CN116769409A - Pressure-sensitive adhesive sheet - Google Patents

Pressure-sensitive adhesive sheet Download PDF

Info

Publication number
CN116769409A
CN116769409A CN202210226553.3A CN202210226553A CN116769409A CN 116769409 A CN116769409 A CN 116769409A CN 202210226553 A CN202210226553 A CN 202210226553A CN 116769409 A CN116769409 A CN 116769409A
Authority
CN
China
Prior art keywords
adhesive sheet
weight
adhesive
parts
peeling
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
CN202210226553.3A
Other languages
Chinese (zh)
Inventor
黄恒昶
侯猛
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.)
Nitto Denko Shanghai Songjiang Co Ltd
Nitto Denko Corp
Original Assignee
Nitto Denko Shanghai Songjiang Co Ltd
Nitto Denko Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nitto Denko Shanghai Songjiang Co Ltd, Nitto Denko Corp filed Critical Nitto Denko Shanghai Songjiang Co Ltd
Priority to CN202210226553.3A priority Critical patent/CN116769409A/en
Priority to TW112106977A priority patent/TW202344395A/en
Priority to KR1020230029106A priority patent/KR20230132709A/en
Priority to JP2023035773A priority patent/JP2023133232A/en
Publication of CN116769409A publication Critical patent/CN116769409A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241—Polyolefin, e.g.rubber
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J1/00—Adhesives based on inorganic constituents
    • 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
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/064—Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
    • 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
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • 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
    • C09J165/00—Adhesives based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/02—Polyamines
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/245—Vinyl resins, e.g. polyvinyl chloride [PVC]
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • 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
    • C09J7/30—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
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/50—Adhesives in the form of films or foils characterised by a primer layer between the carrier and the adhesive
    • 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
    • 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
    • C08K2201/011—Nanostructured additives
    • 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
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • C09J2301/1242—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape the opposite adhesive layers being different
    • 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
    • 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
    • C09J2301/314—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive layer and/or the carrier being conductive
    • 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
    • C09J2423/00—Presence of polyolefin
    • C09J2423/006—Presence of polyolefin in the substrate
    • 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
    • C09J2427/00—Presence of halogenated polymer
    • C09J2427/006—Presence of halogenated polymer in the substrate
    • 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
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention provides an adhesive sheet. The pressure-sensitive adhesive sheet of the present invention comprises: and an adhesive layer provided on one side of the base layer, wherein in a peeling test at a peeling speed of 300mm/min, a peeling static voltage generated by peeling the adhesive sheet from the release film is 500V or less. The adhesive sheet of the present invention can sufficiently suppress peeling static electricity generated at the time of peeling, has excellent antistatic property and stability with time of peeling static voltage, thereby avoiding or reducing damage to an adherend (for example, having excellent static breakdown resistance), and can be easily peeled off without generating residual glue contamination after use.

Description

Pressure-sensitive adhesive sheet
Technical Field
The present invention relates to an adhesive sheet, and more particularly, to an adhesive sheet which has excellent antistatic properties and adhesion and can be easily peeled off after use without generating residual glue contamination.
Background
In a process for producing members such as optical members and electronic members, an adhesive sheet (surface protective film) is usually attached to the exposed surfaces of the members in order to prevent surface damage of the members during processing, assembling, inspection, transportation, and the like. Such an adhesive sheet is peeled from these members when surface protection is not required. The surface protective film, the optical member, and the electronic member have high electrical insulation properties, and static electricity is generated due to friction and peeling. Therefore, static electricity is easily generated when the surface protective film is peeled from members such as optical members and electronic members. In such a case, damage to members such as optical members and electronic members is likely to occur, and the presence of static electricity may also cause dust absorption and deterioration of operability.
In order to prevent static electricity, an operation of applying antistatic treatment to an adhesive sheet is known. For example, the surface layer (top coat layer, back layer) of the adhesive sheet is provided with antistatic function by forming an antistatic layer and applying antistatic coating. However, the adhesive sheet forming the antistatic layer has the following problems: when the release film is peeled from the release film-attached adhesive sheet attached to the exposed surface side of the optical member, the electronic member, or the like, peeling static electricity is generated, and the optical member and the electronic member are damaged. Further, problems such as an increase in surface resistivity and peeling static voltage occur with the lapse of time. If an increase (deterioration) in surface resistivity or the like occurs, static electricity is generated when the pressure-sensitive adhesive sheet is peeled from the adherend, and there is a risk that static electricity carried by the adherend (for example, an electronic component or the like) will deteriorate and break down the built-in electronic component.
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made to solve the above-described conventional problems, and an object of the present invention is to provide an adhesive sheet which is excellent in antistatic properties (peeling-resistant electrostatic properties), re-peeling properties, and adhesion properties, and which can be easily peeled off after use without causing residual adhesive contamination.
Solution for solving the problem
The present inventors have made intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by controlling the peeling static voltage generated by peeling the adhesive sheet from the release film in a peeling test at a peeling speed of 300mm/min within a specific range, and have completed the present invention.
Namely, the present invention is as follows.
[1] An adhesive sheet comprising: a base material layer, and an adhesive layer disposed on one side of the base material layer,
wherein in a peeling test at a peeling speed of 300mm/min, the pressure-sensitive adhesive sheet has a peeling static voltage of 500V or less when peeled from the release film.
[2] The adhesive sheet according to [1], wherein a peeling static voltage generated by peeling the adhesive sheet from the release film in a peeling test at a peeling speed of 30m/min is 200V or less;
preferably, in a peeling test at a peeling speed of 30m/min, the peeling static voltage generated by peeling the adhesive sheet from the release film is 100V or less;
preferably, at least one surface of the adhesive sheet has a surface resistivity of 1.0X10 5 ～1.0×10 11 Ω/□；
Preferably, the surface resistivity of the base layer is 1.0X10 after stretching the adhesive sheet in a 360 DEG direction 1 to 1.5 times 5 ～1.0×10 11 Omega/≡the surface resistivity of the adhesive sheet was 1.0X10 11 Ω/≡or less.
[3] The adhesive sheet according to [1] or [2], wherein the adhesive layer comprises a base polymer, a multifunctional oligomer and an antistatic agent.
[4] The adhesive sheet according to [3], wherein the base polymer comprises an acrylic polymer;
preferably, the base polymer contains 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight, more preferably 3 to 15 parts by weight of a functional monomer based on 100 parts by weight of the entire monomer components of the base polymer;
preferably, the functional monomer includes at least one selected from the group consisting of a hydroxyl group-containing monomer, a carboxyl group-containing monomer, a sulfonic acid group-containing monomer, a phosphoric acid group-containing monomer, an epoxy group-containing monomer, an isocyanate group-containing monomer, an amide group-containing monomer, a ring-containing monomer having a nitrogen atom, a monomer having a succinimide skeleton, a maleimide-based monomer, a itaconimide-based monomer, an aminoalkyl (meth) acrylate-based monomer, an alkoxyalkyl (meth) acrylate-based monomer, a vinyl ether-based monomer, and an olefin-based monomer.
[5] The adhesive sheet according to [3], wherein the polyfunctional oligomer has a functionality of 2 or more, preferably 3 or more, more preferably 5 or more;
Preferably, the multifunctional oligomer comprises at least one selected from the group consisting of an acrylic modified resin, a polyurethane modified resin, an epoxy modified resin, a phenolic modified resin, a polyether modified resin, and a silicone modified resin;
preferably, the multifunctional oligomer comprises at least one of a polyurethane modified acrylic resin, an acrylic modified polyurethane resin, an epoxy modified acrylic resin, an epoxy modified polyurethane resin, an o-cresol formaldehyde modified resin, a phenol formaldehyde modified acrylic resin, a phenol formaldehyde modified polyurethane resin, a phenol formaldehyde modified epoxy resin, a polyether modified acrylate resin, and a silicone modified acrylate resin;
preferably, the multifunctional oligomer comprises at least one selected from the group consisting of polyurethane modified acrylate, epoxy modified acrylate, polyether modified acrylate, and silicone modified acrylate.
Preferably, the content of the multifunctional oligomer is 20 to 200 parts by weight, preferably 30 to 150 parts by weight, more preferably 40 to 120 parts by weight, relative to 100 parts by weight of the base polymer.
[6] The adhesive sheet according to [3], wherein the antistatic agent comprises at least one selected from the group consisting of conductive polymers, conductive inorganic fine particles, metal fine particles or fibers, ionic compounds, and ionic surfactants;
Preferably, the conductive polymer contains at least one selected from the group consisting of polyaniline, polypyrrole, polythiophene, polyquinoxaline, polyacetylene, polyethyleneimine, and allylamine-based polymer;
preferably, the conductive inorganic particles contain at least one selected from the group consisting of conductive metal oxides, carbon nanotubes, graphene, fullerenes, acetylene black, ketjen black, natural graphite, artificial graphite, and titanium black;
preferably, the metal particles or fibers comprise particles or nanowires of gold, silver, copper, aluminum, nickel, or alloys thereof;
preferably, the ionic compound comprises an alkali metal salt and/or an organic cation-anion salt;
preferably, the ionic surfactant comprises at least one selected from the group consisting of cationic surfactants, anionic surfactants, zwitterionic surfactants and nonionic surfactants;
preferably, the antistatic agent is contained in an amount of 0.0001 to 20 parts by weight, preferably 0.0002 to 10 parts by weight, relative to 100 parts by weight of the base polymer.
[7] The adhesive sheet according to any one of [1] to [6], wherein the adhesive layer further comprises a photoinitiator and/or a crosslinking agent;
Preferably, the photoinitiator is contained in an amount of 0.5 to 10 parts by weight, preferably 0.5 to 5 parts by weight, relative to 100 parts by weight of the base polymer;
preferably, the crosslinking agent is contained in an amount of 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, relative to 100 parts by weight of the base polymer.
[8] The adhesive sheet according to any one of [1] to [7], wherein the adhesive sheet satisfies at least one of the following characteristics (a) to (d):
characteristics (a): the adhesive strength reduction ratio of the adhesive sheet calculated by the following formula (1) is 80% or more, and the adhesive strength reduction ratio (%) = [ (N1-N2)/N1 ] ×100 (1)
Wherein N1 represents an adhesive force of the adhesive sheet before ultraviolet irradiation,
n2 represents the cumulative irradiation light quantity of 300mJ/cm of the adhesive sheet 2 Is a uv-post adhesive force;
characteristics (b): the cumulative irradiation light quantity of the adhesive sheet was 300mJ/cm 2 The adhesive force N2 after ultraviolet rays is less than 1N/20 mm;
characteristics (c): the adhesive force N1 of the adhesive sheet before ultraviolet irradiation is 0.5-40N/20 mm;
characteristics (d): the ratio of the tensile breaking strength in the longitudinal direction (MD direction) to the tensile breaking strength in the width direction (TD direction) (tensile breaking strength in the MD direction/tensile breaking strength in the TD direction) of the adhesive sheet is 0.8-1.2.
[9] The adhesive sheet according to any one of [1] to [8], wherein the thickness of the base material layer is 10 to 300. Mu.m, preferably 30 to 200. Mu.m, more preferably 50 to 150. Mu.m;
preferably, the substrate layer comprises at least one selected from the group consisting of thermoplastic polyurethane, polyethylene, polypropylene, polybutylene, ethylene-vinyl acetate copolymer, and polyvinyl chloride;
preferably, the substrate layer comprises an antistatic agent inside and/or on the surface.
[10] The adhesive sheet according to any one of [1] to [9], wherein the adhesive sheet further comprises a primer layer and/or a back coating layer,
the back coating layer is disposed on a side of the substrate layer opposite the adhesive layer,
the primer layer is disposed on the opposite side of the substrate layer from the back coating layer,
preferably, the primer layer includes at least one selected from the group consisting of thermosetting acrylic, polyurethane, and epoxy system resins;
preferably, the back coating layer includes at least one selected from the group consisting of thermosetting acrylic, polyurethane, and epoxy system resins.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, an adhesive sheet which is excellent in antistatic properties (peeling-preventing static properties), re-peeling properties, and adhesion and can be easily peeled off after use without causing residual adhesive contamination can be provided. The adhesive sheet of the present invention can sufficiently suppress peeling static electricity generated at the time of peeling, and realize excellent antistatic property and stability of peeling static voltage with time, thereby avoiding or reducing damage to an adherend (for example, excellent static breakdown resistance).
Drawings
Fig. 1 is a cross-sectional view schematically showing the structure of an adhesive sheet according to an embodiment of the present invention.
Fig. 2 is a cross-sectional view schematically showing the structure of an adhesive sheet according to another embodiment of the present invention.
Fig. 3 is a cross-sectional view schematically showing the structure of an adhesive sheet according to still another embodiment of the present invention.
Description of the reference numerals
1. 2, 3 pressure-sensitive adhesive sheet
10. Substrate layer
20. Adhesive layer
30. Back coating
40. Primer coating
Detailed Description
Hereinafter, preferred embodiments of the present invention will be described. Matters necessary for the practice of the present invention other than matters specifically mentioned in the present specification are understood by those skilled in the art based on the teachings and technical knowledge at the time of application as to the practice of the present invention described in the present specification. The present invention can be implemented based on the content disclosed in the present specification and technical common knowledge in the field.
In the drawings, members and portions that serve the same function are denoted by the same reference numerals, and repeated description thereof may be omitted or simplified. The embodiments described in the drawings are schematically illustrated for the sake of clarity of explanation of the present invention, and do not necessarily accurately represent the dimensions and scale of the product actually provided.
< adhesive sheet >
The adhesive sheet of the present invention comprises: a substrate layer; and an adhesive layer provided on one side of the base material layer, wherein in a peeling test at a peeling speed of 300mm/min, a peeling static voltage generated by peeling the adhesive sheet from the release film is 500V or less.
Fig. 1 is a cross-sectional view schematically showing the structure of an adhesive sheet according to an embodiment of the present invention. As shown in fig. 1, the adhesive sheet 1 includes a base material layer 10 and an adhesive layer 20 provided on one side of the base material layer 10, and the adhesive layer 20 is preferably provided on the entire face of the base material layer 10.
Fig. 2 is a cross-sectional view schematically showing the structure of an adhesive sheet according to another embodiment of the present invention. The adhesive sheet 2 is further provided with a back coating layer 30. As shown in fig. 2, the back coating layer 30 is provided on the opposite side of the substrate layer 10 from the adhesive layer 20.
Fig. 3 is a cross-sectional view schematically showing the structure of an adhesive sheet according to still another embodiment of the present invention. The adhesive sheet 3 further includes a primer layer 40. As shown in fig. 3, the primer layer 40 is provided between the substrate layer 10 and the adhesive layer 20 on the opposite side of the substrate layer 10 from the back coat layer 30.
Although not shown, the pressure-sensitive adhesive sheet of the present invention may be provided with a release liner on the outer side of the pressure-sensitive adhesive layer for the purpose of protecting the pressure-sensitive adhesive surface during the period of time before use.
The term "adhesive sheet" as used herein may include an object called an adhesive tape, an adhesive label, an adhesive film, or the like. The pressure-sensitive adhesive sheet disclosed herein may be a single sheet or may be a pressure-sensitive adhesive sheet further processed into various shapes. In some preferred embodiments, the adhesive sheet of the present invention may be provided in a long strip shape.
The adhesive sheet of the present invention has the following features: in a peeling test at a peeling speed of 300mm/min, the peeling static voltage generated by peeling the pressure-sensitive adhesive sheet from the release film is 500V or less, preferably 200V or less, more preferably 150V or less, still more preferably 100V or less.
In a peeling test at a peeling speed of 30m/min, the peeling static voltage generated by peeling the adhesive sheet from the release film is 200V or less, preferably 100V or less.
In the present invention, by setting the peeling static voltage generated by peeling the adhesive sheet from the release film to the above range, peeling static electricity that may be generated when peeling the adhesive sheet can be suppressed, the adhesive sheet has excellent antistatic properties (peeling static resistance), the adherend is not damaged when peeling, and the occurrence of problems such as electrostatic breakdown can be effectively prevented.
If the peeling static voltage is more than 500V, a large amount of peeling static electricity is generated during peeling, and the adverse effects such as electrostatic breakdown are generated. The stripping electrostatic pressure can be measured, for example, by the method described in examples described below.
In some preferred embodiments, the adhesive sheet of the present invention has a surface resistivity of at least one surface of 1.0X10 5 ～1.0×10 11 Ω/≡preferably 1.0X10) 6 ～1.0×10 9 Ω/≡. If the content is within such a range, the antistatic function can be satisfied, and the electronic component material can be prevented when the adhesive is applied to a member such as an electronic component materialIs a damage to the patient. The surface resistivity was measured in accordance with JIS K6911 (electrode area: 20cm at 23 ℃ C./50% atmosphere) 2 Applying a voltage: 100V, application time: 30 seconds, using concentric circular electrodes (probes)).
In some preferred embodiments, the adhesive sheet of the present invention has a surface resistivity of 1.0X10 of the substrate layer after stretching in a 360 DEG direction 1 to 1.5 times 5 ～1.0×10 11 Ω/≡preferably 1.0X10) 6 ～1.0×10 9 Omega/≡, the surface resistivity of the adhesive sheet was 1.0X10 11 Ω/≡or less.
In some preferred embodiments, the adhesive sheet of the present invention preferably further satisfies at least one of the following characteristics (a) to (d):
characteristics (a): the adhesive strength reduction ratio of the adhesive sheet calculated by the following formula (1) is 80% or more, and the adhesive strength reduction ratio (%) = [ (N1-N2)/N1 ] ×100 (1)
Wherein N1 represents an adhesive force of the adhesive sheet before ultraviolet irradiation,
n2 represents the cumulative irradiation light quantity of 300mJ/cm of the adhesive sheet 2 Is a uv-post adhesive force;
characteristics (b): the cumulative irradiation light quantity of the adhesive sheet was 300mJ/cm 2 The adhesive force N2 after ultraviolet rays is less than 1N/20 mm;
characteristics (c): the adhesive force N1 of the adhesive sheet before ultraviolet irradiation is 0.5-40N/20 mm;
characteristics (d): the ratio of the tensile breaking strength in the longitudinal direction (MD direction) to the tensile breaking strength in the width direction (TD direction) (tensile breaking strength in the MD direction/tensile breaking strength in the TD direction) of the adhesive sheet is 0.8-1.2.
In the above characteristic (a), the adhesive strength reduction ratio of the adhesive sheet calculated by the above formula (1) is more preferably 85% or more.
When the adhesive force lowering rate falls within the above range, the effect of the adhesive property required at the time of use can be sufficiently exhibited, excellent adhesive property can be achieved, and the adhesive can be gently peeled off after use without causing damage to the adherend or occurrence of residual adhesive contamination. If the adhesive strength reduction ratio is less than 80%, peeling operability is poor, and adhesive residue contamination is liable to occur. The adhesive forces N1 and N2 can be measured, for example, by the method described in examples described later.
In the above characteristic (b), the cumulative irradiation light quantity of the adhesive sheet was 300mJ/cm 2 The adhesive force N2 after ultraviolet light is more preferably 0.9N/20mm or less, and still more preferably 0.8N/20mm or less.
When the adhesive force N2 falls within the above range, excellent adhesion can be obtained, and the adhesive can be gently peeled off after use without causing damage to an adherend or generating residual adhesive contamination. If the adhesive force N2 is more than 1N/20mm, peeling operability is poor and residual glue contamination is liable to occur. From the viewpoint of excellent adhesion, the cumulative irradiation light amount of the adhesive sheet was 300mJ/cm 2 The adhesive force N2 after ultraviolet rays of (2) is preferably 0.01N/20mm or more.
In the present invention, the ultraviolet irradiation to which the adhesive sheet is subjected means ultraviolet irradiation (irradiation from the substrate layer side) to the adhesive layer in the adhesive sheet across the substrate layer. 300mJ/cm 2 For example, the ultraviolet irradiation of (C) may be performed at an irradiation intensity of 150mW/cm 2 Is realized by irradiation of ultraviolet rays for 2 seconds.
In the above characteristic (c), the adhesive force N1 of the adhesive sheet before ultraviolet irradiation is more preferably 1 to 30N/20mm, still more preferably 2 to 25N/20mm.
When the adhesive force N1 falls within the above range, excellent adhesion can be achieved. If the adhesive force N1 is less than 0.5N/20mm, peeling of the adhesive sheet due to insufficient adhesion is liable to occur. If the adhesive force N1 is more than 40N/20mm, peeling from the adherend is difficult, peeling workability is poor, and residual glue contamination is liable to occur.
In the above characteristic (d), the ratio of the tensile breaking strength in the longitudinal direction (MD direction) to the tensile breaking strength in the width direction (TD direction) (tensile breaking strength in the MD direction/tensile breaking strength in the TD direction) of the adhesive sheet is more preferably 0.9 to 1.1.
When the tensile breaking strength in the MD direction/the tensile breaking strength in the TD direction of the adhesive sheet falls within the above range, the adhesive sheet is excellent in peelability, and can exhibit good follow-up property to the uneven step of the adherend, and the adhesive sheet is uniformly spread in each direction, and the gap of the processed electric components is uniform, facilitating automatic recognition and pickup by subsequent equipment. If the tensile breaking strength in the MD direction/the tensile breaking strength in the TD direction of the adhesive sheet is less than 0.8 or exceeds 1.2, the flexibility of the adhesive sheet tends to be lowered, and it is difficult to obtain good rebound resilience, and the adhesive sheet tends to have large differences in mechanical performances such as elongation, rebound resilience, follow-up property and the like in each direction, and uneven expansion may cause uneven pitches of devices to be processed, which is disadvantageous for automatic recognition and pickup by subsequent equipment.
In some preferred embodiments, the tensile breaking strength of the adhesive sheet is preferably 10 to 60MPa, more preferably 15 to 50MPa. When the tensile breaking strength of the adhesive sheet in the longitudinal direction (MD direction) falls within the above range, the expansion can be easily achieved, and the breakage or tearing of the adhesive sheet can be appropriately suppressed, and the collapse of the adhesive sheet due to excessive rebound after the stretching can be avoided, further affecting the subsequent processing. The tensile breaking strength can be measured, for example, by the method described in examples described below.
[ adhesive layer ]
In the present invention, the adhesive layer is a layer formed of an adhesive composition. In a preferred embodiment, the adhesive layer is preferably a layer formed from an adhesive composition comprising a base polymer, a multifunctional oligomer and an antistatic agent. The form of the adhesive composition is not particularly limited, and may be, for example, various forms such as a water-dispersible form, a solvent form, a hot-melt form, an active energy ray-curable form (e.g., a photo-curable form), and the like.
The components of the adhesive composition of the present invention will be described in detail below.
(base Polymer)
The adhesive composition of the present invention comprises a base polymer. Examples of the base polymer include acrylic polymers, rubber polymers, polyester polymers, urethane polymers, polyether polymers, silicone polymers, polyamide polymers, and fluorine polymers. Preferably, the adhesive composition comprises an acrylic polymer as a base polymer.
The content of the base polymer is not particularly limited, but is preferably 30 to 90 mass%, more preferably 40 to 80 mass% with respect to the total amount (100 mass%) of the adhesive composition from the viewpoint of obtaining sufficient adhesion reliability. By adjusting the content of the base polymer in the adhesive composition to be within the above range, an adhesive composition having better structural system compatibility, stronger cohesion and excellent adhesion to an adherend can be provided.
The base polymer in the technology disclosed herein is preferably a polymer of the following monomer components: the monomer component contains a soft monomer (viscous monomer), a hard monomer (elastic monomer) as a main monomer, and a functional monomer (copolymerizable monomer) having copolymerizability with the above main monomer. The main monomer herein means the main component of the monomer components constituting the base polymer, i.e., the monomer components contain more than 70% by weight of the components.
In a preferred embodiment, the soft monomer (tacky monomer) comprises an alkyl (meth) acrylate. In the present specification, the term alkyl (meth) acrylate refers to alkyl acrylate and/or alkyl methacrylate.
The alkyl (meth) acrylate is preferably an alkyl (meth) acrylate having an alkyl group with 1 to 20 carbon atoms. Specific examples of the alkyl (meth) acrylate in which the alkyl group has 1 to 20 carbon atoms include, but are not particularly limited to: n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate and eicosyl (meth) acrylate. Among these, n-Butyl Acrylate (BA), 2-ethylhexyl acrylate (2 EHA) and Ethyl Acrylate (EA) are preferable. The alkyl (meth) acrylate may be used alone or in combination of two or more.
The content of the soft monomer (tacky monomer) is preferably 10 to 90 parts by weight, more preferably 15 to 80 parts by weight, based on 100 parts by weight of the total monomer components of the base polymer. When the content of the soft monomer is within the above range, the adhesive has good fluidity and initial adhesion, and can wet the surface to be bonded well, thereby obtaining excellent adhesion.
As the hard monomer, a hard monomer that can form a hard polymer having a relatively high glass transition point can be suitably used. The hard monomer is useful for improving cohesive strength of the adhesive layer. The hard monomer may be used alone or in combination of 2 or more.
As non-limiting specific examples of the hard monomer, there may be mentioned, for example: acrylonitrile (AN), methyl Methacrylate (MMA), methyl Acrylate (MA), vinyl Acetate (VAC), styrene, and the like.
The content of the hard monomer is preferably 5 to 80 parts by weight, more preferably 10 to 75 parts by weight, based on 100 parts by weight of the total monomer components of the base polymer. When the content of the hard monomer is in the above range, the supporting property can be provided for the adhesive system, the elastic modulus, cohesive strength and heat resistance of the adhesive are further improved, and phenomena such as knife sticking and adhesive residue can be well avoided in some cutting processes.
As the functional monomer (copolymerizable monomer), a monomer having a polar group can be suitably used. Monomers having polar groups are useful for introducing crosslinking points into the base polymer or for improving the cohesion of the base polymer. The functional monomer may be used alone or in combination of 2 or more.
Specific non-limiting examples of the functional monomer include a hydroxyl group-containing monomer (hydroxyl group-containing monomer), a carboxyl group-containing monomer (carboxyl group-containing monomer), a sulfonic acid group-containing monomer, a phosphoric acid group-containing monomer, an epoxy group-containing monomer, an isocyanate group-containing monomer, an amide group-containing monomer, a ring-containing monomer having a nitrogen atom, a monomer having a succinimide skeleton, a maleimide-based monomer, a itaconimide-based monomer, an aminoalkyl (meth) acrylate-based monomer, an alkoxyalkyl (meth) acrylate-based monomer, a vinyl ether-based monomer, an olefin-based monomer, and the like. Of these, at least 1 selected from hydroxyl group-containing monomers and carboxyl group-containing monomers is preferable.
The content of the functional monomer is preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight, still more preferably 3 to 15 parts by weight, based on 100 parts by weight of the total monomer components of the base polymer. When the content of the functional monomer is within the above range, the crosslinking density, loss modulus, storage modulus, cohesion and other properties of the adhesive can be conveniently adjusted by the crosslinking agent, and the adhesion can be optimized for different bonding surfaces.
The hydroxyl group-containing monomer means a monomer having at least one hydroxyl group in the molecule. In the case where the monomer component used to constitute the base polymer contains a hydroxyl group-containing monomer, that is, the base polymer contains a monomer unit derived from a hydroxyl group-containing monomer, since a secondary bond such as a hydrogen bond with an adherend is formed, the cohesive force of the base polymer (preferably an acrylic polymer) is improved, the change in adhesive force with time can be more effectively suppressed, and the adhesive residue to the adherend after peeling is less, and the adhesive composition has a higher aggregation property. In addition, when a crosslinking agent is used, a crosslinking reaction with the crosslinking agent can be effectively performed by adding a hydroxyl group-containing monomer to a raw material monomer of the base polymer, and the effect as a binder can be sufficiently exhibited. In addition, breakage of the adherend at the time of peeling operation can also be effectively prevented. The base polymer of the present embodiment may use 1 kind of hydroxyl group-containing monomer, or may use 2 or more kinds of hydroxyl group-containing monomers.
Specific examples of the hydroxyl group-containing monomer include: and hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, and (4-hydroxymethylcyclohexyl) methyl (meth) acrylate.
The content of the hydroxyl group-containing monomer is not particularly limited, and for example, the content of the hydroxyl group-containing monomer is 0.5 to 15 parts by weight, preferably 1 to 13 parts by weight, based on 100 parts by weight of the entire monomer components of the base polymer. When the content of the hydroxyl group-containing monomer is within the above range, since secondary bonds such as hydrogen bonds with an adherend are formed, the cohesive force of the base polymer (preferably, the acrylic polymer) is improved, the change in adhesive force with time can be more effectively suppressed, and the residual adhesive to the adherend after peeling is less, and the adhesive film has higher aggregation. When the content of the hydroxyl group-containing monomer is less than 0.5 parts by weight, sufficient adhesiveness is not obtained, and at the same time, the crosslinking density of the adhesive is too low, the cohesive strength is too low, and the risk of adhesive failure is increased. When the content of the hydroxyl group-containing monomer is more than 15 parts by weight, the adhesive force becomes excessive, and there is a fear that blocking is easily generated. In addition, there is a concern that breakage of the adherend is likely to occur at the time of the peeling operation.
Carboxyl group-containing monomer means a monomer having at least one carboxyl group in the molecule. By including the carboxyl group-containing monomer in the raw material monomer of the base polymer, the cohesive force of the base polymer (preferably, the acrylic polymer) is improved due to the formation of a secondary bond such as a hydrogen bond with the adherend, whereby the change in adhesive force with time can be more effectively suppressed, and the adhesive residue after peeling is less to the adherend, and the adhesive composition has higher aggregation. In addition, by containing the carboxyl group-containing monomer in the raw material monomer of the base polymer, when the crosslinking agent is used, a crosslinking reaction with the crosslinking agent can be effectively performed, the effect as the adhesive can be sufficiently exhibited, and the breakage of the adherend at the time of the peeling operation can be effectively prevented.
Specific examples of the carboxyl group-containing monomer include: acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, maleic acid, citraconic acid, maleic anhydride, itaconic anhydride, and the like. Among these, acrylic acid and methacrylic acid are preferable. The above carboxyl group-containing monomers may be used singly or in combination of any of 1 or more of 2.
The content of the carboxyl group-containing monomer is not particularly limited, and is, for example, preferably 0.5 to 15 parts by weight, more preferably 1 to 12 parts by weight, based on 100 parts by weight of the total monomer components of the base polymer. When the content of the carboxyl group-containing monomer is within the above range, since secondary bonds such as hydrogen bonds with an adherend are formed, the cohesive force of the base polymer (preferably, the acrylic polymer) is improved, the change in adhesive force with time can be more effectively suppressed, and the residual adhesive to the adherend after peeling is less, and the adhesive film has higher aggregation. When the content of the carboxyl group-containing monomer is more than 15 parts by weight, the adhesive force becomes excessive, and there is a fear that blocking is easily generated. In addition, there is a concern that breakage of the adherend is likely to occur at the time of the peeling operation. When the content of the carboxyl group-containing monomer is less than 0.5 parts by weight, sufficient adhesion is not obtained.
Examples of the sulfonic acid group-containing monomer include: styrene sulfonic acid, allyl sulfonic acid, sodium vinyl sulfonate, 2- (meth) acrylamide-2-methylpropanesulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, acryloxynaphthalene sulfonic acid, and the like.
Examples of the phosphate group-containing monomer include: 2-hydroxyethyl acryloyl phosphate, and the like.
Examples of the epoxy group-containing monomer include: glycidyl (meth) acrylate, epoxy group-containing acrylates such as 2-ethyl glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl (meth) acrylate, and the like.
Examples of the isocyanate group-containing monomer include: 2-isocyanatoethyl (meth) acrylate, and the like.
Examples of the amide group-containing monomer include: (meth) acrylamide; n, N-dialkyl (meth) acrylamides such as N, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, N-dipropyl (meth) acrylamide, N-diisopropyl (meth) acrylamide, N-di (N-butyl) (meth) acrylamide, N-di (t-butyl) (meth) acrylamide, and the like; n-alkyl (meth) acrylamides such as N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, and N-N-butyl (meth) acrylamide; n-vinylcarboxylic acid amides such as N-vinylacetamide; n, N-dimethylaminopropyl (meth) acrylamide, hydroxyethyl acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-methylolpropane (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N- (meth) acryloylmorpholine, and the like.
Examples of the monomer having a ring containing a nitrogen atom include: n-vinyl-2-pyrrolidone, N-methyl vinyl pyrrolidone, N-vinyl pyridine, N-vinyl piperidone, N-vinyl pyrimidine, N-vinyl piperazine, N-vinyl pyrazine, N-vinyl pyrrole, N-vinyl imidazole, N-vinyl oxazole, N- (meth) acryl-2-pyrrolidone, N- (meth) acryl piperidine, N- (meth) acryl pyrrolidine, N-vinyl morpholine, N-vinyl-3-morpholinone, N-vinyl-2-caprolactam, N-vinyl-1, 3-oxazin-2-one, N-vinyl-3, 5-morpholinedione, N-vinyl pyrazole, N-vinyl isoxazole, N-vinyl thiazole, N-vinyl isothiazole, N-vinyl pyridazine, and the like.
Examples of the monomer having a succinimide skeleton include: n- (meth) acryloyloxymethylene succinimide, N- (meth) acryl-6-oxahexamethylenesuccinimide, N- (meth) acryl-8-oxahexamethylenesuccinimide, and the like.
Examples of maleimide compounds include: n-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide, and the like.
Examples of the itaconimides include: n-methyl itaconimide, N-ethyl itaconimide, N-butyl itaconimide, N-octyl itaconimide, N-2-ethylhexyl itaconimide, N-cyclohexyl itaconimide, N-month Gui Jiyi itaconimide and the like.
Examples of the aminoalkyl (meth) acrylate include: aminoethyl (meth) acrylate, N-dimethylaminoethyl (meth) acrylate, N-diethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, and the like.
Examples of the alkoxyalkyl (meth) acrylate include: methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxypropyl (meth) acrylate, and the like.
Examples of vinyl ethers include: vinyl alkyl ethers such as methyl vinyl ether and ethyl vinyl ether.
Examples of the olefins include: ethylene, butadiene, isoprene, isobutylene, and the like.
The method for obtaining the base polymer is not particularly limited, and various known polymerization methods such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, and a photopolymerization method can be suitably used. For example, a solution polymerization method can be preferably employed. As a monomer supply method in the case of performing solution polymerization, a batch type in which all monomer raw materials are supplied at once, a continuous supply (drop wise) type, a split supply (drop wise) type, or the like can be suitably employed. The polymerization temperature in the solution polymerization may be appropriately selected depending on the types of monomers and solvents used, the types of polymerization initiators, and the like, and may be set to about 20 to 170℃for example (typically about 40 to 140 ℃).
The solvent (polymerization solvent) used in the solution polymerization may be appropriately selected from conventionally known organic solvents. For example, an aromatic compound (typically, aromatic hydrocarbon) selected from toluene and the like can be used; acetate esters such as ethyl acetate; aliphatic or alicyclic hydrocarbons such as hexane, heptane and cyclohexane; halogenated alkanes such as 1, 2-dichloroethane; lower alcohols such as isopropyl alcohol (for example, monohydric alcohols having 1 to 4 carbon atoms); ethers such as t-butyl methyl ether; any one or a mixture of two or more solvents selected from ketones such as methyl ethyl ketone.
The initiator used in the polymerization may be appropriately selected from conventionally known polymerization initiators depending on the kind of the polymerization method. For example, one or two or more azo polymerization initiators such as 2,2' -Azobisisobutyronitrile (AIBN) may be preferably used. As other examples of the polymerization initiator, there may be mentioned: persulfates such as potassium persulfate; peroxide initiators such as benzoyl peroxide and hydrogen peroxide; substituted ethane initiators such as phenyl substituted ethane; aromatic carbonyl compounds, and the like. As still other examples of the polymerization initiator, there are cited redox-type initiators obtained by combining a peroxide with a reducing agent. Such polymerization initiators may be used singly or in combination of two or more. The amount of the polymerization initiator to be used may be a usual amount, and for example, may be selected from the range of about 0.005 to about 1 part by weight (typically about 0.01 to about 1 part by weight) based on 100 parts by weight of the entire monomer components.
The weight average molecular weight (Mw) of the base polymer (suitably, the acrylic polymer) in the technology disclosed herein is not particularly limited, and may be, for example, 2,000,000 or less, preferably 400,000 or more. In general, when the weight average molecular weight Mw exceeds 2,000,000, the cohesive force tends to increase due to the effect of entanglement of the polymer, and the fluidity tends to decrease, and a sufficient adhesive area may not be obtained, and the adherend may not be fixed.
The weight average molecular weight (Mw) herein refers to a value in terms of standard polystyrene obtained by Gel Permeation Chromatography (GPC). As a GPC apparatus, for example, model name "HLC-8320GPC" (column: TSKgelGMH-H (S), manufactured by Tosoh Co., ltd.) may be used.
(multifunctional oligomer)
The term "multifunctional" as used herein refers to having 2 or more functionalities. In some preferred embodiments, the polyfunctional oligomer has a functionality of preferably 2 or more, more preferably 3 or more, and still more preferably 5 or more, from the viewpoint of both the adhesion reliability of the adhesive layer and the degree of decrease in the adhesive force after UV irradiation.
In some preferred embodiments, the multifunctional oligomer comprises at least one selected from the group consisting of an acrylic modified resin, a polyurethane modified resin, an epoxy modified resin, a phenolic modified resin, a polyether modified resin, a polyester modified resin, and a silicone modified resin.
In some preferred embodiments, the multifunctional oligomer comprises at least one of a polyurethane modified acrylic resin, an acrylic modified polyurethane resin, an epoxy modified acrylic resin, an epoxy modified polyurethane resin, an o-cresol formaldehyde modified resin, a phenolic modified acrylic resin, a phenolic modified polyurethane resin, a phenolic modified epoxy resin, a polyether modified acrylate resin, a polyester modified acrylate resin, and a silicone modified acrylate resin.
In some preferred embodiments, the multifunctional oligomer preferably comprises at least one of the group consisting of polyurethane modified acrylates, epoxy modified acrylates, polyether modified acrylates, polyester modified acrylates, and silicone modified acrylates.
As the urethane-modified acrylate, urethane (meth) acrylate having 2 or more (meth) acryloyl groups as functional groups added to the urethane skeleton can be used. Urethane (meth) acrylates are obtained, for example, by reacting a polyol, an isocyanate, and a hydroxy (meth) acrylate (e.g., 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate). Examples of the isocyanate include: examples of the aromatic isocyanate and the aliphatic isocyanate include toluene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate. Examples of the urethane (meth) acrylate include: the Art Resin UN series manufactured by Ind, new Zhongcun chemical industry Co., ltd., the NK Oligo U series manufactured by Nippon chemical industry Co., ltd., and the Violet UV series manufactured by Japanese synthetic chemical industry Co., ltd.).
The epoxy-modified acrylate may be prepared by reacting an epoxy group of an epoxy resin with a carboxyl group of an acrylic monomer, and examples thereof include: epoxy (meth) acrylate having 2 or more (meth) acryloyl groups as functional groups added to the epoxy skeleton. Epoxy (meth) acrylates are obtained by reacting hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate, and epoxy resins with (meth) acrylic acid to obtain prepolymers having 2 or more functions. Since almost all of the epoxy groups can be theoretically acrylated, the epoxy resin can be bisphenol a type, novolac epoxy type, acid and anhydride modified epoxy type, and the like. The brittleness of the epoxy resin is overcome by introducing a flexible long chain according to the requirement, the photocuring efficiency is improved by introducing unsaturated bonds, and the practical effects of controlling the resin compatibility, the curing shrinkage rate and the like by selecting and adjusting the molecular weight are achieved. Specific examples of the epoxy (meth) acrylate include epoxy ester series manufactured by risoxy SP and risoxy VR manufactured by shiman, and agisn 3050, 2020, 9750, and Kyoeisha Chemical co.
As polyether modified acrylic ester, ethylene oxide or propylene oxide and dihydric alcohol or polyhydric alcohol are subjected to anion ring-opening polymerization in strong alkali to obtain hydroxyl-terminated polyether, and then the hydroxyl-terminated polyether is subjected to acrylic esterification to obtain polyether acrylic ester. Since the esterification reaction is carried out under acidic conditions and the ether linkages are susceptible to acid and are destroyed, transesterification processes are used to prepare polyether acrylates. The hydroxyl-terminated polyether, excessive ethyl acrylate and polymerization inhibitor are mixed and heated, ester exchange reaction is carried out under the action of a catalyst (such as triisopropyl titanate), generated ethanol and ethyl acrylate form an azeotrope to be distilled out, the ethyl acrylate fraction is returned to a reaction kettle again through a fractionating tower, the ethanol is fractionated out, the ester exchange reaction is thoroughly carried out, and excessive ethyl acrylate is distilled out in vacuum. Examples of commercial products of polyether-modified acrylates include: high performance CN550 manufactured by AgiSyn 703 and kingchem Americas, inc. of Dissman, etc.
As polyester modified acrylic ester, can be prepared by reacting hydroxyl acrylate with anhydride to prepare anhydride semi-adduct, and then esterifying with polyester polyol. Polyester polyols may also be obtained from polyacids and polyols and then acrylated. The polyester modified acrylic ester has better flexibility and wettability. In addition, amine modified polyester acrylate can be used, so that oxygen inhibition can be reduced, and the UV reaction rate and the surface hardness of the UV post-adhesive layer can be improved. Examples of the commercial products of the polyester-modified acrylate include: PE44F and PE56F of chang chemical 6312-100, 6331 and basf, etc.
As the organosilicon modified acrylic ester, a hydrosilylation method, an esterification method, a hydrolysis method, a condensation micromolecule removing method and a urethanization addition method can be used for synthesis, for example, dichlorodimethylsilane monomer and hydroxyethyl acrylate are used for hydrolytic condensation under the catalysis of alkali, and HEA is introduced into a polysiloxane chain as a terminal group to obtain the organosilicon modified acrylic prepolymer. As a commercially available product of the silicone-modified acrylate, bossin B-818 and the like can be mentioned.
In some preferred embodiments, the content of the multifunctional oligomer is preferably 20 to 200 parts by weight, more preferably 30 to 150 parts by weight, still more preferably 40 to 120 parts by weight, relative to 100 parts by weight of the base polymer. When the content of the multifunctional oligomer falls within the above range, sufficient adhesion reliability and operability can be obtained, while good compatibility, cohesion and high-efficiency viscosity reduction effect after irradiation of ultraviolet rays can be achieved.
(antistatic agent)
Examples of the antistatic agent contained in the composition for forming an adhesive layer include conductive polymers, conductive inorganic fine particles, metal fine particles or fibers, ionic compounds, and ionic surfactants. These antistatic agents may be used alone or in combination of 2 or more.
< conductive Polymer >
Examples of the conductive polymer include: polyaniline, polypyrrole, polythiophene, polyquinoxaline, polyacetylene, polyethyleneimine, allylamine polymer, and the like. Among these, polyaniline, polythiophene, and the like, which easily form a water-soluble conductive polymer or a water-dispersible conductive polymer, are preferably used. These conductive polymers may be used alone or in combination of 2 or more.
< conductive inorganic particles >
Examples of the conductive inorganic fine particles include: conductive metal oxides, carbon nanotubes, graphene, fullerenes, acetylene black, ketjen black, natural graphite, artificial graphite, titanium black, and the like. These conductive inorganic fine particles may be used alone or in combination of 2 or more.
Examples of the conductive metal oxide include: tin oxides, antimony oxides, indium oxides, zinc oxides, and other metal oxides. Examples of the conductive fine particles of tin oxide include, in addition to tin oxide: antimony doped tin oxide, indium doped tin oxide, aluminum doped tin oxide, tungsten doped tin oxide, a titanium oxide-cerium oxide-tin oxide composite, a titanium oxide-tin oxide composite, and the like. The average particle diameter of the fine particles is 1 to 100nm, preferably 2 to 50nm.
< Metal particles or fibers >
Any suitable polymer may be used as long as the effects of the present invention can be obtained. Examples include: particles, nanowires, etc. of gold, silver, copper, aluminum, nickel, or alloys thereof. These metal fine particles or fibers may be used alone or in combination of 2 or more.
< Ionic Compound >
Examples of the ionic compound include: alkali metal salts and/or organic cation-anion salts, and the like. The term "organic cation-anion salt" as used herein refers to an organic salt having a cation portion composed of an organic substance, and an anion portion may be an organic substance or an inorganic substance. "organic cation-anion salts" are also referred to as ionic liquids, ionic solids. These ionic compounds may be used alone or in combination of 2 or more.
The alkali metal salt may be an organic salt or an inorganic salt of an alkali metal.
Examples of the alkali metal ion constituting the cation portion of the alkali metal salt include ions of lithium, sodium, potassium, and the like. Among these alkali metal ions, lithium ions are preferable.
The anion part of the alkali metal salt may be formed of an organic material or an inorganic material.
Examples of the anion unit constituting the organic salt include: CH (CH) 3 COO - 、CF 3 COO - 、CH 3 SO 3 - 、CF 3 SO 3 - 、(CF 3 SO 2 ) 3 C - 、C 4 F 9 SO 3 - 、C 3 F 7 COO - 、(CF 3 SO 2 )(CF 3 CO)N - 、(FSO 2 ) 2 N - 、 - O 3 S(CF 2 ) 3 SO 3 - 、PF 6 - 、CO 3 2- Anions represented by the following general formulae (1) to (4), and the like.
(1)：(C n F 2n+1 SO 2 ) 2 N - (wherein n is an integer of 1 to 10),
(2)：CF 2 (C m F 2m SO 2 ) 2 N - (wherein m is an integer of 1 to 10),
(3)： - O 3 S(CF 2 ) l SO 3 - (wherein l is an integer of 1 to 10),
(4)：(C p F 2p+1 SO 2 )N - (C q F 2q+1 SO 2 ) (wherein, p and q are integers of 1 to 10). In particular, an ionic compound having good ionization can be obtained in the anion portion containing a fluorine atom, and thus is preferably used.
As the anion part constituting the inorganic salt, cl can be used - 、Br - 、I - 、AlCl 4 - 、Al 2 Cl 7 - 、BF 4 - 、PF 6 - 、ClO 4 - 、NO 3 - 、AsF 6 - 、SbF 6 - 、NbF 6 - 、TaF 6 - 、(CN) 2 N - Etc.
The anion part is preferably (CF) 3 SO 2 ) 2 N - 、(C 2 F 5 SO 2 ) 2 N - And the like represented by the above general formula (1)(perfluoroalkyl sulfonyl) imines, particularly preferred are (CF) 3 SO 2 ) 2 N - Represented by trifluoromethanesulfonyl imide.
Specific examples of the organic salt of an alkali metal include: sodium acetate, sodium alginate, sodium lignin sulfonate, sodium toluene sulfonate, liCF 3 SO 3 、Li(CF 3 SO 2 ) 2 N、Li(CF 3 SO 2 ) 2 N、Li(C 2 F 5 SO 2 ) 2 N、Li(C 4 F 9 SO 2 ) 2 N、Li(CF 3 SO 2 ) 3 C、KO 3 S(CF 2 ) 3 SO 3 K、LiO 3 S(CF 2 ) 3 SO 3 K, etc., of which LiCF is preferred 3 SO 3 、Li(CF 3 SO 2 ) 2 N、Li(C 2 F 5 SO 2 ) 2 N、Li(C 4 F 9 SO 2 ) 2 N、Li(CF 3 SO 2 ) 3 C, etc., more preferably Li (CF 3 SO 2 ) 2 N、Li(C 2 F 5 SO 2 ) 2 N、Li(C 4 F 9 SO 2 ) 2 N and other fluorine-containing imide lithium salt, particularly preferably (perfluoroalkyl sulfonyl) imide lithium salt.
Examples of the inorganic salt of an alkali metal include lithium perchlorate and lithium iodide.
The organic cation-anion salt used in the present invention is composed of a cation component and an anion component, and the cation component is composed of an organic substance. Specific examples of the cationic component include: pyridinium cations, piperidinium cations, pyrrolidinium cations, cations having a pyrroline skeleton, imidazolium cations, tetrahydropyrimidinium cations, dihydropyrimidinium cations, pyrazolinium cations, tetraalkylammonium cations, trialkylsulfonium cations, tetraalkylphosphonium cations, and the like.
Examples of the anionic component include: cl - 、Br - 、I - 、AlCl 4 - 、Al 2 Cl 7 - 、BF 4 - 、PF 6 - 、ClO 4 - 、NO 3 - 、CH 3 COO - 、CF 3 COO - 、CH 3 SO 3 - 、CF 3 SO 3 - 、(CF 3 SO 2 ) 3 C - 、AsF 6 - 、SbF 6 - 、NbF 6 - 、TaF 6 - 、(CN) 2 N - 、C 4 F 9 SO 3 - 、C 3 F 7 COO - 、(CF 3 SO 2 )(CF 3 CO)N - 、(FSO 2 ) 2 N - 、 - O 3 S(CF 2 ) 3 SO 3 - Anions represented by the following general formulae (1) to (4), and the like.
(1)：(C n F 2n+1 SO 2 ) 2 N - (wherein n is an integer of 1 to 10),
(2)：CF 2 (C m F 2m SO 2 ) 2 N - (wherein m is an integer of 1 to 10),
(3)： - O 3 S(CF 2 ) l SO 3 - (wherein l is an integer of 1 to 10),
(4)：(C p F 2p+1 SO 2 )N - (C q F 2q+1 SO 2 ) (wherein, p and q are integers of 1 to 10). Among them, particularly, an anionic component containing a fluorine atom is preferably used because an ionic compound having good ionization can be obtained.
In some preferred embodiments, the organic cation-anion salt is preferably a nitrogen-containing onium salt, a sulfur-containing onium salt, or a phosphonium-containing salt, and more preferably a salt formed from an organic cation component and an anion component represented by the following general formulae (a) to (E) is used. This is because excellent antistatic ability can be exhibited.
In the formula (A), ra represents a hydrocarbon group having 4 to 20 carbon atoms, and Rb and Rc each independently represent hydrogen or a hydrocarbon group having 1 to 16 carbon atoms. Ra, rb, and Rc may contain a heteroatom. In addition, when the nitrogen atom is bonded by a double bond, rc is not present.
In the formula (B), rd represents a hydrocarbon group having 2 to 20 carbon atoms, and Re, rf and Rg each independently represent hydrogen or a hydrocarbon group having 1 to 16 carbon atoms. Rd, re, rf and Rg may contain heteroatoms.
In the formula (C), rh represents a hydrocarbon group having 2 to 20 carbon atoms, and Ri, rj and Rk each independently represent hydrogen or a hydrocarbon group having 1 to 16 carbon atoms. Rh, ri, rj and Rk may contain heteroatoms.
In the formula (D), Z represents a nitrogen, sulfur, or phosphorus atom, and Rl, rm, rn, and Ro each independently represent a hydrocarbon group having 1 to 20 carbon atoms and may contain a hetero atom. Where Z is a sulfur atom, ro is not present.
In the formula (E), rp represents a hydrocarbon group having 1 to 18 carbon atoms, and may contain a hetero atom.
Examples of the cation represented by the formula (a) include a pyridinium cation, a piperidinium cation, a pyrrolidinium cation, a cation having a pyrroline skeleton, and a cation having a pyrrole skeleton. Specific examples include: pyridinium cations such as 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, and 1-butyl-3, 4-dimethylpyridinium cation; piperidinium cations such as 1-propylpiperidinium cation, 1-pentylpiperidinium cation, 1-dimethylpiperidinium cation, 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1-methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl-1-heptylpiperidinium cation, 1-ethyl-1-propylpiperidinium cation, 1-ethyl-1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation, 1-dipropylpiperidinium cation, 1-propyl-1-butylpiperidinium cation, and 1, 1-dibutylpiperidinium cation; pyrrolidinium cations such as 1, 1-dimethylpyrrolidinium cation, 1-methyl-1-ethylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1-hexylpyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1-ethyl-1-pentylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidinium cation, 1-ethyl-1-heptylpyrrolidinium cation, 1-dipropylpyrrolidinium cation, 1-propyl-1-butylpyrrolidinium cation, and 1, 1-dibutylpyrrolidinium cation; 2-methyl-1-pyrroline cation, 1-ethyl-2-phenylindole cation, 1, 2-dimethylindole cation, 1-ethylcarbazole cation, and the like.
Examples of the cation represented by the formula (B) include: imidazolium cations, tetrahydropyrimidinium cations, dihydropyrimidinium cations, and the like. Specific examples include: imidazolium cations such as 1, 3-dimethylimidazolium cation, 1, 3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl-3-methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation, 1, 2-dimethyl-3-propylimidazolium cation, 1-ethyl-2, 3-dimethylimidazolium cation, 1-butyl-2, 3-dimethylimidazolium cation, and 1-hexyl-2, 3-dimethylimidazolium cation; tetrahydropyrimidinium cations such as 1, 3-dimethyl-1, 4,5, 6-tetrahydropyrimidinium cations, 1,2, 3-trimethyl-1, 4,5, 6-tetrahydropyrimidinium cations, 1,2,3, 4-tetramethyl-1, 4,5, 6-tetrahydropyrimidinium cations, and 1,2,3, 5-tetramethyl-1, 4,5, 6-tetrahydropyrimidinium cations; 1-butyl-3-methylpyridinium cations such as 1, 3-dimethyl-1, 4-dihydropyridinium cations, 1, 3-dimethyl-1, 6-dihydropyrimidinium cations, 1,2, 3-trimethyl-1, 4-dihydropyrimidinium cations, 1,2, 3-trimethyl-1, 6-dihydropyrimidinium cations, 1,2,3, 4-tetramethyl-1, 4-dihydropyrimidinium cations, dihydropyrimidinium cations such as 1,2,3, 4-tetramethyl-1, 6-dihydropyrimidinium cations, and 1-butyl-3-methylpyridinium bisimide.
Examples of the cation represented by the formula (C) include: pyrazolium cations, dihydropyrazolium cations, and the like. Specific examples include: 1-methylpyrazolium cation, 3-methylpyrazolium cation, 1-ethyl-2-methyldihydride pyrazolium cation, and the like.
Examples of the cation represented by the formula (D) include: tetraalkylammonium cations, trialkylsulfonium cations, tetraalkylphosphonium cations, and the like. In addition, cations in which a part of the alkyl group of these cations is substituted with an alkenyl group, an alkoxy group, or an epoxy group may also be used. In addition, rl, rm, rn and Ro are hydrocarbon groups having 1 to 20 carbon atoms as described above, and are preferably alkyl groups having 1 to 20 carbon atoms. In addition, rl, rm, rn, and Ro may be an aromatic ring group or an alicyclic group. Specific examples of the cation represented by the formula (D) include: and tetraalkylammonium cations, trialkylsulfonium cations, tetraalkylphosphonium cations, and cations obtained by substituting a part of the above alkyl groups with alkenyl groups, alkoxy groups, and further epoxy groups. Specific examples include: n, N-dimethyl-N-ethyl-N-propylammonium cation, N-dimethyl-N-ethyl-N-butylammonium cation, N-dimethyl-N-ethyl-N-pentylammonium cation, N-dimethyl-N-ethyl-N-hexylammonium cation, N, N-dimethyl-N-ethyl-N-heptylammonium cation, N-dimethyl-N-ethyl-N-nonylammonium cation, N-dimethyl-N, N-dipropylammonium cation, N-dimethyl-N-propyl-N-butylammonium cation, N, N-dimethyl-N-propyl-N-pentylammonium cation, N-dimethyl-N-propyl-N-hexylammonium cation, N-dimethyl-N-propyl-N-heptylammonium cation, N-dimethyl-N-butyl-N-hexylammonium cation, N, N-dimethyl-N-butyl-N-heptylammonium cation, N-dimethyl-N-pentyl-N-hexylammonium cation, N-dimethyl-N, N-dihexylammonium cation, trimethylheptylammonium cation, N-diethyl-N-methyl-N-propylammonium cation, N, N-diethyl-N-methyl-N-pentylammonium cation, N-diethyl-N-methyl-N-heptylammonium cation, N-diethyl-N-propyl-N-pentylammonium cation, triethylmethylammonium cation, triethylpropylammonium cation, triethylpentylammonium cation, triethylheptylammonium cation, N, N-dipropyl-N-methyl-N-ethylammonium cation, N-dipropyl-N-methyl-N-pentylammonium cation, N-dipropyl-N-butyl-N-hexylammonium cation, N-dipropyl-N, N-dihexylammonium cation, N, tetraalkylammonium cations such as N-dibutyl-N-methyl-N-pentylammonium cation, N-dibutyl-N-methyl-N-hexylammonium cation, trioctylmethylammonium cation, N-methyl-N-ethyl-N-propyl-N-pentylammonium cation, tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, tetrahexylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium cation, glycidyl trimethylammonium cation, diallyl dimethylammonium cation, and the like; trialkylsulfonium cations such as trimethylsulfonium cation, triethylsulfonium cation, tributylsulfonium cation, trihexylsulfonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, and dimethyldecylsulfonium cation; and tetraalkylphosphonium cations such as tetramethyl phosphonium cation, tetraethyl phosphonium cation, tetrabutyl phosphonium cation, tetrahexyl phosphonium cation, triethyl methyl phosphonium cation, tributyl ethyl phosphonium cation, and trimethyl decyl phosphonium cation.
In the present invention, from the viewpoint of obtaining particularly excellent antistatic power, it is preferable to use a cation represented by the formula (a) (particularly, an asymmetric tetraalkylammonium cation such as a 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-3, 4-dimethylpyridinium cation, etc.), a cation represented by the formula (D) (particularly, triethylmethylammonium cation, tributylethylammonium cation, trimethyldecyl ammonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecyl sulfonium cation, triethylmethylphosphonium cation, tributylethylphosphonium cation, an asymmetric tetraalkylammonium cation such as trimethyldecyl phosphonium cation, trialkylphosphonium cation, tetraalkylphosphonium cation, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium cation, dimethylsulfonium cation, triglycium, etc.).
Specific examples of the cation represented by the formula (E) include sulfonium salts having, as Rp, an alkyl group having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, octadecyl and the like.
Any suitable anionic component may be used as long as it can form an ionic liquid together with the cationic component. Examples include: cl - 、Br - 、I - 、AlCl 4 - 、Al 2 Cl 7 - 、BF 4 - 、PF 6 - 、ClO 4 - 、NO 3 - 、CH 3 COO - 、CF 3 COO - 、CH 3 SO 3 - 、CF 3 SO 3 - 、(CF 3 SO 2 ) 2 N - 、(CF 3 SO 2 ) 3 C - 、AsF 6 - 、SbF 6 - 、NbF 6 - 、TaF 6 - 、F(HF) n - 、(CN) 2 N - 、C 4 F 9 SO 3 - 、(C 2 F 5 SO 2 ) 2 N - 、C 3 F 7 COO - 、(CF 3 SO 2 )(CF 3 CO) N, and the like. The hydrophobic anionic component tends to be less likely to bleed out to the adhesive surface, and is preferably used from the viewpoint of low contamination. Furthermore, the anionic component containing fluorine atoms can obtain an ionic compound having a low melting point, and is particularly preferably used.
The organic cation-anion salt in the present invention can be suitably selected and used from the above-mentioned combinations of cation components and anion components, and examples thereof include: 1-butylpyridinium tetrafluoroborate, 1-butylpyridinium hexafluorophosphate, 1-butyl-3-methylpyridinium tetrafluoroborate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide salt, 1-butyl-3-methylpyridinium bis (pentafluoroethylsulfonyl) imide salt, 1-hexylpyridinium tetrafluoroborate, 1-dimethylpyrrolidinium bis (trifluoromethanesulfonyl) imide salt, 1-methyl-1-ethylpyrrolidinium bis (trifluoromethanesulfonyl) imide salt, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide salt, 1-methyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide salt, 1-methyl-1-pentylpyrrolidinium bis (trifluoromethanesulfonyl) imide salt, 1-methyl-1-hexylpyrrolidinium bis (trifluoromethanesulfonyl) imide salt, 1-methyl-1-dimethylpyrrolidinium bis (trifluoromethanesulfonyl) imide salt, 1-methylpyrrolidinium bis (trifluoromethanesulfonyl) imide salt, 1-Ethyl-1-hexylpyrrolidinium bis (trifluoromethanesulfonyl) imide salt, 1-Ethyl-1-heptylpyrrolidinium bis (trifluoromethanesulfonyl) imide salt, 1-dipropylpyrrolidinium bis (trifluoromethanesulfonyl) imide salt, 1-propyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide salt, 1-dibutylpyrrolidinium bis (trifluoromethanesulfonyl) imide salt, 1-propylpiperidinium bis (trifluoromethanesulfonyl) imide salt, 1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide salt, 1-dimethylpiperidinium bis (trifluoromethanesulfonyl) imide salt 1-methyl-1-ethylpiperidinium bis (trifluoromethanesulfonyl) imide salt, 1-methyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide salt, 1-methyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide salt, 1-methyl-1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide salt, 1-methyl-1-hexylpiperidinium bis (trifluoromethanesulfonyl) imide salt, 1-methyl-1-heptylpiperidinium bis (trifluoromethanesulfonyl) imide salt, 1-ethyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide salt, 1-ethyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide salt, 1-ethyl-1-pentylpiperidinium bis (trifluoromethylsulfonyl) imide salt, 1-ethyl-1-hexylpiperidinium bis (trifluoromethylsulfonyl) imide salt, 1-ethyl-1-heptylpiperidinium bis (trifluoromethylsulfonyl) imide salt, 1-dipropylpiperidinium bis (trifluoromethylsulfonyl) imide salt, 1-propyl-1-butylpiperidinium bis (trifluoromethylsulfonyl) imide salt, 1-dibutylpiperidinium bis (trifluoromethylsulfonyl) imide salt, 1-dimethylpyrrolidinium bis (pentafluoroethylsulfonyl) imide salt, 1-methyl-1-ethylpyrrolidinium bis (pentafluoroethylsulfonyl) imide salt, 1-methyl-1-propylpyrrolidinium bis (pentafluoroethylsulfonyl) imide salt, 1-methyl-1-butylpyrrolidinium bis (pentafluoroethylsulfonyl) imide salt, 1-methyl-1-pentylpyrrolidinium bis (pentafluoroethylsulfonyl) imide salt, 1-methylsulfonyl-pyrrolidinium bis (pentafluoroethylsulfonyl) imide salt, 1-methyl-1-pentylmethylpyrrolidinium bis (pentafluoroethylsulfonyl) imide salt, penta-1-pyrrolidinium bis (pentafluoroethylsulfonyl) imide salt, penta-1-methylsulfonyl) pyrrolidinium bis (pentafluoroethylpyrrolidinium (pentafluoroethylsulfonyl) imide salt, 1-methyl-1-pentylmethyl-1-pentylmethylpyrrolidinium bis (pentafluoroethylsulfonyl) imide salt 1-ethyl-1-pentylpyrrolidinium bis (pentafluoroethanesulfonyl) imide salt, 1-ethyl-1-hexylpyrrolidinium bis (pentafluoroethanesulfonyl) imide salt, 1-ethyl-1-heptylpyrrolidinium bis (pentafluoroethanesulfonyl) imide salt, 1-dipropylpyrrolidinium bis (pentafluoroethanesulfonyl) imide salt, 1-propyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide salt, 1-dibutylpyrrolidinium bis (pentafluoroethanesulfonyl) imide salt, 1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide salt, 1-pentylpiperidinium bis (pentafluoroethanesulfonyl) imide salt, 1-dimethylpiperidinium bis (pentafluoroethanesulfonyl) imide salt, 1-methyl-1-ethylpiperidinium bis (pentafluoroethanesulfonyl) imide salt, 1-methyl-1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide salt, 1-methyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide salt, 1-methylsulfonyl-penta-ethylpiperidinium bis (pentafluoroethanum) imide salt, 1-methylsulfonyl) bis (pentafluoroethanum) imide salt, 1-ethyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imines, 1-ethyl-1-pentylpiperidinium bis (pentafluoroethanesulfonyl) imines, 1-ethyl-1-hexylpiperidinium bis (pentafluoroethanesulfonyl) imines, 1-ethyl-1-heptylpiperidinium bis (pentafluoroethanesulfonyl) imines, 1-dipropylpiperidinium bis (pentafluoroethanesulfonyl) imines, 1-propyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imines, 1-dibutylpiperidinium bis (pentafluoroethanesulfonyl) imines, 2-methyl-1-pyrroline tetrafluoroborates, 1-ethyl-2-phenylindoline tetrafluoroborates, 1, 2-dimethylindolium tetrafluoroborates, 1-ethylcarbazole tetrafluoroborates, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazolium hepta-1-methylsulfonyl) imines, 1-ethylimidazolium tris (pentafluoroethanesulfonyl) imines, 1-3-methylsulfonylmethane, 1-ethylimidazolium) 3-methylsulfonate, 1-bis (methylsulfonylmethane) 3-methylsulfonylmethane-3-methylsulfonylmethane salts 1-ethyl-3-methylimidazolium bis (pentafluoroethanesulfonyl) iminium salt, 1-ethyl-3-methylimidazolium tris (trifluoromethanesulfonyl) methide, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium trifluoroacetate, 1-butyl-3-methylimidazolium heptafluorobutyrate, 1-butyl-3-methylimidazolium trifluoromethane sulfonate, 1-butyl-3-methylimidazolium perfluorobutanesulfonate, 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) iminium salt, 1-hexyl-3-methylimidazolium bromide, 1-hexyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-3-methylimidazolium trifluoromethane sulfonate, 1-octyl-3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium hexafluoroborate, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-difluoromethyl-2, 2-methylimidazolium tetrafluoroborate, 1-N-difluoromethyl-3-methylimidazolium tetrafluoroborate, N-dimethyl-N-ethyl-N-propylammonium bis (trifluoromethanesulfonyl) imide salt, N-dimethyl-N-ethyl-N-butylammonium bis (trifluoromethanesulfonyl) imide salt, N-dimethyl-N-ethyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide salt, N-dimethyl-N-ethyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide salt, N-dimethyl-N-ethyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide salt, N, N-dimethyl-N-ethyl-N-nonylammonium bis (trifluoromethanesulfonyl) imide salt, N-dimethyl-N, N-dipropylammonium bis (trifluoromethanesulfonyl) imide salt, N-dimethyl-N-propyl-N-butylamino bis (trifluoromethanesulfonyl) imide salt, N-dimethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide salt, N-dimethyl-N-propyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide salt, N-dimethyl-N-propyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide salt, N, N-dimethyl-N-butyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide salt, N-dimethyl-N-butyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide salt, N-dimethyl-N-pentyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide salt, N-dimethyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide salt, trimethylheptylammonium bis (trifluoromethanesulfonyl) imide salt, N-diethyl-N-methyl-N-propylammonium bis (trifluoromethanesulfonyl) imide salt, N, N-diethyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide salt, N-diethyl-N-methyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide salt, N-diethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide salt, triethylpropylammonium bis (trifluoromethanesulfonyl) imide salt, triethylpentylammonium bis (trifluoromethanesulfonyl) imide salt, triethylheptylammonium bis (trifluoromethanesulfonyl) imide salt, N-dipropyl-N-methyl-N-ethylammonium bis (trifluoromethanesulfonyl) imide salt, N, N-dipropyl-N-methyl-N-pentylammonium bis (trifluoromethylsulfonyl) imide salt, N-dipropyl-N-butyl-N-hexylammonium bis (trifluoromethylsulfonyl) imide salt, N-dipropyl-N, N-dihexylammonium bis (trifluoromethylsulfonyl) imide salt, N-dibutyl-N-methyl-N-pentylammonium bis (trifluoromethylsulfonyl) imide salt, N-dibutyl-N-hexylammonium bis (trifluoromethylsulfonyl) imide salt, trioctylmethylammonium bis (trifluoromethylsulfonyl) imide salt, N-methyl-N-ethyl-N-pentylammonium bis (trifluoromethylsulfonyl) imide salt, 1-butylpyridinium (trifluoromethylsulfonyl) trifluoroacetamide salt, 1-butyl-3-methylpyridinium (trifluoromethylsulfonyl) trifluoroacetamide salt, 1-ethyl-3-methylimidazolium (trifluoromethylsulfonyl) trimethylammonium (trifluoromethylsulfonyl) imide salt, tetramethylammonium bis (methylsulfonylmethylammonium) fluoride, diallylammonium bis (methylsulfonylmethylsulfonamide) salt, diallyldiammonium (difluoromethylenesulfonamide) salt, bis (methylsulfonylmethylsulfonamide) fluoride salt, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium tetrafluoroborate, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium trifluoromethanesulfonate, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) imide salt, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (pentafluoroethanesulfonyl) imide salt, glycidyl trimethylammonium trifluoromethanesulfonate, glycidyl trimethylammonium bis (trifluoromethanesulfonyl) imide salt, glycidyl trimethylammonium bis (pentafluoroethanesulfonyl) imide salt, diallyl dimethyl bis (pentafluoroethanesulfonyl) imide salt, and the like.
The method for synthesizing the organic cation-anion salt is not particularly limited as long as the target organic cation-anion salt can be obtained, and in general, a halide method, a hydroxide method, an acid ester method, a complexation method, a neutralization method, or the like described in the literature "ionic liquid-open machine function, the forefront of which is the" in the future- "[ CMC published by the company, can be used. In addition, commercially available organic cation-anion salts may also be used.
< Ionic surfactant >
Examples of the ionic surfactant include: cationic surfactants (e.g., quaternary ammonium salt type, phosphonium salt type, sulfonium salt type, etc.), anionic surfactants (e.g., carboxylic acid type, sulfonate type, sulfate type, phosphate type, phosphite type, etc.), zwitterionic surfactants (e.g., sulfobetaine type, alkyl betaine type, alkyl imidazolium betaine type, etc.), nonionic surfactants (e.g., polyol derivatives, beta-cyclodextrin inclusion compounds, sorbitan fatty acid mono/di-esters, polyoxyalkylene derivatives, amine oxides, etc.), and the like. These gold ionic surfactants may be used alone or in combination of 2 or more.
In some preferred embodiments, the antistatic agent is contained in an amount of preferably 0.0001 to 20 parts by weight, more preferably 0.0002 to 10 parts by weight, relative to 100 parts by weight of the base polymer. When the content of the antistatic agent is within the above range, a sufficient antistatic effect can be obtained, peeling static electricity generated during peeling can be sufficiently suppressed, and occurrence of phenomena such as electrostatic breakdown can be effectively suppressed, thereby avoiding or reducing damage to an adherend.
The adhesive composition of the present invention contains any appropriate other component within a range that does not impair the effects of the present invention. Examples of such other components include a crosslinking agent and a photoinitiator (photopolymerization initiator).
(crosslinking agent)
In the present invention, the adhesive composition preferably contains a crosslinking agent for the purpose of adjusting cohesion and the like. As the crosslinking agent, a conventionally used crosslinking agent can be used, and examples thereof include epoxy crosslinking agents, isocyanate crosslinking agents, melamine crosslinking agents, aziridine crosslinking agents, metal chelate crosslinking agents, and the like. By using these crosslinking agents, a proper crosslinking reaction can be generated, the cohesive force can be sufficiently improved, good adhesion can be ensured, and breakage of an adherend at the time of peeling operation can be effectively prevented. These crosslinking agents may be used alone or in combination of two or more.
As the epoxy-based crosslinking agent, a compound having two or more epoxy groups in one molecule can be used without particular limitation. Preferably an epoxy-based crosslinking agent having 3 to 5 epoxy groups in one molecule. The epoxy crosslinking agent may be used singly or in combination of two or more.
Specific examples of the epoxy-based crosslinking agent include, but are not particularly limited to: bisphenol A, epichlorohydrin-based epoxy resins, ethylene glycidyl ether, N, N, N ', N' -tetraglycidyl m-xylylenediamine, 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane, 1, 6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polyglycidyl ether, and the like. Examples of the commercial products of the epoxy-based crosslinking agent include trade names "tetra-C" and "tetra-X" manufactured by Mitsubishi gas chemical corporation, trade name "EPICLON CR-5L" manufactured by DIC corporation, trade name "DENACOL EX-512" manufactured by Daikovia chemical corporation, and trade name "TEPIC-G" manufactured by Nissan chemical industry corporation.
The amount of the epoxy-based crosslinking agent used is not particularly limited, and is, for example, preferably 0.01 to 3 parts by weight, more preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the base polymer.
In the embodiment containing the epoxy-based crosslinking agent, the epoxy equivalent of the epoxy-based crosslinking agent is preferably 80 to 120g/eq.
As the isocyanate-based crosslinking agent, polyfunctional isocyanates (meaning compounds having an average of two or more isocyanate groups per molecule, including compounds having an isocyanurate structure) can be preferably used. The isocyanate-based crosslinking agent may be used singly or in combination of two or more.
Examples of the polyfunctional isocyanate include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and the like.
Specific examples of the aliphatic polyisocyanate include: 1, 2-ethylene diisocyanate; 1, 2-butanediisocyanate, 1, 3-butanediisocyanate, 1, 4-butanediisocyanate and other butanediisocyanates; hexamethylene diisocyanate such as 1, 2-hexamethylene diisocyanate, 1, 3-hexamethylene diisocyanate, 1, 4-hexamethylene diisocyanate, 1, 5-hexamethylene diisocyanate, 1, 6-hexamethylene diisocyanate and 2, 5-hexamethylene diisocyanate; 2-methyl-1, 5-pentanediisocyanate, 3-methyl-1, 5-pentanediisocyanate, lysine diisocyanate, and the like.
Specific examples of the alicyclic polyisocyanate include: isophorone diisocyanate; cyclohexyl diisocyanate such as 1, 2-cyclohexyl diisocyanate, 1, 3-cyclohexyl diisocyanate, and 1, 4-cyclohexyl diisocyanate; cyclopentyl diisocyanate such as 1, 2-cyclopentyl diisocyanate and 1, 3-cyclopentyl diisocyanate; hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tetramethylxylylene diisocyanate, 4' -dicyclohexylmethane diisocyanate, and the like.
Specific examples of the aromatic polyisocyanate include: 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 4' -diphenylmethane diisocyanate, 2' -diphenylmethane diisocyanate, 4' -diphenyl ether diisocyanate, 2-nitrobiphenyl-4, 4' -diisocyanate, 2' -diphenylpropane-4, 4' -diisocyanate 3,3' -dimethyldiphenylmethane-4, 4' -diisocyanate, 4' -diphenylpropane diisocyanate, isophthalate diisocyanate, p-phenylene diisocyanate, naphthalene-1, 4-diisocyanate, naphthalene-1, 5-diisocyanate, 3' -dimethoxybiphenyl-4, 4' -diisocyanate, xylylene-1, 4-diisocyanate, xylylene-1, 3-diisocyanate, and the like.
As the preferable polyfunctional isocyanate, polyfunctional isocyanates having an average of 3 or more isocyanate groups per molecule can be exemplified. The trifunctional or higher isocyanate may be a polymer (typically a dimer or trimer) of a difunctional or higher isocyanate, a derivative (e.g., an addition reaction product of a polyol and two or more polyfunctional isocyanates), a polymer, or the like. Examples may include: dimers or trimers of diphenylmethane diisocyanate, isocyanurate forms of hexamethylene diisocyanate (isocyanurate-structured trimer adducts), reaction products of trimethylol propane and toluene diisocyanate, reaction products of trimethylol propane and hexamethylene diisocyanate, polymethylene polyphenyl isocyanates, polyether polyisocyanates, polyester polyisocyanates, and other polyfunctional isocyanates. Examples of the commercial products of the polyfunctional isocyanate include "DURANATE TPA-100" manufactured by Asahi chemical Co., ltd., and "CORONATE L" manufactured by Japanese polyurethane Industrial Co., ltd., and "CORONATE HL" manufactured by Japanese polyurethane Industrial Co., ltd., and "CORONATE HK" manufactured by Japanese polyurethane Industrial Co., ltd., and "CORONATE HX" manufactured by Japanese polyurethane Industrial Co., ltd., and "CORONATE2096" manufactured by Japanese polyurethane Industrial Co., ltd.
In the embodiment containing the isocyanate-based crosslinking agent, the isocyanate group content (NCO content) in the isocyanate-based crosslinking agent is preferably 7 to 15%.
The amount of the isocyanate-based crosslinking agent used is not particularly limited, and is, for example, preferably 0.1 to 6 parts by weight, and preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the base polymer.
Examples of melamine-based crosslinking agents include: hexamethylol melamine, butylated melamine resins (e.g., trade name "SUPER BECKAMINE J-820-60N" available from DIC Co., ltd.), and the like.
The amount of the melamine-based crosslinking agent used is not particularly limited, and is, for example, preferably 0.5 to 12 parts by weight, and preferably 1 to 8 parts by weight, based on 100 parts by weight of the base polymer.
Examples of the aziridine crosslinking agent include: trimethylolpropane tris [3- (1-aziridinyl) propionate ], trimethylolpropane tris [3- (1- (2-methyl) aziridinylpropionate) ]. As the aziridine crosslinking agent, commercially available ones can be used. For example, chemitite series (Nippon Shokubai Co., ltd.) such as Chemitite PZ-33 and Chemitite DZ-22E can be used.
Examples of the metal chelate crosslinking agent include: aluminum chelate compounds, titanium chelate compounds, zinc chelate compounds, zirconium chelate compounds, iron chelate compounds, cobalt chelate compounds, nickel chelate compounds, tin chelate compounds, manganese chelate compounds, chromium chelate compounds, and the like.
The amount of the crosslinking agent to be used is preferably 0.01 to 15 parts by weight based on 100 parts by weight of the base polymer. When the amount of the crosslinking agent is within the above range, the cohesive force of the adhesive can be improved, the occurrence of a residual gum on the adherend can be prevented, and the adhesive composition also has proper fluidity, and is liable to have good wettability to the adherend and further to have adhesion. In some embodiments, the amount of the crosslinking agent used is more preferably 10 parts by weight or less relative to 100 parts by weight of the base polymer from the viewpoint of avoiding a decrease in tackiness due to an excessive increase in cohesion.
In order to more effectively perform the above-mentioned crosslinking reaction, a crosslinking catalyst may also be used. As the crosslinking catalyst, for example, a tin catalyst (e.g., dioctyltin dilaurate) can be preferably used. The amount of the crosslinking catalyst used is not particularly limited, and is, for example, preferably 0.0001 to 1 part by weight based on 100 parts by weight of the base polymer.
(photoinitiator)
Examples of the photoinitiator include: benzoin ether photopolymerization initiator, acetophenone photopolymerization initiator, α -ketol photopolymerization initiator, aromatic sulfonyl chloride photopolymerization initiator, photoactive oxime photopolymerization initiator, benzoin photopolymerization initiator, benzil photopolymerization initiator, benzophenone photopolymerization initiator, ketal photopolymerization initiator, thioxanthone photopolymerization initiator, and the like.
Examples of the benzoin ether photopolymerization initiator include: benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-dimethoxy-1, 2-diphenylethane-1-one, anisole methyl ether, and the like. Examples of the acetophenone photopolymerization initiator include: 2, 2-diethoxyacetophenone, 2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 4-phenoxydichloroacetophenone, 4- (tert-butyl) dichloroacetophenone, and the like. Examples of the α -ketol photopolymerization initiator include: 2-methyl-2-hydroxy propiophenone, 1- [4- (2-hydroxyethyl) phenyl ] -2-methylpropan-1-one, and the like. Examples of the aromatic sulfonyl chloride photopolymerization initiator include: 2-naphthalenesulfonyl chloride, and the like. Examples of the photoactive oxime-based photopolymerization initiator include: 1-phenyl-1, 1-propanedione-2- (o-ethoxycarbonyl) -oxime, and the like. Examples of the benzoin photopolymerization initiator include benzoin. Examples of the benzil photopolymerization initiator include benzil. Examples of the benzophenone photopolymerization initiator include benzophenone, benzoyl benzoic acid, 3' -dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, and α -hydroxycyclohexyl phenyl ketone. Examples of the ketal photopolymerization initiator include: benzil dimethyl ketal, and the like. Examples of the thioxanthone photopolymerization initiator include: thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2, 4-dimethylthioxanthone, isopropylthioxanthone, 2, 4-diisopropylthioxanthone, dodecylthioxanthone, and the like.
In some preferred embodiments, the photoinitiator is preferably present in an amount of 0.5 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, relative to 100 parts by weight of the base polymer. By setting the amount of the photoinitiator to be within the above range, adhesion can be improved. When the content of the photoinitiator is less than 0.5 parts by weight, the adhesive is not sufficiently cured upon irradiation with active energy rays. When the content of the photoinitiator is more than 10 parts by weight, the storage stability of the adhesive may be lowered. In addition, too much initiator content may cause a phenomenon that the surface of the adhesive sheet is too hard to be peeled off from the surface to be adhered after UV irradiation.
In addition to the above components, the adhesive composition of the present invention may contain various additives, as necessary, which are usual in the adhesive field, such as plasticizers, softeners, antioxidants, etc., within a range that does not impair the effects of the present invention. Regarding such various additives, conventionally known additives can be used by a conventional method.
(formation of adhesive layer)
The adhesive layer disclosed herein may be formed by a known method. For example, a method (direct method) of forming an adhesive layer by directly applying (typically coating) the adhesive composition onto the substrate layer and drying it can be employed. In addition, a method (transfer method) of forming an adhesive layer on a surface (release surface) having releasability by applying the adhesive composition to the surface and drying the surface, and transferring the adhesive layer to a base material layer may also be employed. The transfer method is preferable from the viewpoint of productivity. The release surface may be a surface of a release liner, a back surface of a base material layer subjected to a release treatment, or the like. The pressure-sensitive adhesive layer disclosed herein is typically formed continuously, but is not limited to such a form, and may be formed in a regular or irregular pattern such as a dot shape or a stripe shape.
The adhesive composition may be applied by using a conventionally known coater such as a gravure roll coater, a die coater, or a bar coater. Alternatively, the adhesive composition may be applied by impregnation, curtain coating, or the like.
Drying of the adhesive composition is preferably performed under heating from the viewpoints of promoting the crosslinking reaction, improving the production efficiency, and the like. The drying temperature can be set, for example, at about 40 to 150℃and is usually preferably set at about 60 to 130 ℃. After drying the adhesive composition, aging may be further performed for the purpose of adjusting migration of components in the adhesive layer, progress of crosslinking reaction, relaxation of strain that may exist in the substrate film or the adhesive layer, and the like.
The thickness of the pressure-sensitive adhesive layer is not particularly limited, and is preferably 1 to 100 μm, more preferably 3 to 50 μm, in view of the balance between adhesiveness to an adherend and cohesiveness. By setting the thickness of the adhesive layer to the above range, good adhesion can be achieved.
[ substrate layer ]
The material of the base layer constituting the pressure-sensitive adhesive sheet disclosed herein is not particularly limited, and may be appropriately selected depending on the purpose of use, the manner of use, and the like of the pressure-sensitive adhesive sheet. Non-limiting examples of the usable base material layer include polyolefin films containing polyolefin such as polyethylene, polypropylene, polybutylene, and ethylene-propylene copolymer as a main component, polyester films containing polyester such as polyethylene terephthalate and polybutylene terephthalate as a main component, polyvinyl chloride films containing polyvinyl chloride as a main component, films containing cast polypropylene as a main component, and plastic films such as thermoplastic polyurethane films; foam sheets formed of a foam such as polyurethane foam, polyethylene foam, polychloroprene foam, or the like; various fibrous substances (natural fibers such as hemp and cotton, synthetic fibers such as polyester and vinylon, semisynthetic fibers such as acetate, etc.), woven fabrics and nonwoven fabrics obtained by blending or the like; paper such as japanese paper, high-quality paper, kraft paper, crepe paper, etc.; metal foil such as aluminum foil and copper foil. Of these, the substrate layer preferably contains at least one selected from the group consisting of thermoplastic polyurethane, polyethylene, polypropylene, polybutylene, ethylene-vinyl acetate copolymer, and polyvinyl chloride. The substrate may be a composite substrate. Examples of such a composite substrate include a substrate having a structure in which a metal foil and the plastic film are laminated, a plastic substrate reinforced with inorganic fibers such as glass cloth, and the like.
The surface of the base material layer of the present invention may be subjected to any surface treatment in order to improve adhesion to an adjacent layer, retention, and the like. Examples of the surface treatment include chemical or physical treatments such as chromic acid treatment, ozone exposure, flame exposure, high-voltage electric shock exposure, and ionizing radiation treatment, and coating treatment.
The thickness of the base material layer of the present invention may be set to any appropriate thickness depending on the desired strength, flexibility, purpose of use, and the like. The thickness of the base material layer is preferably 10 to 300. Mu.m, more preferably 30 to 200. Mu.m, still more preferably 50 to 150. Mu.m.
In one embodiment, the interior and/or surface of the substrate layer may also contain an antistatic agent. As the base material layer containing the antistatic agent, for example, a resin sheet kneaded with the antistatic agent can be used. The resin sheet may be formed from a composition for forming a substrate comprising a resin and an antistatic agent.
Examples of the resin include: thermoplastic polyurethane, polyethylene, polypropylene, polybutylene, ethylene-vinyl acetate copolymer, polyvinyl chloride, and the like.
As the antistatic agent contained in the inside and/or the surface of the substrate layer, any suitable antistatic agent may be used as long as the effects of the present invention can be obtained. For example, the antistatic agent described in the above adhesive layer can be used.
The method for incorporating the antistatic material into the base material is not particularly limited as long as the antistatic material can be uniformly mixed into the resin used for the base material, and examples thereof include a method for incorporating the antistatic material into the base material using a heated roll, a Banbury mixer, a pressure kneader, a twin-screw kneader, or the like.
[ Back coating ]
As shown in fig. 2, the adhesive sheet of the present invention may further include a back surface treatment layer 30, also referred to as a back coating layer, the back coating layer 30 being disposed on the opposite side of the substrate layer 10 from the adhesive layer 20.
The back coating layer forming material is not particularly limited, and 1 or 2 or more of polyurethane-based resins, epoxy-based resins, polyester-based resins, acrylic-based resins, polyamide-based resins, melamine-based resins, olefin-based resins, polystyrene-based resins, phenolic-based resins, isocyanurate-based resins, polyvinyl acetate-based resins, and the like can be used. In the case where an acrylic pressure-sensitive adhesive layer or the like is provided on the resin film base layer, a urethane-based, epoxy-based, polyester-based, or acrylic-based back coating is preferable.
In some preferred embodiments, the back coating preferably includes at least one selected from the group consisting of thermosetting acrylic, polyurethane, and epoxy system resins.
In some preferred embodiments, the back coating preferably comprises an antistatic agent. Thus, the antistatic property of the pressure-sensitive adhesive sheet is improved, and the peeling static voltage can be sufficiently suppressed. The back coating layer may have a single-layer structure or a multilayer structure of 2 or more layers. In the manner of disposing the back coat layer of the multilayer structure, at least 1 layer thereof (typically at least 1 layer including a layer in contact with the substrate layer) is preferably set as the back coat layer including the antistatic agent.
As the antistatic agent, for example, the antistatic agent described in the above adhesive layer and the like can be used. For example, conductive polymers such as polythiophene, polyaniline, polypyrrole, polyethyleneimine, and allylamine polymers; conductive inorganic particles such as conductive metal oxide, carbon nanotube, graphene, fullerene, acetylene black, ketjen black, natural graphite, artificial graphite, and titanium black; metal particles or fibers, and the like. These may be used singly or in combination of 1 or 2 or more.
In the manner of disposing the back coating layer, polythiophene and polyaniline can be exemplified as the conductive polymer that can be contained in the back coating layer. As the polythiophene, a Mw in terms of polystyrene of 40X 10 is preferable 4 Hereinafter, 30X 10 is more preferable 4 The following is given. As polyaniline, a polyaniline having Mw of 50X 10 is preferable 4 Hereinafter, 30X 10 is more preferable 4 The following is given. In addition, these conductive polymers generally preferably Mw 0.1X10 4 The above is more preferably 0.5X10 4 The above. In the present specification, polythiophene means an unsubstituted or substituted thiophene polymer. As hereOne suitable example of a substituted thiophene polymer in the disclosed technology is poly (3, 4-ethylenedioxythiophene).
In some preferred embodiments, the back coating may include polystyrene sulfonate (PSS) as a dopant (e.g., a dopant for a thiophene-based polymer). In some embodiments, the back coating is formed using a composition for back coating formation containing an aqueous polythiophene solution containing PSS (which may be in the form of adding PSS as a dopant to polythiophene). The aqueous solution may be prepared in a ratio of 1:1 to 1:10 weight ratio of polythiophene: PSS. The total content of polythiophene and PSS in the aqueous solution may be, for example, about 1 to 5% by weight.
The amount of the conductive polymer used may be about 10 parts by weight or more, preferably 25 parts by weight or more, and more preferably 40 parts by weight or more, based on 100 parts by weight of the resin contained in the back coating layer, from the viewpoint of improving the antistatic property. In view of compatibility of the conductive polymer in the back coating layer, the amount of the conductive polymer to be used is preferably 200 parts by weight or less (for example, 150 parts by weight or less), more preferably 120 parts by weight or less (for example, 100 parts by weight or less) based on 100 parts by weight of the resin. The amount of the conductive polymer may be 80 parts by weight or less (for example, 60 parts by weight or less) based on 100 parts by weight of the resin.
The total amount of the antistatic agent in the back coating layer (the total amount of all the antistatic agents including the conductive polymer, the conductive inorganic fine particles, and the like) may be set to about 5 wt% (for example, about 10 wt% or more), and it is preferable to set to about 30 wt% or more, for example, more than 50 wt%. The upper limit of the total amount of the antistatic agent in the back coating layer is not particularly limited, and is preferably about 90 wt% or less (for example, 80 wt% or less), and may be about 40 wt% or less (for example, about 30 wt% or less) in view of adhesion to the substrate layer and the like.
The back coating may contain a binder in addition to the above-described conductive agent. As the binder that can be contained in the back coating layer, the above-mentioned back coating layer forming material can be used without particular limitation. Among them, thermosetting polyurethane and/or epoxy system resins are preferably used. The proportion of the binder in the whole back coating layer may be, for example, about 30% by weight or more, and about 40% by weight or more (for example, about 50% by weight or more) is suitable. In addition, in view of antistatic properties and the like, the proportion of the binder is suitably less than 90% by weight (less than 80% by weight).
Additionally, in some embodiments, the back coating contains a crosslinker. As the crosslinking agent, a crosslinking agent such as melamine, isocyanate, or epoxy, which is used for crosslinking a general resin, may be suitably selected and used. Thus, it is preferable to achieve both the anchoring property to the base material layer.
The back coating layer may contain additives such as antioxidants, colorants, fluidity regulators, film forming aids, surfactants, corrosion inhibitors, and the like, as necessary.
In some preferred embodiments, the back coating is preferably formed by a back treatment agent. The back surface treatment agent that can be used for forming the back coating layer is not particularly limited, and any known or conventional one such as a silicone back surface treatment agent, a fluorine back surface treatment agent, a long-chain alkyl back surface treatment agent, and the like can be used depending on the purpose and use. The back surface treating agent may be used singly or in combination of two or more.
The back coating may be suitably formed by the following method: the resin component and the additive to be used if necessary are dispersed or dissolved in an appropriate solvent to form a liquid composition (coating material for forming a back coating layer) which is applied to the substrate layer by using a known or conventional coater such as a gravure roll coater or a reverse roll coater, and if necessary, the liquid composition is formed by drying and curing the composition. The NV (nonvolatile matter) of the coating material may be, for example, 5 wt% or less (typically 0.05 to 5 wt%) from the viewpoint of forming a thin and uniform layer. As the solvent that can constitute the coating material, any of an organic solvent, water, or a mixed solvent thereof can be used, and water or a mixed solvent containing water as a main component (for example, a mixed solvent of water and ethanol) is preferable.
The thickness of the back coat layer in the technology disclosed herein is not particularly limited, and is usually 0.01 μm or more, and from the viewpoint of properly functioning the back coat layer, 0.05 μm or more is preferable, and 0.1 μm or more (for example, 0.2 μm or more) is also preferable. The upper limit of the thickness of the back coating layer may be 50 μm or less (for example, 10 μm or less), and is preferably 3 μm or less, more preferably 1 μm or less (for example, 0.6 μm or less) from the viewpoints of transparency, coatability, and the like.
[ undercoat layer ]
As shown in fig. 3, the adhesive sheet of the present invention may further include a primer treatment layer 40 (also referred to as "primer layer 40"), the primer layer 40 being provided on the opposite side of the substrate layer 10 from the back surface treatment layer 30.
The primer layer forming material is not particularly limited, and one or more of 1 or 2 or more of polyurethane-based resins, epoxy-based resins, polyester-based resins, acrylic-based resins, polyamide-based resins, melamine-based resins, olefin-based resins, polystyrene-based resins, phenol-based resins, isocyanurate-based resins, polyvinyl acetate-based resins, and the like may be used. In the case where an acrylic pressure-sensitive adhesive layer or the like is provided on the resin film base layer, a urethane-based, epoxy-based, polyester-based, or acrylic-based primer layer is preferable.
In some preferred embodiments, the primer layer preferably includes at least one selected from the group consisting of thermosetting acrylic, polyurethane, and epoxy system resins.
Primer in some preferred embodiments, the primer preferably comprises an antistatic agent. Thus, the antistatic property of the pressure-sensitive adhesive sheet is improved, and the peeling static voltage can be sufficiently suppressed. The undercoat layer may have a single-layer structure or a multilayer structure of 2 or more layers. In the manner of disposing the undercoat layer of the multilayer structure, at least 1 layer (typically at least 1 layer including a layer in contact with the substrate layer) thereof is preferably set as the undercoat layer including the antistatic agent.
As the antistatic agent, for example, the antistatic agent described in the above adhesive layer and the like can be used. For example, conductive polymers such as polythiophene, polyaniline, polypyrrole, polyethyleneimine, and allylamine polymers; conductive inorganic particles such as conductive metal oxide, carbon nanotube, graphene, fullerene, acetylene black, ketjen black, natural graphite, artificial graphite, and titanium black; metal particles or fibers, and the like. These may be used singly or in combination of 1 or 2 or more.
The primer layer may also contain any suitable additives. Examples of such additives include light stabilizers such as ultraviolet absorbers, antioxidants, and hindered amine-based light stabilizers, leveling agents, low molecular polymers, preservatives, polymerization inhibitors, silane coupling agents, inorganic and organic fillers (for example, calcium oxide, magnesium oxide, silicon oxide, zinc oxide, and titanium oxide), metal powders, colorants, pigments, and heat stabilizers.
In some preferred embodiments, the primer layer is preferably formed by a primer. The primer to be used for forming the primer layer is not particularly limited, and a primer which is uniform and firm and can effectively improve the adhesive force and anchor bonding performance can be conveniently formed according to the purpose and use. The primer may be used alone or in combination of two or more.
The thickness of the undercoat layer is not particularly limited, but is preferably 0.05 to 2. Mu.m, more preferably 0.1 to 1.5. Mu.m. By setting the thickness of the undercoat layer to the above range, the effect of the present invention can be more effectively achieved.
(method for producing adhesive sheet)
The adhesive sheet of the present invention may be manufactured by any suitable method. For example, the following methods are mentioned: a method of applying the adhesive composition to the substrate layer, a method of transferring a coating layer formed by applying the adhesive composition to any appropriate substrate to the substrate layer, and the like.
As a coating method of the above adhesive composition, any suitable coating method may be employed. For example, each layer may be formed by drying after coating. Examples of the coating method include coating methods using a multiple coater, a die coater, a gravure coater, an applicator, a bar coater, air knife coating, reverse roll coating, lip coating, dip coating, offset printing, flexography, screen printing, and the like. Examples of the drying method include natural drying and heat drying. The heating temperature in the case of the heat drying can be set to any appropriate temperature according to the characteristics of the substance to be dried.
(use)
The pressure-sensitive adhesive sheet of the present invention can be applied to various members or devices such as an optical member and an electronic member, and can sufficiently suppress peeling static electricity generated during peeling, and can realize excellent antistatic property and temporal stability of peeling static voltage, thereby preventing damage (for example, excellent static breakdown resistance) to the surfaces of the optical member and the members such as the electronic member during processing, assembling, inspection, transportation, and the like.
Examples
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. The evaluation method in the examples is as follows. In the examples, "parts" and "%" are weight basis unless otherwise specified. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The materials used, or the instruments, unless otherwise specified, are conventional products available commercially.
(preparation of acrylic Polymer A1)
Into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet pipe and a reflux condenser, 5 parts of n-Butyl Acrylate (BA) (manufactured by Zhejiang satellite), 62 parts of 2-ethylhexyl acrylate (2 EHA), 30 parts of Vinyl Acetate (VAC), 3 parts of 4-hydroxybutyl acrylate (HBA) and 200 to 300 parts of ethyl acetate as a polymerization solvent were charged, stirred at 65℃for 1 to 1.5 hours under a nitrogen atmosphere, then 0.1 part of 2,2' -Azobisisobutyronitrile (AIBN) was charged as a thermal polymerization initiator, the reaction was carried out at 65℃for 6 to 8 hours, and the internal bath temperature was raised to 70 to 90℃and aged for 2 hours. A solution of the acrylic polymer A1 was obtained. The weight average molecular weight Mw of the soluble portion of the acrylic polymer A1 was 120 ten thousand.
(preparation of acrylic polymers A2 to A5)
Acrylic polymers A1 to A5 were produced in the same manner as acrylic polymer A1 except that the kinds and amounts of the monomer components were changed as shown in table 1.
Table 1 (Unit: portion)
< production of adhesive sheet >
Example 1
To a solution of the acrylic polymer A1, 80 parts of a urethane-modified acrylic resin a (having a functionality of 10) as a polyfunctional oligomer, 2 parts of a nano silver wire as an antistatic agent, 5 parts of an isocyanate crosslinking agent (manufactured by japan polyurethane industry company, product number: CORONATE L), 1 part of a modified melamine crosslinking agent (manufactured by DIC corporation, product number: NDS) and 3 parts of a photoinitiator (manufactured by basf, germany, product number: IRGACURE 651) were added, and the mixture was uniformly mixed and diluted with an appropriate ethyl acetate to prepare an adhesive composition D1.
The back coating adhesive E1 (carbon nano tube dispersing agent, manufacturer first Feng nanometer, brand 101371) is diluted to proper concentration in the mixed solution of deionized water and isopropanol, and is coated on one surface of a polyolefin film (PO film) with the thickness of 150 mu m, and then the film is dried in a suspension oven at 80 ℃ for 1 minute to form the back coating with the thickness of less than 1 mu m.
Primer adhesive F1 (polythiophene dispersion, european organic photoelectric, brand Polyelec OE-001) was then applied to the opposite side of the substrate with the back coating using a similar method to the back coating, thereby forming a primer layer, which may be accomplished simultaneously in some multi-functional coating lines.
Next, the adhesive composition D1 was applied to a 50 μm thick polyethylene terephthalate (PET) release layer, and then heated at 130 ℃ for 3 minutes, and transferred to the primer surface of the substrate, thereby completing the production of the adhesive sheet. In some cases, the above-mentioned adhesive sheet may also be cured by being left at an appropriate temperature. The evaluation results are shown in table 2.
Examples 2 to 6
An adhesive sheet was obtained in the same manner as in example 1, except that the kind of the acrylic polymer, the kind and amount of the polyfunctional oligomer, the kind and amount of the antistatic agent, the amount of the crosslinking agent, the kind and amount of the photoinitiator, the thickness of the adhesive layer, the composition of the back coating layer, and the composition of the primer layer were changed as shown in table 2. The evaluation results are shown in table 2.
Comparative examples 1 to 4
An adhesive sheet was obtained in the same manner as in example 1, except that the kind of the acrylic polymer, the kind and amount of the multifunctional oligomer, the kind and amount of the antistatic agent, the amount of the crosslinking agent, the kind and amount of the photoinitiator, and the thickness of the adhesive layer were changed as shown in table 2, and that the back coat layer and the base coat layer were not provided. The evaluation results are shown in table 3.
TABLE 2
/>
PO: polyolefin film
PET: polyethylene terephthalate film
PVC: polyvinyl chloride film
Antistatic PO: the manufacturer: MATAI DC-VS
Polyurethane modified acrylic resin a: functionality is 10, ruo chemical industry manufacturing, commercial number: FSP8531
Aliphatic epoxy modified acrylic resin B: functionality 5, manufactured by vitamin Dou Si electronic materials limited, product number: WDS-5709
Lithium salt: liTFsl, CAS no: 90076-65-6 manufactured by Shanghai Yi technology
Isocyanate crosslinking agent: number of commodity: CORONATE L manufactured by Japanese polyurethane Industrial Co
Modified melamine crosslinking agent: DIC Co., ltd., product number: NDS (New data storage System)
Epoxy crosslinking agent: number of commodity: TETRAD C, mitsubishi gas chemical manufacturing
UV starter: manufactured by basf, germany, product number: IRGACURE 651
UV photosensitizer: hubei Gurun technology, product number: GR-PS-1
"-" indicates that the PET substrate cannot be spread
TABLE 3 Table 3
PO: polyolefin film
PVC: polyvinyl chloride film
PI: polyimide film
Polyurethane modified acrylic resin a: functionality is 10, ruo chemical industry manufacturing, commercial number: FSP8531
Aliphatic epoxy modified acrylic resin B: functionality 5, manufactured by vitamin Dou Si electronic materials limited, product number: WDS-5709
Polyurethane modified acrylic resin C: functionality is 2, ruo chemical industry manufacturing, commercial number: luCure8706
Carbon nanotubes: jiangsu Xianfeng nanometer materials science and technology Co., ltd., product number: XFS28
Isocyanate crosslinking agent: number of commodity: coronate L, manufactured by Japanese polyurethane Industrial Co., ltd., modified melamine crosslinker: DIC Co., ltd., product number: NDS (New data storage System)
Epoxy crosslinking agent: number of commodity: TETRAD C, mitsubishi gas chemical manufacturing
UV starter: manufactured by basf, germany, product number: IRGACURE 651
< evaluation test >
(1) Stripping static voltage
An evaluation sample was prepared by bonding a release film (a silicone-treated PET film, manufactured by Toli Co., ltd., trade name "Cerapeel", thickness: 38 μm) having been subjected to removal of electricity to the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet (width 70 mm. Times.length 130 mm). At this time, the longitudinal end of the release film protruded 30mm from the adhesive sheet. The pressure-sensitive adhesive sheet and the release film were bonded by hand pressure-sensitive adhesive under the conditions (temperature: 23 ℃ C., humidity: 50% RH) based on JIS Z0237 (year 2000).
After the sample for evaluation was left for one day at 23℃under 50% RH, the protruding portion of the release film was grasped, and the release film was peeled in the longitudinal direction at a peeling angle of 150℃and a peeling speed of 300mm/min (or a peeling speed of 30 m/min). The voltage on the surface of the adhesive layer generated at the time of peeling was measured at a position 100mm away from the separation position of the adhesive sheet and the film in the direction perpendicular to the surface of the adhesive, and the maximum value was taken as the peeling voltage. As the measuring instrument, a potentiometric measuring instrument (trade name "KSD-0103", manufactured by electric instruments, spring Co., ltd.) was used. The measurement environment was set at 23℃and 50% RH.
(2) Surface resistivity
The resistivity of the topcoat surface was measured at 23℃under 50% RH atmosphere using a commercially available resistivity meter based on the conditions of 100V applied voltage and 30 seconds applied time at 23℃under 50% RH atmosphere. As the resistivity meter, the trade name "HIRESTA UP MCP-HT450 type" manufactured by MITSUBISHI CHEMICAL ANALYTECH company or the like may be used. Surface resistivity was measured immediately after application of the topcoat (initial surface resistivity) and after irradiation with ultraviolet light (UV irradiation) in an environment of 23 ℃ x 50% rh and standing, as initial surface resistivity [ Ω/≡]Surface resistivity after UV irradiation [ Ω/≡]. The UV irradiation conditions were set to be 90mW/cm using a metal halide lamp 2 Cumulative light quantity 3000mJ/cm 2 . Illuminance and cumulative light were measured using an ultraviolet illuminometer (trade name "EYE UMETER UVPF-A1", headsensor "PD-365", manufactured by EYEGRAPHICS Co.).
The interfacial surface resistivity represents the surface resistivity of the adhesive layer. The surface resistivity of the adhesive surface was measured and the probe contacted the surface of the adhesive layer.
The back surface resistivity represents the surface resistivity of the back surface of the base material layer. The back surface resistivity was measured and the probes contacted the back of the substrate layer, i.e., the side of the substrate layer opposite the adhesive layer.
Back surface resistivity and gel surface resistivity (1.5 times after film expansion)
After the adhesive sheet obtained in example was expanded 1.5 times using a spreading machine, the surface resistivity of the adhesive sheet surface was measured by the method before the above-mentioned spreading.
(3) Adhesion before Ultraviolet (UV) irradiation
The adhesive layer cut into 20mm wide adhesive sheets was adhered to SUS430BA plates (adhering condition: 1 round trip with a 2kg roller) in an environment where 23 ℃ C./50% RH shields ultraviolet light. After the adhesion and lapse of 20 to 40 minutes, the adhesive sheet was peeled off from the SUS430BA plate, and the peel strength (peeling speed: 300 mm/min, peeling angle: 90 DEG) was measured.
(4) Adhesion after UV irradiation (at room temperature, 23 ℃ C.)
The adhesive sheet was stuck to a SUS430BA plate in the same manner as in (3) above, and left to stand in an ultraviolet-shielded environment for 20 to 40 minutes.
Then, the laminate was irradiated with ultraviolet rays (28 mW/cm) from the side of the adhesive sheet using a high-pressure mercury lamp (UM-810 (solar energy Co.)) 2 10 seconds, 280mJ/cm 2 )。
Next, the adhesive sheet was peeled off from the SUS430BA plate, and the peel strength (peel speed: 300 mm/min, peel angle: 90 DEG) was measured.
(5) Tensile breaking strength
For the tensile breaking strength of the adhesive sheet, according to JIS K6251:2010, by a method specified in 2010. More specifically, the tensile test was performed on a test piece formed into a dumbbell shape or a dumbbell shape (width of parallel portion 10 mm) in the longitudinal direction (MD direction) or the width direction (TD direction) under the measurement conditions of a measurement temperature of 25℃and a tensile speed of 200 mm/min and an initial inter-jig distance of 40mm or 20mm using a bench precision universal tester Autograph AG-5KNX (manufactured by Shimadzu corporation). Then, the maximum tensile force recorded until the test piece was cut was obtained and used as the tensile breaking strength (unit: MPa) of the test piece.
(6) Chip arrangement regularity after film expansion
The chips were arranged on the adhesive surface of the adhesive sheet at the same pitch in the horizontal and vertical directions, and after the adhesive sheet was spread 1.5 times by using a film spreading device, the pitch change rate in the horizontal and vertical directions of the chips was measured. The ratio of MD/TD change rate is between 0.8 and 1.2, which is regarded as 'very good'; if the ratio of MD/TD change rate exceeds 1.2 times, but no rupture occurs, it is regarded as O'; if the film cannot be expanded or broken, it is regarded as "X".
(7) Cohesive modulus G' (MPa) of the adhesive layer (23 ℃ C. -before UV)
The temperature of the adhesive layer before UV was scanned using a torsional rheometer ARES G2 from TA company in an oscillation mode at a frequency of 1Hz in a temperature range of-70℃to 100℃and a storage modulus of G' at 23 ℃.
(8) Loss modulus G "(MPa) of adhesive layer (23 ℃ C. -before UV)
The adhesive layer before UV was subjected to temperature scanning using a torsional rheometer ARES G2 from TA company in an oscillation mode at a frequency of 1Hz in a temperature range of-70℃to 100℃and a loss modulus of G at 23 ℃.
(9) Elongation at break
The adhesive sheets obtained in each example and each comparative example were cut into test pieces having a width of 20mm and a length of 150 mm. Then, the test piece was set to 50mm in length, and a tensile test was performed at a tensile rate of 300 mm/min using a universal material tester (product name "AG-X plus electronic universal tester" manufactured by Shimadzu corporation) under a measuring environment having a temperature of 23℃and a relative humidity of 50%, to thereby measure the elongation at break (%) of the sample. The results are shown in tables 2 and 3.
(10) Laminating property to substrate before UV
The adhesive sheet was attached to the package substrate using a 5kg roller, and the package substrate was left for 1H and then observed. Good adhesion and no air bubbles between the adhesive sheet and the package substrate are considered as "verygood"; the presence of air bubbles between the adhesive sheet and the package substrate is regarded as "o".
(11) Mechanical sheet taking rate after UV
Irradiating the processed adhesive sheet with 300mJ/cm 2 The ultraviolet rays of energy use the automatic pick-up device to pick up the electronic components on the adhesive sheet. 99% or more electronic componentCan be automatically picked up and regarded as 'very good'; more than 95% and less than 99% of electronic components can be automatically picked up, and are regarded as O; less than 90% of the electronic components can be picked up automatically, and regarded as "x".
(12) Film expandability (MD/TD)
A3X 3cm grid was drawn on the adhesive sheet, the film was spread under 1.5-fold conditions using an automatic film expander (WE-4U (Meizhon precision electromechanical) test, the rising speed was 5mm/s, the rising height was 56mm, the upper plate was heated to 50 ℃ C.; the lower plate was heated to 170 ℃ C.) to uniformly spread the adhesive sheet by 1.5-fold at 360 ℃, the adhesive sheet was taken out, left for 1H, and then observed, and the change in the grid point pitch was measured. If the adhesive sheet does not collapse and rupture, the space between grid points is not more than 5%, and the adhesive sheet is regarded as 'very good'; if the adhesive sheet is complete, the grid point pitches differ by more than 5%, and the difference is regarded as O; if the pressure-sensitive adhesive sheet collapses and breaks the film, it is regarded as "X".
(13) Crystal trapping
Placing silicon chip with the thickness of 1mm×1mm on the adhesive surface of the adhesive sheet, attaching release film, repeatedly pressing for 5 times with 5kg roller, placing into a 50deg.C environment box for 24H, taking out, and irradiating 300mJ/cm 2 And (3) ultraviolet rays, taking out the chip, and measuring the sinking depth of the chip under a laser microscope. If the sinking depth of the chip is not more than 1/3 of the thickness of the adhesive layer of the adhesive sheet, the chip is regarded as very good; if the chip trapping depth exceeds 1/3 but does not exceed 2/3, the chip is regarded as O; if the chip trapping depth exceeds 2/3, it is regarded as "X".
(14) Residual tackiness
In the above-described test of the UV front and rear adhesion, the SUS430BA plate was observed for the presence of the residual adhesive. The adhesive residue is regarded as 'very good'; the residual glue is regarded as X.
(15) Comprehensive determination
The measured values were excellent and the evaluation results were regarded as "very good"; when at least one of the above measured values is excellent and the evaluation result is "o", it is regarded as "o"; when the measured value is a difference and at least one of the evaluation results is "x", it is regarded as "x".
As shown in table 2, examples 1 to 6 can sufficiently suppress peeling static electricity generated at the time of peeling, have excellent antistatic properties, can avoid or mitigate damage to an adherend (for example, have excellent static breakdown resistance), and can be easily peeled off without generating residual glue contamination after use.
In contrast, as shown in table 3, in comparative examples 1 to 4, static electricity was generated when the adhesive sheet was peeled off from the adherend, and the static electricity carried by the adherend had a risk of causing deterioration and breakdown of the built-in electronic component, and after use, residual glue contamination was generated.
Industrial applicability
The adhesive sheet of the present invention can sufficiently suppress peeling static electricity generated at the time of peeling, has excellent antistatic property and stability with time of peeling static voltage, thereby avoiding or reducing damage to an adherend (for example, having excellent static breakdown resistance), and can be easily peeled off without generating residual glue contamination after use.

Claims (10)

1. An adhesive sheet, characterized by comprising: a base material layer, and an adhesive layer disposed on one side of the base material layer,
wherein in a peeling test at a peeling speed of 300mm/min, the pressure-sensitive adhesive sheet has a peeling static voltage of 500V or less when peeled from the release film.
2. The adhesive sheet according to claim 1, wherein in a peeling test at a peeling speed of 30m/min, a peeling static voltage generated by peeling the adhesive sheet from a release film is 200V or less;
preferably, in a peeling test at a peeling speed of 30m/min, the peeling static voltage generated by peeling the adhesive sheet from the release film is 100V or less;
Preferably, at least one surface of the adhesive sheet has a surface resistivity of 1.0X10 5 ～1.0×10 11 Ω/□；
Preferably, the surface resistivity of the base layer is 1.0X10 after stretching the adhesive sheet in a 360 DEG direction 1 to 1.5 times 5 ～1.0×10 11 Omega/≡the surface resistivity of the adhesive sheet was 1.0X10 11 Ω/≡or less.
3. The adhesive sheet according to claim 1 or 2, wherein the adhesive layer comprises a base polymer, a multifunctional oligomer, and an antistatic agent.
4. The adhesive sheet according to claim 3, wherein the base polymer comprises an acrylic polymer;
preferably, the base polymer contains 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight, more preferably 3 to 15 parts by weight of a functional monomer based on 100 parts by weight of the entire monomer components of the base polymer;
preferably, the functional monomer includes at least one selected from the group consisting of a hydroxyl group-containing monomer, a carboxyl group-containing monomer, a sulfonic acid group-containing monomer, a phosphoric acid group-containing monomer, an epoxy group-containing monomer, an isocyanate group-containing monomer, an amide group-containing monomer, a ring-containing monomer having a nitrogen atom, a monomer having a succinimide skeleton, a maleimide-based monomer, a itaconimide-based monomer, an aminoalkyl (meth) acrylate-based monomer, an alkoxyalkyl (meth) acrylate-based monomer, a vinyl ether-based monomer, and an olefin-based monomer.
5. A sheet according to claim 3, wherein the polyfunctional oligomer has a functionality of 2 or more, preferably 3 or more, more preferably 5 or more;
preferably, the multifunctional oligomer comprises at least one selected from the group consisting of an acrylic modified resin, a polyurethane modified resin, an epoxy modified resin, a phenolic modified resin, a polyether modified resin, a polyester modified resin, and a silicone modified resin;
preferably, the multifunctional oligomer comprises at least one of a polyurethane modified acrylic resin, an acrylic modified polyurethane resin, an epoxy modified acrylic resin, an epoxy modified polyurethane resin, an o-cresol formaldehyde modified resin, a phenol formaldehyde modified acrylic resin, a phenol formaldehyde modified polyurethane resin, a phenol formaldehyde modified epoxy resin, a polyether modified acrylate resin, a polyester modified acrylate resin, and a silicone modified acrylate resin;
preferably, the multifunctional oligomer comprises at least one selected from the group consisting of polyurethane modified acrylate, epoxy modified acrylate, polyether modified acrylate, polyester modified acrylate, and silicone modified acrylate;
preferably, the content of the multifunctional oligomer is 20 to 200 parts by weight, preferably 30 to 150 parts by weight, more preferably 40 to 120 parts by weight, relative to 100 parts by weight of the base polymer.
6. The adhesive sheet according to claim 3, wherein the antistatic agent comprises at least one selected from the group consisting of conductive polymers, conductive inorganic fine particles, metal fine particles or fibers, ionic compounds, and ionic surfactants;
preferably, the conductive polymer contains at least one selected from the group consisting of polyaniline, polypyrrole, polythiophene, polyquinoxaline, polyacetylene, polyethyleneimine, and allylamine-based polymer;
preferably, the conductive inorganic particles contain at least one selected from the group consisting of conductive metal oxides, carbon nanotubes, graphene, fullerenes, acetylene black, ketjen black, natural graphite, artificial graphite, and titanium black;
preferably, the metal particles or fibers comprise particles or nanowires of gold, silver, copper, aluminum, nickel, or alloys thereof;
preferably, the ionic compound comprises an alkali metal salt and/or an organic cation-anion salt;
preferably, the ionic surfactant comprises at least one selected from the group consisting of cationic surfactants, anionic surfactants, zwitterionic surfactants and nonionic surfactants;
Preferably, the antistatic agent is contained in an amount of 0.0001 to 20 parts by weight, preferably 0.0002 to 10 parts by weight, relative to 100 parts by weight of the base polymer.
7. The adhesive sheet according to any one of claims 1 to 6, wherein the adhesive layer further comprises a photoinitiator and/or a crosslinking agent;
preferably, the photoinitiator is contained in an amount of 0.5 to 10 parts by weight, preferably 0.5 to 5 parts by weight, relative to 100 parts by weight of the base polymer;
preferably, the crosslinking agent is contained in an amount of 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, relative to 100 parts by weight of the base polymer.
8. The adhesive sheet according to any one of claims 1 to 7, wherein the adhesive sheet satisfies at least one of the following characteristics (a) to (d):
characteristics (a): the adhesive force reduction rate of the adhesive sheet calculated by the following formula (1) is 80% or more,
adhesive force decrease rate (%) = [ (N1-N2)/N1 ] ×100 (1)
Wherein N1 represents an adhesive force of the adhesive sheet before ultraviolet irradiation,
n2 represents the cumulative irradiation light quantity of 300mJ/cm of the adhesive sheet 2 Is a uv-post adhesive force;
characteristics (b): the cumulative irradiation light quantity of the adhesive sheet was 300mJ/cm 2 The adhesive force N2 after ultraviolet rays is less than 1N/20 mm;
Characteristics (c): the adhesive force N1 of the adhesive sheet before ultraviolet irradiation is 0.5-40N/20 mm;
characteristics (d): the ratio of the tensile breaking strength in the longitudinal direction (MD direction) to the tensile breaking strength in the width direction (TD direction) (tensile breaking strength in the MD direction/tensile breaking strength in the TD direction) of the adhesive sheet is 0.8-1.2.
9. The adhesive sheet according to any one of claims 1 to 8, wherein the thickness of the substrate layer is 10 to 300 μm, preferably 30 to 200 μm, more preferably 50 to 150 μm;
preferably, the substrate layer comprises at least one selected from the group consisting of thermoplastic polyurethane, polyethylene, polypropylene, polybutylene, ethylene-vinyl acetate copolymer, and polyvinyl chloride;
preferably, the substrate layer comprises an antistatic agent inside and/or on the surface.
10. The adhesive sheet according to any one of claims 1 to 9, wherein the adhesive sheet further comprises a primer layer and/or a back coating layer,
the back coating layer is disposed on a side of the substrate layer opposite the adhesive layer,
the primer layer is disposed on the opposite side of the substrate layer from the back coating layer,
preferably, the primer layer includes at least one selected from the group consisting of thermosetting acrylic, polyurethane, and epoxy system resins;
Preferably, the back coating layer includes at least one selected from the group consisting of thermosetting acrylic, polyurethane, and epoxy system resins.
CN202210226553.3A 2022-03-09 2022-03-09 Pressure-sensitive adhesive sheet Pending CN116769409A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN202210226553.3A CN116769409A (en) 2022-03-09 2022-03-09 Pressure-sensitive adhesive sheet
TW112106977A TW202344395A (en) 2022-03-09 2023-02-24 Adhesive sheet which can fully suppress the peeling static electricity generated during peeling, and has excellent anti-static properties and long-term stability of peeling static voltage
KR1020230029106A KR20230132709A (en) 2022-03-09 2023-03-06 Adhesive sheet
JP2023035773A JP2023133232A (en) 2022-03-09 2023-03-08 Pressure sensitive adhesive sheet

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210226553.3A CN116769409A (en) 2022-03-09 2022-03-09 Pressure-sensitive adhesive sheet

Publications (1)

Publication Number Publication Date
CN116769409A true CN116769409A (en) 2023-09-19

Family

ID=87984685

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210226553.3A Pending CN116769409A (en) 2022-03-09 2022-03-09 Pressure-sensitive adhesive sheet

Country Status (4)

Country Link
JP (1) JP2023133232A (en)
KR (1) KR20230132709A (en)
CN (1) CN116769409A (en)
TW (1) TW202344395A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116987454A (en) * 2023-09-28 2023-11-03 武汉市三选科技有限公司 Adhesive tape for wafer thinning, preparation method thereof and wafer grinding method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116987454A (en) * 2023-09-28 2023-11-03 武汉市三选科技有限公司 Adhesive tape for wafer thinning, preparation method thereof and wafer grinding method
CN116987454B (en) * 2023-09-28 2023-12-12 武汉市三选科技有限公司 Adhesive tape for wafer thinning, preparation method thereof and wafer grinding method

Also Published As

Publication number Publication date
TW202344395A (en) 2023-11-16
JP2023133232A (en) 2023-09-22
KR20230132709A (en) 2023-09-18

Similar Documents

Publication Publication Date Title
JP4799900B2 (en) Adhesive composition, adhesive sheet and surface protective film
JP4358190B2 (en) Adhesive composition, adhesive sheet and surface protective film
JP3912686B2 (en) Adhesive composition, adhesive layer, and surface protective film
JP5088806B2 (en) Adhesive composition, adhesive sheet and surface protective film
WO2013150769A1 (en) Adhesive composition, adhesive layer, adhesive sheet, surface protective sheet, optical surface-protective sheet, and optical film with surface protective sheet
WO2011108573A1 (en) Adhesive composition, adhesive sheet, and surface protective film
JP4453977B2 (en) Adhesive composition, adhesive sheet and surface protective film
CN113382860B (en) Adhesive sheet and use thereof
TW201516123A (en) Adhesive layer for chemical liquid treatment, adhesive sheet for chemical liquid treatment, surface protective sheet, and glass substrate
TW202344395A (en) Adhesive sheet which can fully suppress the peeling static electricity generated during peeling, and has excellent anti-static properties and long-term stability of peeling static voltage
JP2006328348A (en) Adhesive composition, adhesive sheets and surface-protecting film
JP2010209190A (en) Pressure sensitive adhesive sheet
JP2010209189A (en) Pressure sensitive adhesive sheet
TW202340412A (en) Adhesive sheet having excellent expandability, adhesion and re-peelability
JP5733867B2 (en) Adhesive composition, adhesive sheet and surface protective film
JP4805062B2 (en) Adhesive composition and adhesive sheet
WO2022224643A1 (en) Acrylic adhesive composition, acrylic adhesive, adhesive film, and flexible device
JP5523365B2 (en) Adhesive composition, adhesive sheet and surface protective film
CN113382859B (en) Surface protective film
JP5863252B2 (en) Adhesive composition, adhesive sheet and surface protective film
KR102658740B1 (en) laminate
KR20150040230A (en) Pressure-sensitive adhesive layer and pressure-sensitive adhesive sheet for chemical solution treatment, surface protective sheet and glass substrate

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication