Liquid Crystal Compound, Liquid Crystal Composition, and Phase Difference Film

Abstract

The present application discloses a liquid crystal compound, a liquid crystal composition, and a retardation film, relating to the technical field of liquid crystal displays. In order to solve the problems of poor alignment order degree, low Δn value, and low crosslinking completion degree in the existing liquid crystal system, the present application sets the structural general formula (I) of the liquid crystal compound and applies it to the retardation film. The liquid crystal compound of the present application adopts a longer liquid crystal main chain, making the arrangement of liquid crystal molecules more orderly. The dense arrangement of chromogenic groups increases the van der Waals force and hydrogen bond interaction between liquid crystal molecules, thereby improving the alignment order degree and Δn value, achieving the purpose of improving dispersion, reducing manufacturing costs, reducing the film thickness requirement, and improving the crosslinking completion degree.

Description

Technical Field

[0001] This application relates to the technical field of optical material preparation, and particularly relates to a liquid crystal compound, a liquid crystal composition, and a retardation film. Background Art

[0002] Optical films are a key component in modern display technologies, and they can affect the performance of display quality such as display brightness, clarity, and large viewing angle color shift. Among them, the retardation film with inverse wavelength dispersion is widely used in polarizers of liquid crystal displays (LCDs) and organic light-emitting diode displays (OLEDs) for anti-reflection and viewing angle compensation due to its unique optical properties. Inverse wavelength dispersion generally means that at a positive viewing angle, the retardation amount is proportional to the wavelength, and it is usually expressed by the condition that the retardation amount R450 at a wavelength of 450 nm and the retardation amount R550 at a wavelength of 550 nm satisfy the following condition: R450 / R550 ≤ 1.0.

[0003] Currently, the main material used to achieve the retardation film with inverse wavelength dispersion is liquid crystal polymer material, and the retardation is caused by the birefringence of the material. Mainly, these liquid crystal polymers usually use a prepolymer coating solution as a precursor, and the precursor contains liquid crystal monomers with polymerizable groups, initiators, solvents, etc. In order to obtain a certain alignment of the liquid crystal, a functional alignment layer should also be provided on the substrate on which it is carried. After the precursor solution is coated on the substrate containing the alignment layer and undergoes a heating and drying step, after the solvent evaporates, the liquid crystal compound forms a liquid crystal phase with a specific orientation (i.e., "alignment") under certain temperature conditions. Subsequently, through a UV light-induced polymerization reaction, the alignment of the liquid crystal is fixed, thereby obtaining an anisotropic polymer thin film with regular orientation, and then having the optical properties of retardation.

[0004] The existing reverse wavelength dispersion monomer molecular structure is mainly composed of a main chain and a chromophore side chain (refer to patents: US20180346614, CN113150792A, WO2017043438, US8323527, US8687259B2, CN1950350). These monomers can exhibit quite good reverse wavelength dispersion. The number of six-membered ring monomers in the main chain is 5 or less, and the chromophore in the side chain is 1 unit / molecule. However, in this molecular structure, the chromophores are not dense, and the presence of chromophores easily disrupts the order of liquid crystal alignment, resulting in poor alignment order in these liquid crystal systems, thus reducing the Δn value. The consequences of low Δn are: first, the problem of a high dispersion R450 / R550 value. To reduce dispersion, the content of reverse wavelength dispersion monomers in the formulation increases, increasing the manufacturing cost. Second, the film thickness required to achieve the target R550 increases, increasing the amount of materials required per unit area and thus increasing the cost. In addition, since the molecular weight of these reverse wavelength dispersion monomers is too small and the polymerizable groups are too dense, when photocuring, the shrinkage rate of the crosslinking system is too large, ultimately resulting in a low degree of crosslinking completion, which is not conducive to the reliability of the system, such as the change in the optical properties of the optical film after high temperature. Summary of the Invention

[0005] The present invention discloses a liquid crystal compound, a liquid crystal composition, and a retardation film to solve the problems of poor alignment order, low Δn value, and low degree of crosslinking completion in existing liquid crystal systems.

[0006] To achieve the above object, the embodiments of this specification adopt the following technical solutions:

[0007] In a first aspect, an embodiment of the present application provides a liquid crystal compound, and the structure of the liquid crystal compound satisfies the general formula (I):

[0008] (I);

[0009] In the general formula (I), 3 ≤ x ≤ 10, 2 ≤ y ≤ 5, where x is a positive integer and y is a positive integer;

[0010] In the general formula (I), A 1 represents , and the two bonding positions * on A 1 can be arbitrarily reversed and flipped, where 0 ≤ m1 + m2 + m3 ≤ 15, m1 is a positive integer, m2 is a positive integer, and m3 is a positive integer; -CH 2 -、-O-、-COO- in A 1 1 can be arranged in any order except for forming -O-O-, and the direction of the ester bond represented by -COO- in A

[0011] ​In general formula (I), A 2 represents , and the two bonding positions * on A 2 can be arbitrarily reversed and flipped, where 0 ≤ n1 + n2 + n3 ≤ 15, n1 is a positive integer, n2 is a positive integer, and n3 is a positive integer; in A 2 , -CH 2 -, -O-, -COO- can be arranged in any order except to form -O-O-, and in A 2 , the direction of the ester bond represented by -COO can be arbitrarily selected as forward or reverse;

[0012] In general formula (I), L 1 ~L x each independently selected from a single bond, , , , , , , , , and the two bonding positions * on them can be arbitrarily reversed and flipped;

[0013] In general formula (I), G 1 ~G x each independently selected from 1,4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, naphthalene-1,4-diyl, tetrahydronaphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl or 1,3-dioxane-2,5-diyl; there is no left or right regulation for the two bonding positions on G 1 ~G x , and they can be arbitrarily selected; H on G 1 ~G x is unsubstituted or substituted by one or more substituents Sp1, and the respective Sp1 groups are the same or different;

[0014] Sp1 is selected from a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorothioalkyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or a linear or branched alkyl chain having 1 to 20 carbon atoms. One -CH 2 - or two or more non-adjacent -CH 2- Each can be independently substituted by -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C-, and any hydrogen atom in the alkyl chain selected by Sp1 can be substituted by a fluorine atom;

[0015] In general formula (I), R 1 , R 2 are each independently selected from a hydrogen atom, a methyl group, a methoxy group, an ethoxy group, , , , or group;

[0016] In general formula (I), Ar 1 ~Ar y is a 5- to 10-membered aromatic ring or aromatic heterocycle; H on Ar 1 ~Ar y can be substituted by SG 1 ~SG y or substituted by one or more substituents Sp2;

[0017] Sp2 is selected from a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorothioalkyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or a linear or branched alkyl chain having 1 to 20 carbon atoms. One -CH2- or two or more non-adjacent -CH2- in the alkyl chain selected by Sp2 can be independently substituted by -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C-, and any hydrogen atom in the alkyl chain selected by Sp2 can be substituted by a fluorine atom;

[0018] In general formula (I), M 1 ~M y are each independently selected from a single bond, , , , , and the two bonding positions * on M 1 ~M y can be arbitrarily reversed;

[0019] In general formula (I), SG 1 ~SG y has the structure of general formula (II):

[0020] (II);

[0021] In general formula (II), J 1 ~J y each independently selected from a single bond, -O-, -S-, -OCH 2 -, -CH 2 O-, -CH 2 CH 2 -, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O-NH-, -SCH 2 -, -CH 2 S-, -CF 2 O-, -OCF 2 -, -CF 2 S-, -SCF 2 -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH2CH 2 -, -OCO-CH 2 CH 2 -, -CH 2 CH 2 -COO-, -CH 2 CH 2 -OCO-, -COO-CH2-, -OCO-CH 2 -, -CH 2 -COO-, -CH 2 -OCO-, -CH=CH-, -N=N-, -CH=N-, -N=CH-, -CH=N-N=CH-, -CF=CF-, -C≡C-, , , or , J 1 ~J y the two bonding positions * on have no left - right direction regulation and can be arbitrarily selected;

[0022] wherein, Q is represented by and T 1 is selected from , The two bonding positions on * can be arbitrarily reversed and flipped; 0 ≤ p1 + p2 + p3 ≤ 16, where p1 is a positive integer, p2 is a positive integer, and p3 is a positive integer; T 1 The -CH 2 -、-O-、-COO- can be arranged in any order except for the formation of -O-O-; T 1 The direction of the ester bond represented by -COO- in can be arbitrarily selected as forward or reverse; R 3 is selected from a hydrogen atom, a methyl group, an ethyl group, a methoxy group, 、 、 、 、 group;

[0023] In general formula (II), E 1 ~E y each independently is selected from a single bond, (1 ≤ q ≤ 5), 、 、 、 、 、 ; E 1 ~E y There is no left - right regulation for the two bonding positions on, and they can be arbitrarily selected; E 1 ~E y is unsubstituted or substituted by one or more substituents Sp3;

[0024] Sp3 is selected from a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorothio group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or a linear or branched alkyl chain with 1 to 20 carbon atoms. One - CH 2 - or two or more non - adjacent -CH 2 - in the alkyl chain selected by Sp3 can each independently be substituted by -O-, -S-, -CO-, -COO-, -OCO-, -CO - S-, -S - CO-, -O - CO - O-, -CO - NH-, -NH - CO-, -CH=CH - COO-, -CH=CH - OCO-, -COO - CH=CH-, -OCO - CH=CH-, -CH=CH-, -CF=CF- or -C≡C-. Any hydrogen atom in the alkyl chain selected by Sp3 can be substituted by a fluorine atom.

[0025] In general formula (II), Z 1 ~Z y is a 5 - to 14 - membered aromatic ring or aromatic heterocyclic ring; Z 1 ~Z yH thereon is unsubstituted, or can be substituted by one or more substituents Sp4, substituted, and linked to E 1 ~E y ;

[0026] Sp4 is selected from a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorothio group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or a linear or branched alkyl chain having 1 to 20 carbon atoms. One -CH 2 - or two or more non - adjacent -CH 2 - in the alkyl chain selected by Sp4 can each independently be substituted by -O-, -S-, -CO-, -COO-, -OCO-, -CO - S-, -S - CO-, -O - CO - O-, -CO - NH-, -NH - CO-, -CH=CH - COO-, -CH=CH - OCO-, -COO - CH=CH-, -OCO - CH=CH-, -CH=CH-, -CF=CF- or -C≡C-. Any hydrogen atom in the alkyl chain selected by Sp4 can be substituted by a fluorine atom;

[0027] In, T 2 is selected from , where r is 0 to 10, and R 4 is selected from methyl, ethyl, methoxy, , , , , groups.

[0028] Optionally, M 1 ~M y each independently is selected from , , , or .

[0029] Optionally, in the general structural formula (II) of SG 1 ~SG y , when J 1 ~J y is selected from , E is a single bond, and Z is a benzothiazole group, p2 + p3≠0 in Q.

[0030] Optionally, the structural formula of SG 1 ~SG y is:

[0031] .

[0032] In a second aspect, an embodiment of the present application provides a liquid crystal composition, including: the above-mentioned liquid crystal compound and a polymerizable liquid crystal compound.

[0033] Optionally, the liquid crystal composition includes: a liquid crystal compound in an amount of greater than or equal to 5 parts by weight, and a polymerizable liquid crystal compound in an amount of greater than or equal to 5 parts by weight.

[0034] Optionally, the liquid crystal composition includes: a liquid crystal compound in an amount of 50 - 90 parts by weight, and a polymerizable liquid crystal compound in an amount of 10 - 50 parts by weight.

[0035] Optionally, the polymerizable liquid crystal compound is selected from the following structures:

[0036]

[0037] In a third aspect, an embodiment of the present application provides a retardation film, which is polymerized from the above-mentioned liquid crystal composition.

[0038] Optionally, the retardation amount R450 of the retardation film at a wavelength of 450 nm and the retardation amount R550 at a wavelength of 550 nm satisfy R450 / R550 ≤ 1.0.

[0039] The above-mentioned at least one technical solution adopted in the embodiment of the present application can achieve the following beneficial effects:

[0040] (1) Improving dispersion: Compared with the monomers in the prior art in which the number of main-chain six-membered rings is 5 or less and the side-chain chromophore is 1 unit / molecule, the monomer structure of the present invention can more effectively improve the order degree of the liquid crystal, thereby reducing dispersion and improving the performance of the optical film.

[0041] (2) Reducing manufacturing cost: Since the inverse wavelength dispersion monomer of the present invention can increase the Δn value, the content of the inverse wavelength dispersion monomer can be reduced in the formulation, thereby reducing the manufacturing cost. Compared with the prior art in which the content of the inverse wavelength dispersion monomer has to be increased to reduce dispersion, the present invention provides a more economical and practical solution.

[0042] (3) Reducing the film thickness requirement: Since the inverse wavelength dispersion monomer of the present invention can increase the Δn value, the retardation amount required to reach the target R550 can be achieved at a lower film thickness. This not only reduces the amount of materials required per unit area, thereby reducing the cost, but also improves the degree of thinning of the optical film, meeting the requirements of modern display technology for thin and light.

[0043] (4) Improve the degree of crosslinking completion: Since the inverse wavelength dispersion monomer of the present invention has a relatively large molecular weight and the polymerizable groups are relatively dispersed, during photocuring, the shrinkage rate of the crosslinking system is small, and the crosslinking reaction proceeds more smoothly, ultimately resulting in a relatively high degree of crosslinking completion. This improves the reliability of the optical film and ensures that the optical film can still maintain good optical properties after being subjected to high temperature or other environmental changes. Specific Embodiments

[0044] To make the objectives, technical solutions, and advantages of the present application clearer, the technical solutions of the present application will be clearly and completely described below in conjunction with specific embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without making creative efforts shall fall within the scope of protection of the present application.

[0045] According to an embodiment of the present application, a liquid crystal compound is provided, and the structure of the liquid crystal compound satisfies the general formula (I):

[0046] (I);

[0047] In the general formula (I), 3 ≤ x ≤ 10, 2 ≤ y ≤ 5, where x is a positive integer, y is a positive integer, and the parentheses in x and y represent group combinations, that is , and can be arranged in any order. Preferably, x is 5, 6, or 7, and y is 2 or 3.

[0048] In the general formula (I), A 1 represents , and the two bonding positions * on A 1 can be arbitrarily reversed, where 0 ≤ m1 + m2 + m3 ≤ 15, m1 is a positive integer, m2 is a positive integer, and m3 is a positive integer; in A 1 , -CH 2 -, -O-, -COO- can be arranged in any order except for forming -O-O-, and the ester bond direction represented by -COO- in A 1 can be arbitrarily selected for positive or negative;

[0049] In the general formula (I), A 2 represents , and the two bonding positions * on A 2 can be arbitrarily reversed, where 0 ≤ n1 + n2 + n3 ≤ 15, n1 is a positive integer, n2 is a positive integer, and n3 is a positive integer; in A 2 , -CH 2 -, -O-, -COO- can be arranged in any order except for forming -O-O-, and in A 2The direction of the ester bond represented by -COO- can be arbitrarily selected as forward or reverse.

[0050] Preferably, A 1 and A 2 is , where * can be connected to G 1 ~G x , L 1 ~L x , Ar 1 ~Ar x or M 1 ~M x groups.

[0051] In general formula (I), L 1 ~L x each independently selected from a single bond, , , , , , , , , the two bonding positions * on

[0052] can be arbitrarily reversed and flipped. 1 ~G x each independently selected from 1,4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, naphthalene-1,4-diyl, tetrahydronaphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl or 1,3-dioxane-2,5-diyl; for G 1 ~G x , there is no left or right regulation for the two bonding positions, and they can be arbitrarily selected; for G 1 ~G x , the H on it is unsubstituted or substituted by one or more substituents Sp1, and the respective Sp1 groups can be the same or different, and one or more here includes one.

[0053] Sp1 is selected from a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorothioalkyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or a linear or branched alkyl chain having 1 to 20 carbon atoms. One -CH 2 - or two or more non-adjacent -CH 2- Each can be independently substituted by -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C-, and any hydrogen atom in the alkyl chain selected by Sp1 can be substituted by a fluorine atom.

[0054] From the perspective of structural generality and availability, G 1 ~G x Preferably used:

[0055] .

[0056] In general formula (I), R 1 , R 2 are each independently selected from a hydrogen atom, a methyl group, a methoxy group, an ethoxy group, , , , or group.

[0057] In general formula (I), Ar 1 ~Ar y is a 5- to 10-membered aromatic ring or aromatic heterocycle; the H on Ar 1 ~Ar y can be substituted by SG 1 ~SG y or substituted by one or more substituents Sp2, where one or more includes one;

[0058] Sp2 is selected from a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorothioalkyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or a linear or branched alkyl chain having 1 to 20 carbon atoms. One -CH2- or two or more non-adjacent -CH2- in the alkyl chain selected by Sp2 can each be independently substituted by -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C-, and any hydrogen atom in the alkyl chain selected by Sp2 can be substituted by a fluorine atom.

[0059] Preferably, Ar 1 ~Ary Preferably used 、 。

[0060] In general formula (I), M 1 ~M y are each independently selected from a single bond, 、 、 、 , and the two bonding positions * on M 1 ~M y can be arbitrarily reversed and flipped.

[0061] Preferably, M 1 ~M y are each independently selected from 、 、 or

[0062] In general formula (I), the structure of SG 1 ~SG y is general formula (II):

[0063] (II);

[0064] In general formula (II), J 1 ~J y are each independently selected from a single bond, -O-, -S-, -OCH 2 -, -CH 2 O-, -CH 2 CH 2 -, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O-NH-, -SCH 2 -, -CH 2 S-, -CF 2 O-, -OCF 2 -, -CF 2 S-, -SCF 2 -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH2CH 2 -, -OCO-CH 2 CH 2 -, -CH 2 CH 2 -COO-, -CH 2 CH 2-OCO-, -COO-CH2-, -OCO-CH 2 -, -CH 2 -COO-, -CH 2 -OCO-, -CH=CH-, -N=N-, -CH=N-, -N=CH-, -CH=N-N=CH-, -CF=CF-, -C≡C-, , , or , J 1 ~J y The two bonding positions * on J have no left - right direction specification and can be arbitrarily selected;

[0065] Among them, Q is represented by , T 1 is selected from , The two bonding positions * on can be arbitrarily reversed and flipped; 0 ≤ p1 + p2 + p3 ≤ 16, p1 is a positive integer, p2 is a positive integer, p3 is a positive integer; -CH 1 in T 2 -, -O-, -COO- can be arranged in any order except to form -O-O-; The ester bond direction represented by -COO- in T 1 can be arbitrarily selected for forward or reverse; R 3 is selected from a hydrogen atom, a methyl group, an ethyl group, a methoxy group, , , , , group.

[0066] Preferably, in the general formula (II) of SG 1 ~SG y , when J 1 ~J y is selected from , E is a single bond, and Z is a benzothiazole group, p2 + p3 ≠ 0 in Q.

[0067] In the general formula (II), E 1 ~E y each independently is selected from a single bond, (1 ≤ q ≤ 5), , , , , , ; The two bonding positions on E 1 ~E y have no left - right specification and can be arbitrarily selected; E 1 ~E yis unsubstituted or substituted by one or more substituents Sp3, where one or more includes one;

[0068] Sp3 is selected from a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorothio group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or a linear or branched alkyl chain having 1 to 20 carbon atoms. One - CH 2 - or two or more non - adjacent - CH 2 - can each independently be substituted by -O-, -S-, -CO-, -COO-, -OCO-, -CO - S-, -S - CO-, -O - CO - O-, -CO - NH-, -NH - CO-, -CH=CH - COO-, -CH=CH - OCO-, -COO - CH=CH-, -OCO - CH=CH-, -CH=CH-, -CF=CF- or -C≡C-. Any hydrogen atom in the alkyl chain selected by Sp3 can be substituted by a fluorine atom.

[0069] In general formula (II), Z 1 ~Z y is a 5 - to 14 - membered aromatic ring or aromatic heterocycle; H on Z 1 ~Z y is unsubstituted, can be substituted by one or more substituents Sp4, substituted, and linked to E 1 ~E y linked.

[0070] Sp4 is selected from a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorothio group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or a linear or branched alkyl chain having 1 to 20 carbon atoms. One - CH 2 - or two or more non - adjacent - CH 2 - can each independently be substituted by -O-, -S-, -CO-, -COO-, -OCO-, -CO - S-, -S - CO-, -O - CO - O-, -CO - NH-, -NH - CO-, -CH=CH - COO-, -CH=CH - OCO-, -COO - CH=CH-, -OCO - CH=CH-, -CH=CH-, -CF=CF- or -C≡C-. Any hydrogen atom in the alkyl chain selected by Sp4 can be substituted by a fluorine atom;

[0071] In, T 2 is selected , where r is from 0 to 10, R 4 is selected from methyl, ethyl, methoxy, , , , , groups.

[0072] Considering the simplicity, convenience and availability of the molecular structure, the following are some preferred structures of SG 1 ~SG y groups:

[0073] .

[0074] The following are preferably liquid crystal compounds conforming to the general formula (I):

[0075]

[0076] The preparation method of the liquid crystal compound of the general formula (I) is not particularly limited and can be synthesized by known methods. For example, it can be prepared by the methods described in CN107108458B, CN101470212B, CN113150792A, CN104245885B, CN1950350A, JP2005208416A, March's Advanced Organic Chemistry (Wiley), Greene’s Protective Groups In Organic Synthesis 4th Edition (Wiley).

[0077] According to an embodiment of the present application, a liquid crystal composition is provided, comprising: a liquid crystal compound, a polymerizable liquid crystal compound.

[0078] The liquid crystal composition comprises: a liquid crystal compound in an amount of not less than 5 parts by weight, and a polymerizable liquid crystal compound in an amount of not less than 5 parts by weight. Preferably, the liquid crystal composition comprises: 50 - 90 parts by weight of the liquid crystal compound, and 10 - 50 parts by weight of the polymerizable liquid crystal compound.

[0079] In the liquid crystal composition, the liquid crystal compound can be used as an inverse wavelength dispersion monomer and one or more kinds conforming to the general formula (I) can be added. The polymerizable liquid crystal compound exhibits positive wavelength dispersion and is blended with the inverse wavelength dispersion monomer to play roles such as adjusting wavelength dispersion, increasing crosslinking density, adjusting refractive index, inducing chiral phase, and reducing costs. The following are preferably polymerizable liquid crystal compounds:

[0080]

[0081] In order to form a crosslinked network by photoinitiated polymerization, a photoinitiator generally needs to be added to the liquid crystal composition. The photoinitiators applicable to the present invention may include, but are not limited to, the compounds represented by the following structural formulas I-1 to I-7. At the same time, some brand photoinitiators such as BASF OXE-03 and OXE-04 can also be added.

[0082]

[0083] In the liquid crystal composition of the present invention, the weight parts of the photoinitiator are 0.2 to 10 parts, preferably 3 to 7 parts. For example, in the liquid crystal composition provided by the present invention, the weight parts of the photoinitiator can be 0.2 part, 0.4 part, 0.6 part, 0.8 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts or any value between these numbers.

[0084] In the actual coating production process, other additives can be added as needed to ensure solution stability, leveling property, photo-crosslinking efficiency, etc. For example, the additives applicable to the liquid crystal composition of the present invention may include a combination of one or more of leveling and defoaming additives, polymerization inhibitors, and chain transfer agents. Among them, the leveling and defoaming additives can be at least one of BYK-300, BYK-306, BYK-358, BYK-354, BYK-515, BYK-3560, BYK-3566 purchased from BYK Company; MEGAFACE F-554 and F-556 purchased from DIC Company; and Zonyl FS-520 and Zonyl 8857A purchased from DuPont Company. The polymerization inhibitors suitable for the present invention may include at least one of benzoquinone, hydroquinone, and 2,6-di-tert-butyl-4-methylphenol (BHT); the chain transfer agents suitable for the present invention may include at least one of dodecyl mercaptan and triethylamine.

[0085] In the liquid crystal composition of the present invention, the weight portion of the auxiliary agent is 0.01 to 5 parts, preferably 0.1 to 1 parts. For example, in the liquid crystal composition of the present invention, the weight portion of the auxiliary agent suitable for addition is 0.01 parts, 0.02 parts, 0.04 parts, 0.06 parts, 0.08 parts, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 parts, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts or any value between these numbers.

[0086] In the actual production process of optical films using liquid crystal compositions, solvents are needed to assist in coating processing. Solvents suitable for the liquid crystal composition of the present invention mainly include benzene, ketones, esters and high polarity solvents. Benzene solvents mainly include: toluene, xylene, chlorobenzene, ethylbenzene; ketone solvents mainly include: butanone, 3-pentanone, cyclopentanone, cyclohexanone, N-methylpyrrolidone, isophorone; ester solvents mainly include: ethyl acetate, butyl acetate, propylene glycol methyl ether acetate; high polarity solvent solvents mainly include: n-butanol, isopropanol, propylene glycol methyl ether, N,N-dimethylformamide, ethanolamine, acetonitrile. In one embodiment, one solvent can be used. In another embodiment, the above solvents can be used in combination. Among them, in terms of weight parts (and calculated by non-volatile content), 100 to 1200 parts by weight of solvent can be added to the above liquid crystal composition, preferably 250 to 350 parts by weight of solvent. For example, in the above-mentioned liquid crystal composition of the present invention, 100, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 295, 300, 305, 310, 311, 312, 313, 314, 315, 316, 317, 318, 319, 320, 325, 330, 335, 340, 350, 360, 370, 380, 390, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200 parts of at least one of the above-mentioned solvents can be added in parts by weight.

[0087] In another embodiment of the present application, an anisotropic body is also provided, wherein the anisotropic body is obtained from the above-mentioned liquid crystal composition of the present application through a polymerization reaction.

[0088] In another embodiment of the present application, an optical film is provided. The optical film includes a polymerized product generated by a polymerization reaction of the liquid crystal composition described in the present application or includes the anisotropic body described in the present application.

[0089] In another embodiment of the present application, a retardation film is further provided. The retardation film includes a polymerization product formed by the polymerization reaction of the liquid crystal composition described in the present application or includes the anisotropic body described above in the present application. Wherein, the retardation amount R450 of the retardation film at a wavelength of 450 nm and the retardation amount R550 at a wavelength of 550 nm satisfy the following condition: R450 / R550 ≤ 1.0.

[0090] The main technical means adopted in this technical solution are as follows: 1. Using a longer liquid crystal main chain: By using a longer liquid crystal main chain (more than 5 six-membered rings), the order degree of the liquid crystal curing system can be enhanced, the △n value can be increased, the dispersion can be reduced, and the crosslinking completion degree can be improved. The longer liquid crystal main chain can provide more steric hindrance, making the arrangement of liquid crystal molecules more orderly, thereby improving the alignment order degree and the △n value. 2. Dense arrangement of chromophore groups: By using a dense arrangement of chromophore groups (more than 2 units per molecule), the interaction between liquid crystal molecules can be enhanced, and the order degree of the liquid crystal curing system can be further improved. The dense arrangement of chromophore groups can increase the van der Waals force and hydrogen bond interaction between liquid crystal molecules, thereby improving the alignment order degree and the △n value.

[0091] Compared with the prior art, this technical solution mainly solves the following problems: 1. Improving the alignment order degree of the inverse wavelength dispersion monomer, increasing the △n value, and reducing the dispersion; 2. Reducing the usage amount of the inverse wavelength dispersion monomer, reducing the manufacturing cost, and reducing the preparation cost of the optical film; 3. Increasing the reliability problems such as the high temperature resistance performance of the optical film.

[0092] The technical solutions provided by each embodiment of the present application are described in detail below.

[0093] Example 1: Synthesis of R-5

[0094] Trans-4-[4-(6-acryloyloxyhexyloxy)phenoxycarbonyl]cyclohexanecarboxylic acid (50 g, 120 mmol), 2,5-dihydroxybenzaldehyde (18.2 g, 132 mmol), 4-dimethylaminopyridine (1.5 g, 12 mmol) were dissolved in 300 mL of dichloromethane. N,N'-Diisopropylcarbodiimide (16.6 g, 132 mmol) was slowly added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 12 hours. The resulting mixture was subjected to column chromatography and crystallization to obtain 37 g of a white solid compound 1a, with a yield of 58%.

[0095] Hydrazinylbenzothiazole (197 g, 120 mmol) and cesium carbonate (78 g, 240 mmol) were dissolved in a mixed solution of 800 mL of tetrahydrofuran and 800 mL of N,N-dimethylformamide, and stirred for 1 hour in an ice-water bath. 2-Chloroethoxy-2-ethoxydiethanol (30 g, 180 mmol) was slowly added dropwise, and the reaction was carried out at 80 °C for 12 hours. Ethyl acetate was added, and the organic phase was washed successively with water and saturated brine, and then concentrated. The resulting mixture was subjected to column chromatography to obtain 210 g of a light brown solid compound 1b with a yield of 59%.

[0096] Trans-1,4-cyclohexanedicarboxylic acid (17.2 g, 100 mmol) was dissolved in 5 mL of thionyl chloride, and a catalytic amount of N,N-dimethylformamide was added, and the mixture was refluxed for 1 hour. It was concentrated under reduced pressure, and the resulting mixture was recrystallized to obtain 11.8 g of colorless needle-like crystals of compound 1c with a yield of 56%.

[0097] Compound 1a (25 g, 46.5 mmol), compound 1c (4.85 g, 23.2 mmol), and N,N-diisopropylethylamine (6 g, 46.5 mmol) were dissolved in 200 mL of DCM, and the reaction was carried out at room temperature for 2 hours. The resulting mixture was subjected to column chromatography and crystallization to obtain 16 g of a white solid compound 1d with a yield of 57%.

[0098] Compound 1d (16 g, 13.2 mmol), compound 1b (8.6 g, 29 mmol), and racemic camphorsulfonic acid (6.1 g, 26.4 mmol) were dissolved in 200 mL of chloroform, and the reaction was carried out at 70 °C for 2 hours. The resulting mixture was subjected to column chromatography and crystallization to obtain 18.9 g of a white solid compound 1e with a yield of 81%.

[0099] Compound 1e (18.9 g, 10.7 mmol) and N,N-diisopropylethylamine (5.5 g, 42.8 mmol) were dissolved in 200 mL of dichloromethane, and acryloyl chloride (3.9 g, 42.8 mmol) was added dropwise in an ice-water bath, and the reaction was carried out at room temperature for 1 hour. The resulting mixture was subjected to column chromatography and crystallization to obtain 16 g of a white solid compound R-5 with a yield of 80%. 1 H NMR (500 MHz, CDCl 3 ) δ8.00 (s, 2H), 7.74 (s, 2H), 7.71-7.64 (m, 4H), 7.37-7.32 (m, 2H), 7.20-7.15(m, 2H), 7.14-7.08 (m, 4H), 6.99 (d, J = 8.7 Hz, 4H), 6.88 (d,J = 8.9 Hz, 4H), 6.43 - 6.33 (m, 4H), 6.17 - 6.04 (m, 4H), 5.84 - 5.73 (m, 4H), 4.48 (t, J = 5.3 Hz, 4H), 4.22 - 4.14 (m, 8H), 3.95 (t, J = 6.4 Hz, 4H), 3.88 (t, J = 5.4 Hz, 4H), 3.65 - 3.56 (m, 12H), 2.78 - 2.72 (m, 2H), 2.69 - 2.59 (m, 4H), 2.43 - 2.28 (m, 12H), 1.84 - 1.76 (m, 8H), 1.75 - 1.65 (m, 12H), 1.55 - 1.43 (m, 8H).

[0100] The specific preparation process is as follows:

[0101]

[0102] Example 2: Synthesis of R-1

[0103] 2-Hydrazinobenzothiazole (7.26 g, 44 mmol) and cesium carbonate (28.7 g, 88 mmol) were dissolved in a mixed solution of 50 mL of tetrahydrofuran and 50 mL of N,N-dimethylformamide, and stirred for 1 hour in an ice-water bath. Diethylene glycol-2-bromoethyl methyl ether (15 g, 66 mmol) was slowly added dropwise, and the reaction was carried out at 80 °C for 12 hours. Ethyl acetate was added, and the organic phase was washed successively with water and saturated brine, and concentrated. The resulting mixture was subjected to column chromatography to obtain 8.2 g of a pale yellow oily compound 2a with a yield of 60%.

[0104] Compound 1d (5 g, 4.1 mmol), compound 2a (2.8 g, 9 mmol), and racemic camphorsulfonic acid (1.9 g, 8.2 mmol) were dissolved in 100 mL of chloroform, and the reaction was carried out at 70 °C for 1 hour. The resulting mixture was subjected to column chromatography and crystallization to obtain 4.4 g of a white solid compound R-1 with a yield of 60%. 1 H NMR (400 MHz, CDCl 3 ) δ 8.01 (s, 2H), 7.75 (s, 2H), 7.72 - 7.64 (m, 4H), 7.37 - 7.32 (m, 2H), 7.20 - 7.15 (m, 2H), 7.14 - 7.08 (s, 4H), 6.99 (d, J= 7.8 Hz, 4H), 6.88 (d, J = 7.9 Hz, 4H), 6.41 (d, J = 17.3 Hz, 2H),6.13 (dd, J = 17.2, 10.5 Hz, 2H), 5.82 (d, J = 10.3 Hz, 2H), 4.51-4.46 (m, 4H),4.18 (t, J = 6.5 Hz, 4H), 3.95 (t, J = 6.1 Hz, 4H), 3.89 (d, J = 4.6 Hz, 4H), 3.67-3.62 (m, 4H), 3.60-3.55 (m, 4H), 3.55-3.50 (m, 4H), 3.42-3.37 (m, 4H), 3.27(s, 6H), 2.79-2.72 (m, 2H), 2.70-2.58 (m, 4H), 2.44-2.29 (m, 12H), 1.84-1.68(m, 20H), 1.56-1.42 (m, 8H).

[0105] The specific preparation process is as follows:

[0106]

[0107] Example 3: Synthesis of R-7

[0108] (E,E)-[1,1'-Bicyclohexyl]-4,4'-dicarboxylic acid (1.72 g, 6.77 mmol) was dissolved in 5 mL of thionyl chloride, and a catalytic amount of N,N-dimethylformamide was added. The mixture was refluxed for 1 hour. After concentration under reduced pressure, the resulting mixture was recrystallized to obtain 1.3 g of colorless needle-like crystal compound 3a in a yield of 66%.

[0109] Compound 1a (2.8 g, 5.25 mmol), compound 3a (0.73 g, 2.5 mmol), and N,N-diisopropylethylamine (0.68 g, 5.25 mmol) were dissolved in 60 mL of dichloromethane and reacted at room temperature for 2 hours. The resulting mixture was subjected to column chromatography and crystallization to obtain 1.9 g of white solid compound 3b in a yield of 59%.

[0110] Compound 3b (1.9 g, 1.47 mmol), compound 1b (0.96 g, 3.23 mmol), and racemic camphorsulfonic acid (0.68 g, 2.94 mmol) were dissolved in 20 mL of chloroform and reacted at 70 °C for 2 hours. The resulting mixture was subjected to column chromatography and crystallization to obtain 1.8 g of white solid compound 3c with a yield of 66%.

[0111] Compound 3c (1.8 g, 0.97 mmol) and N,N-diisopropylethylamine (0.5 g, 3.88 mmol) were dissolved in 4 mL of dichloromethane. Acryloyl chloride (0.35 g, 3.88 mmol) was added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 1 hour. The resulting mixture was subjected to column chromatography and crystallization to obtain 1.5 g of white solid compound R-7 with a yield of 79%. 1 H NMR (400 MHz, CDCl 3 ) δ7.98 (s, 2H), 7.74 (s, 2H), 7.71-7.64 (m, 4H), 7.38-7.31 (m, 2H), 7.21-7.14(m, 2H), 7.13-7.06 (m, 4H), 6.99 (d, J = 7.8 Hz, 4H), 6.88 (d, J = 7.8 Hz, 4H),6.44-6.35 (m, 4H), 6.17-6.05 (m, 4H), 5.84-5.75 (m, 4H), 4.52-4.45 (m, 4H),4.23-4.14 (m, 8H), 3.95 (t, J = 6.0 Hz, 4H), 3.91-3.84 (m, 4H), 3.66-3.61 (m,8H), 3.60-3.55 (m, 4H), 2.69-2.55 (m, 6H), 2.39-2.22 (m, 12H), 1.99-1.90 (m,4H), 1.84-1.56 (m, 20H), 1.55-1.42 (m, 8H), 1.27-1.10 (m, 6H).

[0112] The specific preparation process is as follows:

[0113]

[0114] Example 4: Synthesis of R-3

[0115] Compound 1a (1 g, 1.86 mmol), terephthaloyl chloride (0.18 g, 0.89 mmol), and N,N-diisopropylethylamine (0.34 g, 2.67 mmol) were dissolved in 20 mL of dichloromethane. The reaction was carried out at room temperature for 2 hours. The resulting mixture was subjected to column chromatography and crystallization to obtain 0.84 g of white solid compound 4a in a yield of 80%.

[0116] Compound 4a (0.84 g, 0.48 mmol), compound 1b (0.32 g, 1.08 mmol), and racemic camphorsulfonic acid (0.22 g, 0.96 mmol) were dissolved in 20 mL of chloroform. The reaction was carried out at 70 °C for 2 hours. The resulting mixture was subjected to column chromatography and crystallization to obtain 0.8 g of brown solid compound 4b in a yield of 96%.

[0117] Compound 4b (0.8 g, 0.45 mmol) and N,N-diisopropylethylamine (0.23 g, 1.8 mmol) were dissolved in 20 mL of dichloromethane. Acryloyl chloride (0.16 g, 1.8 mmol) was added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 1 hour. The resulting mixture was subjected to column chromatography and crystallization to obtain 0.62 g of white solid compound R-3 in a yield of 73%. 1 H NMR (400 MHz, CDCl 3 ) δ8.44 (s, 4H), 8.14 (s, 2H), 7.79 (s, 2H), 7.68 - 7.62 (m, 4H), 7.36 - 7.29 (m,4H), 7.24 - 7.12 (m, 4H), 7.00 (d, J = 8.4 Hz, 4H), 6.89 (d, J = 8.4 Hz, 4H), 6.45 - 6.30 (m, 4H), 6.17 - 6.00 (m, 4H), 5.85 - 5.70 (m, 4H), 4.46 - 4.38 (m, 4H), 4.20 - 4.13 (m, 8H), 3.95 (t, J = 6.1 Hz, 4H), 3.85 - 3.77 (m, 4H), 3.59 - 3.54 (m, 4H),3.53 - 3.41 (m, 8H), 2.74 - 2.57 (m, 4H), 2.41 - 2.29 (m, 8H), 1.86 - 1.67 (m, 16H),1.56 - 1.41 (m, 8H).

[0118] The specific preparation process is as follows:

[0119]

[0120] Example 5: Synthesis of R-8

[0121] (E,E)-[1,1'-Bicyclohexyl]-4,4'-dicarboxylic acid (6 g, 23.6 mmol), 2,5-dihydroxybenzaldehyde (6.85 g, 49.6 mmol), 4-dimethylaminopyridine (0.58 g, 4.72 mmol) were dissolved in 150 mL of dichloromethane. N,N'-Diisopropylcarbodiimide (6.25 g, 49.6 mmol) was slowly added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 12 hours. The resulting mixture was subjected to column chromatography and crystallization successively to obtain 10.5 g of white solid compound 5a with a yield of 90%.

[0122] Compound 5a (4.88 g, 9.9 mmol), trans-4-[4-(6-acryloyloxyhexyloxy)phenyl]cyclohexanecarboxylic acid (8.78 g, 21 mmol), 4-dimethylaminopyridine (0.24 g, 2 mmol) were dissolved in 150 mL of dichloromethane. N,N'-Diisopropylcarbodiimide (2.65 g, 21 mmol) was slowly added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 12 hours. The resulting mixture was subjected to column chromatography and crystallization successively to obtain 7.9 g of white solid compound 5b with a yield of 62%.

[0123] Compound 5b (7.9 g, 6.1 mmol), compound 1b (4 g, 13.5 mmol), racemic camphorsulfonic acid (2.84 g, 12.3 mmol) were dissolved in 100 mL of chloroform. The reaction was carried out at 70 °C for 1 hour. The resulting mixture was subjected to column chromatography and crystallization successively to obtain 4 g of white solid compound 5c with a yield of 36%.

[0124] Compound 5c (4 g, 2.1 mmol), N,N-diisopropylethylamine (1.11 g, 8.6 mmol) were dissolved in 50 mL of dichloromethane. Acryloyl chloride (0.78 g, 8.6 mmol) was slowly added dropwise under an ice-water bath, and the reaction was allowed to resume to room temperature for 1 hour. The resulting mixture was subjected to column chromatography and crystallization successively to obtain 2.5 g of white solid compound R-8 with a yield of 76%. 1 H NMR (500 MHz,CDCl 3 ) δ 7.99 (s, 2H), 7.73 (s, 2H), 7.70 (d, J = 7.8 Hz, 2H), 7.66 (d, J= 8.0Hz, 2H), 7.37 - 7.32 (m, 2H), 7.20 - 7.15 (m, 2H), 7.14 - 7.06 (m, 4H), 6.98 (d, J =8.8 Hz, 4H), 6.88 (d, J = 8.9 Hz, 4H), 6.43 - 6.34 (m, 4H), 6.16 - 6.05 (m, 4H), 5.84 - 5.74 (m, 4H), 4.48 (t, J = 5.1 Hz, 4H), 4.22 - 4.13 (m, 8H), 3.94 (t, J = 6.3Hz, 4H), 3.88 (t, J = 5.5 Hz, 4H), 3.65 - 3.56 (m, 12H), 2.74 - 2.67 (m, 2H), 2.63 - 2.51 (m, 4H), 2.39 - 2.28 (m, 8H), 2.27 - 2.22 (m, 4H), 1.97 - 1.91 (m, 4H), 1.83 - 1.77 (m, 4H), 1.76 - 1.56 (m, 16H), 1.54 - 1.42 (m, 8H), 1.27 - 1.12 (m, 6H).

[0125] The specific preparation process is as follows:

[0126]

[0127] Example 6: Synthesis of R - 14

[0128] Trans - 1,4 - cyclohexanedicarboxylic acid (15.6 g, 91 mmol), 2,5 - dihydroxybenzaldehyde (26.3 g, 191 mmol), 4 - dimethylaminopyridine (1.1 g, 9.1 mmol) were dissolved in 150 mL of dichloromethane. N,N'-diisopropylcarbodiimide (25.2 g, 200 mmol) was slowly added dropwise under an ice - water bath, and the reaction was carried out at room temperature for 12 hours. The resulting mixture was subjected to column chromatography and crystallization to obtain 31.5 g of white solid compound 6a with a yield of 84%.

[0129] Compound 6a (31.5 g, 76.5 mmol), compound 6b (61 g, 160 mmol), and 4-dimethylaminopyridine (2.3 g, 19.3 mmol) were dissolved in 200 mL of dichloromethane. N,N'-Diisopropylcarbodiimide (20 g, 160 mmol) was slowly added dropwise under an ice-water bath. The reaction was carried out at room temperature for 12 hours. The resulting mixture was subjected to column chromatography and crystallization to obtain 32 g of white solid compound 6c with a yield of 37%.

[0130] Compound 6c (32 g, 28.1 mmol), compound 1b (18.4 g, 61.9 mmol), and racemic camphorsulfonic acid (13 g, 56.2 mmol) were dissolved in 200 mL of chloroform. The reaction was carried out at 70 °C for 1 hour. The resulting mixture was subjected to column chromatography and crystallization to obtain 37 g of white solid compound 6d with a yield of 77%.

[0131] Compound 6d (37 g, 21.8 mmol) and N,N-diisopropylethylamine (11.2 g, 87.2 mmol) were dissolved in 200 mL of dichloromethane. Acryloyl chloride (7.8 g, 87.2 mmol) was slowly added dropwise under an ice-water bath, and the reaction was allowed to resume to room temperature for 1 hour. The resulting mixture was subjected to column chromatography and crystallization to obtain 18.4 g of white solid compound R-14 with a yield of 47%. 1 H NMR (500MHz, CDCl 3 ) δ7.79 (s, 2H), 7.78-7.66 (m, 4H), 7.54-7.41 (m, 4H), 7.38 (d, J =2.7 Hz, 2H), 7.07 (dd, J = 8.6, 2.8 Hz, 2H), 6.30-6.15 (m, 4H), 6.08-5.93 (m,4H), 5.83-5.70 (m, 4H), 4.31 (t, J = 4.8 Hz, 4H), 4.17-4.07 (m, 8H), 4.09-4.01(m, 4H), 3.97-3.91 (m, 4H), 3.72 (t, J = 4.8 Hz, 4H), 3.70-3.63 (m, 8H), 2.51-2.44 (m, 4H), 2.37-2.25 (m, 2H), 1.99-1.91 (m, 4H), 1.88-1.65 (m, 22H), 1.64-1.43 (m, 22H), 1.33-1.23 (m, 8H).

[0132] The specific preparation process is as follows:

[0133]

[0134] Example 7: Synthesis of R-11

[0135] Monoter-butyl trans-1,4-cyclohexanedicarboxylate (22.5 g, 100 mmol), 2,5-dihydroxybenzaldehyde (15 g, 110 mmol), and 4-dimethylaminopyridine (1.2 g, 10 mmol) were dissolved in 100 mL of dichloromethane. N,N'-Diisopropylcarbodiimide (14 g, 110 mmol) was slowly added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 12 hours. The resulting mixture was successively subjected to column chromatography and crystallization to obtain 31 g of a white solid compound 7a, with a yield of 89%.

[0136] Compound 7a (10 g, 28.7 mmol), compound 7b (9.4 g, 31.6 mmol), and 4-dimethylaminopyridine (0.35 g, 2.87 mmol) were dissolved in 200 mL of dichloromethane. N,N'-Diisopropylcarbodiimide (4 g, 31.6 mmol) was slowly added dropwise under an ice-water bath. The reaction was carried out at room temperature for 12 hours. The resulting mixture was successively subjected to column chromatography and crystallization to obtain 11.5 g of a white solid compound 7c, with a yield of 64%.

[0137] Compound 7c (11.5 g, 18.3 mmol) was dissolved in 50 mL of formic acid and 50 mL of dichloromethane, and the reaction was carried out at 40 °C for 12 hours. Dichloromethane was added, and the mixture was successively washed with water, saturated brine, separated, and the organic phase was concentrated. The resulting mixture was successively subjected to column chromatography and crystallization to obtain 9.3 g of a white solid compound 7d, with a yield of 89%.

[0138] Compound 7d (1 g, 1.75 mmol), hydroquinone (77 mg, 0.7 mmol), and 4-dimethylaminopyridine (17 mg, 0.14 mmol) were dissolved in 20 mL of dichloromethane. N,N'-Diisopropylcarbodiimide (0.194 g, 1.54 mmol) was slowly added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 12 hours. The resulting mixture was successively subjected to column chromatography and crystallization to obtain 0.85 g of a white solid compound 7e, with a yield of 99%.

[0139] Compound 7e (0.85 g, 0.7 mmol), compound 1b (0.46 g, 1.54 mmol), and racemic camphorsulfonic acid (0.32 g, 1.4 mmol) were dissolved in 15 mL of chloroform and reacted at 70 °C for 1 hour. The resulting mixture was subjected to column chromatography and crystallization to obtain 0.9 g of white solid compound 7f in a yield of 75%.

[0140] Compound 7f (0.9 g, 0.51 mmol) and N,N-diisopropylethylamine (0.26 g, 2 mmol) were dissolved in 20 mL of dichloromethane. Acryloyl chloride (0.18 g, 2 mmol) was slowly added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 1 hour. The resulting mixture was subjected to column chromatography and crystallization to obtain 0.8 g of white solid compound R-11 in a yield of 84%. 1 H NMR (500 MHz, CDCl 3 ) δ 7.97 (s, 2H), 7.74 (d, J = 2.1 Hz, 2H), 7.69 (d, J = 7.8 Hz, 2H), 7.66(d, J = 8.0 Hz, 2H), 7.37 - 7.32 (m, 2H), 7.20 - 7.15 (m, 2H), 7.15 - 7.03 (m, 8H), 6.45 - 6.35 (m, 4H), 6.17 - 6.05 (m, 4H), 5.86 - 5.76 (m, 4H), 4.47 (t, J = 5.4 Hz, 4H), 4.23 - 4.18 (m, 8H), 4.16 - 4.10 (m, 4H), 3.87 (t, J = 5.6 Hz, 4H), 3.67 - 3.60 (m, 8H), 3.59 - 3.54 (m, 4H), 2.70 - 2.60 (m, 6H), 2.42 - 2.25 (m, 14H), 2.20 - 2.12 (m, 4H), 1.82 - 1.57 (m, 24H).

[0141] The specific preparation process is as follows:

[0142]

[0143] Example 8: Synthesis of R-15

[0144] Compound 7d (1 g, 1.75 mmol), 2,5-dihydroxybenzaldehyde (97 mg, 0.7 mmol), and 4-dimethylaminopyridine (17 mg, 0.14 mmol) were dissolved in 20 mL of dichloromethane. N,N'-Diisopropylcarbodiimide (0.194 g, 1.54 mmol) was slowly added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 12 hours. The resulting mixture was subjected to column chromatography and crystallization to obtain 0.87 g of white solid compound 8a with a yield of 99%.

[0145] Compound 8a (0.87 g, 0.7 mmol), compound 1b (0.69 g, 2.31 mmol), and racemic camphorsulfonic acid (0.49 g, 2.1 mmol) were dissolved in 20 mL of chloroform, and the reaction was carried out at 70 °C for 1 hour. The resulting mixture was subjected to column chromatography and crystallization to obtain 1.2 g of white solid compound 8b with a yield of 88%.

[0146] Compound 8b (1.2 g, 0.58 mmol) and N,N-diisopropylethylamine (0.45 g, 3.48 mmol) were dissolved in 20 mL of DCM. Acryloyl chloride (0.31 g, 3.48 mmol) was slowly added dropwise under an ice-water bath, and the reaction was allowed to resume to room temperature for 1 hour. The resulting mixture was subjected to column chromatography and crystallization to obtain 0.49 g of white solid compound R-15 with a yield of 38%. 1 H NMR (500 MHz,CDCl 3 ) δ 8.03-7.97 (m, 3H), 7.80-7.73 (m, 3H), 7.72-7.62 (m, 6H), 7.37-7.32(m, 3H), 7.20-7.15 (m, 3H), 7.15-7.06 (m, 6H), 6.46-6.33 (m, 5H), 6.18-6.03(m, 5H), 5.87-5.74 (m, 5H), 4.53-4.45 (m, 6H), 4.26-4.08 (m, 14H), 3.92-3.85(m, 6H), 3.67-3.55 (m, 18H), 2.77-2.62 (m, 6H), 2.42-2.27 (m, 14H), 2.20-2.13(m, 4H), 1.81-1.58 (m, 24H).

[0147] The specific preparation process is as follows:

[0148]

[0149] Example 9: Synthesis of R-5

[0150] Compound 7a (5 g, 14.4 mmol), trans-4-[4-(6-acryloyloxyhexyloxy)phenoxycarbonyl]cyclohexanecarboxylic acid (6 g, 14.4 mmol), and 4-dimethylaminopyridine (175 mg, 1.44 mmol) were dissolved in 50 mL of dichloromethane. N,N'-Diisopropylcarbodiimide (2 g, 15.8 mmol) was slowly added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 12 hours. The resulting mixture was subjected to column chromatography and crystallization to obtain 9 g of white solid compound 9a with a yield of 84%.

[0151] Compound 9a (9 g, 12 mmol) was dissolved in 40 mL of formic acid and 40 mL of dichloromethane, and the reaction was carried out at 40 °C for 12 hours. Dichloromethane was added, and the mixture was washed successively with water and saturated brine, separated, and the organic phase was concentrated. The resulting mixture was subjected to column chromatography and crystallization to obtain 5.7 g of white solid compound 9b with a yield of 69%.

[0152] Compound 9b (1 g, 1.45 mmol), hydroquinone (64 mg, 0.58 mmol), and 4-dimethylaminopyridine (14 mg, 0.12 mmol) were dissolved in 40 mL of dichloromethane. N,N'-Diisopropylcarbodiimide (0.16 g, 1.27 mmol) was slowly added dropwise under an ice-water bath. The reaction was carried out at room temperature for 12 hours. The resulting mixture was subjected to column chromatography and crystallization to obtain 0.84 g of white solid compound 9c with a yield of 99%.

[0153] Compound 9c (0.84 g, 0.58 mmol), compound 1b (0.43 g, 1.45 mmol), and racemic camphorsulfonic acid (0.27 g, 1.45 mmol) were dissolved in 50 mL of chloroform. The reaction was carried out at 70 °C for 1 hour. The resulting mixture was subjected to column chromatography and crystallization to obtain 0.72 g of white solid 9d with a yield of 62%.

[0154] Compound 9d (0.72 g, 0.36 mmol) and N,N-diisopropylethylamine (0.18 g, 1.44 mmol) were dissolved in 20 mL of dichloromethane. Acryloyl chloride (0.13 g, 1.44 mmol) was slowly added dropwise under an ice-water bath, and the reaction was allowed to resume to room temperature for 1 hour. The resulting mixture was subjected to column chromatography and crystallization to obtain 0.6 g of pale yellow solid compound R-13 with a yield of 79%. 1 H NMR (500MHz, CDCl 3 ) δ 7.99 (s, 2H), 7.75 (s, 2H), 7.70 (d, J = 7.9 Hz, 2H), 7.66 (d,J = 8.0 Hz, 2H), 7.37 - 7.32 (m, 2H), 7.20 - 7.15 (m, 2H), 7.15 - 7.05 (m, 8H), 6.98(d, J = 8.9 Hz, 4H), 6.88 (d, J = 9.0 Hz, 4H), 6.43 - 6.34 (m, 4H), 6.17 - 6.06 (m,4H), 5.85 - 5.74 (m, 4H), 4.48 (t, J = 5.3 Hz, 4H), 4.22 - 4.15 (m, 8H), 3.94 (t, J = 6.4 Hz, 4H), 3.88 (t, J = 5.5 Hz, 4H), 3.67 - 3.55 (m, 12H), 2.74 - 2.57 (m, 8H),2.39 - 2.29 (m, 16H), 1.82 - 1.66 (m, 24H), 1.54 - 1.43 (m, 8H).

[0155] The specific preparation process is as follows:

[0156]

[0157] Example 10: Synthesis of R - 9

[0158] Compound 1a (4.2 g, 7.8 mmol), trans - 1,4 - bis(methanesulfonyloxymethyl)cyclohexane (1 g, 3.7 mmol), potassium phosphate (1.7 g, 7.8 mmol) were dissolved in 40 mL of N,N - dimethylformamide and reacted at 80 °C for 8 hours, then cooled to room temperature. Dichloromethane was added, and the mixture was washed successively with water and saturated brine, separated, and the organic phase was concentrated. The resulting mixture was subjected to column chromatography and crystallization to obtain 2.4 g of white solid compound 10a with a yield of 55%.

[0159] Compound 10a (2.4 g, 2 mmol), compound 1b (1.3 g, 4.4 mmol), and racemic camphorsulfonic acid (0.93 g, 4 mmol) were dissolved in 40 mL of chloroform and reacted at 70 °C for 2 hours. The resulting mixture was subjected to column chromatography and crystallization to obtain 2.3 g of white solid compound 10b with a yield of 66%.

[0160] Compound 10b (2.3 g, 1.3 mmol), N,N - diisopropylethylamine (0.67 g, 5.2 mmol) were dissolved in 20 mL of dichloromethane. Acryloyl chloride (0.47 g, 5.2 mmol) was added dropwise under an ice - water bath, and the reaction was carried out at room temperature for 1 hour. The resulting mixture was subjected to column chromatography and crystallization to obtain 1.7 g of white solid compound R - 9 with a yield of 71%. 1 H NMR (500 MHz, CDCl 3 ) δ8.00 (s, 2H), 7.72 - 7.65 (m, 4H), 7.60 (d, J = 2.1 Hz, 2H), 7.37 - 7.32 (m, 2H),7.20 - 7.15 (m, 2H), 7.08 - 6.85 (m, 12H), 6.44 - 6.35 (m, 4H), 6.17 - 6.05 (m, 4H),5.85 - 5.75 (m, 4H), 4.48 (t, J = 5.4 Hz, 4H), 4.24 - 4.15 (m, 8H), 3.95 (t, J = 6.4Hz, 4H), 3.92 - 3.85 (m, 6H), 3.67 - 3.61 (m, 10H), 3.61 - 3.57 (m, 4H), 2.72 - 2.60(m, 4H), 2.43 - 2.28 (m, 12H), 1.90 - 1.66 (m, 22H), 1.56 - 1.41 (m, 8H).

[0161] The specific preparation process is as follows:

[0162]

[0163] Example 11: Composition of Liquid Crystal Composition 1

[0164] Preparation of liquid crystal composition: Taking Example 11 as an example, R - 1, N - 1, OXE - 03, and BYK - 354 were weighed according to the corresponding weight ratio, mixed, and cyclopentanone and N - methylpyrrolidone in the corresponding mass ratio were added. The mixture was stirred and dissolved completely at 50 °C and then cooled to room temperature for standby.

[0165]

[0166] Example 12: Composition of Liquid Crystal Composition 2

[0167]

[0168] Example 13: Composition of Liquid Crystal Composition 1

[0169]

[0170] Example 14: Composition of Liquid Crystal Composition 1

[0171]

[0172] Example 15: Composition of Liquid Crystal Composition 1

[0173]

[0174] Comparative Example 1: Composition of Composition 1

[0175]

[0176] Monomer RC-1 is:

[0177]

[0178] Comparative Example 2: Composition of Composition 2

[0179]

[0180] Monomer RC-2 is:

[0181]

[0182] Performance Test:

[0183] (1) Obtaining a retardation film

[0184] Fabrication of the retardation film

[0185] Wash a 10*10 cm optical glass, and use a spin coater to uniformly coat the photo-alignment agent HSPA-252B (manufactured by Osaka Organic Co., Ltd.) on the glass surface (2300 rpm, 10 s). Then dry at 120 °C. After cooling to room temperature, irradiate the surface with polarized ultraviolet light of 313 nm for 10 mJ to obtain a glass substrate with an alignment layer.

[0186] On the glass substrate with an alignment layer, use a spin coater to uniformly coat the liquid medicines of Examples 11 to 15 and Comparative Examples 1 to 2 above (600 rpm, 30 s), and dry to volatilize the solvent. The drying temperature is slightly lower than the clearing point temperature shown in the above table. Then cool to room temperature, and irradiate the film surface with the composition with a mercury lamp in a nitrogen atmosphere, with a total energy of 1500 mJ / cm 2 , and thus obtain the retardation film.

[0187] (2) Color dispersion test

[0188] The retardation of the retardation film at each wavelength was measured using a polarization measuring instrument Axoscan, and the retardation R450 at 450 nm and the retardation R550 at 550 nm were taken. The chromatic dispersion value was obtained by calculating R450 / R550, and the test results are shown in the following table:

[0189]

[0190] In Examples 11 to 15 and Comparative Example 1, 85 parts of an inverse wavelength dispersion monomer and 15 parts of a positive wavelength dispersion monomer N-1 were used. In Examples 11 to 14, the monomer proposed by the present invention was used, and the chromatic dispersion R450 / 550 was all below 0.906. Comparative Example 1 showed a monomer in the prior art with 5 main-chain six-membered ring monomers and 1 unit / molecule of side-chain chromophore. Its chromophore was the same as that in the examples, but the chromatic dispersion R450 / 550 was the highest. It can be seen that using a longer liquid crystal main chain and a dense arrangement of chromophores helps to improve the chromatic dispersion. Example 15 was a mixture of the monomer proposed by the present invention and RC-1, and its chromatic dispersion could also be improved to a certain extent.

[0191] Comparative Example 2 showed an inverse wavelength dispersion monomer with 3 main-chain six-membered ring monomers and 1 unit / molecule of side-chain chromophore. In this case, effective alignment of the liquid crystal system could not be achieved, so the chromatic dispersion R450 / 550 could not be measured.

[0192] (3)△n test

[0193] The retardation at 550 nm of a fixed point on the retardation film was measured using a polarization measuring instrument Axoscan to obtain R550 at this point. Then, a part of the film surface was removed with tape, and the torn edge was scanned using a white light interferometer (Filmetrics Profilm 3D) to obtain the film thickness d at the cross-section. The △n at this point was calculated according to the following formula: △n = R550 / d.

[0194]

[0195] It can be seen that using the monomer proposed by the present invention helps to increase the △n value of the optical film, which reflects the degree of order of the liquid crystal arrangement.

[0196] (4)Reaction completion test

[0197] The film was transferred from glass to a TAC substrate and scanned using the attenuated total reflection (ATR) mode of a Fourier transform infrared spectrometer (Bruker APLHA II). In the obtained spectrum, according to the acrylate peak (810 cm -1The degree of completion of the photoreaction is calculated from the degree of disappearance of ( ). Using the disappearance of the acrylate peak to determine the degree of completion of the photoreaction is a commonly used method. The reference document is Simon, J. and Langenscheidt, A. (2020) ‘Curing behavior of a UV-curable inkjet ink: Distinction between surface-cure and deep-cure performance’, Journal of Applied Polymer Science, 137(40), pp. 1–9.

[0198]

[0199] It can be seen that using the monomer of the solution proposed in the present invention helps to improve the degree of photocuring of the optical film.

[0200] It should also be noted that the term "comprising", "including" or any other variant thereof is intended to cover non-exclusive inclusion, so that a process, method, commodity or device comprising a series of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, commodity or device. Without further limitation, an element defined by the statement "comprising an..." does not exclude the presence of additional identical elements in the process, method, commodity or device comprising the element.

[0201] The above description is only for the embodiments of the present application and is not intended to limit the present application. For those skilled in the art, the present application may have various changes and modifications. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included within the scope of the claims of the present application.

Claims

1. A liquid crystal compound, characterized in that: The liquid crystal compound is selected from the following structures:

2. A liquid crystal composition, characterized in that: include: The liquid crystal compound and polymerizable liquid crystal compound according to claim 1.

3. The liquid crystal composition according to claim 2, characterized in that: The liquid crystal composition comprises: a liquid crystal compound in an amount of 5 parts by weight or more and a polymerizable liquid crystal compound in an amount of 5 parts by weight or more.

4. The liquid crystal composition according to claim 3, characterized in that: The liquid crystal composition comprises: 50 to 90 parts by weight of a liquid crystal compound and 10 to 50 parts by weight of a polymerizable liquid crystal compound.

5. The liquid crystal composition according to claim 2, characterized in that: The polymerizable liquid crystal compound is selected from the following structures:

6. A phase difference film, characterized in that: The phase difference film is formed by polymerizing the liquid crystal composition described in any one of claims 2 to 5.

7. The phase difference film according to claim 6, characterized in that: The phase difference R450 of the phase difference film at a wavelength of 450 nm and the phase difference R550 at a wavelength of 550 nm are R450 / R550≤1.0.

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