WO2023054478A1 - 粘着剤組成物、粘着シート、及び接合体 - Google Patents
粘着剤組成物、粘着シート、及び接合体 Download PDFInfo
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- WO2023054478A1 WO2023054478A1 PCT/JP2022/036195 JP2022036195W WO2023054478A1 WO 2023054478 A1 WO2023054478 A1 WO 2023054478A1 JP 2022036195 W JP2022036195 W JP 2022036195W WO 2023054478 A1 WO2023054478 A1 WO 2023054478A1
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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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
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
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- 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
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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- 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
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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
- C09J2433/00—Presence of (meth)acrylic polymer
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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
- C09J2467/00—Presence of polyester
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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
- C09J2475/00—Presence of polyurethane
Definitions
- the present invention relates to a pressure-sensitive adhesive composition, a pressure-sensitive adhesive sheet including a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition, and a bonded body of the pressure-sensitive adhesive sheet and an adherend.
- an ionic liquid composed of cations and anions is used as a component forming the pressure-sensitive adhesive composition, and a pressure-sensitive adhesive sheet that is released by applying a voltage to the pressure-sensitive adhesive layer.
- Patent Document 1 Electropeelable pressure-sensitive adhesive sheet
- the electropeelable pressure-sensitive adhesive sheet of Patent Document 1 when a voltage is applied, the cations of the ionic liquid migrate on the cathode side to cause reduction, and the anions of the ionic liquid migrate on the anode side to cause oxidation, resulting in adhesion of the adhesive interface. It is considered that the force becomes weaker and peeling becomes easier.
- Patent Document 2 studies, for example, a pressure-sensitive adhesive composition whose adhesive force is sufficiently reduced by voltage application even in a low-humidity environment such as in winter.
- the electro-peelable pressure-sensitive adhesive sheet can firmly bond the members when no voltage is applied, and can be peeled off with a small force when voltage is applied. Therefore, in the electrically peelable pressure-sensitive adhesive sheet, it is preferable that the rate of decrease in adhesive force due to voltage application is large.
- the rate of decrease in adhesive force due to voltage application may decrease over time.
- the inventors have found a new problem that the rate of decrease in adhesive force due to voltage application becomes small after storage in an environment of high humidity and high temperature such as in summer.
- An object of the present invention is to provide a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition.
- the reason why the rate of decrease in adhesive force due to voltage application after storage in a high-temperature and high-humidity environment is small is that the viscosity of the pressure-sensitive adhesive layer increases in a high-temperature and high-humidity environment, and ion It was found that this is caused by the fact that cations and anions in the liquid become difficult to move.
- the following findings were obtained.
- Tg glass transition temperature
- the second polymer contains an organic polymer compound, and the content of the organic polymer compound in the second polymer is 1 to 50 parts by mass with respect to 100 parts by mass of the first polymer. , the pressure-sensitive adhesive composition according to [1].
- the cation of the ionic liquid includes at least one selected from the group consisting of nitrogen-containing onium cations, sulfur-containing onium cations, and phosphorus-containing onium cations.
- the content of the ionic liquid is 0.5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the first polymer.
- a pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to any one of [1] to [12].
- [14] [13] comprising the pressure-sensitive adhesive sheet and a conductive material, A joined body in which the pressure-sensitive adhesive layer is adhered to the conductive material.
- the adhesive strength of the pressure-sensitive adhesive composition of the present invention is sufficiently reduced by voltage application even after storage in a high-temperature and high-humidity environment.
- FIG. 1 is a cross-sectional view showing an example of the adhesive sheet of the present invention.
- FIG. 2 is a cross-sectional view showing an example of the laminated structure of the pressure-sensitive adhesive sheet of the present invention.
- FIG. 3 is a cross-sectional view showing another example of the laminated structure of the pressure-sensitive adhesive sheet of the present invention.
- FIG. 4 is a cross-sectional view showing an overview of the method of the 180° peel test in Examples.
- a pressure-sensitive adhesive composition according to an embodiment of the present invention is a pressure-sensitive adhesive composition containing a first polymer and an ionic liquid, comprising the first polymer as a base polymer, and having a Tg of It contains a second polymer that is between 40 and 180°C.
- the pressure-sensitive adhesive composition according to embodiments of the present invention is preferably for electro-peeling. The adhesive composition will be described below.
- the first polymer may be referred to as "base polymer".
- the base polymer in the pressure-sensitive adhesive composition according to this embodiment refers to the main component in the polymer contained in the pressure-sensitive adhesive composition.
- the term “main component” refers to a component contained in an amount exceeding 50% by mass, unless otherwise specified.
- the adhesive strength when no voltage is applied is sometimes referred to as "initial adhesive strength”.
- the composition which consists of components other than an ionic liquid among the components contained in an adhesive composition may be called “ionic liquid non-containing adhesive composition.”
- the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition not containing the ionic liquid may be referred to as “the pressure-sensitive adhesive layer not containing the ionic liquid”.
- a pressure-sensitive adhesive composition according to an embodiment of the present invention contains a first polymer as a base polymer.
- the base polymer is not particularly limited as long as it is a general organic polymer compound, and is, for example, a polymer or partial polymer of monomers.
- the monomer may be a single monomer or a mixture of two or more monomers.
- a partially polymerized product means a polymerized product in which at least a part of a monomer or a monomer mixture is partially polymerized.
- the first polymer in the embodiment of the present invention is generally used as an adhesive and is not particularly limited as long as it has adhesiveness.
- examples include acrylic polymers, rubber polymers, vinyl alkyl ether polymers, silicone polymer, polyester-based polymer, polyamide-based polymer, urethane-based polymer, fluorine-based polymer, epoxy-based polymer, and the like.
- the above polymers can be used alone or in combination of two or more.
- the first polymer in the embodiment of the present invention is at least one selected from the group consisting of polyester-based polymers, urethane-based polymers, and acrylic polymers having a carboxyl group, an alkoxy group, a hydroxyl group and/or an amide bond. is preferably included. Since polyester-based polymers and urethane-based polymers have terminal hydroxyl groups that are easily polarized, acrylic polymers having carboxyl groups, alkoxy groups, hydroxyl groups and/or amide bonds have carboxyl groups, alkoxy groups, hydroxyl groups and / Or since the amide bond is easily polarized, by using these polymers, it is possible to obtain a pressure-sensitive adhesive layer that exhibits excellent adhesive strength when no voltage is applied.
- the total content of the base polymer in all polymers contained in the pressure-sensitive adhesive composition according to the embodiment of the present invention is preferably 60% by mass or more, more preferably 80% by mass or more.
- the polymer in the embodiment of the present invention is preferably an acrylic polymer, and has a carboxyl group, an alkoxy group, a hydroxyl group, and/or an amide group. More preferably, it is an acrylic polymer having a bond. That is, the pressure-sensitive adhesive composition according to the embodiment of the present invention is preferably an acrylic pressure-sensitive adhesive composition containing an acrylic polymer as a base polymer.
- the acrylic polymer preferably contains a monomer unit derived from a (meth)acrylic acid alkyl ester (formula (1) below) having an alkyl group having 1 to 14 carbon atoms.
- Such monomer units are suitable for obtaining high initial adhesive strength.
- the number of carbon atoms in the alkyl group R b in the following formula (1) is preferably small, particularly 8 or less. Preferably, it is 4 or less.
- CH2 C( Ra ) COORb (1) [R a in formula (1) is a hydrogen atom or a methyl group, and R b is an alkyl group having 1 to 14 carbon atoms]
- Examples of (meth)acrylic acid alkyl esters having an alkyl group having 1 to 14 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl ( meth)acrylate, sec-butyl (meth)acrylate, 1,3-dimethylbutyl acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, heptyl (meth)acrylate ) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate,
- n-butyl acrylate, 2-ethylhexyl acrylate and isononyl acrylate are preferred.
- the (meth)acrylic acid alkyl esters having an alkyl group of 1 to 14 carbon atoms can be used alone or in combination of two or more.
- the ratio of the (meth)acrylic acid alkyl ester having an alkyl group having 1 to 14 carbon atoms to the total monomer components (100% by mass) constituting the acrylic polymer is not particularly limited, but is preferably 70% by mass or more, more preferably. is 80% by mass or more, more preferably 85% by mass or more. When the proportion of the acrylic polymer is 70% by mass or more, it becomes easier to obtain a large initial adhesive strength.
- the acrylic polymer in addition to the monomer unit derived from (meth)acrylic acid alkyl ester having an alkyl group having 1 to 14 carbon atoms, for the purpose of improving cohesion, heat resistance, crosslinkability, etc. It preferably contains a monomer unit derived from a copolymerizable polar group-containing monomer.
- a monomer unit can provide cross-linking points and is suitable for obtaining a large initial adhesive strength.
- Polar group-containing monomers include, for example, carboxyl group-containing monomers, alkoxy group-containing monomers, hydroxyl group-containing monomers, cyano group-containing monomers, vinyl group-containing monomers, aromatic vinyl monomers, amide group-containing monomers, imide group-containing monomers, amino Examples include group-containing monomers, epoxy group-containing monomers, vinyl ether monomers, N-acryloylmorpholine, sulfo group-containing monomers, phosphoric acid group-containing monomers, and acid anhydride group-containing monomers.
- carboxyl group-containing monomers alkoxy group-containing monomers, hydroxyl group-containing monomers, and amide group-containing monomers are preferable, and carboxyl group-containing monomers are particularly preferable, from the viewpoint of excellent cohesiveness.
- a carboxyl group-containing monomer is particularly suitable for obtaining a large initial adhesive strength.
- Polar group-containing monomers can be used alone or in combination of two or more.
- Carboxyl group-containing monomers include, for example, acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid. Acrylic acid is particularly preferred. Carboxyl group-containing monomers can be used alone or in combination of two or more.
- alkoxy group-containing monomers examples include methoxy group-containing monomers and ethoxy group-containing monomers.
- methoxy group-containing monomers include 2-methoxyethyl acrylate.
- hydroxyl group-containing monomers examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl ( meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl (meth)acrylate, N-methylol (meth)acrylamide, vinyl alcohol, allyl alcohol , 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and diethylene glycol monovinyl ether. 2-Hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate are particularly preferred.
- a hydroxyl group-containing monomer can be used individually or in combination of 2 or more types.
- amide group-containing monomers examples include acrylamide, methacrylamide, N-vinylpyrrolidone, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N,N-diethylacrylamide, N,N-diethylmethacrylamide, N , N′-methylenebisacrylamide, N,N-dimethylaminopropylacrylamide, N,N-dimethylaminopropylmethacrylamide, and diacetoneacrylamide.
- Amido group-containing monomers can be used alone or in combination of two or more.
- cyano group-containing monomers examples include acrylonitrile and methacrylonitrile.
- vinyl group-containing monomers examples include vinyl esters such as vinyl acetate, vinyl propionate, and vinyl laurate, and vinyl acetate is particularly preferred.
- aromatic vinyl monomers examples include styrene, chlorostyrene, chloromethylstyrene, ⁇ -methylstyrene, and other substituted styrenes.
- imide group-containing monomers examples include cyclohexylmaleimide, isopropylmaleimide, N-cyclohexylmaleimide, and itaconimide.
- amino group-containing monomers examples include aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, and N,N-dimethylaminopropyl (meth)acrylate.
- epoxy group-containing monomers examples include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, and allyl glycidyl ether.
- vinyl ether monomers examples include methyl vinyl ether, ethyl vinyl ether, and isobutyl vinyl ether.
- the ratio of the polar group-containing monomer to the total monomer components (100% by mass) constituting the acrylic polymer is preferably 0.1% by mass or more and 35% by mass or less.
- the upper limit of the ratio of the polar group-containing monomer is more preferably 25% by mass, more preferably 20% by mass, and the lower limit is more preferably 0.5% by mass, further preferably 1% by mass. , particularly preferably 2% by weight.
- the ratio of the polar group-containing monomer is 35% by mass or less, it becomes easier to prevent the pressure-sensitive adhesive layer from excessively adhering to the adherend and causing heavy release.
- the amount is 2% by mass or more and 20% by mass or less, it becomes easy to achieve both the releasability from the adherend and the adhesion between the pressure-sensitive adhesive layer and other layers.
- a polyfunctional monomer may be included in order to introduce a crosslinked structure into the acrylic polymer and facilitate the acquisition of the necessary cohesive force.
- polyfunctional monomers examples include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di( meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, divinylbenzene, and N,N'-methylenebisacrylamide.
- a polyfunctional monomer can be used individually or in combination of 2 or more types.
- the content of the polyfunctional monomer with respect to the total monomer components (100% by mass) constituting the acrylic polymer is preferably 0.1% by mass or more and 15% by mass or less.
- the upper limit of the polyfunctional monomer content is more preferably 10% by mass, and the lower limit is more preferably 3% by mass.
- the content of the polyfunctional monomer is 0.1% by mass or more, the flexibility and adhesiveness of the pressure-sensitive adhesive layer are likely to be improved, which is preferable.
- the content of the polyfunctional monomer is 15% by mass or less, the cohesive force does not become too high, making it easier to obtain appropriate adhesiveness.
- Polyester-based polymers are typically composed of polyvalent carboxylic acids such as dicarboxylic acids and derivatives thereof (hereinafter also referred to as “polyvalent carboxylic acid monomers”), and polyhydric alcohols such as diols and derivatives thereof (hereinafter referred to as “polyhydric alcohol monomers”). ”) is a polymer having a condensed structure.
- polyvalent carboxylic acid monomers include, but are not limited to, adipic acid, azelaic acid, dimer acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, dodecenylsuccinic anhydride, fumaric acid, succinic acid, dodecanedioic acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, etc., maleic acid, maleic anhydride, itaconic acid, citraconic acid , and derivatives thereof and the like can be used.
- Polyvalent carboxylic acid monomers can be used alone or in combination of two or more.
- polyhydric alcohol monomers include, but are not limited to, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1, 3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 2,2 ,4-trimethyl-1,5-pentanediol, 2-ethyl-2-butylpropanediol, 1,9-nonanediol, 2-methyloctanediol, 1,10-decanediol, derivatives thereof, etc. can be done.
- a polyhydric alcohol monomer can be used individually or in combination of 2 or more types.
- the first polymer according to the embodiment of the present invention may contain an ionic polymer.
- An ionic polymer is a polymer with ionic functional groups. Since the first polymer contains an ionic polymer, the electrical exfoliation property is improved.
- the content of the ionic polymer is preferably 0.05 parts by mass or more and 2 parts by mass or less with respect to 100 parts by mass of the first polymer.
- the first polymer can be obtained by (co)polymerizing monomer components.
- the polymerization method is not particularly limited, but includes solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, photopolymerization (active energy ray polymerization), and the like.
- the solution polymerization method is preferable from the viewpoint of cost and productivity.
- the first polymer may be a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer, or the like.
- the solution polymerization method is not particularly limited, but examples include a method of dissolving a monomer component, a polymerization initiator, etc. in a solvent and heating and polymerizing to obtain a polymer solution containing the first polymer.
- solvents can be used as the solvent used in the solution polymerization method.
- solvents include aromatic hydrocarbons such as toluene, benzene, and xylene; esters such as ethyl acetate and n-butyl acetate; Alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; organic solvents such as ketones such as methyl ethyl ketone and methyl isobutyl ketone;
- a solvent can be used individually or in combination of 2 or more types.
- the amount of solvent used is not particularly limited, but is preferably 10 parts by mass or more and 1000 parts by mass or less with respect to all the monomer components (100 parts by mass) constituting the first polymer.
- the upper limit of the amount of solvent used is more preferably 500 parts by mass, and the lower limit is more preferably 50 parts by mass.
- the polymerization initiator used in the solution polymerization method is not particularly limited, but includes peroxide-based polymerization initiators, azo-based polymerization initiators, and the like.
- Peroxide-based polymerization initiators are not particularly limited, but include peroxycarbonates, ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, and peroxyesters.
- the azo polymerization initiator is not particularly limited, but 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis(2,4- dimethylvaleronitrile), 2,2′-azobis(2-methylpropionate)dimethyl, 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1′-azobis(cyclohexane-1 -carbonitrile), 2,2′-azobis(2,4,4-trimethylpentane), 4,4′-azobis-4-cyanovaleric acid, 2,2′-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis(2-methylpropionamidine) disulfate, 2,2'-azobis (N,N'-dimethyleneisobutylamidine) hydro
- the amount of the polymerization initiator used is not particularly limited, but is preferably 0.01 parts by mass or more and 5 parts by mass or less with respect to all the monomer components (100 parts by mass) constituting the first polymer.
- the upper limit of the amount of the polymerization initiator used is more preferably 3 parts by mass, and the lower limit is more preferably 0.05 parts by mass.
- the heating temperature for polymerization by heating is not particularly limited, but is, for example, 50°C or higher and 80°C or lower.
- the heating time is not particularly limited, but is, for example, 1 hour or more and 24 hours or less.
- the weight average molecular weight of the first polymer is not particularly limited, it is preferably 100,000 or more and 5,000,000 or less.
- the upper limit of the weight average molecular weight is more preferably 4,000,000, more preferably 3,000,000, and the lower limit is more preferably 200,000, still more preferably 300,000.
- the weight-average molecular weight is 100,000 or more, the cohesive force becomes small, and it is possible to effectively suppress the problem that adhesive residue is left on the surface of the adherend after the pressure-sensitive adhesive layer is peeled off.
- the weight-average molecular weight is 5,000,000 or less, it is possible to effectively suppress the problem that the wettability of the surface of the adherend after the pressure-sensitive adhesive layer is peeled off becomes insufficient.
- the weight average molecular weight is obtained by measuring by a gel permeation chromatograph (GPC) method. ) can be used to measure under the following conditions, and can be calculated from standard polystyrene conversion values.
- GPC gel permeation chromatograph
- the glass transition temperature (Tg) of the first polymer is not particularly limited, but when it is 0° C. or lower, it is preferable because a decrease in initial adhesive strength can be suppressed, more preferably ⁇ 10° C. or lower, and even more preferably. -20°C or less.
- a temperature of ⁇ 40° C. or less is particularly preferable, and most preferably ⁇ 50° C. or less, because the rate of decrease in adhesive strength due to voltage application is particularly large.
- the composition of the monomer component is such that the glass transition temperature (hereinafter also referred to as "glass transition temperature of the polymer") determined by the Fox formula based on the composition of the monomer component is ⁇ 75° C. or higher and ⁇ 10° C. or lower.
- the glass transition temperature (Tg) of the polymer for example, an acrylic polymer, typically an acrylic polymer
- Tg glass transition temperature
- the polymer is suitably ⁇ 15° C. or less, and ⁇ 20° C. or less. It is preferably -25°C or lower, more preferably -30°C or lower, and may be -40°C or lower (for example, -55°C or lower).
- Tg is the glass transition temperature of the copolymer (unit: K)
- Wi is the weight fraction of the monomer i in the copolymer (copolymerization ratio based on weight)
- Tgi is the content of the monomer i. It represents the glass transition temperature (unit: K) of a homopolymer.
- the glass transition temperature of the homopolymer used for calculating the Tg the value described in the known materials shall be used.
- the monomers listed below the following values are used as the glass transition temperatures of the homopolymers of the monomers.
- test sample sheet homopolymer
- This test sample is punched out into a disk shape with a diameter of 7.9 mm, sandwiched between parallel plates, and subjected to shear strain at a frequency of 1 Hz using a viscoelasticity tester (ARES, manufactured by Rheometrics Co., Ltd.) while applying a temperature range of -70 to 150 ° C. , the viscoelasticity is measured in shear mode at a heating rate of 5° C./min, and the peak top temperature of tan ⁇ is defined as the Tg of the homopolymer.
- ARES viscoelasticity tester
- the content of the first polymer in the adhesive composition according to the embodiment of the present invention is preferably 50% by mass or more and 99.9% by mass or less with respect to the total amount of the adhesive composition (100% by mass), and the upper limit is is more preferably 99.5% by mass, still more preferably 99% by mass, and the lower limit is more preferably 60% by mass, still more preferably 70% by mass.
- the pressure-sensitive adhesive composition according to the embodiment of the present invention further contains a second polymer having a glass transition temperature (Tg) of 40-180°C.
- the second polymer should have a glass transition temperature (Tg) of 40 to 180°C.
- Tg glass transition temperature
- any polymer may be used as long as it is different from the first polymer.
- the pressure-sensitive adhesive composition according to the embodiment of the present invention contains a second polymer having a glass transition temperature (Tg) of 40 to 180 ° C., so that the effect of improving the elastic modulus is obtained, and it is excellent when no voltage is applied. It is possible to form a pressure-sensitive adhesive layer having excellent wet heat stability, which exhibits a high adhesive strength, and whose adhesive strength is sufficiently lowered by voltage application even after storage in a high-temperature and high-humidity environment.
- the glass transition temperature (Tg) of the second polymer is preferably 40°C or higher, more preferably 50°C or higher, even more preferably 60°C or higher, further preferably 70°C, from the viewpoint of adhesive properties. It is particularly preferable that it is above. In addition, from the viewpoint of adhesive properties, the temperature must be 180° C. or lower, more preferably 160° C. or lower, even more preferably 140° C. or lower, even more preferably 120° C. or lower, and 100° C. or lower. It is particularly preferred to have The glass transition temperature (Tg) of the second polymer can be calculated in the same manner as the glass transition temperature (Tg) of the first polymer. Further, the glass transition temperature (Tg) of the second polymer can be adjusted by adjusting the type and blending amount of the monomers constituting the second polymer.
- the second polymer is not particularly limited as long as the Tg satisfies the above specific range, and general organic polymer compounds can be used. things are mentioned.
- the above monomer may be a single monomer or a mixture of two or more monomers.
- the partially polymerized product means a polymerized product in which one or two or more components of a monomer or a monomer mixture are partially polymerized.
- the second polymer may be one having adhesiveness, or may be a tackifying resin.
- the second polymer preferably contains a tackifying resin, and more preferably further contains a tackifying resin in addition to the organic polymer compound.
- a tackifying resin in the second polymer, it is possible to form a pressure-sensitive adhesive layer in which the rate of decrease in adhesive force due to voltage application after storage in a high-temperature, high-humidity environment is further improved, which is preferable.
- organic polymer compounds contained in the second polymer include acrylic polymers, rubber polymers, vinyl alkyl ether polymers, silicone polymers, polyester polymers, polyamide polymers, urethane polymers, and fluorine polymers.
- the organic polymer compound in the second polymer refers to a compound that is a polymer or partial polymer of monomers, and refers to a component different from the tackifier resin and the first polymer.
- tackifying resins include rosin-based tackifying resins such as rosin resins, rosin phenol resins, and rosin ester resins; hydrogenated rosin-based tackifying resins obtained by hydrogenating these rosin-based resins; terpene-based resins and terpene phenols.
- terpene-based tackifying resins such as terpene-based resins and aromatic modified terpene-based resins; hydrogenated terpene-based tackifying resins obtained by hydrogenating these terpene-based resins; - C5 petroleum resins obtained by copolymerizing C5 fractions such as pentadiene and hydrogenated petroleum tackifying resins of these C5 petroleum resins; C9 petroleum resin obtained by copolymerizing C9 fraction such as ⁇ -methylstyrene and hydrogenated petroleum tackifying resin of this C9 petroleum resin; phenolic tackifying resin; hydrocarbon tackifying resin, etc. .
- phenol-based tackifying resins include terpene phenol resins, hydrogenated terpene phenol resins, alkylphenol resins, rosin phenol resins, and xylene formaldehyde resins.
- Terpene phenol resin refers to a polymer containing a terpene residue and a phenol residue, a copolymer of terpenes and a phenol compound (terpene-phenol copolymer resin), and a homopolymer or copolymer of terpenes is a concept that includes both phenol-modified (phenol-modified terpene resin).
- terpenes constituting such a terpene phenol resin include monoterpenes such as ⁇ -pinene, ⁇ -pinene, and limonene (including d-, l- and d/l (dipentene)). mentioned.
- a hydrogenated terpene phenol resin refers to a hydrogenated terpene phenol resin having a structure obtained by hydrogenating such a terpene phenol resin, and is sometimes referred to as a hydrogenated terpene phenol resin.
- Alkylphenol resins are resins obtained from alkylphenols and formaldehyde (oily phenolic resins). Alkylphenol resins include, for example, novolak type and resol type.
- rosin phenol resins include phenol-modified rosins and various rosin derivatives (including rosin esters, unsaturated fatty acid-modified rosins, and unsaturated fatty acid-modified rosin esters). Rosin phenol resins include, for example, rosin phenol resins obtained by adding phenol to rosins or various rosin derivatives with an acid catalyst and thermally polymerizing them.
- Terpene-based tackifying resins include, for example, terpene resins, terpene phenol resins, styrene-modified terpene resins, aromatic modified terpene resins, and hydrogenated terpene resins.
- Terpene resins include polymers of terpenes (typically monoterpenes) such as ⁇ -pinene, ⁇ -pinene, d-limonene, l-limonene and dipentene.
- terpene homopolymer includes, for example, ⁇ -pinene polymer, ⁇ -pinene polymer, and dipentene polymer.
- rosin-based tackifying resins includes both rosins and rosin derivative resins.
- rosins include unmodified rosins (fresh rosins) such as gum rosin, wood rosin and tall oil rosin; homogenized rosin, polymerized rosin, other chemically modified rosins, etc.);
- rosin derivative resins include rosin esters such as unmodified rosin esters that are esters of unmodified rosin and alcohols, and modified rosin esters that are esters of denatured rosin and alcohols; Unsaturated fatty acid-modified rosins; rosin esters modified with unsaturated fatty acids; rosins and rosin derivative resins (rosin esters, unsaturated fatty acid-modified rosins, unsaturated fatty acid-modified rosin alcohols obtained by reducing the carboxyl groups of esters, etc.); rosin phenols; metal salts thereof;
- rosin esters include methyl esters, triethylene glycol esters, glycerin esters, pentaerythritol esters, and maleic esters of unmodified rosins or modified rosins (e.g., hydrogenated rosins, disproportionated rosins, polymerized rosins, etc.). is
- hydrocarbon-based tackifying resins examples include aliphatic hydrocarbon resins, aromatic hydrocarbon resins (e.g., styrene-based resins, xylene-based resins, etc.), aliphatic cyclic hydrocarbon resins, aliphatic/aromatic petroleum resins (styrene-olefin copolymers, etc.), aliphatic/alicyclic petroleum resins, hydrogenated hydrocarbon resins, coumarone resins, and coumarone-indene resins.
- aromatic hydrocarbon resins e.g., styrene-based resins, xylene-based resins, etc.
- aliphatic cyclic hydrocarbon resins aliphatic/aromatic petroleum resins (styrene-olefin copolymers, etc.)
- aliphatic/alicyclic petroleum resins hydrogenated hydrocarbon resins
- coumarone resins coumarone-indene resins
- terpene-based tackifying resins or rosin-based tackifying resins are preferable.
- the tackifying resin may be used alone or in combination of two or more.
- the softening point of the tackifier resin is preferably 100°C or higher, more preferably 110°C or higher, even more preferably 120°C or higher, and most preferably 130°C or higher.
- the upper limit of the softening point of the tackifying resin is preferably 200°C or lower, more preferably 180°C or lower, even more preferably 160°C or lower, and most preferably 140°C or lower. preferable.
- the content of the tackifying resin in the pressure-sensitive adhesive composition according to the embodiment of the present invention is preferably 1 to 50 parts by mass, more preferably 1 to 30 parts by mass, with respect to 100 parts by mass of the first polymer. is more preferably 1 to 20 parts by mass, and most preferably 1 to 15 parts by mass.
- acrylic polymers and polyester polymers are preferably used from the viewpoint of adhesive properties.
- the acrylic polymer used as the organic polymer compound in the second polymer may be a commercially available one, or may be obtained by polymerizing an acrylic monomer component.
- acrylic polymers used as the organic polymer compound in the second polymer include ARUFON UH2170 and UC3000 (manufactured by Toagosei Co., Ltd.).
- Any acrylic monomer can be used as the acrylic monomer component, and examples thereof include hydroxyl group-containing acrylic monomers and polymerizable acrylic monomers.
- the acrylic monomer component that constitutes the organic polymer compound in the second polymer preferably contains a polymerizable acrylic monomer.
- the polymerizable acrylic monomer contained in the acrylic monomer component may be of only one type, or may be of two or more types.
- polymerizable monomers examples include acrylic acid (AA), N-vinyl-2-pyrrolidone, dicyclopentanyl methacrylate, methyl acrylate (MA), methyl methacrylate (MMA), cyclohexyl acrylate, cyclohexyl methacrylate (CHMA), iso Bonyl acrylate (IBXMA), ⁇ -carboxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, acrylonitrile, acrylamide, dimethylacrylamide, isopropylacrylamide, hydroxyethylacrylamide, hydroxymethylacrylamide, hydroxybutylacrylamide, acryloylmorpholine (ACMO) , 1-vinylimidazole and the like, and from the viewpoint that the effects of the present invention can be more expressed, acrylic acid, methyl acrylate (MA), methyl methacrylate (MMA), cyclohexyl acrylate, cyclohexyl methacrylate (CHMA
- the content of the polymerizable monomer in the acrylic monomer component is preferably 1% by mass or more, more preferably 10% by mass or more, and even more preferably 30% by mass or more, from the viewpoint of adhesive properties. , more preferably 50% by mass or more, and particularly preferably 80% by mass or more.
- hydroxyl group-containing monomers include 2-hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl acrylate (4HBA), 4-hydroxybutyl methacrylate, and 6-hydroxyhexyl.
- Hydroxyalkyl (meth)acrylates such as (meth)acrylates, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate; (4-hydroxymethylcyclohexyl)methyl hydroxyalkylcycloalkane (meth)acrylates such as (meth)acrylates; other hydroxyl group-containing monomers such as hydroxyethyl (meth)acrylamide, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether; mentioned.
- the hydroxyl group-containing monomer is preferably a hydroxyalkyl (meth)acrylate from the viewpoint of ease of handling and the ability to further express the effects of the present invention. More preferably meth)acrylate, specifically preferably at least one selected from 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate, more preferably 4-hydroxybutyl acrylate (4HBA).
- the content of the hydroxyl group-containing monomer in the acrylic monomer component is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, from the viewpoint of adhesive properties. , more preferably 10% by mass or more, and particularly preferably 15% by mass or more. From the viewpoint of adhesion properties, the content is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less.
- the organic polymer compound in the second polymer according to the embodiment of the invention can be produced by any appropriate polymerization within the range that does not impair the effects of the invention.
- Methods for polymerizing the organic polymer compound in the second polymer according to the embodiment of the present invention include, for example, a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, and a polymerization method by active energy ray irradiation (active energy ray polymerization method).
- active energy ray polymerization method active energy ray polymerization method
- bulk polymerization method and solution polymerization method are preferred, and solution polymerization method is more preferred.
- solvents examples include esters such as ethyl acetate and n-butyl acetate; aromatic hydrocarbons such as toluene and benzene; aliphatic hydrocarbons such as n-hexane and n-heptane; alicyclic hydrocarbons such as methylcyclohexane; ketones such as methyl ethyl ketone and methyl isobutyl ketone; and organic solvents. Only one kind of solvent may be used, or two or more kinds thereof may be used.
- Any suitable polymerization initiator for example, a thermal polymerization initiator, a photopolymerization initiator, etc.
- a thermal polymerization initiator for example, a thermal polymerization initiator, a photopolymerization initiator, etc.
- Only one polymerization initiator may be used, or two or more polymerization initiators may be used.
- an oil-soluble polymerization initiator when performing solution polymerization, it is preferable to use an oil-soluble polymerization initiator.
- thermal polymerization initiator can be used as the thermal polymerization initiator as long as it does not impair the effects of the present invention.
- the thermal polymerization initiator may be used alone or in combination of two or more.
- thermal polymerization initiators include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-2-methylbutyronitrile (AMBN), 2,2'-azobis(2- methylpropionate) dimethyl, 4,4′-azobis-4-cyanovaleric acid, 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis(2,4- dimethylvaleronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (2,4,4-trimethylpentane) and other azo initiators; benzoyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, t-butyl peroxybenz
- the amount of the thermal polymerization initiator to be used is preferably 0.1 parts by mass with respect to 100 parts by mass of the total monomers (monomer composition) that can be used to form the organic polymer compound in the second polymer. ⁇ 15 parts by mass.
- photopolymerization initiator Any appropriate photopolymerization initiator can be employed as the photopolymerization initiator as long as it does not impair the effects of the present invention. Only one type of photopolymerization initiator may be used, or two or more types may be used. Examples of such photopolymerization initiators include benzoin ether-based photopolymerization initiators, acetophenone-based photopolymerization initiators, ⁇ -ketol-based photopolymerization initiators, aromatic sulfonyl chloride-based photopolymerization initiators, and photoactive oxime-based photopolymerization initiators.
- Photoinitiators benzoin photoinitiators, benzyl photoinitiators, benzophenone photoinitiators, ketal photoinitiators, thioxanthone photoinitiators, acylphosphine oxide photoinitiators, etc. is mentioned.
- the amount of the photopolymerization initiator used is, for example, preferably 0.001 part by mass with respect to 100 parts by mass of all the monomers (monomer composition) that can be used to constitute the organic polymer compound in the second polymer. ⁇ 0.5 parts by mass.
- a chain transfer agent may be used in order to adjust the molecular weight during the polymerization of the organic polymer compound in the second polymer.
- chain transfer agents include 2-mercaptoethanol, ⁇ -thioglycerol, 2,3-dimercapto-1-propanol, octyl mercaptan, t-nonyl mercaptan, dodecyl mercaptan (lauryl mercaptan), t-dodecyl mercaptan, glycidyl mercaptan.
- thioglycolic acid methyl thioglycolate, ethyl thioglycolate, propyl thioglycolate, butyl thioglycolate, t-butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, isooctyl thioglycolate, thio decyl glycolate, dodecyl thioglycolate, ethylene glycol thioglycolate, neopentyl glycol thioglycolate, pentaerythritol thioglycolate, ⁇ -methylstyrene dimer and the like.
- 2-mercaptoethanol and methyl thioglycolate are preferred, and 2-mercaptoethanol is particularly preferred, from the viewpoint of suppressing whitening of the double-sided pressure-sensitive adhesive tape of the present invention.
- Only one type of chain transfer agent may be used, or two or more types may be used.
- the amount of the chain transfer agent used is, for example, preferably 0.1 parts by mass to 20 parts by mass with respect to 100 parts by mass of all monomers (monomer composition) that can be used to constitute the organic polymer compound in the second polymer. parts by mass, more preferably 0.2 to 15 parts by mass, still more preferably 0.3 to 10 parts by mass.
- the weight-average molecular weight of the organic polymer compound in the second polymer is not particularly limited, it is preferably 500 or more and 1,000,000 or less.
- the upper limit of the weight average molecular weight is more preferably 800,000, more preferably 600,000, still more preferably 400,000, more preferably 200,000, still more preferably 100,000, still more preferably 10,000. It is more preferably 1,000, still more preferably 2,000, even more preferably 3,000, still more preferably 4,000.
- the weight-average molecular weight is 500 or more, it is possible to effectively suppress the problem of contamination of the adherend surface after the pressure-sensitive adhesive layer is peeled off due to surface segregation. Further, when the weight-average molecular weight is 1,000,000 or less, it is possible to effectively suppress the problem that the cohesive force of the pressure-sensitive adhesive layer is lowered and adhesive residue is generated on the adherend after peeling.
- the second polymer can be used alone or in combination of two or more.
- the content of the organic polymer compound in the second polymer is 100 parts by mass of the first polymer or the monomer mixture which is the raw material of the first polymer With respect to 100 parts by mass, it is preferably 1 part by mass or more from the viewpoint of adhesive properties, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, and 15 parts by mass or more. more preferably 20 parts by mass or more, more preferably 25 parts by mass or more, and even more preferably 30 parts by mass or more. From the viewpoint of adhesive properties, the amount is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, even more preferably 60 parts by mass or less, and even more preferably 50 parts by mass or less. .
- the content of the organic polymer compound in the second polymer may be 1 to 50 parts by mass with respect to 100 parts by mass of the first polymer.
- These second polymers may be added after obtaining the first polymer, or may be added together with the monomer mixture which is the raw material of the first polymer before obtaining the first polymer.
- a polymerization reaction may be performed, but it is preferable that the first polymer and the second polymer are blended after each polymerization reaction.
- the HSP value difference between the first polymer and the second polymer is preferably 0 to 3, and the first polymer and the second polymer More preferably, the HSP value difference of the organic polymer compound is 0-3.
- the HSP value difference ( ⁇ HSP value) between the first polymer and the second polymer is the difference between the HSP value of the first polymer and the HSP value of the second polymer.
- the HSP value difference between the first polymer and the second polymer is preferably 3 or less, more preferably 2.5 or less, and still more preferably 2 or less.
- HSP value is a physical property value possessed by a certain substance.
- ⁇ P which is represented by the hydrogen bond term ( ⁇ H), which is the energy derived from intermolecular hydrogen bond strength, and it is known that substances with similar HSP values exhibit similar physical properties.
- the HSP value may be a known value, or may be calculated using computer software HSPiP (source: http://www.hansen-solubility.com/index.html) or the like.
- the HSP value difference between the first polymer and the second polymer depends on the types of the first polymer and the second polymer used, the blending amount, etc. can be adjusted.
- the ionic liquid in the embodiment of the present invention is not particularly limited as long as it is a molten salt (normal temperature molten salt) that is composed of a pair of anion and cation and is liquid at 25°C. Examples of anions and cations are given below. Of the ionic substances obtained by combining these, those that are liquid at 25°C are ionic liquids, and those that are solid at 25°C are not ionic liquids. is an ionic solid.
- the anions of the ionic liquid are, for example, (FSO 2 ) 2 N ⁇ , (CF 3 SO 2 ) 2 N ⁇ , (CF 3 CF 2 SO 2 ) 2 N ⁇ , (CF 3 SO 2 ) 3 C ⁇ , Br ⁇ , AlCl 4 ⁇ , Al 2 Cl 7 ⁇ , NO 3 ⁇ , BF 4 ⁇ , PF 6 ⁇ , CH 3 COO ⁇ , CF 3 COO ⁇ , CF 3 CF 2 CF 2 COO ⁇ , CF 3 SO 3 ⁇ , CF 3 (CF 2 ) 3 SO 3 ⁇ , AsF 6 ⁇ , SbF 6 ⁇ , F(HF) n ⁇ and the like.
- the anions include sulfonylimide compounds such as (FSO 2 ) 2 N ⁇ [bis(fluorosulfonyl)imide anion] and (CF 3 SO 2 ) 2 N ⁇ [bis(trifluoromethanesulfonyl)imide anion].
- Anions are preferable because they are chemically stable and suitable for improving the electrical strippability. That is, the anion of the ionic liquid preferably contains at least one selected from the group consisting of bis(fluorosulfonyl)imide anions and bis(trifluoromethanesulfonyl)imide anions.
- nitrogen-containing onium, sulfur-containing onium, and phosphorus-containing onium cations are preferable because they are chemically stable and suitable for improving the electrical stripping property.
- pyrrolidinium-based, and pyridinium-based cations are more preferred.
- imidazolium cations include 1-methylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-propyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1 -Pentyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-heptyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-nonyl-3- methylimidazolium cation, 1-undecyl-3-methylimidazolium cation, 1-dodecyl-3-methylimidazolium cation, 1-tridecyl-3-methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation, 1 -pentadecyl-3-methylimidazolium cation,
- pyridinium-based cations examples include 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, and 1-octyl-4-methylpyridinium cation. etc.
- pyrrolidinium-based cations examples include 1-ethyl-1-methylpyrrolidinium cations and 1-butyl-1-methylpyrrolidinium cations.
- ammonium-based cations include tetraethylammonium cation, tetrabutylammonium cation, methyltrioctylammonium cation, tetradecitrihexylammonium cation, glycidyltrimethylammonium cation and trimethylaminoethylacrylate cation.
- the ionic liquid it is preferable to select a cation having a molecular weight of 160 or less as a constituent cation from the viewpoint of increasing the rate of decrease in adhesive strength when a voltage is applied.
- Ionic liquids containing [fluorosulfonyl)imide anion] or (CF 3 SO 2 ) 2 N ⁇ [bis(trifluoromethanesulfonyl)imide anion] and a cation having a molecular weight of 160 or less are particularly preferred.
- Examples of cations having a molecular weight of 160 or less include 1-methylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-propyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-pentyl-3-methylimidazolium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-ethyl-1-methyl pyrrolidinium cation, 1-butyl-1-methylpyrrolidinium cation, tetraethylammonium cation, glycidyltrimethylammonium cation, trimethylaminoethylacrylate cation, and the like.
- R 1 in formula (2-A) represents a hydrocarbon group having 4 to 10 carbon atoms (preferably a hydrocarbon group having 4 to 8 carbon atoms, more preferably a hydrocarbon group having 4 to 6 carbon atoms), A heteroatom may be included, and R 2 and R 3 are the same or different and are a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms (preferably a hydrocarbon group having 1 to 8 carbon atoms, more preferably a hydrocarbon group having 1 to 8 carbon atoms, more preferably to 6 hydrocarbon groups, more preferably hydrocarbon groups having 2 to 4 carbon atoms), which may contain a heteroatom. However, when the nitrogen atom forms a double bond with the adjacent carbon atom, R3 is absent.
- R 4 in formula (2-B) represents a hydrocarbon group having 2 to 10 carbon atoms (preferably a hydrocarbon group having 2 to 8 carbon atoms, more preferably a hydrocarbon group having 2 to 6 carbon atoms), A heteroatom may be included, and R 5 , R 6 and R 7 are the same or different and are a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms (preferably a hydrocarbon group having 1 to 8 carbon atoms, more preferably represents a hydrocarbon group having 2 to 6 carbon atoms, more preferably a hydrocarbon group having 2 to 4 carbon atoms, which may contain a heteroatom.
- R 8 in formula (2-C) represents a hydrocarbon group having 2 to 10 carbon atoms (preferably a hydrocarbon group having 2 to 8 carbon atoms, more preferably a hydrocarbon group having 2 to 6 carbon atoms), A heteroatom may be included, and R 9 , R 10 and R 11 are the same or different and are a hydrogen atom or a hydrocarbon group having 1 to 16 carbon atoms (preferably a hydrocarbon group having 1 to 10 carbon atoms, more preferably represents a hydrocarbon group having 1 to 8 carbon atoms) and may contain a heteroatom.
- X in formula (2-D) represents a nitrogen, sulfur or phosphorus atom
- R 12 , R 13 , R 14 and R 15 are the same or different and are hydrocarbon groups having 1 to 16 carbon atoms ( Preferably a hydrocarbon group having 1 to 14 carbon atoms, more preferably a hydrocarbon group having 1 to 10 carbon atoms, still more preferably a hydrocarbon group having 1 to 8 carbon atoms, particularly preferably a hydrocarbon group having 1 to 6 carbon atoms. ) and may contain heteroatoms. However, when X is a sulfur atom, R 12 does not exist.
- the cation of the ionic liquid preferably contains at least one selected from the group consisting of nitrogen-containing onium cations, sulfur-containing onium cations, and phosphorus-containing onium cations.
- the molecular weight of the cation in the ionic liquid is, for example, 500 or less, preferably 400 or less, more preferably 300 or less, still more preferably 250 or less, particularly preferably 200 or less, and most preferably 160 or less. Moreover, it is usually 50 or more. It is thought that cations in the ionic liquid have the property of moving toward the cathode side in the pressure-sensitive adhesive layer upon application of a voltage and being concentrated near the interface between the pressure-sensitive adhesive layer and the adherend. In the present invention, therefore, the adhesive strength during voltage application is lower than the initial adhesive strength, resulting in electro-peeling. A cation with a low molecular weight such as 500 or less facilitates movement of the cation to the cathode side in the pressure-sensitive adhesive layer, and is suitable for increasing the rate of decrease in adhesive strength upon voltage application.
- ionic liquids include, for example, "Elexel AS-110”, “Elexel MP-442”, “Elexel IL-210”, “Elexel MP-471”, “Elexel MP-” manufactured by Daiichi Kogyo Seiyaku Co., Ltd. 456”, “Elexel AS-804”, “HMI-FSI” manufactured by Mitsubishi Materials Corporation, “CIL-312” and “CIL-313” manufactured by Nippon Carlit Co., Ltd., and the like.
- the ionic conductivity of the ionic liquid is preferably 0.1 mS/cm or more. It is more preferably 1 mS/cm or more, still more preferably 3 mS/cm or more, still more preferably 5 mS/cm or more, even more preferably 10 mS/cm or more, and particularly preferably 15 mS/cm or more. and most preferably 20 mS/cm or more.
- the adhesive strength is sufficiently lowered even at a low voltage.
- the ionic conductivity can be measured by an AC impedance method using, for example, a Solartron 1260 frequency response analyzer.
- the content (blended amount) of the ionic liquid in the pressure-sensitive adhesive composition according to the embodiment of the present invention is 0.5 parts by mass or more with respect to 100 parts by mass of the first polymer. It is preferable from the viewpoint of reducing the force, and 30 parts by mass or less is preferable from the viewpoint of increasing the initial adhesive strength. From the same viewpoint, it is more preferably 20 parts by mass or less, further preferably 15 parts by mass or less, particularly preferably 10 parts by mass or less, and most preferably 5 parts by mass or less. Further, it is more preferably 0.6 parts by mass or more, further preferably 0.8 parts by mass or more, particularly preferably 1.0 parts by mass or more, and 1.5 parts by mass or more. is most preferred.
- the pressure-sensitive adhesive composition according to the embodiment of the present invention contains 1 It can contain one kind or two or more kinds. Other components that may be contained in the pressure-sensitive adhesive composition according to the embodiment of the present invention are described below.
- the adhesive composition according to the embodiment of the present invention may contain an ionic additive for the purpose of controlling the electrical peeling force.
- An ionic solid for example, can be used as the ionic additive.
- An ionic solid is an ionic substance that is solid at 25°C.
- the ionic solid is not particularly limited, for example, among the ionic substances obtained by combining the anions and cations exemplified in the description of the ionic liquid described above, those that are solid can be used.
- the content of the ionic solid is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, relative to 100 parts by mass of the first polymer. Also, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 2.5 parts by mass or less.
- the pressure-sensitive adhesive composition according to the embodiment of the present invention may contain a cross-linking agent as necessary for the purpose of improving creep resistance and shear resistance by cross-linking the polymer.
- cross-linking agents include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, melamine-based cross-linking agents, peroxide-based cross-linking agents, urea-based cross-linking agents, metal alkoxide-based cross-linking agents, metal chelate-based cross-linking agents, and metal salt-based cross-linking agents.
- examples include cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, and amine-based cross-linking agents.
- isocyanate-based cross-linking agents include toluenediisocyanate and methylenebisphenylisocyanate.
- epoxy-based cross-linking agents include N,N,N',N'-tetraglycidyl-m-xylenediamine, diglycidylaniline, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane and 1, 6-hexanediol diglycidyl ether and the like.
- the content is preferably 0.1 parts by mass or more, more preferably 0.7 parts by mass or more, and preferably 50 parts by mass or less with respect to 100 parts by mass of the first polymer. , 10 parts by mass or less, more preferably 3 parts by mass or less.
- a crosslinking agent can be used individually or in combination of 2 or more types.
- the adhesive composition according to the embodiment of the present invention may contain polyethylene glycol or tetraethylene glycol dimethyl ether for the purpose of assisting the movement of the ionic liquid when voltage is applied.
- polyethylene glycol and tetraethylene glycol dimethyl ether those having a number average molecular weight of 100 to 6,000 can be used.
- the content is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more, relative to 100 parts by mass of the first polymer.
- the content is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less.
- the pressure-sensitive adhesive composition according to the embodiment of the present invention may contain a conductive filler as necessary for the purpose of imparting conductivity to the pressure-sensitive adhesive composition.
- the conductive filler is not particularly limited, and general known or commonly used conductive fillers can be used. For example, graphite, carbon black, carbon fiber, metal powder such as silver and copper, etc. can be used. .
- the content is preferably 0.1 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the first polymer.
- the pressure-sensitive adhesive composition according to the embodiment of the present invention may contain a corrosion inhibitor as necessary for the purpose of suppressing corrosion of metal adherends.
- the corrosion inhibitor is not particularly limited, and general known or commonly used corrosion inhibitors can be used.
- carbodiimide compounds, adsorption inhibitors, chelate-forming metal deactivators, and the like can be used.
- Carbodiimide compounds include, for example, 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, N,N'-dicyclohexylcarbodiimide, N,N '-diisopropylcarbodiimide, 1-ethyl-3-tert-butylcarbodiimide, N-cyclohexyl-N'-(2-morpholinoethyl)carbodiimide, N,N'-di-tert-butylcarbodiimide, 1,3-bis(p -tolyl) carbodiimide, polycarbodiimide resins using these as monomers, and the like.
- carbodiimide compounds can be used alone or in combination of two or more.
- the content is preferably 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the first polymer.
- adsorption-type inhibitors examples include alkylamines, carboxylates, carboxylic acid derivatives, and alkyl phosphates.
- An adsorption inhibitor can be used individually or in combination of 2 or more types.
- the adhesive composition according to the embodiment of the present invention contains an alkylamine as an adsorption inhibitor, the content is 0.01 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the first polymer. preferable.
- the adhesive composition according to the embodiment of the present invention contains a carboxylate as an adsorptive inhibitor, the content is 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the first polymer. is preferred.
- the content is 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the first polymer. is preferred.
- the adhesive composition according to the embodiment of the present invention contains an alkyl phosphate as an adsorption inhibitor, the content is 0.01 parts by mass or more and 10 parts by mass with respect to 100 parts by mass of the first polymer. The following are preferred.
- a chelate-forming metal deactivator for example, a triazole group-containing compound or a benzotriazole group-containing compound can be used. These are preferable because they have a high effect of inactivating the surface of metals such as stainless steel and aluminum, and they hardly affect adhesiveness even if they are contained in the adhesive component.
- Chelate-forming metal deactivators can be used alone or in combination of two or more.
- the content is 0.01 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the first polymer. is preferred.
- the total content (compounding amount) of the corrosion inhibitor is preferably 0.01 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the first polymer.
- the pressure-sensitive adhesive composition according to the embodiment of the present invention also includes fillers, plasticizers, anti-aging agents, antioxidants, pigments (dyes), flame retardants, solvents, surfactants (leveling agents), and rust preventives. agents, and various additives such as antistatic agents.
- the total content of these components is not particularly limited as long as the effects of the present invention are exhibited, but is preferably 0.01 parts by mass or more and 20 parts by mass or less, more preferably 100 parts by mass of the first polymer. It is 10 parts by mass or less, more preferably 5 parts by mass or less.
- fillers include silica, iron oxide, zinc oxide, aluminum oxide, titanium oxide, barium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, pyroxene clay, kaolin clay, and calcined clay. .
- plasticizer known and commonly used plasticizers used in general resin compositions can be used.
- oils such as paraffin oil and process oil, liquid polyisoprene, liquid polybutadiene, liquid ethylene-propylene rubber, Liquid rubber, tetrahydrophthalic acid, azelaic acid, benzoic acid, phthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, citric acid and their derivatives, dioctyl phthalate ( DOP), dibutyl phthalate (DBP), dioctyl adipate, diisononyl adipate (DINA), isodecyl succinate, and the like can be used.
- DOP dioctyl phthalate
- DBP dibutyl phthalate
- DINA diisononyl adipate
- antioxidants examples include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).
- BHT butylhydroxytoluene
- BHA butylhydroxyanisole
- pigments include inorganic pigments such as titanium dioxide, zinc oxide, ultramarine blue, red iron oxide, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochlorides and sulfates, organic pigments such as azo pigments, and copper phthalocyanine pigments. is mentioned.
- rust preventives include zinc phosphates, tannic acid derivatives, phosphate esters, basic sulfonates, and various rust preventive pigments.
- Tackifiers include, for example, titanium coupling agents and zirconium coupling agents.
- Antistatic agents generally include quaternary ammonium salts, or hydrophilic compounds such as polyglycolic acid and ethylene oxide derivatives.
- the adhesive strength of the pressure-sensitive adhesive composition according to the embodiment of the present invention can be evaluated by various methods. For example, it can be evaluated by the 180° peel test described in the Examples section.
- the pressure-sensitive adhesive composition according to the embodiment of the present invention forms a pressure-sensitive adhesive sheet as described in Examples, and has an initial adhesive strength of 1.5 N/cm or more as measured by a 180° peel test. is preferably 2.0 N/cm or more, more preferably 2.5 N/cm or more, particularly preferably 3.0 N/cm or more, and 3.5 N/cm or more. Most preferably there is. When the initial adhesive strength is 1.5 N/cm or more, the adhesion to the adherend is sufficient, and the adherend is less likely to peel off or shift.
- the pressure-sensitive adhesive composition according to the embodiment of the present invention is formed into a pressure-sensitive adhesive sheet as described in the section of Examples, left for a predetermined period under an environment of predetermined temperature and humidity, and applied with a voltage of 30 V for 30 minutes. It is preferable that the adhesive force measured by a 180° peel test while applying a voltage of 30 V after being applied for a second is sufficiently smaller than the initial adhesive force.
- the adhesive strength decrease rate obtained by the following formula (C) from the adhesive strength measured by the above method (simply referred to as "adhesive strength during voltage application” in the following formula (C)) and the initial adhesive strength is preferably 75% or more, preferably 80% or more.
- the predetermined temperature, humidity and period are preferably 60° C. 90% RH 168 hours, particularly preferably 60° C. 90% RH 500 hours. If the adhesive strength after 500 hours at 60°C and 90% RH is sufficiently smaller than the initial adhesive strength, the wet heat stability is excellent even after storage in a high-temperature and high-humidity environment.
- Adhesive strength decrease rate (%) ⁇ 1-(adhesive strength during voltage application/initial adhesive strength) ⁇ x 100 (C)
- the applied voltage and voltage application time during the electro-peeling are not limited to those described above, and are not particularly limited as long as the pressure-sensitive adhesive sheet can be peeled off. These preferred ranges are shown below.
- the applied voltage is preferably 1 V or higher, more preferably 3 V or higher, and even more preferably 6 V or higher. Also, it is preferably 100 V or less, more preferably 50 V or less, even more preferably 30 V or less, and particularly preferably 15 V or less.
- the voltage application time is preferably 60 seconds or less, more preferably 40 seconds or less, even more preferably 20 seconds or less, and particularly preferably 10 seconds or less. In such a case, workability is excellent. Also, the shorter the application time, the better, but it is usually 1 second or more.
- the pressure-sensitive adhesive composition of the present invention is not particularly limited, but is produced by appropriately stirring and mixing a polymer, an ionic liquid, additives, and optionally a cross-linking agent, polyethylene glycol, conductive filler, etc. can do.
- the pressure-sensitive adhesive sheet according to the embodiment of the present invention has at least one pressure-sensitive adhesive layer formed from the above-described pressure-sensitive adhesive composition according to the embodiment of the present invention (hereinafter also referred to as "electro-peelable pressure-sensitive adhesive layer”). Not restricted.
- the pressure-sensitive adhesive sheet according to the embodiment of the present invention may have a pressure-sensitive adhesive layer containing no ionic liquid (hereinafter sometimes referred to as "another pressure-sensitive adhesive layer”) other than the electro-peelable pressure-sensitive adhesive layer. good.
- the pressure-sensitive adhesive sheet according to the embodiment of the present invention may have a substrate, a conductive layer, a conductive substrate, an intermediate layer, an undercoat layer, etc., in addition to the above.
- the pressure-sensitive adhesive sheet according to the embodiment of the present invention may be, for example, wound in a roll or in a sheet form.
- the meaning of an "adhesive tape" shall also be included in an "adhesive sheet.” That is, the pressure-sensitive adhesive sheet according to the embodiment of the present invention may be a pressure-sensitive adhesive tape having a tape-like shape.
- the pressure-sensitive adhesive sheet according to the embodiment of the present invention may be a double-sided pressure-sensitive adhesive sheet that does not have a substrate and consists only of an electrically peeling pressure-sensitive adhesive layer, that is, does not contain a substrate layer (substrate-less).
- the pressure-sensitive adhesive sheet according to the embodiment of the present invention may be a double-sided pressure-sensitive adhesive sheet having a base material and pressure-sensitive adhesive layers (electro-peeling pressure-sensitive adhesive layers or other pressure-sensitive adhesive layers) on both sides of the base material. good.
- the pressure-sensitive adhesive sheet according to the embodiment of the present invention is a single-sided pressure-sensitive adhesive sheet having a base material, and only one side of the base material is a pressure-sensitive adhesive layer (electro-peelable pressure-sensitive adhesive layer or other pressure-sensitive adhesive layer). There may be.
- the pressure-sensitive adhesive sheet according to the embodiment of the invention may have a release liner for the purpose of protecting the surface of the pressure-sensitive adhesive layer, but the release liner is not included in the pressure-sensitive adhesive sheet according to the embodiment of the invention. Make it not exist.
- the structure of the pressure-sensitive adhesive sheet according to the embodiment of the present invention is not particularly limited, but pressure-sensitive adhesive sheet X1 shown in FIG. 1, pressure-sensitive adhesive sheet X2 showing a laminated structure in FIG. 2, and pressure-sensitive adhesive sheet X3 showing a laminated structure in FIG. 3 are preferable. mentioned.
- the pressure-sensitive adhesive sheet X1 is a substrate-less double-sided pressure-sensitive adhesive sheet consisting of only the electro-peelable pressure-sensitive adhesive layer 1.
- the pressure-sensitive adhesive sheet X2 is a double-sided pressure-sensitive adhesive sheet with a substrate having a layer configuration of a pressure-sensitive adhesive layer 2, a conductive substrate 5 (a substrate 3 and a conductive layer 4), and an electrically peeling pressure-sensitive adhesive layer 1.
- the pressure-sensitive adhesive sheet X3 includes an adhesive layer 2, a conductive base material 5 (a base material 3 and a conductive layer 4), an electrically peelable pressure-sensitive adhesive layer 1, a conductive base material 5 (a base material 3 and a conductive layer 4), and an adhesive. It is a double-sided pressure-sensitive adhesive sheet with a substrate having a layer structure of Layer 2.
- the base material 3 is not essential, and the conductive layer 4 alone may be used.
- the single-sided adhesive sheet which does not provide the adhesive layer 2 may be used.
- the substrate 3 is not particularly limited, but may be a paper-based substrate such as paper, a fiber-based substrate such as cloth or non-woven fabric, various plastics (polyolefin-based resins such as polyethylene and polypropylene, polyester-based resins such as polyethylene terephthalate, poly Examples include plastic base materials such as films and sheets made of acrylic resins such as methyl methacrylate, laminates thereof, and the like.
- the substrate may have the form of a single layer, or may have the form of multiple layers.
- the base material may be subjected to various treatments such as back surface treatment, antistatic treatment, and undercoating treatment, if necessary.
- the conductive layer 4 is not particularly limited as long as it is a layer having conductivity, but metal (e.g., aluminum, magnesium, copper, iron, tin, gold, etc.) foil, metal plate (e.g., aluminum, magnesium, copper, iron , tin, silver, etc.), a conductive polymer, or the like, or a metal deposition film provided on the substrate 3 may be used.
- metal e.g., aluminum, magnesium, copper, iron, tin, gold, etc.
- metal plate e.g., aluminum, magnesium, copper, iron , tin, silver, etc.
- a conductive polymer e.g., aluminum, magnesium, copper, iron , tin, silver, etc.
- the conductive base material 5 is not particularly limited as long as it is a base material having a conductive layer (conducts current), and examples thereof include those having a metal layer formed on the surface of the base material.
- a metal layer is formed on the surface of the material by a method such as plating, chemical vapor deposition, or sputtering. Examples of the metal layer include the above-exemplified metals, metal plates, conductive polymers, and the like.
- the adherends on both sides are preferably adherends having metal adherend surfaces.
- the adherend on the side of the electro-peelable pressure-sensitive adhesive layer 1 is preferably an adherend having a metal adherend surface.
- the metal adhering surface examples include conductive surfaces made of metals containing aluminum, copper, iron, magnesium, tin, gold, silver, lead, etc. as main components.
- a surface made of metal (for example, stainless steel, etc.) is preferable.
- the adherend having a metal adherend surface includes, for example, sheets, parts, and plates made of a metal containing aluminum, copper, iron, magnesium, tin, gold, silver, lead, or the like as a main component.
- the adherend other than the adherend having a metal adherend surface include, but are not particularly limited to, paper, cloth, fiber sheets such as nonwoven fabric, and various plastic films and sheets.
- the thickness of the electro-peelable pressure-sensitive adhesive layer 1 is preferably 1 ⁇ m or more and 1000 ⁇ m or less.
- the upper limit of the thickness of the electrically peelable pressure-sensitive adhesive layer 1 is more preferably 500 ⁇ m, still more preferably 300 ⁇ m, still more preferably 200 ⁇ m, still more preferably 150 ⁇ m, still more preferably 100 ⁇ m, and even more preferably 100 ⁇ m. is 80 ⁇ m, more preferably 70 ⁇ m, more preferably 60 ⁇ m, still more preferably 50 ⁇ m, the lower limit is more preferably 5 ⁇ m, more preferably 10 ⁇ m, still more preferably 20 ⁇ m, More preferably, it is 30 ⁇ m.
- the thickness of the electropeelable pressure-sensitive adhesive sheet of this embodiment is preferably 20 ⁇ m or more and 3000 ⁇ m or less.
- the upper limit of the thickness is more preferably 1000 ⁇ m, still more preferably 500 ⁇ m, still more preferably 300 ⁇ m, still more preferably 250 ⁇ m, still more preferably 200 ⁇ m, still more preferably 150 ⁇ m, still more preferably It is 100 ⁇ m, and the lower limit is more preferably 30 ⁇ m, still more preferably 50 ⁇ m.
- the thickness of the pressure-sensitive adhesive layer 2 is preferably 1 ⁇ m or more and 2000 ⁇ m or less from the viewpoint of adhesive strength.
- the upper limit of the thickness of the pressure-sensitive adhesive layer 2 is more preferably 1000 ⁇ m, more preferably 500 ⁇ m, particularly preferably 100 ⁇ m, and the lower limit is more preferably 3 ⁇ m, still more preferably 5 ⁇ m, and particularly preferably. is 8 ⁇ m.
- the thickness of the base material 3 is preferably 10 ⁇ m or more and 1000 ⁇ m or less.
- the upper limit of the thickness is more preferably 500 ⁇ m, still more preferably 300 ⁇ m, particularly preferably 100 ⁇ m, and the lower limit is more preferably 12 ⁇ m, still more preferably 25 ⁇ m.
- the thickness of the conductive layer 4 is preferably 0.001 ⁇ m or more and 1000 ⁇ m or less.
- the upper limit of the thickness is more preferably 500 ⁇ m, more preferably 300 ⁇ m, still more preferably 50 ⁇ m, still more preferably 10 ⁇ m, and the lower limit is more preferably 0.01 ⁇ m, more preferably 0.01 ⁇ m.
- the thickness of the conductive substrate 5 is preferably 10 ⁇ m or more and 1000 ⁇ m or less.
- the upper limit of the thickness is more preferably 500 ⁇ m, still more preferably 300 ⁇ m, particularly preferably 100 ⁇ m, and the lower limit is more preferably 12 ⁇ m, still more preferably 25 ⁇ m.
- the surfaces of the electro-peelable pressure-sensitive adhesive layer and other pressure-sensitive adhesive layers of the pressure-sensitive adhesive sheet according to the embodiment of the present invention may be protected by a release liner release liner.
- the release liner is not particularly limited, but includes a release liner in which the surface of a base material (liner base material) such as paper or plastic film is treated with silicone, or the surface of a base material (liner base material) such as paper or plastic film. and a release liner laminated with a polyolefin resin.
- the thickness of the release liner is not particularly limited, but is preferably 10 ⁇ m or more and 100 ⁇ m or less.
- the thickness of the adhesive sheet according to the embodiment of the present invention is preferably 20 ⁇ m or more and 3000 ⁇ m or less.
- the upper limit of the thickness is more preferably 1000 ⁇ m, still more preferably 500 ⁇ m, still more preferably 300 ⁇ m, still more preferably 250 ⁇ m, still more preferably 200 ⁇ m, still more preferably 150 ⁇ m, still more preferably It is 100 ⁇ m, and the lower limit is more preferably 30 ⁇ m, still more preferably 50 ⁇ m.
- the thickness of the adhesive sheet is preferably 50 ⁇ m or more and 2000 ⁇ m or less.
- the upper limit of the thickness is more preferably 1000 ⁇ m, still more preferably 500 ⁇ m, still more preferably 300 ⁇ m, still more preferably 250 ⁇ m, still more preferably 200 ⁇ m, still more preferably 150 ⁇ m, and the lower limit is It is more preferably 80 ⁇ m, and still more preferably 100 ⁇ m.
- the thickness of the adhesive sheet is preferably 20 ⁇ m or more and 3000 ⁇ m or less.
- the upper limit of the thickness is more preferably 1000 ⁇ m, still more preferably 500 ⁇ m, still more preferably 300 ⁇ m, still more preferably 250 ⁇ m, still more preferably 200 ⁇ m, still more preferably 150 ⁇ m, and the lower limit is It is more preferably 50 ⁇ m, still more preferably 80 ⁇ m, and even more preferably 100 ⁇ m.
- the pressure-sensitive adhesive sheet according to the embodiment of the invention may further have a coat layer.
- the coat layer is preferably provided between the electrically-peelable pressure-sensitive adhesive layer and the conductive layer.
- the electro-peeling pressure-sensitive adhesive sheet of the present embodiment further comprises a coat layer, which serves as a barrier for the ionic liquid contained in the electro-peeling pressure-sensitive adhesive layer to penetrate into the conductive layer when a voltage is applied, thereby preventing the conductive layer from peeling off from the substrate. It has a preventive effect.
- the coating layer is in contact with the electro-peeling adhesive layer, the adhesion between the electro-peeling adhesive layer and the conductive layer is improved, and the electro-peeling adhesive layer exposed to a high-temperature environment is improved.
- Heat curing reduces the interfacial adhesive strength between the electrically-peelable pressure-sensitive adhesive layer and a conductive material (for example, an adherend), thereby preventing peeling within the electrically-peelable pressure-sensitive adhesive sheet.
- the coat layer is a layer containing a resin or an inorganic substance as a main component, and can be formed from a resin composition containing a resin component as a main component or a composition containing an inorganic substance as a main component.
- the coating layer contains at least one resin selected from polyester resins, acrylic resins, epoxy resins, and urethane resins, or at least one inorganic material selected from SiNx, SiOx, Al 2 O 3 , Ni, and NiCr. is preferred.
- a known or commonly used manufacturing method can be used as the method for manufacturing the pressure-sensitive adhesive sheet according to the embodiment of the present invention.
- the electro-peelable pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet according to the embodiment of the present invention is formed by coating a release liner with a solution of the pressure-sensitive adhesive composition according to the embodiment of the present invention dissolved in a solvent, followed by drying and drying. / Or the method of hardening, etc. are mentioned.
- Other pressure-sensitive adhesive layers include a method of coating a release liner with a solution of a pressure-sensitive adhesive composition containing no ionic liquid and additives, optionally dissolved in a solvent, and drying and/or curing the solution. be done.
- the solvent and the release liner those mentioned above can be used.
- a conventional coater eg, gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, spray roll coater, etc.
- a conventional coater eg, gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, spray roll coater, etc.
- an electrically peelable pressure-sensitive adhesive layer and other pressure-sensitive adhesive layers can be produced, and the substrate, conductive layer, and electrically-disconnecting substrate may be appropriately coated with an electrically-peeling pressure-sensitive adhesive layer and other pressure-sensitive adhesive layers.
- the pressure-sensitive adhesive sheet according to the embodiment of the present invention can be produced.
- the adhesive sheet may be produced by using the base material, the conductive layer, and the conductive base material, and applying the pressure-sensitive adhesive composition.
- the pressure-sensitive adhesive sheet according to the embodiment of the present invention can be peeled from the adherend by applying a voltage to the electro-peeling pressure-sensitive adhesive layer to generate a potential difference in the thickness direction of the electro-peeling pressure-sensitive adhesive layer.
- a joined body in which the pressure-sensitive adhesive sheet X1 is attached to a conductive adherend can be peeled off by energizing the conductive adherend and applying a voltage to the electrically-peeling pressure-sensitive adhesive layer.
- the electrically-peeling adhesive layer side of the adhesive sheet X2 is an adherend having a metal adherend surface
- the conductive adherend and the conductive layer 4 are energized, and a voltage is applied to the electrically-peeling adhesive layer. It can be peeled off by
- the pressure-sensitive adhesive sheet X3 it can be peeled off by energizing the conductive layers 4 on both sides and applying a voltage to the electrically-peeling pressure-sensitive adhesive layer.
- the energization is preferably performed by connecting terminals to one end and the other end of the pressure-sensitive adhesive sheet so that a voltage is applied to the entire electro-peelable pressure-sensitive adhesive layer.
- the adherend has a metal adherend surface
- the one end and the other end may be part of the adherend having the metal adherend surface.
- the voltage may be applied after water is added to the interface between the metal adhesion surface and the electrically peeling pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive sheet according to the embodiment of the present invention is used for mobile terminals such as smartphones, mobile phones, laptop computers, video cameras, and digital cameras. Suitable for fixing to In addition, the pressure-sensitive adhesive sheet according to the embodiment of the present invention is suitable for fixing vehicle-mounted members (for example, batteries, motors, etc.). And the adhesive sheet according to the embodiment of the present invention is suitable for fixing applications (for example, ceramic capacitors, lithium ion batteries, etc.) in semiconductor manufacturing processes and inspections. Furthermore, the pressure-sensitive adhesive sheet according to the embodiment of the present invention is suitable for protective applications in metalworking processes (for example, stainless steel plates for railways, etc.).
- vehicle-mounted members for example, batteries, motors, etc.
- the adhesive sheet according to the embodiment of the present invention is suitable for fixing applications (for example, ceramic capacitors, lithium ion batteries, etc.) in semiconductor manufacturing processes and inspections.
- the pressure-sensitive adhesive sheet according to the embodiment of the present invention is suitable for protective applications in metalworking processes (for example, stainless steel plates for railways
- Examples of rigid members to be bonded by the pressure-sensitive adhesive sheet according to the embodiment of the present invention include silicon substrates for semiconductor wafers, sapphire substrates for LEDs, SiC substrates and metal base substrates, TFT substrates for displays and Examples include color filter substrates and base substrates for organic EL panels.
- Examples of fragile members to be bonded with double-sided adhesive sheets include semiconductor substrates such as compound semiconductor substrates, silicon substrates for MEMS devices, passive matrix substrates, surface cover glass for smartphones, and touch panel sensors attached to the cover glass.
- OGS One Glass Solution
- substrates organic substrates and organic-inorganic hybrid substrates containing silsesquioxane as a main component
- flexible glass substrates for flexible displays and graphene sheets.
- a joined body according to an embodiment of the present invention includes the pressure-sensitive adhesive sheet according to the embodiment of the present invention and a conductive material, and an electrically-peelable pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is adhered to the conductive material.
- the conductive material is preferably an adherend having a metal adherend surface. Examples of adherends having a metal adherend surface include aluminum, copper, iron, magnesium, tin, gold, silver, and lead. and the like, and metals containing aluminum are particularly preferred.
- bonded body of the present embodiment for example, a bonded body in which the adhesive sheet X1 and the electro-peelable adhesive layer 1 side of the adhesive sheet X1 are adhered to a conductive adherend having, for example, a metal adherend surface. etc.
- bonded body of the present embodiment for example, a bonded body in which the other adhesive layers 2 on both sides of the adhesive sheet X3 are adhered to a conductive material having, for example, a metal adhesion surface, or the adhesive sheet X3 A bonded body in which the other pressure-sensitive adhesive layer 2 is adhered to a non-conductive material.
- the adhesive sheet X1 is a bonded body provided with an adherend having metal adhesion surfaces on both sides of the electro-peelable adhesive layer 1, or the adhesive sheet X2. a joined body having an adherend having a metal adherend surface on the side of the electro-peelable pressure-sensitive adhesive layer 1 and an adherend on the side of the pressure-sensitive adhesive layer 2; Examples include bonded bodies including adherends.
- Tg glass transition temperature
- the second polymer contains an organic polymer compound, and the content of the organic polymer compound in the second polymer is 1 to 50 parts by mass with respect to 100 parts by mass of the first polymer.
- ⁇ 1> or the pressure-sensitive adhesive composition according to ⁇ 2> are examples of the first polymer and the second polymer having a glass transition temperature (Tg) of 40 to 180°C.
- ⁇ 4> Any one of ⁇ 1> to ⁇ 3>, wherein the anion of the ionic liquid includes at least one selected from the group consisting of bis(fluorosulfonyl)imide anions and bis(trifluoromethanesulfonyl)imide anions.
- the adhesive composition described. ⁇ 5> The cation of the ionic liquid includes at least one selected from the group consisting of nitrogen-containing onium cations, sulfur-containing onium cations, and phosphorus-containing onium cations, according to any one of ⁇ 1> to ⁇ 4>.
- Adhesive composition Adhesive composition.
- the first polymer contains at least one selected from the group consisting of a polyester polymer, a urethane polymer, and an acrylic polymer having a carboxyl group, an alkoxy group, a hydroxyl group and/or an amide bond, ⁇ 1 > to the pressure-sensitive adhesive composition according to any one of ⁇ 6>.
- ⁇ 8> The pressure-sensitive adhesive composition according to any one of ⁇ 1> to ⁇ 7>, wherein the second polymer contains a tackifying resin.
- ⁇ 9> The pressure-sensitive adhesive composition according to ⁇ 8>, wherein the tackifying resin has a softening point of 100°C or higher.
- ⁇ 10> The pressure-sensitive adhesive composition according to ⁇ 8> or ⁇ 9>, wherein the content of the tackifying resin is 1 to 50 parts by mass with respect to 100 parts by mass of the first polymer.
- ⁇ 11> The pressure-sensitive adhesive composition according to any one of ⁇ 8> to ⁇ 10>, wherein the tackifying resin is a terpene-based tackifying resin or a rosin-based tackifying resin.
- ⁇ 12> The pressure-sensitive adhesive composition according to any one of ⁇ 1> to ⁇ 11>, which is for electrical peeling.
- ⁇ 13> A pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to any one of ⁇ 1> to ⁇ 12>.
- ⁇ 14> Equipped with the adhesive sheet according to ⁇ 13> and a conductive material, A joined body in which the pressure-sensitive adhesive layer is adhered to the conductive material.
- the present invention will be described in more detail below with reference to examples, but the present invention is not limited by these examples.
- the weight average molecular weights below are those measured by a gel permeation chromatography (GPC) method.
- ⁇ Second polymer> (Polymer 1) As monomer components, cyclohexyl methacrylate (CHMA): 95 parts by mass, acrylic acid (AA): 5 parts by mass, ethyl acetate as a polymerization solvent: 300 parts by mass, and 2-mercaptoethanol (thioglycol) as a chain transfer agent: 3 parts by mass A portion was put into a separable flask and stirred for 1 hour while nitrogen gas was introduced. After removing oxygen in the polymerization system in this way, 2,2′-azobisisobutyronitrile (AIBN): 0.2 parts by mass was added as a polymerization initiator, and the temperature was raised to 65° C. for 3 hours. The mixture was reacted and then reacted at 75° C. for 2 hours to obtain a polymer 1 solution having a solid concentration of 25% by mass.
- CHMA cyclohexyl methacrylate
- AA acrylic acid
- ethyl acetate as a
- Polymer 2 100 parts by mass of isobornyl methacrylate (IBXMA) as a monomer component, 300 parts by mass of ethyl acetate as a polymerization solvent, and 3 parts by mass of 2-mercaptoethanol (thioglycol) as a chain transfer agent were put into a separable flask. , and stirred for 1 hour while nitrogen gas was introduced. After removing oxygen in the polymerization system in this way, 2,2′-azobisisobutyronitrile (AIBN): 0.2 parts by mass was added as a polymerization initiator, and the temperature was raised to 65° C. for 3 hours. The mixture was reacted and then reacted at 75° C. for 2 hours to obtain a polymer 2 solution having a solid concentration of 25% by mass.
- AIBN 2,2′-azobisisobutyronitrile
- Polymer 4 As monomer components, cyclohexyl methacrylate (CHMA): 85 parts by mass, 4 hydroxyl butyl acrylate (4HBA): 15 parts by mass, ethyl acetate as a polymerization solvent: 300 parts by mass, and 2-mercaptoethanol (thioglycol) as a chain transfer agent: 3 parts by mass was put into a separable flask and stirred for 1 hour while nitrogen gas was introduced. After removing oxygen in the polymerization system in this way, 2,2′-azobisisobutyronitrile (AIBN): 0.2 parts by mass was added as a polymerization initiator, and the temperature was raised to 65° C. for 3 hours. The mixture was reacted and then reacted at 75° C. for 2 hours to obtain a polymer 4 solution having a solid concentration of 25% by mass.
- CHMA cyclohexyl methacrylate
- 4HBA 4 hydroxyl butyl acrylate
- Polymer 7 As monomer components, methyl acrylate (MA): 55 parts by mass, N-vinylpyrrolidone: 45 parts by mass, ethyl acetate as a polymerization solvent: 300 parts by mass, and 2-mercaptoethanol (thioglycol) as a chain transfer agent: 3 parts by mass was put into a separable flask and stirred for 1 hour while nitrogen gas was introduced. After removing oxygen in the polymerization system in this way, 2,2′-azobisisobutyronitrile (AIBN): 0.2 parts by mass was added as a polymerization initiator, and the temperature was raised to 65° C. for 3 hours. The mixture was reacted and then reacted at 75° C. for 2 hours to obtain a polymer 7 solution having a solid concentration of 25% by mass.
- MA methyl acrylate
- N-vinylpyrrolidone 45 parts by mass
- ethyl acetate as a polymerization solvent
- the electro-peeling pressure-sensitive adhesive composition (solution) obtained above is applied onto the release-treated surface of a polyethylene terephthalate release liner (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc.) whose surface has been subjected to a release treatment, using an applicator. It was applied so as to have a uniform thickness. Next, heat drying is performed at 150° C. for 3 minutes, and the release-treated surface of the release-treated polyethylene terephthalate release liner (trade name “MRE38”, manufactured by Mitsubishi Plastics, Inc.) is coated with an adhesive layer using a hand roller. It was laminated thereon to obtain an electro-peelable pressure-sensitive adhesive layer (adhesive sheet) having a thickness of 50 ⁇ m.
- a polyethylene terephthalate release liner trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc.
- the resulting electro-peelable pressure-sensitive adhesive layer (adhesive sheet) was made into a sheet with a size of 10 mm ⁇ 80 mm, the MRE release liner was peeled off, and a film with a metal layer (trade name “1005CR”) was applied to the exposed electro-peeling pressure-sensitive adhesive layer surface.
- a film with a metal layer (trade name “1005CR”) was applied to the exposed electro-peeling pressure-sensitive adhesive layer surface.
- thickness 12 ⁇ m, size 10 mm ⁇ 100 mm were laminated to form a single-sided pressure-sensitive adhesive sheet with a substrate.
- Polymer 5 Acrylic polymer, trade name "ARUFON UC3000", manufactured by Toagosei Co., Ltd.
- Polymer 6 Acrylic polymer, trade name "ARUFON UH2170", manufactured by Toagosei Co., Ltd.
- tackifying resin (tackifying resin)
- (ionic liquid) AS-110 cation: 1-ethyl-3-methylimidazolium cation, anion: bis (fluorosulfonyl) imide anion, trade name "ELEXCEL AS-110", manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
- crosslinking agent V-05 Polycarbodiimide resin, trade name "Carbodilite V-05", manufactured by Nisshinbo Chemical Co., Ltd.
- AMINE O 2-(8-heptadecen-1-yl)-4,5-dihydro-1H-imidazole-1-ethanol, trade name “AMINE O”, manufactured by BASF Japan Ltd.
- Irgacor DSSG sodium sebacate, trade name "Irgacor DSSG”, manufactured by BASF Japan Ltd.
- Irgamet 30 N, N-bis (2-ethylhexyl) - [(1,2,4-triazol-1-yl) methyl] amine, trade name "Irgamet 30" BASF Japan Co., Ltd.
- the electro-peelable pressure-sensitive adhesive layers formed from the pressure-sensitive adhesive compositions of Examples 1 to 21 contain a second polymer having a glass transition temperature (Tg) of 40 to 180° C., all of them can be used under a high-temperature and high-humidity environment. Even after storage at room temperature, the rate of decrease in adhesive strength due to voltage application was large, and the wet heat stability was excellent.
- the electro-peelable pressure-sensitive adhesive layers formed from the pressure-sensitive adhesive compositions of Examples 15 to 21 further contained a tackifying resin, so that the rate of decrease in adhesive strength due to voltage application after storage in a high-temperature and high-humidity environment was reduced. Further improvements were seen.
- Adhesive sheet 1 Electro-peeling adhesive layer 2 Adhesive layer 3 Base material 4 Conductive layer 5 Conductive base material
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Abstract
Description
特許文献1の電気剥離型粘着シートでは、電圧の印加により、陰極側ではイオン液体のカチオンが移動して還元が起こり、陽極側ではイオン液体のアニオンが移動して酸化が起こり、接着界面の接着力が弱くなり、剥離しやすくなるものと考えられる。
本発明者らが更に検討を重ねた結果、以下の知見を得た。
ベースポリマーに加え、Tgが40~180℃である重合体を更に含有させることにより、高温高湿環境下での保管後においても電気剥離性が良好であること、即ち、電圧印加による接着力の低下率が大きいことを見出した。
〔1〕
第1の重合体と、イオン液体とを含有する粘着剤組成物であって、
前記第1の重合体をベースポリマーとして含み、
ガラス転移温度(Tg)が40~180℃である第2の重合体を更に含む、粘着剤組成物。
〔2〕
前記第1の重合体と前記第2の重合体のHSP値差が0~3である、〔1〕に記載の粘着剤組成物。
〔3〕
前記第2の重合体が有機高分子化合物を含み、前記第2の重合体における前記有機高分子化合物の含有量は、前記第1の重合体100質量部に対して1~50質量部である、〔1〕に記載の粘着剤組成物。
〔4〕
前記イオン液体のアニオンは、ビス(フルオロスルホニル)イミドアニオン、及びビス(トリフルオロメタンスルホニル)イミドアニオンからなる群より選択される少なくとも1種を含む、〔1〕に記載の粘着剤組成物。
〔5〕
前記イオン液体のカチオンは、窒素含有オニウムカチオン、硫黄含有オニウムカチオン、及びリン含有オニウムカチオンからなる群より選択される少なくとも1種を含む、〔1〕に記載の粘着剤組成物。
〔6〕
前記イオン液体の含有量は、前記第1の重合体100質量部に対して0.5質量部以上30質量部以下である、〔1〕に記載の粘着剤組成物。
〔7〕
前記第1の重合体は、ポリエステル系ポリマー、ウレタン系ポリマー、並びに、カルボキシル基、アルコキシ基、ヒドロキシル基及び/又はアミド結合を有するアクリル系ポリマーからなる群より選ばれる少なくとも1種を含む、〔1〕に記載の粘着剤組成物。
〔8〕
前記第2の重合体が粘着付与樹脂を含む、〔1〕に記載の粘着剤組成物。
〔9〕
前記粘着付与樹脂の軟化点が100℃以上である、〔8〕に記載の粘着剤組成物。
〔10〕
前記粘着付与樹脂の含有量は、前記第1の重合体100質量部に対して1~50質量部である、〔8〕に記載の粘着剤組成物。
〔11〕
前記粘着付与樹脂がテルペン系粘着付与樹脂又はロジン系粘着付与樹脂である、〔8〕に記載の粘着剤組成物。
〔12〕
電気剥離用である、〔1〕に記載の粘着剤組成物。
〔13〕
〔1〕~〔12〕のいずれか一つに記載の粘着剤組成物から形成された粘着剤層を備える、粘着シート。
〔14〕
〔13〕に記載の粘着シートと、導電性の材料とを備え、
前記粘着剤層が前記導電性の材料に貼着した接合体。
本発明の実施形態に係る粘着剤組成物は、第1の重合体と、イオン液体とを含有する粘着剤組成物であって、前記第1の重合体をベースポリマーとして含み、更に、Tgが40~180℃である第2の重合体を含む。
本発明の実施形態に係る粘着剤組成物は、好ましくは電気剥離用である。
以下、粘着剤組成物について説明する。
本実施形態に係る粘着剤組成物におけるベースポリマーとは、粘着剤組成物に含まれるポリマーにおける主成分をいう。また、この明細書において「主成分」とは、特記しない場合、50質量%を超えて含まれる成分を指す。
なお、本明細書において電圧非印加時の接着力のことを「初期接着力」ということがある。
また、粘着剤組成物に含まれる成分のうちイオン液体以外の成分からなる組成物のことを「イオン液体非含有粘着剤組成物」ということがある。
また、イオン液体非含有粘着剤組成物により形成される粘着剤層のことを「イオン液体非含有粘着剤層」ということがある。
また、電圧印加により接着力が低下する性質のことを「電気剥離性」といい、電圧印加による接着力の低下率が大きいことを「電気剥離性に優れる」などということがある。
(第1の重合体(ベースポリマー))
本発明の実施形態に係る粘着剤組成物は、ベースポリマーとして第1の重合体を含有する。本発明の実施形態においてベースポリマーは、一般的な有機高分子化合物であれば特に制限されず、たとえば、モノマーの重合物又は部分重合物である。モノマーは、1種のモノマーであっても、2種以上のモノマー混合物であってもよい。なお、部分重合物とは、モノマー又はモノマー混合物のうちの少なくとも一部が部分的に重合している重合物を意味する。
上記ポリマーは、単独で又は2種以上組み合わせて用いることができる。
すなわち、本発明の実施形態に係る粘着剤組成物は、アクリル系ポリマーをベースポリマーとして含むアクリル系粘着剤組成物であることが好ましい。
CH2=C(Ra)COORb (1)
[式(1)中のRaは、水素原子又はメチル基であり、Rbは炭素数1~14のアルキル基である]
多価カルボン酸モノマーは、単独で又は2種以上組み合わせて用いることができる。
多価アルコールモノマーは、単独で又は2種以上組み合わせて用いることができる。
(重量平均分子量測定条件)
・サンプル濃度:0.2質量%(テトラヒドロフラン溶液)
・サンプル注入量:10μL
・サンプルカラム:TSKguardcolumn SuperHZ-H(1本)+TSKgel SuperHZM-H(2本)
・リファレンスカラム:TSKgel SuperH-RC(1本)
・溶離液:テトラヒドロフラン(THF)
・流量:0.6mL/min
・検出器:示差屈折計(RI)
・カラム温度(測定温度):40℃
1/Tg=Σ(Wi/Tgi)
なお、上記Foxの式において、Tgは共重合体のガラス転移温度(単位:K)、Wiは該共重合体におけるモノマーiの重量分率(重量基準の共重合割合)、Tgiはモノマーiのホモポリマーのガラス転移温度(単位:K)を表す。
n-ブチルアクリレート -55℃
メチルメタクリレート 105℃
メチルアクリレート 8℃
シクロヘキシルメタクリレート 66℃
N-ビニル-2-ピロリドン 54℃
4-ヒドロキシブチルアクリレート -40℃
イソボルニルメタクリレート 180℃
アクリル酸 106℃
アクリロイルモルフォリン(ACMO) 145℃
本発明の実施形態に係る粘着剤組成物は、更に、ガラス転移温度(Tg)が40~180℃である第2の重合体を含む。
本発明の実施形態に係る粘着剤組成物は、ガラス転移温度(Tg)が40~180℃である第2の重合体を含むことにより、弾性率向上の効果が得られ、電圧非印加時には優れた接着力を発揮し、高温高湿環境下での保管後においても電圧の印加により十分に接着力が低下する、湿熱安定性に優れた粘着剤層を形成することができる。
第2の重合体におけるガラス転移温度(Tg)については、第1の重合体におけるガラス転移温度(Tg)と同様の方法により算出できる。
また、第2の重合体におけるガラス転移温度(Tg)は、第2の重合体を構成するモノマーの種類や配合量等により調整することができる。
第2の重合体に含まれる有機高分子化合物としては、例えば、アクリル系ポリマー、ゴム系ポリマー、ビニルアルキルエーテル系ポリマー、シリコーン系ポリマー、ポリエステル系ポリマー、ポリアミド系ポリマー、ウレタン系ポリマー、フッ素系ポリマー、エポキシ系ポリマー等が挙げられる。
なお、本明細書において、第2の重合体における有機高分子化合物とは、モノマーの重合物又は部分重合物である化合物を指し、粘着付与樹脂及び第1の重合体とは異なる成分を指す。
テルペンフェノール樹脂とは、テルペン残基およびフェノール残基を含むポリマーを指し、テルペン類とフェノール化合物との共重合体(テルペン-フェノール共重合体樹脂)と、テルペン類の単独重合体または共重合体をフェノール変性したもの(フェノール変性テルペン樹脂)との双方を包含する概念である。このようなテルペンフェノール樹脂を構成するテルペン類としては、例えば、α-ピネン、β-ピネン、リモネン(d体、l体およびd/l体(ジペンテン)を包含する)などのモノテルペン類などが挙げられる。
水素添加テルペンフェノール樹脂とは、このようなテルペンフェノール樹脂を水素化した構造を有する水素添加テルペンフェノール樹脂をいい、水添テルペンフェノール樹脂と称されることもある。
アルキルフェノール樹脂は、アルキルフェノールとホルムアルデヒドから得られる樹脂(油性フェノール樹脂)である。アルキルフェノール樹脂としては、例えば、ノボラックタイプおよびレゾールタイプが挙げられる。
ロジンフェノール樹脂としては、例えば、ロジン類または各種ロジン誘導体(ロジンエステル類、不飽和脂肪酸変性ロジン類および不飽和脂肪酸変性ロジンエステル類を包含する)のフェノール変性物などが挙げられる。ロジンフェノール樹脂としては、例えば、ロジン類または各種ロジン誘導体にフェノールを酸触媒で付加させ熱重合する方法等により得られるロジンフェノール樹脂などが挙げられる。
テルペン樹脂としては、α-ピネン、β-ピネン、d-リモネン、l-リモネン、ジペンテンなどのテルペン類(典型的にはモノテルペン類)の重合体などが挙げられる。1種のテルペン類の単独重合体としては、例えば、α-ピネン重合体、β-ピネン重合体、ジペンテン重合体などが挙げられる。
ロジン類としては、例えば、ガムロジン、ウッドロジン、トール油ロジンなどの未変性ロジン(生ロジン);これらの未変性ロジンを水素添加、不均化、重合等により変性した変性ロジン(水素添加ロジン、不均化ロジン、重合ロジン、その他の化学的に修飾されたロジンなど);などが挙げられる。
ロジンエステル類としては、例えば、未変性ロジンまたは変性ロジン(例えば、水素添加ロジン、不均化ロジン、重合ロジンなど)のメチルエステル、トリエチレングリコールエステル、グリセリンエステル、ペンタエリスリトールエステル、マレイン酸エステルなどが挙げられる。
本発明の実施形態において、第2の重合体における有機高分子化合物として用いるアクリル系ポリマーは、市販のものを使用してもよいが、アクリル系のモノマー成分を重合して得てもよい。
本発明の実施形態に係る第2の重合体における有機高分子化合物を重合する方法としては、例えば、溶液重合方法、乳化重合方法、塊状重合方法、活性エネルギー線照射による重合方法(活性エネルギー線重合方法)などが挙げられる。これらの中でも、好ましくは、塊状重合方法、溶液重合方法であり、より好ましくは、溶液重合方法である。
第2の重合体における有機高分子化合物の含有量は、第1の重合体100質量部に対して1~50質量部であってもよい。
HSP値は、公知の値を用いてもよいし、パソコンソフトHSPiP(出典:http://www.hansen-solubility.com/index.html)等を使用して算出してもよい。
本発明の実施形態におけるイオン液体は、一対のアニオンとカチオンから構成され、25℃で液体である溶融塩(常温溶融塩)であれば特に限定されない。以下にアニオン及びカチオンの例を挙げるが、これらを組み合わせて得られるイオン性物質のうち、25℃で液体であるものがイオン液体であり、25℃で固体であるものはイオン液体ではなく、後述のイオン性固体である。
本発明の実施形態に係る粘着剤組成物は、必要に応じて本発明の効果を損なわない範囲で、ポリマー及びイオン液体以外の成分(以下、「その他の成分」と称する場合がある)を1種又は2種以上含有することができる。以下、本発明の実施形態に係る粘着剤組成物に含有され得るその他の成分について説明する。
腐食防止剤の総含有量(配合量)は、第1の重合体100質量部に対して、0.01質量部以上30質量部以下が好ましい。
酸化防止剤としては、例えば、ブチルヒドロキシトルエン(BHT)、およびブチルヒドロキシアニソール(BHA)等が挙げられる。
顔料としては、例えば、二酸化チタン、酸化亜鉛、群青、ベンガラ、リトポン、鉛、カドミウム、鉄、コバルト、アルミニウム、塩酸塩、硫酸塩等の無機顔料、アゾ顔料、および銅フタロシアニン顔料等の有機顔料等が挙げられる。
接着付与剤としては、例えば、チタンカップリング剤、およびジルコニウムカップリング剤等が挙げられる。
帯電防止剤としては、一般的に、第4級アンモニウム塩、あるいはポリグリコール酸やエチレンオキサイド誘導体等の親水性化合物等が挙げられる。
本発明の実施形態に係る粘着剤組成物の接着力は種々の方法で評価することができるが、例えば実施例の欄に記載の180°ピール試験により評価できる。
接着力低下率(%)={1-(電圧印加中の接着力/初期接着力)}×100 (C)
印加電圧は、1V以上であることが好ましく、3V以上であることがより好ましく、6V以上であることがさらに好ましい。また、100V以下であることが好ましく、50V以下であることがより好ましく、30V以下であることがさらに好ましく、15V以下であることが特に好ましい。
電圧印加時間は、60秒以下であることが好ましく、40秒以下であることがより好ましく、20秒以下であることがさらに好ましく、10秒以下であることが特に好ましい。このような場合、作業性に優れる。また、印加時間は短いほどよいが、通常1秒以上である。
本発明の粘着剤組成物は、特に制限されないが、ポリマー、イオン液体、添加剤、および必要に応じて配合する、架橋剤、ポリエチレングリコール、導電性フィラー等を適宜撹拌して混合することで製造することができる。
(粘着シートの構成)
本発明の実施形態に係る粘着シートは、上述の本発明の実施形態に係る粘着剤組成物から形成される粘着剤層(以下「電気剥離型粘着剤層」ともいう)を少なくとも一層有する限り特に制限されない。本発明の実施形態に係る粘着シートは、電気剥離型粘着剤層以外の、イオン液体を含有しない粘着剤層(以下、「その他の粘着剤層」と称する場合がある)を有していてもよい。本発明の実施形態に係る粘着シートは、上記以外に基材、導電層、通電用基材、中間層、および下塗り層等を有していてもよい。本発明の実施形態に係る粘着シートは、例えば、ロール状に巻回された形態や、シート状の形態であってもよい。なお、「粘着シート」には、「粘着テープ」の意味も含むものとする。即ち、本発明の実施形態に係る粘着シートは、テープ状の形態を有する粘着テープであってもよい。
本実施形態の電気剥離型粘着シートは、さらにコート層を備えることにより電気剥離型粘着剤層に含まれるイオン液体が電圧印加により導電層へ侵入する障壁となり、導電層が基材から剥がれることを防ぐ効果を奏する。
また、コート層が電気剥離型粘着剤層と接していることにより電気剥離型粘着剤層と導電層との密着力を向上させることとなり、高温環境下に曝された電気剥離型粘着剤層の熱硬化により、電気剥離型粘着剤層と導電性の材料(例えば被着体等)との界面接着力が低下し電気剥離型粘着シート内で剥がれてしまうことを防ぐ効果を奏する。
コート層はポリエステル系樹脂、アクリル系樹脂、エポキシ系樹脂、ウレタン系樹脂より選択される少なくとも一種の樹脂、又はSiNx、SiOx、Al2O3、Ni、NiCrより選択される少なくとも一種の無機物を含むことが好ましい。
本発明の実施形態に係る粘着シートの製造方法は、公知乃至慣用の製造方法を用いることができる。本発明の実施形態に係る粘着シートにおける電気剥離型粘着剤層は、本発明の実施形態に係る粘着剤組成物を必要に応じて溶剤に溶した溶液を、はく離ライナー上に塗布し、乾燥及び/又は硬化する方法等が挙げられる。また、その他の粘着剤層は、イオン液体及び添加剤を含まない粘着剤組成物を必要に応じて溶剤に溶した溶液を、はく離ライナー上に塗布し、乾燥及び/又は硬化する方法等が挙げられる。なお、溶剤及びはく離ライナーは、上記で挙げたものを使用することができる。
本発明の実施形態に係る粘着シートの被着体からの剥離は、電気剥離型粘着剤層への電圧の印加により、電気剥離型粘着剤層の厚み方向に電位差を生じさせることにより行うことができる。
例えば、粘着シートX1を導電性の被着体に貼付した接合体は、導電性の被着体に通電し、電気剥離型粘着剤層に電圧を印加することにより剥離することができる。
粘着シートX2において電気剥離型粘着剤層側が金属被着面を有する被着体である場合、該導電性被着体と導電層4に通電し、電気剥離型粘着剤層に電圧を印加することにより剥離することができる。
粘着シートX3の場合、両面の導電層4に通電し、電気剥離型粘着剤層に電圧を印加することにより剥離することができる。
通電は、電気剥離型粘着剤層全体に電圧がかかるよう、粘着シートの一端と他方の端に端子をつないで行うことが好ましい。なお、上記の一端と他方の端は、被着体が金属被着面を有する場合、金属被着面を有する被着体の一部であってもよい。なお、剥離の際に、金属被着面と電気剥離型粘着剤層の界面に水を添加してから電圧を印加してもよい。
従来の再剥離技術としては、紫外線(UV)照射により硬化させて剥離する粘着剤層や熱により剥離する粘着剤層がある。このような粘着剤層を用いた粘着シートでは、紫外線(UV)照射が困難である場合や熱により被着体である部材にダメージが生じる場合などは使用できない。上記電気剥離型粘着剤層を備える本発明の実施形態に係る粘着シートは、紫外線や熱を使用しないため、被着体である部材を傷めずに、電圧を印加することで容易に剥離が可能である。
上記特性により、本発明の実施形態に係る粘着シートは、スマートフォン、携帯電話、ノートパソコン、ビデオカメラ、デジタルカメラ等のモバイル端末に使用される二次電池(例えば、リチウムイオン電池パック)の筐体への固定用途に好適である。また、本発明の実施形態に係る粘着シートは、車載用部材(例えば、電池、モーター等)の固定用途に好適である。そして、本発明の実施形態に係る粘着シートは、半導体製造プロセス及び検査における固定用途(例えば、セラミックコンデンサやリチウムイオンバッテリー等)に好適である。さらに、本発明の実施形態に係る粘着シートは、金属加工プロセスにおける保護用途(例えば、鉄道向けステンレス板等)に好適である。
本発明の実施形態に係る接合体は、本発明の実施形態に係る粘着シートと、導電性の材料とを備え、粘着シートにおける電気剥離型粘着剤層が導電性の材料に貼着した接合体である。
導電性の材料は金属被着面を有する被着体であることが好ましく、金属被着面を有する被着体としては、例えば、アルミニウム、銅、鉄、マグネシウム、スズ、金、銀、および鉛等を主成分とする金属からなるものが挙げられ、なかでもアルミニウムを含む金属が好ましい。
<1>
第1の重合体と、イオン液体とを含有する粘着剤組成物であって、
前記第1の重合体をベースポリマーとして含み、
ガラス転移温度(Tg)が40~180℃である第2の重合体を更に含む、粘着剤組成物。
<2>
前記第1の重合体と前記第2の重合体のHSP値差が0~3である、<1>に記載の粘着剤組成物。
<3>
前記第2の重合体が有機高分子化合物を含み、前記第2の重合体における前記有機高分子化合物の含有量は、前記第1の重合体100質量部に対して1~50質量部である、<1>又は<2>に記載の粘着剤組成物。
<4>
前記イオン液体のアニオンは、ビス(フルオロスルホニル)イミドアニオン、及びビス(トリフルオロメタンスルホニル)イミドアニオンからなる群より選択される少なくとも1種を含む、<1>~<3>のいずれか一つに記載の粘着剤組成物。
<5>
前記イオン液体のカチオンは、窒素含有オニウムカチオン、硫黄含有オニウムカチオン、及びリン含有オニウムカチオンからなる群より選択される少なくとも1種を含む、<1>~<4>のいずれか一つに記載の粘着剤組成物。
<6>
前記イオン液体の含有量は、前記第1の重合体100質量部に対して0.5質量部以上30質量部以下である、<1>~<5>のいずれか一つに記載の粘着剤組成物。
<7>
前記第1の重合体は、ポリエステル系ポリマー、ウレタン系ポリマー、並びに、カルボキシル基、アルコキシ基、ヒドロキシル基及び/又はアミド結合を有するアクリル系ポリマーからなる群より選ばれる少なくとも1種を含む、<1>~<6>のいずれか一つに記載の粘着剤組成物。
<8>
前記第2の重合体が粘着付与樹脂を含む、<1>~<7>のいずれか一つに記載の粘着剤組成物。
<9>
前記粘着付与樹脂の軟化点が100℃以上である、<8>に記載の粘着剤組成物。
<10>
前記粘着付与樹脂の含有量は、前記第1の重合体100質量部に対して1~50質量部である、<8>又は<9>に記載の粘着剤組成物。
<11>
前記粘着付与樹脂がテルペン系粘着付与樹脂又はロジン系粘着付与樹脂である、<8>~<10>のいずれか一つに記載の粘着剤組成物。
<12>
電気剥離用である、<1>~<11>のいずれか一つに記載の粘着剤組成物。
<13>
<1>~<12>のいずれか一つに記載の粘着剤組成物から形成された粘着剤層を備える、粘着シート。
<14>
<13>に記載の粘着シートと、導電性の材料とを備え、
前記粘着剤層が前記導電性の材料に貼着した接合体。
(アクリル系ポリマー1溶液の作製)
モノマー成分として、n-ブチルアクリレート(BA):87質量部、2-メトキシエチルアクリレート(MEA):10質量部、アクリル酸(AA):3質量部、及び重合溶媒として酢酸エチル:150質量部を、セパラブルフラスコに投入し、窒素ガスを導入しながら1時間攪拌した。このようにして重合系内の酸素を除去した後、重合開始剤として2,2’-アゾビスイソブチロニトリル(AIBN):0.2質量部を加え、63℃に昇温して6時間反応させた。その後、酢酸エチルを加え、固形分濃度40質量%のアクリル系ポリマー1溶液を得た。得られたアクリル系ポリマー1の重量平均分子量は、75万であった。また、Tgは-45℃であった。
モノマー成分として、n-ブチルアクリレート(BA):95質量部、アクリル酸(AA):5質量部、及び重合溶媒として酢酸エチル:150質量部を、セパラブルフラスコに投入し、窒素ガスを導入しながら1時間攪拌した。このようにして重合系内の酸素を除去した後、重合開始剤として2,2’-アゾビスイソブチロニトリル(AIBN):0.2質量部を加え、63℃に昇温して6時間反応させた。その後、酢酸エチルを加え、固形分濃度40質量%のアクリル系ポリマー2溶液を得た。得られたアクリル系ポリマー2の重量平均分子量は、60万であった。また、Tgは-47℃であった。
(重合体1)
モノマー成分として、シクロヘキシルメタクリレート(CHMA):95質量部、アクリル酸(AA):5質量部、重合溶媒として酢酸エチル:300質量部、及び連鎖移動剤として2-メルカプトエタノール(チオグリコール):3質量部をセパラブルフラスコに投入し、窒素ガスを導入しながら1時間攪拌した。このようにして重合系内の酸素を除去した後、重合開始剤として2,2’-アゾビスイソブチロニトリル(AIBN):0.2質量部を加え、65℃に昇温して3時間反応させ、続いて75℃で2時間反応させて固形分濃度25質量%の重合体1溶液を得た。
モノマー成分として、イソボルニルメタクリレート(IBXMA):100質量部、重合溶媒として酢酸エチル:300質量部、及び連鎖移動剤として2-メルカプトエタノール(チオグリコール):3質量部をセパラブルフラスコに投入し、窒素ガスを導入しながら1時間攪拌した。このようにして重合系内の酸素を除去した後、重合開始剤として2,2’-アゾビスイソブチロニトリル(AIBN):0.2質量部を加え、65℃に昇温して3時間反応させ、続いて75℃で2時間反応させて固形分濃度25質量%の重合体2溶液を得た。
モノマー成分として、シクロヘキシルメタクリレート(CHMA):95質量部、4ヒドロキシルブチルアクリレート(4HBA):5質量部、重合溶媒として酢酸エチル:300質量部、及び連鎖移動剤として2-メルカプトエタノール(チオグリコール):3質量部をセパラブルフラスコに投入し、窒素ガスを導入しながら1時間攪拌した。このようにして重合系内の酸素を除去した後、重合開始剤として2,2’-アゾビスイソブチロニトリル(AIBN):0.2質量部を加え、65℃に昇温して3時間反応させ、続いて75℃で2時間反応させて固形分濃度25質量%の重合体3溶液を得た。
モノマー成分として、シクロヘキシルメタクリレート(CHMA):85質量部、4ヒドロキシルブチルアクリレート(4HBA):15質量部、重合溶媒として酢酸エチル:300質量部、及び連鎖移動剤として2-メルカプトエタノール(チオグリコール):3質量部をセパラブルフラスコに投入し、窒素ガスを導入しながら1時間攪拌した。このようにして重合系内の酸素を除去した後、重合開始剤として2,2’-アゾビスイソブチロニトリル(AIBN):0.2質量部を加え、65℃に昇温して3時間反応させ、続いて75℃で2時間反応させて固形分濃度25質量%の重合体4溶液を得た。
モノマー成分として、メチルアクリレート(MA):55質量部、N―ビニルピロリドン:45質量部、重合溶媒として酢酸エチル:300質量部、及び連鎖移動剤として2-メルカプトエタノール(チオグリコール):3質量部をセパラブルフラスコに投入し、窒素ガスを導入しながら1時間攪拌した。このようにして重合系内の酸素を除去した後、重合開始剤として2,2’-アゾビスイソブチロニトリル(AIBN):0.2質量部を加え、65℃に昇温して3時間反応させ、続いて75℃で2時間反応させて固形分濃度25質量%の重合体7溶液を得た。
上記の方法に従いFox式を用いて算出した。
上記の方法に従いパソコンソフトHSPiPを用いて算出した。
<粘着剤組成物の作製>
第1の重合体として上記で得られたアクリル系ポリマー溶液や、上記で得られた第2の重合体、以下に示す第2の重合体、架橋剤、イオン液体、添加剤等の各成分を表1~2に記載のとおり用いて、撹拌、混合し、固形分濃度25質量%に調整した実施例1~21及び比較例1~4の各電気剥離用粘着剤組成物(溶液)を得た。表1~2に各成分の配合量を示す。
なお、表1~2における各成分の値は、質量部を意味する。また、ポリマーの配合量(質量部)は、ポリマー溶液中の固形分の配合量(質量部)を示す。
上記で得られた電気剥離用粘着剤組成物(溶液)を、表面が剥離処理されたポリエチレンテレフタレートはく離ライナー(商品名「MRF38」、三菱樹脂株式会社製)の剥離処理面上に、アプリケータを用いて均一な厚みとなるように塗布した。次に、150℃で3分間の加熱乾燥を行い、表面が剥離処理されたポリエチレンテレフタレートはく離ライナー(商品名「MRE38」、三菱樹脂株式会社製)の剥離処理面をハンドローラーを用いて粘着剤層上にラミネートし、厚み50μmの電気剥離型粘着剤層(粘着シート)を得た。
得られた電気剥離型粘着剤層(粘着シート)を10mm×80mmのサイズのシートとし、のMREはく離ライナーを剥がし、露出した電気剥離型粘着剤層面に、金属層つきフィルム(商品名「1005CR」、東レ株式会社製、厚み12μm、サイズ10mm×100mm)を貼り合わせ、基材付き片面粘着シートとした。
基材付き片面粘着シートのはく離ライナーを剥がし、剥がした面に被着体としてステンレス板(SUS316、サイズ:30mm×120mm)を当該粘着シートの一端が2mm程度被着体からはみ出すように貼り付け、2kgのローラーで1往復押圧し、23℃の環境下で30分間放置し、ステンレス板6/電気剥離型粘着剤層(粘着シート)1’/金属層付きフィルム(通電用基材)5’からなる接合体を得た。当該接合体の概要を図4に示す。
(180°剥離力)
実施例及び比較例の接合体を用いて180°ピール試験を行った。用いた被着材はステンレス板(SUS304、サイズ:30mm×120mm)であった。
剥離試験機(商品名「変角度ピール試験機YSP」、旭精工株式会社製)にて、図4中の矢印方法にピールし、180°ピール試験(引張速度:300mm/min、剥離温度23℃)における接着力を測定し、180°剥離力を測定し、これを初期接着力とした。測定結果を表1~2に示す。
接合体を2kgのローラーで1往復押圧して作製し23℃の環境下で30分間放置した後に、ピールの前に接合体の図4におけるαとβの箇所に直流電流機のマイナス極及びプラス極の電極をそれぞれ取り付け、電圧30Vにて30秒間電圧印加を行い、そのまま電圧を印加しながら、上記の180°剥離力測定と同様にしてピールし、電圧印加中の接着力を測定し初期電気剥離力とした。測定結果を表1~2に示す。
また、上記で測定した初期接着力及び電圧印加中の接着力から、下記の式(C)により接着力低下率を算出した。結果を表1~2に示す。
接着力低下率(%)={1-(電圧印加中の接着力/初期接着力)}×100 (C)
2kgのローラーで1往復押圧した後に、60℃、90%RHの環境下で500時間保管した後に取り出し、熱を冷ますため22℃50%RHに60分静置した後に測定を行った点、及び、ピールの前に接合体の図4におけるαとβの箇所に直流電流機のマイナス極及びプラス極の電極をそれぞれ取り付け、電圧30Vにて30秒間電圧印加を行い、そのまま電圧を印加しながら、上記の180°剥離力測定と同様にしてピールし、電圧印加中の接着力を測定し湿熱保管後の電気剥離力とした。測定結果を表1~2に示す。
重合体5:アクリル系ポリマー、商品名「ARUFON UC3000」、東亞合成株式会社製
重合体6:アクリル系ポリマー、商品名「ARUFON UH2170」、東亞合成株式会社製
YSポリスター T-115:テルペン系粘着付与樹脂、ヤスハラケミカル株式会社製、Tg=65℃、軟化点115℃
YSポリスター U-130:テルペン系粘着付与樹脂、ヤスハラケミカル株式会社製、Tg=80℃、軟化点130℃
ペンセルD125:ロジン系粘着付与樹脂、荒川化学工業株式会社製、Tg=75℃、軟化点125℃
ペンセルD160:ロジン系粘着付与樹脂、荒川化学工業株式会社製、Tg=110℃、軟化点160℃
AS-110:カチオン:1-エチル-3-メチルイミダゾリウムカチオン、アニオン:ビス(フルオロスルホニル)イミドアニオン、商品名「エレクセルAS-110」、第一工業製薬株式会社製
V-05:ポリカルボジイミド樹脂、商品名「カルボジライト V-05」、日清紡ケミカル株式会社製
AMINE O:2-(8-ヘプタデセン-1-イル)-4,5-ジヒドロ-1H-イミダゾール-1-エタノール、商品名「AMINE O」、BASFジャパン株式会社製
Irgacor DSSG:セバシン酸ナトリウム、商品名「Irgacor DSSG」、BASFジャパン株式会社製
Irgamet 30:N,N-ビス(2-エチルヘキシル)-[(1,2,4-トリアゾール-1-イル)メチル]アミン、商品名「Irgamet 30」BASFジャパン株式会社製
EMIM-MeSO3:東京化成工業株式会社製
1 電気剥離型粘着剤層
2 粘着剤層
3 基材
4 導電層
5 通電用基材
Claims (14)
- 第1の重合体と、イオン液体とを含有する粘着剤組成物であって、
前記第1の重合体をベースポリマーとして含み、
ガラス転移温度(Tg)が40~180℃である第2の重合体を更に含む、粘着剤組成物。 - 前記第1の重合体と前記第2の重合体のHSP値差が0~3である、請求項1に記載の粘着剤組成物。
- 前記第2の重合体が有機高分子化合物を含み、前記第2の重合体における前記有機高分子化合物の含有量は、前記第1の重合体100質量部に対して1~50質量部である、請求項1に記載の粘着剤組成物。
- 前記イオン液体のアニオンは、ビス(フルオロスルホニル)イミドアニオン、及びビス(トリフルオロメタンスルホニル)イミドアニオンからなる群より選択される少なくとも1種を含む、請求項1に記載の粘着剤組成物。
- 前記イオン液体のカチオンは、窒素含有オニウムカチオン、硫黄含有オニウムカチオン、及びリン含有オニウムカチオンからなる群より選択される少なくとも1種を含む、請求項1に記載の粘着剤組成物。
- 前記イオン液体の含有量は、前記第1の重合体100質量部に対して0.5質量部以上30質量部以下である、請求項1に記載の粘着剤組成物。
- 前記第1の重合体は、ポリエステル系ポリマー、ウレタン系ポリマー、並びに、カルボキシル基、アルコキシ基、ヒドロキシル基及び/又はアミド結合を有するアクリル系ポリマーからなる群より選ばれる少なくとも1種を含む、請求項1に記載の粘着剤組成物。
- 前記第2の重合体が粘着付与樹脂を含む、請求項1に記載の粘着剤組成物。
- 前記粘着付与樹脂の軟化点が100℃以上である、請求項8に記載の粘着剤組成物。
- 前記粘着付与樹脂の含有量は、前記第1の重合体100質量部に対して1~50質量部である、請求項8に記載の粘着剤組成物。
- 前記粘着付与樹脂がテルペン系粘着付与樹脂又はロジン系粘着付与樹脂である、請求項8に記載の粘着剤組成物。
- 電気剥離用である、請求項1に記載の粘着剤組成物。
- 請求項1~12のいずれか一項に記載の粘着剤組成物から形成された粘着剤層を備える、粘着シート。
- 請求項13に記載の粘着シートと、導電性の材料とを備え、
前記粘着剤層が前記導電性の材料に貼着した接合体。
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JP2006342191A (ja) * | 2005-06-07 | 2006-12-21 | Nitto Denko Corp | 粘着剤組成物および粘着シート類 |
JP2007051271A (ja) | 2005-07-21 | 2007-03-01 | Nitto Denko Corp | 粘着剤組成物、両面粘着テープ、接着方法及び携帯用電子機器 |
JP2016065209A (ja) * | 2014-09-25 | 2016-04-28 | 日東電工株式会社 | 熱剥離型粘着シート |
WO2017064918A1 (ja) | 2015-10-16 | 2017-04-20 | 日東電工株式会社 | 電気剥離用粘着剤組成物、粘着シート、及び接合体 |
JP2020164778A (ja) | 2018-09-03 | 2020-10-08 | 日東電工株式会社 | 粘着剤組成物、粘着シート、及び接合体 |
JP2021161475A (ja) | 2020-03-31 | 2021-10-11 | 日本製鉄株式会社 | クラッド材とその製造方法 |
JP2022026640A (ja) | 2020-07-31 | 2022-02-10 | 旭精工株式会社 | コイン処理装置 |
WO2022065483A1 (ja) * | 2020-09-28 | 2022-03-31 | リンテック株式会社 | 電気剥離性粘着剤組成物、電気剥離性粘着シート、及び電気剥離性粘着シートの使用方法 |
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- 2022-09-28 JP JP2023551604A patent/JPWO2023054478A1/ja active Pending
- 2022-09-28 KR KR1020247010389A patent/KR20240068664A/ko unknown
- 2022-09-30 TW TW111137260A patent/TW202330854A/zh unknown
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JP2006342191A (ja) * | 2005-06-07 | 2006-12-21 | Nitto Denko Corp | 粘着剤組成物および粘着シート類 |
JP2007051271A (ja) | 2005-07-21 | 2007-03-01 | Nitto Denko Corp | 粘着剤組成物、両面粘着テープ、接着方法及び携帯用電子機器 |
JP2016065209A (ja) * | 2014-09-25 | 2016-04-28 | 日東電工株式会社 | 熱剥離型粘着シート |
WO2017064918A1 (ja) | 2015-10-16 | 2017-04-20 | 日東電工株式会社 | 電気剥離用粘着剤組成物、粘着シート、及び接合体 |
JP2020164778A (ja) | 2018-09-03 | 2020-10-08 | 日東電工株式会社 | 粘着剤組成物、粘着シート、及び接合体 |
JP2021161475A (ja) | 2020-03-31 | 2021-10-11 | 日本製鉄株式会社 | クラッド材とその製造方法 |
JP2022026640A (ja) | 2020-07-31 | 2022-02-10 | 旭精工株式会社 | コイン処理装置 |
WO2022065483A1 (ja) * | 2020-09-28 | 2022-03-31 | リンテック株式会社 | 電気剥離性粘着剤組成物、電気剥離性粘着シート、及び電気剥離性粘着シートの使用方法 |
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EP4410916A1 (en) | 2024-08-07 |
KR20240068664A (ko) | 2024-05-17 |
JPWO2023054478A1 (ja) | 2023-04-06 |
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