WO2021233453A1

WO2021233453A1 - Polymerizable composition, retardation film and preparation method for retardation film, display element, and display

Info

Publication number: WO2021233453A1
Application number: PCT/CN2021/095580
Authority: WO
Inventors: 周志华; 李明; 李佳明; 孟劲松; 王一平; 梁志安; 员国良
Original assignee: 石家庄诚志永华显示材料有限公司
Priority date: 2020-05-22
Filing date: 2021-05-24
Publication date: 2021-11-25

Abstract

A polymerizable composition, comprising one or more compounds as shown in formula I, and one or more compounds as shown in formula II. Also provided are a retardation film comprising the polymerizable composition and a preparation method therefor and use thereof. The polymerizable composition involves the use of a combination of an industrially produced resin material and a polymerizable liquid crystal compound, which has a significant cost reduction effect.

Description

Polymerizable composition, retardation film and method for preparing retardation film, display element and display

Technical field

The invention belongs to the field of optical films, and specifically relates to a polymerizable composition, a retardation film containing the polymerizable composition, a preparation method thereof, and applications in display elements and displays.

Background technique

With the continuous development of display technology, people have higher and higher requirements for display performance. However, the display has some inherent technical defects. For example, during the display process of the display device, it will be affected by external light, and when viewing the screen under strong light, the problem of reduced contrast will occur, resulting in poor display effect and narrow viewing angle range. The above problems can be solved by improving the performance of the retardation film in the display. It is required that the wavelength dispersion of the birefringence of the retardation film is small, and even negative dispersion is formed.

In order to solve the above problems, researchers have carried out a series of exploratory work, some of which have also achieved some results. For example, Chinese Patent Application CN106574186A discloses a phase difference film formed by mixing and aligning polymerizable liquid crystal monomers, including three polymerizable liquid crystal monomers. The retardation of the retardation film can be controlled according to the content ratio of the three polymerizable liquid crystal monomers. However, this retardation film still exhibits positive dispersion characteristics and cannot meet the higher performance requirements of the retardation film. Chinese patent application CN109207162A discloses a polymerizable liquid crystal monomer composition, which contains at least two liquid crystal compounds, and can obtain a liquid crystal polymer with a substrate with low wavelength dispersion characteristics and high front contrast. However, in order to realize the negative dispersion optical characteristics, this method requires components with negative dispersion characteristics to realize it. Generally, the production of such negative optical characteristics compounds is relatively difficult and the cost is very high. At the same time, the polymerizable liquid crystal film produced by the polymerizable liquid crystal compound cannot be aligned autonomously, and an alignment layer is needed to solve the alignment problem, otherwise a polymer film that meets the light retardation requirement cannot be obtained.

Summary of the invention

In order to overcome the problem that the polymerizable liquid crystal film produced by the polymerizable liquid crystal compound cannot be aligned autonomously, the present invention provides a polymerizable composition. By using the polymerizable composition, the retardation can be satisfied without the use of an alignment layer. The required negative dispersion characteristic retardation film.

The present invention proposes a new idea of preparing negative dispersion characteristic films, and expands the idea of preparing negative dispersion polymer films and materials.

Specifically, the present invention includes the following contents:

In the first aspect of the present invention, a polymerizable composition is provided, which is characterized by comprising one or more compounds represented by formula I and one or more compounds represented by formula II; Shows that the molecular weight of the compound is between 100 and 1000, and the added mass percentage of the compound shown in formula II is 20% to 60%

In formula I,

L ₁ represents H, F, Cl, -CN or a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, and 2 to 25 carbon atoms The alkynyl group in which one or more non-adjacent -CH ₂ -groups are optionally replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O- CO-O-, -N- substituted, and the substituted groups -O- or -S- atoms are not directly connected to each other, wherein one or more H atoms are each optionally substituted by halogen;

Represents 1,4-cyclohexylene, 1,4-phenylene, 2,6-naphthylene, 1,5-naphthylene, 1,4-naphthylene;

Sp ₁ and Sp ₂ each independently represent a spacer;

P ₁ and P ₂ each independently represent a polymerizable group or H, and _{at least one of P 1} and P ₂ represents a polymerizable group;

a, b, and c each independently represent 1, 2 or 3;

In formula Ⅱ,

T represents -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -N- or -CH ₂ -;

L ₇ represents H, F, Cl, CN or linear alkyl, branched or cyclic alkyl having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, and 2 carbon atoms ~10 alkynyl groups, in which one or more non-adjacent -CH ₂ -groups are optionally replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-,- O-CO-O-, -N- substituted, and the substituted groups -O- or -S- atoms are not directly connected to each other, and one or more H atoms in _{the -CH 2-are each optionally halogen} Substitution; when L ₇ represents a cyclic alkyl group, the cyclic alkyl group is preferably 1,4-cyclohexylene, 1,4-phenylene, 2,6-naphthylene, 1,5-naphthalene Group, 1,4-naphthylene, wherein the H atom on the ring is optionally substituted by halogen;

P ₆ and P ₇ each independently represent a polymerizable group or H, and _{at least one of P 6} and P ₇ represents a polymerizable group;

k ₁ , k _2, or k ₃ each independently represents an integer from 0 to 50, k ₄ represents an integer from 1 to 50, and k ₁ ≤k ₃ and k ₂ ≤k ₃ .

Further preferably, the polymerizable composition is characterized in that it further comprises one or more compounds of formula III and/or one or more compounds of formula IV,

In formula Ⅲ,

R represents H or a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, an alkynyl group having 2 to 25 carbon atoms, one or more of them A non-adjacent -CH ₂ -group is optionally -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -N- Substitution, and the substituted groups -O- or -S- atoms are not directly connected to each other, _{and one or more H atoms in the -CH 2} -are each optionally substituted by halogen;

Z represents a single bond, an alkylene group with 1-10 carbon atoms, and an alkenylene group with 2-10 carbon atoms, where any H atom can be substituted by fluorine, and any one or more unconnected -CH ₂ -Optionally substituted by -O-, -S-, -COO-, -OOC-;

L ₂ and L ₃ each independently represent H, F, Cl, CN or a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, and a carbon atom An alkynyl group with a number of 2-25, wherein one or more non-adjacent -CH ₂ -groups are optionally -O-, -S-, -CO-, -CO-O-, -O-CO -, -O-CO-O-, -N- substituted, and the substituted groups -O- or -S- atoms are not directly connected to each other, and one or more H atoms in _{the -CH 2-are each optional}地 is replaced by halogen;

Represents aryl, heteroaryl, alicyclic, heterocyclic or fused ring, and the H atom on the ring is optionally _{substituted by L 6} mono- or poly-substituted;

The L ₆ represents F, Cl, CN or a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, or a C 2-25 Alkynyl, in which one or more non-adjacent -CH ₂ -groups are optionally -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO -O-, -N- substituted, and the substituted groups -O- or -S- atoms are not directly connected to each other, _{and one or more H atoms in the -CH 2} -are each optionally substituted by halogen;

Sp ₃ represents the spacer base;

P ₃ represents a polymerizable group or H;

d and e each independently represent 0, 1, 2, 3 or 4;

m and n each independently represent 0, 1 or 2, and m+n≥1;

o means 1, 2 or 3.

In formula Ⅳ,

L ₄ and L ₅ each independently represent H, F, Cl, CN or a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, and a carbon atom An alkynyl group with a number of 2-25, wherein one or more non-adjacent -CH ₂ -groups are optionally -O-, -S-, -CO-, -CO-O-, -O-CO -, -O-CO-O-, -N- substituted, and the substituted groups -O- or -S- atoms are not directly connected to each other, and one or more H atoms in _{the -CH 2-are each optional}地 is replaced by halogen;

Represents aryl, heteroaryl, alicyclic, heterocyclic or condensed ring, and the H atom on the ring is optionally _{substituted by L 8} mono- or poly-substituted;

The L ₈ represents F, Cl, CN or a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, or a C 2-25 Alkynyl, in which one or more non-adjacent -CH ₂ -groups are optionally -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO -O-, -N- substituted, and the substituted groups -O- or -S- atoms are not directly connected to each other, _{and one or more H atoms in the -CH 2} -are each optionally substituted by halogen;

g and h each independently represent 1, 2, 3 or 4;

i represents 0, 1 or 2;

f and j each independently represent 1, 2 or 3, and f+j≥3;

Sp ₄ and Sp ₅ each independently represent a spacer;

P ₄ and P ₅ each independently represent a polymerizable group or H.

Further, the polymerizable composition further includes one or more polyester resins, and/or, one or more additives; the additives include antioxidants, surfactants, polymerization inhibitors, chain transfer agents, Sensitizer, anti-ultraviolet agent or polymerization inhibitor.

Further, the polymerizable composition further includes one or more initiators, and the initiators are compounds that can initiate photopolymerization.

In a second aspect of the present invention, a retardation film is provided, which is formed by polymerizing the aforementioned polymerizable composition. The retardation film preferably has a retardation of 120-150 at a light wavelength of 550 nm.

The third aspect of the present invention provides a method for preparing a retardation film, which specifically includes:

Blending the aforementioned polymerizable composition into a solvent to form a polymerizable composition solution;

Coating the aforementioned polymerizable composition solution on the substrate to form a polymerizable composition solution layer;

By drying the aforementioned polymerizable composition solution layer, a polymerizable composition resin layer is obtained;

The resin layer of the polymerizable composition is photopolymerized by visible or ultraviolet light irradiation to form a retardation film.

In a fourth aspect of the present invention, there is provided a display element comprising the aforementioned polymerizable composition or the aforementioned retardation film, and the display element is an active matrix display element or a passive matrix display element.

In a fifth aspect of the present invention, there is provided a display comprising the aforementioned polymerizable composition or the aforementioned retardation film, and the display is an active matrix display or a passive matrix display.

Since the polymerizable composition disclosed in the present invention uses an industrially produced compound represented by formula II and a polymerizable liquid crystal compound to replace the existing polymerizable liquid crystal compound or resin material, it has a significant effect on reducing cost. In addition, this method of preparing a retardation film using an industrially produced compound of formula II and a polymerizable liquid crystal compound has simple steps, easy implementation, low production cost, high production efficiency, and can achieve large-scale production, which is the preparation of retardation film. Provides new ideas. The retardation film prepared by using the polymerizable composition does not require an alignment layer to meet the optical retardation requirements, and can achieve negative dispersion characteristics, and can avoid dust particles, electrostatic residues, brush marks, etc. caused by the configuration of the alignment layer. The problem caused. The display element or display containing the above retardation film can avoid the problem of low manufacturing yield caused by the alignment layer, and effectively simplify the manufacturing process of the display element or display, thereby improving production efficiency and reducing production costs.

Detailed ways

In the present invention, "may also contain..." means that the component may or may not be present in the composition;

The "polyester resin" mentioned in the present invention refers to a polyester resin oligomer formed by polycondensation of a dihydric alcohol or a dibasic acid or a polyhydric alcohol and a polybasic acid, with a molecular weight distribution of 5,000 to 30,000.

The "solvent" mentioned in the present invention refers to an organic solvent and is not particularly limited in type, but is preferably an organic solvent in which the polymerizable composition shows good solubility, and preferably an organic solvent that can be dried at 100°C or less. Examples of such solvents include aromatic hydrocarbons such as toluene, xylene, cumene, mesitylene, ester solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate, methyl Ketone solvents such as ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, ether solvents such as tetrahydrofuran, 1,2-dimethoxyethane, anisole, N,N-dimethyl Carboxamide, N-methyl-2-pyrrolidone and other amide solvents, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, γ-butyrolactone, and chlorobenzene. These organic solvents may be used singly or in combination of two or more, but from the viewpoint of solution stability, it is preferable to use any one or more of ketone solvents, ether solvents, ester solvents, and aromatic hydrocarbon solvents.

If the polymerizable composition used in the present invention is made into an organic solvent solution, the substrate can be coated, and the ratio of the organic solvent used in the polymerizable composition is not particularly limited as long as it does not significantly damage the coated state. However, the total amount of the organic solvent contained in the polymerizable composition is preferably 30 to 90% by mass, more preferably 40 to 85% by mass, and particularly preferably 50 to 80% by mass.

When dissolving the polymerizable composition in an organic solvent, it is preferable to heat and stir in order to dissolve it uniformly. The heating temperature during heating and stirring is preferably adjusted appropriately in consideration of the solubility of the composition used in the organic solvent, but from the viewpoint of productivity, it is preferably 15°C to 110°C, more preferably 15°C to 105°C, and even more preferably 15°C ~100°C, particularly preferably 20°C to 90°C.

The "initiator" mentioned in the present invention refers to a photopolymerization initiator, and preferably contains at least one or more. Specifically, it can include: "Irgacure651", "Irgacure 184", "Darocur 1173", "Irgacure 907", "Irgacure 127", "Irgacure 369", "Irgacure 379", "Irgacure 819" manufactured by BASF Japan Co., Ltd. ", "Irgacure2959", "Irgacure 1800", "Irgacure 250", "Irgacure 754", "Irgacure784", "Irgacure OXE01", "Irgacure OXE02", "Lucirin TPO", "Farocur Cur 1173", "Daro" "Esacure1001M", "Esacure KIP150", "Speedcure BEM", "Speedcure BMS", "Speedcure MBP", "Speedcure PBZ", "Speedcure ITX", "Speedcure DETX", "Speedcure EBD", "Speedcure MBB" manufactured by Lambson ", "Speedcure BP", "Kayacure DMBI" manufactured by Nippon Kayaku Co., Ltd., "TAZ-A" manufactured by Nihon Siber Hegner Co., Ltd. (now DKSH Japan Co., Ltd.), "Adeka Optomer SP-152" manufactured by ADEKA Co., Ltd. ", "Adeka Optomer SP-170", "Adeka Optomer N-1414", "Adeka Optomer N-1606", "Adeka Optomer N-1717", "Adeka Optomer N-1919", etc.

The "907" mentioned in the present invention is a photoinitiator of "Irgacure 907" manufactured by BASF Japan Co., Ltd.

The amount of the photopolymerization initiator used is preferably 0.1 to 10% by mass relative to the polymerizable composition, and particularly preferably 0.5 to 7% by mass. These photopolymerization initiators may be used singly, or two or more of them may be mixed and used. In addition, a sensitizer or the like may be added.

The "additives" mentioned in the present invention are components for improving the stability of the polymerizable composition of the present invention, and include antioxidants, surfactants, polymerization inhibitors, chain transfer agents and the like. These additives can be selectively added one or more or none according to the stability of the formulation.

Polymerization inhibitor: It is preferable to add a polymerization inhibitor to the polymerizable composition of the present invention. Examples of the polymerization inhibitor include phenol-based compounds, quinone-based compounds, amine-based compounds, thioether-based compounds, and nitroso compounds. Examples of phenolic compounds include p-methoxyphenol, cresol, tert-butylcatechol, 3,5-di-tert-butyl-4-hydroxytoluene, 2,2'-methylenebis(4-methyl 6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert Butylphenol), 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol, etc. Examples of quinone compounds include hydroquinone, methylhydroquinone, tert-butylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, tert-butyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, 1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, anthraquinone, diphenoquinone, etc. Examples of amine compounds include: p-phenylenediamine, 4-aminodiphenylamine, N,N'-diphenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine , N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N,N'-bis-2-naphthyl-p-phenylenediamine, diphenylamine, N-phenyl -Β-Naphthylamine, 4,4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, etc. Examples of thioether compounds include phenothiazine, distearyl thiodipropionate, and the like. Examples of nitroso compounds include: N-nitroso diphenylamine, N-nitrosophenyl naphthylamine, N-nitroso dinaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosobenzene, and p-nitrosobenzene. Nitroso diphenylamine, α-nitroso-β-naphthol, etc., N,N-dimethyl p-nitrosoaniline, p-nitroso diphenylamine, p-nitrosodimethylamine, p-nitroso -N,N-Diethylamine, N-nitrosoethanolamine, N-nitroso di-n-butylamine, N-nitroso-N-n-butyl-4-butanolamine, N-nitroso- Diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N －Phenylhydroxylamine ammonium salt, nitrosobenzene, 2,4,6-tri-tert-butylnitrosobenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso -N-ethyl carbamate, N-nitroso-N-n-propyl carbamate, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 1- Nitroso-2-naphthol-3,6-sodium sulfonate, 2-nitroso-1-naphthol-4-sodium sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride, etc. The addition amount of the polymerization inhibitor is preferably 0.01 to 1.0% by mass relative to the polymerizable composition, and more preferably 0.05 to 0.5% by mass.

Antioxidant: In order to improve the stability of the polymerizable composition of the present invention, it is preferable to add an antioxidant or the like. Examples of such compounds include hydroquinone derivatives, nitrosamine-based polymerization inhibitors, hindered phenol-based antioxidants, etc., more specifically, tert-butyl hydroquinone, methyl hydroquinone, and Wako Pure "Q-1300" and "Q-1301" manufactured by Pharmaceutical Industry Co., Ltd., "IRGANOX1010", "IRGANOX1035", "IRGANOX1076", "IRGANOX1098", "IRGANOX1135", "IRGANOX1330", "IRGANOX1425" and " "IRGANOX1520", "IRGANOX1726", "IRGANOX245", "IRGANOX259", "IRGANOX3114", "IRGANOX3790", "IRGANOX5057", "IRGANOX565", etc. The amount of the antioxidant added is preferably 0.01 to 2.0% by mass relative to the polymerizable liquid crystal composition, and more preferably 0.05 to 1.0% by mass.

Surfactant: The polymerizable composition of the present invention may contain at least one or more surfactants in order to reduce unevenness in film thickness when it is made into an optically anisotropic body. Examples of surfactants that may be contained include alkyl carboxylates, alkyl phosphates, alkyl sulfonates, fluoroalkyl carboxylates, fluoroalkyl phosphates, fluoroalkyl sulfonates, poly Oxyethylene derivatives, fluoroalkyl ethylene oxide derivatives, polyethylene glycol derivatives, alkyl ammonium salts, fluoroalkyl ammonium salts, etc., fluorinated surfactants are particularly preferred. Specifically, you can cite: "Megafac F-251", "Megafac F-444", "Megafac F-477", "Megafac F-510", "Megafac F-552", "Megafac F-553", "Megafac F-554", "MegafacF-555", "Megafac F-556", "Megafac F-557", "Megafac F-558", "Megafac F-559", "Megafac F-560", "Megafac F-561", "Megafac F-562", "Megafac F-563", "Megafac F-565", "Megafac F-567", "Megafac F-568", "Megafac F-569", "Megafac F- 570", "Megafac F-571", "Megafac R-40", "Megafac R-40", "Megafac R-43", "Megafac R-94", "Megafac RS-72-K", "Megafac RS -75", "Megafac RS-76-E", "Megafac RS-90", (the above are made by DIC Co., Ltd.), "Ftergent 100", "Ftergent 100C", "Ftergent 110", "Ftergent 150", " Ftergent 150CH", "Ftergent A", "Ftergent 100A-K", "Ftergent 501", "Ftergent300", "Ftergent 310", "Ftergent 320", "Ftergent 400SW", "FTX-400P", "Ftergent251", "Ftergent 215M", "Ftergent 212MH", "Ftergent 250", "Ftergent 222F", "Ftergent 212D", "FTX-218", "FTX-209F", "FTX-213F", "FTX-233F", " Ftergent 245F", "FTX-208G", "FTX-240G", "FTX-206D", "FTX-220D", "FTX-230D", "FTX-240D", "FTX-207S", "FTX-211S ", "FTX-220S", "FTX-230S", "FTX-750FM", "FTX-730FM", "FTX-730FL", "F TX-710FS", "FTX-710FM", "FTX-710FL", "FTX-750LL", "FTX-730LS", "FTX-730LM", "FTX-730LL", "FTX-710LL" (the above are Company Noes), “BYK-300”, “BYK-302”, “BYK-306”, “BYK-307”, “BYK-310”, “BYK-315”, “BYK-320”, “BYK- 322", "BYK-323", "BYK-325", "BYK-330", "BYK-331", "BYK-333", "BYK-337", "BYK-340", "BYK-344" , "BYK-370", "BYK-375", "BYK-377", "BYK-350", "BYK-352", "BYK-354", "BYK-355", "BYK-356", " BYK-358N”, “BYK-361N”, “BYK-357”, “BYK-390”, “BYK-392”, “BYK-UV3500”, “BYK-UV3510”, “BYK-UV3570”, “BYKSilclean3700” (The above is made by BYK-Chemie Japan), "TEGO Rad2100", "TEGO Rad2200N", "TEGO Rad2250", "TEGO Rad2300", "TEGORad2500", "TEGO Rad2600", "TEGO Rad2700" (The above are made by Tego ), "N215", "N535", "N605K", "N935" (the above are manufactured by Solvay Solexis), etc.

The amount of the surfactant added is preferably 0.01 to 2% by mass relative to the mass percentage content of the polymerizable composition, and more preferably 0.05 to 0.5% by mass percentage. In addition, by using the above-mentioned surfactant, when the polymerizable composition of the present invention is made into an optically anisotropic body, the inclination angle of the air interface can be effectively reduced. In addition, by using the above-mentioned surfactant, the orientation can be improved. good. In particular, it was clarified that if the above-mentioned polymerizable haze improver is used in combination with a surfactant, the orientation can be significantly improved by a synergistic effect.

Chain transfer agent: It is also preferable to add a chain transfer agent to the polymerizable composition of the present invention in order to improve the adhesion to the substrate when it is made into an optically anisotropic body. The chain transfer agent is preferably a thiol compound, more preferably a monothiol, dithiol, trithiol, and tetrathiol compound, and still more preferably a trithiol compound. The addition amount of the chain transfer agent is preferably 0.5 to 10% by mass relative to the mass percentage content of the polymerizable liquid crystal composition, and more preferably 1.0 to 5.0% by mass percentage.

The "substrate" mentioned in the present invention is a carrier used to carry the polymerizable composition. The substrate used in the optically anisotropic body of the present invention is mainly used in liquid crystal devices, displays, optical parts, and optical films. There is no particular limitation on the material that has the heat resistance of the substrate and the heat resistance means that it can withstand heating during drying after coating the polymerizable composition of the present invention. Examples of such substrates include organic materials such as glass substrates, metal substrates, ceramic substrates, and plastic substrates. In particular, when the substrate is an organic material, examples include cellulose derivatives, polyolefins, polyesters, polycarbonates, polyacrylates (acrylic resins), polyarylates, polyethersulfones, polyimides, Polyphenylene sulfide, polyphenylene ether, nylon or polystyrene, etc. Among them, plastic substrates such as polyester, polystyrene, polyacrylate, polyolefin, cellulose derivatives, polyarylate, and polycarbonate are preferred, and metal and polyethylene terephthalate (PET) are more preferred. , Cellulose derivatives and other substrates (PVA). As the shape of the substrate, in addition to a flat plate, it may have a curved surface. These base materials may have an electrode layer, an anti-reflection function, and a reflection function as necessary.

The "coating" mentioned in the present invention refers to the coating method used to obtain the polymerizable composition of the present invention, which can be applied by applicator method, bar coating method, spin coating method, roll coating method, direct gravure coating. The cloth method, reverse gravure coating method, flexo coating method, inkjet method, die coating method, cap coating method, dip coating method, slit coating method, etc. are well-known and customary Methods. After coating the polymerizable composition, it is dried as needed.

The "polymerization" mentioned in the present invention refers to the polymerization operation of the polymerizable composition of the present invention. When polymerization is carried out by light irradiation, specifically, it is preferable to irradiate ultraviolet light below 390 nm, and most preferably to irradiate light with a wavelength of 250 to 370 nm. . However, when ultraviolet light of 390 nm or less may cause decomposition of the polymerizable composition, it is sometimes preferable to use ultraviolet light of 390 nm or more for the polymerization treatment. The light is preferably unpolarized light.

The "alignment" mentioned in the present invention refers to the treatment of the surface of the base film by rubbing or a photo-aligning agent, so that the compound molecules can be better arranged on the surface of the base film according to a certain rule.

The "optical anisotropic body" mentioned in the present invention is also called the refractive index anisotropy body, which refers to a type of object in which light propagates and produces birefringence. In this patent, it refers to a retardation film.

The "Re" mentioned in the present invention refers to the amount of retardation in the film, that is, the amount of horizontal retardation, which is the amount of retardation parallel to the film surface of the retardation film.

The "Rth" mentioned in the present invention refers to the amount of vertical retardation, that is, the amount of retardation perpendicular to the surface of the retardation film.

The "retardation film" mentioned in the present invention is a polarization conversion element having optical anisotropy, and is mainly used in optical elements.

The "room temperature" mentioned in the present invention refers to a temperature range of 15°C to 35°C.

The "spacer" mentioned in the present invention means an alkyl group with 1-10 carbon atoms, a fluorine-substituted alkyl group with 1-10 carbon atoms, an alkoxy group with 1-10 carbon atoms, fluorine Substituted alkoxy groups with 1-10 carbon atoms, alkenyl groups with 2-10 carbon atoms, fluorine-substituted alkenyl groups with 2-10 carbon atoms, chains with 3-8 carbon atoms Alkenyloxy or fluorine-substituted alkenyloxy with 3-8 carbon atoms, alkynyl with 2-10 carbon atoms, fluorine-substituted alkynyl with 2-10 carbon atoms, number of carbon atoms Is a 2-8 alkynyloxy group or a fluorine-substituted alkynyloxy group with 3-8 carbon atoms, and any one or more unconnected -CH ₂ -of the groups indicated by the spacer may be individually Independently optionally substituted by -O-, -S-, -COO-, -OOC-;

The "polymerizable group" mentioned in the present invention means a methacrylate group, an acrylate group, a vinyl group or an oxirane group. It is more preferably an acrylate group or a methacrylate group.

[Polymerizable composition]

One aspect of the present invention is a polymerizable composition,

Contains one or more compounds represented by formula I and one or more compounds represented by formula II;

In formula I,

L ₁ represents H, F, Cl, CN or a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, or a C 2-25 Alkynyl, in which one or more non-adjacent -CH ₂ -groups are optionally -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO -O-, -N- substituted, and the substituted groups -O- or -S- atoms are not directly connected to each other, _{and one or more H atoms in the -CH 2} -are each optionally substituted by halogen;

Represents 1,4-cyclohexylene, 1,4-phenylene, 2,6-naphthylene, 1,5-naphthylene or 1,4-naphthylene;

Sp ₁ and Sp ₂ each independently represent a spacer;

a, b, and c each independently represent 1, 2, or 3.

Preferably, the aforementioned compound represented by formula I is selected from the group consisting of I1-I48,

Wherein, t and u each independently represent 1, 2, 3, 4, 5, 6, 7 or 8. According to the solubility and compatibility of the above compounds, and safety standards, formula I 4-8, formula I 10-12, formula I 14-15, formula I 18-23, formula I 25, formula I 27, formula I 29-30, formula I 32-33 are preferred , Formula I36, Formula I38, Formula I40-41.

Further preferably, the compound represented by the above formula I is selected from the group consisting of the compounds represented by the following formula I4-1 to I48-3,

More preferably, the compound represented by the above formula I is selected from the group consisting of formula I 6-2, formula I 6-3, formula I 7-2, formula I 7-3, formula I 11-2, formula I 11-3, formula I 14-2, and formula I 14 -3. Formula I 18-2, Formula I 18-3, Formula I 22-2, Formula I 22-3, Formula I 23-2, Formula I 23-3, Formula I 25-2, Formula I 25-3, Formula I 27-2, Formula I 27 -3. Formula I 32-2, Formula I 32-3, Formula I 33-2, Formula I 36-2, Formula I 36-3, Formula I 38-2, or Formula I 38-3.

In formula Ⅱ,

T represents -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -N- or -CH ₂ -;

L ₇ represents H, F, Cl, CN or a linear alkyl, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and 2 carbon atoms ~10 alkynyl groups, in which one or more non-adjacent -CH ₂ -groups are optionally replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-,- O-CO-O-, -N- substituted, and the substituted groups -O- or -S- atoms are not directly connected to each other, and one or more H atoms in _{the -CH 2-are each optionally halogen} replace;

Preferably, the aforementioned compound represented by formula II is selected from the group consisting of compounds represented by formula II1-II5,

Wherein, L ₇ represents H, F, Cl, CN or a linear alkyl, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and the number of carbon atoms Is an alkynyl group of 2-10, in which one or more non-adjacent -CH ₂ -groups are optionally replaced by -O-, -S-, -CO-, -CO-O-, -O-CO- , -O-CO-O-, -N- substituted, and the substituted groups -O- or -S- atoms are not directly connected to each other, and one or more H atoms in _{the -CH 2-are each optionally} Replaced by halogen;

_{Preferably, the cyclic alkyl group represented by L 7} in the compound represented by formula II is 1,4-cyclohexylene, 1,4-phenylene, 2,6-naphthylene, 1,5-phenylene Naphthyl, 1,4-naphthylene, wherein the H atom on the ring is optionally substituted by halogen.

More preferably, the compound represented by the above formula II is selected from the group consisting of the compounds represented by the following formula II1-1 to formula II4-4,

Wherein, k ₁ , k ₂ or k ₃ each independently represents an integer of 0-50, k ₄ represents an integer of 1-50, and k ₁ ≤k ₃ and k ₂ ≤k ₃ .

More preferably, the compound represented by formula II is selected from the group consisting of compounds represented by formula II1-1-1 to II4-1-6,

The polymerizable composition of the present invention also contains one or more compounds of formula III,

In formula Ⅲ,

L ₆ represents F, Cl, CN or a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, or an alkynyl group having 2 to 25 carbon atoms , Wherein one or more non-adjacent -CH ₂ -groups are optionally -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O -, -N-substituted, and the substituted groups -O- or -S- atoms are not directly connected to each other, _{and one or more H atoms in the -CH 2} -are each optionally substituted by halogen;

Sp ₃ represents the spacer base;

P ₃ represents a polymerizable group or H;

d and e each independently represent 0, 1, 2, 3 or 4;

m and n each independently represent 0, 1 or 2, and m+n≥1;

o means 1, 2 or 3.

Preferably, the compound represented by formula III is selected from the group consisting of compounds represented by formula III1 to III26,

The F atoms in the compounds represented by the above formulas can be independently substituted by Cl atoms, methyl groups, and methoxy groups.

Sp represents the spacer base,

Z represents a single bond, an alkylene group with 1-10 carbon atoms, and an alkenylene group with 2-10 carbon atoms, where any H atom can be substituted by fluorine, and any one or more unconnected -CH ₂ -Optionally substituted by -O-, -S-, -COO-, -OOC-,

R represents H or a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, an alkynyl group having 2 to 25 carbon atoms, one or more of them A non-adjacent -CH ₂ -group is optionally -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -N- Substitution, and the substituted groups -O- or -S- atoms are not directly connected to each other, and one or more H atoms in the _{aforementioned -CH 2-are each optionally substituted by halogen.}

More preferably, the compound represented by the above formula III is specifically selected from the group consisting of the compounds represented by the following formula III3-1 to formula III26-14,

Wherein, R represents H or a linear, branched or cyclic alkyl group with 1 to 25 carbon atoms, an alkenyl group with 2 to 25 carbon atoms, and an alkynyl group with 2 to 25 carbon atoms, one of which Or multiple non-adjacent -CH ₂ -groups are optionally -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-,- N-substitution, and the substituted groups -O- or -S- atoms are not directly connected to each other, _{and one or more H atoms in the -CH 2} -are each optionally substituted by halogen;

Z represents a single bond, an alkylene group with 1-10 carbon atoms, and an alkenylene group with 2-10 carbon atoms, where any H atom can be substituted by fluorine, and any one or more unconnected -CH ₂ -Optionally substituted by -O-, -S-, -COO-, -OOC-.

More preferably, the compound represented by formula III is specifically selected from the group consisting of compounds represented by formula III19-10a1 to formula III25-13a2,

The polymerizable composition described in this patent also contains one or more compounds represented by formula IV,

In formula Ⅳ,

L ₈ represents F, Cl, CN or a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, or an alkynyl group having 2 to 25 carbon atoms , Wherein one or more non-adjacent -CH ₂ -groups are optionally -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O -, -N-substituted, and the substituted groups -O- or -S- atoms are not directly connected to each other, _{and one or more H atoms in the -CH 2} -are each optionally substituted by halogen;

g and h each independently represent 1, 2, 3 or 4;

i represents 0, 1 or 2;

f and j each independently represent 1, 2 or 3, f+j≥3;

Sp ₄ and Sp ₅ each independently represent a spacer;

P ₄ and P ₅ each independently represent a polymerizable group or H.

in,

The preferred structure is:

In the polymerizable composition of the present invention, preferably, the aforementioned one or more compounds represented by formula IV are selected from the group consisting of IV1-IV32, but are not limited to the following compounds;

Among them, the F atom may be substituted by a methyl group or a methoxy group.

The polymerizable composition of the present invention also contains one or more polyester resins, and the mass percentage content in the polymerizable composition is 5% to 25%, preferably 10% to 20%; its molecular weight is 5000 Between ～30,000, the more preferable molecular weight distribution is 10,000～20,000. Adding polyester resin can further improve the adhesion performance between the retardation film and the substrate, and improve the application performance of the product.

In the polymerizable composition of the present invention, the molecular weight of the compound represented by the aforementioned formula II is between 100 and 1,000, preferably between 100 and 700.

In the polymerizable composition of the present invention, the compound represented by the aforementioned formula I has a mass percentage content of 5%-40% in the polymerizable composition, preferably 10%-30%.

In the polymerizable composition of the present invention, the compound represented by the aforementioned formula II has a mass percentage content of 20%-60% in the polymerizable composition, preferably 20%-50%, more preferably 30%-50%. %.

In the polymerizable composition of the present invention, the compound represented by the aforementioned formula III, the mass percentage content of the polymerizable composition is 1%-20%, preferably 1%-15%.

In the polymerizable composition of the present invention, the compound represented by the aforementioned formula IV has a mass percentage content in the polymerizable composition of 1%-20%, preferably 5%-15%.

The polymerizable composition of the present invention may also contain one or more additives, and the addition of additives depends on the formulation, and it is not required that all additives be added.

Preferably, the aforementioned additives are one or more surfactants, chain transfer agents, sensitizers, anti-ultraviolet agents, polymerization inhibitors or antioxidants.

The polymerizable composition of the present invention also includes one or more initiators. The foregoing initiators are any compound that can initiate photopolymerization, and the mass percentage content of the initiator in the polymerizable composition is

1% to 10%, preferably 3% to 7%.

[Retardation film]

Another aspect of the present invention is a retardation film, which is polymerized by containing the aforementioned polymerizable composition.

Preferably, the retardation film of the retardation film has a retardation of 120-150 at a light wavelength of 550 nm.

The retardation film provided by the present invention can realize optical retardation without performing alignment processing on the base film, realize the effect of light phase modulation, and realize the negative dispersion characteristic.

[Method for preparing retardation film]

Another aspect of the present invention provides a method for preparing the aforementioned retardation film, which is specifically as follows:

Blending the aforementioned polymerizable composition containing the initiator into a solvent to form a polymerizable composition solution;

The resin layer of the polymerizable composition is photopolymerized by light irradiation to form a retardation film.

Preferably, the aforementioned light is visible light or ultraviolet light.

The preparation method of the phase difference film provided by the invention has simple steps, easy realization, low production cost, high production efficiency, and can realize large-scale production.

[Liquid crystal display element or liquid crystal display]

Another aspect of the present invention is a display element comprising the aforementioned polymerizable composition or the aforementioned retardation film, and the aforementioned display element is an active matrix display element or a passive matrix display element.

Another aspect of the present invention is a display which comprises the aforementioned polymerizable composition or the aforementioned retardation film, and the aforementioned display is an active matrix display or a passive matrix display.

Preferably, the aforementioned active matrix display element or display is an active matrix addressable liquid crystal display element or liquid crystal display.

Preferably, the aforementioned passive matrix display element or display is an OLED display element or a display.

As a method for preparing the liquid crystal display element or liquid crystal display of the present invention, the following method can be adopted: first, the aforementioned polymerizable composition solution is coated on the display device, and dried as needed. Then, the aforementioned polymerizable composition is irradiated with visible light or ultraviolet light. The polymer film formed by the aforementioned polymerizable composition can replace the traditional retardation film that requires an alignment layer. As a result, it is not only possible to avoid problems such as poor production yield of liquid crystal display elements or liquid crystal display devices caused by dust particles, static electricity residues, and brush marks caused by the arrangement of the alignment layer, and poor heat resistance and aging resistance, but also The preparation process of the liquid crystal display element or the liquid crystal display is effectively simplified, thereby improving the production efficiency and reducing the production cost.

Example

In order to explain the present invention more clearly, the following further describes the present invention in combination with preferred embodiments. Those skilled in the art should understand that the content described below is illustrative rather than restrictive, and should not be used to limit the protection scope of the present invention.

The preparation methods mentioned in the present invention are all conventional methods unless otherwise specified. The raw materials used can be obtained from publicly disclosed commercial channels unless otherwise specified. The percentages refer to mass percentages, the temperature is in degrees Celsius (°C), and other symbols The specific meaning and test conditions are as follows:

Δnd represents the amount of optical retardation, where Δn is the birefringence of the retardation film, d is the film thickness, the test condition is 25±2°C, and the Otsuka tms-100 test;

Adhesion performance test uses 100 grid method, SM600 tape for testing.

As a preferred embodiment, the compounds represented by formula I, formula II, formula III, and formula IV are preferably compounds represented by the following formulas:

The polyester resin is preferably a modified polyester resin (GK255) commercially available from Toyobo.

Example 1

The polymerizable composition solution and retardation film were prepared according to the composition and content of Table 1 below.

The preparation method of the polymerizable composition solution is as follows:

The components were weighed according to the contents shown in Table 1 and put into a brown bottle, added the solvent, placed on a magnetic stirring instrument and stirred for 1 hour, until the mixture was evenly stirred to obtain a polymerizable composition solution.

The preparation method of the retardation film is as follows:

First, prepare a polymerizable composition solution according to the above method;

Then, the above polymerizable composition solution was scraped on the PET substrate with a malt bar at a speed of 10 cm/s, and the scraped sample was dried in a blast drying oven at 80° C. for 40 seconds.

Finally, UV light with a wavelength of 365 nm and an irradiance of 30 Mw/cm ² was used at room temperature to cure for 45 seconds to obtain a retardation film.

The retardation amount and adhesion performance test of the prepared retardation film were carried out.

Table 1 Example 1 Composition and content of polymerizable composition

Ⅰ19-3Ⅰ19-3	Ⅱ1-1-1Ⅱ1-1-1	Ⅲ25-13a2Ⅲ25-13a2	Ⅳ4Ⅳ4	GK255GK255	907907	甲苯Toluene
0.14g0.14g	0.14g0.14g	0.02g0.02g	0.01g0.01g	0.04g0.04g	0.01g0.01g	0.7g0.7g

Example 2

Using the same polymerizable composition and retardation film preparation method as in Example 1, the polymerizable composition solution and retardation film were prepared according to the composition and content of Table 2 below. The retardation amount and adhesion performance test of the prepared retardation film were carried out.

Table 2 Example 2 Composition and content of polymerizable composition

Ⅰ19-3Ⅰ19-3	Ⅱ3-1-1Ⅱ3-1-1	Ⅲ25-13a2Ⅲ25-13a2	Ⅳ4Ⅳ4	GK255GK255	907907	甲苯Toluene
0.14g0.14g	0.14g0.14g	0.02g0.02g	0.01g0.01g	0.04g0.04g	0.01g0.01g	0.7g0.7g

Table 3 shows the retardation test data of the retardation film provided in Example 1 and Example 2 at different wavelengths.

Table 3 Delay amount test data

相位差膜Retardation film	实施例1Example 1	实施例2Example 2
Re[450](nm)Re[450](nm)	111.8111.8	105.9105.9
Re[500](nm)Re[500](nm)	123.7123.7	121.3121.3
Re[550](nm)Re[550](nm)	132.5132.5	132.7132.7
Re[600](nm)Re[600](nm)	139.2139.2	141.3141.3
Re[700](nm)Re[700](nm)	148.5148.5	153.4153.4
Re[750](nm)Re[750](nm)	151.8151.8	157.7157.7
Re[450](nm)/Re[550](nm)Re[450](nm)/Re[550](nm)	0.840.84	0.800.80
Rth[450](nm)Rth[450](nm)	81.481.4	103.7103.7
Rth[500](nm)Rth[500](nm)	110.8110.8	123.2123.2
Rth[550](nm)Rth[550](nm)	132.5132.5	137.7137.7
Rth[600](nm)Rth[600](nm)	149.0149.0	148.8148.8
Rth[700](nm)Rth[700](nm)	172.1172.1	163.9163.9
Rth[750](nm)Rth[750](nm)	180.3180.3	169.4169.4
Rth[450](nm)/Rth[550](nm)Rth[450](nm)/Rth[550](nm)	0.610.61	0.750.75

The adhesion test of the retardation film provided in Example 1 and Example 2 showed that the samples dropped less than 3%.

Example 3

The polymerizable composition solution and retardation film were prepared according to the composition and content of Table 4 below. The preparation method is the same as in Example 1. The retardation amount and adhesion performance test of the prepared retardation film were carried out.

Table 4 Example 3 Composition and content of polymerizable composition

Ⅰ4-3Ⅰ4-3	Ⅱ4-1-1Ⅱ4-1-1	Ⅲ25-13a2Ⅲ25-13a2	Ⅳ4Ⅳ4	GK255GK255	907907	甲苯Toluene
0.14g0.14g	0.14g0.14g	0.02g0.02g	0.01g0.01g	0.04g0.04g	0.01g0.01g	0.7g0.7g

Example 4

The polymerizable composition solution and retardation film were prepared according to the composition and content of Table 5 below. The preparation method is the same as in Example 1. The retardation and adhesion performance of the prepared retardation film were tested.

Table 5 Example 4 Composition and content of polymerizable composition

Ⅰ19-3Ⅰ19-3	Ⅱ1-1-1Ⅱ1-1-1	Ⅲ24-13a1Ⅲ24-13a1	Ⅳ5Ⅳ5	GK255GK255	907907	甲苯Toluene
0.14g0.14g	0.14g0.14g	0.02g0.02g	0.01g0.01g	0.04g0.04g	0.01g0.01g	0.7g0.7g

The retardation test data of the retardation film provided in Example 3 and Example 4 at different wavelengths are shown in Table 6.

Table 6 Delay amount test data

相位差膜Retardation film	实施例3Example 3	实施例4Example 4
Re[450](nm)Re[450](nm)	108.2108.2	103.5103.5
Re[500](nm)Re[500](nm)	117.3117.3	118.0118.0
Re[550](nm)Re[550](nm)	135.0135.0	128.7128.7
Re[600](nm)Re[600](nm)	141.4141.4	136.8136.8
Re[700](nm)Re[700](nm)	148.1148.1	148.2148.2
Re[750](nm)Re[750](nm)	152.8152.8	152.3152.3
Re[450](nm)/Re[550](nm)Re[450](nm)/Re[550](nm)	0.800.80	0.800.80
Rth[450](nm)Rth[450](nm)	18.218.2	75.975.9
Rth[500](nm)Rth[500](nm)	23.923.9	85.585.5
Rth[550](nm)Rth[550](nm)	28.228.2	92.692.6
Rth[600](nm)Rth[600](nm)	31.431.4	98.098.0
Rth[700](nm)Rth[700](nm)	35.935.9	105.6105.6
Rth[750](nm)Rth[750](nm)	37.537.5	108.3108.3
Rth[450](nm)/Rth[550](nm)Rth[450](nm)/Rth[550](nm)	0.650.65	0.820.82

The adhesion test of the retardation film provided in Example 3 and Example 4 showed that the samples dropped less than 3%.

Example 5

The polymerizable composition solution and retardation film were prepared according to the composition and content of Table 7 below. The preparation method is the same as in Example 1. The retardation and adhesion performance of the prepared retardation film were tested.

Table 7 Example 5 Composition and content of polymerizable composition

Ⅰ4-3Ⅰ4-3	Ⅱ3-1-1Ⅱ3-1-1	Ⅲ25-13a2Ⅲ25-13a2	Ⅳ5Ⅳ5	GK255GK255	907907	甲苯Toluene
0.07g0.07g	0.14g0.14g	0.01g0.01g	0.01g0.01g	0.04g0.04g	0.01g0.01g	0.7g0.7g

Example 6

The polymerizable composition solution and retardation film were prepared according to the composition and content of Table 8 below. The preparation method is the same as in Example 1. The retardation and adhesion performance of the prepared retardation film were tested.

Table 8 Example 6 Composition and content of polymerizable composition

Ⅰ19-3Ⅰ19-3	Ⅱ4-1-1Ⅱ4-1-1	Ⅲ24-13a1Ⅲ24-13a1	Ⅳ5Ⅳ5	GK255GK255	907907	甲苯Toluene
0.07g0.07g	0.14g0.14g	0.01g0.01g	0.01g0.01g	0.04g0.04g	0.01g0.01g	0.7g0.7g

The retardation test data of the retardation film provided in Example 5 and Example 6 at different wavelengths are shown in Table 9.

Table 9 Delay amount test data

相位差膜Retardation film	实施例5Example 5	实施例6Example 6
Re[450](nm)Re[450](nm)	108.2108.2	114.2114.2
Re[500](nm)Re[500](nm)	125.7125.7	132.8132.8
Re[550](nm)Re[550](nm)	139.5139.5	140.7140.7
Re[600](nm)Re[600](nm)	154.0154.0	153.2153.2
Re[700](nm)Re[700](nm)	166.6166.6	167.9167.9
Re[750](nm)Re[750](nm)	170.8170.8	172.2172.2
Re[450](nm)/Re[550](nm)Re[450](nm)/Re[550](nm)	0.780.78	0.810.81
Rth[450](nm)Rth[450](nm)	111.3111.3	111.2111.2
Rth[500](nm)Rth[500](nm)	128.4128.4	129.5129.5
Rth[550](nm)Rth[550](nm)	140.4140.4	143.3143.3
Rth[600](nm)Rth[600](nm)	152.7152.7	152.9152.9

Rth[700](nm)Rth[700](nm)	165.3165.3	168.2168.2
Rth[750](nm)Rth[750](nm)	170.3170.3	172.3172.3
Rth[450](nm)/Rth[550](nm)Rth[450](nm)/Rth[550](nm)	0.870.87	0.780.78

The adhesion test of the retardation film provided in Example 5 and Example 6 was performed, and the samples dropped less than 3%.

Example 7

The polymerizable composition solution and retardation film were prepared according to the composition and content of Table 10 below. The preparation method is the same as in Example 1. The retardation and adhesion performance of the prepared retardation film were tested.

Table 10 Example 7 Composition and content of polymerizable composition

Ⅰ19-3Ⅰ19-3	Ⅱ1-1-1Ⅱ1-1-1	Ⅳ15Ⅳ15	GK255GK255	907907	甲苯Toluene
0.07g0.07g	0.14g0.14g	0.02g0.02g	0.04g0.04g	0.01g0.01g	0.7g0.7g

Example 8

The polymerizable composition solution and retardation film were prepared according to the composition and content of Table 11 below. The preparation method is the same as in Example 1. The retardation and adhesion performance of the prepared retardation film were tested.

Table 11 The composition and content of the polymerizable composition of Example 8

Ⅰ4-3Ⅰ4-3	Ⅱ3-1-1Ⅱ3-1-1	Ⅳ15Ⅳ15	GK255GK255	907907	甲苯Toluene
0.07g0.07g	0.14g0.14g	0.02g0.02g	0.04g0.04g	0.01g0.01g	0.7g0.7g

The retardation test data of the retardation film provided in Example 7 and Example 8 at different wavelengths are shown in Table 12.

Table 12 Delay amount test data

相位差膜Retardation film	实施例7Example 7	实施例8Example 8
Re[450](nm)Re[450](nm)	103.7103.7	100.4100.4
Re[500](nm)Re[500](nm)	135.8135.8	111.2111.2
Re[550](nm)Re[550](nm)	149.3149.3	121.5121.5
Re[600](nm)Re[600](nm)	162.6162.6	127.1127.1
Re[700](nm)Re[700](nm)	181.0181.0	136.2136.2
Re[750](nm)Re[750](nm)	186.2186.2	139.8139.8

Re[450](nm)/Re[550](nm)Re[450](nm)/Re[550](nm)	0.690.69	0.830.83
Rth[450](nm)Rth[450](nm)	105.5105.5	103.0103.0
Rth[500](nm)Rth[500](nm)	120.7120.7	120.8120.8
Rth[550](nm)Rth[550](nm)	136.0136.0	135.6135.6
Rth[600](nm)Rth[600](nm)	145.2145.2	146.0146.0
Rth[700](nm)Rth[700](nm)	160.0160.0	160.2160.2
Rth[750](nm)Rth[750](nm)	164.7164.7	166.1166.1
Rth[450](nm)/Rth[550](nm)Rth[450](nm)/Rth[550](nm)	0.780.78	0.760.76

The adhesion test of the retardation film provided in Example 7 and Example 8 showed that the samples dropped less than 3%.

Example 9

The polymerizable composition solution and retardation film were prepared according to the composition and content of Table 13 below. The preparation method is the same as in Example 1. The retardation and adhesion performance of the prepared retardation film were tested.

Table 13 The composition and content of the polymerizable composition of Example 9

Ⅰ19-3Ⅰ19-3	Ⅱ4-1-1Ⅱ4-1-1	Ⅳ15Ⅳ15	GK255GK255	907907	甲苯Toluene
0.07g0.07g	0.14g0.14g	0.02g0.02g	0.04g0.04g	0.01g0.01g	0.7g0.7g

Example 10

The polymerizable composition solution and retardation film were prepared according to the composition and content of Table 13 above. The preparation method is basically the same as in Example 1, but the substrate is replaced with PVA, and other conditions remain unchanged. The retardation and adhesion performance of the prepared retardation film were tested.

Example 11

The polymerizable composition solution and retardation film were prepared according to the composition and content of Table 13 above. The preparation method is basically the same as in Example 1, but the substrate is replaced with ITO, and other conditions remain unchanged. . The retardation and adhesion performance of the prepared retardation film were tested.

The retardation test data of the retardation film provided in Example 9, Example 10 and Example 11 at different wavelengths are shown in Table 14.

Table 14 Delay amount test data

Retardation film

Example 9

Example 10

Example 11

Re[450](nm)Re[450](nm)	99.499.4	109.1109.1	99.599.5
Re[500](nm)Re[500](nm)	123.3123.3	117.8117.8	123.4123.4
Re[550](nm)Re[550](nm)	139.8139.8	124.2124.2	139.6139.6
Re[600](nm)Re[600](nm)	153.2153.2	129.1129.1	153.7153.7
Re[700](nm)Re[700](nm)	170.3170.3	136.1136.1	170.6170.6
Re[750](nm)Re[750](nm)	172.1172.1	138.4138.4	172.5172.5
Re[450](nm)/Re[550](nm)Re[450](nm)/Re[550](nm)	0.710.71	0.880.88	0.710.71
Rth[450](nm)Rth[450](nm)	104.2104.2	48.348.3	104.3104.3
Rth[500](nm)Rth[500](nm)	123.5123.5	45.245.2	123.4123.4
Rth[550](nm)Rth[550](nm)	138.7138.7	43.543.5	138.8138.8
Rth[600](nm)Rth[600](nm)	149.4149.4	42.042.0	149.2149.2
Rth[700](nm)Rth[700](nm)	164.8164.8	40.840.8	164.6164.6
Rth[750](nm)Rth[750](nm)	169.0169.0	39.939.9	169.1169.1
Rth[450](nm)/Rth[550](nm)Rth[450](nm)/Rth[550](nm)	0.750.75	1.111.11	0.750.75

The adhesion test of the retardation film provided in Example 9, Example 10 and Example 11 was performed, and the samples dropped less than 3%.

Example 12

The polymerizable composition solution and retardation film were prepared according to the composition and content of Table 15 below. The preparation method is the same as in Example 1. And carry out delay amount and adhesion performance test.

Table 15 The composition and content of the polymerizable composition of Example 12

Ⅰ4-3Ⅰ4-3	Ⅱ1-1-1Ⅱ1-1-1	907907	甲苯Toluene
0.14g0.14g	0.02g0.02g	0.01g0.01g	0.7g0.7g

The retardation test data of the retardation film provided in Example 12 at different wavelengths is shown in Table 16.

Table 16 Delay test data

相位差膜Retardation film	实施例12Example 12
Re[450](nm)Re[450](nm)	103.2103.2
Re[500](nm)Re[500](nm)	115.7115.7
Re[550](nm)Re[550](nm)	124.3124.3
Re[600](nm)Re[600](nm)	131.2131.2
Re[700](nm)Re[700](nm)	139.4139.4
Re[750](nm)Re[750](nm)	145.2145.2
Re[450](nm)/Re[550](nm)Re[450](nm)/Re[550](nm)	0.830.83
Rth[450](nm)Rth[450](nm)	100.2100.2
Rth[500](nm)Rth[500](nm)	118.3118.3
Rth[550](nm)Rth[550](nm)	131.2131.2
Rth[600](nm)Rth[600](nm)	139.5139.5
Rth[700](nm)Rth[700](nm)	154.8154.8
Rth[750](nm)Rth[750](nm)	157.4157.4
Rth[450](nm)/Rth[550](nm)Rth[450](nm)/Rth[550](nm)	0.760.76

The adhesion test of the retardation film provided in Example 12 showed that 3%<all samples dropped <10%.

Comparative example 1

The polymerizable composition solution and retardation film were prepared according to the composition and content of Table 17 below. The preparation method is the same as in Example 1. The retardation and adhesion performance of the prepared retardation film were tested.

Table 17 Comparative Example 1 Composition and content of polymerizable composition

Ⅰ19-3Ⅰ19-3	Ⅲ25-13a2Ⅲ25-13a2	Ⅳ4Ⅳ4	907907	甲苯Toluene
0.14g0.14g	0.02g0.02g	0.02g0.02g	0.006g0.006g	0.4g0.4g

Comparative example 2

The polymerizable composition solution was prepared with the same composition and content as in Comparative Example 1, and the substrate was replaced with friction-aligned PET, and under other conditions unchanged, a retardation film was prepared. And carry out delay amount and adhesion performance test.

Comparative example 3

The polymerizable composition solution and retardation film were prepared according to the composition and content of Table 18 below. The preparation method is the same as in Example 1. The retardation and adhesion performance of the prepared retardation film were tested.

Table 18 Composition and content of polymerizable composition of Comparative Example 3

Ⅱ4-1-1Ⅱ4-1-1	GK255GK255	907907	甲苯Toluene
0.14g0.14g	0.02g0.02g	0.005g0.005g	0.4g0.4g

Comparative example 4

The biaxially stretched polypropylene film (Toray Co., Ltd., thickness 60μm) was stretched 1.5 times in an air-circulating drying oven (140°C ± 1°C) under a fixed longitudinal width using a roll stretching machine. The retardation film is obtained, and the retardation and adhesion performance of the retardation film are tested.

The retardation test data of the retardation films provided by Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4 at different wavelengths are shown in Table 19.

Table 19 Delay amount test data

相位差膜Retardation film	对比例1Comparative example 1	对比例2Comparative example 2	对比例3Comparative example 3	对比例4Comparative example 4
Re[450](nm)Re[450](nm)	94.294.2	135.2135.2	8.28.2	220.5220.5
Re[500](nm)Re[500](nm)	92.792.7	128.8128.8	9.59.5	241.3241.3
Re[550](nm)Re[550](nm)	88.888.8	120.2120.2	10.410.4	263.6263.6
Re[600](nm)Re[600](nm)	84.184.1	114.3114.3	11.111.1	274.7274.7
Re[700](nm)Re[700](nm)	81.281.2	105.4105.4	12.112.1	281.2281.2
Re[750](nm)Re[750](nm)	73.373.3	92.592.5	12.512.5	287.4287.4
Re[450](nm)/Re[550](nm)Re[450](nm)/Re[550](nm)	1.061.06	1.121.12	0.780.78	0.840.84
Rth[450](nm)Rth[450](nm)	152.9152.9	170.6170.6	1.71.7	114.4114.4
Rth[500](nm)Rth[500](nm)	144.2144.2	160.9160.9	1.61.6	129.7129.7
Rth[550](nm)Rth[550](nm)	122.1122.1	131.7131.7	1.51.5	135.3135.3
Rth[600](nm)Rth[600](nm)	106.2106.2	110.5110.5	1.41.4	141.6141.6

Rth[700](nm)Rth[700](nm)	85.685.6	83.183.1	1.41.4	147.4147.4
Rth[750](nm)Rth[750](nm)	57.057.0	55.755.7	1.41.4	153.3153.3
Rth[450](nm)/Rth[550](nm)Rth[450](nm)/Rth[550](nm)	1.251.25	1.291.29	1.061.06	0.850.85

The adhesion test of the retardation film provided by Comparative Example 1 and Comparative Example 2 showed that the samples dropped> 30%, and the retardation film samples provided by Comparative Example 3 dropped <3%. Comparative Example 4 was made by the stretching method, and the sample did not fall off.

It can be seen from the comparison of the retardation film test data provided by the foregoing Examples 1-12 and Comparative Examples 1 to 4 that the retardation films provided by Examples 1-12 and Comparative Example 1, Comparative Example 2, and Comparative Example 4 all achieved negative results. Dispersion characteristics. The retardation film provided in Comparative Example 1 is a retardation film formed of a pure liquid crystal polymerizable composition without adding the compound of formula II. The retardation on the unaligned PET substrate is too small and cannot meet the requirements of use. The retardation film provided in Comparative Example 3 only contains the compound of formula II, and there is almost no retardation. From the comparison of the phase difference film test data provided by Comparative Example 1 and Comparative Example 2, it can be seen that the retardation can be increased when the PET substrate is aligned. However, the retardation films provided by Comparative Examples 1 to 2 have positive dispersion characteristics, and the adhesion performance of the two to the substrate is poor. The retardation film provided by Comparative Example 4 is a traditional stretched retardation film. The thickness of Comparative Example 4 after being stretched is much larger than that of Examples 1-12, and it is difficult to meet the needs of flexible display devices. It is too large to meet the requirements of quarter-wave plate retardation film. Generally, in order to meet the retardation requirement of the quarter-wave plate retardation film, the retardation (Re[550](nm)) at a wavelength of 550nm needs to be between 120 and 150.

Claims

A polymerizable composition characterized by comprising one or more compounds represented by formula I and one or more compounds represented by formula II;

In formula I,

L 1 represents H, F, Cl, CN or a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, or a C 2-25 Alkynyl, in which one or more non-adjacent -CH 2 -groups are optionally -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO -O-, -N- substituted, and the substituted groups -O- or -S- atoms are not directly connected to each other, and one or more H atoms in the -CH 2 -are each optionally substituted by halogen;

Represents 1,4-cyclohexylene, 1,4-phenylene, 2,6-naphthylene, 1,5-naphthylene or 1,4-naphthylene;

Sp 1 and Sp 2 each independently represent a spacer;

P 1 and P 2 each independently represent a polymerizable group or H, and at least one of P 1 and P 2 represents a polymerizable group;

a, b, and c each independently represent 1, 2 or 3;

In formula Ⅱ,

T represents -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -N- or -CH 2 -;

L 7 represents H, F, Cl, CN or a linear alkyl, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and 2 carbon atoms ~10 alkynyl groups, in which one or more non-adjacent -CH 2 -groups are optionally replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-,- O-CO-O-, -N- substituted, and the substituted groups -O- or -S- atoms are not directly connected to each other, and one or more H atoms in the -CH 2-are each optionally halogen replace;

P 6 and P 7 each independently represent a polymerizable group or H, and at least one of P 6 and P 7 represents a polymerizable group;

k 1 , k 2, or k 3 each independently represents an integer from 0 to 50, k 4 represents an integer from 1 to 50, and k 1 ≤k 3 and k 2 ≤k 3 .
The polymerizable composition according to claim 1, wherein the cyclic alkyl group represented by L 7 in the compound represented by formula II is 1,4-cyclohexylene, 1,4-phenylene , 2,6-naphthylene, 1,5-naphthylene, 1,4-naphthylene, wherein the H atom on the ring is optionally substituted by halogen.
The polymerizable composition of claim 1, further comprising one or more compounds of formula III,

In formula Ⅲ,

R represents H or a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, an alkynyl group having 2 to 25 carbon atoms, one or more of them A non-adjacent -CH 2 -group is optionally -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -N- Substitution, and the substituted groups -O- or -S- atoms are not directly connected to each other, and one or more H atoms in the -CH 2 -are each optionally substituted by halogen;

Z represents a single bond, an alkylene group with 1-10 carbon atoms, and an alkenylene group with 2-10 carbon atoms, where any H atom can be substituted by fluorine, and any one or more unconnected -CH 2 -Optionally substituted by -O-, -S-, -COO-, -OOC-;

L 2 and L 3 each independently represent H, F, Cl, CN or a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, and a carbon atom An alkynyl group with a number of 2-25, wherein one or more non-adjacent -CH 2 -groups are optionally -O-, -S-, -CO-, -CO-O-, -O-CO -, -O-CO-O-, -N- substituted, and the substituted groups -O- or -S- atoms are not directly connected to each other, and one or more H atoms in the -CH 2-are each optional地 is replaced by halogen;

Represents aryl, heteroaryl, alicyclic, heterocyclic or fused ring, and the H atom on the ring is optionally substituted by L 6 mono- or poly-substituted;

The L 6 represents F, Cl, CN or a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, or a C 2-25 Alkynyl, in which one or more non-adjacent -CH 2 -groups are optionally -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO -O-, -N- substituted, and the substituted groups -O- or -S- atoms are not directly connected to each other, and one or more H atoms in the -CH 2 -are each optionally substituted by halogen;

Sp 3 represents the spacer base;

P 3 represents a polymerizable group or H;

d and e each independently represent 0, 1, 2, 3 or 4;

m and n each independently represent 0, 1 or 2, and m+n≥1;

o means 1, 2 or 3.
The polymerizable composition according to claim 1, characterized in that it further comprises one or more compounds represented by formula IV,

In formula Ⅳ,

L 4 and L 5 each independently represent H, F, Cl, CN or a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, and a carbon atom An alkynyl group with a number of 2-25, wherein one or more non-adjacent -CH 2 -groups are optionally -O-, -S-, -CO-, -CO-O-, -O-CO -, -O-CO-O-, -N- substituted, and the substituted groups -O- or -S- atoms are not directly connected to each other, and one or more H atoms in the -CH 2-are each optional地 is replaced by halogen;

Represents aryl, heteroaryl, alicyclic, heterocyclic or condensed ring, and the H atom on the ring is optionally substituted by L 8 mono- or poly-substituted;

The L 8 represents F, Cl, CN or a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, or a C 2-25 Alkynyl, in which one or more non-adjacent -CH 2 -groups are optionally -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO -O-, -N- substituted, and the substituted groups -O- or -S- atoms are not directly connected to each other, and one or more H atoms in the -CH 2 -are each optionally substituted by halogen;

g and h each independently represent 1, 2, 3 or 4;

i represents 0, 1 or 2;

f and j each independently represent 1, 2 or 3, and f+j≥3;

Sp 4 and Sp 5 each independently represent a spacer;

P 4 and P 5 each independently represent a polymerizable group or H.
The polymerizable composition according to claim 1, characterized in that it further comprises one or more polyester resins.
The polymerizable composition according to claim 1, wherein the molecular weight of the compound represented by formula II is between 100 and 1000, and the added mass percentage content is 20% to 60%.
The polymerizable composition of claim 1, further comprising one or more additives; the additives include antioxidants, surfactants, polymerization inhibitors, chain transfer agents, sensitizers, anti-ultraviolet Agent or polymerization inhibitor.
The polymerizable composition according to any one of claims 1 to 7, characterized in that it further comprises one or more initiators, and the initiators are compounds that can initiate photopolymerization.
A retardation film, characterized in that the retardation mode is polymerized by the polymerizable composition of claim 8.
The retardation film according to claim 9, wherein the retardation of the retardation film at a light wavelength of 550 nm is 120 to 150.
A method for preparing retardation film, which is characterized in that:

Mixing the polymerizable composition of claim 8 into a solvent to form a polymerizable composition solution;

Coating the polymerizable composition solution on a substrate to form a polymerizable composition solution layer;

By drying the polymerizable composition solution layer to obtain a polymerizable composition resin layer;

The resin layer of the polymerizable composition is photopolymerized by light irradiation to form a retardation film.
The method for preparing a retardation film according to claim 11, wherein the light is visible light or ultraviolet light.
A display element, comprising the polymerizable composition of claim 8 or the retardation film of any one of claims 9 to 10, and the display element is an active matrix display element or a passive matrix Display components.
A display, characterized in that it comprises the polymerizable composition according to claim 8 or the retardation film according to any one of claims 9 to 10, and the display is an active matrix display or a passive matrix display.