KR20190042046A - Polymerizable liquid crystal composition and optical film using the same - Google Patents

Abstract

And to provide a polymerizable liquid crystal composition excellent in productivity that can improve color purity. Also provided is an optical film obtained by polymerizing the polymerizable liquid crystal composition and having excellent transparency and improved color purity, a laminated film obtained by laminating the optical film and another optical element, and an image display apparatus using the optical film or laminated film will be. The present invention provides a liquid crystal composition comprising at least one polymerizable liquid crystal compound represented by the general formula (I-1), at least one polymerizable liquid crystal compound represented by the general formula (II-1) An optical film obtained by providing a polymerizable liquid crystal composition and polymerizing the polymerizable liquid crystal composition, a laminated film obtained by laminating the optical film and another optical element, and an image display apparatus using the optical film or the laminated film.

Description

Polymerizable liquid crystal composition and optical film using the same

The present invention relates to a polymerizable liquid crystal composition useful as a component of an optical anisotropic element and a reflective polarizing element used for optical compensation of a liquid crystal device, a display, an optical component, a coloring agent, a marking for security, a member for laser emission or a liquid crystal display And an optical film comprising the composition, and an image display apparatus using the optical film.

The polymerizable liquid crystal composition is useful as a constituent member of an optically anisotropic material. The optically anisotropic material is applied to various liquid crystal displays as an optical film such as a polarizing film and a retardation film. The polarizing film and the retardation film can be obtained by applying the polymerizable liquid crystal composition to a substrate, drying the solvent, and then heating or irradiating the polymerizable liquid crystal composition with an active energy ray to align the polymerizable liquid crystal composition Curing. It is also known that a circularly polarized light separation element can be obtained by using a polymerizable cholesteric liquid crystal composition to which a chiral compound is added to a polymerizable liquid crystal composition, and its application to a brightness enhancement film and the like has been studied.

Generally, in a circularly polarized light separation element produced using a polymerizable cholesteric liquid crystal composition, the relation between the selective reflection wavelength (?) And the helical pitch (p) is given by? = P 占 N (Average refractive index of the liquid crystal composition of the liquid crystal composition), and the width of the wavelength DELTA lambda representing the selective reflection is expressed by the product of the birefringence anisotropy (DELTA n) of the polymerizable liquid crystal composition and p.

Up to now, an optical film using a polymerizable cholesteric liquid crystal composition having a narrow selective reflection wavelength band has been proposed in order to increase the color purity of a light source used in a liquid crystal display device (Patent Documents 1 and 2). However, when actually examined, the desired DELTA lambda can not be obtained, and the color purity can not be increased as expected. In addition, there has been a problem because there is room for improvement in permeability and productivity.

Japanese Patent Application Laid-Open No. 2004-262884 Japanese Patent Application Laid-Open No. 2008-129483

A problem to be solved by the present invention is to provide a polymerizable liquid crystal composition excellent in productivity that can improve color purity. Also provided is an optical film obtained by polymerizing the polymerizable liquid crystal composition and having excellent transparency and improved color purity, a laminated film obtained by laminating the optical film and another optical element, and an image display apparatus using the optical film or laminated film will be.

As a result of intensive researches, the present inventors have developed a polymerizable liquid crystal composition containing a plurality of polymerizable liquid crystal compounds having a specific structure. That is, the present invention relates to a liquid crystal composition comprising at least one polymerizable liquid crystal compound represented by the general formula (I-1), at least one polymerizable liquid crystal compound represented by the general formula (II-1) An optical film obtained by polymerizing the polymerizable liquid crystal composition; a laminated film obtained by laminating the optical film and another optical element; and an image display apparatus using the optical film or the laminated film.

The polymerizable liquid crystal composition of the present invention comprises a polymerizable liquid crystal compound having two polymerizable functional groups represented by the general formula (I-1) and a polymerizable liquid crystal compound having no spacer group represented by the general formula (II-1) Is used in combination with a polymerizable liquid crystal compound having one polymerizable functional group. When the polymerizable liquid crystal composition is polymerized, the mesogen skeleton portion present in the polymerizable liquid crystal compound represented by each general formula is preferably anisotropic birefringence anisotropy, since a polymer having a low orientation order can be obtained, (DELTA n) can be suppressed to be low. As a result, it is useful for the use of an optical material such as an optical film in that an optical anisotropic body having good transparency and improved color purity can be obtained.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the best mode of the polymerizable liquid crystal composition according to the present invention will be described. In the present invention, the term " liquid crystal " of the polymerizable liquid crystal composition means a state in which the polymerizable liquid crystal composition is applied to a substrate, So as to exhibit liquid crystallinity. In the present invention, the term " liquid crystal " of the polymerizable liquid crystal compound means a compound which is a compound of only one type of polymerizable liquid crystal compound to be used, or when it is intended to exhibit liquid crystallinity or when it is mixed with other liquid crystal compounds, It is intended to represent sex. Further, the polymerizable liquid crystal composition can be polymerized (formed into a film) by performing a polymerization treatment by irradiation with light such as ultraviolet rays, heating, or a combination thereof.

The polymerizable liquid crystal composition of the present invention comprises a polymerizable liquid crystal compound having two polymerizable functional groups represented by the general formula (I-1) and a polymerizable liquid crystal compound having no spacer group represented by the general formula (II-1) In general, birefringence anisotropy (DELTA n) is the sum of the products of the individual DELTA n of each polymerizable liquid crystal compound in the polymerizable liquid crystal composition and the component ratio, while the polymerizable liquid crystal compound having one polymerizable functional group is used in combination, When the polymerization is carried out in the state where the mesogen skeleton portion in the polymerizable liquid crystal compound having no one spacer group represented by the general formula (II-2) and having one polymerizable functional group directly connected to the cyclic group is deviated from the original orientation axis , The orientation order is specifically lowered. As a result, it is possible to reduce DELTA n, and it is possible to reduce the value of the selective reflection wavelength band DELTA lambda / selective reflection central wavelength lambda when the chiral compound is added to the polymerizable liquid crystal composition.

(Bifunctional polymerizable liquid crystal compound)

(Bifunctional polymerizable liquid crystal compound represented by the general formula (I-1)

The polymerizable liquid crystal composition of the present invention contains a polymerizable liquid crystal compound having two polymerizable functional groups in the molecule (bifunctional polymerizable liquid crystal compound), wherein one or more of the polymerizable liquid crystal compound Is selected from the polymerizable liquid crystal compounds represented by the formula (I-1).

(Wherein P ¹¹¹ and P ¹¹² each independently represent a polymerizable functional group,

Sp ¹¹¹ and Sp ¹¹² each independently represent an alkylene group having 1 to 18 carbon atoms or a single bond and one -CH ₂ - in the alkylene group or two or more non-adjacent -CH ₂ - -COO-, -OCO- or -OCO-O-, one or two or more hydrogen atoms of the alkylene group may be substituted by a halogen atom or a CN group,

X ¹¹¹ and X ¹¹² each independently represent -O-, -S-, -OCH ₂ -, -CH ₂ O-, -CO-, -COO-, -OCO-, -CO-S-, CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH 2 -, -CH 2 S-, -CF 2 O-, -OCF 2 -, -CF 2 S- , -SCF ₂ -, -CH═CH-COO-, -CH═CH-OCO-, -COO-CH═CH-, -OCO-CH═CH-, -COO-CH ₂ CH ₂ -, -OCO- CH ₂ CH ₂ -, -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH ₂ -, -OCO-CH ₂ -, -CH ₂ -COO-, -CH ₂ -OCO -, -CH = CH-, -N = N-, -CH = NN = CH-, -CF = CF-, -C≡C- , or represents a single bond ^{(where, P 111 -Sp 111, P 112} - Sp ¹¹² , Sp ¹¹¹ -X ¹¹¹ and Sp ¹¹² -X ¹¹² do not contain a direct bond between oxygen atoms)

q111 and q112 each independently represent 0 or 1,

A ¹¹ and A ¹² each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group, a bicyclo [2.2.2] octane-1,4-diyl group, a pyridine- Diyl group, a naphthalene-2,6-diyl group, a naphthalene-1,4-diyl group, a tetrahydronaphthalene-2,6-diyl group, a decahydronaphthalene- Or 1,3-dioxane-2,5-diyl group, which groups may be unsubstituted or substituted by one or more substituents L,

L is a group selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group, a nitro group, a cyano group, an isocyanato group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, , A diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, an optionally substituted phenyl group, an optionally substituted phenylalkyl group, an optionally substituted cyclohexylalkyl group, or one -CH ₂ - -CH ₂ - each independently represents -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O- O-, -CO-NR ⁰ -, -NR ⁰ -CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = - CH = CH-, -N = N-, -CR ⁰ = N-, -N = CR ⁰ -, -CH = NN = CH-, -CF = CF- or -C≡C- wherein R ⁰ Represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), which may be substituted by a linear or branched alkyl group having 1 to 20 carbon atoms, And any hydrogen atom in the alkyl group may be substituted with a fluorine atom. When a plurality of L's are present in the compound, they may be the same or different. When a plurality of A ^{11 s} exist, they may be the same or different. , When a plurality of A ¹² exist, they may be the same or different,

Z ¹¹ and Z ¹² each independently represent -O-, -S-, -OCH ₂ -, -CH ₂ O-, -CH ₂ CH ₂ -, -CO-, -COO-, -OCO-, -CO -O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO- -NH-O-, -O-NH-, -SCH 2 -, -CH 2 S-, -CF 2 O-, -OCF 2 -, -CF 2 S-, -SCF 2 -, -CH = CH- -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-, -CH═NN═CH-, -CF═CF-, -C≡C-, or a single bond. When a plurality of Z ¹¹ exist, they are the same And when a plurality of Z < ¹² > s exist, they may be the same or different,

m111 and m112 each independently represent an integer of 0 to 2,

R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom, a cyano group, a hydroxyl group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, An alkylcarbonyloxy group having 2 to 10 carbon atoms, an alkylcarbonyloxy group having 2 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aromatic ring group having 5 to 12 carbon atoms, wherein either R ¹ or R ² is hydrogen Or R ² represents a cyclic group connected to the substituent L of adjacent A ^12. )

In the general formula (I-1), P ¹¹¹ and P ¹¹² each independently represent a polymerizable functional group. The following formulas (P-1) to (P-17)

, And these polymerizable groups are polymerized by radical polymerization, radical addition polymerization, cation polymerization and anionic polymerization. (P-1), formula (P-2), formula (P-3), formula (P- (P-1), P-2, P-3, P-4 and P- (P-1) or (P-10), and more preferably a formula (P-1), a formula (P- P-2) is particularly preferable.

In the general formula (I-1), q111 and q112 each independently represent 0 or 1, and from the standpoint of suppressing the birefringence anisotropy (? N) of the polymer using the obtained polymerizable liquid crystal composition, Is particularly preferable.

In the general formula (I-1), Sp ¹¹¹ and Sp ¹¹² each independently represent an alkylene group having 1 to 18 carbon atoms or a single bond, and one -CH ₂ - in the alkylene group or an adjacent Two or more of -CH ₂ - may be independently substituted with -COO-, -OCO- or -OCO-O-, and one or two or more hydrogen atoms of the alkylene group may be substituted with a halogen atom (a fluorine atom , Chlorine atom, bromine atom, iodine atom) or CN group. Further, each of Sp ¹¹¹ and Sp ¹¹² independently represents an alkylene group having 1 to 12 carbon atoms, more preferably one -CH ₂ - in the alkylene group or two or more non-adjacent -CH ₂ - May each be independently substituted with -COO-, -OCO- or -OCO-O-. It is particularly preferable that Sp ¹¹¹ and Sp ¹¹² each independently represent an alkylene group having 1 to 8 carbon atoms.

In the general formula (I), X ¹¹¹ and X ¹¹² 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 = NN = CH-, -CF = CF-, -C≡C- or a single bond. X ¹¹¹ and X ¹¹² each independently represent -O-, -OCH ₂ -, -CH ₂ O-, -CO-, -COO-, -OCO-, -O-CO-O-, -CF ₂ O-, -OCF ₂ -, -CH═CH-COO-, -CH═CH-OCO-, -COO-CH═CH-, -OCO-CH═CH-, -COO-CH ₂ CH ₂ -, - OCO-CH ₂ CH ₂ -, -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH ₂ -, -OCO-CH ₂ -, -CH ₂ -COO-, -CH ₂ -OCO-, -CH = CH-, -CF = CF-, -C? C-, or a single bond. It is particularly preferable that X ¹¹¹ and X ¹¹² each independently represent -O- or a single bond.

In the general formula (I-1), A ¹¹ and A ¹² each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group, a bicyclo [2.2.2] octane- A pyrimidine-2,5-diyl group, a naphthalene-2,6-diyl group, a naphthalene-1,4-diyl group, a tetrahydronaphthalene-2,6- Dioxane-2,5-diyl group, which groups may be unsubstituted or substituted by one or more substituents L, From the viewpoints of ease of synthesis, availability of raw materials, and liquid crystallinity, A ¹¹ and A ¹² each independently represent a 1,4-phenylene group which may be unsubstituted or substituted by at least one substituent L, a 1,4- A naphthalene-2,6-diyl group, or a naphthalene-1,4-diyl group, and each independently represents a group represented by the following formula A-1) to (A-16)

And R < 2 > (A-1) to (A-7) and (A-10), it is more preferred that each of A ¹¹ and A ¹² present independently represents a group selected from the above formulas are each preferably, is present a ¹¹ and a ¹² is a ¹¹ and a ^12, which is more preferred, and there represent a group each independently selected from the above formula (a-1) to formula (a-7) to independently It is particularly preferable to represent a group selected from the above formulas (A-1) to (A-4). When there are a plurality of A ¹¹ , they may be the same or different, and when a plurality of A ¹² exist, they may be the same or different.

In the general formula (I-1), L represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, a cyano group, an isocyano group, A substituted or unsubstituted alkyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkyl group, Or one -CH ₂ - or two or more non-adjacent -CH ₂ - are each independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -CO-O-, -CO-NR ⁰ -, -NR ⁰ -CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH -, -OCO-CH = CH-, -CH = CH-, -N = N-, -CR ⁰ = N-, -N = CR ⁰ -, -CH = NN = CH-, -CF = CF- or -C≡C- carbon source which may be substituted by (wherein, R ⁰ represents a hydrogen atom or an alkyl group with 1 to 8 carbon atoms.) Represent the number from 1 to 20 linear or branched alkyl group of the art random hydrogen atom in the alkyl group is optionally substituted with fluorine atoms, if present in the compounds L is plural, they may be the same or different. The substituent L is preferably 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 an arbitrary hydrogen atom -CH ₂ - or two or more non-adjacent -CH ₂ - are each independently selected from the group consisting of -O-, -S-, -CO-, -COO-, -OCO-, - O-CO-O-, -CH = CH-, -CF = CF- or -C≡C-, and is preferably a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted , The substituent L may be a fluorine atom, a chlorine atom, or an arbitrary hydrogen atom may be substituted with a fluorine atom, and one -CH ₂ - or two or more non-adjacent -CH ₂ - s are each independently -O-, COO- or -OCO-, which may be substituted by a group selected from a straight-chain Or a branched alkyl group, and the substituent L represents a fluorine atom, a chlorine atom, or a straight or branched alkyl group or alkoxy group having 1 to 12 carbon atoms which may be substituted with a fluorine atom It is more preferable that the substituent L represents a fluorine atom, a chlorine atom, or a straight chain alkyl group or a straight chain alkoxy group having 1 to 8 carbon atoms.

In formula (I-1), Z ¹¹ and Z ¹² each 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-} 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 = NN = CH-, -CF = CF-, -C≡C- or a single bond, When a plurality of Z ^{11 s} exist, they may be the same or different and when a plurality of Z ^{12 s} exist, they may be the same or different. In particular, when it is emphasized that fewer alignment defects are present, Z ¹¹ and Z ¹² may be the same or different from each other when a plurality of Z ¹¹ and Z ¹² are independently present, and -OCH ₂ -, -CH ₂ O-, -CH ₂ CH ₂ - -COO-, -OCO-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -OCO-CH = CH-, -COO-CH 2 CH 2 -, -CH 2 CH 2 -OCO-, -CH = CH-, -N = N-, -CH = N-, -N = CH-, -CH = NN = CH-, -CF = CF-, Z ¹¹ and Z ¹² each independently may be the same or different from each other when a plurality of Z ¹¹ and Z ¹² are present and may be the same or different from each other and represent -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CO-NH -, -NH-CO-, -CH = CH-COO-, -OCO-CH = CH-, -CH = CH-, -N = N-, -CH = NN = CH-, -C≡C-, or a single bond, and Z ¹¹ and Z ¹² each independently may be the same or different when a plurality of Z ¹¹ and Z ¹² are independently present, and -OCH ₂ -, -CH ₂ O-, -COO- , -OCO-, -CO-NH-, -NH-CO- or a single bond, more preferably Z ¹¹ and Z ¹² are each independently They may be the same or different and are particularly preferably -OCH ₂ -, -CH ₂ O-, -COO-, -OCO- or a single bond.

In the general formula (I-1), m111 and m112 each independently represent an integer of 0 to 2, with m111 + m112 being preferably 1 or 2, m111 + m112 being more preferably 2, and m111 and m112 being both 1 Particularly preferred.

In formula (I-1), R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom, a cyano group, a hydroxyl group, a nitro group, an alkyl group having 1 to 10 carbon atoms, An alkoxy group of 1 to 10 carbon atoms, an acyl group of 2 to 10 carbon atoms, an alkylcarbonyloxy group of 2 to 10 carbon atoms, an alkoxycarbonyl group of 2 to 10 carbon atoms, or an aromatic ring group of 5 to 12 carbon atoms, Either R ¹ or R ² represents other than a hydrogen atom. More preferable examples of the group other than the hydrogen atom include a fluorine atom, a cyano group, a hydroxyl group, a nitro group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, More preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. Either R ¹ or R ² represents other than a hydrogen atom, and it is preferable that one of R ¹ and R ² represents a hydrogen atom and the other represents a hydrogen atom.

Or, R ² is connected with a substituent having an A ¹² adjacent to exist L preferably represents a cyclic.

The bifunctional polymerizable liquid crystal compound represented by the general formula (I-1) may be used alone or in combination of two or more. The total content of the bifunctional polymerizable liquid crystal compound represented by the general formula (I-1) In order to specifically reduce Δn in the total amount of the polymerizable liquid crystal compound used in the liquid crystal composition, the content is preferably 10 to 95 mass%, and more preferably 20 to 90 mass%. In order to facilitate the expression of the twisted nematic phase or the cholesteric phase when the chiral compound is added to the polymerizable liquid crystal composition, it is preferable that the polymerizable liquid crystal composition contains 30 to 85% by mass of the total amount of the polymerizable liquid crystal compounds used in the polymerizable liquid crystal composition Particularly preferred. Specifically, when the following general formulas (I-1-1) to (I-1-23) are used, it is preferable that they are contained in the ratio.

As the compound represented by the general formula (I-1), the compounds represented by the following general formulas (I-1-1) to (I-1-23) are preferable.

(Wherein R ^c represents a fluorine atom, a cyano group, a hydroxyl group, a nitro group, an alkyl group having 1 to 10 carbon atoms, a carbon atom (s) An alkoxy group having a number of 1 to 10, an acyl group having 2 to 10 carbon atoms, an alkylcarbonyloxy group having 2 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aromatic ring having 5 to 12 carbon atoms, represents, R ^e and R ^d are each, independently, a hydrogen atom or a methyl group, m1 and m2 each independently represents an integer of 0 ~ 8, n1 and n2 are to represent independently 0 or 1, m1 = 0 N1 = 0, and when m2 = 0, n2 = 0).

The compounds represented by the above general formulas (I-1-1) to (I-1-23) are more specifically represented by the following general formulas (I-1-1-1) to -60), but are not limited thereto.

(Bifunctional polymerizable liquid crystal compound represented by the general formula (I-2)

The polymerizable liquid crystal composition of the present invention contains one or more bifunctional polymerizable liquid crystal compounds represented by the above-mentioned general formula (I-1), wherein the bifunctional polymerization represented by the general formula (I-1) One or more polymerizable liquid crystal compounds selected from the bifunctional polymerizable liquid crystal compounds represented by the following general formula (I-2) may be used in combination with the liquid crystal compound.

(Wherein, P ¹²¹ and P ¹²² each independently represent a polymerizable functional group; Sp ¹²¹ and Sp ¹²² each independently represent an alkylene group having 1 to 18 carbon atoms or a single bond; and 1 in the alkylene group -CH ₂ -, or two or more non-adjacent -CH ₂ - groups may be independently substituted with -COO-, -OCO- or -OCO-O-, and one or two of the alkylene groups Or more of the hydrogen atoms may be substituted by a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) or CN group, and X ¹²¹ and X ¹²² each independently represents -O-, -S-, -OCH ₂ - _{, -CH 2 O-, -CO-, -COO-} , -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- _{, -SCH 2 -, -CH 2 S-} , -CF 2 O-, -OCF 2 -, -CF 2 S-, -SCF 2 -, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH ₂ -, -OCO-CH ₂ CH ₂ -, -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO -, -COO-CH ₂ -, -OCO-CH ₂ -, -CH ₂ -COO-, -CH ₂ -OCO-, -CH═CH-, -N═N-, -CH═NN═CH-, -CF = C (Provided that P ¹²¹ -Sp ¹²¹ , P ¹²² -Sp ¹²² , Sp ¹²¹ -X ¹²¹ and Sp ¹²² -X ¹²² contain a direct bond between heteroatoms) , Q121 and q122 each independently represent 0 or 1, and MG ¹²¹ represents a mesogen group.)

In the general formula (I-2), P ¹²¹ and P ¹²² each independently represent a polymerizable functional group, and the following formulas (P-1) to (P-17)

, And these polymerizable groups are polymerized by radical polymerization, radical addition polymerization, cation polymerization and anionic polymerization. (P-1), formula (P-2), formula (P-3), formula (P- (P-1), P-2, P-3, P-4 and P- (P-1) or (P-10), and more preferably a formula (P-1), a formula (P- P-2) is particularly preferable.

In the general formula (I-2), Sp ¹²¹ and Sp ¹²² each independently represent an alkylene group having 1 to 15 carbon atoms, and one -CH ₂ - in the alkylene group is adjacent to -CH ₂ - each independently may be substituted by -COO-, -OCO- or -OCO-O-, and one or two or more hydrogen atoms of the alkylene group may be replaced by a halogen atom (fluorine Sp ¹¹ and Sp ¹² each independently represent an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 12 carbon atoms in the alkylene group, -CH ₂ - or two or more non-adjacent -CH ₂ - may be independently substituted with -O-, -COO-, -OCO- or -OCO-O-.

In the general formula (I-2), X ¹²¹ and X ¹²² each independently represents -O-, -OCH ₂ -, -CH ₂ O-, -CO-, -COO-, -OCO-, -O -CO-NH-, -NH-CO-, -CF ₂ O-, -OCF ₂ -, -CH = CH-COO-, -CH = CH-OCO-, -COO- -CHO-, -OCO-CH = CH-, -COO-CH ₂ CH ₂ -, -OCO-CH ₂ CH ₂ -, -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, CH ₂ -, -OCO-CH ₂ -, -CH ₂ -COO-, -CH ₂ -OCO-, -CH═CH-, -N═N-, -CH═NN═CH-, , -C≡C- or a single bond, and X ¹²¹ and X ¹²² each independently represent -O-, -OCH ₂ -, -CH ₂ O-, -CO-, -COO-, -OCO -O-CO-O-, -CF ₂ O-, -OCF ₂ -, -CH═CH-COO-, -CH═CH-OCO-, -COO-CH═CH-, -OCO- CH ₂ -, -COO-CH ₂ CH ₂ -, -OCO-CH ₂ CH ₂ -, -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH ₂ - ₂ -, -CH ₂ -COO-, -CH ₂ -OCO-, -CH═CH-, -CF═CF-, -C≡C-, or a single bond.

MG ¹²² represents a mesogen group, and general formula (I-2-b)

In formula (I-2-b), A1, A2 and A3 each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group, a 1,4-cyclohexenyl group, a tetrahydropyran- A 2,5-diyl group, a 1,3-dioxane-2,5-diyl group, a tetrahydrothiopyran-2,5-diyl group, a 1,4-bicyclo (2,2,2) A thiophene-2,5-diyl group, a thiophene-2,5-diyl group, a pyridine-2,5-diyl group, 2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene- , 1,2,3,4,4a, 9,10a-octahydrophenanthrene-2,7-diyl group, 1,4-naphthylene group, benzo [1,2- Dithienophen-2,6-diyl group, [1] benzothieno [3,2-b] thiophene-2,6-diyl group, benzo [1,2- A benzeneselenopheno [3,2-b] selenophene-2,7-diyl group, or a fluorene-2,7-diyl group, Z1 and Z2 represent each _{independently, -COO-, -OCO-, -CH 2 CH} 2 -, -OCH 2 -, -CH _{2 O-, -CH = CH-, -C≡C-} , -CH = CHCOO-, -OCOCH = CH-, -CH 2 CH 2 COO-, -CH 2 CH 2 OCO-, -COOCH 2 CH 2 - , -OCOCH ₂ CH ₂ -, -C═N-, -N═C-, -CONH-, -NHCO-, -C (CF ₃ ) ₂ -, a halogen atom (fluorine, chlorine, bromine, represents the atoms) alkyl group or an import terminal of Fig. the number of carbon atoms of 2 to 10 which is a combined, Z1 and Z2 are independently -COO-, -OCO-, -CH ₂ CH _2, respectively -, -OCH ₂ -, -CH ₂ O-, -CH = CH-, -C≡C-, -CH = CHCOO-, -OCOCH = CH-, -CH 2 CH 2 COO-, -CH 2 CH 2 OCO-, -COOCH 2 CH 2 -, -OCOCH ₂ CH ₂ - or a single bond, and is preferably -COO-, -OCO-, -OCH ₂ -, -CH ₂ O-, -CH ₂ CH ₂ O-, -CH ₂ CH ₂ OCO-, _{COOCH 2 CH 2 -, -OCOCH 2} CH 2 - or a single bond and in that more preferably, r1 represents 0, 1, 2 or 3, in the case of A1 and Z1 are the presence of a plurality, respectively, it is the same, different You can. Of these, A1, A2 and A3 each independently preferably represent a 1,4-phenylene group, a 1,4-cyclohexylene group or a 2,6-naphthylene group.

Examples of the compound represented by the general formula (I-2) include compounds represented by the following general formulas (I-2-1) to (I-2-4), but are not limited to the following general formulas.

In the formula, P ¹²¹ , Sp ¹²¹ , X ¹²¹ , q121, X ¹²² , Sp ¹²² , q122 and P ¹²² each have the same definition as in formula (I-

A11, A12, A13, A2 and A3 are the same as defined in A1 to A3 in the above general formula (I-2-b) and may be the same or different,

Z11, Z12, Z13 and Z2 each have the same definition as Z1 and Z2 in the general formula (I-2-b), and may be the same or different.

Among the compounds represented by the general formulas (I-2-1) to (I-2-4), the compounds represented by the general formulas (I-2-2) to (I- 2-4) The use of a compound having a cyclic structure is preferable because the obtained optically anisotropic substance has good orientation properties, and it is particularly preferable to use a compound represented by the general formula (I-2-2) having three ring structures in the compound.

Examples of the compounds represented by the general formulas (I-2-1) to (I-2-4) include compounds represented by the following general formulas (I-2-1-1) to (I-2-1-36) Compounds to be displayed are exemplified, but are not limited thereto.

R ^d and R ^e each independently represent a hydrogen atom, a fluorine atom, a trifluoromethyl group or a methyl group,

The cyclic group, at least 1 F as a substituent, Cl, CF _3, OCF _3, CN groups, carbon atoms, 1-8 alkyl groups, the number of carbon atoms 1-8 alkoxy group, the number of carbon atoms 1-8 of the alkanoyl An alkanoyloxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, An alkenoyl group having 2 to 8 carbon atoms, an alkenoyloxy group having 2 to 8 carbon atoms,

Each of m1, m2, m3 and m4 independently represents an integer of 0 to 18, preferably an integer of 0 to 8, and n1, n2, n3 and n4 each independently represent 0 or 1.

The bifunctional polymerizable liquid crystal compound represented by the general formula (I-2) may be used alone or in combination of two or more. The total content of the bifunctional polymerizable liquid crystal compound represented by the general formula (I-2) Is preferably contained in an amount of 0 to 50 mass%, more preferably 0 to 30 mass%, in the total amount of the polymerizable liquid crystal compound used in the liquid crystal composition. In order to facilitate the expression of the twisted nematic phase or the cholesteric phase when the chiral compound is added to the polymerizable liquid crystal composition, it is preferable that the structure of the compound is asymmetric or that the compound has a substituent at the mesogen skeleton, And particularly preferably 0 to 20% by mass of the total amount of the polymerizable liquid crystal compound used in the polymerizable liquid crystal composition. Specifically, the compounds represented by the general formulas (I-2-1) to (I-2-4), the compounds represented by the general formulas (I-2-1-1) to -36) is also preferably used in the ratio.

The compounds represented by the general formulas (I-2-1-1) to (I-2-1-36) are more specifically represented by the following general formulas (I-2-2-1) to -2-2-41), but the present invention is not limited thereto.

(Monofunctional polymerizable liquid crystal compound)

(Monofunctional polymerizable liquid crystal compound represented by the general formula (II-1)

The polymerizable liquid crystal composition of the present invention contains a polymerizable liquid crystal compound (monofunctional polymerizable liquid crystal compound) having one polymerizable functional group in the molecule, wherein one or more of the polymerizable liquid crystal compound Is selected from the polymerizable liquid crystal compounds represented by the formula (I-1).

(In the general formula (II-1), P ²¹¹ represents a polymerizable functional group,

A ²¹¹ and A ²¹² each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group, a bicyclo [2.2.2] octane-1,4-diyl group, a pyridine- Diyl group, a naphthalene-2,6-diyl group, a naphthalene-1,4-diyl group, a tetrahydronaphthalene-2,6-diyl group, a decahydronaphthalene- Or 1,3-dioxane-2,5-diyl group, which groups may be unsubstituted or substituted by one or more substituents L,

L is a group selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group, a nitro group, a cyano group, an isocyanato group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, , A diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, an optionally substituted phenyl group, an optionally substituted phenylalkyl group, an optionally substituted cyclohexylalkyl group, or one -CH ₂ - -CH ₂ - each independently represents -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O- O-, -CO-NR ⁰ -, -NR ⁰ -CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = - CH = CH-, -N = N-, -CR ⁰ = N-, -N = CR ⁰ -, -CH = NN = CH-, -CF = CF- or -C≡C- wherein R ⁰ Represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), which may be substituted by a linear or branched alkyl group having 1 to 20 carbon atoms, And any hydrogen atoms in the alkyl group may be substituted with a fluorine atom. When a plurality of L's are present in the compound, they may be the same or different. When a plurality of A ²¹² 's exist, they may be the same or different. ,

Z ²¹¹ _{is, -O-, -S-, -OCH 2 -} , -CH 2 O-, -CH 2 CH 2 -, -CO-, -COO-, -OCO-, -CO-S-, -S -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH- _{-O-NH-, -SCH 2 -,} -CH 2 S-, -CF 2 O-, -OCF 2 -, -CF 2 S-, -SCF 2 -, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-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-, -N = CH-, -CH = NN = CH-, -CF = CF-, -C≡C- or a single bond. When a plurality of Z ²¹¹ exist, they may be the same or different,

m211 represents an integer of 1 to 3,

T ²¹¹ represents a hydrogen atom, -OH group, -SH group, -CN group, -COOH group, -NH ₂ group, -NO ₂ group, -COCH _{3 group, -O (CH 2) n CH} 3, or - ( CH ₂ ) _n CH ₃ , and n represents an integer of 0 to 20.

In the general formula (II-1), P ²¹¹ represents a polymerizable functional group, and the following formulas (P-1) to (P-17)

, And these polymerizable groups are polymerized by radical polymerization, radical addition polymerization, cation polymerization and anionic polymerization. (P-1), formula (P-2), formula (P-3), formula (P- (P-1), P-2, P-3, P-4 and P- (P-1) or (P-10), and more preferably a formula (P-1), a formula (P- P-2) is particularly preferable.

In the general formula (II-1), A ²¹¹ and A ²¹² each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group, a bicyclo [2.2.2] octane- A pyrimidine-2,5-diyl group, a naphthalene-2,6-diyl group, a naphthalene-1,4-diyl group, a tetrahydronaphthalene-2,6- Dioxane-2,5-diyl group, which groups may be unsubstituted or substituted by one or more substituents L, From the viewpoints of ease of synthesis, availability of raw materials, and liquid crystallinity, A ²¹¹ and A ²¹² each independently represent a 1,4-phenylene group which may be unsubstituted or substituted by at least one substituent L, a 1,4- A naphthalene-2,6-diyl group, or a naphthalene-1,4-diyl group, and each independently represents a group represented by the following formula A-1) to (A-16)

And R < 2 > At least one of A ²¹¹ and A ²¹² represents a group selected from the above-mentioned formula (A-2) or formula (A-10), and the remainder each independently represents a group selected from the above- (A-1) to (A-7) and (A-10), and at least one of A ²¹¹ and A ²¹² represents a group selected from the group represented by the formula (A-2) (A-1) to (A-7), and at least one of A ²¹¹ and A ²¹² is a group selected from the above-mentioned formula (A-2) , And the remainder each independently represent a group selected from the above formulas (A-1) to (A-4). When a plurality of A ²¹² exist, they may be the same or different.

In the general formula (II-1), L represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group, a nitro group, a cyano group, an isocyanato group, an amino group, a hydroxyl group, A substituted or unsubstituted alkyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkyl group, Or one -CH ₂ - or two or more non-adjacent -CH ₂ - are each independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -CO-O-, -CO-NR ⁰ -, -NR ⁰ -CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH -, -OCO-CH = CH-, -CH = CH-, -N = N-, -CR ⁰ = N-, -N = CR ⁰ -, -CH = NN = CH-, -CF = CF- or -C≡C- (wherein R ⁰ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms) Represents a linear or branched alkyl group of 1 to 20 in embroidery number, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom. When a plurality of Ls exist in the compound, they may be the same or different. The substituent L is preferably 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 an arbitrary hydrogen atom -CH ₂ - or two or more non-adjacent -CH ₂ - are each independently selected from the group consisting of -O-, -S-, -CO-, -COO-, -OCO-, - O-CO-O-, -CH = CH-, -CF = CF- or -C≡C-, and is preferably a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted , The substituent L may be a fluorine atom, a chlorine atom, or an arbitrary hydrogen atom may be substituted with a fluorine atom, and one -CH ₂ - or two or more non-adjacent -CH ₂ - s are each independently -O-, COO- or -OCO-, which may be substituted by a group selected from a straight-chain Or a branched alkyl group, and the substituent L represents a fluorine atom, a chlorine atom, or a straight or branched alkyl group or alkoxy group having 1 to 12 carbon atoms which may be substituted with a fluorine atom It is more preferable that the substituent L represents a fluorine atom, a chlorine atom, or a straight chain alkyl group or a straight chain alkoxy group having 1 to 8 carbon atoms.

In the general formula (II-1), Z ²¹² 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-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-, , -N = N-, -CH = N- , -N = CH-, -CH = NN = CH-, -CF = CF-, -C≡C- , or represent a single bond, Z ²¹² is a plurality presence They may be the same or different.

In the formula (II-1), when there are a plurality of Z ²¹² , when there are a plurality of alignment defects, they may be the same or different and may be the same or different from each other when -OCH ₂ -, -CH ₂ O-, -CH ₂ CH _{2 -, -COO-, -OCO-, -CO} -NH-, -NH-CO-, -CF 2 O-, -OCF 2 -, -CH = CH-COO-, -OCO-CH = CH-, -COO-CH ₂ CH ₂ -, -CH ₂ CH ₂ -OCO-, -CH = CH-, -N = N-, -CH = N-, -N = CH-, -CH = -CF═CF-, -C≡C- or a single bond, and when there are a plurality of Z ^{212 s} , they may be the same or different and may be different from each other and represent -COO-, -OCO-, -CO-NH-, -NH _{-CO-, -CF 2 O-, -OCF 2} -, -CH = CH-COO-, -OCO-CH = CH-, -CH = CH-, -N = N-, -CH = NN = CH- , -CF = CF-, -C≡C-, or a single bond, and when a plurality of Z ^{212 's} are present, they may be the same or different and are -COO-, -OCO-, -CO- _{-NH-CO-, -CF 2 O-,} -OCF 2 - or a single bond, and more preferably represents a, Z ²¹² is a case that a plurality exists but they may be the same or different It said _{-COO-, -OCO-, -CF 2 O-,} -OCF 2 - is especially preferred that represents a single bond or.

In the general formula (II-1), m211 represents an integer of 1 to 3, m211 is preferably 1 or 2, and m211 is preferably 1.

Wherein in the formula (II-1), T ²¹¹ is a hydrogen atom, -OH group, -SH group, -CN group, -COOH group, -NH ₂ group, -NO ₂ group, -COCH ₃ group, -O (CH ₂ ) _n CH ₃ , or - (CH ₂ ) _n CH ₃ (n represents an integer of 0 to 20), and T ²¹¹ represents a hydrogen atom, -O (CH ₂ ) _n CH ₃ , CH _{2) n} CH _{3 (n} is and it is more preferable that indicates an integer of ^{0 ~ 10), T 211,} -O (CH 2) n CH 3, or _{- (CH 2) n CH 3} (n is Represents an integer of 0 to 8).

The monofunctional polymerizable liquid crystal compound represented by formula (II-1) may be used singly or in combination of two or more. The total content of the monofunctional polymerizable liquid crystal compound represented by formula (II-1) Is preferably contained in an amount of 5 to 85 mass%, more preferably 10 to 80 mass%, in the total amount of the polymerizable liquid crystal compound used in the liquid crystal composition. In order to suppress the birefringence anisotropy (? N) to be low when the polymerizable liquid crystal composition is polymerized, it is particularly preferable that the polymerizable liquid crystal composition contains 15 to 70% by mass of the total amount of polymerizable liquid crystal compounds used in the polymerizable liquid crystal composition. Specifically, when the following general formulas (II-1-1) to (II-1-22) are used, it is also preferable that they are contained in the ratio.

As the compound represented by the general formula (II-1), the compounds represented by the following general formulas (II-1-1) to (II-1-22) are preferable.

In the general formulas (II-1-1) to (II-1-22), R ^c represents a hydrogen atom, a fluorine atom, a trifluoromethyl group or a methyl group, and the cyclic group is a group in which a hydrogen atom is substituted with a substituent A fluorine atom, a chlorine atom, a pentafluorosulfanyl group, a nitro group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group or an arbitrary hydrogen atom may be substituted with a fluorine atom And one -CH ₂ - or two or more non-adjacent -CH ₂ - are each independently selected from the group consisting of -O-, -S-, -CO-, -COO-, -OCO-, -O-CO-O -, -CH = CH-, -CF = CF- or -C≡C-, T ^c represents a hydrogen atom, - OH group, -SH group, -CN group, -COOH group, -NH ₂ group, -NO ₂ group, -COCH ₃ group, -O (CH ₂ ) _n CH ₃ or - (CH ₂ ) _n CH ₃ and n represents an integer of 0 to 20) Produce.

Specific examples of the compounds represented by the general formulas (II-1-1) to (II-1-22) include compounds represented by the following formulas (II-1-1-1) to (II-1-1- ) Is preferable.

(Monofunctional Polymerizable Liquid Crystalline Compound Represented by Formula (II-2)

The polymerizable liquid crystal composition of the present invention contains one or more monofunctional polymerizable liquid crystal compounds represented by the above general formula (II-1), wherein the monofunctional polymerization represented by the general formula (II-1) One or more polymerizable liquid crystal compounds selected from monofunctional polymerizable liquid crystal compounds represented by the following general formula (II-2) may be used in combination with the liquid crystal compound.

In the formula, P ²²¹ represents a polymerizable functional group, Sp ²²¹ represents an alkylene group having 1 to 18 carbon atoms or a single bond, and one -CH ₂ - in the alkylene group or two or more non-adjacent -CH ₂ - may each be independently substituted with -O-, -COO-, -OCO- or -OCO-O-, and one or two or more hydrogen atoms of the alkylene group may be substituted with a halogen atom (a fluorine atom, and may be substituted by a chlorine atom, a bromine atom, an iodine atom), or CN, X ²²¹ is _{-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 - _2- COO-, -CH ₂ -OCO-, -CH═CH-, -N═N-, -CH═NN═CH-, -CF═CF-, -C≡C- or a single bond in, P ²²¹ -Sp ^221, and Sp ²²¹ -X ^221, C, does not include a direct bond between the hetero atom other than H.), MG ²²¹ denotes a mesogen group, R ²²¹ is a hydrogen atom, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a cyano group, a straight chain of 1 to 12 carbon atoms or branched alkyl group, the carbon atom number of 1 to 12 represents a straight chain or branched alkenyl, the alkyl group and alkenyl group of 1 -CH ₂ -, or are not adjacent two or more - CH ₂ - are each independently selected from the group consisting of -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O- NH-, -NH-CO-, -NH-, -N (CH 3) -, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = -CH = CH-, -CF = CF- or -C? C-, and one or two or more hydrogen atoms of the alkyl group and the alkenyl group thereof may be independently substituted with a halogen atom ( A fluorine atom, a chlorine atom, a bromine atom, an iodine atom) or a cyano group, They may be the same or different from each other.

In the general formula (II-2), P ²²¹ represents a polymerizable functional group, and the following formulas (P-1) to (P-17)

, And these polymerizable groups are polymerized by radical polymerization, radical addition polymerization, cation polymerization and anionic polymerization. (P-1), formula (P-2), formula (P-3), formula (P- (P-1), P-2, P-3, P-4 and P- (P-1) or (P-10), and more preferably a formula (P-1), a formula (P- P-2) is particularly preferable.

In the general formula (II-2), Sp ²²¹ represents an alkylene group having 1 to 15 carbon atoms, and one -CH ₂ - in the alkylene group or two or more non-adjacent -CH ₂ - may each independently be replaced by -O-, -COO-, -OCO- or -OCO-O-, and one or two or more hydrogen atoms of the alkylene group may be replaced by a halogen atom (fluorine atom, chlorine An atom, a bromine atom, an iodine atom) or a CN group, and Sp ²² is more preferably an alkylene group having 1 to 12 carbon atoms, and one of -CH ₂ - in the alkylene group or an adjacent Two or more -CH ₂ - may each independently be replaced by -O-, -COO-, -OCO- or -OCO-O-.

In the general formula (II-2), X ²²¹ represents -O-, -OCH ₂ -, -CH ₂ O-, -CO-, -COO-, -OCO-, -O-CO- CO-NH-, -NH-CO-, -CF ₂ O-, -OCF ₂ -, -CH═CH-COO-, -CH═CH-OCO-, -COO-CH═CH-, -OCO-CH _{= CH-, -COO-CH 2 CH} 2 -, -OCO-CH 2 CH 2 -, -CH 2 CH 2 -COO-, -CH 2 CH 2 -OCO-, -COO-CH 2 -, -OCO- CH ₂ -, -CH ₂ -COO-, -CH ₂ -OCO-, -CH═CH-, -N═N-, -CH═NN═CH-, -CF═CF-, -C≡C- or And X ²²¹ represents -O-, -OCH ₂ -, -CH ₂ O-, -CO-, -COO-, -OCO-, -O-CO-O-, -CF ₂ O -, -OCF ₂ -, -CH═CH-COO-, -CH═CH-OCO-, -COO-CH═CH-, -OCO-CH═CH-, -COO-CH ₂ CH ₂ -, -OCO _{-CH 2 CH 2 -, -CH 2} CH 2 -COO-, -CH 2 CH 2 -OCO-, -COO-CH 2 -, -OCO-CH 2 -, -CH 2 -COO-, -CH 2 - OCO-, -CH = CH-, -CF = CF-, -C? C-, or a single bond.

In the general formula (II-2), MG ²²¹ represents a mesogen group, and general formula (II-2-b)

(Wherein A1 and A2 are each independently a 1,4-phenylene group, a 1,4-cyclohexylene group, a 1,4-cyclohexenyl group, a tetrahydropyran-2,5-diyl group, Dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6- , 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 A 2,6-diyl group, a 2,6-naphthylene group, a phenanthrene-2,7-diyl group, a 9,10-dihydrophenanthrene-2,7-diyl group, 4a, 9,10a-octahydrophenanthrene-2,7-diyl group, 1,4-naphthylene group, benzo [1,2- b: 4,5-b '] dithiophene- , Benzo [1,2-b: 4,5-b '] dicselenophen-2,6-diyl group, [1] benzothieno [3,2- b] thiophene- A benzenecenopheno [3,2-b] selenophene-2,7-diyl group, a fluorene-2,7-diyl group, a cholesteryl group or a cholesteryl group, and as the substituent L ² , 1 one or more _{F, Cl, CF 3, OCF} 3 , An CN group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, An alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, an alkenoyl group having 2 to 8 carbon atoms, and / or an alkenoyl group having 2 to 8 carbon atoms And A 1 to A 3 each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group or a 2,6-naphthylene group which may have the substituent L ² The substituent L ² is preferably F, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms.

In the general formula (II-2), R ²²¹ represents a hydrogen atom, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, More preferably a straight-chain or branched alkenyl group having 1 to 8 atoms, and one -CH ₂ - in the alkyl group and alkenyl group or two or more -CH ₂ - groups not adjacent to each other are each independently -O-, -COO-, -OCO-, -O-CO-O-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH -, -CH = CH-, or -C? C-, and one or two or more hydrogen atoms of the alkyl group and the alkenyl group may be substituted with a halogen atom (fluorine atom, chlorine atom, Bromine atom, iodine atom) or a cyano group, and when they are plurally substituted, they may be the same or different.

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

In the formulas, P ²²¹ , Sp ²²¹ , X ²²¹ and R ²²¹ each have the same definition as that of the formula (II-2)

A11, A12, A13, A2 and A3 are the same as defined for A1 to A3 in the general formula (II-2-b) and may be the same or different,

Z11, Z12, Z13 and Z2 are the same as defined for Z1 to Z3 in the general formula (II-2-b), may be the same or different,

Examples of the compounds represented by the general formulas (II-2-1) to (II-2-4) include compounds represented by the following general formulas (II-2-1-1) to (II-2-1-26) Compounds to be displayed are exemplified, but are not limited thereto.

In the general formulas (II-2-1-1) to (II-2-1-26), R ^c represents a hydrogen atom or a methyl group, m represents an integer of 1 to 18, n represents 0 or represents 1, R ²²¹ is the formula (II-2-1) ~ identical to indicate that the definition of (II-2-4), R ²²¹ is a hydrogen atom, a halogen atom (fluorine atom, chlorine atom, bromine A straight chain alkyl group having 1 to 6 carbon atoms or a straight chain alkyl group having 1 to 6 carbon atoms, which may be substituted with -O-, -CO-, -COO-, -OCO-, -CH ₂ - A straight chain alkenyl group having 1 to 6 carbon atoms.

In the general formulas (II-2-1-1) to (II-2-1-26), the cyclic group may have at least one F, Cl, CF ₃ , OCF ₃ , CN group, An alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carbon An alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, an alkenoyl group having 2 to 8 carbon atoms, and an alkenoyloxy group having 2 to 8 carbon atoms.

The monofunctional polymerizable liquid crystal compound represented by formula (II-2) may be used singly or in combination of two or more. The total content of the monofunctional polymerizable liquid crystal compound represented by formula (II-2) Is preferably contained in an amount of 0 to 40 mass%, more preferably 0 to 35 mass%, in the total amount of the polymerizable liquid crystal compound used in the liquid crystal composition. In order to suppress the birefringence anisotropy (? N) to be low when the polymerizable liquid crystal composition is polymerized, it is particularly preferable that the polymerizable liquid crystal composition contains 0 to 30% by mass of the total amount of polymerizable liquid crystal compounds used in the polymerizable liquid crystal composition. More specifically, when the above general formulas (II-2-1) to (II-2-4) are used, the compounds represented by formulas (II-2-1-1) to -1-26) is also preferably used in the ratio.

(Multifunctional polymerizable liquid crystal compound)

The polymerizable liquid crystal composition of the present invention may contain a polymerizable liquid crystal compound having three or more polymerizable functional groups in the molecule within a range that does not impair the physical properties. Examples of the polymerizable liquid crystal compound having three or more polymerizable functional groups in the molecule include compounds represented by the following general formulas (III-1) and (III-2).

(Wherein P ³¹ to P ³⁵ each independently represent a polymerizable functional group; Sp ³¹ to S ³⁵ each independently represent an alkylene group having 1 to 18 carbon atoms or a single bond; -CH ₂ - or two or more non-adjacent -CH ₂ - groups may be independently substituted with -O-, -COO-, -OCO- or -OCO-O-, and the alkylene group having 1 Or two or more hydrogen atoms may be substituted by a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) or CN group, and each of X ³¹ to X ³⁵ independently represents -O-, -S-, -OCH ₂ -, -CH ₂ O-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, _{NH-CO-, -SCH 2 -,} -CH 2 S-, -CF 2 O-, -OCF 2 -, -CF 2 S-, -SCF 2 -, -CH = CH-COO-, -CH = CH -OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH 2 CH 2 -, -OCO-CH 2 CH 2 -, -CH 2 CH 2 -COO-, -CH 2 CH ₂ -OCO-, -COO-CH ₂ -, -OCO-CH ₂ -, -CH ₂ -COO-, -CH ₂ -OCO-, -CH = CH-, -N = N-, -CH = NN = CH-, -CF = CF-, -C? C- (Wherein P ³¹ -Sp ³¹ , P ³² -Sp ³² , P ³³ -Sp ³³ , P ³⁴ -Sp ³⁴ , P ³⁵ -Sp ³⁵ , Sp ³¹ -X ³¹ , Sp ³² -X ³² , Q31, q32, q34, q35, q36, q37, q38 and q39 in the formulas (3) and (3) do not include a direct bond between the oxygen atoms in Sp ³³ -X ³³ , Sp ³⁴ -X ³⁴ and Sp ³⁵ -X ³⁵ Independently represent 0 or 1, j3 represents 0 or 1, and MG ³¹ represents a mesogen group.

In the general formulas (III-1) to (III-2), P ³¹ to P ³⁵ are each independently represented by the following formulas (P-2-1) to (P- 2-20) Is preferably a substituent selected from a polymerizable group which is a polymerizable group.

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

In the general formulas (III-1) to (III-2), Sp ³¹ to Sp ³⁵ each independently represent an alkylene group having 1 to 15 carbon atoms, and one of the alkylene groups -CH ₂ -, or two or more non-adjacent -CH ₂ - groups may be independently substituted with -O-, -COO-, -OCO- or -OCO-O-, one of the alkylene groups Or two or more hydrogen atoms may be substituted with a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) or CN group, and Sp ³¹ to Sp ³⁵ each independently represent an alkylene group having 1 to 12 carbon atoms More preferably one of -CH ₂ - in the alkylene group or two or more non-adjacent -CH ₂ - are each independently -O-, -COO-, -OCO- or -OCO-O- .

In the general formulas (III-1) to (III-2), X ³¹ to X ³⁵ each independently represent -O-, -OCH ₂ -, -CH ₂ O-, -CO-, -COO -, -OCO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CF ₂ O-, -OCF ₂ -, -CH = CH- 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-, -CO-, -C≡C-, or a single bond, and X ³¹ to X ³⁵ each independently represent -O-, -OCH ₂ -, -CH ₂ O-, -CO -COO-, -OCO-, -O-CO-O-, -CF ₂ O-, -OCF ₂ -, -CH = CH-COO-, -CH = CH- -CHO-, -OCO-CH = CH-, -COO-CH ₂ CH ₂ -, -OCO-CH ₂ CH ₂ -, -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, More preferably a group represented by CH ₂ -, -OCO-CH ₂ -, -CH ₂ -COO-, -CH ₂ -OCO-, -CH═CH-, -CF═CF-, -C≡C- or a single bond Do.

In the general formulas (III-1) to (III-2), MG ³¹ represents a mesogen group,

In the formulas, A1, A2 and A3 each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group, a 1,4-cyclohexenyl group, a tetrahydropyran- Dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-di A pyrimidine-2,5-diyl group, a pyridine-2,5-diyl group, a thiophene-2,5-diyl group, a 1,2,3,4-tetrahydro Naphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, , 4a, 9,10a-octahydrophenanthrene-2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5-b '] dithiophene- Diyl group, benzo [1,2-b: 4,5-b '] dicosenophene-2,6-diyl group, [1] benzothieno [3,2- b] thiophene- , [1] benzoselenopheno [3,2-b] selenophene-2,7-diyl group, or fluorene-2,7-diyl group, and at least one F, Cl, CF ₃ , OCF _3, CN groups, the carbon atoms 1-8 alkyl , An alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, An alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and / or an alkenoyloxy group having 2 to 8 carbon atoms. 1) as in any of the present A1, A2 and A3 to the case of forming the structure represented by _{^{- (X 33) q35 - (}} Sp 33) it has an _q34 -P ^33. Z 1 and Z 2 are each independently selected from the group consisting of -COO-, -OCO-, -CH ₂ CH ₂ -, -OCH ₂ -, -CH ₂ O-, -CH═CH-, -C≡C-, -CH═CHCOO _{-, -OCOCH = CH-, -CH 2} CH 2 COO-, -CH 2 CH 2 OCO-, -COOCH 2 CH 2 -, -OCOCH 2 CH 2 -, -C = N-, -N = C-, An alkyl group having 2 to 10 carbon atoms or a single bond which may have a -CONH-, -NHCO-, -C (CF ₃ ) ₂ -, a halogen atom (fluorine, chlorine, bromine or iodine) Z1 and Z2 are each independently _{-COO-, -OCO-, -CH 2 CH 2} -, -OCH 2 -, -CH 2 O-, -CH = CH-, -C≡C-, -CH = CHCOO- _{, -OCOCH = CH-, -CH 2 CH} 2 COO-, -CH 2 CH 2 OCO-, -COOCH 2 CH 2 -, -OCOCH 2 CH 2 - or a single bond is preferable, and r1 is 0, 1, 2 or 3, and when a plurality of A 1 and Z 1 are present, they may be the same or different from each other). Of these, A1, A2 and A3 each independently preferably represent a 1,4-phenylene group, a 1,4-cyclohexylene group or a 2,6-naphthylene group.

As examples of the general formula (III), the following general formulas (III-1-1) to (III-1-8), general formulas (III-2-1) But the compound is not limited to the following general formula.

In the formulas, P ³¹ to P ³⁵ , Sp ³¹ to Sp ³⁵ , X ³¹ to X ³⁵ , and q ³¹ to q 39 MG ³¹ have the same definitions as in the formulas (III-1) to (III-2) ,

A11, A12, A13, A2 and A3 are the same as defined in A1 to A3 in the above formula (III-A), may be the same or different,

Z11, Z12, Z13 and Z2 are the same as defined for Z1 and Z2 in the above formula (III-A), respectively, and may be the same or different.

Examples of the compound represented by the general formula (III-1-1) to the general formula (III-1-8), the general formula (III-2-1) and the general formula (III-2-2) (III-9-1) to (III-9-6), but are not limited thereto.

In the general formulas (III-9-1) to (III-9-6), R ^f , R ^g and R ^h each independently represent a hydrogen atom or a methyl group, and R ⁱ , R ^j and R ^k are A halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a cyano group, Or a halogen atom (fluorine, chlorine, bromine or iodine) in the case of an alkoxy group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, as one or more of F, Cl, CF _3, OCF _3, CN groups, carbon atoms, alkyl of 1 to 8, an alkoxy group of a carbon atom number of 1-8, the number 1 to 8 of the alkanoyl group, carbon atoms carbon atoms An alkanoyloxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms Group, is optionally carbon atoms, an alkenyl noilgi 2-8, carbon atoms, an alkenyl group having 2 to 8 alkanoyl oxy.

m4 to m9 each independently represent an integer of 0 to 18, and n4 to n10 each independently represent 0 or 1;

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

The total content of the multifunctional polymerizable liquid crystal compound having three polymerizable functional groups in the molecule is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, in the total amount of the polymerizable liquid crystal compounds used in the polymerizable liquid crystal composition, , More preferably 0 to 5% by mass.

In the polymerizable liquid crystal composition of the present invention, the bifunctional polymerizable liquid crystal compound represented by general formula (I-1) and the monofunctional polymerizable liquid crystal compound represented by general formula (II-1) An optical film having a birefringence difference? N of 0.1 or less can be obtained.

The polymerizable liquid crystal composition of the present invention contains the bifunctional polymerizable liquid crystal compound represented by formula (I-1) and the monofunctional polymerizable liquid crystal compound represented by formula (II-1) as essential components , The polymerizable liquid crystal compound used in the polymerizable liquid crystal composition preferably contains 60 to 100 mass% of the two essential components, more preferably 70 to 100 mass%, and more preferably 75 to 100 mass% Is particularly preferable.

When a chiral compound to be described later is added to the polymerizable liquid crystal composition and a twisted nematic phase or cholesteric phase is to be expressed, the total amount of the polymerizable liquid crystal compounds used in the polymerizable liquid crystal composition is preferably in the range of It is possible to obtain an optical film having a value of a selective reflection wavelength band (DELTA lambda) / selective reflection central wavelength (lambda) of 0.1 or less by containing 30 to 85 mass% of the bifunctional polymerizable liquid crystal compound to be displayed. Excellent in transparency.

The value of the selective reflection wavelength band (DELTA lambda) / selective reflection central wavelength (?) Of the optical film of the present invention is the value of the polymerizable liquid crystal compound represented by the general formula (II-1) in the polymerizable liquid crystal composition of the present invention The value of the selective reflection wavelength band DELTA lambda / selective reflection central wavelength lambda is more preferably 0.010 or more and 0.095 or less, more preferably 0.020 or more and 0.090 or less, in terms of weight ratio And particularly preferably 0.030 or more and 0.080 or less.

(Other liquid crystal compound)

A compound containing a mesogen group having no polymerizable group may be added to the polymerizable liquid crystal composition of the present invention, and a liquid crystal device such as STN (super twisted nematic) liquid crystal, TN (twisted Nematic liquid crystal, TFT (thin film transistor) liquid crystal, and the like.

The compound containing a mesogenic group which does not have a polymerizable functional group is specifically preferably a compound represented by the following general formula (5).

The mesogen group or mesogenic group represented by MG3 is represented by the general formula (5-b)

(Wherein A1 ^d , A2 ^d and A3 ^d each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group, a 1,4-cyclohexenyl group, a tetrahydropyran- Dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2 Diyl group, pyridin-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene- A tetrahydronaphthalene-2,6-diyl group, a 2,6-naphthylene group, a phenanthrene-2,7-diyl group, a 9,10-dihydrophenanthrene-2,7-diyl group, , 3,4,4a, 9,10a-octahydrophenanthrene-2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5-b '] dithiophen- , 6-diyl group, benzo [1,2-b: 4,5-b '] dicselenophen-2,6-diyl group, [1] benzothieno [3,2- b] thiophene- Diyl group, a [1] benzoselenopheno [3,2-b] selenophene-2,7-diyl group, or a fluorene-2,7-diyl group, and at least one F, Cl , CF ₃ , OCF ₃ , CN group, a group of 1 to 8 carbon atoms An alkyl group, an alkoxy group, an alkanoyl group, an alkanoyloxy group, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group, an alkenoyl group and an alkenoyloxy group,

Z0 ^{d, d} Z1, Z2 and Z3 ^{d d} are each _{independently, -COO-, -OCO-, -CH 2 CH} 2 -, -OCH 2 -, -CH 2 O-, -CH = CH-, -C ≡C-, -CH = CHCOO-, -OCOCH = CH-, -CH 2 CH 2 COO-, -CH 2 CH 2 OCO-, -COOCH 2 CH 2 -, -OCOCH 2 CH 2 -, -CONH-, -NHCO-, an alkylene group or a single bond which may have a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) having 2 to 10 carbon atoms,

n ^e represents 0, 1 or 2,

R ⁵¹ and R ⁵² each independently represent a hydrogen atom, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group or an alkyl group having 1 to 18 carbon atoms, (fluorine atom, chlorine atom, bromine atom, iodine atom) or is substituted by CN, each of the groups during the present one CH ₂ group or not adjacent two or more CH ₂ groups, which independently of each other, an oxygen atom -O-, -S-, -NH-, -N (CH ₃ ) -, -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS - or -C? C-).

Specifically, they are shown below, but are not limited thereto.

Ra and Rb each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, or a cyano group, Or an alkoxy group having 1 to 6 carbon atoms, all of which may be unsubstituted or substituted by one or two or more halogen atoms.

The total content of the compound having a mesogen group is preferably 0% by mass or more and 20% by mass or less with respect to the total amount of the polymerizable liquid crystal composition, and is preferably 1% by mass or more, more preferably 2% Is preferably 5 mass% or more, more preferably 15 mass% or less, and more preferably 10 mass% or less.

(Organic solvent)

An organic solvent may be added to the polymerizable liquid crystal composition of the present invention. The organic solvent to be used is not particularly limited, but an organic solvent in which the polymerizable liquid crystal compound exhibits good solubility is preferable, and an organic solvent which can be dried at a temperature of 100 DEG C or less is preferable. Examples of such solvents include aromatic hydrocarbons such as toluene, xylene, cumene and mesitylene, ester solvents such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate, methyl ethyl ketone (MEK), methyl isobutyl ketone Ketone solvents such as methylene chloride (MIBK), cyclohexanone and cyclopentanone, ether solvents such as tetrahydrofuran, 1,2-dimethoxyethane and anisole, N, N-dimethylformamide, Amide solvents such as pyrrolidone, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate,? -Butyrolactone, and chlorobenzene. These solvents may be used alone or in admixture of two or more, but it is preferable to use at least one of a ketone solvent, an ether solvent, an ester solvent and an aromatic hydrocarbon solvent from the viewpoint of solution stability.

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

When the polymerizable liquid crystal composition is dissolved in an organic solvent, it is preferable to carry out heating and stirring in order to dissolve the polymerizable liquid crystal composition uniformly. The heating temperature at the time of heating and agitation may be suitably adjusted in consideration of the solubility of the composition in the organic solvent. From the standpoint of productivity, the heating temperature is preferably 15 ° C to 110 ° C, more preferably 15 ° C to 105 ° C, More preferably 100 ° C, and particularly preferably 20 ° C to 90 ° C.

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

The number of revolutions of stirring at the time of adding the solvent is preferably adjusted appropriately according to the stirring apparatus to be used. In order to obtain a homogeneous polymerizable liquid crystal composition solution, the number of revolutions of agitation is preferably 10 rpm to 1000 rpm, , More preferably 150 rpm to 600 rpm.

(Polymerization inhibitor)

It is preferable to add a polymerization inhibitor to the polymerizable liquid crystal composition in the present invention. Examples of the polymerization inhibitor include a phenol compound, a quinone compound, an amine compound, a thioether compound, and a nitroso compound.

Examples of the phenol compound include p-methoxyphenol, cresol, t-butyl catechol, 3,5-di-t- Butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-thiobis (3-methyl- 1-naphthol, 4,4'-dialkoxy-2,2'-non-1-naphthol, and the like.

Examples of the quinone compounds include hydroquinone, methylhydroquinone, tert-butylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, tert- 1,4-naphthoquinone, 1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, anthraquinone, diphenoquinone and the like.

Examples of the amine compound include p-phenylenediamine, 4-aminodiphenylamine, N, N'-diphenyl-p-phenylenediamine, Ni- Phenyl-p-phenylenediamine, N, N'-di-2-naphthyl-p-phenylenediamine, diphenylamine, N-phenyl- , 4,4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, and the like.

Examples of thioether compounds include phenothiazine, distearyliodipropionate, and the like.

Examples of the nitroso compounds include N-nitrosophenylamine, N-nitrosophenylnaphthylamine, N-nitrosodinaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, p-nitrophenylamine, p-nitrosoldimethylamine, p-nitroso-N, N-diethylamine, N-nitrosoethanolamine Nitroso-di-isopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5- N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine ammonium salt, nitrosobenzene, 2,4,6-tri-tert-butylnitrosobenzene, N- Nitroso-N-ethyl urethane, N-nitroso-Nn-propyl urethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol Sodium 1-nitroso-2-naphthol-3,6-sulfonate, 2- Trojan small-1-naphthol-4-sulfonate, and the like, 2-nitroso-5-methylamino-phenol hydrochloride, 2-nitroso-5-methylamino-phenol hydrochloride.

The addition amount of the polymerization inhibitor is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass with respect to the polymerizable liquid crystal composition.

(Photopolymerization initiator)

The polymerizable liquid crystal composition in the present invention preferably contains a photopolymerization initiator. It is preferable that at least one photopolymerization initiator is contained. More specifically, IRGACURE 651, IRGACURE 184, DAROCURE 1173, IRGACURE 907, IRGACURE 127, IRGACURE 369, IRGACURE 379, IRGACURE 819 and IRGACURE 819 manufactured by BASF IRGACURE OXE01 "," LUCIRIN TPO "," DAROCURE 1173 "," DAROCURE MBF ", and" IRGACURE 754 "," IRGACURE 784 "," IRGACURE OXE01 " SPEEDCURE MBP, SPEEDCURE PBZ, SPEEDCURE ITX, SPEEDCURE DETX, SPEEDCURE EBD, SPEEDCURE MBB, SPEEDCURE MBX, SPEEDCURE BMS, SPEEDCURE BMS, "SPEEDCURE BP" manufactured by Nippon Kayaku Co., Ltd., "KAYACURE DMBI" manufactured by Nippon Kayaku Co., Ltd., "TAZ-A" manufactured by Nippon Shibel Hegner Co., Ltd. (currently DKSH Co.), "ADEKA OPTOMER SP- 152" ADEKA OPTOMER N-1419 "," ADEKA OPTOMER N-1606 "," ADEKA OPTOMER N-1717 "," ADEKA OPTOMER N-1919 "," CYRACURE UVI-6990 , "CYRACURE UVI-6974" and "CYRACURE UVI-6992", "ADEKA OPTOMER SP-150, SP-152, SP-170 and SP-172" manufactured by Asahi Denka Kogyo Co., Ltd., "PHOTOINITIATOR 2074" "IRGACURE 250" manufactured by GE Silicones, "UV-9380C" manufactured by GE Silicones, and "DTS-102" manufactured by Midori Chemical Industry.

The amount of the photopolymerization initiator to be used is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 7 parts by mass, based on 100 parts by mass of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition. In order to improve the curability of the optically anisotropic material, it is preferable to use at least 3 parts by mass of a photopolymerization initiator per 100 parts by mass of the polymerizable liquid crystal compound. These may be used alone, or two or more kinds may be used in combination, or a sensitizer may be added.

(Thermal polymerization initiator)

In the polymerizable liquid crystal composition of the present invention, a thermal polymerization initiator may be used in combination with a photopolymerization initiator. As the thermal polymerization initiator, those known in the art can be used, and examples thereof include methyl acetoacetate peroxide, cumene hydroperoxide, benzoyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, Benzoate, methyl ethyl ketone peroxide, 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, p-pentahydroperoxide, t-butyl hydroperoxide, dicumylperoxide, iso Organic peroxides such as butyl peroxide, di (3-methyl-3-methoxybutyl) peroxydicarbonate and 1,1-bis (t-butylperoxy) cyclohexane, 2,2'-azobisisobutyronitrile , Azonitrile compounds such as 2,2'-azobis (2,4-dimethylvaleronitrile), azo compounds such as 2,2'-azobis (2-methyl-N-phenylpropionamidine) dihydrochloride Amidine compounds, 2,2'azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] Amide}, azo amide compounds, such as 2,2 'azobis (2,4,4-trimethylpentane) and the like can be used azo compounds such as alkyl. Specific examples thereof include "V-40", "VF-096" manufactured by Wako Pure Chemical Industries, Ltd., "PERHEXYL D" and "PERHEXYL I" manufactured by Nippon Oil Co., Ltd. (now Nichiyu Corporation).

The amount of the thermal polymerization initiator to be used is preferably 0.1 to 10 parts by mass, particularly preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition. These may be used alone or in combination of two or more.

(Surfactants)

The polymerizable liquid crystal composition of the present invention may contain at least one surfactant in order to reduce film thickness unevenness in the case of optically anisotropic. Examples of the surfactant which can be contained include alkylcarboxylic acid salts, alkyl phosphates, alkylsulfonic acid salts, fluoroalkylcarboxylic acid salts, fluoroalkylphosphates, fluoroalkylsulfonic acid salts, polyoxyethylene derivatives, fluoroalkylethylene oxide derivatives , Polyethylene glycol derivatives, alkylammonium salts, and fluoroalkylammonium salts. Of these, fluorine-based and acrylic-based surfactants are particularly preferred.

Specific examples of the MEGAFACE F-251, MEGAFACE F-444, MEGAFACE F-477, MEGAFACE F-510, MEGAFACE F-552, MEGAFACE F- MEGAFACE F-555, MEGAFACE F-555, MEGAFACE F-556, MEGAFACE F-557, MEGAFACE F-559, MEGAFACE F- MEGAFACE F-567 "," MEGAFACE F-569 "," MEGAFACE F-567 "," MEGAFACE F- MEGAFACE RS-72-K "," MEGAFACE RS-75 "," MEGAFACE F-571 "," MEGAFACE R-40 "," MEGAFACE R- MEGAFACE RS-76-E ", " MEGAFACE RS-90 " (manufactured by DIC Corporation)

FTERGENT 100, FTERGENT 100, FTERGENT 110, FTERGENT 150, FTERGENT 150CH, FTERGENT A, FTERGENT 100A-K, FTERGENT 501, FTERGENT 300, FTERGENT 212M "," FTERGENT 212M "," FTERGENT 250 "," FTERGENT 222F "," FTERGENT 212D "," FTX-400P "," FTERGENT 251 "," FTERGENT 215M " FTX-220D "," FTX-209F "," FTX-213F "," FTX-233F "," FTERGENT 245F "," FTX- FTX-230D, FTX-240D, FTX-207S, FTX-211S, FTX-220S, FTX-230S, FTX-750FM, FTX-730FL, FTX-710FS, FTX-710FM, FTX-710FL, FTX-750LL, FTX-730LS, FTX-730LM, FTX- 710LL " (manufactured by Neos Corporation)

BYK-300 "," BYK-302 "," BYK-306 "," BYK-310 "," BYK-315 " BYK-333 "," BYK-333 "," BYK-333 "," BYK- BYK-355 "," BYK-355 "," BYK-358 "," BYK-358 "," BYK- BYK-UV3570 "," BYK-UV3570 "and" BYK-Silclean3700 "(hereinafter referred to as" BYK-361N "," BYK-357 "," BYK-390 " Manufactured by Big Chem Japan Co., Ltd.)

TEGO Rad2000 "," TEGO Rad2000 "," TEGO Flow300 "," TEGO Flow370 "," TEGO Flow425 "," TEGO Rad2000 "," TEGO Rad2000 "," TEGO Rad2200 " &Quot; TEGO Flow ATF2 ", " TEGO Flow ZFS460 " (manufactured by Evonik Industries Co., Ltd.)

N215 "," N535 "," N605K ", and" N935 "(manufactured by Solvay Solexis).

The amount of the surfactant to be added is preferably 0.01 to 2 parts by mass based on 100 parts by mass of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition, More preferably 0.05 to 0.5 parts by mass.

By using the above surfactant, the tilt angle of the air interface can be effectively reduced when the polymerizable liquid crystal composition of the present invention is an optically anisotropic material.

The polymerizable liquid crystal composition according to the present invention is a polymerizable liquid crystal composition containing a repeating unit represented by the following general formula (7), which has an effect of effectively reducing the tilt angle of the air interface in an optically anisotropic form, And a compound having a molecular weight of 100 or more.

In the formulas, 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 the hydrogen atom in the hydrocarbon group is substituted with at least one halogen atom do.

Suitable compounds represented by the general formula (7) include, for example, polyethylene, polypropylene, polyisobutylene, paraffin, liquid paraffin, chlorinated polypropylene, chlorinated paraffin, chlorinated liquid paraffin and the like.

The amount of the compound represented by the general formula (7) is preferably 0.01 to 1 part by mass, and more preferably 0.05 to 0.5 part by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition.

(Non-liquid crystalline compound having a polymerizable group)

The polymerizable composition of the present invention may contain a compound having a polymerizable group but not a liquid crystal compound. Such a compound can be used without particular limitation, as long as it is generally recognized as a polymerizable monomer or a polymerizable oligomer in this technical field. The addition amount of the non-liquid crystalline compound having a polymerizable group is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 1 part by mass, more preferably 0.05 to 1 part by mass, relative to 100 parts by mass of the content of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition 0.05 to 0.5 parts by mass is preferable.

Specific examples thereof include monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl acrylate, propyl (meth) acrylate, 2-hydroxypropyl (meth) (Meth) acrylate, isobutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (Meth) acrylate, isobornyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyloxylethyl (Meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, Acrylate, methoxy (Meth) acrylate, ethyl (meth) acrylate, ethyl carbitol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (N? 2) monoacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxyethyl (meth) acrylate, (Meth) acrylate, (3-ethyloxetan-3-yl) methyl (meth) acrylate, o-phenylphenethoxy (Meth) acrylate, dimethylamino (meth) acrylate, diethylamino (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) , 4,4-hexafluorobutyl (meth) acrylate, 2,2,3,3,4,4,4-heptafluorobutyl (meth) acrylate, 2- (perfluorobutyl) ethyl ) Acrylate, 2- (purple 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H-dodecane (meth) acrylate, 1H-1- (trifluoromethyl) trifluoroethyl (meth) acrylate, 1H, 1H, 3H-hexafluorobutyl (meth) acrylate, 1,2,2 , 1H, 1H-pentadecafluorooctyl (meth) acrylate, 1H, 1H, 2H, 2H-tridecafluorooctyl (meth) acrylate, 2-tetrafluoro-1- Acrylates such as 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, glycidyl (meth) acrylate, 2- Ethylphosphoric acid, acryloylmorpholine, dimethyl acrylamide, dimethylaminopropylacrylamide, isopropylacrylamide, diethylacrylamide, hydroxyethylarc (Meth) acrylate such as 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1-butanediol di (Meth) acrylate, diethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, diethylene glycol di , Triethylene glycol di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 9,9-bis [4- (Meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, an acrylic acid adduct of 1,6-hexanediol diglycidyl ether, 1, Diacrylate such as acrylic acid adduct of 4-butanediol diglycidyl ether and the like , Trimethylolpropane tri (meth) acrylate, ethoxylated isocyanuric acid triacrylate, pentaerythritol tri (meth) acrylate, epsilon -caprolactone modified tris- (2-acryloyloxyethyl) isocyanurate Tetra (meth) acrylate such as tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and ditrimethylol propane tetra (meth) acrylate, dipentaerythritol hexa (meth) (Meth) acrylate of an oligomer type, various urethane acrylates, various macromonomers, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl Epoxy compounds such as ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, and bisphenol A diglycidyl ether, maleimide and the like . These may be used alone or in combination of two or more.

(Chain transfer agent)

In the polymerizable liquid crystal composition of the present invention, it is also preferable to add a chain transfer agent in order to further improve adhesion with a base material in the case of an optically anisotropic material. As the chain transfer agent, thiol compounds are preferable, and monothiol, dithiol, trithiol, and tetrathiol compounds are more preferable, and trithiol compounds are even more preferable. Specifically, the compounds represented by the following general formulas (8-1) to (8-13) are preferable.

In the formula, R ⁶⁵ represents an alkyl group having 2 to 18 carbon atoms, and the alkyl group may be either straight chain or branched. One or more of the methylene groups in the alkyl group is an alkylene group in which an oxygen atom and a sulfur atom are not directly bonded to each other, , Sulfur atom, -CO-, -OCO-, -COO-, or -CH = CH-, R ⁶⁶ represents an alkylene group having 2 to 18 carbon atoms, and at least one of the alkylene groups The methylene group may be an oxygen atom, a sulfur atom, -CO-, -OCO-, -COO-, or -CH = CH- in which oxygen and sulfur atoms are not directly bonded to each other.

The addition amount of the chain transfer agent is preferably 0.5 to 10 parts by mass, more preferably 1.0 to 5.0 parts by mass based on 100 parts by mass of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition.

(Coloring matter)

The polymerizable liquid crystal composition of the present invention may contain a pigment as required. The dye to be used is not particularly limited and may contain a known dye within a range that does not disturb the orientation.

Examples of the dye include dichroic dye, fluorescent dye and the like. Examples of such pigments include polyazo pigments, anthraquinone pigments, cyanine pigments, phthalocyanine pigments, perylene pigments, perinone pigments, and squarylium pigments. From the viewpoint of addition, Is preferable. For example, U.S. Patent No. 2,400,877, Dreyer J. F., Phys. and Colloid Chem., 1948, 52, 808. " The Fixing of Molecular Orientation ", Dreyer JF, Journal de Physique, 1969, 4, 114. " Light Polarization from Films of Lyotropic Nematic Liquid Crystals & , &Quot; Chromonics " in " Handbook of Liquid Crystals Vol.2B: Low Molecular Weight Liquid Crystals II ", D. Demus, Goodby, G. W. Gray, H. W. Spiessm, Villette, Willey-VCH, P.981-1007 (1998), Dichroic Dyes for Liquid Crystal Display, AV lvashchenko CRC Press, 1994, and "New Developments in Functional Color Markets", Chapter 1, CMC Co., Ltd. can be used.

Examples of the dichroic dye include dichroic dyes represented by the following formulas (d-1) to (D-8)

. The amount of the dye such as the dichroic dye is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass based on 100 parts by mass of the total amount of the polymerizable liquid crystal compound contained in the powder mixture.

(filler)

The polymerizable liquid crystal composition of the present invention may contain a filler if necessary. The filler to be used is not particularly limited and may contain a known filler within a range that does not deteriorate the thermal conductivity of the obtained polymer. Specific examples thereof include inorganic fillers such as alumina, titanium white, aluminum hydroxide, talc, clay, mica, barium titanate, zinc oxide and glass fiber; metallic powders such as silver powder and copper powder; aluminum nitride; , Thermally conductive fillers such as silicon carbide, magnesia (aluminum oxide), alumina (aluminum oxide), crystalline silica (silicon oxide), fused silica (silicon oxide), and the like.

(Chiral compound)

In the polymerizable liquid crystal composition of the present invention, the resulting optical film may contain a chiral compound which may exhibit liquid crystallinity or may be non-liquid crystalline in order to have cholesteric liquid crystallinity. Among the chiral compounds, It is preferable to use a polymerizable chiral compound having polymerizability.

The polymerizable chiral compound to be used in the present invention preferably has at least one polymerizable functional group. Such compounds include, for example, those disclosed in Japanese Patent Application Laid-Open Nos. 11-193287, 2001-158788, 2006-52669, 2007-269639, Isosorbide, isomannit, and glucoside as described in, for example, Japanese Patent Application Laid-Open Nos. 2007-269640 and 2009-84178, and includes 1,4-phenylene group, 1 , 4-cyclohexylene group, and a polymerizable chiral compound having a polymerizable functional group such as vinyl group, acryloyl group, (meth) acryloyl group, and maleimide group, Polymerizable chiral compounds comprising terpenoid derivatives such as those described in US Pat. No. 2,396,686, NATURE VOL 35 467-469 (published on November 30, 1995), NATURE VOL 392 476-479 (April 2, 1998 Quot;), and the like, A polymerizable chiral compound composed of a spacer having a chiral moiety or a polymerizable chiral compound containing a binaphthyl group as described in JP-A 2004-504285 and JP 2007-248945 . Among them, a chiral compound having a high helical twisting force (HTP) is preferable for the polymerizable liquid crystal composition of the present invention.

Among the chiral compounds, chiral compounds having a large helical twisting power (HTP) include the following general formulas (3-1) to (3-4), and general formulas (3-1) to (3- 3), more preferably a chiral compound selected from the general formulas (3-1) to (3-3), and the chiral compound having a polymerizable group represented by the following general formula (3-a) It is particularly preferred to use polymeric chiral compounds.

In the formula, Sp ^3a and Sp ^3b each independently represent an alkylene group having 0 to 18 carbon atoms, and the alkylene group may have at least one halogen atom, CN group, or a group having 1 to 8 carbon atoms having a polymerizable functional group optionally substituted by an alkyl group, and, a group of two or more that are present one CH group or not adjoining _two CH ₂ groups are each independently of the, in the form of oxygen atoms are not directly bonded to each other, -O-, -S -, -NH-, -N (CH ₃ ) -, -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C-,

A 1, A 2, A 3, A 4, A 5 and A 6 are each independently a 1,4-phenylene group, a 1,4-cyclohexylene group, a 1,4-cyclohexenyl group, a tetrahydropyran- Dihexylthiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2, Diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group, -Tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene- 2,4,4a, 9,10a- octahydrophenanthrene-2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5- b '] dithiophen- Di-yl group, benzo [1,2-b: 4,5-b '] dicselenophen-2,6-diyl group, [1] benzothieno [3,2- b] thiophene-2,7 -Diiyl group, [1] benzoselenopheno [3,2-b] selenophene-2,7-diyl group, or fluorene-2,7-diyl group, and at least one F, Cl, CF _3, OCF _3, CN groups, carbon atoms, 1-8 Al An alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, An alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, an alkenoyl group having 2 to 8 carbon atoms, and / or an alkenoyloxy group having 2 to 8 carbon atoms. A 1, A 2, A 3, A 4, A 5 and A 6 each independently preferably represent a 1,4-phenylene group, a 1,4-cyclohexylene group or a 2,6-naphthylene group, , A CN group, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 8 carbon atoms.

n, l, k and s each independently represent 0 or 1,

Z0, Z1, Z2, Z3, Z4, Z5, and Z6 are each _{independently, -COO-, -OCO-, -CH 2 CH} 2 -, -OCH 2 -, -CH 2 O-, -CH = CH- , -C≡C-, -CH═CHCOO-, -OCOCH═CH-, -CH ₂ CH ₂ COO-, -CH ₂ CH ₂ OCO-, -COOCH ₂ CH ₂ -, -OCOCH ₂ CH ₂ -, - CONH-, -NHCO-, an alkyl group having 2 to 10 carbon atoms which may have a halogen atom or a single bond,

n5 and m5 each independently represent 0 or 1,

R ^3a and R ^3b represent a hydrogen atom, a halogen atom, a cyano group or an alkyl group having 1 to 18 carbon atoms, which alkyl group may be substituted by at least one halogen atom or CN, CH ₂ groups or two or more CH ₂ groups which are not adjacent to each other are mutually independently bonded to each other in such a form that oxygen atoms are not directly bonded to each other, -O-, -S-, -NH-, -N (CH ₃ ) -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C-,

Or R < ^3a > and R < ^3b >

(Wherein P ^3a represents a polymerizable functional group).

P ^3a preferably represents a substituent selected from the polymerizable groups represented by the following formulas (P-1) to (P-20).

Among these polymerizable functional groups, the formula (P-1) or the formula (P-2), (P-7), (P-12) and (P-13) are preferable from the viewpoint of enhancing the polymerizability and storage stability , (P-1), (P-7) and (P-12).

Specific examples of the polymerizable chiral compound include the compounds of the compounds (3-5) to (3-24), but are not limited to the following compounds.

M, n, k and l each independently represent an integer of 1 to 18; R ¹ to R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, , And 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 two or more halogen atoms.

Among the polymerizable chiral compounds represented by the general formulas (3-5) to (3-24), chiral compounds having a large helical twisting power (HTP) include compounds represented by the general formulas (3-5) It is particularly preferable to use the polymerizable chiral compounds represented by the general formulas (3-12) to (3-14) and the general formulas (3-16) to (3-18)

The blending amount of the polymerizable chiral compound needs to be appropriately adjusted according to the helical organic potential of the compound, but it is preferably contained in the polymerizable liquid crystal composition in an amount of 0 to 25 mass%, more preferably 0 to 20 mass% , And 0 to 15% by mass.

In order to obtain the optical film having cholesteric properties and to obtain an optical film having good permeability, the polymerizable liquid crystal composition of the present invention contains the chiral compound in a total amount of 100 parts by mass of the polymerizable liquid crystal compound used in the polymerizable liquid crystal composition 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and particularly preferably 1.5 to 10 parts by mass are particularly preferably used.

(Other additives)

In order to adjust the physical properties, additives such as a polymerizable compound having no liquid crystalline property, a tin scavenger, an ultraviolet absorber, an infrared absorber, an antioxidant and a surface treatment agent may be added to the extent that does not significantly lower the aligning ability of the liquid crystal have.

(Manufacturing Method of Optical Anisotropic Member)

(Optical anisotropic body)

The optically anisotropic material produced by using the polymerizable liquid crystal composition of the present invention is obtained by sequentially laminating a substrate, an orientation film as required, and a polymer of a polymerizable liquid crystal composition.

(materials)

The substrate used in the optically anisotropic medium of the present invention is a substrate usually used for a liquid crystal device, a display, an optical component or an optical film, and has heat resistance that can withstand heating during application after application of the polymerizable liquid crystal composition of the present invention Is not particularly limited. Examples of such a substrate include an organic material such as a glass substrate, a metal substrate, a ceramic substrate, and a plastic substrate. Particularly, when the base material is an organic material, it is possible to use a cellulose derivative, a polyolefin, a polyester, a polycarbonate, a polyacrylate (acrylic resin), a polyarylate, a polyether sulfone, a polyimide, a polyphenylene sulfide, Polystyrene, and the like. Among them, plastic substrates such as polyester, polystyrene, polyacrylate, polyolefin, cellulose derivatives, polyarylate and polycarbonate are preferable, and substrates such as polyacrylate, polyolefin and cellulose derivatives are more preferable, and COP It is particularly preferable to use TAC (triacetylcellulose) as the cellulose derivative and PMMA (polymethyl methacrylate) as the polyacrylate. The shape of the substrate may be a shape having a curved surface other than a flat plate. These substrates may have an electrode layer, an antireflection function, and a reflection function, if necessary.

In order to improve the coatability and adhesiveness of the polymerizable liquid crystal composition of the present invention, surface treatment of these substrates may be performed. Examples of the surface treatment include ozone treatment, plasma treatment, corona treatment, and silane coupling treatment. In order to adjust the transmittance and reflectance of light, an organic thin film, an inorganic oxide thin film, a metal thin film, or the like is formed on the surface of the substrate by vapor deposition or the like, or optical add- , An optical disk, a phase difference film, a light diffusion film, a color filter, or the like. Among them, a pickup lens, a retardation film, a light diffusion film, and a color filter which have a higher added value are preferable.

(Orientation treatment)

In addition, as the substrate, an alignment film may be provided on a glass substrate alone or on a substrate so that the polymerizable liquid crystal composition is oriented when the polymerizable liquid crystal composition of the present invention is applied and dried. Examples of the alignment treatment include a stretching treatment, a rubbing treatment, a polarized ultraviolet visible light irradiation treatment, and an ion beam treatment. When an alignment film is used, a known alignment film is used. As such an orientation film, a hydrophilic polymer containing polyimide, polyamide, lecithin, hydroxyl group, carboxylic acid group or sulfonic acid group, or a hydrophilic inorganic compound or photo alignment film can be used. Examples of the hydrophilic polymer include polyvinyl alcohol, polyacrylic acid, sodium polyacrylate, polymethacrylic acid, sodium polyallylate, polycarboxymethylcellulose sodium salt, pullulan, and polystyrenesulfonic acid. Examples of the hydrophilic inorganic compound include inorganic compounds such as oxides and fluorides such as Si, Al, Mg and Zr. Since the hydrophilic substrate is effective for aligning the optical axis of the optically anisotropic material substantially in parallel to the normal direction with respect to the substrate, it is preferable to obtain an optically anisotropic substance of the positive C plate. However, when a hydrophilic substrate is subjected to rubbing treatment, Therefore, the rubbing treatment in the hydrophilic polymer layer adversely affects the vertical alignment property, so that it is not preferable to obtain the optically anisotropic substance of the positive C plate.

(apply)

Examples of the coating method for obtaining the optically anisotropic medium of the present invention include an applicator method, a bar coating method, a spin coating method, a roll coating method, a direct gravure coating method, a reverse gravure coating method, a flexo coating method, , A cap coating method, a dip coating method, and a slit coating method. After the application of the polymerizable liquid crystal composition, the solvent contained in the polymerizable liquid crystal composition is heated and dried, if necessary.

(Polymerization step)

With respect to the polymerization operation of the polymerizable liquid crystal composition of the present invention, the liquid crystal compound in the polymerizable liquid crystal composition is generally subjected to ultraviolet light (ultraviolet light) in a state of being horizontally oriented, vertically oriented, hybrid oriented, or cholesteric , Or by heating. When the polymerization is carried out by light irradiation, concretely, it is preferable to irradiate ultraviolet light of 390 nm or less, and it is most preferable to irradiate light of a wavelength of 250 to 370 nm. However, when the polymerizable liquid crystal composition causes decomposition or the like due to ultraviolet light of 390 nm or less, it is sometimes preferable to perform the polymerization treatment with ultraviolet light of 390 nm or more. It is preferable that the light is diffused light and is not polarized light.

(Polymerization method)

Examples of the method for polymerizing the polymerizable liquid crystal composition of the present invention include a method of irradiating an active energy ray or a thermal polymerization method and the like without any heating, Among them, a method of irradiating light such as ultraviolet rays is preferable in view of easy operation.

The temperature at the time of irradiation is preferably 30 ° C or lower as much as possible in order to keep the temperature of the polymerizable liquid crystal composition of the present invention at a temperature at which the liquid crystal phase can be maintained and to prevent the polymerization of the polymerizable liquid crystal composition from being induced. In addition, the liquid crystal composition typically exhibits a nematic phase liquid crystal phase in the order of Cr (crystal) -N (nematic) -I (isotropic liquid) in the heating step, Since the composition exhibits Smectic liquid crystallinity, it exhibits a phase transition of Cr (crystal) -Sm (Smectic) -N (nematic) -I (isotropic liquid) And two liquid crystal phases of a tact phase and a nematic phase. On the other hand, in the temperature raising process, since it takes a thermodynamically unbalanced state, it is not crystallized even at a transition temperature of Cr (crystal) -N (nematic) or Cr (crystal) -Sm (smectic) The Mectic liquid crystal state may be maintained. This state is referred to as a supercooled state. In the present invention, the liquid crystal composition in the supercooled state is also included in the state of retaining the liquid crystal phase. Since the smectic phase has a structure closer to the crystal than the nematic phase in order to have a layered structure, the optically anisotropic substance obtained by irradiating ultraviolet rays in a smectic phase state with respect to the optically anisotropic substance obtained by irradiating ultraviolet rays in a nematic phase state Is an optically anisotropic material having a close structure, it is preferable because it improves alignment and / or heat resistance. The smectic phase is roughly divided into two depending on whether the molecular long axis of the layer normal is vertical or inclined. Smectic phase (SmA) and Smectic B phase (SmB), in which the molecular long axis is perpendicular to the layer normal, have a Smectic phase (SmB) (SmC), a Smectic F phase (SmF), a Smectic G phase (SmG), a Smectic I phase (SmI), and a Smectic J phase (SmJ). A Smectic A phase (SmA) in which the molecular long axis becomes perpendicular to the layer normal when phase transition from a nematic phase oriented to a molecular long axis in the rubbing direction of the polyimide alignment film in a homogeneous orientation to a Smectic phase, , And the Smectic B phase (SmB), it is preferable that the molecular long axis in the layer is oriented along the rubbing direction so that the generation of alignment defects is small and good orientation is obtained.

Specifically, it is preferable to irradiate ultraviolet light of 390 nm or less, and it is most preferable to irradiate light of a wavelength of 250 to 370 nm. However, when the polymerizable composition causes decomposition or the like due to ultraviolet light of 390 nm or less, it is sometimes preferable to perform the polymerization treatment with ultraviolet light of 390 nm or more. It is preferable that the light is diffused light and is not polarized light. The ultraviolet ray irradiation intensity is, the range of ^{0.05kW / m 2 ~ 10kW / m} 2 is preferred. Particularly, a range of 0.2 kW / m ² to 2 kW / m ² is preferable. When the ultraviolet intensity is less than 0.05 kW / m ² , it takes a long time to complete the polymerization. On the other hand, at a strength exceeding ² kW / m ² , the liquid crystal molecules in the polymerizable liquid crystal composition tend to be photodegraded, or a large amount of polymerization heat is generated and the temperature during the polymerization is elevated to change the order parameter of the polymerizable liquid crystal, There is a possibility that an abnormality may occur in the retardation of the subsequent film.

It is possible to use a mask to polymerize only a specific part by ultraviolet irradiation and then change the orientation state of the unpolymerized part by applying an electric field, a magnetic field or a temperature, and then polymerizing the unpolymerized part, An optical anisotropic medium having a plurality of regions can be obtained.

When a specific part of the polymerizable liquid crystal composition is polymerized by ultraviolet irradiation using a mask, alignment is regulated by applying an electric field, a magnetic field, or a temperature to the unpolymerized polymerizable liquid crystal composition in advance, It is possible to obtain an optically anisotropic substance having a plurality of regions having different orientation directions.

The optically anisotropic substance obtained by polymerizing the polymerizable liquid crystal composition of the present invention may be used singly as an optically anisotropic material by being peeled from the substrate or may be used as an optically anisotropic material without peeling from the substrate. Particularly, since it is difficult to contaminate other members, it is useful when used as a laminated substrate or bonded to another substrate.

(Optical film)

The optical film (retardation film) of the present invention is produced in the same manner as a conventional method for producing an optically anisotropic film. The resulting retardation film can be used as various birefringent films and the like. A device or display such as a liquid crystal device, a liquid crystal display, an organic EL device, an organic EL display, a quantum dot EL device, a quantum dot EL display, a micro LED, Film, compensation film, and the like.

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

For example, an alignment mode of a positive A plate, a negative A plate, a positive C plate, a negative C plate, a biaxial plate, a positive O plate, and a negative O plate can be applied. Among them, it is preferable to use a positive A plate and a negative C plate. Further, it is more preferable to laminate the positive A plate and the negative C plate.

Here, the positive A plate refers to an optically anisotropic substance in which the polymerizable liquid crystal composition is homogeneously oriented. The negative C plate means an optically anisotropic substance in which the polymerizable liquid crystal composition is cholesterically aligned.

In the liquid crystal cell using the retardation film, it is preferable to use a positive A plate as the first retardation layer in order to compensate for the viewing angle dependence of the polarization axis orthogonality and widen the viewing angle. When the refractive index in the in-plane slow axis direction of the film is nx, the refractive index in the in-plane fast axis direction is ny, and the refractive index in the thickness direction of the film is nz, , And "nx> ny = nz". As the positive A plate, it is preferable that the in-plane retardation value at a wavelength of 550 nm is in the range of 30 to 500 nm. The retardation value in the thickness direction is not particularly limited. The Nz coefficient is preferably in the range of 0.9 to 1.1.

In order to eliminate the birefringence of the liquid crystal molecule itself, it is preferable to use a so-called negative C plate having negative refractive index anisotropy as the second retardation layer. Further, a negative C plate may be laminated on the positive A plate.

Here, when the refractive index of the retardation layer in the in-plane slow axis direction is nx, the refractive index in the in-plane fast axis direction of the retardation layer is ny, and the refractive index in the thickness direction of the retardation layer is nz, the negative C plate has "nx = ny> Is a retardation layer having a relationship of " The thickness direction retardation value of the negative C plate is preferably in the range of 20 to 400 nm.

Further, the refractive index anisotropy in the thickness direction is expressed by the thickness direction retardation value Rth defined by the following formula (2). The thickness direction retardation value Rth is calculated by using the in-plane retardation value R ₀ , the retardation value R ₅₀ measured by inclining the retardation axis by 50 ° with the slow axis as the tilt axis, the thickness d of the film, and the average refractive index n ₀ of the film, Nx, ny, and nz can be obtained by numerical calculations from the equations (4) to (7), and these can be substituted into the equation (2). Further, the Nz coefficient can be calculated from the equation (3). Hereinafter, the same is applied to the other descriptions of this specification.

_{R 0 = (nx-ny)} × d (1)

Rth = [(nx + ny) / 2-nz] xd (2)

Nz coefficient = (nx-nz) / (nx-ny) (3)

_{R 50 = (nx-ny '} ) × d / cos (φ) (4)

(nx + ny + nz) / 3 = n 0 (5)

here,

? = sin ^-1 [sin (50) / n ₀ ] (6)

ny '= ny × nz / [ny ² × sin ² (φ) + nz ² × cos ² (φ)] ^1/2 (7)

The phase difference measuring apparatus on the market, a numeric calculation shown herein is performed automatically in the apparatus, in many cases, which is adapted to automatically display or the like in-plane retardation value R ₀ and a thickness retardation value Rth. As such a measuring apparatus, for example, RETS-100 (manufactured by Otsuka Chemical Co., Ltd.) can be mentioned.

The optical film of the present invention is used depending on the application. Since the film thickness of the optical film is too thin or too thick, it is difficult to control the orientation when it is produced by application, More preferably 0.1 μm or more and 12 μm or less, and particularly preferably 0.2 μm or more and 6 μm or less.

(Phase difference patterning film)

The optical film of the present invention may be used for a retardation patterning film. The retardation patterning film is obtained by successively laminating a base material, an orientation film, and a polymer of a polymerizable liquid crystal composition, but is patterned so as to obtain partially different retardation in the polymerization process. The patterning may be in different directions, such as linear patterning, lattice patterning, circular patterning, polygonal patterning, and the like. A liquid crystal device, a display, an optical element, an optical component, a coloring agent, a marking for security, a member for laser emission, an optical film, and a compensation film.

As a method for obtaining a partially different phase difference, an orientation film is provided on a substrate, and when the polymerizable liquid crystal composition of the present invention is applied and dried during alignment treatment, the polymerizable liquid crystal composition is processed so as to be patterned. Such alignment treatment may be a micro-rubbing treatment, a polarized ultraviolet visible light irradiation treatment through a photomask, or a fine shape processing treatment. As the alignment layer, a known alignment layer is used. Examples of such an orientation film include a film made of at least one of polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyether sulfone, epoxy resin, epoxy acrylate resin, Compounds, chalcone compounds, cinnamate compounds, peptidic compounds, anthraquinone compounds, azo compounds, and arylethene compounds. The compound that is subjected to the orientation treatment by the fine rubbing preferably promotes the crystallization of the material by applying an orientation treatment or a heating process after the orientation treatment. Among the compounds which are subjected to the orientation treatment other than the rubbing, it is preferable to use a photo-orienting material.

(Luminance enhancement film)

The optical film of the present invention can also be used for a brightness enhancement film. The brightness enhancement film of the present invention is a brightness enhancement film having a? / 4 plate and a reflective polarizer, and the reflective polarizer includes a first light reflection layer, a second light reflection layer and a third light reflection layer in this order from the? / 4 plate side And the first light reflection layer, the second light reflection layer and the third light reflection layer are all fixed by a cholesteric liquid crystal phase, and any one of the first light reflection layer, the second light reflection layer and the third light reflection layer One of which is a green light reflecting layer having a peak of reflectance with a reflection center wavelength of 500 to 599 nm and a half width of 200 nm or less, and one of which is a blue light reflecting layer having a peak wavelength of 600 To 750 nm and a half-width of 150 nm or less, and the signs of Rth (550) of the first light reflection layer and Rth (550) of the second light reflection layer are opposite to each other. With such a configuration, the brightness enhancement film of the present invention can suppress the change in the color tone of the oblique tone when the brightness enhancement film is attached to the liquid crystal display device.

(Color compensation film)

The optical film of the present invention may be used for a color compensation film. The color compensation film is a film that cuts wavelengths of white light emitted from a backlight source, that is, a mixed color of blue, green, and red mixed light. In the case of ordinary white light, the color filter is used to divide the color in the vicinity of 570 to 620 nm into respective colors of green and red. However, by using a color compensation film having a selective reflection wavelength in the vicinity of 570 to 620 nm, color reproducibility can be improved .

(Cholesteric reflective film)

The cholesteric reflective film of the present invention is a cholesteric reflective film constituted by a cured product of a planar-oriented polymerizable liquid crystal composition, wherein the polymerizable liquid crystal composition comprises a liquid crystal having only one polymerizable functional group and having a tolan skeleton Containing one or two or more chiral compounds having at least one polymerizable functional group and containing at least one liquid crystal compound having at least two polymerizable functional groups and at least one polymerizable functional group , And at least one polymerization initiator.

(Antireflection film)

The antireflection film of the present invention is a circularly polarizing plate formed by laminating a phase difference plate in addition to a polarizing plate. A retardation plate or the like is used when changing linearly polarized light to circularly polarized light, changing circularly polarized light to linearly polarized light, or changing polarizing direction of linearly polarized light. Particularly, a so-called quarter wave plate (also referred to as a? / 4 plate) is used as a retardation plate for changing linearly polarized light to circularly polarized light or converting circularly polarized light to linearly polarized light. The 1/2 wavelength plate (also referred to as a? / 2 plate) is usually used when changing the polarization direction of linearly polarized light.

The circularly polarizing plate is effectively used, for example, in the case of adjusting the color tone of an image of a reflection type liquid crystal display device in which an image is a color display, and also has a function of preventing reflection. Examples of the retardation film include an alignment film of a liquid crystal polymer and a film in which an alignment layer of a liquid crystal polymer is supported by a film. The retardation plate may have an appropriate retardation depending on the purpose of use, for example, for the purpose of coloring due to birefringence of various wavelength plates or liquid crystal layers or for compensation of visual observation, etc., or two or more kinds of retardation plates may be laminated Or an optical characteristic such as a phase difference may be controlled.

(Viewing angle compensation film)

The optical film of the present invention may be used as a viewing angle compensation film. The viewing angle compensating film of the present invention is a film for widening the viewing angle so that the image is seen relatively clearly even when the screen of the liquid crystal display device is viewed in a direction slightly inclined rather than perpendicular to the screen. Examples of such a viewing angle compensating film include an orientation film such as a retardation film or a liquid crystal polymer, an orientation film such as a liquid crystal polymer supported on a transparent substrate, and the like. A conventional retardation film uses a birefringent polymer film uniaxially stretched in its plane direction or a uniaxially oriented liquid crystal polymer film while a retardation film used as a viewing angle compensating film has birefringence stretched biaxially in the plane direction A polymer film, a bi-directionally stretched film such as a polymer having a birefringence in which the refractive index in the thickness direction is controlled in the thickness direction and a uniaxially stretched film drawn uniaxially in the surface direction, and the like are used. As the oblique orientation film, for example, there can be mentioned a film in which a liquid crystal polymer is oriented in an oblique direction, and a polymer film polymerized by an active energy ray such as ultraviolet rays in a state in which a polymerizable liquid crystal is obliquely oriented. An appropriate one for the purpose of prevention of coloring due to a change in the viewing angle based on the phase difference caused by the liquid crystal cell and enlargement of the viewing angle of good viewing is used.

In addition, an optically compensatory retardation plate in which an optically anisotropic layer composed of a tilt alignment film of a liquid crystal polymer is supported by an optical film is preferably used, since both viewers achieve a wide viewing angle.

(Reflective polarizer)

The optical film of the present invention can also be used as a reflection type polarizing plate. The reflection type polarizing plate of the present invention is a reflection type polarizing plate in which a cholesteric reflective film, an adhesive layer and a linearly polarizing film are sequentially laminated, and the cholesteric reflective film uses the cholesteric reflective film of the present invention. Further, a phase difference film having at least one retardation film in the reflection type polarizing plate and different retardation of the retardation film may be used. The lamination of the retardation film is obtained by bonding an adhesive or an adhesive film to the resulting retardation film and then joining the cholesteric reflective film of the present invention and the retardation film through an adhesive or an adhesive film. When an adhesive or an adhesive film is used, the adhesive or the adhesive film may be a known adhesive for optical film use.

Example

Hereinafter, the present invention will be described with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited thereto. Unless otherwise stated, "parts" and "%" are on a mass basis.

(Preparation of polymerizable liquid crystal composition)

(A-1) to (A-8), B-1 to B-11 shown in Tables 1 to 5 and Expressions (C- (E-1) to (E-4) as the organic solvent, the compound represented by the formula (F-1) as the antioxidant, the compound represented by the formula (H-1) as a polymerization initiator, (I-1) as a chain transfer agent, and a compound represented by the formula (1) to (28) were obtained by blending the components (I-1) to (J-3) It was prepared.

(Preparation of Polymerizable Liquid Crystal Composition (1)) [

40 parts by mass of the compound represented by the formula (A-1), 40 parts by mass of the compound represented by the formula (A-2) and 20 parts by mass of the compound represented by the formula (B-1) , 0.1 parts by mass of the compound (G-1), 3 parts by mass of (H-1), 0.2 parts by mass of (J-2) And 100 parts by mass of an organic solvent (E-3) and 200 parts by mass of (E-4) were stirred under the conditions of a stirring speed of 500 rpm and a solution temperature of 60 ° C for 1 hour using an agitator having a stirring propeller Thereafter, the mixture was filtered through a 0.2 μm membrane filter to obtain a polymerizable liquid crystal composition (1).

(Preparation of polymerizable liquid crystal compositions (2) to (33) and comparative polymerizable liquid crystal compositions (34) to (38)) [

(A-1) to (A-8), (B-1) to (B-11), (D-1) to (D-3), 100 parts by mass of the compound represented by the formula (C-1) (H-1) to (H-2) as a polymerization initiator, (G-1) as a polymerization initiator, (J-1) to (J-3) as the non-liquid crystalline compound having a polymerizable group and the surfactant as the ratio shown in Tables 1 to 5, Polymerizable liquid crystal compositions (2) to (33) and comparative polymerizable liquid crystal compositions (34) to (38) were obtained under the same conditions as the preparation of the polymerizable liquid crystal composition (1).

Tables 1 to 5 show specific compositions of the polymerizable liquid crystal compositions (1) to (33) and comparative polymerizable liquid crystal compositions (34) to (38) of the present invention.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

Cyclopentanone (E-1)

Methyl isobutyl ketone (E-2)

Methyl ethyl ketone (E-3)

Toluene (E-4)

P-methoxyphenol (G-1)

IRGACURE 907 (H-1)

LUCIRIN TPO (H-2)

Trimethylolpropane tris (3-mercaptopropionate) (I-1)

2-hydroxy-3-phenoxypropyl acrylate (I-2)

MEGAFACE R-40 (J-1)

Polypropylene (Mw = 1960) (J-2)

ZFS460 (manufactured by Ebonic Industries, Ltd.) (J-3)

(Example 1)

(Orientation)

(20 DEG C) at a rotation speed of 100 rpm at room temperature (25 DEG C) for 20 seconds on a glass substrate with polyimide for horizontal orientation (SE-6414 manufactured by Nissan Chemical Industries, Ltd.) rubbed with the prepared polymerizable liquid crystal composition Dried at 70 ° C for 2 minutes, left at 25 ° C for 1 minute, and then irradiated with UV light of 30 mW at room temperature for 30 seconds using a high-pressure mercury lamp, thereby obtaining the thin film of Example 1. The obtained thin film was evaluated under the following conditions.

&Amp; cir &: There were no defects in the naked eye, and no defects were observed in the polarization microscope observation.

DELTA: There is no defect in the naked eye, but in the observation with a polarizing microscope, a non-oriented part exists in a part.

X: Some defects were observed with naked eyes, and even when observed under a polarizing microscope, non-oriented portions were present as a whole.

(Measurement of haze)

The thin film obtained in the above orientation test was measured at three points using a turbidimeter NDH2000 manufactured by Nippon Denshoku Kogyo Co., Ltd. to evaluate the average value.

(?, ??)

The selective reflection central wavelength (?) And the maximum reflectance of the thin film obtained in the above orientation test were measured using a spectrophotometer (V-560, manufactured by Nippon Bunko), and a wavelength bandwidth having a reflectance half of the maximum reflectance was selected And was obtained as a reflection wavelength band DELTA lambda.

The results obtained are shown in the following table.

[Table 6]

[Table 7]

[Table 8]

[Table 9]

(Examples 2 to 33 and Comparative Examples 1 to 5)

A thin film was prepared using the polymerizable liquid crystal compositions (2) to (31), (34) to (38), and the alignment property and the haze measurement result were measured. The results are shown in the above table as Examples 2 to 31 and Comparative Examples 1 to 5, respectively.

In Examples 2 to 18, Examples 22 to 31, Example 32, Example 33, and Comparative Examples 1 to 5, as the materials for the evaluation of orientation and the like, A glass substrate with a horizontal orientation polyimide (SE-6414, manufactured by Nissan Chemical Industries, Ltd.) was used, and the application and curing conditions of the polymerizable liquid crystal composition were the same as those in Example 1.

On the other hand, in Examples 19 to 21, PET was used as a base material for the evaluation of orientation and the like, and the PET substrate was coated at room temperature by a bar coater method. After drying at 60 ° C for 2 minutes, Using a high-pressure mercury lamp, UV light was irradiated by setting the accumulated light quantity to 900 mJ / cm ² .

In Examples 32 and 33 using the polymerizable liquid crystal compositions 32 and 33, since the components (D-1) to (D-3) are not contained in the polymerizable liquid crystal composition, ? N was measured. The retardation? N at 550 nm was measured with a retardation film / optical material inspection apparatus RETS-100 (manufactured by Otsuka Electronics Co., Ltd.) and the film thickness d was measured with a contact type shape measuring device DEKTAK (manufactured by Bruker) And? N was calculated from the relationship of? N x d. As a result,? N of the thin film obtained in Example 22 was 0.090, and? N of the thin film obtained in Example 23 was 0.050.

The polymerizable liquid crystal compound represented by the general formula (I-1) of the present invention represented by the formulas (A-1) to (A-8) and the polymerizable liquid crystal compound represented by the formulas (B- (I-1) of the present invention is a polymerizable liquid crystal composition (Examples 1 to 33) containing a polymerizable liquid crystal compound represented by the general formula (II-1) (Comparative Examples 1 to 5) containing no polymerizable liquid crystal compound represented by the general formula (II-1) or a polymerizable liquid crystal compound represented by the general formula (II-1) , The value of the selective reflection wavelength band DELTA lambda / the selective reflection central wavelength lambda, and the value of DELTA n are low and an optical film excellent in transmittance can be obtained.

Claims (10)

(I-1)

(Wherein P ¹¹¹ and P ¹¹² each independently represent a polymerizable functional group,
Sp ¹¹¹ and Sp ¹¹² each independently represent an alkylene group having 1 to 18 carbon atoms or a single bond and one -CH ₂ - in the alkylene group or two or more non-adjacent -CH ₂ - -COO-, -OCO- or -OCO-O-, one or two or more hydrogen atoms of the alkylene group may be substituted by a halogen atom or a CN group,
X ¹¹¹ and X ¹¹² each independently represent -O-, -S-, -OCH ₂ -, -CH ₂ O-, -CO-, -COO-, -OCO-, -CO-S-, CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH 2 -, -CH 2 S-, -CF 2 O-, -OCF 2 -, -CF 2 S- , -SCF ₂ -, -CH═CH-COO-, -CH═CH-OCO-, -COO-CH═CH-, -OCO-CH═CH-, -COO-CH ₂ CH ₂ -, -OCO- CH ₂ CH ₂ -, -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH ₂ -, -OCO-CH ₂ -, -CH ₂ -COO-, -CH ₂ -OCO -, -CH = CH-, -N = N-, -CH = NN = CH-, -CF = CF-, -C≡C- , or represents a single bond ^{(where, P 111 -Sp 111, P 112} - Sp ¹¹² , Sp ¹¹¹ -X ¹¹¹ and Sp ¹¹² -X ¹¹² do not contain a direct bond between oxygen atoms)
q111 and q112 each independently represent 0 or 1,
A ¹¹ and A ¹² each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group, a bicyclo [2.2.2] octane-1,4-diyl group, a pyridine- Diyl group, a naphthalene-2,6-diyl group, a naphthalene-1,4-diyl group, a tetrahydronaphthalene-2,6-diyl group, a decahydronaphthalene- Or 1,3-dioxane-2,5-diyl group, which groups may be unsubstituted or substituted by one or more substituents L,
L is a group selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group, a nitro group, a cyano group, an isocyanato group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, , A diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, an optionally substituted phenyl group, an optionally substituted phenylalkyl group, an optionally substituted cyclohexylalkyl group, or one -CH ₂ - -CH ₂ - each independently represents -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O- O-, -CO-NR ⁰ -, -NR ⁰ -CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = - CH = CH-, -N = N-, -CR ⁰ = N-, -N = CR ⁰ -, -CH = NN = CH-, -CF = CF- or -C≡C- wherein R ⁰ Represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), which may be substituted by a linear or branched alkyl group having 1 to 20 carbon atoms, And any hydrogen atom in the alkyl group may be substituted with a fluorine atom. When a plurality of L's are present in the compound, they may be the same or different. When a plurality of A ^{11 s} exist, they may be the same or different. , When a plurality of A ¹² exist, they may be the same or different,
Z ¹¹ and Z ¹² each independently represent -O-, -S-, -OCH ₂ -, -CH ₂ O-, -CH ₂ CH ₂ -, -CO-, -COO-, -OCO-, -CO -O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO- -NH-O-, -O-NH-, -SCH 2 -, -CH 2 S-, -CF 2 O-, -OCF 2 -, -CF 2 S-, -SCF 2 -, -CH = CH- -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-, -CH═NN═CH-, -CF═CF-, -C≡C-, or a single bond. When a plurality of Z ¹¹ exist, they are the same And when a plurality of Z < ¹² > s exist, they may be the same or different,
m111 and m112 each independently represent an integer of 0 to 2,
R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom, a cyano group, a hydroxyl group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, An alkylcarbonyloxy group having 2 to 10 carbon atoms, an alkylcarbonyloxy group having 2 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aromatic ring group having 5 to 12 carbon atoms, wherein either R ¹ or R ² is hydrogen Or R ² represents a cyclic group linked to the substituent L of adjacent A ¹² ), and at least one polymerizable liquid crystal compound represented by the following general formula (II- One)

(Wherein P < ²¹¹ > represents a polymerizable functional group,
A ²¹¹ and A ²¹² each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group, a bicyclo [2.2.2] octane-1,4-diyl group, a pyridine- Diyl group, a naphthalene-2,6-diyl group, a naphthalene-1,4-diyl group, a tetrahydronaphthalene-2,6-diyl group, a decahydronaphthalene- Or 1,3-dioxane-2,5-diyl group, which groups may be unsubstituted or substituted by one or more substituents L,
L is a group selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group, a nitro group, a cyano group, an isocyanato group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, , A diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, an optionally substituted phenyl group, an optionally substituted phenylalkyl group, an optionally substituted cyclohexylalkyl group, or one -CH ₂ - -CH ₂ - each independently represents -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O- O-, -CO-NR ⁰ -, -NR ⁰ -CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = - CH = CH-, -N = N-, -CR ⁰ = N-, -N = CR ⁰ -, -CH = NN = CH-, -CF = CF- or -C≡C- wherein R ⁰ Represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), which may be substituted by a linear or branched alkyl group having 1 to 20 carbon atoms, And any hydrogen atoms in the alkyl group may be substituted with a fluorine atom. When a plurality of L's are present in the compound, they may be the same or different. When a plurality of A ²¹² 's exist, they may be the same or different. ,
Z ²¹¹ _{is, -O-, -S-, -OCH 2 -} , -CH 2 O-, -CH 2 CH 2 -, -CO-, -COO-, -OCO-, -CO-S-, -S -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH- _{-O-NH-, -SCH 2 -,} -CH 2 S-, -CF 2 O-, -OCF 2 -, -CF 2 S-, -SCF 2 -, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-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-, -N = CH-, -CH = NN = CH-, -CF = CF-, -C≡C- or a single bond. When a plurality of Z ²¹¹ exist, they may be the same or different,
m211 represents an integer of 1 to 3,
T ²¹¹ represents a hydrogen atom, -OH group, -SH group, -CN group, -COOH group, -NH ₂ group, -NO ₂ group, -COCH _{3 group, -O (CH 2) n CH} 3, or - ( CH ₂ ) _n CH ₃ , and n represents an integer of 0 to 20, in the polymerizable liquid crystal composition. The method according to claim 1,
Wherein the polymerizable liquid crystal composition comprises a polymerizable liquid crystal composition containing 10 to 95% by mass of a polymerizable liquid crystal compound represented by the general formula (I-1) among the entire polymerizable liquid crystal compounds contained in the composition, Composition. The method according to claim 1 or 2,
Wherein the polymerizable liquid crystal composition comprises a polymerizable liquid crystal composition containing 5 to 85% by mass of a polymerizable liquid crystal compound represented by the general formula (II-1) among the entire polymerizable liquid crystal compounds contained in the composition, Composition. An optical film using the polymerizable liquid crystal composition according to any one of claims 1 to 3. The method of claim 4,
The birefringence difference? N is 0.1 or less. The method according to any one of claims 1 to 3,
Wherein the polymerizable liquid crystal composition further comprises a chiral compound. An optical film using the polymerizable liquid crystal composition according to claim 6. The method of claim 7,
Wherein the value of the selective reflection wavelength band (DELTA lambda) / selective reflection central wavelength (?) Is 0.1 or less. A laminated film obtained by laminating the optical film according to claim 4 and / or the optical film according to claim 7 with another optical element. An image display apparatus using the optical film according to claim 4 and / or the optical film according to claim 7.