JP2008239568A - Piperazine compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystalline compound forming optically anisotropic products having few orientation defects and improving adhesion to supporting substrates, when forming a polymerizable liquid crystal composition and composing the optically anisotropic products. <P>SOLUTION: A piperazine compound represented by general formula (I) is provided. As the piperazine compound has excellent solubility with other liquid crystal compounds so the compound is useful as a constituent of a liquid crystal composition. And, as the polymerizable liquid crystal composition containing the piperazine compound gives a polymer having few orientation defects and excellent in adhesion to supporting substrates, so the composition is useful for optical compensation elements such as a polarizing plate and a retardation plate. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a piperazine compound, a polymerizable composition containing the compound, and an optical anisotropic body using the polymerizable composition.

  In recent years, with the progress of the information society, the importance of optical compensation elements used for deflecting plates, retardation plates and the like essential for liquid crystal displays is increasing. In addition, an example in which a polymerizable liquid crystal composition is polymerized has been reported for an optical compensation element that is highly durable and requires high functionality. An optical anisotropic body used for an optical compensation element or the like may be provided not only outside the cell but also inside, and a compound having characteristics corresponding to the purpose is required. In addition to the optical properties, the polymerization rate of the compound, solubility, melting point, glass transition point, transparency of the polymer, mechanical strength of the polymer, heat resistance, moisture resistance, and the support substrate on which the polymer is filmed Adhesion or uniform orientation is also an important factor.

  As a compound constituting the polymerizable liquid crystal composition, conventionally, a compound having a structure in which 1,4-phenylene groups are linked by an ester bond has been mainly used (see Patent Document 1). However, the polymer prepared from the liquid crystal composition composed only of the polymerizable liquid crystal compound described in the cited document has problems in adhesion to the support substrate, heat resistance, and uniform orientation. Therefore, a method of adding a phosphoric acid compound (see Patent Document 2), a silane coupling agent (see Patent Document 3), or a method of introducing a substituent into the compound (see Patent Document 4) has been proposed. The adhesiveness with the supporting substrate was not sufficient, and there was a problem in heat resistance and uniform orientation.

  On the other hand, liquid crystal compounds having a piperazine skeleton have already been disclosed (see Patent Documents 5 and 6). However, since these compounds do not have a polymerizable functional group, it is impossible to constitute a polymerizable liquid crystal composition. Further, a polymerizable compound having a piperidine skeleton as a skeleton similar to the piperazine skeleton has been disclosed (see Patent Document 7). However, the compound is characterized by having a smectic phase and is not intended for use in a nematic phase. As described above, a polymerizable compound having a piperazine skeleton and a polymerizable composition containing the compound are not known at all.

Japanese National Patent Publication No. 10-513457 JP 2001-279245 A JP 2006-126767 A JP 2005-206579 A JP-A-57-206672 JP-A-57-206673 JP 2006-124368 A

  The problem to be solved by the present invention is to provide a polymerizable compound that has a small number of alignment defects and improves adhesion to a support substrate when a polymerizable liquid crystal composition is formed to produce an optical anisotropic body. It is.

As a result of studying various polymerizable compounds, the present inventors have found that a piperazine compound can solve the above-mentioned problems, and have completed the present invention.
The present invention relates to the general formula (I)

(式中、R¹およびR²はお互い独立して下記の構造式群で表される重合性基

(Wherein R ¹ and R ² are each independently a polymerizable group represented by the following structural formula group:

X ¹ and X ² each independently represent an alkylene group, a substituted alkylene group or a single bond, and L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ⁶ are independent from each other -O-, -S-, -OCH _2- , -CH ₂ O-, -OCH ₂ CH _2- , -CH ₂ CH ₂ O-, -CO-, -COO-, -OCO-, -OCOO -, -CONR ^3- , -NR ³ CO-, -SCH _2- , -CH ₂ S-, -CH = CHCOO-, -OCOCH = CH-, -COOCH ₂ CH _2- , -CH ₂ CH ₂ OCO- _{, -OCOCH 2 CH 2 -, -} CH 2 CH 2 COO -, - COOCH 2 -, - CH 2 OCO -, - OCOCH 2 -, - CH 2 COO -, - OCOOCH 2 CH 2 -, - CH 2 CH 2 _{OCOO -, - OCOOCH 2 -,} - CH 2 OCOO -, - CH 2 OCOCH 2 -, - CH 2 COOCH 2 -, - CH 2 CH 2 -, - CH = CH -, - CF = CH -, - CH = CF, —C≡C— or a single bond (wherein R ³ represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom), and M ¹ , M ² , M ³ and M ⁴ are independent of each other. 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, La tetrahydronaphthalene-2,6-diyl group, 1,3-dioxane-2,5-diyl group, or represents a single bond, at least one of M ¹ and M ⁴ is not a single bond, M ^1, M ² , M ³ and M ⁴ may be unsubstituted or substituted with an alkyl group, a halogenated alkyl group, an alkoxy group, a halogen group, a cyano group or a nitro group, and p and q are independent of each other. Represents 0, 1 or 2. And a polymerizable liquid crystal composition using the compound.

  When the piperazine compound of the present invention constitutes a polymerizable liquid crystal composition to produce an optical anisotropic body, it has few alignment defects and is excellent in adhesiveness with a supporting substrate. Useful. Therefore, the piperazine compound of the present invention and the polymerizable liquid crystal composition containing the compound are useful as components of optical compensation elements such as a deflector plate and a retardation plate.

In the general formula (I), R ¹ and R ² are polymerizable groups and are cured by radical polymerization, radical addition polymerization, cationic polymerization, and anionic polymerization. In particular, when performing ultraviolet polymerization as a polymerization method, the formula (R-1), formula (R-2), formula (R-4), formula (R-5), formula (R-7), formula (R -11), formula (R-13) or formula (R-15) is preferred, formula (R-1), formula (R-2), formula (R-7), formula (R-11) or formula ( R-13) is more preferred, and formula (R-1) or formula (R-2) is particularly preferred.

X ¹ and X ² each independently represent an alkylene group, a substituted alkylene group or a single bond, but the carbon atom may be replaced with an oxygen atom as the oxygen atoms in the group are not directly bonded to each other. An alkylene group having 10 carbon atoms is preferred, and an alkylene group having 3 to 8 carbon atoms is more preferred from the viewpoint of liquid crystallinity and compatibility with other liquid crystal compounds.

L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ⁶ are independently of each other -O-, -S-, -OCH _2- , -CH ₂ O-, -OCH ₂ CH _2- , -CH _{2 CH 2 O -, - CO} -, - COO -, - OCO -, - OCOO -, - CONR 3 -, - NR 3 CO -, - SCH 2 -, - CH 2 S -, - CH = CHCOO-, _{-OCOCH = CH -, - COOCH 2} CH 2 -, - CH 2 CH 2 OCO -, - OCOCH 2 CH 2 -, - CH 2 CH 2 COO -, - COOCH 2 -, - CH 2 OCO -, - OCOCH 2 _{-, - CH 2 COO -,} - OCOOCH 2 CH 2 -, - CH 2 CH 2 OCOO -, - OCOOCH 2 -, - CH 2 OCOO -, - CH 2 OCOCH 2 -, - CH 2 COOCH 2 -, - CH ₂ CH _2- , -CH = CH-, -CF = CH-, -CH = CF, -C≡C- or a single bond (wherein R ³ is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom Represents -O-, -OCH _2- , -CH ₂ O-, -OCH ₂ CH _2- , -CH ₂ CH ₂ O-, -CO-, -COO-, -OCO-, -OCOO -, -COOCH ₂ CH _2- , -CH ₂ CH ₂ OCO-, -OCOCH ₂ CH _2- , -CH ₂ CH ₂ COO-, -COOCH _2- , -CH ₂ OCO-, -OCOCH _2- , -CH _{2 COO -, - OCOOCH 2 CH} 2 -, - CH 2 CH 2 OCOO -, - OCOOCH 2 -, - CH 2 OCOO -, - CH 2 OCOCH 2 -, - CH 2 COOCH 2 -, - CH 2 CH 2 - Or a single bond is preferred, -C OOCH ₂ CH _2- , -CH ₂ CH ₂ OCO-, -OCOCH ₂ CH _2- , -CH ₂ CH ₂ COO- or -CH ₂ CH ₂ -are more preferred, and L ⁵ and L ⁶ are independently of each other- _{COOCH 2 CH 2 -, - CH} 2 CH 2 OCO -, - OCOCH 2 CH 2 -, - CH 2 CH 2 COO- or -CH ₂ CH ₂ - and particularly preferably a.

M ¹ , M ² , M ³ and M ⁴ 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, tetrahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl group, but M ¹ , M ² , M ³ and M ⁴ are independent of each other. May be unsubstituted or substituted by an alkyl group, a halogenated alkyl group, an alkoxy group, a halogen group, a cyano group or a nitro group, and independently of each other, a 1,4-phenylene group or a 1,4-cyclohexylene group preferable.

p and q independently represent 0, 1 or 2, but from the viewpoint of liquid crystallinity and heat resistance, p + q is preferably 0, 1 or 2, more preferably 0 or 1. It is particularly preferred that
Specifically, the compounds represented by the general formula (I) are particularly preferably compounds represented by the following general formulas (I-1) to (I-24).

  In the present invention, production examples of the compound represented by the general formula (I) will be given below. Of course, the gist and scope of the present invention are not limited by these production examples.

  The compound (I) of the present invention can be produced, for example, as follows.

  Formula (II)

(Wherein R ¹ , X ¹ , L ¹ , L ² , L ⁵ , M ¹ , M ² and p have the same meaning as in general formula (I)), a piperazine derivative represented by In the presence of palladium, nickel or iron-based transition metal catalysts such as phenylphosphine palladium (0), dichloride (1,2-bis (diphenylphosphino) ethane) nickel (II), tris (acetylacetonato) iron (III) General formula (III)

(In the formula, Z ¹ represents a leaving group such as a chlorine atom, a bromine atom, an iodine atom, a trifluoromethanesulfonyloxy group, a p-toluenesulfonyloxy group, a methanesulfonyloxy group, R ² , X ² , L ³ , L ⁴ , L ⁶ , M ³ , M ⁴ and q have the same meaning as in general formula (I).) By reacting with a compound represented by general formula (I), a compound represented by general formula (I) is obtained. be able to.

  Alternatively, piperazine may be palladium, nickel such as tetrakistriphenylphosphine palladium (0), dichloride (1,2-bis (diphenylphosphino) ethane) nickel (II), tris (acetylacetonato) iron (III), nickel or By reacting with a compound represented by general formula (III) in the presence of an iron-based transition metal catalyst, general formula (Ia)

(Wherein R ² , X ² , L ³ , L ⁴ , L ⁶ , M ³ , M ⁴ and q have the same meanings as in general formula (I)) can be obtained. it can.

  Alternatively, the general formula (IV)

(Wherein, Z ² is _{-CH 2 -, - CH 2 CH} 2 - or a single ^{bond, R 1, X 1, L} 1, L 2, L 5, M 1, M 2 and p have the general formula ( The alcohol represented by (1) is an acid catalyst such as p-toluenesulfonic acid or dicyclohexylcarbodiimide (DCC), 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride ( WSC), carbodiimide derivatives such as diisopropylcarbodiimide (DIC), or azodicarboxylate esters such as ethyl azodicarboxylate (DEAD), isopropyl azodicarboxylate (DIAD), etc.

(式中、Z³は-CH₂-、-CH₂CH₂-あるいは単結合を表し、R²、X²、L³、L⁴、L⁶、M³、M⁴およびqは一般式(I)におけると同じ意味を表す。)で表されるカルボン酸と作用させることにより、一般式(I-b)

(Wherein, Z ³ is _{-CH 2 -, - CH 2 CH} 2 - or a single ^{bond, R 2, X 2, L} 3, L 4, L 6, M 3, M 4 and q have the general formula ( It represents the same meaning as in I). By reacting with the carboxylic acid represented by

(Where R ¹ , R ² , X ¹ , X ² , L ¹ , L ² , L ³ , L ⁴ , L ⁵ , L ⁶ , M ¹ , M ² , M ³ , M ⁴ , p and q are Represents the same meaning as in general formula (I), Z ² represents the same meaning as in general formula (IV), and Z ³ represents the same meaning as in general formula (V).) Obtainable.
Or the general formula (VI)

(Wherein, Z ⁴ is _{-CH 2 -, - CH 2 CH} 2 -. Of or a single bond) a diol represented by an acid catalyst or dicyclohexylcarbodiimide such p- toluenesulfonic acid (DCC), 1- Carbodiimide derivatives such as ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSC) and diisopropylcarbodiimide (DIC) or azodicarboxylic acid esters such as ethyl azodicarboxylate (DEAD) and isopropyl azodicarboxylate (DIAD) In the presence of a dehydration condensing agent of the general formula (Ic) by reacting with the carboxylic acid represented by the general formula (V)

(Wherein R ² , X ² , L ³ , L ⁴ , L ⁶ , M ³ , M ⁴ and q represent the same meaning as in general formula (I), and Z ³ is the same as in general formula (V) Z ⁴ represents the same meaning as in general formula (VI)), and a piperazine compound represented by formula (VI) can be obtained.
Alternatively, the general formula (VII)

(Wherein, Z ⁵ is _{-CH 2 -, - CH 2 CH} 2 - or a single ^{bond, R 1, X 1, L} 1, L 2, L 5, M 1, M 2 and p have the general formula ( I represents the same meaning as in I).) The carboxylic acid represented by) is an acid catalyst such as p-toluenesulfonic acid or dicyclohexylcarbodiimide (DCC), 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSC), carbodiimide derivatives such as diisopropylcarbodiimide (DIC) or azodicarboxylate esters such as ethyl azodicarboxylate (DEAD), isopropyl azodicarboxylate (DIAD), etc.

(Wherein, Z ⁶ are _{-CH 2 -, - CH 2 CH} 2 - or a single ^{bond, R 2, X 2, L} 3, L 4, L 6, M 3, M 4 and q have the general formula ( It represents the same meaning as in I). By reacting with the carboxylic acid represented by

(Where R ¹ , R ² , X ¹ , X ² , L ¹ , L ² , L ³ , L ⁴ , L ⁵ , L ⁶ , M ¹ , M ² , M ³ , M ⁴ , p and q are Z ⁵ represents the same meaning as in general formula (VII), and Z ⁶ represents the same meaning as in general formula (VIII).) Obtainable.

  Or the general formula (IX)

(Wherein, Z ⁷ is _{-CH 2 -, - CH 2 CH} 2 -. Of or a single bond) a dicarboxylic acid represented by the acid catalyst or dicyclohexylcarbodiimide such p- toluenesulfonic acid (DCC), 1 -Carboxyimide derivatives such as ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSC) and diisopropylcarbodiimide (DIC) or azodicarboxylic acid esters such as ethyl azodicarboxylate (DEAD) and isopropyl azodicarboxylate (DIAD) In the presence of a dehydrating condensing agent such as, by reacting with an alcohol represented by the general formula (VIII), the general formula (Ie)

(Wherein R ² , X ² , L ³ , L ⁴ , L ⁶ , M ³ , M ⁴ and q represent the same meaning as in general formula (I), and Z ⁶ is the same as in general formula (VIII). Z ⁷ represents the same meaning as in general formula (IX)), and a piperazine compound represented by formula (IX) can also be obtained.

  Next, the polymerizable liquid crystal composition of the present invention will be described. The polymerizable liquid crystal composition of the present invention is preferably prepared so as to exhibit a smectic A phase or a nematic phase at room temperature. Specifically, it is preferable that the smectic A phase or the nematic phase is maintained even at 35 ° C. or lower, preferably 30 ° C. or lower, more preferably 25 ° C. or lower. The polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition of the present invention preferably has an acryloyloxy group or a methacryloyloxy group as a polymerizable functional group. As the polymerizable liquid crystal compound, those having two or more polymerizable functional groups in the molecule are preferable. As such a bifunctional or higher compound, the general formula (A)

(W ¹ and W ² each independently represent a single bond, -O-, -COO- or -OCO-, and Y ³ and Y ⁴ each independently represent -COO- or -OCO-. , R and s each independently represents an integer of 2 to 18, and the hydrogen atoms of the three 1,4-phenylene groups present in the formula are each independently an alkyl group having 1 to 7 carbon atoms, An alkoxy group, an alkanoyl group, a cyano group, or a halogen atom may be substituted by one or two or more). Among the compounds represented by the general formula (A), compounds represented by (A-1) to (A-8) are particularly preferable.

(Wherein, r and s have the same meaning as in general formula (A).)
r and s are each independently preferably an integer of 3 to 6.
In addition, the general formula (B)

(W ³ and W ⁴ are each independently a single bond, —O—, —COO— or —OCO—, Y ⁵ is —COO— or —OCO—, and p and q are each independently Each of the three kinds of 1,4-phenylene groups present in the formula is independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group, an alkanoyl group, or a cyano group. Alternatively, one or two or more halogen atoms may be substituted.) Is also preferred. Among the compounds represented by the general formula (B), compounds represented by (B-1) to (B-8) are particularly preferable.

(Wherein p and q represent the same meaning as in general formula (B).)
Among such compounds, from the viewpoint of heat resistance and durability, the compound of (B-2), (B-5), (B-6), (B-9) or (B-10) is preferred, The compound B-2) is particularly preferred.
In addition, compounds such as compounds (C-1) to (C-10) can be contained as the polymerizable liquid crystal compound having two or more polymerizable functional groups in the molecule.

(In the formula, u and v independently represent an integer of 2 to 18.)
Of these, the compounds (C-2) and (C-3) are preferred. u and v are preferably an integer of 3 to 18, more preferably an integer of 4 to 16, and particularly preferably 6 to 12.
In addition, the general formula (D)

(In the formula, e represents an integer of 0 to 18, but when e is 0 or 1, f represents 0, or when e represents an integer of 2 to 18, f represents 0 or 1, i represents Represents an integer of 0 to 2, and each of rings C, D and E independently represents 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5- Diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo [2.2.2] octylene group, decahydronaphthalene-2,6-diyl group Pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6- Naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene 2,7-diyl group, Represents a fluorene 2,7-diyl group, the 1,4-phenylene group, Trahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a , 9,10a-Octahydrophenanthrene 2,7-diyl group and fluorene 2,7-diyl group are unsubstituted or substituted as one or more F, Cl, CF ₃ , OCF ₃ or CH ₃ and Y ⁶ and Y ⁷ are each independently a single bond, —COO—, —OCO—, —CH═N—, —N═CH—, —C≡C—, —CH ₂ CH _2- , -CH ₂ CH ₂ CH ₂ CH _2- , -CH ₂ CH ₂ CH ₂ O-, -OCH ₂ CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CH = NN = CH-, -CF = CF-, -CH = CH-, -CH ₂ CH ₂ CH = CH-, -CH = CHCH ₂ CH _2- , -CH ₂ CH = CHCH _2- , -CH = CHCOO-, -OCOCH = CH-, -CH ₂ CH ₂ OCO- or -COOCH ₂ CH _2- , Y ⁸ represents a single bond, -O-, -CO-, -COO-, _{-OCO -, - CH 2 -,} - CH 2 O -, - OCH 2 -, - CONH -, - NHCO -, - CH 2 COO- or an -CH ₂ OCO-, Z 1 to 18 carbon atoms An alkyl group of Represents an alkenyl group having 2 to 18 carbon atoms, a halogen atom, CN or NCS, wherein the alkyl group or alkenyl group is unsubstituted or substituted with one or more F, Cl, CN, CH ₃ Or CF ₃ , wherein one or more CH ₂ groups present in the alkyl or alkenyl group are substituted with O, CO or COO as O atoms are not directly bonded to each other May be. It is also possible to add a monofunctional polymerizable liquid crystal compound represented by

  The addition amount is preferably 50% or less, more preferably 30% or less, and particularly preferably 15% or less. Among the compounds represented by the general formula (D), compounds represented by (D-1) to (D-11) are particularly preferable.

(Wherein e and f represent the same meaning as in general formula (D), and R represents an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms.)
Furthermore, the polymerizable liquid crystal composition of the present invention may be added with a compound having a polymerizable functional group and not exhibiting liquid crystallinity. Such a compound can be used without particular limitation as long as it is generally recognized as a polymer-forming monomer or polymer-forming oligomer in this technical field. It is necessary to adjust to exhibit sex.

  The concentration of the photopolymerization initiator in the polymerizable liquid crystal composition of the present invention is preferably 0.1 to 10%, more preferably 0.2 to 5%. Examples of the photopolymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, and acylphosphine oxides.

  In addition, a stabilizer can be added to the polymerizable liquid crystal composition of the present invention in order to improve its storage stability. Examples of the stabilizer that can be used include hydroquinone, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, nitroso compounds, and the like. . When the stabilizer is used, the addition amount is preferably 0.005 to 1%, more preferably 0.02 to 0.5% with respect to the liquid crystal composition.

  In addition, when the polymerizable liquid crystal composition of the present invention is used for a raw material of a polarizing film or an alignment film, a printing ink, a paint, a protective film or the like, a metal, a metal complex, a dye, or a pigment depending on the purpose. , Dyes, fluorescent materials, phosphorescent materials, surfactants, leveling agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, ion exchange resins, metal oxides such as titanium oxide, etc. Can also be added.

Next, the optical anisotropic body of the present invention will be described. The optical anisotropic body produced by polymerizing the polymerizable liquid crystal composition of the present invention can be used for various applications. For example, when the polymerizable liquid crystal composition of the present invention is polymerized without being oriented, it can be used as a light scattering plate, a depolarizing plate, or a moire fringe prevention plate. Moreover, the optically anisotropic body produced by polymerizing the polymerizable liquid crystal composition of the present invention in an aligned state has optical anisotropy in physical properties and is useful. Such an optical anisotropic element, for example, a substrate a polymerizable liquid crystal composition surface, substrate was rubbed with a cloth or the like, or the formed surface of the substrate and the organic thin film was rubbed with a cloth or the like of the present invention or SiO _2, Can be produced by polymerizing the liquid crystal of the present invention after it is supported on a substrate having an orientation film deposited obliquely or sandwiched between the 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. Examples of the organic solvent include ethyl acetate, tetrahydrofuran, toluene, hexane, methanol, ethanol, dimethylformamide, methylene chloride, isopropanol, acetone, methyl ethyl ketone, acetonitrile, and cellosolves. 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. Providing an intermediate layer such as a polyimide thin film on the substrate is also effective as a means for improving the adhesion when the adhesion between the optically anisotropic substance obtained by polymerizing the polymerizable liquid crystal material and the substrate is not good. .

Examples of the orientation treatment other than the rubbing treatment or the oblique deposition of SiO ₂ include the use of fluid orientation of a liquid crystal material and the 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.

  If proper orientation cannot be obtained by rubbing these substrates with a cloth or the like, an organic thin film such as a polyimide thin film or a polyvinyl alcohol thin film is formed on the substrate surface according to a known method, and this is rubbed with a cloth or the like. Also good. In the case where the alignment state is controlled by an electric field, a substrate having an electrode layer is used. In this case, it is preferable to form an organic thin film such as the aforementioned polyimide thin film on the electrode.

As a method of polymerizing the polymerizable liquid crystal composition of the present invention, since rapid progress of polymerization is desirable, 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. In addition, when polymerization is performed with the liquid crystal composition sandwiched between two substrates, at least the substrate on the irradiation surface side must be given 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 to 2.0 mW / cm ² . If the intensity is 0.1 mW / cm ² or less, it takes a long time to complete the photopolymerization and the productivity deteriorates. If it is 2.0 W / cm ² or more, the polymerizable liquid crystal compound or the polymerizable liquid crystal There is a risk that the composition will deteriorate.

  The optical anisotropic body of the present invention obtained by polymerization can be subjected to 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 of the present invention produced 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 explained in full detail, this invention is not limited to these Examples.

  The phase transition temperature was measured using a polarizing microscope equipped with a temperature control stage and a differential scanning calorimeter (DSC). The structure of the compound was confirmed by nuclear magnetic resonance spectrum (NMR), infrared resonance spectrum (IR), gel permeation chromatography (GPC) and the like.

  In order to confirm the adhesion of the optically anisotropic body to the supporting substrate, a polymerizable composition was applied to the supporting substrate to prepare an optically anisotropic body, and a cellophane tape peel test (JIS-5400 8.5 adhesion ( 8.5.2) was performed, and it was judged that the adhesiveness was excellent when the number of adhesions was large according to the number of adhesions / number of grids.

As an index of the adhesiveness of the polymerizable composition to the supporting substrate, it was confirmed whether repelling occurred or uniform application was possible when the polymerizable liquid crystal composition was applied to the supporting substrate. When the polymerizable liquid crystal composition was applied after being dissolved in a solvent, it was confirmed whether the polymerizable liquid crystal composition was uniformly applied after the solvent was volatilized.
Example 1 Synthesis of 1,4-bis [2- [4- [3- (acryloyloxy) propyloxy] benzoyloxy] ethyl] piperazine (I-7)

4-[3-(アクリロイルオキシ)プロピルオキシ]安息香酸(14.4 g、0.058 mol)、1,4-ビス[(2-ヒドロキシエチル)]ピペラジン(5.0 g、0.029 mol)、1-エチル-3-(3-ジメチルアミノプロピル)カルボジイミド塩酸塩(WSC、16.5 g、0.086 mol)、4-ジメチルアミノピリジン(DMAP、10.5 g、0.086 mol)のジクロロメタン(100 ml)懸濁液を室温で24時間激しく攪拌した後、3 M塩酸に空けて反応を終了させた。有機層を分離し、水層からジクロロメタンで抽出した。有機層を集めた後、水、飽和炭酸水素ナトリウム水溶液、飽和食塩水の順で洗條し、無水硫酸ナトリウムで乾燥した。溶媒を留去し、得られた固体をカラム(アルミナ／ヘキサン＋酢酸エチル)を用いて精製し、再結晶(ヘキサン＋酢酸エチル)することにより、無色の固体(9.0 g)を得た。(収率 49.1%)
¹H-NMR (400MHz, CDCl₃) δ(ppm) 2.19 (pent, 2H), 2.78 (t, 2H), 2.99 (br, 4H), 4.11 (t, 2H), 4.36 (t, 2H), 4.42 (t, 2H), 5.83 (dd, 1H, J₁=10.4Hz, J₂=1.2Hz), 6.12 (dd, 1H, J₁=17.2Hz, J₂=10.4Hz), 6.41 (dd, 1H, J₁=17.2Hz, J₂=1.2Hz), 6.48 (d, 2H), 8.21 (d, 2H)、相転移温度(℃) Cr 87 Iso
（実施例２）1,4-ビス[2-[4-[6-(アクリロイルオキシ)ヘキシルオキシ]ベンゾイルオキシ]エチル]ピペラジン(I-8)の合成

4- [3- (acryloyloxy) propyloxy] benzoic acid (14.4 g, 0.058 mol), 1,4-bis [(2-hydroxyethyl)] piperazine (5.0 g, 0.029 mol), 1-ethyl-3- A suspension of (3-dimethylaminopropyl) carbodiimide hydrochloride (WSC, 16.5 g, 0.086 mol) and 4-dimethylaminopyridine (DMAP, 10.5 g, 0.086 mol) in dichloromethane (100 ml) was vigorously stirred at room temperature for 24 hours. Then, the reaction was terminated by emptying with 3 M hydrochloric acid. The organic layer was separated and extracted from the aqueous layer with dichloromethane. The organic layer was collected, washed with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting solid was purified using a column (alumina / hexane + ethyl acetate) and recrystallized (hexane + ethyl acetate) to obtain a colorless solid (9.0 g). (Yield 49.1%)
¹ H-NMR (400MHz, CDCl ₃ ) δ (ppm) 2.19 (pent, 2H), 2.78 (t, 2H), 2.99 (br, 4H), 4.11 (t, 2H), 4.36 (t, 2H), 4.42 (t, 2H), 5.83 (dd, 1H, J ₁ = 10.4Hz, J ₂ = 1.2Hz), 6.12 (dd, 1H, J ₁ = 17.2Hz, J ₂ = 10.4Hz), 6.41 (dd, 1H, J ₁ = 17.2Hz, J ₂ = 1.2Hz), 6.48 (d, 2H), 8.21 (d, 2H), phase transition temperature (° C) Cr 87 Iso
Example 2 Synthesis of 1,4-bis [2- [4- [6- (acryloyloxy) hexyloxy] benzoyloxy] ethyl] piperazine (I-8)

4-[6-(アクリロイルオキシ)ヘキシルオキシ]安息香酸(16.8 g、0.058 mol)、1,4-ビス[(2-ヒドロキシエチル)]ピペラジン(5.0 g、0.029 mol)、1-エチル-3-(3-ジメチルアミノプロピル)カルボジイミド塩酸塩(WSC、16.5 g、0.086 mol)、4-ジメチルアミノピリジン(DMAP、10.5 g、0.086 mol)のジクロロメタン(100 ml)懸濁液を室温で24時間激しく攪拌した後、3 M塩酸に空けて反応を終了させた。有機層を分離し、水層からジクロロメタンで抽出した。有機層を集めた後、水、飽和炭酸水素ナトリウム水溶液、飽和食塩水の順で洗條し、無水硫酸ナトリウムで乾燥した。溶媒を留去し、得られた固体をカラム(アルミナ／ヘキサン＋酢酸エチル)を用いて精製し、再結晶(ヘキサン＋酢酸エチル)することにより、無色の固体(10.8 g)を得た。(収率 51.9%)
¹H-NMR (400MHz, CDCl₃) δ(ppm) 1.46-1.93 (m, 8H), 2.63 (br, 4H), 2.78 (t, 2H), 4.01 (t, 2H), 4.17 (t, 2H), 4.42 (t, 2H), 5.82 (dd, 1H, J₁=10.4Hz, J₂=1.6Hz), 6.12 (dd, 1H, J₁=17.2Hz, J₂=10.4Hz), 6.40 (dd, 1H, J₁=17.2Hz, J₂=1.6Hz), 6.90 (d, 2H), 7.97 (d, 2H)、相転移温度(℃) Cr 107 Iso
（実施例３）
低粘性で温度範囲の広いネマチック相を示す重合性液晶組成物(H-1)

4- [6- (acryloyloxy) hexyloxy] benzoic acid (16.8 g, 0.058 mol), 1,4-bis [(2-hydroxyethyl)] piperazine (5.0 g, 0.029 mol), 1-ethyl-3- A suspension of (3-dimethylaminopropyl) carbodiimide hydrochloride (WSC, 16.5 g, 0.086 mol) and 4-dimethylaminopyridine (DMAP, 10.5 g, 0.086 mol) in dichloromethane (100 ml) was vigorously stirred at room temperature for 24 hours. Then, the reaction was terminated by emptying with 3 M hydrochloric acid. The organic layer was separated and extracted from the aqueous layer with dichloromethane. The organic layer was collected, washed with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting solid was purified using a column (alumina / hexane + ethyl acetate) and recrystallized (hexane + ethyl acetate) to obtain a colorless solid (10.8 g). (Yield 51.9%)
¹ H-NMR (400MHz, CDCl ₃ ) δ (ppm) 1.46-1.93 (m, 8H), 2.63 (br, 4H), 2.78 (t, 2H), 4.01 (t, 2H), 4.17 (t, 2H) , 4.42 (t, 2H), 5.82 (dd, 1H, J ₁ = 10.4Hz, J ₂ = 1.6Hz), 6.12 (dd, 1H, J ₁ = 17.2Hz, J ₂ = 10.4Hz), 6.40 (dd, 1H, J ₁ = 17.2Hz, J ₂ = 1.6Hz), 6.90 (d, 2H), 7.97 (d, 2H), phase transition temperature (° C) Cr 107 Iso
(Example 3)
Polymeric liquid crystal composition showing nematic phase with low viscosity and wide temperature range (H-1)

The nematic phase upper limit temperature (Tni) was 73.0 ° C.
Next, the polymerizable liquid crystal composition (H-1) 93.0%, photopolymerization initiator Irgacure-651 (manufactured by Ciba Specialty Chemicals) 5.0% and the compound (I-7) obtained in Example 1

A polymerizable liquid crystal composition (M-1) was prepared by adding 2.0% of the above compound. Next, a xylene solution containing 33% by mass of the polymerizable liquid crystal composition (M-1) was prepared, and this xylene solution was spin-coated on a glass substrate with a polyimide alignment film (3,000 rpm / 30 seconds). It was able to apply without generating. The polymerizable liquid crystal composition (M-1) was cured by irradiating the spin-coated substrate with ultraviolet rays (4 mW / cm ² , 120 seconds) in the air.

When the solid thus obtained was observed under a polarizing microscope, an optical anisotropic body having no alignment defect was obtained. Assuming that the phase difference before heating of the obtained optical anisotropic body was 100%, the phase difference after heating at 240 ° C. for 4 hours was 77%, and the phase difference reduction rate was 23%. In addition, the pencil hardness (JIS-K-5400 8.4 pencil scratch test) of the obtained solid was 2H, and the cellophane tape peel test (JIS-5400 8.5 adhesion (8.5.2 cross-cut tape method)) was 100. / 100. Next, when a xylene solution containing 33% by mass of the polymerizable liquid crystal composition (M-1) was spin coated (3,000 rpm / 30 seconds) on an untreated glass substrate, it could be applied without repellency.
Polymeric liquid crystal composition showing nematic phase with low viscosity and wide temperature range (H-2)

Was prepared, and the nematic phase upper limit temperature (Tni) was 46.0 ° C. A polymerizable liquid crystal composition (M-2) was prepared by adding 10% of compound (I-7) to 90% of this polymerizable liquid crystal composition (H-1). I couldn't.
Example 4
Polymerizable liquid crystal composition (H-1) obtained in Example 3 93.0%, photopolymerization initiator Irgacure-651 (manufactured by Ciba Specialty Chemicals) 5.0% and compound (I-8) obtained in Example 2

A polymerizable liquid crystal composition (M-3) was prepared by adding 2.0% of the above compound. Next, a xylene solution containing 33% by mass of the polymerizable liquid crystal composition (M-1) was prepared, and this xylene solution was spin-coated on a glass substrate with a polyimide alignment film (3,000 rpm / 30 seconds). It was able to apply without generating. The polymerizable liquid crystal composition (M-1) was cured by irradiating the spin-coated substrate with ultraviolet rays (4 mW / cm ² , 120 seconds) in the air.

When the solid thus obtained was observed under a polarizing microscope, an optical anisotropic body having no alignment defect was obtained. Assuming that the phase difference before heating of the obtained optical anisotropic body was 100%, the phase difference after heating at 240 ° C. for 4 hours was 79%, and the phase difference reduction rate was 21%. In addition, the pencil hardness (JIS-K-5400 8.4 pencil scratch test) of the obtained solid was 2H, and the cellophane tape peel test (JIS-5400 8.5 adhesion (8.5.2 cross-cut tape method)) was 100. / 100.
Next, when a xylene solution containing 33% by mass of the polymerizable liquid crystal composition (M-3) was spin-coated (3,000 rpm / 30 seconds) on an untreated glass substrate, it could be applied without repellency.
Further, 10% of the compound (I-7) was added to 90% of the polymerizable liquid crystal composition (H-2) obtained in Example 3 to prepare a polymerizable liquid crystal composition (M-4). And no precipitation was observed at room temperature.

(Comparative Example 1)
Polymerization without adding the compound of the present invention, only 5.0% of photopolymerization initiator Irgacure-651 (manufactured by Ciba Specialty Chemicals) was added to 95.0% of the polymerizable liquid crystal composition (H-1) prepared in Example 3. A liquid crystal composition (M-5) was prepared. Next, a xylene solution containing 33% by mass of the polymerizable liquid crystal composition (M-5) was prepared, and this xylene solution was spin-coated on a glass substrate with a polyimide alignment film (3,000 rpm / 30 seconds). It was able to apply without generating. The polymerizable liquid crystal composition (M-3) was cured by irradiating the spin-coated substrate with ultraviolet rays (4 mW / cm ² , 120 seconds) in the air.

  When the solid thus obtained was observed under a polarizing microscope, many alignment defects were observed. Further, assuming that the phase difference before heating of the obtained optical anisotropic body was 100%, the phase difference after heating at 240 ° C. for 4 hours was 75%, and the phase difference reduction rate was 25%. In addition, the pencil hardness (JIS-K-5400 8.4 pencil scratch test) of the obtained solid is 2H, the cellophane tape peel test (JIS-5400 8.5 adhesion (8.5.2 cross-cut tape method)) is 0 / 100.

As described above, the polymerizable liquid crystal composition (M-5) not containing the compound of the present invention has a problem in terms of adhesion to the support base of the produced optical anisotropic body and alignment uniformity. Furthermore, since the retardation reduction rate is slightly larger than the optical anisotropic bodies described in the examples, the optical anisotropic body using the compound of the present invention is superior to the optical anisotropic body of Comparative Example 1 in terms of heat resistance. I understand that.
Further, when a xylene solution containing 33% by mass of the polymerizable liquid crystal composition (M-3) was spin-coated on an untreated glass substrate (3,000 rpm / 30 seconds), repellency occurred and the coating could not be performed.

(Comparative Example 2)
A polymerizable liquid crystal composition was prepared by adding 5.0% of photopolymerization initiator Irgacure-651 (manufactured by Ciba Specialty Chemicals) and 0.04% of vinylphosphonic acid to 94.96% of the polymerizable liquid crystal composition (H-1) obtained in Example 3. A product (M-6) was prepared. Next, a xylene solution containing 33% by mass of the polymerizable liquid crystal composition (M-6) was prepared, and this xylene solution was spin-coated on a glass substrate with a polyimide alignment film (3,000 rpm / 30 seconds). It was able to apply without generating. The polymerizable liquid crystal composition (M-6) was cured by irradiating the spin-coated substrate with ultraviolet rays (4 mW / cm ² , 120 seconds) in the air.

  When the solid thus obtained was observed under a polarizing microscope, many alignment defects were observed. Further, assuming that the phase difference before heating of the obtained optical anisotropic body was 100%, the phase difference after heating at 240 ° C. for 4 hours was 75%, and the phase difference reduction rate was 25%. Moreover, the pencil hardness (JIS-K-5400 8.4 pencil scratch test) of the obtained solid is HB, the cellophane tape peel test (JIS-5400 8.5 adhesion (8.5.2 cross-cut tape method)) is 0 / 100.

  Further, when a xylene solution containing 33% by mass of the polymerizable liquid crystal composition (M-6) was spin-coated on an untreated glass substrate (3,000 rpm / 30 seconds), cissing occurred and the coating could not be performed.

Claims (7)

Formula (I)

(Wherein R ¹ and R ² are each independently a polymerizable group represented by the following structural formula group:

X ¹ and X ² each independently represent an alkylene group, a substituted alkylene group or a single bond, and L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ⁶ are independent from each other -O-, -S-, -OCH _2- , -CH ₂ O-, -OCH ₂ CH _2- , -CH ₂ CH ₂ O-, -CO-, -COO-, -OCO-, -OCOO -, -CONR ^3- , -NR ³ CO-, -SCH _2- , -CH ₂ S-, -CH = CHCOO-, -OCOCH = CH-, -COOCH ₂ CH _2- , -CH ₂ CH ₂ OCO- _{, -OCOCH 2 CH 2 -, -} CH 2 CH 2 COO -, - COOCH 2 -, - CH 2 OCO -, - OCOCH 2 -, - CH 2 COO -, - OCOOCH 2 CH 2 -, - CH 2 CH 2 _{OCOO -, - OCOOCH 2 -,} - CH 2 OCOO -, - CH 2 OCOCH 2 -, - CH 2 COOCH 2 -, - CH 2 CH 2 -, - CH = CH -, - CF = CH -, - CH = CF, —C≡C— or a single bond (wherein R ³ represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom), and M ¹ , M ² , M ³ and M ⁴ are independent of each other. 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, Represents a lahydronaphthalene-2,6-diyl group, a 1,3-dioxane-2,5-diyl group or a single bond, wherein the carbon atoms in the group are each independently unsubstituted or an alkyl group, It may be substituted with a halogenated alkyl group, an alkoxy group, a halogen group, a cyano group or a nitro group, and at least one of M ¹ and M ⁴ is not a single bond, and p and q are each independently 0, Represents 1 or 2. A piperazine compound represented by: The piperazine according to claim 1, wherein X ¹ and X ² each independently represent an alkylene group having 2 to 10 carbon atoms in which the carbon atom may be replaced by an oxygen atom, assuming that the oxygen atoms in the group are not directly bonded to each other. Compound. ^2. The piperazine compound according to claim ¹ , wherein M ¹ , M ² , M ³ and M ⁴ each independently represent a 1,4-phenylene group or a 1,4-cyclohexylene group. The piperazine compound according to claim 1 or 2, wherein p + q represents 0, 1 or 2. Claims wherein L ⁵ and L ⁶ independently represent -COOCH ₂ CH _2- , -CH ₂ CH ₂ OCO-, -OCOCH ₂ CH _2- , -CH ₂ CH ₂ COO- or -CH ₂ CH _2-. The piperazine compound according to 1. A polymerizable liquid crystal composition containing the piperazine compound according to claim 1. 6. An optical anisotropic body using the polymerizable liquid crystal composition according to claim 5.