WO2019102922A1 - Polymerizable liquid crystal composition, polymer of same, optically anisotropic body, and display element - Google Patents

Abstract

Provided is a polymerizable liquid crystal composition which has good solubility and good storage stability at low temperature, and in which good alignment and minimal unevenness in a polymerized film-shaped polymer are obtained. A polymerizable liquid crystal composition including one or more types of a liquid crystalline compound having at least one polymerizable group, a polymerization initiator, and at least one type of solvent, the polymerizable liquid crystal composition being characterized in that 1) the polymerizable liquid crystal composition is in a solution state at 25°C and the solution viscosity thereof measured by an E-type viscometer (20°C) is in the range of 4-500 mPa∙s, and 2) transparency is maintained for 1 week or more and a precipitate does not form in a 0°C or lower temperature environment.

Description

Polymerizable liquid crystal composition, polymer thereof, optically anisotropic body, and display device

The present invention relates to a polymer having optical anisotropy requiring various optical properties, a polymerizable liquid crystal composition useful as a component of a film, an optical anisotropic material comprising the polymerizable liquid crystal composition, a retardation film, Optical compensation film, antireflective film, lens, lens sheet, liquid crystal display device using the polymerizable liquid crystal composition, organic light emitting display device, illumination device, optical component, polarizing film, coloring agent, marking for security, laser emission The present invention relates to a member, a printed matter, a structural material, a restoration material, an article and the like.

A polymerizable liquid crystal composition having a mesogen skeleton is useful as a component of an optically anisotropic body, and the optically anisotropic body is applied to various display elements as, for example, a retardation film. In the retardation film, a polymerizable liquid crystal composition having a mesogen skeleton is applied to a substrate, and the mesogen skeleton in the polymerizable liquid crystal composition and a liquid crystalline molecule having a polymerizable group are aligned by an alignment film or the like. It is obtained by reacting the liquid crystalline molecules by heating or irradiation with active energy rays in the state as described above.

Usually, the above-mentioned polymerizable liquid crystal composition for coating is used in the form of a solution dissolved in a solvent, and therefore, after being coated on a substrate, a drying process is required to remove the solvent by heating or the like. 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, so it is long over a wider temperature range It needs to be well oriented without defects in time. In addition, when the solution is transported, it is necessary to maintain the solution state for a long time in a wider temperature range because it is left under various environments. In particular, at low temperatures, the liquid crystal molecules are easily deposited, and therefore, a polymerizable liquid crystal composition capable of maintaining a solution state in various environments has been desired.

Therefore, as a technique for improving the solubility of the polymerizable liquid crystal compound in the solvent, there is an example (patent documents 1 and 2) in which the solubility is improved by the structure of the compound, but the structure of the compound is limited. In terms of storage stability at low temperatures, the characteristics were insufficient. In addition, although there is an example (Patent Document 3) in which the solubility is improved by combining the organic solvent having a cyclic ketone structure and the organic solvent having a cyclic ether structure, the storage stability at low temperature is insufficient. Due to the low solution viscosity, even the low viscosity is limited to the coating process that can be applied, and it can not cope with various coating methods, and there is no choice but to limit the application. The Further, as another example in which the solvent solubility of the polymerizable liquid crystal compound is improved, there is known a technique in which a diacetate solvent and a ketone solvent are used in combination as an organic solvent (Patent Document 4). However, although such mixed solvent systems have some improvement effect of solvent solubility and improvement of coatability, they are not yet at a sufficient level, and they are inferior in orientation after storage at low temperature.

JP 2008-127336 A JP, 2013-067603, A JP, 2011-068833, A Patent Document 1: Japanese Patent Application Publication No. 2017-146575

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

In order to solve the above problems, the present invention focused on the temperature at which the polymerizable compound dissolves in the solvent, the storage conditions at a low temperature, and the boiling point and structure of the solvent used, and as a result of repeated studies. The present invention has been provided.
That is, the present invention
A polymerizable liquid crystal composition comprising one or more types of liquid crystal compounds having at least one polymerizable group, a polymerization initiator, and at least one type of solvent,
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,
2) maintain transparency for at least 1 week in a temperature environment of 0 ° C. or less, and do not form precipitates,
The present invention relates to a polymerizable liquid crystal composition characterized by

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

The present invention further relates to an optical anisotropic body obtained by curing the non-volatile component of the polymerizable liquid crystal composition.

The present invention further relates to a display device using the optical anisotropic body.

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

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

Hereinafter, the embodiment of the polymerizable liquid crystal composition according to the present invention will be described. In the present invention, the “liquid crystal compound” is intended to indicate a compound having a mesogenic skeleton, and the compound alone is It does not have to show liquid crystallinity. In addition, it can polymerize (film formation) by performing a polymerization process by light irradiation, such as an ultraviolet-ray, or heating of a polymeric liquid crystal composition.

The polymerizable liquid crystal composition of the present invention, as described above, is a polymerizable liquid crystal composition containing one or more liquid crystal compounds having at least one polymerizable group, a polymerization initiator, and at least one or more solvents. There,
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,
2) maintain transparency for at least 1 week in a temperature environment of 0 ° C. or less, and do not form precipitates,
It is characterized by

Here, the condition that “the polymerizable liquid crystal composition is in the solution state at 25 ° C. and the solution viscosity in the E-type viscometer (20 ° C.) is in the range of 4 to 500 mPa · s” in the above 1) is As a polymerizable liquid crystal composition, it means a region having a relatively high viscosity, which makes the coating property good and, in addition, becomes a composition having a suitably high viscosity, which corresponds to various coating means. can do. Usually, in order to shift the viscosity of the polymerizable liquid crystal composition in the solution state to a higher level, it is necessary to increase the concentration of non-volatile components in the solution. In this case, the compatibility is impaired and it tends to cause precipitation of the liquid crystal compound at low temperatures 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 of 1 week or more is maintained under the temperature environment of 0 ° C. or less And the requirement that precipitates not occur is a requirement for improving solubility, low temperature storage stability, and coating property, and improves the orientation and unevenness when the polymer is produced after long-term low temperature storage It can be done. From such a viewpoint, the solution viscosity of the polymerizable liquid crystal composition at 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 crystal compound having at least one polymerizable group as an essential component.

The liquid crystal compound having at least one polymerizable group of the present invention may be any 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, J. W. Goodby, G. W. Gray, H. W. Spiess, V. Vill, published by Wiley-VCH, 1998), Chemical Journal No. 22. Chemistry of liquid crystals (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, A rigid site called mesogen in which a plurality of structures such as 1,4-phenylene group 1,4-cyclohexene group are connected as described in JP-A-11-116538, JP-A-11-148079, etc. And a rod-like polymerizable liquid crystal compound having two or more polymerizable functional groups such as vinyl group, acrylic group and (meth) acrylic group, or those described in JP-A-2004-2373 or JP-A-2004-99446 And rod-like polymerizable liquid crystal compounds having two or more polymerizable groups having a maleimide group. Among them, a rod-like liquid crystal compound having two or more polymerizable groups is preferable because it is easy to make a liquid crystal temperature range including a low temperature around room temperature.

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

In the above formulae, P ¹¹ to P ⁷⁴ each independently represent a polymerizable group,
Each of S ¹¹ to S ⁷² independently represents a spacer group or a single bond, but when there are a plurality of S ¹¹ to S ^72, they may be the same or different.
X ¹¹ to X ⁷² each independently represent -O-, -S-, -OCH _2- , -CH ₂ O-, -CO-, -COO-, -OCO-, -CO-S-, -S- CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S- , -SCF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO- _{CH 2 CH 2 -, - CH} 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, -CH = CH-, -N = N-, -CH = N-N = CH-, -CF = CF-, -C≡C- or a single bond However, when a plurality of X ¹¹ to X ⁷² are present, they may be the same or different, provided that each P- (S—X) -bond does not contain —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 Although the alkyl group of the number 1 to 20 is represented, the alkyl group may be linear or branched, and any hydrogen atom in the alkyl group 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 -, - It may be substituted by CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C-,
m1 to m7, n2 to n7, l4 to 16 and k6 each independently represent an integer of 0 to 5.

The spacer group represented by the above S ¹¹ to S ⁷² represents an alkylene group having 1 to 18 carbon atoms, and the alkylene group is one or more halogen atoms, CN group, an alkyl group having 1 to 8 carbon atoms, or polymerizable functional group may be substituted by an alkyl group having 1 to 8 carbon atoms having a respective 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)

It 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 part of the alkylene group is —O— A substituted linear or branched alkylene group having 5 to 14 carbon atoms, or a linear or branched alkylene group having 5 to 14 carbon atoms in which a part of the alkylene group is replaced by -COO- or -OCO- preferable.
In addition, the polymerizable groups represented by P ¹¹ to P ⁷⁴ have the following formulas (P-1) to (P-20)

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 Formula (P-13) is preferable, and Formula (P-1), Formula (P-7), and Formula (P-12) are more preferable.

The mesogenic group represented by MG ²¹ to MG ⁷¹ has the following formula (8-a)

(In the formula,
A ⁸¹ and A ⁸² each independently represent 1,4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, 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 a single bond is represented, but when a plurality of Z ⁸¹ and / or Z ⁸² appear, they may be the same or different,
M ⁸¹ is 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrofuran 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, Naphthylene-1,6-diyl, Naphthylene-2,6-diyl, phenanthrene-2,7-diyl, 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 '] diselenophene-2,6-diyl group, [1] benzothieno [3,2-b] thiophene-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, wherein these groups are unsubstituted or substituted by one or more L Well,
L represents 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, a dimethylamino group, a diethylamino group, a diisopropylamino group , Trimethylsilyl group, dimethylsilyl group, thioisocyano group, 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 from 1 carbon atom 20 straight A linear or branched alkyl group is represented, but 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. It is represented by). Or a group represented by formula (8-b)

(In the formula,
A ⁸³ and A ⁸⁴ each independently represent 1,4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, 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 groups 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 a formula (M-813) from the following formula (M-81)

And the group may be unsubstituted or substituted by one or more L,
G is an expression (G-86) from the following expression (G-81)

(Wherein R ³ represents a hydrogen atom, or an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, but the alkyl group and the alkenyl group are linear; And any hydrogen atom in the alkyl group may be substituted with a fluorine atom, and one —CH ₂ — or two or more non-adjacent groups in the alkyl group may be substituted. CH ₂ -is each independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO It may be substituted by -NH-, -NH-CO- or -C≡C-,
W ⁸¹ represents a group having 5 to 30 carbon atoms which has at least one aromatic group, but the group 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, but the alkyl group may be linear or branched, and any hydrogen atom in the alkyl group is It 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 may be substituted 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 at least one aromatic group, and having 5 to 30 carbon atoms Group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms, and 1 to 20 carbon atoms And an alkyloxy group having 2 to 20 carbon atoms and 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 , - - -O each independently 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-,
However, when M is selected from Formula (M-81) to Formula (M-812), G is selected from Formula (G-81) to Formula (G-85), and M is a formula (M-813) G is the formula (G-86),
L represents 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, a dimethylamino group, a diethylamino group, a diisopropylamino group And trimethylsilyl group, dimethylsilyl group, thioisocyano group, or an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be linear or branched, and any hydrogen atom is It 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- or a group selected from -C 置換 C- Well, j 83 and j 84 each independently represent an integer of 0 to 5, but j 83 + j 84 represents an integer of 1 to 5. It is represented by).
Furthermore, the above general formulas (1) to (7) have the following general formula (1-a), general formula (1-b), general formula (2-a), general formula (2-b), Formula (3-a), Formula (3-b), Formula (4-a), Formula (4-b), Formula (5-a), Formula (5-b), Formula It is represented by (6-a), general formula (6-b), general formula (7-a), or general formula (7-b).

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), 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), the polymerizable groups P ¹¹ to P ⁷⁴ are each independently represented by the following formula (P-1) to the formula (P-20)

It is preferable to represent a group selected from the group consisting of formula (P-1), formula (P-2), formula (P-7), and the like from the viewpoint of enhancing the polymerizability and storage stability among these polymerizable groups. Formula (P-12) or Formula (P-13) is preferable, and Formula (P-1), Formula (P-7), and Formula (P-12) are more preferable.
Formula (1-a), Formula (1-b), (2-a), Formula (2-b), Formula (3-a), Formula (3-b), Formula (4) -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, but when there are a plurality of S ¹¹ to S ⁷² , they may be identical or different. It is good. The spacer group represents an alkylene group having 1 to 18 carbon atoms, and the alkylene group has one or more halogen atoms, CN, an alkyl group having 1 to 8 carbon atoms, or a polymerizable functional group. 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 part of the alkylene group is —O— A substituted linear or branched alkylene group having 5 to 14 carbon atoms, or a linear or branched alkylene group having 5 to 14 carbon atoms in which a part of the alkylene group is replaced by -COO- or -OCO- preferable.
Formula (1-a), Formula (1-b), Formula (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) In the general formula (7-b), X ¹¹ to X ⁷² each independently represent -O-, -S-, -OCH _2- , -CH ₂ O-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH _2- , -CH ₂ S-, -CF _{2 O -, - OCF 2 -,} - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH- _{, -COO-CH 2 CH 2 -} , _{OCO-CH 2 CH 2 -,} - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO-, -CH = CH-, -N = N-, -CH = N-N = CH-, -CF = CF-, -C≡C- or a single bond, but X ¹¹ to X ⁷² is When there are a plurality of each, they may be the same or different (however, each P- (S-X) _k -does not contain an -O-O- bond). Also, in view of availability of raw materials and easiness of synthesis, when there are a plurality of each, they may be the same or different, and each independently -O-, -S-, -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-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 is preferred, and each is independently -O- or -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 exist, they may be the same or different, and it is particularly preferable that each independently represent -O-, -COO-, -OCO- or a single bond.
Formula (1-a), Formula (1-b), Formula (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) and in the general formula (7-b), each of A ¹¹ to A ⁷² independently represents 1,4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl, pyrimidine-2 , 5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group 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 in view of availability of raw materials and easiness of synthesis; It is preferable to represent a hexylene group or naphthalene-2,6-diyl, each of which is independently represented by the following formula (A-1) to formula (A-11)

It is more preferable to represent a group selected from, each independently to represent a group selected from Formula (A-1) to Formula (A-8), and each independently to be different from Formula (A-1) It is particularly preferable to represent a group selected from Formula (A-4).
Formula (1-a), Formula (1-b), Formula (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) In the general formula (7-b), each of Z ¹¹ to Z ⁷² independently represents —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 a single bond, but a plurality of Z ¹¹ to Z ⁷² appear The cases may be the same or different. Z ¹¹ to Z ⁷² each independently represent a single bond, -OCH _2- , -CH ₂ O-, -COO-, or -OCO- from the viewpoint of liquid crystallinity of the compound, availability of raw materials, and ease of synthesis. _{, -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 a single bond is preferred, and each of Z ¹¹ to Z ⁷² is 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 ^~ Z ⁷² are 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 It is further preferable to represent-or a single bond, and it is particularly preferable to represent each independently -CH ₂ CH _2- , -COO-, -OCO- or a single bond.
In the general formula (1-a), the general formula (1-b) and the general formula (3-a) and the general formula (3-b), 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 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- And a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by —NH—CO— or —C≡C—, but any hydrogen atom in the alkyl group is 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- or -O-CO-O-; More preferably, it represents an atom, a chlorine atom, a cyano group, or a linear alkyl group or linear alkoxy group having 1 to 12 carbon atoms, and a linear alkyl group or linear alkoxy group having 1 to 12 carbon atoms It is particularly preferred to represent.
Formula (1-b), Formula (2-b), Formula (3-b), Formula (4-b), Formula (5-b), Formula (6-b), Formula In (7-b), M is a formula (M-813) from the following formula (M-81)

And the groups may be unsubstituted or substituted by one or more L. M is each independently unsubstituted or substituted with one or more L's, in view of availability of raw materials and easiness of synthesis; formula (M-81) or formula (M-82) or It is preferable to represent a group selected from unsubstituted formula (M-83) to formula (M-86), which may be unsubstituted or substituted by one or more L. Formula (M-81) or formula (M) It is more preferable to represent a group selected from -82), and it is particularly preferable to represent a group selected from unsubstituted formula (M-81) or formula (M-82).
Formula (1-b), Formula (2-b), Formula (3-b), Formula (4-b), Formula (5-b), Formula (6-b), Formula In (7-b), G represents a group selected from Formula (G-81) to Formula (G-86).

In the formula, R ³ represents a hydrogen atom, or one —CH ₂ — or two or more non-adjacent —CH ₂ —s each independently represent —O—, —S—, —CO— or —COO -, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C-, optionally substituted carbon It 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, but any hydrogen atom in the alkyl group or alkenyl group is fluorine It may be substituted by an atom,
W ⁸¹ represents a group having 5 to 30 carbon atoms which has at least one aromatic group, and 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-, and -C1-C20 linear or it 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 , any hydrogen atom may be substituted with a fluorine atom from the viewpoint of liquid crystallinity and easiness of synthesis, and one —CH ₂ — or _two non-adjacent two or more —CH ₂ — may each be A linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted independently by -O-, -COO- or -OCO-, or a linear or branched alkyl group having 2 to 16 carbon atoms It is preferable to represent an alkenyl group, and any hydrogen atom may be substituted with a fluorine atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a linear or branched chain having 2 to 16 carbon atoms It is more preferable to represent a cyclic alkenyl group, and a linear alkyl group having 1 to 12 carbon atoms, one -CH ₂ -or _two non-adjacent 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 at least one aromatic group, and having 5 to 30 carbon atoms Group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms, and 1 to 20 carbon atoms And an alkyloxy group having 2 to 20 carbon atoms and 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 , - - -O each independently 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 bonded via a single bond or a linking group (-OCO-, -COO-, -CO-, -O-) or may form a fused ring. In addition to the aromatic group, W ⁸¹ may contain an acyclic structure and / or a cyclic structure other than the aromatic group. The aromatic group contained in W ⁸¹ may be unsubstituted or may be substituted by one or more L from the following formula (W-1) from the viewpoint of the availability of raw materials and the ease of synthesis: (W-19)

(Wherein, these groups may have a bond at any position, and may form a group in which two or more aromatic groups selected from these groups are linked by 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-, among these aromatic groups. -CH = may be replaced each independently -N =, -CH ₂ - are each independently -O -, - S -, - NR 4 - ( wherein, ^{R 4} is hydrogen or C A group represented by an alkyl group having 1 to 8 atoms)) or -CO- which may be replaced, but which does not contain an -O-O- bond is preferable. As the group represented by the formula (W-1), a group represented by the following formula (W-1-1) which may be unsubstituted or substituted by one or more L ² may be represented by the formula (W-1-8) )

(In the formula, these groups may have a bond at any position.) It is preferable to represent a group selected from, and as the group represented by the formula (W-7), it is unsubstituted Formula (W-7-1) to Formula (W-7-7) below 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 to represent a group selected from, and as the group represented by formula (W-10), it is unsubstituted Formula (W-10-8) from Formula (W-10-1) below which may be substituted by one or more L ²

(Wherein, these groups may have a bond at any position, and R ⁶ preferably represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms). As a group represented by Formula (W-11), Formula (W-11-13) may be unsubstituted or substituted by one or more L ^{2 as represented} by the following Formula (W-11-1) )

(Wherein, these groups may have a bond at any position, and R ⁶ preferably represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms). As a group represented by Formula (W-12), Formula (W-12-19) may be unsubstituted or may be substituted by one or more L from the following Formula (W-12-1)

(In the formula, these groups may have a bond at an arbitrary position, and 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 are respectively identical And the group represented by the formula (W-13) is preferably either unsubstituted or substituted by one or more L. The following formula (W-13-1) is also good from formula (W-13-10)

(In the formula, these groups may have a bond at an arbitrary position, and 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 are respectively identical And the group represented by formula (W-14) is preferably unsubstituted or substituted by one or more L ² groups. From the following formula (W-14-1) may be from formula (W-14-4)

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

(In the formula, these groups may have a bond at an arbitrary position, and 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 are respectively identical And the group represented by the formula (W-16) is preferably either unsubstituted or substituted by one or more L. From the following formula (W-16-1) also good formula (W-16-4)

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

(Wherein, these groups may have a bond at any position, and R ⁶ preferably represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms). As a group represented by Formula (W-18), Formula (W-18-6) from Formula (W-18-1) below 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, and 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 are respectively identical And the group represented by formula (W-19) is preferably unsubstituted or substituted by one or more L. Formula (W-19-9) from the following formula (W-19-1) which is also good

(In the formula, these groups may have a bond at an arbitrary position, and 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 are respectively identical Or a group selected from the group consisting of The aromatic group contained in W ⁸¹ may be unsubstituted or may be substituted by one or more L's (W-1-1), (W-7-1), (W-7) -2), formula (W-7-7), formula (W-8), formula (W-10-6), formula (W-10-7), formula (W-10-8), formula (W -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) which may be unsubstituted or substituted by one or more L, formula (W-7-1), formula (W-) 7-2) It is particularly preferable to represent a group selected from Formula (W-7-7), Formula (W-10-6), Formula (W-10-7) or Formula (W-10-8) . Furthermore, W ⁸¹ is a formula (Wa-6) from the following formula (Wa-1)

It is particularly preferred to represent a group selected from (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-, and -C1-C20 linear or it 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 view of the availability of raw materials and easiness of synthesis, W ⁸² may be substituted with a hydrogen atom or any hydrogen atom, and one —CH ₂ — or _two non-adjacent ones may be substituted Each of the above -CH ₂ -is 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 好 ま し く C—, and is preferably a hydrogen atom or 1 to 20 carbon atoms. It is more preferable to represent a linear or branched alkyl group, and it is particularly preferable to represent 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.} Also, 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 L as described below Formula (W-b-1) to formula (W-b-42)

(Wherein, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms) is preferably a group selected from the group consisting of unsubstituted or from the viewpoint of availability of raw materials and easiness of synthesis Formula (W-b-20), Formula (W-b-21), Formula (W-b-22), Formula (W-b-23), Formula (W) which may be substituted by one or more L It is particularly preferable to represent a group selected from -b-24), formula (W-b-25) or formula (W-b-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 a formula (W-c-81)

(Wherein, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, but when a plurality of R ⁶ are present, they may be the same or different). Preferably, in view of the availability of raw materials and easiness of synthesis, formula (W-c-11), formula (W-c-12), which may be unsubstituted or substituted by one or more L. Formula (W-c-13), Formula (W-c-14), Formula (W-c-53), Formula (W-c-54), Formula (W-c-55), Formula (W-c) It is particularly preferable to represent a group selected from formula (W-c-57) or formula (W-c-78).
The total number of π electrons contained in W ⁸¹ and W ⁸² is preferably 4 to 24 from the viewpoint of wavelength dispersion characteristics, storage stability, liquid crystallinity and easiness 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 at least one aromatic group, and having 5 to 30 carbon atoms Group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms, and 1 to 20 carbon atoms And an alkyloxy group having 2 to 20 carbon atoms and 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 , - - -O each independently 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-, and W ⁸³ is a cyano group, a nitro group, a carboxyl group, 1 -CH ₂ -or ₂ non-adjacent ones Each of the above -CH ₂ -is independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O- , A group selected from an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an acyloxy group and an alkylcarbonyloxy group, which is 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-, Particularly preferred is a group selected from an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an acyloxy group and an alkylcarbonyloxy group, and W ⁸⁴ is a cyano group, a nitro group, a carboxyl group, one -CH ₂ -or adjacent Two or more -CH _2- which are not each independently represent -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O. It is 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- More preferably, a cyano group, a A ruboxyl group, one -CH ₂ -or two or more non-adjacent -CH ₂ -are each independently -CO-, -COO-, -OCO-, -O-CO-O-, -CO A group selected by a group selected from alkyl group having 1 to 20 carbon atoms, alkenyl group, acyloxy group and alkylcarbonyloxy group, which is substituted by -NH-, -NH-CO- or -C≡C- Is particularly preferred.
L represents 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, a dimethylamino group, a diethylamino group, a diisopropylamino group , Trimethylsilyl group, dimethylsilyl group, thioisocyano group, 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 from 1 carbon atom 20 straight Although a chained or branched alkyl group is represented, any hydrogen atom in the alkyl group may be substituted by a fluorine atom. From the viewpoint of liquid crystallinity and easiness 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 The atom may be substituted by a fluorine atom, and one -CH ₂ -or two or more non-adjacent -CH ₂ -are each independently -O-, -S-, -CO-, -COO -1-20 carbon atoms optionally substituted by a group selected from-, -OCO-, -O-CO-O-, -CH = CH-, -CF = CF- or -C≡C- It is preferable to represent a chain or branched alkyl group or a group represented by the above formula (1-c), and a fluorine atom, a chlorine atom, or any hydrogen atom may be substituted by a fluorine atom, 1 -CH ₂ -or not adjacent Two or more -CH ₂ -are each independently substituted by a group selected from -O-, -COO- or -OCO-, and a linear or branched alkyl having 1 to 12 carbon atoms It is more preferable to represent a group, and a fluorine atom, a chlorine atom, or an arbitrary hydrogen atom represents a linear or branched alkyl group having 1 to 12 carbon atoms or an alkoxy group which may be substituted by a fluorine atom. Are more preferable, and it is particularly preferable to represent a fluorine atom, a chlorine atom, or a linear alkyl group or a linear alkoxy group having 1 to 8 carbon atoms.
Formula (1-b), Formula (2-b), Formula (3-b), Formula (4-b), Formula (5-b), Formula (6-b), 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 or a methylamino group , Dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, 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-OC -O-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C-, optionally substituted by 1 to 20 carbon atoms It is more preferable to represent a linear or branched alkyl group.
Formula (1-a), Formula (2-a), Formula (3-a), Formula (4-a), Formula (5-a), Formula (6-a), Formula In (7-a), M ¹¹ to M ^{71 each} represent a 1,4-phenylene group, a 1,4-cyclohexylene group, a 1,4-cyclohexenyl group, a tetrahydropyran-2,5-diyl group, a 1,3- Dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine-2, 5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group , 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 '] Diselenophene-2, 6-diyl group, [1] benzothieno [3, 2-b] thiophene-2, 7-diyl group, [1] benzoselenopheno [3, 2- b] selenophen-2 , 7-diyl group, or a group selected from fluorene-2,7-diyl group, and these groups may be unsubstituted or substituted by one or more L, and M ¹¹ to M ⁷¹ are raw materials From the viewpoint of availability and easiness of synthesis 1,4-phenylene, 1,4-cyclohexylene, naphthylene-1,4-diyl, or naphthylene-2, each of which may be each independently unsubstituted or substituted with one or more L. A 6-diyl group is preferable, and more preferably represents a group selected from a 1,4-phenylene group which may be unsubstituted or substituted by one or more L and a 1,4-cyclohexylene group.
L represents 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, a dimethylamino group, a diethylamino group, a diisopropylamino group , Trimethylsilyl group, dimethylsilyl group, thioisocyano group, 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 from 1 carbon atom 20 straight Although a chained or branched alkyl group is represented, any hydrogen atom in the alkyl group may be substituted by a fluorine atom. From the viewpoint of liquid crystallinity and easiness 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 The atom may be substituted by a fluorine atom, and one -CH ₂ -or two or more non-adjacent -CH ₂ -are each independently -O-, -S-, -CO-, -COO -1-20 carbon atoms optionally substituted by a group selected from-, -OCO-, -O-CO-O-, -CH = CH-, -CF = CF- or -C≡C- It preferably represents a chain or branched alkyl group, and a fluorine atom, a chlorine atom, or any hydrogen atom may be substituted by a fluorine atom, and one or more -CH ₂ -or not adjacent to each other They are each independently - -CH ₂ of More preferably, it 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 a fluorine atom, a chlorine atom, or And any hydrogen atom is more preferably a linear or branched alkyl group having 1 to 12 carbon atoms or an alkoxy group which may be substituted with a fluorine atom, and the fluorine atom, the chlorine atom or the number of carbon atoms It is particularly preferred to represent 1 to 8 linear alkyl groups or linear alkoxy groups.
Formula (1-a), Formula (1-b), Formula (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), m1 to m7, n2, n4 to n7, l4, l6 and k6 each independently represent an integer of 0 to 5, but liquid crystallinity and easy availability of raw materials In terms of size and easiness of synthesis, it is preferable to represent an integer of 0 to 4, more preferably represent an integer of 0 to 2, and further preferably to represent 0 or 1.
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 of 1 to 5, j21 + j22 represents an integer of 1 to 5, j31 + j32 represents an integer of 1 to 5, j41 + j42 represents an integer of 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. J11, j12, j21, j22, j31, j32, j41, j42, j51, j52, j61, j62, j71 and j72 are each independently 1 to 4 from the viewpoint of liquid crystallinity, easiness of synthesis and storage stability It is preferable to represent an integer of 1, more preferably 1 to 3, and most preferably 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 a compound represented by the said General formula (1-a), the compound represented by a following formula (1-a-1) to a formula (1-a-39) is preferable.

In the above formulas, m11 and n11 each independently represent an integer of 1 to 10, and R ¹¹¹ and R ¹¹² each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a fluorine atom. R ¹¹³ represents 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 one —CH ₂ — or adjacent Two or more -CH ₂ -are each independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -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—, but the alkyl group Any hydrogen atom in the group is substituted by a fluorine atom It may be done.
Specifically as a compound represented by General formula (1-b), the compound represented by a following formula (1-b-1) to a formula (1-b-26) is preferable.

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

(Wherein, 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, all of them may be unsubstituted or substituted by one or more halogen atoms. These liquid crystal compounds may be used alone or in combination of two or more.
Specifically as a compound represented by General formula (2-b), the compound represented by following formula (2-b-1) to formula (2-b-23) is preferable.

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

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

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

(Wherein, 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, all of them may be unsubstituted or substituted by one or more halogen atoms. These liquid crystalline compounds may be used alone or in combination of two or more.
Specifically as a compound represented by General formula (4-b), the compound represented by following formula (4-b-1) to formula (4-b-6) is preferable.

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

Specifically as a compound represented by the said General formula (5-a), the compound represented by following formula (5-a-1) to formula (5-a-26) is preferable.

(Wherein each 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. When the 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 with one or more halogen atoms. These liquid crystal compounds can be used alone or in combination of two or more.
Specifically as a compound represented by General formula (5-b), the compound represented by following formula (5-b-1) to formula (5-b-7) is 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 a compound represented by the said General formula (6-a), the compound represented by a following formula (6-a-1) to a formula (6-a-23) is preferable.

(Wherein k, l, 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, When the group is an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, all of the groups are unsubstituted or substituted by one or more halogen atoms. These liquid crystal compounds may be used alone or in combination of two or more.
Specifically as a compound represented by General formula (6-b), the compound represented by following formula (6-b-1) to formula (6-b-7) is preferable.

(Wherein, k, l, m and n each independently represent 1 to 10 carbon atoms.) These liquid crystal compounds can be used alone or in combination of two or more. It can also be done.
Specifically as a compound represented by the said General formula (7-a), the compound represented by a following formula (7-a-1) to a formula (7-a-25) is 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, or carbon In the case of the alkoxy group of the number 1 to 6, all may be unsubstituted or may be 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 can be represented by the following formula (7-b-1) to the formula (7-b-6) The compounds represented by) are preferred.

[B] Solvent The solvent which can be used for the polymerizable liquid crystal composition of the present invention has the following conditions 1) and 2):
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,
2) maintain transparency for at least 1 week in a temperature environment of 0 ° C. or less, and do not form precipitates,
In particular, in order to satisfy the condition 1), it is preferable that the liquid crystal compound [A] can be dissolved at a temperature of 70 ° C. or less.

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)”). Specifically, it is preferred to contain at least one group consisting of -O-, -CO-, -COO-, -OH, -CONR-. For example, aromatic hydrocarbons such as, ester solvents such as cyclohexyl acetate, γ-butyrolactone, methyl benzoate and ethyl carbonate, ether solvents such as methoxytoluene and veratrole, ketone solvents such as isophorone and acetophenone, N-methyl- Amide solvents such as 2-pyrrolidone, 2-pyrrolidone and the like can be mentioned. The high-boiling point solvent (a) can dissolve the liquid crystalline compound [A] at a temperature of 70 ° C. or less, and the dissolved accessory matter changes by 1 week or more at 0 ° C. or less after dissolution. If it does not exist, it may be used alone, but two or more of the solvents may be used.

Further, 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 point solvent (a) in addition to the high boiling point solvent (a). There is no particular limitation as to and it is particularly preferable to have at least one group consisting of -O-, -CO-, -COO-, -OH, -CONR-, -CN. The solvent may have a cyclic structure or a non-cyclic structure, but from the viewpoint of orientation, one having a non-cyclic structure (hereinafter, the boiling point is lower than that of the high boiling point solvent (a), And the solvent of a non-cyclic structure is abbreviated as "low boiling point solvent (b)".

As such a low boiling point solvent (b), for example, aromatic hydrocarbons such as toluene, xylene, cumene, mesitylene etc., methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 3-butoxymethyl acetate, ethyl lactate Ester solvents such as methyl ethyl ketone, methyl isobutyl ketone, ketone solvents such as acetonyl acetone, 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 from the point of solution stability to use any one or more of these ketone solvents, ether solvents, ester solvents and aromatic hydrocarbon solvents.
Such a low boiling point solvent (b) may be one having a boiling point lower than that of the high boiling point solvent (a) used in combination, but it is more preferable to be less than 170 ° C.
The weight ratio of the solvent having a boiling point of 170 ° C. or more to the solvent having a boiling point lower than that of the solvent is not particularly limited as long as it does not impair the storage property or coating property of the polymerizable liquid crystal composition of the present invention at low temperatures. It 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 coated liquid state is not significantly impaired since the polymerizable liquid crystal composition used in the present invention is usually applied by coating. The mass ratio of the liquid crystal compound [A] having at least one polymerizable group to the solvent [B] is preferably 1/99 to 99/1, and more preferably 10/90 to 80/20. And 20/80 to 70/30 are particularly preferable. Further, when the solid content concentration of the finally obtained polymerizable liquid crystal composition is 10 to 80% by mass, particularly 20 to 70% by mass, the coating property and the storage stability at low temperature are good, and It is preferable from the viewpoint that the unevenness in the film-like polymer after polymerization is small and the orientation is excellent.

Moreover, when dissolving the said polymerizable liquid crystalline compound in an organic solvent, in order to dissolve uniformly, it is preferable to carry out heating stirring. 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 the organic solvent, but from the viewpoint of productivity, 15 ° C. to 70 ° C. is preferable, and 30 ° C. to 65 ° C. 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 required. The polymerization initiator used in the polymerizable liquid crystal composition of the present invention is used to polymerize the polymerizable liquid crystal composition of the present invention. The photopolymerization initiator used when the polymerization is carried out by light irradiation is not particularly limited, but it is a polymerizable compound having one polymerizable group and satisfying the formula (I), at least two or more of them Any known and conventional ones can be used to the extent that they do not inhibit the alignment state of the polymerizable liquid crystal compound having a polymerizable group.

For example, 1-hydroxycyclohexyl phenyl ketone "Omnirad 184", 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one "Omnirad 1173", 2-methyl-1-[(methylthio) phenyl] -2-Molyholinopropane-1 "Omnirad 907", 2,2-Dimethoxy-1,2-diphenylethane-1-one "Omnirad BDK", 2-benzyl-2-dimethylamino-1- (4-morpho) Linophenyl) -butanone "Omnirad 369"), 2-Dimethylamino-2- (4-methylbenzyl) -1- (4-morpholino-phenyl) butan-1-one "Omnirad 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 Co., Ltd.), 1,2-octanedione, 1- [4- (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” (BASF Corporation), “ADEKA ARKRULES NCI-831”, “ADEKA ARKLES NCI-930”, “ADEKA ARKLES N-1919” (ADEKA, Inc.) 2,4-diethylthioxanthone (Nippon Kayaku Co., Ltd.) A mixture of “Kayacure DETX”) and ethyl p-dimethylaminobenzoate (“Kayacure EPA” manufactured by Nippon Kayaku Co., Ltd.), isopropylthioxanthone (“Kantacure-ITX” manufactured by Ward Prequinsop) and ethyl p-dimethylaminobenzoate Mixture with “Esacure ONE”, “Esacure KIP150”, “Esacure KIP160”, “Esacure 1001M”, “Esacure A198”, “Esacure KIP IT”, “Esacure KTO 46”, “Esacure TZT” (manufactured by lamberti, Inc.) And “Speed Cure BMS”, “Speed Cure PBZ”, and “benzophenone” (manufactured by LAMBSON). Furthermore, a photoacid generator can be used as a 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 0.1 to 10% by mass, particularly preferably 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.

Further, as a thermal polymerization initiator used in thermal polymerization, known and commonly used ones can be used. 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, 1,1-bis (t-butylperoxy) cyclohexane, 2, 2'-azobisisobutyronitrile, Azonitrile compounds such as 2,2'-azobis (2,4-dimethylvaleronitrile); azoamidines 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}, alkyl azo such as 2,2'azobis (2,4,4-trimethylpentane) Compounds etc. can be used. The content of the thermal polymerization initiator is preferably 0.1 to 10% by mass, particularly preferably 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, if necessary. The polymerization inhibitor to be used is not particularly limited, and known ones can be used.

For example, p-methoxyphenol, cresol, t-butyl catechol, 3.5-di-t-butyl-4-hydroxytoluene, 2.2'-methylenebis (4-methyl-6-t-butylphenol), 2.2 '-Methylenebis (4-ethyl-6-tert-butylphenol), 4.4'-thiobis (3-methyl-6-tert-butylphenol), 4-methoxy-1-naphthol, 4,4'-dialkoxy-2 , 2'-bi-1-naphthol, etc. phenolic compounds, hydroquinone, methylhydroquinone, tert-butylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, tert-butyl-p-benzoquinone, 2,5-diphenylbenzoquinone , 2-hydroxy-1,4-naphthoquinone, 1,4-naphthoquinone, 2,3-dichloro-1, - 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, N.I. Amine compounds such as N'-di-2-naphthyl-p-phenylenediamine, diphenylamine, N-phenyl-β-naphthylamine, 4.4'-dicumyl-diphenylamine, 4.4'-dioctyl-diphenylamine etc., phenothiazine, Thioether compounds such as distearylthiodipropionate, N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, N-nitrosodinaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol Etc., N, N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrone dimethylamine, 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-butyl nitrone benzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane N-nitroso-N-n-propylurethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, sodium 1-nitroso-2-naphthol-3,6-sulfonate, 2-nitroso-1- Sodium naphthol-4-sulfonate, 2-nitroso-5-methylamide Phenol hydrochloride, 2-nitroso-5-methyl-aminophenol hydrochloride, nitroso-based compounds 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, if necessary. Such compounds include hydroquinone derivatives, nitrosamine type polymerization inhibitors, hindered phenol type antioxidants, etc. More specifically, tert-butyl hydroquinone, "Q-1300" manufactured by Wako Pure Chemical Industries, Ltd., “Q-1301”, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate “IRGANOX1010”, thiodiethylene bis [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 "IRGANOX 1520L", "IRGANOX 1726", "IRGANOX 245", "IRGANOX 259", "IRGANOX 3114", "IRGANOX 3790", "IRGANOX 5057", "IRGANOX 565" (all, made by BASF Corporation), made by Adeka Ltd Adekastab AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, Sumitomo Chemical Co., Ltd.'s Sumylizer BHT, Sumilizer BBM-S, Sumilizer GA-80, and the like.

The addition amount of the antioxidant is 0.01 to 2.0% by mass with respect to the total amount of the liquid crystal-forming compound having at least one polymerizable group used in the polymerizable liquid crystal composition of the present invention. Is preferable, and 0.05 to 1.0% by mass is more preferable.
[F] Ultraviolet Absorbent and / or Light Stabilizer The polymerizable liquid crystal composition of the present invention may contain an ultraviolet absorbent and a light stabilizer, as required. The ultraviolet absorber and the light stabilizer to be used are not particularly limited, but those capable of improving the light resistance such as an optical anisotropic body or an optical film are preferable.

Examples of the UV 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", TINUVIN 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 "(above, made by BASF Corporation)," Adekastab LA-32 "," Adekastab LA-34 "," Adekastab LA-36 "," Adekastab LA-31 ", Examples thereof include "Adekastub 1413" and "Adekastab LA-51" (all manufactured by ADEKA Corporation).

As the light stabilizer, for example, "TINUVIN 111FDL", "TINUVIN 123", "TINUVIN 144", "TINUVIN 152", "TINUVIN 292", "TINUVIN 622", "TINUVIN 770", "TINUVIN 765", "TINUVIN 780" “TINUVIN 905”, “TINUVIN 5100”, “TINUVIN 5050”, “TINUVIN 5060”, “TINUVIN 5151”, “CHIMASSORB 119FL”, “CHIMASSORB 944FL”, “CHIMASSORB 944LD” (all manufactured by BASF Corporation), "Adekastab LA-52", "Adekastab LA-57", "Adekastab LA-62", "Adekastab 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 with respect to the total amount of the liquid crystal-forming compound having at least one polymerizable group used in the polymerizable liquid crystal composition of the present invention Is preferable, and 0.05 to 1.0% by mass is more preferable.
[G] Leveling Agent The polymerizable liquid crystal composition of the present invention can optionally contain a leveling agent. The leveling agent to be used is not particularly limited, but in the case of forming a thin film such as an optical anisotropic film or an optical film, one is preferable in order to reduce film thickness unevenness. 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, “Megafuck F-251”, “Megafuck F-281”, “Megafuck F-430”, “Megafuck F-444”, “Megafuck F-472SF”, “Megafuck F- 477 "," Megafuck F-510 "," Megafuck F-552 "," Megafuck F-553 "," Megafuck F-554 "," Megafuck F-555 "," Megafuck F-556 ""MegafuckF-557","MegafuckF-558","MegafuckF-559","MegafuckF-560","MegafuckF-561","MegafuckF-562"," Megafuck F-563, Megafuck F-565, Megafuck F-568, Megafuck F-569, Megafuck F-570, Mega "Ak R-40", "Megafuck R-41", "Megafuck R-94", "Megafuck RS-72-K", "Megafuck RS-75", "Megafuck RS-76-E", "Megafuck RS-76-NS", "Megafuck RS-90", "Megafuck DS-21" (above, made by DIC Corporation),
"Watergent 100", "Watergent 100C", "Watergent 150", "Watergent 150CH", "Watergent 300", "Watergent 400 SW", "Watering 251", "Watering 215M", "Futtering" GENT 212 M, FUTURE GENT 250, FUTURE GENT 212 D, FTX-218, FUTURE GENT 209 F, FUTURE GENT 245 F, FUTURE GENT 208 G, FUTURE GENT 212 P, FUTAR GENT 220 P , "Futagent 228P", "Futagent 601 AD", "Futagent 602A", "Futagent 650A", "Futagent 750FM", "FTX-730FM", "Futagent 730FL", "Futter GENT 710 FS, H-TERgent 710 FM, H-TER-gent 710 FL, H-TER-gent 750 LL, FTX- 730 LS, H-TER-gent 730 LM (all from Neos Corporation),
"BYK-300", "BYK-302", "BYK-306", "BYK-307", "BYK-310", "BYK-315", "BYK-320", "BYK-322", "BYK -323 "," BYK-325 "," BYK-330 "," BYK-331 "," BYK-333 "," BYK-337 "," BYK-340 "," BYK-344 "," BYK-370 " “BYK-375”, “BYK-377”, “BYK-350”, “BYK-352”, “BYK-354”, “BYK-355”, “BYK-356”, “BYK-358N”, "BYK-361N", "BYK-357", "BYK-390", "BYK-392", "BYK-UV3500", "BYK-UV3510", "BYK-UV3570", "B K-Silclean3700 "(manufactured by BYK Co., Ltd.),
"TEGO Rad2100", "TEGO Rad2200N", "TEGO Rad2250", "TEGO Rad2300", "TEGO Rad2500", "TEGO Rad2700", "TEGO Flow300", "TEGO Flow370", "TEGO Flow425", "TEGO Flow ATF2" , "TEGO Flow ZFS 460", "TEGO Glide 100", "TEGO Glide 410", "TEGO Glide 415", "TEGO Glide 432", "TEGO Glide 440", "TEGO Glide 450", "TEGO Glide 482", "TEGO Glide 482" B1484 "," TEGO Glide ZG400 "," TEGO Twin 42 " 0 "," TEGO Wet KL245 "," TEGO Wet260 "," TEGO Wet270 "," TEGO Wet500 ", (manufactured by Evonik Industries Co., Ltd.),
"FC-4430", "FC-4432" (above, 3M Japan Co., Ltd. made),
"Unidyne NS" (above, made 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" , AGC Seimi Chemical Co., Ltd.),
“Disperon 1970”, “Disperon 230”, “Disperon LF-1980”, “Disperon LF-1982”, “Disperon LF-1983”, “Disperon LF-1084”, “Disperon LF-1985”, “Disperon LHP-90 "," Disperon LHP-91 "," Disperon LHP-95 "," Disperon LHP-96 "," Disperon OX-715 "," Disperon 1930N "," Disperon 1933 "," Disperon 1934 "," Disperon 1711EF ", “Disperon 1751 N”, “Disperon 1761”, “Disperon LS-009”, “Disperon LS-001”, (manufactured by Kushimoto Chemical Co., Ltd.),
“PF-151N”, “PF-636”, “PF-6320”, “PF-656”, “PF-6520”, “PF-652-NF”, “PF-3320” (all available from OMNOVA SOLUTIONS, Inc.) ),
"Polyflow No. 7", "Polyflow No. 50E", "Polyflow No. 50EHF", "Polyflow No. 54N", "Polyflow No. 75", "Polyflow No. 77", "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,” (all manufactured by Kyoeisha Chemical Co., Ltd.),
“L-7001”, “L-7002”, “8032 ADDITIVE”, “57 ADDTIVE”, “L-7064”, “FZ-2110”, “FZ-2105”, “67 ADDTIVE”, “8616 ADD TIVE” 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.) )
Examples of such can be given.

The amount of the leveling agent added is 0.01 to the total amount of the liquid crystal compound having at least one polymerizable group, which is used in the polymerizable liquid crystal composition of the present invention, which is used in the polymerizable liquid crystal composition of the present invention. The content is preferably 2.0% by mass, and 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 body by using the above-mentioned leveling agent, there are some which can effectively reduce the tilt angle of the air interface.
[H] Alignment Control Agent The polymerizable liquid crystal composition of the present invention can contain an alignment control agent in order to control the alignment state of the liquid crystal compound. Examples of the orientation control agent to be used include those in which the liquid crystal compound is substantially horizontally aligned, substantially vertically aligned, and substantially hybrid aligned with the substrate. Moreover, when a chiral compound is added, what carries out plane orientation substantially is mentioned. As described above, the surfactant may induce horizontal orientation and planar orientation in some cases, but there is no particular limitation as long as each orientation state is induced, and commonly known ones may be used. Can.
As such an orientation control 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 the tilt angle of the air interface in the case of forming an optically anisotropic material. The compound which is 100 or more and 1,000,000 or less is mentioned.

(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 It may be substituted by the above halogen atoms.)
Further, rod-like liquid crystalline compounds modified with a fluoroalkyl group, discotic liquid crystalline compounds, polymerizable compounds containing long chain aliphatic alkyl groups which may have a branched structure, and the like can also be mentioned.

Cellulose nitrate, cellulose acetate, cellulose propionate, cellulose butyrate, and rod-shaped liquid crystal modified with heteroaromatic ring salt as an agent having the effect of effectively increasing the tilt angle of the air interface in the case of being optically anisotropic. Examples thereof include compounds, rod-like liquid crystalline compounds modified with cyano group and cyanoalkyl group, and the like.
[I] Chain Transfer Agent The polymerizable liquid crystal composition of the present invention can contain a chain transfer agent in order to further improve the adhesion between the polymer or the optically anisotropic member and the substrate. As chain transfer agents, aromatic hydrocarbons, chloroform, halogenated carbons such as carbon tetrachloride, carbon tetrabromide, bromotrichloromethane and the like,
Mercaptan compounds such as octyl mercaptan, n-butyl mercaptan, n-pentyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mell, 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 tetrakil 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, 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, and the alkyl group may be linear or branched, and at least one methylene group in the alkyl group is an oxygen atom And the sulfur atom may be substituted with an oxygen atom, a sulfur atom, -CO-, -OCO-, -COO-, or -CH = CH-, as R ⁹⁶ is not a carbon atom, and R ⁹⁶ is a carbon atom And represents one or more methylene groups in the alkylene group as an oxygen atom and a sulfur atom which is not directly bonded to each other, such as an oxygen atom, a sulfur atom, -CO- or -OCO-. , -COO-, or -CH = CH- may be substituted.

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

Furthermore, in order to adjust physical properties, it is also possible to add a liquid crystal compound or the like which is not polymerizable, as required. The polymerizable compound having no liquid crystallinity is preferably added in the step of preparing the polymerizable solution by mixing the polymerizable compound in an organic solvent and heating and stirring, but the liquid crystal compound etc. which is not polymerizable is then polymerized The solution may be added in the step of mixing the polymerization initiator, or may be added in both steps. The amount of these compounds added 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. Preferably, 5% by mass or less is even more preferable.
[J] Infrared Absorber The polymerizable liquid crystal composition of the present invention may contain an infrared absorber, if necessary. The infrared absorber to be used is not particularly limited, and may be a known conventional one as long as the orientation is not disturbed.

Examples of the infrared absorber include cyanine compounds, phthalocyanine compounds, naphthoquinone compounds, dithiol compounds, diimmonium compounds, azo compounds, aluminum salts and the like.

Specifically, the diimmonium salt type “NIR-IM1”, the aluminum salt type “NIR-AM1” (above, manufactured by Nagase Chemtech Inc.), the “Kurens IR-T”, the “Kalens IR-13F” (the above , Showa Denko Co., Ltd.), “YKR-2200”, “YKR-2100” (above, Yamamoto Chemical Co., Ltd.), “IRA 908”, “IRA 931”, “IRA 955”, “IRA 1034” (above, INDECO Co., Ltd.) Etc.).
[K] Antistatic Agent The polymerizable liquid crystal composition of the present invention may contain an antistatic agent, if necessary. The antistatic agent to be used is not particularly limited, and may contain known and conventional ones as long as the orientation is not disturbed.

As such an antistatic agent, a polymer compound having at least one type of sulfonate group or phosphate group in a molecule, a compound having a quaternary ammonium salt, a surfactant having a polymerizable group, and the like can be mentioned.

Among them, surfactants having a polymerizable group are preferable. For example, among surfactants having a polymerizable group, as anionic ones, "Antox SAD", "Antox MS-2N" Company), “Aqualon KH-05”, “Aqualon KH-10”, “Aqualon KH-20”, “Aqualon KH-0530”, “Aqualon KH-1025” (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Alkylethers such as "ADEKAREASOAP SR-10N", "ADEKAREASOAP SR-20N" (manufactured by ADEKA Corporation), "Latemmul PD-104" (manufactured by Kao Corporation), "Latemul S-120" "Latemur S-120A", "Latemur S-180P", "Latemur S-180A" (above, manufactured by Kao Corporation), "Eleminol" Sulfosuccinates such as “S-2” (manufactured by Sanyo Chemical Industries, Ltd.), “Aqualon H-2855A”, “Aqualon H-3855B”, “Aqualon H-3855C”, “Aqualon H-3856”, “Aqualon HS -05 "," Aqualon 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 "(all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)," Adecaria Soap SDX-222 "," Adecaria Soap SDX-223 "," Adecaria Soap SDX-232, "Adeka Rear Soap SDX-233", "Adeka Rear Soap SDX-259" Alkylphenyl ethers or alkylphenyl esters such as "ADEKAREASOAP SE-10N" and "ADEKAREASOAP SE-20N" (all manufactured by ADEKA Corporation), "Antox MS-60", "Antox MS-" 2N (made by Nippon Emulsifier Co., Ltd.), "Eleminol RS-30" (made by Sanyo Kasei Co., Ltd.), etc. And phosphoric acid esters such as "ADEKAREASOAP PP-70" (manufactured by ADEKA Co., Ltd.).

On the other hand, among the surfactants having a polymerizable group, as nonionic surfactants, for example, “Antox LMA-20”, “Antox LMA-27”, “Antox EMH-20”, “Antox LMH- 20, "Antox SMH-20" (manufactured by Nippon Emulsifier Co., Ltd.), "Adekaria Soap ER-10", "Adekaria Soap ER-20", "Adekaria Soap ER-30", "Adekaria Soap" Alkylethers such as ER-40 (above, ADEKA Co., Ltd.), "Latemul PD-420", "Latemur PD-430", "Latemur PD-450" (above, Kao Corporation), etc., "Aqualon RN-10, Aqualon RN-20, Aqualon RN-30, Aqualon RN-50, Aqualon RN-2025 Above, Dai-ichi Kogyo Seiyaku Co., Ltd.), "Adekaria soap NE-10", "Adekaria soap NE-20", "Adekaria soap NE-30", "Adekaria soap NE-40" (Made by ADEKA Co., Ltd.), alkylphenyl ethers or alkylphenyl esters such as “RMA-564”, “RMA-568”, “RMA-1114” (all manufactured by Nippon Emulsifier Co., Ltd.), etc. An ester type is mentioned.

Other antistatic agents include, 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, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, propoxypolypropylene glycol (meth) acrylate , N-butoxypolypropylene glycol (meth) ac Rate, n-pentaxy polypropylene glycol (meth) acrylate, phenoxy polypropylene glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate, methoxypolytetramethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, hexa Ethylene glycol (meth) acrylate, methoxyhexaethylene glycol (meth) acrylate and the like can be mentioned.

The antistatic agent may 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, 01 to 5% by weight is more preferred.
[L] Dye The polymerizable liquid crystal composition of the present invention can contain a dye, if necessary. The dye to be used is not particularly limited, and may contain commonly known ones as long as the orientation is not disturbed.

Examples of the dye include dichroic dyes and fluorescent dyes. Examples of such dyes include polyazo dyes, anthraquinone dyes, cyanine dyes, phthalocyanine dyes, perylene dyes, perinone dyes, squarylium dyes, etc. From the viewpoint of addition, the dyes are preferably dyes exhibiting liquid crystallinity. .

For example, U.S. Pat. No. 2,400,877, Dreyer J.F., Phys. And Colloid Chem., 1948, 52, 808., "The Fixing of MolecularOrientation", Dreyer JF, Journal de Physique, 1969, 4, 114., "Light Polarization from Films of Lyotropic Nematic Liquid Crystals" and J. Lydon, "Chromonics" in "Handbook of Liquid Crystals Vol. 2B: Low Molecular Weight Liquid Crystals II", D. Demus, J. Goodby, GW Gray , HW Spiessm, V. Vill ed, Willey-VCH, P. 981-1007 (1998), Dichroic Dyes for Liquid Crystal Display A. V. lvashchenko
Dyes described in CRC Press, 1994, and "New Development of Functional Dye Market", Chapter 1, page 1, 1994, CMC Co., Ltd. Luminescence, etc. can be used.
As a dichroic dye, for example, the following formulas (d-1) to (d-9)

Can be mentioned. The amount of the dye such as the dichroic dye added 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 known and conventional ones as long as the thermal conductivity of the obtained polymer does not decrease.
Examples of the filler include inorganic fillers such as alumina, titanium white, aluminum hydroxide, talc, clay, mica, barium titanate, zinc oxide and glass fibers, metal powders such as silver powder and copper powder, aluminum nitride, and nitrides Thermally conductive filler such as boron, silicon nitride, gallium nitride, silicon carbide, magnesia (aluminum oxide), silica, crystalline silica (silicon oxide), fused silica (silicon oxide), graphite, carbon fiber including carbon nanofibers, etc. And silver nanoparticles.

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 (above, Showa Denko KK), A31, A31 B, A32, A33 F, A41 A, A43 A, MM-22, MM-26, MM-P, MM-23 B, LS-110 F, LS-130, LS- 210, LS-242C, LS-250, AHP 300 (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 (above, made by Fuji Titanium Industry 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 Tayca 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, B as aluminum hydroxide -309 (manufactured by Sakai Industry Co., Ltd.), BA173, BA103, B703, B1403, BF013, BE033, BX103, BX043 (Nippon Light Metal Co., Ltd.), Talc as Nano Ace D-1000, Nano Ace D-800, Micro Ace SG-95, Micro Ace P-8, Micro Ace P-6 (above, Nippon Talc Co., Ltd.), FH 104, FH 105, FL 108, FG 106, MG 115, FH 104 S, ML 112 S (above, Fuji Talc Industrial Co., Ltd.), mica As Y-1800, TM-10, A-11, SJ-005 (above, Yama Corporation Gthmica), barium titanate BT-H9DX, HF-9, HF-37N, HF-90D, HF-120D, HT-F (above, Kyoritsu Materials Co., Ltd.), BT-100, HPBT series (above, Fujititan Industry Co., Ltd.), BT series (Sakai Chemical Industry Co., Ltd.), PARCERAM BT (Nippon Chemical Industry Co., Ltd.), zinc oxide as FINEX-30, FINEX-30W-LP2, FINEX-50, FINEX-50S -LP2, XZ-100F (above, Suga Chemical Industry Co., Ltd.), FZO-50 (made by Ishihara Sangyo Co., Ltd.), MZ-300, MZ-306X, MZY-505S, MZ-506X, MZ-510HPSX (above, Taika Co., Ltd.), glass fibers CS6SK-406, CS13C-897, CS3PC- 55, CS3 LCP-256 (above, Nitto Boseki Co., Ltd.), ECS 03-615, ECS 03-650, EFDE 50-01, EFDE 50-31 (above, Central Glass Co., Ltd.), ACS 6 H-103, ACS 6 S- 750 (above, NEC Corporation Glass Co., Ltd., spherical silver powder AG3 as silver powder, AG4, flake silver powder FA5, FA2 (above, DOWA High Tech Co., Ltd.), SPQ03R, SPN05N, SPN08S, Q03R (above, Mitsui Metal Mining Co., Ltd.), AY-6010 AY-6080 (above, made by Tanaka Kikinzoku Co., Ltd.), ASP-100 (by Aida Chemical Industry Co., Ltd.), Ag-coated powder AG / SP (made by Mitsubishi Materials Electronic Chemicals Co., Ltd.), MA-O015K as a copper powder, MA- O02K, MA-O025K (The above, Mitsui Metal ore Ltd., electrolytic copper powder # 52-C, # 6 (above, made by JX Nippon Mining & Metals Co., Ltd.), 10% Ag coated Cu-HWQ (manufactured by Fukuda Metal Foil Powder Industrial Co., Ltd.), copper powder Type- A, Type-B (all manufactured by Dowa Electronics Co., Ltd.), UCP-030 (manufactured by Sumitomo Metal Mining Co., Ltd.),
H grade as aluminum nitride, E grade, HT grade (above, Tokuyama Co., Ltd.), TOYAL TecFiller TFS-A05P, TOYAL TecFiller TFZ-A02P (above, Toyo Aluminum Co., Ltd.), ALN020BF, ALN050BF, ALN020AF, ALN050AF , ALN 020 SF (all, manufactured by Sakai Industry Co., Ltd.), FAN-f05, FAN-f 30 (all, manufactured by Furukawa Electronics Co., Ltd.), Denka boron nitride SGP as boron nitride, Denka boron nitride MGP, Denka boron nitride GP, Denkaboron nitride HGP, Denkaboron nitride SP-2, Denkaboron nitride SGPS (above, manufactured by Denki Kagaku Kogyo Co., Ltd.), UHP-S1, UHP-1K, UHP-2, UHP-EX (above, made by Showa Denko KK) Silicon nitride as SN-9, SN-9S, SN-9S, SN-9FWS, SN-F1, SN-F2 (above, made by Denki Kagaku Kogyo Co., Ltd.), CF0027 , CF0093, CF0018, CF0033 (above, made by Nippon Frit Co., Ltd.), GFM-H type, GMF-H2 type, GMF-LC type (above, Pacific Random Co., Ltd.), HSC1200, HSC1000, HSC059, HSC059I as silicon carbide HSC 007 (above, Sakai Kogyo Co., Ltd.), silica as Saisiria (Fuji Silysia Chemical Ltd.), AEROSIL R972, AEROSIL R104, AEROSIL R202, AEROSIL 805, AEROSIL R812, AEROSIL R7200 (above, This Aerosil Co., Ltd. product, Rheosil series (manufactured by Tokuyama Co., Ltd.), crystalline silica (silicon oxide) as CMC-12, VX-S, VX-SR (all manufactured by Ryumori Co., Ltd.), fused silica As silicon oxide) FB-3SDC, FB-3SDX, SFP-30M, SFP-20M, SFP-30MHE, SFP-130MC, UFP-30 (above, manufactured by Denki Kagaku Kogyo Co., Ltd.), Exelica series (manufactured by Tokuyama Co., Ltd.) ), Aluminum oxide AEROXIDE Alu C, AEROXIDE Alu 65 (above, made by Nippon Aerosil Co., Ltd.), carbon fiber and graphite as Trekhamido fiber MLD-30, Trekgamid fiber MLD-300 (above, Toray Co., Ltd.), CFMP -30X, CFMP-150X (or more Japan Polymer Industry Co., Ltd.), XN-100, HC-600 (above, Japan Graphite Fiber Co., Ltd.), SWeNT SG65, SWeNT SGi, IsoNanoTubes-M, IsoNanoTubes-S, PureTubes, Pyrograf PR-25-XT-PS And PR-25 XT-LHT (manufactured by Sigma-Aldrich Co., Ltd.), and the like.

The fillers may be used alone or in combination of two or more. The amount of the filler added is preferably 0.01 to 80% by weight based on the total amount of the at least one polymerizable group-containing liquid crystal compound used in the polymerizable liquid crystal composition of the present invention. 0.1 to 50% by weight is more preferable.
[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 itself does not have to exhibit liquid crystallinity, and may or may not have a polymerizable group. In addition, the direction of the helix of the chiral compound can be appropriately selected depending on the application of the polymer.

The chiral compound having a polymerizable group is not particularly limited, and known ones can be used, but a large chiral compound having a 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 according to the helical induction force of the compound, but it is contained in an amount of 0.5 to 80% by mass based on the total amount of the liquid crystal compound having a polymerizable group and the chiral compound. Is preferable, containing 3 to 50% by mass is more preferable, and containing 5 to 30% by mass is particularly preferable.

As specific examples of the chiral compound, compounds represented by the following general formulas (10-1) to (10-4) can be mentioned, but the invention is not limited to the following general formulas.

In the above formulas, 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 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 -O-, -S-, -NH-, -N (CH ₃ )-, -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS- in a form not directly bound to Or -C≡C- may be substituted,
A1, A2, A3, A4, A5 and A6 are each independently 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, Pyrimidin-2,5-diyl group, Pyrazine-2,5-diyl group, Thiophene-2,5-diyl group-, 1,2,3,4-Tetrahydronaphthalene-2, 6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydro group Henanthrene-2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5-b ′] dithiophene-2,6-diyl group, benzo [1,2-b: 4, 5-b '] Diselenophene-2, 6-diyl group, [1] benzothieno [3, 2-b] thiophene-2, 7-diyl group, [1] benzoselenopheno [3, 2- b] selenophen-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 -, - Represents CONH-, -NHCO-, an alkyl group having 2 to 10 carbon atoms, or a single bond,
R ^5a and R ^{5b each} 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 by 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 may be replaced by -C≡C-, or R ^5a and R ^5b have the general formula (10-a)

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

As further specific examples of the above chiral compound, compounds represented by the following general formulas (10-5) to (10-38) can be mentioned.

In the above formulas, 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, but when a plurality of R are present, Each may be identical or different.

Specific examples of the chiral compound having no polymerizable group include, for example, cholesterol pelargonic acid having cholesteryl group as a chiral group, cholesterol stearic acid, and a BD manufactured by BD Co., Ltd. having a 2-methylbutyl group as a chiral group. "CB-15", "C-15", "S-1082" manufactured by Merck, "CM-19" manufactured by Chisso, "CM-20", "CM", 1-methylheptyl group as a chiral group "S-811" manufactured by Merck & Co., "CM-21" and "CM-22" manufactured by Chisso, and the like.

When a chiral compound is added, it depends on the use of the polymer of the polymerizable liquid crystal composition of the present invention, but the value obtained by dividing the thickness (d) of the obtained polymer by the helical pitch (P) in the polymer (d It is preferable to add an amount such that / P) is in the range of 0.1 to 100, and a further preferable amount is in the range of 0.1 to 20.
[O] Non-Liquid Crystalline Compound Having Polymerizable Group To the polymerizable liquid crystal composition of the present invention, a compound having a polymerizable group but not a liquid crystal compound can be added. Such compounds can be used without particular limitation as long as they are generally recognized as polymerizable monomers or polymerizable oligomers in this technical field. When it is 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, Dicyclopentanyloxyethyl (meth) acrylate, isobornyl oxylethyl (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-ethyloxetan-3-yl) methyl (meth) acrylate, o-phenylphenol ethoxy (meth) acrylate, dimethylamino (meth) acrylate, diethylamino Meta) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2,2,3,4,4,4-hexafluorobutyl (meth) acrylate, 2,2,3,3,3 4,4,4-Heptafluorobutyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 1H, 1H, 3H-tetrafluoropropyl ( Meta) 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-tetra Trafluoro-1- (trifluoromethyl) ethyl (meth) acrylate, 1H, 1H-pentadecafluorooctyl (meth) acrylate, 1H, 1H, 2H, 2H-tridecafluorooctyl (meth) acrylate, 2- (meta) ) Acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, glycidyl (meth) acrylate, 2- (meth) acryloyloxyethyl phosphoric acid, acryloyl morpholine, dimethyl acrylamide, dimethylaminopropyl acrylamide, ilopropyl Mono (meth) acrylates such as acrylamide, diethyl acrylamide, hydroxyethyl acrylamide, N-acryloyloxyethyl hexahydrophthalimide, 1,4-butanediol di (meth) acrylate , 1,6-Hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyldiol di (meth) acrylate, tripropylene glycol di (meth) acrylate, ethylene glycol di (meth) Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 9,9-bis [4- (2) -Acryloyloxyethoxy) phenyl] fluorene, Glycerin di (meth) acrylate, 2-hydroxy-3-acroyloxypropyl methacrylate, Acrylic acid addition of 1,6-hexanediol diglycidyl ether , Acrylic acid adducts of 1,4-butanediol diglycidyl ether, etc., etc., trimethylolpropane tri (meth) acrylate, ethoxylated isocyanuric acid triacrylate, pentaerythritol tri (meth) acrylate, ε-caprolactone modified Tri (meth) acrylates such as tris- (2-acryloyloxyethyl) isocyanurate, etc., tetra (meth) acrylates such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, etc., dipentaerythritol hexa ( Meta) acrylate, oligomeric (meth) acrylate, various urethane acrylates, various macromonomers, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl Ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl 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 alignmentability is improved in order to improve alignmentability. The alignment material to be used may be a commonly known one as long as it is soluble in a solvent capable of dissolving the liquid crystal compound having a polymerizable group, which is used in the polymerizable liquid crystal composition of the present invention. It can be added in the range which does not deteriorate the orientation remarkably. Specifically, the content is preferably 0.05 to 30% by weight, and more preferably 0.5 to 15% by weight based on the total amount of the at least one polymerizable group-containing liquid crystal compound used in the polymerizable liquid crystal composition of the present invention. % Is more preferable, and 1 to 10% by weight is particularly preferable as polyimide, polyamide, BCB (benzocyclobutene polymer), polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, etc. Polyether sulfone, epoxy resin, epoxy acrylate resin, acrylic resin, coumarin compound, chalcone compound, cinnamate compound, fulgide compound, anthraquinone compound, azo compound, arylethene compound, etc., compounds for photoisomerization or photodimerization To be , Ultraviolet radiation, the material oriented by visible light irradiation (photo-alignment material) is preferable.

As the photo alignment material, for example, polyimide having cyclic cycloalkane, wholly aromatic polyarylate, polyvinyl cinnamate as disclosed in JP-A-5-232473, polyvinyl ester of paramethoxycinnamic acid, JP-A-6-3 No. 287,453, cinnamate derivatives as disclosed in JP-A-6-289374, maleimide derivatives as disclosed in JP-A-2002-265541, and the like. Specifically, compounds represented by the following formulas (12-1) to (12-9) are preferable.

In the above formulae, R ⁵ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group, a nitro group, R ⁶ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, The group may be linear or branched, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, and one —CH ₂ — or adjacent group in the alkyl group may be substituted. Two or more -CH _2- which are not each independently represent -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O. The terminal CH ₃ may be substituted by —CO—O—, —CO—NH—, —NH—CO— or —C≡C—, and the terminal CH ₃ may be CF ₃ , CCl ₃ , a cyano group, a nitro group, an isocyano group And may be substituted with a thioisocyano group. n represents 4 to 100,000, and m represents an integer of 1 to 10.
R ⁷ represents 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 can be obtained by polymerizing the polymerizable liquid crystal composition of the present invention in a state of containing an initiator. The polymer of the present invention is used for optically anisotropic materials, retardation films, lenses, optical parts, polarizing films, colorants, markings for security, coloring materials, printed materials, structural goods, restoration materials and the like.
(Base material)
The base material used for the optical anisotropic material of the present invention is a base material usually used for liquid crystal display elements, organic light emitting display elements, other display elements, optical parts, colorants, markings, printed matter and optical films. The material is not particularly limited as long as it is a material having heat resistance that can withstand heating during drying after application of the polymerizable liquid crystal composition solution of the invention. As such a substrate, an organic material such as a glass substrate, a metal substrate, a ceramic substrate, a plastic substrate or paper can be mentioned. In particular, when the substrate is an organic material, cellulose derivatives, polyolefins, polyesters, polyolefins, polycarbonates, polyacrylates, polyarylates, polyether sulfones, polyimides, polyphenylene sulfides, polyphenylene ethers, nylons, polystyrenes, etc. may be mentioned. Among them, plastic substrates such as polyester, polystyrene, polyolefin, cellulose derivative, polyarylate, polycarbonate and the like are preferable. As a shape of a base material, it may have a curved surface other than a flat plate. These substrates may have an electrode layer, an antireflective function, and a reflective function, as necessary.

In order to improve the coatability of the polymerizable liquid crystal composition of the present invention and the adhesion with a polymer, surface treatment of these substrates may be performed. As surface treatment, ozone treatment, plasma treatment, corona treatment, silane coupling treatment and the like can be mentioned. Moreover, in order to adjust light transmittance and reflectance, an organic thin film, an inorganic oxide thin film, a metal thin film, etc. are provided on the substrate surface by a method such as vapor deposition, or to add optical value. The material may be a pickup lens, a rod lens, an optical disc, 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.
(Alignment processing)
Further, the above-mentioned 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. It is good. Examples of orientation treatment include stretching treatment, rubbing treatment, polarized ultraviolet visible light irradiation treatment, ion beam treatment, and oblique deposition treatment of SiO ₂ on a substrate. When an alignment film is used, known alignment films are used. As such an alignment film, polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyether sulfone, polyether resin, epoxy resin, epoxy acrylate resin, acrylic resin, azo compound, coumarin Examples thereof include compounds such as compounds, chalcone compounds, cinnamate compounds, fulgide compounds, anthraquinone compounds, azo compounds, and arylethene compounds, or polymers and copolymers of the compounds. The compound to be subjected to alignment treatment by rubbing is preferably one that promotes crystallization of the material by introducing a heating step after the alignment treatment or the alignment treatment. Among the compounds to be subjected to alignment treatment other than rubbing, it is preferable to use a photoalignment material.

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 is aligned. Whether the liquid crystal molecules are aligned horizontally with the substrate, or inclined or vertically aligned is largely affected by the method of alignment treatment on the substrate. For example, if an alignment film with a very small pretilt angle, such as that used in an in-plane switching (IPS) liquid crystal display device, is provided on the substrate, a substantially horizontally aligned polymerizable liquid crystal layer can be obtained.

In addition, when an alignment film as used in a TN liquid crystal display element is provided on a substrate, a polymerizable liquid crystal layer with slightly inclined alignment is obtained, and an alignment film as used in a STN liquid crystal display element By using the above, it is possible to obtain a polymerizable liquid crystal layer whose orientation is largely inclined.
(Application)
As a coating method for obtaining the optically anisotropic body of the present invention, an applicator method, bar coating method, spin coating method, roll coating method, direct gravure coating method, reverse gravure coating method, flexo coating method, inkjet method, die coating Methods known in the art such as cap coating method, dip coating method, slit coating method, spray coating method, etc. can be performed. After the polymerizable liquid crystal composition is applied, it is dried.

After application, it is preferable to uniformly align liquid crystal molecules in the polymerizable liquid crystal composition of the present invention in a state in which a smectic phase or a nematic phase is maintained. A heat treatment method is mentioned as one of the methods. Specifically, after the polymerizable liquid crystal composition of the present invention is coated on a substrate, the N (nematic phase) -I (isotropic liquid phase) transition temperature (hereinafter referred to as the NI transition temperature) of the liquid crystal composition The liquid crystal composition is put in an isotropic phase liquid state by heating to the above. From there, it is gradually cooled if necessary to express a nematic phase. At this time, it is desirable to once maintain the temperature at which the liquid crystal phase is exhibited, and sufficiently grow the liquid crystal phase domain into a monodomain. Alternatively, after the polymerizable liquid crystal composition of the present invention is coated on a substrate, heat treatment may be performed so as to maintain the temperature for a certain period within the temperature range in which the nematic phase of the polymerizable liquid crystal composition of the present invention is developed.

When the heating temperature is too high, the polymerizable liquid crystal compound may cause an undesirable polymerization reaction to deteriorate. In addition, if it is cooled too much, the polymerizable liquid crystal composition may undergo phase separation to cause crystal precipitation and a higher order liquid crystal phase such as a smectic phase, which may make the alignment process impossible.

By performing such heat treatment, it is possible to produce a homogeneous optically anisotropic member with less orientation defects as compared to a coating method which is simply applied.
In addition, after performing homogeneous orientation processing in this way, the liquid crystal phase is cooled to the lowest temperature at which phase separation does not occur, that is, to a state of supercooling, and polymerization is performed in this liquid crystal phase when oriented. It is possible to obtain an optical anisotropic material having higher orientational order and excellent transparency.
(Polymerization process)
The polymerization treatment of the dried polymerizable liquid crystal composition is generally performed by light irradiation such as visible ultraviolet light or heating in a uniformly oriented state. When the polymerization is carried out by light irradiation, specifically, it is preferable to irradiate visible ultraviolet light of 420 nm or less, and it is most preferable to irradiate ultraviolet light having a wavelength of 250 to 370 nm. However, when the polymerizable liquid crystal composition causes decomposition or the like by visible ultraviolet light of 420 nm or less, it may be preferable to carry out polymerization treatment with visible ultraviolet light of 420 nm or more.
(Polymerization method)
As a method of polymerizing the polymerizable liquid crystal composition of the present invention, a method of irradiating an active energy ray, a thermal polymerization method, etc. may be mentioned, but heating is not necessary and the reaction proceeds at room temperature. A method of irradiation is preferable, and among them, a method of irradiating light such as ultraviolet light is preferable because the operation is simple. The temperature at the time of irradiation is preferably set to a temperature at which the polymerizable liquid crystal composition of the present invention can maintain the liquid crystal phase and to 30 ° C. or less as much as possible to avoid induction of thermal polymerization of the polymerizable liquid crystal composition. The polymerizable liquid crystal composition generally has a C (solid phase) -N (nematic) transition temperature (hereinafter referred to as a CN transition temperature) and an NI transition temperature within the temperature rising process. Indicates a liquid crystal phase. On the other hand, in the temperature lowering process, since it is thermodynamically non-equilibrium, the liquid crystal state may be maintained without solidification even at the CN transition temperature or lower. This state is called a supercooling state. In the present invention, a liquid crystal composition in a supercooled state is also included in the state of holding a liquid crystal phase. Specifically, irradiation with ultraviolet light of 390 nm or less is preferable, and irradiation with light with a wavelength of 250 to 370 nm is most preferable. However, when the polymerizable liquid crystal composition causes decomposition or the like by ultraviolet light of 390 nm or less, it may be preferable to carry out the polymerization treatment with ultraviolet light of 390 nm or more. The light is preferably diffused light and unpolarized light. The ultraviolet irradiation intensity is preferably in the range of 0.05 mW / cm ² to 10 W / cm ² . In particular, the range of 0.2 mW / cm ² to 2 W / cm ² is preferable. When the ultraviolet 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 be decomposed by light, and a large amount of heat of polymerization is generated to raise the temperature during polymerization, and the order of the polymerizable liquid crystal The parameters may change and may cause retardation in 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.

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

In addition, when polymerizing only a specific part with ultraviolet light using a mask, the alignment was regulated by applying an electric field, a magnetic field, temperature, etc. to the polymerizable liquid crystal composition in the unpolymerized state in advance, and the state was maintained. By irradiating light from above the mask as it is, it is possible to obtain an optically anisotropic body having a plurality of regions having different alignment directions.

The optically anisotropic body obtained by polymerizing the polymerizable liquid crystal composition of the present invention may be peeled off from the substrate and used alone as an optically anisotropic body, or may be used directly as an optically anisotropic body without peeling from the substrate. You can also In particular, since it is hard to contaminate other members, it is useful when using it as a lamination | stacking board | substrate, or bonding and using it to another board | substrate.

The optically anisotropic body can also be heat-aged for stabilization of the solvent resistance and heat resistance of the obtained optically anisotropic body. In this case, it is preferable to heat above the glass transition point of the polymer film. Usually, 50 to 300 ° C. is preferable, 80 to 240 ° C. is more preferable, and 100 to 220 ° C. is particularly preferable.
(Retardation film)
The retardation film of the present invention contains the above-mentioned optical anisotropic material, and the liquid crystal compound forms a uniform continuous alignment state with respect to the substrate, and the in-plane, surface of the substrate is obtained. It suffices to have biaxiality in the outside, both in the plane and out of the plane, or in the plane. In addition, an adhesive, an adhesive layer, an adhesive, an adhesive layer, a protective film, a polarizing film, or the like may be laminated.

As such a retardation film, for example, a positive A plate in which a rod-like liquid crystalline compound is substantially horizontally aligned with respect to a substrate, and a negative A plate in which a discotic liquid crystalline compound is uniaxially oriented perpendicularly to a substrate A positive C plate in which a rod-like liquid crystalline compound is oriented substantially perpendicularly to a substrate, a negative C in which a rod-like liquid crystalline compound is cholesterically aligned with respect to a substrate, or a discotic liquid crystalline compound is uniaxially oriented horizontally The orientation mode of a plate, a biaxial plate, a positive O plate in which a rod-like liquid crystalline compound is hybrid oriented with respect to a substrate, and a negative O plate in which a discotic liquid crystalline compound is hybrid oriented with respect to a substrate can be applied. When used for an optical compensation film of a liquid crystal display element, various orientation modes can be applied without particular limitation as long as the viewing angle dependency is improved.

For example, orientation modes of positive A plate, negative A plate, positive C plate, negative C plate, biaxial plate, positive O plate, 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 to a substrate, and 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 reflective film or an infrared reflective film. In that case, in the retardation film of the present invention, the rod-like liquid crystalline compound is cholesterically oriented substantially in the horizontal direction with respect to the substrate, and in the case of a polarized light reflective film, the pitch is in the visible light region and red 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 base material or a base material having an alignment function, or injected into a lens-shaped mold to uniformly align in a state in which a nematic phase or smectic phase is retained. Can be used for the lens of the present invention by The shape of the lens may be a simple cell type, a prism type, a lenticular type, or the like.
(Liquid crystal display element)
The liquid crystal composition of the present invention is applied by coating the polymerizable liquid crystal composition of the present invention on a base material or a base material having an alignment function, uniformly aligning and polymerizing in a state of holding a nematic phase or smectic phase. 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. The liquid crystal display device has a liquid crystal medium layer, a TFT drive circuit, a black matrix layer, a color filter layer, a spacer, and an electrode circuit corresponding to the liquid crystal medium layer at least on at least two substrates. 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 narrow in the two substrates. It may be held.

Although there are TN mode, VA mode, IPS mode, FFS mode, OCB mode, etc. as an orientation mode of the liquid crystal display element, when used in an optical compensation film or an optical compensation layer, the phase difference corresponding to the orientation mode The film can be made. When used in a patterned retardation film, the liquid crystal compound in the polymerizable liquid crystal composition may be substantially horizontally aligned with respect to the substrate. When used in the overcoat layer, a liquid crystal 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. It is also possible to mix in a liquid crystal medium, and the ratio between the liquid crystal medium and the liquid crystal compound has the effect of improving various characteristics such as response speed and contrast.
(Organic light emitting display element)
The polymerizable liquid crystal composition of the present invention is applied to a base material or a base material having an alignment function, uniformly oriented in a state where a nematic phase or a smectic phase is held, and then polymerized to obtain the organic luminescence of the present invention. It can be used for a display element. As a use form, it can be used as an anti-reflective film of an organic light emitting display element by combining with the retardation film and polarizing plate which were obtained by the said superposition | polymerization. When it is used as an antireflective film, the angle between the polarizing 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, a pressure-sensitive adhesive or the like. Alternatively, the layers may be directly laminated by rubbing treatment, alignment treatment in which a photo alignment film is laminated, or the like on a polarizing plate. The polarizing plate used at this time may be a film having a polarizing function, for example, a film obtained by adsorbing iodine or a dichroic dye to a polyvinyl alcohol-based film and stretched, a polyvinyl alcohol-based film is stretched to obtain iodine or the like A dichroic dye or a film on which a dichroic dye is adsorbed, a film in which an aqueous solution containing a dichroic dye is coated on a substrate to form a polarizing layer, a wire grid polarizer, etc. may be mentioned.

As polyvinyl alcohol-type resin, what saponified polyvinyl acetate-type resin can be used, As polyvinyl acetate-type resin, vinyl acetate with this besides polyvinyl acetate which is a homopolymer of vinyl acetate 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 into a film 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, and is, for example, about 10 to 150 μm.

When using iodine as a dichroic dye, the method of immersing and dye | staining a polyvinyl-alcohol-type resin film the aqueous solution containing an iodine and potassium iodide is employ | adopted normally. In the case of using a dichroic dye as the dichroic dye, generally, a method of dyeing by immersing a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic dye is employed.

In the case of a film in which an aqueous solution containing a dichroic dye is coated on a substrate to form a polarizing layer, examples of the dichroic dye to be coated include direct dyes, acid dyes, etc., depending on the type of substrate used. Water-soluble dyes of the present invention and their acid salts and disperse dyes, water-insoluble dyes such as oil-soluble pigments, and the like. These dyes are usually dissolved in water and an organic solvent, and in some cases, they are applied to a substrate subjected to rubbing and corona treatment by adding a surfactant. The organic solvent varies depending on the solvent resistance of the substrate, but generally, 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-methyl violidone, and aromatic organic solvents such as benzene and toluene. The coating amount of the dye depends 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. Examples of the method for applying the color PfJ solution to a substrate include various coating methods such as bar coder coating spray coating, roll coating, and a gravure coater.

When using a wire grid polarizer, it is preferable to use what was formed with electrically-conductive materials, such as Al, Cu, Ag, Cu, Ni, Cr, and Si.
(Lighting element)
A polymer obtained by polymerizing the polymerizable liquid crystal composition of the present invention in a state of being aligned on a substrate having a nematic phase, a smectic phase, or an alignment function is used as a heat dissipation material for lighting elements, particularly light emitting diode It can also be done. As a form of the heat dissipation 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 it in a state of holding a nematic phase or a smectic phase, or in a state of being combined with an alignment material.
(Colorant)
The polymerizable liquid crystal composition of the present invention can also be used as a colorant by adding a colorant such as a dye or an organic pigment.
(Polarization film)
The polymerizable liquid crystal composition of the present invention can also be used as a polarizing film by being combined with or added to a dichroic dye, lyotropic liquid crystal, chromonic liquid crystal or the like.
(Marking for security)
The polymerizable liquid crystal composition of the present invention can be used as a marking for security or printed matter in combination or addition with a chiral compound, a dichroic dye, a dye, a filler, a magnetic powder, a fluorescent dye and the like.

Hereinafter, the present invention will be described by way of Examples and Comparative Examples, but the present invention is not of course limited thereto. In addition, unless there is particular notice, "part" and "%" are mass references.
(Preparation of Polymerizable Liquid Crystal Composition (1))
40 parts of a compound represented by the formula (A-1), 25 parts of a compound represented by the formula (A-2), 20 parts of a compound represented by the formula (A-3), p-methoxyphenol (MEHQ) 0 .1 part, and after adding 0.2 part of Megafac R-40 (R-40: DIC Corporation) to 172 parts of propylene glycol monomethyl ether acetate (PGMEA) and N-methyl-2-pyrrolidone (NMP), The mixture was heated to 60 ° C., stirred to dissolve, and after dissolution was confirmed, the temperature was returned to room temperature, 5 parts of Irgacure 907 (manufactured by BASF Corporation) was added, and stirring was further performed to obtain a solution. The solution was clear and homogeneous. The resulting solution was filtered with 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 Composition (2) to (83), Comparative Polymerizable Liquid Crystal Composition (C1) to (C23))
Example 2 to Example 2 under the same conditions as in the preparation of the polymerizable liquid crystal composition (1) of Example 1 except that the compounds shown in the following Tables 1 to 11 were changed to the proportions shown in the following Tables 1 to 11, respectively. The polymerizable liquid crystal compositions (C1) to (C23) of the polymerizable liquid crystal compositions (2) to (83) and comparative examples 1 to 23 used for 83 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)

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

(Polymerization initiator)
Irgacure 907 (manufactured by BASF Corporation) (K-1)
Irgacure 819 (manufactured by BASF Corporation) (K-2)
Adeka Cruise NCI-930 (made by Adeka Co., Ltd.) (K-3)
Amnirad 184 (manufactured by IGM Resins) (K-4)
Trimethylolpropane tristhiopropionate (L-1)
ARONIX M-5700 (made by Toagosei Co., Ltd.) (L-2)
Light ester HOB-A (made by Kyoeisha Chemical Co., Ltd.) (L-3)
Megafuck R-40 (made by DIC Corporation) (M-1)
Megafuck F-554 (made by DIC Corporation) (M-2)
Megafuck RS-75 (made by DIC Corporation) (M-3)
Megafuck DS-21 (made by DIC Corporation) (M-4)
Futurgent FTX-218 (made by Neos Co., Ltd.) (M-5)
Futurgent 730 LM (made by Neos Co., Ltd.) (M-6)
TEGO Flow ZFS 460 (manufactured by Evonik Industries Ltd.)
Example 1
The solubility of the polymerizable liquid crystal composition (1) of the present invention, storage stability (preservability), evaluation of orientation, and solution viscosity were measured. The results are shown in Table 1.

(Solubility)
○: After adjustment, a transparent and uniform state can be visually confirmed.
Fair: A transparent and uniform state can be visually confirmed when heated and expanded, but precipitation of the compound is confirmed when the temperature is returned to room temperature.
X: The compound can not be uniformly dissolved even by heating and stirring.
(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 remained in a transparent and uniform state even after one week. Evaluation of storage stability is
○: A transparent and uniform state is maintained even after standing at 0 ° C. for one week.
Δ: Even after leaving for 3 days at 0 ° C., the transparent and uniform state is maintained.
X: Precipitation of the compound is confirmed after standing at 0 ° C. for 1 day.
(Alignment)
A polyimide solution for horizontal alignment film was applied to a glass substrate having a thickness of 0.7 mm using a spin coating method, dried at 100 ° C. for 10 minutes, and baked at 200 ° C. for 60 minutes to obtain a coating film. The resulting coating was rubbed. The rubbing treatment was performed using a commercially available rubbing device.

The polymerizable composition (1) of the present invention immediately after dissolution and after evaluation of storage stability was applied to the rubbed substrate by spin coating and dried at 80 ° C. for 2 minutes. The coated film obtained 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 the optically anisotropic body of Example 1. The obtained optically anisotropic body was evaluated according to the following criteria. As a result, it was found that there were no alignment defects visually and no alignment defects even by polarized microscope observation. In the following criteria, ◎ is the most excellent in orientation, and x is intended to show no orientation at all.

[Evaluation criteria]
Visual observation: Two polarizing plates are arranged on a light box so as to satisfy crossed Nicols conditions, and the obtained optically anisotropic body is placed between the two polarizing plates, and visually observed while rotating the optically anisotropic body. did.
Polarized microscope observation: Observation at a magnification of 200 × ◎: no unevenness in observation under a sodium lamp, and no defect at all in visual observation or polarized light microscope observation.
:: There is some unevenness in observation under a sodium lamp, but there is no defect in visual observation or polarized light microscope observation.
Fair: Slight unevenness in observation under a sodium lamp and no defect in visual observation, but in polarization microscope observation, a non-alignment portion is present as a whole.
X: A lot of unevenness is observed in observation under a sodium lamp, a defect is partially generated by visual observation, and a non-alignment portion is present as a whole by polarized light microscope observation.
(Solution viscosity)
After placing 1.5 g of the polymerizable composition (1) of the present invention in a cup of an E-type viscometer, the rotor of the viscometer was rotated, and the point at which the change in the indicated value disappeared was taken 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 to 56, 64 to 69)
In the same manner as in Example 1, the evaluations in Examples 2 to 56 and 64 to 69 were performed.
(Example 57)
A polyimide solution for vertical alignment film was applied to a glass substrate having a thickness of 0.7 mm using a spin coating method, 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 evaluation of storage stability was applied to the obtained substrate by spin coating and dried at 80 ° C. for 2 minutes. The coated film obtained is left to stand at room temperature for 1 minute and then irradiated with ultraviolet light for 30 seconds at an intensity of 30 mW / cm ² using a high pressure mercury lamp to obtain an optical anisotropic body having homeotropic alignment of Example 55 The The obtained optical anisotropy was evaluated according to the following criteria.

[Evaluation criteria]
Visual observation: Two polarizing plates are arranged on the light box so as to satisfy the crossed Nicols condition, the obtained optically anisotropic body is placed between the two polarizing plates, and the optically anisotropic body is faced front and inclined, It observed visually. In the following criteria, ◎ is the most excellent in orientation, and x is intended to show no orientation at all.
Polarized light microscope observation: Observation at 200 × magnification
◎: There is no unevenness in observation under a sodium lamp, and there are no defects in visual observation or polarization microscope observation.
:: There is some unevenness in observation under a sodium lamp, but there is no defect in visual observation or polarized light microscope observation.
Fair: Slight unevenness in observation under a sodium lamp and no defect in visual observation, but in polarization microscope observation, a non-alignment portion is present as a whole.
X: A lot of unevenness is observed in observation under a sodium lamp, a defect is partially generated by visual observation, and a non-alignment portion is present as a whole by polarized light microscope observation.
(Examples 58 to 60, 70 to 73)
The evaluations of Examples 58 to 60 and 70 to 73 were carried out in the same manner as in Example 57.
(Example 61)
A polyimide solution for alignment film was applied to a glass substrate having a thickness of 0.7 mm using a spin coating method, dried at 100 ° C. for 10 minutes, and baked at 200 ° C. for 60 minutes to obtain a coating film. The resulting coating was rubbed. The rubbing treatment was performed using a commercially available rubbing device.

The polymerizable composition (61) of the present invention immediately after dissolution and after evaluation of storage stability was applied to the rubbed substrate by spin coating and dried at 80 ° C. for 2 minutes. The coated film obtained is left to stand at room temperature for 1 minute, then irradiated with ultraviolet light for 30 seconds at an intensity of 30 mW / cm ² using a high pressure mercury lamp to obtain an optical anisotropic material having selective reflection characteristics of Example 61. The The obtained optical anisotropy was evaluated according to the following criteria. In the following criteria, ◎ is the most excellent in orientation, and x is intended to show no orientation at all.
[Evaluation criteria]
Visual observation: The obtained optically anisotropic body was placed on a black plate, and visually observed while the optical anisotropic body was in front and inclined.
Polarized microscope observation: Observation at a magnification of 200 × ◎: no unevenness in observation under a sodium lamp, and no defect at all in visual observation or polarized light microscope observation.
:: There is some unevenness in observation under a sodium lamp, but there is no defect in visual observation or polarized light microscope observation.
Fair: Slight unevenness in observation under a sodium lamp and no defect in visual observation, but in polarization microscope observation, a non-alignment portion is present as a whole.
X: A lot of unevenness is observed in observation under a sodium lamp, a defect is partially generated by visual observation, and a non-alignment portion is present as a whole by polarized light microscope observation.
(Examples 62 and 63)
The evaluations of Examples 62 and 63 were performed in the same manner as Example 61.

The polymerizable liquid crystal compositions (2) to (56) and (64) to (69) are kept in a transparent and uniform state even after standing at 0 ° C. for one week, and immediately after dissolution, after standing for one week An optically anisotropic material having good orientation was obtained by 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 material obtained from each of the polymerizable liquid crystal compositions, 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 immediately after dissolution, even after being left for one week, visual observation is possible regardless of which polymerizable liquid crystal composition is used. There were no orientation defects at all, and no orientation defects were observed even by polarizing microscope observation.

The polymerizable liquid crystal compositions (58) to (60) and (70) to (73) are in a transparent and uniform state even after being left at 0 ° C. for one week, and immediately after dissolution, after being left for one week. An optically anisotropic material having good orientation was obtained by using any of the polymerizable liquid crystal compositions.
The polymerizable liquid crystal composition (61) is kept in a transparent and uniform state even after being left at 0 ° C. for one week, and immediately after dissolution, even after being left for one week, any liquid crystal composition is visually observed. There were no orientation defects at all, and no orientation defects were observed even by polarizing microscope observation.

The polymerizable liquid crystal compositions (62) to (63) are kept in a transparent and uniform state even after being left at 0 ° C. for one week, and immediately after dissolution, they can be used as polymerizable liquid crystal compositions after leaving for one week. Even when used, an optically anisotropic material 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 horizontal alignment film was applied to a glass substrate having a thickness of 0.7 mm using a spin coating method, and then at 100 ° C. After drying for 10 minutes, a coated film was obtained by baking at 200 ° C. for 60 minutes. The resulting coating 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 resulting coated film was cooled to room temperature over 2 minutes, 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 optical anisotropic body of Example 72. The degree of polarization, transmittance, and contrast of the obtained optical 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, and it turned out that it functions as a polarizing film.
(Example 75)
After the polymerizable liquid crystal composition (75) of the present invention was obtained in the same manner as in Example 1, the obtained polymerizable liquid crystal composition (75) was spin-coated on a glass substrate having a thickness of 0.7 mm. The coating was applied, dried at 70 ° C. for 2 minutes, further dried at 100 ° C. for 2 minutes, and irradiated with 313 nm linearly polarized light for 30 seconds at an intensity of 10 mW / cm ² . Thereafter, the coated film was returned to room temperature, and ultraviolet rays were irradiated at an intensity of 30 mW / cm ² for 30 seconds using a high pressure mercury lamp to obtain an optical anisotropic body of Example 73. When the orientation of the obtained optically anisotropic body was evaluated, it was visually confirmed that there were no defects at all and no defects in polarization microscope observation. In addition, the retardation of the obtained optically anisotropic body was measured with RETS-100 (manufactured by Otsuka Electronics Co., Ltd.). The in-plane retardation (Re (550)) at a wavelength of 550 nm was 137 nm, and the uniformity was good. A phase difference film was obtained.
(Example 76)
In the same manner as in Example 1, after obtaining the polymerizable liquid crystal composition (76) of the present invention, the obtained polymerizable liquid crystal composition (76) was spin-coated on a glass substrate having a thickness of 0.7 mm. The coating was applied, dried at 60 ° C. for 2 minutes, 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 ultraviolet rays were irradiated 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, it was visually confirmed that there were no defects at all and no defects in polarization microscope observation. Further, when the retardation of the obtained optical 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 130 nm, and the uniformity was good. A phase difference film was obtained.

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

When the orientation of the obtained optically anisotropic body was evaluated, it was visually confirmed that there were no defects at all and no defects in polarization microscope observation.
The polymerizable liquid crystal composition (79) is maintained in a transparent and uniform state even after being left at 0 ° C. for one week, and immediately after dissolution, even after being left for one week, any liquid crystal composition may be visually observed. There were no orientation defects at all, and no orientation defects were observed even by polarizing microscope observation.
(Examples 80 to 86)
In the same manner as in Example 1, polymerizable liquid crystal compositions (80) to (86) of the present invention were obtained, and in the same manner as in Example 79, optically anisotropic materials were obtained, and various evaluations were performed.
The polymerizable liquid crystal compositions (80) to (86) are kept in a transparent and uniform state even after being left at 0 ° C. for 1 week, and immediately after dissolution, they can be used as polymerizable liquid crystal compositions after leaving for 1 week. Even when used, an optically anisotropic material having good orientation was obtained.

　

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

The polymerizable liquid crystal composition of the present invention includes an optically anisotropic material, a retardation film, an optical compensation film, an antireflective 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 illumination elements, optical components, polarizing films, colorants, security markings, members for laser emission, coloring materials, printed materials, structural materials, and restoration materials.

Claims (11)

1. A polymerizable liquid crystal composition comprising one or more types of liquid crystal compounds having at least one polymerizable group, a polymerization initiator, and at least one type of solvent,
   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,
   2) maintain transparency for at least 1 week in a temperature environment of 0 ° C. or less, and do not form precipitates,
   Polymerizable liquid crystal composition characterized in that.
2. A polymerizable liquid crystal composition comprising one or more types of a liquid crystal compound having at least one polymerizable group, a polymerization initiator, and at least two or more types of solvents, wherein at least one of the two or more types of solvents 2. The solvent according to claim 1, which is a solvent (a) having a cyclic structure in the molecule and having a boiling point of 170 ° C. or more (hereinafter abbreviated as “high-boiling point solvent (a)”). Polymerizable liquid crystal composition.
3. A polymerizable liquid crystal composition comprising one or more types of a liquid crystal compound having at least one polymerizable group, a polymerization initiator, and at least two or more types of solvents, wherein the above-mentioned at least two types of solvents In addition to the solvent (a), it further contains a solvent (b) having a non-cyclic structure and a boiling point lower than that of the solvent (a) (hereinafter abbreviated as "low-boiling solvent (b)"). The polymerizable liquid crystal composition according to claim 2.
4. 4. The low-boiling solvent (b) comprises at least one of -O-, -CO-, -COO-, -OH, -CONR- and -CN. 4. The polymerizable liquid crystal composition as described in the above.
5. 5. The high-boiling point solvent (a) comprises at least one of -O-, -CO-, -COO-, -OH, -CONR-, according to any one of the preceding claims. Polymerizable liquid crystal composition.
6. The polymerizable liquid crystal composition according to any one of claims 1 to 5, wherein a weight ratio of the liquid crystal compound to the solvent is 1/99 to 90/10.
7. The high-boiling point 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. The polymerizable liquid crystal composition according to any one of 1 to 6.
8. In addition to the high boiling point solvent (a) and the low boiling point solvent (b) as the solvent, a boiling point is further added between the boiling point of the high boiling point solvent (a) and the boiling point of the low boiling point solvent (b) The polymerizable liquid crystal composition according to any one of claims 1 to 7, which contains a solvent.
9. A polymer obtained by curing the non-volatile component of the polymerizable liquid crystal composition according to any one of claims 1 to 8.
10. An optically anisotropic body formed by curing the non-volatile component of the polymerizable liquid crystal composition according to any one of claims 1 to 8.
11. A display element using an optically anisotropic body obtained by curing the non-volatile component of the polymerizable liquid crystal composition according to any one of claims 1 to 8.