WO2022181355A1 - フレキシブルディスプレイ用粘着組成物、粘着材および粘着シート - Google Patents

フレキシブルディスプレイ用粘着組成物、粘着材および粘着シート Download PDF

Info

Publication number
WO2022181355A1
WO2022181355A1 PCT/JP2022/005346 JP2022005346W WO2022181355A1 WO 2022181355 A1 WO2022181355 A1 WO 2022181355A1 JP 2022005346 W JP2022005346 W JP 2022005346W WO 2022181355 A1 WO2022181355 A1 WO 2022181355A1
Authority
WO
WIPO (PCT)
Prior art keywords
meth
flexible
acrylic copolymer
group
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2022/005346
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
正規 石原
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Otsuka Chemical Co Ltd
Higashiyama Film Co Ltd
Original Assignee
Otsuka Chemical Co Ltd
Higashiyama Film Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Otsuka Chemical Co Ltd, Higashiyama Film Co Ltd filed Critical Otsuka Chemical Co Ltd
Priority to CN202280014119.7A priority Critical patent/CN116829670A/zh
Priority to JP2023502278A priority patent/JP7698704B2/ja
Priority to KR1020237027096A priority patent/KR20230152660A/ko
Publication of WO2022181355A1 publication Critical patent/WO2022181355A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • 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
    • C09J2301/302—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 the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C

Definitions

  • the present invention relates to an adhesive composition used for flexible displays, and specifically to an adhesive composition forming an adhesive used for bonding one flexible member and another flexible member.
  • Adhesive materials are generally used to join the components that make up various displays and touch panels for televisions, mobile phones, smartphones, etc.
  • the adhesive material is provided, for example, in the form of a substrate-attached adhesive sheet having an adhesive layer on a supporting substrate, or a substrate-less adhesive sheet having no supporting substrate, and the members are bonded together.
  • Flexible displays include a foldable display that can be folded, a rollable display that can be rolled into a cylindrical shape, etc., and are expected to be used in mobile terminals such as smartphones and tablet terminals, and stationary displays that can be stored.
  • Patent Document 1 discloses one side of an adhesive layer and the other side of the adhesive layer. 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)).
  • the present invention has been made in view of the above circumstances, and forms an adhesive material (adhesive layer) having adhesive strength suitable as an adhesive material (adhesive layer), excellent flexibility, and excellent restorability.
  • An object of the present invention is to provide an adhesive composition capable of
  • the pressure-sensitive adhesive composition for a flexible display of the present invention which can solve the above problems, is a pressure-sensitive adhesive composition for a flexible display for bonding one flexible member and another flexible member constituting a flexible display. , containing a plurality of (meth)acrylic copolymer components and a crosslinking agent, and as the (meth)acrylic copolymer components, at least (A) (meth)acrylic copolymer components and (B) ( containing a meth)acrylic copolymer component, the (A) (meth)acrylic copolymer component has a first reactive group, and has a molecular weight distribution (Mw/Mn) of 3.0 or less; The (B) (meth)acrylic copolymer component has a first reactive group, the molecular weight distribution (Mw/Mn) is greater than 3.0, and the cross-linking agent reacts with the first reactive group. and the content of the (A) (meth)acrylic copolymer component in the plurality
  • the adhesive composition for a flexible display of the present invention By using the adhesive composition for a flexible display of the present invention, it is possible to form an adhesive material (adhesive layer) having suitable adhesive strength as an adhesive material (adhesive layer) and having excellent flexibility and restorability. Therefore, by using the pressure-sensitive adhesive composition for a flexible display of the present invention, even when repeatedly bent, the interface between the pressure-sensitive adhesive layer and the flexible member at the bending portion does not float or peel off, and cracks, waviness, and the like do not occur. A flexible display that can suppress the occurrence of appearance defects can be manufactured.
  • (meth)acrylic means “at least one of acrylic and methacrylic".
  • (Meth)acrylate means “at least one of acrylate and methacrylate”.
  • (Meth)acryloyl means “at least one of acryloyl and methacryloyl”.
  • a "vinyl monomer” refers to a monomer having a radically polymerizable carbon-carbon double bond in the molecule.
  • a “structural unit derived from a vinyl monomer” refers to a structural unit in which a radically polymerizable carbon-carbon double bond of a vinyl monomer is polymerized to form a carbon-carbon single bond.
  • the “structural unit derived from (meth)acrylate” refers to a structural unit in which the radically polymerizable carbon-carbon double bond of (meth)acrylate is polymerized to form a carbon-carbon single bond.
  • a “structural unit derived from a (meth)acrylic monomer” refers to a structural unit in which a radically polymerizable carbon-carbon double bond of a (meth)acrylic monomer is polymerized to form a carbon-carbon single bond.
  • the adhesive composition for a flexible display of the present invention (hereinafter sometimes simply referred to as "adhesive composition") is a flexible display for bonding one flexible member and another flexible member constituting a flexible display. It is an adhesive composition for The adhesive composition contains a plurality of (meth)acrylic copolymer components and a cross-linking agent.
  • the adhesive composition includes at least (A) (meth)acrylic copolymer component (hereinafter sometimes simply referred to as "(A) polymer component") as the (meth)acrylic copolymer component.
  • (B) contains a (meth)acrylic copolymer component (hereinafter sometimes simply referred to as "(B) polymer component”).
  • a mixture containing a plurality of the (meth)acrylic copolymer components may be referred to as a (meth)acrylic copolymer mixture.
  • the (A) (meth)acrylic copolymer component has a first reactive group and a molecular weight distribution (Mw/Mn) of 3.0 or less.
  • the (B) (meth)acrylic copolymer component has a first reactive group and a molecular weight distribution (Mw/Mn) of more than 3.0. Further, the content of the (A) (meth)acrylic copolymer component in the plurality of (meth)acrylic copolymer components is 75% by mass to 99% by mass.
  • the (A) (meth)acrylic copolymer component may be a copolymer containing a structural unit derived from a (meth)acrylic monomer as a main component (50% by mass or more).
  • the polymer component (A) may be of one type or two or more types.
  • the polymer component (A) can contain a structural unit derived from a vinyl monomer other than the (meth)acrylic monomer.
  • the content of the structural unit derived from the (meth)acrylic monomer in the polymer component (A) is preferably 80% by mass or more, more preferably 90% by mass or more, based on 100% by mass of the polymer component.
  • the polymer component (A) may be composed only of structural units derived from (meth)acrylic monomers.
  • the (A) polymer component is preferably a (meth)acrylate copolymer.
  • the (meth)acrylate copolymer may be a copolymer having 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 in which the hydrogen atom of the carboxy group of (meth)acrylic acid is substituted with an organic group.
  • the content of structural units derived from (meth)acrylate in the polymer component (A) is preferably 80% by mass or more, more preferably 90% by mass or more, based on 100% by mass of the polymer component.
  • the (A) polymer component has a first reactive group.
  • the first reactive group is a functional group having high reactivity with a second reactive group of a cross-linking agent, which will be described later.
  • Functional groups that can be the first reactive group include reactive functional groups.
  • the first reactive group includes a hydroxy group, a carboxy group, an epoxy group, etc., preferably a hydroxy group and/or a carboxy group, more preferably a hydroxy group or a carboxy group.
  • the amount of the first reactive group of the polymer component (A) is preferably 0.002 mmol/g or more, more preferably 0.006 mmol/g or more, still more preferably 0.01 mmol/g or more, and 0.8 mmol /g or less, more preferably 0.6 mmol/g or less, still more preferably 0.5 mmol/g or less, particularly preferably 0.2 mmol/g or less, and most preferably 0.1 mmol/g or less.
  • the amount of the first reactive group is 0.002 mmol/g or more, the adhesive material formed is appropriately crosslinked and exhibits a suitable recovery rate, and when the amount is 0.8 mmol/g or less, the adhesive material formed is improved.
  • the distance between cross-linking points is sufficiently long and the flexibility is excellent.
  • the polymer component (A) preferably further has a carboxy group as a functional group other than the first reactive group.
  • the carboxy group content of the copolymer (A) is preferably 0.08 mmol/g or more, more preferably 0.16 mmol/g or more, still more preferably 0.32 mmol/g or more, and 1.3 mmol/g. /g or less, more preferably 0.8 mmol/g or less, still more preferably 0.6 mmol/g or less.
  • the carboxy group and the hydroxy group per unit mass of the polymer component is preferably 4 or more, more preferably 8 or more, still more preferably 16 or more, and preferably 60 or less, more preferably 40 or less, and still more preferably 30 or less. be. If the molar ratio (carboxy group/hydroxy group) is within the above range, the adhesive layer has high restorability and a suitable balance between adhesive strength and flexibility.
  • the polymer component (A) preferably further has a hydroxy group as a functional group other than the first reactive group.
  • the amount of hydroxy groups in the polymer component (A) is preferably 0.01 mmol/g or more, more preferably 0.02 mmol/g or more, still more preferably 0.04 mmol/g or more, and 0.25 mmol/g. /g or less, more preferably 0.20 mmol/g or less, and still more preferably 0.15 mmol/g or less.
  • the carboxy group and the hydroxy group per unit mass of the polymer component
  • the molar ratio of the group (carboxy group/hydroxy group) is preferably 3.0 or more, more preferably 3.5 or more, still more preferably 4.0 or more, preferably 30 or less, more preferably 25 or less, More preferably, it is 20 or less. If the molar ratio (carboxy group/hydroxy group) is within the above range, the adhesive layer has high restorability and a suitable balance between adhesiveness and flexibility.
  • the (A) polymer component may be a random copolymer, a block copolymer, or a graft copolymer, preferably a random copolymer.
  • the weight average molecular weight (Mw) of the polymer component (A) is preferably 100,000 or more, more preferably 200,000 or more, still more preferably 600,000 or more, particularly preferably over 800,000, and preferably 3,000,000 or less. , more preferably 2.5 million or less, still more preferably 2.3 million or less.
  • Mw weight average molecular weight
  • the molecular weight distribution (Mw/Mn) of the polymer component (A) is 3.0 or less, preferably 2.5 or less, more preferably 2.2 or less, and still more preferably 1.8 or less. be.
  • the molecular weight distribution (Mw/Mn) is a value calculated by (weight average molecular weight (Mw))/(number average molecular weight (Mn)), and methods for measuring Mw and Mn will be described later. .
  • the glass transition temperature (Tg) of the polymer component (A) is preferably ⁇ 70° C. or higher, more preferably ⁇ 60° C. or higher, and preferably 0° C. or lower, more preferably ⁇ 10° C. or lower, further preferably -20°C or less. If the Tg is -70 ° C. or higher, the adhesive material is given sufficient cohesive strength, and the durability of the formed adhesive material is improved. As a result, peeling at low temperatures is suppressed, and durability is improved.
  • the Tg of the polymer component is a value calculated by the following FOX formula (formula (1)).
  • Tg represents 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.
  • the (A) polymer component includes a polymer component having a weight average molecular weight of 1,000,000 or more ((A1) polymer component) and a polymer component having a weight average molecular weight of less than 1,000,000 ((A2) polymer component ) is preferably contained.
  • a more flexible adhesive can be formed.
  • the weight average molecular weight (Mw) of the polymer component (A1) is preferably 1,000,000 or more, more preferably 1,300,000 or more, still more preferably 1,500,000 or more, and preferably 3,000,000 or less, more preferably 2,500,000 or less. , and more preferably 2,300,000 or less.
  • the molecular weight distribution (Mw/Mn) of the polymer component (A1) is 3.0 or less, preferably 2.5 or less, more preferably 2.2 or less, and still more preferably 1.8 or less. be.
  • the weight average molecular weight (Mw) of the polymer component (A2) is preferably 100,000 or more, more preferably 200,000 or more, still more preferably 600,000 or more, particularly preferably over 800,000, and preferably less than 1,000,000. , more preferably 950,000 or less, still more preferably 900,000 or less.
  • the molecular weight distribution (Mw/Mn) of the polymer component (A2) is 3.0 or less, preferably 2.5 or less, more preferably 2.2 or less, and still more preferably 1.8 or less. be.
  • the ratio (Mw1/Mw2) of the weight average molecular weight (Mw1) of the (A1) polymer component to the weight average molecular weight (Mw2) of the (A2) polymer component is preferably 1.5 or more, more preferably 2. 0 or more, preferably 4.0 or less, more preferably 3.0 or less. If the ratio (Mw1/Mw2) is within the above range, it is possible to form a more flexible adhesive material while having excellent restorability. When a plurality of (A1) polymer components and (A2) polymer components are contained, the ratio (Mw1/Mw2) is the ratio of the largest weight-average molecular weights among the respective components.
  • the mass ratio (A1/A2) between the (A1) polymer component and the (A2) polymer component in the (A) polymer component is preferably 0.1 or more, more preferably 0.2 or more, and still more preferably is 0.3 or more, preferably 1.0 or less, more preferably 0.8 or less, and still more preferably 0.6 or less. If the mass ratio (A1/A2) is within the above range, it is possible to form a more flexible adhesive material while having excellent restorability. When a plurality of (A1) polymer components and (A2) polymer components are contained, the mass ratio of the polymer component having the largest weight average molecular weight among the respective components is defined as the ratio (A1/A2).
  • the (B) (meth)acrylic copolymer component may be a copolymer whose main component (50% by mass or more) is a structural unit derived from a (meth)acrylic monomer.
  • the polymer component (B) may be of one type or two or more types.
  • the polymer component (B) can contain a structural unit derived from a vinyl monomer other than the (meth)acrylic monomer.
  • the content of the structural unit derived from the (meth)acrylic monomer in the polymer component (B) is preferably 80% by mass or more, more preferably 90% by mass or more, based on 100% by mass of the polymer component.
  • the polymer component (B) may be composed only of structural units derived from (meth)acrylic monomers.
  • the (B) polymer component is preferably a (meth)acrylate copolymer.
  • the (meth)acrylate copolymer may be a copolymer having 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 content of structural units derived from (meth)acrylate in the polymer component (B) is preferably 80% by mass or more, more preferably 90% by mass or more, based on 100% by mass of the polymer component.
  • the (B) polymer component has a first reactive group.
  • the first reactive group is a functional group having high reactivity with a second reactive group of a cross-linking agent, which will be described later.
  • Functional groups that can be the first reactive group include reactive functional groups.
  • the first reactive group is preferably a hydroxy group and/or a carboxy group, more preferably a hydroxy group or a carboxy group.
  • the amount of the first reactive group of the polymer component (B) is preferably 0.002 mmol/g or more, more preferably 0.006 mmol/g or more, still more preferably 0.01 mmol/g or more, and 0.8 mmol /g or less, more preferably 0.6 mmol/g or less, still more preferably 0.5 mmol/g or less, particularly preferably 0.2 mmol/g or less, and most preferably 0.1 mmol/g or less.
  • the amount of the first reactive group is 0.002 mmol/g or more, the adhesive material formed is appropriately crosslinked and exhibits a suitable recovery rate, and when the amount is 0.8 mmol/g or less, the adhesive material formed is improved.
  • the distance between cross-linking points is sufficiently long and the flexibility is excellent.
  • the polymer component (B) preferably further has a carboxy group as a functional group other than the first reactive group.
  • the carboxy group content of the copolymer (B) is preferably 0.08 mmol/g or more, more preferably 0.16 mmol/g or more, still more preferably 0.32 mmol/g or more. /g or less, more preferably 0.8 mmol/g or less, still more preferably 0.6 mmol/g or less.
  • the carboxy group and the hydroxy group per unit mass of the polymer component (B) is preferably 4 or more, more preferably 8 or more, still more preferably 16 or more, and preferably 60 or less, more preferably 40 or less, and still more preferably 30 or less. be. If the molar ratio (carboxy group/hydroxy group) is within the above range, the adhesive layer has high restorability and a suitable balance between adhesive strength and flexibility.
  • the polymer component (B) preferably has a hydroxy group as a functional group other than the first reactive group.
  • the amount of hydroxy groups in the polymer component (B) is preferably 0.01 mmol/g or more, more preferably 0.02 mmol/g or more, still more preferably 0.04 mmol/g or more, and 0.25 mmol/g. /g or less, more preferably 0.20 mmol/g or less, and still more preferably 0.15 mmol/g or less.
  • the carboxy group and the hydroxy group per unit mass of the polymer component (A)
  • the molar ratio of the group (carboxy group/hydroxy group) is preferably 3.0 or more, more preferably 3.5 or more, still more preferably 4.0 or more, preferably 30 or less, more preferably 25 or less, More preferably, it is 20 or less. If the molar ratio (carboxy group/hydroxy group) is within the above range, the adhesive layer has high restorability and a suitable balance between adhesiveness and flexibility.
  • the (B) polymer component may be a random copolymer, a block copolymer, or a graft copolymer, preferably a random copolymer.
  • the weight average molecular weight (Mw) of the polymer component (B) is preferably 100,000 or more, more preferably 200,000 or more, still more preferably 300,000 or more, particularly preferably 400,000 or more, and preferably 3,000,000 or less. , more preferably 1,000,000 or less, and still more preferably 800,000 or less.
  • Mw weight average molecular weight
  • the molecular weight distribution (Mw/Mn) of the polymer component (B) is more than 3.0, preferably 5.0 or more, more preferably 7.0 or more, and preferably 12.0 or less, and more It is preferably 11.0 or less, more preferably 10.0 or less. If Mw/Mn is more than 3.0, an adhesive material with excellent adhesive strength and flexibility can be formed.
  • the glass transition temperature (Tg) of the polymer component (B) is preferably ⁇ 70° C. or higher, more preferably ⁇ 60° C. or higher, and preferably 0° C. or lower, more preferably ⁇ 10° C. or lower, further preferably -20°C or less. If the Tg is -70 ° C. or higher, the adhesive material is given sufficient cohesive strength, and the durability of the formed adhesive material is improved. As a result, peeling at low temperatures is suppressed, and durability is improved.
  • the plurality of (meth)acrylic copolymer components contain at least (A) (meth)acrylic copolymer component and (B) (meth)acrylic copolymer component.
  • the content of the (A) (meth)acrylic copolymer component in the plurality of (meth)acrylic copolymer components is 75% by mass or more, preferably 77% by mass or more, more preferably 80% by mass. 99% by mass or less, preferably 97% by mass or less, more preferably 95% by mass or less. If the content of the (A) (meth)acrylic copolymer component is 75% by mass or more, an adhesive material having an excellent recovery rate can be formed, and if it is 99% by mass or less, adhesive strength and flexibility can form an excellent adhesive.
  • the content of the (B) (meth)acrylic copolymer component in the plurality of (meth)acrylic copolymer components is 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass. 25% by mass or less, preferably 23% by mass or less, more preferably 20% by mass or less. If the content of the (B) (meth)acrylic copolymer component is 1% by mass or more, an adhesive material having excellent adhesive strength and flexibility can be formed, and if it is 25% by mass or less, the recovery rate can form an excellent adhesive.
  • the total content of the (A) (meth)acrylic copolymer component and the (B) (meth)acrylic copolymer component in the plurality of (meth)acrylic copolymer components is 80 mass. % or more, more preferably 90 mass % or more, and still more preferably 95 mass % or more. It is also preferable that the (meth)acrylic copolymer component contains only the (A) (meth)acrylic copolymer component and the (B) (meth)acrylic copolymer component.
  • the mass ratio (A/B) between the (A) polymer component and the (B) polymer component in the plurality of (meth)acrylic copolymer components is preferably 3 or more, more preferably 4 or more, It is more preferably 5 or more, preferably 25 or less, more preferably 20 or less, still more preferably 15 or less.
  • mass ratio (A/B) is 3 or more, an adhesive material with excellent recovery rate can be formed, and when it is 25 or less, an adhesive material with excellent adhesive strength and flexibility can be formed.
  • the plurality of (meth)acrylic copolymer components may contain polymer components other than the (A) polymer component and (B) polymer component.
  • examples of the other polymer component include a (meth)acrylic copolymer component having no first reactive group.
  • the (A) polymer component and (B) polymer component have a first reactive group. That is, the (A) polymer component and (B) polymer component contain the structural unit (a-1) having the first reactive group in their structure.
  • the structural unit (a-1) having the first reactive group may be of only one type, or may be of two or more types.
  • the first reactive group is a structural unit derived from a (meth)acrylic monomer (preferably a (meth)acrylate monomer and/or (meth)acrylic acid), or a structural unit derived from a vinyl monomer other than the (meth)acrylic monomer.
  • the structural unit (a-1) having the first reactive group is derived from (meth)acrylic monomer (preferably (meth)acrylate monomer and/or (meth)acrylic acid) having the first reactive group or a structural unit derived from a vinyl monomer other than a (meth)acrylic monomer having a first reactive group.
  • the content of the structural unit (structural unit (a-1) having the first reactive group) derived from the vinyl monomer having the first reactive group in the polymer component (A) is 100% by mass of the polymer component. Among them, it is preferably 0.03% by mass or more, more preferably 0.09% by mass or more, still more preferably 0.15% by mass or more, preferably 6% by mass or less, more preferably 3% by mass or less, and further Preferably, it is 1% by mass or less.
  • the vinyl monomer having the first reactive group includes vinyl monomers other than the (meth)acrylic monomer having the first reactive group and the (meth)acrylic monomer having the first reactive group.
  • the content of the structural unit (structural unit (a-1) having the first reactive group) derived from the vinyl monomer having the first reactive group in the polymer component (B) is 100% by mass of the polymer component. Among them, it is preferably 0.03% by mass or more, more preferably 0.09% by mass or more, still more preferably 0.15% by mass or more, preferably 6% by mass or less, more preferably 3% by mass or less, and further Preferably, it is 1% by mass or less.
  • the vinyl monomer having the first reactive group includes vinyl monomers other than the (meth)acrylic monomer having the first reactive group and the (meth)acrylic monomer having the first reactive group.
  • Examples of the (meth)acrylic monomer include (b1) a (meth)acrylic monomer having no functional group capable of serving as the first reactive group, and (b2) a (meth)acrylic monomer having a functional group capable of serving as the first reactive group. is mentioned. These monomers may be used alone or in combination of two or more.
  • As the (b1) (meth)acrylic monomer (b1-1) a (meth)acrylate monomer having no functional group capable of serving as a first reactive group is preferable.
  • Examples of the (b2) (meth)acrylic monomer include (b2-1) a (meth)acrylate monomer having a functional group capable of serving as a first reactive group, and (meth)acrylic acid.
  • the (b1) (meth)acrylic monomer having no functional group that can be the first reactive group includes (meth)acrylate having a linear alkyl group, (meth)acrylate having a branched alkyl group, alkoxy (Meth) acrylates having a group, (meth) acrylates having a polyalkylene glycol structural unit, (meth) acrylates having an alicyclic hydrocarbon group, (meth) acrylates having an aromatic group, having a tertiary amino group ( meth)acrylates, (meth)acrylamides, and the like.
  • (meth)acrylates having a linear alkyl group (meth)acrylates having a branched alkyl group, (meth)acrylates having an alicyclic hydrocarbon group, and (meth)acrylates having an aromatic group and (meth)acrylamides are preferred.
  • the (meth)acrylate having a straight-chain alkyl group is preferably a (meth)acrylate having a straight-chain alkyl group having 1 to 20 carbon atoms in the straight-chain alkyl group.
  • (Meth)acrylates having a straight-chain alkyl group with a number of 1 to 15 are more preferred, and (meth)acrylates having a straight-chain alkyl group with a straight-chain alkyl group having a carbon number of 8 to 15 are even more preferred. .
  • Examples of (meth)acrylates 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 linear alkyl (meth)acrylates esters.
  • the (meth)acrylate having a branched-chain alkyl group is preferably a (meth)acrylate having a branched-chain alkyl group having 3 to 20 carbon atoms in the branched-chain alkyl group. (Meth)acrylates with 3 to 10 branched alkyl groups are preferred.
  • Examples of (meth)acrylates having a branched alkyl group include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isooctyl (meth)acrylate, 2 - (meth)acrylic acid branched chain alkyl esters such as ethylhexyl (meth)acrylate, isononyl (meth)acrylate and isodecyl (meth)acrylate.
  • (meth)acrylates having an alkoxy group examples include (meth)acrylic acid alkoxyalkyl esters such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate.
  • Examples of (meth)acrylates having an alicyclic hydrocarbon group include (meth)acrylates having a cyclic alkyl group and (meth)acrylates 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.
  • the cyclic alkyl group includes a cyclic alkyl group having a monocyclic structure (for example, a cycloalkyl group), and may have a chain portion.
  • (meth)acrylates having a cyclic alkyl group having a monocyclic structure include (meth)acrylic acid cyclic alkyl esters such as cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, and cyclododecyl (meth)acrylate. be able to.
  • the (meth)acrylate having a polycyclic structure is preferably a (meth)acrylate having a polycyclic structure with 6 to 12 carbon atoms.
  • the polycyclic structure includes cyclic alkyl groups having a bridged ring structure (eg, adamantyl group, norbornyl group, isobornyl group), and may also have a chain portion.
  • (meth)acrylates having a polycyclic structure include bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, 2-methyl-2- adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) Acrylate, dicyclopentenyloxyethyl (meth)acrylate and the like can be mentioned.
  • the (meth)acrylate having an aromatic group is preferably a (meth)acrylate having an aromatic group having 6 to 12 carbon atoms.
  • the aromatic group include an aryl group, and may have a chain portion such as an alkylaryl group, an araryl group, an aryloxyalkyl group, and the like.
  • 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.
  • a compound having an alkylaryl group directly bonded thereto may be mentioned.
  • 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.
  • Specific examples of (meth)acrylates having an aromatic group include benzyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate and the like.
  • Examples of (meth)acrylates 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, N-methyl(meth) Acrylamide, N-ethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-tert-butyl (meth)acrylamide, N-octyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl ( meth)acrylamide, N-propoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, diacetoneacrylamide, 4-(meth)acryloylmorpholine and the like.
  • the (meth)acrylamides are (meth)acryl monomers, but are not included in (meth)acrylate monomers.
  • the (b2) (meth)acrylic monomer having a functional group capable of serving as a first reactive group includes a (meth)acrylic monomer having a hydroxy group (preferably a (meth)acrylate monomer) and a (meth)acrylic monomer having a carboxy group.
  • Monomers preferably (meth)acrylic acid), epoxy group-containing (meth)acrylic monomers (preferably (meth)acrylate monomers), and the like can be mentioned.
  • a (meth)acrylic monomer having a hydroxy group and/or a (meth)acrylic monomer having a carboxy group are preferred, and a (meth)acrylic monomer having a hydroxy group is more preferred.
  • 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, 6 - hydroxyalkyl (meth)acrylates such as hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate; (4-hydroxymethylcyclohexyl) hydroxyalkylcycloalkyl (meth)acrylates such as methyl (meth)acrylate; and caprolactone adducts of hydroxyalkyl (meth)acrylates.
  • hydroxyalkyl (meth)acrylates are preferred, and (meth)acrylates having a hydroxyalkyl group having 1 to 5 carbon atoms are more preferred.
  • Examples of the (meth)acrylic monomer having a carboxy group include carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl maleate, 2 - Monomers obtained by reacting (meth)acrylates having a hydroxy group such as (meth)acryloyloxyethyl phthalate with acid anhydrides such as maleic anhydride, succinic anhydride, and phthalic anhydride (e.g., 2-acryloyloxy hydrogen succinate) Ethyl, 2-methacryloyloxyethyl hydrogen succinate, 2-(acryloyloxy)ethyl hydrogen hexahydrophthalate, 2-(methacryloyloxyethyl) hydrogen hexahydrophthalate, 1-(2-acryloyloxyethyl) phthalate, phthalate acid 1-(2-methacryl
  • 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 which does not have a functional group that can be the first reactive group, and (b4) a functional group that can be the first reactive group.
  • Examples include vinyl monomers other than (meth)acrylic monomers having a group. These monomers may be used alone or in combination of two or more.
  • Examples of (b3) vinyl monomers other than (meth)acrylic monomers having no functional group that can be the first reactive group include aromatic vinyl monomers, heterocyclic vinyl monomers, vinyl carboxylates, and tertiary amino groups. , vinyl monomers containing a quaternary ammonium base, vinylamides, ⁇ -olefins, dienes, halogenated vinyl monomers, and the like.
  • Examples of the aromatic vinyl monomers include styrene, ⁇ -methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene and 1-vinylnaphthalene.
  • Examples of the vinyl monomer containing the 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, and vinyl benzoate.
  • Examples of vinyl monomers containing a tertiary amino group include N,N-dimethylallylamine.
  • Vinyl monomers containing the quaternary ammonium base include N-methacryloylaminoethyl-N,N,N-dimethylbenzylammonium chloride and the like.
  • vinylamides include N-vinylformamide, N-vinylacetamide, 1-vinyl-2-pyrrolidone, N-vinyl- ⁇ -captolactam and the like.
  • ⁇ -olefin examples include 1-hexene, 1-octene, 1-decene and the like.
  • dienes include butadiene, isoprene, 4-methyl-1,4-hexadiene, and 7-methyl-1,6-octadiene.
  • halogenated vinyl monomers examples include vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, tetrafluoropropylene, vinylidene chloride, vinyl chloride, 1-chloro-1-fluoro Examples include ethylene, 1,2-dichloro-1,2-difluoroethylene, and the like.
  • Vinyl monomers other than the (b4) (meth)acrylic monomer having a functional group capable of serving as the first reactive group include vinyl monomers having a hydroxy group, vinyl monomers having a carboxy group, vinyl monomers containing an epoxy group, and the like. mentioned.
  • Examples of vinyl monomers having a hydroxy group include p-hydroxystyrene and allyl alcohol.
  • vinyl monomers having a carboxyl group include crotonic acid, maleic acid, itaconic acid, citraconic acid, and cinnamic acid.
  • Examples of vinyl monomers containing epoxy groups include 2-allyloxirane, glycidyl vinyl ether, 3,4-epoxycyclohexyl vinyl ether, and the like.
  • the (meth)acrylic copolymer mixture can be prepared, for example, by mixing a plurality of (meth)acrylic copolymer components.
  • the (meth)acrylic copolymer is obtained by polymerizing a (meth)acrylic monomer.
  • a polymerization composition containing a plurality of polymer components it is also possible to obtain a polymerization composition containing a plurality of polymer components, and such a polymerization composition can be obtained by a plurality of (meth)acrylic copolymers. May be used as a coalescing component.
  • the polymer component contained in the polymer composition or the (meth)acrylic copolymer mixture can be confirmed by preparing a differential molecular weight distribution curve by gel permeation chromatography and performing waveform separation on this curve.
  • a polymerization method for polymerizing the monomer composition either a free radical polymerization method or a living radical polymerization method can be employed.
  • the living radical polymerization method maintains the simplicity and versatility of the conventional radical polymerization method. It is easy to precisely control and manufacture a polymer with a uniform composition. Therefore, in the copolymer produced by the living radical polymerization method, the reactive functional groups are uniformly distributed in each molecular chain.
  • a random copolymer can be obtained by using a mixture of each monomer (vinyl monomer).
  • a block copolymer can also be obtained by sequentially reacting vinyl monomers constituting the copolymer.
  • Living radical polymerization methods include methods using compounds that can generate nitroxide radicals (nitroxide method; NMP method); A method of living polymerization from the polymerization initiator compound (ATRP method); a method of using a sulfur-based reversible chain transfer agent (RAFT method); a method of using an organic tellurium compound (TERP method).
  • a method using an organic iodine compound (ITP method) A method using an iodine compound as a polymerization initiator compound and an organic compound such as a phosphorus compound, a nitrogen compound, an oxygen compound, or a hydrocarbon as a catalyst (reversible transfer catalyst polymerization; RTCP method , reversible catalyst-mediated polymerization; RCMP method).
  • TERP method it is preferable to use the TERP method from the viewpoint of the diversity of usable monomers, molecular weight control in the high molecular region, uniform composition, or coloring.
  • the TERP method is a method of polymerizing a radically polymerizable compound (vinyl monomer) using an organic tellurium compound as a chain transfer agent. 2004/072126 and methods described in WO 2004/096870.
  • Specific polymerization methods for the TERP method include the following (a) to (d).
  • 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 each independently a hydrogen atom or an alkyl group 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 amido 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.
  • Specific examples of the organic ditelluride compound represented by formula (2) include dimethyl ditelluride, dibutyl ditelluride, and the like.
  • the azo polymerization initiator can be used without particular limitation as long as it is an azo polymerization initiator used in normal radical polymerization.
  • ADVN ,2′-azobis(2,4-dimethylvaleronitrile)
  • ACBN 1,1′-azobis(1-cyclohexanecarbonitrile)
  • V-70 2,2′-azobis(4-methoxy-2,4- dimethylvaleronitrile)
  • the polymerization step is carried out in a vessel substituted with an inert gas, with a vinyl monomer and an organic tellurium compound of formula (1) for the purpose of promoting the reaction, controlling the molecular weight and molecular weight distribution depending on the type of the vinyl monomer, and further adding an azo A polymerization initiator and/or an organic ditelluride compound of formula (2) are mixed.
  • the inert gas include nitrogen, argon, and helium. Argon and nitrogen are preferred.
  • the amount of the vinyl monomer used in (a), (b), (c) and (d) may be appropriately adjusted according to the physical properties of the intended copolymer.
  • the polymerization reaction can be carried out without a solvent, it may be carried out by using an aprotic or protic solvent generally used in radical polymerization and stirring the mixture.
  • Aprotic solvents that can be used are, for example, acetonitrile, methyl ethyl ketone, anisole, benzene, toluene, propylene glycol monomethyl ether acetate, ethyl acetate, tetrahydrofuran (THF), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), acetone, dioxane, chloroform, carbon tetrachloride and the like.
  • protic solvents examples include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, hexafluoroisopropanol, diacetone alcohol and the like.
  • a solvent may be used individually and may use 2 or more types together.
  • the amount of the solvent to be used may be appropriately adjusted, and is preferably 0.01 ml to 50 ml per 1 g of the vinyl monomer.
  • the reaction temperature and reaction time may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the polymer component to be obtained, but the mixture is usually stirred at 0°C to 150°C for 1 minute to 100 hours.
  • the pressure is usually normal pressure, but may be pressurized or reduced.
  • the desired copolymer can be separated from the resulting reaction mixture by removing the used solvent, residual vinyl monomers, and the like by ordinary separation and purification means.
  • the growing terminal of the copolymer obtained by the polymerization reaction is in the form of —TeR 1 (wherein R 1 is the same as above) derived from the tellurium compound, and is deactivated by an operation in air after the completion of the polymerization reaction.
  • TeR 1 (wherein R 1 is the same as above) derived from the tellurium compound
  • tellurium atoms may remain. Since a copolymer having a tellurium atom remaining at the end thereof is colored or has poor thermal stability, it is preferable to remove the tellurium atom.
  • Examples of the method for removing tellurium atoms include a radical reduction method; a method of adsorption with activated carbon or the like; a method of adsorbing a metal with an ion exchange resin or the like; these methods can also be used in combination.
  • the other end of the copolymer obtained by the polymerization reaction (the end opposite to the growing end) is -CR 2 R 3 R 4 derived from a tellurium compound (wherein R 2 , R 3 and R 4 are represented by the formula The same as R 2 , R 3 and R 4 in (1)).
  • Free radical polymerization method A conventionally known method may be adopted for the free radical polymerization method.
  • Polymerization initiators used in free radical polymerization include azo polymerization initiators, peroxide polymerization initiators, and the like.
  • the azo polymerization initiator include 2,2′-azobis(isobutyronitrile) (AIBN), 2,2′-azobis(2-methylbutyronitrile) (AMBN), 2,2′- azobis(2,4-dimethylvaleronitrile) (ADVN), 1,1′-azobis(1-cyclohexanecarbonitrile) (ACHN), dimethyl-2,2′-azobisisobutyrate (MAIB), 4,4 '-azobis(4-cyanovaleric acid) (ACVA), 1,1'-azobis(1-acetoxy-1-phenylethane), 2,2'-azobis(2-methylbutyramide), 2,2'- Azobis(4-methoxy-2,4-dimethylvaleronitrile
  • the polymerization reaction can be carried out without a solvent, it may be carried out by using an aprotic or protic solvent generally used in radical polymerization and stirring the mixture.
  • Aprotic solvents that can be used are, for example, acetonitrile, anisole, benzene, toluene, N,N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), acetone, 2-butanone.
  • protic solvents include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, hexafluoroisopropanol, and diacetone alcohol.
  • the amount of the solvent to be used may be adjusted as appropriate. For example, it is preferably 0.01 ml or more, more preferably 0.05 ml or more, still more preferably 0.1 ml or more, and 50 ml or less per 1 g of the vinyl monomer. It is preferably 10 ml or less, more preferably 1 ml or less.
  • the reaction temperature and reaction time may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the resulting polymer component, but the mixture is usually stirred at 0°C to 150°C for 1 minute to 100 hours. At this time, the pressure is usually normal pressure, but may be pressurized or reduced.
  • the intended polymer composition can be separated from the resulting reaction mixture by removing the used solvent, residual vinyl monomer, etc., by a conventional separation and purification means.
  • the adhesive composition contains a cross-linking agent.
  • the cross-linking agent is a compound having two or more second reactive groups in one molecule that react with the first reactive groups of the polymer component (A) and the polymer component (B).
  • the 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-based cross-linking agents, melamine resin-based cross-linking agents, and urea resin-based cross-linking agents.
  • the said crosslinking agent may be used individually by 1 type, and may use 2 or more types together.
  • isocyanate-based cross-linking agents and/or epoxy-based cross-linking agents are preferred.
  • an isocyanate-based cross-linking agent or an epoxy-based cross-linking agent is more preferable, and an epoxy-based cross-linking agent is even more preferable, because the recovery rate of the adhesive material to be formed is improved.
  • the average number of second reactive groups in one molecule of the cross-linking agent is 2 or more, more preferably 3 or more, still more preferably 4 or more, particularly preferably 5 or more, and preferably 8 or less. That is, the cross-linking agent is more preferably a polyfunctional cross-linking agent having 4 or more second reactive groups in one molecule. If the cross-linking agent is tetrafunctional or more, the average distance between cross-linking points in the polymer in the adhesive becomes longer. Therefore, the obtained adhesive material has a low initial stress and exhibits a high recovery rate.
  • the molecular weight of the cross-linking agent is preferably 200 or more, more preferably 300 or more, still more preferably 400 or more, and preferably 1500 or less, more preferably 1000 or less, still more preferably 700 or less.
  • the content of the second reactive group in the cross-linking agent is preferably 1.5 mmol/g or more, more preferably 3.0 mmol/g or more, still more preferably 3.7 mmol/g or more, and preferably 10 mmol/g or less. , more preferably 8 mmol/g or less, and still more preferably 6 mmol/g or less. If the content of the second reactive group of the cross-linking agent is within this range, the valence of the cross-linking agent will be low, the cross-linking points will be evenly distributed in the adhesive, and the average distance between cross-linking points will be long. Therefore, the obtained adhesive material has a low initial stress and exhibits a high recovery rate.
  • Examples of the combination of the first reactive group possessed by the polymer component (A) and the polymer component (B) and the second reactive group possessed by the cross-linking agent include the following combinations.
  • the second reactive group of the cross-linking agent is an isocyanate group
  • the first reactive group may be a hydroxy group.
  • the second reactive group of the cross-linking agent is an epoxy group
  • the first reactive group may be a carboxy group.
  • the first reactive group is a hydroxy group
  • the first reactive group is a carboxy group and the second reactive group is an epoxy group
  • the isocyanate-based cross-linking agent is a compound having two or more isocyanate groups (including isocyanate-regenerative functional groups in which the isocyanate groups are temporarily protected by a blocking agent or quantization) as the second reactive groups in one molecule.
  • the isocyanate-based cross-linking agents may be used alone or in combination of two or more.
  • Isocyanate-based cross-linking agents include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, adducts of these with various polyols, polyfunctionalized with isocyanurate bonds, biuret bonds, allophanate bonds, etc. polyisocyanate, and the like.
  • a compound having two isocyanate groups including an isocyanate-regenerative functional group in which the isocyanate group is temporarily protected by a blocking agent or quantification
  • bifunctional isocyanate-based cross-linking agent Compounds having three isocyanate groups (including isocyanate regenerative functional groups temporarily protected by blocking agents or isocyanate groups by quantification) in one molecule (trifunctional isocyanate cross-linking agents), isocyanate groups (isocyanate groups (containing an isocyanate regenerative functional group temporarily protected by a blocking agent or quantification) in one molecule (hexafunctional isocyanate cross-linking agent).
  • Diisocyanate compounds such as aliphatic diisocyanate compounds, alicyclic diisocyanate compounds, and aromatic diisocyanate compounds can be mentioned as bifunctional isocyanate-based cross-linking agents, and adducts of these diisocyanate compounds and diol compounds can also be used.
  • the diol compound is a compound represented by the general formula "HO-Y-OH" (Y is a divalent aliphatic group, a divalent alicyclic group, a divalent aromatic group, etc.). .
  • aliphatic diisocyanate compounds include ethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, 2,2,4- Examples include trimethyl-1,6-hexamethylene diisocyanate, among which aliphatic diisocyanate compounds having 4 to 30 carbon atoms are preferred, and aliphatic diisocyanate compounds having 4 to 10 carbon atoms are more preferred.
  • alicyclic diisocyanate compound examples include isophorone diisocyanate, cyclopentyl diisocyanate, cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tetramethylxylene diisocyanate and the like, among which 7 carbon atoms. ⁇ 30 alicyclic diisocyanate compounds are preferred.
  • diol compound examples include 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-ethyl-2 -Butyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol and other aliphatic diol compounds, among which 3 to 10 carbon atoms is preferred.
  • Examples of the trifunctional isocyanate cross-linking agent and the hexafunctional isocyanate cross-linking agent include the adduct of the diisocyanate compound, the biuret of the diisocyanate compound, the isocyanurate of the diisocyanate compound (cyclic multimer of diisocyanate compounds), and the like. be done.
  • the isocyanate-based cross-linking agent preferably does not have an aromatic ring.
  • the isocyanate-based cross-linking agent includes an aliphatic diisocyanate compound, and a bifunctional isocyanate-based cross-linking agent selected from the group consisting of an adduct of an aliphatic diisocyanate compound and an aliphatic diol compound; Trifunctional or hexafunctional isocyanate-based cross-linking agents selected from the group consisting of adducts, biurets of aliphatic diisocyanate compounds, and isocyanurate compounds of aliphatic diisocyanates are preferred.
  • epoxy cross-linking agent refers to a compound having two or more epoxy groups in one molecule as a second reactive group.
  • the epoxy-based cross-linking agents may be used alone or in combination of two or more.
  • Epoxy-based cross-linking agents include aliphatic epoxy compounds, alicyclic epoxy compounds, aromatic epoxy compounds, heterocyclic epoxy compounds, and the like.
  • Examples of the aliphatic epoxy compounds include ethylene glycidyl ether, ethylene glycol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidyl amine, diamine glycidyl amine, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, and propylene glycol diglycidyl.
  • Ether polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, polyglycerol polyglycidyl ether, trimethylolpropane poly glycidyl ether, diglycidyl adipic acid ester, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane and the like.
  • Examples of the alicyclic epoxy compounds include 1,3-bis(N,N'-diglycidylaminomethyl)cyclohexane, 1,6-hexanediol diglycidyl ether, N,N,N',N'-tetraglycidyl- and m-xylylenediamine.
  • aromatic epoxy compound examples include bisphenol A epichlorohydrin type epoxy resin, diglycidylaniline, o-diglycidyl phthalate, resorcin diglycidyl ether, and bisphenol-S-diglycidyl ether.
  • heterocyclic epoxy compounds examples include triglycidyl-tris(2-hydroxyethyl) isocyanurate, 1,3,5-tris-(2,3-epoxybutyl)-isocyanurate, 1,3,5-tris- (3,4-epoxybutyl)-isocyanurate, 1,3,5-tris-(4,5-epoxypentyl)-isocyanurate, sorbitan polyglycidyl ether and the like.
  • the epoxy-based cross-linking agent a compound having two epoxy groups in one molecule (bifunctional epoxy-based cross-linking agent), a compound having three epoxy groups in one molecule (tri-functional epoxy-based cross-linking agent), or A compound having four epoxy groups in one molecule (tetrafunctional epoxy-based cross-linking agent) is preferred.
  • the cross-linking agent is a bifunctional epoxy cross-linking agent, a tri-functional epoxy cross-linking agent or a tetra-functional epoxy cross-linking agent, the cross-linking points will be evenly distributed in the adhesive material and the average distance between cross-linking points will be long. Therefore, the obtained adhesive material has a low initial stress and exhibits a high recovery rate.
  • the adhesive composition preferably contains only an isocyanate-based cross-linking agent or only an epoxy-based cross-linking agent as a cross-linking agent.
  • an isocyanate-based cross-linking agent is contained as a cross-linking agent, a bifunctional isocyanate-based cross-linking agent having two isocyanate groups in one molecule, a trifunctional isocyanate-based cross-linking agent having three isocyanate groups in one molecule, or one It is preferable to contain only a hexafunctional isocyanate-based cross-linking agent having 6 isocyanate groups in the molecule.
  • a bifunctional epoxy-based cross-linking agent having two epoxy groups in one molecule a trifunctional epoxy-based cross-linking agent having three epoxy groups in one molecule, or , preferably contains only a tetrafunctional epoxy-based cross-linking agent having four epoxy groups in one molecule.
  • the content of the cross-linking agent in the adhesive composition is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and still more preferably 100 parts by mass of the (meth)acrylic copolymer components. It is 0.1 parts by mass or more, preferably 0.2 parts by mass or less, and more preferably 0.17 parts by mass or less.
  • the adhesive strength and the recovery rate are within suitable ranges.
  • the molar ratio of the second reactive group possessed by the cross-linking agent to the first reactive group possessed by the plurality of (meth)acrylic copolymer components is 1 or more, preferably 2 or more, more preferably 3 or more, preferably 70 or less, more preferably 15 or less, still more preferably 10 or less, and particularly preferably 5 or less. If the molar ratio is 1 or more, the cross-linking agent reacts just enough, the second reactive group does not surplus, and a high recovery rate is expressed, and if it is 70 or less, the reaction proceeds sufficiently and the recovery rate is high. express.
  • the molar ratio of the first reactive groups possessed by the plurality of (meth)acrylic copolymer components to the amount (molar amount) of the crosslinking agent is , preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, preferably 250 or less, more preferably 18 or less, still more preferably less than 12, particularly preferably 11 or less, most preferably 8 or less . If the molar ratio is within the above range, the adhesive strength and the recovery rate are within suitable ranges.
  • additives In addition to the copolymer component and the cross-linking agent, other additives may be added to the adhesive composition.
  • Other additives include cross-linking accelerators, cross-linking retarders, tackifying resins (tackifiers), polymerizable compounds, photopolymerization initiators, silane coupling agents, plasticizers, softeners, release aids, dyes, and pigments.
  • dyes include dyes, fluorescent brighteners, antistatic agents, wetting agents, surfactants, thickeners, antifungal agents, preservatives, oxygen absorbers, ultraviolet absorbers, antioxidants, near-infrared absorbers, water-soluble quenchers agents, fragrances, metal deactivators, nucleating agents, alkylating agents, flame retardants, lubricants, processing aids, and the like.
  • Cross-linking accelerator A cross-linking accelerator may be added to the adhesive composition as necessary.
  • cross-linking accelerators include organic tin compounds and metal chelate compounds.
  • the cross-linking accelerators may be used alone, or two or more of them may be used in combination.
  • organic tin compounds examples include dibutyltin dilaurate, dioctiolstin dilaurate, and dibutyltin dioctylate.
  • the metal chelate compound is a complex in which a ligand having two or more coordinating atoms forms a ring and is bound to a central metal.
  • the content of the cross-linking accelerator in the adhesive composition is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, relative to 100 parts by mass of the plurality of (meth)acrylic copolymer components. It is more preferably 0.04 parts by mass or more, preferably 0.5 parts by mass or less, more preferably 0.4 parts by mass or less, and still more preferably 0.3 parts by mass or less.
  • Cross-linking retarder A cross-linking retarder may be added to the adhesive composition as necessary.
  • the cross-linking retarder is a compound capable of suppressing an excessive increase in viscosity of the pressure-sensitive adhesive composition by blocking the functional group of the cross-linking agent in the pressure-sensitive adhesive composition containing the cross-linking agent.
  • cross-linking retarder is not particularly limited, but for example, ⁇ -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 acetoacetate, octyl acetoacetate, oleyl acetoacetate, lauryl acetoacetate and stearyl acetoacetate; benzoylacetone and the like can be used.
  • the cross-linking retarder one capable of acting as a chelating agent is preferable, and ⁇ -diketones and ⁇ -ketoesters are preferable.
  • the content of the cross-linking retarder that can be blended in the adhesive composition is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass with respect to 100 parts by mass of the plurality of (meth)acrylic copolymer components. It is at least 0.5 parts by mass, more preferably at least 0.5 parts by mass, preferably at most 4.0 parts by mass, more preferably at most 3.0 parts by mass, and even more preferably at most 1.5 parts by mass.
  • tackifier resin A tackifier resin other than the copolymer component may be blended in the adhesive composition, if necessary.
  • the tackifier resin is not particularly limited, and examples thereof include rosin-based tackifier resins, terpene-based tackifier resins, phenol-based tackifier resins, and hydrocarbon-based tackifier resins.
  • rosin-based tackifying resins examples include unmodified rosins (fresh rosins) such as gum rosin, wood rosin, tall oil rosin, and modified rosins obtained by modifying these unmodified rosins by polymerization, disproportionation, hydrogenation, etc. rosin, stabilized rosin, disproportionated rosin, completely hydrogenated rosin, partially hydrogenated rosin, and other chemically modified rosins), as well as various rosin derivatives.
  • fresh rosins fresh rosins
  • modified rosins obtained by modifying these unmodified rosins by polymerization, disproportionation, hydrogenation, etc.
  • rosin stabilized rosin, disproportionated rosin, completely hydrogenated rosin, partially hydrogenated rosin, and other chemically modified rosins
  • rosin derivative examples include rosin phenolic resins obtained by adding phenol to rosins (unmodified rosin, modified rosin) with an acid catalyst and thermally polymerizing them; Ester compounds (unmodified rosin esters) and denatured rosin ester compounds obtained by esterifying denatured rosin with alcohols (polymerized rosin esters, stabilized rosin esters, disproportionated rosin esters, completely hydrogenated rosin esters, partially hydrogenated rosin rosin ester-based resins such as esters); unsaturated fatty acid-modified rosin-based resins obtained by modifying unmodified rosin or modified rosin with unsaturated fatty acids; unsaturated fatty acid-modified rosin ester-based resins obtained by modifying rosin ester-based resins with unsaturated fatty acids ; unmodified rosin, modified rosin, rosin alcohol resin obtained by reducing the carboxyl group in unsaturated
  • Terpene-based tackifying resins include, for example, ⁇ -pinene polymer, ⁇ -pinene polymer, terpene-based resins such as dipentene polymer, and modification of these terpene-based resins (phenol modification, aromatic modification, hydrogenation modification, hydrocarbon-modified) modified terpene-based resins (for example, terpene-phenolic resins, styrene-modified terpene-based resins, aromatic modified terpene-based resins, hydrogenated terpene-based resins).
  • phenol modification, aromatic modification, hydrogenation modification, hydrocarbon-modified terpene-based resins for example, terpene-phenolic resins, styrene-modified terpene-based resins, aromatic modified terpene-based resins, hydrogenated terpene-based resins.
  • phenol-based tackifying resins include condensation products of various phenols (e.g., phenol, m-cresol, 3,5-xylenol, p-alkylphenol, resorcinol) and formaldehyde (e.g., alkylphenol-based resins, xylene-formaldehyde-based resins), resoles obtained by addition reaction of the above phenols and formaldehyde with an alkali catalyst, and novolaks obtained by condensation reaction of the above phenols and formaldehyde with an acid catalyst.
  • phenols e.g., phenol, m-cresol, 3,5-xylenol, p-alkylphenol, resorcinol
  • formaldehyde e.g., alkylphenol-based resins, xylene-formaldehyde-based resins
  • resoles obtained by addition reaction of the above phenols and formaldehyde with an alkali
  • hydrocarbon-based tackifying resins include, for example, aliphatic hydrocarbon resins [olefins and dienes having 4 to 5 carbon atoms (olefins such as butene-1, isobutylene, pentene-1; butadiene, Dienes such as 1,3-pentadiene and isoprene), etc.], aliphatic cyclic hydrocarbon resins [so-called “C4 petroleum fraction” and “C5 petroleum fraction” are cyclized dimers Alicyclic hydrocarbon resins polymerized after solidification, polymers of cyclic diene compounds (cyclopentadiene, dicyclopentadiene, ethylidenenorbornene, dipentene, etc.) or hydrogenated products thereof, aromatic hydrocarbon resins such as the following Alicyclic hydrocarbon resins obtained by hydrogenating aromatic rings of aliphatic/aromatic petroleum resins], aromatic hydrocarbon resins [vinyl group-containing
  • the content of the tackifying resin that can be blended in the adhesive composition is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, relative to 100 parts by mass of the plurality of (meth)acrylic copolymer components. , more preferably 20 parts by mass or more, preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 40 parts by mass or less.
  • the adhesive composition may contain a polymerizable compound. Flexibility can be imparted to the adhesive by blending the polymerizable compound and polymerizing the polymerizable compound in the adhesive.
  • Examples of the polymerizable compound include compounds having two or more polymerizable groups in one molecule.
  • Examples of polymerizable groups include ethylenically unsaturated groups.
  • the said polymerizable compound can be used individually or in combination of 2 or more types.
  • Examples of the polymerizable compound include compounds having two or more (meth)acryloyl groups, and polyfunctional monomers and polyfunctional oligomers are preferred.
  • the number of ethylenically unsaturated groups in one molecule of the polymerizable compound is preferably 2 or more, preferably 4 or less, and more preferably 3 or less.
  • Examples of the compound having two or more (meth)acryloyl groups include hexanediol di(meth)acrylate, butanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, and (poly)propylene glycol.
  • the content of the polymerizable compound is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the plurality of (meth)acrylic copolymer components, It is more preferably 2.5 parts by mass or more, preferably 100 parts by mass or less, and more preferably 50 parts by mass or less.
  • photopolymerization initiator When the polymerizable compound is cured with an active energy ray, it is preferable to incorporate a photopolymerization initiator into the adhesive composition. By blending a photopolymerization initiator, the reaction during active energy ray irradiation can be stabilized.
  • the photopolymerization initiator is not particularly limited as long as it generates radicals by the action of light. is mentioned. These photopolymerization initiators can be used alone or in combination of two or more. Among these photopolymerization initiators, photopolymerization initiators of hydrogen abstraction type benzophenones and intramolecular cleavage type acetophenones are preferable from the viewpoint of efficient intermolecular or intramolecular crosslinking.
  • the content of the photopolymerization initiator is preferably 0.01 parts by mass or more with respect to 100 parts by mass of the plurality of (meth)acrylic copolymer components, It is more preferably 0.1 parts by mass or more, still more preferably 0.5 parts by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 2 parts by mass or less. If the content of the photopolymerization initiator is too low, the curing speed tends to decrease or the curing tends to be insufficient.
  • the adhesive composition may contain an auxiliary agent for the photopolymerization initiator.
  • auxiliary agent include triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler's ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoate, and ethyl 4-dimethylaminobenzoate.
  • silane coupling agent A silane coupling agent may be added to the adhesive composition as necessary.
  • the silane coupling agent include, but are not limited to, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, Epoxy group-containing silane coupling agents 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, N-phenyl- ⁇ -aminopropyltrimethoxysilane; 3-acryloxypropyltrimethoxysilane, 3- Examples thereof include (meth)acryl
  • the content of the silane coupling agent that can be blended in the adhesive composition is 0.01% by mass or more, more preferably 0.02% with respect to 100 parts by mass of the plurality of (meth)acrylic copolymer components. % or more, preferably 1 part by mass or less, more preferably 0.6 part by mass or less.
  • plasticizer A plasticizer may be added to the adhesive composition, if necessary.
  • the plasticizer include, but are not limited to, oils such as paraffin oil and process oil; liquid rubbers such as liquid polyisoprene, liquid polybutadiene, and liquid ethylene-propylene rubber; tetrahydrophthalic acid, azelaic acid, benzoic acid, and phthalate.
  • Acids trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, citric acid and their derivatives; dioctyl phthalate (DOP), dibutyl phthalate (DBP), dioctyl adipate, adipine diisononyl acid (DINA), isodecyl succinate, and the like.
  • the said plasticizer may be used individually by 1 type, and may use 2 or more types together. Among these, liquid rubber is preferred.
  • the weight average molecular weight (Mw) of the liquid rubber is preferably 5,000 or more, more preferably 10,000, preferably 600 million or less, and more preferably 500 million or less. By adjusting the Mw of the liquid rubber to the above range, a highly flexible adhesive can be formed. A method for measuring the weight average molecular weight (Mw) will be described later.
  • the content of the plasticizer is preferably 1 part by mass or more, more preferably 5 parts by mass or more with respect to 100 parts by mass of the (meth)acrylic copolymer components. , more preferably 10 parts by mass or more, preferably 50 parts by mass or less, more preferably 40 parts by mass or less, still more preferably 30 parts by mass or less.
  • the adhesive composition can be produced by mixing the copolymer component, the cross-linking agent, and other optional additives.
  • the adhesive composition may contain a solvent derived from the production of the copolymer component, or a solution diluted to a viscosity suitable for forming an adhesive layer by adding an appropriate solvent. may be
  • 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. esters such as ethyl acetate and butyl acetate; cellosolve solvents such as ethyl cellosolve; and glycol ether solvents such as propylene glycol monomethyl ether. These solvents may be used singly or in combination of two or more.
  • the amount of the solvent used may be appropriately adjusted so that the adhesive composition has a viscosity suitable for coating, and is not particularly limited, but 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, more preferably 20% by mass to 70% by mass.
  • the adhesive composition is preferably used for forming a flexible display that can be repeatedly bent and stretched and an adhesive layer (adhesive material) used for the flexible display.
  • Examples of the flexible display that can be used by repeatedly bending and stretching include a foldable display that can be folded and a rollable display that can be rolled into a cylindrical shape.
  • Flexible displays are expected to be used for mobile terminals such as smartphones and tablet terminals, and stationary displays that can be stored.
  • the pressure-sensitive adhesive for flexible displays of the present invention is a cured product of the pressure-sensitive adhesive composition.
  • the adhesive material can be used as an adhesive material for a flexible display for bonding one flexible member and another flexible member that constitute a flexible display.
  • the gel fraction of the cured product is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably more than 70% by mass, and particularly preferably 75% by mass or more and 100% by mass or less. .
  • the gel fraction can be controlled by the blending amount of the cross-linking agent in the adhesive composition, the cross-linking treatment temperature, the cross-linking treatment time, and the like.
  • the pressure-sensitive adhesive sheet for a flexible display of the present invention comprises a pressure-sensitive adhesive layer used for bonding one flexible member and another flexible member constituting a flexible display, and a flexible and a sheet member, wherein the adhesive layer is formed from the adhesive material.
  • the configuration of the pressure-sensitive adhesive sheet includes an embodiment having an adhesive layer and a first flexible sheet member attached to one surface of the adhesive layer; An aspect having a first flexible sheet member and a second flexible sheet member adhered to the other surface of the adhesive layer may be mentioned.
  • FIG. 1 An example of the adhesive sheet of the present invention is shown in FIG.
  • the adhesive sheet 10 in FIG. 1 is composed of an adhesive layer 12, a first flexible sheet member 14 sandwiching the adhesive layer 12, and a second flexible sheet member 16. As shown in FIG. 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, and still more preferably 10 ⁇ m or more from the viewpoint of ensuring sufficient adhesion to the adherend.
  • the thickness of the adhesive layer is preferably 100 ⁇ m or less, more preferably 70 ⁇ m or less, and even more preferably 50 ⁇ m or less from the viewpoint of suppressing the protrusion of the adhesive layer.
  • the flexible sheet members include flexible base sheets and release sheets.
  • the base sheet is a sheet member that supports the adhesive layer, and this sheet member may be a functional sheet member.
  • the functional sheet members include cover films, barrier films, polarizing films, retardation films, optical compensation films, brightness enhancement films, diffusion films, and antireflection films.
  • the release sheet protects the adhesive layer until the adhesive layer is adhered to the adherend, and is peeled off from the adhesive layer before the adhesive layer is adhered to the adherend.
  • sheet is defined in JIS as a flat product that is thin and generally has a small thickness relative to its length and width.
  • a thin flat product with an extremely small thickness and an arbitrarily limited maximum thickness usually supplied in the form of a roll (Japanese Industrial Standard JIS K6900).
  • a thickness of 100 ⁇ m or more is called a sheet, and a thickness of less than 100 ⁇ m is sometimes called a film.
  • the boundary between a sheet and a film is not clear, and there is no need to distinguish between the two in the present invention. But "sheet” is included.
  • the flexible sheet members include polymeric material sheets and glass sheets.
  • the thickness of the flexible sheet member is not particularly limited, it is preferably 2 ⁇ m to 500 ⁇ m, more preferably 2 ⁇ m to 200 ⁇ m from the viewpoint of excellent handleability.
  • Polyimide resin polyester resin such as polyethylene terephthalate resin and polyethylene naphthalate resin; polycarbonate resin; poly(meth)acrylate resin; polystyrene resin; polyamide resin; polyolefin resin such as cycloolefin resin; polyphenylene sulfide resin; polyvinyl chloride resin; polyvinylidene chloride resin;
  • the flexible sheet member may be composed of a single layer comprising a layer containing one or more of the polymeric materials, or a layer containing one or more of the polymeric materials and a layer containing the polymeric material. It may be composed of two or more layers, such as a layer containing one or more polymeric materials different from the layer.
  • the flexible sheet member is preferably a release sheet whose surface in contact with the adhesive layer is subjected to release treatment.
  • Release agents used in the release treatment include, for example, silicone-based, fluorine-based, alkyd-based, unsaturated polyester-based, polyolefin-based, and wax-based 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 sheet member is a first release sheet
  • the second flexible sheet member is a second release sheet
  • the first release sheet and the second release sheet are attached such that the release surfaces of the first release sheet and the second release sheet are in contact with the adhesive layer. is preferred.
  • one of the release sheets 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 preferred.
  • the pressure-sensitive adhesive sheet can be produced, for example, by applying the above-described pressure-sensitive adhesive composition onto a flexible sheet member and, if necessary, curing the composition by drying and heat treatment to form the pressure-sensitive adhesive layer.
  • a reverse gravure coating method for example, a reverse gravure coating method, a direct gravure coating method, a die coating method, a bar coating method, a wire bar coating method, a roll coating method, a spin coating method, a dip coating method, a spray coating method, a knife
  • Various coating methods such as coating method and kiss coating method; inkjet method; various printing methods such as offset printing, screen printing and flexo printing can be employed.
  • 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 heating step is not particularly limited as long as the solvent or the like used in the adhesive composition can be removed and cured, but it is preferable to carry out at a temperature of 60°C to 150°C for about 20 seconds to 300 seconds.
  • the heating temperature is preferably 100°C to 130°C.
  • the adhesive composition is applied to the first flexible sheet member, and the adhesive layer is formed on the first flexible sheet member. is formed, the second flexible sheet member may be adhered to this adhesive layer. Furthermore, the adhesive layer may be cured as necessary.
  • the curing conditions include, for example, 60° C. for about 3 to 7 days.
  • a flexible laminated member of the present invention is a flexible laminated member comprising a first flexible member, a second flexible member, and an adhesive layer for bonding the first flexible member and the second flexible member together,
  • 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, appearance defects such as wavy appearance at the bent portion are suppressed.
  • the flexible laminated member 20 of FIG. 2 includes a first flexible member 22, a second flexible member 24, and an adhesive layer between the first flexible member 22 and the second flexible member 24 for bonding these flexible members together. 12.
  • the configuration of the flexible laminated member includes, for example, a configuration in which both the first flexible member and the second flexible member are constituent members of the flexible device;
  • a configuration that is a functional sheet member bonded to a flexible device may be mentioned.
  • the flexible device include a foldable display that can be folded and a rollable display that can be rolled into a cylinder.
  • the functional sheet members include cover films, barrier films, polarizing films, retardation films, optical compensation films, brightness enhancement films, diffusion films, antireflection films, transparent conductive films, metal mesh films, cushion films, and the like. be done.
  • the first flexible member and the second flexible member are members that can be repeatedly bent or bent for use.
  • Examples of the first flexible member and the second flexible member include flexible substrate materials, functional sheet members, and display elements (organic EL modules, electronic paper modules, etc.). At least one of the first flexible member and the second flexible member is preferably a display element.
  • the flexible laminate member can be used in flexible displays.
  • 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 is attached to the other surface of the adhesive sheet. is peeled off, and the exposed adhesive layer and the second flexible member are adhered to obtain a flexible laminated member.
  • the adhesive layer After coating the adhesive composition on one surface of the first flexible member and curing it by drying and heat treatment as necessary to form an adhesive layer, the adhesive layer has the releasability of a release sheet. Affix the surface. Then, the adhesive layer exposed by peeling off the release sheet is attached to the second flexible member to obtain a flexible laminated member.
  • the order of using the first flexible member and the second flexible member may be changed.
  • the adhesive layer can be formed using various coating methods and printing methods similar to those used in the production of the adhesive sheet, and the same applies to the drying and curing steps. Moreover, you may cure as needed.
  • the release sheet used for manufacturing the flexible laminated member may be the same as the release sheet used for the pressure-sensitive adhesive sheet.
  • the present invention will be described in more detail based on specific examples.
  • the present invention is by no means limited to the following examples, and can be modified as appropriate without changing the gist of the invention.
  • the polymerization rate of the polymer composition, the weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the polymer component, the thickness of the adhesive layer, and the evaluation of the adhesive were evaluated according to the following methods.
  • EHA 2-ethylhexyl acrylate
  • LA lauryl acrylate
  • AA acrylic acid
  • HBA 4-hydroxybutyl acrylate
  • BTEE ethyl 2-methyl-2-n-butyltheranyl-propionate
  • AIBN azobisisobutyronitrile
  • AcOEt ethyl acetate
  • Polystyrene as a standard substance 10,200, 2,630, 440 was used to generate a calibration curve.
  • GPC software manufactured by Tosoh Corporation, Ecosec Peak Separation (Version 1.04)
  • waveform separation is performed by Gaussian approximation for the retention time of 6 to 11 minutes of the measured chromatogram, and the weight average molecular weight of each polymer component ( Mw), molecular weight distribution (Mw/Mn), and content were determined.
  • Waveform separation parameters were set to Threshold: 0.5, SmoothWidth: 8, start retention time: 6, end retention time: 11.
  • Adhesive layer thickness (Adhesive layer thickness) Using a thickness measuring machine ("TH-104" manufactured by Tester Sangyo Co., Ltd.), the total thickness of the entire adhesive sheet is measured, and the thickness of the adhesive layer is obtained by subtracting the thickness of the release sheet from this total thickness. asked for
  • the adhesive layers (adhesive material) constituting the adhesive sheet were laminated together using a hand roller to prepare a laminate having a thickness of 600 ⁇ m, which was used as a test piece.
  • the measurement was performed using a viscoelasticity measuring device (manufactured by Anton Paar, MCR302), sandwiching the sample between 8 mm diameter parallel plates (the adhesion surface of which was roughened with No. 240 sandpaper) in an atmosphere of 25°C.
  • the test piece was compressed with an axial force of 1 N and left to stand for 10 minutes, then the axial force was changed to 0.05 N, and shear stress was immediately applied to strain the specimen up to 400% strain.
  • the strain was kept at 400% for 10 minutes, and the change in shear stress was measured to measure the stress relaxation time.
  • the shear stress was released (0 kPa) and left for 10 minutes, and the final strain after 10 minutes was measured to obtain the recovery rate.
  • the stress relaxation time was the time required for the shear stress to become 0.368 times the initial stress after the strain reached 400%.
  • the shear stress value 0.1 seconds after the start of shear stress application was defined as the initial stress.
  • the adhesive layers (adhesive material) constituting the adhesive sheet were laminated together using a hand roller to prepare a laminate having a thickness of 600 ⁇ m, which was used as a test piece.
  • the measurement was performed using a viscoelasticity measuring device (manufactured by Anton Paar, MCR302), sandwiching the sample between 8 mm diameter parallel plates (the adhesion surface of which was roughened with No. 240 sandpaper) in an atmosphere of 25°C.
  • the adhesive layer (adhesive material) constituting the adhesive sheet was laminated using a hand roller to prepare a laminate having a thickness of 600 ⁇ mm.
  • a test piece having a width of 10 mm and a length of 70 mm was cut out from the laminate.
  • the test was performed using a precision universal testing machine (AUTOGRAPH (registered trademark) AGX manufactured by Shimadzu Corporation). The test was carried out under an environment of 23° C. and 50%, with a distance between grips of 30 mm and a tensile speed of 30 mm/min.
  • the tensile stress was stretched from a state of 0 kPa until the tensile stress became 50 kPa, and then contracted until the tensile stress became 0 kPa. This elongation and contraction was repeated 12 times, and the presence or absence of breakage was confirmed. Those with no breakage were evaluated as "O”, and those with breakage were evaluated as "X".
  • the release sheet is peeled off from the adhesive layer, and the adhesive layer surface is covered with a polyimide film (Kapton (registered trademark) 100V: manufactured by Toray DuPont, thickness 25 ⁇ m) or white plate glass (S9112, manufactured by Matsunami Glass Industry Co., Ltd., 1.0 to 1.2 mm in thickness) was crimped by reciprocating a 2 kg roller twice.
  • a precision universal testing machine "AUTOGRAPH (registered trademark) AGS-1kNX, 50N load cell” manufactured by Shimadzu Corporation, the adhesive strength of the adhesive layer was measured under the conditions of a peel speed of 300 mm/min and a peel angle of 180°.
  • Table 1 shows the polymerization conditions for each polymerization composition.
  • the content of each structural unit in the polymerization composition, the amount of functional groups in 1 g of the polymerization composition, and the glass transition temperature were calculated from the charging ratio and polymerization rate of the monomers used in the polymerization reaction.
  • Polymer Components in Polymer Compositions Y a and Y b Polymeric composition Y a was subjected to gel permeation chromatography and waveform separation, and polymer components Y a 1, Y a 2 and Y a 3 were confirmed. Polymeric composition Yb was subjected to gel permeation chromatography and waveform separation, and polymer components Yb1 , Yb2 and Yb3 were confirmed. Table 3 shows the physical properties of the polymer components Y a 1 to Y a 3 and Y b 1 to Y b 3.
  • Adhesive composition No. 1 0.154 parts by mass of a cross-linking agent A (Duranate (registered trademark) MHG-80B) with respect to 381.7 parts by mass of the solution of the polymer composition X a obtained in Synthesis Example 1 (100 parts by mass of the polymer component), Butyl acetate was added and stirred to obtain adhesive composition No. 20 having a solid content of 20% by mass. got 1.
  • Adhesive composition No. 2 to 11 Adhesive composition No. 1 except that the formulation was changed as described in Tables 4 and 5. Adhesive composition No. 1 was prepared in the same manner as in 1. 2 to 11 were produced.
  • the blending amount of the cross-linking agent A shown in Tables 4 and 5 is the blending amount in terms of solid content.
  • a solid content is a component other than a solvent.
  • Adhesive composition no. 2 to 8 the first reactive group possessed by the polymer components X a 1, Y a 1, Y a 2 and Y a 3 is a hydroxy group, and the second reactive group possessed by the cross-linking agent A is an isocyanate group. be.
  • the first reactive group possessed by the polymer components X b 1, Y b 1, Y b 2 and Y b 3 is a carboxy group
  • the second reactive group possessed by the cross-linking agent B is an epoxy group.
  • Cross-linking agent A Duranate (registered trademark) MHG-80B (manufactured by Asahi Kasei, isocyanate-based cross-linking agent (hexamethylene diisocyanate-isocyanurate, functional group number 6, solid content concentration 80% by mass, NCO content 15.1% by mass))
  • Crosslinking agent B TETRAD (registered trademark)-C (Mitsubishi Gas Chemical Co., Ltd., 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, number of functional groups 4, solid content concentration 100% by mass, epoxy group amount; 9 .8mmol/g)
  • Plasticizer Kuraprene (registered trademark) LIR-410 (liquid isoprene rubber, weight average molecular weight 30000)
  • the pressure-sensitive adhesive composition contains (A) the (meth)acrylic copolymer component, but does not contain the (B) (meth)acrylic copolymer component.
  • the adhesive material formed from No. 1 had a small amount of strain when a shear stress of 20 kPa was applied, and was inferior in flexibility. In addition, the adhesion to glass was low.
  • the pressure-sensitive adhesive composition contains (A) (meth)acrylic copolymer component and (B) (meth)acrylic copolymer component, and (A) ( This is the case where the content of the meth)acrylic copolymer component is 75% by mass to 99% by mass.
  • These adhesive compositions no.
  • the adhesive materials formed from 2 and 3 were good in all of the recovery rate after being distorted to 400% strain, the amount of strain when a shear stress of 20 kPa was applied, and the repeated elongation test. Also, the adhesive strength was good for both glass and PI film.
  • Adhesive composition No. 4 to 8 the adhesive composition contains (A) (meth)acrylic copolymer component and (B) (meth)acrylic copolymer component, but (A) in the total polymer component This is the case where the content of the (meth)acrylic copolymer component is less than 75% by mass.
  • adhesive composition No. The adhesive materials formed from 4 to 6 had poor recovery rates after straining up to 400% strain.
  • adhesive composition No. Adhesives formed from 7 and 8 failed in repeated elongation tests.
  • the pressure-sensitive adhesive composition contains (A) (meth)acrylic copolymer component and (B) (meth)acrylic copolymer component, and (A) ( This is the case where the content of the meth)acrylic copolymer component is 75% by mass to 99% by mass.
  • These adhesive compositions no.
  • the adhesive materials formed from 9 to 11 were good in all of the recovery rate after being distorted to 400% strain, the amount of strain when a shear stress of 20 kPa was applied, and the repeated elongation test. Also, the adhesive strength was good for both glass and PI film.
  • the present invention includes the following aspects.
  • a pressure-sensitive adhesive composition for a flexible display for bonding one flexible member and another flexible member constituting the flexible display comprising a plurality of (meth)acrylic copolymer components and a cross-linking agent.
  • the (meth)acrylic copolymer component contains at least (A) a (meth)acrylic copolymer component and (B) a (meth)acrylic copolymer component, and the (A) (meth) The acrylic copolymer component has a first reactive group and a molecular weight distribution (Mw/Mn) of 3.0 or less, and the (B) (meth)acrylic copolymer component undergoes the first reaction having a molecular weight distribution (Mw/Mn) of greater than 3.0, the cross-linking agent having a second reactive group that reacts with the first reactive group, and the plurality of (meta) A pressure-sensitive adhesive composition for a flexible display, wherein the content of the (A) (meth)acrylic copoly
  • (Aspect 2) The adhesive composition for a flexible display according to Aspect 1, wherein the (A) (meth)acrylic copolymer component and (B) the (meth)acrylic copolymer component have a weight average molecular weight of 100,000 to 3,000,000. .
  • the isocyanate-based cross-linking agent is an aliphatic diisocyanate compound, an adduct of an aliphatic diisocyanate compound and an aliphatic diol compound, an adduct of an aliphatic diisocyanate compound, a biuret of an aliphatic diisocyanate compound, and an isocyanate of an aliphatic diisocyanate compound.
  • a pressure-sensitive adhesive sheet for a flexible display comprising: a pressure-sensitive adhesive layer used for bonding one flexible member and another flexible member constituting a flexible display; and a flexible sheet member adhered to at least one surface of the pressure-sensitive adhesive layer.
  • a pressure-sensitive adhesive sheet for a flexible display wherein the pressure-sensitive adhesive layer is formed from the pressure-sensitive adhesive material according to mode 9 or 10.
  • 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, and the first flexible sheet member is attached to the other surface of the adhesive layer.
  • the sheet member is a first release sheet
  • the second flexible sheet member is a second release sheet
  • the first release sheet and the second release sheet are attached such that the release surfaces of the first release sheet and the second release sheet are in contact with the adhesive layer.
  • a flexible laminated member comprising a first flexible member, a second flexible member, and an adhesive layer for bonding the first flexible member and the second flexible member together, wherein the adhesive layer comprises aspect 9 or 11.
  • a flexible laminated member comprising the adhesive material according to 10.
  • a flexible display comprising the flexible laminate member according to aspect 13 or 14.
  • a (meth)acrylic copolymer mixture used in an adhesive composition for a flexible display comprising at least (A) a (meth)acrylic copolymer component and (B) a (meth)acrylic copolymer component contains, the (A) (meth)acrylic copolymer component has a first reactive group, the molecular weight distribution (Mw/Mn) is 3.0 or less, and the (B) (meth)acrylic The system copolymer component has a first reactive group and has a molecular weight distribution (Mw/Mn) of greater than 3.0, the first reactive group is a hydroxy group and/or a carboxy group, and (Meth)acrylic copolymer, wherein the content of the (A) (meth)acrylic copolymer component in the (meth)acrylic copolymer mixture is 75% by mass to 99% by mass. Combined mixture.
  • Adhesive sheet 12 Adhesive layer 14: First flexible sheet member 16: Second flexible sheet member 20: Flexible laminate member 22: First flexible member 24: Second flexible member

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Adhesives Or Adhesive Processes (AREA)
PCT/JP2022/005346 2021-02-26 2022-02-10 フレキシブルディスプレイ用粘着組成物、粘着材および粘着シート Ceased WO2022181355A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN202280014119.7A CN116829670A (zh) 2021-02-26 2022-02-10 柔性显示器用粘合组合物、粘合材料和粘合片
JP2023502278A JP7698704B2 (ja) 2021-02-26 2022-02-10 フレキシブルディスプレイ用粘着組成物、粘着材および粘着シート
KR1020237027096A KR20230152660A (ko) 2021-02-26 2022-02-10 플렉시블 디스플레이용 점착 조성물, 점착재 및 점착시트

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021-030674 2021-02-26
JP2021030674 2021-02-26

Publications (1)

Publication Number Publication Date
WO2022181355A1 true WO2022181355A1 (ja) 2022-09-01

Family

ID=83049168

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/005346 Ceased WO2022181355A1 (ja) 2021-02-26 2022-02-10 フレキシブルディスプレイ用粘着組成物、粘着材および粘着シート

Country Status (5)

Country Link
JP (1) JP7698704B2 (https=)
KR (1) KR20230152660A (https=)
CN (1) CN116829670A (https=)
TW (1) TW202244224A (https=)
WO (1) WO2022181355A1 (https=)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7829172B2 (ja) * 2021-02-26 2026-03-13 大塚化学株式会社 フレキシブルディスプレイ用粘着組成物、粘着材および粘着シート
TWI806171B (zh) * 2021-09-27 2023-06-21 華碩電腦股份有限公司 色彩校正模組以及具有其之電子裝置

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016047924A (ja) * 2014-08-27 2016-04-07 日本合成化学工業株式会社 粘着剤組成物、粘着剤及び粘着シート
JP2019031598A (ja) * 2017-08-07 2019-02-28 三菱ケミカル株式会社 光硬化型粘着シート
WO2020095870A1 (ja) * 2018-11-06 2020-05-14 三菱ケミカル株式会社 粘着剤層、粘着剤組成物、無溶剤型粘着剤組成物、粘着剤および粘着シート
JP2021134321A (ja) * 2020-02-28 2021-09-13 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

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5554503B2 (ja) 2008-03-18 2014-07-23 リンテック株式会社 再剥離性工程フィルム
JP6611252B2 (ja) 2016-03-28 2019-11-27 リンテック株式会社 半導体加工用シート
CN109790420A (zh) 2016-09-30 2019-05-21 日东电工株式会社 光学用粘合剂层、光学用粘合剂层的制造方法、带粘合剂层的光学膜、及图像显示装置
JP6921836B2 (ja) 2016-09-30 2021-08-18 日東電工株式会社 光学用粘着剤層、光学用粘着剤層の製造方法、粘着剤層付光学フィルム、及び、画像表示装置
WO2019021843A1 (ja) 2017-07-25 2019-01-31 大塚化学株式会社 粘着剤組成物および粘着フィルム
JP7004564B2 (ja) 2017-12-19 2022-01-21 リンテック株式会社 粘着シート、繰り返し屈曲積層部材および繰り返し屈曲デバイス
JP7172409B2 (ja) * 2018-10-10 2022-11-16 東亞合成株式会社 粘着剤組成物及びその製造方法
CN114728507B (zh) 2019-12-06 2023-10-10 大塚化学株式会社 粘合材料、粘合片和弯曲性层叠部件
JP7664697B2 (ja) * 2020-11-16 2025-04-18 大塚化学株式会社 フレキシブルディスプレイ用粘着組成物、粘着材および粘着シート

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016047924A (ja) * 2014-08-27 2016-04-07 日本合成化学工業株式会社 粘着剤組成物、粘着剤及び粘着シート
JP2019031598A (ja) * 2017-08-07 2019-02-28 三菱ケミカル株式会社 光硬化型粘着シート
WO2020095870A1 (ja) * 2018-11-06 2020-05-14 三菱ケミカル株式会社 粘着剤層、粘着剤組成物、無溶剤型粘着剤組成物、粘着剤および粘着シート
JP2021134321A (ja) * 2020-02-28 2021-09-13 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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
JP7282288B1 (ja) * 2021-10-18 2023-05-26 大塚化学株式会社 粘着材および粘着シート

Also Published As

Publication number Publication date
JPWO2022181355A1 (https=) 2022-09-01
CN116829670A (zh) 2023-09-29
KR20230152660A (ko) 2023-11-03
JP7698704B2 (ja) 2025-06-25
TW202244224A (zh) 2022-11-16

Similar Documents

Publication Publication Date Title
JP7282288B1 (ja) 粘着材および粘着シート
KR102762687B1 (ko) 점착재, 점착 시트 및 굴곡성 적층 부재
JP6888181B1 (ja) 粘着材、粘着シートおよび屈曲性積層部材
JP7698704B2 (ja) フレキシブルディスプレイ用粘着組成物、粘着材および粘着シート
CN103242748B (zh) 丙烯酸类压敏胶粘带
JP7829172B2 (ja) フレキシブルディスプレイ用粘着組成物、粘着材および粘着シート
CN111978883A (zh) 粘合片
TW202528504A (zh) 柔性顯示器用黏著片、柔性顯示器用積層體及柔性顯示器
CN117795028A (zh) 粘合片
JP7664697B2 (ja) フレキシブルディスプレイ用粘着組成物、粘着材および粘着シート
JP7602354B2 (ja) フレキシブルディスプレイ用粘着組成物および粘着シート
JP2023060827A (ja) フレキシブルディスプレイ用粘着組成物、粘着材および粘着シート
WO2023080054A1 (ja) 粘着材および粘着シート
CN116034027A (zh) 加强用薄膜、光学构件及电子构件
WO2024135432A1 (ja) 粘着フィルム
JP2025088730A (ja) 粘着組成物、粘着材および粘着シート
JP2024051532A (ja) 保護フィルム付きカバーフィルム
JP2022092984A (ja) 粘着剤用（メタ）アクリル系共重合体およびこれを用いた粘着フィルム

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22759394

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2023502278

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 202280014119.7

Country of ref document: CN

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22759394

Country of ref document: EP

Kind code of ref document: A1