TW200417596A - Polymerised liquid crystal film with improved adhesion - Google Patents

Description

200417596 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to a film containing a polymer liquid crystal (LC) material having improved adhesion to a substrate (especially a plastic substrate), a method for preparing the film, and a method for preparing the film. Polymerizable LC materials for films, claddings comprising the films, and uses of the films, materials, and claddings for optical, electro-optical, decorative, or security devices and applications. [Prior art] Polymerizable liquid crystal (LC) materials are commonly used to prepare optical films in liquid crystal displays. These materials usually contain compounds having a quantitative amount of two or more polymerizable groups (di- or polyfunctional) that are cross-linked to obtain a hard film. However, these hard films are often not easy to adhere to the surface of plastic substrates commonly used in manufacturing processes, because the film shrinks due to the polymerization and cross-linking processes. Therefore, films made from this lc material are usually delaminated and bonded to another substrate, such as glass or plastic for polarizers in liquid crystal displays. However, the process of delamination and application to selective substrates is time and material intensive. This also gives two potential points at which film loss can occur from damage during delamination or relamination, resulting in lower overall product yields. It has been technically reported that the LC polymer film is adhered to a plastic substrate with an adhesive and adjustment layer. For example, U.S. Patent No. 5,631, Q51 discloses a method for preparing an optical compensation sheet on a transparent substrate of triacetyl cellulose (TAC). This method first provides a gelatin adhesive layer on a TAC film. Then, the gelatin layer is coated with a modified polyvinyl alcohol (pvA) chemically modified by adding a polymerizable group, and a mixture is formed so that the surface of the polymerized PVA layer is rubbed and unidirectionally rubbed. O: \ 89 \ 89989 DOC -6- 200417596 Whole floor. Finally, an optically anisotropic layer containing a dlscotic LC material is coated on the rubbed surface of the PVA layer and polymerized. U.S. Patent No. 5,747,121 discloses a method for preparing an optical compensation sheet by coating a transparent substrate with an ethnopolyvinyl alcohol (PVA) chemically modified by adding a polymerizable group. The solution causes the solvent to evaporate and rubs the surface of the PVA layer unidirectionally. An optically anisotropic layer containing a discotic LC material is then coated on the rubbed surface of the PVA layer and polymerized. The film is then subjected to heating, whereby the PVA layer and the discotic LC layer are chemically bonded to each other by free, crosslinkable groups. ^ The above method requires many separate coating steps. In addition, the use of several intermediate layers (e.g., adhesive or adjustment layers) containing an isotropic material (e.g., gelatin or PVA) may negatively affect the optical performance of the optical film. Therefore, it is necessary to provide a film of a crosslinked IX material sufficiently adhered to a plastic substrate by a favorable method, which saves time and allows loss to be reduced by processing damage of the Lc film. The inventors of the present invention have discovered that the above-mentioned prior art methods are deficient

Points can be included by using a low percentage 屮 — 斗 、 夕 A

Knife-by-one or polyfunctional compounds of polymerizable LC materials are used to overcome, for example, the preparation of LC polymer films with a low degree of cross-linking for optical components. This film is more industrious, and it is more suitable for plastic substrates commonly used in the optical film industry. Since the low cross-linked Lc is a &, L ^ ^^^ thick film is soft and sensitive to mechanical stress, it is preferably covered by a hard coating or another polymerized LC film containing a degree of cross-linking. . Highly cross-linked hard LC film Γ 1-…, can be used as a protective layer of soft LC film, and laminated to a plastic substrate or another

First, when special film is used, soft LC film can be used as an adhesive layer for hard LC film.

O: \ 89 \ 89989.DOC 200417596 W0 No. 96/10768 describes the preparation of a film comprising a polymerized LC material with a tilted or open orientation. The orientation of the LC material is obtained by applying a pre-tilted layer that also includes a polymerized LC material. However, WO No. 96/10768 does not disclose the use of LC materials with different amounts of di- or polyfunctional compounds, and does not raise the problem of poor adhesion of hard LC films and / or mechanical damage of soft LC films. [Glossary] "Film π" includes a self-supporting (ie, free standing) film or a material layer showing greater or less significant mechanical stability and flexibility and a coating on a support carrier or between two substrates or Layer. Π liquid crystal or mesogenic material, or, liquid crystal or mesogenic compound, including one or more rod-shaped, plate-shaped or disc-shaped mesogenic groups (ie, has the ability to induce liquid crystal phase characteristics (Group)) materials or compounds. Liquid crystal (LC) compounds with rod-like or plate-like groups are also technically called, catastrophic, and liquid crystals. Liquid crystal compounds with disc-like groups are also technically called , Mesogenic, liquid crystal. Compounds or materials containing mesogenic groups do not necessarily have to exhibit a liquid crystal phase by themselves. They only show no liquid crystal phase in mixtures with other compounds or in poly mesogenic compounds or materials or their mixtures. The characteristics are also possible. Team day—whatever it is, use the earlier in the sentence, and "mesocrystal," the mesogenic group for materials 'Among discotic compounds Preferred orientation of the crystal direction of the middle dielectric preferred orientation direction of the short molecular axis of the liquid crystal material of the middle finger. "Planar structure" or, "a ten-face orientation" refers to a layer of optically anisotropic material in which the optical axes are substantially parallel to the square + plane.

O: \ 89 \ 89989.DOC -8-

Vertical structure " or "Higou A plane. Orientation" refers to a layer in which the optical axis is substantially perpendicular to the layer, especially an anisotropic material. Inclined structure "Formula" and "90. The oblique direction of the door" refers to a layer in which the optical axis is inclined with respect to the layer plane at an outer angle of 0, 0, and an anisotropic material. Wave open structure 丨 ’or 丨 丨 with 丨 6 ^, Khan 疋 direction refers to the inclined orientation as defined above, the inclination angle Λ 0 stone 0 Λ in the middle sound. J ^ r yw's square white and white π monotone variation monotonic change 'is preferably changed from the minimum to the maximum value in a direction perpendicular to the layer plane.卞 Unless otherwise specified, choose M, and the inclination angle of the plane about M open layer is taken as the average inclination angle. "Average of ten average inclination angles Θ are defined as d Σ Θ, (d ') θ d where ^ degrees. (D, ) Is the local inclination angle of the layer's intrinsic thickness d, and d is the total layer thickness 'f spiral winding structure' refers to a thin film of liquid crystal material that includes a layer of liquid crystal, and its different molecular orientations "the soil direction uses its main molecular axis" Orientation, flat. Che Fujia's orientation direction is wound around the spiral axis at an angle φ. "Presented :: Helical winding structure with two faces" refers to the above-mentioned spiral second version, in which the spiral axis is substantially vertical, and is lost in production η 仏, which belongs to the membrane surface, that is, substantially flat; f two H lines. This definition includes 75 degrees to W with respect to the phase plane, excellent δ5_. May 3 a a few LJ into the liquid crystal material alone solid or Luo 5 weight percent (weight ^ total amount of compounds. Li / °) is relative to the material _ solid or liquid

O: \ 89 \ 89989.DOC 200417596 [Summary of the Invention] The present invention relates to a film containing a polymerized liquid crystal (LC) material, which is characterized in that it is obtained from a polymerizable material that contains no more than 7% by weight of Or more polymerizable groups of compounds. The invention further relates to a polymerizable LC material comprising not more than 7% by weight of a compound having two or more polymerizable groups. The present invention relates to a multi-layer including a plastic substrate, at least one polymer film and up to one layer of a hard coating film with improved resistance to mechanical stress provided on the substrate, The hard coating film is provided on a surface of the at least one LC polymer film facing away from the substrate. The invention further relates to a method for preparing a polymer film or cladding according to the invention. The invention further relates to the use of the film, material, cladding or method according to the invention for optical, electro-optical, information storage, decoration or security applications.

The invention further relates to an optical element or device comprising a film, material or cladding according to the invention. S The invention further relates to a liquid crystal display comprising a film, a material or a complex sound according to the invention. The invention further relates to an authentication, verification or security mark or colored image comprising a film, material or laminate according to the invention. The invention further relates to a valued object or document containing a #identification, verification or security mark or image as described herein. [Performance Mode] As mentioned above, the low-crosslinking ^ guide plate according to the present invention is soft and tends to be sensitive to mechanical stress in some applications 0 \ 89 \ 89989 DOC -10- 200417596. Therefore, in a preferred embodiment, the low-parent LC film according to the present invention is protected from damage by a hard coating or a protective film. Suitable hard coatings or protective films are known to the professional and published in the literature. Particularly suitable and preferred hard coatings are selected from cross-linked acrylate formulations containing mono ... di- or polyfunctional acrylates, such as methacrylate, 1,6-hexanediol-diacrylate ( HDDA), tripropylene glycol diacrylate (TPGDA) or tetrapentaerythritol tetraacrylate, and commercially available polymerizable formulations or hard coatings such as Ebecryl (g) 27, 5129 or 35 (from ucb chemical ), Topcoat 604 (from Eques coatings B v, NL) or a mixture or modification of it. The present invention further relates to a method for preparing a multi-layer, by providing a polymerizable LC material layer on a plastic substrate, the material layer containing not more than 7% by weight of a compound having two or more polymerizable groups, -Adjusting the LC material to a consistent orientation as needed,-polymerizing the LC material, and-providing a hard coating on the free surface of the polymerized LC material. The low-crosslinking LC film according to the present invention particularly has an excellent adhesion effect on a plastic substrate, and therefore, can be used as an adhesive or a base coating for a subsequent LC layer that does not sufficiently adhere to the substrate. In addition, the low-crosslinking 1 ^ film according to the present invention can adjust the subsequent IX layer applied on the low-crosslinking LC film. Therefore, it can be used as an adjustment layer for subsequent plutonium. By changing the thickness of the Lc film according to the invention, the orientation of the subsequent M layers can be influenced, especially the tilt angle. For example, a thinner LC film with a planar O: \ 89 \ 89989 D0C -11-200417596 orientation according to the present invention can be used to induce the planar orientation of the subsequent LC layer. A thicker LC film having a tilted or expanded orientation according to the present invention can be used to induce a tilted or expanded orientation of a subsequent LC layer. Therefore, another preferred embodiment of the present invention is directed to a cladding that includes low crosslinking A base layer of a soft LC film, and further comprising at least one additional polymerized L [thin film having a higher degree of parental connection and therefore harder than the base layer. The hard LC film serves as a protective layer for the soft LC film, and the soft LC film serves as an adjustment layer and / or an adhesive layer for the hard LC film when coated or laminated on a plastic substrate or another optical film element in a display or optical device. . In the above-mentioned multi-layer, a soft LC film or a hard film or two kinds of films can be used as the optical layer. The conventional hard coatings containing isotropic or stretched polymers or: protective, adhesion or adjustment layers compared to 'hard and soft ... films have the advantage of' can be improved using lc materials with similar optical properties Optical properties of the final optical product. In the optical film industry, it is necessary to keep the film to the maximum

. This saves the thickness of other layers. It is impossible to reduce the thickness of the above-mentioned multi-layered towel because the thickness of the layer is divided by the required optical properties. Only one of the soft and hard LC films is used as a light.

O: \ 89 \ 89989 DOC -12- It is preferably not more than 1 micron, particularly not more than 0.5 micron, and very preferably not more than 0.2 micron. The invention further relates to a method for preparing a multi-layer, which is provided by-providing a first polymerizable 1 ^ < :: material layer on a plastic substrate, the material layer comprising no more than 7% by weight of two or more The compound of the polymerizable group, depending on whether to adjust the 3 LC-LC material into a uniform orientation, to polymerize the first LC material,-providing a second polymerizable LC material on the free surface of the first polymerized LC material Layer, the material layer containing no more than 20% by weight of a compound having two or more synthesizable groups,-adjusting the second LC material to a uniform orientation as needed, and-polymerizing the second LC material . The low-crosslinking LC film preferably has a planar orientation. The highly crosslinked LC film preferably has a planar or oblique or open orientation. Suitable plastic substrates are known to professionals and published in the literature, such as conventional substrates used in the optical film industry. Particularly suitable and preferred substrates for polymerization are, for example, polyesters such as polyethylene terephthalate (pET) or polyethylene naphthalate (PET), polyvinyl alcohol (PVA) Polycarbonate (pc) or triacetyl cellulose (TAC), particularly preferably pet or TAC. The LC film is preferably prepared from a polymerizable LC material by in-situ polymerization. In a preferred preparation method, a polymerizable LC material is coated on a substrate, oriented in a desired orientation and then polymerized, for example, exposed to heat or actinic radiation, such as WO No. 01/20394, British Patent No. No. 2,3 15,072 or WO No. 98/04651. Therefore, the present invention further relates to a method for preparing a polymerized LC film having improved adhesion to a substrate O: \ 89 \ 89989 DOC -13- 200417596, which is provided by-providing a polymerizable LC material layer on a substrate, which The material layer contains no more than 7% by weight of a compound having two or more polymerizable groups,-adjusting the LC material to a uniform orientation if necessary,-polymerizing the LC material, and-removing the polymerized film from the substrate if necessary. . Particularly preferred polymerizable LC materials for use in preparing low-crosslinking films include (by weight%) -70 to 99%, preferably 85 to 99%, and excellent 93 to 99%. One or more having a polymerizable group A compound of _ greater than 0 to 7%, preferably 1 to 7%, excellent 2 to 7%, most preferably 4 to 7% or more compounds having two or more polymerizable groups, -0 to 15 %, Preferably 0 to 10%, excellent 0 to 5% of a non-polymerizable compound, -0 to 10%, preferably 0 to 6%, one or more polymerization initiators. The polymerizable compound used for the polymerizable LC material is preferably a mesogenic or liquid crystal compound. Therefore, the polymerizable LC material generally includes one or more polymerizable mesogenic or non-opposing mesogenic or liquid crystal compounds. Preference is given to a mixture comprising one or more polymerizable compounds having one polymerizable group (monoreactive) and one or more polymerizable compounds having one or more polymerizable groups (two or more reactive). In another preferred embodiment, the polymerizable LC material comprises up to 20% by weight of a single reactive non-mesocrystalline compound having one polymerizable functional group. "Holy examples are alkyl acrylates or methyl methacrylates having alkyl groups of 1 to 20 carbon atoms.

O: \ 89 \ 89989.DOC -14-200417596 In another preferred embodiment, ^ LC materials do not include;-polymerizable parent film ^ compounds having more than two polymerizable groups. In another preferred embodiment, the IX material is a non-palladium material. § A polymerizable material for preparing a low parent film, that is, it does not contain a palmar compound. Non- "compounds include, for example, additives such as catalysts, sensitizers, Meng Ling, J, ..., Γ 疋 liniments, chain transfer agents, inhibitors, lubricants, interstitial agents, Hydrophobic agent, adhesive, flow improver, defoaming agent, degassing agent, diluent, reactive dilution% " agent colorant, dye or other polymerizable LC materials used to prepare high cross-linked film It preferably includes the compound with a heavy polymerizable group in an amount of%, particularly preferably greater than 4.% by weight, and extremely preferably greater than 6. β In the example of the South Father Union LC film, it can also be selectively or in combination with two-or Multi-reactivity: Polymerization of mesogenic compounds. Up to 20% by weight of non-mesogenic compounds with two or more polymerizable functional groups are added to the polymerizable LC material to increase the degree of crosslinking. For -reactive non-mesogenic single A typical example of a polymer is a diacrylic acid vinegar having 1 to 2 carbon atoms or a methacrylic acid ester. A typical example for a multi-reactive non-mesogenic monomer is trimethylpropane triacrylate or Tetrapentaerythritol tetraacrylate. Polymerizable LC materials described herein This is another object of the present invention. The polymerizable mesogenic mono-, di-, and polyreactive compounds used in the present invention can be prepared by a method known per se, for example, described in standard organic chemistry works such as HOUben_Wey1, Mothoden der organischen Chemie,

Thieme-Verlag, Stuttgart 〇

O: \ 89 \ 89989.DOC -15- 200417596 Examples of suitable polymerizable mesogenic compounds that can be used in the polymerizable LC mixture with the compound according to the invention as monomers or co-monomers are disclosed, for example, in W 〇 No./22397, European Patent No. 0261 712, German Patent No. 195 04 224, WO No. 95/22586, No. 97/00600, and British Patent No. 2 351 734. However, the compounds disclosed in these materials should be used only as non-limiting examples of the scope of the invention.

Examples of particularly useful palmitic and non-palmable polymerizable mesogenization: mesogen) are shown in the following enumeration, which should only be used as: No # • Hope to be limited in any way and used to explain the invention: P- (CH2) xO c〇〇〇 ^^ _ r〇 * (R1) p Ό 咖 (R2) (R3) p (ch2), 〇- ^ coo ^ 〇c〇 ^ r0 (R4) (R5)

O: \ 89 \ 89989.DOC -16- 200417596 P- (CH2) 0-

A)-Z〇- P (CH2) -0

, 〇 A > -R0 (R6)

(R7)

p- (ch2) x0 Qin CH = CH — COO 仏. (R8)

P (CH2) x〇— <. A

Ru (R9) (L) r iL) 「

P (CH2) 0-< A (R10)

(R11) P- (CH2) x〇 一 ^ V (COO)

CH2CH (CH3) C2H5 (R12), ~ Qr

P- (CH2) xO-<; coo -Sv, V- coo V- CH2CH (CH3) C2H (R13) p- (CH2) xo COO-Ter (R14) p- (ch2) x〇 医 COO-Chol (R15)

O: \ 89 \ 89989 DOC -17- 200417596 p- (CH2) xo- < / v- coo (R16) p (ch2) x〇 〇-c〇

(R17)

P (CH2) xO COO 〇c〇

〇 (CH2) yP (R18), < y

P (CH2) X0 ch2ch2 chxh

0 (CH2) yP (R19)

L2 C〇A \ / gt; 〇, 〇

(R20)

P (CH2) x〇-{(^ Z〇 ^ Q- CH = CHO

f: 0 (R21)

OOCCH = CH \ MZ〇 \ A P (CH2) x〇-{(^ Z〇j ^ COO f (R22) 〇 Ξ

, 〇 (ch2) p

.〇 (CH2) yP (R23)

O: \ 89 \ 89989 DOC -18- 200417596 In the above formula, P is a polymerizable group, preferably acrylfluorenyl, methacrylfluorenyl, ethylene, vinyloxy, propyl, cyclic Oxy, oxetane or styryl, X and y are the same or different integers from 1 to 12, and A is a mono-, di- or tri-substituted 丨, 4-phenylene or丨, 4_ cyclohexyl, u and v are independent of each other as 0 or! , Z〇 is 弋 〇〇-〇 (: 〇_ '-CH2CH2-, -CH = CH-, -CeC- or a single bond, Ro is a polar group or a non-polar group. Ter is a terpenoid group For example, menthol, 1] 1 is a cholesteryl group, and L, L1, and L2 are independent of each other as H, F, C1, CN, or optionally an alkyl group or an oxygen group having 1 to 7 carbon atoms. Alkoxy, alkoxy, oxo, oxo, oxo, or oxocarbonyloxy, and r is 0, 1, 2, 3, or 4. The phenyl ring in the above formula consists of 1, 2, 3, or 4 as needed Each group is substituted by L. "Polar group" in this connection means selected from the group consisting of F, Ci, CN, No2, 0H, 0CH3, 0CN, SCN, optionally fluorinated with up to 4 carbon atoms "Alkylcarbonyl, alkoxycarbonyl, alkcarbonyloxy or alkoxycarbonyloxy or mono-, oligo- or polyfluorinated alkyl or alkoxy groups having 1 to 4 carbon atoms." Non-polar group The group π refers to an optionally halogenated alkyl group, alkoxy group, alkoxy group, alkoxy ^ anyl group, having 丨 or more (preferably i to 12) carbon atoms not covered by the above definition of "polar group" Burned oxyoxy or burned oxyoxy. To prepare a spiral wound structure Residual LC films, polymerizable LC materials preferably include one or more non-palladium polymerizable mesogenic compounds and at least one palmar compound. Palmar compounds can be selected from non-polymerizable palmar compounds (eg, Xi Known palmitic dopants) or polymerizable palmitic compounds, all of which can be mesogenic or non-mesogenic. Suitable polymerizable palmitic compounds are, for example, those listed above. More

O: \ 89 \ 89989 DOC -19- 200417596 Suitable palmitic polymerizable compounds are, for example, commercially available paiioc (ii) materials (from BASF AG, Germany). Suitable for non-reactive palmitic dopants. From (for example) commercially available or S-8u, wS_1011, wS, u, Ris_30ii, ws_4〇ii, R- or S-5〇11 or CD5 (from Merck KGaA, D__,

Germany). Excellent is a compound having a high spiral winding power (Ητρ), particularly a sorbitol group-containing compound as described in WO 帛 98/00428, and a hydrogenated benzoin as described in GB 2nd Wind 2G7. Alkyl-based compounds, as described in WO 02/9 bond para-naphthalene derivative, as described in the purchase of 02 / Phase 9 age-sensitive derivative 'as wo Palmitic taddOl derivatives described in G2 / () 6265 and having at least one fluorinated linker and a terminal or central palm as described in WO No. 196 and No. Antagonistic compounds of sex groups. The polymerizable material is preferably dissolved or dispersed in a solvent, and more preferably an organic solvent. The solution or dispersion is then applied to the substrate, for example, by spin coating or other known techniques, and the solvent is evaporated before polymerization. In most cases ^ To promote solvent evaporation, it is suitable to heat the mixture. The polymerizable LC material may additionally include a polymeric adhesive or one or more monomers and / or dispersion aids capable of forming a polymeric adhesive. Suitable adhesives and dispersion aids are disclosed, for example, in Evaluation No. 96 / 〇2597. However, it is particularly preferred to use LC materials without adhesives or dispersing aids. In another preferred embodiment, the polymerizable LC material includes an additive that induces or promotes the adjustment of the material on the substrate. Additives preferably include

OA89 \ 89989.DOC -20- 200417596 or multiple surfactants. Suitable surfactants are described in, for example,] Cognard. Mol. Cryst. Liq. Cryst. 78? Supplement 1, l-77 (1981). Particularly preferred are non-ionic surfactants, and very preferred are fluorocarbon surfactants, such as the commercially available fluorocarbon surfactant FluOrad FC_m⑧ (from 3%) or Zonyl FSN® (from DuPont) . The polymerization of the LC material is preferably polymerized by its exposure to actinic radiation. Actinic radiation refers to irradiation with light (for example, UV, IR, or visible light), irradiation with tritium or 7-rays, or irradiation with high-energy particles (for example, ions or electrons). The polymerization is preferably carried out by light irradiation, particularly by UV light. As a source of actinic radiation, for example, a single UV lamp or a group of ultraviolet lamps can be used. Reduces maturation time when using high lamp power. Another possible source of light irradiation is a laser, such as a νν laser, a set laser, or a visible laser. The polymerization is performed in the presence of an initiator that absorbs the wavelength of actinic radiation. For example, in the polymerization by UV light, a photoinitiator which can be decomposed under UV irradiation to produce a radical-supporting reaction can be used. It is preferred to use a νν photoinitiator, especially a radical UV photoinitiator. Available (for example)

Irgacure® or Darocure® series (both from Ciba Gergy AG) are used as standard initiators for radical polymerization, and in the case of cationic photopolymerization ', commercially available UVI 6974 (Union Carbide) can be used. The polymerizable LC material may additionally include one or more other suitable components, such as catalysts, sensitizers, stabilizers, chain transfer agents, inhibitors, co-reactive monomers, surfactants, lubricants, wetting agents, dispersions Agents, hydrophobic agents, adhesives, flow improvers, defoamers, degassing agents, diluents, reactive diluents, adjuvants, colorants, dyes or pigments. O: \ 89 \ 89989 DOC -21-200417596: To improve the physical properties of polymer films, and also to transfer-or a variety of chains: add polymerizable materials. Particularly preferred is a thiol compound = combined input, such as ten: thiol) or a polyfunctional thiol compound (eg, methylpropane tri (mercaptopropionate)). Once.,)) Excellent for mesogenic or liquid crystal thiolization character. When a chain transfer agent is added, the length of the free polymer chain and the long chain of the polymer chain between two parent links in the polymer film of the present invention or ㈣M can be controlled. § When the amount of chain transfer agent increases, it decreases again. The polymer chain length in the Lc film according to the present invention may be reused, and 70 pieces of light in the night-time display or projection system (such as a polarizer, a complement of 1 shell, and a Η-shaped polarizer Or color filters), as a non-descript image, for the preparation of liquid crystals, or as an effect, especially as a reflective film with a spatially changing reflective color, for example, as a multi-color image for decoration, information storage, or security purposes, such as non-durable documents ( Such as ID cards or credit cards), banknotes, etc. The LC film or multilayer according to the present invention can be used for a display of a transmission or reflection type. They can be used in conventional LCDs, especially those in DAp (Adjusted Phase Deformation) or VA (Vertical Adjustment) modes, such as coffee (electrically controlled birefringence (color super-entropy), VAN or VAC (vertically adjusted nematic or bile) (Retained) display, (multiple 4 vertical adjustment) or PVA (patterned vertical adjustment) display for curved mode display or hybrid display 'for example' 〇CB (optical compensation unit or optical compensation birefringence), R-OCB (Reflected 0CB), HAN (Hybrid Adjusted Nematic), or 7Γ-unit display, further for TN (wrapped nematic), htn (high wound nematic), or STN (super wound nematic) mode displays for AMD A TN (active matrix driven τν) display or an IPS (In-Plane Switching) mode display also used as a "Super TFT, · O: \ 89 \ 89989.DOC -22- 200417596 display. Especially preferred are VA, MVA , PVA, OCB, and 7Γ-unit display. The following examples are used to illustrate the present invention without limiting it. In this document, all temperatures are in degrees Celsius and all percentages are by weight unless otherwise specified. Example 1-Preparation Contains low-crosslinking LC film and high LC multi-layer film with the following formulations having low amounts of double-reactive compounds polymerisable LC mixture Ml

Ml: (1) 41.6% monoreactivity (2) 32.0% monoreactivity (3) 16.2% monoreactivity (4) 5.7% dual reactivity Irgacure 907 4.0% Fluorad FC171 0.5% 〇

CN

O: \ 89 \ 89989 DOC -23- 200417596

IrgaCUre 907 is a commercially available photoinitiator (from Siba-Geigy AG) (Clba

Geigy AG). Fluorad! ^ _ 171 is a commercially available nonionic fluorocarbon surfactant (from 3M Company). A polymerizable wc mixture M2 M2 with a high amount of dual-reactive compounds was prepared as follows: (1) ⑺ (4) Fluorad FC171 Irgacure 907 7 * 0% single-reactivity 21.0% single-reactivity 66.5% dual-reactivity 0.5% 5.0 %

Both Ml and M2 were prepared as a% by weight solution in toluene / cyclohexanone (7: 3). The base material used in all cases was triethylammonium cellulose (butylene A.). The / AC substrate was rubbed at 3 × 100 mm and coated with a solution of mi with a 丄 wire wound rod. The solvent was allowed to evaporate at room temperature, and the resulting film was polymerized 4 times by a Mmicure UV lamp system at 20 m / min. Jinde's special film is a clean, plane-adjusted film, which has 100% adhesion when tested by the cross hatch method. ^ After that, the sacral membrane sample was coated again with a wire wound rod with a% 2 solution, so that

O: \ 89 \ 89989.DOC -24- 200417596 The solvent evaporates at room temperature and is tested in the same manner as described above. In the case where the M2 is coated on the matured M1 without friction, it is generated on top of the M1 layer. A clean, highly crosslinked polymer film of M2 with an inclined structure. The adhesion of the M2 layer to the M1 layer was examined by the intersection method and found to be a post. Therefore, the low-crosslinking film of 'Ml is used as an adhesion and adjustment layer for a crosslinked film. Rubbing the erbium layer before coating with M2 results in adjustment loss, a scattering film, and: adhesion. Example 2-Reducing film thickness A single-layered rod was used to obtain a calculated film thickness of about 1.8 microns using a 30% by weight solution as described in Example i. Coating both dysprosium and M2 with an m-rod produced a film with a total thickness of about 3.0 microns. In applications where Ml is only used as an adjustment and adhesion layer, its thickness 'should be preferably reduced' so as to save relatively expensive LC materials. By using a solution having a higher solvent content, the thickness of the polymerizable layer can be reduced after the solvent is evaporated. Four films were prepared by using a No. 1 rod but diluting the Ml solution to 15%, 10%, 5%, and 1%, and the adhesion and adjustment of the films were examined. The results are shown in the watchmaker. Table 1

RMN solution weight% Μ1 film thickness micron Ml adhesion to M2 film%

O: \ 89 \ 89989.DOC -25- 200417596 The thickness of the film M1 is detected by an optical fringe detection system. A 30% solution gives a measured thickness of 1.3 microns. A 10% solution gives a measured thickness of 0.34 microns. From the above results, it can be seen that there is a minimum thickness of about 0.2 microns, below which no adhesive effect can be obtained. It can also be seen that the thicker film of M 1 produces a tilted film of M 2 rather than the flat film normally expected from a M2 mixture formulation. Example 3-Preparation of Multilayers including Low Crosslinking LC Films and Cholesteric LC (CLC) Films Steroid LC Mixture M3 7.1% Single Reactivity 11.2% Single Reactivity 9.7% Single Reactivity 47.1% Double Reactivity 10.2% Double reactivity 10.2% Double reactivity 0.5% 4.0% Prepare polymerizable bile as follows (1) (2) (3) (4) (5)

Paliocolour LC756 Fluorad FC171 Irgacure 907

〇 〇-, 2) "〇 (5)

Paliocolour LC756 is a commercially available palm polymerizable material (from BASF AG, Ludwigshafen, Germany). The TAC substrate sheet is rubbed 3 × 1000 mm, and coated with a 2 wire wound rod with a 5% solution in Ml (Example 1). The theoretical thickness of the resulting coating was 0.6 microns. O: \ 89 \ 89989 DOC -26- The solvent is evaporated to leave a liquid crystal film, and the limb film is cured under UV light. The resulting film was then rubbed 2 x 1000 mm and coated with a wire-type LC mixture M3 with a wire-wound rod. After the solvent evaporates, the liquid crystal film is aged under UV light. This results in a clean, adjusted CLC film that is reflected on the UV film. The standard intersection method was used to test its adhesion. The adhesive effect is 100%. Example 4-Effects of Surfactants The mixtures M1 and M2 of Example 1 contained 0.5% of the surfactant component Fluorad FC171. M1 and M2 polymer films were prepared as described in Example 1, except that the surfactant FC171 was omitted. The same effects were observed with these mixtures and films as described in the examples. Example 5-Preparation of a multi-layer comprising a low-crosslinking LC film and a crosslinked isotropic hard coat layer A polymer film of M1 (ΠM1 film π) was prepared on a TAC substrate as defined in the examples. Several hard coat formulations D1-75 as shown below were prepared, the formulations were coated on top of the M1 film, and cured by UV exposure.

Irgacure® photoinitiator was purchased from Siba-Geigy AG. Ebecryl® 270, 5129, and 350 were purchased from UCB Chemical Company. Topcoat 604® is available from Eques Coatings B.V. 5a) ΤΙ Ebecryl 270 60% 1,6-hexanediol diacrylate (HDDA) 24% tripropylene glycol dipropionic acid g purpose (TPGDA) 10% O: \ 89 \ 89989.DOC -27- 200417596

Irgacure 907 6% formulation was used as a 25% by weight solution in toluene. The hard coating shows greater scratch resistance than the unprotected M1 film. This is evidenced by a nail test. The durability of the system was further examined by laminating the multi-layer to a glass sheet with a pressure sensitive adhesive (PSA) on the free surface of the TAC substrate. The entire stack of Nie sounds was then placed in a chamber at 60 ° C and 90% relative temperature. For 40 days (after 960 hours), no significant deterioration of the slides occurred. The hard coat surface was then laminated to a second TAC by PSA. At the time of peeling off, the two TAC sheets were separated, and the hard coating and the Ml film were not damaged. 5b) T2 tetrapentaerythritol tetrapropionate 80% HDDA 15%

Irgacure 907 5% formulation was used as a 50% by weight solution in toluene. The coating was found to have excellent scratch resistance. The nail test just marks the coating. 5c) Butyl 3-propionate 47.5% HDDA 26.4% tetrapentaerythritol tetrapropionate 2 1 10 / 〇

Irgacure 907 5.0% formulation is used without solvents. The coating was found to have excellent scratch resistance. Upon lamination with PSA to the second TAC and subsequent delamination, removal of the hard coating from the Ml film did not damage the Ml film. 5d) T4 O: \ 89 \ 89989.DOC -28- 200417596 Topcoat 604® (from Eques Coatings B. V.) was applied to the M 1 film and cured. This material gives a hard coating resistant to severe friction. 5e) T5 74.8% 18.7% 0.9% 5.6%

Ebecryl 5 129 HDDA Ebecryl 350 Irgacure 500 formulations use solvent-free clean, scratch-resistant hard coatings.

O: \ 89 \ 89989.DOC 29-

Claims (1)

200417596 Scope of patent application: 1. A kind of thin film of LC3 material, which is obtained from a polymerizable material, which contains not more than 7% by weight of A compound of two or more polymerizable groups. 2. The film according to item 1 of the scope of the patent application, characterized in that the polymerizable LC material includes ϋ -70 to 99% by weight of-or more compounds having-polymerizable groups,-greater than 0 to 7% by weight -One or more compounds having two or more polymerizable groups,-0 to 15% by weight of a non-polymerizable compound,-0 to 10% by weight of one or more polymerization initiators. 3. The film according to item 1 or 2 of the scope of patent application, characterized in that the polymerizable LC material does not contain a compound having two or more polymerizable groups. 4. Polymerizable materials as defined in the scope of the patent application. 5 · -Multi-layer 'including a plastic substrate, providing at least one layer of an LC polymer film according to item i of the patent application scope, and at least one layer: a hard coating film with improved resistance to mechanical stress' The hard coating film is provided on the surface of the at least one LC polymer film that does not: face the substrate. 6 · = Please refer to the fifth layer of the patent scope ', which is characterized in that the hard coating film is two ..., two- or multifunctional acrylic 3, cross-linked acrylic misalignment. 7. = Please specialize in the fifth paragraph "Multilayer" is characterized in that the hard coating film has a weight of more than 20 weight 9 ^ is right-· ¥ $ 々 compound with — or more polymerizable groups O: \ 89 \ 89989.DOC 8. 物 的Polymerized LC material. A method for preparing a substrate has a method of forming a LC material layer according to the patent application No. 4 on the substrate by polymerizing as defined by a well-adhesive, translucent LC film.- The material is adjusted to a uniform orientation,-the LC material is polymerized, and the polymerized film is removed from the substrate if necessary. A method for preparing a layer according to the scope of the patent application by using 5 or 6 layers, and providing a layer of the LC material according to the application on a plastic substrate. Adjust to a consistent orientation,-polymerize the LC material,-provide a hard coat on the free surface of the polymerized LC material. I0. Two methods for preparing a multi-layer according to the patent application No. 7 by-providing on a plastic substrate a first polymerizable LC material layer defined in accordance with the fourth scope of the patent application,-using as needed The first LC material is adjusted to a uniform orientation, • polymerizing the first LC material,-providing a second polymerizable 10 material layer defined on the free surface of the first polymerized LC material according to item 7 of the scope of patent application It is considered that the 3 LC-LC material is adjusted to a uniform orientation, and O: \ 89 \ 89989.DOC -2-200417596-polymerizes the second LC material. u ·: According to the patent application, the film is used for optical, Gongxun storage, decoration and security applications. 12. An optical element or device comprising a thin film according to the application. 13. A liquid crystal display comprising a thin film according to an application. Science, electro-optics, and the scope of the first scope of the scope of the scope of the first scope of the scope of the scope of the scope of the first scope of the scope of the first scope of the scope of the first scope of the scope of the first 14 of the scope of the scope of the scope of the first category. 15 · = According to the patent, the material in item 4 of the scope of patent is required for optical, lean storage, decoration and security applications. Scientific, electro-optical, 16. Material of an optical element or component. Device, which includes the fourth type of liquid crystal display according to the scope of the patent application, which includes special materials according to the application. 18 ·-A kind of identification, verification or security t% A 乂 colored image, which contains material according to item 4 of the patent. 19. According to the tier 5 of the scope of application for patents, its department, information storage, decoration and security applications. 20 · —An optical element, a dry flying clothing set, which includes a multi-layer according to the application. The 4th profit-seeking range is used in the optical and electro-optical benefit range. 5 21. A liquid crystal display multilayer. °. , Which contains the image according to the scope of patent application No. 5 ′ which contains the multi-layer of the scope of patent application according to 22. An identification, verification or security mark or colored O: \ 89 \ 89989.DOC 200417596. 23.-A valuable object or document that contains an identification, verification or security mark or image in accordance with item 14, 18 or 22 of the scope of the patent application. O: \ 89 \ 89989 DOC -4- 200417596 柒. Designated representative map: (1) The designated representative map in this case is: (none) (II) The representative symbols of the component map are simply explained: 捌, if there is a chemical formula in this case, Please disclose the chemical formula that best shows the characteristics of the invention: (none) O: \ 89 \ 89989 DOC