WO2009122868A1 - 三官能(メタ)アクリレート化合物及び該化合物を含有する重合性組成物 - Google Patents
三官能(メタ)アクリレート化合物及び該化合物を含有する重合性組成物 Download PDFInfo
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- WO2009122868A1 WO2009122868A1 PCT/JP2009/054562 JP2009054562W WO2009122868A1 WO 2009122868 A1 WO2009122868 A1 WO 2009122868A1 JP 2009054562 W JP2009054562 W JP 2009054562W WO 2009122868 A1 WO2009122868 A1 WO 2009122868A1
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- CSNCPNFITVRIBQ-HQICPSFESA-N C=CC(OCCCCOC(Oc(cc1)ccc1C(Oc(cc1)ccc1C(O[C@H](CO[C@H]12)C1OC[C@@H]2OC(c(cc1)ccc1OC(c(cc1)ccc1OC(OCCCCOC(C=C)=O)=O)=O)=O)=O)=O)=O)=O Chemical compound C=CC(OCCCCOC(Oc(cc1)ccc1C(Oc(cc1)ccc1C(O[C@H](CO[C@H]12)C1OC[C@@H]2OC(c(cc1)ccc1OC(c(cc1)ccc1OC(OCCCCOC(C=C)=O)=O)=O)=O)=O)=O)=O)=O CSNCPNFITVRIBQ-HQICPSFESA-N 0.000 description 1
- NRSBJLOHJHMNPS-UHFFFAOYSA-N CC(C(OCCCCCCOc(cc1)ccc1C(Oc(cc1)ccc1-c1ccccc1)=O)=O)=C Chemical compound CC(C(OCCCCCCOc(cc1)ccc1C(Oc(cc1)ccc1-c1ccccc1)=O)=O)=C NRSBJLOHJHMNPS-UHFFFAOYSA-N 0.000 description 1
- REKOZZHQVUCUGY-UHFFFAOYSA-N CC(C(OCCOCC1CCC(COc(cc2)cc(F)c2F)CC1)=O)=C Chemical compound CC(C(OCCOCC1CCC(COc(cc2)cc(F)c2F)CC1)=O)=C REKOZZHQVUCUGY-UHFFFAOYSA-N 0.000 description 1
- JACOACSKQPFJAL-UHFFFAOYSA-N CC(C(OCCOCC1CCC(COc(cc2)ccc2-c2ccccc2)CC1)=O)=C Chemical compound CC(C(OCCOCC1CCC(COc(cc2)ccc2-c2ccccc2)CC1)=O)=C JACOACSKQPFJAL-UHFFFAOYSA-N 0.000 description 1
- PXNUQTPVHGGSSE-UHFFFAOYSA-N COCC1CCC(COc(cc2)ccc2-c(cc2)ccc2O)CC1 Chemical compound COCC1CCC(COc(cc2)ccc2-c(cc2)ccc2O)CC1 PXNUQTPVHGGSSE-UHFFFAOYSA-N 0.000 description 1
- HQCOCVYJSHOMIX-UHFFFAOYSA-N COCC1CCC(COc(cc2)ccc2C(OCCO)=O)CC1 Chemical compound COCC1CCC(COc(cc2)ccc2C(OCCO)=O)CC1 HQCOCVYJSHOMIX-UHFFFAOYSA-N 0.000 description 1
- CPJNIRIPWPWFLJ-UHFFFAOYSA-N COCC1CCC(COc(cc2)ccc2OC(C=C)=O)CC1 Chemical compound COCC1CCC(COc(cc2)ccc2OC(C=C)=O)CC1 CPJNIRIPWPWFLJ-UHFFFAOYSA-N 0.000 description 1
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Definitions
- the present invention relates to a novel trifunctional (meth) acrylate compound having at least one condensed ring, and the polymerizable composition using the compound exhibits excellent heat resistance, hardness, optical properties, solvent resistance, and the like.
- the optical anisotropic body produced by photopolymerizing the polymerizable composition is useful as an optical material such as a retardation film, a polarizing plate, a light polarizing prism, and an optical film for display.
- the liquid crystal substance has its orientation, refractive index, dielectric constant, magnetic susceptibility, elastic modulus. Utilizing the anisotropy of physical properties such as thermal expansion coefficient, it can be applied to optical anisotropic bodies such as retardation plates, polarizing plates, light polarizing prisms, brightness enhancement films, low-pass filters, and various optical filters. It is being considered.
- the optical anisotropic body is, for example, an energy ray such as an ultraviolet ray while maintaining a liquid crystal state after uniformly aligning a liquid crystal compound having a polymerizable functional group or a polymerizable composition containing the liquid crystal compound in a liquid crystal state. However, it is required to fix the alignment state of the liquid crystal compound uniformly and semipermanently.
- liquid crystal phase expression temperature of the polymerizable composition is high, not only photopolymerization by energy rays but also unintentional thermal polymerization is induced, and the uniform alignment state of the liquid crystal molecules is lost, so it is difficult to fix the desired alignment. is there. Accordingly, there is a need for a polymerizable composition that exhibits a liquid crystal phase near room temperature in order to facilitate temperature control during curing.
- a polymer can be obtained by applying a polymerizable composition to a substrate and polymerizing it.
- a non-polymerizable compound if a non-polymerizable compound is contained, the strength of the resulting polymer is insufficient, or stress strain remains in the film. There is a drawback of doing. Further, when the non-polymerizable compound is removed with a solvent or the like, there is a problem that the uniformity of the film cannot be maintained and unevenness occurs. Therefore, in order to obtain a polymer having a uniform film thickness, a method in which a polymerizable composition is dissolved in a solvent is preferably used, and the solvent solubility of the liquid crystal compound or the polymerizable composition containing it is good. Is required.
- the optical anisotropic body is not usually used as a single film, but is laminated with other functional materials on a substrate such as glass, so that there is no problem in coating other functional materials. It is required to exhibit solvent resistance and high hardness.
- a compound having a polymerizable functional group of (meth) acrylic group has high polymerization reactivity, and a highly transparent polymer is obtained.
- a monomer having a bifunctional (meth) acryl group and a trifunctional monomer are known to be effective means for improving the heat resistance and solvent resistance of the polymer.
- Patent Documents 1 to 6 propose trifunctional monomers.
- these monomers are used, there is a problem that crystals may be deposited on the polymer or it may be difficult to control the orientation uniformly.
- an object of the present invention is to provide a polymerizable compound and a polymerizable composition that can obtain a polymer that can control the orientation, is particularly excellent in heat resistance, and is excellent in optical properties and the like.
- the present invention provides a trifunctional (meth) acrylate compound represented by the following general formula (I).
- M 1 , M 2 and M 3 each independently represent a hydrogen atom, a methyl group or a halogen atom
- ring A 1 , ring A 2 and ring A 3 are each independently a benzene ring or cyclohexane.
- ring A 1 , ring A 2 and ring A 3 is a naphthalene ring
- each of Z 1 , Z 2 and Z 3 is independently selected from 1 to 6 represents an alkyl group, a halogen atom or a cyano group, wherein a hydrogen atom of the alkyl group may be substituted with a halogen atom or a cyano group, and the methylene group of the alkyl group is represented by —O— or —CO—.
- X 1 , X 2 and X 3 are each independently a direct bond, —COO—, —OCO—, — (CH 2 ) p —, —CH ⁇ CH—, — (CH 2 ) p O—, —O (CH 2 ) p —, —CH ⁇ CHCH 2 O—, —OCH 2 CH ⁇ CH—, —C ⁇ C—, — (CH 2 ) p COO—, —OCO (CH 2 ) p —, — (CH 2 ) p OCO—O—, —OCO—O (CH 2 ) p —, — (CH 2 ) q O (CH 2 ) r O— or —O (CH 2 ) q O (CH 2 ) r — the stands, Y 1 and Y 2 are each independently, -L 1 -, - L 1 O -, - L 1 O-CO -, - L 1 CO-O- or -L 1
- the alkylene group may be interrupted one to three times with -O-
- a, b and c are each ring A 1, the number of substituents in the ring A 2 and ring A 3
- a, b and c are each independently an integer of 2u + 2 or less
- a, b and c Among them, at least one represents an integer of 1 or more
- p represents each independently an integer of 1 to 8
- q and r each independently represents an integer of 1 to 3
- s and t represent each independently Furthermore, 0 or 1 and s + t ⁇ 1.
- the present invention uses a polymerizable composition containing the trifunctional (meth) acrylate compound, an optical anisotropic body produced by photopolymerizing the polymerizable composition, and the optical isomer.
- An optical film for a display is provided.
- FIG. 1 shows the compound No. 1 of the present invention produced in Example 1-1.
- 1 is a schematic diagram showing the thermal transition behavior of No. 1.
- FIG. FIG. 2 shows the compound No. 1 of the present invention produced in Example 1-2. It is a schematic diagram which shows the thermal transition behavior of 2.
- FIG. 3 shows the compound No. 1 of the present invention produced in Example 1-3. 3 is a schematic diagram showing the thermal transition behavior of No. 3.
- halogen atoms represented by M 1 , M 2 , M 3 , Z 1 , Z 2 and Z 3 , or the number of carbon atoms represented by Z 1 , Z 2 and Z 3 is 1 to Examples of the halogen atom that may substitute the alkyl group of 6 include fluorine, chlorine, bromine, and iodine.
- examples of the alkyl group having 1 to 6 carbon atoms represented by Z 1 , Z 2 and Z 3 include methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, And isobutyl, amyl, isoamyl, t-amyl, hexyl, 2-hexyl, 3-hexyl and the like, which may be substituted with a halogen atom and a cyano group, and the methylene group in the alkyl group is —O— Or it may be interrupted by -CO-.
- the alkylene group having 1 to 8 carbon atoms represented by L 1 and L 2 is methylene, ethylene, propylene, trimethylene, tetramethylene, butane-1,3-diyl, 2- Methylpropane-1,3-diyl, 2-methylbutane-1,3-diyl, pentane-2,4-diyl, pentane-1,4-diyl, 3-methylbutane-1,4-diyl, 2-methylpentane- Examples include 1,4-diyl, pentamethylene, hexamethylene, heptamethylene, octamethylene and the like, and these may be interrupted 1 to 3 times with —O—.
- the ring A 1 , the ring A 2 and the ring A 3 are a benzene ring or a naphthalene ring, and the ring A 1 , the ring A 2 and the ring of a 3, at least one of which is a naphthalene ring trifunctional (meth) acrylate compounds, a wide liquid crystal expressed temperature range, also preferable because the liquid crystal phase stability is high in the low temperature range low crystallinity, X 1 A trifunctional (meth) acrylate compound in which X 2 and X 3 are —COO— or —OCO— is preferable because the liquid crystal orientation is improved.
- a trifunctional (meth) acrylate compound in which the ring A 3 is a naphthalene ring is more preferable because the crystallinity is further lowered, and the trifunctional (meth) capable of holding a liquid crystal phase at 30 ° C. or less alone.
- An acrylate compound is more preferable because it exhibits a liquid crystal phase in a practical temperature range (room temperature).
- the production method of the trifunctional (meth) acrylate compound of the present invention is not particularly limited, and can be produced by applying a known reaction. For example, by first esterifying a (meth) acrylic acid halide with a hydroxyl group of a phenol compound or a naphthol compound (including a hydroxyl group bonded via Y 1 , Y 2 or Y 3 ), ( A (meth) acryloyloxy group intermediate is obtained. Next, two (meth) acryloyloxy group intermediates are reacted according to the reaction formula shown in the following [Chemical Formula 5] to form X 1 , X 2 or X 3, thereby forming the trifunctional (meth) of the present invention. An acrylate compound can be obtained.
- the trifunctional (meth) acrylate compound of the present invention obtained by the reaction formula shown in the following [Chemical Formula 5] is one in which X 1 , X 2 or X 3 is —COO— or —OCO— ) An acryloyloxy group is contained in each of the R 1 and R 2 moieties.
- the trifunctional (meth) acrylate compound of the present invention is blended in a liquid crystal material as necessary, and is a material for producing an optical anisotropic body excellent in hardness, heat resistance, liquid crystal alignment fixing ability, optical characteristics and solvent resistance.
- a polymer dispersion liquid crystal (PDLC) monomer a liquid crystal alignment film, a liquid crystal alignment control agent, a coating material, a protective plate preparation material, and the like.
- the polymerizable composition of the present invention contains the trifunctional (meth) acrylate compound of the present invention and is preferably used as a material for producing an optical anisotropic body.
- the polymerizable composition of the present invention can further contain a liquid crystal compound in addition to the trifunctional (meth) acrylate compound of the present invention.
- the liquid crystal compounds referred to here include conventionally known liquid crystal compounds, liquid crystal analogs, and mixtures thereof.
- the content of the trifunctional (meth) acrylate compound of the present invention is 100 parts by mass of the total content of the trifunctional (meth) acrylate compound and the content of the liquid crystal compound. Is preferably 3 to 100 parts by mass, particularly 5 to 100 parts by mass.
- the ratio of the trifunctional (meth) acrylate compound of the present invention is less than 3 parts by mass, the effects of the present invention may not be obtained.
- it is preferable to increase the ratio of the trifunctional (meth) acrylate compound of the present invention specifically, 70 to 100 parts by mass.
- liquid crystal compound a generally used liquid crystal compound can be used, and specific examples of the liquid crystal compound are not particularly limited, and examples thereof include the following [Chemical Formula 6] and [Chemical Formula 7]. Each compound shown by these is mentioned.
- W 1 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have a branch, an alkoxy group having 1 to 8 carbon atoms which may have a branch, or a branched group.
- a liquid crystal compound having a polymerizable functional group is preferably used as the liquid crystal compound.
- the polymerizable functional group include (meth) acryloyloxy group, fluoroacryl group, chloroacryl group, trifluoromethylacryl group, oxirane ring (epoxy), oxetane ring, styrene compound (styryl group), vinyl group, vinyl ether group. , Vinyl ketone group, maleimide group, phenylmaleimide group and the like are preferable.
- liquid crystal compound having a polymerizable functional group those generally used can be used, and specific examples thereof are not particularly limited, but are described in paragraphs of JP-A-2005-15473. [0172] to [0314], or the compounds shown in the following [Chemical Formula 8] to [Chemical Formula 18].
- Examples of other monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and hexyl.
- the above-mentioned other monomers can be used as long as the effects of the hardness, heat resistance, solvent resistance and optical properties of the polymer produced using the polymerizable composition of the present invention are not impaired.
- the amount of other monomers used is 50 parts by mass or less based on 100 parts by mass of the total amount of the trifunctional (meth) acrylate compound of the present invention and the liquid crystal compound. Is preferable, and 30 parts by mass or less is particularly preferable.
- radical polymerization initiator conventionally known compounds can be used.
- benzoyl peroxide 2,2′-azobisisobutyronitrile, benzophenone, phenylbiphenyl ketone, 1-hydroxy-1- Benzoylcyclohexane, benzyl, benzyldimethyl ketal, 1-benzyl-1-dimethylamino-1- (4′-morpholinobenzoyl) propane, 2-morpholy-2- (4′-methylmercapto) benzoylpropane, thioxanthone, 1-chloro -4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl anthraquinone, 4-benzoyl-4'-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy 2- (4′-isopropyl) benzo
- X 71 represents a halogen atom or an alkyl group
- X 72 represents a hydrogen atom, a halogen atom, an alkyl group or a substituent represented by the following general formula (B)
- R 71 , R 72 and R 73 each independently represents R, OR, COR, SR, CONRR ′ or CN
- R and R ′ each independently represents an alkyl group, an aryl group, an arylalkyl group or a heterocyclic group, and May be substituted with a halogen atom and / or a heterocyclic group, and among these, the alkylene part of the alkyl group and arylalkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond, or an ester bond.
- R and R ′ may be combined to form a ring
- g is an integer of 0 to 4, and when g is 2 or more, a plurality of X 71 may be different groups
- ring M represents a cycloalkane ring, an aromatic ring or a heterocyclic ring
- X 73 represents a halogen atom or an alkyl group
- Y 71 represents an oxygen atom, a sulfur atom or a selenium atom
- Z 71 represents the number of carbon atoms.
- h is an integer of 0 to 4, and when h is 2 or more, the plurality of X 73 may be different groups.
- radical polymerization initiator and sensitizer can be preferably used.
- the sensitizer include thioxanthone, phenothiazine, chlorothioxanthone, xanthone, anthracene, diphenylanthracene, and lupine.
- the addition amount is 10 parts by mass or less with respect to 100 parts by mass of the total amount of the trifunctional (meth) acrylate compound of the present invention and the liquid crystal compound. Is preferably 5 parts by mass or less, and more preferably in the range of 0.1 to 3 parts by mass.
- solvent examples include benzene, toluene, xylene, mesitylene, n-butylbenzene, diethylbenzene, tetralin, methoxybenzene, 1,2-dimethoxybenzene, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane.
- the solvent may be a single compound or a mixture. Among these solvents, those having a boiling point of 60 to 250 ° C. are preferable, and those having a boiling point of 60 to 180 ° C. are particularly preferable. If the temperature is lower than 60 ° C., the solvent is volatilized in the coating process and the film thickness is likely to be uneven. If the temperature is higher than 250 ° C., the solvent remains even when the pressure is reduced in the desolvation step. In some cases, the orientation may be reduced.
- an optically active compound to the polymerizable composition of the present invention, a polymer having a helical structure of a liquid crystal skeleton can be obtained, and a cholesteric liquid crystal phase can be fixed.
- the content thereof is 0.1 to 100 parts by mass with respect to 100 parts by mass of the total amount of the trifunctional (meth) acrylate compound of the present invention and the liquid crystal compound (excluding the solvent). It is preferably in the range of 100 parts by mass, and more preferably in the range of 1 to 50 parts by mass.
- the optically active compound include compounds represented by the following [Chemical Formula 21].
- the polymerizable composition of the present invention preferably further contains a surfactant having an excluded volume effect distributed on the air interface side.
- the surfactant is preferably a surfactant that can easily apply the polymerizable composition to a support substrate or the like or can control the orientation of the liquid crystal phase.
- surfactant examples include quaternary ammonium salts, alkylamine oxides, polyamine derivatives, polyoxyethylene-polyoxypropylene condensates, polyethylene glycol and esters thereof, sodium lauryl sulfate, ammonium lauryl sulfate, amines of lauryl sulfate, Examples include alkyl-substituted aromatic sulfonates, alkyl phosphates, perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl ethylene oxide adducts, and perfluoroalkyl trimethyl ammonium salts.
- the preferred amount of the surfactant used depends on the type of the surfactant, the component ratio of the composition, etc., but with respect to 100 parts by mass of the total amount of the trifunctional (meth) acrylate compound of the present invention and the liquid crystal compound. It is preferably in the range of 0.001 to 5 parts by mass, and more preferably in the range of 0.01 to 1 part by mass.
- an additive may be further used in the polymerizable composition of the present invention as necessary in order to adjust the characteristics of the polymerizable composition.
- additives include storage stabilizers, antioxidants, ultraviolet absorbers, infrared absorbers, fine particles of inorganic substances and organic substances, and functional compounds such as polymers.
- the above storage stabilizer can impart the effect of improving the storage stability of the polymerizable composition.
- stabilizers that can be used include hydroquinone, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, 2-naphthylamines, and 2-hydroxynaphthalenes.
- the addition amount is 1 mass part or less with respect to 100 mass parts of total amounts of the trifunctional (meth) acrylate compound of this invention, and the said liquid crystal compound, 0.5 mass Part or less is particularly preferable.
- the antioxidant is not particularly limited and a known compound can be used. Examples thereof include hydroquinone, 2,6-di-t-butyl-p-cresol, 2,6-di-t-butylphenol, Examples thereof include phenyl phosphite and trialkyl phosphite.
- the ultraviolet absorber is not particularly limited, and a known compound can be used.
- a salicylic acid ester compound for example, a benzophenol compound, a benzotriazole compound, a cyanoacrylate compound, a nickel complex compound, or the like It may have absorptive capacity.
- the fine particles can be used to adjust optical (refractive index) anisotropy ( ⁇ n) or increase the strength of the polymerized film.
- the material of the fine particles include inorganic substances, organic substances, metals, and the like.
- the fine particles can preferably have a particle diameter of 0.001 to 0.1 ⁇ m, more preferably 0.001 to The particle diameter is 0.05 ⁇ m. A sharp particle size distribution is preferred.
- the amount of the fine particles can be preferably used within the range of 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the trifunctional (meth) acrylate compound of the present invention and the liquid crystal compound. .
- the inorganic material examples include ceramics, fluorine phlogopite, fluorine tetrasilicon mica, teniolite, fluorine vermiculite, fluorine hectorite, hectorite, saponite, stevensite, montmorillonite, beidellite, kaolinite, frypontite, ZnO, TiO 2 , CeO 2, Al 2 O 3, Fe 2 O 3, ZrO 2, MgF 2, SiO 2, SrCO 3, Ba (OH) 2, Ca (OH) 2, Ga (OH) 3, Al (OH) 3, Mg (OH) 2 , Zr (OH) 4 and the like.
- Fine particles such as calcium carbonate needle crystals have optical anisotropy, and the optical anisotropy of the polymer can be adjusted by such fine particles.
- the organic substance include carbon nanotubes, fullerenes, dendrimers, polyvinyl alcohol, polymethacrylates, and polyimides.
- the polymer can control the electrical characteristics and orientation of the polymerized film, and a polymer compound soluble in the solvent can be preferably used.
- a polymer compound soluble in the solvent can be preferably used.
- the polymer compound include polyamide, polyurethane, polyurea, polyepoxide, polyester, polyester polyol, and the like.
- Arbitrary components other than the trifunctional (meth) acrylate compound of the present invention described above are not particularly limited, and do not impair the properties of the polymer to be produced.
- the total amount of all optional components is preferably 10 parts by mass or less with respect to 100 parts by mass of the total amount of the trifunctional (meth) acrylate compound of the present invention and the liquid crystal compound.
- the optical anisotropic body of the present invention after dissolving the polymerizable composition in a solvent, it is applied to a support substrate and desolvated in a state where liquid crystal molecules in the polymerizable composition are aligned, and then energy rays are applied. It can be obtained by irradiation and polymerization.
- the support substrate is not particularly limited, but preferred examples include glass plates, polyethylene terephthalate plates, polycarbonate plates, polyimide plates, polyamide plates, polymethyl methacrylate plates, polystyrene plates, polyvinyl chloride plates, polytetrafluoroethylene plates. , Cellulose plate, silicon plate, reflector plate, calcite plate and the like. What provided the polyimide alignment film or the polyvinyl alcohol alignment film on such a support substrate can be used especially preferably.
- known methods can be used, for example, curtain coating method, extrusion coating method, roll coating method, spin coating method, dip coating method, bar coating method, spray coating method, slide coating method.
- the method, the printing coating method, the casting film forming method, and the like can be used.
- the film thickness of the polymerized film is appropriately selected according to the application and the like, but is preferably selected from the range of 0.05 to 10 ⁇ m.
- Examples of a method for aligning the liquid crystal molecules in the polymerizable composition of the present invention include a method in which an alignment treatment is performed on a support substrate in advance.
- an alignment treatment there is a method in which a liquid crystal alignment layer composed of various polyimide alignment films, polyamide alignment films, or polyvinyl alcohol alignment films is provided on a support substrate, and a treatment such as rubbing is performed.
- a magnetic field, an electric field, etc. to the composition on a support substrate is also mentioned.
- a known method using heat or electromagnetic waves can be applied.
- the polymerization reaction using electromagnetic waves include radical polymerization, anionic polymerization, cationic polymerization, coordination polymerization, and living polymerization. This is because it is easy to perform polymerization under the condition that the polymerizable composition exhibits a liquid crystal phase. It is also preferable to crosslink while applying a magnetic field or electric field.
- the liquid crystal (co) polymer formed on the support substrate may be used as it is, but if necessary, it may be peeled off from the support substrate or transferred to another support substrate.
- Preferred types of the light are ultraviolet rays, visible rays, infrared rays and the like. You may use electromagnetic waves, such as an electron beam and an X-ray. Usually, ultraviolet rays or visible rays are preferable. A preferable wavelength range is 150 to 500 nm. A more preferable range is 250 to 450 nm, and a most preferable range is 300 to 400 nm.
- the light source is a low-pressure mercury lamp (sterilization lamp, fluorescent chemical lamp, black light), high-pressure discharge lamp (high-pressure mercury lamp, metal halide lamp), or short arc discharge lamp (super-high pressure mercury lamp, xenon lamp, mercury xenon lamp). Among them, an ultrahigh pressure mercury lamp can be preferably used.
- Light from the light source may be irradiated to the polymerizable composition as it is, or a specific wavelength (or a specific wavelength region) selected by a filter may be irradiated to the polymerizable composition.
- Preferred irradiation energy density is 2 ⁇ 5000mJ / cm 2, more preferred range is 10 ⁇ 3000mJ / cm 2, particularly preferred range is 100 ⁇ 2000mJ / cm 2.
- Preferred illuminance is 0.1 ⁇ 5000mW / cm 2, more preferably illuminance is 1 ⁇ 2000mW / cm 2.
- the temperature at which light is irradiated can be set so that the polymerizable composition has a liquid crystal phase, but the preferable irradiation temperature is 100 ° C. or lower. Polymerization due to heat can occur at a temperature of 100 ° C. or higher, so that good alignment may not be obtained.
- the optical anisotropic body of the present invention can be used as a molded body having optical anisotropy.
- uses of the molded body include a retardation plate (1/2 wavelength plate, 1/4 wavelength plate, etc.), polarizing element, dichroic polarizing plate, liquid crystal alignment film, antireflection film, selective reflection film, field of view. It can be used for optical compensation of an angle compensation film or the like.
- information recording materials such as optical lenses such as liquid crystal lenses and microlenses, polymer dispersed liquid crystal (PDLC) electronic paper, and digital paper.
- Examples 1-1 to 1-3 show production examples of the trifunctional (meth) acrylate compound of the present invention. Further, Examples 2-1 and 2-2 and Comparative Examples 1-1 to 1-3 described below are the polymerizable composition of the present invention, the comparative polymerizable composition, and the production of an optical anisotropic body using the composition. For example, Evaluation Examples 1-1 and 1-2 and Comparative Evaluation Examples 1-1 to 1-3 are comparative evaluations of the optical anisotropic bodies.
- Example 3 and Comparative Example 2 show examples of preparing the polymerizable composition of the present invention containing an optically active compound, a comparative polymerizable composition, and an optical anisotropic body using the composition
- Evaluation Example 2 and Comparative Evaluation Example 2 are comparative evaluations of the optical anisotropic bodies.
- Trifunctional (meth) acrylate compound No. 1 Production of Trifunctional (Meth) acrylate Compound No. 1 1 was produced according to the reaction scheme shown in the following [Chemical Formula 22] by the following procedure.
- Trifunctional (meth) acrylate compound no Production of Trifunctional (meth) acrylate Compound No. 2 2 was produced according to the reaction scheme shown in the following [Chemical Formula 23] by the following procedure.
- IR (KBr): 2937, 1717, 1632, 1598, 1516, 1495, 1474, 1410, 1295, 1265, 1207, 1189, 1160, 1078, 992, 812, 756 cm ⁇ 1 .
- Trifunctional (meth) acrylate compound no Production of Trifunctional (Meth) acrylate Compound No. 3 3 was produced according to the reaction formula shown in the following [Chemical Formula 24] by the following procedure.
- Phenol compound no. 9.20 g (14.2 mmol) of 1,4-7.0 g (18.5 mmol) of 3,4-di- (6-acryloyloxypropyloxy) benzoic acid was dissolved in 108 mL of THF, and 4-dimethylamino was added under ice cooling. 0.87 g (7.12 mmol) of pyridine and 2.80 g (22.2 mmol) of diisopropylcarbodiimide were added, and the mixture was stirred for 30 minutes while being cooled with ice. Acetone was added to the reaction solution, the precipitate was filtered, and then the solvent was distilled off under reduced pressure.
- this compound When this compound is heated to a high temperature, it undergoes thermal polymerization and the isotropic phase transition point (nematic phase ⁇ isotropic phase transition point) is unknown, but when cooled from the temperature at which it melted and became a liquid crystal state (nematic phase) Even at room temperature (25 ° C.), the liquid crystal phase is maintained without being crystallized. Therefore, it is a compound capable of maintaining a liquid crystal phase alone at 30 ° C. or lower.
- ⁇ Uniformity of orientation> The homogeneity of the obtained optical anisotropic body was evaluated using a polarizing microscope. The orientation state of the optical anisotropic body was observed by rotating the stage on which the cured product sample was placed under crossed Nicols, and the uniformity of the orientation was evaluated. ⁇ if the orientation of the optical anisotropic body is uniformly obtained, ⁇ if the surface is whitened or non-uniform even if the orientation is obtained, crystals, etc. are generated in the optical anisotropic body, resulting in orientation defects. If it occurred, it was marked as x.
- ⁇ Heat resistance> The obtained optical anisotropic body was heated in an oven at 150 ° C. for 30 minutes, and the retardation (R) before and after heating was measured. Before and after heating, the retardation (R) was measured. When changed by 10% or more, x was changed by 5-10%, ⁇ was less than 5%, and ⁇ was less than 1%. did. R was measured at a room temperature of 25 ° C. and a wavelength of 546 nm based on the Senarmon method using a polarizing microscope.
- the optical anisotropic body using the polymerizable composition of the present invention has uniform orientation and excellent heat resistance, but the optical anisotropic body composed only of the comparative compound has disordered orientation or heat resistance. It is apparent that the trifunctional (meth) acrylate compound of the present invention is useful because of poor properties.
- ⁇ Uniformity of orientation> The homogeneity of the obtained optical anisotropic body was evaluated using a polarizing microscope. The alignment state of the optical anisotropic body was observed by rotating the stage on which the optical anisotropic sample was placed under crossed Nicols, and the uniformity of the alignment was evaluated. If selective reflection is uniform and no orientation defect is confirmed, ⁇ , selective reflection can be confirmed, but if orientation defect due to oily streak structure is confirmed, ⁇ , if crystallization or orientation unevenness is confirmed, ⁇ It was.
- the optically anisotropic body obtained from the polymerizable composition of the present invention has uniform selective reflection at a specific wavelength and no alignment defect, but the surface of the comparative composition is whitened. It was. Therefore, it is clear that the optical anisotropic body using the trifunctional (meth) acrylate compound of the present invention is particularly useful when used as an optical film.
- the polymerizable composition containing the trifunctional (meth) acrylate compound of the present invention is excellent in solvent solubility and compatibility with other liquid crystal compounds.
- the optically anisotropic body of the present invention produced by subjecting the polymerizable composition to orientation polymerization in a liquid crystal state and photopolymerization is excellent in orientation controllability, optical properties and the like, and is useful as an optical material.
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Abstract
Description
その中でも特に、(メタ)アクリル基が2官能の単量体及び3官能の単量体は、重合体の耐熱性及び耐溶剤性を改善する上で有効な手段であることが知られており、例えば、特許文献1~6には、3官能の単量体が提案されている。
しかし、これらの単量体を用いた場合、重合体に結晶が析出したり、配向の均一制御が困難になったりする場合があるという問題があった。
上記一般式(I)中、M1、M2、M3、Z1、Z2及びZ3で表されるハロゲン原子、又はZ1、Z2及びZ3で表される炭素原子数1~6のアルキル基を置換してもよいハロゲン原子としては、フッ素、塩素、臭素、ヨウ素が挙げられる。
尚、下記〔化5〕に示す反応式により得られる、本発明の三官能(メタ)アクリレート化合物は、X1、X2又はX3が-COO-又は-OCO-のものであり、(メタ)アクリロイルオキシ基は、R1部分及びR2部分それぞれに含まれている。
本発明の重合性組成物は、本発明の三官能(メタ)アクリレート化合物を含有するもので、光学異方体作製用材料として好ましく用いられる。本発明の重合性組成物は、本発明の三官能(メタ)アクリレート化合物の他に、さらに液晶化合物を含有することができる。尚、ここでいう液晶化合物には、従来既知の液晶化合物及び液晶類似化合物並びにそれらの混合物が含まれる。
また、特に重合体の硬度を高めたい場合には、本発明の三官能(メタ)アクリレート化合物の比率を高くする(具体的には70~100質量部)ことが好ましい。特に配向の均質性を高めたい場合には、本発明の三官能(メタ)アクリレート化合物の比率が30~70質量部となるように、上記液晶化合物を併用することが好ましい。
三官能(メタ)アクリレート化合物No.1を下記〔化22〕に示す反応式に従い、以下に示す手法により製造した。
三官能(メタ)アクリレート化合物No.2を下記〔化23〕に示す反応式に従い、以下に示す手法により製造した。
三官能(メタ)アクリレート化合物No.3を下記〔化24〕に示す反応式に従い、以下に示す手法により製造した。
下記の手順([1]重合性組成物溶液の調製、[2]基板への塗布、硬化)に従い、本発明の三官能(メタ)アクリレート化合物及び重合性組成物から光学異方体を作製した。
〔表1〕に記載の配合に従って、三官能(メタ)アクリレート化合物No.1及び比較化合物No.1、No.2の重合性溶液を調製した。
各重合性化合物(組成物)1.0gを溶媒(シクロペンタノン)4.0gに添加して溶解し、ラジカル重合開始剤(アデカオプトマーN-1919;(株)ADEKA製)0.03gを加えて完全に溶解した後に、0.45μmフィルターでろ過処理を実施して、重合性溶液を調製した。
上記[1]で調製した重合性溶液を、ポリイミドを塗布し、ラビングを施したガラス基板上にスピンコーターで塗工した。塗工は、膜厚が約1.0μmになるように、スピンコーターの回転数及び時間を調整して実施した。塗工後、ホットプレートを用いて100℃で3分間乾燥した後に室温下で5分間冷却し、次いで高圧水銀灯を使用し300mJ/cm2に相当する光を照射し、塗工膜を硬化させ、光学異方体を得た。
上記実施例で得られた光学異方体について、物性(配向の均質性及び耐熱性)の評価を以下のようにして実施した。これらの結果を〔表1〕に示す。
得られた光学異方体の均質性を、偏光顕微鏡を用いて評価した。クロスニコル下で硬化物試料を設置したステージを回転させることによって、光学異方体の配向状態を観察し、配向の均質性について評価した。光学異方体の配向が均一に得られていれば○、配向が得られても表面が白化したり不均一であったりすれば△、光学異方体に結晶等が発生して配向欠陥が生じていれば×とした。
得られた光学異方体を150℃オーブンで30分間加熱し、加熱前後のリタデーション(R)を測定した。加熱前後において、リタデーション(R)を測定し、10%以上変化した場合は×、5~10%の変化であった場合は△、5%未満であれば○、1%未満であれば◎とした。
尚、Rは、偏光顕微鏡を用いてセナルモン法に基づいて、室温25℃、波長546nmにおいて測定した。
下記の手順([1]重合性組成物溶液の調製、[2]基板への塗布、硬化)に従い本発明の三官能(メタ)アクリレート化合物及び重合性組成物から光学異方体を作製した。
〔表2〕に記載の配合に従って、三官能(メタ)アクリレート化合物No.2、比較化合物No.2及び液晶化合物No.1の重合性溶液を調製した。
各重合性組成物0.95g及び光学活性化合物No.1の0.05gを溶媒(シクロペンタノン)2.0gに添加して溶解し、ラジカル重合開始剤(アデカオプトマーN-1919;(株)ADEKA製)0.03gを加えて完全に溶解した後に、0.45μmフィルターでろ過処理を実施することによって調製した。
上記[1]で調製した重合性溶液を、ポリイミドを塗布し、ラビングを施したガラス基板上にスピンコーターで塗工した。塗工は、膜厚が約2.0μmになるように、スピンコーターの回転数及び時間を調整して実施した。塗工後、ホットプレートを用いて100℃で3分間乾燥した後に室温下で3分間冷却し、次いで高圧水銀灯を使用し300mJ/cm2に相当する光を照射し、塗工膜を硬化させ、光学異方体を得た。
上記実施例で得られた光学異方体について、物性(配向の均質性、選択反射波長測定)を以下のようにして評価した。これらの評価結果を〔表2〕に示す。
得られた光学異方体の均質性を、偏光顕微鏡を用いて評価した。クロスニコル下で光学異方体試料を設置したステージを回転させることによって、光学異方体の配向状態を観察し、配向の均質性について評価した。選択反射が一様で、配向欠陥が確認されなければ○、選択反射が確認できるが、オイリーストリーク状組織による配向欠陥が確認された場合は△、結晶化や配向ムラが確認された場合は×とした。
5°正反射付属装置を取り付けた分光光度計((株)日立ハイテクノロジーズ製;U-3010形)を使用して、25℃、波長800~400nmの範囲で、光学異方体の反射率測定を実施し、選択反射中心波長(λ)を測定した。
Claims (10)
- 下記一般式(I)で表される三官能(メタ)アクリレート化合物。
- 上記一般式(I)において、環A1、環A2及び環A3が、ベンゼン環又はナフタレン環であり、環A1、環A2及び環A3のうち、少なくとも一つはナフタレン環である請求の範囲第1項に記載の三官能(メタ)アクリレート化合物。
- 上記一般式(I)において、X1、X2及びX3が、-COO-又は-OCO-である請求の範囲第1又は2項に記載の三官能(メタ)アクリレート化合物。
- 上記一般式(I)において、環A3が、ナフタレン環である請求の範囲第1~3項の何れかに記載の三官能(メタ)アクリレート化合物。
- 上記一般式(I)で表される三官能(メタ)アクリレート化合物が、単独で30℃以下で液晶相を保持することが可能である請求の範囲第1~4項の何れかに記載の三官能(メタ)アクリレート化合物
- 請求の範囲第1~5項の何れかに記載の三官能(メタ)アクリレート化合物を含有する重合性組成物。
- さらに、光学活性化合物を含有し、コレステリック液晶相を発現する請求の範囲第6項記載の重合性組成物。
- さらに、ラジカル重合開始剤を含有する請求の範囲第6又は7項に記載の重合性組成物。
- 請求の範囲第6~8項の何れかに記載の重合性組成物を光重合させることにより作製された光学異方体。
- 請求の範囲第9項記載の光学異方体を使用してなるディスプレイ用光学フィルム。
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US12/808,594 US8057701B2 (en) | 2008-04-01 | 2009-03-10 | Trifunctional (meth)acrylate compound and polymerizable composition containing same |
EP09728601.7A EP2261201B1 (en) | 2008-04-01 | 2009-03-10 | Trifunctional (meth)acrylate compound and polymerizable composition containing the compound |
CN2009801018902A CN101910106A (zh) | 2008-04-01 | 2009-03-10 | 三官能(甲基)丙烯酸酯化合物以及含有该化合物的聚合性组合物 |
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EP (1) | EP2261201B1 (ja) |
JP (1) | JP5437993B2 (ja) |
KR (1) | KR20110003312A (ja) |
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JP2010083781A (ja) * | 2008-09-30 | 2010-04-15 | Dic Corp | 重合性液晶化合物 |
JP2011148761A (ja) * | 2009-12-21 | 2011-08-04 | Adeka Corp | 新規重合性液晶化合物、及び該重合性液晶化合物を含有する重合性液晶組成物 |
CN102575167A (zh) * | 2009-11-18 | 2012-07-11 | 株式会社艾迪科 | 含有聚合性化合物的液晶组合物以及使用该液晶组合物的液晶显示元件 |
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WO2014148471A1 (ja) * | 2013-03-21 | 2014-09-25 | Dic株式会社 | 重合性化合物及びそれを用いた液晶組成物 |
CN104099104A (zh) * | 2014-08-04 | 2014-10-15 | 石家庄诚志永华显示材料有限公司 | 液晶组合物 |
JP2015183188A (ja) * | 2014-03-21 | 2015-10-22 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングMerck Patent Gesellschaft mit beschraenkter Haftung | 重合性化合物および液晶ディスプレイにおけるその使用 |
JP2016017034A (ja) * | 2014-07-04 | 2016-02-01 | Dic株式会社 | 重合性化合物及び光学異方体 |
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KR20180019534A (ko) * | 2015-06-19 | 2018-02-26 | 디아이씨 가부시끼가이샤 | 액정 표시 소자 및 그 제조 방법 |
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JP2010083781A (ja) * | 2008-09-30 | 2010-04-15 | Dic Corp | 重合性液晶化合物 |
CN102575167A (zh) * | 2009-11-18 | 2012-07-11 | 株式会社艾迪科 | 含有聚合性化合物的液晶组合物以及使用该液晶组合物的液晶显示元件 |
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EP2502973A4 (en) * | 2009-11-18 | 2014-07-23 | Adeka Corp | LIQUID CRYSTAL COMPOSITION COMPRISING A POLYMERIZABLE COMPOUND AND A LIQUID CRYSTAL DISPLAY ELEMENT COMPRISING THIS LIQUID CRYSTAL COMPOSITION |
JP2011148761A (ja) * | 2009-12-21 | 2011-08-04 | Adeka Corp | 新規重合性液晶化合物、及び該重合性液晶化合物を含有する重合性液晶組成物 |
CN102786936A (zh) * | 2012-05-09 | 2012-11-21 | 深圳市华星光电技术有限公司 | 液晶介质组合物 |
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WO2014148471A1 (ja) * | 2013-03-21 | 2014-09-25 | Dic株式会社 | 重合性化合物及びそれを用いた液晶組成物 |
JP5880992B2 (ja) * | 2013-03-21 | 2016-03-09 | Dic株式会社 | 重合性化合物及びそれを用いた液晶組成物 |
TWI570223B (zh) * | 2013-03-21 | 2017-02-11 | Dainippon Ink & Chemicals | A polymerizable compound and a liquid crystal composition using the same |
JPWO2014148471A1 (ja) * | 2013-03-21 | 2017-02-16 | Dic株式会社 | 重合性化合物及びそれを用いた液晶組成物 |
JP2015183188A (ja) * | 2014-03-21 | 2015-10-22 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングMerck Patent Gesellschaft mit beschraenkter Haftung | 重合性化合物および液晶ディスプレイにおけるその使用 |
JP2016194083A (ja) * | 2014-05-13 | 2016-11-17 | Dic株式会社 | ネマチック液晶組成物及びこれを用いた液晶表示素子 |
JP2016017034A (ja) * | 2014-07-04 | 2016-02-01 | Dic株式会社 | 重合性化合物及び光学異方体 |
CN104099104A (zh) * | 2014-08-04 | 2014-10-15 | 石家庄诚志永华显示材料有限公司 | 液晶组合物 |
Also Published As
Publication number | Publication date |
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CN101910106A (zh) | 2010-12-08 |
US20110037025A1 (en) | 2011-02-17 |
KR20110003312A (ko) | 2011-01-11 |
US8057701B2 (en) | 2011-11-15 |
JP5437993B2 (ja) | 2014-03-12 |
TW201000442A (en) | 2010-01-01 |
EP2261201A4 (en) | 2013-09-04 |
EP2261201A1 (en) | 2010-12-15 |
EP2261201B1 (en) | 2018-05-30 |
TWI490200B (zh) | 2015-07-01 |
JPWO2009122868A1 (ja) | 2011-07-28 |
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