JP6674161B2 - Polymerizable liquid crystal composition, polymer thereof, optically anisotropic body, and display element - Google Patents

Description

  The present invention is a polymer having optical anisotropy requiring various optical properties, a polymerizable liquid crystal composition useful as a constituent member of a film, and an optically anisotropic body comprising the polymerizable liquid crystal composition, a retardation film, Optical compensation film, antireflection film, lens, lens sheet, liquid crystal display device using the polymerizable liquid crystal composition, organic light emitting display device, lighting device, optical component, polarizing film, colorant, security marking, laser emission The present invention relates to members, printed matter, structural materials, restoration materials, articles, and the like.

A polymerizable liquid crystal composition having a mesogen skeleton is useful as a constituent member of an optically anisotropic body, and the optically anisotropic body is applied to various display devices as, for example, a retardation film. The retardation film is formed by applying a polymerizable liquid crystal composition having a mesogen skeleton to a substrate, and aligning the mesogen skeleton in the polymerizable liquid crystal composition with an alignment film, and liquid crystal molecules having a polymerizable group. It is obtained by heating or irradiating with active energy rays in the state where the liquid crystal molecules are reacted.

  Usually, the polymerizable liquid crystal composition to be applied is used in the form of a solution dissolved in a solvent. Therefore, after applying to the base material, a drying step of removing the solvent by heating or the like is required. After the solvent is removed in the drying process, the polymerizable liquid crystal compound in the polymerizable liquid crystal composition needs to be aligned on the substrate, but the process for obtaining the retardation film is diverse, and is longer in a wider temperature range. It is necessary to orient well without time and defects. Further, when transporting the solution, the solution is left to stand in various environments, so it is necessary to maintain the solution state for a longer time in a wider temperature range. In particular, at low temperatures, the liquid crystalline molecules tend to precipitate, and thus a polymerizable liquid crystal composition that can maintain a solution state under various environments has been desired.

  Therefore, as a technique for improving the solubility of a polymerizable liquid crystal compound in a solvent, there is an example in which the solubility is improved by the structure of the compound (Patent Documents 1 and 2), but the structure of the compound is limited. However, the characteristics were insufficient from the viewpoint of storage stability at low temperatures. In addition, although there is an example in which solubility is improved by combining an organic solvent having a cyclic ketone structure and an organic solvent having a cyclic ether structure (Patent Document 3), storage stability at low temperatures is insufficient. Since the solution viscosity is low, it is limited to the coating process that can be applied even if the viscosity is low, and it is not possible to cope with various coating methods, and there is a certain limitation in the application. Was. Further, as another example of improving the solvent solubility of a polymerizable liquid crystal compound, there is known a technique in which a diacetate solvent and a ketone solvent are used in combination as organic solvents (Patent Document 4). However, such a mixed solvent system exhibited a certain effect of improving the solubility of the solvent and improvement of the coating property, but was still not at a sufficient level, and was poor in the orientation after storage at a low temperature.

JP 2008-127336 A JP 2013-067603 A JP 2011-068833 A JP 2017-146575 A

  The problem to be solved by the present invention is to provide a polymer having good solubility, good storage stability at low temperature, and little unevenness in a film-like polymer after polymerization, and good orientation can be obtained. An object of the present invention is to provide a liquid crystal composition, a polymer having less unevenness and excellent alignment, an optically anisotropic substance using the polymer, and a display element.

The present invention, in order to solve the above problems, the temperature at which the polymerizable compound is dissolved in the solvent, storage conditions at low temperature, and focused on the boiling point and structure of the solvent used, as a result of intensive research, The present invention has been provided.
That is, the present invention
A polymerizable liquid crystal composition comprising at least one liquid crystal compound having at least one polymerizable group, a polymerization initiator, and at least one solvent.
1) the polymerizable liquid crystal composition is in a solution state at 25 ° C., and the solution viscosity measured by an E-type viscometer (20 ° C.) is in a range of 4 to 500 mPa · s;
2) In a temperature environment of 0 ° C. or lower, transparency is maintained for 1 week or more, and no precipitate is generated.
The invention relates to a polymerizable liquid crystal composition.

  The present invention further relates to a polymer obtained by curing a nonvolatile component of the polymerizable liquid crystal composition.

  The present invention further relates to an optically anisotropic material obtained by curing a nonvolatile component of the polymerizable liquid crystal composition.

  The present invention further relates to a display element using the optically anisotropic body.

  According to the present invention, a polymerizable liquid crystal composition having good solubility, good storage stability at a low temperature, and little unevenness in a film-like polymer after polymerization and excellent alignment can be obtained. And a polymer having less unevenness and excellent orientation, an optically anisotropic body using the polymer, and a display element.

  In particular, the polymerizable liquid crystal composition according to the present invention can favorably compatibilize the liquid crystal compound with a courageous solvent even under a heating condition of 70 ° C. or lower, and the obtained polymerizable liquid crystal composition The product is excellent in low-temperature storage stability that it is at least 0 ° C. or less and does not change for one week or more.

  Hereinafter, embodiments of the polymerizable liquid crystal composition according to the present invention will be described.In the present invention, the term “liquid crystal compound” is intended to indicate a compound having a mesogenic skeleton. It is not necessary to exhibit liquid crystallinity. 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 or heating.

As described above, the polymerizable liquid crystal composition of the present invention is a polymerizable liquid crystal composition containing at least one liquid crystal compound having at least one polymerizable group, a polymerization initiator, and at least one solvent. So,
1) the polymerizable liquid crystal composition is in a solution state at 25 ° C., and the solution viscosity measured by an E-type viscometer (20 ° C.) is in a range of 4 to 500 mPa · s;
2) In a temperature environment of 0 ° C. or lower, transparency is maintained for 1 week or more, and no precipitate is generated.
It is characterized by the following.

Here, the condition of the above 1) “the polymerizable liquid crystal composition is in a solution state at 25 ° C. and the solution viscosity in an E-type viscometer (20 ° C.) is in the range of 4 to 500 mPa · s” is as follows: As a polymerizable liquid crystal composition, it means a region with a relatively high viscosity, which results in good applicability and a moderately high viscosity, which supports a variety of coating means. can do. Usually, in order to shift the viscosity of the polymerizable liquid crystal composition in a solution state to a higher value, it is necessary to increase the concentration of nonvolatile components in the solution. In this case, the compatibility is impaired, and the liquid crystal compound is likely to be precipitated during low-temperature storage. Become. Therefore, the solution viscosity in the E-type viscometer (20 ° C.) in the present invention is in the range of 4 to 500 mPa · s, and the transparency is maintained for 1 week or more under a temperature environment of 0 ° C. or less, and The requirement that no precipitate is generated is a requirement for improving solubility, low-temperature storage stability, and coatability, and improves orientation and unevenness when a polymer is produced after long-term low-temperature storage. Is what you can do. From such a viewpoint, the solution viscosity of the polymerizable liquid crystal composition measured with an E-type viscometer (20 ° C.) is particularly preferably in the range of 5 to 180 mPa · s.
[A] Liquid crystalline compound having at least one polymerizable group The polymerizable liquid crystal composition of the present invention contains a liquid crystalline compound having at least one polymerizable group as an essential component.

The liquid crystalline compound having at least one polymerizable group of the present invention may be a polymerizable compound having a mesogenic skeleton, and the compound alone may not exhibit liquid crystallinity.
For example, Handbook of Liquid Crystals (edited by D. Demus, JW Goodby, GW Gray, HW Spies, V. Vill, published by Wiley-VCH, 1998), quarterly chemistry review No. 22, Chemistry of liquid crystal (edited by The Chemical Society of Japan, 1994), or JP-A-7-294735, JP-A-8-3111, JP-A-8-29618, JP-A-11-80090, Rigid sites called mesogens in which a plurality of structures such as 1,4-phenylene group and 1,4-cyclohexylene group are connected as described in Kaihei 11-116538 and JP-A-11-148079. And a rod-shaped polymerizable liquid crystal compound having two or more polymerizable functional groups such as a vinyl group, an acrylic group, and a (meth) acryl group, or described in JP-A-2004-2373 and JP-A-2004-99446. Such a rod-shaped polymerizable liquid crystal compound having two or more polymerizable groups having a maleimide group is exemplified. Above all, a rod-shaped liquid crystal compound having two or more polymerizable groups is preferable because a liquid crystal temperature range including a low temperature around room temperature can be easily produced.

  Specific examples of the liquid crystalline compound having at least one polymerizable group include compounds represented by the following general formulas (1) to (7).

In the above formula, P ^{11 to} P ⁷⁴ each independently represent a polymerizable group,
S ^{11 to} S ⁷² each independently represent a spacer group or a single bond, but when a plurality of S ^{11 to} S ⁷² are present, they may be the same or different;
X ¹¹ to X ⁷² 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 = NN-CH-, -CF = CF-, -C≡C- or a single bond. When a plurality of X ^{11 to} X ⁷² are present, they may be the same or different (provided that each P- (SX)-bond does not include -O-O-. ),
MG ^{11 to} MG ⁷¹ each independently represent a mesogenic group,
R ¹¹ and R ³¹ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or a carbon atom Represents an alkyl group of Formulas 1 to 20, wherein the alkyl group may be linear or branched, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom; one -CH ₂ in the alkyl group - 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- or -C≡C-,
m1 to m7, n2 to n7, 14 to 16 and k6 each independently represent an integer of 0 to 5.

The spacer group represented by S ^{11 to} S ⁷² represents an alkylene group having 1 to 18 carbon atoms, wherein the alkylene group is one or more halogen atoms, a CN group, an alkyl group having 1 to 8 carbon atoms, or it may be substituted by an alkyl group having 1 to 8 carbon atoms having a polymerizable functional group, each one CH ₂ group or not adjoining two or more CH ₂ groups that are present mutually in this group independently, in the form of oxygen atoms are not directly bonded to each other, -O a _{-, - S -, - NH} -, - N (CH 3) -, - CO -, - CH (OH) -, CH (COOH ), —COO—, —OCO—, —OCOO—, —SCO—, —COS——C≡C—, or formula (S-1) or formula (S-2)

May be replaced by Among these spacer groups, from the viewpoint of orientation, a linear alkylene group having 2 to 8 carbon atoms, an alkylene group having 2 to 6 carbon atoms substituted with a fluorine atom, and a part of the alkylene group is -O-. A substituted straight-chain having 5 to 14 carbon atoms or a branched alkylene group, a straight-chain or branched alkylene group having 5 to 14 carbon atoms in which part of the alkylene group is replaced with -COO- or -OCO-. preferable.
The polymerizable groups represented by P ^{11 to} P ⁷⁴ are represented by the following formulas (P-1) to (P-20)

Are preferred, and among these polymerizable groups, from the viewpoint of enhancing the polymerizability and storage stability, Formula (P-1), Formula (P-2), Formula (P-7), Formula (P-12), Or, the formula (P-13) is preferable, and the formulas (P-1), (P-7), and (P-12) are more preferable.

The mesogenic groups represented by MG ^{21 to} MG ⁷¹ are represented by the following formula (8-a)

(Where
A ⁸¹ and A ⁸² each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group, a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, a naphthalene-2,6-diyl A naphthalene-1,4-diyl group, a tetrahydronaphthalene-2,6-diyl group, a decahydronaphthalene-2,6-diyl group or a 1,3-dioxane-2,5-diyl group. The group may be unsubstituted or substituted by one or more of the above L, but when a plurality of A ⁸¹ and / or A ⁸² appear, they may be the same or different,
Z ⁸¹ and Z ⁸² are each independently -O-, -S-, -OCH _2- , -CH ₂ O-, -CH ₂ CH _2- , -CO-, -COO-, -OCO-, -CO -S -, - S-CO - , - O-CO-O -, - CO-NH -, - NH-CO -, - 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 -, - CH = N- N = CH -, - CF = CF -, - C≡C- or represents a single ^{bond, if Z 81} and / or ^{Z 82} appears more may each have identical or different,
M ⁸¹ represents 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydro Thiopyran-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, naphthylene-1,4-diyl group, Naphthylene-1,5-diyl group, naphthylene-1,6-diyl group, naphthylene-2,6-diyl group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl Group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene-2,7-diyl 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] thiophen-2,7-diyl group, [1] benzoseleno Represents a group selected from a pheno [3,2-b] selenophene-2,7-diyl group or a fluorene-2,7-diyl group, and these groups are unsubstituted or substituted by one or more L; Well,
L is a fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group , trimethylsilyl group, dimethylsilyl group, Chioisoshiano group, or one -CH ₂ - 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-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF-, or from 1 carbon atom which may be substituted by -C≡C-. 20 straight Represents a chain or branched alkyl group, any hydrogen atom in the alkyl group may be substituted with a fluorine atom,
j81 and j82 each independently represent an integer of 0 to 5, while j81 + j82 represents an integer of 1 to 5. ). Or a group represented by the formula (8-b)

(Where
A ⁸³ and A ⁸⁴ each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group, a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, a naphthalene-2,6-diyl A naphthalene-1,4-diyl group, a tetrahydronaphthalene-2,6-diyl group, a decahydronaphthalene-2,6-diyl group or a 1,3-dioxane-2,5-diyl group. The group may be unsubstituted or substituted by one or more L, but when a plurality of A ⁸³ and / or A ⁸⁴ appear, they may be the same or different,
M is calculated from the following formula (M-81) to formula (M-813)

Wherein these groups may be unsubstituted or substituted by one or more L;
G is the following formula (G-81) to formula (G-86)

(In the formula, R ³ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, wherein the alkyl group and the alkenyl group are linear. also it may be a branched, any hydrogen atom in the alkyl group may be substituted by fluorine atoms, the one in the alkyl radical -CH 2 _- or adjacent have not more than one - CH ₂ -is each independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO -NH-, -NH-CO- or -C≡C- may be substituted,
W ⁸¹ represents a group having 5 to 30 carbon atoms having at least one aromatic group, which may be unsubstituted or substituted by one or more L;
W ⁸² represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. The alkyl group may be linear or branched, and any hydrogen atom in the alkyl group may be may be substituted by a fluorine atom, one -CH ₂ in the alkyl group - 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-, -CH = CH-COO-,- CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C-, or W ⁸² may represent the same meaning as ^{W 81, also, W 81} and ^{W 82} are the same ring connected to each other It may be formed an elephant. ) Represents a group selected from
W ⁸³ and W ⁸⁴ each independently represent a halogen atom, a cyano group, a hydroxy group, a nitro group, a carboxyl group, a carbamoyloxy group, an amino group, a sulfamoyl group, and a C 5 to C 30 atom having at least one aromatic group. Groups, alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cycloalkenyl groups having 3 to 20 carbon atoms, 1 to 20 carbon atoms Represents an alkoxy group, an acyloxy group having 2 to 20 carbon atoms, or an alkylcarbonyloxy group having 2 to 20 carbon atoms, wherein the alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkoxy group, acyloxy group group, one -CH 2 in the alkyl carbonyl group _- or two or more non-adjacent Each independently -O is - - -CH ₂ of, - S -, - CO - , - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O-, -CO-NH-, -NH-CO- or -C≡C-,
However, when the above M is selected from the formulas (M-81) to (M-812), G is selected from the formulas (G-81) to (G-85), and M is the formula (M-813). G represents the formula (G-86),
L is a fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group Represents a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group may be linear or branched, and any hydrogen atom may be may be substituted by a fluorine atom, one -CH ₂ in the alkyl group - 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-, -CH = CH-COO-,- C H = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C- Often, j83 and j84 each independently represent an integer from 0 to 5, while j83 + j84 represents an integer from 1 to 5. ).
Further, the general formulas (1) to (7) are represented by the following general formulas (1-a), (1-b), (2-a), (2-b), General formula (3-a), General formula (3-b), General formula (4-a), General formula (4-b), General formula (5-a), General formula (5-b), General formula (6-a), general formula (6-b), general formula (7-a), and general formula (7-b).

The above general formula (1-a), general formula (1-b), general formula (2-a), general formula (2-b), general formula (3-a), general formula (3-b), general formula Formula (4-a), Formula (4-b), Formula (5-a), Formula (5-b), Formula (6-a), Formula (6-b), Formula (6-b) 7-a) and the general formula (7-b), the polymerizable groups P ^{11 to} P ⁷⁴ are each independently represented by the following formulas (P-1) to (P-20)

And preferably a group selected from the group consisting of the following formulas (P-1), (P-2), (P-7), Formula (P-12) or Formula (P-13) is preferable, and Formula (P-1), Formula (P-7), or Formula (P-12) is more preferable.
Formula (1-a), Formula (1-b), (2-a), Formula (2-b), Formula (3-a), Formula (3-b), Formula (4) -A), general formula (4-b), general formula (5-a), general formula (5-b), general formula (6-a), general formula (6-b), general formula (7-a) )), In the general formula (7-b), S ^{11 to} S ⁷² each independently represent a spacer group or a single bond. When a plurality of S ^{11 to} S ⁷² are present, they are different even if they are the same. May be. The spacer group represents an alkylene group having 1 to 18 carbon atoms, and the alkylene group has at least one halogen atom, a CN group, an alkyl group having 1 to 8 carbon atoms, or a polymerizable functional group. It may be substituted by an alkyl group having 1 to 8 carbon atoms, two or more of CH ₂ groups, independently of one another each of the present in the radical is not one CH ₂ group or adjacent, an oxygen atom in the form but does not bind directly to each _{other, -O -, - S -,} - NH -, - N (CH 3) -, - CO -, - CH (OH) -, CH (COOH), - COO -, - It may be replaced by OCO-, -OCOO-, -SCO-, -COS- or -C≡C-. Among these spacer groups, from the viewpoint of orientation, a linear alkylene group having 2 to 8 carbon atoms, an alkylene group having 2 to 6 carbon atoms substituted with a fluorine atom, and a part of the alkylene group is -O-. A substituted straight-chain having 5 to 14 carbon atoms or a branched alkylene group, a straight-chain or branched alkylene group having 5 to 14 carbon atoms in which part of the alkylene group is replaced with -COO- or -OCO-. preferable.
General formula (1-a), General formula (1-b), General formula (2-a), General formula (2-b), General formula (3-a), General formula (3-b), General formula (4-a), general formula (4-b), general formula (5-a), general formula (5-b), general formula (6-a), general formula (6-b), general formula (7) -a), in the general formula ^{(7-b), X 11} ~X 72 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 represents a single ^bond, X 11 ^{to X 72} is When two or more are present, they may be the same or different (provided that each P- (SX) _k -does not include an -O-O- bond). From the viewpoint of ease of raw material availability and synthesis, if there are a plurality may be different from each be the same, each independently -O -, - S -, - OCH 2 -, _{-CH 2 O -, - COO -} , - OCO -, - CO-S -, - S-CO -, - OCO-O -, - CO-NH -, - NH-CO -, - COO-CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO—, —CH ₂ CH ₂ —OCO— or a single bond, each independently preferably —O—, —OCH _{2 -, - CH 2 O -} , - COO -, - OCO -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 - More preferably, it represents OCO— or a single bond, and each of X ^{11 to} X ⁷² is plural. When they are present, they may be the same or different, and it is particularly preferable that each independently represents -O-, -COO-, -OCO- or a single bond.
General formula (1-a), General formula (1-b), General formula (2-a), General formula (2-b), General formula (3-a), General formula (3-b), General formula (4-a), general formula (4-b), general formula (5-a), general formula (5-b), general formula (6-a), general formula (6-b), general formula (7) -A) and in formula (7-b), A ^{11 to} A ⁷² each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group, a pyridine-2,5-diyl group, a pyrimidine-2. , 5-diyl, naphthalene-2,6-diyl, naphthalene-1,4-diyl, tetrahydronaphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl or 1,3-dioxane represents a 2,5-diyl group, these groups may be substituted by unsubstituted or substituted with one or more L is a ¹¹ ~ ⁷² each may be the same or different if more appear. A ^{11 to} A ⁷² each independently represent a 1,4-phenylene group, which may be unsubstituted or substituted by one or more L ² , 1,4-cycloalkyl, from the viewpoint of availability of raw materials and ease of synthesis. It preferably represents a hexylene group or naphthalene-2,6-diyl, and each independently represents the following formulas (A-1) to (A-11)

More preferably represents a group selected from formula (A-1) to independently represents a group selected from formula (A-8), and each independently represents a group selected from formula (A-1) Particularly preferably, it represents a group selected from the formula (A-4).
General formula (1-a), General formula (1-b), General formula (2-a), General formula (2-b), General formula (3-a), General formula (3-b), General formula (4-a), general formula (4-b), general formula (5-a), general formula (5-b), general formula (6-a), general formula (6-b), general formula (7) -a), in the general formula ^{(7-b), Z 11} ~Z 72 are each independently _{-O -, - S -, -} OCH 2 -, - CH 2 O -, - CH 2 CH 2 -, - CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-,- NH-COO -, - NH- CO-NH -, - NH-O -, - O-NH -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 _{S -, - SCF 2 -,} - CH = CH-CO -, - 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 -, - CH = N-N = CH -, - CF = CF -, - C≡C- or represents a single ^bond, Z 11 ^{to Z 72} appears more In each case, they may be the same or different. Z ¹¹ to Z ⁷² are liquid crystalline compound, from the standpoint of ease of raw material availability and synthesis, each independently a single _{bond, -OCH 2 -, - CH 2} O -, - COO -, - OCO- _{, -CF 2 O -, - OCF} 2 -, - CH 2 CH 2 -, - CF 2 CF 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 -, - CH = CH-, -CF = CF -, - C≡C- or preferably a single ^bond, Z 11 ^{to Z 72} each independently _{-OCH 2 -, - CH 2 O} -, - CH 2 CH 2 -, - COO _{-, - OCO -, - COO} -CH 2 CH 2 -, - OCO-CH 2 CH _{-, - CH 2 CH 2 -COO} -, - CH 2 CH 2 -OCO -, - CH = CH -, - C≡C- or is more preferably a single ^bond, Z 11 ^{to Z 72} each independently , _{- - -CH} 2 _CH 2 Te _{COO -, - OCO -, -} COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO - or more preferably representing a single bond, _-CH 2 _CH 2 each independently -, - COO -, - OCO- or and particularly preferably a single bond.
In the general formulas (1-a), (1-b), (3-a) and (3-b), R ¹¹ and R ³¹ each independently represent a hydrogen atom, a fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, Chioisoshiano group, or one -CH 2 _- 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- or -C≡C- represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted with any hydrogen atom in the alkyl group being a fluorine atom. It may be replaced. R ³¹ is a hydrogen atom in view of easiness of the liquid crystal and synthetic, fluorine atom, chlorine atom, cyano group, or one -CH 2 _- or nonadjacent two or more -CH 2 _- are each independently And preferably represents a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted by -O-, -COO-, -OCO-, -O-CO-O-, and includes a hydrogen atom, fluorine More preferably represents an atom, a chlorine atom, a cyano group, or a straight-chain alkyl group or straight-chain alkoxy group having 1 to 12 carbon atoms, and a straight-chain alkyl group or straight-chain alkoxy group having 1 to 12 carbon atoms. It is particularly preferred to represent.
General formula (1-b), General formula (2-b), General formula (3-b), General formula (4-b), General formula (5-b), General formula (6-b), General formula In (7-b), M is calculated from the following formula (M-81) to formula (M-813)

And these groups may be unsubstituted or substituted by one or more L. M is each independently unsubstituted or may be substituted by one or more L from formula (M-81) or formula (M-82) or It preferably represents a group selected from unsubstituted formula (M-83) to formula (M-86), and may be unsubstituted or substituted by one or more L-formulas (M-81) or (M-81). -82), more preferably a group selected from unsubstituted formula (M-81) or (M-82).
General formula (1-b), General formula (2-b), General formula (3-b), General formula (4-b), General formula (5-b), General formula (6-b), General formula In (7-b), G represents a group selected from formula (G-81) to formula (G-86).

In the formula, R ³ is a hydrogen atom, or one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—, —COO -, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, or carbon optionally substituted by -C≡C- Represents a linear or branched alkyl group having 1 to 20 atoms or a linear or branched alkenyl group having 2 to 20 carbon atoms, and any hydrogen atom in the alkyl group or the alkenyl group is fluorine. May be replaced by an atom,
W ⁸¹ represents a group having 5 to 30 carbon atoms having at least one aromatic group, wherein the group may be unsubstituted or substituted by one or more L;
W ⁸² is a hydrogen atom, or one -CH ₂ -or two or more non-adjacent -CH ₂ -are each independently -O-, -S-, -CO-, -COO-,- OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO- , -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C- which may be substituted by a straight chain having 1 to 20 carbon atoms. or represents a branched alkyl group, any hydrogen atom in the alkyl group may be substituted by a fluorine atom, or, W ⁸² may represent the same meaning as the W ^81, also, W ⁸¹ and W ⁸² may together form a ring structure.

In R ³ , an arbitrary hydrogen atom may be substituted with a fluorine atom from the viewpoint of liquid crystallinity and ease of synthesis, and one —CH ₂ — or two or more non-adjacent —CH ₂ — are each A linear or branched alkyl group having 1 to 12 carbon atoms which may be independently substituted by -O-, -COO- or -OCO-, or a linear or branched alkyl group having 2 to 16 carbon atoms. It preferably represents an alkenyl group, and a linear or branched alkyl group having 1 to 12 carbon atoms, in which an arbitrary hydrogen atom may be substituted by a fluorine atom, or a linear or branched alkyl group having 2 to 16 carbon atoms. it is more preferable that represent Jo alkenyl group, a linear alkyl group having 1 to 12 carbon atoms, one -CH 2 _- or nonadjacent two or more -CH 2 _- are each independently -O -, -COO- or -OCO- And particularly preferably a straight-chain alkenyl group which may carbon atoms from 2 to 16 substituted me.

W ⁸³ and W ⁸⁴ each independently represent a halogen atom, a cyano group, a hydroxy group, a nitro group, a carboxyl group, a carbamoyloxy group, an amino group, a sulfamoyl group, and a C 5 to C 30 atom having at least one aromatic group. Groups, alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cycloalkenyl groups having 3 to 20 carbon atoms, 1 to 20 carbon atoms Represents an alkoxy group, an acyloxy group having 2 to 20 carbon atoms, or an alkylcarbonyloxy group having 2 to 20 carbon atoms, wherein the alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkoxy group, acyloxy group group, one -CH 2 in the alkyl carbonyl group _- or two or more non-adjacent Each independently -O is - - -CH ₂ of, - S -, - CO - , - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O-, It may be substituted by -CO-NH-, -NH-CO- or -C≡C-.

The aromatic group contained in W ⁸¹ may be an aromatic hydrocarbon group or an aromatic hetero group, or may contain both. These aromatic groups may be linked via a single bond or a linking group (-OCO-, -COO-, -CO-, -O-), or may form a condensed ring. In addition, W ⁸¹ may include an acyclic structure and / or a cyclic structure other than the aromatic group in addition to the aromatic group. The aromatic group contained in W ⁸¹ is unsubstituted or may be substituted with one or more L from the following formula (W-1) from the viewpoint of availability of raw materials and ease of synthesis. (W-19)

(Wherein these groups may have a bond at any position, it may form a group linked to two or more aromatic group selected from these groups with a single bond, Q ¹ Represents —O—, —S—, —NR ⁵ — (wherein R ⁵ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms) or —CO—. -CH = may be replaced each independently -N =, -CH ₂ - are each independently -O -, - S -, - NR 4 - ( wherein, ^{R 4} is hydrogen or C Which represents an alkyl group having 1 to 8 atoms) or may be replaced by -CO-, but does not include a -O-O- bond). The group represented by the formula (W-1) includes a group represented by the following formula (W-1-1) which may be unsubstituted or substituted by one or more L ² . )

(In the formula, these groups may have a bond at an arbitrary position.) It is preferable that the group represented by the formula (W-7) is unsubstituted. Or from the following formula (W-7-1) to formula (W-7-7) which may be substituted by one or more L ²

(In the formula, these groups may have a bond at any position.) It is preferable that the group represented by the formula (W-10) is unsubstituted. Or the following formula (W-10-1) to formula (W-10-8) which may be substituted by one or more L ²

(In the formula, these groups may have a bond at any position, and R ⁶ preferably represents a group selected from a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) The group represented by the formula (W-11) includes a group represented by the following formulas (W-11-1) to (W-11-13) which may be unsubstituted or substituted by one or more L ² . )

(In the formula, these groups may have a bond at any position, and R ⁶ preferably represents a group selected from a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) The group represented by the formula (W-12) includes a group represented by the following formulas (W-12-1) to (W-12-19) which may be unsubstituted or substituted by one or more Ls.

(Wherein these groups may have a bond at any position, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, each identical if R ⁶ there are a plurality of And may be different from each other.), And the group represented by the formula (W-13) is unsubstituted or substituted by one or more L. From the following formula (W-13-1) to formula (W-13-10)

(Wherein these groups may have a bond at any position, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, each identical if R ⁶ there are a plurality of And may be different from each other.), And the group represented by the formula (W-14) is unsubstituted or substituted by one or more L ² . The following formula (W-14-1) to formula (W-14-4) may be used.

(In the formula, these groups may have a bond at any position, and R ⁶ preferably represents a group selected from a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) The group represented by the formula (W-15) includes a group represented by the following formulas (W-15-1) to (W-15-18) which may be unsubstituted or substituted by one or more L.

(Wherein these groups may have a bond at any position, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, each identical if R ⁶ there are a plurality of And may be different from each other.), And the group represented by the formula (W-16) is unsubstituted or substituted by one or more L. From the following formula (W-16-1) to formula (W-16-4)

(In the formula, these groups may have a bond at any position, and R ⁶ preferably represents a group selected from a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) The group represented by the formula (W-17) includes a group represented by the following formulas (W-17-1) to (W-17-6) which may be unsubstituted or substituted by one or more Ls.

(In the formula, these groups may have a bond at any position, and R ⁶ preferably represents a group selected from a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) Examples of the group represented by the formula (W-18) include the following formulas (W-18-1) to (W-18-6) which may be unsubstituted or substituted by one or more L ² .

(Wherein these groups may have a bond at any position, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, each identical if R ⁶ there are a plurality of And may be different from each other.), And the group represented by the formula (W-19) is unsubstituted or substituted by one or more L. From the following formula (W-19-1) to formula (W-19-9)

(Wherein these groups may have a bond at any position, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, each identical if R ⁶ there are a plurality of Or a different group). The aromatic group contained in W ⁸¹ may be unsubstituted or substituted by one or more L, represented by the formula (W-1-1), the formula (W-7-1), or the formula (W-7). -2), Formula (W-7-7), Formula (W-8), Formula (W-10-6), Formula (W-10-7), Formula (W-10-8), Formula (W-10-8) 11-8), Formula (W-11-9), Formula (W-11-10), Formula (W-11-11), Formula (W-11-12), or Formula (W-11-13) It is more preferable to represent a group selected from the group consisting of formula (W-1-1), formula (W-7-1), and formula (W-) which may be unsubstituted or substituted by one or more L. 7-2), a group selected from the formula (W-7-7), the formula (W-10-6), the formula (W-10-7) or the formula (W-10-8) is particularly preferable. . Further, ^W81 is calculated from the following formula (Wa-1) to formula (Wa-6)

(Wherein, r represents an integer of 0 to 5, s represents an integer of 0 to 4, and t represents an integer of 0 to 3).
W ⁸² is a hydrogen atom, or one -CH ₂ -or two or more non-adjacent -CH ₂ -are each independently -O-, -S-, -CO-, -COO-,- OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO- , -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C- which may be substituted by a straight chain having 1 to 20 carbon atoms. or represents a branched alkyl group, any hydrogen atom in the alkyl group may be substituted by a fluorine atom, or, W ⁸² may represent the same meaning as the W ^81, also, W ⁸¹ and W ⁸² may together form a ring structure. W ⁸² from the viewpoint of ease of raw material availability and synthesis, a hydrogen atom, or any hydrogen atom may be substituted by a fluorine atom, one -CH 2 _- 2 pcs or nonadjacent more -CH ₂ - are each independently -O -, - CO -, - COO -, - OCO -, - CH = CH-COO -, - OCO-CH = CH -, - CH = CH -, - It preferably represents a linear or branched alkyl group having 1 to 20 carbon atoms, which may be substituted by CF = CF- or -C≡C-, and preferably represents a hydrogen atom or a C1 to C20 alkyl group. More preferably, it represents a linear or branched alkyl group, particularly preferably a hydrogen atom or a linear alkyl group having 1 to 12 carbon atoms. ^{Also, if W 82} represents the same meaning as ^{W 81, W 82} may be different even identical to ^{W 81,} the preferred group is the same as described for ^{W 81.} When W ⁸¹ and W ⁸² together form a ring structure, the cyclic group represented by —NW ⁸¹ W ⁸² may be unsubstituted or substituted by one or more Ls below. From the formula (Wb-1) to the formula (Wb-42)

(Wherein, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), and preferably represents a group selected from the group consisting of unsubstituted or Formula (Wb-20), Formula (Wb-21), Formula (Wb-22), Formula (Wb-23), Formula (Wb-23) which may be substituted by one or more L -B-24), a formula (Wb-25) or a formula (Wb-33).

Further, the cyclic group represented by = CW ⁸¹ W ⁸² may be unsubstituted or substituted by one or more L, from the following formula (W-c-1) to formula (W-c-81).

(In the formula, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and when a plurality of R ⁶ are present, they may be the same or different.) Preferably, from the viewpoint of the availability of raw materials and the ease of synthesis, formulas (W-c-11) and (W-c-12), which may be unsubstituted or substituted by one or more L, Formula (Wc-13), Formula (Wc-14), Formula (Wc-53), Formula (Wc-54), Formula (Wc-55), Formula (Wc) -56), a group selected from the formula (Wc-57) or the formula (Wc-78) is particularly preferable.
The total number of π electrons contained in W ⁸¹ and W ⁸² is preferably 4 to 24 from the viewpoints of wavelength dispersion characteristics, storage stability, liquid crystallinity, and ease of synthesis.
W ⁸³ and W ⁸⁴ each independently represent a halogen atom, a cyano group, a hydroxy group, a nitro group, a carboxyl group, a carbamoyloxy group, an amino group, a sulfamoyl group, and a C 5 to C 30 atom having at least one aromatic group. Groups, alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cycloalkenyl groups having 3 to 20 carbon atoms, 1 to 20 carbon atoms Represents an alkoxy group, an acyloxy group having 2 to 20 carbon atoms, or an alkylcarbonyloxy group having 2 to 20 carbon atoms, wherein the alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkoxy group, acyloxy group group, one -CH 2 in the alkyl carbonyl group _- or two or more non-adjacent Each independently -O is - - -CH ₂ of, - S -, - CO - , - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O-, W ⁸³ may be substituted by —CO—NH—, —NH—CO— or —C≡C—, and W ⁸³ represents a cyano group, a nitro group, a carboxyl group, one —CH ₂ — or _two non-adjacent groups. , - - -O each independently is - more _{-CH 2 S -, - CO -} , - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O- , A group selected from an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an acyloxy group and an alkylcarbonyloxy group substituted by -CO-NH-, -NH-CO- or -C≡C- Preferably, a cyano group, a carboxyl group, one —CH ₂ — or two or more non-adjacent —C H ₂ — is each independently substituted by —CO—, —COO—, —OCO—, —O—CO—O—, —CO—NH—, —NH—CO—, or —C≡C—, A group selected from an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an acyloxy group, and an alkylcarbonyloxy group is particularly preferred, and W ⁸⁴ is a cyano group, a nitro group, a carboxyl group, one —CH ₂ — or an adjacent group. Two or more —CH ₂ — that are not independently represent —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O Selected from an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an acyloxy group and an alkylcarbonyloxy group substituted by -CO-O-, -CO-NH-, -NH-CO- or -C≡C-. Groups are more preferable, and a cyano group, Carboxyl group, one -CH ₂ - or nonadjacent two or more -CH ₂ - are each independently -CO -, - COO -, - OCO -, - OCO-O -, - CO A group selected from an alkyl group, an alkenyl group, an acyloxy group and an alkylcarbonyloxy group having 1 to 20 carbon atoms, which is substituted by -NH-, -NH-CO- or -C≡C- Is particularly preferred.
L is a fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group , trimethylsilyl group, dimethylsilyl group, Chioisoshiano group, or one -CH ₂ - 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-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF-, or from 1 carbon atom which may be substituted by -C≡C-. 20 straight It represents a chain or branched alkyl group, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom. From the viewpoints of liquid crystallinity and ease of synthesis, L ² is a fluorine atom, a chlorine atom, a pentafluorosulfuranyl group, a nitro group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, or any hydrogen. atom may be substituted by a fluorine atom, one -CH ₂ - or nonadjacent two or more -CH ₂ - are each independently -O -, - S -, - CO -, - COO —, —OCO—, —O—CO—O—, —CH ＝ CH—, —CF ＝ CF— or —C≡C—, which has 1 to 20 carbon atoms. It preferably represents a chain or branched alkyl group or a group represented by the above formula (1-c). A fluorine atom, a chlorine atom, or an arbitrary hydrogen atom may be substituted by a fluorine atom. number of -CH ₂ - or Do-adjacent Two or more —CH ₂ — are each independently a linear or branched alkyl having 1 to 12 carbon atoms which may be substituted by a group selected from —O—, —COO—, or —OCO—. More preferably, a fluorine atom, a chlorine atom, or an arbitrary hydrogen atom represents a linear or branched alkyl group or an alkoxy group having 1 to 12 carbon atoms which may be substituted by a fluorine atom. Is more preferable, and particularly preferably represents a fluorine atom, a chlorine atom, or a linear alkyl group or linear alkoxy group having 1 to 8 carbon atoms.
General formula (1-b), General formula (2-b), General formula (3-b), General formula (4-b), General formula (5-b), General formula (6-b), General formula In (7-b), G represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group , dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, Chioisoshiano group, or one -CH 2 _- 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- , -CH = CH-COO-, -CH = CH-OC O-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C- which may have 1 to 20 carbon atoms. More preferably, it represents a chain or branched alkyl group.
General formula (1-a), General formula (2-a), General formula (3-a), General formula (4-a), General formula (5-a), General formula (6-a), General formula In (7-a), M ^{11 to} M ⁷¹ represent 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 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, thiophen-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group , Naphthylene-1,4-diyl group, naphthylene-1,5-diyl group Naphthylene-1,6-diyl group, naphthylene-2,6-diyl group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a , 9,10a-Octahydrophenanthrene-2,7-diyl group, benzo [1,2-b: 4,5-b '] dithiophen-2,6-diyl group, benzo [1,2-b: 4, 5-b '] diselenophen-2,6-diyl group, [1] benzothieno [3,2-b] thiophen-2,7-diyl group, [1] benzoselenopheno [3,2-b] selenophene-2 , 7-diyl group or fluorene-2,7-diyl group, which may be unsubstituted or substituted by one or more L, and M ^{11 to} M ⁷¹ From the viewpoint of availability and ease of synthesis 1,4-phenylene, 1,4-cyclohexylene, naphthylene-1,4-diyl or naphthylene-2, each independently being unsubstituted or optionally substituted by one or more L. A 6-diyl group is preferred, and more preferably a group selected from a 1,4-phenylene group and a 1,4-cyclohexylene group which may be unsubstituted or substituted by one or more L.
L is a fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group , trimethylsilyl group, dimethylsilyl group, Chioisoshiano group, or one -CH ₂ - 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-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF-, or from 1 carbon atom which may be substituted by -C≡C-. 20 straight It represents a chain or branched alkyl group, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom. From the viewpoints of liquid crystallinity and ease of synthesis, L ² is a fluorine atom, a chlorine atom, a pentafluorosulfuranyl group, a nitro group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, or any hydrogen. atom may be substituted by a fluorine atom, one -CH ₂ - or nonadjacent two or more -CH ₂ - are each independently -O -, - S -, - CO -, - COO —, —OCO—, —O—CO—O—, —CH ＝ CH—, —CF ＝ CF— or —C≡C—, which has 1 to 20 carbon atoms. preferably representing a linear or branched alkyl group, a fluorine atom, a chlorine atom, or any of the hydrogen atoms may be substituted by a fluorine atom, one -CH 2 _- or two or more nonadjacent are each independently - -CH ₂ of More preferably represents a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted by a group selected from O-, -COO- or -OCO-, and represents a fluorine atom, a chlorine atom, or More preferably, any hydrogen atom represents a linear or branched alkyl group or an alkoxy group having 1 to 12 carbon atoms which may be substituted by a fluorine atom, and a fluorine atom, a chlorine atom, or a carbon atom It is particularly preferred to represent from 1 to 8 straight-chain alkyl or alkoxy groups.
General formula (1-a), General formula (1-b), General formula (2-a), General formula (2-b), General formula (3-a), General formula (3-b), General formula (4-a), general formula (4-b), general formula (5-a), general formula (5-b), general formula (6-a), general formula (6-b), general formula (7) -A) In the general formula (7-b), m1 to m7, n2, n4 to n7, 14, 16 and k6 each independently represent an integer of 0 to 5, but the liquid crystallinity and availability of raw materials are easy. It is preferable to represent an integer of 0 to 4, more preferably 0 to 2, and even more preferably 0 or 1 from the viewpoints of ease and ease of synthesis.
In the general formulas (1-a) to (7-b), j11, j12, j21, j22, j31, j32, j41, j42, j51, j52, j61, j62, j71, and j72 are each independently. J11 + j12 represents an integer from 1 to 5, j21 + j22 represents an integer from 1 to 5, j31 + j32 represents an integer from 1 to 5, j41 + j42 represents an integer from 1 to 5, j51 + j52. Represents an integer of 1 to 5, j61 + j62 represents an integer of 1 to 5, and j71 + j72 represents an integer of 1 to 5. From the viewpoints of liquid crystallinity, ease of synthesis, and storage stability, j11, j12, j21, j22, j31, j32, j41, j42, j51, j52, j61, j62, j71, and j72 are each independently 1 to 4 Represents preferably an integer of 1 to 3, more preferably represents an integer of 1 to 3, and particularly preferably represents 1 or 2. j11 + j12, j21 + j22, j31 + j32, j41 + j42, j51 + j52, j61 + j62, and j71 + j72 each preferably represent an integer of 1 to 4, and particularly preferably 2 or 3.
Specifically, as the compound represented by the general formula (1-a), compounds represented by the following formulas (1-a-1) to (1-a-39) are preferable.

In the above formula, m11, n11 represents an integer of 1 to 10 ^{independently, R 111} and ^{R 112} are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or represents a fluorine atom , R ¹¹³ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, Chioisoshiano group, or one -CH 2 _- or adjacent Two or more —CH ₂ — that are not independently represent —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, and —O— Represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by CO—O—, —CO—NH—, —NH—CO—, or —C≡C—, Any hydrogen atom in it is replaced with a fluorine atom May be.
Specifically, as the compound represented by the general formula (1-b), compounds represented by the following formulas (1-b-1) to (1-b-26) are preferable.

These liquid crystal compounds can be used alone or in combination of two or more.
Specifically, as the compound represented by the general formula (2-a), compounds represented by the following formulas (2-a-1) to (2-a-33) are preferable.

(In the formula, m and n each independently represent an integer of 1 to 18, and R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group. When these groups are an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, they may be unsubstituted or substituted by one or more halogen atoms. These liquid crystal compounds can be used alone or in combination of two or more.
Specifically, as the compound represented by the general formula (2-b), compounds represented by the following formulas (2-b-1) to (2-b-23) are preferable.

(In the formula, n represents an integer of 1 to 10.) These liquid crystal compounds can be used alone or in combination of two or more.
Specifically, as the compound represented by the general formula (3-a), compounds represented by the following formulas (3-a-1) to (3-a-16) are preferable.

These liquid crystal compounds can be used alone or in combination of two or more.
Specifically, as the compound represented by the general formula (3-b), compounds represented by the following formulas (3-b-1) to (3-b-11) are preferable.

These liquid crystal compounds can be used alone or in combination of two or more.
Specifically, as the compound represented by the general formula (4-a), compounds represented by the following formulas (4-a-1) to (4-a-29) are preferable.

(In the formula, m and n each independently represent an integer of 1 to 10. R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group. When these groups are an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, they may be unsubstituted or substituted by one or more halogen atoms. These liquid crystalline compounds can be used alone or in combination of two or more.
Specifically, as the compound represented by the general formula (4-b), compounds represented by the following formulas (4-b-1) to (4-b-6) are preferable.

(In the formula, m and n each independently represent an integer of 1 to 10.) These liquid crystal compounds can be used alone or in combination of two or more.

Specifically, as the compound represented by the general formula (5-a), compounds represented by the following formulas (5-a-1) to (5-a-26) are preferable.

(In the formula, n independently represents an integer of 1 to 10. R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group. Is an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, all may be unsubstituted or substituted by one or more halogen atoms. ) These liquid crystalline compounds can be used alone or in combination of two or more.
Specifically, as the compound represented by the general formula (5-b), compounds represented by the following formulas (5-b-1) to (5-b-7) are preferable.

(In the formula, n represents 1 to 10 carbon atoms.) These liquid crystal compounds can be used alone or in combination of two or more.
Specifically, as the compound represented by the general formula (6-a), compounds represented by the following formulas (6-a-1) to (6-a-23) are preferable.

(In the formula, k, l, m and n each independently represent an integer of 1 to 10. R is a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, When these groups are an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, they are all unsubstituted or substituted by one or more halogen atoms. These liquid crystal compounds can be used alone or in combination of two or more.
Specifically, as the compound represented by the general formula (6-b), compounds represented by the following formulas (6-b-1) to (6-b-7) are preferable.

(In the formula, k, l, m and n each independently represent 1 to 10 carbon atoms.) These liquid crystal compounds can be used alone or as a mixture of two or more. You can also.
Specifically, as the compound represented by the general formula (7-a), compounds represented by the following formulas (7-a-1) to (7-a-25) are preferable.

(Wherein, R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group. These groups are an alkyl group having 1 to 6 carbon atoms, In the case of the alkoxy groups of Formulas 1 to 6, all may be unsubstituted or substituted by one or more halogen atoms.) These liquid crystal compounds may be used alone. Specific examples of the compound represented by the general formula (7-b) which can be used or can be used as a mixture of two or more kinds include compounds represented by the following formulas (7-b-1) to (7-b-6). ) Is preferred.

[B] Solvent The solvent that can be used in the polymerizable liquid crystal composition of the present invention includes the following conditions 1) and 2):
1) the polymerizable liquid crystal composition is in a solution state at 25 ° C., and the solution viscosity measured by an E-type viscometer (20 ° C.) is in a range of 4 to 500 mPa · s;
2) In a temperature environment of 0 ° C. or lower, transparency is maintained for 1 week or more, and no precipitate is generated.
Any one that satisfies the above condition 1) can be used. Particularly, in order to satisfy the above condition 1), it is preferable that the liquid crystal compound [A] can be dissolved under a temperature condition of 70 ° C. or lower.

  Such a solvent is a solvent (a) having a cyclic structure in the molecule and having a boiling point of 170 ° C. or higher (hereinafter abbreviated as “high boiling point solvent (a)”). More specifically, it preferably contains at least one group consisting of -O-, -CO-, -COO-, -OH, -CONR-. For example, aromatic hydrocarbons such as cyclohexyl acetate, γ-butyrolactone, ester solvents such as methyl benzoate and ethyl carbonate, ether solvents such as methoxytoluene and veratrol, ketone solvents such as isophorone and acetophenone, and N-methyl- Amide solvents such as 2-pyrrolidone and 2-pyrrolidone are exemplified. The high-boiling solvent (a) can dissolve the liquid crystalline compound [A] at a temperature of 70 ° C. or less, and the dissolved adhering material changes at 0 ° C. or less after dissolution for 1 week or more. If not, one solvent may be used, but two or more solvents may be used.

  In the present invention, in order to satisfy the above 1) and 2), it is preferable to use a solvent having a boiling point lower than that of the high boiling solvent (a) in addition to the high boiling solvent (a). Is not particularly limited, but it is particularly preferable to have at least one group consisting of -O-, -CO-, -COO-, -OH, -CONR-, and -CN. Further, the solvent may have a cyclic structure or a non-cyclic structure, but from the viewpoint of orientation, a solvent having a non-cyclic structure (hereinafter, having a lower boiling point than the high boiling solvent (a), In addition, the solvent having an acyclic structure is abbreviated as “low-boiling solvent (b)”).

Examples of such a low boiling solvent (b) include aromatic hydrocarbons such as toluene, xylene, cumene, and mesitylene, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 3-butoxymethyl acetate, and ethyl lactate. Ester solvents such as methyl ethyl ketone, methyl isobutyl ketone, acetonylacetone, cyclohexanone and cyclopentanone; ether solvents such as diisobutyl ether, tetrahydrofuran, 1,2-dimethoxyethane and anisole; N, N- Amide solvents such as dimethylformamide, cyclohexanol, 1-methoxy-2-propanol, 2-butoxyethanol, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol Monomethyl ether, propylene glycol diacetate, propylene glycol monomethyl propyl ether, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether acetate, and chlorobenzene, and the like. It is preferable to use any one or more of these ketone solvents, ether solvents, ester solvents and aromatic hydrocarbon solvents from the viewpoint of solution stability.
The low-boiling solvent (b) may have a boiling point lower than that of the high-boiling solvent (a) used in combination, but is more preferably lower than 170 ° C.
The weight ratio of the solvent having a boiling point of 170 ° C. or higher to the solvent having a boiling point lower than that of the solvent is not particularly limited as long as the low-temperature storability and coatability of the polymerizable liquid crystal composition of the invention are not impaired. The ratio is preferably 0 to 5/95, more preferably 80/20 to 10/90, and particularly preferably 70/30 to 15/85.

  The weight ratio of the solvent in the polymerizable liquid crystal composition of the present invention is not particularly limited as long as the polymerizable liquid crystal composition used in the present invention is usually applied by coating, as long as the coated state is not significantly impaired. The mass ratio of the liquid crystal compound [A] having at least one polymerizable group to the solvent [B] is preferably from 1/99 to 99/1, more preferably from 10/90 to 80/20. , 20/80 to 70/30. Moreover, the solid content concentration of the polymerizable liquid crystal composition finally obtained is 10 to 80% by mass, particularly 20 to 70% by mass, so that the coating property and the storage stability at low temperature are good. It is preferable because unevenness in the film polymer after polymerization is small and the orientation is excellent.

Further, when dissolving the polymerizable liquid crystalline compound in an organic solvent, it is preferable to heat and stir to uniformly dissolve the compound. The heating temperature at the time of heating and stirring may be appropriately adjusted in consideration of the solubility of the polymerizable liquid crystal compound to be used in an organic solvent. Preferably, 40 ° C to 60 ° C is particularly preferred.
[C] Initiator The polymerizable liquid crystal composition of the present invention can contain an initiator [C] as necessary. The polymerization initiator used in the polymerizable liquid crystal composition of the present invention is used for polymerizing the polymerizable liquid crystal composition of the present invention. The photopolymerization initiator used in the case where the polymerization is carried out by light irradiation is not particularly limited, but is a polymerizable compound having the one polymerizable group and satisfying the formula (I), Any known and commonly used polymerizable liquid crystal compound having a polymerizable group can be used to the extent that it does not hinder the alignment state of the polymerizable liquid crystal compound having a polymerizable group.

  For example, 1-hydroxycyclohexylphenyl ketone “Omnilad 184”, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one “Omnirad 1173”, 2-methyl-1-[(methylthio) phenyl] -2-Moriholinopropane-1 "Omnirad 907", 2,2-dimethoxy-1,2-diphenylethan-1-one "Omnirad BDK", 2-benzyl-2-dimethylamino-1- (4-morpho Linophenyl) -butanone "omnilad 369"), 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholino-phenyl) butan-1-one "omnilad 379", 2,2-dimethoxy- 1,2-diphenylethan-1-one, bis (2,4,6-trimethylbenzoyl -Diphenylphosphine oxide "Omnirad TPO", 2,4,6-trimethylbenzoyl-phenyl-phosphine oxide "Omnirad 819" (manufactured by IGM Resins), 1,2-octanedione, 1- [4- (phenylthio) )-, 2- (O-benzoyloxime)], ethanone “Irgacure OXE01”), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O -Acetyl oxime) "Irgacure OXE02", "Irgacure OXE04" (manufactured by BASF), "Adeka Aquel's NCI-831", "Adeka Aquel's NCI-930", "Adeka Aquel's N-1919" (Adeka) ), 2,4-diethylthioxanthone ("Nippon Kayaku Co., Ltd." Cayacure DETX ") and a mixture of ethyl p-dimethylaminobenzoate (" Kayacure EPA "manufactured by Nippon Kayaku Co., Ltd.), isopropylthioxanthone (" Kantacure-ITX "manufactured by Ward Prekinsopp) and ethyl p-dimethylaminobenzoate. Of "Esacure ONE", "Esacure KIP150", "Esacure KIP160", "Esacure 1001M", "Esacure A198", "Esacure KIP IT", "Esacure KTO46", "Esacure TZT" (manufactured by Lamberti Co., Ltd.) "Speed Cure BMS", "Speed Cure PBZ", "Benzophenone" (manufactured by LAMBSON) and the like. Further, a photoacid generator can be used as the photocationic initiator. Examples of the photoacid generator include diazodisulfone compounds, triphenylsulfonium compounds, phenylsulfone compounds, sulfonylpyridine compounds, triazine compounds and diphenyliodonium compounds.

  The content of the photopolymerization initiator is preferably from 0.1 to 10% by mass, particularly preferably from 1 to 7% by mass, based on the total amount of the liquid crystal compound having at least one polymerizable group. These can be used alone or in combination of two or more.

As the thermal polymerization initiator used in the thermal polymerization, known and commonly used thermal polymerization initiators, for example, methyl acetoacetate peroxide, cumene hydroperoxide, benzoyl peroxide, bis (4-t-butylcyclohexyl) Peroxydicarbonate, t-butylperoxybenzoate, methyl ethyl ketone peroxide, 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, p-pentahydroperoxide, t-butylhydro Organic peroxides such as peroxide, dicumyl peroxide, isobutyl peroxide, di (3-methyl-3-methoxybutyl) peroxydicarbonate, and 1,1-bis (t-butylperoxy) cyclohexane; 2′-azobisisobutyronitrile, Azonitrile compounds such as 2,2'-azobis (2,4-dimethylvaleronitrile), azoamidine compounds such as 2,2'-azobis (2-methyl-N-phenylpropion-amidine) dihydrochloride, 2,2 ' Azoamide compounds such as azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide} and alkylazo compounds such as 2,2 ′ azobis (2,4,4-trimethylpentane) Compounds and the like can be used. The content of the thermal polymerization initiator is preferably from 0.1 to 10% by mass, particularly preferably from 1 to 6% by mass. These can be used alone or in combination of two or more.
[D] Polymerization inhibitor The polymerizable liquid crystal composition of the present invention can contain a polymerization inhibitor as needed. The polymerization inhibitor to be used is not particularly limited, and those known in the art can be used.

  For example, 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-t-butylphenol), 4.4'-thiobis (3-methyl-6-t-butylphenol), 4-methoxy-1-naphthol, 4,4'-dialkoxy-2 Phenol compounds such as 2,2'-bi-1-naphthol, 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, quinone compounds such, p- phenylenediamine, 4-aminodiphenylamine, N. N'-diphenyl-p-phenylenediamine, Ni-propyl-N'-phenyl-p-phenylenediamine, N- (1.3-dimethylbutyl) -N'-phenyl-p-phenylenediamine; Amine compounds such as N′-di-2-naphthyl-p-phenylenediamine, diphenylamine, N-phenyl-β-naphthylamine, 4.4′-dicumyl-diphenylamine, 4.4′-dioctyl-diphenylamine, phenothiazine, Thioether compounds such as distearyl thiodipropionate, N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, N-nitrosodinaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol N, N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitronedimethylamine, p-nitrone-N, N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, -Nitroso-N-n-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N -Nitroso N-phenylhydroxylamine ammonium salt, Nitrosobenzene, 2,4.6-tri-tert-butylnitronebenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane , N-nitroso-NN-propyl urethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 1-nitroso-2-naphthol-3,6-sodium sulfonate, 2-nitroso-1- Sodium naphthol-4-sulfonate, 2-nitroso-5-methylamino Nitroso compounds such as phenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride, and the like.

The addition amount of the polymerization inhibitor is preferably 0.01 to 2.0% by mass based on the total amount of the liquid crystal compound having at least one polymerizable group used in the polymerizable liquid crystal composition of the present invention, More preferably, it is 0.05 to 1.0% by mass.
[E] Antioxidant The polymerizable liquid crystal composition of the present invention can contain an antioxidant and the like as necessary. Examples of such a compound include a hydroquinone derivative, a nitrosamine-based polymerization inhibitor, a hindered phenol-based antioxidant, and the like. More specifically, tert-butylhydroquinone, “Q-1300” of Wako Pure Chemical Industries, “Q-1301”, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate “IRGANOX1010”, thiodiethylenebis [3- (3,5-di-tert-butyl-) 4-hydroxyphenyl) propionate “IRGANOX1035”, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate “IRGANOX1076”, “IRGANOX1135”, “IRGANOX1330”, 4,6-bis (octyl) Thiomethi ) -O-cresol "IRGANOX1520L", "IRGANOX1726", "IRGANOX245", "IRGANOX259", "IRGANOX3114", "IRGANOX3790", "IRGANOX5057", "IRGANOX565" (all manufactured by BASF Corporation), manufactured by ADEKA Corporation Adekastab AO-20, AO-30, AO-40, AO-50, AO-60, AO-80 of Sumitomo Chemical Co., Ltd., Sumitomo Chemical Co., Ltd., Sumilizer BHT, Sumilizer BBM-S, Sumilizer GA-80 and the like.

The addition amount of the antioxidant is 0.01 to 2.0% by mass based on the total amount of the liquid compound having at least one polymerizable group used in the polymerizable liquid crystal composition of the present invention. Is more preferable, and more preferably 0.05 to 1.0% by mass.
[F] Ultraviolet Absorber and / or Light Stabilizer The polymerizable liquid crystal composition of the present invention can contain an ultraviolet absorber and a light stabilizer as needed. There are no particular restrictions on the ultraviolet absorber or light stabilizer used, but those that improve light resistance, such as optically anisotropic bodies and optical films, are preferred.

  Examples of the ultraviolet absorber include 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole “tinuvin PS”, “tinuvin 99-2”, “tinuvin 109”, “TINUVIN 213”, "TINUVIN 234", "TINUVIN 326", "TINUVIN 328", "TINUVIN 329", "TINUVIN 384-2", "TINUVIN 571", 2- (2H-benzotriazol-2-yl) -4,6-bis (1-Methyl-1-phenylethyl) phenol "TINUVIN 900", 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3 , 3-tetramethylbutyl) phenol “TINUVIN 928”, “TINU IN 1130 "," TINUVIN 400 "," TINUVIN 405 ", 2,4-bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3,5-triazine" "TINUVIN 460", "TINUVIN 479", "TINUVIN 5236" (all manufactured by BASF Corporation), "ADEKA STAB LA-32", "ADEKA STAB LA-34", "ADEKA STAB LA-36", "ADEKA STAB LA-31", "ADK STAB 1413" and "ADK STAB LA-51" (all manufactured by ADEKA Corporation) and the like.

Examples of the light stabilizer include “TINUVIN 111FDL”, “TINUVIN 123”, “TINUVIN 144”, “TINUVIN 152”, “TINUVIN 292”, “TINUVIN 622”, “TINUVIN 770”, “TINUVIN 765”, and “TINUVIN 780”. "," TINUVIN 905 "," TINUVIN 5100 "," TINUVIN 5050 "," TINUVIN 5060 "," TINUVIN 5151 "," CHIMASSORB 119FL "," CHIMASSORB 944FL "," CHIMASSORB 944LD ", and more. "ADK STAB LA-52", "ADK STAB LA-57", "ADK STAB LA-62", "ADK STAB LA-67", "A Kasutabu LA-63P "," ADK STAB LA-68LD "," ADK STAB LA-77 "," ADEKA STAB LA-82 "," ADK STAB LA-87 "(manufactured by KK ADEKA) and the like.
The amount of the ultraviolet absorber added is 0.01 to 2.0% by mass based on the total amount of the liquid compound having at least one polymerizable group used in the polymerizable liquid crystal composition of the present invention. Is more preferable, and more preferably 0.05 to 1.0% by mass.
[G] Leveling Agent The polymerizable liquid crystal composition of the present invention can contain a leveling agent as needed. The leveling agent to be used is not particularly limited, but is preferably one that reduces unevenness in film thickness when forming a thin film such as an optically anisotropic body or an optical film. Examples of the leveling agent include alkyl carboxylate, alkyl phosphate, alkyl sulfonate, fluoroalkyl carboxylate, fluoroalkyl phosphate, fluoroalkyl sulfonate, polyoxyethylene derivative, fluoroalkyl ethylene oxide derivative, polyethylene Glycol derivatives, alkyl ammonium salts, fluoroalkyl ammonium salts and the like can be mentioned.
Specifically, "MegaFac F-251", "MegaFac F-281", "MegaFac F-430", "MegaFac F-444", "MegaFac F-472SF", "MegaFac F-F" 477, MegaFac F-510, MegaFac F-552, MegaFac F-553, MegaFac F-554, MegaFac F-555, MegaFac F-556 , "MegaFac F-557", "MegaFac F-558", "MegaFac F-559", "MegaFac F-560", "MegaFac F-561", "MegaFac F-562", " MegaFac F-563, MegaFac F-565, MegaFac F-568, MegaFac F-569, MegaFac F-570, MegaFac Fac R-40, Mega Fac R-41, Mega Fac R-94, Mega Fac RS-72-K, Mega Fac RS-75, Mega Fac RS-76-E, "MegaFac RS-76-NS", "MegaFac RS-90", "MegaFac DS-21" (all made by DIC Corporation),
"Fantagent 100", "Futagent 100C", "Futagent 150", "Futagent 150CH", "Futagent 300", "Futagent 400SW", "Futagent 251", "Futagent 215M", "Futagent" Gent 212M "," Fentant 250 "," Fentant 212D "," FTX-218 "," Fentant 209F "," Fentant 245F "," Fentant 208G "," Fentant 212P "," Fentant 220P ""," Fergent 228P "," Fergent 601AD "," Fergent 602A "," Fergent 650A "," Fergent 750FM "," FTX-730FM "," Fergent 730FL "," Ftergent " Gent 710FS "," Futagent 710FM "," Futagent 710FL "," Futagent 750LL "," FTX-730LS "," Futagent 730LM "(all manufactured by Neos Co., Ltd.),
"BYK-300", "BYK-302", "BYK-306", "BYK-307", "BYK-310", "BYK-315", "BYK-320", "BYK-322", "BYK" -323 "," BYK-325 "," BYK-330 "," BYK-331 "," BYK-333 "," BYK-337 "," BYK-340 "," BYK-344 "," BYK-370 ". , "BYK-375", "BYK-377", "BYK-350", "BYK-352", "BYK-354", "BYK-355", "BYK-356", "BYK-358N", "BYK-361N", "BYK-357", "BYK-390", "BYK-392", "BYK-UV3500", "BYK-UV3510", "BYK-UV3570", "B K-Silclean3700 "(manufactured by BYK Co., Ltd.),
"TEGO Rad2100", "TEGO Rad2200N", "TEGO Rad2250", "TEGO Rad2300", "TEGO Rad2500", "TEGO Rad2700", "TEGO Flow300", "TEGO Flow370", "TEGO Flow425F", "TEGO Flow425", "TEGO Flow425F" , “TEGO Flow ZFS460”, “TEGO Glide100”, “TEGO Glide130”, “TEGO Glide410”, “TEGO Glide415”, “TEGO Glide432”, “TEGO Glide440”, “TEGO Glide48,” “TEGO Glide48, TEGO Glide450,” “TEGO Glide450,” “TEGO Glide48, TEGO Glide48, TEGO Glide48, TEGO Glide450,“ TEGO Glide48, TEGO Glide450, “TEGO Glide450,“ TEGO Glide450, “TEGO Glide450,” “TEGO Glide450,” “TEGO Glide450,” “TEGO Glide450,” “TEGO Glide48, TEGO Glide450,“ TEGO Glide450, “TEGO Glide450,” “TEGO Glide450,” “TEGO Glide450,” “TEGO Glide450,” “TEGO Glide450,” “TEGO Glide450,” “TEGO Glide450,” “TEGO Glide450,” “TEGO Glide450” B1484 "," TEGO Glide ZG400 "," TEGO Twin42 " 0 "," TEGO Wet KL245 "," TEGO Wet260 "," TEGO Wet270 "," TEGO Wet500 ", (manufactured by Evonik Industries Co., Ltd.),
"FC-4430", "FC-4432" (all made by 3M Japan KK),
"Unidyne NS" (above, manufactured by Daikin Industries, Ltd.),
"Surflon S-241", "Surflon S-242", "Surflon S-243", "Surflon S-420", "Surflon S-611", "Surflon S-651", "Surflon S-386" (or more) , Manufactured by AGC Seimi Chemical Co., Ltd.)
"Disparon 1970", "Disparon 230", "Disparon LF-1980", "Disparon LF-1982", "Disparon LF-1983", "Disparon LF-1084", "Disparon LF-1985", "Disparon LHP-90" , "Disparon LHP-91", "Disparon LHP-95", "Disparon LHP-96", "Disparon OX-715", "Disparon 1930N", "Disparon 1933", "Disparon 1934", "Disparon 1711EF", "Disparon 1751N", "Disparon 1761", "Disparon LS-009", "Disparon LS-001" (the above, manufactured by Kusumoto Kasei Co., Ltd.),
"PF-151N", "PF-636", "PF-6320", "PF-656", "PF-6520", "PF-652-NF", "PF-3320" (all manufactured by OMNOVA SOLUTIONS) ),
“Polyflow No. 7”, “Polyflow No. 50E”, “Polyflow No. 50EHF”, “Polyflow No. 54N”, “Polyflow No. 75”, “Polyflow No. 77”, “Polyflow No. 85”, “Polyflow No. 85” “Polyflow No. 85HF”, “Polyflow No. 90”, “Polyflow No. 90D-50”, “Polyflow No. 95”, “Polyflow No. 99C”, “Polyflow KL-400K”, “Polyflow KL-400HF”, “Polyflow KL-402”, “Polyflow KL-403”, “Polyflow KL-100”, “Polyflow LE-604”, (manufactured by Kyoeisha Chemical Co., Ltd.),
"L-7001", "L-7002", "8032 ADDITIVE", "57 ADDIVE", "L-7064", "FZ-2110", "FZ-2105", "67 ADDIVE", "8616 ADDIVE" (Toray Dow Silicone Co., Ltd.)
“KP-124”, “KP-341”, “KP-323”, “KP-327”, “KP-611”, “KP-369”, “KP-625” (all manufactured by Shin-Etsu Chemical Co., Ltd.) )
And the like.

  The amount of the leveling agent to be used in the polymerizable liquid crystal composition of the present invention is 0.01 to 0.01% with respect to the total amount of the liquid crystal compound having at least one polymerizable group used in the polymerizable liquid crystal composition of the present invention. The content is preferably 2.0% by mass, more preferably 0.05 to 0.5% by mass.

In addition, when the polymerizable liquid crystal composition of the present invention is used as an optically anisotropic material, the use of the above-mentioned leveling agent can effectively reduce the tilt angle at the air interface.
[H] Alignment control agent The polymerizable liquid crystal composition of the present invention may contain an alignment control agent for controlling the alignment state of the liquid crystal compound. Examples of the alignment controlling agent include those in which the liquid crystal compound is substantially horizontally aligned, substantially vertically aligned, or substantially hybrid aligned with the substrate. In addition, when a chiral compound is added, those which are substantially planarly oriented may be mentioned. As described above, the horizontal orientation and the planar orientation may be induced by the surfactant, but there is no particular limitation as long as the respective orientation states are induced. Can be.
As such an orientation controlling agent, for example, a weight average molecular weight having a repeating unit represented by the following general formula (8), which has an effect of effectively reducing a tilt angle of an air interface when an optically anisotropic material is used. Is 100 or more and 1,000,000 or less.

(Wherein, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and one hydrogen atom in the hydrocarbon group is one It may be substituted with the above halogen atom.)
Further, a rod-like liquid crystalline compound modified with a fluoroalkyl group, a discotic liquid crystalline compound, a polymerizable compound containing a long-chain aliphatic alkyl group which may have a branched structure, and the like are also included.

Those having the effect of effectively increasing the tilt angle at the air interface when used as an optically anisotropic material include cellulose nitrate, cellulose acetate, cellulose propionate, cellulose butyrate, and a heteroaromatic salt-modified rod-like liquid crystal. Compounds, rod-like liquid crystalline compounds modified with cyano groups and cyanoalkyl groups, and the like.
[I] Chain Transfer Agent The polymerizable liquid crystal composition of the present invention may contain a chain transfer agent in order to further improve the adhesion between the polymer or the optically anisotropic material and the substrate. As the chain transfer agent, aromatic hydrocarbons, chloroform, carbon tetrachloride, carbon tetrabromide, halogenated hydrocarbons such as bromotrichloromethane,
Mercaptan compounds such as octyl mercaptan, n-butyl mercaptan, n-pentyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mer, n-dodecyl mercaptan, t-tetradecyl mercaptan, t-dodecyl mercaptan, hexanedithiol, decanedithiol 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane Tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakis Thiopropionate, tris (2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) Thiol compounds such as -4,6-dimercapto-s-triazine, sulfide compounds such as dimethylxanthogen disulfide, diethylxanthogen disulfide, diisopropylxanthogen disulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, and N, N-dimethyl Aniline, N, N-divinylaniline, pentaphenylethane, α-methylstyrene dimer, acrolein, allyl alcohol, terpinolene, α-terpinene, γ-ter Nene, dipentene, but and the like, 2,4-diphenyl-4-methyl-1-pentene, thiol compounds are more preferred.
Specifically, compounds represented by the following formulas (9-1) to (9-12) are preferable.

In the formula, R ⁹⁵ represents an alkyl group having 2 to 18 carbon atoms, the alkyl group may be linear or branched, and one or more methylene groups in the alkyl group may be an oxygen atom And the sulfur atom is not directly bonded to each other, and may be substituted with an oxygen atom, a sulfur atom, -CO-, -OCO-, -COO-, or -CH = CH-, and R ⁹⁶ is a carbon atom. Represents an alkylene group of the formulas 2 to 18, wherein at least one methylene group in the alkylene group is an oxygen atom, a sulfur atom, -CO-, -OCO- , -COO-, or -CH = CH-.

The chain transfer agent is preferably added in the step of mixing the polymerizable liquid crystal compound with the organic solvent and heating and stirring to prepare a polymerizable solution, but is added in the subsequent step of mixing the polymerization initiator into the polymerizable solution. Or may be added in both steps.
The amount of the chain transfer agent to be added is preferably 0.5 to 10% by mass relative to the total amount of the liquid crystal compound having at least one polymerizable group used in the polymerizable liquid crystal composition of the present invention, More preferably, it is 1.0 to 5.0% by mass.

Further, a non-polymerizable liquid crystal compound or the like can be added as needed to adjust physical properties. The polymerizable compound having no liquid crystallinity is preferably added in a step of mixing the polymerizable compound with an organic solvent and heating and stirring to prepare a polymerizable solution. The polymerization initiator may be added in the step of mixing the polymerization initiator into the solution, or may be added in both steps. The addition amount of these compounds is preferably 20% by mass or less, more preferably 10% by mass or less, based on the total amount of the liquid crystal compound having at least one polymerizable group used in the polymerizable liquid crystal composition of the present invention. It is more preferably at most 5% by mass.
[J] Infrared absorber The polymerizable liquid crystal composition of the present invention can contain an infrared absorber as needed. The infrared absorber to be used is not particularly limited, and may include a known and commonly used one as long as the orientation is not disturbed.

  Examples of the infrared absorber include a cyanine compound, a phthalocyanine compound, a naphthoquinone compound, a dithiol compound, a diimmonium compound, an azo compound, and an aluminum salt.

Specifically, “NIR-IM1” of diimmonium salt type, “NIR-AM1” of aluminum salt type (all manufactured by Nagase Chemtech Co., Ltd.), “Karenz IR-T”, “Karenz IR-13F” (all , Showa Denko KK), "YKR-2200", "YKR-2100" (above, manufactured by Yamamoto Kasei Co., Ltd.), "IRA908", "IRA931,""IRA955","IRA1034" (above, INDECO Corporation) ) And the like.
[K] Antistatic agent The polymerizable liquid crystal composition of the present invention can contain an antistatic agent as needed. The antistatic agent to be used is not particularly limited, and may include known and commonly used ones as long as the orientation is not disturbed.

  Examples of such an antistatic agent include a polymer compound having at least one kind of sulfonic acid group or phosphate group in a molecule, a compound having a quaternary ammonium salt, a surfactant having a polymerizable group, and the like.

  Among them, surfactants having a polymerizable group are preferable. For example, among surfactants having a polymerizable group, as anionic surfactants, "Antox SAD" and "Antox MS-2N" (all of which are available from Nippon Emulsifier Co., Ltd.) AQUALON KH-05), "AQUALON KH-10", "AQUALON KH-20", "AQUALON KH-0530", "AQUALON KH-1025" (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Aldehyde soaps SR-10N, Adekaria Soap SR-20N (made by Adeka Corporation), "Latemul PD-104" (made by Kao Corporation), alkyl ethers such as "Latemul S-120" "Latemul S-120A", "Latemul S-180P", "Latemul S-180A" (all manufactured by Kao Corporation), "Eleminor J -2 "(manufactured by Sanyo Chemical Co., Ltd.) and the like," AQUALON H-2855A "," AQUALON H-3855B "," AQUALON H-3855C "," AQUALON H-3856 "," AQUALON HS- " AQUARON HS-10, AQUALON HS-20, AQUALON HS-30, AQUALON HS-1025, AQUALON BC-05, AQUALON BC-10, AQUALON BC-20 , "AQUALON BC-1025", "AQUALON BC-2020" (above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), "Adekaria Soap SDX-222", "Adekaria Soap SDX-223", "Adekaria Soap SDX" 232 "," Adecaria Soap SDX-233 "," Adecaria Soap SDX-259 ", Adecaria Soap SE-10N, Adecaria Soap SE-20N (manufactured by ADEKA Corporation), etc., alkyl phenyl ether or alkyl phenyl ester type, "Antox MS-60", "Antox MS-2N" (The above, manufactured by Nippon Emulsifier Co., Ltd.), (Eriminol RS-30) (manufactured by Sanyo Chemical Co., Ltd.), (meth) acrylate sulfate ester-based, "H-3330P" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Phosphate esters such as "Adecaria Soap PP-70" (manufactured by ADEKA Corporation).

  On the other hand, among surfactants having a polymerizable group, nonionic surfactants such as "Antox LMA-20", "Antox LMA-27", "Antox EMH-20", and "Antox LMH- 20, "Antox SMH-20" (all manufactured by Nippon Emulsifier Co., Ltd.), "Adecaria Soap ER-10", "Adecaria Soap ER-20", "Adecaria Soap ER-30", "Adecaria Soap" Alkyl ethers such as "ER-40" (all manufactured by ADEKA Corporation), "latemul PD-420", "latemul PD-430", and "latemul PD-450" (all manufactured by Kao Corporation); RN-10 "," AQUARON RN-20 "," AQUARON RN-30 "," AQUARON RN-50 "," AQUARON RN-2025 " Above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), "Adekaria Soap NE-20", "Adekaria Soap NE-20", "Adekaria Soap NE-30", "Adekaria Soap NE-40" (all stocks) (Made by ADEKA Co., Ltd.), and (meth) acrylate sulfuric acid such as alkyl phenyl ether type or alkyl phenyl ester type, "RMA-564", "RMA-568", "RMA-1114" (all manufactured by Nippon Emulsifier Co., Ltd.) Ester type is mentioned.

  As other antistatic agents, for example, polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, propoxy polyethylene glycol (meth) acrylate, n-butoxy polyethylene glycol (meth) acrylate , N-pentaxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, ethoxy polypropylene glycol (meth) acrylate, propoxy polypropylene glycol (meth) acrylate , N-butoxy polypropylene glycol (meth) acryl , N-pentaxy polypropylene glycol (meth) acrylate, phenoxy polypropylene glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate, methoxypolytetramethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, Hexaethylene glycol (meth) acrylate, methoxyhexaethylene glycol (meth) acrylate and the like can be mentioned.

The antistatic agent can be used alone or in combination of two or more. The addition amount of the antistatic agent is preferably 0.001 to 10% by weight based on the total amount of the liquid crystal compound having at least one polymerizable group used in the polymerizable liquid crystal composition of the present invention. More preferably, the content is from 01 to 5% by weight.
[L] Dye The polymerizable liquid crystal composition of the present invention can contain a dye as needed. The dye to be used is not particularly limited, and may include known dyes as long as the orientation is not disturbed.

  Examples of the dye include a dichroic dye and a fluorescent dye. Such dyes include, for example, polyazo dyes, anthraquinone dyes, cyanine dyes, phthalocyanine dyes, perylene dyes, perinone dyes, squarylium dyes, and the like.From the viewpoint of addition, the dyes are preferably liquid crystal dyes. .

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 the Functional Dye Market”, Chapter 1, page 1, 1994, CMC Co., Ltd., Emission, can be used.
Examples of the dichroic dye include the following formulas (d-1) to (d-9)

Is mentioned. The amount of the dye such as the dichroic dye is 0.001 to 20% by weight based on the total amount of the liquid crystal compound having at least one polymerizable group used in the polymerizable liquid crystal composition of the present invention. Preferably, 0.01 to 10% by weight is more preferable.
[M] Filler The polymerizable liquid crystal composition of the present invention can contain a filler if necessary. The filler to be used is not particularly limited, and may contain a known and commonly used filler as long as the thermal conductivity of the obtained polymer is not reduced.
Examples of the filler include inorganic fillers such as alumina, titanium white, aluminum hydroxide, talc, clay, mica, barium titanate, zinc oxide, and glass fiber; metal powders such as silver powder and copper powder; aluminum nitride; Thermal conductive fillers such as boron, silicon nitride, gallium nitride, silicon carbide, magnesia (aluminum oxide), silica, crystalline silica (silicon oxide), fused silica (silicon oxide), graphite, carbon fibers including carbon nanofibers, etc. , Silver nanoparticles and the like.

Specifically, as alumina, DAM-70, DAM-45, DAM-07, DAM-05, DAW-45, DAW-05, DAW-03, ASFP-20 (all manufactured by Denki Kagaku Kogyo Co., Ltd.), AL -43-KT, AL-47-H, AL-47-1, AL-160SG-3, AL-43-BE, AS-30, AS-40, AS-50, AS-400, CB-P02, CB -P05 (all manufactured by Showa Denko KK), A31, A31B, A32, A33F, A41A, A43A, MM-22, MM-26, MM-P, MM-23B, LS-110F, LS-130, LS- 210, LS-242C, LS-250, AHP300 (all manufactured by Nippon Light Metal Co., Ltd.), AA-03, AA-04, AA-05, AA-07, AA-2, AA-5, AA-1 , AA-18 (all manufactured by Sumitomo Chemical Co., Ltd.), titanium white G-1, G-10, F-2, F-4, F-6 (all manufactured by Showa Denko KK), TAF-520, TAF-500, TAF-1500, TM-1, TA-100C, TA-100CT (all manufactured by Fuji Titanium Co., Ltd.), MT-01, MT-10EX, MT-05, MT-100S, MT-100TV, MT-100Z, MT-150EX, MT-100AQ, MT-100WP, MT-100SA, MT-100HD, MT-300HD, MT-500SA, MT-600SA, MT-700HD (all manufactured by Teica Corporation), TTO- 51 (A), TTO-51 (C), TTO-55 (A), TTO-55 (B), TTO-55 (C), TTO-55 (D), TTO S-1, TTO-S-2, TTO-S-3, TTO-S-4, MPT-136, TTO-V-3 (all manufactured by Ishihara Sangyo Co., Ltd.), B-309 and B as aluminum hydroxide -309 (above, manufactured by Tomoe Industries Co., Ltd.), BA173, BA103, B703, B1403, BF013, BE033, BX103, BX043 (above, Nippon Light Metal Co., Ltd.), Nano Ace D-1000, Nano Ace D-800, Micro Ace as talc SG-95, Micro Ace P-8, Micro Ace P-6 (all manufactured by Nippon Talc Co., Ltd.), FH104, FH105, FL108, FG106, MG115, FH104S, ML112S (all manufactured by Fuji Talc Industries, Ltd.), Mica Y-1800, TM-10, A-11, SJ-005 (Yama Co., Ltd. BT-H9DX, HF-9, HF-37N, HF-90D, HF-120D, HT-F (or more, manufactured by Kyoritsu Materials Co., Ltd.), BT-100, HPBT series (or more, as barium titanate) BT series (manufactured by Sakai Chemical Industry Co., Ltd.), Parceram BT (manufactured by Nippon Chemical Industry Co., Ltd.), FINEX-30, FINEX-30W-LP2, FINEX-50, FINEX-50S as zinc oxide -LP2, XZ-100F (made by Sakai Chemical Industry Co., Ltd.), FZO-50 (made by Ishihara Sangyo Co., Ltd.), MZ-300, MZ-306X, MZY-505S, MZ-506X, MZ-510HPSX (more than, Teica Co., Ltd.), CS6SK-406, CS13C-897, CS3PC- 55, CS3LCP-256 (all, Nitto Boseki), ECS03-615, ECS03-650, EFDE50-01, EFDE50-31 (all, Central Glass Corporation), ACS6H-103, ACS6S-750 (all, NEC) Glass Co., Ltd.), spherical silver powders AG3 and AG4, flake silver powders FA5 and FA2 (both manufactured by DOWA Hi-Tech Co., Ltd.), SPQ03R, SPN05N, SPN08S, and Q03R (both manufactured by Mitsui Mining & Smelting Co., Ltd.) as silver powder, AY-6010 AY-6080 (all manufactured by Tanaka Kikinzoku Co., Ltd.), ASP-100 (Aida Chemical Industry Co., Ltd.), Ag-coated powder AG / SP (Mitsubishi Materials Electronics Co., Ltd.), copper powder MA-O015K, MA- O02K, MA-O025K (Mitsui Metal Ore Co., Ltd.), electrolytic copper powder # 52-C, # 6 (JX Nippon Mining & Metals Co., Ltd.), 10% Ag-coated Cu-HWQ (Fukuda Metal Foil & Powder Co., Ltd.), copper powder Type- A, Type-B (above, manufactured by DOWA Electronics Co., Ltd.), UCP-030 (manufactured by Sumitomo Metal Mining Co., Ltd.),
H grade, E grade, HT grade (manufactured by Tokuyama Corporation), TOYAL TecFiller TFS-A05P, TOYAL TecFiller TFZ-A02P (manufactured by Toyo Aluminum Co., Ltd.), ALN020BF, ALN050BF, ALN020AF as aluminum nitride , ALN020SF (above, manufactured by Tomoe Kogyo Co., Ltd.), FAN-f05, FAN-f30 (above, manufactured by Furukawa Electronics Co., Ltd.), denkaboron nitride SGP, dencaboron nitride MGP, dencaboron nitride GP as boron nitride, Dencaboron nitride HGP, dencaboron nitride SP-2, dencaboron nitride SGPS (all manufactured by Denki Kagaku Kogyo KK), UHP-S1, UHP-1K, UHP-2, UHP-EX (all manufactured by Showa Denko KK) SN-9, SN-9S, SN-9FWS, SN-F1, SN-F2 (all manufactured by Denki Kagaku Kogyo KK), and CF0027 as silicon nitride , CF0093, CF0018, CF0033 (manufactured by Nippon Frit Co., Ltd.), and silicon carbide GMF-H type, GMF-H2 type, GMF-LC type (manufactured by Taiheiyo Random Corporation), HSC1200, HSC1000, HSC059, HSC059I , HSC007 (above, manufactured by Tomoe Kogyo Co., Ltd.), Silica as silica (Fuji Silysia Chemical Ltd.), AEROSIL R972, AEROSIL R104, AEROSIL R202, AEROSIL 805, AEROSIL R812, AEROSIL R7200 (above, This Aerosil Co., Ltd.), Leoseal series (Tokuyama Co., Ltd.), and crystalline silica (silicon oxide) as CMC-12, VX-S, VX-SR (all, manufactured by Tatsumori Co., Ltd.), fused silica ( FB-3SDC, FB-3SDX, SFP-30M, SFP-20M, SFP-30MHE, SFP-130MC, UFP-30 (all manufactured by Denki Kagaku Kogyo Co., Ltd.), Excelica Series (manufactured by Tokuyama Corporation) as silicon oxide) ), AEROXIDE Alu C and AEROXIDE Alu 65 (all manufactured by Nippon Aerosil Co., Ltd.) as aluminum oxide, Trecamild Fiber MLD-30, Trekamild Fiber MLD-300 (all manufactured by Toray Industries, Inc.) as carbon fiber and graphite, CFMP -30X, CFMP-150X (or more Nippon Polymer Sangyo Co., Ltd.), XN-100, HC-600 (Nippon Graphite Fiber Co., Ltd.), SWeNT SG65, SWeNT SGi, IsoNanoTubes-M, IsoNanoTubes-S, PureTubes, Pyrograf PR-25-XT-PS , PR-25XT-LHT (above, manufactured by Sigma-Aldrich Corp.).

The filler can be used alone or in combination of two or more. The amount of the filler to be added is preferably 0.01 to 80% by weight based on the total amount of the liquid crystal compound having at least one polymerizable group, using the polymerizable liquid crystal composition of the present invention, 0.1 to 50% by weight is more preferred.
[N] Chiral compound The polymerizable liquid crystal composition of the present invention may contain a chiral compound for the purpose of obtaining a chiral nematic phase. The chiral compound need not itself exhibit liquid crystallinity, and may or may not have a polymerizable group. The direction of the helix of the chiral compound can be appropriately selected depending on the intended use of the polymer.

  The chiral compound having a polymerizable group is not particularly limited, and a known compound can be used, but a chiral compound having a large helical twisting power (HTP) is preferable. The polymerizable group is preferably a vinyl group, a vinyloxy group, an allyl group, an allyloxy group, an acryloyloxy group, a methacryloyloxy group, a glycidyl group, or an oxetanyl group, and particularly preferably an acryloyloxy group, a glycidyl group, or an oxetanyl group.

  The compounding amount of the chiral compound needs to be appropriately adjusted depending on the helical inducing force of the compound, but is preferably 0.5 to 80% by mass based on the total amount of the liquid crystal compound having a polymerizable group and the chiral compound. , Preferably 3 to 50% by mass, more preferably 5 to 30% by mass.

  Specific examples of the chiral compound include compounds represented by the following formulas (10-1) to (10-4), but are not limited to the following formulas.

In the above formula, Sp ^5a and Sp ^5b each independently represent an alkylene group having 0 to 18 carbon atoms, and the alkylene group is a carbon atom having one or more halogen atoms, a CN group, or a polymerizable functional group. It may be substituted by an alkyl group having 1 to 8, two or more of CH ₂ groups, independently of one another each of the present in the radical is not one CH ₂ group or adjacent, each other oxygen atom Are not directly bonded to —O—, —S—, —NH—, —N (CH ₃ ) —, —CO—, —COO—, —OCO—, —OCOO—, —SCO—, and —COS—. Or may be replaced by -C≡C-,
A1, A2, A3, A4, A5 and A6 each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group, a 1,4-cyclohexenyl group, a 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, thiophen-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-octahydro Enanthrene-2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5-b '] dithiophen-2,6-diyl group, benzo [1,2-b: 4 5-b '] diselenophen-2,6-diyl group, [1] benzothieno [3,2-b] thiophen-2,7-diyl group, [1] benzoselenopheno [3,2-b] selenophene-2 , 7-diyl group or fluorene-2,7-diyl group, n, l and k each independently represent 0 or 1, and 0 ≦ n + 1 + k ≦ 3;
m5 represents 0 or 1,
Z0, Z1, Z2, Z3, Z4, Z5 and Z6 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 alkyl group or a single bond which may have a halogen atom having 2 to 10 carbon atoms,
R ^5a and R ^5b represent a hydrogen atom, a halogen atom, a cyano group or an alkyl group having 1 to 18 carbon atoms, and the alkyl group may be substituted with one or more halogen atoms or CN. two or more CH ₂ groups not one CH ₂ group or adjacent present in the radical are each, independently of one another, in the form of oxygen atoms are not directly bonded to each other, -O -, - S -, - NH—, —N (CH ₃ ) —, —CO—, —COO—, —OCO—, —OCOO—, —SCO—, —COS—, or —C≡C—, or R ^5a and R ^5b are represented by the general formula (10-a)

(In the formula, P ^5a represents a polymerizable functional group, and Sp ^5a has the same meaning as Sp ^1. )
^P5a represents a substituent selected from the polymerizable groups represented by the following formulas (P-1) to (P-20).

  Further specific examples of the chiral compound include compounds represented by the following general formulas (10-5) to (10-38).

  In the above formula, m and n each independently represent an integer of 1 to 10, R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a fluorine atom. , May be the same or different.

  As the chiral compound having no polymerizable group, specifically, for example, cholesteryl pelargonate having a cholesteryl group as a chiral group, cholesterol stearate, manufactured by DH Corporation having a 2-methylbutyl group as a chiral group "CB-15", "C-15", "S-1082" manufactured by Merck, "CM-19", "CM-20", "CM" manufactured by Chisso, 1-methylheptyl group as a chiral group "S-811" manufactured by Merck and "CM-21" and "CM-22" manufactured by Chisso.

When a chiral compound is added, it depends on the use of the polymer of the polymerizable liquid crystal composition of the present invention. / P) is preferably added in such an amount as to be in the range of 0.1 to 100, more preferably in the range of 0.1 to 20.
[O] Non-liquid crystalline compound having a polymerizable group The polymerizable liquid crystal composition of the present invention may contain a compound having a polymerizable group but not a liquid crystal compound. As such a compound, any compound which is generally recognized as a polymerizable monomer or a polymerizable oligomer in this technical field can be used without particular limitation. When added, it is preferably 15% by mass or less, more preferably 10% by mass or less, based on the total amount of the liquid crystal compound having at least one polymerizable group used in the polymerizable liquid crystal composition of the present invention. 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, methoxyethyl (meth) acrylate, ethyl carbitol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) Acrylate, phenoxyethyl (meth) acrylate, 2-phenoxydiethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxyethyl (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) Methyl (meth) acrylate, (3-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) acrylate, 1H-1- (trifluoromethyl) trifluoroethyl (meth) acrylate, 1H , 1H, 3H-hexafluorobutyl (meth) acrylate, 1,2,2,2-te Trafluoro-1- (trifluoromethyl) ethyl (meth) acrylate, 1H, 1H-pentadecafluorooctyl (meth) acrylate, 1H, 1H, 2H, 2H-tridecafluorooctyl (meth) acrylate, 2- (meth) ) Acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, glycidyl (meth) acrylate, 2- (meth) acryloyloxyethylphosphoric acid, acryloylmorpholine, dimethylacrylamide, dimethylaminopropylacrylamide, iropropyl Mono (meth) acrylates such as acrylamide, diethylacrylamide, hydroxyethylacrylamide, N-acryloyloxyethylhexahydrophthalimide, and 1,4-butanediol di (meth) acrylate Rate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl diol 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] fluorene, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, acrylic acid addition of 1,6-hexanediol diglycidyl ether Acrylates, diacrylates such as 1,4-butanediol diglycidyl ether acrylic acid adduct, trimethylolpropane tri (meth) acrylate, ethoxylated isocyanuric acid triacrylate, pentaerythritol tri (meth) acrylate, ε-caprolactone modified Tri (meth) acrylate such as tris- (2-acryloyloxyethyl) isocyanurate, etc., tetra (meth) acrylate such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, oligomer type (meth) acrylate, various urethane acrylates, various macromonomers, ethylene glycol diglycidyl ether, diethylene glycol diglycidide Ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, bisphenol A diglycidyl ether, epoxy compounds such as maleimide and the like. These can be used alone or in combination of two or more.

[P] Alignment Material The polymerizable liquid crystal composition of the present invention may contain an alignment material whose alignment is improved in order to improve the alignment. The alignment material to be used may be any known and commonly used one as long as it is soluble in a solvent used for the polymerizable liquid crystal composition of the present invention and capable of dissolving a liquid crystal compound having a polymerizable group. Can be added in a range that does not significantly deteriorate the orientation. Specifically, the amount is preferably 0.05 to 30% by weight, and more preferably 0.5 to 15% by weight based on the total amount of the liquid crystal compound having at least one polymerizable group used in the polymerizable liquid crystal composition of the present invention. % Is more preferable, and 1 to 10% by weight is particularly preferable. Specific examples of the alignment material include polyimide, polyamide, BCB (benzocyclobutene polymer), polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, Polyisomer sulfone, epoxy resin, epoxy acrylate resin, acrylic resin, coumarin compound, chalcone compound, cinnamate compound, fulgide compound, anthraquinone compound, azo compound, arylethene compound, etc., such as photoisomerizable or photodimerized compounds. Be , Ultraviolet radiation, the material oriented by visible light irradiation (photo-alignment material) is preferable.

  Examples of the photo-alignment material include polyimide having a cyclic cycloalkane, wholly aromatic polyarylate, polyvinyl cinnamate as disclosed in JP-A-5-232473, polyvinyl ester of paramethoxycinnamic acid, and 287453, cinnamate derivatives as described in JP-A-6-289374, and maleimide derivatives as described in JP-A-2002-265541. Specifically, compounds represented by the following formulas (12-1) to (12-9) are preferable.

In the above formula, R ⁵ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group, a nitro group, and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. group may be a branched be linear, the alkyl arbitrary hydrogen atom in the group may be substituted by a fluorine atom, one -CH in the alkyl group 2 _- or adjacent Two or more —CH ₂ — that are not independently represent —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O -CO-O -, - CO- NH -, - NH-CO- or may be substituted by -C≡C-, CH _{3 termini,} CF 3, CCl _3, a cyano group, a nitro group, an isocyano group Or a thioisocyano group. n shows 4-100,000 and m shows the integer of 1-10.
R ⁷ is a hydrogen atom, a halogen atom, a halogenated alkyl group, an allyloxy group, a cyano group, a nitro group, an alkyl group, a hydroxyalkyl group, an alkoxy group, a carboxy group or an alkali metal salt thereof, an alkoxycarbonyl group, a halogenated methoxy group , Hydroxy group, sulfonyloxy group or alkali metal salt thereof, amino group, carbamoyl group, sulfamoyl group or (meth) acryloyl group, (meth) acryloyloxy group, (meth) acryloylamino group, vinyl group, vinyloxy group and maleimide group Represents a polymerizable functional group selected from the group consisting of
(Polymer)
The polymer of the present invention is obtained by polymerizing the polymerizable liquid crystal composition of the present invention while containing the initiator. The polymer of the present invention is used for an optically anisotropic material, a retardation film, a lens, an optical component, a polarizing film, a colorant, a marking for security, a coloring material, a printed matter, a structural property, a restoration material and the like.
(Base material)
The substrate used for the optically anisotropic body of the present invention is a liquid crystal display element, an organic light emitting display element, other display elements, optical components, a coloring agent, a marking, a substrate usually used for printed matter or an optical film. There is no particular limitation as long as the material has heat resistance that can withstand heating during drying after application of the polymerizable liquid crystal composition solution of the present invention. Examples of such a substrate include organic materials such as a glass substrate, a metal substrate, a ceramic substrate, a plastic substrate, and paper. In particular, when the substrate is an organic material, examples include cellulose derivatives, polyolefins, polyesters, polyolefins, polycarbonates, polyacrylates, polyarylates, polyethersulfones, polyimides, polyphenylene sulfides, polyphenylene ethers, nylons, and polystyrenes. Among them, plastic base materials such as polyester, polystyrene, polyolefin, cellulose derivative, polyarylate, and polycarbonate are preferable. The shape of the substrate may be a flat plate or a curved surface. These base materials may have an electrode layer, an antireflection function, and a reflection function as needed.

In order to improve the coatability of the polymerizable liquid crystal composition of the present invention and the adhesiveness to the polymer, these substrates may be subjected to a surface treatment. Examples of the surface treatment include ozone treatment, plasma treatment, corona treatment, and silane coupling treatment. Also, an organic thin film, an inorganic oxide thin film, a metal thin film, or the like is provided on the surface of the base material by a method such as vapor deposition in order to adjust the light transmittance and the reflectance, or a base material is added 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 microlens sheet, a color filter, or the like. Above all, a pickup lens, a retardation film, a light diffusion film, and a color filter which have higher added value are preferable.
(Orientation treatment)
In addition, the substrate is usually subjected to an alignment treatment or provided with an alignment film so that the polymerizable liquid crystal composition is aligned when the polymerizable liquid crystal composition solution of the present invention is applied and dried. May be. Examples of the orientation treatment include a stretching treatment, a rubbing treatment, a polarized ultraviolet-visible light irradiation treatment, an ion beam treatment, and an oblique deposition treatment of SiO ₂ on a substrate. When an alignment film is used, a known and commonly used alignment film is used. Examples of such an alignment film include polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyether sulfone, epoxy resin, epoxy acrylate resin, acrylic resin, azo compound, and coumarin. Examples thereof include compounds, chalcone compounds, cinnamate compounds, fulgide compounds, anthraquinone compounds, azo compounds, arylethene compounds, and the like, or polymers and copolymers of the above compounds. The compound to be subjected to the alignment treatment by rubbing is preferably one that promotes the crystallization of the material by performing an alignment treatment or a heating step after the alignment treatment. It is preferable to use a photo-alignment material among the compounds that perform an alignment treatment other than rubbing.

  In general, when a liquid crystal composition is brought into contact with a substrate having an alignment function, liquid crystal molecules are aligned in the vicinity of the substrate along the direction in which the substrate has been subjected to alignment processing. Whether the liquid crystal molecules are aligned horizontally, tilted or vertically aligned with the substrate is greatly affected by the alignment treatment method for the substrate. For example, if an alignment film having a very small pretilt angle is provided on a substrate as used in an in-plane switching (IPS) type liquid crystal display device, a polymerizable liquid crystal layer that is substantially horizontally aligned can be obtained.

Further, when an alignment film used for a TN type liquid crystal display element is provided on a substrate, a polymerizable liquid crystal layer having a slightly inclined alignment is obtained, and an alignment film used for an STN type liquid crystal display element is obtained. When a polymerizable liquid crystal layer is used, a polymerizable liquid crystal layer whose orientation is greatly inclined can be obtained.
(Application)
The coating method for obtaining the optically anisotropic material of the present invention includes an applicator method, a bar coating method, a spin coating method, a roll coating method, a direct gravure coating method, a reverse gravure coating method, a flexo coating method, an inkjet method, and a die coating method. A known method such as a coating method, a cap coating method, a dip coating method, a slit coating method, and a spray coating method can be used. After applying the polymerizable liquid crystal composition, it is dried.

  After the application, it is preferable that the liquid crystal molecules in the polymerizable liquid crystal composition of the present invention are uniformly aligned while maintaining a smectic phase or a nematic phase. One of the methods is a heat treatment method. Specifically, after applying the polymerizable liquid crystal composition of the present invention on a substrate, the liquid crystal composition has an N (nematic phase) -I (isotropic liquid phase) transition temperature (hereinafter referred to as NI transition temperature). The liquid crystal composition is heated above to bring the liquid crystal composition into an isotropic liquid phase. From there, a nematic phase is developed by slow cooling if necessary. At this time, it is desirable that the liquid crystal phase be maintained at a temperature once exhibiting a liquid crystal phase, and the liquid crystal phase domain be sufficiently grown to be a monodomain. Alternatively, after applying the polymerizable liquid crystal composition of the present invention on a substrate, a heat treatment may be performed to maintain the temperature within a temperature range in which the nematic phase of the polymerizable liquid crystal composition of the present invention develops for a certain time.

  If the heating temperature is too high, the polymerizable liquid crystal compound may cause an undesirable polymerization reaction and deteriorate. Further, if the temperature is excessively cooled, the polymerizable liquid crystal composition undergoes phase separation, which causes precipitation of crystals and a higher-order liquid crystal phase such as a smectic phase, thereby making it impossible to perform alignment treatment.

By performing such a heat treatment, it is possible to produce a homogeneous optically anisotropic body having less alignment defects as compared with a coating method of simply applying.
Further, after performing the homogeneous alignment treatment in this manner, the liquid crystal phase is cooled to a minimum temperature at which phase separation does not occur, that is, a supercooled state, and polymerization is performed in a state where the liquid crystal phase is aligned at this temperature. An optically anisotropic body having higher orientational order and excellent transparency can be obtained.
(Polymerization step)
The polymerization treatment of the dried polymerizable liquid crystal composition is generally performed by irradiation with light such as visible ultraviolet light or heating in a state of being uniformly aligned. When the polymerization is carried out by light irradiation, specifically, irradiation with visible ultraviolet light having a wavelength of 420 nm or less is preferable, and irradiation with ultraviolet light having a wavelength of 250 to 370 nm is most preferable. However, when the polymerizable liquid crystal composition causes decomposition or the like due to visible ultraviolet light of 420 nm or less, it may be preferable to perform the polymerization treatment with visible ultraviolet light of 420 nm or more.
(Polymerization method)
Examples of a method of polymerizing the polymerizable liquid crystal composition of the present invention include a method of irradiating an active energy ray and a thermal polymerization method, but the method does not require heating and the reaction proceeds at room temperature. Irradiation is preferable, and among them, a method of irradiating light such as ultraviolet rays is preferable because of simple operation. The temperature at the time of irradiation is preferably a temperature at which the polymerizable liquid crystal composition of the present invention can maintain a liquid crystal phase, and is preferably 30 ° C. or less as much as possible to avoid induction of thermal polymerization of the polymerizable liquid crystal composition. In addition, the polymerizable liquid crystal composition generally has a temperature within a range from a C (solid phase) -N (nematic) transition temperature (hereinafter abbreviated as a CN transition temperature) to a NI transition temperature in a temperature rising process. Shows the liquid crystal phase. On the other hand, in the temperature decreasing process, a non-equilibrium state is obtained thermodynamically, so that the liquid crystal state may be maintained without solidification even at a temperature lower than the CN transition temperature. This state is called a supercooled state. In the present invention, a liquid crystal composition in a supercooled state is also included in a state in which a liquid crystal phase is maintained. Specifically, irradiation with ultraviolet light of 390 nm or less is preferable, and irradiation with light having a wavelength of 250 to 370 nm is most preferable. However, when the polymerizable liquid crystal composition causes decomposition or the like due to ultraviolet light having a wavelength of 390 nm or less, it may be preferable to perform the polymerization treatment with ultraviolet light having a wavelength of 390 nm or more. This light is preferably diffused light and unpolarized light. The UV irradiation intensity is preferably in the range of 0.05 mW / cm ^{2 to} 10 W / cm ² . In particular, a range of 0.2 mW / cm ^{2 to 2} W / cm ² is preferable. When the UV intensity is less than 0.05 mW / cm ² , it takes a long time to complete the polymerization. On the other hand, if the strength exceeds ² W / cm ² , the liquid crystal molecules in the polymerizable liquid crystal composition tend to undergo photodecomposition, and a large amount of heat of polymerization is generated to increase the temperature during polymerization, and the order of the polymerizable liquid crystal is increased. Variations in parameters can lead to erratic retardation of the film after polymerization.

The ultraviolet irradiation amount is ^preferably in the range of ^{10mJ / cm 2 ~20J / cm 2} , more preferably ^{50mJ / cm 2 ~10J / cm 2} , 100mJ / cm 2 ~5J / cm 2 is particularly preferred.

  After polymerizing only a specific portion by ultraviolet irradiation using a mask, the orientation state of the unpolymerized portion is changed by applying an electric field, a magnetic field or a temperature, and then the unpolymerized portion is polymerized. It is also possible to obtain an optically anisotropic body having a plurality of regions having orientation directions.

  In addition, when only a specific portion is polymerized by ultraviolet irradiation using a mask, an electric field, a magnetic field, a temperature, or the like is applied to the polymerizable liquid crystal composition in an unpolymerized state in advance to regulate the alignment, and the state is maintained. An optically anisotropic body having a plurality of regions having different alignment directions can be obtained also by irradiating light from above the mask and polymerizing it.

  The optically 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 optically anisotropic body, or used as it is without peeling off from the substrate. You can also. In particular, since other members are unlikely to be contaminated, they are useful when used as a substrate to be laminated or when bonded to another substrate for use.

In order to stabilize the solvent resistance and heat resistance of the obtained optically anisotropic body, the optically anisotropic body can be heat-aged. In this case, it is preferable to heat the polymer film above the glass transition point. Usually, 50 to 300C is preferable, 80 to 240C is more preferable, and 100 to 220C is particularly preferable.
(Retardation film)
The retardation film of the present invention contains the optically anisotropic body, and the liquid crystalline compound forms a uniform and continuous alignment state with respect to the base material, and is in-plane with respect to the base material. It is only necessary to have biaxiality in the outside, in the plane, out of the plane, or in the plane. Further, an adhesive or an adhesive layer, an adhesive or an adhesive layer, a protective film, a polarizing film, or the like may be laminated.

  Examples of such a retardation film include, for example, a positive A plate in which a rod-like liquid crystalline compound is substantially horizontally aligned with a substrate, and a negative A plate in which a discotic liquid crystalline compound is vertically uniaxially aligned with a substrate. A positive C plate in which the rod-like liquid crystal compound is substantially vertically oriented with respect to the substrate; a negative C plate in which the rod-like liquid crystal compound is cholesterically oriented with respect to the base material, or a uniaxially horizontally aligned disc-like liquid crystal compound. Orientation modes of a plate, a biaxial plate, a positive O plate in which a rod-like liquid crystal compound is hybrid-aligned to a substrate, and a negative O-plate in which a discotic liquid crystal compound is hybrid-aligned to a substrate can be applied. When used for an optical compensation film of a liquid crystal display device, various alignment modes can be applied without particular limitation as long as the viewing angle dependency is improved.

For example, the orientation modes of a positive A plate, a negative A plate, a positive C plate, a negative C plate, a biaxial plate, a positive O plate, and a negative O plate can be applied.
The retardation film of the present invention can also be used as a wave plate. When used as a wave plate, the retardation film of the present invention is a positive A plate in which a polymerizable liquid crystal compound is substantially horizontally aligned with respect to a substrate, and is used as a half wave plate or a quarter wave plate. It is preferred to use.

The retardation film of the present invention can also be used as a polarizing reflection film or an infrared reflection film. In that case, in the retardation film of the present invention, the rod-shaped liquid crystalline compound is substantially cholesterically aligned in the horizontal direction with respect to the substrate, and in the case of the polarized light reflecting film, the pitch is in the visible light region, and In the case of an external reflection film, the pitch is preferably in the infrared region.
(lens)
The polymerizable liquid crystal composition of the present invention is coated on a substrate, or a substrate having an alignment function, or injected into a lens-shaped mold, and uniformly aligned while holding a nematic phase or a smectic phase. The polymer can be used for the lens of the present invention by polymerization. The shape of the lens includes a simple cell type, a prism type, a lenticular type, and the like.
(Liquid crystal display device)
The polymerizable liquid crystal composition of the present invention is coated on a base material or a base material having an alignment function, uniformly aligned while holding a nematic phase or a smectic phase, and polymerized, whereby the liquid crystal of the present invention is polymerized. It can be used for a display element. Examples of usage include an optical compensation film, a patterned retardation film of a liquid crystal stereoscopic display device, a retardation correction layer of a color filter, an overcoat layer, an alignment film for a liquid crystal medium, and the like. A liquid crystal display element has a liquid crystal medium layer, a TFT driving circuit, a black matrix layer, a color filter layer, a spacer, and a liquid crystal medium layer on at least two base materials, and at least a corresponding electrode circuit is held therebetween. The layer, the polarizing plate layer, and the touch panel layer are disposed outside the two substrates, but in some cases, the optical compensation layer, the overcoat layer, the polarizing plate layer, and the electrode layer for the touch panel are narrowed within the two substrates. May be carried.

As the alignment mode of the liquid crystal display element, there are TN mode, VA mode, IPS mode, FFS mode, OCB mode and the like. When used in an optical compensation film or an optical compensation layer, a phase difference corresponding to the alignment mode is obtained. Film can be produced. When used in a patterned retardation film, the liquid crystal compound in the polymerizable liquid crystal composition may be substantially horizontally aligned with the substrate. When used in the overcoat layer, a liquid crystalline compound having more polymerizable groups in one molecule may be thermally polymerized. When used in an alignment film for a liquid crystal medium, it is preferable to use a polymerizable liquid crystal composition in which an alignment material and a liquid crystal compound having a polymerizable group are mixed. Further, it can be mixed in a liquid crystal medium, and has an effect of improving various characteristics such as response speed and contrast depending on the ratio of the liquid crystal medium to the liquid crystal compound.
(Organic light emitting display device)
The polymerizable liquid crystal composition of the present invention is applied to a base material or a base material having an alignment function, uniformly aligned while maintaining a nematic phase or a smectic phase, and polymerized, whereby the organic luminescence of the present invention is obtained. It can be used for a display element. As a usage form, by combining a retardation film obtained by the above-mentioned polymerization with a polarizing plate, it can be used as an antireflection film of an organic light emitting display device. When used as an antireflection film, the angle between the polarization axis of the polarizing plate and the slow axis of the retardation film is preferably about 45 °. The polarizing plate and the retardation film may be bonded with an adhesive or a pressure-sensitive adhesive. Further, the layers may be directly laminated by a rubbing treatment or an alignment treatment in which a photo-alignment film is laminated on a polarizing plate. The polarizing plate used at this time may be a film having a polarizing function. Examples include a dichroic dye or a film on which a dichroic dye is adsorbed, a film in which an aqueous solution containing the dichroic dye is applied on a substrate to form a polarizing layer, a wire grid polarizer, and the like.

  As the polyvinyl alcohol-based resin, those obtained by saponifying a polyvinyl acetate-based resin can be used.Examples of the polyvinyl acetate-based resin include polyvinyl acetate, which is a homopolymer of vinyl acetate, and vinyl acetate and Examples thereof include copolymers with other copolymerizable monomers. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group. The method of forming the polyvinyl alcohol-based resin is not particularly limited, and the film can be formed by a known method. The thickness of the polyvinyl alcohol-based raw film is not particularly limited, but is, for example, about 10 to 150 μm.

  When iodine is used as the dichroic dye, a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing iodine and potassium iodide and dyeing the same is usually employed. When a dichroic dye is used as the dichroic dye, a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic dye and dyeing it is usually employed.

  In the case of a film in which a polarizing layer is formed by applying an aqueous solution containing a dichroic dye on a substrate, examples of the dichroic dye to be applied vary depending on the type of the base material used, but include a direct dye, an acid dye, and the like. And water-insoluble dyes, such as water-soluble dyes and their salts and disperse dyes, and oil-soluble dyes. These dyes are usually dissolved in water and an organic solvent, and if necessary, a surfactant is added to the dye to be applied to a rubbed or corona-treated substrate. The organic solvent varies depending on the solvent resistance of the base material, but in general, alcohols such as methanol, ethanol and isopropyl alcohol, cellosolves such as methyl cellosolve and ethyl cellosolve, ketone cheeks such as acetone and methyl ethyl ketone, and dimethylformamide And amides such as N-methylvilolidone, and aromatic organic solvents such as benzene and toluene. The coating amount of the dye varies depending on the polarization performance of the dye, but is generally 0.05 to 1.0 g / po, preferably 0.1 to 0.8 g / rrf. As a method of applying the color PfJ liquid to the base material, various coating methods such as bar coder coating spray coating, roll coating, gravure coating and the like can be mentioned.

When a wire grid polarizer is used, it is preferable to use one formed of a conductive material such as Al, Cu, Ag, Cu, Ni, Cr, and Si.
(Lighting element)
The polymerizable liquid crystal composition of the present invention, a nematic phase or a smectic phase, or a polymer obtained by polymerizing in a state of being oriented on a substrate having an orientation function is used as a heat-radiating material for lighting elements, particularly light-emitting diode elements. You can also. As a form of the heat radiation material, a prepreg, a polymer sheet, an adhesive, a sheet with a metal foil, and the like are preferable.
(Optical parts)
The polymerizable liquid crystal composition of the present invention can be used as an optical component of the present invention by polymerizing in a state where a nematic phase or a smectic phase is maintained, or in a state where the composition is combined with an alignment material.
(Colorant)
The polymerizable liquid crystal composition of the present invention can be used as a colorant by adding a colorant such as a dye or an organic pigment.
(Polarizing film)
The polymerizable liquid crystal composition of the present invention can be used as a polarizing film in combination with or addition to a dichroic dye, a lyotropic liquid crystal or a chromonic liquid crystal.
(Marking for security)
The polymerizable liquid crystal composition of the present invention can be used as a security marking or printed matter in combination or addition with a chiral compound, dichroic dye, dye, filler, magnetic powder, fluorescent dye, or the like.

Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited to these. Unless otherwise specified, “parts” and “%” are based on mass.
(Preparation of polymerizable liquid crystal composition (1))
40 parts of the compound represented by the formula (A-1), 25 parts of the compound represented by the formula (A-2), 20 parts of the compound represented by the formula (A-3), p-methoxyphenol (MEHQ) 0 0.2 part of Megafac R-40 (R-40: manufactured by DIC Corporation) was added to 172 parts of propylene glycol monomethyl ether acetate (PGMEA) and N-methyl-2-pyrrolidone (NMP). The mixture was heated to 60 ° C. and dissolved by stirring. After the dissolution was confirmed, the temperature was returned to room temperature, 5 parts of Irgacure 907 (manufactured by BASF) was added, and the mixture was further stirred to obtain a solution. The solution was clear and homogeneous. The resulting solution was filtered through a 0.20 μm membrane filter to obtain a polymerizable liquid crystal composition (1) used in Example 1 and the like.
(Preparation of Polymerizable Liquid Crystal Compositions (2) to (83) and Comparative Polymerizable Liquid Crystal Compositions (C1) to (C23))
Examples 2 to 4 were prepared under the same conditions as in the preparation of the polymerizable liquid crystal composition (1) of Example 1 except that the compounds shown in Tables 1 to 11 below were changed to the ratios shown in Tables 1 to 11 below. The polymerizable liquid crystal compositions (2) to (83) used in No. 83 and the polymerizable liquid crystal compositions (C1) to (C23) of Comparative Examples 1 to 23 were obtained.
In addition, each component in each composition is as follows.
(Polymerizable liquid crystal compound)

(dye)

(Organic solvent)
PGMEA: Propylene glycol monomethyl ether acetate (H-1) Boiling point 146 ° C
MIBK: Methyl isobutyl ketone (H-2) Boiling point 117 ° C
MPA: 1-methoxy-2-propanol (H-3) boiling point 120 ° C
BA: butyl acetate (H-4) boiling point 126 ° C
TOL: toluene (H-5) boiling point 116 ° C
THF: tetrahydrofuran (H-6) boiling point 66 ° C
CPN: cyclopentanone (H-7) boiling point 131 ° C
NMP: N-methyl-2-pyrrolidone (H-8) boiling point 202 ° C
GBL: γ-butyrolactone (H-9) boiling point 204 ° C.
CHA: cyclohexyl acetate (H-10) boiling point 175 ° C
MBA: Methyl benzoate (H-11) boiling point 198 ° C
IPR: isophorone (H-12) boiling point 215 ° C
CRT: 2- (ethoxyethoxy) ethanol (H-13) boiling point 201 ° C
PGDA: Propylene glycol diacetate (H-14) boiling point 190 ° C
EGBEA: Ethylene glycol monobutyl ether acetate (H-15) boiling point 191 ° C
(Antioxidant)

（Ｉ−２）

(I-2)

(Polymerization inhibitor)
p-methoxyphenol (J-1)

(Polymerization initiator)
Irgacure 907 (manufactured by BASF) (K-1)
Irgacure 819 (manufactured by BASF) (K-2)
ADEKA CRUISE NCI-930 (made by ADEKA Corporation) (K-3)
Amnirad 184 (manufactured by IGM Resins) (K-4)
Trimethylolpropane tristhiopropionate (L-1)
Alonix M-5700 (Toagosei Co., Ltd.) (L-2)
Light ester HOB-A (manufactured by Kyoeisha Chemical Co., Ltd.) (L-3)
Megafac R-40 (manufactured by DIC Corporation) (M-1)
Megafac F-554 (manufactured by DIC Corporation) (M-2)
Megafac RS-75 (manufactured by DIC Corporation) (M-3)
Megafac DS-21 (manufactured by DIC Corporation) (M-4)
Futuregent FTX-218 (manufactured by Neos Corporation) (M-5)
Futuregent 730LM (manufactured by Neos Corporation) (M-6)
TEGO Flow ZFS460 (manufactured by Evonik Industries)
(Example 1)
The solubility, storage stability (preservability), orientation of the polymerizable liquid crystal composition (1) of the present invention, and the solution viscosity were measured. Table 1 shows the results.

(Solubility)
：: After the adjustment, a transparent and uniform state can be visually confirmed.
Δ: A transparent and uniform state can be visually confirmed when heated and expanded, but when the temperature is returned to room temperature, precipitation of the compound is confirmed.
X: The compound cannot be uniformly dissolved even when heated and stirred.
(Storage stability)
The state after leaving the polymerizable liquid crystal composition (1) of the present invention in a thermostat at 0 ° C. for one week was visually observed. The polymerizable liquid crystal composition of the present invention maintained a transparent and uniform state even after one week. The storage stability was evaluated as follows:
：: A transparent and uniform state is maintained even after standing at 0 ° C. for one week.
Δ: A transparent and uniform state is maintained even after standing at 0 ° C. for 3 days.
×: Precipitation of the compound is confirmed after standing at 0 ° C. for one day.
(Orientation)
A polyimide solution for a horizontal alignment film was applied to a glass substrate having a thickness of 0.7 mm by spin coating, dried at 100 ° C. for 10 minutes, and baked at 200 ° C. for 60 minutes to obtain a coating film. The obtained coating film was rubbed. The rubbing treatment was performed using a commercially available rubbing device.

The polymerizable composition (1) of the present invention immediately after dissolution on the rubbed substrate and after the evaluation of storage stability was applied by a spin coating method, and dried at 80 ° C. for 2 minutes. The obtained coating film was left at room temperature for 1 minute, and then irradiated with ultraviolet rays at an intensity of 30 mW / cm ² for 30 seconds using a high-pressure mercury lamp to obtain an optically anisotropic body of Example 1. When the obtained optically anisotropic material was evaluated according to the following criteria, it was found that there was no alignment defect visually, and no alignment defect was observed by a polarizing microscope. In the following criteria, ◎ means the most excellent orientation, and × means no orientation.

[Evaluation criteria]
Visual observation: Two polarizing plates are arranged on a light box so as to satisfy the crossed Nicols condition, the obtained optically anisotropic material is placed between the two polarizing plates, and the optically anisotropic material is visually observed while rotating. did.
Observation with a polarizing microscope: Observed at a magnification of 200 times A: No unevenness was observed under a sodium lamp, and no defect was observed visually or under a polarizing microscope.
：: There is some unevenness in observation under a sodium lamp, but there is no defect both visually and with a polarizing microscope.
Δ: Some unevenness was observed under a sodium lamp, and there was no defect visually, but there was a non-oriented part as a whole observed with a polarizing microscope.
×: Many irregularities were observed under a sodium lamp, some defects were visually observed, and non-aligned portions were entirely present even with a polarizing microscope.
(Solution viscosity)
After 1.5 g of the polymerizable composition (1) of the present invention was placed in a cup of an E-type viscometer, the rotor of the viscometer was rotated, and the point at which the displayed value no longer changed was regarded as the viscosity. The viscosity was measured under the condition that the temperature of the polymerizable composition of the present invention was 20 ° C. The viscosity of the polymerizable composition (1) of the present invention was 6.8 mPa · s.
(Examples 2-56, 64-69)
In the same manner as in Example 1, evaluations of Examples 2 to 56 and 64 to 69 were performed.
(Example 57)
A polyimide solution for a vertical alignment film was applied to a glass substrate having a thickness of 0.7 mm by spin coating, dried at 100 ° C. for 10 minutes, and baked at 200 ° C. for 60 minutes to obtain a coating film.

The polymerizable composition (57) of the present invention immediately after dissolution and after storage stability evaluation were applied to the obtained substrate by spin coating, and dried at 80 ° C. for 2 minutes. After leaving the obtained coating film at room temperature for 1 minute, it was irradiated with ultraviolet light at an intensity of 30 mW / cm ² for 30 seconds using a high-pressure mercury lamp to obtain an optically anisotropic body having homeotropic alignment of Example 55. Was. The obtained optically anisotropic body was evaluated according to the following criteria.

[Evaluation criteria]
Visual observation: two polarizing plates were arranged on a light box so as to satisfy the crossed Nicols condition, and the obtained optically anisotropic material was placed between the two polarizing plates. Observed visually. In the following criteria, ◎ means the most excellent orientation, and × means no orientation.
Polarizing microscope observation: Observed at 200x magnification
：: No unevenness was observed under a sodium lamp, and no defect was observed visually or under a polarizing microscope.
：: There is some unevenness in observation under a sodium lamp, but there is no defect both visually and with a polarizing microscope.
Δ: Some unevenness was observed under a sodium lamp, and there was no defect visually, but there was a non-oriented part as a whole observed with a polarizing microscope.
×: Many irregularities were observed under a sodium lamp, some defects were visually observed, and non-aligned portions were entirely present even with a polarizing microscope.
(Examples 58 to 60, 70 to 73)
Evaluation of Examples 58 to 60 and 70 to 73 was performed in the same manner as in Example 57.
(Example 61)
A polyimide solution for an alignment film was applied to a glass substrate having a thickness of 0.7 mm by spin coating, dried at 100 ° C. for 10 minutes, and baked at 200 ° C. for 60 minutes to obtain a coating film. The obtained coating film was rubbed. The rubbing treatment was performed using a commercially available rubbing device.

The polymerizable composition (61) of the present invention immediately after dissolution on the rubbed substrate and after the evaluation of storage stability was applied by a spin coating method, and dried at 80 ° C. for 2 minutes. The obtained coating film was allowed to stand at room temperature for 1 minute, and then irradiated with ultraviolet light at an intensity of 30 mW / cm ² for 30 seconds using a high-pressure mercury lamp to obtain an optically anisotropic body having selective reflection characteristics of Example 61. Was. The obtained optically anisotropic body was evaluated according to the following criteria. In the following criteria, ◎ means the most excellent orientation, and × means no orientation.
[Evaluation criteria]
Visual observation: The obtained optically anisotropic body was placed on a black plate, and the optically anisotropic body was visually observed while being in front and inclined.
Observation with a polarizing microscope: Observed at a magnification of 200 times A: No unevenness was observed under a sodium lamp, and no defect was observed visually or under a polarizing microscope.
：: There is some unevenness in observation under a sodium lamp, but there is no defect both visually and with a polarizing microscope.
Δ: Some unevenness was observed under a sodium lamp, and there was no defect visually, but there was a non-oriented part as a whole observed with a polarizing microscope.
×: Many irregularities were observed under a sodium lamp, some defects were visually observed, and non-aligned portions were entirely present even with a polarizing microscope.
(Examples 62 and 63)
Evaluation of Examples 62 and 63 was performed in the same manner as in Example 61.

The polymerizable liquid crystal compositions (2) to (56) and (64) to (69) maintain a transparent and uniform state even after being left at 0 ° C. for 1 week, and after being left for 1 week immediately after dissolution. An optically anisotropic body having good orientation was obtained using any of the polymerizable liquid crystal compositions. However, in the polymerizable liquid crystal compositions (C1) to (C21), precipitation is observed after standing for one week, or defects are observed in the optically anisotropic body obtained from each polymerizable liquid crystal composition, Also, both were observed.
The polymerizable liquid crystal composition (57) is maintained in a transparent and uniform state even after being left at 0 ° C. for one week, and is visually observed immediately after dissolution, regardless of which polymerizable liquid crystal composition is used after left for one week. No alignment defect was observed, and no alignment defect was observed even by observation with a polarizing microscope.

The polymerizable liquid crystal compositions (58) to (60) and (70) to (73) maintain a transparent and uniform state even after being left at 0 ° C. for 1 week, and after being left for 1 week immediately after dissolution. An optically anisotropic body having good orientation was obtained using any of the polymerizable liquid crystal compositions.
The polymerizable liquid crystal composition (61) remained transparent and uniform after being left at 0 ° C. for one week, and was visually observed immediately after dissolution, using any of the polymerizable liquid crystal compositions after left for one week. No alignment defect was observed, and no alignment defect was observed even by observation with a polarizing microscope.

Each of the polymerizable liquid crystal compositions (62) to (63) maintained a transparent and uniform state even after being left at 0 ° C. for 1 week, and was left for 1 week immediately after dissolution. Even when used, an optically anisotropic body having good orientation was obtained.
(Example 74)
After the polymerizable liquid crystal composition 74 of the present invention was obtained in the same manner as in Example 1, a polyimide solution for a horizontal alignment film was applied to a 0.7 mm-thick glass substrate by a spin coating method, and was heated at 100 ° C. After drying for 10 minutes, the coating was obtained by baking at 200 ° C. for 60 minutes. The obtained coating film was rubbed. The rubbing treatment was performed using a commercially available rubbing device.

The polymerizable liquid crystal composition (74) of the present invention was applied to the rubbed substrate by spin coating, and dried at 90 ° C. for 2 minutes. The obtained coating film was cooled to room temperature over 2 minutes, and then irradiated with ultraviolet rays at an intensity of 30 mW / cm ² for 30 seconds using a high-pressure mercury lamp to obtain an optically anisotropic body of Example 72. When the degree of polarization, transmittance, and contrast of the obtained optically anisotropic body were measured with RETS-100 (manufactured by Otsuka Electronics Co., Ltd.), the degree of polarization was 95.0%, the transmittance was 42.5%, and the contrast was 93, which proved to function as a polarizing film.
(Example 75)
After obtaining the polymerizable liquid crystal composition (75) of the present invention in the same manner as in Example 1, the obtained polymerizable liquid crystal composition (75) was spin-coated on a 0.7 mm-thick glass substrate. After coating at 70 ° C. for 2 minutes, it was further dried at 100 ° C. for 2 minutes, and irradiated with 313 nm linearly polarized light at an intensity of 10 mW / cm ² for 30 seconds. Thereafter, the coating film was returned to room temperature, and was irradiated with ultraviolet light at an intensity of 30 mW / cm ² for 30 seconds using a high-pressure mercury lamp to obtain an optically anisotropic body of Example 73. When the orientation of the obtained optically anisotropic body was evaluated, no defect was found visually and no defect was observed even by observation with a polarizing microscope. Further, the retardation of the obtained optically anisotropic body was measured by RETS-100 (manufactured by Otsuka Electronics Co., Ltd.). A phase difference film was obtained.
(Example 76)
After obtaining the polymerizable liquid crystal composition (76) of the present invention in the same manner as in Example 1, the obtained polymerizable liquid crystal composition (76) was spin-coated on a 0.7 mm-thick glass substrate. After drying at 60 ° C. for 2 minutes, it was further dried at 110 ° C. for 2 minutes, returned to 60 ° C., and irradiated with 313 nm linearly polarized light at an intensity of 10 mW / cm ² for 50 seconds. Thereafter, the coated film was returned to room temperature, and irradiated with ultraviolet rays at an intensity of 30 mW / cm ² for 30 seconds using a high-pressure mercury lamp to obtain an optically anisotropic body of Example 74. When the orientation of the obtained optically anisotropic body was evaluated, no defect was found visually and no defect was observed even by observation with a polarizing microscope. Further, the retardation of the obtained optically anisotropic body was measured by RETS-100 (manufactured by Otsuka Electronics Co., Ltd.). A phase difference film was obtained.

(Example 77)
After obtaining the polymerizable liquid crystal composition (77) of the present invention in the same manner as in Example 1, the obtained polymerizable liquid crystal composition (77) was spin-coated on a 0.7 mm-thick glass substrate. After drying at 60 ° C. for 2 minutes, it was further dried at 110 ° C. for 2 minutes, returned to 60 ° C., and irradiated with 313 nm linearly polarized light at an intensity of 10 mW / cm ² for 100 seconds. Thereafter, the coated film was returned to room temperature, and irradiated with ultraviolet rays at an intensity of 30 mW / cm ² for 30 seconds using a high-pressure mercury lamp to obtain an optically anisotropic body of Example 75. When the orientation of the obtained optically anisotropic body was evaluated, no defect was found visually and no defect was observed even by observation with a polarizing microscope. When the retardation of the obtained optically anisotropic body was measured by RETS-100 (manufactured by Otsuka Electronics Co., Ltd.), the in-plane retardation (Re (550)) at a wavelength of 550 nm was 108 nm, and the uniformity was good. A phase difference film was obtained.
(Example 78)
After obtaining the polymerizable liquid crystal composition (78) of the present invention in the same manner as in Example 1, the obtained polymerizable liquid crystal composition (78) was spin-coated on a 0.7 mm-thick glass substrate. It was then dried at 60 ° C. for 2 minutes, further dried at 90 ° C. for 2 minutes, returned to room temperature, and irradiated with 365-nm linearly polarized light at an intensity of 10 mW / cm ² for 50 seconds. Thereafter, the coated film was returned to room temperature, and was irradiated with ultraviolet light at an intensity of 30 mW / cm ² for 30 seconds using a high-pressure mercury lamp to obtain an optically anisotropic body of Example 76. When the orientation of the obtained optically anisotropic body was evaluated, no defect was found visually and no defect was observed even by observation with a polarizing microscope. When the retardation of the obtained optically anisotropic material was measured by RETS-100 (manufactured by Otsuka Electronics Co., Ltd.), the in-plane retardation (Re (550)) at a wavelength of 550 nm was 135 nm, and the uniformity was good. A phase difference film was obtained.
(Example 79)
After obtaining the polymerizable liquid crystal composition (79) of the present invention in the same manner as in Example 1, a 50 μm-thick uniaxially stretched PET film was subjected to a rubbing treatment using a commercially available rubbing apparatus, and then the polymerizable liquid crystal composition of the present invention was obtained. The liquid crystal composition (79) was applied by a bar coat method, and dried at 80 ° C. for 2 minutes. After the obtained coating film was cooled to room temperature, it was irradiated with ultraviolet light at a conveyor speed of 5 m / min using a UV conveyor device (manufactured by GS Yuasa) having a lamp output of 2 kW (80 W / cm). An optically anisotropic body was obtained.

When the orientation of the obtained optically anisotropic body was evaluated, no defect was found visually and no defect was observed even by observation with a polarizing microscope.
The polymerizable liquid crystal composition (79) remained transparent and uniform after being left at 0 ° C. for one week, and was visually observed immediately after dissolution, using any of the polymerizable liquid crystal compositions after left for one week. No alignment defect was observed, and no alignment defect was observed even by observation with a polarizing microscope.
(Examples 80 to 86)
Polymerizable liquid crystal compositions (80) to (86) of the present invention were obtained in the same manner as in Example 1, and optically anisotropic bodies were obtained in the same manner as in Example 79, and various evaluations were performed.
Each of the polymerizable liquid crystal compositions (80) to (86) maintains a transparent and uniform state even after being left at 0 ° C. for one week, and is left immediately after dissolution for one week. Even when used, an optically anisotropic body having good orientation was obtained.

(Comparative Examples 1 to 23)
Evaluations of Comparative Examples 1 to 23 were performed in the same manner as in Example 1.

  The polymerizable liquid crystal composition of the present invention is an optically anisotropic material, a retardation film, an optical compensation film, an antireflection film, a lens, a lens sheet, a liquid crystal display device using the polymerizable liquid crystal composition, an organic light emitting display device, It is useful in various applications such as lighting elements, optical components, polarizing films, coloring agents, security markings, laser light emitting members, coloring materials, printed materials, structural materials, and restoration materials.

Claims (10)

A polymerizable liquid crystal composition comprising at least one liquid crystal compound having at least one polymerizable group, a polymerization initiator, and at least two solvents, wherein at least one of the two or more solvents is used. one is, there is having a cyclic structure in the molecule, and its boiling point of 170 ° C. or more solvents (a) (hereinafter, abbreviated as "high-boiling solvent (a)".) der is, furthermore, the A solvent (b) having a lower boiling point than the high boiling point solvent (a) and having an acyclic structure, which is selected from propylene glycol monomethyl ether acetate, methyl isobutyl ketone, 1-methoxy-2-propanol, and butyl acetate , Abbreviated as “low-boiling solvent (b)”) . The polymerizable liquid crystal composition,
1) is in a solution state at 25 ° C., and has a solution viscosity of 4 to 500 mPa · s by an E-type viscometer (20 ° C.),
2) In a temperature environment of 0 ° C. or lower, transparency is maintained for 1 week or more, and no precipitate is generated.
The polymerizable liquid crystal composition according to claim 1, wherein The high-boiling solvent (a) is at least one -O -, - CO -, - COO -, - OH, a polymerizable liquid crystal of claim 1 or claim 2 characterized in that it has a -CONR- Composition. The polymerizable liquid crystal composition according to any one of claims 1 to 3 , wherein the weight ratio of the liquid crystal compound and the solvent is 1/99 to 90/10. The high boiling solvent (a) is one or more selected from the group consisting of cyclohexyl acetate, γ-butyrolactone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and 2-pyrrolidone. 5. The polymerizable liquid crystal composition according to any one of items 1 to 4 . As the solvent, in addition to the high-boiling solvent (a) and the low-boiling solvent (b), the solvent further has a boiling point between the boiling point of the high-boiling solvent (a) and the boiling point of the low-boiling solvent (b). The polymerizable liquid crystal composition according to any one of claims 1 to 5 , further comprising a solvent. Further, polymerization inhibitors, polymerization initiators, antioxidants, ultraviolet absorbers and / or light stabilizers, leveling agents, alignment controllers, chain transfer agents, infrared absorbers, antistatic agents, dyes, fillers, chiral compounds, The polymerizable liquid crystal composition according to any one of claims 1 to 6 , comprising at least one selected from the group consisting of a non-liquid crystal compound having a polymerizable group and an alignment material. Polymerizable polymer obtained by curing a non-volatile components of the liquid crystal composition according to any one of claims 1-7. Polymerizable formed by curing the non-volatile components of the liquid crystal composition optically anisotropic medium according to any one of claims 1-7. Display device using the optically anisotropic medium obtained by curing the non-volatile components of the polymerizable liquid crystal composition according to any one of claims 1-7.