WO2022065483A1 - 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 - Google Patents
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 Download PDFInfo
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- WO2022065483A1 WO2022065483A1 PCT/JP2021/035369 JP2021035369W WO2022065483A1 WO 2022065483 A1 WO2022065483 A1 WO 2022065483A1 JP 2021035369 W JP2021035369 W JP 2021035369W WO 2022065483 A1 WO2022065483 A1 WO 2022065483A1
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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
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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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
- 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
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
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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
- C09J193/00—Adhesives based on natural resins; Adhesives based on derivatives thereof
- C09J193/04—Rosin
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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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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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
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
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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
- 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]
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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
- 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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- 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
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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
- 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
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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
- 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
Definitions
- the present invention relates to an electro-peelable pressure-sensitive adhesive composition, an electro-peelable pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed from the electro-peelable pressure-sensitive adhesive composition, and a method of using the electro-peelable pressure-sensitive adhesive sheet.
- removability may be required in applications such as temporary fixing tape, surface protective film, masking tape for painting or decoration, and removable memo.
- the removable adhesive sheet is required to have an adhesive strength that does not peel off from the adherend during transportation, storage, processing, etc. when it is attached to the adherend, but after it has finished functioning. , Removability that can be easily removed is required.
- Patent Document 1 discloses a composition for energization peeling containing an ionic liquid as a pressure-sensitive adhesive that can be easily peeled off from an adherend after use.
- the present invention is an electrically peelable pressure-sensitive adhesive composition
- a base polymer comprising a base polymer, an ionic compound, and a rosin-containing diol
- an electrically peelable pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed from the electro-peelable pressure-sensitive adhesive composition.
- Specific embodiments of the present invention are as follows [1] to [14].
- An electropeeling pressure-sensitive adhesive composition comprising a base polymer (A), an ionic compound (B), and a rosin-containing diol (C).
- N is an integer of 1 or more.
- Sexual pressure-sensitive adhesive composition [8] Any of the above [1] to [7], wherein the content of the active ingredient that is liquid at 25 ° C. is 1 to 50% by mass with respect to the total amount of the active ingredient in the pressure-sensitive adhesive composition.
- the electrically peelable pressure-sensitive adhesive composition of one preferred embodiment of the present invention has high adhesiveness before voltage application, but can easily reduce the adhesiveness by voltage application.
- the upper limit value and the lower limit value can be arbitrarily combined.
- the range of "20 to 90” and the range of "40 to 120” are also described in the present specification. It is included in the numerical range.
- the numerical range is described as "preferably 20 or more, more preferably 40 or more, preferably 120 or less, more preferably 90 or less", it is referred to as "20 to 90”.
- the range and the range of "40 to 120” are also included in the numerical range described herein.
- the description of "60 to 100” means that the range is "60 or more and 100 or less”.
- the "active ingredient" of the electro-removable pressure-sensitive adhesive composition means a component contained in the electro-removable pressure-sensitive adhesive composition excluding a diluting solvent of water or an organic solvent.
- the mass average molecular weight (Mw) is a polystyrene-equivalent value measured by a gel permeation chromatography (GPC) method, and specifically, a value measured based on the method described in Examples. Is.
- the electroremovable pressure-sensitive adhesive composition of the present invention (hereinafter, also simply referred to as “taste-sensitive adhesive composition”) is a base polymer (A) (hereinafter, also referred to as “component (A)”), an ionic compound (B) ( Hereinafter, it is also referred to as “component (B)”) and a rosin-containing diol (C) (hereinafter, also referred to as “component (C)”).
- a pressure-sensitive adhesive composition comprising a component (A), a component (B), and a component (C) is a component (A) as a raw material of the pressure-sensitive adhesive composition.
- Component (B), and component (C) are used. Therefore, for example, an embodiment in which the component (B) is ionized into a cation and an anion in the pressure-sensitive adhesive composition is also included.
- a general electro-removable pressure-sensitive adhesive composition an ionic compound is blended with a base polymer to impart a property of reducing the pressure-sensitive adhesive by applying electric power.
- the electrically peelable pressure-sensitive adhesive composition containing an ionic compound has insufficient tackiness as compared with the pressure-sensitive adhesive composition containing no ionic compound.
- a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed from such an electrically peelable pressure-sensitive adhesive composition is particularly required to have improved adhesive strength against a metal adherend such as a stainless steel plate or an aluminum plate.
- a pressure-sensitive adhesive is often added in order to improve the stickiness.
- a tackifier when blended with an electroleapable pressure-sensitive adhesive composition composed of a base polymer and an ionic compound, depending on the type of the tackifier, it depends on the type of the tackifier.
- Adhesive composition that has poor compatibility with ionic compounds (particularly ionic liquids) and whose adhesiveness does not sufficiently improve before voltage application, or adhesiveness that does not easily decrease even when voltage is applied. In some cases, it became a sexual composition.
- a tacky composition containing a rosin-containing diol, which is a tackifier, together with a base polymer and an ionic compound has high tackiness before applying a voltage. It was found that while having a property, it has a property that the adhesiveness can be easily lowered by applying a voltage.
- the pressure-sensitive adhesive composition of the present invention has been completed based on the findings.
- the pressure-sensitive adhesive composition according to one aspect of the present invention is further blended with one or more selected from the cross-linking agent (D) and the compound (E) represented by the general formula (e-1). It is preferably a composition, and more preferably a pressure-sensitive adhesive composition in which the components (D) and (E) are blended together. Further, the pressure-sensitive adhesive composition according to one aspect of the present invention may be a pressure-sensitive adhesive composition containing additives other than the components (A) to (E).
- the components (A) and the components (C) is preferably 65 to 100% by mass, more preferably 70 to 100% by mass, based on the total amount (100% by mass) of the active ingredient of the pressure-sensitive adhesive composition. It is more preferably 80 to 100% by mass, still more preferably 85 to 100% by mass, and particularly preferably 90 to 100% by mass.
- the total blending amount of the component (A), the component (B), the component (C), the component (D) and the component (E) is the said.
- the total amount (100% by mass) of the active ingredient of the pressure-sensitive adhesive composition preferably 70 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 85 to 100% by mass, still more preferably 90 to 90 to 100% by mass. It is 100% by mass, particularly preferably 95 to 100% by mass.
- the content of the active ingredient which is liquid at 25 ° C. is determined in the pressure-sensitive adhesive composition. 1 to 50% by mass, more preferably 3 to 40% by mass, still more preferably 5 to 30% by mass, still more preferably 7 to 25% by mass, based on the total amount (100% by mass) of the active ingredient of. Particularly preferably, it is 10 to 20% by mass.
- a pressure-sensitive adhesive composition containing a large amount of liquid components may have insufficient adhesiveness.
- the pressure-sensitive adhesive composition of one aspect of the present invention since the rosin-based diol (C) having good compatibility with the liquid component is blended, the pressure-sensitive adhesive composition has further improved adhesiveness. be able to.
- the above-mentioned "liquid component” is an active ingredient of a liquid at 25 ° C. other than a solvent, and specifically, an ionic liquid (B3) used as the component (B) and a compound (E) used as the component (E). ) Etc. can be mentioned.
- the base polymer (A) used in one embodiment of the present invention may be any polymer having adhesiveness, for example, an acrylic polymer, a urethane polymer, a rubber polymer, an olefin polymer, a silicone polymer, and these. Examples thereof include a curable polymer having a polymerizable functional group in the polymer. These base polymers (A) may be used alone or in combination of two or more. Further, the base polymer (A) used in one aspect of the present invention may be an emulsion type polymer or a non-emulsion type polymer.
- the mass average molecular weight of the base polymer (A) used in one embodiment of the present invention is preferably 10,000 to 2 million, more preferably 20,000 to 2, from the viewpoint of obtaining a pressure-sensitive adhesive composition having high adhesiveness before applying a voltage. It is 1.8 million, more preferably 30,000 to 1.5 million.
- the mass average molecular weight is a polystyrene-equivalent value measured by a gel permeation chromatography (GPC) method, and specifically, a value measured based on the method described in Examples. be.
- the base polymer (A) used in one embodiment of the present invention is acrylic from the viewpoint of making a pressure-sensitive adhesive composition which has high adhesiveness before voltage application and can easily reduce the adhesiveness by voltage application. It is preferable to include a system polymer (A1).
- the content ratio of the acrylic polymer (A1) in the component (A) is the total amount (100) of the component (A) contained in the pressure-sensitive adhesive composition. Mass%), preferably 30 to 100% by mass, more preferably 50 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass. %, Especially preferably 95 to 100% by mass.
- acrylic polymer (A1) used in one embodiment of the present invention examples include polymers having a structural unit (a1) derived from an alkyl (meth) acrylate (hereinafter, also referred to as “monomer (a1 ′)”). From the viewpoint of making a pressure-sensitive adhesive composition which has high adhesiveness before applying a voltage and can easily reduce the adhesiveness by applying a voltage, a functional group-containing monomer (hereinafter, "monomer (a2')" is used together with the structural unit (a1). ) ”), It is preferable that the copolymer has a structural unit (a2).
- the form of the copolymer is not particularly limited and may be any of a random copolymer, a block copolymer, and a graft copolymer.
- the acrylic polymer (A1) used in one aspect of the present invention may be used alone or in combination of two or more.
- the mass average molecular weight of the acrylic polymer (A1) is preferably 50,000 to 2 million, more preferably 100,000 to 1,500,000, still more preferably 100,000 to 1,500,000, from the viewpoint of obtaining a pressure-sensitive adhesive composition having high adhesiveness before applying a voltage.
- the acrylic polymer (A1) used in one embodiment of the present invention is a structural unit (a3) derived from a monomer other than the monomer (a1') and (a2') (hereinafter, also referred to as "monomer (a3')"). ) May be a copolymer.
- the content ratio of the structural units (a1) and (a2) is based on the total amount (100% by mass) of the structural units of the acrylic polymer (A1). It may be 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more, 75% by mass or more, 80% by mass or more, 85% by mass or more, 90% by mass or more, or 95% by mass or more. Further, it may be 100% by mass or less, 99% by mass or less, 95% by mass or less, 90% by mass or less, or 85% by mass or less.
- the monomers and constituent units constituting the acrylic polymer (A1) will be described.
- the alkyl group of the monomer (a1') preferably has 1 to 30, more preferably 1 to 20, more preferably 1 to 16, still more preferably 1 to 12, still more preferably 1 to 8, etc. Particularly preferably, it is 4 to 8.
- the alkyl group of the monomer (a1') may be a linear alkyl group or a branched chain alkyl group.
- the monomer (a1') examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate (n-propyl (meth) acrylate, i-propyl (meth) acrylate), and butyl (.
- the monomer (a1') may be used alone or in combination of two or more.
- the monomer (a1') preferably contains at least an alkyl (meth) acrylate having an alkyl group having 4 to 8 carbon atoms, and is preferably a butyl (meth) acrylate, a pentyl (meth) acrylate, or a hexyl (meth) acrylate.
- Heptyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate are more preferably contained
- butyl (meth) acrylate or 2-ethylhexyl (meth) acrylate is further preferably contained. It is even more preferable to contain at least (meth) acrylate.
- the acrylic polymer (A1) used in one embodiment of the present invention has, as the structural unit (a1), a structural unit (a1-1) derived from an alkyl (meth) acrylate having an alkyl group having 4 to 8 carbon atoms. It is also preferable to have a structural unit (a1-2) derived from an alkyl (meth) acrylate having an alkyl group having 1 to 3 carbon atoms together with the structural unit (a1-1).
- the content ratio of the structural unit (a1-1) is based on the total amount (100% by mass) of the structural unit (a1) contained in the acrylic polymer (A1).
- It is preferably 40% by mass or more, more preferably 50% by mass or more, more preferably 55% by mass or more, still more preferably 60% by mass or more, still more preferably 65% by mass or more, and particularly preferably 70% by mass or more. Further, it may be 100% by mass or less, 99% by mass or less, 98% by mass or less, 95% by mass or less, 90% by mass or less, 85% by mass or less, 80% by mass or less, or 76% by mass.
- the content ratio of the structural unit (a1) is the total amount (100% by mass) of the structural units of the acrylic polymer (A1) before applying a voltage. From the viewpoint of obtaining a pressure-sensitive adhesive composition having better adhesiveness, it is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, still more preferably 60% by mass or more, and particularly preferably. Is 70% by mass or more, and is preferably 99.99% by mass or less, from the viewpoint of obtaining a pressure-sensitive adhesive composition capable of securing the content ratio of the above-mentioned structural unit (a2) and further improving the cohesive force.
- Examples of the monomer (a2') include a hydroxy group-containing monomer, a carboxy group-containing monomer, an epoxy group-containing monomer, and the like. These monomers (a2') may be used alone or in combination of two or more.
- hydroxy-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl (meth).
- Hydroxyalkyl (meth) acrylates such as acrylates and 4-hydroxybutyl (meth) acrylates; unsaturated alcohols such as vinyl alcohols and allyl alcohols may be mentioned.
- the alkyl group of the hydroxyalkyl (meth) acrylates has preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.
- the alkyl group may be a straight chain alkyl group or a branched chain alkyl group.
- carboxy group-containing 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-carboxyl. Examples thereof include ethyl (meth) acrylate.
- epoxy-containing monomer examples include glycidyl (meth) acrylate, ⁇ -methylglycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 3-epoxycyclo-2-hydroxypropyl (meth) acrylate.
- Epoxy group-containing (meth) acrylic acid esters such as glycidyl crotonate, allyl glycidyl ether and the like.
- the acrylic polymer (A1) used in one embodiment of the present invention is preferably a copolymer having a structural unit (a2-1) derived from a hydroxy group-containing monomer as a structural unit (a2). ..
- the content ratio of the structural unit (a2-1) is the total amount (100 mass) of the structural unit (a2) contained in the acrylic polymer (A1). %), More preferably 60 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass. Is.
- the content ratio of the structural unit (a2) is such that the cohesive force is higher than the total amount (100% by mass) of the structural units of the acrylic polymer (A1).
- it is preferably 0.01% by mass or more, more preferably 0.10% by mass or more, still more preferably 1.0% by mass or more, still more preferably 3.0% by mass.
- the above is particularly preferably 4.0% by mass or more, and further 5.0% by mass or more, 7.0% by mass or more, 10.0% by mass or more, 12.0% by mass or more, or 15.0% by mass.
- the above may be sufficient, and from the viewpoint of ensuring the content of the structural unit (a1) and obtaining a pressure-sensitive adhesive composition having better adhesiveness before applying a voltage, it is preferably 60% by mass or less, more preferably 50. It is mass% or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, and particularly preferably 25% by mass or less.
- the monomer (a3') other than the monomers (a1') and (a2') is not particularly limited, but for example, olefins such as ethylene, propylene and isobutylene, halogenated olefins such as vinyl chloride and vinylidene chloride, and the like.
- Diene-based monomers such as butadiene, isoprene, and chloroprene, styrene, ⁇ -methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, (meth) acrylamide, (meth) acrylonitrile, (meth) acryloylmorpholin, N-vinylpyrrolidone. And so on.
- Diene-based monomers such as butadiene, isoprene, and chloroprene, styrene, ⁇ -methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, (meth) acrylamide, (meth) acrylonitrile, (meth) acryloylmorpholin, N-vinylpyrrolidone. And so on.
- These monomers (a3') may be used alone or in combination of two or more.
- the content ratio of the structural unit (a3) is 0% by mass or more with respect to the total amount (100% by mass) of the structural units of the acrylic polymer (A1). It may be 1% by mass or more, 5% by mass or more, 10% by mass or more, or 15% by mass, and 45% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, 25% by mass or less. , 20% by mass or less, 15% by mass or less, 10% by mass or less, or 5% by mass or less.
- the blending amount of the component (A) is such that the pressure-sensitive adhesive composition has high adhesiveness before applying a voltage and can easily reduce the adhesiveness by applying a voltage.
- the (content) is preferably 25% by mass or more, more preferably 30% by mass or more, more preferably 35% by mass or more, still more preferably 35% by mass or more, based on the total amount (100% by mass) of the active ingredient of the pressure-sensitive adhesive composition. Is 40% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, particularly preferably 55% by mass or more, and preferably 98% by mass or less, more preferably 95% by mass or less.
- ionic compound (B) used in one embodiment of the present invention include one or more selected from an alkali metal salt (B1), an organic quaternary ammonium salt (B2), and an ionic liquid (B3). ..
- the component (B) used in one embodiment of the present invention preferably contains at least one selected from an alkali metal salt (B1) and an ionic liquid (B3). Further, as the component (B) used in one embodiment of the present invention, it is preferable to use an alkali metal salt (B1) or an ionic liquid (B3) as a main component.
- the above-mentioned "main component” means the component having the highest content among the components constituting the component (B). Further, a pressure-sensitive adhesive composition having a large amount of a liquid component such as an ionic liquid (B3) may have insufficient adhesiveness.
- the pressure-sensitive adhesive composition of one aspect of the present invention since the rosin-based diol (C) having good compatibility with the ionic liquid (B3) is blended, the pressure-sensitive adhesiveness is further improved and a voltage is applied. It is possible to obtain a pressure-sensitive adhesive composition that can easily reduce the stickiness.
- the content of the component (B) other than the alkali metal salt (B1) is 100 parts by mass with respect to the total amount of the alkali metal salt (B1). Less than 100 parts by mass, 0 to 90 parts by mass, 0 to 50 parts by mass, 0 to 30 parts by mass, 0 to 20 parts by mass, 0 to 10 parts by mass, 0 to 5 parts by mass, 0 to 1 part by mass, 0 to 0 .1 part by mass, 0 to 0.01 part by mass, 0 to 0.001 part by mass, or 0 to 0.0001 part by mass.
- the content of the component (B) other than the ionic liquid (B3) is 100 parts by mass with respect to 100 parts by mass of the total amount of the ionic liquid (B3). Less than, 0 to 90 parts by mass, 0 to 50 parts by mass, 0 to 30 parts by mass, 0 to 20 parts by mass, 0 to 10 parts by mass, 0 to 5 parts by mass, 0 to 1 part by mass, 0 to 0.1 parts by mass. It may be 0 to 0.01 parts by mass, 0 to 0.001 parts by mass, or 0 to 0.0001 parts by mass.
- the blending ratio of the component (B) with respect to 100 parts by mass of the total amount of the component (A) is a viewpoint of obtaining a pressure-sensitive adhesive composition that can easily reduce the adhesiveness by applying a voltage. Therefore, it is preferably 1.0 part by mass or more, more preferably 3.0 part by mass or more, more preferably 5.0 part by mass or more, still more preferably 7.0 part by mass or more, still more preferably 9.0 part by mass or more.
- the pressure-sensitive adhesive composition is particularly preferably 11.0 parts by mass or more, further may be 13.0 parts by mass or more, or 16.0 parts by mass or more, and has high adhesiveness before applying a voltage.
- the blending amount (content) of the component (B) is easily adhered to the total amount (100% by mass) of the active component of the pressure-sensitive adhesive composition by applying a voltage.
- it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, more preferably 1.0% by mass or more, still more preferably 3.0% by mass.
- % Or more more preferably 5.0% by mass or more, particularly preferably 7.0% by mass or more, and preferably 50% by mass from the viewpoint of obtaining a pressure-sensitive adhesive composition having high adhesiveness before applying a voltage.
- % Or less more preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, still more preferably 20% by mass or less, and particularly preferably 15% by mass or less.
- the alkali metal salt (B1) used in one embodiment of the present invention is solid at room temperature (25 ° C.), but may be a compound that ionizes cations (alkali metal ions) and anions in a liquid.
- Specific alkali metal salts (B1) include, for example, MCl, MBr, MI, MAlCl 4 , MAL 2 Cl 7 , MBF 4 , MPF 6 , MSCN, MClO 4 , MNO 3 , CH 3 COOM, C 9 H 19 .
- the alkali metal salt (B1) used as the component (B) in one aspect of the present invention preferably contains the alkali metal salt (B11) represented by the following general formula (b-1).
- RF is independently a fluorine atom or a fluorinated alkyl group.
- the number of carbon atoms of the fluorinated alkyl group is preferably 1 to 10, more preferably 1 to 8, still more preferably 1 to 4, still more preferably 1 to 3, and particularly preferably 1 to 2.
- fluorinated alkyl group means a group in which at least one hydrogen atom of an alkyl group is substituted with a fluorine atom, and may be a straight chain or a branched chain. good.
- the RF is preferably a fluorine atom or a perfluoroalkyl group, which is a fluorine atom, -CF 3 , -C 2 F 5 , -C 3 F 7 , or -C 4 F 9 . Is more preferable, and it is further preferable that it is a fluorine atom or ⁇ CF3 .
- M is an alkali metal atom (lithium atom (Li), sodium atom (Na), potassium atom (K), rubidium atom (Rb), cesium atom (Cs), francium atom (Fr)), but Li, Na.
- Li lithium atom (Li), sodium atom (Na), potassium atom (K), rubidium atom (Rb), cesium atom (Cs), francium atom (Fr)
- Li Na.
- it is preferably K, more preferably Na or K, and even more preferably Na.
- the organic quaternary ammonium salt (B2) used in one embodiment of the present invention may be a compound represented by the following general formula (b-2), which is a solid at room temperature (25 ° C.).
- the organic quaternary ammonium salt (B2) may be used alone or in combination of two or more.
- R 11 to R 14 are independently alkyl groups having 1 to 4 carbon atoms.
- X is F, Cl, Br, I, ClO 4 , BF 4 , PF 6 , or [(R 15 ) 4 N] 2 SO 4 (R 15 is an independently alkyl group having 1 to 4 carbon atoms. )be.
- Specific organic quaternary ammonium salts (B2) include, for example, ammonium bromide or ammonium chloride such as tetrabutyl, tetrapropyl, tetraethyl, tetramethyl, triethylbutyl, triethylpropyl, triethylmethyl; tetrabutyl, tetrapropyl, tetraethyl, Ammonium tetrafluoroborate such as tetramethyl, triethylbutyl, triethylpropyl, triethylmethyl; ammonium hexafluorophosphate such as tetrabutyl, tetrapropyl, tetraethyl, tetramethyl, triethylbutyl, triethylpropyl, triethylmethyl; tetrabutyl, tetrapropyl, tetraethyl ,
- the ionic liquid (B3) used in one embodiment of the present invention may be a molten salt that is liquid at room temperature (25 ° C.) and may be a compound composed of an organic cation and its counterion, an anion.
- Examples of the organic cation constituting the ionic liquid (B3) include cations represented by any of the following general formulas (b-3-i) to (b-3-viii).
- the organic cation constituting the ionic liquid (B3) is preferably a cation represented by the following general formula (b-3-ii).
- Ra is independently an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 1 to 20 carbon atoms.
- R b is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and-(C 2 H 4 O). It is a group represented by n —R c (n is an integer of 1 to 20, R c is an alkyl group having 1 to 20 carbon atoms), or an amino group.
- the alkyl groups that can be selected by R a , R b and R c include, for example, a methyl group, an ethyl group, a propyl group (n-propyl group, i-propyl group), a butyl group (n-butyl group, etc.).
- alkyl group may be a linear alkyl group or a branched chain alkyl group.
- Examples of the alkenyl group that can be selected as R a and R b include an ethenyl group (vinyl group), a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group and a decenyl group. , Dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, octadecenyl group and the like.
- the alkenyl group may be a linear alkyl group or a branched chain alkyl group.
- At least one hydrogen atom bonded to the carbon atom of the cation represented by any of the general formulas (b-3-i) to (b-3-ii) is an alkyl having 1 to 20 carbon atoms. It may be substituted with a group. Specific examples of the alkyl group are as described above.
- Examples of the cation represented by the general formula (b-3-i) and the cation in which at least one hydrogen atom of the cation is substituted with the alkyl group include the following formula (b-3-i-1). )-(B-3-i-11).
- Examples of the cation represented by the general formula (b-3-ii) and the cation in which at least one hydrogen atom of the cation is substituted with the alkyl group include the following formula (b-3-ii-1). )-(B-3-ii-26), and the cations represented by any of the following formulas (b-3-ii-1) to (b-3-ii-15).
- the cation is preferably one of the following formulas (b-3-ii-1) to (b-3-ii-3) and (b-3-ii-9) to (b-3-ii-10).
- the represented cation is more preferable, and the cation represented by any of the following formulas (b-3-ii-1) to (b-3-ii-3) is more preferable, and the following formula (b-3-ii-) is more preferable.
- the cation represented by 2) is even more preferable.
- a cation represented by the general formula (b-3-iii) for example, a cation represented by any of the following formulas (b-3-iii-1) to (b-3-iii-6) can be used. Can be mentioned.
- a cation represented by the general formula (b-3-iv) for example, a cation represented by any of the following formulas (b-3-iv-1) to (b-3-iv-6) can be used. Can be mentioned.
- Examples of the cation represented by any of the general formulas (b-3-v) to (b-3-viii) include cations represented by any of the following formulas.
- Examples of the anions constituting the ionic liquid (B3) include Cl- , Br- , I- , AlCl 4- , Al 2 Cl 7- , BF 4- , PF 6- , SCN- , ClO 4- , NO 3 - , CH 3 COO- , CF 3 COO- , CH 3 SO 3- , CF 3 SO 3- , C 4 F 9 SO 3- , (CF 3 SO 2 ) 2 N- , (C 2 F 5 SO 2 ) 2 N- , (C 3 F 7 SO 2 ) 2 N- , (C 4 F 9 SO 2 ) 2 N- , (CF 3 SO 2 ) 3 C- , AsF 6- , SbF 6- , NbF 6- , TaF 6- , (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 - , C 9 H 19 COO-
- the rosin-containing diol (C) used in one embodiment of the present invention may be any diol having a rosin-derived skeleton, and examples thereof include a reaction product of rosin and an epoxy compound.
- the rosin-containing diol (C) may be used alone or in combination of two or more.
- the rosin constituting the rosin-containing diol (C) means a residual resin obtained from a resin oil obtained from a Pinaceae plant as a raw material and after distilling off a volatile substance such as an essential oil. Usually, it is a mixture containing a resinic acid containing abietic acid and its relatives as main components and a small amount of neutral components.
- the resin acid include abietic acid, dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid, diavietic acid, neoavietic acid, levopipial acid, hydrogenated hydrogenated rosin, and disproportionated rosin obtained by hydrogenating these. And so on.
- Examples of the epoxy compound include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, and tripropylene glycol diglycidyl.
- Acyclic aliphatic diglycidyl ethers such as ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether; 2,2-bis (4-hydroxyphenyl) propan diglycidyl ether.
- Aromatic diglycidyl ethers such as 5,5'-tetramethyl-4,4'-dihydroxybiphenyl diglycidyl ether, 2,2'-bis (4- ( ⁇ -hydroxypropoxy) phenyl) propan diglycidyl ether or cyclic Examples thereof include aliphatic diglycidyl ethers; cyclic aliphatic cyclic oxylanes such as 3,4-epoxycyclohexylmethyl, 3,4-epoxycyclohexanecarboxylate and vinylcyclohexendioxide; and the like. These epoxy compounds may be used alone or in combination of two or more.
- the rosin-containing diol (C) used in one embodiment of the present invention is preferably a compound having two rosin-derived skeletons and two hydroxyl groups in the molecule.
- the softening point of the rosin-containing diol (C) used in one embodiment of the present invention is a voltage obtained by improving the compatibility with the components (A) and (B) (particularly, the compatibility with the component (B)).
- a pressure-sensitive adhesive composition which has high adhesiveness before application but can easily reduce the adhesiveness by applying a voltage
- it is preferably 60 ° C. or higher, more preferably 65 ° C. or higher, still more preferably 70 ° C. or higher. More preferably 75 ° C. or higher, particularly preferably 80 ° C. or higher, and more preferably 160 ° C. or lower, more preferably 150 ° C. or lower, still more preferably 140 ° C.
- the softening point means a value measured according to the ring ball method specified by JIS K5902.
- the acid value of the rosin-containing diol (C) used in one embodiment of the present invention is a voltage due to the good compatibility with the components (A) and (B) (particularly, the compatibility with the component (B)).
- it is preferably 0 to 10.0 mgKOH / g, more preferably 0 to 4.9 mgKOH /. g, more preferably 0 to 1.9 mgKOH / g, even more preferably 0 to 1.4 mgKOH / g, and particularly preferably 0 to 1.1 mgKOH / g.
- the hydroxyl value of the rosin-containing diol (C) used in one embodiment of the present invention has good compatibility with the components (A) and (B) (particularly, compatibility with the component (B)).
- it is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, still more preferable.
- the acid value and the hydroxyl value mean the values measured according to the potentiometric titration method specified by JIS K0070.
- the blending ratio of the component (C) with respect to 100 parts by mass of the total amount of the component (A) is a viewpoint of obtaining a pressure-sensitive adhesive composition that can easily reduce the adhesiveness by applying a voltage. Therefore, it is preferably 2.0 parts by mass or more, more preferably 5.0 parts by mass or more, more preferably 8.0 parts by mass or more, still more preferably 12.0 parts by mass or more, still more preferably 18.0 parts by mass.
- the above is particularly preferably 22.0 parts by mass or more, further may be 25.0 parts by mass or more, or 30.0 parts by mass or more, and is compatible with the components (A) and (B) (particularly).
- Compatibility with the component (B)) is good, and from the viewpoint of obtaining a pressure-sensitive adhesive composition having high adhesiveness before applying a voltage, it is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, and more preferably. 150 parts by mass or less, more preferably 130 parts by mass or less, still more preferably 120 parts by mass or less, particularly preferably 110 parts by mass or less, and further 100 parts by mass or less, 90 parts by mass or less, 80 parts by mass or less, 70. It may be 5 parts by mass or less, 60 parts by mass or less, or 50 parts by mass or less.
- the blending amount (content) of the component (C) is easily adhered to the total amount (100% by mass) of the active component of the pressure-sensitive adhesive composition by applying a voltage. From the viewpoint of making a pressure-sensitive adhesive composition capable of reducing the properties, it is preferably 0.2% by mass or more, more preferably 1.2% by mass or more, more preferably 3.0% by mass or more, and more preferably 5.0% by mass.
- % Or more more preferably 7.0% by mass or more, still more preferably 9.0% by mass or more, still more preferably 11.0% by mass or more, particularly preferably 16.0% by mass or more, and the components ( From the viewpoint of making a pressure-sensitive adhesive composition having good compatibility with A) and (B) (particularly, compatibility with component (B)) and high adhesiveness before applying a voltage, it is preferably 60% by mass or less. , More preferably 55% by mass or less, more preferably 50% by mass or less, still more preferably 45% by mass or less, still more preferably 40% by mass or less, particularly preferably 35% by mass or less, and further preferably 30% by mass or less. , 27% by mass or less, or 25% by mass or less.
- a component with respect to the component (B) from the viewpoint of making a pressure-sensitive adhesive composition which has high adhesiveness before voltage application but can easily reduce the adhesiveness by voltage application.
- the compounding amount ratio [(C) / (B)] of (C) is preferably 0.10 or more, more preferably 0.30 or more, more preferably 0.50 or more, still more preferably 0. 80 or more, more preferably 1.00 or more, still more preferably 1.20 or more, particularly preferably 1.50 or more, and preferably 20.0 or less, more preferably 15.0 or less, more preferably. It is 10.0 or less, more preferably 8.0 or less, still more preferably 6.0 or less, still more preferably 5.0 or less, and particularly preferably 4.0 or less.
- the pressure-sensitive adhesive composition according to one aspect of the present invention may contain a pressure-sensitive adhesive other than the component (C) as long as the effects of the present invention are not impaired.
- Such other tackifiers include rosin-based resins other than the component (C); hydrogenated rosin-based resins obtained by hydrogenating rosin-based resins other than the component (C); terpene-based resins, terpenephenol-based resins, and fragrances.
- Terpen-based resins such as group-modified terpene-based resins; Hydrogenated terpene-based resins obtained by hydrogenating these terpene-based resins; C5 based petroleum resin obtained by copolymerization and hydrogenated petroleum resin of this C5 based petroleum resin; C9 fractions such as inden, vinyltoluene, ⁇ -methylstyrene, ⁇ -methylstyrene produced by thermal decomposition of petroleum naphtha Examples thereof include a C9-based petroleum resin obtained by copolymerization and a hydrogenated petroleum resin of the C9-based petroleum resin. These other tackifiers may be used alone or in combination of two or more.
- the component (C) contained in the pressure-sensitive adhesive composition of one aspect of the present invention is obtained from the viewpoint of obtaining a pressure-sensitive adhesive composition which has high adhesiveness before voltage application and can easily reduce the adhesiveness by voltage application. ),
- the content of the tackifier other than the specific component (C) is preferably less than 10 parts by mass, more preferably less than 100 parts by mass, based on 100 parts by mass of the total amount of the component (C) contained in the pressure-sensitive adhesive composition. It is less than 5 parts by mass, more preferably less than 1 part by mass, still more preferably less than 0.1 parts by mass, and particularly preferably less than 0.01 parts by mass.
- the pressure-sensitive adhesive composition according to one aspect of the present invention is preferably a pressure-sensitive adhesive composition further containing a cross-linking agent (D).
- a cross-linking agent (D) By blending the cross-linking agent (D), it becomes easy to prepare a pressure-sensitive adhesive composition which has high adhesiveness before voltage application but can easily reduce the adhesiveness by voltage application.
- the cross-linking agent (D) may be used alone or in combination of two or more.
- cross-linking agent (D) used in one aspect of the present invention examples include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, imine-based cross-linking agents, and metal chelate-based cross-linking agents.
- isocyanate-based cross-linking agent examples include tolylene diisocyanate compounds such as 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate; Range isocyanate compounds; diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2 , 4'-diisocyanate, lysine isocyanate and the like.
- a trimer of these organic polyvalent isocyanate compounds, a terminal isocyanate urethane prepolymer obtained by reacting these organic polyvalent isocyanate compounds with a polyol compound, and the like can also be used.
- epoxy-based cross-linking agent examples include bisphenol A type epoxy compound, bisphenol F type epoxy compound, 1,3-bis (N, N-diglycidylaminomethyl) toluene, N, N, N', N'-tetraglycidyl. -4,4-diaminodiphenylmethane and the like can be mentioned.
- imine-based cross-linking agent examples include N, N'-diphenylmethane-4,4'-bis (1-aziridinecarboxyamide), trimethylolpropane-tri- ⁇ -aziridinylpropionate, and trimethylolmethane-tri.
- imine-based cross-linking agent examples include N, N'-diphenylmethane-4,4'-bis (1-aziridinecarboxyamide), trimethylolpropane-tri- ⁇ -aziridinylpropionate, and trimethylolmethane-tri.
- examples thereof include - ⁇ -aziridinyl propionate, N, N'-toluene-2,4-bis (1-aziridinecarboxyamide) triethylene melamine and the like.
- metal chelate-based cross-linking agent examples include polyvalent metal coordinating compounds such as aluminum chelate-based compounds such as trisethylacetacetate aluminum, ethylacetate acetate aluminum diisopropyrate, and trisacetylacetonate aluminum.
- the component (A) is easy to prepare with a pressure-sensitive adhesive composition which has high adhesiveness before application of voltage and can easily reduce the adhesiveness by application of voltage.
- the mixing ratio of the component (D) with respect to 100 parts by mass of the total amount of) is preferably 0.001 to 10.0 parts by mass, more preferably 0.005 to 7.0 parts by mass, and further preferably 0.010 to 5 parts. It is 0.0 part by mass, more preferably 0.050 to 2.0 parts by mass, and particularly preferably 0.100 to 1.0 part by mass.
- the pressure-sensitive adhesive composition according to one aspect of the present invention is preferably a pressure-sensitive adhesive composition further containing the compound (E) represented by the following general formula (e-1).
- e-1 the compound represented by the following general formula (e-1)
- the pressure-sensitive adhesive composition can be obtained even before the voltage is applied.
- the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition containing the compound (E) is applied to the aluminum plate before the voltage is applied. It is possible to develop high adhesive strength.
- the compound (E) may be used alone or in combination of two or more.
- R 1 is an alkylene group having 1 to 8 carbon atoms (preferably 1 to 6, more preferably 1 to 4, still more preferably 2 or 3).
- R2 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (preferably 1 to 8, more preferably 1 to 6, still more preferably 1 to 3), or a hydroxy group.
- R 3 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (preferably 1 to 8, more preferably 1 to 6, still more preferably 1 to 3).
- n is an integer of 1 or more.
- alkylene group examples include a methylene group (-CH 2- ), an ethylene group (-CH 2 CH 2- ), an ethylidene group (-CH (CH 3 )-), and a trimethylene group (-CH (CH 3)-).
- R 1 is preferably an ethylene group or a propylene group, and more preferably an ethylene group.
- the alkyl groups that can be selected as R 2 and R 3 include methyl group, ethyl group, propyl group (n-propyl group, i-propyl group), butyl group (n-butyl group, i-butyl group, s). -Butyl group, t-butyl group), pentyl group (n-pentyl group, i-pentyl group, neopentyl group), hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, Dodecyl group and the like can be mentioned.
- the compound (E) used in one embodiment of the present invention is preferably polyalkylene glycol in which R 2 in the general formula (e-1) is a hydroxy group and R 3 is a hydrogen atom, and polyethylene glycol or polypropylene glycol is more preferable.
- polyethylene glycol is even more preferred.
- the mass average molecular weight (Mw) of the compound (E) used in one embodiment of the present invention is preferably 50 to 2,000, more preferably 90 to 1,000, still more preferably 130 to 500, still more preferably 170 to. It is 300.
- the blending ratio of the component (E) with respect to 100 parts by mass of the total amount of the component (A) is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 25 parts by mass, and further preferably 1. It is 0 to 20 parts by mass, more preferably 2.5 to 16 parts by mass, and particularly preferably 4.0 to 12.0 parts by mass.
- the pressure-sensitive adhesive composition according to one aspect of the present invention may contain or contain additives other than the components (A) to (E).
- additives are appropriately selected depending on the use of the pressure-sensitive adhesive sheet using the pressure-sensitive adhesive composition, and for example, a compatibilizer, a wetting agent, a thickener, a defoaming agent, and an antioxidant. Examples thereof include agents, ultraviolet absorbers, softeners (plasticizers), fillers, rust preventives, pigments, dyes and the like.
- additives used in general pressure-sensitive adhesive compositions can be used.
- each additive may be used alone or in combination of two or more.
- the blending amount of each of these other additives is appropriately set according to the type of the additive, but is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the total amount of the component (A). It is preferably 0.05 to 40 parts by mass, more preferably 0.1 to 30 parts by mass, and even more preferably 0.2 to 20 parts by mass.
- the pressure-sensitive adhesive composition according to one aspect of the present invention may be further diluted with an organic solvent to form a solution from the viewpoint of facilitating application to a substrate or the like described later and improving workability.
- organic solvent include methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexane, n-hexane, toluene, xylene, n-propanol, isopropanol and the like.
- the organic solvent used at the time of synthesizing the component (A) may be used as it is, or one or more organic solvents other than the organic solvent used at the time of synthesizing the component (A) may be added. You may.
- the electrically peelable pressure-sensitive adhesive sheet of the present invention (hereinafter, also simply referred to as “adhesive sheet”) has a pressure-sensitive adhesive layer formed from the above-mentioned electro-removable pressure-sensitive adhesive composition of the present invention.
- the pressure-sensitive adhesive sheet according to one aspect of the present invention is not particularly limited as long as it has the pressure-sensitive adhesive layer, and may be, for example, a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer on at least one side of the base material. It may be an adhesive sheet having a structure sandwiched between two release sheets.
- FIG. 1 is a schematic cross-sectional view of the pressure-sensitive adhesive sheet showing an example of the configuration of the electrically peelable pressure-sensitive adhesive sheet according to one aspect of the present invention.
- a specific configuration of the pressure-sensitive adhesive sheet according to one aspect of the present invention for example, as shown in FIG. 1 (a), an electric peeling with a base material having a pressure-sensitive adhesive layer 3 on one surface side of the base material 2 is provided.
- the sex adhesive sheet 1a can be mentioned.
- FIG. 1 (b) there is a configuration such as an electrically peelable pressure-sensitive adhesive sheet 1b with a base material having a pressure-sensitive adhesive layer 3 and a pressure-sensitive adhesive layer 3'on both surface sides of the base material 2. It may be.
- the base material 2 and the pressure-sensitive adhesive layer 3 may be directly laminated as shown in the electrically peelable pressure-sensitive adhesive sheet 1a shown in FIG. 1 (a).
- Another layer may be provided between the material 2 and the pressure-sensitive adhesive layer 3. This also applies to the base material 2 and the pressure-sensitive adhesive layer 3 and the base material 2 and the pressure-sensitive adhesive layer 3'in the electrically peelable pressure-sensitive adhesive sheet 1b shown in FIG. 1 (b).
- the pressure-sensitive adhesive sheet has a structure such as the electrically peelable pressure-sensitive adhesive sheet 1c with a substrate in which the release sheet 4 is further laminated on the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer 3 shown in FIG. 1 (c). It may be.
- the release sheet in the electrically peelable pressure-sensitive adhesive sheet 1b, can be laminated on the pressure-sensitive adhesive surfaces of the pressure-sensitive adhesive layer 3 and the pressure-sensitive adhesive layer 3', respectively.
- the pressure-sensitive adhesive sheet according to one aspect of the present invention has a structure in which the pressure-sensitive adhesive layer 3 is sandwiched between two release sheets 4 and 4'without using a base material as shown in FIG. 1 (d). It may have a structure such as the baseless electrically peelable pressure-sensitive adhesive sheet 1d.
- the materials of the release sheets 4 and 4'of the electrically peelable adhesive sheet 1d may be the same or different, but the materials are adjusted so that the release forces of the release sheet 4 and the release sheet 4'are different. It is preferable to have.
- the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the present invention is a layer formed from the above-mentioned electro-peelable pressure-sensitive adhesive composition of the present invention, and has a property that the pressure-sensitive adhesive force can be reduced by applying a voltage.
- the thickness of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet according to one aspect of the present invention is appropriately adjusted depending on the intended use, etc., but is preferably 0.5 to 120 ⁇ m, more preferably 1 to 100 ⁇ m, and further preferably 3 to 80 ⁇ m. , More preferably 5 to 80 ⁇ m, and particularly preferably 10 to 60 ⁇ m.
- the pressure-sensitive adhesive sheet can be an electrically peelable pressure-sensitive adhesive sheet which is advantageous in terms of productivity and is also good in terms of handleability.
- the base material of the pressure-sensitive adhesive sheet according to one aspect of the present invention is preferably a conductive base material from the viewpoint of applying a voltage to the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet when it is desired to be peeled off from the adherend. That is, it is preferable that the pressure-sensitive adhesive sheet according to one aspect of the present invention has a conductive base material and a pressure-sensitive adhesive layer on at least one surface side of the conductive base material.
- 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 vapor deposition body obtained by depositing the above metal on a resin film such as polyethylene terephthalate may be used as a base material.
- a resin film such as polyethylene terephthalate
- the thickness of the base material is preferably 5 to 300 ⁇ m, more preferably 10 to 150 ⁇ m, and even more preferably 20 to 100 ⁇ m.
- the release sheet of the pressure-sensitive adhesive sheet according to one aspect of the present invention can be obtained by applying a release agent to one side or both sides of the base material for a release sheet.
- the base material for the release sheet include polyethylene such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyethylene, polypropylene, polybutene, polybutadiene, polymethylpentene, polyvinyl chloride, and vinyl chloride copolymer, polyurethane, and ethylene-.
- Resin films such as vinyl acetate copolymer, ionomer resin, ethylene (meth) acrylic acid copolymer, polystyrene, polycarbonate, fluororesin, low-density polyethylene, linear low-density polyethylene, triacetyl cellulose, high-quality paper, coated paper , Paper base material such as glassin paper, laminated paper obtained by laminating a thermoplastic resin such as polyethylene on these paper base materials and the like.
- Examples of the release agent used in one embodiment of the present invention include silicone-based resins, olefin-based resins, long-chain alkyl-based resins, alkyd-based resins, fluororesins, isoprene-based resins, butadiene-based resins, and other rubber-based elastomers. Can be mentioned.
- the thickness of the release sheet is not particularly limited, but is preferably 5 to 300 ⁇ m, more preferably 10 to 200 ⁇ m.
- a polyester film is used as the base material for the release sheet, it is preferably 10 to 100 ⁇ m.
- the method for producing the electrically peelable pressure-sensitive adhesive sheet of the present invention is not particularly limited, and the pressure-sensitive adhesive composition of one aspect of the present invention prepared by the above-mentioned method is applied onto the above-mentioned base material or the above-mentioned release sheet by a known coating method. Can be applied and manufactured. From the viewpoint of improving the coatability on the substrate or the release sheet, it is preferable that the pressure-sensitive adhesive composition according to one aspect of the present invention is diluted with an organic solvent and used in the form of a solution.
- Examples of the method for applying the pressure-sensitive adhesive composition onto a substrate or a release sheet include a spin coating method, a spray coating method, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, and a gravure coating method. And so on.
- the pressure-sensitive adhesive composition On the base material or the release sheet to form a coating film, and then perform a drying treatment.
- As the drying condition of the formed coating film it is preferable to heat it at a temperature of 80 ° C. to 150 ° C. for 30 seconds to 5 minutes (preferably 40 seconds to 3 minutes, more preferably 45 seconds to 2 minutes) and dry it. ..
- an adhesive layer can be formed on the base material or the release sheet.
- a seasoning step of holding the cross-linking agent for a certain period of time (for example, about 1 to 14 days) is performed in order to complete the cross-linking. It is preferable to go through.
- the pressure-sensitive adhesive composition used does not contain a cross-linking agent, it is not necessary to carry out the seasoning step.
- the electrically peelable pressure-sensitive adhesive sheet 1a having the pressure-sensitive adhesive layer 3 on one side of the base material 2 as shown in FIG. 1A is, for example, a solution of the above-mentioned pressure-sensitive adhesive composition on one surface of the base material 2. Can be directly applied to form the pressure-sensitive adhesive layer 3. Further, a solution of the above-mentioned pressure-sensitive adhesive composition is directly applied onto the peel-processed surface of the release sheet to form the pressure-sensitive adhesive layer 3, and then the pressure-sensitive adhesive layer 3 and the base material 2 are bonded to each other to form a release sheet. May be produced by removing.
- the solution of the above-mentioned pressure-sensitive adhesive composition is directly applied to both sides of the base material 2. It can be applied to form pressure-sensitive adhesive layers 3, 3'and produced. Further, two sheets having a pressure-sensitive adhesive layer formed by directly applying the solution of the above-mentioned pressure-sensitive adhesive composition on the peel-off surface of the release sheet are prepared, and each pressure-sensitive adhesive layer is applied to both surfaces of the base material 2. It may be produced by laminating and removing the release sheet.
- the electrically peelable pressure-sensitive adhesive sheet 1c having the pressure-sensitive adhesive layer 3 and the release sheet 4 on the base material 2 as shown in FIG. 1 (c) in this order is, for example, the electrically 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 of the above. Further, a solution of the above-mentioned pressure-sensitive adhesive composition is directly applied onto the peel-processed surface of the peel-off sheet 4 to form the pressure-sensitive adhesive layer 3, and then the pressure-sensitive adhesive layer 3 and the base material 2 are bonded together. You may.
- the electrically peelable pressure-sensitive adhesive sheet 1d having a structure in which the pressure-sensitive adhesive layer 3 is sandwiched between two release sheets 4 and 4'without using a base material as shown in FIG. 1 (d) is, for example, the release sheet 4.
- a solution of the above-mentioned pressure-sensitive adhesive composition is directly applied onto the surface to be peeled off to form a pressure-sensitive adhesive layer 3, and then another release sheet 4'is laminated on the surface of the pressure-sensitive adhesive layer 3. can do.
- the pressure-sensitive adhesive sheet according to one aspect of the present invention has a property of peeling off on the cathode side when a voltage is applied to the pressure-sensitive adhesive layer. That is, the adhesive surface of the adhesive layer connected to the cathode side is peeled off from the adherend or the base material attached to the adhesive surface.
- the electrically peelable pressure-sensitive adhesive sheet 1a according to one aspect of the present invention is to be peeled off from the adherend 11 as shown in FIG. 2A. In FIG.
- the pressure-sensitive adhesive layer 3 is sandwiched between the adherend 11 and the base material 2a, the anode terminal 51 of the voltage applying device 50 is connected to the base material 2a, and the cathode terminal 52 is adhered.
- a voltage can be applied between both surfaces of the pressure-sensitive adhesive layer 3.
- the configuration of the "base material 2a" in FIG. 2 becomes another "adhesive", and the pressure-sensitive adhesive is used.
- the layer 3 is sandwiched between two adherends, and by connecting the anode terminal 51 and the cathode terminal 52 of the voltage applying device 50 to the respective adherends, the layers 3 are formed on both sides of the pressure-sensitive adhesive layer 3. A voltage can be applied between them.
- FIG. 2A When a voltage is applied in the state shown in FIG. 2A, the adhesive surface 3a of the adhesive layer connected to the cathode side and the adhesive surface 3a are attached as shown in FIG. 2B.
- the adhesive strength is reduced between the adherend and the adherend 11, and the electrically peelable adhesive sheet 1a can be easily peeled off from the adherend.
- the applied voltage (applied voltage) is preferably 1 to 200 V, more preferably 3 to 140 V, still more preferably 6 to 120 V, and the time (applied time) for applying the voltage in the range is preferably 1 to 180. Seconds, more preferably 5 to 120 seconds, even more preferably 10 to 90 seconds.
- the adhesive strength before applying a voltage is preferably 5.0 N / 25 mm or more, more preferably 6.0 N. / 25 mm or more, more preferably 7.5 N / 25 mm or more, still more preferably 8.0 N / 25 mm or more, still more preferably 8.5 N / 25 mm or more, still more preferably 9.0 N / 25 mm or more, and particularly preferably 11. It may be 0N / 25mm or more, and may be 13.0N / 25mm or more, 15.0N / 25mm or more, 20.0N / 25mm or more, or 25.0N / 25mm or more.
- the adhesive force of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet according to the present invention is preferably 0.20 N / 25 mm or less after the pressure-sensitive adhesive layer is attached to an aluminum plate as an adherend and a voltage is applied at 10 V for 60 seconds. , More preferably 0.10 N / 25 mm or less, still more preferably 0.05 N / 25 mm or less, still more preferably 0.01 N / 25 mm or less, and particularly preferably 0.005 N / 25 mm or less.
- the adhesive strength before applying a voltage is preferably 3.0 N / 25 mm or more, more preferably 5.0 N. It is / 25 mm or more, more preferably 10.0 N / 25 mm or more, further preferably 12.0 N / 25 mm or more, still more preferably 15.0 N / 25 mm or more, and particularly preferably 20.0 N / 25 mm or more.
- the adhesive force of the adhesive sheet of one aspect of the present invention is preferably 1.10 N / 25 mm or less after the adhesive layer is attached to a stainless steel plate as an adherend and a voltage is applied at 10 V for 60 seconds.
- the electrically peelable adhesive sheet of the present invention can be used by being attached to any 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 layer, the adherend can be used as an electrode as it is. In addition, it is preferable that the adherend has conductivity.
- the conductive adherend include metals such as aluminum, tin-doped indium oxide, copper, iron, silver, platinum, and gold, and alloys of these metals (for example, stainless steel).
- the present invention also provides the usage method described in the following [i].
- [I] A method for using an electrically peelable pressure-sensitive adhesive sheet, wherein the electrically peelable pressure-sensitive adhesive sheet according to one aspect of the present invention is attached to a conductive adherend.
- a voltage is applied to the pressure-sensitive adhesive layer. Then, it can be peeled off from the adherend.
- the voltage is applied by connecting the adhesive sheet so that the adherend side from which the pressure-sensitive adhesive sheet is peeled off serves as a cathode.
- each physical property value is a value measured by the method shown below.
- Mass average molecular weight (Mw) It was measured under the following conditions using a gel permeation chromatograph device (manufactured by Tosoh Corporation, product name "HLC-8020"), and the value measured in terms of standard polystyrene was used. (Measurement condition) -Column: "TSK guard group HXL-L", “TSK gel G2500HXL”, “TSK gel G2000HXL” and “TSK gel G1000HXL” are connected in sequence (all manufactured by Tosoh Corporation).
- Acrylic Polymer 3 A copolymer having a structural unit derived from n-butyl acrylate (BA), methyl acrylate (MA), 2-hydroxyethyl acrylate (2-HEA) (constituent unit ratio: BA / MA).
- "Acrylic Polymer 4" A copolymer having a structural unit derived from n-butyl acrylate (BA), methyl acrylate (MA), 2-hydroxyethyl acrylate (2-HEA) (constituent unit ratio: BA / MA).
- Component (E): Compound> "PEG”: polyethylene glycol with Mw 200 (a compound in which R 1 is an ethylene group, R 2 is a hydroxy group, and R 3 is a hydrogen atom in the general formula (e-1)), at room temperature (25 ° C.). liquid.
- the prepared pressure-sensitive adhesive composition was placed in a transparent container, and the appearance was visually observed to evaluate the compatibility of the components constituting the pressure-sensitive adhesive composition based on the following criteria.
- ⁇ F Separation was seen.
- the pressure-sensitive adhesive compositions prepared in Examples 1 to 7 had good compatibility.
- the pressure-sensitive adhesive composition prepared in Comparative Example 1 was confirmed to be separated to the extent that it was difficult to form a pressure-sensitive adhesive layer, so that the pressure-sensitive adhesive composition was completed without producing a pressure-sensitive adhesive sheet.
- Adhesive Sheet Dry on the peeled surface of a peeling sheet (manufactured by Lintec Corporation, product name "SP-PET38131", thickness: 38 ⁇ m, polyethylene terephthalate (PET) film whose surface has been treated with silicone peeling).
- the pressure-sensitive adhesive composition prepared in the examples is applied to form a coating film so that the subsequent thickness becomes 50 ⁇ m, and the coating film is dried at 100 ° C. for 2 minutes to form a pressure-sensitive adhesive layer on a release sheet. Formed.
- the exposed surface of the formed pressure-sensitive adhesive layer is coated with a PET film with an aluminum foil (manufactured by Asia Aluminum Co., Ltd., thickness: 23 ⁇ m, PET film, adhesive layer, and aluminum foil) as a base material in this order.
- a pressure-sensitive adhesive sheet with a base material having the same structure as that of the electro-peelable pressure-sensitive adhesive sheet 1c shown in FIG.
- the value (unit: N / 25 mm) measured when the test sheet of the sample for measuring the adhesive strength was peeled off was taken as the adhesive strength of the test sheet before the voltage was applied.
- the adhesive strength was measured when the adherend was an aluminum plate and a stainless steel plate, respectively.
- the above-mentioned sample for measuring the adhesive strength is used with a voltage application device 50 (manufactured by Takasago Seisakusho Co., Ltd., product name “KH-100H”), and the anode terminal 51 is based on an aluminum foil.
- a cathode terminal 52 was connected to the adherend 11 to the material 2a, and a voltage of 10 V was applied for 60 seconds.
- the peeling speed is 300 mm / min using a tensile tester (manufactured by Orientec Co., Ltd., trade name "Tencilon”) in an environment of 23 ° C.
- the adhesive strength was measured when the adherend was an aluminum plate and a stainless steel plate, respectively. Then, from the values of the adhesive strength of the test sheet before and after the voltage was applied, the adhesive strength reduction rate was calculated by the following formula.
- the adhesive sheets produced in Examples 1 to 8 have high adhesive strength before the voltage is applied to both the aluminum plate and the stainless steel plate, but they are adhered by the voltage application. The result was a decrease in power.
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Abstract
Description
再剥離性粘着シートは、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、容易に除去し得る再剥離性が求められる。
例えば、特許文献1には、使用後には被着体から容易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。
具体的な本発明の態様としては、下記[1]~[14]のとおりである。
[1]ベースポリマー(A)、イオン性化合物(B)、及びロジン含有ジオール(C)を配合してなる、電気剥離性粘着剤組成物。
[2]成分(B)の配合割合が、成分(A)の全量100質量部に対して、1.0質量部以上である、上記[1]に記載の電気剥離性粘着剤組成物。
[3]成分(C)の配合割合が、成分(A)の全量100質量部に対して、2.0質量部以上である、上記[1]又は[2]に記載の電気剥離性粘着剤組成物。
[4]成分(B)に対する成分(C)の配合量比〔(C)/(B)〕が、質量比で、0.10~20.0である、上記[1]~[3]のいずれか一項に記載の電気剥離性粘着剤組成物。
[5]さらに架橋剤(D)を配合してなる、上記[1]~[4]のいずれか一項に記載の電気剥離性粘着剤組成物。
[6]さらに下記一般式(e-1)で表される化合物(E)を配合してなる、上記[1]~[5]のいずれか一項に記載の電気剥離性粘着剤組成物。
[7]イオン性化合物(B)が、アルカリ金属塩(B1)及びイオン液体(B3)から選ばれる1種以上を含む、上記[1]~[6]のいずれか一項に記載の電気剥離性粘着剤組成物。
[8]25℃で液体である有効成分の含有量が、前記粘着剤組成物中の有効成分の全量に対して、1~50質量%である、上記[1]~[7]のいずれか一項に記載の電気剥離性粘着剤組成物。
[9]上記[1]~[8]のいずれか一項に記載の電気剥離性粘着剤組成物から形成された粘着剤層を有する、電気剥離性粘着シート。
[10]導電性基材を有し、当該導電性基材の少なくとも一方の表面側に前記粘着剤層を有する、上記[9]に記載の電気剥離性粘着シート。
[11]前記粘着剤層に電圧を印加した際、陰極側で剥離する、上記[9]又は[10]に記載の電気剥離性粘着シート。
[12]下記要件(I)を満たす、上記[9]~[11]のいずれか一項に記載の電気剥離性粘着シート。
・要件(I):10V、60秒間での電圧印加の前後における粘着力の変化を示す、下記式(i)から算出される粘着力減少率が、50%以上である。
式(i):〔粘着力減少率(%)〕=100-〔電圧印加後の粘着力〕/〔電圧印加前の粘着力〕×100
[13]上記[9]~[12]のいずれか一項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。
[14]前記電気剥離性粘着シートを、導電性を有する被着体に貼付した後、前記粘着剤層に電圧を印加して被着体から剥離する、上記[13]に記載の電気剥離性粘着シートの使用方法。
加えて、本明細書に記載された数値範囲として、例えば「60~100」との記載は、「60以上、100以下」という範囲であることを意味する。
また、電気剥離性粘着剤組成物の「有効成分」とは、電気剥離性粘着剤組成物に含まれる成分のうち、水や有機溶媒の希釈溶媒を除いた成分を意味する。
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、ベースポリマー(A)(以下、「成分(A)」ともいう)、イオン性化合物(B)(以下、「成分(B)」ともいう)、及びロジン含有ジオール(C)(以下、「成分(C)」ともいう)を配合してなる。
なお、本明細書において、例えば、「成分(A)、成分(B)、及び成分(C)を配合してなる粘着剤組成物」とは、当該粘着剤組成物の原料として、成分(A)、成分(B)、及び成分(C)を用いている旨を意味する。そのため、例えば、成分(B)が、粘着剤組成物中にてカチオンとアニオンに電離した態様等も含まれる。
ここで、一般的な粘着剤組成物において、粘着性を向上させるために、粘着付与剤を配合する場合が多い。しかしながら、本発明者らの検討によれば、ベースポリマーとイオン性化合物とを配合してなる電気剥離性粘着剤組成物に対して、粘着付与剤を配合した場合、粘着付与剤の種類によってはイオン性化合物(特に、イオン液体)との相溶性が悪く、電圧印加前において粘着性が十分に向上しない粘着剤組成物となってしまう場合や、電圧印加しても粘着性を低下し難い粘着性組成物となってしまう場合があった。
そこで、本発明者らは、様々な検討を行ったところ、ベースポリマー及びイオン性化合物と共に、粘着付与剤である、ロジン含有ジオールを配合してなる粘着性組成物は、電圧印加前は高粘着性を有する一方で、電圧印加によって容易に粘着性を低下させ得るという特性を有するという知見を得た。本発明の粘着剤組成物は、その知見に基づいて完成されたものである。
また、本発明の一態様の粘着剤組成物は、成分(A)~(E)以外の他の添加剤を配合してなる粘着剤組成物であってもよい。
なお、液体成分の配合量が多い粘着剤組成物は、粘着性が不十分となる場合もある。しかしながら、本発明の一態様の粘着剤組成物では、液体成分との相溶性が良好であるロジン系ジオール(C)を配合しているため、粘着性をより向上させた粘着剤組成物とすることができる。
なお、上記の「液体成分」は、溶媒以外の25℃で液体の有効成分であり、具体的には、成分(B)として用いるイオン液体(B3)や、成分(E)として用いる化合物(E)等が挙げられる。
本発明の一態様で用いるベースポリマー(A)としては、粘着性を有するポリマーであればよく、例えば、アクリル系ポリマー、ウレタン系ポリマー、ゴム系ポリマー、オレフィン系ポリマー、シリコーン系ポリマー、及びこれらのポリマーに重合性官能基を有する硬化型ポリマー等が挙げられる。
これらのベースポリマー(A)は、単独で用いてもよく、2種以上を併用してもよい。
また、本発明の一態様で用いるベースポリマー(A)は、エマルション型ポリマーであってもよく、非エマルション型ポリマーであってもよい。
なお、本明細書において、質量平均分子量は、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。
上記観点から、本発明の一態様の粘着剤組成物において、成分(A)中のアクリル系ポリマー(A1)の含有割合としては、当該粘着剤組成物に含まれる成分(A)の全量(100質量%)に対して、好ましくは30~100質量%、より好ましくは50~100質量%、より好ましくは70~100質量%、更に好ましくは80~100質量%、より更に好ましくは90~100質量%、特に好ましくは95~100質量%である。
本発明の一態様で用いるアクリル系ポリマー(A1)は、単独で用いてもよく、2種以上を併用してもよい。
以下、アクリル系ポリマー(A1)を構成するモノマー及び構成単位について説明する。
モノマー(a1’)が有するアルキル基の炭素数としては、好ましくは1~30、より好ましくは1~20、より好ましくは1~16、更に好ましくは1~12、より更に好ましくは1~8、特に好ましくは4~8である。
なお、モノマー(a1’)が有するアルキル基は、直鎖アルキル基であってもよく、分岐鎖アルキル基であってもよい。
これらのモノマー(a1’)は、単独で用いてもよく、2種以上を併用してもよい。
これらの中でも、モノマー(a1’)は、炭素数4~8のアルキル基を有するアルキル(メタ)アクリレートを少なくとも含むことが好ましく、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少なくとも1種を含むことがより好ましく、ブチル(メタ)アクリレート又は2-エチルヘキシル(メタ)アクリレートを少なくとも含むことが更に好ましく、ブチル(メタ)アクリレートを少なくとも含むことがより更に好ましい。
本発明の一態様で用いるアクリル系ポリマー(A1)において、構成単位(a1-1)の含有割合は、アクリル系ポリマー(A1)が有する構成単位(a1)の全量(100質量%)に対して、好ましくは40質量%以上、より好ましくは50質量%以上、より好ましくは55質量%以上、更に好ましくは60質量%以上、より更に好ましくは65質量%以上、特に好ましくは70質量%以上であり、また、100質量%以下、99質量%以下、98質量%以下、95質量%以下、90質量%以下、85質量%以下、80質量%以下、又は76質量%としてもよい。
モノマー(a2’)としては、例えば、ヒドロキシ基含有モノマー、カルボキシ基含有モノマー、エポキシ基含有モノマー等が挙げられる。
これらのモノマー(a2’)は、単独で用いてもよく、2種以上を併用してもよい。
なお、ヒドロキシアルキル(メタ)アクリレート類が有するアルキル基の炭素数としては、好ましくは1~10、より好ましくは1~8、更に好ましくは1~6、より更に好ましくは2~4であり、当該アルキル基は、直鎖アルキル基であってもよく、分岐鎖アルキル基であってもよい。
モノマー(a1’)及び(a2’)以外のモノマー(a3’)としては、特に制限は無いが、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。
これらのモノマー(a3’)は、単独で用いてもよく、2種以上を併用してもよい。
本発明の一態様で用いるイオン性化合物(B)としては、例えば、アルカリ金属塩(B1)、有機第四級アンモニウム塩(B2)、及びイオン液体(B3)から選ばれる1種以上が挙げられる。
また、本発明の一態様で用いる成分(B)は、主成分としてアルカリ金属塩(B1)又はイオン液体(B3)を用いることが好ましい。
なお、本明細書において、上記「主成分」とは、成分(B)を構成する成分のうち、最も含有量が多い成分を意味する。
また、イオン液体(B3)のような液体成分の配合量が多い粘着剤組成物は、粘着性が不十分となる場合もある。しかしながら、本発明の一態様の粘着剤組成物では、イオン液体(B3)との相溶性が良好であるロジン系ジオール(C)を配合しているため、粘着性をより向上させると共に、電圧印加によって容易に粘着性を低下させ得る粘着剤組成物とすることができる。
本発明の一態様で用いるアルカリ金属塩(B1)としては、常温(25℃)では固体であるが、液体中でカチオン(アルカリ金属イオン)とアニオンとに電離する化合物であればよい。
具体的なアルカリ金属塩(B1)としては、例えば、MCl、MBr、MI、MAlCl4、MAl2Cl7、MBF4、MPF6、MSCN、MClO4、MNO3、CH3COOM、C9H19COOM、CF3COOM、C3F7COOM、MCH3SO3、MCF3SO3、MC4F9SO3、MC2H5OSO3、MC6H13OSO3、MC8H17OSO3、M(CF3SO2)2N、M(C2F5SO2)2N、M(C3F7SO2)2N、M(C4F9SO2)2N、M(CF3SO2)3C、MAsF6、MSbF6、MNbF6、MTaF6、M(CN)2N、M(CF3SO2)(CF3CO)N、M(CH3)2PO4、M(C2H5)2PO4、MCH3(OC2H4)2OSO3、MC6H4(CH3)SO3、M(C2F5)3PF3、CH3CH(OH)COOM、M(FSO2)2N等(ただし、Mは、アルカリ金属原子である)が挙げられる。Mは、Li、Na、又はKが好ましく、Na又はKがより好ましく、Naが更に好ましい。
これらのアルカリ金属塩(B1)は、単独で用いてもよく、2種以上を併用してもよい。
フッ素化アルキル基の中でも、アルキル基が有するすべての水素原子がフッ素原子に置換された、パーフルオロアルキル基が好ましい。パーフルオロアルキル基の炭素数の好適な範囲は、上記のフッ素化アルキル基の炭素数の好適範囲と同じである。
本発明の一態様において、RFは、フッ素原子、又はパーフルオロアルキル基であることが好ましく、フッ素原子、-CF3、-C2F5、-C3F7、又は-C4F9であることがより好ましく、フッ素原子又は-CF3であることが更に好ましい。
本発明の一態様で用いる有機第四級アンモニウム塩(B2)としては、常温(25℃)では固体であり、下記一般式(b-2)で表される化合物であればよい。
なお、有機第四級アンモニウム塩(B2)は、単独で用いてもよく、2種以上を併用してもよい。
本発明の一態様で用いるイオン液体(B3)としては、常温(25℃)で液体である溶融塩であって、有機カチオンとその対イオンであるアニオンとから構成される化合物であればよい。
イオン液体(B3)を構成する有機カチオンとしては、例えば、下記一般式(b-3-i)~(b-3-viii)のいずれかで表されるカチオンが挙げられる。これらの中でも、イオン液体(B3)を構成する有機カチオンは、下記一般式(b-3-ii)で表されるカチオンが好ましい。
また、上記式(b-3-v)~(b-3-viii)中、Rbは、それぞれ独立して、水素原子、炭素数1~20のアルキル基、-(C2H4O)n-Rcで表される基(nは1~20の整数、Rcは炭素数1~20のアルキル基)、又はアミノ基である。
当該アルキル基は、直鎖アルキル基であってもよく、分岐鎖アルキル基であってもよい。
当該アルケニル基は、直鎖アルキル基であってもよく、分岐鎖アルキル基であってもよい。
これらの中でも、本発明の一態様で用いるイオン液体(B3)を構成するアニオンとしては、(CF3SO2)2N-又は(FSO2)2N-が好ましい。
本発明の一態様で用いるロジン含有ジオール(C)としては、ロジン由来の骨格を有するジオールであればよく、例えば、ロジンとエポキシ化合物との反応物が挙げられる。
なお、ロジン含有ジオール(C)は、単独で用いてもよく、2種以上を併用してもよい。
これらのエポキシ化合物は、単独で用いてもよく、2種以上を併用してもよい。
なお、本明細書において、軟化点は、JIS K5902で規定の環球法に準拠して測定した値を意味する。
また、本発明の一態様で用いるロジン含有ジオール(C)の水酸基価は、成分(A)及び(B)との相溶性(特に、成分(B)との相溶性)を良好とすることで、電圧印加前は高粘着性を有する一方で、電圧印加によって容易に粘着性を低下させ得る粘着剤組成物とする観点から、好ましくは30mgKOH/g以上、より好ましくは50mgKOH/g以上、更に好ましくは70mgKOH/g以上、より更に好ましくは80mgKOH/g以上、特に好ましくは90mgKOH/g以上であり、また、好ましくは300mgKOH/g以下、より好ましくは250mgKOH/g以下、更に好ましくは200mgKOH/g以下、より更に好ましくは180mgKOH/g以下、特に好ましくは150mgKOH/g以下である。
なお、本明細書において、酸価及び水酸基価は、JIS K0070で規定の電位差滴定法に準拠して測定した値を意味する。
本発明の一態様の粘着剤組成物は、本発明の効果を損なわない範囲で、成分(C)以外の他の粘着付与剤を含有してもよい。
そのような他の粘着付与剤としては、成分(C)以外のロジン系樹脂;成分(C)以外の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。
これらの他の粘着付与剤は、単独で用いてもよく、2種以上を併用してもよい。
具体的な成分(C)以外の他の粘着付与剤の含有量は、前記粘着剤組成物に含まれる成分(C)の全量100質量部に対して、好ましくは10質量部未満、より好ましくは5質量部未満、更に好ましくは1質量部未満、より更に好ましくは0.1質量部未満、特に好ましくは0.01質量部未満である。
本発明の一態様の粘着剤組成物は、さらに架橋剤(D)を配合してなる粘着剤組成物であることが好ましい。架橋剤(D)を配合することで、電圧印加前は高粘着性を有する一方で、電圧印加によって容易に粘着性を低下させ得る粘着剤組成物により調製し易くなる。
なお、架橋剤(D)は、単独で用いてもよく、2種以上を併用してもよい。
なお、これらの有機多価イソシアネート化合物の三量体、並びに、これらの有機多価イソシアネート化合物とポリオール化合物とを反応して得られる末端イソシアネートウレタンプレポリマー等も使用することができる。
本発明の一態様の粘着剤組成物は、さらに下記一般式(e-1)で表される化合物(E)を配合してなる粘着剤組成物であることが好ましい。
下記一般式(e-1)で表されるようなエーテル結合を有する化合物(E)を配合することで、電圧印加によって容易に粘着性を低下させ得る粘着剤組成物により調製し易くなる。また、電圧印加前でも高粘着性を有する粘着剤組成物とすることができ、特に、化合物(E)を含む粘着剤組成物から形成した粘着剤層は、電圧印加前に、アルミニウム板に対して高粘着力を発現することができる。
なお、化合物(E)は、単独で用いてもよく、2種以上を併用してもよい。
R2は、水素原子、炭素数1~12(好ましくは1~8、より好ましくは1~6、更に好ましくは1~3)のアルキル基、又はヒドロキシ基である。
R3は、水素原子又は炭素数1~12(好ましくは1~8、より好ましくは1~6、更に好ましくは1~3)のアルキル基である。
nは1以上の整数である。
これらの中でも、R1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。
本発明の一態様の粘着剤組成物は、成分(A)~(E)以外の他の添加剤を配合又は含有してもよい。
そのような他の添加剤としては、当該粘着剤組成物を用いた粘着シートの用途に応じて適宜選択されるが、例えば、相溶化剤、濡れ剤、増粘剤、消泡剤、酸化防止剤、紫外線吸収剤、軟化剤(可塑剤)、充填剤、防錆剤、顔料、染料等が挙げられる。
これらの他の添加剤としては、一般的な粘着剤組成物に使用される添加剤を用いることができる。
また、各添加剤は、単独で用いてもよく、2種以上を併用してもよい。
有機溶媒としては、例えば、メチルエチルケトン、アセトン、酢酸エチル、テトラヒドロフラン、ジオキサン、シクロヘキサン、n-ヘキサン、トルエン、キシレン、n-プロパノール、イソプロパノール等が挙げられる。
なお、これらの有機溶媒は、成分(A)の合成時に使用された有機溶媒をそのまま用いてもよいし、成分(A)の合成時に使用された有機溶媒以外の1種以上の有機溶媒を加えてもよい。
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形成された粘着剤層を有する。
本発明の一態様の粘着シートは、当該粘着剤層を有する構成であれば特に限定されず、例えば、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。
本発明の一態様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の一方の表面側に粘着剤層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の双方の表面側に、それぞれ粘着剤層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のような構成であってもよい。
なお、本発明の一態様の粘着シートにおいて、図1(a)に示す電気剥離性粘着シート1aのように、基材2と粘着剤層3とが直接積層する構成であってもよく、基材2と粘着剤層3との間に他の層を有する構成としてもよい。これは、図1(b)に示す電気剥離性粘着シート1bにおける、基材2と粘着剤層3、及び、基材2と粘着剤層3’についても同様である。
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。
他にも、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。
本発明の粘着シートが有する粘着剤層は、上述の本発明の電気剥離性粘着剤組成物から形成された層であって、電圧印加によって粘着力が低下し得る性質を有する。
本発明の一態様の粘着シートが有する粘着剤層の厚さは、用途等に応じて適宜調整されるが、好ましくは0.5~120μm、より好ましくは1~100μm、更に好ましくは3~80μm、より更に好ましくは5~80μm、特に好ましくは10~60μmである。
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。
本発明の一態様の粘着シートが有する基材としては、被着体から剥離したい際に、粘着シートの粘着剤層に電圧印加を行う観点から、導電性基材であることが好ましい。
つまり、本発明の一態様の粘着シートは、導電性基材を有し、当該導電性基材の少なくとも一方の表面側に粘着剤層を有する構成であることが好ましい。
導電性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。
本発明の一態様の粘着シートが有する剥離シートは、剥離シート用基材の片面又は両面に剥離剤を塗布して得ることができる。
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、上記の方法により調製した本発明の一態様の粘着剤組成物を、上述の基材又は剥離シート上に公知の塗布方法により塗布して製造することができる。
なお、基材又は剥離シートに対する塗布性を良好とする観点から、本発明の一態様の粘着剤組成物は、有機溶媒で希釈して、溶液の形態として用いることが好ましい。
形成した塗布膜の乾燥条件としては、80℃~150℃の温度で、30秒~5分間(好ましくは40秒~3分間、より好ましくは45秒~2分間)加熱し、乾燥させることが好ましい。この乾燥工程を経て、基材又は剥離シート上に粘着剤層を形成することができる。
なお、粘着剤層の形成に用いた粘着剤組成物に架橋剤が配合されている場合には、架橋を完了させるために、一定期間(例えば、1日~14日程度)保持するシーズニング工程を経ることが好ましい。一方で、用いた粘着剤組成物に架橋剤が配合されていない場合には、当該シーズニングの工程を行う必要は無い。
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の一方の表面上に、上述の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、上述の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、上述の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、上述の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。
本発明の一態様の粘着シートは、前記粘着剤層に電圧を印加した際、陰極側で剥離する特性を有する。つまり、陰極側に接続した粘着剤層の粘着表面と、当該粘着表面と貼付した被着体又は基材との間で剥離する。
例えば、図2の(a)のように、本発明の一態様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の双方の表面間に電圧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の両側の面の間に電圧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粘着表面3aと、当該粘着表面3aと貼付した被着体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。
また、本発明の一態様の粘着シートが有する粘着剤層を、被着体であるアルミニウム板に貼付し、10V、60秒間で電圧印加した後における粘着力は、好ましくは0.20N/25mm以下、より好ましくは0.10N/25mm以下、更に好ましくは0.05N/25mm以下、より更に好ましくは0.01N/25mm以下、特に好ましくは0.005N/25mm以下である。
また、本発明の一態様の粘着シートが有する粘着剤層を、被着体であるステンレス板に貼付し、10V、60秒間で電圧印加した後における粘着力は、好ましくは1.10N/25mm以下、より好ましくは0.80N/25mm以下、より好ましくは0.50N/25mm以下、更に好ましくは0.30N/25mm以下、より更に好ましくは0.10N/25mm以下、特に好ましくは0.05N/25mm以下である。
・式(i):〔粘着力減少率(%)〕=100-〔電圧印加後の試験シートの粘着力〕/〔電圧印加前の試験シートの粘着力〕×100
から算出される粘着力減少率は、好ましくは50%以上、より好ましくは70%以上、更に好ましくは80%以上、より更に好ましくは90%以上、特に好ましくは95%以上である。
なお、本明細書において、電圧印加前後における粘着シートの粘着力の測定方法については、後述の実施例に記載の方法に基づくものである。
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、粘着剤層に電圧の印加を容易に行う観点から、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。
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(例えば、ステンレス)等が挙げられる。
[i]本発明の一態様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。
上記[i]に記載の使用方法において、前記電気剥離性粘着シートを、導電性を有する被着体に貼付した後、当該粘着シートを剥離したい際には、粘着剤層に電圧を印加することで、被着体から剥離することができる。
なお、粘着剤層に電圧を印加する際には、粘着シートを剥離する被着体側が陰極となるように接続して電圧を印加する。
また、各物性値については、以下に示す方法で測定した値である。
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。
(測定条件)
・カラム:「TSK guard column HXL-L」、「TSK gel G2500HXL」、「TSK gel G2000HXL」及び「TSK gel G1000HXL」を順次連結したもの(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
(2)軟化点
JIS K5902で規定の環球法に準拠して測定した。
(3)酸価、水酸基価
JIS K0070で規定の電位差滴定法に準拠して測定した。
(1)粘着剤組成物の調製
表1~2に示す種類及び配合量にて、各成分を添加し、希釈溶媒である酢酸エチルで希釈して粘着剤組成物を調製した。
表1~2に記載の実施例及び比較例の粘着剤組成物の調整に用いた各成分の詳細は以下のとおりである。
<成分(A):ベースポリマー>
・「アクリル系ポリマー1」:n-ブチルアクリレート(BA)、メチルアクリレート(MA)、2-ヒドロキシエチルアクリレート(2-HEA)に由来する構成単位を有する共重合体(構成単位比:BA/MA/2-HEA=60/20/20(質量比))、Mw=60万。
・「アクリル系ポリマー2」:n-ブチルアクリレート(BA)、4-アクリロイルモルホリン(ACMO)及び4-ヒドロキシブチルアクリレート(4HBA)に由来する構成単位を有する共重合体(構成単位比:BA/ACMO/4HBA=75/20/5(質量比))、Mw=80万。
・「アクリル系ポリマー3」:n-ブチルアクリレート(BA)、メチルアクリレート(MA)、2-ヒドロキシエチルアクリレート(2-HEA)に由来する構成単位を有する共重合体(構成単位比:BA/MA/2-HEA=75/20/5(質量比))、Mw=66万。
・「アクリル系ポリマー4」:n-ブチルアクリレート(BA)、メチルアクリレート(MA)、2-ヒドロキシエチルアクリレート(2-HEA)に由来する構成単位を有する共重合体(構成単位比:BA/MA/2-HEA=70/20/10(質量比))、Mw=80万。
<成分(B):イオン性化合物>
・「イオン液体」:第一工業製薬株式会社製、製品名「AS-210」、1-エチル-3-メチルイミダゾリウムビス(トリフルオロメタンスルホニル)イミド、常温(25℃)で液体であるイオン液体。
<成分(C):ロジン含有ジオール>
・「ロジン含有ジオール」:荒川化学工業株式会社製、製品名「パインクリスタルD-6011」、ロジン含有ジオール、軟化点=84~99℃、酸価=1mgKOH/g以下、水酸基価=110~125mgKOH/g。
<粘着付与剤>
・「テルペンフェノール」:ヤスハラケミカル株式会社製、製品名「YSポリスターT-115」、テルペンフェノール、軟化点=115℃、水酸基価=60mgKOH/g。
<成分(D):架橋剤>
・「イソシアネート系架橋剤」:東ソー株式会社製、製品名「コロネートL」、イソシアネート系架橋剤。
<成分(E):化合物>
・「PEG」:Mw=200のポリエチレングリコール(前記一般式(e-1)中のR1がエチレン基、R2がヒドロキシ基、R3が水素原子である化合物)、常温(25℃)で液体。
<相溶性の評価>
・A:分離は見られず、均一に相溶していることが確認された。
・B:分離は見られず、わずかに相溶していない箇所もあったが、再度撹拌することで、均一に相溶されることが確認された。
・F:分離が見られた。
その結果は表3~4に示すとおり、実施例1~7で調製した粘着剤組成物は、相溶性が良好であった。一方で、比較例1で調製した粘着剤組成物は、粘着剤層の形成が難しいほどに分離が確認されたため、粘着シートの作製を行わずに終了した。
剥離シート(リンテック株式会社製、製品名「SP-PET381031」、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(PET)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、実施例で調製した粘着剤組成物を塗布して塗膜を形成し、当該塗膜を100℃で2分間乾燥させて剥離シート上に粘着剤層を形成した。
その上で、形成した粘着剤層の表出している表面を、基材であるアルミニウム箔付PETフィルム(アジヤアルミ株式会社製、厚さ:23μm、PETフィルム、接着剤層、及びアルミニウム箔をこの順で積層した導電性基材)のアルミニウム箔側に貼付して、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、基材付き粘着シートを作製した。
作製した基材付き粘着シートを、25mm×75mmの大きさに裁断したものを試験シートとした。
23℃、50%RH(相対湿度)の環境下で、当該試験シートが有する剥離シートを除去し、表出した粘着剤層の粘着表面に、被着体である下記のアルミニウム板又はステンレス板に貼付した。
・アルミニウム板:パルテック株式会社製、製品名「A105OP」を75mm×70mm×1mmの大きさに割断したもの。
・ステンレス板:SUS304、360番研磨
なお、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30分間放置したものを、粘着力測定用サンプルとした。
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、粘着力測定用サンプルの試験シートを剥離した際に測定された値(単位:N/25mm)を電圧印加前の試験シートの粘着力とした。当該粘着力は、被着体がアルミニウム板及びステンレス板のそれぞれの場合について測定した。
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(株式会社高砂製作所製、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、10Vの電圧を60秒間印加した。
電圧印加後、1分間放置した後、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、粘着力測定用サンプルの試験シートを剥離した際に測定された値(単位:N/25mm)を電圧印加後の試験シートの粘着力とした。当該粘着力は、被着体がアルミニウム板及びステンレス板のそれぞれの場合について測定した。
その上で、電圧印加前後の試験シートの粘着力の値から、下記式により、粘着力減少率を算出した。
・〔粘着力減少率(%)〕=100-〔電圧印加後の試験シートの粘着力〕/〔電圧印加前の試験シートの粘着力〕×100
なお、粘着力減少率の値がマイナスとなった場合、電圧印加によって粘着力が上昇したことを示す。
2、2a 基材
3、3’ 粘着剤層
3a、3a’ 粘着表面
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)
- ベースポリマー(A)、イオン性化合物(B)、及びロジン含有ジオール(C)を配合してなる、電気剥離性粘着剤組成物。
- 成分(B)の配合割合が、成分(A)の全量100質量部に対して、1.0質量部以上である、請求項1に記載の電気剥離性粘着剤組成物。
- 成分(C)の配合割合が、成分(A)の全量100質量部に対して、2.0質量部以上である、請求項1又は2に記載の電気剥離性粘着剤組成物。
- 成分(B)に対する成分(C)の配合量比〔(C)/(B)〕が、質量比で、0.10~20.0である、請求項1~3のいずれか一項に記載の電気剥離性粘着剤組成物。
- さらに架橋剤(D)を配合してなる、請求項1~4のいずれか一項に記載の電気剥離性粘着剤組成物。
- イオン性化合物(B)が、アルカリ金属塩(B1)及びイオン液体(B3)から選ばれる1種以上を含む、請求項1~6のいずれか一項に記載の電気剥離性粘着剤組成物。
- 25℃で液体である有効成分の含有量が、前記粘着剤組成物中の有効成分の全量に対して、1~50質量%である、請求項1~7のいずれか一項に記載の電気剥離性粘着剤組成物。
- 請求項1~8のいずれか一項に記載の電気剥離性粘着剤組成物から形成された粘着剤層を有する、電気剥離性粘着シート。
- 導電性基材を有し、当該導電性基材の少なくとも一方の表面側に前記粘着剤層を有する、請求項9に記載の電気剥離性粘着シート。
- 前記粘着剤層に電圧を印加した際、陰極側で剥離する、請求項9又は10に記載の電気剥離性粘着シート。
- 下記要件(I)を満たす、請求項9~11のいずれか一項に記載の電気剥離性粘着シート。
・要件(I):10V、60秒間での電圧印加の前後における粘着力の変化を示す、下記式(i)から算出される粘着力減少率が、50%以上である。
式(i):〔粘着力減少率(%)〕=100-〔電圧印加後の粘着力〕/〔電圧印加前の粘着力〕×100 - 請求項9~12のいずれか一項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。
- 前記電気剥離性粘着シートを、導電性を有する被着体に貼付した後、前記粘着剤層に電圧を印加して被着体から剥離する、請求項13に記載の電気剥離性粘着シートの使用方法。
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WO2023054480A1 (ja) * | 2021-09-30 | 2023-04-06 | 日東電工株式会社 | 粘着剤組成物、粘着シート、及び接合体 |
WO2023054484A1 (ja) * | 2021-09-30 | 2023-04-06 | 日東電工株式会社 | 粘着剤組成物、粘着シート、及び接合体 |
WO2023054478A1 (ja) * | 2021-09-30 | 2023-04-06 | 日東電工株式会社 | 粘着剤組成物、粘着シート、及び接合体 |
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- 2021-09-27 CN CN202180065203.7A patent/CN116194542A/zh active Pending
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