WO2013039053A1 - 重合性液晶組成物および配向フィルム - Google Patents

重合性液晶組成物および配向フィルム Download PDF

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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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English (en)
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/ko
Priority to JP2013533667A priority patent/JP5958471B2/ja
Priority to CN201280044775.8A priority patent/CN103827155B/zh
Publication of WO2013039053A1 publication Critical patent/WO2013039053A1/ja

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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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