CN117567679A - Side chain type liquid crystal polymer, liquid crystal composition, phase difference film, preparation method and display device - Google Patents

Side chain type liquid crystal polymer, liquid crystal composition, phase difference film, preparation method and display device Download PDF

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CN117567679A
CN117567679A CN202311406458.2A CN202311406458A CN117567679A CN 117567679 A CN117567679 A CN 117567679A CN 202311406458 A CN202311406458 A CN 202311406458A CN 117567679 A CN117567679 A CN 117567679A
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liquid crystal
carbon atoms
formula
crystal composition
group
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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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    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/303—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one or more carboxylic moieties in the chain
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen

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Abstract

The application discloses a side chain type liquid crystal polymer, a liquid crystal composition, a phase difference film, a preparation method and a display device, relates to the technical field of liquid crystal display, and aims to solve the problem that the addition of the side chain type liquid crystal polymer can further reduce the adhesive force between the phase difference film and a base material. The side chain type liquid crystal polymer can improve the bending resistance of the phase difference film, so that the reliability and bending resistance of the phase difference film can be improved, and the side chain type liquid crystal polymer has a dimethomorph structure, so that the adhesive force of the phase difference film can be improved, and the bonding force between the phase difference film and a base material can be improved.

Description

Side chain type liquid crystal polymer, liquid crystal 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 side chain type liquid crystal polymer, a liquid crystal 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, wherein a retardation film of positive C type (positive C plate) has an effect of improving viewing angle, and is widely used.
However, the existing positive C-type retardation film has poor bending resistance and interlayer adhesion due to its molecular arrangement, and although other patents have a side chain type liquid crystal polymer added thereto to improve the bending resistance of the retardation film, the addition of the side chain type liquid crystal polymer further reduces the adhesion between the retardation film and the substrate due to the influence of the molecular structure of the existing side chain type liquid crystal polymer.
Disclosure of Invention
The invention discloses a side chain type liquid crystal polymer, a liquid crystal composition, a phase difference film, a preparation method and a display device, which are used for solving the problem that the addition of the side chain type liquid crystal polymer can further reduce the adhesive force between the phase difference film and a base material.
In order to achieve the above object, the embodiment of the present specification adopts the following technical solutions:
in a first aspect, embodiments herein provide a side chain type liquid crystal polymer comprising: a first structural unit represented by formula a and a second structural unit represented by formula b;
the formula a is as follows:
wherein R is 3 Selected from methyl or hydrogen atoms; r is R 4 Is- (CH) 2 ) n -a linking group of formula wherein two non-adjacent carbons can each independently be substituted by-O-, -S-, -OCO-, -COO-, n being an integer from 0 to 10; r is R 5 Selected from methyl, aryl optionally having alkyl substituents OR-OR 7 Wherein R is 7 Represents a hydrogen atom, an alkyl group or an aryl group optionally having an alkyl substituent; m is an integer of 0 to 18 inclusive;
L 3 represents a linking group which is bonded to the substrate, selected from-C-C-, -O-, -S-, -COO-, -OCO-;
selected from aryl, heteroaryl, alicyclic, heterocyclic, fused rings wherein the carbon atoms in the ring may be optionally substituted with N, S atoms;
the formula b is as follows:
wherein R is 1 Is methyl or hydrogen atom.
In a second aspect, embodiments of the present application provide a liquid crystal composition comprising: the side chain type liquid crystal polymer and the polymerizable liquid crystal substance provided in the first aspect of the application, wherein the polymerizable liquid crystal substance comprises a polymerizable liquid crystal compound or a polymerizable liquid crystal composition.
Optionally, the side chain type liquid crystal polymer accounts for 1-10% of the total mass of the liquid crystal composition, and the polymerizable liquid crystal substance accounts for 80-95% of the total mass of the liquid crystal composition. .
Optionally, the polymerizable liquid crystal composition includes: 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 alkyl structure with 1-25 carbon atoms and a branched-chain alkyl structure with 3-25 carbon atoms, a cyclic alkyl with 3-25 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 、Sp 2 represents any one of a straight-chain alkyl structure having 1 to 25 carbon atoms and 3 to 25 carbon atoms and a cyclic alkyl structure having 3 to 25 carbon atoms, wherein any two non-adjacent carbon atoms may be substituted with-O-, -OCO-, -COO-, -S-, -n=;
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;
wherein the polymerizable group comprises The points in the formula of the polymerizable group represent methacrylic bonds;
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 alkyl structure having 1 to 25 carbon atoms, a branched alkyl structure having 3 to 25 carbon atoms, and a cyclic alkyl structure having 3 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 alkyl structure with 1-25 carbon atoms and a branched-chain alkyl structure with 3-25 carbon atoms, a cyclic alkyl with 3-25 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 alkyl structure with 1-25 carbon atoms and a branched-chain alkyl structure with 3-25 carbon atoms, a cyclic alkyl with 3-25 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 wherein the heteroatoms include N, O, and S atoms;
Sp 3 Represents any one of a straight chain alkyl group having 1 to 25 carbon atoms, a branched alkyl group having 3 to 25 carbon atoms and a cyclic alkyl group having 3 to 25 carbon atoms, wherein any two non-adjacent carbon atoms may be substituted by-O-, -OCO-, -COO-, -S-, -n= substitution,
P 3 comprising a polymerisable group or H;
wherein the polymerizable group comprises
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.
Optionally, the first material accounts for 80-95% of the mass of the polymerizable liquid crystal composition; the second material accounts for 5-20% of the mass of the polymerizable liquid crystal composition.
Optionally, the liquid crystal composition further comprises an initiator, wherein the initiator is an initiator for initiating photopolymerization; the addition amount of the initiator is 0.1-10% of the total mass of the polymerizable liquid crystal substance.
Optionally, the liquid crystal 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 a third aspect, embodiments of the present application provide a retardation film polymerized based on the liquid crystal composition provided in the second aspect of the present application.
In a fourth aspect, embodiments of the present application provide a method for preparing a retardation film, the method comprising:
mixing the liquid crystal composition provided in the second aspect of the application with a solvent to obtain a liquid crystal composition solution;
coating the liquid crystal composition solution on the surface of a substrate, and drying to obtain a liquid crystal composition resin layer;
and irradiating the liquid crystal composition resin layer to obtain a phase difference film.
In a fifth aspect, embodiments of the present application provide a display device, where the display device includes the liquid crystal composition provided in the second aspect of the present application or the retardation film provided in the third aspect of the present application after polymerization is completed, and the display device is an active matrix display device or a passive matrix display device.
The above-mentioned at least one technical scheme that this application embodiment adopted can reach following beneficial effect:
by adopting the scheme provided by the embodiment of the application, the side chain type liquid crystal polymer is arranged and applied to the phase difference film. The side chain type liquid crystal polymer can improve the bending resistance of the phase difference film, so that the reliability and bending resistance of the phase difference film can be improved, and the side chain type liquid crystal polymer has a dimethomorph structure, so that the adhesive force of the phase difference film can be improved, and the bonding force between the phase difference film and a base material 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.
According to an embodiment of the present application, there is provided a side chain type liquid crystal polymer which can be used in a liquid crystal composition and also in the preparation of a retardation film.
The side chain type liquid crystal polymer includes: a first structural unit represented by formula a and a second structural unit represented by formula b;
the formula a is as follows:
wherein R is 3 Selected from methyl or hydrogen atoms; r is R 4 Is- (CH) 2 ) n -a linking group of formula wherein two non-adjacent carbons can each independently be substituted by-O-, -S-, -OCO-, -COO-, n being an integer from 0 to 10; r is R 5 Selected from methyl, aryl optionally having alkyl substituents OR-OR 7 Wherein R is 7 Represents a hydrogen atom, an alkyl group or an aryl group optionally having an alkyl substituent; m is an integer of 0 to 18 inclusive;
L 3 represents a linking group which is bonded to the substrate, selected from-C-C-, -O-, -S-, -COO-, -OCO-;
selected from aryl, heteroaryl, alicyclic, heterocyclic, fused rings wherein the carbon atoms in the ring may be optionally substituted with N, S atoms;
the formula b is as follows:
wherein R is 1 Is methyl or hydrogen atom.
The addition of the flexible main chain in the carbon chain formed by polymerization of the side chain type liquid crystal polymer can improve the bending resistance; meanwhile, the heteroatom contained in the side chain structure of the acryloylmorpholine can form strong dispersion force with other layers, so that the adhesive force between the liquid crystal polymer film and other layers can be effectively improved.
In a specific implementation, the side chain type liquid crystal polymer includes a first structural unit having a formula a and a second structural unit having a formula b. Specifically, the first structural unit having the formula a in the side chain type liquid crystal polymer may include any one or more of formulas a1 to a 11.
In the embodiment of the present application, the structural formulas of formulas a1 to a10 may be as follows:
in the above formulae a1 to a11, T is selected from any one of H, a straight chain having 1 to 25 carbon atoms, an alkyl structure having 3 to 25 carbon atoms having a branched chain, and a cyclic alkyl group having 3 to 25 carbon atoms, wherein any two non-adjacent carbon atoms may be optionally substituted with-O-, -S-; n is any integer from 1 to 16.
According to the solubility, film forming property and alignment ability of the compounds of the above formulas a1 to a11, the first structural unit having the formula a in the side chain type liquid crystal polymer may preferably include any one or more of the compounds of the formulas a1 to a4 and a8, specifically as follows:
among the above compounds, the first structural unit having the formula a in the side chain type liquid crystal polymer may further preferably be any one or more of the formulas a1-1, a1-3, a2-1, a3-1, a4-1 and a8-3, depending on the alignment ability and solubility after the polymerization of the compound.
Specifically, the second structural unit having the formula b in the side chain type liquid crystal polymer may include any one or more of the formulas b1 and b 2.
In the embodiment of the present application, the structural formulas of formulas b1 to b2 may be as follows:
In the present embodiment, the method for producing the side chain type liquid crystal polymer is not particularly limited, and for example, the monomer derived from the first structural unit represented by the general formula a and the monomer derived from the second structural unit represented by the general formula b are polymerized by a known polymerization method, and then the obtained polymers are connected to each other, and the polymers may be block polymerized or random polymerized.
In addition, in the case of producing a block copolymer or a random polymer, the following methods are exemplified: the monomers from which the first structural unit represented by the above general formula a is derived and the monomers from which the second structural unit represented by the general formula b is derived may be polymerized by a known polymerization method, respectively, and then the obtained polymers may be linked; one of the monomers from which the first structural unit represented by the above general formula a is derived and the monomers from which the second structural unit represented by the general formula b is derived may be polymerized by a known polymerization method, and then the other monomer may be added to further polymerize.
As the above polymerization method, a method generally used for polymerization of a compound having a vinyl group can be employed, and for example, anionic polymerization, living radical polymerization, or the like can be used. In this embodiment, a method for living polymerization such as Group Transfer Polymerization (GTP) disclosed in "j.am.chem.soc."105, 5706 (1983) is particularly preferably used. When this method is used, the molecular weight, molecular weight distribution, and the like can be easily set to a desired range, and thus the characteristics of the obtained side chain type liquid crystal polymer can be made uniform.
In the present disclosure, the structure of the side chain type liquid crystal polymer may be resolved by combining at least one of nuclear magnetic resonance spectroscopy (NMR), thermal decomposition type gas chromatography mass spectrometry (Py-GC-MS), and matrix assisted laser desorption ionization time of flight type mass spectrometry (MALDI-TOFMS). By Py-GC-MS or MALDI-TOFMS, it was confirmed that 2 or more kinds of structural units having different numbers of carbon atoms including a linking group were contained.
According to an embodiment of the present application, there is provided a liquid crystal composition including: a side chain type liquid crystal polymer, a polymerizable liquid crystal substance, wherein the polymerizable liquid crystal substance comprises a polymerizable liquid crystal compound or a polymerizable liquid crystal composition, and the polymerizable liquid crystal composition can be formed by combining a plurality of polymerizable liquid crystal compounds. The polymerizable liquid crystal substance may undergo polymerization under ultraviolet irradiation.
The conventional liquid crystal composition requires the addition of a homeotropic alignment agent to achieve homeotropic alignment. In the technical scheme of the application, the substance containing hydroxyl in the liquid crystal composition can realize vertical alignment, so that a vertical alignment agent is not required to be added.
The polymerizable liquid crystal compound is a liquid crystal monomer containing a methacrylic bond and/or an acrylic bond.
The polymerizable liquid crystal composition comprises: 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 alkyl structure having 1 to 25 carbon atoms and having 3 to 25 carbon atoms as a branched chain, a cyclic alkyl group having 3 to 25 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, and an alkynyl group having 2 to 25 carbon atomsAny one of them;
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 、Sp 2 represents any one of a straight-chain alkyl structure having 1 to 25 carbon atoms and 3 to 25 carbon atoms and a cyclic alkyl structure having 3 to 25 carbon atoms, wherein any two non-adjacent carbon atoms may be substituted with-O-, -OCO-, -COO-, -S-, -n=;
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;
wherein the polymerizable group comprisesThe points in the formula of the polymerizable group represent methacrylic bonds;
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 alkyl structure having 1 to 25 carbon atoms, a branched alkyl structure having 3 to 25 carbon atoms, and a cyclic alkyl structure having 3 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 alkyl structure with 1-25 carbon atoms and a branched-chain alkyl structure with 3-25 carbon atoms, a cyclic alkyl with 3-25 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 alkyl structure with 1-25 carbon atoms and a branched-chain alkyl structure with 3-25 carbon atoms, a cyclic alkyl with 3-25 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 represents any one of a straight chain alkyl group having 1 to 25 carbon atoms, a branched alkyl group having 3 to 25 carbon atoms and a cyclic alkyl group having 3 to 25 carbon atoms, wherein any two non-adjacent carbon atoms may be substituted by-O-, -OCO-, -COO-, -S-, -n= substitution,
P 3 comprising a polymerisable group or H;
wherein the polymerizable group comprises
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 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 I55.
In the embodiment of the present application, the structural formulas of formulas I1 to I55 may be as follows:
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in the above formulas I1 to I55, 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 I33, formula I36, formula I38, formula I40 to I41, formula I43 to I44, formula I47 to I48 and formula I50 to I52, according to the solubility, compatibility and safety criteria of the compounds of formula I1 to formula I55.
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 I33, formula I36, formula I38, formulae I40 to I41, formulae I43 to I44, formulae I47 to I48, and formulae I50 to I52, 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 comprises a single bond, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a fluorine-substituted carbon atomAlkoxy having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, fluoro-substituted alkenyl having 2 to 10 carbon atoms, alkenyloxy having 3 to 8 carbon atoms or fluoro-substituted alkenyloxy having 3 to 8 carbon atoms, alkynyl having 2 to 10 carbon atoms, fluoro-substituted alkynyl having 2 to 10 carbon atoms or alkynyl having 2 to 8 carbon atoms or fluoro-substituted alkynyl 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 27.
In the embodiment of the present application, the structural formulas of formulas iii 1 to iii 27 may be as follows:
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in the above formulas III 1 to III 27, 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 27, sp is a spacer. R includes a hydrogen atom, 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 27.
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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in the above-mentioned compounds of the formulae III 1 to III 2, III 4 and III 9 to III 10, R is selected from the group consisting of a hydrogen atom, 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 a fluorine-substituted 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 -。
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 particular embodiments, the liquid crystal composition further includes an initiator in order to allow for smooth polymerization of the liquid crystal composition in the subsequent preparation of the retardation film.
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 amount of the initiator to be added may be 0.1 to 10% by mass, preferably 0.5 to 7% by mass, based on the total mass of the polymerizable liquid crystal substance in the liquid crystal composition, and the optimum amount to be added is 0.5 to 3% by mass.
In one embodiment, the liquid crystal 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. Therefore, some or all of the surfactant, chain transfer agent, sensitizer, ultraviolet inhibitor, polymerization inhibitor, and antioxidant may be added.
Wherein the surfactant can prevent uneven film thickness when the liquid crystal 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 amount of the surfactant to be added may be 0.01% to 2%, preferably 0.05% to 0.5% of the total mass of the polymerizable liquid crystal substance in the liquid crystal composition.
In addition, by using a surfactant, the tilt angle of the air interface can be effectively reduced when the liquid crystal 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 liquid crystal 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 amount of the chain transfer agent to be added may be 0.5% to 10%, preferably 1.0% to 5.0% of the total mass of the polymerizable liquid crystal substance in the liquid crystal 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 liquid crystal substance in the liquid crystal 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 may be 0.1 to 2% by weight, more preferably 0.1 to 1% by weight, based on the total mass of the polymerizable liquid crystal substance in the liquid crystal composition.
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%, preferably 0.05 to 0.5% based on the total mass of the polymerizable liquid crystal substance in the liquid crystal composition.
Antioxidants can improve the stability of the liquid crystal 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 amount of the antioxidant to be added may be 0.01 to 2.0% by mass, preferably 0.05 to 1.0% by mass, based on the total mass of the polymerizable liquid crystal substance in the liquid crystal composition.
According to an embodiment of the present application, there is provided a retardation film polymerized based on the liquid crystal composition provided herein. The retardation of the retardation film polymerized by the liquid crystal composition provided by the application is-170 to-60 under the wavelength of 550 nm. The phase difference film is a positive C-type phase difference film.
According to an embodiment of the present application, there is provided a method for producing a retardation film, which is a polarization conversion element having optical anisotropy, that can be used in an optical element. As shown in fig. 1, the preparation method may include the steps of:
step 101, mixing the liquid crystal composition with a solvent to obtain a liquid crystal composition solution.
The liquid crystal composition is provided by the embodiment of the 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 content of the solvent in the liquid crystal composition solution is 30 to 95% by mass, more preferably 40 to 90% by mass, and particularly preferably 50% by mass.
In dissolving the liquid crystal composition in the solvent, heating and stirring are preferable in order to uniformly dissolve the liquid crystal composition. The temperature of the heating and stirring may be adjusted according to the solubility of the liquid crystal composition in the solvent. From the viewpoint of productivity, it is preferably 15℃to 110℃and more preferably 25℃to 105℃and further preferably 25℃to 100℃and particularly preferably 30℃to 60 ℃.
And 102, coating the liquid crystal composition solution on the surface of a substrate, and drying to obtain a liquid crystal composition resin layer.
Wherein, the substrate may be a vertical alignment film. The substrate may be used to carry a liquid crystal composition solution. The base material is heat-resistant, so that the performance of the base material is not affected when the liquid crystal 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 liquid crystal 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 flexo 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 the specific implementation, the substrate coated with the liquid crystal composition solution may be dried in a forced air drying oven at 70 to 90 ℃ for 60 to 80 seconds to obtain a liquid crystal composition resin layer.
And step 103, irradiating the liquid crystal composition resin layer to obtain a phase difference film.
Wherein the liquid crystal 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 liquid crystal composition, when the liquid crystal composition is decomposed by ultraviolet light of 390nm or less, the irradiation may be performed by ultraviolet light of 390nm or more. The light irradiated to the resin layer of the liquid crystal composition is preferably unpolarized light.
Under the irradiation of light, the liquid crystal composition resin layer is photopolymerized, thereby obtaining a retardation film.
The retardation film includes a base material and a polymerized liquid crystal composition resin layer.
It can be understood that, with the retardation film provided in the embodiments of the present application, since the liquid crystal composition includes: an initiator, a side chain type liquid crystal polymer and a polymerizable liquid crystal substance; wherein the side chain type liquid crystal polymer comprises a compound having structural units of formula a and formula b, and the side chain type liquid crystal polymer comprises a first structural unit having formula a and a second structural unit having formula b. The additive can be one or more of surfactant, chain transfer agent, sensitizer, ultraviolet inhibitor, polymerization inhibitor and antioxidant, or the additive can be not added, and the additive is specifically selected according to the actual condition of the formula. The refractive index of the phase difference film prepared by the liquid crystal composition is much larger than that of a stretching film, so that the thickness of the liquid crystal phase difference film is smaller than that of a common stretching phase difference film when the same phase is delayed, and the liquid crystal phase difference film is more suitable for the requirements of bending resistance and light weight of the existing electronic products.
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 liquid crystal composition provided in the above embodiments of the present application, another retardation film is also provided in the embodiments of the present application, and the retardation film is polymerized based on the liquid crystal 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 or a bonding enhancing coating on a substrate;
coating a liquid crystal composition solution on the strippable coating, and drying to obtain a liquid crystal composition resin layer;
step three, irradiating the liquid crystal composition resin layer;
and step four, after the polymerization of the liquid crystal composition resin layer is completed, stripping the liquid crystal composition resin layer 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 liquid crystal composition resin layer peeled off after completion of polymerization.
It can be understood that, with the retardation film provided in the embodiments of the present application, since the liquid crystal composition includes: an initiator, a side chain type liquid crystal polymer and a polymerizable liquid crystal substance; wherein the side chain type liquid crystal polymer comprises a compound having structural units of formula a and formula b, and the side chain type liquid crystal polymer comprises a first structural unit having formula a and a second structural unit having formula b. The additive can be one or more of surfactant, chain transfer agent, sensitizer, ultraviolet inhibitor, polymerization inhibitor and antioxidant, or the additive can be not added, and the additive is specifically selected according to the actual condition of the formula. The refractive index of the phase difference film prepared by the liquid crystal composition is much larger than that of a stretching type film, so that the thickness of the liquid crystal type phase difference film is smaller than that of a common stretching phase difference film when the same phase is delayed, and the liquid crystal type phase difference film is more suitable for bending resistance and light weight of the current electronic products.
The liquid crystal composition included in the display device may specifically be a liquid crystal composition resin layer peeled off after the completion of polymerization in the above-described embodiment. The retardation film included in the display may include a base material and a liquid crystal composition resin layer after completion of polymerization.
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 in the embodiments of the present application, since the composition includes: the side chain type liquid crystal polymer comprises a dimethomorph structure in the side chain type liquid crystal polymer molecule, so that the adhesive force of the phase difference film and a base material can be improved, and the application range of the phase difference film can be increased.
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 preferred structural units of the side chain type liquid crystal polymers of formula a, formula b are those of the following formulae,
wherein the preparation of the compound of the structural unit of the formula a and the formula b is as follows:
sixteen acrylic acid ester:the monomer (1) is used as a monomer,
ethylene glycol monoacrylate:the monomer (2) is used as a monomer,
methacrylic acid:the monomer (3) is used as a monomer,
and dimethomorph:the monomer (4) is used as a monomer,
and a monomer 5.
As a preferred embodiment, the compounds of formula I, formula II and formula III are preferably compounds of the following formulae,
the structure of the polymerizable liquid crystal compound is as follows:
examples 1 to 10:
side chain type liquid crystal polymers were prepared according to the compositions and contents of table 1 below and the following methods.
The preparation method of the side chain type liquid crystal polymer comprises the following steps:
mixing the monomers, heating to react to obtain a mixed solution, and crystallizing the mixed solution to obtain the side chain type liquid crystal polymer. The specific method comprises the following steps: the monomers in Table 1 were prepared into a mixed solution according to the ratio and added to a three-necked flask. After the air was replaced with nitrogen, the temperature was raised. Controlling the temperature to 95 ℃ and reacting for 20 hours. After the reaction was completed, it was cooled to room temperature, and then added dropwise to another vessel in which methanol was being stirred and stirred for 20 minutes. The supernatant was removed, the resulting crude product was stirred again in methanol for 20 minutes, and the supernatant was removed, and the solid was redissolved in butanone and filtered. The solution was transferred to a rotary evaporator and spin dried.
TABLE 1 composition and content of side chain type liquid Crystal Polymer composition (/ g)
TABLE 2 molecular weight distribution of side chain type liquid crystalline polymers (/ g)
Examples 11 to 30 and comparative examples 1 to 6:
liquid crystal composition solutions and retardation films were prepared according to the compositions and contents of tables 3 and 4 below and the following methods.
The preparation method of the liquid crystal composition solution comprises the following steps:
the components were weighed according to the contents shown in tables 3 and 4, placed in a brown bottle, and placed on a magnetic stirrer with a temperature of 40 ℃ to stir for 1 hour, and the mixture was stirred uniformly to obtain a liquid crystal composition solution.
The preparation method of the phase difference film comprises the following steps:
first, a liquid crystal composition is prepared according to the above method;
then, the above liquid crystal composition was scraped onto a PVA film at a speed of 10cm/s with a 20# malt rod, and the scraped sample was dried in a forced air drying oven at 80℃for 60 seconds.
Finally, at room temperature, using a wavelength of 365nm, irradiance of 80Mw/cm 2 And (3) curing for 10s to obtain the phase difference film. Rth, pretilt angle, twist angle, adhesive force and bending resistance of the prepared phase difference film are carried out.
Liquid crystal composition solutions were prepared in the same proportions as in examples 11 to 30, and retardation films were prepared under other conditions as the proportions shown in Table 4. And Rth, pretilt angle, twist angle, adhesive force performance test and bending resistance performance test are carried out.
TABLE 3 liquid crystal compositions and contents of examples 11-20
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TABLE 4 liquid crystal compositions and contents of examples 21-30 and comparative examples 1-6
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The test results were as follows:
table 5 test data
Rth Pretilt angle Twist angle Adhesion force Bending resistance
Example 11 -732 895 02 No falling off by the hundred method Greater than 30 ten thousand times
Example 12 -1112 899 03 No falling off by the hundred method Greater than 30 ten thousand times
Example 13 -783 902 08 No falling off by the hundred method Greater than 30 ten thousand times
Example 14 -1101 898 02 No falling off by the hundred method Greater than 30 ten thousand times
Example 15 -1033 898 05 No falling off by the hundred method Greater than 30 ten thousand times
Example 16 -1132 898 12 No falling off by the hundred method Greater than 30 ten thousand times
Example 17 -1351 901 01 No falling off by the hundred method Greater than 30 ten thousand times
Example 18 -914 903 05 No falling off by the hundred method Greater than 30 ten thousand times
Example 19 -1232 899 07 No falling off by the hundred method Greater than 30 ten thousand times
Example 20 -1126 902 11 No falling off by the hundred method Greater than 30 ten thousand times
Example 21 -863 896 15 No falling off by the hundred method Greater than 30 ten thousand times
Example 22 -772 902 11 No falling off by the hundred method Greater than 30 ten thousand times
Example 23 -798 899 07 No falling off by the hundred method Greater than 30 ten thousand times
Example 24 -1104 902 03 No falling off by the hundred method Greater than 30 ten thousand times
Example 25 -1035 899 02 No falling off by the hundred method Greater than 30 ten thousand times
Example 26 -1016 901 08 No falling off by the hundred method Greater than 30 ten thousand times
Example 27 -1131 898 06 No falling off by the hundred method Greater than 30 ten thousand times
Example 28 -1367 897 08 No falling off by the hundred method Greater than 30 ten thousand times
Example 29 -1472 903 03 No falling off by the hundred method Greater than 30 ten thousand times
Example 30 -883 899 05 No hundred lattice methodShedding off Greater than 30 ten thousand times
Comparative example 1 -862 899 11 ＞5％ Less than 10 ten thousand times
Comparative example 2 -1181 900 15 ＞5％ Less than 10 ten thousand times
Comparative example 3 -105.5 89.7 1.1 ＞5％ Less than 10 ten thousand times
Comparative example 4 -786 902 07 ＞5％ Less than 10 ten thousand times
Comparative example 5 -833 901 03 ＞5％ Less than 10 ten thousand times
Comparative example 6 -65.5 89.6 0.3 ＞5％ Less than 10 ten thousand times
The test results of examples 11 to 30 and comparative example 1 revealed that the retardation film to which no side chain type liquid crystal polymer was added was slightly inferior in bending resistance and lowered in adhesion.
In comparative examples 2 to 6, although the types and proportions of the polymerizable liquid crystal materials in the comparative examples were changed, the bending resistance and the adhesion were not significantly improved, and the side chain type liquid crystal polymers containing the dimethomorph were inferior to those in the examples, so that it was demonstrated that inclusion of the dimethomorph structure in the side chain type liquid crystal polymer can enhance the adhesion while enhancing the bending resistance.
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 side chain type liquid crystal polymer, comprising: a first structural unit represented by formula a and a second structural unit represented by formula b;
the formula a is as follows:
wherein R is 3 Selected from methyl or hydrogen atoms; r is R 4 Is- (CH) 2 ) n -a linking group of formula wherein two non-adjacent carbons can each independently be substituted by-O-, -S-, -OCO-, -COO-, n being an integer from 0 to 10; r is R 5 Selected from methyl, aryl optionally having alkyl substituents OR-OR 7 Wherein R is 7 Represents a hydrogen atom, an alkyl group or an aryl group optionally having an alkyl substituent; m is an integer of 0 to 18 inclusive;
L 3 represents a linking group which is bonded to the substrate, selected from-C-C-, -O-, -S-, -COO-, -OCO-;
selected from aryl, heteroaryl, alicyclic, heterocyclic, fused rings wherein the carbon atoms in the ring may be optionally substituted with N, S atoms;
the formula b is as follows:
Wherein R is 1 Is methyl or hydrogen atom.
2. A liquid crystal composition comprising: the side-chain type liquid crystal polymer, polymerizable liquid crystal substance according to claim 1, wherein the polymerizable liquid crystal substance comprises a polymerizable liquid crystal compound or a polymerizable liquid crystal composition.
3. The liquid crystal composition according to claim 2, wherein the side chain type liquid crystal polymer accounts for 1 to 10% by mass of the total mass of the liquid crystal composition, and the polymerizable liquid crystal substance accounts for 80 to 95% by mass of the total mass of the liquid crystal composition.
4. The liquid crystal composition according to claim 2, wherein the polymerizable liquid crystal composition comprises: 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 alkyl structure with 1-25 carbon atoms and a branched-chain alkyl structure with 3-25 carbon atoms, a cyclic alkyl with 3-25 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 、Sp 2 represents any one of a straight-chain alkyl structure having 1 to 25 carbon atoms and 3 to 25 carbon atoms and a cyclic alkyl structure having 3 to 25 carbon atoms, wherein any two non-adjacent carbon atoms may be substituted with-O-, -OCO-, -COO-, -S-, -n=;
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;
wherein the polymerizable group comprises
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 alkyl structure having 1 to 25 carbon atoms, a branched alkyl structure having 3 to 25 carbon atoms, and a cyclic alkyl structure having 3 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 alkyl structure having 1 to 25 carbon atoms and having 3 to 25 carbon atoms as a branched chain, a cyclic alkyl group having 3 to 25 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, and a carbon atomAny one of alkynyl groups with the number of the children being 2-25;
L 3 comprises H, F, cl, CN, a straight-chain alkyl structure with 1-25 carbon atoms and a branched-chain alkyl structure with 3-25 carbon atoms, a cyclic alkyl with 3-25 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 wherein the heteroatoms include N, O, and S atoms;
Sp 3 represents any one of a straight chain alkyl group having 1 to 25 carbon atoms, a branched alkyl group having 3 to 25 carbon atoms and a cyclic alkyl group having 3 to 25 carbon atoms, wherein any two non-adjacent carbon atoms may be substituted by-O-, -OCO-, -COO-, -S-, -n= substitution,
P 3 comprising a polymerisable group or H;
Wherein the polymerizable group comprises
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.
5. The liquid crystal composition according to claim 4, wherein the first material accounts for 80-95% by mass of the polymerizable liquid crystal composition; the second material accounts for 5-20% of the mass of the polymerizable liquid crystal composition.
6. The liquid crystal composition according to claim 2, further comprising an initiator, the initiator being an initiator that initiates photopolymerization; the addition amount of the initiator is 0.1-10% of the total mass of the polymerizable liquid crystal substance.
7. The liquid crystal composition of claim 2, further comprising 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.
8. A retardation film, which is polymerized based on the liquid crystal composition according to any one of claims 2 to 7.
9. A method for producing a retardation film, comprising:
Mixing the liquid crystal composition according to any one of claims 2 to 7 with a solvent to obtain a liquid crystal composition solution;
coating the liquid crystal composition solution on the surface of a substrate, and drying to obtain a liquid crystal composition resin layer;
and irradiating the liquid crystal composition resin layer to obtain a phase difference film.
10. A display device comprising the retardation film formed by polymerizing the liquid crystal composition according to any one of claims 2 to 7 or the retardation film according to claim 8 or the retardation film produced by the production method according to claim 9, the display device being an active matrix display device or a passive matrix display device.
CN202311406458.2A 2023-10-26 2023-10-26 Side chain type liquid crystal polymer, liquid crystal composition, phase difference film, preparation method and display device Pending CN117567679A (en)

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