WO2019177119A1 - 光学フィルム、偏光板、画像表示装置 - Google Patents
光学フィルム、偏光板、画像表示装置 Download PDFInfo
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- WO2019177119A1 WO2019177119A1 PCT/JP2019/010665 JP2019010665W WO2019177119A1 WO 2019177119 A1 WO2019177119 A1 WO 2019177119A1 JP 2019010665 W JP2019010665 W JP 2019010665W WO 2019177119 A1 WO2019177119 A1 WO 2019177119A1
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- C—CHEMISTRY; METALLURGY
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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
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
- C09K19/3068—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers chain containing -COO- or -OCO- groups
- C09K2019/3075—Cy-COO-Ph
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- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/542—Macromolecular compounds
- C09K2019/548—Macromolecular compounds stabilizing the alignment; Polymer stabilized alignment
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- 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
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- 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
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
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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
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
- C09K2323/03—Viewing layer characterised by chemical composition
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- 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
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
- C09K2323/03—Viewing layer characterised by chemical composition
- C09K2323/035—Ester polymer, e.g. polycarbonate, polyacrylate or polyester
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/86—Arrangements for improving contrast, e.g. preventing reflection of ambient light
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
Definitions
- the present invention relates to an optical film, a polarizing plate, and an image display device.
- Optical films such as optical compensation sheets and retardation films are used in various image display devices in order to eliminate image coloring and expand the viewing angle.
- a stretched birefringent film was used as the optical film, but it was formed from a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound in place of the stretched birefringent film in order to reduce the thickness and increase the functionality of the optical film.
- An optical film having an optically anisotropic film has been proposed.
- Such an optically anisotropic film is known to provide an alignment film in advance on a polymer support for forming the optically anisotropic film in order to align the polymerizable liquid crystal compound.
- a photo-alignment film that has been subjected to a photo-alignment process instead of a rubbing process is known (for example, Patent Documents 1 and 2).
- the photo-alignment film can impart alignment control force only by light irradiation without contact with the film, it is expected to reduce surface defects caused by foreign matter on the alignment film, which has been a problem in the conventional rubbing process. Has been. Further, in the roll-to-roll process, there is an advantage that it is possible to impart an orientation regulating force in a free direction with respect to the film conveying direction only by adjusting the direction of polarized light to be irradiated and the irradiation angle.
- the inventors tried to provide a photo-alignment film on a long polymer support with excellent optical properties in order to apply a photo-alignment treatment to a roll-to-roll process with excellent productivity. It was found that there was a problem in adhesion with the alignment film.
- this invention makes it a subject to provide the optical film which was excellent in the adhesiveness of a polymer support body and a photo-alignment film
- Another object of the present invention is to provide a polarizing plate using the optical film, and an image display device using the optical film or the polarizing plate.
- the present inventors have determined a certain amount of the component derived from the polymer support that is extracted on the surface of the photo-alignment film when the photo-alignment film is formed on the polymer support.
- the present invention was completed. That is, the present inventors have found that the above problem can be solved by the following configuration.
- the optically anisotropic film is formed from a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound having reverse wavelength dispersion,
- the amount of the component derived from the additive of the polymer support contained in the boundary region with the optical anisotropic film is 0.10 to 0.50% by mass with respect to the total mass of the photo-alignment film.
- An optical film. [2] The optical film according to [1], wherein the reverse wavelength-dispersible polymerizable liquid crystal compound is a compound represented by the following general formula (1).
- the photo-alignment film is Formed from a composition for forming a photo-alignment film comprising a polymer containing a crosslinkable group and a low molecular compound having a cinnamate group, or The optical film according to [1] or [2], which is formed from a composition for forming a photo-alignment film that includes a polymer containing a crosslinkable group and a photo-alignment group.
- the additive is a polyester compound or a sugar ester compound.
- membrane and a polymer support body, and has reverse wavelength dispersibility can be provided uniformly.
- the polarizing plate using the said optical film and the image display apparatus using the said optical film or the said polarizing plate can be provided.
- FIG. 1A It is a cross-sectional schematic diagram which shows an example of the optical film of this invention.
- FIG. 1A it is a conceptual diagram specifically explaining in detail the boundary region between the photo-alignment film and the optical anisotropic film.
- FIG. 1A it is a conceptual diagram specifically explaining in detail the boundary region between the photo-alignment film and the optical anisotropic film.
- FIG. 1A it is a conceptual diagram specifically explaining in detail the boundary region between the photo-alignment film and the optical anisotropic film.
- FIG. 1A it is a conceptual diagram specifically explaining in detail the boundary region between the photo-alignment film and the optical anisotropic film.
- FIG. 1A it is a conceptual diagram specifically explaining in detail the boundary region between the photo-alignment film and the optical anisotropic film.
- FIG. 1A it is a conceptual diagram specifically explaining in detail the boundary region between the photo-alignment film and the optical anisotropic film.
- FIG. 1A it is a cross-
- a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
- the description “(meth) acryl” intends “any one or both of acrylic and methacrylic”.
- the description of “(meth) acryloyl group” intends “one or both of acryloyl and methacryloyl”.
- the in-plane retardation (Re ( ⁇ )) and the retardation in the thickness direction (Rth ( ⁇ )) are values measured using AxoScan OPMF-1 (manufactured by Opto Science) and using light having a measurement wavelength. Specifically, by inputting an average refractive index ((nx + ny + nz) / 3) and a film thickness (d ( ⁇ m)) in AxoScan OPMF-1.
- Slow axis direction (°) Re ( ⁇ ) R0 ( ⁇ )
- Rth ( ⁇ ) ((nx + ny) / 2 ⁇ nz) ⁇ d Is calculated. Note that R0 ( ⁇ ) is displayed as a numerical value calculated by AxoScan OPMF-1, and means Re ( ⁇ ).
- the optical film of the present invention is an optical film obtained by laminating a polymer support containing an additive, a photo-alignment film, and an optical anisotropic film in this order.
- the polymer support and the photo-alignment film are in close contact, and the alignment state of the liquid crystalline compound in the optical anisotropic film is controlled by the alignment regulating force of the photo-alignment film.
- the optically anisotropic film may be provided so as not to be peeled in close contact with the photo-alignment film, or may be provided so as to be peeled from the photo-alignment film.
- the optically anisotropic film can be transferred to another transfer target such as a polarizing plate.
- the polymer support includes at least a polymer and an additive.
- a long polymer film is preferable in that it can be applied to a roll-to-roll process. From the viewpoint of providing a long region having a certain performance with little variation and forming a wound body for conveyance, the length of the long polymer film is preferably 500 to 20000 m, more preferably 1000 to 15000 m, and 2000 More preferably, it is ⁇ 10000 m.
- the thickness of the polymer support is not particularly limited. However, when the polymer support and the optically anisotropic film are used separately without being separated, the thickness of the optical film can be reduced. ⁇ 45 ⁇ m is preferred. When the polymer support and the optically anisotropic film are provided so as to be peelable, the thickness is preferably 10 to 80 ⁇ m from the viewpoint of ease of peeling and handleability.
- the polymer support is preferably optically transparent and has a total light transmittance of 80% or more when applied to a display device using the polymer support and the optically anisotropic film integrally without separating them. It is preferable.
- the upper limit value of the total light transmittance is, for example, 100% or less.
- the optical anisotropy of the polymer support can be arbitrarily set.
- the in-plane retardation (Re (550)) at a wavelength of 550 nm is 0 to 10 nm, and the thickness direction at a wavelength of 550 nm is used.
- the retardation (Rth (550)) of -10 to 15 nm.
- the glass transition temperature of the polymer support is preferably 125 ° C. or higher, since it can be heated in the formation of the photo-alignment film and the optical anisotropic film, and 140 ° C. or higher. Is more preferable.
- Such a polymer support does not cause deformation and wrinkle even under a conveying tension in a roll-to-roll process, and makes it possible to obtain a uniform and high-quality optical film.
- the upper limit is not particularly limited, the glass transition temperature of transparent polymer supports that are generally available is often 200 ° C. or less.
- a 20 mg sample of a polymer support is placed in a measurement pan, and this is placed in a nitrogen stream.
- the temperature was raised from 30 ° C. to 120 ° C. at a rate of 10 ° C./min, held for 15 minutes, and then cooled to 30 ° C. at ⁇ 20 ° C./min. Thereafter, the temperature is raised again from 30 ° C. to 250 ° C., and the temperature at which the baseline starts to deviate from the low temperature side is defined as the glass transition temperature Tg.
- polymer constituting the polymer support include a cellulose polymer; an acrylic polymer such as an acrylic polymer having an acrylic ester polymer such as polymethyl methacrylate and a lactone ring-containing polymer; and thermoplasticity.
- Norbornene polymer Polycarbonate polymer; Polyester polymer such as polyethylene terephthalate and polyethylene naphthalate; Styrene polymer such as polystyrene and acrylonitrile / styrene copolymer (AS resin); Polyethylene, polypropylene, and ethylene / propylene copolymer Polyolefin polymers such as coalescence; vinyl alcohol polymers; vinyl butyral polymers; arylate polymers; polyoxymethylene polymers; epoxy polymers; Polymers obtained by mixing these polymers.
- the polymer constituting the polymer support is an acrylic polymer, a thermoplastic norbornene polymer, a polycarbonate polymer, or a cellulose polymer represented by triacetyl cellulose, from the viewpoint of transparency and heat resistance. (Hereinafter also referred to as “cellulose acylate”) and the like. Especially, a cellulose polymer is more preferable at the point which is excellent in heat resistance and transparency especially.
- the polymer support includes an additive.
- the additive herein refers to a compound that is added to modify the above-mentioned polymer constituting the polymer support and / or to enhance the function of the film, such as a plasticizer, a UV (ultraviolet) absorber, Examples include an optical anisotropy agent, an optical anisotropy reducing agent, a hydrophobizing agent, and a durability improving agent.
- the molecular weight of these additives is typically 100 to 5000, preferably 300 to 3000, and more preferably 700 to 2000.
- the compound that can be used as an additive and its function vary depending on the polymer constituting the polymer support. Therefore, in the following, specific combinations of polymers and additives that can be used for the polymer support will be described for each polymer type.
- Cellulose acylate film As a preferred embodiment of the polymer support, a cellulose acylate film can be used. Cellulose acylate is obtained by acylating a hydroxyl group of cellulose, and the substituent can be any acetyl group having 2 carbon atoms in the acyl group to those having 22 carbon atoms.
- the acyl group having 2 to 22 carbon atoms substituted for the hydroxyl group of cellulose is not particularly limited, and may be an aliphatic group or an aromatic group, or may be a single type or a mixture of two or more types.
- Examples of cellulose acylate substituted with these groups include cellulose alkylcarbonyl ester, cellulose alkenylcarbonyl ester, cellulose aromatic carbonyl ester, cellulose aromatic alkylcarbonyl ester, and the like. It may have a group.
- Preferred acyl groups include acetyl, propionyl, butanoyl, benzoyl, naphthylcarbonyl, and cinnamoyl groups.
- an acetyl group, a propionyl group, a butanoyl group, a benzoyl group, a naphthylcarbonyl group, or a cinnamoyl group is preferable, and an acetyl group, a propionyl group, or a butanoyl group is more preferable.
- an acetyl group or a propionyl group is more preferable, and an acetyl group is particularly preferable from the viewpoints of ease of synthesis, cost, and ease of control of substituent distribution.
- the combination of an acetyl group and a propionyl group is preferable.
- the acyl substitution degree to the hydroxyl group of cellulose is not particularly limited, but when used for applications such as a polarizing plate protective film and an optical film, the higher acyl substitution degree is better compatible with various additives. Therefore, it is preferable. Therefore, the acyl substitution degree (total substitution degree) of the hydroxyl group of cellulose is preferably 2.50 to 3.00, more preferably 2.70 to 2.96, and 2.80 to 2 More preferred is .95. Further, when only the acetyl group is substituted in cellulose acylate, the degree of substitution of the acetyl group is preferably 2.70 to 2.96, and more preferably 2.80 to 2.95.
- the degree of substitution of the propionyl group is preferably 0.20 to 2.60.
- the method for measuring the substitution degree (acyl substitution degree) of acetic acid and / or a fatty acid having 3 to 22 carbon atoms substituted on the hydroxyl group of cellulose is a method according to ASTM D-817-91, and An example is NMR (nuclear magnetic resonance).
- cellulose acylate in the cellulose acylate film, can be used by mixing two or more kinds of cellulose acylates, which are single or different, from the viewpoint of substituent, substitution degree, polymerization degree, molecular weight distribution, and the like.
- the additive contained in the cellulose acylate film examples include a plasticizer, a hydrophobizing agent, an ultraviolet absorber, and a retardation adjusting agent. More specific examples of the additive include polyester oligomers, sugar ester compounds, and phosphate ester compounds. As described later, when the film also functions as a polarizer protective film, a polyester oligomer and a sugar ester compound are preferable from the viewpoint of excellent wet heat durability.
- the polyester oligomer has a repeating unit composed of a dicarboxylic acid and a diol, and can be synthesized by a known method such as a dehydration condensation reaction of a dicarboxylic acid and a diol, or an addition of a dicarboxylic anhydride to a diol and a dehydration condensation reaction. .
- dicarboxylic acid aliphatic dicarboxylic acid and aromatic dicarboxylic acid can be used.
- aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, and 1,4-cyclohexanedicarboxylic acid.
- aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, and 1,4-naphthalenedicarboxylic acid.
- diol examples include aliphatic or alicyclic diols having 2 to 12 carbon atoms, alkyl ether diols having 4 to 20 carbon atoms, and aromatic ring-containing diols having 6 to 20 carbon atoms. Two or more selected may be used in combination.
- the aromatic diol preferably has 6 to 12 carbon atoms.
- the terminal is, among others, an aliphatic group having 1 to 22 carbon atoms, an aromatic ring-containing group having 6 to 20 carbon atoms, an aliphatic carbonyl group having 1 to 22 carbon atoms, and an aromatic carbonyl group having 6 to 20 carbon atoms. It is preferably at least one selected from the group.
- the polyester oligomer When both ends are sealed, the polyester oligomer is less likely to be in a solid form at room temperature, and handling is good. As a result, a polymer film excellent in humidity stability and polarizing plate durability can be obtained.
- the content of the polyester oligomer as an additive is preferably 1 to 30% by mass with respect to the cellulose acylate, and preferably 5 to 20% by mass. More preferred is 5 to 15% by mass.
- the sugar ester compound is a compound in which at least one substitutable group (for example, a hydroxyl group and a carboxyl group) in the sugar skeleton structure constituting the compound is ester-bonded with at least one substituent.
- the sugar ester compound referred to here includes a wide range of sugar derivatives, for example, a compound containing a sugar residue such as gluconic acid as a structure. That is, the sugar ester compound includes an ester of glucose and carboxylic acid and an ester of gluconic acid and alcohol.
- the sugar ester compound is a sugar ester compound obtained by alkylating all or part of the OH groups of the compound (M) having one furanose structure or one pyranose structure, or at least one of a furanose structure or a pyranose structure.
- a sugar ester compound in which all or a part of the OH group of the compound (D) in which two species are bonded is alkylesterified is preferable.
- it is a sugar ester compound that is a monocycle of a furanose structure or a pyranose structure, and in which all or part of the hydroxyl groups of the structure are alkyl esterified, and a sugar in which all or part of the hydroxyl groups of the glucose structure are alkyl esterified More preferably, it is an ester compound.
- Examples of the compound (M) include glucose, galactose, mannose, fructose, xylose, and arabinose. Glucose or fructose is preferable, and glucose is more preferable.
- Examples of the compound (D) include lactose, sucrose, nystose, 1F-fructosyl nystose, stachyose, maltitol, lactitol, lactulose, cellobiose, maltose, cellotriose, maltotriose, raffinose, and kestose.
- gentiobiose gentiotriose, gentiotetraose, xylotriose, galactosyl sucrose, etc.
- compounds having both a furanose structure and a pyranose structure are particularly preferable, sucrose, kestose, nystose, 1F-fructosyl nystose, or stachyose is more preferable, and sucrose is more preferable.
- an aliphatic monocarboxylic acid examples include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecylic acid, lauric acid , Saturated fatty acids such as tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, and laccelic acid Unsaturated fatty acids such as unde
- the aliphatic monocarboxylic acid used to alkylate all or a part of the OH group may be two or more aliphatic monocarboxylic acids, at least one of which is a branched chain. It is preferable that it is an aliphatic monocarboxylic acid.
- isobutyric acid is particularly preferable.
- the substituent in the sugar ester compound is preferably an acetyl group and an isobutyryl group.
- a method for producing an aliphatic sugar ester compound substituted with an aliphatic monocarboxylic acid is described, for example, in JP-A-8-245678.
- the content of the above-mentioned additives is preferably 5 to 20% by mass with respect to the cellulose acylate.
- the compound of the following General formula (4) may be added to the cellulose acylate film to be used from a viewpoint of suppressing the wet heat deterioration of a polarizer. it can.
- R 11 , R 13 and R 15 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, An alkenyl group, an aralkyl group having 1 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms is represented.
- the content of JP 2013-174861 A (compounds described in paragraph numbers 0090 to 0122 of the same publication can be used) can be referred to.
- the cellulose acylate film contains the compound represented by the general formula (4)
- the content of the compound represented by the general formula (4) is 1 to 20% by mass with respect to the cellulose acylate polymer. It is preferable.
- the cellulose acylate film preferably contains fine particles as a matting agent.
- fine particles silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, etc. can be used. .
- the fine particles preferably have a primary average particle diameter of 20 nm or less and an apparent specific gravity of 70 g / liter or more. These fine particles usually form secondary particles having an average particle diameter of 0.1 to 3.0 ⁇ m and form irregularities of 0.1 to 3.0 ⁇ m on the film surface.
- the fine particles may be added so that both surfaces of the cellulose acylate film are provided with irregularities.
- the cellulose acylate film is required to make the surface of the photo-alignment film flat. It is preferable to add so that unevenness is provided only on the surface opposite to the side where the photo-alignment film is provided.
- an acrylic resin film As another preferred embodiment of the polymer support, an acrylic resin film can be used.
- the acrylic resin for example, in addition to polymethyl methacrylate (PMMA), a (meth) acrylic resin having a cyclic structure in the main chain can be used in terms of excellent heat resistance.
- PMMA polymethyl methacrylate
- a (meth) acrylic resin having a cyclic structure in the main chain can be used in terms of excellent heat resistance.
- Examples of the (meth) acrylic resin having a cyclic structure in the main chain include a (meth) acrylic resin having a lactone ring structure, a (meth) acrylic resin having a glutarimide ring structure, and a glutaric anhydride ring structure (meta ) Acrylic resins, (meth) acrylic resins having a maleic anhydride ring structure, (meth) acrylic resins having a maleimide ring structure, and the like.
- Examples of the (meth) acrylic resin having a lactone ring structure include JP 2000-230016, JP 2001-151814, JP 2002-120326, JP 2002-254544, and JP 2005.
- the synthesis methods described in Japanese Patent No. 146084 and Japanese Patent Application Laid-Open No. 2006-171464, and those produced thereby can be used.
- Examples of the (meth) acrylic resin having a glutarimide ring structure include International Publication No. 05/054311, International Publication No. 05/108438, Japanese Unexamined Patent Application Publication No. 2010-261025, Japanese Unexamined Patent Application Publication No. 2010-270162, Japanese Unexamined Patent Application Publication No. 2010. Synthesis methods described in JP-A-284840, JP-A-2011-88440, JP-A-2011-138119, JP-A-2011-245624, and the like, and those produced thereby can be used.
- additives examples include plasticizers, hydrophobizing agents, ultraviolet absorbers, retardation modifiers, deterioration inhibitors (for example, antioxidants, peroxide decomposers, radical inhibitors). , Metal deactivators, acid scavengers, amines, etc.), and compounds represented by the general formula (4) described above.
- plasticizers for example, plasticizers, hydrophobizing agents, ultraviolet absorbers, retardation modifiers, deterioration inhibitors (for example, antioxidants, peroxide decomposers, radical inhibitors).
- deterioration inhibitors for example, antioxidants, peroxide decomposers, radical inhibitors.
- Metal deactivators for example, acid scavengers, amines, etc.
- Deterioration inhibitors are described in JP-A-3-199201, JP-A-51907073, JP-A-5-194789, JP-A-5-271471, and JP-A-6-107854. Further, the content of the deterioration preventing agent is preferably 0.01 to 1% by mass, more preferably 0.01 to 0.2% by mass with respect to the solution (dope) to be prepared.
- the content of the deterioration preventing agent in the solution (dope) to be prepared is 0.01% by mass or more, the effect of the deterioration preventing agent is sufficiently exhibited, and if the content is 1% by mass or less, This is preferable because bleed-out (bleeding) of the deterioration preventing agent to the film surface hardly occurs.
- the deterioration preventing agent butylated hydroxytoluene (BHT) or tribenzylamine (TBA) is particularly preferable.
- the photo-alignment film constituting the optical film of the present invention is formed on a polymer support using the composition for forming a photo-alignment film, and the optical anisotropic film is disposed on the surface opposite to the polymer support. Is done.
- the amount of the component derived from the polymer support additive contained in the boundary region on the optically anisotropic film side is 0.10 to 0.50% by mass with respect to the total mass of the photo-alignment film. It is.
- the amount of the component derived from the aforementioned polymer support additive contained in the boundary region with the optically anisotropic film in the photoalignment film is secondary to the boundary region with the optically anisotropic film in the photoalignment film. It calculates
- membrane component is calculated with the analytical curve calculated
- the optically anisotropic film is provided so as to be peelable from the photoalignment film, the surface of the photoalignment film that appears after the optically anisotropic film is peeled off is removed.
- the secondary ion mass spectrometry By using the secondary ion mass spectrometry, it is possible to obtain the normalized secondary ion amount derived from the additive component present in the optical anisotropic film side boundary region of the photo-alignment film. In the case where the optical film of the present invention cannot be peeled between the photo-alignment film and the optical anisotropic film, the area shown in FIG. By measuring the secondary ion mass spectrometry profile of the cross section or cutting surface, the amount of normalized secondary ions derived from the additive component present in the optical anisotropic film side boundary region of the photo-alignment film is determined. Can be sought.
- the boundary region on the optical anisotropic film side of the photo-alignment film here refers to a region from the boundary line between the optical alignment film and the optical anisotropic film observed optically to a depth of about 50 nm.
- the boundary region 15 on the optically anisotropic film side of the photoalignment film refers to the boundary line 13 between the photoalignment film and the optically anisotropic film that is optically observed. It refers to a region up to a depth of about 50 nm.
- the composition for forming the photo-alignment film is applied onto the polymer support as described later.
- the solvent contained in the coating film swells on the surface of the polymer support to cause light.
- the components of the alignment film are entangled with the polymer constituting the polymer support to enhance the adhesion.
- a part of the additive contained in the polymer support is also extracted to the coating film side, so that a certain amount of the component derived from the polymer support may be mixed into the photo-alignment film. It is considered to be an index for guaranteeing the adhesion of the alignment film.
- the concentration of the component derived from the polymer support in the boundary region on the coating film side of the polymerizable liquid crystal composition in the photo-alignment film is sufficiently reduced, the alignment is not affected, but the coating side of the polymerizable liquid crystal composition in the photo-alignment film
- the film thickness of the photo-alignment film can be appropriately selected according to the material and purpose, but is preferably 10 to 1000 nm, and more preferably 10 to 700 nm. Within this range, the light reflected from the upper and lower surfaces does not interfere with the exposure and nonuniform exposure occurs, and sufficient alignment control force can be imparted to the liquid crystalline compound that constitutes the optically anisotropic film. Can be realized.
- composition for forming a photo-alignment film used in the present invention a known composition can be used. It is preferable to select from the viewpoint of adhesion to the polymer support and from the viewpoint of wettability with the polymerizable liquid crystal composition. Moreover, it is preferable that it can bridge
- the composition for forming a photo-alignment film includes a composition for forming a photo-alignment film containing a polymer containing a cross-linkable group and a low molecular compound having a photo-alignment group, and a cross-linkable group and a photo-alignment group.
- the composition for photo-alignment film formation containing the polymer to contain is mentioned.
- Examples of the composition for forming a photoalignment film containing a polymer containing a crosslinkable group and a low molecular weight compound having a photoalignment group include a polymer containing a repeating unit containing a crosslinkable group and a cinnamate group.
- Examples thereof include a composition for forming a photo-alignment film containing a low molecular compound.
- the composition for photo-alignment film formation containing the polymer containing a crosslinkable group and a photoalignment group
- the polymer containing the repeating unit containing a crosslinkable group and the repeating unit containing a cinnamate group is included.
- Examples include a composition for forming a photo-alignment film.
- the composition for forming a photo-alignment film according to the above aspect may or may not contain a low molecular compound having a photo-alignment group.
- the cinnamate group is a group having a cinnamic acid structure containing cinnamic acid or a derivative thereof as a basic skeleton, and a group represented by the following formula (I) or the following formula (II): Say.
- a represents an integer of 0 to 5
- R 1 represents a monovalent organic group
- * represents a bonding position.
- R 2 represents a monovalent organic group.
- Examples of the monovalent organic group represented by R 1 and R 2 in the formula (I) and the formula (II) include, for example, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, Examples thereof include an alkoxy group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms which may have a substituent.
- the composition for forming a photo-alignment film is a composition for forming a photo-alignment film containing a polymer Ap containing a crosslinkable group and a low molecular compound B having a cinnamate group, or a crosslinkable group and a photoalignment property.
- a composition for forming a photo-alignment film containing a polymer Ap ′ containing a group is preferred.
- a polymer Ap containing a crosslinkable group hereinafter also simply referred to as “polymer Ap”.
- polymer Ap containing the said crosslinkable group contains the photo-alignment group further. That is, the polymer Ap containing a crosslinkable group is preferably a polymer Ap ′ containing a crosslinkable group and a photoalignable group.
- the polymer Ap, the low molecular compound B having a cinnamate group, and other additive components will be described.
- the polymer Ap is not particularly limited as long as it contains a crosslinkable group, and a conventionally known polymer can be used.
- Specific examples of the polymer Ap include a polymer containing a repeating unit containing a crosslinkable group (hereinafter also referred to as “repeating unit a1 containing a crosslinkable group”).
- Examples of the main skeleton of the polymer Ap include polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, (meth) acrylic polymer, cycloolefin polymer, polyester, polyamide, polyacetal derivative, polystyrene derivative, and poly Examples include skeletons formed of (styrene-phenylmaleimide) derivatives and the like.
- at least one selected from the group consisting of a (meth) acrylic polymer and a polyorganosiloxane is preferable from the viewpoint of excellent solvent solubility and film handleability.
- the preferred molecular weight of the polymer Ap is preferably from 1,000 to 500,000 in terms of mass average molecular weight, and from 2,000 to 300,000 from the viewpoints of solvent solubility and solution viscosity during coating, and expression and maintenance of alignment regulating force after the alignment treatment. Is more preferable, and 3000 to 200,000 is still more preferable.
- the mass average molecular weight is defined as a polystyrene (PS) equivalent value by gel permeation chromatography (GPC) measurement.
- PS polystyrene
- GPC gel permeation chromatography
- the measurement by GPC in the present invention is performed using HLC-8220GPC (manufactured by Tosoh Corporation) and using TSKgel Super HZM-H, HZ4000, and HZ2000 as columns.
- the polymer Ap further preferably contains a photoalignable group, more preferably a cinnamate group, and a repeating unit containing a cinnamate group (hereinafter also referred to as “repeating unit a2 containing cinnamate”). ) Is further preferable.
- the polymer Ap may further contain other repeating units other than the repeating unit a1 containing a crosslinkable group and the repeating unit a2 containing cinnamate.
- the repeating unit a1 containing a crosslinkable group, the repeating unit a2 containing cinnamate, and other repeating units will be described.
- Repeating unit a1 containing a crosslinkable group >> Although it does not restrict
- the repeating unit represented by a following formula (A1) or (A2) is preferable. .
- R 1 represents a hydrogen atom or a methyl group.
- R 2 represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an oxygen atom. This means that it is bonded to another silicon atom.
- L represents a single bond or a divalent linking group
- Y represents a crosslinkable group described later.
- examples of the alkyl group having 1 to 6 carbon atoms of R 2 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
- a methyl group or an ethyl group is preferable.
- Specific examples of the alkoxy group having 1 to 6 carbon atoms of R 2 include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, and an n-butoxy group. A methoxy group or an ethoxy group is preferred.
- divalent linking group represented by L in the formulas (A1) and (A2) include —CO—, —O—CO—, —O—CO— (CH 2 ) n —.
- O— —CO—O—Ph—, —CO—O—Ph—Ph—, —CO—O— (CH 2 ) n —, — (CH 2 ) n —Cy— and the like can be mentioned.
- Ph represents a divalent benzene ring (for example, a phenylene group) which may have a substituent
- Cy represents a divalent cyclohexane ring (for example, a substituent). Cyclohexane-1,4-diyl group, etc.).
- n an integer of 1 to 4.
- the bonding direction of the divalent group represented by L is not limited unless otherwise specified.
- L when L is —CO—O—, the linking form of L and the adjacent carbon atom and Y may be a carbon atom —CO—O—Y or Y—O—CO—carbon atom. It may be.
- crosslinkable group Y examples include an epoxy group, an oxetanyl group, an amino group, a carboxyl group, a hydroxyl group, —NH—CH 2 —O—R (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). ), A group containing a crosslinkable functional group such as an ethylenically unsaturated group and a blocked isocyanate group.
- an epoxy group, an oxetanyl group, or a 3,4-epoxycyclohexyl group is preferable, and an epoxy group or an oxetanyl group is more preferable.
- a 3-membered cyclic ether group is also called an epoxy group
- a 4-membered cyclic ether group is also called an oxetanyl group.
- repeating unit represented by Formula (A1) and Formula (A2) include the following repeating units.
- R 1 and R 2 each have the same meanings as R 1 and R 2 in the above-mentioned formula (A1) and formula (A2).
- Repeating unit a2 containing cinnamate group examples include those in which Y represents various cinnamate groups in place of the crosslinkable group in the above-described repeating unit represented by the general formula (A1) or (A2). Specific examples of the cinnamate group include the following groups described in paragraph [0016] of JP-A-2015-026050. In the following structure, * indicates a bonding position with L. In the repeating unit represented by the general formula (A1) or (A2), when Y represents the following cinnamate group instead of the crosslinkable group, L in the general formula (A1) or (A2) is Represents a single bond.
- the polymer Ap may have a repeating unit other than the repeating unit a1 and the repeating unit a2 described above.
- the copolymer contains other repeating units, for example, substrate adhesion, solvent solubility, heat resistance, and the like can be improved.
- the other repeating unit that can be contained in the polymer Ap is preferably a repeating unit containing a functional group that adjusts the polarity of the polymer Ap from the viewpoint of adhesion to the substrate and solvent solubility.
- a repeating unit containing a hydroxyl group, a carboxylic acid group, or an ionic group is preferred, and from the viewpoint of imparting lipophilicity, a repeating unit containing a higher alkyl group or an aromatic group is preferred. preferable.
- the repeating unit containing a 5-membered or more heterocyclic ring, a cyclic ketone, or an aromatic ring is preferable from the viewpoint of achieving both substrate adhesion and solvent solubility.
- a repeating unit including a rigid structure is preferable.
- a repeating unit containing a functional group capable of reacting with a component contained in the polymerizable liquid crystal composition is preferable.
- the content of the polymer Ap in the composition for forming a photo-alignment film is from the viewpoint of adjusting to a coating solution viscosity suitable for the roll-to-roll process.
- the amount is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the solvent.
- the low molecular compound B having a cinnamate group (hereinafter also referred to as “low molecular compound B”) is preferably a compound having a cinnamate group and having a molecular weight smaller than that of the polymer Ap.
- the photo-alignment film-forming composition contains the low-molecular compound B, whereby the alignment property of the produced photo-alignment film becomes better.
- the low molecular compound B is a compound having a cinnamate group and a molecular weight smaller than that of the polymer Ap, and a crosslinkable group possessed by the polymer Ap. It is preferable to use a bondable compound and use the reaction product as a photo-alignment film.
- the molecular weight of the low molecular weight compound B is not particularly limited, but is preferably from 200 to 1,000, and more preferably from 250 to 700, from the viewpoint of securing solubility and orientation regulating ability.
- Examples of the low molecular compound B include a compound represented by the following formula (B1).
- a represents an integer of 0 to 5
- R 1 represents a monovalent organic group
- R 2 represents a monovalent organic group.
- the plurality of R 1 may be the same or different from each other.
- the monovalent organic group represented by R 1 include a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a substituent.
- An aryl group having 6 to 20 carbon atoms which may be used, among which an alkoxy group having 1 to 20 carbon atoms is preferable, an alkoxy group having 1 to 6 carbon atoms is more preferable, and a methoxy group or ethoxy group Groups are more preferred.
- Examples of the monovalent organic group for R 2 include, for example, a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, and an optionally substituted 6 to 6 carbon atoms.
- 20 aryl groups and the like can be mentioned. Among them, a linear or branched alkyl group having 1 to 20 carbon atoms is preferable, and a branched alkyl group having 1 to 10 carbon atoms is more preferable. Further, a is preferably 1 , and R 1 is preferably in the para position.
- a substituent which the aryl group mentioned above may have, an alkoxy group, a hydroxy group, a carboxy group, an amino group, etc. are mentioned, for example.
- Specific examples of the compound represented by the formula (B1) include octyl cinnamate, ethyl-4-isopropyl cinnamate, ethyl-2,4-diisopropyl cinnamate, methyl-2,4-diisopropyl cinnamate, Propyl-p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p-methoxycinnamate, 2-ethylhexyl-p-methoxycinnamate, 2-ethoxyethyl-p-methoxycinnamate, 2-hexyldecanyl -P-methoxycinnamate, cyclohexyl-p-methoxycinnamate and the like.
- the content of the low molecular compound B is 10 to 10% by mass with respect to the mass of the repeating unit a1 of the polymer Ap because the orientation of the photo-alignment film to be produced becomes better. 500% by mass is preferable, and 30 to 300% by mass is preferable. Further, when the composition for forming a photoalignment film contains an organic solvent described later, the content of the low molecular compound B is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the solvent, 0.1 to 10 parts by mass is more preferable.
- the composition for forming a photo-alignment film is a polymer separately from the polymer Ap containing the repeating unit a1 containing a crosslinkable group, because the adhesion to the polymer support is improved and the alignment regulating force is improved. It is preferable that the crosslinking agent C which has a crosslinkable group which can react with Ap is included. By appropriately adjusting the amount of the crosslinkable group, extraction of components derived from the additive of the polymer support and diffusion in the coating film can be controlled.
- the molecular weight of the crosslinking agent C is preferably 1000 or less, and more preferably 100 to 500.
- the crosslinkable group is preferably a heat crosslinkable group that causes a curing reaction by the action of heat.
- the crosslinking agent C include a compound having two or more epoxy groups or oxetanyl groups in the molecule, a blocked isocyanate compound (a compound having a protected isocyanato group), an alkoxymethyl group-containing compound, and the like.
- numerator which shows a specific example below, or a block isocyanate compound is preferable.
- Compound with two or more oxetanyl groups in the molecule >> Specific examples of the compound having two or more oxetanyl groups in the molecule include Aron oxetane OXT-121, OXT-221, OX-SQ, and PNOX (manufactured by Toagosei Co., Ltd.).
- the blocked isocyanate compound is not particularly limited as long as the isocyanate group has a chemically protected blocked isocyanate group, but is a compound having two or more blocked isocyanate groups in one molecule from the viewpoint of curability. It is preferable.
- the blocked isocyanate group in this invention is a group which can produce
- the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can illustrate preferably.
- the blocked isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90 ° C. to 250 ° C.
- the skeleton of the blocked isocyanate compound is not particularly limited and may be any as long as it has two isocyanate groups in one molecule, and may be aliphatic, alicyclic or aromatic.
- Polyisocyanates may be used, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene Diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2, '-Diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diiso
- TDI tolylene diisocyanate
- MDI diphenylmethane diisocyanate
- HDI hexamethylene diisocyanate
- IPDI isophorone diisocyanate
- Examples of the mother structure of the blocked isocyanate compound include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
- Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. Can be mentioned. Among these, a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is preferable.
- the blocked isocyanate compound is available as a commercial product.
- Coronate AP Stable M Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (above, manufactured by Nippon Polyurethane Industry Co., Ltd.), Takenate B -830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (manufactured by Mitsui Chemicals, Inc.), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (above, manufactured by Asahi Kasei Chemicals Corporation), Death Module BL1100, BL1265 MPA / X BL3575 / 1, BL3272MPA, BL
- the content of the crosslinking agent C is preferably 1 to 1000 parts by mass with respect to 100 parts by mass of the repeating unit a1 of the polymer Ap. Part by mass is more preferable. Further, when the composition for forming a photoalignment film contains an organic solvent described later, the content of the crosslinking agent C is preferably 0.05 to 50 parts by mass with respect to 100 parts by mass of the solvent, and 1 to 10 parts by mass. Is more preferable.
- the composition for forming a photo-alignment film may contain components other than those described above.
- examples of other components include a crosslinking accelerator, an adhesion improver, a leveling agent, and a plasticizer.
- examples of the crosslinking accelerator include various metal salt chelate compounds and thermal acid generators.
- As the adhesion improver, leveling agent, and plasticizer various known materials known as additives for coating compositions can be used.
- the composition for forming a photo-alignment film preferably contains an organic solvent from the viewpoint of workability for producing the photo-alignment film.
- an organic solvent that is easily compatible with the component derived from the additive of the polymer support is preferable.
- the polymer support is obtained when the composition for forming a photo-alignment film is coated on the polymer support.
- the adhesion to the photo-alignment film can be enhanced by acting on the surface of the body.
- by appropriately adjusting the content of the organic solvent excessive extraction of the component derived from the additive of the polymer support into the composition for forming a photo-alignment film is suppressed, thereby reducing the optical anisotropic film.
- Orientation control can be improved.
- a polymer support is a cellulose acylate film containing an additive and is a polyester compound or a sugar ester compound, it is preferable to include ketones, esters, or propylene glycol ethers as the organic solvent.
- organic solvent examples include ketones (for example, acetone, 2-butanone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, and cyclopentanone), ethers (for example, dioxane, tetrahydrofuran, and the like), fat Aromatic hydrocarbons (for example, hexane), alicyclic hydrocarbons (for example, cyclohexane), aromatic hydrocarbons (for example, toluene, xylene, and trimethylbenzene), halogenated carbons (for example, dichloromethane) , Dichloroethane, dichlorobenzene, and chlorotoluene), esters (eg, methyl acetate, ethyl acetate, and butyl acetate), water, alcohols (eg, ethanol, isopropanol, butanol, and cyclohexanol), cellosolves
- the photo-alignment film constituting the present invention can be produced by a conventionally known production method except that the above-described composition for forming a photo-alignment film is used.
- the photo-alignment film is preferably produced by a roll-to-roll process.
- a manufacturing method including the following step 1, the following step 2, and the following step 3 may be mentioned.
- the optically anisotropic film can be controlled by controlling the extraction of the component derived from the additive of the polymer support while improving the adhesion between the polymer support and the photo-alignment film.
- the orientation control can be improved.
- Step 1 Application step for applying the above-described composition for forming a photo-alignment film to the surface of the above-mentioned polymer support to form a coating film.
- Step 2 A heating step for drying and crosslinking the coating film by heating.
- the application method in the application step is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include spin coating, die coating, gravure coating, flexographic printing, and inkjet printing. In the roll-to-roll process, die coating or gravure coating is particularly preferable.
- coating is performed using the die
- the heating method in the heating step is not particularly limited, and the polymer support with a coating film obtained through Step 1 may be heated by a known method.
- a heating method for example, a method of heating a polymer support with a coating by exposing it to a heating atmosphere, or a method of heating a polymer support with a coating by bringing it into contact with a transport roll or the like through which a heat medium is passed. And the method of heating the polymer support body with a coating film by irradiating with a heat ray is mentioned.
- the heating temperature is preferably 30 to 200 ° C.
- Adhesion between the polymer support and the photo-alignment film is enhanced by appropriately controlling the solvent removal in the coating and the thermal crosslinking reaction of the polymer Ap during the heating step, and the addition of the polymer support
- the extraction control of the component derived from the agent can be controlled to improve the orientation control of the optically anisotropic film.
- the polymer support with a coating film is heated by the heating device 33.
- the polarized light applied to the coating film after drying and crosslinking after Step 2 is not particularly limited, and examples thereof include linearly polarized light, circularly polarized light, and elliptically polarized light, and linearly polarized light is preferable.
- the “oblique direction” for irradiating non-polarized light is not particularly limited as long as it is a direction inclined by a polar angle ⁇ (0 ⁇ ⁇ 90 °) with respect to the normal direction of the coating film surface. Can be selected as appropriate.
- the wavelength in polarized light or non-polarized light is not particularly limited as long as it is a wavelength capable of controlling the orientation of the liquid crystal molecules contained in the coating film after drying and crosslinking, and examples thereof include ultraviolet light, near ultraviolet light, and visible light. Is mentioned. Of these, near ultraviolet rays of 250 nm to 450 nm are particularly preferable.
- the light source for irradiating polarized light or non-polarized light include a xenon lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, and a metal halide lamp.
- linearly polarized light can be obtained by applying a polarizing filter and a polarizing prism to the light from these light sources.
- light sources such as LED (light emitting diode) and a laser
- the same polarized light irradiation is realizable with a simpler structure.
- the accumulated light quantity of polarized light or non-polarized light is not particularly limited as long as it is a wavelength capable of controlling the alignment of liquid crystal molecules contained in the coating film after drying and crosslinking, but is preferably 1 to 600 mJ / cm 2. more preferably ⁇ 300mJ / cm 2, more preferably 5 ⁇ 100mJ / cm 2.
- the illuminance of polarized light or non-polarized light is not particularly limited as long as it is a wavelength capable of controlling the orientation of liquid crystal molecules contained in the dried and crosslinked coating film, but is preferably 0.1 to 300 mW / cm 2 , 1 to 100 mW / cm 2 is more preferable.
- the optically anisotropic film constituting the optical film of the present invention is a layer obtained by curing a composition containing a polymerizable liquid crystal compound having reverse wavelength dispersion (hereinafter also referred to as “polymerizable liquid crystal composition”). is there.
- the alignment state of the liquid crystal compound is fixed. That is, in the optically anisotropic film, the liquid crystal compound forms an alignment state by the alignment regulating force of the photo-alignment film described above, and the polymerizable group in the liquid crystal compound is polymerized by the curing treatment, so that the alignment state is It is fixed.
- reverse wavelength dispersive polymerized liquid crystalline compound intends a polymerizable liquid crystal compound capable of forming an optically anisotropic film having a reverse wavelength dispersive property.
- a specific polymerizable liquid crystal compound described later is preferable.
- the thickness of the optically anisotropic film is not particularly limited, but is preferably 0.1 to 10 ⁇ m, more preferably 0.5 to 5 ⁇ m.
- the optically anisotropic film functions as a positive A plate
- the optically anisotropic film is preferably an optically anisotropic film in which a specific polymerizable liquid crystal compound is homogeneously (horizontal) aligned.
- the optically anisotropic film is a layer obtained by polymerizing (fixing the orientation state) after orienting the polymerizable liquid crystal composition in the smectic phase. Is preferred.
- the optically anisotropic film constituting the optical film of the present invention has a reverse wavelength dispersibility from the viewpoint of exhibiting a uniform polarization conversion function over a wide band and imparting excellent display performance to the display device. ) Is preferably satisfied. 0.75 ⁇ Re (450) / Re (550) ⁇ 1.00 (II)
- Re (450) represents the in-plane retardation of the optically anisotropic film at a wavelength of 450 nm
- Re (550) represents the in-plane retardation of the optically anisotropic film at a wavelength of 550 nm.
- the in-plane retardation value is a value measured using AxoScan OPMF-1 (manufactured by Optoscience) and using light having a measurement wavelength.
- the specific polymerizable liquid crystal compound in the present specification is a polymerizable liquid crystal compound represented by the following formula (1).
- the polymerizable liquid crystal compound represented by the following formula (1) has reverse wavelength dispersion. That is, when the polymerizable liquid crystal compound represented by the following formula (1) is cured to form an optically anisotropic film, the optically anisotropic film exhibits reverse wavelength dispersion.
- D 1 , D 2 , E 1 , E 2 , E 3 , and E 4 are each independently a single bond, —CO—O—, —C ( ⁇ S) O—, — CR 1 R 2 —, —CR 1 R 2 —CR 3 R 4 —, —O—CR 1 R 2 —, —CR 1 R 2 —O—CR 3 R 4 —, —CO—O—CR 1 R 2 —, —O—CO—CR 1 R 2 —, —CR 1 R 2 —O—CO—CR 3 R 4 —, —CR 1 R 2 —CO—O—CR 3 R 4 —, —NR 1 —CR 2 R 3 — or —CO—NR 1 — is represented.
- the bonding direction of the divalent group represented by D 1 , D 2 , E 1 , E 2 , E 3 , and E 4 (for example, —CO—O—) is not particularly limited. There is no limit unless it is.
- D 1 is —CO—O—
- the connecting form of G 1 and Ar 1 adjacent to D 1 may be G 1 —CO—O—Ar 1 or G 1 —O It may be —CO—Ar 1 .
- R 1 , R 2 , R 3 , and R 4 each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
- G 1 and G 2 each independently represent a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms which may have a substituent, One or more of —CH 2 — constituting the hydrocarbon group may be substituted with —O—, —S—, or NH—.
- a 1 and A 2 each independently have an optionally substituted divalent aromatic hydrocarbon group having 6 to 12 carbon atoms or a substituent.
- SP 1 and SP 2 are each independently a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear chain having 1 to 12 carbon atoms.
- One or more of —CH 2 — constituting a linear or branched alkylene group is substituted with —O—, —S—, —NH—, —N (Q) —, or —CO—.
- Q represents a substituent.
- L 1 and L 2 each independently represent a monovalent organic group, and at least one of L 1 and L 2 represents a polymerizable group.
- Ar 1 is an aromatic ring represented by the following formula (Ar-3), at least one of L 1 and L 2 and L 3 and L 4 in the following formula (Ar-3) is a polymerizable group.
- m represents an integer of 0 to 2
- n represents an integer of 0 to 2
- the plurality of E 4 may be the same or different
- the plurality of A 2 are May be the same or different.
- Ar 1 represents any aromatic ring selected from the group consisting of groups represented by formulas (Ar-1) to (Ar-5) described later.
- the alkyl group having 1 to 4 carbon atoms represented by R 1 , R 2 , R 3 , and R 4 may be linear, branched, or cyclic, Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
- the divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms represented by G 1 and G 2 is preferably a 5-membered ring or a 6-membered ring.
- the alicyclic hydrocarbon group may be saturated or unsaturated, but is preferably a saturated alicyclic hydrocarbon group.
- the divalent alicyclic hydrocarbon group represented by G 1 and G 2 for example, the description in paragraph [0078] of JP2012-21068A can be referred to, and the contents thereof are incorporated in the present specification. .
- a cyclohexylene group (a divalent group derived from a cyclohexane ring) is preferable, a 1,4-cyclohexylene group is more preferable, and a trans-1,4-cyclohexylene group is still more preferable.
- the substituent that the divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms represented by G 1 and G 2 may have is represented by the following formula (Ar-1 And the same substituents as those which may be possessed by the aromatic hydrocarbon group having 6 to 12 carbon atoms and the aromatic heterocyclic group having 3 to 12 carbon atoms represented by Y 1 in the formula ( 1 ).
- the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms represented by A 1 and A 2 includes 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene Group, 1,4-naphthylene group, 1,5-naphthylene group, 2,6-naphthylene group and the like. Among them, 1,4-phenylene group is preferable, and trans-1,4-phenylene group is more preferable. preferable.
- Examples of the divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms represented by A 1 and A 2 include the same groups as those described for G 1 and G 2 in the above formula (1).
- a cyclohexylene group (a divalent group derived from a cyclohexane ring) is preferred, a 1,4-cyclohexylene group is more preferred, and a trans-1,4-cyclohexylene group is still more preferred.
- divalent cycloaliphatic in the formula (1) A 1 and A 2 represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and A 1 and A 2 are C 5 -C 8 shown
- the substituent that the formula hydrocarbon group may have include an aromatic hydrocarbon group having 6 to 12 carbon atoms and an aromatic group having 3 to 12 carbon atoms represented by Y 1 in the formula (Ar-1) described later. Examples thereof include the same substituents that the heterocyclic group may have.
- examples of the linear or branched alkylene group having 1 to 12 carbon atoms represented by SP 1 and SP 2 include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, A hexylene group, a methylhexylene group, a heptylene group, or the like is preferable.
- SP 1 and SP 2 are as described above, wherein one or more of —CH 2 — constituting a linear or branched alkylene group having 1 to 12 carbon atoms is —O—, —S—, — It may be a divalent linking group substituted by NH-, -N (Q)-, or -CO-.
- Examples of the substituent represented by Q include an aromatic hydrocarbon group having 6 to 12 carbon atoms and an aromatic heterocyclic group having 3 to 12 carbon atoms represented by Y 1 in the formula (Ar-1) described later. The thing similar to the substituent which may be mentioned is mentioned.
- examples of the monovalent organic group represented by L 1 and L 2 include an alkyl group, an aryl group, a heteroaryl group, and a cyano group.
- the alkyl group may be linear, branched or cyclic, but is preferably linear.
- the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 10 carbon atoms.
- the aryl group may be monocyclic or polycyclic but is preferably monocyclic.
- the aryl group preferably has 6 to 25 carbon atoms, more preferably 6 to 10 carbon atoms.
- the heteroaryl group may be monocyclic or polycyclic.
- the number of heteroatoms constituting the heteroaryl group is preferably 1 to 3.
- the hetero atom constituting the heteroaryl group is preferably a nitrogen atom, a sulfur atom, or an oxygen atom.
- the carbon number of the heteroaryl group is preferably 6-18, more preferably 6-12.
- the alkyl group, aryl group, and heteroaryl group described above may be unsubstituted or may have a substituent. Examples of the substituent include a substituent that may be possessed by an aromatic hydrocarbon group having 6 to 12 carbon atoms and an aromatic heterocyclic group having 3 to 12 carbon atoms represented by Y 1 in formula (Ar-1) described later. The same thing is mentioned.
- the polymerizable group represented by at least one of L 1 and L 2 is not particularly limited, but a polymerizable group capable of radical polymerization (radical polymerizable group) or a polymerizable group capable of cationic polymerization. (Cationically polymerizable group) is preferred.
- a radical polymerizable group a generally known radical polymerizable group can be used, and an acryloyl group or a methacryloyl group is preferable.
- the acryloyl group and the methacryloyl group it is generally known that the polymerization rate of the acryloyl group is faster, and the acryloyl group is preferable from the viewpoint of productivity improvement, but the methacryloyl group is also used as the polymerizable group. it can.
- the cationic polymerizable group generally known cationic polymerizable can be used. Specifically, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester group, and A vinyloxy group etc. are mentioned.
- an alicyclic ether group or a vinyloxy group is preferable, and an epoxy group, an oxetanyl group, or a vinyloxy group is more preferable.
- an epoxy group, an oxetanyl group, or a vinyloxy group is more preferable.
- the polymerizable group those exemplified below are preferable.
- L 1 and L 2 in the above formula (1) are both polymerizable groups, and are an acryloyl group or a methacryloyl group, because the wet heat durability becomes better. It is more preferable.
- Ar 1 represents any aromatic ring selected from the group consisting of groups represented by the following formulas (Ar-1) to (Ar-5).
- * represents a bonding position with D 1 or D 2 in the above formula (I).
- formulas (Ar-1) to (Ar-5) will be described.
- Q 1 represents N or CH
- Q 2 represents —S—, —O—, or —N (R 5 ) —
- R 5 represents Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- Y 1 represents an optionally substituted aromatic hydrocarbon group having 6 to 12 carbon atoms, or an optionally substituted carbon number. 3 to 12 aromatic heterocyclic groups are represented.
- alkyl group having 1 to 6 carbon atoms represented by R 5 include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, Examples thereof include an n-pentyl group and an n-hexyl group.
- aromatic hydrocarbon group having 6 to 12 carbon atoms represented by Y 1 include aryl groups such as a phenyl group, a 2,6-diethylphenyl group, and a naphthyl group.
- Examples of the aromatic heterocyclic group having 3 to 12 carbon atoms represented by Y 1 include heteroaryl groups such as thienyl group, thiazolyl group, furyl group, and pyridyl group.
- Examples of the substituent that the aromatic hydrocarbon group having 6 to 12 carbon atoms and the aromatic heterocyclic group having 3 to 12 carbon atoms represented by Y 1 may have include an alkyl group, an alkoxy group, and a halogen atom. An atom etc. are mentioned.
- alkyl group for example, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group) Group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group, etc.), more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group.
- an alkyl group having 1 to 8 carbon atoms for example, methyl group, ethyl group, propyl group, isopropyl group
- an alkyl group having 1 to 4 carbon atoms for example,
- an alkoxy group having 1 to 18 carbon atoms is preferable, and an alkoxy group having 1 to 8 carbon atoms (for example, a methoxy group, an ethoxy group, an n-butoxy group, and a methoxyethoxy group) is more preferable.
- An alkoxy group having 1 to 4 carbon atoms is more preferable, and a methoxy group or an ethoxy group is particularly preferable.
- a halogen atom a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example, Among these, a fluorine atom or a chlorine atom is preferable.
- Z 1 , Z 2 and Z 3 are each independently a hydrogen atom or a monovalent linear or branched chain having 1 to 20 carbon atoms.
- the monovalent linear or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms.
- Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a methylcyclohexyl group, and ethyl.
- Monocyclic saturated hydrocarbon groups such as cyclohexyl group; cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cyclodecenyl group, cyclopentadienyl group, cyclohexadienyl group, cyclooctadienyl group, and Monocyclic unsaturated hydrocarbon groups such as cyclodecadiene; bicyclo [2.2.1] heptyl group, bicyclo [2.2.2] octyl group, tricyclo [5.2.1.0 2,6 ] decyl Group, tricyclo [3.3.1.1 3,7 ] decyl group, tetracyclo [6.
- dodecyl group polycyclic saturated hydrocarbon group such as adamantyl group, and the like.
- the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a 2,6-diethylphenyl group, a naphthyl group, and a biphenyl group.
- Aryl groups (particularly phenyl groups) are preferred.
- a halogen atom a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, for example, Among these, a fluorine atom, a chlorine atom, or a bromine atom is preferable.
- alkyl group having 1 to 6 carbon atoms represented by R 6 to R 9 , R X , and R Y include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group.
- a 3 and A 4 are each independently —O—, —N (R 10 ) —, —S—, and —CO—.
- R 10 represents a hydrogen atom or a substituent.
- the substituent include the substituents that the aromatic hydrocarbon group having 6 to 12 carbon atoms and the aromatic heterocyclic group having 3 to 12 carbon atoms represented by Y 1 in the above formula (Ar-1) may have. The same thing is mentioned.
- X represents a hydrogen atom or a non-metal atom of Groups 14 to 16 to which a substituent may be bonded.
- examples of the non-metal atoms of Group 14 to 16 represented by X include an oxygen atom, a sulfur atom, a nitrogen atom having a substituent, and a carbon atom having a substituent.
- substituents include Include an alkyl group, an alkoxy group, an alkyl-substituted alkoxy group, a cyclic alkyl group, an aryl group (eg, phenyl group, naphthyl group, etc.), cyano group, amino group, nitro group, alkylcarbonyl group, sulfo group, hydroxyl group, etc. Is mentioned.
- D 3 and D 4 each independently represent a single bond, —CO—O—, —C ( ⁇ S) O—, —CR 1 R 2 —, —CR 1 R 2 —CR 3 R 4 —, —O—CR 1 R 2 —, —CR 1 R 2 —O—CR 3 R 4 —, —CO—O—CR 1 R 2 —, —O—CO—CR 1 R 2 —, —CR 1 R 2 —O—CO—CR 3 R 4 —, —CR 1 R 2 —CO—O—CR 3 R 4 —, —NR 1 —CR 2 R 3 —, or —CO— NR 1 -is represented.
- the bonding direction of the divalent group represented by D 3 and D 4 is not limited unless otherwise specified.
- D 3 is —CO—O—
- the connecting form of D 1 and the adjacent SP 3 and carbon atom may be SP 3 —CO—O—carbon atom, or SP 3 —O. It may be a -CO-carbon atom.
- R 1 , R 2 , R 3 , and R 4 each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
- the alkyl group having 1 to 4 carbon atoms represented by R 1 , R 2 , R 3 , and R 4 may be linear, branched, or cyclic, Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
- each of SP 3 and SP 4 independently represents a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a carbon atom having 1 to 12 carbon atoms.
- One or more of —CH 2 — constituting the linear or branched alkylene group is substituted with —O—, —S—, —NH—, —N (Q) —, or —CO—.
- Q represents a substituent.
- Examples of the linear or branched alkylene group having 1 to 12 carbon atoms are the same as those described for SP 1 and SP 2 in the above formula (1).
- the substituent represented by Q may be an aromatic hydrocarbon group having 6 to 12 carbon atoms and an aromatic heterocyclic group having 3 to 12 carbon atoms represented by Y 1 in the above formula (Ar-1). The thing similar to a good substituent is mentioned.
- L 3 and L 4 each independently represent a monovalent organic group
- L 3 and L 4 and at least one of L 1 and L 2 in the formula (1) Represents a polymerizable group.
- the monovalent organic group include those described for L 1 and L 2 in the above formula (1).
- the polymerizable group include the same as those described in L 1 and L 2 in the formula (1).
- Ax has at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and has 2 to 30 organic groups are represented.
- Ay represents a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or an aromatic hydrocarbon ring.
- the aromatic ring in Ax and Ay may have a substituent, and Ax and Ay may combine to form a ring.
- Q 3 represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms.
- Examples of Ax and Ay include those described in paragraphs [0039] to [0095] of Patent Document 2 (International Publication No. 2014/010325).
- Specific examples of the alkyl group having 1 to 6 carbon atoms represented by Q 3 include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl. Group, n-pentyl group, n-hexyl group and the like.
- examples of the substituent that the alkyl group having 1 to 6 carbon atoms represented by Q 3 may have include an aromatic hydrocarbon group having 6 to 12 carbon atoms represented by Y 1 in the above formula (Ar-1). And the same substituents that the aromatic heterocyclic group having 3 to 12 carbon atoms may have.
- m is 1 and A 1 and G 1 both have a substituent in the above formula (1), because the wet heat durability of the optically anisotropic film becomes better.
- a cyclohexylene group which may be substituted, E 1 is a single bond, n is 1, A 2 and G 2 are both optionally substituted cyclohexylene groups, and E 2 Is preferably a compound representing a single bond.
- the pKa of the diphenol compound represented by HO—Ar 1 —OH derived from the structure of Ar 1 in the above formula (1) is preferably 11 or less.
- THF tetrahydrofuran
- the alkali titration method described on pages 215 to 217 of Experimental Chemistry Course Second Edition published by Maruzen Co., Ltd. can be used.
- K side chain structure in 1-14
- K examples include compounds having side chain structures shown in Table 1 below.
- “*” shown in the side chain structure of K represents the bonding position with the aromatic ring.
- the groups adjacent to the acryloyloxy group and methacryloyl group each represent a propylene group (a group in which a methyl group is substituted with an ethylene group). Represents a mixture of positional isomers having different methyl group positions.
- the polymerizable liquid crystal composition may contain other polymerizable compound having one or more polymerizable groups in addition to the specific polymerizable liquid crystal compound described above.
- the polymerizable group that the other polymerizable compound has is not particularly limited, and examples thereof include a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among these, a (meth) acryloyl group is preferable as the polymerizable group.
- the other polymerizable compound is preferably another polymerizable compound having 1 to 4 polymerizable groups because the durability of the formed optically anisotropic film is further improved. More preferred are other polymerizable compounds having 2-4.
- Examples of such other polymerizable compounds include compounds represented by formula (M1), formula (M2) and formula (M3) described in paragraphs [0030] to [0033] of JP2014-077068A More specifically, specific examples described in paragraphs [0046] to [0055] of the same publication can be given.
- a known polymerizable liquid crystal compound may be added for the purpose of adjusting the size of wavelength dispersion and refractive index anisotropy and adjusting the liquid crystal phase transition temperature of the coating film.
- examples of such polymerizable liquid crystal compounds include various polymerizable liquid crystal compounds described in “Liquid Crystal Handbook” (edited by Liquid Crystal Handbook Editorial Committee, Maruzen).
- the polymerizable liquid crystal composition preferably contains a polymerization initiator.
- the polymerization initiator is preferably a photopolymerization initiator capable of initiating a polymerization reaction by ultraviolet irradiation.
- Examples of the photopolymerization initiator include ⁇ -carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No. 2,448,828), ⁇ -hydrocarbon substitution, and the like.
- Aromatic acyloin compounds described in US Pat. No. 2,722,512
- polynuclear quinone compounds described in US Pat. Nos.
- the polymerization initiator is an oxime type polymerization initiator because the wet heat durability becomes better.
- the polymerization initiator is represented by the following formula (I). More preferably.
- X 2 represents a hydrogen atom or a halogen atom.
- Ar 3 represents a divalent aromatic group
- D 5 represents a divalent organic group having 1 to 12 carbon atoms.
- R 11 represents an alkyl group having 1 to 12 carbon atoms
- Y 2 represents a monovalent organic group.
- examples of the halogen atom represented by X 2 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, a chlorine atom is preferable.
- examples of the aromatic ring constituting the divalent aromatic group represented by Ar 3 include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthroline ring.
- examples of the divalent organic group having 1 to 12 carbon atoms represented by D 5 include a linear or branched alkylene group having 1 to 12 carbon atoms. Specifically, a methylene group, an ethylene group, or a propylene group is preferable.
- the alkyl group having 1 to 12 carbon atoms represented by R 11 is specifically preferably a methyl group, an ethyl group, or a propyl group.
- examples of the monovalent organic group represented by Y 2 include a functional group containing a benzophenone skeleton ((C 6 H 5 ) 2 CO).
- a functional group containing a benzophenone skeleton in which the terminal benzene ring is unsubstituted or mono-substituted such as groups represented by the following formula (Ia) and the following formula (Ib), is preferable.
- * represents a bonding position, that is, a bonding position with the carbon atom of the carbonyl group in the above formula (I).
- Examples of the oxime type polymerization initiator represented by the above formula (I) include a compound represented by the following formula (S-1) and a compound represented by the following formula (S-2). .
- a polymerization initiator may be used individually by 1 type, and may use 2 or more types together.
- the content of the polymerization initiator (the total content when plural types are included) is not particularly limited, but is 0.01 to 20% by mass of the solid content of the polymerizable liquid crystal composition. Is more preferable, and 0.5 to 5% by mass is more preferable.
- the polymerizable liquid crystal composition preferably contains a solvent from the viewpoint of workability and the like for forming the optically anisotropic film.
- a solvent from the viewpoint of workability and the like for forming the optically anisotropic film.
- the solvent include ketones (for example, acetone, 2-butanone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, and cyclopentanone), ethers (for example, dioxane, and tetrahydrofuran), aliphatic carbonization, and the like.
- Hydrogens eg, hexane
- alicyclic hydrocarbons eg, cyclohexane
- aromatic hydrocarbons eg, toluene, xylene, and trimethylbenzene
- halogenated carbons eg, dichloromethane, dichloroethane
- Dichlorobenzene trichloromethane
- chlorotoluene esters
- esters for example, methyl acetate, ethyl acetate, and butyl acetate
- water for example, alcohols (for example, ethanol, isopropanol, butanol, and cyclohexanol), cellosolve
- cellosolve Kind
- methyl cellosolve, and ethyl cellosolve cellosolve acetates
- sulfoxides e.g., dimethyl sulfoxide, etc.
- amides e.g., dimethylformamide, and di
- the polymerizable liquid crystal composition preferably contains a leveling agent from the viewpoint of keeping the surface of the optical anisotropic film smooth and facilitating alignment control.
- a leveling agent is preferably a fluorine-based leveling agent or a silicon-based leveling agent because of its high leveling effect with respect to the amount added, and from the viewpoint of preventing crying (bloom, bleed), a fluorine-based leveling agent. It is more preferable that
- leveling agent examples include compounds described in paragraphs [0079] to [0102] of JP2007-069471, and general formula (I) described in JP2013-047204A. (Especially compounds described in paragraphs [0020] to [0032]), compounds represented by general formula (I) described in JP 2012-211306 (particularly [0022] to [0032] [0029] and the liquid crystal alignment accelerators represented by the general formula (I) described in JP-A No. 2002-129162 (particularly [0076] to [0078] and [0082] to [0084].
- the polymerizable liquid crystal composition may contain an alignment control agent as necessary.
- Various orientation states such as tilted orientation, hybrid orientation, and cholesteric orientation as well as homogeneous orientation can be formed by the orientation control agent, and the specific orientation state can be controlled more uniformly and precisely. be able to.
- a low molecular alignment control agent and a high molecular alignment control agent can be used.
- the low molecular orientation control agent include paragraphs [0009] to [0083] in JP-A No. 2002-20363, paragraphs [0111] to [0120] in JP-A No. 2006-106662, and JP-A 2012-2012.
- the description in paragraphs [0021] to [0029] of the 211306 gazette can be referred to, the contents of which are incorporated herein.
- the polymer orientation control agent for example, refer to paragraphs [0021] to [0057] of JP-A No. 2004-198511 and paragraphs [0121] to [0167] of JP-A No. 2006-106662. The contents of which are incorporated herein by reference.
- the content of the alignment control agent (the total content when there are a plurality of alignment control agents) is 0.01 to based on the total solid mass in the polymerizable liquid crystal composition.
- the content is preferably 10% by mass, and more preferably 0.05 to 5% by mass.
- the content of the alignment control agent is within this range, a uniform and highly transparent optically anisotropic film can be obtained without realizing precipitation, phase separation, alignment defects, and the like while realizing a desired alignment state.
- These alignment control agents may further have a polymerizable functional group, in particular, a polymerizable functional group that can be polymerized with the specific polymerizable liquid crystal compound constituting the polymerizable liquid crystal composition used in the present invention.
- the polymerizable liquid crystal composition may contain other components other than the components described above.
- other components include liquid crystal compounds other than the polymerizable liquid crystal compounds described above, surfactants, tilt angle control agents, alignment aids, plasticizers, and crosslinking agents.
- alignment aid Hisolv MTEM (manufactured by Toho Chemical Co., Ltd.), NK ester A-200 (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like are preferable.
- the method for forming an optically anisotropic film using the polymerizable liquid crystal composition having such components is not particularly limited.
- the polymerizable liquid crystal composition is applied onto the above-described photo-alignment film to form a coating film, and the obtained coating film is subjected to curing treatment (light irradiation treatment (for example, ultraviolet irradiation treatment) or heat treatment). It can be formed by applying.
- curing treatment light irradiation treatment (for example, ultraviolet irradiation treatment) or heat treatment.
- the polymerizable liquid crystal composition can be applied by a known method such as a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, and a die coating method.
- the polymerizable liquid crystal composition is applied by the die 35.
- the same heating process as described in the method for forming the photo-alignment film can be applied.
- the heating step is performed by a heating device 36.
- FIG. 3 shows a process by exposure with the light source 37, but a known light source can be used without limitation.
- a heating device can be provided instead of the light source 37, and the heating device 36 can also serve as this.
- the produced optical film can be wound as a wound body (roll) 39.
- a polarizing plate having various functions can be formed by bonding the optical film of the present invention and a polarizer.
- a polarizing plate is formed by bonding the optical anisotropic film transferred from the optical film and the polarizer. You can also.
- the polarizer is not particularly limited as long as it is a member having a function of converting light into specific linearly polarized light, and a conventionally known absorption polarizer and reflection polarizer can be used.
- an iodine polarizer, a dye polarizer using a dichroic dye, a polyene polarizer, and the like are used.
- Iodine polarizer and dye polarizer include coating polarizers and stretchable polarizers, both of which can be applied. Polarized light produced by adsorbing iodine or dichroic dye to polyvinyl alcohol and stretching. A child is preferred.
- a polarizer in which thin films having different birefringence are laminated a wire grid polarizer, a polarizer in which a cholesteric liquid crystal having a selective reflection region and a quarter wavelength plate are combined, and the like are used. It is done.
- a polyvinyl alcohol resin a polymer containing —CH 2 —CHOH— as a repeating unit, particularly at least one selected from the group consisting of polyvinyl alcohol and an ethylene-vinyl alcohol copolymer. It is preferable that it is a polarizer containing.
- the thickness of the polarizer is not particularly limited, but is preferably 1 to 60 ⁇ m, more preferably 1 to 30 ⁇ m, and still more preferably 2 to 20 ⁇ m.
- the polarizing plate described above has a polarizer supported or sandwiched by a polymer film.
- the polymer constituting such a polymer film include cellulose polymers; acrylic polymers such as acrylic polymers having acrylic ester polymers such as polymethyl methacrylate and lactone ring-containing polymers; thermoplastic norbornene.
- Polycarbonate polymer such as polyethylene terephthalate and polyethylene naphthalate; Styrene polymer such as polystyrene and acrylonitrile / styrene copolymer (AS resin); Polyethylene, polypropylene, and ethylene / propylene copolymer
- Polyolefin polymers such as; vinyl chloride polymers; amide polymers such as nylon and aromatic polyamide; imide polymers; sulfone polymers; Polymers; polyether ether ketone polymers; polyphenylene sulfide polymers; vinylidene chloride polymers; vinyl alcohol polymers; vinyl butyral polymers; arylate polymers; polyoxymethylene polymers; epoxy polymers; The polymer which was made is mentioned.
- a cellulose polymer represented by triacetyl cellulose hereinafter also referred to as “cellulose acylate”.
- an acrylic polymer from the viewpoint of processability and optical performance.
- a film using a cellulosic polymer or an acrylic polymer the same film as that described above can be used.
- a polarizing plate what bonded together the polarizer to the polymer support body mentioned above may be used.
- the thickness of the polymer film is not particularly limited, but is preferably 40 ⁇ m or less because the thickness of the polarizing plate can be reduced. Although a minimum in particular is not restrict
- FIG. 2A is a conceptual diagram of a polarizing plate 20 having a linear polarizer 22, a polymer support 16, a photo-alignment film 14, and an optical anisotropic film 12 in this order.
- An adhesive layer (not shown) may optionally be provided between the linear polarizer 22 and the polymer support 16, and an arbitrary polymer film may be provided on the opposite side of the linear polarizer 22 from the polymer support 16. (Not shown) may be provided.
- FIG. 2B shows a conceptual diagram of a polarizing plate having the linear polarizer 22, the optical anisotropic film 12 transferred from the optical film of the present invention, and the positive C plate 18 in this order.
- An adhesive layer (not shown) such as a pressure-sensitive adhesive layer and an optional polymer film (not shown) may be provided between each layer.
- the absorption axis of the linear polarizer to be combined and the optical film of the present invention or the optical of the present invention A circularly polarizing plate can be obtained by crossing the slow axis of the optically anisotropic film transferred from the film at 45 °.
- the circularly polarizing plate is used as an external light antireflection layer of an image display device to be described later, for the purpose of adjusting the color of the reflected light, the absorption axis of the combined linear polarizer and the optical element of the present invention are used.
- the crossing angle with the slow axis of the optical anisotropic film constituting the film or the optical film of the present invention is preferably adjusted in the range of 45 ° ⁇ 8 °.
- the polarizing plate described above may further contain other layers in addition to the optical film of the present invention or the optical anisotropic film transferred from the optical film of the present invention and the optional polymer film described above.
- Specific examples of the other layers include a decorative layer, an adhesive layer, a light diffusion layer, a gas barrier layer, a colored layer, a conductive layer (touch panel), and an antistatic layer.
- a positive C plate and other retardation films may be further combined.
- the optical film of the present invention or the polarizing plate described above can be applied to an image display device.
- the display element used in the image display device of the present invention is not particularly limited, and examples thereof include a liquid crystal cell, an organic electroluminescence (hereinafter abbreviated as “EL”) display panel, a plasma display panel, and a micro LED display panel.
- EL organic electroluminescence
- the optical film of the present invention or the above-described polarizing plate can be used for the purpose of optical compensation for improving display image quality, and is intended to suppress deterioration in display image quality due to reflection of external light by the display element. Can also be used.
- liquid crystal display device As an example of a liquid crystal display device to which the optical film of the present invention described above or the optical anisotropic film transferred from the optical film of the present invention is applied, it was transferred from the optical film of the present invention described above or the optical film of the present invention.
- a liquid crystal display device having a polarizing plate to which an optically anisotropic film is bonded and a liquid crystal cell can be given.
- the polarizing plate described above is preferably used as the polarizing plate on the front side. If necessary, the display performance in the perspective direction can be improved by further combining a positive C plate or the like.
- the liquid crystal cell which comprises a liquid crystal display device is explained in full detail.
- the liquid crystal cell used in the liquid crystal display device is preferably in a VA (Virtual Alignment Bend) mode, an OCB (Optical Compensated Bend) mode, an IPS (In-Placed Switching) mode, or a TN (Twisted Nematic). It is not limited to.
- a TN mode liquid crystal cell rod-like liquid crystal molecules are substantially horizontally aligned when no voltage is applied, and are twisted and aligned at 60 to 120 °.
- a TN mode liquid crystal cell is most widely used as a color TFT (thin-film-transistor liquid-crystal display) liquid crystal display device, and is described in many documents.
- VA mode liquid crystal cell In a VA mode liquid crystal cell, rod-like liquid crystal molecules are aligned substantially vertically when no voltage is applied.
- the VA mode liquid crystal cell includes: (1) a narrowly defined VA mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. Hei 2-). (2) In addition to (2) Liquid crystal cell (SID97, Digest of tech.Papers (Proceedings) 28 (1997) 845 in which the VA mode is converted into a multi-domain (MVA mode) for viewing angle expansion.
- a liquid crystal cell in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied and twisted multi-domain alignment is applied when a voltage is applied (Preliminary collections 58-59 of the Japan Liquid Crystal Society) (1998)) and (4) SURVIVAL mode liquid crystal cells (announced at LCD International 98).
- any of PVA (Patterned Vertical Alignment) type, optical alignment type (Optical Alignment), and PSA (Polymer-Stained Alignment) may be used. Details of these modes are described in JP-A-2006-215326 and JP-T 2008-538819.
- JP-A-10-54982, JP-A-11-202323, and JP-A-9-292522 are methods for reducing leakage light during black display in an oblique direction and improving the viewing angle using an optical compensation sheet. No. 11-133408, No. 11-305217, and No. 10-307291.
- Organic EL display device In the organic EL display device, by using a circularly polarizing plate to which the optical film of the present invention or an optical anisotropic film transferred from the optical film of the present invention is bonded, external light is reflected on the electrodes of the organic EL panel. Thus, the phenomenon of lowering the display contrast can be suppressed and high-quality display can be realized.
- the organic EL panel known configurations can be widely used, and further, a touch panel can be provided.
- a display device that exhibits an excellent reflection color in the perspective direction can be formed.
- a flask equipped with a condenser, a thermometer, and a stirrer was charged with 5 parts by mass of 2-butanone as a solvent, and refluxed by heating in a water bath while flowing 5 mL / min of nitrogen into the flask.
- 5 parts by mass of monomer m-1, 5 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate (Cyclomer M100, manufactured by Daicel), and 2,2′-azobis (isobutyronitrile) as a polymerization initiator are used.
- a solution prepared by mixing 1 part by mass and 5 parts by mass of 2-butanone as a solvent was added dropwise over 3 hours, and further stirred for 3 hours while maintaining the reflux state.
- the mixture was allowed to cool to room temperature and diluted by adding 30 parts by mass of 2-butanone to obtain a polymer solution of about 20% by mass.
- the obtained polymer solution is poured into a large excess of methanol to precipitate the polymer, and the collected precipitate is filtered off, washed with a large amount of methanol, and then blown and dried at 50 ° C. for 12 hours, A polymer Ap2 having a crosslinkable group and a photoalignable group was obtained.
- composition for photo-alignment film A composition for a photo-alignment film having the following composition (P-1, P-2, P-3) was prepared. In each of the obtained compositions, each polymer and other components were sufficiently dissolved in the solvent according to the amount added.
- composition for photo-alignment film (P-1) ⁇ Compound CIN-1 1.00 parts by mass A solution of the polymer Ap1 (solid content 35% by mass) 2.90 parts by mass A solution of the polymer Ap3 (solid content 25% by mass) 4.00 parts by mass p-toluenesulfonic acid 1 Hydrate 0.10 parts by mass Propylene glycol monomethyl ether 43.7 parts by mass ⁇
- composition for photo-alignment film (P-2) Polymer Ap1 4.60 parts by mass The following compound B2 0.80 parts by mass The following crosslinking agent C-1 3.00 parts by mass Compound D1 0.80 parts by mass Butyl acetate 120 parts by mass ⁇ ⁇
- Crosslinking agent C-1 Polyfunctional epoxy compound (Epolide GT401, manufactured by Daicel Corporation)
- Compound D1 Thermal acid generator (Sun-Aid SI-60, manufactured by Sanshin Chemical Industry Co., Ltd.)
- composition for optically anisotropic film Coating solutions for optically anisotropic films having the following compositions (A-1 to A-3) were prepared.
- Coating liquid for optically anisotropic film (A-1) ⁇
- the groups adjacent to the acryloyloxy groups of the following polymerizable liquid crystal compounds L-1 and L-2 represent propylene groups (groups in which a methyl group is substituted with an ethylene group), and the following polymerizable liquid crystal compounds L-1 and L-2 -2 represents a mixture
- cellulose acylate film 1 (Preparation of cellulose acylate film 1)
- the core layer cellulose acylate dope and the outer layer cellulose acylate dope are filtered through a filter paper having an average pore size of 34 ⁇ m and a sintered metal filter having an average pore size of 10 ⁇ m, and then the core layer cellulose acylate dope and the outer layer cellulose acylate dope on both sides thereof 3 layers were simultaneously cast on a drum at 20 ° C. from a casting port (band casting machine).
- the film was peeled off in a state where the solvent content of the film on the drum was approximately 20% by mass, both ends in the width direction of the film were fixed with tenter clips, and dried while being stretched in the transverse direction at a stretch ratio of 1.1.
- FIG. 1 The core layer of the cellulose acylate film 1 had a thickness of 36 ⁇ m, and the outer layers disposed on both sides of the core layer had a thickness of 2 ⁇ m.
- the resulting cellulose acylate film 1 had an in-plane retardation at a wavelength of 550 nm of 0 nm and a thickness direction retardation of 1 nm.
- Example 1 [Production of optical film] While the produced long cellulose acylate film 1 was fed out and conveyed, the previously prepared composition P-1 for photo-alignment film was continuously applied to one surface of the cellulose acylate film 1. After coating, the film was heated for 150 seconds in an atmosphere of 115 ° C. while being conveyed to form a photoisomerizable composition layer having a thickness of 0.2 ⁇ m. The obtained photoisomerizable composition layer was irradiated with polarized ultraviolet rays (10 mJ / cm 2 , using an ultrahigh pressure mercury lamp) to form a photoalignment film PA-1.
- polarized ultraviolet rays (10 mJ / cm 2 , using an ultrahigh pressure mercury lamp
- the previously prepared coating liquid A-1 for optically anisotropic film was continuously applied on the photo-alignment film to form a composition layer (coating film).
- the formed composition layer was heated to 110 ° C. and then cooled to 60 ° C. to stabilize the orientation. Thereafter, the orientation is fixed by ultraviolet irradiation (500 mJ / cm 2 , using an ultra-high pressure mercury lamp) in a nitrogen atmosphere (oxygen concentration 100 ppm) while maintaining the temperature at 60 ° C. to form an optically anisotropic film having a thickness of 2.3 ⁇ m.
- the optical film 1 of Example 1 was produced.
- the in-plane retardation of the obtained optical laminate at a wavelength of 550 nm was 140 nm.
- Examples 2 to 4, Comparative Example 1 The optical alignment film composition and / or the thickness of the optical alignment film were changed as shown in Table 2, and optical films 2 to 4 of Examples 2 to 4 and optical film 11 of Comparative Example 1 were produced.
- the thickness of the photo-alignment film was changed by changing the coating amount per area of the used photo-alignment film composition. Further, by adjusting the coating amount per area of the composition for forming an optically anisotropic film, the in-plane retardation of the optically anisotropic film of each film at a wavelength of 550 nm was all set to 140 nm.
- Example 5 An optical film 5 of Example 5 was produced in the same manner as in Example 2 except that the coating liquid A-3 for optical anisotropic film was used as the composition for forming an optically anisotropic film.
- the in-plane retardation of the optically anisotropic film at a wavelength of 550 nm was 140 nm.
- Example 6 An optical film 6 of Example 6 was produced in the same manner as in Example 2 except that the coating liquid A-2 for optical anisotropic film was used as the composition for forming an optical anisotropic film.
- the in-plane retardation of the optically anisotropic film at a wavelength of 550 nm was 140 nm.
- Example 2 In Example 1, it replaced with the cellulose acylate film 1 and carried out similarly to Example 1 except having used the polyethylene terephthalate film (FD100, the Fuji Film Co., Ltd. make. In the table
- the optical film 12 of the comparative example 2 was produced.
- Comparative Example 3 In Example 1, the optical film 13 of Comparative Example 3 was produced in the same manner as in Example 1 except that the heating time of the photoisomerized composition layer was set to 100 seconds.
- a calibration curve is prepared by adding 0.1% by mass and 1.0% by mass of the above-described polyester compound B to the composition P-1 for photo-alignment film, based on the total solid content of the composition P-1.
- Compositions P-1 (0.1) and P-1 (1.0) were prepared. After spin-coating each of the optical alignment film composition P-1 and the calibration curve preparation compositions P-1 (0.1) and P-1 (1.0) on a cleaned glass plate at 120 ° C. It heated for 1 minute and produced each 0.3-micrometer-thick model film
- Example 1 to 6 the composition for forming a photo-alignment film and the conditions for forming the photo-alignment film were suitable, so that the adhesion was excellent and the alignment state of the liquid crystal compound was good. Further, from the comparison of Example 2, Example 5, and Example 6, it is obtained when the specific polymerizable liquid crystal compound corresponds to the compounds represented by the above formulas (1-1) to (1-14). In the optical film, the alignment state of the liquid crystal compound was better.
- Comparative Examples 1 to 3 the action of the polymer support and the composition for forming a photo-alignment film, and the conditions for forming the photo-alignment film were not properly designed. And / or the uniformity of the alignment state of the liquid crystal compound. More specifically, in Comparative Example 1, the amount of the solvent that acts on the polymer support because the coating film (photoisomerization composition layer) of the composition for forming a photo-alignment film formed on the polymer support is thick. It is speculated that this is because excessive extraction of the component derived from the additive of the polymer support into the photoisomerized composition layer has occurred.
- the obtained optical film is considered to be inferior in the uniformity of the alignment state of the liquid crystal compound in the photoisomerized composition layer, although it is excellent in the adhesion between the polymer support and the photo-alignment film.
- the solvent in the composition for forming a photo-alignment film does not have the effect of swelling the surface of the polymer support or is extremely weak. Therefore, the adhesion between the polymer support of the obtained optical film and the photo-alignment film Did not meet the desired requirements.
- the heating time of the coating film (photoisomerization composition layer) of the composition for forming a photo-alignment film was shortened, so that the crosslinking density of the photo-alignment film was small.
- a pressure-sensitive adhesive layer is provided on the optically anisotropic film of the optical film 1 of Example 1 and bonded to the polarizing plate, and then the cellulose acylate film 1 is peeled off to obtain a polarizing plate and an optically anisotropic film.
- stacked with the adhesive was produced. Further, the positive C plate film C-1 prepared above was transferred to the optically anisotropic film side via an adhesive, and the forming temporary support was removed to obtain the circularly polarizing plate 1.
- the circularly polarizing plates 2, 4, 5 are the same as the circularly polarizing plate 1 except that the optical films 2, 4, 5, 6 of Examples 2, 4, 5, 6 are used instead of the optical film of Example 1. , 6 were prepared.
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Abstract
Description
光学フィルムとしては延伸複屈折フィルムが使用されていたが、光学フィルムの薄型化及び高機能化の要請から、延伸複屈折フィルムに代えて、重合性液晶化合物を含む重合性液晶組成物から形成される光学異方性膜を有する光学フィルムが提案されている。
また、本発明は、上記光学フィルム用いた偏光板、並びに、上記光学フィルム又は上記偏光板を用いた画像表示装置を提供することを課題とする。
すなわち、以下の構成により上記課題を解決することができることを見出した。
前記光学異方性膜は、逆波長分散性の重合性液晶化合物を含む重合性液晶組成物から形成されており、
上記光配向膜において前記光学異方性膜との境界領域に含まれる、上記ポリマー支持体の添加剤に由来する成分の量が光配向膜全質量に対して0.10~0.50質量%である、光学フィルム。
[2] 上記逆波長分散性の重合性液晶化合物が、後述する一般式(1)で表される化合物である、[1]に記載の光学フィルム。
[3] 上記光配向膜が、
架橋性基を含む重合体と、シンナメート基を有する低分子化合物と、を含む光配向膜形成用組成物から形成されるか、又は、
架橋性基及び光配向性基を含む重合体を含む光配向膜形成用組成物から形成される、[1]又は[2]に記載の光学フィルム。
[4] 上記ポリマー支持体が、添加剤を含むセルロースアシレートフィルムである、[1]~[3]のいずれかに記載の光学フィルム。
[5] 上記添加剤が、ポリエステル化合物又は糖エステル化合物である、[4]に記載の光学フィルム。
[6] 上記ポリマー支持体のRe(550)が0~10nmであり、Rth(550)が-10~15nmである、[4]又は[5]に記載の光学フィルム。
[7] 上記光学異方性膜が、上記光配向膜に対して剥離可能に設けられている、[1]~[6]のいずれかに記載の光学フィルム。
[8] [1]~[7]のいずれかに記載の光学フィルムと、偏光子とを有する、偏光板。
[9][1]~[7]のいずれかに記載の光学フィルム、又は[8]に記載の偏光板を有する、画像表示装置。
また、本発明によれば、上記光学フィルム用いた偏光板、並びに、上記光学フィルム又は上記偏光板を用いた画像表示装置を提供できる。
以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に制限されるものではない。
なお、本明細書において、「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
また、本明細書において「(メタ)アクリル」との記載は、「アクリル及びメタクリルのいずれか一方又は双方」を意図する。また、「(メタ)アクリロイル基」との記載は、「アクリロイル及びメタクリロイルのいずれか一方又は双方」を意図する。
具体的には、AxoScan OPMF-1にて、平均屈折率((nx+ny+nz)/3)と膜厚(d(μm))を入力することにより、
遅相軸方向(°)
Re(λ)=R0(λ)
Rth(λ)=((nx+ny)/2-nz)×d
が算出される。
なお、R0(λ)は、AxoScan OPMF-1で算出される数値として表示されるものであるが、Re(λ)を意味している。
本発明の光学フィルムは、添加剤を含むポリマー支持体、光配向膜、及び光学異方性膜をこの順に積層してなる光学フィルムである。ポリマー支持体と光配向膜とは密着しており、光学異方性膜中の液晶性化合物は、光配向膜の配向規制力により配向状態が制御されている。また、光学異方性膜は、光配向膜と密着して剥離しないように設けられていてもよいし、光配向膜との間で剥離できるように設けられていてもよい。なお、光学異方性膜が光配向膜に対して剥離できるように設けられている場合、偏光板等の他の被転写体に上記光学異方性膜を転写し得る。
ポリマー支持体は、少なくともポリマーと添加剤とを含む。ロールトゥロールプロセスに適用できる点で、長尺状のポリマーフィルムであることが好ましい。バラツキの少ない一定の性能を示す領域を長く設け、搬送のために巻回体にする観点からは、長尺状のポリマーフィルムの長さは500~20000mが好ましく、1000~15000mがより好ましく、2000~10000mがさらに好ましい。
また、ポリマー支持体の光学異方性については任意に設定することができるが、好ましい一例として、波長550nmにおける面内レターデーション(Re(550))が0~10nmであり、波長550nmにおける厚み方向のレターデーション(Rth(550))が-10~15nmである態様が挙げられる。
上記ポリマー支持体を構成するポリマーとしては、具体的には、セルロース系ポリマー;ポリメチルメタクリレート、及びラクトン環含有重合体等のアクリル酸エステル重合体を有するアクリル系ポリマー等のアクリル系ポリマー;熱可塑性ノルボルネン系ポリマー;ポリカーボネート系ポリマー;ポリエチレンテレフタレート、及びポリエチレンナフタレート等のポリエステル系ポリマー;ポリスチレン、及びアクリロニトリル・スチレン共重合体(AS樹脂)等のスチレン系ポリマー;ポリエチレン、ポリプロピレン、及びエチレン・プロピレン共重合体等のポリオレフィン系ポリマー;ビニルアルコール系ポリマー;ビニルブチラール系ポリマー;アリレート系ポリマー;ポリオキシメチレン系ポリマー;エポキシ系ポリマー;並びにこれらのポリマーを混合したポリマー等が挙げられる。
上記ポリマー支持体は、添加剤を含む。
ここでいう添加剤とは、ポリマー支持体を構成する上述のポリマーの改質、及び/又はフィルムの高機能化のために加えられる化合物を指し、例えば、可塑剤、UV(ultraviolet)吸収剤、光学異方性発現剤、光学異方性低減剤、疎水化剤、及び耐久性改良剤等が該当する。
上記ポリマー支持体の好ましい一態様として、セルロースアシレートフィルムを用いることができる。セルロースアシレートはセルロースの水酸基がアシル化されたもので、その置換基はアシル基の炭素原子数が2のアセチル基から炭素原子数が22のものまでいずれも用いることができる。
好ましいアシル基としては、アセチル基、プロピオニル基、ブタノイル基、ベンゾイル基、ナフチルカルボニル基、及びシンナモイル基等が挙げられる。これらの中でも、アセチル基、プロピオニル基、ブタノイル基、ベンゾイル基、ナフチルカルボニル基、又はシンナモイル基が好ましく、アセチル基、プロピオニル基、又はブタノイル基がより好ましい。特に、合成の容易さ、コスト、及び置換基分布の制御のしやすさ等の観点から、アセチル基、又はプロピオニル基が更に好ましく、アセチル基が特に好ましい。また、2種以上のアシル基が置換する場合、アセチル基とプロピオニル基の組み合わせが好ましい。
セルロースアシレートにおいて、セルロースの水酸基に置換する酢酸及び/又は炭素原子数3~22の脂肪酸の置換度(アシル置換度)の測定方法としては、ASTMのD-817-91に準じた方法、及びNMR(核磁気共鳴)法が挙げられる。
化合物(D)としては、ラクトース、スクロース、ニストース、1F-フラクトシルニストース、スタキオース、マルチトール、ラクチトール、ラクチュロース、セロビオース、マルトース、セロトリオース、マルトトリオース、ラフィノース、及びケストースが挙げられる。また、ゲンチオビオース、ゲンチオトリオース、ゲンチオテトラオース、キシロトリオース、及びガラクトシルスクロース等も挙げられる。
これらの化合物(D)の中で、特にフラノース構造とピラノース構造との双方を有する化合物が好ましく、スクロース、ケストース、ニストース、1F-フラクトシルニストース、又はスタキオースがより好ましく、スクロースが更に好ましい。
上記脂肪族モノカルボン酸としては、酢酸、プロピオン酸、酪酸、イソ酪酸、吉草酸、カプロン酸、エナント酸、カプリル酸、ペラルゴン酸、カプリン酸、2-エチル-ヘキサンカルボン酸、ウンデシル酸、ラウリン酸、トリデシル酸、ミリスチン酸、ペンタデシル酸、パルミチン酸、ヘプタデシル酸、ステアリン酸、ノナデカン酸、アラキン酸、ベヘン酸、リグノセリン酸、セロチン酸、ヘプタコサン酸、モンタン酸、メリシン酸、及びラクセル酸等の飽和脂肪酸;ウンデシレン酸、オレイン酸、ソルビン酸、リノール酸、リノレン酸、アラキドン酸、及びオクテン酸等の不飽和脂肪酸;等が挙げられ、それらの中でも酢酸、プロピオン酸、又はイソ酪酸が好ましい。すなわち、上記糖エステル化合物中の上記置換基が、アセチル基、プロピオニル基、又はイソブチリル基であることが好ましい。
上記態様をより具体的に説明すると、前述のOH基の全て若しくは一部は酢酸とイソ酪酸でエステル化することが好ましい。言い換えると、上記糖エステル化合物中の上記置換基がアセチル基とイソブチリル基であることが好ましい。置換基がアセチル基とイソブチリル基のみからなる場合、その割合はアセチル基/イソブチリル基=1/7~4/4であることが好ましく、1/7~3/5であることがより好ましく、2/6であることが更に好ましい。
セルロースアレートフィルムが上記一般式(4)で表される化合物を含む場合、上記一般式(4)で表される化合物の含有量は、セルロースアシレートポリマーに対して1~20質量%であることが好ましい。
上記ポリマー支持体の好ましい他の一態様として、アクリル樹脂フィルムを用いることができる。アクリル樹脂は、例えばポリメチルメタクリレート(PMMA)の他、耐熱性に優れる点で、主鎖に環状構造を有する(メタ)アクリル系樹脂を用いることができる。主鎖に環状構造を有する(メタ)アクリル系樹脂としては、ラクトン環構造を有する(メタ)アクリル系樹脂、グルタルイミド環構造を有する(メタ)アクリル系樹脂、無水グルタル酸環構造を有する(メタ)アクリル系樹脂、無水マレイン酸環構造を有する(メタ)アクリル系樹脂、及び、マレイミド環構造を有する(メタ)アクリル系樹脂等が挙げられる。
グルタルイミド環構造を有する(メタ)アクリル系樹脂としては、国際公開第05/054311号、国際公開第05/108438号、特開2010-261025号公報、特開2010-270162号公報、特開2010-284840号公報、特開2011-88440号公報、特開2011-138119号公報、及び特開2011-245624号公報等に記載の合成法、並びにそれによって製造されたものを用いることができる。
本発明の光学フィルムを構成する光配向膜は、光配向膜形成用組成物を用いてポリマー支持体上に形成されており、ポリマー支持体とは逆側の面に光学異方性膜が配置される。
光配向膜において光学異方性膜側の境界領域に含まれる、前述のポリマー支持体の添加剤に由来する成分の量は、光配向膜全質量に対して0.10~0.50質量%である。
まず、光配向膜中の光学異方性膜との境界領域を二次イオン質量分析法によって分析する。次いで、ポリマー支持体の添加剤(以下「添加剤成分」ともいう。)に由来する二次イオンピーク値を総検出イオン量で除すことで、上記添加剤成分の規格化二次イオン量を求める。そして、別途求めた検量線によって、その他の光配向膜成分に対する上記添加剤成分の質量比を算出する。この算出された数値から、光配向膜中の光学異方性膜との境界領域に含まれる上記添加剤成分に由来する成分の光配向膜全質量に対する量(質量%)が求められる。
本発明の光学フィルムにおいて、光学異方性膜が光配向膜に対して剥離可能に設けられている場合においては、光学異方性膜を剥離除去した後に表出する光配向膜の表面を二次イオン質量分析法に供することで、光配向膜の光学異方性膜側境界領域に存在する上記添加剤成分由来の規格化二次イオン量を求めることができる。本発明の光学フィルムが光配向膜と光学異方性膜との間で剥離できない場合においては、光学フィルムの断面(必要により斜め切削による切削面でもよい)に対し、図1Bに示す要領で領域を特定して、断面若しくは切削面の二次イオン質量分析プロファイルを測定することで、光配向膜の光学異方性膜側境界領域に存在する上記添加剤成分由来の規格化二次イオン量を求めることができる。
ここでいう光配向膜の光学異方性膜側の境界領域とは、光学的に観察される光配向膜と光学異方性膜との境界線から約50nmの深さまでの領域を指すものとする。図1Bを参照して具体的に説明すると、光配向膜の光学異方性膜側の境界領域15とは、光学的に観察される光配向膜と光学異方性膜との境界線13から約50nmの深さまでの領域を指す。
この時、光配向膜中にもともと含まれるポリマー支持体由来の成分の含有量が十分低い、又は重合性液晶組成物の塗膜へポリマー支持体由来の成分が速やかに拡散する等の理由で、光配向膜における重合性液晶組成物の塗膜側の境界領域でのポリマー支持体由来の成分濃度が十分低下すれば配向に影響はないが、光配向膜における重合性液晶組成物の塗膜側の境界領域でのポリマー支持体由来の成分濃度が高いまま工程を進めると液晶性化合物の配向を形成する段階で配向状態に悪影響を及ぼすとの仮説の下、発明者らはポリマー支持体由来の成分の膜中分布とその制御因子を詳細に検討した結果、本発明に至ったものである。
本発明に用いる光配向膜形成用組成物は、公知のものを利用することができる。ポリマー支持体との密着性の観点、並びに、重合性液晶組成物との濡れ性の観点から選ぶことが好ましい。また、配向規制力及び基材との密着性に優れる観点で、架橋可能であることが好ましい。
架橋性基を含む重合体と、光配向性基を有する低分子化合物とを含む光配向膜形成用組成物としては、例えば、架橋性基を含む繰り返し単位を含む重合体と、シンナメート基を有する低分子化合物とを含む光配向膜形成用組成物が挙げられる。
また、架橋性基及び光配向性基を含む重合体を含む光配向膜形成用組成物の一例としては、架橋性基を含む繰り返し単位と、シンナメート基を含む繰り返し単位とを含む重合体を含む光配向膜形成用組成物が挙げられる。上記態様の光配向膜形成用組成物においては、光配向性基を有する低分子化合物を含んでいてもよいし、含んでいなくてもよい。
光配向膜形成用組成物としては、架橋性基を含む重合体Apと、シンナメート基を有する低分子化合物Bとを含む光配向膜形成用組成物であるか、又は架橋性基及び光配向性基を含む重合体Ap’を含む光配向膜形成用組成物が好ましい。
以下において、架橋性基を含む重合体Ap(以下、単に「重合体Ap」ともいう。)について説明する。なお、上記架橋性基を含む重合体Apは、さらに光配向性基を含んでいることが好ましい。つまり、架橋性基を含む重合体Apは、架橋性基及び光配向性基を含む重合体Ap’であることが好ましい。
以下において、重合体Ap及びシンナメート基を有する低分子化合物B、並びにその他の添加成分について各々説明する。
重合体Apとしては、架橋性基を含みさえすれば特に制限されず、従来公知の重合体を用いることができる。重合体Apとしては、具体的には、架橋性基を含む繰り返し単位(以下「架橋性基を含む繰り返し単位a1」ともいう)を含む重合体が挙げられる。
重合体Apの主骨格としては、例えば、ポリアミック酸、ポリアミック酸エステル、ポリイミド、ポリオルガノシロキサン、(メタ)アクリル系重合体、シクロオレフィン系重合体、ポリエステル、ポリアミド、ポリアセタール誘導体、ポリスチレン誘導体、及びポリ(スチレン-フェニルマレイミド)誘導体等により形成される骨格が挙げられる。特に樹脂フィルム上に配向層を設けるにあたっては、溶媒溶解性と膜の取り扱い性に優れる点から(メタ)アクリル系重合体、及びポリオルガノシロキサンよりなる群から選ばれる少なくとも1種が好ましい。
ここで、質量平均分子量は、ゲルパーミエーションクロマトグラフィ(GPC)測定によるポリスチレン(PS)換算値として定義される。本発明におけるGPCによる測定は、具体的には、HLC-8220GPC(東ソー(株)製)を用い、カラムとしてTSKgel Super HZM-H、HZ4000、HZ2000を用いて測定される。
また、後述するように、重合体Apは、さらに架橋性基を含む繰り返し単位a1及びシンナメートを含む繰り返し単位a2以外のその他の繰り返し単位を含んでいてもよい。
以下において、架橋性基を含む繰り返し単位a1、シンナメートを含む繰り返し単位a2、及びその他の繰り返し単位について各々説明する。
架橋性基を含む繰り返し単位a1としては特に制限されないが、例えば(メタ)アクリル系重合体及びポリオルガノシロキサンを例にとると、下記式(A1)又は(A2)で表される繰り返し単位が好ましい。
式(A2)中、R2の炭素数1~6のアルキル基としては、具体的には、メチル基、エチル基、n-プロピル基、イソプロピル基、及びn-ブチル基等が挙げられ、なかでも、メチル基、又はエチル基が好ましい。また、R2の炭素数1~6のアルコキシ基としては、具体的には、メトキシ基、エトキシ基、n-プロピルオキシ基、イソプロピルオキシ基、及びn-ブトキシ基等が挙げられ、なかでも、メトキシ基、又はエトキシ基が好ましい。
以下の具体例において、R1及びR2は、それぞれ、上述した式(A1)及び式(A2)中のR1及びR2と同義である。
シンナメート基を含む繰り返し単位a2としては、上述した一般式(A1)又は(A2)で表される繰り返し単位において、Yが架橋性基に代えて各種のシンナメート基を表すものが挙げられる。
シンナメート基の具体例としては、特開2015-026050号公報の[0016]段落に記載された以下に示す基が挙げられる。下記構造において、*は、Lとの結合位置を示す。なお、一般式(A1)又は(A2)で表される繰り返し単位において、Yが、架橋性基に代えて以下に示すシンナメート基を表す場合、一般式(A1)又は(A2)中のLは、単結合を表すことが好ましい。
上記重合体Apは、上述した繰り返し単位a1及び繰り返し単位a2以外の他の繰り返し単位を有していてもよい。共重合体が他の繰り返し単位を含むことで、例えば、基材密着性、溶媒溶解性、及び耐熱性等が向上し得る。
上記重合体Apが含み得るその他の繰り返し単位としては、基材密着性及び溶媒溶解性の観点からは、重合体Apの極性を調整する官能基を含む繰り返し単位が好ましい。具体的には、親水性を付与する観点では、水酸基、カルボン酸基、又はイオン性基を含む繰り返し単位が好ましく、親油性を付与する観点では、高級アルキル基又は芳香族基を含む繰り返し単位が好ましい。また、基材密着性と溶媒溶解性の両立の観点では、5員環以上の複素環、環状ケトン、又は芳香環を含む繰り返し単位が好ましい。また、耐熱性を高める観点からは、剛直な構造を含む繰り返し単位が好ましい。
さらに、後述する光学異方性膜と密着させたい場合は、重合性液晶組成物に含まれる成分と反応可能な官能基を含む繰り返し単位が好ましい。
シンナメート基を有する低分子化合物B(以下「低分子化合物B」ともいう。)としては、シンナメート基を有し、重合体Apよりも分子量が小さい化合物であることが好ましい。特に、重合体Apがシンナメート基を含む場合においては、光配向膜形成用組成物が低分子化合物Bを含むことで、作製される光配向膜の配向性がより良好となる。
なお、重合体Apがシンナメート基を含まない場合においては、低分子化合物Bとして、シンナメート基を有し、重合体Apよりも分子量が小さい化合物であって、且つ重合体Apが有する架橋性基と結合可能な化合物を使用して、その反応生成物を光配向膜として用いることが好ましい。
また、R1の1価の有機基としては、例えば、炭素数1~20の直鎖状、分岐鎖状、又は環状のアルキル基、炭素数1~20のアルコキシ基、及び、置換基を有していていてもよい炭素数6~20のアリール基等が挙げられ、なかでも、炭素数1~20のアルコキシ基が好ましく、炭素数1~6のアルコキシ基がより好ましく、メトキシ基、又はエトキシ基が更に好ましい。
また、R2の1価の有機基としては、例えば、炭素数1~20の直鎖状、分岐鎖状、又は環状のアルキル基、及び置換基を有していていてもよい炭素数6~20のアリール基等が挙げられ、なかでも、炭素数1~20の直鎖状又は分岐鎖状のアルキル基が好ましく、炭素数1~10の分岐鎖状のアルキル基がより好ましい。
また、aは、1であるのが好ましく、R1がパラ位に有しているのが好ましい。
また、上述したアリール基が有していてもよい置換基としては、例えば、アルコキシ基、ヒドロキシ基、カルボキシ基、及びアミノ基等が挙げられる。
また、光配向膜形成用組成物が後述する有機溶媒を含有する場合、上記低分子化合物Bの含有量は、溶媒100質量部に対して0.01~50質量部が好ましく、0.1~10質量部がより好ましい。
光配向膜形成用組成物は、ポリマー支持体との密着性が向上する、及び配向規制力が向上するといった理由から、架橋性基を含む繰り返し単位a1を含む重合体Apとは別に、重合体Apと反応可能な架橋性基を有する架橋剤Cを含んでいることが好ましい。架橋性基量を適切に調整することで、ポリマー支持体の添加剤由来の成分の抽出及び塗膜内での拡散が制御できる。
上記架橋剤Cの分子量は、1000以下が好ましく、100~500がより好ましい。
上記架橋剤Cとしては、例えば、分子内に2個以上のエポキシ基又はオキセタニル基を有する化合物、ブロックイソシアネート化合物(保護されたイソシアナト基を有する化合物)、及びアルコキシメチル基含有化合物等が挙げられる。
これらのうち、以下に具体例を示す、分子内に2個以上のエポキシ基又はオキセタニル基を有する化合物、又はブロックイソシアネート化合物が好ましい。
分子内に2個以上のエポキシ基を有する化合物の具体例としては、脂肪族エポキシ化合物等が挙げられる。
これらは市販品として入手できる。例えば、デナコールEX-611、EX-612、EX-614、EX-614B、EX-622、EX-512、EX-521、EX-411、EX-421、EX-313、EX-314、EX-321、EX-211、EX-212、EX-810、EX-811、EX-850、EX-851、EX-821、EX-830、EX-832、EX-841、EX-911、EX-941、EX-920、EX-931、EX-212L、EX-214L、EX-216L、EX-321L、EX-850L、DLC-201、DLC-203、DLC-204、DLC-205、DLC-206、DLC-301、及びDLC-402(以上ナガセケムテックス(株)製)、セロキサイド2021P、2081、3000、及びEHPE3150、エポリードGT401、並びに、セルビナースB0134、及びB0177((株)ダイセル製)等が挙げられる。
分子内に2個以上のエポキシ基を有する化合は、1種単独又は2種以上を組み合わせて使用することができる。
分子内に2個以上のオキセタニル基を有する化合物の具体例としては、アロンオキセタンOXT-121、OXT-221、OX-SQ、及びPNOX(以上、東亞合成(株)製)が挙げられる。
ブロックイソシアネート化合物は、イソシアネート基が化学的に保護されたブロックイソシアネート基を有する化合物であれば特に制限はないが、硬化性の観点から、1分子内に2以上のブロックイソシアネート基を有する化合物であることが好ましい。
なお、本発明におけるブロックイソシアネート基とは、熱によりイソシアネート基を生成することが可能な基であり、例えば、ブロック剤とイソシアネート基とを反応させイソシアネート基を保護した基が好ましく例示できる。また、上記ブロックイソシアネート基は、90℃~250℃の熱によりイソシアネート基を生成することが可能な基であることが好ましい。
また、ブロックイソシアネート化合物としては、その骨格は特に制限されるものではなく、1分子中にイソシアネート基を2個有するものであればどのようなものでもよく、脂肪族、脂環族又は芳香族のポリイソシアネートであってよいが、例えば2,4-トリレンジイソシアネート、2,6-トリレンジイソシアネート、イソホロンジイソシアネート、1,6-ヘキサメチレンジイソシアネート、1,3-トリメチレンジイソシアネート、1,4-テトラメチレンジイソシアネート、2,2,4-トリメチルヘキサメチレンジイソシアネート、2,4,4-トリメチルヘキサメチレンジイソシアネート、1,9-ノナメチレンジイソシアネート、1,10-デカメチレンジイソシアネート、1,4-シクロヘキサンジイソシアネート、2,2’-ジエチルエーテルジイソシアネート、ジフェニルメタン-4,4’-ジイソシアネート、o-キシレンジイソシアネート、m-キシレンジイソシアネート、p-キシレンジイソシアネート、メチレンビス(シクロヘキシルイソシアネート)、シクロヘキサン-1,3-ジメチレンジイソシアネート、シクロヘキサン-1,4-ジメチレンジイソシアネート、1,5-ナフタレンジイソシアネート、p-フェニレンジイソシアネート、3,3’-メチレンジトリレン-4,4’-ジイソシアネート、4,4’-ジフェニルエーテルジイソシアネート、テトラクロロフェニレンジイソシアネート、ノルボルナンジイソシアネート、水素化1,3-キシリレンジイソシアネート、及び水素化1,4-キシリレンジイソシアネート等のイソシアネート化合物及びこれらの化合物から派生するプレポリマー型の骨格の化合物を好適に用いることができる。これらのなかでも、トリレンジイソシアネート(TDI)及びジフェニルメタンジイソシアネート(MDI)、ヘキサメチレンジイソシアネート(HDI)、又はイソホロンジイソシアネート(IPDI)が好ましい。
上記ブロックイソシアネート化合物のブロック構造を形成するブロック剤としては、オキシム化合物、ラクタム化合物、フェノール化合物、アルコール化合物、アミン化合物、活性メチレン化合物、ピラゾール化合物、メルカプタン化合物、イミダゾール系化合物、及びイミド系化合物等が挙げられる。これらのなかでも、オキシム化合物、ラクタム化合物、フェノール化合物、アルコール化合物、アミン化合物、活性メチレン化合物、及びピラゾール化合物から選ばれるブロック剤が好ましい。
光配向膜形成用組成物は、上記以外の他の成分を含んでいてもよい。
他の成分としては、例えば、架橋促進剤、密着改良剤、レベリング剤、及び可塑剤等が挙げられる。架橋促進剤としては、種々の金属塩キレート化合物、及び熱酸発生剤等が挙げられる。密着改良剤、レベリング剤、及び可塑剤としては、塗布用組成物の添加剤として知られている種々の公知の材料を利用することができる。
光配向膜形成用組成物は、光配向膜を作製する作業性等の観点から、有機溶媒を含むことが好ましい。溶媒を適切に選択することにより光配向膜形成用組成物をポリマー支持体上に塗工した際にポリマー支持体の表面に作用し、光配向膜との密着が強化され、また、ポリマー支持体の添加剤由来の成分の抽出を制御することで光学異方性膜の配向制御を改善することができる。
なかでも、ポリマー支持体の添加剤由来の成分と相溶し易い有機溶媒が好ましい。光配向膜形成用組成物にポリマー支持体の添加剤由来の成分と相溶し易い有機溶媒を使用することで、光配向膜形成用組成物をポリマー支持体上に塗工した際にポリマー支持体の表面に作用して光配向膜との密着が強化され得る。また、上記有機溶媒の含有量を適切に調整することで、ポリマー支持体の添加剤由来の成分の光配向膜形成用組成物への過度な抽出が抑制されることで光学異方性膜の配向制御が改善され得る。
なお、ポリマー支持体が添加剤を含むセルロースアシレートフィルムであり、かつポリエステル化合物又は糖エステル化合物である場合、有機溶媒として、ケトン類、エステル類、又はプロピレングリコールエーテル類を含むことが好ましい。
有機溶媒は、1種単独で用いてもよく、2種以上を併用してもよい。
本発明を構成する光配向膜は、上述した光配向膜形成用組成物を用いる以外は従来公知の製造方法により製造することができ、特に、ロールトゥロールプロセスで製造することが好ましい。
具体的な製造方法の一例としては、下記工程1、下記工程2、及び下記工程3を含む製造方法が挙げられる。これらの工程の各条件を適切に調整することにより、ポリマー支持体と光配向膜との密着性を高めつつ、ポリマー支持体の添加剤由来の成分の抽出を制御することで光学異方性膜の配向制御を改善することができる。
工程1:上述した光配向膜形成用組成物を上述のポリマー支持体表面に塗布して塗膜を形成する塗布工程
工程2:加熱することによって上記塗膜を乾燥及び架橋する加熱工程
工程3:上記乾燥及び架橋後の塗膜に対して偏光を照射するか、又は上記乾燥及び架橋後の塗膜の表面に対して斜め方向から非偏光を照射する光照射工程
塗布工程における塗布方法は特に制限されず、目的に応じて適宜選択することができ、例えば、スピンコーティング、ダイコーティング、グラビアコーティング、フレキソ印刷、及びインクジェット印刷等が挙げられる。ロールトゥロールプロセスにおいては、なかでも、ダイコーティング、又はグラビアコーティングが好ましい。
図3においては、ポリマー支持体の巻回体(ロール)から巻きだしたポリマー支持体1上にダイ32を用いて塗布を行っている。
加熱工程における加熱方法は特に制限されず、工程1を経て得られる塗膜付きポリマー支持体を公知の方法により加熱すればよい。
加熱方法としては、例えば、加熱雰囲気下に晒すことによって塗膜付きポリマー支持体を加熱する方法、熱媒体を通流させた搬送ロール等に接触させることによって塗膜付きポリマー支持体を加熱する方法、及び熱線を照射することによって塗膜付きポリマー支持体を加熱する方法が挙げられる。加熱温度としては、30~200℃が好ましい。
加熱工程の際に塗膜中の溶媒除去と重合体Apの熱架橋反応とを適切に制御することで、ポリマー支持体と光配向膜との密着性が強化し、かつ、ポリマー支持体の添加剤由来の成分の抽出の制御がなされて光学異方性膜の配向制御が改善し得る。
なお、図3においては、加熱装置33により、塗膜付きポリマー支持体を加熱を行っている。
光照射工程において、工程2を経た上記乾燥及び架橋後の塗膜に対して照射する偏光は特に制限はなく、例えば、直線偏光、円偏光、及び楕円偏光等が挙げられ、直線偏光が好ましい。
また、非偏光を照射する「斜め方向」とは、塗膜表面の法線方向に対して極角θ(0<θ<90°)傾けた方向である限りは特に制限はなく、目的に応じて適宜選択することができる。
なお、LED(light emitting diode)及びレーザー等の光源を用いた場合には、より簡略な構成で同様の偏光照射を実現できる。
偏光又は非偏光の照度としては、上記乾燥及び架橋後の塗膜中に含まれる液晶分子の配向を制御し得る波長であれば特に制限はないが、0.1~300mW/cm2が好ましく、1~100mW/cm2がより好ましい。
本発明の光学フィルムを構成する光学異方性膜は、逆波長分散性の重合性液晶化合物を含む組成物(以下、「重合性液晶組成物」ともいう。)を硬化させて得られる層である。
上記光学異方性膜中、液晶化合物の配向状態は固定されている。つまり、光学異方性膜中、液晶化合物は上述した光配向膜の配向規制力によって配向状態を形成し、且つ、硬化処理により液晶化合物中の重合性基が重合したことで、上記配向状態は固定化されている。
また「逆波長分散性の重合液晶性化合物」とは、逆波長分散性の光学異方性膜を形成し得る重合性液晶化合物を意図する。
重合性液晶化合物としては、後述する特定重合性液晶化合物が好ましい。
更に、上記光学異方性膜の配向性がより向上する理由から、光学異方性膜は、重合性液晶組成物をスメクチック相に配向した後に重合(配向状態を固定化)して得られる層であるのが好ましい。
0.75<Re(450)/Re(550)<1.00 ・・・(II)
ここで、式(II)中、Re(450)は、光学異方性膜の波長450nmにおける面内レターデーションを表し、Re(550)は、光学異方性膜の波長550nmにおける面内レターデーションを表す。
また、上述したように、面内レターデーションの値は、AxoScan OPMF-1(オプトサイエンス社製)を用い、測定波長の光を用いて測定した値をいう。
本明細書における特定重合性液晶化合物とは、下記式(1)で表される重合性液晶化合物である。下記式(1)で表される重合性液晶化合物は、逆波長分散性である。つまり、下記式(1)で表される重合性液晶化合物を硬化して光学異方性膜を形成した時、上記光学異方性膜は逆波長分散性を示す。
また、上記式(1)中、G1及びG2は、それぞれ独立に、置換基を有していてもよい炭素数5~8の2価の脂環式炭化水素基を表し、脂環式炭化水素基を構成する-CH2-の1個以上が-O-、-S-、又はNH-で置換されていてもよい。
また、上記式(1)中、A1及びA2は、それぞれ独立に、置換基を有していてもよい炭素数6~12の2価の芳香族炭化水素基、又は置換基を有していてもよい炭素数5~8の2価の脂環式炭化水素基を表し、脂環式炭化水素基を構成する-CH2-の1個以上が-O-、-S-、又はNH-で置換されていてもよい。
また、上記式(1)中、SP1及びSP2は、それぞれ独立に、単結合、炭素数1~12の直鎖状若しくは分岐鎖状のアルキレン基、又は、炭素数1~12の直鎖状若しくは分岐鎖状のアルキレン基を構成する-CH2-の1個以上が-O-、-S-、-NH-、-N(Q)-、若しくは-CO-に置換された2価の連結基を表し、Qは、置換基を表す。
また、上記式(1)中、L1及びL2は、それぞれ独立に1価の有機基を表し、L1及びL2の少なくとも一方は重合性基を表す。ただし、Ar1が、下記式(Ar-3)で表される芳香環である場合、L1及びL2並びに下記式(Ar-3)中のL3及びL4の少なくとも1つが重合性基を表す。
また、上記式(1)中、mは、0~2の整数を表し、mが2である場合、複数のE3は、それぞれ同一であっても異なっていてもよく、複数のA1は、それぞれ同一であっても異なっていてもよい。
また、上記式(1)中、nは、0~2の整数を表し、nが2である場合、複数のE4は、それぞれ同一であっても異なっていてもよく、複数のA2は、それぞれ同一であっても異なっていてもよい。
また、上記式(1)中、Ar1は、後述する式(Ar-1)~(Ar-5)で表される基からなる群から選択されるいずれかの芳香環を表す。
これらのうち、シクロヘキシレン基(シクロヘキサン環に由来する2価の基)が好ましく、1,4-シクロヘキシレン基がより好ましく、トランス-1,4-シクロヘキシレン基が更に好ましい。
また、上記式(1)中、G1及びG2が示す炭素数5~8の2価の脂環式炭化水素基が有していてもよい置換基としては、後述する式(Ar-1)中のY1が示す炭素数6~12の芳香族炭化水素基及び炭素数3~12の芳香族複素環基が有してもよい置換基と同様のものが挙げられる。
また、A1及びA2が示す炭素数5~8の2価の脂環式炭化水素基としては、上記式(1)中のG1及びG2で説明したものと同様のものが挙げられ、シクロヘキシレン基(シクロヘキサン環に由来する2価の基)が好ましく、1,4-シクロヘキシレン基がより好ましく、トランス-1,4-シクロヘキシレン基が更に好ましい。
また、上記式(1)中、A1及びA2が示す炭素数6~12の2価の芳香族炭化水素基、及びA1及びA2が示す炭素数5~8の2価の脂環式炭化水素基が有していてもよい置換基としては、後述する式(Ar-1)中のY1が示す炭素数6~12の芳香族炭化水素基及び炭素数3~12の芳香族複素環基が有してもよい置換基と同様のものが挙げられる。
アルキル基としては、直鎖状、分岐鎖状、又は環状であってもよいが、直鎖状が好ましい。アルキル基の炭素数は、1~30が好ましく、1~20がより好ましく、1~10が更に好ましい。
また、アリール基は、単環であっても多環であってもよいが単環が好ましい。アリール基の炭素数は、6~25が好ましく、6~10がより好ましい。
また、ヘテロアリール基は、単環であっても多環であってもよい。ヘテロアリール基を構成するヘテロ原子の数は1~3が好ましい。ヘテロアリール基を構成するヘテロ原子は、窒素原子、硫黄原子、又は酸素原子が好ましい。ヘテロアリール基の炭素数は、6~18が好ましく、6~12がより好ましい。
また、上述した、アルキル基、アリール基、及びヘテロアリール基は、無置換であってもよく、置換基を有していてもよい。置換基としては、後述する式(Ar-1)中のY1が示す炭素数6~12の芳香族炭化水素基及び炭素数3~12の芳香族複素環基が有してもよい置換基と同様のものが挙げられる。
ラジカル重合性基としては、一般に知られているラジカル重合性基を用いることができ、アクリロイル基又はメタクリロイル基が好ましい。アクリロイル基及びメタクリロイル基を比較すると、一般的にアクリロイル基の重合速度の方が速いことが知られており、生産性向上の観点からアクリロイル基が好ましいが、メタクリロイル基も重合性基として同様に使用できる。
カチオン重合性基としては、一般に知られているカチオン重合性を用いることができ、具体的には、脂環式エーテル基、環状アセタール基、環状ラクトン基、環状チオエーテル基、スピロオルソエステル基、及びビニルオキシ基等が挙げられる。なかでも、脂環式エーテル基、又はビニルオキシ基が好ましく、エポキシ基、オキセタニル基、又はビニルオキシ基がより好ましい。
重合性基としては、なかでも、下記に例示するものが好ましい。
以下において、式(Ar-1)~(Ar-5)について説明する。
R5が示す炭素数1~6のアルキル基としては、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、及びn-ヘキシル基等が挙げられる。
Y1が示す炭素数6~12の芳香族炭化水素基としては、例えば、フェニル基、2,6-ジエチルフェニル基、及びナフチル基等のアリール基が挙げられる。
Y1が示す炭素数3~12の芳香族複素環基としては、例えば、チエニル基、チアゾリル基、フリル基、及びピリジル基等のヘテロアリール基が挙げられる。
また、Y1が示す炭素数6~12の芳香族炭化水素基及び炭素数3~12の芳香族複素環基が有してもよい置換基としては、例えば、アルキル基、アルコキシ基、及びハロゲン原子等が挙げられる。
アルキル基としては、例えば、炭素数1~18の直鎖状、分岐鎖状、又は環状のアルキル基が好ましく、炭素数1~8のアルキル基(例えば、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、t-ブチル基、及びシクロヘキシル基等)がより好ましく、炭素数1~4のアルキル基が更に好ましく、メチル基又はエチル基が特に好ましい。
アルコキシ基としては、例えば、炭素数1~18のアルコキシ基が好ましく、炭素数1~8のアルコキシ基(例えば、メトキシ基、エトキシ基、n-ブトキシ基、及びメトキシエトキシ基等)がより好ましく、炭素数1~4のアルコキシ基が更に好ましく、メトキシ基又はエトキシ基が特に好ましい。
ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、及びヨウ素原子等が挙げられ、なかでも、フッ素原子、又は塩素原子が好ましい。
炭素数1~20の1価の直鎖状又は分岐鎖状の脂肪族炭化水素基としては、炭素数1~15のアルキル基が好ましく、炭素数1~8のアルキル基がより好ましく、具体的には、メチル基(Me)、エチル基、イソプロピル基、tert-ペンチル基(1,1-ジメチルプロピル基)、tert-ブチル基(tBu)、又は1,1-ジメチル-3,3-ジメチル-ブチル基がより好ましく、メチル基、エチル基、又はtert-ブチル基が更に好ましい。
炭素数3~20の1価の脂環式炭化水素基としては、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロデシル基、メチルシクロヘキシル基、及びエチルシクロヘキシル基等の単環式飽和炭化水素基;シクロブテニル基、シクロペンテニル基、シクロヘキセニル基、シクロヘプテニル基、シクロオクテニル基、シクロデセニル基、シクロペンタジエニル基、シクロヘキサジエニル基、シクロオクタジエニル基、及びシクロデカジエン等の単環式不飽和炭化水素基;ビシクロ[2.2.1]ヘプチル基、ビシクロ[2.2.2]オクチル基、トリシクロ[5.2.1.02,6]デシル基、トリシクロ[3.3.1.13,7]デシル基、テトラシクロ[6.2.1.13,6.02,7]ドデシル基、及びアダマンチル基等の多環式飽和炭化水素基;等が挙げられる。
炭素数6~20の1価の芳香族炭化水素基としては、具体的には、フェニル基、2,6-ジエチルフェニル基、ナフチル基、及びビフェニル基等が挙げられ、炭素数6~12のアリール基(特にフェニル基)が好ましい。
ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、及びヨウ素原子等が挙げられ、なかでも、フッ素原子、塩素原子、又は臭素原子が好ましい。
一方、R6~R9、RX、及びRYが示す炭素数1~6のアルキル基としては、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、及びn-ヘキシル基等が挙げられる。
また、Xが示す第14~16族の非金属原子としては、例えば、酸素原子、硫黄原子、置換基を有する窒素原子、及び置換基を有する炭素原子が挙げられ、置換基としては、具体的には、アルキル基、アルコキシ基、アルキル置換アルコキシ基、環状アルキル基、アリール基(例えば、フェニル基、ナフチル基等)、シアノ基、アミノ基、ニトロ基、アルキルカルボニル基、スルホ基、及び水酸基等が挙げられる。
上記式(1)中、R1、R2、R3、及びR4が示す炭素数1~4のアルキル基としては、直鎖状、分岐鎖状、又は環状のいずれであってもよく、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、及びtert-ブチル基等が挙げられる。
炭素数1~12の直鎖状若しくは分岐鎖状のアルキレン基としては、上記式(1)中のSP1及びSP2において説明したものと同様のものが挙げられる。
Qで示される置換基としては、上記式(Ar-1)中のY1が示す炭素数6~12の芳香族炭化水素基及び炭素数3~12の芳香族複素環基が有してもよい置換基と同様のものが挙げられる。
1価の有機基としては、上記式(1)中のL1及びL2において説明したものと同様のものが挙げられる。
また、重合性基としては、上記式(1)中のL1及びL2において説明したものと同様のものが挙げられる。
また、上記式(Ar-4)及び上記式(Ar-5)中、Ayは、水素原子、置換基を有していてもよい炭素数1~12のアルキル基、又は、芳香族炭化水素環及び芳香族複素環からなる群から選択される少なくとも1つの芳香環を有する、炭素数2~30の有機基を表す。
ここで、Ax及びAyにおける芳香環は、置換基を有していてもよく、AxとAyとが結合して環を形成していてもよい。
また、上記式(Ar-4)及び上記式(Ar-5)中、Q3は、水素原子、又は、置換基を有していてもよい炭素数1~6のアルキル基を表す。
また、Q3が示す炭素数1~6のアルキル基としては、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、及びn-ヘキシル基等が挙げられる。また、Q3が示す炭素数1~6のアルキル基が有していてもよい置換基としては、上記式(Ar-1)中のY1が示す炭素数6~12の芳香族炭化水素基及び炭素数3~12の芳香族複素環基が有してもよい置換基と同様のものが挙げられる。
ここで、pKaは、25℃におけるテトラヒドロフラン(THF)/水=6/4の体積比である混合溶媒中における酸解離定数の値である。
本発明における酸解離定数の測定方法としては、丸善(株)刊 実験化学講座第2版の215ページ~217ページに記載のアルカリ適定法を用いることができる。
なお、下記表1中、Kの側鎖構造に示される「*」は、芳香環との結合位置を表す。
また、下記表1中1-2、1-12で表される側鎖構造において、それぞれアクリロイルオキシ基及びメタクリロイル基に隣接する基は、プロピレン基(メチル基がエチレン基に置換した基)を表し、メチル基の位置が異なる位置異性体の混合物を表す。
重合性液晶組成物は、上述した特定重合性液晶化合物以外に、重合性基を1個以上有する他の重合性化合物を含んでいてもよい。
ここで、他の重合性化合物が有する重合性基は特に制限されず、例えば、(メタ)アクリロイル基、ビニル基、スチリル基、アリル基等が挙げられる。重合性基としては、なかでも、(メタ)アクリロイル基が好ましい。
重合性液晶組成物は、重合開始剤を含むことが好ましい。
重合開始剤としては、紫外線照射によって重合反応を開始可能な光重合開始剤であるのが好ましい。
光重合開始剤としては、例えば、α-カルボニル化合物(米国特許第2367661号、及び同2367670号の各明細書記載)、アシロインエーテル(米国特許第2448828号明細書記載)、α-炭化水素置換芳香族アシロイン化合物(米国特許第2722512号明細書記載)、多核キノン化合物(米国特許第3046127号、及び同2951758号の各明細書記載)、トリアリールイミダゾールダイマーとp-アミノフェニルケトンとの組み合わせ(米国特許第3549367号明細書記載)、アクリジン及びフェナジン化合物(特開昭60-105667号公報、及び米国特許第4239850号明細書記載)及びオキサジアゾール化合物(米国特許第4212970号明細書記載)、並びにアシルフォスフィンオキシド化合物(特公昭63-40799号公報、特公平5-29234号公報、特開平10-95788号公報、及び特開平10-29997号公報記載)等が挙げられる。
また、上記式(I)中、Ar3は、2価の芳香族基を表し、D5は、炭素数1~12の2価の有機基を表す。
また、上記式(I)中、R11は、炭素数1~12のアルキル基を表し、Y2は、1価の有機基を表す。
また、上記式(I)中、Ar3が示す2価の芳香族基を構成する芳香環としては、例えば、ベンゼン環、ナフタレン環、アントラセン環、及びフェナンスロリン環等の芳香族炭化水素環;フラン環、ピロール環、チオフェン環、ピリジン環、チアゾール環、及びベンゾチアゾール環等の芳香族複素環;等が挙げられる。
また、上記式(I)中、D5が示す炭素数1~12の2価の有機基としては、例えば、炭素数1~12の直鎖状若しくは分岐鎖状のアルキレン基が挙げられ、具体的には、メチレン基、エチレン基、又はプロピレン基が好ましい。
また、上記式(I)中、R11が示す炭素数1~12のアルキル基としては、具体的には、メチル基、エチル基、又はプロピル基が好ましい。
また、上記式(I)中、Y2が示す1価の有機基としては、例えば、ベンゾフェノン骨格((C6H5)2CO)を含む官能基が挙げられる。具体的には、下記式(Ia)及び下記式(Ib)で表される基のように、末端のベンゼン環が無置換又は1置換であるベンゾフェノン骨格を含む官能基が好ましい。なお、下記式(Ia)及び下記式(Ib)中、*は結合位置、すなわち、上記式(I)におけるカルボニル基の炭素原子との結合位置を表す。
重合性液晶組成物中、重合開始剤の含有量(複数種含まれる場合はその合計含有量)は特に制限されないが、重合性液晶組成物の固形分の0.01~20質量%であることが好ましく、0.5~5質量%であることがより好ましい。
重合性液晶組成物は、光学異方性膜を形成する作業性等の観点から、溶媒を含むことが好ましい。溶媒を適切に選択することにより、重合性液晶化合物の配向状態をより精密に制御することができる。
溶媒としては、具体的には、ケトン類(例えば、アセトン、2-ブタノン、メチルイソブチルケトン、メチルエチルケトン、シクロヘキサノン、及びシクロペンタノン等)、エーテル類(例えば、ジオキサン、及びテトラヒドロフラン等)、脂肪族炭化水素類(例えば、ヘキサン等)、脂環式炭化水素類(例えば、シクロヘキサン等)、芳香族炭化水素類(例えば、トルエン、キシレン、及びトリメチルベンゼン等)、ハロゲン化炭素類(例えば、ジクロロメタン、ジクロロエタン、ジクロロベンゼン、トリクロロメタン、及びクロロトルエン等)、エステル類(例えば、酢酸メチル、酢酸エチル、及び酢酸ブチル等)、水、アルコール類(例えば、エタノール、イソプロパノール、ブタノール、及びシクロヘキサノール等)、セロソルブ類(例えば、メチルセロソルブ、及びエチルセロソルブ等)、セロソルブアセテート類、スルホキシド類(例えば、ジメチルスルホキシド等)、及びアミド類(例えば、ジメチルホルムアミド、及びジメチルアセトアミド等)等が挙げられる。
有機溶媒は、1種単独で用いてもよく、2種以上を併用してもよい。
重合性液晶組成物は、光学異方性膜の表面を平滑に保ち、配向制御を容易にする観点から、レベリング剤を含むことが好ましい。
このようなレベリング剤としては、添加量に対するレベリング効果が高い理由から、フッ素系レベリング剤又はケイ素系レベリング剤であることが好ましく、泣き出し(ブルーム、ブリード)を起こしにくい観点から、フッ素系レベリング剤であることがより好ましい。
重合性液晶組成物は、必要に応じて、配向制御剤を含んでいてもよい。
配向制御剤により、ホモジニアス配向の他、傾斜配向、ハイブリッド配向、及びコレステリック配向等の種々の配向状態を形成することができ、また、特定の配向状態をより均一かつより精密に制御して実現することができる。
低分子の配向制御剤としては、例えば、特開2002-20363号公報の[0009]~[0083]段落、特開2006-106662号公報の[0111]~[0120]段落、及び特開2012-211306公報の[0021]~[0029]段落の記載を参酌することができ、この内容は本願明細書に組み込まれる。
また、高分子の配向制御剤としては、例えば、特開2004-198511号公報の[0021]~[0057]段落、及び特開2006-106662号公報の[0121]~[0167]段落を参酌することができ、この内容は本願明細書に組み込まれる。
これらの配向制御剤は、さらに重合性官能基、特に、本発明に用いる重合性液晶組成物を構成する特定重合性液晶化合物と重合可能な重合性官能基を有していてもよい。
重合性液晶組成物は、上述した成分以外のその他の成分を含んでいてもよい。その他の成分としては、例えば、上述した重合性液晶化合物以外の液晶化合物、界面活性剤、チルト角制御剤、配向助剤、可塑剤、及び架橋剤等が挙げられる。配向助剤としては、ハイソルブMTEM(東邦化学工業社製)、及びNKエステルA-200(新中村化学工業社製)等が好ましい。
例えば、上述した光配向膜上に、重合性液晶組成物を塗布して塗膜を形成し、得られた塗膜に対して硬化処理(光照射処理(例えば紫外線照射処理)又は加熱処理)を施すことにより形成することができる。なお、光学異方性膜の形成工程は、図3に示すように、光配向膜の形成工程と連続して行うことが好ましい。
重合性液晶組成物の塗布は、例えば、ワイヤーバーコーティング法、押し出しコーティング法、ダイレクトグラビアコーティング法、リバースグラビアコーティング法、及びダイコーティング法等の公知の方法により実施できる。なお、図3においては、重合性液晶組成物の塗布は、ダイ35によって行われる。
塗膜から溶媒を除去するに当たっては、光配向膜の形成方法で述べたのと同様の加熱工程を適用できる。加熱条件、特に塗膜から溶媒を除去する条件を調整することによってポリマー支持体の添加剤由来の成分の抽出及び塗膜内での拡散を制御することで、光学異方性膜の配向状態を改善することができる。
なお、図3においては、上記加熱工程は、加熱装置36によって行われる。
本発明の光学フィルムと偏光子とを貼り合わせることにより各種の機能を付与した偏光板を構成することができる。また、本発明の光学フィルム中の光学異方性膜が光配向膜と剥離可能である場合、光学フィルムから転写された光学異方性膜と偏光子とを貼り合わせることによって偏光板を構成することもできる。
偏光子としては光を特定の直線偏光に変換する機能を有する部材であれば特に制限されず、従来公知の吸収型偏光子及び反射型偏光子を利用することができる。
また、基材上にポリビニルアルコール層を形成した積層フィルムの状態で延伸及び染色を施すことで偏光子を得る方法として、特許第5048120号公報、特許第5143918号公報、特許第5048120号公報、特許第4691205号公報、特許第4751481号公報、及び特許第4751486号公報等を挙げることができ、これらの偏光子に関する公知の技術も好ましく利用することができる。
上述した反射型偏光子としては、複屈折の異なる薄膜を積層した偏光子、ワイヤーグリッド型偏光子、及び、選択反射域を有するコレステリック液晶と1/4波長板とを組み合わせた偏光子等が用いられる。
なかでも、取り扱い性の点から、ポリビニルアルコール系樹脂(-CH2-CHOH-を繰り返し単位として含むポリマー、特に、ポリビニルアルコール及びエチレン-ビニルアルコール共重合体からなる群から選択される少なくとも1つ)を含む偏光子であることが好ましい。
セルロース系ポリマー又はアクリル系ポリマーを用いたフィルムとしては、上述したポリマー支持体と同じものを用いることができる。なお、偏光板としては、上述したポリマー支持体を偏光子とを貼り合わせたものであってもよい。
図2Aは、直線偏光子22、ポリマー支持体16、光配向膜14、光学異方性膜12をこの順に有する偏光板20の概念図である。直線偏光子22とポリマー支持体16との間は任意に接着層(図示せず)を設けてもよいし、また、直線偏光子22のポリマー支持体16とは反対の面に任意のポリマーフィルム(図示せず)を設けてもよい。
図2Bは、直線偏光子22、本発明の光学フィルムから転写した光学異方性膜12、及びポジティブCプレート18をこの順に有する偏光板の概念図を示す。各層間には感圧性接着層等の接着層(図示せず)及び任意のポリマーフィルム(図示せず)を設けてもよい。
本発明の光学フィルム又は本発明の光学フィルムから転写された光学異方性膜がλ/4プレートの特性を有する場合、組み合わせる直線偏光子の吸収軸と、本発明の光学フィルム又は本発明の光学フィルムから転写された光学異方性膜の遅相軸とを45°で交差させることにより、円偏光板を得ることができる。
更に、上記円偏光板を後述する画像表示装置の外光反射防止層として用いる場合においては、反射光の色味を調整することを目的として、組み合わせる直線偏光子の吸収軸と、本発明の光学フィルムあるいは本発明の光学フィルムを構成する光学異方性膜の遅相軸との交差角を45°±8°の範囲で調整することが好ましい。
上述した偏光板には、本発明の光学フィルム又は本発明の光学フィルムから転写された光学異方性膜、及び上述した任意のポリマーフィルムの他に、さらにその他の層を含んでいてもよい。その他の層としては、具体的には、加飾層、接着層、光拡散層、ガスバリア層、着色層、導電層(タッチパネル)、及び帯電防止層等が挙げられる。また、斜め透過光の偏光変換の最適化を目的として、例えばポジティブCプレート及びその他の位相差フィルムをさらに組合せてもよい。
本発明の光学フィルム又は上述した偏光板は、画像表示装置に適用できる。
本発明の画像表示装置に用いられる表示素子としては特に制限されず、例えば、液晶セル、有機エレクトロルミネッセンス(以下、「EL」と略す。)表示パネル、プラズマディスプレイパネル、及びマイクロLEDディスプレイパネル等が挙げられる。本発明の光学フィルム又は上述した偏光板は、表示画質を向上させるための光学補償の目的で使用することもできるし、外光が表示素子で反射されることによる表示画質の低下を抑制する目的で使用することもできる。
上述した本発明の光学フィルム又は本発明の光学フィルムから転写された光学異方性膜を適用した液晶表示装置の一例としては、上述した本発明の光学フィルム又は本発明の光学フィルムから転写された光学異方性膜を貼り合わせた偏光板と、液晶セルとを有する液晶表示装置が挙げられる。
なお、本発明においては、液晶セルの両側に設けられる偏光板のうち、フロント側の偏光板として上述した偏光板を用いるのが好ましい。必要に応じ、ポジティブCプレート等をさらに組み合わせて、斜視方向の表示性能を改善することができる。
以下に、液晶表示装置を構成する液晶セルについて詳述する。
液晶表示装置に利用される液晶セルは、VA(Virtical Alignment)モード、OCB(Optical Compensated Bend)モード、IPS(In-Place-Switching)モード、又はTN(Twisted Nematic)であることが好ましいが、これらに制限されるものではない。
TNモードの液晶セルでは、電圧無印加時に棒状液晶性分子が実質的に水平配向し、更に60~120゜にねじれ配向している。TNモードの液晶セルは、カラーTFT(thin-film-transistor liquid-crystal display)液晶表示装置として最も多く利用されており、多数の文献に記載がある。
有機EL表示装置において、本発明の光学フィルム又は本発明の光学フィルムから転写された光学異方性膜を貼り合わせた円偏光板を用いることにより、外部光が有機ELパネルの電極等に反射して表示コントラストを低下させる現象を抑制し高画質の表示を可能にできる。有機ELパネルとしては公知の構成が広く利用でき、また、さらにタッチパネルを具備するものであることができる。上述した円偏光板には、ポジティブCプレートをさらに組み合わせることにより、斜視方向にも優れた反射色味を呈する表示装置を構成することができる。
<重合体Ap1の合成>
冷却管、温度計、及び撹拌機を備えたフラスコに、n-ブトキシメチルアクリレート60.0質量部、アクリルアミド 40.0質量部、重合開始剤として2,2’-アゾビス(イソブチロニトリル)4.8質量部、及びプロピレングリコールモノメチルエーテル 313.9質量部を仕込み、85℃にて20時間反応させることにより、架橋性基を有する重合体Ap1の溶液(固形分濃度25質量%)を得た。得られた重合体Ap1のMnは3,560、Mwは4,820であった。
Langmuir,32(36),9245-9253,(2016年)に記載された方法に従い、2-ヒドロキシエチルメタクリレート(HEMA)(東京化成試薬)と下記桂皮酸クロリド誘導体を用いて、以下に示すモノマーm-1を合成した。
冷却管、温度計、及び撹拌機を備えたフラスコに、メタクリル酸2.5質量部、メチルメタクリレート 9.2質量部、2-ヒドロキシエチルメタクリレート5.0質量部、重合開始剤として2,2’-アゾビス(イソブチロニトリル)0.2質量部、プロピレングリコールモノメチルエーテル50.7質量部を仕込み、70℃にて20時間反応させることにより、架橋性基を有する重合体Ap3の溶液(固形分濃度25質量%)を得た。得られたアクリル共重合体のMnは19,600、Mwは45,200であった。
下記組成(P-1、P-2、P-3)の光配向膜用組成物を調製した。なお、得られた各組成物では、各重合体並びに他の成分は添加した量どおりに溶媒に十分に溶解していた。
光配向膜用組成物(P-1)
―――――――――――――――――――――――――――――――――
化合物CIN-1 1.00質量部
上記重合体Ap1の溶液(固形分量35質量%) 2.90質量部
上記重合体Ap3の溶液(固形分量25質量%) 4.00質量部
パラトルエンスルホン酸1水和物 0.10質量部
プロピレングリコールモノメチルエーテル 43.7質量部
―――――――――――――――――――――――――――――――――
光配向膜用組成物(P-2)
―――――――――――――――――――――――――――――――――
上記重合体Ap1 4.60質量部
下記化合物B2 0.80質量部
下記架橋剤C-1 3.00質量部
化合物D1 0.80質量部
酢酸ブチル 120質量部
―――――――――――――――――――――――――――――――――
(化合物D1)熱酸発生剤(サンエイドSI-60、三新化学工業株式会社製)
光配向膜用組成物(P-3)
―――――――――――――――――――――――――――――――――
上記重合体Ap2 10.00質量部
上記化合物D1 0.50質量部
イソプロピルアルコール 1.65質量部
酢酸ブチル 107.20質量部
メチルエチルケトン 26.80質量部
―――――――――――――――――――――――――――――――――
下記組成(A-1~A-3)の光学異方性膜用塗布液を調製した。
光学異方性膜用塗布液(A-1)
―――――――――――――――――――――――――――――――――
・下記重合性液晶化合物L-1 42.00質量部
・下記重合性液晶化合物L-2 42.00質量部
・下記重合性化合物A-1 16.00質量部
・下記重合開始剤S-1 0.50質量部
・レベリング剤(下記化合物G-1) 0.20質量部
・ハイソルブMTEM(東邦化学工業社製) 2.00質量部
・NKエステルA-200(新中村化学工業社製) 1.00質量部
・メチルエチルケトン 424.8質量部
―――――――――――――――――――――――――――――――――
なお、下記重合性液晶化合物L-1及びL-2のアクリロイルオキシ基に隣接する基は、プロピレン基(メチル基がエチレン基に置換した基)を表し、下記重合性液晶化合物L-1及びL-2は、メチル基の位置が異なる位置異性体の混合物を表す。
(光学異方性膜用塗布液A-2)
―――――――――――――――――――――――――――――――――
・下記重合性液晶化合物L-3 95.00質量部
・下記重合性液晶化合物L-4 5.00質量部
・上記重合開始剤S-1 0.50質量部
・上記レベリング剤G-1 0.20質量部
・シクロペンタノン 570.00質量部
―――――――――――――――――――――――――――――――――
光学異方性膜用塗布液(A-3)
―――――――――――――――――――――――――――――――――
・上記重合性液晶化合物L-1 42.00質量部
・上記重合性液晶化合物L-2 42.00質量部
・上記重合性化合物A-1 16.00質量部
・上記重合開始剤S-1 0.50質量部
・レベリング剤(上記化合物G-1) 0.20質量部
・ハイソルブMTEM(東邦化学工業社製) 2.00質量部
・NKエステルA-200(新中村化学工業社製) 1.00質量部
・シクロペンタノン 424.8質量部
―――――――――――――――――――――――――――――――――
(コア層セルロースアシレートドープの作製)
下記の組成物をミキシングタンクに投入し、攪拌して、各成分を溶解し、コア層セルロースアシレートドープとして用いるセルロースアセテート溶液を調製した。
─────────────────────────────────
コア層セルロースアシレートドープ
─────────────────────────────────
アセチル置換度2.88のセルロースアセテート 100質量部
特開2015-227955号公報の実施例に
記載されたポリエステル化合物B 12質量部
下記の化合物F 2質量部
メチレンクロライド(第1溶媒) 430質量部
メタノール(第2溶媒) 64質量部
─────────────────────────────────
上記のコア層セルロースアシレートドープ90質量部に下記のマット剤溶液を10質量部加え、外層セルロースアシレートドープとして用いるセルロースアセテート溶液を調製した。
─────────────────────────────────
マット剤溶液
─────────────────────────────────
平均粒子サイズ20nmのシリカ粒子
(AEROSIL R972、日本アエロジル(株)製) 2質量部
メチレンクロライド(第1溶媒) 76質量部
メタノール(第2溶媒) 11質量部
上記のコア層セルロースアシレートドープ 1質量部
─────────────────────────────────
上記コア層セルロースアシレートドープと上記外層セルロースアシレートドープを平均孔径34μmのろ紙及び平均孔径10μmの焼結金属フィルターでろ過した後、上記コア層セルロースアシレートドープとその両側に外層セルロースアシレートドープとを3層同時に流延口から20℃のドラム上に流延した(バンド流延機)。ドラム上のフィルムの溶媒含有率が略20質量%の状態でフィルムを剥ぎ取り、フィルムの幅方向の両端をテンタークリップで固定し、横方向に延伸倍率1.1倍で延伸しつつ乾燥した。その後、熱処理装置のロール間を搬送することにより、さらに乾燥し、厚み40μmのセルロースアシレートフィルムを作製し、これを実施例1のポリマー支持体(セルロースアシレートフィルム1)とした。セルロースアシレートフィルム1のコア層は厚み36μm、コア層の両側に配置された外層はそれぞれ厚み2μmであった。得られたセルロースアシレートフィルム1の波長550nmにおける面内レターデーションは0nmであり、厚み方向のレターデーションは、1nmであった。
〔光学フィルムの作製〕
作製した長尺状のセルロースアシレートフィルム1を繰り出して搬送しながら、セルロースアシレートフィルム1の片側の面に、先に調製した光配向膜用組成物P-1を連続的に塗布した。
塗布後、搬送しながら115℃の雰囲気下で150秒間加熱し、厚さ0.2μmの光異性化組成物層を形成した。
得られた光異性化組成物層に偏光紫外線照射(10mJ/cm2、超高圧水銀ランプ使用)することで、光配向膜PA-1を形成した。
次いで、光配向膜上に、先に調製した光学異方性膜用塗布液A-1を連続的に塗布し、組成物層(塗膜)を形成した。
形成した組成物層を110℃まで加熱した後、60℃に冷却し配向を安定化させた。その後、60℃に保ち、窒素雰囲気下(酸素濃度100ppm)で紫外線照射(500mJ/cm2、超高圧水銀ランプ使用)によって配向を固定化し、厚さ2.3μmの光学異方性膜を形成し、実施例1の光学フィルム1を作製した。得られた光学積層体の波長550nmにおける面内レターデーションは140nmであった。
光配向膜用組成物及び/又は光配向膜の厚さを表2に記載のように変更し、実施例2~4の光学フィルム2~4、比較例1の光学フィルム11を作製した。なお、光配向膜の厚さの変更は、使用した光配向膜用組成物の面積あたりの塗布量を変更することによって行った。また、光学異方性膜形成用組成物の面積あたりの塗布量を調整することにより、各フィルムの光学異方性膜の波長550nmにおける面内レターデーションは全て140nmとした。
光学異方性膜形成用組成物として光学異方性膜用塗布液A-3を用いた以外は実施例2と同様にして、実施例5の光学フィルム5を作製した。光学異方性膜の波長550nmにおける面内レターデーションは140nmであった。
光学異方性膜形成用組成物として光学異方性膜用塗布液A-2を用いた以外は実施例2と同様にして、実施例6の光学フィルム6を作製した。光学異方性膜の波長550nmにおける面内レターデーションは140nmであった。
実施例1において、セルロースアシレートフィルム1に代えフィルム2としてポリエチレンテレフタレートフィルム(FD100、富士フイルム(株)製。表中ではフィルム2と称する。)を用いた以外は、実施例1と同様にして比較例2の光学フィルム12を作製した。
実施例1において、光異性化組成物層の加熱時間を100秒とした以外は、実施例1と同様にして比較例3の光学フィルム13を作製した。
<支持体と光配向膜との密着性>
上記の光学フィルム作製工程中において、支持体上に光配向膜が積層された積層体を取りだし、JIS D0202-1988に準拠して、碁盤目テープ剥離試験を行った。セロハンテープ(商品名:CT24、ニチバン(株)製)を用い、擦り棒を用いてフィルムに密着させた後、剥離した。判定は100マスの内、剥離するマス目の数で表し、下記の基準に従い評価した。
A:剥離したマスが無い
B:1~9マスの剥離が見られる
C:剥離したマスが10マス以上
<光配向膜表面の支持体由来成分量>
[検量線の作成]
上記の光配向膜用組成物P-1に、上述したポリエステル化合物Bを、組成物P-1の全固形分量に対して0.1質量%、1.0質量%添加した検量線作成用の組成物P-1(0.1)、P-1(1.0)をそれぞれ調製した。光配向膜用組成物P-1、並びに検量線作成用の組成物P-1(0.1)及びP-1(1.0)を洗浄したガラス板上にそれぞれスピンコートした後120℃で1分間加熱し、ガラス板上に設けられた厚さ0.3μmのモデル膜をそれぞれ作製した。
得られたモデル膜について、Ulvac-PHI社製質量分析装置「TRIFT V Nano TOF(一次イオンBi3 ++、加速電圧30kV)」を用いて、モデル膜にAr-GCIB銃(15kV、2.5nA、500μm四方)でエッチングしながら、膜に含まれるポリエステル化合物B由来のフラグメントイオンの膜厚方向の総和を総検出イオン量で規格化することで、光配向膜用組成物P-1に含まれるポリエステル化合物B比率を測定することにより計算上含まれるポリエステル化合物Bの量と検出イオン量との相関を求め、光配向膜中に含まれるポリエステル化合物B含有量の検量線を作成した。
上述した化合物Fについても、同様の操作により検量線を作成した。
また、光配向膜用組成物P-2、P-3についても同様の手順により上述のポリエステル化合物B含有量及び化合物F含有量の検量線を作成した。
作製した光学フィルム1、2、4、5、6、11、12、及び13について、光学異方性膜を粘着テープを用いて光配向膜上から除去した後、表出した光配向膜PA-1の表面を二次イオン質量分析装置で分析した。また、作製した光学フィルム3については、フィルム面から0.6°の角度で斜め切削してその切削面に表出した光配向膜の部位を二次イオン質量分析装置で分析した。得られた各化合物の規格化二次イオンピーク量から、上述した検量線に基づいて、それらの含有量の総量を算出した。つまり、光配向膜全質量に対する、光配向膜において光学異方性膜との境界領域に含まれるポリマー支持体の添加剤に由来する成分の量(質量%)を求めた。結果を表2に示す。
作製した光学フィルムについて、偏光顕微鏡を用いて消光位から2度ずらした状態で観察した。その結果、以下の基準で評価した。結果を下記表2に示す。
A:液晶ダイレクタが均一に整って配向している
B:液晶ダイレクタの乱れがなく、面状が安定している
C:液晶ダイレクタの乱れが部分的であり、面状が安定している
D:液晶ダイレクタが広く乱れており、面状が安定していない
AxoScan OPMF-1(オプトサイエンス社製)を用い、面内レターデーション(Re(450nm)とRe(550nm))測定波長の光を用いて測定し、波長分散Re(450nm)/Re(550nm)の値を示す。
また、実施例2、実施例5、及び実施例6の対比から、特定重合性液晶化合物が上述した式(1-1)~(1-14)で表される化合物に該当する場合、得られる光学フィルムは、液晶化合物の配向状態がより良好であった。
より具体的には、比較例1においては、ポリマー支持体上に形成される光配向膜形成用組成物の塗膜(光異性化組成物層)が厚いことからポリマー支持体に作用する溶媒量が多く、これに起因して、ポリマー支持体の添加剤由来の成分の光異性化組成物層への過度な抽出が生じたことが理由であると推測される。この結果、得られる光学フィルムは、ポリマー支持体と光配向膜との密着性には優れるものの、光異性化組成物層の液晶化合物の配向状態の均一性に劣ると考えられる。
また、比較例2においては、光配向膜形成用組成物中の溶媒がポリマー支持体表面を膨潤する作用がない又は著しく弱いため、得られる光学フィルムのポリマー支持体と光配向膜との密着性が所望の要求を満たさなかったと考えられる。
また、比較例3においては、光配向膜形成用組成物の塗膜(光異性化組成物層)の塗膜の加熱時間を短くしたため光配向膜の架橋密度が小さく、これに起因して、光配向膜上に光学異方性膜形成用組成物の塗膜を形成した際に、ポリマー支持体の添加剤由来の成分の光異性化組成物層への過度な抽出が生じたことが理由であると推測される。この結果、得られる光学フィルムは、光異性化組成物層の液晶化合物の配向状態の均一性に劣ると考えられる。
(ポジティブCプレート膜1の作製)
特開2015-200861号公報の[0124]段落に記載に記載されたポジティブCプレートと同様の方法で、形成用仮支持体上にポジティブCプレート膜C-1を有するフィルムを作製した。ただし、Rth(550)が-69nmとなるように、ポジティブCプレートの厚みは制御した。
実施例1の光学フィルム1の光学異方性膜上に粘着剤層を設け、偏光板と貼合させた後セルロースアシレートフィルム1を剥離除去して、偏光板と光学異方性膜とが粘着剤で積層された積層体を作製した。さらに、光学異方性膜側に、粘着剤を介して上記で作製したポジティブCプレート膜C-1を転写し、形成用仮支持体は除去し、円偏光板1を得た。
実施例1の光学フィルムに代えて実施例2、4、5、6の光学フィルム2、4、5、6を用いた以外は円偏光板1と同様にして、円偏光板2、4、5、6をそれぞれ作製した。
実施例3の光学フィルム3の光学異方性膜側に、粘着剤を介して上記で作製したポジティブCプレート膜C-1を転写し、形成用仮支持体は除去した。また、光学積層体のセルロースアシレートフィルム1側に粘着剤を介して偏光板を貼り合わせて円偏光板3を得た。
次に、有機ELパネル搭載のSAMSUNG社製GALAXY SIIを分解し、円偏光板を剥離して、上記で作製した円偏光板1~6を、ポジティブCプレート側がパネル側となるよう粘着剤を介して貼合し、それぞれに対応する表示装置を作製した。
得られた表示装置に白表示、黒表示、画像表示をして、極角60度から蛍光灯を映し込んだときの反射光を観察したところ、いずれの円偏光板を用いた表示装置も黒浮きが全くなく、黒表示時のパネル色味はニュートラルであり、表示装置として極めて優れたものであった。
3、12 光学異方性膜
2、14 光配向膜
1、16 ポリマー支持体
11 光学異方性膜の光配向膜側の境界領域
13 光配向膜と光学異方性膜との界面
15 光配向膜の光学異方性膜側の境界領域
18 ポジティブCプレート
20 偏光板
22 偏光子
30 光学フィルムの製造工程
31、39 ロール
32、35 ダイ
33、36 加熱装置
34、37 光源
38 バックアップロール
Claims (9)
- 添加剤を含むポリマー支持体、光配向膜、及び光学異方性膜をこの順に積層してなる光学フィルムであって、
前記光学異方性膜は、逆波長分散性の重合性液晶化合物を含む重合性液晶組成物から形成されており、
前記光配向膜において前記光学異方性膜との境界領域に含まれる、前記ポリマー支持体の添加剤に由来する成分の量が光配向膜全質量に対して0.10~0.50質量%である、光学フィルム。 - 前記逆波長分散性の重合性液晶化合物が、下記一般式(1)で表される化合物である、請求項1に記載の光学フィルム。
L1-SP1-(E3-A1)m-E1-G1-D1-Ar1-D2-G2-E2-(A2-E4)n-SP2-L2 ・・・(1)
式(1)中、D1、D2、E1、E2、E3及びE4は、それぞれ独立に、単結合、-CO-O-、-C(=S)O-、-CR1R2-、-CR1R2-CR3R4-、-O-CR1R2-、-CR1R2-O-CR3R4-、-CO-O-CR1R2-、-O-CO-CR1R2-、-CR1R2-O-CO-CR3R4-、-CR1R2-CO-O-CR3R4-、-NR1-CR2R3-、又は-CO-NR1-を表す。R1、R2、R3及びR4は、それぞれ独立に、水素原子、フッ素原子、又は炭素数1~4のアルキル基を表す。
G1及びG2は、それぞれ独立に、置換基を有していてもよい炭素数5~8の2価の脂環式炭化水素基を表し、前記脂環式炭化水素基を構成する-CH2-の1個以上が-O-、-S-、又はNH-で置換されていてもよい。
A1及びA2は、それぞれ独立に、置換基を有していてもよい炭素数6~12の2価の芳香族炭化水素基、又は置換基を有していてもよい炭素数5~8の2価の脂環式炭化水素基を表し、前記脂環式炭化水素基を構成する-CH2-の1個以上が-O-、-S-、又はNH-で置換されていてもよい。
SP1及びSP2は、それぞれ独立に、単結合、炭素数1~12の直鎖状若しくは分岐鎖状のアルキレン基、又は、炭素数1~12の直鎖状若しくは分岐鎖状のアルキレン基を構成する-CH2-の1個以上が-O-、-S-、-NH-、-N(Q)-、若しくは-CO-に置換された2価の連結基を表し、Qは、置換基を表す。
L1及びL2は、それぞれ独立に1価の有機基を表し、L1及びL2の少なくとも一方は重合性基を表す。ただし、Ar1が、下記式(Ar-3)で表される芳香環である場合、L1及びL2並びに下記式(Ar-3)中のL3及びL4の少なくとも1つが重合性基を表す。
mは、0~2の整数を表し、mが2である場合、複数のE3は、それぞれ同一であっても異なっていてもよく、複数のA1は、それぞれ同一であっても異なっていてもよい。
nは、0~2の整数を表し、nが2である場合、複数のE4は、それぞれ同一であっても異なっていてもよく、複数のA2は、それぞれ同一であっても異なっていてもよい。
Ar1は、下記式(Ar-1)~式(Ar-5)で表される基からなる群から選択されるいずれかの芳香環を表す。
Q1は、N又はCHを表す。
Q2は、-S-、-O-、又は、-N(R5)-を表し、R5は、水素原子又は炭素数1~6のアルキル基を表す。
Y1は、置換基を有してもよい炭素数6~12の芳香族炭化水素基、又は置換基を有してもよい炭素数3~12の芳香族複素環基を表す。
Z1、Z2、及びZ3は、それぞれ独立に、水素原子、炭素数1~20の1価の直鎖状又は分岐鎖状の脂肪族炭化水素基、炭素数3~20の1価の脂環式炭化水素基、炭素数6~20の1価の芳香族炭化水素基、ハロゲン原子、シアノ基、ニトロ基、-OR6、-NR7R8、-SR9、-COORX、又は-OCORYを表し、R6~R9、RX、及びRYは、それぞれ独立に、水素原子又は炭素数1~6のアルキル基を表し、Z1及びZ2は、互いに結合して芳香環を形成してもよい。
A3及びA4は、それぞれ独立に、-O-、-N(R10)-、-S-、及び-CO-からなる群から選択される基を表し、R10は、水素原子又は置換基を表す。
Xは、水素原子、又は置換基が結合していてもよい第14~16族の非金属原子を表す。
D3及びD4は、それぞれ独立に、単結合、-CO-O-、-C(=S)O-、-CR1R2-、-CR1R2-CR3R4-、-O-CR1R2-、-CR1R2-O-CR3R4-、-CO-O-CR1R2-、-O-CO-CR1R2-、-CR1R2-O-CO-CR3R4-、-CR1R2-CO-O-CR3R4-、-NR1-CR2R3-、又は-CO-NR1-を表す。R1、R2、R3、及びR4は、それぞれ独立に、水素原子、フッ素原子、又は炭素数1~4のアルキル基を表す。
SP3及びSP4は、それぞれ独立に、単結合、炭素数1~12の直鎖状若しくは分岐鎖状のアルキレン基、又は、炭素数1~12の直鎖状若しくは分岐鎖状のアルキレン基を構成する-CH2-の1個以上が-O-、-S-、-NH-、-N(Q)-、若しくは、-CO-に置換された2価の連結基を表し、Qは、置換基を表す。
L3及びL4は、それぞれ独立に1価の有機基を表し、L3及びL4並びに前記式(1)中のL1及びL2の少なくとも1つが重合性基を表す。
Axは、芳香族炭化水素環及び芳香族複素環からなる群から選ばれる少なくとも1つの芳香環を有する、炭素数2~30の有機基を表す。
Ayは、水素原子、置換基を有していてもよい炭素数1~12のアルキル基、又は、芳香族炭化水素環及び芳香族複素環からなる群から選択される少なくとも1つの芳香環を有する、炭素数2~30の有機基を表す。
Ax及びAyにおける芳香環は、置換基を有していてもよく、AxとAyとが結合して環を形成していてもよい。
Q3は、水素原子、又は、置換基を有していてもよい炭素数1~6のアルキル基を表す。 - 前記光配向膜が、
架橋性基を含む重合体と、シンナメート基を有する低分子化合物と、を含む光配向膜形成用組成物から形成されるか、又は、
架橋性基及び光配向性基を含む重合体を含む光配向膜形成用組成物から形成される、請求項1又は2に記載の光学フィルム。 - 前記ポリマー支持体が、添加剤を含むセルロースアシレートフィルムである、請求項1~3のいずれか1項に記載の光学フィルム。
- 前記添加剤が、ポリエステル化合物又は糖エステル化合物である、請求項4に記載の光学フィルム。
- 前記ポリマー支持体のRe(550)が0~10nmであり、Rth(550)が-10~15nmである、請求項4又は5に記載の光学フィルム。
- 前記光学異方性膜が、前記光配向膜に対して剥離可能に設けられている、請求項1~6のいずれか1項に記載の光学フィルム。
- 請求項1~7のいずれか1項に記載の光学フィルムと、偏光子とを有する、偏光板。
- 請求項1~7のいずれか1項に記載の光学フィルム、又は請求項8に記載の偏光板を有する、画像表示装置。
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