WO2013039053A1 - Polymerizable liquid crystal composition and alignment film - Google Patents

Polymerizable liquid crystal composition and alignment film Download PDF

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Publication number
WO2013039053A1
WO2013039053A1 PCT/JP2012/073161 JP2012073161W WO2013039053A1 WO 2013039053 A1 WO2013039053 A1 WO 2013039053A1 JP 2012073161 W JP2012073161 W JP 2012073161W WO 2013039053 A1 WO2013039053 A1 WO 2013039053A1
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liquid crystal
polymerizable liquid
film
crystal composition
compound
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PCT/JP2012/073161
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French (fr)
Japanese (ja)
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ダニエルアントニオ 櫻葉汀
真 畑中
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日産化学工業株式会社
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Priority to KR1020147006183A priority Critical patent/KR102045532B1/en
Priority to CN201280044775.8A priority patent/CN103827155B/en
Priority to JP2013533667A priority patent/JP5958471B2/en
Publication of WO2013039053A1 publication Critical patent/WO2013039053A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F224/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3016—Polarising elements involving passive liquid crystal elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers

Definitions

  • the present invention relates to a polymerizable liquid crystal composition, a polymer obtained using the polymerizable liquid crystal composition, and an alignment film.
  • a polymerizable liquid crystal composition that can be suitably used for a material having optical characteristics such as a display device or a recording material, in particular, an optical compensation film such as a polarizing plate for a liquid crystal display or a retardation plate, and obtained using the same.
  • the present invention relates to a polymer and a hybrid alignment film obtained by using these.
  • the polymerizable liquid crystal compound used here is generally a liquid crystal compound having a polymerizable group and a liquid crystal structure part (structure part having a spacer part and a mesogen part), and an acrylic group is widely used as the polymerizable group. ing.
  • Such a polymerizable liquid crystal compound is generally made into a polymer (film) by a method of polymerizing by irradiation with radiation such as ultraviolet rays.
  • a method of polymerizing by irradiation with radiation such as ultraviolet rays.
  • a method in which a specific polymerizable liquid crystal compound having an acrylic group is supported between supports and a polymer is obtained by irradiating radiation while maintaining the compound in a liquid crystal state Patent Document 1
  • Patent Document 2 a method of obtaining a polymer by adding a photopolymerization initiator to a mixture of two kinds of polymerizable liquid crystal compounds or a composition obtained by mixing a chiral liquid crystal with this mixture and irradiating ultraviolet rays.
  • the polymer (film) obtained by each of the above methods is a display device used in a high-temperature environment such as in a car as well as a display device such as a monitor or a television as a polarizing plate or a retardation film. Mounted on. For this reason, maintaining transparency in a high temperature environment is very important as a display device material. However, since a film obtained from a polymerizable liquid crystal compound has a glass transition temperature (hereinafter referred to as Tg) that is lower than the temperature of the use environment, particularly in a high temperature environment, molecular fluctuations occur. The orientation may be disturbed, and the optical anisotropy may be significantly reduced.
  • Tg glass transition temperature
  • the orientation mode (for example, horizontal or hybrid) of the obtained film can be easily controlled by adding a small amount of a specific compound to the liquid crystal composition, it can be widely applied in the liquid crystal display field. If a single material can be used to change the process and a horizontal or hybrid alignment film can be easily created, a wide range of applications can be expected in the liquid crystal display field.
  • Patent Document 4 describes that a polyfunctional polymerizable compound having no liquid crystallinity can be added to a liquid crystal composition using a polymerizable liquid crystal compound having an acrylic group (0 to 20%).
  • the addition of the polyfunctional polymerizable compound is for the purpose of improving the heat resistance of the film, and it is not described that the alignment mode can be controlled.
  • the tilt angle can be controlled by combining polymerizable liquid crystal compounds for vertical and horizontal alignment films. Among them, it has been reported that the tilt angle of the O-plate film can be controlled, but no data other than the tilt angle ( ⁇ nd, haze value, etc.) has been reported (Patent Document 3).
  • the present invention has been made in view of such circumstances, and has excellent optical anisotropy, and the retardation value and transparency are stably maintained even at high temperatures, and is excellent in chemical resistance and heat resistance.
  • An object of the present invention is to provide a polymerizable liquid crystal composition in which a polymer is provided and the alignment mode is easily controlled, a polymer obtained by using the composition, and a hybrid alignment film obtained by using these.
  • the present inventors add a small amount of a certain polyvalent acrylate compound to a polymerizable liquid crystal composition for a horizontal alignment film containing a certain polymerizable liquid crystal compound.
  • a certain polyvalent acrylate compound to a polymerizable liquid crystal composition for a horizontal alignment film containing a certain polymerizable liquid crystal compound.
  • the orientation mode can be easily controlled.
  • a stable polymerizable liquid crystal composition can be obtained, a polymer or film obtained from the polymerizable liquid crystal composition has excellent optical anisotropy and heat resistance, and a hybrid alignment film can be obtained.
  • the present invention has been completed.
  • the present invention 1. (A) at least one selected from polymerizable liquid crystal compounds represented by the following formula [1], (B) at least one selected from polymerizable liquid crystal compounds represented by the following formula [2], and (C) at least one structure selected from a trimethylolpropane structure, a pentaerythritol structure, and an ethylene glycol structure, or from these Containing at least one selected from polyhydric acrylate compounds obtained from polyhydric alcohols having 3 to 50 oxygen atoms in total and acrylic acid or derivatives thereof, having a structure in which at least one selected is condensed.
  • a polymerizable liquid crystal composition characterized by [Wherein R 1 , R 3 and R 4 each independently represents the following formula [3] or [4] (In the formula, X is a hydrogen atom or a methyl group. The broken line is a bond.) It is an organic group represented by.
  • R 2 is a hydrogen atom, a halogen atom, a cyano group or a methoxy group.
  • n1, n2 and n3 are each independently an integer of 2 to 10.
  • q is 0 or 1.
  • p is 1 when q is 0, and 0 or 1 when q is 1.
  • r is 1 or 2;
  • s is 1 when r is 1 and 0 when r is 2. ] 2.
  • polymerizable liquid crystal composition wherein the polyvalent acrylate compound (C) is represented by the following formula [5] or [6]: (In the formula, R 5 represents a methyl group, or the following formula [7] or [8]. It is an organic group represented by. n4 to n10 are each independently an integer of 0 to 10. n11 is an integer of 4 to 10. A broken line is a bond. ) 3.
  • the polymerizable liquid crystal compound (B) is a polymerizable liquid crystal composition of 1 or 2 represented by the following formula [9]: (Wherein n2, n3, r and s are the same as above) 4.
  • the polymerizable liquid crystal composition of the present invention not only has excellent optical anisotropy, but also gives a polymer having stable anisotropy and transparency in a high temperature environment.
  • the polymerizable liquid crystal composition of the present invention has an advantage that the orientation mode (horizontal, hybrid) of a film obtained therefrom can be easily controlled by containing a small amount of the polyvalent acrylate compound (C). ing. Therefore, the polymer obtained from the composition of the present invention can be suitably used as an optically anisotropic film such as a polarizing plate or a retardation plate.
  • Polymerizable liquid crystal compound means a compound having a polymerizable portion such as an acryl group and an ⁇ -methylene- ⁇ -butyrolactone ring and a liquid crystal structure portion in the molecule and exhibiting a liquid crystal phase.
  • the “liquid crystal structure” means a structure having a spacer portion and a mesogen portion, which is generally used for representing liquid crystal molecules.
  • Liquid crystal composition means a composition having a characteristic of exhibiting a liquid crystal phase.
  • Liquid crystallinity means exhibiting a liquid crystal phase.
  • the polymerizable liquid crystal compounds (A) and (B) used in the present invention have a liquid crystal structure portion, and further have one or both of an acrylic group and an ⁇ -methylene- ⁇ -butyrolactone structure.
  • ⁇ -Methylene- ⁇ -butyrolactone is less affected by steric hindrance than ⁇ -alkylidene- ⁇ -butyrolactone having a polymerizable group, and can exhibit a very excellent effect of having high polymerizability. And it is effective in order to provide high Tg and heat resistance to the polymer obtained using this compound.
  • polymerizable liquid crystal compound (A) The polymerizable liquid crystal compound (A) used in the present invention is represented by the following formula [1].
  • R 1 represents the following formula [3] or [4] (In the formula, X is a hydrogen atom or a methyl group. The broken line is a bond.) It is an organic group represented by.
  • R 2 is a hydrogen atom, a halogen atom, a cyano group or a methoxy group.
  • a fluorine atom is particularly preferable.
  • R 2 is preferably a hydrogen atom, a methoxy group or a cyano group, more preferably a hydrogen atom or a cyano group.
  • the repeating part of a methylene group is a part called a spacer part.
  • n1 represents the number of repeating methylene groups and is independently an integer of 2 to 10, preferably an integer of 3 to 6.
  • q is 0 or 1.
  • p is 1 when q is 0, and 0 or 1 when q is 1.
  • the polymerizable liquid crystal compound (A) exhibits a liquid crystal phase such as a smectic phase or a nematic phase. This characteristic is useful in the field of application utilizing optical anisotropy such as a polarizing plate and a retardation plate.
  • polymerizable liquid crystal compound (A) examples include, but are not limited to, compounds represented by the following formulas (1) to (25).
  • Me represents a methyl group.
  • Polymerizable liquid crystal compound (B) The polymerizable liquid crystal compound (B) used in the present invention is represented by the following formula [2].
  • R 3 and R 4 have the same meaning as R 1 described above and may be the same or different from each other.
  • n2 and n3 each represents the number of repeating methylene groups, each independently an integer of 2 to 10, preferably an integer of 3 to 6.
  • r is 1 or 2;
  • s is 1 when r is 1 and 0 when r is 2.
  • R 3 and R 4 are preferably an organic group represented by the formula [3].
  • a compound represented by the following formula [9] is particularly preferable. (Wherein n2, n3, r and s are the same as above)
  • polymerizable liquid crystal compound (B) examples include compounds represented by the following formulas (26) to (116), but are not limited thereto.
  • the polyvalent acrylate compound (C) used in the present invention has at least one structure selected from a trimethylolpropane structure, a pentaerythritol structure and an ethylene glycol structure, or a structure in which at least one selected from these is condensed.
  • R 5 represents a methyl group or the following formula [7] or [8]. It is an organic group represented by. n4 to n10 are each independently an integer of 0 to 10. n11 is an integer of 4 to 10. A broken line is a bond. )
  • polyvalent acrylate compound (C) examples include compounds represented by the following formulas (117) to (127), but are not limited thereto.
  • polyvalent acrylate compound (C) Commercially available products can be used as the polyvalent acrylate compound (C), and examples thereof include KAYARAD DPHA, PET30 manufactured by Nippon Kayaku Co., Ltd., ATM-35E manufactured by Shin-Nakamura Chemical Co., Ltd., and ADPH. .
  • the polymerizable liquid crystal composition according to the present invention contains at least one polymerizable liquid crystal compound (A), at least one polymerizable liquid crystal compound (B), and at least one polyvalent acrylate compound (C).
  • a polyvalent acrylate compound (C) the compound represented by the said Formula [5] or [6] is preferable.
  • the content of the polymerizable liquid crystal compound (A) is 100 to 1,900 parts by mass, preferably 400 to 900 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound (B).
  • the content of the polyvalent acrylate compound (C) is 0.5 to 5 with respect to 100 parts by mass of the total of the polymerizable liquid crystal compounds (A) and (B) (hereinafter collectively referred to as the total liquid crystal compound).
  • Mass parts are preferred, more preferably 1 to 3 parts by mass.
  • a photopolymerization initiator a thermal polymerization initiator, and a photosensitizer can be added for the purpose of improving the polymerization reactivity.
  • the photopolymerization initiator examples include benzoin ethers such as benzoin methyl ether, acetophenones such as diethoxyacetophenone, benzyl ketals such as benzyldimethyl ketal, and the like. Such a photoinitiator may be used individually by 1 type or in combination of multiple types.
  • the addition amount of the photopolymerization initiator is preferably 5 parts by mass or less, more preferably 0.5 to 2.0 parts by mass with respect to 100 parts by mass of the total liquid crystalline compounds.
  • thermal polymerization initiator examples include 2,2'-azobisisobutyronitrile.
  • the thermal polymerization initiator may be used alone or in combination of two or more.
  • the addition amount is preferably 5 parts by mass or less, more preferably 0.5 to 2.0 parts by mass with respect to 100 parts by mass of the total liquid crystal compounds.
  • the photosensitizer examples include anthracene photosensitizers such as anthracene.
  • a photosensitizer may be used alone or in combination of two or more.
  • the addition amount is preferably 5 parts by mass or less with respect to 100 parts by mass of the total liquid crystal compounds.
  • the above-mentioned photopolymerization initiator can be used in combination with at least one of a thermal polymerization initiator and a photosensitizer.
  • a stabilizer may be added to the polymerizable liquid crystal composition of the present invention for the purpose of improving its storage stability.
  • the stabilizer include hydroquinone monoalkyl ethers such as hydroquinone and hydroquinone monomethyl ether, and 4-t-butylcatechol.
  • a stabilizer may be used alone or in combination of two or more. The addition amount is preferably 0.1 parts by mass or less with respect to 100 parts by mass of the total liquid crystal compounds.
  • an adhesion promoter may be added to the polymerizable liquid crystal composition of the present invention for the purpose of improving the adhesion to the substrate.
  • adhesion promoters chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, vinyltrichlorosilane; trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxy Silane, phenyltriethoxysilane, ⁇ -chloropropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - (N-piperidinyl) prop
  • the adhesion promoter may be used alone or in combination of two or more.
  • the addition amount is preferably 1 part by mass or less with respect to 100 parts by mass of the total liquid crystal compounds.
  • an organic solvent can be added to the polymerizable liquid crystal composition of the present invention for the purpose of adjusting the viscosity.
  • liquid crystal properties may not be exhibited in a state containing an organic solvent.
  • organic solvent examples include ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene and xylene; polar solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone; Esters such as butyl acetate and ethyl lactate; methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, 2-ethoxypropionic acid Alkoxy esters such as ethyl; glycol dialkyl ethers such as ethylene glycol dimethyl ether and propylene glycol dimethyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Diglycol dialkyl ethers such as ruethyl ether and dipropylene glycol dimethyl ether
  • organic solvents may be used alone or in combination of two or more.
  • the amount of the organic solvent used is preferably about 60 to 95% by mass in the polymerizable liquid crystal composition.
  • a surfactant may be added to the polymerizable liquid crystal composition of the present invention for the purpose of improving the affinity with the substrate.
  • the surfactant is not particularly limited, and examples thereof include fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, etc., but fluorine-based surfactants having a high effect of improving affinity with the substrate. Agents are preferred.
  • fluorosurfactants hereinafter referred to as trade names
  • EFTOP EF301, EF303, EF352 manufactured by Tochem Products
  • MegaFuck F171, F173, R-30 manufactured by DIC Corporation
  • FLORARD FC430, FC431 Suditomo 3M Co., Ltd.
  • Asahi Guard AG710 Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.), etc.
  • the surfactants may be used alone or in combination of two or more.
  • the polymerizable liquid crystal compound (A) is 400 to 900 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound (B).
  • C) is 1 to 3 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compounds (A) and (B), and the photoinitiator is 100 parts by mass of the polymerizable liquid crystal compounds (A) and (B).
  • the preparation method of the polymerizable liquid crystal composition of the present invention is not particularly limited, and each component constituting the polymerizable liquid crystal composition may be mixed at one time or sequentially.
  • the order of adding the components in the sequential mixing is arbitrary.
  • the mixture which mixed them previously and other components may be mixed, and you may mix with another component separately, respectively.
  • the polymerizable liquid crystal composition of the present invention avoids unintentional induction of thermal polymerization in photopolymerization in a liquid crystal state and facilitates fixing of a uniform alignment state of molecules when producing an optical anisotropic body. It is preferable that the liquid crystal phase exhibits an entropy at room temperature (20 to 40 ° C., the same shall apply hereinafter). Further, when the polymerizable liquid crystal composition contains an organic solvent, it is preferable that an enantiomeric liquid crystal phase is exhibited at room temperature when the solvent is removed.
  • the polymerizable liquid crystal composition of the present invention can be suitably used as a composition for forming an orientation film or a coating solution.
  • a polymer can be obtained by subjecting the polymerizable liquid crystal composition of the present invention described above to light irradiation or heat treatment.
  • a film can be obtained by applying a polymerizable liquid crystal composition to a substrate by spin coating, a casting method, or the like, and performing light irradiation treatment.
  • the substrate glass, quartz, a color filter, a plastic sheet such as triacetyl cellulose (TAC), a film, or the like can be used.
  • TAC triacetyl cellulose
  • the substrate to be used is preferably subjected to an orientation treatment so as to obtain a tilt.
  • an alignment treatment method an alignment material containing a polyimide precursor, polyimide, polyvinyl cinnamate, etc. is applied, and an alignment treatment is performed by irradiating with rubbing or polarized ultraviolet rays obliquely, and a silicon dioxide oblique deposition film is formed.
  • an alignment method capable of obtaining a tilt in any case.
  • a step of heating with a hot plate or the like may be added as needed during the step of applying the polymerizable liquid crystal composition and the step of polymerizing with light or heat. This step is particularly effective as a means for removing the organic solvent from the composition when a polymerizable liquid crystal composition (coating liquid) containing the organic solvent is used.
  • an oriented film having optical anisotropy can be obtained by polymerizing the polymerizable liquid crystal composition in a state of exhibiting a liquid crystal phase.
  • a film having optical anisotropy can be obtained, and this film can be suitably used for a polarizing plate, a retardation plate and the like.
  • this film since this film has good transparency at high temperatures, it can be suitably used for electronic devices used in high-temperature environments such as in-vehicle display devices.
  • Retardation value of film The retardation value at a wavelength of 590 nm was measured using a retardation measuring device (RETS-100, manufactured by Otsuka Electronics Co., Ltd.).
  • FTS-100 retardation measuring device
  • AXOMETRIX Average Tilt Angle of Film The average tilt angle was measured using an AxoScan TM Mueller Matrix Polarimeter (manufactured by AXOMETRIX).
  • intermediate compound (I2) obtained above in a state where 2.2 g (10.0 mmol) of pyridinium chlorochromate (PCC) and 30.0 mL of dichloromethane were added to a 200 mL three-necked flask equipped with a condenser and stirred and mixed.
  • a solution prepared by dissolving 2.95 g (10.0 mmol) in 50.0 mL of dichloromethane was added dropwise, and the mixture was further stirred at 40 ° C. for 0.5 hour.
  • the solvent of the obtained solution was distilled off to obtain 1.3 g of a colorless solid.
  • the result of having measured this solid by NMR is shown below. From this result, it was confirmed that this colorless solid was an intermediate compound (F3) (yield 50%).
  • Examples and Comparative Examples Polymerizable liquid crystal composition and polymer (film) thereof
  • the compounds used in the following examples and comparative examples are as follows.
  • the compositions of the compositions used in Examples 1 to 8 are shown in Table 1, and the compositions of the compositions used in Comparative Examples 1 to 5 are shown in Table 2.
  • the following compounds (C1), (C2), (C3), (C5) and (E1) are products of Shin-Nakamura Chemical Co., Ltd.
  • compound (C4) is a product of Nippon Kayaku Co., Ltd. Yes
  • compound (E2) is a product of Tokyo Chemical Industry Co., Ltd.
  • Compound (E3) is known.
  • Polymerizable liquid crystal composition and polymer (film) thereof 150 mg of polymerizable liquid crystal compound (A1), 90 mg of polymerizable liquid crystal compound (A2), 60 mg of polymerizable liquid crystal compound (B1), 9 mg of polyvalent acrylate compound (C1), Irgacure 369 manufactured by Ciba Geigy Co., Ltd. (trade name) 4 mg and 0.6 mg of surfactant R30 (manufactured by DIC Corporation) were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
  • This polymerizable liquid crystal composition is applied to the liquid crystal alignment film surface of the substrate with a liquid crystal alignment film by spin coating (1,000 rpm, 20 seconds), pre-baked on a hot plate at 100 ° C. for 60 seconds, and then allowed to cool to room temperature. did. At this time, the polymerizable composition on the substrate was in a liquid crystal state.
  • the substrate with a liquid crystal alignment film used here has a thickness obtained by applying a liquid crystal alignment agent (SE-1410 manufactured by Nissan Chemical Industries, Ltd.) to the ITO surface of a glass substrate with ITO by spin coating and baking at 230 ° C. A 100-nm thin film is formed and then subjected to a rubbing treatment.
  • the coating film formed on the substrate with a liquid crystal alignment film was irradiated with light having a strength of 2,000 mJ / cm 2 using a metal halide lamp in a nitrogen atmosphere to polymerize the polymerizable liquid crystal composition. .
  • the film thickness of the obtained film was 1.8 ⁇ m, and when observed with a polarizing microscope, it was confirmed that the film was hybrid-aligned on the substrate surface (average tilt 40 °).
  • the retardation value was 117 nm and the haze value was 1.44.
  • the retardation value was 109 nm and the haze value was 1.30.
  • Polymerizable liquid crystal composition and polymer (film) thereof 150 mg of polymerizable liquid crystal compound (A1), 90 mg of polymerizable liquid crystal compound (A2), 60 mg of polymerizable liquid crystal compound (B1), 15 mg of polyvalent acrylate compound (C2), Irgacure 369 manufactured by Ciba Geigy Co., Ltd. (trade name) 4 mg and 0.6 mg of surfactant R30 (manufactured by DIC Corporation) were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
  • a film was produced in the same manner as in Example 1 except that this polymerizable liquid crystal composition was used.
  • the polymerizable composition on the substrate after pre-baking was in a liquid crystal state.
  • the film thickness of the obtained film was 1.8 ⁇ m, and when observed with a polarizing microscope, it was confirmed that the film was hybrid-aligned on the substrate surface (average tilt 40 °).
  • the retardation value was 121 nm and the haze value was 0.66.
  • the retardation value was 109 nm and the haze value was 0.38.
  • Polymerizable liquid crystal composition and polymer (film) thereof 150 mg of polymerizable liquid crystal compound (A1), 90 mg of polymerizable liquid crystal compound (A2), 60 mg of polymerizable liquid crystal compound (B1), 15 mg of polyvalent acrylate compound (C3), Irgacure 369 manufactured by Ciba Geigy Co., Ltd. (trade name) 4 mg and 0.6 mg of surfactant R30 (manufactured by DIC Corporation) were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
  • a film was produced in the same manner as in Example 1 except that this polymerizable liquid crystal composition was used.
  • the polymerizable composition on the substrate after pre-baking was in a liquid crystal state.
  • the film thickness of the obtained film was 1.8 ⁇ m, and when observed with a polarizing microscope, it was confirmed that the film was hybrid-aligned on the substrate surface (average tilt 40 °).
  • the retardation value was 115 nm and the haze value was 0.08.
  • the retardation value was 98 nm and the haze value was 0.07.
  • Polymerizable liquid crystal composition and polymer (film) thereof 150 mg of polymerizable liquid crystal compound (A1), 90 mg of polymerizable liquid crystal compound (A2), 60 mg of polymerizable liquid crystal compound (B1), 9 mg of polyvalent acrylate compound (C4), Irgacure 369 manufactured by Ciba Geigy Co., Ltd. (trade name) 4 mg and 0.6 mg of surfactant R30 (manufactured by DIC Corporation) were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
  • a film was produced in the same manner as in Example 1 except that this polymerizable liquid crystal composition was used.
  • the polymerizable composition on the substrate after pre-baking was in a liquid crystal state.
  • the film thickness of the obtained film was 1.8 ⁇ m, and when observed with a polarizing microscope, it was confirmed that the film was hybrid-aligned on the substrate surface (average tilt 40 °).
  • the retardation value was 101 nm, and the haze value was 0.05.
  • the retardation value was 92 nm and the haze value was 0.07.
  • Polymerizable liquid crystal composition and polymer (film) thereof 150 mg of polymerizable liquid crystal compound (A1), 90 mg of polymerizable liquid crystal compound (A2), 60 mg of polymerizable liquid crystal compound (B1), 15 mg of polyvalent acrylate compound (C4), Irgacure 369 manufactured by Ciba Geigy Co., Ltd. (trade name) 4 mg and 0.6 mg of surfactant R30 (manufactured by DIC Corporation) were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
  • a film was produced in the same manner as in Example 1 except that this polymerizable liquid crystal composition was used.
  • the polymerizable composition on the substrate after pre-baking was in a liquid crystal state.
  • the film thickness of the obtained film was 1.8 ⁇ m, and when observed with a polarizing microscope, it was confirmed that the film was hybrid-aligned on the substrate surface (average tilt 40 °).
  • the retardation value was 96 nm and haze value was 1.15. When this film was heated on a hot plate at 200 ° C. for 30 minutes, the retardation value was 95 nm and the haze value was 2.18.
  • Polymerizable liquid crystal composition and polymer (film) thereof 150 mg of polymerizable liquid crystal compound (A1), 90 mg of polymerizable liquid crystal compound (A2), 60 mg of polymerizable liquid crystal compound (B1), 3 mg of polyvalent acrylate compound (C5), Irgacure 369 manufactured by Ciba Geigy Co., Ltd. (trade name) 4 mg and 0.6 mg of surfactant R30 (manufactured by DIC Corporation) were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
  • a film was produced in the same manner as in Example 1 except that this polymerizable liquid crystal composition was used.
  • the polymerizable composition on the substrate after pre-baking was in a liquid crystal state.
  • the film thickness of the obtained film was 1.8 ⁇ m, and when observed with a polarizing microscope, it was confirmed that the film was hybrid-aligned on the substrate surface (average tilt 40 °).
  • the retardation value was 106 nm and the haze value was 0.03.
  • the retardation value was 99 nm and the haze value was 0.08.
  • a film was produced in the same manner as in Example 1 except that this polymerizable liquid crystal composition was used.
  • the polymerizable composition on the substrate after pre-baking was in a liquid crystal state.
  • the film thickness of the obtained film was 1.7 ⁇ m, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented (tilt ⁇ 10 °) on the substrate surface.
  • the retardation value was 296 nm and the haze value was 0.08.
  • the retardation value was 201 nm and the haze value was 0.08.
  • a film was produced in the same manner as in Example 1 except that this polymerizable liquid crystal composition was used.
  • the polymerizable composition on the substrate after pre-baking was in a liquid crystal state.
  • the film thickness of the obtained film was 1.9 ⁇ m, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented (tilt ⁇ 10 °) on the substrate surface.
  • the retardation value was 261 nm and the haze value was 0.08.
  • the retardation value was 144 nm and the haze value was 0.08.
  • a film was produced in the same manner as in Example 1 except that this polymerizable liquid crystal composition was used.
  • the polymerizable composition on the substrate after pre-baking was in a liquid crystal state.
  • the film thickness of the obtained film was 1.9 ⁇ m, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented (tilt ⁇ 10 °) on the substrate surface.
  • the retardation value was 328 nm and haze value was 0.16. When this film was heated on a hot plate at 200 ° C. for 30 minutes, the retardation value was 265 nm and the haze value was 0.16.
  • a film was produced in the same manner as in Example 1 except that this polymerizable liquid crystal composition was used.
  • the polymerizable composition on the substrate after pre-baking was in a liquid crystal state.
  • the film thickness of the obtained film was 1.8 ⁇ m, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented (tilt ⁇ 10 °) on the substrate surface.
  • the retardation value was 289 nm and haze value was 0.16.
  • the retardation value was 209 nm and the haze value was 0.16.
  • a film was produced in the same manner as in Example 1 except that this polymerizable liquid crystal composition was used.
  • the polymerizable composition on the substrate after pre-baking was in a liquid crystal state.
  • the film thickness of the obtained film was 1.8 ⁇ m, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented (tilt ⁇ 10 °) on the substrate surface.
  • the retardation value was 258 nm and haze value was 1.49. When this film was heated on a hot plate at 200 ° C. for 30 minutes, the retardation value was 18 nm and the haze value was 0.24.
  • Example 3 The summary of Examples 1 to 6 and Comparative Examples 1 to 5 is shown in Table 3 below.
  • ⁇ nd value thermal stability (%) is the ratio of ⁇ nd value after baking to ⁇ nd value before baking.
  • retardation value angle dependency of the films prepared in Examples 1 to 6 at a wavelength of 590 nm is shown in FIG. 1
  • retardation value angle dependency of the films prepared in Comparative Examples 1 to 5 at a wavelength of 590 nm is shown in FIG. Show.
  • Example 7 Polymerizable liquid crystal composition and polymer (film) thereof Polymerizable liquid crystal compound (A1) 150 mg, polymerizable liquid crystal compound (A2) 90 mg, polymerizable liquid crystal compound (B1) 60 mg, and polyvalent acrylate compound (C4) 4.5 mg, Irgacure 369 manufactured by Ciba Geigy Co., which is a photopolymerization initiator (Product name) 4 mg and surfactant R30 (manufactured by DIC Corporation) 0.6 mg were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
  • Irgacure 369 manufactured by Ciba Geigy Co.
  • surfactant R30 manufactured by DIC Corporation
  • This polymerizable liquid crystal composition is applied to the liquid crystal alignment film surface of the substrate with a liquid crystal alignment film by spin coating (1,000 rpm, 20 seconds), pre-baked on a hot plate at 100 ° C. for 60 seconds, and then allowed to cool to room temperature. did. At this time, the polymerizable composition on the substrate was in a liquid crystal state.
  • the substrate with a liquid crystal alignment film used here has a thickness obtained by applying a liquid crystal alignment agent (PAOC-120 manufactured by Nissan Chemical Industries, Ltd.) to the ITO surface of a glass substrate with ITO by spin coating and baking at 130 ° C. After forming a 200 nm thin film, it is irradiated with polarized UV light of 500 mJ / cm 2 obliquely (40 °).
  • the coating film formed on the substrate with a liquid crystal alignment film was irradiated with light having a strength of 2,000 mJ / cm 2 using a metal halide lamp in a nitrogen atmosphere to polymerize the polymerizable liquid crystal composition. .
  • the film thickness of the obtained film was 1.8 ⁇ m, and when observed with a polarizing microscope, it was confirmed that the film was hybrid-aligned on the substrate surface (average tilt 40 °).
  • the retardation value was 143 nm and the haze value was 0.13.
  • Example 8 Polymerizable liquid crystal composition and polymer (film) thereof
  • the polymerizable liquid crystal composition obtained in Example 7 was applied to the liquid crystal alignment film surface of the substrate with a liquid crystal alignment film by spin coating (1,000 rpm, 20 seconds) and prebaked on a hot plate at 100 ° C. for 60 seconds. Then, it was left to cool to room temperature. At this time, the polymerizable composition on the substrate was in a liquid crystal state.
  • the substrate with a liquid crystal alignment film used here has a thickness obtained by applying a liquid crystal alignment agent (PAOC-120 manufactured by Nissan Chemical Industries, Ltd.) to the ITO surface of a glass substrate with ITO by spin coating and baking at 130 ° C. After forming a 200 nm thin film, it was irradiated with polarized UV light of 1,000 mJ / cm 2 from directly above.
  • a liquid crystal alignment agent PAOC-120 manufactured by Nissan Chemical Industries, Ltd.
  • the coating film formed on the substrate with a liquid crystal alignment film was irradiated with light having a strength of 2,000 mJ / cm 2 using a metal halide lamp in a nitrogen atmosphere to polymerize the polymerizable liquid crystal composition. .
  • the film thickness of the obtained film was 1.8 ⁇ m, and when observed with a polarizing microscope, it was confirmed that the film was horizontally aligned on the substrate surface.
  • the retardation value was 306 nm and the haze value was 0.13.
  • FIG. 3 shows the retardation value angle dependency of the films prepared in Examples 7 and 8 at a wavelength of 590 nm.
  • the polymer obtained from the composition of the present invention can be suitably used as an optically anisotropic film such as a polarizing plate or a retardation plate.

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Abstract

Provided is a polymerizable liquid crystal composition characterized in comprising: (A) at least one species selected from polymerizable liquid crystal compounds represented by formula [1]; (B) at least one species selected from polymerizable liquid crystal compounds represented by formula [2]; and (C) at least one species selected from polyvalent acrylate compounds having at least one type of structure selected from the group consisting of a trimethylolpropane structure, a pentaerythritol structure, and an ethylene glycol structure, or a structure in which at least one species selected from the above structures is condensed. (In the formulae, R1, R3, and R4 are each independently an organic group represented by formula [3] or [4] (in which X is hydrogen or methyl, and the dashed lines are atomic bonds); R2 is hydrogen, halogen, cyano, or methoxy; n1, n2, and n3 are each independently an integer 2-10; q is 0 or 1; p is 1 when q is 0, and is 0 or 1 when q is 1; r is 1 or 2; and s is 1 when r is 1, and is 0 when r is 2.)

Description

重合性液晶組成物および配向フィルムPolymerizable liquid crystal composition and alignment film
　本発明は、重合性液晶組成物、これを用いて得られる重合体、及び配向フィルムに関する。詳しくは、表示装置や記録材料等の光学特性を有する材料、特に、液晶ディスプレイ用の偏光板、位相差板等の光学補償フィルムに好適に利用できる重合性液晶組成物、これを用いて得られる重合体、及びこれらを用いて得られるハイブリッド配向フィルムに関する。 The present invention relates to a polymerizable liquid crystal composition, a polymer obtained using the polymerizable liquid crystal composition, and an alignment film. Specifically, a polymerizable liquid crystal composition that can be suitably used for a material having optical characteristics such as a display device or a recording material, in particular, an optical compensation film such as a polarizing plate for a liquid crystal display or a retardation plate, and obtained using the same. The present invention relates to a polymer and a hybrid alignment film obtained by using these.
　液晶表示装置の表示品位の向上や軽量化等の要求から、偏光板や位相差板等の光学補償フィルムとして、内部の分子配向構造が制御された高分子フィルムの要求が高まっている。この要求に応えるべく、重合性液晶化合物が有する光学異方性を利用したフィルムの開発がなされている。
　ここで用いられる重合性液晶化合物は、一般に、重合性基と液晶構造部位（スペーサ部とメソゲン部とを有する構造部位）とを有する液晶化合物であり、この重合性基としてアクリル基が広く用いられている。 Due to demands for improving the display quality and weight reduction of liquid crystal display devices, there is an increasing demand for polymer films with controlled internal molecular orientation structures as optical compensation films such as polarizing plates and retardation plates. In order to meet this demand, development of a film utilizing the optical anisotropy of the polymerizable liquid crystal compound has been made.
The polymerizable liquid crystal compound used here is generally a liquid crystal compound having a polymerizable group and a liquid crystal structure part (structure part having a spacer part and a mesogen part), and an acrylic group is widely used as the polymerizable group. ing.
　このような重合性液晶化合物は、一般的に、紫外線等の放射線を照射して重合する方法で重合体（フィルム）とされる。
　例えば、アクリル基を有する特定の重合性液晶化合物を支持体間に担持し、この化合物を液晶状態に保持しつつ放射線を照射して重合体を得る方法（特許文献１）や、アクリル基を有する２種類の重合性液晶化合物の混合物又はこの混合物にカイラル液晶を混合した組成物に光重合開始剤を添加し、紫外線を照射して重合体を得る方法が知られている（特許文献２）。 Such a polymerizable liquid crystal compound is generally made into a polymer (film) by a method of polymerizing by irradiation with radiation such as ultraviolet rays.
For example, a method in which a specific polymerizable liquid crystal compound having an acrylic group is supported between supports and a polymer is obtained by irradiating radiation while maintaining the compound in a liquid crystal state (Patent Document 1), or having an acrylic group There is known a method of obtaining a polymer by adding a photopolymerization initiator to a mixture of two kinds of polymerizable liquid crystal compounds or a composition obtained by mixing a chiral liquid crystal with this mixture and irradiating ultraviolet rays (Patent Document 2).
　上記各方法により得られる重合体（フィルム）は、偏光板や位相差板用のフィルム等として、モニタやテレビ等の表示装置だけでなく、自動車内等のような高温環境で使用される表示装置に搭載される。このため、高温環境下において、透明性を維持することは表示装置用材料として非常に重要である。
　しかし、重合性液晶化合物から得られたフィルムは、そのガラス転移温度（以下、Ｔｇと称する）が使用環境の温度以下の場合、特に高温環境下では、分子の微視的な揺らぎが発生するため配向が乱れ、光学異方性が著しく低下する場合がある。 The polymer (film) obtained by each of the above methods is a display device used in a high-temperature environment such as in a car as well as a display device such as a monitor or a television as a polarizing plate or a retardation film. Mounted on. For this reason, maintaining transparency in a high temperature environment is very important as a display device material.
However, since a film obtained from a polymerizable liquid crystal compound has a glass transition temperature (hereinafter referred to as Tg) that is lower than the temperature of the use environment, particularly in a high temperature environment, molecular fluctuations occur. The orientation may be disturbed, and the optical anisotropy may be significantly reduced.
　更に、ディスプレイの分野では近年、これらの材料をＩｎ　Ｃｅｌｌ位相差フィルムとして用いるプロセス簡略化の検討が積極的に進められている。このＩｎ　Ｃｅｌｌ技術に用いられる材料は、さらに高い熱安定性及び耐薬品性が要求されている。 Furthermore, in the field of displays, in recent years, studies on simplification of processes using these materials as In Cell retardation films have been actively promoted. The material used for this In Cell technology is required to have higher thermal stability and chemical resistance.
　一方、重合性液晶化合物の配向モードの違いによって、水平、垂直、ハイブリッド配向等の各種配向フィルムが得られ、さまざまな平均チルト角度を示すハイブリッド配向フィルムも報告されている（特許文献３）。 On the other hand, various alignment films such as horizontal, vertical and hybrid alignment are obtained depending on the alignment mode of the polymerizable liquid crystal compound, and hybrid alignment films exhibiting various average tilt angles have been reported (Patent Document 3).
　ところで、液晶組成物に、ある特定の化合物を少量添加するだけで、得られたフィルムの配向モード（例えば、水平、ハイブリッド）を簡単にコントロールが可能となれば、液晶ディスプレイ分野で幅広く応用できる。
　また、一つの材料を用いて、プロセスを変えることにより、水平又はハイブリッド配向フィルムを簡単に作り分けることが可能となれば、液晶ディスプレイ分野で幅広い応用が期待される。 By the way, if the orientation mode (for example, horizontal or hybrid) of the obtained film can be easily controlled by adding a small amount of a specific compound to the liquid crystal composition, it can be widely applied in the liquid crystal display field.
If a single material can be used to change the process and a horizontal or hybrid alignment film can be easily created, a wide range of applications can be expected in the liquid crystal display field.
　特許文献４には、アクリル基を有する重合性液晶性化合物を用いる液晶組成物に液晶性を示さない多官能性重合性化合物を添加することができる（０～２０％）と記載されている。しかし、多官能性重合性化合物の添加はフィルムの耐熱性の向上のためであり、それによって配向モードのコントロールが得られることについては記載されていない。 Patent Document 4 describes that a polyfunctional polymerizable compound having no liquid crystallinity can be added to a liquid crystal composition using a polymerizable liquid crystal compound having an acrylic group (0 to 20%). However, the addition of the polyfunctional polymerizable compound is for the purpose of improving the heat resistance of the film, and it is not described that the alignment mode can be controlled.
　また、垂直及び水平配向フィルム用の重合性液晶化合物を組み合わせることによりチルト角度のコントロールができることが報告されている。その中で、Ｏ－プレートフィルムのチルト角度のコントロールが得られることが報告されているが、チルト角度以外のデータ（Δｎｄ、ヘイズ値等）は報告されていない（特許文献３）。 It has also been reported that the tilt angle can be controlled by combining polymerizable liquid crystal compounds for vertical and horizontal alignment films. Among them, it has been reported that the tilt angle of the O-plate film can be controlled, but no data other than the tilt angle (Δnd, haze value, etc.) has been reported (Patent Document 3).
特開昭６２－７０４０７号公報JP-A-62-70407 特開平９－２０８９５７号公報JP-A-9-208957 国際公開第２００８／０５２３７６号International Publication No. 2008/052376 国際公開第９８／０４６５１号International Publication No. 98/04651
　本発明は、このような事情に鑑みてなされたものであり、優れた光学異方性を有するとともに、高温においてもリタデーション値及び透明性が安定に保たれ、耐薬品性及び耐熱性に優れた重合体を与え、更に配向モードのコントロールが容易な重合性液晶組成物、これを用いて得られる重合体、及びこれらを用いて得られるハイブリッド配向フィルムを提供することを目的とする。 The present invention has been made in view of such circumstances, and has excellent optical anisotropy, and the retardation value and transparency are stably maintained even at high temperatures, and is excellent in chemical resistance and heat resistance. An object of the present invention is to provide a polymerizable liquid crystal composition in which a polymer is provided and the alignment mode is easily controlled, a polymer obtained by using the composition, and a hybrid alignment film obtained by using these.
　本発明者らは、上記課題を解決すべく鋭意検討を重ねた結果、ある種の重合性液晶化合物を含む水平配向フィルム用の重合性液晶組成物にある種の多価アクリレート化合物を少量添加することで、配向モードのコントロールが容易になることを見出した。更に、安定な重合性液晶性組成物が得られること、その重合性液晶性組成物から得られる重合体やフィルムが優れた光学異方性及び耐熱性を有すること、並びにハイブリッド配向フィルムが得られることを見出し、本発明を完成した。 As a result of intensive studies to solve the above problems, the present inventors add a small amount of a certain polyvalent acrylate compound to a polymerizable liquid crystal composition for a horizontal alignment film containing a certain polymerizable liquid crystal compound. Thus, it was found that the orientation mode can be easily controlled. Furthermore, a stable polymerizable liquid crystal composition can be obtained, a polymer or film obtained from the polymerizable liquid crystal composition has excellent optical anisotropy and heat resistance, and a hybrid alignment film can be obtained. As a result, the present invention has been completed.
　すなわち、本発明は、
１．（Ａ）下記式［１］で表される重合性液晶化合物から選ばれる少なくとも１種、
（Ｂ）下記式［２］で表される重合性液晶化合物から選ばれる少なくとも１種、及び
（Ｃ）トリメチロールプロパン構造、ペンタエリスリトール構造及びエチレングリコール構造から選ばれる少なくとも１種の構造又はこれらから選ばれる少なくとも１種が縮合した構造を有する、全体で３以上５０以下の酸素原子を有する多価アルコールとアクリル酸又はその誘導体とから得られる多価アクリレート化合物から選ばれる少なくとも１種
を含有することを特徴とする重合性液晶組成物、
Figure JPOXMLDOC01-appb-C000006
 ［式中、Ｒ1、Ｒ3及びＲ4は、それぞれ独立に下記式［３］又は［４］
Figure JPOXMLDOC01-appb-C000007
 （式中、Ｘは、水素原子又はメチル基である。破線は結合手である。）
で表される有機基である。Ｒ2は、水素原子、ハロゲン原子、シアノ基又はメトキシ基である。ｎ１、ｎ２及びｎ３は、それぞれ独立に２～１０の整数である。ｑは０又は１である。ｐは、ｑが０のときは１、ｑが１のときは０又は１である。ｒは１又は２である。ｓは、ｒが１のときは１、ｒが２のときは０である。］
２．上記多価アクリレート化合物（Ｃ）が、下記式［５］又は［６］で表される１の重合性液晶組成物、
Figure JPOXMLDOC01-appb-C000008
 （式中、Ｒ5は、メチル基、又は下記式［７］若しくは［８］
Figure JPOXMLDOC01-appb-C000009
 で表される有機基である。ｎ４～ｎ１０は、それぞれ独立に０～１０の整数である。ｎ１１は４～１０の整数である。破線は結合手である。）
３．前記重合性液晶化合物（Ｂ）が、下記式［９］で表される１又は２の重合性液晶組成物、
Figure JPOXMLDOC01-appb-C000010
 （式中、ｎ２、ｎ３、ｒ及びｓは上記と同じ。）
４．１～３のいずれかの重合性液晶組成物から得られる重合体、
５．１～３のいずれかの重合性液晶組成物から得られる被膜、
６．１～３のいずれかの重合性液晶組成物から得られるハイブリッド配向フィルム、
７．６の配向フィルムを備える光学部材
を提供する。 That is, the present invention
1. (A) at least one selected from polymerizable liquid crystal compounds represented by the following formula [1],
(B) at least one selected from polymerizable liquid crystal compounds represented by the following formula [2], and (C) at least one structure selected from a trimethylolpropane structure, a pentaerythritol structure, and an ethylene glycol structure, or from these Containing at least one selected from polyhydric acrylate compounds obtained from polyhydric alcohols having 3 to 50 oxygen atoms in total and acrylic acid or derivatives thereof, having a structure in which at least one selected is condensed. A polymerizable liquid crystal composition characterized by
Figure JPOXMLDOC01-appb-C000006
 [Wherein R 1 , R 3 and R 4 each independently represents the following formula [3] or [4]
Figure JPOXMLDOC01-appb-C000007
 (In the formula, X is a hydrogen atom or a methyl group. The broken line is a bond.)
It is an organic group represented by. R 2 is a hydrogen atom, a halogen atom, a cyano group or a methoxy group. n1, n2 and n3 are each independently an integer of 2 to 10. q is 0 or 1. p is 1 when q is 0, and 0 or 1 when q is 1. r is 1 or 2; s is 1 when r is 1 and 0 when r is 2. ]
2. 1 polymerizable liquid crystal composition, wherein the polyvalent acrylate compound (C) is represented by the following formula [5] or [6]:
Figure JPOXMLDOC01-appb-C000008
 (In the formula, R 5 represents a methyl group, or the following formula [7] or [8].
Figure JPOXMLDOC01-appb-C000009
 It is an organic group represented by. n4 to n10 are each independently an integer of 0 to 10. n11 is an integer of 4 to 10. A broken line is a bond. )
3. The polymerizable liquid crystal compound (B) is a polymerizable liquid crystal composition of 1 or 2 represented by the following formula [9]:
Figure JPOXMLDOC01-appb-C000010
 (Wherein n2, n3, r and s are the same as above)
4. A polymer obtained from any one of the polymerizable liquid crystal compositions of 1 to 3,
5.1 A film obtained from the polymerizable liquid crystal composition of any one of 1 to 3,
6.1 A hybrid alignment film obtained from the polymerizable liquid crystal composition according to any one of 1 to 3;
An optical member comprising an oriented film of 7.6 is provided.
　本発明の重合性液晶組成物は、優れた光学異方性を有するだけでなく、かつ、高温環境下における異方性及び透明性が安定な重合体を与える。また、本発明の重合性液晶組成物は、多価アクリレート化合物（Ｃ）を少量含有することで、これから得られたフィルムの配向モード（水平、ハイブリッド）を簡単にコントロールができるという利点を有している。
　したがって、本発明の組成物から得られる重合体は、偏光板や位相差板等の光学異方性フィルムとして好適に利用することができる。 The polymerizable liquid crystal composition of the present invention not only has excellent optical anisotropy, but also gives a polymer having stable anisotropy and transparency in a high temperature environment. In addition, the polymerizable liquid crystal composition of the present invention has an advantage that the orientation mode (horizontal, hybrid) of a film obtained therefrom can be easily controlled by containing a small amount of the polyvalent acrylate compound (C). ing.
Therefore, the polymer obtained from the composition of the present invention can be suitably used as an optically anisotropic film such as a polarizing plate or a retardation plate.
実施例１～６で得られた各フィルムの波長５９０ｎｍにおけるリタデーション値角度依存性を示す図である。It is a figure which shows the retardation value angle dependence in wavelength 590nm of each film obtained in Examples 1-6. 比較例１～５で得られた各フィルムの波長５９０ｎｍにおけるリタデーション値角度依存性を示す図である。It is a figure which shows the retardation value angle dependence in wavelength 590nm of each film obtained by Comparative Examples 1-5. 実施例７～８で得られた各フィルムの波長５９０ｎｍにおけるリタデーション値角度依存性を示す図である。It is a figure which shows the retardation value angle dependency in wavelength 590nm of each film obtained in Examples 7-8.
　この明細書における用語の使い方は次のとおりである。
　「重合性液晶化合物」は、分子中にアクリル基、α－メチレン－γ－ブチロラクトン環等の重合可能部位と液晶構造部位とを有し、かつ、液晶相を呈する化合物を意味する。この「液晶構造」とは、一般に液晶分子を表す場合に用いられる、スペーサ部とメソゲン部とを有する構造を意味する。「液晶組成物」は、液晶相を呈する特性を有する組成物を意味する。「液晶性」は、液晶相を呈することを意味する。 Terms used in this specification are as follows.
“Polymerizable liquid crystal compound” means a compound having a polymerizable portion such as an acryl group and an α-methylene-γ-butyrolactone ring and a liquid crystal structure portion in the molecule and exhibiting a liquid crystal phase. The “liquid crystal structure” means a structure having a spacer portion and a mesogen portion, which is generally used for representing liquid crystal molecules. “Liquid crystal composition” means a composition having a characteristic of exhibiting a liquid crystal phase. "Liquid crystallinity" means exhibiting a liquid crystal phase.
　本発明で用いる重合性液晶化合物（Ａ）及び（Ｂ）は、液晶構造部位を有し、更にアクリル基及びα－メチレン－γ－ブチロラクトン構造のどちらか一方又は両方を有する。
　α－メチレン－γ－ブチロラクトンは、重合性基を有するα－アルキリデン－γ－ブチロラクトンの中でも立体障害による影響が少なく、高い重合性を有するという非常に優れた効果を発揮し得る。そして、この化合物を用いて得られる重合体に高いＴｇや耐熱性を付与するために有効である。 The polymerizable liquid crystal compounds (A) and (B) used in the present invention have a liquid crystal structure portion, and further have one or both of an acrylic group and an α-methylene-γ-butyrolactone structure.
α-Methylene-γ-butyrolactone is less affected by steric hindrance than α-alkylidene-γ-butyrolactone having a polymerizable group, and can exhibit a very excellent effect of having high polymerizability. And it is effective in order to provide high Tg and heat resistance to the polymer obtained using this compound.
［重合性液晶化合物（Ａ）］
　本発明で用いる重合性液晶化合物（Ａ）は、下記式［１］で表される。
Figure JPOXMLDOC01-appb-C000011
 [Polymerizable liquid crystal compound (A)]
The polymerizable liquid crystal compound (A) used in the present invention is represented by the following formula [1].
Figure JPOXMLDOC01-appb-C000011
　式［１］中、Ｒ1は、下記式［３］又は［４］
Figure JPOXMLDOC01-appb-C000012
 （式中、Ｘは、水素原子又はメチル基である。破線は結合手である。）
で表される有機基である。 In the formula [1], R 1 represents the following formula [3] or [4]
Figure JPOXMLDOC01-appb-C000012
 (In the formula, X is a hydrogen atom or a methyl group. The broken line is a bond.)
It is an organic group represented by.
　式［１］中、Ｒ2は、水素原子、ハロゲン原子、シアノ基又はメトキシ基である。上記ハロゲン原子としては、特にフッ素原子が好ましい。Ｒ2としては、水素原子、メトキシ基又はシアノ基が好ましく、水素原子又はシアノ基がより好ましい。
　メチレン基の繰り返し部位は、いわゆるスペーサ部と呼ばれる部位である。ｎ１はメチレン基の繰り返し数を表し、それぞれ独立に２～１０の整数であるが、好ましくは３～６の整数である。
　ｑは０又は１である。ｐは、ｑが０のときは１、ｑが１のときは０又は１である。 In the formula [1], R 2 is a hydrogen atom, a halogen atom, a cyano group or a methoxy group. As the halogen atom, a fluorine atom is particularly preferable. R 2 is preferably a hydrogen atom, a methoxy group or a cyano group, more preferably a hydrogen atom or a cyano group.
The repeating part of a methylene group is a part called a spacer part. n1 represents the number of repeating methylene groups and is independently an integer of 2 to 10, preferably an integer of 3 to 6.
q is 0 or 1. p is 1 when q is 0, and 0 or 1 when q is 1.
　重合性液晶化合物（Ａ）は、スメクチック相やネマチック相といった液晶相を示す。この特性は、偏光板や位相差板等の光学異方性を利用する用途分野において有用である。 The polymerizable liquid crystal compound (A) exhibits a liquid crystal phase such as a smectic phase or a nematic phase. This characteristic is useful in the field of application utilizing optical anisotropy such as a polarizing plate and a retardation plate.
　重合性液晶化合物（Ａ）の具体例として、下記式（１）～（２５）で表される化合物を挙げることができるが、これらに限定されない。なお、式中、Ｍｅはメチル基を示す。 Specific examples of the polymerizable liquid crystal compound (A) include, but are not limited to, compounds represented by the following formulas (1) to (25). In the formula, Me represents a methyl group.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
［重合性液晶化合物（Ｂ）］
　本発明で用いる重合性液晶化合物（Ｂ）は、下記式［２］で表される。
Figure JPOXMLDOC01-appb-C000017
 [Polymerizable liquid crystal compound (B)]
The polymerizable liquid crystal compound (B) used in the present invention is represented by the following formula [2].
Figure JPOXMLDOC01-appb-C000017
　式［２］中、Ｒ3及びＲ4は上記Ｒ1と同義であり、互いに同一であっても異なっていてもよい。ｎ２及びｎ３は、メチレン基の繰り返し数を表し、それぞれ独立に２～１０の整数であるが、好ましくは３～６の整数である。ｒは１又は２である。ｓは、ｒが１のときは１、ｒが２のときは０である。 In the formula [2], R 3 and R 4 have the same meaning as R 1 described above and may be the same or different from each other. n2 and n3 each represents the number of repeating methylene groups, each independently an integer of 2 to 10, preferably an integer of 3 to 6. r is 1 or 2; s is 1 when r is 1 and 0 when r is 2.
　式［２］において、Ｒ3及びＲ4の少なくとも一方は、式［３］で表される有機基であることが好ましい。重合性液晶化合物（Ｂ）としては、下記式［９］で表されるものが特に好ましい。
Figure JPOXMLDOC01-appb-C000018
 （式中、ｎ２、ｎ３、ｒ及びｓは上記と同じ。） In the formula [2], at least one of R 3 and R 4 is preferably an organic group represented by the formula [3]. As the polymerizable liquid crystal compound (B), a compound represented by the following formula [9] is particularly preferable.
Figure JPOXMLDOC01-appb-C000018
 (Wherein n2, n3, r and s are the same as above)
　重合性液晶化合物（Ｂ）の具体例として、下記式（２６）～（１１６）で表される化合物を挙げることができるが、これらに限定されない。 Specific examples of the polymerizable liquid crystal compound (B) include compounds represented by the following formulas (26) to (116), but are not limited thereto.
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
［多価アクリレート化合物（Ｃ）］
　本発明で用いる多価アクリレート化合物（Ｃ）は、トリメチロールプロパン構造、ペンタエリスリトール構造及びエチレングリコール構造から選ばれる少なくとも１種の構造又はこれらから選ばれる少なくとも１種が縮合した構造を有する、全体で３以上５０以下の酸素原子を有する多価アルコールとアクリル酸又はその誘導体とから得られる多価アクリレート化合物である。その具体例としては、下記式［５］又は［６］で表されるもの等が挙げられる。 [Polyvalent acrylate compound (C)]
The polyvalent acrylate compound (C) used in the present invention has at least one structure selected from a trimethylolpropane structure, a pentaerythritol structure and an ethylene glycol structure, or a structure in which at least one selected from these is condensed. A polyvalent acrylate compound obtained from a polyhydric alcohol having 3 to 50 oxygen atoms and acrylic acid or a derivative thereof. Specific examples thereof include those represented by the following formula [5] or [6].
Figure JPOXMLDOC01-appb-C000030
 （式中、Ｒ5は、メチル基又は下記式［７］若しくは［８］
Figure JPOXMLDOC01-appb-C000031
 で表される有機基である。ｎ４～ｎ１０は、それぞれ独立に０～１０の整数である。ｎ１１は４～１０の整数である。破線は結合手である。）
Figure JPOXMLDOC01-appb-C000030
 (In the formula, R 5 represents a methyl group or the following formula [7] or [8].
Figure JPOXMLDOC01-appb-C000031
 It is an organic group represented by. n4 to n10 are each independently an integer of 0 to 10. n11 is an integer of 4 to 10. A broken line is a bond. )
　多価アクリレート化合物（Ｃ）の具体例として、下記式（１１７）～（１２７）で表される化合物を挙げることができるが、これらに限定されない。
Figure JPOXMLDOC01-appb-C000032
 Specific examples of the polyvalent acrylate compound (C) include compounds represented by the following formulas (117) to (127), but are not limited thereto.
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
　多価アクリレート化合物（Ｃ）としては市販品を用いることができ、例えば、日本化薬（株）製ＫＡＹＡＲＡＤ　ＤＰＨＡ、ＰＥＴ３０、新中村化学工業（株）製ＡＴＭ－３５Ｅ、ＡＤＰＨ等を挙げることができる。 Commercially available products can be used as the polyvalent acrylate compound (C), and examples thereof include KAYARAD DPHA, PET30 manufactured by Nippon Kayaku Co., Ltd., ATM-35E manufactured by Shin-Nakamura Chemical Co., Ltd., and ADPH. .
［重合性液晶組成物］
　本発明に係る重合性液晶組成物は、少なくとも１種の重合性液晶化合物（Ａ）、少なくとも１種の重合性液晶化合物（Ｂ）、及び少なくとも１種多価アクリレート化合物（Ｃ）を含有する。なお、多価アクリレート化合物（Ｃ）としては、上記式［５］又は［６］で表される化合物が好ましい。 [Polymerizable liquid crystal composition]
The polymerizable liquid crystal composition according to the present invention contains at least one polymerizable liquid crystal compound (A), at least one polymerizable liquid crystal compound (B), and at least one polyvalent acrylate compound (C). In addition, as a polyvalent acrylate compound (C), the compound represented by the said Formula [5] or [6] is preferable.
　重合性液晶化合物（Ａ）の含有量は、重合性液晶化合物（Ｂ）１００質量部に対して１００～１，９００質量部であり、好ましくは４００～９００質量部である。多価アクリレート化合物（Ｃ）の含有量は、重合性液晶化合物（Ａ）及び（Ｂ）の合計（以下、両者を併せて合計液晶性化合物と称する）１００質量部に対して０．５～５質量部が好ましく、より好ましくは１～３質量部である。 The content of the polymerizable liquid crystal compound (A) is 100 to 1,900 parts by mass, preferably 400 to 900 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound (B). The content of the polyvalent acrylate compound (C) is 0.5 to 5 with respect to 100 parts by mass of the total of the polymerizable liquid crystal compounds (A) and (B) (hereinafter collectively referred to as the total liquid crystal compound). Mass parts are preferred, more preferably 1 to 3 parts by mass.
　本発明の重合性液晶組成物には、その重合反応性を向上させる目的として、光重合開始剤、熱重合開始剤、光増感剤を添加することもできる。 In the polymerizable liquid crystal composition of the present invention, a photopolymerization initiator, a thermal polymerization initiator, and a photosensitizer can be added for the purpose of improving the polymerization reactivity.
　上記光重合開始剤としては、例えば、ベンゾインメチルエーテル等のベンゾインエーテル類、ジエトキシアセトフェノン等のアセトフェノン類、ベンジルジメチルケタール等のベンジルケタール類等が挙げられる。このような光重合開始剤は、１種単独でも複数種を組み合わせて用いてもよい。上記光重合開始剤の添加量は、合計液晶性化合物１００質量部に対して５質量部以下が好ましく、より好ましくは０．５～２．０質量部である。 Examples of the photopolymerization initiator include benzoin ethers such as benzoin methyl ether, acetophenones such as diethoxyacetophenone, benzyl ketals such as benzyldimethyl ketal, and the like. Such a photoinitiator may be used individually by 1 type or in combination of multiple types. The addition amount of the photopolymerization initiator is preferably 5 parts by mass or less, more preferably 0.5 to 2.0 parts by mass with respect to 100 parts by mass of the total liquid crystalline compounds.
　上記熱重合開始剤としては、例えば、２，２’－アゾビスイソブチロニトリル等が挙げられる。熱重合開始剤は、１種単独でも複数種を組み合わせて用いてもよい。その添加量は、合計液晶性化合物１００質量部に対して５質量部以下が好ましく、より好ましくは０．５～２．０質量部である。 Examples of the thermal polymerization initiator include 2,2'-azobisisobutyronitrile. The thermal polymerization initiator may be used alone or in combination of two or more. The addition amount is preferably 5 parts by mass or less, more preferably 0.5 to 2.0 parts by mass with respect to 100 parts by mass of the total liquid crystal compounds.
　光増感剤としては、例えば、アントラセン等のアントラセン系光増感剤が挙げられる。光増感剤は、１種単独でも複数種を組み合わせて用いてもよい。その添加量は、合計液晶性化合物１００質量部に対して５質量部以下が好ましい。 Examples of the photosensitizer include anthracene photosensitizers such as anthracene. A photosensitizer may be used alone or in combination of two or more. The addition amount is preferably 5 parts by mass or less with respect to 100 parts by mass of the total liquid crystal compounds.
　なお、上述の光重合開始剤は、熱重合開始剤及び光増感剤のうち少なくとも１種と組み合わせて用いることができる。 The above-mentioned photopolymerization initiator can be used in combination with at least one of a thermal polymerization initiator and a photosensitizer.
　本発明の重合性液晶組成物には、その保存安定性を向上させる目的で、安定剤を添加してもよい。上記安定剤としては、例えば、ヒドロキノン、ヒドロキノンモノメチルエーテル等のヒドロキノンモノアルキルエーテル類、４－ｔ－ブチルカテコール等が挙げられる。安定剤は、１種単独でも複数種を組み合わせて用いてもよい。その添加量は、合計液晶性化合物１００質量部に対して０．１質量部以下が好ましい。 A stabilizer may be added to the polymerizable liquid crystal composition of the present invention for the purpose of improving its storage stability. Examples of the stabilizer include hydroquinone monoalkyl ethers such as hydroquinone and hydroquinone monomethyl ether, and 4-t-butylcatechol. A stabilizer may be used alone or in combination of two or more. The addition amount is preferably 0.1 parts by mass or less with respect to 100 parts by mass of the total liquid crystal compounds.
　また、本発明の重合性液晶組成物には、基板との密着性を向上させる目的で、密着促進剤を添加してもよい。密着促進剤としては、トリメチルクロロシラン、ジメチルビニルクロロシラン、メチルジフェニルクロロシラン、クロロメチルジメチルクロロシラン、ビニルトリクロロシラン等のクロロシラン類；トリメチルメトキシシラン、ジメチルジエトキシシラン、メチルジメトキシシラン、ジメチルビニルエトキシシラン、ジフェニルジメトキシシラン、フェニルトリエトキシシラン、γ－クロロプロピルトリメトキシシラン、γ－アミノプロピルトリエトキシシラン、γ－メタクリロキシプロピルトリメトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－（Ｎ－ピペリジニル）プロピルトリメトキシシラン等のアルコキシシラン類；ヘキサメチルジシラザン、Ｎ，Ｎ’－ビス（トリメチルシリル）ウレア、ジメチルトリメチルシリルアミン、Ｎ－トリメチルシリルイミダゾール等のシラザン類；ベンゾトリアゾール、ベンズイミダゾール、インダゾール、イミダゾール、２－メルカプトベンズイミダゾール、２－メルカプトベンゾチアゾール、２－メルカプトベンゾオキサゾール、ウラゾール、チオウラシル、メルカプトイミダゾール、メルカプトピリミジン等の複素環状化合物；１，１－ジメチルウレア、１，３－ジメチルウレア等の尿素化合物；チオ尿素化合物等が挙げられる。 In addition, an adhesion promoter may be added to the polymerizable liquid crystal composition of the present invention for the purpose of improving the adhesion to the substrate. As adhesion promoters, chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, vinyltrichlorosilane; trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxy Silane, phenyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- (N-piperidinyl) propyl Alkoxysilanes such as trimethoxysilane; hexamethyldisilazane, N, N′-bis (trimethylsilyl) urea, dimethyltrimethylsilyl Silazanes such as amine and N-trimethylsilylimidazole; benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, mercaptopyrimidine, etc. Heterocyclic compounds; urea compounds such as 1,1-dimethylurea and 1,3-dimethylurea; and thiourea compounds.
　密着促進剤は、１種単独でも複数種を組み合わせて用いてもよい。その添加量は、合計液晶性化合物１００質量部に対して１質量部以下が好ましい。 The adhesion promoter may be used alone or in combination of two or more. The addition amount is preferably 1 part by mass or less with respect to 100 parts by mass of the total liquid crystal compounds.
　更に、本発明の重合性液晶組成物には、粘度調整等を目的として有機溶媒を添加することもできる。この場合、有機溶媒を含有した状態では液晶性を呈しなくても構わない。 Furthermore, an organic solvent can be added to the polymerizable liquid crystal composition of the present invention for the purpose of adjusting the viscosity. In this case, liquid crystal properties may not be exhibited in a state containing an organic solvent.
　有機溶媒としては、例えば、テトラヒドロフラン、ジオキサン等のエーテル類、ベンゼン、トルエン、キシレン等の芳香族炭化水素類；Ｎ，Ｎ－ジメチルホルムアミド、Ｎ－メチル－２－ピロリドン等の極性溶媒；酢酸エチル、酢酸ブチル、乳酸エチル等のエステル類；３－メトキシプロピオン酸メチル、２－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、２－メトキシプロピオン酸エチル、３－エトキシプロピオン酸エチル、２－エトキシプロピオン酸エチル等のアルコキシエステル類；エチレングリコールジメチルエーテル、プロピレングリコールジメチルエーテル等のグリコールジアルキルエーテル類；ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールメチルエチルエーテル、ジプロピレングリコールジメチルエーテル等のジグリコールジアルキルエーテル類；エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル等のグリコールモノアルキルエーテル類；ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル等のジグリコールモノアルキルエーテル類；プロピレングリコールモノメチルエーテルアセテート、カルビトールアセテート、エチルセロソルブアセテート等のグリコールモノアルキルエーテルエステル類；シクロヘキサノン、メチルエチルケトン、メチルイソブチルケトン、２－ヘプタノン等のケトン類等を挙げることができる。これらの中でも地球環境、作業環境への安全性観点からプロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、乳酸エチル等が好ましい。 Examples of the organic solvent include ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene and xylene; polar solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone; Esters such as butyl acetate and ethyl lactate; methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, 2-ethoxypropionic acid Alkoxy esters such as ethyl; glycol dialkyl ethers such as ethylene glycol dimethyl ether and propylene glycol dimethyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Diglycol dialkyl ethers such as ruethyl ether and dipropylene glycol dimethyl ether; glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether; diethylene glycol monomethyl ether and diethylene glycol Diglycol monoalkyl ethers such as monoethyl ether, dipropylene glycol monomethyl ether and dipropylene glycol monoethyl ether; glycol monoalkyl ether esters such as propylene glycol monomethyl ether acetate, carbitol acetate and ethyl cellosolve acetate; cyclohexanone, methyl ethyl Tons, methyl isobutyl ketone and 2-heptanone. Among these, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate and the like are preferable from the viewpoint of safety to the global environment and the working environment.
　これらの有機溶媒は、１種単独でも２種以上を組み合わせて用いてもよい。有機溶媒の使用量は、重合性液晶組成物中、６０～９５質量％程度とすることが好適である。 These organic solvents may be used alone or in combination of two or more. The amount of the organic solvent used is preferably about 60 to 95% by mass in the polymerizable liquid crystal composition.
　また、本発明の重合性液晶組成物には、基板との親和性を向上させる目的で界面活性剤を添加してもよい。界面活性剤としては、特に限定されるものではなく、フッ素系界面活性剤、シリコーン系界面活性剤、ノニオン系界面活性剤等が挙げられるが、基板との親和性改善効果の高いフッ素系界面活性剤が好ましい。 Further, a surfactant may be added to the polymerizable liquid crystal composition of the present invention for the purpose of improving the affinity with the substrate. The surfactant is not particularly limited, and examples thereof include fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, etc., but fluorine-based surfactants having a high effect of improving affinity with the substrate. Agents are preferred.
　フッ素系界面活性剤の具体例としては（以下、商品名）、エフトップＥＦ３０１、ＥＦ３０３、ＥＦ３５２（（株）トーケムプロダクツ製）、メガファックＦ１７１、Ｆ１７３、Ｒ－３０（ＤＩＣ（株）製）、フロラードＦＣ４３０、ＦＣ４３１（住友スリーエム（株）製）、アサヒガードＡＧ７１０、サーフロンＳ－３８２、ＳＣ１０１、ＳＣ１０２、ＳＣ１０３、ＳＣ１０４、ＳＣ１０５、ＳＣ１０６（旭硝子（株）製）等が挙げられるが、これらに限定されない。なお、界面活性剤は、１種単独でも複数種を組み合わせて用い用いてもよい。 Specific examples of fluorosurfactants (hereinafter referred to as trade names), EFTOP EF301, EF303, EF352 (manufactured by Tochem Products), MegaFuck F171, F173, R-30 (manufactured by DIC Corporation) , FLORARD FC430, FC431 (Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.), etc. Not. The surfactants may be used alone or in combination of two or more.
　本発明の重合性液晶組成物の好適例としては、重合性液晶化合物（Ａ）が重合性液晶化合物（Ｂ）１００質量部に対して４００質量部～９００質量部であり、多価アクリレート化合物（Ｃ）が重合性液晶化合物（Ａ）及び（Ｂ）の合計１００質量部に対して１～３質量部であり、及び光開始剤が重合性液晶化合物（Ａ）及び（Ｂ）の合計１００質量部に対して５質量部以下からなるもの等が挙げられるが、これに限定されない。 As a preferred example of the polymerizable liquid crystal composition of the present invention, the polymerizable liquid crystal compound (A) is 400 to 900 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound (B). C) is 1 to 3 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compounds (A) and (B), and the photoinitiator is 100 parts by mass of the polymerizable liquid crystal compounds (A) and (B). Although what consists of 5 mass parts or less with respect to a part is mentioned, It is not limited to this.
　本発明の重合性液晶組成物の調製方法は特に限定されず、重合性液晶組成物を構成する各成分を一度に混合してもよいし、順次混合してもよい。順次混合する際における各成分の添加順序は任意である。
　なお、１つの成分に複数種の化合物を使用する場合は、予めそれらを混合した混合物とその他の成分とを混合してもよく、それぞれ別個にその他の成分と混合してもよい。 The preparation method of the polymerizable liquid crystal composition of the present invention is not particularly limited, and each component constituting the polymerizable liquid crystal composition may be mixed at one time or sequentially. The order of adding the components in the sequential mixing is arbitrary.
In addition, when using multiple types of compounds for one component, the mixture which mixed them previously and other components may be mixed, and you may mix with another component separately, respectively.
　本発明の重合性液晶組成物は、光学異方体を製造する際に、液晶状態での光重合において意図しない熱重合の誘起を避け、分子の均一な配向状態の固定を容易にするために、室温（２０～４０℃、以下同じ）においてエナンチオトロピックな液晶相を示すことが好ましい。また、重合性液晶組成物が有機溶媒を含有する場合は、溶媒を除去した際に室温において、エナンチオトロピックな液晶相を示すことが好ましい。 The polymerizable liquid crystal composition of the present invention avoids unintentional induction of thermal polymerization in photopolymerization in a liquid crystal state and facilitates fixing of a uniform alignment state of molecules when producing an optical anisotropic body. It is preferable that the liquid crystal phase exhibits an entropy at room temperature (20 to 40 ° C., the same shall apply hereinafter). Further, when the polymerizable liquid crystal composition contains an organic solvent, it is preferable that an enantiomeric liquid crystal phase is exhibited at room temperature when the solvent is removed.
　本発明の重合性液晶組成物は、配向性被膜形成用の組成物や塗布液として好適に利用できる。 The polymerizable liquid crystal composition of the present invention can be suitably used as a composition for forming an orientation film or a coating solution.
［重合体及びフィルム］
　以上説明した本発明の重合性液晶組成物に対し、光照射や加熱処理することで重合体が得られる。また、基板に重合性液晶組成物をスピンコートやキャスト法等により塗布し、光照射処理することで、フィルムが得られる。 [Polymer and film]
A polymer can be obtained by subjecting the polymerizable liquid crystal composition of the present invention described above to light irradiation or heat treatment. In addition, a film can be obtained by applying a polymerizable liquid crystal composition to a substrate by spin coating, a casting method, or the like, and performing light irradiation treatment.
　この際、基板としては、ガラス、石英、カラーフィルタ、トリアセチルセルロース（ＴＡＣ）等のプラスチックシート又はフィルム等を用いることができる。 At this time, as the substrate, glass, quartz, a color filter, a plastic sheet such as triacetyl cellulose (TAC), a film, or the like can be used.
　使用する基板には、得られるフィルムのハイブリッド配向性を向上させる目的で、チルトが得られるように配向処理を施すことが好ましい。配向処理の方法としては、ポリイミド前駆体、ポリイミド、ポリビニルシンナメート等を含有する配向材を塗布し、ラビング又は偏光紫外線を斜めから照射して配向処理する方法、二酸化ケイ素の斜法蒸着膜を形成する方法、ラングミュア膜を形成する方法等の公知の方法から適宜選択して用いることができるが、ハイブリッド配向フィルムを作製するために、いずれにおいてもチルトが得られる配向方法を用いることが好ましい。 For the purpose of improving the hybrid orientation of the resulting film, the substrate to be used is preferably subjected to an orientation treatment so as to obtain a tilt. As an alignment treatment method, an alignment material containing a polyimide precursor, polyimide, polyvinyl cinnamate, etc. is applied, and an alignment treatment is performed by irradiating with rubbing or polarized ultraviolet rays obliquely, and a silicon dioxide oblique deposition film is formed. However, in order to produce a hybrid alignment film, it is preferable to use an alignment method capable of obtaining a tilt in any case.
　フィルムを作製する方法において、重合性液晶組成物を塗布する工程と光や熱によって重合させる工程との途中に、必要に応じてホットプレート等で加熱する工程を加えてもよい。この工程は、特に、有機溶媒を含有する重合性液晶組成物（塗布液）を用いる場合に、当該組成物から有機溶媒を除去する手段として有効である。 In the method for producing a film, a step of heating with a hot plate or the like may be added as needed during the step of applying the polymerizable liquid crystal composition and the step of polymerizing with light or heat. This step is particularly effective as a means for removing the organic solvent from the composition when a polymerizable liquid crystal composition (coating liquid) containing the organic solvent is used.
　上記のいずれの方法においても、重合性液晶組成物が液晶相を呈する状態で重合することで、配向した光学異方性を有するフィルムを得ることができる。 In any of the above methods, an oriented film having optical anisotropy can be obtained by polymerizing the polymerizable liquid crystal composition in a state of exhibiting a liquid crystal phase.
　本発明の重合性液晶組成物を用いることで、光学異方性を有するフィルムが得られ、このフィルムは偏光板や位相差板等に好適に用いることができる。しかも、このフィルムは高温での透明性が良好なため、車載用表示装置等の高温環境下で使用される電子機器に好適に利用できる。 By using the polymerizable liquid crystal composition of the present invention, a film having optical anisotropy can be obtained, and this film can be suitably used for a polarizing plate, a retardation plate and the like. In addition, since this film has good transparency at high temperatures, it can be suitably used for electronic devices used in high-temperature environments such as in-vehicle display devices.
　以下、合成例、実施例及び比較例を挙げて本発明をより具体的に説明するが、本発明は実施例に限定されない。なお、実施例における各物性の測定方法及び測定条件は、以下のとおりである。
［１］ＮＭＲ
　化合物を重水素化クロロホルム（ＣＤＣｌ3）又は重水素化ジメチルスルホキシド（ＤＭＳＯ－ｄ６）に溶解し、核磁気共鳴装置（３００ＭＨｚ、ジオール社製）を用いて1Ｈ－ＮＭＲを測定した。
［２］液晶相の観察
　液晶相の同定は、ホットステージ（ＭＡＴＳ－２００２Ｓ、（株）東海ヒット製）上で試料を加熱し、偏光顕微鏡（（株）ニコン製）を用いて観察して行った。相転移温度はブルカー・エイエックスエス（株）製示差走査熱分析装置（ＤＳＣ３１００ＳＲ）を用い、スキャンスピード（Ｓｃａｎ　Ｒａｔｅ）１０℃／分の条件で測定した。
［３］ヘイズ値
　（有）東京電色製Ｓｐｅｃｔｒａｌ　Ｈａｚｅ　Ｍｅｔｅｒ（ＴＣ－１８００Ｈ）を用いてフィルムのヘイズ値を測定した。
［４］フィルムのリタデーション値
　リタデーション測定装置（ＲＥＴＳ－１００、大塚電子（株）製）を用いて波長５９０ｎｍのリタデーション値を測定した。
［５］フィルムの平均チルト角度
　ＡｘｏＳｃａｎTM　Ｍｕｅｌｌｅｒ　Ｍａｔｒｉｘ　Ｐｏｌａｒｉｍｅｔｅｒ（ＡＸＯＭＥＴＲＩＸ社製）を用いて平均チルト角度を測定した。 EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to an Example. In addition, the measuring method and measuring conditions of each physical property in an Example are as follows.
[1] NMR
The compound was dissolved in deuterated chloroform (CDCl 3 ) or deuterated dimethyl sulfoxide (DMSO-d6), and 1 H-NMR was measured using a nuclear magnetic resonance apparatus (300 MHz, manufactured by Diol).
[2] Observation of liquid crystal phase The liquid crystal phase is identified by heating the sample on a hot stage (MATS-2002S, manufactured by Tokai Hit Co., Ltd.) and using a polarizing microscope (manufactured by Nikon Co., Ltd.). It was. The phase transition temperature was measured using a differential scanning calorimeter (DSC3100SR) manufactured by Bruker AXS Co., Ltd. at a scan speed of 10 ° C./min.
[3] Haze value The haze value of the film was measured using a specular haze meter (TC-1800H) manufactured by Tokyo Denshoku.
[4] Retardation value of film The retardation value at a wavelength of 590 nm was measured using a retardation measuring device (RETS-100, manufactured by Otsuka Electronics Co., Ltd.).
[5] Average Tilt Angle of Film The average tilt angle was measured using an AxoScan ™ Mueller Matrix Polarimeter (manufactured by AXOMETRIX).
［合成例１］重合性液晶化合物（Ａ１）の合成
［１］中間体化合物（Ｉ１）の合成
Figure JPOXMLDOC01-appb-C000034
 [Synthesis Example 1] Synthesis of polymerizable liquid crystal compound (A1) [1] Synthesis of intermediate compound (I1)
Figure JPOXMLDOC01-appb-C000034
　冷却管付き５００ｍＬナスフラスコに、４－シアノ－４’－ヒドロキシビフェニル９．８ｇ（５０．０ｍｍｏｌ）、３－ブロモ－１－プロパノール７．０ｇ（５０．０ｍｍｏｌ）、炭酸カリウム１３．８ｇ（１００ｍｍｏｌ）、及びアセトン１５０ｍＬを加えて混合物とし、６４℃で４８時間撹拌しながら反応させた。反応終了後、減圧下で溶媒を留去し、黄色の湿潤固体を得た。その後、この固体と水１４０ｍＬとを混合し、そこにジエチルエーテル１００ｍＬを加えて抽出した。抽出は３回行った。分液した有機層は、無水硫酸マグネシウムを加えて乾燥し、ろ過した後に減圧下で溶媒を留去し、黄色固体を得た。この固体をヘキサン／酢酸エチル＝２／１（ｖ／ｖ）の混合溶媒を用いた再結晶により精製し、白色固体８．７ｇを得た。この固体のＮＭＲ測定結果を以下に示す。この結果から、この白色固体が中間体化合物（Ｉ１）であることが確認された（収率７０％）。
1H-NMR (CDCl3) δ:2.09 (m, 2H), 3.90 (t, 2H), 4.20 (t, 2H), 6.99 (d, 2H), 7.52 (d, 2H), 7.66 (m, 4H) In a 500 mL eggplant flask equipped with a condenser tube, 9.8 g (50.0 mmol) of 4-cyano-4′-hydroxybiphenyl, 7.0 g (50.0 mmol) of 3-bromo-1-propanol, 13.8 g (100 mmol) of potassium carbonate , And 150 mL of acetone were added to form a mixture, which was reacted at 64 ° C. for 48 hours with stirring. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a yellow wet solid. Thereafter, this solid and 140 mL of water were mixed, and 100 mL of diethyl ether was added thereto for extraction. Extraction was performed three times. The separated organic layer was dried by adding anhydrous magnesium sulfate, filtered, and then the solvent was distilled off under reduced pressure to obtain a yellow solid. This solid was purified by recrystallization using a mixed solvent of hexane / ethyl acetate = 2/1 (v / v) to obtain 8.7 g of a white solid. The NMR measurement result of this solid is shown below. From this result, it was confirmed that this white solid was intermediate compound (I1) (yield 70%).
1 H-NMR (CDCl 3 ) δ: 2.09 (m, 2H), 3.90 (t, 2H), 4.20 (t, 2H), 6.99 (d, 2H), 7.52 (d, 2H), 7.66 (m, 4H )
［２］重合性液晶化合物（Ａ１）の合成
Figure JPOXMLDOC01-appb-C000035
 [2] Synthesis of polymerizable liquid crystal compound (A1)
Figure JPOXMLDOC01-appb-C000035
　上記で得られた中間体化合物（Ｉ１）１２．０ｇを、トリエチルアミン７．７ｍＬと少量の２，６－ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール（ＢＨＴ）と共に、テトラヒドロフラン（ＴＨＦ）４０ｍＬに溶解させて室温にて撹拌し、水浴による冷却下、塩化アクリロイル４．６ｍＬをＴＨＦ４０ｍＬに溶解した溶液を１５分間かけて滴下した。滴下後、３０分間撹拌し、水浴を除去して室温に戻しながら終夜撹拌を続けて析出したトリエチルアミン塩酸塩をろ過した。得られたろ液からＴＨＦを約３／４留去してジクロロメタン５０ｍＬを添加し、その有機層を飽和炭酸水素ナトリウム水溶液５０ｍＬ、０．５ｍｏｌ／Ｌ塩酸５０ｍＬ、飽和食塩水５０ｍＬにて順次洗浄し、硫酸マグネシウムで乾燥後、溶媒を留去して生成物を得た。エタノールによる再結晶後、重合性液晶化合物（Ａ１）６．０ｇを得た。
1H-NMR(CDCl3) δ：2.20(m, 2H), 4.10(t, 2H), 4.40(t, 2H), 5.81(d, 1H), 6.15(m, 1H), 6.41(d, 1H), 6.99(d, 2H), 7.55(d, 2H), 7.66(m, 4H) 12.0 g of the intermediate compound (I1) obtained above was dissolved in 40 mL of tetrahydrofuran (THF) together with 7.7 mL of triethylamine and a small amount of 2,6-di-tert-butyl-p-cresol (BHT). The solution which stirred at room temperature and melt | dissolved acryloyl chloride 4.6mL in THF40mL was dripped over 15 minutes under cooling by a water bath. After dropping, the mixture was stirred for 30 minutes, and the water bath was removed, and stirring was continued overnight while returning to room temperature, and the precipitated triethylamine hydrochloride was filtered. About 3/4 of the THF was distilled off from the obtained filtrate, 50 mL of dichloromethane was added, and the organic layer was washed successively with 50 mL of saturated aqueous sodium bicarbonate, 50 mL of 0.5 mol / L hydrochloric acid, and 50 mL of saturated brine, After drying with magnesium sulfate, the solvent was distilled off to obtain the product. After recrystallization from ethanol, 6.0 g of a polymerizable liquid crystal compound (A1) was obtained.
1 H-NMR (CDCl 3 ) δ: 2.20 (m, 2H), 4.10 (t, 2H), 4.40 (t, 2H), 5.81 (d, 1H), 6.15 (m, 1H), 6.41 (d, 1H ), 6.99 (d, 2H), 7.55 (d, 2H), 7.66 (m, 4H)
［合成例２］重合性液晶化合物（Ａ２）の合成
［１］中間体化合物（Ｉ２）の合成
Figure JPOXMLDOC01-appb-C000036
 [Synthesis Example 2] Synthesis of polymerizable liquid crystal compound (A2) [1] Synthesis of intermediate compound (I2)
Figure JPOXMLDOC01-appb-C000036
　冷却管付き１００ｍＬナスフラスコに、４－シアノ－４’－ヒドロキシビフェニル５．０ｇ（２５．６ｍｍｏｌ）、６－ブロモ－１－ヘキサノール４．６ｇ（２５．６ｍｍｏｌ）、炭酸カリウム７．０ｇ（５０ｍｍｏｌ）、及びアセトン５０ｍＬを加えて混合物とし、６４℃で２４時間撹拌しながら反応させた。反応終了後、減圧下で溶媒を留去し、黄色の湿潤固体を得た。その後、この固体と水７０ｍＬとを混合し、ジエチルエーテル５０ｍＬを加えて抽出した。抽出は３回行った。分液した有機層は、無水硫酸マグネシウムを加えて乾燥し、ろ過した後に減圧下で溶媒を留去し、黄色固体を得た。この固体を酢酸エチル３ｍＬに溶解し、シリカゲルカラムクロマトグラフィ（カラム：シリカゲル６０，０．０６３－０．２００ｍｍ，メルク社製、溶出液：へキサン／酢酸エチル＝１／１（ｖ／ｖ））により精製した。得られた溶液から溶媒を留去し、白色固体６．９ｇを得た。この固体のＮＭＲ測定結果を以下に示す。この結果から、この白色固体が中間体化合物（Ｉ２）であることが確認された（収率９１％）。
1H-NMR(DMSO-d6) δ：1.26(m, 6H), 1.69(m, 2H), 3.37(t, 2H), 4.03(t, 2H), 7.06(d, 2H), 7.69(d, 2H), 7.85(m, 4H) In a 100 mL eggplant flask equipped with a condenser tube, 5.0 g (25.6 mmol) of 4-cyano-4′-hydroxybiphenyl, 4.6 g (25.6 mmol) of 6-bromo-1-hexanol, 7.0 g (50 mmol) of potassium carbonate And acetone (50 mL) were added to form a mixture, which was reacted at 64 ° C. with stirring for 24 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a yellow wet solid. Then, this solid and 70 mL of water were mixed, and 50 mL of diethyl ether was added and extracted. Extraction was performed three times. The separated organic layer was dried by adding anhydrous magnesium sulfate, filtered, and then the solvent was distilled off under reduced pressure to obtain a yellow solid. This solid was dissolved in 3 mL of ethyl acetate and purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck & Co., eluent: hexane / ethyl acetate = 1/1 (v / v)). Purified. The solvent was distilled off from the resulting solution to obtain 6.9 g of a white solid. The NMR measurement result of this solid is shown below. From this result, it was confirmed that this white solid was intermediate compound (I2) (yield 91%).
1 H-NMR (DMSO-d6) δ: 1.26 (m, 6H), 1.69 (m, 2H), 3.37 (t, 2H), 4.03 (t, 2H), 7.06 (d, 2H), 7.69 (d, 2H), 7.85 (m, 4H)
［２］中間体化合物（Ｆ２）の合成
Figure JPOXMLDOC01-appb-C000037
 [2] Synthesis of intermediate compound (F2)
Figure JPOXMLDOC01-appb-C000037
　次に、冷却管付き２００ｍＬ三口フラスコにピリジニウムクロロクロマート（ＰＣＣ）２．２ｇ（１０．０ｍｍｏｌ）及びジクロロメタン３０．０ｍＬを加えて撹拌混合した状態で、上記で得られた中間体化合物（Ｉ２）２．９５ｇ（１０．０ｍｍｏｌ）をジクロロメタン５０．０ｍＬに溶解した溶液を滴下し、４０℃で０．５時間、更に撹拌した。その後、フラスコの壁に付着したオイル状物を除いた溶液に、ジエチルエーテル９０ｍＬを加えて減圧ろ過した後、減圧下で溶媒を留去して、濃緑色の湿潤な固体を得た。この固体を酢酸エチル３ｍＬに溶解し、シリカゲルカラムクロマトグラフィ（カラム：シリカゲル６０，０．０６３－０．２００ｍｍ，メルク社製、溶出液：ヘキサン／酢酸エチル＝１／１（ｖ／ｖ））で精製した。得られた溶液の溶媒を留去して、無色固体２．８ｇを得た。この固体のＮＭＲ測定結果を以下に示す。この結果から、この無色固体が中間体化合物（Ｆ２）であることが確認された（収率９３％）。
1H-NMR(CDCl3) δ：1.84(m, 6H), 2.50(m, 2H), 4.02(m, 2H), 6.99(d, 2H), 7.53(d, 2H), 7.91(m, 4H), 9.80(s, 1H) Next, intermediate compound (I2) obtained above in a state where 2.2 g (10.0 mmol) of pyridinium chlorochromate (PCC) and 30.0 mL of dichloromethane were added to a 200 mL three-necked flask equipped with a condenser and stirred and mixed. A solution prepared by dissolving 2.95 g (10.0 mmol) in 50.0 mL of dichloromethane was added dropwise, and the mixture was further stirred at 40 ° C. for 0.5 hour. Thereafter, 90 mL of diethyl ether was added to the solution excluding the oily substance adhering to the wall of the flask and filtered under reduced pressure, and then the solvent was distilled off under reduced pressure to obtain a dark green wet solid. This solid was dissolved in 3 mL of ethyl acetate and purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck & Co., eluent: hexane / ethyl acetate = 1/1 (v / v)). did. The solvent of the obtained solution was distilled off to obtain 2.8 g of a colorless solid. The NMR measurement result of this solid is shown below. From this result, it was confirmed that this colorless solid was an intermediate compound (F2) (yield 93%).
1 H-NMR (CDCl 3 ) δ: 1.84 (m, 6H), 2.50 (m, 2H), 4.02 (m, 2H), 6.99 (d, 2H), 7.53 (d, 2H), 7.91 (m, 4H ), 9.80 (s, 1H)
［３］重合性液晶化合物（Ａ２）の合成
Figure JPOXMLDOC01-appb-C000038
 [3] Synthesis of polymerizable liquid crystal compound (A2)
Figure JPOXMLDOC01-appb-C000038
　最後に、冷却管付き５０ｍＬナスフラスコに、上記で得られた中間体化合物（Ｆ２）２．９ｇ（１０．０ｍｍｏｌ）、２－（ブロモメチル）アクリル酸１．６５ｇ（１０．０ｍｍｏｌ）、Ａｍｂｅｒｌｙｓｔ（登録商標）１５（ロームエンドハース社　商品名）１．６ｇ、ＴＨＦ１６．０ｍＬ、塩化スズ（ＩＩ）１．９ｇ（１０．０ｍｍｏｌ）、及び純水４．０ｍＬを加えて混合物とし、７０℃で７時間撹拌して反応させた。反応終了後、反応液を減圧ろ過して純水３０ｍＬと混合し、そこにジエチルエーテル５０ｍＬを加えて抽出した。抽出は３回行った。抽出後の有機層に、無水硫酸マグネシウムを加えて乾燥し、減圧ろ過した後の溶液から溶媒を留去し、黄色固体を得た。この固体を酢酸エチル２ｍＬに溶解し、シリカゲルカラムクロマトグラフィ（カラム：シリカゲル６０，０．０６３－０．２００ｍｍ，メルク社製、溶出液：ヘキサン／酢酸エチル＝２／１（ｖ／ｖ））により精製した。得られた溶液の溶媒を留去して、白色固体１．５ｇを得た。この固体のＮＭＲ測定結果を以下に示す。この結果から、この白色固体が目的の重合性液晶化合物（Ａ２）であることが確認された（収率４１％）。
1H-NMR(CDCl3) δ：1.57(m, 6H), 1.85(m, 2H), 2.60(m, 1H), 3.05(m, 1H), 4.01(t, 2H), 4.54(m, 1H), 5.63(m, 1H), 6.23(m, 1H), 7.00(d, 2H), 7.52(d, 2H), 7.68(m, 4H)
　なお、この重合性液晶化合物（A２）の液晶性を観察した結果、８４℃で等方性液体状態となり、降温時、６１℃で液晶相（ネマチック相）へ相転移した。 Finally, in a 50 mL eggplant flask equipped with a cooling tube, 2.9 g (10.0 mmol) of the intermediate compound (F2) obtained above, 1.65 g (10.0 mmol) of 2- (bromomethyl) acrylic acid, Amberlyst (registered) Trademark) 15 (Rohm End Haas Co., Ltd.) 1.6 g, THF 16.0 mL, tin (II) chloride 1.9 g (10.0 mmol), and pure water 4.0 mL were added to form a mixture, and the mixture was at 70 ° C. for 7 hours. Stir to react. After completion of the reaction, the reaction solution was filtered under reduced pressure and mixed with 30 mL of pure water, and 50 mL of diethyl ether was added thereto for extraction. Extraction was performed three times. The organic layer after extraction was dried by adding anhydrous magnesium sulfate, and the solvent was distilled off from the solution after filtration under reduced pressure to obtain a yellow solid. This solid was dissolved in 2 mL of ethyl acetate and purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck & Co., eluent: hexane / ethyl acetate = 2/1 (v / v)). did. The solvent of the obtained solution was distilled off to obtain 1.5 g of a white solid. The NMR measurement result of this solid is shown below. From this result, it was confirmed that this white solid was the target polymerizable liquid crystal compound (A2) (yield 41%).
1 H-NMR (CDCl 3 ) δ: 1.57 (m, 6H), 1.85 (m, 2H), 2.60 (m, 1H), 3.05 (m, 1H), 4.01 (t, 2H), 4.54 (m, 1H ), 5.63 (m, 1H), 6.23 (m, 1H), 7.00 (d, 2H), 7.52 (d, 2H), 7.68 (m, 4H)
As a result of observing the liquid crystal properties of this polymerizable liquid crystal compound (A2), it became an isotropic liquid state at 84 ° C., and phase transitioned to a liquid crystal phase (nematic phase) at 61 ° C. when the temperature was lowered.
［合成例３］重合性液晶化合物（Ｂ１）の合成
［１］中間体化合物（Ｉ３）の合成
Figure JPOXMLDOC01-appb-C000039
 [Synthesis Example 3] Synthesis of polymerizable liquid crystal compound (B1) [1] Synthesis of intermediate compound (I3)
Figure JPOXMLDOC01-appb-C000039
　冷却管付き２００ｍＬナスフラスコに、４－ヒドロキシ安息香酸メチル７．６１ｇ（５０．０ｍｍｏｌ）、６－ブロモ－１－ヘキサノール９．１ｇ（５０．０ｍｍｏｌ）、炭酸カリウム１３．８ｇ（１００ｍｍｏｌ）、及びアセトン７０ｍＬを加えて混合物とし、６４℃（加熱還流下）で２４時間撹拌しながら反応させた。反応終了後、反応液を減圧ろ過して減圧下で溶媒を留去し、黄色の湿潤固体を得た。この固体を、シリカゲルカラムクロマトグラフィ（カラム：シリカゲル６０，０．０６３－０．２００ｍｍ，メルク社製、溶出液：へキサン／酢酸エチル＝１／１（ｖ／ｖ））により精製した。得られた溶液から溶媒を留去し、白色の固体１１．３ｇを得た。この固体のＮＭＲ測定結果を以下に示す。この結果から、この白色固体が中間体化合物（Ｉ３）であることが確認された（収率９０％）。
1H-NMR(CDCl3) δ:1.3-1.7 (m, 8H), 3.67 (m, 2H), 3.88 (s, 3H), 4.03 (t, 2H), 6.91 (d, 2H), 7.99 (d, 2H) In a 200 mL eggplant flask with a condenser tube, 7.61 g (50.0 mmol) of methyl 4-hydroxybenzoate, 9.1 g (50.0 mmol) of 6-bromo-1-hexanol, 13.8 g (100 mmol) of potassium carbonate, and acetone 70 mL was added to make a mixture, and the mixture was reacted at 64 ° C. (under heating under reflux) with stirring for 24 hours. After completion of the reaction, the reaction solution was filtered under reduced pressure, and the solvent was distilled off under reduced pressure to obtain a yellow wet solid. This solid was purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck & Co., eluent: hexane / ethyl acetate = 1/1 (v / v)). The solvent was distilled off from the resulting solution to obtain 11.3 g of a white solid. The NMR measurement result of this solid is shown below. From this result, it was confirmed that this white solid was intermediate compound (I3) (yield 90%).
1 H-NMR (CDCl 3 ) δ: 1.3-1.7 (m, 8H), 3.67 (m, 2H), 3.88 (s, 3H), 4.03 (t, 2H), 6.91 (d, 2H), 7.99 (d , 2H)
［２］中間体化合物（Ｆ３）の合成
Figure JPOXMLDOC01-appb-C000040
 [2] Synthesis of intermediate compound (F3)
Figure JPOXMLDOC01-appb-C000040
　次に、冷却管付き１００ｍＬ三口フラスコに、ＰＣＣ２．２ｇ（１０．０ｍｍｏｌ）、及びジクロロメタン１５．０ｍＬを入れて撹拌混合した状態で、上記で得られた中間体化合物（Ｉ３）２．５ｇ（１０．０ｍｍｏｌ）をジクロロメタン１５．０ｍＬに溶解した溶液を滴下し、室温で６時間さらに撹拌した。その後、フラスコの壁に付着したオイル状物を除いた溶液に、ジエチルエーテル９０ｍＬを加えて減圧ろ過した後、減圧下で溶媒を留去し、濃緑色の湿潤固体を得た。この固体をシリカゲルカラムクロマトグラフィ（カラム：シリカゲル６０，０．０６３－０．２００ｍｍ，メルク社製、溶出液：ヘキサン／酢酸エチル＝２／１（ｖ／ｖ））で精製した。得られた溶液の溶媒を留去し、無色固体１．３ｇを得た。この固体をＮＭＲで測定した結果を以下に示す。この結果からこの無色固体が、中間体化合物（Ｆ３）であることが確認された（収率５０％）。
1H-NMR(CDCl3) δ:1.3-1.8 (m, 6H), 2.49 (t, 2H), 3.88 (s, 3H), 3.99 (t, 2H), 6.87 (d, 2H), 7.99 (d, 2H), 9.78 (s, 1H) Next, in a 100 mL three-necked flask with a condenser tube, 2.2 g (10.0 mmol) of PCC and 15.0 mL of dichloromethane were stirred and mixed, and 2.5 g of the intermediate compound (I3) obtained above (10 0.0 mmol) in 15.0 mL of dichloromethane was added dropwise, and the mixture was further stirred at room temperature for 6 hours. Thereafter, 90 mL of diethyl ether was added to the solution excluding the oily substance adhering to the flask wall and filtered under reduced pressure, and then the solvent was distilled off under reduced pressure to obtain a dark green wet solid. This solid was purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck & Co., eluent: hexane / ethyl acetate = 2/1 (v / v)). The solvent of the obtained solution was distilled off to obtain 1.3 g of a colorless solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this colorless solid was an intermediate compound (F3) (yield 50%).
1 H-NMR (CDCl 3 ) δ: 1.3-1.8 (m, 6H), 2.49 (t, 2H), 3.88 (s, 3H), 3.99 (t, 2H), 6.87 (d, 2H), 7.99 (d , 2H), 9.78 (s, 1H)
［３］中間体化合物（Ｇ３）の合成
Figure JPOXMLDOC01-appb-C000041
 [3] Synthesis of intermediate compound (G3)
Figure JPOXMLDOC01-appb-C000041
　次に、冷却管付き５０ｍＬナスフラスコに、上記で得られた中間体化合物（Ｆ３）１．２５ｇ（５．０ｍｍｏｌ）、２－（ブロモメチル）アクリル酸０．８３ｇ（５．０ｍｍｏｌ）、Ａｍｂｅｒｌｙｓｔ（登録商標）１５（ロームエンドハース社　商品名）０．８ｇ、ＴＨＦ８．０ｍＬ、塩化スズ（ＩＩ）０．９５ｇ（５．０ｍｍｏｌ）、及び純水２．０ｍＬを加えて混合物とし、７０℃で５時間撹拌して反応させた。反応終了後、反応液を減圧ろ過して純水４０ｍＬと混合し、そこにジエチルエーテル５０ｍＬを加えて抽出した。抽出は３回行った。抽出後の有機層に、無水硫酸マグネシウムを加えて乾燥し、減圧ろ過した後の溶液から溶媒を留去し、無色固体１．５ｇを得た。この固体のＮＭＲ測定結果を以下に示す。この結果から、この無色固体が中間体化合物（Ｇ３）であることが確認された（収率９４％）。
1H-NMR(DMSO-d6) δ:1.3-1.8 (m, 8H), 2.62 (m, 1H), 3.04 (s, 1H), 3.81 (s, 3H), 4.05 (t, 2H), 4.54 (m, 1H), 5.70 (s, 1H), 6.01 (s, 1H), 7.03 (d, 2H), 7.89 (d, 2H) Next, 1.25 g (5.0 mmol) of the intermediate compound (F3) obtained above, 0.83 g (5.0 mmol) of 2- (bromomethyl) acrylic acid, Amberlyst (registered) Trademark) 15 (Rohm End Haas Co., Ltd. trade name) 0.8 g, THF 8.0 mL, tin (II) chloride 0.95 g (5.0 mmol), and pure water 2.0 mL were added to form a mixture, and the mixture was kept at 70 ° C. for 5 hours. Stir to react. After completion of the reaction, the reaction solution was filtered under reduced pressure and mixed with 40 mL of pure water, and 50 mL of diethyl ether was added thereto for extraction. Extraction was performed three times. The organic layer after extraction was dried by adding anhydrous magnesium sulfate, and the solvent was distilled off from the solution after filtration under reduced pressure to obtain 1.5 g of a colorless solid. The NMR measurement result of this solid is shown below. From this result, it was confirmed that this colorless solid was an intermediate compound (G3) (yield 94%).
1 H-NMR (DMSO-d6) δ: 1.3-1.8 (m, 8H), 2.62 (m, 1H), 3.04 (s, 1H), 3.81 (s, 3H), 4.05 (t, 2H), 4.54 ( m, 1H), 5.70 (s, 1H), 6.01 (s, 1H), 7.03 (d, 2H), 7.89 (d, 2H)
［４］中間体化合物（Ｈ３）の合成
Figure JPOXMLDOC01-appb-C000042
 [4] Synthesis of intermediate compound (H3)
Figure JPOXMLDOC01-appb-C000042
　冷却管付き１００ｍＬナスフラスコに、エタノール３５ｍＬ、上記で得られた中間体化合物（Ｇ３）１．５ｇ（４．７ｍｍｏｌ）、及び１０質量％水酸化ナトリウム水溶液５ｍＬを加えて混合物とし、８５℃で３時間撹拌しながら反応させた。反応終了後、５００ｍＬのビーカーに水３００ｍＬと反応液とを加えて、３０分間室温で撹拌した後、１０質量％ＨＣｌ水溶液５ｍＬを滴下した後、ろ過して白色固体１．３ｇを得た。次に、冷却管付き５０ｍＬナスフラスコに、得られた白色固体１．１ｇ、Ａｍｂｅｒｌｙｓｔ（登録商標）１５（ロームエンドハース社　商品名）１．０ｇ、及びＴＨＦ２０．０ｍＬを加えて混合物とし、７０℃で５時間撹拌して反応させた。反応終了後、反応液を減圧ろ過した後の溶液から溶媒を留去し、黄色固体を得た。この黄色固体を再結晶（ヘキサン／酢酸エチル＝１／１（ｖ／ｖ））で精製した後、白色固体０．９ｇを得た。この固体のＮＭＲ測定結果を以下に示す。この結果から、この白色固体が目的の中間体化合物（Ｈ３）であることが確認された（収率７１％）。
1H-NMR(DMSO-d6) δ:1.2-1.8 (m, 8H), 2.60 (m, 1H), 3.09 (m, 1H), 4.04 (m, 2H), 4.55 (m, 1H), 5.69 (s, 1H), 6.02 (s, 1H), 6.99 (d, 2H), 7.88 (d, 2H), 12.5 (s, broad, 1H) To a 100 mL eggplant flask equipped with a condenser tube, 35 mL of ethanol, 1.5 g (4.7 mmol) of the intermediate compound (G3) obtained above, and 5 mL of 10% by mass aqueous sodium hydroxide solution were added to form a mixture. The reaction was allowed to stir for an hour. After completion of the reaction, 300 mL of water and the reaction solution were added to a 500 mL beaker, and the mixture was stirred for 30 minutes at room temperature. Then, 5 mL of a 10% by mass aqueous HCl solution was added dropwise, followed by filtration to obtain 1.3 g of a white solid. Next, 1.1 g of the obtained white solid, Amberlyst (registered trademark) 15 (trade name of Rohm End Haas Co., Ltd.) 1.0 g, and 20.0 mL of THF are added to a 50 mL eggplant flask with a condenser tube to obtain a mixture, For 5 hours with stirring. After completion of the reaction, the solvent was distilled off from the solution after filtering the reaction solution under reduced pressure to obtain a yellow solid. The yellow solid was purified by recrystallization (hexane / ethyl acetate = 1/1 (v / v)) to obtain 0.9 g of a white solid. The NMR measurement result of this solid is shown below. From this result, it was confirmed that this white solid was the target intermediate compound (H3) (yield 71%).
1 H-NMR (DMSO-d6) δ: 1.2-1.8 (m, 8H), 2.60 (m, 1H), 3.09 (m, 1H), 4.04 (m, 2H), 4.55 (m, 1H), 5.69 ( s, 1H), 6.02 (s, 1H), 6.99 (d, 2H), 7.88 (d, 2H), 12.5 (s, broad, 1H)
　［５］化合物（Ｐ３）の合成
Figure JPOXMLDOC01-appb-C000043
 [5] Synthesis of compound (P3)
Figure JPOXMLDOC01-appb-C000043
　３－ブロモ－１－プロパノール１９．２ｇ（１３８．０ｍｍｏｌ）をトリエチルアミン（ＴＥＡ）１８．９ｍＬと少量のＢＨＴと共にＴＨＦ１００ｍＬに溶解させて室温にて攪拌し、水浴による冷却下、ＴＨＦ５０ｍＬに溶解した１２．２ｍＬ（１５０ｍｍｏｌ）の塩化アクリロイルを１５分間かけて滴下して３０分間攪拌し、水浴を除去して室温に戻しながら終夜攪拌を続けた。析出したＴＥＡ塩酸塩をろ過し、そのろ液よりＴＨＦを留去してジエチルエーテル１００ｍＬを添加し、その有機層を順次各８０ｍＬ飽和炭酸水素ナトリウム水溶液、０．５ｍｏｌ／Ｌ塩酸、飽和食塩水にて洗浄し、硫酸マグネシウムで乾燥後、溶媒を留去して化合物（Ｐ３）１８．２ｇを得た。この固体をＮＭＲで測定した結果を以下に示す。
1H-NMR (CDCl3) δ: 2.20 (m, 2H), 3.45 (t, 2H), 4.33 (t, 2H), 5.84 (d, 1H), 6.13 (ｍ, 1H), 6.44 (d, 1H) 13.1 g (138.0 mmol) of 3-bromo-1-propanol was dissolved in 100 mL of THF together with 18.9 mL of triethylamine (TEA) and a small amount of BHT, stirred at room temperature, and dissolved in 50 mL of THF under cooling with a water bath. 2 mL (150 mmol) of acryloyl chloride was added dropwise over 15 minutes and the mixture was stirred for 30 minutes. The water bath was removed, and the mixture was stirred overnight while returning to room temperature. The precipitated TEA hydrochloride was filtered, THF was distilled off from the filtrate, 100 mL of diethyl ether was added, and the organic layer was successively added to each 80 mL saturated aqueous sodium bicarbonate solution, 0.5 mol / L hydrochloric acid, and saturated brine. After washing with magnesium sulfate, the solvent was distilled off to obtain 18.2 g of Compound (P3). The result of having measured this solid by NMR is shown below.
1 H-NMR (CDCl 3 ) δ: 2.20 (m, 2H), 3.45 (t, 2H), 4.33 (t, 2H), 5.84 (d, 1H), 6.13 (m, 1H), 6.44 (d, 1H )
　［６］中間体化合物（Ｊ３）の合成
Figure JPOXMLDOC01-appb-C000044
 [6] Synthesis of intermediate compound (J3)
Figure JPOXMLDOC01-appb-C000044
　冷却官付き５００ｍＬのナスフラスコに、４－ヒドロキシ－４'－ビフェノール１７．６ｇ（９４．３ｍｍｏｌ）、化合物（Ｐ３）１８．２ｇ（９４．３ｍｍｏｌ）、炭酸カリウム２４．０ｇ（１９０ｍｍｏｌ）、アセトン２５０ｍＬを加えて混合物とし、温度５４℃で２０時間攪拌しながら反応させた。反応終了後、反応液を減圧ろ過して減圧下で溶媒を留去し黄色の湿潤固体を得た。この固体を、カラムクロマトグラフィー（カラム：シリカゲル６０，０．０６３－０．２００ｍｍ，メルク社製、溶出液：へキサン／酢酸エチル＝２／１）により精製した。ここで得られた溶液から溶媒を留去し、白色の固体６．１ｇを得た。この固体をＮＭＲで測定した結果を以下に示す。この結果から、この白色固体が中間体化合物（Ｊ３）であることが確認された（収率２２％）。
1H-NMR (CDCl3) δ: 2.21 (m, 2H), 4.13 (t, 2H), 4.40 (t, 2H), 4.99 (s, 1H), 5.87 (d, 1H), 6.15 (ｍ, 1H), 6.40 (d, 1H), 6.87 (d, 2H), 6.99 (d, 2H), 7.46 (m, 4H) In a 500 mL eggplant flask equipped with a cooling officer, 17.6 g (94.3 mmol) of 4-hydroxy-4′-biphenol, 18.2 g (94.3 mmol) of compound (P3), 24.0 g (190 mmol) of potassium carbonate, 250 mL of acetone Was added to make a mixture, and the mixture was reacted at a temperature of 54 ° C. with stirring for 20 hours. After completion of the reaction, the reaction solution was filtered under reduced pressure, and the solvent was distilled off under reduced pressure to obtain a yellow wet solid. This solid was purified by column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck & Co., eluent: hexane / ethyl acetate = 2/1). The solvent was distilled off from the solution obtained here to obtain 6.1 g of a white solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid was an intermediate compound (J3) (yield 22%).
1 H-NMR (CDCl 3 ) δ: 2.21 (m, 2H), 4.13 (t, 2H), 4.40 (t, 2H), 4.99 (s, 1H), 5.87 (d, 1H), 6.15 (m, 1H ), 6.40 (d, 1H), 6.87 (d, 2H), 6.99 (d, 2H), 7.46 (m, 4H)
［７］重合性液晶化合物（Ｂ１）の合成
Figure JPOXMLDOC01-appb-C000045
 [7] Synthesis of polymerizable liquid crystal compound (B1)
Figure JPOXMLDOC01-appb-C000045
　上記で得られた中間体化合物（Ｈ３）６．１ｇ（２０．０ｍｍｏｌ）、中間体化合物（Ｊ３）６．０ｇ（２０．０ｍｍｏｌ）、Ｎ，Ｎ－ジメチル－４－アミノピリジン（ＤＭＡＰ）０．０８ｇ及び少量の２，６－ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール（ＢＨＴ）を室温にて撹拌下、ジクロロメタン１０ｍＬに懸濁させ、それにジクロロメタン２０ｍＬに溶解させたジシクロヘキシルカルボジイミド（ＤＣＣ）４．７ｇ（２３．０ｍｍｏｌ）を加えて終夜撹拌後、析出したＤＣＣウレアをろ別し、そのろ液を、順次、各６０ｍＬの０．５ｍｏｌ／Ｌ塩酸と飽和炭酸水素ナトリウム水溶液と飽和食塩水にて２回洗浄し、硫酸マグネシウムで乾燥後、溶媒を留去し、エタノールによる再結晶操作で、重合性液晶化合物（Ｂ１）８．８ｇを得た（収率は７５％）。この固体をＮＭＲで測定した結果を以下に示す。
1H-NMR (CDCl3) δ： 1.53 (m, 6H), 1.81 (m, 2H), 2.20 (m, 2H), 2.60 (m, 1H), 3.07 (m, 1H), 4.06 (t, 2H), 4.12 (t, 2H), 4.40 (t, 2H), 4.54 (m, 1H), 5.63 (d, 1H), 5.85 (d, 1H), 6.10 (m, 1H), 6.24 (d, 1H),  6.42 (d, 1H), 6.97 (d, 4H), 7.25 (m, 2H), 7.54 (m, 2H), 7.59 (m, 2H), 8.17 (d, 2H)
　なお、重合性液晶化合物（Ｂ１）の液晶相を観察した結果、昇温時、１０９℃でスメックチックＸ相に相転移し、１４４℃でネマチック相に相転移し、１６８℃で等方性液体状態となった。 Intermediate compound (H3) 6.1 g (20.0 mmol), intermediate compound (J3) 6.0 g (20.0 mmol) obtained above, N, N-dimethyl-4-aminopyridine (DMAP) 0. 08 g and a small amount of 2,6-di-tert-butyl-p-cresol (BHT) were suspended in 10 mL of dichloromethane with stirring at room temperature, and 4.7 g of dicyclohexylcarbodiimide (DCC) dissolved in 20 mL of dichloromethane. 23.0 mmol) was added and stirred overnight, and the precipitated DCC urea was filtered off, and the filtrate was washed twice with 60 mL of 0.5 mol / L hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution and saturated brine successively. After washing and drying with magnesium sulfate, the solvent was distilled off, and 8.8 g of a polymerizable liquid crystal compound (B1) was obtained by recrystallization with ethanol (yield). 75%). The result of having measured this solid by NMR is shown below.
1 H-NMR (CDCl3) δ: 1.53 (m, 6H), 1.81 (m, 2H), 2.20 (m, 2H), 2.60 (m, 1H), 3.07 (m, 1H), 4.06 (t, 2H) , 4.12 (t, 2H), 4.40 (t, 2H), 4.54 (m, 1H), 5.63 (d, 1H), 5.85 (d, 1H), 6.10 (m, 1H), 6.24 (d, 1H), 6.42 (d, 1H), 6.97 (d, 4H), 7.25 (m, 2H), 7.54 (m, 2H), 7.59 (m, 2H), 8.17 (d, 2H)
As a result of observing the liquid crystal phase of the polymerizable liquid crystal compound (B1), the phase transition to the smectic X phase at 109 ° C. during the temperature rise, the phase transition to the nematic phase at 144 ° C., and the isotropic liquid state at 168 ° C. It became.
［実施例、比較例］重合性液晶組成物及びその重合物（フィルム）
　以下の実施例及び比較例で使用した化合物は下記のとおりである。また、実施例１～８で用いた組成物の組成を表１に示し、比較例１～５で用いた組成物の組成を表２に示す。
　なお、下記化合物（Ｃ１）、（Ｃ２）、（Ｃ３）、（Ｃ５）及び（Ｅ１）は新中村化学工業（株）の製品であり、化合物（Ｃ４）は日本化薬（株）の製品であり、化合物（Ｅ２）は東京化成工業（株）の製品である。化合物（Ｅ３）は公知である。 [Examples and Comparative Examples] Polymerizable liquid crystal composition and polymer (film) thereof
The compounds used in the following examples and comparative examples are as follows. The compositions of the compositions used in Examples 1 to 8 are shown in Table 1, and the compositions of the compositions used in Comparative Examples 1 to 5 are shown in Table 2.
The following compounds (C1), (C2), (C3), (C5) and (E1) are products of Shin-Nakamura Chemical Co., Ltd., and compound (C4) is a product of Nippon Kayaku Co., Ltd. Yes, compound (E2) is a product of Tokyo Chemical Industry Co., Ltd. Compound (E3) is known.
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-T000049
Figure JPOXMLDOC01-appb-T000049
Figure JPOXMLDOC01-appb-T000050
Figure JPOXMLDOC01-appb-T000050
［実施例１］重合性液晶組成物及びその重合物（フィルム）
　重合性液晶化合物（Ａ１）１５０ｍｇ、重合性液晶化合物（Ａ２）９０ｍｇ、重合性液晶化合物（Ｂ１）６０ｍｇ、多価アクリレート化合物（Ｃ１）９ｍｇ、光重合開始剤であるチバガイギー社製イルガキュア３６９（商品名）４ｍｇ、及び界面活性剤であるＲ３０（ＤＩＣ（株）製）０．６ｍｇをシクロヘキサノン０．７ｇに溶解し、重合性液晶組成物を得た。 [Example 1] Polymerizable liquid crystal composition and polymer (film) thereof
150 mg of polymerizable liquid crystal compound (A1), 90 mg of polymerizable liquid crystal compound (A2), 60 mg of polymerizable liquid crystal compound (B1), 9 mg of polyvalent acrylate compound (C1), Irgacure 369 manufactured by Ciba Geigy Co., Ltd. (trade name) 4 mg and 0.6 mg of surfactant R30 (manufactured by DIC Corporation) were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
　この重合性液晶組成物を、液晶配向膜付基板の液晶配向膜面にスピンコート（１，０００ｒｐｍ、２０秒間）により塗布し、１００℃のホットプレート上で６０秒間プリベークした後、室温まで放冷した。このとき、基板上の重合性組成物は液晶状態であった。ここで用いた液晶配向膜付基板は、ＩＴＯ付ガラス基板のＩＴＯ面に、液晶配向剤（日産化学工業（株）製ＳＥ－１４１０）をスピンコートにより塗布し、２３０℃で焼成して厚さ１００ｎｍの薄膜を形成した後、ラビング処理を施したものである。 This polymerizable liquid crystal composition is applied to the liquid crystal alignment film surface of the substrate with a liquid crystal alignment film by spin coating (1,000 rpm, 20 seconds), pre-baked on a hot plate at 100 ° C. for 60 seconds, and then allowed to cool to room temperature. did. At this time, the polymerizable composition on the substrate was in a liquid crystal state. The substrate with a liquid crystal alignment film used here has a thickness obtained by applying a liquid crystal alignment agent (SE-1410 manufactured by Nissan Chemical Industries, Ltd.) to the ITO surface of a glass substrate with ITO by spin coating and baking at 230 ° C. A 100-nm thin film is formed and then subjected to a rubbing treatment.
　次に、液晶配向膜付基板に形成された塗膜を、窒素雰囲気中で、メタルハライドランプを用いて２，０００ｍＪ／ｃｍ2の強さの光を照射して重合性液晶組成物を重合させた。
　得られたフィルムの膜厚は１．８μｍであり、偏光顕微鏡でそれを観察したところ、フィルムが基板面にハイブリッド配向している（平均チルト４０°）ことを確認した。そのリタデーション値は１１７ｎｍであり、ヘイズ値は１．４４であった。
　このフィルムを２００℃のホットプレート上で３０分間加熱したところ、リタデーション値は１０９ｎｍであり、ヘイズ値は１．３０であった。 Next, the coating film formed on the substrate with a liquid crystal alignment film was irradiated with light having a strength of 2,000 mJ / cm 2 using a metal halide lamp in a nitrogen atmosphere to polymerize the polymerizable liquid crystal composition. .
The film thickness of the obtained film was 1.8 μm, and when observed with a polarizing microscope, it was confirmed that the film was hybrid-aligned on the substrate surface (average tilt 40 °). The retardation value was 117 nm and the haze value was 1.44.
When this film was heated on a hot plate at 200 ° C. for 30 minutes, the retardation value was 109 nm and the haze value was 1.30.
［実施例２］重合性液晶組成物及びその重合物（フィルム）
　重合性液晶化合物（Ａ１）１５０ｍｇ、重合性液晶化合物（Ａ２）９０ｍｇ、重合性液晶化合物（Ｂ１）６０ｍｇ、多価アクリレート化合物（Ｃ２）１５ｍｇ、光重合開始剤であるチバガイギー社製イルガキュア３６９（商品名）４ｍｇ、及び界面活性剤であるＲ３０（ＤＩＣ（株）製）０．６ｍｇをシクロヘキサノン０．７ｇに溶解し、重合性液晶組成物を得た。 [Example 2] Polymerizable liquid crystal composition and polymer (film) thereof
150 mg of polymerizable liquid crystal compound (A1), 90 mg of polymerizable liquid crystal compound (A2), 60 mg of polymerizable liquid crystal compound (B1), 15 mg of polyvalent acrylate compound (C2), Irgacure 369 manufactured by Ciba Geigy Co., Ltd. (trade name) 4 mg and 0.6 mg of surfactant R30 (manufactured by DIC Corporation) were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
　この重合性液晶組成物を用いた以外は実施例１と同様にしてフィルムを作製した。なお、プリベーク後の基板上の重合性組成物は液晶状態であった。
　得られたフィルムの膜厚は１．８μｍであり、偏光顕微鏡でそれを観察したところ、フィルムが基板面にハイブリッド配向している（平均チルト４０°）ことを確認した。そのリタデーション値は１２１ｎｍであり、ヘイズ値は０．６６であった。
　このフィルムを２００℃のホットプレート上で３０分間加熱したところ、リタデーション値は１０９ｎｍであり、ヘイズ値は０．３８であった。 A film was produced in the same manner as in Example 1 except that this polymerizable liquid crystal composition was used. The polymerizable composition on the substrate after pre-baking was in a liquid crystal state.
The film thickness of the obtained film was 1.8 μm, and when observed with a polarizing microscope, it was confirmed that the film was hybrid-aligned on the substrate surface (average tilt 40 °). The retardation value was 121 nm and the haze value was 0.66.
When this film was heated on a hot plate at 200 ° C. for 30 minutes, the retardation value was 109 nm and the haze value was 0.38.
［実施例３］重合性液晶組成物及びその重合物（フィルム）
　重合性液晶化合物（Ａ１）１５０ｍｇ、重合性液晶化合物（Ａ２）９０ｍｇ、重合性液晶化合物（Ｂ１）６０ｍｇ、多価アクリレート化合物（Ｃ３）１５ｍｇ、光重合開始剤であるチバガイギー社製イルガキュア３６９（商品名）４ｍｇ、及び界面活性剤であるＲ３０（ＤＩＣ（株）製）０．６ｍｇをシクロヘキサノン０．７ｇに溶解し、重合性液晶組成物を得た。 [Example 3] Polymerizable liquid crystal composition and polymer (film) thereof
150 mg of polymerizable liquid crystal compound (A1), 90 mg of polymerizable liquid crystal compound (A2), 60 mg of polymerizable liquid crystal compound (B1), 15 mg of polyvalent acrylate compound (C3), Irgacure 369 manufactured by Ciba Geigy Co., Ltd. (trade name) 4 mg and 0.6 mg of surfactant R30 (manufactured by DIC Corporation) were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
　この重合性液晶組成物を用いた以外は実施例１と同様にしてフィルムを作製した。なお、プリベーク後の基板上の重合性組成物は液晶状態であった。
　得られたフィルムの膜厚は１．８μｍであり、偏光顕微鏡でそれを観察したところ、フィルムが基板面にハイブリッド配向している（平均チルト４０°）ことを確認した。そのリタデーション値は１１５ｎｍであり、ヘイズ値は０．０８であった。
　このフィルムを２００℃のホットプレート上で３０分間加熱したところ、リタデーション値は９８ｎｍであり、ヘイズ値は０．０７であった。 A film was produced in the same manner as in Example 1 except that this polymerizable liquid crystal composition was used. The polymerizable composition on the substrate after pre-baking was in a liquid crystal state.
The film thickness of the obtained film was 1.8 μm, and when observed with a polarizing microscope, it was confirmed that the film was hybrid-aligned on the substrate surface (average tilt 40 °). The retardation value was 115 nm and the haze value was 0.08.
When this film was heated on a hot plate at 200 ° C. for 30 minutes, the retardation value was 98 nm and the haze value was 0.07.
［実施例４］重合性液晶組成物及びその重合物（フィルム）
　重合性液晶化合物（Ａ１）１５０ｍｇ、重合性液晶化合物（Ａ２）９０ｍｇ、重合性液晶化合物（Ｂ１）６０ｍｇ、多価アクリレート化合物（Ｃ４）９ｍｇ、光重合開始剤であるチバガイギー社製イルガキュア３６９（商品名）４ｍｇ、及び界面活性剤であるＲ３０（ＤＩＣ（株）製）０．６ｍｇをシクロヘキサノン０．７ｇに溶解し、重合性液晶組成物を得た。 [Example 4] Polymerizable liquid crystal composition and polymer (film) thereof
150 mg of polymerizable liquid crystal compound (A1), 90 mg of polymerizable liquid crystal compound (A2), 60 mg of polymerizable liquid crystal compound (B1), 9 mg of polyvalent acrylate compound (C4), Irgacure 369 manufactured by Ciba Geigy Co., Ltd. (trade name) 4 mg and 0.6 mg of surfactant R30 (manufactured by DIC Corporation) were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
　この重合性液晶組成物を用いた以外は実施例１と同様にしてフィルムを作製した。なお、プリベーク後の基板上の重合性組成物は液晶状態であった。
　得られたフィルムの膜厚は１．８μｍであり、偏光顕微鏡でそれを観察したところ、フィルムが基板面にハイブリッド配向している（平均チルト４０°）ことを確認した。そのリタデーション値は１０１ｎｍであり、ヘイズ値は０．０５であった。
　このフィルムを２００℃のホットプレート上で３０分間加熱したところ、リタデーション値は９２ｎｍであり、ヘイズ値は０．０７であった。 A film was produced in the same manner as in Example 1 except that this polymerizable liquid crystal composition was used. The polymerizable composition on the substrate after pre-baking was in a liquid crystal state.
The film thickness of the obtained film was 1.8 μm, and when observed with a polarizing microscope, it was confirmed that the film was hybrid-aligned on the substrate surface (average tilt 40 °). The retardation value was 101 nm, and the haze value was 0.05.
When this film was heated on a hot plate at 200 ° C. for 30 minutes, the retardation value was 92 nm and the haze value was 0.07.
［実施例５］重合性液晶組成物及びその重合物（フィルム）
　重合性液晶化合物（Ａ１）１５０ｍｇ、重合性液晶化合物（Ａ２）９０ｍｇ、重合性液晶化合物（Ｂ１）６０ｍｇ、多価アクリレート化合物（Ｃ４）１５ｍｇ、光重合開始剤であるチバガイギー社製イルガキュア３６９（商品名）４ｍｇ、及び界面活性剤であるＲ３０（ＤＩＣ（株）製）０．６ｍｇをシクロヘキサノン０．７ｇに溶解し、重合性液晶組成物を得た。 [Example 5] Polymerizable liquid crystal composition and polymer (film) thereof
150 mg of polymerizable liquid crystal compound (A1), 90 mg of polymerizable liquid crystal compound (A2), 60 mg of polymerizable liquid crystal compound (B1), 15 mg of polyvalent acrylate compound (C4), Irgacure 369 manufactured by Ciba Geigy Co., Ltd. (trade name) 4 mg and 0.6 mg of surfactant R30 (manufactured by DIC Corporation) were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
　この重合性液晶組成物を用いた以外は実施例１と同様にしてフィルムを作製した。なお、プリベーク後の基板上の重合性組成物は液晶状態であった。
　得られたフィルムの膜厚は１．８μｍであり、偏光顕微鏡でそれを観察したところ、フィルムが基板面にハイブリッド配向している（平均チルト４０°）ことを確認した。そのリタデーション値は９６ｎｍであり、ヘイズ値は１．１５であった。
　このフィルムを２００℃のホットプレート上で３０分間加熱したところ、リタデーション値は９５ｎｍであり、ヘイズ値は２．１８であった。 A film was produced in the same manner as in Example 1 except that this polymerizable liquid crystal composition was used. The polymerizable composition on the substrate after pre-baking was in a liquid crystal state.
The film thickness of the obtained film was 1.8 μm, and when observed with a polarizing microscope, it was confirmed that the film was hybrid-aligned on the substrate surface (average tilt 40 °). The retardation value was 96 nm and haze value was 1.15.
When this film was heated on a hot plate at 200 ° C. for 30 minutes, the retardation value was 95 nm and the haze value was 2.18.
［実施例６］重合性液晶組成物及びその重合物（フィルム）
　重合性液晶化合物（Ａ１）１５０ｍｇ、重合性液晶化合物（Ａ２）９０ｍｇ、重合性液晶化合物（Ｂ１）６０ｍｇ、多価アクリレート化合物（Ｃ５）３ｍｇ、光重合開始剤であるチバガイギー社製イルガキュア３６９（商品名）４ｍｇ、及び界面活性剤であるＲ３０（ＤＩＣ（株）製）０．６ｍｇをシクロヘキサノン０．７ｇに溶解し、重合性液晶組成物を得た。 [Example 6] Polymerizable liquid crystal composition and polymer (film) thereof
150 mg of polymerizable liquid crystal compound (A1), 90 mg of polymerizable liquid crystal compound (A2), 60 mg of polymerizable liquid crystal compound (B1), 3 mg of polyvalent acrylate compound (C5), Irgacure 369 manufactured by Ciba Geigy Co., Ltd. (trade name) 4 mg and 0.6 mg of surfactant R30 (manufactured by DIC Corporation) were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
　この重合性液晶組成物を用いた以外は実施例１と同様にしてフィルムを作製した。なお、プリベーク後の基板上の重合性組成物は液晶状態であった。
　得られたフィルムの膜厚は１．８μｍであり、偏光顕微鏡でそれを観察したところ、フィルムが基板面にハイブリッド配向している（平均チルト４０°）ことを確認した。そのリタデーション値は１０６ｎｍであり、ヘイズ値は０．０３であった。
　このフィルムを２００℃のホットプレート上で３０分間加熱したところ、リタデーション値は９９ｎｍであり、ヘイズ値は０．０８であった。 A film was produced in the same manner as in Example 1 except that this polymerizable liquid crystal composition was used. The polymerizable composition on the substrate after pre-baking was in a liquid crystal state.
The film thickness of the obtained film was 1.8 μm, and when observed with a polarizing microscope, it was confirmed that the film was hybrid-aligned on the substrate surface (average tilt 40 °). The retardation value was 106 nm and the haze value was 0.03.
When this film was heated on a hot plate at 200 ° C. for 30 minutes, the retardation value was 99 nm and the haze value was 0.08.
［比較例１］重合性液晶組成物及びその重合物（フィルム）
　重合性液晶化合物（Ａ１）１５０ｍｇ、重合性液晶化合物（Ａ２）９０ｍｇ、重合性液晶化合物（Ｂ１）６０ｍｇ、化合物（Ｅ１）１５ｍｇ、光重合開始剤であるチバガイギー社製イルガキュア３６９（商品名）４ｍｇ、及び界面活性剤であるＲ３０（ＤＩＣ（株）製）０．６ｍｇをシクロヘキサノン０．７ｇに溶解し、重合性液晶組成物を得た。 [Comparative Example 1] Polymerizable liquid crystal composition and polymer (film)
150 mg of polymerizable liquid crystal compound (A1), 90 mg of polymerizable liquid crystal compound (A2), 60 mg of polymerizable liquid crystal compound (B1), 15 mg of compound (E1), 4 mg of Irgacure 369 (trade name) manufactured by Ciba Geigy Co., which is a photopolymerization initiator, In addition, 0.6 mg of surfactant R30 (manufactured by DIC Corporation) was dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
　この重合性液晶組成物を用いた以外は実施例１と同様にしてフィルムを作製した。なお、プリベーク後の基板上の重合性組成物は液晶状態であった。
　得られたフィルムの膜厚は１．７μｍであり、偏光顕微鏡でそれを観察したところ、フィルムが基板面に水平配向（チルト＜１０°）していることを確認した。そのリタデーション値は２９６ｎｍであり、ヘイズ値は０．０８であった。
　このフィルムを２００℃のホットプレート上で３０分間加熱したところ、リタデーション値は２０１ｎｍであり、ヘイズ値は０．０８であった。 A film was produced in the same manner as in Example 1 except that this polymerizable liquid crystal composition was used. The polymerizable composition on the substrate after pre-baking was in a liquid crystal state.
The film thickness of the obtained film was 1.7 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented (tilt <10 °) on the substrate surface. The retardation value was 296 nm and the haze value was 0.08.
When this film was heated on a hot plate at 200 ° C. for 30 minutes, the retardation value was 201 nm and the haze value was 0.08.
［比較例２］重合性液晶組成物及びその重合物（フィルム）
　重合性液晶化合物（Ａ１）１５０ｍｇ、重合性液晶化合物（Ａ２）９０ｍｇ、重合性液晶化合物（Ｂ１）６０ｍｇ、化合物（Ｅ２）３０ｍｇ、光重合開始剤であるチバガイギー社製イルガキュア３６９（商品名）４ｍｇ、及び界面活性剤であるＲ３０（ＤＩＣ（株）製）０．６ｍｇをシクロヘキサノン０．７ｇに溶解し、重合性液晶組成物を得た。 [Comparative Example 2] Polymerizable liquid crystal composition and polymer (film)
150 mg of polymerizable liquid crystal compound (A1), 90 mg of polymerizable liquid crystal compound (A2), 60 mg of polymerizable liquid crystal compound (B1), 30 mg of compound (E2), 4 mg of Irgacure 369 (trade name) manufactured by Ciba Geigy Co., which is a photopolymerization initiator, In addition, 0.6 mg of surfactant R30 (manufactured by DIC Corporation) was dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
　この重合性液晶組成物を用いた以外は実施例１と同様にしてフィルムを作製した。なお、プリベーク後の基板上の重合性組成物は液晶状態であった。
　得られたフィルムの膜厚は１．９μｍであり、偏光顕微鏡でそれを観察したところ、フィルムが基板面に水平配向（チルト＜１０°）していることを確認した。そのリタデーション値は２６１ｎｍであり、ヘイズ値は０．０８であった。
　このフィルムを２００℃のホットプレート上で３０分間加熱したところ、リタデーション値は１４４ｎｍであり、ヘイズ値は０．０８であった。 A film was produced in the same manner as in Example 1 except that this polymerizable liquid crystal composition was used. The polymerizable composition on the substrate after pre-baking was in a liquid crystal state.
The film thickness of the obtained film was 1.9 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented (tilt <10 °) on the substrate surface. The retardation value was 261 nm and the haze value was 0.08.
When this film was heated on a hot plate at 200 ° C. for 30 minutes, the retardation value was 144 nm and the haze value was 0.08.
［比較例３］重合性液晶組成物及びその重合物（フィルム）
　重合性液晶化合物（Ａ１）１５０ｍｇ、重合性液晶化合物（Ａ２）９０ｍｇ、重合性液晶化合物（Ｂ１）６０ｍｇ、化合物（Ｅ３）３０ｍｇ、光重合開始剤であるチバガイギー社製イルガキュア３６９（商品名）４ｍｇ、及び界面活性剤であるＲ３０（ＤＩＣ（株）製）０．６ｍｇをシクロヘキサノン０．７ｇに溶解し、重合性液晶組成物を得た。 [Comparative Example 3] Polymerizable liquid crystal composition and polymer (film) thereof
150 mg of polymerizable liquid crystal compound (A1), 90 mg of polymerizable liquid crystal compound (A2), 60 mg of polymerizable liquid crystal compound (B1), 30 mg of compound (E3), 4 mg of Irgacure 369 (trade name) manufactured by Ciba Geigy Co., which is a photopolymerization initiator, In addition, 0.6 mg of surfactant R30 (manufactured by DIC Corporation) was dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
　この重合性液晶組成物を用いた以外は実施例１と同様にしてフィルムを作製した。なお、プリベーク後の基板上の重合性組成物は液晶状態であった。
　得られたフィルムの膜厚は１．９μｍであり、偏光顕微鏡でそれを観察したところ、フィルムが基板面に水平配向（チルト＜１０°）していることを確認した。そのリタデーション値は３２８ｎｍであり、ヘイズ値は０．１６であった。
　このフィルムを２００℃のホットプレート上で３０分間加熱したところ、リタデーション値は２６５ｎｍであり、ヘイズ値は０．１６であった。 A film was produced in the same manner as in Example 1 except that this polymerizable liquid crystal composition was used. The polymerizable composition on the substrate after pre-baking was in a liquid crystal state.
The film thickness of the obtained film was 1.9 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented (tilt <10 °) on the substrate surface. The retardation value was 328 nm and haze value was 0.16.
When this film was heated on a hot plate at 200 ° C. for 30 minutes, the retardation value was 265 nm and the haze value was 0.16.
［比較例４］重合性液晶組成物及びその重合物（フィルム）
　重合性液晶化合物（Ａ１）１５０ｍｇ、重合性液晶化合物（Ａ２）９０ｍｇ、重合性液晶化合物（Ｂ１）６０ｍｇ、光重合開始剤であるチバガイギー社製イルガキュア３６９（商品名）４ｍｇ、及び界面活性剤であるＲ３０（ＤＩＣ（株）製）０．６ｍｇをシクロヘキサノン０．７ｇに溶解し、重合性液晶組成物を得た。 [Comparative Example 4] Polymerizable liquid crystal composition and polymer (film) thereof
Polymerizable liquid crystal compound (A1) 150 mg, polymerizable liquid crystal compound (A2) 90 mg, polymerizable liquid crystal compound (B1) 60 mg, Ciba Geigy's Irgacure 369 (trade name) 4 mg as a photopolymerization initiator, and a surfactant. 0.6 mg of R30 (manufactured by DIC Corporation) was dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
　この重合性液晶組成物を用いた以外は実施例１と同様にしてフィルムを作製した。なお、プリベーク後の基板上の重合性組成物は液晶状態であった。
　得られたフィルムの膜厚は１．８μｍであり、偏光顕微鏡でそれを観察したところ、フィルムが基板面に水平配向（チルト＜１０°）していることを確認した。そのリタデーション値は２８９ｎｍであり、ヘイズ値は０．１６であった。
　このフィルムを２００℃のホットプレート上で３０分間加熱したところ、リタデーション値は２０９ｎｍであり、ヘイズ値は０．１６であった。 A film was produced in the same manner as in Example 1 except that this polymerizable liquid crystal composition was used. The polymerizable composition on the substrate after pre-baking was in a liquid crystal state.
The film thickness of the obtained film was 1.8 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented (tilt <10 °) on the substrate surface. The retardation value was 289 nm and haze value was 0.16.
When this film was heated on a hot plate at 200 ° C. for 30 minutes, the retardation value was 209 nm and the haze value was 0.16.
［比較例５］重合性液晶組成物及びその重合物（フィルム）
　重合性液晶化合物（Ａ１）１５０ｍｇ、重合性液晶化合物（Ａ２）１５０ｍｇ、多価アクリレート化合物（Ｃ４）９ｍｇ、光重合開始剤であるチバガイギー社製イルガキュア３６９（商品名）４ｍｇ、及び界面活性剤であるＲ３０（ＤＩＣ（株）製）０．６ｍｇをシクロヘキサノン０．７ｇに溶解し、重合性液晶組成物を得た。 [Comparative Example 5] Polymerizable liquid crystal composition and polymer (film) thereof
Polymeric liquid crystal compound (A1) 150 mg, polymerizable liquid crystal compound (A2) 150 mg, polyvalent acrylate compound (C4) 9 mg, Ciba Geigy's Irgacure 369 (trade name) 4 mg, which is a photopolymerization initiator, and a surfactant. 0.6 mg of R30 (manufactured by DIC Corporation) was dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
　この重合性液晶組成物を用いた以外は実施例１と同様にしてフィルムを作製した。なお、プリベーク後の基板上の重合性組成物は液晶状態であった。
　得られたフィルムの膜厚は１．８μｍであり、偏光顕微鏡でそれを観察したところ、フィルムが基板面に水平配向（チルト＜１０°）していることを確認した。そのリタデーション値は２５８ｎｍであり、ヘイズ値は１．４９であった。
　このフィルムを２００℃のホットプレート上で３０分間加熱したところ、リタデーション値は１８ｎｍであり、ヘイズ値は０．２４であった。 A film was produced in the same manner as in Example 1 except that this polymerizable liquid crystal composition was used. The polymerizable composition on the substrate after pre-baking was in a liquid crystal state.
The film thickness of the obtained film was 1.8 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented (tilt <10 °) on the substrate surface. The retardation value was 258 nm and haze value was 1.49.
When this film was heated on a hot plate at 200 ° C. for 30 minutes, the retardation value was 18 nm and the haze value was 0.24.
　上記実施例１～６及び比較例１～５のまとめを下記表３に示す。なお、表３中Δｎｄ値の熱安定性（％）とは、ベーク前Δｎｄ値に対するベーク後Δｎｄ値の割合である。
　また、上記実施例１～６で作製したフィルムの波長５９０ｎｍにおけるリタデーション値角度依存性を図１に示し、上記比較例１～５で作製したフィルムの波長５９０ｎｍにおけるリタデーション値角度依存性を図２に示す。 The summary of Examples 1 to 6 and Comparative Examples 1 to 5 is shown in Table 3 below. In Table 3, Δnd value thermal stability (%) is the ratio of Δnd value after baking to Δnd value before baking.
In addition, the retardation value angle dependency of the films prepared in Examples 1 to 6 at a wavelength of 590 nm is shown in FIG. 1, and the retardation value angle dependency of the films prepared in Comparative Examples 1 to 5 at a wavelength of 590 nm is shown in FIG. Show.
Figure JPOXMLDOC01-appb-T000051
Figure JPOXMLDOC01-appb-T000051
　次に、配向フィルム作製プロセスによる配向モード（水平又はハイブリッド）のコントロールについて、実施例を挙げて説明する。 Next, the control of the alignment mode (horizontal or hybrid) by the alignment film manufacturing process will be described with examples.
［実施例７］重合性液晶組成物及びその重合物（フィルム）
　重合性液晶化合物（Ａ１）１５０ｍｇ、重合性液晶化合物（Ａ２）９０ｍｇ、重合性液晶化合物（Ｂ１）６０ｍｇ、及び多価アクリレート化合物（Ｃ４）４．５ｍｇ、光重合開始剤であるチバガイギー社製イルガキュア３６９（商品名）４ｍｇ、及び界面活性剤であるＲ３０（ＤＩＣ（株）製）０．６ｍｇをシクロヘキサノン０．７ｇに溶解し、重合性液晶組成物を得た。 [Example 7] Polymerizable liquid crystal composition and polymer (film) thereof
Polymerizable liquid crystal compound (A1) 150 mg, polymerizable liquid crystal compound (A2) 90 mg, polymerizable liquid crystal compound (B1) 60 mg, and polyvalent acrylate compound (C4) 4.5 mg, Irgacure 369 manufactured by Ciba Geigy Co., which is a photopolymerization initiator (Product name) 4 mg and surfactant R30 (manufactured by DIC Corporation) 0.6 mg were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.
　この重合性液晶組成物を、液晶配向膜付基板の液晶配向膜面にスピンコート（１，０００ｒｐｍ、２０秒間）により塗布し、１００℃のホットプレート上で６０秒間プリベークした後、室温まで放冷した。このとき、基板上の重合性組成物は液晶状態であった。ここで用いた液晶配向膜付基板は、ＩＴＯ付ガラス基板のＩＴＯ面に、液晶配向剤（日産化学工業（株）製ＰＡＯＣ－１２０）をスピンコートにより塗布し、１３０℃で焼成して厚さ２００ｎｍの薄膜を形成した後、斜め（４０°）から５００ｍＪ／ｃｍ2の偏光ＵＶ光を照射したものである。 This polymerizable liquid crystal composition is applied to the liquid crystal alignment film surface of the substrate with a liquid crystal alignment film by spin coating (1,000 rpm, 20 seconds), pre-baked on a hot plate at 100 ° C. for 60 seconds, and then allowed to cool to room temperature. did. At this time, the polymerizable composition on the substrate was in a liquid crystal state. The substrate with a liquid crystal alignment film used here has a thickness obtained by applying a liquid crystal alignment agent (PAOC-120 manufactured by Nissan Chemical Industries, Ltd.) to the ITO surface of a glass substrate with ITO by spin coating and baking at 130 ° C. After forming a 200 nm thin film, it is irradiated with polarized UV light of 500 mJ / cm 2 obliquely (40 °).
　次に、液晶配向膜付基板に形成された塗膜を、窒素雰囲気中で、メタルハライドランプを用いて２，０００ｍＪ／ｃｍ2の強さの光を照射して重合性液晶組成物を重合させた。
　得られたフィルムの膜厚は１．８μｍであり、偏光顕微鏡でそれを観察したところ、フィルムが基板面にハイブリッド配向している（平均チルト４０°）ことを確認した。そのリタデーション値は１４３ｎｍであり、ヘイズ値は０．１３であった。 Next, the coating film formed on the substrate with a liquid crystal alignment film was irradiated with light having a strength of 2,000 mJ / cm 2 using a metal halide lamp in a nitrogen atmosphere to polymerize the polymerizable liquid crystal composition. .
The film thickness of the obtained film was 1.8 μm, and when observed with a polarizing microscope, it was confirmed that the film was hybrid-aligned on the substrate surface (average tilt 40 °). The retardation value was 143 nm and the haze value was 0.13.
［実施例８］重合性液晶組成物及びその重合物（フィルム）
　実施例７で得られた重合性液晶組成物を、液晶配向膜付基板の液晶配向膜面にスピンコート（１，０００ｒｐｍ、２０秒間）により塗布し、１００℃のホットプレート上で６０秒間プリベークした後、室温まで放冷した。このとき、基板上の重合性組成物は液晶状態であった。ここで用いた液晶配向膜付基板は、ＩＴＯ付ガラス基板のＩＴＯ面に、液晶配向剤（日産化学工業（株）製ＰＡＯＣ－１２０）をスピンコートにより塗布し、１３０℃で焼成して厚さ２００ｎｍの薄膜を形成した後、真上から１，０００ｍＪ／ｃｍ2の偏光ＵＶ光を照射したものである。 [Example 8] Polymerizable liquid crystal composition and polymer (film) thereof
The polymerizable liquid crystal composition obtained in Example 7 was applied to the liquid crystal alignment film surface of the substrate with a liquid crystal alignment film by spin coating (1,000 rpm, 20 seconds) and prebaked on a hot plate at 100 ° C. for 60 seconds. Then, it was left to cool to room temperature. At this time, the polymerizable composition on the substrate was in a liquid crystal state. The substrate with a liquid crystal alignment film used here has a thickness obtained by applying a liquid crystal alignment agent (PAOC-120 manufactured by Nissan Chemical Industries, Ltd.) to the ITO surface of a glass substrate with ITO by spin coating and baking at 130 ° C. After forming a 200 nm thin film, it was irradiated with polarized UV light of 1,000 mJ / cm 2 from directly above.
　次に、液晶配向膜付基板に形成された塗膜を、窒素雰囲気中で、メタルハライドランプを用いて２，０００ｍＪ／ｃｍ2の強さの光を照射して重合性液晶組成物を重合させた。
　得られたフィルムの膜厚は１．８μｍであり、偏光顕微鏡でそれを観察したところ、フィルムが基板面に水平配向していることを確認した。そのリタデーション値は３０６ｎｍであり、ヘイズ値は０．１３であった。 Next, the coating film formed on the substrate with a liquid crystal alignment film was irradiated with light having a strength of 2,000 mJ / cm 2 using a metal halide lamp in a nitrogen atmosphere to polymerize the polymerizable liquid crystal composition. .
The film thickness of the obtained film was 1.8 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally aligned on the substrate surface. The retardation value was 306 nm and the haze value was 0.13.
　上記実施例７、８で作製したフィルムの波長５９０ｎｍにおけるリタデーション値角度依存性を図３に示す。 FIG. 3 shows the retardation value angle dependency of the films prepared in Examples 7 and 8 at a wavelength of 590 nm.
　本発明の組成物から得られる重合体は、偏光板や位相差板等の光学異方性フィルムとして好適に利用することができる。 The polymer obtained from the composition of the present invention can be suitably used as an optically anisotropic film such as a polarizing plate or a retardation plate.

Claims (7)

  1. 　（Ａ）下記式［１］で表される重合性液晶化合物から選ばれる少なくとも１種、
    （Ｂ）下記式［２］で表される重合性液晶化合物から選ばれる少なくとも１種、及び
    （Ｃ）トリメチロールプロパン構造、ペンタエリスリトール構造及びエチレングリコール構造から選ばれる少なくとも１種の構造又はこれらから選ばれる少なくとも１種が縮合した構造を有する、全体で３以上５０以下の酸素原子を有する多価アルコールとアクリル酸又はその誘導体とから得られる多価アクリレート化合物から選ばれる少なくとも１種
    を含有することを特徴とする重合性液晶組成物。
    Figure JPOXMLDOC01-appb-C000001
     ［式中、Ｒ1、Ｒ3及びＲ4は、それぞれ独立に下記式［３］又は［４］
    Figure JPOXMLDOC01-appb-C000002
     （式中、Ｘは、水素原子又はメチル基である。破線は結合手である。）
    で表される有機基である。Ｒ2は、水素原子、ハロゲン原子、シアノ基又はメトキシ基である。ｎ１、ｎ２及びｎ３は、それぞれ独立に２～１０の整数である。ｑは０又は１である。ｐは、ｑが０のときは１、ｑが１のときは０又は１である。ｒは１又は２である。ｓは、ｒが１のときは１、ｒが２のときは０である。］     (A) at least one selected from polymerizable liquid crystal compounds represented by the following formula [1],
    (B) at least one selected from polymerizable liquid crystal compounds represented by the following formula [2], and (C) at least one structure selected from a trimethylolpropane structure, a pentaerythritol structure, and an ethylene glycol structure, or from these Containing at least one selected from polyhydric acrylate compounds obtained from polyhydric alcohols having 3 to 50 oxygen atoms in total and acrylic acid or derivatives thereof, having a structure in which at least one selected is condensed. A polymerizable liquid crystal composition characterized by the above.
    Figure JPOXMLDOC01-appb-C000001
     [Wherein R 1 , R 3 and R 4 each independently represents the following formula [3] or [4]
    Figure JPOXMLDOC01-appb-C000002
     (In the formula, X is a hydrogen atom or a methyl group. The broken line is a bond.)
    It is an organic group represented by. R 2 is a hydrogen atom, a halogen atom, a cyano group or a methoxy group. n1, n2 and n3 are each independently an integer of 2 to 10. q is 0 or 1. p is 1 when q is 0, and 0 or 1 when q is 1. r is 1 or 2; s is 1 when r is 1 and 0 when r is 2. ]
  2. 　上記多価アクリレート化合物（Ｃ）が、下記式［５］又は［６］で表される請求項１記載の重合性液晶組成物。
    Figure JPOXMLDOC01-appb-C000003
     （式中、Ｒ5は、メチル基、又は下記式［７］若しくは［８］
    Figure JPOXMLDOC01-appb-C000004
     で表される有機基である。ｎ４～ｎ１０は、それぞれ独立に０～１０の整数である。ｎ１１は４～１０の整数である。破線は結合手である。）     The polymerizable liquid crystal composition according to claim 1, wherein the polyvalent acrylate compound (C) is represented by the following formula [5] or [6].
    Figure JPOXMLDOC01-appb-C000003
     (In the formula, R 5 represents a methyl group, or the following formula [7] or [8].
    Figure JPOXMLDOC01-appb-C000004
     It is an organic group represented by. n4 to n10 are each independently an integer of 0 to 10. n11 is an integer of 4 to 10. A broken line is a bond. )
  3. 　前記重合性液晶化合物（Ｂ）が、下記式［９］で表される請求項１又は２記載の重合性液晶組成物。
    Figure JPOXMLDOC01-appb-C000005
     （式中、ｎ２、ｎ３、ｒ及びｓは上記と同じ。）     The polymerizable liquid crystal composition according to claim 1, wherein the polymerizable liquid crystal compound (B) is represented by the following formula [9].
    Figure JPOXMLDOC01-appb-C000005
     (Wherein n2, n3, r and s are the same as above)
  4. 　請求項１～３のいずれか１項記載の重合性液晶組成物から得られる重合体。 A polymer obtained from the polymerizable liquid crystal composition according to any one of claims 1 to 3.
  5. 　請求項１～３のいずれか１項記載の重合性液晶組成物から得られる被膜。 A film obtained from the polymerizable liquid crystal composition according to any one of claims 1 to 3.
  6. 　請求項１～３のいずれか１項記載の重合性液晶組成物から得られるハイブリッド配向フィルム。 A hybrid alignment film obtained from the polymerizable liquid crystal composition according to any one of claims 1 to 3.
  7. 　請求項６記載の配向フィルムを備える光学部材。 An optical member comprising the oriented film according to claim 6.
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