WO2021230010A1 - Circularly polarizing plate - Google Patents
Circularly polarizing plate Download PDFInfo
- Publication number
- WO2021230010A1 WO2021230010A1 PCT/JP2021/015832 JP2021015832W WO2021230010A1 WO 2021230010 A1 WO2021230010 A1 WO 2021230010A1 JP 2021015832 W JP2021015832 W JP 2021015832W WO 2021230010 A1 WO2021230010 A1 WO 2021230010A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- layer
- polarizing plate
- circularly polarizing
- retardation
- retardation layer
- Prior art date
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- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- WOTCTOFEBNHWND-UHFFFAOYSA-M potassium;oxaldehydate Chemical compound [K+].[O-]C(=O)C=O WOTCTOFEBNHWND-UHFFFAOYSA-M 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012508 resin bead Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- SOEVVANXSDKPIY-UHFFFAOYSA-M sodium glyoxylate Chemical compound [Na+].[O-]C(=O)C=O SOEVVANXSDKPIY-UHFFFAOYSA-M 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3016—Polarising elements involving passive liquid crystal elements
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/022—Mechanical properties
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
-
- 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
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/50—OLEDs integrated with light modulating elements, e.g. with electrochromic elements, photochromic elements or liquid crystal elements
Definitions
- the present invention relates to a circularly polarizing plate, and particularly to a thin bending-resistant circularly polarizing plate.
- a circularly polarizing plate is provided on the visible surface of the organic EL display in order to solve problems such as reflection of external light and reflection of the background.
- a circularly polarizing plate has a circularly polarized light function by laminating a ⁇ / 4 retardation layer on a linearly polarized light layer.
- a positive C layer is attached to the ⁇ / 4 retardation layer for the purpose of optical compensation such as preventing the reflected light from being colored when viewed from an angle.
- a liquid crystal coating type is usually used as the retardation layer such as the ⁇ / 4 retardation layer and the positive C layer.
- the liquid crystal coating type retardation layer refers to a retardation layer formed by applying a composition for forming a retardation layer on an alignment layer and curing the coating film.
- Patent Document 1 describes a liquid crystal coated elliptical polarizing plate having a polarizing layer, a ⁇ / 4 retardation layer, a vertically oriented liquid crystal curing layer, and a reinforcing layer.
- a reinforcing layer is introduced between the polarizing layer and the ⁇ / 4 retardation layer to improve the mechanical strength, and when the liquid crystal cured film is cut, problems such as waviness at the cut end face occur.
- Excellent processing characteristics are obtained (Examples 7 to 9, Comparative Example 2).
- Patent Document 2 describes a base material, a polarizing coating layer formed on one surface of the base material, a first adhesive layer formed on the polarizing coating layer, a first retardation coating layer formed on the first adhesive layer, and a first position.
- the soft layer includes a second adhesive layer formed on the phase difference coating layer, a second retardation coating layer formed on the second adhesive layer, and a soft layer formed on the second retardation coating layer.
- the maximum stress indicates the stress at the fracture point in the stress-deformation rate graph
- the maximum deformation rate indicates the deformation rate at the fracture point in the stress-deformation rate graph.
- a polarizing plate having a modified toughness of 1,000 to 40,000 MPa ⁇ % as defined in the above is described.
- the modified toughness of the soft layer corresponding to the reinforcing layer in Patent Document 1 is defined as described above, and by selecting an appropriate film satisfying this, the circularly polarizing plate is made flexible. ing.
- Patent Document 1 does not mention the improvement of bending resistance of the polarizing plate. Further, in the circularly polarizing plate described in Patent Document 2, a relatively rigid resin such as bifunctional urethane acrylate, triacetyl cellulose, or polyethylene terephthalate is used as a soft layer corresponding to the reinforcing layer, and is flexible. (Flexibility) is insufficient.
- a relatively rigid resin such as bifunctional urethane acrylate, triacetyl cellulose, or polyethylene terephthalate is used as a soft layer corresponding to the reinforcing layer, and is flexible. (Flexibility) is insufficient.
- the present invention solves the problems of the conventional circularly polarizing plate, and an object of the present invention is to provide a circularly polarizing plate having excellent flexibility and excellent bending resistance.
- the present invention A circularly polarizing plate having a polarizing layer including a linear polarizing layer and a retardation layer including a liquid crystal coating type retardation layer.
- the circularly polarizing plate has a crack strain of 15% or more.
- the crack strain is the elongation rate (%) when cracks occur in the circularly polarizing plate by pulling both ends of a circularly polarizing plate having a length of 5 cm and a width of 10 mm at a speed of 4 mm / min in the length direction.
- a circularly polarizing plate Provided is a circularly polarizing plate.
- the retardation layer comprises a ⁇ / 4 retardation layer, a retardation layer bonding layer, and a positive C layer.
- the retardation layer bonded layer has an elastic modulus of 1 GPa or more.
- the retardation layer bonding layer has a thickness of 1 to 5 ⁇ m.
- the positive C layer is a liquid crystal coating type retardation layer.
- the retardation layer has a reinforcing layer on at least one of its surfaces.
- the reinforcing layer is formed on top of the retardation layer.
- the reinforcing layer is formed below the retardation layer.
- the reinforcing layer is formed on the upper part and the lower part of the retardation layer.
- the circularly polarizing plate has a thickness of 5 to 50 ⁇ m.
- the circularly polarizing plate is cracked or broken in the retardation layer when the operation of bending and stretching 180 ° with a bending radius of 1 mm with the polarizing layer inside is repeated 300,000 times. Has bending resistance that does not occur.
- a circularly polarizing plate having excellent flexibility and excellent bending resistance is provided.
- the circularly polarizing plate of the present invention can be bent with a small bending radius of, for example, a bending radius of 1 mm. Further, in the circularly polarizing plate of the present invention, the retardation layer is not cracked or broken when the operation of bending and stretching 180 ° at a bending radius of 1 mm is repeated 300,000 times with the polarizing layer inside. ..
- FIG. 1 is a cross-sectional view showing an example of the structure of the circularly polarizing plate 100 according to the present invention.
- the circular polarizing plate 100 shown in FIG. 1 includes a polarizing layer 10, an adhesive layer 20, and a retardation layer 30 in this order from the polarizing layer side.
- the polarizing layer 10 includes a linear polarizing layer 12.
- the retardation layer 30 includes a ⁇ / 4 retardation layer 31, a retardation layer bonding layer 32, and a positive C layer 33 in this order from the polarizing layer side.
- a front plate may be further laminated on the polarizing layer 10 side of the circular polarizing plate 100.
- the polarizing layer 10 includes a protective layer 11, a linear polarizing layer 12, and an overcoat layer 13 in this order from the visible outside.
- the protective layer 11 is provided on the linearly polarized light layer and has a function of protecting the linearly polarized light layer 12.
- the material of the protective layer is not particularly limited, but for example, a cyclic polyolefin resin, a triacetyl cellulose (TAC), a cellulose acetate resin composed of a resin such as diacetyl cellulose, polyethylene terephthalate, polyethylene naphthalate, and the like.
- TAC triacetyl cellulose
- a cellulose acetate resin composed of a resin such as diacetyl cellulose, polyethylene terephthalate, polyethylene naphthalate, and the like.
- resins known in the art such as polyester-based resins made of resins such as polybutylene terephthalate, polycarbonate-based resins, (meth) acrylic-based resins, and polypropylene-based resins.
- the thickness of the protective layer is usually 100 ⁇ m or less, preferably 80 ⁇ m or less, more preferably 50 ⁇ m or less, and usually 5 ⁇ m or more, and 20 ⁇ m or more.
- the protective layer may be a film, and the film-like protective layer may have a phase difference.
- the protective layer is a film, the linearly polarized light layer and the protective layer can be laminated via an adhesive layer or an adhesive layer.
- the protective layer 11 may be an overcoat layer described later, and may be an organic layer or an inorganic layer.
- the organic or inorganic layer can be a layer formed by the coating.
- the organic layer can be formed by using a composition for forming a protective layer, for example, a (meth) acrylic resin composition, an epoxy resin composition, a polyimide resin composition, or the like.
- the composition for forming a protective layer may be an active energy ray-curable type or a thermosetting type.
- the inorganic layer can be formed from, for example, silicon oxide.
- the protective layer 11 is an organic layer, the protective layer may be called a hard coat layer.
- the protective layer 11 When the protective layer 11 is an organic layer, the protective layer can be produced, for example, by applying an active energy ray-curable protective layer forming composition on a base film and irradiating it with active energy to cure it. .. As the base film, the description of the resin plate-like body of the front plate described later is applied. The substrate film is usually stripped and removed. Examples of the method for applying the protective layer forming composition include a bar coating method and a spin coating method. When the protective layer 11 is an inorganic layer, the protective layer can be formed by, for example, a sputtering method, a vapor deposition method, or the like. When the protective layer 11 is an organic layer or an inorganic layer, the thickness of the protective layer 11 may be, for example, 0.1 ⁇ m or more and 10 ⁇ m or less, preferably 0.5 ⁇ m or more and 5 ⁇ m or less.
- the linearly polarized light layer 12 is a layer having a function of selectively transmitting unidirectional linearly polarized light from unpolarized light rays such as natural light.
- the linear polarizing layer 12 contains, for example, a cured product of a polymerizable liquid crystal compound and a dichroic dye, and the dichroic dye is dispersed and oriented in the cured product of the polymerizable liquid crystal compound.
- the dimensional change of the linearly polarizing layer 12 is small as compared with the linearly polarizing layer in which a dichroic dye such as iodine is adsorbed and oriented on a polyvinyl alcohol-based resin because the shrinkage amount in the moist heat test is small. Therefore, it can be suitably used for a circularly polarizing plate used in an environment where wet and heat durability is required.
- the polymerizable liquid crystal compound is a compound having a polymerizable reactive group and exhibiting liquid crystallinity.
- the polymerizable reactive group is a group involved in the polymerization reaction, and is preferably a photopolymerizable reactive group.
- the photopolymerizable reactive group refers to a group that can participate in the polymerization reaction by an active radical, an acid, or the like generated from the photopolymerization initiator.
- Examples of the photopolymerizable functional group include a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, an oxylanyl group, an oxetanyl group and the like.
- acryloyloxy group, methacryloyloxy group, vinyloxy group, oxylanyl group and oxetanyl group are preferable, and acryloyloxy group is more preferable.
- the type of the polymerizable liquid crystal compound is not particularly limited, and a rod-shaped liquid crystal compound, a disk-shaped liquid crystal compound, and a mixture thereof can be used.
- the liquid crystal property of the polymerizable liquid crystal compound may be a thermotropic liquid crystal or a lyotropic liquid crystal, and the phase-ordered structure may be a nematic liquid crystal or a smectic liquid crystal.
- a dichroic dye is a dye having a property in which the absorbance in the major axis direction and the absorbance in the minor axis direction of the molecule are different.
- the dichroic dye preferably has an absorption maximum wavelength ( ⁇ MAX) in the range of 300 to 700 nm.
- ⁇ MAX absorption maximum wavelength
- examples of such dichroic dyes include acridine dyes, oxazine dyes, cyanine dyes, naphthalene dyes, azo dyes, anthraquinone dyes and the like, and among these, azo dyes are preferable.
- the azo dye examples include a monoazo dye, a bisazo dye, a trisazo dye, a tetrakisazo dye, a stilbene azo dye and the like, and a bisazo dye and a trisazo dye are preferable.
- the dichroic dye may be used alone or in combination of two or more, but it is preferable to use three or more in combination. In particular, it is preferable to combine three or more kinds of azo compounds.
- a part of the dichroic dye may have a reactive group or may have a liquid crystallinity.
- the linearly polarizing layer 12 for example, a composition for forming a linearly polarizing layer containing a polymerizable liquid crystal compound and a dichroic dye is applied onto an alignment layer formed on the protective layer 11, and the polymerizable liquid crystal compound is polymerized. It can be formed by curing.
- the linearly polarizing layer 12 may be formed by applying a composition for forming a linearly polarized light layer on the base material layer to form a coating film and stretching the coating film together with the base material layer.
- the alignment layer has an orientation regulating force that orients the polymerizable liquid crystal compound in a desired direction.
- the oriented layer include an oriented polymer layer formed of an oriented polymer, a photo-oriented polymer layer formed of a photo-aligned polymer, and a grub-aligned layer having an uneven pattern or a plurality of grubs (grooves) on the layer surface. Can be done.
- the thickness of the alignment layer is usually 10 to 500 nm, preferably 10 to 200 nm.
- the oriented polymer layer is formed by applying a composition in which an oriented polymer is dissolved in a solvent to a base material layer or a base material layer for a retardation layer to remove the solvent, and if necessary, rubbing treatment. Can be done.
- the orientation restricting force can be arbitrarily adjusted depending on the surface condition and rubbing conditions of the oriented polymer.
- the photo-oriented polymer layer can be formed by applying a composition containing a polymer or monomer having a photoreactive group and a solvent to a base material layer or a base material layer for a retardation layer and irradiating with polarized light. ..
- the orientation restricting force can be arbitrarily adjusted in the photo-alignment polymer layer depending on the polarization irradiation conditions for the photo-alignment polymer.
- the grub alignment layer is a method of forming an uneven pattern by exposure, development, or the like through an exposure mask having a pattern-shaped slit on the surface of a photosensitive polyimide film, or a plate-shaped master having a groove on the surface.
- compositions for forming a linearly polarizing layer containing a polymerizable liquid crystal compound and a dichroic dye examples include JP-A-2013-37353 and JP-A-2013-3324. , Japanese Unexamined Patent Publication No. 2017-83843, and the like.
- the composition for forming a linear polarizing layer further contains additives such as a solvent, a polymerization initiator, a cross-linking agent, a leveling agent, an antioxidant, a plasticizer, and a sensitizer. It may be included. Each of these components may be used alone or in combination of two or more.
- the thickness of the linearly polarizing layer 12 is, for example, 0.3 to 10 ⁇ m, preferably 0.5 to 8 ⁇ m, and more preferably 1 to 5 ⁇ m.
- the overcoat layer 13 is provided for the purpose of protecting the linearly polarized light layer 12, suppressing the migration of the dichroic dye in the linearly polarized light layer 12, and imparting a barrier property to oxygen and water.
- the overcoat layer 13 may be provided on both sides of the linearly polarizing layer 12.
- the overcoat layer 13 can be formed, for example, by applying a material (composition) for forming the overcoat layer 13 on the surface of the linearly polarized light layer 12.
- the overcoat layer 13 is preferably excellent in solvent resistance, transparency, mechanical strength, thermal stability, shielding property, isotropic property, and the like.
- Examples of the material constituting the overcoat layer 13 include a photocurable resin and a water-soluble polymer.
- Examples of the photocurable resin include (meth) acrylic resin, urethane resin, (meth) acrylic urethane resin, epoxy resin, silicone resin and the like.
- Examples of the water-soluble polymer include poly (meth) acrylamide-based polymers; polyvinyl alcohol and ethylene-vinyl alcohol copolymers, ethylene-vinyl acetate copolymers, (meth) acrylic acid or its anhydride-vinyl alcohol co-weight.
- Examples thereof include vinyl alcohol-based polymers such as coalesced; carboxyvinyl-based polymers; polyvinylpyrrolidone; starches; sodium alginate; polyethylene oxide-based polymers.
- the thickness of the overcoat layer 13 is, for example, 0.1 to 5 ⁇ m, preferably 0.3 to 4 ⁇ m, and more preferably 0.5 to 3 ⁇ m.
- the adhesive layer 20 is a layer in which a polarizing layer 10 and a retardation layer 30 are bonded together.
- the adhesive layer 20 is an adhesive layer or an adhesive layer.
- the pressure-sensitive adhesive is an adhesive having pressure-sensitive adhesiveness.
- the adhesive layer 20 is preferably an adhesive layer.
- the adhesive layer 20 When the adhesive layer 20 is an adhesive layer, the adhesive layer contains, for example, a resin such as (meth) acrylic, rubber, urethane, ester, silicone, or polyvinyl ether as a main component. Consists of a pressure-sensitive adhesive composition. Among these, a pressure-sensitive adhesive composition using a (meth) acrylic resin having excellent transparency, weather resistance, heat resistance and the like as a base polymer is preferable.
- the pressure-sensitive adhesive composition may be an active energy ray-curable type or a thermosetting type.
- Examples of the (meth) acrylic resin (base polymer) used in the pressure-sensitive adhesive composition include butyl (meth) acrylate, ethyl (meth) acrylate, isooctyl (meth) acrylate, and 2- (meth) acrylate.
- a polymer or copolymer having one or more of (meth) acrylic acid esters such as ethylhexyl as a monomer is preferably used. It is preferable that the base polymer is copolymerized with a polar monomer.
- Examples of the polar monomer include (meth) acrylic acid, 2-hydroxypropyl (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, and glycidyl ( Examples thereof include monomers having a carboxyl group, a hydroxyl group, an amide group, an amino group, an epoxy group and the like, such as meth) acrylate.
- the pressure-sensitive adhesive composition may consist of the base polymer alone, but usually further contains a cross-linking agent.
- the cross-linking agent is a divalent or higher metal ion that forms a carboxylic acid metal salt with a carboxyl group; a polyamine compound that forms an amide bond with a carboxyl group; Examples thereof include polyepoxy compounds and polyols that form an ester bond with a carboxyl group; polyisocyanate compounds that form an amide bond with a carboxyl group, and the like. Among these, a polyisocyanate compound is preferable.
- the active energy ray-curable pressure-sensitive adhesive composition has a property of being cured by being irradiated with active energy rays such as ultraviolet rays and electron beams, and has adhesiveness even before irradiation with active energy rays. It can be brought into close contact with an adherend such as a film. It can be cured by irradiation with active energy rays and the adhesion can be adjusted.
- the active energy ray-curable pressure-sensitive adhesive composition is preferably an ultraviolet-curable type.
- the active energy ray-curable pressure-sensitive adhesive composition contains an active energy ray-polymerizable compound in addition to the base polymer and the cross-linking agent as described above. It also contains a photopolymerization initiator, a photosensitizer and the like as appropriate.
- the pressure-sensitive adhesive composition includes fine particles for imparting light scattering properties, beads (resin beads, glass beads, etc.), glass fibers, resins other than the base polymer, adhesive adhesive-imparting agents, fillers (metal powder and other materials). Additives such as (inorganic powder, etc.), antioxidants, ultraviolet absorbers, dyes, pigments, colorants, defoaming agents, corrosion inhibitors, photopolymerization initiators, etc. may be further contained.
- the pressure-sensitive adhesive layer can be formed by applying an organic solvent diluted solution of the pressure-sensitive adhesive composition on a substrate and drying it.
- the formed pressure-sensitive adhesive layer can be irradiated with active energy rays to obtain a cured product having a desired degree of curing.
- the thickness of the pressure-sensitive adhesive layer is, for example, 0.1 to 30 ⁇ m, preferably 0.5 to 20 ⁇ m, and more preferably 1 to 10 ⁇ m.
- the adhesive layer 20 is an adhesive layer
- the adhesive layer is formed from, for example, a water-based adhesive or an active energy ray-curable adhesive.
- water-based adhesive examples include a polyvinyl alcohol-based resin aqueous solution and a water-based two-component urethane-based emulsion adhesive composition, and a polyvinyl alcohol-based resin aqueous solution is preferable.
- the content of the polyvinyl alcohol-based resin is preferably 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of water, and 1 part by mass or more and 5 parts by mass or less. The following is more preferable.
- a polyhydric aldehyde, a water-soluble epoxy compound, a melamine compound, a zirconia compound, a zinc compound, or the like may be added to the water-based adhesive as an additive.
- the water-based adhesive preferably contains a curable component such as a metal salt of glyoxylic acid, glyoxal, and a water-soluble epoxy resin and / or a cross-linking agent in order to improve the adhesiveness.
- a curable component such as a metal salt of glyoxylic acid, glyoxal, and a water-soluble epoxy resin and / or a cross-linking agent in order to improve the adhesiveness.
- the metal salt of glyoxylic acid is preferably an alkali metal salt or an alkaline earth metal salt, and examples thereof include sodium glyoxylate, potassium glyoxylate, magnesium glyoxylate, and calcium glyoxylate.
- the water-soluble epoxy resin is a polyamide polyamine epoxy resin obtained by reacting a polyamide amine obtained by reacting a polyalkylene polyamine such as diethylenetriamine or triethylenetetramine with a dicarboxylic acid such as adipic acid with epichlorohydrin. Can be preferably used.
- the active energy ray-curable adhesive contains an active energy ray-curable compound.
- the active energy ray-curable compound include a cationically polymerizable compound and a radically polymerizable compound.
- a cationically polymerizable compound or a radically polymerizable compound is contained, the effect of increasing the hardness of the adhesive layer can be expected.
- Examples of the cationically polymerizable compound include an oxetane compound and an epoxy compound.
- the content of the cationically polymerizable compound is preferably 10 parts by mass or more and 99 parts by mass or less, and 40 parts by mass or more and 99 parts by mass or less, with respect to 100 parts by mass of the active energy ray-curable adhesive composition. Is more preferable.
- the active energy ray-curable adhesive may contain only one type of oxetane compound, or may contain two or more types.
- the active energy ray-curable adhesive may contain only one type of epoxy compound, or may contain two or more types of epoxy compounds.
- Examples of the radically polymerizable compound include (meth) acrylic compounds and (meth) acrylamide compounds.
- Examples of the (meth) acrylic compound include a (meth) acrylate monomer having at least one (meth) acryloyloxy group in the molecule and a (meth) acrylate having at least two (meth) acryloyloxy groups in the molecule.
- Examples include oligomers. These may be used alone or in combination of two or more.
- Examples of the (meth) acrylamide compound include N-substituted (meth) acrylamide compounds.
- the N-substituted (meth) acrylamide compound is a (meth) acrylamide compound having a substituent at the N-position.
- a typical example of the substituent is an alkyl group.
- the substituents at the N-position may be bonded to each other to form a ring, and -CH 2- which constitutes this ring may be substituted with an oxygen atom.
- N-substituted (meth) acrylamide can generally be produced by the reaction of (meth) acrylic acid or its chloride with a primary or secondary amine.
- the content of the radically polymerizable compound is preferably 1 part by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the active energy ray-curable adhesive, and more preferably 10 parts by mass or more and 60 parts by mass or less. ..
- the active energy ray-curable adhesive may contain only one type of radically polymerizable compound, or may contain two or more types.
- the active energy ray-curable adhesive can further contain a cationic polymerization initiator or a radical polymerization initiator.
- the active energy ray-curable adhesive may contain only one type of polymerization initiator, or may contain two or more types of polymerization initiators.
- the active energy ray-curing adhesive may contain a photosensitizer, a solvent, a leveling agent, an antioxidant, a light stabilizer, an ultraviolet absorber and the like.
- the thickness of the adhesive layer is, for example, 0.1 to 5 ⁇ m, preferably 0.5 to 3 ⁇ m.
- the retardation layer includes a liquid crystal coating type retardation layer. Since the liquid crystal coating type retardation layer is thin, cracks tend to occur when bent, but according to the present invention, cracks during bending can be prevented.
- the retardation layer 30 includes a ⁇ / 4 retardation layer 31, a retardation layer bonding layer 32, and a positive C layer 33 in this order from the polarizing layer 10 side.
- the retardation layer includes a ⁇ / 2 retardation layer, a retardation layer bonding layer, and a ⁇ / 4 retardation layer in this order from the polarizing layer 10 side.
- the ⁇ / 4 retardation layer 31 has a function of imparting a ⁇ / 4 retardation to the incident light.
- the ⁇ / 4 retardation layer 31 can have, for example, an in-plane retardation value of 100 to 160 nm with respect to light having a wavelength of 550 nm.
- the ⁇ / 4 retardation layer 31 contains a cured product of a polymerizable liquid crystal compound.
- the ⁇ / 4 retardation layer 31 may have an alignment layer.
- the polymerizable liquid crystal compound for example, the polymerizable liquid crystal compound used for the linearly polarizing layer 12 can be used.
- the polymerizable liquid crystal compound forming the linearly polarizing layer 12 and the polymerizable liquid crystal compound forming the ⁇ / 4 retardation layer 31 may be of the same type or may be of different types.
- the ⁇ / 4 retardation layer 31 is preferably a liquid crystal coating type retardation layer from the viewpoint of thinning.
- the liquid crystal coating type ⁇ / 4 retardation layer is formed by applying a composition for forming a retardation layer containing a polymerizable liquid crystal compound on an alignment layer for the retardation layer, and polymerizing and curing the polymerizable liquid crystal compound. Can be formed.
- the thickness of the ⁇ / 4 retardation layer 31 is, for example, 0.3 to 10 ⁇ m, preferably 0.5 to 8 ⁇ m, and more preferably 1 to 5 ⁇ m.
- the retardation layer bonding layer 32 is a layer for bonding the ⁇ / 4 retardation layer 31 and the positive C layer 33, or a layer for bonding the ⁇ / 2 retardation layer and the ⁇ / 4 retardation layer. ..
- the retardation layer bonding layer 32 is formed from the same material as the adhesive layer 20 by the same method.
- the adhesive layer 20 is preferably an adhesive layer, and more preferably formed from an active energy ray-curable adhesive.
- the thickness of the retardation layer bonded layer 32 is, for example, 0.1 to 30 ⁇ m, preferably 0.5 to 20 ⁇ m, more preferably 1 to 10 ⁇ m, and further preferably 1 to 5 ⁇ m or less. If the thickness of the retardation layer bonded layer 32 is less than 1 ⁇ m, the bending resistance of the obtained circularly polarizing plate may be insufficient, and if it exceeds 30 ⁇ m, the flexibility of the obtained circularly polarizing plate may be insufficient. May become.
- the elastic modulus of the retardation layer bonded layer is measured by the method described in Examples described later.
- the elastic modulus of the retardation layer bonded layer can be a value at a temperature of 25 ° C.
- the elastic modulus of the retardation layer bonded layer 32 is 1 GPa or more, preferably 1.5 to 6 GPa, and more preferably 2 to 5 GPa. If the elastic modulus of the retardation layer bonded layer 32 is less than 1 GPa, the bending resistance of the obtained circularly polarizing plate may be insufficient. If the elastic modulus of the retardation layer bonded layer 32 is too large, the flexibility of the circularly polarizing plate may be insufficient.
- the positive C layer 33 is a layer that compensates for the optical function of the circularly polarizing plate, such as preventing the reflected light from appearing colored when the surface is viewed from an oblique direction.
- the refractive index is n z
- it means the property of satisfying the relationship of n z > n x ⁇ n y (optical axis: n z direction).
- the positive C layer 33 contains a cured product of the polymerizable liquid crystal compound.
- the positive C layer 33 may have an alignment layer.
- the polymerizable liquid crystal compound for example, the polymerizable liquid crystal compound used for the linearly polarizing layer 12 can be used.
- the polymerizable liquid crystal compound forming the linearly polarized light layer 12 and the polymerizable liquid crystal compound forming the positive C layer 33 may be of the same type or different types.
- Examples of the polymerizable liquid crystal compound include a disk-shaped liquid crystal material (discotic liquid crystal material) and a rod-shaped liquid crystal material. Dispersibility can be controlled by changing the main chain and the side chain, and the wavelength can be controlled. It is more preferable to use a rod-shaped liquid crystal material because the dispersibility can be easily adjusted.
- the positive C layer 33 is preferably a liquid crystal coating type retardation layer from the viewpoint of thinning.
- the liquid crystal coating type positive C layer is formed by applying a composition for forming a retardation layer containing a polymerizable liquid crystal compound on an alignment layer for a retardation layer, and polymerizing and curing the polymerizable liquid crystal compound. Can be done.
- the thickness of the positive C layer 33 is, for example, 0.01 to 10 ⁇ m, preferably 0.1 to 8 ⁇ m, and more preferably 0.3 to 5 ⁇ m.
- the ⁇ / 2 phase difference layer has a function of imparting a ⁇ / 2 phase difference to the incident light.
- the ⁇ / 2 retardation layer can have, for example, an in-plane retardation value of 200 to 350 nm with respect to light having a wavelength of 550 nm.
- the ⁇ / 2 retardation layer can contain a cured product of a polymerizable liquid crystal compound.
- the ⁇ / 2 retardation layer may have an alignment layer.
- the polymerizable liquid crystal compound for example, the polymerizable liquid crystal compound used for the ⁇ / 4 retardation layer can be used.
- the polymerizable liquid crystal compound forming the ⁇ / 4 retardation layer and the polymerizable liquid crystal compound forming the ⁇ / 2 retardation layer may be of the same type or may be different types.
- the ⁇ / 2 retardation layer is preferably a liquid crystal coating type retardation layer from the viewpoint of thinning.
- the liquid crystal coating type ⁇ / 2 retardation layer is formed by applying a composition for forming a retardation layer containing a polymerizable liquid crystal compound on an alignment layer for the retardation layer, and polymerizing and curing the polymerizable liquid crystal compound. Can be formed.
- the thickness of the ⁇ / 2 retardation layer is, for example, 0.3 to 10 ⁇ m, preferably 0.5 to 8 ⁇ m, and more preferably 1 to 5 ⁇ m.
- the circularly polarizing plate 100 can be manufactured, for example, by the following method. That is, the linearly polarizing layer 12 and the overcoat layer 13 are formed on the protective layer 11 to obtain the polarizing layer 10.
- the ⁇ / 4 retardation layer 31 is formed on the separately prepared base material, and the positive C layer 33 is formed on the separately prepared base material.
- the ⁇ / 4 retardation layer 31 and the positive C layer 33 are bonded together using the adhesive for the retardation layer bonding layer 32 to obtain the retardation layer 30.
- the base material on the ⁇ / 4 retardation layer 31 side is removed, and the adhesive for the adhesive layer 20 is used to ⁇ / 4 of the overcoat layer 13 of the polarizing layer 10 and the retardation layer 30.
- the retardation layer 31 is bonded to obtain a circularly polarizing plate 100.
- FIGS. 2 to 4 are cross-sectional views showing the structure of a circularly polarizing plate according to another embodiment of the present invention.
- the retardation layer 30 has a reinforcing layer on at least one surface thereof.
- the first reinforcing layer 41 is formed on the upper portion of the retardation layer 30.
- the second reinforcing layer 42 is formed below the retardation layer 30.
- the first reinforcing layer 41 is formed above the retardation layer 30, and the second reinforcing layer 42 is formed below the retardation layer 30.
- the reinforcing layer is formed from the same material as the adhesive layer 20 by the same method.
- the reinforcing layer is preferably formed by using the above-mentioned active energy ray-curable adhesive.
- the outer surface of the retardation layer 30, that is, the exposed surface of the ⁇ / 4 retardation layer 31 is adhered to the first reinforcing layer 41.
- the first reinforcing layer 41 can be formed.
- the second reinforcing layer is applied by applying the adhesive for the second reinforcing layer 42 to the inner surface of the retardation layer 30, that is, the exposed surface of the positive C layer 33. 42 can be formed.
- the adhesive can be cured by heating the adhesive or irradiating the adhesive with active energy rays.
- the thickness of the reinforcing layer is, for example, 0.1 to 30 ⁇ m, preferably 0.3 to 10 ⁇ m, and more preferably 0.5 to 5 ⁇ m. If the thickness of the reinforcing layer is less than 0.1 ⁇ m, the bending resistance of the obtained circularly polarizing plate may be insufficient, and if it exceeds 30 ⁇ m, the flexibility of the obtained circularly polarizing plate may be insufficient. There is.
- the elastic modulus of the reinforcing layer is, for example, 1 GPa or more, preferably 1.5 to 6 GPa, and more preferably 2 to 5 GPa. If the elastic modulus of the reinforcing layer is less than 1 GPa, the bending resistance of the obtained circularly polarizing plate may be insufficient. If the elastic modulus of the reinforcing layer is too large, the flexibility of the circularly polarizing plate may be insufficient.
- the elastic modulus of the reinforcing layer is measured by the method described in Examples described later.
- the elastic modulus of the reinforcing layer can be a value at a temperature of 25 ° C.
- the circularly polarizing plate of the present invention has a thickness of 100 ⁇ m or less, preferably 5 to 50 ⁇ m, and more preferably 10 to 30 ⁇ m from the viewpoint of facilitating the imparting of excellent flexibility. If the thickness of the circularly polarizing plate exceeds 150 ⁇ m, the flexibility may be insufficient.
- the circularly polarizing plate of the present invention has a crack strain of 15% or more, preferably 18% or more, more preferably 20% or more, still more preferably 26% or more from the viewpoint of having excellent bending resistance.
- the upper limit of the crack strain is not particularly limited, but the crack strain may be, for example, 50% or less, or 35% or less. If the crack strain of the circularly polarizing plate is less than 15%, the bending resistance may be insufficient.
- the crack strain means a limit elongation rate (%) at which cracks do not occur when the material is pulled and stretched in one direction under predetermined conditions.
- the measurement conditions of the crack strain are as described as Examples.
- the crack strain can be prepared by the material and thickness of the layers constituting the circularly polarizing plate.
- the crack strain can be increased by providing the retarding layer with a reinforcing layer or increasing the number of reinforcing layers. Further, the crack strain can be increased by heat-treating the circularly polarizing plate at, for example, 50 to 100 ° C. for 0.5 to 24 hours.
- the front plate (not shown in the drawing) is generally arranged above the protective layer 11 and constitutes the outermost side of the polarizing layer 10.
- the front plate is a plate-like layer having integrality and translucency.
- the front plate may be composed of two or more layers.
- front plates include resin plate-like bodies (eg, resin plates, resin sheets, resin films), glass plate-like bodies (eg, glass plates), resin plate-like bodies and glass plates. Examples thereof include a laminated body with a shaped body.
- the material may be, for example, an acrylic resin such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; and a polyolefin resin such as polyethylene, polypropylene, polymethylpentene and polystyrene.
- Cellular resins such as triacetyl cellulose, acetyl cellulose butyrate, propionyl cellulose, butyryl cellulose and acetyl propionyl cellulose; polyvinyl acetate such as ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol and polyvinyl acetal.
- Sulfon-based resin such as polysulfone and polyether sulfone
- Ketone-based resin such as polyether ketone and polyether ether ketone
- Polyetherimide Polycarbonate resin
- Polyester resin Polyimide resin
- Polyamideimide-based resin and Examples thereof include polyamide resins.
- These polymers can be used alone or in admixture of two or more.
- the front plate may be a film made of the above resin, and may have a hard coat layer on at least one surface of the film.
- the hard coat layer may be formed on the outer surface of the film or may be formed on both surfaces. By providing the hard coat layer, it is possible to obtain a resin film having improved hardness and scratch resistance.
- the hard coat layer is, for example, a cured layer of an ultraviolet curable resin. Examples of the ultraviolet curable resin include acrylic resins, silicone resins, polyester resins, urethane resins, amide resins, epoxy resins and the like.
- the hard coat layer may contain additives in order to improve the hardness.
- the additive is not particularly limited as long as it does not inhibit the translucency of the front plate, and inorganic fine particles, organic fine particles, or a mixture thereof can be used.
- the front plate When the circularly polarizing plate 100 is used for a display panel, the front plate may have a function as a window film in the display panel.
- the front plate may further have a function as a touch sensor, a blue light cut function, a viewing angle adjusting function, and the like.
- the thickness of the front plate is, for example, 1 to 100 ⁇ m, preferably 10 to 70 ⁇ m, and more preferably 20 to 60 ⁇ m.
- a back plate (not shown in the drawing) can be laminated on the lower portion of the retardation layer 30 via an adhesive layer.
- As the back plate a plate-like body capable of transmitting light, a component used in a normal display device, or the like can be used.
- the thickness of the back plate may be, for example, 5 ⁇ m to 2000 ⁇ m, preferably 10 ⁇ m to 1000 ⁇ m, and more preferably 15 ⁇ m to 500 ⁇ m.
- the plate-shaped body used for the back plate may be composed of only one layer, may be composed of two or more layers, and an example of the plate-shaped body described in the front plate can be used.
- Examples of the components used in a normal display device used for the back plate include a separator, a touch sensor panel, an organic EL display element, and the like.
- the stacking order of the components in the display device is, for example, front plate / circular polarizing plate / separator, front plate / circular polarizing plate / organic EL display element, front plate / circular polarizing plate / touch sensor panel / organic EL display element, front.
- Examples thereof include a face plate / touch sensor panel / circularly polarizing plate / organic EL display element.
- the present invention will be described in more detail by way of examples.
- the present invention is not limited to these examples.
- the unit "part" of the mixing ratio of the substance is based on the weight unless otherwise specified.
- (A) Method for measuring the thickness of the layer The thickness of the layer constituting the circularly polarizing plate was measured using a contact-type film thickness measuring device (“MS-5C” (trade name) manufactured by Nikon Corporation). However, the polarizing layer and the alignment layer were measured using a laser microscope (“OLS3000” (trade name) manufactured by Olympus Corporation).
- MS-5C contact-type film thickness measuring device
- OLS3000 laser microscope
- the adhesive composition is applied to glass (thickness 1.0 mm) on the coating film obtained.
- a COP film manufactured by Nippon Zeon Co., Ltd., thickness 50 ⁇ m
- the coating film was subjected to an ultraviolet irradiation device (manufactured by Fusion UV Systems, equipped with an H-valve of an electrodeless ultraviolet lamp), and the light irradiation intensity was 400 mW / cm 2 , and the integrated light amount at a wavelength of 280 to 320 nm was obtained.
- Ultraviolet rays were irradiated so as to be 1500 mJ / cm 2, and the adhesive composition was cured to obtain a laminated sheet having a layer structure of glass / adhesive layer / COP film.
- the exposed adhesive layer is compressively elasticized using Nano Indicator (HM-500, manufactured by Fisher Instruments) at a temperature of 25 ° C., a relative humidity of 50%, and a pressure of 1 mN. The rate was measured.
- HM-500 Nano Indicator
- the composition for forming a linear polarizing layer includes 75 parts of compound (1-1), 25 parts of compound (1-2), and the above formulas (2-1a), (2-1b), and (2-2-) as a bicolor dye.
- 1.2 parts of the polyacrylate compound (BYK-361N, manufactured by BYK) as a leveling agent was mixed with 400 parts of toluene as a solvent, and the obtained mixture was stirred at 80 ° C. for 1 hour to prepare.
- composition for forming an overcoat layer is 100 parts of water, polyvinyl alcohol resin powder (KL-318, manufactured by Kuraray Co., Ltd., average degree of polymerization 18000) 3 A part and 1.5 parts of a polyamide epoxy resin (SR650 (30), manufactured by Sumika Chemtex Co., Ltd.) as a cross-linking agent were mixed and prepared.
- polyvinyl alcohol resin powder KL-318, manufactured by Kuraray Co., Ltd., average degree of polymerization 18000
- SR650 (30) manufactured by Sumika Chemtex Co., Ltd.
- Laminate A triacetyl cellol (TAC) film (KC2UA, manufactured by Konica Minolta Co., Ltd., thickness 25 ⁇ m) is used as the protective layer 11 under the conditions of an output of 0.3 kW and a processing speed of 3 m / min. , Corona treated. Then, the prepared composition for forming an alignment layer (1) was applied to the corona-treated surface of the film by a bar coating method, and heated and dried in a drying oven at a temperature of 80 ° C. for 1 minute.
- TAC triacetyl cellol
- the obtained film was passed through a wire grid (UIS-27132 ##, manufactured by Ushio, Inc.) and irradiated with ultraviolet rays adjusted so that the integrated light intensity at a wavelength of 365 nm was 100 mJ / cm 2.
- An oriented layer having a thickness of 100 nm was obtained.
- the prepared composition for forming a linear polarizing layer was applied to the obtained alignment layer by a bar coating method, and the coating film was heated and dried in a drying oven at a temperature of 120 ° C. for 1 minute and cooled to room temperature.
- the linearly polarizing layer 12 having a thickness of 2.0 ⁇ m was formed by irradiating this with ultraviolet rays adjusted so that the integrated light amount at a wavelength of 365 nm was 1200 mJ / cm 2.
- the prepared composition for forming an overcoat layer was applied onto the formed linearly polarized light layer by a bar coating method so that the thickness after drying was 1.0 ⁇ m, and dried at a temperature of 80 ° C. for 3 minutes.
- a polarizing layer 10 including a protective layer 11 (thickness 25 ⁇ m), a linear polarizing layer 12 (thickness 2.0 ⁇ m), and an overcoat layer 13 (thickness 1.0 ⁇ m) was manufactured in this order.
- ⁇ Manufacturing example 2> (Manufacturing of Adhesive for Adhesive Layer 20) While stirring 70 parts of butyl acrylate, 20 parts of methyl acrylate, 2.0 parts of acrylate, and 0.2 part of radical polymerization initiator (2,2'-azobisisobutyronitrile) in a nitrogen atmosphere. Acrylic resin was obtained by reacting at 55 ° C. Then, 100 parts of the acrylic resin, 1.0 part of the cross-linking agent (“Coronate L” manufactured by Tosoh Corporation), and 0.5 part of the silane coupling agent (“X-12-981” manufactured by Shin-Etsu Chemical Co., Ltd.) are mixed.
- the cross-linking agent (“Coronate L” manufactured by Tosoh Corporation)
- silane coupling agent (“X-12-981” manufactured by Shin-Etsu Chemical Co., Ltd.)
- a pressure-sensitive adhesive composition was obtained.
- the obtained pressure-sensitive adhesive composition was applied to the release-treated surface of a polyethylene terephthalate (PET) film (thickness 38 ⁇ m) that had been released-treated so that the thickness after drying was 5 ⁇ m using an applicator. ..
- the coated layer was dried at 100 ° C. for 1 minute to obtain a pressure-sensitive adhesive layer for the pressure-sensitive adhesive layer 20 with a PET film.
- another release-treated polyethylene terephthalate (PET) film was attached to this pressure-sensitive adhesive layer, and cured under the conditions of a temperature of 23 ° C.
- the pressure-sensitive adhesive layer for the pressure-sensitive adhesive layer 20 had an elastic modulus (storage elastic modulus) of 0.7 MPa.
- the PET film as the base material was appropriately peeled off in the process of manufacturing the circularly polarizing plate.
- composition for forming ⁇ / 4 retardation layer 31 was obtained by mixing each of the following components. The mixture was prepared by stirring at 80 ° C. for 1 hour.
- -Polymerization initiator (Irgacure 369, manufactured by BASF): 6 parts-Leveling agent (BYK-361N, polyacrylate compound, manufactured by BYK): 0.1 part-Solvent (cyclopentanone): 400 parts
- the composition for forming an alignment layer (1) is applied onto a base material of a polyethylene terephthalate (PET) film (thickness 100 ⁇ m) by a bar coat method, and a drying oven at a temperature of 80 ° C. is applied. It was heated and dried for 1 minute.
- the obtained coating film was subjected to polarized UV irradiation treatment to form an alignment layer.
- the polarized UV treatment was carried out using a UV irradiation device (SPOT CURE SP-7, manufactured by Ushio, Inc.) under the condition that the integrated light amount at a wavelength of 365 nm was 100 mJ / cm 2. Further, the polarization direction of the polarized UV was set to 45 ° with respect to the absorption axis of the linearly polarized light layer.
- the composition for forming a ⁇ / 4 retardation layer was applied onto the formed alignment layer by a bar coating method, heated and dried in a drying oven at a temperature of 120 ° C. for 1 minute, and then cooled to room temperature.
- the obtained coating film was irradiated with ultraviolet rays adjusted so that the integrated light amount at a wavelength of 365 nm was 1000 mJ / cm 2 , to form a ⁇ / 4 retardation layer having a thickness of 2.0 ⁇ m, and ⁇ with a PET film was formed.
- a / 4 retardation layer 31 was obtained. This ⁇ / 4 retardation layer showed anti-wavelength dispersibility.
- a photopolymerizable nematic liquid crystal compound manufactured by Merck & Co., RMM28B
- a solvent a mixed solvent was used in which methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), and cyclohexanone (CHN) were mixed at a mass ratio (MEK: MIBK: CHN) of 35:30:35. ..
- a polyethylene terephthalate (PET) film having a thickness of 38 ⁇ m was prepared as a substrate.
- the composition for forming an alignment layer (2) was applied to one side of the substrate so as to have a film thickness of 3 ⁇ m, and the alignment layer was prepared by irradiating with ultraviolet rays of 200 mJ / cm 2.
- a composition for forming a positive C layer was applied onto the alignment layer by die coating.
- the coating amount was 4 to 5 g (wet).
- the coating film was dried at a drying temperature of 75 ° C. and a drying time of 120 seconds. Then, the coating film was irradiated with ultraviolet rays (UV) to polymerize the polymerizable liquid crystal compound.
- UV ultraviolet rays
- the thickness of the obtained coating film was measured with a laser microscope (LEXT, manufactured by Olympus Corporation) and found to be 4 ⁇ m in total with the alignment layer.
- Laminating of retardation layer 70 parts of 3', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (trade name: CEL2021P, manufactured by Daicel Co., Ltd.), which is a photocationic curable resin, neopentyl glycol diglycidyl ether (EX-211, manufactured by Nagase ChemteX Corporation) 20 parts, 2-ethylhexyl glycidyl ether (EX-121, manufactured by Nagase ChemteX Co., Ltd.) 10 parts, photocationic polymerization initiator (CPI-100, manufactured by Sun Appro Co., Ltd.) 2.25 parts, a photocationic polymerization sensitizer is mixed in a blending ratio of 1,4-diethoxynaphthalene in a blending ratio of 1,4-diethoxynaphthalene, and then degassed. Was prepared.
- the photocationic polymerization initiator
- Ultraviolet rays adjusted so that the integrated light amount at a wavelength of 365 nm is 300 mJ / cm 2 is irradiated from the PET film base material side of the positive C layer 33 of the laminated retardation layer 30, and the laminated layer of the retardation layer is exposed to ultraviolet rays. It was cured. By this procedure, a retardation layer 30 including a ⁇ / 4 retardation layer 31, a retardation layer bonding layer 32, and a positive C layer 33 was manufactured in this order.
- the cured retardation layer bonded layer had an elastic modulus (compressive elastic modulus) of 2.4 GPa.
- the PET film as the base material was appropriately peeled off in the process of manufacturing the circularly polarizing plate.
- Example 1 Manufacture of circularly polarizing plate 200 shown in FIG. 2.
- the surface of the polarizing layer 10 obtained in Production Example 1 on the overcoat layer 13 side was subjected to corona treatment (conditions: output .0.3 kW, processing speed .3 m / min), and the adhesive layer obtained in Production Example 2 was applied.
- the surfaces of the pressure-sensitive adhesive layer for 20 were subjected to corona treatment, and the surfaces treated with corona were bonded to each other. 2.
- the surface of the retardation layer 30 obtained in Production Example 3 on the ⁇ / 4 retardation layer 31 side was subjected to corona treatment, and this and a cycloolefin polymer (COP) film (thickness 23 ⁇ m) were obtained in Production Example 3.
- the film was laminated with a nip roll via an adhesive for a laminated layer (thickness 1 to 2 ⁇ m).
- ultraviolet rays adjusted so that the integrated light amount at a wavelength of 365 nm was 300 mJ / cm 2 was irradiated to obtain a first reinforcing layer 41 having a thickness of 1.5 ⁇ m.
- the COP film was removed by peeling after forming the first reinforcing layer 41. 3.
- the surface of the adhesive adhesive of the bonded body obtained in step 1 is subjected to corona treatment
- the surface of the first reinforcing layer 41 formed in step 2 is subjected to corona treatment
- the surfaces treated with corona are bonded to each other, resulting in a phase difference.
- a circularly polarizing plate 200 having a first reinforcing layer 41 on the upper part of the layer 30 was obtained.
- Example 2 Manufacture of circularly polarizing plate 300 shown in FIG. 3.
- the surface of the polarizing layer 10 obtained in Production Example 1 on the overcoat layer 13 side was subjected to corona treatment, and the surface of the pressure-sensitive adhesive layer for the adhesive layer 20 obtained in Production Example 2 was subjected to corona treatment. It was pasted together.
- Example 3 Manufacture of Circular Polarizing Plate 400 shown in FIG. 4 Corona treatment was performed on the surface of the circularly polarizing plate 200 obtained in Example 1 on the positive C layer side. Next, this and a separately prepared COP film (thickness 23 ⁇ m) were laminated by a nip roll via the retardation layer bonding layer adhesive (thickness 1.5 ⁇ m) obtained in Production Example 3. After that, the COP film side is irradiated with ultraviolet rays adjusted so that the integrated light amount at a wavelength of 365 nm is 300 mJ / cm 2 , the COP film is removed, and the first reinforcing layer 41 is placed on the upper part of the retardation layer 30. A circularly polarizing plate 400 having a second reinforcing layer 42 under the retardation layer 30 was obtained.
- Circular Polarizing Plate 100 shown in FIG. 1 Circularly polarizing plate 100 was obtained in the same manner as in steps 1 and 2 of Example 2. This circularly polarizing plate was further cured at 80 ° C. for 1 hour.
- ⁇ Comparative Example 1> The output of 0.3 kW and the processing speed of 3 m / on the ⁇ / 4 retardation layer side of the ⁇ / 4 retardation layer 31 with PET film obtained in Production Example 3 and the positive C layer side of the positive C layer 33 with PET film. Corona treatment was performed under the condition of minutes.
- the pressure-sensitive adhesive layer for the pressure-sensitive adhesive layer 20 obtained in Production Example 2 was placed between the ⁇ / 4 retardation layer 31 and the positive C layer 33, and both were bonded together.
- a retardation layer including a ⁇ / 4 retardation layer (thickness 2.0 ⁇ m), a retardation layer bonding layer (thickness 5 ⁇ m), and a positive C layer (thickness 450 nm) was prepared in this order.
- the PET film as the base material was appropriately peeled off in the process of manufacturing the circularly polarizing plate.
- a circularly polarizing plate was obtained in the same manner as in Procedures 1 and 2 of Example 2 except that the above-mentioned retardation layer was used instead of the retardation layer 30 obtained in Production Example 3.
- the structure of the obtained circularly polarizing plate is the same as that of the fourth embodiment, except that the elastic modulus (storage elastic modulus) of the retarded layer bonded layer is 0.0007 GPa.
- a circularly polarizing plate was obtained in the same manner as in Comparative Example 1 except that the obtained positive C layer with a TAC film was used. As a result, a circularly polarizing plate having a TAC film (thickness 25 ⁇ m) as a reinforcing layer under the retardation layer was obtained.
- ⁇ Dynamic bending resistance test> The dynamic bending test was performed under room temperature conditions (temperature 25 ° C., humidity 50%).
- a polyimide polymer resin film (front plate, thickness 40 ⁇ m) having a hard coat layer (thickness 10 ⁇ m) on one side is bonded onto the protective layer of the circularly polarizing plate manufactured in Examples and Comparative Examples, and positive.
- Two polyimide films (back plate, both thickness 38 ⁇ m, tensile elastic modulus 5 GPa or more) were doubly bonded on the C layer to obtain a laminate for bending test.
- a bending test pressure-sensitive adhesive layer (thickness 25 ⁇ m) prepared in the same manner as in Production Example 2 was used except that the amount of the cross-linking agent used was changed to 3.0 parts.
- the obtained laminate for bending test was installed in a dynamic bending tester (“STS-VRT-500” (product name) manufactured by Science Town) in a flat state (not bent), and the front plate layer side was It was bent 180 ° so that it was on the inside (infold method), and then returned to its original flat state.
- the bending radius was 1.0 mm under room temperature conditions.
- the operation of bending and returning to flatness was counted as one bending, and this operation was repeated.
- the bending speed was 60 rpm.
- the number of times of bending when a crack (cracking or breaking) occurred in the retardation layer of the lowermost layer in the region bent by the bending operation was recorded in Table 1 as the limit number of times of bending.
- FIG. 5 is a cross-sectional view showing a method of a static bending durability test (mandrel bending test) of the circularly polarizing plate of the present invention.
- the laminate for bending test was cut into test pieces of 1 cm ⁇ 10 cm.
- the bending test laminate 52 cut on the test plate 51 was placed so that the front plate side thereof was on the upper side, and an iron rod 53 having a diameter of 3 mm was placed on the laminated body 52 (FIG. 5A).
- the test plate 51 and the laminate for bending test 52 were manually folded by 180 ° and fixed with the iron rod 53 sandwiched between them (FIG. 5 (b)).
- the laminated body 52 for bending test in a folded state was placed under high temperature and high humidity conditions (temperature 60 ° C., humidity 90%).
- the static bending durability was evaluated as follows, based on the time when a crack occurred in the retardation layer of the lowest layer among the layers constituting the circularly polarizing plate in the region bent by the bending operation. The results are shown in Table 1.
- Example 4 it was cured at 80 ° C. for 1 hour.
- the circularly polarizing plate of the present invention having a high crack strain has excellent bending resistance.
- the circularly polarizing plate having the reinforcing layers at the upper and lower portions of the retardation layer had particularly excellent bending resistance.
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Abstract
The objective of the present invention is to provide a circularly polarizing plate having excellent flexibility and excellent bending resistance. The present invention provides a circularly polarizing plate having a polarizing layer that is formed so as to include a linear polarizing layer, and a phase difference layer that is formed so as to include a λ/4 phase difference layer, a phase difference layer bonding layer, and a positive C layer, wherein the phase difference layer attachment layer has an elastic modulus of 1 GPa or greater, the circularly polarizing plate has a crack strain of 15% or more, the crack strain being the elongation (%) when both ends of a circularly polarizing plate with a length of 5 cm and a width of 10 mm are pulled with a speed of 4 mm/minute in the length direction and a crack occurs in the circularly polarizing plate.
Description
本発明は、円偏光板に関し、特に薄型耐屈曲性円偏光板に関する。
The present invention relates to a circularly polarizing plate, and particularly to a thin bending-resistant circularly polarizing plate.
外光反射や背景の映り込み等の問題を解消するため、有機ELディスプレイの視認面には円偏光板が設けられる。円偏光板は、一般に、直線偏光層にλ/4位相差層を積層することにより円偏光機能を出している。λ/4位相差層には、斜めから見たときの反射光の色付きを防ぐ等光学補償の目的で、ポジティブC層が貼合される。
A circularly polarizing plate is provided on the visible surface of the organic EL display in order to solve problems such as reflection of external light and reflection of the background. Generally, a circularly polarizing plate has a circularly polarized light function by laminating a λ / 4 retardation layer on a linearly polarized light layer. A positive C layer is attached to the λ / 4 retardation layer for the purpose of optical compensation such as preventing the reflected light from being colored when viewed from an angle.
近年では、屈曲可能な有機ELディスプレイに使用するために、薄型で耐屈曲性に優れた円偏光板が求められている。薄型円偏光板では、通常、λ/4位相差層及びポジティブC層等の位相差層として、液晶塗布型のものが使用される。液晶塗布型の位相差層とは、配向層上に位相差層形成用組成物を塗布し、その塗膜を硬化させて形成する位相差層をいう。
In recent years, there has been a demand for a thin circularly polarizing plate having excellent bending resistance for use in a bendable organic EL display. In the thin circular polarizing plate, a liquid crystal coating type is usually used as the retardation layer such as the λ / 4 retardation layer and the positive C layer. The liquid crystal coating type retardation layer refers to a retardation layer formed by applying a composition for forming a retardation layer on an alignment layer and curing the coating film.
特許文献1には、偏光層、λ/4位相差層、垂直配向液晶硬化層、及び補強層を有する液晶塗布型楕円偏光板が記載されている。この楕円偏光板では、偏光層とλ/4位相差層との間に補強層を導入することで、機械的強度を向上させ、液晶硬化膜を切断した際に切断端面で波うち等の不具合が発生しない、優れた加工特性を得ている(実施例7~9、比較例2)。
Patent Document 1 describes a liquid crystal coated elliptical polarizing plate having a polarizing layer, a λ / 4 retardation layer, a vertically oriented liquid crystal curing layer, and a reinforcing layer. In this elliptical polarizing plate, a reinforcing layer is introduced between the polarizing layer and the λ / 4 retardation layer to improve the mechanical strength, and when the liquid crystal cured film is cut, problems such as waviness at the cut end face occur. Excellent processing characteristics are obtained (Examples 7 to 9, Comparative Example 2).
特許文献2には、基材、基材の一面に形成した偏光コーティング層、偏光コーティング層上に形成した第1接着層、第1接着層上に形成した第1位相差コーティング層、第1位相差コーティング層上に形成した第2接着層、第2接着層上に形成した第2位相差コーティング層及び第2位相差コーティング層上に形成したソフト層を含み、ソフト層が式:
Patent Document 2 describes a base material, a polarizing coating layer formed on one surface of the base material, a first adhesive layer formed on the polarizing coating layer, a first retardation coating layer formed on the first adhesive layer, and a first position. The soft layer includes a second adhesive layer formed on the phase difference coating layer, a second retardation coating layer formed on the second adhesive layer, and a soft layer formed on the second retardation coating layer.
[式中、最大応力は応力-変形率グラフで破壊点での応力を示し、最大変形率は応力-変形率グラフで破壊点での変形率を示す。]
[In the formula, the maximum stress indicates the stress at the fracture point in the stress-deformation rate graph, and the maximum deformation rate indicates the deformation rate at the fracture point in the stress-deformation rate graph. ]
で定義した修正靭性が1,000ないし40,000MPa・%である偏光板、が記載されている。この円偏光板では、特許文献1での補強層に相当するソフト層の修正靭性を上記のように規定し、これを満たす適当なフィルムを選定することで、円偏光板に屈曲性を持たせている。
A polarizing plate having a modified toughness of 1,000 to 40,000 MPa ·% as defined in the above is described. In this circularly polarizing plate, the modified toughness of the soft layer corresponding to the reinforcing layer in Patent Document 1 is defined as described above, and by selecting an appropriate film satisfying this, the circularly polarizing plate is made flexible. ing.
液晶塗布型位相差層を備える円偏光板は、小さい屈曲半径(例えば、屈曲半径1mm)で屈曲(例えば、インフォールディング方式)した際には、屈曲部において位相差層が劣化し、破断し易いという問題がある。
When a circularly polarizing plate provided with a liquid crystal coating type retardation layer is bent with a small bending radius (for example, a bending radius of 1 mm) (for example, an infolding method), the retardation layer deteriorates at the bent portion and is easily broken. There is a problem.
特許文献1には、偏光板の耐屈曲性の向上に関し、言及されていない。また、特許文献2に記載の円偏光板では、補強層に相当するソフト層として、2官能ウレタンアクリレート、トリアセチルセルロース、又はポリエチレンテレフタレート等の比較的剛直な樹脂が用いられており、可撓性(フレキシビリティ)が不十分である。
Patent Document 1 does not mention the improvement of bending resistance of the polarizing plate. Further, in the circularly polarizing plate described in Patent Document 2, a relatively rigid resin such as bifunctional urethane acrylate, triacetyl cellulose, or polyethylene terephthalate is used as a soft layer corresponding to the reinforcing layer, and is flexible. (Flexibility) is insufficient.
本発明は、上記従来の円偏光板が抱える問題を解決するものであり、その目的とするところは、優れた可撓性及び優れた耐屈曲性を有する円偏光板を提供することである。
The present invention solves the problems of the conventional circularly polarizing plate, and an object of the present invention is to provide a circularly polarizing plate having excellent flexibility and excellent bending resistance.
本発明は、
直線偏光層を含んで成る偏光層と、液晶塗布型位相差層を含んで成る位相差層とを、有する円偏光板であって、
該円偏光板は、15%以上のクラックストレインを有し、
該クラックストレインは、5cm長×10mm幅の円偏光板の両端を長さ方向に4mm/分の速度で引張り、該円偏光板にクラックが発生した時の伸び率(%)である、
円偏光板、を提供する。 The present invention
A circularly polarizing plate having a polarizing layer including a linear polarizing layer and a retardation layer including a liquid crystal coating type retardation layer.
The circularly polarizing plate has a crack strain of 15% or more.
The crack strain is the elongation rate (%) when cracks occur in the circularly polarizing plate by pulling both ends of a circularly polarizing plate having a length of 5 cm and a width of 10 mm at a speed of 4 mm / min in the length direction.
Provided is a circularly polarizing plate.
直線偏光層を含んで成る偏光層と、液晶塗布型位相差層を含んで成る位相差層とを、有する円偏光板であって、
該円偏光板は、15%以上のクラックストレインを有し、
該クラックストレインは、5cm長×10mm幅の円偏光板の両端を長さ方向に4mm/分の速度で引張り、該円偏光板にクラックが発生した時の伸び率(%)である、
円偏光板、を提供する。 The present invention
A circularly polarizing plate having a polarizing layer including a linear polarizing layer and a retardation layer including a liquid crystal coating type retardation layer.
The circularly polarizing plate has a crack strain of 15% or more.
The crack strain is the elongation rate (%) when cracks occur in the circularly polarizing plate by pulling both ends of a circularly polarizing plate having a length of 5 cm and a width of 10 mm at a speed of 4 mm / min in the length direction.
Provided is a circularly polarizing plate.
ある一形態においては、前記位相差層は、λ/4位相差層、位相差層貼合層、及びポジティブC層を含んで成る。
In one embodiment, the retardation layer comprises a λ / 4 retardation layer, a retardation layer bonding layer, and a positive C layer.
ある一形態においては、前記位相差層貼合層は、1GPa以上の弾性率を有する。
In one embodiment, the retardation layer bonded layer has an elastic modulus of 1 GPa or more.
ある一形態においては、前記位相差層貼合層は、1~5μmの厚さを有する。
In one embodiment, the retardation layer bonding layer has a thickness of 1 to 5 μm.
ある一形態においては、前記ポジティブC層は、液晶塗布型の位相差層である。
In one form, the positive C layer is a liquid crystal coating type retardation layer.
ある一形態においては、前記位相差層は、その少なくとも一方の面に補強層を有する。
In one embodiment, the retardation layer has a reinforcing layer on at least one of its surfaces.
ある一形態においては、前記補強層は、前記位相差層の上部に形成されている。
In one embodiment, the reinforcing layer is formed on top of the retardation layer.
ある一形態においては、前記補強層は、前記位相差層の下部に形成されている。
In one embodiment, the reinforcing layer is formed below the retardation layer.
ある一形態においては、前記補強層は、前記位相差層の上部及び下部に形成されている。
In one embodiment, the reinforcing layer is formed on the upper part and the lower part of the retardation layer.
ある一形態においては、前記円偏光板は、5~50μmの厚さを有する。
In one form, the circularly polarizing plate has a thickness of 5 to 50 μm.
ある一形態においては、前記円偏光板は、偏光層を内側にして、屈曲半径1mmにて180°屈曲させては伸ばす操作を30万回繰り返し行った場合に、位相差層に割れ又は破断が生じない耐屈曲性を有する。
In one embodiment, the circularly polarizing plate is cracked or broken in the retardation layer when the operation of bending and stretching 180 ° with a bending radius of 1 mm with the polarizing layer inside is repeated 300,000 times. Has bending resistance that does not occur.
本発明によれば、優れた可撓性及び優れた耐屈曲性を有する円偏光板が提供される。本発明の円偏光板は、例えば、屈曲半径1mmという小さい屈曲半径で屈曲することができる。また、本発明の円偏光板は、偏光層を内側にして、屈曲半径1mmにて180°屈曲させては伸ばす操作を30万回繰り返し行った場合に、位相差層に割れ又は破断が生じない。
According to the present invention, a circularly polarizing plate having excellent flexibility and excellent bending resistance is provided. The circularly polarizing plate of the present invention can be bent with a small bending radius of, for example, a bending radius of 1 mm. Further, in the circularly polarizing plate of the present invention, the retardation layer is not cracked or broken when the operation of bending and stretching 180 ° at a bending radius of 1 mm is repeated 300,000 times with the polarizing layer inside. ..
図1は、本発明による円偏光板100の構造の一例を示す断面図である。図1に示す円偏光板100は、偏光層10、粘接着剤層20、及び位相差層30を偏光層の側からこの順に備える。該偏光層10は直線偏光層12を含んで成る。該位相差層30は、λ/4位相差層31、位相差層貼合層32、及びポジティブC層33を、偏光層の側からこの順に含んで成る。円偏光板100における偏光層10側に、前面板をさらに積層してもよい。
FIG. 1 is a cross-sectional view showing an example of the structure of the circularly polarizing plate 100 according to the present invention. The circular polarizing plate 100 shown in FIG. 1 includes a polarizing layer 10, an adhesive layer 20, and a retardation layer 30 in this order from the polarizing layer side. The polarizing layer 10 includes a linear polarizing layer 12. The retardation layer 30 includes a λ / 4 retardation layer 31, a retardation layer bonding layer 32, and a positive C layer 33 in this order from the polarizing layer side. A front plate may be further laminated on the polarizing layer 10 side of the circular polarizing plate 100.
〔偏光層10〕
図1の実施形態において、偏光層10は、保護層11、直線偏光層12及びオーバーコート層13を、視認される外側からこの順に備える。 [Polarizing layer 10]
In the embodiment of FIG. 1, the polarizinglayer 10 includes a protective layer 11, a linear polarizing layer 12, and an overcoat layer 13 in this order from the visible outside.
図1の実施形態において、偏光層10は、保護層11、直線偏光層12及びオーバーコート層13を、視認される外側からこの順に備える。 [Polarizing layer 10]
In the embodiment of FIG. 1, the polarizing
(保護層11)
保護層11は直線偏光層に設けられて直線偏光層12を保護する機能を有する。保護層の材料としては、特に限定されるものではないが、例えば、環状ポリオレフィン系樹脂、トリアセチルセルロース(TAC)、ジアセチルセルロースのような樹脂からなる酢酸セルロース系樹脂、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンテレフタレートのような樹脂からなるポリエステル系樹脂、ポリカーボネート系樹脂、(メタ)アクリル系樹脂、ポリプロピレン系樹脂等、当分野において公知の樹脂を挙げることができる。保護層の厚みは、屈曲性を高める観点から、通常100μm以下であり、80μm以下であることが好ましく、50μm以下であることがより好ましく、また、通常5μm以上であり、20μm以上であることが好ましい。保護層は、フィルムあってもよく、フィルム状の保護層は、位相差を有していてもよい。保護層がフィルムである場合、直線偏光層と保護層とは、粘着剤層や接着剤層を介して積層することができる。 (Protective layer 11)
Theprotective layer 11 is provided on the linearly polarized light layer and has a function of protecting the linearly polarized light layer 12. The material of the protective layer is not particularly limited, but for example, a cyclic polyolefin resin, a triacetyl cellulose (TAC), a cellulose acetate resin composed of a resin such as diacetyl cellulose, polyethylene terephthalate, polyethylene naphthalate, and the like. Examples thereof include resins known in the art such as polyester-based resins made of resins such as polybutylene terephthalate, polycarbonate-based resins, (meth) acrylic-based resins, and polypropylene-based resins. From the viewpoint of enhancing flexibility, the thickness of the protective layer is usually 100 μm or less, preferably 80 μm or less, more preferably 50 μm or less, and usually 5 μm or more, and 20 μm or more. preferable. The protective layer may be a film, and the film-like protective layer may have a phase difference. When the protective layer is a film, the linearly polarized light layer and the protective layer can be laminated via an adhesive layer or an adhesive layer.
保護層11は直線偏光層に設けられて直線偏光層12を保護する機能を有する。保護層の材料としては、特に限定されるものではないが、例えば、環状ポリオレフィン系樹脂、トリアセチルセルロース(TAC)、ジアセチルセルロースのような樹脂からなる酢酸セルロース系樹脂、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンテレフタレートのような樹脂からなるポリエステル系樹脂、ポリカーボネート系樹脂、(メタ)アクリル系樹脂、ポリプロピレン系樹脂等、当分野において公知の樹脂を挙げることができる。保護層の厚みは、屈曲性を高める観点から、通常100μm以下であり、80μm以下であることが好ましく、50μm以下であることがより好ましく、また、通常5μm以上であり、20μm以上であることが好ましい。保護層は、フィルムあってもよく、フィルム状の保護層は、位相差を有していてもよい。保護層がフィルムである場合、直線偏光層と保護層とは、粘着剤層や接着剤層を介して積層することができる。 (Protective layer 11)
The
保護層11は、後述のオーバーコート層であってもよく、有機物層または無機物層であることができる。有機物層または無機物層は、コーティングにより形成される層であることができる。有機物層は、保護層形成用組成物、例えば(メタ)アクリル系樹脂組成物、エポキシ系樹脂組成物、ポリイミド系樹脂組成物等を用いて形成することができる。保護層形成用組成物は、活性エネルギー線硬化型であってもよいし、熱硬化型であってもよい。
無機物層は、例えばシリコン酸化物等から形成することができる。保護層11が有機物層である場合、保護層はハードコート層と呼ばれるものであってもよい。 Theprotective layer 11 may be an overcoat layer described later, and may be an organic layer or an inorganic layer. The organic or inorganic layer can be a layer formed by the coating. The organic layer can be formed by using a composition for forming a protective layer, for example, a (meth) acrylic resin composition, an epoxy resin composition, a polyimide resin composition, or the like. The composition for forming a protective layer may be an active energy ray-curable type or a thermosetting type.
The inorganic layer can be formed from, for example, silicon oxide. When theprotective layer 11 is an organic layer, the protective layer may be called a hard coat layer.
無機物層は、例えばシリコン酸化物等から形成することができる。保護層11が有機物層である場合、保護層はハードコート層と呼ばれるものであってもよい。 The
The inorganic layer can be formed from, for example, silicon oxide. When the
保護層11が有機物層である場合、例えば活性エネルギー線硬化型の保護層形成用組成物を基材フィルム上に塗布し、活性エネルギーを照射して硬化させることにより保護層を作製することができる。基材フィルムは、後述の前面板の樹脂製の板状体の説明が適用される。基材フィルムは通常、剥離して除去される。保護層形成用組成物を塗布する方法としては、例えばバーコート法、スピンコート法等が挙げられる。保護層11が無機物層である場合、例えばスパッタリング法、蒸着法等によって保護層を形成することができる。
保護層11が有機物層または無機物層である場合、保護層11の厚みは、例えば0.1μm以上10μm以下であってよく、好ましくは0.5μm以上5μm以下である。 When theprotective layer 11 is an organic layer, the protective layer can be produced, for example, by applying an active energy ray-curable protective layer forming composition on a base film and irradiating it with active energy to cure it. .. As the base film, the description of the resin plate-like body of the front plate described later is applied. The substrate film is usually stripped and removed. Examples of the method for applying the protective layer forming composition include a bar coating method and a spin coating method. When the protective layer 11 is an inorganic layer, the protective layer can be formed by, for example, a sputtering method, a vapor deposition method, or the like.
When theprotective layer 11 is an organic layer or an inorganic layer, the thickness of the protective layer 11 may be, for example, 0.1 μm or more and 10 μm or less, preferably 0.5 μm or more and 5 μm or less.
保護層11が有機物層または無機物層である場合、保護層11の厚みは、例えば0.1μm以上10μm以下であってよく、好ましくは0.5μm以上5μm以下である。 When the
When the
(直線偏光層12)
直線偏光層12は、自然光等の非偏光な光線からある一方向の直線偏光を選択的に透過させる機能を有する層である。直線偏光層12は、例えば、重合性液晶化合物の硬化物及び二色性色素を含み、二色性色素は、重合性液晶化合物の硬化物中に分散し、配向している。かかる直線偏光層12は、ポリビニルアルコール系樹脂にヨウ素等の二色性色素を吸着配向させた直線偏光層と比較すると、湿熱試験における収縮量が小さいため寸法変化が小さい。そのため、湿熱耐久性が要求される環境下で使用される円偏光板に好適に用いることができる。 (Linear polarizing layer 12)
The linearlypolarized light layer 12 is a layer having a function of selectively transmitting unidirectional linearly polarized light from unpolarized light rays such as natural light. The linear polarizing layer 12 contains, for example, a cured product of a polymerizable liquid crystal compound and a dichroic dye, and the dichroic dye is dispersed and oriented in the cured product of the polymerizable liquid crystal compound. The dimensional change of the linearly polarizing layer 12 is small as compared with the linearly polarizing layer in which a dichroic dye such as iodine is adsorbed and oriented on a polyvinyl alcohol-based resin because the shrinkage amount in the moist heat test is small. Therefore, it can be suitably used for a circularly polarizing plate used in an environment where wet and heat durability is required.
直線偏光層12は、自然光等の非偏光な光線からある一方向の直線偏光を選択的に透過させる機能を有する層である。直線偏光層12は、例えば、重合性液晶化合物の硬化物及び二色性色素を含み、二色性色素は、重合性液晶化合物の硬化物中に分散し、配向している。かかる直線偏光層12は、ポリビニルアルコール系樹脂にヨウ素等の二色性色素を吸着配向させた直線偏光層と比較すると、湿熱試験における収縮量が小さいため寸法変化が小さい。そのため、湿熱耐久性が要求される環境下で使用される円偏光板に好適に用いることができる。 (Linear polarizing layer 12)
The linearly
重合性液晶化合物は、重合性反応基を有し、かつ、液晶性を示す化合物である。重合性反応基は、重合反応に関与する基であり、光重合性反応基であることが好ましい。光重合性反応基は、光重合開始剤から発生した活性ラジカルや酸等によって重合反応に関与し得る基をいう。光重合性官能基としては、ビニル基、ビニルオキシ基、1-クロロビニル基、イソプロペニル基、4-ビニルフェニル基、アクリロイルオキシ基、メタクリロイルオキシ基、オキシラニル基、オキセタニル基等が挙げられる。これらの中でも、アクリロイルオキシ基、メタクリロイルオキシ基、ビニルオキシ基、オキシラニル基及びオキセタニル基が好ましく、アクリロイルオキシ基がより好ましい。重合性液晶化合物の種類は特に限定されず、棒状液晶化合物、円盤状液晶化合物、及びこれらの混合物を用いることができる。重合性液晶化合物の液晶性は、サーモトロピック性液晶でもリオトロピック性液晶でもよく、相秩序構造としてはネマチック液晶でもスメクチック液晶でもよい。
The polymerizable liquid crystal compound is a compound having a polymerizable reactive group and exhibiting liquid crystallinity. The polymerizable reactive group is a group involved in the polymerization reaction, and is preferably a photopolymerizable reactive group. The photopolymerizable reactive group refers to a group that can participate in the polymerization reaction by an active radical, an acid, or the like generated from the photopolymerization initiator. Examples of the photopolymerizable functional group include a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, an oxylanyl group, an oxetanyl group and the like. Among these, acryloyloxy group, methacryloyloxy group, vinyloxy group, oxylanyl group and oxetanyl group are preferable, and acryloyloxy group is more preferable. The type of the polymerizable liquid crystal compound is not particularly limited, and a rod-shaped liquid crystal compound, a disk-shaped liquid crystal compound, and a mixture thereof can be used. The liquid crystal property of the polymerizable liquid crystal compound may be a thermotropic liquid crystal or a lyotropic liquid crystal, and the phase-ordered structure may be a nematic liquid crystal or a smectic liquid crystal.
二色性色素は、分子の長軸方向における吸光度と短軸方向における吸光度とが異なる性質を有する色素をいう。二色性色素としては、300~700nmの範囲に吸収極大波長(λMAX)を有するものが好ましい。かかる二色性色素としては、例えば、アクリジン色素、オキサジン色素、シアニン色素、ナフタレン色素、アゾ色素、及びアントラキノン色素等が挙げられるが、これらの中でもアゾ色素が好ましい。アゾ色素としては、モノアゾ色素、ビスアゾ色素、トリスアゾ色素、テトラキスアゾ色素、及びスチルベンアゾ色素等が挙げられ、好ましくはビスアゾ色素、及びトリスアゾ色素である。二色性色素は単独で使用しても、2種以上を組み合わせて使用してもよいが、3種以上を組み合わせて使用することが好ましい。特に、3種以上のアゾ化合物を組み合わせることが好ましい。二色性色素の一部が反応性基を有していてもよく、また液晶性を有していてもよい。
A dichroic dye is a dye having a property in which the absorbance in the major axis direction and the absorbance in the minor axis direction of the molecule are different. The dichroic dye preferably has an absorption maximum wavelength (λMAX) in the range of 300 to 700 nm. Examples of such dichroic dyes include acridine dyes, oxazine dyes, cyanine dyes, naphthalene dyes, azo dyes, anthraquinone dyes and the like, and among these, azo dyes are preferable. Examples of the azo dye include a monoazo dye, a bisazo dye, a trisazo dye, a tetrakisazo dye, a stilbene azo dye and the like, and a bisazo dye and a trisazo dye are preferable. The dichroic dye may be used alone or in combination of two or more, but it is preferable to use three or more in combination. In particular, it is preferable to combine three or more kinds of azo compounds. A part of the dichroic dye may have a reactive group or may have a liquid crystallinity.
直線偏光層12は、例えば、保護層11上に形成した配向層上に、重合性液晶化合物及び二色性色素を含む直線偏光層形成用組成物を塗布し、重合性液晶化合物を重合して硬化させることにより形成することができる。あるいは、基材層上に、直線偏光層形成用組成物を塗布して塗膜を形成し、この塗膜を基材層とともに延伸することにより、直線偏光層12を形成してもよい。
For the linearly polarizing layer 12, for example, a composition for forming a linearly polarizing layer containing a polymerizable liquid crystal compound and a dichroic dye is applied onto an alignment layer formed on the protective layer 11, and the polymerizable liquid crystal compound is polymerized. It can be formed by curing. Alternatively, the linearly polarizing layer 12 may be formed by applying a composition for forming a linearly polarized light layer on the base material layer to form a coating film and stretching the coating film together with the base material layer.
配向層は、重合性液晶化合物を所望の方向に液晶配向させる、配向規制力を有する。配向層としては、配向性ポリマーで形成された配向性ポリマー層、光配向ポリマーで形成された光配向性ポリマー層、層表面に凹凸パターンや複数のグルブ(溝)を有するグルブ配向層を挙げることができる。配向層の厚さは、通常10~500nm、好ましくは10~200nmである。
The alignment layer has an orientation regulating force that orients the polymerizable liquid crystal compound in a desired direction. Examples of the oriented layer include an oriented polymer layer formed of an oriented polymer, a photo-oriented polymer layer formed of a photo-aligned polymer, and a grub-aligned layer having an uneven pattern or a plurality of grubs (grooves) on the layer surface. Can be done. The thickness of the alignment layer is usually 10 to 500 nm, preferably 10 to 200 nm.
配向性ポリマー層は、配向性ポリマーを溶剤に溶解した組成物を、基材層や位相差層用基材層に塗布して溶剤を除去し、必要に応じてラビング処理をして形成することができる。この場合、配向規制力は、配向性ポリマーで形成された配向性ポリマー層では、配向性ポリマーの表面状態やラビング条件によって任意に調整することが可能である。
The oriented polymer layer is formed by applying a composition in which an oriented polymer is dissolved in a solvent to a base material layer or a base material layer for a retardation layer to remove the solvent, and if necessary, rubbing treatment. Can be done. In this case, in the oriented polymer layer formed of the oriented polymer, the orientation restricting force can be arbitrarily adjusted depending on the surface condition and rubbing conditions of the oriented polymer.
光配向性ポリマー層は、光反応性基を有するポリマー又はモノマーと溶剤とを含む組成物を基材層や位相差層用基材層に塗布し、偏光を照射することにより形成することができる。この場合、配向規制力は、光配向性ポリマー層では、光配向性ポリマーに対する偏光照射条件等によって任意に調整することが可能である。
The photo-oriented polymer layer can be formed by applying a composition containing a polymer or monomer having a photoreactive group and a solvent to a base material layer or a base material layer for a retardation layer and irradiating with polarized light. .. In this case, the orientation restricting force can be arbitrarily adjusted in the photo-alignment polymer layer depending on the polarization irradiation conditions for the photo-alignment polymer.
例えば、グルブ配向層は、感光性ポリイミド膜表面にパターン形状のスリットを有する露光用マスクを介して露光、現像等を行って凹凸パターンを形成する方法、表面に溝を有する板状の原盤に、活性エネルギー線硬化性樹脂の未硬化の層を形成し、この層を基材層や位相差層用基材層に転写して硬化する方法、基材層や位相差層用基材層に活性エネルギー線硬化性樹脂の未硬化の層を形成し、この層に、凹凸を有するロール状の原盤を押し当てる等により凹凸を形成して硬化させる方法等によって形成することができる。
For example, the grub alignment layer is a method of forming an uneven pattern by exposure, development, or the like through an exposure mask having a pattern-shaped slit on the surface of a photosensitive polyimide film, or a plate-shaped master having a groove on the surface. A method of forming an uncured layer of an active energy ray-curable resin and transferring this layer to a base material layer or a base material layer for a retardation layer for curing, which is active in a base material layer or a base material layer for a retardation layer. It can be formed by a method of forming an uncured layer of an energy ray-curable resin, forming irregularities by pressing a roll-shaped master having irregularities against this layer, and curing the layer.
重合性液晶化合物及び二色性色素を含む直線偏光層形成用組成物、及びこの組成物を用いた直線偏光層の製造方法としては、特開2013-37353号公報、特開2013-33249号公報、特開2017-83843号公報等に記載のものを挙げることができる。直線偏光層形成用組成物は、重合性液晶化合物及び二色性色素に加えて、溶媒、重合開始剤、架橋剤、レベリング剤、酸化防止剤、可塑剤、増感剤などの添加剤をさらに含んでいてもよい。これらの成分は、各々、単独で又は2種以上を組み合わせて用いてよい。
Examples of a composition for forming a linearly polarizing layer containing a polymerizable liquid crystal compound and a dichroic dye, and a method for producing a linearly polarizing layer using this composition are JP-A-2013-37353 and JP-A-2013-3324. , Japanese Unexamined Patent Publication No. 2017-83843, and the like. In addition to the polymerizable liquid crystal compound and the dichroic dye, the composition for forming a linear polarizing layer further contains additives such as a solvent, a polymerization initiator, a cross-linking agent, a leveling agent, an antioxidant, a plasticizer, and a sensitizer. It may be included. Each of these components may be used alone or in combination of two or more.
直線偏光層12の厚さは、例えば、0.3~10μm、好ましくは0.5~8μm、より好ましくは1~5μmである。
The thickness of the linearly polarizing layer 12 is, for example, 0.3 to 10 μm, preferably 0.5 to 8 μm, and more preferably 1 to 5 μm.
(オーバーコート層13)
オーバーコート層13は、直線偏光層12の保護、直線偏光層12中の二色性色素の移行の抑制、酸素や水分に対するバリア性の付与等を目的として設ける。オーバーコート層13は、直線偏光層12の両面に設けられていてもよい。オーバーコート層13は、例えば、直線偏光層12の表面にオーバーコート層13を形成するための材料(組成物)を塗布することによって形成することができる。 (Overcoat layer 13)
Theovercoat layer 13 is provided for the purpose of protecting the linearly polarized light layer 12, suppressing the migration of the dichroic dye in the linearly polarized light layer 12, and imparting a barrier property to oxygen and water. The overcoat layer 13 may be provided on both sides of the linearly polarizing layer 12. The overcoat layer 13 can be formed, for example, by applying a material (composition) for forming the overcoat layer 13 on the surface of the linearly polarized light layer 12.
オーバーコート層13は、直線偏光層12の保護、直線偏光層12中の二色性色素の移行の抑制、酸素や水分に対するバリア性の付与等を目的として設ける。オーバーコート層13は、直線偏光層12の両面に設けられていてもよい。オーバーコート層13は、例えば、直線偏光層12の表面にオーバーコート層13を形成するための材料(組成物)を塗布することによって形成することができる。 (Overcoat layer 13)
The
オーバーコート層13は、耐溶剤性、透明性、機械的強度、熱安定性、遮蔽性、及び等方性等に優れるものが好ましい。オーバーコート層13を構成する材料としては、例えば、光硬化性樹脂や水溶性ポリマー等が挙げられる。
The overcoat layer 13 is preferably excellent in solvent resistance, transparency, mechanical strength, thermal stability, shielding property, isotropic property, and the like. Examples of the material constituting the overcoat layer 13 include a photocurable resin and a water-soluble polymer.
光硬化性樹脂としては、例えば、(メタ)アクリル系樹脂、ウレタン系樹脂、(メタ)アクリルウレタン系樹脂、エポキシ系樹脂、シリコーン系樹脂等が挙げられる。水溶性ポリマーとしては、例えば、ポリ(メタ)アクリルアミド系ポリマー;ポリビニルアルコール、およびエチレン-ビニルアルコール共重合体、エチレン-酢酸ビニル共重合体、(メタ)アクリル酸又はその無水物-ビニルアルコール共重合体等のビニルアルコール系ポリマー;カルボキシビニル系ポリマー;ポリビニルピロリドン;デンプン類;アルギン酸ナトリウム;ポリエチレンオキシド系ポリマー等が挙げられる。
Examples of the photocurable resin include (meth) acrylic resin, urethane resin, (meth) acrylic urethane resin, epoxy resin, silicone resin and the like. Examples of the water-soluble polymer include poly (meth) acrylamide-based polymers; polyvinyl alcohol and ethylene-vinyl alcohol copolymers, ethylene-vinyl acetate copolymers, (meth) acrylic acid or its anhydride-vinyl alcohol co-weight. Examples thereof include vinyl alcohol-based polymers such as coalesced; carboxyvinyl-based polymers; polyvinylpyrrolidone; starches; sodium alginate; polyethylene oxide-based polymers.
オーバーコート層13の厚さは、例えば、0.1~5μm、好ましくは0.3~4μm、より好ましくは0.5~3μmである。
The thickness of the overcoat layer 13 is, for example, 0.1 to 5 μm, preferably 0.3 to 4 μm, and more preferably 0.5 to 3 μm.
〔粘接着剤層20〕
図1の実施形態において、粘接着剤層20は偏光層10と位相差層30とを貼合する層である。粘接着剤層20は、粘着剤層または接着剤層である。尚、粘着剤とは感圧接着性を有する接着剤をいう。粘接着剤層20は、粘着剤層であることが好ましい。 [Adhesive layer 20]
In the embodiment of FIG. 1, theadhesive layer 20 is a layer in which a polarizing layer 10 and a retardation layer 30 are bonded together. The adhesive layer 20 is an adhesive layer or an adhesive layer. The pressure-sensitive adhesive is an adhesive having pressure-sensitive adhesiveness. The adhesive layer 20 is preferably an adhesive layer.
図1の実施形態において、粘接着剤層20は偏光層10と位相差層30とを貼合する層である。粘接着剤層20は、粘着剤層または接着剤層である。尚、粘着剤とは感圧接着性を有する接着剤をいう。粘接着剤層20は、粘着剤層であることが好ましい。 [Adhesive layer 20]
In the embodiment of FIG. 1, the
粘接着剤層20が粘着剤層である場合、粘着剤層は、例えば、(メタ)アクリル系、ゴム系、ウレタン系、エステル系、シリコーン系、ポリビニルエーテル系のような樹脂を主成分とする粘着剤組成物で構成する。これらの中でも、透明性、耐候性、耐熱性等に優れる(メタ)アクリル系樹脂をベースポリマーとする粘着剤組成物が好ましい。粘着剤組成物は、活性エネルギー線硬化型、熱硬化型であってもよい。
When the adhesive layer 20 is an adhesive layer, the adhesive layer contains, for example, a resin such as (meth) acrylic, rubber, urethane, ester, silicone, or polyvinyl ether as a main component. Consists of a pressure-sensitive adhesive composition. Among these, a pressure-sensitive adhesive composition using a (meth) acrylic resin having excellent transparency, weather resistance, heat resistance and the like as a base polymer is preferable. The pressure-sensitive adhesive composition may be an active energy ray-curable type or a thermosetting type.
粘着剤組成物に用いられる(メタ)アクリル系樹脂(ベースポリマー)としては、例えば、(メタ)アクリル酸ブチル、(メタ)アクリル酸エチル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸2-エチルヘキシル等の(メタ)アクリル酸エステルのうちの1種又は2種以上をモノマーとする重合体又は共重合体が好ましく用いられる。ベースポリマーには、極性モノマーを共重合させることが好ましい。極性モノマーとしては、例えば、(メタ)アクリル酸、(メタ)アクリル酸2-ヒドロキシプロピル、(メタ)アクリル酸ヒドロキシエチル、(メタ)アクリルアミド、N,N-ジメチルアミノエチル(メタ)アクリレート、グリシジル(メタ)アクリレートのような、カルボキシル基、水酸基、アミド基、アミノ基、エポキシ基等を有するモノマーが挙げられる。
Examples of the (meth) acrylic resin (base polymer) used in the pressure-sensitive adhesive composition include butyl (meth) acrylate, ethyl (meth) acrylate, isooctyl (meth) acrylate, and 2- (meth) acrylate. A polymer or copolymer having one or more of (meth) acrylic acid esters such as ethylhexyl as a monomer is preferably used. It is preferable that the base polymer is copolymerized with a polar monomer. Examples of the polar monomer include (meth) acrylic acid, 2-hydroxypropyl (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, and glycidyl ( Examples thereof include monomers having a carboxyl group, a hydroxyl group, an amide group, an amino group, an epoxy group and the like, such as meth) acrylate.
粘着剤組成物は、前記ベースポリマー単独でなるものであってよいが、通常は架橋剤を更に含む。該架橋剤としては、2価以上の金属イオンであって、カルボキシル基との間でカルボン酸金属塩を形成するもの;ポリアミン化合物であって、カルボキシル基との間でアミド結合を形成するもの;ポリエポキシ化合物やポリオールであって、カルボキシル基との間でエステル結合を形成するもの;ポリイソシアネート化合物であって、カルボキシル基との間でアミド結合を形成するもの等が挙げられる。これらの中でも、ポリイソシアネート化合物が好適である。
The pressure-sensitive adhesive composition may consist of the base polymer alone, but usually further contains a cross-linking agent. The cross-linking agent is a divalent or higher metal ion that forms a carboxylic acid metal salt with a carboxyl group; a polyamine compound that forms an amide bond with a carboxyl group; Examples thereof include polyepoxy compounds and polyols that form an ester bond with a carboxyl group; polyisocyanate compounds that form an amide bond with a carboxyl group, and the like. Among these, a polyisocyanate compound is preferable.
活性エネルギー線硬化型粘着剤組成物は、紫外線や電子線のような活性エネルギー線の照射を受けて硬化する性質を有しており、活性エネルギー線照射前においても粘接着性を有してフィルム等の被着体に密着させることができる。活性エネルギー線の照射により硬化して密着力の調整をすることができる。活性エネルギー線硬化型粘着剤組成物は、紫外線硬化型であることが好ましい。活性エネルギー線硬化型粘着剤組成物は、前記のようにベースポリマー、架橋剤に加えて、活性エネルギー線重合性化合物を含む。光重合開始剤や光増感剤等も適宜含む。
The active energy ray-curable pressure-sensitive adhesive composition has a property of being cured by being irradiated with active energy rays such as ultraviolet rays and electron beams, and has adhesiveness even before irradiation with active energy rays. It can be brought into close contact with an adherend such as a film. It can be cured by irradiation with active energy rays and the adhesion can be adjusted. The active energy ray-curable pressure-sensitive adhesive composition is preferably an ultraviolet-curable type. The active energy ray-curable pressure-sensitive adhesive composition contains an active energy ray-polymerizable compound in addition to the base polymer and the cross-linking agent as described above. It also contains a photopolymerization initiator, a photosensitizer and the like as appropriate.
粘着剤組成物は、光散乱性を付与するための微粒子、ビーズ(樹脂ビーズ、ガラスビーズ等)、ガラス繊維、ベースポリマー以外の樹脂、粘接着性付与剤、充填剤(金属粉やその他の無機粉末等)、酸化防止剤、紫外線吸収剤、染料、顔料、着色剤、消泡剤、腐食防止剤、光重合開始剤等の添加剤を更に含んでもよい。
The pressure-sensitive adhesive composition includes fine particles for imparting light scattering properties, beads (resin beads, glass beads, etc.), glass fibers, resins other than the base polymer, adhesive adhesive-imparting agents, fillers (metal powder and other materials). Additives such as (inorganic powder, etc.), antioxidants, ultraviolet absorbers, dyes, pigments, colorants, defoaming agents, corrosion inhibitors, photopolymerization initiators, etc. may be further contained.
粘着剤層は、粘着剤組成物の有機溶剤希釈液を基材上に塗布し、乾燥させることにより形成することができる。活性エネルギー線硬化型粘着剤組成物を用いた場合は、形成された粘着剤層に、活性エネルギー線を照射することにより所望の硬化度を有する硬化物とすることができる。
The pressure-sensitive adhesive layer can be formed by applying an organic solvent diluted solution of the pressure-sensitive adhesive composition on a substrate and drying it. When the active energy ray-curable pressure-sensitive adhesive composition is used, the formed pressure-sensitive adhesive layer can be irradiated with active energy rays to obtain a cured product having a desired degree of curing.
粘着剤層の厚さは、例えば、0.1~30μm、好ましくは0.5~20μm、より好ましくは1~10μmである。
The thickness of the pressure-sensitive adhesive layer is, for example, 0.1 to 30 μm, preferably 0.5 to 20 μm, and more preferably 1 to 10 μm.
粘接着剤層20が接着剤層である場合、接着剤層は、例えば、水系接着剤または活性エネルギー線硬化型接着剤から形成する。
When the adhesive layer 20 is an adhesive layer, the adhesive layer is formed from, for example, a water-based adhesive or an active energy ray-curable adhesive.
水系接着剤は、ポリビニルアルコール系樹脂水溶液、水系二液型ウレタン系エマルジョン接着剤組成物などが挙げられ、ポリビニルアルコール系樹脂水溶液であることが好ましい。
Examples of the water-based adhesive include a polyvinyl alcohol-based resin aqueous solution and a water-based two-component urethane-based emulsion adhesive composition, and a polyvinyl alcohol-based resin aqueous solution is preferable.
水系接着剤がポリビニルアルコール系樹脂を含む場合、ポリビニルアルコール系樹脂の含有量は、水100質量部に対して、1質量部以上10質量部以下であることが好ましく、1質量部以上5質量部以下であることがより好ましい。
When the water-based adhesive contains a polyvinyl alcohol-based resin, the content of the polyvinyl alcohol-based resin is preferably 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of water, and 1 part by mass or more and 5 parts by mass or less. The following is more preferable.
水系接着剤には、多価アルデヒド、水溶性エポキシ化合物、メラミン系化合物、ジルコニア化合物、亜鉛化合物などが添加剤として添加されていてもよい。
A polyhydric aldehyde, a water-soluble epoxy compound, a melamine compound, a zirconia compound, a zinc compound, or the like may be added to the water-based adhesive as an additive.
水系接着剤は、接着性を向上させるために、グリオキシル酸の金属塩、グリオキザール、水溶性エポキシ樹脂などの硬化性成分および/または架橋剤を含むことが好ましい。グリオキシル酸の金属塩としては、アルカリ金属塩又はアルカリ土類金属塩であることが好ましく、例えば、グリオキシル酸ナトリウム、グリオキシル酸カリウム、グリオキシル酸マグネシウム、グリオキシル酸カルシウムなどが挙げられる。水溶性エポキシ樹脂としては、例えばジエチレントリアミン、トリエチレンテトラミンなどのポリアルキレンポリアミンと、アジピン酸などのジカルボン酸との反応で得られるポリアミドアミンに、エピクロロヒドリンを反応させて得られるポリアミドポリアミンエポキシ樹脂を好適に用いることができる。
The water-based adhesive preferably contains a curable component such as a metal salt of glyoxylic acid, glyoxal, and a water-soluble epoxy resin and / or a cross-linking agent in order to improve the adhesiveness. The metal salt of glyoxylic acid is preferably an alkali metal salt or an alkaline earth metal salt, and examples thereof include sodium glyoxylate, potassium glyoxylate, magnesium glyoxylate, and calcium glyoxylate. The water-soluble epoxy resin is a polyamide polyamine epoxy resin obtained by reacting a polyamide amine obtained by reacting a polyalkylene polyamine such as diethylenetriamine or triethylenetetramine with a dicarboxylic acid such as adipic acid with epichlorohydrin. Can be preferably used.
活性エネルギー線硬化型接着剤は、活性エネルギー線硬化型の化合物を含む。活性エネルギー線硬化型の化合物としては、カチオン重合性化合物またはラジカル重合性化合物が挙げられる。カチオン重合性化合物またはラジカル重合性化合物を含む場合、接着剤層の硬度を高める効果が期待できる。
The active energy ray-curable adhesive contains an active energy ray-curable compound. Examples of the active energy ray-curable compound include a cationically polymerizable compound and a radically polymerizable compound. When a cationically polymerizable compound or a radically polymerizable compound is contained, the effect of increasing the hardness of the adhesive layer can be expected.
カチオン重合性化合物としては、例えばオキセタン化合物またはエポキシ化合物などが挙げられる。カチオン重合性化合物の含有量は、活性エネルギー線硬化性の接着剤組成物100質量部に対して、10質量部以上99質量部以下であることが好ましく、40質量部以上99質量部以下であることがより好ましい。
Examples of the cationically polymerizable compound include an oxetane compound and an epoxy compound. The content of the cationically polymerizable compound is preferably 10 parts by mass or more and 99 parts by mass or less, and 40 parts by mass or more and 99 parts by mass or less, with respect to 100 parts by mass of the active energy ray-curable adhesive composition. Is more preferable.
活性エネルギー線硬化型接着剤は、オキセタン化合物を、1種のみ含んでもよいし、2種以上含んでもよい。活性エネルギー線硬化型接着剤は、エポキシ化合物は、1種のみ含んでもよいし、2種以上含んでもよい。
The active energy ray-curable adhesive may contain only one type of oxetane compound, or may contain two or more types. The active energy ray-curable adhesive may contain only one type of epoxy compound, or may contain two or more types of epoxy compounds.
ラジカル重合性化合物としては、(メタ)アクリル化合物、(メタ)アクリルアミド化合物などを挙げることができる。
Examples of the radically polymerizable compound include (meth) acrylic compounds and (meth) acrylamide compounds.
(メタ)アクリル系化合物としては、分子内に少なくとも1個の(メタ)アクリロイルオキシ基を有する(メタ)アクリレートモノマーや、分子内に少なくとも2個の(メタ)アクリロイルオキシ基を有する(メタ)アクリレートオリゴマーなどが挙げられる。これらはそれぞれ単独で使用してもよいし、2種以上を併用してもよい。
Examples of the (meth) acrylic compound include a (meth) acrylate monomer having at least one (meth) acryloyloxy group in the molecule and a (meth) acrylate having at least two (meth) acryloyloxy groups in the molecule. Examples include oligomers. These may be used alone or in combination of two or more.
(メタ)アクリルアミド系化合物としては、N-置換(メタ)アクリルアミド化合物が挙げられる。N-置換(メタ)アクリルアミド化合物は、N-位に置換基を有する(メタ)アクリルアミド化合物である。その置換基の典型的な例は、アルキル基である。N-位の置換基は互いに結合して環を形成していてもよく、この環を構成する-CH2-は、酸素原子に置換されていてもよい。さらに、その環を構成する炭素原子には、アルキル基やオキソ基(=O)のような置換基が結合していてもよい。N-置換(メタ)アクリルアミドは一般に、(メタ)アクリル酸またはその塩化物と1級または2級アミンとの反応によって製造できる。
Examples of the (meth) acrylamide compound include N-substituted (meth) acrylamide compounds. The N-substituted (meth) acrylamide compound is a (meth) acrylamide compound having a substituent at the N-position. A typical example of the substituent is an alkyl group. The substituents at the N-position may be bonded to each other to form a ring, and -CH 2- which constitutes this ring may be substituted with an oxygen atom. Further, a substituent such as an alkyl group or an oxo group (= O) may be bonded to the carbon atom constituting the ring. N-substituted (meth) acrylamide can generally be produced by the reaction of (meth) acrylic acid or its chloride with a primary or secondary amine.
ラジカル重合性化合物の含有量は、活性エネルギー線硬化型接着剤100質量部に対して1質量部以上70質量部以下であることが好ましく、10質量部以上60質量部以下であることがより好ましい。
The content of the radically polymerizable compound is preferably 1 part by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the active energy ray-curable adhesive, and more preferably 10 parts by mass or more and 60 parts by mass or less. ..
活性エネルギー線硬化型接着剤は、ラジカル重合性化合物を、1種のみ含んでもよいし、2種以上含んでもよい。
The active energy ray-curable adhesive may contain only one type of radically polymerizable compound, or may contain two or more types.
活性エネルギー線硬化型接着剤は、さらにカチオン重合開始剤またはラジカル重合開始剤を含むことができる。活性エネルギー線硬化型接着剤は、重合開始剤を1種のみ含んでもよいし、2種以上含んでもよい。
The active energy ray-curable adhesive can further contain a cationic polymerization initiator or a radical polymerization initiator. The active energy ray-curable adhesive may contain only one type of polymerization initiator, or may contain two or more types of polymerization initiators.
(その他の添加剤)
活性エネルギー線硬化接着剤は、光増感剤、溶剤、レベリング剤、酸化防止剤、光安定剤、紫外線吸収剤などを含んでもよい。 (Other additives)
The active energy ray-curing adhesive may contain a photosensitizer, a solvent, a leveling agent, an antioxidant, a light stabilizer, an ultraviolet absorber and the like.
活性エネルギー線硬化接着剤は、光増感剤、溶剤、レベリング剤、酸化防止剤、光安定剤、紫外線吸収剤などを含んでもよい。 (Other additives)
The active energy ray-curing adhesive may contain a photosensitizer, a solvent, a leveling agent, an antioxidant, a light stabilizer, an ultraviolet absorber and the like.
接着剤層の厚さは、例えば、0.1~5μmであり、好ましくは0.5~3μmである。
The thickness of the adhesive layer is, for example, 0.1 to 5 μm, preferably 0.5 to 3 μm.
〔位相差層30〕
位相差層は、液晶塗布型位相差層を含んで成るものである。液晶塗布型位相差層は、薄いため、屈曲したときにクラックが生じやすい傾向にあるが、本発明によれば、屈曲時のクラックを防止し得る。図1の実施形態において、位相差層30は、λ/4位相差層31、位相差層貼合層32及びポジティブC層33を偏光層10側からこの順に備える。別の実施形態において、位相差層は、λ/2位相差層、位相差層貼合層及びλ/4位相差層を偏光層10側からこの順に備える。 [Phase difference layer 30]
The retardation layer includes a liquid crystal coating type retardation layer. Since the liquid crystal coating type retardation layer is thin, cracks tend to occur when bent, but according to the present invention, cracks during bending can be prevented. In the embodiment of FIG. 1, theretardation layer 30 includes a λ / 4 retardation layer 31, a retardation layer bonding layer 32, and a positive C layer 33 in this order from the polarizing layer 10 side. In another embodiment, the retardation layer includes a λ / 2 retardation layer, a retardation layer bonding layer, and a λ / 4 retardation layer in this order from the polarizing layer 10 side.
位相差層は、液晶塗布型位相差層を含んで成るものである。液晶塗布型位相差層は、薄いため、屈曲したときにクラックが生じやすい傾向にあるが、本発明によれば、屈曲時のクラックを防止し得る。図1の実施形態において、位相差層30は、λ/4位相差層31、位相差層貼合層32及びポジティブC層33を偏光層10側からこの順に備える。別の実施形態において、位相差層は、λ/2位相差層、位相差層貼合層及びλ/4位相差層を偏光層10側からこの順に備える。 [Phase difference layer 30]
The retardation layer includes a liquid crystal coating type retardation layer. Since the liquid crystal coating type retardation layer is thin, cracks tend to occur when bent, but according to the present invention, cracks during bending can be prevented. In the embodiment of FIG. 1, the
(λ/4位相差層)
λ/4位相差層31は、入射光にλ/4の位相差を付与する機能を有するものである。
λ/4位相差層31は、例えば、波長550nmの光に対する面内位相差値が100~160nmであることができる。λ/4位相差層31は、重合性液晶化合物の硬化物を含む。λ/4位相差層31は、配向層を有してもよい。重合性液晶化合物としては、例えば、前記直線偏光層12に用いた重合性液晶化合物を用いることができる。直線偏光層12を形成する重合性液晶化合物と、λ/4位相差層31を形成する重合性液晶化合物とは、同じ種類であってもよいし、異なる種類であってもよい。 (Λ / 4 phase difference layer)
The λ / 4retardation layer 31 has a function of imparting a λ / 4 retardation to the incident light.
The λ / 4retardation layer 31 can have, for example, an in-plane retardation value of 100 to 160 nm with respect to light having a wavelength of 550 nm. The λ / 4 retardation layer 31 contains a cured product of a polymerizable liquid crystal compound. The λ / 4 retardation layer 31 may have an alignment layer. As the polymerizable liquid crystal compound, for example, the polymerizable liquid crystal compound used for the linearly polarizing layer 12 can be used. The polymerizable liquid crystal compound forming the linearly polarizing layer 12 and the polymerizable liquid crystal compound forming the λ / 4 retardation layer 31 may be of the same type or may be of different types.
λ/4位相差層31は、入射光にλ/4の位相差を付与する機能を有するものである。
λ/4位相差層31は、例えば、波長550nmの光に対する面内位相差値が100~160nmであることができる。λ/4位相差層31は、重合性液晶化合物の硬化物を含む。λ/4位相差層31は、配向層を有してもよい。重合性液晶化合物としては、例えば、前記直線偏光層12に用いた重合性液晶化合物を用いることができる。直線偏光層12を形成する重合性液晶化合物と、λ/4位相差層31を形成する重合性液晶化合物とは、同じ種類であってもよいし、異なる種類であってもよい。 (Λ / 4 phase difference layer)
The λ / 4
The λ / 4
λ/4位相差層31は、薄型化の観点から、好ましくは、液晶塗布型位相差層である。
液晶塗布型のλ/4位相差層は、位相差層用配向層上に、重合性液晶化合物を含む位相差層形成用組成物を塗布し、重合性液晶化合物を重合して硬化させることにより形成することができる。 The λ / 4retardation layer 31 is preferably a liquid crystal coating type retardation layer from the viewpoint of thinning.
The liquid crystal coating type λ / 4 retardation layer is formed by applying a composition for forming a retardation layer containing a polymerizable liquid crystal compound on an alignment layer for the retardation layer, and polymerizing and curing the polymerizable liquid crystal compound. Can be formed.
液晶塗布型のλ/4位相差層は、位相差層用配向層上に、重合性液晶化合物を含む位相差層形成用組成物を塗布し、重合性液晶化合物を重合して硬化させることにより形成することができる。 The λ / 4
The liquid crystal coating type λ / 4 retardation layer is formed by applying a composition for forming a retardation layer containing a polymerizable liquid crystal compound on an alignment layer for the retardation layer, and polymerizing and curing the polymerizable liquid crystal compound. Can be formed.
λ/4位相差層31の厚さは、例えば、0.3~10μm、好ましくは0.5~8μm、より好ましくは1~5μmである。
The thickness of the λ / 4 retardation layer 31 is, for example, 0.3 to 10 μm, preferably 0.5 to 8 μm, and more preferably 1 to 5 μm.
(位相差層貼合層32)
位相差層貼合層32は、λ/4位相差層31とポジティブC層33とを貼合する層、またはλ/2位相差層とλ/4位相差層とを貼合する層である。位相差層貼合層32は粘接着剤層20と同様の材料から同様の方法により形成される。粘接着剤層20は、接着剤層であることが好ましく、活性エネルギー線硬化型接着剤から形成することがより好ましい。 (Phase difference layer bonded layer 32)
The retardationlayer bonding layer 32 is a layer for bonding the λ / 4 retardation layer 31 and the positive C layer 33, or a layer for bonding the λ / 2 retardation layer and the λ / 4 retardation layer. .. The retardation layer bonding layer 32 is formed from the same material as the adhesive layer 20 by the same method. The adhesive layer 20 is preferably an adhesive layer, and more preferably formed from an active energy ray-curable adhesive.
位相差層貼合層32は、λ/4位相差層31とポジティブC層33とを貼合する層、またはλ/2位相差層とλ/4位相差層とを貼合する層である。位相差層貼合層32は粘接着剤層20と同様の材料から同様の方法により形成される。粘接着剤層20は、接着剤層であることが好ましく、活性エネルギー線硬化型接着剤から形成することがより好ましい。 (Phase difference layer bonded layer 32)
The retardation
位相差層貼合層32の厚さは、例えば、0.1~30μm、好ましくは0.5~20μm、より好ましくは1~10μmであり、さらに好ましくは1~5μm以下である。位相差層貼合層32の厚さが1μm未満であると得られる円偏光板の耐屈曲性が不十分になることがあり、30μmを超えると得られる円偏光板の可撓性が不十分になることがある。
位相差層貼合層の弾性率は、後述の実施例に記載された方法で測定される。位相差層貼合層の弾性率は、温度25℃における値であることができる。 The thickness of the retardation layer bondedlayer 32 is, for example, 0.1 to 30 μm, preferably 0.5 to 20 μm, more preferably 1 to 10 μm, and further preferably 1 to 5 μm or less. If the thickness of the retardation layer bonded layer 32 is less than 1 μm, the bending resistance of the obtained circularly polarizing plate may be insufficient, and if it exceeds 30 μm, the flexibility of the obtained circularly polarizing plate may be insufficient. May become.
The elastic modulus of the retardation layer bonded layer is measured by the method described in Examples described later. The elastic modulus of the retardation layer bonded layer can be a value at a temperature of 25 ° C.
位相差層貼合層の弾性率は、後述の実施例に記載された方法で測定される。位相差層貼合層の弾性率は、温度25℃における値であることができる。 The thickness of the retardation layer bonded
The elastic modulus of the retardation layer bonded layer is measured by the method described in Examples described later. The elastic modulus of the retardation layer bonded layer can be a value at a temperature of 25 ° C.
位相差層貼合層32の弾性率は1GPa以上、好ましくは1.5~6GPa、より好ましくは2~5GPaである。位相差層貼合層32の弾性率が1GPa未満であると得られる円偏光板の耐屈曲性が不十分になることがある。位相差層貼合層32の弾性率が大きすぎると円偏光板の可撓性が不十分になることがある。
The elastic modulus of the retardation layer bonded layer 32 is 1 GPa or more, preferably 1.5 to 6 GPa, and more preferably 2 to 5 GPa. If the elastic modulus of the retardation layer bonded layer 32 is less than 1 GPa, the bending resistance of the obtained circularly polarizing plate may be insufficient. If the elastic modulus of the retardation layer bonded layer 32 is too large, the flexibility of the circularly polarizing plate may be insufficient.
(ポジティブC層33)
ポジティブC層33は、表面を斜め方向から見た場合に反射光が色付いて見えるのを防ぐ等、円偏光板による光学的機能を補償する層である。「ポジティブC」とは、ポジティブC層の層面に沿ったX軸方向の屈折率をnx、層面に沿った方向でX軸に直交するY軸方向の屈折率をny、層厚方向の屈折率をnzとしたと場合に、nz>nx≒ny(光軸:nz方向)の関係を満たす性質をいう。 (Positive C layer 33)
Thepositive C layer 33 is a layer that compensates for the optical function of the circularly polarizing plate, such as preventing the reflected light from appearing colored when the surface is viewed from an oblique direction. The "positive C", the positive C layer of the layer surface along the X-axis direction of the refractive index n x, the refractive index n y in the Y-axis direction orthogonal to the X axis direction along the layer plane, of the layer thickness direction When the refractive index is n z , it means the property of satisfying the relationship of n z > n x ≈ n y (optical axis: n z direction).
ポジティブC層33は、表面を斜め方向から見た場合に反射光が色付いて見えるのを防ぐ等、円偏光板による光学的機能を補償する層である。「ポジティブC」とは、ポジティブC層の層面に沿ったX軸方向の屈折率をnx、層面に沿った方向でX軸に直交するY軸方向の屈折率をny、層厚方向の屈折率をnzとしたと場合に、nz>nx≒ny(光軸:nz方向)の関係を満たす性質をいう。 (Positive C layer 33)
The
ポジティブC層33は、重合性液晶化合物の硬化物を含む。ポジティブC層33は配向層を有してもよい。重合性液晶化合物としては、例えば、前記直線偏光層12に用いた重合性液晶化合物を用いることができる。直線偏光層12を形成する重合性液晶化合物と、ポジティブC層33を形成する重合性液晶化合物とは、同じ種類であってもよいし、異なる種類であってもよい。該重合性液晶化合物としては、円盤状液晶材料(ディスコティック液晶材料)及び棒状液晶材料等が挙げられるが、主鎖と側鎖を変更することで分散性を制御することが可能であり、波長分散性の調整も容易であることから、棒状液晶材料を使用することがより好ましい。
The positive C layer 33 contains a cured product of the polymerizable liquid crystal compound. The positive C layer 33 may have an alignment layer. As the polymerizable liquid crystal compound, for example, the polymerizable liquid crystal compound used for the linearly polarizing layer 12 can be used. The polymerizable liquid crystal compound forming the linearly polarized light layer 12 and the polymerizable liquid crystal compound forming the positive C layer 33 may be of the same type or different types. Examples of the polymerizable liquid crystal compound include a disk-shaped liquid crystal material (discotic liquid crystal material) and a rod-shaped liquid crystal material. Dispersibility can be controlled by changing the main chain and the side chain, and the wavelength can be controlled. It is more preferable to use a rod-shaped liquid crystal material because the dispersibility can be easily adjusted.
ポジティブC層33は、薄型化の観点から、好ましくは、液晶塗布型位相差層である。
液晶塗布型のポジティブC層は、位相差層用配向層上に、重合性液晶化合物を含む位相差層形成用組成物を塗布し、重合性液晶化合物を重合して硬化させることにより形成することができる。 Thepositive C layer 33 is preferably a liquid crystal coating type retardation layer from the viewpoint of thinning.
The liquid crystal coating type positive C layer is formed by applying a composition for forming a retardation layer containing a polymerizable liquid crystal compound on an alignment layer for a retardation layer, and polymerizing and curing the polymerizable liquid crystal compound. Can be done.
液晶塗布型のポジティブC層は、位相差層用配向層上に、重合性液晶化合物を含む位相差層形成用組成物を塗布し、重合性液晶化合物を重合して硬化させることにより形成することができる。 The
The liquid crystal coating type positive C layer is formed by applying a composition for forming a retardation layer containing a polymerizable liquid crystal compound on an alignment layer for a retardation layer, and polymerizing and curing the polymerizable liquid crystal compound. Can be done.
ポジティブC層33の厚さは、例えば、0.01~10μm、好ましくは0.1~8μm、より好ましくは0.3~5μmである。
The thickness of the positive C layer 33 is, for example, 0.01 to 10 μm, preferably 0.1 to 8 μm, and more preferably 0.3 to 5 μm.
(λ/2位相差層)
λ/2位相差層は、入射光にλ/2の位相差を付与する機能を有するものである。λ/2位相差層は、例えば、波長550nmの光に対する面内位相差値が200~350nmであることができる。λ/2位相差層は、重合性液晶化合物の硬化物を含むことができる。λ/2位相差層は、配向層を有してもよい。重合性液晶化合物としては、例えば、前記λ/4位相差層に用いた重合性液晶化合物を用いることができる。λ/4位相差層を形成する重合性液晶化合物と、λ/2位相差層を形成する重合性液晶化合物とは、同じ種類であってもよいし、異なる種類であってもよい。 (Λ / 2 phase difference layer)
The λ / 2 phase difference layer has a function of imparting a λ / 2 phase difference to the incident light. The λ / 2 retardation layer can have, for example, an in-plane retardation value of 200 to 350 nm with respect to light having a wavelength of 550 nm. The λ / 2 retardation layer can contain a cured product of a polymerizable liquid crystal compound. The λ / 2 retardation layer may have an alignment layer. As the polymerizable liquid crystal compound, for example, the polymerizable liquid crystal compound used for the λ / 4 retardation layer can be used. The polymerizable liquid crystal compound forming the λ / 4 retardation layer and the polymerizable liquid crystal compound forming the λ / 2 retardation layer may be of the same type or may be different types.
λ/2位相差層は、入射光にλ/2の位相差を付与する機能を有するものである。λ/2位相差層は、例えば、波長550nmの光に対する面内位相差値が200~350nmであることができる。λ/2位相差層は、重合性液晶化合物の硬化物を含むことができる。λ/2位相差層は、配向層を有してもよい。重合性液晶化合物としては、例えば、前記λ/4位相差層に用いた重合性液晶化合物を用いることができる。λ/4位相差層を形成する重合性液晶化合物と、λ/2位相差層を形成する重合性液晶化合物とは、同じ種類であってもよいし、異なる種類であってもよい。 (Λ / 2 phase difference layer)
The λ / 2 phase difference layer has a function of imparting a λ / 2 phase difference to the incident light. The λ / 2 retardation layer can have, for example, an in-plane retardation value of 200 to 350 nm with respect to light having a wavelength of 550 nm. The λ / 2 retardation layer can contain a cured product of a polymerizable liquid crystal compound. The λ / 2 retardation layer may have an alignment layer. As the polymerizable liquid crystal compound, for example, the polymerizable liquid crystal compound used for the λ / 4 retardation layer can be used. The polymerizable liquid crystal compound forming the λ / 4 retardation layer and the polymerizable liquid crystal compound forming the λ / 2 retardation layer may be of the same type or may be different types.
λ/2位相差層は、薄型化の観点から、好ましくは、液晶塗布型位相差層である。液晶塗布型のλ/2位相差層は、位相差層用配向層上に、重合性液晶化合物を含む位相差層形成用組成物を塗布し、重合性液晶化合物を重合して硬化させることにより形成することができる。
The λ / 2 retardation layer is preferably a liquid crystal coating type retardation layer from the viewpoint of thinning. The liquid crystal coating type λ / 2 retardation layer is formed by applying a composition for forming a retardation layer containing a polymerizable liquid crystal compound on an alignment layer for the retardation layer, and polymerizing and curing the polymerizable liquid crystal compound. Can be formed.
λ/2位相差層の厚さは、例えば、0.3~10μm、好ましくは0.5~8μm、より好ましくは1~5μmである。
The thickness of the λ / 2 retardation layer is, for example, 0.3 to 10 μm, preferably 0.5 to 8 μm, and more preferably 1 to 5 μm.
〔円偏光板100の製造〕
図1の実施形態において、円偏光板100は、例えば、次の方法により製造することができる。即ち、保護層11の上に直線偏光層12及びオーバーコート層13を形成して、偏光層10を得る。別途準備した基材の上にλ/4位相差層31を形成し、別途準備した基材の上にポジティブC層33を形成する。次いで、位相差層貼合層32用粘接着剤を使用して、λ/4位相差層31とポジティブC層33とを貼合して、位相差層30を得る。
その後、λ/4位相差層31側の基材を除去し、粘接着剤層20用粘接着剤を使用して、偏光層10のオーバーコート層13と位相差層30のλ/4位相差層31とを貼合して、円偏光板100を得る。 [Manufacturing of circularly polarizing plate 100]
In the embodiment of FIG. 1, the circularlypolarizing plate 100 can be manufactured, for example, by the following method. That is, the linearly polarizing layer 12 and the overcoat layer 13 are formed on the protective layer 11 to obtain the polarizing layer 10. The λ / 4 retardation layer 31 is formed on the separately prepared base material, and the positive C layer 33 is formed on the separately prepared base material. Next, the λ / 4 retardation layer 31 and the positive C layer 33 are bonded together using the adhesive for the retardation layer bonding layer 32 to obtain the retardation layer 30.
After that, the base material on the λ / 4retardation layer 31 side is removed, and the adhesive for the adhesive layer 20 is used to λ / 4 of the overcoat layer 13 of the polarizing layer 10 and the retardation layer 30. The retardation layer 31 is bonded to obtain a circularly polarizing plate 100.
図1の実施形態において、円偏光板100は、例えば、次の方法により製造することができる。即ち、保護層11の上に直線偏光層12及びオーバーコート層13を形成して、偏光層10を得る。別途準備した基材の上にλ/4位相差層31を形成し、別途準備した基材の上にポジティブC層33を形成する。次いで、位相差層貼合層32用粘接着剤を使用して、λ/4位相差層31とポジティブC層33とを貼合して、位相差層30を得る。
その後、λ/4位相差層31側の基材を除去し、粘接着剤層20用粘接着剤を使用して、偏光層10のオーバーコート層13と位相差層30のλ/4位相差層31とを貼合して、円偏光板100を得る。 [Manufacturing of circularly polarizing plate 100]
In the embodiment of FIG. 1, the circularly
After that, the base material on the λ / 4
〔その他の実施形態〕
図2~4は本発明の他の実施形態である円偏光板の構造を示す断面図である。図2~4の円偏光板は、位相差層30が、その少なくとも一方の面に補強層を有する。図2の円偏光板200では、第1補強層41が位相差層30の上部に形成されている。図3の円偏光板300では、第2補強層42が位相差層30の下部に形成されている。図4の円偏光板400では、第1補強層41が位相差層30の上部に、第2補強層42が位相差層30の下部に形成されている。図2~4の円偏光板は、補強層を有することで、より優れた耐屈曲性を示すようになる。 [Other embodiments]
2 to 4 are cross-sectional views showing the structure of a circularly polarizing plate according to another embodiment of the present invention. In the circularly polarizing plate of FIGS. 2 to 4, theretardation layer 30 has a reinforcing layer on at least one surface thereof. In the circularly polarizing plate 200 of FIG. 2, the first reinforcing layer 41 is formed on the upper portion of the retardation layer 30. In the circularly polarizing plate 300 of FIG. 3, the second reinforcing layer 42 is formed below the retardation layer 30. In the circularly polarizing plate 400 of FIG. 4, the first reinforcing layer 41 is formed above the retardation layer 30, and the second reinforcing layer 42 is formed below the retardation layer 30. By having the reinforcing layer, the circularly polarizing plates of FIGS. 2 to 4 exhibit more excellent bending resistance.
図2~4は本発明の他の実施形態である円偏光板の構造を示す断面図である。図2~4の円偏光板は、位相差層30が、その少なくとも一方の面に補強層を有する。図2の円偏光板200では、第1補強層41が位相差層30の上部に形成されている。図3の円偏光板300では、第2補強層42が位相差層30の下部に形成されている。図4の円偏光板400では、第1補強層41が位相差層30の上部に、第2補強層42が位相差層30の下部に形成されている。図2~4の円偏光板は、補強層を有することで、より優れた耐屈曲性を示すようになる。 [Other embodiments]
2 to 4 are cross-sectional views showing the structure of a circularly polarizing plate according to another embodiment of the present invention. In the circularly polarizing plate of FIGS. 2 to 4, the
補強層は粘接着剤層20と同様の材料から同様の方法により形成される。補強層は、前述の活性エネルギー線硬化型接着剤を用いて形成することが好ましい。例えば、位相差層30を形成した後、偏光層10と貼合する前に、位相差層30の外側面、即ち、λ/4位相差層31の露出面に、第1補強層41用粘接着剤を塗布することで、第1補強層41を形成することができる。また、位相差層30を形成した後に、位相差層30の内側面、即ち、ポジティブC層33の露出面に、第2補強層42用粘接着剤を塗布することで、第2補強層42を形成することができる。必要に応じて、粘接着剤を加熱したり、粘接着剤に活性エネルギー線を照射したりして、粘接着剤を硬化させることができる。
The reinforcing layer is formed from the same material as the adhesive layer 20 by the same method. The reinforcing layer is preferably formed by using the above-mentioned active energy ray-curable adhesive. For example, after the retardation layer 30 is formed and before being bonded to the polarizing layer 10, the outer surface of the retardation layer 30, that is, the exposed surface of the λ / 4 retardation layer 31, is adhered to the first reinforcing layer 41. By applying the adhesive, the first reinforcing layer 41 can be formed. Further, after the retardation layer 30 is formed, the second reinforcing layer is applied by applying the adhesive for the second reinforcing layer 42 to the inner surface of the retardation layer 30, that is, the exposed surface of the positive C layer 33. 42 can be formed. If necessary, the adhesive can be cured by heating the adhesive or irradiating the adhesive with active energy rays.
補強層の厚さは、例えば、0.1~30μm、好ましくは0.3~10μm、より好ましくは0.5~5μmである。補強層の厚さが0.1μm未満であると得られる円偏光板の耐屈曲性が不十分になることがあり、30μmを超えると得られる円偏光板の可撓性が不十分になることがある。
The thickness of the reinforcing layer is, for example, 0.1 to 30 μm, preferably 0.3 to 10 μm, and more preferably 0.5 to 5 μm. If the thickness of the reinforcing layer is less than 0.1 μm, the bending resistance of the obtained circularly polarizing plate may be insufficient, and if it exceeds 30 μm, the flexibility of the obtained circularly polarizing plate may be insufficient. There is.
補強層の弾性率は、例えば、1GPa以上、好ましくは1.5~6GPa、より好ましくは2~5GPaである。補強層の弾性率が1GPa未満であると得られる円偏光板の耐屈曲性が不十分になることがある。補強層の弾性率が大きすぎると円偏光板の可撓性が不十分になることがある。補強層の弾性率は、後述の実施例に記載された方法で測定される。補強層の弾性率は、温度25℃における値であることができる。
The elastic modulus of the reinforcing layer is, for example, 1 GPa or more, preferably 1.5 to 6 GPa, and more preferably 2 to 5 GPa. If the elastic modulus of the reinforcing layer is less than 1 GPa, the bending resistance of the obtained circularly polarizing plate may be insufficient. If the elastic modulus of the reinforcing layer is too large, the flexibility of the circularly polarizing plate may be insufficient. The elastic modulus of the reinforcing layer is measured by the method described in Examples described later. The elastic modulus of the reinforcing layer can be a value at a temperature of 25 ° C.
〔円偏光板〕
本発明の円偏光板は、優れた可撓性を付与しやすくする観点から、100μm以下、好ましくは5~50μm、より好ましくは10~30μmの厚さを有する。円偏光板の厚さが150μmを超えると可撓性が不十分になることがある。 [Circular polarizing plate]
The circularly polarizing plate of the present invention has a thickness of 100 μm or less, preferably 5 to 50 μm, and more preferably 10 to 30 μm from the viewpoint of facilitating the imparting of excellent flexibility. If the thickness of the circularly polarizing plate exceeds 150 μm, the flexibility may be insufficient.
本発明の円偏光板は、優れた可撓性を付与しやすくする観点から、100μm以下、好ましくは5~50μm、より好ましくは10~30μmの厚さを有する。円偏光板の厚さが150μmを超えると可撓性が不十分になることがある。 [Circular polarizing plate]
The circularly polarizing plate of the present invention has a thickness of 100 μm or less, preferably 5 to 50 μm, and more preferably 10 to 30 μm from the viewpoint of facilitating the imparting of excellent flexibility. If the thickness of the circularly polarizing plate exceeds 150 μm, the flexibility may be insufficient.
本発明の円偏光板は、優れた耐屈曲性を有する観点から、15%以上、好ましくは18%以上、より好ましくは20%以上、さらに好ましくは26%以上のクラックストレインを有する。クラックストレインの上限は特に限定されないが、クラックストレインは、例えば50%以下であってもよいし、35%以下であってもよい。円偏光板のクラックストレインが15%未満であると耐屈曲性が不十分になることがある。ここで、クラックストレインとは、所定の条件下で材料を一方向に引っ張って伸ばした場合に、クラックが発生しない限界の伸び率(%)をいう。クラックストレインの測定条件は、実施例として記載した通りである。クラックストレインは、円偏光板を構成する層の材料や厚みなどで調製することが可能である。例えば、位相差層が補強層を備えたり、補強層の数が増えたりすることで、クラックストレインを増大させることができる。また、円偏光板を例えば50~100℃で0.5~24時間加熱処理をすることで、クラックストレインを増大させることもできる。
The circularly polarizing plate of the present invention has a crack strain of 15% or more, preferably 18% or more, more preferably 20% or more, still more preferably 26% or more from the viewpoint of having excellent bending resistance. The upper limit of the crack strain is not particularly limited, but the crack strain may be, for example, 50% or less, or 35% or less. If the crack strain of the circularly polarizing plate is less than 15%, the bending resistance may be insufficient. Here, the crack strain means a limit elongation rate (%) at which cracks do not occur when the material is pulled and stretched in one direction under predetermined conditions. The measurement conditions of the crack strain are as described as Examples. The crack strain can be prepared by the material and thickness of the layers constituting the circularly polarizing plate. For example, the crack strain can be increased by providing the retarding layer with a reinforcing layer or increasing the number of reinforcing layers. Further, the crack strain can be increased by heat-treating the circularly polarizing plate at, for example, 50 to 100 ° C. for 0.5 to 24 hours.
(前面板)
前面板(図面には非表示)は、一般に、保護層11の上部に配置され、偏光層10の最外側を構成する。前面板は、一体性及び透光性を有する板状の層である。前面板は2層以上から構成されてもよい。前面板の例としては、樹脂製の板状体(例えば、樹脂板、樹脂シート、樹脂フィルム)、ガラス製の板状体(例えば、ガラス板)、樹脂製の板状体とガラス製の板状体との積層体等が挙げられる。 (Front plate)
The front plate (not shown in the drawing) is generally arranged above theprotective layer 11 and constitutes the outermost side of the polarizing layer 10. The front plate is a plate-like layer having integrality and translucency. The front plate may be composed of two or more layers. Examples of front plates include resin plate-like bodies (eg, resin plates, resin sheets, resin films), glass plate-like bodies (eg, glass plates), resin plate-like bodies and glass plates. Examples thereof include a laminated body with a shaped body.
前面板(図面には非表示)は、一般に、保護層11の上部に配置され、偏光層10の最外側を構成する。前面板は、一体性及び透光性を有する板状の層である。前面板は2層以上から構成されてもよい。前面板の例としては、樹脂製の板状体(例えば、樹脂板、樹脂シート、樹脂フィルム)、ガラス製の板状体(例えば、ガラス板)、樹脂製の板状体とガラス製の板状体との積層体等が挙げられる。 (Front plate)
The front plate (not shown in the drawing) is generally arranged above the
前面板が樹脂製の板状体である場合、材料としては、例えば、ポリメチル(メタ)アクリレート及びポリエチル(メタ)アクリレート等のアクリル系樹脂;ポリエチレン、ポリプロピレン、ポリメチルペンテン及びポリスチレン等のポリオレフィン系樹脂;トリアセチルセルロース、アセチルセルロースブチレート、プロピオニルセルロース、ブチリルセルロース及びアセチルプロピオニルセルロース等のセルロース系樹脂;エチレン-酢酸ビニル共重合体、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリビニルアルコール及びポリビニルアセタール等のポリビニル系樹脂;ポリスルホン及びポリエーテルスルホン等のスルホン系樹脂;ポリエーテルケトン及びポリエーテルエーテルケトン等のケトン系樹脂;ポリエーテルイミド;ポリカーボネート系樹脂;ポリエステル系樹脂;ポリイミド系樹脂;ポリアミドイミド系樹脂;及びポリアミド系樹脂等が挙げられる。これらの高分子は単独で又は2種以上を混合して用いることができる。これらの中でも強度及び透明性向上の観点から、ポリカーボネート系樹脂、ポリエステル系樹脂、ポリイミド系樹脂、ポリアミドイミド系樹脂、又はポリアミド系樹脂を用いることが好ましい。
When the front plate is a resin plate-like body, the material may be, for example, an acrylic resin such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; and a polyolefin resin such as polyethylene, polypropylene, polymethylpentene and polystyrene. Cellular resins such as triacetyl cellulose, acetyl cellulose butyrate, propionyl cellulose, butyryl cellulose and acetyl propionyl cellulose; polyvinyl acetate such as ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol and polyvinyl acetal. Based resin; Sulfon-based resin such as polysulfone and polyether sulfone; Ketone-based resin such as polyether ketone and polyether ether ketone; Polyetherimide; Polycarbonate resin; Polyester resin; Polyimide resin; Polyamideimide-based resin; and Examples thereof include polyamide resins. These polymers can be used alone or in admixture of two or more. Among these, from the viewpoint of improving strength and transparency, it is preferable to use a polycarbonate-based resin, a polyester-based resin, a polyimide-based resin, a polyamide-imide-based resin, or a polyamide-based resin.
前面板は、上記樹脂からできたフィルムであってよく、フィルムの少なくとも一方の面にハードコート層を有してもよい。ハードコート層は、フィルムの外側の面に形成されていても、両方の面に形成されていてもよい。ハードコート層を設けることにより、硬度及び耐スクラッチ性を向上させた樹脂フィルムとすることができる。ハードコート層は、例えば、紫外線硬化型樹脂の硬化層である。紫外線硬化型樹脂としては、例えば、アクリル系樹脂、シリコーン系樹脂、ポリエステル系樹脂、ウレタン系樹脂、アミド系樹脂、エポキシ系樹脂等が挙げられる。ハードコート層は、硬度を向上させるために、添加剤を含んでいてもよい。添加剤は前面板の透光性を阻害するものでなければ、特に限定されることはなく、無機系微粒子、有機系微粒子、又はこれらの混合物を使用することができる。
The front plate may be a film made of the above resin, and may have a hard coat layer on at least one surface of the film. The hard coat layer may be formed on the outer surface of the film or may be formed on both surfaces. By providing the hard coat layer, it is possible to obtain a resin film having improved hardness and scratch resistance. The hard coat layer is, for example, a cured layer of an ultraviolet curable resin. Examples of the ultraviolet curable resin include acrylic resins, silicone resins, polyester resins, urethane resins, amide resins, epoxy resins and the like. The hard coat layer may contain additives in order to improve the hardness. The additive is not particularly limited as long as it does not inhibit the translucency of the front plate, and inorganic fine particles, organic fine particles, or a mixture thereof can be used.
円偏光板100がディスプレイパネルに用いられる場合、前面板は、ディスプレイパネルにおけるウィンドウフィルムとしての機能を有していてもよい。前面板は、さらにタッチセンサとしての機能、ブルーライトカット機能、視野角調整機能等を有するものであってもよい。
When the circularly polarizing plate 100 is used for a display panel, the front plate may have a function as a window film in the display panel. The front plate may further have a function as a touch sensor, a blue light cut function, a viewing angle adjusting function, and the like.
前面板の厚さは、例えば、1~100μm、好ましくは10~70μm、より好ましくは20~60μmである。
The thickness of the front plate is, for example, 1 to 100 μm, preferably 10 to 70 μm, and more preferably 20 to 60 μm.
(背面板)
位相差層30の下部には、粘着剤層を介して背面板(図面には非表示)が積層されることができる。背面板としては、光を透過可能な板状体、または通常の表示装置に用いられる構成要素等を用いることができる。 (Back plate)
A back plate (not shown in the drawing) can be laminated on the lower portion of theretardation layer 30 via an adhesive layer. As the back plate, a plate-like body capable of transmitting light, a component used in a normal display device, or the like can be used.
位相差層30の下部には、粘着剤層を介して背面板(図面には非表示)が積層されることができる。背面板としては、光を透過可能な板状体、または通常の表示装置に用いられる構成要素等を用いることができる。 (Back plate)
A back plate (not shown in the drawing) can be laminated on the lower portion of the
背面板の厚さは、例えば5μm~2000μmであってよく、好ましくは10μm~1000μmであり、より好ましくは15μm~500μmである。
The thickness of the back plate may be, for example, 5 μm to 2000 μm, preferably 10 μm to 1000 μm, and more preferably 15 μm to 500 μm.
背面板に用いる板状体は、1層のみから構成されてよく、2層以上から構成されたものであってよく、前面板において述べた板状体について例示したものを用いることができる。
The plate-shaped body used for the back plate may be composed of only one layer, may be composed of two or more layers, and an example of the plate-shaped body described in the front plate can be used.
背面板に用いる通常の表示装置に用いられる構成要素としては、例えばセパレータ、タッチセンサパネル、有機EL表示素子等が挙げられる。表示装置における構成要素の積層順としては、例えば前面板/円偏光板/セパレータ、前面板/円偏光板/有機EL表示素子、前面板/円偏光板/タッチセンサパネル/有機EL表示素子、前面板/タッチセンサパネル/円偏光板/有機EL表示素子等が挙げられる。
Examples of the components used in a normal display device used for the back plate include a separator, a touch sensor panel, an organic EL display element, and the like. The stacking order of the components in the display device is, for example, front plate / circular polarizing plate / separator, front plate / circular polarizing plate / organic EL display element, front plate / circular polarizing plate / touch sensor panel / organic EL display element, front. Examples thereof include a face plate / touch sensor panel / circularly polarizing plate / organic EL display element.
以降、実施例により本発明を更に詳細に説明する。本発明はこれらの実施例に限定されるものではない。本実施例中、物質を配合する割合の単位「部」は、特に断らない限り、重量基準とする。
Hereinafter, the present invention will be described in more detail by way of examples. The present invention is not limited to these examples. In this example, the unit "part" of the mixing ratio of the substance is based on the weight unless otherwise specified.
(a)層の厚さの測定方法
円偏光板を構成する層の厚さは、接触式膜厚測定装置(株式会社ニコン製「MS-5C」(商品名))を用いて測定した。ただし、偏光層及び配向層は、レーザー顕微鏡(オリンパス株式会社製「OLS3000」(商品名))を用いて測定した。 (A) Method for measuring the thickness of the layer The thickness of the layer constituting the circularly polarizing plate was measured using a contact-type film thickness measuring device (“MS-5C” (trade name) manufactured by Nikon Corporation). However, the polarizing layer and the alignment layer were measured using a laser microscope (“OLS3000” (trade name) manufactured by Olympus Corporation).
円偏光板を構成する層の厚さは、接触式膜厚測定装置(株式会社ニコン製「MS-5C」(商品名))を用いて測定した。ただし、偏光層及び配向層は、レーザー顕微鏡(オリンパス株式会社製「OLS3000」(商品名))を用いて測定した。 (A) Method for measuring the thickness of the layer The thickness of the layer constituting the circularly polarizing plate was measured using a contact-type film thickness measuring device (“MS-5C” (trade name) manufactured by Nikon Corporation). However, the polarizing layer and the alignment layer were measured using a laser microscope (“OLS3000” (trade name) manufactured by Olympus Corporation).
(b)弾性率(G’)の測定方法
粘接着剤層20および補強層が粘着剤層である場合、粘着剤層を150μmになるように積み重ねて、サンプルを作製した。弾性率(G’)は、レオメーター(Anton Parr社製「MCR-301」(商品名))を用いて、貯蔵弾性率を測定した。測定条件は、温度25℃、応力1%及び周波数1Hzとした。 (B) Method for measuring elastic modulus (G') When theadhesive layer 20 and the reinforcing layer are adhesive layers, the adhesive layers were stacked so as to be 150 μm to prepare a sample. The elastic modulus (G') was measured by using a rheometer (“MCR-301” (trade name) manufactured by Antonio Parr). The measurement conditions were a temperature of 25 ° C., a stress of 1%, and a frequency of 1 Hz.
粘接着剤層20および補強層が粘着剤層である場合、粘着剤層を150μmになるように積み重ねて、サンプルを作製した。弾性率(G’)は、レオメーター(Anton Parr社製「MCR-301」(商品名))を用いて、貯蔵弾性率を測定した。測定条件は、温度25℃、応力1%及び周波数1Hzとした。 (B) Method for measuring elastic modulus (G') When the
また、粘接着剤層20および補強層が粘着剤層ではない接着剤層である場合、ガラス(厚み1.0mm)に接着剤組成物を塗工して得られた塗膜の上に、COPフィルム(日本ゼオン株式会社製、厚み50μm)を積層した。その後、塗膜に対して、紫外線照射装置(フュージョンUVシステムズ社製、無電極紫外線ランプのHバルブを備えるもの)を用いて光照射強度が400mW/cm2、波長280~320nmでの積算光量が1500mJ/cm2となるよう紫外線を照射し、接着剤組成物を硬化させて、ガラス/接着剤層/COPフィルムの層構造を有する積層シートを得た。積層シートからCOPフィルムを剥がした後、 露出した接着剤層をNano Indenter(HM-500、フィッシャー・インスツルメンツ社製)を用いて、温度25℃、相対湿度50%、圧力1mNの条件で、圧縮弾性率の測定を行った。圧子には、Berkovich三角錘圧子を用いた。
When the adhesive layer 20 and the reinforcing layer are adhesive layers that are not adhesive layers, the adhesive composition is applied to glass (thickness 1.0 mm) on the coating film obtained. A COP film (manufactured by Nippon Zeon Co., Ltd., thickness 50 μm) was laminated. After that, the coating film was subjected to an ultraviolet irradiation device (manufactured by Fusion UV Systems, equipped with an H-valve of an electrodeless ultraviolet lamp), and the light irradiation intensity was 400 mW / cm 2 , and the integrated light amount at a wavelength of 280 to 320 nm was obtained. Ultraviolet rays were irradiated so as to be 1500 mJ / cm 2, and the adhesive composition was cured to obtain a laminated sheet having a layer structure of glass / adhesive layer / COP film. After peeling the COP film from the laminated sheet, the exposed adhesive layer is compressively elasticized using Nano Indicator (HM-500, manufactured by Fisher Instruments) at a temperature of 25 ° C., a relative humidity of 50%, and a pressure of 1 mN. The rate was measured. As an indenter, a Berkovich triangular weight indenter was used.
<製造例1>
(偏光層10の製造)
配向層形成用組成物の調製
以下の構造式で表される光反応性基を有するポリマーを、濃度5%で、シクロペンタノンに溶解した溶液を配向層形成用組成物(1)として調製した。 <Manufacturing example 1>
(Manufacturing of polarizing layer 10)
Preparation of Alignment Layer Forming Composition A solution prepared by dissolving a polymer having a photoreactive group represented by the following structural formula in cyclopentanone at a concentration of 5% was prepared as the alignment layer forming composition (1). ..
(偏光層10の製造)
配向層形成用組成物の調製
以下の構造式で表される光反応性基を有するポリマーを、濃度5%で、シクロペンタノンに溶解した溶液を配向層形成用組成物(1)として調製した。 <Manufacturing example 1>
(Manufacturing of polarizing layer 10)
Preparation of Alignment Layer Forming Composition A solution prepared by dissolving a polymer having a photoreactive group represented by the following structural formula in cyclopentanone at a concentration of 5% was prepared as the alignment layer forming composition (1). ..
直線偏光層形成用組成物の調製
以下の構造で表される化合物(1-1)及び化合物(1-2)を重合性液晶化合物として用いた。化合物(1-1)および化合物(1-2)は、Lub et al.Recl.Trav.Chim.Pays-Bas、115、321-328(1996)記載の方法により合成した。 Preparation of Composition for Forming a Linearly Polarized Layer The compound (1-1) and the compound (1-2) represented by the following structures were used as the polymerizable liquid crystal compound. Compound (1-1) and compound (1-2) are described in Lub et al. Recl. Trav. Chim. It was synthesized by the method described in Pays-Bas, 115, 321-328 (1996).
以下の構造で表される化合物(1-1)及び化合物(1-2)を重合性液晶化合物として用いた。化合物(1-1)および化合物(1-2)は、Lub et al.Recl.Trav.Chim.Pays-Bas、115、321-328(1996)記載の方法により合成した。 Preparation of Composition for Forming a Linearly Polarized Layer The compound (1-1) and the compound (1-2) represented by the following structures were used as the polymerizable liquid crystal compound. Compound (1-1) and compound (1-2) are described in Lub et al. Recl. Trav. Chim. It was synthesized by the method described in Pays-Bas, 115, 321-328 (1996).
・化合物(1-1)
-Compound (1-1)
・化合物(1-2)
-Compound (1-2)
以下の構造で表される化合物(2-1a)、化合物(2-1b)、及び化合物(2-2)を二色性色素として用いた。
Compound (2-1a), compound (2-1b), and compound (2-2) represented by the following structures were used as dichroic dyes.
・化合物(2-1a)
-Compound (2-1a)
・化合物(2-1b)
-Compound (2-1b)
・化合物(2-2)
-Compound (2-2)
直線偏光層形成用組成物は、化合物(1-1)75部、化合物(1-2)25部、二色性色素としての上記式(2-1a)、(2-1b)、(2-2)で示されるアゾ色素各2.5部、重合開始剤としての2-ジメチルアミノ-2-ベンジル-1-(4-モルホリノフェニル)ブタン-1-オン(Irgacure369、BASF社製)6部、及びレベリング剤としてのポリアクリレート化合物(BYK-361N、BYK社製)1.2部を、溶剤のトルエン400部に混合し、得られた混合物を80℃で1時間撹拌することにより調製した。
The composition for forming a linear polarizing layer includes 75 parts of compound (1-1), 25 parts of compound (1-2), and the above formulas (2-1a), (2-1b), and (2-2-) as a bicolor dye. 2.5 parts each of the azo dye shown in 2), 6 parts of 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butane-1-one (Irgacure 369, manufactured by BASF) as a polymerization initiator, And 1.2 parts of the polyacrylate compound (BYK-361N, manufactured by BYK) as a leveling agent was mixed with 400 parts of toluene as a solvent, and the obtained mixture was stirred at 80 ° C. for 1 hour to prepare.
オーバーコート層形成用組成物の調製
オーバーコート層を形成するためのオーバーコート層形成用組成物は、水100部、ポリビニルアルコール樹脂粉末(KL-318、株式会社クラレ製、平均重合度18000)3部、架橋剤としてのポリアミドエポキシ樹脂(SR650(30)、住化ケムテックス株式会社製)1.5部を混合して調製した。 Preparation of composition for forming an overcoat layer The composition for forming an overcoat layer for forming an overcoat layer is 100 parts of water, polyvinyl alcohol resin powder (KL-318, manufactured by Kuraray Co., Ltd., average degree of polymerization 18000) 3 A part and 1.5 parts of a polyamide epoxy resin (SR650 (30), manufactured by Sumika Chemtex Co., Ltd.) as a cross-linking agent were mixed and prepared.
オーバーコート層を形成するためのオーバーコート層形成用組成物は、水100部、ポリビニルアルコール樹脂粉末(KL-318、株式会社クラレ製、平均重合度18000)3部、架橋剤としてのポリアミドエポキシ樹脂(SR650(30)、住化ケムテックス株式会社製)1.5部を混合して調製した。 Preparation of composition for forming an overcoat layer The composition for forming an overcoat layer for forming an overcoat layer is 100 parts of water, polyvinyl alcohol resin powder (KL-318, manufactured by Kuraray Co., Ltd., average degree of polymerization 18000) 3 A part and 1.5 parts of a polyamide epoxy resin (SR650 (30), manufactured by Sumika Chemtex Co., Ltd.) as a cross-linking agent were mixed and prepared.
積層体の作製
保護層11としてトリアセチルセルロール(TAC)フィルム(KC2UA、コニカミノルタ株式会社製、厚さ25μm)を使用して、これに出力0.3kW、処理速度3m/分の条件の下、コロナ処理を施した。その後、フィルムのコロナ処理面に、前記調製した配向層形成用組成物(1)をバーコート法により塗布し、温度80℃の乾燥オーブン中で1分間加熱乾燥した。得られた被膜に対し、ワイヤーグリッド(UIS-27132##、ウシオ電機株式会社製)を透過させて、波長365nmでの積算光量が100mJ/cm2となるように調整した紫外線を照射して、厚さ100nmの配向層を得た。その後、得られた配向層に、前記調製した直線偏光層形成用組成物をバーコート法により塗布し、被膜を温度120℃の乾燥オーブン中で1分間加熱乾燥して室温まで冷却した。波長365nmでの積算光量が1200mJ/cm2となるように調整した紫外線をこれに照射し、厚さ2.0μmの直線偏光層12を形成した。形成した直線偏光層上に、前記調製したオーバーコート層形成用組成物を、乾燥後の厚さが1.0μmとなるよう、バーコート法により塗布し、温度80℃で3分間乾燥した。かかる手順で、保護層11(厚さ25μm)、直線偏光層12(厚さ2.0μm)、及びオーバーコート層13(厚さ1.0μm)をこの順に備える偏光層10を製造した。 Preparation of Laminate A triacetyl cellol (TAC) film (KC2UA, manufactured by Konica Minolta Co., Ltd., thickness 25 μm) is used as theprotective layer 11 under the conditions of an output of 0.3 kW and a processing speed of 3 m / min. , Corona treated. Then, the prepared composition for forming an alignment layer (1) was applied to the corona-treated surface of the film by a bar coating method, and heated and dried in a drying oven at a temperature of 80 ° C. for 1 minute. The obtained film was passed through a wire grid (UIS-27132 ##, manufactured by Ushio, Inc.) and irradiated with ultraviolet rays adjusted so that the integrated light intensity at a wavelength of 365 nm was 100 mJ / cm 2. An oriented layer having a thickness of 100 nm was obtained. Then, the prepared composition for forming a linear polarizing layer was applied to the obtained alignment layer by a bar coating method, and the coating film was heated and dried in a drying oven at a temperature of 120 ° C. for 1 minute and cooled to room temperature. The linearly polarizing layer 12 having a thickness of 2.0 μm was formed by irradiating this with ultraviolet rays adjusted so that the integrated light amount at a wavelength of 365 nm was 1200 mJ / cm 2. The prepared composition for forming an overcoat layer was applied onto the formed linearly polarized light layer by a bar coating method so that the thickness after drying was 1.0 μm, and dried at a temperature of 80 ° C. for 3 minutes. By this procedure, a polarizing layer 10 including a protective layer 11 (thickness 25 μm), a linear polarizing layer 12 (thickness 2.0 μm), and an overcoat layer 13 (thickness 1.0 μm) was manufactured in this order.
保護層11としてトリアセチルセルロール(TAC)フィルム(KC2UA、コニカミノルタ株式会社製、厚さ25μm)を使用して、これに出力0.3kW、処理速度3m/分の条件の下、コロナ処理を施した。その後、フィルムのコロナ処理面に、前記調製した配向層形成用組成物(1)をバーコート法により塗布し、温度80℃の乾燥オーブン中で1分間加熱乾燥した。得られた被膜に対し、ワイヤーグリッド(UIS-27132##、ウシオ電機株式会社製)を透過させて、波長365nmでの積算光量が100mJ/cm2となるように調整した紫外線を照射して、厚さ100nmの配向層を得た。その後、得られた配向層に、前記調製した直線偏光層形成用組成物をバーコート法により塗布し、被膜を温度120℃の乾燥オーブン中で1分間加熱乾燥して室温まで冷却した。波長365nmでの積算光量が1200mJ/cm2となるように調整した紫外線をこれに照射し、厚さ2.0μmの直線偏光層12を形成した。形成した直線偏光層上に、前記調製したオーバーコート層形成用組成物を、乾燥後の厚さが1.0μmとなるよう、バーコート法により塗布し、温度80℃で3分間乾燥した。かかる手順で、保護層11(厚さ25μm)、直線偏光層12(厚さ2.0μm)、及びオーバーコート層13(厚さ1.0μm)をこの順に備える偏光層10を製造した。 Preparation of Laminate A triacetyl cellol (TAC) film (KC2UA, manufactured by Konica Minolta Co., Ltd., thickness 25 μm) is used as the
<製造例2>
(粘接着剤層20用粘着剤の製造)
アクリル酸ブチル70部、アクリル酸メチル20部、アクリル酸2.0部、およびラジカル重合開始剤(2,2’-アゾビスイソブチロニトリル)0.2部を、窒素雰囲気下で撹拌しながら55℃で反応させることによりアクリル樹脂を得た。その後、該アクリル樹脂100部、架橋剤(東ソー株式会社製「コロネートL」)1.0部、シランカップリング剤(信越化学工業株式会社製「X-12-981」)0.5部を混合し、固形分濃度が10%になるように酢酸エチルを添加して、粘着剤組成物を得た。得られた粘着剤組成物を離型処理されたポリエチレンテレフタレート(PET)フィルム(厚さ38μm)の離型処理面に、アプリケータを利用して乾燥後の厚さが5μmになるように塗布した。塗布層を100℃で1分間乾燥して、PETフィルム付き粘接着剤層20用粘着剤層を得た。
その後、この粘着剤層に、離型処理された別のポリエチレンテレフタレート(PET)フィルム(厚さ38μm)を貼合し、温度23℃、相対湿度50%RHの条件で7日間養生した。粘接着剤層20用粘着剤層は0.7MPaの弾性率(貯蔵弾性率)を有していた。
基材であるPETフィルムは、円偏光板を製造する過程で適宜剥離した。 <Manufacturing example 2>
(Manufacturing of Adhesive for Adhesive Layer 20)
While stirring 70 parts of butyl acrylate, 20 parts of methyl acrylate, 2.0 parts of acrylate, and 0.2 part of radical polymerization initiator (2,2'-azobisisobutyronitrile) in a nitrogen atmosphere. Acrylic resin was obtained by reacting at 55 ° C. Then, 100 parts of the acrylic resin, 1.0 part of the cross-linking agent (“Coronate L” manufactured by Tosoh Corporation), and 0.5 part of the silane coupling agent (“X-12-981” manufactured by Shin-Etsu Chemical Co., Ltd.) are mixed. Then, ethyl acetate was added so that the solid content concentration became 10%, and a pressure-sensitive adhesive composition was obtained. The obtained pressure-sensitive adhesive composition was applied to the release-treated surface of a polyethylene terephthalate (PET) film (thickness 38 μm) that had been released-treated so that the thickness after drying was 5 μm using an applicator. .. The coated layer was dried at 100 ° C. for 1 minute to obtain a pressure-sensitive adhesive layer for the pressure-sensitive adhesive layer 20 with a PET film.
Then, another release-treated polyethylene terephthalate (PET) film (thickness 38 μm) was attached to this pressure-sensitive adhesive layer, and cured under the conditions of a temperature of 23 ° C. and a relative humidity of 50% RH for 7 days. The pressure-sensitive adhesive layer for the pressure-sensitive adhesive layer 20 had an elastic modulus (storage elastic modulus) of 0.7 MPa.
The PET film as the base material was appropriately peeled off in the process of manufacturing the circularly polarizing plate.
(粘接着剤層20用粘着剤の製造)
アクリル酸ブチル70部、アクリル酸メチル20部、アクリル酸2.0部、およびラジカル重合開始剤(2,2’-アゾビスイソブチロニトリル)0.2部を、窒素雰囲気下で撹拌しながら55℃で反応させることによりアクリル樹脂を得た。その後、該アクリル樹脂100部、架橋剤(東ソー株式会社製「コロネートL」)1.0部、シランカップリング剤(信越化学工業株式会社製「X-12-981」)0.5部を混合し、固形分濃度が10%になるように酢酸エチルを添加して、粘着剤組成物を得た。得られた粘着剤組成物を離型処理されたポリエチレンテレフタレート(PET)フィルム(厚さ38μm)の離型処理面に、アプリケータを利用して乾燥後の厚さが5μmになるように塗布した。塗布層を100℃で1分間乾燥して、PETフィルム付き粘接着剤層20用粘着剤層を得た。
その後、この粘着剤層に、離型処理された別のポリエチレンテレフタレート(PET)フィルム(厚さ38μm)を貼合し、温度23℃、相対湿度50%RHの条件で7日間養生した。粘接着剤層20用粘着剤層は0.7MPaの弾性率(貯蔵弾性率)を有していた。
基材であるPETフィルムは、円偏光板を製造する過程で適宜剥離した。 <Manufacturing example 2>
(Manufacturing of Adhesive for Adhesive Layer 20)
While stirring 70 parts of butyl acrylate, 20 parts of methyl acrylate, 2.0 parts of acrylate, and 0.2 part of radical polymerization initiator (2,2'-azobisisobutyronitrile) in a nitrogen atmosphere. Acrylic resin was obtained by reacting at 55 ° C. Then, 100 parts of the acrylic resin, 1.0 part of the cross-linking agent (“Coronate L” manufactured by Tosoh Corporation), and 0.5 part of the silane coupling agent (“X-12-981” manufactured by Shin-Etsu Chemical Co., Ltd.) are mixed. Then, ethyl acetate was added so that the solid content concentration became 10%, and a pressure-sensitive adhesive composition was obtained. The obtained pressure-sensitive adhesive composition was applied to the release-treated surface of a polyethylene terephthalate (PET) film (thickness 38 μm) that had been released-treated so that the thickness after drying was 5 μm using an applicator. .. The coated layer was dried at 100 ° C. for 1 minute to obtain a pressure-sensitive adhesive layer for the pressure-
Then, another release-treated polyethylene terephthalate (PET) film (thickness 38 μm) was attached to this pressure-sensitive adhesive layer, and cured under the conditions of a temperature of 23 ° C. and a relative humidity of 50% RH for 7 days. The pressure-sensitive adhesive layer for the pressure-
The PET film as the base material was appropriately peeled off in the process of manufacturing the circularly polarizing plate.
<製造例3>
(位相差層30の製造)
λ/4位相差層31形成用組成物の調製
λ/4位相差層31を形成するためのλ/4位相差層31形成用組成物は、以下に示す各成分を混合し、得られた混合物を80℃で1時間撹拌することにより調製した。 <Manufacturing example 3>
(Manufacturing of retardation layer 30)
Preparation of composition for forming λ / 4retardation layer 31 The composition for forming λ / 4 retardation layer 31 for forming λ / 4 retardation layer 31 was obtained by mixing each of the following components. The mixture was prepared by stirring at 80 ° C. for 1 hour.
(位相差層30の製造)
λ/4位相差層31形成用組成物の調製
λ/4位相差層31を形成するためのλ/4位相差層31形成用組成物は、以下に示す各成分を混合し、得られた混合物を80℃で1時間撹拌することにより調製した。 <Manufacturing example 3>
(Manufacturing of retardation layer 30)
Preparation of composition for forming λ / 4
・下記の構造式で表される化合物:80部
-Compound represented by the following structural formula: 80 parts
・下記の構造式で表される化合物:20部
-Compound represented by the following structural formula: 20 parts
・重合開始剤(Irgacure369、BASF社製):6部・レベリング剤(BYK-361N、ポリアクリレート化合物、BYK社製):0.1部・溶剤(シクロペンタノン):400部
-Polymerization initiator (Irgacure 369, manufactured by BASF): 6 parts-Leveling agent (BYK-361N, polyacrylate compound, manufactured by BYK): 0.1 part-Solvent (cyclopentanone): 400 parts
λ/4位相差層31の作製
ポリエチレンテレフタレート(PET)フィルム(厚さ100μm)の基材上に、前記配向層形成用組成物(1)をバーコート法により塗布し、温度80℃の乾燥オーブン中で1分間加熱乾燥した。得られた塗膜に偏光UV照射処理を施して配向層を形成した。偏光UV処理は、UV照射装置(SPOT CURE SP-7、ウシオ電機株式会社製)を用いて、波長365nmでの積算光量が100mJ/cm2となる条件で行った。また、偏光UVの偏光方向は直線偏光層の吸収軸に対して45°となるように行った。 Preparation of λ / 4Phase Difference Layer 31 The composition for forming an alignment layer (1) is applied onto a base material of a polyethylene terephthalate (PET) film (thickness 100 μm) by a bar coat method, and a drying oven at a temperature of 80 ° C. is applied. It was heated and dried for 1 minute. The obtained coating film was subjected to polarized UV irradiation treatment to form an alignment layer. The polarized UV treatment was carried out using a UV irradiation device (SPOT CURE SP-7, manufactured by Ushio, Inc.) under the condition that the integrated light amount at a wavelength of 365 nm was 100 mJ / cm 2. Further, the polarization direction of the polarized UV was set to 45 ° with respect to the absorption axis of the linearly polarized light layer.
ポリエチレンテレフタレート(PET)フィルム(厚さ100μm)の基材上に、前記配向層形成用組成物(1)をバーコート法により塗布し、温度80℃の乾燥オーブン中で1分間加熱乾燥した。得られた塗膜に偏光UV照射処理を施して配向層を形成した。偏光UV処理は、UV照射装置(SPOT CURE SP-7、ウシオ電機株式会社製)を用いて、波長365nmでの積算光量が100mJ/cm2となる条件で行った。また、偏光UVの偏光方向は直線偏光層の吸収軸に対して45°となるように行った。 Preparation of λ / 4
次に、形成した配向層上に、前記λ/4位相差層形成用組成物をバーコート法により塗布し、温度120℃の乾燥オーブン中で1分間加熱乾燥した後、室温まで冷却した。得られた塗膜に、波長365nmでの積算光量が1000mJ/cm2となるように調整した紫外線を照射し、厚さ2.0μmのλ/4位相差層を形成して、PETフィルム付きλ/4位相差層31を得た。このλ/4位相差層は、逆波長分散性を示した。
Next, the composition for forming a λ / 4 retardation layer was applied onto the formed alignment layer by a bar coating method, heated and dried in a drying oven at a temperature of 120 ° C. for 1 minute, and then cooled to room temperature. The obtained coating film was irradiated with ultraviolet rays adjusted so that the integrated light amount at a wavelength of 365 nm was 1000 mJ / cm 2 , to form a λ / 4 retardation layer having a thickness of 2.0 μm, and λ with a PET film was formed. A / 4 retardation layer 31 was obtained. This λ / 4 retardation layer showed anti-wavelength dispersibility.
ポジティブC層33の作製
2-フェノキシエチルアクリレートと、テトラヒドロフルフリルアクリレートと、ジペンタエリスリトールトリアクリレートと、ビス(2-ビニルオキシエチル)エーテルとを1:1:4:5の割合で混合し、重合開始剤としてLUCIRIN TPOを4%の割合で添加した配向層形成用組成物(2)を調製した。 Preparation ofPositive C Layer 33 2-Phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, dipentaerythritol triacrylate, and bis (2-vinyloxyethyl) ether were mixed at a ratio of 1: 1: 4: 5. A composition (2) for forming an orientation layer was prepared by adding LUCIRIN TPO as a polymerization initiator at a ratio of 4%.
2-フェノキシエチルアクリレートと、テトラヒドロフルフリルアクリレートと、ジペンタエリスリトールトリアクリレートと、ビス(2-ビニルオキシエチル)エーテルとを1:1:4:5の割合で混合し、重合開始剤としてLUCIRIN TPOを4%の割合で添加した配向層形成用組成物(2)を調製した。 Preparation of
ポジティブC層形成用組成物として光重合性ネマチック液晶化合物(メルク社製,RMM28B)と溶媒とを、固形分が1~1.5gとなるように調製して作製した。溶媒は、メチルエチルケトン(MEK)と、メチルイソブチルケトン(MIBK)と、シクロヘキサノン(CHN)とを、質量比(MEK:MIBK:CHN)で35:30:35の割合で 混合させた混合溶媒を用いた。
As a composition for forming a positive C layer, a photopolymerizable nematic liquid crystal compound (manufactured by Merck & Co., RMM28B) and a solvent were prepared so as to have a solid content of 1 to 1.5 g. As the solvent, a mixed solvent was used in which methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), and cyclohexanone (CHN) were mixed at a mass ratio (MEK: MIBK: CHN) of 35:30:35. ..
厚み38μmのポリエチレンテレフタレート(PET)フィルムを基材として準備した。基材の片面に配向層形成用組成物(2)を膜厚3μmになるように塗布し、200mJ/cm2の紫外線を照射して、配向層を作製した。
A polyethylene terephthalate (PET) film having a thickness of 38 μm was prepared as a substrate. The composition for forming an alignment layer (2) was applied to one side of the substrate so as to have a film thickness of 3 μm, and the alignment layer was prepared by irradiating with ultraviolet rays of 200 mJ / cm 2.
前記配向層上に、ポジティブC層形成用組成物を、ダイコーティングにより塗工した。
塗工量は4~5g(wet)であった。乾燥温度を75℃、乾燥時間を120秒間として、塗膜を乾燥させた。その後、塗膜に紫外線(UV)照射して、重合性液晶化合物を重合させた。得られた塗膜の厚みをレーザー顕微鏡(LEXT、オリンパス株式会社製)で測定したところ、配向層との合計で4μmであった。 A composition for forming a positive C layer was applied onto the alignment layer by die coating.
The coating amount was 4 to 5 g (wet). The coating film was dried at a drying temperature of 75 ° C. and a drying time of 120 seconds. Then, the coating film was irradiated with ultraviolet rays (UV) to polymerize the polymerizable liquid crystal compound. The thickness of the obtained coating film was measured with a laser microscope (LEXT, manufactured by Olympus Corporation) and found to be 4 μm in total with the alignment layer.
塗工量は4~5g(wet)であった。乾燥温度を75℃、乾燥時間を120秒間として、塗膜を乾燥させた。その後、塗膜に紫外線(UV)照射して、重合性液晶化合物を重合させた。得られた塗膜の厚みをレーザー顕微鏡(LEXT、オリンパス株式会社製)で測定したところ、配向層との合計で4μmであった。 A composition for forming a positive C layer was applied onto the alignment layer by die coating.
The coating amount was 4 to 5 g (wet). The coating film was dried at a drying temperature of 75 ° C. and a drying time of 120 seconds. Then, the coating film was irradiated with ultraviolet rays (UV) to polymerize the polymerizable liquid crystal compound. The thickness of the obtained coating film was measured with a laser microscope (LEXT, manufactured by Olympus Corporation) and found to be 4 μm in total with the alignment layer.
位相差層の貼合
光カチオン硬化性樹脂である3’,4’-エポキシシクロヘキシルメチル3,4-エポキシシクロヘキサンカルボキシレート(商品名:CEL2021P、株式会社ダイセル製)70部、ネオペンチルグリコールジグリシジルエーテル(EX-211、ナガセケムテックス株式会社製)20部、2-エチルヘキシルグリシジルエーテル(EX-121、ナガセケムテックス株式会社製)10部、光カチオン重合開始剤(CPI-100、サンアプロ株式会社製)2.25部、光カチオン重合増感剤を1,4-ジエトキシナフタレン2部の配合比で混合した後、脱気して、光硬化型接着剤である位相差層貼合層用接着剤を調製した。光カチオン重合開始剤は50%炭酸プロピレン溶液として混合した。 Laminating of retardation layer 70 parts of 3', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (trade name: CEL2021P, manufactured by Daicel Co., Ltd.), which is a photocationic curable resin, neopentyl glycol diglycidyl ether (EX-211, manufactured by Nagase ChemteX Corporation) 20 parts, 2-ethylhexyl glycidyl ether (EX-121, manufactured by Nagase ChemteX Co., Ltd.) 10 parts, photocationic polymerization initiator (CPI-100, manufactured by Sun Appro Co., Ltd.) 2.25 parts, a photocationic polymerization sensitizer is mixed in a blending ratio of 1,4-diethoxynaphthalene in a blending ratio of 1,4-diethoxynaphthalene, and then degassed. Was prepared. The photocationic polymerization initiator was mixed as a 50% propylene carbonate solution.
光カチオン硬化性樹脂である3’,4’-エポキシシクロヘキシルメチル3,4-エポキシシクロヘキサンカルボキシレート(商品名:CEL2021P、株式会社ダイセル製)70部、ネオペンチルグリコールジグリシジルエーテル(EX-211、ナガセケムテックス株式会社製)20部、2-エチルヘキシルグリシジルエーテル(EX-121、ナガセケムテックス株式会社製)10部、光カチオン重合開始剤(CPI-100、サンアプロ株式会社製)2.25部、光カチオン重合増感剤を1,4-ジエトキシナフタレン2部の配合比で混合した後、脱気して、光硬化型接着剤である位相差層貼合層用接着剤を調製した。光カチオン重合開始剤は50%炭酸プロピレン溶液として混合した。 Laminating of retardation layer 70 parts of 3', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (trade name: CEL2021P, manufactured by Daicel Co., Ltd.), which is a photocationic curable resin, neopentyl glycol diglycidyl ether (EX-211, manufactured by Nagase ChemteX Corporation) 20 parts, 2-ethylhexyl glycidyl ether (EX-121, manufactured by Nagase ChemteX Co., Ltd.) 10 parts, photocationic polymerization initiator (CPI-100, manufactured by Sun Appro Co., Ltd.) 2.25 parts, a photocationic polymerization sensitizer is mixed in a blending ratio of 1,4-diethoxynaphthalene in a blending ratio of 1,4-diethoxynaphthalene, and then degassed. Was prepared. The photocationic polymerization initiator was mixed as a 50% propylene carbonate solution.
前記PETフィルム付きλ/4位相差層31のλ/4位相差層側と、PETフィルム付きポジティブC層33のポジティブC層側とに、出力0.3kW、処理速度3m/分の条件下、コロナ処理を一度行った。λ/4位相差層31とポジティブC層33との間に、厚さが1.5μmとなるように上記位相差層貼合層用接着剤を塗布して、ニップロールで貼合した。貼合した位相差層30のポジティブC層33のPETフィルム基材側から、波長365nmでの積算光量が300mJ/cm2となるように調整した紫外線を照射し、位相差層貼合層を紫外線硬化させた。かかる手順で、λ/4位相差層31、位相差層貼合層32、及びポジティブC層33をこの順に備える位相差層30を製造した。硬化した位相差層貼合層は2.4GPaの弾性率(圧縮弾性率)を有していた。基材であるPETフィルムは、円偏光板を製造する過程で適宜剥離した。
Under the conditions of an output of 0.3 kW and a processing speed of 3 m / min on the λ / 4 retardation layer side of the λ / 4 retardation layer 31 with a PET film and the positive C layer side of the positive C layer 33 with a PET film. Corona treatment was performed once. The adhesive for the retardation layer bonding layer was applied between the λ / 4 retardation layer 31 and the positive C layer 33 so as to have a thickness of 1.5 μm, and the adhesive was bonded by a nip roll. Ultraviolet rays adjusted so that the integrated light amount at a wavelength of 365 nm is 300 mJ / cm 2 is irradiated from the PET film base material side of the positive C layer 33 of the laminated retardation layer 30, and the laminated layer of the retardation layer is exposed to ultraviolet rays. It was cured. By this procedure, a retardation layer 30 including a λ / 4 retardation layer 31, a retardation layer bonding layer 32, and a positive C layer 33 was manufactured in this order. The cured retardation layer bonded layer had an elastic modulus (compressive elastic modulus) of 2.4 GPa. The PET film as the base material was appropriately peeled off in the process of manufacturing the circularly polarizing plate.
<実施例1>
図2に示す円偏光板200の製造
1.製造例1で得た偏光層10のオーバーコート層13側の面にコロナ処理(条件:出力.0.3kW、処理速度.3m/分)を行い、製造例2で得た粘接着剤層20用粘着剤層の面にコロナ処理を行い、コロナ処理面同士で貼合した。
2.製造例3で得た位相差層30のλ/4位相差層31側の面にコロナ処理を行い、これと、シクロオレフィンポリマー(COP)フィルム(厚さ23μm)とを、製造例3で得た位相差層貼合層用接着剤(厚さ1~2μm)を介して、ニップロールで積層した。その後、COPフィルム側から、波長365nmでの積算光量が300mJ/cm2となるように調整した紫外線を照射し、厚さ1.5μmの第1補強層41を得た。COPフィルムは、第1補強層41を形成後、剥離して除去した。
3.手順1で得た貼合体の粘接着剤の面にコロナ処理を行い、手順2で形成した第1補強層41の面にコロナ処理を行い、コロナ処理面同士で貼合して、位相差層30の上部に第1補強層41を有する円偏光板200を得た。 <Example 1>
Manufacture of circularlypolarizing plate 200 shown in FIG. 2. The surface of the polarizing layer 10 obtained in Production Example 1 on the overcoat layer 13 side was subjected to corona treatment (conditions: output .0.3 kW, processing speed .3 m / min), and the adhesive layer obtained in Production Example 2 was applied. The surfaces of the pressure-sensitive adhesive layer for 20 were subjected to corona treatment, and the surfaces treated with corona were bonded to each other.
2. 2. The surface of theretardation layer 30 obtained in Production Example 3 on the λ / 4 retardation layer 31 side was subjected to corona treatment, and this and a cycloolefin polymer (COP) film (thickness 23 μm) were obtained in Production Example 3. The film was laminated with a nip roll via an adhesive for a laminated layer (thickness 1 to 2 μm). Then, from the COP film side, ultraviolet rays adjusted so that the integrated light amount at a wavelength of 365 nm was 300 mJ / cm 2 was irradiated to obtain a first reinforcing layer 41 having a thickness of 1.5 μm. The COP film was removed by peeling after forming the first reinforcing layer 41.
3. 3. The surface of the adhesive adhesive of the bonded body obtained in step 1 is subjected to corona treatment, the surface of the first reinforcinglayer 41 formed in step 2 is subjected to corona treatment, and the surfaces treated with corona are bonded to each other, resulting in a phase difference. A circularly polarizing plate 200 having a first reinforcing layer 41 on the upper part of the layer 30 was obtained.
図2に示す円偏光板200の製造
1.製造例1で得た偏光層10のオーバーコート層13側の面にコロナ処理(条件:出力.0.3kW、処理速度.3m/分)を行い、製造例2で得た粘接着剤層20用粘着剤層の面にコロナ処理を行い、コロナ処理面同士で貼合した。
2.製造例3で得た位相差層30のλ/4位相差層31側の面にコロナ処理を行い、これと、シクロオレフィンポリマー(COP)フィルム(厚さ23μm)とを、製造例3で得た位相差層貼合層用接着剤(厚さ1~2μm)を介して、ニップロールで積層した。その後、COPフィルム側から、波長365nmでの積算光量が300mJ/cm2となるように調整した紫外線を照射し、厚さ1.5μmの第1補強層41を得た。COPフィルムは、第1補強層41を形成後、剥離して除去した。
3.手順1で得た貼合体の粘接着剤の面にコロナ処理を行い、手順2で形成した第1補強層41の面にコロナ処理を行い、コロナ処理面同士で貼合して、位相差層30の上部に第1補強層41を有する円偏光板200を得た。 <Example 1>
Manufacture of circularly
2. 2. The surface of the
3. 3. The surface of the adhesive adhesive of the bonded body obtained in step 1 is subjected to corona treatment, the surface of the first reinforcing
<実施例2>
図3に示す円偏光板300の製造
1.製造例1で得た偏光層10のオーバーコート層13側の面にコロナ処理を行い、製造例2で得た粘接着剤層20用粘着剤層の面にコロナ処理を行い、コロナ処理面同士で貼合した。 <Example 2>
Manufacture of circularlypolarizing plate 300 shown in FIG. 3. The surface of the polarizing layer 10 obtained in Production Example 1 on the overcoat layer 13 side was subjected to corona treatment, and the surface of the pressure-sensitive adhesive layer for the adhesive layer 20 obtained in Production Example 2 was subjected to corona treatment. It was pasted together.
図3に示す円偏光板300の製造
1.製造例1で得た偏光層10のオーバーコート層13側の面にコロナ処理を行い、製造例2で得た粘接着剤層20用粘着剤層の面にコロナ処理を行い、コロナ処理面同士で貼合した。 <Example 2>
Manufacture of circularly
2.得られた貼合体の粘接着剤層20用粘着剤層の面にコロナ処理を行い、製造例3で得た位相差層30のλ/4位相差層側の面にコロナ処理を行い、コロナ処理面同士で貼合した。
3.得られた貼合体のポジティブC層側の面にコロナ処理を行ったものと、別途用意したCOPフィルム(厚さ23μm)とを、製造例3で得た位相差層貼合層用接着剤(厚さ1.5μm)を介して、ニップロールで積層した。その後、COPフィルム側から、波長365nmでの積算光量が300mJ/cm2となるように調整した紫外線を照射し、COPフィルムを除去して、位相差層の下部に第2補強層42を有する円偏光板300を得た。 2. 2. The surface of the pressure-sensitive adhesive layer for the pressure-sensitive adhesive layer 20 of the obtained bonded body was subjected to corona treatment, and the surface of the retardation layer 30 obtained in Production Example 3 on the λ / 4 retardation layer side was subjected to corona treatment. The corona-treated surfaces were pasted together.
3. 3. A corona-treated surface of the obtained bonded body on the positive C layer side and a separately prepared COP film (thickness 23 μm) were used as an adhesive for the retardation layer bonded layer obtained in Production Example 3. Laminated with a nip roll via a thickness of 1.5 μm). Then, from the COP film side, ultraviolet rays adjusted so that the integrated light amount at a wavelength of 365 nm is 300 mJ / cm 2 is irradiated to remove the COP film, and a circle having a second reinforcinglayer 42 under the retardation layer. A polarizing plate 300 was obtained.
3.得られた貼合体のポジティブC層側の面にコロナ処理を行ったものと、別途用意したCOPフィルム(厚さ23μm)とを、製造例3で得た位相差層貼合層用接着剤(厚さ1.5μm)を介して、ニップロールで積層した。その後、COPフィルム側から、波長365nmでの積算光量が300mJ/cm2となるように調整した紫外線を照射し、COPフィルムを除去して、位相差層の下部に第2補強層42を有する円偏光板300を得た。 2. 2. The surface of the pressure-sensitive adhesive layer for the pressure-
3. 3. A corona-treated surface of the obtained bonded body on the positive C layer side and a separately prepared COP film (thickness 23 μm) were used as an adhesive for the retardation layer bonded layer obtained in Production Example 3. Laminated with a nip roll via a thickness of 1.5 μm). Then, from the COP film side, ultraviolet rays adjusted so that the integrated light amount at a wavelength of 365 nm is 300 mJ / cm 2 is irradiated to remove the COP film, and a circle having a second reinforcing
<実施例3>
図4に示す円偏光板400の製造
実施例1で得た円偏光板200のポジティブC層側の面にコロナ処理を行った。 次に、これと、別途用意したCOPフィルム(厚さ23μm)とを、製造例3で得た位相差層貼合層用接着剤(厚さ1.5μm)を介して、ニップロールで積層した。その後、COPフィルム側から、波長365nmでの積算光量が300mJ/cm2となるように調整した紫外線を照射し、COPフィルムを除去して、位相差層30の上部に第1補強層41を、位相差層30の下部に第2補強層42を有する円偏光板400を得た。 <Example 3>
Manufacture of CircularPolarizing Plate 400 shown in FIG. 4 Corona treatment was performed on the surface of the circularly polarizing plate 200 obtained in Example 1 on the positive C layer side. Next, this and a separately prepared COP film (thickness 23 μm) were laminated by a nip roll via the retardation layer bonding layer adhesive (thickness 1.5 μm) obtained in Production Example 3. After that, the COP film side is irradiated with ultraviolet rays adjusted so that the integrated light amount at a wavelength of 365 nm is 300 mJ / cm 2 , the COP film is removed, and the first reinforcing layer 41 is placed on the upper part of the retardation layer 30. A circularly polarizing plate 400 having a second reinforcing layer 42 under the retardation layer 30 was obtained.
図4に示す円偏光板400の製造
実施例1で得た円偏光板200のポジティブC層側の面にコロナ処理を行った。 次に、これと、別途用意したCOPフィルム(厚さ23μm)とを、製造例3で得た位相差層貼合層用接着剤(厚さ1.5μm)を介して、ニップロールで積層した。その後、COPフィルム側から、波長365nmでの積算光量が300mJ/cm2となるように調整した紫外線を照射し、COPフィルムを除去して、位相差層30の上部に第1補強層41を、位相差層30の下部に第2補強層42を有する円偏光板400を得た。 <Example 3>
Manufacture of Circular
<実施例4>
図1に示す円偏光板100の製造
実施例2の手順1及び2と同様にして円偏光板100を得た。この円偏光板をさらに80℃で1時間養生した。 <Example 4>
Manufacture of CircularPolarizing Plate 100 shown in FIG. 1 Circularly polarizing plate 100 was obtained in the same manner as in steps 1 and 2 of Example 2. This circularly polarizing plate was further cured at 80 ° C. for 1 hour.
図1に示す円偏光板100の製造
実施例2の手順1及び2と同様にして円偏光板100を得た。この円偏光板をさらに80℃で1時間養生した。 <Example 4>
Manufacture of Circular
<比較例1>
製造例3で得たPETフィルム付きλ/4位相差層31のλ/4位相差層側と、PETフィルム付きポジティブC層33のポジティブC層側とに、出力0.3kW、処理速度3m/分の条件下、コロナ処理を行った。λ/4位相差層31とポジティブC層33との間に、製造例2で得た粘接着剤層20用粘着剤層を配置して、両者を貼合した。かかる手順で、λ/4位相差層(厚さ2.0μm)、位相差層貼合層(厚さ5μm)、及びポジティブC層(厚さ450nm)をこの順に備える位相差層を作製した。基材であるPETフィルムは、円偏光板を製造する過程で適宜剥離した。 <Comparative Example 1>
The output of 0.3 kW and the processing speed of 3 m / on the λ / 4 retardation layer side of the λ / 4retardation layer 31 with PET film obtained in Production Example 3 and the positive C layer side of the positive C layer 33 with PET film. Corona treatment was performed under the condition of minutes. The pressure-sensitive adhesive layer for the pressure-sensitive adhesive layer 20 obtained in Production Example 2 was placed between the λ / 4 retardation layer 31 and the positive C layer 33, and both were bonded together. By this procedure, a retardation layer including a λ / 4 retardation layer (thickness 2.0 μm), a retardation layer bonding layer (thickness 5 μm), and a positive C layer (thickness 450 nm) was prepared in this order. The PET film as the base material was appropriately peeled off in the process of manufacturing the circularly polarizing plate.
製造例3で得たPETフィルム付きλ/4位相差層31のλ/4位相差層側と、PETフィルム付きポジティブC層33のポジティブC層側とに、出力0.3kW、処理速度3m/分の条件下、コロナ処理を行った。λ/4位相差層31とポジティブC層33との間に、製造例2で得た粘接着剤層20用粘着剤層を配置して、両者を貼合した。かかる手順で、λ/4位相差層(厚さ2.0μm)、位相差層貼合層(厚さ5μm)、及びポジティブC層(厚さ450nm)をこの順に備える位相差層を作製した。基材であるPETフィルムは、円偏光板を製造する過程で適宜剥離した。 <Comparative Example 1>
The output of 0.3 kW and the processing speed of 3 m / on the λ / 4 retardation layer side of the λ / 4
製造例3で得た位相差層30の代わりに上記位相差層を用いること以外は実施例2の手順1及び2と同様にして、円偏光板を得た。得られた円偏光板の構造は実施例4と同様であるが、位相差層貼合層の弾性率(貯蔵弾性率)が0.0007GPaである点で相違する。
A circularly polarizing plate was obtained in the same manner as in Procedures 1 and 2 of Example 2 except that the above-mentioned retardation layer was used instead of the retardation layer 30 obtained in Production Example 3. The structure of the obtained circularly polarizing plate is the same as that of the fourth embodiment, except that the elastic modulus (storage elastic modulus) of the retarded layer bonded layer is 0.0007 GPa.
<比較例2>
PETフィルムの代わりに、保護層としても使用したTACフィルムを使用すること以外は製造例3と同様にして、TACフィルム上にポジティブC層を形成した。 <Comparative Example 2>
A positive C layer was formed on the TAC film in the same manner as in Production Example 3 except that the TAC film used as the protective layer was used instead of the PET film.
PETフィルムの代わりに、保護層としても使用したTACフィルムを使用すること以外は製造例3と同様にして、TACフィルム上にポジティブC層を形成した。 <Comparative Example 2>
A positive C layer was formed on the TAC film in the same manner as in Production Example 3 except that the TAC film used as the protective layer was used instead of the PET film.
得られたTACフィルム付きポジティブC層を使用すること以外は比較例1と同様にして、円偏光板を得た。これにより、位相差層の下部に補強層としてTACフィルム(厚さ25μm)を有する円偏光板を得た。
A circularly polarizing plate was obtained in the same manner as in Comparative Example 1 except that the obtained positive C layer with a TAC film was used. As a result, a circularly polarizing plate having a TAC film (thickness 25 μm) as a reinforcing layer under the retardation layer was obtained.
<クラックストレインの測定>
各円偏光板を5cm長×10mm幅のサイズに裁断し、サンプルを調製した。UTM (Universal Testing Machine、株式会社島津製作所製「オートグラフAG-X」(製品名))を使用して、調製したサンプルの両端をクリップでつかみ、長さ方向に4mm/分の速度で引張りながら、目視でサンプル表面を観察した。サンプルにクラックが発生した時の伸び率をクラックストレイン(%)として記録した。例えば、実施例1においてクラックが発生したときのサンプルの長さは6.25cmであったので、クラックストレインは、100×(6.25-5)/5=25%と算出される。 <Measurement of crack strain>
Each circularly polarizing plate was cut into a size of 5 cm length × 10 mm width to prepare a sample. Using UTM (Universal Testing Machine, "Autograph AG-X" (product name) manufactured by Shimadzu Corporation), grasp both ends of the prepared sample with clips and pull at a speed of 4 mm / min in the length direction. , The surface of the sample was visually observed. The elongation rate when cracks occurred in the sample was recorded as a crack strain (%). For example, since the length of the sample when the crack occurred in Example 1 was 6.25 cm, the crack strain is calculated as 100 × (6.25-5) / 5 = 25%.
各円偏光板を5cm長×10mm幅のサイズに裁断し、サンプルを調製した。UTM (Universal Testing Machine、株式会社島津製作所製「オートグラフAG-X」(製品名))を使用して、調製したサンプルの両端をクリップでつかみ、長さ方向に4mm/分の速度で引張りながら、目視でサンプル表面を観察した。サンプルにクラックが発生した時の伸び率をクラックストレイン(%)として記録した。例えば、実施例1においてクラックが発生したときのサンプルの長さは6.25cmであったので、クラックストレインは、100×(6.25-5)/5=25%と算出される。 <Measurement of crack strain>
Each circularly polarizing plate was cut into a size of 5 cm length × 10 mm width to prepare a sample. Using UTM (Universal Testing Machine, "Autograph AG-X" (product name) manufactured by Shimadzu Corporation), grasp both ends of the prepared sample with clips and pull at a speed of 4 mm / min in the length direction. , The surface of the sample was visually observed. The elongation rate when cracks occurred in the sample was recorded as a crack strain (%). For example, since the length of the sample when the crack occurred in Example 1 was 6.25 cm, the crack strain is calculated as 100 × (6.25-5) / 5 = 25%.
<動的耐屈曲性試験>
動的屈曲試験は、室温条件下(温度25℃、湿度50%)で行った。実施例及び比較例で製造した円偏光板の保護層上に、片面上にハードコート層(厚さ10μm)を有するポリイミド系高分子樹脂フィルム(前面板、厚さ40μm)を貼合し、ポジティブC層上に、2枚のポリイミドフィルム(背面板、厚さはどちらも38μm、引張弾性率5GPa以上)を二重に貼合して、屈曲試験用積層体を得た。上記フィルムの貼合には、架橋剤の使用量を3.0部に変更すること以外は製造例2と同様にして調製した屈曲試験用粘着剤層(厚さ25μm)を用いた。 <Dynamic bending resistance test>
The dynamic bending test was performed under room temperature conditions (temperature 25 ° C., humidity 50%). A polyimide polymer resin film (front plate, thickness 40 μm) having a hard coat layer (thickness 10 μm) on one side is bonded onto the protective layer of the circularly polarizing plate manufactured in Examples and Comparative Examples, and positive. Two polyimide films (back plate, both thickness 38 μm, tensile elastic modulus 5 GPa or more) were doubly bonded on the C layer to obtain a laminate for bending test. For the bonding of the films, a bending test pressure-sensitive adhesive layer (thickness 25 μm) prepared in the same manner as in Production Example 2 was used except that the amount of the cross-linking agent used was changed to 3.0 parts.
動的屈曲試験は、室温条件下(温度25℃、湿度50%)で行った。実施例及び比較例で製造した円偏光板の保護層上に、片面上にハードコート層(厚さ10μm)を有するポリイミド系高分子樹脂フィルム(前面板、厚さ40μm)を貼合し、ポジティブC層上に、2枚のポリイミドフィルム(背面板、厚さはどちらも38μm、引張弾性率5GPa以上)を二重に貼合して、屈曲試験用積層体を得た。上記フィルムの貼合には、架橋剤の使用量を3.0部に変更すること以外は製造例2と同様にして調製した屈曲試験用粘着剤層(厚さ25μm)を用いた。 <Dynamic bending resistance test>
The dynamic bending test was performed under room temperature conditions (temperature 25 ° C., humidity 50%). A polyimide polymer resin film (front plate, thickness 40 μm) having a hard coat layer (
得られた屈曲試験用積層体を動的屈曲試験機(Science Town社製「STS-VRT-500」(製品名))に平坦な状態(屈曲していない状態)で設置し、前面板層側が内側となるよう(インフォ―ルド方式)を180°屈曲させ、その後、元の平坦な状態に戻した。屈曲半径は、室温条件下では1.0mmとした。
The obtained laminate for bending test was installed in a dynamic bending tester (“STS-VRT-500” (product name) manufactured by Science Town) in a flat state (not bent), and the front plate layer side was It was bent 180 ° so that it was on the inside (infold method), and then returned to its original flat state. The bending radius was 1.0 mm under room temperature conditions.
屈曲させて平坦に戻す操作を1回行ったことを屈曲回数1回と数え、この動作を繰り返し行った。屈曲速度は60rpmとした。屈曲操作で屈曲した領域において最下層の位相差層にクラック(割れ又は破断)が生じたときの屈曲回数を、限界屈曲回数として表1に記録した。
The operation of bending and returning to flatness was counted as one bending, and this operation was repeated. The bending speed was 60 rpm. The number of times of bending when a crack (cracking or breaking) occurred in the retardation layer of the lowermost layer in the region bent by the bending operation was recorded in Table 1 as the limit number of times of bending.
<静的屈曲耐久性試験>
図5は、本発明の円偏光板の静的屈曲耐久性試験(マンドレル屈曲試験)の方法を示す断面図である。まず、上記屈曲試験用積層体を1cm×10cmの試験片に裁断した。試験板51上に裁断した屈曲試験用積層体52を、その前面板側が上側になるように置き、その上に直径3mmの鉄製棒53を置いた(図5(a))。鉄製棒53を挟んで試験板51及び屈曲試験用積層体52を手で180°折り、固定した(図5(b))。その後、折り畳んだ状態の屈曲試験用積層体52を、高温高湿条件下(温度60℃、湿度90%)で載置した。 <Static bending durability test>
FIG. 5 is a cross-sectional view showing a method of a static bending durability test (mandrel bending test) of the circularly polarizing plate of the present invention. First, the laminate for bending test was cut into test pieces of 1 cm × 10 cm. Thebending test laminate 52 cut on the test plate 51 was placed so that the front plate side thereof was on the upper side, and an iron rod 53 having a diameter of 3 mm was placed on the laminated body 52 (FIG. 5A). The test plate 51 and the laminate for bending test 52 were manually folded by 180 ° and fixed with the iron rod 53 sandwiched between them (FIG. 5 (b)). Then, the laminated body 52 for bending test in a folded state was placed under high temperature and high humidity conditions (temperature 60 ° C., humidity 90%).
図5は、本発明の円偏光板の静的屈曲耐久性試験(マンドレル屈曲試験)の方法を示す断面図である。まず、上記屈曲試験用積層体を1cm×10cmの試験片に裁断した。試験板51上に裁断した屈曲試験用積層体52を、その前面板側が上側になるように置き、その上に直径3mmの鉄製棒53を置いた(図5(a))。鉄製棒53を挟んで試験板51及び屈曲試験用積層体52を手で180°折り、固定した(図5(b))。その後、折り畳んだ状態の屈曲試験用積層体52を、高温高湿条件下(温度60℃、湿度90%)で載置した。 <Static bending durability test>
FIG. 5 is a cross-sectional view showing a method of a static bending durability test (mandrel bending test) of the circularly polarizing plate of the present invention. First, the laminate for bending test was cut into test pieces of 1 cm × 10 cm. The
屈曲操作で屈曲した領域において、円偏光板を構成する層のうちで最下層の位相差層にクラックが生じたときを基準に、静的屈曲耐久性を次のように評価した。結果を表1に示す。
The static bending durability was evaluated as follows, based on the time when a crack occurred in the retardation layer of the lowest layer among the layers constituting the circularly polarizing plate in the region bent by the bending operation. The results are shown in Table 1.
A:30日経過した時点でクラックが発生していなかった。
B:30日経過した時点でクラック発生していた。
C:20日経過した時点でクラックが発生していた。
D:10日経過した時点でクラックが発生していた。 A: No cracks occurred after 30 days.
B: A crack had occurred after 30 days had passed.
C: A crack had occurred after 20 days had passed.
D: A crack had occurred after 10 days had passed.
B:30日経過した時点でクラック発生していた。
C:20日経過した時点でクラックが発生していた。
D:10日経過した時点でクラックが発生していた。 A: No cracks occurred after 30 days.
B: A crack had occurred after 30 days had passed.
C: A crack had occurred after 20 days had passed.
D: A crack had occurred after 10 days had passed.
表1より、クラックストレインが高い本発明の円偏光板は、優れた耐屈曲性を有することがわかる。中でも、位相差層の上部、下部に補強層を有する円偏光板は、特に優れた耐屈曲性を有していた。
From Table 1, it can be seen that the circularly polarizing plate of the present invention having a high crack strain has excellent bending resistance. Among them, the circularly polarizing plate having the reinforcing layers at the upper and lower portions of the retardation layer had particularly excellent bending resistance.
10…偏光層、
11…保護層、
12…直線偏光層、
13…オーバーコート層、
20…粘接着剤層、
30…位相差層、
31…λ/4位相差層、
32…位相差層貼合層、
33…ポジティブC層、
41…第1補強層、
42…第2補強層、
51…試験板、
52…屈曲試験用積層体、
53…鉄製棒、
100、200、300、400…円偏光板。 10 ... Polarizing layer,
11 ... Protective layer,
12 ... Linearly polarizing layer,
13 ... Overcoat layer,
20 ... Adhesive layer,
30 ... Phase difference layer,
31 ... λ / 4 phase difference layer,
32 ... Phase difference layer bonded layer,
33 ... Positive C layer,
41 ... First reinforcing layer,
42 ... Second reinforcing layer,
51 ... Test board,
52 ... Laminated body for bending test,
53 ... Iron rod,
100, 200, 300, 400 ... Circularly polarizing plate.
11…保護層、
12…直線偏光層、
13…オーバーコート層、
20…粘接着剤層、
30…位相差層、
31…λ/4位相差層、
32…位相差層貼合層、
33…ポジティブC層、
41…第1補強層、
42…第2補強層、
51…試験板、
52…屈曲試験用積層体、
53…鉄製棒、
100、200、300、400…円偏光板。 10 ... Polarizing layer,
11 ... Protective layer,
12 ... Linearly polarizing layer,
13 ... Overcoat layer,
20 ... Adhesive layer,
30 ... Phase difference layer,
31 ... λ / 4 phase difference layer,
32 ... Phase difference layer bonded layer,
33 ... Positive C layer,
41 ... First reinforcing layer,
42 ... Second reinforcing layer,
51 ... Test board,
52 ... Laminated body for bending test,
53 ... Iron rod,
100, 200, 300, 400 ... Circularly polarizing plate.
Claims (11)
- 直線偏光層を含んで成る偏光層と、液晶塗布型位相差層を含んで成る位相差層とを、有する円偏光板であって、
該円偏光板は、15%以上のクラックストレインを有し、
該クラックストレインは、5cm長×10mm幅の円偏光板の両端を長さ方向に4mm/分の速度で引張り、該円偏光板にクラックが発生した時の伸び率(%)である、
円偏光板。 A circularly polarizing plate having a polarizing layer including a linear polarizing layer and a retardation layer including a liquid crystal coating type retardation layer.
The circularly polarizing plate has a crack strain of 15% or more.
The crack strain is the elongation rate (%) when cracks occur in the circularly polarizing plate by pulling both ends of a circularly polarizing plate having a length of 5 cm and a width of 10 mm at a speed of 4 mm / min in the length direction.
Circularly polarized light. - 前記位相差層は、λ/4位相差層、位相差層貼合層、及びポジティブC層を含んで成る、請求項1に記載の円偏光板。 The circularly polarizing plate according to claim 1, wherein the retardation layer includes a λ / 4 retardation layer, a retardation layer bonded layer, and a positive C layer.
- 前記位相差層貼合層は、1GPa以上の弾性率を有する、請求項2に記載の円偏光板。 The circularly polarizing plate according to claim 2, wherein the retardation layer bonded layer has an elastic modulus of 1 GPa or more.
- 前記位相差層貼合層は、1~5μmの厚さを有する、請求項2又は3に記載の円偏光板。 The circularly polarizing plate according to claim 2 or 3, wherein the retarded layer bonded layer has a thickness of 1 to 5 μm.
- 前記ポジティブC層は、液晶塗布型の位相差層である、請求項2~4のいずれか一項に記載の円偏光板。 The circularly polarizing plate according to any one of claims 2 to 4, wherein the positive C layer is a liquid crystal coating type retardation layer.
- 前記位相差層が、その少なくとも一方の面に補強層を有する、請求項1~5のいずれか一項に記載の円偏光板。 The circularly polarizing plate according to any one of claims 1 to 5, wherein the retardation layer has a reinforcing layer on at least one surface thereof.
- 前記補強層が、前記位相差層の上部に形成されている、請求項6に記載の円偏光板。 The circularly polarizing plate according to claim 6, wherein the reinforcing layer is formed on the upper portion of the retardation layer.
- 前記補強層が、前記位相差層の下部に形成されている、請求項6に記載の円偏光板。 The circularly polarizing plate according to claim 6, wherein the reinforcing layer is formed below the retardation layer.
- 前記補強層が、前記位相差層の上部及び下部に形成されている、請求項6に記載の円偏光板。 The circularly polarizing plate according to claim 6, wherein the reinforcing layer is formed on the upper portion and the lower portion of the retardation layer.
- 5~50μmの厚さを有する、請求項1~9のいずれか一項に記載の円偏光板。 The circularly polarizing plate according to any one of claims 1 to 9, which has a thickness of 5 to 50 μm.
- 偏光層を内側にして、屈曲半径1mmにて180°屈曲させては伸ばす操作を30万回繰り返し行った場合に、位相差層に割れ又は破断が生じない耐屈曲性を有する、請求項1~10のいずれか一項に記載の円偏光板。 1. 10. The circularly polarizing plate according to any one of 10.
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- 2021-04-26 TW TW110114845A patent/TW202142900A/en unknown
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WO2016158300A1 (en) * | 2015-03-31 | 2016-10-06 | 富士フイルム株式会社 | Circular polarizing plate and bendable display device |
KR20170013143A (en) * | 2015-07-27 | 2017-02-06 | 삼성전자주식회사 | Optical film and display device |
JP2017102443A (en) * | 2015-11-20 | 2017-06-08 | 日東電工株式会社 | Optical laminated body and organic electroluminescence display device using same |
JP2019091023A (en) * | 2017-11-10 | 2019-06-13 | 住友化学株式会社 | Circularly polarizing plate |
JP2019207391A (en) * | 2018-05-25 | 2019-12-05 | 住友化学株式会社 | Manufacturing method for optical laminate |
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WO2024024119A1 (en) * | 2022-07-29 | 2024-02-01 | 住友化学株式会社 | Optical laminate |
Also Published As
Publication number | Publication date |
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TW202142900A (en) | 2021-11-16 |
CN115516348A (en) | 2022-12-23 |
KR20230006806A (en) | 2023-01-11 |
JP2021179599A (en) | 2021-11-18 |
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