JP2015151383A - Polymerizable compound and optical anisotropic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable compound that exhibits high storage stability and great refractive index anisotropy without inducing crystallization or the like when added to a polymerizable composition, and a polymerizable composition containing the above polymerizable compound, which prevents disturbance in orientation when a lens-shaped polymer obtained by polymerizing the polymerizable composition is heated, and to provide a polymer obtained by polymerizing the polymerizable composition, and an optical anisotropic material using the polymer.SOLUTION: The present invention discloses a compound represented by general formula (I), and also discloses a polymerizable composition and polymerizable liquid crystal composition each containing the above compound, a polymer obtained by polymerizing the composition, and an optical anisotropic material using the polymer.

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 a polarizing plate, a retardation plate necessary for a display, a lenticular lens necessary for performing 3D display, and the like. 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.

  Humans feel depth and three-dimensionality when images from the left and right eyes are integrated in the brain. The 3D display is a mechanism that gives a sense of depth and stereoscopic effect by sending images taken at different angles for the right eye and the left eye to the right eye and the left eye, respectively. A method using a lenticular lens is known as a method of sending each image for right eye and left eye to each eye.

  When a polymerizable compound is used for a lenticular lens, when the polymerizable composition before polymerization is prepared, the polymerizable compound in the component is precipitated from the polymerizable composition even if stored for a long time. It is important that there is no. In the case where a polymerizable composition that tends to cause precipitation is used, the possibility that precipitation occurs during the period until the polymer is produced after the preparation of the polymerizable composition is increased. In that case, the polymerizable composition in which precipitation has occurred must be dissolved again by an operation such as heating, which is extremely disadvantageous in terms of the process. In addition, when a lenticular lens is used for 3D display, the thickness of the lenticular lens is reduced from the viewpoint of layout freedom of the internal parts of the display, design of the display itself, and portability especially for portable 3D display. It is preferable to be as small as possible. Therefore, it is desired that the polymerizable compound to be used has a large refractive index anisotropy without adversely affecting other properties. In some cases, after the polymerizable composition is polymerized to prepare a lenticular lens, post-baking, that is, heat treatment is performed for the purpose of completely curing the polymerizable composition. In that case, it is preferable that the orientation of the lenticular lens is not disturbed after post-baking. For example, when a lenticular lens in which the orientation disorder is remarkably generated is used for a 3D display, the quality of the 3D display is deteriorated, the brightness and contrast of the display are lowered, and the quality of the display product is greatly reduced. There is a problem.

  Existing compounds in the field have insufficient refractive index anisotropy (Patent Document 1). In addition, various polymerizable compounds are known as compounds having a large refractive index anisotropy in the field. However, when these polymerizable compounds are added to the polymerizable composition, crystal precipitation occurs, resulting in storage stability. There is a problem that the alignment property is insufficient (Patent Documents 2 and 3), or when the post-baking treatment is performed on the lenticular lens obtained by polymerizing the polymerizable composition, the alignment disorder is remarkably generated ( Patent Documents 2, 3, 4).

JP 2004-269525 A Japanese translation of PCT publication No. 2002-521354 JP-A-5-132524 JP 2012-240945 A

  The problem to be solved by the present invention is to provide a polymerizable compound having high storage stability without causing crystal precipitation or the like when added to the polymerizable composition and having a large refractive index anisotropy. Another object of the present invention is to provide a polymerizable composition which is less likely to cause disorder of orientation when a lens-like polymer obtained by polymerizing a polymerizable composition containing a polymerizable compound is heat-treated. Furthermore, it is providing the polymer obtained by polymerizing the said polymeric composition, and the optical anisotropic body using the said polymer.

  The present invention relates to the general formula (I)

(In the formula, P ¹ and P ² each independently represent a polymerizable group, S ¹ and S ² each independently represent a spacer group, and when a plurality of S ¹ and / or S ² are present, X ¹ and X ² may be independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO. -, - CO-S -, - S-CO -, - O-CO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O- _{, -OCF 2 -, - CF 2} S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO—, —CH ₂ CH ₂ —OCO— _{, -COO-CH 2 -, -} OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH- , —CF═CF—, —C≡C— or a single bond, and when a plurality of X ¹ and / or X ² are present, they may be the same or different, and A ¹ and A ² are Each may be the same or different and each independently represents 1,4-phenylene, naphthalene-1,4-diyl or naphthalene-2,6-diyl, these groups being unsubstituted or one or more In the formula (B-1) to the formula (B-4)

And these groups may be unsubstituted or substituted by one or more L, and L is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group. Represents an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, or a dimethylsilyl group. Well, n1 and n2 represent an integer of 0 to 8, but at least one of n1 or n2 represents an integer other than 0. ), A polymerizable composition containing the compound, a polymerizable liquid crystal composition, a polymer obtained by polymerizing the composition, and an optical system using the polymer. Provides an anisotropic body.

  The compound of the present invention is useful as a component of the polymerizable composition because it has a high storage stability and a large refractive index anisotropy when the polymerizable composition is constituted. An optical anisotropic body using a composition containing the compound of the present invention is useful for applications of optical materials such as a lenticular lens because disorder of alignment hardly occurs after post-baking.

  The present invention provides a compound represented by the general formula (I), together with a polymerizable composition containing the compound, a polymerizable liquid crystal composition, a polymer obtained by polymerizing the composition, and the heavy polymer. An optical anisotropic body using a coalescence is provided.

In the general formula (I), P ¹ and P ² represent a polymerizable group, but P ¹ and P ² may be the same or different, and the following formulas (P-1) to (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).

S ¹ and S ² each independently represent a spacer group, but when a plurality of S ¹ and / or S ² are present, they may be the same or different. From the viewpoint of liquid crystallinity, availability of raw materials, and ease of synthesis, one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —COO—, It preferably represents an alkylene group having 1 to 20 carbon atoms that may be replaced by —OCO— or —OCO—O— (provided that P ¹ —S ¹ , S ¹ —X ¹ , X ² —S ² , And S ² —P ² does not include —O—O—, —NH—O—, —O—NH—, —O—S— or —S—O— groups.) One —CH ₂ -Or two or more non-adjacent —CH ₂ — may each independently represent an alkylene group having 1 to 10 carbon atoms which may be replaced by —O—, —COO— or —OCO—. It is particularly preferable that each independently represents an alkylene group having 1 to 8 carbon atoms.

X ¹ and X ² are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —CO—S—, —S—. CO -, - O-CO- O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S- _{, -SCF 2 -, - CH =} CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO- _{CH 2 CH 2 -, - CH} 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO —, —CH═CH—, —N═N—, —CH═N—N═CH—, —CF═CF—, —C≡C— or a single bond. But they may be the same or different if X ¹ and / or X ² there are a plurality. From the viewpoint of availability of raw materials and ease of synthesis, each independently represents —O—, —S—, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CO—S—, -S-CO -, - OCO- O -, - CO-NH -, - NH-CO -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 - COO—, —CH ₂ CH ₂ —OCO— or a single bond is preferably represented, and each independently represents —O—, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —COO—. _{CH 2 CH 2 -, - OCO} -CH 2 CH 2 -, - CH 2 CH 2 -COO -, - it is more preferable that represent _CH 2 CH 2 -OCO- or a single bond, each independently -O-, It is particularly preferable to represent —COO—, —OCO— or a single bond.

A ¹ and A ² each independently represent 1,4-phenylene, naphthalene-1,4-diyl or naphthalene-2,6-diyl which may be unsubstituted or substituted by one or more L, 1,4-phenylene or naphthalene-2,6-diyl which are each independently unsubstituted or may be substituted with one or more L from the viewpoints of stability, storage stability, availability of raw materials and ease of synthesis Are preferably represented by the following formulas (a-1) to (a-6):

Or the following formula (a-7) to formula (a-14)

Is more preferable, and each independently represents a group selected from Formula (a-1) to Formula (a-6) or Formula (a-7) to Formula (a-9). Further preferably, it is particularly preferable that each independently represents a group selected from the formula (a-1) to the formula (a-6) or the formula (a-7), and the formula (a-1) to the formula (a-6). ) Is most preferred.

  B may be unsubstituted or substituted by one or more Ls (B-1) to (B-4)

From the viewpoints of storage stability, availability of raw materials, and ease of synthesis, from the following formulas (b-1) to (b-3):

The following formula (b-4) to formula (b-18)

Or the following formula (b-19) to formula (b-26)

It is preferable to represent a group selected from formula (b-1), formula (b-4) to formula (b-14), formula (b-19), formula (b-21), formula (b-23). ) And a group selected from formula (b-25), and more preferably, a group selected from formula (b-1), formula (b-4) to formula (b-9), formula (b-12), formula (b) -19), particularly preferably a group selected from formula (b-21) and formula (b-23).

L is a fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, cyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group. Alternatively, it represents a dimethylsilyl group, but represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, or a cyano group from the viewpoint of liquid crystallinity, ease of synthesis, and availability of raw materials. It is particularly preferred that it represents a fluorine atom or a chlorine atom, and most preferably represents a fluorine atom. Further, from the viewpoint of storage stability, it is preferable that at least one group of the ring structures of A ¹ , A ² , and B is substituted with L, and from the viewpoint of ease of synthesis, A ¹ , It is more preferable that at least one group of 1,4-phenylene of A ² or B is substituted with L.

  n1 and n2 each independently represents an integer of 0 to 8, but at least one of n1 and n2 represents an integer other than 0. From the viewpoint of liquid crystallinity, storage stability, availability of raw materials, and ease of synthesis, at least one of n1 and n2 preferably represents an integer of 1 to 4, more preferably 1 or 2. 1 is particularly preferable, and from the viewpoints of storage stability and availability of raw materials, it is most preferable that both n1 and n2 represent 1.

  Specifically, compounds represented by the following formulas (I-1) to (I-98) are preferable as the compounds represented by the general formula (I).

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

(In the formula, P ¹ , P ² , S ¹ , S ² , and L each independently represent the same as defined in the general formula (I), and r each independently represents an integer of 0 to 4) S each independently represents an integer of 0 to 3, halogen represents a halogen atom or a halogen equivalent, and PG represents a protecting group.)
The hydroxyl group of the compound represented by formula (S-1) is protected with a protecting group (PG). The protecting group (PG) is not particularly limited as long as it can be stably protected until the deprotection step. For example, GREEN'S PROTECTIVE GROUPS IN ORGANIC SYNTHESIS ((Fourth Edition), PETER GM. Protecting groups (PG) listed in WUTS, THEODORA W. GREENE, A John Wiley & Sons, Inc., Publication) and the like are preferred. Specific examples of the protecting group include a tetrahydropyranyl group.

  The compound represented by the general formula (S-3) is obtained by boring the compound represented by the general formula (S-2). As the borated method, the compound represented by the general formula (S-2) is derived into a Grignard reagent, reacted with a borate ester, and then hydrolyzed, or represented by the general formula (S-2). A method of lithiating a compound to be obtained by a halogen lithium exchange reaction, reacting with a borate ester, and then hydrolyzing the compound is mentioned. Specific examples of the boric acid ester include trimethyl borate and triisopropyl borate. Specific examples of the lithiating agent include butyl lithium, sec-butyl lithium, tert-butyl lithium and the like.

  The compound represented by general formula (S-5) can be obtained by reacting the compound represented by general formula (S-3) with the compound represented by general formula (S-4). Examples of the reaction include a method of cross coupling in the presence of a metal catalyst and a base. Specific examples of the metal catalyst include [1,1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloride, palladium (II) acetate, tetrakis (triphenylphosphine) palladium (0) and the like. Specific examples of the base include potassium carbonate, potassium phosphate, cesium carbonate and the like. Reaction conditions include, for example, Metal-Catalyzed Cross-Coupling Reactions (Co-authored by Armin de Meijere, Francois Diedrich, Wiley-VCH), Palladium Reagents and Catalysts: New Perspective. Cross-Coupling Reactions: A Practical Guide (Topics in Current Chemistry) (SL Buchwald, K. Fugami, T. Hiyama, M. Kourai, M. Miura, N. A. M.Nomura, E.Shirakawa, K.Tamao al, include the methods described in literature Springer) and the like.

  The compound represented by the general formula (S-7) is obtained by reacting the compound represented by the general formula (S-5) with a compound represented by the general formula (S-6) in the presence of a base, for example. Specific examples of the base include potassium carbonate and cesium carbonate.

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

  The compound represented by the general formula (S-10) is obtained by reacting the compound represented by the general formula (S-8) with, for example, a compound represented by the general formula (S-9) in the presence of a base. Examples of the base include those described above.

  Examples of reaction conditions other than those described in each of the above steps include, for example, an experimental chemistry course (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd.), Organic Synthesis (A John Wiley & Sons, Inc., Publication), and Bilstein Handbook of Organic Chemistry (Chemical Chemistry). -Described in Institute for Reiter der Organischen Chemie, Springer-Verlag Berlin and Heidelberg GmbH, Co. K, Fiesers' Reagents for Organic Science. mical Abstracts Service, American Chemical Society), include those listed in databases such as Reaxys (Elsevier Ltd.).

  In each step, a reaction solvent can be appropriately used. Specific examples of the solvent include ethanol, tetrahydrofuran, toluene, dichloromethane, water and the like. When the reaction is carried out in an organic solvent and water two-phase system, a phase transfer catalyst can be added. Specific examples of the phase transfer catalyst include benzyltrimethylammonium bromide and tetrabutylammonium bromide.

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. Specific examples of the purification agent include silica gel, alumina, activated carbon and the like.
(Manufacturing method 2) Manufacture of the compound represented by a following formula (S-24)

(In the formula, P ¹ , P ² , S ¹ , S ² , and L each independently represent the same as defined in the general formula (I), and r each independently represents an integer of 0 to 4) S each independently represents an integer of 0 to 3, halogen represents a halogen atom or a halogen equivalent, and PG represents a protecting group.)
The compound represented by the general formula (S-13) is obtained by reacting the compound represented by the general formula (S-11) with, for example, a compound represented by the general formula (S-12) in the presence of a base. Specific examples of the base include potassium carbonate and cesium carbonate.

  The hydroxyl group of the compound represented by formula (S-13) is protected with a protecting group (PG). As the protecting group (PG), those listed in the literature described in Production Method 1 are preferable. Specific examples of the protecting group include a tetrahydropyranyl group.

  The compound represented by the general formula (S-15) is obtained by boring the compound represented by the general formula (S-14). As the borated method, a compound represented by the general formula (S-14) is derived into a Grignard reagent, reacted with a borate ester, and then hydrolyzed, or represented by the general formula (S-14). A method of lithiating a compound to be obtained by a halogen lithium exchange reaction, reacting with a borate ester, and then hydrolyzing the compound is mentioned. Specific examples of the boric acid ester include trimethyl borate and triisopropyl borate. Specific examples of the lithiating agent include butyl lithium, sec-butyl lithium, tert-butyl lithium and the like.

  The compound represented by the general formula (S-17) can be obtained by cross-coupling the compound represented by the general formula (S-15) with the compound represented by the general formula (S-16). Examples of the metal catalyst, base and reaction conditions include those described in Production Method 1.

  The compound represented by the general formula (S-18) is obtained by boring the compound represented by the general formula (S-17). Examples of the borated method include a method in which a proton on the aromatic ring of the compound represented by the general formula (S-17) is extracted with a strong base, reacted with a borate ester, and then hydrolyzed. Examples of the strong base include butyl lithium, sec-butyl lithium, tert-butyl lithium, lithium diisopropylamide and the like. Tetramethylethylenediamine or the like may be added as necessary. Examples of the boric acid ester include those described above. Moreover, after halogenating the compound represented by general formula (S-17), the method of borated like the above is also mentioned.

  The compound represented by the general formula (S-20) can be obtained by cross-coupling the compound represented by the general formula (S-18) with the compound represented by the general formula (S-19). Examples of the metal catalyst, base and reaction conditions include those described in Production Method 1.

  A compound represented by the general formula (S-22) is obtained by reacting the compound represented by the general formula (S-20) with the compound represented by the general formula (S-21) by Mitsunobu reaction. Specific examples of the azodicarboxylic acid include diethyl azodicarboxylate and diisopropyl azodicarboxylate. Specific examples of phosphine include triphenylphosphine. A Kakuda reagent such as cyanomethylenetributylphosphorane may also be used.

  The protecting group (PG) of the compound represented by formula (S-22) is deprotected. As reaction conditions for deprotection, those listed in the literature described in production method 1 are preferable.

  A compound represented by the general formula (S-24) is obtained by introducing a polymerizable group into the compound represented by the general formula (S-23).

  Examples of reaction conditions other than those described in the respective steps include those described in the literature described in production method 1 or those listed in the database. Further, a reaction solvent can be appropriately used in each step as in Production Method 1. As in production method 1, purification can be performed as necessary in each step.

  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 reactive compound of the present invention, a compound other than the present invention may be added.

  Specific examples of other reactive compounds used by mixing with the reactive compound of the present invention include those represented by the general formula (II-1).

And / or general formula (II-2)

(In the formula, P ³ , P ⁴ and P ⁵ each independently represent the same meaning as P ¹ or P ² in formula (I), and S ³ , S ⁴ and S ⁵ are each independently a single bond or Represents an alkylene group having 1 to 20 carbon atoms, and one —CH ₂ — or two or more non-adjacent —CH ₂ — represents —O—, —COO—, —OCO—, —OCOO—. X ³ , X ⁴ and X ⁵ are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—. , -CO-S -, - S -CO -, - O-CO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O-, _{-OCF 2 -, - CF 2 S} -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH-, _{-OCO-CH = CH -, -} COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 - , —OCO—CH ₂ —, —CH ₂ —COO—, —CH ₂ —OCO—, —CH═CH—, —CF═CF—, —C≡C— or a single bond, Z ¹ and Z ² Are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CO—, —CO—S—, —S—CO—, —O. _{-CO-O -, - CO-} NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 - _{, -CH 2 CH 2 -, -} CH 2 CF 2 -, - CF 2 CH 2 -, - CF 2 CF 2 -, - CH = CH-COO- , —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO _{-, - CH 2 CH 2 -OCO} -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - CF = CF- represents -C≡C- or a single bond (provided ^{that, P 3 -S 3, S 3} -X 3, X 4 -S 4, S 4 -P 4, P 5 -S 5, and ^S 5 -X ⁵ , Does not include —O—O—, —NH—O—, —O—NH—, —O—S—, or —S—O— groups. ), A ³ , A ⁴ , A ⁵ and A ⁶ are each independently 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl. Represents a group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl group, A ³ , A ⁴ , A ⁵ and A ⁶ are each independently unsubstituted or halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group having 1 to 20 carbon atoms, halogenated alkyl group, alkoxy Group, a halogenated alkoxy group, a cyano group or a nitro group, R ¹ may be a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, Toro group, isocyano 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 1 to 20 carbon atoms which may be substituted by —OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF— or —C≡C—. Represents a linear or branched alkyl group, and m1 and m2 represent 0, 1, 2, or 3, but when m1 and / or m2 represents 2 or 3, two or three A ³ , A ⁵ , Z ¹ and / or Z ² may be the same or different, but may be represented by the general formula (I). Excluded compounds. ) Is preferable, and P ³ , P ^4, and P ⁵ are particularly preferably each independently an acryl group or a methacryl group. Specifically, as the compound represented by the general formula (II-1), the general formula (II-1A)

Wherein W ¹ and W ² each independently represent hydrogen or a methyl group, S ⁶ and S ⁷ each independently represent an alkylene group having 2 to 18 carbon atoms, and X ⁶ and X ⁷ each independently -O Te -, - COO -, - OCO- or a single bond, ^{Z 3} and ^{Z 4} each independently represents a -COO- or ^{-OCO-, a 7,} a ⁸ and ^{a 9} are each independently Or a 1,4-phenylene group substituted by a fluorine atom, a chlorine atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms). The compounds represented by the following formulas (II-1A-1) to (II-1A-8) are particularly preferable.

(Wherein W ¹ and W ² each independently represent hydrogen or a methyl group, S ⁸ represents the same meaning as S ⁶ in formula (II-1A), and S ⁹ represents formula (II-1A)). represents the same meaning as ^{S 7} in.) in the above formula (II-1A-1) from the formula (II-1A-8), an alkylene group of ^{S 8} and ^{S 9} are each independently a carbon atom number of 2 to 8 Certain compounds are more preferred.

  Moreover, general formula (II-1B)

Wherein W ¹ and W ² each independently represent hydrogen or a methyl group, S ¹⁰ and S ¹¹ each independently represent an alkylene group having 2 to 18 carbon atoms, and X ⁸ and X ⁹ each independently -O Te -, - COO -, - OCO- or a single bond, ^{Z 5} represents -COO- or ^-OCO-, a ^{10, a 11} and ^{a 12} are each independently an unsubstituted or fluorine atom, A compound represented by the following formula (II-1B): a chlorine atom, a 1,4-phenylene group substituted by an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. The compound represented by formula (II-1B-8) is particularly preferable.

(Wherein W ¹ and W ² each independently represent hydrogen or a methyl group, S ¹² represents the same meaning as S ¹⁰ in formula (II-1B), and S ¹³ represents formula (II-1B)). represents the same meaning as ^{S 11} in.) in the above formula (II-1B-1) from the formula (II-1B-8), in view of heat resistance and durability, the formula (II-1B-2), formula ( II-1B-5), the formula (II-1B-6), the formula (II-1B-7) and the compound represented by the formula (II-1B-8) are preferred, and the formula (II-1B-2) The compound represented is more preferable, and the compound in which S ¹² and S ¹³ are each independently an alkylene group having 2 to 8 carbon atoms is particularly preferable.

  In addition, preferable bifunctional polymerizable compounds include compounds represented by the following general formulas (II-1C-1) to (II-1C-8).

(W ¹ and W ² each independently represent hydrogen or a methyl group, and S ¹⁴ and S ¹⁵ each independently represent an alkylene group having 2 to 18 carbon atoms.) The above formula (II-1C -1) to formula (II-1C-8), formula (II-1C-2), formula (II-1C-3), formula (II-1C-4), formula (II-1C-6), Compounds represented by formula (II-1C-7) and formula (II-1C-8) are preferred, and compounds in which S ¹⁴ and S ¹⁵ are each independently an alkylene group having 2 to 8 carbon atoms are particularly preferred. .

  Specific examples of the compound represented by the general formula (II-2) include compounds represented by the following general formulas (II-2-1) to (II-2-9).

(In the formula, P ⁶ represents the same meaning as P ¹ or P ² in formula (I), and S ¹⁶ 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—, —OCOO—, and X ¹⁰ is a single bond, —O—, —COO—. , —OCO—, Z ⁶ is a single bond, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, —CH═CH—, —CF═CF— or — C≡C— and A ¹³ represents a 1,4-phenylene group or a naphthalene-2,6-diyl group, and A ¹³ is unsubstituted or an alkyl group, a halogenated alkyl group, an alkoxy group, a halogen atom Substituted with an alkoxy group, halogen atom, cyano group or nitro group At best, ^{L 1} is fluorine atom, chlorine atom, one -CH ₂ - or nonadjacent two or more -CH ₂ - are each independently -O -, - COO -, - OCO- in Represents a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted; r represents an integer of 0 to 4; R ² represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group; Carbon in which one —CH ₂ — or two or more non-adjacent —CH ₂ — may be independently replaced by —O—, —COO—, —OCO—, —OCO—O— Represents a linear or branched alkyl group having 1 to 20 atoms.)
A polymerizable compound that does not exhibit liquid crystallinity can be added to the polymerizable liquid crystal composition containing the compound of the present invention to such an extent that the liquid crystallinity of the composition is not significantly impaired. Specifically, any compound that is recognized as a polymer-forming monomer or polymer-forming oligomer in this technical field can be used without particular limitation. Specific examples include those described in “Photocuring Technology Data Book, Materials (Monomer, Oligomer, Photopolymerization Initiator)” (supervised by Kunihiro Ichimura, Kiyosuke Kato, Technonet).

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

  In addition, a stabilizer can be added to the liquid crystal composition of the present invention in order to improve its storage stability. Examples of the stabilizer that can be used include hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, nitroso compounds, and the like. It is done. When the stabilizer is used, the addition amount is preferably in the range of 0.005% by mass to 1% by mass, more preferably 0.02% by mass to 0.8% by mass, and 0.03% by mass with respect to the composition. To 0.5% by mass is more preferable. One kind of stabilizer may be used, or two or more kinds of stabilizers may be used in combination. Specifically, as the stabilizer, the formula (III-1) to the formula (III-36)

(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, reduced pressure drying, or reduced pressure heat drying can be used. In order to further improve the applicability of the polymerizable liquid crystal material, it is also effective to provide an intermediate layer such as a polyimide thin film on the substrate or to add a leveling agent to the polymerizable liquid crystal material. The method of providing an intermediate layer such as a polyimide thin film on a substrate is effective for improving the adhesion between a polymer obtained by polymerizing a polymerizable liquid crystal material and the substrate.

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

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

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

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

EXAMPLES Hereinafter, although an Example is given and this invention is further described, this invention is not limited to these Examples. Further, “%” in the compositions of the following Examples and Comparative Examples means “% by mass”.
Example 1 Production of Compound Represented by Formula (I-1)

  10.0 g (0.0448 mol) of a compound represented by the formula (I-1-1), 5.51 g (0.0583 mol) of 3-chloropropanol, 21.9 g (0.0672 mol) of cesium carbonate in a reaction vessel ), 100 mL of dimethyl sulfoxide was added, and the mixture was heated and stirred at 65 ° C. for 5 hours. Diluted with dichloromethane, washed with water and brine, purified by column chromatography (silica gel) and recrystallization, 10.7 g (0.0381 mol) of compound represented by formula (I-1-2) Got.

  In a reaction vessel, 10.7 g (0.0381 mol) of the compound represented by the formula (I-1-2), 5.33 g (0.0381 mol) of the compound represented by the formula (I-1-3), carbonic acid 7.90 g (0.0572 mol) of potassium, 100 mL of tetrahydrofuran, and 100 mL of water were added. After substituting the system with nitrogen, 0.44 g (0.38 mmol) of tetrakis (triphenylphosphine) palladium (0) was added and heated to reflux for 7 hours. Dilute with ethyl acetate and wash with hydrochloric acid and brine. Purification was performed by column chromatography (silica gel) to obtain 9.03 g (0.0305 mol) of a compound represented by the formula (I-1-4).

  To a reaction vessel equipped with a dropping funnel was added 9.03 g (0.0305 mol) of the compound represented by formula (I-1-4), 0.38 g (1.52 mmol) of pyridinium paratoluenesulfonate, and 100 mL of dichloromethane. It was. While cooling with ice, 3.85 g (0.0457 mol) of 3,4-dihydro-2H-pyran was added dropwise. The mixture was stirred at room temperature for 10 hours, washed with saturated aqueous sodium hydrogen carbonate and brine, purified by column chromatography (alumina), and 11.0 g (0.0290 mol) of the compound represented by the formula (I-1-5). )

  To a reaction vessel equipped with a dropping funnel, 11.0 g (0.0290 mol) of the compound represented by the formula (I-1-5) and 100 mL of tetrahydrofuran were added. 38 mL of a sec-butyllithium solution (1.0 mol / L) was added dropwise at -70 ° C. After stirring for 2 hours, 7.08 g (0.0376 mol) of triisopropyl borate was added dropwise. After stirring for 2 hours, 100 mL of 10% hydrochloric acid was added dropwise at 0 ° C. The mixture was stirred at room temperature for 1 hour and washed with brine. By concentrating and drying, 9.36 g (0.0275 mol) of the compound represented by the formula (I-1-6) was obtained.

  In a reaction vessel, 15.0 g (0.0682 mol) of a compound represented by the formula (I-1-7), 8.38 g (0.0886 mol) of 3-chloropropanol, 33.3 g (0.102 mol) of cesium carbonate ), 150 mL of dimethyl sulfoxide was added, and the mixture was heated and stirred at 65 ° C. for 5 hours. After diluting with dichloromethane and washing with hydrochloric acid, water, and brine, purification is performed by column chromatography (silica gel) to obtain 17.1 g (0.0614 mol) of the compound represented by the formula (I-1-8). Obtained.

  In a reaction vessel, 2.00 g (7.19 mmol) of the compound represented by the formula (I-1-8), 2.45 g (7.19 mmol) of the compound represented by the formula (I-1-6), carbonic acid 1.49 g (0.0108 mol) of potassium, 25 mL of tetrahydrofuran and 25 mL of water were added. After the atmosphere in the system was replaced with nitrogen, 83.1 mg (0.072 mmol) of tetrakis (triphenylphosphine) palladium (0) was added, and the mixture was heated to reflux for 7 hours. Dilute with toluene / ethyl acetate and wash with hydrochloric acid, water, and brine. Purification was performed by column chromatography (silica gel) and recrystallization to obtain 2.57 g (5.75 mmol) of the compound represented by the formula (I-1-9).

To a reaction vessel equipped with a dropping funnel, 2.57 g (5.75 mmol) of the compound represented by the formula (I-1-9), 1.86 g (14.4 mmol) of diisopropylethylamine and 25 mL of dichloromethane were added. While cooling with ice, 1.20 g (13.2 mmol) of acryloyl chloride was added dropwise. The mixture was stirred at room temperature for 5 hours, washed with 5% hydrochloric acid and brine, and purified by column chromatography (silica gel) and recrystallization to obtain 2.23 g of the compound represented by the formula (I-1).
Transition temperature (temperature increase 5 ° C./min): C 105 S 198-215 N
¹ H NMR (CDCl ₃ ) δ 2.20 (quin, 2H), 2.25 (quin, 2H), 4.13 (t, 2H), 4.21 (t, 2H), 4.40 (t, 2H), 4.43 (t, 2H), 5.85 (dd, 2H), 6.14 (dd, 1H), 6.15 (dd, 1H), 6.44 (m, 2H), 7. 00 (d, 2H), 7.18 (m, 2H), 7.47-7.57 (m, 5H), 7.72 (dd, 1H), 7.81 (d, 2H), 8.00 (S, 1H) ppm.
¹³ C NMR (CDCl ₃ ) δ 28.58, 28.60, 61.34, 61.40, 64.30, 64.35, 106.31, 114.41, 114.49, 114.65, 119. 33, 119.53, 122.86, 122.89, 125.55, 126.13, 127.02, 127.16, 127.42, 128.03, 128.32, 129.11, 129.82, 130.08, 130.11, 130.68, 130.73, 130.95, 130.99, 133.97, 134.68, 134.70, 141.63, 141.71, 157.08, 158. 41, 158.81, 161.27, 166.20, 166.22 ppm.
Example 2 Production of Compound Represented by Formula (I-2)

The same method as in Example 1, except that 3-chloropropanol was replaced with 6-chlorohexanol and the compound represented by the formula (I-1-3) was replaced with a compound represented by the formula (I-2-2). The compound represented by Formula (I-2) was obtained.
IR: 3060-3030, 2975-2920, 1725, 1630, 1200, 1160, 1130, 750, 690 cm ⁻¹ .
LRMS: 656
Example 3 Production of Compound Represented by Formula (I-3)

A compound represented by the formula (I-3-1) was produced according to the method described in JP2012-240945A. In Example 1, the compound represented by the formula (I-1-1) is changed to the compound represented by the formula (I-2-6), and the compound represented by the formula (I-1-7) is changed to the formula (I-1-7). A compound represented by the formula (I-3) was obtained in the same manner except that the compound represented by -3-1) was replaced.
IR: 3060-3030, 2975-2920, 1725, 1630, 1200, 1160, 1130, 750, 690 cm ⁻¹ .
LRMS: 598
Example 4 Production of Compound Represented by Formula (I-4)

  In a reaction vessel, 1.00 g (3.08 mmol) of the compound represented by formula (I-3-2), 1.05 g (3.08 mmol) of the compound represented by formula (I-1-6), carbonic acid 0.64 g (4.61 mmol) of potassium, 15 mL of tetrahydrofuran and 15 mL of water were added. After the system was purged with nitrogen, 0.18 g (0.154 mmol) of tetrakis (triphenylphosphine) palladium (0) was added, and the mixture was heated to reflux for 7 hours. Dilute with toluene / ethyl acetate and wash with hydrochloric acid, water, and brine. Purification was performed by column chromatography (silica gel) and recrystallization to obtain 1.33 g (2.46 mmol) of the compound represented by the formula (I-4-1).

To a reaction vessel equipped with a dropping funnel, 1.33 g (2.46 mmol) of the compound represented by the formula (I-4-1), 0.79 g (6.15 mmol) of diisopropylethylamine, and 15 mL of dichloromethane were added. While cooling with ice, 0.51 g (5.66 mmol) of acryloyl chloride was added dropwise. The mixture was stirred at room temperature for 5 hours, washed with 5% hydrochloric acid and brine, and purified by column chromatography (silica gel) and recrystallization to obtain 1.12 g of the compound represented by the formula (I-4).
IR: 3060-3030, 2975-2920, 1725, 1630, 1200, 1160, 1130, 750, 690 cm ⁻¹ .
LRMS: 648
Example 5 Production of Compound Represented by Formula (I-5)

In Example 1, the compound represented by the formula (I-1-3) is changed to the compound represented by the formula (I-2-2), and the compound represented by the formula (I-1-8) is changed to the formula (I-1-8). A compound represented by the formula (I-5) was obtained by the same method except that the compound represented by -2) was replaced.
IR: 3060-3030, 2975-2920, 1725, 1630, 1200, 1160, 1130, 750, 690 cm ⁻¹ .
LRMS: 666
Example 6 Production of Compound Represented by Formula (I-6)

In Example 1, 3-chloropropanol is represented by 6-chlorohexanol, the compound represented by formula (I-1-1) is represented by formula (I-2-6), and formula (I-1-3). The compound represented by formula (I-2-2), the compound represented by formula (I-1-8) was replaced with the compound represented by formula (I-3-2), and acryloyl chloride was replaced with methacryloyl chloride. Except for the above, a compound represented by the formula (I-6) was obtained in the same manner.
IR: 3060-3030, 2975-2920, 1725, 1630, 1200, 1160, 1130, 750, 690 cm ⁻¹ .
LRMS: 686
Example 7 Production of Compound Represented by Formula (I-7)

  A compound represented by the formula (I-7-1) was produced by the method described in JP-A-2005-047838. The same method as in Example 1, except that 3-chloropropanol was replaced with 6-chlorohexanol and the compound represented by formula (I-1-1) was replaced with a compound represented by formula (I-7-1). To obtain a compound represented by the formula (I-7-2).

  The compound represented by formula (I-7-4) was prepared in the same manner as in Example 1 except that the compound represented by formula (I-1-4) was replaced with the compound represented by formula (I-7-2). The compound obtained was obtained.

In Example 1, the compound represented by the formula (I-1-8) is changed to the compound represented by the formula (I-7-5), and the compound represented by the formula (I-1-6) is changed to the formula (I-1-6). A compound represented by formula (I-7) was obtained in the same manner except that the compound represented by -7-4) was replaced.
IR: 3060-3030, 2975-2920, 1725, 1630, 1200, 1160, 1130, 750, 690 cm ⁻¹ .
LRMS: 574
Example 8 Production of Compound Represented by Formula (I-8)

  In a reaction vessel, 5.00 g (0.0178 mol) of the compound represented by the formula (I-1-2), 4.97 g (0.0196 mol) of bis (pinacolato) diboron, 5.24 g of potassium acetate (0.0534) Mol), and 50 mL of dimethyl sulfoxide was added. After substituting the system with nitrogen, 0.39 g (0.534 mmol) of [1,1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloride was added and heated at 85 ° C. for 15 hours. Dilute with toluene / ethyl acetate and wash with brine. Purification was performed by column chromatography (silica gel) to obtain 4.67 g (0.0142 mol) of a compound represented by the formula (I-8-1).

  4.67 g (0.0142 mol) of a compound represented by the formula (I-8-1), 4.52 g (0.0142 mol) of a compound represented by the formula (I-8-2), carbonic acid 2.95 g (0.0213 mol) of potassium, 40 mL of tetrahydrofuran and 40 mL of water were added. After replacing the system with nitrogen, 0.16 g (0.142 mmol) of tetrakis (triphenylphosphine) palladium (0) was added, and the mixture was heated to reflux for 5 hours. Dilute with toluene / ethyl acetate and wash with hydrochloric acid, water, and brine. Purification was performed by column chromatography (silica gel) and recrystallization to obtain 4.18 g (0.0107 mol) of a compound represented by the formula (I-8-3).

Similarly, the compound represented by the formula (I-8-7) was obtained by repeating the coupling reaction. It is represented by the formula (I-8) by the same method except that the compound represented by the formula (I-1-9) in Example 1 is replaced with the compound represented by the formula (I-8-7). A compound was obtained.
IR: 3060-3030, 2975-2920, 1725, 1630, 1200, 1160, 1130, 750, 690 cm ⁻¹ .
LRMS: 680
Example 9 Production of Compound Represented by Formula (I-9)

  The same method as in Example 1, except that the compound represented by formula (I-1-1) was replaced by the compound represented by formula (I-7-5) and 3-chloropropanol was replaced by 4-chlorobutanol. To obtain a compound represented by the formula (I-9-1).

  In a reaction vessel, 2.00 g (7.97 mmol) of the compound represented by the formula (I-9-2), 1.12 g (0.0104 mol) of 4-chlorobutanol, 1,8-diazabicyclo [5.4. 0] -7-undecene (1.82 g, 0.0119 mol) and toluene (20 mL) were added. After stirring with heating at 100 ° C. for 5 hours, the mixture was diluted with ethyl acetate and washed with hydrochloric acid, water and brine. Purification by column chromatography (silica gel) gave 2.06 g (6.37 mmol) of the compound represented by the formula (I-9-3).

  The compound represented by formula (I-9-4) was prepared in the same manner as in Example 8 except that the compound represented by formula (I-1-2) was replaced with the compound represented by formula (I-9-3). The compound obtained was obtained.

  In Example 8, the compound represented by the formula (I-8-6) is changed to the compound represented by the formula (I-9-4), and the compound represented by the formula (I-3-3) is changed to the formula (I A compound represented by the formula (I-9-5) was obtained by the same method except that the compound represented by -9-1) was replaced.

In a reaction vessel equipped with a dropping funnel, 3.00 g (6.19 mmol) of the compound represented by the formula (I-9-5), 1.65 g (0.0142 mol) of 3-ethyl-3-oxetanemethanol, 3.73 g (0.0142 mol) of phenylphosphine and 30 mL of tetrahydrofuran were added. While cooling with ice, 2.75 g (0.0136 mol) of diisopropyl azodicarboxylate was added dropwise. After stirring at room temperature for 5 hours, methanol / water was added. The precipitate was filtered and dried, and then purified by column chromatography (silica gel) and recrystallization to obtain 2.95 g of a compound represented by the formula (I-9).
LRMS: 680
Example 10 Production of Compound Represented by Formula (I-10)

  The compound represented by formula (I-10-2) was prepared in the same manner as in Example 1 except that the compound represented by formula (I-1-1) was replaced with the compound represented by formula (I-10-1). The compound obtained was obtained.

  A compound represented by the formula (I-10-6) was obtained by repeating the coupling reaction in the same manner as in Example 8.

In a reaction vessel, 2.00 g (3.89 mmol) of a compound represented by the formula (I-10-6), 1.20 g (8.55 mmol) of 2- (trifluoromethyl) acrylic acid, N, N-dimethyl Aminopyridine 95.0 mg (0.78 mmol) and dichloromethane 30 mL were added. While cooling with ice, 1.08 g (8.55 mmol) of diisopropylcarbodiimide was added dropwise. After stirring at room temperature for 8 hours, the precipitate was filtered and the solvent was distilled off. Purification was performed by column chromatography (silica gel) and recrystallization to obtain 2.06 g of a compound represented by the formula (I-10).
LRMS: 758
The compounds represented by the following formulas (I-11) to (I-98) were produced using the same methods as in Examples 1 to 10 and methods known in the art.

(Examples 11-20, Comparative Examples 1-4)
Compounds represented by formula (I-1) to formula (I-10) described in Example 1 to Example 10, compound (R-1) described in Patent Document 1, compound (R-) described in Patent Document 2 2) The compound (R-3) described in Patent Document 3 and the compound (R-4) described in Patent Document 4 were evaluated compounds.

  In order to evaluate the storage stability, the stable storage concentration of the compound to be evaluated was measured. The stable storage concentration was determined by preparing a composition in which the compound to be evaluated was added to the base liquid crystal in 5% increments from 5% to 20%, and after leaving the prepared composition at 19.2 ° C. for 3 weeks, Is defined as the maximum concentration of the compound at which no precipitation occurs. A compound having a large maximum addition concentration has a high stable storage concentration, meaning that no crystal precipitation occurs even after long-term storage.

  In order to measure the stable storage concentration, a liquid crystal composition composed of compounds represented by the following compounds (X-1) to (X-4) was used as a base liquid crystal (X). Moreover, the refractive index anisotropy of the evaluation object compound was evaluated. Table 1 shows the composition of the base liquid crystal (X), and Table 2 shows the stable storage concentration and refractive index anisotropy of the compound to be evaluated.

From Table 2, all the compounds represented by the formulas (I-1) to (I-10) of the present invention are compared with the comparative compounds (R-2) to (R) having the same refractive index anisotropy. Compared with -4), the maximum addition concentration at which no crystal precipitation occurs is high, indicating that high storage stability is exhibited.
(Example 21 to Example 30, Comparative Example 5 to Comparative Example 8)
The polyimide solution for alignment film was applied to a glass substrate having a thickness of 0.7 mm using a spin coating method, dried at 120 ° C. for 8 minutes, and then baked at 180 ° C. for 80 minutes to obtain a coating film. The obtained coating film was rubbed. The rubbing treatment was performed using a commercially available rubbing apparatus.

A photopolymerization initiator Irgacure 907 (manufactured by BASF Corp.) is used for each of the compositions in which the amount of the compound to be evaluated is adjusted in the base liquid crystal (X) so that the refractive index anisotropy of the obtained lenticular lens is 0.165. 1) and 0.1% 4-methoxyphenol. This composition was applied to a rubbed glass substrate at 90 ° C. by a spin coating method. The resin mold having been subjected to the alignment treatment on the obtained coating film was placed so that the alignment direction of the glass substrate rubbed with the alignment direction of the resin mold was parallel, and then cooled to room temperature. Thereafter, ultraviolet rays were irradiated for 40 seconds at an intensity of 50 mW / cm ² using a high-pressure mercury lamp. Next, the resin mold was slowly removed to obtain a lenticular lens (see FIG. 1). Each of the obtained lenticular lenses had a film thickness of 50 μm and a refractive index anisotropy of 0.165. In order to completely cure the polymerizable composition, the obtained lenticular lens was post-baked, that is, heat-treated at 230 ° C. for 5 minutes.

  The disorder of orientation after post-baking was observed using a polarizing microscope. In the case where there was no alignment disorder, ◎, in the case where the alignment disorder was very small, ◯, in the case where the alignment disorder was slightly large, Δ, and in the case where the alignment disorder was very large, X was marked. The results are shown in Table 3 below.

  From Table 3, all the lenticular lenses produced using the compounds represented by the formulas (I-1) to (I-10) of the present invention are the comparative compound (R-1) to the comparative compound (R-4). It can be seen that there is less orientation disturbance after post-baking as compared to the lenticular lens produced using.

  From the above results, the compounds represented by the formulas (I-1) to (I-10), which are the inventions of the present invention described in Examples 1 to 10, are storage stability when constituting a polymerizable composition. The refractive index anisotropy is high, and the optical anisotropic body using the composition containing the compound of the present invention is found to be less susceptible to orientation disorder after post-baking. Therefore, the compound of the present invention is useful as a constituent member of the polymerizable composition. Moreover, the optical anisotropic body using the composition containing the compound of this invention is useful for uses, such as an optical film.

The structure of a lenticular lens is shown with a schematic diagram.

1: Resin mold 2: Polymer after removing resin mold 3: Glass substrate

Claims (13)

Formula (I)

(In the formula, P ¹ and P ² each independently represent a polymerizable group, S ¹ and S ² each independently represent a spacer group, and when a plurality of S ¹ and / or S ² are present, X ¹ and X ² may be independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO. -, - CO-S -, - S-CO -, - O-CO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O- _{, -OCF 2 -, - CF 2} S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO—, —CH ₂ CH ₂ —OCO— _{, -COO-CH 2 -, -} OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N-N = CH- , —CF═CF—, —C≡C— or a single bond, and when there are a plurality of X ¹ and / or X ^2, they may be the same or different (provided that P ¹ —S ¹ , S ¹ -X ¹ , X ² -S ² , and S ² -P ² are —O—O—, —NH—O—, —O—NH—, —O—S—, or —S—O. -Not containing groups), A ¹ and A ² each independently represent 1,4-phenylene, naphthalene-1,4-diyl or naphthalene-2,6-diyl, these groups being unsubstituted or One or more L may be substituted, and B is represented by the following formulas (B-1) to (B-4):

And these groups may be unsubstituted or substituted by one or more L, and L is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group. Represents an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, or a dimethylsilyl group. Well, n1 and n2 each independently represents an integer of 0 to 8, but at least one of n1 or n2 represents an integer other than 0, and when n1 and n2 are 2 to 8, S1, X1, S2 , X2 may be the same or different. ) A compound represented by In the general formula (I), S ¹ , S ² , X ¹ , X ² , A ¹ , A ² , B, L, n1 and n2 represent the same as defined in claim 1, and P ¹ and P ² may be the same or different, and the following formulas (P-1) to (P-20)

The compound according to claim 1, which represents a group selected from: In the general formula (I), P ¹ , P ² , X ¹ , X ² , A ¹ , A ² , B, L, n1 and n2 represent the same as defined in claim 1 or claim 2. , S ¹ and S ² are each independently one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —COO—, —OCO— or —OCO. The alkylene group having 1 to 20 carbon atoms which may be replaced by -O-, and when a plurality of S ¹ and / or S ² are present, they may be the same or different. The compound according to claim 2. In general formula (I), P ¹ , P ² , S ¹ , S ² , A ¹ , A ² , B, L, n1 and n2 are the same as defined in any one of claims 1 to 3. X ¹ and X ² each independently represent —O—, —COO—, —OCO— or a single bond, and when there are a plurality of X ¹ and / or X ^2, they may be the same 4. A compound according to any one of claims 1 to 3 which may be different. In the general formula (I), P ¹ , P ² , S ¹ , S ² , X ¹ , X ² , B, L, n1 and n2 are the same as defined in any one of claims 1 to 4 A ¹ and A ² each independently represent the following formulas (a-1) to (a-6)

And the following formula (a-7) to formula (a-14)

The compound according to claim 1, which represents a group selected from: In the general formula (I), P ¹ , P ² , S ¹ , S ² , X ¹ , X ² , A ¹ , A ² , L, n1 and n2 are defined in any one of claims 1 to 5 And B represents the following formula (b-1) to formula (b-3)

The following formula (b-4) to formula (b-18)

And the following formula (b-19) to formula (b-26)

The compound as described in any one of Claims 1-5 showing group selected from these. In the general formula (I), P ¹ , P ² , S ¹ , S ² , X ¹ , X ² , A ¹ , A ² , B, n1 and n2 are defined in any one of claims 1 to 6 The compound as described in any one of Claims 1-6 which represents the same thing as a thing, and L represents a fluorine atom or a chlorine atom. In the general formula (I), P ¹ , P ² , S ¹ , S ² , X ¹ , X ² , A ¹ , A ² , B, and L are defined in any one of claims 1 to 7. The compound as described in any one of Claims 1-7 which represents the same thing as a thing, and n1 and n2 represent 1.   The polymeric composition containing the compound as described in any one of Claims 1-8.   The polymeric liquid crystal composition containing the compound as described in any one of Claims 1-8.   A polymer obtained by polymerizing the composition according to claim 9 or 10.   An optical anisotropic body using the polymer according to claim 11.   A resin, a resin additive, an oil, a filter, an adhesive, a pressure-sensitive adhesive, an oil, a fat, an ink, a pharmaceutical, a cosmetic, a detergent, a building material, a liquid crystal material, an electronic device using the compound according to any one of claims 1 to 8. Materials, agricultural chemicals, foods and products using them.

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