WO2019244499A1 - フレキシブル画像表示装置用粘着剤層、フレキシブル画像表示装置用積層体、及び、フレキシブル画像表示装置 - Google Patents

フレキシブル画像表示装置用粘着剤層、フレキシブル画像表示装置用積層体、及び、フレキシブル画像表示装置 Download PDF

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WO2019244499A1
WO2019244499A1 PCT/JP2019/018567 JP2019018567W WO2019244499A1 WO 2019244499 A1 WO2019244499 A1 WO 2019244499A1 JP 2019018567 W JP2019018567 W JP 2019018567W WO 2019244499 A1 WO2019244499 A1 WO 2019244499A1
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WIPO (PCT)
Prior art keywords
meth
sensitive adhesive
pressure
display device
image display
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PCT/JP2019/018567
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English (en)
French (fr)
Japanese (ja)
Inventor
大器 下栗
崇弘 野中
昌邦 藤田
雄祐 外山
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日東電工株式会社
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Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to KR1020217001690A priority Critical patent/KR102649511B1/ko
Priority to SG11202012953VA priority patent/SG11202012953VA/en
Priority to CN201980041327.4A priority patent/CN112292433B/zh
Publication of WO2019244499A1 publication Critical patent/WO2019244499A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • 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
    • C09J133/00—Adhesives based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • 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
    • C09J133/00—Adhesives based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G09F9/301—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light

Definitions

  • the present invention relates to a pressure-sensitive adhesive layer for a flexible image display device.
  • the present invention also relates to a laminate for a flexible image display device to which, for example, an optical film including at least a polarizing film is applied together with the pressure-sensitive adhesive layer for a flexible image display device.
  • the present invention also relates to a flexible image display device on which the laminate for a flexible image display device is arranged.
  • an optical laminate 20 is provided on the viewing side of the organic EL display panel 10, and a touch panel 30 is provided on the viewing side of the optical laminate 20.
  • the optical laminate 20 includes a polarizing film 1 having protective films 2-1 and 2-2 bonded on both surfaces thereof and a retardation film 3, and the polarizing film 1 is provided on the viewing side of the retardation film 3.
  • the touch panel 30 has a structure in which the transparent conductive films 4-1 and 4-2 having a structure in which the base films 5-1 and 5-2 and the transparent conductive layers 6-1 and 6-2 are laminated are provided with the spacer 7 interposed therebetween. It has an arranged structure (for example, see Patent Document 1).
  • the conventional organic EL display device as disclosed in Patent Document 1 is not designed with bending in mind. If a plastic film is used for the organic EL display panel base material, the organic EL display panel can have flexibility. Further, even in a case where a plastic film is used for a touch panel and incorporated in an organic EL display panel, it is possible to impart flexibility to the organic EL display panel. However, there is a problem that an optical film including a conventional polarizing film and the like, which is laminated on the organic EL display panel, inhibits the flexibility of the organic EL display device.
  • the conventional organic EL display device is repeatedly bent at normal temperature to cause minute distortion in layers and each layer such as an optical film and an adhesive layer constituting the organic EL display device, thereby causing peeling or cracking (breakage). ) Occur. Furthermore, in addition to the problem at room temperature, when bending is performed in a high-temperature environment, cohesive failure of the pressure-sensitive adhesive layer occurs, and peeling tends to be remarkable.
  • Patent Document 2 from the viewpoints of bending resistance and heat resistance, the storage elastic modulus G ′ at ⁇ 20 ° C. is 1 ⁇ 10 5 Pa or less, and the storage elastic modulus G ′ at 85 ° C. is 1 ⁇ 10 4 Pa or more. It has been proposed to use an adhesive layer. Further, Patent Document 3 proposes to use a pressure-sensitive adhesive layer having a storage elastic modulus G 'of 3.0 ⁇ 10 5 Pa or less at 23 ° C. from the viewpoint of adhesive strength and low-temperature bending resistance. Further, in Patent Document 4, from the viewpoint of bending resistance at a low temperature, the storage elastic modulus G ′ at ⁇ 20 ° C.
  • an object of the present invention is to provide a pressure-sensitive adhesive layer for a flexible image display device, which can satisfy the bending resistance from a low temperature to a high temperature.
  • the present invention provides a laminate for a flexible image display device to which an optical film including at least a polarizing film is applied, together with the pressure-sensitive adhesive layer for a flexible image display device, and further, the laminate for a flexible image display device is provided. It is an object of the present invention to provide an arranged flexible image display device.
  • the present inventors have found the following pressure-sensitive adhesive layer for a flexible image display device, and have completed the present invention.
  • the present invention provides a storage elastic modulus G ′ at ⁇ 20 ° C. of 3.5 ⁇ 10 4 to 1.7 ⁇ 10 5 Pa
  • the storage elastic modulus G ′ at 23 ° C. is 1.0 ⁇ 10 4 to 5.0 ⁇ 10 4 Pa
  • the present invention relates to a pressure-sensitive adhesive layer for a flexible image display device, wherein the difference between the storage elastic modulus G ′ at 23 ° C. and the storage elastic modulus G ′ at 85 ° C. is 5.2 ⁇ 10 3 Pa or more.
  • the average value of the storage elastic modulus G ′ at ⁇ 20 ° C. and the storage elastic modulus G ′ at 23 ° C. is 4.5 ⁇ 10 4 to 1.5 ⁇ 10 5 Pa. It is preferable that
  • the gel fraction is preferably 70% by weight or more.
  • the pressure-sensitive adhesive layer for a flexible image display device can be formed by a pressure-sensitive adhesive composition containing a (meth) acryl-based polymer containing an alkyl (meth) acrylate as a monomer unit.
  • the alkyl (meth) acrylate contains an alkyl (meth)) acrylate having an alkyl group having 10 or more carbon atoms.
  • the (meth) acrylic polymer preferably contains an N-vinyl group-containing lactam monomer as a monomer unit in addition to the alkyl (meth) acrylate.
  • the present invention also relates to a laminate for a flexible image display device, comprising the pressure-sensitive adhesive layer and an optical film including at least a polarizing film.
  • the present invention includes the laminate for a flexible image display device and an organic EL display panel, wherein the laminate for a flexible image display device is arranged on the viewing side with respect to the organic EL display panel.
  • the present invention relates to a flexible image display device.
  • a window is arranged on the viewing side with respect to the flexible image display device laminate.
  • the pressure-sensitive adhesive layer bonded to the base material needs a stress that follows the minute deformation of the adjacent base material.
  • the cohesive force of the pressure-sensitive adhesive layer decreases at high temperatures, and when repeatedly bent, cohesive failure of the pressure-sensitive adhesive layer occurs due to repeated strain applied to the pressure-sensitive adhesive layer, and peeling occurs it is conceivable that.
  • the pressure-sensitive adhesive layer of the present invention has a predetermined storage modulus at a predetermined temperature, the pressure-sensitive adhesive layer may be distorted even when exposed to any of low-temperature, normal-temperature, and high-temperature environments. The stress can be dispersed, and the strain applied to the substrate can be reduced.
  • the pressure-sensitive adhesive layer is easily deformed by minute distortion, and the distortion applied to the other layers (each layer) can be reduced.
  • the pressure-sensitive adhesive layer of the present invention has no cracks, peeling or breakage of the substrate even with repeated bending, and can satisfy the bending resistance, and the peeling between the substrate and the pressure-sensitive adhesive layer can be achieved. This can be prevented from occurring and can be suitably applied to the use of the flexible image display device.
  • minute distortion is likely to occur in each layer, and there is a high possibility that cracks occur in the base material and peeling between the adhesive layer and the pressure-sensitive adhesive layer of the present invention is suitably applied. Is done.
  • FIG. 11 is a cross-sectional view illustrating a conventional organic EL display device.
  • 1 is a cross-sectional view illustrating a flexible image display device according to an embodiment of the present invention.
  • FIG. 6 is a cross-sectional view illustrating a flexible image display device according to another embodiment of the present invention.
  • FIG. 6 is a cross-sectional view illustrating a flexible image display device according to another embodiment of the present invention. It is a figure which shows a bending test ((A) bending angle 0 degree, (B) bending angle 180 degree). It is sectional drawing which shows the sample for evaluation used in an Example. It is a figure showing the manufacturing method of the phase difference used in the example.
  • the pressure-sensitive adhesive layer for a flexible image display device of the present invention has a storage modulus G ′ at ⁇ 20 ° C. of 3.5 ⁇ 10 4 to 1.7 ⁇ 10 5 Pa, and a storage modulus G ′ at 23 ° C. Is 1.0 ⁇ 10 4 to 5.0 ⁇ 10 4 Pa, and the difference between the storage elastic modulus G ′ at 23 ° C. and the storage elastic modulus G ′ at 85 ° C. is 5.2 ⁇ 10 3 Pa That is all.
  • the pressure-sensitive adhesive layer of the present invention can control the storage elastic modulus G ′ at ⁇ 20 ° C. in the range of 3.5 ⁇ 10 4 to 1.7 ⁇ 10 5 Pa, and thus can operate under a low-temperature environment. Satisfies the bending resistance.
  • the storage elastic modulus G ′ at ⁇ 20 ° C. is preferably 5 ⁇ 10 4 to 1.6 ⁇ 10 5 Pa, and more preferably 7.0 ⁇ 10 4 to 1. 5 ⁇ 10 5 Pa is preferred.
  • the pressure-sensitive adhesive layer of the present invention controls the storage elastic modulus G ′ at 23 ° C. in the range of 1.0 ⁇ 10 4 to 5.0 ⁇ 10 4 Pa, and the storage elastic modulus G at 23 ° C.
  • the range of the storage modulus G ′ at 23 ° C. is preferably designed to be lower than the range of the storage modulus G ′ at ⁇ 20 ° C., and is preferable in satisfying the bending resistance under a normal temperature environment. Further, by designing the storage elastic modulus G ′ at 85 ° C.
  • the bending resistance under a high-temperature environment is satisfied. That is, in addition to the control of the storage elastic modulus G ′ at ⁇ 20 ° C., it is possible to satisfy the bending resistance in a wide temperature range from a low temperature to a high temperature where reliability is required.
  • the storage elastic modulus G ′ at 23 ° C. is preferably from 1.3 ⁇ 10 4 to 4.0 ⁇ 10 4 Pa, more preferably from 1.5 ⁇ 10 4 to 3. 5 ⁇ 10 4 Pa is preferred.
  • the difference between the storage elastic modulus G ′ at 23 ° C. and the storage elastic modulus G ′ at 85 ° C. is 5.3 ⁇ 10 3 Pa or more, more preferably 5 ⁇ 10 3 Pa, from the viewpoint of bending resistance in a high-temperature environment. It is preferable to control the pressure to be 0.5 ⁇ 10 3 Pa or more. If the difference in the storage elastic modulus G ′ is too large, the fluidity of the pressure-sensitive adhesive becomes high. Therefore, from the viewpoint of processing, 8.0 ⁇ 10 3 Pa or less, and further 7.0 ⁇ 10 3 Pa or less. It is preferable to control so that
  • the pressure-sensitive adhesive layer of the present invention has an average value of the storage elastic modulus G ′ at ⁇ 20 ° C. and the storage elastic modulus G ′ at 23 ° C. from the viewpoint of satisfying the bending resistance under both low temperature and normal temperature environments. Is preferably 4.0 ⁇ 10 4 to 1.5 ⁇ 10 5 Pa. The average value is more preferably from 4.5 ⁇ 10 4 to 1.0 ⁇ 10 5 Pa.
  • the pressure-sensitive adhesive layer of the present invention has a storage elastic modulus G ′ at ⁇ 20 ° C. and a storage elastic modulus at 23 ° C. from the viewpoint of satisfying the flex resistance under any of low temperature, normal temperature and high temperature environments.
  • the average value of G ′ and the storage modulus G ′ at 85 ° C. is preferably from 5.0 ⁇ 10 4 to 4.0 ⁇ 10 5 Pa. More preferably, the average value is from 8.0 ⁇ 10 4 to 3.0 ⁇ 10 5 Pa.
  • the gel fraction of the pressure-sensitive adhesive layer of the present invention is preferably 70% by weight or more, more preferably 70 to 95% by weight, more preferably 80 to 90% by weight, still more preferably 82 to 90% by weight. Even more preferably, it is 85 to 90% by weight.
  • the cohesive force of the pressure-sensitive adhesive layer can be increased, and the appearance (e.g., a dent of glue), workability, durability, and flexibility can be improved. Flexibility under normal temperature and high temperature environments is easily compatible, which is a preferable embodiment.
  • the glass transition temperature (Tg) of the pressure-sensitive adhesive layer of the present invention is not particularly limited, but the upper limit is preferably 5 ° C. or lower. In consideration of the flexibility in a low-temperature environment or in a high-speed region, the temperature is more preferably ⁇ 20 ° C. or lower, and still more preferably ⁇ 25 ° C. or lower. When the Tg of the pressure-sensitive adhesive layer is in such a range, the pressure-sensitive adhesive layer is hardly hardened even in a low-temperature environment or at a bending speed in a high-speed region such as a bending speed exceeding 1 second / time, and is excellent in stress relaxation.
  • a bendable or foldable laminate for a flexible image display device, and a flexible image display device on which the laminate for a flexible image display device is arranged can be realized.
  • the glass transition temperature (Tg) is a theoretical value derived from the Fox equation.
  • the total light transmittance (according to JIS K7136) in the visible light wavelength region of the pressure-sensitive adhesive layer used in the laminate for a flexible image display device of the present invention is preferably 85% or more, more preferably 90% or more.
  • an acrylic pressure-sensitive adhesive As the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer of the present invention, an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, a vinyl alkyl ether-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, a polyester-based pressure-sensitive adhesive, a polyamide-based pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive , A fluorine-based adhesive, an epoxy-based adhesive, a polyether-based adhesive, and the like.
  • the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is used alone or in combination of two or more. However, it is preferable to use an acrylic pressure-sensitive adhesive (composition) containing a (meth) acrylic polymer alone in terms of transparency, processability, durability, adhesion, and bending resistance.
  • a (meth) acryl-based monomer containing, as a monomer unit, an alkyl (meth) acrylate having a linear or branched alkyl group having 1 to 30 carbon atoms. It preferably contains a polymer.
  • the linear or branched alkyl (meth) acrylate having an alkyl group having 1 to 30 carbon atoms a pressure-sensitive adhesive layer having excellent flexibility can be obtained.
  • the (meth) acrylic polymer refers to an acrylic polymer and / or a methacrylic polymer
  • the (meth) acrylate refers to acrylate and / or methacrylate.
  • linear or branched alkyl (meth) acrylate having an alkyl group having 1 to 30 carbon atoms which constitutes the main skeleton of the (meth) acrylic polymer include methyl (meth) acrylate, ethyl ( (Meth) acrylate, n-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, n- Hexyl (meth) acrylate, isohexyl (meth) acrylate, isoheptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nony
  • alkyl (meth) acrylates having a linear or branched alkyl group having 6 to 30 carbon atoms (hereinafter referred to as “length”).
  • the alkyl (meth) acrylate having a long-chain alkyl group preferably contains an alkyl (meth)) acrylate having an alkyl group having 10 or more carbon atoms.
  • alkyl (meth) acrylate having a long-chain alkyl group n-dodecyl (meth) acrylate (lauryl (meth) acrylate) is more preferable.
  • the alkyl (meth) acrylate having the long-chain alkyl group the entanglement of the polymer is reduced, and the polymer is easily deformed by a minute strain, which is a preferable embodiment for the flexibility.
  • Tg glass transition temperature
  • an alkyl (meth) acrylate having the above alkyl group and among them, 2-ethylhexyl acrylate.
  • the alkyl (meth) acrylate one or more kinds can be used.
  • the long-chain alkyl (meth) acrylate a mixture of an alkyl (meth) acrylate having an alkyl group having 10 to 30 carbon atoms and an alkyl (meth) acrylate having an alkyl group having 6 to 9 carbon atoms is used. Is preferred.
  • a mixture of an alkyl (meth) acrylate having an alkyl group having 10 to 30 carbon atoms and an alkyl (meth) acrylate having an alkyl group having 6 to 9 carbon atoms comprises n-dodecyl (meth) acrylate and 2-ethylhexyl acrylate Is preferably used in combination.
  • the alkyl (meth) acrylate having a linear or branched alkyl group having 1 to 30 carbon atoms is a main component in all monomers constituting the (meth) acrylic polymer.
  • the main component refers to 50 to 100% by weight of a linear or branched alkyl (meth) acrylate having an alkyl group having 1 to 30 carbon atoms in all monomers constituting the (meth) acrylic polymer. Is preferably 80 to 100% by weight, more preferably 90 to 99.9% by weight, and particularly preferably 94 to 99.9% by weight.
  • the monomer component constituting the (meth) acrylic polymer may be a copolymerizable monomer (copolymer) in addition to the linear or branched alkyl (meth) acrylate having an alkyl group having 1 to 30 carbon atoms. (Polymerizable monomer).
  • the copolymerizable monomers may be used alone or in combination of two or more.
  • the copolymerizable monomer is not particularly limited, but is preferably a copolymerizable monomer having a reactive functional group having a polymerizable unsaturated double bond.
  • a hydroxyl group-containing monomer is preferable.
  • the hydroxyl group-containing monomer is a compound containing a hydroxyl group in its structure and containing a polymerizable unsaturated double bond such as a (meth) acryloyl group or a vinyl group.
  • hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8-hydroxyethyl (meth) acrylate.
  • examples include hydroxyalkyl (meth) acrylates such as octyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, and 12-hydroxylauryl (meth) acrylate, and (4-hydroxymethylcyclohexyl) -methyl acrylate.
  • hydroxyl group-containing monomers 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable from the viewpoint of durability and adhesion.
  • the hydroxyl group-containing monomer one type or two or more types can be used.
  • Examples of the copolymerizable monomer having a reactive functional group include a carboxyl group-containing monomer, an amino group-containing monomer, and an amide group-containing monomer having a reactive functional group. These monomers are preferable from the viewpoint of humidification and adhesion in a high-temperature environment.
  • the carboxyl group-containing monomer is a compound containing a carboxyl group in its structure and containing a polymerizable unsaturated double bond such as a (meth) acryloyl group or a vinyl group.
  • carboxyl group-containing monomer examples include, for example, (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and the like.
  • the amino group-containing monomer is a compound containing an amino group in its structure and containing a polymerizable unsaturated double bond such as a (meth) acryloyl group and a vinyl group.
  • the amide group-containing monomer is a compound containing an amide group in its structure and containing a polymerizable unsaturated double bond such as a (meth) acryloyl group or a vinyl group.
  • amide group-containing monomers are preferable, and N-vinyl group-containing lactam monomers are particularly preferable. N-vinyl group-containing lactam monomers are preferred from the viewpoint of improving the adhesion to the adherend, particularly from the viewpoint of improving the adhesion during heating.
  • the copolymerizable monomer having a reactive functional group it is preferable to use a hydroxyl group-containing monomer and an amide group-containing monomer (in particular, an N-vinyl group-containing lactam monomer) in combination.
  • the proportion of the copolymerizable monomer having a reactive functional group exemplified above is 20% by weight or less in all the monomers constituting the (meth) acrylic polymer. Is preferably 15% by weight or less, more preferably 10% by weight or less.
  • the mixing ratio is preferably 0.01 to 8% by weight, more preferably 0.01 to 5% by weight, and further preferably 0.05 to 3% by weight.
  • the mixing ratio is preferably 0.01 to 15% by weight, and 0.1 to 12% by weight. %, More preferably 0.1 to 10% by weight.
  • the N-vinyl group-containing lactam monomer is preferably used in an amount of 3 to 12% by weight, more preferably 4 to 10% by weight. If the proportion of the N-vinyl group-containing lactam monomer is too large, the glass transition temperature increases, and the storage modulus G ′ increases at room temperature (23 ° C.), which may cause peeling or cracking in a bending test. Therefore, the N-vinyl group-containing lactam monomer is preferably used in the above range.
  • copolymerizable monomer other than the copolymerizable monomer having a reactive functional group described above, other copolymerizable monomers can be used as long as the effects of the present invention are not impaired.
  • Examples of the other copolymerizable monomers include, for example, alkoxyalkyl (meth) acrylates [eg, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, and methoxytrimethyl (meth) acrylate].
  • alkoxyalkyl (meth) acrylates eg, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, and methoxytrimethyl (meth) acrylate.
  • the mixing ratio of the other copolymerized monomer is not particularly limited, but is preferably 30% by weight or less, more preferably 10% by weight or less, and more preferably 10% by weight or less of all the monomers constituting the (meth) acrylic polymer. preferable. If it exceeds 30% by weight, especially when a material other than alkyl (meth) acrylate is used, the number of reaction points between the pressure-sensitive adhesive layer and other layers (films, substrates) tends to decrease, and the adhesion tends to decrease.
  • the monomer component constituting the (meth) acrylic polymer includes a multifunctional monomer having a plurality of the reactive functional groups in addition to the single functional monomer having a reactive functional group of the polymerizable unsaturated double bond described above. Functional monomers can be used.
  • the polyfunctional monomer is not particularly limited.
  • the polyfunctional acrylate 1,6-hexanediol diacrylate, dipentaerythritol hexa (meth) acrylate.
  • the polyfunctional monomers may be used alone or in combination of two or more.
  • the blending ratio of the polyfunctional monomer is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and more preferably 3 parts by weight or less, based on 100 parts by weight of the total amount of the monofunctional monomer constituting the (meth) acrylic polymer. More preferred.
  • the blending ratio of the polyfunctional monomer increases, the number of crosslinking points increases, and the flexibility of the pressure-sensitive adhesive (layer) is lost. Therefore, the stress relaxation property tends to be poor.
  • the pressure-sensitive adhesive layer is formed of a pressure-sensitive adhesive composition
  • the pressure-sensitive adhesive composition may be a pressure-sensitive adhesive composition having any form, for example, an emulsion type, a solvent type (solution type). , Active energy ray curing type, hot melting type (hot melt type) and the like.
  • the above-mentioned pressure-sensitive adhesive composition is preferably a solvent-type pressure-sensitive adhesive composition or an active energy ray-curable pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive composition is preferably a mixture of monomer components constituting a (meth) acrylic polymer in view of productivity, influence on the environment, and ease of obtaining a thick pressure-sensitive adhesive layer ( It is preferably an active energy ray-curable pressure-sensitive adhesive composition containing a monomer mixture) or a partially polymerized product thereof as an essential component.
  • the (meth) acrylic polymer is obtained by polymerizing the monomer component. More specifically, it can be obtained by polymerizing the monomer component, the monomer mixture or a partial polymer thereof by a known and commonly used method.
  • the polymerization method include solution polymerization, emulsion polymerization, bulk polymerization, and polymerization by irradiation with heat or active energy rays (thermal polymerization or active energy ray polymerization).
  • solution polymerization and active energy ray polymerization are preferred in terms of transparency, water resistance, cost and the like.
  • the polymerization is preferably performed while avoiding contact with oxygen from the viewpoint of suppressing polymerization inhibition by oxygen.
  • the (meth) acrylic polymer obtained may be any of a random copolymer, a block copolymer, a graft copolymer and the like.
  • Examples of the active energy rays irradiated during the active energy ray polymerization (photopolymerization) include ionizing radiation such as ⁇ -rays, ⁇ -rays, ⁇ -rays, neutron rays, and electron beams, and ultraviolet rays. Is preferred.
  • the irradiation energy, irradiation time, irradiation method and the like of the active energy ray are not particularly limited as long as the photopolymerization initiator can be activated to cause a reaction of the monomer component.
  • solvents can be used.
  • examples of such a solvent include esters such as ethyl acetate and n-butyl acetate; aromatic hydrocarbons such as toluene and benzene; aliphatic hydrocarbons such as n-hexane and n-heptane; cyclohexane and methyl.
  • Organic solvents such as alicyclic hydrocarbons such as cyclohexane; ketones such as methyl ethyl ketone and methyl isobutyl ketone;
  • the said solvent may be used individually or in combination of 2 or more types.
  • a polymerization initiator such as a photopolymerization initiator (photoinitiator) or a thermal polymerization initiator may be used depending on the type of the polymerization reaction.
  • the polymerization initiator may be used alone or in combination of two or more.
  • the photopolymerization initiator is not particularly limited.
  • a benzoin ether-based photopolymerization initiator an acetophenone-based photopolymerization initiator, an ⁇ -ketol-based photopolymerization initiator, an aromatic sulfonyl chloride-based photopolymerization initiator, Active oxime-based photopolymerization initiators, benzoin-based photopolymerization initiators, benzyl-based photopolymerization initiators, ketal-based photopolymerization initiators, and thioxanthone-based photopolymerization initiators are exemplified.
  • Examples of the ⁇ -ketol-based photopolymerization initiator include 2-methyl-2-hydroxypropiophenone and 1- [4- (2-hydroxyethyl) phenyl] -2-methylpropan-1-one.
  • Can be Examples of the aromatic sulfonyl chloride-based photopolymerization initiator include 2-naphthalene sulfonyl chloride.
  • Examples of the photoactive oxime-based photopolymerization initiator include 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime.
  • Examples of the benzoin-based photopolymerization initiator include benzoin.
  • Examples of the benzyl-based photopolymerization initiator include benzyl and the like.
  • benzophenone-based photopolymerization initiator examples include benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, ⁇ -hydroxycyclohexylphenyl ketone, and the like.
  • ketal-based photopolymerization initiator examples include benzyl dimethyl ketal.
  • thioxanthone-based photopolymerization initiator examples include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone, and the like.
  • the amount of the photopolymerization initiator is not particularly limited, but is preferably 0.01 to 1 part by weight, more preferably 0.05 to 0.5 part by weight, based on 100 parts by weight of the total amount of the monomer components.
  • polymerization initiator used in the solution polymerization examples include, for example, an azo polymerization initiator, a peroxide polymerization initiator (eg, dibenzoyl peroxide, tert-butyl permaleate, etc.), a redox polymerization initiator, and the like. Is mentioned. Among them, azo polymerization initiators disclosed in JP-A-2002-69411 are preferable. Examples of the azo polymerization initiator include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis-2-methylbutyronitrile, and 2,2′-azobis (2-methylpropionic acid). ) Dimethyl, 4,4'-azobis-4-cyanovaleric acid and the like.
  • AIBN 2,2′-azobisisobutyronitrile
  • 2,2′-azobis-2-methylbutyronitrile 2,2′-azobis-2-methylbutyronitrile
  • 2,2′-azobis (2-methylpropionic acid 2,2′
  • the amount of the azo polymerization initiator is not particularly limited, but is preferably 0.05 to 0.5 part by weight, more preferably 0.1 to 0.3 part by weight, based on 100 parts by weight of the total amount of the monomer components. It is.
  • the polyfunctional monomer (polyfunctional acrylate) used as the copolymerizable monomer can be used for a solvent-type or active energy ray-curable pressure-sensitive adhesive composition.
  • a polyfunctional monomer (polyfunctional acrylate) and the photopolymerization initiator are mixed and used, active energy ray curing is performed after thermal drying.
  • the (meth) acrylic polymer used in the solvent-based pressure-sensitive adhesive composition one having a weight average molecular weight (Mw) in the range of 1,000,000 to 2.5,000,000 is usually used. In consideration of durability, especially heat resistance and flexibility, it is preferably 1.2 million to 2,000,000, more preferably 1.4 million to 1.8 million. When the weight average molecular weight is smaller than 1,000,000, the number of crosslinking points is increased as compared with those having a weight average molecular weight of 1,000,000 or more when the polymer chains are crosslinked to ensure durability.
  • Mw weight average molecular weight
  • the strain on the outer side (convex side) and the inner side (concave side) of the bending generated between the layers (films) at the time of bending cannot be alleviated, and the layers easily break.
  • the weight average molecular weight is more than 2.5 million, a large amount of a diluting solvent is required to adjust the viscosity for coating, which is not preferable because the cost is increased. Since the entanglement of the polymer chains of the polymer is complicated, the flexibility is inferior, and each layer (film) is easily broken at the time of bending.
  • the weight average molecular weight (Mw) is a value measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene.
  • the pressure-sensitive adhesive composition may contain a (meth) acrylic oligomer.
  • a (meth) acrylic oligomer it is preferable to use a polymer having a smaller weight average molecular weight (Mw) than that of the (meth) acrylic polymer.
  • Mw weight average molecular weight
  • Examples of the monomer constituting the (meth) acrylic oligomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth).
  • Examples of the (meth) acrylic oligomer include alkyl (meth) acrylates having a branched alkyl group such as isobutyl (meth) acrylate and t-butyl (meth) acrylate; cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.
  • Acrylates such as dicyclopentanyl (meth) acrylates and esters of (meth) acrylic acid with alicyclic alcohols; cyclic structures such as aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate
  • aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate
  • an alkyl (meth) acrylate having a branched structure or an ester with an alicyclic alcohol can be suitably used as a monomer constituting the (meth) acrylic oligomer.
  • suitable (meth) acrylic oligomers include, for example, a copolymer of butyl acrylate (BA), methyl acrylate (MA), and acrylic acid (AA), cyclohexyl methacrylate (CHMA), and isobutyl methacrylate ( (IBMA) copolymer, copolymer of cyclohexyl methacrylate (CHMA) and isobornyl methacrylate (IBXMA), copolymer of cyclohexyl methacrylate (CHMA) and acryloyl morpholine (ACMO), cyclohexyl methacrylate (CHMA) and diethyl acrylamide ( DEAA), 1-adamantyl acrylate (ADA) and methyl methacrylate (MMA), dicyclopentanyl methacrylate (DCPMA) and isobornyl methacrylate (IBXMA) copolymer, dicyclopentanyl methacrylate (DCPMA),
  • the polymerization method of the (meth) acrylic oligomer as in the case of the (meth) acrylic polymer, solution polymerization, emulsion polymerization, bulk polymerization, emulsion polymerization, polymerization by irradiation of heat or active energy rays (thermal polymerization, active energy Linear polymerization).
  • solution polymerization and active energy ray polymerization are preferred in terms of transparency, water resistance, cost and the like.
  • the obtained (meth) acrylic oligomer may be any of a random copolymer, a block copolymer, a graft copolymer and the like.
  • the (meth) acrylic oligomer can be used for the solvent-based pressure-sensitive adhesive composition and the active energy ray-curable pressure-sensitive adhesive composition, like the (meth) acrylic polymer.
  • the active energy ray-curable pressure-sensitive adhesive composition the (meth) acrylic oligomer may be further added to a mixture (monomer mixture) of monomer components constituting the (meth) acrylic polymer or a partial polymer thereof. Can be mixed and used.
  • the pressure-sensitive adhesive composition can be heated and dried to remove the solvent, and then the active energy ray curing can be completed to obtain a pressure-sensitive adhesive layer.
  • the weight average molecular weight (Mw) of the (meth) acrylic oligomer used in the solvent-based pressure-sensitive adhesive composition is preferably 1,000 or more, more preferably 2,000 or more, still more preferably 3,000 or more, and particularly preferably 4,000 or more. .
  • the weight average molecular weight (Mw) of the (meth) acrylic oligomer is preferably 30,000 or less, more preferably 15,000 or less, still more preferably 10,000 or less, and particularly preferably 7000 or less.
  • the weight average molecular weight (Mw) of the (meth) acrylic oligomer is adjusted within the above range, for example, when used in combination with the (meth) acrylic polymer, the ) Acrylic oligomer intervenes, entanglement of (meth) acrylic polymer is reduced, adhesive layer is easily deformed by minute strain, strain on other layers can be reduced, cracks and adhesion of each layer The peeling between the agent layer and other layers can be suppressed, which is a preferable embodiment.
  • the weight average molecular weight (Mw) of the (meth) acrylic oligomer is measured by GPC (gel permeation chromatography) in the same manner as the (meth) acrylic polymer, and the value calculated in terms of polystyrene is used. Say.
  • the pressure-sensitive adhesive composition of the present invention may contain a crosslinking agent.
  • a crosslinking agent an organic cross-linking agent or a polyfunctional metal chelate can be used in any of the solvent-type and active energy ray-curable pressure-sensitive adhesive compositions.
  • the organic crosslinking agent include an isocyanate crosslinking agent, a peroxide crosslinking agent, an epoxy crosslinking agent, and an imine crosslinking agent.
  • Multifunctional metal chelates are those in which a polyvalent metal is covalently or coordinated with an organic compound.
  • Examples of the polyvalent metal atom include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, and Ti.
  • the atom in the organic compound which forms a covalent bond or a coordinate bond includes an oxygen atom and the like, and the organic compound includes an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, a ketone compound and the like.
  • a peroxide-based crosslinking agent or an isocyanate crosslinking agent is preferred, and among them, a peroxide-based crosslinking agent is preferably used.
  • the peroxide-based crosslinking agent generates radicals by, for example, extracting hydrogen from the side chains of the (meth) acrylic polymer, and promotes crosslinking between the side chains of the (meth) acrylic polymer.
  • a cross-linking agent for example, a polyfunctional isocyanate-based cross-linking agent
  • This is a preferred embodiment in terms of achieving both flexibility (suppression of cracking and peeling) under normal temperature and high temperature environments.
  • isocyanate-based cross-linking agents are preferable in terms of durability, and a peroxide-based cross-linking agent and an isocyanate-based cross-linking agent (particularly, a bifunctional isocyanate-based cross-linking agent) Is preferred from the viewpoint of flexibility.
  • peroxide-based crosslinkers and bifunctional isocyanate-based crosslinkers form flexible two-dimensional crosslinks, whereas trifunctional isocyanate-based crosslinkers form stronger three-dimensional crosslinks.
  • two-dimensional crosslinking which is a more flexible crosslinking, is advantageous.
  • the active energy ray-curable pressure-sensitive adhesive composition it is preferable to obtain a cross-linking effect by polymerization using the polyfunctional monomer from the viewpoint of productivity and thick film coating. Alternatively, it can be used in combination with the polyfunctional monomer.
  • a crosslinking agent is mixed with a mixture of monomer components (monomer mixture) or a partial polymer thereof constituting the (meth) acrylic polymer, and crosslinked by thermal drying before and after the active energy ray curing of the pressure-sensitive adhesive composition.
  • the reaction of the agent can be completed.
  • the peroxide crosslinking agent When used alone, it is preferably 0.5 to 5 parts by weight, more preferably 1 to 3 parts by weight, based on 100 parts by weight of the (meth) acrylic polymer. Within the above range, the cohesive force can be sufficiently increased while maintaining the ease of deformation with respect to minute strain, and the durability and bending resistance can be improved, which is a preferable embodiment.
  • the lower limit of the weight ratio of the peroxide-based crosslinking agent to the isocyanate-based crosslinking agent (peroxide-based crosslinking agent / isocyanate-based crosslinking agent). Is preferably 1.2 or more, more preferably 1.5 or more, and still more preferably 3 or more.
  • the upper limit of the weight ratio is preferably 500 or less, more preferably 300 or less, and even more preferably 200 or less.
  • the pressure-sensitive adhesive composition of the present invention may contain other known additives, for example, various silane coupling agents, polyalkylene glycol polyether compounds such as polypropylene glycol, coloring agents, pigments, and the like. Powders, dyes, surfactants, plasticizers, tackifiers, surface lubricants, leveling agents, softeners, antioxidants, antioxidants, light stabilizers, ultraviolet absorbers, polymerization inhibitors, antistatic It can be added as appropriate depending on the use of an agent (such as an alkali metal salt or an ionic liquid as an ionic compound, or an ionic solid), an inorganic or organic filler, metal powder, particles, or a foil. Further, a redox system to which a reducing agent is added may be employed within a controllable range.
  • an agent such as an alkali metal salt or an ionic liquid as an ionic compound, or an ionic solid
  • an inorganic or organic filler such as an alkali metal salt or an i
  • a solvent-type acrylic pressure-sensitive adhesive composition includes a (meth) acryl-based polymer, It is produced by mixing components (for example, the (meth) acrylic oligomer, cross-linking agent, silane coupling agent, solvent, additive, etc.) added as necessary.
  • the active energy ray-curable acrylic pressure-sensitive adhesive composition includes a monomer mixture or a partially polymerized product thereof, and components added as necessary (for example, the photopolymerization initiator, the polyfunctional monomer, (Meth) acrylic oligomer, crosslinking agent, silane coupling agent, solvent, additive, etc.).
  • the conversion of the partially polymerized product is determined as follows. A part of the partially polymerized product is sampled to obtain a sample. The sample is precisely weighed and its weight is determined to be "the weight of the partially polymerized product before drying”. Next, the sample is dried at 130 ° C. for 2 hours, and the sample after drying is precisely weighed and its weight is obtained, which is referred to as “the weight of the partially polymerized product after drying”. Then, from the “weight of the partially polymerized product before drying” and “the weight of the partially polymerized product after drying”, the weight of the sample reduced by drying at 130 ° C. for 2 hours is obtained, and “weight loss amount” (volatility, Unreacted monomer weight).
  • ⁇ ⁇ ⁇ ⁇ ⁇ Silicone release liners are preferably used as the release-treated separator.
  • a method for drying the pressure-sensitive adhesive may be appropriately selected depending on the purpose. .
  • a method of heating and drying the coating film is used.
  • the heating and drying temperature is, for example, preferably 40 to 200 ° C., more preferably 50 to 180 ° C., particularly preferably 70 to 180 ° C. when preparing an acrylic pressure-sensitive adhesive using a (meth) acrylic polymer. 170 ° C.
  • the drying time is, for example, preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and particularly preferably 10 seconds to 5 minutes when preparing an acrylic pressure-sensitive adhesive using a (meth) acrylic polymer. Minutes.
  • Various methods are used for applying the pressure-sensitive adhesive composition. Specifically, for example, by roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, die coater, etc. A method such as an extrusion coating method may be used.
  • the thickness of the pressure-sensitive adhesive layer of the present invention is preferably 1 to 200 ⁇ m, more preferably 5 to 150 ⁇ m, and further preferably 10 to 100 ⁇ m.
  • the pressure-sensitive adhesive layer may be a single layer or may have a laminated structure. Within the above range, a preferred embodiment is obtained without obstructing bending and also in terms of adhesion (holding resistance). When a plurality of pressure-sensitive adhesive layers are provided, all pressure-sensitive adhesive layers are preferably within the above range.
  • the laminate for a flexible image display device of the present invention is characterized by including an adhesive layer and an optical film.
  • the thickness of the optical film is preferably 92 ⁇ m or less, more preferably 60 ⁇ m or less, and further preferably 10 to 50 ⁇ m. If it is in the said range, it will become a preferable aspect, without obstructing bending.
  • the polarizing film may be provided with a protective film on at least one side by an adhesive (layer) as long as the characteristics of the present invention are not impaired (not shown in the drawings).
  • An adhesive can be used for the bonding treatment between the polarizing film and the protective film.
  • the adhesive include an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gelatin-based adhesive, a vinyl latex-based adhesive, and a water-based polyester.
  • the adhesive is generally used as an adhesive composed of an aqueous solution, and usually contains a solid content of 0.5 to 60% by weight.
  • examples of the adhesive between the polarizing film and the protective film include an ultraviolet curable adhesive, an electron beam curable adhesive, and the like.
  • the electron beam-curable adhesive for polarizing films exhibits suitable adhesiveness to the above various protective films.
  • the adhesive used in the present invention can contain a metal compound filler.
  • a polarizing film and a protective film bonded together with an adhesive (layer) may be referred to as a polarizing film (polarizing plate).
  • a production method including a step of dyeing a monolayer body of a PVA-based resin and a step of stretching as described in JP-A-2004-341515 (single-layer stretching method) ).
  • JP-A-51-069644, JP-A-2000-338329, JP-A-2001-343521, WO 2010/100917, JP-A-2012-073563, and JP-A-2011-2816 Described above, a production method including a step of stretching a PVA-based resin layer and a resin substrate for stretching in a state of a laminate and a step of dyeing the same. According to this production method, even if the PVA-based resin layer is thin, it can be stretched without any trouble such as breakage due to stretching, because it is supported by the stretching resin base material.
  • the production method including the step of stretching and the step of dyeing in the state of a laminate are described in JP-A-51-069694, JP-A-2000-338329, and JP-A-2001-343521.
  • a step of stretching in a boric acid aqueous solution as described in WO 2010/100917 and JP-A-2012-073563, in that the film can be stretched at a high magnification and the polarization performance can be improved.
  • a production method (two-stage stretching method) including a step of performing auxiliary in-air stretching before stretching in an aqueous boric acid solution as described in JP-A-2012-073563 is preferred.
  • a method of stretching a PVA-based resin layer and a stretching resin base material in the state of a laminate, excessively dyeing the PVA-based resin layer, and then decoloring the same. is also preferable.
  • the polarizing film included in the optical film of the present invention is made of a polyvinyl alcohol-based resin in which iodine is oriented as described above, and a polarizing film stretched in a two-stage stretching step including auxiliary stretching in air and stretching in boric acid in water. can do.
  • the polarizing film is made of a polyvinyl alcohol-based resin in which iodine is oriented as described above, by excessively dyeing the stretched body of the stretched PVA-based resin layer and the stretched resin base material, and then by decoloring.
  • the manufactured polarizing film can be used.
  • the thickness of the polarizing film is 20 ⁇ m or less, preferably 12 ⁇ m or less, more preferably 9 ⁇ m or less, further preferably 1 to 8 ⁇ m, and particularly preferably 3 to 6 ⁇ m. If it is in the said range, it will become a preferable aspect, without obstructing bending.
  • the optical film used in the present invention may include a retardation film, and the retardation film (also referred to as a retardation film) is obtained by stretching a polymer film or aligns and fixes a liquid crystal material. Can be used.
  • the retardation film refers to a film having birefringence in a plane and / or a thickness direction.
  • the retardation film examples include an antireflection retardation film (see JP-A-2012-133303, [0221], [0222], and [0228]), and a viewing-angle compensation phase difference film (JP-A-2012-133303, [0225]). ], [0226]), and an inclined alignment retardation film for viewing angle compensation (see JP-A-2012-133303, [0227]).
  • the retardation film as long as the retardation film has substantially the above function, for example, the retardation value, the arrangement angle, the three-dimensional birefringence, whether a single layer or a multilayer is not particularly limited, and a known retardation film is used. Can be used.
  • the laminate for a flexible image display device of the present invention is a laminate for a flexible image display device including an adhesive layer, wherein the adhesive layer has the predetermined storage modulus.
  • the pressure-sensitive adhesive layer may be a single layer, but is used for laminating a transparent conductive film, an organic EL display panel, a window, a decorative printing film, a retardation layer, a protective film, and the like in addition to the optical film.
  • a plurality of pressure-sensitive adhesive layers are included in a laminate for a flexible image display device such as a first pressure-sensitive adhesive layer and a second pressure-sensitive adhesive layer, for example, as shown in FIG. Etc.
  • the first pressure-sensitive adhesive layer is disposed on the opposite side of the protective film from the surface in contact with the polarizing film. Is preferable (see FIG. 2).
  • the second pressure-sensitive adhesive layer may be disposed on the side opposite to the surface in contact with the polarizing film with respect to the retardation film. (See FIG. 2).
  • the third pressure-sensitive adhesive layer is in contact with the first pressure-sensitive adhesive layer with respect to the transparent conductive layer constituting the touch sensor. It can be located on the opposite side of the surface (see FIG. 3).
  • the member having a transparent conductive layer is not particularly limited, and a known member can be used. However, a member having a transparent conductive layer on a transparent substrate such as a transparent film, or a transparent conductive layer and a liquid crystal A member having a cell can be given.
  • the transparent substrate may be any material as long as it has transparency, and examples thereof include a substrate made of a resin film or the like (for example, a sheet, film, or plate-like substrate).
  • the thickness of the transparent substrate is not particularly limited, but is preferably about 10 to 200 ⁇ m, more preferably about 15 to 150 ⁇ m.
  • the material of the resin film is not particularly limited, but various plastic materials having transparency can be used.
  • the material include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, and (meth) acrylic resins.
  • polyester resins, polyimide resins and polyethersulfone resins are particularly preferred.
  • the transparent substrate is subjected to an etching treatment or undercoating treatment such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical conversion, oxidation or the like on the surface in advance, and the transparent conductive layer provided on this You may make it improve the adhesiveness with respect to a transparent base material.
  • dust removal and cleaning may be performed by solvent cleaning or ultrasonic cleaning as necessary.
  • the constituent material of the transparent conductive layer is not particularly limited, and is selected from the group consisting of indium, tin, zinc, gallium, antimony, titanium, silicon, zirconium, magnesium, aluminum, gold, silver, copper, palladium, tungsten, and molybdenum. At least one kind of metal or metal oxide to be used, or an organic conductive polymer such as polythiophene is used.
  • the metal oxide may further contain the metal atom shown in the above group, if necessary.
  • indium oxide (ITO) containing tin oxide, tin oxide containing antimony, and the like are preferably used, and ITO is particularly preferably used.
  • the ITO preferably contains 80 to 99% by weight of indium oxide and 1 to 20% by weight of tin oxide.
  • examples of the ITO include crystalline ITO and non-crystalline (amorphous) ITO.
  • Crystalline ITO can be obtained by applying a high temperature during sputtering or by further heating amorphous ITO.
  • the thickness of the transparent conductive layer of the present invention is preferably 0.005 to 10 ⁇ m, more preferably 0.01 to 3 ⁇ m, and further preferably 0.01 to 1 ⁇ m. If the thickness of the transparent conductive layer is less than 0.005 ⁇ m, the change in the electrical resistance of the transparent conductive layer tends to increase. On the other hand, if it exceeds 10 ⁇ m, the productivity of the transparent conductive layer tends to decrease, the cost increases, and the optical characteristics tend to decrease.
  • the total light transmittance of the transparent conductive layer of the present invention is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more.
  • the density of the transparent conductive layer of the present invention is preferably 1.0 to 10.5 g / cm 3 , and more preferably 1.3 to 3.0 g / cm 3 .
  • an undercoat layer, an oligomer prevention layer, and the like can be provided between the transparent conductive layer and the transparent substrate, if necessary.
  • the transparent conductive layer constituting the touch sensor is disposed on the side opposite to the surface in contact with the retardation film with respect to the second adhesive layer. (See FIG. 2).
  • the transparent conductive layer constituting the touch sensor may be arranged on the side opposite to the surface in contact with the protective film with respect to the first adhesive layer. (See FIG. 3).
  • the transparent conductive layer constituting the touch sensor can be disposed between the protective film and the window film (OCA) (see FIG. 3).
  • the transparent conductive layer can be suitably applied to a liquid crystal display device having a built-in touch sensor such as an in-cell type or an on-cell type when used in a flexible image display device.
  • a touch sensor is built in an organic EL display panel. (Even if it is incorporated).
  • the laminate for a flexible image display device of the present invention may have a conductive layer (conductive layer, antistatic layer). Since the laminate for a flexible image display device has a bending function and has a very thin thickness configuration, the laminate has high reactivity to weak static electricity generated in a manufacturing process and the like, and is easily damaged. By providing a conductive layer on the substrate, a load due to static electricity in a manufacturing process or the like is greatly reduced, which is a preferable embodiment.
  • the conductive layer may be an undercoat layer having a conductive function, may be an adhesive containing a conductive component, or may be a surface treatment layer further containing a conductive component.
  • a method of forming a conductive layer between a polarizing film and a pressure-sensitive adhesive layer using an antistatic composition containing a conductive polymer such as polythiophene and a binder can be employed.
  • an adhesive containing an ionic compound as an antistatic agent can also be used.
  • the conductive layer preferably has one or more layers, and may include two or more layers.
  • a flexible image display device of the present invention includes the above-described laminate for a flexible image display device and an organic EL display panel, and the laminate for a flexible image display device is arranged on the viewing side with respect to the organic EL display panel, and is bent. It is configured to be possible. Although optional, a window can be arranged on the viewing side with respect to the flexible image display device laminate (see FIGS. 2 to 4).
  • FIG. 2 is a sectional view showing one embodiment of the flexible image display device according to the present invention.
  • the flexible image display device 100 includes a laminate 11 for a flexible image display device and an organic EL display panel 10 that is configured to be foldable.
  • the laminate 11 for a flexible image display device is arranged on the viewing side with respect to the organic EL display panel 10, and the flexible image display device 100 is configured to be bendable.
  • a transparent window 40 can be disposed on the viewing side of the laminate 11 for a flexible image display device via the first pressure-sensitive adhesive layer 12-1.
  • the laminate 11 for a flexible image display device includes the optical laminate 20, and further, an adhesive layer constituting the second adhesive layer 12-2 and the third adhesive layer 12-3.
  • the optical laminate 20 includes the polarizing film 1, the protective film 2 made of a transparent resin material, and the retardation film 3.
  • the protective film 2 made of a transparent resin material is bonded to the first surface on the viewing side of the polarizing film 1.
  • the retardation film 3 is bonded to a second surface different from the first surface of the polarizing film 1.
  • the polarizing film 1 and the retardation film 3 generate, for example, circularly polarized light in order to prevent light that has entered inside from the viewing side of the polarizing film 1 from being internally reflected and emitted to the viewing side, or a viewing angle. Or to compensate for it.
  • the protective film is provided on both surfaces of the conventional polarizing film, whereas the protective film is provided on only one surface, and the polarizing film itself is used in the conventional organic EL display device.
  • the thickness of the optical laminate 20 can be reduced by using a polarizing film having a very thin thickness (20 ⁇ m or less) as compared with a polarizing film that is present. Further, since the polarizing film 1 is much thinner than a polarizing film used in a conventional organic EL display device, stress due to expansion and contraction generated under temperature or humidity conditions is extremely small.
  • the possibility that the stress generated by the shrinkage of the polarizing film causes deformation such as warpage in the adjacent organic EL display panel 10 is greatly reduced, and the deterioration in display quality and the destruction of the panel sealing material due to the deformation are greatly reduced. Can be suppressed. Further, the use of a polarizing film having a small thickness does not hinder bending, which is a preferable embodiment.
  • the thickness (for example, 92 ⁇ m or less) of the optical laminate 20 is reduced, and the first having the characteristics of 100% modulus and 500% modulus as described above.
  • the pressure-sensitive adhesive layer 12-1 By arranging the pressure-sensitive adhesive layer 12-1 on the side opposite to the retardation film 3 with respect to the protective film 2, it is possible to reduce the stress applied to the optical laminated body 20, whereby the optical laminated body 20 is bent. This makes it possible to suppress cracking of each layer and peeling of the pressure-sensitive adhesive layer at the bent portion, and finally, it is possible to bend the laminate 11 for a flexible image display device. Therefore, appropriate ranges of 100% modulus and 500% modulus may be set according to the environmental temperature in which the flexible image display device is used.
  • a foldable transparent conductive layer 6 constituting a touch sensor may be further disposed on the side opposite to the protective film 2 with respect to the retardation film 3.
  • the transparent conductive layer 6 is configured to be directly bonded to the retardation film 3 by a manufacturing method as described in, for example, JP-A-2014-219667, so that the thickness of the optical laminate 20 is reduced. Can be further reduced when the optical laminate 20 is bent.
  • an adhesive layer constituting the third adhesive layer 12-3 may be further disposed on the side opposite to the retardation film 3 with respect to the transparent conductive layer 6.
  • the second pressure-sensitive adhesive layer 12-2 is directly bonded to the transparent conductive layer 6.
  • the flexible image display device shown in FIG. 3 is almost the same as that shown in FIG. 2, but the flexible image display device shown in FIG.
  • the foldable transparent conductive layer 6 is disposed on the side opposite to the protective film 2 with respect to the first adhesive layer 12-1.
  • a foldable transparent conductive layer 6 constituting the touch sensor.
  • the third pressure-sensitive adhesive layer 12-3 is disposed on the side opposite to the retardation film 3 with respect to the transparent conductive layer 2
  • the flexible image display device is different in that the second pressure-sensitive adhesive layer 12-2 is disposed on the side opposite to the protective film 2 with respect to the retardation film 3.
  • the third pressure-sensitive adhesive layer 12-3 can be disposed when the window 40 is disposed on the viewing side with respect to the flexible image display device laminate 11.
  • the flexible image display device of the present invention can be suitably used as a flexible liquid crystal display device, an organic EL (electroluminescence) display device, an image display device such as electronic paper, or the like. Further, it can be used irrespective of a touch panel system such as a resistive film system or a capacitance system.
  • the flexible image display device of the present invention is also used as an in-cell type flexible image display device in which a transparent conductive layer 6 constituting a touch sensor is built in an organic EL display panel 10-1. It is possible to do.
  • Example 1 Preparation of prepolymer> A monomer mixture containing 59 parts by weight of lauryl acrylate (LA), 40 parts by weight of 2-ethylhexyl acrylate (2EHA), and 1 part by weight of 4-hydroxybutyl acrylate (4HBA) and 2,2-dimethoxy-1 as a photopolymerization initiator , 2-diphenylethan-1-one (trade name "Irgacure 651", BASF Japan Ltd.) and 1-hydroxy-cyclohexyl-phenyl-ketone (trade name “Irgacure 184", BASF Japan Ltd.) 0.05 parts by weight of each was put into a four-necked flask, and irradiated with ultraviolet light under a nitrogen atmosphere until the viscosity (BH viscosity system No. 5 rotor, 10 rpm, temperature 30 ° C.) became about 15 Pa ⁇ s. , By photopolymerization, partially polymerized monomer syrup (partial polymerized mono
  • the acrylic pressure-sensitive adhesive composition is applied onto a release-treated surface of a release film (trade name “MRF # 38”, manufactured by Mitsubishi Plastics, Inc.) so that the thickness after forming the pressure-sensitive adhesive layer is 70 ⁇ m. Then, a pressure-sensitive adhesive composition layer was formed, and then a release film (trade name “MRN # 38”, manufactured by Mitsubishi Plastics, Inc.) was bonded to the surface of the pressure-sensitive adhesive composition layer. Thereafter, ultraviolet irradiation was performed under the conditions of illuminance: 4 mW / cm 2 and light amount: 1200 mJ / cm 2 , and the pressure-sensitive adhesive composition layer was light-cured to form a pressure-sensitive adhesive layer. Then, an adhesive layer in which both surfaces of the adhesive layer were protected by a release film was obtained.
  • a release film trade name “MRF # 38”, manufactured by Mitsubishi Plastics, Inc.
  • Examples 2 and 3 Comparative Examples 1 to 5
  • the monomer mixture (type, composition) of the prepolymer was changed as shown in Table 2, and in the preparation of the acrylic pressure-sensitive adhesive composition, the additional monomer (type, blending amount) was changed.
  • the preparation of the prepolymer and the preparation of the acrylic pressure-sensitive adhesive composition were performed in the same manner as in Example 1 except for the change as shown in Table 2, and then the pressure-sensitive adhesive layer was formed.
  • thermoplastic resin substrate an amorphous polyethylene terephthalate (hereinafter also referred to as “PET”) (IPA copolymerized PET) film (thickness: 100 ⁇ m) having an isophthalic acid unit of 7 mol% is prepared, and the surface is corona-treated ( 58 W / m 2 / min).
  • PET amorphous polyethylene terephthalate
  • acetoacetyl-modified PVA manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: Gosefimer Z200 (average degree of polymerization: 1200, degree of saponification: 98.5 mol%, degree of acetoacetylation: 5 mol%)
  • 1% by weight of added PVA polymerization degree 4200, saponification degree 99.2%
  • a coating solution of a PVA aqueous solution containing 5.5% by weight of a PVA-based resin was prepared.
  • the colored laminate is prepared by adding the stretched laminate to a dye solution containing iodine and potassium iodide at a liquid temperature of 30 ° C. so that the PVA layer constituting the polarizing film finally formed has a single transmittance of 40 to 44%.
  • the PVA layer contained in the stretched laminate was dyed with iodine by immersing the PVA layer in an arbitrary time.
  • the dyeing solution was adjusted to have an iodine concentration of 0.1 to 0.4% by weight and a potassium iodide concentration of 0.7 to 2.8% by weight using water as a solvent.
  • the ratio of the concentrations of iodine and potassium iodide is 1: 7.
  • a step of subjecting the PVA molecules of the PVA layer to which iodine had been adsorbed to a crosslinking treatment by immersing the colored laminate in a 30 ° C. aqueous boric acid crosslinking aqueous solution for 60 seconds was performed.
  • the boric acid crosslinking aqueous solution in this step had a boric acid content of 3 parts by weight with respect to 100 parts by weight of water and a potassium iodide content of 3 parts by weight with respect to 100 parts by weight of water.
  • the obtained colored laminate was stretched in a boric acid aqueous solution at a stretching temperature of 70 ° C., and stretched 3.05 times in the same direction as the stretching in the air (stretching in boric acid in water).
  • An optical film laminate having a stretching ratio of 5.50 was obtained.
  • the optical film laminate was taken out from the boric acid aqueous solution, and the boric acid attached to the surface of the PVA layer was washed with an aqueous solution having a potassium iodide content of 4 parts by weight with respect to 100 parts by weight of water.
  • the washed optical film laminate was dried by a drying process using hot air at 60 ° C.
  • the thickness of the polarizing film contained in the obtained optical film laminate was 5 ⁇ m.
  • the polarizing film and the protective film were adhered to each other using an adhesive shown below to obtain a polarizing film.
  • ACMO acryloylmorpholine
  • AAEM 2-acetoacetoxyethyl methacrylate, manufactured by Nippon Synthetic Chemical Company
  • UP-1190 ARUFON UP- 1190
  • Toagosei IRG907 IRGACURE907, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one
  • BASF DETX-S KAYACURE DETX-S, diethylthioxanthone, Nippon Kagaku Yakusha
  • the adhesive was cured by irradiating ultraviolet rays to form an adhesive layer.
  • ultraviolet rays a gallium-enclosed metal halide lamp (manufactured by Fusion UV Systems, Inc., trade name “Light HAMMER10”, bulb: V bulb, peak illuminance: 1600 mW / cm 2 , cumulative irradiation amount 1000 / mJ / cm 2 (wavelength 380-440 nm)).
  • the retardation film (1/4 wavelength retardation plate) of this embodiment is composed of two layers, a 1/4 wavelength plate retardation layer and a 1/2 wavelength plate retardation layer, in which the liquid crystal material is aligned and fixed.
  • the retardation film was constituted. Specifically, it was manufactured as follows.
  • Liquid crystal material A polymerizable liquid crystal material exhibiting a nematic liquid crystal phase (manufactured by BASF: trade name: Paliocolor LC242) was used as a material for forming the retardation layers for the ⁇ wavelength plate and the ⁇ wavelength plate.
  • a photopolymerization initiator for the polymerizable liquid crystal material (manufactured by BASF, trade name: Irgacure 907) was dissolved in toluene. Further, for the purpose of improving coating properties, DIC Megafac series was added in an amount of about 0.1 to 0.5% depending on the liquid crystal thickness to prepare a liquid crystal coating liquid.
  • the liquid crystal coating liquid was applied on an alignment base material using a bar coater, dried by heating at 90 ° C. for 2 minutes, and fixed by ultraviolet curing in a nitrogen atmosphere.
  • a material such as PET, which can transfer a liquid crystal coating layer later, was used.
  • a fluoropolymer which is a Megafac series manufactured by DIC, is added in an amount of about 0.1% to 0.5% depending on the thickness of the liquid crystal layer, and MIBK (methyl isobutyl ketone), cyclohexanone, or MIBK is added.
  • MIBK methyl isobutyl ketone
  • This coating solution was applied to a substrate using a wire bar, a drying process was performed at 65 ° C. for 3 minutes, and the orientation was fixed by ultraviolet curing under a nitrogen atmosphere to produce a coating.
  • a material such as PET, which can transfer a liquid crystal coating layer later, was used.
  • the manufacturing process of this embodiment will be described. Note that the numbers in FIG. 7 are different from the numbers in the other drawings.
  • the substrate 14 was provided by a roll, and the substrate 14 was supplied from a supply reel 21.
  • a coating liquid of the ultraviolet curable resin 10 was applied to the substrate 14 by the die 22.
  • the roll plate 30 was a cylindrical molding die in which the irregularities related to the quarter-wave plate alignment film of the quarter-wave retardation plate were formed on the peripheral side surface.
  • the base material 14 coated with the ultraviolet curable resin is pressed against the peripheral side surface of the roll plate 30 by the pressure roller 24, and the ultraviolet curable resin is irradiated with ultraviolet light by an ultraviolet irradiation device 25 composed of a high-pressure mercury lamp. Cured.
  • an ultraviolet irradiation device 25 composed of a high-pressure mercury lamp.
  • the irregularities formed on the peripheral side surface of the roll plate 30 were transferred to the substrate 14 so as to be at an angle of 75 ° with respect to the MD direction.
  • the base material 14 was peeled off from the roll plate 30 integrally with the ultraviolet curable resin 10 cured by the peeling roller 26, and a liquid crystal material was applied by a die 29.
  • the liquid crystal material was cured by irradiating ultraviolet rays with the ultraviolet irradiating device 27, and thereby, a configuration relating to the retardation layer for a ⁇ wavelength plate was prepared.
  • the base material 14 is conveyed to the die 32 by the conveying roller 31, and the coating liquid of the ultraviolet curable resin 12 is applied to the quarter-wave plate retardation layer of the base material 14 by the die 32.
  • the roll plate 40 was a cylindrical molding die in which the irregularities related to the half-wave plate alignment film of the quarter-wave retardation plate were formed on the peripheral side surface.
  • the base material 14 coated with the ultraviolet curable resin is pressed against the peripheral side surface of the roll plate 40 by the pressure roller 34, and the ultraviolet curable resin is irradiated with ultraviolet light by an ultraviolet irradiation device 35 composed of a high-pressure mercury lamp. Cured.
  • an ultraviolet irradiation device 35 composed of a high-pressure mercury lamp.
  • the uneven shape formed on the peripheral side surface of the roll plate 40 was transferred to the base material 14 so as to be at an angle of 15 ° with respect to the MD direction.
  • the base material 14 was peeled off from the roll plate 40 integrally with the ultraviolet curable resin 12 cured by the peeling roller 36, and a liquid crystal material was applied by a die 39.
  • the liquid crystal material is cured by irradiating the liquid crystal material with ultraviolet light by the ultraviolet irradiation device 37, thereby forming a configuration relating to the retardation layer for the ⁇ wavelength plate.
  • a 7 ⁇ m thick retardation film composed of two retardation layers for a plate was obtained.
  • optical film optical laminate
  • the retardation film obtained as described above and the polarizing film obtained as described above are continuously bonded using the above-mentioned adhesive by using a roll-to-roll method, and axes of a slow axis and an absorption axis.
  • a laminated film (optical laminated body) was produced so that the angle was 45 °.
  • the first to third pressure-sensitive adhesive layers (together with the respective transparent substrates) obtained as described above are applied to a PET film which is a transparent substrate 8-1 having a thickness of 25 ⁇ m, and , The third pressure-sensitive adhesive layer 12-3 on the retardation film 3, and the transparent base material 8- on which the second pressure-sensitive adhesive layer 12-2 is bonded.
  • a laminate 11 for a flexible image display device was produced.
  • ⁇ Storage modulus G 'of pressure-sensitive adhesive layer The separator was peeled off from the pressure-sensitive adhesive layer obtained in each of the examples and comparative examples, and a plurality of pressure-sensitive adhesive layers were laminated to produce a test sample having a thickness of about 2 mm.
  • the test sample was punched out into a disk shape having a diameter of 7.9 mm, sandwiched between parallel plates, and subjected to dynamic viscoelasticity measurement under the following conditions using "Advanced Rheometric Expansion System (ARES)" manufactured by Rheometric Scientific, under the following conditions. From the results, the storage elastic modulus G ′ of the pressure-sensitive adhesive layer at ⁇ 20 ° C., 23 ° C., and 85 ° C. was read.
  • Deformation mode torsion Measurement temperature: -70 ° C to 150 ° C Heating rate: 5 ° C / min
  • Sample 1 was obtained by scraping about 0.2 g from the pressure-sensitive adhesive layer formed on the release-treated surface of the separator film one week after the preparation. After wrapping the sample 1 in a Teflon (registered trademark) film having a diameter of 0.2 ⁇ m (trade name “NTF1122”, manufactured by Nitto Denko Corporation), the sample was tied with a kite string, and this was designated as sample 2. The weight of Sample 2 before being subjected to the following test was measured, and this was designated as Weight A. The weight A is the total weight of Sample 1 (adhesive layer), Teflon (registered trademark) film, and kite string.
  • the total weight of the Teflon (registered trademark) film and the kite string was defined as weight B.
  • the sample 2 was placed in a 50 ml container filled with ethyl acetate, and allowed to stand at 23 ° C. for one week. Thereafter, the sample 2 was taken out of the container, dried in a dryer at 130 ° C. for 2 hours to remove ethyl acetate, and the weight of the sample 2 was measured. The weight of the sample 2 after the test was measured, and this was defined as a weight C.
  • the gel fraction of the pressure-sensitive adhesive layer is preferably from 55 to 90% by weight, more preferably from 57 to 90% by weight, still more preferably from 60 to 88% by weight, still more preferably from 62 to 88% by weight. Preferably it is 65-86% by weight, most preferably 70-86% by weight.
  • appearance e.g., glue dents
  • workability e.g., workability, durability, and flexibility are improved, and both flexibility under a normal temperature environment and a high temperature environment is compatible. This is a preferred embodiment.
  • ⁇ Measurement of thickness> The thicknesses of the polarizing film, the retardation film, the protective film, the optical laminate, and the pressure-sensitive adhesive layer were measured using a dial gauge (manufactured by Mitutoyo).
  • FIGS. 5A and 5B are schematic diagrams of a bending test based on a U-shaped expansion / contraction tester (Yuasa System Equipment Co., Ltd.).
  • the testing machine has a mechanism of repeating 180 ° bending in a U-shape with no load on a planar workpiece in a constant temperature bath, and adjusting a distance between the surfaces bent in a U-shape to reduce a bending radius. Can be changed.
  • the laminate for a flexible image display device of 2.5 cm ⁇ 10 cm obtained in each of the examples and comparative examples was set on a testing machine so that it could be bent in the long side direction. Evaluation was performed at RH and 85 ° C.
  • the configuration shown in FIG. 6 was adopted, with the transparent substrate 8-2 (PET film) being on the concave side (inside) and the substrate 9 (PI film) being on the convex side (outside). ) And evaluated by bending in the long side direction near the center. The bending strength was evaluated by the number of times until cracking or peeling between layers occurred at the bent portion of the laminate for a flexible image display device. Here, when the number of times of bending reached 200,000 times, the test was terminated.
  • this sample was subjected to a stress (N / D) at an elongation of 100%, 500%, and 700% modulus from a load-elongation curve measured at a chuck distance of 10 mm and a tensile speed of 300 mm / min. mm 2 ).
  • 100% elongation refers to a state where the distance between chucks is 20 mm
  • 500% elongation refers to a state where the distance between chucks is 60 mm
  • 700% elongation refers to a state where the distance between chucks is 80 mm.
  • ⁇ Adhesion> The PI film, the optical laminate, and the PET film used above were bonded and fixed on a glass plate via a general-purpose double-sided tape (No. 500, manufactured by Nitto Denko Corporation) to produce an adherend.
  • a pressure-sensitive adhesive layer having a release film (trade name “MRF # 38”, manufactured by Mitsubishi Plastics, Inc.) having a thickness of 50 ⁇ m was prepared on both sides.
  • the layer may be cracked (bent) or peeled with repeated bending.
  • the layer may be cracked (bent) or peeled with repeated bending.
  • Comparative Examples 1 to 4 are not included in the storage elastic modulus G ′ in the predetermined range, and therefore, according to the bending resistance (continuous bending) test, ⁇ 20 ° C., 25 ° C. ⁇ 50% RH, and 85 ° C. When exposed to a low-temperature, normal-temperature, or high-temperature environment), cracking (breaking) or peeling was at a practically problematic level, and was inferior in either bending resistance or adhesion.
  • Reference Signs List 1 polarizing film 2 protective film 2-1 protective film 2-2 protective film 3 retardation layer 4-1 transparent conductive film 4-2 transparent conductive film 5-1 base film 5-2 base film 6 transparent conductive layer 6 1 Transparent conductive layer 6-2 Transparent conductive layer 7 Spacer 8 Transparent substrate 8-1 Transparent substrate (PET film) 8-2 Transparent substrate (PET film) 9 Base material (PI film) 10 Organic EL display panel 10-1 Organic EL display panel (with touch sensor) 11 Laminate for Flexible Image Display (Laminate for Organic EL Display) 12 pressure-sensitive adhesive layer 12-1 first pressure-sensitive adhesive layer 12-2 second pressure-sensitive adhesive layer 12-3 third pressure-sensitive adhesive layer 13 decorative printing film 14 double-sided pressure-sensitive adhesive tape 20 optical laminate 30 touch panel 40 window 100 flexible Image display device (organic EL display device) P Bending point UV UV irradiation L Liquid crystal material

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PCT/JP2019/018567 2018-06-22 2019-05-09 フレキシブル画像表示装置用粘着剤層、フレキシブル画像表示装置用積層体、及び、フレキシブル画像表示装置 WO2019244499A1 (ja)

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CN201980041327.4A CN112292433B (zh) 2018-06-22 2019-05-09 挠性图像显示装置用粘合剂层、挠性图像显示装置用层叠体、及挠性图像显示装置

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