WO2014192502A1 - Polymerizable composition, polymer, optical adhesive sheet, image display device, and method for producing same - Google Patents

Polymerizable composition, polymer, optical adhesive sheet, image display device, and method for producing same Download PDF

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Publication number
WO2014192502A1
WO2014192502A1 PCT/JP2014/062093 JP2014062093W WO2014192502A1 WO 2014192502 A1 WO2014192502 A1 WO 2014192502A1 JP 2014062093 W JP2014062093 W JP 2014062093W WO 2014192502 A1 WO2014192502 A1 WO 2014192502A1
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component
polymerizable composition
image display
polymer
meth
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PCT/JP2014/062093
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French (fr)
Japanese (ja)
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一彦 大賀
律子 東
眸 上野
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昭和電工株式会社
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
    • B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by features of form at particular places, e.g. in edge regions
    • B32B3/08—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by added members at particular parts
    • 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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
    • B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
    • B32B3/18—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by an internal layer formed of separate pieces of material which are juxtaposed side-by-side
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/04—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters
    • C08F299/0485—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters from polyesters with side or terminal unsaturations
    • C08F299/0492—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters from polyesters with side or terminal unsaturations the unsaturation being in acrylic or methacrylic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C08G18/735—Polyisocyanates or polyisothiocyanates acyclic containing one isocyanate or isothiocyanate group linked to a primary carbon atom and at least one isocyanate or isothiocyanate group linked to a tertiary carbon atom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
    • C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
    • C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
    • C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/414—Translucent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/718—Weight, e.g. weight per square meter
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • 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
    • B32B2551/00—Optical elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers
    • C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates

Definitions

  • the present invention relates to a polymerizable composition used in an image display device such as a liquid crystal display device used in, for example, smartphones and tablet PCs, a polymer obtained by polymerizing the composition, and an optical having a layer of the polymer
  • the present invention relates to a pressure-sensitive adhesive sheet, a method for producing an image display device using the composition, and an image display device produced by the method.
  • a liquid crystal display device 101 shown in FIG. 6 is known as this type of image display device.
  • the liquid crystal display device 101 has a transparent protective part 103 made of, for example, glass or resin on a liquid crystal display panel 102.
  • a gap 104 is provided between the liquid crystal display panel 102 and the protective part 103 by interposing a spacer 104 between the protective part 103 and the liquid crystal display panel 102. Is provided.
  • the presence of the gap 105 between the liquid crystal display panel 102 and the protection unit 103 causes light scattering, resulting in a decrease in contrast and brightness, and the presence of the gap 105 hinders thinning of the panel. It has become.
  • a resin plate generally has a tendency to have larger distortion and warpage than glass, and there is a demand for the resin that exhibits good adhesion to the resin plate and does not peel off.
  • JP 2012-46658 A discloses a photocurable adhesive composition containing a (meth) acrylate oligomer having an ultraviolet crosslinkable site and a hindered amine, and the composition. Is disclosed for use in bonding an optical display panel and a protective panel.
  • Japanese Patent Application Laid-Open No. 2012-46658 discloses the tensile modulus and adhesion to glass, but does not disclose the storage modulus and durability of peeling, and in particular, resistance to peeling with a resin protective part. Is not disclosed, and there is no disclosure of high dielectric constant.
  • JP 2012-41456 A discloses a (meth) acrylic acid ester monomer having a hydrocarbon group having 1 to 12 carbon atoms, a hydroxyl group-containing (meth) acrylic acid ester monomer, an amide group.
  • An acrylic resin having a weight average molecular weight of 400,000 to 2,000,000 and a dielectric constant of 3 to 6 obtained by copolymerization of a monomer component containing a monomer and a vinyl ester monomer A polymer compound is disclosed, and it is disclosed that the acrylic polymer compound is used for a pressure-sensitive adhesive composition for a touch panel, and that the composition is excellent in adhesion to a glass plate and a resin plate.
  • JP2012-41456A does not disclose the durability of peeling.
  • a curable resin composition is applied to a base having an image display part or a translucent protective part arranged on the image display part, and the base and the protective part are provided.
  • a method for manufacturing an image display device having a process of forming a resin cured material layer between a base portion and a protective portion by being placed in close proximity to each other and cured, and as a curable resin composition, polyurethane acrylate, polyisoprene acrylate Or one or more polymers selected from esterified products thereof, terpene hydrogenated resins and butadiene polymers, and one or more acrylates selected from isobornyl acrylate, dicyclopentenyloxyethyl methacrylate and 2-hydroxybutyl methacrylate.
  • the present invention relates to a polymerizable composition for forming a polymer layer interposed between an image display unit and a translucent protective unit of an image display device, and prevents peeling of the display unit and the protective unit.
  • both the display unit and the protective unit are made of glass, but recently, the protective unit is made of resin (polycarbonate or PMMA), and not only the resistance to peeling from the glass plate but also the resin plate Therefore, an object of the present invention is to provide a polymerizable composition that is excellent not only in peeling resistance with a glass plate but also in peeling resistance with a resin plate. Further, the peeling resistance requires durability and is evaluated under conditions of high temperature and high humidity, and therefore cannot be solved only by improving adhesiveness. An object of the present invention is to provide durable peeling resistance.
  • the present inventors limited the molecular weight of the (meth) acryloyl group-containing polymer compound, which is the main component of the polymerizable composition, to a specific range, and then polymerizable composition.
  • the inventors have found that the above problems can be solved by limiting the storage elastic modulus of the polymer obtained by polymerizing the product to a certain range, and have completed the present invention.
  • the present invention (I) is a polymerizable composition for forming a polymer layer interposed between an image display part and a translucent protective part of an image display device, the polymerizable composition But, (Component 1) containing a (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 15000, and (Component 2) a photopolymerization initiator, and obtained by polymerizing the polymerizable composition.
  • the present invention relates to a polymerizable composition characterized by having a storage elastic modulus of 1 ⁇ 10 3 to 1 ⁇ 10 5 Pa at 25 ° C. and a frequency of 0.1 Hz.
  • the present invention (II) is a polymerizable composition for forming a polymer layer interposed between the image display part and the translucent protective part of the image display device, the polymerizable composition comprising: (Component 1) (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 15000, Polymerization obtained by polymerizing the polymerizable composition, comprising (Component 2) a photopolymerization initiator, and (Component 3) a radical polymerizable unsaturated group-containing compound having at least one of an alcoholic hydroxyl group and an amide group.
  • the present invention relates to a polymerizable composition characterized by having a storage elastic modulus of 1 ⁇ 10 3 to 1 ⁇ 10 5 Pa at 25 ° C. and a frequency of 0.1 Hz.
  • the present invention (III) is a polymerizable composition for forming a polymer layer interposed between the image display part of the image display device and the translucent protective part, the polymerizable composition comprising: (Component 1) (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 15000, (Component 2) Photopolymerization initiator, (Component 3) a radical polymerizable unsaturated group-containing compound having at least one of an alcoholic hydroxyl group and an amide group, and (Component 4) no alcoholic hydroxyl group or amide group, and a viscosity of 25 ° C.
  • a polymer obtained by polymerizing the polymerizable composition containing a (meth) acryloyl group-containing compound that is 500 mPa ⁇ s or less has a storage elastic modulus at 25 ° C. and a frequency of 0.1 Hz of 1 ⁇ 10 3 to
  • the present invention relates to a polymerizable composition characterized by being 1 ⁇ 10 5 Pa.
  • the present invention (IV) is a polymerizable composition for forming a polymer layer interposed between the image display part of the image display device and the translucent protective part, the polymerizable composition comprising: (Component 1) (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 15000, (Component 2) Photopolymerization initiator, (Component 3) Radical polymerizable unsaturated group-containing compound having at least one of an alcoholic hydroxyl group and an amide group, (Component 4) a (meth) acryloyl group-containing compound which does not have any group of an alcoholic hydroxyl group and an amide group and has a viscosity of 500 mPa ⁇ s or less at 25 ° C.
  • Nonionic surfactant having no (meth) acryloyl group and (Component 6) No (meth) acryloyl group in the molecule, a function for suppressing radical polymerization, a function for inhibiting radical polymerization, light Liquid or solid at 25 ° C., which has neither a polymerization initiation function nor a surface-active function, and is composed of carbon atoms and hydrogen atoms, or is composed of carbon atoms, hydrogen atoms and oxygen atoms
  • the storage modulus of the polymer obtained by polymerizing the polymerizable composition at 25 ° C. and a frequency of 0.1 Hz is 1 ⁇ 10 3 to 1 ⁇ 10 5 Pa.
  • the present invention relates to a polymerizable composition.
  • the present invention (V) relates to a polymer obtained by polymerizing the polymerizable composition of the present invention (I) to the present invention (IV).
  • the present invention (VI) is a polymerizable composition for producing an optical pressure-sensitive adhesive sheet used as a polymer layer interposed between an image display portion and a translucent protective portion of an image display device.
  • the present invention also relates to a polymerizable composition characterized in that the polymerizable composition is the polymerizable composition of the present invention (I) to the present invention (IV).
  • the present invention (VII) has a thickness obtained by applying the polymerizable composition of the present invention (VI), irradiating the polymerizable composition with light capable of being photosensitized by the photopolymerization initiator, and polymerizing the polymerizable composition.
  • the present invention relates to an optical pressure-sensitive adhesive sheet having a polymer layer of 10 to 1000 ⁇ m.
  • the present invention (VIII) is a method for producing an image display device comprising a base having an image display portion, a translucent protective portion, and a polymer layer interposed between the base and the protective portion, The method comprises the step of interposing the polymerizable composition of the present invention (IV) between the base part and the protective part, and irradiating the polymerizable composition with light that can be photosensitized by a photopolymerization initiator.
  • the present invention relates to a method for manufacturing an image display device including a step of forming a polymer layer.
  • This invention (IX) is a manufacturing method of an image display apparatus which has the process of sticking the base which has an image display part, and a translucent protective part using an optical adhesive sheet, Comprising: This optical adhesive sheet is And an optical pressure-sensitive adhesive sheet according to the present invention (VII).
  • the present invention (X) relates to an image display device manufactured by the manufacturing method of the image display device of the present invention (VIII) or the present invention (IX).
  • a polymerizable composition for forming a polymer layer interposed between an image display portion and a translucent protective portion of an image display device comprising: (Component 1) containing a (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 15000, and (Component 2) a photopolymerization initiator, and obtained by polymerizing the polymerizable composition.
  • a polymerizable composition having a storage elastic modulus of 1 ⁇ 10 3 to 1 ⁇ 10 5 Pa at 25 ° C. and a frequency of 0.1 Hz.
  • the component 5 is a nonionic surfactant having no (meth) acryloyl group, wherein the HLB value of Griffin is 3.0 to 6.0 [7] or [7] 8].
  • a polymerizable composition for producing an optical pressure-sensitive adhesive sheet used as a polymer layer interposed between an image display portion and a translucent protective portion of an image display device, wherein the polymerizable composition A polymerizable composition, wherein the composition is the polymerizable composition according to any one of [1] to [10].
  • a method for manufacturing an image display device comprising: a base having an image display portion; a translucent protective portion; and a polymer layer interposed between the base portion and the protective portion, the method comprising: [7] to [9]
  • the polymerizable composition according to any one of [7] to [9] is interposed between the base portion and the protective portion, and light capable of being photosensitized by a photopolymerization initiator is added to the polymerizable composition.
  • the manufacturing method of the image display apparatus characterized by including the process of irradiating and forming a polymer layer.
  • a method for manufacturing an image display device including a step of attaching a base portion having an image display portion and a translucent protective portion using an optical pressure-sensitive adhesive sheet, the optical pressure-sensitive adhesive sheet according to [12]
  • a method for producing an image display device which is the optical pressure-sensitive adhesive sheet according to claim 1.
  • the polymerizable composition of the present invention can be used to form a polymer layer interposed between an image display portion and a translucent protective portion of an image display device, and is made of a glass display portion or protective portion. It is excellent not only in peeling resistance but also in peeling resistance with a resin-made display part and protective part, and it is possible to impart durable peeling resistance.
  • FIG. 1 is a cross-sectional view showing a main part of an embodiment of a display device according to the present invention.
  • FIG. 2 is a cross-sectional view showing a main part of an embodiment of the display device according to the present invention.
  • FIG. 3 is a cross-sectional view showing a main part of an embodiment of the display device according to the present invention.
  • FIG. 4 is a cross-sectional view showing a main part of an embodiment of the display device according to the present invention.
  • FIG. 5 is a cross-sectional view showing a main part of an embodiment of the display device according to the present invention.
  • FIG. 6 is a cross-sectional view showing a main part of a display device according to the prior art.
  • polyester polyol that can be a raw material of Component 1, which is an essential raw material component of the polymerizable composition of the present invention (I), a polyol (that is, a —COO— bond) that is a raw material of the polyester polyol.
  • this polyol is also defined as being included in the polyester polyol.
  • a polyol which is a raw material component of the polyester polyol to be used is newly added, and the essential component of the polymerizable composition of the present invention (I) When component 1 is produced, the added polyol is included in the polyester polyol even if it has no —COO— bond (carboxylic acid ester bond).
  • a polycarbonate polyol that can be a raw material of Component 1, which is an essential raw material component of the polymerizable composition of the present invention (I)
  • a polyol that is, a carbonate bond
  • this polyol is also included in the polycarbonate polyol.
  • a polyol which is a raw material component of the polycarbonate polyol to be used is newly added, and the essential component of the polymerizable composition of the present invention (I) When component 1 is produced, this added polyol shall be included in the polycarbonate polyol.
  • a polyol that can be a raw material of Component 1, which is an essential raw material component of the polymerizable composition of the present invention (I) when producing a polyether polyol that can be a raw material of Component 1, which is an essential raw material component of the polymerizable composition of the present invention (I), a polyol that is a raw material of the polyether polyol (ie, When a polyol having no ether bond) remains, this polyol is also included in the polyether polyol.
  • a polyol which is a raw material component of the polyether polyol to be used is newly added to the polymerizable composition of the present invention (I).
  • component 1, which is an essential component is produced, the added polyol shall be included in the polyether polyol.
  • the present invention (I) is a polymerizable composition for forming a polymer layer interposed between the image display part of the image display device and the translucent protective part, the polymerizable composition comprising: (Component 1) containing a (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 15000, and (Component 2) a photopolymerization initiator, and obtained by polymerizing the polymerizable composition.
  • a polymerizable composition having a storage elastic modulus of 1 ⁇ 10 3 to 1 ⁇ 10 5 Pa at 25 ° C. and a frequency of 0.1 Hz.
  • component 1 which is an essential component of the polymerizable composition of the present invention (I) is a (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 15000.
  • Component 1 is not particularly limited as long as it is a polymer compound having a number average molecular weight in the range of 1000 to 15000 and having a (meth) acryloyl group.
  • the “polymer compound” described in the present specification means a polymer having a molecular weight distribution.
  • the “number average molecular weight” described in the present specification is a number average molecular weight measured in terms of polystyrene by gel permeation chromatography (hereinafter referred to as “GPC”).
  • the number average molecular weight of the polymer compound of component 1 which is an essential component in the present invention (I) is in the range of 1000 to 15000.
  • the range is preferably 1200 to 8000, and more preferably 1500 to 6000.
  • the number average molecular weight is less than 1000, the volume shrinkage during polymerization of the polymer obtained by polymerizing the composition of the present invention (I) may increase, or the polymer may become too hard.
  • the number average molecular weight is 15000 or more, the viscosity may be too high.
  • the (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 15000 include, for example, polyether (meth) acrylate and polyester (meth) having a number average molecular weight in the range of 1000 to 15000.
  • Acrylate epoxy (meth) acrylate, urethane (meth) acrylate, urethane (meth) acrylamide, polycarbonate (meth) acrylate, and the like.
  • the “(meth) acrylate” in the present specification means at least one group selected from acrylate and methacrylate.
  • “(meth) acrylamide” in the present specification means at least one group selected from acrylamide and methacrylamide.
  • the polyether (meth) acrylate is a (meth) acrylate produced by a dehydration condensation reaction between a polyether polyol and (meth) acrylic acid or a transesterification reaction between the polyether polyol and (meth) acrylic acid ester.
  • (meth) acrylic acid” in the present specification means at least one group selected from acrylic acid and methacrylic acid.
  • the polyester (meth) acrylate is a (meth) acrylate produced by a dehydration condensation reaction between a polyester polyol and (meth) acrylic acid or a transesterification reaction between the polyester polyol and (meth) acrylic acid ester.
  • Epoxy (meth) acrylate has a reaction product of an epoxy group-containing compound having an ether bond, an ester bond or a hydrocarbon chain and (meth) acrylic acid, a polyester polycarboxylic acid, an aliphatic hydrocarbon chain, or an aromatic ring.
  • a reaction product of a polycarboxylic acid such as a polycarboxylic acid or a polycarboxylic acid having a heterocyclic ring and an epoxy group-containing (meth) acryloyl group-containing compound such as glycidyl (meth) acrylate or (meth) acryloyloxybutyl glycidyl ether is there.
  • Urethane (meth) acrylate is a polyaddition reaction using polyol, organic polyisocyanate compound and alcoholic hydroxyl group-containing (meth) acrylate as essential materials, or (meth) acrylate having a polyol and isocyanate group as essential materials.
  • a compound having a urethane bond in the molecule and one or more (meth) acrylate groups by a polyaddition reaction Urethane (meth) acrylamide has a urethane bond in the molecule by a polyaddition reaction using polyol, organic polyisocyanate compound and alcoholic hydroxyl group-containing (meth) acrylamide as essential raw materials, and one or more (meta) ) A compound having an acrylate group.
  • the polycarbonate (meth) acrylate is a (meth) acrylate produced by a condensation reaction between a polycarbonate polyol and (meth) acrylic acid or a transesterification reaction between a polycarbonate polyol and (meth) acrylic acid ester.
  • a (meth) acryloyl group-containing polymer compound having a urethane bond is preferable.
  • urethane (meth) acrylate and urethane (meth) acrylamide are preferable in consideration of the adhesion between the image display unit of the image display device and the translucent protective unit.
  • the “urethane (meth) acrylate” in the present specification is a compound having a urethane bond in the molecule and one or more acrylate groups or methacrylate groups.
  • the “urethane (meth) acrylamide” in the present specification is a compound having a urethane bond in the molecule and having one or more acrylamide groups or methacrylamide groups.
  • urethane (meth) acrylate and urethane (meth) acrylamide are not particularly limited, but can be produced, for example, by the following method.
  • urethane (meth) acrylate is obtained using polyol, organic polyisocyanate compound and alcoholic hydroxyl group-containing (meth) acrylate as essential raw material components.
  • the polyol used in the production of this urethane (meth) acrylate has 2 or more alcoholic hydroxyl groups in one molecule, preferably 2 to 3 alcoholic hydroxyl groups, more preferably 2 Is to have.
  • the preferred structure of the polyol is polyester polyol, polycarbonate polyol, or polyether polyol, more preferably polyester polyol or polycarbonate polyol, and most preferably polyester polyol.
  • the hydroxyl value of this polyol is preferably 10 to 120 mgKOH / g, more preferably 15 to 100 mgKOH / g, and particularly preferably 20 to 80 mgKOH / g.
  • the hydroxyl value of the polyol is less than 10 mgKOH / g, the molecular weight and viscosity of the resulting polyurethane (meth) acrylate are too high, handling properties tend to be poor, and handling tends to be difficult.
  • the hydroxyl value of the polyol is greater than 120 mgKOH / g, the volume shrinkage during polymerization becomes too large, or the cohesive strength of the polymer becomes too high, and the adhesive performance of the polymer is not sufficiently exhibited. There is.
  • the organic polyisocyanate compound is not particularly limited as long as it is an organic compound having two or more isocyanato groups in one molecule.
  • the component 1 which is an essential component of the polymerizable composition of the present invention (I) preferably has a low viscosity in consideration of the degree of freedom of subsequent blending.
  • organic polyisocyanate compounds that meet this purpose include 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, 2,4,4-trimethylhexamethylene diisocyanate, 2,2 , 4-trimethylhexanemethylene diisocyanate, 1,6-hexamethylene diisocyanate and norbornane diisocyanate are preferred, more preferably 1,3-bis (isocyanatomethyl) cyclohexane, 2,4,4-trimethylhexamethylene diisocyanate and 2, 2,4-trimethylhexanemethylene diisocyanate, most preferred are 2,4,4-trimethylhexamethylene diisocyanate and 2,2,4-trimethylhexanemethylene diisocyanate It is.
  • the alcoholic hydroxyl group-containing (meth) acrylate is not particularly limited as long as it is a (meth) acrylate having an alcoholic hydroxyl group in one molecule.
  • component 1 which is an essential component of the present invention (I)
  • 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate and 4-hydroxybutyl acrylate are preferable, and 4-hydroxybutyl acrylate is most preferable.
  • a polyol, an organic polyisocyanate compound, and an alcoholic hydroxyl group-containing (meth) acrylate As a method of reacting a polyol, an organic polyisocyanate compound, and an alcoholic hydroxyl group-containing (meth) acrylate, a polyol, an organic polyisocyanate, in the presence or absence of a known urethanization catalyst such as dibutyltin dilaurate or dioctyltin dilaurate
  • a known urethanization catalyst such as dibutyltin dilaurate or dioctyltin dilaurate
  • the compound can be synthesized by reacting the alcoholic hydroxyl group-containing (meth) acrylate, but the reaction in the presence of a catalyst is preferable in terms of shortening the reaction time.
  • the amount used is polyol, organic polyisocyanate compound, alcoholic hydroxyl group-containing (meth) acrylate.
  • the total amount is preferably 0.001 to 1 part by mass with respect to 100 parts by mass.
  • the order in which the raw materials are charged is not particularly limited.
  • the organic polyisocyanate compound and, if necessary, the urethanization catalyst are charged into the reactor and stirred, and then the temperature in the reactor is set to 40 ° C. to 40 ° C.
  • the temperature in the reactor is set to 40 ° C. to 40 ° C.
  • the temperature in the reactor is 50 ° C. to 160 ° C., preferably 60 ° C. to 140 ° C. React.
  • the temperature in the reactor is 30 ° C. to 120 ° C., preferably 50 ° C.
  • a polymerization inhibitor and a urethanization catalyst are added if necessary, and an alcoholic hydroxyl group-containing (meth) acrylate is added dropwise.
  • the temperature in the reactor is preferably maintained at 30 ° C. to 120 ° C., desirably 50 ° C. to 100 ° C.
  • the temperature in the reactor is maintained at 30 ° C. to 120 ° C., preferably 50 ° C. to 100 ° C., to complete the reaction.
  • an organic polyisocyanate compound, a polymerization inhibitor and / or a urethanization catalyst as necessary are charged into the reactor, and stirred, and then the temperature in the reactor is changed from 30 ° C. to 30 ° C.
  • the alcoholic hydroxyl group-containing (meth) acrylate is added dropwise at 120 ° C., preferably 50 ° C. to 110 ° C.
  • the temperature in the reactor is preferably maintained at 30 ° C. to 120 ° C., desirably 50 ° C. to 110 ° C.
  • the temperature in the reactor is maintained at 30 ° C. to 120 ° C., preferably 50 ° C.
  • reaction product is charged into the reactor containing the polyol while stirring so that the temperature in the reactor can be maintained at 30 ° C. to 120 ° C., preferably 50 ° C. to 100 ° C.
  • the temperature in the reactor is maintained at 30 ° C. to 120 ° C., preferably 50 ° C. to 100 ° C., to complete the reaction.
  • Component 1 which is an essential component of the present invention (I)
  • Component 1 which is an essential component of the present invention (I)
  • only a part of the end of the compound is alcohol. It is desirable that the oligomer be sealed with a compound having one hydroxyl group in the molecule containing a functional hydroxyl group-containing (meth) acrylate.
  • the total number of hydroxyl groups of the polyol used is used. It is necessary to increase the total number of isocyanato groups in the organic polyisocyanate compound. In this case, if the ratio of the total number of hydroxyl groups of the polyol used and the total number of isocyanato groups in the organic polyisocyanate compound is close to 1.0, the average molecular weight of the compound to be produced increases. The average molecular weight decreases as the value decreases.
  • the feed molar ratio of the raw material is not particularly limited, but the ratio of the total number of hydroxyl groups in the polyol used and the number of isocyanate groups in the organic polyisocyanate compound is organic with respect to 1 equivalent of the total number of hydroxyl groups in the polyol.
  • the isocyanate group in the polyisocyanate compound is preferably 1.5 equivalents or more. If the total number of hydroxyl groups in the polyol is less than 1.5 equivalents of the isocyanate group in the organic polyisocyanate compound relative to 1 equivalent, the viscosity may be too high.
  • the polyol used and the alcoholic hydroxyl group-containing (meth) acrylate are used.
  • the total number of hydroxyl groups when a compound having one hydroxyl group in the molecule is added to the total number of isocyanato groups of the organic polyisocyanate compound to be used.
  • the total number of hydroxyl groups and the total number of isocyanato groups in the organic polyisocyanate compound when a compound having one hydroxyl group in the molecule including the polyol and alcoholic hydroxyl group-containing (meth) acrylate is combined.
  • the ratio of the total number of isocyanato groups in the organic polyisocyanate compound is equal to the number of hydroxyl groups when a compound having one hydroxyl group in the molecule including a polyol and an alcoholic hydroxyl group-containing (meth) acrylate is used with respect to 1 equivalent.
  • the total number is preferably 2 equivalents or less. More preferably, it is 1.0 to 1.5 equivalents, and most preferably 1.0 to 1.2 equivalents.
  • the total number of isocyanato groups in the organic polyisocyanate compound is 1 equivalent, and the total number of hydroxyl groups when the compound having one hydroxyl group in the molecule including a polyol and alcoholic hydroxyl group-containing (meth) acrylate is combined is 2
  • the amount is larger than the equivalent amount, the number of molecules having no (meth) acryloyl group increases, and the shape retention of the polymer after polymerization may be deteriorated.
  • the ratio of the total number of hydroxyl groups and the total number of isocyanato groups in the organic polyisocyanate compound when a compound having one hydroxyl group in the molecule including a polyol and an alcoholic hydroxyl group-containing (meth) acrylate is combined is different. Two or more kinds of component 1 may be used in combination in the polymerizable composition.
  • Urethane (meth) acrylamide is an alcoholic hydroxyl group-containing (meth) which is a raw material of the urethane (meth) acrylate produced using a polyol, an organic polyisocyanate compound and an alcoholic hydroxyl group-containing (meth) acrylate as essential raw material components. It can be produced by using alcoholic hydroxyl group-containing (meth) acrylamide instead of acrylate.
  • the production conditions of urethane (meth) acrylamide can be produced under the same conditions as the production conditions of urethane (meth) acrylate.
  • urethane (meth) acrylate is obtained using (meth) acrylate having a polyol and an isocyanato group as essential raw material components.
  • the polyol is as described above.
  • Examples of the (meth) acrylate having an isocyanato group that can be used as the raw material include 2-isocyanatoethyl acrylate and 2-isocyanatoethyl methacrylate.
  • Examples of 2-isocyanatoethyl acrylate include Karenz AOI (registered trademark) manufactured by Showa Denko KK.
  • 2-isocyanatoethyl methacrylate include Karenz MOI (registered trademark) manufactured by Showa Denko KK and the like.
  • a urethane (meth) acrylate obtained by using a polyol and a (meth) acrylate having one isocyanato group in one molecule as an essential raw material component is generally synthesized by the following method. Even if the total amount of hydroxyl groups of the polyol is reacted with the (meth) acrylate having an isocyanato group, only a part of the hydroxyl groups of the polyol are reacted with the (meth) acrylate having an isocyanato group, and some of the hydroxyl groups are converted. It doesn't matter if you leave it.
  • the ratio of the total number of hydroxyl groups of the polyol to the total number of isocyanate groups of the isocyanate group-containing (meth) acrylate used is 1 or less.
  • the isocyanate group-containing (meth) used is determined from the total number of hydroxyl groups of the polyol. It is necessary to charge a small total number of isocyanate groups of acrylate.
  • a polyol, a polymerization inhibitor and, if necessary, a urethanization catalyst and an antioxidant are added, put into the reactor, stirring is started, and the temperature in the reactor is increased.
  • the temperature is raised to 40 ° C to 120 ° C, preferably 50 ° C to 100 ° C.
  • (meth) acrylate having an isocyanato group is dropped.
  • the temperature in the reactor is controlled to 40 ° C to 130 ° C, preferably 50 ° C to 110 ° C.
  • the temperature in the reactor is maintained at 40 ° C. to 120 ° C., preferably 50 ° C. to 100 ° C. while stirring is continued to complete the reaction.
  • Component 1 is a structural unit derived from a diol having 4 to 9 carbon atoms and a component having 4 to 10 carbon atoms.
  • a (meth) acryloyl group-containing polymer compound having a polyester structural unit containing a structural unit derived from dicarboxylic acid is preferred.
  • the “structural unit derived from a diol having 4 to 9 carbon atoms” means a structure in which hydrogen in at least one hydroxyl group of two hydroxyl groups of the diol having 4 to 9 carbon atoms is removed. Means.
  • structural unit derived from a dicarboxylic acid having 4 to 10 carbon atoms means OH in two carboxyl groups (—C ( ⁇ O) OH) of the dicarboxylic acid having 4 to 10 carbon atoms. It means a structure in which a group is removed.
  • diol having 4 to 9 carbon atoms examples include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5- Pentanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1 , 5-pentanediol and the like, and these can be used alone or in combination of two or more.
  • 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, and 3-methyl-1,5-pentanediol are more preferable.
  • 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and most preferred is 3-methyl-1,5-pentanediol.
  • dicarboxylic acid having 4 to 10 carbon atoms include succinic acid, glutaric acid, methyl succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, and phthalic acid.
  • glutaric acid methyl succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,1-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 12-cyclohexane- 1,1-dicarboxylic acid, more preferably glutaric acid, methylsuccinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid, and most preferably adipic acid.
  • component 2 which is an essential component of the polymerizable composition of the present invention (I) is a photopolymerization initiator.
  • the photopolymerization initiator of component 2 is not particularly limited as long as it is a compound that generates radicals that contribute to the initiation of radical polymerization upon irradiation with light such as near infrared rays, visible rays, and ultraviolet rays.
  • photopolymerization initiator of Component 2 include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 1,2-hydroxy-2-methyl-1 -Phenylpropan-1-one, ⁇ -hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- (4-isopropylphenyl) propane- 1-one, 2-hydroxy-2-methyl-1- (4-dodecylphenyl) propan-1-one, and 2-hydroxy-2-methyl-1-[(2-hydroxyethoxy) phenyl] propanone, benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methyl Benzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzone, 2-
  • bisacylphosphine oxides include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- ( 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6- Trimethylbenzoyl) phenyl phosphite Oxide, (2,5,6-trimethylbenzo
  • a metallocene compound can be used as a photopolymerization initiator.
  • the metallocene compound the transition metal represented by Fe, Ti, V, Cr, Mn, Co, Ni, Mo, Ru, Rh, Lu, Ta, W, Os, Ir, etc. can be used as the metallocene compound,
  • An example is bis ( ⁇ 5-2,4-cyclopentadien-1-yl) -bis [2,6-difluoro-3- (pyrrol-1-yl) phenyl] titanium.
  • photopolymerization initiators can be used alone or in combination of two or more.
  • 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4, 6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide particularly preferable examples include 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, most preferably 2,4,6-trimethylbenzoyldiphenylphosphine oxide used alone, 1-hydroxycyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone
  • 1,4 to 4 may have a function of cutting the ultraviolet region from the viewpoint of protecting the display unit 2 from ultraviolet rays.
  • 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethyl which is a photopolymerization initiator that can be sensitized even in the visible light region.
  • Benzoylethoxyphenylphosphine oxide is preferably used, and 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide are particularly preferable.
  • the amount of Component 2 used in the present invention (I) is 0.05 to 10.0 parts by weight with respect to 100 parts by weight of the total amount of the polymerizable composition of the present invention (I) excluding Component 2. More preferably, it is 0.1 to 7.0 parts by mass, and particularly preferably 0.2 to 5.0 parts by mass.
  • the amount of component 2 used is less than 0.05 parts by mass relative to 100 parts by mass of component 2 from the total amount of the polymerizable composition of the present invention (I), the polymerization initiator has insufficient polymerization initiation performance. It may become.
  • the polymerizable composition of the present invention the storage modulus at a frequency 0.1Hz is at 25 ° C. of the polymer obtained by polymerizing it was 1 ⁇ 10 3 ⁇ 1 ⁇ 10 5 Pa, 1 ⁇ 10 4 It is preferably ⁇ 1 ⁇ 10 5 Pa.
  • the storage elastic modulus of the polymer at 25 ° C. at a frequency of 0.1 Hz means that a 2.5 mm thick test piece (polymer) is a rheometer manufactured by Auton Pear in an environment of 25 ° C. Is a storage elastic modulus at a frequency of 0.1 Hz measured in vibration mode using MRC301 as a measurement jig and also using a plate PP25 manufactured by Autoon Pear.
  • the storage elastic modulus of the polymer measured under the above conditions is less than 1 ⁇ 10 3 , the polymer may not be able to maintain its shape in a high temperature and high humidity environment or a high temperature environment. Moreover, in the case of 1 ⁇ 10 5 Pa or more, the polymer becomes too hard and sufficient adhesion may not be obtained.
  • the blending amount of the monomer having the alicyclic structure or the aromatic structure among all the raw material monomers constituting Component 1 is 70 mass. % Or less, more preferably 50% by mass or less, and further preferably 5% by mass or more and 40% by mass or less.
  • the storage elastic modulus tends to increase.
  • the number of (meth) acryloyl groups contained in the component 1 compound is preferably 1 to 2 on average per molecule. When the average number exceeds two, the storage elastic modulus increases, and when the average number is less than one, the storage elastic modulus tends to decrease. As described above, the amount of the monomer having an alicyclic structure or an aromatic structure and the number of (meth) acryloyl groups contained in the compound of Component 1 are increased or decreased at a frequency of 0.1 Hz at 25 ° C.
  • the storage elastic modulus can be controlled to be 1 ⁇ 10 3 to 1 ⁇ 10 5 Pa.
  • the present invention (II) is a polymerizable composition for forming a polymer layer interposed between the image display part and the translucent protective part of the image display device, the polymerizable composition comprising: (Component 1) (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 15000, Polymerization obtained by polymerizing the polymerizable composition, comprising (Component 2) a photopolymerization initiator, and (Component 3) a radical polymerizable unsaturated group-containing compound having at least one of an alcoholic hydroxyl group and an amide group.
  • Component 1 (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 15000
  • Polymerization obtained by polymerizing the polymerizable composition comprising (Component 2) a photopolymerization initiator, and (Component 3) a radical polymerizable unsaturated group-containing compound having at least one of an alcoholic
  • Component 1 and Component 2 of the present invention (II) are the same as Component 1 and Component 2 of the present invention (I), respectively.
  • the amount of component 2 is the same as the amount of component 2 described above. The reason why the amount used is preferable is also as described above.
  • component 3 which is an essential component of the polymerizable composition of the present invention (II) is a radical polymerizable unsaturated group-containing compound having at least one of an alcoholic hydroxyl group and an amide group.
  • a (meth) acryloyl group-containing polymer compound having at least one of an alcoholic hydroxyl group and an amide group and having a number average molecular weight in the range of 1000 to 15000 is not included in Component 3. Define.
  • a (meth) acryloyl group-containing polymer compound having at least one of an alcoholic hydroxyl group and an amide group and having a number average molecular weight in the range of 1000 to 15000 is not included in Component 3, and the present invention It is included in Component 1 which is an essential component of the polymerizable composition.
  • the “radical polymerizable unsaturated group” means a carbon-carbon double bond capable of addition polymerization by a radical generated by a radical polymerization initiator or the like.
  • radical polymerizable unsaturated group-containing compound having an amide group as Component 3 include, for example, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-acryloylmorpholine, N-isopropylacrylamide, N- tert-butylacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, Nn-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide, N- Methacryloylmorpholine, N-isopropylmethacrylamide, N-tert-butylmethacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylmethacrylamide, Nn-butoxymethylmethacrylate And N-isobutoxymethylmethacrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide
  • N, N-diethylacrylamide, N-acryloylmorpholine, N-tert-butylacrylamide, N-tert-butylacrylamide, N-ethoxymethylacrylamide, Nn-butoxymethylacrylamide, N -Isobutoxymethylacrylamide and N-vinylpyrrolidone more preferably N, N-diethylacrylamide, N-acryloylmorpholine, N-ethoxymethylacrylamide, Nn-butoxymethylacrylamide, N-isobutoxymethylacrylamide Most preferred is N-acryloylmorpholine.
  • radical polymerizable unsaturated group-containing compound having an alcoholic hydroxyl group as component 3 include, for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate.
  • 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate and 2-hydroxybutyl methacrylate are preferable, and 4-hydroxybutyl acrylate is more preferable.
  • the amount of component 3 used in the present invention (II) is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, particularly based on the total amount of component 1 and component 3 combined. Preferably, it is 3 to 10% by mass.
  • the amount of component 3 used in the present invention (II) is less than 1% by mass relative to the total amount of component 1 and component 3, the polymer of the present invention (V) described later and the optical pressure-sensitive adhesive sheet May whiten in a hot and humid environment.
  • the usage-amount of the component 3 in this invention (II) is more than 30 mass% with respect to the total amount which combined the component 1 and the component 3, at the time of superposition
  • the amount of component 1 used in the present invention (II) is preferably 70 to 99% by mass, more preferably 80 to 98% by mass, based on the total amount of component 1 and component 3 combined. Particularly preferred is 90 to 97% by mass.
  • the usage-amount of the component 3 in this invention (II) is less than 70 mass% with respect to the total amount which combined the component 1 and the component 3, the volume shrinkage at the time of superposition
  • the usage-amount of the component 1 in this invention (II) is 99 mass% or more with respect to the total amount which combined the component 1 and the component 3, the viscosity of polymeric composition may become high too much. is there.
  • the present invention (III) is a polymerizable composition for forming a polymer layer interposed between the image display part of the image display device and the translucent protective part, the polymerizable composition comprising: (Component 1) (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 15000, (Component 2) Photopolymerization initiator, (Component 3) a radical polymerizable unsaturated group-containing compound having at least one of an alcoholic hydroxyl group and an amide group, and (Component 4) no alcoholic hydroxyl group or amide group, and a viscosity of 25 ° C.
  • a polymer obtained by polymerizing the polymerizable composition containing a (meth) acryloyl group-containing compound that is 500 mPa ⁇ s or less has a storage elastic modulus at 25 ° C. and a frequency of 0.1 Hz of 1 ⁇ 10 3 to The polymerizable composition is 1 ⁇ 10 5 Pa.
  • Component 1 and Component 2 of the present invention (III) are the same as Component 1 and Component 2 of the present invention (I), respectively, and Component 3 of the present invention (III) is a component of the present invention (II). It is the same as 3.
  • the amount of component 2 is the same as the amount of component 2 described above. The reason why the amount used is preferable is also as described above.
  • Component 4 is a (meth) acryloyl group-containing compound which does not have any group of alcoholic hydroxyl group and amide group and has a viscosity of 500 mPa ⁇ s or less at 25 ° C.
  • the group-containing polymer compound is defined as not included in Component 4.
  • the group-containing polymer compound is not included in Component 4, but is included in Component 1 which is an essential component of the polymerizable composition of the present invention.
  • component 4 include, for example, cyclohexyl acrylate, isobornyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentanyl ethyl acrylate, 4-tert-butylcyclohexyl acrylate.
  • the amount of component 4 used in the present invention (III) is preferably 3 to 40% by mass based on the total amount of component 1, component 3 and component 4 as essential components of the present invention (III).
  • the amount is preferably 5 to 35% by mass, particularly preferably 7 to 30% by mass.
  • component 4 used in the present invention (III) is more than 40% by mass with respect to the total amount of component 1, component 3 and component 4 which are essential components of the present invention (III), There is a possibility that the volumetric shrinkage during polymerization of the polymerizable composition of the invention (III) is increased.
  • the amount of component 3 used in the present invention (III) is the same as the preferred amount used for component 3 in the present invention (II) with respect to the total amount of components 1, 3 and 4 combined.
  • the reason why the amount used is preferable is also as described above.
  • the amount of component 1 used in the present invention (III) is preferably 50 to 96% by mass, more preferably 55 to 93% by mass, based on the total amount of component 1, component 3 and component 4 combined. %, Particularly preferably 60 to 90% by mass. The reason why the above range is preferable is the same as in the case of the present invention (II).
  • the present invention (IV) is a polymerizable composition for forming a polymer layer interposed between the image display part of the image display device and the translucent protective part, the polymerizable composition comprising: (Component 1) (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 15000, (Component 2) Photopolymerization initiator, (Component 3) Radical polymerizable unsaturated group-containing compound having at least one of an alcoholic hydroxyl group and an amide group, (Component 4) a (meth) acryloyl group-containing compound which does not have any group of an alcoholic hydroxyl group and an amide group and has a viscosity of 500 mPa ⁇ s or less at 25 ° C.
  • Nonionic surfactant having no (meth) acryloyl group and (Component 6) No (meth) acryloyl group in the molecule, a function for suppressing radical polymerization, a function for inhibiting radical polymerization, light Liquid or solid at 25 ° C., which has neither a polymerization initiation function nor a surface-active function, and is composed of carbon atoms and hydrogen atoms, or is composed of carbon atoms, hydrogen atoms and oxygen atoms
  • the storage modulus of the polymer obtained by polymerizing the polymerizable composition at 25 ° C. and a frequency of 0.1 Hz is 1 ⁇ 10 3 to 1 ⁇ 10 5 Pa.
  • the present invention relates to a polymerizable composition.
  • Component 1 and Component 2 of the present invention (IV) are respectively the same as Component 1 and Component 2 of the present invention (I), and Component 3 of the present invention (IV) is a component of the present invention (II). 3, component 4 of the present invention (IV) is the same as component 4 of the present invention (III).
  • the amount of component 2 is the same as the amount of component 2 described above. The reason why the blending amount is preferable is also as described above.
  • component 5 which is an essential component of the polymerizable composition of the present invention (IV) will be described.
  • Component 5 is a nonionic surfactant that does not have a (meth) acryloyl group.
  • surfactant in this specification is a generic name for substances having a portion that is familiar with water (hydrophilic group) and a portion that is familiar with oil (lipophilic group / hydrophobic group). And a vesicle, a lamellar structure, and the like, thereby having a property capable of uniformly mixing a polar substance and a nonpolar substance.
  • Griffin's HLB Hydrophilicity-Lipophile Balance
  • HLB value of Griffin is 3.0 to 9.0, more preferably 3. It is 0 to 7.5, and particularly preferably 3.0 to 6.0.
  • component 6 that is an essential component of the polymerizable composition of the present invention (IV) will be described.
  • Component 6 has no (meth) acryloyl group in the molecule, does not have any function of suppressing radical polymerization, function of inhibiting radical polymerization, photopolymerization initiating function, or surface-active function, and carbon atom And a hydrogen atom or a compound composed of a carbon atom, a hydrogen atom and an oxygen atom, which is liquid or solid at 25 ° C.
  • Component 6 is preferably a compound composed of only carbon atoms and hydrogen atoms, or a compound composed of only carbon atoms, hydrogen atoms and oxygen atoms and having no ethylenic double bond.
  • an image display device is manufactured using a manufacturing method including a step of forming a polymer layer by interposing a polymerizable composition between a base portion having an image display portion and a translucent protective portion and polymerizing the polymerizable composition.
  • the polymerizable composition used in this step preferably contains component 6 for the purpose of keeping the volume shrinkage during polymerization low. In addition to suppressing the volume shrinkage during polymerization, it may be used for the purpose of increasing the adhesion of the polymer to an adherend such as glass or acrylic resin.
  • the component 6 a compound that is liquid at 25 ° C. or a compound that is solid at 25 ° C. can be used.
  • Examples of compounds used as component 6 that are liquid at 25 ° C. include poly ( ⁇ -olefin) liquid, ethylene-propylene copolymer liquid, ethylene- ⁇ -olefin copolymer liquid, and propylene- ⁇ -olefin.
  • the poly ( ⁇ -olefin) liquid is a liquid produced by polymerization of ⁇ -olefin, and the ⁇ -olefin is a hydrocarbon compound having one carbon-carbon double bond at the molecular end.
  • the ethylene- ⁇ -olefin copolymer liquid is a liquid polymer produced by copolymerizing ethylene and ⁇ -olefin.
  • An ⁇ -olefin is a hydrocarbon compound having one carbon-carbon double bond at the molecular end, such as 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, Examples thereof include 1-tetradecene, 1-hexadecene, 1-octadecene and the like.
  • the propylene- ⁇ -olefin copolymer liquid material is a liquid polymer produced by copolymerizing propylene and ⁇ -olefin.
  • An ⁇ -olefin is a hydrocarbon compound having one carbon-carbon double bond at the molecular end, such as 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, Examples thereof include 1-tetradecene, 1-hexadecene, 1-octadecene and the like.
  • Liquid polybutene is a liquid polymer containing isobutene or n-butene as a (co) polymerization component, such as homopolymerization of isobutene, homopolymerization of n-butene, copolymerization of isobutene and n-butene. It is a compound having a carbon-carbon unsaturated bond.
  • Examples of commercially available liquid polybutene include Nisseki Polybutene LV-7, LV-50, LV-100, HV-15, HV-35, HV-50, HV-100, manufactured by JX Nippon Mining & Energy Corporation. And HV-300.
  • the liquid hydrogenated polybutene is a liquid material having a side chain obtained by hydrogenating the liquid polybutene.
  • palm reel 4 palm reel 6, palm reel 18, palm reel 24 manufactured by NOF Corporation.
  • palm reel EX palm reel EX.
  • Liquid polybutadiene is a butadiene polymer that is liquid at room temperature.
  • POLYVEST110, POLYVEST130 manufactured by Evonik Degussa NISSO-PB B-1000, NISSO-PB B-2000, NISSO-PB B- manufactured by Nippon Soda Co., Ltd. 3000 etc. can be mentioned.
  • the liquid hydrogenated polyptadiene is a liquid material obtained at a normal temperature obtained by reductive hydrogenation of a butadiene polymer.
  • Examples thereof include NISSO-PB BI-2000 and NISSO-PB B-3000 manufactured by Nippon Soda Co., Ltd. Can do.
  • Liquid polyisoprene is a liquid isoprene polymer at room temperature, and examples thereof include Kuraray LIR-30 manufactured by Kuraray Co., Ltd.
  • Liquid hydrogenated polyisoprene is a compound that is liquid at room temperature obtained by reductive hydrogenation of an isoprene polymer, and examples thereof include LIR-200 manufactured by Kuraray Co., Ltd.
  • the liquid polybutadiene polyol is a polymer that is liquid at room temperature and has two or more hydroxyl groups at the molecular terminals and has a polybutadiene structural unit.
  • Examples thereof include G-2000, NISSO-PB G-3000, and Poly bd manufactured by Idemitsu Kosan Co., Ltd.
  • the liquid hydrogenated polybutadiene polyol is a liquid polyol having a structure obtained by reductive hydrogenation of polybutadiene polyol or polybutadiene polycarboxylic acid.
  • NISSO-PB GI-3000 manufactured by Nippon Soda Co., Ltd.
  • the liquid polyisoprene polyol is a polymer that is liquid at room temperature and has two or more hydroxyl groups at the molecular ends and a polyisoprene structural unit, and examples thereof include poly ip manufactured by Idemitsu Kosan Co., Ltd. .
  • the liquid hydrogenated polyisoprene polyol is a liquid polyol having a structure obtained by reductive hydrogenation of polyisoprene polyol or polyisoprene polycarboxylic acid, and examples thereof include Epole manufactured by Idemitsu Kosan Co., Ltd.
  • polyether polyol examples include polypropylene glycol, polytetramethylene glycol, and propylene oxide-tetrahydrofuran copolymer.
  • polyester polyol examples include a polycondensate of a polyol and a polycarboxylic acid, a transesterification product of an ester of a polyol and a polycarboxylic acid, a ring-opening polymer of a cyclic ester into a polyol, and the like.
  • polycarbonate polyol examples include a polycondensate of polyol and phosgene, or a transesterification product of a polyol with an organic carbonate such as dimethyl carbonate, diethyl carbonate, or ethylene carbonate.
  • Polyols used as raw materials for polycarbonate polyols include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,8 -Octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, Examples thereof include trimethylolethane and trimethylolpropane. These can be used alone or in combination of two or more.
  • 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, and 3-methyl-1,5-pentanediol are more preferable.
  • examples thereof include 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol and the like, and most preferred is 3-methyl-1,5-pentanediol.
  • a compound that is solid at 25 ° C. can be used as component 6.
  • the compound used as component 6 that is solid at 25 ° C. is preferably a compound having no carbon-carbon unsaturated bond in the molecule.
  • examples of such compounds include a solid epoxy resin at 25 ° C., a polyester resin solid at 25 ° C., a polyol resin solid at 25 ° C., a hydrogenated petroleum resin solid at 25 ° C., and a terpene hydrogenated resin.
  • Mention may be made of tackifiers such as resins and hydrogenated rosin esters. Among these, preferred are tackifiers such as hydrogenated petroleum resins, terpene hydrogenated resins, and hydrogenated rosin esters.
  • Hydrogenated petroleum resin is a resin obtained by hydrogen reduction of petroleum-based resin.
  • Examples of petroleum resins that are raw materials for hydrogenated petroleum resins include aliphatic petroleum resins, aromatic petroleum resins, aliphatic-aromatic copolymer petroleum resins, alicyclic petroleum resins, dicyclopentadiene resins, and the like.
  • Modified products such as hydrogenated products of The synthetic petroleum resin may be C5 or C9.
  • the terpene-based hydrogenated resin is a resin obtained by reductive hydrogenation of a terpene-based resin.
  • Terpenic resins that are raw materials for terpene hydrogenated resins include ⁇ -pinene resins, ⁇ -pinene resins, ⁇ -limonene resins, ⁇ -limonene resins, pinene-limonene copolymer resins, and pinene-limonene-styrene copolymer resins.
  • the hydrogenated rosin ester is a resin obtained by hydrogenating a rosin ester obtained by esterifying a hydrogenated rosin obtained by hydrogenating a rosin resin or esterifying a rosin.
  • the rosin resin tackifier include modified rosins such as gum rosin, tall oil rosin, wood rosin, disproportionated rosin, polymerized rosin and maleated rosin.
  • a compound in which some alcoholic hydroxyl groups of polyhydric alcohol are esterified with hydrogenated rosin and a compound in which all alcoholic hydroxyl groups of polyhydric alcohol are esterified with hydrogenated rosin Both are defined as being included in the hydrogenated rosin ester.
  • hydrogenated rosin esters and terpene-phenol resins are more preferable, hydrogenated rosin esters are more preferable, and triols such as glycerin, trimethylolpropane, and trimethylolethane are particularly preferable.
  • hydrogenated rosin ester which is esterification of tetraol such as pentaerythritol and hydrogenated rosin, or triol such as glycerin, trimethylolpropane and trimethylolethane or tetraol and rosin ester such as pentaerythritol (rosin ester) ) Hydrogenated rosin ester obtained by hydrogen reduction.
  • the compound of Component 6 includes a compound that is liquid at 25 ° C. and 25 ° C.
  • a solid compound can be used in combination. More preferably, it is a combined use of polyether polyol, polyester polyol or polycarbonate polyol which is liquid at 25 ° C., and a tackifier which is solid at 25 ° C., and particularly preferably polyester polyol or polycarbonate polyol, It is to use together with hydrogenated rosin ester.
  • a preferred combination ratio is 25 by mass ratio with respect to 90 equivalents of the compound that is liquid at 25 ° C. 10 equivalents of the compound that is solid at 25 ° C. to 90 equivalents of the compound that is solid at 25 ° C., more preferably 10 equivalents of the compound that is liquid at 25 ° C. 15 equivalents of the compound that is solid at 25 ° C. with respect to the equivalent amount to 85 equivalents of the compound that is solid at 25 ° C. with respect to 15 equivalents of the compound that is liquid at 25 ° C.
  • the amount of component 5 used in the present invention (IV) is 3 to 40% by mass based on the total amount of component 1, component 3, component 4, component 5 and component 6 as essential components of the present invention (IV). It is preferably 4 to 35% by mass, more preferably 5 to 30% by mass.
  • the amount of component 5 used is less than 3% by mass based on the total amount of component 1, component 3, component 4, component 5 and component 6 as essential components of the present invention (IV)
  • the transparency of the coating film of the polymer obtained by polymerizing the polymerizable composition of IV) may be lost.
  • the usage-amount of the component 5 is contained exceeding 40 mass% with respect to the total amount which combined the component 1, the component 3, the component 4, the component 5, and the component 6 which are essential components of this invention (IV).
  • the film strength of the polymer obtained by polymerizing the polymerizable composition of the present invention (IV) may be too low.
  • the amount of component 6 used in the present invention (IV) is 15 to 85% by mass based on the total amount of component 1, component 3, component 4, component 5 and component 6 as essential components of the present invention (IV). It is preferably 30 to 70% by mass, more preferably 40 to 60% by mass.
  • the usage-amount of the component 6 in this invention (IV) is less than 15 mass% with respect to the total amount which combined the component 1, the component 3, the component 4, the component 5, and the component 6 which are essential components of this invention (IV). In some cases, the effect of adding the component 6 (that is, the effect of reducing the volumetric shrinkage during polymerization) cannot be obtained.
  • the usage-amount of the component 6 in this invention (IV) is 85 mass% with respect to the total amount which combined the component 1, the component 3, the component 4, the component 5, and the component 6 which are essential components of this invention (IV).
  • the coating strength of the polymer obtained by polymerizing the polymerizable composition of the present invention (IV) may become too low.
  • the amount of component 1 used in the present invention (IV) is preferably 10 to 40% by mass, more preferably based on the total amount of component 1, component 3, component 4, component 5 and component 6 combined. Is from 13 to 37% by mass, particularly preferably from 15 to 35% by mass.
  • the amount of component 1 used in the present invention (IV) is less than 10% by mass with respect to the total amount of component 1, component 3, component 4, component 5 and component 6, the image display unit of the image display device There is a possibility that the adhesion strength of the polymer obtained by polymerizing the polymerizable composition of the present invention (IV) to the above material or the material of the translucent protective part is lowered.
  • the usage-amount of the component 1 in this invention (IV) is 40 mass% or more with respect to the total amount which combined the component 1, the component 3, the component 4, the component 5, and the component 6, In some cases, the viscosity becomes too high, or the storage elastic modulus becomes too high.
  • the amount of Component 3 used in the present invention (IV) is preferably 1 to 15% by mass, more preferably, based on the total amount of Component 1, Component 3, Component 4, Component 5 and Component 6. It is 2 to 10% by mass, and particularly preferably 2 to 8% by mass. The reason is the same as in the case of the present invention (II) or the present invention (III).
  • the amount of Component 4 used in the present invention (IV) is 3 to 20% by mass based on the total amount of Component 1, Component 3, Component 4, Component 5 and Component 6 as essential components of the present invention (IV). It is preferably 4 to 19% by mass, more preferably 5 to 18% by mass. The reason is the same as in the case of the present invention (III).
  • the volume shrinkage ratio at the time of polymerization of the polymerizable composition of the present invention (IV). Is preferably 3.5% or less, more preferably 2.7% or less, and most preferably 2.3% or less.
  • the volumetric shrinkage during polymerization of the polymerizable composition of the present invention (IV) is greater than 3.5%, the internal stress accumulated in the polymer increases when the polymerizable composition is polymerized. In some cases, the interface between the polymer layer 5a or 5b and the display unit 2, the protection unit 3 or the touch panel 7 in contact with the polymer layer 5a or 5b may be distorted.
  • the viscosity of the polymerizable composition of the present invention (I) to the present invention (IV) at 25 ° C. is not particularly limited, but is preferably 10000 mPa ⁇ s or less, more preferably 7000 mPa ⁇ s or less in terms of handling. Especially preferably, it is 5000 mPa ⁇ s or less.
  • the viscosity described in this specification is a cone / plate viscometer (manufactured by Brookfield, model: DV-II + Pro, spindle model number: CPE-42) for a composition having a viscosity of 10000 mPa ⁇ s or less at 25 ° C. ) Using a temperature of 25.0 ° C.
  • the viscosity of the polymerizable composition of the present invention (I) to the present invention (IV) is set to 1000 mPa ⁇ s or less at 25 ° C.
  • the polymerizable composition of the present invention (I) to the present invention (IV) is used in a dispenser.
  • the spread of the liquid becomes easy after application, and as a result, it becomes easy to spread the composition with a uniform thickness at the required location, and further, the entrainment of bubbles is suppressed. It becomes easy to be done.
  • a polymerization inhibitor, an inhibitor and an antioxidant can be preferably added.
  • the polymerization inhibitor and the polymerization inhibitor are not particularly limited as long as they have a polymerization inhibition ability or a function to inhibit polymerization.
  • hydroquinone p-methoxyphenol, p-benzoquinone, naphthoquinone, phenanthraquinone, 2,5-diacetoxy-p-benzoquinone, 2,5-dicaproxy-p-benzoquinone, 2,5-acyloxy-p- Benzoquinone, pt-butylcatechol, 2,5-di-t-butylhydroquinone, p-tert-butylcatechol, mono-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, di-t-butyl -Paracresol hydroquinone monomethyl ether and phenothiazine are preferably used.
  • the polymerization inhibitor can be adjusted so as to be added in an amount of 0.01 to 5% by mass based on the total amount of the polymerizable composition of the present invention (I) to the present invention (IV).
  • the amount of the polymerization inhibitor is a value obtained by adding the polymerization inhibitor contained in the component 1, component 2, component 3, component 4 and component 6 when the polymerization inhibitor is contained in advance. It is. That is, generally, a polymerization inhibitor is previously contained in component 1, component 2, component 3, component 4 and component 6, but the total amount of this polymerization inhibitor and the newly added polymerization inhibitor is This means that the added amount is 0.01 to 5% by mass based on the total amount of the polymerizable composition of the present invention (I) to the present invention (IV).
  • the polymerization inhibitor When the polymerization inhibitor is less than 0.01% by mass with respect to the total amount of the polymerizable composition of the present invention (I) to the present invention (IV), the storage stability of the compound is reduced due to insufficient polymerization inhibiting ability. There may be a shortage.
  • the amount of the polymerization inhibitor is more than 5% by mass relative to the total amount of the polymerizable composition of the present invention (I) to the present invention (IV)
  • the color becomes darker due to coloring during heat-resistant storage, The polymerization rate at the time of polymerization may decrease.
  • an antioxidant can be added to the polymerizable compositions of the present invention (I) to the present invention (IV) and is preferable.
  • the antioxidant is not particularly limited.
  • pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
  • octadecyl-3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate
  • thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] 3,5-di-tert-butyl-4 7-C9 alkyl ester of hydroxybenzenepropanoic acid, 4,6-bis (octylthiomethyl) -o-cresol, 3,9-bis [2- [3- (3-tert-butyl-4- Hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethyl
  • Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate triethylene glycol bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, n-octadecyl 3- (4'-hydroxy-3 ', 5'-di-tert-butylphenyl) propionate, more preferably pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate], triethylene glycol Bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, n-octadecyl 3- (4'-hydroxy-3 ', 5'-di-tert-butylphenyl) propionate, particularly preferred Is triethylene glycol bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, n-octadecyl
  • the antioxidant can be adjusted so as to be added in an amount of 0.01 to 5% by mass relative to the total amount of the polymerizable composition of the present invention (I) to the present invention (IV).
  • the amount of the antioxidant is a value in consideration of the antioxidant contained in the other components such as the component 6 in advance. That is, when an antioxidant is preliminarily contained in the component 6 or the like, the total amount of this antioxidant and the newly added antioxidant is the present invention (I) to the present invention (IV ) To 0.01 to 5% by mass based on the total amount of the polymerizable composition.
  • the antioxidant When the antioxidant is less than 0.01% by mass relative to the total amount of the polymerizable composition of the present invention (I) to the present invention (IV), the addition effect (that is, the antioxidant effect) may not be exhibited. is there. Further, when the amount of the polymerization inhibitor is more than 5% by mass based on the total amount of the polymerizable composition of the present invention (I) to the present invention (IV), the polymer of the present invention (V) described later or the later described From the optical pressure-sensitive adhesive sheet, an antioxidant may precipitate or bleed.
  • the present invention (V) is a polymer obtained by polymerizing the polymerizable composition of the present invention (I) to the present invention (IV).
  • the polymer of the present invention (V) is a low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, xenon lamp, metal halide lamp, electrodeless lamp, LED, etc. It is obtained by polymerizing the polymerizable composition by irradiation through a glass or plastic substrate.
  • the polymer of this invention (V) is a polymer used as a polymer layer interposed between the image display part of an image display apparatus, and a translucent protection part.
  • This polymer must have a storage modulus of 1 ⁇ 10 3 to 1 ⁇ 10 5 Pa at 25 ° C. and a frequency of 0.1 Hz.
  • the “storage modulus of the polymer at 25 ° C. and a frequency of 0.1 Hz” is as defined above.
  • a more preferable value of the storage elastic modulus is 1 ⁇ 10 4 to 1 ⁇ 10 5 Pa.
  • the storage elastic modulus of the polymer is less than 1 ⁇ 10 3 , the polymer cannot maintain its shape in a high-temperature and high-humidity environment or in a high-temperature environment, and sufficient adhesion may not be obtained. . Moreover, in the case of 1 ⁇ 10 5 Pa or more, the polymer becomes too hard and sufficient adhesion may not be obtained.
  • the polymer of the present invention (V) is applied to the polymer (layer) 5b filled between the image display unit 2 and the translucent protection unit 3 in the In-Cell type capacitive touch panel display shown.
  • the dielectric constant of the polymer of the present invention (V) is high.
  • the dielectric constant of the polymer measured at 23 ° C., frequency 1 MHz, and applied voltage 100 mV means that a 2 mm-thick test piece (polymer) is manufactured by Agilent Technologies in an environment of 23 ° C. 4294A Precision Impedance Analyzer 40Hz-110MHz is used as the impedance analyzer, and 16451B dielectric test fixture manufactured by Agilent Technologies is used as the test fixture, and the frequency is 1MHz and the applied voltage is 100mV.
  • a more preferable dielectric constant value is a dielectric constant measured under the above conditions of 5.5 or more, more preferably 6.0 or more, and particularly preferably 6.1 or more.
  • the dielectric constant of the polymer measured under the above conditions is less than 5.0, the sensitivity of the capacitive touch panel may decrease.
  • the upper limit of the dielectric constant is not particularly limited. However, when the dielectric constant is increased, the polarity increases, and as a result, the water resistance tends to decrease. In order to prevent the water resistance from being extremely impaired, the dielectric constant is 40 Or less, more preferably 20 or less, and most preferably 10 or less.
  • a urethane using a polyol and (meth) acrylate having one isocyanato group in one molecule as an essential raw material component
  • (meth) acrylate is obtained, a (meth) acryloyl group-containing polymer having a structural unit derived from a diol having 4 to 9 carbon atoms and a structural unit derived from a dicarboxylic acid having 4 to 10 carbon atoms It is preferable to use molecular compounds.
  • the “structural unit derived from a diol having 4 to 9 carbon atoms” means a structure in which hydrogen in at least one of the two hydroxyl groups of the diol having 4 to 9 carbon atoms is removed. Means. Further, in this specification, “structural unit derived from a dicarboxylic acid having 4 to 10 carbon atoms” means OH in two carboxyl groups (—C ( ⁇ O) OH) of the dicarboxylic acid having 4 to 10 carbon atoms. It means a structure in which a group is removed. When only a diol having 3 or less carbon atoms is used, the hydrophilicity of the polymer obtained by polymerizing component 1 may become too high and the water resistance may be weakened.
  • the dielectric constant of a polymer obtained by polymerizing component 1 may decrease.
  • polymerizing the component 1 of the said polymerization composition may become high too much, and may become weak in water resistance.
  • polymerizing the component 1 of the said polymerization composition may fall.
  • the diol having 4 to 9 carbon atoms are as described above.
  • Specific examples of the dicarboxylic acid having 4 to 10 carbon atoms are as described above.
  • Component 4 is methoxyethyl (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, phenoxyethyl (meth) acrylate, 3-methyl-3-oxetanylmethyl (meth) acrylate, 1,4-dioxaspiro [4.5] dec-2-ylmethyl (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolane-4- (Il) (meth) acryloyl group having a cyclic ester such as (meth) acryloyl group-containing compound having an ether bond in the molecule such as methyl (meth) acrylate, ⁇ -methacryloxy- ⁇ -butyrolactone, ⁇ -acryloxy- ⁇ -butyrolactone
  • it is a contained compound, more preferred Examples include methoxyeth
  • the refractive index of the polymer of the present invention (V) at 25 ° C. is preferably 1.45 to 1.55, and more preferably 1.48 to 1.52.
  • the refractive index at 25 ° C. is less than 1.45 or larger than 1.55, it is too low compared to the refractive index of the optical glass or the like that is the material of the protective part, so the interface between the display part and the protective part.
  • the difference in the refractive index of the image becomes slightly larger, and the scattering and attenuation of the image light from the display portion become slightly larger.
  • the volume shrinkage during polymerization of the polymer of the present invention is preferably 3.5% or less, more preferably 2.7% or less, and most preferably 2.3% or less. become.
  • the internal stress accumulated in the polymer layer when the polymerizable composition is polymerized can be reduced, and the interface between the polymer layer 5a and the touch panel 7 or the protective part 3, or the polymer layer 5b and the touch panel. 7.
  • the polymerizable composition is interposed between the touch panel 7 and the protection unit 3, between the touch panel 7 and the display unit 2, or between the display unit 2 and the protection unit 3, and the polymerizable composition is polymerized.
  • the scattering of light generated at the interface between the polymer layer 5 and the display unit 2, the protection unit 3, and the touch panel 7 can be reduced, and the brightness of the display image can be increased and the visibility can be improved. it can.
  • the volume shrinkage during polymerization is larger than 3.5%, the internal stress accumulated in the polymer when the polymerizable composition is polymerized becomes too large, and the polymer layer 5a or 5b and those May be distorted at the interface with the display unit 2, the protection unit 3, or the touch panel 7 in contact with the touch panel.
  • the component 1 is added to the total amount of the polymerizable composition of the present invention (I) to the present invention (IV).
  • the component 1 is contained in an amount of 10 to 40% by mass based on the total amount of the polymerizable composition of the present invention (I) to the present invention (IV), and the total amount of the component 3 and the component 4 is It is preferable to contain 1 to 25% by mass with respect to the total amount of component 1, component 3, component 4, component 5, and component 6, which are essential components of the present invention (IV).
  • the polymerized product of the present invention (V) was interposed between two glasses at a thickness of 200 ⁇ m to form a laminate, and the polymerization was performed when the laminate was peeled in a direction perpendicular to the glass at 500 mm / min It is desirable that the breaking strength between the object and the glass is 20 N / cm 2 or more.
  • the “laminate” described in the present specification includes a polymerizable composition interposed between two optical glasses having a thickness of 0.7 mm (manufactured by Corning, trade name: Eagle XG (registered trademark)), By irradiating light that can be sensitized by the photopolymerization initiator through the optical glass, using a low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, xenon lamp, metal halide lamp, electrodeless lamp, LED, etc. as a light source It is a laminate composed of any of the polymer layers obtained by preparing a polymer having a thickness of 200 ⁇ m and glass existing outside the polymer layer.
  • the portion sandwiched between the two sheets of glass outside the polymer layer does not contain any spacers, gaskets, or sealants.
  • the breaking strength of the polymer and the glass when the laminate is peeled in the direction perpendicular to the glass at 500 mm / min is 20 N / cm 2 or more” means the outer glass surface (both sides).
  • a plastic jig was affixed using a double-sided tape so that it could be sandwiched between chucks of a tensile tester (manufactured by Shimadzu Corporation, EZ Test / CE). Attach two glass with polymer film with plastic jig attached to Shimadzu EZ Test / CE, and pull the glass on both sides at a speed of 500mm / min.
  • the breaking strength of the polymer and the glass when the property is evaluated is 20 N / cm 2 or more.
  • the breaking strength of the polymer and glass measured under the above conditions is less than 20 N / cm 2 , an image display unit, a translucent protective unit, and an image display device in which a polymer layer is interposed therebetween are produced. Further, peeling may occur between the image display portion and the polymer layer, or between the light-transmitting protective portion and the polymer layer.
  • component 1 is added to the total amount of the polymerizable composition of the present invention (I) to the present invention (IV).
  • the content is preferably 10 to 40% by mass. More preferably, the amount of component 5 used is 5 to 30% by mass based on the total amount of component 1, component 3, component 4, component 5 and component 6 as essential components of the present invention (IV), The amount of component 6 used is preferably 40 to 60% by mass based on the total amount of component 1, component 3, component 4, component 5 and component 6 as essential components of the present invention (IV).
  • a laminate was prepared by interposing the polymer of the present invention (V) with glass, a resin plate and a thickness of 200 ⁇ m between them, and stored in an environment of 60 ° C. and 90% RH for 72 hours, and at 23 ° C. and 50% RH. It is preferable that no peeling occurs between the polymer and the glass and / or between the polymer and the resin plate after storage for 48 hours in an environment of 23 ° C. and 50% RH.
  • a laminate is prepared by interposing the polymer with a glass, a resin plate and a thickness of 200 ⁇ m therebetween” refers to one optical glass having a thickness of 0.7 mm (trade name: manufactured by Corning).
  • the present invention (VI) is a polymerizable composition for producing an optical pressure-sensitive adhesive sheet used as a polymer layer interposed between an image display part and a translucent protective part of an image display device.
  • the polymerizable composition is a polymerizable composition according to the present invention (I) to the present invention (IV). Using the polymerizable composition of the present invention (I) to the present invention (IV) as a raw material, the optical pressure-sensitive adhesive sheet can be produced.
  • the present invention (VII) has a thickness obtained by applying the polymerizable composition of the present invention (VI), irradiating the polymerizable composition with light capable of being photosensitized by the photopolymerization initiator, and polymerizing the polymerizable composition.
  • An optical pressure-sensitive adhesive sheet having a polymer layer of 10 to 1000 ⁇ m.
  • the optical pressure-sensitive adhesive sheet can be obtained by polymerizing a polymerization composition by irradiating light similar to the conditions under which the polymer of the present invention (V) is polymerized.
  • the optical pressure-sensitive adhesive sheet may be a double-sided pressure-sensitive adhesive sheet in which both surfaces of the sheet are pressure-sensitive adhesive surfaces (pressure-sensitive adhesive layer surface), or only one surface of the sheet is a pressure-sensitive adhesive surface (pressure-sensitive adhesive layer surface).
  • a single-sided adhesive sheet may be sufficient. Especially, it is preferable that it is a double-sided adhesive sheet from a viewpoint of bonding two members together.
  • the term “adhesive sheet” includes a tape-shaped material, that is, “adhesive tape”.
  • the optical pressure-sensitive adhesive sheet is a so-called “baseless-less type” optical pressure-sensitive adhesive sheet (hereinafter sometimes referred to as a “baseless-less optical pressure-sensitive adhesive sheet”) that does not have a base material (base material layer). It may also be an optical pressure-sensitive adhesive sheet having a base material.
  • the substrate-less optical pressure-sensitive adhesive sheet include, for example, a double-sided pressure-sensitive adhesive sheet composed only of the polymer layer composed of the polymer of the present invention, and a polymer layer composed of the polymer of the present invention and a pressure-sensitive adhesive other than the polymer layer. Examples thereof include a double-sided pressure-sensitive adhesive sheet composed of layers.
  • a pressure-sensitive adhesive sheet for baseless optics pressure-sensitive adhesive sheet for baseless double-sided optics
  • base material base material layer
  • release liner separator
  • the thickness of the polymer layer of the optical pressure-sensitive adhesive sheet is 10 to 1000 ⁇ m, preferably 20 to 700 ⁇ m, and more preferably 30 to 500 ⁇ m. If the thickness of the polymer layer exceeds 1000 ⁇ m, wrinkles may occur during winding during coating, or white turbidity may be easily caused by humidification. When the thickness of the polymer layer is less than 10 ⁇ m, since the polymer layer is thin, the stress cannot be dispersed and peeling may easily occur.
  • the optical pressure-sensitive adhesive sheet is used as a polymer layer interposed between an image display part of an image display device and a translucent protective part.
  • the optical pressure-sensitive adhesive sheet is used for the polymer (layer) 5b filled between the image display unit 2 and the translucent protection unit 3 in the display device mounted with the In-Cell capacitive touch panel shown in FIG.
  • the optical adhesive sheet has a high dielectric constant. Specifically, it is the same as the physical property values and effects described above for the dielectric constant in the present invention (V).
  • the optical pressure-sensitive adhesive sheet must have a storage elastic modulus of 1 ⁇ 10 3 to 1 ⁇ 10 5 Pa at 25 ° C. and a frequency of 0.1 Hz.
  • the storage elastic modulus of the optical pressure-sensitive adhesive sheet at 25 ° C. and a frequency of 0.1 Hz described in the present specification is as defined above, and the storage elastic modulus was previously described in the present invention (V). The physical property values and effects are the same.
  • the refractive index of the optical pressure-sensitive adhesive sheet at 25 ° C. is the same as the physical properties and effects described above for the refractive index in the present invention (V).
  • the method for forming the polymer layer of the optical pressure-sensitive adhesive sheet may be a known or conventional method for forming a polymer layer, and is not particularly limited, but has an acryloyl group as in the polymerizable composition of the present invention.
  • the polymerizable composition is polymerized to form the polymer layer of the optical pressure-sensitive adhesive sheet, for example, the following methods (1) to (3) can be mentioned.
  • a polymerizable composition having an acryloyl group containing a photopolymerization initiator is coated (coated) with a composition containing additives as necessary on a substrate or a separator (release liner), and a low-pressure mercury lamp , Using a light source such as a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a xenon lamp, a metal halide lamp, an electrodeless lamp, and an LED, the photopolymerization initiator irradiates light capable of being polymerized to polymerize the composition. Thus, a polymer layer is formed.
  • a light source such as a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a xenon lamp, a metal halide lamp, an electrodeless lamp, and an LED
  • a polymerizable composition having an acryloyl group containing a photopolymerization initiator and a composition (solution) further containing a solvent and, if necessary, an additive are applied (coated) on a substrate or a separator (release liner). And then irradiate the photopolymerization initiator with sensitive light using a light source such as a low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, xenon lamp, metal halide lamp, electrodeless lamp, or LED. Then, a polymer layer is formed by polymerizing the composition. (3) The polymer layer formed in (1) above is further dried.
  • a known coating method can be used for coating (coating) in the method for forming the polymer layer, and a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip coater can be used.
  • a roll coater, bar coater, knife coater, spray coater, comma coater, direct coater or the like can be used.
  • the substrate is not particularly limited, and examples thereof include various optical films such as a plastic film, an antireflection (AR) film, a polarizing plate and a retardation plate.
  • the material such as the plastic film include, for example, polyester resins such as polyethylene terephthalate (PET), acrylic resins such as polymethyl methacrylate (PMMA), polycarbonate, triacetyl cellulose (TAC), polysulfone, polyarylate, polyimide, Polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, ethylene-propylene copolymer, trade name “ARTON (cyclic olefin polymer; manufactured by JSR Corporation)”, trade name “ZEONOR (cycloolefin polymer; ZEON CORPORATION)
  • a plastic material such as a cyclic olefin polymer.
  • a plastic material can be used individually or in combination of 2 or more types.
  • the above-mentioned “base material” is a portion that is attached to the adherend together with the adhesive layer when the optical adhesive sheet is used (attached) to the adherend (optical member or the like).
  • a separator (release liner) that is peeled off when the adhesive sheet is used (attached) is not included in the “base material”.
  • a transparent substrate is preferable as the substrate.
  • the “transparent substrate” means, for example, a substrate having a total light transmittance (according to JIS K7361) of 85% or more in the visible light wavelength region, more preferably 88% or more.
  • the haze of the substrate is, for example, preferably 1.5% or less, and more preferably 1.0% or less.
  • the transparent substrate include PET films and non-oriented films such as trade names “Arton” and trade names “Zeonoa”.
  • the thickness of the substrate is not particularly limited and is preferably 12 to 75 ⁇ m, for example.
  • the said base material may have any form of a single layer and a multilayer.
  • the surface of the substrate may be appropriately subjected to known and conventional surface treatments such as physical treatment such as corona discharge treatment and plasma treatment, and chemical treatment such as undercoating treatment.
  • the pressure-sensitive adhesive sheet of the present invention becomes a pressure-sensitive adhesive functional film having the pressure-sensitive adhesive layer of the present invention on at least one side of the functional film.
  • optical functionality polarizability, photorefractive property, light reflectivity, light transmittance, light absorption property, light diffraction property, optical rotation property, visibility, etc.
  • a hard coat film (a film on which at least one surface of a plastic film such as a PET film is hard-coated), a polarizing film, a wave plate, a retardation film, an optical compensation film, a brightness enhancement film, a light guide plate , Reflective film, antireflection film, transparent conductive film (such as ITO film), design film, decorative film, surface protective film, prism, color filter and the like.
  • said "plate” and “film” shall include forms, such as plate shape, film shape, and sheet shape, respectively, for example, “polarizing film” shall also include “polarizing plate” and “polarizing sheet”.
  • the “functional film” includes “functional plate” and “functional sheet”.
  • the other pressure-sensitive adhesive layer is not particularly limited, and examples thereof include a urethane-based pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, and a silicone-based pressure sensitive adhesive layer.
  • examples include known and commonly used pressure-sensitive adhesive layers formed from known pressure-sensitive adhesives such as pressure-sensitive adhesives, polyester-based pressure-sensitive adhesives, polyamide-based pressure-sensitive adhesives, epoxy-based pressure-sensitive adhesives, vinyl alkyl ether-based pressure-sensitive adhesives, and fluorine-based pressure-sensitive adhesives.
  • the above adhesives can be used alone or in combination of two or more.
  • the optical pressure-sensitive adhesive sheet contains neither a base material nor another pressure-sensitive adhesive layer, a polymer layer obtained by polymerizing the polymerizable composition of the present invention (I) to the present invention (IV)
  • a polymer layer obtained by polymerizing the polymerizable composition of the present invention (I) to the present invention (IV) is combined with this other pressure-sensitive adhesive layer.
  • a polymer layer obtained by polymerizing the polymerizable composition of the present invention (I) to the present invention (IV), a layer combining this substrate When both the pressure-sensitive adhesive layer and the substrate are included, the polymer layer obtained by polymerizing the polymerizable composition of the present invention (I) to the present invention (IV), the other pressure-sensitive adhesive layer and the substrate are combined.
  • Layer is defined as “adhesive layer”.
  • the pressure-sensitive adhesive layer surface (adhesive surface) of the optical pressure-sensitive adhesive sheet may be protected by a separator (release liner) until use.
  • a separator release liner
  • each pressure-sensitive adhesive surface may be protected by two separators, respectively, or a single separator whose both surfaces are release surfaces, You may protect in the form wound by the shape.
  • the separator is used as a protective material for the pressure-sensitive adhesive layer, and is peeled off when being applied to an adherend.
  • a separator also plays the role of the support body of an adhesive layer. Note that the separator is not necessarily provided.
  • a conventional release paper or the like can be used, and is not particularly limited.
  • a substrate having a release treatment layer a low adhesive substrate made of a fluoropolymer, a low adhesive substrate made of a nonpolar polymer, etc.
  • a base material which has the said peeling process layer the plastic film, paper, etc. which were surface-treated with peeling processing agents, such as a silicone type, a long-chain alkyl type, a fluorine type, and molybdenum sulfide, are mentioned, for example.
  • fluorine-based polymer in the low-adhesive substrate made of the above-mentioned fluoropolymer examples include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chloro Examples include fluoroethylene-vinylidene fluoride copolymer.
  • nonpolar polymer olefin resin (for example, polyethylene, a polypropylene, etc.) etc. are mentioned, for example.
  • the separator can be formed by a known or conventional method. Further, the thickness of the separator is not particularly limited.
  • the polymerizable composition of the present invention (I) ⁇ (IV) is storage modulus at frequency 0.1Hz at 25 ° C. as measured by the conditions when polymerizing the polymerizable composition is 1 ⁇ 10 3 ⁇
  • the essential constituents of the present invention (I) to (IV) may be mixed uniformly.
  • the temperature when mixing each component is preferably in the range of 20 to 100 ° C., more preferably in the range of 30 to 95 ° C. And particularly preferably in the range of 40 to 90 ° C.
  • the compound that is solid at 25 ° C. is component 5 alone, a mixture of component 4 and component 5, component 5 and component 6 It is preferable to dissolve in a mixture of compounds that are liquid at 25 ° C. or a mixture of compounds that are component 4, component 5 and component 6 that are liquid at 25 ° C. to obtain a uniform liquid mixture.
  • the temperature at which the compound that is solid at 25 ° C. of the component 6 is desirably higher than the softening point of the component 6 that is solid at 25 ° C. in consideration of the dissolution rate.
  • component 4 is used for dissolution, it is desirable to dissolve at a temperature of 130 ° C.
  • the polymerizable composition of the present invention (I) to (IV) is produced using the uniform liquid mixture in which the compound that is solid at 25 ° C. is dissolved, this mixed liquid is used.
  • the temperature at the time of mixing each of the components is preferably in the range of 20 to 100 ° C., more preferably in the range of 30 to 95 ° C., and particularly preferably in the range of 40 to 90 ° C.
  • the polymer of the image device of the present application and the optical pressure-sensitive adhesive sheet have coloring resistance and high transparency.
  • the color resistance can be evaluated by satisfying the following physical property values.
  • the color coordinate b * value described in JIS Z 8729 after storing the polymer adjusted to a thickness of 200 ⁇ m existing between two glasses at a temperature of 85 ° C. for 500 hours is It is less than 1.6.
  • the polymer obtained by polymerizing the polymerizable composition of the present invention has high transparency. Specifically, the polymer is adjusted to a thickness of 200 ⁇ m existing between two glasses.
  • the haze is preferably 0.4 or less, and more preferably 0.2 or less.
  • polymerized to a thickness of 200 ⁇ m existing between two glasses means two optical glasses having a thickness of 0.7 mm (trade name: Eagle XG, manufactured by Corning). Initiating photopolymerization using a low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, xenon lamp, metal halide lamp, electrodeless lamp, LED, etc.
  • the polymer is a polymer having a thickness of 200 ⁇ m obtained by irradiating light capable of being exposed to light, and a spacer, a gasket, a sealant, or the like is provided between the two glass layers outside the polymer layer. Is not included at all.
  • the “color coordinate b * value described in JIS Z 8729 after storage at 85 ° C. for 500 hours” described in the present specification is adjusted to a thickness of 200 ⁇ m existing between the two glasses.
  • the polymer was held at 85 ° C. for 500 hours, and then measured at 23 ° C. in accordance with the method described in JIS Z 8729 using the value of b * of the measured color coordinates (psychometric chroma coordinates). is there.
  • the reference used when measuring the value of b * is one optical glass (manufactured by Corning, trade name: Eagle XG) having a thickness of 0.7 mm.
  • the value of b * measured on the said conditions is 1.6 or less. More preferably, it is 1.2 or less, More preferably, it is 1.0 or less.
  • an appropriate amount of an antioxidant may be added to the polymerizable composition.
  • the amount of the antioxidant used is preferably 0.01 to 5 parts by mass with respect to the total amount of the polymerizable composition of the present invention (I) to the present invention (IV).
  • the amount of the antioxidant is a value in consideration of the antioxidant contained in the other components such as the component 6 in advance. That is, when an antioxidant is preliminarily contained in the component 6 or the like, the total amount of this antioxidant and the newly added antioxidant is the present invention (I) to the present invention (IV ) To 0.01 to 5 parts by mass relative to the total amount of the polymerizable composition.
  • the amount of the antioxidant used is more preferably 0.01 to 4 parts by mass, particularly preferably 0.01 to 3 parts by mass.
  • the addition effect that is, the antioxidant effect
  • the value of b * may exceed 1.6 under the above conditions.
  • the amount of the polymerization inhibitor is more than 5 parts by mass relative to the total amount of the polymerizable composition of the present invention (I) to the present invention (IV)
  • the color coordinate b * value described in JIS Z 8729 after storing the polymer adjusted to a thickness of 200 ⁇ m existing between the two sheets of glass at 95 ° C. for 500 hours is also the above-mentioned 85 ° C. It is preferable to satisfy the physical property values of The measurement method at this time is the same as the method at 85 ° C. described above.
  • the haze described in JIS K 7136 after storing the polymer adjusted to a thickness of 200 ⁇ m existing between two glasses at a temperature of 60 ° C. and 90% for 500 hours is 0.4 or less. It is preferable. More preferably, it is 0.2 or less. In this case as well, the measurement method is the same as that described above. When the haze is 0.4 or more, the light transmittance is reduced.
  • the amount of component 3 used is an essential component of the present invention (IV).
  • the total amount of Component 1, Component 3, Component 4, Component 5 and Component 6 is preferably 1 to 30 parts by mass. More preferably, it is 2 to 20 parts by mass, and particularly preferably 3 to 10 parts by mass.
  • the present invention (VIII) is a method for producing an image display device comprising a base having an image display portion, a translucent protective portion, and a polymer layer interposed between the base and the protective portion, The method comprises the step of interposing the polymerizable composition of the present invention (IV) between the base part and the protective part, and irradiating the polymerizable composition with light that can be photosensitized by a photopolymerization initiator.
  • the present invention relates to a method for manufacturing an image display device including a step of forming a polymer layer.
  • between the base portion having the image display portion and the translucent protective portion means all the portions between the base portion having the image display portion and the translucent protective portion. For example, it means that any of the locations 5a and 5b in FIG. 5 is included in the expression “between the base portion having the image display portion and the translucent protective portion”.
  • FIG. 2, FIG. 3 and FIG. 4 are cross-sectional views showing the main parts of one embodiment of the image display device according to the present invention.
  • the display device 1 of the present embodiment is connected to a drive circuit (not shown) and displays an image display unit 2 that performs a predetermined image display.
  • a translucent protective portion 3 disposed in close proximity to each other at a distance of.
  • the “image display device” described in the present specification is not particularly limited as long as it is a device that displays an image, and can be applied to various devices.
  • a liquid crystal display device or an organic EL display device such as a mobile phone or a mobile game device can be used.
  • the image display unit 2 of the present embodiment is a liquid crystal display panel of a liquid crystal display device.
  • polarizing plates 6a and 6b are provided on the surface thereof as shown in FIG. 2, FIG. 3, or FIG.
  • the spacer 4 and a jetty are provided on the peripheral portion on the image display unit 2, and the region of the present invention (IV) is provided in the inner region thereof.
  • a predetermined amount of the polymerizable composition is dropped.
  • the protective part 3 is arranged on the spacer 4 of the image display part (liquid crystal display panel) 2, and the polymerization of the present invention (IV) is performed in the gap between the image display part (liquid crystal display panel) 2 and the protective part 3.
  • the composition is filled without gaps.
  • the component 2 which is an essential component of the polymerizable composition of the present invention (IV) is irradiated with light capable of being exposed to the polymerizable composition of the present invention (IV) via the protective part 3.
  • the polymerizable composition of the present invention (IV) is polymerized. Thereby, the target image display apparatus 1 is obtained.
  • the refractive index of the polymer layer 5 and the protective part 3 are equal, the brightness and contrast can be increased to improve the visibility.
  • the process of irradiating the component 2 with photosensitive light is a general ultraviolet irradiation device using a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp, an electrodeless lamp or the like as a light source.
  • a general ultraviolet irradiation device using a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp, an electrodeless lamp or the like as a light source.
  • UV irradiation dose is generally from about 1000 mJ / cm 2 ⁇ about 8000 mJ / cm 2.
  • the influence of the stress caused by the volume shrinkage during polymerization of the polymerizable composition can be suppressed to the image display unit (liquid crystal display panel) 2 and the protection unit 3, the liquid crystal display panel 2 and the protection unit 3 can be protected. As a result, the image display unit (liquid crystal display panel) 2 is not deformed, so that it is possible to display an image with high brightness and high contrast without display defects.
  • the dielectric constant of the polymer in the polymer layer 5b is maintained high. Even if the thickness of the polymer layer is increased to some extent, it is possible to prevent the sensitivity of the touch sensor from being lowered.
  • This invention (IX) is a manufacturing method of an image display apparatus which has the process of sticking the base which has an image display part, and a translucent protective part using an optical adhesive sheet, Comprising:
  • This optical adhesive sheet is A method for manufacturing an image display device, which is the optical pressure-sensitive adhesive sheet according to the present invention (VII).
  • “attaching a base portion having an image display portion and a translucent protective portion using an optical adhesive sheet” means that the base portion having an image display portion and a translucent portion are used. Meaning that any part between the protective part and the protective part is included in the expression "the base having the image display part and the translucent protective part are attached using an optical adhesive sheet". For example, even if the adhesive sheet is attached to either 5a or 5b in FIG. 5, "the base having the image display part and the translucent protective part are attached using the optical adhesive sheet” It is included in the expression.
  • the first base material is a touch sensor integrated protective portion
  • a manufacturing process in the display device of FIG. 4 in which the base material is a display unit with a polarizing plate will be described as an example.
  • the step of arranging the optical pressure-sensitive adhesive sheet adjacent to one side of the translucent protective part as the first base material, and the surface of the display part with a polarizing plate as the second base material for the optical A step of arranging adjacent to the pressure-sensitive adhesive sheet, a step of heating and / or pressing the optical pressure-sensitive adhesive sheet to follow a step or a ridge, and a photopolymerization initiator on the optical pressure-sensitive adhesive sheet as necessary. It can be manufactured by a method including a step of irradiating photosensitive light. These steps can be performed in various orders.
  • one surface of the optical pressure-sensitive adhesive sheet is disposed adjacent to one side of the translucent protective portion which is the first base material, and the second base material is used.
  • the surface of the display part with a certain polarizing plate is arrange
  • the optical pressure-sensitive adhesive sheet is heated and / or pressurized to cause the pressure-sensitive adhesive sheet to follow a step or a bump.
  • the optical pressure-sensitive adhesive sheet passes through these substrates from the side of the translucent protective part (first base material) and / or the display part (second base material) with a polarizing plate.
  • the photopolymerization initiator is irradiated with light capable of being exposed to light.
  • the translucent protective part (first base material) and the polarizing plate are attached without forming a gap in the vicinity of the step or the bulge of the translucent protective part (first base material).
  • the display portion (second base material) can be adhered.
  • a translucent protective part (first base material) and a display part with a polarizing plate (second base material) are adjacent to the optical pressure-sensitive adhesive sheet, and then the pressure-sensitive adhesive sheet is heated and In order to pressurize, when there is a step or a bulge on the adherend surface of the display unit (second base material) with a polarizing plate (that is, the adhesive sheet is applied on the polarizing plate attached to the image display module)
  • the pressure-sensitive adhesive sheet can be made to follow the steps and bulges of the display portion (second base material) with the polarizing plate, and the formation of voids can be prevented even in the vicinity of the shape.
  • the photopolymerization initiator when the photopolymerization initiator irradiates light capable of being sensitized, at least one of the first base material and the second base material passes through them to the optical pressure-sensitive adhesive sheet, and the photopolymerization initiator is present. It is at least partially transparent so that it can be irradiated with photosensitive light.
  • the step or bulge portion of the first base material does not transmit ultraviolet light
  • the ultraviolet light when the ultraviolet light is irradiated from the first base material side, the ultraviolet light is not irradiated directly below the step or bulge portion, but the irradiated portion
  • the polymerization of the pressure-sensitive adhesive sheet proceeds to some extent even in the non-irradiated part due to the movement of radicals generated in the above.
  • one surface of the optical pressure-sensitive adhesive sheet is a surface side having a step or a bulge in the translucent protective portion (first base material) (that is, a person does not touch during use)
  • the pressure-sensitive adhesive sheet is heated and / or pressurized to cause the pressure-sensitive adhesive sheet to follow a step or a bump.
  • the display unit with the polarizing plate (second base material) is placed on the pressure-sensitive adhesive sheet. It arrange
  • the pressure-sensitive adhesive sheet can be irradiated with ultraviolet rays through the release film, if necessary.
  • the pressure-sensitive adhesive sheet can be polymerized more uniformly.
  • the first base material is at least partially transparent so that the photopolymerization initiator necessary for the polymerization of the pressure-sensitive adhesive sheet can irradiate light capable of being sensitized, from the first base material side, if necessary. Irradiation with ultraviolet rays is also possible. In this way, the first base material and the second base material can be bonded together without forming a gap near the step or bulge of the first base material.
  • the heating step can be performed using a convection oven, a hot plate, a heat laminator, an autoclave, or the like.
  • a convection oven a hot plate
  • a heat laminator a heat laminator
  • an autoclave a heat laminator
  • Pressurization using an autoclave is particularly advantageous for defoaming the optical pressure-sensitive adhesive sheet.
  • the heating temperature of the optical pressure-sensitive adhesive sheet of the present invention may be any temperature as long as the pressure-sensitive adhesive sheet softens or flows and sufficiently follows a step or a bump, and is generally about 30 ° C. or higher, about 40 ° C. or higher, or about 60 ° C.
  • the temperature may be about 150 ° C. or lower, about 120 ° C. or lower, or about 100 ° C. or lower.
  • the applied pressure can be generally about 0.05 MPa or more, or about 0.1 MPa or more, about 2 MPa or less, or about 1 MPa or less.
  • the step of irradiating light that can be photosensitized by the above-described photopolymerization initiator, which is performed as necessary, is the same as the step of irradiating light that can be sensitized by the component 2 described above.
  • the present invention (X) is an image display device manufactured by the manufacturing method of the image display device of the present invention (VIII) or the present invention (IX).
  • the image display device of the present invention (X) generally has a refractive index (n D ) of 1.49 to 1.52 when the main body of the display device is made of optical glass.
  • n D refractive index
  • the protection unit 3 is formed from a plate-like, sheet-like, or film-like translucent member having the same size as the display unit 2.
  • optical glass or plastic acrylic resin such as polymethyl methacrylate
  • An optical layer such as an antireflection film, a light shielding film, or a viewing angle control film may be formed on the front surface or the back surface of the protection unit 3.
  • the protective part 3 is made of an acrylic resin, its refractive index (n D ) is generally 1.49 to 1.51.
  • the protection unit 3 is provided on the display unit 2 via a spacer 4 provided on the peripheral edge of the display unit 2.
  • the spacer 4 has a thickness of about 0.05 to 1.5 mm, whereby the distance between the surfaces of the image display unit 2 and the protection unit 3 is maintained at about 1 mm.
  • a frame-shaped light shielding portion (not shown) is provided at the peripheral portion of the protection portion 3 in order to improve luminance and contrast.
  • the image display device manufactured by the method for manufacturing the image display device of the present invention (VIII) will be described in detail. Between the image display part 2 and the protection part 3, polymer layers 5a and 5b are interposed.
  • the polymer of the present invention (V) is interposed in the polymer layer 5a and the polymer layer 5b.
  • the transmittance in the visible light region is 90% or more.
  • the thickness of the polymer layer 5a or the polymer layer 5b is preferably 10 to 2000 ⁇ m. More preferably, it is 20 to 1700 ⁇ m, and particularly preferably 30 to 1300 ⁇ m.
  • the refractive index (n D ) at 25 ° C. is described in the above-mentioned present invention (V).
  • the physical property values and effects are the same.
  • the polymer composition of the present invention (V) is interposed in the polymer layer 5a and the polymer layer 5b, and therefore the polymerizable composition.
  • the physical properties of the volume shrinkage during polymerization are the same as the physical properties and effects described for the volume shrinkage in the present invention (V).
  • the polymer of this invention (V) for the polymer layer 5b, since the dielectric constant of these polymers is high, the sensitivity when a person touches can be enlarged. Further, when the image display device is produced by the method for producing an image display device of the present invention (IX), the polymer is interposed in the polymer layer 5a and the polymer layer 5b, and therefore the present invention (V) described above. The effects and characteristics obtained when an image display device is manufactured by this method for manufacturing an image display device can be obtained.
  • the image display apparatus manufactured by the image display apparatus manufacturing method of the present invention (IX) will be described in detail.
  • a polymer layer 5a and a polymer layer 5b or a polymer layer 5b are interposed.
  • the optical adhesive sheet is interposed in the polymer layer 5a and the polymer layer 5b, so that the visible light region Of 90% or more.
  • the thickness of the polymer layer 5a and the polymer layer 5b is preferably 10 to 1000 ⁇ m. More preferably, the thickness is 20 to 700 ⁇ m, and particularly preferably 30 to 500 ⁇ m.
  • the refractive index at 25 ° C. (n D ) is the refractive index in the present invention (VIII) first. This is the same as the physical property values and effects described above.
  • the optical pressure-sensitive adhesive sheet has flexibility, even if the protection unit 3, the display unit 2, and the touch panel 7 have an uneven shape, a layer having an uneven surface shape on the display surface of the image display unit. Even if (for example, a polarizing plate) is provided, the internal residual stress of the sheet itself is relaxed, and display unevenness in the image display device can be prevented.
  • the display surface (for example, a polarizing plate) of the image display unit 2 can be used even in a high temperature and high humidity environment.
  • Air bubbles and peeling do not occur at the interface with the optical pressure-sensitive adhesive sheet (that is, the polymer layer 5b) and at the interface between the optical pressure-sensitive adhesive sheet (that is, the polymer layer 5b) and the translucent protective portion 3. No whitening occurs.
  • optical glass plate used in the image display device of the present invention those used as a glass plate for sandwiching the liquid crystal of the liquid crystal cell or a protective plate for the liquid crystal cell can be preferably used.
  • acrylic resin board used what is used as a protective plate of a liquid crystal cell can be used preferably.
  • the average surface roughness of these optical glass plates and acrylic resin plates is usually 1.0 nm or less.
  • the image display device of the present invention (X) includes a polymer layer 5a or a polymer obtained by using the polymer of the present invention (V) or the optical pressure-sensitive adhesive sheet between the image display unit 2 and the protection unit 3. Since the layer 5b is filled, it is strong against impact. In addition, it can be formed thinner than the conventional example in which a gap is provided between the image display unit 2 and the protection unit 3.
  • the image display device of the present invention (X) can take various forms.
  • the image display device 1 may be manufactured by omitting the spacer 4.
  • the photopolymerizable composition of any one of the present invention (I) to the present invention (IV) is applied onto the polarizing plate 6a on the display unit 2, and the above-mentioned Or, for example, as shown in FIG. 5, a laminate composed of the protective portion 3, the polymer layer 5b, the touch panel 7 and the polymer layer 5a (that is, the optical pressure-sensitive adhesive sheet 5a) is formed. It can be obtained by bonding to the display surface on the image display unit 2 (that is, the surface of the polarizing plate 6a).
  • the present invention can be applied not only to the liquid crystal display device described above but also to various panel displays such as an organic EL and a plasma display device.
  • the polymerizable composition of the present invention it is possible to minimize the stress due to volume shrinkage when it is applied between the image display part and the protective part and polymerized, so that the image display part is provided.
  • an image display device is manufactured using a process of forming a polymer layer by interposing a polymerizable composition between a base and a translucent protective part and polymerizing the image display part, The influence on the protection unit can be minimized. Therefore, according to the image display device of the present invention, distortion hardly occurs in the image display unit and the protection unit.
  • the polymerizable composition of the present invention does not contain a volatile solvent (that is, no solvent)
  • the polymer obtained by polymerizing the polymerizable composition of the present invention is divided into an image display part and a protective part.
  • a volatile solvent that is, no solvent
  • the cured product obtained by polymerizing the polymerizable composition of the present invention between the image display part and the protective part has high adhesion to the glass used in the protective part.
  • the polymer and the optical adhesive sheet of the present invention have a refractive index that is a configuration panel of the image display unit or a configuration of the protection unit as compared with a gap that is conventionally provided between the liquid crystal display panel and the protection unit. It is close to the refractive index of the panel, and the light at the interface between the protective part and the polymer, the interface between the polymer and the image display part, the interface between the protective part and the optical adhesive sheet, or the interface between the optical adhesive sheet and the image display part. Reflection is suppressed. As a result, according to the image display device of the present invention, high luminance and high contrast display without display defects becomes possible.
  • the image display unit is a liquid crystal display panel
  • display defects such as disorder of alignment of the liquid crystal material can be reliably prevented and high-quality display can be performed.
  • the image display device of the present invention since the polymer or the optical adhesive sheet is interposed between the image display unit and the protection unit, the image display device is resistant to impact. Furthermore, since the polymer and the optical adhesive sheet of the present invention are not easily colored even when subjected to a thermal history, it is possible to maintain high brightness and high contrast display for a long time. In addition, according to the present invention, it is possible to provide a thin image display device as compared with the conventional example in which a gap is provided between the image display unit and the protection unit.
  • ⁇ Measurement of viscosity> For samples having a viscosity of less than 10 Pa ⁇ s at a temperature of 25.0 ° C., the viscosity was measured by the following method. Using a 1 mL sample, the viscosity was measured at a temperature of 25.0 ° C. and a rotation speed of 5 rpm using a cone / plate viscometer (manufactured by Brookfield, model: DV-II + Pro, spindle model: CPE-42). The value when it became almost constant was measured. For a sample having a viscosity of 10 Pa ⁇ s or more at a temperature of 25.0 ° C., the viscosity was measured by the following method.
  • the number average molecular weight is a value in terms of polystyrene measured by GPC under the following conditions.
  • Device name HPLC unit HSS-2000 manufactured by JASCO Corporation Column: Shodex column LF-804
  • Mobile phase Tetrahydrofuran Flow rate: 1.0 mL / min Detector: RI-2031Plus manufactured by JASCO Corporation Temperature: 40.0 ° C
  • Sample volume Sample loop 100 ⁇ L
  • Sample concentration prepared at around 0.5 wt%
  • Pripol (registered trademark) 2033 (clad hydrogenated dimer diol, hydroxyl value 202 mg KOH / g) 26.2 parts by mass, 1,4-butanediol (Mitsubishi Chemical Corporation) in a 2000 mL reaction vessel equipped with a stirrer and a distillation apparatus 47.2 parts by mass of company), 656.3 parts by mass of 3-methyl-1,5-pentanediol (manufactured by Kuraray Co., Ltd.), 721.4 parts by mass of adipic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), Pripol (registered) Trademark) 1009 (clad hydrogenated dimer acid) 241.5 parts by weight and stannous chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.5 parts by weight were charged, and water was distilled off starting at about 170 ° C.
  • polyester polyol A A polyester polyol having a hydroxyl value of 57.0 mgKOH / g (hereinafter referred to as polyester polyol A) was obtained.
  • Example synthesis example 2-1 In a 100 mL reaction vessel equipped with a stirrer, thermometer, dropping funnel and condenser, a mixture of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate (trade name: VESTANAT®) ) TMDI, manufactured by Evonik Degussa) 15.28 g, dioctyltin dilaurate 15 mg and p-methoxyphenol 24 mg were charged into a reaction vessel, and 10.48 g of 4-hydroxybutyl acrylate was added dropwise using a dropping funnel. During the dropping, the temperature in the reaction vessel was adjusted to 70 ° C. or lower.
  • reaction product ⁇ a reaction product (hereinafter referred to as reaction product ⁇ ).
  • reaction product ⁇ a reaction product (number average molecular weight 2030) was charged, and stirring was started. Thereafter, the total amount of the reaction product ⁇ maintained at 60 ° C. was introduced into the reaction vessel in several portions. Meanwhile, the temperature in the reactor was not allowed to rise above 70 ° C. Thereafter, the temperature in the reactor was maintained at 70 to 75 ° C., and stirring was continued.
  • urethane acrylate 1 having a number average molecular weight of 2380 (hereinafter referred to as “urethane acrylate 1”) was obtained. Since it is considered that 1-fold molar amount of acryloyl group derived from 4-hydroxybutyl acrylate is introduced relative to polyester polyol A, the number of acryloyl groups contained in this urethane acrylate 1 is 1 on average per molecule. It can be assumed that there is.
  • Example synthesis example 2-2 In a 100 mL reaction vessel equipped with a stirrer, thermometer, dropping funnel and condenser, a mixture of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate (trade name: VESTANAT®) ) TMDI, manufactured by Evonik Degussa) 27.83 g, dioctyltin dilaurate 30 mg and p-methoxyphenol 24 mg were charged into a reaction vessel, and 4-hydroxybutyl acrylate 19.08 g was added dropwise using a dropping funnel. During the dropping, the temperature in the reaction vessel was adjusted to 70 ° C. or lower.
  • reaction product ⁇ a reaction product (hereinafter referred to as reaction product ⁇ ).
  • reaction product ⁇ a reaction product (number average molecular weight 2030) was charged, and stirring was started. Thereafter, the total amount of the reaction product ⁇ maintained at a temperature of 60 ° C. was introduced into the reaction vessel in several portions. Meanwhile, the temperature in the reactor was not allowed to rise above 70 ° C. Thereafter, the temperature in the reactor was maintained at 70 to 75 ° C., and stirring was continued.
  • urethane acrylate 2 having a number average molecular weight of 2670 (hereinafter referred to as “urethane acrylate 2”) was obtained. Since it is considered that acryloyl groups derived from 4-hydroxybutyl acrylate in a molar amount of 1.8 times that of polyester polyol A are introduced, the number of acryloyl groups contained in this urethane acrylate 2 is 1 on an average per molecule. .8 can be assumed.
  • urethane acrylate 3 having a number average molecular weight of 2560 (hereinafter referred to as “urethane acrylate 3”) was obtained.
  • urethane acrylate 3 since it is considered that 1.5 times mole amount of acryloyl group derived from 4-hydroxybutyl acrylate with respect to polyester polyol A is introduced, the number of acryloyl groups contained in this urethane acrylate 3 is 1 on an average per molecule. .5 can be assumed.
  • Example synthesis example 2-4 In a 300 mL reaction vessel equipped with a stirrer, a thermometer and a condenser, the above-mentioned polyester polyol A (number average molecular weight 2030) 150 g, 4-hydroxybutyl acrylate 19.08 g, dioctyltin dilaurate 30 mg and p-methoxyphenol 24 mg were reacted. The container was charged and stirring was started.
  • urethane acrylate 4 having a number average molecular weight of 2670. Since it is considered that acryloyl groups derived from 4-hydroxybutyl acrylate in a molar amount of 1.8 times that of polyester polyol A are introduced, the number of acryloyl groups contained in this urethane acrylate 4 is 1 on average per molecule. .8 can be assumed.
  • Example synthesis 2-5 In a 100 mL reaction vessel equipped with a stirrer, thermometer, dropping funnel and condenser, a mixture of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate (trade name: VESTANAT®) ) TMDI, manufactured by Evonik Degussa) 22.94 g, 30 mg of dioctyltin dilaurate and 24 mg of p-methoxyphenol were added to the reaction vessel, and 15.73 g of 4-hydroxybutyl acrylate was added dropwise using a dropping funnel. During the dropping, the temperature in the reaction vessel was adjusted to 70 ° C. or lower.
  • reaction product ⁇ a reaction product (hereinafter referred to as reaction product ⁇ ).
  • polyester polyol trade name: Kuraray polyol P-2050, hydroxyl value 57.0 mg KOH / g, manufactured by Kuraray Co., Ltd., sebacic acid and 3-methyl-1
  • polyester polyol (trade name: Kuraray polyol P-2010, hydroxyl value 57.0 mg KOH / g, manufactured by Kuraray Co., Ltd., adipic acid and A polyester polyol produced using 3-methyl-1,5-pentanediol as a raw material, number average molecular weight 2000) 75 g was added, and stirring was started.
  • urethane acrylate 5 urethane acrylate having a number average molecular weight of 2520
  • Example synthesis 2-6 In a 100 mL reaction vessel equipped with a stirrer, thermometer, dropping funnel and condenser, a mixture of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate (trade name: VESTANAT®) ) TMDI, manufactured by Evonik Degussa) 27.83 g, dioctyltin dilaurate 30 mg and p-methoxyphenol 24 mg were charged into a reaction vessel, and 4-hydroxybutyl acrylate 19.08 g was added dropwise using a dropping funnel. During the dropping, the temperature in the reaction vessel was adjusted to 70 ° C. or lower.
  • reaction product ⁇ a reaction product (hereinafter referred to as reaction product ⁇ ).
  • reaction product ⁇ a reaction product (trade name: Kuraray polyol P-2050, hydroxyl value 57.0 mg KOH / g, manufactured by Kuraray Co., Ltd., number average molecular weight 1980)
  • polyester polyol Product name: Kuraray polyol P-2010, hydroxyl value 57.0 mgKOH / g, manufactured by Kuraray Co., Ltd., number average molecular weight 2000) was added in an amount of 75 g, and stirring was started.
  • Example of formulation 1 Urethane acrylate 5 99.0 parts by mass, 1-hydroxycyclohexyl phenyl ketone (trade name: IRGACURE (registered trademark) 184, manufactured by BASF) 0.8 parts by mass, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name: 0.2 parts by weight of SpeedCure TPO, manufactured by Lambson) and pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX (registered trademark) 1010, manufactured by BASF) 1.0 part by mass was mixed using a rotation / revolution mixer (manufactured by Shinky Co., Ltd., trade name: Rentaro Awatori ARE-310). This blend was designated as a polymerizable composition A1. The viscosity at 25 ° C. of the polymerizable composition A1 was 33,690
  • Example formulation examples 2 to 6 and comparative formulation examples 1 and 2 In the same manner as in Example 1 of blending, blending was performed according to the blending composition shown in Table 1.
  • the formulations prepared in Examples 2 to 6 were designated as polymerizable compositions A2 to A6, respectively, and the formulations prepared in comparative formulation examples 1 and 2 were designated as polymerizable compositions B1 and B2.
  • the unit of the number of each component of the implementation formulation example and the comparative formulation example described in Table 1 is “parts by mass”.
  • a conveyor type ultraviolet irradiation device using a metal halide lamp (GS Yuasa Lighting Co., Ltd.) Manufactured under the trade name: GSN2-40), and ultraviolet rays were irradiated through a silicone-coated PET film under the conditions of irradiation intensity of 190 mW / cm 2 (value of 365 nm) and irradiation amount of 6000 mJ / cm 2 (value of 365 nm).
  • the film thickness is about 2 between the exposed PET film and the release PET film.
  • optical pressure-sensitive adhesive sheet for 0 .mu.m.
  • the optical pressure-sensitive adhesive sheets produced using the polymerizable compositions A1 to A6 and the polymerizable compositions B1 and B2 were referred to as pressure-sensitive adhesive sheets A1 to A6 and pressure-sensitive adhesive sheets B1 and B2, respectively.
  • the adhesive sheets A1 to A6 and the adhesive sheets B1 and B2 each have two glass plates (50 mm ⁇ 50 mm ⁇ 0.7 mm, glass type, product name: EAGLE XG () so that air bubbles do not enter the interface.
  • a test piece was prepared by adhering the adhesive sheet so as to be sandwiched from both sides with a registered trademark and CORNING.
  • Test pieces prepared using the pressure-sensitive adhesive sheets A1 to A6 and the pressure-sensitive adhesive sheets B1 and B2 were referred to as test pieces AS1-1 to AS6-1 and test pieces BS1-1 and BS2-1, respectively. The adhesion of these test pieces to glass was measured by the method described below.
  • the adhesive sheets A1 to A6 and the adhesive sheets B1 and B2 each have two glass plates (50 mm ⁇ 50 mm ⁇ 0.7 mm, glass type, product name: EAGLE XG () so that air bubbles do not enter the interface. (Registered trademark), CORNING) and resin plate (Mitsubishi Gas Chemical Co., Ltd., trade name: MR-85, or Mitsubishi Rayon Co., Ltd., trade name: Acrylite MR-200).
  • a test piece was prepared.
  • a polymer film for an evaluation test which was manufactured using the polymerizable compositions A1 to A6 and the polymerizable compositions B1 and B2 and was sandwiched between the glass plate and the resin plate and having a thickness of about 200 ⁇ m, was tested.
  • the specimens AS1-2 to AS6-2 and specimens BS1-2 and BS2-2 were used.
  • the adhesion of these test pieces to the resin plate was measured by the method described later.
  • the results are shown in Table 4.
  • the below-mentioned peeling resistance test was done using these test pieces.
  • the results are shown in Table 4.
  • “PMMA and glass plate peeling resistance test” described in Table 4 is a test when MR-200 is used for the resin plate.
  • the “Peeling resistance test between PC and glass plate” shown in Table 4 is a test when MR-85 is used for the resin plate.
  • the polymerizable composition A4 to the polymerizable composition A6 and the polymerizable compositions B1 and B2 are each applied to a glass plate so as to have a film thickness of 200 ⁇ m, and sandwiched between glass plates of the same type and shape. Polymerization was performed by irradiating with ultraviolet rays under the same irradiation conditions as the exposure conditions for producing the pressure-sensitive adhesive sheet, and a polymer film for an evaluation test having a thickness of about 200 ⁇ m sandwiched between glass plates was obtained.
  • the polymerizable composition A4 to the polymerizable composition A6 and the polymerizable compositions B1 and B2 are each applied to a glass plate so as to have a film thickness of 200 ⁇ m, and sandwiched between resin plates (the above-mentioned two types).
  • the glass plate is irradiated with ultraviolet rays under the same irradiation conditions as described above to polymerize the glass.
  • a polymer film for an evaluation test having a film thickness of about 200 ⁇ m sandwiched between the plate and the resin plate was obtained.
  • a polymer film for an evaluation test which was manufactured using the polymerizable compositions A4 to A6 and the polymerizable compositions B1 and B2 and was sandwiched between the glass plate and the resin plate and having a thickness of about 200 ⁇ m, was tested.
  • the specimens AL4-2 to AL6-2 and specimens BL1-2 and BL2-2 were used.
  • the adhesion of these test pieces to the resin plate was measured by the method described later.
  • the results are shown in Table 4.
  • the below-mentioned peeling resistance test was done using these test pieces.
  • the results are shown in Table 5.
  • the peeling resistance test means that the above-mentioned test piece is placed in a thermostatic chamber of 60 ° C. and 90% RH and left for 72 hours, and the test piece is taken out in an environment of 23 ° C. and 50% RH and then tested for 48 hours. The piece was allowed to stand in an environment of 23 ° C. and 50% RH. Thereafter, the resin plate and the test pieces AS1-2 to AS6-2 and the test pieces BS1-2 and BS2-2 and the test piece AL4-2 to the test pieces AL6-2 and the test pieces BL1-2 and BL2-2 are visually observed.
  • a polymer film having a thickness of 2 mm obtained by polymerizing the polymerizable composition A1 to the polymerizable composition A6 and the polymerizable compositions B1 and B2 and peeling the PET film coated with silicone was respectively obtained.
  • Polymer film A1 to polymer film A6 and polymer films B1 and B2 are used.
  • Test piece AS1-2 to test piece AS6-2, test piece AL4-2 to test piece AL6-2, test piece BS1-2, BS2-2 and test piece BL1-2, BL2-2, outer glass surface and A plastic jig was affixed to the resin plate surface using a double-sided tape so that each could be sandwiched between chuck portions of a tensile tester. Thereafter, the film was pulled in the direction of peeling perpendicularly to the glass surface in the same manner as in the adhesion test to glass described above. The value obtained by dividing the breaking force by the coating area at that time was evaluated as the adhesion between the resin plate and the glass. The results are shown in Table 4.
  • the polymers obtained by polymerizing the polymerizable compositions of the present invention (I) to the present invention (III) have good adhesion to glass and are used under high temperature conditions or at high temperatures. It was found that even when stored for a long time under humid conditions, appearance changes such as coloring hardly occur, and good light transmittance can be maintained.
  • the polymerizable composition of the present invention (IV) has a low volume shrinkage during polymerization, and the polymer obtained by polymerizing the polymerizable composition of the present invention (IV) has an adhesive property to glass. It was found that good peeling resistance can be maintained even when stored for a long time under high temperature conditions or high temperature and high humidity conditions.
  • the polymer film obtained by polymerizing the polymerizable composition of the present invention (I) to the present invention (III) has good adhesion to glass and is used under high temperature conditions or high temperature and high humidity conditions. Even when stored for a long time, good peeling resistance can be maintained. Also, the dielectric constant is high. Furthermore, the polymerizable composition of the present invention (IV) has a low volume shrinkage during polymerization, and the polymer film obtained by polymerizing the polymerizable composition of the present invention (IV) is adhered to the resin plate. Good peeling resistance can be maintained even when stored for a long time under high temperature conditions or high temperature and high humidity conditions. Therefore, when the polymer film is used as a transparent optical resin layer interposed between the image display portion and the translucent protective portion of the image display device, a good optical adhesive layer can be provided. . Therefore, it is useful to use the polymer in an image display device.

Abstract

Provided is a polymerizable composition for forming a polymer layer to be interposed between an image display part of an image display device and a light-transmissive protective part, the polymerizable composition exhibiting excellent peeling resistance with respect to the display part and the protective part. This polymerizable composition comprises a (meth)acryloyl-group-containing polymer compound having a number-average molecular weight within the range of from 1000 to 15000, and a photopolymerization initiator, wherein the polymer obtained by polymerizing said polymerizable composition has a storage modulus of from 1×103 to 1×105 Pa at 25°C at a frequency of 0.1 Hz. The polymerizable composition may also comprise, for example: a radical-polymerizable-unsaturated-group-containing compound including an alcoholic hydroxyl group and/or an amido group; a (meth)acryloyl-group-containing compound that includes no alcoholic hydroxyl group nor amide group and that has a viscosity of 500 mPa·s or less at 25°C; and/or a nonionic surfactant that includes no (meth)acryloyl group.

Description

重合性組成物、重合物、光学用粘着シート、画像表示装置およびその製造方法Polymerizable composition, polymer, optical pressure-sensitive adhesive sheet, image display device and method for producing the same
　本発明は、例えばスマートフォンやタブレットＰＣ等に用いられる液晶表示装置等の画像表示装置に使用される重合性組成物、該組成物を重合して得られる重合物、該重合物の層を有する光学用粘着シート、該組成物を用いた画像表示装置の製造方法およびその製造方法により製造された画像表示装置に関する。 The present invention relates to a polymerizable composition used in an image display device such as a liquid crystal display device used in, for example, smartphones and tablet PCs, a polymer obtained by polymerizing the composition, and an optical having a layer of the polymer The present invention relates to a pressure-sensitive adhesive sheet, a method for producing an image display device using the composition, and an image display device produced by the method.
　従来、この種の画像表示装置としては、例えば図６に示す液晶表示装置１０１が知られている。
　図６に示すように、この液晶表示装置１０１は、液晶表示パネル１０２上に、例えば、ガラスや樹脂からなる透明な保護部１０３を有している。
　この場合、液晶表示パネル１０２表面および偏光板（図示せず）を保護するため、保護部１０３との間にスペーサ１０４を介在させることによって液晶表示パネル１０２と保護部１０３との間に空隙１０５が設けられている。
　しかし、液晶表示パネル１０２と保護部１０３との間の空隙１０５の存在により、光の散乱がおき、それに起因してコントラストや輝度が低下し、また空隙１０５の存在はパネルの薄型化の妨げとなっている。 Conventionally, for example, a liquid crystal display device 101 shown in FIG. 6 is known as this type of image display device.
As shown in FIG. 6, the liquid crystal display device 101 has a transparent protective part 103 made of, for example, glass or resin on a liquid crystal display panel 102.
In this case, in order to protect the surface of the liquid crystal display panel 102 and a polarizing plate (not shown), a gap 104 is provided between the liquid crystal display panel 102 and the protective part 103 by interposing a spacer 104 between the protective part 103 and the liquid crystal display panel 102. Is provided.
However, the presence of the gap 105 between the liquid crystal display panel 102 and the protection unit 103 causes light scattering, resulting in a decrease in contrast and brightness, and the presence of the gap 105 hinders thinning of the panel. It has become.
　このような問題に鑑み、液晶表示パネルと保護部との間の空隙に樹脂を充填すること（図１参照）も提案されている（例えば特開２００５－５５６４１号公報）。しかし、樹脂板からなる保護部を用いた場合には、高温環境下において、樹脂板と充填した樹脂との界面の剥がれによる欠陥が発生し、耐久性においての問題も有している。そのため、保護部が樹脂板の場合でも、剥がれの発生を抑制し得る耐久性に優れた樹脂が求められている。 In view of such a problem, it has also been proposed to fill a gap between the liquid crystal display panel and the protective portion (see FIG. 1) (for example, JP-A-2005-55641). However, when a protective part made of a resin plate is used, a defect due to peeling of the interface between the resin plate and the filled resin occurs in a high temperature environment, and there is a problem in durability. Therefore, even when the protective part is a resin plate, there is a demand for a resin having excellent durability that can suppress the occurrence of peeling.
　近年、携帯電話においてはスマートフォンが主流になりつつあり、タブレットＰＣと言われる機器も急速に広まっている。このような機器には静電容量方式のタッチパネルが搭載されているのが一般的である。スマートフォンやタブレットＰＣと言われる機器に対して用いられる際には、そのような機器のデザイン性を高めるため、保護板には、加工のしやすさ、成型の容易さが求められ、樹脂板を用いることが望まれている。しかし、樹脂板は一般的にガラスに比べ、歪みや反りが大きい傾向があり、樹脂板に良好な密着性を示し、剥がれ等が発生しない、前記樹脂が求められている。 In recent years, smartphones are becoming mainstream in mobile phones, and devices called tablet PCs are rapidly spreading. Such devices are generally equipped with a capacitive touch panel. When used for devices such as smartphones and tablet PCs, the protective plate must be easy to process and easy to mold in order to improve the design of such devices. It is desired to use it. However, a resin plate generally has a tendency to have larger distortion and warpage than glass, and there is a demand for the resin that exhibits good adhesion to the resin plate and does not peel off.
　上記問題点を解決するために、例えば、特開２０１２－４６６５８号公報には、紫外線架橋性部位を有する（メタ）アクリレートオリゴマーとヒンダードアミンとを含む光硬化型接着組成物が開示され、その組成物は光学表示パネルと保護パネルとの貼り合せ用等に用いられることが開示されている。特開２０１２－４６６５８号公報には、引張弾性率やガラスとの接着性について開示されているが、貯蔵弾性率や剥がれの耐久性については開示がなく、特に樹脂製保護部との耐剥がれ性については開示がなく、また、高誘電率についても開示がない。 In order to solve the above problems, for example, JP 2012-46658 A discloses a photocurable adhesive composition containing a (meth) acrylate oligomer having an ultraviolet crosslinkable site and a hindered amine, and the composition. Is disclosed for use in bonding an optical display panel and a protective panel. Japanese Patent Application Laid-Open No. 2012-46658 discloses the tensile modulus and adhesion to glass, but does not disclose the storage modulus and durability of peeling, and in particular, resistance to peeling with a resin protective part. Is not disclosed, and there is no disclosure of high dielectric constant.
　また、特開２０１２－４１４５６号公報には、炭素数１～１２の炭化水素基を有する（メタ）アクリル酸エステル系単量体、ヒドロキシル基含有（メタ）アクリル酸エステル系単量体、アミド基を含有する単量体およびビニルエステル系単量体を含む単量体成分を共重合して得られる、重量平均分子量が４０万～２００万であり、誘電率が３～６である、アクリル系高分子化合物が開示され、そのアクリル系高分子化合物をタッチパネル用粘着剤組成物に用いること、その組成物はガラス板および樹脂板との接着性に優れることが開示されている。しかし、特開２０１２－４１４５６号公報には剥がれの耐久性については開示がない。 JP 2012-41456 A discloses a (meth) acrylic acid ester monomer having a hydrocarbon group having 1 to 12 carbon atoms, a hydroxyl group-containing (meth) acrylic acid ester monomer, an amide group. An acrylic resin having a weight average molecular weight of 400,000 to 2,000,000 and a dielectric constant of 3 to 6 obtained by copolymerization of a monomer component containing a monomer and a vinyl ester monomer A polymer compound is disclosed, and it is disclosed that the acrylic polymer compound is used for a pressure-sensitive adhesive composition for a touch panel, and that the composition is excellent in adhesion to a glass plate and a resin plate. However, JP2012-41456A does not disclose the durability of peeling.
　特開２００９－１８６９５９号公報には、画像表示部を有する基部、または該画像表示部上に配置される透光性の保護部に硬化型樹脂組成物を塗工し、基部と保護部とを近接対向配置し、硬化させて基部と保護部との間に樹脂硬化物層を形成する工程を有する画像表示装置の製造方法が開示され、硬化型樹脂組成物として、ポリウレタンアクリレート、ポリイソプレン系アクリレートまたはそのエステル化物、テルペン系水素添加樹脂およびブタジエン重合体から選ばれる１種以上のポリマーと、イソボルニルアクリレート、ジシクロペンテニルオキシエチルメタクリレートおよび２－ヒドロキシブチルメタクリレートから選ばれる１種以上のアクリレート系モノマーと、光重合開始剤とを含有する光硬化型樹脂組成物を用いること、硬化型樹脂組成物への気泡の混入を防止することが開示されている。しかし、ガラス板や樹脂板との接着性や剥がれについては開示がない。 In JP 2009-186959 A, a curable resin composition is applied to a base having an image display part or a translucent protective part arranged on the image display part, and the base and the protective part are provided. Disclosed is a method for manufacturing an image display device having a process of forming a resin cured material layer between a base portion and a protective portion by being placed in close proximity to each other and cured, and as a curable resin composition, polyurethane acrylate, polyisoprene acrylate Or one or more polymers selected from esterified products thereof, terpene hydrogenated resins and butadiene polymers, and one or more acrylates selected from isobornyl acrylate, dicyclopentenyloxyethyl methacrylate and 2-hydroxybutyl methacrylate. Use of a photocurable resin composition containing a monomer and a photopolymerization initiator, curing Preventing mixing of bubbles into the resin composition is disclosed. However, there is no disclosure about adhesiveness or peeling with a glass plate or a resin plate.
特開２００５－５５６４１号公報JP 2005-55641 A 特開２０１２－４６６５８号公報JP 2012-46658 A 特開２０１２－４１４５６号公報JP 2012-41456 A 特開２００９－１８６９５９号公報JP 2009-186959 A
　本発明は、画像表示装置の画像表示部と透光性の保護部との間に介在させる重合物層を形成するための重合性組成物において、表示部や保護部との剥がれを防止することを課題とする。従来、表示部と保護部は、共にガラス製が多かったが、最近は保護部に樹脂製（ポリカーボネートやＰＭＭＡ）を使用することが増え、ガラス板との耐剥がれ性だけでなく、樹脂板との耐剥がれ性が要求されているので、本発明は、ガラス板との耐剥がれ性のみならず、樹脂板との耐剥がれ性にも優れた重合性組成物を提供することを課題とする。また、耐剥がれ性は、耐久性が必要であって、高温高湿の条件で評価されるものなので、単なる接着性向上だけでは解決できないものである。本発明は、耐久性のある耐剥がれ性を課題とする。 The present invention relates to a polymerizable composition for forming a polymer layer interposed between an image display unit and a translucent protective unit of an image display device, and prevents peeling of the display unit and the protective unit. Is an issue. Conventionally, both the display unit and the protective unit are made of glass, but recently, the protective unit is made of resin (polycarbonate or PMMA), and not only the resistance to peeling from the glass plate but also the resin plate Therefore, an object of the present invention is to provide a polymerizable composition that is excellent not only in peeling resistance with a glass plate but also in peeling resistance with a resin plate. Further, the peeling resistance requires durability and is evaluated under conditions of high temperature and high humidity, and therefore cannot be solved only by improving adhesiveness. An object of the present invention is to provide durable peeling resistance.
　本発明者らは、上記課題を解決すべく研究を重ねた結果、重合性組成物の主成分である（メタ）アクリロイル基含有高分子化合物の分子量を特定範囲に限定したうえで、重合性組成物を重合することにより得られる重合物の貯蔵弾性率を一定の範囲に限定することにより上記課題が解決できることを見出し、本発明を完成するに至った。 As a result of repeated studies to solve the above-mentioned problems, the present inventors limited the molecular weight of the (meth) acryloyl group-containing polymer compound, which is the main component of the polymerizable composition, to a specific range, and then polymerizable composition. The inventors have found that the above problems can be solved by limiting the storage elastic modulus of the polymer obtained by polymerizing the product to a certain range, and have completed the present invention.
　即ち、本発明（Ｉ）は、画像表示装置の画像表示部と透光性の保護部との間に介在させる重合物層を形成するための重合性組成物であって、該重合性組成物が、
（成分１）数平均分子量が１０００～１５０００の範囲である（メタ）アクリロイル基含有高分子化合物、および
（成分２）光重合開始剤
を含み、かつ該重合性組成物を重合することにより得られる重合物の２５℃で周波数０．１Ｈｚでの貯蔵弾性率が１×１０３～１×１０５Ｐａであることを特徴とする重合性組成物に関する。
　本発明（ＩＩ）は、画像表示装置の画像表示部と透光性の保護部との間に介在させる重合物層を形成するための重合性組成物であって、該重合性組成物が、
（成分１）数平均分子量が１０００～１５０００の範囲である（メタ）アクリロイル基含有高分子化合物、
（成分２）光重合開始剤、および
（成分３）アルコール性水酸基とアミド基の少なくとも一方を有するラジカル重合性不飽和基含有化合物
を含み、かつ該重合性組成物を重合することにより得られる重合物の２５℃で周波数０．１Ｈｚでの貯蔵弾性率が１×１０３～１×１０５Ｐａであることを特徴とする重合性組成物に関する。
　本発明（ＩＩＩ）は、画像表示装置の画像表示部と透光性の保護部との間に介在させる重合物層を形成するための重合性組成物であって、該重合性組成物が、
（成分１）数平均分子量が１０００～１５０００の範囲である（メタ）アクリロイル基含有高分子化合物、
（成分２）光重合開始剤、
（成分３）アルコール性水酸基とアミド基の少なくとも一方を有するラジカル重合性不飽和基含有化合物、および
（成分４）アルコール性水酸基とアミド基のいずれの基も有さず、かつ粘度が２５℃で５００ｍＰａ・ｓ以下である（メタ）アクリロイル基含有化合物
を含み、かつ該重合性組成物を重合することにより得られる重合物の２５℃で周波数０．１Ｈｚでの貯蔵弾性率が１×１０３～１×１０５Ｐａであることを特徴とする重合性組成物に関する。
　本発明（ＩＶ）は、画像表示装置の画像表示部と透光性の保護部との間に介在させる重合物層を形成するための重合性組成物であって、該重合性組成物が、
（成分１）数平均分子量が１０００～１５０００の範囲である（メタ）アクリロイル基含有高分子化合物、
（成分２）光重合開始剤、
（成分３）アルコール性水酸基とアミド基の少なくとも一方を有するラジカル重合性不飽和基含有化合物、
（成分４）アルコール性水酸基とアミド基のいずれの基も有さず、かつ粘度が２５℃で５００ｍＰａ・ｓ以下である（メタ）アクリロイル基含有化合物、
（成分５）（メタ）アクリロイル基を有さない非イオン界面活性剤、および
（成分６）分子内に（メタ）アクリロイル基がなく、ラジカル重合を抑制する機能、ラジカル重合を禁止する機能、光重合性開始機能および界面活性作用のいずれの機能も有さず、かつ炭素原子と水素原子とから構成されるか、または炭素原子、水素原子および酸素原子から構成された、２５℃で液状または固体状である化合物
を含み、かつ該重合性組成物を重合することにより得られる重合物の２５℃で周波数０．１Ｈｚでの貯蔵弾性率が１×１０３～１×１０５Ｐａであることを特徴とする重合性組成物に関する。
　本発明（Ｖ）は、本発明（Ｉ）～本発明（ＩＶ）の重合性組成物を重合して得られる重合物に関する。
　本発明（ＶＩ）は、画像表示装置の画像表示部と透光性の保護部との間に介在させる重合物層として使用される光学用粘着シートを製造するための重合性組成物であって、該重合性組成物が本発明（Ｉ）～本発明（ＩＶ）の重合性組成物であることを特徴とする重合性組成物に関する。
　本発明（ＶＩＩ）は、本発明（ＶＩ）の重合性組成物を塗布し、光重合開始剤が感光可能な光を該重合性組成物に照射して、重合させることによって得られる、厚さ１０～１０００μｍの重合物層を有する光学用粘着シートに関する。
　本発明（ＶＩＩＩ）は、画像表示部を有する基部と、透光性の保護部と、前記基部と前記保護部との間に介在する重合物層を含む画像表示装置の製造方法であって、該方法が、本発明（ＩＶ）の重合性組成物を、前記基部と前記保護部との間に介在させる工程、および光重合開始剤が感光可能な光を前記重合性組成物に照射して重合物層を形成する工程を含むことを特徴とする画像表示装置の製造方法に関する。
　本発明（ＩＸ）は、画像表示部を有する基部と透光性の保護部とを光学用粘着シートを用いて貼り付ける工程を有する画像表示装置の製造方法であって、該光学用粘着シートが、本発明（ＶＩＩ）に記載の光学用粘着シートであることを特徴とする画像表示装置の製造方法に関する。
　本発明（Ｘ）は、本発明（ＶＩＩＩ）または本発明（ＩＸ）の画像表示装置の製造方法によって製造された画像表示装置に関する。 That is, the present invention (I) is a polymerizable composition for forming a polymer layer interposed between an image display part and a translucent protective part of an image display device, the polymerizable composition But,
(Component 1) containing a (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 15000, and (Component 2) a photopolymerization initiator, and obtained by polymerizing the polymerizable composition. The present invention relates to a polymerizable composition characterized by having a storage elastic modulus of 1 × 10 3 to 1 × 10 5 Pa at 25 ° C. and a frequency of 0.1 Hz.
The present invention (II) is a polymerizable composition for forming a polymer layer interposed between the image display part and the translucent protective part of the image display device, the polymerizable composition comprising:
(Component 1) (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 15000,
Polymerization obtained by polymerizing the polymerizable composition, comprising (Component 2) a photopolymerization initiator, and (Component 3) a radical polymerizable unsaturated group-containing compound having at least one of an alcoholic hydroxyl group and an amide group. The present invention relates to a polymerizable composition characterized by having a storage elastic modulus of 1 × 10 3 to 1 × 10 5 Pa at 25 ° C. and a frequency of 0.1 Hz.
The present invention (III) is a polymerizable composition for forming a polymer layer interposed between the image display part of the image display device and the translucent protective part, the polymerizable composition comprising:
(Component 1) (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 15000,
(Component 2) Photopolymerization initiator,
(Component 3) a radical polymerizable unsaturated group-containing compound having at least one of an alcoholic hydroxyl group and an amide group, and (Component 4) no alcoholic hydroxyl group or amide group, and a viscosity of 25 ° C. A polymer obtained by polymerizing the polymerizable composition containing a (meth) acryloyl group-containing compound that is 500 mPa · s or less has a storage elastic modulus at 25 ° C. and a frequency of 0.1 Hz of 1 × 10 3 to The present invention relates to a polymerizable composition characterized by being 1 × 10 5 Pa.
The present invention (IV) is a polymerizable composition for forming a polymer layer interposed between the image display part of the image display device and the translucent protective part, the polymerizable composition comprising:
(Component 1) (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 15000,
(Component 2) Photopolymerization initiator,
(Component 3) Radical polymerizable unsaturated group-containing compound having at least one of an alcoholic hydroxyl group and an amide group,
(Component 4) a (meth) acryloyl group-containing compound which does not have any group of an alcoholic hydroxyl group and an amide group and has a viscosity of 500 mPa · s or less at 25 ° C.
(Component 5) Nonionic surfactant having no (meth) acryloyl group, and (Component 6) No (meth) acryloyl group in the molecule, a function for suppressing radical polymerization, a function for inhibiting radical polymerization, light Liquid or solid at 25 ° C., which has neither a polymerization initiation function nor a surface-active function, and is composed of carbon atoms and hydrogen atoms, or is composed of carbon atoms, hydrogen atoms and oxygen atoms The storage modulus of the polymer obtained by polymerizing the polymerizable composition at 25 ° C. and a frequency of 0.1 Hz is 1 × 10 3 to 1 × 10 5 Pa. The present invention relates to a polymerizable composition.
The present invention (V) relates to a polymer obtained by polymerizing the polymerizable composition of the present invention (I) to the present invention (IV).
The present invention (VI) is a polymerizable composition for producing an optical pressure-sensitive adhesive sheet used as a polymer layer interposed between an image display portion and a translucent protective portion of an image display device. The present invention also relates to a polymerizable composition characterized in that the polymerizable composition is the polymerizable composition of the present invention (I) to the present invention (IV).
The present invention (VII) has a thickness obtained by applying the polymerizable composition of the present invention (VI), irradiating the polymerizable composition with light capable of being photosensitized by the photopolymerization initiator, and polymerizing the polymerizable composition. The present invention relates to an optical pressure-sensitive adhesive sheet having a polymer layer of 10 to 1000 μm.
The present invention (VIII) is a method for producing an image display device comprising a base having an image display portion, a translucent protective portion, and a polymer layer interposed between the base and the protective portion, The method comprises the step of interposing the polymerizable composition of the present invention (IV) between the base part and the protective part, and irradiating the polymerizable composition with light that can be photosensitized by a photopolymerization initiator. The present invention relates to a method for manufacturing an image display device including a step of forming a polymer layer.
This invention (IX) is a manufacturing method of an image display apparatus which has the process of sticking the base which has an image display part, and a translucent protective part using an optical adhesive sheet, Comprising: This optical adhesive sheet is And an optical pressure-sensitive adhesive sheet according to the present invention (VII).
The present invention (X) relates to an image display device manufactured by the manufacturing method of the image display device of the present invention (VIII) or the present invention (IX).
　さらに言えば、本発明は、以下の［１］～［１５］に関する。
　［１］　画像表示装置の画像表示部と透光性の保護部との間に介在させる重合物層を形成するための重合性組成物であって、該重合性組成物が、
（成分１）数平均分子量が１０００～１５０００の範囲である（メタ）アクリロイル基含有高分子化合物、および
（成分２）光重合開始剤
を含み、かつ該重合性組成物を重合することにより得られる重合物の２５℃で周波数０．１Ｈｚでの貯蔵弾性率が１×１０３～１×１０５Ｐａであることを特徴とする重合性組成物。
　［２］　前記成分１が炭素数４～９のジオールから誘導される構造単位および炭素数４～１０のジカルボン酸から誘導される構造単位を含むポリエステル構造単位を有する（メタ）アクリロイル基含有高分子化合物であることを特徴とする［１］に記載の重合性組成物。
　［３］　前記成分１がウレタン結合を有する（メタ）アクリロイル基含有高分子化合物であることを特徴とする［１］または［２］に記載の重合性組成物。
　［４］　（成分３）アルコール性水酸基とアミド基の少なくとも一方を有するラジカル重合性不飽和基含有化合物
をさらに含む［１］～［３］のいずれかに記載の重合性組成物。
　［５］　（成分４）アルコール性水酸基とアミド基のいずれの基も有さず、かつ粘度が２５℃で５００ｍＰａ・ｓ以下である（メタ）アクリロイル基含有化合物
をさらに含む［１］～［４］のいずれかに記載の重合性組成物。
　［６］　前記成分４がエーテル結合を有することを特徴とする［５］に記載の重合性組成物。
　［７］　（成分５）（メタ）アクリロイル基を有さない非イオン界面活性剤、および
（成分６）分子内に（メタ）アクリロイル基がなく、ラジカル重合を抑制する機能、ラジカル重合を禁止する機能、光重合性開始機能および界面活性作用のいずれの機能も有さず、かつ炭素原子と水素原子とから構成されるか、または炭素原子、水素原子および酸素原子から構成された、２５℃で液状または固体状である化合物
をさらに含む［１］～［６］のいずれかに記載の重合性組成物。
　［８］　前記成分６が、ポリエステルポリオール、ポリカーボネートポリオールおよび粘着付与剤からなる群から選ばれる少なくとも１種であることを特徴とする［７］に記載の重合性組成物。
　［９］　前記成分５が、グリフィンのＨＬＢの値が３．０～６．０である、（メタ）アクリロイル基を有さない非イオン界面活性剤であることを特徴とする［７］または［８］に記載の重合性組成物。
　［１０］　［１］～［９］のいずれかに記載の重合性組成物を重合して得られる重合物。
　［１１］　画像表示装置の画像表示部と透光性の保護部との間に介在させる重合物層として使用される光学用粘着シートを製造するための重合性組成物であって、該重合性組成物が［１］～［１０］のいずれかに記載の重合性組成物であることを特徴とする重合性組成物。
　［１２］　［１１］に記載の重合性組成物を塗布し、光重合開始剤が感光可能な光を該重合性組成物に照射して、重合させることによって得られる、厚さ１０～１０００μｍの重合物層を有する光学用粘着シート。
　［１３］　画像表示部を有する基部と、透光性の保護部と、前記基部と前記保護部との間に介在する重合物層を含む画像表示装置の製造方法であって、該方法が、
［７］～［９］のいずれかに記載の重合性組成物を、前記基部と前記保護部との間に介在させる工程、および
光重合開始剤が感光可能な光を前記重合性組成物に照射して重合物層を形成する工程
を含むことを特徴とする画像表示装置の製造方法。
　［１４］　画像表示部を有する基部と透光性の保護部とを光学用粘着シートを用いて貼り付ける工程を有する画像表示装置の製造方法であって、該光学用粘着シートが［１２］に記載の光学用粘着シートであることを特徴とする画像表示装置の製造方法。
　［１５］　［１３］または［１４］に記載の画像表示装置の製造方法によって製造された画像表示装置。 Furthermore, the present invention relates to the following [1] to [15].
[1] A polymerizable composition for forming a polymer layer interposed between an image display portion and a translucent protective portion of an image display device, the polymerizable composition comprising:
(Component 1) containing a (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 15000, and (Component 2) a photopolymerization initiator, and obtained by polymerizing the polymerizable composition. A polymerizable composition having a storage elastic modulus of 1 × 10 3 to 1 × 10 5 Pa at 25 ° C. and a frequency of 0.1 Hz.
[2] A (meth) acryloyl group-containing polymer having a structural unit derived from a diol having 4 to 9 carbon atoms and a structural unit derived from a dicarboxylic acid having 4 to 10 carbon atoms. The polymerizable composition as described in [1], which is a compound.
[3] The polymerizable composition as described in [1] or [2], wherein the component 1 is a (meth) acryloyl group-containing polymer compound having a urethane bond.
[4] (Component 3) The polymerizable composition according to any one of [1] to [3], further comprising a radical polymerizable unsaturated group-containing compound having at least one of an alcoholic hydroxyl group and an amide group.
[5] (Component 4) [1] to [4] further containing a (meth) acryloyl group-containing compound which does not have any group of an alcoholic hydroxyl group and an amide group and has a viscosity of 500 mPa · s or less at 25 ° C. ] The polymerizable composition in any one of.
[6] The polymerizable composition as described in [5], wherein the component 4 has an ether bond.
[7] (Component 5) Nonionic surfactant having no (meth) acryloyl group, and (Component 6) No (meth) acryloyl group in the molecule, inhibiting radical polymerization, and prohibiting radical polymerization No function, photopolymerization initiating function, or surface activity, and composed of carbon and hydrogen atoms, or composed of carbon, hydrogen, and oxygen atoms at 25 ° C The polymerizable composition according to any one of [1] to [6], further comprising a liquid or solid compound.
[8] The polymerizable composition as described in [7], wherein the component 6 is at least one selected from the group consisting of a polyester polyol, a polycarbonate polyol, and a tackifier.
[9] The component 5 is a nonionic surfactant having no (meth) acryloyl group, wherein the HLB value of Griffin is 3.0 to 6.0 [7] or [7] 8].
[10] A polymer obtained by polymerizing the polymerizable composition according to any one of [1] to [9].
[11] A polymerizable composition for producing an optical pressure-sensitive adhesive sheet used as a polymer layer interposed between an image display portion and a translucent protective portion of an image display device, wherein the polymerizable composition A polymerizable composition, wherein the composition is the polymerizable composition according to any one of [1] to [10].
[12] A film having a thickness of 10 to 1000 μm obtained by applying the polymerizable composition according to [11], irradiating the polymerizable composition with light that can be photosensitized by the photopolymerization initiator, and polymerizing the polymerizable composition. An optical pressure-sensitive adhesive sheet having a polymer layer.
[13] A method for manufacturing an image display device, comprising: a base having an image display portion; a translucent protective portion; and a polymer layer interposed between the base portion and the protective portion, the method comprising:
[7] to [9] The polymerizable composition according to any one of [7] to [9] is interposed between the base portion and the protective portion, and light capable of being photosensitized by a photopolymerization initiator is added to the polymerizable composition. The manufacturing method of the image display apparatus characterized by including the process of irradiating and forming a polymer layer.
[14] A method for manufacturing an image display device including a step of attaching a base portion having an image display portion and a translucent protective portion using an optical pressure-sensitive adhesive sheet, the optical pressure-sensitive adhesive sheet according to [12] A method for producing an image display device, which is the optical pressure-sensitive adhesive sheet according to claim 1.
[15] An image display device manufactured by the method for manufacturing an image display device according to [13] or [14].
　本発明の重合性組成物は、画像表示装置の画像表示部と透光性の保護部との間に介在させる重合物層を形成するために用いることができ、ガラス製の表示部や保護部との耐剥がれ性のみならず樹脂製の表示部や保護部との耐剥がれ性にも優れ、しかも耐久性のある耐剥がれ性を付与することができる。 The polymerizable composition of the present invention can be used to form a polymer layer interposed between an image display portion and a translucent protective portion of an image display device, and is made of a glass display portion or protective portion. It is excellent not only in peeling resistance but also in peeling resistance with a resin-made display part and protective part, and it is possible to impart durable peeling resistance.
図１は、本発明に係る表示装置の実施形態の要部を示す断面図である。FIG. 1 is a cross-sectional view showing a main part of an embodiment of a display device according to the present invention. 図２は、本発明に係る表示装置の実施形態の要部を示す断面図である。FIG. 2 is a cross-sectional view showing a main part of an embodiment of the display device according to the present invention. 図３は、本発明に係る表示装置の実施形態の要部を示す断面図である。FIG. 3 is a cross-sectional view showing a main part of an embodiment of the display device according to the present invention. 図４は、本発明に係る表示装置の実施形態の要部を示す断面図である。FIG. 4 is a cross-sectional view showing a main part of an embodiment of the display device according to the present invention. 図５は、本発明に係る表示装置の実施形態の要部を示す断面図である。FIG. 5 is a cross-sectional view showing a main part of an embodiment of the display device according to the present invention. 図６は、従来技術に係る表示装置の要部を示す断面図である。FIG. 6 is a cross-sectional view showing a main part of a display device according to the prior art.
　以下、本発明を具体的に説明する。
　なお、本明細書に記載の「重合物」とは、重合性組成物を重合して得られる重合物であれば、形態等に特に制限はなく、本明細書に記載の「光学用粘着シート」も重合物に含まれることを意味する。
　本明細書では、本発明（Ｉ）の重合性組成物の必須原料成分である成分１の原料になり得るポリエステルポリオールを製造する際に、ポリエステルポリオールの原料であるポリオール（即ち、－ＣＯＯ－結合（カルボン酸エステル結合）を有さないポリオール）が残存する場合には、このポリオールもポリエステルポリオールには含まれるものと定義する。加えて、本明細書では、ポリエステルポリオール中に含まれる原料ポリオールの他に、新たに、使用するポリエステルポリオールの原料成分であるポリオールを加えて、本発明（Ｉ）の重合性組成物の必須成分である成分１が製造された場合、この加えられたポリオールは、例え－ＣＯＯ－結合（カルボン酸エステル結合）を有さないポリオールであっても、ポリエステルポリオールに含まれるものとする。
　また、本明細書では、本発明（Ｉ）の重合性組成物の必須原料成分である成分１の原料になり得るポリカーボネートポリオールを製造する際に、ポリカーボネートポリオールの原料であるポリオール（即ち、カーボネート結合を有さないポリオール）が残存する場合には、このポリオールもポリカーボネートポリオールには含まれるものとする。加えて、本明細書では、ポリカーボネートポリオール中に含まれる原料ポリオールの他に、新たに、使用するポリカーボネートポリオールの原料成分であるポリオールを加えて、本発明（Ｉ）の重合性組成物の必須成分である成分１が製造された場合、この加えられたポリオールは、ポリカーボネートポリオールに含まれるものとする。
　また、本明細書では、本発明（Ｉ）の重合性組成物の必須原料成分である成分１の原料になり得るポリエーテルポリオールを製造する際に、ポリエーテルポリオールの原料であるポリオール（即ち、エーテル結合を有さないポリオール）が残存する場合には、このポリオールもポリエーテルポリオールには含まれるものとする。加えて、本明細書では、ポリエーテルポリオール中に含まれる原料ポリオールの他に、新たに、使用するポリエーテルポリオールの原料成分であるポリオールを加えて、本発明（Ｉ）の重合性組成物の必須成分である成分１が製造された場合、この加えられたポリオールは、ポリエーテルポリオールに含まれるものとする。 Hereinafter, the present invention will be specifically described.
In addition, there is no restriction | limiting in particular in a form etc. as long as it is a polymer obtained by superposing | polymerizing polymeric composition as "polymerized substance" as described in this specification, "optical adhesive sheet as described in this specification "Also means included in the polymer.
In the present specification, when producing a polyester polyol that can be a raw material of Component 1, which is an essential raw material component of the polymerizable composition of the present invention (I), a polyol (that is, a —COO— bond) that is a raw material of the polyester polyol. In the case where (polyol having no carboxylic ester bond) remains, this polyol is also defined as being included in the polyester polyol. In addition, in this specification, in addition to the raw material polyol contained in the polyester polyol, a polyol which is a raw material component of the polyester polyol to be used is newly added, and the essential component of the polymerizable composition of the present invention (I) When component 1 is produced, the added polyol is included in the polyester polyol even if it has no —COO— bond (carboxylic acid ester bond).
Further, in the present specification, when producing a polycarbonate polyol that can be a raw material of Component 1, which is an essential raw material component of the polymerizable composition of the present invention (I), a polyol (that is, a carbonate bond) that is a raw material of the polycarbonate polyol. In the case where a polyol (which does not have any) remains, this polyol is also included in the polycarbonate polyol. In addition, in this specification, in addition to the raw material polyol contained in the polycarbonate polyol, a polyol which is a raw material component of the polycarbonate polyol to be used is newly added, and the essential component of the polymerizable composition of the present invention (I) When component 1 is produced, this added polyol shall be included in the polycarbonate polyol.
Further, in the present specification, when producing a polyether polyol that can be a raw material of Component 1, which is an essential raw material component of the polymerizable composition of the present invention (I), a polyol that is a raw material of the polyether polyol (ie, When a polyol having no ether bond) remains, this polyol is also included in the polyether polyol. In addition, in the present specification, in addition to the raw material polyol contained in the polyether polyol, a polyol which is a raw material component of the polyether polyol to be used is newly added to the polymerizable composition of the present invention (I). When component 1, which is an essential component, is produced, the added polyol shall be included in the polyether polyol.
　まず、本発明（Ｉ）について説明する。
　本発明（Ｉ）は、画像表示装置の画像表示部と透光性の保護部との間に介在させる重合物層を形成するための重合性組成物であって、該重合性組成物が、
（成分１）数平均分子量が１０００～１５０００の範囲である（メタ）アクリロイル基含有高分子化合物、および
（成分２）光重合開始剤
を含み、かつ該重合性組成物を重合することにより得られる重合物の２５℃で周波数０．１Ｈｚでの貯蔵弾性率が１×１０３～１×１０５Ｐａであることを特徴とする重合性組成物である。 First, the present invention (I) will be described.
The present invention (I) is a polymerizable composition for forming a polymer layer interposed between the image display part of the image display device and the translucent protective part, the polymerizable composition comprising:
(Component 1) containing a (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 15000, and (Component 2) a photopolymerization initiator, and obtained by polymerizing the polymerizable composition. A polymerizable composition having a storage elastic modulus of 1 × 10 3 to 1 × 10 5 Pa at 25 ° C. and a frequency of 0.1 Hz.
　まず、本発明（Ｉ）の重合性組成物の必須成分である成分１について説明する。
　本発明（Ｉ）の重合性組成物の必須成分である成分１は、数平均分子量が１０００～１５０００の範囲である（メタ）アクリロイル基含有高分子化合物である。
　成分１は、数平均分子量が１０００～１５０００の範囲にあり、かつ（メタ）アクリロイル基を有する高分子化合物であれば、特に制限はない。
　なお、本明細書に記載の「高分子化合物」とは、分子量分布を有する重合体であることを意味する。
　また、本明細書に記載の「数平均分子量」とは、ゲルパーミエーションクロマトグラフ法（以下、「ＧＰＣ」と記す。）による、ポリスチレン換算として測定された、数平均分子量のことである。 First, component 1 which is an essential component of the polymerizable composition of the present invention (I) will be described.
Component 1 which is an essential component of the polymerizable composition of the present invention (I) is a (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 15000.
Component 1 is not particularly limited as long as it is a polymer compound having a number average molecular weight in the range of 1000 to 15000 and having a (meth) acryloyl group.
The “polymer compound” described in the present specification means a polymer having a molecular weight distribution.
Further, the “number average molecular weight” described in the present specification is a number average molecular weight measured in terms of polystyrene by gel permeation chromatography (hereinafter referred to as “GPC”).
　本発明（Ｉ）に必須成分である成分１の高分子化合物の数平均分子量は、１０００～１５０００の範囲である。好ましくは、１２００～８０００の範囲であり、さらに好ましくは、１５００～６０００の範囲である。数平均分子量が、１０００未満の場合には、本発明（Ｉ）の組成物を重合して得られる重合物の重合時の体積収縮率が大きくなったり、重合物が硬くなりすぎる場合がある。また、数平均分子量が、１５０００以上の場合には、粘度が高くなりすぎる場合がある。 The number average molecular weight of the polymer compound of component 1 which is an essential component in the present invention (I) is in the range of 1000 to 15000. The range is preferably 1200 to 8000, and more preferably 1500 to 6000. When the number average molecular weight is less than 1000, the volume shrinkage during polymerization of the polymer obtained by polymerizing the composition of the present invention (I) may increase, or the polymer may become too hard. When the number average molecular weight is 15000 or more, the viscosity may be too high.
　数平均分子量が１０００～１５０００の範囲である（メタ）アクリロイル基含有高分子化合物の具体例としては、例えば、数平均分子量が１０００～１５０００の範囲である、ポリエーテル（メタ）アクリレート、ポリエステル（メタ）アクリレート、エポキシ（メタ）アクリレート、ウレタン（メタ）アクリレート、ウレタン（メタ）アクリルアミド、ポリカーボネート（メタ）アクリレート等を挙げることができる。 Specific examples of the (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 15000 include, for example, polyether (meth) acrylate and polyester (meth) having a number average molecular weight in the range of 1000 to 15000. ) Acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, urethane (meth) acrylamide, polycarbonate (meth) acrylate, and the like.
　本明細書における「（メタ）アクリレート」とは、アクリレートおよびメタクリレートから選ばれる少なくとも一方の基を意味する。さらに、本明細書における「（メタ）アクリルアミド」とは、アクリルアミドおよびメタクリルアミドから選ばれる少なくとも一方の基を意味する。
　ポリエーテル（メタ）アクリレートとは、ポリエーテルポリオールと（メタ）アクリル酸の脱水縮合反応、あるいはポリエーテルポリオールと（メタ）アクリル酸エステルとのエステル交換反応により製造される（メタ）アクリレートである。
　なお、本明細書における「（メタ）アクリル酸」とは、アクリル酸およびメタクリル酸から選ばれる少なくとも一方の基を意味する。
　ポリエステル（メタ）アクリレートとは、ポリエステルポリオールと（メタ）アクリル酸の脱水縮合反応、あるいはポリエステルポリオールと（メタ）アクリル酸エステルとのエステル交換反応により製造される（メタ）アクリレートである。
　エポキシ（メタ）アクリレートとは、エーテル結合、エステル結合あるいは炭化水素鎖を有するエポキシ基含有化合物と（メタ）アクリル酸の反応生成物や、ポリエステルポリカルボン酸や脂肪族炭化水素鎖、芳香環を有するポリカルボン酸あるいは複素環を有するポリカルボン酸等のポリカルボン酸と、グリシジル（メタ）アクリレート、（メタ）アクリロイルオキシブチルグリシジルエーテル等のエポキシ基含有（メタ）アクリロイル基含有化合物との反応生成物である。
　ウレタン（メタ）アクリレートとは、ポリオール、有機ポリイソシアネート化合物およびアルコール性水酸基含有（メタ）アクリレートを必須原料に用いた重付加反応、あるいはポリオールおよびイソシアナト基を有する（メタ）アクリレートを必須原料に用いた重付加反応により、分子中にウレタン結合を有し、かつ１つ以上の（メタ）アクリレート基を有する化合物である。
　ウレタン（メタ）アクリルアミドとは、ポリオール、有機ポリイソシアネート化合物およびアルコール性水酸基含有（メタ）アクリルアミドを必須原料に用いた重付加反応により、分子中にウレタン結合を有し、かつ１つ以上の（メタ）アクリレート基を有する化合物である。
　ポリカーボネート（メタ）アクリレートとは、ポリカーボネートポリオールと（メタ）アクリル酸との縮合反応、あるいはポリカーボネートポリオールと（メタ）アクリル酸エステルとのエステル交換反応により製造される（メタ）アクリレートである。 The “(meth) acrylate” in the present specification means at least one group selected from acrylate and methacrylate. Furthermore, “(meth) acrylamide” in the present specification means at least one group selected from acrylamide and methacrylamide.
The polyether (meth) acrylate is a (meth) acrylate produced by a dehydration condensation reaction between a polyether polyol and (meth) acrylic acid or a transesterification reaction between the polyether polyol and (meth) acrylic acid ester.
In addition, “(meth) acrylic acid” in the present specification means at least one group selected from acrylic acid and methacrylic acid.
The polyester (meth) acrylate is a (meth) acrylate produced by a dehydration condensation reaction between a polyester polyol and (meth) acrylic acid or a transesterification reaction between the polyester polyol and (meth) acrylic acid ester.
Epoxy (meth) acrylate has a reaction product of an epoxy group-containing compound having an ether bond, an ester bond or a hydrocarbon chain and (meth) acrylic acid, a polyester polycarboxylic acid, an aliphatic hydrocarbon chain, or an aromatic ring. A reaction product of a polycarboxylic acid such as a polycarboxylic acid or a polycarboxylic acid having a heterocyclic ring and an epoxy group-containing (meth) acryloyl group-containing compound such as glycidyl (meth) acrylate or (meth) acryloyloxybutyl glycidyl ether is there.
Urethane (meth) acrylate is a polyaddition reaction using polyol, organic polyisocyanate compound and alcoholic hydroxyl group-containing (meth) acrylate as essential materials, or (meth) acrylate having a polyol and isocyanate group as essential materials. A compound having a urethane bond in the molecule and one or more (meth) acrylate groups by a polyaddition reaction.
Urethane (meth) acrylamide has a urethane bond in the molecule by a polyaddition reaction using polyol, organic polyisocyanate compound and alcoholic hydroxyl group-containing (meth) acrylamide as essential raw materials, and one or more (meta) ) A compound having an acrylate group.
The polycarbonate (meth) acrylate is a (meth) acrylate produced by a condensation reaction between a polycarbonate polyol and (meth) acrylic acid or a transesterification reaction between a polycarbonate polyol and (meth) acrylic acid ester.
　画像表示装置の画像表示部と透光性の保護部との密着性を考慮すると、これらの中で、好ましいものとしては、ウレタン結合を有する（メタ）アクリロイル基含有高分子化合物である。即ち、具体的には、画像表示装置の画像表示部と透光性の保護部との密着性を考慮すると、ウレタン（メタ）アクリレート、ウレタン（メタ）アクリルアミドが好ましい。
　なお、本明細書における「ウレタン（メタ）アクリレート」とは、分子中にウレタン結合を有し、かつ１つ以上のアクリレート基かメタクリレート基を有する化合物である。また、本明細書における「ウレタン（メタ）アクリルアミド」とは、分子中にウレタン結合を有し、かつ１つ以上のアクリルアミド基かメタクリルアミド基を有する化合物である。 In view of the adhesion between the image display part of the image display device and the translucent protective part, among these, a (meth) acryloyl group-containing polymer compound having a urethane bond is preferable. Specifically, urethane (meth) acrylate and urethane (meth) acrylamide are preferable in consideration of the adhesion between the image display unit of the image display device and the translucent protective unit.
The “urethane (meth) acrylate” in the present specification is a compound having a urethane bond in the molecule and one or more acrylate groups or methacrylate groups. The “urethane (meth) acrylamide” in the present specification is a compound having a urethane bond in the molecule and having one or more acrylamide groups or methacrylamide groups.
　これら、ウレタン（メタ）アクリレートやウレタン（メタ）アクリルアミドの製造方法としては、特に制限はないが、例えば、以下の方法によって製造することができる。 These production methods of urethane (meth) acrylate and urethane (meth) acrylamide are not particularly limited, but can be produced, for example, by the following method.
　まず、ポリオール、有機ポリイソシアネート化合物およびアルコール性水酸基含有（メタ）アクリレートを必須原料成分に用いて、ウレタン（メタ）アクリレートを得る場合について説明する。
　このウレタン（メタ）アクリレートの製造に用いられるポリオールは、１分子中にアルコール性水酸基を２個以上有するものであるが、アルコール性水酸基を２～３個有することが好ましく、さらに好ましくは、２個有することである。また、ポリオールの好ましい構造は、ポリエステルポリオール、ポリカーボネートポリオール、あるいはポリエーテルポリオールであり、より好ましくは、ポリエステルポリオールまたはポリカーボネートポリオールであり、最も好ましくは、ポリエステルポリオールである。
　また、このポリオールの水酸基価は、１０～１２０ｍｇＫＯＨ／ｇであることが好ましく、さらに好ましくは１５～１００ｍｇＫＯＨ／ｇ、特に好ましくは２０～８０ｍｇＫＯＨ／ｇである。ポリオールの水酸基価が１０ｍｇＫＯＨ／ｇより小さくなると、得られるポリウレタン（メタ）アクリレートの分子量と粘度が高くなりすぎ、ハンドリング性も悪くなり、取り扱いが困難となる傾向にある。また、ポリオールの水酸基価が１２０ｍｇＫＯＨ／ｇより大きくなると、重合時の体積収縮率は大きくなりすぎたり、重合物の凝集力が高くなりすぎたりして、重合物の粘着性能が十分に発揮されない場合がある。 First, the case where urethane (meth) acrylate is obtained using polyol, organic polyisocyanate compound and alcoholic hydroxyl group-containing (meth) acrylate as essential raw material components will be described.
The polyol used in the production of this urethane (meth) acrylate has 2 or more alcoholic hydroxyl groups in one molecule, preferably 2 to 3 alcoholic hydroxyl groups, more preferably 2 Is to have. The preferred structure of the polyol is polyester polyol, polycarbonate polyol, or polyether polyol, more preferably polyester polyol or polycarbonate polyol, and most preferably polyester polyol.
The hydroxyl value of this polyol is preferably 10 to 120 mgKOH / g, more preferably 15 to 100 mgKOH / g, and particularly preferably 20 to 80 mgKOH / g. When the hydroxyl value of the polyol is less than 10 mgKOH / g, the molecular weight and viscosity of the resulting polyurethane (meth) acrylate are too high, handling properties tend to be poor, and handling tends to be difficult. Also, when the hydroxyl value of the polyol is greater than 120 mgKOH / g, the volume shrinkage during polymerization becomes too large, or the cohesive strength of the polymer becomes too high, and the adhesive performance of the polymer is not sufficiently exhibited. There is.
　有機ポリイソシアネート化合物は、１分子中に２個以上のイソシアナト基を有する有機化合物であれば特に制限はない。具体的には、例えば、１，４－シクロヘキサンジイソシアネート、イソホロンジイソシアネート、メチレンビス（４－シクロヘキシルイソシアネート）、１，３－ビス（イソシアナトメチル）シクロヘキサン、１，４－ビス（イソシアナトメチル）シクロヘキサン、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、ジフェニルメタン－４，４′－ジイソシアネート、１，３－キシリレンジイソシアネート、１，４－キシリレンジイソシアネート、リシントリイソシアネート、リシンジイソシアネート、ヘキサメチレンジイソシアネート、２，４，４－トリメチルヘキサメチレンジイソシアネート、２，２，４－トリメチルヘキサンメチレンジイソシアネートおよびノルボルナンジイソシアネート等を挙げることができ、これらを単独で、または２種以上組合せて使用することができる。 The organic polyisocyanate compound is not particularly limited as long as it is an organic compound having two or more isocyanato groups in one molecule. Specifically, for example, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, , 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, lysine triisocyanate, lysine diisocyanate, hexamethylene diisocyanate 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexanemethylene diisocyanate, norbornane diisocyanate, etc. , It may be used in combination of these alone, or two or more.
　本発明（Ｉ）の重合性組成物の必須成分である成分１は、その後の配合の自由度を考慮すると、粘度が低いことが望ましい。この目的に合致する有機ポリイソシアネート化合物としては、１，３－ビス（イソシアナトメチル）シクロヘキサン、１，４－ビス（イソシアナトメチル）シクロヘキサン、２，４，４－トリメチルヘキサメチレンジイソシアネート、２，２，４－トリメチルヘキサンメチレンジイソシアネート、１，６－ヘキサメチレンジイソシアネートおよびノルボルナンジイソシアネートが好ましく、さらに好ましくは、１，３－ビス（イソシアナトメチル）シクロヘキサン、２，４，４－トリメチルヘキサメチレンジイソシアネートおよび２，２，４－トリメチルヘキサンメチレンジイソシアネートであり、最も好ましいのは、２，４，４－トリメチルヘキサメチレンジイソシアネートおよび２，２，４－トリメチルヘキサンメチレンジイソシアネートである。 The component 1 which is an essential component of the polymerizable composition of the present invention (I) preferably has a low viscosity in consideration of the degree of freedom of subsequent blending. Examples of organic polyisocyanate compounds that meet this purpose include 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, 2,4,4-trimethylhexamethylene diisocyanate, 2,2 , 4-trimethylhexanemethylene diisocyanate, 1,6-hexamethylene diisocyanate and norbornane diisocyanate are preferred, more preferably 1,3-bis (isocyanatomethyl) cyclohexane, 2,4,4-trimethylhexamethylene diisocyanate and 2, 2,4-trimethylhexanemethylene diisocyanate, most preferred are 2,4,4-trimethylhexamethylene diisocyanate and 2,2,4-trimethylhexanemethylene diisocyanate It is.
　アルコール性水酸基含有（メタ）アクリレートは、１分子中にアルコール性水酸基を有する（メタ）アクリレートであれば特に制限はない。具体的には、２－ヒドロキシエチルアクリレート、２－ヒドロキシプロピルアクリレート、３－ヒドロキシプロピルアクリレート、２－ヒドロキシブチルアクリレート、４－ヒドロキシブチルアクリレート、２－ヒドロキシ－３－フェノキシプロピルアクリレート、２－ヒドロキシ－３－（ｏ－フェニルフェノキシ）プロピルアクリレート、２－ヒドロキシエチルアクリルアミド、２－ヒドロキシエチルメタクリレート、２－ヒドロキシプロピルメタクリレート、３－ヒドロキシプロピルメタクリレート、２－ヒドロキシブチルメタクリレート、４－ヒドロキシブチルメタクリレート、２－ヒドロキシ－３－フェノキシプロピルメタクリレート、２－ヒドロキシ－３－（ｏ－フェニルフェノキシ）プロピルメタクリレート等を挙げることができる。 The alcoholic hydroxyl group-containing (meth) acrylate is not particularly limited as long as it is a (meth) acrylate having an alcoholic hydroxyl group in one molecule. Specifically, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3 -(O-phenylphenoxy) propyl acrylate, 2-hydroxyethyl acrylamide, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxy- Examples include 3-phenoxypropyl methacrylate and 2-hydroxy-3- (o-phenylphenoxy) propyl methacrylate. That.
　これらの中で、本発明（Ｉ）の必須成分である成分１の重合速度を考慮すると、好ましいものとしては、２－ヒドロキシエチルアクリレート、２－ヒドロキシプロピルアクリレート、３－ヒドロキシプロピルアクリレート、２－ヒドロキシブチルアクリレート、４－ヒドロキシブチルアクリレート、２－ヒドロキシ－３－フェノキシプロピルアクリレート、２－ヒドロキシ－３－（ｏ－フェニルフェノキシ）プロピルアクリレートである。イソシアネート基との反応性を考慮すると、２－ヒドロキシエチルアクリレート、３－ヒドロキシプロピルアクリレート、４－ヒドロキシブチルアクリレートが好ましく、最も好ましいのは、４－ヒドロキシブチルアクリレートである。 Among these, considering the polymerization rate of component 1, which is an essential component of the present invention (I), preferred are 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxy Butyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3- (o-phenylphenoxy) propyl acrylate. In consideration of the reactivity with the isocyanate group, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate and 4-hydroxybutyl acrylate are preferable, and 4-hydroxybutyl acrylate is most preferable.
　ポリオール、有機ポリイソシアネート化合物およびアルコール性水酸基含有（メタ）アクリレートを反応させる方法として、ジブチル錫ジラウリレート、ジオクチル錫ジラウレートのような公知のウレタン化触媒の存在下または非存在下で、ポリオール、有機ポリイソシアネート化合物およびアルコール性水酸基含有（メタ）アクリレートを反応させることにより合成が出来るが、触媒の存在下で反応させたほうが、反応時間を短縮する意味では好ましい。ただし、多く使用しすぎると、最終的に硬化膜としての実使用時の物性値に悪影響を及ぼす可能性があるので、使用量は、ポリオール、有機ポリイソシアネート化合物、アルコール性水酸基含有（メタ）アクリレートの総量１００質量部に対して０．００１～１質量部であることが好ましい。 As a method of reacting a polyol, an organic polyisocyanate compound, and an alcoholic hydroxyl group-containing (meth) acrylate, a polyol, an organic polyisocyanate, in the presence or absence of a known urethanization catalyst such as dibutyltin dilaurate or dioctyltin dilaurate The compound can be synthesized by reacting the alcoholic hydroxyl group-containing (meth) acrylate, but the reaction in the presence of a catalyst is preferable in terms of shortening the reaction time. However, if too much is used, there is a possibility that the physical property value at the time of actual use as a cured film will be adversely affected, so the amount used is polyol, organic polyisocyanate compound, alcoholic hydroxyl group-containing (meth) acrylate. The total amount is preferably 0.001 to 1 part by mass with respect to 100 parts by mass.
　原料の仕込みを行う順番については特に制約はないが、例えば、有機ポリイソシアネート化合物および必要に応じてウレタン化触媒を反応器に投入し、撹拌を行い、その後、反応器内の温度を４０℃～１４０℃、好ましくは５０℃～１２０℃で、ポリオール、さらに必要に応じて、ポリオールを順次投入し、その後、反応器内の温度を５０℃～１６０℃、好ましくは６０℃～１４０℃でこれらを反応させる。その後、反応器内の温度を３０℃～１２０℃、好ましくは５０℃～１００℃で、重合禁止剤および必要に応じてウレタン化触媒を添加し、滴下によりアルコール性水酸基含有（メタ）アクリレートを投入する。滴下中、反応器内の温度を３０℃～１２０℃、望ましくは５０℃～１００℃に維持することが好ましい。滴下終了後、反応器内の温度を３０℃～１２０℃、望ましくは５０℃～１００℃に維持し、反応を完結させる。 The order in which the raw materials are charged is not particularly limited. For example, the organic polyisocyanate compound and, if necessary, the urethanization catalyst are charged into the reactor and stirred, and then the temperature in the reactor is set to 40 ° C. to 40 ° C. At 140 ° C., preferably 50 ° C. to 120 ° C., polyols and, if necessary, polyols are sequentially added, and then the temperature in the reactor is 50 ° C. to 160 ° C., preferably 60 ° C. to 140 ° C. React. Thereafter, the temperature in the reactor is 30 ° C. to 120 ° C., preferably 50 ° C. to 100 ° C., a polymerization inhibitor and a urethanization catalyst are added if necessary, and an alcoholic hydroxyl group-containing (meth) acrylate is added dropwise. To do. During the dropping, the temperature in the reactor is preferably maintained at 30 ° C. to 120 ° C., desirably 50 ° C. to 100 ° C. After completion of the dropwise addition, the temperature in the reactor is maintained at 30 ° C. to 120 ° C., preferably 50 ° C. to 100 ° C., to complete the reaction.
　また、他の方法としては、例えば、有機ポリイソシアネート化合物、必要に応じて重合禁止剤および／またはウレタン化触媒を反応器に投入し、撹拌を行い、その後、反応器内の温度を３０℃～１２０℃、好ましくは５０℃～１１０℃で、アルコール性水酸基含有（メタ）アクリレートを滴下により投入する。滴下中、反応器内の温度を３０℃～１２０℃、望ましくは５０℃～１１０℃に維持することが好ましい。滴下終了後、反応器内の温度を３０℃～１２０℃、望ましくは５０℃～１１０℃に維持し、反応させる。その後、上記反応生成物を、ポリオールを入れた反応器に、撹拌しながら、反応器内の温度を３０℃～１２０℃、好ましくは５０℃～１００℃に維持できるように投入し、投入後、反応器内の温度を３０℃～１２０℃、望ましくは５０℃～１００℃に維持し、反応を完結させる。 In addition, as another method, for example, an organic polyisocyanate compound, a polymerization inhibitor and / or a urethanization catalyst as necessary, are charged into the reactor, and stirred, and then the temperature in the reactor is changed from 30 ° C. to 30 ° C. The alcoholic hydroxyl group-containing (meth) acrylate is added dropwise at 120 ° C., preferably 50 ° C. to 110 ° C. During the dropping, the temperature in the reactor is preferably maintained at 30 ° C. to 120 ° C., desirably 50 ° C. to 110 ° C. After completion of the dropwise addition, the temperature in the reactor is maintained at 30 ° C. to 120 ° C., preferably 50 ° C. to 110 ° C., and reacted. Thereafter, the reaction product is charged into the reactor containing the polyol while stirring so that the temperature in the reactor can be maintained at 30 ° C. to 120 ° C., preferably 50 ° C. to 100 ° C. The temperature in the reactor is maintained at 30 ° C. to 120 ° C., preferably 50 ° C. to 100 ° C., to complete the reaction.
　本発明（Ｉ）の必須成分である成分１として用いたとき、オリゴマーの粘度上昇の抑制あるいは重合時の体積収縮率の低減の必要がある場合には、化合物の末端の一部のみを、アルコール性水酸基含有（メタ）アクリレートを含む水酸基を分子中に１つ有する化合物で封止されるオリゴマーであることが望ましい。 When used as Component 1 which is an essential component of the present invention (I), when it is necessary to suppress the increase in the viscosity of the oligomer or to reduce the volume shrinkage during polymerization, only a part of the end of the compound is alcohol. It is desirable that the oligomer be sealed with a compound having one hydroxyl group in the molecule containing a functional hydroxyl group-containing (meth) acrylate.
　原料の仕込みモル比（即ち、（ポリオールの水酸基の総数）／（使用された有機ポリイソシアネート化合物のイソシアナト基の総数）／（アルコール性水酸基含有（メタ）アクリレートを含む水酸基を分子中に１つ有する化合物の使用数を合わせたときの水酸基の総数））は、目的とするポリウレタンの分子量に応じて調節する。 Charge molar ratio of raw materials (that is, (total number of hydroxyl groups of polyol) / (total number of isocyanato groups of organic polyisocyanate compound used) / (one hydroxyl group containing alcoholic hydroxyl group-containing (meth) acrylate) The total number of hydroxyl groups)) when the number of compounds used is adjusted is adjusted according to the molecular weight of the target polyurethane.
　ただし、化合物の末端を、アルコール性水酸基含有（メタ）アクリレートを含む水酸基を分子中に１つ有する化合物でほぼ完全に封止される場合には、使用されるポリオールの水酸基の総数より使用される有機ポリイソシアネート化合物のイソシアナト基の総数を多くする必要がある。
　この場合には、使用されるポリオールの水酸基の総数と、有機ポリイソシアネート化合物中のイソシアナト基の総数の比が、１．０に近いと製造される化合物の平均分子量が大きくなり、１．０より小さくなるにつれてその平均分子量は小さくなる。
　原料の仕込みモル比には特に制限はないが、使用されるポリオールの水酸基の総数と有機ポリイソシアネート化合物中のイソシアナト基の数の比は、ポリオールの水酸基の総数が１等量に対して、有機ポリイソシアネート化合物中のイソシアナト基が１．５等量以上であることが好ましい。
　ポリオールの水酸基の総数が１等量に対して有機ポリイソシアネート化合物中のイソシアナト基が１．５等量よりも小さい場合には、粘度が高くなりすぎる場合がある。 However, when the end of the compound is almost completely sealed with a compound having one hydroxyl group in the molecule containing an alcoholic hydroxyl group-containing (meth) acrylate, the total number of hydroxyl groups of the polyol used is used. It is necessary to increase the total number of isocyanato groups in the organic polyisocyanate compound.
In this case, if the ratio of the total number of hydroxyl groups of the polyol used and the total number of isocyanato groups in the organic polyisocyanate compound is close to 1.0, the average molecular weight of the compound to be produced increases. The average molecular weight decreases as the value decreases.
The feed molar ratio of the raw material is not particularly limited, but the ratio of the total number of hydroxyl groups in the polyol used and the number of isocyanate groups in the organic polyisocyanate compound is organic with respect to 1 equivalent of the total number of hydroxyl groups in the polyol. The isocyanate group in the polyisocyanate compound is preferably 1.5 equivalents or more.
If the total number of hydroxyl groups in the polyol is less than 1.5 equivalents of the isocyanate group in the organic polyisocyanate compound relative to 1 equivalent, the viscosity may be too high.
　また、化合物の末端の一部のみを、アルコール性水酸基含有（メタ）アクリレートを含む水酸基を分子中に１つ有する化合物で封止する場合には、使用するポリオールおよびアルコール性水酸基含有（メタ）アクリレートを含む水酸基を分子中に１つ有する化合物を合わせたときの水酸基の総数を、使用される有機ポリイソシアネート化合物のイソシアナト基の総数より多くする必要がある。
　ただし、この場合には、使用するポリオールおよびアルコール性水酸基含有（メタ）アクリレートを含む水酸基を分子中に１つ有する化合物を合わせたときの水酸基の総数と有機ポリイソシアネート化合物中のイソシアナト基の総数の比は、有機ポリイソシアネート化合物中のイソシアナト基の総数が１等量に対して使用するポリオールおよびアルコール性水酸基含有（メタ）アクリレートを含む水酸基を分子中に１つ有する化合物を合わせたときの水酸基の総数が２等量以下であることが好ましい。さらに好ましくは１．０等量以上１．５等量以下、もっとも好ましくは１．０等量以上１．２等量以下であることが好ましい。
　有機ポリイソシアネート化合物中のイソシアナト基の総数が１等量に対して使用するポリオールおよびアルコール性水酸基含有（メタ）アクリレートを含む水酸基を分子中に１つ有する化合物を合わせたときの水酸基の総数が２等量よりも大きい場合には、（メタ）アクリロイル基を有さない分子が多くなり、重合後の重合物の形状保持性が悪化する場合がある。
　また、合成時に使用するポリオールおよびアルコール性水酸基含有（メタ）アクリレートを含む水酸基を分子中に１つ有する化合物を合わせたときの水酸基の総数と有機ポリイソシアネート化合物中のイソシアナト基の総数の比が異なる成分１を、該重合性組成物中に２種類以上併用してもよい。 When only a part of the end of the compound is sealed with a compound having one hydroxyl group containing an alcoholic hydroxyl group-containing (meth) acrylate in the molecule, the polyol used and the alcoholic hydroxyl group-containing (meth) acrylate are used. The total number of hydroxyl groups when a compound having one hydroxyl group in the molecule is added to the total number of isocyanato groups of the organic polyisocyanate compound to be used.
However, in this case, the total number of hydroxyl groups and the total number of isocyanato groups in the organic polyisocyanate compound when a compound having one hydroxyl group in the molecule including the polyol and alcoholic hydroxyl group-containing (meth) acrylate is combined. The ratio of the total number of isocyanato groups in the organic polyisocyanate compound is equal to the number of hydroxyl groups when a compound having one hydroxyl group in the molecule including a polyol and an alcoholic hydroxyl group-containing (meth) acrylate is used with respect to 1 equivalent. The total number is preferably 2 equivalents or less. More preferably, it is 1.0 to 1.5 equivalents, and most preferably 1.0 to 1.2 equivalents.
The total number of isocyanato groups in the organic polyisocyanate compound is 1 equivalent, and the total number of hydroxyl groups when the compound having one hydroxyl group in the molecule including a polyol and alcoholic hydroxyl group-containing (meth) acrylate is combined is 2 When the amount is larger than the equivalent amount, the number of molecules having no (meth) acryloyl group increases, and the shape retention of the polymer after polymerization may be deteriorated.
The ratio of the total number of hydroxyl groups and the total number of isocyanato groups in the organic polyisocyanate compound when a compound having one hydroxyl group in the molecule including a polyol and an alcoholic hydroxyl group-containing (meth) acrylate is combined is different. Two or more kinds of component 1 may be used in combination in the polymerizable composition.
　ウレタン（メタ）アクリルアミドは、ポリオール、有機ポリイソシアネート化合物およびアルコール性水酸基含有（メタ）アクリレートを必須原料成分に用いて製造される前記のウレタン（メタ）アクリレートの原料であるアルコール性水酸基含有（メタ）アクリレートの代わりに、アルコール性水酸基含有（メタ）アクリルアミドを使用することによって製造することができる。ウレタン（メタ）アクリルアミドの製造条件は、前記のウレタン（メタ）アクリレートの製造条件と同様の条件で製造可能である。 Urethane (meth) acrylamide is an alcoholic hydroxyl group-containing (meth) which is a raw material of the urethane (meth) acrylate produced using a polyol, an organic polyisocyanate compound and an alcoholic hydroxyl group-containing (meth) acrylate as essential raw material components. It can be produced by using alcoholic hydroxyl group-containing (meth) acrylamide instead of acrylate. The production conditions of urethane (meth) acrylamide can be produced under the same conditions as the production conditions of urethane (meth) acrylate.
　次に、ポリオールおよびイソシアナト基を有する（メタ）アクリレートを必須原料成分に用いて、ウレタン（メタ）アクリレートを得る場合について説明する。
　ポリオールに関しては、前述の通りである。
　上記の原料になり得るイソシアナト基を有する（メタ）アクリレートとしては、例えば、２－イソシアナトエチルアクリレート、２－イソシアナトエチルメタクリレート等を挙げることができる。
　２－イソシアナトエチルアクリレートとしては、例えば、昭和電工株式会社製のカレンズＡＯＩ（登録商標）等を挙げることができる。
　２－イソシアナトエチルメタクリレートとしては、例えば、昭和電工株式会社製のカレンズＭＯＩ（登録商標）等を挙げることができる。 Next, the case where urethane (meth) acrylate is obtained using (meth) acrylate having a polyol and an isocyanato group as essential raw material components will be described.
The polyol is as described above.
Examples of the (meth) acrylate having an isocyanato group that can be used as the raw material include 2-isocyanatoethyl acrylate and 2-isocyanatoethyl methacrylate.
Examples of 2-isocyanatoethyl acrylate include Karenz AOI (registered trademark) manufactured by Showa Denko KK.
Examples of 2-isocyanatoethyl methacrylate include Karenz MOI (registered trademark) manufactured by Showa Denko KK and the like.
　ポリオールおよび１分子中に１つイソシアナト基を有する（メタ）アクリレートを必須原料成分に用いて得られるウレタン（メタ）アクリレートは、一般的に、以下の方法によって合成される。
　なお、ポリオールの水酸基の全量を、イソシアナト基を有する（メタ）アクリレートと反応させても、ポリオールの水酸基の一部のみを、イソシアナト基を有する（メタ）アクリレートと反応させて、一部の水酸基を残してもいっこうにかまわない。
　ポリオールの水酸基の全てを、イソシアナト基を有する（メタ）アクリレートと反応させる場合には、ポリオールの水酸基の総数と、使用したイソシアナト基含有（メタ）アクリレートのイソシアナト基の総数の比が１以下である必要がある。
　ポリオールの水酸基の一部のみを、イソシアナト基を有する（メタ）アクリロイル基含有化合物と反応させて、一部の水酸基を残す場合には、ポリオールの水酸基の総数より、使用したイソシアナト基含有（メタ）アクリレートのイソシアナト基の総数を少なく仕込む必要がある。 A urethane (meth) acrylate obtained by using a polyol and a (meth) acrylate having one isocyanato group in one molecule as an essential raw material component is generally synthesized by the following method.
Even if the total amount of hydroxyl groups of the polyol is reacted with the (meth) acrylate having an isocyanato group, only a part of the hydroxyl groups of the polyol are reacted with the (meth) acrylate having an isocyanato group, and some of the hydroxyl groups are converted. It doesn't matter if you leave it.
When all the hydroxyl groups of the polyol are reacted with the (meth) acrylate having an isocyanate group, the ratio of the total number of hydroxyl groups of the polyol to the total number of isocyanate groups of the isocyanate group-containing (meth) acrylate used is 1 or less. There is a need.
When only a part of the hydroxyl group of the polyol is reacted with the (meth) acryloyl group-containing compound having an isocyanato group to leave a part of the hydroxyl group, the isocyanate group-containing (meth) used is determined from the total number of hydroxyl groups of the polyol. It is necessary to charge a small total number of isocyanate groups of acrylate.
　製造方法には特に制約はないが、一般に、ポリオール、重合禁止剤および必要に応じてウレタン化触媒や酸化防止剤を添加し、反応器内に投入し、撹拌を開始し、反応器内の温度を４０℃～１２０℃、好ましくは５０℃～１００℃に昇温する。その後、イソシアナト基を有する（メタ）アクリレートを滴下投入する。滴下の間、反応器内の温度を４０℃～１３０℃、好ましくは５０℃～１１０℃に制御する。滴下終了後、撹拌を継続しながら、反応器内の温度を４０℃～１２０℃、好ましくは５０℃～１００℃に維持し、反応を完結させる。 There are no particular restrictions on the production method, but in general, a polyol, a polymerization inhibitor and, if necessary, a urethanization catalyst and an antioxidant are added, put into the reactor, stirring is started, and the temperature in the reactor is increased. The temperature is raised to 40 ° C to 120 ° C, preferably 50 ° C to 100 ° C. Thereafter, (meth) acrylate having an isocyanato group is dropped. During the addition, the temperature in the reactor is controlled to 40 ° C to 130 ° C, preferably 50 ° C to 110 ° C. After completion of the dropwise addition, the temperature in the reactor is maintained at 40 ° C. to 120 ° C., preferably 50 ° C. to 100 ° C. while stirring is continued to complete the reaction.
　本発明の重合性組成物を重合することにより得られる重合物の誘電率を高くすることを考えると、成分１は炭素数４～９のジオールから誘導される構造単位および炭素数４～１０のジカルボン酸から誘導される構造単位を含むポリエステル構造単位を有する（メタ）アクリロイル基含有高分子化合物であることが好ましい。なお、本明細書における「炭素数４～９のジオールから誘導される構造単位」とは、炭素数４～９のジオールの２つの水酸基のうち、少なくとも１つの水酸基中の水素が除かれた構造を意味する。また、本明細書における「炭素数４～１０のジカルボン酸から誘導される構造単位」とは、炭素数４～１０のジカルボン酸の２つのカルボキシル基（－Ｃ（＝Ｏ）ＯＨ）中のＯＨ基が除かれた構造を意味する。 In consideration of increasing the dielectric constant of a polymer obtained by polymerizing the polymerizable composition of the present invention, Component 1 is a structural unit derived from a diol having 4 to 9 carbon atoms and a component having 4 to 10 carbon atoms. A (meth) acryloyl group-containing polymer compound having a polyester structural unit containing a structural unit derived from dicarboxylic acid is preferred. In the present specification, the “structural unit derived from a diol having 4 to 9 carbon atoms” means a structure in which hydrogen in at least one hydroxyl group of two hydroxyl groups of the diol having 4 to 9 carbon atoms is removed. Means. Further, in this specification, “structural unit derived from a dicarboxylic acid having 4 to 10 carbon atoms” means OH in two carboxyl groups (—C (═O) OH) of the dicarboxylic acid having 4 to 10 carbon atoms. It means a structure in which a group is removed.
　炭素数４～９のジオールの例としては、具体的には、１，４－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、ネオペンチルグリコール、３－メチル－１，５－ペンタンジオール、１，８－オクタンジオール、１，９－ノナンジオール、２－メチル－１，８－オクタンジオール、２－ブチル－２－エチル－１，３－プロパンジオール、２，４－ジエチル－１，５－ペンタンジオール等を挙げることができ、これらを単独あるいは２種類以上を併用して用いることができる。これらの中で、好ましいものとしては、１，４－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、ネオペンチルグリコール、３－メチル－１，５－ペンタンジオールであり、さらに好ましいものとしては、１，５－ペンタンジオール、ネオペンチルグリコール、３－メチル－１，５－ペンタンジオールであり、最も好ましいものは、３－メチル－１，５－ペンタンジオールである。 Specific examples of the diol having 4 to 9 carbon atoms include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5- Pentanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1 , 5-pentanediol and the like, and these can be used alone or in combination of two or more. Among these, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, and 3-methyl-1,5-pentanediol are more preferable. Among them, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and most preferred is 3-methyl-1,5-pentanediol.
　炭素数４～１０のジカルボン酸の例としては、具体的には、コハク酸、グルタル酸、メチルコハク酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、テレフタル酸、イソフタル酸、フタル酸、１，１－シクロヘキサンジカルボン酸、１，３－シクロヘキサンジカルボン酸、１，４－シクロヘキサンジカルボン酸、２－シクロヘキサン－１，１－ジカルボン酸等を挙げることができ、これらを単独あるいは２種類以上を併用して用いることができる。これらの中で好ましいものとしては、グルタル酸、メチルコハク酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、１，１－シクロヘキサンジカルボン酸、１，３－シクロヘキサンジカルボン酸、１２－シクロヘキサン－１，１－ジカルボン酸であり、さらに好ましくは、グルタル酸、メチルコハク酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸であり、最も好ましくは、アジピン酸である。 Specific examples of the dicarboxylic acid having 4 to 10 carbon atoms include succinic acid, glutaric acid, methyl succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, and phthalic acid. 1,1-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-cyclohexane-1,1-dicarboxylic acid and the like. It can be used in combination. Of these, glutaric acid, methyl succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,1-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 12-cyclohexane- 1,1-dicarboxylic acid, more preferably glutaric acid, methylsuccinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid, and most preferably adipic acid.
　次に、本発明（Ｉ）の重合性組成物の必須成分である成分２について説明する。
　本発明（Ｉ）の重合性組成物の必須成分である成分２は、光重合開始剤である。
　成分２の光重合開始剤は、近赤外線、可視光線、紫外線等の光の照射により、ラジカル重合の開始に寄与するラジカルを発生する化合物であれば、特に制限はない。 Next, component 2 which is an essential component of the polymerizable composition of the present invention (I) will be described.
Component 2 which is an essential component of the polymerizable composition of the present invention (I) is a photopolymerization initiator.
The photopolymerization initiator of component 2 is not particularly limited as long as it is a compound that generates radicals that contribute to the initiation of radical polymerization upon irradiation with light such as near infrared rays, visible rays, and ultraviolet rays.
　成分２の光重合開始剤としては、具体的には、アセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、ジエトキシアセトフェノン、１－ヒドロキシシクロヘキシルフェニルケトン、１，２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、α－ヒドロキシシクロヘキシルフェニルケトン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、２－ヒドロキシ－２－メチル－１－（４－イソプロピルフェニル）プロパン－１－オン、２－ヒドロキシ－２－メチル－１－（４－ドデシルフェニル）プロパン－１－オン、および２－ヒドロキシ－２－メチル－１－［（２－ヒドロキシエトキシ）フェニル］プロパノン、ベンゾフェノン、２－メチルベンゾフェノン、３－メチルベンゾフェノン、４－メチルベンゾフェノン、４－メトキシベンゾフェノン、２－クロロベンゾフェノン、４－クロロベンゾフェノン、４－ブロモベンゾフェノン、２－カルボキシベンゾフェノン、２－エトキシカルボニルベンゾフェノン、４－ベンゾイル－４′－メチルジフェニルスルフィド、ベンゾフェノンテトラカルボン酸またはそのテトラメチルエステル、４，４′－ビス（ジアルキルアミノ）ベンゾフェノン類（例えば４，４′－ビス（ジメチルアミノ）ベンゾフェノン、４，４′－ビス（ジシクロヘキシルアミノ）ベンゾフェノン、４，４′－ビス（ジエチルアミノ）ベンゾフェノン、４，４′－ビス（ジヒドロキシエチルアミノ）ベンゾフェノン）、４－メトキシ－４′－ジメチルアミノベンゾフェノン、４，４′－ジメトキシベンゾフェノン、４－ジメチルアミノベンゾフェノン、４－ジメチルアミノアセトフェノン、ベンジル、アントラキノン、２－ｔ－ブチルアントラキノン、２－メチルアントラキノン、フェナントラキノン、フルオレノン、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）－１－ブタノン、２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルホリニル）フェニル］－１－ブタノン、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノ－１－プロパノン、２－ヒドロキシ－２－メチル－［４－（１－メチルビニル）フェニル］プロパノールオリゴマー、ベンゾイン、ベンゾインエーテル類（例えばベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインプロピルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、ベンゾインフェニルエーテル、ベンジルジメチルケタール）、アクリドン、クロロアクリドン、Ｎ－メチルアクリドン、Ｎ－ブチルアクリドン、Ｎ－ブチル－クロロアクリドン、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド、２，６－ジメトキシベンゾイルジフェニルホスフィンオキサイド、２，６－ジクロロベンゾイルジフェニルホスフィンオキサイド、２，４，６－トリメチルベンゾイルメトキシフェニルホスフィンオキサイド、２，４，６－トリメチルベンゾイルエトキシフェニルホスフィンオキサイド、２，３，５，６－テトラメチルベンゾイルジフェニルホスフィンオキサイド、ベンゾイルジ－（２，６－ジメチルフェニル）ホスホネートなどが挙げられる。ビスアシルフォスフィンオキサイド類としては、ビス－（２，６－ジクロロベンゾイル）フェニルフォスフィンオキサイド、ビス－（２，６－ジクロロベンゾイル）－２，５－ジメチルフェニルフォスフィンオキサイド、ビス－（２，６－ジクロロベンゾイル）－４－プロピルフェニルフォスフィンオキサイド、ビス－（２，６－ジクロロベンゾイル）－１－ナフチルフォスフィンオキサイド、ビス－（２，６－ジメトキシベンゾイル）フェニルフォスフィンオキサイド、ビス－（２，６－ジメトキシベンゾイル）－２，４，４－トリメチルペンチルフォスフィンオキサイド、ビス－（２，６－ジメトキシベンゾイル）－２，５－ジメチルフェニルフォスフィンオキサイド、ビス－（２，４，６－トリメチルベンゾイル）フェニルフォスフィンオキサイド、（２，５，６－トリメチルベンゾイル）－２，４，４－トリメチルペンチルフォスフィンオキサイド、２－イソプロピルチオキサントン、４－イソプロピルチオキサントン、２，４－ジエチルチオキサントン、２，４－ジクロロチオキサントン、１－クロロ－４－プロポキシチオキサントンなどが挙げられる。 Specific examples of the photopolymerization initiator of Component 2 include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 1,2-hydroxy-2-methyl-1 -Phenylpropan-1-one, α-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- (4-isopropylphenyl) propane- 1-one, 2-hydroxy-2-methyl-1- (4-dodecylphenyl) propan-1-one, and 2-hydroxy-2-methyl-1-[(2-hydroxyethoxy) phenyl] propanone, benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methyl Benzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, benzophenone tetracarboxylic acid or its Tetramethyl esters, 4,4'-bis (dialkylamino) benzophenones (eg 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (dicyclohexylamino) benzophenone, 4,4'-bis (diethylamino) ) Benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone), 4-methoxy-4′-dimethylaminobenzophenone, 4,4′-dimethoxybenzophenone, 4-dimethyl Tylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, fluorenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholino-1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (eg benzoin methyl ether, benzoin ethyl ether) , Benzoinpropyl ether, ben Inisopropyl ether, benzoin isobutyl ether, benzoin phenyl ether, benzyldimethyl ketal), acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone, 2,4,6-trimethyl Benzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi- (2,6-dimethylphenyl) phosphonate And the like. Examples of bisacylphosphine oxides include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- ( 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6- Trimethylbenzoyl) phenyl phosphite Oxide, (2,5,6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1 -Chloro-4-propoxythioxanthone and the like.
　また、光重合開始剤として、メタロセン化合物を使用することもできる。メタロセン化合物としては、中心金属がＦｅ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｃｏ、Ｎｉ、Ｍｏ、Ｒｕ、Ｒｈ、Ｌｕ、Ｔａ、Ｗ、Ｏｓ、Ｉｒなどに代表される遷移元素を用いることができ、例えば、ビス（η５－２，４－シクロペンタジエン－１－イル）－ビス［２，６－ジフルオロ－３－（ピロール－１－イル）フェニル］チタニウムを挙げることができる。 Also, a metallocene compound can be used as a photopolymerization initiator. As the metallocene compound, the transition metal represented by Fe, Ti, V, Cr, Mn, Co, Ni, Mo, Ru, Rh, Lu, Ta, W, Os, Ir, etc. can be used as the metallocene compound, An example is bis (η5-2,4-cyclopentadien-1-yl) -bis [2,6-difluoro-3- (pyrrol-1-yl) phenyl] titanium.
　これらの光重合開始剤は、それぞれ単独で、あるいは２種以上を組み合わせて使用することができる。
　これらの中で、好ましいものとしては、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、１－ヒドロキシシクロヘキシルフェニルケトン、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド、２，４，６－トリメチルベンゾイルエトキシフェニルホスフィンオキサイド、２，３，５，６－テトラメチルベンゾイルジフェニルホスフィンオキサイドであり、特に好ましいものとしては、１－ヒドロキシシクロヘキシルフェニルケトン、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド、２，４，６－トリメチルベンゾイルエトキシフェニルホスフィンオキサイドであり、最も好ましくは、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイドの単独使用、２，４，６－トリメチルベンゾイルエトキシフェニルホスフィンオキサイドの単独使用、１－ヒドロキシシクロヘキシルフェニルケトンと２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイドの併用、１－ヒドロキシシクロヘキシルフェニルケトンと２，４，６－トリメチルベンゾイルエトキシフェニルホスフィンオキサイドの併用、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイドと２，４，６－トリメチルベンゾイルエトキシフェニルホスフィンオキサイドの併用あるいは１－ヒドロキシシクロヘキシルフェニルケトン、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイドおよび２，４，６－トリメチルベンゾイルエトキシフェニルホスフィンオキサイドの３種の併用である。 These photopolymerization initiators can be used alone or in combination of two or more.
Of these, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4, 6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, particularly preferable examples include 1-hydroxycyclohexyl phenyl ketone, 2,4,6- trimethylbenzoyldiphenylphosphine oxide 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, most preferably 2,4,6-trimethylbenzoyldiphenylphosphine oxide used alone, 1-hydroxycyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone and 2,4,6- trimethylbenzoylethoxyphenylphosphine oxide 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide or 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2 , 4,6-Trimethylbenzoylethoxyphenylphosphine oxide.
　また、図１～図４における保護部３には、表示部２に対する紫外線保護の観点から紫外線領域をカットする機能が付与されている場合がある。その場合、可視光領域でも感光可能な光重合開始剤である２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド、２，３，５，６－テトラメチルベンゾイルジフェニルホスフィンオキサイド、２，４，６－トリメチルベンゾイルエトキシフェニルホスフィンオキサイドを使用することが好ましく、特に好ましくは、２，４，６－トリメチルベンゾイルエトキシフェニルホスフィンオキサイド、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイドである。 1 to 4 may have a function of cutting the ultraviolet region from the viewpoint of protecting the display unit 2 from ultraviolet rays. In that case, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethyl, which is a photopolymerization initiator that can be sensitized even in the visible light region. Benzoylethoxyphenylphosphine oxide is preferably used, and 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide are particularly preferable.
　本発明（Ｉ）における成分２の使用量は、本発明（Ｉ）の重合性組成物の全量から成分２を除いた量１００質量部に対して０．０５～１０．０質量部であることが好ましく、さらに好ましくは、０．１～７．０質量部であり、特に好ましくは、０．２～５．０質量部である。成分２の使用量が、本発明（Ｉ）の重合性組成物の全量から成分２を除いた量１００質量部に対して０．０５質量部未満であると、重合開始剤の重合開始性能不足になる場合がある。また、本発明の成分２の使用量が、本発明（Ｉ）の重合性組成物の全量から成分２を除いた量１００質量部に対して１０．０質量部より多くなると、後述の本発明（Ｖ）の重合物あるいは後述の前記光学用粘着シートを、高温環境下においた場合に、着色しやすくなる場合がある。 The amount of Component 2 used in the present invention (I) is 0.05 to 10.0 parts by weight with respect to 100 parts by weight of the total amount of the polymerizable composition of the present invention (I) excluding Component 2. More preferably, it is 0.1 to 7.0 parts by mass, and particularly preferably 0.2 to 5.0 parts by mass. When the amount of component 2 used is less than 0.05 parts by mass relative to 100 parts by mass of component 2 from the total amount of the polymerizable composition of the present invention (I), the polymerization initiator has insufficient polymerization initiation performance. It may become. Moreover, when the usage-amount of the component 2 of this invention becomes more than 10.0 mass parts with respect to 100 mass parts of quantity remove | excluding the component 2 from the whole quantity of the polymeric composition of this invention (I), this invention mentioned later is mentioned. When the polymer (V) or the optical pressure-sensitive adhesive sheet described later is placed in a high temperature environment, it may be easily colored.
　本発明の重合性組成物は、それを重合することにより得られる重合物の２５℃で周波数０．１Ｈｚでの貯蔵弾性率が１×１０３～１×１０５Ｐａであり、１×１０４～１×１０５Ｐａであることが好ましい。
　なお、「重合物の２５℃で周波数０．１ Ｈｚでの貯蔵弾性率」とは、２．５ｍｍ厚の試験片（重合物）を、２５℃の環境下で、Ａｕｔｏｎ　Ｐｅａｒ社製のレオメーターとしてＭＲＣ３０１を使用して、測定治具として同じくＡｕｔｏｎ　Ｐｅａｒ社製プレートＰＰ２５を使用して振動モードで測定した周波数０．１Ｈｚでの貯蔵弾性率である。
　上記条件で測定された重合物の貯蔵弾性率が１×１０３未満の場合には、高温多湿の環境下、あるいは高温の環境下で重合物が形状を維持できない可能性がある。また、１×１０５Ｐａ以上の場合は、重合物が硬くなりすぎ、十分な密着性が得られない可能性がある。重合物の貯蔵弾性率を１×１０３～１×１０５Ｐａにするためには、成分１を構成する全原料モノマーのうち、脂環構造または芳香族構造を有するモノマーの配合量は７０質量％以下であることが好ましく、より好ましくは５０質量％以下であり、さらに好ましくは５質量％以上、４０質量％以下である。７０質量％を超えると貯蔵弾性率が高くなる傾向がある。また、成分１の化合物に含まれる（メタ）アクリロイル基の数は１分子当たり平均で１～２個であることが好ましい。平均で２個を超えると貯蔵弾性率が高くなり、平均で１個を下回ると貯蔵弾性率が低くなる傾向がある。上記のように、脂環構造または芳香族構造を有するモノマーの配合量や成分１の化合物に含まれる（メタ）アクリロイル基の数を増減することによって重合物の２５℃で周波数０．１Ｈｚでの貯蔵弾性率が１×１０３～１×１０５Ｐａとなるように制御することができる。 The polymerizable composition of the present invention, the storage modulus at a frequency 0.1Hz is at 25 ° C. of the polymer obtained by polymerizing it was 1 × 10 3 ~ 1 × 10 5 Pa, 1 × 10 4 It is preferably ˜1 × 10 5 Pa.
“The storage elastic modulus of the polymer at 25 ° C. at a frequency of 0.1 Hz” means that a 2.5 mm thick test piece (polymer) is a rheometer manufactured by Auton Pear in an environment of 25 ° C. Is a storage elastic modulus at a frequency of 0.1 Hz measured in vibration mode using MRC301 as a measurement jig and also using a plate PP25 manufactured by Autoon Pear.
When the storage elastic modulus of the polymer measured under the above conditions is less than 1 × 10 3 , the polymer may not be able to maintain its shape in a high temperature and high humidity environment or a high temperature environment. Moreover, in the case of 1 × 10 5 Pa or more, the polymer becomes too hard and sufficient adhesion may not be obtained. In order to set the storage elastic modulus of the polymer to 1 × 10 3 to 1 × 10 5 Pa, the blending amount of the monomer having the alicyclic structure or the aromatic structure among all the raw material monomers constituting Component 1 is 70 mass. % Or less, more preferably 50% by mass or less, and further preferably 5% by mass or more and 40% by mass or less. If it exceeds 70% by mass, the storage elastic modulus tends to increase. The number of (meth) acryloyl groups contained in the component 1 compound is preferably 1 to 2 on average per molecule. When the average number exceeds two, the storage elastic modulus increases, and when the average number is less than one, the storage elastic modulus tends to decrease. As described above, the amount of the monomer having an alicyclic structure or an aromatic structure and the number of (meth) acryloyl groups contained in the compound of Component 1 are increased or decreased at a frequency of 0.1 Hz at 25 ° C. The storage elastic modulus can be controlled to be 1 × 10 3 to 1 × 10 5 Pa.
　次に、本発明（ＩＩ）について説明する。
　本発明（ＩＩ）は、画像表示装置の画像表示部と透光性の保護部との間に介在させる重合物層を形成するための重合性組成物であって、該重合性組成物が、
（成分１）数平均分子量が１０００～１５０００の範囲である（メタ）アクリロイル基含有高分子化合物、
（成分２）光重合開始剤、および
（成分３）アルコール性水酸基とアミド基の少なくとも一方を有するラジカル重合性不飽和基含有化合物
を含み、かつ該重合性組成物を重合することにより得られる重合物の２５℃で周波数０．１Ｈｚでの貯蔵弾性率が１×１０３～１×１０５Ｐａであることを特徴とする重合性組成物である。
　本発明（ＩＩ）の成分１および成分２は、それぞれ、本発明（Ｉ）の成分１および成分２と同様のものである。また成分２の配合量は、前述の成分２の配合量と同じである。また、その使用量が好ましい理由も前述のとおりである。 Next, the present invention (II) will be described.
The present invention (II) is a polymerizable composition for forming a polymer layer interposed between the image display part and the translucent protective part of the image display device, the polymerizable composition comprising:
(Component 1) (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 15000,
Polymerization obtained by polymerizing the polymerizable composition, comprising (Component 2) a photopolymerization initiator, and (Component 3) a radical polymerizable unsaturated group-containing compound having at least one of an alcoholic hydroxyl group and an amide group. It is a polymerizable composition characterized by having a storage elastic modulus of 1 × 10 3 to 1 × 10 5 Pa at 25 ° C. and a frequency of 0.1 Hz.
Component 1 and Component 2 of the present invention (II) are the same as Component 1 and Component 2 of the present invention (I), respectively. The amount of component 2 is the same as the amount of component 2 described above. The reason why the amount used is preferable is also as described above.
　次に、本発明（ＩＩ）の重合性組成物の必須成分である成分３について説明する。
　本発明（ＩＩ）の重合性組成物の必須成分である成分３は、アルコール性水酸基とアミド基の少なくとも一方を有するラジカル重合性不飽和基含有化合物である。
　ただし、本明細書において、アルコール性水酸基とアミド基の少なくとも一方を有する、数平均分子量が１０００～１５０００の範囲である（メタ）アクリロイル基含有高分子化合物は、成分３には含まれないものと定義する。つまり、本明細書において、アルコール性水酸基とアミド基の少なくとも一方を有する、数平均分子量が１０００～１５０００の範囲である（メタ）アクリロイル基含有高分子化合物は、成分３には含まれず、本発明の重合性組成物の必須成分である成分１に含まれることを意味する。
　なお、本明細書における「ラジカル重合性不飽和基」とは、ラジカル重合開始剤等により発生するラジカルにより付加重合することが可能な炭素－炭素二重結合を意味する。 Next, component 3 which is an essential component of the polymerizable composition of the present invention (II) will be described.
Component 3 which is an essential component of the polymerizable composition of the present invention (II) is a radical polymerizable unsaturated group-containing compound having at least one of an alcoholic hydroxyl group and an amide group.
However, in this specification, a (meth) acryloyl group-containing polymer compound having at least one of an alcoholic hydroxyl group and an amide group and having a number average molecular weight in the range of 1000 to 15000 is not included in Component 3. Define. That is, in this specification, a (meth) acryloyl group-containing polymer compound having at least one of an alcoholic hydroxyl group and an amide group and having a number average molecular weight in the range of 1000 to 15000 is not included in Component 3, and the present invention It is included in Component 1 which is an essential component of the polymerizable composition.
In the present specification, the “radical polymerizable unsaturated group” means a carbon-carbon double bond capable of addition polymerization by a radical generated by a radical polymerization initiator or the like.
　成分３であるアミド基を有するラジカル重合性不飽和基含有化合物の具体例としては、例えば、Ｎ，Ｎ－ジメチルアクリルアミド、Ｎ，Ｎ－ジエチルアクリルアミド、Ｎ－アクリロイルモルホリン、Ｎ－イソプロピルアクリルアミド、Ｎ－ｔｅｒｔ－ブチルアクリルアミド、Ｎ－メトキシメチルアクリルアミド、Ｎ－エトキシメチルアクリルアミド、Ｎ－ｎ－ブトキシメチルアクリルアミド、Ｎ－イソブトキシメチルアクリルアミド、Ｎ，Ｎ－ジメチルメタクリルアミド、Ｎ，Ｎ－ジエチルメタクリルアミド、Ｎ－メタクリロイルモルホリン、Ｎ－イソプロピルメタクリルアミド、Ｎ－ｔｅｒｔ－ブチルメタクリルアミド、Ｎ－メトキシメチルメタクリルアミド、Ｎ－エトキシメチルメタクリルアミド、Ｎ－ｎ－ブトキシメチルメタクリルアミド、Ｎ－イソブトキシメチルメタクリルアミド、Ｎ－ビニルピロリドン、Ｎ－ビニルカプロラクタム、Ｎ－ビニルホルムアミド、Ｎ－ビニルアセトアミド、２－ヒドロキシエチルアクリルアミド、２－ヒドロキシエチルメタクリルアミド等の化合物を挙げることができる。これらの化合物を、単独で使用することも、２種類以上を併用して用いることもできる。
　これらの中で好ましいものとしては、Ｎ，Ｎ－ジエチルアクリルアミド、Ｎ－アクリロイルモルホリン、Ｎ－ｔｅｒｔ－ブチルアクリルアミド、Ｎ－ｔｅｒｔ－ブチルアクリルアミド、Ｎ－エトキシメチルアクリルアミド、Ｎ－ｎ－ブトキシメチルアクリルアミド、Ｎ－イソブトキシメチルアクリルアミド、Ｎ－ビニルピロリドンであり、さらに好ましくは、Ｎ，Ｎ－ジエチルアクリルアミド、Ｎ－アクリロイルモルホリン、Ｎ－エトキシメチルアクリルアミド、Ｎ－ｎ－ブトキシメチルアクリルアミド、Ｎ－イソブトキシメチルアクリルアミドであり、最も好ましいものとしては、Ｎ－アクリロイルモルホリンである。 Specific examples of the radical polymerizable unsaturated group-containing compound having an amide group as Component 3 include, for example, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-acryloylmorpholine, N-isopropylacrylamide, N- tert-butylacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, Nn-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide, N- Methacryloylmorpholine, N-isopropylmethacrylamide, N-tert-butylmethacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylmethacrylamide, Nn-butoxymethylmethacrylate And N-isobutoxymethylmethacrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinylacetamide, 2-hydroxyethylacrylamide, 2-hydroxyethylmethacrylamide and the like. . These compounds can be used alone or in combination of two or more.
Among these, N, N-diethylacrylamide, N-acryloylmorpholine, N-tert-butylacrylamide, N-tert-butylacrylamide, N-ethoxymethylacrylamide, Nn-butoxymethylacrylamide, N -Isobutoxymethylacrylamide and N-vinylpyrrolidone, more preferably N, N-diethylacrylamide, N-acryloylmorpholine, N-ethoxymethylacrylamide, Nn-butoxymethylacrylamide, N-isobutoxymethylacrylamide Most preferred is N-acryloylmorpholine.
　また、成分３であるアルコール性水酸基を有するラジカル重合性不飽和基含有化合物の具体例としては、例えば、２－ヒドロキシエチルアクリレート、２－ヒドロキシプロピルアクリレート、３－ヒドロキシプロピルアクリレート、２－ヒドロキシブチルアクリレート、４－ヒドロキシブチルアクリレート、２－ヒドロキシ－３－フェノキシプロピルアクリレート、２－ヒドロキシ－３－（ｏ－フェニルフェノキシ）プロピルアクリレート、２－ヒドロキシエチルアクリルアミド、２－ヒドロキシエチルメタクリレート、２－ヒドロキシプロピルメタクリレート、３－ヒドロキシプロピルメタクリレート、２－ヒドロキシブチルメタクリレート、４－ヒドロキシブチルメタクリレート、２－ヒドロキシ－３－フェノキシプロピルメタクリレート、２－ヒドロキシ－３－（ｏ－フェニルフェノキシ）プロピルメタクリレート、２－ヒドロキシエチルアクリルアミド、２－ヒドロキシエチルメタクリルアミド等を挙げることができる。これらの化合物を、単独で使用することも、２種類以上を併用して用いることもできる。
　これらの中で好ましいものとしては、２－ヒドロキシブチルアクリレート、４－ヒドロキシブチルアクリレート、２－ヒドロキシプロピルメタクリレート、３－ヒドロキシプロピルメタクリレート、２－ヒドロキシブチルメタクリレートであり、さらに好ましくは、４－ヒドロキシブチルアクリレート、２－ヒドロキシプロピルメタクリレート、３－ヒドロキシプロピルメタクリレート、２－ヒドロキシブチルメタクリレートであり、最も好ましくは、２－ヒドロキシプロピルメタクリレートである。 Specific examples of the radical polymerizable unsaturated group-containing compound having an alcoholic hydroxyl group as component 3 include, for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate. 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3- (o-phenylphenoxy) propyl acrylate, 2-hydroxyethyl acrylamide, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate , Mention may be made of 2-hydroxy-3-(o-phenylphenoxy) propyl methacrylate, 2-hydroxyethyl acrylamide, 2-hydroxyethyl methacrylamide. These compounds can be used alone or in combination of two or more.
Among these, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate and 2-hydroxybutyl methacrylate are preferable, and 4-hydroxybutyl acrylate is more preferable. 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, and most preferably 2-hydroxypropyl methacrylate.
　本発明（ＩＩ）における成分３の使用量は、成分１と成分３を合わせた総量に対して、１～３０質量％であることが好ましく、さらに好ましくは、２～２０質量％であり、特に好ましくは、３～１０質量％である。本発明（ＩＩ）における成分３の使用量が、成分１と成分３を合わせた総量に対して、１質量％未満であると、後述の本発明（Ｖ）の重合物や前記光学用粘着シートが高温多湿の環境下で白化してしまう場合がある。また、本発明（ＩＩ）における成分３の使用量が、成分１と成分３を合わせた総量に対して３０質量％より多い場合には、本発明（ＩＩ）の重合性組成物の重合時の体積収縮率が大きくなる可能性がある。
　また、本発明（ＩＩ）における成分１の使用量は、成分１と成分３を合わせた総量に対して、７０～９９質量％であることが好ましく、さらに好ましくは、８０～９８質量％であり、特に好ましくは、９０～９７質量％である。本発明（ＩＩ）における成分３の使用量が、成分１と成分３を合わせた総量に対して７０質量％未満の場合には、本発明（ＩＩ）の重合性組成物の重合時の体積収縮率が大きくなる場合がある。また、本発明（ＩＩ）における成分１の使用量が、成分１と成分３を合わせた総量に対して９９質量％以上の場合には、重合性組成物の粘度が高くなりすぎてしまう場合がある。 The amount of component 3 used in the present invention (II) is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, particularly based on the total amount of component 1 and component 3 combined. Preferably, it is 3 to 10% by mass. When the amount of component 3 used in the present invention (II) is less than 1% by mass relative to the total amount of component 1 and component 3, the polymer of the present invention (V) described later and the optical pressure-sensitive adhesive sheet May whiten in a hot and humid environment. Moreover, when the usage-amount of the component 3 in this invention (II) is more than 30 mass% with respect to the total amount which combined the component 1 and the component 3, at the time of superposition | polymerization of the polymeric composition of this invention (II) There is a possibility that the volume shrinkage rate becomes large.
In addition, the amount of component 1 used in the present invention (II) is preferably 70 to 99% by mass, more preferably 80 to 98% by mass, based on the total amount of component 1 and component 3 combined. Particularly preferred is 90 to 97% by mass. When the usage-amount of the component 3 in this invention (II) is less than 70 mass% with respect to the total amount which combined the component 1 and the component 3, the volume shrinkage at the time of superposition | polymerization of the polymeric composition of this invention (II) The rate may increase. Moreover, when the usage-amount of the component 1 in this invention (II) is 99 mass% or more with respect to the total amount which combined the component 1 and the component 3, the viscosity of polymeric composition may become high too much. is there.
　次に、本発明（ＩＩＩ）について説明する。
　本発明（ＩＩＩ）は、画像表示装置の画像表示部と透光性の保護部との間に介在させる重合物層を形成するための重合性組成物であって、該重合性組成物が、
（成分１）数平均分子量が１０００～１５０００の範囲である（メタ）アクリロイル基含有高分子化合物、
（成分２）光重合開始剤、
（成分３）アルコール性水酸基とアミド基の少なくとも一方を有するラジカル重合性不飽和基含有化合物、および
（成分４）アルコール性水酸基とアミド基のいずれの基も有さず、かつ粘度が２５℃で５００ｍＰａ・ｓ以下である（メタ）アクリロイル基含有化合物
を含み、かつ該重合性組成物を重合することにより得られる重合物の２５℃で周波数０．１Ｈｚでの貯蔵弾性率が１×１０３～１×１０５Ｐａであることを特徴とする重合性組成物である。 Next, the present invention (III) will be described.
The present invention (III) is a polymerizable composition for forming a polymer layer interposed between the image display part of the image display device and the translucent protective part, the polymerizable composition comprising:
(Component 1) (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 15000,
(Component 2) Photopolymerization initiator,
(Component 3) a radical polymerizable unsaturated group-containing compound having at least one of an alcoholic hydroxyl group and an amide group, and (Component 4) no alcoholic hydroxyl group or amide group, and a viscosity of 25 ° C. A polymer obtained by polymerizing the polymerizable composition containing a (meth) acryloyl group-containing compound that is 500 mPa · s or less has a storage elastic modulus at 25 ° C. and a frequency of 0.1 Hz of 1 × 10 3 to The polymerizable composition is 1 × 10 5 Pa.
　本発明（ＩＩＩ）の成分１および成分２は、それぞれ、本発明（Ｉ）の成分１および成分２と同様のものであり、本発明（ＩＩＩ）の成分３は、本発明（ＩＩ）の成分３と同様のものである。また成分２の配合量は前述の成分２の配合量と同じである。また、その使用量が好ましい理由も前述のとおりである。 Component 1 and Component 2 of the present invention (III) are the same as Component 1 and Component 2 of the present invention (I), respectively, and Component 3 of the present invention (III) is a component of the present invention (II). It is the same as 3. The amount of component 2 is the same as the amount of component 2 described above. The reason why the amount used is preferable is also as described above.
　次に、本発明（ＩＩＩ）の重合性組成物の必須成分である成分４について説明する。
　成分４は、アルコール性水酸基とアミド基のいずれの基も有さず、かつ粘度が２５℃で５００ｍＰａ・ｓ以下である（メタ）アクリロイル基含有化合物である。
　ただし、本明細書において、アルコール性水酸基とアミド基のいずれの基も有さず、かつ粘度が２５℃で５００ｍＰａ・ｓ以下である、数平均分子量が１０００～１５０００の範囲である（メタ）アクリロイル基含有高分子化合物は、成分４には含まれないものと定義する。つまり、本明細書において、アルコール性水酸基とアミド基のいずれの基も有さず、かつ粘度が２５℃で５００ｍＰａ・ｓ以下である、数平均分子量が１０００～１５０００の範囲である（メタ）アクリロイル基含有高分子化合物は、成分４には含まれず、本発明の重合性組成物の必須成分である成分１に含まれることを意味する。 Next, component 4 which is an essential component of the polymerizable composition of the present invention (III) will be described.
Component 4 is a (meth) acryloyl group-containing compound which does not have any group of alcoholic hydroxyl group and amide group and has a viscosity of 500 mPa · s or less at 25 ° C.
However, in the present specification, (meth) acryloyl having no alcoholic hydroxyl group and no amide group and having a viscosity of 500 mPa · s or less at 25 ° C. and a number average molecular weight in the range of 1000 to 15000 The group-containing polymer compound is defined as not included in Component 4. That is, in the present specification, (meth) acryloyl having no alcoholic hydroxyl group or amide group and having a viscosity of 500 mPa · s or less at 25 ° C. and a number average molecular weight in the range of 1000 to 15000. The group-containing polymer compound is not included in Component 4, but is included in Component 1 which is an essential component of the polymerizable composition of the present invention.
　成分４の具体例としては、例えば、シクロヘキシルアクリレート、イソボルニルアクリレート、ジシクロペンテニルアクリレート、ジシクロペンテニルオキシエチルアクリレート、ジシクロペンタニルアクリレート、ジシクロペンタニルエチルアクリレート、４－ｔｅｒｔ－ブチルシクロヘキシルアクリレート、イソボルニルメタクリレート、ジシクロペンテニルメタクリレート、ジシクロペンテニルオキシエチルメタクリレート、ジシクロペンタニルメタクリレート、ジシクロペンタニルエチルメタクリレート、４－ｔｅｒｔ－ブチルシクロヘキシルメタクリレート等の環状脂肪族基を有する（メタ）アクリロイル基含有化合物、ヘキシルアクリレート、ラウリルアクリレート、イソノニルアクリレート、２－プロピルヘプチルアクリレート、４－メチル－２－プロピルヘキシルアクリレート、イソオクタデシルアクリレート、２－ヘプチルウンデシルアクリレート、ラウリルメタクリレート、イソノニルメタクリレート、２－プロピルヘプチルメタクリレート、４－メチル－２－プロピルヘキシルメタクリレート、イソオクタデシルメタクリレート、２－ヘプチルウンデシルメタクリレート等の鎖状脂肪族基を有する（メタ）アクリロイル基含有化合物、メトキシエチル（メタ）アクリレート、ジエチレングリコールモノエチルエーテル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、３－メチル－３－オキセタニルメチル（メタ）アクリレート、１，４－ジオキサスピロ［４．５］デカ－２－イルメチル（メタ）アクリレート、（２－メチル－２－エチル－１，３－ジオキソラン－４－イル）メチル（メタ）アクリレート等の分子中にエーテル結合を有する（メタ）アクリロイル基含有化合物、α－メタクリロキシ－γ－ブチロラクトン、α－アクリロキシ－γ－ブチロラクトン等の環状エステルを有する（メタ）アクリロイル基含有化合物等を挙げることができる。 Specific examples of component 4 include, for example, cyclohexyl acrylate, isobornyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentanyl ethyl acrylate, 4-tert-butylcyclohexyl acrylate. (Meth) acryloyl having a cyclic aliphatic group such as isobornyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentanyl methacrylate, dicyclopentanylethyl methacrylate, 4-tert-butylcyclohexyl methacrylate Group-containing compounds, hexyl acrylate, lauryl acrylate, isononyl acrylate, 2-propylheptyl acrylate 4-methyl-2-propylhexyl acrylate, isooctadecyl acrylate, 2-heptylundecyl acrylate, lauryl methacrylate, isononyl methacrylate, 2-propylheptyl methacrylate, 4-methyl-2-propylhexyl methacrylate, isooctadecyl methacrylate, (Meth) acryloyl group-containing compounds having a chain aliphatic group such as 2-heptylundecyl methacrylate, methoxyethyl (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, phenoxyethyl (meth) acrylate, 3-methyl- 3-Oxetanylmethyl (meth) acrylate, 1,4-dioxaspiro [4.5] dec-2-ylmethyl (meth) acrylate, (2-methyl-2-ethyl (Meth) acryloyl group-containing compounds having an ether bond in the molecule such as 1,3-dioxolan-4-yl) methyl (meth) acrylate, cyclic such as α-methacryloxy-γ-butyrolactone, α-acryloxy-γ-butyrolactone Examples include (meth) acryloyl group-containing compounds having an ester.
　本発明（ＩＩＩ）における成分４の使用量は、本発明（ＩＩＩ）の必須成分である成分１、成分３および成分４を合わせた総量に対して３～４０質量％であることが好ましく、さらに好ましくは、５～３５質量％であり、特に好ましくは、７～３０質量％である。本発明（ＩＩＩ）における成分４の使用量が、本発明（ＩＩＩ）の必須成分である成分１、成分３および成分４を合わせた総量に対して３質量％未満であると、本発明（ＩＩＩ）の重合性組成物の粘度が高くなりすぎる場合がある。また、本発明（ＩＩＩ）における成分４の使用量が、本発明（ＩＩＩ）の必須成分である成分１、成分３および成分４を合わせた総量に対して４０質量％より多い場合には、本発明（ＩＩＩ）の重合性組成物の重合時の体積収縮率が大きくなる可能性がある。 The amount of component 4 used in the present invention (III) is preferably 3 to 40% by mass based on the total amount of component 1, component 3 and component 4 as essential components of the present invention (III). The amount is preferably 5 to 35% by mass, particularly preferably 7 to 30% by mass. When the usage-amount of the component 4 in this invention (III) is less than 3 mass% with respect to the total amount which combined the component 1, the component 3, and the component 4 which are essential components of this invention (III), this invention (III ) Of the polymerizable composition may become too high. Further, when the amount of component 4 used in the present invention (III) is more than 40% by mass with respect to the total amount of component 1, component 3 and component 4 which are essential components of the present invention (III), There is a possibility that the volumetric shrinkage during polymerization of the polymerizable composition of the invention (III) is increased.
　本発明（ＩＩＩ）における成分３の使用量は、成分１、成分３および成分４を合わせた総量に対して、本発明（ＩＩ）において成分３に対して好ましい使用量と同じである。また、その使用量が好ましい理由も前述のとおりである。 The amount of component 3 used in the present invention (III) is the same as the preferred amount used for component 3 in the present invention (II) with respect to the total amount of components 1, 3 and 4 combined. The reason why the amount used is preferable is also as described above.
　また、本発明（ＩＩＩ）における成分１の使用量は、成分１、成分３および成分４を合わせた総量に対して、５０～９６質量％であることが好ましく、さらに好ましくは、５５～９３質量％であり、特に好ましくは、６０～９０質量％である。前述の範囲が好ましい理由は本発明（ＩＩ）の場合と同様である。 In addition, the amount of component 1 used in the present invention (III) is preferably 50 to 96% by mass, more preferably 55 to 93% by mass, based on the total amount of component 1, component 3 and component 4 combined. %, Particularly preferably 60 to 90% by mass. The reason why the above range is preferable is the same as in the case of the present invention (II).
　次に本発明（ＩＶ）について説明する。
　本発明（ＩＶ）は、画像表示装置の画像表示部と透光性の保護部との間に介在させる重合物層を形成するための重合性組成物であって、該重合性組成物が、
（成分１）数平均分子量が１０００～１５０００の範囲である（メタ）アクリロイル基含有高分子化合物、
（成分２）光重合開始剤、
（成分３）アルコール性水酸基とアミド基の少なくとも一方を有するラジカル重合性不飽和基含有化合物、
（成分４）アルコール性水酸基とアミド基のいずれの基も有さず、かつ粘度が２５℃で５００ｍＰａ・ｓ以下である（メタ）アクリロイル基含有化合物、
（成分５）（メタ）アクリロイル基を有さない非イオン界面活性剤、および
（成分６）分子内に（メタ）アクリロイル基がなく、ラジカル重合を抑制する機能、ラジカル重合を禁止する機能、光重合性開始機能および界面活性作用のいずれの機能も有さず、かつ炭素原子と水素原子とから構成されるか、または炭素原子、水素原子および酸素原子から構成された、２５℃で液状または固体状である化合物を含み、かつ該重合性組成物を重合することにより得られる重合物の２５℃で周波数０．１Ｈｚでの貯蔵弾性率が１×１０３～１×１０５Ｐａであることを特徴とする重合性組成物に関する。 Next, the present invention (IV) will be described.
The present invention (IV) is a polymerizable composition for forming a polymer layer interposed between the image display part of the image display device and the translucent protective part, the polymerizable composition comprising:
(Component 1) (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 15000,
(Component 2) Photopolymerization initiator,
(Component 3) Radical polymerizable unsaturated group-containing compound having at least one of an alcoholic hydroxyl group and an amide group,
(Component 4) a (meth) acryloyl group-containing compound which does not have any group of an alcoholic hydroxyl group and an amide group and has a viscosity of 500 mPa · s or less at 25 ° C.
(Component 5) Nonionic surfactant having no (meth) acryloyl group, and (Component 6) No (meth) acryloyl group in the molecule, a function for suppressing radical polymerization, a function for inhibiting radical polymerization, light Liquid or solid at 25 ° C., which has neither a polymerization initiation function nor a surface-active function, and is composed of carbon atoms and hydrogen atoms, or is composed of carbon atoms, hydrogen atoms and oxygen atoms The storage modulus of the polymer obtained by polymerizing the polymerizable composition at 25 ° C. and a frequency of 0.1 Hz is 1 × 10 3 to 1 × 10 5 Pa. The present invention relates to a polymerizable composition.
　本発明（ＩＶ）の成分１および成分２は、それぞれ、本発明（Ｉ）の成分１および成分２と同様のものであり、本発明（ＩＶ）の成分３は、本発明（ＩＩ）の成分３と同様のものであり、本発明（ＩＶ）の成分４は、本発明（ＩＩＩ）の成分４と同様のものである。また成分２の配合量は前述の成分２の配合量と同じである。また、該配合量が好ましい理由も前述のとおりである。 Component 1 and Component 2 of the present invention (IV) are respectively the same as Component 1 and Component 2 of the present invention (I), and Component 3 of the present invention (IV) is a component of the present invention (II). 3, component 4 of the present invention (IV) is the same as component 4 of the present invention (III). The amount of component 2 is the same as the amount of component 2 described above. The reason why the blending amount is preferable is also as described above.
　次に、本発明（ＩＶ）の重合性組成物の必須成分である成分５について説明する。
　成分５は、（メタ）アクリロイル基を有さない非イオン界面活性剤である。なお、本明細書における「界面活性剤」とは、分子内に水になじみやすい部分（親水基）と、油になじみやすい部分（親油基・疎水基）を持つ物質の総称であり、ミセルやベシクル、ラメラ構造等を形成することで、極性物質と非極性物質を均一に混合させる働きをすることのできる性質を有する化合物である。
　非イオン界面活性剤の親水性と疎水性（親油性）の度合いを表す尺度として、グリフィン（Griffin）のＨＬＢ（Hydrophile-Lipophile Balanceの略）を用いることが多い。グリフィンのＨＬＢとは、親水基を全く持たないものはＨＬＢ＝０、また、ポリエチレングリコールのように親水基のみのものはＨＬＢ＝２０とし、求められている値であり、詳しくは、早野茂夫，油化学，第１３巻，４号，２２０（１９６４）に記載されているものである。 Next, component 5 which is an essential component of the polymerizable composition of the present invention (IV) will be described.
Component 5 is a nonionic surfactant that does not have a (meth) acryloyl group. The term “surfactant” in this specification is a generic name for substances having a portion that is familiar with water (hydrophilic group) and a portion that is familiar with oil (lipophilic group / hydrophobic group). And a vesicle, a lamellar structure, and the like, thereby having a property capable of uniformly mixing a polar substance and a nonpolar substance.
As a scale representing the degree of hydrophilicity and hydrophobicity (lipophilicity) of nonionic surfactants, Griffin's HLB (Hydrophile-Lipophile Balance) is often used. The HLB of Griffin is a required value with HLB = 0 having no hydrophilic group at all, and HLB = 20 having only a hydrophilic group such as polyethylene glycol. For details, see Shigeo Hayano, This is described in Yukagaku, Vol. 13, No. 4, 220 (1964).
　成分５の具体例としては、グリセリンモノステアレート（グリフィンのＨＬＢ＝４．３）、グリセリンモノラウレート（グリフィンのＨＬＢ＝５．４）、グリセリンモノカプレート（グリフィンのＨＬＢ＝６．８）、グリセリンモノカプリレート（グリフィンのＨＬＢ＝７．０）等のグリセリンモノ脂肪酸エステル、プロピレングリコールモノラウレート（グリフィンのＨＬＢ＝４．２）、プロピレングリコールモノパルミテート（グリフィンのＨＬＢ＝３．８）、プロピレングリコールモノステアレート（グリフィンのＨＬＢ＝３．７）、プロピレングリコールモノオレート（グリフィンのＨＬＢ＝３．６）、プロピレングリコールモノベヘネート（グリフィンのＨＬＢ＝３．４）等のプロピレングリコールモノ脂肪酸エステル、ソルビタンモノラウレート（グリフィンのＨＬＢ＝８．６）、ソルビタンモノオレエート（グリフィンのＨＬＢ＝４．３）、ソルビタンモノステアレート（グリフィンのＨＬＢ＝４．７）等のソルビタンモノ脂肪酸エステル、ソルビタントリステアレート（グリフィンのＨＬＢ＝３．０）、ソルビタントリオレート（グリフィンのＨＬＢ＝３．０）、ソルビタントリベヘネート（グリフィンのＨＬＢ＝２．５）等のソルビタントリ脂肪酸エステル、ポリオキシエチレン（グリフィンのエチレンオキサイドの平均付加数＝２０ｍｏｌ）ソルビタントリオレート（グリフィンのＨＬＢ＝１１．０）、ポリオキシエチレン（エチレンオキサイドの平均付加数＝５ｍｏｌ）グリセリンモノステアレート（グリフィンのＨＬＢ＝８．７）等のポリオキシエチレン構造を有する脂肪酸エステル等を挙げることができる。
　これらを単独で使用してもよく、２種類以上を併用して使用することもできる。
　これらの（メタ）アクリロイル基を有さない非イオン界面活性剤の中で、好ましいものとしては、グリフィンのＨＬＢの値が３．０～９．０であることが望ましく、さらに好ましくは、３．０～７．５であり、特に好ましくは、３．０～６．０である。 Specific examples of component 5 include glycerin monostearate (HLP of Griffin = 4.3), glycerin monolaurate (HLB of Griffin = 5.4), glycerin monocaprate (HLB of Griffin = 6.8), glycerin Glycerin monofatty acid ester such as monocaprylate (HLP of Griffin = 7.0), propylene glycol monolaurate (HLB of Griffin = 4.2), propylene glycol monopalmitate (HLB of Griffin = 3.8), propylene Propylene glycol monofatty acid esters such as glycol monostearate (Glyphine HLB = 3.7), propylene glycol monooleate (Glyffin HLB = 3.6), propylene glycol monobehenate (Glyphine HLB = 3.4), Sorbita Sorbitan monofatty acid esters such as monolaurate (Glyphine HLB = 8.6), sorbitan monooleate (HLP of Griffin = 4.3), sorbitan monostearate (HLB of Griffin = 4.7), sorbitan tristearate Sorbitan trifatty acid esters such as rate (griffin HLB = 3.0), sorbitan trioleate (griffin HLB = 3.0), sorbitan tribehenate (griffin HLB = 2.5), polyoxyethylene (griffin) Average addition number of ethylene oxide = 20 mol) sorbitan trioleate (HLB of Griffin = 11.0), polyoxyethylene (average addition number of ethylene oxide = 5 mol) glycerin monostearate (HLB of Griffin = 8.7), etc. Of polyoxyethylene And fatty acid esters having a granulation.
These may be used alone or in combination of two or more.
Among these nonionic surfactants having no (meth) acryloyl group, it is preferable that the HLB value of Griffin is 3.0 to 9.0, more preferably 3. It is 0 to 7.5, and particularly preferably 3.0 to 6.0.
　次に、本発明（ＩＶ）の重合性組成物の必須成分である成分６について説明する。
　成分６は、分子内に（メタ）アクリロイル基がなく、ラジカル重合を抑制する機能、ラジカル重合を禁止する機能、光重合性開始機能および界面活性作用のいずれの機能も有さず、かつ炭素原子と水素原子とから構成されるか、または炭素原子、水素原子および酸素原子から構成された、２５℃で液状または固体状である化合物である。成分６としては、炭素原子および水素原子のみで構成された化合物、または炭素原子、水素原子および酸素原子のみで構成された化合物であって、かつエチレン性二重結合を有さない化合物が好ましい。
　特に、画像表示部を有する基部と、透光性の保護部との間に重合性組成物を介在させ、重合させて重合物層を形成する工程を有する製造方法を用いて画像表示装置が製造される場合、この工程で使用される重合性組成物には、重合時の体積収縮率を低く抑える目的で成分６を含むことが好ましい。また、重合時の体積収縮率を抑制する他、ガラスやアクリル樹脂等の被着体への重合物の密着性を増加させる目的で使用される場合もある。
　成分６としては、２５℃で液状である化合物、あるいは、２５℃で固体状である化合物を用いることができる。 Next, component 6 that is an essential component of the polymerizable composition of the present invention (IV) will be described.
Component 6 has no (meth) acryloyl group in the molecule, does not have any function of suppressing radical polymerization, function of inhibiting radical polymerization, photopolymerization initiating function, or surface-active function, and carbon atom And a hydrogen atom or a compound composed of a carbon atom, a hydrogen atom and an oxygen atom, which is liquid or solid at 25 ° C. Component 6 is preferably a compound composed of only carbon atoms and hydrogen atoms, or a compound composed of only carbon atoms, hydrogen atoms and oxygen atoms and having no ethylenic double bond.
In particular, an image display device is manufactured using a manufacturing method including a step of forming a polymer layer by interposing a polymerizable composition between a base portion having an image display portion and a translucent protective portion and polymerizing the polymerizable composition. In this case, the polymerizable composition used in this step preferably contains component 6 for the purpose of keeping the volume shrinkage during polymerization low. In addition to suppressing the volume shrinkage during polymerization, it may be used for the purpose of increasing the adhesion of the polymer to an adherend such as glass or acrylic resin.
As the component 6, a compound that is liquid at 25 ° C. or a compound that is solid at 25 ° C. can be used.
　成分６として用いられる、２５℃で液状である化合物としては、例えば、ポリ（α－オレフィン）液状物、エチレン－プロピレン共重合液状物、エチレン－α－オレフィン共重合液状物、プロピレン－α－オレフィン共重合液状物、液状ポリブテン、液状水添ポリブテン、液状ポリブタジエン、液状水添ポリブタジエン、液状ポリイソプレン、液状水添ポリイソプレン、液状ポリブタジエンポリオール、液状水添ポリブタジエンポリオール、液状ポリイソプレンポリオール、液状水添ポリイソプレンポリオール、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオール等を挙げることができる。 Examples of compounds used as component 6 that are liquid at 25 ° C. include poly (α-olefin) liquid, ethylene-propylene copolymer liquid, ethylene-α-olefin copolymer liquid, and propylene-α-olefin. Copolymer liquid, liquid polybutene, liquid hydrogenated polybutene, liquid polybutadiene, liquid hydrogenated polybutadiene, liquid polyisoprene, liquid hydrogenated polyisoprene, liquid polybutadiene polyol, liquid hydrogenated polybutadiene polyol, liquid polyisoprene polyol, liquid hydrogenated poly Examples include isoprene polyol, polyether polyol, polyester polyol, and polycarbonate polyol.
　ポリ（α－オレフィン）液状物とは、α－オレフィンの重合により製造される液状物であり、α－オレフィンとは炭素－炭素二重結合を分子末端に１つ有する炭化水素化合物であり、例えば、１－ブテン、１－ペンテン、１－ヘキセン、１－オクテン、１－デセン、１－ドデセン、１－テトラデセン、１－ヘキサデセン、１－オクタデセン等を挙げることができる。 The poly (α-olefin) liquid is a liquid produced by polymerization of α-olefin, and the α-olefin is a hydrocarbon compound having one carbon-carbon double bond at the molecular end. 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and the like.
　エチレン－α－オレフィン共重合液状物とは、エチレンとα－オレフィンとを共重合することによって製造される液状重合物である。α－オレフィンとは炭素－炭素二重結合を分子末端に１つ有する炭化水素化合物であり、例えば、１－ブテン、１－ペンテン、１－ヘキセン、１－オクテン、１－デセン、１－ドデセン、１－テトラデセン、１－ヘキサデセン、１－オクタデセン等を挙げることができる。 The ethylene-α-olefin copolymer liquid is a liquid polymer produced by copolymerizing ethylene and α-olefin. An α-olefin is a hydrocarbon compound having one carbon-carbon double bond at the molecular end, such as 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, Examples thereof include 1-tetradecene, 1-hexadecene, 1-octadecene and the like.
　プロピレン－α－オレフィン共重合液状物とは、プロピレンとα－オレフィンとを共重合することによって製造される液状重合物である。α－オレフィンとは炭素－炭素二重結合を分子末端に１つ有する炭化水素化合物であり、例えば、１－ブテン、１－ペンテン、１－ヘキセン、１－オクテン、１－デセン、１－ドデセン、１－テトラデセン、１－ヘキサデセン、１－オクタデセン等を挙げることができる。 The propylene-α-olefin copolymer liquid material is a liquid polymer produced by copolymerizing propylene and α-olefin. An α-olefin is a hydrocarbon compound having one carbon-carbon double bond at the molecular end, such as 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, Examples thereof include 1-tetradecene, 1-hexadecene, 1-octadecene and the like.
　液状ポリブテンとは、イソブテンの単独重合、ｎ－ブテンの単独重合、イソブテンおよびｎ－ブテンの共重合等のイソブテンあるいはｎ－ブテンを（共）重合成分に含む液状重合物であり、末端の一方に炭素－炭素不飽和結合を有する化合物である。液状ポリブテンの市販品としては、例えば、ＪＸ日鉱日石エネルギー株式会社製の日石ポリブテンＬＶ－７、ＬＶ－５０、ＬＶ－１００、ＨＶ－１５、ＨＶ－３５、ＨＶ－５０、ＨＶ－１００、ＨＶ－３００等を挙げることができる。 Liquid polybutene is a liquid polymer containing isobutene or n-butene as a (co) polymerization component, such as homopolymerization of isobutene, homopolymerization of n-butene, copolymerization of isobutene and n-butene. It is a compound having a carbon-carbon unsaturated bond. Examples of commercially available liquid polybutene include Nisseki Polybutene LV-7, LV-50, LV-100, HV-15, HV-35, HV-50, HV-100, manufactured by JX Nippon Mining & Energy Corporation. And HV-300.
　液状水添ポリブテンとは、前記液状ポリブテンを、水素添加して得られる側鎖を有する液状物であり、例えば、日油株式会社製のパームリール４、パームリール６、パームリール１８、パームリール２４、パームリールＥＸ等を挙げることができる。 The liquid hydrogenated polybutene is a liquid material having a side chain obtained by hydrogenating the liquid polybutene. For example, palm reel 4, palm reel 6, palm reel 18, palm reel 24 manufactured by NOF Corporation. And palm reel EX.
　液状ポリブタジエンとは、常温で液状のブタジエン重合物であり、例えば、エボニックデグサ製のＰＯＬＹＶＥＳＴ１１０、ＰＯＬＹＶＥＳＴ１３０や日本曹達株式会社製のＮＩＳＳＯ－ＰＢ　Ｂ－１０００、ＮＩＳＳＯ－ＰＢ　Ｂ－２０００、ＮＩＳＳＯ－ＰＢ　Ｂ－３０００等を挙げることができる。 Liquid polybutadiene is a butadiene polymer that is liquid at room temperature. For example, POLYVEST110, POLYVEST130 manufactured by Evonik Degussa, NISSO-PB B-1000, NISSO-PB B-2000, NISSO-PB B- manufactured by Nippon Soda Co., Ltd. 3000 etc. can be mentioned.
　液状水添ポリプタジエンとは、ブタジエン重合物を還元水素化して得られる、常温で液状物であり、例えば、日本曹達株式会社製のＮＩＳＳＯ－ＰＢ　ＢＩ－２０００、ＮＩＳＳＯ－ＰＢ　Ｂ－３０００等を挙げることができる。 The liquid hydrogenated polyptadiene is a liquid material obtained at a normal temperature obtained by reductive hydrogenation of a butadiene polymer. Examples thereof include NISSO-PB BI-2000 and NISSO-PB B-3000 manufactured by Nippon Soda Co., Ltd. Can do.
　液状ポリイソプレンとは、常温で液状のイソプレン重合物であり、例えば、株式会社クラレ製のクラプレン　ＬＩＲ－３０等を挙げることができる。 Liquid polyisoprene is a liquid isoprene polymer at room temperature, and examples thereof include Kuraray LIR-30 manufactured by Kuraray Co., Ltd.
　液状水添ポリイソプレンとは、イソプレン重合物を還元水素化して得られる、常温で液状の化合物であり、株式会社クラレ製のＬＩＲ－２００等を挙げることができる。 Liquid hydrogenated polyisoprene is a compound that is liquid at room temperature obtained by reductive hydrogenation of an isoprene polymer, and examples thereof include LIR-200 manufactured by Kuraray Co., Ltd.
　液状ポリブタジエンポリオールとは、分子末端に水酸基を２つ以上有しかつポリブタジエン構造単位を有する、常温で液状の重合物であり、例えば、日本曹達株式会社製のＮＩＳＳＯ－ＰＢ　Ｇ－１０００、ＮＩＳＳＯ－ＰＢ　Ｇ－２０００、ＮＩＳＳＯ－ＰＢ　Ｇ－３０００、出光興産株式会社製のＰｏｌｙ　ｂｄ等を挙げることができる。 The liquid polybutadiene polyol is a polymer that is liquid at room temperature and has two or more hydroxyl groups at the molecular terminals and has a polybutadiene structural unit. For example, NISSO-PB G-1000, NISSO-PB manufactured by Nippon Soda Co., Ltd. Examples thereof include G-2000, NISSO-PB G-3000, and Poly bd manufactured by Idemitsu Kosan Co., Ltd.
　液状水添ポリブタジエンポリオールとは、ポリブタジエンポリオールあるいはポリブタジエンポリカルボン酸を還元水素化して得られる構造を有する液状ポリオールであり、日本曹達株式会社製のＮＩＳＳＯ－ＰＢ　ＧＩ－１０００、ＮＩＳＳＯ－ＰＢ　ＧＩ－２０００、ＮＩＳＳＯ－ＰＢ　ＧＩ－３０００等を挙げることができる。 The liquid hydrogenated polybutadiene polyol is a liquid polyol having a structure obtained by reductive hydrogenation of polybutadiene polyol or polybutadiene polycarboxylic acid. NISSO-PB GI-1000, NISSO-PB GI-2000 manufactured by Nippon Soda Co., Ltd. And NISSO-PB GI-3000.
　液状ポリイソプレンポリオールとは、分子末端に水酸基を２つ以上有しかつポリイソプレン構造単位を有する、常温で液状の重合物であり、例えば、出光興産株式会社製のＰｏｌｙ　ｉｐ等を挙げることができる。 The liquid polyisoprene polyol is a polymer that is liquid at room temperature and has two or more hydroxyl groups at the molecular ends and a polyisoprene structural unit, and examples thereof include poly ip manufactured by Idemitsu Kosan Co., Ltd. .
　液状水添ポリイソプレンポリオールとは、ポリイソプレンポリオールあるいはポリイソプレンポリカルボン酸を還元水素化して得られる構造を有する液状ポリオールであり、例えば、出光興産株式会社製のエポール等を挙げることができる。 The liquid hydrogenated polyisoprene polyol is a liquid polyol having a structure obtained by reductive hydrogenation of polyisoprene polyol or polyisoprene polycarboxylic acid, and examples thereof include Epole manufactured by Idemitsu Kosan Co., Ltd.
　ポリエーテルポリオールしては、例えば、ポリプロピレングリコール、ポリテトラメチレングリコール、プロピレンオキサイド－テトラヒドロフラン共重合体等を挙げることができる。 Examples of the polyether polyol include polypropylene glycol, polytetramethylene glycol, and propylene oxide-tetrahydrofuran copolymer.
　ポリエステルポリオールとしては、ポリオールとポリカルボン酸の重縮合物あるは、ポリオールとポリカルボン酸のエステルのエステル交換反応物、ポリオールへの環状エステルの開環重合物等を挙げることができる。 Examples of the polyester polyol include a polycondensate of a polyol and a polycarboxylic acid, a transesterification product of an ester of a polyol and a polycarboxylic acid, a ring-opening polymer of a cyclic ester into a polyol, and the like.
　ポリカーボネートポリオールとしては、ポリオールとホスゲンの重縮合物、あるいはジメチルカーボネート、ジエチルカーボネート、エチレンカーボネート等の有機炭酸エステル類とのポリオールのエステル交換反応物を挙げることができる。
　ポリカーボネートポリオールの原料として用いられるポリオールとしては、１，４－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、ネオペンチルグリコール、３－メチル－１，５－ペンタンジオール、１，８－オクタンジオール、１，９－ノナンジオール、２－メチル－１，８－オクタンジオール、２－ブチル－２－エチル－１，３－プロパンジオール、２，４－ジエチル－１，５－ペンタンジオール、トリメチロールエタン、トリメチロールプロパン等を挙げることができ、これらを単独あるいは２種類以上を併用して用いることができる。これらの中で、好ましいものとしては、１，４－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、ネオペンチルグリコール、３－メチル－１，５－ペンタンジオールであり、さらに好ましいものとしては、１，５－ペンタンジオール、ネオペンチルグリコール、３－メチル－１，５－ペンタンジオール等であり、最も好ましいものは、３－メチル－１，５－ペンタンジオールである。 Examples of the polycarbonate polyol include a polycondensate of polyol and phosgene, or a transesterification product of a polyol with an organic carbonate such as dimethyl carbonate, diethyl carbonate, or ethylene carbonate.
Polyols used as raw materials for polycarbonate polyols include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,8 -Octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, Examples thereof include trimethylolethane and trimethylolpropane. These can be used alone or in combination of two or more. Among these, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, and 3-methyl-1,5-pentanediol are more preferable. Examples thereof include 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol and the like, and most preferred is 3-methyl-1,5-pentanediol.
　また、本発明（ＩＶ）の重合性組成物では、成分６として、２５℃で固体状である化合物を使用することもできる。
　成分６として用いられる、２５℃で固体状である化合物としては、分子内に炭素－炭素不飽和結合を有さない化合物であることが好ましい。
　このような化合物としては、２５℃で固体状のエポキシ樹脂、２５℃で固体状のポリエステル樹脂、２５℃で固体状のポリオール樹脂や、２５℃で固体状の水添石油樹脂、テルペン系水添樹脂、水添ロジンエステル等の粘着付与剤を挙げることができる。
　これらの中で、好ましいものとしては、水添石油樹脂、テルペン系水添樹脂、水添ロジンエステル等の粘着付与剤を挙げることができる。 In the polymerizable composition of the present invention (IV), a compound that is solid at 25 ° C. can be used as component 6.
The compound used as component 6 that is solid at 25 ° C. is preferably a compound having no carbon-carbon unsaturated bond in the molecule.
Examples of such compounds include a solid epoxy resin at 25 ° C., a polyester resin solid at 25 ° C., a polyol resin solid at 25 ° C., a hydrogenated petroleum resin solid at 25 ° C., and a terpene hydrogenated resin. Mention may be made of tackifiers such as resins and hydrogenated rosin esters.
Among these, preferred are tackifiers such as hydrogenated petroleum resins, terpene hydrogenated resins, and hydrogenated rosin esters.
　水添石油樹脂とは、石油系樹脂を水素還元して得られる樹脂である。水添石油樹脂の原料である石油系樹脂としては、脂肪族系石油樹脂、芳香族系石油樹脂、脂肪族－芳香族共重合系石油樹脂、脂環族系石油樹脂、ジシクロペンタジエン樹脂およびこれらの水添物等の変性物が挙げられる。合成石油樹脂は、Ｃ５系でも、Ｃ９系でもよい。 Hydrogenated petroleum resin is a resin obtained by hydrogen reduction of petroleum-based resin. Examples of petroleum resins that are raw materials for hydrogenated petroleum resins include aliphatic petroleum resins, aromatic petroleum resins, aliphatic-aromatic copolymer petroleum resins, alicyclic petroleum resins, dicyclopentadiene resins, and the like. Modified products such as hydrogenated products of The synthetic petroleum resin may be C5 or C9.
　テルペン系水添樹脂とは、テルペン系樹脂を還元水素化して得られる樹脂である。テルペン系水添樹脂の原料であるテルペン系樹脂としては、β－ピネン樹脂、α－ピネン樹脂、β－リモネン樹脂、α－リモネン樹脂、ピネン－リモネン共重合樹脂、ピネン－リモネン－スチレン共重合樹脂、テルペン－フェノール樹脂、芳香族変性テルペン樹脂などが挙げられる。これらのテルペン系樹脂の多くは、極性基を有しない樹脂である。 The terpene-based hydrogenated resin is a resin obtained by reductive hydrogenation of a terpene-based resin. Terpenic resins that are raw materials for terpene hydrogenated resins include β-pinene resins, α-pinene resins, β-limonene resins, α-limonene resins, pinene-limonene copolymer resins, and pinene-limonene-styrene copolymer resins. Terpene-phenol resin, aromatic modified terpene resin and the like. Many of these terpene resins are resins having no polar group.
　水添ロジンエステルとは、ロジン系樹脂を水添して得られる水添ロジンをエステル化あるいはロジンをエステル化して得られるロジンエステルを水素還元して得られた樹脂である。ロジン系樹脂粘着付与剤としては、ガムロジン、トール油ロジン、ウッドロジン、不均化ロジン、重合ロジン、マレイン化ロジンなどの変性ロジンなどが挙げられる。
　なお、本明細書においては、多価アルコールの一部のアルコール性水酸基が水添ロジンでエステル化された化合物も、多価アルコールのすべてのアルコール性水酸基が水添ロジンでエステル化された化合物もともに、水添ロジンエステルに含まれると定義する。 The hydrogenated rosin ester is a resin obtained by hydrogenating a rosin ester obtained by esterifying a hydrogenated rosin obtained by hydrogenating a rosin resin or esterifying a rosin. Examples of the rosin resin tackifier include modified rosins such as gum rosin, tall oil rosin, wood rosin, disproportionated rosin, polymerized rosin and maleated rosin.
In this specification, a compound in which some alcoholic hydroxyl groups of polyhydric alcohol are esterified with hydrogenated rosin, and a compound in which all alcoholic hydroxyl groups of polyhydric alcohol are esterified with hydrogenated rosin Both are defined as being included in the hydrogenated rosin ester.
　これらの中で、より好ましいものとしては、水添ロジンエステル、テルペン－フェノール樹脂であり、さらに好ましくは、水添ロジンエステルであり、特に好ましくは、グリセリン、トリメチロールプロパン、トリメチロールエタン等のトリオールまたはペンタエリスリトール等のテトラオールと水添ロジンとのエステル化である水添ロジンエステル、あるいはグリセリン、トリメチロールプロパン、トリメチロールエタン等のトリオールまたはペンタエリスリトール等のテトラオールとロジンのエステル物（ロジンエステル）を水素還元して得られた水添ロジンエステルである。 Among these, hydrogenated rosin esters and terpene-phenol resins are more preferable, hydrogenated rosin esters are more preferable, and triols such as glycerin, trimethylolpropane, and trimethylolethane are particularly preferable. Or hydrogenated rosin ester which is esterification of tetraol such as pentaerythritol and hydrogenated rosin, or triol such as glycerin, trimethylolpropane and trimethylolethane or tetraol and rosin ester such as pentaerythritol (rosin ester) ) Hydrogenated rosin ester obtained by hydrogen reduction.
　また、本発明（ＩＶ）の重合性組成物と粘度や重合物の被着体への密着性のバランスをとるために、成分６の化合物としては、２５℃で液状である化合物と、２５℃で固体状である化合物とを併用することができかつ好ましい。
　さらに好ましくは、２５℃で液状であるポリエーテルポリオール、ポリエステルポリオールまたはポリカーボネートポリオールと、２５℃で固体状である粘着付与剤とを併用することであり、特に好ましくは、ポリエステルポリオールまたはポリカーボネートポリオールと、水添ロジンエステルとを併用することである。 In addition, in order to balance the polymerizable composition of the present invention (IV) and the viscosity and adhesion of the polymer to the adherend, the compound of Component 6 includes a compound that is liquid at 25 ° C. and 25 ° C. And a solid compound can be used in combination.
More preferably, it is a combined use of polyether polyol, polyester polyol or polycarbonate polyol which is liquid at 25 ° C., and a tackifier which is solid at 25 ° C., and particularly preferably polyester polyol or polycarbonate polyol, It is to use together with hydrogenated rosin ester.
　成分６において、２５℃で液状である化合物と、２５℃で固体状である化合物とを併用する場合の好ましい併用割合は、質量比で、２５℃で液状である化合物９０等量に対して２５℃で固体状である化合物１０等量～２５℃で液状である化合物１０等量に対して２５℃で固体状である化合物９０等量であり、さらに好ましくは、２５℃で液状である化合物８５等量に対して２５℃で固体状である化合物１５等量～２５℃で液状である化合物１５等量に対して２５℃で固体状である化合物８５等量である。 In Component 6, when a compound that is liquid at 25 ° C. and a compound that is solid at 25 ° C. are used in combination, a preferred combination ratio is 25 by mass ratio with respect to 90 equivalents of the compound that is liquid at 25 ° C. 10 equivalents of the compound that is solid at 25 ° C. to 90 equivalents of the compound that is solid at 25 ° C., more preferably 10 equivalents of the compound that is liquid at 25 ° C. 15 equivalents of the compound that is solid at 25 ° C. with respect to the equivalent amount to 85 equivalents of the compound that is solid at 25 ° C. with respect to 15 equivalents of the compound that is liquid at 25 ° C.
　本発明（ＩＶ）における成分５の使用量は、本発明（ＩＶ）の必須成分である成分１、成分３、成分４、成分５および成分６を合わせた総量に対して、３～４０質量％であることが好ましく、さらに好ましくは、４～３５質量％であり、特に好ましくは５～３０質量％である。成分５の使用量が、本発明（ＩＶ）の必須成分である成分１、成分３、成分４、成分５および成分６を合わせた総量に対して３質量％未満の場合には、本発明（ＩＶ）の重合性組成物を重合して得られる重合物の塗膜の透明性が失われる場合がある。また、成分５の使用量が、本発明（ＩＶ）の必須成分である成分１、成分３、成分４、成分５および成分６を合わせた総量に対して４０質量％を超えて含まれる場合には、本発明（ＩＶ）の重合性組成物を重合して得られる重合物の塗膜強度が低くなりすぎる場合がある。 The amount of component 5 used in the present invention (IV) is 3 to 40% by mass based on the total amount of component 1, component 3, component 4, component 5 and component 6 as essential components of the present invention (IV). It is preferably 4 to 35% by mass, more preferably 5 to 30% by mass. When the amount of component 5 used is less than 3% by mass based on the total amount of component 1, component 3, component 4, component 5 and component 6 as essential components of the present invention (IV), The transparency of the coating film of the polymer obtained by polymerizing the polymerizable composition of IV) may be lost. Moreover, when the usage-amount of the component 5 is contained exceeding 40 mass% with respect to the total amount which combined the component 1, the component 3, the component 4, the component 5, and the component 6 which are essential components of this invention (IV). The film strength of the polymer obtained by polymerizing the polymerizable composition of the present invention (IV) may be too low.
　本発明（ＩＶ）における成分６の使用量は、本発明（ＩＶ）の必須成分である成分１、成分３、成分４、成分５および成分６を合わせた総量に対して１５～８５質量％であることが好ましく、さらに好ましくは、３０～７０質量％であり、特に好ましくは、４０～６０質量％である。本発明（ＩＶ）における成分６の使用量が、本発明（ＩＶ）の必須成分である成分１、成分３、成分４、成分５および成分６を合わせた総量に対して１５質量％未満であると、成分６を添加した効果（即ち、重合時の体積収縮率の低減効果）が得られえなくなる場合がある。また、本発明（ＩＶ）における成分６の使用量が、本発明（ＩＶ）の必須成分である成分１、成分３、成分４、成分５および成分６を合わせた総量に対して８５質量％より多くなると、本発明（ＩＶ）の重合性組成物を重合して得られる重合物の塗膜強度が低くなりすぎる場合がある。 The amount of component 6 used in the present invention (IV) is 15 to 85% by mass based on the total amount of component 1, component 3, component 4, component 5 and component 6 as essential components of the present invention (IV). It is preferably 30 to 70% by mass, more preferably 40 to 60% by mass. The usage-amount of the component 6 in this invention (IV) is less than 15 mass% with respect to the total amount which combined the component 1, the component 3, the component 4, the component 5, and the component 6 which are essential components of this invention (IV). In some cases, the effect of adding the component 6 (that is, the effect of reducing the volumetric shrinkage during polymerization) cannot be obtained. Moreover, the usage-amount of the component 6 in this invention (IV) is 85 mass% with respect to the total amount which combined the component 1, the component 3, the component 4, the component 5, and the component 6 which are essential components of this invention (IV). When it increases, the coating strength of the polymer obtained by polymerizing the polymerizable composition of the present invention (IV) may become too low.
　また、本発明（ＩＶ）における成分１の使用量は、成分１、成分３、成分４、成分５および成分６を合わせた総量に対して、１０～４０質量％であることが好ましく、さらに好ましくは、１３～３７質量％であり、特に好ましくは、１５～３５質量％である。本発明（ＩＶ）における成分１の使用量が、成分１、成分３、成分４、成分５および成分６を合わせた総量に対して１０質量％未満の場合には、画像表示装置の画像表示部の材料や透光性の保護部の材料への、本発明（ＩＶ）の重合性組成物を重合して得られる重合物の密着強度が低くなる恐れがある。また、本発明（ＩＶ）における成分１の使用量が、成分１、成分３、成分４、成分５および成分６を合わせた総量に対して４０質量％以上の場合には、重合性組成物の粘度が高くなりすぎてしまったり、貯蔵弾性率が高くなりすぎてしまったりする場合がある。 In addition, the amount of component 1 used in the present invention (IV) is preferably 10 to 40% by mass, more preferably based on the total amount of component 1, component 3, component 4, component 5 and component 6 combined. Is from 13 to 37% by mass, particularly preferably from 15 to 35% by mass. When the amount of component 1 used in the present invention (IV) is less than 10% by mass with respect to the total amount of component 1, component 3, component 4, component 5 and component 6, the image display unit of the image display device There is a possibility that the adhesion strength of the polymer obtained by polymerizing the polymerizable composition of the present invention (IV) to the above material or the material of the translucent protective part is lowered. Moreover, when the usage-amount of the component 1 in this invention (IV) is 40 mass% or more with respect to the total amount which combined the component 1, the component 3, the component 4, the component 5, and the component 6, In some cases, the viscosity becomes too high, or the storage elastic modulus becomes too high.
　本発明（ＩＶ）における成分３の使用量は、成分１、成分３、成分４、成分５および成分６を合わせた総量に対して、１～１５質量％であることが好ましく、さらに好ましくは、２～１０質量％であり、特に好ましくは、２～８質量％である。その理由は本発明（ＩＩ）や本発明（ＩＩＩ）の場合と同様である。 The amount of Component 3 used in the present invention (IV) is preferably 1 to 15% by mass, more preferably, based on the total amount of Component 1, Component 3, Component 4, Component 5 and Component 6. It is 2 to 10% by mass, and particularly preferably 2 to 8% by mass. The reason is the same as in the case of the present invention (II) or the present invention (III).
　本発明（ＩＶ）における成分４の使用量は、本発明（ＩＶ）の必須成分である成分１、成分３、成分４、成分５および成分６を合わせた総量に対して３～２０質量％であることが好ましく、さらに好ましくは、４～１９質量％であり、特に好ましくは、５～１８質量％である。その理由は本発明（ＩＩＩ）の場合と同様である。 The amount of Component 4 used in the present invention (IV) is 3 to 20% by mass based on the total amount of Component 1, Component 3, Component 4, Component 5 and Component 6 as essential components of the present invention (IV). It is preferably 4 to 19% by mass, more preferably 5 to 18% by mass. The reason is the same as in the case of the present invention (III).
　また、本発明（ＩＶ）の重合性組成物を後述の本発明（ＶＩＩＩ）の画像表示装置の製造方法に用いる場合には、本発明（ＩＶ）の重合性組成物の重合時の体積収縮率は、３．５％以下であることが好ましく、さらに好ましくは、２．７％以下であり、もっとも好ましいのは２．３％以下である。本発明（ＩＶ）の重合性組成物の重合時の体積収縮率が、３．５％よりも大きい場合には、重合性組成物が重合する際に重合物に蓄積される内部応力が大きくなりすぎ、重合物層５ａあるいは５ｂと、それらに接している表示部２、保護部３またはタッチパネル７との界面に歪みができてしまう場合がある。 In addition, when the polymerizable composition of the present invention (IV) is used in a method for producing an image display device of the present invention (VIII) described later, the volume shrinkage ratio at the time of polymerization of the polymerizable composition of the present invention (IV). Is preferably 3.5% or less, more preferably 2.7% or less, and most preferably 2.3% or less. When the volumetric shrinkage during polymerization of the polymerizable composition of the present invention (IV) is greater than 3.5%, the internal stress accumulated in the polymer increases when the polymerizable composition is polymerized. In some cases, the interface between the polymer layer 5a or 5b and the display unit 2, the protection unit 3 or the touch panel 7 in contact with the polymer layer 5a or 5b may be distorted.
　本発明（Ｉ）～本発明（ＩＶ）の重合性組成物の２５℃における粘度は、特に制限はないが、ハンドリング上、１００００ｍＰａ・ｓ以下であることが好ましく、さらに好ましくは、７０００ｍＰａ・ｓ以下であり、特に好ましくは、５０００ｍＰａ・ｓ以下である。
　なお、本明細書に記載の粘度は、２５℃で１００００ｍＰａ・ｓ以下の粘度の組成物に関しては、コーン／プレート型粘度計（Ｂｒｏｏｋｆｉｅｌｄ社製、型式：ＤＶ－ＩＩ＋Ｐｒｏ、スピンドルの型番：ＣＰＥ－４２）を用いて、温度２５．０℃、回転数５ｒｐｍの条件で測定した値である。
　２５℃における、本発明（Ｉ）～本発明（ＩＶ）の重合性組成物の粘度を１０００ｍＰａ・ｓ以下にすると、本発明（Ｉ）～本発明（ＩＶ）の重合性組成物をディスペンサーを用いた線引き塗布法で塗布する場合には、塗布後、液の広がりが容易になり、その結果、必要箇所に均一の厚みで該組成物がいきわたることが容易になり、さらに、気泡の巻き込みが抑制されやすくなる。 The viscosity of the polymerizable composition of the present invention (I) to the present invention (IV) at 25 ° C. is not particularly limited, but is preferably 10000 mPa · s or less, more preferably 7000 mPa · s or less in terms of handling. Especially preferably, it is 5000 mPa · s or less.
The viscosity described in this specification is a cone / plate viscometer (manufactured by Brookfield, model: DV-II + Pro, spindle model number: CPE-42) for a composition having a viscosity of 10000 mPa · s or less at 25 ° C. ) Using a temperature of 25.0 ° C. and a rotation speed of 5 rpm.
When the viscosity of the polymerizable composition of the present invention (I) to the present invention (IV) is set to 1000 mPa · s or less at 25 ° C., the polymerizable composition of the present invention (I) to the present invention (IV) is used in a dispenser. In the case of applying by the conventional drawing method, the spread of the liquid becomes easy after application, and as a result, it becomes easy to spread the composition with a uniform thickness at the required location, and further, the entrainment of bubbles is suppressed. It becomes easy to be done.
　本発明（Ｉ）～本発明（ＩＶ）の重合性組成物は、重合抑制剤や禁止剤、酸化防止剤を添加することができかつ好ましい。 In the polymerizable composition of the present invention (I) to the present invention (IV), a polymerization inhibitor, an inhibitor and an antioxidant can be preferably added.
　重合禁止剤や重合抑制剤としては、重合禁止能あるいは重合を抑制する機能を有していれば、特に限定されるものではないが、例えば、フェノチアジン、ヒドロキノン、ｐ－メトキシフェノール、ｐ－ベンゾキノン、ナフトキノン、フェナンスラキノン、トルキノン、２，５－ジアセトキシ－ｐ－ベンゾキノン、２，５－ジカプロキシ－ｐ－ベンゾキノン、２，５－アシロキシ－ｐ－ベンゾキノン、ｐ－ｔ－ブチルカテコール、２，５－ジ－ｔ－ブチルヒドロキノン、ｐ－ｔｅｒｔ－ブチルカテコール、モノ－ｔ－ブチルヒドロキノン、２，５－ジ－ｔ－アミルヒドロキノン、ジ－ｔ－ブチル・パラクレゾールヒドロキノンモノメチルエーテル、アルファナフトール、アセトアミジンアセテート、アセトアミジンサルフェート、フェニルヒドラジン塩酸塩、ヒドラジン塩酸塩、トリメチルベンジルアンモニウムクロライド、ラウリルピリジニウムクロライド、セチルトリメチルアンモニウムクロライド、フェニルトリメチルアンモニウムクロライド、トリメチルベンジルアンモニウムオキザレート、ジ（トリメチルベンジルアンモニウム）オキザレート、トリメチルベンジルアンモニウムマレート、トリメチルベンジルアンモニウムタータレート、トリメチルベンジルアンモニウムグリコレート、フェニル－β－ナフチルアミン、パラベンジルアミノフェノール、ジ－β－ナフチルパラフェニレンジアミン、ジニトロベンゼン、トリニトロトルエン、ピクリン酸、シクロヘキサノンオキシム、ピロガロール、タンニン酸、レゾルシン、トリエチルアミン塩酸塩、ジメチルアニリン塩酸塩およびジブチルアミン塩酸塩等が挙げられる。
　これらは単独でも、あるいは２種以上を適宜組み合わせて使用することができる。
　これらの中でも、ヒドロキノン、ｐ－メトキシフェノール、ｐ－ベンゾキノン、ナフトキノン、フェナンスラキノン、２，５－ジアセトキシ－ｐ－ベンゾキノン、２，５－ジカプロキシ－ｐ－ベンゾキノン、２，５－アシロキシ－ｐ－ベンゾキノン、ｐ－ｔ－ブチルカテコール、２，５－ジ－ｔ－ブチルヒドロキノン、ｐ－ｔｅｒｔ－ブチルカテコール、モノ－ｔ－ブチルヒドロキノン、２，５－ジ－ｔ－アミルヒドロキノン、ジ－ｔ－ブチル・パラクレゾールヒドロキノンモノメチルエーテルおよびフェノチアジンが好適に用いられる。 The polymerization inhibitor and the polymerization inhibitor are not particularly limited as long as they have a polymerization inhibition ability or a function to inhibit polymerization. For example, phenothiazine, hydroquinone, p-methoxyphenol, p-benzoquinone, Naphthoquinone, phenanthraquinone, tolquinone, 2,5-diacetoxy-p-benzoquinone, 2,5-dicaproxy-p-benzoquinone, 2,5-acyloxy-p-benzoquinone, pt-butylcatechol, 2,5- Di-t-butylhydroquinone, p-tert-butylcatechol, mono-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, di-t-butylparacresol hydroquinone monomethyl ether, alpha naphthol, acetamidine acetate , Acetamidine sulfate, Phenyl hydride Gin hydrochloride, hydrazine hydrochloride, trimethylbenzylammonium chloride, laurylpyridinium chloride, cetyltrimethylammonium chloride, phenyltrimethylammonium chloride, trimethylbenzylammonium oxalate, di (trimethylbenzylammonium) oxalate, trimethylbenzylammonium malate, trimethylbenzyl Ammonium tartrate, trimethylbenzylammonium glycolate, phenyl-β-naphthylamine, parabenzylaminophenol, di-β-naphthylparaphenylenediamine, dinitrobenzene, trinitrotoluene, picric acid, cyclohexanone oxime, pyrogallol, tannic acid, resorcin, triethylamine Hydrochloride, dimethylaniline hydrochloride And dibutylamine hydrochloride salts.
These may be used alone or in combination of two or more.
Among these, hydroquinone, p-methoxyphenol, p-benzoquinone, naphthoquinone, phenanthraquinone, 2,5-diacetoxy-p-benzoquinone, 2,5-dicaproxy-p-benzoquinone, 2,5-acyloxy-p- Benzoquinone, pt-butylcatechol, 2,5-di-t-butylhydroquinone, p-tert-butylcatechol, mono-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, di-t-butyl -Paracresol hydroquinone monomethyl ether and phenothiazine are preferably used.
　通常、重合禁止剤は、本発明（Ｉ）～本発明（ＩＶ）の重合性組成物の総量に対し、０．０１～５質量％の添加量になるよう調整することができる。ただし、重合禁止剤の量は、成分１、成分２、成分３、成分４および成分６に予め重合禁止剤が含まれている場合には、これらに含まれている重合禁止剤を加味した値である。即ち、一般には、成分１、成分２、成分３、成分４および成分６に予め重合禁止剤が含まれているが、この重合禁止剤と新たに添加する重合禁止剤の総量を併せた量が、本発明（Ｉ）～本発明（ＩＶ）の重合性組成物の総量に対し、０．０１～５質量％の添加量になることを意味する。
　本発明（Ｉ）～本発明（ＩＶ）の重合性組成物の総量に対し、重合禁止剤が０．０１質量％未満の場合には、重合禁止能の不足により、配合物の保存安定性が不足する場合がある。また、本発明（Ｉ）～本発明（ＩＶ）の重合性組成物の総量に対し、重合禁止剤の量が５質量％より多い場合には、耐熱保存時の着色で色が濃くなったり、重合時の重合速度が低下したりする場合がある。 Usually, the polymerization inhibitor can be adjusted so as to be added in an amount of 0.01 to 5% by mass based on the total amount of the polymerizable composition of the present invention (I) to the present invention (IV). However, the amount of the polymerization inhibitor is a value obtained by adding the polymerization inhibitor contained in the component 1, component 2, component 3, component 4 and component 6 when the polymerization inhibitor is contained in advance. It is. That is, generally, a polymerization inhibitor is previously contained in component 1, component 2, component 3, component 4 and component 6, but the total amount of this polymerization inhibitor and the newly added polymerization inhibitor is This means that the added amount is 0.01 to 5% by mass based on the total amount of the polymerizable composition of the present invention (I) to the present invention (IV).
When the polymerization inhibitor is less than 0.01% by mass with respect to the total amount of the polymerizable composition of the present invention (I) to the present invention (IV), the storage stability of the compound is reduced due to insufficient polymerization inhibiting ability. There may be a shortage. In addition, when the amount of the polymerization inhibitor is more than 5% by mass relative to the total amount of the polymerizable composition of the present invention (I) to the present invention (IV), the color becomes darker due to coloring during heat-resistant storage, The polymerization rate at the time of polymerization may decrease.
　また、本発明（Ｉ）～本発明（ＩＶ）の重合性組成物には、酸化防止剤を添加することができかつ好ましい。
　酸化防止剤としては、特に限定されるものではないが、例えば、ペンタエリスリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、オクタデシル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、チオジエチレンビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンゼンプロパン酸の炭素数７～９のアルキルエステル、４，６－ビス（オクチルチオメチル）－ｏ－クレゾール、３，９－ビス［２－［３－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオニルオキシ］－１，１－ジメチルエチル］－２，４，８，１０－テトラオキサスピロ［５，５］－ウンデカン、２，２′－メチレンビス（６－ｔｅｒｔ－ブチル－４－メチルフェノール）、４，４′－ブチリデンビス（６－ｔｅｒｔ－ブチル－３－メチルフェノール）、４，４′－チオビス（２－ｔｅｒｔ－ブチル－５－メチルフェノール）、Ｎ，Ｎ′，Ｎ″－トリス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）イソシアヌレート、１，１，３－トリス（２－メチル－４－ヒドロキシ－５－ｔｅｒｔ－ブチルフェニル）ブタン、１，１－ビス（２－メチル－４－ヒドロキシ－５－ｔｅｒｔ－ブチルフェニル）ブタン、トリエチレングリコールビス（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオネート、ｎ－オクタデシル３－（４′－ヒドロキシ－３′，５′－ジ－ｔｅｒｔ－ブチルフェニル）プロピオネート等のフェノール系酸化防止剤を挙げることができる。これらの中で、好ましいものは、ペンタエリスリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、オクタデシル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、トリエチレングリコールビス（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオネート、ｎ－オクタデシル３－（４′－ヒドロキシ－３′，５′－ジ－ｔｅｒｔ－ブチルフェニル）プロピオネートであり、さらに好ましいのは、ペンタエリスリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、トリエチレングリコールビス（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオネート、ｎ－オクタデシル３－（４′－ヒドロキシ－３′，５′－ジ－ｔｅｒｔ－ブチルフェニル）プロピオネートであり、特に好ましいのは、トリエチレングリコールビス（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオネート、ｎ－オクタデシル３－（４′－ヒドロキシ－３′，５′－ジ－ｔｅｒｔ－ブチルフェニル）プロピオネートである。 In addition, an antioxidant can be added to the polymerizable compositions of the present invention (I) to the present invention (IV) and is preferable.
The antioxidant is not particularly limited. For example, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,5-di-tert-butyl-4 7-C9 alkyl ester of hydroxybenzenepropanoic acid, 4,6-bis (octylthiomethyl) -o-cresol, 3,9-bis [2- [3- (3-tert-butyl-4- Hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxa Pyro [5,5] -undecane, 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 4,4'-butylidenebis (6-tert-butyl-3-methylphenol), 4,4 '-Thiobis (2-tert-butyl-5-methylphenol), N, N', N "-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,1,3- Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,1-bis (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, triethylene glycol bis (3-tert -Butyl-4-hydroxy-5-methylphenyl) propionate, n-octadecyl 3- (4'-hydroxy-3 ', 5'-di-tert Mention may be made of phenolic antioxidants such as butylphenyl) propionate, among which pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] is preferred. , Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, triethylene glycol bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, n-octadecyl 3- (4'-hydroxy-3 ', 5'-di-tert-butylphenyl) propionate, more preferably pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate], triethylene glycol Bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, n-octadecyl 3- (4'-hydroxy-3 ', 5'-di-tert-butylphenyl) propionate, particularly preferred Is triethylene glycol bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, n-octadecyl 3- (4'-hydroxy-3 ', 5'-di-tert-butylphenyl) propionate is there.
　通常、酸化防止剤は、本発明（Ｉ）～本発明（ＩＶ）の重合性組成物の総量に対し、０．０１～５質量％の添加量になるよう調整することができる。ただし、酸化防止剤の量は、成分６等の他の成分に予め含まれている酸化防止剤を加味した値である。即ち、成分６等に予め酸化防止剤が含まれている場合があるとき、この酸化防止剤と新たに添加する酸化防止剤の総量を併せた量が、本発明（Ｉ）～本発明（ＩＶ）の重合性組成物の総量に対し、０．０１～５質量％の添加量になることを意味する。
　本発明（Ｉ）～本発明（ＩＶ）の重合性組成物の総量に対し、酸化防止剤が０．０１質量％未満の場合には、添加効果（即ち、酸化防止効果）が発現されない場合がある。また、本発明（Ｉ）～本発明（ＩＶ）の重合性組成物の総量に対し、重合禁止剤の量が５質量％より多い場合には、後述の本発明（Ｖ）の重合物あるいは後述の前記光学用粘着シートから、酸化防止剤が析出したり、ブリードしたりする場合がある。 Usually, the antioxidant can be adjusted so as to be added in an amount of 0.01 to 5% by mass relative to the total amount of the polymerizable composition of the present invention (I) to the present invention (IV). However, the amount of the antioxidant is a value in consideration of the antioxidant contained in the other components such as the component 6 in advance. That is, when an antioxidant is preliminarily contained in the component 6 or the like, the total amount of this antioxidant and the newly added antioxidant is the present invention (I) to the present invention (IV ) To 0.01 to 5% by mass based on the total amount of the polymerizable composition.
When the antioxidant is less than 0.01% by mass relative to the total amount of the polymerizable composition of the present invention (I) to the present invention (IV), the addition effect (that is, the antioxidant effect) may not be exhibited. is there. Further, when the amount of the polymerization inhibitor is more than 5% by mass based on the total amount of the polymerizable composition of the present invention (I) to the present invention (IV), the polymer of the present invention (V) described later or the later described From the optical pressure-sensitive adhesive sheet, an antioxidant may precipitate or bleed.
　次に、本発明（Ｖ）について説明する。
　本発明（Ｖ）は、本発明（Ｉ）～本発明（ＩＶ）の重合性組成物を重合して得られる重合物である。
　本発明（Ｖ）の重合物は、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプ、メタルハライドランプ、無電極ランプ、ＬＥＤ等を光源として、光重合開始剤が感光可能な光を、ガラスやプラスチックの基材を介して照射して、重合性組成物を重合することにより得られるものである。 Next, the present invention (V) will be described.
The present invention (V) is a polymer obtained by polymerizing the polymerizable composition of the present invention (I) to the present invention (IV).
The polymer of the present invention (V) is a low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, xenon lamp, metal halide lamp, electrodeless lamp, LED, etc. It is obtained by polymerizing the polymerizable composition by irradiation through a glass or plastic substrate.
　また、本発明（Ｖ）の重合物は、画像表示装置の画像表示部と、透光性の保護部との間に介在させる重合物層として使用される重合物である。この重合物の２５℃で周波数０．１ Ｈｚでの貯蔵弾性率が１×１０３～１×１０５Ｐａでなければならない。
　なお、「重合物の２５℃で周波数０．１Ｈｚでの貯蔵弾性率」とは、先に定義したとおりである。より好ましい貯蔵弾性率の値は１×１０４～１×１０５Ｐａである。
　重合物の貯蔵弾性率が１×１０３未満の場合には、高温多湿の環境下、あるいは高温の環境下で重合物が形状を維持できず、十分な密着力が得られない可能性がある。また、１×１０５Ｐａ以上の場合は、重合物が硬くなりすぎ、十分な密着性が得られない可能性がある。 Moreover, the polymer of this invention (V) is a polymer used as a polymer layer interposed between the image display part of an image display apparatus, and a translucent protection part. This polymer must have a storage modulus of 1 × 10 3 to 1 × 10 5 Pa at 25 ° C. and a frequency of 0.1 Hz.
The “storage modulus of the polymer at 25 ° C. and a frequency of 0.1 Hz” is as defined above. A more preferable value of the storage elastic modulus is 1 × 10 4 to 1 × 10 5 Pa.
When the storage elastic modulus of the polymer is less than 1 × 10 3 , the polymer cannot maintain its shape in a high-temperature and high-humidity environment or in a high-temperature environment, and sufficient adhesion may not be obtained. . Moreover, in the case of 1 × 10 5 Pa or more, the polymer becomes too hard and sufficient adhesion may not be obtained.
　図２に示すＯｎ－Ｃｅｌｌ型静電容量方式タッチパネル搭載表示装置中の画像表示部２と透光性の保護部３との間に充填される重合物（層）５ｂ、図３および図４に示すＩｎ－Ｃｅｌｌ型静電容量方式タッチパネル搭載表示装置中の画像表示部２と透光性の保護部３との間に充填される重合物（層）５ｂに本発明（Ｖ）の重合物を使用する場合には、本発明（Ｖ）の重合物の誘電率は高いことが望ましい。具体的には、２３℃、周波数１ＭＨｚ、印加電圧１００ｍＶの条件下での重合物の誘電率が５．０以上になる重合物を使用することが好ましく、さらに好ましくは、５．５以上になる重合物を使用することである。
　なお、「重合物の２３℃、周波数１ＭＨｚ、印加電圧１００ｍＶの条件で測定された誘電率」とは、２ｍｍ厚の試験片（重合物）を、２３℃の環境下で、Ａｇｉｌｅｎｔ　Ｔｅｃｈｎｏｌｏｇｉｅｓ社製のインピーダンスアナライザとして、４２９４Ａ　プレシジョン　インピーダンス・アナライザ　４０Ｈｚ－１１０ＭＨｚを使用し、テストフィクスチャとして、Ａｇｉｌｅｎｔ　Ｔｅｃｈｎｏｌｏｇｉｅｓ社製の１６４５１Ｂ　誘電体テスト・フィクスチャを使用して測定された、周波数１ＭＨｚ、印加電圧１００ｍＶの条件下での重合物の誘電率である。
　より好ましい誘電率の値は、上記条件で測定された誘電率が５．５以上であり、さらに好ましくは６．０以上であり、特に好ましくは６．１以上である。
　上記条件で測定された重合物の誘電率が５．０未満の場合には、静電容量型タッチパネルの感度が低下する場合がある。
　誘電率の上限は特に限定されないが、誘電率を高くすると極性が増し、その結果、耐水性が低くなる傾向にあり、耐水性が極端に損なわれないようにするためには誘電率は、４０以下であることが好ましく、さらに好ましくは２０以下、最も好ましくは１０以下である。 A polymer (layer) 5b filled between the image display unit 2 and the translucent protective unit 3 in the on-cell capacitive touch panel display shown in FIG. 2, and FIG. 3 and FIG. The polymer of the present invention (V) is applied to the polymer (layer) 5b filled between the image display unit 2 and the translucent protection unit 3 in the In-Cell type capacitive touch panel display shown. When used, it is desirable that the dielectric constant of the polymer of the present invention (V) is high. Specifically, it is preferable to use a polymer having a dielectric constant of 5.0 or more, more preferably 5.5 or more under the conditions of 23 ° C., frequency 1 MHz, and applied voltage 100 mV. It is to use a polymer.
“The dielectric constant of the polymer measured at 23 ° C., frequency 1 MHz, and applied voltage 100 mV” means that a 2 mm-thick test piece (polymer) is manufactured by Agilent Technologies in an environment of 23 ° C. 4294A Precision Impedance Analyzer 40Hz-110MHz is used as the impedance analyzer, and 16451B dielectric test fixture manufactured by Agilent Technologies is used as the test fixture, and the frequency is 1MHz and the applied voltage is 100mV. Is the dielectric constant of the polymer.
A more preferable dielectric constant value is a dielectric constant measured under the above conditions of 5.5 or more, more preferably 6.0 or more, and particularly preferably 6.1 or more.
When the dielectric constant of the polymer measured under the above conditions is less than 5.0, the sensitivity of the capacitive touch panel may decrease.
The upper limit of the dielectric constant is not particularly limited. However, when the dielectric constant is increased, the polarity increases, and as a result, the water resistance tends to decrease. In order to prevent the water resistance from being extremely impaired, the dielectric constant is 40 Or less, more preferably 20 or less, and most preferably 10 or less.
　前記重合組成物の成分１を重合して得られる重合物の誘電率を高くすることを考えると、ポリオールおよび１分子中に１つイソシアナト基を有する（メタ）アクリレートを必須原料成分に用いてウレタン（メタ）アクリレートを得る際、炭素数４～９のジオールから誘導される構造単位および炭素数４～１０のジカルボン酸から誘導される構造単位を含むポリエステル構造単位を有する（メタ）アクリロイル基含有高分子化合物を用いることが好ましい。なお、本明細書における「炭素数４～９のジオールから誘導される構造単位」とは、炭素数４～９のジオールの２つの水酸基のうち、少なくとも１つの水酸基中の水素が除かれた構造を意味する。また、本明細書における「炭素数４～１０のジカルボン酸から誘導される構造単位」とは、炭素数４～１０のジカルボン酸の２つのカルボキシル基（－Ｃ（＝Ｏ）ＯＨ）中のＯＨ基が除かれた構造を意味する。
　炭素数３以下のジオールのみを用いると、成分１を重合して得られる重合物の親水性が、高くなりすぎ、耐水性に弱くなる場合がある。また、炭素数１０以上のジオールのみを用いると、成分１を重合して得られる重合物の誘電率が低下する場合がある。
　また、炭素数３以下のジカルボン酸のみを使用すると、前記重合組成物の成分１を重合して得られる重合物の親水性が、高くなりすぎ、耐水性に弱くなる場合がある。また、炭素数１０以上のジカルボン酸のみを用いると、前記重合組成物の成分１を重合して得られる重合物の誘電率が低下する場合がある。
　炭素数４～９のジオールの具体例は、先に記載したとおりである。
　炭素数４～１０のジカルボン酸の具体例は、先に記載したとおりである。 Considering to increase the dielectric constant of the polymer obtained by polymerizing component 1 of the polymerization composition, a urethane using a polyol and (meth) acrylate having one isocyanato group in one molecule as an essential raw material component When (meth) acrylate is obtained, a (meth) acryloyl group-containing polymer having a structural unit derived from a diol having 4 to 9 carbon atoms and a structural unit derived from a dicarboxylic acid having 4 to 10 carbon atoms It is preferable to use molecular compounds. In the present specification, the “structural unit derived from a diol having 4 to 9 carbon atoms” means a structure in which hydrogen in at least one of the two hydroxyl groups of the diol having 4 to 9 carbon atoms is removed. Means. Further, in this specification, “structural unit derived from a dicarboxylic acid having 4 to 10 carbon atoms” means OH in two carboxyl groups (—C (═O) OH) of the dicarboxylic acid having 4 to 10 carbon atoms. It means a structure in which a group is removed.
When only a diol having 3 or less carbon atoms is used, the hydrophilicity of the polymer obtained by polymerizing component 1 may become too high and the water resistance may be weakened. In addition, when only a diol having 10 or more carbon atoms is used, the dielectric constant of a polymer obtained by polymerizing component 1 may decrease.
Moreover, when only C3 or less dicarboxylic acid is used, the hydrophilicity of the polymer obtained by superposing | polymerizing the component 1 of the said polymerization composition may become high too much, and may become weak in water resistance. Moreover, when only C10 or more dicarboxylic acid is used, the dielectric constant of the polymer obtained by superposing | polymerizing the component 1 of the said polymerization composition may fall.
Specific examples of the diol having 4 to 9 carbon atoms are as described above.
Specific examples of the dicarboxylic acid having 4 to 10 carbon atoms are as described above.
　また、本発明の重合物あるいは後述の光学用粘着シートの誘電率を高くするためには、成分４がメトキシエチル（メタ）アクリレート、ジエチレングリコールモノエチルエーテル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、３－メチル－３－オキセタニルメチル（メタ）アクリレート、１，４－ジオキサスピロ［４．５］デカ－２－イルメチル（メタ）アクリレート、（２－メチル－２－エチル－１，３－ジオキソラン－４－イル）メチル（メタ）アクリレート等の分子中にエーテル結合を有する（メタ）アクリロイル基含有化合物、α－メタクリロキシ－γ－ブチロラクトン、α－アクリロキシ－γ－ブチロラクトン等の環状エステルを有する（メタ）アクリロイル基含有化合物であることが好ましく、より好ましいものとしては、メトキシエチル（メタ）アクリレート、ジエチレングリコールモノエチルエーテル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、３－メチル－３－オキセタニルメチル（メタ）アクリレート、１，４－ジオキサスピロ［４．５］デカ－２－イルメチル（メタ）アクリレート、（２－メチル－２－エチル－１，３－ジオキソラン－４－イル）メチル（メタ）アクリレート等の分子中にエーテル結合を有する（メタ）アクリロイル基含有化合物であり、特に好ましいものとしては、ジエチレングリコールモノエチルエーテル（メタ）アクリレート、３－メチル－３－オキセタニルメチル（メタ）アクリレート、１，４－ジオキサスピロ［４．５］デカ－２－イルメチル（メタ）アクリレート、（２－メチル－２－エチル－１，３－ジオキソラン－４－イル）メチル（メタ）アクリレートである。 In order to increase the dielectric constant of the polymer of the present invention or the optical pressure-sensitive adhesive sheet described later, Component 4 is methoxyethyl (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, phenoxyethyl (meth) acrylate, 3-methyl-3-oxetanylmethyl (meth) acrylate, 1,4-dioxaspiro [4.5] dec-2-ylmethyl (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolane-4- (Il) (meth) acryloyl group having a cyclic ester such as (meth) acryloyl group-containing compound having an ether bond in the molecule such as methyl (meth) acrylate, α-methacryloxy-γ-butyrolactone, α-acryloxy-γ-butyrolactone Preferably it is a contained compound, more preferred Examples include methoxyethyl (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, phenoxyethyl (meth) acrylate, 3-methyl-3-oxetanylmethyl (meth) acrylate, 1,4-dioxaspiro [4.5] (Meth) acryloyl group-containing compounds having an ether bond in the molecule, such as deca-2-ylmethyl (meth) acrylate and (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate Particularly preferred are diethylene glycol monoethyl ether (meth) acrylate, 3-methyl-3-oxetanylmethyl (meth) acrylate, 1,4-dioxaspiro [4.5] dec-2-ylmethyl (meth) acrylate , (2-Methyl-2- Ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate.
　２５℃における、本発明（Ｖ）の重合物の屈折率は、１．４５～１．５５であることが好ましく、さらに好ましくは、１．４８～１．５２である。２５℃における屈折率が、１．４５未満あるいは１．５５より大きくなる場合、保護部の材質である光学ガラス等の屈折率に比べて低くなりすぎるので、表示部から保護部に至る間の界面における屈折率差がやや大きくなり、表示部から映像光の散乱および減衰がやや大きくなる場合がある。 The refractive index of the polymer of the present invention (V) at 25 ° C. is preferably 1.45 to 1.55, and more preferably 1.48 to 1.52. When the refractive index at 25 ° C. is less than 1.45 or larger than 1.55, it is too low compared to the refractive index of the optical glass or the like that is the material of the protective part, so the interface between the display part and the protective part In some cases, the difference in the refractive index of the image becomes slightly larger, and the scattering and attenuation of the image light from the display portion become slightly larger.
　さらに本発明（Ｖ）の重合物の重合時の体積収縮率が、３．５％以下であることが好ましく、さらに好ましくは、２．７％以下であり、もっとも好ましいのは２．３％以下になる。これにより、重合性組成物が重合する際に重合物層に蓄積される内部応力を低減させることができ、重合物層５ａとタッチパネル７または保護部３との界面や、重合物層５ｂとタッチパネル７、表示部２あるいは保護部３との界面に歪みができることを防止できる。したがって、重合性組成物を、タッチパネル７と保護部３との間、タッチパネル７と表示部２との間、あるいは表示部２と保護部３との間に介在させ、その重合性組成物を重合させた場合に、重合物層５と表示部２、保護部３、タッチパネル７との界面で生じる光の散乱を低減させることができ、表示画像の輝度を高めると共に、視認性を向上させることができる。
　重合時の体積収縮率が、３．５％よりも大きい場合には、重合性組成物が重合する際に重合物に蓄積される内部応力が大きくなりすぎ、重合物層５ａあるいは５ｂと、それらに接している表示部２、保護部３またはタッチパネル７との界面に歪みができてしまう場合がある。本発明（Ｖ）の重合物の重合時の体積収縮率を、３．５％以下にするためには、成分１を本発明（Ｉ）～本発明（ＩＶ）の重合性組成物の総量に対し、１０～３０質量％含むようにすることが好ましい。また、さらに好ましくは、成分１を本発明（Ｉ）～本発明（ＩＶ）の重合性組成物の総量に対し、１０～４０質量％含むようにしたうえで、成分３と成分４の総量が本発明（ＩＶ）の必須成分である成分１、成分３、成分４、成分５および成分６を合わせた総量に対し、１～２５質量％含むようにすることが好ましい。 Furthermore, the volume shrinkage during polymerization of the polymer of the present invention (V) is preferably 3.5% or less, more preferably 2.7% or less, and most preferably 2.3% or less. become. Thereby, the internal stress accumulated in the polymer layer when the polymerizable composition is polymerized can be reduced, and the interface between the polymer layer 5a and the touch panel 7 or the protective part 3, or the polymer layer 5b and the touch panel. 7. It is possible to prevent the interface with the display unit 2 or the protection unit 3 from being distorted. Therefore, the polymerizable composition is interposed between the touch panel 7 and the protection unit 3, between the touch panel 7 and the display unit 2, or between the display unit 2 and the protection unit 3, and the polymerizable composition is polymerized. In this case, the scattering of light generated at the interface between the polymer layer 5 and the display unit 2, the protection unit 3, and the touch panel 7 can be reduced, and the brightness of the display image can be increased and the visibility can be improved. it can.
When the volume shrinkage during polymerization is larger than 3.5%, the internal stress accumulated in the polymer when the polymerizable composition is polymerized becomes too large, and the polymer layer 5a or 5b and those May be distorted at the interface with the display unit 2, the protection unit 3, or the touch panel 7 in contact with the touch panel. In order to reduce the volume shrinkage during polymerization of the polymer of the present invention (V) to 3.5% or less, the component 1 is added to the total amount of the polymerizable composition of the present invention (I) to the present invention (IV). On the other hand, it is preferable to contain 10 to 30% by mass. More preferably, the component 1 is contained in an amount of 10 to 40% by mass based on the total amount of the polymerizable composition of the present invention (I) to the present invention (IV), and the total amount of the component 3 and the component 4 is It is preferable to contain 1 to 25% by mass with respect to the total amount of component 1, component 3, component 4, component 5, and component 6, which are essential components of the present invention (IV).
　また、本発明（Ｖ）の重合物を２枚のガラス間に２００μｍ厚で介在させ、積層物を作成し、該積層物を５００ｍｍ／分でガラスに対して垂直方向に剥離させた際の重合物とガラスの破断強度が、２０Ｎ／ｃｍ２以上であることが望ましい。
　本明細書に記載の「積層物」とは、厚さ０．７ｍｍの２枚の光学ガラス（コーニング社製、商品名：イーグルＸＧ（登録商標））の間に重合性組成物を介在させ、前記光学ガラス越しに、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプ、メタルハライドランプ、無電極ランプ、ＬＥＤ等を光源として、光重合開始剤が感光可能な光を照射することにより得られる、厚さ２００μｍの重合物を作成して得られる重合物層のいずれかと、前記重合物層の外側に存在するガラスからなる積層物のことである。また、重合物層の外側の２枚のガラスに挟まれた部分には、スペーサ、ガスケット、あるいは封止剤等が全く含まれていないものである。
　さらに、「該積層物を５００ｍｍ／分でガラスに対して垂直方向に剥離させた際の重合物とガラスの破断強度が、２０Ｎ／ｃｍ２以上であること」とは外側のガラス面（両面）に、それぞれ、引張試験機（株式会社島津製作所製、ＥＺ　Ｔｅｓｔ／ＣＥ）のチャック部で挟み込むことができるように、両面テープを用いてプラスチック治具を貼り付け、その後、引張試験機（株式会社島津製作所製、ＥＺ　Ｔｅｓｔ／ＣＥ）に、プラスチック治具が貼り付けられた重合物膜付の２枚のガラスを取り付け、５００ｍｍ／ｍｉｎの速度で両面のガラスを剥がす方向に引っ張り、ガラスへの密着性を評価した際の重合物とガラスの破断強度が、２０Ｎ／ｃｍ２以上であるという意味である。
　上記条件で測定された重合物とガラスの破断強度が、２０Ｎ／ｃｍ２未満であると、画像表示部、透光性の保護部およびその間に重合物層が介在する画像表示装置を製造した際、画像表示部と重合物層との間、または透光性の保護部と重合物層との間に剥がれが生じる可能性がある。 In addition, the polymerized product of the present invention (V) was interposed between two glasses at a thickness of 200 μm to form a laminate, and the polymerization was performed when the laminate was peeled in a direction perpendicular to the glass at 500 mm / min It is desirable that the breaking strength between the object and the glass is 20 N / cm 2 or more.
The “laminate” described in the present specification includes a polymerizable composition interposed between two optical glasses having a thickness of 0.7 mm (manufactured by Corning, trade name: Eagle XG (registered trademark)), By irradiating light that can be sensitized by the photopolymerization initiator through the optical glass, using a low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, xenon lamp, metal halide lamp, electrodeless lamp, LED, etc. as a light source It is a laminate composed of any of the polymer layers obtained by preparing a polymer having a thickness of 200 μm and glass existing outside the polymer layer. In addition, the portion sandwiched between the two sheets of glass outside the polymer layer does not contain any spacers, gaskets, or sealants.
Furthermore, “the breaking strength of the polymer and the glass when the laminate is peeled in the direction perpendicular to the glass at 500 mm / min is 20 N / cm 2 or more” means the outer glass surface (both sides). A plastic jig was affixed using a double-sided tape so that it could be sandwiched between chucks of a tensile tester (manufactured by Shimadzu Corporation, EZ Test / CE). Attach two glass with polymer film with plastic jig attached to Shimadzu EZ Test / CE, and pull the glass on both sides at a speed of 500mm / min. This means that the breaking strength of the polymer and the glass when the property is evaluated is 20 N / cm 2 or more.
When the breaking strength of the polymer and glass measured under the above conditions is less than 20 N / cm 2 , an image display unit, a translucent protective unit, and an image display device in which a polymer layer is interposed therebetween are produced. Further, peeling may occur between the image display portion and the polymer layer, or between the light-transmitting protective portion and the polymer layer.
　また、上記条件で測定された重合物とガラスの破断強度が、２０Ｎ／ｃｍ２以上であるためには、成分１を本発明（Ｉ）～本発明（ＩＶ）の重合性組成物の総量に対し、１０～４０質量％含むようにすることが好ましい。さらに好ましくは、成分５の使用量を、本発明（ＩＶ）の必須成分である成分１、成分３、成分４、成分５および成分６を合わせた総量に対して、５～３０質量％にし、成分６の使用量を、本発明（ＩＶ）の必須成分である成分１、成分３、成分４、成分５および成分６を合わせた総量に対して、４０～６０質量％にすることが好ましい。 In addition, in order for the breaking strength of the polymer and glass measured under the above conditions to be 20 N / cm 2 or more, component 1 is added to the total amount of the polymerizable composition of the present invention (I) to the present invention (IV). On the other hand, the content is preferably 10 to 40% by mass. More preferably, the amount of component 5 used is 5 to 30% by mass based on the total amount of component 1, component 3, component 4, component 5 and component 6 as essential components of the present invention (IV), The amount of component 6 used is preferably 40 to 60% by mass based on the total amount of component 1, component 3, component 4, component 5 and component 6 as essential components of the present invention (IV).
　さらに本発明（Ｖ）の重合物をガラス、樹脂板およびその間に２００μｍ厚で介在させ積層物を作成し、６０℃、９０％ＲＨの環境下に７２時間保存し、２３℃、５０％ＲＨの環境下にとりだして２３℃、５０％ＲＨの環境下で４８時間保存した後、前記重合物とガラス間、および／または前記重合物と樹脂板間に剥がれが発生しないことが好ましい。
　本明細書に記載の「該重合物をガラス、樹脂板およびその間に２００μｍ厚で介在させ積層物を作成」とは、厚さ０．７ｍｍの１枚の光学ガラス（コーニング社製、商品名：イーグルＸＧ（登録商標））と樹脂板（三菱ガス化学社製、商品名：ＭＲ－８５、または三菱レイヨン社製、商品名：アクリライト　ＭＲ－２００）の間に重合性組成物を介在させ、前記光重合開始剤が感光可能な光を照射することにより得られる、厚さ２００μｍの重合物を作成して得られる重合物層と、前記重合物層の外側に存在するガラスと前記樹脂板からなる積層物を形成することである。また、重合物層の外側のガラスと前記樹脂板に挟まれた部分には、スペーサ、ガスケット、あるいは封止剤等が全く含まれていないものである。
　また、「６０℃、９０％ＲＨの環境下に７２時間保存し、２３℃、５０％ＲＨの環境下にとりだして２３℃、５０％ＲＨの環境下で４８時間保存した後、前記重合物とガラス間、または前記重合物と樹脂板間に剥がれが発生しないこと」とは、上記積層物を６０℃、９０％ＲＨの環境下に７２時間保存し、２３℃、５０％ＲＨの環境下にとりだした後、２３℃、５０％ＲＨの環境下で４８時間保存した後、前記重合物とガラス間および／または前記重合物と樹脂板間に剥がれが発生しないということである。
　上記積層物を６０℃、９０％ＲＨの環境下に７２時間保存し、２３℃、５０％ＲＨの環境下にとりだした後、２３℃、５０％ＲＨの環境下で４８時間保存した後、前記重合物とガラス間、または前記重合物と樹脂板間に剥がれが発生すると、本発明（Ｖ）の重合物を画像表示装置の画像表示部と透光性の保護部との間に介在させる重合物層として使用した際、剥がれてしまう可能性がある。 Further, a laminate was prepared by interposing the polymer of the present invention (V) with glass, a resin plate and a thickness of 200 μm between them, and stored in an environment of 60 ° C. and 90% RH for 72 hours, and at 23 ° C. and 50% RH. It is preferable that no peeling occurs between the polymer and the glass and / or between the polymer and the resin plate after storage for 48 hours in an environment of 23 ° C. and 50% RH.
As described in this specification, “a laminate is prepared by interposing the polymer with a glass, a resin plate and a thickness of 200 μm therebetween” refers to one optical glass having a thickness of 0.7 mm (trade name: manufactured by Corning). Eagle XG (registered trademark)) and a resin plate (Mitsubishi Gas Chemical Co., Ltd., trade name: MR-85, or Mitsubishi Rayon Co., Ltd., trade name: Acrylite MR-200) From the polymer layer obtained by producing a polymer having a thickness of 200 μm, which is obtained by irradiating light capable of photosensitizing the photopolymerization initiator, the glass existing outside the polymer layer, and the resin plate Forming a laminate. Further, the portion sandwiched between the glass outside the polymer layer and the resin plate does not contain any spacers, gaskets or sealants.
In addition, after being stored in an environment of 60 ° C. and 90% RH for 72 hours, taken out in an environment of 23 ° C. and 50% RH and stored in an environment of 23 ° C. and 50% RH for 48 hours, “No peeling occurs between the glass or between the polymer and the resin plate” means that the laminate is stored in an environment of 60 ° C. and 90% RH for 72 hours, and in an environment of 23 ° C. and 50% RH. After taking out, after being stored for 48 hours in an environment of 23 ° C. and 50% RH, no peeling occurs between the polymer and glass and / or between the polymer and resin plate.
The laminate was stored in an environment of 60 ° C. and 90% RH for 72 hours, taken out in an environment of 23 ° C. and 50% RH, and then stored in an environment of 23 ° C. and 50% RH for 48 hours. When peeling occurs between the polymer and the glass or between the polymer and the resin plate, polymerization is performed by interposing the polymer of the present invention (V) between the image display part of the image display device and the translucent protective part. When used as a physical layer, it may peel off.
　次に、本発明（ＶＩ）および本発明（ＶＩＩ）について説明する。
　本発明（ＶＩ）は、画像表示装置の画像表示部と透光性の保護部との間に介在させる重合物層として使用される光学用粘着シートを製造するための重合性組成物であって、該重合性組成物が本発明（Ｉ）～本発明（ＩＶ）の重合性組成物であることを特徴とする重合性組成物である。
　本発明（Ｉ）～本発明（ＩＶ）の重合性組成物を原料に使用して、前記光学用粘着シートを製造することができる。
　本発明（ＶＩＩ）は、本発明（ＶＩ）の重合性組成物を塗布し、光重合開始剤が感光可能な光を該重合性組成物に照射して、重合させることによって得られる、厚さ１０～１０００μｍの重合物層を有する光学用粘着シートである。 Next, the present invention (VI) and the present invention (VII) will be described.
The present invention (VI) is a polymerizable composition for producing an optical pressure-sensitive adhesive sheet used as a polymer layer interposed between an image display part and a translucent protective part of an image display device. The polymerizable composition is a polymerizable composition according to the present invention (I) to the present invention (IV).
Using the polymerizable composition of the present invention (I) to the present invention (IV) as a raw material, the optical pressure-sensitive adhesive sheet can be produced.
The present invention (VII) has a thickness obtained by applying the polymerizable composition of the present invention (VI), irradiating the polymerizable composition with light capable of being photosensitized by the photopolymerization initiator, and polymerizing the polymerizable composition. An optical pressure-sensitive adhesive sheet having a polymer layer of 10 to 1000 μm.
　前記光学用粘着シートは、本発明（Ｖ）の重合物を、重合した条件と同様の光を照射して重合組成物を重合することにより得られる。 The optical pressure-sensitive adhesive sheet can be obtained by polymerizing a polymerization composition by irradiating light similar to the conditions under which the polymer of the present invention (V) is polymerized.
　前記光学用粘着シートは、シートの両面が粘着面（粘着剤層表面）となっている両面粘着シートであってもよいし、シートの片面のみが粘着面（粘着剤層表面）となっている片面粘着シートであってもよい。中でも、２つの部材同士を貼り合わせる観点からは、両面粘着シートであることが好ましい。なお、本明細書において、「粘着シート」という場合には、テープ状のもの、即ち、「粘着テープ」も含まれるものとする。 The optical pressure-sensitive adhesive sheet may be a double-sided pressure-sensitive adhesive sheet in which both surfaces of the sheet are pressure-sensitive adhesive surfaces (pressure-sensitive adhesive layer surface), or only one surface of the sheet is a pressure-sensitive adhesive surface (pressure-sensitive adhesive layer surface). A single-sided adhesive sheet may be sufficient. Especially, it is preferable that it is a double-sided adhesive sheet from a viewpoint of bonding two members together. In the present specification, the term “adhesive sheet” includes a tape-shaped material, that is, “adhesive tape”.
　前記光学用粘着シートは、基材（基材層）を有しない、いわゆる「基材レスタイプ」の光学用粘着シート（以下、「基材レス光学用粘着シート」と称する場合がある。）であってもよいし、基材を有するタイプの光学用粘着シートであってもよい。上記基材レス光学用粘着シートとしては、例えば、本発明の重合物からなる重合物層のみからなる両面粘着シートや、本発明の重合物からなる重合物層と該重合物層以外の粘着剤層からなる両面粘着シート等が挙げられる。基材を有するタイプの粘着シートとしては、基材の少なくとも片面側に本発明の重合物からなる重合物層を有していればよい。中でも、光学用粘着シートの薄膜化、透明性などの光学物性向上の観点からは、基材レス光学用粘着シート（基材レス両面光学用粘着シート）が好ましく、より好ましくは、本発明の重合物からなる重合物層のみからなる基材レス両面の光学用粘着シートである。なお、上記の「基材（基材層）」には、粘着シートの使用（貼付）時に剥離されるセパレータ（剥離ライナー）は含まない。 The optical pressure-sensitive adhesive sheet is a so-called “baseless-less type” optical pressure-sensitive adhesive sheet (hereinafter sometimes referred to as a “baseless-less optical pressure-sensitive adhesive sheet”) that does not have a base material (base material layer). It may also be an optical pressure-sensitive adhesive sheet having a base material. Examples of the substrate-less optical pressure-sensitive adhesive sheet include, for example, a double-sided pressure-sensitive adhesive sheet composed only of the polymer layer composed of the polymer of the present invention, and a polymer layer composed of the polymer of the present invention and a pressure-sensitive adhesive other than the polymer layer. Examples thereof include a double-sided pressure-sensitive adhesive sheet composed of layers. As a type of pressure-sensitive adhesive sheet having a substrate, it is only necessary to have a polymer layer made of the polymer of the present invention on at least one side of the substrate. Among them, from the viewpoint of reducing the thickness of the optical pressure-sensitive adhesive sheet and improving the optical properties such as transparency, a pressure-sensitive adhesive sheet for baseless optics (pressure-sensitive adhesive sheet for baseless double-sided optics) is preferable, and more preferably polymerization of the present invention. It is a base-less double-sided optical pressure-sensitive adhesive sheet consisting only of a polymer layer made of a product. The “base material (base material layer)” does not include a separator (release liner) that is peeled off when the pressure-sensitive adhesive sheet is used (attached).
　前記光学用粘着シートの重合物層の厚みは、１０～１０００μｍであり、好ましくは、２０～７００μｍであり、さらに好ましくは、３０～５００μｍである。重合物層の厚さが１０００μｍを超えると、塗工時の巻き取り時にシワが生じたり、加湿により白濁化しやすくなる場合がある。重合物層の厚さが１０μｍ未満では、重合物層が薄いために応力分散ができなくなり、剥がれが生じやすくなる場合がある。 The thickness of the polymer layer of the optical pressure-sensitive adhesive sheet is 10 to 1000 μm, preferably 20 to 700 μm, and more preferably 30 to 500 μm. If the thickness of the polymer layer exceeds 1000 μm, wrinkles may occur during winding during coating, or white turbidity may be easily caused by humidification. When the thickness of the polymer layer is less than 10 μm, since the polymer layer is thin, the stress cannot be dispersed and peeling may easily occur.
　前記光学用粘着シートは、画像表示装置の画像表示部と、透光性の保護部との間に介在させる重合物層として使用されるものである。例えば、図２に示すＯｎ－Ｃｅｌｌ型静電容量方式タッチパネル搭載表示装置中の画像表示部２と透光性の保護部３との間に充填される重合物（層）５ｂ、図３および図４に示すＩｎ－Ｃｅｌｌ型静電容量方式タッチパネル搭載表示装置中の画像表示部２と透光性の保護部３との間に充填される重合物（層）５ｂに前記光学用粘着シートを使用する場合には、前記光学用粘着シートの誘電率は高いことが望ましい。具体的には、先に本発明（Ｖ）で誘電率について述べた物性値と効果と同様である。 The optical pressure-sensitive adhesive sheet is used as a polymer layer interposed between an image display part of an image display device and a translucent protective part. For example, a polymer (layer) 5b filled between the image display unit 2 and the translucent protection unit 3 in the on-cell capacitive touch panel display shown in FIG. 2, FIG. 3 and FIG. The optical pressure-sensitive adhesive sheet is used for the polymer (layer) 5b filled between the image display unit 2 and the translucent protection unit 3 in the display device mounted with the In-Cell capacitive touch panel shown in FIG. In that case, it is desirable that the optical adhesive sheet has a high dielectric constant. Specifically, it is the same as the physical property values and effects described above for the dielectric constant in the present invention (V).
　また、前記光学用粘着シートは２５℃で周波数０．１Ｈｚでの貯蔵弾性率が１×１０３～１×１０５Ｐａでなければならない。
　本明細書に記載の「光学用粘着シートの２５℃で周波数０．１Ｈｚでの貯蔵弾性率」とは、先に定義したとおりであり、先に本発明（Ｖ）で貯蔵弾性率について述べた物性値と効果と同様である。 The optical pressure-sensitive adhesive sheet must have a storage elastic modulus of 1 × 10 3 to 1 × 10 5 Pa at 25 ° C. and a frequency of 0.1 Hz.
“The storage elastic modulus of the optical pressure-sensitive adhesive sheet at 25 ° C. and a frequency of 0.1 Hz” described in the present specification is as defined above, and the storage elastic modulus was previously described in the present invention (V). The physical property values and effects are the same.
　２５℃における、前記光学用粘着シートの屈折率は、先に本発明（Ｖ）で屈折率について述べた物性値と効果と同様である。 The refractive index of the optical pressure-sensitive adhesive sheet at 25 ° C. is the same as the physical properties and effects described above for the refractive index in the present invention (V).
　光学用粘着シートの重合物層の形成方法は、公知あるいは慣用の重合物層の形成方法を用いることが可能であり、特に限定されないが、本発明の重合性組成物のようなアクリロイル基を有する重合性組成物を重合させて、光学用粘着シートの重合物層を形成させる場合には、例えば、以下の（１）～（３）などの方法が挙げることができる。
（１）光重合開始剤を含むアクリロイル基を有する重合性組成物に、必要に応じて添加剤を含む組成物を、基材またはセパレータ（剥離ライナー）上に塗布（塗工）し、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプ、メタルハライドランプ、無電極ランプ、ＬＥＤ等の光源を用いて、光重合開始剤が感光可能な光を照射して、該組成物を重合することにより重合物層を形成する。
（２）光重合開始剤を含むアクリロイル基を有する重合性組成物に、さらに溶剤、必要に応じて添加剤を含む組成物（溶液）を、基材またはセパレータ（剥離ライナー）上に塗布（塗工）し、乾燥および低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプ、メタルハライドランプ、無電極ランプ、ＬＥＤ等の光源を用いて、光重合開始剤が感光可能な光を照射して、該組成物を重合することにより重合物層を形成する。
（３）上記（１）で形成した重合物層をさらに乾燥させる。 The method for forming the polymer layer of the optical pressure-sensitive adhesive sheet may be a known or conventional method for forming a polymer layer, and is not particularly limited, but has an acryloyl group as in the polymerizable composition of the present invention. In the case where the polymerizable composition is polymerized to form the polymer layer of the optical pressure-sensitive adhesive sheet, for example, the following methods (1) to (3) can be mentioned.
(1) A polymerizable composition having an acryloyl group containing a photopolymerization initiator is coated (coated) with a composition containing additives as necessary on a substrate or a separator (release liner), and a low-pressure mercury lamp , Using a light source such as a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a xenon lamp, a metal halide lamp, an electrodeless lamp, and an LED, the photopolymerization initiator irradiates light capable of being polymerized to polymerize the composition. Thus, a polymer layer is formed.
(2) A polymerizable composition having an acryloyl group containing a photopolymerization initiator and a composition (solution) further containing a solvent and, if necessary, an additive are applied (coated) on a substrate or a separator (release liner). And then irradiate the photopolymerization initiator with sensitive light using a light source such as a low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, xenon lamp, metal halide lamp, electrodeless lamp, or LED. Then, a polymer layer is formed by polymerizing the composition.
(3) The polymer layer formed in (1) above is further dried.
　なお、上記の重合物層の形成方法における塗布（塗工）には、公知のコーティング法を用いることが可能であり、慣用のコーター、例えば、グラビヤロールコーター、リバースロールコーター、キスロールコーター、ディップロールコーター、バーコーター、ナイフコーター、スプレーコーター、コンマコーター、ダイレクトコーターなどを用いることができる。 In addition, a known coating method can be used for coating (coating) in the method for forming the polymer layer, and a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip coater can be used. A roll coater, bar coater, knife coater, spray coater, comma coater, direct coater or the like can be used.
　前記光学用粘着シートが基材を有する場合、基材としては、特に制限されないが、プラスチックフィルム、反射防止（ＡＲ）フィルム、偏光板、位相差板などの各種光学フィルムが挙げられる。上記プラスチックフィルムなどの素材としては、例えば、ポリエチレンテレフタレート（ＰＥＴ）等のポリエステル系樹脂、ポリメチルメタクリレート（ＰＭＭＡ）等のアクリル系樹脂、ポリカーボネート、トリアセチルセルロース（ＴＡＣ）、ポリサルフォン、ポリアリレート、ポリイミド、ポリ塩化ビニル、ポリ酢酸ビニル、ポリエチレン、ポリプロピレン、エチレン－プロピレン共重合体、商品名「アートン（環状オレフィン系ポリマー；ＪＳＲ株式会社製）」、商品名「ゼオノア（環状オレフィン系ポリマー；日本ゼオン株式会社製）」等の環状オレフィン系ポリマーなどのプラスチック材料が挙げられる。なお、プラスチック材料は単独で、または２種以上を組み合わせて使用することができる。また、上記の「基材」とは、光学用粘着シートを被着体（光学部材等）に使用（貼付）する際には、粘着剤層とともに被着体に貼付される部分である。粘着シートの使用時（貼付時）に剥離されるセパレータ（剥離ライナー）は「基材」には含まない。 When the optical pressure-sensitive adhesive sheet has a substrate, the substrate is not particularly limited, and examples thereof include various optical films such as a plastic film, an antireflection (AR) film, a polarizing plate and a retardation plate. Examples of the material such as the plastic film include, for example, polyester resins such as polyethylene terephthalate (PET), acrylic resins such as polymethyl methacrylate (PMMA), polycarbonate, triacetyl cellulose (TAC), polysulfone, polyarylate, polyimide, Polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, ethylene-propylene copolymer, trade name “ARTON (cyclic olefin polymer; manufactured by JSR Corporation)”, trade name “ZEONOR (cycloolefin polymer; ZEON CORPORATION) A plastic material such as a cyclic olefin polymer. In addition, a plastic material can be used individually or in combination of 2 or more types. In addition, the above-mentioned “base material” is a portion that is attached to the adherend together with the adhesive layer when the optical adhesive sheet is used (attached) to the adherend (optical member or the like). A separator (release liner) that is peeled off when the adhesive sheet is used (attached) is not included in the “base material”.
　上記の中でも、基材としては、透明基材が好ましい。上記「透明基材」とは、例えば、可視光波長領域における全光線透過率（ＪＩＳ　Ｋ７３６１に準じる）が８５％以上である基材が好ましく、さらに好ましくは８８％以上である基材をいう。また、基材のヘーズ（ＪＩＳ　Ｋ７３６１に準じる）は、例えば、１．５％以下が好ましく、より好ましくは１．０％以下である。上記透明基材としては、ＰＥＴフィルムや、商品名「アートン」、商品名「ゼオノア」などの無配向フィルムなどが挙げられる。 Among these, a transparent substrate is preferable as the substrate. The “transparent substrate” means, for example, a substrate having a total light transmittance (according to JIS K7361) of 85% or more in the visible light wavelength region, more preferably 88% or more. The haze of the substrate (according to JIS K7361) is, for example, preferably 1.5% or less, and more preferably 1.0% or less. Examples of the transparent substrate include PET films and non-oriented films such as trade names “Arton” and trade names “Zeonoa”.
　上記基材の厚さは、特に限定されず、例えば、１２～７５μｍが好ましい。なお、上記基材は単層および複層のいずれの形態を有していてもよい。また、基材表面には、例えば、コロナ放電処理、プラズマ処理等の物理的処理、下塗り処理等の化学的処理などの公知慣用の表面処理が適宜施されていてもよい。 The thickness of the substrate is not particularly limited and is preferably 12 to 75 μm, for example. In addition, the said base material may have any form of a single layer and a multilayer. The surface of the substrate may be appropriately subjected to known and conventional surface treatments such as physical treatment such as corona discharge treatment and plasma treatment, and chemical treatment such as undercoating treatment.
　前記光学用粘着シートが基材を有する場合、基材としては各種の機能性フィルムを用いることもできる。その場合、本発明の粘着シートは、機能性フィルムの少なくとも片面に本発明の粘着剤層を有する粘着型機能性フィルムとなる。上記の機能性フィルムとしては、特に限定されないが、例えば、光学的機能性（偏光性、光屈折性、光反射性、光透過性、光吸収性、光回折性、旋光性、視認性など）を有するフィルム、導電性を有するフィルム（ＩＴＯフィルムなど）、紫外線カット性を有するフィルム、ハードコート性（耐傷付き性）を有するフィルム等が挙げられる。さらに具体的には、ハードコートフィルム（ＰＥＴフィルムなどのプラスチックフィルムの少なくとも片面にハードコート処理が施されたフィルム）、偏光フィルム、波長板、位相差フィルム、光学補償フィルム、輝度向上フィルム、導光板、反射フィルム、反射防止フィルム、透明導電フィルム（ＩＴＯフィルムなど）、意匠フィルム、装飾フィルム、表面保護フィルム、プリズム、カラーフィルターなどが挙げられる。なお、上記の「板」および「フィルム」は、それぞれ板状、フィルム状、シート状等の形態を含むものとし、たとえば、「偏光フィルム」は、「偏光板」、「偏光シート」も含むものとする。また、「機能性フィルム」は「機能性板」、「機能性シート」を含むものとする。 When the optical pressure-sensitive adhesive sheet has a base material, various functional films can be used as the base material. In that case, the pressure-sensitive adhesive sheet of the present invention becomes a pressure-sensitive adhesive functional film having the pressure-sensitive adhesive layer of the present invention on at least one side of the functional film. Although it does not specifically limit as said functional film, For example, optical functionality (polarizability, photorefractive property, light reflectivity, light transmittance, light absorption property, light diffraction property, optical rotation property, visibility, etc.) A film having conductivity, a film having conductivity (such as an ITO film), a film having ultraviolet cutting property, a film having hard coat properties (scratch resistance), and the like. More specifically, a hard coat film (a film on which at least one surface of a plastic film such as a PET film is hard-coated), a polarizing film, a wave plate, a retardation film, an optical compensation film, a brightness enhancement film, a light guide plate , Reflective film, antireflection film, transparent conductive film (such as ITO film), design film, decorative film, surface protective film, prism, color filter and the like. In addition, said "plate" and "film" shall include forms, such as plate shape, film shape, and sheet shape, respectively, for example, "polarizing film" shall also include "polarizing plate" and "polarizing sheet". The “functional film” includes “functional plate” and “functional sheet”.
　また、前記光学用粘着シートが、他の粘着剤層を有する場合、他の粘着剤層としては、特に制限されず、例えば、ウレタン系粘着剤、アクリル系粘着剤、ゴム系粘着剤、シリコーン系粘着剤、ポリエステル系粘着剤、ポリアミド系粘着剤、エポキシ系粘着剤、ビニルアルキルエーテル系粘着剤、フッ素系粘着剤などの公知の粘着剤から形成された公知慣用の粘着剤層が挙げられる。上記粘着剤は単独で、または２種以上を組み合わせて用いることができる。 In addition, when the optical pressure-sensitive adhesive sheet has another pressure-sensitive adhesive layer, the other pressure-sensitive adhesive layer is not particularly limited, and examples thereof include a urethane-based pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, and a silicone-based pressure sensitive adhesive layer. Examples include known and commonly used pressure-sensitive adhesive layers formed from known pressure-sensitive adhesives such as pressure-sensitive adhesives, polyester-based pressure-sensitive adhesives, polyamide-based pressure-sensitive adhesives, epoxy-based pressure-sensitive adhesives, vinyl alkyl ether-based pressure-sensitive adhesives, and fluorine-based pressure-sensitive adhesives. The above adhesives can be used alone or in combination of two or more.
　なお、前記光学用粘着シートにおいては、基材も他の粘着剤層も含まない場合には、本発明（Ｉ）～本発明（ＩＶ）の重合性組成物を重合して得られる重合物層、また、他の粘着剤層を含む場合には、本発明（Ｉ）～本発明（ＩＶ）の重合性組成物を重合して得られる重合物層と、この他の粘着剤層を合わせた層、また、基材を含む場合には、本発明（Ｉ）～本発明（ＩＶ）の重合性組成物を重合して得られる重合物層と、この基材を合わせた層、また、他の粘着剤層と基材をともに含む場合には、本発明（Ｉ）～本発明（ＩＶ）の重合性組成物を重合して得られる重合物層、他の粘着剤層および基材を合わせた層を「粘着剤層」と定義する。 When the optical pressure-sensitive adhesive sheet contains neither a base material nor another pressure-sensitive adhesive layer, a polymer layer obtained by polymerizing the polymerizable composition of the present invention (I) to the present invention (IV) In addition, when another pressure-sensitive adhesive layer is included, the polymer layer obtained by polymerizing the polymerizable composition of the present invention (I) to the present invention (IV) is combined with this other pressure-sensitive adhesive layer. In the case where a layer or a substrate is included, a polymer layer obtained by polymerizing the polymerizable composition of the present invention (I) to the present invention (IV), a layer combining this substrate, When both the pressure-sensitive adhesive layer and the substrate are included, the polymer layer obtained by polymerizing the polymerizable composition of the present invention (I) to the present invention (IV), the other pressure-sensitive adhesive layer and the substrate are combined. Layer is defined as “adhesive layer”.
　前記光学用粘着シートの粘着剤層表面（粘着面）は、使用時まではセパレータ（剥離ライナー）により保護されていてもよい。なお、本発明の光学用粘着シートが両面粘着シートである場合、各粘着面は、２枚のセパレータによりそれぞれ保護されていてもよいし、両面が剥離面となっているセパレータ１枚により、ロール状に巻回される形態で保護されていてもよい。セパレータは粘着剤層の保護材として用いられており、被着体に貼付する際に剥がされる。また、本発明の粘着シートが基材レス粘着シートの場合には、セパレータは粘着層の支持体の役割も担う。なお、セパレータは必ずしも設けられていなくてもよい。上記セパレータとしては、慣用の剥離紙などを使用でき、特に限定されないが、例えば、剥離処理層を有する基材、フッ素ポリマーからなる低接着性基材や無極性ポリマーからなる低接着性基材などを用いることができる。上記剥離処理層を有する基材としては、例えば、シリコーン系、長鎖アルキル系、フッ素系、硫化モリブデン等の剥離処理剤により表面処理されたプラスチックフィルムや紙等が挙げられる。上記フッ素ポリマーからなる低接着性基材におけるフッ素系ポリマーとしては、例えば、ポリテトラフルオロエチレン、ポリクロロトリフルオロエチレン、ポリフッ化ビニル、ポリフッ化ビニリデン、テトラフルオロエチレン－ヘキサフルオロプロピレン共重合体、クロロフルオロエチレン－フッ化ビニリデン共重合体等が挙げられる。また、上記無極性ポリマーとしては、例えば、オレフィン系樹脂（例えば、ポリエチレン、ポリプロピレンなど）等が挙げられる。なお、セパレータは公知ないし慣用の方法により形成することができる。また、セパレータの厚さ等も特に制限されない。 The pressure-sensitive adhesive layer surface (adhesive surface) of the optical pressure-sensitive adhesive sheet may be protected by a separator (release liner) until use. In the case where the optical pressure-sensitive adhesive sheet of the present invention is a double-sided pressure-sensitive adhesive sheet, each pressure-sensitive adhesive surface may be protected by two separators, respectively, or a single separator whose both surfaces are release surfaces, You may protect in the form wound by the shape. The separator is used as a protective material for the pressure-sensitive adhesive layer, and is peeled off when being applied to an adherend. Moreover, when the adhesive sheet of this invention is a base material-less adhesive sheet, a separator also plays the role of the support body of an adhesive layer. Note that the separator is not necessarily provided. As the separator, a conventional release paper or the like can be used, and is not particularly limited. For example, a substrate having a release treatment layer, a low adhesive substrate made of a fluoropolymer, a low adhesive substrate made of a nonpolar polymer, etc. Can be used. As a base material which has the said peeling process layer, the plastic film, paper, etc. which were surface-treated with peeling processing agents, such as a silicone type, a long-chain alkyl type, a fluorine type, and molybdenum sulfide, are mentioned, for example. Examples of the fluorine-based polymer in the low-adhesive substrate made of the above-mentioned fluoropolymer include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chloro Examples include fluoroethylene-vinylidene fluoride copolymer. Moreover, as said nonpolar polymer, olefin resin (for example, polyethylene, a polypropylene, etc.) etc. are mentioned, for example. The separator can be formed by a known or conventional method. Further, the thickness of the separator is not particularly limited.
　本発明（Ｉ）～（ＩＶ）の重合性組成物は、該重合性組成物を重合したときに前記条件で測定された２５℃で周波数０．１Ｈｚでの貯蔵弾性率が１×１０３～１×１０５Ｐａである重合物が得られる重合性組成物を製造するためには、本発明（Ｉ）～（ＩＶ）の必須構成成分を均一に混合すればよい。 The polymerizable composition of the present invention (I) ~ (IV) is storage modulus at frequency 0.1Hz at 25 ° C. as measured by the conditions when polymerizing the polymerizable composition is 1 × 10 3 ~ In order to produce a polymerizable composition from which a polymer of 1 × 10 5 Pa is obtained, the essential constituents of the present invention (I) to (IV) may be mixed uniformly.
　成分６として、２５℃で液状である化合物のみを使用する場合には、各成分を混合する際の温度は２０～１００℃の範囲であることが好ましく、さらに好ましくは、３０～９５℃の範囲であり、特に好ましくは、４０～９０℃の範囲である。 When only a compound that is liquid at 25 ° C. is used as component 6, the temperature when mixing each component is preferably in the range of 20 to 100 ° C., more preferably in the range of 30 to 95 ° C. And particularly preferably in the range of 40 to 90 ° C.
　また、成分６として、２５℃で固体状である化合物を使用する場合には、この２５℃で固体状である化合物は、成分５単独、成分４と成分５の混合物、成分５、成分６の２５℃で液状である化合物の混合物、あるいは成分４、成分５および成分６の２５℃で液状の化合物の混合物等にあらかじめ溶解させて、均一な液状の混合物にしておくことが好ましい。
　成分６の２５℃で固体状である化合物を溶解する際の温度としては、溶解速度を考慮すると、２５℃で固体状である成分６の軟化点以上であることが望ましい。また、溶解に成分４を使用する場合には、溶解時に重合を抑制するためには、１３０℃以下の温度で溶解することが望ましい。
　この成分６の２５℃で固体状である化合物が溶解された均一な液状の混合物を用いて、本発明（Ｉ）～（ＩＶ）の重合性組成物を製造する際には、この混合液を含む各成分を混合する際の温度は２０～１００℃の範囲であることが好ましく、さらに好ましくは、３０～９５℃の範囲であり、特に好ましくは、４０～９０℃の範囲である。 In addition, when a compound that is solid at 25 ° C. is used as component 6, the compound that is solid at 25 ° C. is component 5 alone, a mixture of component 4 and component 5, component 5 and component 6 It is preferable to dissolve in a mixture of compounds that are liquid at 25 ° C. or a mixture of compounds that are component 4, component 5 and component 6 that are liquid at 25 ° C. to obtain a uniform liquid mixture.
The temperature at which the compound that is solid at 25 ° C. of the component 6 is desirably higher than the softening point of the component 6 that is solid at 25 ° C. in consideration of the dissolution rate. When component 4 is used for dissolution, it is desirable to dissolve at a temperature of 130 ° C. or lower in order to suppress polymerization during dissolution.
When the polymerizable composition of the present invention (I) to (IV) is produced using the uniform liquid mixture in which the compound that is solid at 25 ° C. is dissolved, this mixed liquid is used. The temperature at the time of mixing each of the components is preferably in the range of 20 to 100 ° C., more preferably in the range of 30 to 95 ° C., and particularly preferably in the range of 40 to 90 ° C.
　さらに高性能の画像装置とするためには本願の画像装置の重合物や光学用粘着シートは耐着色性、高透明であることも望まれている。耐着色性は具体的には、以下の物性値を満たすことによって評価できる。
　好ましい耐着色性としては、２枚のガラス間に存在する２００μｍ厚に調整された当該重合物の、８５℃で５００時間の条件で保存した後のＪＩＳ　Ｚ　８７２９に記載の色座標ｂ＊値が１．６未満になることである。また、本発明の重合性組成物を重合することにより得られる重合物は、透明度が高いことが好ましく、具体的には、２枚のガラス間に存在する２００μｍ厚に調整された当該重合物のヘーズが、０．４以下であることが好ましく、さらに好ましくは、０．２以下である。 In order to obtain a higher-performance image device, it is also desired that the polymer of the image device of the present application and the optical pressure-sensitive adhesive sheet have coloring resistance and high transparency. Specifically, the color resistance can be evaluated by satisfying the following physical property values.
As a preferable color resistance, the color coordinate b * value described in JIS Z 8729 after storing the polymer adjusted to a thickness of 200 μm existing between two glasses at a temperature of 85 ° C. for 500 hours is It is less than 1.6. Moreover, it is preferable that the polymer obtained by polymerizing the polymerizable composition of the present invention has high transparency. Specifically, the polymer is adjusted to a thickness of 200 μm existing between two glasses. The haze is preferably 0.4 or less, and more preferably 0.2 or less.
　また、本明細書に記載の「２枚のガラス間に存在する２００μｍ厚に調整された重合物」とは厚さ０．７ｍｍの２枚の光学ガラス（コーニング社製、商品名：イーグルＸＧ）の間に重合性組成物を介在させ、前記光学ガラス越しに、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプ、メタルハライドランプ、無電極ランプ、ＬＥＤ等を光源として、光重合開始剤が感光可能な光を照射することにより得られる、厚さ２００μｍの重合物であり、重合物層の外側の２枚のガラスに挟まれた部分には、スペーサ、ガスケット、あるいは封止剤等が全く含まれていないものである。 In addition, “polymerized to a thickness of 200 μm existing between two glasses” described in this specification means two optical glasses having a thickness of 0.7 mm (trade name: Eagle XG, manufactured by Corning). Initiating photopolymerization using a low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, xenon lamp, metal halide lamp, electrodeless lamp, LED, etc. The polymer is a polymer having a thickness of 200 μm obtained by irradiating light capable of being exposed to light, and a spacer, a gasket, a sealant, or the like is provided between the two glass layers outside the polymer layer. Is not included at all.
　さらに、本明細書に記載の「８５℃で５００時間の条件で保存した後のＪＩＳ　Ｚ　８７２９に記載の色座標ｂ＊値」とは、前記２枚のガラス間に存在する２００μｍ厚に調整された重合物を、８５℃の環境下で、５００時間保持した後、２３℃の環境下で、ＪＩＳ　Ｚ　８７２９に記載の方法により、測定された色座標（psychometric chroma coordinates）のｂ＊の値である。ただし、このｂ＊の値を測定する際に用いられたリファレンスは厚さ０．７ｍｍの光学ガラス（コーニング社製、商品名：イーグルＸＧ）１枚である。本発明（Ｖ）においては、上記条件で測定されたｂ＊の値は１．６以下であることが好ましい。より好ましくは１．２以下であり、さらに好ましくは１．０以下である。上記条件で測定されたｂ＊の値が１．６より大きくなると、経時で３７０～４５０ｎｍの光の透過率が減少することにつながる。 Furthermore, the “color coordinate b * value described in JIS Z 8729 after storage at 85 ° C. for 500 hours” described in the present specification is adjusted to a thickness of 200 μm existing between the two glasses. The polymer was held at 85 ° C. for 500 hours, and then measured at 23 ° C. in accordance with the method described in JIS Z 8729 using the value of b * of the measured color coordinates (psychometric chroma coordinates). is there. However, the reference used when measuring the value of b * is one optical glass (manufactured by Corning, trade name: Eagle XG) having a thickness of 0.7 mm. In this invention (V), it is preferable that the value of b * measured on the said conditions is 1.6 or less. More preferably, it is 1.2 or less, More preferably, it is 1.0 or less. When the value of b * measured under the above conditions becomes larger than 1.6, the transmittance of light of 370 to 450 nm is decreased with time.
　耐着色性を向上させるためには、酸化防止剤を重合性組成物に適当量加えるとよい。酸化防止剤の使用量は、本発明（Ｉ）～本発明（ＩＶ）の重合性組成物の総量に対し、０．０１～５質量部が好ましい。ただし、酸化防止剤の量は、成分６等の他の成分に予め含まれている酸化防止剤を加味した値である。即ち、成分６等に予め酸化防止剤が含まれている場合があるとき、この酸化防止剤と新たに添加する酸化防止剤の総量を併せた量が、本発明（Ｉ）～本発明（ＩＶ）の重合性組成物の総量に対し、０．０１～５質量部の添加量になることを意味する。また、酸化防止剤の使用量はさらに好ましくは０．０１～４質量部、特に好ましくは０．０１～３質量部である。
　本発明（Ｉ）～本発明（ＩＶ）の重合性組成物の総量に対し、酸化防止剤が０．０１質量部未満の場合には、添加効果（即ち、酸化防止効果）が発現されない場合があり、上記条件でｂ＊の値が１．６を超えてしまう場合がある。また、本発明（Ｉ）～本発明（ＩＶ）の重合性組成物の総量に対し、重合禁止剤の量が５質量部より多い場合には、後述の本発明（Ｖ）の重合物あるいは後述の前記光学用粘着シートから、酸化防止剤が析出したり、ブリードしたりする場合がある。 In order to improve the color resistance, an appropriate amount of an antioxidant may be added to the polymerizable composition. The amount of the antioxidant used is preferably 0.01 to 5 parts by mass with respect to the total amount of the polymerizable composition of the present invention (I) to the present invention (IV). However, the amount of the antioxidant is a value in consideration of the antioxidant contained in the other components such as the component 6 in advance. That is, when an antioxidant is preliminarily contained in the component 6 or the like, the total amount of this antioxidant and the newly added antioxidant is the present invention (I) to the present invention (IV ) To 0.01 to 5 parts by mass relative to the total amount of the polymerizable composition. The amount of the antioxidant used is more preferably 0.01 to 4 parts by mass, particularly preferably 0.01 to 3 parts by mass.
When the antioxidant is less than 0.01 parts by mass with respect to the total amount of the polymerizable composition of the present invention (I) to the present invention (IV), the addition effect (that is, the antioxidant effect) may not be exhibited. Yes, the value of b * may exceed 1.6 under the above conditions. Further, when the amount of the polymerization inhibitor is more than 5 parts by mass relative to the total amount of the polymerizable composition of the present invention (I) to the present invention (IV), the polymer of the present invention (V) described later or the later described From the optical pressure-sensitive adhesive sheet, an antioxidant may precipitate or bleed.
　また、２枚のガラス間に存在する２００μｍ厚に調整された当該重合物の、９５℃で５００時間の条件で保存した後のＪＩＳ　Ｚ　８７２９に記載の色座標ｂ＊値も前述の８５℃での物性値を満たすことが好ましい。この際の測定方法は前述の８５℃での方法と同様である。 Also, the color coordinate b * value described in JIS Z 8729 after storing the polymer adjusted to a thickness of 200 μm existing between the two sheets of glass at 95 ° C. for 500 hours is also the above-mentioned 85 ° C. It is preferable to satisfy the physical property values of The measurement method at this time is the same as the method at 85 ° C. described above.
　さらに、２枚のガラス間に存在する２００μｍ厚に調整された当該重合物の、６０℃９０％で５００時間の条件で保存した後のＪＩＳ　Ｋ　７１３６に記載のヘーズが、０．４以下であることが好ましい。さらに好ましくは、０．２以下である。この場合も測定方法は前記条件と同様である。ヘーズが０．４以上である場合は、光の透過率が減少することにつながる。
　６０℃９０％で５００時間の条件で保存した後のＪＩＳ　Ｋ　７１３６に記載のヘーズが、０．４以下となるためには、成分３の使用量が、本発明（ＩＶ）の必須成分である成分１、成分３、成分４、成分５および成分６を合わせた総量に対して、１～３０質量部であることが好ましい。さらに好ましくは、２～２０質量部であり、特に好ましくは、３～１０質量部である。 Furthermore, the haze described in JIS K 7136 after storing the polymer adjusted to a thickness of 200 μm existing between two glasses at a temperature of 60 ° C. and 90% for 500 hours is 0.4 or less. It is preferable. More preferably, it is 0.2 or less. In this case as well, the measurement method is the same as that described above. When the haze is 0.4 or more, the light transmittance is reduced.
In order for the haze described in JIS K 7136 to be 0.4 or less after being stored at 60 ° C. and 90% for 500 hours, the amount of component 3 used is an essential component of the present invention (IV). The total amount of Component 1, Component 3, Component 4, Component 5 and Component 6 is preferably 1 to 30 parts by mass. More preferably, it is 2 to 20 parts by mass, and particularly preferably 3 to 10 parts by mass.
　次に、本発明（ＶＩＩＩ）について説明する。
　本発明（ＶＩＩＩ）は、画像表示部を有する基部と、透光性の保護部と、前記基部と前記保護部との間に介在する重合物層を含む画像表示装置の製造方法であって、該方法が、本発明（ＩＶ）の重合性組成物を、前記基部と前記保護部との間に介在させる工程、および光重合開始剤が感光可能な光を前記重合性組成物に照射して重合物層を形成する工程を含むことを特徴とする画像表示装置の製造方法に関する。
　なお、本明細書に記載の「画像表示部を有する基部と、透光性の保護部との間」とは、画像表示部を有する基部と、透光性の保護部との間の全て部分を意味し、例えば、図５の５ａと５ｂのいずれの場所も「画像表示部を有する基部と、透光性の保護部との間」という表現に含まれることを意味する。 Next, the present invention (VIII) will be described.
The present invention (VIII) is a method for producing an image display device comprising a base having an image display portion, a translucent protective portion, and a polymer layer interposed between the base and the protective portion, The method comprises the step of interposing the polymerizable composition of the present invention (IV) between the base part and the protective part, and irradiating the polymerizable composition with light that can be photosensitized by a photopolymerization initiator. The present invention relates to a method for manufacturing an image display device including a step of forming a polymer layer.
Note that “between the base portion having the image display portion and the translucent protective portion” described in the present specification means all the portions between the base portion having the image display portion and the translucent protective portion. For example, it means that any of the locations 5a and 5b in FIG. 5 is included in the expression “between the base portion having the image display portion and the translucent protective portion”.
　以下に、画像表示装置の好ましい実施の形態について図面を参照して、より具体的に説明する。なお、各図中、同一符号は同一または同等の構成要素を表している。
　例えば、図２、図３および図４は、本発明に係る画像表示装置の一実施形態の要部を示す断面図である。
　図２、図３および図４に示すように、本実施の形態の表示装置１は、図示しない駆動回路に接続され、所定の画像表示を行う画像表示部２と、この画像表示部２に所定の距離をおいて近接対向配置された透光性の保護部３とを有している。 Hereinafter, preferred embodiments of the image display device will be described more specifically with reference to the drawings. In each figure, the same numerals indicate the same or equivalent components.
For example, FIG. 2, FIG. 3 and FIG. 4 are cross-sectional views showing the main parts of one embodiment of the image display device according to the present invention.
As shown in FIGS. 2, 3, and 4, the display device 1 of the present embodiment is connected to a drive circuit (not shown) and displays an image display unit 2 that performs a predetermined image display. And a translucent protective portion 3 disposed in close proximity to each other at a distance of.
　なお、本明細書に記載の「画像表示装置」としては、画像を表示する装置であれば、特に限定されるものではなく、種々のものに適用することができる。例えば、携帯電話、携帯ゲ－ム機器等の液晶表示装置あるいは有機ＥＬ表示装置が挙げられる。本実施形態の画像表示部２は、液晶表示装置の液晶表示パネルである。
　なお、画像表示部２が液晶表示パネルである場合には、図２、図３あるいは図４に示すように、その表面に偏光板６ａ、６ｂが設けられている。 The “image display device” described in the present specification is not particularly limited as long as it is a device that displays an image, and can be applied to various devices. For example, a liquid crystal display device or an organic EL display device such as a mobile phone or a mobile game device can be used. The image display unit 2 of the present embodiment is a liquid crystal display panel of a liquid crystal display device.
When the image display unit 2 is a liquid crystal display panel, polarizing plates 6a and 6b are provided on the surface thereof as shown in FIG. 2, FIG. 3, or FIG.
　本実施形態の画像表示装置１の製造方法としては、例えば、まず、画像表示部２上の周縁部に、スペーサ４と図示しない突堤部を設け、これらの内側の領域に本発明（ＩＶ）の重合性組成物を所定量滴下する。
　そして、画像表示部（液晶表示パネル）２のスペーサ４上に保護部３を配置し、画像表示部（液晶表示パネル）２と保護部３との間の空隙に、本発明（ＩＶ）の重合性組成物を隙間なく充填する。
　その後、保護部３を介して、本発明（ＩＶ）の重合性組成物に対して、本発明（ＩＶ）の重合性組成物の必須成分である成分２が感光可能な光を照射することにより、本発明（ＩＶ）の重合性組成物を重合させる。これにより、目的とする画像表示装置１を得る。 As a manufacturing method of the image display device 1 of the present embodiment, for example, first, the spacer 4 and a jetty (not shown) are provided on the peripheral portion on the image display unit 2, and the region of the present invention (IV) is provided in the inner region thereof. A predetermined amount of the polymerizable composition is dropped.
Then, the protective part 3 is arranged on the spacer 4 of the image display part (liquid crystal display panel) 2, and the polymerization of the present invention (IV) is performed in the gap between the image display part (liquid crystal display panel) 2 and the protective part 3. The composition is filled without gaps.
Then, the component 2 which is an essential component of the polymerizable composition of the present invention (IV) is irradiated with light capable of being exposed to the polymerizable composition of the present invention (IV) via the protective part 3. The polymerizable composition of the present invention (IV) is polymerized. Thereby, the target image display apparatus 1 is obtained.
　この画像表示装置１によれば、重合物層５と保護部３との屈折率が同等であるため、輝度やコントラストを高めて視認性を向上させることができる。 According to this image display device 1, since the refractive index of the polymer layer 5 and the protective part 3 are equal, the brightness and contrast can be increased to improve the visibility.
　なお、成分２が感光可能な光を照射する工程は、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプ、メタルハライドランプ、無電極ランプなどを光源として用いる、一般的な紫外線照射装置、例えばベルトコンベア式の紫外線照射装置を用いて行うことができる。紫外線照射量は、一般に、約１０００ｍＪ／ｃｍ２～約８０００ｍＪ／ｃｍ２である。 The process of irradiating the component 2 with photosensitive light is a general ultraviolet irradiation device using a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp, an electrodeless lamp or the like as a light source. For example, it can be performed using a belt conveyor type ultraviolet irradiation device. UV irradiation dose is generally from about 1000 mJ / cm 2 ~ about 8000 mJ / cm 2.
　また、画像表示部（液晶表示パネル）２および保護部３に対し、重合性組成物の重合時の体積収縮により引き起こされる応力の影響を最小限に抑えることができるので、液晶表示パネル２および保護部３において歪みがほとんど発生せず、その結果、画像表示部（液晶表示パネル）２に変形が発生しないので、表示不良のない高輝度および高コントラストの画像表示が可能になる。 Further, since the influence of the stress caused by the volume shrinkage during polymerization of the polymerizable composition can be suppressed to the image display unit (liquid crystal display panel) 2 and the protection unit 3, the liquid crystal display panel 2 and the protection unit 3 can be protected. As a result, the image display unit (liquid crystal display panel) 2 is not deformed, so that it is possible to display an image with high brightness and high contrast without display defects.
　また、図２や図３、図４の５ｂの重合物層に本発明（Ｖ）の重合物が用いられた場合には、５ｂの重合物層の重合物の誘電率は高く維持されるので、この重合物層の厚みをある程度厚くしても、タッチセンサーの感度が低下するのを防止することができる。 When the polymer of the present invention (V) is used for the polymer layer 5b in FIGS. 2, 3 and 4, the dielectric constant of the polymer in the polymer layer 5b is maintained high. Even if the thickness of the polymer layer is increased to some extent, it is possible to prevent the sensitivity of the touch sensor from being lowered.
　次に、本発明（ＩＸ）について説明する。
　本発明（ＩＸ）は、画像表示部を有する基部と透光性の保護部とを光学用粘着シートを用いて貼り付ける工程を有する画像表示装置の製造方法であって、該光学用粘着シートが、本発明（ＶＩＩ）に記載の光学用粘着シートであることを特徴とする画像表示装置の製造方法である。
　なお、本明細書に記載の「画像表示部を有する基部と、透光性の保護部とを光学用粘着シートを用いて貼り付ける」とは、画像表示部を有する基部と、透光性の保護部との間のいずれの部分を貼り付けても、「画像表示部を有する基部と、透光性の保護部とを光学用粘着シートを用いて貼り付ける」という表現に含まれることを意味し、例えば、図５の５ａと５ｂのどちらに粘着シートを用いて貼り付けても、「画像表示部を有する基部と、透光性の保護部とを光学用粘着シートを用いて貼り付ける」という表現に含まれることを意味する。 Next, the present invention (IX) will be described.
This invention (IX) is a manufacturing method of an image display apparatus which has the process of sticking the base which has an image display part, and a translucent protective part using an optical adhesive sheet, Comprising: This optical adhesive sheet is A method for manufacturing an image display device, which is the optical pressure-sensitive adhesive sheet according to the present invention (VII).
As used herein, “attaching a base portion having an image display portion and a translucent protective portion using an optical adhesive sheet” means that the base portion having an image display portion and a translucent portion are used. Meaning that any part between the protective part and the protective part is included in the expression "the base having the image display part and the translucent protective part are attached using an optical adhesive sheet". For example, even if the adhesive sheet is attached to either 5a or 5b in FIG. 5, "the base having the image display part and the translucent protective part are attached using the optical adhesive sheet" It is included in the expression.
　画像表示部を有する基部と、透光性の保護部とを光学用粘着シートを用いて貼り付ける工程の例示を目的として、第１の基材がタッチセンサー一体型保護部であり、第２の基材が偏光板付きの表示部である図４の表示装置での製造工程を例に説明する。
　前記光学用粘着シートを、第１の基材である透光性の保護部の片面で隣接させて配置する工程と、第２の基材である偏光板付きの表示部の表面を前記光学用粘着シートと隣接させて配置する工程と、前記光学用粘着シートを加熱および／または加圧して段差または隆起に追従させる工程と、さらに、必要に応じて前記光学用粘着シートに光重合開始剤が感光可能な光を照射する工程を含む方法によって製造することができる。これらの工程は様々な順序で行うことができる。 For the purpose of exemplifying the step of attaching the base portion having the image display portion and the translucent protective portion using the optical adhesive sheet, the first base material is a touch sensor integrated protective portion, A manufacturing process in the display device of FIG. 4 in which the base material is a display unit with a polarizing plate will be described as an example.
The step of arranging the optical pressure-sensitive adhesive sheet adjacent to one side of the translucent protective part as the first base material, and the surface of the display part with a polarizing plate as the second base material for the optical A step of arranging adjacent to the pressure-sensitive adhesive sheet, a step of heating and / or pressing the optical pressure-sensitive adhesive sheet to follow a step or a ridge, and a photopolymerization initiator on the optical pressure-sensitive adhesive sheet as necessary. It can be manufactured by a method including a step of irradiating photosensitive light. These steps can be performed in various orders.
　例えば１つの具体的方法として、最初に、前記光学用粘着シートの一方の面を第１の基材である透光性の保護部の片面側で隣接させて配置し、第２の基材である偏光板付きの表示部の表面を前記光学用粘着シートのもう一方の面と隣接させて配置する。すなわち前記光学用粘着シートに段差または隆起を有する表面が向くようにして、透光性の保護部（第１の基材）と偏光板付きの表示部（第２の基材）で前記光学用粘着シートを挟む。
　次に、前記光学用粘着シートを加熱および／または加圧して、粘着シートを段差または隆起に追従させる。その後、必要に応じて、透光性の保護部（第１の基材）側および／または偏光板付きの表示部（第２の基材）側から、これらの基材を通して前記光学用粘着シートに光重合開始剤が感光可能な光を照射する。このようにして、透光性の保護部（第１の基材）の段差または隆起の近傍に空隙を形成することなく、透光性の保護部（第１の基材）と偏光板付きの表示部（第２の基材）を接着することができる。この実施態様では、透光性の保護部（第１の基材）と偏光板付きの表示部（第２の基材）を前記光学用粘着シートに隣接させてから、当該粘着シートを加熱および／または加圧するため、偏光板付きの表示部（第２の基材）の被着表面に段差や隆起がある場合（即ち、画像表示モジュールに取り付けられた偏光板上に当該粘着シートを適用する場合）に、偏光板付きの表示部（第２の基材）の段差や隆起にも当該粘着シートを追従させて、それらの形状近傍においても空隙の形成を防止することができる。
　上記方法では、光重合開始剤が感光可能な光を照射する場合には、第１の基材および第２の基材の少なくとも一方が、それらを通して前記光学用粘着シートに、光重合開始剤が感光可能な光を照射できるように、少なくとも部分的に透明である。第１の基材の段差または隆起の部分が紫外線を透過しない場合、第１の基材側から紫外線を照射すると、その段差または隆起の部分の直下には紫外線が照射されないが、照射された部分で発生したラジカルの移動などにより非照射部分においても粘着シートの重合がある程度進行する。 For example, as one specific method, first, one surface of the optical pressure-sensitive adhesive sheet is disposed adjacent to one side of the translucent protective portion which is the first base material, and the second base material is used. The surface of the display part with a certain polarizing plate is arrange | positioned adjacent to the other surface of the said optical adhesive sheet. That is, with the optical adhesive sheet facing the surface having a step or a ridge, the optically transparent portion (first substrate) and the display portion (second substrate) with a polarizing plate are used for the optical. Insert an adhesive sheet.
Next, the optical pressure-sensitive adhesive sheet is heated and / or pressurized to cause the pressure-sensitive adhesive sheet to follow a step or a bump. Then, if necessary, the optical pressure-sensitive adhesive sheet passes through these substrates from the side of the translucent protective part (first base material) and / or the display part (second base material) with a polarizing plate. The photopolymerization initiator is irradiated with light capable of being exposed to light. In this way, the translucent protective part (first base material) and the polarizing plate are attached without forming a gap in the vicinity of the step or the bulge of the translucent protective part (first base material). The display portion (second base material) can be adhered. In this embodiment, a translucent protective part (first base material) and a display part with a polarizing plate (second base material) are adjacent to the optical pressure-sensitive adhesive sheet, and then the pressure-sensitive adhesive sheet is heated and In order to pressurize, when there is a step or a bulge on the adherend surface of the display unit (second base material) with a polarizing plate (that is, the adhesive sheet is applied on the polarizing plate attached to the image display module) In the case), the pressure-sensitive adhesive sheet can be made to follow the steps and bulges of the display portion (second base material) with the polarizing plate, and the formation of voids can be prevented even in the vicinity of the shape.
In the above method, when the photopolymerization initiator irradiates light capable of being sensitized, at least one of the first base material and the second base material passes through them to the optical pressure-sensitive adhesive sheet, and the photopolymerization initiator is present. It is at least partially transparent so that it can be irradiated with photosensitive light. When the step or bulge portion of the first base material does not transmit ultraviolet light, when the ultraviolet light is irradiated from the first base material side, the ultraviolet light is not irradiated directly below the step or bulge portion, but the irradiated portion The polymerization of the pressure-sensitive adhesive sheet proceeds to some extent even in the non-irradiated part due to the movement of radicals generated in the above.
　別の具体的方法としては、前記光学用粘着シートの一方の面を透光性の保護部（第１の基材）に段差または隆起を有する表面側（即ち、使用の際に人が触れない面側）で隣接させて配置した後、当該粘着シートを加熱および／または加圧して、当該粘着シートを段差または隆起に追従させる。その後、必要に応じて、前記光学用粘着シートの開放面に紫外線を照射して、当該粘着シートをさらに重合した後、偏光板付きの表示部（第２の基材）を当該粘着シートのもう一方の面に隣接させて配置して、第２の基材を当該粘着シートに貼り付ける。剥離フィルムが透明であれば、必要に応じて、剥離フィルムを通して粘着シートに紫外線を照射することもできる。この例では、当該粘着シート全面に光重合開始剤が感光可能な光を照射することができるため、より均一に当該粘着シートを重合することができる。第１の基材が、当該粘着シートの重合に必要な光重合開始剤が感光可能な光を照射できるように少なくとも部分的に透明であれば、必要に応じて、第１の基材側から紫外線を照射することもできる。このようにして、第１の基材の段差または隆起の近傍に空隙を形成することなく、第１の基材と第２の基材を接着することができる。 As another specific method, one surface of the optical pressure-sensitive adhesive sheet is a surface side having a step or a bulge in the translucent protective portion (first base material) (that is, a person does not touch during use) After being placed adjacent to each other on the surface side, the pressure-sensitive adhesive sheet is heated and / or pressurized to cause the pressure-sensitive adhesive sheet to follow a step or a bump. Then, if necessary, after irradiating the open surface of the optical pressure-sensitive adhesive sheet with ultraviolet rays to further polymerize the pressure-sensitive adhesive sheet, the display unit with the polarizing plate (second base material) is placed on the pressure-sensitive adhesive sheet. It arrange | positions adjacent to one surface, and a 2nd base material is affixed on the said adhesive sheet. If the release film is transparent, the pressure-sensitive adhesive sheet can be irradiated with ultraviolet rays through the release film, if necessary. In this example, since the photopolymerization initiator can be irradiated with light capable of being exposed to the entire surface of the pressure-sensitive adhesive sheet, the pressure-sensitive adhesive sheet can be polymerized more uniformly. If the first base material is at least partially transparent so that the photopolymerization initiator necessary for the polymerization of the pressure-sensitive adhesive sheet can irradiate light capable of being sensitized, from the first base material side, if necessary. Irradiation with ultraviolet rays is also possible. In this way, the first base material and the second base material can be bonded together without forming a gap near the step or bulge of the first base material.
　上記加熱工程は、対流式オーブン、ホットプレート、ヒートラミネーター、オートクレーブなどを用いて行うことができる。粘着シートの流動を促進して、より効率的に粘着シートを段差または隆起に追従させるために、ヒートラミネーター、オートクレーブなどを用いて、加熱と同時に加圧することが好ましい。オートクレーブを用いた加圧は、光学用粘着シートの脱泡に特に有利である。本発明の光学用粘着シートの加熱温度は、当該粘着シートが軟化または流動して段差または隆起に十分に追従する温度であればよく、一般に約３０℃以上、約４０℃以上、または約６０℃以上とすることができ、約１５０℃以下、約１２０℃以下、または約１００℃以下とすることができる。粘着シートを加圧する場合、与える圧力は、一般に約０．０５ＭＰａ以上、または約０．１ＭＰａ以上、約２ＭＰａ以下、または約１ＭＰａ以下とすることができる。 The heating step can be performed using a convection oven, a hot plate, a heat laminator, an autoclave, or the like. In order to promote the flow of the pressure-sensitive adhesive sheet and cause the pressure-sensitive adhesive sheet to follow the step or the protrusion more efficiently, it is preferable to pressurize simultaneously with heating using a heat laminator, an autoclave or the like. Pressurization using an autoclave is particularly advantageous for defoaming the optical pressure-sensitive adhesive sheet. The heating temperature of the optical pressure-sensitive adhesive sheet of the present invention may be any temperature as long as the pressure-sensitive adhesive sheet softens or flows and sufficiently follows a step or a bump, and is generally about 30 ° C. or higher, about 40 ° C. or higher, or about 60 ° C. The temperature may be about 150 ° C. or lower, about 120 ° C. or lower, or about 100 ° C. or lower. When the pressure-sensitive adhesive sheet is pressurized, the applied pressure can be generally about 0.05 MPa or more, or about 0.1 MPa or more, about 2 MPa or less, or about 1 MPa or less.
　必要に応じて行われる、上記の光重合開始剤が感光可能な光を照射する工程は、前述の成分２が感光可能な光を照射する工程と同様である。 The step of irradiating light that can be photosensitized by the above-described photopolymerization initiator, which is performed as necessary, is the same as the step of irradiating light that can be sensitized by the component 2 described above.
　最後に、本発明（Ｘ）について説明する。
　本発明（Ｘ）は、本発明（ＶＩＩＩ）または本発明（ＩＸ）の画像表示装置の製造方法によって製造された画像表示装置である。
　本発明（Ｘ）の画像表示装置は、表示装置の本体が光学ガラスから形成されている場合、一般的にその屈折率（ｎＤ）は、１．４９～１．５２となる。なお、屈折率（ｎＤ）が、１．５５程度の強化ガラスも存在する。
　保護部３は、表示部２と同程度の大きさの板状、シート状またはフィルム状の透光性部材から形成されている。この透光性部材としては、例えば、光学ガラスやプラスチック（ポリメタクリル酸メチル等のアクリル樹脂等）を好適に用いることができる。保護部３の表面もしくは裏面には、反射防止膜、遮光膜、視野角制御膜等の光学層を形成してもよい。
　保護部３がアクリル樹脂から形成されている場合には、一般的にその屈折率（ｎＤ）は１．４９～１．５１となる。
　保護部３は、表示部２の周縁部に設けられたスペーサ４を介して表示部２上に設けられている。このスペーサ４の厚さは０．０５～１．５ｍｍ程度であり、これにより画像表示部２と保護部３との表面間距離が１ｍｍ程度に保持される。
　また、保護部３の周縁部には、輝度およびコントラストを向上させるため、図示しない枠状の遮光部が設けられている。 Finally, the present invention (X) will be described.
The present invention (X) is an image display device manufactured by the manufacturing method of the image display device of the present invention (VIII) or the present invention (IX).
The image display device of the present invention (X) generally has a refractive index (n D ) of 1.49 to 1.52 when the main body of the display device is made of optical glass. There is also a tempered glass having a refractive index (n D ) of about 1.55.
The protection unit 3 is formed from a plate-like, sheet-like, or film-like translucent member having the same size as the display unit 2. As this translucent member, for example, optical glass or plastic (acrylic resin such as polymethyl methacrylate) can be suitably used. An optical layer such as an antireflection film, a light shielding film, or a viewing angle control film may be formed on the front surface or the back surface of the protection unit 3.
When the protective part 3 is made of an acrylic resin, its refractive index (n D ) is generally 1.49 to 1.51.
The protection unit 3 is provided on the display unit 2 via a spacer 4 provided on the peripheral edge of the display unit 2. The spacer 4 has a thickness of about 0.05 to 1.5 mm, whereby the distance between the surfaces of the image display unit 2 and the protection unit 3 is maintained at about 1 mm.
In addition, a frame-shaped light shielding portion (not shown) is provided at the peripheral portion of the protection portion 3 in order to improve luminance and contrast.
　まず、本発明（ＶＩＩＩ）の画像表示装置の製造方法によって製造された画像表示装置について詳しく説明する。
　画像表示部２と保護部３との間には、重合物層５ａ、５ｂが介在している。本発明（ＶＩＩＩ）の画像表示装置の製造方法によって製造された画像表示装置の場合には、この重合物層５ａや重合物層５ｂには、本発明（Ｖ）の重合物が介在するため、可視光領域の透過率が９０％以上になる。ここで、重合物層５ａや重合物層５ｂの厚みは１０～２０００μｍとなるようにすることが好ましい。さらに好ましくは、２０～１７００μｍであり、特に好ましくは、３０～１３００μｍである。また、重合物層５ａや重合物層５ｂには、本発明（Ｖ）の重合物が介在するため、２５℃における屈折率（ｎＤ）は先述の本発明（Ｖ）で屈折率について述べた物性値および効果と同様である。 First, the image display device manufactured by the method for manufacturing the image display device of the present invention (VIII) will be described in detail.
Between the image display part 2 and the protection part 3, polymer layers 5a and 5b are interposed. In the case of the image display device manufactured by the method for manufacturing the image display device of the present invention (VIII), the polymer of the present invention (V) is interposed in the polymer layer 5a and the polymer layer 5b. The transmittance in the visible light region is 90% or more. Here, the thickness of the polymer layer 5a or the polymer layer 5b is preferably 10 to 2000 μm. More preferably, it is 20 to 1700 μm, and particularly preferably 30 to 1300 μm. Further, since the polymer of the present invention (V) is present in the polymer layer 5a and the polymer layer 5b, the refractive index (n D ) at 25 ° C. is described in the above-mentioned present invention (V). The physical property values and effects are the same.
　本発明（ＶＩＩＩ）の画像表示装置の製造方法によって画像表示装置を製造する場合、重合物層５ａや重合物層５ｂには、本発明（Ｖ）の重合物が介在するため、重合性組成物の重合時の体積収縮率の物性値は前述の本発明（Ｖ）で体積収縮率について述べた物性値と効果と同様である。 When an image display device is produced by the method for producing an image display device of the present invention (VIII), the polymer composition of the present invention (V) is interposed in the polymer layer 5a and the polymer layer 5b, and therefore the polymerizable composition. The physical properties of the volume shrinkage during polymerization are the same as the physical properties and effects described for the volume shrinkage in the present invention (V).
　また、本発明（Ｖ）の重合物を重合物層５ｂに用いる場合には、これらの重合物の誘電率が高いので、人が触れた際の感度を大きくすることができる。
　また、本発明（ＩＸ）の画像表示装置の製造方法によって画像表示装置を製造する場合、重合物層５ａや重合物層５ｂには、前記重合物が介在するため、先述の本発明（Ｖ）の画像表示装置の製造方法によって画像表示装置を製造する場合に得られる効果、特性を得ることができる。 Moreover, when using the polymer of this invention (V) for the polymer layer 5b, since the dielectric constant of these polymers is high, the sensitivity when a person touches can be enlarged.
Further, when the image display device is produced by the method for producing an image display device of the present invention (IX), the polymer is interposed in the polymer layer 5a and the polymer layer 5b, and therefore the present invention (V) described above. The effects and characteristics obtained when an image display device is manufactured by this method for manufacturing an image display device can be obtained.
　次に、本発明（ＩＸ）の画像表示装置の製造方法によって製造された画像表示装置について詳しく説明する。
　画像表示部２と保護部３との間には、重合物層５ａと重合物層５ｂ、あるいは重合物層５ｂが介在している。本発明（ＩＸ）の画像表示装置の製造方法によって製造された画像表示装置の場合には、この重合物層５ａや重合物層５ｂには、前記光学用粘着シートが介在するため、可視光領域の透過率が９０％以上になる。ここで、重合物層５ａや重合物層５ｂの厚みは１０～１０００μｍとなるようにすることが好ましい。さらに好ましくは、２０～７００μｍであり、特に好ましくは、３０～５００μｍである。
　また、重合物層５ａや重合物層５ｂには、本発明（Ｖ）の光学用粘着シートが介在するため、２５℃における屈折率（ｎＤ）については先に本発明（ＶＩＩＩ）で屈折率について述べた物性値及び効果と同様である。 Next, the image display apparatus manufactured by the image display apparatus manufacturing method of the present invention (IX) will be described in detail.
Between the image display part 2 and the protection part 3, a polymer layer 5a and a polymer layer 5b or a polymer layer 5b are interposed. In the case of the image display device manufactured by the manufacturing method of the image display device of the present invention (IX), the optical adhesive sheet is interposed in the polymer layer 5a and the polymer layer 5b, so that the visible light region Of 90% or more. Here, the thickness of the polymer layer 5a and the polymer layer 5b is preferably 10 to 1000 μm. More preferably, the thickness is 20 to 700 μm, and particularly preferably 30 to 500 μm.
In addition, since the optical adhesive sheet of the present invention (V) is interposed in the polymer layer 5a and the polymer layer 5b, the refractive index at 25 ° C. (n D ) is the refractive index in the present invention (VIII) first. This is the same as the physical property values and effects described above.
　また、本発明（ＩＸ）の画像表示装置の製造方法によって画像表示装置を製造する場合、重合物層５ａや重合物層５ｂには、前記光学用粘着シートが介在するため、先述の本発明（ＶＩＩＩ）の画像表示装置の製造方法によって画像表示装置を製造する場合に得られる効果、特性を得ることができる。 Moreover, when manufacturing an image display apparatus by the manufacturing method of the image display apparatus of this invention (IX), since the said adhesive sheet for optics interposes in the polymer layer 5a and the polymer layer 5b, the above-mentioned invention ( The effects and characteristics obtained when the image display device is manufactured by the manufacturing method of the image display device of VIII) can be obtained.
　また、前記光学用粘着シートは柔軟性を有するので、保護部３や表示部２、タッチパネル７が凹凸形状を有していても、さらには、画像表示ユニットの表示面に凹凸表面形状を有する層（例えば、偏光板）が設けられていたとしても、シート自体の内部残留応力が緩和されており、画像表示装置における表示ムラを防止することができる。例えば、図４の表示装置の場合、光学用粘着シートは充分な接着力及び親水性を有しているため、高温高湿環境下でも、画像表示部２の表示面（例えば、偏光板）と光学用粘着シート（即ち、重合物層５ｂ）との界面、及び光学用粘着シート（即ち、重合物層５ｂ）と透光性の保護部３との界面で気泡や剥がれが発生せず、また、白化も生じない。 In addition, since the optical pressure-sensitive adhesive sheet has flexibility, even if the protection unit 3, the display unit 2, and the touch panel 7 have an uneven shape, a layer having an uneven surface shape on the display surface of the image display unit. Even if (for example, a polarizing plate) is provided, the internal residual stress of the sheet itself is relaxed, and display unevenness in the image display device can be prevented. For example, in the case of the display device of FIG. 4, since the optical pressure-sensitive adhesive sheet has sufficient adhesive force and hydrophilicity, the display surface (for example, a polarizing plate) of the image display unit 2 can be used even in a high temperature and high humidity environment. Air bubbles and peeling do not occur at the interface with the optical pressure-sensitive adhesive sheet (that is, the polymer layer 5b) and at the interface between the optical pressure-sensitive adhesive sheet (that is, the polymer layer 5b) and the translucent protective portion 3. No whitening occurs.
　本発明（Ｘ）の画像表示装置に使用される光学ガラス板としては、液晶セルの液晶を挟持するガラス板や液晶セルの保護板として使用されているものを好ましく使用できる。また、使用されるアクリル樹脂板としては、液晶セルの保護板として使用されているものを好ましく使用できる。これらの光学ガラス板やアクリル樹脂板の平均表面粗度は、通常、１．０ｎｍ以下である。 As the optical glass plate used in the image display device of the present invention (X), those used as a glass plate for sandwiching the liquid crystal of the liquid crystal cell or a protective plate for the liquid crystal cell can be preferably used. Moreover, as an acrylic resin board used, what is used as a protective plate of a liquid crystal cell can be used preferably. The average surface roughness of these optical glass plates and acrylic resin plates is usually 1.0 nm or less.
　また、本発明（Ｘ）の画像表示装置は、画像表示部２と保護部３との間に本発明（Ｖ）の重合物または前記光学用粘着シートが用いられた重合物層５ａや重合物層５ｂが充填されているので、衝撃に強い。
　加えて、画像表示部２と保護部３との間に空隙を設けていた従来例に比して薄型に形成することができる。 In addition, the image display device of the present invention (X) includes a polymer layer 5a or a polymer obtained by using the polymer of the present invention (V) or the optical pressure-sensitive adhesive sheet between the image display unit 2 and the protection unit 3. Since the layer 5b is filled, it is strong against impact.
In addition, it can be formed thinner than the conventional example in which a gap is provided between the image display unit 2 and the protection unit 3.
　また、本発明（Ｘ）の画像表示装置は種々の態様をとることができる。例えば、図４に示すように、スペーサ４を省略して画像表示装置１を製造してもよい。図４の重合物層５ｂの場合には、例えば、表示部２上の偏光板６ａ上に、本発明（Ｉ）～本発明（ＩＶ）のいずれかの光重合性組成物を塗布し、前述と同様に光重合を行うか、あるいは、例えば、図５に示すように、保護部３、重合物層５ｂ、タッチパネル７および重合物層５ａ（即ち、光学用粘着シート５ａ）からなる積層体を画像表示部２上の表示面（即ち、偏光板６ａ表面）に貼り合わせることで得られる。 The image display device of the present invention (X) can take various forms. For example, as illustrated in FIG. 4, the image display device 1 may be manufactured by omitting the spacer 4. In the case of the polymer layer 5b of FIG. 4, for example, the photopolymerizable composition of any one of the present invention (I) to the present invention (IV) is applied onto the polarizing plate 6a on the display unit 2, and the above-mentioned Or, for example, as shown in FIG. 5, a laminate composed of the protective portion 3, the polymer layer 5b, the touch panel 7 and the polymer layer 5a (that is, the optical pressure-sensitive adhesive sheet 5a) is formed. It can be obtained by bonding to the display surface on the image display unit 2 (that is, the surface of the polarizing plate 6a).
　また、本発明は、上述した液晶表示装置のみならず、例えば、有機ＥＬ、プラズマディスプレイ装置等の種々のパネルディスプレイに適用することができる。 Further, the present invention can be applied not only to the liquid crystal display device described above but also to various panel displays such as an organic EL and a plasma display device.
　本発明の重合性組成物によれば、それを画像表示部と保護部との間に適用して重合させたときの体積収縮による応力を最小限に抑えることができるので、画像表示部を有する基部と、透光性の保護部との間に重合性組成物を介在させ、重合させて重合物層を形成する工程を用いて画像表示装置を製造する際に、この応力の画像表示部と保護部とに対する影響も最小限に抑えることができる。したがって、本発明の画像表示装置によれば、画像表示部および保護部において歪みがほとんど発生しない。
　さらに、本発明の重合性組成物は、揮発性の溶剤を含まない（即ち、無溶剤）ため、本発明の重合性組成物を重合して得られる重合物を、画像表示部と保護部との間に適用する際の製造工程において、溶剤の揮発工程がなく、エネルギー的にも有利でありかつ環境負荷も少ない。
　さらに、本発明の重合性組成物を画像表示部と保護部との間に適用して重合させた硬化物は、保護部に使用されているガラスとの密着性が大きい。
　また、本発明の重合物および光学粘着シートは、その屈折率が、従来、液晶表示パネルと保護部との間に設けられていた空隙に比して画像表示部の構成パネルや保護部の構成パネルの屈折率に近く、保護部と重合物との界面や重合物と画像表示部との界面、保護部と光学粘着シートとの界面や光学粘着シートと画像表示部との界面での光の反射が抑制される。その結果、本発明の画像表示装置によれば、表示不良のない高輝度および高コントラスト表示が可能になる。
　さらに、画像表示部が液晶表示パネルである場合には、液晶材料の配向乱れ等の表示不良を確実に防止して高品位の表示を行うことができる。
　さらに、本発明の画像表示装置によれば、画像表示部と保護部との間に重合物または光学粘着シートが介在するので、衝撃に強くなる。
　さらに、本発明の重合物および光学粘着シートは、熱履歴を受けた場合でも、着色しにくいので、高輝度および高コントラスト表示を長時間持続させることが可能である。
　加えて、本発明によれば、画像表示部と保護部との間に空隙を設けていた従来例に比して薄型の画像表示装置を提供することができる。 According to the polymerizable composition of the present invention, it is possible to minimize the stress due to volume shrinkage when it is applied between the image display part and the protective part and polymerized, so that the image display part is provided. When an image display device is manufactured using a process of forming a polymer layer by interposing a polymerizable composition between a base and a translucent protective part and polymerizing the image display part, The influence on the protection unit can be minimized. Therefore, according to the image display device of the present invention, distortion hardly occurs in the image display unit and the protection unit.
Furthermore, since the polymerizable composition of the present invention does not contain a volatile solvent (that is, no solvent), the polymer obtained by polymerizing the polymerizable composition of the present invention is divided into an image display part and a protective part. There is no solvent volatilization step in the manufacturing process when applied between the two, which is advantageous in terms of energy and has a low environmental impact.
Furthermore, the cured product obtained by polymerizing the polymerizable composition of the present invention between the image display part and the protective part has high adhesion to the glass used in the protective part.
In addition, the polymer and the optical adhesive sheet of the present invention have a refractive index that is a configuration panel of the image display unit or a configuration of the protection unit as compared with a gap that is conventionally provided between the liquid crystal display panel and the protection unit. It is close to the refractive index of the panel, and the light at the interface between the protective part and the polymer, the interface between the polymer and the image display part, the interface between the protective part and the optical adhesive sheet, or the interface between the optical adhesive sheet and the image display part. Reflection is suppressed. As a result, according to the image display device of the present invention, high luminance and high contrast display without display defects becomes possible.
Furthermore, when the image display unit is a liquid crystal display panel, display defects such as disorder of alignment of the liquid crystal material can be reliably prevented and high-quality display can be performed.
Furthermore, according to the image display device of the present invention, since the polymer or the optical adhesive sheet is interposed between the image display unit and the protection unit, the image display device is resistant to impact.
Furthermore, since the polymer and the optical adhesive sheet of the present invention are not easily colored even when subjected to a thermal history, it is possible to maintain high brightness and high contrast display for a long time.
In addition, according to the present invention, it is possible to provide a thin image display device as compared with the conventional example in which a gap is provided between the image display unit and the protection unit.
　以下、実施例により本発明を更に具体的に説明するが、本発明は以下の実施例にのみ制限されるものではない。 Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited only to the following examples.
＜粘度の測定＞
　温度２５．０℃で粘度１０Ｐａ・ｓ未満の試料については、以下の方法により、粘度を測定した。
　試料１ｍＬを使用して、コーン／プレート型粘度計（Ｂｒｏｏｋｆｉｅｌｄ社製、型式：ＤＶ－ＩＩ＋Ｐｒｏ、スピンドルの型番：ＣＰＥ－４２）を用いて、温度２５．０℃、回転数５ｒｐｍの条件で粘度がほぼ一定になったときの値を測定した。
　温度２５．０℃で粘度１０Ｐａ・ｓ以上の試料については、以下の方法により、粘度を測定した。
　試料０．５ｍＬを使用して、コーン／プレート型粘度計（Ｂｒｏｏｋｆｉｅｌｄ社製、型式：ＤＶ－ＩＩ＋Ｐｒｏ、スピンドルの型番：ＣＰＥ－５２）を用いて、温度２５．０℃、回転数５ｒｐｍの条件で粘度がほぼ一定になったときの値を測定した。 <Measurement of viscosity>
For samples having a viscosity of less than 10 Pa · s at a temperature of 25.0 ° C., the viscosity was measured by the following method.
Using a 1 mL sample, the viscosity was measured at a temperature of 25.0 ° C. and a rotation speed of 5 rpm using a cone / plate viscometer (manufactured by Brookfield, model: DV-II + Pro, spindle model: CPE-42). The value when it became almost constant was measured.
For a sample having a viscosity of 10 Pa · s or more at a temperature of 25.0 ° C., the viscosity was measured by the following method.
Using a 0.5 mL sample, a cone / plate viscometer (manufactured by Brookfield, model: DV-II + Pro, spindle model: CPE-52) under the conditions of a temperature of 25.0 ° C. and a rotation speed of 5 rpm The value when the viscosity became almost constant was measured.
＜水酸基価の測定＞
　ＪＩＳ　Ｋ　００７０に準拠して測定した。 <Measurement of hydroxyl value>
The measurement was performed according to JIS K 0070.
＜数平均分子量＞
　数平均分子量は下記条件でＧＰＣにより測定したポリスチレン換算の値である。
　装置名：日本分光株式会社製ＨＰＬＣユニット　ＨＳＳ－２０００
　カラム：ＳｈｏｄｅｘカラムＬＦ－８０４
　移動相：テトラヒドロフラン
　流速：１．０ｍＬ／ｍｉｎ
　検出器：日本分光株式会社製　ＲＩ－２０３１Ｐｌｕｓ
　温度：４０．０℃
　試料量：サンプルループ　１００μＬ
　試料濃度：０．５ｗｔ％前後に調製 <Number average molecular weight>
The number average molecular weight is a value in terms of polystyrene measured by GPC under the following conditions.
Device name: HPLC unit HSS-2000 manufactured by JASCO Corporation
Column: Shodex column LF-804
Mobile phase: Tetrahydrofuran Flow rate: 1.0 mL / min
Detector: RI-2031Plus manufactured by JASCO Corporation
Temperature: 40.0 ° C
Sample volume: Sample loop 100 μL
Sample concentration: prepared at around 0.5 wt%
（実施合成例１－１）
　攪拌装置および蒸留装置を備えた２０００ｍＬの反応容器中にＰｒｉｐｏｌ（登録商標）２０３３（クローダ製水添ダイマージオール、水酸基価２０２ｍｇＫＯＨ／ｇ）２６．２質量部、１，４－ブタンジオール（三菱化学株式会社製）４７．２質量部、３－メチル－１，５－ペンタンジオール（株式会社クラレ製）６５６．３質量部、アジピン酸（東京化成工業株式会社製）７２１．４質量部、Ｐｒｉｐｏｌ（登録商標）１００９（クローダ製水添ダイマー酸）２４１．５質量部および塩化第一錫（東京化成工業株式会社製）０．５質量部を仕込み、約１７０℃、常圧下から始めて水を留出させながら、徐々に２４０℃まで昇温し、縮合反応を継続した。その後、減圧しつつ縮合反応をさらに継続した。水が留出しなくなって２時間さらに反応を継続した後、系内を常圧に戻し反応を終了した。水酸基価５７．０ｍｇＫＯＨ／ｇであるポリエステルポリオール（以下、ポリエステルポリオールＡと記す。）を得た。 (Exemplary Synthesis Example 1-1)
Pripol (registered trademark) 2033 (clad hydrogenated dimer diol, hydroxyl value 202 mg KOH / g) 26.2 parts by mass, 1,4-butanediol (Mitsubishi Chemical Corporation) in a 2000 mL reaction vessel equipped with a stirrer and a distillation apparatus 47.2 parts by mass of company), 656.3 parts by mass of 3-methyl-1,5-pentanediol (manufactured by Kuraray Co., Ltd.), 721.4 parts by mass of adipic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), Pripol (registered) Trademark) 1009 (clad hydrogenated dimer acid) 241.5 parts by weight and stannous chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.5 parts by weight were charged, and water was distilled off starting at about 170 ° C. under normal pressure. The temperature was gradually raised to 240 ° C., and the condensation reaction was continued. Thereafter, the condensation reaction was further continued while reducing the pressure. After the water stopped distilling, the reaction was further continued for 2 hours, and then the system was returned to normal pressure to complete the reaction. A polyester polyol having a hydroxyl value of 57.0 mgKOH / g (hereinafter referred to as polyester polyol A) was obtained.
（実施合成例２－１）
　攪拌装置、温度計、滴下ロートおよびコンデンサーを備えた１００ｍＬの反応容器に、２，２，４－トリメチルヘキサメチレンジイソシアネートと２，４，４－トリメチルヘキサメチレンジイソシアネートの混合物（商品名：ＶＥＳＴＡＮＡＴ（登録商標）ＴＭＤＩ、エボニックデグサ製）１５．２８ｇ、ジオクチル錫ジラウレート１５ｍｇおよびｐ－メトキシフェノール２４ｍｇを反応容器に投入し、４－ヒドロキシブチルアクリレート１０．４８ｇを、滴下ロートを用いて滴下投入した。滴下中、反応容器内の温度は７０℃以下になるようにした。滴下終了後、２時間、反応器内の温度を７０～７５℃に維持したまま、撹拌を継続して反応生成物（以下、反応生成物αと記す。）を得た。
　攪拌装置、温度計およびコンデンサーを備えた３００ｍＬの反応容器に、前述のポリエステルポリオールＡ（数平均分子量２０３０）１５０ｇを投入し、撹拌を開始した。その後、６０℃に温度を維持した前記反応生成物αの全量を数回に分けて反応容器内に投入した。その間、反応器内の温度は、７０℃より高くならないようにした。その後、反応器内の温度を７０～７５℃に維持して撹拌を継続した。ＩＲでイソシアナト基のＣ＝Ｏ伸縮振動の吸収がなくなったことを確認し、数平均分子量２３８０のウレタンアクリレート（以下、「ウレタンアクリレート１」と記す。）を得た。
　尚、ポリエステルポリオールＡに対して１倍モル量の４－ヒドロキシブチルアクリレート由来のアクリロイル基が導入されたとみなされるので、このウレタンアクリレート１に含まれるアクリロイル基の数は１分子当たり平均で１個であると想定できる。 (Example synthesis example 2-1)
In a 100 mL reaction vessel equipped with a stirrer, thermometer, dropping funnel and condenser, a mixture of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate (trade name: VESTANAT®) ) TMDI, manufactured by Evonik Degussa) 15.28 g, dioctyltin dilaurate 15 mg and p-methoxyphenol 24 mg were charged into a reaction vessel, and 10.48 g of 4-hydroxybutyl acrylate was added dropwise using a dropping funnel. During the dropping, the temperature in the reaction vessel was adjusted to 70 ° C. or lower. After completion of the dropwise addition, stirring was continued while maintaining the temperature in the reactor at 70 to 75 ° C. for 2 hours to obtain a reaction product (hereinafter referred to as reaction product α).
Into a 300 mL reaction vessel equipped with a stirrer, a thermometer and a condenser, 150 g of the aforementioned polyester polyol A (number average molecular weight 2030) was charged, and stirring was started. Thereafter, the total amount of the reaction product α maintained at 60 ° C. was introduced into the reaction vessel in several portions. Meanwhile, the temperature in the reactor was not allowed to rise above 70 ° C. Thereafter, the temperature in the reactor was maintained at 70 to 75 ° C., and stirring was continued. It was confirmed by IR that the absorption of C═O stretching vibration of the isocyanate group was lost, and urethane acrylate having a number average molecular weight of 2380 (hereinafter referred to as “urethane acrylate 1”) was obtained.
Since it is considered that 1-fold molar amount of acryloyl group derived from 4-hydroxybutyl acrylate is introduced relative to polyester polyol A, the number of acryloyl groups contained in this urethane acrylate 1 is 1 on average per molecule. It can be assumed that there is.
（実施合成例２－２）
　攪拌装置、温度計、滴下ロートおよびコンデンサーを備えた１００ｍＬの反応容器に、２，２，４－トリメチルヘキサメチレンジイソシアネートと２，４，４－トリメチルヘキサメチレンジイソシアネートの混合物（商品名：ＶＥＳＴＡＮＡＴ（登録商標）ＴＭＤＩ、エボニックデグサ製）２７．８３ｇ、ジオクチル錫ジラウレート３０ｍｇおよびｐ－メトキシフェノール２４ｍｇを反応容器に投入し、４－ヒドロキシブチルアクリレート１９．０８ｇを滴下ロートを用いて滴下投入した。滴下中、反応容器内の温度は７０℃以下になるようにした。滴下終了後、２時間、反応器内の温度を７０～７５℃に維持したまま、撹拌を継続して反応生成物（以下、反応生成物βと記す。）を得た。
　攪拌装置、温度計およびコンデンサーを備えた３００ｍＬの反応容器に、前述のポリエステルポリオールＡ（数平均分子量２０３０）１５０ｇを投入し、撹拌を開始した。その後、６０℃に温度を維持した前記反応生成物βの全量を数回に分けて反応容器内に投入した。その間、反応器内の温度は、７０℃より高くならないようにした。その後、反応器内の温度を７０～７５℃に維持して撹拌を継続した。ＩＲでイソシアナト基のＣ＝Ｏ伸縮振動の吸収がなくなったことを確認し、数平均分子量２６７０のウレタンアクリレート（以下、「ウレタンアクリレート２」と記す。）を得た。
　尚、ポリエステルポリオールＡに対して１．８倍モル量の４－ヒドロキシブチルアクリレート由来のアクリロイル基が導入されたとみなされるので、このウレタンアクリレート２に含まれるアクリロイル基の数は１分子当たり平均で１．８個であると想定できる。 (Example synthesis example 2-2)
In a 100 mL reaction vessel equipped with a stirrer, thermometer, dropping funnel and condenser, a mixture of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate (trade name: VESTANAT®) ) TMDI, manufactured by Evonik Degussa) 27.83 g, dioctyltin dilaurate 30 mg and p-methoxyphenol 24 mg were charged into a reaction vessel, and 4-hydroxybutyl acrylate 19.08 g was added dropwise using a dropping funnel. During the dropping, the temperature in the reaction vessel was adjusted to 70 ° C. or lower. After completion of the dropwise addition, stirring was continued for 2 hours while maintaining the temperature in the reactor at 70 to 75 ° C. to obtain a reaction product (hereinafter referred to as reaction product β).
Into a 300 mL reaction vessel equipped with a stirrer, a thermometer and a condenser, 150 g of the aforementioned polyester polyol A (number average molecular weight 2030) was charged, and stirring was started. Thereafter, the total amount of the reaction product β maintained at a temperature of 60 ° C. was introduced into the reaction vessel in several portions. Meanwhile, the temperature in the reactor was not allowed to rise above 70 ° C. Thereafter, the temperature in the reactor was maintained at 70 to 75 ° C., and stirring was continued. It was confirmed by IR that the absorption of C═O stretching vibration of the isocyanato group was lost, and urethane acrylate having a number average molecular weight of 2670 (hereinafter referred to as “urethane acrylate 2”) was obtained.
Since it is considered that acryloyl groups derived from 4-hydroxybutyl acrylate in a molar amount of 1.8 times that of polyester polyol A are introduced, the number of acryloyl groups contained in this urethane acrylate 2 is 1 on an average per molecule. .8 can be assumed.
（実施合成例２－３）
　攪拌装置、温度計およびコンデンサーを備えた３００ｍＬの反応容器に、前述のポリエステルポリオールＡ（数平均分子量２０３０）１５０ｇ、４－ヒドロキシブチルアクリレート１５．７３ｇ、ジオクチル錫ジラウレート３０ｍｇおよびｐ－メトキシフェノール２４ｍｇを反応容器を投入し、撹拌を開始した。その後、２，２，４－トリメチルヘキサメチレンジイソシアネートと２，４，４－トリメチルヘキサメチレンジイソシアネートの混合物（商品名：ＶＥＳＴＡＮＡＴ（登録商標）ＴＭＤＩ、エボニックデグサ製）２２．９４ｇを、滴下ロートを用いて滴下投入した。滴下中、反応容器内の温度は７０℃以下になるようにした。その後、反応器内の温度を７０～７５℃に維持して撹拌を継続した。ＩＲでイソシアナト基のＣ＝Ｏ伸縮振動の吸収がなくなったことを確認し、数平均分子量２５６０のウレタンアクリレート（以下、「ウレタンアクリレート３」と記す。）を得た。
　尚、ポリエステルポリオールＡに対して１．５倍モル量の４－ヒドロキシブチルアクリレート由来のアクリロイル基が導入されたとみなされるので、このウレタンアクリレート３に含まれるアクリロイル基の数は１分子当たり平均で１．５個であると想定できる。 (Exemplary Synthesis Example 2-3)
In a 300 mL reaction vessel equipped with a stirrer, a thermometer and a condenser, the above-mentioned polyester polyol A (number average molecular weight 2030) 150 g, 4-hydroxybutyl acrylate 15.73 g, dioctyltin dilaurate 30 mg and p-methoxyphenol 24 mg were reacted. The container was charged and stirring was started. Thereafter, 22.94 g of a mixture of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate (trade name: VESTANAT (registered trademark) TMDI, manufactured by Evonik Degussa) was added using a dropping funnel. Added dropwise. During the dropping, the temperature in the reaction vessel was adjusted to 70 ° C. or lower. Thereafter, the temperature in the reactor was maintained at 70 to 75 ° C., and stirring was continued. It was confirmed by IR that absorption of C═O stretching vibration of the isocyanato group was lost, and urethane acrylate having a number average molecular weight of 2560 (hereinafter referred to as “urethane acrylate 3”) was obtained.
In addition, since it is considered that 1.5 times mole amount of acryloyl group derived from 4-hydroxybutyl acrylate with respect to polyester polyol A is introduced, the number of acryloyl groups contained in this urethane acrylate 3 is 1 on an average per molecule. .5 can be assumed.
（実施合成例２－４）
　攪拌装置、温度計およびコンデンサーを備えた３００ｍＬの反応容器に、前述のポリエステルポリオールＡ（数平均分子量２０３０）１５０ｇ、４－ヒドロキシブチルアクリレート１９．０８ｇ、ジオクチル錫ジラウレート３０ｍｇおよびｐ－メトキシフェノール２４ｍｇを反応容器を投入し、撹拌を開始した。その後、２，２，４－トリメチルヘキサメチレンジイソシアネートと２，４，４－トリメチルヘキサメチレンジイソシアネートの混合物（商品名：ＶＥＳＴＡＮＡＴ（登録商標）ＴＭＤＩ、エボニックデグサ製）２７．８３ｇを、滴下ロートを用いて滴下投入した。滴下中、反応容器内の温度は７０℃以下になるようにした。その後、反応器内の温度を７０～７５℃に維持して撹拌を継続した。ＩＲでイソシアナト基のＣ＝Ｏ伸縮振動の吸収がなくなったことを確認し、数平均分子量２６７０のウレタンアクリレート（以下、「ウレタンアクリレート４」と記す。）を得た。
　尚、ポリエステルポリオールＡに対して１．８倍モル量の４－ヒドロキシブチルアクリレート由来のアクリロイル基が導入されたとみなされるので、このウレタンアクリレート４に含まれるアクリロイル基の数は１分子当たり平均で１．８個であると想定できる。 (Example synthesis example 2-4)
In a 300 mL reaction vessel equipped with a stirrer, a thermometer and a condenser, the above-mentioned polyester polyol A (number average molecular weight 2030) 150 g, 4-hydroxybutyl acrylate 19.08 g, dioctyltin dilaurate 30 mg and p-methoxyphenol 24 mg were reacted. The container was charged and stirring was started. Thereafter, 27.83 g of a mixture of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate (trade name: VESTANAT (registered trademark) TMDI, manufactured by Evonik Degussa) was added using a dropping funnel. Added dropwise. During the dropping, the temperature in the reaction vessel was adjusted to 70 ° C. or lower. Thereafter, the temperature in the reactor was maintained at 70 to 75 ° C., and stirring was continued. It was confirmed by IR that absorption of C═O stretching vibration of the isocyanate group was lost, and urethane acrylate having a number average molecular weight of 2670 (hereinafter referred to as “urethane acrylate 4”) was obtained.
Since it is considered that acryloyl groups derived from 4-hydroxybutyl acrylate in a molar amount of 1.8 times that of polyester polyol A are introduced, the number of acryloyl groups contained in this urethane acrylate 4 is 1 on average per molecule. .8 can be assumed.
（実施合成例２－５）
　攪拌装置、温度計、滴下ロートおよびコンデンサーを備えた１００ｍＬの反応容器に、２，２，４－トリメチルヘキサメチレンジイソシアネートと２，４，４－トリメチルヘキサメチレンジイソシアネートの混合物（商品名：ＶＥＳＴＡＮＡＴ（登録商標）ＴＭＤＩ、エボニックデグサ製）２２．９４ｇ、ジオクチル錫ジラウレート３０ｍｇおよびｐ－メトキシフェノール２４ｍｇを反応容器に投入し、４－ヒドロキシブチルアクリレート１５．７３ｇを滴下ロートを用いて滴下投入した。滴下中、反応容器内の温度は７０℃以下になるようにした。滴下終了後、２時間、反応器内の温度を７０～７５℃に維持したまま、撹拌を継続して反応生成物（以下、反応生成物γと記す。）を得た。
　攪拌装置、温度計およびコンデンサーを備えた３００ｍＬの反応容器に、ポリエステルポリオール（商品名：クラレポリオールＰ－２０５０、水酸基価５７．０ｍｇＫＯＨ／ｇ、株式会社クラレ製、セバシン酸および３－メチル－１，５－ペンタンジオールを原料に用いて製造されたポリエステルポリオール、数平均分子量１９８０）７５ｇ、ポリエステルポリオール（商品名：クラレポリオールＰ－２０１０、水酸基価５７．０ｍｇＫＯＨ／ｇ、株式会社クラレ製、アジピン酸および３－メチル－１，５－ペンタンジオールを原料に用いて製造されたポリエステルポリオール、数平均分子量２０００）７５ｇを投入し、撹拌を開始した。その後、６０℃に温度を維持した前記反応生成物γの全量を数回に分けて反応容器内に投入した。その間、反応器内の温度は、７０℃より高くならないようにした。その後、反応器内の温度を７０～７５℃に維持して撹拌を継続した。ＩＲでイソシアナト基のＣ＝Ｏ伸縮振動の吸収がなくなったことを確認し、数平均分子量２５２０のウレタンアクリレート（以下、「ウレタンアクリレート５」と記す。）を得た。
　尚、ポリエステルポリオールに対して１．５倍モル量の４－ヒドロキシブチルアクリレート由来のアクリロイル基が導入されたとみなされるので、このウレタンアクリレート５に含まれるアクリロイル基の数は１分子当たり平均で１．５個であると想定できる。 (Example synthesis 2-5)
In a 100 mL reaction vessel equipped with a stirrer, thermometer, dropping funnel and condenser, a mixture of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate (trade name: VESTANAT®) ) TMDI, manufactured by Evonik Degussa) 22.94 g, 30 mg of dioctyltin dilaurate and 24 mg of p-methoxyphenol were added to the reaction vessel, and 15.73 g of 4-hydroxybutyl acrylate was added dropwise using a dropping funnel. During the dropping, the temperature in the reaction vessel was adjusted to 70 ° C. or lower. After completion of the dropping, stirring was continued for 2 hours while maintaining the temperature in the reactor at 70 to 75 ° C. to obtain a reaction product (hereinafter referred to as reaction product γ).
In a 300 mL reaction vessel equipped with a stirrer, a thermometer and a condenser, polyester polyol (trade name: Kuraray polyol P-2050, hydroxyl value 57.0 mg KOH / g, manufactured by Kuraray Co., Ltd., sebacic acid and 3-methyl-1, Polyester polyol produced using 5-pentanediol as a raw material, number average molecular weight 1980) 75 g, polyester polyol (trade name: Kuraray polyol P-2010, hydroxyl value 57.0 mg KOH / g, manufactured by Kuraray Co., Ltd., adipic acid and A polyester polyol produced using 3-methyl-1,5-pentanediol as a raw material, number average molecular weight 2000) 75 g was added, and stirring was started. Thereafter, the total amount of the reaction product γ maintained at 60 ° C. was divided into several times and charged into the reaction vessel. Meanwhile, the temperature in the reactor was not allowed to rise above 70 ° C. Thereafter, the temperature in the reactor was maintained at 70 to 75 ° C., and stirring was continued. It was confirmed by IR that absorption of C═O stretching vibration of the isocyanate group was lost, and urethane acrylate having a number average molecular weight of 2520 (hereinafter referred to as “urethane acrylate 5”) was obtained.
Since it is considered that 1.5 times mole amount of acryloyl group derived from 4-hydroxybutyl acrylate was introduced relative to the polyester polyol, the number of acryloyl groups contained in this urethane acrylate 5 is 1. It can be assumed that there are five.
（実施合成例２－６）
　攪拌装置、温度計、滴下ロートおよびコンデンサーを備えた１００ｍＬの反応容器に、２，２，４－トリメチルヘキサメチレンジイソシアネートと２，４，４－トリメチルヘキサメチレンジイソシアネートの混合物（商品名：ＶＥＳＴＡＮＡＴ（登録商標）ＴＭＤＩ、エボニックデグサ製）２７．８３ｇ、ジオクチル錫ジラウレート３０ｍｇおよびｐ－メトキシフェノール２４ｍｇを反応容器に投入し、４－ヒドロキシブチルアクリレート１９．０８ｇを滴下ロートを用いて滴下投入した。滴下中、反応容器内の温度は７０℃以下になるようにした。滴下終了後、２時間、反応器内の温度を７０～７５℃に維持したまま、撹拌を継続して反応生成物（以下、反応生成物ωと記す。）を得た。
　攪拌装置、温度計およびコンデンサーを備えた３００ｍＬの反応容器に、ポリエステルポリオール（商品名：クラレポリオールＰ－２０５０、水酸基価５７．０ｍｇＫＯＨ／ｇ、株式会社クラレ製、数平均分子量１９８０）７５ｇ、ポリエステルポリオール（商品名：クラレポリオールＰ－２０１０、水酸基価５７．０ｍｇＫＯＨ／ｇ、株式会社クラレ製、数平均分子量２０００）７５ｇを投入し、撹拌を開始した。その後、６０℃に温度を維持した前記反応生成物ωの全量を数回に分けて反応容器内に投入した。その間、反応器内の温度は、７０℃より高くならないようにした。その後、反応器内の温度を７０～７５℃に維持して撹拌を継続した。ＩＲでイソシアナト基のＣ＝Ｏ伸縮振動の吸収がなくなったことを確認し、数平均分子量２６３０のウレタンアクリレート（以下、「ウレタンアクリレート６」と記す。）を得た。
　尚、ポリエステルポリオールに対して１．８倍モル量の４－ヒドロキシブチルアクリレート由来のアクリロイル基が導入されたとみなされるので、このウレタンアクリレート６に含まれるアクリロイル基の数は１分子当たり平均で１．８個であると想定できる。 (Example synthesis 2-6)
In a 100 mL reaction vessel equipped with a stirrer, thermometer, dropping funnel and condenser, a mixture of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate (trade name: VESTANAT®) ) TMDI, manufactured by Evonik Degussa) 27.83 g, dioctyltin dilaurate 30 mg and p-methoxyphenol 24 mg were charged into a reaction vessel, and 4-hydroxybutyl acrylate 19.08 g was added dropwise using a dropping funnel. During the dropping, the temperature in the reaction vessel was adjusted to 70 ° C. or lower. After completion of the dropwise addition, stirring was continued while maintaining the temperature in the reactor at 70 to 75 ° C. for 2 hours to obtain a reaction product (hereinafter referred to as reaction product ω).
In a 300 mL reaction vessel equipped with a stirrer, a thermometer and a condenser, 75 g of polyester polyol (trade name: Kuraray polyol P-2050, hydroxyl value 57.0 mg KOH / g, manufactured by Kuraray Co., Ltd., number average molecular weight 1980), polyester polyol (Product name: Kuraray polyol P-2010, hydroxyl value 57.0 mgKOH / g, manufactured by Kuraray Co., Ltd., number average molecular weight 2000) was added in an amount of 75 g, and stirring was started. Thereafter, the entire amount of the reaction product ω maintained at 60 ° C. was divided into several times and charged into the reaction vessel. Meanwhile, the temperature in the reactor was not allowed to rise above 70 ° C. Thereafter, the temperature in the reactor was maintained at 70 to 75 ° C., and stirring was continued. It was confirmed by IR that absorption of C═O stretching vibration of the isocyanato group was lost, and urethane acrylate having a number average molecular weight of 2630 (hereinafter referred to as “urethane acrylate 6”) was obtained.
Since it is considered that 1.8 times mole amount of acryloyl group derived from 4-hydroxybutyl acrylate was introduced relative to the polyester polyol, the number of acryloyl groups contained in this urethane acrylate 6 was 1. It can be assumed that there are eight.
（実施配合例１）
　ウレタンアクリレート５　９９．０質量部、１－ヒドロキシシクロヘキシルフェニルケトン（商品名：ＩＲＧＡＣＵＲＥ（登録商標）１８４、ＢＡＳＦ製）０．８質量部、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド（商品名：ＳｐｅｅｄＣｕｒｅ　ＴＰＯ、Ｌａｍｂｓｏｎ製）０．２質量部およびペンタエリスリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］（商品名：ＩＲＧＡＮＯＸ（登録商標）１０１０、ＢＡＳＦ製）１．０質量部を、自転・公転ミキサー（株式会社シンキー製、商品名：あわとり錬太郎　ＡＲＥ－３１０）を用いて混合した。この配合物を重合性組成物Ａ１とした。重合性組成物Ａ１の２５℃での粘度は３３，６９０ｍＰａ・ｓであった。 (Example of formulation 1)
Urethane acrylate 5 99.0 parts by mass, 1-hydroxycyclohexyl phenyl ketone (trade name: IRGACURE (registered trademark) 184, manufactured by BASF) 0.8 parts by mass, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name: 0.2 parts by weight of SpeedCure TPO, manufactured by Lambson) and pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX (registered trademark) 1010, manufactured by BASF) 1.0 part by mass was mixed using a rotation / revolution mixer (manufactured by Shinky Co., Ltd., trade name: Rentaro Awatori ARE-310). This blend was designated as a polymerizable composition A1. The viscosity at 25 ° C. of the polymerizable composition A1 was 33,690 mPa · s.
（実施配合例２～６および比較配合例１、２）
　実施配合例１と同様の方法によって、表１に示す配合組成に従って配合した。実施配合例２～６で調製した配合物を、それぞれ重合性組成物Ａ２～Ａ６とし、比較配合例１および２で調製した配合物を重合性組成物Ｂ１、Ｂ２とした。
　なお、表１中に記載の実施配合例および比較配合例の各成分の数字の単位は「質量部」である。 (Example formulation examples 2 to 6 and comparative formulation examples 1 and 2)
In the same manner as in Example 1 of blending, blending was performed according to the blending composition shown in Table 1. The formulations prepared in Examples 2 to 6 were designated as polymerizable compositions A2 to A6, respectively, and the formulations prepared in comparative formulation examples 1 and 2 were designated as polymerizable compositions B1 and B2.
In addition, the unit of the number of each component of the implementation formulation example and the comparative formulation example described in Table 1 is “parts by mass”.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　※１　Ｎ，Ｎ－ジエチルアクリルアミド（商品名：ＤＥＡＡ、興人フィルム＆ケミカルズ株式会社製）
　※２　トリシクロデカンジメタノールジアクリレート（商品名；ＡＤＣＰ、共栄社化学株式会社製）
　※３　２－ヒドロキシプロピルメタクリレート（商品名：ＨＰＭＡ、株式会社日本触媒製）
　※４　４－ヒドロキシブチルアクリレート（商品名：４ＨＢＡ、大阪有機化学工業株式会社製）
　※５　２－ヒドロキシブチルメタクリレート（商品名：ライトエステルＨＯＢ（Ｎ）、共栄社化学株式会社製）
　※６　ジエチレングリコールモノエチルエーテルアクリレート（商品名：ビスコート＃１９０、大阪有機化学工業株式会社製、粘度（２５℃）：３ｍＰａ・ｓ）
　※７　ラウリルアクリレート（商品名：ブレンマーＬＡ、日油株式会社製、粘度（２５℃）：４ｍＰａ・ｓ）
　※８　グリセリンモノラウレート（商品名：ポエム　Ｍ－３００、理研ビタミン株式会社製）
　※９　水添ロジンエステル樹脂（商品名：パインクリスタル　ＫＥ－１００、ヤスハラケミカル株式会社製）
　※１０　水添ロジンエステル樹脂（商品名：パインクリスタル　ＫＥ－３１１、ヤスハラケミカル株式会社製）
　※１１　テルペン－フェノール樹脂（商品名：ＹＳポリスター　ＴＨ１３０、ヤスハラケミカル株式会社製）
　※１２　ポリエステルポリオール（商品名：クラレポリオール　Ｐ－２０１１、株式会社クラレ製）
　※１３　脂肪族ポリエステルジオール（商品名：プラクセルＬ２２０ＡＬ 　株式会社ダイセル製）
　※１４　ＩＲＧＡＮＯＸ（登録商標）１０１０（化合物名：ペンタエリスリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、ＢＡＳＦ製）
　※１５　光重合開始剤　ＳｐｅｅｄＣｕｒｅ　ＴＰＯ（化合物名：２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド、Ｌａｍｂｓｏｎ製）
　※１６　光重合開始剤　ＩＲＧＡＣＵＲＥ（登録商標）１８４（化合物名：１－ヒドロキシシクロヘキシルフェニルケトン、ＢＡＳＦ製） * 1 N, N-diethylacrylamide (trade name: DEAA, manufactured by Kojin Film & Chemicals Co., Ltd.)
* 2 Tricyclodecane dimethanol diacrylate (trade name; ADCP, manufactured by Kyoeisha Chemical Co., Ltd.)
* 3 2-Hydroxypropyl methacrylate (trade name: HPMA, manufactured by Nippon Shokubai Co., Ltd.)
* 4 4-hydroxybutyl acrylate (trade name: 4HBA, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
* 5 2-hydroxybutyl methacrylate (trade name: Light Ester HOB (N), manufactured by Kyoeisha Chemical Co., Ltd.)
* 6 Diethylene glycol monoethyl ether acrylate (trade name: Biscoat # 190, manufactured by Osaka Organic Chemical Industry Co., Ltd., viscosity (25 ° C.): 3 mPa · s)
* 7 Lauryl acrylate (trade name: Bremmer LA, manufactured by NOF Corporation, viscosity (25 ° C.): 4 mPa · s)
* 8 Glycerol monolaurate (trade name: Poem M-300, manufactured by Riken Vitamin Co., Ltd.)
* 9 Hydrogenated rosin ester resin (trade name: Pine Crystal KE-100, manufactured by Yasuhara Chemical Co., Ltd.)
* 10 Hydrogenated rosin ester resin (trade name: Pine Crystal KE-311, manufactured by Yasuhara Chemical Co., Ltd.)
* 11 Terpene-phenol resin (trade name: YS Polystar TH130, manufactured by Yasuhara Chemical Co., Ltd.)
* 12 Polyester polyol (trade name: Kuraray polyol P-2011, manufactured by Kuraray Co., Ltd.)
* 13 Aliphatic polyester diol (trade name: Plaxel L220AL, manufactured by Daicel Corporation)
* 14 IRGANOX (registered trademark) 1010 (compound name: pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by BASF)
* 15 Photopolymerization initiator SpeedCure TPO (compound name: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, manufactured by Lambson)
* 16 Photopolymerization initiator IRGACURE (registered trademark) 184 (compound name: 1-hydroxycyclohexyl phenyl ketone, manufactured by BASF)
＜光学用粘着シートの製造＞
　表１に示す重合性組成物Ａ１～重合性組成物Ａ６および重合性組成物Ｂ１、Ｂ２を、それぞれ、アプリケーターを用い、膜厚が２００μｍとなるようにシリコーンでコートされたポリエチレンテレフタレート（以下、ＰＥＴと記す。）フィルム（１００ｍｍ×１００ｍｍ×５０μｍ）に塗布し、上面を２５μｍ厚のシリコーンでコートされたＰＥＴフィルムで覆った後、メタルハライドランプを用いたコンベア式紫外線照射装置（株式会社ジーエス・ユアサライティング製、商品名：ＧＳＮ２－４０）を用い、シリコーンでコートされたＰＥＴフィルム越しに、照射強度１９０ｍＷ／ｃｍ２（３６５ｎｍの値）、照射量６０００ｍＪ／ｃｍ２（３６５ｎｍの値）の条件で紫外線を照射して重合させ、離型ＰＥＴフィルムに挟まれた膜厚が約２００μｍの光学用粘着シートを得た。重合性組成物Ａ１～重合性組成物Ａ６および重合性組成物Ｂ１、Ｂ２を用いて製造された前記光学用粘着シートを、それぞれ、粘着シートＡ１～粘着シートＡ６および粘着シートＢ１、Ｂ２とした。 <Manufacture of optical adhesive sheet>
Polymeric compositions A1 to A6 and polymerizable compositions B1 and B2 shown in Table 1 were each coated with silicone terephthalate (hereinafter referred to as PET) using an applicator and having a film thickness of 200 μm. After coating on a film (100 mm × 100 mm × 50 μm) and covering the upper surface with a PET film coated with 25 μm thick silicone, a conveyor type ultraviolet irradiation device using a metal halide lamp (GS Yuasa Lighting Co., Ltd.) Manufactured under the trade name: GSN2-40), and ultraviolet rays were irradiated through a silicone-coated PET film under the conditions of irradiation intensity of 190 mW / cm 2 (value of 365 nm) and irradiation amount of 6000 mJ / cm 2 (value of 365 nm). The film thickness is about 2 between the exposed PET film and the release PET film. To obtain an optical pressure-sensitive adhesive sheet for 0 .mu.m. The optical pressure-sensitive adhesive sheets produced using the polymerizable compositions A1 to A6 and the polymerizable compositions B1 and B2 were referred to as pressure-sensitive adhesive sheets A1 to A6 and pressure-sensitive adhesive sheets B1 and B2, respectively.
＜前記粘着シートを用いた試験片の作製方法＞
　前記粘着シートＡ１～粘着シートＡ６および粘着シートＢ１、Ｂ２で、それぞれ、気泡が界面に入らないように、２枚のガラス板（５０ｍｍ×５０ｍｍ×０．７ｍｍ、ガラスの種類　商品名：ＥＡＧＬＥ　ＸＧ（登録商標）、ＣＯＲＮＩＮＧ製）で該粘着シートの両面から挟むように貼りつけることにより、試験片を作製した。
　粘着シートＡ１～粘着シートＡ６および粘着シートＢ１、Ｂ２を用いて作製された試験片を、それぞれ、試験片ＡＳ１－１～試験片ＡＳ６－１および試験片ＢＳ１－１、ＢＳ２－１とした。これらの試験片のガラスへの密着性を後述の方法により測定した。その結果を表３に記す。
　前記粘着シートＡ１～粘着シートＡ６および粘着シートＢ１、Ｂ２で、それぞれ、気泡が界面に入らないように、２枚のガラス板（５０ｍｍ×５０ｍｍ×０．７ｍｍ、ガラスの種類　商品名：ＥＡＧＬＥ　ＸＧ（登録商標）、ＣＯＲＮＩＮＧ製）と樹脂板（三菱ガス化学社製　商品名：ＭＲ－８５、または三菱レイヨン社製　商品名 ：アクリライト　ＭＲ－２００）で該粘着シートの両面から挟むように貼りつけることにより、試験片を作製した。
　重合性組成物Ａ１～Ａ６および重合性組成物Ｂ１、Ｂ２を用いて製造された、前記ガラス板と前記樹脂板に挟まれた膜厚が約２００μｍの評価試験用の重合物膜を、それぞれ試験片ＡＳ１－２～試験片ＡＳ６－２および試験片ＢＳ１－２、ＢＳ２－２とした。これらの試験片の樹脂板への密着性を後述の方法により測定した。その結果を表４に記す。また、これらの試験片を用いて、後述の耐剥がれ試験を行った。その結果を表４に示す。また、表４に記載の「ＰＭＭＡとガラス板との耐剥がれ試験」とは、前記樹脂板にＭＲ－２００を用いた場合の試験のことである。また、表４に記載の「ＰＣとガラス板との耐剥がれ試験」とは、前記樹脂板にＭＲ－８５を用いた場合の試験のことである。 <Method for producing test piece using the pressure-sensitive adhesive sheet>
The adhesive sheets A1 to A6 and the adhesive sheets B1 and B2 each have two glass plates (50 mm × 50 mm × 0.7 mm, glass type, product name: EAGLE XG () so that air bubbles do not enter the interface. A test piece was prepared by adhering the adhesive sheet so as to be sandwiched from both sides with a registered trademark and CORNING.
Test pieces prepared using the pressure-sensitive adhesive sheets A1 to A6 and the pressure-sensitive adhesive sheets B1 and B2 were referred to as test pieces AS1-1 to AS6-1 and test pieces BS1-1 and BS2-1, respectively. The adhesion of these test pieces to glass was measured by the method described below. The results are shown in Table 3.
The adhesive sheets A1 to A6 and the adhesive sheets B1 and B2 each have two glass plates (50 mm × 50 mm × 0.7 mm, glass type, product name: EAGLE XG () so that air bubbles do not enter the interface. (Registered trademark), CORNING) and resin plate (Mitsubishi Gas Chemical Co., Ltd., trade name: MR-85, or Mitsubishi Rayon Co., Ltd., trade name: Acrylite MR-200). Thus, a test piece was prepared.
A polymer film for an evaluation test, which was manufactured using the polymerizable compositions A1 to A6 and the polymerizable compositions B1 and B2 and was sandwiched between the glass plate and the resin plate and having a thickness of about 200 μm, was tested. The specimens AS1-2 to AS6-2 and specimens BS1-2 and BS2-2 were used. The adhesion of these test pieces to the resin plate was measured by the method described later. The results are shown in Table 4. Moreover, the below-mentioned peeling resistance test was done using these test pieces. The results are shown in Table 4. Further, “PMMA and glass plate peeling resistance test” described in Table 4 is a test when MR-200 is used for the resin plate. The “Peeling resistance test between PC and glass plate” shown in Table 4 is a test when MR-85 is used for the resin plate.
＜試験片の作製方法＞
　前記重合性組成物Ａ４～重合性組成物Ａ６および重合性組成物Ｂ１、Ｂ２を、それぞれ、膜厚が２００μｍとなるようにガラス板に塗布し、同種同形のガラス板で挟みこみ、前述の光学用粘着シートの製造の露光条件と同様の照射条件で紫外線を照射して重合させ、ガラス板に挟まれた膜厚が約２００μｍの評価試験用の重合物膜を得た。重合性組成物Ａ４～Ａ６および重合性組成物Ｂ１、Ｂ２を用いて製造された、前記ガラス板に挟まれた膜厚が約２００μｍの評価試験用の重合物膜を、それぞれ試験片ＡＬ４－１～試験片ＡＬ６－１および試験片ＢＬ１－１、ＢＬ２－１とした。これらの試験片のガラスへの密着性を後述の方法により測定した。その結果を表３に記す。
　前記重合性組成物Ａ４～重合性組成物Ａ６および重合性組成物Ｂ１、Ｂ２を、それぞれ、膜厚が２００μｍとなるようにガラス板に塗布し、樹脂板（前述の２種）で挟みこみ、メタルハライドランプを用いたコンベア式紫外線照射装置（株式会社ジーエス・ユアサライティング製、商品名：ＧＳＮ２－４０）を用い、ガラス板越しに、前述と同様の照射条件で紫外線を照射して重合させ、ガラス板と樹脂板に挟まれた膜厚が約２００μｍの評価試験用の重合物膜を得た。重合性組成物Ａ４～Ａ６および重合性組成物Ｂ１、Ｂ２を用いて製造された、前記ガラス板と前記樹脂板に挟まれた膜厚が約２００μｍの評価試験用の重合物膜を、それぞれ試験片ＡＬ４－２～試験片ＡＬ６－２および試験片ＢＬ１－２、ＢＬ２－２とした。これらの試験片の樹脂板への密着性を後述の方法により測定した。その結果を表４に記す。また、これらの試験片を用いて、後述の耐剥がれ試験を行った。その結果を表５に示す。 <Method for preparing specimen>
The polymerizable composition A4 to the polymerizable composition A6 and the polymerizable compositions B1 and B2 are each applied to a glass plate so as to have a film thickness of 200 μm, and sandwiched between glass plates of the same type and shape. Polymerization was performed by irradiating with ultraviolet rays under the same irradiation conditions as the exposure conditions for producing the pressure-sensitive adhesive sheet, and a polymer film for an evaluation test having a thickness of about 200 μm sandwiched between glass plates was obtained. A polymer film for evaluation test having a film thickness of about 200 μm, sandwiched between the glass plates, produced using the polymerizable compositions A4 to A6 and the polymerizable compositions B1 and B2, was used as a test piece AL4-1. Test piece AL6-1 and test pieces BL1-1 and BL2-1 were used. The adhesion of these test pieces to glass was measured by the method described below. The results are shown in Table 3.
The polymerizable composition A4 to the polymerizable composition A6 and the polymerizable compositions B1 and B2 are each applied to a glass plate so as to have a film thickness of 200 μm, and sandwiched between resin plates (the above-mentioned two types). Using a conveyor type ultraviolet irradiation device (trade name: GSN2-40, manufactured by GS Yuasa Lighting Co., Ltd.) using a metal halide lamp, the glass plate is irradiated with ultraviolet rays under the same irradiation conditions as described above to polymerize the glass. A polymer film for an evaluation test having a film thickness of about 200 μm sandwiched between the plate and the resin plate was obtained. A polymer film for an evaluation test, which was manufactured using the polymerizable compositions A4 to A6 and the polymerizable compositions B1 and B2 and was sandwiched between the glass plate and the resin plate and having a thickness of about 200 μm, was tested. The specimens AL4-2 to AL6-2 and specimens BL1-2 and BL2-2 were used. The adhesion of these test pieces to the resin plate was measured by the method described later. The results are shown in Table 4. Moreover, the below-mentioned peeling resistance test was done using these test pieces. The results are shown in Table 5.
＜耐剥がれ試験＞
　耐剥がれ試験とは、前述の試験片を６０℃、９０％ＲＨの恒温室槽に入れ、７２時間静置し、試験片を２３℃、５０％ＲＨの環境下取り出した後、４８時間、試験片を２３℃、５０％ＲＨの環境下に静置した。その後目視で樹脂板と試験片ＡＳ１－２～試験片ＡＳ６－２および試験片ＢＳ１－２、ＢＳ２－２および、試験片ＡＬ４－２～試験片ＡＬ６－２および試験片ＢＬ１－２、ＢＬ２－２との間または、ガラス板と試験片ＡＳ１－２～試験片ＡＳ６－２および試験片ＢＳ１－２、ＢＳ２－２および、試験片ＡＬ４－２～試験片ＡＬ６－２および試験片ＢＬ１－２、ＢＬ２－２との間に剥がれがないか目視で確認した。剥がれがあった場合は×、剥がれがなかった場合は○と表５に記す。 <Peeling resistance test>
The peeling resistance test means that the above-mentioned test piece is placed in a thermostatic chamber of 60 ° C. and 90% RH and left for 72 hours, and the test piece is taken out in an environment of 23 ° C. and 50% RH and then tested for 48 hours. The piece was allowed to stand in an environment of 23 ° C. and 50% RH. Thereafter, the resin plate and the test pieces AS1-2 to AS6-2 and the test pieces BS1-2 and BS2-2 and the test piece AL4-2 to the test pieces AL6-2 and the test pieces BL1-2 and BL2-2 are visually observed. Between the glass plate and the test piece AS1-2 to the test piece AS6-2 and the test piece BS1-2 and BS2-2, and the test piece AL4-2 to the test piece AL6-2 and the test piece BL1-2 and BL2. -2 was visually checked for peeling. In case of peeling, “X” is shown. In case of no peeling, “◯” is shown.
＜誘電率の測定＞
　２枚のシリコーンでコートされたＰＥＴフィルムを用いて、その間に、重合性組成物Ａ１～重合性組成物Ａ６および重合性組成物Ｂ１を、膜厚が約２ｍｍになるように挟み込み、前述と同様の照射条件で紫外線を照射して重合させ、シリコーンでコートされたＰＥＴフィルムに挟まれた膜厚が約２ｍｍの評価試験用の重合物膜を得た。この重合物膜をシリコーンでコートされたＰＥＴフィルムから剥離し、インピーダンスアナライザ（アジレント・テクノロジー株式会社製、商品名：４２９４Ａ　プレシジョン・インピーダンス・アナライザ　４０Ｈｚ－１１０ＭＨｚ）を用いて測定した。その結果を表２に記す。
　なお、重合性組成物Ａ１～重合性組成物Ａ６および重合性組成物Ｂ１、Ｂ２を重合して得られた、シリコーンでコートされたＰＥＴフィルムを剥離した厚さ２ｍｍの重合物膜を、それぞれ、重合物膜Ａ１～重合物膜Ａ６および重合物膜Ｂ１、Ｂ２とする。 <Measurement of dielectric constant>
Using two silicone-coated PET films, the polymerizable composition A1 to the polymerizable composition A6 and the polymerizable composition B1 are sandwiched between them so that the film thickness is about 2 mm. Under the irradiation conditions, ultraviolet rays were irradiated for polymerization to obtain a polymer film for evaluation test having a thickness of about 2 mm sandwiched between silicone-coated PET films. This polymer film was peeled off from the PET film coated with silicone, and measured using an impedance analyzer (trade name: 4294A Precision Impedance Analyzer 40 Hz-110 MHz, manufactured by Agilent Technologies, Inc.). The results are shown in Table 2.
A polymer film having a thickness of 2 mm obtained by polymerizing the polymerizable composition A1 to the polymerizable composition A6 and the polymerizable compositions B1 and B2 and peeling the PET film coated with silicone was respectively obtained. Polymer film A1 to polymer film A6 and polymer films B1 and B2 are used.
＜重合時の体積収縮率の測定＞
　重合前の重合性組成物Ａ１～Ａ６および重合性組成物Ｂ１、Ｂ２と、それらを重合した重合物の密度を、自動比重計（型式：ＤＭＡ－２２０Ｈ、新光電子株式会社製）を用いて、２３℃の温度条件で測定し、下記の式から重合時の体積収縮率を求めた。
　重合時の体積収縮率（％）＝（重合物の密度－重合性組成物の密度）／（重合物の密度）×１００
　その結果を表２に記す。 <Measurement of volumetric shrinkage during polymerization>
The polymerizable compositions A1 to A6 and the polymerizable compositions B1 and B2 before polymerization and the density of the polymer obtained by polymerizing them were measured using an automatic hydrometer (model: DMA-220H, manufactured by Shinko Denshi Co., Ltd.) The measurement was performed under a temperature condition of 23 ° C., and the volume shrinkage during polymerization was determined from the following formula.
Volume shrinkage during polymerization (%) = (polymer density−polymerizable composition density) / (polymer density) × 100
The results are shown in Table 2.
＜屈折率の測定＞
　前記重合物膜Ａ１～重合物膜Ａ６および重合物膜Ｂ１、Ｂ２を使用して、ＪＩＳ　Ｋ　７１０５に準拠して測定した。その結果を表２に記す。 <Measurement of refractive index>
Using the polymer film A1 to polymer film A6 and the polymer films B1 and B2, the measurement was performed according to JIS K 7105. The results are shown in Table 2.
＜貯蔵弾性率の測定＞
　前記重合物膜Ａ１～重合物膜Ａ６および重合物膜Ｂ１、Ｂ２を、それぞれレオメーター（Ａｕｔｏｎ　Ｐｅａｒ社製　ＭＲＣ３０１　測定治具　Ａｕｔｏｎ　Ｐｅａｒ社製　プレート ＰＰ２５）で２５℃において試験を行った。周波数０．１Ｈｚでの貯蔵弾性率を表２に記す。 <Measurement of storage modulus>
The polymer film A1 to polymer film A6 and the polymer films B1 and B2 were each tested at 25 ° C. with a rheometer (MRC301 measuring jig manufactured by Auton Pear, plate PP25 manufactured by Auton Pear). Table 2 shows the storage elastic modulus at a frequency of 0.1 Hz.
＜ガラスへの密着性＞
　前記試験片ＡＳ１－１～試験片ＡＳ６－１、試験片ＡＬ４－１～試験片ＡＬ６－１、試験片ＢＳ１－１、ＢＳ２－１および試験片ＢＬ１－１、ＢＬ２－１の外側のガラス面（両面）に、それぞれ、引張試験機（株式会社島津製作所製、ＥＺ　Ｔｅｓｔ／ＣＥ）のチャック部で挟み込むことができるように、両面テープを用いてプラスチック治具を貼り付けた。その後、引張試験機に、プラスチック治具が貼り付けられた重合物膜付の２枚のガラスを取り付け、５００ｍｍ／ｍｉｎの速度で両面のガラスをガラス面に対して垂直に剥がす方向に引っ張った。その際の破断時の力を塗布面積で割った値をガラスへの密着性として評価した。その結果を表４に記す。 <Adhesion to glass>
Outer glass surfaces of the test pieces AS1-1 to AS6-1, test pieces AL4-1 to test pieces AL6-1, test pieces BS1-1 and BS2-1, and test pieces BL1-1 and BL2-1 ( A plastic jig was affixed to the both surfaces using a double-sided tape so that each could be sandwiched between chuck portions of a tensile tester (manufactured by Shimadzu Corporation, EZ Test / CE). Thereafter, two glasses with a polymer film to which a plastic jig was attached were attached to a tensile tester, and pulled at a speed of 500 mm / min in a direction to peel the glass on both sides perpendicular to the glass surface. A value obtained by dividing the breaking force by the coating area at that time was evaluated as adhesion to glass. The results are shown in Table 4.
＜樹脂板とガラス板への密着性＞
　前記試験片ＡＳ１－２～試験片ＡＳ６－２、試験片ＡＬ４－２～試験片ＡＬ６－２、試験片ＢＳ１－２、ＢＳ２－２および試験片ＢＬ１－２、ＢＬ２－２の外側のガラス面と樹脂板面に、それぞれ、引張試験機のチャック部で挟み込むことができるように、両面テープを用いてプラスチック治具を貼り付けた。その後前述のガラスへの密着性試験と同様にしてガラス面に対して垂直に剥がす方向に引っ張った。その際の破断時の力を塗布面積で割った値を樹脂板とガラスへの密着性として評価した。その結果を表４に記す。 <Adhesion to resin plate and glass plate>
Test piece AS1-2 to test piece AS6-2, test piece AL4-2 to test piece AL6-2, test piece BS1-2, BS2-2 and test piece BL1-2, BL2-2, outer glass surface and A plastic jig was affixed to the resin plate surface using a double-sided tape so that each could be sandwiched between chuck portions of a tensile tester. Thereafter, the film was pulled in the direction of peeling perpendicularly to the glass surface in the same manner as in the adhesion test to glass described above. The value obtained by dividing the breaking force by the coating area at that time was evaluated as the adhesion between the resin plate and the glass. The results are shown in Table 4.
＜光学特性評価＞
　先述の試験片試験片ＡＳ１－１～試験片ＡＳ６－１および試験片ＢＳ１－１、ＢＳ２－１、ＡＬ４－１～試験片ＡＬ６－１および試験片ＢＬ１－１、ＢＬ２－１の全光線透過率、ｂ＊、ヘーズを後述の方法により測定した。その結果を表６に記す。また、８５℃、９５℃、６０℃９０％中で５００時間静置したのちの測定結果も合わせて表６に記す。 <Optical characteristic evaluation>
Total light transmittance of the test piece test piece AS1-1 to the test piece AS6-1 and the test pieces BS1-1, BS2-1, AL4-1 to the test piece AL6-1 and the test pieces BL1-1 and BL2-1. , B * and haze were measured by the methods described below. The results are shown in Table 6. Table 6 also shows the measurement results after standing at 85 ° C., 95 ° C., 60 ° C. and 90% for 500 hours.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　表２～表５の結果より、本発明（Ｉ）～本発明（ＩＩＩ）の重合性組成物を重合して得られた重合物は、ガラスへの密着性が良好で、高温条件下あるいは高温多湿条件下で長期間保存した場合にも、着色等の外観変化が起こりにくく、良好な光透過性を維持できることがわかった。
　また、本発明（ＩＶ）の重合性組成物は、重合時の体積収縮率が低く、かつ本発明（ＩＶ）の重合性組成物を重合して得られた重合物は、ガラスへの密着性が良好で、高温条件下あるいは高温多湿条件下で長期間保存した場合にも、良好な耐剥がれ性を維持できることがわかった。 From the results in Tables 2 to 5, the polymers obtained by polymerizing the polymerizable compositions of the present invention (I) to the present invention (III) have good adhesion to glass and are used under high temperature conditions or at high temperatures. It was found that even when stored for a long time under humid conditions, appearance changes such as coloring hardly occur, and good light transmittance can be maintained.
In addition, the polymerizable composition of the present invention (IV) has a low volume shrinkage during polymerization, and the polymer obtained by polymerizing the polymerizable composition of the present invention (IV) has an adhesive property to glass. It was found that good peeling resistance can be maintained even when stored for a long time under high temperature conditions or high temperature and high humidity conditions.
　以上のように、本発明（Ｉ）～本発明（ＩＩＩ）の重合性組成物を重合して得られた重合物膜は、ガラスへの密着性が良好で、高温条件下あるいは高温多湿条件下で長期間保存した場合にも、良好な耐剥がれ性を維持できる。また、誘電率も高い。さらに本発明（ＩＶ）の重合性組成物は、重合時の体積収縮率が低く、かつ本発明（ＩＶ）の重合性組成物を重合して得られた重合物膜は、樹脂板への密着性が良好で、高温条件下あるいは高温多湿条件下で長期間保存した場合にも、良好な耐剥がれ性を維持できる。従って、該重合物膜を、画像表示装置の画像表示部と透光性の保護部との間に介在させる透明光学樹脂層として使用した場合には、良好な光学粘着層を提供することができる。
　従って、該重合物を画像表示装置に使用することは有用である。 As described above, the polymer film obtained by polymerizing the polymerizable composition of the present invention (I) to the present invention (III) has good adhesion to glass and is used under high temperature conditions or high temperature and high humidity conditions. Even when stored for a long time, good peeling resistance can be maintained. Also, the dielectric constant is high. Furthermore, the polymerizable composition of the present invention (IV) has a low volume shrinkage during polymerization, and the polymer film obtained by polymerizing the polymerizable composition of the present invention (IV) is adhered to the resin plate. Good peeling resistance can be maintained even when stored for a long time under high temperature conditions or high temperature and high humidity conditions. Therefore, when the polymer film is used as a transparent optical resin layer interposed between the image display portion and the translucent protective portion of the image display device, a good optical adhesive layer can be provided. .
Therefore, it is useful to use the polymer in an image display device.
　１　　表示装置
　２　　表示部
　３　　保護部
　４　　スペーサ
　５ａ、５ｂ　　重合物（層）
　６ａ、６ｂ　　偏光板
　７　　タッチセンサー DESCRIPTION OF SYMBOLS 1 Display apparatus 2 Display part 3 Protection part 4 Spacer 5a, 5b Polymer (layer)
6a, 6b Polarizing plate 7 Touch sensor

Claims (15)

  1. 　画像表示装置の画像表示部と透光性の保護部との間に介在させる重合物層を形成するための重合性組成物であって、該重合性組成物が、
    （成分１）数平均分子量が１０００～１５０００の範囲である（メタ）アクリロイル基含有高分子化合物、および
    （成分２）光重合開始剤
    を含み、かつ該重合性組成物を重合することにより得られる重合物の２５℃で周波数０．１Ｈｚでの貯蔵弾性率が１×１０３～１×１０５Ｐａであることを特徴とする重合性組成物。     A polymerizable composition for forming a polymer layer interposed between an image display portion and a translucent protective portion of an image display device, the polymerizable composition comprising:
    (Component 1) containing a (meth) acryloyl group-containing polymer compound having a number average molecular weight in the range of 1000 to 15000, and (Component 2) a photopolymerization initiator, and obtained by polymerizing the polymerizable composition. A polymerizable composition having a storage elastic modulus of 1 × 10 3 to 1 × 10 5 Pa at 25 ° C. and a frequency of 0.1 Hz.
  2. 　前記成分１が炭素数４～９のジオールから誘導される構造単位および炭素数４～１０のジカルボン酸から誘導される構造単位を含むポリエステル構造単位を有する（メタ）アクリロイル基含有高分子化合物であることを特徴とする請求項１に記載の重合性組成物。 The component 1 is a (meth) acryloyl group-containing polymer compound having a polyester structural unit including a structural unit derived from a diol having 4 to 9 carbon atoms and a structural unit derived from a dicarboxylic acid having 4 to 10 carbon atoms. The polymerizable composition according to claim 1.
  3. 　前記成分１がウレタン結合を有する（メタ）アクリロイル基含有高分子化合物であることを特徴とする請求項１または２に記載の重合性組成物。 The polymerizable composition according to claim 1 or 2, wherein the component 1 is a (meth) acryloyl group-containing polymer compound having a urethane bond.
  4. 　（成分３）アルコール性水酸基とアミド基の少なくとも一方を有するラジカル重合性不飽和基含有化合物
    をさらに含む請求項１～３のいずれか１項に記載の重合性組成物。     (Component 3) The polymerizable composition according to any one of claims 1 to 3, further comprising a radical polymerizable unsaturated group-containing compound having at least one of an alcoholic hydroxyl group and an amide group.
  5. 　（成分４）アルコール性水酸基とアミド基のいずれの基も有さず、かつ粘度が２５℃で５００ｍＰａ・ｓ以下である（メタ）アクリロイル基含有化合物
    をさらに含む請求項１～４のいずれか１項に記載の重合性組成物。     (Component 4) The compound according to any one of claims 1 to 4, further comprising a (meth) acryloyl group-containing compound having no alcoholic hydroxyl group or amide group and having a viscosity of 500 mPa · s or less at 25 ° C. The polymerizable composition according to item.
  6. 　前記成分４がエーテル結合を有することを特徴とする請求項５に記載の重合性組成物。 The polymerizable composition according to claim 5, wherein the component 4 has an ether bond.
  7. 　（成分５）（メタ）アクリロイル基を有さない非イオン界面活性剤、および
    （成分６）分子内に（メタ）アクリロイル基がなく、ラジカル重合を抑制する機能、ラジカル重合を禁止する機能、光重合性開始機能および界面活性作用のいずれの機能も有さず、かつ炭素原子と水素原子とから構成されるか、または炭素原子、水素原子および酸素原子から構成された、２５℃で液状または固体状である化合物
    をさらに含む請求項１～６のいずれか１項に記載の重合性組成物。     (Component 5) Nonionic surfactant having no (meth) acryloyl group, and (Component 6) No (meth) acryloyl group in the molecule, a function for suppressing radical polymerization, a function for inhibiting radical polymerization, light Liquid or solid at 25 ° C., which has neither a polymerization initiation function nor a surface-active function, and is composed of carbon atoms and hydrogen atoms, or is composed of carbon atoms, hydrogen atoms and oxygen atoms The polymerizable composition according to any one of claims 1 to 6, further comprising a compound in the form of a catalyst.
  8. 　前記成分６が、ポリエステルポリオール、ポリカーボネートポリオールおよび粘着付与剤からなる群から選ばれる少なくとも１種であることを特徴とする請求項７に記載の重合性組成物。 The polymerizable composition according to claim 7, wherein the component 6 is at least one selected from the group consisting of a polyester polyol, a polycarbonate polyol, and a tackifier.
  9. 　前記成分５が、グリフィンのＨＬＢの値が３．０～６．０である、（メタ）アクリロイル基を有さない非イオン界面活性剤であることを特徴とする請求項７または８に記載の重合性組成物。 The component 5 is a nonionic surfactant having no (meth) acryloyl group, wherein the Griffin has an HLB value of 3.0 to 6.0. Polymerizable composition.
  10. 　請求項１～９のいずれか１項に記載の重合性組成物を重合して得られる重合物。 A polymer obtained by polymerizing the polymerizable composition according to any one of claims 1 to 9.
  11. 　画像表示装置の画像表示部と透光性の保護部との間に介在させる重合物層として使用される光学用粘着シートを製造するための重合性組成物であって、該重合性組成物が請求項１～１０のいずれか１項に記載の重合性組成物であることを特徴とする重合性組成物。 A polymerizable composition for producing an optical pressure-sensitive adhesive sheet used as a polymer layer interposed between an image display portion and a translucent protective portion of an image display device, wherein the polymerizable composition is A polymerizable composition, which is the polymerizable composition according to any one of claims 1 to 10.
  12. 　請求項１１に記載の重合性組成物を塗布し、光重合開始剤が感光可能な光を該重合性組成物に照射して、重合させることによって得られる、厚さ１０～１０００μｍの重合物層を有する光学用粘着シート。 A polymer layer having a thickness of 10 to 1000 μm obtained by applying the polymerizable composition according to claim 11 and irradiating the polymerizable composition with light that can be photosensitized by a photopolymerization initiator. An optical pressure-sensitive adhesive sheet comprising:
  13. 　画像表示部を有する基部と、透光性の保護部と、前記基部と前記保護部との間に介在する重合物層を含む画像表示装置の製造方法であって、該方法が、
    請求項７～９のいずれか１項に記載の重合性組成物を、前記基部と前記保護部との間に介在させる工程、および
    光重合開始剤が感光可能な光を前記重合性組成物に照射して重合物層を形成する工程
    を含むことを特徴とする画像表示装置の製造方法。     A method for manufacturing an image display device, comprising: a base having an image display portion; a translucent protective portion; and a polymer layer interposed between the base portion and the protective portion, the method comprising:
    A step of interposing the polymerizable composition according to any one of claims 7 to 9 between the base portion and the protective portion, and light capable of being photosensitized by a photopolymerization initiator to the polymerizable composition. The manufacturing method of the image display apparatus characterized by including the process of irradiating and forming a polymer layer.
  14. 　画像表示部を有する基部と透光性の保護部とを光学用粘着シートを用いて貼り付ける工程を有する画像表示装置の製造方法であって、該光学用粘着シートが請求項１２に記載の光学用粘着シートであることを特徴とする画像表示装置の製造方法。 It is a manufacturing method of the image display apparatus which has the process of affixing the base which has an image display part, and a translucent protection part using an optical adhesive sheet, Comprising: This optical adhesive sheet is an optical of Claim 12. A method for manufacturing an image display device, which is a pressure-sensitive adhesive sheet.
  15. 　請求項１３または１４に記載の画像表示装置の製造方法によって製造された画像表示装置。 An image display device manufactured by the method for manufacturing an image display device according to claim 13 or 14.
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