JP2018035126A - Polymerizable compound and optically anisotropic body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable compound which has high storage stability and can form a film-like polymer while being difficult to cause alignment defects, where the film-like polymer is less likely to be separated from a substrate even when irradiated with ultraviolet for a long time.SOLUTION: The invention provides a compound represented by general formula (I), and a polymer thereof. A composition comprising the compound is useful as a polymerizable liquid crystal composition. (For example, the compound is bis[4-(acryloyloxyethoxy-ethoxy-ethoxy)phenyl]1,4-cyclohexanedicarboxylate.)SELECTED DRAWING: None

Description

  The present invention relates to a compound having a polymerizable group, a polymerizable composition containing the compound, a polymerizable liquid crystal composition, and an optical anisotropic body using the polymerizable liquid crystal composition.

  Polymerizable compounds are used as materials for various films. For example, it is possible to produce a film having a uniform orientation by polymerizing after aligning a polymerizable compound in a liquid crystal state. Thus, the produced film can be used for a polarizing plate, a phase difference plate, etc. which are required for a liquid crystal display. As such a polymerizable compound, the compounds described in Patent Documents 1 to 3 are known.

  The polymerizable compound can also be used to produce a film having a cholesteric structure. In particular, a polymerizable liquid crystal compound having a low refractive index anisotropy (Δn) is useful as a material for a film having a cholesteric phase having a narrow selective reflection wavelength width. In many cases, two or more types of polymerizability are required to satisfy the required optical properties, polymerization rate, solubility, melting point, glass transition temperature, film transparency, mechanical strength, surface hardness, heat resistance and light resistance. Compositions consisting of compounds are used. At that time, the polymerizable compound to be used is required to bring good physical properties to the composition without adversely affecting other properties. In particular, when the purpose is to produce a film having a cholesteric structure, a polymerizable compound that can exist as a nematic phase or a cholesteric phase in a wide temperature range and has a high nematic phase or cholesteric phase liquid crystal orientation is required.

  When a polymerizable composition containing a polymerizable compound is used as an optical film material for a display or the like, it is preferable that there are few orientation defects when the polymerizable composition is applied to a substrate and polymerized. Further, from the viewpoint of the process, it is preferable that the polymerizable composition in the component does not precipitate even when the polymerizable composition is stored for a long period of time and has high storage stability. Moreover, when using an optical film for a mobile device, it is preferable that peeling from a base material does not occur easily when ultraviolet light is irradiated for a long time.

WO2003 / 062286A1 JP, 2006-017034, A WO2005 / 022260A1 publication

  Conventionally known compounds have many problems mainly in terms of reliability. That is, precipitation occurs when it is added to the polymerizable composition and stored for a long period of time, alignment defects occur when a film is produced, or when the obtained film is irradiated with ultraviolet light for a long time, It is a problem that peeling does not occur.

  The present invention provides a polymerizable compound useful as a raw material for an optical anisotropic body, in which such problems are improved.

  That is, the polymerizable compound of the present invention exhibits high storage stability when added to the polymerizable composition.

  In addition, according to the polymerizable composition containing the polymerizable compound, it is possible to produce a film-like polymer that is less likely to cause orientation defects and is less likely to peel from the substrate when irradiated with ultraviolet light for a long time. Can do.

  The present invention provides a film-like polymer that hardly causes such alignment defects and that hardly peels off from a substrate when irradiated with ultraviolet light for a long time.

  As a result of intensive studies to solve the above problems, the present inventors have developed a polymerizable compound having a specific structure. That is, the present invention provides a compound represented by the general formula (I), a polymerizable composition containing the compound, a resin using the compound, a resin additive, an oil, a filter, an adhesive, and an adhesive. Agents, oils and fats, inks, pharmaceuticals, cosmetics, detergents, building materials, packaging materials, liquid crystal materials, organic EL materials, organic semiconductor materials, electronic materials, display elements, electronic devices, communication equipment, automobile parts, aircraft parts, machine parts, Agrochemicals and foods, products using them, polymerizable liquid crystal compositions, polymers obtained by polymerizing the polymerizable liquid crystal compositions, and optical anisotropic bodies using the polymers are provided.

  The compound of the present invention has high storage stability when added to a polymerizable composition containing another polymerizable compound, and when a film-like polymer is produced, alignment defects are less likely to occur. When the polymer is irradiated with ultraviolet light for a long time, it is difficult to peel off from the base material, and therefore, it is useful as a constituent member of the polymerizable composition. Moreover, the said polymeric composition is useful for the use of optical materials, such as a phase difference film and a selective reflection film.

  The present invention provides a compound having a specific structure (hereinafter also referred to as a polymerizable compound), a polymerizable composition containing the compound, a resin using the compound, a resin additive, an oil, a filter, Adhesives, adhesives, oils and fats, inks, pharmaceuticals, cosmetics, detergents, building materials, packaging materials, liquid crystal materials, organic EL materials, organic semiconductor materials, electronic materials, display elements, electronic devices, communication equipment, automobile parts, aircraft parts , Mechanical parts, agricultural chemicals and foods, products using them, polymerizable liquid crystal compositions, polymers obtained by polymerizing the polymerizable liquid crystal compositions, and optical anisotropic bodies using the polymers.

  The compound of the present invention is represented by the following general formula (I).

(Wherein P ¹ represents a group that is polymerized by radical polymerization, cationic polymerization, or anionic polymerization, k1 represents an integer of 2 to 10, and X ¹ represents —CH ₂ —, —CO—, —CF ₂ —, — COO -, - CO-S - , - CO-NH -, - CO-CH = CH -, - COO-CH = CH -, - CO-CH 2 CH 2 -, - COO-CH 2 CH 2 -, - CO—CH ₂ —, —COO—CH ₂ — or a single bond, each of A ¹ and A ² is independently 1,4-phenylene group, 1,4-cyclohexylene group, bicyclo [2.2.2 ] Octane-1,4-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2 , 6-Diyl group, decahydronaphthalene-2 Represents a 6-diyl group or 1,3-dioxane-2,5-diyl group, these groups may be substituted by unsubstituted or substituted with one or more substituents L, A ¹ is more present In this case, they may be the same or different, and L is a fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group , Mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, optionally substituted phenyl group, optionally substituted phenylalkyl group, substituted good cyclohexylalkyl group optionally or one -CH ₂ - or nonadjacent two or more -CH ₂ - Each independently -O -, - S -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-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 = N-N = CH-, -CF = CF- or -C≡C- (wherein R ⁰ is a hydrogen atom or a carbon atom number) Represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by 1) to 8), and any hydrogen atom in the alkyl group is substituted with a fluorine atom. Or L may represent a group represented by P ^L — (CH ₂ CH ₂ O) _kL —X ^L —, where P ^L Radical polymerization, a group of polymerization by cationic polymerization or anionic polymerization, kL is an integer of from 2 to ^10, X _L is _{-CH 2 -, - CO -,} - CF 2 -, - COO -, - CO- S -, - CO-NH - , - CO-CH = CH -, - COO-CH = CH -, - CO-CH 2 CH 2 -, - COO-CH 2 CH 2 -, - CO-CH 2 -, —COO—CH ₂ — or a single bond, and when a plurality of Ls are present in the compound, they may be the same or different, and Z ¹ represents —O—, —S—, —OCH ₂ —. _{, -CH 2 O -, - CH} 2 CH 2 -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-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═N—N═CH—, —CF═CF—, —C≡C— or a single bond, but when multiple Z ¹ are present, they are the same a be different even better than, m1 represents an integer of 0 to 5, R ² is a hydrogen atom, a fluorine atom, a chlorine atom, Atom, iodine atom, pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, Chioisoshiano group, or one -CH 2 _- or nonadjacent two or more -CH 2 _- are each independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH Represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by -CO-, -CH = CH-, -CF = CF- or -C≡C-. Any hydrogen atom in the above may be substituted with a fluorine atom, or R ² is a group represented by —X ² — (OCH ₂ CH ₂ ) _k2 —P ² (wherein P ² is radical polymerization, cation Represents a group that is polymerized by polymerization or anionic polymerization, and k2 is 2 to 10 Represents an ^integer, X ₂ is _{-CH 2 -, - CO -,} - CF 2 -, - OCO -, - S-CO, -NH-CO -, - CH = CH-CO -, - CH = CH-OCO _{-, - CH 2 CH 2 -CO} -, - CH 2 CH 2 -OCO -, - CH 2 -CO -, - represents a CH 2 -OCO- or a single bond. At least one of Z ¹ present represents a group other than a single bond, and at least one of A ¹ and A ² present is a 1,4-cyclohexylene group, bicyclo [2.2.2]. Represents an octane-1,4-diyl group, a decahydronaphthalene-2,6-diyl group or a 1,3-dioxane-2,5-diyl group, these groups being unsubstituted or one or more The substituent L may be substituted. )
Since the compound represented by the general formula (I) has the above structure, the refractive index anisotropy (Δn) can be set to a low value. As Δn of the compound of the present invention, the lower limit is preferably 0.01 or more. The upper limit is preferably 0.30 or less, more preferably 0.25 or less, more preferably 0.20 or less, more preferably 0.10 or less, and 0.08 or less. It is particularly preferred that Since the compound of the present invention can keep the Δn value low, it is particularly preferable as a material for a film having a cholesteric structure having a narrow selective reflection wavelength width.

In the compound represented by the general formula (I), the number of aromatic rings contained in the structure is preferably 3 or less, more preferably 1 or 2 from the viewpoint of further reducing Δn. preferable. Moreover, it is also preferable not to have a partial structure in which A ¹ adjacent to each other through Z ¹ and A ¹ and A ² are both aromatic rings in the molecule. Since the compound represented by the general formula (I) has the above structure, when added to a liquid crystal composition exhibiting cholesteric alignment, the cholesteric alignment of the liquid crystal composition is not hindered and maintained well. can do.

In general formula (I), P ¹ and P ² present each independently represent a group that is polymerized by radical polymerization, cationic polymerization, or anionic polymerization, and each independently represents the following formula (P-1) to formula ( P-20)

It is preferable to represent a group selected from: In particular, when ultraviolet polymerization is performed as a polymerization method, the formula (P-1), formula (P-2), formula (P-3), formula (P-4), formula (P-5), formula (P -7), formula (P-8), formula (P-11), formula (P-13), formula (P-15) or formula (P-18) are preferred, and formula (P-1), formula (P-18) P-2), formula (P-3), formula (P-8), formula (P-11) or formula (P-13) are more preferred, and formula (P-1), formula (P-2) or Formula (P-3) is more preferable, and formula (P-1) or formula (P-2) is particularly preferable.

  In general formula (I), k1 and existing k2 each independently represent an integer of 2 to 10, but from the viewpoint of ease of synthesis and liquid crystallinity, each independently represents an integer of 2 to 8. More preferably, each independently represents an integer of 2 to 6, more preferably each independently represents an integer of 2 to 4, each independently independently more preferably 2 or 3, and each represents 3. It is particularly preferred.

In the general formula (I), X ¹ represents —CH ₂ —, —CO—, —CF ₂ —, —COO—, —CO—S—, —CO—NH—, —CO—CH═CH—, —COO. _{-CH = CH -, - CO-} CH 2 CH 2 -, - COO-CH 2 CH 2 -, - CO-CH 2 -, - COO-CH 2 - or a single bond. From the viewpoints of availability of raw materials and ease of synthesis, X ¹ represents —CO—, —COO—, —CO—CH═CH—, —CO—CH ₂ CH ₂ —, —COO—CH ₂ CH ₂ —. Or a single bond, preferably —CO—, —COO—, —CO—CH ₂ CH ₂ —, —COO—CH ₂ CH ₂ — or a single bond, and more preferably —CO—, —COO. It is more preferable to represent-or a single bond, and it is even more preferable to represent -CO- or a single bond. From the viewpoint of the availability of raw materials and the ease of synthesis, and the solubility of the compound in a solvent, the group represented by A ¹ directly bonded to X ¹ is a 1,4-phenylene group, pyridine-2,5 -Diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl When it represents a group or a 1,3-dioxane-2,5-diyl group, X ¹ particularly preferably represents a single bond. When the group represented by A ¹ directly bonded to X ¹ represents a 1,4-cyclohexylene group or a bicyclo [2.2.2] octane-1,4-diyl group, X ¹ is − It is particularly preferred to represent CO-.

In the general formula (I), X ² present is —CH ₂ —, —CO—, —CF ₂ —, —OCO—, —S—CO, —NH—CO—, —CH═CH—CO—, — _{CH = CH-OCO -, -} CH 2 CH 2 -CO -, - CH 2 CH 2 -OCO -, - CH 2 -CO -, - represents a CH 2 -OCO- or a single bond. From the viewpoint of availability of raw materials and ease of synthesis, X ² present is —CO—, —OCO—, —CH═CH—CO—, —CH ₂ CH ₂ —CO—, —CH ₂ CH ₂ —. preferably representing the OCO- or a single _{bond, -CO -, - OCO -,} - CH 2 CH 2 -CO -, - it is more preferable that represent _CH 2 CH 2 -OCO- or a single bond, -CO-, It is further preferable to represent —OCO— or a single bond, and it is even more preferable to represent —CO— or a single bond. From the viewpoint of availability of raw materials and ease of synthesis, and solubility of the compound in a solvent, the group represented by A ² directly bonded to X ¹ is a 1,4-phenylene group, pyridine-2,5. -Diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl When it represents a group or a 1,3-dioxane-2,5-diyl group, it is particularly preferred that X ² present represents a single bond. Further, when the group represented by A ² directly bonded to X ¹ represents a 1,4-cyclohexylene group or a bicyclo [2.2.2] octane-1,4-diyl group, the existing X ² Particularly preferably represents —CO—.

In the general formula (I), A ¹ and A ² are each independently 1,4-phenylene group, 1,4-cyclohexylene group, bicyclo [2.2.2] octane-1,4-diyl group, pyridine. -2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2 , 6-diyl group or 1,3-dioxane-2,5-diyl group, these groups may be unsubstituted or substituted by one or more substituents L. In the general formula (I), a plurality of A ¹ may exist, provided that at least one of A ¹ and A ² present is a 1,4-cyclohexylene group, bicyclo [2.2.2] octane- Represents a 1,4-diyl group, a decahydronaphthalene-2,6-diyl group or a 1,3-dioxane-2,5-diyl group, these groups being unsubstituted or one or more substituents It may be replaced by L. In view of ease of synthesis, availability of raw materials, and liquid crystallinity, A ¹ and A ² are each independently unsubstituted or may be substituted with one or more substituents L -Represents a phenylene group, 1,4-cyclohexylene group, bicyclo [2.2.2] octane-1,4-diyl group, naphthalene-2,6-diyl group or naphthalene-1,4-diyl group. Preferably, each independently of the following formulas (A-1) to (A-16)

It is more preferable to represent a group selected from: In addition, from the viewpoint of low refractive index anisotropy, at least one of A ¹ and A ² present represents a group selected from the above formula (A-2) or formula (A-10), More preferably, each of the remaining groups independently represents a group selected from the above formulas (A-1) to (A-7) and (A-10), and at least one of A ¹ and A ² present Represents a group represented by the above formula (A-2), and it is even more preferable that the rest each independently represents a group selected from the above formulas (A-1) to (A-7). And at least one of A ¹ and A ² present represents a group represented by the above formula (A-2), and the rest each independently represents the above formula (A-1) to the formula (A-4). It is particularly preferred to represent a group selected from

A ¹ and A ² are preferably groups independently represented by the above formula (A-3) or formula (A-4) from the viewpoint of constituting the cholesteric liquid crystal composition. This is because when the compound of the present invention has a substituent at a lateral position of the ring structure, it becomes easy to wind a helical pitch when a cholesteric liquid crystal composition is formed. In addition, if A ¹ and A ² are each independently a group represented by the above formula (A-3) or (A-4), the objectivity of the molecular structure of the compound of the present invention decreases. The solubility in the liquid crystal composition can be improved. In the general formula (I), 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, an amino group, a hydroxyl group, a mercapto group, a methylamino group, A dimethylamino group, a diethylamino 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, Alternatively, one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—. S -, - S-CO - , - O-COO -, - 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 = Number of carbon atoms that may be substituted by N—N═CH—, —CF═CF—, or —C≡C— (wherein R ⁰ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms). 1 to 20 linear or branched alkyl groups are represented, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or L is P ^L — (CH ₂ CH ₂ O) _kL The group represented by -X ^L- may be represented, but when a plurality of L are present in the compound, they may be the same or different. From the viewpoint of liquid crystallinity and ease of synthesis, the substituent L is a fluorine atom, chlorine atom, pentafluorosulfuranyl group, nitro group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, or any A hydrogen atom may be substituted with a fluorine atom, and one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—, —COO. A straight chain having 1 to 20 carbon atoms which may be substituted by a group selected from-, -OCO-, -O-CO-O-, -CH = CH-, -CF = CF- or -C≡C-. It is preferable to represent a chain or branched alkyl group, and the substituent L may be a fluorine atom, a chlorine atom, or an arbitrary hydrogen atom may be substituted with a fluorine atom, one —CH ₂ — or adjacent. not two or more -CH ₂ - is More preferably, it represents a linear or branched alkyl group having 1 to 12 carbon atoms which may be independently substituted with a group selected from —O—, —COO— or —OCO—. More preferably, L represents a fluorine atom, a chlorine atom, or an arbitrary hydrogen atom, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group or an alkoxy group, which may be substituted with a fluorine atom, The substituent L particularly preferably represents a fluorine atom, a chlorine atom, or a linear alkyl group or linear alkoxy group having 1 to 8 carbon atoms. The substitution group L _{^{P L - (CH 2 CH 2}} O) kL -X L - may represent a group represented by ^but, P L, ^X preferred structure of ^L and kL are each formula (I ) In P ¹ , X ¹ and k ¹ .

In the general formula (I), Z ¹ 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═N—N═CH—, —CF═CF—, —C≡C— Or although it represents a single bond, when a plurality of Z ¹ are present, they may be the same or different. However, at least one of Z ¹ present represents a group other than a single bond.

In particular, when emphasizing the balance between storage stability and liquid crystallinity, when there are a plurality of Z ^{1 s,} they may be the same or different from each other, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH _2. -, - COO -, - OCO -, - NH-O -, - O-NH -, - CH = CH-COO -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO- _{CH 2 CH 2 -, - CH} 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N -, - N = CH -, - CH ═N—N═CH—, —CF═CF—, —C≡C— or a single bond is preferred, and when there are a plurality of Z ^{1 s,} they may be the same or different, —OCH _{2 -, - CH 2 O -,} - CH 2 CH 2 -, - COO -, - OCO -, - CH = CH _{-COO -, - OCO-CH =} CH -, - COO-CH 2 CH 2 -, - CH 2 CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH -, -CF = CF-, -C≡C- or a single bond is more preferable, and when there are a plurality of Z ^{1 s,} they may be the same or different. -OCH _2- , -CH _{2 O -, - CH 2 CH 2} -, - COO -, - OCO -, - COO-CH 2 CH 2 - or and particularly preferably a _-CH 2 _CH 2 -OCO-.

In particular, when importance is attached to the small number of orientation defects, when there are a plurality of Z ^{1 s,} they may be the same or different, —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 = N-N = CH-, -CF = CF-, -C≡C- or simple It is preferable to represent a bond, and when a plurality of Z ¹ are present, they may be the same or different, —COO—, —OCO—, —CO—NH—, —NH—CO—, —CH═CH -COO-, -OCO-CH = CH-, -CH = CH-, -N = N-, -CH = N-N = CH , -CF = CF -, - C≡C- or is more preferably a single bond, ^{Z 1} is them if there are a plurality may be different even in the same -COO -, - OCO -, - It is more preferable to represent CO—NH— or —NH—CO—, and when a plurality of Z ¹ are present, they may be the same or different, and it is particularly preferable to represent —COO— or —OCO—.

In particular, when importance is attached to the difficulty of peeling from the substrate when irradiated with ultraviolet light for a long time, when there are a plurality of Z ^{1 s,} they may be the same or different, -O-, -OCH _{2 -, - CH 2 O -} , - CH 2 CH 2 -, - CO -, - COO -, - OCO -, - OCO-O -, - CO-NH -, - NH-CO -, - OCO —NH—, —NH—COO—, —NH—CO—NH—, —NH—O—, —O—NH—, —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 -, - CH = N -, - N = CH -, - CF = CF -, - C≡C- or preferably a single bond, ^{Z 1} is them if there are a plurality in the same may -OCH ₂ also be different _{-, - CH 2 O -,} - CH 2 CH 2 -, - COO -, - OCO -, - OCO-O -, - CO-NH -, - NH-CO _{-, - COO-CH 2 CH} 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, -CH ₂ -COO-, -CH ₂ -OCO- or a single bond is more preferable, and when there are a plurality of Z ^{1 s,} they may be the same or different -OCH ₂ -,- _{CH 2 O -, - CH 2} CH 2 -, - COO -, - OCO- or single More preferably representing a case, Z ¹ is them if there are a plurality may be different even in the same -COO -, - OCO- or even more preferably a single bond, Z ¹ is a single bond Is particularly preferred.

Especially when importance is placed on the balance between the availability of raw materials and ease of synthesis, liquid crystallinity, storage stability, few alignment defects, and the difficulty of peeling from the substrate when irradiated with ultraviolet light for a long time. , Z ¹ may be the same or different when a plurality of Z ¹ exist, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ —, —COO—, —OCO—, —CH═CH _{-COO -, - OCO-CH =} CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - CH ═CH—, —CF═CF—, —C≡C— or a single bond is preferred, and when there are a plurality of Z ^{1 s,} they may be the same or different, —OCH ₂ —, —CH ₂ O-, -CH ₂ CH _2- , -COO-,- _{OCO -, - COO-CH 2} CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - CH = CH -, - C≡C- Or more preferably a single bond, and when there are a plurality of Z ^{1 s,} they may be the same or different, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —COO. _{-CH 2 CH 2 -, - CH} 2 CH 2 -OCO- or more preferably a single bond, ^{Z 1} is them if there are a plurality may be different even in the same -OCH ₂ -, - Even more preferably, it represents CH ₂ O—, —COO—, —OCO— or a single bond. In addition, when placing importance on the balance between the availability of raw materials and ease of synthesis, liquid crystallinity, storage stability, few alignment defects, and the difficulty of peeling from the substrate when irradiated with ultraviolet light for a long time. , in the compound represented by the general formula (I), it is preferable that the ratio of the Z ¹ represents a single bond of Z ¹ is as small as possible. More specifically, when m1 represents 1, Z ¹ particularly preferably represents —OCH ₂ —, —CH ₂ O—, —COO— or —OCO—, and when m1 represents 2, two one is -OCH ₂ of ^{Z 1} that is present _{-, - CH 2 O -,} - COO -, - OCO- or a single bond, the other is _{-OCH 2 -, - CH 2 O} -, - COO- or It is even more preferable that —OCO— is represented, and two Z ¹ may be the same or different and may represent —OCH ₂ —, —CH ₂ O—, —COO— or —OCO—. Particularly preferably, when m1 represents 3, one of the three Z ¹ presents represents —OCH ₂ —, —CH ₂ O—, —COO—, —OCO— or a single bond, and the remaining two represent —OCH. _2- , -CH ₂ O-, -COO- or -OCO- Are particularly preferred, m1 may represent 4, four of one of the ^{Z 1} present _{-OCH 2 -, - CH 2 O} -, - COO -, - OCO- or a single bond, the remaining are three - OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, or when m1 represents 4, two of the four Z ¹ are —OCH ₂ —, —CH ₂ O— , -COO -, - OCO- or a single bond, but the remaining two _{-OCH 2 -, - CH 2 O} -, - particularly preferably represents an COO- or -OCO-, if m1 represents 5, Of the five Z ¹ , one represents —OCH ₂ —, —CH ₂ O—, —COO—, —OCO— or a single bond, and the remaining four represent —OCH ₂ —, —CH ₂ O—, — Represents COO- or -OCO-, or 5 if m1 represents 5 Two are -OCH ₂ out of ^{Z 1} to _{-, - CH 2 O -,} - COO -, - OCO- or a single bond, but the remaining three _{-OCH 2 -, - CH 2 O} -, - COO- or It is particularly preferable to represent —OCO—.

In general formula (I), m1 independently represents an integer of 0 to 5, but m1 preferably represents an integer of 1 to 4 from the viewpoints of solubility in a solvent, liquid crystallinity, and storage stability. . In addition, from the viewpoint of ease of synthesis and yield, when R ² represents a group represented by —X ² — (OCH ₂ CH ₂ ) _k2 —P ² , m1 represents ² , 3 or 4. More preferably, it represents 2 or 4, and when R ² represents a group other than the group represented by —X ² — (OCH ₂ CH ₂ ) _k2 —P ² , m1 represents 1 to 3. It is more preferable to represent an integer, and it is particularly preferable to represent 1 or 2.

In the general formula (I), R ² represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or one — CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—. 1 carbon atom which may be substituted by CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-, -CF = CF- or -C≡C- To 20 straight-chain or branched alkyl groups, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or R ² represents —X ² — (OCH ₂ CH ₂ ) _k2. It represents a group represented by -P ^2. When importance is attached to the flexibility in the case of a film, R ² preferably represents a group other than the group represented by —X ² — (OCH ₂ CH ₂ ) _k2 —P ^2. When importance is attached to strength, R ² preferably represents a group represented by —X ² — (OCH ₂ CH ₂ ) _k2 —P ² .
When R ² represents a group other than the group represented by —X ² — (OCH ₂ CH ₂ ) _k2 —P ² , R ² represents a hydrogen atom, a fluorine atom, chlorine from the viewpoint of liquid crystallinity and ease of synthesis. An atom, a cyano group, or one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —CO—, —COO—, —OCO—, —O. A straight chain having 1 to 12 carbon atoms which may be substituted by —CO—O—, —CO—NH—, —NH—CO—, —CH═CH—, —CF═CF— or —C≡C— Or it is preferable to represent a branched alkyl group, and R ² is a hydrogen atom, a fluorine atom, a chlorine atom, or one —CH ₂ — or two or more non-adjacent —CH ₂ — each independently — Substituted by O-, -CO-, -COO-, -OCO- or -O-CO-O- It is more preferable that represent have linear or branched alkyl group having a carbon number of 1 to 12, R ² is a hydrogen atom, a fluorine atom, a chlorine atom, or a number of 1 to 12 carbon atoms straight-chain alkyl group or straight chain alkoxy It is more preferable that R ² represents a group, and R ² particularly preferably represents a linear alkyl group having 1 to 12 carbon atoms or a linear alkoxy group.

Further, ^{R 2} is ^-X 2 _- if a group represented by _{(OCH 2 CH 2) k2 -P} 2, the preferred structure of P 2, ^{X 2} and k2 are each as defined above.

  Examples of the compound represented by the general formula (I) include the following general formula (IA) or general formula (IB)

(Wherein P ¹ , P ² , X ¹ , X ² , A ¹ , A ² , Z ¹ , m 1, k ¹ and k 2 are respectively P ¹ , P ² , X ¹ , X ² , A ¹ , A ² , Z ¹ , m 1, k ¹ and k 2 have the same meaning, and when there are a plurality of A ¹ and Z ^1, they may be the same or different, R ²¹ is a hydrogen atom, A fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or one —CH ₂ — or two or more non-adjacent — CH ₂ — is independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO. By —NH—, —NH—CO—, —CH═CH—, —CF═CF— or —C≡C—. Represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom). preferable.

  As the compound represented by the general formula (I), the following general formula (IA-1) to general formula (IB-5)

(* Mark in the formula indicates connection of structure)

(* Mark in the formula indicates connection of structure)

^{(Wherein, P 1, P 2, X} 1, X 2, k1 and k2 each represent the same meaning as ^{P 1, P 2, X 1} , X 2, k1 and k2 in Formula ^{(I), A 11} _, A ¹² _, A ¹³ and A ²¹ are a group selected from the above formulas (A-1) to (A-7) which may be unsubstituted or substituted by one or more of the above substituents L. And the preferred structure of the substituent L is the same as the preferred structure of the substituent L in the general formula (I), and Z ¹¹ _, Z ¹² _, Z ¹³ and Z ¹⁴ are —OCH ₂ —, —CH ₂ O—. _{, -CH 2 CH 2 -, -} COO -, - OCO -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - CH = CH -, - C≡C- or represents a single bond, there ^{Z _11,} At least one of Z ¹² _, Z ¹³ and Z ¹⁴ represents a group other than a single bond, and R ²² represents a hydrogen atom, a fluorine atom, a chlorine atom, or one —CH ₂ — or _two not adjacent to each other. A straight chain having 1 to 12 carbon atoms, in which the above —CH ₂ — may be independently substituted with —O—, —CO—, —COO—, —OCO— or —O—CO—O—, or Represents a branched alkyl group.), And the following general formula (IA-1-1) to general formula (IB-5-1):

(* Mark in the formula indicates connection of structure)

(* Mark in the formula indicates connection of structure)

(* Mark in the formula indicates connection of structure)

^(Wherein the same meaning as ^{P 1, P 2, X 1} , X 2, k1, P 1, P 2 in the k2 and L are each formula ^{(I), X 1, X} 2, k1, k2 and L Z ¹¹¹ _, Z ¹²¹ _, Z ¹³¹ and Z ¹⁴¹ are —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —COO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —OCO—. Or a single bond, but at least one of Z ¹¹¹ _, Z ¹²¹ _, Z ¹³¹ and Z ^{141 present} represents a group other than a single bond, R ²¹¹ represents a hydrogen atom, a fluorine atom, a chlorine atom, or a carbon atom. A compound represented by a linear alkyl group of 1 to 12 or a linear alkoxy group, wherein r represents an integer of 0 to 4, is more preferable, and the following general formula (IA-1-2) 1) to general formula (IB-4-2-1)

(* Mark in the formula indicates connection of structure)

(* Mark in the formula indicates connection of structure)

Wherein W ¹ and W ² represent a hydrogen atom, a methyl group or a trifluoromethyl group, X ¹¹ and X ²¹ represent —CO—, X ¹² and X ²² represent a single bond, and k ¹¹ and k ²¹ represent 2, 3 or 4, Z ¹¹¹¹ _, Z ¹²¹¹ _, Z ¹³¹¹ and Z ¹⁴¹¹ represent —OCH ₂ —, —CH ₂ O—, —COO— or —OCO—, and Z ¹¹¹² _, Z ¹²¹² and Z ¹⁴¹² represent —OCH ₂ —, —CH ₂ O—, —COO—, —OCO— or a single bond is represented, and L ¹ is a fluorine atom, a chlorine atom, or a carbon atom in which an arbitrary hydrogen atom may be substituted with a fluorine atom A linear or branched alkyl group or an alkoxy group having 1 to 12 is represented, and r represents an integer of 0 to 4.

  Further, from the viewpoint of liquid crystallinity, 1,4-cyclohexylene group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl contained in the compound represented by the general formula (I) The group and decahydronaphthalene-2,6-diyl group may be either a cis isomer or a trans isomer or a mixture of both, but the trans isomer is the main component from the viewpoint of liquid crystallinity. It is particularly preferable that only the trans isomer is present.

  Specifically, compounds represented by the following formulas (I-1) to (I-63) are preferable as the compounds represented by the general formula (I).

(* Mark in the formula indicates connection of structure)

(* Mark in the formula indicates connection of structure)

(* Mark in the formula indicates connection of structure)

(* Mark in the formula indicates connection of structure)

(* Mark in the formula indicates connection of structure)

(* Mark in the formula indicates connection of structure)
The compound of this invention can be manufactured with the following manufacturing methods.
(Production method 1) Production of a compound represented by the following formula (S-10)

(* Mark in the formula indicates connection of structure)
(Wherein L represents the same meaning as L in formula (I), W ^s1 represents a hydrogen atom, a methyl group or a trifluoromethyl group, ks1 represents an integer of 1 to 9, and r represents 0 to 4 PG represents a protecting group, and halogen represents a halogen atom or a halogen equivalent.)
The carboxyl group of the compound represented by the formula (S-1) is protected with a protecting group (PG). The protecting group (PG) is not particularly limited as long as it can be stably protected until the deprotection step. For example, GREEN'S PROTECTIVE GROUPS IN ORGANIC SYNTHESIS ((Fourth Edition), PETER GM. Protecting groups (PG) mentioned in WUTS, THEODORA W. GREENE, John Wiley & Sons, Inc., Publication) and the like are preferred. Specific examples of the protecting group include a tetrahydropyranyl group, a tert-butyl group, a methoxymethyl group, an ethoxymethyl group, a methyl group, an ethyl group, and a benzyl group.

  The protecting group (PG) of the compound represented by the formula (S-2) is deprotected. The reaction conditions for deprotection are not particularly limited as long as they give the compound represented by formula (S-3), but those listed in the above-mentioned literature are preferable. It is also possible to obtain a compound represented by the formula (S-3) by protecting only one carboxyl group of the compound represented by the formula (S-1) with a protecting group (PG).

  A compound represented by the formula (S-6) is obtained by subjecting the compound represented by the formula (S-4) to dehydration condensation with a compound represented by the formula (S-5) in the presence of an acid. Examples of the acid catalyst include sulfuric acid and p-toluenesulfonic acid monohydrate. Examples of the solvent include toluene and xylene. Alternatively, a method of transesterifying the lower alcohol ester of the compound represented by the formula (S-5) and the compound represented by the formula (S-4) is also included.

  The compound represented by the formula (S-7) can be obtained by reacting the compound represented by the formula (S-6) with a compound represented by the formula (S-3) in the presence of a base. Examples of the base include potassium carbonate, cesium carbonate, triethylamine and the like.

  The protecting group (PG) of the compound represented by the formula (S-7) is deprotected. The reaction conditions for deprotection are not particularly limited as long as they give the compound represented by formula (S-8), but those listed in the above-mentioned literature are preferable.

The compound represented by the formula (S-10) can be obtained by reacting the compound represented by the formula (S-8) with a compound represented by the formula (S-9). As the reaction conditions, for example, a method using a condensing agent or a compound represented by the formula (S-8) is converted into an acid chloride, mixed acid anhydride or carboxylic acid anhydride, and then represented by the general formula (S-9). The method of making it react with a compound in base presence is mentioned. When a condensing agent is used, examples of the condensing agent include N, N′-dicyclohexylcarbodiimide, N, N′-diisopropylcarbodiimide, and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride. Examples of the base include triethylamine and diisopropylethylamine.
(Production method 2) Production of a compound represented by the following formula (S-16)

(* Mark in the formula indicates connection of structure)
(Wherein L represents the same meaning as L in formula (I), W ^s1 represents a hydrogen atom, a methyl group or a trifluoromethyl group, ks1 represents an integer of 1 to 9, and r represents 0 to 4 PG represents a protecting group, and halogen represents a halogen atom or a halogen equivalent.)
The compound represented by the formula (S-13) can be obtained by reacting the compound represented by the formula (S-11) with the compound represented by the formula (S-12) in the presence of a base. Examples of the base include potassium carbonate, cesium carbonate, triethylamine and the like.

  The protecting group (PG) of the compound represented by the formula (S-13) is deprotected. The reaction conditions for deprotection are not particularly limited as long as they give the compound represented by formula (S-14), but those listed in the above-mentioned literature are preferable.

  The compound represented by the formula (S-16) can be obtained by reacting the compound represented by the formula (S-14) with the compound represented by the formula (S-15). As the reaction conditions, for example, a method using a condensing agent or a compound represented by the formula (S-15) is converted to an acid chloride, mixed acid anhydride or carboxylic acid anhydride, and then represented by the general formula (S-14). The method of making it react with a compound in base presence is mentioned. When a condensing agent is used, examples of the condensing agent include N, N′-dicyclohexylcarbodiimide, N, N′-diisopropylcarbodiimide, and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride. Examples of the base include triethylamine and diisopropylethylamine.

  Examples of reaction conditions other than those described in each step of production method 1 and production method 2 include, for example, an experimental chemistry course (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd.), Organic Synthesis (John Wiley & Sons, Inc., Publication), and Bilstein Handbook of. Organic Chemistry (Beilstein-Institut fuer Literatur der Organischen Chemie, Springer-Verlag Berlin and Heidelberg GmbH & Co.K), Fiesers' Reagents for Organic Synthesis (John Wiley & Sons, Inc.) conditions or SciFind described in the literature such as r (Chemical Abstracts Service, American Chemical Society) or Reaxys conditions provided from the online search services (Elsevier Ltd.) and the like.

  In each step, a reaction solvent can be appropriately used. The solvent is not particularly limited as long as it gives the target compound. For example, isopropyl alcohol, ethylene glycol, methanol, ethanol, chloroform, dichloromethane, 1,2-dichloroethane, acetone, acetonitrile, N, N-dimethylformamide, N , N-dimethylacetamide, dimethyl sulfoxide, diethyl ether, ethylene glycol monoethyl ether, xylene, ethyl acetate, 1,4-dioxane, tetrahydrofuran, pyridine, 1-methyl-2-pyrrolidinone, toluene, hexane, cyclohexane, heptane, methyl Examples include isobutyl ketone, tert-butyl methyl ether, and methyl ethyl ketone. When the reaction is carried out in an organic solvent and water two-phase system, a phase transfer catalyst can be added. Examples of the phase transfer catalyst include benzyltrimethylammonium chloride, polyoxyethylene (20) sorbitan monolaurate [Tween 20], sorbitan monooleate [Span 80], and the like.

  In each step, purification can be performed as necessary. Examples of the purification method include chromatography, recrystallization, distillation, sublimation, reprecipitation, adsorption, and liquid separation treatment. When using a purification agent, silica gel, alumina, activated carbon, activated clay, celite, zeolite, mesoporous silica, carbon nanotube, carbon nanohorn, Bincho charcoal, charcoal, graphene, ion exchange resin, acid clay, silicon dioxide, diatomaceous earth, Examples include perlite, cellulose, organic polymer, and porous gel.

The compound of the present invention is preferably used for nematic liquid crystal compositions, smectic liquid crystal compositions, chiral smectic liquid crystal compositions and cholesteric liquid crystal compositions, and particularly preferably used for chiral smectic liquid crystal compositions and cholesteric liquid crystal compositions. .
Yes. In the liquid crystal composition using the reactive compound of the present invention, a compound other than the present invention may be added.

  Specific examples of the other polymerizable compound used by mixing with the compound of the present invention include those represented by the general formula (X-11).

And / or general formula (X-12)

(Wherein P ¹¹ , P ¹² and P ¹³ each independently represent a group which is polymerized by radical polymerization, cationic polymerization or anionic polymerization, and Sp ¹¹ , Sp ¹² and Sp ¹³ are each independently a single bond or a carbon atom. Represents an alkylene group of 1 to 20, but one —CH ₂ — or two or more non-adjacent —CH ₂ — is replaced by —O—, —COO—, —OCO—, —OCOO—. X ¹¹ , X ¹² and X ¹³ are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, — CO-S -, - S- CO -, - O-CO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF _{2 -, - CF 2 S -} , - SCF 2 -, - CH = CH-COO -, - CH = H-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, and Z ¹¹ and Z ¹² are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CO—, — 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 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CH 2 -, —CF ₂ CF ₂ —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH ₂ CH ₂ —, —OCO _{-CH 2 CH 2 -, - CH} 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 - OCO-, -CH = CH-, -CF = CF-, -C≡C- or a single bond, and A ¹¹ , A ¹² , A ¹³ and A ¹⁴ are each independently a 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6 A diyl group or 1,3-dioxane-2,5 -Represents a diyl group, but A ¹¹ , A ¹² , A ¹³ and A ¹⁴ are each independently unsubstituted or an alkyl group, a halogenated alkyl group, an alkoxy group, a halogenated alkoxy group, a halogen atom, a cyano group Or a nitro group, R ¹¹ may be a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or One —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—. , -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH- , -OCO-CH = CH-,- Represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by H═CH—, —CF═CF— or —C≡C—, and m11 and m12 represent 0, 1, 2 or 3; However, when m11 and / or m12 represents 2 or 3, two or three A ¹¹ , A ¹³ , Z ¹¹ and / or Z ¹² may be the same or different. ) Is preferred, and the case where P ¹¹ , P ¹² and P ¹³ are acrylic groups or methacrylic groups is particularly preferred. Specifically, the compound represented by the general formula (X-11) is represented by the general formula (X-11a).

Wherein W ¹¹ and W ¹² each independently represent a hydrogen atom or a methyl group, Sp ¹⁴ and Sp ¹⁵ each independently represent an alkylene group having 2 to 18 carbon atoms, and X ¹⁴ and X ¹⁵ each independently to -O -, - COO -, - OCO- or a single ^{bond, Z 13} and ^{Z 14} are each independently represents a -COO- or ^{-OCO-, a 15,} a ¹⁶ and ^{a 17} are each independently And may be unsubstituted or substituted by a fluorine atom, a chlorine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkoxy group having 1 to 4 carbon atoms. , A 4-phenylene group) is preferable, and the following formulas (X-11a-1) to (X-11a-4)

(Wherein, W ¹¹ , W ¹² , Sp ¹⁴ and Sp ¹⁵ represent the same meaning as in the general formula (X-11a)) are particularly preferable. In the above formulas (X-11a-1) to (X-11a-4), compounds in which Sp ¹⁴ and Sp ¹⁵ are each independently an alkylene group having 2 to 8 carbon atoms are particularly preferable.

  In addition, preferable bifunctional polymerizable compounds include those represented by the following general formulas (X-11b-1) to (X-11b-3):

(Wherein W ¹³ and W ¹⁴ each independently represent a hydrogen atom or a methyl group, and Sp ¹⁶ and Sp ¹⁷ each independently represent an alkylene group having 2 to 18 carbon atoms). Is mentioned. In the above formulas (X-11b-1) to (X-11b-3), compounds in which Sp ¹⁶ and Sp ¹⁷ are each independently an alkylene group having 2 to 8 carbon atoms are particularly preferable.

  Specific examples of the compound represented by the general formula (X-12) include the following general formula (X-12-1) to formula (X-12-7).

(In the formula, P ¹⁴ represents a group that is polymerized by radical polymerization, cationic polymerization, or anionic polymerization, and Sp ¹⁸ represents a single bond or an alkylene group having 1 to 20 carbon atoms, but one —CH ₂ — or Two or more non-adjacent —CH ₂ — may be replaced by —O—, —COO—, —OCO—, —O—CO—O—, and X ¹⁶ is a single bond, —O—, — Represents COO— or —OCO—, Z ¹⁵ represents a single bond, —COO— or —OCO—, and L ¹¹ represents a fluorine atom, a chlorine atom, one —CH ₂ — or two or more not adjacent to each other. Each of —CH ₂ — independently represents a linear or branched alkyl group having 1 to 10 carbon atoms which may be independently replaced by —O—, —COO—, or —OCO—, and s11 represents 0 to 4 represents an integer, R ¹² is a hydrogen atom, a fluorine atom, a chlorine atom Cyano group, nitro group, one -CH ₂ - or nonadjacent two or more -CH ₂ - independently are each -O -, - S -, - CO -, - COO -, - OCO- , -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-,- Linear or branched having 1 to 20 carbon atoms which may be replaced by COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF— or —C≡C— And a compound represented by the following formula:

  A polymerizable compound that does not exhibit liquid crystallinity can be added to the polymerizable liquid crystal composition containing the compound of the present invention to such an extent that the liquid crystallinity of the composition is not significantly impaired. Specifically, any compound that is recognized as a polymer-forming monomer or polymer-forming oligomer in this technical field can be used without particular limitation. Specific examples include those described in “Photocuring Technology Data Book, Materials (Monomer, Oligomer, Photopolymerization Initiator)” (supervised by Kunihiro Ichimura, Kiyosuke Kato, Technonet).

  The compound of the present invention can be polymerized without using a photopolymerization initiator, but a photopolymerization initiator may be added depending on the purpose. In this case, the concentration of the photopolymerization initiator is preferably 0.1% by mass to 15% by mass, more preferably 0.2% by mass to 10% by mass, and 0.4% by mass to 8% by mass with respect to the compound of the present invention. % Is more preferable. Examples of the photopolymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, and acylphosphine oxides. Specific examples of the photopolymerization initiator include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (IRGACURE 907), benzoic acid [1- [4- (phenylthio) benzoyl] heptylidene]. Amino (IRGACURE OXE 01) etc. are mentioned. Examples of the thermal polymerization initiator include azo compounds and peroxides. Specific examples of the thermal polymerization initiator include 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (isobutyronitrile) and the like. One type of polymerization initiator may be used, or two or more types of polymerization initiators may be used in combination.

  In addition, a stabilizer can be added to the liquid crystal composition of the present invention in order to improve its storage stability. Examples of the stabilizer that can be used include hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, nitroso compounds, and the like. It is done. When the stabilizer is used, the addition amount is preferably in the range of 0.005% by mass to 1% by mass, more preferably 0.02% by mass to 0.8% by mass, and 0.03% by mass with respect to the composition. To 0.5% by mass is more preferable. One kind of stabilizer may be used, or two or more kinds of stabilizers may be used in combination. Specifically, as the stabilizer, the formula (X-13-1) to the formula (X-13-35)

(Wherein n represents an integer of 0 to 20) is preferred.

  When the compound of the present invention is used in a cholesteric liquid crystal composition or a chiral smectic liquid crystal composition, the chiral compound used by mixing with the compound of the present invention is represented by the following general formula (X-14-1) to general formula: (X-14-4)

(In the formula, each of P ⁴¹ and P ⁴² independently represents a group that is polymerized by radical polymerization, cationic polymerization or anionic polymerization, and Sp ⁴¹ , Sp ⁴² , Sp ⁴³ and Sp ⁴⁴ are each independently a single bond or a carbon atom. Represents an alkylene group of 1 to 20, but one —CH ₂ — or two or more non-adjacent —CH ₂ — is replaced by —O—, —COO—, —OCO—, —OCOO—. X ⁴¹ , X ⁴² , X ⁴³ and X ⁴⁴ are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO. -, - CO-S -, - S-CO -, - O-CO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O- _{, -OCF 2 -, - CF 2} S -, - SCF 2 -, - CH = CH-COO- , —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO _{-, - CH 2 CH 2 -OCO} -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - CF = CF- , -C≡C- or a single bond, each of A ⁴¹ and A ⁴² independently represents 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2 , 5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl group, A ⁴¹ and A ⁴² are each independently unsubstituted. Or an alkyl group, a halogenated alkyl group, an alkoxy group, a halogenated alkoxy group, a halogen atom, a cyano group or a nitro group, and Z ⁴¹ and Z ⁴² each independently represent —O—, — _{S -, - OCH 2 -,} - CH 2 O -, - COO -, - OCO -, - CO -, - CO-S -, - S-CO -, - OCO-O -, - CO-NH _{-, - NH-CO -,} - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH 2 CH 2 -, - CH ₂ CF ₂ —, —CF ₂ CH ₂ —, —CF ₂ CF ₂ —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH— _{, -COO-CH 2 CH 2 -} , - OCO-CH 2 CH 2 -, - CH 2 _{H 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, m41 and m42 represent 0, 1, 2 or 3, but when m41 and / or m42 represents 2 or 3, there are 2 or 3 A ⁴¹ , A ⁴² , Z ⁴¹ and / or Z ⁴² may be the same or different, and L ⁴¹ , L ⁴² , L ⁴³ and L ⁴⁴ are a hydrogen atom, an alkyl group, a halogenated alkyl group, an alkoxy group. Represents a group, a halogenated alkoxy group, a halogen atom, an aromatic group, a cyano group or a nitro group, and one —CH ₂ — or adjacent group in the alkyl group, halogenated alkyl group, alkoxy group and halogenated alkoxy group. do it No more than one -CH ₂ - are each independently -O -, - CO -, - COO -, - OCO -, - OCO-O -, - CO-NH -, - by NH-CO- It may be replaced. ) Is preferable, and P ⁴¹ and P ⁴² are particularly preferably an acrylic group or a methacryl group, and the following general formulas (X-14-1-1) to (X-14-4-) 8)

(* Mark in the formula indicates connection of structure)

(* Mark in the formula indicates connection of structure)

(* Mark in the formula indicates connection of structure)

(* Mark in the formula indicates connection of structure)

(* Mark in the formula indicates connection of structure)

(* Mark in the formula indicates connection of structure)

(* Mark in the formula indicates connection of structure)

(W ⁴¹ and W ⁴² each independently represent a hydrogen atom or a methyl group, and Sp ⁴⁵ and Sp ⁴⁶ each independently represent a single bond or an alkylene group having 2 to 18 carbon atoms (provided that Sp ^{When 45} or Sp ⁴⁶ represents a single bond, one of the oxygen atoms directly bonded to both sides of Sp ⁴⁵ or Sp ⁴⁶ is a single bond.), R ⁴¹ and R ⁴² are straight chain having 1 to 20 carbon atoms Or a branched alkyl group, and L ⁴⁵ represents a fluorine atom, a chlorine atom, one —CH ₂ — or two or more non-adjacent —CH ₂ —, each independently —O—, —COO—, Represents a linear or branched alkyl group having 1 to 10 carbon atoms which may be replaced by —OCO—, and when a plurality of L ⁴⁵ are present, they may be the same or different, and s41 Represents an integer from 0 to 4.) The compounds represented are more preferred.

  Further, when the polymerizable liquid crystal composition containing the compound of the present invention is used for applications such as films, optical elements, functional pigments, pharmaceuticals, cosmetics, coating agents, synthetic resins, Depending on the purpose, metals, metal complexes, dyes, pigments, dyes, fluorescent materials, phosphorescent materials, surfactants, leveling agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants Further, metal oxides such as ion exchange resin and titanium oxide can be added.

The polymer obtained by polymerizing the polymerizable liquid crystal composition containing the compound of the present invention can be used for various applications. For example, a polymer obtained by polymerizing a polymerizable liquid crystal composition containing the compound of the present invention without orientation can be used as a light scattering plate, a depolarizing plate, and a moire fringe prevention plate. Moreover, the polymer obtained by superposing | polymerizing after orientating has optical anisotropy, and is useful. Such an optical anisotropic body includes, for example, a substrate obtained by rubbing a polymerizable liquid crystal composition containing the compound of the present invention with a cloth, a substrate on which an organic thin film is formed, or an alignment film on which SiO ₂ is obliquely deposited. It can be produced by polymerizing the polymerizable liquid crystal composition after it is supported on a substrate having it or sandwiched between substrates.

  Examples of the method for supporting the polymerizable liquid crystal composition on the substrate include spin coating, die coating, extrusion coating, roll coating, wire bar coating, gravure coating, spray coating, dipping, and printing. . Further, an organic solvent may be added to the polymerizable liquid crystal composition during coating. As the organic solvent, hydrocarbon solvents, halogenated hydrocarbon solvents, ether solvents, alcohol solvents, ketone solvents, ester solvents, aprotic solvents and the like can be used. The solvent is toluene or hexane, the halogenated hydrocarbon solvent is methylene chloride, the ether solvent is tetrahydrofuran, acetoxy-2-ethoxyethane or propylene glycol monomethyl ether acetate, and the alcohol solvent is methanol, ethanol or Isopropanol, acetone, methyl ethyl ketone, cyclohexanone, γ-butyl lactone or N-methylpyrrolidinone as the ketone solvent, ethyl acetate or cellosolve as the ester solvent, dimethyl as the aprotic solvent It can be mentioned formamide or acetonitrile. These may be used alone or in combination, and may be appropriately selected in consideration of the vapor pressure and the solubility of the polymerizable liquid crystal composition. As a method for volatilizing the added organic solvent, natural drying, heat drying, reduced pressure drying, or reduced pressure heat drying can be used. In order to further improve the applicability of the polymerizable liquid crystal material, it is also effective to provide an intermediate layer such as a polyimide thin film on the substrate or to add a leveling agent to the polymerizable liquid crystal material. The method of providing an intermediate layer such as a polyimide thin film on a substrate is effective for improving the adhesion between a polymer obtained by polymerizing a polymerizable liquid crystal material and the substrate.

  Examples of the alignment treatment other than the above include use of fluid alignment of a liquid crystal material, use of an electric field or a magnetic field. These orientation means may be used alone or in combination. Furthermore, a photo-alignment method can be used as an alignment treatment method instead of rubbing. As a shape of the substrate, in addition to a flat plate, a curved surface may be included as a constituent part. The material which comprises a board | substrate can be used regardless of an organic material and an inorganic material. Examples of the organic material used as the substrate material include polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethyl methacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polychlorotrifluoroethylene, polyarylate, polysulfone, and triacetyl. Cellulose, cellulose, polyetheretherketone and the like can be mentioned, and examples of the inorganic material include silicon, glass and calcite.

When the polymerizable liquid crystal composition containing the compound of the present invention is polymerized, it is desirable that the polymerization proceeds rapidly. Therefore, a method of polymerizing by irradiating active energy rays such as ultraviolet rays or electron beams is preferable. When ultraviolet rays are used, a polarized light source or a non-polarized light source may be used. Further, when the polymerization is carried out with the liquid crystal composition sandwiched between two substrates, at least the substrate on the irradiation surface side must have appropriate transparency to the active energy rays. Moreover, after polymerizing only a specific part using a mask at the time of light irradiation, the orientation state of the unpolymerized part is changed by changing conditions such as an electric field, a magnetic field, or temperature, and further irradiation with active energy rays is performed. Then, it is possible to use a means for polymerization. Moreover, it is preferable that the temperature at the time of irradiation exists in the temperature range by which the liquid crystal state of the polymeric liquid crystal composition of this invention is hold | maintained. In particular, when an optical anisotropic body is to be produced by photopolymerization, the polymerization is carried out at a temperature as close to room temperature as possible from the viewpoint of avoiding unintentional induction of thermal polymerization, that is, typically at a temperature of 25 ° C. It is preferable to make it. The intensity of the active energy ray is preferably 0.1 mW / cm ^{2 to 2} W / cm ² . When the intensity is 0.1 mW / cm ² or less, a great amount of time is required to complete the photopolymerization and the productivity is deteriorated. When the intensity is 2 W / cm ² or more, the polymerizable liquid crystal compound or the polymerizable liquid crystal is used. There is a risk that the composition will deteriorate.

  The optical anisotropic body obtained by polymerization can be subjected to a heat treatment for the purpose of reducing initial characteristic changes and achieving stable characteristic expression. The heat treatment temperature is preferably in the range of 50 to 250 ° C., and the heat treatment time is preferably in the range of 30 seconds to 12 hours.

  The optical anisotropic body manufactured by such a method may be peeled off from the substrate and used alone or without being peeled off. Further, the obtained optical anisotropic bodies may be laminated or bonded to another substrate for use.

EXAMPLES Hereinafter, although an Example is given and this invention is further described, this invention is not limited to these Examples. Further, “%” in the compositions of the following Examples and Comparative Examples means “% by mass”. When handling a substance unstable to oxygen and / or moisture in each step, it is preferable to work in an inert gas such as nitrogen gas or argon gas. In addition to the operations specifically described below, as necessary, operations such as quenching, separation / extraction, neutralization, washing, separation, purification, drying, concentration, etc. that are commonly performed among those skilled in the art May be performed.
Example 1 Production of Compound Represented by Formula (I-1)

  To a reaction vessel equipped with a Dean-Stark apparatus, 10.0 g of a compound represented by the formula (I-1-1), 4.7 g of acrylic acid, 0.2 g of p-toluenesulfonic acid monohydrate, and 100 mL of toluene are added, The mixture was heated to reflux for 10 hours while removing water. Cooled and washed with saturated aqueous sodium bicarbonate and brine. Purification was performed by column chromatography (silica gel, toluene) to obtain 12.5 g of a compound represented by the formula (I-1-2).

  Under a nitrogen atmosphere, 5.0 g of the compound represented by the formula (I-1-3), 0.2 g of pyridinium p-toluenesulfonate, and 30 mL of dichloromethane were added to the reaction vessel. While cooling with ice, 2.3 g of 3,4-dihydro-2H-pyran was added dropwise and stirred at room temperature for 6 hours. After washing with a saturated aqueous sodium hydrogen carbonate solution and brine, purification was performed by column chromatography (alumina, dichloromethane) to obtain 6.7 g of a compound represented by the formula (I-1-4).

  6.7 g of the compound represented by the formula (I-1-4), 70 mL of tetrahydrofuran, 20 mL of ethanol, 10 mL of pyridine, 0.7 g of 5% palladium carbon (containing 60% water) is added to a pressure vessel at 0.5 MPa at 50 ° C. The mixture was stirred for 8 hours. Palladium was removed by filtration and the solvent was distilled off. It was dissolved in ethyl acetate and washed sequentially with 1% hydrochloric acid, water and brine. Purification was performed by column chromatography (alumina, ethyl acetate) to obtain 4.1 g of a compound represented by the formula (I-1-5).

  In a reaction vessel, 3.0 g of the compound represented by the formula (I-1-5), 4.1 g of the compound represented by the formula (I-1-2), 3.2 g of potassium carbonate, 40 mL of N, N-dimethylformamide And heated and stirred at 90 ° C. for 10 hours. The reaction mixture was poured into 1% hydrochloric acid and extracted with dichloromethane. After washing with water and brine, purification was performed by column chromatography (alumina, dichloromethane) to obtain 4.7 g of a compound represented by the formula (I-1-6).

  To the reaction vessel was added 4.7 g of the compound represented by the formula (I-1-6), 20 mL of methanol, 20 mL of tetrahydrofuran, and 0.2 mL of concentrated hydrochloric acid, and the mixture was stirred at room temperature for 5 hours. After diluting with ethyl acetate, it was washed with water and brine. Purification was performed by column chromatography (silica gel, ethyl acetate) to obtain 3.5 g of a compound represented by the formula (I-1-7).

Under a nitrogen atmosphere, 3.5 g of the compound represented by the formula (I-1-7) in a reaction vessel, 1.0 g of trans-1,4-cyclohexanedicarboxylic acid, 0.1 g of N, N-dimethylaminopyridine, and 40 mL of dichloromethane Was added. While cooling with ice, 1.6 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 10 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 1% hydrochloric acid, water and brine. Purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 3.0 g of a compound represented by the formula (I-1).
Phase transition temperature (heating rate: 5 ° C./min) C 90 N 98 I
¹ H NMR (CDCl ₃ ) δ 1.66 (m, 4H), 2.27 (m, 4H), 2.57 (m, 2H), 3.68-3.77 (m, 12H); 85 (t, 4H), 4.11 (t, 4H), 4.33 (t, 4H), 5.83 (dd, 2H), 6.15 (dd, 2H), 6.43 (dd, 2H) ), 6.89-6.99 (m, 8H) ppm.
LCMS: 729 [M + 1]
Example 2 Production of Compound Represented by Formula (I-2)

  Under a nitrogen atmosphere, 20.0 g of trans-1,4-cyclohexanedicarboxylate monomethyl, 8.8 g of tert-butyl alcohol, 1.3 g of N, N-dimethylaminopyridine, and 100 mL of dichloromethane were added to the reaction vessel. While cooling with ice, 16.3 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 8 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid and brine. Purification was performed by column chromatography (silica gel, dichloromethane) to obtain 20.8 g of a compound represented by the formula (I-2-2).

  To the reaction vessel, 20.8 g of the compound represented by the formula (I-2-2), 200 mL of methanol, and 30 mL of 25% aqueous sodium hydroxide solution were added, and the mixture was heated and stirred at 60 ° C. Cool and add chloroform. 10% hydrochloric acid was added to adjust the pH of the aqueous layer to 4 to 5, followed by liquid separation treatment. The organic layer was washed with brine and dried over sodium sulfate. The insoluble material was filtered through Celite, and the solvent was evaporated and dried to obtain 17.7 g of a compound represented by the formula (I-2-3) (cis / trans ratio = 0.5: 99.5). ).

  Under a nitrogen atmosphere, 3.7 g of the compound represented by the formula (I-2-3), 1.0 g of the compound represented by the formula (I-2-4), N, N-dimethylaminopyridine 1 g and 40 mL of dichloromethane were added. While cooling with ice, 2.2 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 10 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 1% hydrochloric acid, water and brine. Purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 3.5 g of a compound represented by the formula (I-2-5).

  To the reaction vessel, 3.5 g of the compound represented by the formula (I-2-5), 25 mL of dichloromethane, and 15 mL of formic acid were added and heated at 40 ° C. for 8 hours. After distilling off the solvent, 2.6 g of the compound represented by the formula (I-2-6) was obtained by dispersing and washing with diisopropyl ether.

  In a reaction vessel, 2.6 g of the compound represented by the formula (I-2-6), 2.3 g of the compound represented by the formula (I-2-7), 2.5 g of potassium carbonate, 50 mL of N, N-dimethylformamide And heated and stirred at 90 ° C. for 15 hours. The reaction was cooled and poured into 5% hydrochloric acid. Extracted with ethyl acetate and washed with water and brine. Purification was performed by column chromatography (silica gel, dichloromethane / ethyl acetate) to obtain 3.4 g of a compound represented by the formula (I-2-8).

Under a nitrogen atmosphere, 3.4 g of the compound represented by the formula (I-2-8), 1.5 g of diisopropylethylamine, and 50 mL of dichloromethane were added to the reaction vessel. While cooling with ice, 0.9 g of acryloyl chloride was added dropwise, and the mixture was stirred at room temperature for 6 hours. After washing with 1% hydrochloric acid, water and brine, purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) gave 2.8 g of the compound represented by formula (I-2). It was.
LCMS: 805 [M + 1]
Example 3 Production of Compound Represented by Formula (I-3)

Under a nitrogen atmosphere, 1.0 g of the compound represented by the formula (I-3-1), 1.4 g of the compound represented by the formula (I-3-2), N, N-dimethylaminopyridine,. 2 g, 10 mL dichloromethane was added. While cooling with ice, 0.6 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 10 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 1% hydrochloric acid, water and brine. Purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 1.6 g of a compound represented by the formula (I-3).
LCMS: 989 [M + 1]
Example 4 Production of Compound Represented by Formula (I-4)

  Under a nitrogen atmosphere, 3.0 g of trans-1,4-cyclohexanedicarboxylic acid, 20 mL of dichloromethane, 6.6 g of oxalyl chloride, and 0.1 g of N, N-dimethylformamide were added to the reaction vessel, and the mixture was heated and stirred at 40 ° C. for 4 hours. After distilling off the solvent, 3.6 g of the compound represented by the formula (I-4-2) was obtained by drying.

  Under a nitrogen atmosphere, 5.3 g of the compound represented by the formula (I-4-3), 4.1 g of pyridine, and 50 mL of dichloromethane were added to the reaction vessel. A solution prepared by dissolving 3.6 g of the compound represented by the formula (I-4-2) in 10 mL of dichloromethane was added dropwise with ice cooling, and the mixture was stirred at room temperature for 6 hours. After washing with 1% hydrochloric acid, water and brine, purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) gave 6.1 g of the compound represented by the formula (I-4-4). Got.

  An aqueous solution obtained by dissolving 6.1 g of the compound represented by the formula (I-4-4), 80 mL of methanol, and 2.5 g of sodium dihydrogen phosphate dihydrate in 30 mL of water in a reaction vessel, 30% hydrogen peroxide solution 5.0 g was added. An aqueous solution in which 5.0 g of sodium chlorite was dissolved in 50 mL of water was dropped, and the mixture was heated and stirred at 45 ° C. for 5 hours. Water was added and the precipitated solid was filtered and washed with water. By drying, 5.3 g of a compound represented by the formula (I-4-5) was obtained.

In a reaction vessel, 5.3 g of the compound represented by the formula (I-4-5), 5.2 g of the compound represented by the formula (I-4-6), 4.6 g of potassium carbonate, 40 mL of N, N-dimethylformamide And heated and stirred at 90 ° C. for 8 hours. Diluted with dichloromethane and washed sequentially with water and brine. Purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 6.6 g of a compound represented by the formula (I-4).
LCMS: 845 [M + 1]
Example 5 Production of Compound Represented by Formula (I-5)

  Under a nitrogen atmosphere, 3.0 g of the compound represented by formula (I-5-1), 1.6 g of the compound represented by formula (I-5-2), N, N-dimethylaminopyridine,. 1 g and 40 mL of dichloromethane were added. While cooling with ice, 2.0 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 10 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 1% hydrochloric acid, water and brine. Purification was performed by column chromatography (silica gel, dichloromethane) to obtain 3.5 g of a compound represented by the formula (I-5-3).

  To the reaction vessel, 3.5 g of the compound represented by the formula (I-5-3), 15 mL of dichloromethane, and 15 mL of formic acid were added and heated at 40 ° C. for 8 hours. After the solvent was distilled off, it was diluted with ethyl acetate and washed with water and brine. Purification was performed by column chromatography (alumina, ethyl acetate) to obtain 2.6 g of a compound represented by the formula (I-5-4).

Under a nitrogen atmosphere, 2.6 g of a compound represented by the formula (I-5-4), 2.8 g of a compound represented by the formula (I-5-5), N, N-dimethylaminopyridine 1 g and 40 mL of dichloromethane were added. While cooling with ice, 1.4 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 10 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 1% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) gave 3.7 g of the compound represented by formula (I-5).
LCMS: 555 [M + 1]
Example 6 Production of Compound Represented by Formula (I-6)

  To a reaction vessel equipped with a Dean-Stark apparatus, 10.0 g of a compound represented by the formula (I-6-1), 6.4 g of acrylic acid, 0.2 g of p-toluenesulfonic acid monohydrate, and 100 mL of toluene are added, The mixture was heated to reflux for 10 hours while removing water. Cooled and washed with saturated aqueous sodium bicarbonate and brine. Purification was performed by column chromatography (silica gel, toluene) to obtain 12.9 g of a compound represented by the formula (I-6-2).

In a reaction vessel, 2.0 g of the compound represented by formula (I-6-2), 3.1 g of the compound represented by formula (I-6-3), 2.3 g of potassium carbonate, 30 mL of N, N-dimethylformamide. And heated and stirred at 90 ° C. for 15 hours. The reaction was cooled and poured into 5% hydrochloric acid. Extracted with dichloromethane and washed with water and brine. Purification was performed by column chromatography (silica gel, dichloromethane) to obtain 3.3 g of a compound represented by the formula (I-6).
LCMS: 419 [M + 1]
Example 7 Production of Compound Represented by Formula (I-7)

  While adding 10.0 g of the compound represented by the formula (I-7-1), 3.5 g of ethyl acrylate, 0.5 g of dibutyltin oxide, and 100 mL of toluene to a reaction vessel equipped with a Dean-Stark apparatus, the reaction solvent is removed. The mixture was heated to reflux for 10 hours while adding new toluene. The reaction solution was washed with water and brine, and then purified by column chromatography (silica gel, hexane / ethyl acetate) to obtain 5.9 g of a compound represented by the formula (I-7-2).

  Under a nitrogen atmosphere, 3.0 g of the compound represented by the formula (I-7-2), 0.8 g of pyridine, and 20 mL of dichloromethane were added to the reaction vessel. While cooling with ice, 1.1 g of methanesulfonyl chloride was added dropwise and stirred at room temperature for 3 hours. Poured into water and washed sequentially with 5% hydrochloric acid and brine. Purification was performed by column chromatography (silica gel, hexane / ethyl acetate) to obtain 3.0 g of a compound represented by the formula (I-7-3).

  In a reaction vessel, 3.0 g of the compound represented by the formula (I-7-3), 0.9 g of the compound represented by the formula (I-7-4), 1.5 g of potassium carbonate, 30 mL of N, N-dimethylformamide And heated and stirred at 90 ° C. for 15 hours. The reaction was cooled and poured into 5% hydrochloric acid. Extracted with dichloromethane and washed with water and brine. Purification was performed by column chromatography (silica gel, dichloromethane / ethyl acetate) to obtain 2.5 g of a compound represented by the formula (I-7-5).

  An aqueous solution in which 2.5 g of a compound represented by the formula (I-7-5), 40 mL of methanol, and 1.3 g of sodium dihydrogen phosphate dihydrate are dissolved in 15 mL of water in a reaction vessel, 30% hydrogen peroxide solution 2.5g was added. An aqueous solution in which 2.5 g of sodium chlorite was dissolved in 25 mL of water was dropped, and the mixture was heated and stirred at 45 ° C. for 5 hours. Water was added and extracted with ethyl acetate. By distilling off the solvent and drying, 2.3 g of a compound represented by the formula (I-7-6) was obtained.

Under a nitrogen atmosphere, 2.3 g of the compound represented by the formula (I-7-6), 1.1 g of the compound represented by the formula (I-7-7), N, N-dimethylaminopyridine. 2 g, 10 mL dichloromethane was added. While cooling with ice, 0.8 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 10 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 1% hydrochloric acid, water and brine. Purification was performed by column chromatography (silica gel, dichloromethane) to obtain 2.4 g of a compound represented by the formula (I-7).
LCMS: 657 [M + 1]
Example 8 Production of Compound Represented by Formula (I-8)

  In a reaction vessel, 3.0 g of the compound represented by the formula (I-8-1), 3.1 g of the compound represented by the formula (I-8-2), 2.8 g of potassium carbonate, 30 mL of N, N-dimethylformamide And heated and stirred at 90 ° C. for 8 hours. Diluted with dichloromethane and washed sequentially with water and brine. Purification was performed by column chromatography (silica gel, dichloromethane) to obtain 4.5 g of a compound represented by the formula (I-8-3).

  To the reaction vessel, 4.5 g of the compound represented by the formula (I-8-3), 25 mL of dichloromethane and 15 mL of formic acid were added and heated at 40 ° C. for 8 hours. After the solvent was distilled off, it was diluted with ethyl acetate and washed with water and brine. The solvent was distilled off and dried to obtain 3.5 g of a compound represented by the formula (I-8-4).

Under a nitrogen atmosphere, 3.5 g of the compound represented by the formula (I-8-4), 2.1 g of the compound represented by the formula (I-8-5), N, N-dimethylaminopyridine,. 1 g and 40 mL of dichloromethane were added. While cooling with ice, 1.5 g of diisopropylcarbodiimide was added dropwise and stirred at room temperature for 10 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 1% hydrochloric acid, water and brine. Purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 3.8 g of a compound represented by the formula (I-8).
LCMS: 559 [M + 1]
A compound represented by the formula (I-9) to the formula (I-63) was produced by combining the same method as described above and a known method.
(Examples 9 to 60, Comparative Examples 1 to 9)
Compounds represented by formulas (I-1) to (I-8) described in Example 1 to Example 8, compounds described in Patent Document 1 (R-1), compounds described in Patent Document 2 (R- 2) The compound (R-3) described in Patent Document 3 was used as an evaluation target compound.

  Further, compound (X-1) described in JP-A-2005-015473: 35%, compound (X-2) described in JP-A-10-87565: 25%, compound described in JP-T-2002-537280 A liquid crystal composition composed of (X-3): 35% and a compound (X-4): 5% described in WO02 / 094805A1 as a chiral compound was used as a base liquid crystal (X).

  In order to evaluate the storage stability, a polymerizable liquid crystal composition was prepared by adding the compound to be evaluated to the base liquid crystal (X) from 30% to 70% in increments of 5% and heating and dissolving at 70 ° C. . After the prepared polymerizable liquid crystal composition is stored at 18 ° C. for 5 weeks, the maximum addition concentration of the compound to be evaluated at which no crystal precipitation occurs is described in the table below.

  From the above results, it can be seen that the compounds represented by the formulas (I-1) to (I-8) of the present invention all have good storage stability.

  The polyimide solution for forming an alignment film was applied to a glass substrate having a thickness of 0.7 mm using a spin coating method, dried at 100 ° C. for 10 minutes, and then baked at 200 ° C. for 60 minutes to obtain a coating film. The obtained coating film was rubbed. The rubbing treatment was performed using a commercially available rubbing apparatus.

11.87% of the base liquid crystal (X), 7.91% of the compound to be evaluated (40% based on the total content of the base liquid crystal (X) and the compound), photopolymerization initiator Irgacure 907 (manufactured by BASF) Was mixed with 0.20%, 4-methoxyphenol 0.02% and cyclohexanone 80.00%. This coating solution was applied to a rubbed glass substrate using a bar coater (No. 9), and then placed on a hot plate at 100 ° C. to evaporate the solvent. Then, the film of evaluation object was produced by irradiating an ultraviolet-ray with the intensity | strength of 40 mW / cm < ² > for 25 second using a high pressure mercury lamp. The obtained film was evaluated for alignment defects by observation with a polarizing microscope. The film was divided into 10 squares × 10 squares, for a total of 100 squares, and the number of squares having orientation defects was counted. It means that there are few orientation defects, so that a value is small. The results are shown in the table below.

  Since the film of Comparative Example 6 to which the comparative compound (R-3) was added did not show uniform orientation, the orientation defect was not evaluated. From the above results, it can be seen that the compounds represented by the formulas (I-1) to (I-8) of the present invention have few alignment defects in the obtained cholesteric liquid crystal phase.

  Next, 60 mW light was irradiated for 500 hours with the LED lamp (365 nm) with respect to the evaluation object film. About the obtained film, the degree of peeling was evaluated by observation with a polarizing microscope. The film was divided into an area of 10 squares by 10 squares, for a total of 100 squares, and the number of squares where peeling occurred was counted. A smaller value means less peeling. Since the film of Comparative Example 9 to which the comparative compound (R-3) was added did not exhibit uniform orientation, peeling was not evaluated. The results are shown in the table below.

  From the above results, the compounds represented by the formulas (I-1) to (I-8) of the present invention hardly peel off from the base material when the obtained film is irradiated with ultraviolet light for a long time. I understand that.

  From the above results, all the compounds represented by the formulas (I-1) to (I-8) of the present invention are compared with the comparative compound (R-1) to the comparative compound (R-3). When added to a polymerizable composition containing a polymerizable compound, it has high storage stability, and when a film-like polymer is produced, alignment defects are less likely to occur, and the film-like polymer is irradiated with ultraviolet light for a long time. Since peeling from the substrate hardly occurs when irradiated, it is useful as a constituent member of the polymerizable composition. Moreover, the said polymeric composition is useful for the use of optical materials, such as a phase difference film and a selective reflection film.

Claims (9)

The following general formula (I)

(Wherein P ¹ represents a group which is polymerized by radical polymerization, cationic polymerization or anionic polymerization,
k1 represents an integer of 2 to 10,
X ¹ represents —CH ₂ —, —CO—, —CF ₂ —, —COO—, —CO—S—, —CO—NH—, —CO—CH═CH—, —COO—CH═CH—, — CO—CH ₂ CH ₂ —, —COO—CH ₂ CH ₂ —, —CO—CH ₂ —, —COO—CH ₂ — or a single bond,
A ¹ and A ² are each independently 1,4-phenylene group, 1,4-cyclohexylene group, bicyclo [2.2.2] octane-1,4-diyl group, pyridine-2,5-diyl group. , Pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1 , 3-dioxane-2,5-diyl groups, these groups may be unsubstituted or substituted by one or more substituents L, and when there are multiple A ¹ they are the same Can be different or different,
L is fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, Diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, optionally substituted phenyl group, optionally substituted phenylalkyl group, optionally substituted cyclohexylalkyl group, or one —CH _2- or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO. ^{-, - OCO-O -,} - CO-NR 0 -, - NR 0 -CO -, - CH = CH-COO -, - CH = CH-OCO -, - C O-CH = CH -, - OCO-CH = CH -, - CH = CH -, - N = N -, - CR 0 = N -, - N = CR 0 -, - CH = N-N = CH- , —CF═CF— or —C≡C— (wherein R ⁰ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), and is a straight chain having 1 to 20 carbon atoms. A hydrogen atom in the alkyl group may be substituted with a fluorine atom, or L is represented by P ^L — (CH ₂ CH ₂ O) _kL —X ^L —. may represent a group, wherein ^{P L} represents a group of polymerization by radical polymerization, cationic polymerization or anionic polymerization, kL is an integer of from 2 to 10, ^{X L} is _-CH 2 -, - CO- , —CF ₂ —, —COO—, —CO—S—, —CO—NH—, —CO—CH═CH _{-, - COO-CH = CH} -, - CO-CH 2 CH 2 -, - COO-CH 2 CH 2 -, - CO-CH 2 -, - COO-CH 2 - or represents a single bond, the compound When there are a plurality of L, they may be the same or different,
Z ¹ 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 = N-N = CH -, - CF = CF -, - C≡C- or represents a single bond, Z ^When there are multiple 1s, they may be the same or different,
m1 represents an integer of 0 to 5,
R ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or one —CH ₂ — or adjacent. Two or more —CH ₂ — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO. A straight chain having 1 to 20 carbon atoms which may be substituted by —O—, —CO—NH—, —NH—CO—, —CH═CH—, —CF═CF— or —C≡C—, or A branched alkyl group is represented, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or R ² is represented by —X ² — (OCH ₂ CH ₂ ) _k2 —P ^2. Group (wherein P ² is used for radical polymerization, cationic polymerization or anionic polymerization) Represents a more polymerizable group, k2 represents an integer of 2 to 10, X ² represents —CH ₂ —, —CO—, —CF ₂ —, —OCO—, —S—CO, —NH—CO—, — _{CH = CH-CO -, -} CH = CH-OCO -, - CH 2 CH 2 -CO -, - CH 2 CH 2 -OCO -, - CH 2 -CO -, - CH 2 -OCO- or a single bond Wherein at least one of Z ¹ present represents a group other than a single bond, and at least one of A ¹ and A ² present is 1,4-cyclohexylene group, bicyclo [2. 2.2] represents an octane-1,4-diyl group, a decahydronaphthalene-2,6-diyl group or a 1,3-dioxane-2,5-diyl group, these groups being unsubstituted or It may be substituted by one or more substituents L. ) A compound represented by R ² is ^-X 2 _{- (OCH} 2 _{CH 2)} in a group represented by (wherein in k2 -P ^{2, P 2} represents the radical polymerization, polymerization is group by cationic polymerization or anionic polymerization, k2 is from 2 to 10 Represents an integer, and X ² represents —CH ₂ —, —CO—, —CF ₂ —, —OCO—, —S—CO, —NH—CO—, —CH═CH—CO—, —CH═CH—OCO. _{-, - CH 2 CH 2 -CO} -, - CH 2 CH 2 -OCO -, - CH 2 -CO -, -. the CH represents a 2 --OCO) compound of claim 1 which is.   The compound according to claim 1 or 2, wherein the number of aromatic rings contained in the structure is one or two.   The composition containing the compound of any one of Claim 1 to 3.   A liquid crystal composition comprising the compound according to claim 1.   The polymer obtained by superposing | polymerizing the compound of any one of Claim 1 to 3.   A polymer obtained by polymerizing the composition according to claim 4.   An optical anisotropic body using the polymer according to claim 7.   Resins, resin additives, oils, filters, adhesives, adhesives, oils, fats, inks, pharmaceuticals, cosmetics, detergents, building materials, packaging materials, liquid crystals using the compound according to any one of claims 1 to 3 Materials, organic EL materials, organic semiconductor materials, electronic materials, display elements, electronic devices, communication equipment, automobile parts, aircraft parts, machine parts, agricultural chemicals and foods, and products using them.