WO2022220177A1 - Plaque polarisante, stratifié et dispositif d'affichage - Google Patents

Plaque polarisante, stratifié et dispositif d'affichage Download PDF

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Publication number
WO2022220177A1
WO2022220177A1 PCT/JP2022/017098 JP2022017098W WO2022220177A1 WO 2022220177 A1 WO2022220177 A1 WO 2022220177A1 JP 2022017098 W JP2022017098 W JP 2022017098W WO 2022220177 A1 WO2022220177 A1 WO 2022220177A1
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Prior art keywords
formula
group
protective film
resin
film
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PCT/JP2022/017098
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English (en)
Japanese (ja)
Inventor
ボラム 片
雅明 筒渕
▲ビョン▼▲フン▼ 宋
柱烈 張
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住友化学株式会社
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Priority to KR1020237029533A priority Critical patent/KR20230169078A/ko
Priority to CN202280028080.4A priority patent/CN117120897A/zh
Publication of WO2022220177A1 publication Critical patent/WO2022220177A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • 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
    • G02B5/3083—Birefringent or phase retarding 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation

Definitions

  • the present invention relates to a polarizing plate, a laminate, and a display device.
  • Patent Document 1 describes a laminate for a flexible image display device, in which an optical laminate including a polarizing film and a window are bonded with an adhesive layer.
  • a window is a member that constitutes the outermost surface of the display device. Conventionally, glass has been used for the front plate.
  • Patent Document 2 proposes replacing the front plate with a resin film.
  • Patent Document 3 Japanese National Publication of International Patent Application No. 2008-529038 (Patent Document 3) describes a polarizing plate.
  • This polarizing plate has a cycloolefin polymer film laminated on one side of a polarizer and a cellulose acylate film laminated on the other side of the polarizer.
  • a protective film and a polarizer, The polarizer and the protective film are adjacent to each other, A polarizing plate in which the protective film has a yield strain of 4.0% or more when a tensile test is performed at a speed of 100 mm/min.
  • the protective film has a thickness direction retardation value Rth of 200 nm or more.
  • the polarizing plate which is hard to produce a dent in a screen is provided. Further, according to the present invention, a laminate and a display device having such a polarizing plate are provided.
  • a polarizing plate includes a protective film and a polarizer.
  • the polarizer and protective film are adjacent.
  • the polarizing plate can further comprise a retardation film, other protective films, an adhesive layer, and the like, which will be described later.
  • "Adjacent" means adjacent and in contact, i.e., there is nothing between the polarizer and the protective film, as well as being in a neighboring relationship, i.e., the polarizer and the protective film. is arranged via a thin layer (for example, a layer having a thickness of 10 ⁇ m or less) such as an adhesive layer or an alignment film.
  • a polarizing plate 10 in FIG. 1 includes a protective film 12 and a polarizer 11 .
  • the polarizer 11 and the protective film 12 are bonded together with an adhesive layer 13 .
  • Polarizing plate 20 in FIG. 2 includes protective film 22 , polarizer 21 and protective film 24 .
  • the polarizer 21 and the protective film 22 are bonded together with an adhesive layer 23 .
  • the polarizer 21 and protective film 24 are bonded together with an adhesive layer 25 .
  • the polarizer 20 comprises protective films 22, 24 on both sides of the polarizer 21, respectively.
  • a polarizing plate 30 in FIG. 3 includes a protective film 32 , a polarizer 31 and a retardation film 35 .
  • the polarizer 31 and the protective film 32 are bonded with an adhesive layer 33 .
  • the polarizer 31 and the retardation film 35 are laminated with an adhesive layer 34 .
  • the polarizing plate 30 can be a so-called circular polarizing plate. In this specification, a circularly polarizing plate, an elliptically polarizing plate, and the like may be simply referred to as a polarizing plate.
  • the thickness of the polarizing plate is not particularly limited because it varies depending on the functions required of the polarizing plate, the application of the polarizing plate, and the like.
  • the thickness of the polarizing plate is, for example, 10 ⁇ m or more and 500 ⁇ m or less, preferably 20 ⁇ m or more and 200 ⁇ m or less, and more preferably 30 ⁇ m or more and 100 ⁇ m or less.
  • the planar shape of the polarizing plate may be, for example, a square shape, preferably a square shape having long sides and short sides, more preferably a rectangle.
  • the length of the long side may be, for example, 10 mm or more and 1400 mm or less, preferably 50 mm or more and 600 mm or less.
  • the length of the short side is, for example, 5 mm or more and 800 mm or less, preferably 30 mm or more and 500 mm or less, and more preferably 50 mm or more and 300 mm or less.
  • Each layer constituting the polarizing plate may have rounded corners, notched edges, or perforated edges.
  • a polarizer has a function of selectively transmitting linearly polarized light in one direction from non-polarized light such as natural light.
  • the polarizer comprises a stretched film or stretched layer to which a dichroic dye is adsorbed, a cured product of a polymerizable liquid crystal compound and a dichroic dye, and the dichroic dye is dispersed in the cured product of the polymerizable liquid crystal compound, It can be an oriented liquid crystal layer or the like.
  • a dichroic dye is a dye that has different absorbances in the long-axis direction and the short-axis direction of the molecule.
  • a polarizing plate using a liquid crystal layer as a polarizer is preferred because there is no limitation in the bending direction compared to a stretched film or stretched layer to which a dichroic dye is adsorbed.
  • a polarizer which is a stretched film or stretched layer to which a dichroic dye is adsorbed, is usually produced by a process of uniaxially stretching a polyvinyl alcohol resin film and dyeing the polyvinyl alcohol resin film with a dichroic dye such as iodine. It can be produced through a step of adsorbing a chromatic dye, a step of treating a polyvinyl alcohol resin film on which a dichroic dye is adsorbed with an aqueous boric acid solution, and a step of washing with water after treatment with an aqueous boric acid solution.
  • the thickness of the polarizer is usually 30 ⁇ m or less, preferably 18 ⁇ m or less, more preferably 15 ⁇ m or less. Reducing the thickness of the polarizer is advantageous for thinning the polarizing plate.
  • the thickness of the polarizer is usually 1 ⁇ m or more, and may be, for example, 5 ⁇ m or more.
  • a polyvinyl alcohol-based resin is obtained by saponifying a polyvinyl acetate-based resin.
  • Polyvinyl acetate-based resins include polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate and other monomers copolymerizable therewith.
  • Other monomers copolymerizable with vinyl acetate include, for example, unsaturated carboxylic acid-based compounds, olefin-based compounds, vinyl ether-based compounds, unsaturated sulfone-based compounds, and (meth)acrylamide-based compounds having an ammonium group.
  • (meth)acrylic means either acrylic or methacrylic.
  • (Meth) such as (meth)acrylate has the same meaning.
  • the degree of saponification of the polyvinyl alcohol resin is generally about 85 mol % or more and 100 mol % or less, preferably 98 mol % or more.
  • the polyvinyl alcohol-based resin may be modified, and aldehyde-modified polyvinyl formal, polyvinyl acetal, and the like can also be used.
  • the degree of polymerization of the polyvinyl alcohol resin is usually 1000 or more and 10000 or less, preferably 1500 or more and 5000 or less.
  • a polarizer which is a stretched layer to which a dichroic dye is adsorbed, is usually produced by applying a coating solution containing the polyvinyl alcohol resin onto a base film, uniaxially stretching the resulting laminated film, and uniaxially stretching.
  • a base film used to form a polarizer may be used as a protective film for the polarizer. If necessary, the base film may be peeled off from the polarizer.
  • the material and thickness of the base film may be the same as the material and thickness of the resin film described below.
  • a polarizer which is a stretched film or stretched layer to which a dichroic dye is adsorbed, may be used as a polarizing plate as it is, or may be laminated with a protective film described later on one or both sides thereof.
  • a resin film which will be described later, can be used as the protective film.
  • the polymerizable liquid crystal compound used for forming the liquid crystal layer is a compound having a polymerizable reactive group and exhibiting liquid crystallinity.
  • the polymerizable reactive group is a group that participates in a polymerization reaction, and is preferably a photopolymerizable reactive group.
  • a photopolymerizable reactive group refers to a group that can participate in a polymerization reaction by an active radical generated from a photopolymerization initiator, an acid, or the like.
  • Photopolymerizable functional groups include vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group and oxetanyl group. Among them, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group and an oxetanyl group are preferred, and an acryloyloxy group is more preferred.
  • the type of polymerizable liquid crystal compound is not particularly limited, and rod-like liquid crystal compounds, discotic liquid crystal compounds, and mixtures thereof can be used.
  • the liquid crystallinity of the polymerizable liquid crystal compound may be thermotropic liquid crystal or lyotropic liquid crystal.
  • the phase-ordered structure may be a nematic liquid crystal or a smectic liquid crystal.
  • Dichroic dyes used in polarizers which are liquid crystal layers, preferably have a maximum absorption wavelength ( ⁇ MAX) in the range of 300 to 700 nm.
  • dichroic dyes include acridine dyes, oxazine dyes, cyanine dyes, naphthalene dyes, azo dyes, and anthraquinone dyes, among which azo dyes are preferred.
  • azo dyes include monoazo dyes, bisazo dyes, trisazo dyes, tetrakisazo dyes, and stilbene azo dyes, and preferably bisazo dyes and trisazo dyes.
  • Dichroic dyes may be used alone or in combination of two or more, preferably in combination of three or more. In particular, it is more preferable to combine three or more azo compounds.
  • a part of the dichroic dye may have a reactive group and may have liquid crystallinity.
  • a polarizer which is a liquid crystal layer, is obtained by, for example, coating an alignment film formed on a substrate film with a polarizer-forming composition containing a polymerizable liquid crystal compound and a dichroic dye, and polymerizing the polymerizable liquid crystal compound. It can be formed by curing.
  • a polarizer may be formed by coating a polarizer-forming composition on a substrate film to form a coating film, and stretching the coating film together with the substrate film.
  • a base film used to form a polarizer may be used as a protective film for the polarizer. The material and thickness of the base film may be the same as the material and thickness of the resin film described below.
  • a polarizer-forming composition containing a polymerizable liquid crystal compound and a dichroic dye, and a method for producing a polarizer using this composition are disclosed in JP-A-2013-37353, JP-A-2013-33249, JP-A-2013-33249, JP-A-2013-33249, Examples include those described in JP-A-2017-83843.
  • the polarizer-forming composition further contains additives such as a solvent, a polymerization initiator, a cross-linking agent, a leveling agent, an antioxidant, a plasticizer, and a sensitizer, in addition to the polymerizable liquid crystal compound and the dichroic dye. You can stay. Each of these components may be used alone or in combination of two or more.
  • the polymerization initiator that may be contained in the polarizer-forming composition is a compound capable of initiating the polymerization reaction of the polymerizable liquid crystal compound. Initiators are preferred. Specifically, photopolymerization initiators capable of generating active radicals or acids by the action of light may be mentioned, and among these, photopolymerization initiators capable of generating radicals by the action of light are preferred.
  • the content of the polymerization initiator is preferably 1 part by mass or more and 10 parts by mass or less, more preferably 3 parts by mass or more and 8 parts by mass or less with respect to 100 parts by weight of the total amount of the polymerizable liquid crystal compound. Within this range, the reaction of the polymerizable group proceeds sufficiently, and the alignment state of the liquid crystal compound is easily stabilized.
  • the thickness of the polarizer which is the liquid crystal layer, is usually 10 ⁇ m or less, preferably 0.5 ⁇ m or more and 8 ⁇ m or less, and more preferably 1 ⁇ m or more and 5 ⁇ m or less.
  • the polarizer which is a liquid crystal layer, may be used as a polarizing plate without peeling off the base film, or may be used as a polarizing plate by peeling off the base film from the polarizer.
  • a polarizer which is a liquid crystal layer, may be used as a polarizing plate by laminating a protective film on one or both sides thereof. A resin film described later can be used as the protective film.
  • the polarizer which is a liquid crystal layer, may have an overcoat layer on one side or both sides of the polarizer for the purpose of protecting the polarizer.
  • the overcoat layer can be formed, for example, by applying a material (composition) for forming the overcoat layer on the polarizer.
  • Materials constituting the overcoat layer include, for example, photocurable resins and water-soluble polymers.
  • a (meth)acrylic resin, a polyvinyl alcohol resin, or the like can be used as a material for forming the overcoat layer.
  • a polarizing plate has a protective film on at least one surface of a polarizer.
  • the polarizing plate preferably has a protective film at least on the viewing side of the polarizer.
  • the polarizer and protective film are adjacent.
  • the protective film may be attached to the polarizer with an adhesive layer.
  • the polarizer and the protective film may be laminated via an alignment film.
  • a protective film having a yield strain (hereinafter sometimes referred to as yield strain) of 4.0% or more when a tensile test is performed at a rate of 100 mm/min is used.
  • the polarizing plate may be provided with a protective film having a yield strain of 4.0% or more on at least one surface of the polarizer, preferably on at least the viewing side of the polarizer.
  • the polarizing plate is provided with a protective film having a yield strain of 4.0% or more on one side of the polarizer, the other side may or may not have the protective film. good.
  • the protective film laminated on the other side may have a yield strain of 4.0% or more or less than 4.0%.
  • Yield strain means the magnitude of strain at the yield point. Yield strain is a physical property representing strain until the protective film is plastically deformed. Since the yield strain of the protective film is 4.0% or more, it is possible to restore the original shape without leaving a dent on the screen even after a large deformation. .
  • the yield strain is preferably 4.5% or more, more preferably 5.0% or more, and even more preferably 6.0% or more. Yield strain can be, for example, 10% or less.
  • the yield strain of the protective film is measured by the method described in Examples below.
  • the protective film can be a resin film.
  • Resin films include, for example, cycloolefin resin films; cellulose acetate resin films made of resins such as triacetyl cellulose and diacetyl cellulose; polyester resin films made of resins such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate; resin film; (meth)acrylic resin film; polypropylene resin film; polyamide resin film; polyimide resin film; From the viewpoint of increasing the yield strain, the protective film preferably contains at least one selected from the group consisting of polyimide resins, polyamide resins, and polyamideimide resins, and the following polyimide resins or polyamideimide resins. It is more preferable to include
  • the polyimide resin has the formula (1): [In formula (1), Y represents a tetravalent organic group, X represents a divalent organic group, and * represents a bond].
  • Polyamideimide resin is a structural unit represented by formula (1), and formula (3): [In formula (3), Z and X independently represent a divalent organic group, * represents a bond] It can be a resin having a structural unit represented by.
  • Formulas (1) and (3) will be described below, but the description of formula (1) relates to both polyimide resins and polyamideimide resins, and the description of formula (3) relates to polyamideimide resins. Regarding.
  • the structural unit represented by formula (1) is a structural unit formed by reacting a tetracarboxylic acid compound and a diamine compound.
  • the structural unit represented by formula (3) is a structural unit formed by reacting a dicarboxylic acid compound and a diamine compound. At least one of a tetracarboxylic acid compound, a diamine compound and a dicarboxylic acid compound constituting the structural unit represented by formula (1) and the structural unit represented by formula (3) is an aromatic compound (aromatic tetracarboxylic acid compounds, aromatic diamine compounds and/or aromatic dicarboxylic acid compounds).
  • Y in formula (1) represents a tetravalent organic group, preferably a tetravalent organic group having 4 to 80 carbon atoms, more preferably a tetravalent organic group having 4 to 60 carbon atoms and having a cyclic structure represents a group.
  • Cyclic structures include alicyclic structures, aromatic ring structures, and heterocyclic structures.
  • the organic group is an organic group in which a hydrogen atom in the organic group may be substituted with a substituent, and the substituent is preferably a halogen atom or a monovalent group optionally having a halogen atom.
  • hydrocarbon group for example, an alkyl group, an aryl group, etc.
  • an alkoxy group for example, an alkyl group, an aryl group, etc.
  • the number of carbon atoms in the monovalent hydrocarbon group, alkoxy group or aryloxy group which may have a halogen atom as the substituent is preferably 1 to 8.
  • the structural unit represented by formula (1) is a repeating unit, and the polyimide resin has a plurality of structural units represented by formula (1).
  • Y may be the same or different.
  • the polyimide-based resin may have one structure or two or more structures for Y in formula (1).
  • the polyimide resin or polyamideimide resin has a structural unit represented by formula (1), and as Y in formula (1), Formula (2):
  • R 1 independently represents a halogen atom or an alkyl group, alkoxy group, aryl group, or aryloxy group which may have a halogen atom
  • R 2 to R 5 are , mutually independently represent a hydrogen atom or a monovalent hydrocarbon group which may have a halogen atom
  • m independently represents an integer of 0 to 3
  • n represents an integer of 1 to 4
  • * represents a bond, provided that in at least one benzene ring having R 2 to R 5 , at least one of R 2 to R 5 represents a monovalent hydrocarbon group which may have a halogen atom.
  • the polyamideimide resin has a structural unit represented by the formula (1) and a structural unit represented by the formula (3), As Z in equation (3), equation (4′′): [In the formula (4′′), W are each independently a single bond, —O—, a diphenylmethylene group, a divalent hydrocarbon group optionally having a halogen atom, —SO 2 —, —S—, —CO—, —PO—, —PO 2 —, —N(R C1 )— or —Si(R C2 ) 2 —, wherein R C1 and R C2 independently represent a hydrogen atom or a halogen atom; represents an optionally substituted alkyl group, R 8′ independently represents an alkyl group or an alkoxy group optionally containing a halogen atom, and p′ independently represents an integer of
  • the present inventors have found that when the polyimide resin or polyamideimide resin contains a structure represented by formula (2) as Y in formula (1), and the polyamideimide resin is represented by formula (1) and a structural unit represented by formula (3), and when Z in formula (3) contains a structure represented by formula (4′′), the resulting yellow protective film It was found that the index (YI) can be easily reduced, and the yield strain can be easily increased.
  • the polyimide resin or polyamideimide resin has the structure represented by formula (2) and / or , the structure represented by the formula (4′′) is included.
  • the structure represented by formula (2) and the structure represented by formula (4′′) both have an aromatic main chain and has a substituent.Such a structure is a structure that inhibits intermolecular packing because the resin skeleton is rigid and the side chain has a substituent.Polyimide resin or polyamide By including such a structure in the imide-based resin, the protective film has a high elastic modulus and high toughness, and it is thought that the stress up to yielding becomes higher.In addition, the obtained protective film has high transparency. As a result, the protective film can achieve both excellent yield strain and excellent optical properties.
  • Each R 1 in formula (2) independently represents a halogen atom, or an alkyl group, alkoxy group, aryl group, or aryloxy group which may have a halogen atom.
  • An alkyl group, an alkoxy group, an aryl group, or an aryloxy group which may have a halogen atom is an alkyl group which may have a halogen atom, an alkoxy group which may have a halogen atom, or a halogen atom.
  • Halogen atoms include, for example, fluorine, chlorine, bromine and iodine atoms.
  • alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, 2-methyl-butyl group and 3-methylbutyl. groups, 2-ethyl-propyl groups, n-hexyl groups, and the like.
  • alkoxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, isobutoxy, tert-butoxy, pentyloxy, hexyloxy and cyclohexyloxy groups.
  • aryl groups include phenyl, tolyl, xylyl, naphthyl, and biphenyl groups.
  • the aryloxy group includes, for example, a phenoxy group, a naphthyloxy group, a biphenyloxy group and the like.
  • R 1 is each independently preferably a halogen atom, or an optionally halogen atom-containing alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, Alternatively, it represents an aryloxy group having 6 to 12 carbon atoms.
  • n in formula (2) independently represents an integer of 0 to 3; m is preferably an integer of 0 to 2, more preferably 0 or 1, still more preferably 0, from the viewpoint of easily increasing the yield strain, elastic modulus and transparency of the protective film.
  • R 2 , R 3 , R 4 and R 5 each independently represent a hydrogen atom or a monovalent hydrocarbon group which may have a halogen atom.
  • monovalent hydrocarbon groups include aromatic hydrocarbon groups, alicyclic hydrocarbon groups, and aliphatic hydrocarbon groups.
  • aromatic hydrocarbon group include aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group and biphenyl group.
  • the alicyclic hydrocarbon group includes cycloalkyl groups such as cyclopentyl group and cyclohexyl group.
  • Examples of aliphatic hydrocarbon groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, 2-methyl-butyl group, Alkyl groups such as 3-methylbutyl group, 2-ethyl-propyl group, n-hexyl, n-heptyl group, n-octyl group, tert-octyl group, n-nonyl group, n-decyl group and the like are included.
  • Halogen atoms include those described above.
  • R 2 to R 5 are each independently preferably a hydrogen atom, or an aryl group having 6 to 12 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, or a cycloalkyl group having 4 to 8 carbon atoms, or 1 to 1 carbon atoms, which may have a halogen atom. represents an alkyl group of 6. From the viewpoint of easily increasing the solubility of the resin in a solvent and easily improving the yield strain, elastic modulus and transparency of the protective film, each of R 2 to R 5 independently preferably has a hydrogen atom or a halogen atom.
  • alkyl group that may have a hydrogen atom or a halogen atom, more preferably represents a hydrogen atom or 1 to 6 alkyl groups that may have a halogen atom, more preferably a hydrogen atom or 1 to 6 that may have a halogen atom 3 represents an alkyl group.
  • At least one of R 2 to R 5 represents a monovalent hydrocarbon group optionally having a halogen atom. It is preferable from the viewpoint that it is easy to improve both the yield strain and the optical properties of the glass.
  • at least one benzene ring having R 2 to R 5 preferably has 2 to 4 of R 2 to R 5 One, more preferably three or four, still more preferably three are monovalent hydrocarbon groups which may have a halogen atom.
  • At least one of R 2 to R 5 more preferably represents a monovalent hydrocarbon group which may have a halogen atom. More preferably, at least one of R5 represents a monovalent hydrocarbon group which may have a halogen atom.
  • n in formula (2) represents an integer of 1 to 4, and from the viewpoint of easily improving the elastic modulus and transparency of the protective film and easily improving the yield strain of the protective film, n is preferably 1 to It is an integer of 3, more preferably 2 or 3, and still more preferably 2.
  • the structural unit represented by formula (1) may contain only one type of structure represented by formula (2) as Y, or may contain a plurality of types.
  • formula (2) is represented by formula (2′): [In formula (2′), * represents a bond] is represented by That is, the polyimide-based resin or polyamide-imide-based resin preferably contains a structure represented by formula (2′) as Y in formula (1).
  • the polyimide-based resin or polyamide-imide-based resin contains the structure represented by the formula (2′) as Y in the formula (1), the yield strain, elastic modulus, and transparency of the protective film are likely to be improved.
  • the polyimide-based resin or polyamide-imide-based resin includes a structure represented by formula (2) as Y in formula (1)
  • formula (1 ) in which Y is a structure represented by formula (2) (preferably formula (2')) is the total molar amount (100 mol%) of the structural units represented by formula (1) , preferably 30 mol% or more, more preferably 35 mol% or more, still more preferably 40 mol% or more, usually 100 mol% or less, preferably 90 mol% or less, more preferably 80 mol% or less, More preferably, it is 70 mol % or less.
  • the proportion of the structural unit represented by Y is the formula (2) is at least the above lower limit, the yield strain and elastic modulus of the protective film are likely to be increased. Moreover, it is easy to raise the breaking strain and transparency of a protective film as it is below said upper limit.
  • the ratio of structural units in which Y is represented by formula (2) can be measured using, for example, 1 H-NMR, or can be calculated from the charging ratio of raw materials.
  • the tetravalent organic group for Y in the above formula (1) includes formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), Formula (26), Formula (27), Formula (28) and Formula (29): The structure represented by is mentioned.
  • W 1 is a single bond, -O-, a diphenylmethylene group, a divalent hydrocarbon group optionally having a halogen atom (eg - CH 2 -, -CH 2 -CH 2 -, -CH(CH 3 )-, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -), -Ar-, -SO 2 -, -S -, -CO-, -PO-, -PO 2 -, -N(R W1 )-, -Si(R W2 ) 2 -, -O-Ar-O-, -Ar-O-Ar-, -Ar represents -CH 2 -Ar-, -Ar-C(CH 3 ) 2 -Ar-, or -Ar-SO 2 -Ar-.
  • a halogen atom eg - CH 2 -, -CH 2 -CH 2 -,
  • Ar represents an arylene group having 6 to 20 carbon atoms which may have a fluorine atom, and specific examples thereof include a phenylene group.
  • R W1 and R W2 each independently represent a hydrogen atom or an alkyl group which may have a halogen atom.
  • the hydrogen atoms on the rings in formulas (20) to (29) are substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. good too.
  • Examples of the alkyl group having 1 to 6 carbon atoms, the alkoxy group having 1 to 6 carbon atoms and the aryl group having 6 to 12 carbon atoms include those exemplified above as R 1 in formula (2).
  • W 1 is preferably a single bond, —O—, —CH 2 —, —CH 2 —CH 2 —, —, from the viewpoint of easily improving the yield strain, breaking strain, elastic modulus and transparency of the protective film.
  • Polyimide-based resin or polyamideimide-based resin in the embodiment containing the structure represented by the formula (2) as Y in the formula (1), the polyimide-based resin or polyamideimide-based resin is represented by the formula (1)
  • the structural unit Y is represented by formula (2)
  • Y in formula (1) further has a structural unit represented by formula (26), the yield strain of the protective film is more likely to be improved. preferable from this point of view.
  • Formula (26) is preferably represented by formula (5):
  • B is a single bond, -O-, a diphenylmethylene group, a divalent hydrocarbon group optionally having a halogen atom, -SO 2 -, -S-, -CO-, - represents COO-, -PO-, -PO 2 -, -N(R B1 )- or -Si(R B2 ) 2 -, wherein R B1 and R B2 each independently have a hydrogen atom or a halogen atom; R 7 independently represents a halogen atom or an alkyl group, alkoxy group, aryl group, or aryloxy group which may have a halogen atom; t each represents independently represents an integer from 0 to 3, * represents a bond] is represented by
  • Y in the formula (1) is a structural unit represented by the formula (5) in the polyimide-based resin or polyamideimide
  • R 7 in formula (5) independently represents a halogen atom, or an alkyl group, alkoxy group, aryl group, or aryloxy group which may have a halogen atom.
  • the halogen atom and the alkyl group, alkoxy group, aryl group and aryloxy group which may have a halogen atom include those exemplified above as R 1 in formula (2).
  • R 7 is each independently preferably an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, and more It preferably represents an alkyl group having 1 to 3 carbon atoms which may have a halogen atom.
  • t in (5) independently represents an integer of 0 to 3, and is preferably an integer of 0 to 2 from the viewpoint of easily improving the yield strain, breaking strain, elastic modulus and transparency of the protective film. , more preferably 0 or 1, more preferably 0.
  • B in formula (5) is a single bond, —O—, a diphenylmethylene group, a divalent hydrocarbon group optionally having a halogen atom, —SO 2 —, —S—, —CO—, —COO -, -PO-, -PO 2 -, -N(R B1 )- or -Si(R B2 ) 2 -, wherein R B1 and R B2 each independently have a hydrogen atom or a halogen atom; represents an alkyl group that may be
  • a hydrogen atom is further Divalent groups excluding one are included.
  • a divalent hydrocarbon group which may have a halogen atom forms a ring in place of two hydrogen atoms among the hydrogen atoms contained in the group, i.e., the two hydrogen atoms are replaced as a bond, The two bonds may be linked to form a ring, and examples of the ring include a cycloalkane ring having 3 to 12 carbon atoms.
  • the alkyl group optionally substituted with a halogen atom for R B1 and R B2 in —N(R B1 )— and —Si(R B2 ) 2 — contained in B in formula (5) includes:
  • Examples of the alkyl group optionally having a halogen atom for R 1 in formula (2) include those exemplified above.
  • B in formula (5) is preferably a single bond or a divalent hydrocarbon optionally having a halogen atom from the viewpoint of easily improving the yield strain, breaking strain, elastic modulus and transparency of the protective film.
  • a group more preferably a single bond, -CH 2 -, -CH 2 -CH 2 -, -CH(CH 3 )-, -C(CH 3 ) 2 - or -C(CF 3 ) 2 - , more preferably a single bond, —C(CH 3 ) 2 — or —C(CF 3 ) 2 —, even more preferably a single bond or —C(CF 3 ) 2 —, particularly preferably —C (CF 3 ) 2 -.
  • Equation (5) is derived from Equation (5′): [in formula (5′), * represents a bond] is preferably represented by That is, it is preferable that the polyimide-based resin or polyamide-imide-based resin has at least a part of the structural units represented by the formula (1) in which Y has a structural unit represented by the formula (5′). In this case, the yield strain, transparency, elastic modulus and flex resistance of the protective film are likely to be improved.
  • Polyimide-based resin or polyamideimide-based resin when Y in formula (1) contains a structural unit represented by formula (5), among the structural units represented by formula (1), in formula (1)
  • the ratio of structural units in which Y is a structure represented by formula (5), preferably formula (5′), is based on the total molar amount (100 mol%) of the structural units represented by formula (1). , preferably 30 mol% or more, more preferably 35 mol% or more, still more preferably 40 mol% or more, preferably 90 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less .
  • the proportion of the structural unit represented by Y is the formula (5) is at least the above lower limit, the solubility of the resin in the solvent and the transparency of the protective film are likely to be improved. Moreover, it is easy to raise the yield strain and elastic modulus of a protective film as it is below said upper limit.
  • the ratio of structural units in which Y in formula (1) is represented by formula (5) can be measured using 1 H-NMR, for example, or can be calculated from the charging ratio of raw materials.
  • Y in formula (1) is a structural unit represented by formula (2), and Y in formula (1) contains a structural unit represented by formula (5)
  • the total ratio of the structural unit Y is represented by formula (2) and the structural unit Y is represented by formula (5) is based on the total molar amount of the structural units represented by formula (1) is preferably 50 mol % or more, more preferably 70 mol % or more, still more preferably 90 mol % or more, and usually 100 mol % or less.
  • the total ratio can be measured using, for example, 1 H-NMR, or can be calculated from the charging ratio of raw materials.
  • X in formula (1) represents a divalent organic group, preferably a divalent organic group having 4 to 40 carbon atoms.
  • Polyimide resin or polyamideimide resin from the viewpoint of easily improving the yield strain, breaking strain, elastic modulus and transparency of the protective film, as X in formula (1), a divalent aromatic group, divalent It preferably contains at least one of an alicyclic group and a divalent aliphatic group, and more preferably contains a divalent aromatic group.
  • the divalent aromatic group for example, among the hydrogen atoms in the monovalent aromatic hydrocarbon groups exemplified above as R 2 to R 5 in formula (2), one hydrogen atom is replaced with a bond.
  • divalent aromatic hydrocarbon group groups in which at least one or more of the divalent aromatic hydrocarbon groups are linked by a linking group, for example, a linking group such as V1 described later.
  • a linking group for example, a linking group such as V1 described later.
  • the divalent alicyclic group for example, among the hydrogen atoms in the monovalent alicyclic hydrocarbon groups exemplified above as R 2 to R 5 in formula (2), one hydrogen atom is a bond a divalent alicyclic hydrocarbon group substituted with; among the divalent alicyclic hydrocarbon groups, groups in which at least one or more of the divalent alicyclic hydrocarbon groups are linked by a linking group, for example, a linking group such as V1 described later. be done.
  • divalent aliphatic group for example, among the hydrogen atoms in the monovalent aliphatic hydrocarbon groups exemplified above as R 2 to R 5 in formula (2), one hydrogen atom is replaced with a bond. divalent aliphatic hydrocarbon group; groups in which at least one or more of the divalent aliphatic hydrocarbon groups are linked by a linking group such as V1 described later.
  • X in formula (1) preferably represents a divalent organic group having 4 to 40 carbon atoms having a cyclic structure (alicyclic structure, aromatic ring structure, heterocyclic structure, etc.), more preferably 4 to It represents a 40 divalent aromatic group or a C4-40 divalent alicyclic group, more preferably a C4-40 divalent aromatic group.
  • a hydrogen atom in the organic group may be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group.
  • the number is preferably 1-8.
  • the polyimide resin or polyamideimide resin may contain multiple types of X, and the multiple types of X may be the same or different.
  • X is represented by formula (10), formula (11), formula (12), formula (13), formula (14), formula (15), formula (16), formula (17) and formula (18) groups represented by formulas (10) to (18) in which hydrogen atoms are substituted with methyl, fluoro, chloro or trifluoromethyl groups.
  • the hydrogen atoms on the rings in formulas (10) to (18) are substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. good too.
  • Examples of the alkyl group having 1 to 6 carbon atoms, the alkoxy group having 1 to 6 carbon atoms and the aryl group having 6 to 12 carbon atoms include those exemplified above as R 1 in formula (2).
  • V 1 , V 2 and V 3 are each independently a single bond, -O-, -S-, -CH 2 -, -CH 2 represents -CH 2 -, -CH(CH 3 )-, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -SO 2 -, -CO- or -N(Q)-.
  • Q represents a monovalent hydrocarbon group having 1 to 12 carbon atoms which may have a halogen atom.
  • the above monovalent hydrocarbon group which may have a halogen atom for R 2 to R 5 in formula (2) are exemplified.
  • V 1 and V 3 are a single bond, -O- or -S- and V 2 is -CH 2 -, -C(CH 3 ) 2 -, -C(CF 3 ) 2- or -SO 2 -.
  • the bonding positions of V 1 and V 2 to each ring and the bonding positions of V 2 and V 3 to each ring independently of each other are preferably meta-positions or para-positions, and more Para position is preferred.
  • A is a single bond, -O-, a diphenylmethylene group, a divalent hydrocarbon group optionally having a halogen atom, -SO 2 -, -S-, -CO-, - represents PO-, -PO 2 -, -N(R A1 )- or -Si(R A2 ) 2 -, wherein R A1 and R A2 may independently have a hydrogen atom or a halogen atom; represents an alkyl group, R 6 independently represents a halogen atom, or an alkyl group, alkoxy group, aryl group, or aryloxy group which may have a halogen atom; s independently represents 0 to represents an integer of 4 and * represents a bond].
  • Polyimide-based resin or polyamideimide-based resin when X in the formula (1) has a structural unit represented by the formula (6), the yield strain of the protective film, breaking strain, elastic modulus and transparency are likely to be improved.
  • the polyimide-based resin or polyamide-imide-based resin may contain one or more groups represented by the formula (6) as X in the structural unit represented by the formula (1).
  • Each R 6 in formula (6) independently represents a halogen atom, or an alkyl group, alkoxy group, aryl group, or aryloxy group which may have a halogen atom.
  • Examples of the halogen atom, or the alkyl group, alkoxy group, aryl group, or aryloxy group which may have a halogen atom include those exemplified above as R 1 in formula (2).
  • R 6 is each independently preferably an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms. It represents a halogenated alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms or a fluoroalkyl group having 1 to 6 carbon atoms (preferably a perfluoroalkyl group).
  • R 6 independently of one another represents a methyl group, a chloro group or a trifluoromethyl group.
  • s independently represents an integer of 0 to 4, preferably an integer of 1 to 3, more preferably 1 or 2 from the viewpoint of easily improving the yield strain, breaking strain, elastic modulus and transparency of the protective film , and more preferably 1.
  • s is 1, R 6 is substituted ortho to -A-, and R 6 is methyl, fluoro, chloro or trifluoro A methyl group is preferred.
  • the positions of the bonds are independent of each other, based on -A-, preferably meta-position or para-position. position, more preferably para position.
  • a in formula (6) is a single bond, —O—, a diphenylmethylene group, a divalent hydrocarbon group optionally having a halogen atom, —SO 2 —, —S—, —CO—, —PO -, -PO 2 -, -N(R A1 )- or -Si(R A2 ) 2 -, wherein R A1 and R A2 are independently of each other alkyl optionally having a hydrogen atom or a halogen atom represents a group.
  • the divalent hydrocarbon group which may have a halogen atom among the monovalent hydrocarbon groups which may have a halogen atom in R 2 to R 5 in formula (2), one hydrogen atom divalent groups other than A divalent hydrocarbon group which may have a halogen atom may form a ring in place of two hydrogen atoms among the hydrogen atoms contained in the group, i.e., the two hydrogen atoms are bonded Instead of the hand, the two bonds may be linked to form a ring.
  • the ring includes, for example, a cycloalkane ring having 3 to 12 carbon atoms.
  • Examples of the alkyl group optionally having a halogen atom represented by R A1 and R A2 include those exemplified above as the alkyl group optionally having a halogen atom for R 1 in formula (2). .
  • a in formula (6) is preferably a single bond, —CH 2 —, —CH 2 —CH 2 —, —CH, from the viewpoint of easily improving the yield strain, breaking strain, elastic modulus and transparency of the protective film.
  • R 6 is each independently a C 1-6 represents a halogenated alkyl group, s represents 1 or 2, and A preferably represents a single bond, -C(CH 3 ) 2 - or -C(CF 3 ) 2 -.
  • Formula (6) is preferably represented by formula (6′): is represented by That is, at least some of the plurality of X's in Formula (1) are preferably represented by Formula (6'). Such a form tends to improve yield strain, breaking strain, elastic modulus and transparency of the protective film.
  • the ratio of structural units in which X in formula (1) is a structure represented by formula (6) is the total number of structural units represented by formula (1).
  • the molar amount (100 mol %) is preferably 50 mol % or more, more preferably 70 mol % or more, still more preferably 80 mol % or more, and usually 100 mol % or less.
  • the proportion of the structural unit represented by formula (6) for X is at least the above lower limit, the transparency of the protective film can be more easily improved. Moreover, it is easy to raise the yield strain of a protective film as it is below said upper limit.
  • the ratio of structural units in which X in formula (1) is represented by formula (6) can be measured, for example, using 1 H-NMR, or can be calculated from the charging ratio of raw materials.
  • Polyamideimide resin as described above, in addition to the structural unit represented by formula (1), formula (3): It can have a structural unit represented by
  • Z in formula (3) represents a divalent organic group, preferably a hydrocarbon group having 1 to 8 carbon atoms or a fluorine-substituted hydrocarbon group having 1 to 8 carbon atoms.
  • Cyclic structures include alicyclic structures, aromatic ring structures, and heterocyclic structures.
  • the divalent organic group having an alicyclic structure and an aromatic ring structure includes a group in which two non-adjacent bonds of the groups represented by the above formulas (20) to (29) are replaced with hydrogen atoms, and divalent chain hydrocarbon groups having 6 or less carbon atoms.
  • a divalent organic group having a heterocyclic structure includes a group having a thiophene ring skeleton. From the viewpoint of easily reducing the YI value of the protective film, among the bonds of the groups represented by formulas (20) to (29), two non-adjacent bonds are replaced with hydrogen atoms, and it has a thiophene ring skeleton. groups are preferred.
  • a divalent organic group represented by is more preferable.
  • the hydrogen atoms on the rings in formulas (20) to (29) and formulas (20') to (29') are alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, or It may be substituted with an aryl group having 6 to 12 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms, the alkoxy group having 1 to 6 carbon atoms and the aryl group having 6 to 12 carbon atoms include those exemplified above as R 1 in formula (2).
  • Polyamideimide resin is represented by formula (4) as Z in formula (3):
  • W are each independently a single bond, -O-, a diphenylmethylene group, a divalent hydrocarbon group optionally having a halogen atom, -SO 2 -, -S-, - represents CO—, —PO—, —PO 2 —, —N(R C1 )— or —Si(R C2 ) 2 —, wherein R C1 and R C2 each independently have a hydrogen atom or a halogen atom; R 8 independently represents an alkyl group, an alkoxy group, an aryl group, or an aryloxy group which may have a halogen atom or a halogen atom; independently represents an integer of 0 to 4, q represents an integer of 0 to 4, * represents a bond] can include structures represented by When the polyamide-imide resin has a structural unit represented by formula (3) in which Z is formula (4), the yield strain, breaking
  • the bonding positions of W are independent of each other, preferably meta-position or para-position based on the bond. and more preferably at the para position.
  • Equation (4) is derived from Equation (4′): [In formula (4′), W, R 8 , p and q are as defined in formula (4)] is preferably represented by In other words, Z in formula (3) is preferably represented by formula (4′) in at least part of the structural units represented by formula (3) that may be contained in the polyamideimide resin. In this case, the yield strain, breaking strain, elastic modulus and transparency of the protective film are likely to be improved.
  • R 8 independently represents a halogen atom, or an alkyl group, alkoxy group, aryl group, or aryloxy group which may have a halogen atom.
  • examples of the halogen atom, or the alkyl group, alkoxy group, aryl group, or aryloxy group which may have a halogen atom include those exemplified above as R 1 in formula (2).
  • R 8 is independently of each other, from the viewpoint of easily improving the yield strain, breaking strain, elastic modulus and transparency of the protective film, preferably it may have a halogen atom, and has 1 to 6 carbon atoms. It represents an alkyl group or an alkoxy group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. Each p independently represents an integer of 0 to 4, preferably an integer of 0 to 2 from the viewpoint of easily improving the yield strain, breaking strain, elastic modulus and transparency of the protective film.
  • W in formulas (4) and (4′) is independently a single bond, —O—, a diphenylmethylene group, a divalent hydrocarbon group optionally having a halogen atom, —SO 2 —, —S—, —CO—, —PO—, —PO 2 —, —N(R C1 )—, or —Si(R C2 ) 2 —, and the yield strain, breaking strain, elastic modulus and transparency of the protective film From the viewpoint of facilitating improvement, preferably -O- or -S-, more preferably -O-.
  • R 1 C1 and R 2 C2 each independently represent a monovalent hydrocarbon group having 1 to 12 carbon atoms which may have a hydrogen atom or a halogen atom.
  • the monovalent hydrocarbon group having 1 to 12 carbon atoms which may have a halogen atom the above monovalent hydrocarbon group which may have a halogen atom for R 2 to R 5 in formula (2) are exemplified.
  • q in the formulas (4) and (4′) is an integer in the range of 0 to 4, and when q is within this range, the yield strain, breaking strain, elastic modulus and transparency of the protective film are improved.
  • easy to let q in formulas (4) and (4') is preferably an integer in the range of 0 to 3, more preferably an integer in the range of 0 to 2.
  • a structural unit represented by formula (4) or formula (4′) in which q is 0 is, for example, a structural unit derived from terephthalic acid or isophthalic acid, and the structural unit is represented by formula (4) or formula (4 ') in p and q are each 0, or q is 0 and p is 1 or 2 (preferably R 8 is an alkyl group having 1 to 3 carbon atoms, a fluorinated alkyl group, or a carbon number 1 to 3 alkoxy groups).
  • the polyamide-imide resin preferably contains structural units derived from terephthalic acid.
  • Z may contain one or more structural units represented by the formula (4) or (4').
  • Z is represented by formula (4)
  • the ratio of the structural units is preferably 30 mol% or more, more preferably 50 mol% or more, still more preferably 70 mol% or more, relative to the total molar amount of the structural units represented by formula (3). It is 100 mol % or less.
  • the proportion of structural units in which Z in formula (3) is represented by formula (4) can be measured, for example, using 1 H-NMR, or can be calculated from the charging ratio of raw materials.
  • the above description of preferred proportions applies equally to the structure represented by formula (4′) and the structure represented by formula (4′′).
  • Z is represented by formula (4 ) is preferably 5 mol% or more, more preferably is 15 mol % or more, more preferably 30 mol % or more, particularly preferably 50 mol % or more, and usually 100 mol % or less.
  • the proportion of the structural unit represented by formula (4) for Z in formula (3) is at least the above lower limit, the yield strain, breaking strain, elastic modulus and transparency of the light protective film are likely to be improved.
  • the proportion of structural units in which Z in formula (3) is represented by formula (4) can be measured, for example, using 1 H-NMR, or can be calculated from the charging ratio of raw materials.
  • the above description of preferred proportions applies equally to the structure represented by formula (4′) and the structure represented by formula (4′′).
  • Examples of the alkyl group having 1 to 6 carbon atoms, the alkoxy group having 1 to 6 carbon atoms and the aryl group having 6 to 12 carbon atoms in R 24 include those exemplified above as R 1 in formula (2). be done.
  • the ratio of the structural unit represented by the formula (d1) is the structural unit represented by the formula (1) and the formula (3). is preferably 0.01 mol% or more, more preferably 0.1 mol% or more, still more preferably 1 mol% or more, and preferably 30 mol% or less, based on the total molar amount of the represented structural unit; It is more preferably 20 mol % or less, still more preferably 10 mol % or less.
  • the ratio can be measured using, for example, 1 H-NMR, or can be calculated from the charging ratio of raw materials.
  • Examples of X in formula (3) include those exemplified above as X in formula (1), and preferred forms are also the same. Moreover, X in Formula (1) and X in Formula (3) may be the same or different. In one embodiment, the structural unit represented by formula (1) and/or the structural unit represented by formula (3) have one or more structures (or groups) represented by formula (6) as X. May contain seeds.
  • the ratio of structural units represented by formula (6) is Preferably 30 mol% or more, more preferably 50 mol% or more, still more preferably 70 mol% or more, relative to the total molar amount of the structural unit represented by 1) and the structural unit represented by formula (3) and is usually 100 mol % or less.
  • the ratio of the structural unit represented by formula (6) for X is within the above range, the yield strain, breaking strain, elastic modulus and transparency of the protective film are likely to be improved.
  • the ratio of structural units in which X is represented by formula (6) can be measured using, for example, 1 H-NMR, or can be calculated from the charging ratio of raw materials.
  • Polyamideimide resin in addition to the structural unit represented by the formula (1), the structural unit represented by the formula (3), further, the structural unit represented by the formula (30) and / or the formula (31) It may contain a structural unit represented by
  • Y 1 is a tetravalent organic group, preferably an organic group in which a hydrogen atom in the organic group may be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group.
  • Y 1 is represented by formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), formula (26), formula (27), formula (28) and a group represented by the formula (29), a group in which a hydrogen atom in the group represented by the formulas (20) to (29) is substituted with a methyl group, a fluoro group, a chloro group or a trifluoromethyl group, and A tetravalent chain hydrocarbon group having 6 or less carbon atoms is exemplified.
  • the structural unit represented by formula (30) may contain multiple types of structures represented by Y 1 , and the multiple types of Y 1 may be the same or different. good too.
  • Y 2 is a trivalent organic group, preferably an organic group in which a hydrogen atom in the organic group may be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group.
  • the structural unit represented by formula (31) may contain multiple types of structures represented by Y 2 , and the multiple types of Y 2 may be the same or different. good too.
  • X 1 and X 2 are each independently a divalent organic group, preferably a hydrocarbon group or a hydrocarbon group in which a hydrogen atom in the organic group is substituted with fluorine. is an organic group optionally substituted with As X 1 and X 2 , the above formula (10), formula (11), formula (12), formula (13), formula (14), formula (15), formula (16), formula (17) and a group represented by the formula (18); a group in which hydrogen atoms in the groups represented by the formulas (10) to (18) are substituted with a methyl group, a fluoro group, a chloro group or a trifluoromethyl group; and A chain hydrocarbon group having 6 or less carbon atoms is exemplified.
  • the total ratio of the structural units represented by the formula (1) and the structural unit represented by the formula (3) is preferably 0.01 mol% or more, and more It is preferably 0.1 mol % or more, more preferably 1 mol % or more, preferably 30 mol % or less, more preferably 20 mol % or less, still more preferably 10 mol % or less.
  • the ratio can be measured, for example, using 1 H-NMR, or can be calculated from the charging ratio of raw materials.
  • the proportion of the structural unit represented by the formula (1) is expressed by the formula (1) Preferably 10 mol% or more, more preferably 15 mol% or more, still more preferably 20 mol%, relative to the total molar amount (100 mol%) of the structural unit represented by the structural unit represented by formula (3) and the structural unit represented by formula (3)
  • the content is particularly preferably 25 mol% or more, preferably 90 mol% or less, more preferably 70 mol% or less, still more preferably 60 mol% or less, and particularly preferably 50 mol% or less.
  • the proportion of the structural unit represented by the formula (1) when the proportion of the structural unit represented by the formula (1) is at least the above lower limit, thickening due to hydrogen bonding between the amide bonds in the formula (3) is suppressed, and the polyamideimide varnish is Viscosity can be reduced and production of protective films is easy.
  • the proportion of the structural unit represented by formula (1) in the polyamideimide resin is equal to or less than the above upper limit, the protective film containing the polyamideimide resin exhibits high surface hardness.
  • the above ratio can be measured, for example, using 1 H-NMR, or can be calculated from the charging ratio of raw materials.
  • the weight average molecular weight (hereinafter sometimes referred to as Mw) of the polyimide resin or polyamideimide resin contained in the protective film is preferably 100,000 or more, more preferably 150,000 or more, and still more preferably is 200,000 or more, more preferably 300,000 or more, more preferably 400,000 or more, still more preferably 500,000 or more, still more preferably 600,000 or more, preferably It is 1,500,000 or less, more preferably 1,200,000 or less, still more preferably 1,000,000 or less, still more preferably 800,000 or less.
  • Mw of the polyimide-based resin or the polyamide-imide-based resin is at least the above lower limit, the yield strain, breaking strain and elastic modulus of the resulting protective film are likely to be improved.
  • Mw can be determined, for example, by gel permeation chromatography (hereinafter sometimes referred to as GPC) measurement and standard polystyrene conversion, for example, it can be determined by the method described in Examples.
  • GPC gel permeation chromatography
  • the polyimide-based resin or polyamide-imide-based resin may contain halogen atoms such as fluorine atoms, which can be introduced by, for example, the fluorine-containing substituents described above.
  • halogen atoms such as fluorine atoms
  • the YI value of the protective film is likely to be reduced, and the breaking strain and elastic modulus are likely to be increased.
  • the elastic modulus of the protective film is high, it is easy to suppress the occurrence of scratches, wrinkles, and the like.
  • the YI value of the protective film is low, it becomes easier to improve the transparency and visibility of the film.
  • a halogen atom is preferably a fluorine atom.
  • Preferable fluorine-containing substituents for containing fluorine atoms in the polyimide resin or polyamideimide resin include, for example, a fluoro group and a trifluoromethyl group.
  • the content thereof when the polyimide resin or polyamideimide resin contains a halogen atom, the content thereof, respectively, based on the weight of the polyimide resin or polyamideimide resin, preferably 1 to 40 mass%, more preferably 5 to 40% by mass, more preferably 5 to 30% by mass.
  • the halogen atom content is at least the above lower limit, the YI value of the protective film is likely to be reduced, and the breaking strain and elastic modulus are likely to be increased. If the content of halogen atoms is below the above upper limit, synthesis becomes easier.
  • the imidization rate of the polyimide resin or polyamideimide resin is preferably 90% or more, more preferably 93% or more, and still more preferably 96% or more. From the viewpoint of easily increasing the yield strain and optical properties of the protective film, the imidization rate is preferably at least the above lower limit. Moreover, the upper limit of the imidization rate is 100% or less.
  • the imidization rate indicates the ratio of the molar amount of imide bonds in the resin to twice the molar amount of structural units derived from the tetracarboxylic acid compound in the polyimide resin or polyamideimide resin.
  • the polyimide resin or polyamideimide resin contains a tricarboxylic acid compound
  • a value twice the molar amount of the structural unit derived from the tetracarboxylic acid compound in the polyimide resin, derived from the tricarboxylic acid compound It shows the ratio of the molar amount of imide bonds in the polyimide resin to the total molar amount of the constituent units.
  • the imidization rate can be determined by IR method, NMR method, or the like.
  • the yellowness index (hereinafter sometimes referred to as YI value) of the protective film is preferably less than 3.0.
  • YI value is 3.0 or more, the YI value of the protective film is too high, so that the visibility of an image or the like through the protective film decreases.
  • the YI value of the protective film is preferably 2.8 or less, more preferably 2.6 or less, still more preferably 2.5 or less, preferably -5 or more, more preferably -2 or more is.
  • the YI value of the protective film is equal to or less than the above upper limit, the transparency becomes good, and when applied to a protective film or a front plate described later, it can contribute to high visibility.
  • the method for adjusting the YI value of the protective film to the above range is not particularly limited, but the method of using the above-mentioned polyimide resin or polyamideimide resin, the method of adding a blue dye, the method of thinning, the monomer mainly Examples include a method of introducing a side chain into the aromatic ring of the chain.
  • the tensile elastic modulus of the protective film is preferably 4.8 GPa or more, more preferably 5, from the viewpoint of easily improving the flex resistance of the polarizing plate and the laminate and from the viewpoint of easily preventing wrinkles, scratches, and the like. .2 GPa or more, more preferably 6.0 GPa or more, and usually 100 GPa or less.
  • the tensile modulus can be measured using a tensile tester (distance between chucks: 50 mm, tensile speed: 10 mm/min).
  • a method for increasing the tensile modulus a method of adding a rigid inorganic filler and a method of introducing a crosslinked structure are known.
  • the total light transmittance of the protective film is preferably 85% or higher, more preferably 88% or higher, still more preferably 89% or higher, still more preferably 90% or higher.
  • the total light transmittance is at least the above lower limit, visibility is likely to be improved when the protective film is incorporated into a display device.
  • the upper limit of total light transmittance is usually 100% or less.
  • the total light transmittance can be measured using a haze computer according to JIS K 7361-1:1997, for example.
  • the total light transmittance may be the total light transmittance within the thickness range of the protective film, which will be described later.
  • the plane orientation coefficient ⁇ P absolute value of the protective film is preferably 0.003 or more, more preferably 0.010 or more, and may be 0.050 or more, from the viewpoint of making it difficult for dents to occur.
  • the planar orientation coefficient ⁇ P absolute value of the protective film may be 0.600 or less, or may be 0.100 or less.
  • the plane orientation coefficient ⁇ P is a physical property value that is an index of the orientation state of the molecular chains of the polymer constituting the protective film, and the larger the plane orientation coefficient, the higher the degree of orientation of the protective film.
  • the plane orientation coefficient ⁇ P is defined by n x as the refractive index in the in-plane slow axis direction of the protective film (the direction in which the refractive index is maximized in the plane), and the in-plane fast axis direction (perpendicular to the in-plane slow axis direction
  • Planar orientation coefficient ⁇ P (n x +n y )/2-n z defined by
  • the in-plane retardation value R 0 of the protective film is preferably 0 nm or more and 200 nm or less, and more preferably 0 nm or more and 100 nm or less, from the viewpoint of making it difficult for dents to occur.
  • the thickness direction retardation value R th of the protective film is preferably 200 nm or more, more preferably 1000 nm or more.
  • the thickness direction retardation value R th of the protective film may be 10000 nm or less, or may be 5000 nm or less. In this specification, the retardation value and the like may be values at a wavelength of 590 nm.
  • the in-plane retardation value R 0 and the thickness direction retardation value R th are the refractive index in the in-plane slow axis direction (the direction in which the refractive index is maximized in the plane) of the film, and the in-plane fast axis direction
  • In-plane retardation value R 0 (n x ⁇ n y ) ⁇ d
  • the thickness of the protective film is usually 100 ⁇ m or less, preferably 80 ⁇ m or less, more preferably 60 ⁇ m or less, still more preferably 40 ⁇ m or less, and even more preferably 30 ⁇ m or less.
  • the thickness of the protective film is usually 5 ⁇ m or more, preferably 10 ⁇ m or more. Within such a range, the bending resistance of the polarizing plate can be easily increased.
  • a hard coat layer may be formed on the resin film.
  • the hard coat layer may be formed on one side of the resin film, or may be formed on both sides.
  • the method for producing the polyimide resin and the polyamideimide resin is not particularly limited. In one embodiment, it can be produced using a tetracarboxylic acid compound and a diamine compound, which will be described later, as main raw materials, optionally using a dicarboxylic acid compound together.
  • a step of reacting a diamine compound and a tetracarboxylic acid compound to obtain a polyamic acid and when the polyimide resin is a polyamideimide resin, reacting the polyamic acid and a dicarboxylic acid to obtain a polyamideimide
  • It can be produced by a method including a step of obtaining a resin precursor and a step of imidizing the polyamic acid or the polyamide-imide resin precursor.
  • a tricarboxylic acid compound may be reacted.
  • the structural units represented by formulas (1) and (30) are usually derived from a diamine compound and a tetracarboxylic acid compound.
  • the structural unit represented by formula (3) is usually derived from a diamine compound and a dicarboxylic acid compound.
  • the structural unit represented by formula (31) is usually derived from a diamine compound and a tricarboxylic acid compound.
  • the tetracarboxylic acid compound used in the production of polyimide resins and polyamideimide resins has at least the formula (X): [In Formula (X), R 1 to R 5 , m and n are respectively the same as R 1 to R 5 , m and n in Formula (2)] It is preferable that the compound represented by is included.
  • the compound represented by formula (X) may be obtained by a conventional method such as reacting trimellitic anhydride or a derivative thereof with an aromatic diol, or a commercially available product may be used.
  • the tetracarboxylic acid compound in addition to the compound represented by formula (X), further has formula (Y): [in formula (Y), B, R 7 and t are respectively the same as B, R 7 and t in formula (5)] It is preferable that the compound represented by is included.
  • tetracarboxylic acid compounds include aromatic tetracarboxylic acid compounds such as aromatic tetracarboxylic dianhydride; and aliphatic tetracarboxylic acid compounds such as aliphatic tetracarboxylic dianhydride.
  • a tetracarboxylic acid compound may be used independently and may be used in combination of 2 or more type.
  • the tetracarboxylic acid compound may be a dianhydride or a tetracarboxylic acid compound analog such as an acid chloride compound.
  • aromatic tetracarboxylic dianhydrides include non-condensed polycyclic aromatic tetracarboxylic dianhydrides, monocyclic aromatic tetracarboxylic dianhydrides and condensed polycyclic aromatic tetracarboxylic dianhydrides.
  • Carboxylic acid dianhydrides are mentioned.
  • Non-condensed polycyclic aromatic tetracarboxylic dianhydrides include, for example, esters of trimellitic anhydride and 2,2',3,3',5,5'-hexamethyl-4,4'-biphenol compound (hereinafter sometimes referred to as TAHMBP), an ester of trimellitic anhydride and 2,2′,3,3′-tetramethyl-4,4′-biphenol (hereinafter referred to as TA23X-BP ), esters of trimellitic anhydride and 3,3′,5,5′-tetramethyl-4,4′-biphenol, 4,4′-oxydiphthalic dianhydride, 3,3′, 4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride (hereinafter , BPDA), 2,2′,3,
  • Examples of monocyclic aromatic tetracarboxylic dianhydrides include 1,2,4,5-benzenetetracarboxylic dianhydride [also called pyromellitic dianhydride (hereinafter referred to as PMDA). There is)], and examples of the condensed polycyclic aromatic tetracarboxylic dianhydride include 2,3,6,7-naphthalenetetracarboxylic dianhydride.
  • TAHMBP Trimellitic anhydride
  • TA23X-BP an ester of trimellitic anhydride and 3,3′,5,5′-tetramethyl-4,4′-biphenol
  • 4,4′-oxydiphthalic dianhydride BPDA, 2,2′,3,3′-biphenyltetracarboxylic dianhydride, 6FDA, bis(3,4-dicarboxyphenyl)methane dianhydride, and 4,4′-(p-phenylenedioxy)diphthalic acid dianhydrides.
  • BPDA 2,2′,3,3′-biphenyltetracarboxylic dianhydride
  • 6FDA bis(3,4-dicarboxyphenyl)methane dianhydride
  • 4,4′-(p-phenylenedioxy)diphthalic acid dianhydrides can be used singly or in combination of two or more.
  • Aliphatic tetracarboxylic dianhydrides include cyclic or acyclic aliphatic tetracarboxylic dianhydrides.
  • the cyclic aliphatic tetracarboxylic dianhydride is a tetracarboxylic dianhydride having an alicyclic hydrocarbon structure, and specific examples thereof include 1,2,4,5-cyclohexanetetracarboxylic dianhydride.
  • 1,2,3,4-cyclobutanetetracarboxylic dianhydride 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cycloalkanetetracarboxylic dianhydride such as 1,2,3,4-cyclopentanetetracarboxylic dianhydride, bicyclo[2.2 .2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, dicyclohexyl-3,3′,4,4′-tetracarboxylic dianhydride and positional isomers thereof be done. These can be used alone or in combination of two or more.
  • acyclic aliphatic tetracarboxylic dianhydride examples include 1,2,3,4-butanetetracarboxylic dianhydride and 1,2,3,4-pentanetetracarboxylic dianhydride. and these can be used alone or in combination of two or more.
  • a cyclic aliphatic tetracarboxylic dianhydride and an acyclic aliphatic tetracarboxylic dianhydride may also be used in combination.
  • TAHMBP TA23X-BP
  • trimellitic anhydride 3,3′,5,5′-tetramethyl-4 are used from the viewpoint of easily improving the yield strain and transparency of the protective film.
  • Dicarboxylic acid compounds used in the synthesis of polyamideimide resins aromatic dicarboxylic acids, aliphatic dicarboxylic acids and their analogous acid chloride compounds, acid anhydrides, etc., may be used in combination of two or more. .
  • terephthalic acid 2,5-bis(trifluoromethyl)terephthalic acid; isophthalic acid; 2,5-dimethylterephthalic acid; 2,5-dimethoxyterephthalic acid; naphthalenedicarboxylic acid; dicarboxylic acid; 3,3'-biphenyldicarboxylic acid; 2,2'-bis(trifluoromethyl)-4,4'-biphenyldicarboxylic acid; chain hydrocarbon having 8 or less carbon atoms, and 2 compounds in which two benzoic acids are linked by a single bond, —O—, —CH 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —SO 2 — or a phenylene group;
  • Examples include acid chloride compounds.
  • dicarboxylic acid compounds 4,4′-oxybisbenzoic acid, terephthalic acid, isophthalic acid, 2-methoxyterephthalic acid, and 2,5-dimethylterephthalic acid are used from the viewpoint of easily improving the yield strain and transparency of the protective film.
  • the polyimide resin in addition to the tetracarboxylic acid compound used in the synthesis of the polyimide resin, other tetracarboxylic acids and tricarboxylic acids and their anhydrides and A derivative may be further reacted.
  • tetracarboxylic acids include water adducts of the above tetracarboxylic acid compound anhydrides.
  • tricarboxylic acid compounds include aromatic tricarboxylic acids, aliphatic tricarboxylic acids, their analogous acid chloride compounds, acid anhydrides, and the like, and two or more of them may be used in combination. Specific examples include anhydride of 1,2,4-benzenetricarboxylic acid; 2,3,6-naphthalenetricarboxylic acid-2,3-anhydride; a single bond between phthalic anhydride and benzoic acid; , —CH 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —SO 2 — or compounds linked by a phenylene group.
  • Diamine compounds include, for example, aliphatic diamines, aromatic diamines, and mixtures thereof.
  • aromatic diamine refers to a diamine in which an amino group is directly bonded to an aromatic ring, and part of its structure may contain an aliphatic group or other substituents.
  • This aromatic ring may be a single ring or a condensed ring, and examples include, but are not limited to, benzene ring, naphthalene ring, anthracene ring, and fluorene ring. Among these, a benzene ring is preferred.
  • aliphatic diamine refers to a diamine in which an amino group is directly bonded to an aliphatic group, and part of its structure may contain an aromatic ring or other substituents.
  • Aliphatic diamines include, for example, acyclic aliphatic diamines such as hexamethylenediamine, as well as 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, norbornanediamine and 4,4' - Cycloaliphatic diamines such as diaminodicyclohexylmethane. These can be used alone or in combination of two or more.
  • aromatic diamines examples include p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, m-xylylenediamine, p-xylylenediamine, 1,5-diaminonaphthalene and 2,6-diaminonaphthalene.
  • Preferred aromatic diamines include 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 1,4-bis(4-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2′-dimethylbenzidine, TFMB, 6FDAM, 4, 4'-bis(4-aminophenoxy)bipheny
  • diamine compounds 2,2′-dimethylbenzidine, TFMB, 4,4′-bis(4-aminophenoxy)biphenyl, 6FDAM and 4,4 It is more preferable to use one or more selected from the group consisting of '-diaminodiphenyl ether, and it is even more preferable to use TFMB and/or 6FDAM.
  • the amounts of the diamine compound, the tetracarboxylic acid compound and the dicarboxylic acid compound to be used can be appropriately selected depending on the ratio of each constituent unit of the desired resin.
  • the amount of the diamine compound used is preferably 0.94 mol or more, more preferably 0.96 mol or more, based on the total molar amount of the tetracarboxylic acid compound and optionally the dicarboxylic acid compound contained as 1 mol, More preferably 0.98 mol or more, particularly preferably 0.99 mol or more, preferably 1.20 mol or less, more preferably 1.10 mol or less, still more preferably 1.05 mol or less, particularly preferably 1 0.02 mol or less.
  • the polyimide resin and the polyamideimide resin have a structure represented by formula (2). However, it is easy to obtain a high-molecular-weight resin, and as a result, it is easy to improve the yield strain and transparency of the resulting protective film.
  • the reaction temperature of the diamine compound and the tetracarboxylic acid compound is not particularly limited, and may be, for example, 5 to 200° C.
  • the reaction time is also not particularly limited, and may be, for example, about 30 minutes to 72 hours.
  • the reaction temperature is The temperature is preferably 5 to 50°C, more preferably 5 to 40°C, still more preferably 5 to 25°C, and the reaction time is preferably 3 to 24 hours, more preferably 5 to 20 hours.
  • the reaction between the diamine compound and the tetracarboxylic acid compound is preferably carried out in a solvent.
  • the solvent is not particularly limited as long as it does not affect the reaction, but examples include water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, alcohol solvents such as 2-butoxyethanol and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, ⁇ -butyrolactone, ⁇ -valerolactone, propylene glycol methyl ether acetate and ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, methyl isobutyl ketone;
  • the solvent used in the reaction is preferably a solvent that has been rigorously dehydrated to a water content of 700 ppm or less.
  • the reaction between the diamine compound and the tetracarboxylic acid compound may be carried out, if necessary, under an inert atmosphere such as a nitrogen atmosphere or an argon atmosphere, or under reduced pressure conditions. It is preferably carried out with stirring in a strictly controlled dehydrated solvent under the same inert atmosphere as in the above.
  • an inert atmosphere such as a nitrogen atmosphere or an argon atmosphere, or under reduced pressure conditions. It is preferably carried out with stirring in a strictly controlled dehydrated solvent under the same inert atmosphere as in the above.
  • the conditions for producing the polyamic acid and the dicarboxylic acid may be appropriately selected from the conditions for producing the reaction between the diamine compound and the tetracarboxylic acid compound.
  • Examples of the imidization catalyst used in the imidization step include aliphatic amines such as tripropylamine, dibutylpropylamine and ethyldibutylamine; N-ethylpiperidine, N-propylpiperidine, N-butylpyrrolidine, N-butylpiperidine, and cycloaliphatic amines (monocyclic) such as N-propylhexahydroazepine; azabicyclo[2.2.1]heptane, azabicyclo[3.2.1]octane, azabicyclo[2.2.2]octane, and Alicyclic amines (polycyclic) such as azabicyclo[3.2.2]nonane; and pyridine, 2-methylpyridine (2-picoline), 3-methylpyridine (3-picoline), 4-methylpyridine (4 -picoline), 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine,
  • Acid anhydrides include conventional acid anhydrides used in imidization reactions, and specific examples thereof include aliphatic acid anhydrides such as acetic anhydride, propionic anhydride and butyric anhydride, and aromatic acid anhydrides such as phthalic acid. and acid anhydrides.
  • the imidization step it is preferred to carry out the imidization step in stages, increasing the temperature to the optimum reaction temperature.
  • the stepwise imidization suppresses the decomposition of the resin, making it easier to obtain a high-molecular-weight polyimide resin.
  • the reaction temperature to be raised in the stepwise imidization step is preferably 40 to 85°C, more preferably 45 to 80°C. When the reaction temperature is within the above range, the imidization reaction tends to proceed sufficiently, and the Mw tends to increase sufficiently.
  • the reaction time is preferably 30 minutes to 10 hours, more preferably 30 minutes to 5 hours.
  • reaction time When the reaction time is within the above range, it is easy to suppress a decrease in Mw due to decomposition of the resin, and it is easy to suppress a decrease in imidization rate and reduction in molecular weight in the subsequent steps.
  • a resin having a high molecular weight By controlling the imidization step in addition to the synthesis conditions described above, a resin having a high molecular weight can be obtained.
  • the polyimide resin or polyamideimide resin is separated and purified by a conventional method such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, or a combination thereof.
  • the resin can be isolated by adding a large amount of alcohol such as methanol to the reaction solution containing the resin to precipitate the resin, followed by concentration, filtration, drying, and the like.
  • a protective film can be obtained by forming a film from the obtained resin by a known means such as a solvent casting method or a melt extrusion method.
  • the protective film may contain at least one filler in addition to the resin.
  • the filler include organic particles and inorganic particles, preferably inorganic particles.
  • Inorganic particles include metal oxide particles such as silica, zirconia, alumina, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide, antimony oxide, and cerium oxide, magnesium fluoride, sodium fluoride, and the like.
  • silica particles, zirconia particles, and alumina particles more preferably silica particles.
  • the protective film may further contain an ultraviolet absorber.
  • the ultraviolet absorber can be appropriately selected from those commonly used as ultraviolet absorbers in the field of resin materials.
  • the ultraviolet absorber may contain a compound that absorbs light with a wavelength of 400 nm or less.
  • Examples of the ultraviolet absorber include at least one compound selected from the group consisting of benzophenone-based compounds, salicylate-based compounds, benzotriazole-based compounds, and triazine-based compounds.
  • Ultraviolet absorbers can be used alone or in combination of two or more.
  • the protective film may further contain additives other than fillers and ultraviolet absorbers.
  • additives include, for example, antioxidants, release agents, stabilizers, bluing agents, flame retardants, pH adjusters, silica dispersants, lubricants, thickeners, and leveling agents.
  • the adhesive layer can be a layer that bonds the polarizer and the protective film together.
  • the adhesive layer can be formed from, for example, a water-based adhesive or an active energy ray-curable adhesive.
  • the thickness of the adhesive layer is, for example, 0.01-5 ⁇ m, preferably 0.1-3 ⁇ m.
  • water-based adhesives examples include polyvinyl alcohol-based resin aqueous solutions and water-based two-liquid type urethane-based emulsion adhesives.
  • Active energy ray-curable adhesives are adhesives that are cured by irradiation with active energy rays such as ultraviolet rays.
  • active energy ray-curable adhesives include adhesives containing a polymerizable compound and a photopolymerization initiator, adhesives containing a photoreactive resin, adhesives containing a binder resin and a photoreactive cross-linking agent, and the like. can.
  • Examples of the polymerizable compound include photopolymerizable monomers such as photocurable epoxy monomers, photocurable acrylic monomers, and photocurable urethane monomers, and oligomers derived from these monomers.
  • Examples of photopolymerization initiators include compounds containing substances that generate active species such as neutral radicals, cations, and anions upon irradiation with active energy rays such as ultraviolet rays.
  • a polarizing plate may comprise a retardation film.
  • the retardation film has at least one retardation layer.
  • the retardation layer included in the retardation film may be one layer or two or more layers.
  • the retardation layer is preferably laminated on the opposite side of the polarizer to the front plate side.
  • the retardation layer may have an overcoat layer for protecting its surface, a substrate film for supporting the retardation layer, and the like.
  • the retardation layer includes a ⁇ /4 layer and may further include at least one of a ⁇ /2 layer and a positive C layer. When the retardation layer includes a ⁇ /2 layer, a ⁇ /2 layer and a ⁇ /4 layer are laminated in order from the linear polarizing plate side.
  • the ⁇ / 4 layer and the positive C layer may be laminated in order from the linear polarizing plate side, and the positive C layer and ⁇ / 4 layer are laminated in order from the linear polarizing plate side. good too.
  • the thickness of the retardation layer is, for example, 0.1 ⁇ m or more and 10 ⁇ m or less, preferably 0.5 ⁇ m or more and 8 ⁇ m or less, and more preferably 1 ⁇ m or more and 6 ⁇ m or less.
  • the retardation layer may be formed from a resin film exemplified as a material for the protective film, or may be formed from a layer obtained by curing a polymerizable liquid crystal compound.
  • the retardation layer may further include an alignment film.
  • the retardation layer may have an adhesive layer or a pressure-sensitive adhesive layer for bonding the ⁇ /4 layer, the ⁇ /2 layer and the positive C layer.
  • the retardation layer can be formed by applying a composition containing the polymerizable liquid crystal compound to the substrate film and curing the composition.
  • An alignment film may be formed between the substrate film and the coating layer.
  • the material and thickness of the base film may be the same as the material and thickness of the thermoplastic resin film.
  • the retardation layer may be incorporated into the polarizing plate in a form having an alignment film and a base film.
  • the retardation layer can be laminated via a pressure-sensitive adhesive layer or an adhesive layer.
  • the pressure-sensitive adhesive layer can be a pressure-sensitive adhesive layer for bonding the polarizing plate and the front plate.
  • the pressure-sensitive adhesive layer can be a pressure-sensitive adhesive layer for bonding the polarizing plate and the touch sensor or display element.
  • the pressure-sensitive adhesive layer can be a pressure-sensitive adhesive layer for bonding the retardation film and the polarizer or the protective film.
  • the pressure-sensitive adhesive layer can be composed of, for example, a pressure-sensitive adhesive composition whose main component is a (meth)acrylic, rubber, urethane, ester, silicone, polyvinyl ether, or other resin. Among them, a pressure-sensitive adhesive composition using a (meth)acrylic resin as a base polymer, which is excellent in transparency, weather resistance, heat resistance, etc., is preferable.
  • the adhesive composition may be active energy ray-curable or heat-curable.
  • Examples of the (meth)acrylic resin (base polymer) used in the adhesive composition include butyl (meth)acrylate, ethyl (meth)acrylate, isooctyl (meth)acrylate, and 2-(meth)acrylate. Polymers or copolymers containing one or more of (meth)acrylic acid esters such as ethylhexyl as monomers are preferably used.
  • the base polymer is preferably copolymerized with polar monomers.
  • Examples of polar monomers include (meth)acrylic acid, 2-hydroxypropyl (meth)acrylate, hydroxyethyl (meth)acrylate, (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylate, glycidyl ( Examples thereof include monomers having a carboxyl group, a hydroxyl group, an amide group, an amino group, an epoxy group, such as meth)acrylate.
  • the adhesive composition may consist of the base polymer alone, but usually further contains a cross-linking agent.
  • the cross-linking agent is a metal ion having a valence of 2 or more, which forms a carboxylic acid metal salt with a carboxyl group; a polyamine compound, which forms an amide bond with a carboxyl group; Epoxy compounds and polyols that form ester bonds with carboxyl groups; and polyisocyanate compounds that form amide bonds with carboxyl groups.
  • polyisocyanate compounds are preferred.
  • the active energy ray-curable pressure-sensitive adhesive composition has the property of being cured by being irradiated with an active energy ray such as an ultraviolet ray or an electron beam. It can be brought into close contact with an adherend such as a film. It can be cured by irradiation with active energy rays to adjust adhesion.
  • the active energy ray-curable pressure-sensitive adhesive composition is preferably UV-curable.
  • 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. A photopolymerization initiator, a photosensitizer, and the like are also included as appropriate.
  • the adhesive composition includes fine particles for imparting light-scattering properties, beads (resin beads, glass beads, etc.), glass fibers, resins other than base polymers, adhesiveness imparting agents, fillers (metal powders and other inorganic powder, etc.), antioxidants, ultraviolet absorbers, dyes, pigments, colorants, antifoaming agents, corrosion inhibitors, photopolymerization initiators, and other additives.
  • the pressure-sensitive adhesive layer can be formed by applying an organic solvent-diluted solution of the pressure-sensitive adhesive composition onto a substrate and drying it.
  • an active energy ray-curable pressure-sensitive adhesive composition When an active energy ray-curable pressure-sensitive adhesive composition is used, a cured product having a desired degree of curing can be obtained by irradiating the formed pressure-sensitive adhesive layer with an active energy ray.
  • the thickness of the adhesive layer is, for example, 0.1-30 ⁇ m, preferably 0.5-20 ⁇ m, more preferably 1-10 ⁇ m.
  • the storage modulus of the pressure-sensitive adhesive layer is, for example, 0.001 to 1 MPa, preferably 0.01 to 0.3 MPa, more preferably 0.05 to 0.1 MPa at 25°C.
  • the storage elastic modulus of the pressure-sensitive adhesive layer can be measured with a rheometer. For example, a sample is prepared by stacking adhesive layers to a thickness of 150 ⁇ m, and the storage elastic modulus (G′) is measured using a rheometer (manufactured by Anton Parr, “MCR-301” (trade name)). be able to.
  • the measurement conditions can be a temperature of 25° C., a stress of 1% and a frequency of 1 Hz.
  • a laminate according to the present invention includes a front plate, an adhesive layer, and the polarizing plate of the present invention.
  • the front plate and the protective film are bonded with an adhesive layer.
  • the laminate can further include a touch sensor or the like, which will be described later.
  • a laminate 40 in FIG. 4 includes a front plate 47 , a protective film 42 , a polarizer 41 and a retardation film 45 .
  • the polarizer 41 and the protective film 42 are bonded with an adhesive layer 43 .
  • the polarizer 41 and the retardation film 45 are laminated with an adhesive layer 44 .
  • the front plate 47 and the protective film 42 are laminated with an adhesive layer 46 .
  • the laminate is preferably bendable. Bendable means that it can be bent without cracking.
  • the laminate may be bendable with at least one of the front plate side inside and outside, preferably bendable with the front plate side inside, and more preferably bendable with the front plate side inside. Cracks tend not to occur even when repeatedly bent with a radius of 2 mm.
  • bending includes a form of bending in which a curved surface is formed at the bent portion. In the form of bending, the radius of curvature of the bent inner surface is not particularly limited.
  • Bending also includes a form of refraction in which the angle of refraction of the inner surface is greater than 0° and less than 180°, and a form of folding in which the radius of curvature of the inner surface is close to zero or the angle of refraction of the inner surface is 0°. .
  • the material and thickness of the front plate are not limited as long as it is a plate-like body that can transmit light, and it may be composed of only one layer, or may be composed of two or more layers.
  • a glass plate for example, a glass plate, a glass film, etc.
  • a resin plate for example, a resin plate, a resin sheet, a resin film, etc.
  • a laminate with a plate-like body is exemplified.
  • the front plate can be a layer forming the outermost layer on the viewing side of the display device. The effect of the present invention is remarkable when the front plate is provided with a plate-like body made of resin.
  • the thickness of the front plate may be, for example, 20 ⁇ m or more and 200 ⁇ m or less, preferably 30 ⁇ m or more and 200 ⁇ m or less, and more preferably 40 ⁇ m or more and 100 ⁇ m or less.
  • resin plate-like bodies examples include cyclopolyolefin resin films; cellulose acetate resin films made of resins such as triacetyl cellulose and diacetyl cellulose; polyester films made of resins such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; resin film; polycarbonate resin film; (meth)acrylic resin film; polypropylene resin film; polyamide resin film; polyimide resin film; From the viewpoint of reducing dents remaining on the screen, the front plate preferably contains at least one selected from the group consisting of polyimide-based resins, polyamide-based resins, and polyamide-imide-based resins. Resins suitable for the front plate include the same resins as those suitable for the protective film described above.
  • the yield strain of the resin film is preferably 4.5% or more, more preferably 5.0% or more, from the viewpoint of reducing the dent remaining on the screen. 0% or more is more preferable. Yield strain can be, for example, 10% or less. The yield strain of the resin film is measured by the same method as the yield strain of the protective film.
  • the front plate may be a film having a hard coat layer on at least one surface of the resin film.
  • the front plate preferably has a hard coat layer on the surface opposite to the polarizing plate.
  • the hard coat layer may be formed on one surface of the resin film, or may be formed on both surfaces.
  • a resin film having a hard coat layer is preferably used because the surface of the front panel serves as a touch surface. By providing a hard coat layer, a resin film having improved hardness and scratch resistance can be obtained.
  • the hard coat layer is, for example, a cured layer of an ultraviolet curable resin.
  • UV curable resins examples include (meth)acrylic resins, silicone resins, polyester resins, urethane resins, amide resins, and epoxy resins.
  • the hard coat layer may contain additives to improve strength. Additives are not limited and include inorganic fine particles, organic fine particles, or mixtures thereof.
  • an abrasion resistant layer is formed on the visible side of the hard coat layer.
  • the wear-resistant layer can improve wear resistance and prevent contamination with sebum and the like.
  • the front plate can have a wear-resistant layer, and the wear-resistant layer can be a layer that constitutes the viewing side surface of the front plate.
  • the abrasion resistant layer can include structures derived from fluorine compounds.
  • the fluorine compound a compound having a silicon atom and having a hydrolyzable group such as an alkoxy group or a halogen group on the silicon atom is preferable.
  • a coating film can be formed by the dehydration condensation reaction of the hydrolyzable groups, and the adhesion of the wear-resistant layer can be improved by reacting with active hydrogen on the substrate surface.
  • the fluorine compound preferably has a perfluoroalkyl group or a perfluoropolyether structure because it can impart water repellency.
  • Particularly preferred are fluorine-containing polyorganosiloxane compounds having a perfluoropolyether structure and a long-chain alkyl group having 4 or more carbon atoms. It is also preferable to use two or more kinds of compounds as the fluorine compound.
  • a fluorine compound that is preferably further contained is a fluorine-containing organosiloxane compound containing an alkylene group having 2 or more carbon atoms and a perfluoroalkylene group.
  • the thickness of the wear-resistant layer is, for example, 1 nm or more and 20 nm or less. Further, the wear-resistant layer has water repellency and a water contact angle of, for example, 110 to 125°. The contact angle hysteresis and sliding angle measured by the sliding method can be 3-20° and 2-55°, respectively. Furthermore, the wear-resistant layer contains a silanol condensation catalyst, an antioxidant, an antirust agent, an ultraviolet absorber, a light stabilizer, an antifungal agent, an antibacterial agent, an anti-biadhesion agent, a deodorant, a pigment, a flame retardant, and an antistatic agent. It may contain various additives such as agents.
  • a primer layer may be provided between the wear-resistant layer and the hard coat layer.
  • primer agents include UV-curing, heat-curing, moisture-curing, and two-liquid-curing epoxy compounds.
  • polyamic acid may be used, and it is also preferable to use a silane coupling agent.
  • the thickness of the primer layer is, for example, 0.001-2 ⁇ m.
  • the glass plate tempered glass for displays is preferably used.
  • the thickness of the glass plate is, for example, 20 ⁇ m or more and 1000 ⁇ m or less, and can be 20 ⁇ m or more and 100 ⁇ m or less.
  • the front plate can have excellent mechanical strength and surface hardness.
  • the front panel may not only have a function of protecting the front surface of the display device, but also have a function as a touch sensor, a blue light cut function, a viewing angle adjustment function, and the like.
  • the detection method is not limited as long as it is a sensor that can detect the touched position, and the detection method is not limited, such as resistive film method, capacitive coupling method, optical sensor method, ultrasonic method, electromagnetic induction coupling.
  • a touch sensor panel such as a system, a surface acoustic wave system, or the like is exemplified. Due to their low cost, touch sensor panels of resistive film type and capacitive coupling type are preferably used.
  • An example of a resistive touch sensor panel includes a pair of substrates facing each other, an insulating spacer sandwiched between the pair of substrates, and a transparent spacer provided as a resistive film on the entire inner surface of each substrate. It is composed of a conductive film and a touch position detection circuit.
  • a display device provided with a resistive touch sensor panel, when the surface of the front plate is touched, the opposed resistive films are short-circuited and current flows through the resistive films.
  • a touch position detection circuit detects the voltage change at this time, and the touched position is detected.
  • An example of a capacitive touch sensor panel includes a substrate, a position detection transparent electrode provided on the entire surface of the substrate, and a touch position detection circuit.
  • a display device provided with a capacitive coupling type touch sensor panel
  • the transparent electrode is grounded via the human body's capacitance at the touched point.
  • a touch position sensing circuit senses the grounding of the transparent electrode and the touched position is detected.
  • the display element is not particularly limited, and examples thereof include an organic electroluminescence (organic EL) display element, an inorganic electroluminescence (inorganic EL) display element, a liquid crystal display element, and the like.
  • a display device includes the laminate according to the present invention.
  • the laminate is arranged such that the front plate constitutes the viewing side surface.
  • the display device is not particularly limited, and examples thereof include display devices such as an organic EL display device, an inorganic EL display device, and a liquid crystal display device.
  • display devices such as an organic EL display device, an inorganic EL display device, and a liquid crystal display device.
  • the display device according to this embodiment can also be used as a flexible display that can be bent or rolled.
  • the display device according to the present invention can be used as mobile devices such as smartphones and tablets, televisions, digital photo frames, electronic signboards, measuring instruments and gauges, office equipment, medical equipment, computing equipment, and the like.
  • a polarizing plate and a laminate can be produced by a method including a step of bonding members together via a pressure-sensitive adhesive layer or an adhesive layer.
  • the laminate is, for example, a step of manufacturing a polarizing plate, a step of bonding the polarizing plate and the retardation film with an adhesive layer to obtain a circularly polarizing plate, and bonding the circularly polarizing plate and the front plate with an adhesive layer. It can be manufactured from a process including a step of obtaining a laminate by pressing.
  • the step of bonding the circularly polarizing plate and the front plate together with the adhesive layer to obtain the laminate can be performed so that the protective film and the front plate face each other with the adhesive layer interposed therebetween.
  • phase difference value Using a phase difference meter “KOBRA (registered trademark)-WPR” manufactured by Oji Scientific Instruments Co., Ltd., the in-plane retardation value and the thickness direction retardation value at a wavelength of 590 nm were measured at a temperature of 23°C.
  • the protective film to be measured was cut into JIS K6251 dumbbell shape No. 2 using a dumbbell cutter. Both ends of the small piece in the long side direction were sandwiched between upper and lower grips of a tensile tester [Autograph AGS-X tester manufactured by Shimadzu Corporation] so that the distance between the grips was 80 mm. A stress-strain curve was created by pulling the small piece in its long side direction at a tensile speed of 100 mm/min under an environment of temperature 23° C. and relative humidity 50%. In the resulting curve, the time when the linearity first became non-linear was defined as the yield point, and the strain (%) at that point was determined as the yield strain.
  • ⁇ -Butyrolactone (GBL) was added to the obtained PAI-1 resin to prepare 7.7% by mass of PAI-1 varnish.
  • the obtained PAI-1 varnish is applied on the smooth surface of the glass substrate using an applicator so that the thickness of the film finally obtained is 30 ⁇ m, dried at 140 ° C. for 30 minutes, and is freestanding.
  • a membrane was obtained.
  • the resulting self-supporting film was fixed to a metal frame and dried at 210° C. for 90 minutes to obtain a protective film A with a film thickness of 30 ⁇ m.
  • ⁇ Protective film B PAI-2>
  • 313.6 g of DMAc was added to a 1 L separable flask equipped with a stirring blade, and 16.77 g (52.37 mmol) of TFMB was added with stirring at room temperature to dissolve in DMAc.
  • 4.797 g (10.80 mmol) of 6FDA and 6.679 g (10.80 mmol) of tetracarboxylic dianhydride (TAHMBP) represented by the following formula (A) were added and stirred at room temperature for 16 hours.
  • TAHMBP tetracarboxylic dianhydride
  • TPC terephthaloyl chloride
  • 5.582 g (43.19 mmol) of N,N-diisopropylethylamine, 7.716 g (75.58 mmol) of acetic anhydride, and 4.022 g (43.19 mmol) of 4-methylpyridine were added to the flask and stirred at room temperature for 30 minutes. After that, the temperature was raised to 70° C. using an oil bath, and the mixture was further stirred for 3 hours to obtain a reaction liquid.
  • the resulting reaction solution is cooled to room temperature, stirred, and gradually added with methanol in an amount of 1.385 times the weight of the reaction solution, and then added in an amount of 0.6924 times the weight of the reaction solution. Water was added gradually. The deposited precipitate was taken out and washed with methanol. Next, the precipitate was dried under reduced pressure at 80° C. to obtain PAI-2 resin.
  • DMAc was added to the obtained PAI-2 resin to prepare 10.5% by mass of PAI-2 varnish.
  • the obtained PAI-2 varnish is applied on the smooth surface of the glass substrate using an applicator so that the thickness of the film finally obtained is 30 ⁇ m, dried at 140 ° C. for 30 minutes, and is freestanding.
  • a membrane was obtained.
  • the resulting self-supporting film was fixed to a metal frame and dried at 210° C. for 90 minutes to obtain a protective film B with a thickness of 30 ⁇ m.
  • COP-1> Cycloolefin polymer (COP) film manufactured by Nippon Zeon Co., Ltd., Zeonor film product name: ZF14, film thickness 23 ⁇ m
  • the following polarizer-forming composition was prepared.
  • the polarizer-forming composition comprises 75 parts by mass of compound (1-6), 25 parts by mass of compound (1-7), and the above formulas (2-1a), (2-1b), and (2) as dichroic dyes.
  • Polymerization initiator (Irgacure 369, 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl) butan-1-one, manufactured by BASF Japan): 6 parts by mass Leveling agent (BYK-361N, polyacrylate compound, BYK -Chemie): 0.1 parts by mass Solvent (cyclopentanone): 400 parts by mass
  • the composition for forming an alignment film was applied onto the substrate film by a bar coating method, and dried by heating in a drying oven at 80° C. for 1 minute.
  • the resulting dry film was subjected to polarized UV irradiation treatment to form an alignment film.
  • polarized UV irradiation treatment light emitted from a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Inc.) is transmitted through a wire grid (UIS-27132##, manufactured by Ushio Inc.) to obtain a wavelength of The measurement was performed under the condition that the integrated amount of light measured at 365 nm was 100 mJ/cm 2 .
  • the polarization direction of the polarized UV was set at 45° with respect to the absorption axis of the polarizer.
  • a laminate composed of "base film/alignment film” was obtained.
  • the thickness of the alignment film was 100 nm.
  • the retardation layer composition was applied onto the alignment film by a bar coating method, dried by heating in a drying oven at 120° C. for 1 minute, and then cooled to room temperature.
  • a retardation layer was formed by irradiating the obtained dry film with ultraviolet light at an integrated light amount of 1000 mJ/cm 2 (365 nm standard) using the above UV irradiation device.
  • the thickness of the obtained retardation layer was measured with a laser microscope (OLS3000 manufactured by Olympus Corporation), it was 2.0 ⁇ m.
  • the retardation layer was a ⁇ /4 layer with reverse wavelength dispersion exhibiting a retardation value of ⁇ /4 in the in-plane direction.
  • a laminate was obtained.
  • the varnish coating was heated at 80° C. for 10 minutes, further heated at 100° C. for 10 minutes, and further heated at 90° C. for 10 minutes. After that, the coating film was heated (post-baked) at 200° C. for 25 minutes to obtain a polyimide film having a thickness of 40 ⁇ m.
  • the photocurable resin composition was applied by a roll-to-roll method so that the thickness after drying was 10 ⁇ m. After that, it was dried in an oven at 80° C. for 3 minutes and cured by irradiation with ultraviolet rays to obtain a front plate.
  • a high-pressure mercury lamp was used to irradiate the ultraviolet rays so that the lamination light amount was 500 mJ/cm 2 .
  • the thickness of the hard coat layer on the front plate was 10 ⁇ m.
  • the polarizer-forming composition was applied onto the formed alignment film by a bar coating method, dried by heating in a drying oven at 120° C. for 1 minute, and then cooled to room temperature.
  • a polarizer was formed by irradiating the dry film with ultraviolet rays at an integrated light amount of 1200 mJ/cm 2 (365 nm standard) using the above UV irradiation apparatus.
  • OLS3000 manufactured by Olympus Corporation When the thickness of the obtained polarizer was measured with a laser microscope (OLS3000 manufactured by Olympus Corporation), it was 1.8 ⁇ m.
  • a composition for a protective layer (overcoat layer, OC layer) was prepared.
  • the protective layer composition is composed of 3 parts by weight of polyvinyl alcohol resin powder (manufactured by Kuraray Co., Ltd., average degree of polymerization: 18000, trade name: KL-318) and polyamide epoxy resin (crosslinking agent, resin) per 100 parts by weight of water.
  • Ka Chemtex Co., Ltd., trade name: SR650 (30) was mixed with 1.5 parts by mass.
  • the protective layer composition was applied onto the polarizer 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.
  • the front plate and the circularly polarizing plate were laminated with an acrylic pressure-sensitive adhesive layer such that the surface of the front plate on which the hard coat layer was not formed faced the protective film surface of the circularly polarizing plate.
  • the laminate has a layer structure of "front plate/adhesive layer/circularly polarizing plate".
  • a sample was prepared by bonding the laminate to a substitute for an organic EL panel via an adhesive layer.
  • a substitute for the organic EL panel is "cycloolefin polymer (COP) film (thickness 25 ⁇ m) / acrylic adhesive layer (thickness 50 ⁇ m) / COP film (thickness 25 ⁇ m) / acrylic adhesive layer (thickness 50 ⁇ m) / glass plate ” layer structure.
  • the laminate was attached to a substitute for the organic EL panel so that the front plate constituted the surface of the sample.
  • Pen The tip is composed of polyacetal.
  • Polyacetal has a tensile modulus of about 3 GPa.
  • test pen was fixed to the surface of the front plate so as to contact it at an angle of 90 degrees.
  • a load of 200 gf or 500 gf was applied to the test pen.
  • the test pen was reciprocated once in a straight line of 30 mm at a speed of 500 mm/min. After that, the sample was allowed to stand in an environment of 23° C. and 50% relative humidity for 2 hours.
  • the recesses of the scratch marks were measured using a two-dimensional measuring machine (DEKTAK T-Standard 6M; manufactured by Veeco).
  • the dent of the scratch mark is the maximum depth (dent from the surroundings) on a straight line where the test pen is reciprocated on the front plate surface of the sample.
  • Table 1 shows the measured values of the scratch mark indentations.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)

Abstract

L'invention concerne une plaque polarisante comprenant un film protecteur et un polariseur, le polariseur et le film protecteur étant adjacents l'un à l'autre et le film protecteur ayant une limite d'élasticité de 4,0 % ou plus lorsqu'il est soumis à un essai de traction à une vitesse de 100 mm/minute.
PCT/JP2022/017098 2021-04-15 2022-04-05 Plaque polarisante, stratifié et dispositif d'affichage WO2022220177A1 (fr)

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CN202280028080.4A CN117120897A (zh) 2021-04-15 2022-04-05 偏振片、层叠体和显示装置

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JP2021068853A JP2022163804A (ja) 2021-04-15 2021-04-15 偏光板、積層体、及び表示装置

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018159285A1 (fr) * 2017-03-02 2018-09-07 東洋紡株式会社 Film de polyester en tant que film de protection de surface pour un dispositif d'affichage pliable et son application
WO2020138046A1 (fr) * 2018-12-28 2020-07-02 住友化学株式会社 Film optique
JP2021002070A (ja) * 2013-05-14 2021-01-07 東洋紡株式会社 液晶表示装置、偏光板及び偏光子保護フィルム

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JP5080258B2 (ja) 2005-02-03 2012-11-21 富士フイルム株式会社 液晶表示装置
KR101862252B1 (ko) 2015-08-03 2018-05-29 주식회사 엘지화학 플렉시블 플라스틱 필름
JP7268967B2 (ja) 2018-06-22 2023-05-08 日東電工株式会社 フレキシブル画像表示装置用粘着剤層、フレキシブル画像表示装置用積層体、及び、フレキシブル画像表示装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021002070A (ja) * 2013-05-14 2021-01-07 東洋紡株式会社 液晶表示装置、偏光板及び偏光子保護フィルム
WO2018159285A1 (fr) * 2017-03-02 2018-09-07 東洋紡株式会社 Film de polyester en tant que film de protection de surface pour un dispositif d'affichage pliable et son application
WO2020138046A1 (fr) * 2018-12-28 2020-07-02 住友化学株式会社 Film optique

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