η T ). Additives such as chain transfer agents may also be added to the polymerizable material to improve the physical properties of the polymer film of the present invention. When a chain transfer agent is added to the polymerizable material, such as a monofunctional sulfur-carrying compound (such as, for example, dodecanesulfurate) or a polyfunctional sulfur-carrying compound (such as, for example, trimethylpropane tris(3-nonyl) The acid ester)) can control the length of the free polymer chain and/or the length of the polymer chain between the two crosslinking agents in the polymer film of the present invention. When the chain transfer dose is increased, the polymer chain length in the obtained polymer film is lowered. In order to increase polymer cross-linking, or in addition to di- or polyfunctional polymerizable liquid crystal-forming compounds, it is also possible to add up to 20% of non-liquid crystalline compounds having two or more polymerizable functional groups. In the polymerizable material to increase the crosslinking of the polymer. Typical examples of the difunctional non-liquid crystal generating monomer are: [to 20 C atomic alkyl diacrylate or alkyl dimethacrylate. A typical example of a non-liquid crystalline monomer having more than two polymerizable groups is trimethylpropane trimethacrylate or pentaerythritol tetraacrylate. The paper size is applicable to the Chinese National Standard (CNS) Α4 specification. (210X297 mm) I--- ------------^-- (Please read the notes on the back and fill out this page) Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives - 35- 1295314 Λ7 B7 V. Inventive Note (33) In another preferred embodiment, the polymerizable CLC mixture contains up to 70% of a non-liquid crystalline compound having a polymerizable group, from 3 to 50% is preferred. Typical examples of monofunctional non-liquid crystalline monomers are alkyl acrylates or alkyl methacrylates. It is also possible to add, for example, up to 20% by weight of a non-polymerizable liquid crystalline compound to accommodate the optical properties of the optical retardation film. In a preferred embodiment of the invention, the polymerization of the polymerizable C L C mixture is carried out under an inert gas to optimize it under nitrogen. The choice of suitable polymerization temperature will depend primarily on the point of purification of the polymerizable material, for example, depending on the softening point of the substrate. The polymerization temperature is preferably at least 30 ° C lower than the purification point of the polymerizable liquid crystal forming mixture, preferably in optical and electrooptical devices such as liquid crystal displays or projection systems, or in decorative or security applications. The mixtures and films of the invention are used. The planarly arranged polymer film obtained with the mixture of the present invention is particularly suitable as, for example, a polarizer, a compensator, a spectroscope, a reflective film, a color filter, a decorative or security imprint, a colored image, a laser imaging element, An optical film for hot-film-foiled foils, and an optical film for liquid crystal pigments for the preparation of decorative or decorative lines such as anti-counterfeit marks or security lines on currency or other value documents. The polymerizable cholesteric liquid crystal mixture and the polymer film obtained therefrom are particularly suitable for use in a part of a film-system composite crystal cell, such as a lining layer or a color filter. For example, a nematic mixture is particularly suitable as an alignment layer, and a cholesteric mixer is particularly suitable as a color filter. This paper scale is applicable to China National Standard (CNS) Α4 specification (210X297 mm) -----Ί-----装-- (Please read the note on the back and fill out this page)

1T Line Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed -36· 1295314 at B7 V. Invention Description (34) No further careful scrutiny is required. Those who are familiar with this technique will make full use of the above instructions. The overall scope of the invention. The following examples are to be construed as merely illustrative, and are not intended to limit the invention in any way. In the above and below examples, all temperatures are expressed in uncorrected degrees Celsius, unless otherwise specified, and all parts and percentages are by weight. The liquid crystal phase behavior of the compounds is exemplified using the following abbreviations: K = crystalline; N = nematic; S = smectic; Ch = cholesteric; 1 = isotropic. The number between the symbols indicates the phase transition temperature in °C. Example 1 As shown in Table 1, three polymerizable cholesteric liquid crystal mixtures A, B and C were formulated. Mixture A includes a polymerizable surfactant, Mixture B is a non-polymerizable surfactant and mixture c does not include a surfactant-----------^! (Please read the notes on the back and fill in On this page) Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperatives Printed Paper Size Applicable to China National Standard (CNS) A4 Specification (210X29*7 Gongchu) -37- 1295314 A7 B7 L, Invention Description (35) Table 1: Aggregation Composition of cholesteric mixture ABC Compound (1) 50.00% 50.00% 50.00% Compound (2) 12.5 0% 12.50% 12.50% Compound (3) 9.02% 9.02% 9.02% Compound (4) 21.95% 21.95% 21.95% Compound (5) 4.5 0 % 4.50% 4.50% 4-methoxyxan 0.03% 0.03% 0.03% TP0 1.00% 1.00% 1.00% Fluorad FX-13 ® 1.00% 1.00% 0.00% FC171 ® 0.00% 1.00% 0.00% CH2=CHC 〇2(CH2)3〇CH.{^C00(^0C0〇-0(— (1) CH2=CHC02(CH2)60 ch3 I coo oco o- 0(CH2)602CCH=CH2 (2) I Binding I line (please Read the notes on the back and fill out this page.) Ministry of Economic Affairs, Intellectual Property Office, Staff and Consumers Co., Ltd. Print CH2=CHCOO(CH2)6〇-o coo O~cn

Ch2=chc〇〇(ch2)6o o coo OCK This paper scale applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) (3) (4) -38- 1295314 A7 B7 V. Description of invention (36

Η 〇C〇 OC6H13 (5) Ministry of Economic Affairs Intellectual Property Bureau employee consumption combined printing can be prepared in a manner similar to the method described in w Ο 9 3 / 2 2 3 9 7 to prepare compounds (1) and (2). Compounds (3) and (4) can be produced in a manner similar to that described by Makromol. Chem. 1 90, 3 20 1 - 3 2 1 5 (1 9 8 9 ) by D. J. Broer et al. The preparation of the palm dopant (5) is illustrated in W 0 9 8 / 0 0 4 2 8 . FX-1 3® is a polymerizable interface active agent of the above formula IX, which is commercially available from 3 M (St. Paul, Minnesota, USA). TP〇(2,4,6-trimethylphenylhydrazine-diphenylphosphine oxide) is a photoinitiator sold under the trademark Lucirin® T P 0 by B A S F (Ludwigshafen, Germany). 4-methoxyphene is a commercially available stabilizer. FC 1 7 1 Formula C n F 2 n + i S 〇2 N ( C 2 Η 5 ) (CH2CH 2 〇) XCH3 non-polymerizable fluorocarbon surfactant 'where η is an integer from 4 to 12 and X system An integer from 5 to 15 is a commercial item of 3 M (St. Paul, Minnesota, USA). Preparation of Membrane A 50% by weight solution of each of the mixtures A, B and C was prepared in xylene. The solution was filtered through a 0.2 μm P T F E membrane filter before use. The first layer of mixture A and B are respectively at 3, 〇〇〇 / this paper scale applies Chinese National Standard (CNS) A4 specification (210X297 mm) -----------^---- --1T—————————^ (Please read the notes on the back and fill out this page) -39- 1295314 B7 V. INSTRUCTIONS (37) After 30 minutes, spin coating on the honing On a polyimide/glass substrate. The film was annealed at 70 ° C for 30 seconds, and photopolymerized at 19 ° C for 60 seconds using a UV-A radiation of 19 · 5 mW in nitrogen at 70 ° C. Next, the second layer mixture C was directly coated on the first layer mixture A and B by rotation, respectively, to prepare a stacked film. The second layer was annealed at 70 ° C for 30 seconds and photopolymerized at room temperature for 60 seconds using U 9.5 MPa of 19.5 mW in nitrogen. Surface energy measurement The surface energy of the mono- and bilayer films produced was measured by contact angle measurement using a Kruss DSA10 instrument connected to P C . Analyze using professional software supplied by the instrument. The contact angles of water (B D Η, Η P L C grade), ethylene glycol (Aldrich 9 9 + % spectrophotometric grade) and diiodomethane (Aldrich 9 9 %) were measured to determine the surface energy of the membrane. Use the solvent supplied. All measurements were taken at 2 2 °C. The contact angles used were based on the average enthalpy measured by Young-LaPlace at least 4 times. Surface energy was obtained using the 〇wen-Wendt-Rabel-Kaelbe (〇W R K ) theory. The data is collected in Table 2. This paper scale applies to China National Standard (CNS) A4 specification (210X29*7 mm) ----------11^ — I (please read the notes on the back and fill out this page) Intellectual Property Office Staff Consumer Cooperative Printed -40- 1295314 A7 B7 V. INSTRUCTIONS (38) Table 2: Measurement of single- and double-layer polymer films of mixtures A, B and C and surface energy y Stacking water/° Ethylene glycol broad diiodomethane wide 7 / mNm * 1 7, d / mNm - 1 7 p / mNm * 1 A 101.78 ± 1.82 77.97 ± 1.04 64 · 04 ± 1.32 25.16 24.65 0.51 B 78.67 ± 0.90 57.23 ± L09 37.72 ± 1.89 39.45 35.67 3.78 C 71.60±1.33 54.51±0.56 41·11±1·55 40.23 33.24 6.98 A+C 70.79±1.06 54.07±1.59 33·49±1·48 42.30 35.92 6.38 B+C 80.84±1.39 59.96±1.95 44.48 ±1.41 36.61 32.87 3.74 ----------^丨| (Please read the notes on the back and fill out this page) The small letters d and p indicate the dispersion of surface energy and polar components. Analysis of the surface energy data of the wire mixture A, B and C films showed that the addition of the surfactant to the liquid crystal mixture reduced the surface energy of the film. The addition of the polymerizable surfactant F X 13 3 makes the overall surface energy reduction of the polymeric film more effective than the non-polymerizable surfactant F C 17 1 . Contact angle measurement analysis using OWRK theory allows the determination of surface energy dispersion and polar components (Table 2). These results demonstrate that the surface energy of the film (A) containing the polymerizable surfactant FX 13 is intrinsically dispersed only by small polarity. The surface energy of the film containing no surfactant (C) exhibits the greatest surface energy with an increase in both the polarity and the size of the dispersed component. The surface energy dispersing component of the film (B) containing the non-polymerizable surfactant F C 17 7 is similar to that of the pure liquid crystal film (C), whereas the size of the polar component is remarkably lowered as compared with (c). Therefore, it is checked that the dispersion of the surface energy of the film and the polarity promoting allow the surfactant to move through the stacked layer to be detected. Add a liquid crystal mixture containing no surfactant (C) in the second layer (a) and (This paper scale applies Chinese National Standard (CNS) A4 specification (210X297 public Chu) -41 - 1295314 A7 B7 Economic Lang Intellectual Property Bureau Employee consumption cooperation 钍 printing five, invention description (39) B) in the two films to produce a stacked film. The surface energy dispersion and polarity promotion of the stacked films of (A) + (B) are very similar only to those of the liquid crystal mixture film containing no surfactant (C), suggesting that the polymerizable surfactant does not move from the lower layer. The upper layer or its movement has been significantly reduced. The dispersion contributions of the films (B) and (C) have similar sizes. Thus, for this example, it is not suitable to use the size of the dispersion of the surface energy of the stacked film (B) + (C) as an index of the movement of the surfactant. However, the polarity in these membranes contributes completely differently. The polarity of the surface energy of the stacked film (B) + (C) is similar to that of the film (B) containing the non-polymerizable surfactant FC 1 7 1 , suggesting that fc 1 7 1 has moved from the first layer to the second Floor. It has then been demonstrated that the use of polymerizable surfactants significantly reduces the movement of the surfactant in the stacked film. Example 2 The following polymerizable nematic mixture was formulated. Compound (1) 99.0% Fluorad FX-13 ® 0.5% Irgacure 651 ® 0.5% Irgacure 651® is a commercially available photoinitiator from Ciba AG (Basel, Switzerland). Example 3 Formulation of the following polymerizable cholesterol type mixture compounds (1) 92.0% Paliocolor LC756 ® 7.0% (Please read the back note and then fill out this page). Loading and setting paper standards apply to Chinese national standards (CNS) A4 size (210X 297 mm) -42- ^齐郎知曰鋈吋轰βίΓΜΚΙΙ肖费乂&乍i Zhongchu 1295314 A7 B7 V. Invention description () 40

Fluorad FX-13 ® 0.5%

Irgacure 651® 0.5%

Paliocolor 756 ® is a two-reactive palmitic compound commercially available from BASF AG (Ludwigshafen, Germany). Example 4 The following polymerizable nematic mixture was formulated. Compound (3) 25.0% Compound (4) 25.0% Compound (6) 49.0%

Fluorad FX-13 ® 0.5%

Irgacure 651® 0.5%

Compound (6) can be prepared in a manner similar to that described in W Ο 9 3 / 2 2 3 9 7. Example 5 Formulation of the following polymerizable cholesteric mixture compounds (3) 25.0% Compound (4) 25.0% This paper size is applicable to China National Standard (CNS) A4 specification (21〇X297 mm). I Gutter (please read first) Precautions on the back side of this page) -43- 1295314 A7 B7 V. INSTRUCTIONS (41) Compound (5) 5.0% Compound (6) 44.0%

Fluorad FX-1 3 ® 0.5%

Irgacure 651 ® 0.5% The above-mentioned steps were repeated with similar achievements by substituting the reactants used in the above steps for the reactants used in the above steps and/or repeating the conditions of the present invention. The person skilled in the art can readily ascertain the basic characteristics of the present invention from the above description, and various changes and modifications can be made to the various uses and conditions without departing from the spirit and scope of the invention. — — — — — 装 — I II 订 (Please read the notes on the back and fill out this page) Line This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -44-

Claims (1)

13⁄41295314 Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives Printed VI. Scope of Application for Patent 彳-1 · A polymerizable liquid crystal material characterized in that it contains one or a kind of polymerizable liquid crystal formability (mesogenic) Compound P-(Sp-X)n.MG-R I wherein P is a polymerizable group, s P has a spacer of 1 to 25 C atoms, X is a 〇-, a S-, a c-one , a C00 —, a C C , a CO — NH — , an NH—C〇, a CH 2 CH 2 —, a 0CH 2 —, a CH 2 〇 , a SCH 2 —, —CH 2 S —, a CH=CH −, -CH = CH-COO - ' - 0C0~CH=CH - ^ -CeC~ or single bond, η system or 1, MG liquid crystal generating group, and R system H, CN, N〇2, halogen or a linear or branched alkyl group having up to 25 C atoms which may be unsubstituted or mono- or polysubstituted with halogen or C oxime, or it may be one or more non-contiguous CH 2 groups in each case Independent of each other - s -, one ΝΗ -, one N (CH3) -, one C 〇 one, one C 〇〇 one, one 〇 C 〇 one, one 〇 C 〇 one 、 one, one s - C 〇 one , , C 〇 S — or C — is replaced in such a manner that oxygen atoms are not directly connected to each other, or R represents P 〜(Sp — X) η —, and 〇·0 1 to 15% by weight of the polymerizable surface The active compound, the polymerizable surface-active compound is a polymerizable fluorocarbon surfactant. Please read the back of the CC first. v|Notes: Fill in the education] -Installation ir -45 1295314 Λ8 B8 C8 D8 々, patent application scope 2 2 ·According to the polymerizable liquid crystal material of the first application patent scope, It is characterized in that it contains less than 20% by weight of a polymerizable liquid crystal forming compound having a nonpolar end. The polymerizable liquid crystal material according to claim 1 or 2, wherein the polymerizable surface-active compound comprises one or two selected from the group consisting of an acrylic group, a methacryl group, an epoxy group, a vinyl group, and an ethylene group. A polymerizable group of an oxy group, a styrene or a propylene ether group. 4. The polymerizable liquid crystal material according to claim 1 or 2, wherein the polymerizable surface active compound is selected from the group consisting of a compound of the formula CnF2n + 1S02N(C2H5)CH2CH20C0CH = CH2 IX(FX-13) CnF2n + 1S02N(C2H5)CH2CH20C0C(CH3) = CH2 X(FX-14) wherein n is an integer from 4 to 8, and the perfluoroalkyl group may be straight or branched. 5. The polymerizable liquid crystal material according to claim 1, characterized in that it is basically composed of a) 5 to 80% by weight of up to five kinds of single reactive liquid crystals having polar terminal groups. Compound, b) 10 to 90% by weight of up to four di-reactive polymerizable liquid crystal-forming compounds, c) from 1 to 15% by weight of up to three non-polymerizable pairs of palmitic dopants , d) 5·5 to 10% by weight of polymerization initiator, e) 〇· 〇1 to 6% by weight of one or more polymerizable surface paper sizes applicable to China National Standard (CNS) A4 specification (210X297厘) ------^----装-- (Please read the «Precautions on the back and fill out this page) Customs Department of Intellectual Property Intelligence Bureau Staff Consumer Cooperative Print -46-1295314 A8 B8 C8 D8 VI. Apply for a patent range of 3 compounds. 6. The polymerizable liquid crystal material according to claim i of the patent application, characterized in that it consists essentially of a) 〇 to 30% by weight of up to five single reactive liquid crystals having polar terminal groups a compounding compound, b) up to four di-reactive polymerizable liquid crystal-forming compounds of 90% by weight or more, C) 1. 1 to 15% by weight of up to three non-polymerizable palmitic admixtures a dopant, d) from 0.5 to 10% by weight of a polymerization initiator, e) from 0 to 0.1 to 6% by weight of one or more polymerizable surface-active compounds. 7. The polymerizable liquid crystal material according to claim 1, wherein it is substantially composed of a) 80% by weight or more of up to five single reactivitys having polar terminal groups. a liquid crystal forming compound, b) 0 to 20% by weight of up to four kinds of direactive polymerizable liquid crystal forming compounds, c) 1. 1 to 15% by weight of up to three non-polymerizable palms a dopant, d) 5. 5 to 10% by weight of a polymerization initiator, e) 01. 01 to 6% by weight of one or more polymerizable surface-active compounds. 8 · A variety of papers with a low inclination angle and arranged in a plane are applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) ------:----^-- (please first Read the notes on the back and fill out this page. Customize the Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumer Cooperatives Printed -47-1295314 A8 B8 C8 D8 Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives Printed VI, Patented 4 Polymers A film method of coating a substrate with a polymerizable liquid crystal material according to claim 1 of the patent application, arranging the materials in a planar orientation and polymerizing the material. 9. An anisotropic polymer film arranged in a plane obtained from the polymerizable liquid crystal material according to item 1 of the patent application. The anisotropic polymer film ‘ according to claim 9 of the patent application is characterized in that the inclination angle is less than 3 degrees. An anisotropic polymer film according to claim 9 or 10, which exhibits a helical twist molecular orientation. 1 2. The polymerizable liquid crystal material according to the scope of the patent application section 1 is used in optical devices, in decorative or security applications, polarizers, compensators, beamsplitters, alignment layers, reflective films, color filters, lightning Photographic elements, hot stamping foils, pigmented images, decorative or security imprints, and liquid crystal pigments for decorative or security applications. 1 3 · Anisotropic polymer film according to item 9 of the patent application scope is used in optical devices, in decorative or security applications, polarizers, compensators, beamsplitters, alignment layers, reflective films, color filters, Laser photographic elements, hot stamping boxes, color images, decorative or security imprints, and liquid crystal pigments for decorative or security applications. A colorant comprising the polymerizable liquid crystal material according to item 1 of the patent application or the anisotropic polymer film according to item 9 of the patent application. 1 5 · an arrangement layer comprising a polymerizable liquid crystal material according to item 1 of the patent application scope or an offset paper according to item 9 of the patent application scope Hi Hi s® Jia Xian (public) ---- ------^------Book ------0 (Please read the note on the back of the Jing and then fill out this page) -48- 1295314 as C8 D8 VI. Patent application scope 5 Film. (Please read the note on the back of the department and then fill out this page) -Installation - Line Printed by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) -49-