JP6414367B2 - Polymerizable liquid crystal composition - Google Patents

Description

  The present invention relates to a polymerizable liquid crystal composition useful as a liquid crystal device, a display, an optical component, a colorant, a security marking, a member for laser emission, or a component of an optical anisotropic body used for optical compensation such as a liquid crystal display. And an optically anisotropic body, a retardation film, a viewing angle compensation film, an antireflection film, a polarizing plate and a display element comprising the composition.

  The polymerizable liquid crystal composition is useful as a constituent member of an optical anisotropic body, and after coating a polymerizable liquid crystal material contained in the polymerizable liquid crystal composition on a substrate, it is photopolymerized in an aligned state to thereby form a retardation film. An optical anisotropic body such as can be manufactured. When photopolymerization is performed in a state where the polymerizable liquid crystal material exhibits a smectic phase, the layer structure of the smectic phase is fixed in the optical anisotropic body, so that it is closer to the crystal structure than when it is fixed in the nematic phase. An optical anisotropic body having a higher order structure can be obtained. In general, in order to produce an optically anisotropic body having excellent uniformity, a polymerizable liquid crystal material that suppresses unnecessary induction of thermal polymerization and exhibits a smectic phase at room temperature is preferable. Such a polymerizable liquid crystal material exhibiting a smectic phase at room temperature is described in Patent Document 1, but since it is mainly composed of monofunctional liquid crystal acrylate, it is difficult to photopolymerize in air, It is necessary to photopolymerize in a nitrogen atmosphere. Therefore, the handling in the manufacturing process becomes complicated, and there is a problem that the manufacturing cost is increased. In order to solve this problem, Patent Document 2 discloses a method for solving this problem by using a polymerizable liquid crystal composition in which a monofunctional polymerizable liquid crystal compound and a bifunctional polymerizable liquid crystal compound are mixed. However, the method described in Patent Document 2 has a problem that when the transition temperature (Tni) from the nematic phase to the isotropic liquid is increased, the upper limit temperature of the smectic phase is lowered. For this reason, since the smectic phase state having a layer structure closer to the crystal structure than the nematic phase can be maintained only at a lower temperature, there is a problem that the heat resistance of the obtained optical anisotropic body is lowered.

Japanese Patent Laid-Open No. 08-283718 JP 2005-272561 A

  The problem to be solved by the present invention is that a polymerizable liquid crystal material exhibiting a smectic phase at room temperature has a high transition temperature (Tni) to an isotropic liquid and an upper limit temperature (Tna) for forming a smectic phase. It is to provide a polymerizable liquid crystal composition that contains a highly polymerizable liquid crystal material and is photopolymerizable in air. Furthermore, the present invention provides a polymer obtained by polymerizing the polymerizable liquid crystal composition, having good orientation, high durability (retardation retention ratio), little repelling, and an optical anisotropic body using the polymer. It is to be.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have developed a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound having a specific structure. That is, the present invention comprises at least two polymerizable liquid crystal compounds having two polymerizable functional groups in the molecule, one of which is a polymerizable liquid crystal compound represented by the general formula (I-1). A polymerizable liquid crystal composition to be selected is provided, and a polymer obtained by polymerizing the polymerizable liquid crystal composition and an optical anisotropic body using the polymer are provided.

  The polymerizable liquid crystal composition of the present invention contains a polymerizable liquid crystal material having a high transition temperature (Tni) to an isotropic liquid and a high upper limit temperature (Tna) for forming a smectic phase. A possible polymerizable liquid crystal composition is provided. Since the polymerizable liquid crystal composition of the present invention can obtain a layer structure derived from a smectic phase that has undergone phase transition to a smectic liquid crystal having a higher alignment order than a nematic liquid crystal, the alignment property is good and the durability (retardation) Since an optically anisotropic body having a high retention ratio and low repellency can be obtained, it is useful for applications of optical materials such as a retardation film.

The best mode of the polymerizable liquid crystal composition according to the present invention will be described below. In the present invention, the “liquid crystal” of the polymerizable liquid crystal composition refers to removing the organic solvent after coating the polymerizable liquid crystal composition on a substrate. It is intended to show liquid crystal properties in the state. In the present invention, the “liquid crystal” of the polymerizable liquid crystal compound means a case where it is intended to show liquid crystal properties with only one type of polymerizable liquid crystal compound used, or a mixture with other liquid crystal compounds. It is intended to exhibit liquid crystal properties. The polymerizable liquid crystal composition can be polymerized (formed into a film) by performing a polymerization treatment by irradiation with light such as ultraviolet rays, heating, or a combination thereof.
(Bifunctional polymerizable liquid crystal compound)
(Bifunctional polymerizable liquid crystal compound represented by formula (I-1))
The polymerizable liquid crystal composition of the present invention contains at least two kinds of polymerizable liquid crystal compounds (bifunctional polymerizable liquid crystal compounds) having two polymerizable functional groups in the molecule, one of which is The essential component is selected from polymerizable liquid crystal compounds represented by the following general formula (I-1).

(Wherein P ¹¹¹ and P ¹¹² each independently represent a polymerizable functional group, and Sp ¹¹¹ and Sp ¹¹² each independently represent an alkylene group having 1 to 18 carbon atoms or a single bond, One —CH ₂ — or two or more non-adjacent —CH ₂ — may be each independently replaced by —O—, —COO—, —OCO— or —OCO—O—, One or more hydrogen atoms of the alkylene group may be substituted with a halogen atom or a CN group, and X ¹¹¹ and X ¹¹² are each independently —O—, —S—, —OCH _{2. -, - CH 2 O -,} - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O -, - CO-NH -, - NH-CO _{-, - SCH 2 -, -} CH 2 S -, - CF 2 O _{, -OCF 2 -, - CF 2} S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - _{, - - COO-CH 2 CH} 2 OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH ₂ —COO—, —CH ₂ —OCO—, —CH═CH—, —N═N—, —CH═N—N═CH—, —CF═CF—, —C≡C— or a single bond. (However, P ¹¹¹ -Sp ¹¹¹ , P ¹¹² -Sp ¹¹² , Sp ¹¹¹ -X ¹¹¹ and Sp ¹¹² -X ¹¹² do not include a direct bond between oxygen atoms), Y ¹¹¹ , Y ¹¹² and Y ¹¹³ are Each independently -COO- or -OCO -And q111 and q112 each independently represents an integer of 0 to 5.)
In general formula (I-1), ^P111 and ^P112 each independently represent a polymerizable functional group, but the following formulas (P-1) to (P-20)

Preferably, these polymerizable groups are polymerized by radical polymerization, radical addition polymerization, cationic polymerization and anionic polymerization. In particular, when ultraviolet polymerization is performed as a polymerization method, the formula (P-1), formula (P-2), formula (P-3), formula (P-4), formula (P-5), formula (P -7), formula (P-11), formula (P-13), formula (P-15) or formula (P-18) are preferred, and formula (P-1), formula (P-2), formula (P-18) P-7), formula (P-11) or formula (P-13) is more preferred, formula (P-1), formula (P-2) or formula (P-3) is more preferred, and formula (P- 1) or formula (P-2) is particularly preferred.

  In general formula (I-1), q111 and q112 each independently represent an integer of 0 to 5, more preferably an integer of 0 to 2, and particularly preferably 1.

In General Formula (I-1), Sp ¹¹¹ and Sp ¹¹² each independently represent an alkylene group having 1 to 18 carbon atoms or a single bond, and one —CH ₂ — in the alkylene group or adjacent to each other. And two or more —CH ₂ — may be each independently substituted by —O—, —COO—, —OCO— or —OCO—O—, and one or more of the alkylene group has The hydrogen atom may be substituted by a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) or a CN group. Moreover, it is more preferable that Sp ¹¹¹ and Sp ¹¹² each independently represent an alkylene group having 1 to 12 carbon atoms, and one —CH ₂ — or two or more non-adjacent ones in the alkylene group. Each —CH ₂ — may be independently substituted with —O—, —COO—, —OCO— or —OCO—O—. Furthermore, it is particularly preferable that Sp ¹¹¹ and Sp ¹¹² each independently represent an alkylene group having 1 to 8 carbon atoms.

In general formula (I-1), X ¹¹¹ and X ¹¹² are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—. , -CO-S -, - S -CO -, - O-CO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O-, _{-OCF 2 -, - CF 2 S} -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO _{-CH 2 CH 2 -, - OCO} -CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH _{2 -COO -, - CH 2 -OCO} -, - CH = CH -, - N = N -, - CH = N-N = CH-, CF = CF -, - C≡C- or a single bond. X ¹¹¹ and X ¹¹² are each independently —O—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —O—CO—O—, —CF. ₂ O—, —OCF ₂ —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH ₂ CH ₂ —, _{-OCO-CH 2 CH 2 -,} - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH More preferably, it represents _2- OCO-, -CH = CH-, -CF = CF-, -C≡C- or a single bond. Furthermore, it is particularly preferable that X ¹¹¹ and X ¹¹² each independently represent —O— or a single bond.

In General Formula (I-1), Y ¹¹¹ , Y ¹¹² and Y ¹¹³ each independently represent —COO— or —OCO—.

  The bifunctional polymerizable liquid crystal compound represented by the general formula (I-1) may be used alone or in combination of two or more, but the total content of the bifunctional polymerizable liquid crystal compound represented by the general formula (I-1) is included. The amount is preferably 1 to 70% by mass, more preferably 1 to 60% by mass, and more preferably 5 to 55% by mass in the total amount of the polymerizable liquid crystal compound used in the polymerizable liquid crystal composition. It is particularly preferred. When it is important to give the obtained optical anisotropic body a higher-order structure close to the crystal structure derived from the smectic phase, the lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more. When placing importance on lowering the melting point of the resulting polymerizable liquid crystal composition, the upper limit is preferably 40% by mass or less, and more preferably 30% by mass or less.

  Specifically, the compounds represented by the general formula (I-1) are preferably compounds represented by the following formulas (I-1-1) to (I-1-12).

(Bifunctional polymerizable liquid crystal compound represented by formula (I-2))
The polymerizable liquid crystal composition of the present invention contains at least two kinds of polymerizable liquid crystal compounds (bifunctional polymerizable liquid crystal compounds) having two polymerizable functional groups in the molecule. It is preferable to use together with the polymerizable liquid crystal compound represented by 1) one or more polymerizable liquid crystal compounds selected from the polymerizable liquid crystal compounds represented by the following general formula (I-2).

(In the formula, P ¹²¹ and P ¹²² each independently represent a polymerizable functional group, Sp ¹²¹ and Sp ¹²² each independently represent an alkylene group having 1 to 18 carbon atoms or a single bond, and the alkylene group In which one —CH ₂ — or two or more non-adjacent —CH ₂ — may be each independently substituted by —O—, —COO—, —OCO— or —OCO—O—. One or two or more hydrogen atoms of the alkylene group may be substituted with a halogen atom or a CN group, and X ¹²¹ and X ¹²² are each independently —O—, —S—, —OCH. _{2 -, - CH 2 O -} , - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O -, - CO-NH -, - NH- _{CO -, - SCH 2 -,} - CH 2 S -, - CF 2 _{-, - OCF 2 -, -} CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH-, _{, - - -COO-CH 2 CH} 2 OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, _{-CH 2 -COO -, - CH 2} -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH -, - CF = CF -, - C≡C- or a single bond (However, P ¹²¹ -Sp ¹²¹ , P ¹²² -Sp ¹²² , Sp ¹²¹ -X ¹²¹ and Sp ¹²² -X ¹²² do not include a direct bond between oxygen atoms), and Y ¹²¹ and Y ¹²² are independent of each other. -COO- or -OCO- The q121 and q122 each independently represents 0 or 1.)
In General Formula (I-2), P ¹²¹ and P ¹²² each independently represent a polymerizable functional group, but the following Formula (P-1) to Formula (P-20)

Preferably, these polymerizable groups are polymerized by radical polymerization, radical addition polymerization, cationic polymerization and anionic polymerization. In particular, when ultraviolet polymerization is performed as a polymerization method, the formula (P-1), formula (P-2), formula (P-3), formula (P-4), formula (P-5), formula (P -7), formula (P-11), formula (P-13), formula (P-15) or formula (P-18) are preferred, and formula (P-1), formula (P-2), formula (P-18) P-7), formula (P-11) or formula (P-13) is more preferred, formula (P-1), formula (P-2) or formula (P-3) is more preferred, and formula (P- 1) or formula (P-2) is particularly preferred.

  In general formula (I-2), q121 and q122 each independently represent an integer of 0 to 5, more preferably an integer of 0 to 2, and particularly preferably 1. .

In the general formula (I-2), Sp ¹²¹ and Sp ¹²² each independently represent an alkylene group having 1 to 18 carbon atoms or a single bond, and one —CH ₂ — in the alkylene group or adjacent to each other. And two or more —CH ₂ — may be each independently substituted by —O—, —COO—, —OCO— or —OCO—O—, and one or more of the alkylene group has The hydrogen atom may be substituted by a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) or a CN group. Moreover, it is more preferable that Sp ¹²¹ and Sp ¹²² each independently represent an alkylene group having 1 to 12 carbon atoms, and one —CH ₂ — or two or more non-adjacent ones in the alkylene group. Each —CH ₂ — may be independently substituted with —O—, —COO—, —OCO— or —OCO—O—. Furthermore, it is particularly preferable that Sp ¹²¹ and Sp ¹²² each independently represent an alkylene group having 1 to 8 carbon atoms.

In the general formula (I-2), X ¹²¹ and X ¹²² are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—. , -CO-S -, - S -CO -, - O-CO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O-, _{-OCF 2 -, - CF 2 S} -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO _{-CH 2 CH 2 -, - OCO} -CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH _{2 -COO -, - CH 2 -OCO} -, - CH = CH -, - N = N -, - CH = N-N = CH-, CF = CF -, - C≡C- or a single bond. X ¹²¹ and X ¹²² are each independently —O—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —O—CO—O—, —CF. ₂ O—, —OCF ₂ —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH ₂ CH ₂ —, _{-OCO-CH 2 CH 2 -,} - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH More preferably, it represents _2- OCO-, -CH = CH-, -CF = CF-, -C≡C- or a single bond. Furthermore, it is particularly preferable that X ¹²¹ and X ¹²² each independently represent —O— or a single bond.

In General Formula (I-2), Y ¹²¹ and Y ¹²² each independently represent —COO— or —OCO—.

The bifunctional polymerizable liquid crystal compound represented by the general formula (I-2) may be used alone or in combination of two or more, but the total content of the bifunctional polymerizable liquid crystal compound represented by the general formula (I-2) is included. The amount is preferably 0 to 80% by mass, more preferably 0 to 75% by mass, and more preferably 5 to 60% by mass in the total amount of the polymerizable liquid crystal compound used in the polymerizable liquid crystal composition. It is particularly preferred. When it is important to give the obtained optical anisotropic body a higher order structure close to the crystal structure derived from the smectic phase, the lower limit is preferably 10% by mass or more, more preferably 20% by mass or more. When placing importance on lowering the melting point of the resulting polymerizable liquid crystal composition, the upper limit value is preferably less than 60% by mass, and more preferably 50% by mass or less.
The mass ratio of the bifunctional polymerizable liquid crystal compound represented by the general formula (I-1) to the total content of the bifunctional polymerizable liquid crystal compound represented by the general formula (I-2) [general formula (I -1) / general formula (I-2)] has a high transition temperature (Tni) to the isotropic liquid and is within the range of 1/2 to 7/1, and an upper limit temperature for forming a smectic phase ( Tna) is preferable from the viewpoint of becoming a polymerizable liquid crystal material.

  Specifically, the compounds represented by the general formula (I-2) are preferably compounds represented by the following formulas (I-2-1) to (I-2-12).

(Other bifunctional polymerizable liquid crystal compounds)
The polymerizable liquid crystal composition of the present invention contains at least two kinds of polymerizable liquid crystal compounds (bifunctional polymerizable liquid crystal compounds) having two polymerizable functional groups in the molecule. The polymerizable liquid crystal compound represented by the above general formula (I-2) and / or the polymerizable liquid crystal compound represented by the following general formula (I-3) is used in combination with the polymerizable liquid crystal compound represented by 1). It is preferable.

( ^Wherein P ¹³¹ and P ¹³² each independently represent a polymerizable functional group, Sp ¹³¹ and Sp ¹³² each independently represent an alkylene group having 1 to 18 carbon atoms or a single bond, 1 —CH ₂ — or 2 or more non-adjacent —CH ₂ — in the group may be each independently substituted by —O—, —COO—, —OCO— or —OCO—O—. Preferably, one or more hydrogen atoms of the alkylene group may be substituted with a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) or a CN group, and X ¹³¹ and X ¹³² are each _{independently, -O -, - S -,} - OCH 2 -, - CH 2 O -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - O- CO-O-, -CO-NH-, -NH- _{O -, - SCH 2 -,} - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO _{-, - COO-CH = CH} -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 _{-OCO -, - COO-CH 2} -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N ═CH—, —CF═CF—, —C≡C— or a single bond (wherein P ¹³¹ -Sp ¹³¹ , P ¹³² -Sp ¹³² , Sp ¹³¹ -X ¹³¹ and Sp ¹³² -X ¹³² are oxygen atoms) Does not include a direct bond between each other), q131 and q132 Respectively independently, represent 0 or ^{1, MG 131} may represent a mesogenic group, excluding the compound represented by the general formula (I-1) and the general formula (I-2).)
In General Formula (I-3), P ¹³¹ and P ¹³² are each independently a substituent selected from a polymerizable group represented by Formula (P-2-1) to Formula (P-2-20). Is preferably represented.

  Among these polymerizable functional groups, from the viewpoint of increasing the polymerizability, the formulas (P-2-1), (P-2-2), (P-2-7), (P-2-12), ( P-2-13) is preferable, and formulas (P-2-1) and (P-2-2) are more preferable.

  In general formula (I-3), q131 and q132 each independently represent 0 or 1, but q131 and q132 are preferably 1.

In the general formula (I-3), Sp ¹³¹ and Sp ¹³² each independently preferably represent an alkylene group having 1 to 15 carbon atoms, and one —CH ₂ — in the alkylene group or adjacent to each other. Two or more —CH ₂ — that are not present may be each independently substituted by —O—, —COO—, —OCO—, or —OCO—O—, and one or more of the alkylene group has The hydrogen atom may be substituted by a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) or a CN group, and Sp ¹³¹ and Sp ¹³² are each independently an alkylene group having 1 to 12 carbon atoms. In the alkylene group, one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —COO—, —OCO— or —. OC It may be replaced by -O-.

In General Formula (I-3), X ¹³¹ and X ¹³² each independently represent —O—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —O—. CO—O—, —CO—NH—, —NH—CO—, —CF ₂ O—, —OCF ₂ —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH _{-, - OCO-CH = CH} -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH _{2 -, - OCO-CH 2} -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH -, - CF = CF -, - C≡C- or preferably a single ^{bond, X 131} and ^{X 132} each independently _{-O -, - OCH 2 -,} - CH 2 O -, - CO -, - COO -, - OCO -, - OCO-O -, - CF 2 O -, - OCF 2 -, - CH = CH -COO -, - CH = CH- OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH _{2 -COO -, - CH 2 CH} 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - CF More preferably, it represents ═CF—, —C≡C— or a single bond.

In the general formula (I-3), MG ¹³¹ represents a mesogenic group, and a group represented by the general formula (I-3-b) is preferable.

In the formula, A1, A2 and A3 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3. -Dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine-2 , 5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2,6-diyl Group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenant Les -2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5-b '] dithiophene-2,6-diyl group, benzo [1,2-b: 4,5 -B '] diselenophen-2,6-diyl group, [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2-b] selenophene-2, Represents a 7-diyl group or a fluorene-2,7-diyl group, and has one or more F, Cl, CF ₃ , OCF ₃ , CN groups, an alkyl group having 1 to 8 carbon atoms, or the number of carbon atoms as a substituent. An alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, carbon C2-C8 alkenyloxy group, carbon atoms 8 alkenoyl groups, and / or it may have a alkenoyloxy group having from 2 to 8 carbon atoms, the Z1 and Z2 each independently, -COO -, - OCO -, - CH 2 CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CH═CH—, —C≡C—, —CH═CHCOO—, —OCOCH═CH—, —CH ₂ CH ₂ COO—, —CH ₂ CH ₂ OCO—, —COOCH ₂ CH ₂ —, —OCOCH ₂ CH ₂ —, —C═N—, —N═C—, —CONH—, —NHCO—, —C (CF ₃ ) ₂ —, a halogen atom ( A fluorine atom, a chlorine atom, a bromine atom, an iodine atom) which may have an alkyl group having 2 to 10 carbon atoms or a single bond, Z1 and Z2 are each independently -COO-, -OCO-,- _{CH 2 CH 2 -, - OCH} 2 -, - CH 2 O -, - CH = H -, - C≡C -, - CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 - Or a single bond, and preferably —COO—, —OCO—, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ O—, —CH ₂ CH ₂ OCO—, —COOCH ₂ CH ₂ —. , —OCOCH ₂ CH ₂ — or a single bond is more preferable, r1 represents 0, 1, 2 or 3, and when a plurality of A1 and Z1 are present, they may be the same or different. May be. Among these, it is preferable that A1, A2, and A3 each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group, or a 2,6-naphthylene group.

  The bifunctional polymerizable liquid crystal compound represented by the general formula (I-3) may be used alone or in combination of two or more, but the total content of the bifunctional polymerizable liquid crystal compound represented by the general formula (I-3) is included. The amount is preferably 0 to 40% by mass, more preferably 0 to 30% by mass, and more preferably 10 to 20% by mass in the total amount of the polymerizable liquid crystal compound used in the polymerizable liquid crystal composition. It is particularly preferred. When importance is attached to the curability of the obtained optical anisotropic body, the lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, and importance is attached to the flexibility of the obtained optical anisotropic body. When it does, it is preferable to make an upper limit into 30 mass% or less, and it is more preferable to set it as 20 mass% or less.

  Among the polymerizable liquid crystal compounds represented by the above general formula (I-3), when the viscosity of the polymerizable liquid crystal composition is decreased while maintaining curability, the following general formula (I-3-1) It is preferable to use a polymerizable liquid crystal compound represented by the formula:

(In the formula, P ¹³¹¹ and P ¹³¹² each independently represent a polymerizable functional group, and Sp ¹³¹¹ and Sp ¹³¹² each independently represent an alkylene group having 1 to 18 carbon atoms or a single bond, One —CH ₂ — or two or more non-adjacent —CH ₂ — may be each independently replaced by —O—, —COO—, —OCO— or —OCO—O—, One or more hydrogen atoms of the alkylene group may be substituted with a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) or a CN group, and X ¹³¹¹ and X ¹³¹² are each independently _{Te, -O -, - S -,} - OCH 2 -, - CH 2 O -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - O-CO- O-, -CO-NH-, _{NH-CO -, - SCH 2} -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH -OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 _{CH 2 -OCO -, - COO-} CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N —N═CH—, —CF═CF—, —C≡C— or a single bond (wherein P ¹³¹¹ -Sp ¹³¹¹ , P ¹³¹² -Sp ¹³¹² , Sp ¹³¹¹ -X ¹³¹¹ and Sp ¹³¹² -X ¹³¹² are (Does not include direct bonds between oxygen atoms.) Y ¹³¹¹ is -COO -, - OCO -, - CH 2 CH 2 -, - OCH 2 -, - CH 2 O -, - CH = CH -, - C≡C -, - CH = CHCOO -, - OCOCH = _{CH -, - CH 2 CH 2} COO -, - CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 -, - C = N -, - N = C -, - CONH -, - NHCO-, -C (CF ₃ ) _2- , an alkyl group having 2 to 10 carbon atoms which may have a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom) or a single bond, q1311 and q1312 independently represents 0 or 1.)
In General Formula (I-3-1), P ¹³¹¹ and P ¹³¹² are each independently selected from a polymerizable group represented by Formula (P-2-1) to Formula (P-2-20). It is preferable to represent a substituent. From the viewpoint of improving the polymerizability, the formulas (P-2-1), (P-2-2), (P-2-7), (P-2-12), (P -2-13) is preferable, and formulas (P-2-1) and (P-2-2) are more preferable.

  In general formula (I-3-1), q1311 and q1312 each independently represent 0 or 1, but q1311 and q1312 are preferably 1.

In the general formula (I-3-1), Sp ¹³¹¹ and Sp ¹³¹² each independently preferably represent an alkylene group having 1 to 15 carbon atoms, and one —CH ₂ — in the alkylene group or Two or more non-adjacent —CH ₂ — may be each independently substituted by —O—, —COO—, —OCO— or —OCO—O—, and one or two of the alkylene group One or more hydrogen atoms may be substituted by a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) or a CN group, and Sp ¹³¹¹ and Sp ¹³¹² each independently have 1 to 12 carbon atoms. it is more preferably an alkylene group, one -CH ₂ in the alkylene group - or nonadjacent two or more -CH ₂ - are each independently -O -, - COO -, - OCO Or may be substituted by --OCO-O-.

In General Formula (I-3-1), X ¹³¹¹ and X ¹³¹² each independently represent —O—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, — O—CO—O—, —CO—NH—, —NH—CO—, —CF ₂ O—, —OCF ₂ —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH _{= CH -, - OCO-CH} = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO _{-CH 2 -, - OCO-CH} 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH -, - CF = CF -, - C≡C- or preferably a single ^{bond, X 1311} and ^{X 1312} is it Is _{independently, -O -, - OCH 2 -} , - CH 2 O -, - CO -, - COO -, - OCO -, - OCO-O -, - CF 2 O -, - OCF 2 - , —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ — _{, -CH 2 CH 2 -COO -,} - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = More preferably, it represents CH—, —CF═CF—, —C≡C— or a single bond.

In the general formula (I-3-1), Y ¹³¹¹ represents —COO—, —OCO—, —CH ₂ CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CH═CH—, —C≡C. -, - CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 -, - C = N-, —N═C—, —CONH—, —NHCO—, —C (CF ₃ ) ₂ —, and a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) which may have 2 to 10 carbon atoms Y ¹³¹¹ represents —COO—, —OCO—, —CH ₂ CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CH═CHCOO—, —OCOCH═CH—. _{, -CH 2 CH 2 COO -,} - CH 2 CH 2 OCO -, - COOCH 2 _{H 2 -, - OCOCH 2 CH} 2 - or a single bond are ^{preferred, Y 1311} is -COO -, - OCO -, - CH 2 CH 2 -, - OCH 2 -, - CH 2 O- or a single bond is more preferable Y ¹³¹¹ is particularly preferably —COO—, —OCO— or a single bond.

  The bifunctional polymerizable liquid crystal compound represented by the general formula (I-3-1) may be used alone or in combination of two or more, but the bifunctional polymerizable liquid crystal represented by the general formula (I-3-1) The total content of the compound is preferably 0 to 40% by mass, more preferably 0 to 30% by mass, out of the total amount of the polymerizable liquid crystal compound used in the polymerizable liquid crystal composition, and 10 to 20%. It is particularly preferable to contain it by mass%. When importance is attached to the curability of the obtained optical anisotropic body, the lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, and the flexibility of the obtained optical anisotropic body is improved. When importance is attached, the upper limit value is preferably 30% by mass or less, and more preferably 20% by mass or less.

  Specifically, the compounds represented by the general formula (I-3-1) are preferably compounds represented by the following formulas (I-3-1-1) to (I-3-1-12). . Among the formulas (I-3-1-1) to (I-3-1-1-12), the formulas (I-3-1-1) to (I-3-1-4) are preferable, The formula (I-3-1-1) is particularly preferable.

  In the general formulas (I-3-1) to (I-3-6), each n independently represents an integer of 1 to 18, and each n is independently preferably an integer of 1 to 10. , N are each independently preferably an integer of 3-6.

  Specifically, the following formulas (I-3-1-1-1) to (I-3-1-1-6) are particularly preferable as the formula (I-3-1-1).

  Further, specific examples of the compound represented by the above general formula (I-3) include the following general formula (I-3-2-1) other than the compound represented by the above formula (I-3-1). ) To the compound represented by the general formula (I-3-2-234), but is not limited to the following general formula.

In the general formula (I-3-2-1) to the general formula (I-3-2-234), R ^d and R ^e each independently represent a hydrogen atom or a methyl group,
The cyclic group has one or more F, Cl, CF ₃ , OCF ₃ , CN groups, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and 1 to 1 carbon atoms as a substituent. An alkanoyl group having 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, and a carbon atom It may have an alkenoyl group having 2 to 8 carbon atoms or an alkenoyloxy group having 2 to 8 carbon atoms,
m1 and m2 each independently represent an integer of 0 to 18, and n1, n2, n3, and n4 each independently represent 0 or 1.

Total content of the bifunctional polymerizable liquid crystal compound having two polymerizable functional groups in the molecule represented by the general formula (I-1), general formula (I-2) and general formula (I-3) Is preferably 20 to 100% by mass, more preferably 40 to 100% by mass, and 65 to 85% by mass of the total amount of the polymerizable liquid crystal compound used in the polymerizable liquid crystal composition. Is particularly preferred.
(Trifunctional polymerizable liquid crystal compound)
The polymerizable liquid crystal composition of the present invention may contain a polymerizable liquid crystal compound having three polymerizable functional groups in the molecule as long as the physical properties are not impaired. Examples of the polymerizable liquid crystal compound having three polymerizable functional groups in the molecule include compounds represented by the following general formula (III).

(Wherein P ^{31 to} P ³³ each independently represents a polymerizable functional group, and Sp ^{31 to} S ³³ each independently represents an alkylene group having 1 to 18 carbon atoms or a single bond, 1 —CH ₂ — or 2 or more non-adjacent —CH ₂ — in the group may be each independently substituted by —O—, —COO—, —OCO— or —OCO—O—. Preferably, one or more hydrogen atoms of the alkylene group may be substituted with a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) or a CN group, and X ^{31 to} X ³³ are each _{independently, -O -, - S -,} - OCH 2 -, - CH 2 O -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - O- CO-O-, -CO-NH-, -NH-CO-, -SCH _{2 -, - CH 2 S -,} - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH _{= CH -, - OCO-CH} = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO _{-CH 2 -, - OCO-CH} 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH -, - CF = CF-, -C≡C- or a single bond (provided that P ³¹ -Sp ³¹ , P ³² -Sp ³² , Sp ³¹ -X ³¹ , Sp ³² -X ³² , Sp ³³ -X ³³ , and Sp ³³⁾ in -X ^33, does not include a direct bond between the oxygen atom.), q31, q3 , Q34, and q35 are each independently 0 or 1, ^{MG 31} represents a mesogen group.)
In the general formula (III), P ^{31 to} P ³³ each independently represent a substituent selected from a polymerizable group represented by the following formula (P-2-1) to formula (P-2-20). Preferably it represents.

  Among these polymerizable functional groups, from the viewpoint of increasing the polymerizability, the formulas (P-2-1), (P-2-2), (P-2-7), (P-2-12), ( P-2-13) is preferable, and formulas (P-2-1) and (P-2-2) are more preferable.

In the general formula (III), Sp ^{31 to} Sp ³³ each independently preferably represent an alkylene group having 1 to 15 carbon atoms, and one —CH ₂ — in the alkylene group or not adjacent to each other. Two or more —CH ₂ — may be each independently substituted by —O—, —COO—, —OCO— or —OCO—O—, and one or more hydrogens of the alkylene group The atom may be substituted by a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) or a CN group, and Sp ^{31 to} Sp ³³ each independently represents an alkylene group having 1 to 12 carbon atoms. more preferably, one -CH ₂ in the alkylene group - or nonadjacent two or more -CH ₂ - are each independently -O -, - COO -, - OCO- or -OCO- O- It may be substituted me. X ^{31 to} X ³³ are each independently —O—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —O—CO—O—, —CO—NH. _{-, - NH-CO -,} - CF 2 O -, - OCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH- , —COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO—, —CH ₂ CH ₂ —OCO—, —COO—CH ₂ —, —OCO—CH ₂ — _{, -CH 2 -COO -, - CH} 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH -, - CF = CF -, - C≡C- or a single preferably represents a ^bond, X 11 ^{to X 13} are each _{independently, -O -, - OCH 2 -} , - CH 2 O _{, -CO -, - COO -,} - OCO -, - OCO-O -, - CF 2 O -, - OCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO _{-CH = CH -, - OCO-} CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO-, —COO—CH ₂ —, —OCO—CH ₂ —, —CH ₂ —COO—, —CH ₂ —OCO—, —CH═CH—, —CF═CF—, —C≡C— or a single bond is represented. It is more preferable.

In the general formula (III), MG ³¹ represents a mesogenic group, and the general formula (III-A)

In the formula, A1, A2 and A3 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3. -Dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine-2 , 5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2,6-diyl Group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenant Les -2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5-b '] dithiophene-2,6-diyl group, benzo [1,2-b: 4,5 -B '] diselenophen-2,6-diyl group, [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2-b] selenophene-2, Represents a 7-diyl group or a fluorene-2,7-diyl group, and has one or more F, Cl, CF ₃ , OCF ₃ , CN groups, an alkyl group having 1 to 8 carbon atoms, or the number of carbon atoms as a substituent. An alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, carbon C2-C8 alkenyloxy group, carbon atoms 8 alkenoyl groups, and / or, but may have a alkenoyloxy group having from 2 to 8 carbon atoms, in either existing A1, A2 and _{^{A3 - (X 33) q35 -}} (Sp ³³⁾ having _q34 -P ³³ groups. Z1 and Z2 are each independently —COO—, —OCO—, —CH ₂ CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CH═CH—, —C≡C—, —CH═. CHCOO -, - OCOCH = CH - , - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 -, - C = N -, - N = C- , —CONH—, —NHCO—, —C (CF ₃ ) ₂ —, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) or an alkyl group having 2 to 10 carbon atoms or a single atom. Z1 and Z2 each independently represent —COO—, —OCO—, —CH ₂ CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CH═CH—, —C≡C—, -CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - CH ₂ CH ₂ OCO—, —COOCH ₂ CH ₂ —, —OCOCH ₂ CH ₂ — or a single bond is preferable, r1 represents 0, 1, 2 or 3, and when A1 and Z1 are plurally present These may be the same or different. ). Among these, it is preferable that A1, A2, and A3 each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group, or a 2,6-naphthylene group.
Examples of the general formula (III) include compounds represented by the following general formulas (III-1) to (III-8), but are not limited to the following general formula.

In the formula, P ³¹ , Sp ³¹ , X ³¹ , q ³¹ , X ³² , Sp ³² , q ³² , P ³² , X ³³ , q 35, Sp ³³ , q 34, P ³³ are as defined in the general formula (III) above. Represent the same thing,
A11, A12, A13, A2, and A3 each represent the same definition as A1 to A3 in the general formula (III-A), and may be the same or different,
Z11, Z12, Z13, and Z2 each represent the same definition as Z1 and Z2 in the general formula (III-A), and may be the same or different.

  Examples of the compounds represented by the general formulas (III-1) to (III-8) include compounds represented by the following general formulas (III-9-1) to (III-9-6). However, it is not necessarily limited to these.

In general formulas (III-9-1) to (III-9-6), R ^f , R ^g and R ^h each independently represent a hydrogen atom or a methyl group, and R ⁱ , R ^j and R ^k are Each independently represents a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group. In the case of an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, all of them are unsubstituted, or one or two or more halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine) The cyclic group may be substituted with one or more F, Cl, CF ₃ , OCF ₃ , CN groups, an alkyl group having 1 to 8 carbon atoms, 1 to 1 carbon atoms. 8 alkoxy groups, 1 to 8 carbon atoms Canoyl group, alkanoyloxy group having 1 to 8 carbon atoms, alkoxycarbonyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 8 carbon atoms, alkenyloxy group having 2 to 8 carbon atoms, 2 carbon atoms It may have an -8 alkenoyl group or an alkenoyloxy group having 2 to 8 carbon atoms.
m4 to m9 each independently represents an integer of 0 to 18, and n4 to n10 each independently represents 0 or 1.

  The polyfunctional polymerizable liquid crystal compound having three polymerizable functional groups can be used alone or in combination of two or more.

The total content of the polyfunctional polymerizable liquid crystal compound having three polymerizable functional groups in the molecule may be 0 to 20% by mass in the total amount of the polymerizable liquid crystal compound used in the polymerizable liquid crystal composition. The content is preferably 0 to 10% by mass, and more preferably 0 to 5% by mass.
(Monofunctional polymerizable liquid crystal compound)
The polymerizable liquid crystal composition of the present invention has a monofunctional compound having one polymerizable functional group in the molecule in order to give the obtained optical anisotropic body a higher-order structure close to the crystal structure derived from the smectic phase. It is preferable to contain one or more polymerizable liquid crystal compounds. One or more polymerizable liquid crystal compounds selected from the group represented by the following general formula (II-1) may be used as a monofunctional polymerizable liquid crystal compound having one polymerizable functional group in the molecule. Particularly preferred.

(In the formula, P ²¹ represents a polymerizable functional group, Sp ²¹ represents an alkylene group having 1 to 18 carbon atoms or a single bond, and one —CH ₂ — in the alkylene group or not adjacent thereto. Two or more —CH ₂ — may be each independently substituted by —O—, —COO—, —OCO— or —OCO—O—, and one or more hydrogens of the alkylene group The atom may be substituted with a halogen atom or a CN group, and X ²¹ represents —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, -CO-S -, - S- CO -, - O-CO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - _{OCF 2 -, - CF 2 S} -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OC _{-, - COO-CH = CH} -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 _{-OCO -, - COO-CH 2} -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N ═CH—, —CF═CF—, —C≡C— or a single bond (wherein P ²¹ -Sp ²¹ and Sp ²¹ -X ²¹ do not include a direct bond between oxygen atoms), Y ²¹ -COO is -, - OCO- or a single bond, q21 is 0 or ^1, T 21 is _{-OH, -SH, -CN, -COOH,} -NH 2, -NO 2, -COCH 3, - _{O (CH 2) n CH 3} , or - represents a _{(CH 2) n CH 3,} n It represents an integer of 0 to 20.)
In the general formula (II-1), P ²¹ represents a polymerizable functional group, and is a substituent selected from the polymerizable groups represented by the following formulas (P-2-1) to (P-2-20) It preferably represents a group.

  Among these polymerizable functional groups, from the viewpoint of increasing the polymerizability, the formulas (P-2-1), (P-2-2), (P-2-7), (P-2-12), ( P-2-13) is preferable, and formulas (P-2-1) and (P-2-2) are more preferable.

  In general formula (II-1), q21 represents 0 or 1, but q21 is preferably 1.

In the general formula (II-1), Sp ²¹ represents an alkylene group having 1 to 18 carbon atoms or a single bond, and one —CH ₂ — in the alkylene group or two or more — that are not adjacent to each other. CH ₂ — may be independently substituted with —O—, —COO—, —OCO— or —OCO—O—, and one or more hydrogen atoms of the alkylene group may be a halogen atom. Alternatively, it may be substituted by a CN group. Sp ²¹ more preferably represents an alkylene group or a single bond having 1 to 12 carbon atoms, one -CH ₂ in the alkylene group - or nonadjacent two or more -CH ₂ - are each independently And may be substituted by -O-, -COO-, -OCO- or -OCO-O-. Sp ²¹ preferably represents an alkylene group having 1 to 8 carbon atoms or a single bond, and Sp ²¹ particularly preferably represents an alkylene group having 1 to 8 carbon atoms.

In General Formula (II-1), Y ²¹ represents —COO—, —OCO—, or a single bond, and Y ²¹ is preferably a single bond.

In General Formula (II-1), T ²¹ represents —OH, —SH, —CN, —COOH, —NH ₂ , —NO ₂ or —COCH ₃ , —O (CH ₂ ) _n CH ₃ , or — (CH ₂ ) _n CH ₃ and n represents an integer of 0 to 20, but T ²¹ represents —OH, —SH, —CN, —COCH from the viewpoint that the polymerizable liquid crystal composition of the present invention exhibits smectic properties. ₃ , —O (CH ₂ ) _n CH ₃ , or — (CH ₂ ) _n CH ₃ (n is an integer of 0 or 5 or more and 20 or less), and T ²¹ is —CN, —OCH ₃ , —CO (CH _{2) n} CH _3, or _{-CS (CH 2) n CH 3} (n is 0 or 8 to 20 integer) are more ^{preferable, T 21} is -CN, more preferably -OCH ^{_3, T 21} is -CN Is particularly preferred.

The total content of the monofunctional polymerizable liquid crystal compound represented by the general formula (II-1) is preferably 0 to 80% by mass in the total amount of the polymerizable liquid crystal compound used in the polymerizable liquid crystal composition. The content is more preferably 0 to 75% by mass, further preferably 5 to 60% by mass, and particularly preferably 10 to 40% by mass. When it is important to give the obtained optical anisotropic body a higher order structure close to the crystal structure derived from the smectic phase, the lower limit is preferably 10% by mass or more, more preferably 15% by mass or more. When considering the curability of the obtained optical anisotropic body, the upper limit value is preferably less than 65% by mass, and more preferably 40% by mass or less.
Moreover, the monofunctional polymerizable liquid crystal compound represented by the general formula (II-1) is represented by the bifunctional polymerizable liquid crystal compound represented by the general formula (I-1) and the general formula (I-2). It is preferable to use together with the bifunctional polymerizable liquid crystal compound from the viewpoint that the transition temperature (Tni) to the isotropic liquid and the upper limit temperature (Tna) for forming the smectic phase become higher. In this case, the general formula (I-1 ), A bifunctional polymerizable liquid crystal compound represented by general formula (I-2), a monofunctional polymerizable liquid crystal compound represented by general formula (II-1), and The blending ratio of [(I-1) / (I-2) / (II-1)] is a ratio of (10-60) / (5-40) / (20-40) on a mass basis. Is the transition temperature (Tni) to the isotropic liquid and the upper limit temperature (Tna) for forming the smectic phase. Preferable from a higher point.

  Specifically, the compounds represented by the general formula (II-1) are preferably compounds represented by the following formulas (II-1-1) to (II-1-25).

(Other monofunctional polymerizable liquid crystal compounds)
The polymerizable liquid crystal composition of the present invention preferably contains one or more monofunctional polymerizable liquid crystal compounds having one polymerizable functional group in the molecule, and the above general formula (II-1) It is preferable to use together the polymerizable liquid crystal compound represented by the following general formula (II-2) together with the polymerizable liquid crystal compound represented by formula (II).

(In the formula, P ²² represents a polymerizable functional group, Sp ²² represents an alkylene group having 1 to 18 carbon atoms or a single bond, and one —CH ₂ — in the alkylene group or not adjacent 2. more than five -CH ₂ - are each independently -O -, - COO -, - OCO- or --OCO-O-may be substituted by, one or more hydrogen atoms possessed by said alkylene group May be substituted with a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) or a CN group, and X ²² represents —O—, —S—, —OCH ₂ —, —CH ₂ O—, — CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —SCH ₂ —, —CH _{2 S -, - CF 2 O} -, - OCF 2 -, - CF 2 S -, - SCF 2 -, CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - _{CH 2 CH 2 -COO -, -} CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH- , —N═N—, —CH═N—N═CH—, —CF═CF—, —C≡C— or a single bond (wherein P ²² -Sp ²² and Sp ²² -X ²² Q22 represents 0 or 1, MG ²² represents a mesogenic group, R ²² represents a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom). , Cyano group, straight or branched chain having 1 to 12 carbon atoms Alkyl group, a linear or branched alkenyl group having 1 to 12 carbon atoms, the alkyl group and one -CH 2 in the alkenyl _- or nonadjacent two or more -CH 2 _- are each independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH _{-CO -, - NH -, -} N (CH 3) -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - CH ═CH—, —CF═CF— or —C≡C— may be substituted, and one or more hydrogen atoms of the alkyl group and the alkenyl group are each independently a halogen atom (fluorine Atom, chlorine atom, bromine atom, iodine atom) or cyano group In the case where a plurality of substituents are substituted, they may be the same or different, but the polymerizable liquid crystal compound represented by the general formula (II-2) is represented by the above general formula (II-1). The polymerizable liquid crystal compound is not included.

In the general formula (II-2), P ²² preferably represents a substituent selected from the polymerizable groups represented by the following formulas (P-2-1) to (P-2-20).

  Among these polymerizable functional groups, from the viewpoint of increasing the polymerizability, the formulas (P-2-1), (P-2-2), (P-2-7), (P-2-12), ( P-2-13) is preferable, and formulas (P-2-1) and (P-2-2) are more preferable.

In the general formula (II-2), Sp ²² preferably represents an alkylene group having 1 to 15 carbon atoms, and one —CH ₂ — in the alkylene group or two or more —CH 2 not adjacent to each other. _2- may be each independently substituted with -O-, -COO-, -OCO- or -OCO-O-, and one or more hydrogen atoms of the alkylene group may be a halogen atom ( A fluorine atom, a chlorine atom, a bromine atom, an iodine atom) or a CN group, Sp ²² preferably represents an alkylene group having 1 to 12 carbon atoms, and one — CH ₂ — or two or more non-adjacent —CH ₂ — may each independently be replaced by —O—, —COO—, —OCO— or —OCO—O—.

In the general formula (II-2), X ²² represents —O—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —O—CO—O—, —CO—. NH—, —NH—CO—, —CF ₂ O—, —OCF ₂ —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH _{-, - COO-CH 2 CH} 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 —, —CH ₂ —COO—, —CH ₂ —OCO—, —CH═CH—, —N═N—, —CH═N—N═CH—, —CF═CF—, —C≡C— or preferably represents a single ^bond, X 22 is _{-O -, - OCH 2 -,} - CH 2 O -, - CO -, - COO-, _{OCO -, - OCO-O -} , - CF 2 O -, - OCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH _{= CH -, - COO-CH} 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO- More preferably, it represents CH ₂ —, —CH ₂ —COO—, —CH ₂ —OCO—, —CH═CH—, —CF═CF—, —C≡C— or a single bond.

In the general formula (II-2), MG ²² represents a mesogenic group, and preferably represents the following general formula (II-2-b).

In general formula (II-2-b), A1, A2 and A3 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2, 5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2, 6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4 Tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-oct Hydrophenanthrene-2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5-b ′] dithiophene-2,6-diyl group, benzo [1,2-b: 4 , 5-b ′] diselenophen-2,6-diyl group, [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2-b] selenophene- 2,7-diyl group, or fluorene-2,7-diyl group, one or more F, Cl, CF ₃ , OCF ₃ , CN group, C 1-8 alkyl group, carbon as a substituent An alkoxy group having 1 to 8 atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and an alkenyl group having 2 to 8 carbon atoms , Alkenyl having 2 to 8 carbon atoms It may have a xyl group, an alkenoyl group having 2 to 8 carbon atoms, and / or an alkenoyloxy group having 2 to 8 carbon atoms, among which A1, A2 and A3 are each independently It preferably represents a 1,4-phenylene group, a 1,4-cyclohexylene group or a 2,6-naphthylene group which may have the above-described substituent.

In general formula (II-2-b), Z1 and Z2 are each independently —COO—, —OCO—, —CH ₂ CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CH═CH. -, - C≡C -, - CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 -, It may have —C═N—, —N═C—, —CONH—, —NHCO—, —C (CF ₃ ) ₂ —, and a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom). represents an alkyl group or a single bond having 2 to 10 carbon atoms, the Z1 and Z2 each independently -COO -, - OCO -, - CH 2 CH 2 -, - OCH 2 -, - CH 2 O -, - CH═CH—, —C≡C—, —CH═CHCOO—, —OCOCH═CH—, —C H ₂ CH ₂ COO—, —CH ₂ CH ₂ OCO—, —COOCH ₂ CH ₂ —, —OCOCH ₂ CH ₂ — or a single bond is preferable.

  In general formula (II-2-b), r1 represents 0, 1, 2 or 3, and when a plurality of A1 and Z1 are present, they may be the same or different.

In the general formula (II-2), R ²² is a hydrogen atom, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a cyano group, a linear or branched alkyl group having 1 to 8 carbon atoms, carbon more preferably represents a straight-chain or branched alkenyl group having the number of atoms of 1 to 8, one -CH 2 in the alkyl group and alkenyl group of 2 _- or nonadjacent two or more -CH 2 _- are each independently -O-, -CO-, -COO-, -OCO-, -O-CO-O-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, or -C≡C- may be substituted, and one or more hydrogen atoms of the alkyl group and the alkenyl group are each independently , Halogen atoms (fluorine atoms, chlorine atoms A bromine atom, may be substituted by an iodine atom) or a cyano group, even each identical If a plurality substituted, may be different.

However, the polymerizable liquid crystal compound represented by the general formula (II-2) does not include the polymerizable liquid crystal compound represented by the general formula (II-1).
Examples of the general formula (II-2) include compounds represented by the following general formulas (II-2-1) to (II-2-4), but are not limited to the following general formulas. is not.

In the formula, P ²² , Sp ²² , X ²² , q 1 and R ²² each represent the same definition as in the general formula (II-2),
A11, A12, A13, A2, and A3 represent the same definitions as A1 to A3 in the general formula (II-2-b), and may be the same or different,
Z11, Z12, Z13, and Z2 represent the same definitions as Z1 to Z3 in the general formula (II-2-b), and may be the same or different,
The compounds represented by the general formulas (II-2-1) to (II-2-4) are represented by the following formulas (II-2-1-1) to (II-2-1-24). The compounds represented are exemplified, but not limited thereto.

In the above formula (II-2-1-1) to formula (II-2-1-24), R ^c represents a hydrogen atom or a methyl group, m represents an integer of 0 to 18, and n represents 0 or 1 R ²¹ represents the same definition as in the general formulas (II-2-1) to (II-2-4), but R ²¹ represents a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, A bromine atom, an iodine atom), a cyano group, one —CH ₂ — may be substituted by —O—, —CO—, —COO—, —OCO—, a linear chain having 1 to 6 carbon atoms It preferably represents an alkyl group or a linear alkenyl group having 1 to 6 carbon atoms.

In the above formulas (II-2-1-1) to (II-2-1-24), the cyclic group is one or more F, Cl, CF ₃ , OCF ₃ , CN groups, carbon atoms as substituents. An alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, It may have an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, an alkenoyl group having 2 to 8 carbon atoms, or an alkenoyloxy group having 2 to 8 carbon atoms.

  The monofunctional polymerizable liquid crystal compound represented by the general formula (II-2) may be used alone or in combination of two or more, but the total content of the monofunctional polymerizable liquid crystal compound represented by the general formula (II-2) The amount is preferably 0 to 80% by mass, more preferably 0 to 60% by mass, and more preferably 5 to 40% by mass in the total amount of the polymerizable liquid crystal compound used in the polymerizable liquid crystal composition. It is particularly preferred. When importance is attached to the adhesion between the obtained optical anisotropic body and the substrate, the lower limit value is preferably 5% by mass or more, more preferably 10% by mass or more. When emphasizing curability, the upper limit value is preferably 40% by mass or less, and more preferably 20% by mass or less.

The total content of the monofunctional polymerizable liquid crystal compound having one polymerizable functional group in the molecule represented by general formula (II-1) or general formula (II-2) is used for the polymerizable liquid crystal composition. The total amount of the polymerizable liquid crystal compound is preferably 0 to 80% by mass, more preferably 5 to 75% by mass, and particularly preferably 5 to 70% by mass. When importance is attached to the adhesion of the obtained coating film to the substrate, the lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, and importance is given to the curability of the resulting coating film. When it does, it is preferable to make an upper limit into 50 mass% or less, and it is more preferable to set it as 40 mass% or less.
(Other liquid crystal compounds)
Further, the polymerizable liquid crystal composition of the present invention may contain a compound containing a mesogenic group having no polymerizable group, such as a normal liquid crystal device, for example, STN (super twisted nematic) liquid crystal, Examples thereof include compounds used for TN (twisted nematic) liquid crystal, TFT (thin film transistor) liquid crystal, and the like.

  Specifically, the compound containing a mesogenic group having no polymerizable functional group is preferably a compound represented by the following general formula (5).

  The mesogenic group or mesogenic supporting group represented by MG3 has the general formula (5-b)

(In the formula, A1 ^d , A2 ^d and A3 ^d are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group. 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group Pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2 , 6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a- Octahydrof Enanthrene-2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5-b ′] dithiophene-2,6-diyl group, benzo [1,2-b: 4, 5-b ′] diselenophen-2,6-diyl group, [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2-b] selenophene-2 , 7-diyl group, or fluorene-2,7-diyl group, and one or more F, Cl, CF ₃ , OCF ₃ , CN groups, C 1-8 alkyl groups, alkoxy groups as substituents , An alkanoyl group, an alkanoyloxy group, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group, an alkenoyl group, an alkenoyloxy group,
Z0 ^d , Z1 ^d , Z2 ^d and Z3 ^d are each independently —COO—, —OCO—, —CH ₂ CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CH═CH—, — _{C≡C -, - CH = CHCOO -} , - OCOCH = CH -, - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 -, - CONH- , -NHCO-, an alkylene group which may have a halogen atom having 2 to 10 carbon atoms (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom) or a single bond;
n ^e represents 0, 1 or 2,
R ⁵¹ and R ⁵² each independently represent a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a cyano group, or an alkyl group having 1 to 18 carbon atoms. one or more halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom) may be substituted by or CN, this is not one CH ₂ group or adjacent present in group two or more CH ₂ The groups are independent of each other, and in a form in which oxygen atoms are not directly bonded to each other, —O—, —S—, —NH—, —N (CH ₃ ) —, —CO—, —COO—, —OCO -, -OCOO-, -SCO-, -COS- or -C≡C- may be substituted. ).

  Specifically, although shown below, it is not necessarily limited to these.

  Ra and Rb each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, or a cyano group, and these groups have 1 carbon atom. In the case of a -6 alkyl group or a C1-C6 alkoxy group, all may be unsubstituted or may be substituted by one or more halogen atoms.

The total content of the compound having a mesogenic group is preferably 0% by mass or more and 20% by mass or less with respect to the total amount of the polymerizable liquid crystal composition, and when used, it is preferably 1% by mass or more. It is preferably at least mass%, preferably at least 5 mass%, more preferably at most 15 mass%, preferably at most 10 mass%.
(Organic solvent)
An organic solvent may be added to the polymerizable liquid crystal composition in the present invention. Although there is no limitation in particular as an organic solvent to be used, the organic solvent in which a polymeric liquid crystal compound shows favorable solubility is preferable, and it is preferable that it is an organic solvent which can be dried at the temperature of 100 degrees C or less. Examples of such solvents include aromatic hydrocarbons such as toluene, xylene, cumene and mesitylene, ester solvents such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate, methyl ethyl ketone (MEK), methyl isobutyl ketone ( MIBK), ketone solvents such as cyclohexanone and cyclopentanone, ether solvents such as tetrahydrofuran, 1,2-dimethoxyethane and anisole, amide solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone , Propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, γ-butyrolactone and chlorobenzene. These can be used alone or in combination of two or more, but any one of ketone solvents, ether solvents, ester solvents and aromatic hydrocarbon solvents It is preferable to use the above from the viewpoint of solution stability.

  The composition used in the present invention can be applied to a substrate as an organic solvent solution, and the ratio of the organic solvent used in the polymerizable liquid crystal composition is not particularly limited as long as the applied state is not significantly impaired. However, the total amount of organic solvents contained in the polymerizable liquid crystal composition is preferably 10 to 95% by mass, more preferably 12 to 90% by mass, and particularly preferably 15 to 85% by mass. preferable.

  When the polymerizable liquid crystal composition is dissolved in the organic solvent, it is preferably heated and stirred in order to uniformly dissolve the polymerizable liquid crystal composition. The heating temperature at the time of heating and stirring may be appropriately adjusted in consideration of the solubility of the composition to be used in the organic solvent, but is preferably 15 ° C to 110 ° C, more preferably 15 ° C to 105 ° C from the viewpoint of productivity, 15 to 100 degreeC is further more preferable, and it is especially preferable to set it as 20 to 90 degreeC.

  Moreover, when adding a solvent, it is preferable to stir and mix with a dispersion stirrer. Specific examples of the dispersion stirrer include a disperser having a stirring blade such as a disper, a propeller, and a turbine blade, a paint shaker, a planetary stirring device, a shaker, a shaker, or a rotary evaporator. In addition, an ultrasonic irradiation apparatus can be used.

The stirring rotation speed when adding the solvent is preferably adjusted appropriately depending on the stirring device used, but in order to obtain a uniform polymerizable liquid crystal composition solution, the stirring rotation speed is preferably 10 rpm to 1000 rpm, preferably 50 rpm to 800 rpm is more preferable, and 150 rpm to 600 rpm is particularly preferable.
(Polymerization inhibitor)
It is preferable to add a polymerization inhibitor to the polymerizable liquid crystal composition in the present invention. Examples of the polymerization inhibitor include phenol compounds, quinone compounds, amine compounds, thioether compounds, nitroso compounds, and the like.

  Examples of phenolic compounds include p-methoxyphenol, cresol, t-butylcatechol, 3.5-di-t-butyl-4-hydroxytoluene, 2.2'-methylenebis (4-methyl-6-t-butylphenol) 2.2′-methylenebis (4-ethyl-6-tert-butylphenol), 4.4′-thiobis (3-methyl-6-tert-butylphenol), 4-methoxy-1-naphthol, 4,4′- Dialkoxy-2,2′-bi-1-naphthol, and the like.

  As quinone compounds, hydroquinone, methylhydroquinone, tert-butylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, tert-butyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone 1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, anthraquinone, diphenoquinone and the like.

  Examples of amine compounds include p-phenylenediamine, 4-aminodiphenylamine, N.I. N'-diphenyl-p-phenylenediamine, Ni-propyl-N'-phenyl-p-phenylenediamine, N- (1.3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N.I. N′-di-2-naphthyl-p-phenylenediamine, diphenylamine, N-phenyl-β-naphthylamine, 4.4′-dicumyl-diphenylamine, 4.4′-dioctyl-diphenylamine and the like.

  Examples of thioether compounds include phenothiazine and distearyl thiodipropionate.

  Examples of nitroso compounds include N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, N-nitrosodinaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, and N, N-dimethyl. p-nitrosoaniline, p-nitrosodiphenylamine, p-nitronedimethylamine, p-nitrone-N, N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-Nn-butyl- 4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine Ammonium salt, ditrosobenzene, 2,4.6-tri-tert-butylnitronebenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-N- n-propyl urethane, 1-nitroso-2-naphthol, 2-nitroso 1-naphthol, sodium 1-nitroso-2-naphthol-3,6-sulfonate, sodium 2-nitroso-1-naphthol-4-sulfonate, Examples include 2-nitroso-5-methylaminophenol hydrochloride and 2-nitroso-5-methylaminophenol hydrochloride.

The addition amount of the polymerization inhibitor is preferably 0.01 to 1.0% by mass and more preferably 0.05 to 0.5% by mass with respect to the polymerizable liquid crystal composition.
(Photopolymerization initiator)
The polymerizable liquid crystal composition in the present invention preferably contains a photopolymerization initiator. It is preferable to contain at least one photopolymerization initiator. Specifically, “Irgacure 651”, “Irgacure 184”, “Darocur 1173”, “Irgacure 907”, “Irgacure 127”, “Irgacure 369”, “Irgacure 379”, “Irgacure 819”, “ "Irgacure 2959", "Irgacure 1800", "Irgacure 250", "Irgacure 754", "Irgacure 784", "Irgacure OXE01", "Irgacure OXE02", "Lucirin TPO", "Darocure 1173", "Darocure MBF" and LAMBSON “Esacure 1001M”, “Esacure KIP150”, “Speed Cure BEM”, “Speed Cure BMS”, “Speed Cure MBP”, “Speed Cure PBZ”, “Speed Cure ITX” “Speed Cure DETX”, “Speed Cure EBD”, “Speed Cure MBB”, “Speed Cure BP”, “Kayacure DMBI” manufactured by Nippon Kayaku Co., Ltd., “TAZ-A” manufactured by Nippon Sybel Hegner (currently DKSH) "Adekaoptomer SP-152", "Adekaoptomer SP-170", "Adekaoptomer N-1414", "Adekaoptomer N-1606", "Adekaoptomer N-1717" manufactured by ADEKA, “Adekaoptomer N-1919”, “Syracure UVI-6990”, “Syracure UVI-6974” and “Syracure UVI-6922” manufactured by UCC, “Adekaoptomer SP-150” manufactured by Asahi Denka Kogyo Co., Ltd. , SP-152, SP-170, SP-172 "or Rhodia's" PHOTOINI " IATOR2074 ", BASF Corp. of" Irgacure 250 ", GE Silicones Co., Ltd. of" UV-9380C ", Midori Chemical Co., Ltd. of the" DTS-102 ", and the like.

The amount of the photopolymerization initiator used is preferably 0.1 to 10 parts by mass, and 0.5 to 7 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition. Is particularly preferred. In order to improve the curability of the optical anisotropic body, it is preferable to use a photopolymerization initiator of 3 parts by mass or more with respect to 100 parts by mass of the polymerizable liquid crystal compound. These can be used alone or in combination of two or more, and a sensitizer or the like may be added.
(Thermal polymerization initiator)
In the polymerizable liquid crystal composition of the present invention, a thermal polymerization initiator may be used in combination with a photopolymerization initiator. Known and commonly used thermal polymerization initiators can be used, such as methyl acetoacetate peroxide, cumene hydroperoxide, benzoyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butyl. Peroxybenzoate, methyl ethyl ketone peroxide, 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, p-pentahydroperoxide, t-butylhydroperoxide, dicumyl peroxide, isobutyl Peroxides, organic peroxides such as di (3-methyl-3-methoxybutyl) peroxydicarbonate, 1,1-bis (t-butylperoxy) cyclohexane, 2,2′-azobisisobutyronitrile , 2,2′-azobis (2,4 Azonitrile compounds such as dimethylvaleronitrile), azoamidin compounds such as 2,2′-azobis (2-methyl-N-phenylpropion-amidin) dihydrochloride, 2,2′azobis {2-methyl-N- [1, An azoamide compound such as 1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, an alkylazo compound such as 2,2′azobis (2,4,4-trimethylpentane), and the like can be used. Specifically, “V-40”, “VF-096” manufactured by Wako Pure Chemical Industries, Ltd., “Perhexyl D”, “Perhexyl I” of Nippon Oil & Fats Co., Ltd. (currently Nippon Oil Co., Ltd.) Etc.

The amount of the thermal polymerization initiator used is preferably from 0.1 to 10 parts by weight, particularly preferably from 0.5 to 5 parts by weight, based on 100 parts by weight of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition. . These can be used alone or in combination of two or more.
(Surfactant)
The polymerizable liquid crystal composition in the present invention may contain at least one surfactant in order to reduce film thickness unevenness when an optical anisotropic body is used. Surfactants that can be included include alkyl carboxylates, alkyl phosphates, alkyl sulfonates, fluoroalkyl carboxylates, fluoroalkyl phosphates, fluoroalkyl sulfonates, polyoxyethylene derivatives, fluoro Examples thereof include alkylethylene oxide derivatives, polyethylene glycol derivatives, alkylammonium salts, fluoroalkylammonium salts and the like, and fluorine-containing surfactants are particularly preferable.

Specifically, "Megafuck F-251", "Megafuck F-444", "Megafuck F-477", "Megafuck F-510", "Megafuck F-552", "Megafuck F-""553","MegafuckF-554","MegafuckF-555","MegafuckF-556","MegafuckF-557","MegafuckF-558","MegafuckF-559" , “Megafuck F-560”, “Megafuck F-561”, “Megafuck F-562”, “Megafuck F-563”, “Megafuck F-565”, “Megafuck F-567”, “ “Megafuck F-568”, “Megafuck F-569”, “Megafuck F-570”, “Megafuck F-571”, “Megafuck R-40” , “Megafuck R-41”, “Megafuck R-43”, “Megafuck R-94”, “Megafuck RS-72-K”, “Megafuck RS-75”, “Megafuck RS-76-” E "," Megafuck RS-90 "(above, manufactured by DIC Corporation),
“Furgent 100”, “Furgent 100C”, “Furgent 110”, “Furgent 150”, “Furgent 150CH”, “Furgent A”, “Furgent 100A-K”, “Furgent 501”, "Factent 300", "Factent 310", "Factent 320", "Factent 400SW", "FTX-400P", "Factent 251", "Factent 215M", "Factent 212MH", "Footer Gent 250, Fategent 222F, Fategent 212D, FTX-218, FTX-209F, FTX-213F, FTX-233F, Fate 245F, FTX-208G ”,“ FTX-240G ”,“ FT -206D "," FTX-220D "," FTX-230D "," FTX-240D "," FTX-207S "," FTX-211S "," FTX-220S "," FTX-230S "," FTX-750FM " ”,“ FTX-730FM ”,“ FTX-730FL ”,“ FTX-710FS ”,“ FTX-710FM ”,“ FTX-710FL ”,“ FTX-750LL ”,“ FTX-730LS ”,“ FTX-730LM ”, "FTX-730LL", "FTX-710LL" (above, manufactured by Neos Corporation),
“BYK-300”, “BYK-302”, “BYK-306”, “BYK-307”, “BYK-310”, “BYK-315”, “BYK-320”, “BYK-322”, “BYK” -323 "," BYK-325 "," BYK-330 "," BYK-331 "," BYK-333 "," BYK-337 "," BYK-340 "," BYK-344 "," BYK-370 " ”,“ BYK-375 ”,“ BYK-377 ”,“ BYK-350 ”,“ BYK-352 ”,“ BYK-354 ”,“ BYK-355 ”,“ BYK-356 ”,“ BYK-358N ”, “BYK-361N”, “BYK-357”, “BYK-390”, “BYK-392”, “BYK-UV3500”, “BYK-UV3510”, “BYK-UV3570”, “B K-Silclean3700 "(manufactured by BYK Japan KK),
“TEGO Rad2100”, “TEGO Rad2200N”, “TEGO Rad2250”, “TEGO Rad2300”, “TEGO Rad2500”, “TEGO Rad2600”, “TEGO Rad2700” (above, manufactured by TEGO)
Examples include “N215”, “N535”, “N605K”, “N935” (above, manufactured by Solvay Solexis).

  In the present invention, the surfactant is not an essential component, but when added, the surfactant is added in an amount of 0.001 part by mass relative to 100 parts by mass of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition. It is preferably 01 to 2 parts by mass, and more preferably 0.05 to 0.5 parts by mass.

  In addition, by using the surfactant, when the polymerizable liquid crystal composition of the present invention is an optical anisotropic body, the tilt angle of the air interface can be effectively reduced.

  The polymerizable liquid crystal composition according to the present invention has the effect of effectively reducing the tilt angle of the air interface in the case of an optical anisotropic body, and is represented by the following general formula (7) except for the surfactant. Examples thereof include compounds having a unit having a weight average molecular weight of 100 or more.

In the formula, each of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ independently represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and one or more hydrogen atoms in the hydrocarbon group It may be substituted with a halogen atom.

  Suitable examples of the compound represented by the general formula (7) include polyethylene, polypropylene, polyisobutylene, paraffin, liquid paraffin, chlorinated polypropylene, chlorinated paraffin, and chlorinated liquid paraffin.

The amount of the compound represented by the general formula (7) is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition. It is more preferable that it is 0.05-0.5 mass part.
(Non-liquid crystalline compound having a polymerizable group)
In the polymerizable composition of the present invention, a compound having a polymerizable group but not a liquid crystal compound can be added. Such a compound can be used without particular limitation as long as it is generally recognized as a polymerizable monomer or polymerizable oligomer in this technical field. The addition amount of the non-liquid crystalline compound having a polymerizable group is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition. It is more preferable that it is 0.05-1 mass part, and 0.05-0.5 mass part is especially preferable.
Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl acrylate, propyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, Dicyclopentanyloxylethyl (meth) acrylate, isobornyloxylethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethyl Damantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethyl carbitol (meth) acrylate, tetrahydroflur Furyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-phenoxydiethylene glycol (meth) acrylate, ω-carboxy-polycaprolactone (n≈2) monoacrylate, 2-hydroxy-3-phenoxypropyl Acrylate, 2-hydroxy-3-phenoxyethyl (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, ( -Ethyloxetane-3-yl) methyl (meth) acrylate, o-phenylphenol ethoxy (meth) acrylate, dimethylamino (meth) acrylate, diethylamino (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (Meth) acrylate, 2,2,3,4,4,4-hexafluorobutyl (meth) acrylate, 2,2,3,3,4,4,4-heptafluorobutyl (meth) acrylate, 2- ( Perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 1H, 1H, 3H-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate 1H, 1H, 7H-dodecafluoroheptyl (meth) Chryrate, 1H-1- (trifluoromethyl) trifluoroethyl (meth) acrylate, 1H, 1H, 3H-hexafluorobutyl (meth) acrylate, 1,2,2,2-tetrafluoro-1- (trifluoromethyl) ) Ethyl (meth) acrylate, 1H, 1H-pentadecafluorooctyl (meth) acrylate, 1H, 1H, 2H, 2H-tridecafluorooctyl (meth) acrylate, 2- (meth) acryloyloxyethylphthalic acid, 2- (Meth) acryloyloxyethyl hexahydrophthalic acid, glycidyl (meth) acrylate, 2- (meth) acryloyloxyethyl phosphoric acid, acryloylmorpholine, dimethylacrylamide, dimethylaminopropylacrylamide, isopropylpropylacrylamide, diethylacetate Mono (meth) acrylates such as rilamide, hydroxyethylacrylamide, N-acryloyloxyethylhexahydrophthalimide, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9- Nonanediol di (meth) acrylate, neopentyldiol di (meth) acrylate, tripropylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Ethylene oxide modified bisphenol A di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] phenyl Orene, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, acrylic acid adduct of 1,6-hexanediol diglycidyl ether, acrylic acid adduct of 1,4-butanediol diglycidyl ether , Etc. Diacrylate such as trimethylolpropane tri (meth) acrylate, ethoxylated isocyanuric acid triacrylate, pentaerythritol tri (meth) acrylate, ε-caprolactone modified tris- (2-acryloyloxyethyl) isocyanurate Tetra (meth) acrylates such as (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, etc., dipentaerythritol hexa (meth) acrylate Rate, oligomeric (meth) acrylate, various urethane acrylates, various macromonomers, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl Examples thereof include epoxy compounds such as ether, glycerin diglycidyl ether, and bisphenol A diglycidyl ether, and maleimide. These can be used alone or in combination of two or more.
(Chain transfer agent)
The polymerizable liquid crystal composition in the present invention preferably further includes a chain transfer agent in order to further improve the adhesion with the base material in the case of an optical anisotropic body. The chain transfer agent is preferably a thiol compound, more preferably a monothiol, dithiol, trithiol, or tetrathiol compound, and even more preferably a trithiol compound. Specifically, compounds represented by the following general formulas (8-1) to (8-13) are preferable.

In the formula, R ⁶⁵ represents an alkyl group having 2 to 18 carbon atoms, and the alkyl group may be linear or branched, and one or more methylene groups in the alkyl group are oxygen atoms. And a sulfur atom that is not directly bonded to each other, may be substituted with an oxygen atom, a sulfur atom, —CO—, —OCO—, —COO—, or —CH═CH—, and R ⁶⁶ is a carbon atom. Represents an alkylene group of 2 to 18, wherein one or more methylene groups in the alkylene group are oxygen atoms, sulfur atoms, -CO-, -OCO- , —COO—, or —CH═CH— may be substituted.

The addition amount of the chain transfer agent is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition, and preferably 1.0 to 5.0. More preferably, it is part by mass.
(Dye)
The polymerizable liquid crystal composition of the present invention may contain a dye as necessary. The dye to be used is not particularly limited, and may include known and commonly used dyes as long as the orientation is not disturbed.

Examples of the dye include a dichroic dye and a fluorescent dye. Examples of such dyes include polyazo dyes, anthraquinone dyes, cyanine dyes, phthalocyanine dyes, perylene dyes, perinone dyes, squarylium dyes and the like. From the viewpoint of addition, the dye is preferably a liquid crystal dye. . For example, U.S. Pat. No. 2,400,877, Dreyer J. F., Phys. And Colloid Chem., 1948, 52, 808., "The Fixing of Molecular Orientation", Dreyer JF, Journal de Physique, 1969, 4, 114., "LightPolarization from Films of Lyotropic Nematic Liquid Crystals" and J. Lydon, "Chromonics" in "Handbook of Liquid Crystals Vol.2B: Low MolecularWeight Liquid Crystals II", D. Demus, J. Goodby, GW Gray , HW Spiessm, V. Villed, Willey-VCH, P. 981-1007 (1998), Dichroic Dyes for Liquid Crystal Display A. V. lvashchenko
The dyes described in CRC Press, 1994, and “New Developments in Functional Dye Market”, Chapter 1, Page 1, 1994, CMC Corporation Luminescence, etc. can be used.

  Examples of the dichroic dye include the following formulas (d-1) to (d-8).

Is mentioned. The added amount of the dichroic dye or the like is preferably 0.001 to 10 parts by mass, and 0.01 to 5 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable liquid crystal compound contained in the powder mixture. More preferably, it is a part.
(Filler)
The polymerizable liquid crystal composition of the present invention may contain a filler as necessary. The filler to be used is not particularly limited, and may contain known and commonly used fillers as long as the thermal conductivity of the obtained polymer is not lowered. Specifically, inorganic fillers such as alumina, titanium white, aluminum hydroxide, talc, clay, mica, barium titanate, zinc oxide, glass fiber, metal powder such as silver powder, copper powder, aluminum nitride, boron nitride, Examples thereof include thermally conductive fillers such as silicon nitride, gallium nitride, silicon carbide, magnesia (aluminum oxide), alumina (aluminum oxide), crystalline silica (silicon oxide), fused silica (silicon oxide), and silver nanoparticles. .
(Other additives)
Furthermore, in order to adjust the physical properties, additives such as polymerizable compounds that do not have liquid crystallinity, thixotropic agents, ultraviolet absorbers, infrared absorbers, antioxidants, surface treatment agents, etc., do not significantly reduce the alignment ability of liquid crystals. To the extent that can be added.
(Optical anisotropic body manufacturing method)
(Optical anisotropic)
The optical anisotropic body produced using the polymerizable liquid crystal composition of the present invention is obtained by sequentially laminating a base material, if necessary, an alignment film, and a polymer of the polymerizable liquid crystal composition.
(Base material)
The substrate used for the optical anisotropic body of the present invention is a substrate that is usually used for liquid crystal devices, displays, optical components and optical films, and is heated during drying after the application of the polymerizable liquid crystal composition of the present invention. If it is the material which has heat resistance which can endure, there will be no restriction | limiting in particular. Examples of such a substrate include organic materials such as a glass substrate, a metal substrate, a ceramic substrate, and a plastic substrate. In particular, when the substrate is an organic material, examples thereof include cellulose derivatives, polyolefins, polyesters, polycarbonates, polyacrylates (acrylic resins), polyarylate, polyether sulfone, polyimide, polyphenylene sulfide, polyphenylene ether, nylon, and polystyrene. Among them, plastic base materials such as polyester, polystyrene, polyacrylate, polyolefin, cellulose derivative, polyarylate, and polycarbonate are preferable, and base materials such as polyacrylate, polyolefin, and cellulose derivative are more preferable, and COP (cycloolefin polymer) is used as the polyolefin. It is particularly preferable to use TAC (triacetyl cellulose) as the cellulose derivative and PMMA (polymethyl methacrylate) as the polyacrylate. As a shape of a base material, you may have a curved surface other than a flat plate. These base materials may have an electrode layer, an antireflection function, and a reflection function as needed.

In order to improve the applicability and adhesiveness of the polymerizable liquid crystal composition of the present invention, these substrates may be subjected to surface treatment. Examples of the surface treatment include ozone treatment, plasma treatment, corona treatment, silane coupling treatment, and the like. In addition, in order to adjust the light transmittance and reflectance, an organic thin film, an inorganic oxide thin film, a metal thin film, etc. are provided on the surface of the substrate by a method such as vapor deposition, or in order to add optical added value. The material may be a pickup lens, a rod lens, an optical disk, a retardation film, a light diffusion film, a color filter, or the like. Among these, a pickup lens, a retardation film, a light diffusion film, and a color filter that have higher added value are preferable.
(Orientation treatment)
In addition, as the substrate, a glass substrate alone or an alignment film is provided on the substrate so that the polymerizable liquid crystal composition is aligned when the polymerizable liquid crystal composition of the present invention is applied and dried. Also good. Examples of the alignment treatment include stretching treatment, rubbing treatment, polarized ultraviolet visible light irradiation treatment, ion beam treatment, and the like. When the alignment film is used, a known and conventional alignment film is used. As such an alignment film, a hydrophilic polymer containing polyimide, polyamide, lecithin, hydroxyl group, carboxylic acid group or sulfonic acid group, a hydrophilic inorganic compound, a photo-alignment film, or the like can be used. Examples of the hydrophilic polymer include polyvinyl alcohol, polyacrylic acid, polyacrylic acid soda, polymethacrylic acid, sodium polyalginate, polycarboxymethylcellulose soda salt, pullulan, and polystyrene sulfonic acid. Examples of hydrophilic inorganic compounds include oxides such as Si, Al, Mg, and Zr, and inorganic compounds such as fluoride. Since the hydrophilic base material is effective for orienting the optical axis of the optical anisotropic body almost parallel to the normal direction with respect to the base material, it is preferable for obtaining the optical anisotropic body of the positive C plate. However, since it acts as a horizontal alignment film when a rubbing treatment is performed on a hydrophilic substrate, the rubbing treatment adversely affects the vertical alignment in the hydrophilic polymer layer, so that an optical anisotropic body of a positive C plate is obtained. Is not preferred.
(Application)
Application methods for obtaining the optical anisotropic body of the present invention include applicator method, bar coating method, spin coating method, roll coating method, direct gravure coating method, reverse gravure coating method, flexo coating method, ink jet method, and die coating. A publicly known method such as a method, a cap coating method, a dip coating method, or a slit coating method can be used. After coating the polymerizable liquid crystal composition, the solvent contained in the polymerizable liquid crystal composition is dried by heating as necessary.
(Polymerization process)
Regarding the polymerization operation of the polymerizable liquid crystal composition of the present invention, the liquid crystal compound in the polymerizable liquid crystal composition is generally in a state in which it is horizontally aligned, vertically aligned, hybrid aligned, or cholesteric aligned (planar aligned) with respect to the substrate. It is performed by irradiation with light such as ultraviolet rays or by heating. When the polymerization is performed by light irradiation, specifically, it is preferable to irradiate ultraviolet light having a wavelength of 390 nm or less, and it is most preferable to irradiate light having a wavelength of 250 to 370 nm. However, when the polymerizable liquid crystal composition causes decomposition or the like due to ultraviolet light of 390 nm or less, it may be preferable to perform polymerization treatment with ultraviolet light of 390 nm or more. This light is preferably diffused light and unpolarized light.
(Polymerization method)
Examples of the method for polymerizing the polymerizable liquid crystal composition of the present invention include a method of irradiating active energy rays and a thermal polymerization method. However, since the reaction proceeds at room temperature without requiring heating, active energy rays are used. A method of irradiating is preferable, and among them, a method of irradiating light such as ultraviolet rays is preferable because the operation is simple.

The temperature at the time of irradiation is preferably set to 30 ° C. or less as much as possible in order to avoid the induction of thermal polymerization of the polymerizable liquid crystal composition so that the polymerizable liquid crystal composition of the present invention can maintain the liquid crystal phase. The liquid crystal composition usually exhibits a nematic phase only liquid crystal phase by phase transition in the order of Cr (crystal) -N (nematic) -I (isotropic liquid) in the temperature rising process. In the case of the polymerizable liquid crystal composition, the phase transition of Cr (crystal) -Sm (smectic) -N (nematic) -I (isotropic liquid) is caused in the temperature rising process because of the characteristic of exhibiting smectic liquid crystal properties. For the sake of illustration, two liquid crystal phases, a smectic phase and a nematic phase, are shown. On the other hand, in the temperature lowering process, since it takes a thermodynamically non-equilibrium state, it does not crystallize below the Cr (crystal) -N (nematic) or Cr (crystal) -Sm (smectic) transition temperature. The liquid crystal state may be maintained. This state is called a supercooled state. In the present invention, the liquid crystal composition in a supercooled state is also included in the state in which the liquid crystal phase is retained. Because the smectic phase has a layer structure, it has a structure closer to the crystal than the nematic phase, so it irradiates ultraviolet rays in the smectic phase state rather than the optical anisotropic body obtained by irradiating ultraviolet rays in the nematic phase state. The optically anisotropic body obtained in this manner is preferable because it becomes an optically anisotropic body having a structure closer to a crystal, and orientation order and / or heat resistance is improved. The smectic phase is roughly classified into two types depending on whether the molecular long axis is perpendicular or inclined with respect to the layer normal. The smectic phase in which the molecular long axis is perpendicular to the layer normal includes a smectic A phase (SmA) and a smectic B phase (SmB), and the smectic phase whose molecular long axis is inclined with respect to the layer normal is smectic C. A phase (SmC), a smectic F phase (SmF), a smectic G phase (SmG), a smectic I phase (SmI), and a smectic J phase (SmJ) are known. In the homogeneous alignment, when the phase transition from the nematic phase whose molecular long axis is aligned in the rubbing direction of the polyimide alignment film to the smectic phase, the smectic phase in which the molecular long axis is perpendicular to the layer normal, specifically smectic A In the phase (SmA) and smectic B (SmB), the molecular major axis in the layer is oriented along the rubbing direction, and therefore, the occurrence of orientation defects is small and favorable orientation is preferable.
Specifically, the method of irradiating light such as ultraviolet rays preferably irradiates ultraviolet light of 390 nm or less, and most preferably irradiates light having a wavelength of 250 to 370 nm. However, when the polymerizable composition causes decomposition or the like due to ultraviolet light of 390 nm or less, it may be preferable to perform the polymerization treatment with ultraviolet light of 390 nm or more. This light is preferably diffused light and unpolarized light. The ultraviolet irradiation intensity is preferably in the range of 0.05 kW / m ^{2 to} 10 kW / m ² . In particular, a range of 0.2 kW / m ^{2 to 2} kW / m ² is preferable. When the ultraviolet intensity is less than 0.05 kW / m ² , it takes a lot of time to complete the polymerization. On the other hand, when the strength exceeds ² kW / m ² , liquid crystal molecules in the polymerizable liquid crystal composition tend to be photodegraded, or a large amount of polymerization heat is generated to increase the temperature during polymerization. The parameter may change, and the retardation of the film after polymerization may be distorted.

  After only a specific part is polymerized by UV irradiation using a mask, the orientation state of the unpolymerized part is changed by applying an electric field, a magnetic field or temperature, and then the unpolymerized part is polymerized. An optical anisotropic body having a plurality of regions having orientation directions can also be obtained.

  Further, when only a specific portion was polymerized by ultraviolet irradiation using a mask, the alignment was regulated in advance by applying an electric field, magnetic field or temperature to the unpolymerized polymerizable liquid crystal composition, and the state was maintained. An optical anisotropic body having a plurality of regions having different orientation directions can also be obtained by irradiating light from above the mask and polymerizing it.

The optical anisotropic body obtained by polymerizing the polymerizable liquid crystal composition of the present invention can be peeled off from the substrate and used alone as an optical anisotropic body, or it can be used as an optical anisotropic body as it is without peeling off from the substrate. You can also In particular, since it is difficult to contaminate other members, it is useful when used as a laminated substrate or by being attached to another substrate.
(Retardation film)
The retardation film of the present invention is prepared in the same manner as the optical anisotropic body of the present invention. Specifically, when polymerization is performed in a state where the molecular long axis of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition is aligned horizontally with respect to the substrate, the obtained cured product is a retardation film of a positive A plate. Can be used as When polymerized in a state where the molecular long axis of the polymerizable liquid crystal compound is aligned perpendicular to the substrate, the obtained cured product can be used as a retardation film of a positive C plate. When the polymerizable liquid crystal compound and the polymerizable chiral compound form a helix and polymerize in a state where the helix axis is perpendicular to the substrate, the obtained cured product is used as a retardation film of a negative C plate. can do. In addition, the cured product obtained by polymerization in a state where the molecular length of the polymerizable liquid crystal compound is inclined at a certain angle (tilted orientation) with respect to the substrate can be used as a retardation film of an O plate. Polymerization can also be performed in a state (hybrid orientation) in which the molecular long axis is perpendicular to the substrate as it is perpendicular to the substrate near the interface and closer to the air interface. In the liquid crystal state of the smectic phase, it is preferable to polymerize in homeotropic alignment or homogeneous alignment. When the substrate has a retardation, a retardation film having birefringence obtained by adding the birefringence of the substrate and the birefringence of the retardation film of the present invention can be obtained. In the retardation film, the birefringence of the base material and the birefringence of the retardation film may be in the same direction or different directions in the plane of the base material. The liquid crystal device, the display, the optical element, the optical component, the colorant, the marking for security, the member for laser emission, the optical film, and the compensation film are applied in a form suitable for the application.
(Viewing angle compensation film)
The viewing angle compensation film of the present invention is produced in the same manner as the optical anisotropic body of the present invention. The viewing angle compensation film, which is a homeotropically aligned liquid crystal film, is incorporated in an IPS (In-Plane Switching) type liquid crystal display device, and the color and contrast of an image viewed when the liquid crystal display device is viewed from an oblique direction. Is used to reduce the problem of changing.
(Antireflection film)
The antireflection film of the present invention is prepared in the same manner as the optical anisotropic body of the present invention. When a circularly polarizing plate in which a polarizing plate and a quarter-wave plate are laminated is applied to an organic EL element, the circularly polarizing plate functions ideally for incident light from a direction perpendicular to the circularly polarizing plate, For incident light from an oblique direction, a deviation from a quarter wavelength occurs, and the light does not function as an ideal circularly polarizing plate. When the optically anisotropic body that is homeotropically aligned is used in a circularly polarizing plate for the purpose of preventing external light reflection, the viewing angle dependency in black display can be reduced even for incident light from an oblique direction.
(Polarizer)
The polarizing plate of the present invention is prepared in the same manner as the optical anisotropic body of the present invention. An optical anisotropic body obtained by adding a dye or a pigment to the polymerizable liquid crystal composition of the present invention includes infrared light having a wavelength of 800 nm or more, ultraviolet light having a wavelength of 250 nm or less, and visible light having a wavelength of 250 to 800 nm. In particular, the polymerizable liquid crystal composition of the present invention is preferably used for a coating type polarizing plate, and the optical anisotropic body of the present invention is preferably used as a coating type polarizing plate. .

Hereinafter, the present invention will be described with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” are based on mass.
(Preparation of polymerizable liquid crystal composition)
With respect to 100 parts by mass of the total amount of the compounds represented by formulas (A-1) to (A-7) and formulas (B-1) to (B-3) shown in Tables 1 and 2, (C- 1) to (C-2), (D-1), (E-1) to (E-3), (F-1), (F-2), and organic solvents (G-1) to Polymeric liquid crystal compositions (1) to (15) were prepared by blending (G-4) in proportions (parts by mass) shown in Tables 1 and 2, respectively.
(Preparation of polymerizable liquid crystal composition (1))
As shown in Table 1, 15 parts by mass of the compound represented by the formula (A-1), 28.3 parts by mass of the compound represented by the formula (A-4), and the compound 22 represented by the formula (A-5) 7 parts by mass, 3 parts by mass of polymerization initiator (C-1) and p-methoxyphenol as a polymerization inhibitor with respect to 100 parts by mass of the total of 34 parts by mass of the compound represented by formula (B-1) (MEHQ) (D-1) 0.1 parts by mass, surfactant (E-1) 0.2 parts by mass, and toluene (G-2) 70 parts by mass as an organic solvent, and having a stirring propeller Using a stirrer, the mixture was stirred for 1 hour under conditions of a stirring speed of 500 rpm and a solution temperature of 60 ° C., and then filtered through a 0.2 μm membrane filter to obtain a polymerizable liquid crystal composition (1).
(Preparation of polymerizable liquid crystal compositions (2) to (13) and comparative polymerizable liquid crystal compositions (14) to (15))
Similarly to the preparation of the polymerizable liquid crystal composition (1) of the present invention, the compounds represented by the formulas (A-1) to (A-7) shown in Tables 1 to 3 and the formulas (B-1) to (B-1) to Compound represented by formula (B-3), polymerization initiator (C-1) to formula (C-2), polymerization inhibitor (D-1), surfactant (E-1) to formula (E- 2) The components of the non-liquid crystalline compounds (F-1) and (F-2) having a polymerizable group and the organic solvents (G-1) to (G-4) are shown in Tables 1 and 2, respectively. The polymerizable liquid crystal compositions (2) to (13) and the comparative polymerizable liquid crystal compositions (14) to (15) are the same as the preparation of the polymerizable liquid crystal composition (1) except that the ratio is changed to the ratio shown. )

Tables 1 and 2 show specific compositions of the polymerizable liquid crystal compositions (1) to (13) and the comparative polymerizable liquid crystal compositions (14) to (15) of the present invention.

Irgacure 907 (C-1)
Irgacure OXE02 (C-2)
MEHQ (D-1)
Liquid paraffin (E-1)
Mega Fuck F-554 (E-2)
Dicyclopentanyl acrylate (F-1)
2-Hydroxy-3-phenoxypropyl acrylate (F-2)
Cyclopentanone (G-1)
Toluene (G-2)
MIBK (G-3)
MEK (G-4)
Example 1
(Orientation)
The prepared polymerizable liquid crystal composition (1) was rubbed on a glass substrate with a horizontal alignment polyimide (SE-6514 manufactured by Nissan Chemical Co., Ltd.) using a bar coater # 4 and dried at 60 ° C. for 2 minutes. Then, after leaving at 25 ° C. for 1 minute, a thin film of Example 1 was obtained by irradiating UV light set so that the amount of light was 300 mJ / cm ² using a conveyor type high-pressure mercury lamp. .
(Double-circle): There is no defect visually and there is no defect also by polarization microscope observation.
A: There are no defects visually, but a non-oriented portion exists in part by observation with a polarizing microscope.
Δ: There are no defects visually, but there are non-oriented portions as a whole by observation with a polarizing microscope.
X: Some defects are visually observed, and non-oriented portions are present as a whole by observation with a polarizing microscope.
(durability)
The thin film obtained in the orientation evaluation test was held at 85 ° C. for 500 hours to obtain a thin film for durability measurement.
<Phase difference change (rate) measurement>
Phase difference Re after incident heating θ = 50 ° before and after the heating test was measured with Otsuka Electronics RETS-100 (wavelength is 550 nm), and the phase difference after heating was set to 100% before heating. The rate of change was evaluated.
◎: Less than 3% change ○: 3% or more to less than 7% decrease △: 7% or more to less than 10% decrease ×: 10% or more decrease (repel evaluation)
The repellency of the coating film whose orientation was measured was visually observed.
A: No repellency defects are observed on the coating surface.
◯: Slight repellency defects are observed on the coating film surface.
(Triangle | delta): A little repellency defect is observed on the coating-film surface.
X: Many repelling defects are observed on the coating film surface.
The results obtained are shown in the table below.
(Tni, Tna measurement)
After applying the prepared polymerizable liquid crystal composition (1) on a glass substrate with a horizontal alignment polyimide (SE-6514 manufactured by Nissan Chemical Co., Ltd.) rubbed with a spin coat (2000 rpm × 15 seconds), 1 at 80 ° C. It was dried for a minute to obtain a thin film of a polymerizable liquid crystal composition. The thin film of this polymerizable liquid crystal composition is heated to an isotropic liquid with a polarizing microscope with a hot stage, and then observed while cooling at minus 2 ° C./min, whereby the transition temperature from the isotropic liquid to the nematic phase ( Tni) and the temperature (Tna) at which the nematic phase transitions to the smectic phase were measured. As a result, Tni was 97.1 ° C. and Tna 59.7 ° C.

(Examples 2-13, Comparative Examples 1-2)
Thin films were prepared using the polymerizable liquid crystal compositions (2) to (15), and the orientation, durability, and repellency were measured. The results are shown in the above table as Examples 2 to 12 and Comparative Examples 1 and 2, respectively.

In Examples 2 to 13 and Comparative Examples 1 and 2, as a base material for evaluation of orientation, etc., as in Example 1, a rubbed polyimide for horizontal alignment (SE- manufactured by Nissan Chemical Co., Ltd.) was used. 6514) Using a glass substrate, the application and curing conditions of the polymerizable liquid crystal composition were as follows: each polymerizable liquid crystal composition was applied at room temperature using a bar coater # 4, dried at 60 ° C. for 2 minutes, and then 25 ° C. Then, using a conveyor type high-pressure mercury lamp, the UV light was set so that the amount of light was 300 mJ / cm ² . For the phase difference change (rate) measurement, the phase difference Re of incident light θ = 50 ° before and after the heating test was measured with RETS-100 manufactured by Otsuka Electronics (wavelength was 550 nm), and the phase difference before heating was 100%. The rate of change in phase difference after heating was evaluated. The phase transition temperature of the polymerizable liquid crystal material comprising the polymerizable liquid crystal composition (14) used in Comparative Example 1 was measured by the same method as in Example (1), Tni was 72.0 ° C., Tna was 51. The polymerizable liquid crystal material comprising the polymerizable liquid crystal composition (15) used in Comparative Example 2 had a Tni of 68.0 ° C. and a Tna of 55.0 ° C.

Example 13 uses a COP (cycloolefin polymer) substrate laminated with a silane coupling type vertical alignment film, and the coating and curing conditions of the polymerizable liquid crystal composition are as follows. was applied at room temperature using a # 4, after two minutes drying at 60 ° C., after standing for 1 min at 25 ° C., using a high pressure mercury lamp of the conveyor type, and set to the amount of light is 300 mJ / cm ² Thus, the conditions for UV light irradiation were set. For the phase difference change (rate) measurement, the phase difference Re of incident light θ = 50 ° before and after the heating test was measured with RETS-100 manufactured by Otsuka Electronics (wavelength was 550 nm), and the phase difference before heating was 100%. The rate of change in phase difference after heating was evaluated.

  As a result, a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound represented by formula (I-1) of the present invention represented by formula (A-1) to formula (A-2) (Example 1). To Example 13) is an isotropic liquid as compared with the polymerizable liquid crystal compositions not containing the polymerizable liquid crystal compound represented by formula (I-1) of the present invention (Comparative Examples 1 to 6). Since the polymerizable liquid crystal material has a high transition temperature (Tni) and a high upper limit temperature (Tna) for forming a smectic phase, it has a good homogeneous alignment or homeotropic alignment, and has excellent durability. An optical anisotropic body with few repelling defects can be obtained. On the other hand, the polymerizable liquid crystal composition not containing the polymerizable liquid crystal compound represented by the general formula (I-1) of the present invention forms a smectic phase although the transition temperature (Tni) to the isotropic liquid is high. Since the polymerizable liquid crystal material does not have a high maximum temperature (Tna), the orientation is poor, and repellency defects are generated, so that it is not possible to obtain an optically anisotropic body having good homogeneous alignment or homeotropic alignment.

  In particular, the polymerizable liquid crystal compound represented by the general formula (I-1) of the present invention, the polymerizable liquid crystal compound represented by the general formula (II-1) of the present invention, and the general formula (I-2) of the present invention. The polymerizable liquid crystal composition used in combination with the polymerizable liquid crystal compound represented by the formula can have an optically anisotropic body having better homogeneous alignment or homeotropic alignment, excellent durability, and few repelling defects. .

Claims (9)

Contains at least two polymerizable liquid crystal compounds having two polymerizable functional groups in the molecule, one of which is represented by the general formula (I-1)

(Wherein P ¹¹¹ and P ¹¹² each independently represent a polymerizable functional group, and Sp ¹¹¹ and Sp ¹¹² each independently represent an alkylene group having 1 to 18 carbon atoms or a single bond, One —CH ₂ — or two or more non-adjacent —CH ₂ — may be each independently replaced by —O—, —COO—, —OCO— or —OCO—O—, One or more hydrogen atoms of the alkylene group may be substituted with a halogen atom or a CN group, and X ¹¹¹ and X ¹¹² are each independently —O—, —S—, —OCH _{2. -, - CH 2 O -,} - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O -, - CO-NH -, - NH-CO _{-, - SCH 2 -, -} CH 2 S -, - CF 2 O _{, -OCF 2 -, - CF 2} S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - _{, - - COO-CH 2 CH} 2 OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH ₂ —COO—, —CH ₂ —OCO—, —CH═CH—, —N═N—, —CH═N—N═CH—, —CF═CF—, —C≡C— or a single bond. (However, P ¹¹¹ -Sp ¹¹¹ , P ¹¹² -Sp ¹¹² , Sp ¹¹¹ -X ¹¹¹ and Sp ¹¹² -X ¹¹² do not include a direct bond between oxygen atoms), Y ¹¹¹ , Y ¹¹² and Y ¹¹³ are Each independently -COO- or -OCO Q111 and q112 each independently represents an integer of 0 to 5)), and is selected from the polymerizable liquid crystal compounds represented by
As the polymerizable liquid crystal compound having two polymerizable functional groups in the molecule, the following formulas (I-2-1) to (I-2-12)

Containing one or more compounds represented by the formula (hereinafter abbreviated as “compound (I-2)”), and
The following general formula (II-1)

(In the formula, P ²¹ represents a polymerizable functional group, Sp ²¹ represents an alkylene group having 1 to 18 carbon atoms or a single bond, and one —CH ₂ — in the alkylene group or not adjacent thereto. Two or more —CH ₂ — may be each independently substituted by —O—, —COO—, —OCO— or —OCO—O—, and one or more hydrogens of the alkylene group The atom may be substituted with a halogen atom or a CN group, and X ²¹ represents —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, -CO-S -, - S- CO -, - O-CO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - _{OCF 2 -, - CF 2 S} -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OC _{-, - COO-CH = CH} -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 _{-OCO -, - COO-CH 2} -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N ═CH—, —CF═CF—, —C≡C— or a single bond (wherein P ²¹ -Sp ²¹ and Sp ²¹ -X ²¹ do not include a direct bond between oxygen atoms), Y ²¹ It represents a single bond, q21 is 0 or ^1, T 21 is _{-OH, -SH, -CN, -COOH,} -NH 2, -NO 2, -COCH 3, -O (CH 2) n CH 3 or it represents - _{(CH 2)} n CH _3, n is an integer of 0 to 20). The polymerizable liquid crystal compound represented and contain one or more,
Mass ratio of the total amount of the bifunctional polymerizable liquid crystal compound represented by the general formula (I-1) and the total amount of the compound (I-2) [general formula (I-1) / compound (I-2)] Is in the range of 1/2 to 7/1, a polymerizable liquid crystal composition. The polymerizable liquid crystal according to claim 1 , wherein the polymerizable liquid crystal compound represented by the general formula (I-1) is contained in an amount of 1 to 70% by mass based on the total amount of the polymerizable liquid crystal compound used in the polymerizable liquid crystal composition. Composition. A polymer obtained by polymerizing the polymerizable liquid crystal composition according to any one of claims 1 to 2. Optically anisotropic medium obtained by using the polymerizable liquid crystal composition according to any one of claims 1 to 2. Phase difference film formed by using the polymerizable liquid crystal composition according to any one of claims 1 to 2. Viewing angle compensation film formed by using the polymerizable liquid crystal composition according to any one of claims 1 to 2. Antireflection film formed by using the polymerizable liquid crystal composition according to any one of claims 1 to 2. Polarizing plate obtained by using the polymerizable liquid crystal composition according to any one of claims 1 to 2. Display element obtained by using the polymerizable liquid crystal composition according to any one of claims 1 to 2.