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  • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C255/00—Carboxylic acid nitriles
  • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
  • C07C255/54—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and etherified hydroxy groups bound to the carbon skeleton
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
  • C09K19/06—Non-steroidal liquid crystal compounds
  • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
  • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
  • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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  • C09K19/00—Liquid crystal materials
  • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
  • C09K19/38—Polymers
  • C09K19/3833—Polymers with mesogenic groups in the side chain
  • C09K19/3842—Polyvinyl derivatives
  • C09K19/3847—Polyvinylethers
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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  • C09K19/00—Liquid crystal materials
  • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
  • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
  • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
  • C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2219/00—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used
  • C09K2219/03—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used in the form of films, e.g. films after polymerisation of LC precursor

Definitions

• Polymerizable compound Polymerizable liquid crystal composition, polymer and film thereof
• the present invention relates to a polymerizable compound having a polymerizable moiety and a liquid crystal structure moiety, a polymerizable liquid crystal composition containing the polymerizable compound, and a polymer and a film obtained using them.
• the application is a material having optical characteristics such as a display device and a recording material, particularly an optical compensation film such as a polarizing plate and a retardation plate for a liquid crystal display.
• the polymerizable liquid crystal compound used here is generally a liquid crystal compound having a polymerizable group and a liquid crystal structure part (a structure part having a spacer part and a mesogen part), and an acrylic group as a polymerizable group. Widely used.
• a polymer obtained using such a polymerizable liquid crystal compound can be obtained by a method of polymerizing by irradiation with radiation such as ultraviolet rays in a liquid crystal state.
• a method in which a specific polymerizable liquid crystal compound having an acrylic group is supported between supports and polymerized by irradiation with radiation while maintaining the compound in a liquid crystal state see, for example, Patent Document 1 or acrylic.
• a polymer can be obtained by adding a photopolymerization initiator to a mixture of two kinds of polymerizable liquid crystal compounds having a group, or a composition in which chiral liquid crystal is mixed with the mixture, and irradiating with ultraviolet rays. Yes.
• Patent Document 2 For example, see Patent Document 2
• Patent Document 1 Japanese Patent Laid-Open No. 62-70407
• Patent Document 2 Japanese Patent Laid-Open No. 9-208957
• Non-patent document 1 C. Doornkamp et al. “2004 SID International Symposium Digest of Technical Papers, Volume XXXV, book I”, USA , (2004), 35 ⁇ , p. 670
• the present invention has been made in view of such circumstances, and has its own polymerizability, and when it is added to a polymerizable liquid crystal compound to form a polymerizable liquid crystal composition, its crystallization temperature.
• the first object is to provide a novel polymerizable compound capable of lowering (Tc).
• Another object of the present invention is to provide a polymerizable liquid crystal composition comprising the polymerizable compound and having a low crystallization temperature and exhibiting stable liquid crystallinity in a normal environment.
• a fourth object is to provide a highly transparent film obtained by polymerizing the polymerizable liquid crystal composition in an isotropic liquid state.
• H 2 C C-CH 2 -0- (CH 2 ) — O— X 1 — X 2 -X 3 [1]
• n an integer of 1 to 12
• X 1 represents divalent benzene, biphenyl, or cyclohexane
• X 2 represents divalent benzene, biphenyl, cyclohexyl, COO, OCO
• HC N
• X 3 is CN group, CF group, halogen atom, hydrogen atom, carbon number 1 ⁇
• X 1 is divalent benzene
• X 2 is divalent benzene or cyclohexyl
• X 3 is CN group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms or a halogen atom
• n is an integer of 5 to 12
• a polymerizable liquid crystal composition comprising at least one of the polymerizable compounds described in 1 or 2 above and one or more polymerizable liquid crystal compounds,
• a method for forming a film comprising a step of applying the polymerizable liquid crystal composition described in 4 or 5 above to a substrate by spin coating and irradiating with ultraviolet rays,
• a method for forming a film comprising a step of applying the polymerizable liquid crystal composition described in 4 or 5 above to a substrate by spin coating, then heating and irradiating ultraviolet rays while blowing nitrogen gas
• the invention's effect [0007]
• the polymerizable compound of the present invention has good compatibility with the polymerizable liquid crystal compound and can be added to the polymerizable liquid crystal compound to lower the crystallization temperature. For this reason, the polymerizable liquid crystal composition of the present invention containing this polymerizable compound exhibits a stable liquid crystal state in a normal environment and has good handling properties.
• polymerizable compound means a compound having a polymerizable site such as an acrylic group.
• polymerizable liquid crystal compound means a compound having a polymerizable portion such as an acrylic group or a rataton ring and a liquid crystal structure site in the molecule and exhibiting a liquid crystal phase.
• liquid crystal structure means a structure having a part of a spacer and a mesogenic part that are generally used to represent liquid crystal molecules.
• polymerizable liquid crystal composition means a composition containing, as a main component, a mixture of a polymerizable liquid crystal compound or a mixture of a polymerizable liquid crystal compound and a polymerizable compound, and has a characteristic of exhibiting a liquid crystal phase.
• liquid crystalline means exhibiting a liquid crystal phase.
• the polymerizable compound of the present invention is a compound having an exomethylene structure site and a liquid crystal structure site, which are polymerizable sites, and is represented by the formula [1].
• H 2 C C-CH 2 -0- (CH 2 ) — 0— X 1 — X 2 -X 3 L 1 ]
• X 1 represents divalent benzene, biphenyl, or cyclohexyl, and is preferably divalent benzene.
• X 2 represents divalent benzene, biphenyl, cyclohexyl, COO, OCO, HC ⁇ N, or N ⁇ CH, and is preferably divalent benzene or cyclohexyl.
• X 3 represents a CN group, a CF group, a halogen atom, a hydrogen atom, an alkoxy group having 1 to 6 carbon atoms,
• n represents an integer of 1 to 12, preferably an integer of 5 to 12, and more preferably an integer of 8 to 10.
• examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, and an n-propyl group.
• alkoxy group having 1 to 6 carbon atoms examples include methoxy group, ethoxy group, n-propoxy group, i propoxy group, n -butoxy group, s-butoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group. Groups and the like.
• X 1 is a divalent benzene
• X 2 is a divalent benzene or cyclohexyl
• X 3 Is a CN group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms or a halogen atom
• n is an integer of 5 to 12.
• Examples of such polymerizable compounds include the following compounds, but are not limited thereto.
• n an integer of 8 to 10.
• the polymerizable compound represented by the above formula [1] is excellent in compatibility with the polymerizable liquid crystal compound, and therefore can be mixed well with the polymerizable liquid crystal compound. As a result, the polymerizable liquid crystal composition The crystallization temperature as a product can be lowered.
• the polymerizable compound represented by the formula [9] is a polymerizable liquid crystal compound exhibiting liquid crystallinity, and the polymerizability represented by the formula [1] of the polymerizable liquid crystal composition as described later. It can also be used as a compound or a polymerizable liquid crystal compound.
• the method for synthesizing the polymerizable compound of the present invention can be synthesized by combining techniques in organic synthetic chemistry, and is not limited to, for example, the force capable of being synthesized by the following method.
• the polymerizable compound represented by the formula [1] of the present invention is an alcohol represented by 2- (bromomethyl) acrylic acid ester and compound (i) as shown in the following synthesis scheme (A). Can be synthesized.
• the alcohol represented by the formula (i) is the same as the alcohol represented by the formula (ii) as shown in the following synthesis scheme (B). It can be synthesized by reacting with terminal bromoalcohol such as xanol.
• the raw materials used in the synthesis schemes (A) and (B) may be commercially available compounds, or may be synthesized separately if necessary.
• polymerizable liquid crystal composition One aspect of the polymerizable liquid crystal composition of the present invention is a polymerizable containing at least one of the polymerizable compounds represented by the formula [1] and one or more polymerizable liquid crystal compounds. It is a liquid crystal composition.
• the polymerizable liquid crystal compound used in the polymerizable liquid crystal composition has a compatibility with the polymerizable compound represented by the above formula [1], and is a polymerization in which the polymerizable compound represented by the above formula [1] coexists.
• the liquid crystal composition is not particularly limited as long as it is a compound exhibiting liquid crystallinity.
• the polymerizable liquid crystal compound may be monofunctional or polyfunctional.
• polymerizable liquid crystal compounds include, but are not limited to, compounds of the formulas [10] to [15].
• the compounding amount of the polymerizable liquid crystal compound is preferably 300 to 1800 parts by mass with respect to 100 parts by mass of the polymerizable compound of the formula [1]. More preferably, it is 500 to 900 parts by mass.
• the total U preferably the total amount meets the above range.
• the polymerizable compound represented by the formula [9] is a polymerizable liquid crystal compound, and can also be used as a polymerizable liquid crystal compound constituting the polymerizable liquid crystal composition. At that time, a plurality of types can be used in combination.
• polymerizable liquid crystal composition of the present invention is a polymerizable liquid crystal composition containing one or more of the polymerizable compounds represented by the above formula [9].
• the polymerizable compound represented by the formula [9] is a polymerizable liquid crystal compound exhibiting liquid crystallinity
• other polymerizable liquid crystal compounds other than the polymerizable compound represented by the formula [9] May or may not be used in combination.
• 1800 with respect to 100 parts by mass of the polymerizable compound represented by the formula [9] More preferred is less than or equal to 900 parts by weight.
• this polymerizable liquid crystal composition examples include those containing two kinds of polymerizable compounds represented by the above formula [9]. Specifically, in the above formula [9], a composition containing a compound in which n is 8 and a compound in which n is 10 is exemplified.
• the power of the polymerizable liquid crystal composition of the present invention has two aspects. Both have a crystallization compared to the composition not containing the polymerizable compound of the present invention. The temperature drops. Therefore, it exhibits stable liquid crystallinity under a normal environment. Furthermore, it is preferable that this liquid crystal phase is an enantioselective liquid crystal phase at room temperature because the liquid crystal state is more stable and easy to handle.
• the polymerizable liquid crystal composition of the present invention is a polymerizable compound other than the present invention or a liquid crystal compound having no polymerizable group (hereinafter referred to as other mixture) as long as the effects of the present invention are not impaired. 1 type or 2 types or more can be mixed. In this case, the polymerizable compound other than the present invention may be monofunctional or polyfunctional.
• Such compounds include nematic liquid crystals, ferroelectric liquid crystals, and commercially available liquid crystal compositions.
• the blending amount of the other mixture contains a polymerizable compound represented by the formula [1] and a polymerizable liquid crystal compound (including a polymerizable liquid crystal compound represented by the formula [9]). Even when blended in a polymerizable liquid crystal composition, it contains two or more polymerizable compounds represented by the above formula [9]. Even when blended in the polymerizable liquid crystal composition, the total amount of the polymerizable liquid crystal compound in each composition (hereinafter referred to as the total polymerizable liquid crystal compound) is preferably 10 parts by mass or less with respect to 100 parts by mass.
• a photopolymerization initiator and a thermal polymerization initiator can be added to the polymerizable liquid crystal composition of the present invention for the purpose of improving the polymerization reactivity.
• photopolymerization initiator examples include ilgacure (registered trademark, the same shall apply hereinafter) 184, ilgacure 651, ilgacure 500, ilgacure 2959, ilgacure 369, ilgacure 907, ilgacure 300, manufactured by Ciba 'Specialty' Chemicals.
• Ilgacure 819, Irgacure 1700, Irgacure 1800, Irgacure 1850, Irgacure 784 and the like are not limited thereto.
• Such photopolymerization initiators can be used in combination of two or more.
• the addition amount is preferably 5 parts by mass or less, more preferably 1 part by mass or less, with respect to 100 parts by mass of the total polymerizable liquid crystal compound force S.
• thermal polymerization initiator examples include AIBN.
• thermal polymerization initiators can be used in combination of two or more types, and the addition amount thereof is preferably 5 parts by mass or less, more preferably 1 part by mass with respect to 100 parts by mass of the total polymerizable liquid crystal compound.
• the polymerizable liquid crystal composition of the present invention may be added with a stabilizer such as hydroquinone or hydroquinone monoalkyl ether in order to improve the storage stability.
• a stabilizer such as hydroquinone or hydroquinone monoalkyl ether
• methylhydroquinone, 2, 6-di-butyl-p-taresole and the like can be mentioned.
• these stabilizers can be used in combination of two or more kinds, and the addition amount is preferably 0.1 parts by mass or less with respect to 100 parts by mass of the total polymerizable liquid crystal compound.
• the polymerizable liquid crystal composition of the present invention may contain an adhesion promoter for the purpose of improving the adhesion to the substrate. At that time, a plurality of types of adhesion promoters may be used in combination.
• adhesion promoters include trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane.
• Silanes such as sidoxypropinole trimethoxysilane and ⁇ - ( ⁇ piperidyl) propyltrimethoxysilane; benzotriazole, benzimidazole, indazole, imidazole, 2-mercapto Heterocyclic compounds such as benzimidazole, 2-mercaptobenzobenzothiazole, 2-mercaptobenzoxazole, urazole, thuracil, mercaptoimidazole, mercaptopyrimidine; urea or thiourea compounds such as 1,1-dimethylurea, 1,3 dimethylurea Etc.
• An organic solvent can also be added to the polymerizable liquid crystal composition of the present invention. In that case, it does not need to exhibit liquid crystallinity 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 ⁇ , ⁇ ⁇ ⁇ ⁇ dimethylformamide and ⁇ -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-ethoxy Alkoxy esters such as propionate ethyl; glycol dialkyl ethers such as ethylene glycol dimethyl ether and propylene glycol dimethyl ether; diethylene glycol dimethyl ether, diethylene glycol jetyl ether, diethylene glycol methyl ether Diglycol dialkyl ethers such as ether and dipropylene glyco
• ketones such as methyl isobutyl ketone and 2-heptanone.
• organic solvents may be used alone or in combination of two or more.
• propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and ethyl lactate are preferable from the viewpoint of safety in the global environment and working environment.
• the polymerizable liquid crystal composition of the present invention may contain a surfactant for the purpose of improving the affinity with the substrate.
• a surfactant for the purpose of improving the affinity with the substrate.
• Such surfactants are not particularly limited, such as fluorine-based surfactants, silicone-based surfactants, and non-ionic surfactants.
• the fluorine-based surfactants have a high effect of improving affinity with the substrate.
• fluorine-based surfactants have a high effect of improving affinity with the substrate.
• fluorosurfactants hereinafter referred to as trade names
• F-top EF301, EF30 3, EF352 manufactured by Tochem Products
• MegaFuck F171, F173, R-30 Density of the Fluorosurfactants
• Florard FC430, FC431 Suditomo 3EM Co., Ltd.
• a plurality of surfactants can be used in combination.
• Examples of preferred polymerizable liquid crystal compositions include 100 parts by mass of the polymerizable compound represented by the formula [1], 300 to 900 parts by mass of one or more polymerizable liquid crystal compounds, and 5 photoinitiators.
• the polymerizable liquid crystal composition having a mass part of not more than 100, the polymerizable compound represented by the formula [9] is 100 parts by mass, and the polymerizable liquid crystal composition has a polymerizable liquid crystal compound of 900 parts by mass or less. .
• the method for obtaining the polymerizable liquid crystal composition of the present invention is not particularly limited.
• the components of the polymerizable liquid crystal composition may be mixed at once or sequentially. At that time, when one component is composed of a plurality of types of compounds, the other components may be mixed in the state of mixing them in advance, or they may be added individually and sequentially.
• the polymerizable liquid crystal composition of the present invention prevents the induction of thermal polymerization, which is not intended for photopolymerization in a liquid crystal state when producing an optical anisotropic body, and provides a uniform alignment state of molecules. In order to facilitate fixation, it is preferable to exhibit an enantioselective liquid crystal phase at room temperature. Ma In the case where 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 compound of the present invention (when the polymerizable liquid crystal compound represented by the formula [9] is used) or the polymerizable liquid crystal composition can be made into a polymer by irradiation with light or heating.
• the photoinitiator, thermal polymerization initiator, sensitizer and the like described in the polymerizable liquid crystal composition are used. Each can be used in the stated amounts.
• a polymerizable liquid crystal compound it can be used in an amount corresponding to an amount obtained by replacing 100 parts by mass of the total polymerizable liquid crystal compound with 100 parts by mass of the polymerizable liquid crystal compound. The same amount can also be used when obtaining a polymer with a polymerizable compound.
• a polymerizable liquid crystal compound or a polymerizable liquid crystal composition is sandwiched between two substrates, light is irradiated to polymerize, a spin coating method, a casting method, or the like is used.
• a method of applying a polymerizable liquid crystal compound or a polymerizable liquid crystal composition to the substrate and irradiating with light include a method of applying a polymerizable liquid crystal compound or a polymerizable liquid crystal composition to the substrate and irradiating with light.
• the substrate glass, quartz, plastic sheet, color filter, plastic film such as triacetyl cell port (TAC), or the like can be used.
• TAC triacetyl cell port
• a glass, plastic sheet, plastic film, or a belt drum on which a metal such as stainless steel, chrome, or aluminum is plated or vapor-deposited is used. It is also possible. Further, for the purpose of improving the orientation of the film, it is preferable to subject the substrate to an orientation treatment.
• a method for the alignment treatment a generally known method for applying alignment treatment by applying a alignment material containing a polyimide precursor, polyimide, polybulcinnamate, or the like and irradiating with rubbing or polarized ultraviolet rays, Examples include the method of forming an oblique deposition film of silicon dioxide and the method of forming a Langmuir film.
• a cell in which a gap is formed between the two substrates by using a spacer or the like is created, and a capillary phenomenon or a cell gap is formed.
• the polymerizable liquid crystal compound or polymerizable liquid crystal composition is selected by a method such as reducing the pressure of the liquid crystal. After being injected into the glass, it is polymerized by irradiation with light.
• a polymerizable liquid crystal compound or a polymerizable liquid crystal composition is placed on a substrate provided with a spacer, etc., and the other substrate is overlaid to create a cell.
• the polymerizable liquid crystal compound or the polymerizable liquid crystal composition may be fluidized or may be fluidized by heating or the like after being placed on the substrate.
• a hot plate or the like may be used as needed during the steps of applying the compound or liquid crystal composition and polymerizing with light or heat. You may add the process heated by. This step is particularly effective when the polymerizable liquid crystal compound or polymerizable liquid crystal composition containing the organic solvent is used, because the organic solvent can be removed.
• a multi-domain method in the polymerization step or a multi-domain method of substrate orientation treatment is used.
• a polymerizable liquid crystal composition is applied to a substrate by spin coating, and the polymerizable liquid crystal composition is heated on an hot plate until it is in an isotropic liquid state, and held for 20 seconds to 5 minutes.
• the polymerizable liquid crystal composition is cooled to a temperature range showing a liquid crystal to be in a liquid crystal state.
• the film is polymerized by irradiating ultraviolet rays with a high-pressure mercury lamp or the like in a nitrogen atmosphere or while blowing nitrogen gas, thereby obtaining an oriented optically anisotropic film.
• the method of forming a multi-domain in the polymerization step is a method for forming a polymerizable liquid crystal compound or a polymer in a liquid crystal state.
• Examples include a method in which a polymerized domain is formed by exposing the compatible liquid crystal composition to ultraviolet rays through a mask, and the remaining domains are polymerized in an isotropic liquid state.
• examples of the method of making the alignment treatment of the substrate multi-domain include a method of rubbing the alignment material formed on the substrate through a mask and a method of irradiating ultraviolet rays through a mask.
• a method of rubbing the alignment material formed on the substrate through a mask and a method of irradiating ultraviolet rays through a mask.
• a multi-domained substrate is obtained in which the rubbed domain and the ultraviolet-irradiated domain are the part subjected to the orientation treatment, and the rest are the untreated parts.
• the polymerizable liquid crystal compound or polymerizable liquid crystal composition formed on the multi-domained substrate is multi-domained under the influence of the alignment material layer.
• a method using an electric field or a magnetic field can also be used.
• the polymerizable compound of the present invention has good compatibility with the polymerizable liquid crystal composition, and the crystallization temperature can be lowered by adding the polymerizable compound to the polymerizable liquid crystal composition. Therefore, the polymerizable liquid crystal composition of the present invention has good handling properties under normal circumstances, can provide a polymer having optical anisotropy, and can be suitably used for polarizing plates, retardation plates, and the like. it can.
• a polymerizable liquid crystal composition using a liquid crystalline compound of the polymerizable compound of the present invention can obtain a highly transparent polymer when polymerized in an isotropic liquid state. Therefore, it can be suitably used for a multi-domain film.
• the compound was dissolved in deuterated chloroform and measured using 300 MHz 1 H-NMR (manufactured by JEOL Ltd.).
• the liquid crystal phase was identified by heating the sample on a hot stage (MATS-2002S, manufactured by Tokai Hit) and observing it using a polarizing microscope (manufactured by Nikon Corporation).
• the phase transition temperature was measured using a differential scanning thermal analyzer (DSC3100SR) (hereinafter referred to as DSC) manufactured by Mac Science. It was measured.
• the sample was dissolved in tetrahydrofuran for high-speed chromatography so as to be 0.5% by mass and measured using a room temperature gel permeation chromatography (hereinafter referred to as GPC) apparatus manufactured by JSACO.
• GPC room temperature gel permeation chromatography
• JSACO room temperature gel permeation chromatography
• the glass transition temperature was measured using a differential scanning thermal analyzer (DSC3100SR) manufactured by Mac Science.
• the transmittance was measured at a wavelength of 600 nm using (UV3100PC, manufactured by SHIMADZU).
• the retardation value of the film was measured using a retardation measuring device (RETS-100, manufactured by Otsuka Electronics Co., Ltd.).
• the melting point of the obtained polymerizable compound (Q3) was measured with a differential scanning calorimeter (DSC3100SR) manufactured by Mac Science, and as a result, it was 24 ° C.
• the melting point of the obtained polymerizable compound (Q5) was measured with a differential scanning calorimeter (DSC3100SR) manufactured by Mac Science, and as a result, it was 37 ° C.
• Example 6 In a 10 ml eggplant flask, 0.94 g of the polymerizable compound (Q6) obtained in Example 6 was obtained. Xan 2. Oml and AIBN 6.6 mg were charged, a condenser tube and a nitrogen balloon were attached, the inside of the container was placed in a nitrogen atmosphere, and the reaction was carried out at 70 ° C with stirring for 24 hours. After completion of the reaction, the reaction solution was poured into 80 ml of methanol, and the precipitated white solid was filtered and dried under reduced pressure to obtain 0.71 g of a polymer. The results of NMR measurement of the obtained polymer are shown below. From this result, it was confirmed that the obtained polymer was a polymer of polymerizable compound (Q6). This polymer had a number average molecular weight of 4400 and a weight average molecular weight of 9000.
• the compound (K1) 100.4 mg obtained in Reference Synthesis Example 3 and the compound (K2) 100.2 mg obtained in Reference Synthesis Example 4 were mixed.
• the liquid crystal properties of this mixture were evaluated. It became an isotropic liquid and formed a nematic phase at 51.8 ° C when the temperature decreased.
• the transition temperature from the liquid crystal phase to the crystal phase was 14.0 ° C., which was higher than that of the liquid crystal composition of Example 14.
• Img were mixed and polymerized.
• the polymerizable liquid crystal composition was placed on the surface of the substrate on which the spacers were dispersed to form an isotropic liquid state.
• a cell was fabricated by superposing the ITO surface of another glass substrate with ITO on the spacer of this substrate so as to contact.
• the cell was kept at 90 ° C. and irradiated with light at an intensity of 42 jZcm 2 using a high-pressure mercury lamp to polymerize the polymerizable liquid crystal composition, thereby obtaining a cell sandwiched between film substrates.
• the cell thus obtained was measured for transmittance at 600 nm using a blank cell prepared without a polymerizable liquid crystal composition as a blank. As a result, the transmittance was 90.78%.
• Example 15 the polymerizable compound (Q6) was replaced with 50. Img of the polymerizable compound (Q 4) obtained in Example 4 and the polymerizable compound obtained in Example 6. (Q6) Instead of 30.3 mg, as a photopolymerization initiator, Ciba 'Specialty Chemicals Irgacure (registered trademark) 369 (trade name) 2. Mix with Omg and perform the same operation to create a cell and evaluate it. went. As a result, the transmittance was 88.93%.
• Example 15 a polymerizable compound (Q6) was replaced with the compound (Z2) obtained in Reference Synthesis Example 2 in the same manner, and a cell was prepared and evaluated. As a result, the transmittance was 1.49%.
• Example 15 the polymerizable compound (Q6) 100. Omg was replaced with the compound (Zl) 50. Omg obtained in Reference Synthesis Example 1 and the compound (Z2) obtained in Reference Synthesis Example 2. 50. Same as Omg A cell was created by performing the same operations and evaluated. As a result, the transmittance was 9.25%.
• the substrate with the liquid crystal alignment film on which the spacer was dispersed was heated to 30 ° C. on a hot plate, and the above polymerizable liquid crystal composition was placed on the surface of the substrate where the spacer was dispersed. It was confirmed that the polymerizable liquid crystal composition had fluidity, and another substrate with a liquid crystal alignment film was stacked so that the liquid crystal alignment film was in contact with the polymerizable liquid crystal composition to form a cell. At that time, the two substrates with a liquid crystal alignment film were overlapped so that the rubbing direction was at an angle of 180 °.
• the substrate with a liquid crystal alignment film used here is a thin film having a thickness of lOOnm by spin-coating SE-1411 manufactured by Nissan Chemical Industries, Ltd.
• the cell thus prepared was kept at 30 ° C, and a high pressure mercury lamp was used to irradiate light with an intensity of 42jZcm 2 to polymerize the polymerizable liquid crystal composition, and the film was narrowed to two substrates. The held cell was obtained.
• Example 17 a polymerizable compound (Q6) was replaced with the compound (Z2) obtained in Reference Synthesis Example 2 in the same manner, and a cell was prepared and evaluated. As a result, the polymer in the cell was not oriented.
• Example 18 Polymerizable compound (Q4) 50. Omg obtained in Example 4, Polymerizable compound (K3) 50. lmg obtained in Reference Synthesis Example 5, Irgacure 369 (manufactured by Ciba-Geigy Co., Ltd.) as a photopolymerization initiator (Product name) 1. 2 mg and 204.2 mg of propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a polymerizable liquid crystal composition.
• this polymerizable liquid crystal composition was spin coated (1000 rpm, 20 seconds) on the liquid crystal alignment film surface of the substrate to form a film.
• the substrate was heated for 1 minute on a hot plate heated to a temperature of 55 ° C. to obtain an isotropic liquid state, and then cooled to 32 ° C. to obtain a liquid crystal state.
• the polymerizable liquid crystal composition was polymerized by irradiating light of 42 jZcm 2 with a high-pressure mercury lamp to form an optically anisotropic film on the substrate.
• the substrate used at that time was spin coated with SE-1140 manufactured by Nissan Chemical Industries, Ltd.
• the retardation value of this film was 82.92.
• the transmittance of the obtained optically anisotropic film at 600 nm was measured using a substrate with a liquid crystal alignment film as a blank, which was 98.01%.
• Example 18 The polymerizable liquid crystal composition prepared in Example 18 was applied in the same manner as in Example 18 to form a coating film on the substrate with a liquid crystal alignment film.
• This substrate was placed on a hot plate heated to a temperature of 55 ° C. to obtain an isotropic liquid state, and this state was maintained. Then, while blowing nitrogen gas, a high pressure mercury lamp was used to irradiate light with an intensity of 42 jZcm 2 to form a film on the substrate.
• the obtained film was observed with a polarizing microscope and confirmed to be an isotropic film. Further, the transmittance of the obtained film at 600 nm was measured using a substrate with a liquid crystal alignment film as a blank, and it was 96.98%.
• Example 19 was prepared using this polymerizable liquid crystal composition. A film was formed on the substrate with a liquid crystal alignment film by the same method as described above.
• the transmittance at 600 nm was measured using a substrate with a liquid crystal alignment film as a blank, and found to be 35.68%.
• the polymerizable liquid crystal composition containing the polymerizable compound of the present invention is useful as a material for optical compensation films such as polarizing plates and retardation plates for display devices, and optical anisotropic films such as multidomain films.

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