JP6418476B1 - Polymerizable compound and optical anisotropic body - Google Patents

Abstract

Polymer that is particularly suitable as a raw material for optical films, has low wavelength dispersibility or reverse wavelength dispersibility, is less likely to generate bubbles when formed into a paint, and has excellent substrate adhesion when formed into a film-like polymer. Sex compounds are provided. Furthermore, the present invention provides a polymerizable composition containing the polymerizable compound, a polymer obtained by polymerizing the polymerizable composition, and an optical anisotropic body using the polymer. This invention is a compound represented by general formula (I) of Claim 1. Furthermore, this invention is a composition containing the compound represented by general formula (I), and is a polymer obtained using this composition.

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.

  A compound having a polymerizable group (polymerizable compound) is used in various optical materials. For example, it is possible to produce a polymer having a uniform orientation by aligning a polymerizable composition containing a polymerizable compound in a liquid crystal state and then polymerizing it. Such a polymer can be used for polarizing plates, retardation plates and the like necessary for displays. In many cases, two or more types of polymerization are used to satisfy the required optical properties, polymerization rate, solubility, melting point, glass transition temperature, polymer transparency, mechanical strength, surface hardness, heat resistance and light resistance. A polymerizable composition containing a functional compound is used. In that case, the polymerizable compound to be used is required to bring good physical properties to the polymerizable composition without adversely affecting other properties.

  In order to improve the viewing angle of the liquid crystal display, it is required to make the wavelength dispersion of the birefringence in the retardation film small or negative. As a material for that purpose, various polymerizable compounds having low wavelength dispersion or reverse wavelength dispersion have been developed. (Patent Document 1).

WO2014-010325A1

  Polymerizable compounds that have low wavelength dispersion or that exhibit reverse wavelength dispersion are limited in usefulness compared to polymerizable compounds that are forward wavelength-dispersible, and there are significant restrictions on the molecular structure. . For this reason, although improvement of the wavelength dispersion of the polymerizable compound is progressing, practical aspects such as productivity and handleability have not been sufficiently examined.

  For example, conventional polymerizable compounds have the following problems due to their foamability. Usually, when a film-like polymer is produced using a polymerizable compound, a polymerizable composition containing the polymerizable compound is dissolved in various solvents to form a paint, and the resulting paint is applied and dried. Turn into. However, bubbles tend to be generated in the coating step, and the optical film finally obtained due to this tends to contain fine bubbles. If such optical film containing bubbles is used for a display, the brightness of the screen may become uneven or the target optical characteristics may not be obtained, greatly reducing the quality of the display product. There was a problem.

  An optical film obtained from a polymerizable composition containing a polymerizable compound generally has low adhesion to various substrates (or alignment films) such as glass and plastic. For this reason, there existed a problem that it was easy to produce peeling etc. and durability of a film was low.

  Attempts have been made to solve these problems by adding additives to the polymerizable composition. However, in this method, not only the manufacturing process becomes more complicated, but also the liquid crystallinity of the polymerizable composition is lowered, and as a result, the optical properties of the optical film are lowered. . Therefore, development of the polymeric compound which has the low wavelength dispersion property or reverse wavelength dispersion property which can solve these problems was calculated | required.

  The present invention is a raw material for optical films that has low wavelength dispersibility or reverse wavelength dispersibility, and is less likely to generate bubbles when made into a paint, and has excellent substrate adhesion when formed into a film-like polymer. Particularly suitable polymerizable compounds are provided. Furthermore, it is providing the polymeric composition containing the said polymeric compound, the polymer obtained by polymerizing the said polymeric composition, and the optical anisotropic body using the said polymer.

As a result of intensive studies to solve the above problems, the present inventors have developed a polymerizable compound capable of solving the above problems. That is, the present invention relates to the general formula (I)

(Wherein R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 80 carbon atoms, the group may have a substituent, and any carbon atom is hetero An atom may be substituted, but at least one of R ¹ and R ² represents a group represented by the general formula (I-0-R),

(In the formula, P ⁰ represents a polymerizable group, and Sp ⁰ represents a linear or branched alkylene group having 1 to 30 carbon atoms or a single bond, and the alkylene group represents 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—, —CF ₂ O—, —OCF ₂ —, —CF ₂ S—, —SCF ₂ —, —CH═CH—COO—, — CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -N = N-, -CH = N-N = CH-, -CF = CF- Alternatively, -C≡C may be substituted, and when a plurality of Sp ⁰ are present, they may be the same or different, and X ^{0 is-} O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, _{-CO-NH -, - NH-} CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH- COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —CH ₂ CH _{2 -COO -, - CH 2 CH 2} -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N- N = CH -, - CF = CF -, - C≡C- or represents a single bond, ^{if X 0} there are multiple These may be different even in the same ^{(although, P 0 - (Sp 0 -X} 0) k0 -. The free of -O-O- bonds), the integer k0 from 0 10 R ³ is a hydrogen atom, or one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—, — COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = 1 to 20 carbon atoms which may be substituted by CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF— or —C≡C—. In which a hydrogen atom in the alkyl group may be substituted with a fluorine atom, , R ³ is a group represented by the general formula (I-0-R), W is a divalent cyclic hydrocarbon group having 80 from 1 carbon atoms, of the cyclic hydrocarbon group One or more arbitrary carbon atoms may be substituted with a heteroatom, and one or more arbitrary hydrogen atoms of the cyclic hydrocarbon group may be substituted with L ^W , L ^W 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, or one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—. , -C -, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, Represents a linear or branched substituted alkyl group having 2 to 20 carbon atoms substituted by —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, any hydrogen atom in the group may be substituted by a fluorine atom, or, ^{L W} is _{^{P LW - (Sp LW -X LW}} ) kLW - may represent a group represented by wherein ^{P LW} is Sp ^LW represents a polymerizable group, and Sp ^LW is a group in which one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently substituted by —O—, —COO—, or —OCO—. Represents a good linear alkylene group of 1 to 10 carbon atoms or a single bond, but S When a plurality of p ^LWs are present, they may be the same or different, and X ^LW is —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, -OCO -, - CO-S - , - S-CO -, - O-CO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 _{O -, - OCF 2 -,} - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH- , —COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO—, —CH ₂ CH ₂ —OCO—, —COO—CH ₂ —, —OCO—CH ₂ — _{, -CH 2 -COO -, - CH} 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = H -, - CF = CF - , - C≡C- or it represents a single ^bond, they ^{if X LW} there are a plurality or different and the same ^(however, P ^LW - ^(Sp LW - X ^LW ) _kLW − does not contain an —O—O— bond. ), KLW represents an integer of from 0 to 10, L ^W is may be those when there are multiple different be the same, Y is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, penta Fluorosulfuranyl 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 or 1 number of -CH ₂ - or nonadjacent two or more -CH ₂ - are each independently -O -, - S -, - CO -, - COO -, - OCO -, - CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = C Represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by —, —OCO—CH═CH—, —CH═CH—, —CF═CF— or —C≡C—. However, any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or Y may represent a group represented by P ^Y — (Sp ^Y —X ^Y ) _kY —, where P ^Y is Sp ^Y represents a polymerizable group, and Sp ^Y represents a case where one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently substituted by —O—, —COO—, or —OCO—. Represents a good linear alkylene group having 1 to 10 carbon atoms or a single bond, but when a plurality of Sp ^Y are present, they may be the same or different, and ^XY represents —O—, —S—. _{, -OCH 2 -, - CH 2} O -, - CO -, - COO -, - OCO-, CO-S -, - S- CO -, - O-CO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF _{2 -, - CF 2 S -} , - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO—, —CH ₂ CH ₂ —OCO—, —COO—CH ₂ —, —OCO—CH ₂ —, —CH ₂ — COO—, —CH ₂ —OCO—, —CH═CH—, —N═N—, —CH═N—N═CH—, —CF═CF—, —C≡C— or a single bond, When there are a plurality of ^XY, they may be the same or different (provided that P ^Y- (Sp ^Y -X ^Y ) _kY -Does not include -O-O- bond. ), KY represents an integer of 0 to 10, and A ¹ and A ² are each independently 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, decahydronaphthalene-2,6-diyl group or 1,3-dioxane- Represents a 2,5-diyl group, these groups may be unsubstituted or substituted by one or more substituents L, where L is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, pentafluoro Sulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, tri Chirushiriru group, dimethylsilyl group, Chioisoshiano group, or one -CH ₂ - or nonadjacent two or more -CH ₂ - are each independently -O -, - S -, - CO -, - COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = 1 to 20 carbon atoms which may be substituted by CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF— or —C≡C—. In which an arbitrary hydrogen atom in the alkyl group may be substituted with a fluorine atom, or L is represented by P ^L- (Sp ^L -X ^L ) _kL-. may represent a group, wherein P ^L represents a polymerizable group, Sp ^L is one - H ₂ - or nonadjacent two or more -CH ₂ - are each independently -O -, - COO -, - straight-chain alkylene group having from 10 to good carbon atoms 1 be replaced by OCO- or it represents a single bond, they if Sp ^L there are a plurality or different and are identical, ^{X L} is _{-O -, - S -, -} OCH 2 -, - CH 2 O -, - CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —SCH ₂ —, —CH ₂ S—, —CF ₂ O—, —OCF ₂ —, —CF ₂ S—, —SCF ₂ —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, _{-OCO-CH = CH -, -} COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH ₂ —COO—, —CH ₂ CH ₂ —OCO—, —COO—CH ₂ —, —OCO—CH ₂ —, —CH ₂ —COO—, —CH ₂ —OCO—, —CH═CH—, — N = N -, - CH = N-N = CH -, - CF = CF -, - C≡C- or represents a single bond, they ^{if X L} there are a plurality optionally be the same or different (However, P ^L- (Sp ^L -X ^L ) _kL -does not contain an -O-O- bond. ), KL represents an integer of 0 to 10, but when a plurality of L are present in the compound, they may be the same or different, and when a plurality of A ¹ are present, they are the same or different. When a plurality of A ² are present, they may be the same or different, and Z ¹ and Z ² are each independently —O—, —S—, —OCH ₂ —, —CH. ₂ O—, —CH ₂ CH ₂ —, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, — NH—CO—, —OCO—NH—, —NH—COO—, —NH—CO—NH—, —NH—O—, —O—NH—, —SCH ₂ —, —CH ₂ S—, —CF _{2 O -, - OCF 2 -} , - CF 2 S -, - SCF 2 -, - CH = CH-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 there are a plurality of Z ^1, they may be the same or different. In the case where a plurality of Z ² are present, they may be the same or different, and G is represented by the following formulas (G-1) to (G-8):

Represents a group selected from, corresponding horizontal bonds in these formulas is a horizontal bond G, these groups are substituted by unsubstituted or substituted with one or more L ^{G LG} 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, 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- OO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF— or —C≡C— may be substituted. It represents a linear or branched alkyl group having 1 to 20 carbon atoms, optional hydrogen atom in the alkyl group may be substituted by a fluorine atom, or, L ^G is P ^{LG -} (Sp ^{LG -} X ^LG ) _kLG- may be used, where P ^LG represents a polymerizable group, and Sp ^LG represents one -CH ₂ -or two or more non-adjacent -CH _2- groups. Each independently represents a linear alkylene group having 1 to 10 carbon atoms which may be substituted by -O-, -COO-, or -OCO- or a single bond, and when a plurality of Sp ^LG are present, They may be the same or different and X ^LG is − O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, _{-CO-NH -, - NH-} CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH- COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —CH ₂ CH _{2 -COO -, - CH 2 CH 2} -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N- N = CH -, - CF = CF -, - C≡C- or represents a single ^{bond, a} place ^{X LG} there are multiple They may be different even in the same ^{(however, P LG - (Sp LG -X} LG) kLG - to contain no -O-O- bonds. ), KLG represents an integer of 0 to 10, if L ^G there are a plurality in the compounds they may be different even in the same, m1 and m2 integer from 0 to 6 each independently is M1 + m2 represents an integer of 0 to 6), a polymerizable composition containing the compound, a resin using the compound, a resin additive, an oil, a filter, and an adhesive Agents, 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, Provided are mechanical parts, agricultural chemicals and foods, products using them, a polymerizable liquid crystal composition, a polymer obtained by polymerizing the polymerizable liquid crystal composition, and an optical anisotropic body using the polymer.

  According to the polymerizable compound of the present invention, it is possible to improve the defoaming property of the coating material for an optical film and the substrate adhesion of the optical film. Therefore, the polymerizable compound of the present invention is useful for optical materials such as a retardation film.

  The present invention provides a low wavelength dispersible or reverse wavelength dispersible compound having a specific structure in the molecule, and a polymerizable composition containing the compound, a resin using the compound, a resin additive, an oil, Filters, 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, Providing aircraft parts, machine 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 To do.

As used herein, “normal dispersion” and “reverse dispersion” conform to the following definitions. In the graph in which the wavelength λ of incident light with respect to the retardation film is plotted on the horizontal axis and the birefringence Δn is plotted on the vertical axis, when the birefringence Δn increases as the wavelength λ decreases, the film is “positively dispersed”. If the birefringence Δn decreases as the wavelength λ decreases, the film is generally referred to by those skilled in the art as being “reverse wavelength dispersive” or “reverse dispersive”. In the present invention, the value Re (450) / Re (550) obtained by dividing the in-plane retardation (Re (450)) at a wavelength of 450 nm by the in-plane retardation Re (550) at a wavelength of 550 nm is 0.95 or less. A compound constituting the retardation film is referred to as a reverse dispersion compound. A compound constituting a retardation film having Re (450) / Re (550) of greater than 0.95 and 1.05 or less is referred to as a low wavelength dispersible compound. The method for measuring the phase difference is as follows.
<Measurement of phase difference>
A polyimide solution for preparing an alignment film is 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 is rubbed using a commercially available rubbing apparatus.

A cyclopentanone solution containing 20% by mass of the compound to be evaluated is applied onto the rubbed substrate by spin coating, and the coating film is dried at 100 ° C. for 2 minutes. After the obtained dried film is cooled to room temperature, a film to be evaluated is obtained by irradiating with an ultraviolet ray at an intensity of 30 mW / cm ² for 30 seconds using a high-pressure mercury lamp. The retardation of the obtained film is measured using a retardation film / optical material inspection apparatus RETS-100 (manufactured by Otsuka Electronics Co., Ltd.).

  When the compound to be evaluated does not dissolve in cyclopentanone, chloroform is used as a solvent. In addition, when the compound to be evaluated does not exhibit liquid crystallinity alone, the compound represented by the following formula (A) (50 mass%) and the compound represented by the formula (B) (50 mass%)

A film is prepared using a composition in which the evaluation target compound (10% by mass, 20% by mass or 30% by mass) is added to the base liquid crystal composed of the above, and the retardation value is measured by extrapolation.

The compound represented by the general formula (I) of the present invention has a characteristic site of a cyclic hydrocarbon group W and a specific group L ^W that is directly bonded to the group ^W , thereby providing an antifoaming property or a film. It is possible to have excellent adhesion at the time. The reason is not clear, the presence of such groups L ^W, improved lubricity of the compound, presumably because it can contribute to a low viscosity at the time of constructing a composition.

In the general formula (I), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 80 carbon atoms, and the group may have a substituent, and any carbon atom May be substituted with a hetero atom, but at least one of R ¹ and R ² represents a group represented by the general formula (I-0-R). When R ¹ or R ² represents a group other than the group represented by the general formula (I-0-R), each of R ^{1 and} R ² is independently a hydrogen atom from the viewpoint of liquid crystallinity and ease of synthesis. Fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, cyano group, nitro group, isocyano group, thioisocyano group, or any hydrogen atom in the group may be substituted with a fluorine atom, One —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO. -, - OCO -, - CO -S -, - S-CO -, - OCO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - _{CF 2 O -, - OCF 2} -, - CF 2 S -, - SCF 2 -, - CH = CH-COO-, CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO-, _{-CH 2 CH 2 -OCO -, -} COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - It preferably represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by CH═N—N═CH—, —CF═CF— or —C≡C—, each independently. A hydrogen atom, a fluorine atom, a chlorine atom, or one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —COO—, —OCO—, — A straight chain of 1 to 12 carbon atoms which may be substituted by O—CO—O—. Or a branched alkyl group, more preferably a hydrogen atom, a fluorine atom, a chlorine atom, or a straight-chain alkyl group having 1 to 12 carbon atoms or a straight-chain alkoxy group, more preferably 1 to 1 carbon atom. It is particularly preferred to represent 12 linear alkyl groups or linear alkoxy groups. In addition, R ¹ and R ² are independent from the viewpoints of mechanical strength and retardation stability (presence / absence of change in retardation over time), surface hardness, polymerization rate, heat resistance, and light resistance when an optical film is formed. represents a group represented by the general formula (I-0-R) Te, or represents a group other than ^{a group R 3} is represented by the general formula ^(I-0-R), R 1, R 2 and ^{R 3} Each independently represents a group represented by the general formula (I-0-R). In the general formula (I-0-R), P ⁰ represents a polymerizable group, and the following formula (P-1) to formula (P-20)

Preferably, these polymerizable groups are polymerized by radical polymerization, radical addition polymerization, cationic polymerization and anionic polymerization. In particular, when ultraviolet polymerization is performed as a polymerization method, the formula (P-1), formula (P-2), formula (P-3), formula (P-4), formula (P-5), formula (P -7), formula (P-11), formula (P-13), formula (P-15) or formula (P-18) are preferred, and formula (P-1), formula (P-2), formula (P-18) P-3), formula (P-7), formula (P-11) or formula (P-13) is more preferred, and formula (P-1), formula (P-2) or formula (P-3) is more preferred. More preferred is formula (P-1) or (P-2).
In the general formula (I-0-R), Sp ⁰ represents a linear or branched alkylene group having 1 to 30 carbon atoms or a single bond, and the alkylene group is one —CH ₂ — or not adjacent. Two or more —CH ₂ — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—. _{O -, - CO-NH -} , - NH-CO -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH- OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —N═N—, —CH═N—N═CH—, —CF═CF— or —C≡. may be replaced by C, and they may be different even if the same if the Sp ⁰ there are a plurality, availability of raw materials Ease, Sp ⁰ in terms of ease and liquid synthetic is one -CH ₂ - or nonadjacent two or more -CH ₂ - are each independently -O -, - COO -, - preferably representing the OCO- or -O-CO-O-, in linear from a good carbon atoms 1 be replaced 20 or branched alkylene group or a single bond, one -CH ₂ - or adjacent More preferably, two or more —CH ₂ — that are not represented each represent a linear alkylene group having 1 to 12 carbon atoms that may be independently replaced by —O—.
In the general formula (I-0-R), X ⁰ represents —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —CO—S—, -S-CO -, - O- CO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF ₂ S—, —SCF ₂ —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH ₂ CH ₂ —, _{-OCO-CH 2 CH 2 -,} - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH _{2 -OCO -, - CH = CH} -, - N = N -, - CH = N-N = CH -, - CF = CF -, - C≡C- or a single Represents the total, may be they have be the same or different ^{if X 0} there are a plurality ^{(however, P 0 - (Sp 0 -X} 0) k0 - to contain no -O-O- bonds ), X ⁰ is —O—, —S—, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CO— from the viewpoint of availability of raw materials and synthesis. _{S -, - S-CO -} , - OCO-O -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 - It preferably represents OCO- or a single bond, and more preferably represents -O-, -COO-, -OCO- or a single bond.
In general formula (I-0-R), k0 represents an integer of 0 to 10, and preferably represents an integer of 0 to 3 from the viewpoint of liquid crystallinity and availability of raw materials. From the viewpoint of curing shrinkage when formed into a film, k0 independently preferably represents an integer of 1 to 3, more preferably 1.
In the general formula (I), R ³ is a hydrogen atom, or one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—. , -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-,- 1 carbon atom which may be substituted by CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF— or —C≡C— To 20 straight-chain or branched alkyl groups, any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or R ³ is represented by the general formula (I-0-R). Represents a group. When R ³ represents a group other than the group represented by the general formula (I-0-R), R ³ is a hydrogen atom or one — CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —CO—, —COO—, —OCO—, —O—CO—O—, —CH═CH—. COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF— or —C≡C— may be substituted. It preferably represents a linear or branched alkyl group having 1 to 20 carbon atoms, and each independently represents a hydrogen atom, or one —CH ₂ — or two or more —CH ₂ — not adjacent to each other. 1 to 20 carbon atoms which may be substituted by -O-, -COO- or -OCO- It is more preferable to represent a linear or branched alkyl group, and a hydrogen atom or one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently substituted by —O—. More preferably, it represents a linear alkyl group having 1 to 12 carbon atoms which may be prepared. From the viewpoint of difficulty in generating polymer impurities when the compound represented by the general formula (I) is dissolved in an organic solvent and stored for a long period of time, R ³ is represented by the general formula (I-0-R). In the case of representing a group other than the group to be formed, one —CH ₂ — or two or more non-adjacent —CH ₂ — may be each independently substituted with —O—. It is particularly preferable to represent a linear alkyl group of From the viewpoint of the mechanical strength and the phase difference stability when the optical film, it is also preferable to represent a group R ³ is represented by the general formula (I-0-R).
In the general formula (I), W represents a divalent cyclic hydrocarbon group having 1 to 80 carbon atoms, and one or more arbitrary carbon atoms of the cyclic hydrocarbon group are substituted with hetero atoms. may be, one or more arbitrary hydrogen atoms of the cyclic hydrocarbon group may be substituted with L ^W. From the viewpoint of liquid crystallinity, availability of raw materials, and ease of synthesis, W represents the following formulas (W-1) to (W-6).

(In the formula, each group has a bond on two arbitrary carbon atoms, and one or more arbitrary carbon atoms may be substituted with a hetero atom, and any hydrogen atom may be L ^W. Any —CH═ may be independently replaced by —N═, and any —CH ₂ — may independently be —O—, —S—, —NR ^T. -(Wherein R ^T represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), -CS- or -CO- may be substituted, but does not include a -O-O- bond. Or a polycyclic group in which two or more identical or different groups selected from these groups are connected by a single bond.

  Here, each group represented by the formula (W-1) to the formula (W-6) preferably has two bonds at least at the following positions,

  Examples of the group represented by the above formula (W-1) include the following formula (W-1-1) to formula (W-1-7).

(In the formula, each group has a bond on two arbitrary carbon atoms, one or more arbitrary hydrogen atoms may be substituted with L ^W , and ^RT is a hydrogen atom or carbon. It preferably represents a group selected from 1 to 8 alkyl groups.

  Examples of the group represented by the above formula (W-2) include the following formulas (W-2-1) to (W-2-8).

(In the formula, each group has a bond on two arbitrary carbon atoms, and one or two or more arbitrary hydrogen atoms may be substituted with L ^W ). It is preferable.

  Examples of the group represented by the above formula (W-3) include the following formula (W-3-1) to formula (W-3-8).

(In the formula, each group has a bond on two arbitrary carbon atoms, one or more arbitrary hydrogen atoms may be substituted with L ^W , and ^RT is a hydrogen atom or carbon. It preferably represents a group selected from 1 to 8 alkyl groups.

  Examples of the group represented by the above formula (W-4) include the following formula (W-4-1) to formula (W-4-7).

(In the formula, each group has a bond on two arbitrary carbon atoms, and one or two or more arbitrary hydrogen atoms may be substituted with L ^W ). It is preferable.

  Examples of the group represented by the above formula (W-5) include the following formula (W-5-1) to formula (W-5-4).

(In the formula, each group has a bond on two arbitrary carbon atoms, one or more arbitrary hydrogen atoms may be substituted with L ^W , and ^RT is a hydrogen atom or carbon. It preferably represents a group selected from 1 to 8 alkyl groups.

  Examples of the group represented by the above formula (W-6) include the following formula (W-6-1) to formula (W-6-8).

(In the formula, each group has a bond on two arbitrary carbon atoms, and one or two or more arbitrary hydrogen atoms may be substituted with L ^W ). It is preferable.

  Among them, W is a formula (W-1-3), a formula (W-1-6), a formula (W-1-7), a formula (W-2-1) to a formula (W-2-8), a formula (W-3-1), Formula (W-3-4), Formula (W-3-5), Formula (W-3-8), Formula (W-4-1) to Formula (W-4-) 7), preferably represents a group represented by formula (W-5-1), formula (W-5-4) or formula (W-6-1) to formula (W-6-8). It is more preferable to represent a group represented by (W-2-1) to Formula (W-2-3).

In the general formula (I), L ^W 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, or a methylamino group. , Dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, or one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, a straight chain having 2 to 20 carbon atoms substituted by -OCO-CH = CH- Although a branched substituted alkyl group, any hydrogen atom in the alkyl group may be substituted by a fluorine atom, or, ^{L W} is ^P LW ^- represented by _- ^{(Sp _LW} -X _^LW) kLW In which P ^LW represents a polymerizable group, and Sp ^LW represents one —CH ₂ — or two or more non-adjacent —CH ₂ — each independently —O—, Represents a linear alkylene group having 1 to 10 carbon atoms which may be substituted by —COO— or —OCO— or a single bond, and when a plurality of Sp ^LWs are present, they may be the same or different. Well, X ^LW is —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —CO—S—, —S— ^CO— , —O. -CO-O -, - CO- NH -, - NH-CO -, - SCH 2 -, - CH ₂ S—, —CF ₂ O—, —OCF ₂ —, —CF ₂ S—, —SCF ₂ —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, _{-OCO-CH = CH -, -} COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 - _{, -OCO-CH 2 -, -} CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH -, - CF = CF-, -C≡C- or represents a single ^{bond, X LW} is they If there are multiple or different and the same ^{(however, P LW - (Sp LW -X} LW) kLW - the -O Does not include -O- bond. ), KLW represents an integer of 0 to 10. From the viewpoints of reverse wavelength dispersibility, ease of synthesis, difficulty in generating bubbles when made into paints, and adhesion to various substrates (or alignment films), L ^W is a fluorine atom, a chlorine atom, pentafluorosulfur. A furanyl group, a nitro group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, or one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently — O—, —CO—, —COO—, —OCO—, —O—CO—O—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH— or —OCO—. It preferably represents a linear or branched substituted alkyl group having 2 to 20 carbon atoms substituted by CH═CH—, and includes a fluorine atom, a chlorine atom, a methylamino group, a dimethylamino group, a diethylamino group, a diamino group, Isopropyl amino group, or one -CH ₂ - or nonadjacent two or more -CH ₂ - are each independently -O -, - CO -, - COO- or substituted by -OCO- More preferably represents a linear or branched substituted alkyl group having 2 to 12 carbon atoms, a dimethylamino group, a diethylamino group, a diisopropylamino group, or one —CH ₂ — or not adjacent to each other. It is further possible that two or more —CH ₂ — each independently represents a linear alkyl group having 2 to 8 carbon atoms substituted by —O—, —CO—, —COO— or —OCO—. preferable.

In the general formula (I), -W-L ^W is represented by the following formula (from the viewpoint of reverse wavelength dispersibility, difficulty of foam generation when formed into a paint, and adhesion to various substrates (or alignment films): It is particularly preferable to select from WL-1) to (WL-6).

(In the formula, each group has a bond on one arbitrary carbon atom in the six-membered ring structure.)
Here, a group represented by the formula (WL-1) ~ (WL -6) preferably has a bond to the para position relative to L ^W in six-membered ring structure.

In general formula (I), Y represents a hydrogen atom, 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, or methylamino. Group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, or one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O. -, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, By —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF— or —C≡C—. A linear or branched alkyl group having 1 to 20 carbon atoms that may be substituted is represented, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or Y is P ^Y- ( Sp ^Y —X ^Y ) _kY — may be represented, P ^Y represents a polymerizable group, and Sp ^Y represents one —CH ₂ — or two or more —CH ₂ not adjacent to each other. -Each independently represents a linear alkylene group having 1 to 10 carbon atoms which may be substituted by -O-, -COO-, or -OCO- or a single bond, and when a plurality of Sp ^Y are present, May be the same or different, and ^XY represents —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —CO—S. -, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-,- _{CH 2 -, - CH 2 S} -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO _{-CH = CH -, - OCO-} CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO-, _{-COO-CH 2 -, - OCO} -CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH-, -CF = CF -, - C≡C- or represents a single bond, ^{X Y} is they If there are multiple or different and the same ^{(although, P Y - (Sp Y -X} Y) _kY- does not include an -O-O- bond. ), KY represents an integer of 0 to 10. From the viewpoint of liquid crystallinity and ease of synthesis, Y may be a hydrogen atom, a fluorine atom, a chlorine atom, a nitro group, a cyano group, or any hydrogen atom in the group may be substituted with a fluorine atom. ₂ - or nonadjacent two or more -CH ₂ - are each independently -O -, - S -, - CO -, - COO- or from a good carbon atoms 1 be replaced by -OCO- Preferably, it represents a 20 straight chain or branched alkyl group, and a straight chain or branched alkyl group having 1 to 12 carbon atoms in which a hydrogen atom or any hydrogen atom in the group may be substituted with a fluorine atom More preferably, a hydrogen atom or a linear alkyl group having 1 to 12 carbon atoms is more preferable, and a hydrogen atom is particularly preferable.
In the general formula (I), A ¹ and A ² are each independently 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, decahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl group Wherein these groups are unsubstituted or may be substituted by one or more substituents L, where 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, Chioisoshiano group, or 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 A straight chain of 1 to 20 carbon atoms which may be substituted by —, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF— or —C≡C— A hydrogen atom in the alkyl group may be substituted with a fluorine atom, or L is a group represented by P ^L- (Sp ^L -X ^L ) _kL-. may represent, where ^{P L} represents a polymerizable group, Sp ^L is one -CH ₂ - Wakashi -O independently are each - _- it is nonadjacent two or more -CH 2, - COO -, - OCO- linear alkylene group or a single bond 10 from good carbon atoms 1 be replaced by represents a, they if Sp ^L there are a plurality or different and are identical, ^{X L} is _{-O -, - S -, -} OCH 2 -, - CH 2 O -, - CO-, -COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S- _{, -CF 2 O -, - OCF} 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO- _{CH = CH -, - COO-} CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -CO _{-, - CH 2 CH 2 -OCO} -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N- , -CH = N-N = CH -, - CF = CF -, - C≡C- or represents a single bond, ^{if X L} there are a plurality thereof may be different even if the same (although , P ^L- (Sp ^L -X ^L ) _kL -does not contain an -O-O- bond. ), KL represents an integer of 0 to 10, but when a plurality of L are present in the compound, they may be the same or different, and when a plurality of A ¹ are present, they are the same or different. In the case where a plurality of A ² are present, they may be the same or different. In view of ease of synthesis, availability of raw materials, and liquid crystallinity, A ¹ and A ² are each independently unsubstituted or optionally substituted by one or more substituents L It preferably represents a phenylene group, a 1,4-cyclohexylene group, or a naphthalene-2,6-diyl group, and each independently represents the following formulas (A-1) to (A-11):

More preferably, each independently represents a group selected from the formula (A-1) to the formula (A-8), and each independently represents a group selected from the formula (A-1). It is particularly preferable to represent a group selected from the formula (A-4). From the viewpoint of reverse wavelength dispersion, tables in Z ² adjacent to the group represented by group and G ¹ is represented by A ¹ that binds to a group represented by Z ¹ adjacent to the group represented by G ¹ The group represented by A ² bonded to the group to be represented is a 1,4-cyclohexylene group which is each independently unsubstituted or may be substituted by one or more of the above-described substituents L. It is preferable that the group represented by the above formula (A-2) is more preferable. Further, A ¹ and when the group represented by A ² there are a plurality of refractive index anisotropy, from the viewpoint of solubility in ease of synthesis and solvent, adjacent to the G ¹ side A ¹ and A ² As the group represented by A ¹ and A ² other than ^1, 1,4-phenylene group, naphthalene-2,6, which may be independently unsubstituted or substituted by one or more substituents L -It preferably represents a diyl group, more preferably each independently represents a group selected from the above formula (A-1), formula (A-3) to formula (A-11), and each independently. It is more preferable to represent a group selected from Formula (A-1) and Formula (A-3) to Formula (A-8), and each independently represents Formula (A-1), Formula (A-3), Formula It is particularly preferable to represent a group selected from (A-4). From the viewpoint of liquid crystallinity and ease of synthesis, the substituent L is a fluorine atom, a chlorine atom, or one —CH ₂ — in which an arbitrary hydrogen atom may be replaced by a fluorine atom, or _two that are not adjacent to each other. The above —CH ₂ — each preferably independently represents a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted with —O—, —COO— or —OCO—, and fluorine More preferably, the atom, chlorine atom, or any hydrogen atom represents a linear or branched alkyl group or alkoxy group having 1 to 12 carbon atoms which may be substituted with a fluorine atom. Or a linear alkyl group having 1 to 8 carbon atoms or a linear alkoxy group is more preferable, and a fluorine atom, a chlorine atom, a methyl group or a methoxy group is particularly preferable.
In the general formula (I), Z ¹ and Z ² are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ —, —CO—, —COO—, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH _{-CO-NH -, - NH-} O -, - O-NH -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 - , —CH═CH—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, when a plurality of Z ¹ are present, they may be the same or different, and when a plurality of Z ² are present, they are the same or different. Also good. Z ¹ and Z ² are —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CF ₂ O—, —OCF from the viewpoint of liquid crystallinity, availability of raw materials, and ease of synthesis. _{2 -, - CH 2 CH 2} -, - CF 2 CF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO—, —CH ₂ CH ₂ —OCO—, —CH═CH—, —CF═CF—, —C≡ it is preferable to represent a C- or a single _{bond, -OCH 2 -, - CH 2} O -, - COO -, - OCO -, - CF 2 O -, - OCF 2 -, - CH 2 CH 2 -, - 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 a single bond is more preferable, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO— or more preferably represents a single _{bond, -OCH 2 -, - CH 2} O -, - and particularly preferably a COO- or -OCO-.

  In general formula (I), G represents the following formulas (G-1) to (G-8):

Represents a group selected from, corresponding horizontal bonds in these formulas is a horizontal bond G, these groups are substituted by unsubstituted or substituted with one or more L ^{G LG} 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, 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- OO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF— or —C≡C— may be substituted. It represents a linear or branched alkyl group having 1 to 20 carbon atoms, optional hydrogen atom in the alkyl group may be substituted by a fluorine atom, or, L ^G is P ^{LG -} (Sp ^{LG -} X ^LG ) _kLG- may be used, where P ^LG represents a polymerizable group, and Sp ^LG represents one -CH ₂ -or two or more non-adjacent -CH _2- groups. Each independently represents a linear alkylene group having 1 to 10 carbon atoms which may be substituted by -O-, -COO-, or -OCO- or a single bond, and when a plurality of Sp ^LG are present, They may be the same or different and X ^LG is − O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, _{-CO-NH -, - NH-} CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH- COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —CH ₂ CH _{2 -COO -, - CH 2 CH 2} -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N- N = CH -, - CF = CF -, - C≡C- or represents a single ^{bond, a} place ^{X LG} there are multiple They may be different even in the same ^{(however, P LG - (Sp LG -X} LG) kLG - to contain no -O-O- bonds. ), KLG represents an integer of 0 to 10, they may be different even in the same case where L ^G is more present in the compound. From the viewpoint of solubility in a solvent, liquid crystallinity, and ease of synthesis, G preferably represents a group represented by Formula (G-1) to Formula (G-6), and is represented by Formula (G-1) or It is more preferable to represent the group represented by the formula (G-2). From the viewpoint of the ease of the liquid crystal and synthetic, L ^G is fluorine atom, a chlorine atom, a nitro group, a cyano group, a dimethylamino group, or any hydrogen atom is -CH also be one which is substituted with a fluorine atom ₂ or two or more non-adjacent —CH ₂ — are each independently a linear or branched group having 1 to 12 carbon atoms which may be substituted by —O—, —COO— or —OCO—. It preferably represents an alkyl group, and a fluorine atom, a chlorine atom, a nitro group, a cyano group, a dimethylamino group, or an arbitrary hydrogen atom is a straight chain having 1 to 12 carbon atoms, which may be substituted with a fluorine atom, or It is more preferably a branched alkyl group or an alkoxy group, and further preferably a fluorine atom, a chlorine atom, a nitro group, a cyano group, a dimethylamino group, a methyl group or a methoxy group.
In general formula (I), m1 and m2 each independently represent an integer of 0 to 6, while m1 + m2 represents an integer of 0 to 6. From the viewpoints of solubility in a solvent, liquid crystallinity, and adhesion to various substrates (or alignment films), m1 and m2 preferably each independently represent an integer of 1 to 3, and each independently 1 or More preferably, 2 is represented. Moreover, it is preferable that m1 and m2 are the same from a viewpoint of the ease of a synthesis | combination.
In the general formula (I), (A ¹ -Z ¹ ) _m1 -G or G- (Z ² -A ² ) _m2 is represented by the following formulas (AZG-1) to (AZG-10) from the viewpoint of reverse wavelength dispersion. It is preferable to represent a group selected from

  The compound represented by the general formula (I) is a liquid crystal phase temperature range, solubility in an organic solvent, wavelength dispersibility, balance between wavelength dispersibility and refractive index anisotropy, melting point, From the viewpoint of difficulty in generation and adhesion to a substrate, the following general formula (Ii)

(In the formula, A ¹ , A ² , Z ¹ , Z ² , m 1, m ² and R ³ represent the same meaning as in general formula (I), and P ¹ and P ² are radical polymerization, radical addition polymerization, cationic polymerization or Represents a group that is polymerized by anionic polymerization, and a preferred structure is the same as P ⁰ , Sp ¹ and Sp ² represent a linear or branched alkylene group having 1 to 30 carbon atoms or a single bond, and the alkylene group is 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 -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OC -CH = CH -, - CH = CH -, - N = N -, - CH = N-N = CH -, - CF = CF- or may be replaced by -C≡C, Sp ¹ and When a plurality of Sp ² are present, they may be the same or different, and X ¹ and X ² are —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, — COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —SCH ₂ —, —CH ₂ S—, _{-CF 2 O -, - OCF 2} -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH _{= CH -, - COO-CH} 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 _{-OCO -, - COO-CH 2} -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N ═CH—, —CF═CF—, —C≡C— or a single bond, but when a plurality of X ¹ and X ² are present, they may be the same or different, and k1 and k2 are 0 Represents an integer of 10 to 10 (provided that P ^1- (Sp ¹ -X ¹ ) _k1- and-(X ² -Sp ² ) _k2 -P ² do not include an -O-O- bond), G ¹ each represents a group selected from the formula (G-8) from the above equation (G-1), may be replaced by these groups or is unsubstituted or one or more of the above L ^G, Y ¹ Is a hydrogen atom, fluorine atom, chlorine atom, nitro group, cyano group or any hydrogen atom in the group may be replaced by a fluorine atom. In addition, one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently substituted by —O—, —S—, —CO—, —COO— or —OCO—. Represents a linear or branched alkyl group having 1 to 20 carbon atoms, and W ¹ represents the above formula (W-1-1) to formula (W-1-7), formula (W-2-1). ) To formula (W-2-8), formula (W-3-1) to formula (W-3-8), formula (W-4-1) to formula (W-4-7), formula (W -5-1) represents a group selected from the groups represented by formula (W-5-4) and formula (W-6-1) to formula (W-6-8), but these groups are none. Which may be substituted or substituted with one or more of the above L ^W , L ^W1 is fluorine atom, chlorine atom, pentafluorosulfuranyl group, nitro group, methylamino group, dimethylamino group, diethyl A ruamino group, a diisopropylamino group, or one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —CO—, —COO—, —OCO—, 2 to 20 carbon atoms substituted by —O—CO—O—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH— or —OCO—CH═CH— Represents a linear or branched substituted alkyl group. Is preferably represented by the following general formula (I-i-i)

(Wherein P ¹¹ and P ²¹ are each independently the above formula (P-1), formula (P-2), formula (P-3), formula (P-4), formula (P-5) Represents a group selected from Formula (P-7), Formula (P-11), Formula (P-13), Formula (P-15) or Formula (P-18), and one Sp ¹¹ and Sp ²¹ -CH ₂ — or two or more non-adjacent —CH ₂ — may be each independently replaced by —O—, —COO—, —OCO— or —O—CO—O—. A linear or branched alkylene group having a number of 1 to 20 or a single bond is represented, but when a plurality of Sp ¹¹ and Sp ²¹ are present, they may be the same or different, and X ¹¹ and X ²¹ are- _{O -, - S -, -} OCH 2 -, - CH 2 O -, - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O- , —COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO—, —CH ₂ CH ₂ —OCO— or a single bond, but a plurality of X ¹¹ and X ²¹ when present they may be different even in the same, k11 and k21 is an integer of 0 3 ^{(where, P 11 - (Sp 11 -X} 11) k11 - and ^- (X 21 ^{-Sp 21} ) _k21 the -P ²¹ does not contain -O-O- ^{bond.), a 11, a 12} , a 21 and ^{a 22} are each independently formula from the above equation (a-1) (a- 11) Z ¹¹ , Z ¹² , Z ²¹ and Z ²² are each independently —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CF ₂ O—, —OCF. _{2 -, - CH 2 CH 2} -, - COO-CH 2 CH _{-, - OCO-CH 2 CH} 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - CH = CH -, - C≡C- or a single ^{bond, G 11} is the of it from the formula (G-1) represents a group selected from the formula (G-6), may be replaced by these or groups are unsubstituted or one or more of the above L ^G, Y ¹¹ is hydrogen An arbitrary hydrogen atom in the atom or group represents a linear or branched alkyl group having 1 to 12 carbon atoms that may be substituted with a fluorine atom, and W ¹¹ represents the formula (W-1-3), the formula ( W-1-6), Formula (W-1-7), Formula (W-2-1) to Formula (W-2-8), Formula (W-3-1), Formula (W-3-4) ), Formula (W-3-5), Formula (W-3-8), Formula (W-4-1) to Formula (W-4-7), Formula (W-5-1), Formula (W -5-4) or formula (W-6-1) ) To a group selected from formula (W-6-8), and L ^W11 represents a fluorine atom, a chlorine atom, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, or one —CH ₂ —. Or a linear or branched group having 2 to 12 carbon atoms in which two or more non-adjacent —CH ₂ — are each independently substituted by —O—, —CO—, —COO— or —OCO—. R ³¹ is a hydrogen atom, or one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —CO—, —COO. -, -OCO-, -O-CO-O-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH -, -CF = CF- or -C≡C- Linear or branched alkyl group having optionally a carbon atom number of 1 may be substituted 20 ^{Te, P 31 - (Sp 31 -X} 31) k31 - group (wherein represented ^{by, P 31} is the above formula ( P-1), Formula (P-2), Formula (P-3), Formula (P-4), Formula (P-5), Formula (P-7), Formula (P-11), Formula (P -13), a group selected from the formula (P-15) or the formula (P-18), and Sp ³¹ is independent of one —CH ₂ — or two or more non-adjacent —CH ₂ —. Represents a linear or branched alkylene group having 1 to 20 carbon atoms which may be replaced by -O-, -COO-, -OCO- or -O-CO-O-, or a single bond, Sp ³¹ they if there exist a plurality may be different even in the ^{same, X 31} is _{-O -, - S -, -} OCH 2 -, - CH 2 O-, COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 —COO—, —CH ₂ CH ₂ —OCO— or a single bond is represented, and when a plurality of X ³¹ are present, they may be the same or different, and k31 represents an integer of 0 to 3 (provided that ^{, P 31 - (Sp 31 -X} 31) k31 - to contain no -O-O- bonds. ). ). Is more preferably represented by the following general formula (I-i-i)

(Wherein P ¹¹¹ and P ²¹¹ are each independently the above formula (P-1), formula (P-2), formula (P-3), formula (P-7), formula (P-11)). or represents a group selected from the formulas ^{(P-13), Sp 111} and ^{Sp 211} is one -CH ₂ - replaced by are each independently -O- - or nonadjacent two or more -CH ₂ Represents a straight-chain alkylene group having 1 to 12 carbon atoms, and when there are a plurality of Sp ¹¹¹ and Sp ^211, they may be the same or different, and X ¹¹¹ and X ²¹¹ are — O—, —COO—, —OCO— or a single bond is represented, but when a plurality of X ¹¹¹ and X ²¹¹ are present, they may be the same or different, and k111 and k211 represent an integer of 1 to 3. It represents ^{(wherein, P 111 - (Sp 111 -X} 111) ₁₁₁ - and _{^{-. (X 211 -Sp 211)}} k211 in ^{-P 211} without the -O-O- ^{bonds), A 111, A 121,} A 211 and ^{A 221} each independently the above formula (A -1) to a group selected from formula (A-4), and Z ¹¹¹ , Z ¹²¹ , Z ²¹¹ and Z ²²¹ are each independently —OCH ₂ —, —CH ₂ O—, —COO—, —OCO. - or a single bond, G ¹¹¹ each represents a group selected from the above equation (G-1) or formula (G-2), or these groups are unsubstituted or one or more of the above L ^G Y ¹¹¹ represents a hydrogen atom or a linear alkyl group having 1 to 12 carbon atoms, and W ¹¹¹ represents the following formula (W-2-1-1) to formula (W-2- 3-6)

(In the formula, the bond in the lower left direction is bonded to N, and the remaining bond is bonded to ^LW111 .) ^LW111 represents a dimethylamino group, diethylamino group, diisopropylamino. A group or a carbon in which one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently substituted by —O—, —CO—, —COO— or —OCO—. Represents a linear alkyl group having 2 to 8 atoms, R ³¹¹ represents a hydrogen atom, or one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—. , A linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by —COO— or —OCO—, a group represented by P ³¹¹ — (Sp ³¹¹ —X ³¹¹ ) _k311 — (in the formula, , ^{P 311} is above Formula (P-1), formula (P-2), formula (P-3), formula (P-7), represents a group selected from the formula (P-11) or formula ^{(P-13), Sp 311} Represents a linear alkylene group having 1 to 12 carbon atoms in which one —CH ₂ — or two or more non-adjacent —CH ₂ — may be each independently replaced by —O—. , they ^{if Sp 311} there are a plurality may be different even in the ^{same, X 311} is -O -, - COO -, - OCO- or represents a single ^bond, their ^{If X 311} there are a plurality of may be different even identical, K311 is an integer from 1 to 3 ^(but, P ³¹¹ - to contain no -O-O- bond _{^{- (Sp 311 -X 311) k311}} .) Represents.) It is more preferable that the following general formula (I-i-i-i)

(In the formula, P ¹¹¹¹ and P ²¹¹¹ each independently represent a group selected from the above formula (P-1), formula (P-2) or formula (P-3), and Sp ¹¹¹¹ and Sp ²¹¹¹ are 1 Each of —CH ₂ — or two or more non-adjacent —CH ₂ — independently represents a linear alkylene group having 1 to 12 carbon atoms which may be replaced by —O—. ^{If 1111} and ^{Sp 2111} there are a plurality thereof may be different even in the ^{same, X 1111} and ^{X 2111} is -O -, - COO -, - OCO- or represents a single ^{bond, X 1111} and X ^When two or more ²¹¹¹ exist, they may be the same or different, and k1111 and k2111 represent an integer of 1 to 3 (provided that P ¹¹¹¹ − (Sp ¹¹¹¹ −X ¹¹¹¹ ) _k1111 − and -(X ²¹¹¹ -Sp ²¹¹¹ ) _k2111 -P ²¹¹¹ does not contain an —O—O— bond.), A ¹¹¹¹ and A ²²¹¹ are each independently represented by the following formulas (A-1-1) to (A -4-1)

(In the formula, L ¹¹¹¹ represents a linear or branched alkyl group or alkoxy group having 1 to 12 carbon atoms in which a fluorine atom, a chlorine atom, or an arbitrary hydrogen atom may be substituted with a fluorine atom.) A ¹²¹¹ and A ²¹¹¹ represent a group represented by the above formula (A-2-1), and Z ¹¹¹¹ , Z ¹²¹¹ , Z ²¹¹¹ and Z ²²¹¹ each independently represent —OCH _2. -, -CH ₂ O-, -COO-, -OCO- or a single bond, G ¹¹¹¹ represents a group selected from the above-mentioned formula (G-1) or formula (G-2), and Y ¹¹¹¹ represents a hydrogen atom, W ¹¹¹¹ represents a group selected from the above formulas (W-2-1-1) to (W-2-2-10), L ^W1111 represents a dimethylamino group, a diethylamino group, Diisopropylamino group, Is one -CH ₂ - or nonadjacent two or more -CH ₂ - are each independently -O -, - CO -, - COO- or number of carbon atoms which is substituted by -OCO- ^{Represents a} linear alkyl group of 2 to 8, R ³¹¹¹ is a hydrogen atom, or one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently substituted by —O—. is from a good carbon atoms 1 be of 12 linear alkyl ^{group, P 3111 - (Sp 3111 -X} 3111) k3111 - group (wherein represented ^{by, P 3111} is above formula (P-1), ^Represents a group selected from the formula (P-2) or the formula (P-3), and Sp ³¹¹¹ is a group in which one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O. Straight-chain alkyl having 1 to 12 carbon atoms which may be replaced by- Represents an alkylene ^{group, Sp 3111} is those if there exist a plurality may be different even in the ^{same, X 3111} is -O -, - COO -, - OCO- or represents a single ^bond, is ^{X 3111} they If there are multiple may be different even in the same, K3111 is an integer from 1 to 3 (provided ^{that, P 3111 - (Sp 3111 -X} 3111) k3111 - in the the -O-O- bond Not included))). Is more preferably represented by the following general formula (I-i-i-i-i)

( ^Wherein P ¹¹¹¹¹ and P ²¹¹¹¹ each independently represent a group selected from the above formula (P-1) or formula (P-2), and Sp ¹¹¹¹¹ and Sp ²¹¹¹¹ are each a straight chain having 1 to 12 carbon atoms. ^{Represents a} chain alkylene group, X ¹¹¹¹¹ and X ²¹¹¹¹ represent -O-, ^{-COO-, -OCO-} or a single bond, A ¹¹¹¹¹ and A ²²¹¹¹ represent a 1,4-phenylene group, A ¹²¹¹¹ and A ²¹¹¹¹ 1,4 ^{cyclohexylene, Z 11111, Z 12111, Z} 21111 and ^{Z 22111} are each independently _{-OCH 2 -, - CH 2 O} -, - COO- or an ^{-OCO-, G 11111} represents a group selected from unsubstituted above formula (G-1) or formula ^{(G-2), Y 11111} represents a hydrogen ^{atom, W 11111} is above formula ( -2-1-1), represents a group selected from the formula (W-2-2-1) or formula ^{(W-2-2-5), L W11111} dimethylamino group, dimethylamino group, diethylamino group, Represents an alkoxy group having 1 to 7 carbon atoms, an alkanoyl group having 2 to 8 carbon atoms, or an alkoxycarbonyl group having 1 to 7 carbon atoms, and R ³¹¹¹¹ represents a hydrogen atom or the following formula (W2-a-1) Formula (W2-a-6)

(Wherein k2a represents an integer of 1 to 12, k2b represents 1 or 2, k2c represents an integer of 2 to 11, and k2d represents an integer of 1 to 3) or a group selected from Formula (W2-a-7) to Formula (W2-a-9)

(Wherein W ^A3 each independently represents a hydrogen atom or a methyl group, k2c represents an integer of 2 to 11, and k2d represents an integer of 1 to 3). It is even more preferable that it is represented by the following general formula (IA-1)

( ^Wherein W ^A1 and W ^A2 each independently represent a hydrogen atom or a methyl group, Sp ^A1 and Sp ^A2 each independently represent a linear alkylene group having 2 to 10 carbon atoms, and Sp ^A1 and Sp ^A2 preferably represents a linear alkylene group having 2 to 8 carbon atoms, and W ^1A1 is represented by the following formula (W-2-1-1) to formula (W-2-2-5):

(Wherein, the bond in the lower left direction is bonded to N, and the bond in the upper right direction is bonded to L ^WA1 ), and represents a group selected from the above formula (W-2-2-1). ) Or a group selected from formula (W-2-2-5) is preferable, a group represented by the above formula (W-2-2-5) is particularly preferable, and L ^WA1 is represented by the following formula (LW-A) -1) to formula (LW-A-5)

(Wherein R ^A1 represents an alkyl group having 1 to 7 carbon atoms, preferably represents an alkyl group having 1 to 3 carbon atoms, particularly preferably represents a methyl group, and R ^A2 represents 1 carbon atom) Represents an alkyl group having 1 to 7 carbon atoms, preferably represents an alkyl group having 1 to 3 carbon atoms, particularly preferably represents a methyl group, and R ^A3 represents an alkyl group having 1 to 6 carbon atoms, A group selected from 1 to 3 alkyl groups, particularly preferably a methyl group or an ethyl group, and a group selected from the above formulas (LW-A-1) and (LW-A-2). ), A group selected from the formula (LW-A-4) or the formula (LW-A-5), and the above formula (LW-A-1), the formula (LW-A-2) or the formula (LW- A group selected from A-5) is more preferable, and the above formula (LW- Particularly preferred groups represented by ^{-5), R 3A1} formula from hydrogen atom or the following formula (W2-a-3-1) ( W2-a-7-2)

( ^Wherein W ^A3 each independently represents a hydrogen atom or a methyl group), and R ^3A1 represents the above formula (W2 from the viewpoint of long-term storage stability of a solution dissolved in an organic solvent. -A-3-1) to a group selected from formulas (W2-a-7-2) are preferred, and the above formulas (W2-a-3-1) and (W2-a-7-1) are preferred. ) Or a group selected from formula (W2-a-7-2) is more preferable. ) Is particularly preferable.

  The 1,4-cyclohexylene group, 1,3-dioxane-2,5-diyl group and decahydronaphthalene-2,6-diyl group contained in the compound of the present invention are only one of the cis isomer and the trans isomer. However, the trans isomer is preferably the main component from the viewpoint of liquid crystallinity, the trans isomer is more preferably 70% or more, and the trans isomer is 90% or more. More preferably, the trans isomer is more preferably 95% or more, even more preferably 99% or more, and particularly preferably only the trans isomer.

  Specifically, compounds represented by the following formula (I-1) to formula (I-201) are preferable as the compound represented by the general formula (I).

The compound of the present invention can be produced by a conventionally known production method. For example, the following manufacturing methods can be mentioned.
[Production Method 1] Production of a compound represented by the following formula (S-12)

(Wherein, ^{P S} represents the same meaning as ^{P 0} in the general formula (I-0-R), Sp S has the same meaning as Sp ⁰ in the general formula (I-0-R), X S is generally X ⁰ in Formula (I-0-R) represents the same meaning, W ^S represents the same meaning as W in General Formula (I), R ^S represents the same meaning as R ³ in General Formula (I), Lw ^S has the same meaning as Lw in the general formula (I), ^{r s} represents the same meaning as r in the general formula ^{(I), L S1} has the same meaning as L in formula ^{(I), L S2 Represents the} same meaning as LG in formula (I), each s independently represents an integer of 0 to 4, t represents an integer of 0 to 3, PG represents a protecting group, and halogen represents a halogen atom. Or represents 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. 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, and an ethoxymethyl group.

  The compound represented by the formula (S-4) can be obtained by reacting the compound represented by the formula (S-2) with the compound represented by the formula (S-3). As the reaction conditions, for example, a method using a condensing agent or a compound represented by the formula (S-2) is converted to an acid chloride, mixed acid anhydride or carboxylic acid anhydride, and then represented by the general formula (S-3). 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.

  The protecting group (PG) of the compound represented by the formula (S-4) is deprotected. The reaction conditions for deprotection are not particularly limited as long as they give the compound represented by the formula (S-5), but those listed in the above-mentioned literature are preferable.

  The compound represented by the formula (S-7) can be obtained by reacting the compound represented by the formula (S-5) with the compound represented by the formula (S-6). Examples of the reaction conditions include the same as those described above.

  The compound represented by the formula (S-9) can be obtained by reacting the compound represented by the formula (S-8) with, for example, hydrazine monohydrate.

  The compound represented by the formula (S-11) can be obtained by reacting the compound represented by the formula (S-9) with the compound represented by the formula (S-10) in the presence of a base. Examples of the base include potassium carbonate, cesium carbonate, triethylamine and the like.

The compound represented by the formula (S-12) can be obtained by reacting the compound represented by the formula (S-11) with a compound represented by the formula (S-7) in the presence of an acid catalyst. . Examples of the acid include p-toluenesulfonic acid, pyridinium p-toluenesulfonate, 10-camphorsulfonic acid, and the like.
[Production Method 2] Production of a compound represented by the following formula (S-18)

(Wherein, ^{P S} represents the same meaning as ^{P 0} in the general formula (I-0-R), Sp S has the same meaning as Sp ⁰ in the general formula (I-0-R), X S is generally X ⁰ in formula (I-0-R) represents the same meaning, W ^S represents the same meaning as W in general formula (I), L ^S1 represents the same meaning as L in general formula (I), L ^S2 are the same meaning as ^{L G} in the general formula (I), s each represents an integer of independently from 0 4, t represents an integer from 0 3, PG represents a protecting group, halogen is halogen Represents an atomic or halogen equivalent.)
The carboxyl group of the compound represented by the formula (S-1) is protected with a protecting group (PG). Examples of the protecting group (PG) include those described in Production Method 1.

  The compound represented by the formula (S-13) can be obtained by reducing the compound represented by the formula (S-2). Examples of the reducing agent include borane complexes such as borane-tetrahydrofuran complex and borane-dimethyl sulfide complex, and diborane.

  The compound represented by the formula (S-14) can be obtained by halogenating the compound represented by the formula (S-13). The conditions for halogenation include a method of reacting with iodine in the presence of triphenylphosphine and imidazole, a method of reacting with carbon tetrabromide or N-bromosuccinimide in the presence of triphenylphosphine, and a reaction with lithium chloride in the presence of a base. A method is mentioned. In addition, a method of inducing to a halogen equivalent by reacting with methanesulfonyl chloride or p-toluenesulfonyl chloride in the presence of a base can be mentioned.

  The compound represented by the formula (S-15) can be obtained by reacting the compound represented by the formula (S-14) with a compound represented by the formula (S-6) in the presence of a base. Examples of the base include those described in Production Method 1.

  The protecting group (PG) of the compound represented by the formula (S-15) is deprotected. The reaction conditions for deprotection are not particularly limited as long as they give the compound represented by formula (S-16), but those listed in the above-mentioned literature are preferable.

The compound represented by the formula (S-17) can be obtained by reacting the compound represented by the formula (S-16) with the compound represented by the formula (S-3). Examples of the reaction conditions include those described in Production Method 1.
The compound represented by the formula (S-18) can be obtained by reacting the compound represented by the formula (S-17) with a compound represented by the formula (S-11) in the presence of an acid catalyst. . Examples of the acid include those described in Production Method 1.

  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 er (Chemical Abstracts Service, American Chemical Society) or Reays (Elsevier Ltd.).

  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, diethylene glycol, methanol, ethanol, propanol, chloroform, dichloromethane, 1,2-dichloroethane, acetone, acetonitrile, N, N- Dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, diethyl ether, ethylene glycol monoethyl ether, xylene, ethyl acetate, butyl acetate, propyl acetate, methyl acetate, cyclohexanone, 1,4-dioxane, dichloromethane, styrene, tetrahydrofuran, Pyridine, 1-methyl-2-pyrrolidinone, toluene, hexane, cyclohexane, heptane, benzene, methyl isobutyl ketone, tert-butyl Chirueteru, 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, acidic clay, silicon dioxide, diatomaceous earth, Examples include perlite, cellulose, organic polymer, and porous gel.
The compound of the present invention is preferably used in a nematic liquid crystal composition, a smectic liquid crystal composition, a chiral smectic liquid crystal composition, and a cholesteric liquid crystal composition. In the liquid crystal composition using the 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)

(In the formula, P ¹¹ , P ¹² and P ¹³ each independently represent a polymerizable group, and Sp ¹¹ , Sp ¹² and Sp ¹³ each independently represent a single bond or an alkylene group having 1 to 20 carbon atoms. represents but one -CH ₂ - or nonadjacent two or more _-CH 2 - is -O -, - COO -, - OCO -, - OCOO- may be replaced ^{by, 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 = CH-OCO -, - COO-CH = CH -, - OCO- _{H = 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, Z 11} and ^{Z 12} are each independently _, - - S _-, - _-O and 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 -, - C = 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 Represents ≡C— or a single bond, and A ¹¹ , A ¹² , A ¹³ and A ¹⁴ each independently represents a 1,4-phenylene group, a 1,4-cyclohexylene group, a 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 It represents ^{but, A 11, A 12, A} 13 and ¹⁴ are each independently unsubstituted or substituted by an alkyl group, a halogenated alkyl group, alkoxy group, halogenated alkoxy group, a halogen atom, may be substituted with a cyano group or a nitro group, R ¹¹ 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. —NH—, —NH—CO—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —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 m11 and m12 represent 0, 1, 2 or 3, but 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. , 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).

(Wherein P ¹⁴ represents a polymerizable group, 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 represents a single bond, —O—, —COO—, or —OCO—. , Z ¹⁵ represents a single bond, —COO— or —OCO—, and L ¹¹ is independently a fluorine atom, a chlorine atom, one —CH ₂ — or two or more non-adjacent —CH ₂ —. Te -O -, - COO -, - OCO- the replaced represents a linear or branched alkyl group having optionally a carbon atom number of 1 even of 10, s11 represents an integer from 0 ^{4, R 12} represents hydrogen Atom, fluorine atom, chlorine atom, cyano group, nitro group, one -CH2- or adjacent Two or more —CH 2 — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—. O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH—, —CF═CF— or —C≡C— represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted.

  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 type of stabilizer may be used, or two or more types 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.

  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, vacuum drying, and vacuum 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 peeling. 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. “%” In the compositions of the following examples and comparative examples means “% by mass”. Further, the cis / trans isomer in the cyclohexane ring represents the trans isomer unless otherwise specified. 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.
Example 1 Production of Compound Represented by Formula (I-1)

To the reaction vessel, 43.9 g of hydrazine monohydrate and 100 mL of ethanol were added. 32.1 g of a compound represented by the formula (I-1-1) was added dropwise at 60 ° C. and stirred at the same temperature for 3 hours. Ethanol was distilled off from the reaction solution to obtain 51.9 g of a solid containing a compound represented by the formula (I-1-2).
To the reaction vessel, 3.6 g of the compound represented by the formula (I-1-3), 1.9 g of triethylamine, and 15 mL of 1,2-dimethoxyethane were added. 3.2 g of a solid containing the compound represented by the above formula (I-1-2) was dissolved in 10 mL of 1,2-dimethoxyethane, added dropwise at 50 ° C., and stirred at 65 ° C. for 18 hours. The reaction solution was diluted with dichloromethane, washed with water and then brine, and the solvent was distilled off. Purification was performed by column chromatography (alumina) to obtain 4.7 g of a compound represented by the formula (I-1-4).
To the reaction vessel, 100.0 g of the compound represented by the formula (I-1-5) and 400 mL of tetrahydrofuran were added. A 1 mol / L borane / tetrahydrofuran solution was added dropwise while cooling with ice, followed by stirring at room temperature for 3 hours. The reaction mixture was diluted with dichloromethane and washed with hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution and brine in this order. After drying with sodium sulfate, the solvent was distilled off. Purification was performed by distillation to obtain 64.6 g of a compound represented by the formula (I-1-6).
To the reaction vessel, 127.0 g of the compound represented by the formula (I-1-6), 70 g of pyridine, and 250 mL of dichloromethane were added. 92.9 g of methanesulfonyl chloride was added dropwise with ice cooling, and the mixture was stirred at room temperature for 3 hours. The reaction solution was washed with hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution and brine in this order. After drying with sodium sulfate, the solvent was distilled off. Purification was performed by column chromatography (silica gel) and recrystallization (acetone / methanol, toluene / hexane) to obtain 141.7 g of a compound represented by the formula (I-1-7).
To the reaction vessel, 100.1 g of the compound represented by the formula (I-1-7), 27.6 g of 2,5-dihydroxybenzaldehyde, 127.4 g of potassium phosphate and 400 mL of dimethylformamide were added, and the mixture was stirred at 90 ° C. for 6 hours. did. The reaction solution was diluted with ethyl acetate and washed with hydrochloric acid, water and brine in this order. After drying with sodium sulfate, the solvent was distilled off. Purification was performed by column chromatography (silica gel) and recrystallization (acetone / methanol, toluene / hexane) to obtain 63.8 g of a compound represented by the formula (I-1-8).
To the reaction vessel, 63.4 g of the compound represented by the formula (I-1-8), 250 mL of tetrahydrofuran, and 150 mL of methanol were added. 68.2 g of 25% aqueous sodium hydroxide solution was added dropwise at room temperature and stirred for 3 hours. By distilling off the organic solvent from the reaction solution, acidifying with hydrochloric acid and washing with water. 58.9 g of a compound represented by the formula (I-1-9) was obtained.
To the reaction vessel was added 10.0 g of the compound represented by formula (I-1-9), 14.2 g of the compound represented by formula (I-1-10), 580 mg of N, N-dimethylaminopyridine, and 240 mL of dichloromethane. It was. 6.6 g of diisopropylcarbodiimide was added dropwise with ice cooling, and the mixture was stirred at room temperature for 7 hours. The reaction solution was filtered, and the filtrate was purified by column chromatography (silica gel) and recrystallization (dichloromethane / methanol) to obtain 16.8 g of a compound represented by the formula (I-1-11).
In a reaction vessel, 3.0 g of the compound represented by the formula (I-1-11), 1.2 g of the compound represented by the formula (I-1-4), 150 mg of (±) -10-camphorsulfonic acid, 30 mL of tetrahydrofuran And stirred at room temperature for 7 hours. The reaction solution was diluted with dichloromethane, washed with water and brine in this order, and the solvent was distilled off. Purification was performed by column chromatography (silica gel / alumina) and recrystallization (dichloromethane / methanol) to obtain 1.9 g of a compound represented by the formula (I-1).
Transition temperature (heating rate 5 ° C./min) C 73 S 94 N 114 I
¹ H NMR (CDCl ₃ ) δ 1.10-1.96 (m, 29H), 2.08 (m, 4H), 2.24 (m, 4H), 2.54 (t, 2H), 3. 32 (s, 3H), 3.52 (t, 2H), 3.66 (t, 2H), 3.77 (t, 2H), 3.85 (m, 4H), 3.94 (t, 4H) ), 4.18 (t, 4H), 4.37 (q, 2H), 4.60 (t, 2H), 5.82 (d, 2H), 6.13 (dd, 2H), 6.4 (D, 2H), 6.87 (d, 6H), 6.97 (d, 4H), 7.51 (s, 1H), 7.68 (d, 1H), 8.16 (d, 1H) , 8.36 (s, 1H), 8.87 (s, 1H) ppm.

LCMS: 1177 [M + 1]
Example 2 Production of Compound Represented by Formula (I-2)

To the reaction vessel, 6.8 g of the compound represented by the formula (I-2-1), 4.8 g of triethylamine, and 40 mL of 1,2-dimethoxyethane were added. 8.0 g of the solid containing the compound represented by the above formula (I-1-2) was dissolved in 25 mL of 1,2-dimethoxyethane, added dropwise at 50 ° C., and stirred at 65 ° C. for 18 hours. The reaction solution was diluted with dichloromethane, washed with water and then brine, and the solvent was distilled off. Purification was performed by column chromatography (alumina) to obtain 8.9 g of a compound represented by the formula (I-2-2).
In a reaction vessel, 5.0 g of the compound represented by the formula (I-1-11), 1.5 g of the compound represented by the formula (I-2-2), 250 mg of (±) -10-camphorsulfonic acid, 50 mL of tetrahydrofuran And stirred at room temperature for 7 hours. The reaction solution was diluted with dichloromethane, washed with water and brine in this order, and the solvent was distilled off. Purification was performed by column chromatography (silica gel / alumina) and recrystallization (dichloromethane / methanol) to obtain 3.4 g of a compound represented by the formula (I-2).
LCMS: 1134 [M + 1]
Example 3 Production of Compound Represented by Formula (I-3)

To the reaction vessel, 8.8 g of a compound represented by the formula (I-3-1), 4.8 g of triethylamine, and 40 mL of 1,2-dimethoxyethane were added. 8.0 g of the solid containing the compound represented by the above formula (I-1-2) was dissolved in 25 mL of 1,2-dimethoxyethane, added dropwise at 50 ° C., and stirred at 65 ° C. for 18 hours. The reaction solution was diluted with dichloromethane, washed with water and then brine, and the solvent was distilled off. Purification was performed by column chromatography (alumina) to obtain 12.1 g of a compound represented by the formula (I-3-2).
In a reaction vessel, 10.0 g of the compound represented by the formula (I-1-11), 3.4 g of the compound represented by the formula (I-3-2), 510 mg of (±) -10-camphorsulfonic acid, 100 mL of tetrahydrofuran And stirred at room temperature for 2 hours. The reaction solution was diluted with dichloromethane, washed with water and brine in this order, and the solvent was distilled off. Purification was performed by column chromatography (silica gel / alumina) and recrystallization (dichloromethane / methanol) to obtain 8.5 g of a compound represented by the formula (I-3).
LCMS: 1176 [M + 1]
Example 4 Production of Compound Represented by Formula (I-4)

To the reaction vessel, 7.4 g of the compound represented by the formula (I-4-1), 4.8 g of triethylamine, and 40 mL of 1,2-dimethoxyethane were added. 8.0 g of the solid containing the compound represented by the above formula (I-1-2) was dissolved in 25 mL of 1,2-dimethoxyethane, added dropwise at 50 ° C., and stirred at 65 ° C. for 13 hours. The reaction solution was diluted with dichloromethane, washed with water and then brine, and the solvent was distilled off. Purification was performed by column chromatography (alumina) to obtain 10.5 g of a compound represented by the formula (I-4-2).
In a reaction vessel, 5.0 g of the compound represented by the formula (I-1-11), 1.5 g of the compound represented by the formula (I-4-2), 250 mg of (±) -10-camphorsulfonic acid, 50 mL of tetrahydrofuran And stirred at room temperature for 4 hours. The reaction solution was diluted with dichloromethane, washed with water and brine in this order, and the solvent was distilled off. Purification was performed by column chromatography (silica gel / alumina) and recrystallization (dichloromethane / methanol) to obtain 1.7 g of a compound represented by the formula (I-4).
LCMS: 1146 [M + 1]
Example 5 Production of Compound Represented by Formula (I-5)

To the reaction vessel, 7.5 g of the compound represented by the formula (I-5-1), 4.8 g of triethylamine, and 40 mL of 1,2-dimethoxyethane were added. 8.0 g of the solid containing the compound represented by the above formula (I-1-2) was dissolved in 25 mL of 1,2-dimethoxyethane, added dropwise at 50 ° C., and stirred at 65 ° C. for 8 hours. The reaction solution was diluted with dichloromethane, washed with water and then brine, and the solvent was distilled off. Purification was performed by column chromatography (alumina) to obtain 10.2 g of a compound represented by the formula (I-5-2).
9.6 g of a compound represented by formula (I-5-3), 9.0 g of a compound represented by formula (I-1-9), 260 mg of N, N-dimethylaminopyridine, and 200 mL of dichloromethane were added to a reaction vessel. It was. Diisopropylcarbodiimide (6.0 g) was added dropwise with ice cooling, and the mixture was stirred at room temperature for 15 hours. The reaction solution was filtered, and the filtrate was washed with hydrochloric acid, water and brine in this order. Purification was performed by column chromatography (silica gel) and recrystallization (dichloromethane / methanol) to obtain 7.9 g of a compound represented by the formula (I-5-4).
In a reaction vessel, 5.0 g of the compound represented by the formula (I-5-4), 1.7 g of the compound represented by the formula (I-5-2), 280 mg of (±) -10-camphorsulfonic acid, 50 mL of tetrahydrofuran And stirred at room temperature for 7 hours. The reaction solution was diluted with dichloromethane, washed with water and brine in this order, and the solvent was distilled off. Purification was performed by column chromatography (silica gel / alumina) and recrystallization (dichloromethane / methanol) to obtain 4.6 g of a compound represented by the formula (I-5).
LCMS: 1065 [M + 1]
Example 6 Production of Compound Represented by Formula (I-6)

To the reaction vessel, 7.5 g of the compound represented by the formula (I-6-1), 4.8 g of triethylamine, and 40 mL of 1,2-dimethoxyethane were added. 8.0 g of the solid containing the compound represented by the above formula (I-1-2) was dissolved in 25 mL of 1,2-dimethoxyethane, added dropwise at 50 ° C., and stirred at 65 ° C. for 15 hours. The reaction solution was diluted with dichloromethane, washed with water and then brine, and the solvent was distilled off. Purification was performed by column chromatography (alumina) to obtain 10.9 g of a compound represented by the formula (I-6-2).
To the reaction vessel was added 6.3 g of the compound represented by formula (I-1-9), 8.4 g of the compound represented by formula (I-6-3), 370 mg of N, N-dimethylaminopyridine, and 70 mL of dichloromethane. It was. Diisopropylcarbodiimide (4.2 g) was added dropwise with ice cooling, and the mixture was stirred at room temperature for 7 hours. The reaction solution was filtered, and the filtrate was washed with hydrochloric acid, water and brine in this order. Purification was performed by column chromatography (silica gel) and recrystallization (dichloromethane / methanol) to obtain 10.1 g of a compound represented by the formula (I-6-4).
In a reaction vessel, 10.0 g of the compound represented by the formula (I-6-4), 3.0 g of the compound represented by the formula (I-6-2), 490 mg of (±) -10-camphorsulfonic acid, 100 mL of tetrahydrofuran And stirred at room temperature for 3 hours. The reaction solution was diluted with dichloromethane, washed with water and brine in this order, and the solvent was distilled off. Purification was performed by column chromatography (silica gel / alumina) and recrystallization (dichloromethane / methanol) to obtain 7.0 g of a compound represented by the formula (I-6).
LCMS: 1176 [M + 1]
Example 7 Production of Compound Represented by Formula (I-7)

To the reaction vessel, 250 mL of hydrazine monohydrate and 250 mL of ethanol were added. An ethanol solution of 25.0 g of 1-bromohexane was added dropwise and stirred at 50 ° C. The reaction solution was diluted with dichloromethane and washed with water and brine in this order. After drying with sodium sulfate, the solvent was distilled off to obtain 14.0 g of a compound represented by the formula (I-7-1).
To the reaction vessel, 11.2 g of the compound represented by the formula (I-1-3), 6.1 g of triethylamine, and 35 mL of 1,2-dimethoxyethane were added. 7.0 g of the compound represented by the formula (I-7-1) was dissolved in 20 mL of 1,2-dimethoxyethane and added dropwise at 50 ° C., followed by stirring at 65 ° C. for 6 hours. The reaction solution was diluted with dichloromethane, washed with water and then brine, and the solvent was distilled off. Purification was performed by column chromatography (alumina) to obtain 12.9 g of a compound represented by the formula (I-7-2).
To the reaction vessel, 440.0 g of a compound represented by the formula (I-1-5), 175.1 g of t-butanol, 28.9 g of N, N-dimethylaminopyridine, and 1760 mL of dichloromethane were added. 357.8 g of diisopropylcarbodiimide was added dropwise with ice cooling, and the mixture was stirred at room temperature for 4 hours. The reaction solution was filtered, and the filtrate was washed with hydrochloric acid, water and brine in this order. Purification was performed by column chromatography (silica gel) to obtain 416.6 g of a compound represented by the formula (I-7-3).
To the reaction vessel, 416.6 g of a compound represented by the formula (I-7-3) and 1430 mL of methanol were added. 228.8 g of 30% aqueous sodium hydroxide solution was added dropwise, and the mixture was stirred at room temperature for 7 hours. Methanol was distilled off from the reaction solution and acidified with hydrochloric acid. The precipitate was extracted into dichloromethane, and the dichloromethane was distilled off to obtain 325.4 g of a compound represented by the formula (I-7-4).
In a reaction vessel, 220.0 g of the compound represented by the formula (I-7-4), 254.7 g of the compound represented by the formula (I-1-10), 5.9 g of N, N-dimethylaminopyridine, 1300 mL of dichloromethane Was added. 145.9 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 8 hours. The reaction solution was filtered, and the filtrate was washed with hydrochloric acid, water and brine in this order. Purification was performed by column chromatography (silica gel) and recrystallization (dichloromethane / methanol) to obtain 350.1 g of a compound represented by the formula (I-7-5).
To the reaction vessel were added 350.1 g of the compound represented by the formula (I-7-5), 1750 mL of dichloromethane, and 1400 mL of formic acid, and the mixture was stirred at room temperature for 5 hours. Dichloromethane was distilled off from the reaction solution, and purification was performed by recrystallization (diisopropyl ether / formic acid) to obtain 247.4 g of a compound represented by the formula (I-7-6).
To the reaction vessel, 9.1 g of the compound represented by the formula (I-7-6), 1.5 g of 2,5-dihydroxybenzaldehyde, 0.1 g of N, N-dimethylaminopyridine, and 150 mL of dichloromethane were added. 3.4 g of diisopropylcarbodiimide was added dropwise with ice cooling, and the mixture was stirred at room temperature for 10 hours. The reaction solution was filtered, and the filtrate was washed with 1% hydrochloric acid, water and brine in this order. After recrystallization (dichloromethane / methanol), purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 7.1 g of a compound represented by the formula (I-7-7). Obtained.
In a reaction vessel, 7.1 g of the compound represented by the formula (I-7-7), 2.2 g of the compound represented by the formula (I-7-2), 350 mg of (±) -10-camphorsulfonic acid, 70 mL of tetrahydrofuran And stirred at room temperature for 4 hours. The reaction solution was diluted with dichloromethane, washed with water and brine in this order, and the solvent was distilled off. Purification was performed by column chromatography (silica gel / alumina) and recrystallization (dichloromethane / methanol) to obtain 6.0 g of a compound represented by the formula (I-7).
LCMS: 1187 [M + 1]
Example 8 Production of Compound Represented by Formula (I-8)

13.5 g of hydrazine monohydrate and 25 mL of ethanol were added to the reaction vessel. An ethanol solution of 5.0 g of the compound represented by the formula (I-1-3) was added dropwise and stirred at 50 ° C. The reaction solution was diluted with dichloromethane and washed with water and brine in this order. After drying with sodium sulfate, the solvent was distilled off to obtain 4.4 g of a compound represented by the formula (I-8-1).
To the reaction vessel, 10.0 g of the compound represented by the formula (I-8-2), 2.4 g of 2,5-dihydroxybenzaldehyde, 420 mg of N, N-dimethylaminopyridine, and 50 mL of dichloromethane were added. Diisopropylcarbodiimide (4.7 g) was added dropwise with ice cooling, and the mixture was stirred at room temperature for 4 hours. The reaction solution was filtered, and the filtrate was washed with hydrochloric acid, water and brine in this order. Purification was performed by column chromatography (silica gel) and recrystallization (dichloromethane / methanol) to obtain 10.5 g of a compound represented by the formula (I-8-3).
In the reaction vessel, 10.5 g of the compound represented by the formula (I-8-3), 3.0 g of the compound represented by the formula (I-8-1), 700 mg of (±) -10-camphorsulfonic acid, 100 mL of tetrahydrofuran And stirred at room temperature for 2 hours. The reaction solution was diluted with dichloromethane, washed with water and brine in this order, and the solvent was distilled off. Purification by column chromatography (silica gel / alumina) and recrystallization (dichloromethane / methanol) gave 6.8 g of a compound represented by the formula (I-8).
LCMS: 850 [M + 1]
Example 9 Production of Compound Represented by Formula (I-9)

To the reaction vessel were added 5.0 g of the compound represented by the formula (I-9-1), 2.1 g of paraformaldehyde, 3.3 g of magnesium chloride, 20 mL of triethylamine, and 80 mL of acetonitrile, and the mixture was stirred at 60 ° C. The reaction solution was diluted with ethyl acetate, washed with hydrochloric acid and brine in this order, and the solvent was distilled off. Purification was performed by column chromatography (silica gel) to obtain 5.4 g of a compound represented by the formula (I-9-2).
To the reaction vessel, 9.0 g of the compound represented by formula (I-7-6), 5.3 g of the compound represented by formula (I-9-2), 260 mg of N, N-dimethylaminopyridine, and 135 mL of dichloromethane were added. It was. Diisopropylcarbodiimide (3.0 g) was added dropwise with ice cooling, and the mixture was stirred at room temperature for 3 hours. The reaction solution was filtered and washed with hydrochloric acid, water and brine in this order. Purification was performed by column chromatography (silica gel) and recrystallization (dichloromethane / methanol) to obtain 7.2 g of a compound represented by the formula (I-9-3).
In a reaction vessel, 7.2 g of the compound represented by formula (I-9-3), 3.5 g of the compound represented by formula (I-1-4), 510 mg of (±) -10-camphorsulfonic acid, 70 mL of tetrahydrofuran And stirred at room temperature for 5 hours. The reaction solution was diluted with dichloromethane, washed with water and brine in this order, and the solvent was distilled off. Purification by column chromatography (silica gel / alumina) and recrystallization (dichloromethane / methanol) gave 6.5 g of the compound represented by formula (I-9).
LCMS: 912 [M + 1]
Example 10 Production of Compound Represented by Formula (I-10)

To the reaction vessel, 50 g of the compound represented by the formula (I-10-1) and 250 mL of dichloromethane were added. Boron tribromide (50 g) was added dropwise with ice cooling, and the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into water, and the precipitated solid was washed with water to obtain 22.8 g of a compound represented by the formula (I-10-2).
To the reaction vessel were added 19.8 g of the compound represented by the formula (I-10-2), 5.9 g of paraformaldehyde, 9.4 g of magnesium chloride, 40 mL of triethylamine, and 260 mL of acetonitrile, and the mixture was stirred at 60 ° C. for 50 hours. The reaction solution was diluted with ethyl acetate and washed with hydrochloric acid, water and brine in this order. Purification was performed by column chromatography (silica gel) to obtain 11.8 g of a compound represented by the formula (I-10-3).
To the reaction vessel was added 2.0 g of the compound represented by formula (I-10-3), 2.5 g of the compound represented by formula (I-7-6), 400 mg of N, N-dimethylaminopyridine, and 30 mL of dichloromethane. It was. 0.9 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature. The reaction solution was filtered, and the filtrate was washed with hydrochloric acid, water and brine in this order. Purification was performed by column chromatography (silica gel) and recrystallization (dichloromethane / hexane) to obtain 3.5 g of a compound represented by the formula (I-10-4).
In a reaction vessel, 3.5 g of the compound represented by the formula (I-10-4), 1.5 g of the compound represented by the formula (I-3-2), 220 mg of (±) -10-camphorsulfonic acid, 35 mL of tetrahydrofuran And stirred at room temperature for 5 hours. The reaction solution was diluted with dichloromethane, washed with water and brine in this order, and the solvent was distilled off. Purification was performed by column chromatography (silica gel / alumina) and recrystallization (dichloromethane / methanol) to obtain 2.8 g of a compound represented by the formula (I-10).
LCMS: 994 [M + 1]
(Example 11) Production of compounds represented by formula (I-102) and formula (I-42)

  Under a nitrogen atmosphere, 17.7 g of the compound represented by the formula (1-42-1) and 100 mL of tetrahydrofuran were added to the reaction vessel. While cooling with ice, 103 mL of 0.9 mol / L borane-tetrahydrofuran complex was added dropwise and stirred for 1 hour. After 5% hydrochloric acid was added dropwise, the mixture was extracted with ethyl acetate and washed with brine. By drying with sodium sulfate and distilling off the solvent, 14.9 g of a compound represented by the formula (1-42-2) was obtained.

  Under a nitrogen atmosphere, 14.9 g of the compound represented by the formula (1-42-2), 7.2 g of pyridine, and 150 mL of dichloromethane were added to the reaction vessel. While cooling with ice, 8.8 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) and recrystallization (acetone / hexane) to obtain 16.3 g of a compound represented by the formula (1-42-3).

  Under a nitrogen atmosphere, 2.5 g of the compound represented by the formula (1-42-4), 10.6 g of the compound represented by the formula (1-42-3), 7.5 g of potassium carbonate, N, N -Dimethylformamide 70mL was added and it heat-stirred at 90 degreeC for 3 days. The mixture was poured into water, extracted with toluene, and washed with brine. Purification was performed by column chromatography (silica gel, toluene) and recrystallization (acetone / methanol) to obtain 7.7 g of a compound represented by the formula (1-42-5).

  To the reaction vessel, 7.7 g of the compound represented by the formula (1-42-5), 150 mL of dichloromethane, and 100 mL of trifluoroacetic acid were added and stirred. After distilling off the solvent, the obtained solid was washed with water and dried to obtain 5.5 g of a compound represented by the formula (1-42-6).

  In a nitrogen atmosphere, 5.5 g of the compound represented by the formula (1-42-6), 6.9 g of the compound represented by the formula (1-42-7), N, N-dimethylaminopyridine. 8 g and 200 mL dichloromethane were added. While cooling with ice, 4.1 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. After recrystallization (dichloromethane / methanol), purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) gave 8.4 g of the compound represented by the formula (1-42-8). Obtained.

  To the reaction vessel, 10.0 g of hydrazine monohydrate and 50 mL of ethanol were added. 11.2 g of the compound represented by the formula (I-42-9) was added dropwise, and the mixture was heated and stirred at 60 ° C. for 3 hours. The solvent was distilled off and dried to obtain 10.9 g of a compound represented by the formula (I-42-9).

  To the reaction vessel, 5.0 g of the compound represented by the formula (I-42-11), 3.0 g of triethylamine, and 30 mL of 1,2-dimethoxyethane were added. 4.4 g of a compound represented by the formula (I-42-9) was added, and the mixture was heated and stirred at 65 ° C. for 15 hours. The reaction solution was diluted with dichloromethane and washed successively with water and brine. Purification was performed by column chromatography (alumina) to obtain 4.2 g of a compound represented by the formula (I-42-12).

In a reaction vessel, 3.0 g of a compound represented by formula (I-42-8), 1.0 g of a compound represented by formula (I-42-12), 0.3 g of (±) -10-camphorsulfonic acid, Tetrahydrofuran 10mL and ethanol 10mL were added, and it heated and stirred at 50 degreeC for 8 hours. The solvent was distilled off, and purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain 3.2 g of a compound represented by the formula (I-102).
LCMS: 1207 [M + 1]
Under a nitrogen atmosphere, 2.0 g of the compound represented by the formula (I-102), 0.3 g of N-ethyldiisopropylamine, and 20 mL of dichloromethane were added to the reaction vessel. While cooling with ice, 0.2 g of acryloyl chloride was added and stirred. The reaction solution was washed successively with 5% hydrochloric acid, saturated aqueous sodium hydrogen carbonate and brine. Purification was performed by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane / methanol) to obtain a compound represented by the formula (I-42).
LCMS: 1261 [M + 1]
(Example 12) Production of compounds represented by formula (I-101) and formula (I-100)

The compound represented by formula (I-101) was prepared in the same manner as in Example 11 except that the compound represented by formula (I-42-9) was replaced with the compound represented by formula (I-100-1). A compound was prepared.
LCMS: 1163 [M + 1]
A compound represented by formula (I-100) was produced in the same manner as in Example 11 except that the compound represented by formula (I-102) was replaced with the compound represented by formula (I-101). did.
LCMS: 1217 [M + 1]

Using the same methods as in Examples 1 to 12 and known methods, the above-mentioned formulas (I-11) to (I-41), formulas (I-43) to (I-99) and formulas are used. A compound represented by the formula (I-201) was produced from (I-103).
(Examples 13 to 26, Comparative Examples 1 to 3) Antifoam test Formulas (I-1) to (I-10), (I-42) and (I--) described in Examples 1 to 12 100) to the compound represented by formula (I-102), compounds (R-1) and (R-2) described in Patent Document 1, and an original comparative compound (R-3) were evaluated.

A coating solution (coating material) having a composition of 40.0% by weight of the compound to be evaluated and 60% by weight of chloroform was prepared. The coating solution was applied onto a 15 cm × 15 cm tin plate using a medium wool wool roller (Otsuka Brush Manufacturing Co., Ltd., product name: Woo Roller), and photographs were taken immediately after application (0 seconds) and after 30 seconds. Based on each photograph, bubbles generated in the central portion (5 cm × 5 cm) of the tin plate were visually counted and the results are shown in Table 1.

From Table 1, the compounds represented by formula (I-1) to formula (I-10), formula (I-42) and formula (I-100) to formula (I-102) of the present invention are comparative compounds ( It can be seen that the antifoaming properties are higher than those of (R-1) to (R-3). This is presumed to be because the paint of the compound of the example has a generally lower viscosity than the paint of the compound of the comparative example, so that the rising speed of the bubbles to the air interface is faster and bubbles break faster.
(Examples 27 to 40, Comparative Examples 4 to 6) Adhesion test Formulas (I-1) to (I-10), (I-42) and (I--) described in Examples 1 to 10 were used. 100) to the compound represented by the formula (I-102) and the comparative compound (R-1) to the comparative compound (R-3) were evaluated compounds. Further, compound (X-1) described in JP-A No. 2005-015473: 50%, compound (X-2) described in JP-A No. 10-87565: 30%, and compound described in JP-T-2002-537280 (X-3): A liquid crystal composition comprising 20% was used as the base liquid crystal (X).

The polyimide solution for alignment film was applied to a cycloolefin polymer substrate using a spin coating method, dried at 60 ° C. for 10 minutes, and then baked at 100 ° 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. On the other hand, a polymerizable composition for evaluation comprising 50% of the base liquid crystal (X) and 50% of the compound to be evaluated was prepared. Furthermore, a coating solution having a composition of 18.9% polymerizable composition for evaluation, 1% photopolymerization initiator Irgacure 907 (manufactured by BASF), 0.1% 4-methoxyphenol and 80% chloroform was prepared. This coating solution was applied to the substrate by a spin coat method. After drying at 80 ° C. for 2 minutes, it was dried at 120 ° C. for 1 minute. Furthermore, the evaluation coating film was produced by irradiating ultraviolet rays with an intensity of 40 mW / cm ² for 25 seconds using a high pressure mercury lamp. Table 2 below shows the results of measuring the adhesion of the coating film according to JIS K5600-5-6, which was cut into a 2-mm square grid with a cutter. The meanings of the terms in the table below are as follows.
Classification 0: No peeling on any base.
Classification 1: Small peeling of the coating film at the intersection of cuts is confirmed (less than 5%).
Classification 2: The coating film is peeled off at the intersection along the cut line (5% or more and less than 15%).
Classification 3: The coating film is partially or totally peeled along the cut line (15% or more and less than 35%).
Classification 4: The coating film is largely and completely peeled along the cut line (35% or more and less than 65%).
Classification 5: Classification 4 or more (65% or more).

  From Table 2, the compounds represented by formulas (I-1) to (I-10), (I-42) and (I-100) to (I-102) of the present invention are comparative compounds. It can be seen that the degree of peeling is equal to or less than that of (R-1) to (R-3).

  Therefore, the compound of the present invention is useful as a constituent member of the polymerizable composition. Moreover, the optical anisotropic body using the polymeric liquid crystal composition containing the compound of this invention is useful for uses, such as an optical film.

Claims (9)

Formula (I)

(Wherein R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 80 carbon atoms, the group may have a substituent, and any carbon atom is hetero An atom may be substituted, but at least one of R ¹ and R ² represents a group represented by the general formula (I-0-R),

(In the formula, P ⁰ represents a polymerizable group, and Sp ⁰ represents a linear or branched alkylene group having 1 to 30 carbon atoms or a single bond, and the alkylene group represents 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—, —CF ₂ O—, —OCF ₂ —, —CF ₂ S—, —SCF ₂ —, —CH═CH—COO—, — CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -N = N-, -CH = N-N = CH-, -CF = CF- Alternatively, -C≡C may be substituted, and when a plurality of Sp ⁰ are present, they may be the same or different, and X ^{0 is-} O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, _{-CO-NH -, - NH-} CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH- COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —CH ₂ CH _{2 -COO -, - CH 2 CH 2} -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N- N = CH -, - CF = CF -, - C≡C- or represents a single bond, ^{if X 0} there are multiple These may be different even in the same ^{(although, P 0 - (Sp 0 -X} 0) k0 -. The free of -O-O- bonds), the integer k0 from 0 10 Represent),
R ³ is a hydrogen atom, or one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—, —COO—, — OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO- , —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF— or —C═C—straight chain which may be substituted by —C≡C— Or, although it represents a branched alkyl group, any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or R ³ represents a group represented by the general formula (I-0-R),
W is the following formula (W-2-1) to formula (W-2-8)

(In the formula, each group has a bond on two arbitrary carbon atoms, and one or two or more arbitrary hydrogen atoms may be substituted with L ^W. )
Represented by
^LW 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 , A diisopropylamino group, a trimethylsilyl group, a dimethylsilyl 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. Linear or branched substituted alkyl having 2 to 20 carbon atoms substituted by —, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH— It represents an arbitrary hydrogen atom in the alkyl group may be substituted by a fluorine atom, or, ^{L W} is ^P LW ^- may represent a group represented by _- ^{(Sp _LW} -X _^LW) kLW Here, P ^LW represents a polymerizable group, and Sp ^LW represents one —CH ₂ — or two or more non-adjacent —CH ₂ —, each independently —O—, —COO—, —OCO. -Represents a linear alkylene group having 1 to 10 carbon atoms which may be substituted by-or a single bond, but when there are a plurality of Sp ^LWs, they may be the same or different, and X ^{LW is-} O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, -CO-NH -, - NH- CO -, - SCH 2 -, - CH 2 S -, - CF 2 O- _{, -OCF 2 -, - CF 2} S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - _{, - - COO-CH 2 CH} 2 OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH ₂ —COO—, —CH ₂ —OCO—, —CH═CH—, —N═N—, —CH═N—N═CH—, —CF═CF—, —C≡C— or a single bond. It represents but ^may be those ^{if X LW} there are multiple different be the same ^{(although, P LW - (Sp LW -X} LW) kLW - to contain no -O-O- bonds. ), KLW represents an integer of 0 to 10, they if L ^W there are a plurality may be the same or different and
Y is a hydrogen atom, 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, A diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl 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. Carbon that may be substituted by —, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF— or —C≡C—. A linear or branched alkyl group having 1 to 20 atoms is represented, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or Y is P ^Y- (Sp ^Y -X ^Y ). _kY - may represent a group represented by, ^{P Y} represents a polymerizable group, Sp ^Y is one -CH ₂ - or nonadjacent two or more -CH ₂ - are each independently A linear alkylene group having 1 to 10 carbon atoms which may be substituted by -O-, -COO-, or -OCO- or a single bond is represented, but when a plurality of Sp ^Y are present, they may be the same ^XY may be different, and ^XY represents —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO. -, - O-CO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH _{S -, - CF 2 O -} , - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO—CH═CH—, —COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO—, —CH ₂ CH ₂ —OCO—, —COO—CH ₂ —, —OCO—CH ₂ —, —CH ₂ —COO—, —CH ₂ —OCO—, —CH═CH—, —N═N—, —CH═N—N═CH—, —CF═CF—, — C≡C— or a single bond, but when a plurality of ^XY are present, they may be the same or different (provided that P ^Y — (Sp ^Y —X ^Y ) _kY — has —O— Does not contain O-bonds. ), KY represents an integer from 0 to 10,
A ¹ and A ² are each independently 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, decahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl group, The group may be unsubstituted or substituted by one or more substituents L, where 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, Oisoshiano group, or one -CH ₂ - or nonadjacent two or more -CH ₂ - are each independently -O -, - S -, - CO -, - COO -, - OCO-, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —CH═CH—COO—, —CH═CH—OCO—, —COO. Linear or branched having 1 to 20 carbon atoms which may be substituted by —CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF— or —C≡C— Represents an alkyl group, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or L may represent a group represented by P ^L- (Sp ^L -X ^L ) _kL-. well, where ^{P L} represents a polymerizable group, Sp ^L is one -CH ₂ - not or adjacent 2 More -CH ₂ - are each independently of -O -, - COO -, - OCO- represents a straight-chain alkylene group or a single bond 10 from good carbon atoms 1 be replaced by, the Sp ^L they If there are multiple or different and are ^identical, X L is _{-O -, - S -, -} OCH 2 -, - CH 2 O -, - CO -, - COO -, - OCO- , -CO-S -, - S -CO -, - O-CO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O-, _{-OCF 2 -, - CF 2 S} -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO _{-CH 2 CH 2 -, - OCO} -CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH _{-OCO -, - COO-CH 2} -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH -, - CF = CF -, - C≡C- or represents a single bond, they ^{if X L} there are a plurality or different and the same ^(however, P L - (Sp ^L -X ^L ) _kL -does not contain an -O-O- bond. ), KL represents an integer of 0 to 10, but when a plurality of L are present in the compound, they may be the same or different, and when a plurality of A ¹ are present, they are the same or different. And when a plurality of A ² are present, they may be the same or different,
Z ¹ and Z ² are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ —, —CO—, —COO—, —OCO—, —CO. -S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, _{-NH-O -, - O-} NH -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH- 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 -OCO -, - CH = CH - , - N = N -, - CH = N -, - N = CH -, - CH = N-N = CH -, - CF = CF -, - C≡C- or Represents a single bond, when a plurality of Z ¹ are present, they may be the same or different; when a plurality of Z ² are present, they may be the same or different;
G is the following formula (G-1) to formula (G-8)

Represents a group selected from, corresponding horizontal bonds in these formulas is a horizontal bond G, these groups are substituted by unsubstituted or substituted with one or more L ^{G LG} 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, 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- OO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF— or —C≡C— may be substituted. It represents a linear or branched alkyl group having 1 to 20 carbon atoms, optional hydrogen atom in the alkyl group may be substituted by a fluorine atom, or, L ^G is P ^{LG -} (Sp ^{LG -} X ^LG ) _kLG- may be used, where P ^LG represents a polymerizable group, and Sp ^LG represents one -CH ₂ -or two or more non-adjacent -CH _2- groups. Each independently represents a linear alkylene group having 1 to 10 carbon atoms which may be substituted by -O-, -COO-, or -OCO- or a single bond, and when a plurality of Sp ^LG are present, They may be the same or different and X ^LG is − O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, _{-CO-NH -, - NH-} CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH- COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —CH ₂ CH _{2 -COO -, - CH 2 CH 2} -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N- N = CH -, - CF = CF -, - C≡C- or represents a single ^{bond, a} place ^{X LG} there are multiple They may be different even in the same ^{(however, P LG - (Sp LG -X} LG) kLG - to contain no -O-O- bonds. ), KLG represents an integer of 0 to 10, if L ^G there are a plurality in the compounds they may be the same or different and
m1 and m2 each independently represents an integer of 0 to 6, but m1 + m2 represents an integer of 0 to 6). In general formula (I-0-R), P ⁰ represents formula (P-1) to formula (P-20) below.

The compound of Claim 1 represented by either. In general formula (I), G represents the following formula (G-1) or formula (G-2)

The compound of Claim 1 or Claim 2 represented by (In formula, the horizontal bond corresponds to the horizontal bond of G). In the general formula (I), W represents the following formula (W-2-1) to formula (W-2-3)

(In the formula, each group has a bond on any two carbon atoms.)
Represented by
^LW 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 , A diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —CO—, The compound as described in any one of Claims 1-3 which represents the C2-C20 linear or branched alkyl group substituted by -COO- or -OCO-. The composition containing the compound as described in any one of Claims 1-4. The liquid crystal composition containing the compound as described in any one of Claims 1-4. The polymer using the composition of Claim 5 or Claim 6. An optical anisotropic body using the polymer according to claim 7. A resin, a resin additive, an oil, a filter, an adhesive, an adhesive, a fat, an ink, a pharmaceutical, a cosmetic, a detergent, a building material, a packaging material using the compound according to any one of claims 1 to 4. , Liquid crystal 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.