WO2015019929A1 - 偏光板、それを具備した液晶表示装置 - Google Patents
偏光板、それを具備した液晶表示装置 Download PDFInfo
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- WO2015019929A1 WO2015019929A1 PCT/JP2014/070157 JP2014070157W WO2015019929A1 WO 2015019929 A1 WO2015019929 A1 WO 2015019929A1 JP 2014070157 W JP2014070157 W JP 2014070157W WO 2015019929 A1 WO2015019929 A1 WO 2015019929A1
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- optical film
- polarizing plate
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
Definitions
- the present invention relates to a polarizing plate and a liquid crystal display device including the polarizing plate. More specifically, the present invention relates to a polarizing plate in which generation of color unevenness and point defects is suppressed, and a liquid crystal display device including the polarizing plate.
- a liquid crystal display device is generally composed of a liquid crystal cell in which a transparent electrode, a liquid crystal layer, a color filter and the like are sandwiched between glass plates, and two polarizing plates provided on both sides thereof. Each polarizing plate is usually configured by sandwiching a polarizer between two transparent resin films.
- a liquid crystal display device has a major drawback that the viewing angle dependency of a display image is large.
- a wide viewing angle liquid crystal mode such as a VA mode has been put into practical use, and thereby, a high-quality image such as a television can be obtained.
- the demand for liquid crystal display devices is expanding rapidly.
- the liquid crystal cell in the non-driven state is aligned with the liquid crystal molecules of the liquid crystal cell perpendicular to the substrate. Pass through. For this reason, by arranging the linearly polarizing plates so that the absorption axes are orthogonal to each other above and below the liquid crystal panel, almost complete black display can be obtained when viewed from the front, and a high contrast ratio can be obtained. .
- the inner (liquid crystal cell side) resin film is a film having an optical compensation function, and the outer resin film on the side far from the liquid crystal cell.
- a cellulose acylate film is conventionally known as such a resin film.
- the cellulose acylate film is thinned for this purpose, there arises a problem that the mechanical strength is lowered and the moisture permeability becomes high as a protective film.
- the optical compensation film has a problem that the phase difference value largely fluctuates with respect to environmental humidity fluctuations.
- Patent Document 1 proposes a technique using polyethylene terephthalate (PET) as a protective film for a polarizing plate.
- Patent Document 2 proposes a technique using a norbornene resin as a retardation film.
- Patent Document 3 the resin film outside the polarizing plate is made of acrylic resin, and the resin film inside the polarizing plate (liquid crystal cell side) is made of a cellulose-based resin film so that moisture in the external environment is moderate
- a technique is disclosed that absorbs or discharges, prevents moisture from accumulating inside the polarizing plate, and suppresses defects caused by moisture.
- the present invention has been made in view of the above problems and situations, and a problem to be solved is to provide a polarizing plate in which the occurrence of color unevenness and point defects is suppressed. Moreover, it is providing the liquid crystal display device provided with it.
- the present inventor used a protective film having low moisture permeability on the outside of the polarizing plate, and cellulose resin on the inner side (liquid crystal cell side) of the polarizing plate. It has been found that the above-mentioned problems can be solved by using a compound having a specific structure having a biphenyl skeleton and an ether structure, an ester structure or an amide structure together with an acylate resin.
- An optical film A, a polarizer and an optical film B are polarizing plates laminated in this order, and the optical film A is an optical film containing at least one of an acrylic resin or a polyester resin, and the optical film B is a retardation film containing a cellulose acylate resin having an acyl group substitution degree in the range of 2.1 to 3.0 and a compound having a structure represented by the following general formula (1).
- a characteristic polarizing plate is polarizing plates laminated in this order, and the optical film A is an optical film containing at least one of an acrylic resin or a polyester resin, and the optical film B is a retardation film containing a cellulose acylate resin having an acyl group substitution degree in the range of 2.1 to 3.0 and a compound having a structure represented by the following general formula (1).
- R 1 to R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
- R 5 and R 6 each independently represents an alkyl group having a substituent or a substituent.
- .L 1 represents an aromatic hydrocarbon ring which may have a group.
- the substituent is at least one epoxy group, hydroxy group, an alkoxy group, selected from the group consisting of acyloxy group and an aromatic group
- L 2 represents O, C ( ⁇ O) O or C ( ⁇ O) NR, wherein R represents a hydrogen atom or an alkyl group.
- the retardation value Ro in the in-plane direction and the retardation value Rt in the thickness direction of the optical film B are within the following ranges, respectively, in an environment of 23 ° C. and 55% RH.
- the compound having the structure represented by the general formula (1) is a compound having a structure represented by the following general formula (2), any one of items 1 to 5
- R 1 to R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
- R 5 and R 6 each independently represents an alkyl group having a substituent or a substituent.
- An aromatic hydrocarbon ring which may have a group, wherein the substituent is at least one selected from the group consisting of an epoxy group, a hydroxy group, an alkoxy group, an acyloxy group and an aromatic group. 7).
- the water vapor permeability at 40 ° C. and 90% RH of the optical film A is in the range of 20 to 120 g / m 2 ⁇ 24 hr, wherein the optical film A is any one of items 1 to 6 Polarizing plate.
- the nitrogen-containing retardation increasing agent is at least one selected from compounds having a carbazole ring, a quinoxaline ring, a benzoxazole ring, an oxadiazole ring, an oxazole ring, a triazole ring, and a pyrazole ring.
- Item 10 The polarizing plate according to item 9.
- a liquid crystal display device comprising the polarizing plate according to any one of items 1 to 11.
- the above-mentioned means of the present invention can provide a polarizing plate in which the occurrence of color unevenness and point defects is suppressed.
- a liquid crystal display device including the same can be provided.
- the outer resin film (protective film) is a film with low moisture permeability
- the inner resin film (retardation film) is a film with high moisture permeability such as cellulose acylate resin.
- the outer resin film (protective film) can also reduce the influence of moisture from the outside, and has the effect of suppressing the occurrence of color unevenness. Therefore, in the present invention, it is considered that both of the color unevenness and the point-like defect of the display device that have been difficult to achieve both of the conventional methods can be solved.
- the polarizing plate of the present invention is a polarizing plate in which an optical film A, a polarizer, and an optical film B are laminated in this order, and the optical film A contains at least one of an acrylic resin or a polyester resin.
- the optical film B includes a cellulose acylate resin having an acyl group substitution degree of 2.1 to 3.0 and a compound having a structure represented by the general formula (1). It is a retardation film. This feature is a technical feature common to the inventions according to claims 1 to 12.
- the cellulose acylate resin contained in the optical film B is preferably a cellulose acetate resin having an acetyl group substitution degree in the range of 2.1 to 2.7. Further, a cellulose acetate resin having an acetyl group substitution degree in the range of 2.6 to 2.7 is preferable.
- the compound having a structure represented by the general formula (1) is a compound having a structure represented by the general formula (2).
- the water vapor permeability of the optical film A at 40 ° C. and 90% RH is preferably in the range of 20 to 120 g / m 2 ⁇ 24 hr.
- the optical film B preferably contains a nitrogen-containing retardation increasing agent, and the nitrogen-containing retardation increasing agent is a carbazole ring, quinoxaline ring, benzoxazole ring, oxadiazole ring, oxazole ring, triazole ring. And at least one selected from compounds having a pyrazole ring.
- the polarizing plate of the present invention can be suitably provided in a liquid crystal display device.
- ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
- the polarizing plate of the present invention is a polarizing plate in which an optical film A, a polarizer, and an optical film B are laminated in this order, and the optical film A contains at least one of an acrylic resin or a polyester resin.
- the optical film B includes a cellulose acylate resin having an acyl group substitution degree of 2.1 to 3.0 and a compound having a structure represented by the general formula (1). It is a retardation film.
- the optical film A is preferably a resin film outside the polarizing plate and functions as a protective film for the polarizing plate.
- the optical film B is preferably a resin film on the inner side (liquid crystal cell side) of the polarizing plate, and functions as a retardation film.
- an inner resin film As an inner resin film (retardation film), a compound having a structure represented by the general formula (1) having a biphenyl skeleton and an ether structure, an ester structure or an amide structure is allowed to coexist with the cellulose acylate resin, thereby making this compound. It is considered that the ether structure, ester structure or amide structure portion of this has an interaction with the side chain and hydrogen atom of the cellulose acylate resin, and the interaction between the cellulose acylate resin and water is weakened. In addition, the hydrophobic structure of the biphenyl skeleton is considered to further weaken the interaction between the cellulose acylate resin and water and suppress the occurrence of phase difference fluctuations due to fluctuations in environmental humidity.
- the outer resin film (protective film) is a film with low moisture permeability
- the inner resin film (retardation film) is a film with high moisture permeability such as cellulose acylate resin.
- the outer resin film (protective film) can also reduce the influence of moisture from the outside, and has the effect of suppressing the occurrence of color unevenness. Therefore, in the present invention, it is considered that both of the color unevenness and the point-like defect of the display device that have been difficult to achieve both of the conventional methods can be solved.
- the compound having a structure represented by the following general formula (1) is included in the optical film B.
- the polarizing plate is used in a liquid crystal display device, the occurrence of phase difference fluctuation due to fluctuations in environmental humidity is suppressed, and the occurrence of color unevenness is suppressed. Point-like defects due to accumulation of moisture can be suppressed. Furthermore, it can function as a phase difference increasing agent.
- R 1 to R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
- R 5 and R 6 each independently represents an alkyl group having a substituent or an aromatic hydrocarbon ring which may have a substituent.
- the substituent is at least one selected from the group consisting of an epoxy group, a hydroxy group, an alkoxy group, an acyloxy group, and an aromatic group.
- L 1 and L 2 represent O, C ( ⁇ O) O, or C ( ⁇ O) NR.
- R represents a hydrogen atom or an alkyl group.
- R 5 and R 6 each independently represents an alkyl group having a substituent or an aromatic hydrocarbon ring which may have a substituent. At this time, R 5 and R 6 may be the same or different.
- the substituent is at least one selected from the group consisting of an epoxy group, a hydroxy group, an alkoxy group, an acyloxy group, and an aromatic group.
- the acyloxy group is represented by the formula: —O—C ( ⁇ O) —R, wherein R is a linear or branched alkyl group having 1 to 8 carbon atoms or an aromatic group.
- the alkyl group and aromatic group are as defined below.
- R 5 and R 6 are aromatic hydrocarbon rings, they are preferably benzene rings.
- an alkoxy group and an acyloxy group are preferable.
- the alkoxy group preferably has an alkyl chain having 1 to 3 carbon atoms, more preferably a methoxy group.
- the acyloxy group is preferably an acetic acid group or a propionate group.
- R 5 and R 6 are preferably an alkyl group having a substituent.
- the substituent for the alkyl group in R 5 and R 6 preferably has an epoxy group, an acyloxy group, or a hydroxy group.
- the epoxy group is preferably unsubstituted.
- the alkyl group as R 5 and R 6 is not particularly limited, but is methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group. And a linear or branched alkyl group having 1 to 8 carbon atoms such as neopentyl group, hexyl group, heptyl group and octyl group. Among these, an alkyl group having 1 to 5 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable.
- the aromatic group may be an aromatic hydrocarbon ring group having 6 to 24 carbon atoms. More specifically, a phenyl group, p-tolyl group, naphthyl group, biphenyl group, fluorenyl group, anthryl group, pyrenyl group, azulenyl group, acenaphthylenyl group, terphenyl group, phenanthryl group and the like can be mentioned. Of these, a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.
- the aromatic ring group may have a substituent.
- the aromatic group is phenyl group, methylphenyl group, methylphenylphenyl. It is preferably a group.
- L 1 and L 2 represent O, C ( ⁇ O) O, or C ( ⁇ O) NR.
- R represents a hydrogen atom or an alkyl group.
- the alkyl group is not particularly limited, but an alkyl group having 1 to 5 carbon atoms is preferable.
- the compounds described in JP2011-140637A and JP2011-116912A have a structure represented by the general formula (2). Included in the compound. More specifically, the following is mentioned as a more preferable example of the compound which has a structure represented by General formula (2). In addition, a compound is prescribed
- each R independently represents a hydrogen atom (H), an acetic acid group (OAc) or a propionate group (OPr).
- the content of the compound having a structure represented by the general formula (1), the general formula (2), or the general formula (1a) is not particularly limited.
- the content of the compound having the structure represented by the general formula (1), the general formula (2) or the general formula (1a) is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the cellulose acylate resin, for example. More preferably, it is 1 to 20 parts by mass, particularly preferably 2 to 10 parts by mass.
- the compound that forms the optical film B may be added as a powder. After dissolving in a solvent, it may be added to the resin forming the retardation film.
- the water vapor permeability of the optical film A at 40 ° C. and 90% RH is preferably in the range of 20 to 120 g / m 2 ⁇ 24 hr.
- the water vapor permeability can be measured by a method based on JIS K 7129 (1992).
- acrylic resin An acrylic resin means a (meth) acrylic resin and is a concept including both an acrylic resin and a methacrylic resin. Hereinafter, the acrylic resin will be described.
- the acrylic resin is a (meth) acrylic resin, and means a polymer of acrylic acid ester or methacrylic acid ester.
- the polymer of the methacrylic acid ester for example, a polymer composed mainly of an alkyl methacrylate is preferable.
- the monomer composition of the alkyl methacrylate is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more, based on a total of 100% by mass of all monomers. And alkyl methacrylate is 99% by mass or less.
- the monomer other than alkyl methacrylate may be a monofunctional monomer having one polymerizable carbon-carbon double bond in the molecule, or two or more polymerizable carbons in the molecule.
- -It may be a polyfunctional monomer having a carbon double bond.
- monofunctional monomers are preferably used, and examples thereof include alkyl acrylates such as methyl acrylate and ethyl acrylate, and further, such as styrene and alkyl styrene as long as the effects of the present invention are not impaired. Examples include styrene monomers and unsaturated nitriles such as acrylonitrile and methacrylonitrile.
- alkyl acrylate is used as a copolymerization component, the carbon number is usually 1-8.
- the acrylic resin preferably has no glutarimide derivative, glutaric anhydride derivative, lactone ring structure, or the like. These acrylic resins may not provide sufficient mechanical strength and heat-and-moisture resistance as an acrylic resin film.
- the weight average molecular weight of the acrylic resin is preferably in the range of 100,000 to 4000000.
- the weight average molecular weight of the acrylic resin according to the present invention can be measured by gel permeation chromatography.
- the measurement conditions are as follows.
- the rubber elastic particles are particles containing a rubber elastic body, and may be particles composed only of a rubber elastic body, or may be particles having a multilayer structure having a rubber elastic body layer.
- the rubber elastic body include olefin-based elastic polymers, diene-based elastic polymers, styrene-diene-based elastic copolymers, and acrylic-based elastic polymers.
- an acrylic elastic polymer is preferable from the viewpoint of surface hardness, light resistance, and transparency of the acrylic resin film.
- the rubber elastic particle containing the acrylic elastic polymer is preferably a particle having a multilayer structure having an acrylic elastic polymer layer, and a polymer mainly composed of alkyl methacrylate outside the acrylic elastic polymer. It may be a two-layer structure having the above-mentioned layer, or a three-layer structure having a polymer layer mainly composed of alkyl methacrylate inside the acrylic elastic polymer.
- the example of the monomer composition of the polymer mainly composed of alkyl methacrylate constituting the layer formed on the outside or inside of the acrylic elastic polymer is the same as the alkyl methacrylate previously mentioned as an example of the acrylic resin. This is the same as the monomer composition example of the main polymer.
- Such acrylic rubber elastic particles having a multilayer structure can be produced, for example, by the method described in Japanese Patent Publication No. 55-27576.
- the rubber elastic particles those having a number average particle diameter of 10 to 300 nm of the rubber elastic material contained therein can be used. Thereby, when an acrylic resin film is laminated
- the number average particle diameter of the rubber elastic body is preferably 50 nm or more and 250 nm or less.
- the rubber elastic particle in which the outermost layer is a polymer mainly composed of methyl methacrylate and the acrylic elastic polymer is encapsulated in the polymer when the rubber elastic particle is mixed with the base acrylic resin, the rubber elastic particle The outermost layer is mixed with the base acrylic resin. Therefore, in the cross section, when the acrylic elastic polymer is dyed with ruthenium oxide and observed with an electron microscope, the rubber elastic particles can be observed as particles excluding the outermost layer.
- the inner layer is an acrylic elastic polymer. The portion is dyed and observed as particles having a single layer structure.
- the center part of the innermost layer particle is not dyed, and only the acrylic elastic polymer part of the intermediate layer is dyed and observed as a two-layered particle.
- the number average particle diameter of the rubber elastic particles is, as described above, when the rubber elastic particles are mixed with the base resin and the cross section is dyed with ruthenium oxide, and is dyed in a substantially circular shape. It is the number average value of the diameters of the parts observed in FIG.
- the blending amount of the rubber elastic particles is not particularly limited. For example, 25 to 45% by mass of rubber elastic particles having a number average particle diameter of 10 to 300 nm are blended in a transparent acrylic resin. Those are preferred.
- the acrylic resin may be produced, for example, by obtaining rubber elastic particles and then polymerizing a monomer as a raw material of the acrylic resin in the presence thereof to produce a base acrylic resin, or rubber. After obtaining the elastic particles and the acrylic resin, they may be produced by mixing them by melt kneading or the like.
- the glass transition temperature Tg of the acrylic resin is preferably in the range of 80 to 120 ° C. Further, the acrylic resin preferably has a high surface hardness when formed into a film, specifically, a pencil hardness (load 500 g, conforming to JIS K 5600-5-4) of B or higher.
- the layer that can exist other than the layer of the acrylic resin composition is not particularly limited in its composition.
- it is an acrylic resin that does not contain rubber elastic particles or a layer of the composition. It may be a layer made of an acrylic resin in which the content of the rubber elastic body particles and the average particle diameter of the rubber elastic body in the rubber elastic body particles are outside the above-mentioned regulations.
- a two-layer or three-layer structure for example, a two-layer structure including an acrylic resin layer / an acrylic resin not containing rubber elastic particles or a layer of the composition thereof, or an acrylic resin.
- a three-layer structure comprising an acrylic resin not containing rubber elastic particles or a composition layer / acrylic resin composition layer may be employed. What is necessary is just to let the surface of the layer of an acrylic resin composition be a bonding surface with a polarizing film in the multilayered acrylic resin film.
- the content of each layer of the rubber elastic particles and the above compounding agent may be different from each other.
- a layer containing an ultraviolet absorber and / or an infrared absorber and a layer not containing an ultraviolet absorber and / or an infrared absorber may be laminated with this layer interposed therebetween.
- the content of the ultraviolet absorber in the acrylic resin composition layer may be higher than the content of the ultraviolet absorber in the acrylic resin or the composition layer containing no rubber elastic particles, Specifically, the former is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass, and the latter is preferably 0 to 1% by mass, more preferably 0 to 0.5% by mass.
- the acrylic resin film may be non-oriented or non-oriented, and may be drawn.
- the stretching treatment is not performed, the thickness of the polarizing plate is likely to increase because the thickness is increased.
- the handling property of the acrylic resin film is improved because the thickness is increased.
- Such an acrylic resin film can be obtained from an unstretched film (raw film) obtained by forming an acrylic resin composition.
- stretched it is easy to develop a phase difference, but stretching has an advantage that the thickness of the acrylic resin film is reduced and the rigidity is improved.
- the stretched film can be produced by stretching an unstretched film by an arbitrary method.
- the extrusion molding method for example, there is a method of forming a film in a state where the acrylic resin composition is sandwiched between two rolls. At this time, by varying the rigidity of the roll surface, it is possible to make one surface of the acrylic resin film smooth and the other surface rough.
- the extrusion molding method for example, there is a method of forming a film in a state where the acrylic resin composition is sandwiched between two metal rolls.
- the metal roll is preferably a mirror roll.
- the unstretched film excellent in surface smoothness can be obtained.
- the said acrylic resin composition should just be formed into a film after multilayer extrusion with another acrylic resin composition.
- the thickness of the unstretched film thus obtained is preferably 5 to 200 ⁇ m, more preferably 10 to 85 ⁇ m.
- the polyester resin that forms the optical film A is not particularly limited.
- the polyester film can be obtained by, for example, a method in which the above polyester resin is melt-extruded into a film shape and cooled and solidified with a casting drum to form a film.
- any of an unstretched film and a stretched film can be used.
- an unstretched film can be suitably used.
- a stretched film can be suitably used.
- a stretched film, particularly a biaxially stretched film, is also preferably used from the viewpoint of strength.
- Polyester film is more durable than TAC (triacetylcellulose) film, but unlike TAC film, it has birefringence, so when it is used as a polarizer protective film, it has a rainbow-like color when observed from an oblique direction. Unevenness occurs and image quality deteriorates.
- At least one of the optical films A containing a polyester resin is preferably a polyester film having a retardation in the in-plane direction of 3000 to 30000 nm.
- the polarizer protective film on the exit light side of the polarizing plate disposed on the exit light side with respect to the liquid crystal cell is preferably a film made of a polyester film having a retardation of 3000 to 30000 nm.
- the ratio value (Ro / Rt) of the in-plane retardation (Ro) and the thickness direction retardation (Rt) of the polyester film is preferably 0.2 or more.
- Such a polyester resin may be polyethylene terephthalate or polyethylene naphthalate, but may contain other copolymerization components. These resins are excellent in transparency and excellent in thermal and mechanical properties, and the retardation can be easily controlled by stretching.
- polyethylene terephthalate is the most suitable material because it has a large intrinsic birefringence and a relatively large retardation can be obtained even if the film is thin.
- the retardation can be obtained by measuring the refractive index and thickness in the biaxial direction, or by using a commercially available automatic birefringence measuring device such as KOBRA-21ADH (Oji Scientific Instruments). it can.
- the polyester film according to the present invention may be a uniaxially stretched film or a biaxially stretched film, but when the biaxially stretched film is used as a polarizer protective film, it is observed from directly above the film surface. Although no rainbow-like color unevenness is observed, rainbow-like color unevenness may be observed when observed from an oblique direction.
- This phenomenon is because the biaxially stretched film consists of refractive index ellipsoids having different refractive indexes in the running direction, width direction, and thickness direction, and the in-plane retardation is zero due to the light transmission direction inside the film. This is because there exists a direction in which the refractive index ellipsoid appears to be a perfect circle. Therefore, when the liquid crystal display screen is observed from a specific oblique direction, a point where the retardation in the in-plane direction becomes zero may occur, and rainbow-like color unevenness occurs concentrically around that point. Become.
- the present invention has biaxiality (biaxiality) in a range that does not substantially cause rainbow-like color unevenness or a range that does not cause rainbow-like color unevenness in the viewing angle range required for a liquid crystal display screen. It is preferable.
- the ratio of the retardation (retardation in the in-plane direction) value of the protective film to the retardation (Rt) value in the thickness direction It is preferable to control so that the value falls within a specific range.
- the smaller the difference between the in-plane retardation and the retardation in the thickness direction the more isotropic the birefringence action due to the observation angle, so the change in retardation due to the observation angle becomes smaller. For this reason, it is considered that rainbow-like color unevenness due to the observation angle hardly occurs.
- the ratio value (Ro / Rt) of the retardation in the in-plane direction and the retardation in the thickness direction of the polyester film according to the present invention is preferably 0.2 or more, more preferably 0.5 or more, and still more preferably 0. .6 or more.
- the ratio value (Ro / Rt) of the retardation in the in-plane direction to the retardation in the thickness direction is 2.0.
- the mechanical strength in the direction orthogonal to the orientation direction is significantly lowered as the film approaches a complete uniaxial (uniaxial symmetry) film.
- the ratio value (Ro / Rt) of the retardation in the in-plane direction and the retardation in the thickness direction of the polyester film according to the present invention is preferably 1.2 or less, more preferably 1.0 or less.
- the ratio value (Ro / Rt) between the retardation in the in-plane direction and the thickness direction phase difference need not be 2.0, 1.2 or less is sufficient. Even if the ratio is 1.0 or less, it is possible to satisfy the viewing angle characteristics (180 degrees left and right, 120 degrees up and down) required for the liquid crystal display device.
- the longitudinal stretching temperature and the transverse stretching temperature are preferably 80 to 130 ° C., particularly preferably 90 to 120 ° C.
- the longitudinal draw ratio is preferably 1.0 to 3.5 times, particularly preferably 1.0 to 3.0 times.
- the transverse draw ratio is preferably 2.5 to 6.0 times, and particularly preferably 3.0 to 5.5 times.
- the ratio of the longitudinal draw ratio and the transverse draw ratio In order to control the retardation within the above range, it is preferable to control the ratio of the longitudinal draw ratio and the transverse draw ratio. If the difference between the vertical and horizontal draw ratios is too small, it is difficult to increase the retardation, which is not preferable.
- setting the stretching temperature low is a preferable measure for increasing the retardation.
- the treatment temperature is preferably from 100 to 250 ° C., particularly preferably from 180 to 245 ° C.
- the thickness unevenness of the film is small. Since the stretching temperature and the stretching ratio greatly affect the thickness unevenness of the film, it is necessary to optimize the film forming conditions from the viewpoint of the thickness unevenness. In particular, when the longitudinal stretching ratio is lowered to increase the retardation, unevenness in the longitudinal thickness may be deteriorated. Since there is a region where the vertical thickness unevenness becomes extremely worse within a specific range of the draw ratio, it is desirable to set the film forming conditions outside this range.
- the stretching ratio, the stretching temperature, and the thickness of the film can be appropriately set.
- the higher the stretching ratio, the lower the stretching temperature, and the thicker the film the higher the retardation.
- the lower the stretching ratio, the higher the stretching temperature, and the thinner the film the lower the retardation.
- the thickness of the polyester film according to the present invention is arbitrary, but is preferably in the range of 15 to 300 ⁇ m, more preferably in the range of 15 to 200 ⁇ m. Even with a film thickness of less than 15 ⁇ m, it is possible in principle to obtain a retardation of 3000 nm or more. However, in that case, the anisotropy of the mechanical properties of the film becomes remarkable, and the film tends to be torn or torn, and the practicality as an industrial material may be lowered. A particularly preferable lower limit of the thickness is 25 ⁇ m. On the other hand, if the upper limit of the thickness of the polarizer protective film exceeds 300 ⁇ m, the thickness of the polarizing plate increases.
- the upper limit of the thickness is preferably 200 ⁇ m.
- a particularly preferable upper limit of the thickness is 100 ⁇ m, which is about the same as a general TAC film.
- polyethylene terephthalate is suitable as the polyester used as the film substrate.
- the optical film B is a retardation film containing a cellulose acylate resin having an acyl group substitution degree in the range of 2.1 to 3.0 and a compound having a structure represented by the general formula (1). .
- the cellulose acylate resin constituting the optical film B according to the present invention is a cellulose acylate resin having an acyl group substitution degree in the range of 2.1 to 3.0.
- Examples of the raw material cellulose include cotton linter and wood pulp (hardwood pulp, conifer pulp).
- Cellulose acylate obtained from any raw material cellulose can be used, and in some cases, it may be mixed and used.
- Detailed descriptions of these raw material celluloses can be found, for example, by Marusawa and Uda, “Plastic Materials Course (17) Fibrous Resin”, published by Nikkan Kogyo Shimbun (published in 1970), and the Japan Institute of Invention and Technology Publication No. 2001
- the cellulose described in No.-1745 pages 7 to 8) can be used.
- Optical film B is a cellulose acylate resin having an acyl group substitution degree in the range of 2.1 to 3.0.
- the cellulose acylate resin is preferably a cellulose acetate having an acetyl group substitution degree in the range of 2.1 to 2.7, more preferably a cellulose acetate having an acetyl group substitution degree in the range of 2.6 to 2.7. It is.
- the total substitution degree of acyl groups is preferably 2.1 to 3.0, more preferably 2.1 to 2.7 from the viewpoint of improving water resistance.
- the total substitution degree of acyl groups of cellulose acylate is 2.1 to 2.5. It is preferable.
- the cellulose acylate resin according to the present invention is preferably at least one selected from cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate benzoate, cellulose propionate, and cellulose butyrate.
- more preferred cellulose acylate resins are cellulose acetate, cellulose acetate propionate, and triacetyl cellulose.
- the degree of substitution of the acetyl group and the degree of substitution of other acyl groups can be determined by the method prescribed in ASTM-D817-96.
- the weight average molecular weight (Mw) of the cellulose acylate resin according to the present invention is preferably 75,000 or more, more preferably in the range of 75,000 to 300,000, still more preferably in the range of 100,000 to 24,000, and 160000. Those having a molecular weight of ⁇ 24,000 are particularly preferred. If the weight average molecular weight (Mw) of the cellulose acylate resin is 75000 or more, the self-film-forming property and adhesion improving effect of the cellulose acylate layer itself are exhibited, which is preferable. In the present invention, two or more kinds of cellulose acylate resins can be mixed and used.
- the retardation value Ro in the in-plane direction and the retardation value Rt in the thickness direction of the optical film B according to the present invention are preferably in the following ranges, respectively, in an environment of 23 ° C. and 55% RH. By setting the retardation value within such a range, a polarizing plate having good polarization characteristics can be obtained.
- the retardation value can be measured at an optical wavelength of 590 nm using an automatic birefringence meter KOBRA-21ADH (Oji Scientific Instruments).
- the optical film in an environment of 55% RH, for 3-dimensional refractive index measured at 10 points at a wavelength of 590 nm, the refractive indices n x, n y, the average value of n z
- the retardation value Ro in the in-plane direction and the retardation value Rt in the thickness direction can be calculated according to the following formulas (i) and (ii).
- n x represents a refractive index in the direction x in which the refractive index is maximized in the plane direction of the film.
- n y in-plane direction of the film, the refractive index in the direction y perpendicular to the direction x.
- nz represents the refractive index in the thickness direction z of the film.
- d represents the thickness (nm) of the film.
- the film thickness of the optical film B according to the present invention is preferably in the range of 10 to 90 nm. More preferably, it is in the range of 10 to 40 nm.
- the optical film B according to the present invention can contain a retardation increasing agent.
- the phase difference increasing agent is preferably a nitrogen-containing phase difference increasing agent.
- the nitrogen-containing retardation increasing agent is preferably at least one selected from compounds having a carbazole ring, a quinoxaline ring, a benzoxazole ring, an oxadiazole ring, an oxazole ring, a triazole ring, and a pyrazole ring. .
- the optical film B of the present invention preferably contains a compound represented by the following general formula (3) as a nitrogen-containing retardation increasing agent.
- a 1 , A 2 and B are each independently an alkyl group (methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group, 2-ethylhexyl). Group), a cycloalkyl group (cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group, etc.), an aromatic hydrocarbon ring or an aromatic heterocyclic ring.
- an aromatic hydrocarbon ring or an aromatic heterocyclic ring is preferable, and a 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring having a NICS value smaller than or equal to that of the benzene ring is particularly preferable.
- the NICS value is an index used for quantification of aromaticity by magnetic properties. If the ring is aromatic, the ring current effect strongly shields the center of the ring, and if the ring is antiaromatic, Shielded. Depending on the magnitude of the NICS value, it is possible to determine the strength of the ring current, that is, the degree of contribution of ⁇ electrons to the aromaticity of the ring.
- the aromatic compound represented by the general formula (3) having at least three specific aromatic rings having a specific NICS value and having the aromatic rings closely connected to each other is a water adsorbent such as cellulose acylate.
- the CH / ⁇ interaction functions between the CH portion of the resin and the ⁇ electron of the aromatic compound. Therefore, rather than the interaction between the water molecule and the water-soluble resin, the compound represented by the general formula (3) and the resin The interaction becomes stronger, and as a result, water can be prevented from entering between the water-adsorbing resin and the additive, and fluctuations in optical properties can be suppressed.
- the NICS value is calculated using Gaussian 03 (Revision B.03, US Gaussian software). Specifically, from the structure optimized using B3LYP (density functional method) as the calculation method and 6-31 + G (function in which the diffusion gauss function is added to the split valence basis set) as the basis function, the NMR shielding constant It is calculated by a calculation method (GIAO).
- GIAO a calculation method
- the structure of the 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring is not limited.
- the 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocycle which is a NICS value of the benzene ring represented by A 1 , A 2 and B may have a substituent.
- a halogen atom fluorine atom, chlorine atom, bromine atom, iodine atom, etc.
- alkyl group methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group, 2 -Ethylhexyl group etc.
- cycloalkyl group cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group etc.
- alkenyl group vinyl group, allyl group etc.
- cycloalkenyl group (2-cyclopenten-1-yl, 2 -Cyclohexen-1-yl group), alkynyl group (
- T 1 and T 2 preferably each independently represent a pyrrole ring, a pyrazole ring, an imidazole ring, a 1,2,3-triazole ring or a 1,2,4-triazole ring. .
- a pyrazole ring or a 1,2,4-triazole ring is preferable because a resin composition particularly excellent in the effect of suppressing fluctuation in optical properties and particularly excellent in durability can be obtained.
- the pyrazole ring, imidazole ring, 1,2,3-triazole ring or 1,2,4-triazole ring represented by T 1 and T 2 may be a tautomer. Specific structures of the pyrrole ring, pyrazole ring, imidazole ring, 1,2,3-triazole ring or 1,2,4-triazole ring are shown below.
- R 5 represents a hydrogen atom or a non-aromatic substituent.
- the non-aromatic substituent represented by R5 include the same groups as the non-aromatic substituent among the substituents that A1 in General Formula (3) may have.
- the substituent represented by R5 is an aromatic group-containing substituent, A 1 and T 1 or B and T 1 are easily twisted, and A 1 , B, and T 1 are CH / ⁇ mutual with the water adsorbent resin. Since it becomes impossible to form an action, it is difficult to suppress fluctuations in optical characteristics.
- R 5 is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an acyl group having 1 to 5 carbon atoms, and particularly preferably a hydrogen atom.
- T 1 and T 2 may have a substituent, and examples of the substituent include a substituent that A 1 and A 2 in the general formula (3) may have Similar groups can be mentioned.
- L 1 , L 2 , L 3 and L 4 each independently represent a single bond or a divalent linking group, and are 5 or 6 via 2 or less atoms. Membered aromatic hydrocarbon rings or aromatic heterocycles are linked.
- the term “via two or less atoms” refers to the minimum number of atoms existing between the connected substituents among the atoms constituting the linking group.
- the divalent linking group having 2 or less linking atoms is not particularly limited, but includes an alkylene group, an alkenylene group, an alkynylene group, O, (C ⁇ O), NR, S, and (O ⁇ S ⁇ O). It is a divalent linking group selected from the group consisting of or a linking group in which two of them are combined.
- R represents a hydrogen atom or a substituent.
- substituent represented by R include an alkyl group (methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group, 2-ethylhexyl group, etc.), cycloalkyl group ( Cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group, etc.), aromatic hydrocarbon ring group (phenyl group, p-tolyl group, naphthyl group, etc.), aromatic heterocyclic group (2-furyl group, 2-thienyl group, etc.) Group, 2-pyrimidinyl group, 2-benzothiazolyl group, 2-pyridyl group, etc.), cyano group and the like.
- the divalent linking group represented by L 1 , L 2 , L 3 and L 4 may have a substituent, and the substituent is not
- L 1 , L 2 , L 3 and L 4 are CH / ⁇ mutual with the water-adsorbing resin by increasing the planarity of the compound represented by the general formula (3). Since the action becomes stronger and fluctuations in optical properties are suppressed, a single bond, or O, (C ⁇ O) —O, O— (C ⁇ O), (C ⁇ O) —NR or NR— (C ⁇ O), and more preferably a single bond.
- a 1 , A 2 , T 1 , T 2 , L 1 , L 2 , L 3 and L 4 are respectively A 1 , A 2 , T 1 , T 2 , L in the general formula (3).
- 1, L 2, L 3 and L 4 as synonymous .A 3 and T 3, .L 5 and L 6 represent the same group as a 1 and T 1 in the general formula (3), respectively, the general And represents the same group as L 1 in Formula (3)
- Q 1 , Q 2 , Q 3 and Q 4 represent a carbon atom or a nitrogen atom
- m represents an integer of 0 to 4.
- a smaller m is more compatible with cellulose acylate, and therefore m is preferably an integer of 0 to 2, more preferably an integer of 0 to 1.
- the triazole compound having a structure represented by the general formula (3.1) is preferably a triazole compound having a structure represented by the following general formula (3.2).
- Z represents the structure of the following general formula (3.2a).
- Q represents an integer of 2 to 3.
- At least two Zs represent at least one Z substituted on a benzene ring. Bonded to ortho or meta position.
- R 10 represents a hydrogen atom, an alkyl group or an alkoxy group.
- P represents an integer of 1 to 5.
- * represents a bonding position with a benzene ring.
- T 1 represents a 1,2,4-triazole ring.
- the compound represented by the general formula (3), (4), (3.1) or (3.2) may form a hydrate, a solvate or a salt.
- the hydrate may contain an organic solvent
- the solvate may contain water. That is, “hydrate” and “solvate” include mixed solvates containing both water and organic solvents. Salts include acid addition salts formed with inorganic or organic acids.
- inorganic acids include, but are not limited to, hydrohalic acids (hydrochloric acid, hydrobromic acid, etc.), sulfuric acid, phosphoric acid, and the like.
- organic acids include acetic acid, trifluoroacetic acid, propionic acid, butyric acid, oxalic acid, citric acid, benzoic acid, alkylsulfonic acid (methanesulfonic acid, etc.), allylsulfonic acid (benzenesulfonic acid, 4-toluene) Sulfonic acid, 1,5-naphthalenedisulfonic acid, and the like), but are not limited thereto.
- hydrochloride, acetate, propionate and butyrate are preferable.
- salts are those in which the acidic moiety present in the parent compound is a metal ion (eg, an alkali metal salt, such as sodium or potassium salt, an alkaline earth metal salt, such as calcium or magnesium salt, an ammonium salt, an alkali metal ion, alkaline earth And salts formed when substituted with organic bases (ethanolamine, diethanolamine, triethanolamine, morpholine, piperidine, etc.) It is not limited. Of these, sodium salts and potassium salts are preferred.
- a metal ion eg, an alkali metal salt, such as sodium or potassium salt, an alkaline earth metal salt, such as calcium or magnesium salt, an ammonium salt, an alkali metal ion, alkaline earth
- organic bases ethanolamine, diethanolamine, triethanolamine, morpholine, piperidine, etc.
- sodium salts and potassium salts are preferred.
- Examples of the solvent contained in the solvate include any common organic solvent. Specifically, alcohol (eg, methanol, ethanol, 2-propanol, 1-butanol, 1-methoxy-2-propanol, t-butanol), ester (eg, ethyl acetate), hydrocarbon (eg, toluene, hexane) , Heptane), ether (eg, tetrahydrofuran), nitrile (eg, acetonitrile), ketone (acetone) and the like.
- alcohol eg, methanol, ethanol, 2-propanol, 1-butanol, 1-methoxy-2-propanol, t-butanol
- ester eg, ethyl acetate
- hydrocarbon eg, toluene, hexane
- Heptane Heptane
- ether eg, tetrahydrofuran
- nitrile
- solvates of alcohols eg, methanol, ethanol, 2-propanol, 1-butanol, 1-methoxy-2-propanol, t-butanol.
- solvents may be a reaction solvent used at the time of synthesizing the compound, a solvent used at the time of crystallization purification after synthesis, or a mixture thereof.
- two or more kinds of solvents may be included at the same time, or a form containing water and a solvent (for example, water and alcohol (for example, methanol, ethanol, t-butanol, etc.), etc.).
- a solvent for example, water and alcohol (for example, methanol, ethanol, t-butanol, etc.), etc.).
- the molecular weight of the compound represented by the general formula (3), (4), (3.1) or (3.2) is not particularly limited, but the smaller it is, the better the compatibility with the resin is.
- the value is preferably 150 to 2000, more preferably 200 to 1500, and more preferably 300 to 1000.
- the compound represented by the general formula (3) can be synthesized by a known method.
- any compound having a 1,2,4-triazole ring may be used, but there is a method of reacting a nitrile derivative or imino ether derivative with a hydrazide derivative. preferable.
- the solvent used for the reaction may be any solvent as long as it does not react with the raw material, but may be any ester type (eg, ethyl acetate, methyl acetate), amide type (dimethylformamide, dimethylacetamide, etc.), ether type (Ethylene glycol dimethyl ether, etc.), alcohols (eg, methanol, ethanol, propanol, isopropanol, n-butanol, 2-butanol, ethylene glycol, ethylene glycol monomethyl ether, etc.), aromatic hydrocarbons (eg, toluene, xylene, etc.) ), Water can be mentioned.
- an alcohol solvent is preferable. These solvents may be used as a mixture.
- the amount of the solvent used is not particularly limited, but is preferably in the range of 0.5 to 30 times the amount of the hydrazide derivative used, more preferably 1.0 to 25 times the amount. Yes, particularly preferably in the range of 3.0 to 20 times the amount.
- a catalyst When reacting a nitrile derivative and a hydrazide derivative, it is not necessary to use a catalyst, but it is preferable to use a catalyst in order to accelerate the reaction.
- a catalyst to be used an acid may be used and a base may be used.
- the acid include hydrochloric acid, sulfuric acid, nitric acid, acetic acid and the like, preferably hydrochloric acid.
- the acid may be added after diluted in water, or may be added by a method of blowing a gas into the system.
- Bases include inorganic bases (potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, potassium hydroxide, sodium hydroxide, etc.) and organic bases (sodium methylate, sodium ethylate, potassium methylate, potassium ethylate, Sodium butyrate, potassium butyrate, diisopropylethylamine, N, N′-dimethylaminopyridine, 1,4-diazabicyclo [2.2.2] octane, N-methylmorpholine, imidazole, N-methylimidazole, pyridine, etc.) Any of them may be used, and the inorganic base is preferably potassium carbonate, and the organic base is preferably sodium ethylate, sodium ethylate or sodium butyrate.
- the inorganic base may be added as a powder or may be added in a state dispersed in a solvent.
- the organic base may be added in a state dissolved in a solvent (for example, a
- the target product can be obtained by heating in a solvent.
- the addition method of the raw material, solvent and catalyst used for the reaction is not particularly limited, and the catalyst may be added last, or the solvent may be added last. Also preferred is a method of dispersing or dissolving a nitrile derivative in a solvent, adding a catalyst, and then adding a hydrazide derivative.
- the solution temperature during the reaction may be any temperature as long as the reaction proceeds, but is preferably in the range of 0 to 150 ° C., more preferably in the range of 20 to 140 ° C. Moreover, you may react, removing the water to produce
- any method may be used for treating the reaction solution, but when a base is used as a catalyst, a method of neutralizing the reaction solution by adding an acid is preferable.
- the acid used for neutralization include hydrochloric acid, sulfuric acid, nitric acid, and acetic acid. Acetic acid is particularly preferable.
- the amount of the acid used for neutralization is not particularly limited as long as the pH of the reaction solution is in the range of 4 to 9, but is preferably 0.1 to 3 moles, particularly preferably, relative to the base used. , In the range of 0.2 to 1.5 moles.
- the precipitate collected by filtration was dissolved in 80 ml of methanol, 300 ml of pure water was added, and acetic acid was added dropwise until the pH of the solution reached 7.
- the precipitated crystals were collected by filtration, washed with pure water, and blown dry at 50 ° C. to obtain 38.6 g of Exemplified Compound 1.
- the yield was 70% based on benzoylhydrazine.
- the 1 H-NMR spectrum of the obtained exemplary compound 176 is as follows. In order to avoid complication of chemical shift due to the presence of tautomers, the measurement was performed by adding a few drops of trifluoroacetic acid to the measurement solvent.
- the compound represented by the general formula (3) according to the present invention can be appropriately adjusted to be contained in the optical film, but the addition amount is a resin that forms the optical film (for example, cellulose acylate) ) To 1 to 15% by mass, and particularly preferably 2 to 10% by mass. If it is in this range, the fluctuation of the optical value depending on the change of the environmental humidity can be reduced without impairing the mechanical strength of the optical film of the present invention.
- the addition amount is a resin that forms the optical film (for example, cellulose acylate) ) To 1 to 15% by mass, and particularly preferably 2 to 10% by mass. If it is in this range, the fluctuation of the optical value depending on the change of the environmental humidity can be reduced without impairing the mechanical strength of the optical film of the present invention.
- the compound represented by the general formula (3) it may be added to the resin forming the optical film as a powder, or after being dissolved in a solvent, it is added to the resin forming the optical film. May be.
- Preferred examples of the retardation increasing agent include compounds having structures represented by the following general formulas (5) to (9).
- R represents an aliphatic alcohol group having 1 to 20 carbon atoms.
- R represents an aryl group having 6 to 20 carbon atoms, each containing or not containing a hetero atom.
- R ′ represents hydrogen or an aliphatic alkyl group having 1 to 20 carbon atoms.
- R represents a substituted or unsubstituted aliphatic group having 1 to 20 carbon atoms or a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms.
- R and R ′ each represent an aliphatic alkyl group having 1 to 20 carbon atoms. The difference in molecular weight between R and R ′ is 20 to 200.
- R ′′ represents an aliphatic alkyl group having 1 to 20 carbon atoms.
- the compound having the structure represented by the general formula (3) to the general formula (10) according to the present invention can be contained in the optical film B by adjusting the amount as appropriate.
- the content is preferably 1 to 15% by mass, particularly 2 to 10% by mass, based on the acylcellulose resin to be formed. If it is in this range, the fluctuation of the optical value depending on the change of the environmental humidity can be reduced without impairing the mechanical strength of the optical film of the present invention.
- additives may be used for the optical film B according to the present invention.
- additives include plasticizers, ultraviolet absorbers, fluorine-based surfactants, release agents, matting agents, deterioration preventing agents, optical anisotropy control agents, infrared absorbers, and the like. Can be used.
- a plasticizer may be used to impart flexibility to the optical film A, improve dimensional stability, and improve moisture resistance.
- the octanol / water partition coefficient (log P value) can be measured by a flask soaking method described in Japanese Industrial Standard (JIS) Z 7260-107 (2000).
- plasticizer to be added include low molecular to oligomeric compounds having a molecular weight of about 190 to 5000 within the above physical properties.
- phosphoric acid esters, carboxylic acid esters, polyol esters and the like are used.
- phosphate ester examples include triphenyl phosphate (TPP), tricresyl phosphate (TCP), cresyl diphenyl phosphate, octyl diphenyl phosphate, biphenyl diphenyl phosphate, trioctyl phosphate (TOP), tributyl phosphate and the like. Triphenyl phosphate and biphenyl diphenyl phosphate are preferable.
- plasticizers are liquid except for TPP (melting point: about 50 ° C.) at 25 ° C., and the boiling point is 250 ° C. or higher.
- Examples of other carboxylic acid esters include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters.
- Examples of glycolic acid esters include triacetin, tributyrin, butyl phthalyl butyl glycolate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, methyl phthalyl methyl glycolate, propyl phthalyl Examples include propyl glycolate, butyl phthalyl butyl glycolate, and octyl phthalyl octyl glycolate.
- Plasticizers described in publications and the like are also preferably used. According to these publications, there are many preferable descriptions regarding not only examples of plasticizers but also their usage or characteristics, and they are preferably used in the present invention.
- plasticizers include dipentaerythritol esters described in JP-A No. 11-124445, glycerol esters described in JP-A No. 11-246704, diglycerol esters described in JP-A No. 2000-63560, Citric acid esters described in Kaihei 11-92574, substituted phenyl phosphates described in JP-A-11-90946, ester compounds containing an aromatic ring and a cyclohexane ring described in JP-A 2003-165868, etc. Is preferably used.
- a polymer plasticizer having a resin component having a molecular weight of 1,000 to 100,000 is also preferably used.
- plasticizers may be used alone or in combination of two or more.
- the amount of the plasticizer to be added is generally 2 to 120 parts by weight with respect to 100 parts by weight of the thermoplastic resin contained in each dope, preferably 2 to 70 parts by weight, more preferably 2 to 30 parts by weight. In particular, 5 to 20 parts by mass is preferable.
- the dope used for forming the cellulose acylate layer used in the present invention is dope (A) and the dope used for forming the acrylic layer is dope (B)
- the dope used for forming the adjacent layer is It is preferable to use a common plasticizer from the viewpoint of less occurrence of disturbance at the dope interface during casting, better adhesion at the interface, and curl reduction.
- an ultraviolet absorber is preferably used from the viewpoint of preventing deterioration of the polarizing plate or liquid crystal cell due to light or the like.
- the ultraviolet absorber those which are excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less and have little absorption of visible light having a wavelength of 400 nm or more are preferably used from the viewpoint of good liquid crystal display properties.
- Specific examples of the ultraviolet absorber preferably used in the present invention include, for example, hindered phenol compounds, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex salts Compound etc. are mentioned.
- the amount of these ultraviolet light inhibitors added is preferably in the range of 1 ppm to 1.0% by weight, more preferably in the range of 10 to 1000 ppm, with respect to the polyester resin or acrylic resin.
- UV absorbers include UV-1 to UV-3 shown below, but UV absorbers applicable to the present invention are not limited to these.
- the optical film according to the present invention preferably contains 0.01% by mass to 20% by mass of an organic acid that satisfies the following requirements (1) to (3) with respect to the resin.
- (1) Includes a structure in which a polyhydric alcohol and a polycarboxylic acid are bonded by forming an ester bond.
- (2) The total number of molecules of the polyhydric alcohol and polycarboxylic acid forming the compound is 3 or more.
- an organic acid satisfying the above requirements (1) to (3) it is possible to improve the releasability from the solution film-forming equipment (the metal support when the dope is poured) by the unsubstituted carboxy group. Then, an organic acid satisfying the above requirements (1) to (3) can be used as a peeling accelerator.
- the unsubstituted carboxy group adheres to the metal surface of the support, and the polyhydric alcohol part or the hydrophobic group part substituted by the polyvalent alcohol part blocks the metal surface of the support from an oxidizing agent such as oxygen.
- an oxidizing agent such as oxygen.
- the polyvalent carboxylic acid used for the organic acid that satisfies the requirements (1) to (3) is not particularly limited, but for example, succinic acid, citric acid, tartaric acid, diacetyltartaric acid, malic acid, and adipic acid are preferable.
- the number of polyvalent carboxylic acid molecules is preferably 1 to 20, more preferably 1 to 15, and more preferably 1 to 10. Particularly preferred.
- the number of molecules of the polyhydric alcohol is preferably 1 to 20, more preferably 1 to 15, and particularly preferably 1 to 10. preferable.
- the organic acid satisfying the above requirements (1) to (3) is a monovalent acid having a substituent having 4 or more carbon atoms. It may have a structure in which an ester bond is formed with a part of the hydroxy group of the polyhydric alcohol.
- Specific examples of the monovalent acid having a substituent having 4 or more carbon atoms are given below.
- the substituent in the monovalent acid having a substituent having 4 or more carbon atoms means R when the monovalent acid having a substituent having 4 or more carbon atoms is represented as RCOOH.
- fatty acid Caproic acid, heptylic acid, caprylic acid, pelargonic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, ricinolenic acid, undecanoic acid.
- Alkyl sulfate Myristyl sulfate, cetyl sulfate, oleyl sulfate.
- Alkylbenzene sulfonic acid Dodecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid.
- Alkyl naphthalene sulfonic acid Sesquibutyl naphthalene sulfonic acid, diisobutyl naphthalene sulfonic acid.
- a monovalent acid having a substituent having 4 or more carbon atoms which is a fatty acid, is preferable, caprylic acid, lauric acid, stearic acid, and oleic acid are more preferable, and oleic acid is particularly preferable.
- the number of molecules of the monovalent acid having a substituent having 4 or more carbon atoms is preferably 0 to 4, and preferably 0 to 3. More preferably, 0 to 2 is particularly preferable.
- the organic acid satisfying the requirements (1) to (3) preferably has a total number of molecules of polyhydric alcohol and polycarboxylic acid forming the compound of 3 or more, preferably 3 to 30. More preferably, it is ⁇ 20.
- the ratio of the polyvalent carboxylic acid, the polyhydric alcohol, and the monovalent acid having a substituent having 4 or more carbon atoms in the organic acid that satisfies the requirements (1) to (3) is not particularly limited. Two or more unsubstituted hydroxyl groups may remain, or an unsubstituted hydroxyl group may remain.
- the organic acid that satisfies the requirements (1) to (3) has at least one unsubstituted carboxy group derived from a polyvalent carboxylic acid, and has 1 to 40 unsubstituted carboxy groups derived from the polyvalent carboxylic acid. It is preferable to have 1 to 30.
- the organic acid that satisfies the requirements (1) to (3) may be used alone or as a mixture.
- the organic acid that satisfies the requirements (1) to (3) may be ionized depending on the case, and may form a salt with any metal ion depending on the case.
- An organic acid (partial condensate of organic acid) having the following composition is preferable.
- the amount of the organic acid that satisfies the requirements (1) to (3) contained in the optical film according to the present invention is 0.01 to 20% by mass with respect to the resin, and 0.05 to 10 It is particularly preferable that the content is 1% by mass, and more preferable is 0.1 to 5% by mass. Note that the amount of the organic acid that satisfies the requirements (1) to (3) described above is such that when the organic acid that satisfies the requirements (1) to (3) is a mixture, all of the above (1) to (3) It means the total amount of organic acid that satisfies the requirement 3).
- the added amount is 0.001% or more, the polarizer durability improving effect and the peelability improving effect are sufficient.
- An addition amount of 20% by mass or less is preferable because the organic acid hardly bleeds out at a high temperature and high humidity, and the orthogonal transmittance of the polarizing plate hardly increases.
- the releasability can be achieved even at an addition amount of about 0.001 to 0.01% by combining with a peelability improving technique such as cooling of the peeling part of the casting support. Improvement can be expected.
- fine particles are generally added from the viewpoint of imparting scratch resistance and smooth transportability when handled. They are generally called matting agents, anti-blocking agents or anti-scratching agents and are conventionally used. They are not particularly limited as long as they exhibit the above-mentioned functions, and the matting agent may be an inorganic matting agent composed of an inorganic compound or an organic matting agent composed of an organic compound. Good.
- Preferred examples of the inorganic matting agent composed of an inorganic compound include inorganic compounds containing silicon (for example, silicon dioxide, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, etc.), titanium oxide, Preferred are zinc oxide, aluminum oxide, barium oxide, zirconium oxide, strontium oxide, antimony oxide, tin oxide, tin oxide / antimony, calcium carbonate, talc, clay, calcined kaolin and calcium phosphate, and more preferably inorganic compounds containing silicon.
- silicon dioxide is particularly preferably used from the viewpoint of reducing the turbidity (also referred to as haze) of the optical film.
- silicon dioxide fine particles for example, commercially available products having trade names such as Aerosil R972, R974, R812, 200, 300, R202, OX50, TT600 (above, manufactured by Nippon Aerosil Co., Ltd.) can be used.
- fine particles of zirconium oxide for example, those commercially available under trade names such as Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) can be used.
- the fine particle comprised from polymers such as a silicone resin, a fluororesin, and an acrylic resin, for example is preferable
- silicone resins those having a three-dimensional network structure are particularly preferable.
- Tospearl 103, Tospearl 105, Tospearl 108, Tospearl 120, Tospearl 145, Tospearl 3120, and Tospearl 240 (above, manufactured by Toshiba Silicone Co., Ltd.) ) Etc. can be used.
- the method is not particularly limited, and any method can be used as long as a desired resin solution can be prepared.
- the matting agent may be contained in the step of mixing the resin and the solvent, or the matting agent may be added after preparing the mixed solution with the resin and the solvent.
- the dope containing the resin may be added and mixed immediately before casting, which is a so-called immediately preceding addition method, and the mixing is used by installing a screw-type kneading member online.
- a static mixer such as an in-line mixer is preferable, and as the in-line mixer, for example, a static mixer SWJ (Toray stationary in-pipe mixer Hi-Mixer, manufactured by Toray Engineering Co., Ltd.) Is preferred.
- SWJ Toray stationary in-pipe mixer Hi-Mixer, manufactured by Toray Engineering Co., Ltd.
- the optical film according to the present invention is a laminated film composed of a core layer and a skin layer
- the fact that the layer located in at least one of the outermost layers contains a matting agent indicates that the film surface has a scratch resistance and a wide width due to a reduction in the coefficient of friction.
- both surface layers preferably contain a matting agent, so that scratch resistance and creaking are effective. Particularly preferable from the viewpoint of reduction.
- the matting agent is not added in a large amount, the haze of the film does not increase, and when it is actually used in an LCD (Liquid Crystal Display liquid crystal display), the contrast is lowered and the bright spot is reduced. Inconvenience such as occurrence is less likely to occur. If the amount is too small, the above-mentioned creaking and scratch resistance can be realized. From these viewpoints, it is preferably included in a proportion of 0.01 to 5.0% by mass, more preferably included in a proportion of 0.03 to 3.0% by mass, and a proportion of 0.05 to 1.0% by mass. It is particularly preferable to include
- the optical film A and the optical film B can be manufactured by a solution casting method or a melt casting method.
- the solution casting method is preferable from the viewpoint of suppressing optical defects such as coloring of the optical film, foreign matter defects, and die lines, and the melt casting method is preferable from the viewpoint of suppressing the solvent from remaining in the optical film.
- a method for producing an optical film containing cellulose acylate by the solution casting method is, for example, A1) Dope by dissolving at least cellulose acylate and, if necessary, other additives in a solvent.
- A2) a step of casting a dope on an endless metal support, A3) a step of evaporating a solvent from the cast dope to form a web, A4) a step of peeling the web from the metal support, A5) After drying the web, it may include a step of drawing to obtain a film.
- A1) Dope preparation step In a dissolution vessel, a dope is prepared by dissolving a resin and, if necessary, other additives in a solvent.
- the method of dissolving the resin in the solvent can be, for example, a method of dissolving under heating and pressure.
- a higher heating temperature is preferable from the viewpoint of increasing the solubility of cellulose acylate. If the temperature is too high, it is necessary to increase the pressure, and the productivity is lowered. Therefore, the heating temperature is preferably in the range of 45 to 120 ° C.
- the additive may be added batchwise to the dope, or an additive solution may be separately prepared and added inline.
- an additive solution may be separately prepared and added inline.
- an in-line mixer such as a static mixer (manufactured by Toray Engineering) or SWJ (Toray static type in-pipe mixer Hi-Mixer) is preferably used.
- the obtained dope may contain insoluble matters such as impurities contained in a resin as a raw material, for example. Such an insoluble matter can become a bright spot foreign material in the obtained film. In order to remove insoluble matter, it is preferable to further filter the obtained dope.
- A2) Casting step The dope is cast on the endless metal support from the slit of the pressure die.
- the metal support a stainless steel belt or a drum whose surface is plated with a casting is preferably used.
- the surface of the metal support is preferably mirror-finished.
- the cast width can be in the range of 1-4m.
- the surface temperature of the metal support in the casting step is set to ⁇ 50 ° C. or more and below the temperature at which the solvent boils and does not foam. A higher temperature is preferable because the web can be dried at a higher speed, but it is within a temperature range in which foaming of the web and deterioration of flatness can be prevented.
- the method for adjusting the temperature of the metal support is not particularly limited, and there are a method of blowing hot air or cold air, and a method of bringing hot water into contact with the back side of the metal support. It is preferable to use warm water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is short.
- A3) Solvent evaporation step The web (dope film obtained by casting the dope on the metal support) is heated on the metal support to evaporate the solvent.
- the drying method and drying conditions of the web can be the same as in the above-described A2) casting step.
- A4) Peeling Step The web obtained by evaporating the solvent on the metal support is peeled off at the peeling position on the metal support.
- the residual solvent amount of the web at the time of peeling at the peeling position on the metal support is preferably in the range of 10 to 150% by mass, and 20 to 40% by mass in order to improve the flatness of the obtained film. % Or in the range of 60 to 130% by mass, and more preferably in the range of 20 to 30% by mass or 70 to 120% by mass.
- the amount of residual solvent in the web is defined by the following formula.
- Residual solvent amount (%) (mass before web heat treatment ⁇ mass after web heat treatment) / (mass after web heat treatment) ⁇ 100 Note that the heat treatment for measuring the residual solvent amount means a heat treatment at 115 ° C. for 1 hour.
- the web obtained by peeling from the metal support is dried as necessary and then stretched.
- the web may be dried while being conveyed by a large number of rollers arranged above and below, or may be dried while being conveyed while fixing both ends of the web with clips.
- the method for drying the web may be a method of drying with hot air, infrared rays, a heating roller, microwaves, or the like, and a method of drying with hot air is preferable because it is simple.
- the optical film having a desired retardation is obtained by stretching the web.
- the retardation of the optical compensation film can be controlled by adjusting the magnitude of tension on the web.
- the web is stretched in either the web width direction (TD direction) or the transport direction (MD direction).
- the web may be stretched uniaxially or biaxially.
- Biaxial stretching may be sequential biaxial stretching or simultaneous biaxial stretching.
- the draw ratio depends on the film thickness of the obtained optical film and the required retardation, but for example, the draw ratio in the biaxial direction perpendicular to each other is finally 0.8 to 1 in the casting direction.
- the draw ratio in the biaxial direction perpendicular to each other is finally 0.8 to 1 in the casting direction.
- Within a range of 5 times preferably within a range of 1.1 to 2.5 times in the width direction, within a range of 0.8 to 1.0 times in the casting direction, and 1.2 to 2 times in the width direction It is more preferable to be within the range of 2.0 times.
- the stretch ratio is represented by the ratio W / W0 of the film length in the stretching direction before and after stretching (W represents the length before stretching and W0 represents the length before stretching).
- W represents the length before stretching
- W0 represents the length before stretching
- the stretching temperature is preferably in the range of 120 to 230 ° C., more preferably in the range of 130 to 220 ° C., and even more preferably in the range of greater than 130 ° C. and 210 ° C. or less.
- the stretching method of the web is not particularly limited, and a method of making a difference in circumferential speed between a plurality of rollers and stretching in the casting direction (conveying direction) using the circumferential speed difference (roller stretching method), both ends of the web Fix with clips and pins, widen the gap between clips and pins in the casting direction and stretch in the casting direction, spread in the width direction and stretch in the width direction, both in the casting direction and in the width direction It may be a method of expanding and stretching in both the casting direction and the width direction (tenter stretching method).
- the residual solvent of the web at the start of stretching is preferably 20% by mass or less, more preferably 15% by mass or less.
- the film after stretching is dried as necessary and then wound.
- the film may be dried while being transported by a large number of rollers arranged on the top and bottom (roller method), or may be dried while being transported while fixing both ends of the web with clips. (Tenter method).
- B) Melt casting method The method of producing by the melt casting method is as follows: B1) Step of producing molten pellets (pelletizing step), B2) Step of extruding after melting and kneading the molten pellets (melt extrusion step), B3) A step of cooling and solidifying the molten resin to obtain a web (cooling and solidifying step), and B4) a step of stretching the web (stretching step).
- the resin composition containing the thermoplastic resin as the main component of the optical film is previously kneaded and pelletized.
- the pelletization can be performed by a known method.
- a resin composition containing the above-described thermoplastic resin and, if necessary, an additive such as a plasticizer is melt-kneaded in an extruder, and then die-molded. Extruded into strands. The molten resin extruded in a strand form can be cooled with water or air, and then cut to obtain pellets.
- the raw material of the pellet is preferably dried before being supplied to the extruder in order to prevent decomposition.
- the extruder it is preferable to knead at a low shearing force or at a low temperature so as not to cause deterioration of the resin (decrease in molecular weight, coloring, gel formation, etc.).
- a twin-screw extruder it is preferable to use a deep groove type screw so that the rotational directions of the two screws are the same.
- two screw shapes mesh with each other.
- An optical film may be produced by melting and kneading a thermoplastic resin that has not been melt-kneaded as a raw material with an extruder as it is, without pelletizing the resin composition containing the thermoplastic resin.
- the melting temperature of the film material in the extruder is preferably in the range of Tg to (Tg + 100) ° C., more preferably when the glass transition temperature of the film is Tg (° C.), although it depends on the type of film material. Is in the range of (Tg + 10) to (Tg + 90) ° C.
- the molten resin extruded from the extruder is filtered with a leaf disc filter or the like as necessary, and further mixed with a static mixer or the like, and extruded from a die into a film.
- the extrusion flow rate is preferably stabilized using a gear pump.
- the leaf disk filter used for removal of a foreign material is a stainless fiber sintered filter.
- the stainless steel fiber sintered filter is an integrated, intricately intertwined stainless steel fiber body that is compressed and sintered by integrating the contact points. The density is changed according to the thickness of the fiber and the amount of compression, and the filtration accuracy is adjusted. it can.
- Cooling and solidifying step The resin extruded from the die is nipped between the cooling roller and the elastic touch roller to make the film-like molten resin a predetermined thickness. Then, the film-like molten resin is cooled and solidified stepwise by a plurality of cooling rollers.
- the elastic touch roller is also called a pinching rotary body.
- a commercially available elastic touch roller can also be used.
- the film surface temperature on the elastic touch roller side can be in the range of Tg to (Tg + 110) ° C. of the film.
- Stretching step The obtained web is stretched with a stretching machine to obtain a film. Stretching is performed either in the web width direction or in the transport direction.
- the web stretching method, stretching ratio, and stretching temperature may be the same as described above.
- the optical film according to the present invention can be used in the polarizing plate of the present invention and the liquid crystal display device of the present invention using the polarizing plate. Since the optical film according to the present invention is a film that also functions as a polarizing plate protective film, it is not necessary to prepare an optical film having a phase difference separately from the polarizing plate protective film, so the thickness of the liquid crystal display device is reduced. The manufacturing process can be simplified.
- the polarizing plate according to the present invention is preferably bonded to both surfaces of the liquid crystal cell via an adhesive layer.
- a polarizing plate protective film can also be bonded using an active energy ray-curable adhesive.
- the optical film A and the optical film B are bonded to the polarizer using an active energy ray-curable adhesive, respectively, because moisture permeability can be effectively controlled.
- the configuration of the liquid crystal display device will be specifically described below.
- FIG. 1 is a schematic diagram showing an example of the configuration of a liquid crystal display device.
- the optical film B (105) and the polarizer 104 are preferably bonded via an active energy ray-curable adhesive 103B.
- the optical film A (102) and the polarizer 104 are preferably bonded via an active energy ray-curable adhesive 103A. It is preferable to use an active energy ray-curable adhesive.
- the adhesive may be a solvent system using an organic solvent as a medium, or an aqueous system such as an emulsion type, a colloidal dispersion liquid type, or an aqueous solution type that is a medium containing water as a main component, or a solvent-free type. It may be a mold.
- concentration of the adhesive solution may be appropriately determined depending on the film thickness after bonding, the coating method, the coating conditions, and the like, and is usually 0.1 to 50% by mass.
- active energy ray curable adhesive Preferred examples of the active energy ray-curable adhesive include, for example, ( ⁇ ) cationically polymerizable compound, ( ⁇ ) photocationic polymerization initiator, and ( ⁇ ) as disclosed in JP 2011-028234 A Examples include an active energy ray-curable adhesive composition containing components of a photosensitizer that exhibits maximum absorption in light having a wavelength longer than 380 nm and ( ⁇ ) a naphthalene photosensitizer. Of course, other active energy ray-curable adhesive compositions may be used.
- the polarizing plate can be produced by bonding the optical film of the present invention to one surface of the polarizer using an active energy ray-curable adhesive.
- an active energy ray-curable adhesive When the adhesiveness is different between the two surfaces of the retardation film, it is preferable to bond them to the one having good adhesiveness.
- the polarizing plate includes an adhesive application step of forming an adhesive layer by applying the following active energy ray-curable adhesive to at least one of the adhesive surfaces of the polarizer and the retardation film, and the adhesive layer A bonding step in which the polarizer and the retardation film are bonded and bonded via the adhesive layer, and a curing step in which the adhesive layer is cured in a state where the polarizer and the retardation film are bonded via the adhesive layer; It can manufacture with the manufacturing method containing. Moreover, there may be a pretreatment step in which the surface of the retardation film to which the polarizer is adhered is subjected to an easy adhesion treatment.
- Pretreatment process In the pretreatment step, the surface of the retardation film that adheres to the polarizer is subjected to easy adhesion treatment. When the retardation film and the protective film are bonded to both surfaces of the polarizer, easy adhesion treatment is performed on each of the retardation film and the protective film. In the next adhesive application process, the surface subjected to easy adhesion treatment is treated as a bonding surface with a polarizer, so on both surfaces of the retardation film, on the surface to be bonded with the active energy ray-curable adhesive, Apply easy adhesion treatment. Examples of the easy adhesion treatment include corona treatment and plasma treatment.
- the active energy ray-curable adhesive is applied to at least one of the adhesive surfaces of the polarizer and the retardation film.
- the application method is not particularly limited. For example, various wet coating methods such as a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater can be used.
- various wet coating methods such as a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater can be used.
- the method of pressing with a roller etc. and spreading uniformly can also be utilized.
- Bonding process After apply
- this bonding step for example, when an active energy ray-curable adhesive is applied to the surface of the polarizer in the previous application step, a retardation film is superimposed thereon.
- a polarizer is superimposed thereon.
- an active energy ray-curable adhesive is cast between the polarizer and the retardation film, the polarizer and the retardation film are superposed in that state.
- both sides of the polarizer are respectively attached via an active energy ray curable adhesive.
- a phase difference film and a protective film are overlaid.
- both sides in this state when the retardation film is overlaid on one side of the polarizer, when the retardation film and the protective film are overlaid on the polarizer side and the retardation film side, and on both sides of the polarizer
- rollers or the like As the material of the roller, metal, rubber or the like can be used.
- the rollers arranged on both sides may be made of the same material or different materials.
- an active energy ray curable adhesive is irradiated with active energy rays, and a cationic polymerizable compound (eg, epoxy compound or oxetane compound) or a radical polymerizable compound (eg, acrylate compound, acrylamide type).
- a cationic polymerizable compound eg, epoxy compound or oxetane compound
- a radical polymerizable compound eg, acrylate compound, acrylamide type.
- the active energy ray-curable adhesive containing the compound or the like is cured, and the polarizer and the retardation film, or the polarizer and the retardation film, which are superposed via the active energy ray-curable adhesive, are adhered.
- the active energy ray may be irradiated from either the polarizer side or the retardation film side.
- the active energy is in a state where the retardation film and the protective film are superimposed on both sides of the polarizer via an active energy ray-curable adhesive, respectively. It is advantageous to irradiate the line and simultaneously cure the active energy ray curable adhesive on both sides.
- Visible light, ultraviolet rays, X-rays, electron beams, etc. can be used as the active energy rays applied for curing, but electron beams and ultraviolet rays are generally preferred because they are easy to handle and have a sufficient curing rate. Used.
- the acceleration voltage is preferably in the range of 5 to 300 kV, more preferably in the range of 10 to 250 kV. If the acceleration voltage is less than 5 kV, the electron beam may not reach the adhesive and may be insufficiently cured. If the acceleration voltage exceeds 300 kV, the penetrating force through the sample is too strong and the electron beam rebounds. There is a risk of damaging the polarizer.
- the irradiation dose is in the range of 5 to 100 kGy, more preferably in the range of 10 to 75 kGy.
- the adhesive becomes insufficiently cured, and when it exceeds 100 kGy, the retardation film and the polarizer are damaged, resulting in a decrease in mechanical strength and yellowing to obtain predetermined optical characteristics. I can't.
- Arbitrary appropriate conditions can be employ
- the dose of ultraviolet rays in the range of 50 ⁇ 1500mJ / cm 2 in accumulated light amount, and even more preferably in the range of within the range of 100 ⁇ 500mJ / cm 2.
- the line speed depends on the curing time of the adhesive, but is preferably in the range of 1 to 500 m / min, more preferably 5 to 300 m / min, and still more preferably 10 to 100 m. / Min. If the line speed is too slow, the productivity is poor, or the retardation film is damaged too much, and a polarizing plate that can withstand a durability test cannot be produced. When the line speed is too high, the adhesive is not sufficiently cured, and the target adhesiveness may not be obtained.
- the thickness of the adhesive layer is not particularly limited, but is usually in the range of 0.01 to 10, and preferably in the range of 0.5 to 5 ⁇ m.
- the polarizing plate protective film used on the surface side of the display device preferably has an antireflection layer, an antistatic layer, an antifouling layer, and a backcoat layer in addition to the antiglare layer or the clear hard coat layer.
- a polarizer which is a main component of a polarizing plate, is an element that allows only light of a plane of polarization in a certain direction to pass.
- a typical polarizer currently known is a polyvinyl alcohol-based polarizing film, which is polyvinyl alcohol.
- iodine is dyed on a system film and one in which dichroic dye is dyed.
- the polarizer is preferably formed by forming a polyvinyl alcohol aqueous solution into a film and dyeing it by uniaxial stretching, or uniaxially stretching after dyeing and then performing a durability treatment with a boron compound.
- the thickness of the polarizer is preferably in the range of 5 to 30 ⁇ m, particularly preferably in the range of 10 to 20 ⁇ m.
- the polarizing plate of the present invention is provided in a liquid crystal display device.
- FIG. 1 is a schematic cross-sectional view showing an example of the configuration of a liquid crystal display device 100 in which the above-described polarizing plates 101A and 101B of the present invention are arranged on both surfaces of a liquid crystal cell 101C.
- a liquid crystal cell 101C is configured by sandwiching both surfaces of a liquid crystal layer 107 between glass substrates 108A and 108B as transparent substrates, and an adhesive layer 106 is formed on each surface of each glass substrate 108A and 108B. Accordingly, polarizing plates 101A and 101B having the configuration shown in FIG. 1 are arranged to constitute the liquid crystal display device 100.
- the liquid crystal cell 101C is configured by arranging an alignment film, a transparent electrode, and a glass substrate (glass base materials 108A and 108B) on both surfaces of a liquid crystal substance.
- the glass substrate constituting the liquid crystal cell can be thinned, and as a result, the thinned liquid crystal is achieved.
- a display device can be obtained.
- Examples of the material constituting the glass base materials 108A and 108B that can be used for the liquid crystal cell 101C include soda lime glass and silicate glass, and is preferably silicate glass. Silica glass or borosilicate glass is more preferable.
- the glass constituting the glass substrate is preferably a non-alkali glass that does not substantially contain an alkali component, specifically, a glass having an alkali component content of 1000 ppm or less.
- the content of the alkali component in the glass substrate is preferably 500 ppm or less, and more preferably 300 ppm or less.
- substitution of cations occurs on the film surface, and soda blowing phenomenon tends to occur. Thereby, the density of the film surface layer tends to be lowered, and the glass substrate is easily damaged.
- the thickness of the glass substrates 108A and 108B of the liquid crystal cell constituting the liquid crystal display device is preferably within the range of 0.4 to 0.6 mm for the liquid crystal display. Such a thickness is preferable in that it can contribute to the formation of a thin liquid crystal display device.
- the glass substrate can be formed by a known method such as a float method, a down draw method, an overflow down draw method or the like. Of these, the overflow downdraw method is preferred because the surface of the glass substrate does not come into contact with the molded member during molding and the surface of the resulting glass substrate is hardly damaged.
- such a glass base material can also be obtained as a commercial item, for example, non-alkali glass AN100 (thickness 500 ⁇ m) manufactured by Asahi Glass Co., Ltd., a glass substrate EAGLE XG (r) Slim (thickness manufactured by Corning) 300 ⁇ m, 400 ⁇ m, etc.), a glass substrate (thickness 100 to 200 ⁇ m) manufactured by Nippon Electric Glass Co., Ltd., and the like.
- the polarizing plates 101A and 101B as shown in FIG. 1 and the glass base materials 108A and 108B constituting the liquid crystal cell 101C are bonded via an adhesive layer 106.
- a double-sided tape for example, a 25 ⁇ m-thick double-sided tape (baseless tape MO-3005C) manufactured by Lintec Corporation or the composition used for forming the active energy ray-curable resin layer is applied. be able to.
- Bonding between the surface of the polarizing plate on the side of the retardation film and at least one surface of the liquid crystal cell can be performed by a known method. Depending on the case, it may be bonded through an adhesive layer.
- the mode (driving method) of the liquid crystal display device is not particularly limited, and liquid crystal display devices of various drive modes such as STN, TN, OCB, HAN, VA (MVA, PVA), IPS, OCB, and the like can be used.
- N1 9H-carbazole-9-ethanol
- N2 n-hexylcarbazole
- N3 2,3-diphenylquinoxaline
- N4 2-methylbenzoxazole
- N5 2- (4-tert-butylphenyl) -5- (4-biphenyl) -1,3,4-oxadiazole
- N8 cyclohexane is substituted with trans at positions 1 and 4.
- N11 Exemplary compound 1 of the compound having a structure represented by the general formula (3)
- N12 Exemplary compound 6 having a structure represented by the general formula (3) 6
- N13 Exemplary compound 176 having a structure represented by general formula (3)
- EG represents ethylene glycol
- PG represents propylene glycol
- BG represents butylene glycol
- TPA represents terephthalic acid
- PA represents phthalic acid
- AA adipic acid
- SA succinic acid.
- S9 Trimethylolpropane tribenzoate
- S11 Triphenyl phosphate
- S12 Diphenyl biphenyl phosphate
- S14 Dibutyl phthalate
- S15 An organic acid having the following composition (mass ratio) (in addition to polyhydric alcohol and polycarboxylic acid, a monovalent acid having a substituent having 4 or more carbon atoms is one of the polyhydric alcohols). Part of the hydroxyl group and a structure in which an ester bond is formed).
- Preparation of optical films T1-2, T1-4 and T1-6 (Acrylic resin and acrylic elastic polymer particles)
- acrylic resin a copolymer having a mass ratio of methyl methacrylate / methyl acrylate of 96/4 was used.
- elastic rubber particles acrylic elastic polymer particles having a three-layer structure including an innermost layer, an intermediate layer, and an outermost layer were used.
- the innermost layer is a hard polymer obtained by polymerizing methyl methacrylate with a small amount of allyl methacrylate
- the intermediate layer is mainly composed of butyl acrylate, styrene and a small amount of Soft elastic body polymerized using allyl methacrylate
- outermost layer is made of a hard polymer polymerized with a small amount of ethyl acrylate in methyl methacrylate, and the average particle size up to the elastic body that is the intermediate layer The diameter is 240 nm.
- the amount of extrusion through the T-shaped die was adjusted to produce an optical film T1-4 having a thickness of 60 ⁇ m and an optical film T1-6 having a thickness of 80 ⁇ m, respectively.
- corona discharge treatment One side of the (meth) acrylic resin film obtained above was subjected to corona discharge treatment (corona discharge electron irradiation amount: 77 W / m 2 / min).
- the obtained easy-adhesive composition was applied to the corona discharge-treated surface of the (meth) acrylic resin film subjected to corona discharge treatment with a bar coater (# 6) so that the thickness after drying was 350 nm. . Thereafter, the (meth) acrylic resin film is put into a hot air dryer (140 ° C.), and the easy-adhesive composition is dried for about 5 minutes to form an easy-adhesion layer (0.3 to 0.5 ⁇ m). Film T1-3 was produced.
- the obtained polyethylene terephthalate resin (A) had an intrinsic viscosity of 0.62 dl / g and contained substantially no inert particles and internally precipitated particles.
- PET (A) (Hereafter, abbreviated as PET (A).)
- PET (B) (Production Example 2-Polyester B) Next, 10 parts by weight of a dried UV absorber (2,2 ′-(1,4-phenylene) bis (4H-3,1-benzoxazinon-4-one), PET (A) containing no particles 90 parts by mass (inherent viscosity is 0.62 dl / g) was mixed, and a polyethylene terephthalate resin (B) containing an ultraviolet absorber was obtained using a kneading extruder (hereinafter abbreviated as PET (B)).
- a dried UV absorber (2,2 ′-(1,4-phenylene) bis (4H-3,1-benzoxazinon-4-one)
- PET (B) containing no particles 90 parts by mass (inherent viscosity is 0.62 dl / g) was mixed, and a polyethylene terephthalate resin (B) containing an
- a transesterification reaction and a polycondensation reaction were carried out by a conventional method, and as a dicarboxylic acid component (based on the whole dicarboxylic acid component) 46 mol% terephthalic acid, 46 mol% isophthalic acid and 8 mol% sodium 5-sulfonatoisophthalate, A water-dispersible sulfonic acid metal group-containing copolymer polyester resin having a composition of 50 mol% ethylene glycol and 50 mol% neopentyl glycol (relative to the entire glycol component) was prepared as a glycol component.
- the unstretched film on which this coating layer was formed was guided to a tenter stretching machine, guided to a hot air zone at a temperature of 125 ° C. while being gripped by a clip, and stretched 4.0 times in the width direction.
- the film is processed at a temperature of 225 ° C. for 30 seconds, and further subjected to a relaxation treatment of 3% in the width direction, and is an uniaxially oriented PET film having a film thickness of 60 ⁇ m. T1-5 was obtained.
- the thickness of the unstretched film was changed so that the thickness was changed from 60 ⁇ m to 80 ⁇ m, 100 ⁇ m, and 110 ⁇ m, respectively, in the same manner as T1-5, T1-7, T1-8, and T1 -9 was obtained.
- Optical film T1-10 >> (Production of cyclic olefin resin film (COP)) ZEONOR (manufactured by Nippon Zeon Co., Ltd.) was used as a retardation film made of a cyclic olefin (COP) resin.
- COP cyclic olefin resin film
- Water vapor transmission rate of optical films T1-1 to T1-10 was evaluated by measuring the water vapor permeability at 40 ° C. and 90% RH by a method according to JIS K 7129 (1992).
- Table 7 shows the film thickness and water vapor permeability of each of the optical films T1-1 to T1-10.
- Preparation of optical film B >> ⁇ Preparation of retardation film T2-1 >> ⁇ Fine particle dispersion 1> Fine particles (Aerosil R812 manufactured by Nippon Aerosil Co., Ltd.) 11 parts by mass Ethanol 89 parts by mass The above was stirred and mixed with a dissolver for 50 minutes, and then dispersed with Manton Gorin.
- a main dope having the following composition was prepared. First, methylene chloride and ethanol were added to the pressure dissolution tank. Cellulose acetate having an acetyl group substitution degree of 2.60 was added to a pressure dissolution tank containing a solvent while stirring. This is completely dissolved with heating and stirring. This was designated as Azumi Filter Paper No. The main dope was prepared by filtration using 244.
- the solvent was evaporated until the amount of residual solvent in the cast (cast) film reached 75%, and then peeled off from the stainless steel belt support with a peeling tension of 130 N / m.
- the peeled retardation film was stretched 30% in the width direction using a tenter while applying heat at 150 ° C. (stretching ratio: 1.3).
- the residual solvent at the start of stretching was 15%.
- Triarylsulfonium hexafluorophosphate was blended as a 50% propylene carbonate solution, and the solid content of triarylsulfonium hexafluorophosphate was shown below.
- the corona discharge treatment was performed at a corona output intensity of 2.0 kW and a line speed of 18 m / min.
- the above-prepared adhesive layer forming coating solution 1 is applied to the corona discharge treated surface of T2-1 with a bar coater so that the film thickness after curing is about 3 ⁇ m, and the active energy ray-curable resin layer is applied.
- Also referred to as an adhesive layer.
- the prepared polyvinyl alcohol-iodine polarizer was bonded to the obtained active energy ray-curable resin layer.
- the optical film T1-8 produced above was used as the optical film A, and the surface thereof was subjected to corona discharge treatment.
- the conditions of the corona discharge treatment were a corona output intensity of 2.0 kW and a speed of 18 m / min.
- the above-prepared coating solution 1 for forming an adhesive layer is applied to the corona discharge treated surface of the optical film T1-8 with a bar coater so that the film thickness after curing is about 3 ⁇ m. A resin layer was formed.
- a polarizer bonded to one side of the optical film T2-1 is bonded to the active energy ray curable resin layer, and the optical film T1-8 / active energy ray curable resin layer / polarizer / active energy ray is bonded.
- a laminate in which the curable resin layer / optical film T2-1 was laminated was obtained. At that time, the optical film T2-1 was bonded so that the slow axis of the optical film T2-1 and the absorption axis of the polarizer were orthogonal to each other.
- the direction of bonding of the polarizing plate is such that the surfaces of the retardation films T2-1 to T2-7 are on the liquid crystal cell side and in the same direction as the polarizing plate previously bonded.
- the liquid crystal display devices 1 to 7 corresponding to the polarizing plates 1 to 7 were respectively produced so that the absorption axes were directed.
- the liquid crystal display device produced above was laid and placed on a stand or the like, and Bencot (registered trademark, manufactured by Asahi Kasei Fibers) was placed on a part of the polarizing plate for evaluation to contain water.
- Bencot registered trademark, manufactured by Asahi Kasei Fibers
- the bencott was covered with 100 ⁇ m PET so that it would not dry, a black display signal was input to the TV from the PC, and the TV was turned on for 24 hours (the room temperature was set at 23 ° C., the panel temperature was 38 ° C.). After 24 hours, remove the becot.
- the L * (brightness) of the portion where there was a becot was measured by EZ contrast (manufactured by ELDIM) as L * of the water-immersed portion. It was measured with EZ Contrast Bencot of the free portion of the L * a non-submerged portion L *.
- the measurement with EZ contrast was performed in the color mode with the TV displayed in black. The conditions for water immersion were such that the panel was turned on and was allowed to stand for 24 hours in a state where a bencott sufficiently soaked in water was attached. Subsequently, the value of the ratio L * of the water-immersed part / L * of the non-immersed part was calculated, and color unevenness was evaluated according to the following criteria.
- A 1.05 or more and 1.30 or less: No occurrence of color unevenness is observed at all.
- ⁇ More than 1.30 and 1.55 or less: Very slight weak color unevenness is observed, but there is no problem in practical use.
- ⁇ More than 1.55 and less than 1.80: Color unevenness is slightly observed, but it is a level with no problem in practical use.
- ⁇ More than 1.80: Strong color unevenness occurs, and there is a problem in moisture resistance.
- the value of the ratio of L * of the water-immersed part / L * of the non-immersed part was 1.05 or more, there was no sample in which point-like defects were observed, but the ratio value was 1. Since the case of less than 05 includes the case where a point-like defect occurs, the evaluation of color unevenness was confirmed by visual evaluation.
- the liquid crystal display devices 2 to 7 of the present invention are favorable with less color unevenness and point defects as compared with the liquid crystal display device 1 of the comparative example.
- Example 2 In the production of the polarizing plate 2 of Example 1, the optical film A was changed from T1-8 to T1-1 to T1-10 as shown in Table 5 to produce polarizing plates 11 to 20, and then each polarizing plate In the same manner as in Example 1, liquid crystal display devices 11 to 20 were manufactured.
- Example 3 In the production of the polarizing plate 2 of Example 1, the cellulose acylate resin used for the production of the optical film T2-2 (optical film B) was changed from C5 to C1 to C7 as shown in Table 11, and the measurement was carried out. Polarizing plates 31 to 37 were produced in the same manner as in Example 1. Thereafter, liquid crystal display devices 31 to 37 were produced in the same manner as in Example 1 using the respective polarizing plates.
- the liquid crystal display devices 31 to 37 were evaluated for color unevenness and point defects in the same manner as in Example 1. The results are shown in Table 11.
- Example 4 In the production of the polarizing plate 2 of Example 1, the amount of the compound having the structure represented by the general formula (1) used for the production of the optical film T2-2 (optical film B) is as shown in Table 12. Instead, polarizing plates 41 to 46 were produced in the same manner as in Example 1. Thereafter, liquid crystal display devices 41 to 46 were produced in the same manner as in Example 1 using the respective polarizing plates. Further, the liquid crystal display devices 47 to 53 were produced in the same manner as in Example 1 except that the film thickness of the optical film B was changed as shown in Table 12.
- the liquid crystal display devices 41 to 53 were evaluated for color unevenness and point defects in the same manner as in Example 1. The results are shown in Table 12.
- the addition amount of the compound having the chemical structure represented by the general formula (1) contained in the optical film B is 5 to 10 per 100 parts by mass of the cellulose acylate resin. It turns out that it is preferable that the mass part is contained.
- Example 5 In the production of the optical film T2-2 (optical film B) in the production of the polarizing plate 2 of Example 1, a retardation increasing agent was added as shown in Table 13, and the polarizing plates 61 to 73 were produced in the same manner as in Example 1. Was made. Thereafter, liquid crystal display devices 61 to 73 were produced in the same manner as in Example 1 using the respective polarizing plates.
- the liquid crystal display devices 61 to 73 were evaluated for color unevenness and point defects in the same manner as in Example 1. The results are shown in Table 13.
- the optical film B preferably contains a nitrogen-containing retardation increasing agent even within the present invention.
- Example 6 In the production of the optical film T2-2 (optical film B) in the production of the polarizing plate 2 of Example 1, the plasticizers were added as shown in Table 14, and the polarizing plates 81 to 96 were produced in the same manner as in Example 1. did. Thereafter, liquid crystal display devices 81 to 96 were produced in the same manner as in Example 1 using the respective polarizing plates.
- the liquid crystal display devices 81 to 96 were evaluated for color unevenness and point defects in the same manner as in Example 1. The results are shown in Table 14.
- Example 7 Production of Polarizing Plate 101 >> A polarizing plate 101 was prepared in the same manner as the polarizing plate 2 in Example 1.
- Step 1 Retardation films T1-8 and T2 having been dipped in a 2 mol / L sodium hydroxide solution at 60 ° C. for 90 seconds, then washed with water and dried, and subjected to saponification treatment on the side to be bonded to the polarizer -2.
- Step 2 The polarizer was immersed in a polyvinyl alcohol adhesive tank having a solid content of 2% by mass for 1 to 2 seconds.
- Step 3 Excess adhesive adhered to the polarizer in Step 2 was gently wiped off, and this was placed on the retardation film T2-2 processed in Step 1.
- Step 4 The retardation film T2-2, the polarizer and the back side T1-8 laminated in Step 3 were bonded at a pressure of 20 to 30 N / cm 2 and a conveying speed of about 2 m / min.
- Step 5 A sample obtained by bonding the polarizer prepared in Step 4 and the retardation films T2-2 and T1-8 in a dryer at 80 ° C. was dried for 2 minutes to prepare a polarizing plate 103.
- Example 8 In the production of the optical film T2-2 (optical film B) in the production of the polarizing plate 2 of Example 1, a cellulose acylate resin, a compound having a structure represented by the general formula (1), a retardation increasing agent, a plasticizer Polarizers 110 to 150 were produced in the same manner as in Example 1 except that the type and amount of the agent and the film thickness of the optical film B were changed as shown in Table 16. Thereafter, liquid crystal display devices 110 to 150 were produced in the same manner as in Example 1 using the respective polarizing plates.
- the liquid crystal display devices 110 to 150 were evaluated for color unevenness and point defects in the same manner as in Example 1. The results are shown in Table 16 and Table 17.
- Example 9 As the optical film B, a cellulose acylate film T2-131 having a three-layer structure was produced by the three-layer simultaneous casting method (co-casting method) according to the following procedure.
- ⁇ Preparation of retardation film T2-131 >> Using the co-casting die shown in FIG. 2, a cellulose acylate film T2-131 having a three-layer structure (C4 / C1 / C4) is produced by the three-layer simultaneous casting method (co-casting method) according to the following procedure. did.
- Dope S is supplied to the co-casting die 50 at the same time, and is a multilayer structure composed of a skin layer (B surface) 61 / core layer 62 / skin layer (A surface) 63 by a single casting operation.
- the organic solvent in the obtained dope film was evaporated until the residual solvent amount reached 100% by mass to form a web, and then the web was peeled from the stainless steel band support.
- the obtained web was further pre-dried at 110 ° C. for 10 minutes, and then the web was stretched 1.3 times with respect to the original width in the TD direction at 160 ° C. with a tenter.
- the residual solvent amount of the web at the start of stretching was 2.0% by mass.
- relaxation is performed at 130 ° C. for 5 minutes, and thereafter, the temperature is maintained at 135 ° C. by a dryer (bending zone), and facing the A side of the web by a conveying roller in the dryer zone.
- the diameter and arrangement of the transport rollers are set so that the value of 1 / a is 0.040 mm ⁇ 1.
- the web was conveyed at a conveyance speed of 20 m / min by repeating the bending of the times.
- the obtained film was slit to 2.0 m width, 10 mm wide and 5 ⁇ m knurled at both ends of the film, wound on a core of 15.24 cm in inner diameter with an initial tension of 220 N / m and a final tension of 110 N / m.
- a retardation film T2-131 having a long three-layer structure having a thickness of 4000 m and a film thickness of 50 ⁇ m was obtained.
- a polarizing plate 161 was produced in the same manner as in Example 1 using T1-8 as the optical film A. Thereafter, a liquid crystal display device 161 was produced using the polarizing plate 161 in the same manner as in Example 1.
- the liquid crystal display device 161 was evaluated for color unevenness and point defects in the same manner as in Example 1. The results are shown in Table 18.
- liquid crystal display device 161 of the present invention is excellent in reducing color unevenness and point defects.
- the polarizing plate of the present invention can provide a polarizing plate in which the occurrence of color unevenness and point-like defects is suppressed, and can provide a liquid crystal display device having the polarizing plate.
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Abstract
Description
2.前記光学フィルムBの面内方向のリターデーション値Roと厚さ方向のリターデーション値Rtとが、23℃・55%RHの環境下で、それぞれ下記の範囲内であることを特徴とする第1項に記載の偏光板。
Rt:100~300nm
3.前記光学フィルムBの膜厚が、10~90μmの範囲内であることを特徴とする第1項又は第2項に記載の偏光板。
7.前記光学フィルムAの40℃・90%RHにおける水蒸気透過度が、20~120g/m2・24hrの範囲内であることを特徴とする第1項から第6項までのいずれか一項に記載の偏光板。
本発明の偏光板は、光学フィルムA、偏光子及び光学フィルムBが、この順で積層された偏光板であって、前記光学フィルムAは、アクリル樹脂又はポリエステル樹脂の少なくともいずれかを含有する光学フィルムであり、前記光学フィルムBは、アシル基置換度が2.1~3.0の範囲内のセルロースアシレート樹脂と、前記一般式(1)で表される構造を有する化合物とを含有する位相差フィルムであることを特徴とする。
下記一般式(1)で表される構造を有する化合物は光学フィルムBに含まれる。この化合物をセルロースアシレート樹脂とともに用いることにより、偏光板を液晶表示装置に用いたとき、環境湿度の変動による位相差変動の発生を抑え、色ムラの発生を抑制し、また、偏光板内部に水分がたまることによる点状欠陥を抑制することができる。
さらに、位相差上昇剤としても機能することができる。
ここで、R1~R6は、一般式(1)におけるR1~R6、とそれぞれ同義である。
本発明に係る光学フィルムBにおいて、一般式(1)、一般式(2)又は一般式(1a)で表される構造を有する化合物の含有量は、特に制限されない。一般式(1)、一般式(2)又は一般式(1a)で表される構造を有する化合物の含有量は、例えば、セルロースアシレート樹脂100質量部に対して、好ましくは1~30質量部、より好ましくは1~20質量部、特に好ましくは2~10質量部である。
光学フィルムAは、アクリル樹脂又はポリエステル樹脂の少なくともいずれかを含有する光学フィルムである。光学フィルムAは保護フィルムとして、液晶表示装置において、偏光板の外側の樹脂フィルムであることが好ましい。そのため、光学フィルムAは保護フィルムの透湿性は低いことが好ましい。
アクリル樹脂とは、(メタ)アクリル樹脂を意味し、アクリル樹脂とメタクリル系樹脂の両方を含む概念である。以下、アクリル樹脂について説明する。
アクリル樹脂は、上述したように(メタ)アクリル樹脂であり、アクリル酸エステルやメタクリル酸エステルの重合体を意味する。メタクリル酸エステルの重合体としては、例えば、メタクリル酸アルキルを主体とする重合体からなるものが好ましい。メタクリル酸アルキルの単量体組成は、全単量体の合計100質量%を基準として、メタクリル酸アルキルが、好ましくは70質量%以上、より好ましくは80質量%以上、更に好ましくは90質量%以上であり、かつメタクリル酸アルキルが99質量%以下である。なお、アクリル樹脂としては、メタクリル酸アルキルの単独重合体であってもよいし、メタクリル酸アルキル50質量%以上とメタクリル酸アルキル以外の単量体50質量%以下との共重合体であってもよい。メタクリル酸アルキルとしては、通常、そのアルキル基の炭素数が1~4のものが用いられ、中でもメタクリル酸メチルが好ましく用いられる。
カラム:Shodex K806、K805、K803G(昭和電工(株)製を3本接続して使用した)
カラム温度:25℃
試料濃度:0.1質量%
検出器:RI Model 504(GLサイエンス社製)
ポンプ:L6000(日立製作所(株)製)
流量:1.0ml/min
校正曲線:標準ポリスチレンSTK standard ポリスチレン(東ソー(株)製)Mw=500~2800000までの13サンプルによる校正曲線を使用した。13サンプルは、ほぼ等間隔に用いることが好ましい。
柔軟性を向上させてハンドリング性を高めるため、アクリル樹脂にはゴム弾性体粒子を配合していることが好ましい。ゴム弾性体粒子は、ゴム弾性体を含有する粒子であり、ゴム弾性体のみからなる粒子であってもよいし、ゴム弾性体の層を有する多層構造の粒子であってもよい。ゴム弾性体としては、例えば、オレフィン系弾性重合体、ジエン系弾性重合体、スチレン-ジエン系弾性共重合体、アクリル系弾性重合体が挙げられる。中でも、アクリル樹脂フィルムの表面硬度や耐光性、透明性の点からは、アクリル系弾性重合体が好ましい。
光学フィルムAを形成するポリエステル樹脂は特に限定されないが、例えば、テレフタル酸、イソフタル酸、オルトフタル酸、2,5-ナフタレンジカルボン酸、2,6-ナフタレンジカルボン酸、1,4-ナフタレンジカルボン酸、1,5-ナフタレンジカルボン酸、ジフェニルカルボン酸、ジフェノキシエタンジカルボン酸、ジフェニルスルホンカルボン酸、アントラセンジカルボン酸、1,3-シクロペンタンジカルボン酸、1,3-シクロヘキサンジカルボン酸、1,4-シクロヘキサンジカルボン酸、ヘキサヒドロテレフタル酸、ヘキサヒドロイソフタル酸、マロン酸、ジメチルマロン酸、コハク酸、3,3-ジエチルコハク酸、グルタル酸、2,2-ジメチルグルタル酸、アジピン酸、2-メチルアジピン酸、トリメチルアジピン酸、ピメリン酸、アゼライン酸、ダイマー酸、セバシン酸、スベリン酸、ドデカジカルボン酸等のジカルボン酸と、エチレングリコール、プロピレングリコール、ヘキサメチレングリコール、ネオペンチルグリコール、1,2-シクロヘキサンジメタノール、1,4-シクロヘキサンジメタノール、デカメチレングリコール、1,3-プロパンジオール、1,4-ブタンジオール、1,5-ペンタンジオール、1,6-ヘキサジオール、2,2-ビス(4-ヒドロキシフェニル)プロパン、ビス(4-ヒドロキシフェニル)スルホン等のジオールを、それぞれ1種を重縮合してなるホモポリマー、又はジカルボン酸1種以上とジオール2種以上を重縮合してなる共重合体、あるいはジカルボン酸2種以上とジオールを1種以上重縮合してなる共重合体、及びこれらのホモポリマーや共重合体を2種以上ブレンドしてなるブレンド樹脂のいずれかのポリエステル樹脂を挙げることができる。中でも、ポリエチレンテレフタレート樹脂が好ましく用いられる。また、上記の樹脂を混合して用いることもできる。
光学フィルムBは、アシル基置換度が2.1~3.0の範囲内のセルロースアシレート樹脂と、前記一般式(1)で表される構造を有する化合物とを含有する位相差フィルムである。
本発明に係る光学フィルムBを構成するセルロースアシレート樹脂は、アシル基置換度が2.1~3.0の範囲内にあるセルロースアシレート樹脂である。
本発明に係る光学フィルムBの面内方向のリターデーション値Roと厚さ方向のリターデーション値Rtとは、23℃・55%RHの環境下で、それぞれ下記の範囲内であることが好ましい。このような範囲内のリターデーション値とすることで、良好な偏光特性を備えた偏光板とすることができる。
Rt:100~300nm
リターデーション値の測定は、光波長590nmで、自動複屈折計KOBRA-21ADH(王子計測機器)を用いて行うことができる。
式(ii):Rt(590)={(nx+ny)/2-nz}×d
〔式(i)及び式(ii)において、nxは、フィルムの面内方向において屈折率が最大になる方向xにおける屈折率を表す。nyは、フィルムの面内方向において、前記方向xと直交する方向yにおける屈折率を表す。nzは、フィルムの厚さ方向zにおける屈折率を表す。dは、フィルムの厚さ(nm)を表す。〕
本発明に係る光学フィルムBの膜厚は10~90nmの範囲内であることが好ましい。より好ましくは10~40nmの範囲内である。
本発明に係る光学フィルムBには、位相差上昇剤を含有することができる。位相差上昇剤は含窒素位相差上昇剤であることが好ましい。具体的には含窒素位相差上昇剤が、カルバゾール環、キノキサリン環、ベンゾオキサゾール環、オキサジアゾール環、オキサゾール環、トリアゾール環及びピラゾール環を有する化合物から選ばれる少なくともいずれか一種であることが好ましい。
本発明光学フィルムBにおいては、含窒素位相差上昇剤として下記一般式(3)で表される化合物を含有することが好ましい。
一般式(3)で表される化合物は一般式(4)で表される化合物であることが好ましい。
mが小さい方がセルロースアシレートとの相溶性に優れるため、mは0~2の整数であることが好ましく、0~1の整数であることがより好ましい。
一般式(3)で表される構造を有する化合物は、下記一般式(3.1)で表される構造を有するトリアゾール化合物であることが好ましい。
さらに、上記一般式(3.1)で表される構造を有するトリアゾール化合物は、下記一般式(3.2)で表される構造を有するトリアゾール化合物であることが好ましい。
前記一般式(3)、(4)、(3.1)又は(3.2)で表される化合物は、水和物、溶媒和物若しくは塩を形成してもよい。なお、本発明において、水和物は有機溶媒を含んでいてもよく、また溶媒和物は水を含んでいてもよい。即ち、「水和物」及び「溶媒和物」には、水と有機溶媒のいずれも含む混合溶媒和物が含まれる。塩としては、無機又は有機酸で形成された酸付加塩が含まれる。無機酸の例として、ハロゲン化水素酸(塩酸、臭化水素酸など)、硫酸、リン酸などが含まれ、またこれらに限定されない。また、有機酸の例には、酢酸、トリフルオロ酢酸、プロピオン酸、酪酸、シュウ酸、クエン酸、安息香酸、アルキルスルホン酸(メタンスルホン酸など)、アリルスルホン酸(ベンゼンスルホン酸、4-トルエンスルホン酸、1,5-ナフタレンジスルホン酸など)などが挙げられ、またこれらに限定されない。これらのうち好ましくは、塩酸塩、酢酸塩、プロピオン酸塩、酪酸塩である。
前記一般式(3)で表わされる化合物において、1,2,4-トリアゾール環を有する化合物は、いかなる原料を用いても構わないが、ニトリル誘導体又はイミノエーテル誘導体と、ヒドラジド誘導体を反応させる方法が好ましい。反応に用いる溶媒としては、原料と反応しないと溶媒であれば、いかなる溶媒でも構わないが、エステル系(例えば、酢酸エチル、酢酸メチル等)、アミド系(ジメチルホルムアミド、ジメチルアセトアミド等)、エーテル系(エチレングリコールジメチルエーテル等)、アルコール系(例えば、メタノール、エタノール、プロパノール、イソプロパノール、n-ブタノール、2-ブタノール、エチレングリコール、エチレングリコールモノメチルエーテル等)、芳香族炭化水素系(例えば、トルエン、キシレン等)、水を挙げられることができる。使用する溶媒として、好ましくは、アルコール系溶媒である。また、これらの溶媒は、混合して用いても良い。
(例示化合物6の合成)
例示化合物6は以下のスキームによって合成することができる。
(例示化合物176の合成)
例示化合物176は以下のスキームによって合成することができる。
その他の化合物についても同様の方法によって合成が可能である。
本発明に係る前記一般式(3)で表される化合物は、適宜量を調整して光学フィルムに含有することができるが、添加量としては光学フィルムを形成する樹脂(例えば、セルロースアシレート等)に対して、1~15質量%含むことが好ましく、特に、2~10質量%含むことが好ましい。この範囲内であれば、本発明の光学フィルムの機械強度を損なうことなく、環境湿度の変化に依存した光学値の変動を低減することができる。
本発明に係る前記一般式(3)~一般式(10)で表される構造を有する化合物は、適宜量を調整して光学フィルムBに含有することができるが、添加量としては光学フィルムを形成するアシルセルロース樹脂に対して、1~15質量%含むことが好ましく、特に、2~10質量%含むことが好ましい。この範囲内であれば、本発明の光学フィルムの機械強度を損なうことなく、環境湿度の変化に依存した光学値の変動を低減することができる。
本発明においては、光学フィルムAに柔軟性を与え、寸法安定性を向上させ、耐湿性を向上させるために可塑剤を用いてもよい。
本発明に係る光学フィルムAには、偏光板又は液晶セル等の光等による劣化防止の観点から、紫外線吸収剤が好ましく用いられる。
本発明に係る光学フィルムは、下記(1)~(3)の要件を満たす有機酸を樹脂に対して0.01質量%~20質量%含有することが好ましい。
(1)多価アルコールと多価カルボン酸がエステル結合を形成して結合した構造を含む。(2)該化合物を形成する多価アルコールと多価カルボン酸の分子数の合計が3以上である。
(3)多価カルボン酸由来の無置換のカルボキシ基を少なくとも1つ有する。
カプロン酸、ヘプチル酸、カプリル酸、ペラルゴン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、リノール酸、リノレン酸、リシノレン酸、ウンデカン酸。
ミリスチル硫酸、セチル硫酸、オレイル硫酸。
ドデシルベンゼンスルフォン酸、ペンタデシルベンゼンスルフォン酸。
セスキブチルナフタレンスルフォン酸、ジイソブチルナフタレンスルフォン酸。
本発明に係る光学フィルムAには、ハンドリングされる際の耐傷性やスムーズな搬送性を付与する観点から、微粒子を添加することが一般に行われる。それらは、一般に、マット剤、ブロッキング防止剤あるいはキシミ防止剤と称されて、従来から利用されている。それらは、前述の機能を発現する素材であれば特に限定されず、マット剤としては、無機化合物から構成される無機マット剤であっても、有機化合物から構成される有機マット剤であってもよい。
光学フィルムA及び光学フィルムBは、溶液流延法又は溶融流延法で製造され得る。光学フィルムの着色や異物欠点、ダイライン等の光学欠点を抑制する観点では、溶液流延法が好ましく、光学フィルムに溶媒が残留するのを抑制する観点では、溶融流延法が好ましい。
セルロースアシレートを含む光学フィルムを溶液流延法で製造する方法は、例えば、A1)少なくともセルロースアシレートと、必要に応じて他の添加剤とを溶剤に溶解させてドープを調製する工程、A2)ドープを無端の金属支持体上に流延する工程、A3)流延したドープから溶媒を蒸発させてウェブとする工程、A4)ウェブを金属支持体から剥離する工程、A5)ウェブを乾燥後、延伸してフィルムを得る工程を含むことができる。
溶解釜において、樹脂と、必要に応じて他の添加剤とを溶剤に溶解させてドープを調製する。
ドープを、加圧ダイのスリットから無端状の金属支持体上に流延させる。
ウェブ(ドープを金属支持体上に流延して得られたドープ膜)を金属支持体上で加熱し、溶媒を蒸発させる。ウェブの乾燥方法や乾燥条件は、前述のA2)流延工程と同様とし得る。
金属支持体上で溶媒を蒸発させたウェブを、金属支持体上の剥離位置で剥離する。
なお、残留溶媒量を測定する際の加熱処理は、115℃で1時間の加熱処理を意味する。
金属支持体から剥離して得られたウェブを、必要に応じて乾燥させた後、延伸する。ウェブの乾燥は、ウェブを、上下に配置した多数のローラーにより搬送しながら乾燥させてもよいし、ウェブの両端部をクリップで固定して搬送しながら乾燥させてもよい。
溶融流延法で製造する方法は、B1)溶融ペレットを製造する工程(ペレット化工程)、B2)溶融ペレットを溶融混練した後、押し出す工程(溶融押出し工程)、B3)溶融樹脂を冷却固化してウェブを得る工程(冷却固化工程)、B4)ウェブを延伸する工程(延伸工程)、を含む。
光学フィルムの主成分である熱可塑性樹脂を含む樹脂組成物は、あらかじめ混練してペレット化しておくことが好ましい。ペレット化は、公知の方法で行うことができ、例えば前述の熱可塑性樹脂と、必要に応じて可塑剤等の添加剤とを含む樹脂組成物を、押出機にて溶融混錬した後、ダイからストランド状に押し出す。ストランド状に押し出された溶融樹脂を、水冷又は空冷した後、カッティングしてペレットを得ることができる。
得られた溶融ペレットと、必要に応じて他の添加剤とを、ホッパーから押出機に供給する。ペレットの供給は、ペレットの酸化分解を防止するため等から、真空下、減圧下又は不活性ガス雰囲気下で行うことが好ましい。そして、押出機にて、フィルム材料である溶融ペレット、必要に応じて他の添加剤を溶融混練する。
ダイから押し出された樹脂を、冷却ローラーと弾性タッチローラーとでニップして、フィルム状の溶融樹脂を所定の厚さにする。そして、フィルム状の溶融樹脂を、複数の冷却ローラーで段階的に冷却して固化させる。
得られたウェブを、延伸機にて延伸してフィルムを得る。延伸は、ウェブの幅方向又は搬送方向のいずれかに行う。
本発明に係る光学フィルムは、本発明の偏光板、それを用いた本発明の液晶表示装置に使用することができる。本発明に係る光学フィルムは、偏光板保護フィルムの機能を兼ねたフィルムであるため偏光板保護フィルムと別に位相差を有する光学フィルムを別途用意する必要がないため、液晶表示装置の厚さを薄くし製造プロセスを簡略化することができる。
活性エネルギー線硬化性接着剤の好ましい例としては、例えば、特開2011-028234号公報に開示されているような、(α)カチオン重合性化合物、(β)光カチオン重合開始剤、(γ)380nmより長い波長の光に極大吸収を示す光増感剤、及び(δ)ナフタレン系光増感助剤の各成分を含有する活性エネルギー線硬化性接着剤組成物が挙げられる。ただし、これ以外の活性エネルギー線硬化性接着剤組成物が用いられても、もちろんよい。
前処理工程では、偏光子と接着する位相差フィルムの表面が易接着処理される。偏光子の両面にそれぞれ位相差フィルム及び保護フィルムが接着される場合は、位相差フィルム及び保護フィルムのそれぞれに対し易接着処理が行われる。次の接着剤塗布工程では、易接着処理された表面が偏光子との貼合面として扱われるので、位相差フィルムの両表面のうち、活性エネルギー線硬化性接着剤と貼合する面に、易接着処理を施す。易接着処理としては、コロナ処理、プラズマ処理等が挙げられる。
接着剤塗布工程では、偏光子と位相差フィルムとの接着面のうち少なくとも一方に、上記活性エネルギー線硬化性接着剤が塗布される。偏光子又は位相差フィルムの表面に直接、活性エネルギー線硬化性接着剤を塗布する場合、その塗布方法に特別な限定はない。例えば、ドクターブレード、ワイヤーバー、ダイコーター、カンマコーター、グラビアコーター等、種々の湿式塗布方式が利用できる。また、偏光子と位相差フィルムの間に、活性エネルギー線硬化性接着剤を流延させたのち、ローラー等で加圧して均一に押し広げる方法も利用できる。
上記の方法により活性エネルギー線硬化性接着剤を塗布した後は、貼合工程で処理される。この貼合工程では、例えば、先の塗布工程で偏光子の表面に活性エネルギー線硬化性接着剤を塗布した場合、そこに位相差フィルムが重ね合わされる。先の塗布工程で位相差フィルムの表面に活性エネルギー線硬化性接着剤を塗布した場合は、そこに偏光子が重ね合わされる。また、偏光子と位相差フィルムの間に活性エネルギー線硬化性接着剤を流延させた場合は、その状態で偏光子と位相差フィルムとが重ね合わされる。偏光子の両面に位相差フィルム及び保護フィルムを接着する場合であって、両面とも活性エネルギー線硬化性接着剤用いる場合は、偏光子の両面にそれぞれ、活性エネルギー線硬化性接着剤を介して位相差フィルム及び保護フィルムが重ね合わされる。そして通常は、この状態で両面(偏光子の片面に位相差フィルムを重ね合わせた場合は、偏光子側と位相差フィルム側、また偏光子の両面に位相差フィルム及び保護フィルムを重ね合わせた場合は、その両面の位相差フィルム及び保護フィルム側)からローラー等で挟んで加圧することになる。ローラーの材質は、金属やゴム等を用いることが可能である。両面に配置されるローラーは、同じ材質であってもよいし、異なる材質であってもよい。
硬化工程では、未硬化の活性エネルギー線硬化性接着剤に活性エネルギー線を照射して、カチオン重合性化合物(例えば、エポキシ化合物やオキセタン化合物)やラジカル重合性化合物(例えば、アクリレート系化合物、アクリルアミド系化合物等)を含む活性エネルギー線硬化性接着剤を硬化させ、活性エネルギー線硬化性接着剤を介して重ね合わせた偏光子と位相差フィルム、あるいは偏光子と位相差フィルムとを接着させる。偏光子の片面に位相差フィルムを貼合する場合、活性エネルギー線は、偏光子側又は位相差フィルム側のいずれから照射してもよい。また、偏光子の両面に位相差フィルム及び保護フィルムを貼合する場合、偏光子の両面にそれぞれ活性エネルギー線硬化性接着剤を介して位相差フィルム及び保護フィルムを重ね合わせた状態で、活性エネルギー線を照射し、両面の活性エネルギー線硬化性接着剤を同時に硬化させるのが有利である。
本発明の偏光板は、液晶表示装置に具備することを特徴とする。
EAGLE XG(r) Slim(厚さ300μm、400μm等)、日本電気硝子社製のガラス基材(厚さ100~200μm)等を挙げることができる。
以下の実施例で用いた化合物をその略号とともに以下に示す。
〔一般式(1)で表される構造を有する化合物〕
B1:一般式(1)で表される構造を有する化合物の例示化合物(1-2)
B2:一般式(1)で表される構造を有する化合物の例示化合物(1-1)
B3:一般式(1)で表される構造を有する化合物の例示化合物(1-3)
N1:9H-カルバゾール-9-エタノール
N2:n-ヘキシルカルバゾール
N3:2,3-ジフェニルキノキサリン
N4:2-メチルベンゾオキサゾール
N5:2-(4-tert-ブチルフェニル)-5-(4-ビフェニル)-1,3,4-オキサジアゾール
N11:一般式(3)で表される構造を有する化合物の例示化合物1
N12:一般式(3)で表される構造を有する化合物の例示化合物6
N13:一般式(3)で表される構造を有する化合物の例示化合物176
S4〈重縮合エステル〉
重縮合エステルS4は以下のようにして調製した。
S5〈重縮合エステル〉
重縮合エステルS5は以下のようにして調製した。
S9:トリメチロールプロパントリベンゾアート
S12:ジフェニルビフェニルホスフェート
S15:以下の組成(質量比)からなる有機酸(多価アルコールと多価カルボン酸に加え、炭素数が4以上の置換基を有する一価の酸が該多価アルコールの一部のヒドロキシル基とエステル結合を形成した構造)を用いた。
〔実施例1〕
《光学フィルムAの作製》
《光学フィルムT1-1の作製》
光学フィルムT1-1は、厚さ60μmの市販の保護フィルムであるコニカミノルタ製KC6UAをそのまま用いた。
(アクリル樹脂とアクリル弾性系重合体粒子)
アクリル樹脂として、メタクリル酸メチル/アクリル酸メチルの質量比96/4の共重合体を使用した。また、ゴム弾性体粒子として、最内層、中間層、最外層からなる3層構造のアクリル系弾性重合体粒子を使用した。このアクリル系弾性重合体粒子は、最内層は、メタクリル酸メチルに少量のメタクリル酸アリルを用いて重合された硬質の重合体、中間層は、アクリル酸ブチルを主成分とし、さらにスチレン及び少量のメタクリル酸アリルを用いて重合された軟質の弾性体、最外層は、メタクリル酸メチルに少量のアクリル酸エチルを用いて重合された硬質の重合体からなり、中間層である弾性体までの平均粒径が240nmである。
上記のアクリル樹脂と上記のアクリル系弾性重合体粒子が前者/後者=70/30の質量比で配合されているペレットを二軸押出機で溶融混練しつつ、アクリル樹脂組成物のペレットとした。このペレットを65mmφの一軸押出機に投入し、設定温度275℃のT型ダイを介して押し出し、押し出されたフィルム状溶融樹脂の両面を、45℃に温度設定された鏡面を有するポリシングロール(冷却ロール)と、表面が金属材料で形成され内部に流体が充填された弾性率の高い金属弾性ロール(弾性ロール)とで挟み込んで冷却し、厚さ30μmのアクリル樹脂からなる光学フィルムT1-2を作製した。
((メタ)アクリル樹脂フィルムの作製)
[下記式中、R1は水素原子、R2およびR3はメチル基を表す、ラクトン環構造を有する(メタ)アクリル樹脂{共重合モノマー質量比=メタクリル酸メチル/2-(ヒドロキシメチル)アクリル酸メチル=8/2、ラクトン環化率約100%、ラクトン環構造の含有割合19.4%、重量平均分子量133000、メルトフローレート6.5g/10分(240℃、10kgf)、Tg131℃}90質量部と、アクリロニトリル-スチレン(AS)樹脂{トーヨーAS AS20、東洋スチレン社製}10質量部との混合物;Tg127℃]のペレットを二軸押し出し機に供給し、約280℃でシート状に溶融押し出しして、厚さ110μmのラクトン環構造を有する(メタ)アクリル樹脂シートを得た。この未延伸シートを、160℃の温度条件下、縦2.0倍、横2.4倍に延伸して(メタ)アクリル樹脂フィルム(厚さ:40μm、面内位相差値Ro:0.8nm、厚さ方向位相差値Rt:1.5nm)を得た。
上記で得られた(メタ)アクリル樹脂フィルムの片側に、コロナ放電処理(コロナ放電電子照射量:77W/m2/min)を施した。
(製造例1-ポリエステルA)
エステル化反応缶を昇温し200℃に到達した時点で、テレフタル酸を86.4質量部及びエチレングリコール64.6質量部を仕込み、撹拌しながら触媒として三酸化アンチモンを0.017質量部、酢酸マグネシウム4水和物を0.064質量部、トリエチルアミン0.16質量部を仕込んだ。次いで、加圧昇温を行いゲージ圧0.34MPa、240℃の条件で加圧エステル化反応を行った後、エステル化反応缶を常圧に戻し、リン酸0.014質量部を添加した。さらに、15分かけて260℃に昇温し、リン酸トリメチル0.012質量部を添加した。次いで15分後に、高圧分散機で分散処理を行い、15分後、得られたエステル化反応生成物を重縮合反応缶に移送し、280℃で減圧下重縮合反応を行った。
(製造例2-ポリエステルB)
次に、乾燥させた紫外線吸収剤(2,2′-(1,4-フェニレン)ビス(4H-3,1-ベンズオキサジノン-4-オン)10質量部、粒子を含有しないPET(A)(固有粘度が0.62dl/g)90質量部を混合し、混練押出機を用い、紫外線吸収剤含有するポリエチレンテレフタレート樹脂(B)を得た(以後、PET(B)と略す。)。
常法によりエステル交換反応及び重縮合反応を行って、ジカルボン酸成分として(ジカルボン酸成分全体に対して)テレフタル酸46モル%、イソフタル酸46モル%及び5-スルホナトイソフタル酸ナトリウム8モル%、グリコール成分として(グリコール成分全体に対して)エチレングリコール50モル%及びネオペンチルグリコール50モル%の組成の水分散性スルホン酸金属塩基含有共重合ポリエステル樹脂を調製した。次いで、水51.4質量部、イソプロピルアルコール38質量部、n-ブチルセルソルブ5質量部、ノニオン系界面活性剤0.06質量部を混合した後、加熱撹拌し、77℃に達したら、上記水分散性スルホン酸金属塩基含有共重合ポリエステル樹脂5質量部を加え、樹脂の固まりが無くなるまで撹拌し続けた後、樹脂水分散液を常温まで冷却して、固形分濃度5.0質量%の均一な水分散性共重合ポリエステル樹脂液を得た。さらに、凝集体シリカ粒子(富士シリシア(株)製、サイリシア310)3質量部を水50質量部に分散させた後、上記水分散性共重合ポリエステル樹脂液99.46質量部にサイリシア310の水分散液0.54質量部を加えて、撹拌しながら水20質量部を加えて、接着性改質塗布液を得た。
基材フィルム中間層用原料として粒子を含有しないPET(A)樹脂ペレット90質量部と紫外線吸収剤を含有したPET(B)樹脂ペレット10質量部を135℃で6時間減圧乾燥(1Torr)した後、押出機2(中間層II層用)に供給し、また、PET(A)を常法により乾燥して押出機1(外層I層及び外層III用)にそれぞれ供給し、285℃で溶解した。この2種のポリマーを、それぞれステンレス焼結体の濾材(公称濾過精度10μm粒子95%カット)で濾過し、2種3層合流ブロックにて、積層し、口金よりシート状にして押し出した後、静電印加キャスト法を用いて表面温度30℃のキャスティングドラムに巻きつけて冷却固化し、未延伸フィルムを作った。この時、I層、II層、III層の厚さの比は10:80:10となるように各押出機の吐出量を調整した。
(環状オレフィン系樹脂フィルム(COP)の作製)
環状オレフィン(COP)系樹脂からなる位相差フィルムとして、ZEONOR(日本ゼオン(株)製)を使用した。
光学フィルムT1-1~T1-10の透湿度の評価は、40℃・90%RHにおける水蒸気透過度をJIS K 7129(1992)に準拠した方法で測定して行った。
《位相差フィルムT2-1の作製》
〈微粒子分散液1〉
微粒子(アエロジル R812 日本アエロジル(株)製)
11質量部
エタノール 89質量部
以上をディゾルバーで50分間撹拌混合した後、マントンゴーリンで分散を行った。
メチレンクロライドを入れた溶解タンクに十分撹拌しながら、微粒子分散液1をゆっくりと添加した。更に、二次粒子の粒径が所定の大きさとなるようにアトライターにて分散を行った。これを日本精線(株)製のファインメットNFで濾過し、微粒子添加液1を調製した。
微粒子分散液1 5質量部
下記組成の主ドープを調製した。まず加圧溶解タンクにメチレンクロライドとエタノールを添加した。溶剤の入った加圧溶解タンクにアセチル基置換度2.60のセルロースアセテートを撹拌しながら投入した。これを加熱し、撹拌しながら、完全に溶解し。これを安積濾紙(株)製の安積濾紙No.244を使用して濾過し、主ドープを調製した。
メチレンクロライド 365質量部
エタノール 50質量部
セルロースアシレート(C5) 100質量部
微粒子添加液1 1質量部
以上を密閉されている主溶解釜1に投入し、撹拌しながら溶解してドープを調製した。
位相差フィルムT2-1において、主ドープの組成を表9に示されるように、セルロースアシレート樹脂100質量部に対して一般式(1)で表される構造を有する化合物を5質量部加えて調製し、その後は位相差フィルムT2-1と同様にして位相差フィルムT2-2~T2-7を作製した。
得られた光学フィルムBである位相差フィルムT2-1~T2-7の各々について、下記方法でリターデーション値を測定した。
得られた位相差フィルムから試料35mm×35mmを切り出し、23℃・55%RHで2時間調湿し、自動複屈折計(KOBRA-WR、王子計測(株))で、光波長590nmにおける垂直方向から測定した値とフィルム面を傾けながら同様に測定したリターデーション値の外挿値から以下の式より算出した。
式(ii) Rt={(nx+ny)/2-nz}×d
(式中、nxはフィルム面内の遅相軸方向の屈折率であり、nyはフィルム面内の進相軸方向の屈折率であり、nzはフィルムの厚さ方向の屈折率であり、dはフィルムの厚さ(nm)である。)
なお、リターデーション値Ro、Rtは、KOBRA-21ADH(王子計測機器株式会社製)を用いて、温度23℃、湿度55%RHの環境下で、波長が590nmで測定した。
(偏光子の調製)
厚さ50μmのポリビニルアルコールフィルムを、35℃の水で膨潤させた。得られたフィルムを、ヨウ素0.075g、ヨウ化カリウム5g及び水100gからなる水溶液に60秒間浸漬し、さらにヨウ化カリウム3g、ホウ酸7.5g及び水100gからなる45℃の水溶液に浸漬した。得られたフィルムを、延伸温度55℃、延伸倍率5倍の条件で一軸延伸した。この一軸延伸フィルムを、水洗した後、乾燥させて、厚さ10μmの偏光子1得た。
下記の方法に従って、カチオン重合型の活性エネルギー線硬化性接着剤液である接着層形成用塗布液1を調製した。
ンカルボキシレート 45質量部
エポリードGT-301(ダイセル化学社製の脂環式エポキシ樹脂)
40質量部
1,4-ブタンジオールジグリシジルエーテル 15質量部
トリアリールスルホニウムヘキサフルオロホスフェート
2.3質量部
9,10-ジブトキシアントラセン 0.1質量部
1,4-ジエトキシナフタレン 2.0質量部
(偏光板の作製)
まず、光学フィルムBとしてT2-1を用い、その表面にコロナ放電処理を施した。なお、コロナ放電処理の条件は、コロナ出力強度2.0kW、ライン速度18m/分とした。次いで、T2-1のコロナ放電処理面に、上記調製した接着層形成用塗布液1を、硬化後の膜厚が約3μmとなるようにバーコーターで塗工して活性エネルギー線硬化性樹脂層(接着層ともいう。)を形成した。得られた活性エネルギー線硬化性樹脂層に、上記調製したポリビニルアルコール-ヨウ素系の偏光子を貼合した。
偏光板1の作製において、位相差フィルムT2-1を位相差フィルムT2-2~T2-7に代えて、偏光板1の作製と同様にして偏光板2~7を作製した。
市販のVA型液晶表示装置(SONY製40型ディスプレイKLV-40J3000)のあらかじめ貼合されていた両面の偏光板を剥がして、上記作製した偏光板1~7をそれぞれ液晶セルのガラス面の両面に、貼合した。
上記作製した各液晶表示装置について、色ムラと点状欠陥の各評価を行った。
上記作製した液晶表示装置を寝かせて台の上などに置き、ベンコット(登録商標、旭化成せんい社製)を評価用偏光板の一部に載せて水を含ませた。ベンコットが乾かないよう100μmPETで覆い、テレビにPCから黒表示の信号を入力、テレビの電源ONで24時間放置した(室温は23℃に設定、パネル温度は38℃)。24時間後、ベンコットを取り除く。ベンコットのあった部分のL*(輝度)を水浸漬部のL*としてEZコントラスト(ELDIM社製)で測定した。ベンコットのない部分のL*を非浸漬部のL*としてEZコントラストで測定した。なお、EZコントラストでの測定はTVを黒表示にしてカラーモードにて行った。水浸漬の条件はパネルの電源をONにし、かつ水を十分に浸み込ませたベンコットを貼り付けた状態で24時間静置する条件とした。次いで、水浸漬部のL*/非浸漬部のL*の比の値を算出し、下記の基準に従って色ムラの評価を行った。
○:1.30超1.55以下:ごく僅かに弱い色ムラの発生が認められるが、実用上問題のない品質である
△:1.55超1.80以下:色ムラの発生が僅かに認められるが、実用上問題のないレベルである
×:1.80超:強い色ムラが発生し、耐湿性に問題のある品質である
なお、水浸漬部のL*/非浸漬部のL*の比の値が1.05以上の場合、点状欠陥が認められる試料はなかったが、比の値が1.05未満の場合は、点状欠陥が発生した場合を含むため、色ムラの評価は目視での評価で確認した。
フィルムを偏光板に貼合する。これを液晶表示装置に組み込み、黒表示にしたときの点状あるいは面状で現れる明暗を目視で観察し、下記基準でランク付けした。
ランク 基準
◎ :光の抜けはなく全体に均一な暗視野
○ :部分的にごく僅かに明暗が認められる
○△:部分的に僅かに明暗が認められる
△ :全体的に僅かに明暗が認められるが、実用上問題のないレベルである
× :全体に明暗が認められる
なお、従来色ムラと点状欠陥を両立させることは難しく、上記評価で色ムラと点状欠陥の両方のランクが△以上であれば、実用に供することができる。
実施例1の偏光板2の作製において、光学フィルムAをT1-8から表5に示したようにT1-1~T1-10に代え、偏光板11~20を作製し、その後それぞれの偏光板を用い実施例1と同様にして液晶表示装置11~20を作製した。
実施例1の偏光板2の作製において、光学フィルムT2-2(光学フィルムB)の作製に用いた、セルロースアシレート樹脂をC5からC1~C7を用いて表11に記載のように変え、実施例1と同様にして偏光板31~37を作製した。その後それぞれの偏光板を用い実施例1と同様にして液晶表示装置31~37を作製した。
実施例1の偏光板2の作製において、光学フィルムT2-2(光学フィルムB)の作製に用いた、一般式(1)で表される構造を有するを有する化合物の量を表12のように変えて、実施例1と同様にして偏光板41~46を作製した。その後それぞれの偏光板を用い実施例1と同様にして液晶表示装置41~46を作製した。及び光学フィルムBの膜厚を表12のように変えて実施例1と同様にして液晶表示装置47~53を作製した。
実施例1の偏光板2の作製における、光学フィルムT2-2(光学フィルムB)の作製において、位相差上昇剤を表13のように加えて、実施例1と同様にして偏光板61~73を作製した。その後それぞれの偏光板を用い実施例1と同様にして液晶表示装置61~73を作製した。
実施例1の偏光板2の作製における、光学フィルムT2-2(光学フィルムB)の作製において、可塑剤を表14のように加えて、実施例1と同様にして偏光板81~96を作製した。その後それぞれの偏光板を用い実施例1と同様にして液晶表示装置81~96を作製した。
《偏光板101の作製》
実施例1における偏光板2の作製と同様にして、偏光板101を作成した。
実施例1における偏光板2の作製において、偏光子と光学フィルムA及びBとの接着層として、下記に示すラジカル重合型の接着層形成用塗布液2を用いた以外は同様にして、偏光板102を作製した。この接着層の形成方法を、「UV接着2」と称す。
N-ヒドロキシエチルアクリルアミド100質量部に、光重合開始剤(BASFジャパン(株)製;商品名イルガキュア127)3質量部を配合したものを接着層形成用塗布液2として用いた。
上記偏光板2の作製において、光学フィルムAと偏光子、及び光学フィルムBと偏光子との接着は、実施例1と同様に偏光子を作成したあと、下記工程1~5を経て行った。
《液晶表示装置の作製》
上記作製した偏光板101~103を用いて、実施例1と同様にして、液晶表示装置101、及び102をそれぞれ作製して実施例1と同様に評価した。結果を表15に示す。
実施例1の偏光板2の作製における、光学フィルムT2-2(光学フィルムB)の作製において、セルロースアシレート樹脂、一般式(1)で表される構造を有する化合物、位相差上昇剤、可塑剤の種類と量、及び光学フィルムBの膜厚を、表16のようにそれぞれ変えて、実施例1と同様にして偏光板110~150を作製した。その後それぞれの偏光板を用い実施例1と同様にして液晶表示装置110~150を作製した。
以下のようにして光学フィルムBとして、下記の手順に従って、3層同時流延法(共流延法)により、3層構成のセルロースアシレートフィルムT2-131を作製した。
図2に示す共流延ダイを用いて、下記の手順に従って、3層同時流延法(共流延法)により3層構成(C4/C1/C4)のセルロースアシレートフィルムT2-131を作製した。
実施例1の主ドープの調製において、セルロースアシレートをC5からC1、C4に変え、一般式(1)で表される構造を有する化合物、位相差上昇剤及び可塑剤を表17に示す量を加えて、コア用のドープCとスキン用のドープSをそれぞれ調製した。
上記ドープを用いて、図2に示す流延用の金属支持体である無端ベルト面側より、スキン層(B面)としてドープSを、コア層としてドープCを、スキン層(A面)としてドープSを、同時に共流延ダイ50に供給し、一度の流延操作によって、スキン層(B面)61/コア層62/スキン層(A面)63から構成される積層体である多層構造ウェブ60を無端ベルト上に供給した。各ドープの供給量は、最終的に乾燥が完了した後の各層の膜厚が、スキン層(B面)/コア層/スキン層(A面)=5μm/40μm/5μmとなる条件とした。
101A、101B 偏光板
101C 液晶セル
102 光学フィルムA
103A、103B 活性エネルギー線硬化性接着剤
104 偏光子
105 光学フィルムB
106 粘着層
107 液晶層
108A、108B ガラス基材
BL バックライト
50 共流延ダイ
51 口金部分
53、55 層B、層C用スリット
54 層A用スリット
56 金属支持体
57、59 層B、層C用ドープ
58 層A用ドープ
60 多層構造ウェブ
61 スキン層
62 コア層
63 スキン層
Claims (12)
- 光学フィルムA、偏光子及び光学フィルムBが、この順で積層された偏光板であって、前記光学フィルムAは、アクリル樹脂又はポリエステル樹脂の少なくともいずれかを含有する光学フィルムであり、前記光学フィルムBは、アシル基置換度が2.1~3.0の範囲内のセルロースアシレート樹脂と、下記一般式(1)で表される構造を有する化合物とを含有する位相差フィルムであることを特徴とする偏光板。
- 前記光学フィルムBの面内方向のリターデーション値Roと厚さ方向のリターデーション値Rtとが、23℃・55%RHの環境下で、それぞれ下記の範囲内であることを特徴とする請求項1に記載の偏光板。
Ro:20~130nm
Rt:100~300nm - 前記光学フィルムBの膜厚が、10~90μmの範囲内であることを特徴とする請求項1又は請求項2に記載の偏光板。
- 前記光学フィルムBに含まれるセルロースアシレート樹脂が、アセチル基置換度が2.1~2.7の範囲内のセルロースアセテート樹脂であることを特徴とする請求項1から請求項3までのいずれか一項に記載の偏光板。
- 前記光学フィルムBに含まれるセルロースアシレート樹脂が、アセチル基置換度が2.6~2.7の範囲内のセルロースアセテート樹脂であることを特徴とする請求項1から請求項4までのいずれか一項に記載の偏光板。
- 前記光学フィルムAの40℃・90%RHにおける水蒸気透過度が、20~120g/m2・24hrの範囲内であることを特徴とする請求項1から請求項6までのいずれか一項に記載の偏光板。
- 前記光学フィルムBの膜厚が、10~40μmの範囲内であることを特徴とする請求項1から請求項8までのいずれか一項に記載の偏光板。
- 前記光学フィルムBが、含窒素位相差上昇剤を含有していることを特徴とする請求項1から請求項8までのいずれか一項に記載の偏光板。
- 前記含窒素位相差上昇剤が、カルバゾール環、キノキサリン環、ベンゾオキサゾール環、オキサジアゾール環、オキサゾール環、トリアゾール環及びピラゾール環を有する化合物から選ばれる少なくともいずれか一種であることを特徴とする請求項9に記載の偏光板。
- 前記光学フィルムAと前記光学フィルムBとが、それぞれ活性エネルギー線硬化性接着剤を用いて前記偏光子と貼合されていることを特徴とする請求項1から請求項10までのいずれか一項に記載の偏光板。
- 請求項1から請求項11までのいずれか一項に記載の偏光板が具備されていることを特徴とする液晶表示装置。
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WO2016052226A1 (ja) * | 2014-10-03 | 2016-04-07 | Dic株式会社 | エポキシエステル化合物、セルロースエステル樹脂組成物、光学フィルム及び液晶表示装置 |
JP2016173467A (ja) * | 2015-03-17 | 2016-09-29 | Dic株式会社 | 光学フィルム及び液晶表示装置 |
CN106094347A (zh) * | 2015-04-27 | 2016-11-09 | 柯尼卡美能达株式会社 | 相位差膜、偏振片、垂直取向型液晶显示装置及相位差膜的制造方法 |
JP2017040757A (ja) * | 2015-08-19 | 2017-02-23 | コニカミノルタ株式会社 | 位相差フィルム、偏光板および液晶表示装置 |
JP2017072775A (ja) * | 2015-10-09 | 2017-04-13 | コニカミノルタ株式会社 | 位相差フィルム、偏光板および液晶表示装置 |
JP2017122918A (ja) * | 2015-04-10 | 2017-07-13 | 東洋紡株式会社 | 液晶表示装置 |
JP2020090614A (ja) * | 2018-12-06 | 2020-06-11 | コニカミノルタ株式会社 | 樹脂組成物及びそれを用いた成形体 |
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KR20170066363A (ko) * | 2014-10-03 | 2017-06-14 | 디아이씨 가부시끼가이샤 | 에폭시에스테르 화합물, 셀룰로오스에스테르 수지 조성물, 광학 필름 및 액정 표시 장치 |
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KR102399287B1 (ko) | 2014-10-03 | 2022-05-19 | 디아이씨 가부시끼가이샤 | 에폭시에스테르 화합물, 셀룰로오스에스테르 수지 조성물, 광학 필름 및 액정 표시 장치 |
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Also Published As
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KR20160027988A (ko) | 2016-03-10 |
JPWO2015019929A1 (ja) | 2017-03-02 |
JP6465025B2 (ja) | 2019-02-06 |
KR101778477B1 (ko) | 2017-09-13 |
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