Polymerizable liquid crystal mixture, polymerizable liquid crystal composition

Abstract

A polymerizable liquid crystal compound represented by Equation (1) that is capable of lowering the phase transition temperature of a liquid crystal composition without impairing optical properties.

Description

Technology Field

[0001] The present invention relates to a polymerizable liquid crystal compound, a polymerizable liquid crystal composition comprising said polymerizable liquid crystal compound, a phase difference film formed from said polymerizable liquid crystal composition, a polarizer, and an optical display. Background Technology

[0002] As an optical film such as a phase difference film used in a flat panel display device (FPD), there is, for example, an optical film obtained by dissolving a polymerizable liquid crystal compound in a solvent, applying the resulting coating solution to a support substrate, and then polymerizing it. Conventionally, polymerizable liquid crystal compounds are known, for example, nematic liquid crystal compounds with a rod-like structure in which about 2 to 4 six-membered rings are connected.

[0003] Meanwhile, as one of the characteristics of a phase difference film, it is required that it be capable of polarization conversion over the entire wavelength range. For example, it is known that, in a wavelength range where the value [Re(λ) / Re(550)] obtained by dividing the phase difference value Re(λ) at a certain wavelength λ by the phase difference value Re(550) at 550 nm is close to 1, or in a wavelength range exhibiting inverse wavelength dispersion [Re(450) / Re(550)] < 1, a certain polarization conversion is theoretically possible. Polymerizable liquid crystal compounds capable of constituting such a phase difference film are disclosed, for example, in Patent Documents 1 to 3. Prior art literature

[0004] Japanese Published Patent Application No. 2016-121339, Japanese Published Patent Application No. 2019-156733, Japanese Published Patent Application No. 2020-41026 The problem to be solved

[0005] When orienting a polymerizable liquid crystal compound, for example, after applying a coating solution containing the polymerizable liquid crystal compound to a support substrate, it is necessary to induce a phase transition by heating to a temperature higher than the phase transition temperature of the polymerizable liquid crystal compound. If the phase transition temperature of the polymerizable liquid crystal compound is high, it may have undesirable effects on the support substrate, limit the usable support substrates, or reduce manufacturing efficiency due to the high heating temperature. Furthermore, if additives are added to the polymerizable liquid crystal compound to lower the phase transition temperature, the molecular orientation of the liquid crystal compound may be disrupted by the additives, resulting in a failure to obtain the desired optical properties. Additionally, the desired optical properties may not be obtained if the additives or the polymerizable liquid crystal compound precipitate as crystals.

[0006] The present invention aims to provide a compound capable of lowering the phase transition temperature of a liquid crystal composition without impairing optical properties. means of solving the problem

[0007] The inventors, as a result of careful consideration to solve the above problem, have completed the present invention. That is, the present invention provides the following preferred embodiments.

[0008] [1] A polymerizable liquid crystal compound represented by formula (1).

[0009] [Chemical Formula 1]

[0010]

[0011] [Essence (1),

[0012] k11, k12, and l each independently represent integers greater than or equal to 1;

[0013] B 11 and B 12 is, each independently, -CR 1 R 2-, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S- or representing a single bond, R 1 and R 2 Each represents, independently, a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms;

[0014] E 11 and E 12 is, each independently, -CR 1 R 2 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S- or represents a single bond;

[0015] G 11 and G 12 Each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, and the hydrogen atoms included in the alicyclic hydrocarbon group are halogen atoms, -R 3 , -OR 3 , may be substituted with a cyano group or a nitro group, and the -CH2- included in the alicyclic hydrocarbon group may be substituted with -O-, -S- or -NH-, and R 3 ... represents an alkyl group having 1 to 4 carbon atoms, and the hydrogen atoms included in the alkyl group may be substituted with fluorine atoms;

[0016] A 11 and A 12Each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the hydrogen atoms included in the alicyclic hydrocarbon group and the aromatic hydrocarbon group are halogen atoms, -R 3 , -OR 3 , may be substituted with cyano groups or nitro groups ;

[0017] F 11 and F 12 Each independently represents an alkanedyl group having 1 to 12 carbon atoms, and the hydrogen atoms included in the alkanedyl group are -OR 3 Or it may be substituted with a halogen atom, and the -CH2- included in the alkandyl group may be substituted with -O- or -CO- ;

[0018] P 11 and P 12 Each independently represents a hydrogen atom or a polymerizable group (where P 11 and P 12 At least one of them is a polymerizable group) ;

[0019] M each independently represents a divalent aliphatic hydrocarbon group having 3 to 13 carbon atoms that may have substituents;

[0020] Ar 11 and Ar 12 Each represents a divalent aromatic group that may have a substituent, independently.

[0021] [2] A polymerizable liquid crystal compound described in [1] above, wherein M in formula (1) is a divalent aliphatic hydrocarbon group having 2n carbon atoms (n represents an integer from 2 to 4) that may have a substituent.

[0022] [3] Ar in formula (1) 11 and Ar 12a, each independently, a polymerizable liquid crystal compound described in [1] or [2] above, which is represented by any of the following formulas (Ar-1) to (Ar-5).

[0023] [Chemical Formula 2]

[0024]

[0025] [Among the formulas (Ar-1) ~ (Ar-5),

[0026] * indicates a joint ;

[0027] Q 1 -S-, -O-, or -NR 11 - represents, and R 11 represents a carbon-1 to carbon-6 alkyl group that may have hydrogen atoms or substituents, and

[0028] Q 2 represents a C1 to C6 alkyl group that may have hydrogen atoms or substituents;

[0029] W 1 and W 2 are, respectively, -O-, -S-, -CO-, -NR 11 - represents, and R 11 represents a C1 to C6 alkyl group that may have hydrogen atoms or substituents;

[0030] Y 1 ...represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group that may have substituents, or an aromatic complex ring group, and

[0031] Y 2 represents a C1 to C12 alkyl group that may have a CN group or a substituent, wherein a hydrogen atom included in the alkyl group may be substituted with a halogen atom, and -CH2- included in the alkyl group may be substituted with -O-, -CO-, -O-CO-, or -CO-O-;

[0032] Z 1 , Z 2 and Z3 Each independently, a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group, a dicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, -NR 11 R 12 or -SR 11 Represents, and Z 1 and Z 2 They may combine with each other to form an aromatic ring or an aromatic complex ring, and R 11 and R 12 Each represents, independently, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;

[0033] Ax represents an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic complex rings, and Ay represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms that may have substituents, or an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic complex rings, and Ax and Ay may combine to form a ring;

[0034] Y 3 and Y 4 is, respectively, the following formula (Y 3 -1) :

[0035] [Chemical Formula 3]

[0036]

[0037] Equation (Y 3 -1) Among,

[0038] R Y1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl group comprises one or more substituents X 3 It may be substituted by, and substituent X 3Silver, fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, or, one -CH2- or two or more non-adjacent -CH2- may 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-, the number of carbon atoms that may be substituted It represents a straight-chain or branched alkyl group of 1 to 20, wherein any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or, -B 31 -F 31 -P 31 It also serves as the contribution represented by, and B 31 , F 31 and P 31 Each is B in the above formula (1). 11 , F 11 and P 11 Defined identically to, and each B in Equation (1) 11 , F 11 and P 11 It may be the same as or different from ;

[0039] U 1 ...represents an organic group having 2 to 30 carbon atoms having an aromatic hydrocarbon group, wherein any carbon atom of the aromatic hydrocarbon group may be substituted with a heteroatom, and the aromatic hydrocarbon group comprises one or more of the above-mentioned substituent X 3 It may be substituted by ;

[0040] T 1 Silver, -O-, -S-, -COO-, -OCO-, -OCO-O-, -NU 2 -, -N=CU2 -, -CO-NU 2 -, -OCO-NU 2 - or O-NU 2 - represents, and U 2 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, an aromatic hydrocarbon group (any carbon atom of the aromatic hydrocarbon group may be substituted with a heteroatom), or an organic group having 2 to 30 carbon atoms having (E 31 -A 31 ) q -B 32 -F 32 -P 32 Representing, wherein the alkyl group, cycloalkyl group, cycloalkenyl group, and aromatic hydrocarbon group are each unsubstituted or have one or more substituents X 3 It may be substituted by, and the alkyl group may be substituted by the cycloalkyl group or cycloalkenyl group, and one -CH2- or two or more non-adjacent -CH2- in the alkyl group may each independently be substituted by -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -SO2-, -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 one -CH2- or two or more non-adjacent -CH2- in the cycloalkyl group or cycloalkenyl group may each independently be substituted by -O-, -CO-, -COO-, -OCO- or It may be substituted with O-CO-O-, and E 31 , A 31 , B 32 , F 32 and P 32 is, respectively, E in Equation (1) 11 , A 11 , B 11 , F 11 and P11 Defined identically to, and respectively the above E 11 , A 11 , B 11 , F 11 and P 11 It may be the same as or different from, where q represents an integer from 0 to 4, and E 31 and / or A 31 In cases where multiple exist, each may be identical or different, U 1 and U 2 [It is acceptable for them to combine to form a ring]

[0041] Represents the energy selected from.

[0042] [4] A polymerizable liquid crystal composition comprising a polymerizable liquid crystal compound described in any one of [1] to [3] above and a polymerizable liquid crystal compound represented by formula (2).

[0043] [Chemical Formula 4]

[0044]

[0045] [Essence (2),

[0046] k21 and k22 each independently represent integers greater than or equal to 1;

[0047] B 21 and B 22 is, each independently, -CR 1 R 2 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S- or representing a single bond, R 1 and R 2 Each represents, independently, a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.

[0048] E 21 and E22 is, each independently, -CR 1 R 2 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S- or represents a single bond;

[0049] G 21 and G 22 Each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, and the hydrogen atoms included in the alicyclic hydrocarbon group are halogen atoms, -R 3 , -OR 3 , may be substituted with a cyano group or a nitro group, and the -CH2- included in the alicyclic hydrocarbon group may be substituted with -O-, -S- or -NH-, and R 3 ... represents an alkyl group having 1 to 4 carbon atoms, and the hydrogen atoms included in the alkyl group may be substituted with fluorine atoms;

[0050] A 21 and A 22 Each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the hydrogen atoms included in the alicyclic hydrocarbon group and the aromatic hydrocarbon group are halogen atoms, -R 3 , -OR 3 , may be substituted with cyano groups or nitro groups ;

[0051] F 21 and F 22 Each independently represents an alkanedyl group having 1 to 12 carbon atoms, and the hydrogen atoms included in the alkanedyl group are -OR 3Or it may be substituted with a halogen atom, and the -CH2- included in the alkandyl group may be substituted with -O- or -CO- ;

[0052] P 21 and P 22 Each independently represents a hydrogen atom or a polymerizable group (where P 21 and P 22 At least one of them is a polymerizable group) ;

[0053] Ar 21 Each represents a divalent aromatic group that may have a substituent, independently.

[0054] [5] A polymerizable liquid crystal composition described in [4] above, wherein the ratio of the peak area of ​​the polymerizable liquid crystal compound (1) to the total peak area of ​​the polymerizable liquid crystal compound (2), as measured by liquid chromatography, is 0.1% or more and 50% or less.

[0055] [6] A in equation (1) 11 , A 12 , B 11 , B 12 , E 11 , E 12 , F 11 , F 12 , G 11 , G 12 , P 11 and P 12 The giga represented by , respectively, A in equation (2). 21 , A 22 , B 21 , B 22 , E 21 , E 22 , F 21 , F 22 , G 21 , G 22 , P 21 and P 22 It is identical to the qi represented by , and Ar in Equation (1) 11 and Ar 12 The giga represented by is each Ar in Equation (2).21 A polymerizable liquid crystal composition identical to the one represented by [4] or [5] above.

[0056] [7] A polymerizable liquid crystal composition described in any one of [4] to [6], further comprising a photopolymerization initiator and an organic solvent.

[0057] [8] A phase difference film formed from a polymerizable liquid crystal composition described in any one of [4] to [7] above.

[0058] [9] A polarizing plate comprising the phase difference film described in [8] above.

[0059]

[10] An optical display comprising the polarizing plate described in [9] above. Effects of the invention

[0060] According to the present invention, a compound capable of lowering the phase transition temperature of a liquid crystal composition without impairing optical properties can be provided. Specific details for implementing the invention

[0061] The embodiments of the present invention will be described in detail below. Furthermore, the scope of the present invention is not limited to the embodiments described herein, and various modifications may be made within the scope that does not deviate from the spirit of the invention.

[0062] <Polymerizable Liquid Crystal Compounds>

[0063] The polymerizable liquid crystal compound of the present invention is, Formula (1):

[0064] [Chemical Formula 5]

[0065]

[0066] It is represented by [formula]. Hereinafter, the polymerizable liquid crystal compound of the present invention represented by formula (1) is also referred to as "polymerizable liquid crystal compound (1)".

[0067] In Equation (1), k11 and k12 each independently represent an integer greater than or equal to 1, and may be, for example, integers from 1 to 5. The sum of k11 and k12 is preferably 2 to 6, more preferably 2 to 4. From the viewpoint of excellent liquid crystallization, it is preferable that k11 and k12 each independently be 1 or 2, and from the viewpoint of ease of manufacturing the polymerizable liquid crystal compound (1), it is preferable that k11 and k12 are the same number, and in a preferred embodiment of the present invention, k11 and k12 are both 1.

[0068] In Equation (1), l represents an integer greater than or equal to 1, and may be, for example, an integer from 1 to 8. From the perspective of excellent liquid crystal properties, it is preferable that l be from 1 to 6.

[0069] In Equation (1), B 11 and B 12 is, each independently, -CR 1 R 2 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S- or representing a single bond, R 1 and R 2 Each represents, independently, a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms. B 11 and B 12 are, respectively, -CO-O-, -O-CO-, -O-CO-O-, -CO-NR 1 -, -NR 2 It is preferable that it be -CO-, -CH2-O-, -O-CH2-, -CH2-S-, -S-CH2- or a single bond, and more preferably -O-CO- or -CO-O-. B 11 and B 12In the case where there are multiple instances, they may be identical or different from each other, but from the perspective of ease of manufacturing the polymerizable liquid crystal compound (1), multiple instances of B 11 It is desirable that it be of the same cause, and B exists in multiple instances. 12 It is desirable that it be of the same cause. Also, B 11 and B 12 It is more desirable for everything to be identical.

[0070] R 1 and R 2 Examples of alkyl groups having 1 to 4 carbon atoms represented by are methyl groups, ethyl groups, propyl groups, butyl groups, isopropyl groups, isobutyl groups, tert-butyl groups, etc., preferably alkyl groups having 1 or 2 carbon atoms, and more preferably methyl groups.

[0071] In Equation (1), E 11 and E 12 is, each independently, -CR 1 R 2 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S- or represents a single bond. E 11 and E 12 Each is independently, preferably -CO-O-, -O-CO-, -O-CO-O-, -CO-NR 1 -, -NR 2 -CO-, -CH2-O-, -O-CH2-, -CH2-S-, -S-CH2- or a single bond, more preferably -O-CO- or -CO-O-. In terms of ease of preparation of the polymerizable liquid crystal compound (1), E 11 and E 12 They may be identical or different, but it is desirable that they be of the same origin.

[0072] G11 and G 12 Each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms. The hydrogen atoms included in the alicyclic hydrocarbon group are halogen atoms, -R 3 , -OR 3 , may be substituted with a cyano group or a nitro group, and the -CH2- included in the alicyclic hydrocarbon group may be substituted with -O-, -S-, or -NH-. R 3 ... represents an alkyl group having 1 to 4 carbon atoms, and the hydrogen atoms included in the alkyl group may be substituted with fluorine atoms. G 11 and G 12 As for the divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms represented by, for example, a divalent alicyclic hydrocarbon group that may include heteroatoms represented by formulas (g-1) to (g-10), and a 5-membered or 6-membered alicyclic hydrocarbon group is preferred.

[0073] [Chemical Formula 6]

[0074]

[0075] The groups represented by the above formulas (g-1) to (g-10) may be substituted with alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, isopropyl, and tert-butyl groups; alkoxy groups having 1 to 4 carbon atoms, such as methoxy and ethoxy groups; fluoroalkyl groups having 1 to 4 carbon atoms, such as trifluoromethyl groups; cyano groups; nitro groups; and halogen atoms, such as fluorine, chlorine, and bromine atoms.

[0076] G 11 and G 12In each case, an alicyclic hydrocarbon group of a 5-membered ring or a 6-membered ring represented by any of formulas (g-1) to (g-4) is more preferable, an alicyclic hydrocarbon group consisting of a 6-membered ring represented by formula (g-1) is even more preferable, a cyclohexane-1,4-diyl group is particularly preferable, and a trans-cyclohexane-1,4-diyl group is particularly preferable.

[0077] G 11 and G 12 They may be identical or different, but if they are identical, it is advantageous in terms of ease of industrial manufacturing and productivity of the polymerizable liquid crystal compound (1).

[0078] In Equation (1), A 11 and A 12 Each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the hydrogen atoms included in the alicyclic hydrocarbon group and the aromatic hydrocarbon group are halogen atoms, -R 3 , -OR 3 , may be substituted with a cyano group or a nitro group.

[0079] A 11 and A 12 Examples of dicyclic hydrocarbon groups having 3 to 16 carbon atoms or dicyclic aromatic hydrocarbon groups having 6 to 20 carbon atoms include dicyclic hydrocarbon groups consisting of 5-membered rings or 6-membered rings, etc., represented by the above formulas (g-1) to (g-10), or aromatic hydrocarbon groups having 6 to 20 carbon atoms represented by the above formulas (a-1) to (a-8).

[0080] [Chemical Formula 7]

[0081]

[0082] Also, A 11 and A 12As such, some of the hydrogen atoms of the group exemplified above may be substituted with alkyl groups having 1 to 4 carbon atoms, such as methyl groups, ethyl groups, isopropyl groups, or tert-butyl groups; alkoxy groups having 1 to 4 carbon atoms, such as methoxy groups or ethoxy groups; fluoroalkyl groups having 1 to 4 carbon atoms, such as trifluoromethyl groups; cyano groups; nitro groups; or halogen atoms, such as fluorine atoms, chlorine atoms, or bromine atoms.

[0083] A 11 and A 12 For Ro, a cyclohexane-1,4-diyl group or a 1,4-phenylene group is preferred. When k11 and k12 are 1, A 11 and A 12 It is preferable that each is a 1,4-phenylene group, and if k11 and k12 are 2 or more, E 11 A that combines with 11 and E 12 A that combines with 12 It is desirable that they are identical to each other, and E 11 A that combines with 11 and E 12 A that combines with 12 It is preferable that α is a 1,4-phenylene group. A 11 and A 12 If there are multiple instances, they may be identical or different from each other.

[0084] In Equation (1), F 11 and F 12 Each independently represents an alkanedyl group having 1 to 12 carbon atoms, and the hydrogen atoms included in the alkanedyl group are -OR 3 Alternatively, it may be substituted with a halogen atom, and the -CH2- included in the alkandyl group may be substituted with -O- or -CO-. F 11 and F 12In each case, independently, an alkanedyl group having 3 to 10 carbon atoms, -(CF2)4-, -(CF2)6-, or -(CF2)8- is preferred, and an alkanedyl group having 4 or 6 carbon atoms [-(CH2)4- or -(CH2)6-] is more preferred. E 11 and E 12 They may be identical or different, but if they are identical, it is advantageous in terms of ease of industrial manufacturing and productivity of the polymerizable liquid crystal compound (1).

[0085] P 11 and P 12 Each represents, independently, a hydrogen atom or a polymerizable group. P 11 and P 12 At least one of them is a polymerizable group, and P 11 and P 12 It is desirable that all of them are polymerizable groups in terms of the film hardness of the liquid crystal cured film obtained using the polymerizable liquid crystal compound.

[0086] The polymerizable group is any reactive group capable of polymerizing the polymerizable liquid crystal compound (1), and specifically, examples include a vinyl group, vinyloxy group, styryl group, p-(2-phenylethenyl)phenyl group, acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, carboxyl group, acetyl group, hydroxyl group, carbamoyl group, N-alkylamino group having 1 to 4 carbon atoms, amino group, oxiranyl group, oxetanyl group, formyl group, isocyanato group, isothiocyanato group, etc. In addition, the polymerizable group includes the groups exemplified above and F 11 or F 12 It may include ether bonds or ester bonds that bind, and it is preferable that they are each bonded via an ether bond. P 11 and P 12 For example, a radical polymerization group or a cation polymerization group suitable for photopolymerization is preferred, and an acryloyloxy group or a methacryloyloxy group is preferred in that it is easy to handle and easy to manufacture, and an acryloyloxy group is more preferred.

[0087] In Formula (1), M represents a divalent aliphatic hydrocarbon group having 3 to 13 carbon atoms that may independently have a substituent. If M in Formula (1) is a divalent aliphatic hydrocarbon group having 3 to 13 carbon atoms, it is easy to improve the solubility of other polymerizable liquid crystal compounds having a structure similar to that of the polymerizable liquid crystal compound (1) in the molecular structure, for example, the polymerizable liquid crystal compound represented by Formula (2) described later, and has an excellent effect of lowering the phase transition temperature of the polymerizable liquid crystal compound. Since it has an excellent effect of lowering the phase transition temperature of the polymerizable liquid crystal compound, a liquid crystal cured film can be obtained from the polymerizable liquid crystal compound at a lower processing temperature, which is advantageous in terms of reducing the influence on the optical properties of the liquid crystal cured film caused by heating and in terms of manufacturing efficiency. This effect tends to be significantly higher, particularly when M in Equation (1) has a cyclic structure such as an alicyclic hydrocarbon group or an aromatic hydrocarbon group. The reason for this is not limited to, but includes, divalent aromatic groups (Ar 11 and / or Ar 12 It is speculated that because the group M placed between ) does not have a rigid ring structure, the flexibility of the molecule increases, making it easier to improve solubility and resulting in a significant decrease in the phase transition temperature.

[0088] The divalent aliphatic hydrocarbon group having 3 to 13 carbon atoms may be of the straight-chain type or the branched type, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, but it is preferable that it be a saturated hydrocarbon group, and more preferable that it be a straight-chain saturated hydrocarbon group. Specifically, examples of divalent aliphatic hydrocarbon groups having 3 to 13 carbon atoms include, for instance, alkanedyl groups having 3 to 13 carbon atoms such as n-propanediyl, i-propanediyl, n-butanediyl, n-pentanediyl, n-hexanedyl, n-heptanediyl, n-octanedyl, n-nonandyl, and n-decandyl. When multiple Ms exist, they may be identical or different from each other.

[0089] The hydrogen atoms included in the above divalent aliphatic hydrocarbon group having 3 to 13 carbon atoms may be substituted with substituents. When M in Formula (1) is a divalent aliphatic hydrocarbon group having 3 to 13 carbon atoms having substituents, it is preferable that no cyclic structure exists in M ​​including the substituents. In other words, the polymerizable liquid crystal compound (1) of the present invention is -(Ar in Formula (1). 11 In the structure represented as -O-CO-M-CO-O)-, the Ar 11 It does not include a ring structure other than an alicyclic hydrocarbon group or an aromatic hydrocarbon group represented by. Substituents that may be had by a divalent aliphatic hydrocarbon group having 3 to 13 carbon atoms include, for example, a halogen atom, an alkoxyl group having 1 to 4 carbon atoms, etc.

[0090] In addition, the number of carbon atoms included in the substituent is not included in the number of carbon atoms of the aliphatic hydrocarbon group represented by M in Equation (1).

[0091] In addition, if M in Equation (1) is a divalent aliphatic hydrocarbon group having 2n carbon atoms (where n is an integer from 2 to 4) that may have a substituent, the liquid crystal cured film obtained can exhibit superior reverse wavelength dispersibility while sufficiently securing the effect of lowering the phase transition temperature of the polymerizable liquid crystal compound and the effect of improving solubility. As for the divalent aliphatic hydrocarbon group having 2n carbon atoms, an alkanedyl group having 2n carbon atoms is preferred, specifically, an n-butanediyl group, an n-hexanedyl group, or an n-octanedyl group.

[0092] M in formula (1) is preferably a divalent alkanedyl group having 3 to 11 carbon atoms that may have a substituent, more preferably a divalent alkanedyl group having 4 to 10 carbon atoms that may have a substituent, even more preferably a divalent alkanedyl group having 4, 6, or 8 carbon atoms that may have a substituent, and particularly preferably an n-butanediyl group, an n-hexanedyl group, and an n-octanedyl group.

[0093] In formula (1), Ar 11 and Ar 12 Each represents a divalent aromatic group that may have a substituent, independently. The divalent aromatic group that may have a substituent may be a divalent aromatic hydrocarbon group and a divalent aromatic complex ring. In the present invention, the divalent aromatic hydrocarbon group that may have a substituent refers to a divalent linker comprising at least one aromatic hydrocarbon ring, and the divalent aromatic complex ring that may have a substituent refers to a divalent linker comprising at least one aromatic complex ring. The aromatic hydrocarbon ring and aromatic complex ring referred to herein mean that the ring structure has [4n + 2] π electrons according to Hückel's rule (where n represents an integer) (in the case of an aromatic complex ring, it satisfies Hückel's rule by including non-covalent electron pairs on heteroatoms such as -N= or -S-). Ar11 and Ar 12 It may contain one aromatic hydrocarbon ring or an aromatic complex ring, or two or more. In the case where it contains one aromatic hydrocarbon ring or an aromatic complex ring, Ar 11 and Ar 12 Each may independently be a divalent aromatic hydrocarbon group that may have a substituent, or a divalent aromatic complex ring that may have a substituent. When containing two or more aromatic hydrocarbon rings or aromatic complex rings, it may contain only aromatic hydrocarbon rings or multiple aromatic complex rings, or one or more aromatic hydrocarbon rings and one or more aromatic complex rings. Two or more aromatic hydrocarbon rings and / or aromatic complex rings may be connected to each other by single bonds, divalent bonding groups such as -CO-O-, -O-, etc.

[0094] Ar 11 and Ar 12 They may be identical or different, but if they are identical, it is advantageous in terms of ease of industrial manufacturing and productivity of the polymerizable liquid crystal compound (1). Also, Ar 11 If this plural exists, the plural Ar 11 It may be the same or different, but it is preferable that it be the same cause, and multiple Ar 11 and Ar 12 It is more desirable for everything to be identical.

[0095] Ar 11 and Ar 12 Aromatic hydrocarbon rings that may be included include, for example, benzene rings, naphthalene rings, anthracene rings, etc., and benzene rings and naphthalene rings are preferred.

[0096] Examples of aromatic complex rings include furan rings, benzofuran rings, pyrrole rings, indole rings, thiophene rings, benzothiophene rings, pyridine rings, pyrazine rings, pyrimidine rings, triazole rings, pyrroline rings, imidazole rings, pyrazol rings, thiazole rings, benzothiazole rings, thienothiazole rings, oxazole rings, benzoxazole rings, and phenanthroline rings. Ar 11 and Ar 12 When nitrogen atoms are included, it is desirable for the nitrogen atoms to have π electrons.

[0097] Among them, Ar 11 and Ar 12 It is preferable that it has an aromatic complex ring comprising at least two heteroatoms selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms, more preferable that it has a thiazole ring, a benzothiazole ring, or a benzofuran ring, and even more preferable that it has a benzothiazole ring. Additionally, Ar 11 and Ar 12 If ga has an aromatic complex ring comprising at least two heteroatoms selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms, said aromatic complex ring is G in Equation (1). 11 , M or G 12 A divalent linker may be formed by directly bonding to the adjacent -CO-O- or -O-CO- to constitute the main chain of the compound represented by Formula (1), and G 11 , M or G 12 It may be included as a substituent of a divalent linker that directly bonds to the adjacent -CO-O- or -O-CO-, respectively, and Ar comprising the aromatic complex ring. 11 or Ar 12 It is desirable that the entire structure be arranged in a direction approximately orthogonal to the molecular orientation direction.

[0098] In formula (1), Ar11 and Ar 12 The total number of π electrons N contained in a divalent aromatic group that may have a substituent represented by . π Each is preferably 8 or more, more preferably 12 or more, particularly preferably 16 or more, and particularly preferably 20 or more. Also, preferably 36 or less, more preferably 32 or less, even more preferably 30 or less, particularly preferably 26 or less, and particularly preferably 24 or less.

[0099] Ar in formula (1) 11 and Ar 12 Examples of divalent aromatic groups that may have a substituent represented by are groups represented by the following formulas (Ar-1) to (Ar-5).

[0100] [Chemical Formula 8]

[0101]

[0102] In formulas (Ar-1) ~ (Ar-5), * indicates a bond.

[0103] Among the formula (Ar-1), Q 1 -S-, -O-, or -NR 11 - represents, and R 11 represents a C1 to C6 alkyl group that may have a hydrogen atom or a substituent. In formulas (Ar-3) and (Ar-4), Q 2 represents a carbon-1 to carbon-6 alkyl group that may have a hydrogen atom or a substituent.

[0104] In formula (Ar-2), W 1 and W 2 are, respectively, -O-, -S-, -CO-, -NR 11 - represents, and R 11 It represents an alkyl group having 1 to 6 carbon atoms that may have hydrogen atoms or substituents.

[0105] In the formula (Ar-1), Y 1represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group that may have substituents, or an aromatic complex ring group. In formula (Ar-2), Y 2 represents a carbon-1 to carbon-12 alkyl group that may have a CN group or a substituent. Here, the hydrogen atom included in the alkyl group may be substituted with a halogen atom, and the -CH2- included in the alkyl group may be substituted with -O-, -CO-, -O-CO-, or -CO-O-.

[0106] Among the formulas (Ar-1) ~ (Ar-5), Z 1 , Z 2 and Z 3 Each independently, a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group, a dicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, -NR 11 R 12 or -SR 11 Represents, and Z 1 and Z 2 They may combine with each other to form an aromatic ring or an aromatic complex ring. R 11 and R 12 Each represents, independently, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0107] In formulas (Ar-3) and (Ar-4), Ax represents an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic complex rings, and Ay represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms that may have a substituent, or an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic complex rings, and Ax and Ay may combine to form a ring.

[0108] In the formula (Ar-1), Y1 The aromatic hydrocarbon group or aromatic complex ring group that may preferably have a substituent is more preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic complex ring group having 3 to 12 carbon atoms that may have a substituent. The aromatic hydrocarbon group or aromatic complex ring group that may have a substituent is preferably a polycyclic aromatic hydrocarbon group or a polycyclic aromatic complex ring group that may be substituted. In this specification, "polycyclic aromatic hydrocarbon group" means an aromatic hydrocarbon group having at least two aromatic rings, and examples include a condensed aromatic hydrocarbon group formed by the condensation of two or more aromatic rings and an aromatic hydrocarbon group formed by the combination of two or more aromatic rings. "Polycyclic aromatic complex ring" refers to an aromatic complex ring having at least one complex directional ring and at least one ring selected from the group consisting of a directional ring and a complex directional ring, and may include an aromatic complex ring formed by the condensation of one or more aromatic complex rings and one or more rings selected from the group consisting of a directional ring and a complex directional ring, and an aromatic complex ring formed by the combination of at least one complex directional ring and at least one ring selected from the group consisting of a directional ring and a complex directional ring.

[0109] Substituents that the above aromatic hydrocarbon group or aromatic complex ring group may have include a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, a nitroso group, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxyl group, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylsulfanyl group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 4 carbon atoms, an N,N-dialkylamino group having 2 to 8 carbon atoms, a sulfamoyl group, an N-alkylsulfamoyl group having 1 to 6 carbon atoms, and an N,N-dialkylsulfamoyl group having 2 to 12 carbon atoms.

[0110] Y 1 For example, the following formula (Y 1 -1) ∼ (Y 1 -7) Can be cited as the energy represented by.

[0111] [Chemical Formula 9]

[0112]

[0113] Equation (Y 1 -1) ∼ Equation (Y 1 -7) * indicates the connecting part.

[0114] Equation (Y 1 -1) ∼ Equation (Y 1 -7) Among, Z 4 Each of the elements independently represents a halogen atom or an organic group having 1 to 20 carbon atoms, for example, a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, an isopropyl group, a sec-butyl group, a cyano group, a nitro group, a sulfone group, a nitroxide group, a carboxyl group, a trifluoromethyl group, a methoxy group, a thiomethyl group, an N,N-dimethylamino group, or an N-methylamino group is preferred, a halogen atom, a methyl group, an ethyl group, an isopropyl group, a sec-butyl group, a cyano group, a nitro group, or a trifluoromethyl group is more preferred, and a methyl group, an ethyl group, an isopropyl group, a sec-butyl group, a pentyl group, or a hexyl group is particularly preferred.

[0115] Equation (Y1 -1) ∼ Equation (Y 1 -7) Among, V 1 and V 2 -CO-, -S-, -NR 13 Represents -, -O-, -Se-, or -SO2-, and -S-, -NR 13 It is preferable to be - or -O-. R 13 It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0116] Equation (Y 1 -1) ∼ Equation (Y 1 -7) Among, W 3 ~ W 7 Each represents -C= or -N= independently.

[0117] Equation (Y 1 -1) ∼ Equation (Y 1 -7) Among, V 1 , V 2 and W 3 ~ W 7 It is preferable that at least one of them represents a group containing S, N, or O.

[0118] Equation (Y 1 -1) ∼ Equation (Y 1 -7) Among, a represents an integer from 0 to 3 independently, and is preferably 0 or 1. b represents an integer from 0 to 2 independently, and is preferably 0.

[0119] Equation (Y 1 -1) ∼ Equation (Y 1 A certain energy represented by -7) is the following equation (Y 1 -8) ∼ Equation (Y 1 It is preferable that it be any one represented by -13), and the formula (Y 1 It is more desirable to use -8) as the cause. Also, * indicates the connection part.

[0120] [Chemical Formula 10]

[0121]

[0122] Equation (Y 1 -8) ∼ Equation (Y 1 -13) Among, Z 4 , a, b, V 1 , V 2 and W 3 is, formula (Y 1 -1) ∼ Equation (Y 1 -7) Z in 4 , a, b, V 1 , V 2 and W 3 It represents the same meaning as .

[0123] Y 1 Specific examples include, for instance, the group represented by formulas (ar-1) to (ar-840) described in Japanese Patent Publication No. 2019-003177. Among these, the group represented by the following formula is preferred.

[0124] [Chemical Formula 11]

[0125]

[0126] In one embodiment of the present invention, the group represented by formula (Ar-1) is specifically, the following formula (Ar 1 -1) ∼ (Ar 1 Examples of forms represented as -126) include the * part in the formula, which indicates a connection.

[0127] [Chemical Formula 12]

[0128]

[0129] [Chemical Formula 13]

[0130]

[0131] [Chemical Formula 14]

[0132]

[0133] [Chemical Formula 15]

[0134]

[0135] [Chemical Formula 16]

[0136]

[0137] [Chemical Formula 17]

[0138]

[0139] In one embodiment of the present invention, the group represented by formula (Ar-2) is specifically, the following formula (Ar 2 -1) ∼ (Ar 2 -13) can be used as an example. In the formula, * indicates a connecting part.

[0140] [Chemical Formula 18]

[0141]

[0142] In one embodiment of the present invention, the group represented by formula (Ar-3) is specifically, the following formula (Ar 3 -1) ∼ (Ar 3 -23) can be used as an example. In the formula, * indicates a connecting part.

[0143] [Chemical Formula 19]

[0144]

[0145] [Chemical Formula 20]

[0146]

[0147] The group represented by formulas (Ar-1) to (Ar-4) includes, in addition to the group specifically exemplified above, contributions described in, for example, Japanese Patent Publication No. 2011-207765, Japanese Patent Publication No. 2008-107767, WO2014 / 010325, etc.

[0148] In the formula (Ar-5), Y 3 and Y 4 is, respectively, the following formula (Y 3 -1) :

[0149] [Chemical Formula 21]

[0150]

[0151] It is selected from the representation.

[0152] Equation (Y 3 -1) Among, R Y1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The alkyl group comprises one or more substituents X 3 It may be substituted by.

[0153] Substituent X 3 Silver, fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, or, one -CH2- or two or more non-adjacent -CH2- may 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-, the number of carbon atoms that may be substituted It represents a straight-chain or branched alkyl group of 1 to 20, wherein any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or, -B 31 -F 31 -P 31 It also serves as the contribution represented by, and B 31 , F 31 and P 31 Each is B in the above formula (1). 11 , F 11 and P 11 Defined identically to, and each B in Equation (1) 11 , F 11 and P 11 It may be the same as or different from.

[0154] Substituent X 3As, preferably, it is a fluorine atom, a chlorine atom, -CF3, -OCF3, or a cyano group. R Y1 The alkyl group having 1 to 6 carbon atoms is preferably unsubstituted or substituted with a hydrogen atom or one or more fluorine atoms, and more preferably is a hydrogen atom.

[0155] Equation (Y 3 -1) Among, U 1 ... represents an organic group having 2 to 30 carbon atoms having an aromatic hydrocarbon group. Any carbon atom of the aromatic hydrocarbon group may be substituted with a heteroatom, and U 1 is an organic group having 2 to 30 carbon atoms, having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocyclic rings. The aromatic hydrocarbon group comprises one or more of the above-mentioned substituent X 3 It may be substituted by.

[0156] U 1 In terms of good wavelength dispersion, it is preferable that the organic group be an aromatic complex ring in which one or more carbon atoms are substituted with heteroatoms. 1 It is more preferable for the organic group to have an aromatic complex ring, which is a condensed ring of a 5-membered ring and a 6-membered ring, in that it exhibits good wavelength dispersion and high birefringence.

[0157] Specifically, U 1 It is preferable that the device has a mechanism represented by the following formula. Furthermore, in the following formula, these devices are T at any position 1 It has a joint hand with.

[0158] [Chemical Formula 22]

[0159]

[0160] Equation (Y 3 -1) Among, T 1 Silver, -O-, -S-, -COO-, -OCO-, -OCO-O-, -NU2 -, -N=CU 2 -, -CO-NU 2 -, -OCO-NU 2 - or O-NU 2 - represents, and U 2 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, an aromatic hydrocarbon group (any carbon atom of the aromatic hydrocarbon group may be substituted with a heteroatom), or an organic group having 2 to 30 carbon atoms having (E 31 -A 31 ) q -B 32 -F 32 -P 32 It represents. The alkyl group, cycloalkyl group, cycloalkenyl group, and aromatic hydrocarbon group are each unsubstituted or have one or more substituents X 3 It may be substituted by, and the alkyl group may be substituted by the cycloalkyl group or the cycloalkenyl group. One -CH2- in the alkyl group or two or more non-adjacent -CH2- may each be independently substituted with -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -SO2-, -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 one -CH2- in the cycloalkyl group or cycloalkenyl group or two or more non-adjacent -CH2- may each be independently substituted with -O-, -CO-, -COO-, -OCO-, or O-CO-O-. E 31 , A 31 , B 32 , F 32 and P 32 is, respectively, E in Equation (1) 11 , A 11 , B 11, F 11 and P 11 Defined identically to, and respectively the above E 11 , A 11 , B 11 , F 11 and P 11 It may be the same as or different from, where q represents an integer from 0 to 4, and E 31 and / or A 31 In cases where multiple such cases exist, each may be identical or different.

[0161] T 1 Silver, in terms of good birefringence and ease of synthesis, -O-, -S-, -N=CU 2 - or -NU 2 It is desirable that -O-, -S-, or -NU are used in terms of facilitating the improvement of wavelength dispersion and birefringence. 2 - It is more desirable.

[0162] U 2 is one or more of the above substituent X 3 It is preferable that the alkyl group or alkenyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or a cycloalkenyl group having 3 to 12 carbon atoms, or the alkyl group or alkenyl group having 3 to 12 carbon atoms, be substituted by the cycloalkyl group, cycloalkenyl group, or aryl group, and the alkyl group or alkenyl group may be substituted by the cycloalkyl group, cycloalkenyl group, or aryl group.

[0163] Among them, U 2 It is more preferable that the alkyl group be a straight-chain type having 1 to 20 carbon atoms, in terms of birefringence and solvent solubility, wherein a hydrogen atom may be substituted with a fluorine atom, and one -CH2- or two or more non-adjacent -CH2- may each be independently substituted with -O-, -CO-, -COO- or -OCO-.

[0164] U 1 and U 2 It may combine to form a ring. In that case, for example, -NU 1 U 2 A ring-shaped group represented by, or -N=CU 1 U 2 Examples include ring-shaped structures represented by [this].

[0165] In terms of the fact that the raw material is easily available, has good solubility, and exhibits high birefringence, Y 3 and Y 4 are respectively the following equations (Y 3' -1) ∼ Equation (Y 3' It is particularly desirable to represent the selected energy in -47).

[0166] [Chemical Formula 23]

[0167]

[0168] [Chemical Formula 24]

[0169]

[0170] [Chemical Formula 25]

[0171]

[0172] In the interest of improving the orientation of the polymerizable liquid crystal compound (1) and making it easy to manufacture industrially to improve productivity, the group represented by formula (Ar-5) specifically includes the following group. The following (Ar 5 -1) ∼ (Ar 5 -20) Among * is, G 11 , M or G 12 It represents the bonding portion with the adjacent -CO-O- or -O-CO- respectively.

[0173] [Chemical Formula 26]

[0174]

[0175] [Chemical Formula 27]

[0176]

[0177] [Chemical Formula 28]

[0178]

[0179] Among formulas (Ar-1) to (Ar-5), formulas (Ar-1), (Ar-2), and (Ar-5) are preferred, formulas (Ar-1) and (Ar-5) are more preferred, and formula (Ar-1) is even more preferred.

[0180] In Equation (1), *-O-CO-G 11 -E 11 -(A 11 -B 11 ) k11 -F 11 -P 11 , and *-O-CO-G 12 -E 12 -(A 12 -B 12 ) k12 -F 12 -P 12 Specific examples of this include structures represented by formulas (R-1) to (R-100).

[0181] Among the foods, * is, Ar 11 or Ar 12 It represents the bonding loss for, and n represents an integer from 2 to 12. In addition, the cyclohexane ring may be trans or cis, but it is preferred to be trans.

[0182] [Chemical Formula 29]

[0183]

[0184] [Chemical Formula 30]

[0185]

[0186] [Chemical Formula 31]

[0187]

[0188] [Chemical Formula 32]

[0189]

[0190] [Chemical Formula 33]

[0191]

[0192] [Chemical Formula 34]

[0193]

[0194] [Chemical Formula 35]

[0195]

[0196] [Chemical Formula 36]

[0197]

[0198] [Chemical Formula 37]

[0199]

[0200] The polymerizable liquid crystal composition of the present invention comprises the polymerizable liquid crystal compound (1) of the present invention and formula (2):

[0201] [Chemical Formula 38]

[0202]

[0203] [Essence (2),

[0204] k21 and k22 each independently represent integers greater than or equal to 1;

[0205] B 21 and B 22 is, each independently, -CR 1 R 2 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S- or representing a single bond, R 1 and R 2 Each represents, independently, a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.

[0206] E 21 and E 22is, each independently, -CR 1 R 2 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S- or represents a single bond;

[0207] G 21 and G 22 Each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, and the hydrogen atoms included in the alicyclic hydrocarbon group are halogen atoms, -R 3 , -OR 3 , may be substituted with a cyano group or a nitro group, and the -CH2- included in the alicyclic hydrocarbon group may be substituted with -O-, -S- or -NH-, and R 3 ... represents an alkyl group having 1 to 4 carbon atoms, and the hydrogen atoms included in the alkyl group may be substituted with fluorine atoms;

[0208] A 21 and A 22 Each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the hydrogen atoms included in the alicyclic hydrocarbon group and the aromatic hydrocarbon group are halogen atoms, -R 3 , -OR 3 , may be substituted with cyano groups or nitro groups ;

[0209] F 21 and F 22 Each independently represents an alkanedyl group having 1 to 12 carbon atoms, and the hydrogen atoms included in the alkanedyl group are -OR 3Or it may be substituted with a halogen atom, and the -CH2- included in the alkandyl group may be substituted with -O- or -CO- ;

[0210] P 21 and P 22 Each independently represents a hydrogen atom or a polymerizable group (where P 21 and P 22 At least one of them is a polymerizable group) ;

[0211] Ar 21 Each represents a divalent aromatic group that may have a substituent, independently.

[0212] It includes a polymerizable liquid crystal compound represented by (hereinafter also referred to as "polymerizable liquid crystal compound (2)"). By using a combination of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2), the phase transition temperature of the polymerizable liquid crystal compound (2) can be effectively lowered while suppressing the occurrence of orientation defects. Although the reason for this is not clear, it is thought that when the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) of the present invention have similar structural units, the compatibility between them is increased by the polymerizable liquid crystal compound (1), which has high molecular flexibility and M in formula (1) is an aliphatic hydrocarbon, and in this state, the phase transition temperature can be significantly lowered while maintaining the high orientation order of the two types of polymerizable liquid crystal compounds included. If a phase transition is possible at a low temperature, a liquid crystal cured film can be manufactured from the polymerizable liquid crystal compound at a lower processing temperature, and such a liquid crystal cured film can reduce the effects of heating.

[0213] In particular, from the perspective of easily lowering the phase transition temperature of a polymerizable liquid crystal compound [as a mixture of polymerizable liquid crystal compounds (1) and (2)] without impairing optical properties while suppressing the occurrence of orientation defects, the -O-CO-G of the polymerizable liquid crystal compound (1) of the present invention11 -E 11 -(A 11 -B 11 ) k11 -F 11 -P 11 , and -O-CO-G 12 -E 12 -(A 12 -B 12 ) k12 -F 12 -P 12 Wow, -O-CO-G of the polymerizable liquid crystal compound (2) 21 -E 21 -(A 21 -B 21 ) k21 -F 21 -P 21 , and -O-CO-G 22 -E 22 -(A 22 -B 22 ) k22 -F 22 -P 22 It is desirable for them to have structural units similar to each other.

[0214] k21 and k22 in Equation (2) each independently represent an integer greater than or equal to 1, and may be, for example, integers from 1 to 5. The sum of k21 and k22 is preferably 2 to 6, more preferably 2 to 4. From the perspective of excellent liquid crystallization, it is preferable that k21 and k22 each independently be 1 or 2, and from the perspective of ease of manufacturing the polymerizable liquid crystal compound (2), it is preferable that k21 and k22 are the same number, and in a preferred embodiment of the present invention, k21 and k22 are both 1. Also, from the perspective of excellent liquid crystallization, it is preferable that k11 and k12 in Equation (1) and k21 and k22 in Equation (2) are all the same number, and more preferable that they are all 1.

[0215] B in Equation (2) 21, B 22 , E 21 , E 22 , G21 , G 22 , A 21 , A 22 , F 21 , F 22 , P 21 and P 22 The paths represented by are each B in Equation (1). 11 , B 12 , E 11 , E 12 , G 11 , G 12 , A 11 , A 12 , F 11 , F 12 , P 11 and P 12 As a reference to the reference represented by , the same reference as exemplified can be given, and the same applies to each preferred mode. Also, Ar in Equation (2) 21 The path represented by is Ar in Equation (1). 11 , Ar 12 The same as the example given can be cited as a representation, and the same applies to the desirable mode.

[0216] A in Equation (1) 11 , A 12 , B 11 , B 12 , E 11 , E 12 , F 11 , F 12 , G 11 , G 12 , P 11 and P 12 The giga represented by , respectively, A in equation (2). 21 , A 22 , B 21 , B 22 , E 21 , E 22 , F 21 , F 22 , G 21 , G 22 , P 21 and P 22 It is identical to the qi represented by , and Ar in Equation (1)11 and Ar 12 The giga represented by is each Ar in Equation (2). 21 It is desirable that the above group in Formula (1) and the above group in Formula (2) have such a relationship, the compatibility between the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) is likely to increase, and the phase transition temperature is likely to be significantly lowered while suppressing orientation defects.

[0217] The content of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) in the polymerizable liquid crystal composition of the present invention may be appropriately determined within the range in which the effects of the present invention are obtained, depending on the type of the polymerizable liquid crystal compound (1) and / or the polymerizable liquid crystal compound (2), etc. It is preferable that the ratio of the peak area of ​​the polymerizable liquid crystal compound (1) to the total peak area of ​​the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2), measured by liquid chromatography (hereinafter also referred to as the "area percentage value") is 0.1% or more and 50% or less. More preferably, it is 1 mass% or more, even more preferably 2 mass% or more, and particularly preferably 3 mass% or more. If the content of the polymerizable liquid crystal compound (1) is greater than or equal to the above lower limit value, the solubility of the polymerizable liquid crystal compound in a solvent is easily improved, and the phase transition temperature is easily lowered sufficiently. In addition, if the content of the polymerizable liquid crystal compound (1) is less than or equal to the upper limit value, the orientation state of the liquid crystal can be maintained well when manufacturing a liquid crystal curing film from a polymerizable liquid crystal composition containing the polymerizable liquid crystal compound, so an optical film with excellent optical properties can be obtained. In addition, when a plurality of polymerizable liquid crystal compounds corresponding to the polymerizable liquid crystal compound (1) and / or the polymerizable liquid crystal compound (2) are included, the area percentage value of the polymerizable liquid crystal compound (1) is calculated with respect to the total peak area of ​​the total polymerizable liquid crystal compound (1) and the total polymerizable liquid crystal compound (2). The area percentage value can be calculated based on the peak area measured by liquid chromatography, and in detail, can be measured and calculated by the method described in the example below.

[0218] The polymerizable liquid crystal composition of the present invention can significantly lower the phase transition temperature compared to the case where the polymerizable liquid crystal compound (2) is used alone by including a combination of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2). For example, the phase transition temperature of the liquid crystal mixture of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) constituting the polymerizable liquid crystal composition of the present invention is preferably 153°C or lower, more preferably 150°C or lower, and even more preferably 145°C or lower.

[0219] In addition, when the polymerizable liquid crystal compound (1) of the present invention is used in combination with the polymerizable liquid crystal compound (2), the phase transition temperature can be lowered, preferably 8°C or more, more preferably 10°C or more, even more preferably 12°C or more, and particularly preferably 15°C or more, compared to when the polymerizable liquid crystal compound (2) is used alone.

[0220] In addition, in the present invention, the phase transition temperature of a polymerizable liquid crystal compound can be measured by the method described in the examples below. When two or more polymerizable liquid crystal compounds are included, the phase transition temperature is measured using a polymerizable liquid crystal compound (mixture) having the same composition as the polymerizable liquid crystal compound constituting the polymerizable liquid crystal composition.

[0221] In addition, the polymerizable liquid crystal composition of the present invention includes a combination of a polymerizable liquid crystal compound (1) and a polymerizable liquid crystal compound (2), and compared to the case where the polymerizable liquid crystal compound (2) is used alone, the effect of increasing the solubility of the polymerizable liquid crystal compound in a solvent is excellent.

[0222] The method of manufacturing the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) constituting the polymerizable liquid crystal composition of the present invention is not particularly limited, and they can be manufactured by appropriately combining known organic synthesis reactions (e.g., condensation reaction, esterification reaction, Williamson reaction, Ullmann reaction, Wittig reaction, Schiff base generation reaction, benzylation reaction, Sonogashira reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Hiyama reaction, Birchwald-Hartwick reaction, Fledel-Crafts reaction, Hex reaction, aldol reaction, etc.) described in Methoden der Organischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, New Experimental Chemistry Lectures, etc., according to their structure.

[0223] For example, A in Equation (1) 11 Department A 12 , B 11 and B 12 , E 11 and E 12 , F 11 and F 12 , G 11 and G 12 , P 11 and P 12 , Ar 11 and Ar 12 Each identical polymerizable liquid crystal compound (1) can be prepared by esterifying the compound represented by formula (1-1) (hereinafter also referred to as "compound (1-1)"), the compound represented by formula (1-2) (hereinafter also referred to as "compound (1-2)"), and the compound represented by formula (1-3) (hereinafter also referred to as "compound (1-3)"). In addition, P, F, B, A, E, and G in formula (1-1) are each P in formula (1). 11 and P 12 , F 11 and F 12 , B 11 and B12 , A 11 Department A 12 , E 11 and E 12 , G 11 and G 12 It is identical to what is defined as. Also, M in the above equation (1-2) and Ar in equation (1-3) are respectively M and Ar in equation (1). 11 , Ar 12 It is identical to what is defined as. P, F, B, A, E, G, and Ar are determined corresponding to the desired polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2).

[0224] [Chemical Formula 39]

[0225]

[0226] [Chemical Formula 40]

[0227]

[0228] [Chemical Formula 41]

[0229]

[0230] It is preferable to carry out the reaction of compounds (1-1) to (1-3) in the presence of a condensation agent.

[0231] As condensation agents, for example, 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimidemeto-para-toluenesulfonate, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (some water-soluble carbodiimides are commercially available as WSC), carbodiimides such as bis(2,6-diisopropylphenyl)carbodiimide, bis(trimethylsilyl)carbodiimide, and N,N'-diisopropylcarbodiimide, 2-methyl-6-nitrobenzoic anhydride, 2,2'-carbonylbis-1H-imidazole, 1,1'-oxalyldiimidazole, diphenylphosphorylazide, 1-(4-nitrobenzenesulfonyl)-1H-1,2,4-triazole, 1H-benzotriazole-1-yloxytripyrrolidinophosphonium hexafluorophosphate, 1H-benzotriazole-1-yloxytris(dimethylamino)phosphonium hexafluorophosphate, N,N,N',N'-tetramethyl-O-(N-succinimidyl)uronium tetrafluoroborate, N-(1,2,2,2-tetrachloroethoxycarbonyloxy)succinimide, N-carbobenzoxisuccinimide, O-(6-chlorobenzotriazole-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate, O-(6-chlorobenzotriazole-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, Examples include 2-bromo-1-ethylpyridinium tetrafluoroborate, 2-chloro-1,3-dimethylimidazolinium chloride, 2-chloro-1,3-dimethylimidazolinium hexafluorophosphate, 2-chloro-1-methylpyridinium iodide, 2-chloro-1-methylpyridinium para-toluenesulfonate, 2-fluoro-1-methylpyridinium para-toluenesulfonate, trichloroacetic acid pentachlorophenyl ester, etc.

[0232] Dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, bis(2,6-diisopropylphenyl)carbodiimide, bis(trimethylsilyl)carbodiimide, N,N'-diisopropylcarbodiimide, and 2,2'-carbonylbis-1H-imidazole are preferred as condensation agents due to their reactivity, cost, and wide range of available solvent options.

[0233] The polymerizable liquid crystal compound (2) can be prepared, for example, by reacting the compound (1-1) with the compound (1-3).

[0234] In the present invention, the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) constituting the polymerizable liquid crystal composition may be prepared separately and then mixed to be used as a liquid crystal mixture. Alternatively, the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) may be obtained as a liquid crystal mixture by reacting the compounds (1-1) to (1-3) in a suitable ratio. Without isolating each polymerizable liquid crystal compound from the obtained liquid crystal mixture, the desired polymerizable liquid crystal mixture may be prepared by controlling the content of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) in the liquid crystal mixture as needed, by mixing the liquid crystal mixture with the polymerizable liquid crystal compound (1) or mixing the liquid crystal mixture with the polymerizable liquid crystal compound (2), without isolating each polymerizable liquid crystal compound from the obtained liquid crystal mixture.

[0235] When prepared by the former method, it is easy to adjust the content of the polymerizable liquid crystal compound (1) or the polymerizable liquid crystal compound (2) to a desired range, making it easy to control the solvent solubility of the polymerizable liquid crystal compound. On the other hand, when prepared by the latter method, the synthesis is simple, and the polymerizable liquid crystal composition can be manufactured more efficiently.

[0236] When preparing a liquid crystal mixture of a polymerizable liquid crystal compound (1) and a polymerizable liquid crystal compound (2), the amount of compound (1-2) used for the reaction is preferably 0.01 parts by mass or more and 30 parts by mass or less per 100 parts by mass of compound (1-1), and more preferably 0.1 parts by mass or more and 20 parts by mass or less. In addition, the amount of compound (1-3) used for the reaction is preferably 1 part by mass or more and 70 parts by mass or less per 100 parts by mass of compound (1-1), and more preferably 10 parts by mass or more and 65 parts by mass or less. By adjusting the amounts of compound (1-1), compound (1-2), and compound (1-3) within the above ranges, it is easy to prepare a liquid crystal mixture containing the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) in a desired ratio.

[0237] The polymerizable liquid crystal composition of the present invention may include polymerizable liquid crystal compounds other than the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2), provided that such compounds do not affect the effects of the present invention. Examples of such polymerizable liquid crystal compounds include, for instance, compounds described in Chapter 3, Molecular Structure and Liquid Crystalline Properties, of the Liquid Crystal Handbook (compiled by the Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd. on October 30, 2000), specifically in Section 3,

[0238] When the polymerizable liquid crystal composition of the present invention includes a polymerizable liquid crystal compound other than the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2), the content thereof is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less, based on 100 parts by mass of the total of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2). In particular, if the content of a liquid crystal compound having a molecular structure significantly different from that of the polymerizable liquid crystal compound (1) or the polymerizable liquid crystal compound (2) becomes excessively high, it may cause phase separation and impair the appearance; therefore, it is preferable that the polymerizable liquid crystal compound constituting the polymerizable liquid crystal composition of the present invention be substantially composed of a polymerizable liquid crystal compound having a structure similar to that of the polymerizable liquid crystal compound (1). Furthermore, the above "similar" refers, for example, to the -O-CO-G of the polymerizable liquid crystal compound (1). 11 -E 11 -(A 11 -B 11 ) k11 -F 11 -P 11 , -O-CO-G 12 -E 12 -(A 12 -B 12 ) k12 -F 12 -P 12 The part represented by or Ar 11 or Ar 12 It refers to a case having a structure common to the part represented by, and the above “substantially composed” means that the content of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) is 90 mass% or more with respect to the total mass of the polymerizable liquid crystal compound included in the polymerizable liquid crystal composition of the present invention. In one embodiment of the present invention, the polymerizable liquid crystal composition does not include a polymerizable liquid crystal compound other than the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2).

[0239] The content of the polymerizable liquid crystal compound (total amount of all polymerizable liquid crystal compounds) in the polymerizable liquid crystal composition of the present invention is, for example, 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass, more preferably 85 to 98 parts by mass, and even more preferably 90 to 95 parts by mass, with respect to 100 parts by mass of the solid content of the polymerizable liquid crystal composition. If the total mass of the polymerizable liquid crystal compound is within the above range, it is advantageous in terms of the orientation of the obtained liquid crystal cured film. Furthermore, in this specification, the polymerizable liquid crystal compound includes a polymerizable liquid crystal compound (1), a polymerizable liquid crystal compound (2), and, if included, other polymerizable liquid crystal compounds different from these (hereinafter, these are collectively referred to as a "polymerizable liquid crystal mixture"). The solid content of the polymerizable liquid crystal composition refers to all components of the polymerizable liquid crystal composition excluding volatile components such as organic solvents.

[0240] The polymerizable liquid crystal composition of the present invention may additionally include additives such as an organic solvent, a photopolymerization initiator, a polymerization inhibitor, a photosensitizer, and a leveling agent in addition to the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2). Each of these components may be used as a single type or in combination of two or more types.

[0241] In the present invention, since the polymerizable liquid crystal mixture is typically applied to a substrate, etc., while dissolved in a solvent, it is preferable to include a solvent. As for the solvent, it is preferable to have a solvent capable of dissolving polymerizable liquid crystal compounds such as polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2), and also preferably a solvent that is inert to the polymerization reaction of the polymerizable liquid crystal compound. By including a combination of polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2) in the polymerizable liquid crystal composition of the present invention, the solvent solubility of the polymerizable liquid crystal compound (2) can be significantly improved compared to the case where the polymerizable liquid crystal compound (2) is dissolved in a solvent alone. For this reason, various solvents can be applied. As for the solvent, for example, alcohol solvents such as water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxyethanol, and propylene glycol monomethyl ether; Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; alicyclic hydrocarbon solvents such as ethylcyclohexane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; chlorine-containing solvents such as chloroform and chlorobenzene; Examples include amide-based solvents such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone (NMP), and 1,3-dimethyl-2-imidazolidinone. These solvents may be used alone or in combination of two or more.Among these, organic solvents are preferred, alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide solvents, and aromatic hydrocarbon solvents are more preferred, and from the perspective of productivity, at least one selected from the group consisting of methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and N-methylpyrrolidone is even more preferred.

[0242] The solvent content in the polymerizable liquid crystal composition is preferably 50 to 98 parts by mass, more preferably 50 to 95 parts by mass, with respect to 100 parts by mass of the polymerizable liquid crystal composition. Accordingly, the solid content in 100 parts by mass of the polymerizable liquid crystal composition is preferably 2 to 50 parts by mass, and more preferably 5 to 50 parts by mass. If the solid content is 50 parts by mass or less, the viscosity of the polymerizable liquid crystal composition is lowered, so the thickness of the film becomes approximately uniform and non-uniformity tends not to occur easily. The above solid content can be appropriately determined by considering the thickness of the liquid crystal cured film to be manufactured. The polymerizable liquid crystal composition of the present invention is advantageous in that it can reduce the amount of organic solvent used during coating and preservation, etc., because it has excellent solubility in solvents by combining the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2).

[0243] The polymerizable liquid crystal composition of the present invention preferably includes a photopolymerization initiator. A photopolymerization initiator is a compound capable of initiating a polymerization reaction of a polymerizable liquid crystal, etc. by generating a reaction-active species upon the contribution of light. Examples of reaction-active species include radicals, cations, or anions. Among these, a photopolymerization initiator that generates radicals upon light irradiation is preferred from the perspective of ease of reaction control. As a photopolymerization initiator, only one type may be used, or two or more types may be used in combination.

[0244] Examples of photopolymerization initiators include, for instance, benzoin compounds, benzophenone compounds, benzyl ketal compounds, alkylphenone compounds, acylphosphine oxide compounds, α-hydroxyketone compounds, α-aminoketone compounds, triazine compounds, iodonium salts, and sulfonium salts. Specifically, Irgacure (registered trademark) 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369, Irgacure 379, Irgacure 127, Irgacure 2959, Irgacure 754, Irgacure 379EG (all manufactured by BASF Japan, Inc.), Seikul BZ, Seikul Z, Seikul BEE (all manufactured by Seiko Chemical, Inc.), Kayacure BP100 (manufactured by Nippon Kagaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow), Adeka Optomer SP-152, Adeka Optomer SP-170, Adeka Optomer N-1717, Adeka Optomer Examples include N-1919, ADEKA Arcles NCI-831, ADEKA Arcles NCI-930 (all manufactured by ADEKA Corporation), TAZ-A, TAZ-PP (all manufactured by Nippon Sieberhegner Corporation), and TAZ-104 (manufactured by Sanwa Chemical Corporation).

[0245] In the present invention, the polymerizable liquid crystal composition preferably comprises at least one photopolymerization initiator, and may also comprise two or more photopolymerization initiators.

[0246] Since the photopolymerization initiator can fully utilize the energy emitted from the light source and has excellent productivity, it is preferable that the maximum absorption wavelength be 300 nm to 400 nm, and more preferable that it be 300 nm to 380 nm; among these, α-acetophenone-based photopolymerization initiators and oxime-based photopolymerization initiators are preferred.

[0247] Examples of α-acetophenone compounds include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, and 2-dimethylamino-1-(4-morpholinophenyl)-2-(4-methylphenylmethyl)butan-1-one, and more preferably, 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one and 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one. Examples of commercially available α-acetophenone compounds include Yirgacure 369, 379EG, 907 (manufactured by BASF Japan Co., Ltd.) and Seikul BEE (manufactured by Seiko Chemical Co., Ltd.).

[0248] Oxime-based photopolymerization initiators generate methyl radicals upon irradiation with light. These methyl radicals facilitate the polymerization of polymerizable liquid crystal compounds within the core of the formed liquid crystal curing film. Furthermore, from the perspective of promoting the polymerization reaction within the core of the formed liquid crystal curing film more efficiently, it is preferable to use a photopolymerization initiator capable of efficiently utilizing ultraviolet rays with a wavelength of 350 nm or longer. As photopolymerization initiators capable of efficiently utilizing ultraviolet rays with a wavelength of 350 nm or longer, triazine compounds or oxime ester-type carbazole compounds are preferred, and from the perspective of sensitivity, oxime ester-type carbazole compounds are more preferred. Examples of oxime ester type carbazole compounds include 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanol, and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyloxime). Examples of commercially available oxime ester type carbazole compounds include Yirgacure OXE-01, Yirgacure OXE-02, Yirgacure OXE-03 (all manufactured by BASF Japan Co., Ltd.), ADEKA Optomer N-1919, and ADEKA Arcles NCI-831 (all manufactured by ADEKA Co., Ltd.).

[0249] The amount of photopolymerization initiator added is typically 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass, and more preferably 1 to 15 parts by mass, per 100 parts by mass of the polymerizable liquid crystal compound. Within the above range, the reaction of the polymerizable group proceeds sufficiently, and the orientation of the polymerizable liquid crystal compound is not easily disrupted.

[0250] By using a photosensitizer, the photopolymerization initiator can be made highly sensitive. Examples of photosensitizers include xanthones such as xanthone and thioxanthone; anthracenes having substituents such as anthracene and alkyl ethers; phenothiazines; and rubrene. The content of the photosensitizer is typically 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the total amount of polymerizable liquid crystal compound.

[0251] By incorporating a polymerization inhibitor, the polymerization reaction of a polymerizable liquid crystal compound can be controlled. Examples of polymerization inhibitors include hydroquinones having substituents such as hydroquinone and alkyl ethers; catechols having substituents such as butylcatechol and alkyl ethers; radical scavengers such as pyrogallols and 2,2,6,6-tetramethyl-1-piperidinyloxy radicals; thiophenols; β-naphthylamines and β-naphthols. In order to polymerize the polymerizable liquid crystal compound (1) without disturbing the orientation, the content of the polymerization inhibitor is typically 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the total amount of the polymerizable liquid crystal compound.

[0252] In addition, the polymerizable liquid crystal composition of the present invention may include a leveling agent. The leveling agent is an additive that has the function of adjusting the fluidity of the polymerizable liquid crystal composition and making the film obtained by applying it flatter, and examples include silicon-based, polyacrylate-based, and perfluoroalkyl-based leveling agents.Specifically, DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all manufactured by Toray Dow Corning Corp.), KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001 (all manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (all manufactured by Momentive Performance Materials Japan), fluorinert (registered trademark) FC-72, FC-40, and the FC-43, FC-3283 (all manufactured by Sumitomo 3M Corp.), MegaPac (registered trademark) R-08, R-30, R-90, F-410, F-411, F-443, F-445, F-470, F-477, F-479, F-482, F-483 (all manufactured by DIC Corp.), F-Top (product name) EF301, EF303, EF351, EF352 (all manufactured by Mitsubishi Material Electronics Kasei Corp.), Suplon (registered trademark) S-381, S-382, S-383, S-393, SC-101, SC-105, KH-40, SA-100 (all manufactured by AGC Seimi Examples include BYK-352, BYK-353, and BYK-361N (all manufactured by BM Chemie Co., Ltd.), product name E1830, product name E5844 (manufactured by Daikin Fine Chemical Research Institute Co., Ltd.), BM-1000, BM-1100, BYK-352, BYK-353, and BYK-361N (all product names: manufactured by BM Chemie Co., Ltd.). Among these, polyacrylate-based leveling agents and perfluoroalkyl-based leveling agents are preferred.

[0253] The content of the leveling agent in the polymerizable liquid crystal composition is preferably 0.01 to 5 parts by mass and more preferably 0.05 to 3 parts by mass, based on 100 parts by mass of the total amount of the polymerizable liquid crystal compound.

[0254] It is desirable that the content of the leveling agent be within the above range, as this facilitates the orientation of the polymerizable liquid crystal compound and also tends to result in a smoother liquid crystal cured film. The polymerizable liquid crystal composition may contain two or more types of leveling agents.

[0255] The polymerizable liquid crystal composition of the present invention can be prepared by adding additives such as a solvent, a photopolymerization initiator, a polymerization inhibitor, a photosensitizer, or a leveling agent to the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) as needed, and stirring and mixing at a predetermined temperature.

[0256] Phase difference film

[0257] The polymerizable liquid crystal composition of the present invention has a low phase transition temperature of the polymerizable liquid crystal compound, allowing the liquid crystal curing film to be manufactured at a lower processing temperature. This reduces the influence of heating, thereby enabling the production of a liquid crystal curing film with excellent optical properties. Furthermore, because it has high solubility in solvents and excellent coating and film-forming properties, it is possible to suppress the occurrence of orientation defects caused by undissolved polymerizable liquid crystal compounds or precipitates and deposits within the composition. Therefore, by using the polymerizable liquid crystal composition of the present invention, it is possible to form a film without degrading the optical properties that the polymerizable liquid crystal compound can inherently exhibit, thereby enabling the production of a liquid crystal curing film with excellent optical properties. Accordingly, the present invention relates to a phase difference film comprising a liquid crystal curing film formed by curing the polymerizable liquid crystal composition of the present invention, particularly, as a cured product of the polymerizable liquid crystal composition, the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) in the polymerizable liquid crystal composition in an oriented state. The phase difference film composed of the above liquid crystal curing film can sufficiently exhibit the optical properties that the polymerizable liquid crystal compound used can inherently exhibit, and thus can be a phase difference film having high optical performance.

[0258] The liquid crystal curing film constituting the phase difference film of the present invention may be composed of a homopolymer of a polymerizable liquid crystal compound (1) in an oriented state and a homopolymer of a polymerizable liquid crystal compound (2), or it may be composed of a copolymer in an oriented state of a mixture of a polymerizable liquid crystal compound (1) and a polymerizable liquid crystal compound (2). Since the polymerization reaction is easy and it is easy to obtain a uniform liquid crystal curing film, it is preferable that the liquid crystal curing film constituting the phase difference film of the present invention be composed of a copolymer in an oriented state of a mixture of a polymerizable liquid crystal compound (1) and a polymerizable liquid crystal compound (2).

[0259] In one embodiment of the present invention, the phase difference film of the present invention comprises a liquid crystal cured film having optical properties represented by the following formulas (i), (ii), and (iii), which is a cured product of the polymerizable liquid crystal composition of the present invention. The liquid crystal cured film is typically a cured product formed by curing a polymerizable liquid crystal compound in a state oriented horizontally with respect to the plane of the liquid crystal cured film (hereinafter also referred to as a "horizontally oriented liquid crystal cured film").

[0260] Re(450) / Re(550) ≤ 1.00 (i)

[0261] 1.00 ≤ Re(650) / Re(550) (ii)

[0262] 100 nm ≤ Re(550) ≤ 180 nm (iii)

[0263] [In the formula, Re(λ) represents the in-plane phase difference value of the liquid crystal cured film at a wavelength λ nm, and Re = (nx(λ) - ny(λ)) × d (d represents the thickness of the liquid crystal cured film, nx represents the principal refractive index at a wavelength λ nm in a direction parallel to the plane of the liquid crystal cured film in the refractive index ellipsoid formed by the liquid crystal cured film, and ny represents the refractive index at a wavelength λ nm in a direction parallel to the plane of the liquid crystal cured film and also orthogonal to the direction of nx in the refractive index ellipsoid formed by the liquid crystal cured film).]

[0264] When a horizontally oriented liquid crystal cured film satisfies equations (i) and (ii), the horizontally oriented liquid crystal cured film exhibits so-called inverse wavelength dispersibility, in which the in-plane phase difference value at short wavelengths becomes smaller than the in-plane phase difference value at long wavelengths. In order to improve inverse wavelength dispersibility and further improve the optical properties of the phase difference film, Re(450) / Re(550) is preferably 0.70 or higher, more preferably 0.78 or higher, and also preferably 0.90 or lower, more preferably 0.88 or lower, even more preferably 0.86 or lower, particularly preferably 0.85 or lower, and especially preferably 0.84 or lower. Additionally, Re(650) / Re(550) is preferably 1.00 or higher, more preferably 1.01 or higher, and even more preferably 1.02 or higher.

[0265] The above in-plane phase difference value can be adjusted by the thickness d of the horizontally oriented liquid crystal cured film. Since the in-plane phase difference value is determined by the above equation Re(λ) = (nx(λ) - ny(λ)) × d, in order to obtain the desired in-plane phase difference value (Re(λ): in-plane phase difference value of the horizontally oriented liquid crystal cured film at wavelength λ (nm), the three-dimensional refractive index and the film thickness d can be adjusted.

[0266] In addition, when the horizontally aligned liquid crystal cured film satisfies Equation (iii), the effect of improving the front reflection color (effect of suppressing discoloration) is excellent when an elliptical polarizer equipped with a phase difference film including the horizontally aligned liquid crystal cured film is applied to an organic EL display device. A more preferred range of the in-plane phase difference value is 120 nm ≤ Re(550) ≤ 170 nm, and an even more preferred range is 130 nm ≤ Re(550) ≤ 150 nm.

[0267] In one embodiment of the present invention, the phase difference film of the present invention comprises a liquid crystal cured film having optical properties represented by the following formulas (iv), (v) and (vi), which is a cured product of the polymerizable liquid crystal composition of the present invention. The liquid crystal cured film is typically a cured product formed by curing a polymerizable liquid crystal compound in a state oriented perpendicularly to the plane of the liquid crystal cured film (hereinafter also referred to as a "vertically oriented liquid crystal cured film").

[0268] Rth(450) / Rth(550) ≤ 1.00 (iv)

[0269] 1.00 ≤ Rth(650) / Rth(550) (v)

[0270] -100 ㎚ ≤ Rth(550) ≤ -40 ㎚ (vi)

[0271] [In the formula, Rth(λ) represents the phase difference value in the thickness direction at a wavelength λ nm of the liquid crystal cured film, and Rth = ((nx(λ) + ny(λ)) / 2 - nz) × d (where d represents the thickness of the liquid crystal cured film, nx represents the principal refractive index at a wavelength λ nm in the direction parallel to the plane of the liquid crystal cured film in the refractive index ellipsoid formed by the liquid crystal cured film, ny represents the refractive index at a wavelength λ nm in the direction parallel to the plane of the liquid crystal cured film and also orthogonal to the direction of nx in the refractive index ellipsoid formed by the liquid crystal cured film, and nz represents the refractive index at a wavelength λ nm in the direction perpendicular to the plane of the liquid crystal cured film in the refractive index ellipsoid formed by the liquid crystal cured film).]

[0272] When a vertically oriented liquid crystal cured film satisfies equations (iv) and (v), in an elliptical polarizer having a phase difference film including said vertically oriented liquid crystal cured film, the decrease in ellipticity on the short wavelength side can be suppressed and the oblique reflection color can be improved. The value of Rth (450) / Rth (550) in the vertically oriented liquid crystal cured film is preferably 0.70 or higher, more preferably 0.78 or higher, and also preferably 0.90 or lower, more preferably 0.88 or lower, even more preferably 0.86 or lower, particularly preferably 0.85 or lower, and especially preferably 0.84 or lower. Also, Rth (650) / Rth (550) is preferably 1.0 or higher, more preferably 1.01 or higher, and even more preferably 1.02 or higher.

[0273] In addition, when the vertically oriented liquid crystal cured film satisfies Equation (vi), the four-directional reflection color can be improved when an elliptical polarizer having a phase difference film including the vertically oriented liquid crystal cured film is applied to an organic EL display device. The phase difference value Rth (550) in the film thickness direction of the vertically oriented liquid crystal cured film is more preferably -90 nm or more, even more preferably -80 nm or more, and even more preferably -50 nm or less.

[0274] The phase difference film of the present invention is, for example,

[0275] A process of forming a film of the polymerizable liquid crystal composition of the present invention, drying the film, and also orienting a polymerizable liquid crystal compound in the polymerizable liquid crystal composition, and

[0276] It can be manufactured by a method including a process of polymerizing a polymerizable liquid crystal compound by light irradiation while maintaining an orientation state to form a liquid crystal curing film.

[0277] A film of a polymerizable liquid crystal composition can be formed by applying the polymerizable liquid crystal composition onto a substrate or onto an alignment film described later, etc.

[0278] Examples of substrates include glass substrates or film substrates, but a resin film substrate is preferred from the perspective of processability. Examples of resins constituting the film substrate include polyolefins such as polyethylene, polypropylene, and norbornene-based polymers; cyclic olefin resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylic acid esters; polyacrylic acid esters; cellulose esters such as triacetylcellulose, diacetylcellulose, and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyethersulfone; polyetherketone; and plastics such as polyphenylene sulfide and polyphenylene oxide. Such resins can be formed into a film using known means such as solvent casting or melt extrusion to serve as the substrate. The surface of the substrate may have a protective layer formed of acrylic resin, methacrylate resin, epoxy resin, oxetane resin, urethane resin, melamine resin, etc., and may also have surface treatments such as release treatment like silicone treatment, corona treatment, plasma treatment, etc.

[0279] Commercially available products may be used as substrates. Examples of commercially available cellulose ester substrates include, for instance, cellulose ester substrates manufactured by Fuji Photo Film Co., Ltd., such as Fuji Tac Film; cellulose ester substrates manufactured by Konica Minolta Opt Co., Ltd., such as “KC8UX2M”, “KC8UY”, and “KC4UY”. Examples of commercially available cyclic olefin resins include, for instance, cyclic olefin resins manufactured by Ticona (Germany), such as “Topas (registered trademark)”; cyclic olefin resins manufactured by JSR Co., Ltd., such as “Aton (registered trademark)”; cyclic olefin resins manufactured by Nippon Zeon Co., Ltd., such as “ZEONOR (registered trademark)” and “ZEONEX (registered trademark)”; and cyclic olefin resins manufactured by Mitsui Chemical Co., Ltd., such as “Apel (registered trademark)”. Commercially available cyclic olefin resin substrates may also be used. Examples of commercially available cyclic olefin resin substrates include cyclic olefin resin substrates manufactured by Sekisui Chemical Industry Co., Ltd., such as “Escina (registered trademark)” and “SCA40 (registered trademark)”; cyclic olefin resin substrates manufactured by Optes Co., Ltd., such as “Zeonor Film (registered trademark)”; and cyclic olefin resin substrates manufactured by JSR Co., Ltd., such as “Aton Film (registered trademark)”.

[0280] From the perspective of thinning the phase difference film, ease of peeling the substrate, and handling ability of the substrate, the thickness of the substrate is typically 5 to 300 μm, and preferably 10 to 150 μm.

[0281] Known methods for applying a polymerizable liquid crystal composition to a substrate, etc. include spin coating, extrusion, gravure coating, die coating, bar coating, applicator coating, and printing methods such as flexographic methods.

[0282] Subsequently, a dry film is formed by removing the solvent through drying or the like. Examples of drying methods include natural drying, air drying, heat drying, and vacuum drying. At this time, by heating the film obtained from the polymerizable liquid crystal composition, the solvent is dried and removed from the film, and the polymerizable liquid crystal compound can be oriented in a desired direction (e.g., horizontal or vertical direction) with respect to the film plane. The heating temperature of the film can be appropriately determined by considering the polymerizable liquid crystal compound used and the material of the substrate forming the film, but in order to transition the polymerizable liquid crystal compound to a liquid crystal state, it is typically necessary to have a temperature above the liquid crystal phase transition temperature.

[0283] In order to remove the solvent included in the polymerizable liquid crystal composition and to bring the polymerizable liquid crystal compound to a desired orientation state, for example, the polymerizable liquid crystal compound included in the polymerizable liquid crystal composition may be heated to a temperature above the liquid crystal phase transition temperature (smectic phase transition temperature or nematic phase transition temperature) of the polymerizable liquid crystal compound.

[0284] The polymerizable liquid crystal composition of the present invention comprises a polymerizable liquid crystal compound (1) and a polymerizable liquid crystal compound (2), and typically, each polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2) can be transitioned to a liquid crystal phase at a temperature lower than the temperature at which they transition to a liquid crystal phase. In one embodiment of the present invention, the solid-liquid crystal phase transition temperature of the polymerizable liquid crystal mixture constituting the polymerizable liquid crystal composition of the present invention is preferably 25°C or higher and 153°C or lower. If the phase transition temperature to the liquid crystal phase is within the above range, a liquid crystal cured film can be manufactured at a lower processing temperature, thereby enabling the production of a liquid crystal cured film having high optical properties inherently exhibited by the polymerizable liquid crystal compound while suppressing the degradation of optical properties caused by heating. Furthermore, in the manufacture of a phase difference film using the polymerizable liquid crystal composition of the present invention, excessive consumption of thermal energy can be suppressed, thereby improving production efficiency. In addition, since the liquid crystal phase transition can be performed by heating at a relatively low temperature, there is also an advantage such as widening the options for the support substrate to which the polymerizable liquid crystal composition is applied. In the present invention, the solid-to-liquid crystal phase transition temperature of the polymerizable liquid crystal mixture is typically 40°C or higher, more preferably 50°C or higher, and even more preferably 60°C or higher, from the perspective that the resulting liquid crystal cured film is a compound capable of exhibiting inverse wavelength dispersion characteristics; and more preferably 150°C or lower, even more preferably 145°C or lower, and particularly preferably 144°C or lower, from the perspective of achieving a more significant effect of the present invention.

[0285] In addition, the liquid crystal phase transition temperature can be measured using, for example, a polarizing microscope equipped with a temperature control stage, a differential scanning calorimeter (DSC), a thermogravimetric differential thermal analysis device (TG-DTA), etc. The phase transition temperature in the polymerizable liquid crystal mixture of the present invention comprising at least two types of polymerizable liquid crystal compounds refers to a temperature measured using a mixture of polymerizable liquid crystal compounds in which the total polymerizable liquid crystal compounds constituting the polymerizable liquid crystal mixture are mixed in the same ratio as the composition in the polymerizable liquid crystal mixture.

[0286] The heating time can be appropriately determined depending on the heating temperature, the type of polymerizable liquid crystal compound used, the type of solvent, its boiling point and amount, etc., but typically it is 15 seconds to 10 minutes, and preferably 0.5 to 5 minutes.

[0287] The removal of the solvent from the coating film may be carried out simultaneously with heating above the liquid crystal phase transition temperature of the polymerizable liquid crystal compound or separately, but it is preferable to carry out the removal simultaneously for the sake of productivity improvement. Before heating above the liquid crystal phase transition temperature of the polymerizable liquid crystal compound, a preliminary drying process may be provided to appropriately remove the solvent from the coating film under conditions where the polymerizable liquid crystal compound contained in the coating film obtained from the polymerizable liquid crystal composition is not polymerized. Examples of drying methods in such a preliminary drying process include natural drying, air drying, heat drying, and vacuum drying, and the drying temperature (heating temperature) in the drying process can be appropriately determined according to the type of polymerizable liquid crystal compound used, the type of solvent, its boiling point, and its amount.

[0288] Subsequently, in the obtained dried film, a liquid crystal cured film is formed by polymerizing the polymerizable liquid crystal compound by light irradiation while maintaining the orientation state of the polymerizable liquid crystal compound, which is a polymer of the polymerizable liquid crystal compound existing in a desired orientation state. Since the polymerizable liquid crystal composition of the present invention can be highly polymerized by light irradiation such as high-intensity ultraviolet light while suppressing damage to the polymerizable liquid crystal compound, photopolymerization is typically used as the polymerization method. In photopolymerization, the light irradiated onto the dried film is appropriately selected according to the type of polymerization initiator, the type of polymerizable liquid crystal compound, and the amount thereof included in the dried film. Specific examples thereof may include one or more types of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, and γ-rays, or active electron beams. Among these, ultraviolet light is preferred due to the ease of controlling the progress of the polymerization reaction and the ability to use photopolymerization devices that are widely used in the field. It is also desirable to select the type of polymerizable liquid crystal compound or polymerization initiator contained in the polymerizable liquid crystal composition so that photopolymerization is possible by ultraviolet light. Furthermore, the polymerization temperature can be controlled by irradiating light while cooling the dried film with an appropriate cooling means during polymerization. By employing such cooling means, polymerization of the polymerizable liquid crystal compound can be carried out at a lower temperature, allowing a liquid crystal cured film to be formed properly even if a substrate with relatively low heat resistance is used. Additionally, it is possible to accelerate the polymerization reaction by increasing the polymerization temperature within a range where problems caused by heat during light irradiation (such as deformation of the substrate due to heat) do not occur. A patterned cured film can also be obtained by performing masking or development during photopolymerization.

[0289] Examples of light sources for the above active energy lines include, for instance, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, halogen lamps, carbon arc lamps, tungsten lamps, gallium lamps, excimer lasers, LED light sources emitting light in a wavelength range of 380 to 440 nm, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, etc.

[0290] The ultraviolet irradiation intensity is typically 10 to 3,000 mW / cm². The ultraviolet irradiation intensity is preferably an intensity in a wavelength range effective for activating the photopolymerization initiator. The time for irradiating light is typically 0.1 seconds to 10 minutes, preferably 0.1 seconds to 5 minutes, more preferably 0.1 seconds to 3 minutes, and even more preferably 0.1 seconds to 1 minute. When irradiated once or multiple times with such ultraviolet irradiation intensity, the accumulated light amount is 10 to 3,000 mJ / cm², preferably 50 to 2,000 mJ / cm², and more preferably 100 to 1,000 mJ / cm².

[0291] The thickness of the liquid crystal curing film can be appropriately selected depending on the applied display device, preferably 0.2 to 3 μm, more preferably 0.2 to 2 μm.

[0292] A film of the polymerizable liquid crystal composition may be formed on an alignment layer. The alignment layer possesses an orientation regulating force that aligns the polymerizable liquid crystal compound in a desired direction. For example, there are horizontal alignment layers having an orientation regulating force that aligns the polymerizable liquid crystal compound in a horizontal direction, and vertical alignment layers having an orientation regulating force that aligns it in a vertical direction. The orientation regulating force can be arbitrarily adjusted by the type of alignment layer, surface condition, rubbing conditions, etc., and if the alignment layer is formed of a photo-alignable polymer, it can be arbitrarily adjusted by polarized light irradiation conditions, etc.

[0293] As for the alignment film, it is desirable to have solvent resistance such that it is not dissolved by the application of a polymerizable liquid crystal composition, and also to have heat resistance during the removal of the solvent or heat treatment for the orientation of the polymerizable liquid crystal compound described later. Examples of alignment films include an alignment film comprising an oriented polymer, a photoalignment film, a groove alignment film having an uneven pattern or a plurality of grooves on its surface, and a stretched film stretched in the orientation direction; a photoalignment film is preferred from the perspective of the precision of the alignment angle and quality.

[0294] Examples of orientation polymers include polyamides or gelatins having amide bonds within the molecule, polyimides having imide bonds within the molecule and polyamic acids, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyoxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid, and polyacrylic acid esters. Among these, polyvinyl alcohol is preferred. Orientation polymers may be used alone or in combination of two or more types.

[0295] An alignment film comprising an oriented polymer is typically obtained by applying a composition in which the oriented polymer is dissolved in a solvent (hereinafter referred to as an "oriented polymer composition") to a substrate and removing the solvent, or by applying the oriented polymer composition to a substrate, removing the solvent, and rubbing (rubbing method). As for the solvent, the same as the solvents previously exemplified can be used as solvents for polymerizable liquid crystal compositions.

[0296] The concentration of the oriented polymer in the oriented polymer composition may be within a range where the oriented polymer material can be completely dissolved in a solvent, and is preferably 0.1 to 20% in terms of solid content relative to the solution, and more preferably about 0.1 to 10%.

[0297] As an oriented polymer composition, commercially available alignment film materials may be used as is. Examples of commercially available alignment film materials include SunEver (registered trademark, manufactured by Nissan Chemical Industry Co., Ltd.) and Optimo (registered trademark, manufactured by JSR Corporation).

[0298] A method for applying an oriented polymer composition to a substrate can be the same as the method exemplified for applying a polymerizable liquid crystal composition to a substrate.

[0299] Methods for removing solvents included in an oriented polymer composition include natural drying, ventilation drying, heat drying, and vacuum drying.

[0300] In order to impart orientation regulating force to the orientation film, a rubbing treatment may be performed as needed (rubbing method). An example of a method for imparting orientation regulating force by the rubbing method is a method in which an orientation polymer composition is applied to a substrate and annealed to a rubbing roll that is wound and rotating, thereby bringing the orientation polymer film formed on the surface of the substrate into contact with the substrate. If masking is performed when performing the rubbing treatment, multiple regions (patterns) with different orientation directions may be formed on the orientation film.

[0301] A photoalignment film is typically obtained by applying a composition (hereinafter also referred to as a "composition for forming a photoalignment film") comprising a polymer or monomer having photoreactive groups and a solvent to a substrate, and then irradiating polarized light (preferably polarized UV) after removing the solvent. The photoalignment film is also advantageous in that the direction of the orientation regulating force can be arbitrarily controlled by selecting the polarization direction of the irradiated polarized light.

[0302] A photoreactive group refers to a group that generates liquid crystal orientation ability upon light irradiation. Specifically, it may include a group involved in photoreactions that are the origin of liquid crystal orientation ability, such as molecular orientation induction, isomerization, dimerization, photocrosslinking, or photodecomposition reactions, which are caused by light irradiation. Among these, a group involved in dimerization or photocrosslinking is preferred in that it exhibits excellent orientation. As a photoreactive group, a group having an unsaturated bond, particularly a double bond, is preferred, and a group having at least one selected from the group consisting of a carbon-carbon double bond (C=C bond), a carbon-nitrogen double bond (C=N bond), a nitrogen-nitrogen double bond (N=N bond), and a carbon-oxygen double bond (C=O bond) is particularly preferred.

[0303] Examples of photoreactive groups having a C=C bond include vinyl groups, polyene groups, stilbene groups, stilbasol groups, stilbazolium groups, chalcone groups, and cinnamoyl groups.

[0304] Examples of photoreactive groups having a C=N bond include groups having structures such as aromatic Schiff bases and aromatic hydrazones. Examples of photoreactive groups having an N=N bond include azobenzene groups, azonaphthalene groups, aromatic heterocyclic azo groups, bis-azo groups, forma groups, and groups having azoxybenzene structures. Examples of photoreactive groups having a C=O bond include benzophenone groups, coumarin groups, anthraquinone groups, and maleimide groups. These groups may have substituents such as alkyl groups, alkoxy groups, aryl groups, allyloxy groups, cyano groups, alkoxycarbonyl groups, hydroxyl groups, sulfonic acid groups, and alkyl halide groups.

[0305] Among these, cinnamoyl groups and chalcone groups are preferred because they allow for the formation of a photo-aligned film that is easy to obtain, has a photoreactive group involved in photodimerization, requires a relatively small amount of polarized light irradiation for photoorientation, and has excellent thermal stability and time-dependent stability. As for the polymer having photoreactive groups, it is particularly preferred that the end portion of the polymer side chain has a cinnamoyl group having a cinnamic acid structure.

[0306] A photo-alignment-inducing layer can be formed on a substrate by applying a composition for forming a photo-alignment layer onto the substrate. As for the solvent included in the composition, the same as the solvent previously exemplified as a solvent usable in polymerizable liquid crystal compositions may be cited, and it can be appropriately selected according to the solubility of the polymer or monomer having photoreactive groups.

[0307] The content of a polymer or monomer having a photoreactive group in a composition for forming a photoalignment film can be appropriately adjusted depending on the type of polymer or monomer or the thickness of the intended photoalignment film, but it is preferable to have at least 0.2 mass% with respect to the mass of the composition for forming a photoalignment film, and a range of 0.3 to 10 mass% is more preferable. Within a range where the characteristics of the photoalignment film are not significantly impaired, the composition for forming a photoalignment film may include polymer materials such as polyvinyl alcohol or polyimide or a photosensitizer.

[0308] A method for applying a composition for forming a photo-alignment film to a substrate is the same as a method for applying an oriented polymer composition to a substrate. Methods for removing the solvent from the applied composition for forming a photo-alignment film include, for example, natural drying, ventilation drying, heat drying, and vacuum drying.

[0309] To irradiate polarized light, the method may involve directly irradiating polarized UV light onto the composition for forming a photoalignment film coated on a substrate from which the solvent has been removed, or by irradiating polarized light from the substrate side and transmitting the polarized light. Furthermore, it is particularly preferable that the polarized light be substantially parallel light. The wavelength of the polarized light to be irradiated should be in a wavelength range in which the photoreactive groups of a polymer or monomer having photoreactive groups can absorb light energy. Specifically, UV (ultraviolet) light in the wavelength range of 250 to 400 nm is particularly preferred. Examples of light sources used for the polarized light irradiation include xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and ultraviolet lasers such as KrF and ArF, with high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps being more preferred. Among these, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps are preferred because they have a high emission intensity of ultraviolet light at a wavelength of 313 nm. Polarized UV can be irradiated by passing light from the above light source through a suitable polarizer. As such a polarizer, a polarizing filter, a polarizing prism such as a Glen Thomson or Glen Taylor, or a wire grid type polarizer can be used.

[0310] In addition, if masking is performed when rubbing or polarizing irradiation is performed, multiple regions (patterns) with different liquid crystal orientation directions may be formed.

[0311] A groove alignment film is a film having an uneven pattern or a plurality of grooves on the film surface. When a polymerizable liquid crystal compound is applied to a film having a plurality of straight grooves arranged at equal intervals, liquid crystal molecules are oriented along the grooves.

[0312] Methods for obtaining a groove alignment film include: a method of forming an uneven pattern by interposing an exposure mask having a pattern-shaped slit on the surface of a photosensitive polyimide film, and then performing development and rinsing treatments after exposure; a method of forming a layer of UV-curing resin before curing on a plate-shaped disc having grooves on the surface, transferring the formed resin layer to a substrate and then curing it; and a method of forming unevenness by pressing a roll-shaped disc having multiple grooves against a film of UV-curing resin before curing formed on a substrate, and then curing it.

[0313] In addition, as a material exhibiting an orientation restricting force that orients a polymerizable liquid crystal compound in a direction perpendicular to the plane of the liquid crystal curing film, in addition to the orientation polymers described above, fluorine-based polymers such as perfluoroalkyls, silane compounds, and polysiloxane compounds obtained by the condensation reaction thereof may be used.

[0314] When using a silane compound as a material for forming an alignment film, a compound containing Si and C elements in its constituent elements is preferred and a silane compound can be preferably used, from the perspective of easily lowering surface tension and easily increasing adhesion to a layer adjacent to the alignment film. Silane-containing ionic compounds, etc., can be used as the silane compound, and by using such a silane compound, the vertical orientation restrictive force can be increased. As for the silane compound, one type may be used alone, two or more types may be used in combination, or it may be used mixed with other materials. When the silane compound is a nonionic silane compound, a silane compound having an alkyl group at the molecular end is preferred from the perspective of easily increasing the vertical orientation restrictive force, and a silane compound having an alkyl group having 3 to 30 carbon atoms is more preferred.

[0315] The thickness of the alignment layer (an alignment layer or photoalignment layer containing an oriented polymer) is typically in the range of 10 to 10,000 nm, preferably in the range of 10 to 1,000 nm, more preferably in the range of 10 to 500 nm, even more preferably in the range of 10 to 300 nm, and particularly preferably in the range of 50 to 250 nm.

[0316] The present invention includes a polarizing plate (elliptical polarizing plate) comprising a phase difference film of the present invention. The polarizing plate of the present invention typically includes a phase difference film and a polarizing film of the present invention.

[0317] A polarizing film is a film having a polarizing function, and examples include a film containing a polarizer that is a stretched film adsorbed with a pigment having absorption anisotropy or a film coated with a pigment having absorption anisotropy. Examples of pigments having absorption anisotropy include dichroic pigments.

[0318] A film comprising a polarizer having an absorption anisotropy and adsorbed as a stretched film is typically manufactured by uniaxially stretching a polyvinyl alcohol-based resin film, dyeing the polyvinyl alcohol-based resin film with a dichroic pigment to adsorb the dichroic pigment, treating the polyvinyl alcohol-based resin film with the adsorbed dichroic pigment with an aqueous boric acid solution, and washing with water after treatment with the aqueous boric acid solution, and then clamping a transparent protective film with an adhesive interposed on at least one surface of the polarizer.

[0319] Polyvinyl alcohol-based resins are obtained by saponifying polyvinyl acetate-based resins. As polyvinyl acetate-based resins, in addition to polyvinyl acetate, which is a homopolymer of vinyl acetate, copolymers of vinyl acetate and other monomers copolymerizable thereto are used. Examples of other monomers copolymerizable to vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having ammonium groups.

[0320] The degree of saponification of the polyvinyl alcohol-based resin is typically about 85 to 100 mol%, and preferably 98 mol% or more. The polyvinyl alcohol-based resin may be modified, and for example, polyvinyl formal or polyvinyl acetal modified with aldehydes may be used. The degree of polymerization of the polyvinyl alcohol-based resin is typically about 1,000 to 10,000, and preferably in the range of 1,500 to 5,000.

[0321] A polyvinyl alcohol-based resin of this type is used as a base film for a polarizing film. The method of forming the polyvinyl alcohol-based resin is not particularly limited and can be formed by a known method. The film thickness of the polyvinyl alcohol-based base film can be, for example, about 10 to 150 μm.

[0322] Uniaxial stretching of a polyvinyl alcohol-based resin film can be performed before, simultaneously with, or after dyeing with a dichroic dye. When uniaxial stretching is performed after dyeing, this uniaxial stretching may be performed before or during boric acid treatment. It is also possible to perform uniaxial stretching at multiple of these stages. Uniaxial stretching may be performed uniaxially between rolls of different peripheral speeds or uniaxially using a hot roll. Furthermore, uniaxial stretching may be dry stretching performed in the atmosphere or wet stretching performed while the polyvinyl alcohol-based resin film is swollen using a solvent. The stretching ratio is typically about 3 to 8 times.

[0323] Dyeing of a polyvinyl alcohol-based resin film with a dichroic dye is carried out, for example, by a method of immersing the polyvinyl alcohol-based resin film in an aqueous solution containing a dichroic dye.

[0324] Specifically, iodine or dichroic organic dyes are used as dichroic pigments. Examples of dichroic organic dyes include dichroic direct dyes composed of disazo compounds such as CI DIRECT RED 39, and dichroic direct dyes composed of compounds such as trisazo and tetrakisazo. It is preferable to perform a water immersion treatment on the polyvinyl alcohol-based resin film before dyeing.

[0325] When iodine is used as a dichroic dye, a method of dyeing by immersing a polyvinyl alcohol-based resin film in an aqueous solution containing iodine and potassium iodide is typically employed.

[0326] The iodine content in this aqueous solution is typically about 0.01 to 1 part by mass per 100 parts by mass of water. Also, the potassium iodide content is typically about 0.5 to 20 parts by mass per 100 parts by mass of water. The temperature of the aqueous solution used for dyeing is typically about 20 to 40°C. Also, the immersion time (dyeing time) in this aqueous solution is typically about 20 to 1,800 seconds.

[0327] Meanwhile, when a dichroic organic dye is used as a dichroic pigment, a method of dyeing by immersing a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic dye is typically employed.

[0328] The content of the dichroic organic dye in this aqueous solution is typically 1 × 10⁻⁶ per 100 parts by mass of water. -4 It is approximately 10 parts by mass, preferably 1 × 10 -3 ~ 1 part by mass, and more preferably 1 × 10 -3 ~ 1 × 10 -2It is a part by mass. This aqueous solution may contain an inorganic salt, such as sodium sulfate, as a dyeing aid. The temperature of the aqueous solution of the dichroic dye used for dyeing is typically about 20 to 80°C. Also, the immersion time (dyeing time) in this aqueous solution is typically about 10 to 1,800 seconds.

[0329] Boric acid treatment after dyeing with a dichroic dye can typically be carried out by immersing the dyed polyvinyl alcohol-based resin film in an aqueous boric acid solution. The boric acid content in this aqueous boric acid solution is typically about 2 to 15 parts by mass per 100 parts by mass of water, and preferably 5 to 12 parts by mass. When iodine is used as the dichroic dye, it is preferable that this aqueous boric acid solution contains potassium iodide, and in that case, the potassium iodide content is typically about 0.1 to 15 parts by mass per 100 parts by mass of water, and preferably 5 to 12 parts by mass. The immersion time in the aqueous boric acid solution is typically about 60 to 1,200 seconds, preferably 150 to 600 seconds, and more preferably 200 to 400 seconds. The temperature of the boric acid treatment is typically 50°C or higher, preferably 50 to 85°C, and more preferably 60 to 80°C.

[0330] The polyvinyl alcohol-based resin film after boric acid treatment is typically washed with water. The washing treatment can be carried out, for example, by immersing the boric acid-treated polyvinyl alcohol-based resin film in water. The temperature of the water during the washing treatment is typically about 5 to 40°C.

[0331] Also, the immersion time is typically about 1 to 120 seconds.

[0332] After washing, a drying treatment is performed to obtain a polarizer. The drying treatment can be carried out, for example, using a hot air dryer or a far-infrared heater. The temperature of the drying treatment is typically about 30 to 100°C, and preferably 50 to 80°C. The time of the drying treatment is typically about 60 to 600 seconds, and preferably 120 to 600 seconds. Through the drying treatment, the moisture content of the polarizer is reduced to a practical level. The moisture content is typically about 5 to 20 mass%, and preferably 8 to 15 mass%. If the moisture content is within the above range, it is easy to obtain a polarizer having appropriate flexibility and excellent thermal stability.

[0333] The thickness of the polarizer obtained by uniaxially stretching, dyeing with a dichroic dye, treating with boric acid, washing, and drying a polyvinyl alcohol-based resin film in this way is preferably 5 to 40 μm.

[0334] Examples of films coated with a pigment having absorption anisotropy include a composition containing a dichroic pigment having liquid crystallization, or a film obtained by coating a composition containing a dichroic pigment and a polymerizable liquid crystal. The film preferably has a protective film on one or both sides thereof. Examples of the protective film include the same resin film exemplified above as a substrate that can be used to manufacture a liquid crystal curing film.

[0335] A film coated with a pigment having absorption anisotropy is preferably thin, but if it is excessively thin, the strength is reduced and processability tends to decrease. The thickness of the film is typically 20 μm or less, preferably 5 μm or less, and more preferably 0.5 to 3 μm.

[0336] Specifically, examples of films coated with a pigment having the above-mentioned absorption anisotropy include films described in Japanese Patent Publication No. 2012-33249, etc.

[0337] The polarizing film may have a transparent protective film laminated on at least one surface of the polarizer obtained in this way, with an adhesive interposed therebetween. As the transparent protective film, a transparent film identical to the resin film exemplified above may preferably be used as a substrate that can be used to manufacture a liquid crystal curing film.

[0338] The polarizing plate of the present invention is composed of a phase difference film and a polarizing film of the present invention, and, for example, an elliptical polarizing plate of the present invention can be obtained by laminating the phase difference film and the polarizing film of the present invention with an adhesive layer or a pressure-sensitive adhesive layer interposed therein.

[0339] In one embodiment of the present invention, when a phase difference film of the present invention comprising a horizontally oriented liquid crystal curing film and a polarizing film are laminated, it is preferable to laminate them such that the angle formed by the ground axis (optical axis) of the horizontally oriented liquid crystal curing film constituting the phase difference film and the absorption axis of the polarizing film is 45 ± 5°.

[0340] The polarizing plate of the present invention may have a configuration such as that of a conventional general elliptical polarizing plate, or a polarizing film and a phase difference film. Examples of such configurations include an adhesive layer (sheet) for bonding the elliptical polarizing plate to a display element such as an organic EL, and a protect film used to protect the surface of the polarizing film or phase difference film from scratches or contamination.

[0341] The polarizing plate of the present invention can be used in various display devices, particularly optical displays.

[0342] A display device is a device having a display element, and includes a light-emitting element or a light-emitting device as a light source. Examples of display devices include liquid crystal displays, organic electroluminescence (EL) displays, inorganic electroluminescence (EL) displays, touch panel displays, electron emission displays (e.g., field emission displays (FEDs), surface field emission displays (SEDs)), electronic paper (display devices using electronic ink or electrophoretic elements, plasma displays, projection displays (e.g., grating light valve (GLV) displays, displays having digital micromirror devices (DMDs)), and piezoelectric ceramic displays. Liquid crystal displays include all types of transmissive liquid crystal displays, transflective liquid crystal displays, reflective liquid crystal displays, direct-view liquid crystal displays, and projection liquid crystal displays. These display devices may be display devices that display two-dimensional images or stereoscopic display devices that display three-dimensional images. In particular, the elliptical polarizer of the present invention is preferably used in organic electroluminescence (EL) displays and inorganic electroluminescence (EL) displays. These display devices (optical displays) can exhibit good image display characteristics by being equipped with the polarizing plate of the present invention, which has excellent optical properties.

[0343] Examples

[0344] The present invention will be explained in more detail below through examples. In addition, "%" and "parts" in the examples refer to mass % and mass parts, respectively, unless otherwise noted.

[0345] [HPLC Measurement]

[0346] HPLC measurement may be performed under any condition that allows for the separation of peaks originating from the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2). An example of HPLC measurement conditions is shown below.

[0347] (Measurement conditions)

[0348] Measuring device: HPLC LC-10AT (Manufactured by Shimadzu Corporation)

[0349] Column: L-Column ODS (Inner diameter 3.0 mm, Length 150 mm, Particle size 3 µm) Temperature: 40 ℃

[0350] Mobile phase A: 0.1 % (v / v)-TFA / water

[0351] Mobile Phase B: 0.1 % (v / v)-TFA / acetonitrile

[0352] Gradient: 0 min 70 %-B

[0353] 30 min 100 %-B

[0354] 60 min 100 %-B

[0355] 60.01 min 70 %-B

[0356] 75 min 70 %-B

[0357] Flow rate: 0.5 mL / min

[0358] Injection volume: 5 μL

[0359] Detection wavelength: 254 nm

[0360] <Preparation of Polymerizable Liquid Crystal Compounds>

[0361] Synthesis Example 1: Preparation of a polymerizable liquid crystal compound (2)

[0362] A polymerizable liquid crystal compound represented by the following formula (2-1-1) (hereinafter referred to as "polymerizable liquid crystal compound (2-1-1)") was synthesized according to the following scheme.

[0363] [Chemical Formula 42]

[0364]

[0365] A nitrogen atmosphere was created inside a 100 mL four-necked flask equipped with a Dimrod condenser and a thermometer, and 11.02 g of compound (E-1) synthesized with reference to Patent Document (Japanese Patent Publication No. 2010-31223), 4.22 g of compound (D-2) synthesized with reference to Patent Document (Japanese Patent Publication No. 2011-207765), 0.02 g of DMAP (manufactured by Wako Pure Chemical Industry Co., Ltd.), 0.20 g of BHT (manufactured by Wako Pure Chemical Industry Co., Ltd.), and 58 g of chloroform (manufactured by Kanto Chemical Co., Ltd.) were added and mixed. Then, 4.05 g of IPC (manufactured by Wako Pure Chemical Industry Co., Ltd.) was additionally added using a dropping funnel, and the mixture was reacted overnight at 0°C. After the reaction was completed, insoluble components were removed by filtration. The obtained chloroform solution was added dropwise to acetonitrile (manufactured by Wako Pure Chemical Industry Co., Ltd.) at a mass three times that of the chloroform contained in the solution, and a solid was precipitated. Subsequently, the precipitated solid was removed by filtration, washed three times with 20 g of acetonitrile, and dried under reduced pressure at 30°C to obtain 11.75 g of polymerizable liquid crystal compound (2-1-1). The yield of the polymerizable liquid crystal compound (2-1-1) was 81% based on compound (D-2).

[0366] Synthesis Example 2: Preparation of a mixture of polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2)

[0367] [Chemical Formula 43]

[0368]

[0369] A 100 mL four-necked flask equipped with a Dimrod condenser and a thermometer was placed under a nitrogen atmosphere, and 10.91 g of compound (E-1), 4.22 g of compound (D-2), 0.06 g of compound (F-3) (manufactured by Wako Pure Chemical Industry Co., Ltd.), 0.02 g of DMAP (manufactured by Wako Pure Chemical Industry Co., Ltd.), 0.20 g of BHT (manufactured by Wako Pure Chemical Industry Co., Ltd.), and 58 g of chloroform (manufactured by Kanto Chemical Co., Ltd.) were added and mixed. Then, 4.05 g of IPC (manufactured by Wako Pure Chemical Industry Co., Ltd.) was additionally added using a dropping funnel, and the mixture was reacted overnight at 0°C. After the reaction was completed, insoluble components were removed by filtration. The obtained chloroform solution was added dropwise to acetonitrile (manufactured by Wako Pure Pharmaceutical Industry Co., Ltd.) with a mass three times that of the chloroform contained in the solution, and a solid was precipitated.

[0370] Subsequently, the precipitated solid was removed by filtration, washed three times with 20 g of acetonitrile, and dried under reduced pressure at 30 ℃ to obtain 12.34 g of a mixture of polymerizable liquid crystal compound (2-1-1) and polymerizable liquid crystal compound (1-1-1). The obtained mixture contained 5.0% of the polymerizable liquid crystal compound (1-1-1) relative to the total mass of the mixture. The yield of the mixture was 85.0% based on compound (D-2). In addition, n in the above formula (1-1-1) is n = 2.

[0371] Synthesis Examples 3 to 13

[0372] Liquid crystal mixtures (1) to (12) containing a polymerizable liquid crystal compound (2-1-1) and any one of each polymerizable liquid crystal compound (1-1-2) to (1-1-10) were prepared in the same manner as in Synthesis Example 2, except that a compound (F-4) to (F-10), (F-1) or (F-2) shown in Table 1 was used instead of compound (F-3). Additionally, polymerizable liquid crystal compounds (1-1-2) to (1-1-10) each have a structure in which the propylene group in the structure represented by -O-CO-(C3H6)-CO-O- in the above formula (1-1-1) is substituted with an aliphatic hydrocarbon group or a dicyclic group derived from compounds (F-4) to (F-10), (F-1) or (F-2).

[0373]

[0374] <Solubility Evaluation>

[0375] At 25°C, 1.00 g of N-methylpyrrolidone (NMP) and a stirrer were placed in a vial, and the synthetic compounds were added while stirring with a magnetic stirrer (HS-30DN, As One) until a dissolved residue was visually confirmed. At the point when the dissolved residue was confirmed, the solubility of each liquid crystal mixture and polymerizable liquid crystal compound in NMP was calculated as a weight percentage concentration from (weight of each liquid crystal mixture and polymerizable liquid crystal compound) / (weight of each liquid crystal mixture and polymerizable liquid crystal compound + weight of NMP). The results are shown in Table 3.

[0376] <Preparation of Polymerizable Liquid Crystal Composition>

[0377] Example 1

[0378] A liquid crystal mixture (1) of the polymerizable liquid crystal compound (1-1-1) obtained in Synthesis Example 2 and the polymerizable liquid crystal compound (2-1-1) was introduced into a vial, a polymerization initiator, a leveling agent, a polymerization inhibitor, and a solvent were injected according to the composition listed in Table 2, and the mixture was stirred at 80°C for 30 minutes using a carousel to obtain a polymerizable liquid crystal composition (1).

[0379] In addition, the amounts of polymerization initiator, leveling agent, and polymerization inhibitor shown in Table 2 are the injection amounts per 100 parts by mass of the liquid crystal mixture (1). Also, the amount of solvent is set so that the mass % of the solid content is 13% of the total amount of the polymerizable liquid crystal composition.

[0380]

[0381] Polymerization initiator: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one (Irgacure 369; manufactured by BASF Japan)

[0382] Leveling agent: Polyacrylate compound (BYK-361N; manufactured by Big Chem Japan)

[0383] Polymerization Inhibitor: BHT (Manufactured by Wako Pure Chemical Industry Co., Ltd.)

[0384] Solvent: N-methylpyrrolidone (NMP; manufactured by Kanto Chemical Co., Ltd.)

[0385] Example 2

[0386] A polymerizable liquid crystal composition (2) was obtained in the same manner as in Example 1, except that 510 mg of a liquid crystal mixture (2) of the polymerizable liquid crystal compound (1-1-2) obtained in Synthesis Example 3 and the polymerizable liquid crystal compound (2-1-1) obtained in Synthesis Example 3 were mixed and used, and 490 mg of the compound (2-1-1) obtained in Synthesis Example 1 was mixed and used. HPLC analysis was performed under the above measurement conditions using the obtained polymerizable liquid crystal composition (2), and the area percentage value of the polymerizable liquid crystal compound (1-1-2) was calculated based on the total amount of the polymerizable liquid crystal compound (2-1-1) and the polymerizable liquid crystal compound (1-1-2).

[0387] Examples 3 to 8 and 10 to 12

[0388] Polymerizable liquid crystal compositions (3) to (8) and (10) to (12) were obtained in the same manner as in Example 1, except that liquid crystal mixtures (2) to (10) were used instead of liquid crystal mixture (1).

[0389] Example 9

[0390] A polymerizable liquid crystal composition (9) was obtained in the same manner as in Example 1, except that 500 mg of a liquid crystal mixture (8) of the polymerizable liquid crystal compound (1-1-6) obtained in Synthesis Example 9 and the polymerizable liquid crystal compound (2-1-1) obtained in Synthesis Example 1 was mixed and used as the polymerizable liquid crystal compound. Using the obtained polymerizable liquid crystal composition (9), HPLC analysis was performed under the above measurement conditions, and the area percentage value of the polymerizable liquid crystal compound (1-1-6) was measured based on the total amount of the polymerizable liquid crystal compound (2-1-1) and the polymerizable liquid crystal compound (1-1-6).

[0391] Comparative Example 1

[0392] A polymerizable liquid crystal composition (13) was obtained in the same manner as in Example 1, except that the polymerizable liquid crystal compound (2-1-1) obtained in Synthesis Example 1 was used instead of the liquid crystal mixture (1).

[0393] Comparative Examples 2 and 3

[0394] Polymerizable liquid crystal compositions (14) and (15) were obtained in the same manner as in Example 1, except that instead of the liquid crystal mixture (1), the liquid crystal mixture (11) or (12) obtained in Synthesis Example 12 or 13, respectively, according to Table 3 was used.

[0395] <Measurement of Phase Transition Temperature>

[0396] The liquid crystal mixtures used in the polymerizable liquid crystal compositions (1) to (15) were each weighed in a vial at a rate of 1000 mg and dissolved by adding an additional 2 g of chloroform. The resulting solution was applied to a glass substrate formed with a PVA alignment film that had undergone rubbing treatment and dried. The substrate was placed on a cooling heating device ("LNP94-2" manufactured by Japan Hitech Co., Ltd.) and heated from room temperature to 180 ℃, then cooled to room temperature. The appearance during temperature change was observed using a polarizing microscope (LEXT, manufactured by Olympus), and the temperature at which the nematic phase was formed was measured and set as the nematic phase transition temperature.

[0397] The results are shown in Table 3.

[0398]

[0399] <Measurement of Optical Properties (α Value)>

[0400] For polymerizable liquid crystal compositions (1), (3), (4), (6), (8), (10) to (12) and (15) in which M in formula (1) is an aliphatic hydrocarbon group, optical films (phase difference films) were prepared and optical properties were evaluated. The results are shown in Table 4.

[0401] [Preparation of a composition for forming a light alignment film]

[0402] A composition for forming a photo-alignment film was obtained by mixing the following components and stirring the resulting mixture at 80°C for 1 hour.

[0403] Photo-oriented materials represented by the following formula (Part 5):

[0404] [Chemical Formula 44]

[0405]

[0406] (Number average molecular weight: approx. 28,000)

[0407] Solvent (Part 95): Cyclopentanone

[0408] [Manufacturing of Optical Film (Phase Difference Film)]

[0409] An optical film was manufactured as follows. A cycloolefin polymer film (COP) (ZF-14, manufactured by Nippon Zeon Co., Ltd.) was treated once using a corona treatment device (AGF-B10, manufactured by Kasuga Electric Co., Ltd.) under conditions of an output of 0.3 kW and a processing speed of 3 m / min. The above composition for forming a photo-alignment film was applied to the corona-treated surface using a bar coater, dried at 80°C for 1 minute, and polarized UV exposure was performed using a polarized UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Electric Co., Ltd.) with an integrated light amount of 100 mJ / cm². The film thickness of the obtained alignment film was measured using a laser microscope (LEXT, manufactured by Olympus Corporation) and was found to be 100 nm.

[0410] Polymerizable liquid crystal compositions (1), (3), (4), (6), (8), (10) to (12) and (15) were each coated onto an alignment film using a bar coater, dried at 120°C for 1 minute, and then an optical film was prepared by irradiating with ultraviolet light using a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by Ushio Electric Co., Ltd.) (under a nitrogen atmosphere, wavelength: 365 nm, integrated light intensity at wavelength 365 nm: 1000 mJ / cm²).

[0411] The optical film prepared above was used as a measurement sample, and a measuring instrument ("KOBRA-WR" manufactured by Oji Measuring Instruments Co., Ltd.) was used to measure the front phase difference value for light with wavelengths of 450 nm and 550 nm, and the α value = Re(450) / Re(550) was calculated.

[0412]

Claims

Claim 1 A polymerizable liquid crystal compound represented by formula (1). [In Equation (1), k11, k12 and l each independently represent integers greater than or equal to 1; B 11 and B 12 is, each independently, -CR 1 R 2 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S- or representing a single bond, R 1 and R 2 Each represents, independently, a hydrogen atom, a fluorine atom, or a C1-C4 alkyl group;E 11 and E 12 is, each independently, -CR 1 R 2 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S- or represents a single bond ;G 11 and G 12 Each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, and the hydrogen atoms included in the alicyclic hydrocarbon group are halogen atoms, -R 3 , -OR 3 , may be substituted with a cyano group or a nitro group, and the -CH2- included in the alicyclic hydrocarbon group may be substituted with -O-, -S- or -NH-, and R 3 ... represents an alkyl group having 1 to 4 carbon atoms, and the hydrogen atoms included in the alkyl group may be substituted with fluorine atoms ;A 11 and A 12 Each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the hydrogen atoms included in the alicyclic hydrocarbon group and the aromatic hydrocarbon group are halogen atoms, -R 3 , -OR 3 , may be substituted with a cyano group or a nitro group ;F 11 and F 12 Each independently represents an alkanedyl group having 1 to 12 carbon atoms, and the hydrogen atoms included in the alkanedyl group are -OR 3 Or it may be substituted with a halogen atom, and the -CH2- included in the alkandyl group may be substituted with -O- or -CO- ;P 11 and P 12 Each independently represents a hydrogen atom or a polymerizable group (where P 11 and P 12 At least one of them is a polymerizable group) ;M each independently represents a divalent aliphatic hydrocarbon group having 2n carbon atoms (n represents an integer from 2 to 4) that may have substituents ;Ar 11 and Ar 12 are, respectively, the following formula (Ar-1) [In formula (Ar-1), * indicates a joint ; Q 1 -S-, -O-, or -NR 11 - represents, and R 11 represents a C1 to C6 alkyl group that may have hydrogen atoms or substituents ;Y 1 represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group that may have substituents, or an aromatic complex ring group ;Z 1 and Z 2 Each independently, a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group, a dicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, -NR 11 R 12 or -SR 11 Represents, and Z 1 and Z 2 They may combine with each other to form an aromatic ring or an aromatic complex ring, and R 11 and R 12 Each represents, independently, a hydrogen atom or a carbon-1 to carbon-6 alkyl group selected from]. Claim 2 delete Claim 3 delete Claim 4 A polymerizable liquid crystal composition comprising a polymerizable liquid crystal compound described in claim 1 and a polymerizable liquid crystal compound represented by formula (2). [In Equation (2), k21 and k22 each independently represent integers greater than or equal to 1; B 21 and B 22 is, each independently, -CR 1 R 2 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S- or representing a single bond, R 1 and R 2 Each represents, independently, a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms. 21 and E 22 is, each independently, -CR 1 R 2 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 1 -, -NR 2 -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S- or represents a single bond ;G 21 and G 22 Each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, and the hydrogen atoms included in the alicyclic hydrocarbon group are halogen atoms, -R 3 , -OR 3 , may be substituted with a cyano group or a nitro group, and the -CH2- included in the alicyclic hydrocarbon group may be substituted with -O-, -S- or -NH-, and R 3 ... represents an alkyl group having 1 to 4 carbon atoms, and the hydrogen atoms included in the alkyl group may be substituted with fluorine atoms ;A 21 and A 22 Each independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the hydrogen atoms included in the alicyclic hydrocarbon group and the aromatic hydrocarbon group are halogen atoms, -R 3 , -OR 3 , may be substituted with a cyano group or a nitro group ;F 21 and F 22 Each independently represents an alkanedyl group having 1 to 12 carbon atoms, and the hydrogen atoms included in the alkanedyl group are -OR 3 Or it may be substituted with a halogen atom, and the -CH2- included in the alkandyl group may be substituted with -O- or -CO- ;P 21 and P 22 Each independently represents a hydrogen atom or a polymerizable group (where P 21 and P 22 At least one of them is a polymerizable group) ;Ar 21 Each independently, the following formula (Ar-1) [In formula (Ar-1), * indicates a joint ; Q 1 -S-, -O-, or -NR 11 - represents, and R 11 represents a C1 to C6 alkyl group that may have hydrogen atoms or substituents ;Y 1 represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group that may have substituents, or an aromatic complex ring group ;Z 1 and Z 2 Each independently, a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group, a dicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, -NR 11 R 12 or -SR 11 Represents, and Z 1 and Z 2 They may combine with each other to form an aromatic ring or an aromatic complex ring, and R 11 and R 12 Each represents, independently, a hydrogen atom or a carbon-1 to carbon-6 alkyl group selected from]. Claim 5 A polymerizable liquid crystal composition according to claim 4, wherein the ratio of the peak area of ​​the polymerizable liquid crystal compound (1) to the total peak area of ​​the polymerizable liquid crystal compound (2), as measured by liquid chromatography, is 0.1% or more and 50% or less. Claim 6 In claim 4 or 5, A in formula (1) 11 , A 12 , B 11 , B 12 , E 11 , E 12 , F 11 , F 12 , G 11 , G 12 , P 11 and P 12 The giga represented by , respectively, A in equation (2). 21 , A 22 , B 21 , B 22 , E 21 , E 22 , F 21 , F 22 , G 21 , G 22 , P 21 and P 22 It is identical to the qi represented by , and Ar in Equation (1) 11 and Ar 12 The giga represented by is each Ar in Equation (2). 21 A polymerizable liquid crystal composition identical to the one represented by . Claim 7 A polymerizable liquid crystal composition according to claim 4 or 5, further comprising a photopolymerization initiator and an organic solvent. Claim 8 A phase difference film formed from a polymerizable liquid crystal composition as described in claim 4 or 5. Claim 9 A polarizing plate comprising a phase difference film as described in claim 8. Claim 10 An optical display comprising a polarizing plate as described in claim 9.

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