CN114930209A - Polarizing plate and display device - Google Patents
Polarizing plate and display device Download PDFInfo
- Publication number
- CN114930209A CN114930209A CN202180007932.7A CN202180007932A CN114930209A CN 114930209 A CN114930209 A CN 114930209A CN 202180007932 A CN202180007932 A CN 202180007932A CN 114930209 A CN114930209 A CN 114930209A
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- China
- Prior art keywords
- film
- optical film
- polarizing plate
- resin
- polarizer
- Prior art date
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- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
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- HTEAGOMAXMOFFS-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C HTEAGOMAXMOFFS-UHFFFAOYSA-N 0.000 description 1
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- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- 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
- 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
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Nonlinear Science (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Mathematical Physics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Polarising Elements (AREA)
Abstract
The invention provides a polarizing plate and a display device, wherein the polarizing plate at least comprises a polarizer and an optical film, the polarizer and the optical film are directly laminated or laminated through an adhesive, the thickness of the optical film is 0.1-10 mu m, the tensile strength is 50-1000 MPa, and the absolute value of the thickness direction retardation Rth is less than 25 nm.
Description
Technical Field
The invention relates to a polarizing film and a display device.
Background
The optical film has various uses, and is used as one of them for a polarizing plate.
Polarizing plates are used as components of liquid crystal display devices (LCDs), organic electroluminescence (organic EL) displays (OLEDs), and the like, and play an important role in their display performance. A general polarizing plate has a structure in which an optical film is bonded to one surface or both surfaces of a polarizer in which a dichroic dye such as an iodine complex is adsorbed and oriented to a polyvinyl alcohol (PVA) resin.
In recent years, display devices have been increased in size, thickness, and flexibility, and accordingly, polarizing plates have been required to have functions and thicknesses different from those of conventional polarizing plates.
In order to make the polarizing plate thin, it is necessary to make the optical film constituting the polarizing plate thin. For example, patent document 1 describes the following method: a polarizing plate having a coating film with a thickness of less than 10 μm attached thereto is produced by providing a coating film on a dummy support, attaching a polarizer to the coating film, and then peeling the dummy support from the coating film.
Such a thin polarizing plate has low durability and tends to be easily broken at high temperature or when thermal shock is applied.
Prior art documents
Patent literature
Patent document 1: international publication No. 2014/199934
Disclosure of Invention
Technical problem to be solved by the invention
In view of the above problems, an object of the present invention is to provide a polarizing plate and a display device, the polarizing plate having excellent crack resistance, particularly at high temperatures or when thermal shock is applied, and having excellent display performance when mounted on a display device.
Means for solving the technical problem
The present inventors have found that the above-mentioned problems can be solved by controlling the tensile strength and the retardation in the thickness direction of the thin optical film.
Specifically, it was found that the above problems can be solved by the following method.
[1]
A polarizing plate comprising at least a polarizer and an optical film,
the polarizer is laminated directly or via an adhesive to the optical film,
the optical film has a film thickness of 0.1 to 10 μm, a tensile strength of 50 to 1000MPa, and an absolute value of retardation Rth in the thickness direction of 25nm or less.
[2]
The polarizing plate according to [1], wherein a moisture absorption rate of a base material constituting the optical film is 2.0 mass% or less.
[3]
The polarizing plate according to [1] or [2], wherein the optical film contains an additive having any one of properties I to III described below.
The elastic modulus of the additive is higher than that of the matrix material
II the additive has a higher elongation at break than the matrix material
III the additive has a higher breaking strength than the matrix material
[4]
A display device comprising the polarizing plate according to any one of [1] to [3], wherein an adhesive layer is laminated on a surface of the optical film opposite to the polarizer, and a substrate is further laminated thereon,
the elastic modulus of the bonding layer is 0.01 to 100MPa,
the elastic modulus of the substrate is 6GPa to 100 GPa.
[5]
A display device comprising the polarizing plate according to any one of [1] to [3 ].
Effects of the invention
According to the present invention, it is possible to provide a polarizing plate having excellent crack resistance even under an environment of high temperature or thermal shock and excellent display performance when mounted on a display device, and a display device.
Detailed Description
The present invention will be described in detail. The following description of the constituent elements may be completed based on the exemplary embodiment of the present invention, but the present invention is not limited to this embodiment. In the present specification, "to" is used to include numerical values before and after the "to" as a lower limit value and an upper limit value.
[ polarizing plate ]
The polarizing plate of the present invention comprises at least a polarizer and an optical film, wherein the polarizer and the optical film are directly laminated or laminated via an adhesive, the optical film has a film thickness of 0.1 to 10 [ mu ] m, a tensile strength of 50 to 1000MPa, and an absolute value of retardation Rth in the thickness direction of 25nm or less.
Hereinafter, each constituent element of the polarizing plate of the present invention will be described.
[ polarizer ]
The polarizer is not particularly limited, and for example, a polarizer obtained by immersing and stretching a polyvinyl alcohol film in an iodine solution, a polarizer coated with a dichroic dye and subjected to an alignment treatment, and the like are preferably used. Specifically, a film containing an iodine-polyvinyl alcohol complex or the like can be used as the polarizer. For a polarizer composed of polyvinyl alcohol (PVA) and dichroic molecules, for example, reference can be made to the description of jp 2009-237376 a. The thickness of the polarizer may be 1 to 50 μm, preferably 2 to 30 μm, and more preferably 3 to 20 μm.
[ polarizer protective film ]
The optical film of the present invention may be further bonded to the polarizer on the side opposite to the side to which the optical film (hereinafter, also referred to as the optical film of the present invention) described later used in the present invention is bonded, or a conventionally known polarizer protective film may be bonded.
The conventionally known polarizer protective film is not particularly limited in terms of optical properties and materials, and films containing (or as a main component) a cellulose ester resin, an acrylic resin, and/or a cyclic olefin resin, a polyester resin can be preferably used, and optically isotropic films and optically anisotropic retardation films can be used.
As the conventionally known polarizer protective film, for example, FUJITAC TD40UC, FUJITAC TJ25 (manufactured by Fujifilm Corporation), and the like can be used as a film containing a cellulose ester resin.
As the conventionally known polarizer protective film, a polarizer protective film containing a (meth) acrylic resin containing a styrene resin described in japanese patent No. 4570042, a polarizer protective film containing a (meth) acrylic resin having a glutarimide ring structure in the main chain described in japanese patent No. 5041532, a polarizer protective film containing a (meth) acrylic resin having a lactone ring structure described in japanese patent No. 2009-122664, and a polarizer protective film containing a (meth) acrylic resin having a glutaric anhydride unit described in japanese patent No. 2009-139754 can be used as films containing an acrylic resin.
As the film containing a cyclic olefin resin, the conventionally known polarizer protective film described above can be used a cyclic olefin resin film described in paragraph [0029] of jp 2009-237376 a, or a cyclic olefin resin film containing an additive for reducing Rth described in jp 4881827 a and 2008-063536 a.
In addition, as the conventionally known polarizer protective film, a polyester resin-containing film such as COSMOSHINE SRF (manufactured by TOYOBO co., ltd.) made of polyethylene terephthalate may be used.
In addition, when a polarizer protective film using an acrylic resin is used, the effect of improving the crack resistance by using the optical film of the present invention can be further exhibited.
Conventionally known polarizer protective films can be hydrophilized by surface treatment (as described in Japanese patent application laid-open Nos. 6-94915 and 6-118232), and for example, it is preferable to perform glow discharge treatment, corona discharge treatment, alkali saponification treatment, or the like. As the surface treatment, corona discharge treatment is most preferably used.
[ Adhesives ]
In the polarizing plate of the present invention, the polarizer and the optical film are laminated directly or via an adhesive.
The adhesive used for lamination via an adhesive is preferably an adhesive containing at least one polymerizable compound. The polymerizable compound preferably contains at least one cationically polymerizable compound.
The adhesive is preferably a system containing a cationically polymerizable compound and an acid generator (so-called initiator). In addition, in order to increase the curing rate, a sensitizer is preferably added, and heating may be performed after irradiation with active energy rays. In addition, in the case where the optical film is a releasable laminated film including a releasable base film, the base film may be appropriately released and then irradiated with an active energy ray.
As the compound of the adhesive or sensitizer, a general compound can be used, and specific examples of the cationically polymerizable compound or acid generator (initiator) are described in [0014] to [0066] of Japanese patent laid-open publication No. 2018-41079. Specific examples of the sensitizer include anthracene series ([ 0103] of Japanese patent laid-open publication No. 2018-25771), thioxanthone series, and the like. Two or more of these initiators and sensitizers can be selected and used simultaneously.
The polarizing plate of the present invention is also preferably in the following manner: the optical film and the polarizer are laminated on at least one surface of the polarizer via an adhesive containing at least one polymerizable compound, and the polymerizable compound does not substantially permeate into the optical film.
The polymerizable compound does not substantially permeate the optical film means that a small amount of the polymerizable compound can permeate the optical film within a range that does not affect the appearance or performance of the optical film. For example, the polymerizable compound that penetrates into the optical film includes a polymerizable compound having a maximum penetration depth of 0.001 to 3 μm. Preferably 0.005 to 1 μm, and more preferably 0.01 to 0.5. mu.m.
In the present invention, the surface of the optical film opposite to the side having the adhesive is measured by ATR-IR, the state of the adhesive penetration is determined, and when no absorption peak derived from the adhesive is detected, the optical film is set to be substantially free from the adhesive penetration. ATR is the abbreviation for Attenuated Total Reflection and IR for infrared spectroscopy. Specifically, the evaluation can be performed by attaching an ATR prism (for example, MKII Golden Gate Single Reflection ATR System, Specac) composed of Ge, KRS-5, diamond, ZnSe, or the like to a fourier transform infrared spectrometer (for example, NICOLET6700, manufactured by Thermo Fisher Scientific inc.) and measuring the measurement in a Reflection mode to observe a characteristic absorption peak area.
[ optical film ]
The optical film included in the polarizing plate of the present invention will be explained.
The optical film used in the present invention has a film thickness of 0.1 to 10 μm, a tensile strength of 50 to 1000MPa, and an absolute value of retardation Rth in the thickness direction of 25nm or less.
The total light transmittance of visible light (wavelength 380-780 nm) of the optical film is preferably 80% or more, more preferably 82% or more, and still more preferably 85% or more.
The material constituting the optical film is not particularly limited, and a material having the highest mass ratio, such as a polymer resin or a cured composition of a composition containing a reactive monomer, can be used as the matrix material. From the viewpoint of improving the tensile strength, a material having high cohesiveness can be selected, and as an additive having high hardness or tensile strength among the raw material monomers, a strength-improving agent described later is preferably added.
< substrate Material >
From the viewpoint of a function of imparting barrier properties to an optical film, the moisture absorption rate (when not particularly described, the equilibrium moisture absorption rate at 25 ℃ and 80% RH) of the matrix material is preferably 2.0% by mass or less, more preferably 0 to 1.5% by mass, and still more preferably 0 to 1.0% by mass. The RH represents relative humidity.
The moisture absorption rate of the above-mentioned matrix material was measured as follows.
After a sample of the matrix material was humidified at 25 ℃ and a relative humidity of 80% for 24 hours, the moisture absorption rate was measured by the Karl Fischer method using a moisture meter, sample drying devices "CA-03" and "VA-05" { both manufactured by Mitsubishi Chemical Corporation }.
The matrix material is preferably a resin described later, more preferably a styrene resin, a cyclic polyolefin resin, or a polyester resin, and even more preferably a styrene resin or a cyclic polyolefin resin.
The matrix material is preferably 45 mass% or more, more preferably 50 to 90 mass%, and further preferably 55 to 80 mass% with respect to the total mass of the optical film.
When an optical film is produced from the polymer resin or the composition (coating solution) containing the reactive monomer, the total mass of the optical film is determined by subtracting the solvent from the total mass of the coating solution.
< thickness of optical film >
The thickness of the optical film is 0.1 to 10 μm. When the thickness exceeds 10 μm, it becomes difficult to make the polarizing plate thin, and when it is thinner than 0.1. mu.m, the moist heat resistance of the polarization degree is lowered. The thickness of the optical film is preferably 1 to 9 μm, and more preferably 3 to 6 μm.
< tensile Strength of optical film >
The tensile strength of the optical film used in the present invention is 50 to 1000 MPa. When the tensile strength is less than 50MPa, the crack resistance of the polarizer is deteriorated. When the tensile strength exceeds 1000MPa, the transparency may be impaired.
The tensile strength of the optical film is preferably 70 to 500MPa, more preferably 90 to 300MPa, from the viewpoint of improving crack resistance.
In the present specification, tensile strength means the maximum stress (maximum point stress) observed until fracture when a sample of 150mm × 10mm is cut out from an optical film and the stress against elongation is measured at a tensile rate of 10%/min in an atmosphere of 25 ℃ and 60% RH using an universal tensile tester "stmt 50 BP" manufactured by Toyo Baldwin co.
< retardation of optical film >
In the present invention, Re and Rth represent in-plane retardation and retardation in the thickness direction at a wavelength of 590nm, respectively.
In the present invention, Re and Rth are values measured at a wavelength of 590nm in Axoscan OPMF-1 (manufactured by Opto Science, Inc.). By inputting the average refractive index ((nx + ny + nz)/3) and the film thickness (d) in AxoSacan, it is possible to calculate
Slow axis direction (°)
Re＝(nx-ny)×d
Rth ═ ((nx + ny)/2-nz) × d. nx is a refractive index in a slow axis direction of the film, ny is a refractive index in a fast axis direction of the film, and nz is a refractive index in a thickness direction of the film.
The absolute value of Rth of the optical film used in the polarizing plate of the present invention is 25nm or less, that is, -25 to 25 nm. When the Rth of the optical film is within the above range, light leakage from an oblique direction is improved, and display quality can be improved.
From the above viewpoint, when the pretilt angle of the liquid crystalline compound in the liquid crystal cell of the IPS mode is larger than 1.0 DEG, Rth is preferably-20 to 5nm, and more preferably-10 to 0 nm. When the pretilt angle of the liquid crystalline compound in the liquid crystal cell of the IPS mode is 1.0 DEG or less, the Rth is preferably-5 to 25nm, and more preferably 0 to 20 nm.
The Re of the optical film used in the polarizing plate of the present invention is not particularly limited, and from the viewpoint of further improving light leakage from an oblique direction and improving display quality, in the case of using the optical film in an IPS mode liquid crystal display device, the Re is preferably 0 to 20nm, more preferably 0 to 10nm, and further preferably 0 to 5 nm.
< other characteristics >
The optical film may have performance equivalent to that of a commonly known polarizing plate protective film, and preferably has performance required for a so-called inner film disposed between a polarizer and a liquid crystal cell in a liquid crystal display device. Specific characteristic values include haze, spectral characteristics, retardation moist heat resistance, and the like associated with display characteristics, and dimensional change rate, glass transition temperature, equilibrium moisture absorption rate, moisture permeability, contact angle, and the like associated with a moist heat thermostat associated with mechanical characteristics and suitability for polarizing plate processing.
< layer Structure >
The optical film may have a single layer or a laminated structure of two or more layers, and may further include a functional layer having optical anisotropy, scattering, or the like directly or via an adhesive or the like. However, the optical film preferably satisfies the above characteristics in addition to the functional layer. The optical film is preferably a single layer.
< resin >
The optical film preferably contains at least one resin.
The resin contained in the optical film will be explained.
The resin contained in the optical film is not particularly limited, but from the viewpoint of ensuring the barrier property of the compound having an ionic functional group having an effect of improving the moist heat resistance of the polarizing plate, the SP value (solubility parameter value) by the Hoy method is preferably 20MPa 0.5 The following.
The SP value by the Hoy method was calculated by the method described in the Polymer Handbook four e part, depending on the molecular structure of the resin. When the resin is a mixture of a plurality of resins, the SP value of each constituent unit is calculated as the SP value.
More specifically, the optical film was cut with a razor, the molecular structure was analyzed by thermal decomposition GC (gas chromatograph)/MS (mass spectrometer), and the composition ratio was analyzed by Nuclear Magnetic Resonance (NMR).
The resin may be a linear resin or a mesh resin.
Specific examples of the resin include acrylic resins such as styrene resins, cyclic polyolefin resins, epoxy resins, and methyl methacrylate resins (PMMA); cellulose resins such as polyester resins and cellulose acetate; the polymer containing a compound having an ethylenically unsaturated double bond is preferably a resin containing at least one selected from styrene resins, cyclic polyolefin resins, polyester resins, and polymers containing a cyclic aliphatic hydrocarbon group and a compound having an ethylenically unsaturated double bond, more preferably a polymer containing a styrene resin, a cyclic polyolefin resin, a cellulose resin, and a compound containing a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated double bond, and even more preferably a styrene resin, a cyclic polyolefin resin, or a cellulose resin, as a matrix material, from the viewpoint of the resistance to moist heat as a polarizer protective film.
(styrene resin)
The styrene-based resin refers to a resin in which the monomer unit having the highest ratio among the monomer units constituting the resin is a monomer unit derived from a styrene-based monomer. For example, in the case of a resin composed of 2-component system, it means a resin containing 50 mass% or more of monomer units derived from a styrene monomer. Here, the styrenic monomer means a monomer having a styrene skeleton in its structure.
The styrene-based resin preferably contains 70 mass% or more, more preferably 85 mass% or more, of monomer units derived from a styrene-based monomer.
Specific examples of the styrene-based resin include homopolymers of styrene or a derivative thereof, and binary or higher copolymers of styrene or a derivative thereof and another copolymerizable monomer. The styrene derivative is a compound in which another group is bonded to styrene, and examples thereof include an alkylstyrene such as o-methylstyrene, m-methylstyrene, p-methylstyrene, 2, 4-dimethylstyrene, o-ethylstyrene and p-ethylstyrene, and a substituted styrene in which a hydroxyl group, an alkoxy group, a carboxyl group, a halogen or the like is introduced into the benzene nucleus of styrene such as hydroxystyrene, t-butoxystyrene, vinylbenzoic acid, o-chlorostyrene and p-chlorostyrene.
The styrene resin also includes a product obtained by copolymerizing a styrene monomer component with another monomer component. Examples of the copolymerizable monomer include alkyl methacrylates such as methyl methacrylate, cyclohexyl methacrylate, methylphenyl methacrylate and isopropyl methacrylate; unsaturated carboxylic acid alkyl ester monomers such as alkyl acrylates including methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and cyclohexyl acrylate; unsaturated carboxylic acid monomers such as methacrylic acid, acrylic acid, itaconic acid, maleic acid, fumaric acid, and cinnamic acid; unsaturated dicarboxylic anhydride monomers as anhydrides such as maleic anhydride, itaconic acid, ethyl maleic acid, methyl itaconic acid, and chloromaleic acid; unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile; conjugated dienes such as 1, 3-butadiene, 2-methyl-1, 3-butadiene (isoprene), 2, 3-dimethyl-1, 3-butadiene, 1, 3-pentadiene and 1, 3-hexadiene, and two or more of these can be copolymerized.
AS-70 described later can be contained in the styrene resin.
As the styrene-based resin, a plurality of styrene-based resins having different compositions, molecular weights, and the like can be used simultaneously.
Styrenic resins can be obtained by well-known anionic, bulk, suspension, emulsion or solution polymerization methods. Also, in the styrenic resin, the unsaturated double bond of the benzene ring of the conjugated diene or styrenic monomer may be hydrogenated. The hydrogenation rate can be measured by Nuclear Magnetic Resonance (NMR).
(Compound having Cyclic aliphatic hydrocarbon group and group having ethylenically unsaturated double bond)
The cyclic aliphatic hydrocarbon group is preferably a group derived from an alicyclic compound having 7 or more carbon atoms, more preferably a group derived from an alicyclic compound having 10 or more carbon atoms, and still more preferably a group derived from an alicyclic compound having 12 or more carbon atoms.
The cyclic aliphatic hydrocarbon group is particularly preferably a group derived from a polycyclic compound such as a bicyclic compound or a tricyclic compound.
More preferably, a central skeleton of the compound described in Japanese patent application laid-open No. 2006-215096, a central skeleton of the compound described in Japanese patent application laid-open No. 2001-10999, a skeleton of an adamantane derivative, or the like is mentioned.
Specific examples of the cyclic aliphatic hydrocarbon group include norbornyl, tricyclodecanyl, tetracyclododecyl, pentacyclopentadecyl, adamantyl, and adamantyl.
The compound containing a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated double bond preferably has two or more groups having an ethylenically unsaturated double bond in the molecule.
The cyclic aliphatic hydrocarbon group (including a linking group) is preferably a group represented by any one of the following formulae (I) to (V), more preferably a group represented by the following formula (I), (II) or (IV), and still more preferably a group represented by the following formula (I).
That is, the compound containing a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated double bond is preferably a compound having a structure represented by any one of the following general formulae (I) to (V), more preferably a compound having a structure represented by the following general formulae (I), (II), or (IV), and still more preferably a compound having a structure represented by the following general formula (I).
[ chemical formula 1]
In the general formula (I), L 1 And L 2 Each independently represents a single bond or a linking group having a valence of 2 or more. n represents an integer of 1 to 3.
[ chemical formula 2]
In the general formula (II), L 1 And L 2 Each independently represents a single bond or a linking group having a valence of 2 or more. n represents an integer of 1 to 2.
[ chemical formula 3]
In the general formula (III), L 1 And L 2 Each independently represents a single bond or a linking group having a valence of 2 or more. n represents an integer of 1 to 2.
[ chemical formula 4]
In the general formula (IV), L 1 And L 2 Each independently represents a single bond or a linking group having a valence of 2 or more, L 3 Represents a hydrogen atom, a single bond or a linking group having a valence of 2 or more.
[ chemical formula 5]
In the general formula (V), L 1 And L 2 Each independently represents a single bond or a linking group having a valence of 2 or more.
As to L 1 、L 2 And L 3 The linking group having a valence of 2 or more in (a) includes an alkylene group having 1 to 6 carbon atoms which may be substituted, an amide bond which may be substituted at the N-position, a urethane bond which may be substituted at the N-position, an ester bond, an oxycarbonyl group, an ether bond and the like, and a combination of two or more of these.
The compound containing a cyclic aliphatic hydrocarbon group and a group having 2 or more ethylenically unsaturated double bonds in the molecule is constituted by bonding the cyclic aliphatic hydrocarbon group and the group having an ethylenically unsaturated double bond via a linking group.
These compounds can be easily synthesized by a one-stage or two-stage reaction of a polyol such as a diol or triol having the cyclic aliphatic hydrocarbon group and a compound having a (meth) acryloyl group, a vinyl group, a styryl group, an allyl group, or the like such as a carboxylic acid, a carboxylic acid derivative, an epoxy derivative, an isocyanate derivative, or the like.
It is preferable that the compound can be synthesized by reacting a polyol having the cyclic aliphatic hydrocarbon group with a compound such as (meth) acrylic acid, (meth) acryloyl chloride, (meth) acrylic anhydride, glycidyl (meth) acrylate, or a compound described in WO2012/00316A (for example, 1, 1-bis (acryloyloxymethyl) ethyl isocyanate).
Preferred specific examples of the compound containing a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated double bond are shown below, but the present invention is not limited to these.
[ chemical formula 6]
[ chemical formula 7]
(Cyclic polyolefin resin)
The cyclic polyolefin resin means a polymer resin having a cyclic olefin structure.
The polymer having a preferred cyclic olefin structure is a cyclic polyolefin resin which is an addition (co) polymer containing at least one or more repeating units represented by the following general formula (II) and, if necessary, a cyclic polyolefin resin which is an addition (co) polymer further containing at least one or more repeating units represented by the general formula (I). Also, a ring-opened (co) polymer containing at least one repeating unit represented by the general formula (III) can also be suitably used.
[ chemical formula 8]
[ chemical formula 9]
[ chemical formula 10]
In the formulas (I) to (III), m represents an integer of 0 to 4. R is 1 ～R 6 X represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms 1 ～X 3 、Y 1 ～Y 3 Represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom, -COOR 10 、-(CH 2 ) n COOR 11 、-(CH 2 ) n OCOR 12 、-(CH 2 ) n NCO、-(CH 2 ) n NO 2 、-(CH 2 ) n CN、-(CH 2 ) n CONR 13 R 14 、-(CH 2 ) n NR 13 R 14 、-(CH 2 ) n OZ、-(CH 2 ) n W or from X 1 And Y 1 Or X 2 And Y 2 Or X 3 And Y 3 Formed (-CO) 2 O、(-CO) 2 NR 15 . In addition, R 10 ，R 11 ，R 12 ，R 13 ，R 14 ，R 15 Represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, Z represents a hydrocarbon group or a halogen-substituted hydrocarbon group, and W represents SiR 16 p D 3-p (R 16 A hydrocarbon group having 1 to 10 carbon atoms, D represents a halogen atom or-OCOR 16 OR-OR 16 P represents an integer of 0 to 3), and n represents an integer of 0 to 10.
Furthermore, hydrogenated norbornene-based polymers can also be preferably used, for example, Japanese patent application laid-open Nos. 1-240517, 7-196736 and 7Japanese patent laid-open Nos. 60-26024, 62-19801, 2003-1159767, 2004-309979 and the like, and the polycyclic unsaturated compound is subjected to addition polymerization or metathesis ring-opening polymerization and then hydrogenated. In the norbornene-based polymer, R 5 ～R 6 Preferably a hydrogen atom or-CH 3 ，X 3 And Y 3 Preferably a hydrogen atom, Cl, -COOCH 3 Other groups may be appropriately selected.
Further, norbornene addition (co) polymers can be preferably used, and are disclosed in Japanese patent laid-open No. 10-7732, Japanese Kokai publication No. 2002-504184, U.S. Pat. No. 2004229157A1, WO2004/070463A1 and the like. Obtained by addition polymerization of norbornene polycyclic unsaturated compounds to each other. Further, if necessary, the norbornene polycyclic unsaturated compound may be mixed with ethylene, propylene, butene; conjugated dienes such as butadiene and isoprene; non-conjugated dienes such as ethylidene norbornene; addition polymerization of linear diene compounds such as acrylonitrile, acrylic acid, methacrylic acid, maleic anhydride, acrylic acid esters, methacrylic acid esters, maleimide, vinyl acetate, and vinyl chloride.
(acrylic resin)
As the acrylic resin, any suitable (meth) acrylic resin can be used. Examples thereof include poly (meth) acrylates such as polymethyl methacrylate, methyl methacrylate- (meth) acrylic acid copolymers, methyl methacrylate- (meth) acrylic acid ester copolymers, methyl methacrylate-acrylic acid ester- (meth) acrylic acid copolymers, methyl (meth) acrylate-styrene copolymers (such as MS resins), and polymers having alicyclic hydrocarbon groups (for example, methyl methacrylate-cyclohexyl methacrylate copolymers, methyl methacrylate- (meth) acrylic acid norbornyl ester copolymers, etc.). Preferred examples thereof include a C1-6 alkyl (meth) acrylate such as polymethyl (meth) acrylate. More preferably, the resin composition contains a methyl methacrylate resin containing methyl methacrylate as a main component (50 to 100% by mass, preferably 70 to 100% by mass). Further, (meth) acrylic resins having a glutaric anhydride structure, (meth) acrylic resins having a glutarimide structure, and (meth) acrylic resins having a lactone ring structure are preferable, and (meth) acrylic resins having a lactone ring structure can also be used.
The weight average molecular weight of the acrylic resin used as the strength improver is not particularly limited, but is preferably 1 to 500 ten thousand, more preferably 5 to 200 ten thousand, and still more preferably 10 to 150 ten thousand from the viewpoint of improving mechanical strength.
Commercially available acrylic resins include Dianal SE-5437, SE-5102, SE-5377, SE-5649, SE-5466, SE-5482, HR-169, HR-124, HR-1127, HR-116, HR-113, HR-148, HR-131, HR-470, HR-634, HR-606, HR-607, LR-1065, LR-574, LR-143, LR-396, LR-637, LR-162, LR-469, LR-216, BR-50, BR-52, BR-60, BR-64, BR-73, BR-75, BR-77, BR-79, BR-80, BR-83, BR-85, BR-87, BR-88, BR-90, LTD, manufactured by LTD BR-93, BR-95, BR-100, BR-101, BR-102, BR-105, BR-106, BR107, BR-108, BR-112, BR-113, BR-115, BR-116, BR-117; esrex PSE-0020, SE-0040, SE-0070, SE-0100, SE-1010, SE-1035, manufactured by SEKISUI CHEMICAL CO., LTD.; sanyo Chemical Industries, Ltd. HIMER ST95, ST 120; FM601 manufactured by Mitsui Chemicals, inc.
(polyester resin)
Specific examples of the polyester resin include polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), and the like, and PEN is particularly preferable.
The weight average molecular weight (Mw) of the resin used as the matrix material of the optical film is not particularly limited, and is preferably 3,000 to 1,000,000, more preferably 10,000 to 500,000.
The weight average molecular weight of the resin was measured under the following conditions in terms of weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) in terms of standard polystyrene. In addition, Mn is a number average molecular weight in terms of standard polystyrene.
Using GPC: gel permeation chromatography device (HLC-8220 GPC manufactured by TOSOH CORPORATION), column: sequentially connecting a protective column HXL-H, a TSK gel G7000HXL, 2 TSK gel GMHXL and a TSK gel G2000HXL manufactured by TOSOH CORPORATION, and an eluent: tetrahydrofuran, flow rate: 1mL/min, sample concentration: 0.7-0.8 mass%, sample injection amount: 70. mu.L, measurement temperature: 40 ℃, detector: differential Refractometer (RI) 40 ℃ and composition curve: calibration curves for 7 samples up to a TSK standard polystyrene Mw of 2800000 to 1050(Mw/Mn of 1.03 to 1.06) manufactured by TOSOH.
The resin used for the optical film may contain one kind or two or more kinds. When the optical film is formed of a plurality of layers, the resins of the respective layers may be the same or different.
The content of the resin in the optical film is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more, relative to the total mass of the optical film. The content of the resin in the optical film is preferably 99.5% by mass or less based on the total mass of the optical film.
< other additives >
Known additives can be incorporated into the optical film. Examples of the additives, strength improvers and known additives to be added for the purpose of improving the tensile strength of the optical film include low-molecular plasticizers, oligomer-based plasticizers, retardation regulators, delustering agents, ultraviolet absorbers, deterioration inhibitors, peeling accelerators, infrared absorbers, antioxidants, fillers, surfactants, compatibilizing agents, pigments and the like. Among these, from the viewpoint of improving the tensile strength, as an additive having high hardness or tensile strength in the raw material monomer, a strength improver described later can be preferably used. The kind and amount of each raw material are not particularly limited as long as the effect of the present invention can be obtained. In addition, in the case where the optical film is formed of a plurality of layers, the kind and amount of the additive may be different in each layer.
(Strength improver)
Among known additives, an additive having any one of properties I to III below can be blended to improve the strength of the optical film. Specific examples thereof include an inorganic filler, an organic filler, and the resin described below. The amount of such an additive is not particularly limited, but is preferably 0.1% by mass or more, and more preferably 0.5 to 49% by mass, based on the total amount of the optical film. When the additive is an inorganic substance, the amount added is more preferably 0.5 to 25% by mass, and most preferably 1 to 15% by mass, from the viewpoint of film workability and transparency. In the case of an organic material, from the viewpoint of achieving both the strength-improving effect and other properties, the content is more preferably 4.5 to 49% by mass, most preferably 10 to 35% by mass, based on the total amount of the optical film.
The elastic modulus of the additive is higher than that of the matrix material
II the elongation at break of the additive is higher than that of the matrix material
III the additive has a higher breaking strength than the matrix material
I additives having an elastic modulus higher than that of the matrix material
As the strength improver, an additive having an elastic modulus higher than that of the matrix material is preferably used. The difference between the elastic modulus of the additive and the elastic modulus of the matrix material is preferably 100MPa or more, more preferably 500MPa or more, and still more preferably 1,000MPa or more.
The elastic modulus of the additive itself depends on the type of the matrix material, and is preferably 1,000 to 100,000MPa, more preferably 2,000 to 70,000MPa, and still more preferably 3,000 to 50,000 MPa.
The elastic modulus of the additive and the matrix material in the present invention is a value measured at 25 ℃ and 60% RH at a tensile rate of 10 mm/min by TENSILON (manufactured by A & D Company, Limited) after shaping the additive and the matrix material to have a width of 10mm, a thickness of 0.04mm, and a collet pitch of 100 mm. The elastic modulus of the filler (particles, fibers, etc.) is a value measured by using a micro compression tester (MCT-211, manufactured by Shimadzu Corporation).
Specific examples of the additive having an elastic modulus higher than that of the matrix material include high-elastic-modulus resins such as inorganic substances and engineering plastics, and cellulose-based resins.
II additives with higher elongation at break than the matrix material
As the strength improver, an additive having a higher elongation at break than that of the matrix material is preferably used. The difference between the elongation at break of the additive and the elongation at break of the matrix material is preferably 1% or more, more preferably 3% or more, and still more preferably 10% or more.
The elongation at break of the additive itself depends on the type of the matrix material, and is preferably 1% to 500%, more preferably 5% to 300%, and still more preferably 10% to 100%.
The elongation at break of the additive and matrix material in the present invention was determined as the elongation at break (%) at the time of sample breaking by shaping the additive and matrix material to have a width of 10mm, a thickness of 0.04mm and a chuck pitch of 100mm in conformity with JIS K5600, leaving the resultant to stand at 25 ℃ under 60% RH for 2 hours, and then immediately drawing the resultant at a drawing rate of 10%/min in an atmosphere of 25 ℃ under 60% RH by TENSILON (manufactured by A & D Company, Limited).
Specific examples of the additive having a higher elongation at break than the matrix material include resins having a high molecular weight (e.g., ultrahigh molecular weight acrylic), cellulose resins, polycarbonates, polyesters, polyethylenes, and the like.
III additives having a higher fracture strength than the matrix material
As the strength improver, an additive having a higher breaking strength than that of the matrix material is preferably used. The difference between the fracture strength of the additive and the fracture strength of the matrix material is preferably 1MPa or more, more preferably 5MPa or more, and still more preferably 10MPa or more.
The fracture strength of the additive itself depends on the type of the matrix material, and is preferably 50 to 1,000MPa, more preferably 60 to 500MPa, and still more preferably 70 to 300 MPa.
The breaking strength of the additive and the matrix material in the present invention is determined as the breaking strength (MPa) at the time of breaking of the sample in the same measurement as the above-mentioned breaking elongation.
Specific examples of the additive having a higher breaking strength than the matrix material include resins such as acrylic, cellulose resins, polycarbonate, and polyester.
The strength improver is preferably an additive having any of the properties I to III described above, and more preferably an additive compatible with the matrix resin or an additive that is not compatible with the matrix material and is dispersed in the matrix resin.
Fillers
The additive having any of the properties I to III is preferably a filler.
Spherical fillers such as silica fine particles and metal fine particles, rod-shaped fillers such as whiskers, fibrous fillers (organic and/or inorganic), and the like can be used. For example, Japanese patent laid-open publication No. 2016-053232 and the like.
The filler is preferably an organic filler. Specifically, the organic filler is preferably a cellulose polymer or an elastomer nanofiber material.
The cellulose-based polymer as the nanofiber material is preferably any of cellulose acylate, nitrocellulose, ethyl cellulose, and carboxymethylethylcellulose. More preferably, the cellulose acylate is cellulose acetate, cellulose propionate, cellulose butyrate or cellulose acetate propionate. Cellulose acetate is more preferably cellulose triacetate or cellulose diacetate. When a cellulose-based polymer is used as the nanofiber material, cellulose triacetate is particularly preferable.
The elastomer of the nanofiber material is preferably any one of an acrylic elastomer, a styrene elastomer, an olefin elastomer, a vinyl chloride elastomer, a polyurethane elastomer, and an amide elastomer. In the case of using an elastomer as the nanofiber material, an acrylic elastomer is particularly preferable.
The additive is preferably an additive which is compatible with the matrix material and has a higher elastic modulus, higher elongation at break, or higher strength at break than the matrix material, or an additive which is not compatible with the matrix material and is dispersed in the matrix material and has a higher elastic modulus, higher elongation at break, or higher strength at break than the matrix material.
Regarding the compatibility of the additive and the matrix material, a Differential Scanning Calorimeter (DSC) was used, and when characteristic signals (glass transition temperature, melting point, and the like) derived from the respective raw materials in the additive and the matrix material were observed at the same time, it was judged as incompatible, and when the signal was a single signal, it was judged as compatible.
Resins as strength improvers
The additive having any of the properties I to III is preferably the resin. Among them, acrylic resins, cycloolefin resins, cellulose resins, and polyester resins are preferable, and acrylic resins are more preferable.
The acrylic resin is preferably a poly (meth) acrylate such as polymethyl methacrylate, a polyacrylate, or a copolymer thereof, more preferably polymethyl methacrylate, polymethyl acrylate, or a copolymer thereof, and still more preferably polymethyl methacrylate.
The weight average molecular weight of the acrylic resin when the acrylic resin is used as the strength-improving agent is not particularly limited, but is preferably 1 to 500 ten thousand, more preferably 5 to 200 ten thousand, and further preferably 10 to 150 ten thousand, from the viewpoint of improving the mechanical strength.
As described above, in the polarizing plate of the present invention, the polarizer and the optical film are laminated directly or via the adhesive.
When the polarizing plate of the present invention is manufactured, a releasable laminated film formed of an optical film and a releasable substrate film is also preferably used.
[ peelable laminated film ]
A description will be given of a releasable laminated film composed of an optical film and a releasable base film (also simply referred to as "base film").
The following peelable laminate film is preferred: the releasable laminated film is a laminate comprising a substrate film comprising polyethylene terephthalate and an optical film,
the substrate film is in direct contact with the optical film,
the thickness of the optical film is 0.1 to 10 μm.
The base film of the releasable laminated film that can be used in the present invention can be released from the optical film. The stress when the substrate film is peeled from the optical film is preferably 0.05N/25mm or more and 2.00N/25mm or less, more preferably 0.08N/25mm or more and 0.50N/25mm or less, and still more preferably 0.11N/25mm or more and 0.20N/25mm or less.
When the stress is 0.05N/25mm or more, peeling is not likely to occur in the middle of the polarizing plate processing process, and therefore, it is preferable that the stress is 2.00N/25mm or less, because the polarizing plate is not bent when the substrate film is peeled.
After the surface of the optical film of the releasable laminated film cut to have a width of 25mm and a length of 80mm was bonded to a glass substrate via an acrylic pressure-sensitive adhesive sheet and fixed, a 90 ° peel test (following Japanese Industrial Standards (JIS) K6854-1: 1999 "adhesive-peel adhesion strength test method-part 1: 90 degree peel") was performed at a crosshead speed (holding movement speed) of 200 mm/min under an atmosphere of 23 ℃ and 60% relative humidity with a tensile tester (RTF-1210 manufactured by a & D Company, Limited) with the substrate film at one end (side of 25mm width) in the longitudinal direction of the test piece sandwiched therebetween, whereby the stress at the time of peeling the substrate film of the releasable laminated film from the optical film could be evaluated.
< substrate film >
A base film of a releasable laminated film will be described.
The base film of the releasable laminate film is not particularly limited, and the main component of the base film (the component having the largest content on a mass basis among the components constituting the base film) is preferably a polyester resin.
The substrate film preferably contains polyethylene terephthalate (PET).
From the viewpoint of the mechanical strength of the substrate, the weight average molecular weight of PET contained in the substrate film is preferably 20,000 or more, more preferably 30,000 or more, and further preferably 40,000 or more.
The weight average molecular weight of PET was determined by the aforementioned GPC method by dissolving the substrate film in Hexafluoroisopropanol (HFIP).
The thickness of the base film is not particularly limited, but is preferably 5 to 100. mu.m, more preferably 10 to 75 μm, and still more preferably 15 to 55 μm.
As a known surface treatment, corona treatment, glow discharge treatment, undercoating, and the like may be performed on the base material film.
< method for producing peelable laminated film >
A method for producing a peelable laminate film will be described.
The releasable laminated film is preferably produced by applying a solution containing the resin and a solvent to the base film and drying the solution to form an optical film. The solvent can be appropriately selected from the viewpoints of dissolving or dispersing the resin, easily forming a uniform planar shape in the coating step and the drying step, ensuring the storage stability of the solution, having an appropriate saturated vapor pressure, and the like. In addition, it is not necessary to perform surface treatment on the base film before coating the resin solution for forming the optical film.
In order to obtain the optical film used in the present invention, the optical film is preferably formed on the base film by coating as described above, but the base film may not necessarily be used. For example, when the resin contained in the optical film is a resin capable of melt film formation such as a polyester resin, the optical film may be produced by melt film formation.
In the case of producing an optical film by melt film formation, it is preferable to suppress orientation or crystallization by setting the stretching conditions to a low stretching ratio/a high stretching temperature from the viewpoint of setting the absolute value of Rth of the optical film to 25 or less.
In the polarizing plate of the present invention, the optical film of the present invention may be further bonded to the polarizer on the side opposite to the side to which the optical film is bonded, or the above-mentioned conventionally known polarizing plate protective film may be bonded.
The polarizing plate of the present invention may further comprise a film having a relatively high Re or Rth of 25nm or more. Specifically, the optical compensation film includes a polymer film-based optical compensation film, a liquid crystal compound-based optical compensation film, and the like. In another embodiment, the polarizing plate of the present invention may further include an inorganic sputtering-based antireflection layer. The film of the present invention can suppress cracking of these members and polarizing plates.
[ method for producing polarizing plate ]
The method for producing a polarizing plate of the present invention includes a step of laminating the optical film on a polarizer directly or via the adhesive. Among them, it is preferable to include a step of irradiating a polarizer with an active energy ray after laminating the optical film on the polarizer via the adhesive.
In the case of using the above-mentioned releasable laminated film, the method for producing a polarizing plate of the present invention includes a step of laminating a surface of the optical film opposite to the interface on the substrate film side on a polarizer via the adhesive, and then irradiating an active energy ray from the substrate film side, and preferably further includes a step of releasing the substrate film.
Preferably, the optical film is brought into contact with the adhesive and is irradiated with an active energy ray after 0.1 to 30 seconds.
The method for producing a polarizing plate of the present invention is preferably a method for producing a polarizing plate, in which a surface of an optical film of a releasable laminated film opposite to the substrate film-side interface is bonded to a polarizer via an adhesive, and then the substrate film is peeled to obtain a polarizing plate having the polarizer and the optical film. The penetration depth of the optical film varies depending on the condition (temperature, time) with time after the adhesive and the optical film come into contact with each other, in addition to the SP value difference between the adhesive and the optical film, and for example, a condition of low temperature and short time is preferable for suppressing the penetration. In addition, since the penetration rate can be reduced by temporarily irradiating the penetration depth with active energy rays, it is effective to additionally irradiate the polarizing plate for the purpose of promoting curing in order to secure durability of the polarizing plate after the penetration depth is suppressed by the temporary irradiation.
If necessary, the surface of the optical film to be bonded to the polarizer may be subjected to hydrophilization treatment by glow discharge treatment, corona treatment, alkali saponification treatment, or the like. When a releasable laminated film is used, the surface of the optical film of the releasable laminated film opposite to the interface on the substrate film side may be subjected to hydrophilization treatment by glow discharge treatment, corona treatment, alkali saponification treatment, or the like, as necessary.
< peeling of substrate film >
In the case of using a releasable laminated film, the substrate film can be peeled by the same method as in the peeling step of a separator (release film) using a general polarizing plate with an adhesive. The base film may be peeled off immediately after the step of laminating the optical film and the polarizer directly or via an adhesive and drying them, or may be peeled off separately in a subsequent step after the drying step by being temporarily wound into a roll shape.
[ display device ]
The polarizing plate of the present invention can be used for a liquid crystal display device, an organic EL display device, or the like.
The liquid crystal display device includes a liquid crystal cell and a polarizing plate.
In the liquid crystal display device, the polarizing plate may be arbitrarily arranged, but the optical film in the polarizing plate is preferably arranged on the liquid crystal cell side of the polarizer.
The liquid crystal display device further includes a backlight, and the polarizing plate is preferably disposed on the backlight side or the viewing side. The backlight is not particularly limited, and a known backlight can be used. The liquid crystal display device preferably includes a backlight, a backlight-side polarizing plate, a liquid crystal cell, and a viewing-side polarizing plate laminated in this order.
As for the other structure, any structure of a known liquid crystal display device can be adopted. The mode (mode) of the Liquid Crystal cell is not particularly limited, and various display mode Liquid Crystal display devices such as a TN (Twisted Nematic) Liquid Crystal cell, an IPS (In-Plane Switching) Liquid Crystal cell, an FLC (Ferroelectric Liquid Crystal) Liquid Crystal cell, an AFLC (Anti-Ferroelectric Liquid Crystal) Liquid Crystal cell, an OCB (Optically compensated Bend) Liquid Crystal cell, an STN (super Twisted Nematic) Liquid Crystal cell, a VA (vertical alignment) Liquid Crystal cell, and a HAN (Hybrid Aligned Nematic) Liquid Crystal cell can be configured. Among them, the liquid crystal cell is preferably of the IPS system.
As for the other structure, any structure of a known liquid crystal display device or organic EL display device can be adopted.
The present invention also relates to a display device in which an adhesive layer is laminated on a surface of the optical film included in the polarizing plate of the present invention, the surface being opposite to the polarizer, and a substrate is further laminated, wherein the elastic modulus of the adhesive layer is 0.01 to 100MPa, and the elastic modulus of the substrate is 6 to 100 GPa.
The elastic modulus of the adhesive layer in the present invention is a value measured at 25 ℃ and 60% RH at a tensile rate of 10 mm/min by TENSILON (manufactured by A & D Company, Limited) after shaping the adhesive layer to 5mm in width, 1mm in thickness and 10mm in chuck pitch.
In the present invention, the elastic modulus of the adhesive layer is preferably 0.001 to 100MPa, more preferably 0.01 to 10MPa, and still more preferably 0.03 to 1 MPa. When the elastic modulus is within the above range, the polarizing plate of the present invention can be bonded to glass or the like with good adhesion.
In the present invention, the thickness of the adhesive layer is preferably 3 to 30 μm, and more preferably 5 to 20 μm.
As the component contained in the adhesive layer, an acrylic resin, and/or an epoxy resin, and/or an olefin resin can be used.
The adhesive layer can contain an inorganic filler such as a weather resistant stabilizer, a tackifier, a plasticizer, a softening agent, a dye, a pigment, a silane coupling agent, and conductive fine particles/light scattering fine particles, which are generally used in such a field.
Examples of the substrate in the present invention include a glass substrate of a liquid crystal cell used in the display device of the present invention.
The elastic modulus of the substrate in the present invention is a value measured according to ISO14577 (indentation modulus) using a micro hardness tester (manufactured by FISCER INSTRUMENTS K.K., equipment name; Picodenter HM2000) and Berkovich indenter.
In the present invention, the substrate elastic modulus is preferably 6 to 100GPa, more preferably 10 to 90GPa, and still more preferably 30 to 80 GPa. By setting the elastic modulus within the above range, warpage of the substrate can be suppressed.
The thickness of the substrate is not particularly limited, but is preferably 10 to 1000. mu.m, more preferably 10 to 500. mu.m, and still more preferably 20 to 200. mu.m.
The present invention also relates to a display device comprising the polarizing plate of the present invention.
Examples
The present invention will be further specifically described below with reference to examples. The materials, the amounts used, the ratios, the contents of the processes, the process order, and the like shown in the following examples can be appropriately modified without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.
Determination of
[ degree of substitution ]
The degree of acyl substitution of cellulose acylate to be used as filler 1 described later is utilized by the method described in Carbohydr. Res.273(1995)83-91(Tezuka et al) 13 C-NMR was obtained.
[ delay ]
Measured by the method described previously.
[ tensile Strength ]
A 150mm × 10mm sample was cut out from the optical film thus produced, and the stress against elongation was measured at a tensile rate of 10%/min in an atmosphere of 25 ℃ and 60% RH using an universal tensile tester "STM T50 BP" manufactured by Toyo Baldwin co., ltd.
In addition, when the retardation and the tensile strength of the optical films were measured, samples were cut out from the releasable laminated films having the optical films for the optical films a1 to A3 and a6 to a12, and then the substrate films were peeled off to prepare evaluation samples.
[ moisture absorption Rate ]
After a sample of the matrix material was humidified at 25 ℃ and a relative humidity of 80% for 24 hours, the moisture absorption rate was measured by the Karl Fischer method using a moisture meter, sample drying devices "CA-03" and "VA-05" { both manufactured by Mitsubishi Chemical Corporation }.
[ modulus of elasticity ]
The elastic modulus of the additive and the matrix material is a value measured at 25 ℃ 60% RH at a tensile rate of 10 mm/min by TENSILON (manufactured by A & D Company, Limited) after shaping the additive and the matrix material to a width of 10mm, a thickness of 0.04mm, and a collet pitch of 100 mm. The elastic modulus of filler 1 is a value measured by a micro compression tester (MCT-211, manufactured by Shimadzu Corporation).
[ elongation at Break ]
The elongation at break of the additive and matrix material was determined as the elongation at break (%) at the time of sample breaking by shaping the additive and matrix material to a width of 10mm, a thickness of 0.04mm and a chuck pitch of 100mm in conformity with JIS K5600, leaving the sample at 25 ℃ with 60% RH for 2 hours, and then immediately drawing the sample at a drawing rate of 10%/min in an atmosphere of 25 ℃ with 60% RH using TENSILON (manufactured by A & D Company, Limited).
[ breaking Strength ]
The breaking strength of the additive and the matrix material was determined as the breaking strength (MPa) at break of the sample in the same measurement as the above-mentioned breaking elongation.
< production of a releasable laminated film having an optical film A1 >
An optical film a1 was formed on the base film by the following method to produce a releasable laminated film.
1) Preparation of coating liquid
Coating liquid 1 for forming optical film a1 was prepared with the following composition.
2) Composition of coating liquid 1
The obtained coating liquid was filtered with a filter having an absolute filtration accuracy of 1 μm.
The materials used are shown below.
RX 4500: commercially available ARTON (manufactured by JSR, RX4500) was heated at 110 ℃ and returned to room temperature (25 ℃) for use. The equilibrium moisture absorption rate was 0.6 mass%.
Filler 1: the procedure was carried out in the same manner as in example 1([0057]) of Japanese patent application laid-open No. 2018-135615, except that a cellulose triacetate having an acetyl substitution degree of 2.85 was used.
Surfactant 1: a surfactant of the following structure was used.
[ chemical formula 11]
3) Coating of peelable laminated film
An optical film a1 was produced using a commercially available polyethylene terephthalate film or Emblet S38 (38 μm thick, manufactured by UnitikaLtd.) as a base film and coating solution 1 so that the film thickness became 5 μm, and a peelable laminated film (43 μm thick) was obtained. Specifically, coating solution 1 was applied to a substrate film by a die coating method using a slit die described in example 1 of jp 2006-a 122889 at a carrying speed of 30 m/min, and dried at 110 ℃ for 30 seconds. Then, winding was performed.
Production of a peelable laminated film having an optical film A2
An optical film a2 was formed on the same base material film as described above in the same manner as the optical film a1 except that the coating liquid 2 obtained by removing the filler 1 from the coating liquid 1 of the optical film a1 was used, and a releasable laminated film (film thickness 43 μm) was obtained.
< production of a releasable laminated film having an optical film A3 >
An optical film A3 was formed on the same base film as described above in the same manner as the optical film a1 except that the coating solution 1 of the optical film a1 was replaced with the coating solution 3 described below, to obtain a releasable laminated film (film thickness 43 μm).
Composition of coating liquid 3
The obtained coating liquid was filtered with a filter having an absolute filtration accuracy of 1 μm.
The materials used are shown below.
AS-70: acrylonitrile-styrene copolymer resin [ NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD. The equilibrium moisture absorption rate was 0.7 mass%.
SMA2000P (manufactured by Cray Valley, styrene/maleic anhydride copolymer, adhesion modifier)
vYLON500(TOYOBO CO., LTD. manufacture, adhesion modifier)
< optical film A4 >
A commercially available biaxially stretched PET film (TORAY ADVANCED FILM co., ltd., Lumirror #5A-F53, film thickness 5 μm) was used as the optical film a 4.
< optical film A5 >
A resin of polyethylene naphthalate (Teonex TN8050SC, manufactured by TEIJIN limited, hereinafter also referred to as PEN) was polymerized and melt-formed into an unstretched PEN, and then stretched at 110 ℃ to form a film having a thickness of 5 μm, thereby obtaining an optical film a 5.
Production of a peelable laminated film having an optical film A6
An optical film a6 was formed on the same substrate film as described above in the same manner as the optical film A3 except that the coating solution 3 of the optical film A3 was replaced with the coating solution 4 described below, to obtain a releasable laminated film (film thickness 43 μm).
Composition of coating liquid 4
The obtained coating liquid was filtered with a filter having an absolute filtration accuracy of 1 μm.
< production of a releasable laminated film having an optical film A7 >
An optical film a7 was formed on the same base film as described above in the same manner as the optical film A3 except that the coating solution 3 of the optical film A3 was replaced with the coating solution 5 described below, to obtain a releasable laminated film (film thickness 43 μm).
Composition of coating liquid 5
The obtained coating liquid was filtered with a filter having an absolute filtration accuracy of 1 μm.
The materials used are shown below.
BR-88: acrylic resin [ MITSUBISHI RAYON CO., LTD., manufactured by Dianal ].
< production of a releasable laminated film having an optical film A8 >
An optical film A8 was formed on the same base film as the above-described optical film a7, except that the thickness of the optical film was 3 μm, to obtain a releasable laminated film (thickness: 41 μm).
< production of a releasable laminated film having an optical film A9 >
An optical film a9 was formed on the same base film as the above in the same manner as the optical film a7 except that the thickness of the optical film was set to 7 μm, to obtain a releasable laminated film (thickness: 45 μm).
Production of a peelable laminated film having an optical film A10
An optical film a10 was formed on the same substrate film as described above in the same manner as the optical film A3 except that the coating solution 3 of the optical film A3 was replaced with the coating solution 6 described below, to obtain a releasable laminated film (film thickness 43 μm).
Composition of coating liquid 6
The obtained coating liquid was filtered with a filter having an absolute filtration accuracy of 1 μm.
< production of a releasable laminated film having an optical film A11 >
An optical film a11 was formed on the same base film as described above in the same manner as the optical film a7 except that the drying condition of the optical film a7 was changed to 120 ℃ for 30 seconds, to obtain a releasable laminated film (film thickness 43 μm).
Production of a peelable laminated film having an optical film A12
An optical film a12 was formed on the same base film as described above in the same manner as the optical film a11 except that the coating solution 5 of the optical film a11 was replaced with the coating solution 7 described below, to obtain a releasable laminated film (film thickness 43 μm).
Composition of coating liquid 7
The obtained coating liquid was filtered with a filter having an absolute filtration accuracy of 1 μm.
< production of a releasable laminated film having an optical film A13 >
An optical film a13 was formed on the same base film as described above in the same manner as the optical film a12 except that the coating solution 7 of the optical film a12 was replaced with the coating solution 8 described below, to obtain a releasable laminated film (film thickness 43 μm).
Composition of coating liquid 8
The obtained coating liquid was filtered with a filter having an absolute filtration accuracy of 1 μm.
LT-35: a commercially available cellulose acetate (LT-35, manufactured by Daicel Corporation) was heated at 110 ℃ and returned to normal temperature for use. The equilibrium moisture absorption rate was 3 mass%.
< fabrication of polarizing plate >
1) Production of Adhesives
Adhesive 1:
adhesive 1 was prepared with the following composition.
The materials used are shown below.
(polymerizable Compound)
M1: EPIOL EH-N (2-ethylhexyl glycidyl ether) [ manufactured by NOF CORPORATION ]
M2: RIKARESIN DME-100(1, 4-cyclohexanedimethanol diglycidyl ether) [ New Japan Chemical Co., Ltd. ]
M3: CELLOXIDE 2021P (3, 4-epoxycyclohexylmethyl-3, 4' -epoxycyclohexanecarboxylic acid) [ manufactured by Da icel Corporation ]
(initiator)
A: CPI-100P/IRGACURE290 ═ 1/4 mixtures
(sensitizer)
A: DarocuritX (maximum absorption wavelength 385nm) [ manufactured by BASF corporation ]
Adhesive 2:
as the adhesive, a 3% aqueous solution of polyvinyl alcohol (KURARAY co., LTD, PVA-117H) was used.
2) Production of opposed films
Counter film B1
A polymethyl methacrylate film having a thickness of 60 μm was prepared as a counter film B1 in accordance with example 1 of Japanese patent laid-open publication No. 2015-227458.
Counter film B2
A counter film B2 was obtained in the same manner as the counter film B1 except that the thickness of the counter film B1 was changed to 80 μm.
Counter film B3
A polyethylene terephthalate film having a thickness of 80 μm was produced as the opposite film B3 in accordance with the method of the polarizer protective film 1 of Japanese patent application laid-open No. 2017-201417.
Counter film B4
FUJITAC TJ25 (manufactured by Fujifilm Corporation) was immersed in a 4.5mol/L sodium hydroxide solution (saponification solution) adjusted to 37 ℃ for 1 minute, and then the film was washed with water, and then immersed in a 0.05mol/L sulfuric acid aqueous solution for 30 seconds, and then further subjected to a water bath. Then, dehydration was repeated 3 times with an air knife, and after removing water, the film was left in a drying zone at 70 ℃ for 15 seconds and dried, thereby obtaining a counter film B4.
3) Surface treatment of thin films
In the release laminated film produced above, the surface opposite to the interface on the base film side of the optical films a1 to A3 and a6 to a13, and one surface of the optical film a4, the optical film a5, and the opposite films B1 to B4 were subjected to corona treatment.
4) Fabrication of polarizer
Polarizer P1
According to example 1 of Japanese patent laid-open No. 2001-141926, a polarizer having a thickness of 15 μm was produced by forming a peripheral speed difference between 2 pairs of nip rollers and stretching it in the longitudinal direction.
Polarizer P2
A polarizer P2 was obtained in the same manner as the polarizer P1 except that the thickness of the above polarizer P1 was changed to 23 μm.
Polarizer P3
A polarizer P3 was obtained in the same manner as the polarizer P1 except that the thickness of the above polarizer P1 was changed to 8 μm.
5) Bonding
The polarizer thus obtained, a peelable laminated film containing the optical film subjected to the surface treatment, and an opposing film subjected to the surface treatment were used, and the polarizer was sandwiched by the surfaces subjected to the surface treatment, and then laminated by roll-to-roll using the adhesive so that the absorption axis of the polarizer, the longitudinal directions of the optical film, and the opposing film were parallel to each other. Next, an air-cooled metal halide lamp (EYE GRAPHICS co., ltd.) was used to irradiate the irradiation dose 300mJ/cm 2 Is cured by Ultraviolet (UV) light.
Next, the base film of the peelable laminated film was continuously peeled off by the same peeling device as the separator to produce a polarizing plate.
Polarizing plates were produced in the same manner as in the case of the polarizing plates using the optical films a4 and a5, except that the optical films a4 and a5 were used instead of the above-described releasable laminated film.
6) Evaluation of
The evaluation results of the crack resistance of the produced polarizing plate are shown in table 1.
(crack resistance)
The polarizing plate was cut into a size of 12 inches with a thomson blade, conditioned at 25 ℃ and 50% RH for 24 hours, and then bonded to glass (elastic modulus 70GPa) via an adhesive (elastic modulus 0.2MPa) applied to the surface of the polarizing plate on the optical film side.
[ Dry conditions ] Next, the temperature was increased to 80 ℃ and 30% RH500hr, the temperature was returned to 25 ℃ and 55% RH, and the occurrence of cracks was visually observed and evaluated according to the following criteria.
[ HS Condition ] Next, the sample was put into a thermal shock tester (TSA series of cold and thermal shock tests, manufactured by ESPEC CORP) at-70 ℃ to 40 ℃ and left at-70 ℃ for 30 minutes, and then the temperature was instantaneously raised to 40 ℃ for 1 cycle. After 150 cycles of the test, the test was returned to 25 ℃ and 55% RH, and the occurrence of cracks was visually observed and evaluated according to the following criteria.
A: no cracking occurred.
B: a crack slightly visually recognizable in the vicinity of the end face of the polarizer chip was generated.
C: more than 1 through-polarizing plate chip was broken. A practical, unproblematic reference is the reference A, B.
7) Evaluation of mounting to liquid Crystal display device (mounting to IPS type liquid Crystal display device)
Instead of the front-side polarizing plate and the rear-side polarizing plate of the IPS mode liquid crystal television (ultra-thin 55-type liquid crystal television having a gap between a backlight and a cell of 0.5mm), the polarizing plate produced above was bonded to the liquid crystal cell via an adhesive (elastic modulus of 0.2MPa) so that the optical film side was disposed on the liquid crystal cell side. The obtained liquid crystal television was visually observed to evaluate the light unevenness. (light leakage level at 60 ℃ polar Angle of Tilt Direction)
A: light leakage was not visually recognized in an environment of 100lx illuminance
B: light leakage was slightly visually recognized in an environment of 100lx illuminance
C: light leakage was visually recognized under an environment of 100lx illuminance
D: in an environment with an illuminance of 100lx, clear light leakage and uneven light amount were visually recognized.
A practical, unproblematic reference is the reference A, B, C.
[ Table 1]
As is clear from table 1 above, the polarizing plates of the examples had good crack resistance and excellent display performance.
Industrial applicability
According to the present invention, it is possible to provide a thin polarizing plate having excellent crack resistance even under an environment of high temperature or thermal shock and excellent display performance when mounted on a display device, and a display device.
While the present invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be added thereto without departing from the spirit and scope thereof.
The present application is based on Japanese patent application No. 1/29 in 2020 (Japanese patent application No. 2020-.
Claims (4)
1. A polarizing plate comprising at least a polarizer and an optical film,
the polarizer is laminated directly to the optical film or via an adhesive,
the optical film has a film thickness of 0.1 to 10 μm, a tensile strength of 50 to 1000MPa, and an absolute value of retardation Rth in the thickness direction of 25nm or less.
2. The polarizing plate according to claim 1,
the moisture absorption rate of the matrix material constituting the optical film is 2.0 mass% or less.
3. A display device comprising the optical film contained in the polarizing plate according to claim 1 or 2, wherein an adhesive layer is laminated on a surface of the optical film opposite to the polarizer, and a substrate is further laminated thereon,
the elastic modulus of the bonding layer is 0.01-100 MPa,
the elastic modulus of the substrate is 6 GPa-100 GPa.
4. A display device comprising the polarizing plate of claim 1 or 2.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
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| JP2020012849 | 2020-01-29 | ||
| JP2020-012849 | 2020-01-29 | ||
| JP2020069974 | 2020-04-08 | ||
| JP2020-069974 | 2020-04-08 | ||
| JP2020089716 | 2020-05-22 | ||
| JP2020-089716 | 2020-05-22 | ||
| JP2020106310 | 2020-06-19 | ||
| JP2020-106310 | 2020-06-19 | ||
| PCT/JP2021/003113 WO2021153696A1 (en) | 2020-01-29 | 2021-01-28 | Polarizing plate and display device |
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|---|---|---|---|---|
| CN101276089A (en) * | 2007-03-30 | 2008-10-01 | 富士胶片株式会社 | Liquid crystal display |
| JP2017078840A (en) * | 2015-10-22 | 2017-04-27 | 株式会社巴川製紙所 | Protective film, film laminate and polarizing plate |
| CN108474895A (en) * | 2016-01-05 | 2018-08-31 | 富士胶片株式会社 | Polarizing film and liquid crystal display device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2002365624A (en) | 2001-06-04 | 2002-12-18 | Matsushita Electric Ind Co Ltd | Manufacturing method and manufacturing device for liquid crystal display element |
| JP2003207624A (en) | 2002-01-10 | 2003-07-25 | Fuji Photo Film Co Ltd | Circularly polarizing plate and liquid crystal display device |
| JP2004020827A (en) * | 2002-06-14 | 2004-01-22 | Fuji Photo Film Co Ltd | Circularly polarizing plate and its manufacturing method, and liquid crystal display |
| JP2007176982A (en) | 2005-12-27 | 2007-07-12 | Toray Ind Inc | Method for producing acrylic film and acrylic film produced thereby |
| JP2009069720A (en) | 2007-09-18 | 2009-04-02 | Fujifilm Corp | Image display device |
| JP5825619B2 (en) | 2009-09-18 | 2015-12-02 | 綜研化学株式会社 | Adhesive composition for optical film and optical film using the same |
| JP2012018360A (en) | 2010-07-09 | 2012-01-26 | Jsr Corp | Polarizer protective film and display device including the same |
| JP5535167B2 (en) | 2011-10-04 | 2014-07-02 | 学校法人慶應義塾 | Optical film and liquid crystal display device including the same |
| TWI645010B (en) * | 2014-03-17 | 2018-12-21 | 日商住友化學股份有限公司 | Resin film with adhesive and optical laminate using the same |
| JP6327222B2 (en) | 2014-09-30 | 2018-05-23 | 住友化学株式会社 | Polarizing plate, polarizing plate with adhesive, and liquid crystal display device |
| JP2016155320A (en) | 2015-02-25 | 2016-09-01 | 三菱樹脂株式会社 | Production method of film, and film obtained therefrom |
| JP6600618B2 (en) | 2016-02-05 | 2019-10-30 | 富士フイルム株式会社 | Laminated body and liquid crystal display device |
| JP2019035019A (en) * | 2017-08-14 | 2019-03-07 | 三菱ケミカル株式会社 | (meth)acrylic resin composition, (meth)acrylic optical film, and polarizing plate |
| JP7180617B2 (en) | 2018-02-05 | 2022-11-30 | 三菱瓦斯化学株式会社 | Polyimide resin composition and polyimide film |
| JP2019197181A (en) * | 2018-05-11 | 2019-11-14 | 住友化学株式会社 | Polarizing plate and display device |
| KR20200141490A (en) | 2018-05-15 | 2020-12-18 | 후지필름 가부시키가이샤 | Polarizing plate and its manufacturing method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101276089A (en) * | 2007-03-30 | 2008-10-01 | 富士胶片株式会社 | Liquid crystal display |
| JP2017078840A (en) * | 2015-10-22 | 2017-04-27 | 株式会社巴川製紙所 | Protective film, film laminate and polarizing plate |
| CN108474895A (en) * | 2016-01-05 | 2018-08-31 | 富士胶片株式会社 | Polarizing film and liquid crystal display device |
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