WO2014157408A1 - 電気剥離性粘着剤組成物、及び電気剥離性粘着シート、並びに電気剥離性粘着シートの使用方法 - Google Patents
電気剥離性粘着剤組成物、及び電気剥離性粘着シート、並びに電気剥離性粘着シートの使用方法 Download PDFInfo
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- 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
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- 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
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
- C08L71/03—Polyepihalohydrins
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- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
- C09J171/02—Polyalkylene oxides
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- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
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- 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
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- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/202—Conductive
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/748—Releasability
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2405/00—Adhesive articles, e.g. adhesive tapes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2451/00—Decorative or ornamental articles
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
- C09J2301/502—Additional features of adhesives in the form of films or foils characterized by process specific features process for debonding adherents
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- C09J2433/00—Presence of (meth)acrylic polymer
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- C09J2471/00—Presence of polyether
Definitions
- the present invention relates to an electrically peelable pressure-sensitive adhesive composition whose adhesiveness can be reduced by applying a voltage, an electrically peelable pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition, and the electrically peelable pressure-sensitive adhesive sheet. About how to use.
- peelability may be required in applications such as a surface protective film, a coating or decorative masking tape, and a peelable memo.
- an adhesive sheet When such an adhesive sheet is affixed to an adherend, it is required to have an adhesive strength that does not peel from the adherend during transportation, storage, processing, etc. It is required that it can be easily peeled off and removed.
- Patent Document 1 discloses an electrochemically debondable adhesive containing an electrolyte and a high load-resistant binding polymer having high mechanical strength.
- Patent Document 2 discloses a composition for energization peeling containing an ionic liquid as an adhesive that can be peeled off when a voltage is applied.
- an ionic liquid is a molten salt that is liquid at room temperature, has no vapor pressure, and has properties such as high heat resistance, nonflammability, and high chemical stability.
- Patent Document 1 when an adhesive sheet disclosed in Patent Document 1 is used to form a pressure-sensitive adhesive sheet, workability is inferior because it takes about 10 to 15 minutes to peel off the pressure-sensitive adhesive sheet from the adherend.
- the ionic liquid contained in the composition disclosed in Patent Document 2 is a compound having a special structure as described in the document, it is expensive and provides an inexpensive adhesive tape using them. It is difficult to do.
- the pressure-sensitive adhesive sheet using the composition disclosed in Patent Document 2 still has room for improvement in the rate of decrease in adhesive strength before and after voltage application.
- the present invention provides an electro-releasable pressure-sensitive adhesive composition that can reduce adhesiveness effectively by applying a short-time voltage application, and a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition. It aims at providing the usage method of the electric peelable adhesive sheet which has, and an electric peelable adhesive sheet.
- an electroreleasable pressure-sensitive adhesive composition containing a combination of an acrylic salt with a (poly) alkylene polyol having a specific number average molecular weight and an ammonium salt can solve the above-mentioned problems.
- the headline and the present invention were completed.
- an electropeelable pressure-sensitive adhesive composition containing an acrylic polymer (A), a (poly) alkylene polyol (B) having a number average molecular weight of 2000 or less, and an ammonium salt (C).
- an acrylic polymer (A) a (poly) alkylene polyol (B) having a number average molecular weight of 2000 or less
- an ammonium salt (C) a compound represented by the following general formula (c-1).
- R 1 represents any one of an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and an aryl group which may have a substituent. Includes a polycyclic aromatic hydrocarbon group
- R 2 represents an optionally substituted alkylene group having 1 to 10 carbon atoms
- n represents a real number of 1 or more.
- the compound represented by the general formula (b-1) when the compound represented by the general formula (b-1) is a copolymer of EO and PO, it may be a compound formed by block copolymerization or formed by random copolymerization. It may be a compound.
- the electroreleasable pressure-sensitive adhesive composition according to any one of the above [1] to [6], wherein the content of the component (B) is 3 to 250 parts by mass with respect to 100 parts by mass of the component (A). [8]
- the component (A) contains 60 to 99.9% by mass of the structural unit (a1) derived from the (meth) acrylic acid alkyl ester and the structural unit (a2) derived from the functional group-containing unsaturated monomer is 0.
- the electrodetachable pressure-sensitive adhesive sheet according to [10] wherein the pressure-sensitive adhesive layer is provided on at least one surface of a conductive substrate.
- the electric peelable pressure-sensitive adhesive composition of the present invention has high adhesiveness before voltage application, but it can effectively reduce the adhesiveness by applying voltage for a short time. Therefore, the electrically peelable pressure-sensitive adhesive sheet of the present invention having a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition has excellent adhesive force and is excellent in peelability due to voltage application.
- this adhesive sheet shows an example of a structure of the electrically peelable adhesive sheet of this invention. It is a figure which shows the difference of (a) the said adhesive sheet before voltage application, (b) the said adhesive sheet after voltage application regarding the electrically peelable adhesive sheet of this invention. It is a figure which shows the difference of (a) the said adhesive sheet before voltage application, (b) the said adhesive sheet after voltage application regarding the electrically peelable adhesive sheet of this invention.
- (meth) acrylic acid is a term indicating both “acrylic acid” and “methacrylic acid”
- (poly) alkylene polyol means “polyalkylene polyol” and It is used as a term indicating both “alkylene polyol”.
- Mw mass average molecular weight
- Mn number average molecular weight
- the electropeelable pressure-sensitive adhesive composition of the present invention (hereinafter also simply referred to as “pressure-sensitive adhesive composition”) is an acrylic polymer (A), a (poly) alkylene polyol (B) having a number average molecular weight of 2000 or less, And an ammonium salt (C).
- the pressure-sensitive adhesive composition of the present invention contains, together with the acrylic polymer (A), a (poly) alkylene polyol (B) having a number average molecular weight of 2000 or less and an ammonium salt (C) in combination.
- the adhesiveness before voltage application is high, it becomes an electrically peelable adhesive composition that can effectively reduce the adhesiveness by applying voltage for a short time.
- the acrylic polymer (A) contained in the pressure-sensitive adhesive composition of the present invention is a polymer containing a structural unit (a1) derived from (meth) acrylic acid alkyl ester (hereinafter also referred to as “monomer (a1)”). It is.
- the component (A) may be a polymer containing only the structural unit (a1), but is derived from the functional group-containing unsaturated monomer (hereinafter also referred to as monomer (a2)) together with the structural unit (a1). It is preferable that it is an acrylic copolymer containing the structural unit (a2).
- the acrylic copolymer is a copolymer containing a structural unit (a3) derived from another monomer other than the monomers (a1) and (a2) (hereinafter also referred to as “monomer (a3)”). Also good.
- the component (A) is a copolymer, the form of copolymerization is not particularly limited, and may be any of a random copolymer, a block copolymer, and a graft copolymer. In the present invention, the component (A) may be used alone or in combination of two or more.
- the weight average molecular weight (Mw) of the acrylic polymer (A) is preferably 200,000 to 1,500,000, more preferably 350,000 to 1,200,000, and still more preferably, from the viewpoint of improving the tackiness of the resulting pressure-sensitive adhesive composition. Is 450,000 to 150,000, more preferably 550,000 to 900,000. If Mw of (A) component is 200,000 or more, the cohesive force of the obtained adhesive composition will improve and sufficient adhesiveness will be obtained. On the other hand, if the Mw of the component (A) is 1.5 million or less, it is possible to suppress a phenomenon in which the adhesive force of the pressure-sensitive adhesive layer is reduced due to an excessively high elastic modulus of the pressure-sensitive adhesive layer of the formed pressure-sensitive adhesive sheet. .
- the structural unit (a1) derived from a (meth) acrylic acid alkyl ester, and a functional group-containing unsaturated monomer An acrylic copolymer containing the structural unit (a2) derived from (hereinafter also referred to as “monomer (a2)”) is preferable.
- the monomers (a1) and (a2) as raw materials for the acrylic copolymer will be described.
- Examples of the monomer (a1) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and hexyl (meth) acrylate.
- Heptyl (meth) acrylate 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, etc.
- Examples include acid alkyl esters. These monomers (a1) may be used alone or in combination of two or more.
- alkyl (meth) acrylates having an alkyl group having 4 to 12 carbon atoms are preferred from the viewpoint of improving the tackiness of the resulting pressure-sensitive adhesive composition, and alkyl (meta) having an alkyl group having 4 to 8 carbon atoms is preferred. ) Acrylate is more preferred.
- Suitable monomer (a1) is preferably at least one selected from butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate, One or more selected from butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate is more preferable, and butyl (meth) acrylate is more preferable.
- the content of the structural unit (a1) derived from the monomer (a1) is preferably 60 to 99.9% by mass, more preferably 70% with respect to the total structural unit (100% by mass) of the acrylic polymer (A). It is ⁇ 99 mass%, more preferably 80 to 97 mass%, and still more preferably 85 to 95 mass%. If content of a structural unit (a1) is 60 mass% or more, the adhesiveness before the voltage application of the adhesive composition obtained can be made favorable. Moreover, if the said content is 99.9 mass% or less, content of the structural unit (a2) derived from the above-mentioned monomer (a2) can be ensured, cohesive force is improved, and the adhesive composition obtained The stickiness of the product can be further improved.
- the content of the structural unit derived from the alkyl (meth) acrylate having an alkyl group having 4 to 12 carbon atoms is selected from the viewpoint of improving the tackiness before voltage application of the obtained pressure-sensitive adhesive composition. Is preferably 50 to 100% by mass, more preferably 65 to 100% by mass, still more preferably 80 to 100% by mass, and still more preferably 95 to 100% by mass with respect to the total amount (100% by mass).
- the functional group-containing unsaturated monomer of the monomer (a2) is a compound having a functional group in the molecule and one or more double bonds.
- the functional group of the monomer (a2) serves as a cross-linking point for the cross-linking reaction, improves the cohesive force, and can improve the electric peelability of the pressure-sensitive adhesive sheet using the resulting pressure-sensitive adhesive composition.
- Examples of the monomer (a2) include a carboxy group-containing unsaturated monomer, a hydroxyl group-containing unsaturated monomer, and an epoxy group-containing unsaturated monomer.
- carboxy group-containing unsaturated monomer examples include ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid and citraconic acid; 2 -Carboxyethyl (meth) acrylate and the like.
- hydroxyl group-containing unsaturated monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxy Examples thereof include hydroxyalkyl (meth) acrylates such as butyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and glycerin di (meth) acrylate.
- epoxy group-containing unsaturated monomer examples include glycidyl (meth) acrylate.
- These monomers (a2) may be used alone or in combination of two or more.
- a carboxy group-containing unsaturated monomer is preferable, and an ethylenically unsaturated monocarboxylic acid is more preferable.
- (Meth) acrylic acid is more preferred, and acrylic acid is even more preferred.
- the content of the structural unit (a2) derived from the monomer (a2) is the total structural unit (100 mass) of the acrylic polymer (A) from the viewpoint of improving the adhesive strength of the pressure-sensitive adhesive sheet using the obtained pressure-sensitive adhesive composition. %) Is preferably 0.1 to 40% by mass, more preferably 0.4 to 25% by mass, still more preferably 0.7 to 18% by mass, and still more preferably 1.0 to 12% by mass. It is.
- a cross-linking bond can be sufficiently formed with the cross-linking agent, the cohesive force is improved, and a pressure-sensitive adhesive sheet using the resulting pressure-sensitive adhesive composition It is possible to further improve the adhesive strength.
- the content of the structural unit (a2) is 40% by mass or less, the content of the structural unit (a1) derived from the monomer (a1) can be ensured, and thus the resulting pressure-sensitive adhesive composition was used.
- the adhesive strength of the adhesive sheet can be made good.
- the acrylic polymer (A) may further be a copolymer having a structural unit (a3) derived from the monomer (a3) other than the monomers (a1) and (a2).
- the other monomer (a3) include olefins such as ethylene, propylene and isobutylene, halogenated olefins such as vinyl chloride and vinylidene chloride, diene monomers such as butadiene, isoprene and chloroprene, styrene and ⁇ -methyl.
- the content of the structural unit (a3) derived from the monomer (a3) is preferably 0 to 20% by mass, more preferably 0%, based on the total structural unit (100% by mass) of the acrylic polymer (A). -10% by mass, more preferably 0-5% by mass, and still more preferably 0-2% by mass.
- the method for synthesizing the acrylic polymer (A) is not particularly limited, and it can be synthesized by a known polymerization method in the presence or absence of a solvent.
- a solvent to be used include ethyl acetate and toluene.
- a polymerization initiator may be used in the polymerization reaction.
- the polymerization initiator include azobisisobutyronitrile and benzoyl peroxide.
- the polymerization conditions are not particularly limited, but the polymerization is preferably performed at a polymerization temperature of 50 to 90 ° C. and a reaction time of 2 to 30 hours.
- the content of the acrylic polymer (A) is preferably 25 to 97% by mass with respect to the total amount (100% by mass) of the adhesive composition from the viewpoint of improving the adhesiveness of the obtained adhesive composition.
- it is more preferably 35 to 94% by mass, still more preferably 50 to 90% by mass, and still more preferably 70 to 85% by mass.
- it is more preferably 25 to 70% by mass, still more preferably 25 to 65% by mass, and still more preferably 25 to 50% by mass. %.
- the pressure-sensitive adhesive composition of the present invention has a number average molecular weight of 2000 or less, together with the component (C) described later, from the viewpoint of making the pressure-sensitive adhesive composition capable of effectively reducing the adhesiveness after voltage application (poly). Contains alkylene polyol (B).
- the number average molecular weight of the component (B) is preferably 100 to 2000, more preferably 120 to 1600, more preferably from the viewpoint of obtaining a pressure-sensitive adhesive composition that can effectively reduce the adhesiveness after voltage application. 140 to 1300, more preferably 180 to 1000, still more preferably 250 to 900, and still more preferably 320 to 760.
- Examples of the (poly) alkylene polyol as component (B) include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol, and polyethylene polypropylene glycol; ethylene glycol, propylene glycol, 1,3-propanediol, 1, 4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2, Alkylene glycols or diols such as 2,2-trimethylpentanediol, 3,3-dimethylolheptane, diethylene glycol and triethylene glycol; triols such as glycerin and trimethylolpropane Include the polyhydric alcohol and the like. These (poly) alkylene polyols may be used alone or in combination of two or more.
- the component (B) it is preferable to contain (poly) alkylene glycol from the viewpoint of obtaining a pressure-sensitive adhesive composition that can effectively reduce the adhesiveness after voltage application, and polyethylene glycol, triethylene glycol. More preferably, at least one selected from diethylene glycol and ethylene glycol is included.
- the content of the (poly) alkylene glycol in the component (B) is preferably 50 to 100% by mass, more preferably 70% with respect to the total amount (100% by mass) of the component (B) from the same viewpoint as described above. To 100% by mass, more preferably 85 to 100% by mass, and still more preferably 95 to 100% by mass.
- the (poly) alkylene glycol used in the present invention is preferably a compound represented by the following general formula (b-1) from the viewpoint of obtaining a pressure-sensitive adhesive composition capable of effectively reducing the adhesiveness after voltage application, Polyethylene glycol is more preferred.
- EO represents ethylene oxide
- PO represents propylene oxide
- p and q are real numbers that satisfy p ⁇ 0, q ⁇ 0, and p + q ⁇ 1.
- the compound represented by the general formula (b-1) when it is a copolymer of EO and PO, it may be a compound formed by block copolymerization or formed by random copolymerization. It may be a compound.
- the values of p and q are preferably adjusted so that the number average molecular weight of the compound represented by the general formula (b-1) belongs to the above range.
- the amount is preferably 3 to 250 parts by weight, more preferably 4 to 220 parts by weight, more preferably 6 to 190 parts by weight, more preferably 12 to 170 parts by weight, and still more preferably 100 parts by weight of the component (A). Is 20 to 150 parts by mass, more preferably 35 to 140 parts by mass, and still more preferably 50 to 130 parts by mass.
- content of (B) component is 3 mass parts or more, the adhesive composition which can reduce the adhesiveness after a voltage application effectively can be obtained. On the other hand, if content of (B) component is 250 mass parts or less, the fall of the adhesiveness before the voltage application of the adhesive composition obtained can be suppressed, and adhesiveness can be kept favorable.
- the adhesive composition of this invention contains ammonium salt (C) with the above-mentioned (B) component from a viewpoint made into the adhesive composition which can reduce the adhesiveness after a voltage application effectively.
- ammonium salt any compound that generates ammonium ions when ionized can be used. From the viewpoint of making a pressure-sensitive adhesive composition that can effectively reduce the adhesiveness after voltage application, ammonium sulfonate is used. A salt is preferred.
- the ammonium salt refers to a salt having a cation represented by NH 4 + and does not include a quaternary ammonium salt.
- the ammonium salt of sulfonic acid is more preferably a compound represented by the following general formula (c-1).
- R 1 represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and an aryl group which may have a substituent.
- the aryl group includes a polycyclic aromatic hydrocarbon group.
- R 2 represents an alkylene group having 1 to 10 carbon atoms which may have a substituent.
- n represents a real number of 1 or more, preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 14, and still more preferably 2 to 12.
- alkyl group, alkenyl group, aryl group, and alkylene group may have include, for example, an alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, an acyl group, a carboxyl group, an ester group, and a carbamoyl group. Groups and the like.
- alkyl group examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a pentyl group, and a hexyl group. Cycloalkyl groups such as cyclopentyl group and cyclohexyl group are also included.
- the alkyl group preferably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, and still more preferably 1 to 6 carbon atoms.
- aryl group examples include a phenyl group, a biphenylyl group, a terphenyl group, a group represented by the following formula (c-2), and the like, and polycyclic rings such as a naphthyl group and an anthryl group Aromatic hydrocarbon groups (condensed aryl groups) are also included. Note that the ring-forming carbon number of the aryl group is preferably 6 to 24, more preferably 6 to 18, and still more preferably 6 to 12.
- X represents an alkylene group having 1 to 10 carbon atoms or an oxygen atom
- * represents a bonding portion with an oxygen atom
- the benzene ring in formula (c-2) may have a substituent.
- the substituent include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, an acyl group, a carboxyl group, an ester group, and a carbamoyl group.
- Examples of the alkylene group having 1 to 10 carbon atoms are the same as those for R 2 .
- alkylene group which can be selected as R 2 examples include methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, n-pentylene group, n-hexylene group and n-heptylene. Group, n-octylene group, 2-ethylhexylene group, n-nonylene group, n-decylene group and the like.
- the alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, still more preferably 1 to 4, and still more preferably 2 to 3.
- R 1 in formula (c-1) is preferably an aryl group which may have a substituent, more preferably a group represented by formula (c-2) or a naphthyl group.
- R 2 in formula (c-1) is preferably an ethylene group or a propylene group, and more preferably an ethylene group.
- the number average molecular weight (Mn) of the component (C) is preferably 100 to 3000, more preferably 150 to 2500, still more preferably 200 to 2000, and still more preferably 300 to 1500.
- the component (C) may be used alone or in combination of two or more.
- the amount is preferably 3 to 250 parts by weight, more preferably 4 to 220 parts by weight, more preferably 6 to 190 parts by weight, more preferably 12 to 170 parts by weight, and still more preferably 100 parts by weight of the component (A). Is 20 to 150 parts by mass, more preferably 35 to 140 parts by mass, and still more preferably 50 to 130 parts by mass.
- content of (C) component is 3 mass parts or more, the adhesive composition which can reduce the adhesiveness after a voltage application effectively can be obtained. On the other hand, if content of (C) component is 250 mass parts or less, the fall of the adhesiveness before the voltage application of the adhesive composition obtained can be suppressed, and adhesiveness can be kept favorable.
- the mass ratio [(B) / (C)] of the component (B) and the component (C) in the pressure-sensitive adhesive composition of the present invention can effectively reduce the pressure-sensitive adhesiveness after voltage application. And from the viewpoint of maintaining good tackiness before voltage application of the resulting pressure-sensitive adhesive composition, preferably 5/95 to 95/5, more preferably 10/90 to 90/10, and still more preferably 15 / 85 to 85/15, more preferably 20/80 to 80/20.
- the pressure-sensitive adhesive composition of the present invention preferably further contains a cross-linking agent (D) from the viewpoint of increasing cohesive force and expressing desired adhesiveness.
- the crosslinking agent (D) is a compound that, when the component (A) includes the structural unit (a2) derived from the monomer (a2) and has the above-described functional group, crosslinks with the functional group.
- crosslinking agent (D) examples include an isocyanate crosslinking agent, an epoxy crosslinking agent, an oxazoline crosslinking agent, a carbodiimide crosslinking agent, an aziridine crosslinking agent, a polyisocyanate crosslinking agent, a melamine crosslinking agent, and a metal complex crosslinking agent. Hydrazine derivatives such as an agent, an amine-based crosslinking agent, adipic acid dihydrazide, and sebacic acid dihydrazide. These crosslinking agents may be used alone or in combination of two or more. Among these, an isocyanate type crosslinking agent is preferable from the viewpoint of expressing high adhesiveness in the obtained pressure-sensitive adhesive composition.
- an epoxy-based crosslinking agent is preferable.
- the content of (D) is preferably 0.01 to 10 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the acrylic polymer (A), from the viewpoint of expressing high adhesiveness in the obtained adhesive composition. Is 0.05 to 6 parts by mass, more preferably 0.07 to 4 parts by mass.
- the pressure-sensitive adhesive composition of the present invention further contains a tackifier resin from the viewpoint of further improving the pressure-sensitive adhesive property before voltage application of the obtained pressure-sensitive adhesive composition. Also good.
- tackifying resins include rosin resins such as rosin resins, rosin phenol resins, and rosin ester resins; hydrogenated rosin resins obtained by hydrogenating these rosin resins; terpene resins, terpene phenol resins, aromatic modifications Terpene resins such as terpene resins; hydrogenated terpene resins obtained by hydrogenating these terpene resins; copolymerization of C5 fractions such as pentene, isoprene, piperine and 1.3-pentadiene produced by thermal decomposition of petroleum naphtha C5 petroleum resin and hydrogenated petroleum resin of this C5 petroleum resin; C9 fractions such as indene, vinyltoluene, ⁇ -methylstyrene, ⁇ -methylstyrene, etc. produced by thermal decomposition of petroleum naphtha are copolymerized C9 petroleum resin obtained by hydrogenation and hydrogenated petroleum resin of this C9 petroleum resin; and the like.
- the softening point of the tackifying resin is preferably 60 to 170 ° C., more preferably 75 to 150 ° C., and still more preferably 85 to 140 ° C., from the viewpoint of further improving the tackiness before voltage application of the obtained pressure-sensitive adhesive composition. More preferably, the temperature is 90 to 130 ° C.
- the value of the softening point of the tackifier resin is a value measured in accordance with JIS K 2531.
- the pressure-sensitive adhesive composition of the present invention may contain general-purpose additives other than those described above as long as the effects of the present invention are not impaired.
- General-purpose additives include antioxidants, ultraviolet absorbers, light stabilizers, resin stabilizers, softeners (plasticizers), fillers, rust inhibitors, pigments, dyes, and the like.
- the content of each general-purpose additive is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts per 100 parts by mass of the acrylic polymer (A). Part by mass, more preferably 0.1 to 3 parts by mass.
- the electric peelable pressure-sensitive adhesive sheet of the present invention (hereinafter also simply referred to as “pressure-sensitive adhesive sheet”) has a pressure-sensitive adhesive layer made of the above-described electric peelable pressure-sensitive adhesive composition of the present invention. If the adhesive sheet of this invention has an adhesive layer which consists of an adhesive composition of this invention, the structure will not be specifically limited, It is an adhesive sheet which has an adhesive layer in the at least single side
- FIG. 1 is a cross-sectional view of an electrically peelable pressure-sensitive adhesive sheet having a configuration of the electrically peelable adhesive sheet of the present invention.
- a specific configuration of the pressure-sensitive adhesive sheet of the present invention for example, as shown in FIG. 1 (a), a base-equipped electro-peelable pressure-sensitive adhesive sheet 1a having a pressure-sensitive adhesive layer 3 on one surface of a base material 2 is provided. Can be mentioned. Further, as shown in FIG. 1 (b), a base-equipped electro-peelable pressure-sensitive adhesive sheet 1b having a pressure-sensitive adhesive layer 3 and a pressure-sensitive adhesive layer 3 ′ on both sides of the base material 2, and FIG. 1 (c).
- Examples also include a base-attached electro-peelable pressure-sensitive adhesive sheet 1c in which a release sheet 4 is further laminated on the pressure-sensitive adhesive layer 3 formed on one side of the base material 2 as shown.
- the electrically peelable adhesive sheet 1b may be further provided with a release sheet on the adhesive layers 3 and 3 ′.
- a baseless electro-peelable adhesive having a configuration in which an adhesive layer 3 is sandwiched between two release sheets 4, 4 ′ without using a base material. It may be a sheet 1d.
- the material of the release sheets 4 and 4 ′ of the electric peelable adhesive sheet 1 d may be the same or different, but is a material adjusted so that the release force between the release sheet 4 and the release sheet 4 ′ is different. Preferably there is.
- an electrically peelable pressure-sensitive adhesive sheet having a structure in which a pressure-sensitive adhesive layer is provided on one side of a release sheet whose surface has been subjected to a release treatment is wound into a roll shape.
- the pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive that is connected to the cathode side when a voltage is applied between two adherends, or between both surfaces of the pressure-sensitive adhesive layer sandwiched between the adherend and the substrate. Peeling occurs between the surface of the layer and the adherend or substrate in contact with the surface. That is, as shown in FIG. 2 (a), consider a case where the electro-peelable pressure-sensitive adhesive sheet 1a of the present invention is to be peeled from the adherend 11. In FIG. 2A, the pressure-sensitive adhesive layer 3 is sandwiched between the adherend 11 and the substrate 2a, the anode terminal 51 of the voltage application device 50 is connected to the substrate 2a, and the cathode terminal 52 is adhered.
- electrodes By connecting to the body 11, electrodes can be applied from both sides of the pressure-sensitive adhesive layer 3.
- the structure of the “base material 2a” in FIG. The layer 3 is sandwiched between two adherends.
- the electrodes By connecting the anode terminal 51 and the cathode terminal 52 of the voltage application device 50 to the respective adherends, the electrodes are attached from both sides of the adhesive layer 3. Can be applied.
- a voltage is applied in the state shown in FIG. 2 (a), as shown in FIG. 2 (b), the surface 3a of the adhesive layer connected to the cathode side and the adhesive connected to the cathode side. Adhesive strength is reduced between the surface 11a of the agent layer and the adherend 11 so that the electroreleasable pressure-sensitive adhesive sheet 1a can be easily peeled from the adherend.
- the voltage to be applied is preferably 10 to 200 V, more preferably 40 to 140 V, and even more preferably 70 to 120 V.
- the time for applying the voltage in the range is preferably 1 to 180 V. Second, more preferably 5 to 120 seconds, still more preferably 10 to 90 seconds.
- the larger the applied voltage the shorter the applied time, while the smaller the applied voltage, the longer the applied time. For example, when the applied voltage is 10 to 50 V, peeling is possible with an application time of 30 to 300 seconds.
- the pressure-sensitive adhesive force before voltage application of the pressure-sensitive adhesive sheet of the present invention is preferably 2.0 N / 25 mm or more, more preferably 3.0 N / 25 mm or more, and still more preferably 4.0 N / 25 mm or more.
- a decreasing rate of the adhesive force after the voltage application of the adhesive sheet of this invention Preferably it is 20% or more, More preferably, it is 30% or more, More preferably, it is 45% or more, More preferably, it is 70% or more.
- the adhesive force before the voltage application of the adhesive sheet of this invention and the decreasing rate of the adhesive force after a voltage application mean the value measured by the method as described in an Example.
- the thickness of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the present invention is appropriately adjusted according to the use etc., but is preferably 0.5 to 120 ⁇ m, more preferably 1 to 100 ⁇ m, and still more preferably 3 to 60 ⁇ m.
- the thickness of the pressure-sensitive adhesive layer is 0.5 ⁇ m or more, good adhesive force can be expressed regardless of the type of adherend.
- the thickness of the pressure-sensitive adhesive layer is 120 ⁇ m or less, it is advantageous in terms of productivity and can be an electro-releasable pressure-sensitive adhesive sheet that is also excellent in terms of handling properties.
- the base material of the pressure-sensitive adhesive sheet of the present invention is preferably a conductive base material in order to apply a voltage to the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet when it is desired to peel from the adherend.
- the material constituting the conductive substrate include metals such as aluminum, tin-doped indium oxide, copper, iron, silver, platinum, and gold, and alloys of these metals.
- a metal on the resin film it is preferable to deposit the metal on the surface of the resin film in contact with the adhesive layer.
- the thickness of the substrate is preferably 5 to 300 ⁇ m, more preferably 10 to 150 ⁇ m, and still more preferably 20 to 100 ⁇ m.
- the release sheet used in the pressure-sensitive adhesive sheet of the present invention can be obtained by applying a release agent to one side or both sides of the release sheet substrate.
- the base material for the release sheet include polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyethylene, polypropylene, polybutene, polybutadiene, polymethylpentene, polyvinyl chloride, vinyl chloride copolymer, polyurethane, and ethylene- Vinyl acetate copolymer, ionomer resin, ethylene (meth) acrylic acid copolymer, polystyrene, polycarbonate, fluororesin, low density polyethylene, linear low density polyethylene, triacetyl cellulose resin film, fine paper, coated paper And paper base materials such as glassine paper, and laminated paper obtained by laminating a thermoplastic resin such as polyethylene on these paper base materials.
- release agent examples include silicone-based resins, olefin-based resins, long-chain alkyl-based resins, alkyd-based resins, fluorine-based resins, rubber-based elastomers such as isoprene-based resins and butadiene-based resins.
- the thickness of the release sheet is not particularly limited, but is preferably 5 to 300 ⁇ m, more preferably 10 to 200 ⁇ m. In the case where a polyethylene terephthalate film is used as the release sheet substrate, the thickness is preferably 10 to 100 ⁇ m.
- the pressure-sensitive adhesive composition is prepared by blending an organic solvent such as toluene, ethyl acetate, or methyl ethyl ketone with the pressure-sensitive adhesive composition of the present invention.
- examples include a method of preparing a pressure-sensitive adhesive sheet by adjusting a solution of a product, applying and drying the solution on a release treatment surface of a base material or a release sheet by a known application method, and forming a pressure-sensitive adhesive layer.
- the active ingredient (solid content) concentration of the adhesive composition solution is preferably 10 to 80% by mass, more preferably 25 to 70% by mass, and still more preferably 45 to 65% by mass.
- Examples of the method for applying the adhesive composition solution onto a substrate or a release sheet include spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure. Examples thereof include a coating method.
- a drying treatment is performed to prevent the solvent and low-boiling components from remaining in the formed pressure-sensitive adhesive layer. It is preferable to remove these residues.
- an electro-peelable pressure-sensitive adhesive sheet 1a having a pressure-sensitive adhesive layer 3 on one side of a base material 2, for example, a solution of the pressure-sensitive adhesive composition directly on one side of the base material It can apply
- the adhesive composition solution is directly applied on the release treatment surface of the release sheet to form the adhesive layer 3, and then the adhesive layer 3 and the substrate 2 are bonded together to remove the release sheet. You may make it.
- the electro-peelable pressure-sensitive adhesive sheet 1 b having the pressure-sensitive adhesive layers 3 and 3 ′ on both surfaces of the substrate 2 as shown in FIG. 1B for example, a solution of the pressure-sensitive adhesive composition is directly applied to both surfaces of the substrate 2.
- the pressure-sensitive adhesive layers 3 and 3 ′ can be formed and manufactured.
- two sheets of the pressure-sensitive adhesive composition solution applied directly on the release-treated surface of the release sheet to form a pressure-sensitive adhesive layer are prepared, and the respective pressure-sensitive adhesive layers are bonded to both surfaces of the substrate 2. Then, the release sheet may be removed for production.
- An electro-peelable pressure-sensitive adhesive sheet 1c having a pressure-sensitive adhesive layer 3 and a release sheet 4 in this order on a substrate 2 as shown in FIG. 1C is, for example, an electro-peelable pressure-sensitive adhesive sheet 1a obtained as described above.
- the release sheet 4 can be laminated on the surface of the pressure-sensitive adhesive layer 3. Moreover, after apply
- an electro-peelable pressure-sensitive adhesive sheet 1 d having a configuration in which the pressure-sensitive adhesive layer 3 is sandwiched between two release sheets 4 and 4 ′ without using a substrate is, for example, The adhesive composition solution is directly applied on the release-treated surface to form the adhesive layer 3, and then another release sheet 4 ′ is laminated on the surface of the adhesive layer 3. Can do.
- it is preferable to adjust so that peeling force may differ between peeling sheet 4 and peeling sheet 4 '.
- the electric peelable pressure-sensitive adhesive sheet of the present invention can be used by being attached to an arbitrary adherend.
- the adherend is not particularly limited, and may or may not have conductivity. However, from the viewpoint of easily applying a voltage to the pressure-sensitive adhesive surface, the adherend is directly used as an electrode. Thus, an adherend having conductivity is preferable. Therefore, from the above viewpoint, as a method for using the electro-releasable pressure-sensitive adhesive sheet of the present invention, a method of using the pressure-sensitive adhesive sheet of the present invention after being attached to an adherend having conductivity is preferable.
- the adherend having conductivity include an adherend made of a metal such as aluminum, tin-doped indium oxide, copper, iron, silver, platinum, gold, or an alloy of these metals.
- Examples 1 to 15 and Comparative Examples 1 to 10 The following components are blended in the amounts shown in Table 1 (effective component ratio (solid content ratio)), and toluene is added as an organic solvent, and the active component (solid content) concentration is 26% by mass.
- a coating solution for the agent composition was prepared.
- an active ingredient means components other than the water and organic solvent which remain
- the coating liquid of the prepared electro-peelable pressure-sensitive adhesive composition was peeled off from a release sheet (product name “SP-PET381130” manufactured by Lintec Corporation, thickness: 38 ⁇ m, polyethylene terephthalate film whose surface was subjected to silicone release treatment).
- ⁇ (D) component cross-linking agent> “TETRAD-C”: trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd., epoxy-based crosslinking agent.
- the adhesive strength of the pressure-sensitive adhesive sheet before and after voltage application was measured based on the following method using the base-attached electro-peelable pressure-sensitive adhesive sheet prepared in Examples and Comparative Examples. The results are shown in Table 1.
- the voltage application device 50 (product name “KH-100H” manufactured by Takasago Seisakusho Co., Ltd.)
- the anode terminal 51 was connected to the aluminum foil substrate 2a
- the cathode terminal 52 was connected to the adherend 11, and a voltage of 100 V was applied for 60 seconds.
- the sample was left for 30 seconds, and then peeled at 300 mm / min using a tensile tester (Orientec, trade name “Tensilon”) in the same environment of 23 ° C. and 50% RH (relative humidity).
- the value (unit: N / 25 mm) measured when the pressure-sensitive adhesive sheet was peeled off at a peeling angle of 180 ° was defined as the pressure-sensitive adhesive strength of the pressure-sensitive adhesive sheet after voltage application.
- the electrically peelable pressure-sensitive adhesive sheets of Examples 1 to 15 have low adhesive strength after voltage application and a high rate of decrease in adhesive strength due to voltage application.
- FIG. 2B it was confirmed that the adhesive layers of Examples 1 to 15 were peeled from the cathode side after voltage application, as shown in FIG.
- the electro-releasable adhesive sheets of Comparative Examples 1 to 10 had higher adhesive strength after voltage application than the Examples, and the results showed little decrease in adhesive strength before and after voltage application.
- the electric peelable pressure-sensitive adhesive sheet of the present invention has a good adhesive force and is excellent in peelability due to voltage application. Therefore, the electrically peelable pressure-sensitive adhesive sheet of the present invention is suitable for uses such as a surface protective film, a coating or decorative masking tape, and a peelable memo.
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Abstract
Description
このような粘着シートは、被着体に貼付された際に、運搬時、貯蔵時、加工時等においては被着体から剥離しない程度の粘着力が求められる一方、機能を果たし終えた後には、容易に剥離して除去できることが求められる。
例えば、特許文献1には、高機械強度を有する高負荷耐性の結合性ポリマーを含むと共に電解質を含む電気化学的に結合解除可能な接着剤が開示されている。
また、特許文献2には、電圧印加時に剥離可能な粘着剤として、イオン性液体を含む通電剥離用組成物が開示されている。特許文献2によれば、イオン性液体とは、室温で液体である溶融塩であり、蒸気圧がなく、高耐熱性、不燃性、高化学安定性等の性質を有するとされている。
また、特許文献2に開示の組成物に含まれるイオン性液体は、当該文献に記載されているように特殊な構造を有する化合物であるため価格が高く、それらを用いて安価な粘着テープを提供することは困難である。さらに、特許文献2に開示の組成物を用いた粘着シートは、電圧印加前後の粘着力の低下率が未だ改良の余地がある。
〔1〕アクリル系重合体(A)、数平均分子量が2000以下である(ポリ)アルキレンポリオール(B)、及びアンモニウム塩(C)を含有する、電気剥離性粘着剤組成物。
〔2〕(C)成分が、スルホン酸のアンモニウム塩である、上記〔1〕に記載の電気剥離性粘着剤組成物。
〔3〕前記スルホン酸のアンモニウム塩が、下記一般式(c-1)で表される化合物である、上記〔2〕に記載の電気剥離性粘着剤組成物。
〔4〕(A)成分100質量部に対する(C)成分の含有量が、3~250質量部である、上記〔1〕~〔3〕のいずれかに記載の電気剥離性粘着剤組成物。
〔5〕(B)成分が、(ポリ)アルキレングリコールを含む、上記〔1〕~〔4〕のいずれかに記載の電気剥離性粘着剤組成物。
〔6〕前記(ポリ)アルキレングリコールが、下記一般式(b-1)で表される化合物である、上記〔5〕に記載の電気剥離性粘着剤組成物。
〔7〕(A)成分100質量部に対する(B)成分の含有量が、3~250質量部である、上記〔1〕~〔6〕のいずれかに記載の電気剥離性粘着剤組成物。
〔8〕(A)成分が、(メタ)アクリル酸アルキルエステル由来の構成単位(a1)を60~99.9質量%、及び官能基含有不飽和単量体由来の構成単位(a2)を0.1~40質量%含むアクリル系共重合体である、上記〔1〕~〔7〕のいずれかに記載の電気剥離性粘着剤組成物。
〔9〕さらに架橋剤(D)を含有する、上記〔1〕~〔8〕のいずれかに記載の電気剥離性粘着剤組成物。
〔10〕上記〔1〕~〔9〕のいずれかに記載の電気剥離性粘着剤組成物からなる粘着剤層を有する、電気剥離性粘着シート。
〔11〕導電性の基材の少なくとも片面に、前記粘着剤層を有する、上記〔10〕に記載の電気剥離性粘着シート。
〔12〕前記粘着剤層が、2枚の剥離シートに挟持された構成を有する、上記〔10〕に記載の電気剥離性粘着シート。
〔13〕2枚の被着体、もしくは被着体及び基材に挟持された前記粘着剤層の両側の面の間に電圧を印加した際、陰極側に接続した前記粘着剤層の面と、該面と接触する前記被着体又は前記基材との間で剥離する、上記〔10〕~〔12〕のいずれかに記載の電気剥離性粘着シート。
〔14〕上記〔10〕~〔13〕のいずれかに記載の電気剥離性粘着シートを、導電性を有する被着体に貼付する、電気剥離性粘着シートの使用方法。
また、本発明において、質量平均分子量(Mw)及び数平均分子量(Mn)の値は、ゲルパーミエーションクロマトグラフィー(GPC)法で測定される標準ポリスチレン換算の値であり、具体的には実施例に記載の方法に基づいて測定された値である。
本発明の電気剥離性粘着剤組成物(以下、単に「粘着剤組成物」ともいう)は、アクリル系重合体(A)、数平均分子量が2000以下である(ポリ)アルキレンポリオール(B)、及びアンモニウム塩(C)を含有する。
本発明の粘着剤組成物は、アクリル系重合体(A)と共に、数平均分子量が2000以下である(ポリ)アルキレンポリオール(B)と、アンモニウム塩(C)とを組み合わせて含有することで、電圧印加前の粘着性は高いが、短時間の電圧印加により、粘着性を効果的に低下し得る電気剥離性粘着剤組成物となる。
本発明の粘着剤組成物中に含まれるアクリル系重合体(A)は、(メタ)アクリル酸アルキルエステル(以下、「モノマー(a1)」ともいう)由来の構成単位(a1)を含む重合体である。
(A)成分は、当該構成単位(a1)のみを含む重合体であってもよいが、構成単位(a1)と共に、官能基含有不飽和単量体(以下、モノマー(a2)ともいう)由来の構成単位(a2)を含むアクリル系共重合体であることが好ましい。
また、当該アクリル系共重合体は、モノマー(a1)及び(a2)以外のその他のモノマー(以下、「モノマー(a3)」ともいう)由来の構成単位(a3)を含む共重合体であってもよい。
(A)成分が共重合体である場合、共重合の形態については、特に制限はなく、ランダム共重合体、ブロック共重合体、グラフト共重合体のいずれであってもよい。
なお、本発明において、(A)成分は、単独で又は2種以上を組み合わせて用いてもよい。
(A)成分のMwが20万以上であれば、得られる粘着剤組成物の凝集力が向上し、十分な粘着性が得られる。一方、(A)成分のMwが150万以下であれば、形成した粘着シートの粘着剤層の弾性率が高くなり過ぎることによる、当該粘着剤層の粘着力が低下する現象を抑えることができる。
以下、当該アクリル系共重合体の原料となるモノマー(a1)及び(a2)について説明する。
モノマー(a1)としては、例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、イソプロピル(メタ)アクリレート、ブチル(メタ)アクリレート、ペンチル(メタ)アクリレート、ヘキシル(メタ)アクリレート、ヘプチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、オクチル(メタ)アクリレート、ノニル(メタ)アクリレート、デシル(メタ)アクリレート、トリデシル(メタ)アクリレート、ステアリル(メタ)アクリレート等の(メタ)アクリル酸アルキルエステルが挙げられる。
これらのモノマー(a1)は、単独で又は2種以上を組み合わせて用いてもよい。
好適なモノマー(a1)としては、ブチル(メタ)アクリレート、ペンチル(メタ)アクリレート、ヘキシル(メタ)アクリレート、ヘプチル(メタ)アクリレート、及び2-エチルヘキシル(メタ)アクリレートから選ばれる1種以上が好ましく、ブチル(メタ)アクリレート及び2-エチルヘキシル(メタ)アクリレートから選ばれる1種以上がより好ましく、ブチル(メタ)アクリレートが更に好ましい。
構成単位(a1)の含有量が60質量%以上であれば、得られる粘着剤組成物の電圧印加前の粘着性を良好とすることができる。また、当該含有量が99.9質量%以下であれば、上述のモノマー(a2)由来の構成単位(a2)の含有量を確保することができ、凝集力を向上させ、得られる粘着剤組成物の粘着性を更に向上させることができる。
モノマー(a2)の官能基含有不飽和単量体は、分子中に官能基を有し、且つ二重結合を一つ以上有する化合物である。モノマー(a2)が有する官能基は、架橋反応の架橋点となり、凝集力を向上させ、得られる粘着剤組成物を用いた粘着シートの電気剥離性を向上させることができる。
モノマー(a2)としては、例えば、カルボキシ基含有不飽和モノマー、ヒドロキシル基含有不飽和モノマー、エポキシ基含有不飽和モノマー等が挙げられる。
これらの中でも、汎用性の観点、並びに得られる粘着剤組成物を用いた粘着シートの粘着力の向上の観点から、カルボキシ基含有不飽和モノマーが好ましく、エチレン性不飽和モノカルボン酸がより好ましく、(メタ)アクリル酸が更に好ましく、アクリル酸がより更に好ましい。
構成単位(a2)の含有量が0.1質量%以上であると、架橋剤と十分に架橋結合を形成することができ、凝集力が向上させ、得られる粘着剤組成物を用いた粘着シートの粘着力を更に向上させることができる。一方、構成単位(a2)の含有量が40質量%以下であれば、モノマー(a1)由来の構成単位(a1)の含有量を確保することができるため、得られる粘着剤組成物を用いた粘着シートの粘着力を良好とすることができる。
なお、アクリル系重合体(A)は、さらにモノマー(a1)及び(a2)以外のその他のモノマー(a3)由来の構成単位(a3)を有する共重合体であってもよい。
その他のモノマー(a3)としては、例えば、エチレン、プロピレン、イソブチレン等のオレフィン類、塩化ビニル、ビニリデンクロリド等のハロゲン化オレフィン類、ブタジエン、イソプレン、クロロプレン等のジエン系モノマー類、スチレン、α-メチルスチレン、ビニルトルエン、ギ酸ビニル、酢酸ビニル、アクリロニトリル、(メタ)アクリルアミド、(メタ)アクリロニトリル、(メタ)アクリロイルモルホリン、N-ビニルピロリドン等が挙げられる。
モノマー(a3)由来の構成単位(a3)の含有量としては、アクリル系重合体(A)の全構成単位(100質量%)に対して、好ましくは0~20質量%で、より好ましくは0~10質量%、更に好ましくは0~5質量%、より更に好ましくは0~2質量%である。
用いる溶媒としては、例えば、酢酸エチル、トルエン等を挙げられる。
なお、重合反応に際し、重合開始剤を用いてもよい。重合開始剤としては、例えば、アゾビスイソブチロニトリル、ベンゾイルパーオキサイド等を挙げられる。
また、重合条件としては、特に限定されないが、重合温度50~90℃で、反応時間2~30時間の条件で行われることが好ましい。
本発明の粘着剤組成物は、電圧印加後の粘着性を効果的に低下させ得る粘着剤組成物とする観点から、後述の(C)成分と共に、数平均分子量が2000以下である(ポリ)アルキレンポリオール(B)を含有する。
そのため、(B)成分の数平均分子量は、電圧印加後の粘着性が効果的に低下し得る粘着剤組成物を得る観点から、好ましくは100~2000、より好ましくは120~1600、より好ましくは140~1300、更に好ましくは180~1000、更に好ましくは250~900、より更に好ましくは320~760である。
これらの(ポリ)アルキレンポリオールは、単独で又は2種以上を組み合わせて用いてもよい。
(B)成分中の(ポリ)アルキレングリコールの含有量は、上記と同様の観点から、(B)成分の全量(100質量%)に対して、好ましくは50~100質量%、より好ましくは70~100質量%、更に好ましくは85~100質量%、より更に好ましくは95~100質量%である。
なお、p、qの値は、上記一般式(b-1)で表される化合物の数平均分子量が上述の範囲に属するように調整された値であることが好ましい。
(B)成分の含有量としては、電圧印加後の粘着性を効果的に低下させ得る粘着剤組成物を得る観点、並びに得られる粘着剤組成物の電圧印加前の粘着性を良好に保つ観点から、(A)成分100質量部に対して、好ましくは3~250質量部、より好ましくは4~220質量部、より好ましくは6~190質量部、より好ましくは12~170質量部、更に好ましくは20~150質量部、更に好ましくは35~140質量部、より更に好ましくは50~130質量部である。
(B)成分の含有量が3質量部以上であれば、電圧印加後の粘着性を効果的に低下させ得る粘着剤組成物を得ることができる。一方、(B)成分の含有量が250質量部以下であれば、得られる粘着剤組成物の電圧印加前の粘着性の低下を抑え、粘着性を良好に保つことができる。
本発明の粘着剤組成物は、電圧印加後の粘着性を効果的に低下させ得る粘着剤組成物とする観点から、上述の(B)成分と共に、アンモニウム塩(C)を含有する。
アンモニウム塩としては、電離した際にアンモニウムイオンが生じる化合物であれば使用することができるが、電圧印加後の粘着性を効果的に低下させ得る粘着剤組成物とする観点から、スルホン酸のアンモニウム塩であることが好ましい。
なお、本発明において、アンモニウム塩とは、NH4 +で示されるカチオンを有する塩を指し、第四級アンモニウム塩はこれに含まれない。
さらに、スルホン酸のアンモニウム塩としては、下記一般式(c-1)で表される化合物がより好ましい。
R2は、置換基を有していてもよい炭素数1~10のアルキレン基を示す。
nは1以上の実数を示すが、好ましくは1~30、より好ましくは1~20、更に好ましくは1~14、より更に好ましくは2~12である。
当該アルキル基の炭素数は、好ましくは1~18、より好ましくは1~12、更に好ましくは1~6である。
なお、当該アリール基の環形成炭素数は、好ましくは6~24、より好ましくは6~18、更に好ましくは6~12である。
炭素数1~10のアルキレン基としては、R2と同じものが挙げられる。
当該アルキレン基の炭素数は、好ましくは1~10であるが、より好ましくは1~6、更に好ましくは1~4、より更に好ましくは2~3である。
また、式(c-1)中のR2としては、エチレン基、又はプロピレン基が好ましく、エチレン基がより好ましい。
(C)成分の含有量としては、電圧印加後の粘着性を効果的に低下させ得る粘着剤組成物を得る観点、並びに得られる粘着剤組成物の電圧印加前の粘着性を良好に保つ観点から、(A)成分100質量部に対して、好ましくは3~250質量部、より好ましくは4~220質量部、より好ましくは6~190質量部、より好ましくは12~170質量部、更に好ましくは20~150質量部、更に好ましくは35~140質量部、より更に好ましくは50~130質量部である。
(C)成分の含有量が3質量部以上であれば、電圧印加後の粘着性を効果的に低下させ得る粘着剤組成物を得ることができる。一方、(C)成分の含有量が250質量部以下であれば、得られる粘着剤組成物の電圧印加前の粘着性の低下を抑え、粘着性を良好に保つことができる。
本発明の粘着剤組成物は、凝集力を高めて所望の粘着性を発現させる観点から、さらに架橋剤(D)を含有することが好ましい。
架橋剤(D)は、(A)成分がモノマー(a2)由来の構成単位(a2)を含み上述の官能基を有する場合、当該官能基と架橋する化合物である。
これらの架橋剤は、単独で又は2種以上を組み合わせて用いてもよい。
これらの中でも、得られる粘着剤組成物に高い粘着性を発現させる観点から、イソシアネート系架橋剤が好ましい。
また、(B)成分のポリオキシアルキレンポリエーテルとは反応せずに、効率的に(A)成分のアクリル系重合体と架橋し、(B)成分の水酸基を系内に残存させ、電圧印加後の粘着性を効果的に低下させ得る粘着剤組成物とする観点から、エポキシ系架橋剤が好ましい。
本発明の粘着剤組成物には、上記(A)~(D)成分以外に、得られる粘着剤組成物の電圧印加前の粘着性をより向上させる観点から、さらに粘着付与樹脂を含有してもよい。
粘着付与樹脂としては、例えば、ロジン樹脂、ロジンフェノール樹脂、ロジンエステル樹脂等のロジン系樹脂;これらロジン系樹脂を水素化した水素化ロジン系樹脂;テルペン系樹脂、テルペンフェノール系樹脂、芳香族変性テルペン系樹脂等のテルペン系樹脂;これらテルペン系樹脂を水素化した水素化テルペン系樹脂;石油ナフサの熱分解で生成するペンテン、イソプレン、ピペリン、1.3-ペンタジエン等のC5留分を共重合して得られるC5系石油樹脂及びこのC5系石油樹脂の水素化石油樹脂;石油ナフサの熱分解で生成するインデン、ビニルトルエン、α-メチルスチレン、β-メチルスチレン等のC9留分を共重合して得られるC9系石油樹脂及びこのC9系石油樹脂の水素化石油樹脂;等が挙げられる。
本発明の粘着剤組成物には、本発明の効果を損なわない範囲において、上述以外の汎用添加剤を含有してもよい。
汎用添加剤としては、酸化防止剤、紫外線吸収剤、光安定剤、樹脂安定剤、軟化剤(可塑剤)、充填剤、防錆剤、顔料、染料等が挙げられる。
汎用添加剤を添加する場合、各々の汎用添加剤の含有量は、アクリル系重合体(A)100質量部に対して、好ましくは0.01~10質量部、より好ましくは0.05~5質量部、更に好ましくは0.1~3質量部である。
本発明の電気剥離性粘着シート(以下、単に「粘着シート」ともいう)は、上述の本発明の電気剥離性粘着剤組成物からなる粘着剤層を有する。
本発明の粘着シートは、本発明の粘着剤組成物からなる粘着剤層を有するものであれば、その構成は特に限定されず、基材の少なくとも片面に粘着剤層を有する粘着シートであってもよく、粘着剤層が2枚の剥離シートにより挟持された構成を有する粘着シートであってもよい。
本発明の粘着シートの具体的な構成として、例えば、図1(a)に示されたような、基材2の片面上に粘着剤層3を有する、基材付き電気剥離性粘着シート1aが挙げられる。
また、図1(b)に示されたような、基材2の両面上に粘着剤層3及び粘着剤層3’を有する基材付き電気剥離性粘着シート1bや、図1(c)に示されたような、基材2の片面に形成した粘着剤層3上に、さらに剥離シート4が積層された基材付き電気剥離性粘着シート1c等も挙げられる。なお、電気剥離性粘着シート1bは、粘着剤層3及び3’上に、さらに剥離シートが設けられていてもよい。
この電気剥離性粘着シート1dの剥離シート4、4’の素材は、同じものでもよく、異なるものでもよいが、剥離シート4と剥離シート4’との剥離力が異なるように調整された素材であることが好ましい。
本発明の粘着シートの他の構成としては、表面が剥離処理された剥離シートの片面に粘着剤層を設けたものをロール状に巻いた構成を有する電気剥離性粘着シート等も挙げられる。
つまり、図2の(a)のように、本発明の電気剥離性粘着シート1aを被着体11から剥離しようとする場合を考える。この図2(a)では、粘着剤層3は、被着体11及び基材2aに挟持されており、電圧印加装置50の陽極端子51を基材2aに接続し、陰極端子52を被着体11に接続することで、粘着剤層3の両面から電極を印加することができる。
なお、図1の(d)のような基材無し電気剥離性粘着シート1dを用いる場合には、図2中の「基材2a」の構成が、別の「被着体」となり、粘着剤層3は、2枚の被着体に挟持された構成となり、電圧印加装置50の陽極端子51、陰極端子52とそれぞれの被着体に接続することで、粘着剤層3の両面から電極を印加することができる。
この図2の(a)に示された状態で、電圧を印加すると、図2の(b)に示すように、陰極側に接続した粘着剤層の面3aと、当該陰極側に接続した粘着剤層の面3aと接触する被着体11との間で、粘着力が低下し、電気剥離性粘着シート1aを被着体から容易に剥離することができる。
なお、一般的に印加電圧が大きい程、印加時間は短く、一方、印加電圧が小さい程、印加時間は長くなる。例えば、印加電圧が10~50Vである場合、印加時間は30~300秒で剥離が可能となる。
また、本発明の粘着シートの電圧印加後の粘着力の減少率としては、好ましくは20%以上、より好ましくは30%以上、更に好ましくは45%以上、より更に好ましくは70%以上である。
なお、本発明の粘着シートの電圧印加前の粘着力、及び電圧印加後の粘着力の減少率は、実施例に記載の方法により測定された値を意味する。
当該粘着剤層の厚さが0.5μm以上であれば、被着体の種類に依らずに、良好な粘着力を発現させることができる。一方、当該粘着剤層の厚さが120μm以下であれば、生産性の面で利点があると共に、取扱性の面でも良好な電気剥離性粘着シートとなり得る。
導電性の基材を構成する材料としては、例えば、アルミニウム、スズドープ酸化インジウム、銅、鉄、銀、白金、金等の金属及びこれら金属の合金等が挙げられる。
また、ポリエチレンテレフタレート等の樹脂フィルムに、上記金属を蒸着させてなる金属蒸着体を基材として用いてもよい。樹脂フィルムに金属を蒸着させる場合は、粘着剤層と接する樹脂フィルムの面に金属を蒸着させることが好ましい。
剥離シート用基材としては、例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステル、ポリエチレン、ポリプロピレン、ポリブテン、ポリブタジエン、ポリメチルペンテン、ポリ塩化ビニル、塩化ビニル共重合体、ポリウレタン、エチレン-酢酸ビニル共重合体、アイオノマー樹脂、エチレン(メタ)アクリル酸共重合体、ポリスチレン、ポリカーボネート、フッ素樹脂、低密度ポリエチレン、直鎖低密度ポリエチレン、トリアセチルセルロース等の樹脂フィルムや、上質紙、コート紙、グラシン紙等の紙基材、これらの紙基材にポリエチレン等の熱可塑性樹脂をラミネートしたラミネート紙等が挙げられる。
本発明の電気剥離性粘着シートの製造方法としては、特に制限はなく、例えば、本発明の粘着剤組成物に対して、トルエン、酢酸エチル、メチルエチルケトン等の有機溶媒を配合して、粘着剤組成物の溶液を調整し、基材又は剥離シートの剥離処理面に、公知の塗布方法により、当該溶液を塗布及び乾燥し、粘着剤層を形成させて、粘着シートを得る方法等が挙げられる。
また、基材や剥離シートの剥離層面に粘着剤組成物を有機溶媒に溶解した溶液を塗布した後、形成される粘着剤層中に溶媒や低沸点成分が残留することを防ぐために、乾燥処理をし、これらの残留物を除去することが好ましい。
まず、図1(a)のような基材2の片面に粘着剤層3を有する電気剥離性粘着シート1aは、例えば、基材2の一方の面上に、粘着剤組成物の溶液を直接塗布して、粘着剤層3を形成して作製することができる。
また、剥離シートの剥離処理面上に、粘着剤組成物の溶液を直接塗布して、粘着剤層3を形成した後、その粘着剤層3と基材2とを貼り合わせ、剥離シートを除去して作製してもよい。
また、剥離シートの剥離処理面上に、粘着剤組成物の溶液を直接塗布して、粘着剤層を形成したものを2枚用意し、それぞれの粘着剤層を基材2の両面に貼り合わせて、剥離シートを除去して作製してもよい。
また、剥離シート4の剥離処理面上に、粘着剤組成物の溶液を直接塗布して、粘着剤層3を形成した後、その粘着剤層3と基材2とを貼り合わせて作製してもよい。
なお、上述のとおり、剥離シート4と剥離シート4’とは、剥離力が異なるように調整することが好ましい。
本発明の電気剥離性粘着シートは、任意の被着体に貼付して使用することができる。
被着体としては、特に限定されず、導電性を有していても有さなくてもよいが、粘着剤面に電圧を印加することが容易となる観点から、被着体がそのまま電極となるように、導電性を有する被着体であることが好ましい。
そのため、上記観点から、本発明の電気剥離性粘着シートの使用方法としては、本発明の粘着シートを、導電性を有する被着体に貼付して使用する方法が好ましい。
導電性を有する被着体としては、例えば、アルミニウム、スズドープ酸化インジウム、銅、鉄、銀、白金、金等の金属やそれら金属の合金等からなる被着体が挙げられる。
また、以下の実施例及び比較例で使用した成分の質量平均分子量(Mw)又は数平均分子量(Mn)については、下記方法に基づいて測定した値を用いた。
ゲル浸透クロマトグラフ装置(東ソー株式会社製、製品名「HLC-8020」)を用いて、下記の条件下で測定し、標準ポリスチレン換算にて測定した値を用いた。
(質量平均分子量(Mw)の測定条件)
・カラム:「TSK guard column HXL-H」「TSK gel GMHXL(×2)」「TSK gel G2000HXL」(いずれも東ソー株式会社製)
・カラム温度:40℃
・展開溶媒:テトラヒドロフラン
・流速:1.0mL/min
(数平均分子量(Mn)の測定条件)
・カラム:「TSK guard column HXL-L」「TSK gel G2500HXL」「TSK gel G2000HXL」「TSK gel G1000HXL」(いずれも東ソー株式会社製)
・カラム温度:40℃
・展開溶媒:テトラヒドロフラン
・流速:1.0mL/min
下記に示す成分を表1に記載の配合量(有効成分比(固形分比))で配合し、さらに有機溶媒としてトルエンを添加して有効成分(固形分)濃度26質量%の電気剥離性粘着剤組成物の塗布液を調製した。(なお、有効成分とは、粘着剤組成物中に残留する水及び有機溶媒以外の成分を意味する。)
次いで、この調製した電気剥離性粘着剤組成物の塗布液を、剥離シート(リンテック社製、製品名「SP-PET381130」、厚さ:38μm、表面がシリコーン剥離処理されたポリエチレンテレフタレートフィルム)の剥離処理面上に、乾燥後の厚さが50μmになるように塗布し、100℃で120秒間乾燥させて、剥離シート上に粘着剤層を形成した。
そして、形成した粘着剤層の面上に、基材として、アルミニウム箔基材(日本金属箔工業社製、製品名「アルミタンタイSツヤ50フクオカ」、厚さ:50μm)を貼付して、図1の(c)に示す電気剥離性粘着シート1cと同様の構成を有する、基材付きタイプの電気剥離性粘着シートを作製した。
実施例及び比較例で使用した各成分の詳細は以下のとおりである。
n-ブチルアクリレート(BA)90質量部、及びアクリル酸(AA)10質量部から合成されたアクリル系共重合体の酢酸エチル溶液(BA/AA=90/10(質量%)、Mw=70万、固形分濃度=33.6質量%)。
ポリエチレングリコール(Mn=400)。
(C1):下記式(C1)で示される、ポリオキシエチレンβ-ナフチルエーテルサルフェートのアンモニウム塩(Mn=500、式(C1)中のmはエチレンオキサイド鎖の繰り返し単位数を示す)。
「TETRAD-C」:商品名、三菱瓦斯化学(株)製、エポキシ系架橋剤。
実施例及び比較例で作製した基材付き電気剥離性粘着シートを、25mm×300mmの大きさに裁断し、23℃、50%RH(相対湿度)の環境下で、剥離シートを剥がし、表出した粘着剤層を、被着体であるアルミニウム板(パルテック社製、製品名「A105OP」、150mm×70mm×1mm)に貼付した。貼付に際しては、重さ2kgのローラーを用い、1往復させて、被着体に圧着し、23℃、50%RH(相対湿度)の環境下で、貼付後24時間放置し、粘着力測定用サンプルを作製した。
そして、23℃、50%RH(相対湿度)の環境下で、引張試験機(オリエンテック社製、製品名「テンシロン」)を用いて、剥離速度300mm/分、剥離角度180°の条件で粘着シートを剥離した際に測定された値(単位:N/25mm)を電圧印加前の粘着シートの粘着力とした。
上述の粘着力測定用サンプルを、図2の(a)に示すように、電圧印加装置50(高砂製作所社製、製品名「KH-100H」)を用い、陽極端子51をアルミニウム箔の基材2aに、陰極端子52を被着体11に接続し、100Vの電圧を60秒間印加した。
電圧印加後、30秒間放置した後、同じ23℃、50%RH(相対湿度)の環境下で、引張試験機(オリエンテック社製、商品名「テンシロン」)を用いて、剥離速度300mm/分、剥離角度180°の条件で粘着シートを剥離した際に測定された値(単位:N/25mm)を電圧印加後の粘着シートの粘着力とした。
なお、表1中の粘着力減少率は、下記式により算出した値である。
〔粘着力の減少率(%)〕=100-〔電圧印加後の粘着シートの粘着力〕/〔電圧印加前の粘着シートの粘着力〕×100
一方、比較例1~10の電気剥離性粘着シートは、実施例に比べ、電圧印加後の粘着力が高く、電圧印加前後での粘着力の減少があまり見られない結果となった。
2 基材
2a アルミニウム箔基材
3、3’ 粘着剤層
3a、3a’ 陰極側に接続した粘着剤層の面
4、4’ 剥離シート
11 被着体
50 電圧印加装置
51 陽極端子
52 陰極端子
Claims (14)
- アクリル系重合体(A)、数平均分子量が2000以下である(ポリ)アルキレンポリオール(B)、及びアンモニウム塩(C)を含有する、電気剥離性粘着剤組成物。
- (C)成分が、スルホン酸のアンモニウム塩である、請求項1に記載の電気剥離性粘着剤組成物。
- (A)成分100質量部に対する(C)成分の含有量が、3~250質量部である、請求項1に記載の電気剥離性粘着剤組成物。
- (B)成分が、(ポリ)アルキレングリコールを含む、請求項1に記載の電気剥離性粘着剤組成物。
- (A)成分100質量部に対する(B)成分の含有量が、3~250質量部である、請求項1に記載の電気剥離性粘着剤組成物。
- (A)成分が、(メタ)アクリル酸アルキルエステル由来の構成単位(a1)を60~99.9質量%、及び官能基含有不飽和単量体由来の構成単位(a2)を0.1~40質量%含むアクリル系共重合体である、請求項1に記載の電気剥離性粘着剤組成物。
- さらに架橋剤(D)を含有する、請求項1に記載の電気剥離性粘着剤組成物。
- 請求項1~9のいずれかに記載の電気剥離性粘着剤組成物からなる粘着剤層を有する、電気剥離性粘着シート。
- 導電性の基材の少なくとも片面に、前記粘着剤層を有する、請求項10に記載の電気剥離性粘着シート。
- 前記粘着剤層が、2枚の剥離シートに挟持された構成を有する、請求項10に記載の電気剥離性粘着シート。
- 2枚の被着体、もしくは被着体及び基材に挟持された前記粘着剤層の両側の面の間に電圧を印加した際、陰極側に接続した前記粘着剤層の面と、該面と接触する前記被着体又は前記基材との間で剥離する、請求項10に記載の電気剥離性粘着シート。
- 請求項10に記載の電気剥離性粘着シートを、導電性を有する被着体に貼付する、電気剥離性粘着シートの使用方法。
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US11623429B2 (en) | 2018-03-08 | 2023-04-11 | Nitto Denko Corporation | Electrical debonding adhesive sheet, joined body, and joining and separation method for adherend |
WO2019172304A1 (ja) * | 2018-03-08 | 2019-09-12 | 日東電工株式会社 | 電気剥離型粘着シート、接合体、並びに被着体の接合及び分離方法 |
US11964462B2 (en) | 2018-03-08 | 2024-04-23 | Nitto Denko Corporation | Electrical debonding adhesive sheet, joined body, and joining and separation method for adherend |
US12037522B2 (en) | 2018-03-08 | 2024-07-16 | Nitto Denko Corporation | Electrical debonding type adhesive sheet, joined body, and debonding method for joined body |
JP7556933B2 (ja) | 2018-03-08 | 2024-09-26 | 日東電工株式会社 | 電気剥離型粘着シート、接合体及び接合体の剥離方法 |
WO2022065480A1 (ja) * | 2020-09-28 | 2022-03-31 | リンテック株式会社 | 電気剥離性粘着シート、及び電気剥離性粘着シートの使用方法 |
WO2022065483A1 (ja) * | 2020-09-28 | 2022-03-31 | リンテック株式会社 | 電気剥離性粘着剤組成物、電気剥離性粘着シート、及び電気剥離性粘着シートの使用方法 |
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CN105102568A (zh) | 2015-11-25 |
EP2960313A1 (en) | 2015-12-30 |
US20160009961A1 (en) | 2016-01-14 |
EP2960313A4 (en) | 2016-08-17 |
EP2960313B1 (en) | 2018-11-21 |
JP6280916B2 (ja) | 2018-02-14 |
CN105102568B (zh) | 2017-12-29 |
JPWO2014157408A1 (ja) | 2017-02-16 |
US10604684B2 (en) | 2020-03-31 |
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