CN116285716A - Adhesive sheet for flexible display, laminate, and method for producing flexible display - Google Patents

Adhesive sheet for flexible display, laminate, and method for producing flexible display Download PDF

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Publication number
CN116285716A
CN116285716A CN202211529811.1A CN202211529811A CN116285716A CN 116285716 A CN116285716 A CN 116285716A CN 202211529811 A CN202211529811 A CN 202211529811A CN 116285716 A CN116285716 A CN 116285716A
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CN
China
Prior art keywords
flexible display
adhesive layer
layer
mass
acrylic
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.)
Pending
Application number
CN202211529811.1A
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Chinese (zh)
Inventor
田邉慎吾
古野寛之
早坂努
福田克哲
石智文
入江刚史
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.)
Toyochem Co Ltd
Artience Co Ltd
Original Assignee
Toyo Ink SC Holdings Co Ltd
Toyochem Co Ltd
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Filing date
Publication date
Application filed by Toyo Ink SC Holdings Co Ltd, Toyochem Co Ltd filed Critical Toyo Ink SC Holdings Co Ltd
Publication of CN116285716A publication Critical patent/CN116285716A/en
Pending legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • 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]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • 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
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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
    • 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
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • 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
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/017—Additives being an antistatic agent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • 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
    • C09J2483/00—Presence of polysiloxane
    • C09J2483/005—Presence of polysiloxane in the release coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Theoretical Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention provides an adhesive sheet, a laminate and a method for manufacturing a flexible display, which can form a flexible display with excellent bending property, winding offset resistance and dust resistance. The object is achieved by an adhesive sheet for flexible display, comprising an acrylic adhesive layer on a release agent layer of an antistatic release film, wherein the release agent layer has a surface resistance value of 1X 10 under an atmosphere of 23-50% RH 11 The main component of the release agent layer is linear silicone, the content of branched silicone is 1 mass% or less, and the glass transition temperature of the acrylic adhesive layer is-55 ℃ or less.

Description

Adhesive sheet for flexible display, laminate, and method for producing flexible display
Technical Field
The present invention relates to an adhesive sheet for forming a flexible display, a laminate having an adhesive layer formed of the adhesive sheet, and a flexible display.
Background
In recent years, an input device using an image display device such as a liquid crystal display (liquid crystal display, LCD) or an organic light-emitting diode (OLED) in combination with a touch panel (touch panel) has been popular. Transparent conductive films used in touch panels are laminated on a member such as a support glass via an adhesive layer. In addition, a polarizing plate film used in an image display device is attached to a liquid crystal module or an organic EL module via an adhesive layer.
As the image display device, a flat panel display using a glass substrate is the mainstream, but in recent years, a flexible display such as a Foldable display (folding display) or a roll display (roll display) using a flexible substrate such as plastic has been developed. Such a flexible display has various advantages such as light weight, thickness, flexibility, and the like, and also excellent design properties, as compared with a conventional flat panel display using a glass substrate.
Such an adhesive sheet has conventionally been required to have a property of not causing foaming or peeling in a high-temperature environment or a high-temperature and high-humidity environment, but in recent years, flexibility has been further required. As an example of the market, flexibility is becoming a fundamental property in the case of a flexible display device that can be used for a folding display device. However, although attempts have been made to improve the flexibility at a specific place, there has been no improvement in an adhesive sheet that satisfies the flexibility at a plurality of places at the same time. The flexibility is required to have such a property that foaming, floating and peeling do not occur when repeatedly bending.
In order to solve these problems, patent document 1 discloses an adhesive comprising a base polymer, a photocurable compound, and a photoinitiator. Patent document 2 discloses a flexible device carrier sheet including a base material having antistatic properties, an adhesive layer, and a release sheet.
[ Prior Art literature ]
[ patent literature ]
[ patent document 1] Japanese patent laid-open No. 2020-097737
[ patent document 2] Japanese patent application laid-open No. 2018-203873
Disclosure of Invention
[ problem to be solved by the invention ]
Further, in recent years, a scroll display has been attracting attention as a more advanced display. As an adhesive sheet used for a roll type display, a tighter bending property than before is required, and in addition to a specific bending property (folding bending property), a strain adaptability capable of withstanding bending properties at a plurality of places (roll bending property) is required in order to cope with such an operation as twisting. In addition, in scroll displays, in order to make the definition of the display image directly visible, the market demand level for dust resistance that does not allow dust or dust to be mixed in is at a higher level than before. In addition, in the case of mass production of the adhesive sheet, when curing in a state of being wound from roll to roll, there is a concern that the sharpness of the image quality may be impaired due to a positional displacement (winding displacement) of the adhesive layer in the shearing direction.
Accordingly, an object of the present invention is to provide an adhesive sheet capable of forming a flexible display excellent not only in bending property than before but also in winding displacement resistance and dust resistance.
The present invention also aims to provide an adhesive sheet having excellent strain adaptability, which can be applied to applications requiring stricter bending properties such as a roll display.
[ means of solving the problems ]
The present inventors have made diligent studies and as a result, have found that the following aspects can solve the problems of the present invention, and have completed the present invention.
Namely, the present invention relates to an adhesive sheet for flexible display, comprising an acrylic adhesive layer on a release agent layer of an antistatic release film, wherein the release agent layer has a surface resistance value of 1X 10 under an atmosphere of 23 to 50% RH 11 The main component of the release agent layer is linear silicone, the content of branched silicone is 1 mass% or less, and the glass transition temperature of the acrylic adhesive layer is-55 ℃ or less.
The present invention also relates to the adhesive sheet for flexible display, wherein the film thickness of the acrylic adhesive layer is 50 μm or more.
The present invention also relates to the pressure-sensitive adhesive sheet for flexible displays, wherein the acrylic pressure-sensitive adhesive layer contains an acrylic copolymer (a), and the acrylic copolymer (a) contains an acrylic copolymer having a mass average molecular weight of 80 ten thousand or more.
The present invention also relates to the adhesive sheet for flexible display, wherein the acrylic copolymer (a) is a copolymer of a monomer mixture containing at least any one of an alkyl (meth) acrylate monomer (a-1) having an alkyl group having 1 or 2 carbon atoms and an alkyl (meth) acrylate monomer (a-2) having an alicyclic structure.
The present invention also relates to the pressure-sensitive adhesive sheet for flexible displays, wherein the monomer mixture further contains an alkyl (meth) acrylate monomer (a-3) having an alkyl group having 8 to 12 carbon atoms, and the content of the monomer (a-3) is 80 mass% or more in 100 mass% of the monomer mixture.
The present invention also relates to the adhesive sheet for flexible display, wherein the acrylic adhesive layer contains an antistatic agent, and the acrylic adhesive layer has a surface resistance value of 1X 10 under an atmosphere of 23-50% RH 10 Omega/gamma or less.
The present invention also relates to a method for producing a laminate including an adherend and an acrylic adhesive layer, the method comprising: and a step of peeling the antistatic treatment release film from the flexible display adhesive sheet and attaching an acrylic adhesive layer to an adherend.
The present invention also relates to a method for manufacturing a flexible display including a flexible image display portion and an acrylic adhesive layer, the method comprising: and a step of peeling the antistatic treatment release film from the flexible display adhesive sheet and attaching an acrylic adhesive layer to a flexible image display unit.
[ Effect of the invention ]
The present invention can provide an adhesive sheet which can form a flexible display having not only excellent bending properties but also excellent winding displacement resistance and dust resistance.
Further, the adhesive sheet of the present invention can be applied to applications requiring more severe flexibility such as a roll display, and can provide a flexible display which is small in storage, large in screen when used, and excellent in visibility.
Drawings
Fig. 1 is a schematic cross-sectional view partially showing an example of an adhesive sheet of the present invention.
Fig. 2 is a schematic cross-sectional view partially showing a laminate as an example of use of the adhesive sheet of the present invention.
Fig. 3 is a schematic cross-sectional view partially showing a display as an example of use of the adhesive sheet of the present invention.
[ description of symbols ]
1: adhesive layer 1
2: antistatic treatment release film
3: film base material (cover panel)
4: polarizing plate
5: adhesive layer 2
6: barrier layer
7: organic EL layer
8: support body
9: organic EL unit
Detailed Description
The following describes structural examples of the adhesive sheet, the laminate, and the display of the present invention, but is not limited thereto.
Definitions are made for terms used in the present specification. The term (meth) acrylate includes acrylate and methacrylate. The monomer is a monomer containing an ethylenically unsaturated group. The adherend is an object to which the adhesive sheet is to be attached. In the present invention, sheet, film and tape are synonymous, "RH" means relative humidity.
In the present specification, "acrylic copolymer (a)" is sometimes referred to as "copolymer (a)", "adhesive for flexible display" is referred to as "adhesive", the "alkyl (meth) acrylate monomer (a 1) having an alkyl group of 1 or 2 carbon atoms" is referred to as "monomer (a 1)", the "alkyl (meth) acrylate monomer (a 2) having an alicyclic structure" is referred to as "monomer (a 2)", the "alkyl (meth) acrylate monomer (a 3) having an alkyl group of 8 to 12 carbon atoms" is referred to as "monomer (a 3)", the "monomer (a 4) having a hydroxyl group or the" monomer (a 4) ", and the" other monomer (a 5) copolymerizable with the monomers (a-1) to (a-4) "are referred to as" monomer (a 5) ".
Further, each component appearing in the present specification may be used singly or in combination of two or more, unless otherwise noted.
Adhesive sheet "
The adhesive sheet of the present invention includes an acrylic adhesive layer on a release agent layer of an antistatic treatment release film, and is used for forming a flexible display.
The antistatic treatment release film was the following film: an antistatic layer is included on one or both sides of the film substrate, and a stripper layer is further included on an upper surface thereof with respect to the antistatic layer, and a stripper layer is included on the film substrate with respect to a side not including the antistatic layer.
Can be formed by coating an adhesive on the release agent layer of the antistatic treatment release film by a known method.
Acrylic adhesive layer
The glass transition temperature (Tg) of the acrylic adhesive layer is not higher than-55 ℃ as a result of differential scanning calorimetric analysis (differential scanning calorimetry, DSC) of the adhesive layer. Preferably at-57℃or lower, more preferably at-60℃or lower. The acrylic adhesive layer has a glass transition temperature of-55 ℃ or lower, and thus exhibits sufficient strain adaptability.
The acrylic adhesive layer is a sheet obtained by forming a film on a release film of an acrylic adhesive containing the acrylic copolymer (a) and optionally containing a curing agent, additives, and the like by a known method.
The acrylic pressure-sensitive adhesive layer preferably contains an acrylic copolymer having a mass average molecular weight of 80 ten thousand or more as the acrylic copolymer (a). In addition, it is preferable to contain an antistatic agent.
(acrylic copolymer (A))
The acrylic copolymer (A) is a copolymer of a monomer mixture.
The monomers constituting the acrylic copolymer (A) can be classified into the following monomers (a-1) to (a-5).
(a-1) alkyl (meth) acrylate monomer having alkyl group of 1 or 2 carbon atoms
(a-2) alkyl (meth) acrylate monomer having alicyclic structure
(a-3) alkyl (meth) acrylate monomer having an alkyl group having 8 to 12 carbon atoms
(a-4) a monomer having a hydroxyl group, or a monomer having a carboxyl group
(a-5) other monomers copolymerizable with the monomers (a-1) to (a-4)
The acrylic copolymer (A) is a copolymer of a monomer mixture containing at least any one of the monomers (a-1) and (a-2), and therefore has a substituent that generates cohesive force in a side chain. Thus, an adhesive sheet excellent in bendability and adhesive force can be produced, and is preferable.
The content of the monomer (a-1) and the monomer (a-2) is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, based on 100% by mass of the monomer mixture. When both the monomer (a-1) and the monomer (a-2) are contained, the total amount of the both is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, in 100% by mass of the monomer mixture.
When the content is 1 mass% or more, a sufficient cohesive force can be easily obtained. In addition, the content of 30 mass% or less is preferable because it is easy to achieve both of the cohesive force and the moderation.
[ monomer (a-1) ]
The monomer (a-1) is an alkyl (meth) acrylate monomer having an alkyl group having 1 or 2 carbon atoms, and specifically, methyl (meth) acrylate, ethyl (meth) acrylate, or the like can be exemplified. Among them, methyl (meth) acrylate is preferable from the viewpoints of flexibility and adhesion.
[ monomer (a-2) ]
The monomer (a-2) is an alkyl (meth) acrylate monomer having an alicyclic structure, and specifically, may be exemplified by: cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and the like. Among them, isobornyl (meth) acrylate is preferable from the viewpoints of bendability and adhesion.
[ monomer (a-3) ]
The monomer (a-3) is an alkyl (meth) acrylate monomer having an alkyl group having 8 to 12 carbon atoms, and specifically, examples thereof include: octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, and the like. Among them, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and lauryl (meth) acrylate are preferable from the viewpoint of flexibility.
Further, the use of the alkyl (meth) acrylate monomer (a-3) having an alkyl group having 8 to 12 carbon atoms is more preferable because the mildness of the adhesive is improved, a strong adhesive layer can be obtained, and the flexibility can be improved.
The content of the monomer (a-3) in 100% by mass of the monomer mixture is preferably 50% by mass to 98% by mass, more preferably 65% by mass to 98% by mass, and still more preferably 80% by mass to 95% by mass.
When the content is 50 mass% or more, sufficient moderation can be easily obtained. In addition, the content of the monomer (a-1) or the monomer (a-2) generating the cohesive force and the monomer (a-4) forming the crosslinking point is preferably 98 mass% or less because the content is easily ensured, and the moderation and the cohesive force are easily compatible.
[ monomer (a-4) ]
The monomer (a-4) is a monomer having a hydroxyl group or a monomer having a carboxyl group.
The monomer having a hydroxyl group is not limited as long as it has a hydroxyl group in the molecule, and specifically, examples thereof include: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like. Among them, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable from the viewpoints of cohesive force and adhesive force.
The carboxyl group-containing monomer is not limited as long as it has a carboxyl group in the molecule, and specifically, examples thereof include: (meth) acrylic acid, p-carboxybenzyl acrylate, beta-carboxyethyl acrylate, maleic acid, monoethyl maleic acid, itaconic acid, citraconic acid, fumaric acid, and the like. Among them, (meth) acrylic acid is preferable from the viewpoints of cohesive force and adhesive force.
In addition, the inclusion of the monomer (a-4) is more preferable because the cohesive force of the adhesive is improved, a strong adhesive layer can be obtained, and the adhesive force can be improved.
The content of the monomer (a-4) is preferably 0.5 to 2.5 mass% and more preferably 0.5 to 2.0 mass% based on 100 mass% of the monomer mixture. When both the monomer having a hydroxyl group and the monomer having a carboxyl group are contained, the total amount of the two is preferably 0.5 to 2.5 mass%, more preferably 0.5 to 2.0 mass% in 100 mass% of the monomer mixture.
A content of 0.5 mass% or more is preferable because sufficient cohesive force can be easily obtained, and a content of 2.5 mass% or less is preferable because cohesive force and moderation can be easily achieved.
From the viewpoint of easily satisfying both the cohesive force and the moderation, the case where both the monomer having a hydroxyl group and the monomer having a carboxyl group are contained is preferable to the case where each is contained alone.
[ monomer (a-5) ]
The monomer (a-5) is another monomer copolymerizable with the monomers (a-1) to (a-4), and the acrylic pressure-sensitive adhesive (A) of the present invention may contain the monomer (a-5) in addition to the monomers (a-1) to (a-4).
The monomers (a-5) may be exemplified by: alkyl (meth) acrylate monomers other than the monomers (a-1) to (a-3), epoxy group-containing (meth) acrylic monomers, amino group-containing (meth) acrylic monomers, alkyleneoxy group-containing monomers, other vinyl monomers, and the like.
Examples of the alkyl (meth) acrylate monomer other than the monomers (a-1) to (a-3) include: propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, and the like.
Examples of the monomer having an epoxy group include: glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, 6-methyl-3, 4-epoxycyclohexylmethyl (meth) acrylate, and the like.
Examples of the monomer having an amino group include: mono (meth) acrylic acid monoalkylamino esters such as mono (meth) acrylic acid monoethyl ester, mono (meth) acrylic acid monoethyl amino ethyl ester, mono (meth) acrylic acid monomethyl amino propyl ester, and mono (meth) acrylic acid monoethyl amino propyl ester.
Examples of the monomer having an alkyleneoxy group include a monomer represented by the following general formula (1) and a monomer represented by the following general formula (2).
[ chemical 1]
Figure BDA0003972711350000061
[ chemical 2]
Figure BDA0003972711350000062
In the general formula (1) and the general formula (2), R 1 、R 2 Each independently represents a hydrogen atom or a methyl group, n and m are integers representing a repeating unit, and 1+.n+.25, 1+.m+.25, preferably 1+.n+.13, 1+.m+.5.
Examples of the commercially available monomers represented by the general formula (1) include: methoxyethyl acrylate (manufactured by Osaka organic chemical industry Co., ltd.; in the formula (1), R 1 Is a hydrogen atom, n=1), methoxy diethylene glycol acrylate (manufactured by osaka organic chemical industry company; in the formula (1), R 1 Is a hydrogen atom, n=2), methoxy triethylene glycol acrylate (manufactured by osaka organic chemical industry company; in the formula (1), R 1 Is a hydrogen atom, n=3), methoxy group polymerEthylene glycol #400 acrylate (manufactured by Xinzhongcun chemical industry Co., ltd.; in the formula (1), R 1 Is a hydrogen atom, n=9), methoxypolyethylene glycol #600 acrylate (manufactured by new middle village chemical industry company; in the formula (1), R 1 Is a hydrogen atom, n=13), methoxypolyethylene glycol #1000 acrylate (manufactured by new middle village chemical industry company; in the formula (1), R 1 Is a hydrogen atom, n=23), methoxy diethylene glycol methacrylate (manufactured by new middle village chemical industry company; in the formula (1), R 1 Methyl, n=2), methoxy triethylene glycol methacrylate (manufactured by new middle village chemical industry company; in the formula (1), R 1 Methyl, n=3), methoxy tetraethylene glycol methacrylate (manufactured by new middle village chemical industry company; in the formula (1), R 1 Methyl, n=4), methoxypolyethylene glycol #400 methacrylate (manufactured by new middle village chemical industry company; in the formula (1), R 1 Is a hydrogen atom, n=9), methoxypolyethylene glycol #600 methacrylate (manufactured by new middle village chemical industry company; in the formula (1), R 1 Is a hydrogen atom, n=13), methoxypolyethylene glycol #1000 methacrylate (manufactured by new middle village chemical industry company; in the formula (1), R 1 Is a hydrogen atom, n=23).
Examples of the commercially available monomer represented by the general formula (2) include methoxy tripropylene glycol acrylate (produced by Xinzhou chemical industry Co., ltd.; in the formula (2), R 2 Hydrogen atom, m=3).
Examples of the vinyl monomer include: vinyl acetate, vinyl butenoate, styrene, acrylonitrile, and the like.
The content of the monomer (a-5) is preferably 5 to 50% by mass based on 100% by mass of the monomer mixture. If the content is 5 mass% or more, the cohesive force is improved. In addition, if the content is 50 mass% or less, it is easy to achieve both the cohesive force and the bendability, and therefore, it is preferable.
[ production of acrylic copolymer (A) ]
The acrylic copolymer (a) can be produced by polymerizing a monomer mixture. The polymerization may be a known polymerization method such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, etc., and is preferably solution polymerization. The solvent used in the solution polymerization is preferably, for example, acetone, methyl acetate, ethyl acetate, toluene, xylene, anisole, methyl ethyl ketone, cyclohexanone, or the like. The polymerization temperature is preferably 60℃to 120℃in boiling point reaction. The polymerization time is preferably about 5 hours to 12 hours.
The polymerization initiator used in the polymerization is preferably a radical polymerization initiator. The radical polymerization initiator is generally a peroxide or azo compound. Examples of peroxides include: dialkyl peroxides such as di-t-butyl peroxide, diisopropylphenyl peroxide, t-butylcumyl peroxide, α' -bis (t-butylperoxy-m-isopropyl) benzene, and 2, 5-di (t-butylperoxy) hexyne-3; peroxy esters such as t-butyl peroxybenzoate, t-butyl peroxyacetate, and 2, 5-dimethyl-2, 5-bis (benzoylperoxy) hexane; ketone peroxides such as cyclohexanone peroxide, 3, 5-trimethylcyclohexanone peroxide, and methylcyclohexanone peroxide; peroxyketals such as 2, 2-bis (4, 4-di-t-butylperoxycyclohexyl) propane, 1-bis (t-butylperoxy) 3, 5-trimethylcyclohexane, 1-bis (t-butylperoxy) cyclohexane, n-butyl-4, 4-bis (t-butylperoxy) valerate, and the like; hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2, 5-dimethylcyclohexane-2, 5-dihydroperoxide and the like; diacyl peroxides such as benzoyl peroxide, decanoyl peroxide, lauroyl peroxide and 2, 4-dichlorobenzoyl peroxide; and peroxydicarbonates such as bis (t-butylcyclohexyl) peroxydicarbonate.
Examples of the azo compound include: 2,2' -azobisisobutyronitrile (AIBN (2, 2' -azobisisobutyronitrile)), 2' -azobis (2-methylbutyronitrile) and the like; 2,2' -azobisvaleronitrile such as 2,2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile) and 2,2' -azobis (2, 4-dimethylvaleronitrile); 2,2 '-azobispropionitrile such as 2,2' -azobis (2-hydroxymethyl propionitrile); 1,1 '-azobis-1-alkylnitrile (alkenenitrile) such as 1,1' -azobis (cyclohexane-1-carbonitrile) and the like.
The polymerization initiator is preferably used in an amount of 0.01 to 10 parts by mass, more preferably 0.05 to 2 parts by mass, based on 100 parts by mass of the monomer mixture.
[ Mass average molecular weight (Mw) ]
The mass average molecular weight of the copolymer (A) is preferably 60 to 200 tens of thousands, more preferably 80 to 180 tens of thousands, and still more preferably 100 to 150 tens of thousands. When the amount is in the range of 60 to 200 ten thousand, the cohesive force is further improved, and bending properties such as winding displacement resistance and strain adaptability and adhesive force are further improved. The mass average molecular weight is a polystyrene-equivalent value measured by gel permeation chromatography (gel permeation chromatography, GPC).
(hardener)
The curing agent reacts with the hydroxyl group and/or carboxyl group of the copolymer (a) to increase the cohesive force of the adhesive layer and to increase the bendability or the adhesive force.
Examples of the hardening agent include: isocyanate compounds, epoxy compounds, aziridine compounds, carbodiimide compounds, metal chelates, or the like. Among these, isocyanate compounds are preferable because they can improve the bendability by using them as a hardener.
The isocyanate compound is an isocyanate having two or more isocyanate groups. The isocyanate compound is preferably an isocyanate monomer such as an aromatic polyisocyanate, an aliphatic polyisocyanate, an aromatic aliphatic polyisocyanate, or a cycloaliphatic polyisocyanate, and a biuret, a urethane (nurate) or an adduct of these.
Examples of the aromatic polyisocyanate include: 1, 3-phenylene diisocyanate, 4' -diphenyl diisocyanate, 1, 4-phenylene diisocyanate, 4' -diphenylmethane diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 4' -toluidine diisocyanate, 2,4, 6-triisocyanate toluene, 1,3, 5-triisocyanate benzene, benzidine diisocyanate, 4' -diphenyl ether diisocyanate, 4',4 "-triphenylmethane triisocyanate, and the like.
Examples of aliphatic polyisocyanates include: trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (alias: HMDI (hexamethylene diisocyanate)), pentamethylene diisocyanate, 1, 2-propylene diisocyanate, 2, 3-butylene diisocyanate, 1, 3-butylene diisocyanate, dodecamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, and the like.
Examples of the aromatic aliphatic polyisocyanate include: omega, omega '-diisocyanate-1, 3-dimethylbenzene, omega' -diisocyanate-1, 4-diethylbenzene, 1, 4-tetramethylxylylene diisocyanate, 1, 3-tetramethylxylylene diisocyanate, and the like.
Examples of the alicyclic polyisocyanate include: 3-isocyanatomethyl-3, 5-trimethylcyclohexyl isocyanate (alias: IPDI (isophorone diisocyanate), isophorone diisocyanate), 1, 3-cyclopentane diisocyanate, 1, 3-cyclohexane diisocyanate, 1, 4-cyclohexane diisocyanate, methyl-2, 6-cyclohexane diisocyanate, 4' -methylenebis (cyclohexyl isocyanate), 1, 4-bis (isocyanatomethyl) cyclohexane, and the like.
The biuret is a self-condensate with biuret bond formed by self-condensing isocyanate monomers. The biuret is exemplified by the biuret of hexamethylene diisocyanate.
The allophanate is a trimer of isocyanate monomers. Examples include: trimers of hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, and the like.
The adduct is a difunctional or higher isocyanate compound obtained by reacting an isocyanate monomer with a difunctional or higher compound containing a low-molecular active hydrogen. The adducts can be exemplified by: a compound obtained by reacting trimethylolpropane with hexamethylene diisocyanate, a compound obtained by reacting trimethylolpropane with toluene diisocyanate, a compound obtained by reacting trimethylolpropane with xylylene diisocyanate, a compound obtained by reacting trimethylolpropane with isophorone diisocyanate, a compound obtained by reacting 1, 6-hexane diol with hexamethylene diisocyanate, and the like.
The isocyanate compound is preferably a trifunctional isocyanate compound from the viewpoint of forming a sufficient crosslinked structure. The isocyanate compound is more preferably an adduct, which is a reaction product of an isocyanate monomer and a trifunctional, low-molecular active hydrogen-containing compound, and an allophanate body. The isocyanate compound is preferably a trimethylolpropane adduct of hexamethylene diisocyanate, an allophanate of hexamethylene diisocyanate, a trimethylolpropane adduct of toluene diisocyanate, an allophanate of toluene diisocyanate, a trimethylolpropane adduct of isophorone diisocyanate, an allophanate of isophorone diisocyanate, more preferably a trimethylolpropane adduct of hexamethylene diisocyanate, a trimethylolpropane adduct of toluene diisocyanate, a trimethylolpropane adduct of isophorone diisocyanate.
Examples of the epoxy compound include: glycerol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, N ' -tetraglycidyl-m-xylylenediamine, 1, 3-bis (N, N ' -diglycidyl aminomethyl) cyclohexane, N ' -tetraglycidyl aminophenylmethane, and the like.
Examples of the aziridine compound include: n, N ' -diphenylmethane-4, 4' -bis (1-carbonyl aziridine), tris-2, 4,6- (1-aziridinyl) -1,3, 5-triazine, 4' -bis (methyleneiminocarbonylamino) diphenylmethane, and the like.
The carbodiimide compound is preferably a high molecular weight polycarbodiimide produced by subjecting a diisocyanate compound to a decarbonated condensation reaction in the presence of a carbodiimidization catalyst. The commercial product of the high molecular weight polycarbodiimide is preferably carbodile series (Carbodilite series) from the Hill-opening products. Among them, carbodile (Carbodilite) V-03, 07, 09 is preferable because of excellent compatibility with an organic solvent.
The metal chelate is preferably, for example: and complex compounds of polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium with acetylacetone or ethyl acetoacetate. Examples of the metal chelate include: aluminum ethylacetoacetate-diisopropanol, aluminum triacetylacetonate, aluminum diethylacetoacetate-monoacetylacetonate, aluminum alkylacetoacetate-diisopropanol.
The curing agent is preferably contained in an amount of 0.01 to 1.0 parts by mass, more preferably 0.03 to 0.5 parts by mass, based on 100 parts by mass of the copolymer (a). If the content is 0.01 parts by mass or more, the cohesion is further improved, and if the content is 4 parts by mass or less, both the cohesion and the flexibility are easily achieved, which is preferable.
(antistatic agent)
The acrylic adhesive of the present specification may contain an antistatic agent within a range that does not hinder the effects of the present invention. When the antistatic agent is contained, adhesion of dust or dust can be reduced when the release film is peeled from the adhesive sheet, and on the other hand, there is a concern that adhesion to the adherend is impaired. In use, it is important to achieve both the dust resistance and the adhesion by using the kind and amount of the antistatic agent.
Examples of antistatic agents include: inorganic salts, ionic liquids, ionic solids, surfactants, and the like. Of these, ionic liquids are preferred. In addition, "ionic liquids" are also known as normal temperature molten salts, and exhibit a liquid behavior at 25 ℃.
Examples of the inorganic salt include: sodium chloride, potassium chloride, lithium perchlorate, ammonium chloride, potassium chlorate, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, ammonium sulfate, potassium nitrate, sodium carbonate, sodium thiocyanate, and the like.
The ionic liquid is a salt of a cation and an anion, and the cation is preferably, for example, an imidazolium ion, a pyridinium ion, an ammonium ion, or the like.
Examples of the ionic liquid containing an imidazolium ion include: 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, 1, 3-dimethylimidazolium bis (trifluoromethylsulfonyl) imide, 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, and the like.
Examples of the ionic liquid containing pyridinium ions include: 1-methylpyridinium bis (trifluoromethylsulfonyl) imide, 1-butylpyridinium bis (trifluoromethylsulfonyl) imide, 1-hexylpyridinium bis (trifluoromethylsulfonyl) imide, 1-octylpyridinium bis (trifluoromethylsulfonyl) imide, 1-hexyl-4-methylpyridinium hexafluorophosphate, 1-octyl-4-methylpyridinium bis (trifluoromethylsulfonyl) imide, 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imide, 1-methylpyridinium bis (perfluoroethylsulfonyl) imide, 1-methylpyridinium bis (perfluorobutylsulfonyl) imide, and the like.
Examples of the ionic liquid containing ammonium ions include: trimethyl heptyl ammonium bis (trifluoromethanesulfonyl) imide, N-diethyl-N-methyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N-diethyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N-diethyl-N-methyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, tri-N-butylmethylammonium bis trifluoromethanesulfonyl imide, and the like.
In addition, known ionic liquids whose cations are pyrrolidinium ions, phosphonium ions, sulfonium ions, and the like can be suitably used.
The ionic solid is a salt of a cation and an anion as in the ionic liquid, but shows a solid state at 25 ℃ under normal pressure. The cation is preferably, for example, an alkali metal ion, a phosphonium ion, a pyridinium ion, an ammonium ion, or the like.
Examples of ionic solids containing alkali metal ions include: lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethylsulfonyl) imide, lithium bis (pentafluoroethylsulfonyl) imide, lithium bis (heptafluoropropyl) sulfonyl imide, lithium bis (nonane) fluorobutyl sulfonyl imide, sodium bis (fluorosulfonyl) imide, sodium bis (trifluoromethylsulfonyl) imide, sodium bis (pentafluoroethylsulfonyl) imide, sodium bis (heptafluoropropyl) sulfonyl imide, sodium bis (nonane) fluorobutyl sulfonyl imide, potassium bis (fluorosulfonyl) imide, potassium bis (trifluoromethylsulfonyl) imide, potassium bis (pentafluoroethylsulfonyl) imide, potassium bis (heptafluoropropyl) sulfonyl imide, potassium bis (nonane) fluorobutyl sulfonyl imide, and the like.
Examples of ionic solids containing phosphonium ions include: tetrabutylphosphonium bis-trifluoromethylsulfonyl imide, tetrabutylphosphonium bis-pentafluoroethylsulfonyl imide, tetrabutylphosphonium bis-heptafluoropropylsulfonyl imide, tetrabutylphosphonium bis-nonane-fluorobutylsulfonyl imide, tributyl-hexadecylphosphonium bis-fluorosulfonyl imide, tributyl-hexadecylphosphonium bis-trifluoromethylsulfonyl imide, tributyl-hexadecylphosphonium bis-pentafluoroethylsulfonyl imide, tributyl-hexadecylphosphonium bis-heptafluoropropylsulfonyl imide, tributyl-hexadecylphosphonium bis-nonane-fluorobutylsulfonyl imide, tetraoctyl-phosphonium bis-pentafluoroethylsulfonyl imide, tetraoctyl-phosphonium bis-heptafluoropropylsulfonyl imide, tetraoctyl-phosphonium bis-nonane-fluorobutylsulfonyl imide, and the like.
Examples of the ionic solid containing pyridinium ions include: 1-hexadecyl-4-methylpyridinium bis-fluorosulfonyl imide, 1-hexadecyl-4-methylpyridinium bis-trifluoromethylsulfonyl imide, 1-hexadecyl-4-methylpyridinium bis-pentafluoroethylsulfonyl imide, 1-hexadecyl-4-methylpyridinium bis-heptafluoropropylsulfonyl imide, 1-hexadecyl-4-methylpyridinium bis-nonane fluorobutylsulfonyl imide, and the like.
Examples of the ionic solid containing ammonium ions include: tributylmethyl bis (trifluoromethyl) sulfonyl imide, tributylmethyl bis (pentafluoroethyl) sulfonyl imide, tributylmethyl bis (heptafluoro) propyl sulfonyl imide, tributylmethyl bis (nonane) fluoro butyl sulfonyl imide, octyl tributyl (trifluoromethyl) sulfonyl imide, octyl tributyl (pentafluoro) ethyl sulfonyl imide, octyl tributyl (heptafluoro) propyl sulfonyl imide, octyl (tributyl) bis (nonane) fluoro butyl sulfonyl imide, tetrabutyl (bis) fluoro methyl sulfonyl imide, tetrabutyl (bis) bis (pentafluoroethyl) sulfonyl imide, tetrabutyl (bis) heptafluoro (heptafluoro) propyl sulfonyl imide, tetrabutyl (bis) nonane fluoro butyl sulfonyl imide, and the like.
In addition, known ionic solids in which cations are pyrrolidinium ions, imidazolium ions, sulfonium ions, and the like can be suitably used.
Surfactants can be classified into nonionic, anionic, cationic, and amphoteric types.
Examples of the nonionic surfactant include: glycerol fatty acid esters, polyoxyalkylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkylamines, polyoxyethylene alkylamine fatty acid esters, fatty acid diethanolamides, polyether ester amide types, ethylene oxide-epichlorohydrin types, polyether ester types, and the like.
Examples of anionic surfactants (excluding ionic liquids and ionic solids) include: alkyl sulfonates, alkylbenzene sulfonates, alkyl phosphates, polystyrene sulfonic acid type, and the like.
Examples of the cationic surfactant include: tetraalkylammonium salts, trialkylbenzylammonium salts, acrylate polymers containing quaternary ammonium salt groups, and the like.
The amphoteric surfactants include, for example: amino acid type amphoteric surfactants such as alkyl betaine and alkyl imidazolium betaine, higher alkyl aminopropionate, and betaine type amphoteric surfactants such as higher alkyl dimethyl betaine and higher alkyl dihydroxyethyl betaine.
Antistatic agents are distinguished as liquids or solids at 25 ℃.
An antistatic agent that is liquid at 25 ℃ is easily transferred to the interface between the adhesive layer and the adherend, and thus more excellent antistatic properties can be easily obtained, as compared with a solid at 25 ℃.
In addition, an antistatic agent that is solid at 25 ℃ is partially easily present in the adhesive layer in the form of islands of sea-island structure, compared with a liquid at 25 ℃. Thus, the adhesive layer has an improved moderation property, and thus good flexibility can be easily obtained.
Of these, the antistatic agent is preferably 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imide or tetrabutylphosphonium bis (trifluoromethanesulfonyl imide).
In the case of using an antistatic agentThe surface resistance of the acrylic adhesive layer under an atmosphere of 23 to 50% RH is preferably 1X 10 5 Omega/gamma above and 1×10 10 Omega/gamma or less. By blending a proper amount of antistatic agent, the dustproof property, the adhesive force and the strain adaptability can be highly considered.
The content of the antistatic agent for exhibiting the surface resistance value is preferably 0.05 to 1 part by mass, more preferably 0.1 to 0.8 part by mass, and even more preferably 0.1 to 0.5 part by mass, based on 100 parts by mass of the acrylic copolymer (a), although the content depends on the structure of the antistatic agent.
(organosilane compound)
The acrylic adhesive of the present invention may further contain an organosilane compound. Examples of the organosilane compound include: alkoxysilane compounds having a (meth) acryloxy group such as 3- (meth) acryloxypropyl trimethoxysilane, 3- (meth) acryloxypropyl triethoxysilane, 3- (meth) acryloxypropyl tripropoxysilane, 3- (meth) acryloxypropyl tributoxysilane, 3- (meth) acryloxypropyl methyldimethoxysilane, and 3- (meth) acryloxypropyl methyldiethoxysilane; alkoxysilane compounds having a vinyl group such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinylmethyldimethoxysilane, and vinylmethyldiethoxysilane; an alkoxysilane compound having an amino group such as 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-aminopropyl tripropoxysilane, 3-aminopropyl methyldimethoxysilane, 3-aminopropyl methyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropyl triethoxysilane, N- (2-aminoethyl) -3-aminopropyl methyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyl methyldiethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane; alkoxysilane compounds having a mercapto group such as 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 3-mercaptopropyl tripropoxysilane, 3-mercaptopropyl methyldimethoxysilane, and 3-mercaptopropyl methyldiethoxysilane; alkoxysilane compounds having an epoxy group such as 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl tripropoxysilane, 3-glycidoxypropyl tributoxysilane, 3-glycidoxypropyl methyldimethoxysilane, 3-glycidoxypropyl methyldiethoxysilane, and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane; tetraalkoxysilane compounds such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and the like; 3-chloropropyl trimethoxysilane, N-hexyltrimethoxysilane, N-hexyltriethoxysilane, N-decyltrimethoxysilane, N-decyltriethoxysilane, styryltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethylbutylidene) propylamine, 1,3, 5-tris (3-trimethoxysilylpropyl) isocyanurate, 3-isocyanatopropyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, hexamethyldisilazane, silicone resins having an alkoxysilane group in the molecule, and the like.
The organic silane compound is preferably contained in an amount of 0.01 to 2 parts by mass, more preferably 0.05 to 1 part by mass, per 100 parts by mass of the acrylic copolymer (a). By containing 0.01 to 2 parts by mass of the organosilane compound, an adhesive layer excellent in strain adaptability is easily formed.
The pressure-sensitive adhesive sheet of the present invention may contain various resins, oils, softeners, dyes, pigments, antioxidants, ultraviolet absorbers, weather stabilizers, plasticizers, fillers, anti-aging agents, antistatic agents, and the like as optional components as long as the problems can be solved.
< antistatic treatment Release film >)
The antistatic treatment release film includes a release agent layer and an antistatic layer. The stripping agent layer and the antistatic layer are respectively and independently formed on one side or two sides of the substrate.
The layer structure is not particularly limited, and the pressure-sensitive adhesive sheet is preferably excellent in dust resistance in the case of "a release agent layer/an antistatic layer/a base material" and in winding offset resistance in the case of "a release agent layer/a base material/an antistatic layer" from the side in contact with the pressure-sensitive adhesive layer.
Optionally "stripper layer/antistatic layer/substrate/antistatic layer" and the like.
Further, other layers may be provided between the layers within a range that does not hinder the effects of the present invention.
(substrate)
As the substrate, there is no particular limitation, and a transparent plastic substrate may be preferably used. Examples of the material for the transparent plastic substrate include: polyesters such as polyethylene terephthalate (polyethylene terephthalate, PET) and polyethylene naphthalate (polyethylene naphthalate, PEN), acrylic resins such as polymethyl methacrylate (polymethyl methacrylate, PMMA), and plastic materials such as polycarbonate, triacetyl cellulose, polysulfone, polyarylate, and polycycloolefin. In addition, the plastic material may be used singly or in combination of two or more.
Among the transparent plastic substrates described above, a transparent plastic substrate excellent in heat resistance, that is, a transparent plastic substrate in which deformation is suppressed or prevented under severe conditions such as high temperature, high humidity, and the like can be preferably used. As the transparent plastic substrate, a PET film or PEN film or a PET sheet or PEN sheet is particularly preferable.
The thickness of the transparent plastic substrate is not particularly limited, and is preferably 10 μm to 200 μm, more preferably 25 μm to 150 μm, for example.
(stripper layer)
The stripper layer is formed of a stripper. Examples of the release agent include: silicone-based, fluorine-based, olefin-based, alkyd-based, long chain alkyl-based, and the like. In the present invention, a silicone-based release agent is used in the sense of making the range of the magnitude of the release strength large.
The main component of the stripping agent of the invention is straight-chain silicone, and the content of branched silicone is below 1 mass%.
The silicone release agent contains silicone having a siloxane bond in the main chain. As the silicone, for example, a type (M unit) having three organic substituents and one oxygen atom bonded to silicon, a type (D unit) having two organic substituents and two oxygen atoms bonded to silicon, a type (T unit) having one organic substituent and three oxygen atoms bonded to silicon, and a type (Q unit) having no organic substituents and four oxygen atoms bonded to silicon can be combined to obtain various silicones having different peeling properties, and the magnitude of peeling strength can be controlled by the ratio of these. In many cases, the linear silicone containing M units and D units can be used to adjust the peeling direction, and the branched silicone containing T units or Q units in the structure of the linear silicone can be used to adjust the peeling direction.
The linear silicone preferably has a composition containing D units as a main component and M units as appropriate for adjusting the molecular weight. The organic substituent represents a hydrogen atom, a hydroxyl group, an alkyl group or an aryl group, and is preferably an alkyl group or an aryl group, more preferably a methyl group or a phenyl group, from the viewpoint of being easily dissolved in an organic solvent.
The linear silicone imparts various resistances, and thus may take a crosslinked structure. The linear silicone preferably has two or more vinyl groups at its terminal and/or side chain as crosslinking points. As the crosslinking agent, there are hydrogen-modified silicones and the like, and it is necessary to have two or more SiH groups in one molecule.
The hydrogen-modified silicone is preferably contained in an amount of 0.1 to 20 parts by mass per 100 parts by mass of the linear silicone.
The branched silicone preferably has a T unit and/or a Q unit, and the T unit and/or the Q unit is preferably 70 mass% or more in 100 mass% of the branched silicone. In addition to having T units and/or Q units, branched silicones may also have M units, D units.
The stripper layer is formed of a stripper. The stripping agent of the invention comprises linear silicone: branched silicone = 100:0 to 99: the ratio of 1 (mass ratio) contains linear silicone and branched silicone. By containing 1 mass% or less of branched silicone relative to the total mass of the release agent (linear silicone, hydrogen-modified silicone, and branched silicone), the dust resistance and the winding displacement resistance are improved. The proportion of the branched silicone is more preferably 0.5% by mass or less, and still more preferably 0.2% by mass or less.
The total content of the linear silicone, the hydrogen-modified silicone, and the branched silicone is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass, based on 100% by mass of the total mass of the release agent.
The silicone release agent may be synthesized by an addition reaction, a peroxide condensation reaction, or an ultraviolet crosslinking reaction, but is preferably formed by an addition reaction. The addition reaction is a cross-linking of the vinyl groups contained in the linear silicone with the SiH groups contained in the hydrogen modified silicone.
In the case of synthesizing a stripping agent by an addition reaction, a catalyst is included. The catalyst is not particularly limited, but is preferably a platinum-based catalyst, and more preferably chloroplatinic acid such as chloroplatinic acid or chloroplatinic acid, an alcohol compound of chloroplatinic acid, an aldehyde compound, a complex of chloroplatinic acid and various olefins, or the like.
The amount of the catalyst to be added is preferably 0.01 to 10 mass%, more preferably 0.2 to 2 mass%, based on 100 mass% of the total mass of the stripping agent.
The release agent may contain any suitable component other than the catalyst within a range that does not impair the effects of the present invention, in addition to the linear silicone and the branched silicone. Examples include: reaction inhibitors, inorganic fillers, organic fillers, colorants (dyes or pigments, etc.), plasticizers, ultraviolet absorbers, antioxidants, and the like.
The method for forming the release agent layer is preferably formed by applying the release agent composition to a release substrate.
The release agent may contain a solvent when applied to form the release agent layer. The solvent is not particularly limited, and examples thereof include: hydrocarbon solvents such as n-hexane, cyclohexane, and n-heptane; aromatic solvents such as toluene and xylene; ester solvents such as ethyl acetate and methyl acetate; ketone solvents such as acetone and methyl ethyl ketone; organic solvents such as alcohol solvents including methanol, ethanol and butanol.
Examples of the application method of the release agent include a micro gravure coater and a gravure coater.
The stripping agent can be 0.1g/m based on the mass of the solid component 2 ～2.0g/m 2 Preferably 0.5g/m 2 ～1.2g/m 2 The coating was performed in a left-right manner, and the release agent layer was provided by hardening.
As the hardening method, thermal hardening is preferable in order to advance the addition reaction. The curing temperature is not particularly limited, but is preferably 80℃or more and less than 130 ℃. When the temperature is 80℃or higher, long-term heating is not required for sufficient hardening, and further excellent productivity can be obtained. In addition, if the temperature is less than 130 ℃, the occurrence of wrinkles due to heat can be reduced in the substrate or the release substrate.
The thickness of the release agent layer is not particularly limited, but is preferably 0.1 μm to 2 μm, and more preferably 0.5 μm to 1.2 μm. When the thickness is 0.1 μm or more, the peeling property is sufficiently exhibited, and when the thickness is 2 μm or less, the winding displacement from the peeling agent layer is less likely to occur.
(antistatic layer)
The release film of the present invention is required to form an antistatic layer. By forming the antistatic layer on the release film, dust or dust can be suppressed from being mixed into the adhesive layer at the time of processing such as peeling or lamination in the lamination process.
The antistatic layer may be formed of an antistatic agent including an antistatic component. As the antistatic agent, known materials can be used. The antistatic component is not particularly limited, and examples thereof include conductive polymers. The conductive polymer component is preferably a water-soluble conductive polymer or a water-dispersible conductive polymer. By using the conductive polymer, peeling antistatic property based on the antistatic layer can be satisfied. The conductive polymer is "water-soluble" or "water-dispersible", but can be fixed in the antistatic layer by using a crosslinking agent (for example, melamine-based or isocyanate-based crosslinking agent) described later, thereby improving water resistance. By using the water-soluble conductive polymer or the water-dispersible conductive polymer, the surface resistance value of the antistatic layer can be suppressed to be low, and thus the dust resistance can be improved.
The water-soluble conductive polymer may be used without particular limitation, and examples thereof include: polyaniline sulfonic acid, poly (isothioindenodiyl-sulfonate) compounds, quaternary ammonium salt-containing (meth) acrylate-based polymers, and the like. The water-dispersible conductive polymer may be used without particular limitation, and examples thereof include polythiophenes and polyaniline doped with polyanions. Among these, polyaniline sulfonic acid is preferably used as the water-soluble conductive polymer, and polythiophenes doped with polyanions are preferably used as the water-dispersible conductive polymer.
Examples of polythiophenes that can be used as the water-dispersible conductive polymer include: poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3-butylthiophene), poly (3-hexylthiophene), poly (3-heptylthiophene), poly (3-octylthiophene), poly (3-decylthiophene), poly (3-dodecylthiophene), poly (3-octadecylthiophene), poly (3-bromothiophene), poly (3-chlorothiophene), poly (3-iodothiophene), poly (3-cyanothiophene), poly (3-phenylthiophene), poly (3, 4-dimethylthiophene), poly (3, 4-dibutylthiophene), poly (3-hydroxythiophene), poly (3-methoxythiophene), poly (3-ethoxythiophene), poly (3-butoxythiophene), poly (3-hexyloxythiophene), poly (3-heptyloxythiophene), poly (3-octyloxythiophene), poly (3-decyloxythiophene), poly (3-dodecyloxythiophene), poly (3-octadecyloxythiophene), poly (3, 4-dihydroxythiophene), poly (3, 4-dimethoxythiophene), poly (3, 4-dipropyloxy thiophene), poly (3, 4-dibutoxythiophene), poly (3, 4-dihexyloxy thiophene), poly (3, 4-diheptyloxy thiophene), poly (3, 4-dioctyloxy thiophene), poly (3, 4-didecyloxy thiophene), poly (3, 4-didodecyloxy thiophene), poly (3, 4-ethylenedioxythiophene), poly (3, 4-propylenedioxythiophene), poly (3, 4-butylenedioxythiophene), poly (3-methyl-4-methoxythiophene), poly (3-methyl-4-ethoxythiophene), poly (3-carboxythiophene), poly (3-methyl-4-carboxyethylthiophene), poly (3-methyl-4-carboxybutylthiophene). These may be used alone or in combination of two or more. Among them, poly (3, 4-ethylenedioxythiophene) (PEDOT) is preferable from the viewpoint of conductivity.
The polythiophenes preferably have a polymerization degree of 2 to 1000, more preferably 5 to 100. When the polymerization degree is in the range of 2 to 1000, the electrical conductivity is excellent, and thus the dust resistance is improved.
Polyanions are polymers having structural units of anionic groups and function as dopants for polythiophenes. Examples of the polyanion include: polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallylsulfonic acid, polypropylene sulfonic acid, polymethylpropenyl sulfonic acid, poly (2-acrylamide-2-methylpropanesulfonic acid), polyisoprene sulfonic acid, polyethyl methacrylate, poly (4-sulfobutyl methacrylate), polymethyloxyphenylsulfonic acid, polyvinylcarboxylic acid, polystyrene carboxylic acid, polyallylcarboxylic acid, polypropylene carboxylic acid, polymethylpropenyl carboxylic acid, poly (2-acrylamide-2-methylpropanecarboxylic acid), polyisoprene carboxylic acid, polyacrylic acid, polysulfonated phenylacetylene, and the like. Among them, polystyrene sulfonic acid (polystyrene sulfonic acid, PSS) is preferable from the viewpoint of improving conductivity and dispersibility of polythiophenes. These may be homopolymers or two or more kinds of copolymers.
The mass average molecular weight (Mw) of the polyanion is preferably 1000 to 100 ten thousand, more preferably 2000 to 50 ten thousand. In the range of 1000 to 100 ten thousand, the polythiophenes are preferable because of excellent doping and dispersibility.
For example, when poly (3, 4-ethylenedioxythiophene) (PEDOT) is used as the polythiophene and polystyrene sulfonic acid (PSS) is used as the polyanion capable of doping the polythiophene, the PEDOT interacts with the PSS, and electrons of the PEDOT are extracted by the PSS due to the presence of the very close distance, so that the antistatic layer exhibits conductivity and the dust resistance is improved.
Examples of commercial products of polythiophenes doped with polyanions include: the polymer is "Bayer (Bayer) brand" Bayer (Bytron) P "manufactured by poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonic acid (PEDOT/PSS)," Sipulex Jida (Sepiegyda) "manufactured by Xinyue polymer company, and" Verazol "manufactured by Utility chemical company.
The polystyrene-equivalent mass average molecular weight (Mw) of the polyaniline sulfonic acid which can be used as the water-soluble conductive polymer component is preferably 5X 10 5 Hereinafter, more preferably 3×10 5 The following is given. In addition, these conductive polymers generally preferably have a mass average molecular weight of 1X 10 3 The above is more preferably 5×10 3 The above.
As a commercial product of polyaniline sulfonic acid, trade name "aquaPASS" manufactured by Mitsubishi Rayon corporation, and the like are exemplified.
The antistatic layer may be formed of an antistatic agent containing an antistatic component such as a conductive polymer in a known resin. The known resin is not particularly limited, but preferably contains a polyester resin as a binder. The polyester resin may use a known resin material containing polyester as a main component.
As the crosslinking agent, a crosslinking agent such as melamine, isocyanate, or epoxy, which is used for general resin crosslinking, can be suitably selected and used.
The amount of the conductive polymer used is preferably 10 to 200 parts by mass, more preferably 25 to 150 parts by mass, and even more preferably 40 to 120 parts by mass, based on 100 parts by mass of the binder. When the amount of the conductive polymer is 10 to 200 parts by mass, more sufficient dust resistance can be ensured.
As a method for forming the antistatic layer, a method of applying a coating material (antistatic agent composition) for forming the antistatic layer to one or both surfaces of a base film and drying (or curing) the same may be employed, and as a conductive polymer component for preparing the coating material, a water-soluble conductive polymer or a water-dispersible conductive polymer, or a polyester resin as a binder may be contained, and a substance in which the conductive polymer is dissolved/dispersed in water may be preferably used. The aqueous conductive polymer solution or dispersion can be prepared, for example, by dissolving/dispersing a conductive polymer having a hydrophilic functional group in water. Examples of the hydrophilic functional group include: sulfo, amino, amido, imino, hydroxyl, mercapto, hydrazine, carboxyl, quaternary ammonium, sulfate, phosphate, and the like. The hydrophilic functional groups may form salts.
The thickness of the antistatic layer is preferably 3nm to 500nm, more preferably 3nm to 100nm, and still more preferably 3nm to 50nm. When the antistatic layer has a thickness of 3nm to 500nm, an adhesive sheet excellent in dust resistance can be formed.
Regarding the release film, the surface resistance value (Ω/y) measured on the surface of the release agent was 1×10 10 Omega/gamma or less, preferably 1X 10 9 Omega/gamma or less, more preferably 1X 10 8 Omega/gamma or less, more preferably 1X 10 7 Omega/gamma or less. The surface resistance value was shown to be 1X 10 10 The release film having an Ω/γ or less is preferably used as a film used in processing or conveying an article in which dust or dust is mixed due to static electricity is prevented.
The lower limit of the surface resistance value is not particularly limited, but is preferably 1×10 5 Omega/gamma.
The surface resistance value can be calculated from the surface resistance value measured in an atmosphere of 23% RH to 50% RH using a commercially available resistance measuring device.
As other treatments of the release film, for example, there may be implemented: physical treatments such as corona discharge treatment and plasma treatment; suitable surface treatments such as chemical treatments such as priming treatments.
< manufacturing of adhesive sheet >
The adhesive sheet of the present invention can be manufactured according to a usual method for manufacturing an adhesive sheet. For example, the method can be used for manufacturing: a method in which an acrylic adhesive agent, which is a mixture of the acrylic copolymer (a) and a curing agent or the like, is directly applied to the release agent layer side of the release film so that the thickness after drying becomes a predetermined thickness to form an adhesive agent layer, and another release film is attached; or on the release agent layer side of the two release films, the thickness after drying is regulated And a method of forming two adhesive layers by applying an adhesive to the thickness of the adhesive layer, and then attaching the adhesive layers. At least any one of the release films used at this time is an antistatic release film in which the surface resistance value of the release agent layer under an atmosphere of 23 to 50% RH is 1X 10 11 The main component of the stripper layer is linear silicone, and the content of branched silicone is below 1 mass%. Among them, it is preferable that both of the release films are the antistatic treatment release film.
The lower limit of the film thickness of the adhesive layer is 25 μm or more, and the upper limit is not particularly limited, and for example, it is preferably 50 μm to 500 μm, more preferably 50 μm to 200 μm. When the film thickness of the adhesive layer is 25 μm to 500 μm, a sufficient cohesive force is easily obtained, and the strain adaptability and the adhesive force can be highly compatible, which is preferable.
In addition, in the application of the adhesive, a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, or a spray coater may be used.
The adhesive sheet may be cut to a suitable width and wound in a roll form to have a roll-form adhesive tape.
"laminate"
The laminate comprises an adherend and an acrylic adhesive layer formed using the adhesive sheet of the present invention.
Specifically, for example, an antistatic treatment release film can be peeled from the adhesive sheet for a flexible display of the present invention, and an adhesive layer can be attached to an adherend such as a film base (cover panel), a touch sensor (including a transparent conductive layer, a refractive index adjusting layer, and a protective layer as the outermost layer), a reinforcing metal plate, a polarizing plate, or an optical element to form a laminate.
Fig. 2 shows an example of a schematic cross-sectional view of a laminate which is a use example of the adhesive sheet of the present invention. In fig. 2, 3 is a film substrate, 1 is an adhesive layer 1, and 4 is a polarizing plate.
In the laminate shown in fig. 2, the film base material is attached to the polarizing plate via the adhesive layer containing the adhesive of the present invention. As described above, the adhesive sheet of the present invention can be used in a form in which an acrylic adhesive layer formed of an acrylic adhesive is attached to a film base material (cover sheet) and a polarizing plate.
As the film substrate (cover panel), there is no particular limitation, and a transparent plastic substrate or an ultra-thin glass (UTG) substrate may be preferably used. Examples of the material for the transparent plastic substrate include: acrylic resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polymethyl methacrylate (PMMA), and plastic materials such as polycarbonate, polycycloolefin, and polyimide. In addition, the plastic material or the glass material may be used singly or in combination of two or more.
As the film base material (cover sheet), in the case of the transparent plastic base material as described above, a transparent plastic base material excellent in heat resistance, that is, a transparent plastic base material whose deformation is suppressed or prevented under severe conditions such as high temperature, high humidity, and the like can be preferably used. Particularly preferred transparent plastic substrates are polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycycloolefin, and polyimide.
The thickness of the film base material (cover sheet) is not particularly limited, and is preferably 100 μm to 2000 μm, more preferably 200 μm to 1000 μm, for example.
Flexible display "
The flexible display includes an optical element and an acrylic adhesive layer formed using the adhesive sheet of the present invention.
The flexible display has flexibility and resistance to breakage even when bent or twisted, and the optical element is not particularly limited, and examples thereof include a liquid crystal element and an organic EL element.
The optical element is, for example, an image display section in which an organic electroluminescent element layer (hereinafter, referred to as an OLED layer), a liquid crystal element layer, or the like is deformable, and is a member which can be deformed from a planar state to some extent, such as bending or bending. The deformation may be temporary or permanent.
Examples of the OLED layer include a structure in which an anode, a hole injection/transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, a cathode, a sealing material, and an inorganic barrier layer are sequentially stacked on a film substrate. Various materials or layer structures constituting the OLED layer and fabrication methods may be used as known.
The flexible display has an adhesive layer formed using the adhesive sheet of the present invention.
Specifically, for example, the antistatic treatment release film may be peeled from the adhesive sheet for a flexible display of the present invention, and the exposed acrylic adhesive layer may be attached to an adherend such as a film base material or a polarizing plate to form a laminate, and then attached to an optical element via another adhesive layer, thereby producing a flexible display.
Fig. 3 shows an example of a schematic cross-sectional view of a display device which is a use example of the adhesive sheet of the present invention. In fig. 3, 3 is a film base material (cover sheet), 1 is an adhesive layer 1,4 is a polarizing plate, 5 is an adhesive layer 2,6 is a barrier layer of silicon nitride or the like, 7 is an organic EL layer, 8 is a support of polyimide or the like, and 9 is an organic EL unit. The structure of the display is not limited to fig. 3.
In the display shown in fig. 3, a film base material (cover sheet) can be attached to a polarizing plate via an adhesive sheet including an adhesive layer 1 formed of the adhesive of the present invention, and further attached to an organic EL unit via an adhesive layer for a polarizing plate (adhesive layer 2), thereby producing a flexible display.
In addition, the present invention can also be used to form an adhesive layer (adhesive layer 2) for a polarizing plate shown in fig. 3, and in this case, specifically, for example, an antistatic treatment release film can be peeled off from the adhesive sheet for a flexible display of the present invention, the exposed acrylic adhesive layer can be attached to an optical element to form a laminate, and then the other release film can be peeled off and attached to a laminate including a polarizing plate or the like to produce a flexible display.
That is, for example, in fig. 3, the adhesive of the present invention can be used for either one of the adhesive layer 1 and the adhesive layer 2.
The application of the display is not particularly limited, and examples thereof include an organic EL television, an organic EL smart phone, an organic EL tablet computer, and an organic EL smart watch.
Examples (example)
Next, examples are shown to further explain the details, but the present invention is not limited by these. In the examples, "parts" means "parts by mass", "%" means "% by mass", and "RH" means relative humidity unless otherwise specified. The amounts in the tables are parts by mass. In addition, blank columns in the table indicate undeployed.
The glass transition temperature, mass average molecular weight, and surface resistance value of the antistatic release film of the acrylic copolymer and the acrylic adhesive layer were measured as follows.
< calculation of glass transition temperature of acrylic copolymer and acrylic adhesive layer >
The glass transition temperature (Tg) of the acrylic adhesive layer was measured by a robotic DSC ("RDC 220" manufactured by the company of fine instruments (Seiko Instruments)). About 2mg of the sample was placed in an aluminum flat plate, weighed and placed in a differential scanning calorimeter, and after holding at 100℃for 5 minutes with reference to the same type of aluminum flat plate in which the sample was not placed, it was quenched to-120℃using liquid nitrogen. Then, the temperature was raised at a temperature-raising rate of 5℃per minute, and the glass transition temperature (Tg, unit: DEG C) was determined from the obtained DSC chart.
< determination of mass average molecular weight of acrylic copolymer >
For the measurement of the mass average molecular weight (Mw), a gel permeation chromatograph (gel permeation chromatograph, GPC) "LC-GPC system" manufactured by Shimadzu corporation was used, and the mass average molecular weight (Mw) was determined by conversion based on polystyrene having a known molecular weight.
Device name: manufactured by Shimadzu corporation, LC-GPC System "Japanese (Prominance)".
And (3) pipe column: four GMHXLs manufactured by Tosoh corporation and one HXL-H manufactured by Tosoh corporation are connected.
Mobile phase solvent: tetrahydrofuran (THF)
Flow rate: 1.0 ml/min
Column temperature: 40 DEG C
Acrylic pressure-sensitive adhesive layer and measurement of surface resistance value of antistatic Release film
The surface resistance value of the surface of the acrylic adhesive layer and the surface of the release agent layer of the antistatic release film were measured using a sea-Laplace (Hiresta) -UX MCP-HT800 (manufactured by Nitto Seiko analysis technology (Nittoseiko Analytech)).
Production example of acrylic copolymer
(acrylic copolymer (A-1))
A reaction vessel (hereinafter, simply referred to as "reaction vessel") including a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen inlet tube was charged with 100 parts of ethyl acetate, 80 parts of 2-ethylhexyl acrylate (2-ethylhexyl acrylate,2 EHA), 15 parts of Butyl Acrylate (BA), 3 parts of Methyl Acrylate (MA), 1 part of Acrylic Acid (AA), 1 part of 2-hydroxyethyl acrylate (HEA), and 0.1 part of 2,2' -azobisisobutyronitrile (hereinafter, simply referred to as "AIBN (azobisisobutyronitrile)") as an initiator, and the atmosphere in the reaction vessel was replaced with nitrogen. Then, the reaction was started by heating to 65℃with stirring under a nitrogen atmosphere. Then, the reaction solution was allowed to react at 65℃for 4 hours. After the completion of the reaction, the mixture was cooled and diluted with ethyl acetate to obtain a 30% nonvolatile acrylic copolymer (A-1) solution. The mass average molecular weight of the obtained acrylic copolymer (A-1) was 80 ten thousand.
(acrylic copolymers (A-2 to A-6))
Acrylic copolymers (A-2 to A-6) were produced by the same method as the production of the acrylic copolymer (A-1), except that the composition and the blending amount (parts by mass) described in Table 1 were changed.
The mass average molecular weights (Mw) of the obtained adhesives (A-1, A-2 to A-6) are shown in Table 1.
TABLE 1
Table 1.
Figure BDA0003972711350000181
The abbreviations in the tables are as follows.
(monomer (a-1))
MA: methyl acrylate (C1)
(monomer (a-2))
IBXA: isobornyl acrylate
(monomer (a-3))
2EHA: 2-ethylhexyl acrylate (C8)
(monomer (a-4))
AA: acrylic acid
HEA: acrylic acid 2-hydroxy ethyl ester
(monomer (a-5))
BA: butyl acrylate (C4)
< manufacturing of antistatic treatment Release film >
(antistatic treatment Release film (B-1))
100 parts of Lailong (Vylonal) MD-1480 (manufactured by Toyo-yo corporation), 70 parts of Alquarpas (aquaPASS) (manufactured by Mitsubishi chemical (Mitsubishi Chemical)) as a conductive polymer, 10 parts of diisopropylamine block-type hexamethylene diisocyanate-urea acid ester as a crosslinking agent, and 20 parts of oleamide as a lubricant were diluted with water and thoroughly mixed with stirring to prepare an antistatic agent.
The antistatic agent was applied to a polyethylene terephthalate (PET) film having a film thickness of 50 μm by a gravure coater so that the film thickness after drying became 25nm, and dried at 140 ℃ for 2 minutes to form an antistatic layer.
Next, the release agent was prepared by mixing and stirring the components so that 100 parts of addition reaction silicone, 1 part of platinum catalyst, and 200 parts of toluene were added to 100 parts of methyl group and 5 mol% vinyl group in the silicone as the main binder.
The addition reaction type silicone contains a linear silicone having two or more vinyl groups as crosslinking reaction groups and a hydrogen-modified silicone, and the content of the branched silicone is 0 mass%.
The prepared release agent was applied to the antistatic layer by a gravure coater so that the film thickness after drying became 1 μm, and dried at 120℃for 2 minutes to form a release agent layer, to obtain an antistatic-treated release film (B-1) having a layer structure of a base material/antistatic layer/release agent layer.
(antistatic treatment Release films (B-2, B-3), antistatic treatment Release film (B' -1))
An antistatic release film (B-2, B-3) and an antistatic release film (B' -1) each having a layer structure of a base material, an antistatic layer, and a release agent layer were obtained by forming a release agent in the same manner as in the antistatic release film (B-1) except that the release agent was changed to those shown in Table 2.
Regarding the release agent, a release agent was obtained in which the addition-reaction type silicone contained a linear silicone having two or more vinyl groups as crosslinking reactive groups and a hydrogen-modified silicone, and a branched silicone was contained at the content ratio described in table 2 according to the conditions at the time of production.
(antistatic treatment Release film (B-4))
An antistatic agent and a release agent were produced in the same manner as in the production of the antistatic-treated release film (B-1).
The antistatic agent was applied to a polyethylene terephthalate (PET) film having a film thickness of 50 μm by a gravure coater so that the film thickness after drying became 25nm, and dried at 140 ℃ for 2 minutes to form an antistatic layer.
Then, a release agent was applied to the surface of the base material opposite to the antistatic layer by a gravure coater so that the film thickness after drying became 1 μm, and the release agent layer was formed by drying at 120℃for 2 minutes, to obtain an antistatic-treated release film (B-4) having a layer structure of an antistatic layer/base material/release agent layer.
In the release agent, the addition reaction type silicone contains a linear silicone having two or more vinyl groups as crosslinking reaction groups and a hydrogen-modified silicone, and the content of the branched silicone is 0 mass%.
(Release film (B' -2))
The stripping agent was produced in the same manner as in the production of the antistatic-treated stripping film (B-1).
The release agent was applied to a polyethylene terephthalate (PET) film having a film thickness of 50 μm by a gravure coater so that the film thickness after drying became 1 μm, and dried at 120 ℃ for 2 minutes to form a release agent layer, thereby obtaining a release film (B' -2) having a layer structure including a base material/release agent layer.
Table 2 shows the compositions, surface resistance values, and layer structures of the release agents of the antistatic release films (B-2 to B-4), the antistatic release film (B '-1), and the release film (B' -2).
TABLE 2
Table 2.
Figure BDA0003972711350000201
Example 1
< preparation of adhesive >)
To 100 parts of the nonvolatile component of the acrylic copolymer (A-1), 0.1 part of toluene diisocyanate-trimethylolpropane adduct as a curing agent and 0.2 part of 3-glycidoxypropyl trimethoxysilane (S-1) as an organosilane compound were blended, and ethyl acetate was blended so that the nonvolatile component became 20%, and the mixture was stirred to obtain an acrylic adhesive.
< manufacturing of adhesive sheet >
The obtained acrylic adhesive was applied to the release agent layer of the antistatic-treated release film (B-1) (release film 1) so that the thickness after drying became 75. Mu.m, and dried at 110℃for 3 minutes, thereby forming an adhesive layer. Then, a release agent layer of an antistatic treatment release film (B-2) (release film 2) was bonded to the adhesive layer, and cured at a temperature of 25 ℃ under a relative humidity of 55% for 1 week to obtain an adhesive sheet having a structure of "antistatic treatment release film (B-1)/adhesive layer/antistatic treatment release film (B-2)".
(examples 2 to 13, comparative example 1, and comparative example 2)
Acrylic adhesives were obtained in the same manner as in example 1, except that the types and blending amounts (parts by mass) of the acrylic copolymer, the curing agent, the antistatic agent, and the organosilane compound were changed as shown in tables 3 and 4. Then, using the release films shown in tables 3 and 4, adhesive sheets were produced in the same manner as in example 1.
Evaluation of adhesive sheet
Using the obtained adhesive sheet, the dust resistance, the winding displacement resistance, the strain adaptability, and the adhesive force were evaluated. The results are shown in tables 3 and 4.
In the production of the laminate, when one surface of the release film peeled from the adhesive sheet is an antistatic release film, the acrylic adhesive layer exposed after peeling the antistatic release film is attached to the adherend to produce the laminate, and evaluation is performed. When the release film has antistatic treatment release films on both sides, first, a laminate is produced by sequentially peeling from an antistatic treatment release film (release film 1) which has a light peeling force and is easily peeled off, and evaluation is performed.
< dustproof Property >)
In a clean room (class 1000) environment, an antistatic treatment release film was peeled from the produced adhesive sheet and laminated on a base film (cover sheet) to form a laminate. The dust resistance of the obtained laminate was measured in an area of 25cm wide by 100cm long using a defect inspection machine.
[ evaluation criterion ]
And (3) the following materials: no foreign matter such as dust or dust was confirmed at all, and the product was excellent.
O: it was confirmed that one foreign matter such as dust or dust was good.
Delta: two or three kinds of foreign matters such as dust or dust were confirmed, and there was no problem in practical use.
X: it was confirmed that four or more foreign matters such as dust and the like are practically problematic.
< winding offset resistance >)
A sample obtained by cutting the obtained adhesive sheet into 4cm square was prepared, and 2kg/cm of the adhesive sheet was applied using a blocking tester (blocking tester) 2 Is allowed to stand at 40℃for 24 hours. Then, the sample was taken out of the tester and allowed to stand at 23℃for 1 hour, and the degree of offset between the cured antistatic treatment release film and the adhesive layer was evaluated visually. The evaluation criteria are as follows.
[ evaluation criterion ]
And (3) the following materials: no winding displacement occurs at all, and the winding is excellent.
O: a winding displacement of 0.1mm or less is generated, and is excellent.
Delta: a winding displacement in the range of more than 0.1mm and 0.3mm or less occurs, and there is no problem in practical use.
X: winding displacement exceeding 0.3mm occurs, which is practically problematic.
< adaptive to Strain >
From the obtained adhesive sheet, the antistatic treatment release film was peeled off from the adhesive layer, and the exposed adhesive layer was laminated on the polyimide film. Then, the other side of the antistatic treatment release film was peeled off from the adhesive layer, and the exposed adhesive layer was laminated on the easy-to-adhere PET film. The laminate was placed in an autoclave and maintained at 50℃for 20 minutes. Then, the laminate was taken out and left standing at 23 to 50% RH for 30 minutes, and then, the laminate was prepared in a size of 70mm in width and 100mm in length, to obtain a laminate for test comprising a PET film, an adhesive layer and a polyimide.
Then, the test laminate was twisted left and right by a flat body no-load torsion tester (manufactured by euasa System) under an atmosphere of 50% rh at 25 ℃, and then returned to the state before twisting, and the above was repeated for 20 ten thousand cycles with one cycle. The test was performed with n=5, and the appearance after the test was evaluated. The evaluation criteria are as follows.
[ evaluation criterion ]
And (3) the following materials: the generation of bubbles, the floating/flaking, and the like were not confirmed at all in the five times, and the product was excellent.
O: the generation of bubbles, the floating/flaking were slightly confirmed only once, and the effect was good.
Delta: the generation, floating and flaking of bubbles were slightly confirmed at a frequency of two or three times, and there was no problem in practical use.
X: the generation, floating and peeling of bubbles were slightly confirmed at four times or more, or the generation, floating and peeling of bubbles were once confirmed clearly, which was practically problematic.
< adhesion >
In the obtained adhesive sheet, the antistatic treatment release film was peeled off from the adhesive layer, and the exposed adhesive layer was laminated on the easy-to-adhere PET film. Then, the other side of the antistatic treatment release film was peeled off from the adhesive layer, and the exposed adhesive layer was laminated on the polyimide film. The obtained easy-to-attach PET film/adhesive layer/polyimide was prepared into a measurement sample having a width of 25mm and a length of 100 mm. Then, crimping was performed once back and forth with a 2kg roller under an atmosphere of 23 to 50% RH. Then, the mixture was left at 23℃for 24 hours. The adhesion between the adhesive layer and the polyimide was measured using a tensile tester at a peeling speed of 300 mm/min and a peeling angle of 180℃in an environment of 23 ℃. The evaluation criteria are as follows.
[ evaluation criterion ]
And (3) the following materials: is more than 20N/25mm, and is excellent.
O: it is preferably 15N/25mm or more and less than 20N/25 mm.
Delta: the diameter is 10N/25mm or more and less than 15N/25mm, and the method has no practical problem.
X: less than 10N/25mm, has practical problems.
TABLE 3
Table 3.
Figure BDA0003972711350000221
TABLE 4
TABLE 4 Table 4
Figure BDA0003972711350000231
The abbreviations in the tables are as follows.
< hardener >
NCO: toluene diisocyanate-trimethylolpropane adducts
< antistatic agent >
E-1: 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imide
< organosilane Compound >
S-1: 3-glycidoxypropyl trimethoxysilane
From the results shown in tables 3 and 4, it was confirmed that the adhesive sheets of examples were excellent in winding displacement resistance and antistatic property, and also excellent in all of roll bending properties. Thus, the laminate using the adhesive sheet of the present invention is excellent in winding displacement resistance, antistatic property, and reel bending property of a display. Further, the display of the present invention is excellent in convenience and visibility. On the other hand, the adhesive sheets of comparative examples 1 and 2 could not satisfy all of the above characteristics.

Claims (8)

1. An adhesive sheet for flexible display, wherein,
an acrylic adhesive layer is included on the release agent layer of the antistatic treatment release film,
The surface resistance value of the stripping agent layer under 23-50% RH atmosphere is 1X 10 11 The ratio of omega to gamma is lower than or equal to that of gamma,
the main component of the stripper layer is linear silicone, the content of branched silicone is below 1 mass%,
the glass transition temperature of the acrylic adhesive layer is-55 ℃ or lower.
2. The adhesive sheet for flexible display according to claim 1, wherein the film thickness of the acrylic adhesive layer is 50 μm or more.
3. The adhesive sheet for flexible display according to claim 1 or 2, wherein the acrylic adhesive layer comprises an acrylic copolymer (A),
the acrylic copolymer (A) contains an acrylic copolymer having a mass average molecular weight of 80 ten thousand or more.
4. The adhesive sheet for flexible display according to claim 3, wherein the acrylic copolymer (a) is a copolymer of a monomer mixture comprising at least any one of an alkyl (meth) acrylate monomer (a-1) having an alkyl group of 1 or 2 carbon atoms and an alkyl (meth) acrylate monomer (a-2) having an alicyclic structure.
5. The adhesive sheet for flexible display use according to claim 4, wherein the monomer mixture further comprises an alkyl (meth) acrylate monomer (a-3) having an alkyl group having 8 to 12 carbon atoms,
The content of the monomer (a-3) in 100 mass% of the monomer mixture is 80 mass% or more.
6. The adhesive sheet for flexible display use according to any one of claims 1 to 5, wherein the acrylic adhesive layer contains an antistatic agent,
the surface resistance value of the acrylic adhesive layer under 23-50% RH atmosphere is 1X 10 10 Omega/gamma or less.
7. A method for producing a laminate including an adherend and an acrylic adhesive layer, the method comprising:
the step of peeling the antistatic treatment release film from the adhesive sheet for a flexible display according to any one of claims 1 to 6, and attaching an acrylic adhesive layer to an adherend.
8. A method of manufacturing a flexible display including an optical element and an acrylic adhesive layer, the method comprising:
a step of peeling the antistatic treatment release film from the adhesive sheet for a flexible display according to any one of claims 1 to 6, and attaching an acrylic adhesive layer to an optical element.
CN202211529811.1A 2021-12-03 2022-11-30 Adhesive sheet for flexible display, laminate, and method for producing flexible display Pending CN116285716A (en)

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