CN116444732B - Polymerizable composition, phase difference film, preparation method and display device - Google Patents

Polymerizable composition, phase difference film, preparation method and display device Download PDF

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CN116444732B
CN116444732B CN202310474708.XA CN202310474708A CN116444732B CN 116444732 B CN116444732 B CN 116444732B CN 202310474708 A CN202310474708 A CN 202310474708A CN 116444732 B CN116444732 B CN 116444732B
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carbon atoms
formula
polymerizable composition
group
compound
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CN116444732A (en
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周志华
高�玉
王晨阳
张东升
王建
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Chengdu Reboke Material Technology Co ltd
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—Birefringent or phase retarding elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/08—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of polarising materials
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation

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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The application provides a polymerizable composition, a phase difference film, a preparation method and a display device, relates to the technical field of liquid crystal display, and solves the technical problems of poor reliability and poor bending resistance of the existing phase difference film. The polymerizable composition comprises: acrylic resin, a first material and a second material; wherein the first material comprises a compound having formula I and the second material comprises a compound having formula II and/or a compound having formula III.

Description

Polymerizable composition, phase difference film, preparation method and display device
Technical Field
The application relates to the technical field of liquid crystal display, in particular to a polymerizable composition, a phase difference film, a preparation method and a display device.
Background
The display device has some inherent technical defects, so that the display device can be influenced by external light in the display process. For example, people have poor viewing experiences such as reduced contrast, narrow viewing angle range, etc. when viewing a screen under intense light. In order to solve the above-mentioned problems, a retardation film is generally introduced in the related art.
However, the reliability and bending resistance of the current retardation film are poor, so that a display device including the retardation film is easily deteriorated during use.
Disclosure of Invention
The application provides a polymerizable composition, a phase difference film, a preparation method and a display device, which can be used for solving the technical problems of poor reliability and poor bending resistance of the existing phase difference film.
In a first aspect, embodiments herein provide a polymerizable composition, characterized in that the polymerizable composition comprises: acrylic resin, a first material and a second material;
wherein the first material comprises a compound having formula I, and the second material comprises a compound having formula II and/or a compound having formula iii;
the formula I is as follows:
wherein L is 1 Comprises H, F, cl, CN, a straight chain with 1-25 carbon atoms, a branched chain with 1-25 carbon atoms, a cyclic alkyl with 1-25 carbon atoms, an alkenyl with 2-25 carbon atoms and an alkynyl with 2-25 carbon atoms;
in said formula IComprises any one of 1, 4-cyclohexylene, 1, 4-phenylene, 2, 6-naphthylene, 1, 5-naphthylene and 1, 4-naphthylene;
In said formula IComprises any one of 1, 4-cyclohexylene, 1, 4-phenylene, 2, 6-naphthylene, 1, 5-naphthylene and 1, 4-naphthylene;
in said formula IComprises any one of 1, 4-cyclohexylene, 1, 4-phenylene, 2, 6-naphthylene, 1, 5-naphthylene and 1, 4-naphthylene;
Sp 1 is a spacer, sp 2 Is a spacer;
P 1 comprising a polymerisable group or H; p (P) 2 Comprising a polymerisable group or H; and P is 1 And P 2 At least one of which is a polymerizable group;
a is 1, 2 or 3; b is 1, 2 or 3; c is 1, 2 or 3;
the formula II is as follows:
the formula III is as follows:
in the formula II and the formula III, R includes any one of H, a straight chain having 1 to 25 carbon atoms, a branched chain having 1 to 25 carbon atoms, and a cyclic alkyl group having 1 to 25 carbon atoms;
z comprises any one of a single bond, an alkyl group having 1 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms;
L 2 comprises H, F, cl, CN, a straight chain with 1-25 carbon atoms, a branched chain with 1-25 carbon atoms, a cyclic alkyl with 1-25 carbon atoms, an alkenyl with 2-25 carbon atoms and an alkynyl with 2-25 carbon atoms;
L 3 Comprises H, F, cl, CN, a straight chain with 1-25 carbon atoms, a branched chain with 1-25 carbon atoms, a cyclic alkyl with 1-25 carbon atoms, an alkenyl with 2-25 carbon atoms and an alkynyl with 2-25 carbon atoms;
said formula II and said formula IIIIncluding any of aryl, heteroaryl, alicyclic, heterocyclic, and fused rings;
Sp 3 comprising a spacer; p (P) 3 Comprising a polymerisable group or H;
d is 0, 1, 2, 3 or 4; e is 0, 1, 2, 3 or 4; f is 0, 1, 2, 3 or 4; g is 0, 1, 2, 3 or 4;
m is 0, 1 or 2, n is 0, 1 or 2, and m+n is not less than 1;
o is 1, 2 or 3, h is 1, 2 or 3.
In a second aspect, embodiments of the present application provide a retardation film polymerized based on the polymerizable composition provided in the first aspect of the present application.
In a third aspect, embodiments of the present application provide a method for preparing a retardation film, the method comprising:
mixing the polymerizable composition provided in the first aspect of the present application with a solvent to obtain a polymerizable composition solution;
coating the polymerizable composition solution on the surface of a substrate, and drying to obtain a polymerizable composition resin layer;
And irradiating the polymerizable composition resin layer to obtain a retardation film.
In a fourth aspect, embodiments of the present application provide a display device comprising the polymerizable composition provided in the first aspect or the phase difference film provided in the second aspect of the present application, the display device being an active matrix display device or a passive matrix display device
The beneficial effects brought by the embodiment of the application are as follows:
with the solution provided in the embodiments of the present application, the setting of the polymerizable composition includes: acrylic resin, a first material and a second material; wherein the first material comprises a compound having formula I and the second material comprises a compound having formula II and/or a compound having formula III. Therefore, the crosslinking density of the phase difference film can be improved, a network structure is formed, and the reliability and bending resistance of the phase difference film can be improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. In the drawings:
Fig. 1 is a schematic flow chart of a preparation method of a retardation film according to an embodiment of the present application.
Detailed Description
For the purposes, technical solutions and advantages of the present application, the technical solutions of the present application will be clearly and completely described below with reference to specific embodiments of the present application and corresponding drawings. It will be apparent that the described embodiments are only some, but not all, of the embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
As described in the background of the present application, retardation films currently have reliability and bending resistance. In view of this, the present embodiments provide a polymerizable composition that can be used to prepare a retardation film. Specifically, the polymerizable composition may comprise: acrylic resin, a first material and a second material; the first material comprises a compound having formula I, and the second material comprises a compound having formula II and/or a compound having formula iii.
Wherein, the acrylic resin may be a methacrylic resin. The methacrylic resin may be a methacrylic monomer or a methacrylic modified resin. The acrylic resin is specifically a multifunctional compound, has a plurality of (three) acrylic bonds, further has more reaction sites, and can improve the crosslinking density of the phase difference film, so that a network structure is formed among materials.
In the embodiment of the present application, the refractive index of the acrylic resin is 1.40 to 1.60, and the acrylic resin has no liquid crystallinity, i.e., no birefringent property. Further, the rigidity of the acrylic resin is weaker than the first material and the second material, and the reliability and bending resistance of the retardation film can be improved. In particular, an acrylic resin having a molecular weight of 200 to 2000 may be preferable, and a molecular weight of 300 to 1500 may be more preferable, so that the stability of the polymerizable composition can be further improved, and the bending resistance of the retardation film can be further improved. In addition, the addition of the acrylic resin can also improve the adhesion performance between the phase difference film and the base material and improve the reliability of the product.
In an embodiment of the present application, the structural formula of formula I may be as follows:
wherein L is 1 May include H, F, cl, CN, a straight chain having 1 to 25 carbon atoms, a branched chain having 1 to 25 carbon atoms, a cyclic alkyl having 1 to 25 carbon atoms, an alkenyl having 2 to 25 carbon atoms, or an alkynyl having 2 to 25 carbon atoms. Further, at L 1 With one or more-CH 2 In the case of groups, in which one or more-CH 2 The groups may each optionally be substituted with-O-, -S-, -CO-, -CO-O-, -O-CO-O-, or-N-substitution. Wherein, when a plurality of-CH 2 -when substituted, substituted-CH 2 -being unconnected-CH 2 -. After substitution, -O-and-O-are not directly connected to each other, -O-and-S-are not directly connected to each other, and-S-are not directly connected to each other. In addition, at L 1 Having one or more H atomsEach H atom may be optionally substituted with a halogen atom.
In formula IAny one of 1, 4-cyclohexylene group, 1, 4-phenylene group, 2, 6-naphthylene group, 1, 5-naphthylene group, and 1, 4-naphthylene group may be included.
In formula IAny one of 1, 4-cyclohexylene group, 1, 4-phenylene group, 2, 6-naphthylene group, 1, 5-naphthylene group, and 1, 4-naphthylene group may be included.
In formula IAny one of 1, 4-cyclohexylene group, 1, 4-phenylene group, 2, 6-naphthylene group, 1, 5-naphthylene group and 1, 4-naphthylene group may be used.
Sp 1 Is a spacer, sp 2 Is a spacer; wherein the spacer may include an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a fluorine-substituted alkynyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 8 carbon atoms or a fluorine-substituted alkynyl group having 3 to 8 carbon atoms. Further, one or more-CH's are present in the spacer 2 In the case of groups, in which one or more-CH 2 The groups may each optionally be substituted with-O-, -S-, -COO-or-OOC-substitution. Wherein, when a plurality of-CH 2 -when substituted, substituted-CH 2 -being unconnected-CH 2 -。
P 1 May include a polymerizable group or H; p (P) 2 May include a polymerizable group or H; and P is 1 And P 2 At least one ofEach is a polymerizable group. Wherein the polymerizable group comprises a methacrylate group, an acrylate group, a vinyl group or an ethylene oxide group, preferably an acrylate group or a methacrylate group.
a may be 1, 2 or 3; b may be 1, 2 or 3; c may be 1, 2 or 3.
In an embodiment of the present application, the structural formula of formula II may be as follows:
the structural formula of the formula III can be as follows:
in the formula II and the formula III, R may include any one of H, a straight chain having 1 to 25 carbon atoms, a branched chain having 1 to 25 carbon atoms, and a cyclic alkyl having 1 to 25 carbon atoms. Further, having one or more-CH's at R 2 In the case of groups, in which one or more-CH 2 The groups may each optionally be substituted with-O-, -S-, -CO-, -CO-O-, -O-CO-O-, or-N-substitution. Wherein, when a plurality of-CH 2 -when substituted, substituted-CH 2 -being unconnected-CH 2 -. After substitution, -O-and-O-are not directly connected to each other, -O-and-S-are not directly connected to each other, and-S-are not directly connected to each other. In addition, in the case where R has one or more H atoms, each H atom may be optionally substituted with a halogen atom or a methyl group.
Z may include any one of a single bond, an alkyl group having 1 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms. Further, any of the H atoms in Z may be substituted with a fluorine atom. In the presence of one or more-CH 2 In the case of groups, in which one or more-CH 2 The groups may each optionally be substituted with-O-, -S-, -COO-or-OOC-substitution. Wherein, when a plurality of-CH 2 -when it is substituted, the amino acid sequence,substituted-CH 2 -being unconnected-CH 2 -. Z in the formulas II and III may be the same or different.
L 2 May include H, F, cl, CN, a straight chain having 1 to 25 carbon atoms, a branched chain having 1 to 25 carbon atoms, a cyclic alkyl having 1 to 25 carbon atoms, an alkenyl having 2 to 25 carbon atoms, or an alkynyl having 2 to 25 carbon atoms. Further, at L 2 With one or more-CH 2 In the case of groups, in which one or more-CH 2 The groups may each optionally be substituted with-O-, -S-, -CO-, -CO-O-, -O-CO-O-, or-N-substitution. Wherein, when a plurality of-CH 2 -when substituted, substituted-CH 2 -being unconnected-CH 2 -. After substitution, -O-and-O-are not directly connected to each other, -O-and-S-are not directly connected to each other, and-S-are not directly connected to each other. In addition, at L 2 With one or more H atoms, each H atom may be optionally substituted with a halogen atom.
L 3 May include H, F, cl, CN, a straight chain having 1 to 25 carbon atoms, a branched chain having 1 to 25 carbon atoms, a cyclic alkyl having 1 to 25 carbon atoms, an alkenyl having 2 to 25 carbon atoms, or an alkynyl having 2 to 25 carbon atoms. Further, at L 3 With one or more-CH 2 In the case of groups, in which one or more-CH 2 The groups may each optionally be substituted with-O-, -S-, -CO-, -CO-O-, -O-CO-O-, or-N-substitution. Wherein, when a plurality of-CH 2 -when substituted, substituted-CH 2 -being unconnected-CH 2 -. After substitution, -O-and-O-are not directly connected to each other, -O-and-S-are not directly connected to each other, and-S-are not directly connected to each other. In addition, at L 3 With one or more H atoms, each H atom may be optionally substituted with a halogen atom.
In formula II and IIIMay include aryl, heteroarylAny one of alicyclic group, heterocyclic group and condensed ring. Further, aryl, heteroaryl, alicyclic, heterocyclic and condensed rings may be substituted with L 6 Single or multiple substitutions.
The L is 6 May include H, F, cl, CN, a straight chain having 1 to 25 carbon atoms, a branched chain having 1 to 25 carbon atoms, a cyclic alkyl having 1 to 25 carbon atoms, an alkenyl having 2 to 25 carbon atoms, or an alkynyl having 2 to 25 carbon atoms. Further, at L 6 With one or more-CH 2 In the case of groups, in which one or more-CH 2 The groups may each optionally be substituted with-O-, -S-, -CO-, -CO-O-, -O-CO-O-, or-N-substitution. Wherein, when a plurality of-CH 2 -when substituted, substituted-CH 2 -being unconnected-CH 2 -. After substitution, -O-and-O-are not directly connected to each other, -O-and-S-are not directly connected to each other, and-S-are not directly connected to each other. In addition, at L 6 With one or more H atoms, each H atom may be optionally substituted with a halogen atom.
Sp 3 The spacer may be a spacer, and specific selection of the spacer may be referred to in the foregoing, and will not be described herein.
P 3 May include a polymerizable group or H; specific choices of polymerizable groups can be found in the foregoing and are not described in detail herein. P in formulae II and III 3 May be the same or different.
d may be 0, 1, 2, 3 or 4; e may be 0, 1, 2, 3 or 4; f may be 0, 1, 2, 3 or 4; g may be 0, 1, 2, 3 or 4.m can be 0, 1 or 2, n can be 0, 1 or 2, and m+n is not less than 1.o may be 1, 2 or 3; h may be 1, 2 or 3.
It is understood that with the polymerizable composition provided in the examples of the present application, the polymerizable composition comprises: acrylic resin, a first material and a second material; wherein the first material comprises a compound having formula I and the second material comprises a compound having formula II and/or a compound having formula III. Therefore, the crosslinking density of the phase difference film can be improved, a network structure is formed, and the reliability and bending resistance of the phase difference film can be improved.
On the other hand, the related art generally requires the addition of a homeotropic alignment agent to achieve homeotropic alignment. In the above embodiment of the present application, the compound having formula II has a hydroxyl group at the end and the compound having formula iii has an amino group at the end, both of which have strong polarities, and thus vertical alignment can be achieved, so that no vertical alignment agent is required to be added.
In the related art, only a polymerizable liquid crystal compound is generally used for preparing the phase difference film, and the cost of the phase difference film is greatly reduced by adding cheap and easily available acrylic resin to prepare the phase difference film in the embodiment of the application. Meanwhile, after the acrylic resin is added, the viscosity of the system is increased, and the uniformity of coating can be improved when coating is carried out later.
In particular embodiments, the first material includes a compound having formula I, which may include one or more. Specifically, the compound having formula I included in the first material may include any one or more of formulas I1 to I53.
In the embodiment of the present application, the structural formulas of formulas I1 to I53 may be as follows:
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in the above formulas I1 to I53, t may be 0, 1, 2, 3, 4, 5, 6, 7 or 8; u may be 0, 1, 2, 3, 4, 5, 6, 7 or 8.
The first material may preferably comprise any one or more of the compounds of formula I4 to I8, formula I10 to I12, formula I14 to I15, formula I18 to I23, formula I25, formula I27, formula I29 to I30, formula I32 to I34, formula I36, formula I38, formula I40 to I41, formula I43 to I44, formula I47 to I48 and formula I50 to I53, according to the solubility, compatibility and safety criteria of the compounds of formula I1 to formula I53.
Further, among the compounds of the formulae I4 to I8, formulae I10 to I12, formulae I14 to I15, formulae I18 to I23, formulae I25, formula I27, formulae I29 to I30, formulae I32 to I34, formula I36, formula I38, formulae I40 to I41, formulae I43 to I44, formulae I47 to I48, and formulae I50 to I53, the compounds having the formula I included in the first material may further preferably include any one or more of the following compounds:
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of the above compounds, the first material may further preferably comprise a compound having the formula I, wherein the compound has any one or more of the formula I6-2, the formula I6-3, the formula I7-2, the formula I7-3, the formula I11-2, the formula I11-3, the formula I14-2, the formula I14-3, the formula I18-2, the formula I18-3, the formula I22-2, the formula I22-3, the formula I23-2, the formula I23-3, the formula I25-2, the formula I25-3, the formula I27-2, the formula I27-3, the formula I32-2, the formula I32-3, the formula I33-2, the formula I36-3, the formula I38-2, the formula I38-3, the formula I51-1, the formula I51-3, the formula I52-1 and the formula I52-3.
In particular embodiments, when the second material comprises a compound having formula II, which may comprise one or more. Specifically, the compound having formula II included in the second material may include any one or more of formulas II 1 to II 37.
In the embodiment of the present application, the structural formulas of formulas ii 1 to ii 37 may be as follows:
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in the above formulas II 1 to II 37, in the case where the compound has an F atom, the F atom may be further substituted with a Cl atom, a methyl group or a methoxy group.
In the above formulas II 1 to II 37, sp is a spacer. R includes a single bond, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a fluorine-substituted alkynyl group having 2 to 10 carbon atoms or an alkynyl group having 2 to 8 carbon atoms or a fluorine-substituted alkynyl group having 3 to 8 carbon atoms. And, at R, one or more-CH 2 In the case of groups, in which one or more-CH 2 The groups may each optionally be substituted with-O-, -S-, -COO-or-OOC-substitution. Wherein, when a plurality of-CH 2 -when substituted, substituted-CH 2 -being unconnected-CH 2 -。
The second material may preferably include any one or more of the compounds of formulas II 1 to II 2, II 4 and formulas II 9 to II 10, according to the solubility, compatibility and safety criteria of the compounds of formulas II 1 to II 37.
Further, among the compounds of formulae ii 1 to ii 2, ii 4 and formulae ii 9 to ii 10, the compound having formula ii included in the second substance may further preferably include any one or more of the following compounds:
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further, the compound of formula ii included in the second material may preferably include any one or more of the following:
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in particular embodiments, when the second material comprises a compound having formula III, which may comprise one or more. Specifically, the compound having the formula iii included in the second material may include any one or more of the formulas iii 1 to iii 37.
In the embodiment of the present application, the structural formulas of formulas iii 1 to iii 37 may be as follows:
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in the above formulas III 1 to III 37, in the case where the compound has an F atom, the F atom may be further substituted with a Cl atom, a methyl group or a methoxy group.
In the above formulas III 1 to III 37, sp is a spacer. R includes a single bond, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a fluorine-substituted alkynyl group having 2 to 10 carbon atoms or an alkynyl group having 2 to 8 carbon atoms or a fluorine-substituted alkynyl group having 3 to 8 carbon atoms. And, at R, one or more-CH 2 In the case of groups, in which one or more-CH 2 The groups may each optionally be substituted with-O-, -S-, -COO-or-OOC-substitution. Wherein, when a plurality of-CH 2 -when substituted, substituted-CH 2 -being unconnected-CH 2 -。
The second material may preferably include any one or more of the compounds of formulas III 1 to III 2, III 4 and III 9 to III 10, according to the solubility, compatibility and safety criteria of the compounds of formulas III 1 to III 37.
Further, among the compounds of formulae iii 1 to iii 2, iii 4, and formulae iii 9 to iii 10, the compound having formula iii included in the second substance may preferably include any one or more of the following compounds:
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further, the compound of formula iii included in the second material may preferably include any one or more of the following:
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in practical application, in the preparation raw materials of the polymerizable composition, the mass percentage of the acrylic resin is 3% -30%; the mass percentage of the first material is 5% -60%; the mass percentage of the second material is 1-20%. Thus, a polymer having a more stable structure can be produced. Wherein, the mass percent of the acrylic resin is more preferably 3-15%, the mass percent of the first material is more preferably 30-60%, and the mass percent of the second material is more preferably 5-20%.
In order to further improve the reliability and bending resistance of the retardation film, in one embodiment, the preparation raw material of the polymerizable composition further comprises a third material comprising a compound having formula iv and/or a compound having formula v.
The compound having formula iv and the compound having formula v are acrylic compounds, and the acrylic polymeric group may be substituted with a methacrylic group.
In this embodiment, the structural formula of formula iv may be as follows:
in the formula IV, hydrogen on methyl may be substituted by F, cl, CN, a straight chain having 1 to 25 carbon atoms, a branched chain having 1 to 25 carbon atoms, or a cyclic alkyl having 1 to 25 carbon atoms.
p may be 1, 2, 3 or 4; q may be 1, 2, 3 or 4; r may be 1, 2, 3 or 4.
s may be 0, 1, 2 or 3;
the structural formula of formula V may be as follows:
wherein in the formula V, hydrogen on the methyl group is substituted with F, cl, CN, a straight chain having 1 to 25 carbon atoms, a branched chain having 1 to 25 carbon atoms, or a cyclic alkyl having 1 to 25 carbon atoms.
t may be 1, 2, 3 or 4; u may be 1, 2, 3 or 4; v may be 1, 2, 3 or 4.
In particular embodiments, when the third material comprises a compound having formula iv, the third material may comprise one or more compounds having formula iv. Specifically, the third material may include a compound having formula IV, and may include any one or more of formulas IV-1 to IV-4.
In the embodiment of the application, the structural formulas of the formulas IV-1 to IV-4 can be as follows:
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in the above formulas IV-1 to IV-4, s may be 0, 1, 2 or 3.
Further, among the compounds of the formulae IV-1 to IV-4, the compound having the formula IV included in the third material may preferably include any one or more of the following compounds:
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in particular implementations, when the third material includes a compound having formula v, which may include one or more. Specifically, the compound having formula V included in the third material may include any one or more of formulas V-1 to V-4.
In the embodiment of the present application, the structural formulas of formulas v 1 to v 4 may be as follows:
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in practical application, in the case that the preparation raw materials of the polymerizable composition further comprise a third material, the mass percentage of the addition of the third material is 3% -20%. More preferably, the mass percentage of the second material is 3% -15%.
To further improve the reliability and kink resistance of the retardation film polymerized based on the polymerizable composition, in one embodiment, the polymerizable composition is prepared from a raw material further comprising one or more single-polymerized liquid crystal monomers.
The structural general formula of the single-polymerization liquid crystal monomer is similar to that of the formula II or the formula III, and the difference is that the tail end does not contain hydroxyl and amino with orientation function and the tail end is alkyl. In addition, the further modification of the structural general formula of the single polymerized liquid crystal monomer can refer to the further modification of the formulas II and III, and will not be described herein. In the case where the polymerizable composition further includes a single-polymerized liquid crystal monomer, the single-polymerized liquid crystal monomer may be added in a mass percentage of 3% to 20%.
In particular embodiments, to enable smooth polymerization of the polymerizable monomers in the polymerizable composition, in one embodiment, the polymerizable composition further comprises an initiator.
Wherein the initiator may comprise one or more. The initiator may be an initiator that initiates photopolymerization.
The initiator may specifically include any one or more of the following initiators:
"Irgacure651", "Irgacure 184", "Darocure 1173", "Irgacure 907", "Irgacure127", "Irgacure 369", "Irgacure 379", "Irgacure 819", "Irgacure2959", "Irgacure 1800", "Irgacure 250", "Irgacure 754", "Irgacure784", "Irgacure OXE01", "Irgacure OXE02", "Lucirin TPO", "Darocure 1173", "Darocur MBF", manufactured by BASF Japanese Co., ltd; "Esacure1001M", "Esacure KIP150", "Speedcure BEM", "Speedcure BMS", "Speedcure MBP", "Speedcure PBZ", "Speedcure ITX", "Speedcure DETX", "Speedcure EBD", "Speedcure MBB", "Speedcure BP", manufactured by LAMBSON; "Kayacure DMBI" manufactured by Kayacure Corp; nihon Siber Hegner "TAZ-A" manufactured by DKSH Japan Co., ltd.; "Adeka Optomer SP-152", "Adeka Optomer SP-170", "Adeka Optomer N-1414", "Adeka Optomer N-1606", "Adeka Optomer N-1717", "Adeka Optomer N-1919", etc. manufactured by Adeka.
The initiator may be added in an amount of 0.1% to 10%, preferably 0.5% to 7% by mass of the total mass of the polymerizable compounds in the polymerizable composition, with an optimum addition amount of 0.5% to 3%.
In one embodiment, the polymerizable composition further comprises an additive comprising any one or more of a surfactant, a chain transfer agent, a sensitizer, an anti-uv agent, a polymerization inhibitor, and an antioxidant.
In the embodiment of the application, the surfactant, the chain transfer agent, the sensitizer, the anti-ultraviolet agent, the polymerization inhibitor and the antioxidant can be added according to the actual condition of the formula. Thus, a part of or the whole of the surfactant, chain transfer agent, sensitizer, ultraviolet inhibitor, polymerization inhibitor and antioxidant may be added.
Wherein the surfactant can avoid uneven film thickness when the polymerizable composition is made into an optically anisotropic body. The optically anisotropic body, also called refractive index anisotropic body, refers to a type of body in which light propagates to generate birefringence, and may be referred to as a retardation film in this application.
The surfactant may comprise any one or more of the following:
alkyl carboxylates, alkyl phosphates, alkyl sulfonates, fluoroalkyl carboxylates, fluoroalkyl phosphates, fluoroalkyl sulfonates, polyoxyethylene derivatives, fluoroalkyl ethylene oxide derivatives, polyethylene glycol derivatives, alkyl ammonium salts, fluoroalkyl ammonium salts, and the like, with fluorosurfactants being particularly preferred. Specifically, for example: "Megafac F-251", "Megafac F-444", "Megafac F-477", "Megafac F-510", "Megafac F-552", "Megafac F-553", "Megafac F-554", "Megafac F-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-40", "Megafac R-41", "Megafac R-43", "Megafac R-94", "Megafac RS-72", "Megafac RS-75", "Megafac RS-76" and "are DIC-90; "Ftergent 100", "Ftergent 100C", "Ftergent 110", "Ftergent 150", "Ftergent A", "Ftergent 100A-K", "Ftergent 501", "Ftergent300", "Ftergent 310", "Ftergent 320", "Ftergent 400SW", "FTX-400P", "Ftergent251", "Ftergent 215M", "Ftergent212MH", "Ftergent 250", "Ftergent 222F", "Ftergent 212D", "FTX-218", "FTX-209F", "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-730FL", "FTX-710FS", "FTX-710FM", "FTX-710FL", "FTX-750LL", "FTX-730LS", "FTX-730LM", "FTX-730LL", "FTX-710LL", and the above are manufactured by Noes of Kyoto Co., ltd.); "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", "BYKSilean 3700" (manufactured by K-Chemie Japan company); "TEGO Rad2100", "TEGO Rad2200N", "TEGO Rad2250", "TEGO Rad2300", "TEGO Rad2500", "TEGO Rad2600", "TEGO Rad2700" (the above is manufactured by Tego Corp.); "N215", "N535", "N605K", "N935" (above is made by Solvay Solexis corporation), and the like.
The surfactant may be added in an amount of 0.01% to 2%, preferably 0.05% to 0.5% of the total mass of the polymerizable compounds in the polymerizable composition.
In addition, by using a surfactant, the tilt angle of the air interface can be effectively reduced when the polymerizable composition is made into an optically anisotropic body. And, by using a surfactant, the orientation of the retardation film can be made good. In addition, the surfactant and the polymerizable haze improver are used in combination, and the orientation of the retardation film can be further improved due to the synergistic effect of the two.
The chain transfer agent can improve adhesion between the optically anisotropic body obtained from the polymerizable composition and the substrate. The chain transfer agent may be a thiol compound, and specifically may include any one or more of a monothiol compound, a dithiol compound, a trithiol compound, and a tetrathiol compound; among them, a trithiol compound is preferable.
The chain transfer agent may be added in an amount of 0.5% to 10%, preferably 1.0% to 5.0% by mass of the total mass of the polymerizable compounds in the polymerizable composition.
The sensitizer may increase the efficiency of the polymerization reaction. The sensitizer may include any one or more of benzophenone, thioxanthone, and the like.
The sensitizer may be added in an amount of 0.1 to 3% by weight, more preferably 0.2 to 2% by weight, based on the total mass of the polymerizable compounds in the polymerizable composition.
The uv inhibitor may be a light stabilizing stabilizer that produces a stabilizing effect by absorbing and converting the destructive uv portion of sunlight. Ultraviolet absorbers are mainly used in plastic products, such as thick products like plates, cables, pipes, etc., and in many cases, ultraviolet absorbers are also added into the plastic films to inhibit or delay the negative effect of ultraviolet light on the protected articles or substances. The anti-ultraviolet agent may include any one or more of benzophenones, salicylates, benzotriazoles, substituted acrylonitriles, triazines, and the like. The amount of the ultraviolet inhibitor added may be 0.1% to 2% by weight of the total mass of the polymerizable compounds in the polymerizable composition, and more preferably 0.1% to 1% by weight.
In unsaturated compound systems, the polymerization inhibitor can preferentially react with free radicals in the system to form substances with non-free radicals or form free radicals which have low activity and are not enough to reinitiate, so that chain polymerization of the free radicals can be effectively blocked. Has great advantages for the stability, storage and transportation of the resin. The polymerization inhibitor may include any one or more of the following:
Phenolic compounds, quinone compounds, amine compounds, thioether compounds, nitroso compounds, and the like. Examples of the phenol compound include p-methoxyphenol, cresol, t-butylcatechol, 3, 5-di-t-butyl-4-hydroxytoluene, 2' -methylenebis (4-methyl-6-t-butylphenol), 2' -methylenebis (4-ethyl-6-t-butylphenol), 4' -thiobis (3-methyl-6-t-butylphenol), 4-methoxy-1-naphthol, and 4,4' -dialkoxy-2, 2' -bi-1-naphthol.
Wherein the quinone compound may comprise any one or more of the following:
hydroquinone, methylhydroquinone, t-butylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, t-butyl-p-benzoquinone, 2, 5-diphenylbenzoquinone, 2-hydroxy-1, 4-naphthoquinone, 2, 3-dichloro-1, 4-naphthoquinone, anthraquinone, diphenoquinone, and the like.
The amine-based compound may include any one or more of the following:
p-phenylenediamine, 4-aminodiphenylamine, N '-diphenyl-p-phenylenediamine, N-isopropyl-N' -phenyl-p-phenylenediamine, N- (1, 3-dimethylbutyl) -N '-phenyl-p-phenylenediamine, N' -di-2-naphthyl-p-phenylenediamine, diphenylamine, N-phenyl-beta-naphthylamine, 4 '-dicumyl-diphenylamine, 4' -dioctyl-diphenylamine, and the like.
The thioether compound may include any one or more of phenothiazine, distearyl thiodipropionate, and the like.
The nitroso compound may include any one or more of the following:
n-nitrosodiphenylamine, N-nitrosophenyl-naphthylamine, N-nitrosodinaphthylamine, p-nitrosophenol, nitrone, p-nitrosodiphenylamine, alpha-nitroso-beta-naphthol and the like, N-dimethyl-p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitroso-N, N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-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, nitrone, 2,4, 6-tri-tert-butylnitrone, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylcarbamate, N-nitroso-N-N-propylcarbamate, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 1-nitroso-2-naphthol-3, 6-sodium nitroso-naphthol-1-4-methyl-phenolsulfonate, 2-aminophenol hydrochloride and the like.
The polymerization inhibitor may be added in an amount of 0.01 to 1.0% by mass, preferably 0.05 to 0.5% by mass, based on the total mass of the polymerizable compounds in the polymerizable composition.
Antioxidants can improve the stability of the polymerizable composition. The antioxidant may include any one or more of hydroquinone derivatives, nitrosoamine-based inhibitors, and hindered phenol-based antioxidants.
Specifically, the antioxidant may include any one or more of the following:
tertiary butylhydroquinone, methylhydroquinone, and "Q-1300", "Q-1301" manufactured by photoplethysmography, ltd, BASF corporation, "IRGANOX1010", "IRGANOX1035", "IRGANOX1076", "IRGANOX1098", "IRGANOX1135", "IRGANOX1330", "IRGANOX1425", "IRGANOX1520", "IRGANOX1726", "IRGANOX245", "IRGANOX259", "IRGANOX3114", "IRGANOX3790", "IRGANOX5057", "IRGANOX565", and the like.
The antioxidant may be added in an amount of 0.01% to 2.0%, preferably 0.05% to 1.0% by mass of the total mass of the polymerizable compounds in the polymerizable composition.
Based on the polymerizable composition provided in the above embodiments of the present application, the embodiments of the present application also provide a retardation film polymerized based on the polymerizable composition provided in the above embodiments of the present application. The retardation of the retardation film polymerized by the polymerizable composition provided by the embodiment of the application is-170 to-60 under the wavelength of 550 nm.
The embodiment of the application also provides a preparation method of the phase difference film, wherein the phase difference film is a polarization conversion element with optical anisotropy and can be used in an optical element. As shown in fig. 1, the preparation method may include the steps of:
step 101, mixing the polymerizable composition with a solvent to obtain a polymerizable composition solution.
Wherein the polymerizable composition is provided in the above embodiments of the present application.
The solvent may be an organic solvent, and preferably an organic solvent that can be volatilized and dried at 100 ℃ or less.
The solvent may include any one or more of the following:
aromatic hydrocarbons such as toluene, xylene, cumene, and mesitylene, ester solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone, ether solvents such as tetrahydrofuran, 1, 2-dimethoxyethane, and anisole, amide solvents such as N, N-dimethylformamide, and N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, γ -butyrolactone, and chlorobenzene, and the like. From the viewpoint of solution stability, the solvent is preferably a ketone-based solvent, an ether-based solvent, an ester-based solvent, or an aromatic hydrocarbon-based solvent.
The amount of the solvent to be added is not particularly limited as long as the state of coating is not significantly impaired. The solvent content in the polymerizable composition solution is 30 to 95% by mass, more preferably 40 to 90% by mass, and particularly preferably 50% by mass.
In dissolving the polymerizable composition in the solvent, stirring with heating is preferable in order to uniformly dissolve the polymerizable composition. The temperature of the heating and stirring may be adjusted according to the solubility of the polymerizable composition in the solvent. From the viewpoint of productivity, it is preferably 15 to 110 ℃, more preferably 15 to 105 ℃, still more preferably 15 to 100 ℃, particularly preferably 20 to 60 ℃.
And 102, coating the polymerizable composition solution on the surface of a substrate, and drying to obtain a polymerizable composition resin layer.
Wherein, the substrate may be a vertical alignment film. The substrate may be used to carry a solution of the polymerizable composition. The material of the base material is heat-resistant, so that the performance of the base material is not affected when the polymerizable composition solution coated on the surface is heated and dried subsequently.
The substrate may include organic materials such as glass substrates, metal substrates, ceramic substrates, plastic substrates, and the like. In the case where the substrate is an organic material, the substrate may include a cellulose derivative, polyolefin, polyester, polycarbonate, polyacrylate (acrylic resin), polyarylate, polyethersulfone, polyimide, polyphenylene sulfide, polyphenylene oxide, nylon, polystyrene, or the like. Among them, plastic substrates such as polyester, polystyrene, polyacrylate, polyolefin, cellulose derivative, polyarylate, and polycarbonate are preferable, and substrates such as metal, polyethylene terephthalate (PET), and cellulose derivative (PVA) are more preferable. The shape of the substrate may be a curved surface, in addition to a flat plate. The substrate may also have an electrode layer, an antireflection function, a reflection function, and the like according to actual needs.
The polymerizable composition solution is applied to the surface of the substrate by a coating method such as an applicator method, a bar coating method, a spin coating method, a roll coating method, a direct gravure coating method, a reverse gravure coating method, a flexographic coating method (flexo coating method), an ink jet method, a die coating method, a cap coating method (cap coating method), a dip coating method, or a slit coating method.
In specific practice, the substrate coated with the polymerizable composition solution may be dried in a forced air drying oven at 70 to 90 ℃ for 60 to 80 seconds to obtain a polymerizable composition resin layer.
Step 103, irradiating the polymerizable composition resin layer to obtain a retardation film.
Wherein the polymerizable composition resin layer may be irradiated with visible light or ultraviolet light. Specifically, it is preferable to irradiate ultraviolet light of 390nm or less, and more preferably to irradiate light of 250 to 370 nm. In practical applications, depending on the formulation of the polymerizable composition, irradiation with ultraviolet light of 390nm or more may be used when the ultraviolet light of 390nm or less causes decomposition of the polymerizable composition. The light that irradiates the polymerizable composition resin layer is preferably unpolarized light.
Under the irradiation of light, the polymerizable composition resin layer is photopolymerized, thereby obtaining a retardation film.
The retardation film includes a base material and a polymerized polymerizable composition resin layer.
It can be appreciated that with the retardation film provided in the examples of the present application, since the polymerizable composition includes: acrylic resin, a first material and a second material; wherein the first material comprises a compound having formula I and the second material comprises a compound having formula II and/or a compound having formula III. Therefore, the crosslinking density of the phase difference film can be improved, a network structure is formed, and the reliability and bending resistance of the phase difference film can be improved.
In addition, the phase difference film prepared by the simple preparation method of coating and illumination in the embodiment can replace the traditional phase difference film prepared by stretching, and the preparation process of the phase difference film can be effectively simplified, so that the production efficiency can be improved, and the production cost can be reduced.
Based on the polymerizable composition provided in the above embodiments of the present application, another retardation film is also provided in the embodiments of the present application, which is polymerized based on the polymerizable composition provided in the above embodiments of the present application.
The embodiment of the application also provides a preparation method of the phase difference film, which can comprise the following steps:
Step one, coating a strippable coating on a substrate;
coating a polymerizable composition solution on the strippable coating layer, and drying to obtain a polymerizable composition resin layer;
step three, irradiating the polymerizable composition resin layer;
and step four, stripping the polymerizable composition resin layer after the polymerization of the polymerizable composition resin layer is completed, so as to obtain the phase difference film.
The second and third steps may refer to the contents of the foregoing steps 101 to 103, which are not described herein.
The retardation film may be a polymerizable composition resin layer peeled off after completion of polymerization.
It can be appreciated that with the retardation film provided in the examples of the present application, since the polymerizable composition includes: acrylic resin, a first material and a second material; wherein the first material comprises a compound having formula I and the second material comprises a compound having formula II and/or a compound having formula III. Therefore, the crosslinking density of the phase difference film can be improved, a network structure is formed, and the reliability and bending resistance of the phase difference film can be improved.
Embodiments also provide a display device including a polymerizable composition or a phase difference film.
The polymerizable composition included in the display device may be specifically a polymerizable composition resin layer peeled off after completion of polymerization in the above-described embodiment. The retardation film included in the display may include a base material and a polymerizable composition resin layer after polymerization is completed.
The display device may comprise a display element or a display. The display device may be an active matrix display device or a passive matrix display device.
Further, the display device may be an active matrix addressed liquid crystal display device or an OLED display device.
It can be appreciated that with the display device provided by the embodiments of the present application, since the polymerizable composition includes: acrylic resin, a first material and a second material; wherein the first material comprises a compound having formula I and the second material comprises a compound having formula II and/or a compound having formula III. Therefore, the cross-linking density of the phase difference film can be improved, a network structure is formed, the reliability and bending resistance of the phase difference film can be improved, and the service life of the display device can be prolonged.
In order to facilitate the description of the solutions provided in the embodiments of the present application, the following description will be made with reference to specific embodiments, comparative examples, and corresponding test data.
In the examples below, the raw materials used are available from published commercial sources, percentages are by mass, temperatures in degrees celsius (c) and the specific meanings of the other symbols and test conditions are as follows:
rth represents the optical retardation in the film perpendicular direction, i.e., the retardation perpendicular to the surface of the retardation film, under the test conditions of 25.+ -. 2 ℃ in the X-Scan apparatus. Adhesion performance test the SM600 tape was tested using the hundred method. Pretilt angle and twist angle tests were performed using an X-Scan apparatus. The bending resistance was tested using a bending resistance strength tester. Reliability testing the tests were performed using a constant temperature and humidity cabinet.
As a preferred embodiment, the compounds of the formulae I, II and III are preferably those of the formulae,
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the structure of the single polymerization liquid crystal compound is as follows:
MIBK: methyl isobutyl ketone examples 1 to 16
The polymerizable composition solutions and the retardation films were prepared according to the compositions and contents of table 1 below and the following methods.
The preparation method of the polymerizable composition solution is as follows:
the components were weighed according to the contents shown in Table 1, placed in a brown bottle, added with a solvent, placed on a magnetic stirring apparatus and stirred for 1 hour, and the mixture was stirred uniformly to obtain a polymerizable composition solution.
The preparation method of the phase difference film comprises the following steps:
first, a polymerizable composition solution is prepared according to the above-described method;
then, the above polymerizable composition solution was scraped onto a PVA film at a speed of 10cm/s with 10#, 20#, 25# malt bars, and the scraped sample was dried in a forced air drying oven at 80℃for 60 seconds.
Finally, the film was cured with ultraviolet light having a wavelength of 365nm and irradiance of 30Mw/cm2 at room temperature for 60 seconds to obtain a retardation film. Rth, pretilt angle, twist angle, adhesive force and bending resistance and high temperature and high humidity aging test (60 ℃/90%240 h) are carried out on the prepared phase difference film.
Table 1 examples and comparative examples polymerizable compositions composition and content
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Comparative examples 1 to 5
By the same method as in examples 1 to 16, a polymerizable composition solution was prepared in the proportions and amounts shown in Table 1, and a retardation film was prepared under other conditions. Rth, pretilt angle, twist angle, adhesion performance test and high temperature high humidity aging test (60 ℃/90%240 h) were performed.
Table 2 test data
The test results of examples and comparative examples 1 and 3 show that the polymerizable liquid crystal compound films to which the compounds of formula II and III are not added show isotropy, i.e., no alignment is performed, and therefore it can be known that the addition of formula II and III can increase the vertical alignment of the vertically aligned retardation film.
The films and substrates formed without the addition of the compounds of formulas IV and V in comparative examples 2 and 4 were inferior in adhesion properties and bending resistance as well as in the examples.
Comparative example 5 and example the formulations without the addition of formulas II and III show that the polymerizable liquid crystal molecules are not homeotropically aligned as shown by the test results after film formation of the formulations. The formula without the formula IV and V has the bending resistance and the adhesive force test process which are also inferior to those of the formula IV and V.
According to the ageing test results of the examples and the comparative examples 2 and 4, after the IV and V compounds are added, the high-temperature and high-humidity resistance of the polymerizable liquid crystal composition after film formation is obviously improved, and the optical parameter variation before and after ageing is reduced to within 3% from the previous 10%, so that the ageing resistance of the composition after film formation is improved due to the addition of IV and V.
It should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article or apparatus that comprises the element.
The foregoing is merely exemplary of the present application and is not intended to limit the present application. Various modifications and changes may be made to the present application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc. which are within the spirit and principles of the present application are intended to be included within the scope of the claims of the present application.

Claims (10)

1. A polymerizable composition, wherein the polymerizable composition comprises: acrylic resin, a first material and a second material;
wherein the first material comprises a compound having formula I, and the second material comprises a compound having formula II and/or a compound having formula iii;
the formula I is as follows:
wherein L is 1 Comprises H, F, cl, CN, a straight chain having 1 to 25 carbon atoms, a branched chain having 1 to 25 carbon atoms, a cyclic alkyl having 1 to 25 carbon atoms, and a cyclic alkyl having 2 to more carbon atoms25, an alkenyl group having 2 to 25 carbon atoms, or an alkynyl group having 2 to 25 carbon atoms;
in said formula IComprises any one of 1, 4-cyclohexylene, 1, 4-phenylene, 2, 6-naphthylene, 1, 5-naphthylene and 1, 4-naphthylene;
in said formula IComprises any one of 1, 4-cyclohexylene, 1, 4-phenylene, 2, 6-naphthylene, 1, 5-naphthylene and 1, 4-naphthylene;
In said formula IComprises any one of 1, 4-cyclohexylene, 1, 4-phenylene, 2, 6-naphthylene, 1, 5-naphthylene and 1, 4-naphthylene;
Sp 1 is a spacer, sp 2 Is a spacer;
P 1 comprising a polymerisable group or H; p (P) 2 Comprising a polymerisable group or H; and P is 1 And P 2 At least one of which is a polymerizable group;
a is 1, 2 or 3; b is 1, 2 or 3; c is 1, 2 or 3;
the formula II is as follows:
the formula III is as follows:
in the formula II and the formula III, R includes any one of a single bond, a straight chain having 1 to 25 carbon atoms, a branched chain having 1 to 25 carbon atoms, and a cyclic alkyl group having 1 to 25 carbon atoms;
z comprises any one of a single bond, an alkyl group having 1 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms;
L 2 comprises H, F, cl, CN, a straight chain with 1-25 carbon atoms, a branched chain with 1-25 carbon atoms, a cyclic alkyl with 1-25 carbon atoms, an alkenyl with 2-25 carbon atoms and an alkynyl with 2-25 carbon atoms;
L 3 comprises H, F, cl, CN, a straight chain with 1-25 carbon atoms, a branched chain with 1-25 carbon atoms, a cyclic alkyl with 1-25 carbon atoms, an alkenyl with 2-25 carbon atoms and an alkynyl with 2-25 carbon atoms;
Said formula II and said formula IIIIncluding any of aryl, heteroaryl, alicyclic, heterocyclic, and fused rings;
Sp 3 is a spacer; p (P) 3 Comprising a polymerizable group;
d is 0, 1, 2, 3 or 4; e is 0, 1, 2, 3 or 4; f is 0, 1, 2, 3 or 4; g is 0, 1, 2, 3 or 4;
m is 0, 1 or 2, n is 0, 1 or 2, and m+n is not less than 1;
o is 1, 2 or 3, h is 1, 2 or 3;
wherein the acrylic resin comprises a plurality of acrylic bonds.
2. The polymerizable composition of claim 1 further comprising a third material comprising a compound having formula iv and/or a compound having formula v;
the formula IV is as follows:
in the formula IV, hydrogen on methyl is replaced by F, cl, CN, straight chain with 1-25 carbon atoms, branched chain with 1-25 carbon atoms or cyclic alkyl with 1-25 carbon atoms;
p is 1, 2, 3 or 4; q is 1, 2, 3 or 4; r is 1, 2, 3 or 4;
s is 0, 1, 2 or 3;
the formula V is as follows:
in the formula V, hydrogen on the methyl group is substituted with F, cl, CN, a straight chain having 1 to 25 carbon atoms, a branched chain having 1 to 25 carbon atoms, or a cyclic alkyl having 1 to 25 carbon atoms;
t is 1, 2, 3 or 4; u is 1, 2, 3 or 4; v is 1, 2, 3 or 4.
3. The polymerizable composition of claim 1 wherein the acrylic resin has a refractive index of from 1.40 to 1.60 and a molecular weight of from 200 to 2000.
4. The polymerizable composition according to claim 1, wherein the acrylic resin is added in the polymerizable composition in a mass percentage of 3% to 30%; the mass percentage of the first material is 5% -60%; the mass percentage of the second material is 1-20%.
5. The polymerizable composition of claim 2 wherein, where the polymerizable composition further comprises the third material, the third material is added in a mass percent of 1% to 20%.
6. The polymerizable composition of claim 2 wherein the polymerizable composition further comprises a single polymerized liquid crystal monomer.
7. The polymerizable composition of any one of claims 1-6 wherein the polymerizable composition further comprises an initiator and an additive;
the additive comprises any one or more of a surfactant, a chain transfer agent, a sensitizer, an anti-ultraviolet agent, a polymerization inhibitor and an antioxidant.
8. A retardation film, which is polymerized based on the polymerizable composition according to claim 7.
9. A method for producing a retardation film, comprising:
mixing the polymerizable composition of claim 7 with a solvent to obtain a polymerizable composition solution;
coating the polymerizable composition solution on the surface of a substrate, and drying to obtain a polymerizable composition resin layer;
and irradiating the polymerizable composition resin layer to obtain a retardation film.
10. A display device comprising the polymerizable composition according to any one of claims 1 to 7 or the phase difference film according to claim 8, the display device being an active matrix display device or a passive matrix display device.
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