WO2021111995A1 - 粘着材、粘着シートおよび屈曲性積層部材 - Google Patents

粘着材、粘着シートおよび屈曲性積層部材 Download PDF

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WO2021111995A1
WO2021111995A1 PCT/JP2020/044153 JP2020044153W WO2021111995A1 WO 2021111995 A1 WO2021111995 A1 WO 2021111995A1 JP 2020044153 W JP2020044153 W JP 2020044153W WO 2021111995 A1 WO2021111995 A1 WO 2021111995A1
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meth
flexible
acrylate
sheet
pressure
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PCT/JP2020/044153
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English (en)
French (fr)
Japanese (ja)
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正規 石原
幸男 白神
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大塚化学株式会社
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Priority to CN202080079545.XA priority Critical patent/CN114728507B/zh
Priority to JP2021521081A priority patent/JP6888181B1/ja
Priority to KR1020227017062A priority patent/KR20220110736A/ko
Publication of WO2021111995A1 publication Critical patent/WO2021111995A1/ja

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives 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
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/14Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered 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
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives 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
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38Pressure-sensitive adhesives [PSA]
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38Pressure-sensitive adhesives [PSA]
    • C09J7/381Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385Acrylic polymers
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/133305Flexible substrates, e.g. plastics, organic film
    • GPHYSICS
    • G09EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09FDISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30Indicating 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
    • G09F9/301Indicating 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
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10Substrates, e.g. flexible substrates
    • H10K77/111Flexible substrates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00Electrical equipment
    • B32B2457/20Displays, e.g. liquid crystal displays, plasma displays

Definitions

  • the present invention relates to an adhesive material used for bonding one flexible member and another flexible member constituting a flexible laminated member that is repeatedly bent and used.
  • the pressure-sensitive adhesive material is provided, for example, in the form of a base-based pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer on a support base material or a base material-less pressure-sensitive adhesive sheet without a support base material, and the members are bonded to each other.
  • Flexible displays that are repeatedly bent and used in image display devices such as liquid crystal display devices and organic electroluminescence (organic EL) display devices have attracted attention.
  • Flexible displays include foldable foldable displays, rollable displays that can be rolled into a tubular shape, and the like, and are expected to be used for mobile terminals such as smartphones and tablet terminals, and stationary displays that can be stored.
  • Patent Document 1 describes one surface and the other of the adhesive layer.
  • Adhesive material for repetitive bending devices in which the ratio of shear stress 60 seconds after 1000% displacement to the maximum shear stress when the surfaces are displaced 1000% in opposite directions and the gel fraction are controlled within a predetermined range. Is disclosed (see Patent Document 1 (Claim 1)).
  • An object of the present invention is to provide an adhesive material that can be used.
  • the pressure-sensitive adhesive material of the present invention that has been able to solve the above problems is a pressure-sensitive adhesive material used for bonding one flexible member and another flexible member, and the pressure-sensitive adhesive material has a reactive functional group. It is a cured product of a pressure-sensitive adhesive composition containing a (meth) acrylic copolymer and a cross-linking agent, and the (meth) acrylic copolymer is obtained by living radical polymerization, and the molecular weight distribution thereof.
  • the Young's modulus of the adhesive material is 10 kPa to 1000 kPa, and the adhesive material is stretched until the tensile stress becomes 50 kPa, and then a shrinkage test for releasing the tensile stress is performed.
  • the ratio of the elastic modulus at contraction of the 10th time to the elastic modulus at contraction of the first time is 60% or more.
  • the length of the obtained molecular chain is non-uniform, and the composition of each molecular chain is also non-uniform. Therefore, when such a copolymer is used as a pressure-sensitive adhesive, the distance between the cross-linking points cross-linked by the cross-linking agent becomes non-uniform, and it is considered that the obtained pressure-sensitive adhesive has a location where the elastic modulus is locally different. It is considered that the adhesive material having a non-uniform distance between the cross-linking points has a non-uniform elastic modulus when bent and stretched repeatedly, so that local fracture is likely to occur and plastic deformation is likely to occur.
  • the (meth) acrylic copolymer produced by living radical polymerization has a narrow molecular weight distribution and a uniform composition of each molecular chain. That is, the number of reactive functional groups contained in each molecular chain of the (meth) acrylic polymer becomes uniform. Therefore, when such a (meth) acrylic copolymer is used as the pressure-sensitive adhesive material, the distances between the cross-linking points cross-linked by the cross-linking agent are uniform, and the obtained cured product (adhesive material) has almost the same elastic modulus as a whole. Come to have a rate. Since the entire adhesive material has almost the same elastic modulus, the occurrence of local fracture is suppressed even when bending and stretching are repeated, and the decrease in the force for returning to the original shape is suppressed even when bending and stretching are repeated. it can.
  • the adhesive material has a predetermined Young's modulus and the maintenance rate of the elastic modulus at the time of contraction is high in repeated shrinkage tests, the adhesive material can follow the deformation of bending and stretching of the flexible member. Therefore, by using the pressure-sensitive adhesive material of the present invention, deformation of the flexible laminated member at the bent portion can be suppressed. In addition, since there is little deformation at the bent portion, it can be expected that the occurrence of appearance defects such as waviness can be suppressed.
  • the adhesive material of the present invention is used for laminating the flexible members constituting the flexible laminated member, even if the flexible laminated member is repeatedly bent, deformation at the bent portion can be suppressed.
  • (meth) acrylic means “at least one of acrylic and methacrylic”.
  • (Meta) acrylate refers to “at least one of acrylate and methacrylate”.
  • (Meta) acryloyl” means “at least one of acryloyl and methacryloyl”.
  • the "vinyl monomer” refers to a monomer having a carbon-carbon double bond capable of radical polymerization in the molecule.
  • the "structural unit derived from a vinyl monomer” means a structural unit in which a radically polymerizable carbon-carbon double bond of a vinyl monomer is polymerized into a carbon-carbon single bond.
  • the “structural unit derived from (meth) acrylate” refers to a structural unit obtained by polymerizing a radically polymerizable carbon-carbon double bond of (meth) acrylate into a carbon-carbon single bond.
  • the “structural unit derived from the (meth) acrylic monomer” refers to a structural unit obtained by polymerizing a radically polymerizable carbon-carbon double bond of the (meth) acrylic monomer into a carbon-carbon single bond.
  • the pressure-sensitive adhesive material of the present invention is a pressure-sensitive adhesive material used for bonding one flexible member and another flexible member constituting a flexible laminated member that is repeatedly bent and used.
  • the pressure-sensitive adhesive is a cured product of a pressure-sensitive adhesive composition containing a (meth) acrylic copolymer having a reactive functional group and a cross-linking agent, and the (meth) acrylic copolymer is subjected to living radical polymerization. It is obtained, and its molecular weight distribution (Mw / Mn) is 3.0 or less.
  • the Young's modulus of the pressure-sensitive adhesive material is 10 kPa to 1000 kPa, and the pressure-sensitive adhesive material is stretched until the tensile stress reaches 50 kPa, and then the shrinkage test for releasing the tensile stress is repeated 10 times.
  • the ratio of the elastic modulus at the time of the tenth contraction to the elastic modulus is 60% or more.
  • the Young's modulus of the pressure-sensitive adhesive is preferably 10 kPa or more, 25 kPa or more, more preferably 50 kPa or more, further preferably 90 kPa or more, preferably 1000 kPa or less, 600 kPa or less, more preferably 500 kPa or less, still more preferably 400 kPa or less. is there. If the Young's modulus is 10 kPa or more, appearance defects such as waviness can be suppressed even in a high temperature environment, and if it is 1000 kPa or less, floating and peeling at the time of bending can be suppressed even in a low temperature environment.
  • the ratio of the elastic modulus at contraction of the 10th time to the elastic modulus at contraction of the first time was 60. % Or more.
  • the ratio is 60% or more, the amount of plastic deformation of the adhesive material is small even when the adhesive material is repeatedly bent and stretched. Therefore, when it is used for a flexible laminated member, it is possible to suppress the occurrence of appearance defects such as deformation marks at the bent portion.
  • the ratio is preferably 70% or more, more preferably 80% or more, and the upper limit is 100%.
  • the elastic modulus of the pressure-sensitive adhesive material at the time of first shrinkage is preferably 0.1 MPa or more, more preferably 0.2 MPa or more, further preferably 0.5 MPa or more, preferably 10 MPa or less, and more preferably 5.0 MPa or less. , More preferably 3.0 MPa or less.
  • the elongation (first elongation) when the tensile stress is 50 kPa is preferably 10% or more, more preferably. It is 100% or more, more preferably 250% or more, and particularly preferably 500% or more. If the elongation is 10% or more, the aberration of the film at the time of bending can be absorbed.
  • the upper limit of the elongation is not particularly limited, but is usually about 1000%.
  • the gel fraction of the pressure-sensitive adhesive material is preferably 20% to 100%, more preferably 50% to 100%, and particularly preferably 70% to 100% from the viewpoint of durability and adhesive strength. preferable. If the gel fraction is too low, lack of durability due to insufficient cohesive force is likely to occur.
  • the gel fraction can be controlled by the blending amount of the crosslinking agent in the pressure-sensitive adhesive composition, the crosslinking treatment temperature, and the crosslinking treatment time.
  • the pressure-sensitive adhesive is a cured product of a pressure-sensitive adhesive composition containing a (meth) acrylic copolymer having a reactive functional group and a cross-linking agent.
  • the pressure-sensitive adhesive composition contains (A) a (meth) acrylic copolymer having a reactive functional group and (B) a cross-linking agent.
  • ((A) (Meta) acrylic copolymer having a reactive functional group) The (meth) acrylic copolymer having the (A) reactive functional group (hereinafter, may be simply referred to as “(A) copolymer”) is obtained by living radical polymerization. It is a (meth) acrylic copolymer having a molecular weight distribution (Mw / Mn) of less than 3.0 and having a reactive functional group.
  • the (meth) acrylic copolymer may be a copolymer containing a structural unit derived from the (meth) acrylic monomer as a main component (50% by mass or more), and is a vinyl monomer other than the (meth) acrylic monomer. Can contain structural units derived from.
  • the content of the structural unit derived from the (meth) acrylic monomer in the copolymer (A) is preferably 80% by mass or more, more preferably 90% by mass or more, based on 100% by mass of the entire copolymer.
  • the copolymer (A) may be composed of only structural units derived from the (meth) acrylic monomer.
  • the (A) copolymer is preferably a (meth) acrylate-based copolymer.
  • the (meth) acrylate-based copolymer may be a copolymer containing a structural unit derived from (meth) acrylate as a main component (50% by mass or more), and is derived from a vinyl monomer other than (meth) acrylate. It can contain structural units.
  • the (meth) acrylate is an ester compound produced from (meth) acrylic acid and a compound having a hydroxy group.
  • the content of the structural unit derived from the (meth) acrylate in the (A) copolymer is preferably 80% by mass or more, more preferably 90% by mass or more, based on 100% by mass of the entire copolymer.
  • the (A) copolymer has a reactive functional group.
  • the reactive functional group is a functional group that can react with the functional group of the (B) cross-linking agent described later.
  • Examples of the reactive functional group include one or more selected from the group consisting of a hydroxy group, a carboxy group and an epoxy group, and a hydroxy group and / or a carboxy group are preferable.
  • Examples of the combination of the reactive functional group of the (A) copolymer and the functional group of the (B) cross-linking agent include the following combinations.
  • the functional group of the (B) cross-linking agent is an isocyanate group
  • examples of the reactive functional group of the (A) copolymer include a hydroxy group.
  • the functional group of the (B) cross-linking agent is an epoxy group
  • the reactive functional group of the (A) copolymer includes a carboxy group.
  • the amount of the reactive functional group per 100 g of the (A) copolymer is preferably 0.5 mmol / 100 g or more, more preferably 1 mmol / 100 g or more, still more preferably 5 mmol / 100 g or more, and particularly preferably 10 mmol / 100 g or more. , Most preferably 15 mL / 100 g, preferably 150 mmol / 100 g or less, more preferably 100 mmol / 100 g or less, still more preferably 70 mmol / 100 g or less, and particularly preferably 50 mmol / 100 g or less.
  • the amount of the reactive functional group is 0.5 mmol / 100 g or more, the durability of the pressure-sensitive adhesive material is excellent, and when the amount is 150 mmol / 100 g or less, the adhesion of the pressure-sensitive adhesive material to the adherend is excellent.
  • the amount of the carboxy group per 100 g of the (A) copolymer is preferably 0.5 mmol / 100 g or more, more preferably 1 mmol / 100 g or more, still more preferably. 5 mmol / 100 g or more, particularly preferably 10 mmol / 100 g or more, most preferably 15 mL / 100 g, preferably 150 mmol / 100 g or less, more preferably 100 mmol / 100 g or less, still more preferably 70 mmol / 100 g or less, and particularly preferably. It is 50 mmol / 100 g or less.
  • the amount of carboxy group per 100 g of the (A) copolymer is preferably 0.5 mmol / 100 g or more, more preferably 1 mmol / 100 g or more, still more preferably. 5 mmol / 100 g or more, particularly preferably 10 mmol / 100 g or more, most preferably 15 mmol / 100 g or more, preferably 150 mmol / 100 g or less, more preferably 100 mmol / 100 g or less, still more preferably 70 mmol / 100 g or less, and particularly preferably. Is 50 mmol / 100 g or less.
  • the copolymer (A) has a reactive functional group. That is, the copolymer (A) contains a structural unit (a-1) having a reactive functional group in its structure.
  • the structural unit (a-1) having the reactive functional group may have only one kind or two or more kinds.
  • the reaction functional group is a structural unit derived from a (meth) acrylic monomer (preferably (meth) acrylate monomer and / or (meth) acrylic acid), or a structural unit derived from a vinyl monomer other than the (meth) acrylic monomer. It may have any of them.
  • the structural unit (a-1) having a reactive functional group is a structure derived from a (meth) acrylic monomer having a reactive functional group (preferably (meth) acrylate monomer and / or (meth) acrylic acid).
  • a reactive functional group preferably (meth) acrylate monomer and / or (meth) acrylic acid.
  • examples thereof include a unit or a structural unit derived from a vinyl monomer other than the (meth) acrylic monomer having a reactive functional group.
  • the content of the structural unit (structural unit (a-1) having a reactive functional group) derived from the vinyl monomer having a reactive functional group in the (A) copolymer is 100% by mass of the whole copolymer. In, 0.1% by mass or more is preferable, more preferably 0.5% by mass or more, further preferably 1% by mass or more, particularly preferably 3% by mass or more, preferably 20% by mass or less, and more preferably. Is 15% by mass or less, more preferably 10% by mass or less, and particularly preferably 8% by mass or less. When the content of the structural unit (a-1) is within the above range, an adhesive material having an excellent balance between adhesion to an adherend and durability can be obtained.
  • the vinyl monomer having a reactive functional group includes a (meth) acrylic monomer having a reactive functional group and a vinyl monomer other than the (meth) acrylic monomer having a reactive functional group.
  • the copolymer (A) has a structural unit derived from a vinyl monomer having no reactive functional group (structural unit having no reactive functional group (a-2)).
  • the structural unit (a-2) having no reactive functional group includes a (meth) acrylate having a linear alkyl group, a (meth) acrylate having a branched alkyl group, and a (meth) having an alkoxy group.
  • Acrylic (meth) acrylate having a polyalkylene glycol structural unit, (meth) acrylate having an alicyclic hydrocarbon group, (meth) acrylate having an aromatic group, (meth) acrylate having a cyclic ether group, tertiary amino Examples thereof include structural units derived from (meth) acrylates and (meth) acrylamides having a group.
  • the structural unit (a-2) having no reactive functional group includes a (meth) acrylate having a linear alkyl group, a (meth) acrylate having a branched alkyl group, and an alicyclic hydrocarbon.
  • Structural units derived from at least one selected from the group consisting of (meth) acrylates having a hydrogen group, (meth) acrylates having an aromatic group, and (meth) acrylamides are preferred.
  • a (meth) acrylate having a linear alkyl group As the structural unit (a-2) in which the copolymer (A) does not have a reactive functional group, a (meth) acrylate having a linear alkyl group, a (meth) acrylate having a branched alkyl group, and the like.
  • the total content of these is preferably 60% by mass or more, more preferably 70% by mass. % Or more, more preferably 80% by mass or more, preferably 97.9% by mass or less, more preferably 97% by mass or less, still more preferably 90% by mass or less.
  • the content thereof is 0.1% by mass.
  • the above is preferable, more preferably 1% by mass or more, further preferably 3% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less.
  • Examples of the (meth) acrylic monomer include (b1) a (meth) acrylic monomer having no reactive functional group and (b2) a (meth) acrylic monomer having a reactive functional group. These monomers may be used alone or in combination of two or more. As the (meth) acrylic monomer having no (b1) reactive functional group, a (meth) acrylic rate monomer having no (b1-1) reactive functional group is preferable. Examples of the (meth) acrylic monomer having the (b2) reactive functional group include (b2-1) the (meth) acrylate monomer having the reactive functional group.
  • the (meth) acrylic monomer having no (b1) reactive functional group includes a (meth) acrylate having a linear alkyl group, a (meth) acrylate having a branched alkyl group, and an alkoxy group (meth). ) Acrylate, (meth) acrylate having a polyalkylene glycol structural unit, (meth) acrylate having an alicyclic hydrocarbon group, (meth) acrylate having an aromatic group, (meth) acrylate having a cyclic ether group, tertiary Examples thereof include (meth) acrylates having an amino group and (meth) acrylamides.
  • (meth) acrylate having a linear alkyl group (meth) acrylate having a branched alkyl group, (meth) acrylate having an alicyclic hydrocarbon group, and (meth) acrylate having an aromatic group. And at least one selected from the group consisting of (meth) acrylamides is preferred.
  • the (meth) acrylate having a linear alkyl group a (meth) acrylate having a linear alkyl group having 1 to 20 carbon atoms is preferable, and the carbon of the linear alkyl group is preferable.
  • Examples of the (meth) acrylate having a linear alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, and n-hexyl (meth) acrylate.
  • N-octyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-lauryl (meth) acrylate, n-stearyl (meth) acrylate and other (meth) acrylate linear alkyl Esther can be mentioned.
  • the (meth) acrylate having a branched chain alkyl group a (meth) acrylate having a branched chain alkyl group having 3 to 20 carbon atoms of the branched chain alkyl group is preferable, and the carbon of the branched chain alkyl group is preferable.
  • Examples of the (meth) acrylate having a branched alkyl group include isopropyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and isooctyl (meth) acrylate, 2 -Examples include (meth) acrylic acid branched chain alkyl esters such as ethylhexyl (meth) acrylate, isononyl (meth) acrylate, and isodecyl (meth) acrylate.
  • Examples of the (meth) acrylate having an alkoxy group include (meth) acrylic acid alkoxyalkyl esters such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate.
  • Examples of the (meth) acrylate having an alicyclic hydrocarbon group include a (meth) acrylate having a cyclic alkyl group and a (meth) acrylate having a polycyclic structure.
  • the (meth) acrylate having a cyclic alkyl group is preferably a (meth) acrylate having a cyclic alkyl group having 6 to 12 carbon atoms in the cyclic alkyl group.
  • Examples of the cyclic alkyl group include a cyclic alkyl group having a monocyclic structure (for example, a cycloalkyl group), and may also have a chain portion.
  • the (meth) acrylate having a polycyclic structure is preferably a (meth) acrylate having a polycyclic structure having 6 to 12 carbon atoms.
  • the polycyclic structure include a cyclic alkyl group having a crosslinked ring structure (for example, an adamantyl group, a norbonyl group, an isobornyl group), and may also have a chain portion.
  • Specific examples of the (meth) acrylate having a polycyclic structure include bornyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, and 2-methyl-2-.
  • the (meth) acrylate having an aromatic group is preferably a (meth) acrylate having an aromatic group having 6 to 12 carbon atoms in the aromatic group.
  • the aromatic group include an aryl group and the like, and may have a chain portion such as an alkylaryl group, an araryl group, an aryloxyalkyl group and the like.
  • Examples of the (meth) acrylate having an aromatic group include a compound in which an aryl group is directly bonded to a (meth) acryloyloxy group, a compound in which an aralkyl group is directly bonded to a (meth) acryloyloxy group, and a (meth) acryloyloxy group.
  • Examples thereof include compounds in which an alkylaryl group is directly bonded.
  • the aryl group preferably has 6 to 12 carbon atoms.
  • the aralkyl group preferably has 6 to 12 carbon atoms.
  • the alkylaryl group preferably has 6 to 12 carbon atoms.
  • Examples of the (meth) acrylate having an aromatic group include benzyl (meth) acrylate, phenyl (meth) acrylate, and phenoxyethyl (meth) acrylate.
  • Examples of the (meth) acrylate having a cyclic ether group include 2- (4-morpholinyl) ethyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate, and (2-methyl-2-ethyl). -1,3-Dioxolan-4-yl) methyl (meth) acrylate, cyclic trimethylolpropane formal (meth) acrylate, 2-[(2-tetrahydropyranyl) oxy] ethyl (meth) acrylate, 1,3-dioxane -(Meta) acrylate and the like can be mentioned.
  • Examples of the (meth) acrylate having a tertiary amino group include 2- (dimethylamino) ethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate.
  • Examples of the (meth) acrylamides include N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, (meth) acrylamide, and N-methyl (meth).
  • the (meth) acrylamides are (meth) acrylic monomers, but are not included in the (meth) acrylate monomers.
  • Examples of the (meth) acrylic monomer having the (b2) reactive functional group include a (meth) acrylic monomer having a hydroxy group (preferably a (meth) acrylate monomer) and a (meth) acrylic monomer having a carboxy group (preferably (meth) acrylic monomer.
  • Examples thereof include (meth) acrylic acid) and (meth) acrylic monomers having an epoxy group (preferably (meth) acrylate monomers).
  • a (meth) acrylic monomer having a hydroxy group and / or a (meth) acrylic monomer having a carboxy group is preferable.
  • Examples of the (meth) acrylic monomer having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6.
  • Hydroxyalkyl (meth) acrylates such as -hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate; (4-hydroxymethylcyclohexyl) Hydroxyalkylcycloalkane (meth) acrylates such as methyl (meth) acrylates; caprolactone adducts of hydroxyalkyl (meth) acrylates and the like can be mentioned.
  • hydroxyalkyl (meth) acrylate is preferable, and (meth) acrylate having a hydroxyalkyl group having 1 to 5 carbon atoms is more preferable.
  • the (meth) acrylic monomer having a carboxy group includes a monomer obtained by reacting a (meth) acrylate having a hydroxy group with an acid anhydride, a carboxyethyl (meth) acrylate, a carboxypentyl (meth) acrylate, and a (meth) acrylic acid. And so on.
  • Examples of the monomer obtained by reacting the (meth) acrylate having a hydroxy group with an acid anhydride include 2- (meth) acryloyloxyethyl succinic acid and 2- ( Examples thereof include meta) acryloyloxyethyl maleic acid and 2- (meth) acryloyloxyethyl phthalic acid.
  • an acid anhydride for example, maleic anhydride, succinic anhydride, phthalic anhydride
  • a monomer obtained by reacting (meth) acrylic acid or (meth) acrylate having a hydroxy group with an acid anhydride is preferable.
  • Examples of the (meth) acrylic acid ester having an epoxy group include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate.
  • Examples of the vinyl monomer other than the (meth) acrylic monomer include (b3) a vinyl monomer other than the (meth) acrylic monomer having no reactive functional group and (b4) a vinyl monomer other than the (meth) acrylic monomer having a reactive functional group.
  • Vinyl monomers can be mentioned. These monomers may be used alone or in combination of two or more.
  • Examples of the vinyl monomer other than the (meth) acrylic monomer having no reactive functional group (b3) include an aromatic vinyl monomer, a vinyl monomer containing a heterocycle, vinyl carboxylate, and a vinyl monomer containing a tertiary amino group. , Vinyl monomers containing a quaternary ammonium base, vinylamides, ⁇ -olefins, dienes, vinyl halide monomers and the like.
  • Examples of the aromatic vinyl monomer include styrene, ⁇ -methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, 1-vinylnaphthalene and the like.
  • Examples of the vinyl monomer containing a heterocycle include 2-vinylthiophene, N-methyl-2-vinylpyrrole, 2-vinylpyridine, 4-vinylpyridine and the like.
  • Examples of the vinyl carboxylate include vinyl acetate, vinyl pivalate, vinyl benzoate and the like.
  • Examples of the vinyl monomer containing a tertiary amino group include N, N-dimethylallylamine and the like.
  • Examples of the vinyl monomer containing a quaternary ammonium base include N-methacryloylaminoethyl-N, N, N-dimethylbenzylammonium chloride and the like.
  • Examples of the vinylamides include N-vinylformamide, N-vinylacetamide, 1-vinyl-2-pyrrolidone, N-vinyl- ⁇ -captolactam and the like.
  • Examples of the ⁇ -olefin include 1-hexene, 1-octene, 1-decene and the like.
  • Examples of the diene include butadiene, isoprene, 4-methyl-1,4-hexadiene, 7-methyl-1,6-octadien and the like.
  • vinyl halide monomer examples include vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, tetrafluoropropylene, vinylidene chloride, vinyl chloride, and 1-chloro-1-fluoro. Examples thereof include ethylene and 1,2-dichloro-1,2-difluoroethylene.
  • Examples of the vinyl monomer other than the (meth) acrylic monomer having the (b4) reactive functional group include a vinyl monomer having a hydroxy group, a vinyl monomer having a carboxy group, and a vinyl monomer containing an epoxy group.
  • Examples of the vinyl monomer having a hydroxy group include p-hydroxystyrene and allyl alcohol.
  • Examples of the vinyl monomer having a carboxy group include crotonic acid, maleic acid, itaconic acid, citraconic acid, cinnamic acid, (meth) acrylic acid and the like.
  • Examples of the vinyl monomer containing an epoxy group include 2-allyloxylane, glycidyl vinyl ether, and 3,4-epoxycyclohexylvinyl ether.
  • the copolymer (A) may be any of a random copolymer, a block copolymer, and a graft copolymer, and is preferably a random copolymer.
  • the weight average molecular weight (Mw) of the copolymer (A) is preferably 200,000 or more, more preferably 300,000 or more, further preferably 400,000 or more, 2 million or less, and more preferably 1.8 million or less. , More preferably 1.5 million or less, and particularly preferably 1 million or less.
  • Mw of the copolymer (A) is 200,000 or more, the cohesive force is increased and the heat resistance of the pressure-sensitive adhesive is improved, and when it is 2 million or less, the coating workability of the pressure-sensitive adhesive composition is further improved.
  • the method for measuring the weight average molecular weight (Mw) will be described later.
  • the molecular weight distribution (PDI) of the (A) copolymer is less than 3.0, preferably less than 2.5, more preferably less than 2.2, and even more preferably less than 1.8.
  • the PDI is less than 3.0, a pressure-sensitive adhesive material having a small molecular weight or a large molecular weight is low in comparison with the molecular weight of the designed copolymer, and a pressure-sensitive adhesive material having excellent bending resistance can be obtained.
  • the molecular weight distribution (PDI) is a value calculated by (weight average molecular weight (Mw)) / (number average molecular weight (Mn)), and a method for measuring Mw and Mn will be described later.
  • the glass transition temperature (Tg) of the copolymer (A) is preferably ⁇ 70 ° C. or higher, more preferably ⁇ 60 ° C. or higher, preferably 0 ° C. or lower, more preferably ⁇ 10 ° C. or lower, still more preferably ⁇ 10 ° C. or lower. It is -20 ° C or lower.
  • Tg glass transition temperature
  • the glass transition temperature (Tg) of the copolymer (A) is a value calculated by the following FOX formula (mathematical formula (1)).
  • Tg indicates the glass transition temperature (° C.) of the copolymer.
  • Tgi indicates the glass transition temperature (° C.) when the vinyl monomer i forms a homopolymer.
  • i is a natural number from 1 to n.
  • Table 1 shows the glass transition temperature of a typical homopolymer.
  • the copolymer (A) is produced by radically polymerizing a vinyl monomer by a living radical polymerization method.
  • the living radical polymerization method maintains the convenience and versatility of the conventional radical polymerization method, but is less likely to cause a termination reaction or chain transfer, and grows without being hindered by a side reaction that deactivates the growth end. It is easy to produce a polymer with a uniform composition and precise control. Therefore, in the copolymer produced by the living radical polymerization method, the reactive functional groups are uniformly distributed in each molecular chain. Therefore, if a copolymer produced by the living radical polymerization method is used, the crosslink point density in the pressure-sensitive adhesive becomes uniform as a whole.
  • a random copolymer can be obtained by using a mixture of each monomer (vinyl monomer) constituting the (A) copolymer. Further, a block copolymer can be obtained by sequentially reacting vinyl monomers constituting the copolymer.
  • the living radical polymerization method includes a method using a transition metal catalyst (ATRP method); a method using a sulfur-based reversible chain transfer agent (RAFT method); and an organotellurium compound, depending on the method for stabilizing the polymerization growth end.
  • ATRP method transition metal catalyst
  • RAFT method sulfur-based reversible chain transfer agent
  • organotellurium compound depending on the method for stabilizing the polymerization growth end.
  • the TERP method is a method of polymerizing a radically polymerizable compound (vinyl monomer) using an organic tellurium compound as a chain transfer agent.
  • a radically polymerizable compound vinyl monomer
  • organic tellurium compound as a chain transfer agent
  • Specific polymerization methods of the TERP method include the following (a) to (d).
  • A) A method of polymerizing a vinyl monomer using an organic tellurium compound represented by the formula (1).
  • (B) A method of polymerizing a vinyl monomer using a mixture of an organic tellurium compound represented by the formula (1) and an azo-based polymerization initiator.
  • (C) A method of polymerizing a vinyl monomer using a mixture of an organic tellurium compound represented by the formula (1) and an organic diterlide compound represented by the formula (2).
  • D) A method of polymerizing a vinyl monomer using a mixture of an organic tellurium compound represented by the formula (1), an azo-based polymerization initiator and an organic diterlide compound represented by the formula (2).
  • R 1 is an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group.
  • R 2 and R 3 are independently hydrogen atoms or alkyl groups having 1 to 8 carbon atoms.
  • R 4 is an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amide group, an oxycarbonyl group, a cyano group, an allyl group or a propargyl group.
  • R 1 is an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group.
  • the organic tellurium compound represented by the formula (1) is ethyl-2-methyl-2-n-butylteranyl-propionate, ethyl-2-n-butylteranyl-propionate, (2-hydroxyethyl) -2-.
  • examples thereof include the organotellurium compounds described in International Publication No. 2004/14848, International Publication No. 2004/14962, International Publication No. 2004/072126, and International Publication No. 2004/0968870, such as methyl-methylteranyl-propionate.
  • Specific examples of the organic diterlide compound represented by the formula (2) include dimethyl diterlide, dibutyl diterlide and the like.
  • the azo-based polymerization initiator can be used without particular limitation as long as it is an azo-based polymerization initiator used in ordinary radical polymerization.
  • AIBN 2,2'-azobis (isobutyronitrile)
  • ADVN 2,4-dimethylvaleronitrile
  • ADVN 1,1'-azobis (1-cyclohexanecarbonitrile)
  • ACBN 1,1'-azobis (1-cyclohexanecarbonitrile
  • V-70 2,2'-azobis (4-methoxy-2,4- Dimethylvaleronitrile
  • the polymerization step is a container substituted with an inert gas, and the vinyl monomer and the organic tellurium compound of the formula (1) are further azo-based for the purpose of promoting a reaction depending on the type of the vinyl monomer, controlling the molecular weight and the molecular weight distribution, and the like.
  • the polymerization initiator and / or the organic diterlide compound of the formula (2) are mixed.
  • examples of the inert gas include nitrogen, argon, and helium. Argon and nitrogen are preferable.
  • the amount of the vinyl monomer used in the above (a), (b), (c) and (d) may be appropriately adjusted according to the physical characteristics of the target copolymer.
  • the polymerization reaction can be carried out without a solvent, but the mixture may be carried out by stirring using an aprotic solvent or a protic solvent generally used in radical polymerization.
  • aprotic solvents that can be used include anisole, benzene, toluene, propylene glycol monomethyl ether acetate, ethyl acetate, tetrahydrofuran (THF) and the like.
  • the protonic solvent include water, methanol, 1-methoxy-2-propanol and the like.
  • the solvent may be used alone or in combination of two or more.
  • the amount of the solvent used may be appropriately adjusted, and for example, 0.01 ml to 50 ml is preferable with respect to 1 g of the vinyl monomer.
  • the reaction temperature and reaction time may be appropriately adjusted according to the molecular weight or molecular weight distribution of the obtained copolymer, but usually, the mixture is stirred at 0 ° C. to 150 ° C. for 1 minute to 100 hours.
  • the solvent used, the residual vinyl monomer, and the like can be removed from the obtained reaction mixture by ordinary separation and purification means to separate the desired copolymer.
  • the growth end of the copolymer obtained by the polymerization reaction is in the form of -TeR 1 derived from the tellurium compound (R 1 is the same as above in the formula), and is inactivated by an operation in air after the completion of the polymerization reaction.
  • R 1 is the same as above in the formula
  • tellurium atoms remain. Since the copolymer in which the tellurium atom remains at the terminal is colored or has poor thermal stability, it is preferable to remove the tellurium atom.
  • Examples of the method for removing the tellurium atom include a radical reduction method; a method of adsorbing with activated carbon or the like; a method of adsorbing a metal with an ion exchange resin or the like, and these methods can also be used in combination.
  • the other end of the copolymer obtained by the polymerization reaction (the end opposite to the growth end) is -CR 2 R 3 R 4 derived from the tellurium compound (in the formula, R 2 , R 3 and R 4 are of the formula. It is the same as R 2 , R 3 and R 4 in (1)).
  • the pressure-sensitive adhesive composition contains (B) a cross-linking agent.
  • the (B) cross-linking agent is a compound having two or more reactive groups in one molecule capable of reacting with the reactive functional groups of the above-mentioned (A) copolymer.
  • the (B) cross-linking agent is not particularly limited, and examples thereof include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, aziridine-based cross-linking agents, metal chelate-type cross-linking agents, melamine resin-based cross-linking agents, and urea resin-based cross-linking agents. ..
  • isocyanate-based cross-linking agents isocyanate-based cross-linking agents, epoxy-based cross-linking agents, and aziridine-based cross-linking agents are preferable, and epoxy-based cross-linking agents are more preferable from the viewpoint of easy control of the degree of progress of the cross-linking reaction and bending resistance. ..
  • the isocyanate-based cross-linking agent is a compound having two or more isocyanate groups (including an isocyanate regenerated functional group in which the isocyanate group is temporarily protected by a blocking agent or quantification) as a reactive group in one molecule.
  • the isocyanate-based cross-linking agent may be used alone or in combination of two or more.
  • isocyanate-based cross-linking agent examples include aromatic polyisocyanates, alicyclic polyisocyanates, aliphatic polyisocyanates, adducts of these and various polyols, isocyanurate bonds, burette bonds, allophanate bonds, and the like.
  • examples thereof include polyisocyanate. More specifically, for example, lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, 1,3-bis (isocyanatomethyl).
  • Alicyclic polyisocyanates such as cyclohexane; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate
  • Aromatic polyisocyanates such as isocyanate, tetramethylxylylene diisocyanate, 1,5-naphthalenediocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate; trimethylolpropane / tolylene diisocyanate trimer adduct, trimethylolpropane / Hexamethylene diisocyanate trimeric adduct, isocyanate adduct such as isocyanurate of hexamethylene diisocyanate; trimethylol propane adduct of xylylene diisocyanate; trimethylol
  • an aliphatic polyisocyanate it is preferable to use an aliphatic polyisocyanate, and an isocyanurate form of an aliphatic diisocyanate (for example, an isocyanurate form of hexamethylene diisocyanate) is more preferable.
  • an isocyanurate form of an aliphatic diisocyanate for example, an isocyanurate form of hexamethylene diisocyanate
  • Epoxy cross-linking agent refers to a compound having two or more epoxy groups in one molecule as a reactive group.
  • the epoxy-based cross-linking agent may be used alone or in combination of two or more.
  • epoxy-based cross-linking agent examples include bisphenol A, epichlorohydrin-type epoxy resin, ethylene glycidyl ether, N, N, N', N'-tetraglycidyl-m-xylene diamine, diglycidyl aniline, diamine glycidyl amine, 1 , 3-Bis (N, N-diglycidylaminomethyl) cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether , Polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, glycerin diglycidyl
  • the aziridine-based cross-linking agent refers to a compound having two or more aziridine groups in one molecule as a reactive group.
  • the aziridine-based cross-linking agent may be used alone or in combination of two or more.
  • aziridine-based cross-linking agent examples include tris-2,4,6- (1-aziridinyl) -1,3,5-triazine, tris [1- (2-methyl) -aziridinyl] phosphine oxide, and hexa [1- (2). -Methyl) -aziridinyl] Triphosphatriazine and the like can be mentioned.
  • the content of the reactive group of the cross-linking agent (B) is preferably 0.5 mmol / g or more, more preferably 1.0 mmol / g or more, still more preferably 3.0 mmol / g or more, and particularly preferably 6. It is 0 mmol / g or more, preferably 20 mmol / g or less, more preferably 15.0 mmol / g or less, still more preferably 12.0 mmol / g or less.
  • the content of the reactive group of the cross-linking agent (B) is within this range, the cohesive force of the pressure-sensitive adhesive becomes preferable, and even if it is bent, the occurrence of deformation at the bent portion can be further suppressed.
  • the content of the cross-linking agent (B) in the pressure-sensitive adhesive composition is preferably 0.01 part by mass or more, more preferably 0.03 part by mass or more, and 1 part by mass with respect to 100 parts by mass of the copolymer (A).
  • the following is preferable, and more preferably 0.5 parts by mass or less.
  • the content of the cross-linking agent (B) is 0.01 parts by mass or more, sufficient cohesive force is exhibited and excellent flexibility is exhibited. If it is 1 part by mass or less, sufficient adhesion to the base material can be exhibited and the occurrence of floating and peeling at the time of bending can be suppressed.
  • the pressure-sensitive adhesive composition has a molar ratio of reactive functional groups (molar amount of reactive functional groups / molar amount of reactive groups) of the copolymer (A) to the reactive groups of the cross-linking agent (B). It is preferably 1 or more, more preferably 2 or more, further preferably 10 or more, preferably 1000 or less, more preferably 200 or less, still more preferably 100 or less.
  • additives In addition to the (A) copolymer and (B) cross-linking agent, other additives may be blended and used in the pressure-sensitive adhesive composition.
  • Other additives include cross-linking accelerators, cross-linking retarders, tackifiers, plasticizers, softeners, peeling aids, silane coupling agents, dyes, pigments, dyes, fluorescent whitening agents, etc.
  • Antistatics wetting agents, surfactants, thickeners, fungicides, preservatives, oxygen absorbers, UV absorbers, antioxidants, near-infrared absorbers, water-soluble photochromic agents, fragrances, metal deactivators , Nucleating agents, alkylating agents, flame retardants, lubricants, processing aids and the like. These are appropriately selected and blended according to the use and purpose of use of the adhesive material.
  • Cross-linking accelerator If necessary, a cross-linking accelerator can be blended and used in the pressure-sensitive adhesive composition.
  • examples of the cross-linking accelerator include an organotin compound and a metal chelate compound.
  • the cross-linking accelerator may be used alone or in combination of two or more.
  • organotin compound examples include dibutyltin dilaurate, dioctiolstin dilaurylate, and dibutyltin dioctylate.
  • the metal chelate compound is a complex in which ligands having two or more coordination atoms form a ring and are bonded to a central metal.
  • the content of the cross-linking accelerator in the pressure-sensitive adhesive composition is preferably 0.01 part by mass or more, more preferably 0.02 part by mass or more, and further preferably 0. It is 04 parts by mass or more, preferably 0.5 parts by mass or less, more preferably 0.4 parts by mass or less, and further preferably 0.3 parts by mass or less.
  • a cross-linking retarder can be blended and used in the pressure-sensitive adhesive composition.
  • the cross-linking retarder is a compound in a pressure-sensitive adhesive composition containing a cross-linking agent, which can suppress an excessive increase in viscosity of the pressure-sensitive adhesive composition by blocking the functional groups of the cross-linking agent.
  • the type of the cross-linking retarder is not particularly limited, but ⁇ -diketones such as acetylacetone, hexane-2,4-dione, heptane-2,4-dione, octane-2,4-dione; ⁇ -ketoesters such as methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetic acid, octyl acetoacetic acid, oleyl acetoacetic acid, lauryl acetoacetic acid and stearyl acetoacetic acid; As the cross-linking retarder, those capable of acting as a chelating agent are preferable, and ⁇ -diketones and ⁇ -ketoesters are preferable.
  • the content of the cross-linking retarder that can be blended in the pressure-sensitive adhesive composition is preferably 0.1 part by mass or more, more preferably 0.2 part by mass or more, and further, with respect to 100 parts by mass of the (A) copolymer. It is preferably 0.5 parts by mass or more, preferably 4.0 parts by mass or less, more preferably 3.0 parts by mass or less, and further preferably 1.5 parts by mass or less.
  • silane coupling agent If necessary, a silane coupling agent can be blended and used in the pressure-sensitive adhesive composition.
  • the silane coupling agent is not particularly limited, but for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and the like.
  • Epoxy group-containing silane coupling agent such as 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane; 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3- Amino group-containing silane coupling agents such as triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine and N-phenyl- ⁇ -aminopropyltrimethoxysilane; 3-acryloxypropyltrimethoxysilane, 3- Examples thereof include (meth) acrylic group-containing silane coupling agents such as metharoxypropyltriethoxysilane; and isocyanate group-containing silane coupling agents such as 3-isocyanatepropyltriethoxysilane.
  • the content of the silane coupling agent that can be blended in the pressure-sensitive adhesive composition is preferably 1 part by mass or less, more preferably 0.01 part by mass to 1 part by mass, based on 100 parts by mass of the (A) copolymer. More preferably, it is 0.02 parts by mass to 0.6 parts by mass.
  • the pressure-sensitive adhesive composition can be produced by mixing the (A) copolymer, (B) cross-linking agent, and other additives used as necessary.
  • the pressure-sensitive adhesive composition may contain a solvent derived from the production of the (A) copolymer, or a suitable solvent may be added to dilute the pressure-sensitive adhesive composition so as to have a viscosity suitable for forming the pressure-sensitive adhesive layer. It may be a solution.
  • the solvent examples include aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and ethylene chloride; acetone, methyl ethyl ketone, 2-pentanone, isophorone and cyclohexanone.
  • ketones esters such as ethyl acetate and butyl acetate
  • cellosolve-based solvents such as ethyl cellosolve
  • glycol ether-based solvents such as propylene glycol monomethyl ether.
  • One of these solvents may be used alone, or two or more of these solvents may be mixed and used.
  • the amount of the solvent used may be appropriately adjusted so that the pressure-sensitive adhesive composition has a viscosity suitable for coating, and is not particularly limited. However, from the viewpoint of coatability, for example, 1% by mass to 90% by mass is preferable. , More preferably 10% by mass to 80% by mass, still more preferably 20% by mass to 70% by mass.
  • the adhesive material is used to bond one flexible member to another flexible member.
  • the flexible member is preferably a flexible member that constitutes a flexible display.
  • the use of the adhesive material is not particularly limited and can be used for a wide range of applications, but is particularly preferably used for a flexible display that can be repeatedly bent and stretched and used, and a member used for a flexible display.
  • a foldable foldable display for example, a rollable display that can be rolled into a cylinder, and the like are known.
  • Flexible displays are expected to be used in mobile terminals such as smartphones and tablet terminals, and stationary displays that can be stored.
  • the adhesive sheet of the present invention has an adhesive layer used for bonding one flexible member and another flexible member, and a flexible sheet member attached to at least one surface of the adhesive layer.
  • the pressure-sensitive adhesive layer is formed from the pressure-sensitive adhesive material.
  • the structure of the adhesive sheet includes an adhesive layer and a first flexible sheet member attached to one surface of the adhesive layer; the adhesive layer and one surface of the adhesive layer are attached.
  • An embodiment having a first flexible sheet member and a second flexible sheet member attached to the other surface of the adhesive layer can be mentioned.
  • FIG. 1 shows an example of the adhesive sheet of the present invention.
  • the adhesive sheet 10 of FIG. 1 is composed of an adhesive layer 12, a first flexible sheet member 14 that sandwiches the adhesive layer 12, and a second flexible sheet member 16.
  • the adhesive layer 12 is in contact with the releasable surfaces of the first flexible sheet member 14 and the second flexible sheet member 16.
  • the adhesive layer is formed from the adhesive material.
  • the film thickness of the adhesive layer is preferably 2 ⁇ m or more, more preferably 5 ⁇ m or more, still more preferably 10 ⁇ m or more, from the viewpoint of sufficiently ensuring the adhesiveness with the adherend.
  • the thickness of the adhesive layer is preferably 100 ⁇ m or less, more preferably 70 ⁇ m or less, still more preferably 50 ⁇ m or less, from the viewpoint of suppressing protrusion of the adhesive layer.
  • the flexible sheet member examples include a flexible base sheet and a release sheet.
  • the base material sheet is a sheet member that supports the adhesive layer, and this sheet member may be a functional sheet member.
  • the functional sheet member examples include a cover film, a barrier film, a polarizing film, a retardation film, an optical compensation film, a brightness improving film, a diffusion film, an antireflection film and the like.
  • the release sheet protects the adhesive layer until the adhesive layer is attached to the adherend, and is peeled off from the adhesive layer before the adhesive layer is attached to the adherend.
  • a "sheet” is a flat product that is thin by definition in JIS and whose thickness is generally small for its length and width, and a “film” is generally referred to as a “film” in comparison with its length and width.
  • a film having a thickness of 100 ⁇ m or more may be referred to as a sheet, and a film having a thickness of less than 100 ⁇ m may be referred to as a film.
  • the flexible sheet member examples include a polymer material sheet and a glass sheet.
  • the thickness of the flexible sheet member is not particularly limited, but is preferably 2 ⁇ m to 500 ⁇ m, more preferably 2 ⁇ m to 200 ⁇ m, from the viewpoint of excellent handleability and the like.
  • polyester resins such as polyethylene terephthalate resin and polyethylene naphthalate resin; polycarbonate resin; poly (meth) acrylate resin; polystyrene resin; polyamide resin; polyacrylonitrile resin; polypropylene resin, polyethylene resin, and polycycloolefin resin.
  • Polyphenylene sulfide resin polyimide resin; polyvinyl chloride resin; polyvinylidene chloride resin; polyvinyl alcohol resin and the like.
  • the flexible sheet member may be composed of a single layer composed of a layer containing one or more of the polymer materials, or may be composed of a layer containing one or more of the polymer materials and a layer containing one or more of the polymer materials. It may be composed of two or more layers such as a layer containing one kind or two or more kinds of polymer materials different from this layer.
  • the flexible sheet member is preferably a release sheet in which the surface in contact with the adhesive layer is subjected to a mold release treatment.
  • the mold release agent used in the mold release treatment include silicone-based, fluorine-based, alkyd-based, unsaturated polyester-based, polyolefin-based, and wax-based mold release agents.
  • the adhesive sheet has a first flexible sheet member attached to one surface of the adhesive layer and a second flexible sheet member attached to the other surface of the adhesive layer.
  • the flexible sheet member is the first release sheet
  • the second flexible sheet member is the second release sheet
  • the first release sheet and the second release sheet are attached so that their respective release surfaces are in contact with the adhesive layer. It is preferable that it is worn.
  • one release sheet should be a heavy release type release sheet with a large release force
  • the other release sheet should be a light release type release sheet with a small release force. Is preferable.
  • the pressure-sensitive adhesive sheet can be produced, for example, by applying the above-mentioned pressure-sensitive adhesive composition onto a flexible sheet member and, if necessary, curing it by a dry heat treatment to form a pressure-sensitive adhesive layer.
  • the adhesive composition for example, reverse gravure coating method, direct gravure coating method, die coating method, bar coating method, wire bar coating method, roll coating method, spin coating method, dip coating method, spray coating method, knife.
  • Various coating methods such as a coating method and a kiss coating method, and various printing methods such as an inkjet method, offset printing, screen printing, and flexographic printing can be adopted.
  • the surface of the release sheet may be subjected to surface treatment such as corona treatment, plasma treatment, hot air treatment, ozone treatment, and ultraviolet treatment.
  • the drying and curing steps are not particularly limited as long as the solvent and the like used in the pressure-sensitive adhesive composition can be removed and cured, but the drying and curing steps are preferably performed at a temperature of 60 ° C. to 150 ° C. for about 20 seconds to 300 seconds. .. In particular, the drying temperature is preferably 100 ° C. to 130 ° C.
  • the adhesive composition is applied to the first flexible sheet member, and the first flexible sheet member is applied.
  • the second flexible sheet member may be attached to the adhesive layer.
  • the adhesive layer may be cured if necessary. Examples of the curing conditions include, for example, about 3 to 7 days at 40 ° C.
  • the flexible laminated member of the present invention includes a first flexible member, a second flexible member, and an adhesive layer for bonding the first flexible member and the second flexible member to each other. It is a laminated member, and the adhesive layer is made of the adhesive material. Since the adhesive layer of the flexible laminated member is formed from the adhesive material, even when the flexible laminated member is repeatedly bent, poor appearance such as wavy appearance of the bent portion is suppressed.
  • FIG. 2 shows an example of the flexible laminated member of the present invention.
  • the flexible laminated member 20 of FIG. 2 is located between the first flexible member 22, the second flexible member 24, and the first flexible member 22 and the second flexible member 24, and these bending members are connected to each other. It is provided with an adhesive layer 12 to be bonded.
  • both the first flexible member and the second flexible member are constituent members of the flexible device; the second flexible member is the flexible device, and the first Examples thereof include a configuration in which the flexible member is a functional sheet member bonded to the flexible device.
  • the flexible device include a foldable foldable display and a rollable display that can be rolled into a tubular shape.
  • the functional sheet member include a cover film, a barrier film, a polarizing film, a retardation film, an optical compensation film, a brightness improving film, a diffusion film, an antireflection film, a transparent conductive film, a metal mesh film, a cushion film and the like. Be done.
  • the first flexible member and the second flexible member are members that can be repeatedly bent and used.
  • Examples of the first flexible member and the second flexible member include a flexible substrate material, a functional sheet member, a display element (organic EL module, electronic paper module, etc.) and the like. It is preferable that at least one of the first flexible member and the second flexible member is a display element.
  • the method for producing the flexible laminated member of the present invention is not particularly limited, and examples thereof include the following methods (1) to (4).
  • the release sheet attached to one surface of the adhesive sheet is peeled off, the exposed adhesive layer is attached to the first flexible member, and then the release sheet attached to the other surface of the adhesive sheet.
  • the pressure-sensitive adhesive composition is applied to one surface of the first flexible member and, if necessary, cured by dry heat treatment to form a pressure-sensitive adhesive layer, and then the pressure-sensitive adhesive layer is provided with the releasability of the release sheet. Attach the surface to be held. Then, a method of obtaining a flexible laminated member by peeling off the release sheet and attaching the exposed adhesive layer and the second flexible member.
  • An adhesive composition is applied to one surface of the first flexible member and, if necessary, cured by dry heat treatment to form an adhesive layer, and then the second flexible member is attached to the adhesive layer.
  • the pressure-sensitive adhesive composition is applied onto the releasable surface of the release sheet and, if necessary, cured by dry heat treatment to form a pressure-sensitive adhesive layer, and then the first flexible member is attached to the pressure-sensitive adhesive layer. To wear. Then, a method of obtaining a flexible laminated member by peeling off the release sheet and attaching the exposed adhesive layer and the second flexible member.
  • the order in which the first flexible member and the second flexible member are used may be changed.
  • various coating methods and various printing methods similar to those for producing the pressure-sensitive adhesive sheet can be used, and the same applies to the drying and curing steps.
  • it may be cured if necessary.
  • the release sheet used in the manufacture of the flexible laminated member may be the same as the release sheet used for the adhesive sheet.
  • the present invention will be described in more detail based on specific examples.
  • the present invention is not limited to the following examples, and can be appropriately modified and implemented without changing the gist thereof.
  • the polymerization rate, weight average molecular weight (Mw), molecular weight distribution (PDI), gel fraction of adhesive material, adhesive layer thickness, Young's modulus, elastic modulus at shrinkage, etc. of block copolymers are evaluated according to the following methods. did.
  • EHA 2-ethylhexyl acrylate
  • LA lauryl acrylate
  • AA acrylic acid
  • A-SA 2-acryloyloxyethyl succinate
  • HBA 4-hydroxybutyl acrylate
  • BA n-butyl acrylate
  • ACMO 4-acryloylmorpholin
  • IBXA isobornyl Acrylate
  • DMAAm N, N-Dimethylacrylamide
  • BTEE Ethyl-2-methyl-2-n-butylteranyl-propionate
  • AIBN Azobisisobutyronitrile
  • AcOEt Ethyl acetate
  • the thickness of the adhesive layer is measured by measuring the total thickness of the entire adhesive sheet using a thickness measuring machine (manufactured by Tester Sangyo Co., Ltd., "TH-104") and dividing the thickness of the release sheet from this total thickness. Asked.
  • a sheet-shaped adhesive material (thickness 1 mm) was cut into a size of 5 mm in width and 70 mm in length to prepare a test piece.
  • the tensile test was performed using a precision universal testing machine (AUTOGRAPH® AGX manufactured by Shimadzu Corporation). In the test, the distance between the gripping tools was 30 mm, the tensile speed was 30 mm / min, and the tensile stress was extended from 0 kPa to 50 kPa in an environment of 23 ° C. and 50%.
  • the Young's modulus was defined as the average value of the slopes of the tangents at the distance between the grips of 30.9 to 31.8 mm (displacement from the initial distance between the grips of 3 to 6%).
  • the contractile elastic modulus is the tensile stress and displacement at a displacement of 0.97, where 1 is the displacement from the test piece length at the tensile stress of 50 kPa at the nth contraction to the test piece length at the tensile stress of 0 kPa at the nth contraction. It was obtained from the tensile stress at 0.94.
  • a pressure-sensitive adhesive sheet having PET films bonded to both sides of the pressure-sensitive adhesive layer was cut into a size of 20 mm in width and 80 mm in length to prepare a test piece for bending test.
  • the test was carried out using a precision universal testing machine (AUTOGRAPH® AGX manufactured by Shimadzu Corporation) in an environment of 23 ° C. and 50%, and the distance between the gripping tools was 30 mm.
  • the test piece was bent at a compression rate of 10 mm / min until the bending diameter became 6 mm (diameter), and then extended at a speed of 10 mm / min until the bending diameter became 0 mm.
  • test piece taken out from the testing machine was allowed to stand on the glass plate with the convex portion facing up, and after 10 seconds, the convex portion of the test piece was removed from the glass plate. The height was measured using a ruler.
  • Adhesive Composition No. 1 The copolymer No. obtained in Synthesis Example 1 Add 0.427 parts by mass of a cross-linking agent (TETRAD (registered trademark) -C) and AcOEt to 270 parts by mass of the solution of A (100 parts by mass of the copolymer component), and stir to obtain the adhesive composition No. 1. Obtained.
  • a cross-linking agent TTRAD (registered trademark) -C
  • Adhesive Composition Nos. 2 to 18 Adhesive Composition No., except that the formulation was changed as shown in Table 4. In the same manner as in No. 1, the adhesive composition No. 2 to 18 were prepared.
  • TETRAD®-C Mitsubishi Gas Chemical Company, Ltd., 1,3-bis (N, N-diglycidylaminoethyl) cyclohexane (epoxy group amount; 9.76 mmol / g)
  • TPA-100 Duranate (registered trademark) TPA-100 manufactured by Asahi Kasei Corporation (isocyanurate form of hexamethylene diisocyanate (NCO%; 23.1% by mass))
  • MHG Asahi Kasei Corporation, Duranate (registered trademark) MHG-80B (Cyclic multimer of hexamethylene diisocyanate (NCO%; 15.1% by mass))
  • U-810 Neostan (registered trademark)
  • U-810 Dioctyl tin) manufactured by Nitto Kasei Co., Ltd. AcAc; Acetylacetone
  • ⁇ Sheet adhesive material> Using a release sheet (polyethylene terephthalate (PET) film with mold release treatment on the surface, Clean Sepa (registered trademark) HY-S10: manufactured by Higashiyama Film, thickness 38 ⁇ m), the surface that has undergone mold release treatment is on the inside. A container having a length of 70 mm, a width of 70 mm, and a height of 20 mm was produced in such a manner. Each pressure-sensitive adhesive composition is added to this container so that the film thickness after drying is 1.0 mm, dried at 60 ° C. for 12 hours using a constant temperature dryer, and then taken out of the container to prepare a sheet-shaped pressure-sensitive adhesive material. did. The evaluation results of each sheet-shaped adhesive material are shown in Table 5.
  • the sheet-like adhesive material No. 1 to 11 and 16 to 18 are cured products of a pressure-sensitive adhesive composition containing a (meth) acrylic copolymer having a reactive functional group and a cross-linking agent, and the (meth) acrylic copolymer is It is obtained by living radical polymerization, and the pressure-sensitive adhesive has a predetermined Young ratio and a retention rate of elastic ratio at the time of shrinkage.
  • a film after drying using a baker-type applicator on the release surface of the first release sheet (PET film whose surface has been released, Clean Sepa (registered trademark) HY-S10: manufactured by Higashiyama Film, thickness 38 ⁇ m). After applying the pressure-sensitive adhesive composition so as to have a thickness of 25 ⁇ m, it was dried at 120 ° C. for 3 minutes using a constant temperature dryer. Next, the adhesive layer formed on the first release sheet was coated with the second release sheet (PET film whose surface was subjected to a mold release treatment, Clean Sepa (registered trademark) HY-S10: manufactured by Higashiyama Film, thickness 38 ⁇ m). After the release surfaces were bonded together, aging was performed at 40 ° C. for 3 days to prepare an adhesive layer sandwiched between two release sheets.
  • the adhesive sheet No. In 21 to 24 and 29 to 31, the adhesive layer is the sheet-like adhesive material No. It is made up of 1, 3, 4, 5 and 16-18. Deflection of these adhesive sheets was suppressed even when they were repeatedly bent and stretched.
  • the present invention includes the following embodiments.
  • the pressure-sensitive adhesive is a cured product of a pressure-sensitive adhesive composition containing a (meth) acrylic copolymer having a reactive functional group and a cross-linking agent.
  • the (meth) acrylic copolymer is obtained by living radical polymerization, and its molecular weight distribution (Mw / Mn) is 3.0 or less.
  • the Young's modulus of the adhesive material is 10 kPa to 1000 kPa.
  • An adhesive sheet having an adhesive layer used for bonding one flexible member and another flexible member, and a flexible sheet member attached to at least one surface of the adhesive layer.
  • the adhesive sheet has a first flexible sheet member attached to one surface of the adhesive layer and a second flexible sheet member attached to the other surface of the adhesive layer.
  • the first flexible sheet member is a first release sheet
  • the second flexible sheet member is a second release sheet.
  • a flexible laminated member including a first flexible member, a second flexible member, and an adhesive layer for bonding the first flexible member and the second flexible member to each other.
  • one flexible member for example, a functional sheet member constituting a flexible display that can be repeatedly bent and extended and used is bonded to another flexible member (for example, a display element).
  • another flexible member for example, a display element
  • Adhesive sheet 12 Adhesive layer 14: First flexible sheet member 16: Second flexible sheet member 20: Flexible laminated member 22: First flexible member 24: Second flexible member

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  • Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Laminated Bodies (AREA)
PCT/JP2020/044153 2019-12-06 2020-11-27 粘着材、粘着シートおよび屈曲性積層部材 WO2021111995A1 (ja)

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WO2023068009A1 (ja) * 2021-10-18 2023-04-27 大塚化学株式会社 粘着材および粘着シート
JP7502870B2 (ja) 2020-02-28 2024-06-19 東山フイルム株式会社 粘着材、粘着シートおよび屈曲性積層部材
KR20240087772A (ko) 2021-11-02 2024-06-19 히가시야마 필름 가부시키가이샤 점착재 및 점착 시트

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