WO2020050169A1 - Adhesive composition, adhesive sheet and bonded body - Google Patents
Adhesive composition, adhesive sheet and bonded body Download PDFInfo
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- WO2020050169A1 WO2020050169A1 PCT/JP2019/034143 JP2019034143W WO2020050169A1 WO 2020050169 A1 WO2020050169 A1 WO 2020050169A1 JP 2019034143 W JP2019034143 W JP 2019034143W WO 2020050169 A1 WO2020050169 A1 WO 2020050169A1
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- pressure
- sensitive adhesive
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- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/064—Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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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
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.
- a double-sided pressure-sensitive adhesive sheet having a certain adhesive force and a certain releasability may be used for joining members in an electronic component manufacturing process or the like.
- Patent Documents 1 to 3 As a double-sided pressure-sensitive adhesive sheet realizing the above-mentioned adhesive strength and peelability, a pressure-sensitive adhesive sheet which is peeled off by applying a voltage to the pressure-sensitive adhesive layer using an ionic liquid composed of a cation and an anion as a component forming the pressure-sensitive adhesive composition (Electrically peelable pressure-sensitive adhesive sheets) are known (Patent Documents 1 to 3).
- Application of a voltage causes cations of the ionic liquid to move on the cathode side to cause reduction, and anions of the ionic liquid to move on the anode side to cause oxidation. It is considered that the adhesive strength of the resin is weakened and the film is easily peeled off.
- JP 2010-037354 A Japanese Patent No. 6097112 Japanese Patent No. 4,139,851
- the electro-peelable pressure-sensitive adhesive sheet can strongly bond the members when no voltage is applied, and can be peeled off with a small force when a voltage is applied. Therefore, it is preferable that the rate of decrease in the adhesive force due to voltage application is large in the electrically peelable pressure-sensitive adhesive sheet.
- a low humidity environment such as in winter, for example, there has been a problem that the rate of decrease in adhesive strength due to voltage application is small.
- the present invention has been completed in view of the above, and includes a pressure-sensitive adhesive composition and a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition, the adhesion of which is sufficiently reduced by application of a voltage even in a low humidity environment. It is intended to provide an adhesive sheet.
- the rate of decrease in adhesive strength due to voltage application in a low humidity environment decreases because the moisture content of the pressure-sensitive adhesive layer decreases in a low humidity environment, and the cation and anion of the ionic liquid are reduced. Is difficult to move.
- the relative permittivity of components other than the ionic liquid in the pressure-sensitive adhesive layer has a correlation with the rate of decrease in adhesive force due to voltage application. By increasing the relative permittivity, the rate of decrease in adhesive force due to voltage application Can be increased.
- the ionic conductivity of the pressure-sensitive adhesive layer and the capacitance per unit area of the interface between the pressure-sensitive adhesive layer and the adherend have a correlation with the rate of decrease in adhesive force due to voltage application, and the ionic conductivity and It has been found that by increasing the capacitance per unit area of the interface between the pressure-sensitive adhesive layer and the adherend, the rate of decrease in adhesive force due to voltage application can be increased.
- One pressure-sensitive adhesive composition of the present invention completed based on the first finding is a pressure-sensitive adhesive composition containing a polymer and an ionic liquid, and among components contained in the pressure-sensitive adhesive composition, other than the ionic liquid
- a pressure-sensitive adhesive layer at a frequency of 100 Hz after the pressure-sensitive adhesive layer is formed by forming a pressure-sensitive adhesive layer from the composition consisting of the following components, and left under an environment of 22 ° C. and 20% RH for 3 days. It is.
- Another pressure-sensitive adhesive composition of the present invention completed on the basis of the second finding is a pressure-sensitive adhesive composition containing a polymer and an ionic liquid, and forms a pressure-sensitive adhesive layer with the pressure-sensitive adhesive composition according to JIS. H4000: A5052P H2014 in 2014 attached to an aluminum plate made of H32 and left for 7 days in an environment of 22 ° C. and 15% RH, the capacitance per unit area of the interface between the pressure-sensitive adhesive layer and the aluminum plate is 0. 9 ⁇ F / cm 2 or more, and the ionic conductivity of the pressure-sensitive adhesive layer is 10 ⁇ S / m or more.
- a pressure-sensitive adhesive layer is formed from the pressure-sensitive adhesive composition, and is adhered to an aluminum plate made of A5052P H32 according to JIS H4000: 2014.
- the capacitance per unit area of the interface between the pressure-sensitive adhesive layer and the aluminum plate after standing for days may be 1.2 ⁇ F / cm 2 or more, and the ionic conductivity of the pressure-sensitive adhesive layer may be 20 ⁇ S / m or more.
- the pressure-sensitive adhesive composition may further include an ionic solid.
- the polymer may include an ionic polymer.
- the polymer is 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.
- a polyester polymer e.g., polyethylene glycol dimethacrylate copolymer
- a urethane polymer e.g., polystyrene-styrenethacrylate
- acrylic polymer having a carboxyl group, an alkoxy group, a hydroxyl group and / or an amide bond.
- One type may be included.
- another pressure-sensitive adhesive composition of the present invention contains a polymer and an ionic liquid, and the ionic liquid is 0.5 to 30 parts by mass and the ionic solid is 0.5 to 10 parts by mass with respect to 100 parts by mass of the polymer.
- Another adhesive composition of the present invention contains a polymer and an ionic liquid, and contains 0.5 to 30 parts by mass of the ionic liquid based on 100 parts by mass of the polymer. And 0.05 to 2 parts by mass.
- Another pressure-sensitive adhesive composition of the present invention is a pressure-sensitive adhesive composition containing 100 parts by mass of an acrylic polymer and 0.5 to 30 parts by mass of an ionic liquid, wherein all monomer components constituting the acrylic polymer are The ratio of the polar group-containing monomer is 0.1 to 35% by mass.
- the pressure-sensitive adhesive composition is for electric stripping.
- the pressure-sensitive adhesive sheet of the present invention includes a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention.
- the joined body of the present invention includes an adherend having a metal adhered surface and the pressure-sensitive adhesive sheet of the present invention, and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the present invention is joined to the metal adhered surface.
- the pressure-sensitive adhesive composition of the present invention has a sufficiently low adhesive strength even under a low humidity environment by application of a voltage.
- FIG. 3 is a top view of a composite sample for measuring capacitance and ionic conductivity.
- FIG. 4 is an equivalent circuit diagram of a composite sample for measuring capacitance and ionic conductivity.
- Each of the pressure-sensitive adhesive compositions of the first and second embodiments of the present invention contains a polymer and an ionic liquid.
- a pressure-sensitive adhesive layer is formed by a composition composed of components other than the ionic liquid among the components included in the pressure-sensitive adhesive composition of the first embodiment, and the pressure-sensitive adhesive layer is placed in an environment of 22 ° C. and 20% RH for 3 days. After standing, the relative permittivity of the pressure-sensitive adhesive layer at a frequency of 100 Hz is 5 or more. Further, a pressure-sensitive adhesive layer was formed from the pressure-sensitive adhesive composition of the second embodiment, attached to an aluminum plate made of A5052P H32 in JIS H4000: 2014, and left for 7 days in an environment of 22 ° C.
- the capacitance per unit area at the interface between the pressure-sensitive adhesive layer and the aluminum plate is 0.9 ⁇ F / cm 2 or more, and the ion conductivity of the pressure-sensitive adhesive layer is 10 ⁇ S / m or more.
- These pressure-sensitive adhesive compositions have a property that the adhesive force is reduced by application of a voltage, and are suitable as pressure-sensitive adhesive compositions for electric stripping.
- the above first and second embodiments are not exclusive, and if there is a pressure-sensitive adhesive composition corresponding to any of the first and second embodiments, an adhesive composition corresponding to only one of them There are also agent compositions. If the pressure-sensitive adhesive composition falls under any one of the first and second embodiments, the effects of the present invention can be obtained. Hereinafter, these pressure-sensitive adhesive compositions will be described.
- the first and second embodiments of the present invention may be collectively referred to as “the present embodiment”.
- the adhesive force when no voltage is applied may be referred to as “initial adhesive force”.
- a composition composed of components other than the ionic liquid among the components contained in the pressure-sensitive adhesive composition may be referred to as “non-ionic liquid-containing pressure-sensitive adhesive composition”.
- the pressure-sensitive adhesive layer formed by the non-ionic liquid-containing pressure-sensitive adhesive composition may be referred to as “non-ionic liquid-containing pressure-sensitive adhesive layer”.
- electro-peeling property the property that the adhesive force is reduced by applying a voltage
- excellent in electro-peeling property the fact that the rate of decrease in the adhesive force by applying a voltage is large.
- the pressure-sensitive adhesive composition of the present embodiment contains a polymer.
- the 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 a monomer.
- the monomer may be a single monomer or a mixture of two or more monomers.
- the partially polymerized product means a polymer in which at least a part of the monomer or the monomer mixture is partially polymerized.
- the polymer in the present embodiment is usually used as an adhesive, and is not particularly limited as long as it has tackiness.
- examples thereof include an acrylic polymer, a rubber polymer, a vinylalkyl ether polymer, a silicone polymer, and a polyester polymer.
- the polymers can be used alone or in combination of two or more. To increase the relative permittivity of components other than the ionic liquid of the obtained pressure-sensitive adhesive layer, and also to increase the ionic conductivity and the capacitance per unit area of the bonding interface of the obtained pressure-sensitive adhesive layer, and to improve the electrical peelability.
- the polymer has a large relative dielectric constant.
- the polymer in the present embodiment particularly includes a polyester-based polymer, a urethane-based polymer, and a carboxyl group, an alkoxy group, a hydroxyl group, and / or an amide bond. It is preferable to include at least one selected from the group consisting of acrylic polymers.
- polyester-based polymers and urethane-based polymers have easily polarizable hydroxyl groups at the terminals
- acrylic polymers having carboxyl groups, alkoxy groups, hydroxyl groups and / or amide bonds include carboxyl groups, alkoxy groups, hydroxyl groups and Since the amide bond is easily polarized, a polymer having a relatively large relative dielectric constant can be obtained by using these polymers.
- the total content of the polyester polymer and the acrylic polymer having a carboxyl group, an alkoxy group, a hydroxyl group and / or an amide bond in the polymer of the present embodiment is preferably 60% by mass or more, and 80% by mass or more. More preferably, it is the above.
- the polymer in the present embodiment is preferably an acrylic polymer. That is, the pressure-sensitive adhesive composition of the present embodiment is preferably an acrylic pressure-sensitive adhesive composition containing an acrylic polymer as a polymer.
- the acrylic polymer preferably contains a monomer unit derived from an alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms (the following formula (1)). Such a monomer unit is suitable for obtaining a large initial adhesive force. Furthermore, the relative permittivity of components other than the ionic liquid of the pressure-sensitive adhesive layer is increased, and the ionic conductivity and the capacitance per unit area of the bonding interface of the obtained pressure-sensitive adhesive layer are increased, thereby improving the electrical peelability.
- the alkyl group Rb preferably has a small carbon number, particularly preferably 8 or less, more preferably 4 or less.
- R a in the formula (1) is a hydrogen atom or a methyl group
- R b is an alkyl group having 1 to 14 carbon atoms.
- alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and 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) A) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (
- alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms can be used alone or in combination of two or more.
- the ratio of the alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms to all the 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 is easy to obtain a large initial adhesive force.
- the acrylic polymer in addition to a monomer unit derived from an alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms, it is used for the purpose of improving cohesion, heat resistance, crosslinkability, and the like. It is preferable to include a monomer unit derived from a copolymerizable polar group-containing monomer.
- the monomer unit can provide a crosslinking point and is suitable for obtaining a large initial adhesive force.
- the relative permittivity of components other than the ionic liquid of the pressure-sensitive adhesive layer is increased, and the ionic conductivity of the obtained pressure-sensitive adhesive layer and the capacitance per unit area of the bonding interface are increased, thereby improving the electrical peelability. From the viewpoint as well, it is preferable to include a monomer unit derived from a polar group-containing monomer.
- Examples of the polar group-containing monomer include a carboxyl group-containing monomer, an alkoxy group-containing monomer, a hydroxyl group-containing monomer, a cyano group-containing monomer, a vinyl group-containing monomer, an aromatic vinyl monomer, an amide group-containing monomer, an imide group-containing monomer, and amino.
- Examples include a group-containing monomer, an epoxy group-containing monomer, a vinyl ether monomer, N-acryloylmorpholine, a sulfo group-containing monomer, a phosphoric acid group-containing monomer, and an acid anhydride group-containing monomer.
- a carboxyl group-containing monomer, an alkoxy group-containing monomer, a hydroxyl group-containing monomer, and an amide group-containing monomer are preferable from the viewpoint of excellent cohesiveness, and a carboxyl group-containing monomer is particularly preferable.
- Carboxyl group-containing monomers are particularly suitable for obtaining a large initial adhesive strength.
- the polar group-containing monomers can be used alone or in combination of two or more.
- carboxyl group-containing monomer examples include acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
- acrylic acid is preferred.
- the carboxyl group-containing monomers can be used alone or in combination of two or more.
- alkoxy group-containing monomer examples include a methoxy group-containing monomer and an ethoxy group-containing monomer.
- methoxy group-containing monomer examples include 2-methoxyethyl acrylate.
- hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 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. Particularly, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable.
- the hydroxyl group-containing monomers can be used alone or in combination of two or more.
- amide group-containing monomer 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, diacetoneacrylamide and the like.
- the amide group-containing monomers can be used alone or in combination of two or more.
- Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.
- vinyl group-containing monomer examples include vinyl esters such as vinyl acetate, vinyl propionate, and vinyl laurate, with vinyl acetate being particularly preferred.
- aromatic vinyl monomer examples include styrene, chlorostyrene, chloromethylstyrene, ⁇ -methylstyrene, and other substituted styrenes.
- Examples of the imide group-containing monomer include cyclohexylmaleimide, isopropylmaleimide, N-cyclohexylmaleimide, and itaconimide.
- amino group-containing monomer examples include, for example, aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and N, N-dimethylaminopropyl (meth) acrylate.
- Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and allyl glycidyl ether.
- vinyl ether monomer examples include methyl vinyl ether, ethyl vinyl ether, and isobutyl vinyl ether.
- the ratio of the polar group-containing monomer to all the monomer components (100% by mass) constituting the acrylic polymer is preferably from 0.1% by mass to 35% by mass.
- the upper limit of the proportion of the polar group-containing monomer is more preferably 25% by mass, further preferably 20% by mass, and the lower limit is more preferably 0.5% by mass, and still more preferably 1% by mass. And particularly preferably 2% by mass.
- the proportion of the polar group-containing monomer is 30% by mass or less, it becomes easy to prevent the pressure-sensitive adhesive layer from being excessively adhered to the adherend and heavy peeling.
- the content is 2% by mass or more and 20% by mass or less, it is easy to achieve both releasability from the adherend and adhesion between the pressure-sensitive adhesive layer and another layer.
- a polyfunctional monomer may be contained in order to introduce a crosslinked structure into the acrylic polymer to easily obtain a necessary cohesive force.
- polyfunctional monomer examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1,6-hexanediol di ( Examples thereof include (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, divinylbenzene, and N, N'-methylenebisacrylamide.
- the polyfunctional monomers can be used alone or in combination of two or more.
- the content of the polyfunctional monomer with respect to all monomer components (100% by mass) constituting the acrylic polymer is preferably from 0.1% by mass to 15% by mass.
- the upper limit of the content of the polyfunctional monomer 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 adhesion of the pressure-sensitive adhesive layer are easily improved, which is preferable.
- the content of the polyfunctional monomer is 15% by mass or less, the cohesive force does not become too high, and it becomes easy to obtain appropriate adhesiveness.
- the polyester-based polymer is typically a polycarboxylic acid such as dicarboxylic acid or a derivative thereof (hereinafter also referred to as “polycarboxylic acid monomer”), a polyhydric alcohol such as a diol or a derivative thereof (hereinafter “polyhydric alcohol monomer”). ”) Is a polymer having a condensed structure.
- the polyvalent carboxylic acid monomer is not particularly limited, but includes, for example, 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, dodecenyl succinic anhydride, fumaric acid, succinic acid, dodecane diacid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, etc., maleic acid, maleic anhydride, itaconic acid, citraconic acid , And derivatives thereof.
- the polycarboxylic acid monomers can be used alone or in combination of two or more.
- the polyhydric alcohol monomer is not particularly restricted but includes, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-butane Diols, 1,3-butanediol, 1,4-butanediol, 1,5-pentaneddiol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, diethylene glycol, diethylene glycol Propylene glycol, 2,2,4-trimethyl-1,5-pentanediol, 2-ethyl-2-butylpropanediol, 1,9-nonanediol, 2-methyloctanediol, 1,10-decanediol, and these And the like can be used.
- the polyhydric alcohol monomers can be used alone or in combination of two or more.
- the polymer of the present embodiment may include an ionic polymer.
- An ionic polymer is a polymer having an ionic functional group.
- the dielectric constant of the polymer is increased, and the electrical stripping property is improved.
- the content of the ionic polymer is preferably 0.05 part by mass or more and 2 parts by mass or less based on 100 parts by mass of the polymer.
- the polymer can be obtained by (co) polymerizing a monomer component.
- the polymerization method is not particularly limited, and examples thereof include solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, and photopolymerization (active energy ray polymerization). Particularly, a solution polymerization method is preferable from the viewpoint of cost and productivity.
- the polymer is copolymerized, it may be any of a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer and the like.
- the solution polymerization method is not particularly limited, and examples thereof include a method of dissolving a monomer component, a polymerization initiator, and the like in a solvent, heating and polymerizing to obtain a polymer solution containing a polymer.
- Various general solvents can be used as the solvent used in the solution polymerization method.
- a solvent polymerization solvent
- examples of such a solvent include aromatic hydrocarbons such as toluene, benzene, and xylene; esters such as ethyl acetate and n-butyl acetate; and n-hexane and n-heptane.
- the solvents can be used alone or in combination of two or more.
- the amount of the solvent used is not particularly limited, but is preferably from 10 parts by mass to 1,000 parts by mass based on all the monomer components (100 parts by mass) constituting the polymer.
- the upper limit of the amount of the 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, and examples thereof include a peroxide-based polymerization initiator and an azo-based polymerization initiator.
- the peroxide-based polymerization initiator is not particularly limited, and examples thereof include peroxycarbonate, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, and peroxyester.
- the azo polymerization initiator is not particularly limited, but includes 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis (2,4- Dimethylvaleronitrile), 2,2'-azobis (2-methylpropionic acid) 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-methylpropionamidi) ) Disulfate, 2,2'-azobis (N, N'-dimethyleneisobutylamidine) hydro
- the amount of the polymerization initiator used is not particularly limited, but is preferably 0.01 part by mass or more and 5 parts by mass or less based on all monomer components (100 parts by mass) constituting the polymer.
- the upper limit of the use amount of the polymerization initiator is more preferably 3 parts by mass, and the lower limit is more preferably 0.05 parts by mass.
- the heating temperature at the time of polymerization by heating in the solution polymerization method is not particularly limited, but is, for example, 50 ° C. or more and 80 ° C. or less.
- 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 polymer is not particularly limited, but is preferably from 100,000 to 5,000,000.
- the upper limit of the weight average molecular weight is more preferably 4,000,000, further preferably 3,000,000, and the lower limit is more preferably 200,000, further preferably 300,000.
- the weight average molecular weight is 100,000 or more, the cohesive force is reduced, and the problem that adhesive residue remains on the surface of the adherend after peeling off the pressure-sensitive adhesive layer can be effectively suppressed.
- 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 peeling the pressure-sensitive adhesive layer becomes insufficient.
- the weight average molecular weight is obtained by measurement by gel permeation chromatography (GPC), and more specifically, for example, as a GPC measuring device, trade name “HLC-8220GPC” (manufactured by Tosoh Corporation) Can be measured under the following conditions, and can be calculated by a standard polystyrene conversion value.
- GPC gel permeation chromatography
- the glass transition temperature (Tg) of the polymer is not particularly limited, but is preferably 0 ° C. or lower, because it can suppress a decrease in initial adhesive strength, more preferably ⁇ 10 ° C. or lower, and still more preferably ⁇ 20 ° C. or lower. It is. Further, it is particularly preferable that the temperature is ⁇ 40 ° C. or lower, since the rate of decrease in adhesive force due to voltage application becomes particularly large, and most preferably ⁇ 50 ° C. or lower.
- the above formula (Y) is a calculation formula in the case where the polymer is composed of n kinds of monomer components of monomer 1, monomer 2,..., Monomer n.
- the glass transition temperature when a homopolymer is formed means the glass transition temperature of a homopolymer of the monomer, and only a certain monomer (sometimes referred to as “monomer X”) is formed as a monomer component. It means the glass transition temperature (Tg) of the polymer. Specifically, numerical values are listed in "Polymer Handbook” (3rd edition, John Wiley & Sons, Inc., 1989). The glass transition temperature (Tg) of a homopolymer not described in the literature refers to, for example, a value obtained by the following measurement method.
- a reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser was charged with 100 parts by mass of monomer X, 0.2 parts by mass of 2,2'-azobisisobutyronitrile, and 200 parts by mass of ethyl acetate as a polymerization solvent.
- a mass part is charged and stirred for 1 hour while introducing nitrogen gas.
- the temperature is raised to 63 ° C. and the reaction is performed for 10 hours.
- the mixture is cooled to room temperature to obtain a homopolymer solution having a solid content of 33% by mass.
- the homopolymer solution is cast on a release liner and dried to prepare a test sample (sheet-like homopolymer) having a thickness of about 2 mm. Then, about 1-2 mg of this test sample was weighed into an aluminum open cell, and a nitrogen atmosphere of 50 ml / min was measured using a temperature-modulated DSC (trade name “Q-2000” manufactured by TIA Instruments Inc.). Under the heating rate of 5 ° C./min, the reversing heat flow (specific heat component) behavior of the homopolymer is obtained.
- the obtained reversing heat flow has a low temperature side base line and a high temperature side base line, and a straight line equidistant in the vertical axis direction, and a stepwise change in glass transition.
- the temperature at the point where the curves intersect with each other is defined as the glass transition temperature (Tg) when the homopolymer is used.
- the content of the polymer in the pressure-sensitive adhesive composition of the present embodiment is preferably from 50% by weight to 99.9% by weight based on the total amount of the pressure-sensitive adhesive composition (100% by weight), and the upper limit is more preferably 99.9% by weight. It is 5% by mass, more preferably 99% by mass, and the lower limit is more preferably 60% by mass, further preferably 70% by mass.
- the ionic liquid in the present embodiment is not particularly limited as long as it is composed of a pair of anion and cation and is a molten salt (normal temperature molten salt) which 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 and will be described later. Is an ionic solid.
- the anions of the ionic liquid include, 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 ⁇ , and F (HF) n ⁇ .
- examples of the anion 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 preferred because they are chemically stable and are suitable for improving the electrical stripping property.
- the cations in the ionic liquid are preferably nitrogen-containing onium, sulfur-containing onium, and phosphorus-containing onium cations because they are chemically stable and suitable for improving electrical stripping properties, and are preferably imidazolium-based and ammonium-based onium cations. , Pyrrolidinium-based, and pyridinium-based cations are more preferred.
- imidazolium-based cation examples include 1-methylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-propyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, -Pentyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-heptyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-nonyl-3- Methyl imidazolium cation, 1-undecyl-3-methyl imidazolium cation, 1-dodecyl-3-methyl imidazolium cation, 1-tridecyl-3-methyl imidazolium cation, 1-tetradecyl-3-methyl imidazolium cation, 1 -Penta Sil-3-methylimidazolium cation
- Examples of the pyridinium-based cation include 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, and 1-octyl-4-methylpyridinium cation And the like.
- Examples of the pyrrolidinium cation include a 1-ethyl-1-methylpyrrolidinium cation and a 1-butyl-1-methylpyrrolidinium cation.
- ammonium-based cation examples include a tetraethylammonium cation, a tetrabutylammonium cation, a methyltrioctylammonium cation, a tetradecitrihexylammonium cation, a glycidyltrimethylammonium cation, and a 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 force when voltage is applied, and the above-mentioned (FSO 2 ) 2 N ⁇ [bis ( An ionic liquid 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 is particularly preferable.
- Examples of the cation 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
- Examples include a pyrrolidinium cation, a 1-butyl-1-methylpyrrolidinium cation, a tetraethylammonium cation, a glycidyltrimethylammonium cation, and a trimethylaminoethylacrylate cation.
- R 1 in the 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);
- R 2 and R 3 may be the same or different and each may be 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 2 to 2 carbon atoms).
- To 6 hydrocarbon groups more preferably a hydrocarbon group having 2 to 4 carbon atoms), and may contain a hetero atom. However, when a nitrogen atom forms a double bond with an adjacent carbon atom, R 3 is not present.
- R 4 in the 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);
- R 5 , R 6 and R 7 may be the same or different and each may be 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, and may contain a hetero atom.
- R 8 in the 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);
- R 9 , R 10 , and R 11 may be the same or different and may be 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 hetero atom.
- X in the 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 each have a hydrocarbon group of 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, further preferably a hydrocarbon group having 1 to 8 carbon atoms, particularly preferably a hydrocarbon group having 1 to 6 carbon atoms. ), And may include a hetero atom.
- R 12 is absent.
- 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, further preferably 250 or less, particularly preferably 200 or less, and most preferably 160 or less. Also, it is usually 50 or more. It is considered that the cation in the ionic liquid moves to the cathode side when a voltage is applied in the pressure-sensitive adhesive layer, and has a property of being biased near the interface between the pressure-sensitive adhesive layer and the adherend. In the present invention, for this reason, the adhesive force during the application of a voltage is reduced with respect to the initial adhesive force, resulting in electrical peelability.
- a cation having a small molecular weight, such as a molecular weight of 500 or less, is suitable in that the movement of the cation to the cathode side in the pressure-sensitive adhesive layer becomes easier, and the rate of decrease in the adhesive force when a voltage is applied is suitable.
- ionic liquids include, for example, "Elexel AS-110", “Elexel MP-442”, “Elexel IL-210", “Elexel MP-471”, “Elexel MP-471” 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.
- the ionic conductivity of the ionic liquid is preferably from 0.1 mS / cm to 10 mS / cm.
- the upper limit of the ionic conductivity is more preferably 5 mS / cm, further preferably 3 mS / cm, and the lower limit is more preferably 0.3 mS / cm, and still more preferably 0.5 mS / cm.
- the ionic conductivity can be measured by, for example, an AC impedance method using a 1260 frequency response analyzer manufactured by Solartron.
- the content (blending amount) of the ionic liquid in the pressure-sensitive adhesive composition of the present embodiment is preferably 0.5 parts by mass or more with respect to 100 parts by mass of the polymer, from the viewpoint of reducing the adhesive force during voltage application. , 30 parts by mass or less is preferable from the viewpoint of increasing the initial adhesive strength. From the same viewpoint, the amount 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 at least 0.6 part by mass, further preferably at least 0.8 part by mass, particularly preferably at least 1.0 part by mass, and at least 1.5 parts by mass. Is most preferred.
- the pressure-sensitive adhesive composition of the present embodiment may contain one or two components other than the polymer and the ionic liquid (hereinafter, may be referred to as “other components”) as long as the effects of the present invention are not impaired. More than one species can be contained.
- other components that can be contained in the pressure-sensitive adhesive composition of the present embodiment will be described.
- the pressure-sensitive adhesive composition of the present embodiment may contain an ionic additive for the purpose of controlling the relative dielectric constant, ionic conductivity, and capacitance.
- an ionic additive for example, an ionic solid can be used.
- Ionic solids are ionic substances that are solid at 25 ° C.
- the ionic solid is not particularly limited.
- a solid ionic substance can be used among the ionic substances obtained by combining an anion and a cation exemplified in the description of the ionic liquid described above.
- the content of the ionic solid is preferably at least 0.5 part by mass, more preferably at least 1 part by mass, and preferably at least 10 parts by mass, based on 100 parts by mass of the polymer. Or less, more preferably 5 parts by mass or less, even more preferably 2.5 parts by mass or less.
- the pressure-sensitive adhesive composition of the present embodiment may contain a crosslinking agent as needed for the purpose of improving creep property and shearing property by crosslinking a polymer.
- a crosslinking agent include isocyanate crosslinking agents, epoxy crosslinking agents, melamine crosslinking agents, peroxide crosslinking agents, urea crosslinking agents, metal alkoxide crosslinking agents, metal chelate crosslinking agents, and metal salt crosslinking agents.
- Crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, and amine crosslinking agents are exemplified.
- Examples of the isocyanate-based cross-linking agent include toluene diisocyanate, methylene bisphenyl isocyanate, and the like.
- Examples of the epoxy crosslinking agent include N, N, N ′, N′-tetraglycidyl-m-xylenediamine, diglycidylaniline, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, 6-hexanediol diglycidyl ether and the like.
- the content is preferably 0.1 part by mass or more, more preferably 0.7 part by mass or more, and preferably 50 parts by mass or less, and more preferably 10 parts by mass with respect to 100 parts by mass of the polymer. Is more preferably not more than 3 parts by mass.
- the crosslinking agent can be used alone or in combination of two or more.
- the pressure-sensitive adhesive composition of the present embodiment may contain polyethylene glycol or tetraethylene glycol dimethyl ether, if necessary, for the purpose of assisting the movement of the ionic liquid when applying a voltage.
- polyethylene glycol or tetraethylene glycol dimethyl ether those having a number average molecular weight of 100 to 6000 can be used.
- the content is preferably at least 0.1 part by mass, more preferably at least 0.5 part by mass, still more preferably at least 1 part by mass, based on 100 parts by mass of the polymer. It is preferably at most 20 parts by mass, more preferably at most 20 parts by mass, even more preferably at most 15 parts by mass.
- the pressure-sensitive adhesive composition of the present embodiment may contain a conductive filler as needed for the purpose of imparting conductivity to the pressure-sensitive adhesive composition.
- the conductive filler is not particularly limited, and a commonly known or commonly used conductive filler can be used. For example, graphite, carbon black, carbon fiber, metal powder such as silver or copper can be used. .
- the content is preferably from 0.1 part by mass to 200 parts by mass with respect to 100 parts by mass of the polymer.
- the pressure-sensitive adhesive composition of the present embodiment may contain a corrosion inhibitor as needed for the purpose of suppressing corrosion of the metal adherend.
- the corrosion inhibitor is not particularly limited, and a generally known or commonly used corrosion inhibitor can be used.
- a carbodiimide compound, an adsorption inhibitor, a chelate-forming metal deactivator, and the like can be used.
- carbodiimide compound examples include 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, and polycarbodiimide resins using these as monomers.
- carbodiimide compounds can be used alone or in combination of two or more.
- the content is preferably 0.01 part by mass or more and 10 parts by mass or less based on 100 parts by mass of the polymer.
- the adsorption-type inhibitor include an alkylamine, a carboxylate, a carboxylic acid derivative, and an alkyl phosphate.
- the adsorption inhibitors can be used alone or in combination of two or more.
- the pressure-sensitive adhesive composition of this embodiment contains an alkylamine as an adsorption inhibitor, the content is preferably from 0.01 to 20 parts by mass based on 100 parts by mass of the polymer.
- the content is preferably 0.01 part by mass or more and 10 parts by mass or less based on 100 parts by mass of the polymer.
- the carboxylic acid derivative is contained in the pressure-sensitive adhesive composition of the present embodiment as an adsorption-type inhibitor, the content is preferably 0.01 part by mass or more and 10 parts by mass or less based on 100 parts by mass of the polymer.
- the pressure-sensitive adhesive composition of the present embodiment contains an alkyl phosphate as an adsorption-type inhibitor, the content is preferably 0.01 part by mass or more and 10 parts by mass or less based on 100 parts by mass of the polymer.
- the chelate-forming metal deactivator for example, a compound containing a triazole group or a compound containing a benzotriazole group can be used. These are preferable because they have a high effect of inactivating the surface of a metal such as aluminum and do not easily affect the adhesiveness even when contained in a tacky component.
- the chelate-forming metal deactivators can be used alone or in combination of two or more.
- the content of the chelate-forming metal deactivator in the pressure-sensitive adhesive composition of the present embodiment is preferably 0.01 part by mass or more and 20 parts by mass or less based on 100 parts by mass of the polymer.
- the total content (blending amount) of the corrosion inhibitor is preferably from 0.01 part by mass to 30 parts by mass with respect to 100 parts by mass of the polymer.
- the pressure-sensitive adhesive composition of the present embodiment further includes a filler, a plasticizer, an antioxidant, an antioxidant, a pigment (dye), a flame retardant, a solvent, a surfactant (leveling agent), a rust inhibitor, and an adhesive.
- Various additives such as an application resin and an antistatic agent may be contained.
- 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 to 20 parts by mass, more preferably 10 parts by mass or less, based on 100 parts by mass of the polymer. And more preferably 5 parts by mass or less.
- the filler examples include silica, iron oxide, zinc oxide, aluminum oxide, titanium oxide, barium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, pyrite clay, kaolin clay, and calcined clay.
- plasticizer known and commonly used plasticizers used for general resin compositions and the like can be used.
- plasticizer include oils such as paraffin oil and process oil, liquid polyisoprene, liquid polybutadiene, and liquid ethylene-propylene rubber.
- DOP dioctyl phthalate
- DBP dibutyl phthalate
- DINA diisononyl adipate
- isodecyl succinate and the like can be used.
- the anti-aging agent include hindered phenol compounds, aliphatic and aromatic hindered amine compounds, and the like.
- antioxidant examples include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).
- pigments include, for example, inorganic pigments such as titanium dioxide, zinc oxide, ultramarine blue, red iron oxide, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, and sulfate; azo pigments; and organic pigments such as copper phthalocyanine pigments. Is mentioned.
- examples of the rust preventive include zinc phosphate, tannic acid derivatives, phosphates, basic sulfonates, and various rust preventive pigments.
- adhesion-imparting agent examples include a titanium coupling agent and a zirconium coupling agent.
- Examples of the antistatic agent generally include quaternary ammonium salts, hydrophilic compounds such as polyglycolic acid and ethylene oxide derivatives.
- examples of the tackifying resin include a rosin-based tackifying resin, a terpene-based tackifying resin, a phenol-based tackifying resin, a hydrocarbon-based tackifying resin, a ketone-based tackifying resin, a polyamide-based tackifying resin, and an epoxy-based tackifying resin. And a tackifying resin.
- the tackifier resins can be used alone or in combination of two or more.
- the pressure-sensitive adhesive composition of the first embodiment comprises a pressure-sensitive adhesive layer (ionic liquid) composed of a composition (ionic liquid-free pressure-sensitive adhesive composition) composed of components other than the ionic liquid among the components contained in the pressure-sensitive adhesive composition.
- ionic liquid a composition
- ionic liquid-free pressure-sensitive adhesive composition a composition
- Non-containing pressure-sensitive adhesive layer and after leaving the pressure-sensitive adhesive layer in an environment of 22 ° C. and 20% RH for 3 days, the pressure-sensitive adhesive layer has a relative dielectric constant of 5 or more at a frequency of 100 Hz.
- the above-mentioned relative permittivity refers to the relative permittivity measured as follows. First, an ionic liquid-free pressure-sensitive adhesive having a thickness of 30 ⁇ m was applied by uniformly applying the ionic liquid-free pressure-sensitive adhesive composition on the release surface of a separator whose surface was subjected to a release treatment, and drying by heating at 130 ° C. for 3 minutes. Get the layers. Next, the obtained ionic liquid-free pressure-sensitive adhesive layer is allowed to stand under an environment of 22 ° C. and 20% RH for 3 days. Then, the relative permittivity is measured under the following conditions.
- Measurement conditions of relative permittivity Measurement method: volumetric method (apparatus: using Agilent Technologies 4294A Precision Impedance Analyzer) Electrode configuration: 12.1 mm ⁇ , 0.5 mm thick aluminum plate Counter electrode: 60 ⁇ m thick aluminum foil Measurement environment: 23 ⁇ 1 ° C., 52 ⁇ 1% RH
- the relative dielectric constant of the ionic liquid-free pressure-sensitive adhesive layer has a correlation with the mobility of the ionic liquid in the pressure-sensitive adhesive layer formed by the pressure-sensitive adhesive composition containing the ionic liquid.
- the pressure-sensitive adhesive composition according to the first embodiment has a relative dielectric constant of 5 at a frequency of 100 Hz after leaving the ionic liquid-free pressure-sensitive adhesive layer in an environment of 22 ° C. and 20% RH for 3 days. As described above, even in a low humidity environment, it is possible to form an adhesive whose adhesive strength is sufficiently reduced by applying a voltage.
- the relative dielectric constant of the ionic liquid-free pressure-sensitive adhesive layer is controlled, for example, by appropriately adjusting the type of the polymer component in the pressure-sensitive adhesive composition and the type and content of the ionic additive within the above-described preferable range. Can be.
- the pressure-sensitive adhesive composition of the second embodiment forms a pressure-sensitive adhesive layer from the pressure-sensitive adhesive composition, and is attached to an aluminum plate made of A5052P H32 in JIS H4000: 2014 under an environment of 22 ° C. and 15% RH. After standing for 7 days, the capacitance per unit area of the interface between the adhesive layer and the aluminum plate is 0.9 ⁇ F / cm 2 or more, and the ionic conductivity of the adhesive layer is 10 ⁇ S / m or more.
- the ionic conductivity of the pressure-sensitive adhesive layer has a correlation with the ease of movement of the ionic liquid in the pressure-sensitive adhesive layer. The higher the ionic conductivity, the easier the ionic liquid moves.
- the capacitance per unit area of the interface between the pressure-sensitive adhesive layer and the adherend has a correlation with the easiness of the presence of the ionic liquid at the interface between the pressure-sensitive adhesive layer and the adherend. A large amount of ionic liquid is likely to exist at the interface between the layer and the adherend.
- the pressure-sensitive adhesive composition of the second embodiment forms a pressure-sensitive adhesive layer from the pressure-sensitive adhesive composition, and is attached to an aluminum plate made of A5052P H32 in JIS H4000: 2014 under an environment of 22 ° C. and 15% RH.
- the capacitance per unit area of the interface between the adhesive layer and the aluminum plate is 0.9 ⁇ F / cm 2 or more, and the ionic conductivity of the adhesive layer is 10 ⁇ S / m or more.
- the capacitance per unit area is 1.2 ⁇ F / cm 2 or more
- the ionic conductivity of the pressure-sensitive adhesive layer is 20 ⁇ S / m or more.
- the above-mentioned ionic conductivity and capacitance are, for example, by appropriately adjusting the components of the polymer in the pressure-sensitive adhesive composition, the type and content of the ionic liquid, and the type and content of the ionic additive within the above-described suitable range. , Can be controlled.
- ionic conductivity and capacitance refer to the ionic conductivity and capacitance measured as described below.
- the pressure-sensitive adhesive composition is uniformly applied to the aluminum-deposited surface side of an aluminum-deposited PET film 100 (trade name “Metal Me TS” manufactured by Toray Industries, Ltd.). In this case, in order to bring the electrode into contact with the aluminum vapor-deposited surface, a part to which the pressure-sensitive adhesive composition is not applied is partially provided.
- the adhesive layer 200 is formed by heating and drying at 130 ° C. for 3 minutes to obtain an adhesive sheet sample. Thereafter, the adhesive surface of the obtained adhesive sheet sample is attached to an aluminum plate 300 (A5052P H32 (JIS H4000: 2014)) to obtain a joined body sample 400 having a shape as shown in FIGS.
- FIG. 5 is a side view
- FIG. 6 is a top view.
- an LCR meter for example, IM3533 manufactured by Hioki Electric Co., Ltd.
- an alternating voltage of 0.5 V is applied between the aluminum plate 300 and the aluminum-deposited surface of the aluminum-deposited PET film 100 using an LCR meter, and the frequency is changed from 0.5 Hz to 200 kHz to obtain a cole-col plot. .
- the bulk of the pressure-sensitive adhesive layer 200 is regarded as a parallel circuit of a resistance component R adh and a capacitance component C adh
- the interface of the pressure-sensitive adhesive layer 200 is regarded as a parallel circuit of a resistance component R p and a capacitance component C dl.
- the equivalent circuit of the conjugate sample is set as shown in FIG. 7, and the obtained cole-col plot is fitted by the following equation (A). Note that the resistance component R0 is a wiring resistance.
- ⁇ is an angular frequency
- the capacitance per unit area of the interface between the adhesive layer 200 and the aluminum plate 300 can be obtained.
- the ionic conductivity ⁇ of the pressure-sensitive adhesive layer can be determined by using the following expression (B) using the bulk resistance component Radh of the pressure-sensitive adhesive layer 200 determined by the expression (A).
- l is the thickness of the pressure-sensitive adhesive layer
- A is the area of the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer 200.
- the adhesive force of the pressure-sensitive adhesive composition of the present embodiment can be evaluated by various methods.
- the adhesive force can be evaluated by a 180 ° peel test described in Examples.
- the pressure-sensitive adhesive composition of this embodiment forms a pressure-sensitive adhesive sheet as described in the Examples section, and preferably has an initial adhesive force of 1.0 N / cm or more measured by performing a 180 ° peel test. , 1.5 N / cm or more, more preferably 2.0 N / cm or more, particularly preferably 2.5 N / cm or more, and preferably 3.0 N / cm or more. Most preferred.
- the initial adhesive strength is 1.0 N / cm or more, the adhesion to the adherend is sufficient, and the adherend is less likely to peel or shift.
- the pressure-sensitive adhesive composition of this embodiment forms a pressure-sensitive adhesive sheet as described in the Examples section, is left under a predetermined temperature and humidity environment for a predetermined period, and a voltage of 10 V is applied for 30 seconds. It is preferable that the adhesive strength measured by a 180 ° peel test while applying a voltage of 10 V later is sufficiently smaller than the initial adhesive strength. That is, the adhesive force decrease rate determined by the following formula (C) from the adhesive force measured by the above method (in the following formula (C), simply referred to as “adhesive force during voltage application”) and the initial adhesive force. Is preferably at least 60%, more preferably at least 70%, even more preferably at least 80%.
- the above-mentioned predetermined temperature, humidity and period are preferably 22 ° C. and 20% RH for 3 days, more preferably 22 ° C. and 15% RH for 7 days.
- Adhesive strength reduction rate (%) ⁇ 1 ⁇ (adhesive strength during application of voltage / initial adhesive strength) ⁇ ⁇ 100 (C)
- the applied voltage and the voltage application time at the time of electric peeling are not limited to the above, and are not particularly limited as long as the pressure-sensitive adhesive sheet can be peeled. These preferred ranges are described below.
- the applied voltage is preferably 1 V or more, more preferably 3 V or more, and even more preferably 6 V or more. Further, the voltage is preferably 100 V or less, more preferably 50 V or less, further 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, further preferably 20 seconds or less, and particularly preferably 10 seconds or less. In such a case, workability is excellent. The shorter the application time, the better, but usually it is 1 second or more.
- the pressure-sensitive adhesive composition of the present invention is not particularly limited, it is produced by appropriately stirring and mixing a polymer, an ionic liquid, an additive, and a crosslinking agent, polyethylene glycol, a conductive filler, and the like to be blended as necessary. can do.
- the pressure-sensitive adhesive sheet of the present embodiment is not particularly limited as long as it has at least one pressure-sensitive adhesive layer (hereinafter also referred to as an “electropeelable pressure-sensitive adhesive layer”) formed from the pressure-sensitive adhesive composition of the present embodiment.
- the pressure-sensitive adhesive sheet of the present embodiment may have a pressure-sensitive adhesive layer that does not contain an ionic liquid (hereinafter, may be referred to as “other pressure-sensitive adhesive layer”) other than the electrodeposition type pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive sheet of the present embodiment may have a base material, a conductive layer, a conductive base material, an intermediate layer, an undercoat layer, and the like.
- the pressure-sensitive adhesive sheet of the present embodiment may be, for example, in a form wound in a roll or in a sheet form.
- the term “adhesive sheet” includes the meaning of “adhesive tape”. That is, the adhesive sheet of the present embodiment may be an adhesive tape having a tape-like form.
- the pressure-sensitive adhesive sheet of the present embodiment may be a double-sided pressure-sensitive adhesive sheet having no base material and consisting only of an electro-peelable pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive sheet of the present embodiment may be a double-sided pressure-sensitive adhesive sheet having a base material and both sides of the base material being a pressure-sensitive adhesive layer (an electro-peelable pressure-sensitive adhesive layer or another pressure-sensitive adhesive layer).
- the pressure-sensitive adhesive sheet of the present embodiment may be a single-sided pressure-sensitive adhesive sheet having a base material, and only one surface of the base material is a pressure-sensitive adhesive layer (an electrically-peelable pressure-sensitive adhesive layer or another pressure-sensitive adhesive layer).
- the pressure-sensitive adhesive sheet of the present embodiment may have a separator (release liner) for protecting the surface of the pressure-sensitive adhesive layer, but the separator is not included in the pressure-sensitive adhesive sheet of the present embodiment. .
- the structure of the pressure-sensitive adhesive sheet of the present embodiment is not particularly limited, but preferably includes a pressure-sensitive adhesive sheet X1 shown in FIG. 1, a pressure-sensitive adhesive sheet X2 having a laminated structure in FIG. 2, and a pressure-sensitive adhesive sheet X3 having a laminated structure in FIG.
- the pressure-sensitive adhesive sheet X1 is a substrate-less double-sided pressure-sensitive adhesive sheet composed of only the electrically peelable pressure-sensitive adhesive layer 1.
- the pressure-sensitive adhesive sheet X ⁇ b> 2 is a double-sided pressure-sensitive adhesive sheet with a substrate having a layer configuration of the pressure-sensitive adhesive layer 2, the current-carrying base material 5 (the base material 3 and the conductive layer 4), and the electrically-peelable pressure-sensitive adhesive layer 1.
- the pressure-sensitive adhesive sheet X3 includes a pressure-sensitive adhesive layer 2, a current-carrying base material 5 (base material 3 and a conductive layer 4), an electrically-peelable pressure-sensitive adhesive layer 1, a current-carrying substrate 5 (base material 3 and a conductive layer 4), and a pressure-sensitive adhesive. It is a double-sided pressure-sensitive adhesive sheet with a substrate having the layer configuration of Layer 2.
- the base material 3 for conducting electricity of the adhesive sheets X2 and X3 is not essential, and may be only the conductive layer 4. Further, in the pressure-sensitive adhesive sheet X2 of FIG. 2, a single-sided pressure-sensitive adhesive sheet without the pressure-sensitive 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 nonwoven fabric, various plastics (a polyolefin resin such as polyethylene or polypropylene, a polyester resin such as polyethylene terephthalate, Plastic-based substrates such as films and sheets of acrylic resins such as methyl methacrylate, etc., and laminates thereof.
- the substrate may have a single-layer form or a multi-layer form.
- the base material may be subjected to various treatments such as a back surface treatment, an antistatic treatment, and a primer treatment as needed.
- the conductive layer 4 is not particularly limited as long as it is a layer having conductivity, but a metal (for example, aluminum, magnesium, copper, iron, tin, gold, etc.) foil, a metal plate (for example, aluminum, magnesium, copper, iron) , Tin, silver, etc.), a conductive polymer, or the like, or a metal-deposited film provided on the substrate 3.
- a metal for example, aluminum, magnesium, copper, iron, tin, gold, etc.
- a metal plate for example, aluminum, magnesium, copper, iron
- Tin silver, etc.
- the current-carrying substrate 5 is not particularly limited as long as it is a substrate having a conductive layer (current-carrying), and examples thereof include a substrate having a metal layer formed on the surface of the substrate.
- a material in which a metal layer is formed on a surface of a material by a method such as a plating method, a chemical vapor deposition method, and a sputtering method may be used.
- the metal layer include the metals, metal plates, and conductive polymers exemplified above.
- the adherends on both sides are preferably adherends having a metal adherend surface.
- the adherend on the side of the electrically-peelable pressure-sensitive adhesive layer 1 is an adherend having a metal-applied surface.
- Examples of the metal-coated surface include surfaces having conductivity, for example, a surface composed of a metal containing aluminum, copper, iron, magnesium, tin, gold, silver, lead, or the like as a main component. Is preferred.
- Examples of the adherend having a metal adhered surface include a sheet, a component, and a plate made of a metal mainly containing aluminum, copper, iron, magnesium, tin, gold, silver, lead, and the like.
- the adherend other than the adherend having a metal adherend surface is not particularly limited, and examples thereof include fiber sheets such as paper, cloth, and nonwoven fabric, and films and sheets of various plastics.
- the thickness of the electrically peelable pressure-sensitive adhesive layer 1 is preferably 1 ⁇ m or more and 1000 ⁇ m or less from the viewpoint of initial adhesive strength.
- the upper limit of the thickness of the electrodeposition type pressure-sensitive adhesive layer 1 is more preferably 500 ⁇ m, further preferably 100 ⁇ m, particularly preferably 30 ⁇ m, and the lower limit is more preferably 3 ⁇ m, and still more preferably 5 ⁇ m. And particularly preferably 8 ⁇ m.
- the pressure-sensitive adhesive sheet is a substrate-less double-sided pressure-sensitive adhesive sheet (pressure-sensitive adhesive sheet X1 shown in FIG. 1) composed of only one pressure-sensitive adhesive layer, the thickness of the pressure-sensitive adhesive sheet is determined by the thickness of the pressure-sensitive adhesive sheet. Becomes
- 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, further preferably 500 ⁇ m, particularly preferably 100 ⁇ m, and the lower limit is more preferably 3 ⁇ m, further 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, further preferably 300 ⁇ m, and particularly preferably 100 ⁇ m, and the lower limit is more preferably 12 ⁇ m, and 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, still more preferably 300 ⁇ m, still more preferably 50 ⁇ m, and still more preferably 10 ⁇ m, and the lower limit is more preferably 0.01 ⁇ m, more preferably 0.1 ⁇ m. It is 03 ⁇ m, more preferably 0.05 ⁇ m.
- the thickness of the current-carrying substrate 5 is preferably 10 ⁇ m or more and 1000 ⁇ m or less.
- the upper limit of the thickness is more preferably 500 ⁇ m, further preferably 300 ⁇ m, and particularly preferably 100 ⁇ m, and the lower limit is more preferably 12 ⁇ m, and still more preferably 25 ⁇ m.
- the surfaces of the electrically peelable pressure-sensitive adhesive layer and the other pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the present embodiment may be protected by a separator (release liner).
- the separator is not particularly limited, but a release liner in which the surface of a substrate (liner substrate) such as paper or plastic film is silicone-treated, or the surface of a substrate (liner substrate) such as paper or plastic film is polyolefin-based A release liner laminated with a resin may, for example, be mentioned.
- the thickness of the separator is not particularly limited, but is preferably 10 ⁇ m or more and 100 ⁇ m or less.
- the thickness of the pressure-sensitive adhesive sheet of the present 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 300 ⁇ m, and particularly preferably 200 ⁇ m, and the lower limit is more preferably 30 ⁇ m, and 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, and still more preferably 200 ⁇ m, and the lower limit is more preferably 80 ⁇ m, and still more preferably 100 ⁇ m.
- the thickness of the adhesive sheet is preferably 100 ⁇ m or more and 3000 ⁇ m or less.
- the upper limit of the thickness is more preferably 1000 ⁇ m, and still more preferably 300 ⁇ m, and the lower limit is more preferably 150 ⁇ m, and still more preferably 200 ⁇ m.
- the other pressure-sensitive adhesive layer includes a method in which a solution obtained by dissolving a pressure-sensitive adhesive composition containing no ionic liquid and additives in a solvent, if necessary, is coated on a separator, and dried and / or cured.
- the solvent and the separator can use the thing mentioned above.
- a conventional coater for example, gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, spray roll coater, etc.
- a conventional coater for example, gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, spray roll coater, etc.
- an electric peeling type pressure-sensitive adhesive layer, and other pressure-sensitive adhesive layers can be produced, and as appropriate, a base material, a conductive layer, a current-carrying substrate, an electric peeling type pressure-sensitive adhesive layer, and other pressure-sensitive adhesive layers.
- the pressure-sensitive adhesive sheet of the present embodiment can be manufactured.
- the peeling of the pressure-sensitive adhesive sheet of this embodiment from the adherend can be performed by applying a voltage to the pressure-sensitive adhesive layer to generate a potential difference in the thickness direction of the pressure-sensitive adhesive layer.
- a voltage for example, when both surfaces of the pressure-sensitive adhesive sheet X1 are adherends each having a metal-adhered surface, electricity can be applied to both metal-adhered surfaces, and the pressure-sensitive adhesive layer can be peeled off by applying a voltage to the adhesive layer.
- the electrically peelable pressure-sensitive adhesive layer side of the pressure-sensitive adhesive sheet X2 is an adherend having a metal adhered surface
- a current is applied to the conductive adherend and the conductive layer 4
- a voltage is applied to the electrically peelable pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive sheet X3 it can be peeled off by applying a current to the conductive layers 4 on both sides and applying a voltage to the electrically peelable pressure-sensitive adhesive layer.
- the energization is preferably performed by connecting a terminal to one end and the other end of the pressure-sensitive adhesive sheet so that a voltage is applied to the entire electrically peelable pressure-sensitive adhesive layer.
- the one end and the other end may be a part of the adherend having the metal adhered surface.
- a voltage may be applied after water is added to the interface between the metal-coated surface and the electrically peelable pressure-sensitive adhesive layer.
- the adhesive sheet of the present embodiment is used for fixing a secondary battery (for example, a lithium ion battery pack) used in a mobile terminal such as a smartphone, a mobile phone, a notebook computer, a video camera, and a digital camera to a housing. It is suitable for.
- a secondary battery for example, a lithium ion battery pack
- Examples of the rigid member to be joined by the adhesive sheet of the present embodiment include a silicon substrate for a semiconductor wafer, a sapphire substrate for an LED, a SiC substrate and a metal base substrate, a TFT substrate for a display, and a color filter substrate. And a base substrate for an organic EL panel.
- Examples of the fragile member to be bonded by the double-sided adhesive sheet include a semiconductor substrate such as a compound semiconductor substrate, a silicon substrate for MEMS devices, a passive matrix substrate, a surface cover glass for a smartphone, and a touch panel sensor attached to the cover glass.
- OGS One Glass Solution
- substrate an organic substrate and an organic-inorganic hybrid substrate containing silsesquioxane as a main component
- a flexible glass substrate for a flexible display and a graphene sheet.
- the joined body of the present embodiment has a laminated structure including an adherend having a metal adhered surface and an adhesive sheet having an electrically peelable adhesive layer joined to the metal adhered surface.
- adherend having a metal-applied surface include, for example, those composed of a metal containing aluminum, copper, iron, magnesium, tin, gold, silver, lead, or the like as a main component. Is preferred.
- Examples of the bonded body of the present embodiment include a pressure-sensitive adhesive sheet X1 and a bonded body including an adherend having a metal-applied surface on both surfaces of the electro-peelable pressure-sensitive adhesive layer 1; A bonded body comprising an adherend having a metal adhered surface on the side of the peelable pressure-sensitive adhesive layer 1 and an adherend on the side of the pressure-sensitive adhesive layer 2, a pressure-sensitive adhesive sheet X3 having adherends on both surfaces of the pressure-sensitive adhesive layer 2 And the like.
- AIBN 2,2′-azobisisobutyronitrile
- n-butyl acrylate (BA): 67 parts by mass, methyl methacrylate (MMA): 33 parts by mass, and ethyl acetate: 150 parts by mass as a polymerization solvent are charged into a separable flask, and nitrogen gas is introduced. While stirring for 1 hour. After removing oxygen in the polymerization system in this manner, 0.2 parts by mass of 2,2′-azobisisobutyronitrile (AIBN) as a polymerization initiator was added, and the temperature was raised to 63 ° C. for 6 hours. Reacted. Thereafter, ethyl acetate was added to obtain an acrylic polymer 4 solution having a solid content concentration of 40% by mass.
- AIBN 2,2′-azobisisobutyronitrile
- AIBN 2,2′-azobisisobutyronitrile
- Byron UR-V8700 a urethane-modified polyester resin, trade name “Byron UR-V8700”, manufactured by Toyobo Co., Ltd.
- Byron BX1001 polyester resin, trade name “Byron BX1001”, manufactured by Toyobo Co., Ltd.
- Somalex 530 anionic polyacrylamide polymer (ionic polymer ), Trade name "Somarex 530", manufactured by Somar Corporation (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.
- EMI-nitrate 1-ethyl-3-methylimidazolium nitrate, manufactured by Tokyo Chemical Industry Co., Ltd.
- Zn-nitrate zinc nitrate hexahydrate, manufactured by Wako Pure Chemical Industries, Ltd.
- BTC-5B barium titanate 27776: Carbon black
- ⁇ Measurement of relative dielectric constant of ionic liquid-free pressure-sensitive adhesive layer An ionic liquid-free adhesive obtained by stirring and mixing materials in the same manner as in Examples 1-1 to 1-8 and Comparative examples 1-1 to 1-5 except that no ionic liquid was added.
- the composition was applied on a release-treated surface of a polyethylene terephthalate separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc.), the surface of which was subjected to a release treatment, using an applicator so as to have a uniform thickness. Next, heating and drying were performed at 130 ° C. for 3 minutes to obtain a 30 ⁇ m-thick ionic liquid-free pressure-sensitive adhesive layer.
- the relative permittivity of the pressure-sensitive adhesive layer at a frequency of 100 kHz is determined according to JIS K 6911 as follows. It was measured under the conditions. (Measurement condition) Measurement method: volumetric method (apparatus: using Agilent Technologies 4294A Precision Impedance Analyzer) Electrode configuration: 12.1 mm ⁇ , 0.5 mm thick aluminum plate Counter electrode: 3 oz copper plate Measurement environment: 23 ⁇ 1 ° C., 52 ⁇ 1% RH
- the obtained electrically peelable pressure-sensitive adhesive layer (pressure-sensitive adhesive sheet) was formed into a sheet having a size of 10 mm ⁇ 80 mm, and a film having a metal layer as a substrate (trade name “BR1075”, Toray Film Processing Co., Ltd.) ) Co., Ltd., 25 ⁇ m thick, size 10 mm ⁇ 100 mm) metal layer surface was bonded to obtain a single-sided pressure-sensitive adhesive sheet with a substrate.
- the separator of the single-sided pressure-sensitive adhesive sheet with the base material was peeled off, and an aluminum plate (A5052P H32 (JIS H4000: 2014)) was adhered to the peeled surface so that one end of the pressure-sensitive adhesive sheet protruded about 2 mm from the adherend, Pressed back and forth with a 2 kg roller once, and allowed to stand for 30 minutes in an environment of 23 ° C., from the stainless steel plate 6 / electrically peelable pressure-sensitive adhesive layer (pressure-sensitive adhesive sheet) 1 ′ / film with metal layer (substrate for conducting electricity) 5 ′.
- FIG. 4 shows an outline of the joined body.
- the film was peeled by a peeling tester (trade name “Yang angle peeling tester YSP”, manufactured by Asahi Seiko Co., Ltd.) in the arrow method in FIG. 4, and a 180 ° peel test (tensile speed: 300 mm / min, (The peeling temperature was 23 ° C.). Table 1 shows the measurement results.
- AIBN 2,2′-azobisisobutyronitrile
- AIBN 2,2′-azobisisobutyronitrile
- AIBN 2,2′-azobisisobutyronitrile
- Irgamet 30 N, N-bis (2-ethylhexyl) -1,2,4-triazol-1-ylmethanamine, trade name “Irgamet 30”, manufactured by BASF IrgacorDSSG: disodium sebacate, trade name “IrgametDSSG”, BASF AminO: imidazoline derivative, trade name "Amin O”, PEG400: polyethylene glycol, trade name "PEG400", trade name "PEG400", Tokyo Chemical Industry Co., Ltd. Coronate L: isocyanate compound, trade name "Coronate L", manufactured by Tosoh Corporation
- ⁇ Measurement of ionic conductivity and capacitance per unit area of adhesive layer Using the pressure-sensitive adhesive composition of each example, a measurement sample (composite sample) was prepared as follows, and the capacitance at the adhesive interface and the ionic conductivity of the pressure-sensitive adhesive layer were determined by the following methods. Table 2 shows the results.
- the pressure-sensitive adhesive composition was uniformly applied to the aluminum-deposited surface side of an aluminum-deposited PET film 100 (trade name “Metal Me TS” manufactured by Toray Film Processing Co., Ltd.). At this time, in order to bring the electrode into contact with the aluminum-deposited surface, a part to which the adhesive composition was not applied was partially provided. Then, the adhesive layer 200 was formed by heating and drying at 130 ° C. for 3 minutes to obtain an adhesive sheet sample. Thereafter, the adhesive surface of the obtained adhesive sheet sample was attached to an aluminum plate 300 (A5052P H32 (JIS H4000: 2014)) to obtain a joined body sample 400 having a shape as shown in FIGS. FIG. 5 is a side view, and FIG. 6 is a top view.
- the bulk of the pressure-sensitive adhesive layer 200 is regarded as a parallel circuit of a resistance component R adh and a capacitance component C adh
- the interface of the pressure-sensitive adhesive layer 200 is regarded as a parallel circuit of a resistance component R p and a capacitance component C dl.
- the equivalent circuit of the conjugate sample was set as shown in FIG. 7, and the obtained cole-col plot was fitted by the following equation (A). Note that the resistance component R0 is a wiring resistance.
- ⁇ is an angular frequency
- the capacitance per unit area of the interface between the adhesive layer 200 and the aluminum plate 300 was determined by dividing the obtained C dl by the area A of the adhesive surface of the adhesive layer 200.
- the ionic conductivity ⁇ of the pressure-sensitive adhesive layer was determined using the following equation (B) using the bulk resistance component Radh of the pressure-sensitive adhesive layer 200 determined from the equation (A).
- l is the thickness of the pressure-sensitive adhesive layer
- A is the area of the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer 200.
- Example 2 The pressure-sensitive adhesive composition of each example was prepared in the same manner as in Example 1 except that the pressure-sensitive adhesive layer was formed on the aluminum-deposited surface using an aluminum-deposited PET film (trade name “Metal Me TS” manufactured by Toray Film Processing Co., Ltd.) as a substrate.
- the initial adhesive strength was measured in the same manner as in Examples 1 to 1-8 and Comparative Examples 1-1 to 1-5. Table 2 shows the measurement results.
- Adhesive force during voltage application after storage for 3 days in an environment of 22 ° C. and 20% RH After pressing back and forth with a 2 kg roller for one round, left for 3 days in an environment of 22 ° C. and 20% RH, and before the peel, the minus pole of the DC current machine was placed at the positions ⁇ and ⁇ in FIG. And a positive electrode were attached, and a voltage was applied at a voltage of 10 V for 30 seconds. While applying the voltage as it was, the adhesive force during the application of the voltage was measured in the same manner as in the initial adhesive force measurement except that the peeling was performed. It measured and evaluated the electrical peelability by the following criteria. Table 2 shows the measurement results. :: Adhesion reduction rate is 60% or more. X: The adhesive strength reduction rate is less than 60%.
- a pressure-sensitive adhesive layer was formed from the pressure-sensitive adhesive composition, attached to an aluminum plate made of A5052P H32 according to JIS H4000: 2014, and allowed to stand at 22 ° C. and 15% RH for 7 days.
- a pressure-sensitive adhesive layer was formed from the pressure-sensitive adhesive composition, attached to an aluminum plate made of A5052P H32 according to JIS H4000: 2014, and allowed to stand at 22 ° C. and 15% RH for 7 days.
- the pressure-sensitive adhesive compositions of Examples 3-1 to 3-5 in which the capacitance per unit area of the interface of the aluminum plate is 0.9 ⁇ F / cm 2 or more and the ionic conductivity of the pressure-sensitive adhesive layer is 10 ⁇ S / m or more, In each case, the rate of decrease in the adhesive force due to the application of the voltage was large.
- Adhesive sheet 1 Electric release type adhesive layer 2 Adhesive layer 3 Base material 4 Conductive layer 5 Conductive base material 100 Aluminum evaporated PET film 200 Adhesive layer 300 Aluminum plate 400 Joint sample
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Abstract
Description
本発明は、粘着剤組成物、当該粘着剤組成物から形成された粘着剤層を含む粘着シート、及び当該粘着シートと被着体の接合体に関する。 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.
電子部品製造工程等において、歩留まり向上のためのリワークや、使用後に部品を分解して回収するリサイクル等に関する要望が増している。このような要望に応えるべく、電子部品製造工程等で部材間を接合するうえで、一定の接着力とともに一定の剥離性をも伴った両面粘着シートが利用される場合がある。 要 望 In the electronic component manufacturing process, there is an increasing demand for rework for improving the yield and recycling for disassembling and collecting components after use. In order to meet such a demand, a double-sided pressure-sensitive adhesive sheet having a certain adhesive force and a certain releasability may be used for joining members in an electronic component manufacturing process or the like.
上記の接着力と剥離性を実現する両面粘着シートとして、粘着剤組成物を形成する成分に、カチオンとアニオンからなるイオン液体を使用し、粘着剤層に電圧を印加することにより剥離する粘着シート(電気剥離型粘着シート)が知られている(特許文献1~3)。
特許文献1~3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。
As a double-sided pressure-sensitive adhesive sheet realizing the above-mentioned adhesive strength and peelability, a pressure-sensitive adhesive sheet which is peeled off by applying a voltage to the pressure-sensitive adhesive layer using an ionic liquid composed of a cation and an anion as a component forming the pressure-sensitive adhesive composition (Electrically peelable pressure-sensitive adhesive sheets) are known (
In the electro-peelable pressure-sensitive adhesive sheets of
電気剥離型粘着シートは、電圧非印加時には部材を強固に接合し、電圧印加時には少ない力で剥離できることが好ましい。したがって、電気剥離型粘着シートにおいて、電圧印加による接着力の低下率は大きいことが好ましい。しかし、例えば冬季等の湿度が低い環境においては、電圧印加による接着力の低下率が小さくなることが問題となっていた。 (4) It is preferable that the electro-peelable pressure-sensitive adhesive sheet can strongly bond the members when no voltage is applied, and can be peeled off with a small force when a voltage is applied. Therefore, it is preferable that the rate of decrease in the adhesive force due to voltage application is large in the electrically peelable pressure-sensitive adhesive sheet. However, in a low humidity environment such as in winter, for example, there has been a problem that the rate of decrease in adhesive strength due to voltage application is small.
本発明は上記に鑑みて完成されたものであり、低湿度環境下においても電圧の印加により十分に接着力が低下する粘着剤組成物及び当該粘着剤組成物から形成される粘着剤層を備える粘着シートを提供することを目的とする。 The present invention has been completed in view of the above, and includes a pressure-sensitive adhesive composition and a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition, the adhesion of which is sufficiently reduced by application of a voltage even in a low humidity environment. It is intended to provide an adhesive sheet.
本発明者らの検討によれば、低湿度環境下において電圧印加による接着力の低下率が小さくなるのは、低湿度環境下では粘着剤層の含水率が低下し、イオン液体のカチオン及びアニオンが移動しにくくなることに起因する。
本発明者らが更に検討を重ねた結果、以下の知見を得た。
第1に、粘着剤層のイオン液体以外の成分の比誘電率が電圧印加による接着力の低下率と相関性を有し、当該比誘電率を大きくすることで電圧印加による接着力の低下率を大きくすることができることを見出した。また、低湿度環境下に置かれて粘着剤層の含水率が低下した場合においても、当該比誘電率が大きければ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。
第2に、粘着剤層のイオン伝導度及び、粘着剤層と被着体の界面の単位面積あたりのキャパシタンスが電圧印加による接着力の低下率と相関性を有し、当該イオン伝導度及び、粘着剤層と被着体の界面の単位面積あたりのキャパシタンスを大きくすることで電圧印加による接着力の低下率を大きくすることができることを見出した。また、低湿度環境下に置かれて粘着剤層の含水率が低下した場合においても、当該イオン伝導度及び、粘着剤層と被着体の界面の単位面積あたりのキャパシタンスが大きければ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。
According to the study of the present inventors, the rate of decrease in adhesive strength due to voltage application in a low humidity environment decreases because the moisture content of the pressure-sensitive adhesive layer decreases in a low humidity environment, and the cation and anion of the ionic liquid are reduced. Is difficult to move.
As a result of further studies by the present inventors, the following findings were obtained.
First, the relative permittivity of components other than the ionic liquid in the pressure-sensitive adhesive layer has a correlation with the rate of decrease in adhesive force due to voltage application. By increasing the relative permittivity, the rate of decrease in adhesive force due to voltage application Can be increased. In addition, even when the moisture content of the pressure-sensitive adhesive layer is lowered under a low humidity environment, the larger the relative dielectric constant, the better the electrical peeling property, that is, the lowering rate of the adhesive force due to voltage application. I found it great.
Second, the ionic conductivity of the pressure-sensitive adhesive layer and the capacitance per unit area of the interface between the pressure-sensitive adhesive layer and the adherend have a correlation with the rate of decrease in adhesive force due to voltage application, and the ionic conductivity and It has been found that by increasing the capacitance per unit area of the interface between the pressure-sensitive adhesive layer and the adherend, the rate of decrease in adhesive force due to voltage application can be increased. In addition, even when the moisture content of the pressure-sensitive adhesive layer is lowered in a low-humidity environment, if the ionic conductivity and the capacitance per unit area of the interface between the pressure-sensitive adhesive layer and the adherend are large, the electrical peeling property is improved. Was good, that is, the rate of decrease in the adhesive force due to voltage application was large.
上記第1の知見に基づいて完成された本発明の一の粘着剤組成物は、ポリマーとイオン液体とを含む粘着剤組成物であって、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により粘着剤層を形成し、該粘着剤層を22℃、20%RHの環境下で3日間放置した後の、該粘着剤層の周波数100Hzにおける比誘電率が5以上である。 One pressure-sensitive adhesive composition of the present invention completed based on the first finding is a pressure-sensitive adhesive composition containing a polymer and an ionic liquid, and among components contained in the pressure-sensitive adhesive composition, other than the ionic liquid A pressure-sensitive adhesive layer at a frequency of 100 Hz after the pressure-sensitive adhesive layer is formed by forming a pressure-sensitive adhesive layer from the composition consisting of the following components, and left under an environment of 22 ° C. and 20% RH for 3 days. It is.
上記第2の知見に基づいて完成された本発明の他の粘着剤組成物は、ポリマーとイオン液体とを含む粘着剤組成物であって、粘着剤組成物により粘着剤層を形成してJIS H4000:2014におけるA5052P H32からなるアルミニウム板に貼付し、22℃、15%RHの環境下で7日間放置した後の、該粘着剤層と該アルミニウム板の界面の単位面積あたりのキャパシタンスが0.9μF/cm2以上、該粘着剤層のイオン伝導度が10μS/m以上である。 Another pressure-sensitive adhesive composition of the present invention completed on the basis of the second finding is a pressure-sensitive adhesive composition containing a polymer and an ionic liquid, and forms a pressure-sensitive adhesive layer with the pressure-sensitive adhesive composition according to JIS. H4000: A5052P H2014 in 2014 attached to an aluminum plate made of H32 and left for 7 days in an environment of 22 ° C. and 15% RH, the capacitance per unit area of the interface between the pressure-sensitive adhesive layer and the aluminum plate is 0. 9 μF / cm 2 or more, and the ionic conductivity of the pressure-sensitive adhesive layer is 10 μS / m or more.
本発明の粘着剤組成物の一態様において、粘着剤組成物により粘着剤層を形成してJIS H4000:2014におけるA5052P H32からなるアルミニウム板に貼付し、22℃、15%RHの環境下で7日間放置した後の、該粘着剤層と該アルミニウム板の界面の単位面積あたりのキャパシタンスが1.2μF/cm2以上、該粘着剤層のイオン伝導度が20μS/m以上であってもよい。 In one embodiment of the pressure-sensitive adhesive composition of the present invention, a pressure-sensitive adhesive layer is formed from the pressure-sensitive adhesive composition, and is adhered to an aluminum plate made of A5052P H32 according to JIS H4000: 2014. The capacitance per unit area of the interface between the pressure-sensitive adhesive layer and the aluminum plate after standing for days may be 1.2 μF / cm 2 or more, and the ionic conductivity of the pressure-sensitive adhesive layer may be 20 μS / m or more.
本発明の粘着剤組成物の一態様において、粘着剤組成物はイオン性固体をさらに含んでもよい。 に お い て In one embodiment of the pressure-sensitive adhesive composition of the present invention, the pressure-sensitive adhesive composition may further include an ionic solid.
本発明の粘着剤組成物の一態様において、ポリマーはイオン性ポリマーを含んでもよい。 に お い て In one embodiment of the pressure-sensitive adhesive composition of the present invention, the polymer may include an ionic polymer.
本発明の粘着剤組成物の一態様において、ポリマーは、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種を含んでもよい。 In one embodiment of the pressure-sensitive adhesive composition of the present invention, the polymer is 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. One type may be included.
また、本発明の他の粘着剤組成物は、ポリマーとイオン液体とを含み、ポリマー100質量部に対して、イオン液体0.5~30質量部と、イオン性固体0.5~10質量部とを含む。 Further, another pressure-sensitive adhesive composition of the present invention contains a polymer and an ionic liquid, and the ionic liquid is 0.5 to 30 parts by mass and the ionic solid is 0.5 to 10 parts by mass with respect to 100 parts by mass of the polymer. And
また、本発明の他の粘着剤組成物は、ポリマーとイオン液体とを含み、ポリマー100質量部に対して、イオン液体0.5~30質量部を含み、ポリマーにはイオン性ポリマーが0.05~2質量部含まれる。 Another adhesive composition of the present invention contains a polymer and an ionic liquid, and contains 0.5 to 30 parts by mass of the ionic liquid based on 100 parts by mass of the polymer. And 0.05 to 2 parts by mass.
また、本発明の他の粘着剤組成物は、アクリル系ポリマー100質量部と、イオン液体0.5~30質量部とを含む粘着剤組成物であって、アクリル系ポリマーを構成する全モノマー成分に対する極性基含有モノマーの割合が0.1~35質量%である。 Another pressure-sensitive adhesive composition of the present invention is a pressure-sensitive adhesive composition containing 100 parts by mass of an acrylic polymer and 0.5 to 30 parts by mass of an ionic liquid, wherein all monomer components constituting the acrylic polymer are The ratio of the polar group-containing monomer is 0.1 to 35% by mass.
本発明の一態様において、粘着剤組成物は電気剥離用である。 に お い て In one embodiment of the present invention, the pressure-sensitive adhesive composition is for electric stripping.
また、本発明の粘着シートは、本発明の粘着剤組成物から形成される粘着剤層を備える。 粘着 The pressure-sensitive adhesive sheet of the present invention includes a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention.
また、本発明の接合体は、金属被着面を有する被着体と、本発明の粘着シートとを備え、本発明の粘着シートの粘着剤層が金属被着面に接合している。 接合 Further, the joined body of the present invention includes an adherend having a metal adhered surface and the pressure-sensitive adhesive sheet of the present invention, and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the present invention is joined to the metal adhered surface.
本発明の粘着剤組成物は、低湿度環境下においても電圧の印加により十分に接着力が低下する。 粘着 The pressure-sensitive adhesive composition of the present invention has a sufficiently low adhesive strength even under a low humidity environment by application of a voltage.
以下、本発明を実施するための形態について詳細に説明する。なお、本発明は、以下に説明する実施形態に限定されるものではない。 Hereinafter, embodiments for carrying out the present invention will be described in detail. Note that the present invention is not limited to the embodiments described below.
[粘着剤組成物]
本発明の第1及び第2の実施形態の粘着剤組成物は、いずれもポリマーとイオン液体とを含む。
第1の実施形態の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により粘着剤層を形成し、該粘着剤層を22℃、20%RHの環境下で3日間放置した後の、該粘着剤層の周波数100Hzにおける比誘電率は、5以上である。
また、第2の実施形態の粘着剤組成物により粘着剤層を形成してJIS H4000:2014におけるA5052P H32からなるアルミニウム板に貼付し、22℃、15%RHの環境下で7日間放置した後の、該粘着剤層と該アルミニウム板の界面の単位面積あたりのキャパシタンスが0.9μF/cm2以上、該粘着剤層のイオン伝導度が10μS/m以上である。
これらの粘着剤組成物は、電圧印加により接着力が低下する性質を有し、電気剥離用粘着剤組成物として好適である。
なお、上記の第1及び第2の実施形態は、排他的なものではなく、第1及び第2の実施形態のいずれにも該当する粘着剤組成物もあれば、いずれかにのみ該当する粘着剤組成物もある。第1又は第2の実施形態のいずれかに該当する粘着剤組成物であれば、本発明の効果を奏する。
以下、これらの粘着剤組成物について説明する。
[Adhesive composition]
Each of the pressure-sensitive adhesive compositions of the first and second embodiments of the present invention contains a polymer and an ionic liquid.
A pressure-sensitive adhesive layer is formed by a composition composed of components other than the ionic liquid among the components included in the pressure-sensitive adhesive composition of the first embodiment, and the pressure-sensitive adhesive layer is placed in an environment of 22 ° C. and 20% RH for 3 days. After standing, the relative permittivity of the pressure-sensitive adhesive layer at a frequency of 100 Hz is 5 or more.
Further, a pressure-sensitive adhesive layer was formed from the pressure-sensitive adhesive composition of the second embodiment, attached to an aluminum plate made of A5052P H32 in JIS H4000: 2014, and left for 7 days in an environment of 22 ° C. and 15% RH. The capacitance per unit area at the interface between the pressure-sensitive adhesive layer and the aluminum plate is 0.9 μF / cm 2 or more, and the ion conductivity of the pressure-sensitive adhesive layer is 10 μS / m or more.
These pressure-sensitive adhesive compositions have a property that the adhesive force is reduced by application of a voltage, and are suitable as pressure-sensitive adhesive compositions for electric stripping.
The above first and second embodiments are not exclusive, and if there is a pressure-sensitive adhesive composition corresponding to any of the first and second embodiments, an adhesive composition corresponding to only one of them There are also agent compositions. If the pressure-sensitive adhesive composition falls under any one of the first and second embodiments, the effects of the present invention can be obtained.
Hereinafter, these pressure-sensitive adhesive compositions will be described.
なお、本明細書において、本発明の第1及び第2の実施形態をまとめて「本実施形態」ということがある。
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。
In this specification, the first and second embodiments of the present invention may be collectively referred to as “the present embodiment”.
In this specification, the adhesive force when no voltage is applied may be referred to as “initial adhesive force”.
In addition, a composition composed of components other than the ionic liquid among the components contained in the pressure-sensitive adhesive composition may be referred to as “non-ionic liquid-containing pressure-sensitive adhesive composition”.
In addition, the pressure-sensitive adhesive layer formed by the non-ionic liquid-containing pressure-sensitive adhesive composition may be referred to as “non-ionic liquid-containing pressure-sensitive adhesive layer”.
In addition, the property that the adhesive force is reduced by applying a voltage is referred to as “electro-peeling property”, and the fact that the rate of decrease in the adhesive force by applying a voltage is large is referred to as “excellent in electro-peeling property”.
<粘着剤組成物の成分>
(ポリマー)
本実施形態の粘着剤組成物は、ポリマーを含有する。本実施形態においてポリマーは、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。
<Components of pressure-sensitive adhesive composition>
(polymer)
The pressure-sensitive adhesive composition of the present embodiment contains a polymer. In the present embodiment, the 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 a monomer. The monomer may be a single monomer or a mixture of two or more monomers. In addition, the partially polymerized product means a polymer in which at least a part of the monomer or the monomer mixture is partially polymerized.
本実施形態におけるポリマーは、通常粘着剤として使用され、粘着性を有するものである限り特に限定されないが、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、およびエポキシ系ポリマー等である。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。
得られる粘着剤層のイオン液体以外の成分の比誘電率を大きくし、また、得られる粘着剤層のイオン伝導度及び接着界面の単位面積あたりのキャパシタンスを大きくし、電気剥離性を向上させるためには、ポリマーの比誘電率が大きいことが好ましく、この観点からは特に本実施形態におけるポリマーは、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種を含むことが好ましい。ポリエステル系ポリマー及びウレタン系ポリマーは末端に分極しやすい水酸基を有することから、また、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は、カルボキシル基、アルコキシ基、ヒドロキシル基及び/又はアミド結合が分極しやすいことから、これらのポリマーを用いることで、比誘電率が比較的大きいポリマーを得ることができる。本実施形態のポリマー中のポリエステル系ポリマー、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の含有量は、合計で60質量%以上であることが好ましく、80質量%以上であることがより好ましい。
また、特に、コストや生産性、及び初期接着力を大きくするためには、本実施形態におけるポリマーは、アクリル系ポリマーであることが好ましい。
すなわち、本実施形態の粘着剤組成物は、アクリル系ポリマーを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。
The polymer in the present embodiment is usually used as an adhesive, and is not particularly limited as long as it has tackiness. Examples thereof include an acrylic polymer, a rubber polymer, a vinylalkyl ether polymer, a silicone polymer, and a polyester polymer. , Polyamide-based polymers, urethane-based polymers, fluorine-based polymers, and epoxy-based polymers. The polymers can be used alone or in combination of two or more.
To increase the relative permittivity of components other than the ionic liquid of the obtained pressure-sensitive adhesive layer, and also to increase the ionic conductivity and the capacitance per unit area of the bonding interface of the obtained pressure-sensitive adhesive layer, and to improve the electrical peelability. It is preferable that the polymer has a large relative dielectric constant. From this viewpoint, the polymer in the present embodiment particularly includes a polyester-based polymer, a urethane-based polymer, and a carboxyl group, an alkoxy group, a hydroxyl group, and / or an amide bond. It is preferable to include at least one selected from the group consisting of acrylic polymers. Since polyester-based polymers and urethane-based polymers have easily polarizable hydroxyl groups at the terminals, acrylic polymers having carboxyl groups, alkoxy groups, hydroxyl groups and / or amide bonds include carboxyl groups, alkoxy groups, hydroxyl groups and Since the amide bond is easily polarized, a polymer having a relatively large relative dielectric constant can be obtained by using these polymers. The total content of the polyester polymer and the acrylic polymer having a carboxyl group, an alkoxy group, a hydroxyl group and / or an amide bond in the polymer of the present embodiment is preferably 60% by mass or more, and 80% by mass or more. More preferably, it is the above.
In particular, in order to increase the cost, productivity, and initial adhesive strength, the polymer in the present embodiment is preferably an acrylic polymer.
That is, the pressure-sensitive adhesive composition of the present embodiment is preferably an acrylic pressure-sensitive adhesive composition containing an acrylic polymer as a polymer.
アクリル系ポリマーは、炭素数1~14のアルキル基を有する(メタ)アクリル酸アルキルエステル(下記式(1))に由来するモノマーユニットを含むことが好ましい。このようなモノマーユニットは、大きな初期接着力を得るために好適である。さらに、粘着剤層のイオン液体以外の成分の比誘電率を大きくし、また、得られる粘着剤層のイオン伝導度及び接着界面の単位面積あたりのキャパシタンスを大きくし、電気剥離性を向上させるには下記式(1)におけるアルキル基Rbの炭素数は小さいことが好ましく、特に8以下であることが好ましく、4以下であることがより好ましい。
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]
The acrylic polymer preferably contains a monomer unit derived from an alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms (the following formula (1)). Such a monomer unit is suitable for obtaining a large initial adhesive force. Furthermore, the relative permittivity of components other than the ionic liquid of the pressure-sensitive adhesive layer is increased, and the ionic conductivity and the capacitance per unit area of the bonding interface of the obtained pressure-sensitive adhesive layer are increased, thereby improving the electrical peelability. In the formula (1), the alkyl group Rb preferably has a small carbon number, particularly preferably 8 or less, more preferably 4 or less.
CH 2 CC (R a ) COOR b (1)
[R a in the formula (1) is a hydrogen atom or a methyl group, and R b is an alkyl group having 1 to 14 carbon atoms.]
炭素数1~14のアルキル基を有する(メタ)アクリル酸アルキルエステルとしては、例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、イソプロピル(メタ)アクリレート、n-ブチル(メタ)アクリレート、sec-ブチル(メタ)アクリレート、1,3-ジメチルブチルアクリレート、ペンチル(メタ)アクリレート、イソペンチル(メタ)アクリレート、へキシル(メタ)アクリレート、2-エチルブチル(メタ)アクリレート、ヘプチル(メタ)アクリレート、n-オクチル(メタ)アクリレート、イソオクチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、n-ノニル(メタ)アクリレート、イソノニル(メタ)アクリレート、n-デシル(メタ)アクリレート、イソデシル(メタ)アクリレート、n-ドデシル(メタ)アクリレート、n-トリデシル(メタ)アクリレート、およびn-テトラデシル(メタ)アクリレート等が挙げられる。中でもn-ブチルアクリレート、2-エチルヘキシルアクリレート、イソノニルアクリレートが好ましい。炭素数1~14のアルキル基を有する(メタ)アクリル酸アルキルエステルは、単独で又は2種以上組み合わせて用いることができる。 Examples of the alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and 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) A) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) a Relate, isodecyl (meth) acrylate, n- dodecyl (meth) acrylate, n- tridecyl (meth) acrylate, and n- tetradecyl (meth) acrylate. Among them, n-butyl acrylate, 2-ethylhexyl acrylate and isononyl acrylate are preferred. The alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms can be used alone or in combination of two or more.
アクリル系ポリマーを構成する全モノマー成分(100質量%)に対する炭素数1~14のアルキル基を有する(メタ)アクリル酸アルキルエステルの割合は、特に限定されないが、70質量%以上が好ましく、より好ましくは80質量%以上、さらに好ましくは85質量%以上である。アクリル系ポリマーの割合が70質量%以上であると、大きな初期接着力を得やすくなる。 The ratio of the alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms to all the 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 is easy to obtain a large initial adhesive force.
アクリル系ポリマーとしては、凝集力、耐熱性、架橋性等の改質を目的として、炭素数1~14のアルキル基を有する(メタ)アクリル酸アルキルエステルに由来するモノマーユニットの他に、これと共重合可能な極性基含有モノマーに由来するモノマーユニットを含むことが好ましい。モノマーユニットは、架橋点を付与することができ、大きな初期接着力を得るために好適である。さらに、粘着剤層のイオン液体以外の成分の比誘電率を大きくし、また、得られる粘着剤層のイオン伝導度及び接着界面の単位面積あたりのキャパシタンスを大きくし、電気剥離性を向上させるという観点からも、極性基含有モノマーに由来するモノマーユニットを含むことが好ましい。 As the acrylic polymer, in addition to a monomer unit derived from an alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms, it is used for the purpose of improving cohesion, heat resistance, crosslinkability, and the like. It is preferable to include a monomer unit derived from a copolymerizable polar group-containing monomer. The monomer unit can provide a crosslinking point and is suitable for obtaining a large initial adhesive force. Furthermore, the relative permittivity of components other than the ionic liquid of the pressure-sensitive adhesive layer is increased, and the ionic conductivity of the obtained pressure-sensitive adhesive layer and the capacitance per unit area of the bonding interface are increased, thereby improving the electrical peelability. From the viewpoint as well, it is preferable to include a monomer unit derived from a polar group-containing monomer.
極性基含有モノマーとしては、例えば、カルボキシル基含有モノマー、アルコキシ基含有モノマー、ヒドロキシル基含有モノマー、シアノ基含有モノマー、ビニル基含有モノマー、芳香族ビニルモノマー、アミド基含有モノマー、イミド基含有モノマー、アミノ基含有モノマー、エポキシ基含有モノマー、ビニルエーテルモノマー、N-アクリロイルモルホリン、スルホ基含有モノマー、リン酸基含有モノマー、および酸無水物基含有モノマー等が挙げられる。中でも凝集性に優れる点から、カルボキシル基含有モノマー、アルコキシ基含有モノマー、ヒドロキシル基含有モノマー、アミド基含有モノマーが好ましく、特に、カルボキシル基含有モノマーが好ましい。カルボキシル基含有モノマーは、特に大きな初期接着力を得るために好適である。極性基含有モノマーは、単独で又は2種以上組み合わせて用いることができる。 Examples of the polar group-containing monomer include a carboxyl group-containing monomer, an alkoxy group-containing monomer, a hydroxyl group-containing monomer, a cyano group-containing monomer, a vinyl group-containing monomer, an aromatic vinyl monomer, an amide group-containing monomer, an imide group-containing monomer, and amino. Examples include a group-containing monomer, an epoxy group-containing monomer, a vinyl ether monomer, N-acryloylmorpholine, a sulfo group-containing monomer, a phosphoric acid group-containing monomer, and an acid anhydride group-containing monomer. Among them, a carboxyl group-containing monomer, an alkoxy group-containing monomer, a hydroxyl group-containing monomer, and an amide group-containing monomer are preferable from the viewpoint of excellent cohesiveness, and a carboxyl group-containing monomer is particularly preferable. Carboxyl group-containing monomers are particularly suitable for obtaining a large initial adhesive strength. The polar group-containing monomers can be used alone or in combination of two or more.
カルボキシル基含有モノマーとしては、例えば、アクリル酸、メタクリル酸、カルボキシエチル(メタ)アクリレート、カルボキシペンチル(メタ)アクリレート、イタコン酸、マレイン酸、フマル酸、クロトン酸、およびイソクロトン酸等が挙げられる。特に、アクリル酸が好ましい。カルボキシル基含有モノマーは、単独で又は2種以上組み合わせて用いることができる。 Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid. In particular, acrylic acid is preferred. The carboxyl group-containing monomers can be used alone or in combination of two or more.
アルコキシ基含有モノマーとしては、例えばメトキシ基含有モノマーやエトキシ基含有モノマーが挙げられる。メトキシ基含有モノマーとしては、例えば、2-メトキシエチルアクリレートが挙げられる。 (4) Examples of the alkoxy group-containing monomer include a methoxy group-containing monomer and an ethoxy group-containing monomer. Examples of the methoxy group-containing monomer include 2-methoxyethyl acrylate.
ヒドロキシル基含有モノマーとしては、例えば、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート、6-ヒドロキシヘキシル(メタ)アクリレート、8-ヒドロキシオクチル(メタ)アクリレート、10-ヒドロキシデシル(メタ)アクリレート、12-ヒドロキシラウリル(メタ)アクリレート、(4-ヒドロキシメチルシクロへキシル)メチル(メタ)アクリレート、N-メチロール(メタ)アクリルアミド、ビニルアルコール、アリルアルコール、2-ヒドロキシエチルビニルエーテル、4-ヒドロキシブチルビニルエーテル、およびジエチレングリコールモノビニルエーテル等が挙げられる。特に、2-ヒドロキシエチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレートが好ましい。ヒドロキシル基含有モノマーは、単独で又は2種以上組み合わせて用いることができる。 Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 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. Particularly, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable. The hydroxyl group-containing monomers can be used alone or in combination of two or more.
アミド基含有モノマーとしては、例えば、アクリルアミド、メタクリルアミド、N-ビニルピロリドン、N,N-ジメチルアクリルアミド、N,N-ジメチルメタクリルアミド、N,N-ジエチルアクリルアミド、N,N-ジエチルメタクリルアミド、N,N´-メチレンビスアクリルアミド、N,N-ジメチルアミノプロピルアクリルアミド、N,N-ジメチルアミノプロピルメタクリルアミド、およびジアセトンアクリルアミド等が挙げられる。アミド基含有モノマーは、単独で又は2種以上組み合わせて用いることができる。 Examples of the amide group-containing monomer 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, diacetoneacrylamide and the like. The amide group-containing monomers can be used alone or in combination of two or more.
シアノ基含有モノマーとしては、例えば、アクリロニトリル、およびメタクリロニトリル等が挙げられる。 Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.
ビニル基含有モノマーとしては、例えば、酢酸ビニル、プロピオン酸ビニル、およびラウリン酸ビニル等のビニルエステル類等が挙げられ、特に酢酸ビニルが好ましい。 Examples of the vinyl group-containing monomer include vinyl esters such as vinyl acetate, vinyl propionate, and vinyl laurate, with vinyl acetate being particularly preferred.
芳香族ビニルモノマーとしては、例えば、スチレン、クロロスチレン、クロロメチルスチレン、α-メチルスチレン、およびその他の置換スチレン等が挙げられる。 Examples of the aromatic vinyl monomer include styrene, chlorostyrene, chloromethylstyrene, α-methylstyrene, and other substituted styrenes.
イミド基含有モノマーとしては、例えば、シクロヘキシルマレイミド、イソプロピルマレイミド、N-シクロヘキシルマレイミド、およびイタコンイミド等が挙げられる。 Examples of the imide group-containing monomer include cyclohexylmaleimide, isopropylmaleimide, N-cyclohexylmaleimide, and itaconimide.
アミノ基含有モノマーとしては、例えば、アミノエチル(メタ)アクリレート、N,N-ジメチルアミノエチル(メタ)アクリレート、およびN,N-ジメチルアミノプロピル(メタ)アクリレート等が挙げられる。 Examples of the amino group-containing monomer include, for example, aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and N, N-dimethylaminopropyl (meth) acrylate.
エポキシ基含有モノマーとしては、例えば、グリシジル(メタ)アクリレート、メチルグリシジル(メタ)アクリレート、およびアリルグリシジルエーテル等が挙げられる。 {Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and allyl glycidyl ether.
ビニルエーテルモノマーとしては、例えば、メチルビニルエーテル、エチルビニルエーテル、およびイソブチルビニルエーテル等が挙げられる。 Examples of the vinyl ether monomer include methyl vinyl ether, ethyl vinyl ether, and isobutyl vinyl ether.
アクリル系ポリマーを構成する全モノマー成分(100質量%)に対する極性基含有モノマーの割合は、0.1質量%以上35質量%以下が好ましい。極性基含有モノマーの割合の上限は、より好ましくは25質量%であり、さらに好ましくは20質量%であり、下限は、より好ましくは0.5質量%であり、さらに好ましくは1質量%であり、特に好ましくは2質量%である。極性基含有モノマーの割合が0.1質量%以上であると、凝集力が得やすくなるため、粘着剤層を剥離した後の被着体表面に糊残りが生じにくくなり、また、電気剥離性が向上する。また、極性基含有モノマーの割合が30質量%以下であると、粘着剤層が被着体に過度に密着し重剥離化することを防ぎやすくなる。特に2質量%以上20質量%以下であると、被着体に対する剥離性と、粘着剤層と他の層との密着性との両立が図りやすくなる。 (4) The ratio of the polar group-containing monomer to all the monomer components (100% by mass) constituting the acrylic polymer is preferably from 0.1% by mass to 35% by mass. The upper limit of the proportion of the polar group-containing monomer is more preferably 25% by mass, further preferably 20% by mass, and the lower limit is more preferably 0.5% by mass, and still more preferably 1% by mass. And particularly preferably 2% by mass. When the proportion of the polar group-containing monomer is 0.1% by mass or more, a cohesive force is easily obtained, so that adhesive residue hardly remains on the adherend surface after the pressure-sensitive adhesive layer is peeled off. Is improved. Further, when the proportion of the polar group-containing monomer is 30% by mass or less, it becomes easy to prevent the pressure-sensitive adhesive layer from being excessively adhered to the adherend and heavy peeling. In particular, when the content is 2% by mass or more and 20% by mass or less, it is easy to achieve both releasability from the adherend and adhesion between the pressure-sensitive adhesive layer and another layer.
また、アクリル系ポリマーを構成するモノマー成分としては、アクリル系ポリマーに架橋構造を導入して、必要な凝集力を得やすくするために、多官能モノマーが含まれていてもよい。 モ ノ マ ー Further, as a monomer component constituting the acrylic polymer, a polyfunctional monomer may be contained in order to introduce a crosslinked structure into the acrylic polymer to easily obtain a necessary cohesive force.
多官能モノマーとしては、例えば、エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、1,6-へキサンジオールジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、ジビニルベンゼン、およびN,N´-メチレンビスアクリルアミド等が挙げられる。多官能モノマーは、単独で又は2種以上組み合わせて用いることができる。 Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1,6-hexanediol di ( Examples thereof include (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, divinylbenzene, and N, N'-methylenebisacrylamide. The polyfunctional monomers can be used alone or in combination of two or more.
アクリル系ポリマーを構成する全モノマー成分(100質量%)に対する多官能モノマーの含有量は、0.1質量%以上15質量%以下が好ましい。多官能モノマーの含有量の上限は、より好ましくは10質量%であり、下限は、より好ましくは3質量%である。多官能モノマーの含有量が、0.1質量%以上であると、粘着剤層の柔軟性、接着性が向上しやすくなり好ましい。多官能モノマーの含有量が、15質量%以下であると、凝集力が高くなりすぎず、適度な接着性が得やすくなる。 (4) The content of the polyfunctional monomer with respect to all monomer components (100% by mass) constituting the acrylic polymer is preferably from 0.1% by mass to 15% by mass. The upper limit of the content of the polyfunctional monomer is more preferably 10% by mass, and the lower limit is more preferably 3% by mass. When the content of the polyfunctional monomer is 0.1% by mass or more, the flexibility and adhesion of the pressure-sensitive adhesive layer are easily improved, which is preferable. When the content of the polyfunctional monomer is 15% by mass or less, the cohesive force does not become too high, and it becomes easy to obtain appropriate adhesiveness.
ポリエステル系ポリマーは、典型的にはジカルボン酸等の多価カルボン酸やその誘導体(以下「多価カルボン酸モノマー」ともいう)と、ジオール等の多価アルコールやその誘導体(以下「多価アルコールモノマー」)とが縮合した構造を有するポリマーである。 The polyester-based polymer is typically a polycarboxylic acid such as dicarboxylic acid or a derivative thereof (hereinafter also referred to as “polycarboxylic acid monomer”), a polyhydric alcohol such as a diol or a derivative thereof (hereinafter “polyhydric alcohol monomer”). ") Is a polymer having a condensed structure.
多価カルボン酸モノマーとしては、特に限定されないが例えば、アジピン酸、アゼライン酸、ダイマー酸、セバシン酸、1,4-シクロヘキサンジカルボン酸、1,3-シクロヘキサンジカルボン酸、1,2-シクロヘキサンジカルボン酸、4-メチル-1,2-シクロヘキサンジカルボン酸、ドデセニル無水コハク酸、フマル酸、コハク酸、ドデカン二酸、ヘキサヒドロ無水フタル酸、テトラヒドロ無水フタル酸等、マレイン酸、無水マレイン酸、イタコン酸、シトラコン酸、およびこれらの誘導体等を用いることができる。
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。
The polyvalent carboxylic acid monomer is not particularly limited, but includes, for example, 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, dodecenyl succinic anhydride, fumaric acid, succinic acid, dodecane diacid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, etc., maleic acid, maleic anhydride, itaconic acid, citraconic acid , And derivatives thereof.
The polycarboxylic acid monomers can be used alone or in combination of two or more.
多価アルコールモノマーとしては、特に限定されないが例えば、エチレングリコ-ル、1,2-プロピレングリコール、1,3-プロパンジオ-ル、2-メチル-1,3-プロパンジオール、1,2-ブタンジオール、1,3-ブタンジオール、1,4-ブタンジオール、1,5-ペンタンジオ-ル、1,6-ヘキサンジオ-ル、3-メチル-1,5-ペンタンジオール、ネオペンチルグリコール、ジエチレングリコール、ジプロピレングリコール、2,2,4-トリメチル-1,5-ペンタンジオール、2-エチル-2-ブチルプロパンジオール、1,9-ノナンジオール、2-メチルオクタンジオール、1,10-デカンジオール、およびこれらの誘導体等を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。
The polyhydric alcohol monomer is not particularly restricted but includes, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-butane Diols, 1,3-butanediol, 1,4-butanediol, 1,5-pentaneddiol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, diethylene glycol, diethylene glycol Propylene glycol, 2,2,4-trimethyl-1,5-pentanediol, 2-ethyl-2-butylpropanediol, 1,9-nonanediol, 2-methyloctanediol, 1,10-decanediol, and these And the like can be used.
The polyhydric alcohol monomers can be used alone or in combination of two or more.
また、本実施形態のポリマーは、イオン性ポリマーを含んでもよい。イオン性ポリマーは、イオン性官能基を有するポリマーである。ポリマーがイオン性ポリマーを含むことで、ポリマーの比誘電率が増加し、電気剥離性が向上する。ポリマーがイオン性ポリマーを含む場合、イオン性ポリマーの含有量は、ポリマー100質量部に対して、0.05質量部以上2質量部以下が好ましい。 ポ リ マ ー In addition, the polymer of the present embodiment may include an ionic polymer. An ionic polymer is a polymer having an ionic functional group. When the polymer contains an ionic polymer, the dielectric constant of the polymer is increased, and the electrical stripping property is improved. When the polymer contains an ionic polymer, the content of the ionic polymer is preferably 0.05 part by mass or more and 2 parts by mass or less based on 100 parts by mass of the polymer.
本実施形態においてポリマーは、モノマー成分を(共)重合することにより得ることができる。重合方法としては、特に限定されないが、溶液重合、乳化重合、塊状重合、懸濁重合、光重合(活性エネルギー線重合)法等が挙げられる。特に、コストや生産性の観点から、溶液重合法が好ましい。ポリマーは、共重合させた場合、ランダム共重合体、ブロック共重合体、交互共重合体、グラフト共重合体等いずれでもよい。 ポ リ マ ー In the present embodiment, the polymer can be obtained by (co) polymerizing a monomer component. The polymerization method is not particularly limited, and examples thereof include solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, and photopolymerization (active energy ray polymerization). Particularly, a solution polymerization method is preferable from the viewpoint of cost and productivity. When the polymer is copolymerized, it may be any of a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer and the like.
溶液重合法としては、特に限定されないが、モノマー成分、重合開始剤等を、溶剤に溶解し、加熱して重合し、ポリマーを含むポリマー溶液を得る方法等が挙げられる。 The solution polymerization method is not particularly limited, and examples thereof include a method of dissolving a monomer component, a polymerization initiator, and the like in a solvent, heating and polymerizing to obtain a polymer solution containing a polymer.
溶液重合法に用いられる溶剤としては、各種の一般的な溶剤を用いることができる。このような溶剤(重合溶剤)としては、例えば、トルエン、ベンゼン、およびキシレン等の芳香族炭化水素類;酢酸エチル、および酢酸n-ブチル等のエステル類;n-ヘキサン、およびn-ヘプタン等の脂肪族炭化水素類;シクロヘキサン、およびメチルシクロヘキサン等の脂環式炭化水素類;メチルエチルケトン、およびメチルイソブチルケトン等のケトン類等の有機溶剤等が挙げられる。溶剤は、単独で又は2種以上組み合わせて用いることができる。 各種 Various general solvents can be used as the solvent used in the solution polymerization method. Examples of such a solvent (polymerization solvent) include aromatic hydrocarbons such as toluene, benzene, and xylene; esters such as ethyl acetate and n-butyl acetate; and n-hexane and n-heptane. Aliphatic hydrocarbons; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; and organic solvents such as methyl ethyl ketone and ketones such as methyl isobutyl ketone. The solvents can be used alone or in combination of two or more.
溶剤の使用量は、特に限定されないが、ポリマーを構成する全モノマー成分(100質量部)に対して、10質量部以上1000質量部以下が好ましい。溶剤の使用量の上限は、より好ましくは500質量部であり、下限は、より好ましくは50質量部である。 使用 The amount of the solvent used is not particularly limited, but is preferably from 10 parts by mass to 1,000 parts by mass based on all the monomer components (100 parts by mass) constituting the polymer. The upper limit of the amount of the solvent used is more preferably 500 parts by mass, and the lower limit is more preferably 50 parts by mass.
溶液重合法に用いられる重合開始剤としては、特に限定されないが、過酸化物系重合開始剤、アゾ系重合開始剤等が挙げられる。過酸化物系重合開始剤としては、特に限定されないが、パーオキシカーボネート、ケトンパーオキサイド、パーオキシケタール、ハイドロパーオキサイド、ジアルキルパーオキサイド、ジアシルパーオキサイド、およびパーオキシエステル等が挙げられ、より具体的には、ベンゾイルパーオキサイド、t-ブチルハイドロパーオキサイド、ジ-t-ブチルパーオキサイド、t-ブチルパーオキシベンゾエート、ジクミルパーオキサイド、1,1-ビス(t-ブチルパーオキシ)-3,3,5-トリメチルシクロヘキサン、および1,1-ビス(t-ブチルパーオキシ)シクロドデカン等が挙げられる。アゾ系重合開始剤としては、特に限定されないが、2,2′-アゾビスイソブチロニトリル、2,2′-アゾビス-2-メチルブチロニトリル、2,2′-アゾビス(2,4-ジメチルバレロニトリル)、2,2′-アゾビス(2-メチルプロピオン酸)ジメチル、2,2′-アゾビス(4-メトキシ-2,4-ジメチルバレロニトリル)、1,1′-アゾビス(シクロヘキサン-1-カルボニトリル)、2,2′-アゾビス(2,4,4-トリメチルペンタン)、4,4′-アゾビス-4-シアノバレリアン酸、2,2′-アゾビス(2-アミジノプロパン)ジヒドロクロライド、2,2′-アゾビス[2-(5-メチル-2-イミダゾリン-2-イル)プロパン]ジヒドロクロライド、2,2′-アゾビス(2-メチルプロピオンアミジン)二硫酸塩、2,2′-アゾビス(N,N′-ジメチレンイソブチルアミジン)ヒドロクロライド、および2,2′-アゾビス[N-(2-カルボキシエチル)-2-メチルプロピオンアミジン]ハイドレート等が挙げられる。重合開始剤は、単独で又は2種以上組み合わせて用いることができる。 重合 The polymerization initiator used in the solution polymerization method is not particularly limited, and examples thereof include a peroxide-based polymerization initiator and an azo-based polymerization initiator. The peroxide-based polymerization initiator is not particularly limited, and examples thereof include peroxycarbonate, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, and peroxyester. Specifically, benzoyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, t-butylperoxybenzoate, dicumyl peroxide, 1,1-bis (t-butylperoxy) -3, 3,5-trimethylcyclohexane and 1,1-bis (t-butylperoxy) cyclododecane. The azo polymerization initiator is not particularly limited, but includes 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis (2,4- Dimethylvaleronitrile), 2,2'-azobis (2-methylpropionic acid) 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-methylpropionamidi) ) Disulfate, 2,2'-azobis (N, N'-dimethyleneisobutylamidine) hydrochloride, and 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate And the like. The polymerization initiators can be used alone or in combination of two or more.
重合開始剤の使用量は、特に限定されないが、ポリマーを構成する全モノマー成分(100質量部)に対して、0.01質量部以上5質量部以下が好ましい。重合開始剤の使用量の上限は、より好ましくは3質量部であり、下限は、より好ましくは0.05質量部である。 使用 The amount of the polymerization initiator used is not particularly limited, but is preferably 0.01 part by mass or more and 5 parts by mass or less based on all monomer components (100 parts by mass) constituting the polymer. The upper limit of the use amount of the polymerization initiator is more preferably 3 parts by mass, and the lower limit is more preferably 0.05 parts by mass.
溶液重合法で、加熱して重合する際の加熱温度は、特に限定されないが、例えば50℃以上80℃以下である。加熱時間は、特に限定されないが、例えば1時間以上24時間以下である。 (4) The heating temperature at the time of polymerization by heating in the solution polymerization method is not particularly limited, but is, for example, 50 ° C. or more and 80 ° C. or less. The heating time is not particularly limited, but is, for example, 1 hour or more and 24 hours or less.
ポリマーの重量平均分子量は、特に限定されないが、10万以上500万以下が好ましい。重量平均分子量の上限は、より好ましくは400万であり、さらに好ましくは300万であり、下限は、より好ましくは20万であり、さらに好ましくは30万である。重量平均分子量が10万以上であると、凝集力が小さくなり、粘着剤層を剥離した後の被着体表面に糊残りが生じるという不具合を効果的に抑制できる。また、重量平均分子量が500万以下であると、粘着剤層を剥離した後の被着体表面の濡れ性が不十分となるという不具合を効果的に抑制できる。 重量 The weight average molecular weight of the polymer is not particularly limited, but is preferably from 100,000 to 5,000,000. The upper limit of the weight average molecular weight is more preferably 4,000,000, further preferably 3,000,000, and the lower limit is more preferably 200,000, further preferably 300,000. When the weight average molecular weight is 100,000 or more, the cohesive force is reduced, and the problem that adhesive residue remains on the surface of the adherend after peeling off the pressure-sensitive adhesive layer can be effectively suppressed. Further, when 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 peeling the pressure-sensitive adhesive layer becomes insufficient.
重量平均分子量は、ゲルパーミエーションクロマトグラフ(GPC)法により測定して得られたものであり、より具体的には、例えば、GPC測定装置として、商品名「HLC-8220GPC」(東ソー社製)を用いて、下記の条件にて測定し、標準ポリスチレン換算値により算出することができる。(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℃
The weight average molecular weight is obtained by measurement by gel permeation chromatography (GPC), and more specifically, for example, as a GPC measuring device, trade name “HLC-8220GPC” (manufactured by Tosoh Corporation) Can be measured under the following conditions, and can be calculated by a standard polystyrene conversion value. (Weight average molecular weight measurement conditions)
-Sample concentration: 0.2% by mass (tetrahydrofuran solution)
・ Sample injection volume: 10 μL
-Sample column: TSKguardcolumn SuperHZ-H (1) + TSKgel SuperHZM-H (2)
・ Reference column: TSKgel SuperH-RC (1)
・ Eluent: tetrahydrofuran (THF)
・ Flow rate: 0.6 mL / min
・ Detector: Differential refractometer (RI)
・ Column temperature (measurement temperature): 40 ° C
ポリマーのガラス転移温度(Tg)は、特に限定されないが、0℃以下であると、初期接着力の低下を抑制できるため好ましく、より好ましくは-10℃以下であり、さらに好ましくは-20℃以下である。また、-40℃以下であると電圧印加による接着力の低下率が特に大きくなるため特に好ましく、最も好ましくは-50℃以下である。 The glass transition temperature (Tg) of the polymer is not particularly limited, but is preferably 0 ° C. or lower, because it can suppress a decrease in initial adhesive strength, more preferably −10 ° C. or lower, and still more preferably −20 ° C. or lower. It is. Further, it is particularly preferable that the temperature is −40 ° C. or lower, since the rate of decrease in adhesive force due to voltage application becomes particularly large, and most preferably −50 ° C. or lower.
ガラス転移温度(Tg)は、例えば、下記式(Y)(Fox式)に基づいて計算することができる。
1/Tg=W1/Tg1+W2/Tg2+・・・+Wn/Tgn (Y)
[式(Y)中、Tgはポリマーのガラス転移温度(単位:K)、Tgi(i=1、2、・・・n)はモノマーiがホモポリマーを形成した際のガラス転移温度(単位:K)、Wi(i=1、2、・・・n)はモノマーiの全モノマー成分中の質量分率を表す]
上記式(Y)は、ポリマーが、モノマー1、モノマー2、・・・、モノマーnのn種類のモノマー成分から構成される場合の計算式である。
The glass transition temperature (Tg) can be calculated based on, for example, the following formula (Y) (Fox formula).
1 / Tg = W1 / Tg1 + W2 / Tg2 +... + Wn / Tgn (Y)
[In the formula (Y), Tg is the glass transition temperature of the polymer (unit: K), and Tgi (i = 1, 2,... N) is the glass transition temperature (unit: K) and Wi (i = 1, 2,... N) represent the mass fraction of monomer i in all monomer components]
The above formula (Y) is a calculation formula in the case where the polymer is composed of n kinds of monomer components of
なお、ホモポリマーを形成した際のガラス転移温度とは、当該モノマーの単独重合体のガラス転移温度を意味し、あるモノマー(「モノマーX」と称する場合がある)のみをモノマー成分として形成される重合体のガラス転移温度(Tg)を意味する。具体的には、「Polymer Handbook」(第3版、John Wiley & Sons,Inc,1989年)に数値が挙げられている。なお、当該文献に記載されていない単独重合体のガラス転移温度(Tg)は、例えば、以下の測定方法により得られる値をいう。すなわち、温度計、撹拌機、窒素導入管及び還流冷却管を備えた反応器に、モノマーX100質量部、2,2´-アゾビスイソブチロニトリル0.2質量部および重合溶媒として酢酸エチル200質量部を投入し、窒素ガスを導入しながら1時間撹拌する。このようにして重合系内の酸素を除去した後、63℃に昇温し10時間反応させる。次いで、室温まで冷却し、固形分濃度33質量%のホモポリマー溶液を得る。次いで、このホモポリマー溶液を剥離ライナー上に流延塗布し、乾燥して厚み約2mmの試験サンプル(シート状のホモポリマー)を作製する。そして、この試験サンプルをアルミニウム製のオープンセルに約1~2mg秤量し、温度変調DSC(商品名「Q-2000」 ティー・エイ・インスツルメント社製)を用いて、50ml/minの窒素雰囲気下で昇温速度5℃/minにて、ホモポリマーのReversing Heat Flow(比熱成分)挙動を得る。JIS-K-7121を参考にして、得られたReversing Heat Flowの低温側のベースラインと高温側のベースラインを延長した直線から縦軸方向に等距離にある直線と、ガラス転移の階段状変化部分の曲線とが交わる点の温度をホモポリマーとした時のガラス転移温度(Tg)とする。 The glass transition temperature when a homopolymer is formed means the glass transition temperature of a homopolymer of the monomer, and only a certain monomer (sometimes referred to as “monomer X”) is formed as a monomer component. It means the glass transition temperature (Tg) of the polymer. Specifically, numerical values are listed in "Polymer Handbook" (3rd edition, John Wiley & Sons, Inc., 1989). The glass transition temperature (Tg) of a homopolymer not described in the literature refers to, for example, a value obtained by the following measurement method. That is, a reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser was charged with 100 parts by mass of monomer X, 0.2 parts by mass of 2,2'-azobisisobutyronitrile, and 200 parts by mass of ethyl acetate as a polymerization solvent. A mass part is charged and stirred for 1 hour while introducing nitrogen gas. After removing the oxygen in the polymerization system in this way, the temperature is raised to 63 ° C. and the reaction is performed for 10 hours. Next, the mixture is cooled to room temperature to obtain a homopolymer solution having a solid content of 33% by mass. Next, the homopolymer solution is cast on a release liner and dried to prepare a test sample (sheet-like homopolymer) having a thickness of about 2 mm. Then, about 1-2 mg of this test sample was weighed into an aluminum open cell, and a nitrogen atmosphere of 50 ml / min was measured using a temperature-modulated DSC (trade name “Q-2000” manufactured by TIA Instruments Inc.). Under the heating rate of 5 ° C./min, the reversing heat flow (specific heat component) behavior of the homopolymer is obtained. Referring to JIS-K-7121, the obtained reversing heat flow has a low temperature side base line and a high temperature side base line, and a straight line equidistant in the vertical axis direction, and a stepwise change in glass transition. The temperature at the point where the curves intersect with each other is defined as the glass transition temperature (Tg) when the homopolymer is used.
本実施形態の粘着剤組成物におけるポリマーの含有量は、粘着剤組成物全量(100質量%)に対して、50質量%以上99.9質量%以下が好ましく、上限は、より好ましくは99.5質量%、さらに好ましくは99質量%であり、下限は、より好ましくは60質量%、さらに好ましくは70質量%である。 The content of the polymer in the pressure-sensitive adhesive composition of the present embodiment is preferably from 50% by weight to 99.9% by weight based on the total amount of the pressure-sensitive adhesive composition (100% by weight), and the upper limit is more preferably 99.9% by weight. It is 5% by mass, more preferably 99% by mass, and the lower limit is more preferably 60% by mass, further preferably 70% by mass.
(イオン液体)
本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。
(Ionic liquid)
The ionic liquid in the present embodiment is not particularly limited as long as it is composed of a pair of anion and cation and is a molten salt (normal temperature molten salt) which 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 and will be described later. Is an ionic solid.
イオン液体のアニオンは、例えば、(FSO2)2N-、(CF3SO2)2N-、(CF3CF2SO2)2N-、(CF3SO2)3C-、Br-、AlCl4 -、Al2Cl7 -、NO3 -、BF4 -、PF6 -、CH3COO-、CF3COO-、CF3CF2CF2COO-、CF3SO3 -、CF3(CF2)3SO3 -、AsF6 -、SbF6 -、およびF(HF)n -等が挙げられる。なかでもアニオンとしては、(FSO2)2N-[ビス(フルオロスルホニル)イミドアニオン]、および(CF3SO2)2N-[ビス(トリフルオロメタンスルホニル)イミドアニオン]などのスルホニルイミド系化合物のアニオンが、化学的に安定であり、電気剥離性を良好にするために好適であることから好ましい。 The anions of the ionic liquid include, 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 − , and F (HF) n − . Above all, examples of the anion 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 preferred because they are chemically stable and are suitable for improving the electrical stripping property.
イオン液体におけるカチオンは、窒素含有オニウム、硫黄含有オニウム、およびリン含有オニウムカチオンが、化学的に安定であり、電気剥離性を良好にするために好適であることから好ましく、イミダゾリウム系、アンモニウム系、ピロリジニウム系、およびピリジニウム系カチオンがより好ましい。 The cations in the ionic liquid are preferably nitrogen-containing onium, sulfur-containing onium, and phosphorus-containing onium cations because they are chemically stable and suitable for improving electrical stripping properties, and are preferably imidazolium-based and ammonium-based onium cations. , Pyrrolidinium-based, and pyridinium-based cations are more preferred.
イミダゾリウム系カチオンとしては、例えば、1-メチルイミダゾリウムカチオン、1-エチル-3-メチルイミダゾリウムカチオン、1-プロピル-3-メチルイミダゾリウムカチオン、1-ブチル-3-メチルイミダゾリウムカチオン、1-ペンチル-3-メチルイミダゾリウムカチオン、1-ヘキシル-3-メチルイミダゾリウムカチオン、1-へプチル-3-メチルイミダゾリウムカチオン、1-オクチル-3-メチルイミダゾリウムカチオン、1-ノニル-3-メチルイミダゾリウムカチオン、1-ウンデシル-3-メチルイミダゾリウムカチオン、1-ドデシル-3-メチルイミダゾリウムカチオン、1-トリデシル-3-メチルイミダゾリウムカチオン、1-テトラデシル-3-メチルイミダゾリウムカチオン、1-ペンタデシル-3-メチルイミダゾリウムカチオン、1-ヘキサデシル-3-メチルイミダゾリウムカチオン、1-ヘプタデシル-3-メチルイミダゾリウムカチオン、1-オクタデシル-3-メチルイミダゾリウムカチオン、1-ウンデシル-3-メチルイミダゾリウムカチオン、1-ベンジル-3-メチルイミダゾリウムカチオン、1-ブチル-2,3-ジメチルイミダゾリウムカチオン、および1,3-ビス(ドデシル)イミダゾリウムカチオン等が挙げられる。 Examples of the imidazolium-based cation include 1-methylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-propyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, -Pentyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-heptyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-nonyl-3- Methyl imidazolium cation, 1-undecyl-3-methyl imidazolium cation, 1-dodecyl-3-methyl imidazolium cation, 1-tridecyl-3-methyl imidazolium cation, 1-tetradecyl-3-methyl imidazolium cation, 1 -Penta Sil-3-methylimidazolium cation, 1-hexadecyl-3-methylimidazolium cation, 1-heptadecyl-3-methylimidazolium cation, 1-octadecyl-3-methylimidazolium cation, 1-undecyl-3-methylimidazo Examples include a lithium cation, a 1-benzyl-3-methylimidazolium cation, a 1-butyl-2,3-dimethylimidazolium cation, and a 1,3-bis (dodecyl) imidazolium cation.
ピリジニウム系カチオンとしては、例えば、1-ブチルピリジニウムカチオン、1-ヘキシルピリジニウムカチオン、1-ブチル-3-メチルピリジニウムカチオン、1-ブチル-4-メチルピリジニウムカチオン、および1-オクチル-4-メチルピリジニウムカチオン等が挙げられる。 Examples of the pyridinium-based cation include 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, and 1-octyl-4-methylpyridinium cation And the like.
ピロリジニウム系カチオンとしては、例えば、1-エチル-1-メチルピロリジニウムカチオンおよび1-ブチル-1-メチルピロリジニウムカチオン等が挙げられる。 Examples of the pyrrolidinium cation include a 1-ethyl-1-methylpyrrolidinium cation and a 1-butyl-1-methylpyrrolidinium cation.
アンモニウム系カチオンとしては、例えば、テトラエチルアンモニウムカチオン、テトラブチルアンモニウムカチオン、メチルトリオクチルアンモニウムカチオン、テトラデシトリヘキシルアンモニウムカチオン、グリシジルトリメチルアンモニウムカチオンおよびトリメチルアミノエチルアクリレートカチオン等が挙げられる。 Examples of the ammonium-based cation include a tetraethylammonium cation, a tetrabutylammonium cation, a methyltrioctylammonium cation, a tetradecitrihexylammonium cation, a glycidyltrimethylammonium cation, and a trimethylaminoethylacrylate cation.
イオン液体としては、電圧印加時の接着力の低下率を大きくするという観点から、構成するカチオンとしては分子量160以下のカチオンを選択することが好ましく、上記の(FSO2)2N-[ビス(フルオロスルホニル)イミドアニオン]又は(CF3SO2)2N-[ビス(トリフルオロメタンスルホニル)イミドアニオン]と分子量160以下のカチオンとを含むイオン液体が特に好ましい。分子量160以下のカチオンとしては、例えば、1-メチルイミダゾリウムカチオン、1-エチル-3-メチルイミダゾリウムカチオン、1-プロピル-3-メチルイミダゾリウムカチオン、1-ブチル-3-メチルイミダゾリウムカチオン、1-ペンチル-3-メチルイミダゾリウムカチオン、1-ブチルピリジニウムカチオン、1-ヘキシルピリジニウムカチオン、1-ブチル-3-メチルピリジニウムカチオン、1-ブチル-4-メチルピリジニウムカチオン、1-エチル-1-メチルピロリジニウムカチオン、1-ブチル-1-メチルピロリジニウムカチオン、テトラエチルアンモニウムカチオン、グリシジルトリメチルアンモニウムカチオン、およびトリメチルアミノエチルアクリレートカチオン等が挙げられる。 As 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 force when voltage is applied, and the above-mentioned (FSO 2 ) 2 N − [bis ( An ionic liquid 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 is particularly preferable. Examples of the cation 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 Examples include a pyrrolidinium cation, a 1-butyl-1-methylpyrrolidinium cation, a tetraethylammonium cation, a glycidyltrimethylammonium cation, and a trimethylaminoethylacrylate cation.
また、イオン液体のカチオンとしては、下記式(2-A)~(2-D)で表されるカチオンも好ましい。
式(2-A)中のR1は、炭素数4~10の炭化水素基(好ましくは炭素数4~8の炭化水素基、より好ましくは炭素数4~6の炭化水素基)を表し、ヘテロ原子を含んでも良く、R2及びR3は、同一又は異なって、水素原子若しくは炭素数1~12の炭化水素基(好ましくは炭素数1~8の炭化水素基、より好ましくは炭素数2~6の炭化水素基、さらに好ましくは炭素数2~4の炭化水素基)を表し、ヘテロ原子を含んでも良い。但し、窒素原子が隣接する炭素原子と2重結合を形成する場合、R3は存在しない。 R 1 in the 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); R 2 and R 3 may be the same or different and each may be 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 2 to 2 carbon atoms). To 6 hydrocarbon groups, more preferably a hydrocarbon group having 2 to 4 carbon atoms), and may contain a hetero atom. However, when a nitrogen atom forms a double bond with an adjacent carbon atom, R 3 is not present.
式(2-B)中のR4は、炭素数2~10の炭化水素基(好ましくは炭素数2~8の炭化水素基、より好ましくは炭素数2~6の炭化水素基)を表し、ヘテロ原子を含んでも良く、R5、R6、及びR7は、同一又は異なって、水素原子若しくは炭素数1~12の炭化水素基(好ましくは炭素数1~8の炭化水素基、より好ましくは炭素数2~6の炭化水素基、さらに好ましくは炭素数2~4の炭化水素基)を表し、ヘテロ原子を含んでも良い。 R 4 in the 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); R 5 , R 6 and R 7 may be the same or different and each may be 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, and may contain a hetero atom.
式(2-C)中のR8は、炭素数2~10の炭化水素基(好ましくは炭素数2~8の炭化水素基、より好ましくは炭素数2~6の炭化水素基)を表し、ヘテロ原子を含んでも良く、R9、R10、及びR11は、同一又は異なって、水素原子若しくは炭素数1~16の炭化水素基(好ましくは炭素数1~10の炭化水素基、より好ましくは炭素数1~8の炭化水素基)を表し、ヘテロ原子を含んでも良い。 R 8 in the 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); R 9 , R 10 , and R 11 may be the same or different and may be 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 hetero atom.
式(2-D)中のXは、窒素、硫黄、又はリン原子を表し、R12、R13、R14、及びR15は、同一又は異なって、炭素数1~16の炭化水素基(好ましくは炭素数1~14の炭化水素基、より好ましくは炭素数1~10の炭化水素基、さらに好ましくは炭素数1~8の炭化水素基、特に好ましくは炭素数1~6の炭化水素基)を表し、ヘテロ原子を含んでも良い。但し、Xが硫黄原子の場合、R12は存在しない。 X in the formula (2-D) represents a nitrogen, sulfur, or phosphorus atom, and R 12 , R 13 , R 14 , and R 15 are the same or different and each have a hydrocarbon group of 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, further preferably a hydrocarbon group having 1 to 8 carbon atoms, particularly preferably a hydrocarbon group having 1 to 6 carbon atoms. ), And may include a hetero atom. Provided that when X is a sulfur atom, R 12 is absent.
イオン液体におけるカチオンの分子量は、例えば500以下、好ましくは400以下、より好ましくは300以下、さらに好ましくは250以下、特に好ましくは200以下、最も好ましくは160以下である。また、通常は50以上である。イオン液体におけるカチオンは、粘着剤層中で電圧印加時に陰極側に移動して、粘着剤層と被着体の界面付近に偏る性質を有すると考えられる。本発明では、このため初期接着力に対して電圧印加中の接着力が低下し、電気剥離性が生じる。分子量が500以下といった分子量が小さいカチオンは、粘着剤層中の陰極側へのカチオンの移動がより容易になり、電圧印加時における接着力の低下率を大きくするうえで好適である。 カ チ オ ン 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, further preferably 250 or less, particularly preferably 200 or less, and most preferably 160 or less. Also, it is usually 50 or more. It is considered that the cation in the ionic liquid moves to the cathode side when a voltage is applied in the pressure-sensitive adhesive layer, and has a property of being biased near the interface between the pressure-sensitive adhesive layer and the adherend. In the present invention, for this reason, the adhesive force during the application of a voltage is reduced with respect to the initial adhesive force, resulting in electrical peelability. A cation having a small molecular weight, such as a molecular weight of 500 or less, is suitable in that the movement of the cation to the cathode side in the pressure-sensitive adhesive layer becomes easier, and the rate of decrease in the adhesive force when a voltage is applied is suitable.
イオン液体の市販品としては、例えば、第一工業製薬株式会社製の「エレクセルAS-110」、「エレクセルMP-442」、「エレクセルIL-210」、「エレクセルMP-471」、「エレクセルMP-456」、「エレクセルAS-804」、三菱マテリアル株式会社製の「HMI-FSI」、日本カーリット株式会社製の「CIL-312」、および「CIL-313」等が挙げられる。 Commercially available ionic liquids include, for example, "Elexel AS-110", "Elexel MP-442", "Elexel IL-210", "Elexel MP-471", "Elexel MP-471" 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.
イオン液体のイオン伝導率は、0.1mS/cm以上10mS/cm以下が好ましい。イオン伝導率の上限は、より好ましくは5mS/cmであり、さらに好ましくは3mS/cmであり、下限は、より好ましくは0.3mS/cmであり、さらに好ましくは0.5mS/cmである。この範囲のイオン伝導率を有することで、低い電圧であっても十分に接着力が低下する。なお、イオン伝導率は、例えば、Solartron社製1260周波数応答アナライザを用い、ACインピーダンス法により測定することができる。 イ オ ン The ionic conductivity of the ionic liquid is preferably from 0.1 mS / cm to 10 mS / cm. The upper limit of the ionic conductivity is more preferably 5 mS / cm, further preferably 3 mS / cm, and the lower limit is more preferably 0.3 mS / cm, and still more preferably 0.5 mS / cm. By having the ionic conductivity in this range, the adhesive strength is sufficiently reduced even at a low voltage. The ionic conductivity can be measured by, for example, an AC impedance method using a 1260 frequency response analyzer manufactured by Solartron.
本実施形態の粘着剤組成物におけるイオン液体の含有量(配合量)は、ポリマー100質量部に対して、0.5質量部以上であることが電圧印加中の接着力を低下させる観点から好ましく、30質量部以下であることが初期接着力を高くする観点から好ましい。同様の観点から20質量部以下であることがより好ましく、15質量部以下であることがさらに好ましく、10質量部以下であることが特に好ましく、5質量部以下であることが最も好ましい。また、0.6質量部以上であることがより好ましく、0.8質量部以上であることがさらに好ましく、1.0質量部以上であることが特に好ましく、1.5質量部以上であることが最も好ましい。 The content (blending amount) of the ionic liquid in the pressure-sensitive adhesive composition of the present embodiment is preferably 0.5 parts by mass or more with respect to 100 parts by mass of the polymer, from the viewpoint of reducing the adhesive force during voltage application. , 30 parts by mass or less is preferable from the viewpoint of increasing the initial adhesive strength. From the same viewpoint, the amount 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 at least 0.6 part by mass, further preferably at least 0.8 part by mass, particularly preferably at least 1.0 part by mass, and at least 1.5 parts by mass. Is most preferred.
(その他の成分)
本実施形態の粘着剤組成物は、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、本実施形態の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。
(Other components)
The pressure-sensitive adhesive composition of the present embodiment may contain one or two components other than the polymer and the ionic liquid (hereinafter, may be referred to as “other components”) as long as the effects of the present invention are not impaired. More than one species can be contained. Hereinafter, other components that can be contained in the pressure-sensitive adhesive composition of the present embodiment will be described.
本実施形態の粘着剤組成物は、比誘電率やイオン伝導率、キャパシタンスを制御する目的でイオン性添加剤を含有してもよい。イオン性添加剤としては、例えばイオン性固体を用いることができる。 粘着 The pressure-sensitive adhesive composition of the present embodiment may contain an ionic additive for the purpose of controlling the relative dielectric constant, ionic conductivity, and capacitance. As the ionic additive, for example, an ionic solid can be used.
イオン性固体は、25℃で固体であるイオン性物質である。イオン性固体は特に限定されないが、例えば、先述のイオン性液体の説明の欄において例示したアニオンとカチオンを組み合わせて得られるイオン性物質のうち、固体であるものを用いることができる。粘着剤組成物がイオン性固体を含有する場合、イオン性固体の含有量は、ポリマー100質量部に対して、0.5質量部以上が好ましく、1質量部以上がより好ましく、また、10質量部以下が好ましく、5質量部以下がより好ましく、2.5質量部以下がさらに好ましい。 Ionic solids are ionic substances that are solid at 25 ° C. The ionic solid is not particularly limited. For example, a solid ionic substance can be used among the ionic substances obtained by combining an anion and a cation exemplified in the description of the ionic liquid described above. When the pressure-sensitive adhesive composition contains an ionic solid, the content of the ionic solid is preferably at least 0.5 part by mass, more preferably at least 1 part by mass, and preferably at least 10 parts by mass, based on 100 parts by mass of the polymer. Or less, more preferably 5 parts by mass or less, even more preferably 2.5 parts by mass or less.
本実施形態の粘着剤組成物は、ポリマーを架橋させることによりクリープ性やせん断性を改良する目的で、必要に応じて架橋剤を含有してもよい。架橋剤としては、例えば、イソシアネート系架橋剤や、エポキシ系架橋剤、メラミン系架橋剤、過酸化物系架橋剤、尿素系架橋剤、金属アルコキシド系架橋剤、金属キレート系架橋剤、金属塩系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、およびアミン系架橋剤等が挙げられる。イソシアネート系架橋剤としては、例えば、トルエンジイソシアネート、およびメチレンビスフェニルイソシアネート等が挙げられる。エポキシ系架橋剤としては、例えば、N,N,N´,N´-テトラグリシジル-m-キシレンジアミン、ジグリシジルアニリン、1,3-ビス(N,N-ジグリシジルアミノメチル)シクロヘキサンおよび1,6-ヘキサンジオールジグリシジルエーテル等が挙げられる。架橋剤を含有する場合の含有量は、ポリマー100質量部に対して、0.1質量部以上が好ましく、0.7質量部以上がより好ましく、また、50質量部以下が好ましく、10質量部以下がより好ましく、3質量部以下がさらに好ましい。なお、架橋剤は、単独で又は2種以上組み合わせて用いることができる。 粘着 The pressure-sensitive adhesive composition of the present embodiment may contain a crosslinking agent as needed for the purpose of improving creep property and shearing property by crosslinking a polymer. Examples of the crosslinking agent include isocyanate crosslinking agents, epoxy crosslinking agents, melamine crosslinking agents, peroxide crosslinking agents, urea crosslinking agents, metal alkoxide crosslinking agents, metal chelate crosslinking agents, and metal salt crosslinking agents. Crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, and amine crosslinking agents are exemplified. Examples of the isocyanate-based cross-linking agent include toluene diisocyanate, methylene bisphenyl isocyanate, and the like. Examples of the epoxy crosslinking agent include N, N, N ′, N′-tetraglycidyl-m-xylenediamine, diglycidylaniline, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, 6-hexanediol diglycidyl ether and the like. When the crosslinking agent is contained, the content is preferably 0.1 part by mass or more, more preferably 0.7 part by mass or more, and preferably 50 parts by mass or less, and more preferably 10 parts by mass with respect to 100 parts by mass of the polymer. Is more preferably not more than 3 parts by mass. In addition, the crosslinking agent can be used alone or in combination of two or more.
本実施形態の粘着剤組成物は、電圧印加時のイオン液体の移動を助ける目的で必要に応じて、ポリエチレングリコールやテトラエチレングリコールジメチルエーテルを含有してもよい。ポリエチレングリコールやテトラエチレングリコールジメチルエーテルとしては、100~6000の数平均分子量を有するものを使用できる。これらの成分を含有する場合の含有量は、ポリマー100質量部に対して、0.1質量部以上が好ましく、0.5質量部以上がより好ましく、1質量部以上がさらに好ましく、また、30質量部以下が好ましく、20質量部以下がより好ましく、15質量部以下がさらに好ましい。 The pressure-sensitive adhesive composition of the present embodiment may contain polyethylene glycol or tetraethylene glycol dimethyl ether, if necessary, for the purpose of assisting the movement of the ionic liquid when applying a voltage. As polyethylene glycol or tetraethylene glycol dimethyl ether, those having a number average molecular weight of 100 to 6000 can be used. When these components are contained, the content is preferably at least 0.1 part by mass, more preferably at least 0.5 part by mass, still more preferably at least 1 part by mass, based on 100 parts by mass of the polymer. It is preferably at most 20 parts by mass, more preferably at most 20 parts by mass, even more preferably at most 15 parts by mass.
本実施形態の粘着剤組成物は、粘着剤組成物に導電性を付与する目的で必要に応じて、導電性フィラーを含有してもよい。導電性フィラーとしては、特に限定されず、一般的な公知乃至慣用の導電性フィラーを用いることができ、例えば、黒鉛、カーボンブラック、炭素繊維、銀や銅等の金属粉等を用いることができる。導電性フィラーを含有する場合の含有量は、ポリマー100質量部に対して、0.1質量部以上200質量部以下が好ましい。 粘着 The pressure-sensitive adhesive composition of the present embodiment may contain a conductive filler as needed for the purpose of imparting conductivity to the pressure-sensitive adhesive composition. The conductive filler is not particularly limited, and a commonly known or commonly used conductive filler can be used. For example, graphite, carbon black, carbon fiber, metal powder such as silver or copper can be used. . When the conductive filler is contained, the content is preferably from 0.1 part by mass to 200 parts by mass with respect to 100 parts by mass of the polymer.
本実施形態の粘着剤組成物は、金属被着体の腐食を抑制する目的で必要に応じて、腐食防止剤を含有してもよい。腐食防止剤としては、特に限定されず、一般的な公知乃至慣用の腐食防止剤を用いることができ、例えば、カルボジイミド化合物、吸着型インヒビター、キレート形成型金属不活性剤等を用いることができる。
カルボジイミド化合物としては、例えば、1-[3-(ジメチルアミノ)プロピル]-3-エチルカルボジイミド、1-エチル-3-(3-ジメチルアミノプロピル)カルボジイミド、N,N´-ジシクロヘキシルカルボジイミド、N,N´-ジイソプロピルカルボジイミド、1-エチル-3-tert-ブチルカルボジイミド、N-シクロヘキシル-N´-(2-モルホリノエチル)カルボジイミド、N,N´-ジ-tert-ブチルカルボジイミド、1,3-ビス(p-トリル)カルボジイミド、およびこれらをモノマーとするポリカルボジイミド樹脂等が挙げられる。これらのカルボジイミド化合物は、単独で又は2種以上組み合わせて用いることができる。本実施形態の粘着剤組成物にカルボジイミド化合物を含有させる場合の含有量は、ポリマー100質量部に対して、0.01質量部以上10質量部以下が好ましい。
吸着型インヒビターとしては、例えばアルキルアミン、カルボン酸塩、カルボン酸誘導体、アルキルリン酸塩などが挙げられる。吸着型インヒビターは、単独で又は2種以上組み合わせて用いることができる。本実施形態の粘着剤組成物に吸着型インヒビターとしてアルキルアミンを含有させる場合の含有量は、ポリマー100質量部に対して、0.01質量部以上20質量部以下が好ましい。本実施形態の粘着剤組成物に吸着型インヒビターとしてカルボン酸塩を含有させる場合の含有量は、ポリマー100質量部に対して、0.01質量部以上10質量部以下が好ましい。本実施形態の粘着剤組成物に吸着型インヒビターとしてカルボン酸誘導体を含有させる場合の含有量は、ポリマー100質量部に対して、0.01質量部以上10質量部以下が好ましい。本実施形態の粘着剤組成物に吸着型インヒビターとしてアルキルリン酸塩を含有させる場合の含有量は、ポリマー100質量部に対して、0.01質量部以上10質量部以下が好ましい。
キレート形成型金属不活性剤としては、例えば、トリアゾール基含有化合物またはベンゾトリアゾール基含有化合物を用いることができる。これらは、アルミニウムなどの金属の表面を不活性化する作用が高く、また粘着成分中に含有させても接着性に影響を及ぼしにくいことから好ましい。キレート形成型金属不活性剤は、単独で又は2種以上組み合わせて用いることができる。本実施形態の粘着剤組成物にキレート形成型金属不活性剤を含有させる場合の含有量は、ポリマー100質量部に対して、0.01質量部以上20質量部以下が好ましい。
腐食防止剤の総含有量(配合量)は、ポリマー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。
The pressure-sensitive adhesive composition of the present embodiment may contain a corrosion inhibitor as needed for the purpose of suppressing corrosion of the metal adherend. The corrosion inhibitor is not particularly limited, and a generally known or commonly used corrosion inhibitor can be used. For example, a carbodiimide compound, an adsorption inhibitor, a chelate-forming metal deactivator, and the like can be used.
Examples of the carbodiimide compound include 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, and polycarbodiimide resins using these as monomers. These carbodiimide compounds can be used alone or in combination of two or more. When the carbodiimide compound is contained in the pressure-sensitive adhesive composition of the present embodiment, the content is preferably 0.01 part by mass or more and 10 parts by mass or less based on 100 parts by mass of the polymer.
Examples of the adsorption-type inhibitor include an alkylamine, a carboxylate, a carboxylic acid derivative, and an alkyl phosphate. The adsorption inhibitors can be used alone or in combination of two or more. When the pressure-sensitive adhesive composition of this embodiment contains an alkylamine as an adsorption inhibitor, the content is preferably from 0.01 to 20 parts by mass based on 100 parts by mass of the polymer. When the pressure-sensitive adhesive composition of the present embodiment contains a carboxylate as an adsorption-type inhibitor, the content is preferably 0.01 part by mass or more and 10 parts by mass or less based on 100 parts by mass of the polymer. When the carboxylic acid derivative is contained in the pressure-sensitive adhesive composition of the present embodiment as an adsorption-type inhibitor, the content is preferably 0.01 part by mass or more and 10 parts by mass or less based on 100 parts by mass of the polymer. When the pressure-sensitive adhesive composition of the present embodiment contains an alkyl phosphate as an adsorption-type inhibitor, the content is preferably 0.01 part by mass or more and 10 parts by mass or less based on 100 parts by mass of the polymer.
As the chelate-forming metal deactivator, for example, a compound containing a triazole group or a compound containing a benzotriazole group can be used. These are preferable because they have a high effect of inactivating the surface of a metal such as aluminum and do not easily affect the adhesiveness even when contained in a tacky component. The chelate-forming metal deactivators can be used alone or in combination of two or more. The content of the chelate-forming metal deactivator in the pressure-sensitive adhesive composition of the present embodiment is preferably 0.01 part by mass or more and 20 parts by mass or less based on 100 parts by mass of the polymer.
The total content (blending amount) of the corrosion inhibitor is preferably from 0.01 part by mass to 30 parts by mass with respect to 100 parts by mass of the polymer.
本実施形態の粘着剤組成物は、他にも充填剤、可塑剤、老化防止剤、酸化防止剤、顔料(染料)、難燃剤、溶剤、界面活性剤(レベリング剤)、防錆剤、接着付与樹脂、および帯電防止剤等の各種添加剤を含有してもよい。これらの成分の総含有量は、本発明の効果を奏する限りにおいて特に制限されないが、ポリマー100質量部に対して、0.01質量部以上20質量部以下が好ましく、より好ましくは10質量部以下、さらに好ましくは5質量部以下である。 The pressure-sensitive adhesive composition of the present embodiment further includes a filler, a plasticizer, an antioxidant, an antioxidant, a pigment (dye), a flame retardant, a solvent, a surfactant (leveling agent), a rust inhibitor, and an adhesive. Various additives such as an application resin and an antistatic agent may be contained. 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 to 20 parts by mass, more preferably 10 parts by mass or less, based on 100 parts by mass of the polymer. And more preferably 5 parts by mass or less.
充填剤としては、例えば、シリカ、酸化鉄、酸化亜鉛、酸化アルミニウム、酸化チタン、酸化バリウム、酸化マグネシウム、炭酸カルシウム、炭酸マグネシウム、炭酸亜鉛、ろう石クレー、カオリンクレー、および焼成クレー等が挙げられる。
可塑剤は、一般的な樹脂組成物等に用いられる公知慣用の可塑剤を用いることができ、例えば、パラフィンオイル、プロセスオイル等のオイル、液状ポリイソプレン、液状ポリブタジエン、液状エチレン-プロピレンゴム等の液状ゴム、テトラヒドロフタル酸、アゼライン酸、安息香酸、フタル酸、トリメリット酸、ピロメリット酸、アジピン酸、セバシン酸、フマル酸、マレイン酸、イタコン酸、クエン酸、およびこれらの誘導体、ジオクチルフタレート(DOP)、ジブチルフタレート(DBP)、アジピン酸ジオクチル、アジピン酸ジイソノニル(DINA)、およびコハク酸イソデシル等を用いることができる。
老化防止剤としては、例えば、ヒンダードフェノール系、脂肪族および芳香族のヒンダードアミン系等の化合物が挙げられる。
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。
防錆剤としては、例えば、ジンクホスフェート、タンニン酸誘導体、リン酸エステル、塩基性スルホン酸塩、および各種防錆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。
粘着付与樹脂としては、例えば、ロジン系粘着付与樹脂、テルペン系粘着付与樹脂、フェノール系粘着付与樹脂、炭化水素系粘着付与樹脂、ケトン系粘着付与樹脂の他、ポリアミド系粘着付与樹脂、エポキシ系粘着付与樹脂、およびエラストマー系粘着付与樹脂等が挙げられる。なお、粘着付与樹脂は、単独で又は2種以上組み合わせて用いることができる。
Examples of the filler include silica, iron oxide, zinc oxide, aluminum oxide, titanium oxide, barium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, pyrite clay, kaolin clay, and calcined clay. .
As the plasticizer, known and commonly used plasticizers used for general resin compositions and the like can be used. Examples of the plasticizer include oils such as paraffin oil and process oil, liquid polyisoprene, liquid polybutadiene, and 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 derivatives thereof, dioctyl phthalate ( DOP), dibutyl phthalate (DBP), dioctyl adipate, diisononyl adipate (DINA), isodecyl succinate and the like can be used.
Examples of the anti-aging agent include hindered phenol compounds, aliphatic and aromatic hindered amine compounds, and the like.
Examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).
Examples of pigments include, for example, inorganic pigments such as titanium dioxide, zinc oxide, ultramarine blue, red iron oxide, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, and sulfate; azo pigments; and organic pigments such as copper phthalocyanine pigments. Is mentioned.
Examples of the rust preventive include zinc phosphate, tannic acid derivatives, phosphates, basic sulfonates, and various rust preventive pigments.
Examples of the adhesion-imparting agent include a titanium coupling agent and a zirconium coupling agent.
Examples of the antistatic agent generally include quaternary ammonium salts, hydrophilic compounds such as polyglycolic acid and ethylene oxide derivatives.
Examples of the tackifying resin include a rosin-based tackifying resin, a terpene-based tackifying resin, a phenol-based tackifying resin, a hydrocarbon-based tackifying resin, a ketone-based tackifying resin, a polyamide-based tackifying resin, and an epoxy-based tackifying resin. And a tackifying resin. The tackifier resins can be used alone or in combination of two or more.
<イオン液体非含有粘着剤層の比誘電率>
第1の実施形態の粘着剤組成物は、該粘着剤組成物中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(イオン液体非含有粘着剤組成物)により粘着剤層(イオン液体非含有粘着剤層)を形成し、該粘着剤層を22℃、20%RHの環境下で3日間放置した後の、該粘着剤層の周波数100Hzにおける比誘電率が5以上である。
<Relative dielectric constant of ionic liquid-free pressure-sensitive adhesive layer>
The pressure-sensitive adhesive composition of the first embodiment comprises a pressure-sensitive adhesive layer (ionic liquid) composed of a composition (ionic liquid-free pressure-sensitive adhesive composition) composed of components other than the ionic liquid among the components contained in the pressure-sensitive adhesive composition. Non-containing pressure-sensitive adhesive layer), and after leaving the pressure-sensitive adhesive layer in an environment of 22 ° C. and 20% RH for 3 days, the pressure-sensitive adhesive layer has a relative dielectric constant of 5 or more at a frequency of 100 Hz.
なお、上述の比誘電率とは、以下のように測定された比誘電率をいうものとする。
まず、イオン液体非含有粘着剤組成物を表面が剥離処理されたセパレーターの剥離表面上に、均一に塗布し、130℃で3分間加熱乾燥を行うことで、厚み30μmのイオン液体非含有粘着剤層を得る。次いで、得られたイオン液体非含有粘着剤層を、22℃、20%RHの環境下で3日間放置する。その後、以下の条件で比誘電率を測定する。
(比誘電率の測定条件)
測定方法:容量法(装置:Agilent Technologies 4294A Precision Impedance Analyzer使用)
電極構成:12.1mmΦ、0.5mm厚みのアルミ板
対向電極:60μm厚みのアルミ箔
測定環境:23±1℃、52±1%RH
The above-mentioned relative permittivity refers to the relative permittivity measured as follows.
First, an ionic liquid-free pressure-sensitive adhesive having a thickness of 30 μm was applied by uniformly applying the ionic liquid-free pressure-sensitive adhesive composition on the release surface of a separator whose surface was subjected to a release treatment, and drying by heating at 130 ° C. for 3 minutes. Get the layers. Next, the obtained ionic liquid-free pressure-sensitive adhesive layer is allowed to stand under an environment of 22 ° C. and 20% RH for 3 days. Then, the relative permittivity is measured under the following conditions.
(Measurement conditions of relative permittivity)
Measurement method: volumetric method (apparatus: using Agilent Technologies 4294A Precision Impedance Analyzer)
Electrode configuration: 12.1 mmΦ, 0.5 mm thick aluminum plate Counter electrode: 60 μm thick aluminum foil Measurement environment: 23 ± 1 ° C., 52 ± 1% RH
イオン液体非含有粘着剤層の比誘電率は、イオン液体を含む粘着剤組成物により形成される粘着剤層におけるイオン液体の動きやすさと相関を有する。イオン液体非含有粘着剤層の比誘電率が大きいほど、イオン液体を含む粘着剤組成物により形成される粘着剤層においてイオン液体が移動しやすく、そのため、電圧を印加した際に接着力が低下しやすくなる。
第1の実施形態の粘着剤組成物は、イオン液体非含有粘着剤層を22℃、20%RHの環境下で3日間放置した後の、該粘着剤層の周波数100Hzにおける比誘電率が5以上であるため、低湿度環境下においても電圧の印加により十分に接着力が低下する接着を形成可能である。
The relative dielectric constant of the ionic liquid-free pressure-sensitive adhesive layer has a correlation with the mobility of the ionic liquid in the pressure-sensitive adhesive layer formed by the pressure-sensitive adhesive composition containing the ionic liquid. The larger the relative dielectric constant of the non-ionic liquid-containing pressure-sensitive adhesive layer, the more easily the ionic liquid moves in the pressure-sensitive adhesive layer formed by the pressure-sensitive adhesive composition containing the ionic liquid, and therefore, the lower the adhesive force when a voltage is applied. Easier to do.
The pressure-sensitive adhesive composition according to the first embodiment has a relative dielectric constant of 5 at a frequency of 100 Hz after leaving the ionic liquid-free pressure-sensitive adhesive layer in an environment of 22 ° C. and 20% RH for 3 days. As described above, even in a low humidity environment, it is possible to form an adhesive whose adhesive strength is sufficiently reduced by applying a voltage.
イオン液体非含有粘着剤層の比誘電率は、例えば粘着剤組成物におけるポリマーの成分や、イオン性添加剤の種類や含有量を、先述の好適な範囲で適宜調整することにより、制御することができる。 The relative dielectric constant of the ionic liquid-free pressure-sensitive adhesive layer is controlled, for example, by appropriately adjusting the type of the polymer component in the pressure-sensitive adhesive composition and the type and content of the ionic additive within the above-described preferable range. Can be.
<粘着剤層のイオン伝導度及び粘着剤層と被着体の界面の単位面積あたりのキャパシタンス>
第2の実施形態の粘着剤組成物は、該粘着剤組成物により粘着剤層を形成してJIS H4000:2014におけるA5052P H32からなるアルミニウム板に貼付し、22℃、15%RHの環境下で7日間放置した後の、該粘着剤層と該アルミニウム板の界面の単位面積あたりのキャパシタンスが0.9μF/cm2以上、該粘着剤層のイオン伝導度が10μS/m以上である。
<Ionic conductivity of the pressure-sensitive adhesive layer and capacitance per unit area of the interface between the pressure-sensitive adhesive layer and the adherend>
The pressure-sensitive adhesive composition of the second embodiment forms a pressure-sensitive adhesive layer from the pressure-sensitive adhesive composition, and is attached to an aluminum plate made of A5052P H32 in JIS H4000: 2014 under an environment of 22 ° C. and 15% RH. After standing for 7 days, the capacitance per unit area of the interface between the adhesive layer and the aluminum plate is 0.9 μF / cm 2 or more, and the ionic conductivity of the adhesive layer is 10 μS / m or more.
粘着剤層のイオン伝導度は、粘着剤層におけるイオン液体の動きやすさと相関を有し、イオン伝導度が大きいほど、イオン液体が移動しやすい。また、粘着剤層と被着体の界面の単位面積あたりのキャパシタンスは、粘着剤層と被着体の界面へのイオン液体の存在しやすさと相関を有し、このキャパシタンスが大きいほどが粘着剤層と被着体の界面にイオン液体が多く存在しやすくなる。
第2の実施形態の粘着剤組成物は、該粘着剤組成物により粘着剤層を形成してJIS H4000:2014におけるA5052P H32からなるアルミニウム板に貼付し、22℃、15%RHの環境下で7日間放置した後の、該粘着剤層と該アルミニウム板の界面の単位面積あたりのキャパシタンスが0.9μF/cm2以上であり、該粘着剤層のイオン伝導度が10μS/m以上であるため、低湿度環境下においても電圧の印加により十分に接着力が低下する接着を形成可能である。また、上記の単位面積あたりのキャパシタンスが1.2μF/cm2以上であり、該粘着剤層のイオン伝導度が20μS/m以上であることがより好ましい。
The ionic conductivity of the pressure-sensitive adhesive layer has a correlation with the ease of movement of the ionic liquid in the pressure-sensitive adhesive layer. The higher the ionic conductivity, the easier the ionic liquid moves. In addition, the capacitance per unit area of the interface between the pressure-sensitive adhesive layer and the adherend has a correlation with the easiness of the presence of the ionic liquid at the interface between the pressure-sensitive adhesive layer and the adherend. A large amount of ionic liquid is likely to exist at the interface between the layer and the adherend.
The pressure-sensitive adhesive composition of the second embodiment forms a pressure-sensitive adhesive layer from the pressure-sensitive adhesive composition, and is attached to an aluminum plate made of A5052P H32 in JIS H4000: 2014 under an environment of 22 ° C. and 15% RH. After standing for 7 days, the capacitance per unit area of the interface between the adhesive layer and the aluminum plate is 0.9 μF / cm 2 or more, and the ionic conductivity of the adhesive layer is 10 μS / m or more. In addition, even in a low humidity environment, it is possible to form an adhesive whose adhesive strength is sufficiently reduced by applying a voltage. More preferably, the capacitance per unit area is 1.2 μF / cm 2 or more, and the ionic conductivity of the pressure-sensitive adhesive layer is 20 μS / m or more.
上記のイオン伝導度及びキャパシタンスは、例えば粘着剤組成物におけるポリマーの成分や、イオン液体の種類や含有量、イオン性添加剤の種類や含有量を、先述の好適な範囲で適宜調整することにより、制御することができる。 The above-mentioned ionic conductivity and capacitance are, for example, by appropriately adjusting the components of the polymer in the pressure-sensitive adhesive composition, the type and content of the ionic liquid, and the type and content of the ionic additive within the above-described suitable range. , Can be controlled.
なお、上述のイオン伝導度及びキャパシタンスとは、以下のように測定されたイオン伝導度及びキャパシタンスをいうものとする。 Note that the above-described ionic conductivity and capacitance refer to the ionic conductivity and capacitance measured as described below.
(測定用サンプル(複合体サンプル)の製造)
まず、アルミ蒸着PETフィルム100(商品名「メタルミーTS」東レフィルム加工社製)のアルミ蒸着面側に粘着剤組成物を均一に塗布する。なお、この際アルミ蒸着面に電極を接触させるために、部分的に粘着剤組成物が塗布されない部分を設ける。次いで、130℃で3分間加熱乾燥を行い粘着剤層200を形成し、粘着シートサンプルを得る。
その後、得られた粘着シートサンプルの粘着面をアルミニウム板300(A5052P H32(JIS H4000:2014))に貼り付け、図5及び6に示すような形状の接合体サンプル400を得る。なお、図5は側面図、図6は上面図である。
(Production of measurement sample (composite sample))
First, the pressure-sensitive adhesive composition is uniformly applied to the aluminum-deposited surface side of an aluminum-deposited PET film 100 (trade name “Metal Me TS” manufactured by Toray Industries, Ltd.). In this case, in order to bring the electrode into contact with the aluminum vapor-deposited surface, a part to which the pressure-sensitive adhesive composition is not applied is partially provided. Next, the
Thereafter, the adhesive surface of the obtained adhesive sheet sample is attached to an aluminum plate 300 (A5052P H32 (JIS H4000: 2014)) to obtain a joined
(キャパシタンス及びイオン伝導度の測定)
キャパシタンス及びイオン伝導度の測定には、LCRメーター(例えば、日置電機株式会社製IM3533)を使用する。
まず、LCRメーターを用いてアルミニウム板300とアルミ蒸着PETフィルム100のアルミ蒸着面の間に0.5Vの交流電圧を印加し、周波数を0.5Hzから200kHzまで変化させてcole-coleプロットを得る。
(Measurement of capacitance and ionic conductivity)
For the measurement of the capacitance and the ionic conductivity, an LCR meter (for example, IM3533 manufactured by Hioki Electric Co., Ltd.) is used.
First, an alternating voltage of 0.5 V is applied between the
次に、粘着剤層200のバルクを抵抗成分Radhと静電容量成分Cadhとの並列回路、粘着剤層200の界面を抵抗成分Rpと静電容量成分Cdlとの並列回路とみなし、接合体サンプルの等価回路を図7に示すように設定し、得られたcole-coleプロットを下記式(A)によりフィッティングする。なお、抵抗成分R0は配線抵抗である。
Next, the bulk of the pressure-
なお、式(A)において、ωは角周波数である。 Ω In the equation (A), ω is an angular frequency.
得られたCdlを粘着剤層200の粘着面の面積Aで割ることにより、粘着剤層200とアルミニウム板300の界面の単位面積あたりのキャパシタンスを求めることができる。
By dividing the obtained C dl by the area A of the adhesive surface of the
次いで、式(A)より求められた粘着剤層200のバルクの抵抗成分Radhを用いて下記式(B)を用いて粘着剤層のイオン伝導度σを求めることができる。
Next, the ionic conductivity σ of the pressure-sensitive adhesive layer can be determined by using the following expression (B) using the bulk resistance component Radh of the pressure-
なお、式(B)において、lは粘着剤層の厚み、Aは粘着剤層200の粘着面の面積である。
In the formula (B), l is the thickness of the pressure-sensitive adhesive layer, and A is the area of the pressure-sensitive adhesive surface of the pressure-
<初期接着力、電圧印加による接着力の低下率>
本実施形態の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。
<Initial adhesive strength, rate of decrease in adhesive strength due to voltage application>
The adhesive force of the pressure-sensitive adhesive composition of the present embodiment can be evaluated by various methods. For example, the adhesive force can be evaluated by a 180 ° peel test described in Examples.
本実施形態の粘着剤組成物は、実施例の欄に記載のように粘着シートを形成し、180°ピール試験をおこなって測定される初期接着力が1.0N/cm以上であることが好ましく、1.5N/cm以上であることがより好ましく、2.0N/cm以上であることがさらに好ましく、2.5N/cm以上であることが特に好ましく、3.0N/cm以上であることが最も好ましい。初期接着力が1.0N/cm以上であると、被着体との接着が十分であり、被着体が剥がれたり、ずれたりしにくい。 The pressure-sensitive adhesive composition of this embodiment forms a pressure-sensitive adhesive sheet as described in the Examples section, and preferably has an initial adhesive force of 1.0 N / cm or more measured by performing a 180 ° peel test. , 1.5 N / cm or more, more preferably 2.0 N / cm or more, particularly preferably 2.5 N / cm or more, and preferably 3.0 N / cm or more. Most preferred. When the initial adhesive strength is 1.0 N / cm or more, the adhesion to the adherend is sufficient, and the adherend is less likely to peel or shift.
また、本実施形態の粘着剤組成物は、実施例の欄に記載のように粘着シートを形成し、所定の温度及び湿度の環境下で所定の期間放置し、10Vの電圧を30秒間印加した後に10Vの電圧を印加しながら180°ピール試験で測定した接着力が、初期接着力に対して十分に小さいことが好ましい。
即ち、上記の方法で測定された接着力(下式(C)において単に「電圧印加中の接着力」と表記する)と、初期接着力とから下式(C)で求められる接着力低下率が、60%以上であることが好ましく、70%以上であることがより好ましく、80%以上であることが更に好ましい。上記所定の温度及び湿度並びに期間は、22℃20%RH3日間が好ましく、22℃15%RH7日間がより好ましい。
接着力低下率(%)={1-(電圧印加中の接着力/初期接着力)}×100 (C)
Further, the pressure-sensitive adhesive composition of this embodiment forms a pressure-sensitive adhesive sheet as described in the Examples section, is left under a predetermined temperature and humidity environment for a predetermined period, and a voltage of 10 V is applied for 30 seconds. It is preferable that the adhesive strength measured by a 180 ° peel test while applying a voltage of 10 V later is sufficiently smaller than the initial adhesive strength.
That is, the adhesive force decrease rate determined by the following formula (C) from the adhesive force measured by the above method (in the following formula (C), simply referred to as “adhesive force during voltage application”) and the initial adhesive force. Is preferably at least 60%, more preferably at least 70%, even more preferably at least 80%. The above-mentioned predetermined temperature, humidity and period are preferably 22 ° C. and 20% RH for 3 days, more preferably 22 ° C. and 15% RH for 7 days.
Adhesive strength reduction rate (%) = {1− (adhesive strength during application of voltage / initial adhesive strength)} × 100 (C)
なお、電気剥離の際の印加電圧及び電圧印加時間は上記のものに限定されず、粘着シートの剥離ができる限り特に限定されない。これらの好適な範囲について以下に示す。
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。
In addition, the applied voltage and the voltage application time at the time of electric peeling are not limited to the above, and are not particularly limited as long as the pressure-sensitive adhesive sheet can be peeled. These preferred ranges are described below.
The applied voltage is preferably 1 V or more, more preferably 3 V or more, and even more preferably 6 V or more. Further, the voltage is preferably 100 V or less, more preferably 50 V or less, further 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, further preferably 20 seconds or less, and particularly preferably 10 seconds or less. In such a case, workability is excellent. The shorter the application time, the better, but usually it is 1 second or more.
<粘着剤組成物の製造方法>
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。
<Method for producing pressure-sensitive adhesive composition>
Although the pressure-sensitive adhesive composition of the present invention is not particularly limited, it is produced by appropriately stirring and mixing a polymer, an ionic liquid, an additive, and a crosslinking agent, polyethylene glycol, a conductive filler, and the like to be blended as necessary. can do.
[粘着シート]
(粘着シートの構成)
本実施形態の粘着シートは、上述の本実施形態の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。本実施形態の粘着シートは、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。本実施形態の粘着シートは、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。本実施形態の粘着シートは、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、本実施形態の粘着シートは、テープ状の形態を有する粘着テープであってもよい。
[Adhesive sheet]
(Structure of adhesive sheet)
The pressure-sensitive adhesive sheet of the present embodiment is not particularly limited as long as it has at least one pressure-sensitive adhesive layer (hereinafter also referred to as an “electropeelable pressure-sensitive adhesive layer”) formed from the pressure-sensitive adhesive composition of the present embodiment. The pressure-sensitive adhesive sheet of the present embodiment may have a pressure-sensitive adhesive layer that does not contain an ionic liquid (hereinafter, may be referred to as “other pressure-sensitive adhesive layer”) other than the electrodeposition type pressure-sensitive adhesive layer. In addition to the above, the pressure-sensitive adhesive sheet of the present embodiment may have a base material, a conductive layer, a conductive base material, an intermediate layer, an undercoat layer, and the like. The pressure-sensitive adhesive sheet of the present embodiment may be, for example, in a form wound in a roll or in a sheet form. In addition, the term “adhesive sheet” includes the meaning of “adhesive tape”. That is, the adhesive sheet of the present embodiment may be an adhesive tape having a tape-like form.
本実施形態の粘着シートは、基材を有さず電気剥離型粘着剤層のみからなる、即ち、基材層を含まない(基材レス)両面粘着シートであってもよい。本実施形態の粘着シートは、基材を有し、当該基材の両面が粘着剤層(電気剥離型粘着剤層、又はその他の粘着剤層)である両面粘着シートであってもよい。また、本実施形態の粘着シートは、基材を有し、当該基材の片面のみが粘着剤層(電気剥離型粘着剤層、又はその他の粘着剤層)である片面粘着シートであってもよい。なお、本実施形態の粘着シートは、粘着剤層表面を保護する目的のセパレーター(剥離ライナー)を有していてもよいが、当該セパレーターは、本実施形態の粘着シートに含まれないものとする。 粘着 The pressure-sensitive adhesive sheet of the present embodiment may be a double-sided pressure-sensitive adhesive sheet having no base material and consisting only of an electro-peelable pressure-sensitive adhesive layer. The pressure-sensitive adhesive sheet of the present embodiment may be a double-sided pressure-sensitive adhesive sheet having a base material and both sides of the base material being a pressure-sensitive adhesive layer (an electro-peelable pressure-sensitive adhesive layer or another pressure-sensitive adhesive layer). Further, the pressure-sensitive adhesive sheet of the present embodiment may be a single-sided pressure-sensitive adhesive sheet having a base material, and only one surface of the base material is a pressure-sensitive adhesive layer (an electrically-peelable pressure-sensitive adhesive layer or another pressure-sensitive adhesive layer). Good. The pressure-sensitive adhesive sheet of the present embodiment may have a separator (release liner) for protecting the surface of the pressure-sensitive adhesive layer, but the separator is not included in the pressure-sensitive adhesive sheet of the present embodiment. .
本実施形態の粘着シートの構造としては、特に制限されないが、図1に示す粘着シートX1、図2に積層構造を示す粘着シートX2、図3に積層構造を示す粘着シートX3が好ましく挙げられる。粘着シートX1は、電気剥離型粘着剤層1のみからなる基材レス両面粘着シートである。粘着シートX2は、粘着剤層2、通電用基材5(基材3及び導電層4)、電気剥離型粘着剤層1の層構成を有する基材付き両面粘着シートである。粘着シートX3は、粘着剤層2、通電用基材5(基材3及び導電層4)、電気剥離型粘着剤層1、通電用基材5(基材3及び導電層4)、粘着剤層2の層構成を有する基材付き両面粘着シートである。図2及び3に示す粘着シートX2及びX3の通電用基材5において、基材3は必須ではなく、導電層4のみであってもよい。また、図2の粘着シートX2において、粘着剤層2を設けない片面粘着シートであってもよい。
構造 The structure of the pressure-sensitive adhesive sheet of the present embodiment is not particularly limited, but preferably includes a pressure-sensitive adhesive sheet X1 shown in FIG. 1, a pressure-sensitive adhesive sheet X2 having a laminated structure in FIG. 2, and a pressure-sensitive adhesive sheet X3 having a laminated structure in FIG. The pressure-sensitive adhesive sheet X1 is a substrate-less double-sided pressure-sensitive adhesive sheet composed of only the electrically peelable pressure-
基材3としては、特に限定されないが、紙等の紙系基材、布、不織布等の繊維系基材、各種プラスチック(ポリエチレン、ポリプロピレン等のポリオレフィン系樹脂、ポリエチレンテレフタレート等のポリエステル系樹脂、ポリメチルメタクリレート等のアクリル系樹脂等)によるフィルムやシート等のプラスチック系基材、これらの積層体等が挙げられる。基材は単層の形態を有していてもよく、また、複層の形態を有していてもよい。なお、基材には、必要に応じて、背面処理、帯電防止処理、下塗り処理等の各種処理が施されていてもよい。
The
導電層4としては、導電性を有する層である限り特に限定されないが、金属(例えば、アルミニウム、マグネシウム、銅、鉄、スズ、金等)箔、金属板(例えば、アルミニウム、マグネシウム、銅、鉄、スズ、銀等)等の金属系基材、導電性ポリマー、などであってもよく、また、基材3上に設けられた金属蒸着膜などであってもよい。
The conductive layer 4 is not particularly limited as long as it is a layer having conductivity, but a metal (for example, aluminum, magnesium, copper, iron, tin, gold, etc.) foil, a metal plate (for example, aluminum, magnesium, copper, iron) , Tin, silver, etc.), a conductive polymer, or the like, or a metal-deposited film provided on the
通電用基材5としては、導電層を有する(通電する)基材である限り特に限定されないが、基材の表面に金属層を形成させたもの等が挙げられ、例えば、上記に例示した基材の表面に、メッキ法、化学蒸着法、スパッタリング等の方法により金属層を形成させたものが挙げられる。金属層としては、上記に例示した金属、金属板、導電性ポリマー等が挙げられる。
The current-carrying
粘着シートX1においては、両面の被着体が、金属被着面を有する被着体であることが好ましい。粘着シートX2においては、電気剥離型粘着剤層1側の被着体が金属被着面を有する被着体であることが好ましい。
に お い て In the pressure-sensitive adhesive sheet X1, the adherends on both sides are preferably adherends having a metal adherend surface. In the pressure-sensitive adhesive sheet X2, it is preferable that the adherend on the side of the electrically-peelable pressure-
金属被着面としては、導電性を有する、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面が挙げられ、なかでもアルミニウムを含む金属からなる面が好ましい。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シート、部品、および板等が挙げられる。金属被着面を有する被着体以外の被着体としては、特に限定されないが、紙、布、および不織布等の繊維シート、各種プラスチックのフィルムやシート等が挙げられる。 Examples of the metal-coated surface include surfaces having conductivity, for example, a surface composed of a metal containing aluminum, copper, iron, magnesium, tin, gold, silver, lead, or the like as a main component. Is preferred. Examples of the adherend having a metal adhered surface include a sheet, a component, and a plate made of a metal mainly containing aluminum, copper, iron, magnesium, tin, gold, silver, lead, and the like. The adherend other than the adherend having a metal adherend surface is not particularly limited, and examples thereof include fiber sheets such as paper, cloth, and nonwoven fabric, and films and sheets of various plastics.
電気剥離型粘着剤層1の厚みは1μm以上1000μm以下であることが、初期接着力の観点から好ましい。電気剥離型粘着剤層1の厚みの上限は、より好ましくは500μmであり、さらに好ましくは100μmであり、特に好ましくは30μmであり、下限は、より好ましくは3μmであり、さらに好ましくは5μmであり、特に好ましくは8μmである。なお、粘着シートが、1つの電気剥離型粘着剤層のみからなる基材レス両面粘着シート(図1に示す粘着シートX1)である場合、電気剥離型粘着剤層の厚みは、粘着シートの厚みとなる。
The thickness of the electrically peelable pressure-
粘着剤層2の厚みは1μm以上2000μm以下であることが、接着力の観点から好ましい。粘着剤層2の厚みの上限は、より好ましくは1000μmであり、さらに好ましくは500μmであり、特に好ましくは100μmであり、下限は、より好ましくは3μmであり、さらに好ましくは5μmであり、特に好ましくは8μmである。
(4) The thickness of the pressure-
基材3の厚みは、10μm以上1000μm以下が好ましい。厚みの上限は、より好ましくは500μmであり、さらに好ましくは300μmであり、特に好ましくは100μmであり、下限は、より好ましくは12μmであり、さらに好ましくは25μmである。
厚 み The thickness of the
導電層4の厚みは、0.001μm以上1000μm以下が好ましい。厚みの上限は、より好ましくは500μmであり、さらに好ましくは300μmであり、さらに好ましくは50μmであり、さらに好ましくは10μmであり、下限は、より好ましくは0.01μmであり、より好ましくは0.03μmであり、さらに好ましくは0.05μmである。 厚 み The thickness of the conductive layer 4 is preferably 0.001 μm or more and 1000 μm or less. The upper limit of the thickness is more preferably 500 μm, still more preferably 300 μm, still more preferably 50 μm, and still more preferably 10 μm, and the lower limit is more preferably 0.01 μm, more preferably 0.1 μm. It is 03 μm, more preferably 0.05 μm.
通電用基材5の厚みは、10μm以上1000μm以下が好ましい。厚みの上限は、より好ましくは500μmであり、さらに好ましくは300μmであり、特に好ましくは100μmであり、下限は、より好ましくは12μmであり、さらに好ましくは25μmである。
厚 み The thickness of the current-carrying
本実施形態の粘着シートの電気剥離型粘着剤層、及びその他の粘着剤層の表面は、セパレーター(剥離ライナー)によって保護されていてもよい。セパレーターとしては、特に限定されないが、紙やプラスチックフィルム等の基材(ライナー基材)の表面がシリコーン処理された剥離ライナー、紙やプラスチックフィルム等の基材(ライナー基材)の表面がポリオレフィン系樹脂によりラミネートされた剥離ライナー等が挙げられる。セパレーターの厚みは、特に限定されないが、10μm以上100μm以下が好ましい。 表面 The surfaces of the electrically peelable pressure-sensitive adhesive layer and the other pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the present embodiment may be protected by a separator (release liner). The separator is not particularly limited, but a release liner in which the surface of a substrate (liner substrate) such as paper or plastic film is silicone-treated, or the surface of a substrate (liner substrate) such as paper or plastic film is polyolefin-based A release liner laminated with a resin may, for example, be mentioned. The thickness of the separator is not particularly limited, but is preferably 10 μm or more and 100 μm or less.
本実施形態の粘着シートの厚みは、20μm以上3000μm以下が好ましい。厚みの上限は、より好ましくは1000μmであり、さらに好ましくは300μmであり、特に好ましくは200μmであり、下限は、より好ましくは30μm、さらに好ましくは50μmである。 粘着 The thickness of the pressure-sensitive adhesive sheet of the present embodiment is preferably 20 μm or more and 3000 μm or less. The upper limit of the thickness is more preferably 1000 μm, still more preferably 300 μm, and particularly preferably 200 μm, and the lower limit is more preferably 30 μm, and still more preferably 50 μm.
特に、図2に示す粘着シートX2である場合、粘着シートの厚みは、50μm以上2000μm以下が好ましい。厚みの上限は、より好ましくは1000μmであり、さらに好ましくは200μmであり、下限は、より好ましくは80μm、さらに好ましくは100μmである。 Especially, in the case of the adhesive sheet X2 shown in FIG. 2, the thickness of the adhesive sheet is preferably 50 μm or more and 2000 μm or less. The upper limit of the thickness is more preferably 1000 μm, and still more preferably 200 μm, and the lower limit is more preferably 80 μm, and still more preferably 100 μm.
特に、図3に示す粘着シートX3である場合、粘着シートの厚みは、100μm以上3000μm以下が好ましい。厚みの上限は、より好ましくは1000μmであり、さらに好ましくは300μmであり、下限は、より好ましくは150μm、さらに好ましくは200μmである。 Particularly, in the case of the adhesive sheet X3 shown in FIG. 3, the thickness of the adhesive sheet is preferably 100 μm or more and 3000 μm or less. The upper limit of the thickness is more preferably 1000 μm, and still more preferably 300 μm, and the lower limit is more preferably 150 μm, and still more preferably 200 μm.
(粘着シートの製造方法)
本実施形態の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。本実施形態の粘着シートにおける電気剥離型粘着剤層は、本実施形態の粘着剤組成物を必要に応じて溶剤に溶した溶液を、セパレーター上に塗布し、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、セパレーター上に塗布し、乾燥及び/又は硬化する方法等が挙げられる。なお、溶剤及びセパレーターは、上記で挙げたものを使用することができる。
(Production method of adhesive sheet)
As a method for producing the pressure-sensitive adhesive sheet of the present embodiment, a known or commonly used production method can be used. For the electrodeposition type pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet of the present embodiment, a method in which a solution obtained by dissolving the pressure-sensitive adhesive composition of the present embodiment in a solvent, if necessary, is applied on a separator, and dried and / or cured. No. The other pressure-sensitive adhesive layer includes a method in which a solution obtained by dissolving a pressure-sensitive adhesive composition containing no ionic liquid and additives in a solvent, if necessary, is coated on a separator, and dried and / or cured. . In addition, the solvent and the separator can use the thing mentioned above.
塗布に際しては、慣用のコーター(例えば、グラビヤロールコーター、リバースロールコーター、キスロールコーター、ディップロールコーター、バーコーター、ナイフコーター、スプレーロールコーター等)を用いることができる。 For coating, a conventional coater (for example, gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, spray roll coater, etc.) can be used.
上記方法により、電気剥離型粘着剤層、およびその他の粘着剤層を製造することができ、適宜、基材、導電層、通電用基材に電気剥離型粘着剤層、およびその他の粘着剤層を積層させることで、本実施形態の粘着シートを製造することができる。なお、セパレーターの代わりに、基材、導電層、通電用基材を用いて、粘着剤組成物を塗布して粘着シートを製造してもよい。 By the above method, an electric peeling type pressure-sensitive adhesive layer, and other pressure-sensitive adhesive layers can be produced, and as appropriate, a base material, a conductive layer, a current-carrying substrate, an electric peeling type pressure-sensitive adhesive layer, and other pressure-sensitive adhesive layers. Are laminated, the pressure-sensitive adhesive sheet of the present embodiment can be manufactured. In addition, you may manufacture an adhesive sheet by apply | coating an adhesive composition using a base material, a conductive layer, and a base material for electricity supply instead of a separator.
(粘着シートの電気剥離方法)
本実施形態の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において両面が金属被着面を有する被着体である場合、両面の金属被着面に通電し、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。
(Electrical peeling method of adhesive sheet)
The peeling of the pressure-sensitive adhesive sheet of this embodiment from the adherend can be performed by applying a voltage to the pressure-sensitive adhesive layer to generate a potential difference in the thickness direction of the pressure-sensitive adhesive layer. For example, when both surfaces of the pressure-sensitive adhesive sheet X1 are adherends each having a metal-adhered surface, electricity can be applied to both metal-adhered surfaces, and the pressure-sensitive adhesive layer can be peeled off by applying a voltage to the adhesive layer. When the electrically peelable pressure-sensitive adhesive layer side of the pressure-sensitive adhesive sheet X2 is an adherend having a metal adhered surface, a current is applied to the conductive adherend and the conductive layer 4, and a voltage is applied to the electrically peelable pressure-sensitive adhesive layer. Can be peeled off. In the case of the pressure-sensitive adhesive sheet X3, it can be peeled off by applying a current to the conductive layers 4 on both sides and applying a voltage to the electrically peelable pressure-sensitive adhesive layer. The energization is preferably performed by connecting a terminal to one end and the other end of the pressure-sensitive adhesive sheet so that a voltage is applied to the entire electrically peelable pressure-sensitive adhesive layer. Note that, when the adherend has a metal adhered surface, the one end and the other end may be a part of the adherend having the metal adhered surface. At the time of peeling, a voltage may be applied after water is added to the interface between the metal-coated surface and the electrically peelable pressure-sensitive adhesive layer.
(粘着シートの用途)
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実施形態の粘着シートは、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。よって、本実施形態の粘着シートは、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)の筐体への固定の用途に好適である。
(Use of adhesive sheet)
Conventional re-peeling techniques include a pressure-sensitive adhesive layer that is cured and released by ultraviolet (UV) irradiation and a pressure-sensitive adhesive layer that is released by heat. A pressure-sensitive adhesive sheet using such a pressure-sensitive adhesive layer cannot be used when it is difficult to irradiate ultraviolet (UV) light or when heat causes damage to a member as an adherend. Since the pressure-sensitive adhesive sheet of the present embodiment including the above-mentioned electro-peelable pressure-sensitive adhesive layer does not use ultraviolet light or heat, it can be easily peeled off by applying a voltage without damaging the member to be adhered. Therefore, the adhesive sheet of the present embodiment is used for fixing a secondary battery (for example, a lithium ion battery pack) used in a mobile terminal such as a smartphone, a mobile phone, a notebook computer, a video camera, and a digital camera to a housing. It is suitable for.
また、本実施形態の粘着シートによる接合の対象としての剛性部材としては、例えば、半導体ウエハ用途のシリコン基板、LED用のサファイア基板、SiC基板および金属ベース基板、ディスプレイ用のTFT基板およびカラーフィルター基板、並びに有機ELパネル用のベース基板が挙げられる。両面粘着シートによる接合の対象としての脆弱部材としては、例えば、化合物半導体基板などの半導体基板、MEMSデバイス用途のシリコン基板、パッシブマトリックス基板、スマートフォン用の表面カバーガラス、当該カバーガラスにタッチパネルセンサーが付設されてなるOGS(One Glass Solution)基板、シルセスキオキサンなどを主成分とする有機基板および有機無機ハイブリッド基板、フレキシブルディスプレイ用のフレキシブルガラス基板、並びにグラフェンシートが挙げられる。 Examples of the rigid member to be joined by the adhesive sheet of the present embodiment include a silicon substrate for a semiconductor wafer, a sapphire substrate for an LED, a SiC substrate and a metal base substrate, a TFT substrate for a display, and a color filter substrate. And a base substrate for an organic EL panel. Examples of the fragile member to be bonded by the double-sided adhesive sheet include a semiconductor substrate such as a compound semiconductor substrate, a silicon substrate for MEMS devices, a passive matrix substrate, a surface cover glass for a smartphone, and a touch panel sensor attached to the cover glass. OGS (One Glass Solution) substrate, an organic substrate and an organic-inorganic hybrid substrate containing silsesquioxane as a main component, a flexible glass substrate for a flexible display, and a graphene sheet.
[接合体]
本実施形態の接合体は、金属被着面を有する被着体と、電気剥離型粘着剤層が金属被着面に接合している粘着シートとを含む積層構造部を有する。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。
[Joint body]
The joined body of the present embodiment has a laminated structure including an adherend having a metal adhered surface and an adhesive sheet having an electrically peelable adhesive layer joined to the metal adhered surface. Examples of the adherend having a metal-applied surface include, for example, those composed of a metal containing aluminum, copper, iron, magnesium, tin, gold, silver, lead, or the like as a main component. Is preferred.
本実施形態の接合体としては、例えば、粘着シートX1であって、電気剥離型粘着剤層1の両面に金属被着面を有する被着体を備える接合体、粘着シートX2であって、電気剥離型粘着剤層1側に金属被着面を有する被着体を備え、粘着剤層2側に被着体を備える接合体、粘着シートX3であって粘着剤層2の両面に被着体を備える接合体等が挙げられる。
Examples of the bonded body of the present embodiment include a pressure-sensitive adhesive sheet X1 and a bonded body including an adherend having a metal-applied surface on both surfaces of the electro-peelable pressure-
以下、実施例により本発明をより具体的に説明するが、本発明はこれらの実施例により限定されるものではない。下記の重量平均分子量は、ゲルパーミエーションクロマトグラフ(GPC)法により上記記載の方法で測定されたものである。 Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. The following weight average molecular weights were measured by the method described above by gel permeation chromatography (GPC).
[実施例1-1~1-8、比較例1-1~1-5]
<ポリマー溶液の作成>
(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):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1溶液を得た。
[Examples 1-1 to 1-8, Comparative Examples 1-1 to 1-5]
<Preparation of polymer solution>
(Preparation of
As a monomer component, 95 parts by mass of n-butyl acrylate (BA), 5 parts by mass of acrylic acid (AA), and 150 parts by mass of ethyl acetate as a polymerization solvent were charged into a separable flask, and nitrogen gas was introduced. While stirring for 1 hour. After removing oxygen in the polymerization system in this manner, 0.2 parts by mass of 2,2′-azobisisobutyronitrile (AIBN) as a polymerization initiator was added, and the temperature was raised to 63 ° C. for 6 hours. Reacted. Thereafter, ethyl acetate was added to obtain an
(アクリル系ポリマー2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):90質量部、4-ヒドロキシブチルアクリレート(4HBA):10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30質量%のアクリル系ポリマー2溶液を得た。
(Preparation of
90 parts by mass of n-butyl acrylate (BA), 10 parts by mass of 4-hydroxybutyl acrylate (4HBA) as a monomer component, and 150 parts by mass of ethyl acetate as a polymerization solvent were charged into a separable flask, and nitrogen gas was added. While stirring for 1 hour. After removing oxygen in the polymerization system in this manner, 0.2 parts by mass of 2,2′-azobisisobutyronitrile (AIBN) as a polymerization initiator was added, and the temperature was raised to 63 ° C. for 6 hours. Reacted. Thereafter, ethyl acetate was added to obtain an
(アクリル系ポリマー3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):67質量部、2-メトキシエチルアクリレート(MEA):30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3溶液を得た。
(Preparation of
As monomer components, n-butyl acrylate (BA): 67 parts by mass, 2-methoxyethyl acrylate (MEA): 30 parts by mass, acrylic acid (AA): 3 parts by mass, and ethyl acetate: 150 parts by mass as a polymerization solvent. , And stirred for one hour while introducing nitrogen gas. After removing oxygen in the polymerization system in this manner, 0.2 parts by mass of 2,2′-azobisisobutyronitrile (AIBN) as a polymerization initiator was added, and the temperature was raised to 63 ° C. for 6 hours. Reacted. Thereafter, ethyl acetate was added to obtain an
(アクリル系ポリマー4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):67質量部、メタクリル酸メチル(MMA):33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4溶液を得た。
(Preparation of Acrylic Polymer 4 Solution)
As a monomer component, n-butyl acrylate (BA): 67 parts by mass, methyl methacrylate (MMA): 33 parts by mass, and ethyl acetate: 150 parts by mass as a polymerization solvent are charged into a separable flask, and nitrogen gas is introduced. While stirring for 1 hour. After removing oxygen in the polymerization system in this manner, 0.2 parts by mass of 2,2′-azobisisobutyronitrile (AIBN) as a polymerization initiator was added, and the temperature was raised to 63 ° C. for 6 hours. Reacted. Thereafter, ethyl acetate was added to obtain an acrylic polymer 4 solution having a solid content concentration of 40% by mass.
(アクリル系ポリマー5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、4-ヒドロキシブチルアクリレート(4HBA):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30質量%のアクリル系ポリマー5溶液を得た。
(Preparation of
As monomer components, n-butyl acrylate (BA): 87 parts by mass, 4-hydroxybutyl acrylate (4HBA): 10 parts by mass, acrylic acid (AA): 3 parts by mass, and ethyl acetate: 150 parts by mass as a polymerization solvent. , And stirred for one hour while introducing nitrogen gas. After removing oxygen in the polymerization system in this manner, 0.2 parts by mass of 2,2′-azobisisobutyronitrile (AIBN) as a polymerization initiator was added, and the temperature was raised to 63 ° C. for 6 hours. Reacted. Thereafter, ethyl acetate was added to obtain an
<粘着剤組成物の作製>
上記で得られたアクリル系ポリマー溶液や以下に示すポリマー、架橋剤、イオン液体、添加剤を加えて撹拌、混合し、実施例1-1~1-8及び比較例1-1~1-5の粘着剤組成物を得た。表1に各成分の配合量を示す。
なお、表1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。
表1におけるポリマー、架橋剤、イオン液体、および添加剤の略称については、以下の通りである。
(ポリマー)
バイロンUR-V8700:ウレタン変性ポリエステル樹脂、商品名「バイロンUR-V8700」、東洋紡社製
バイロンBX1001:ポリエステル樹脂、商品名「バイロンBX1001」、東洋紡社製
ソマレックス530:アニオン性ポリアクリルアミドポリマー(イオン性ポリマー)、商品名「ソマレックス530」、ソマール株式会社製
(イオン液体)
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社製
(架橋剤)
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
タケネートD110:トリメチロールプロパンキシリレンジイソシアネート、商品名「タケネートD110N」、三井化学株式会社製(添加剤)
EMI-nitrate:1-エチル-3-メチルイミダゾリウムニトレート、東京化成工業社製
Zn-nitrate:硝酸亜鉛6水和物、和光純薬工業社製
BTC-5B:チタン酸バリウム
No.27776:カーボンブラック
<Preparation of pressure-sensitive adhesive composition>
The acrylic polymer solution obtained above, the polymer shown below, a cross-linking agent, an ionic liquid, and additives were added thereto, followed by stirring and mixing. Examples 1-1 to 1-8 and Comparative Examples 1-1 to 1-5 Was obtained. Table 1 shows the amount of each component.
In addition, the value of each component in Table 1 means a mass part. The compounding amount (parts by mass) of the polymer indicates the compounding amount (parts by mass) of the solid content in the polymer solution.
The abbreviations of the polymer, the crosslinking agent, the ionic liquid, and the additive in Table 1 are as follows.
(polymer)
Byron UR-V8700: a urethane-modified polyester resin, trade name “Byron UR-V8700”, manufactured by Toyobo Co., Ltd. Byron BX1001: polyester resin, trade name “Byron BX1001”, manufactured by Toyobo Co., Ltd. Somalex 530: anionic polyacrylamide polymer (ionic polymer ), Trade name "Somarex 530", manufactured by Somar Corporation (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. Takenate D110: trimethylolpropane xylylene diisocyanate, trade name "Takenate D110N", manufactured by Mitsui Chemicals, Inc. (additive)
EMI-nitrate: 1-ethyl-3-methylimidazolium nitrate, manufactured by Tokyo Chemical Industry Co., Ltd. Zn-nitrate: zinc nitrate hexahydrate, manufactured by Wako Pure Chemical Industries, Ltd. BTC-5B: barium titanate 27776: Carbon black
<イオン液体非含有粘着剤層の比誘電率の測定>
イオン液体を添加しなかった点以外は上記実施例1-1~1-8、比較例1-1~1-5と同様にして材料を撹拌、混合して得られたイオン液体非含有粘着剤組成物を、表面が剥離処理されたポリエチレンテレフタレートセパレーター(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、130℃で3分間の加熱乾燥を行い、厚み30μmのイオン液体非含有粘着剤層を得た。次いで、得られたイオン液体非含有粘着剤層を22℃、20%RHの環境下で3日間放置した後に、該粘着剤層の周波数100kHzでの比誘電率をJIS K 6911に準じて、下記条件で測定した。
(測定条件)
測定方法:容量法(装置:Agilent Technologies 4294A Precision Impedance Analyzer使用)
電極構成:12.1mmΦ、0.5mm厚みのアルミ板
対向電極:3oz 銅板
測定環境:23±1℃、52±1%RH
<Measurement of relative dielectric constant of ionic liquid-free pressure-sensitive adhesive layer>
An ionic liquid-free adhesive obtained by stirring and mixing materials in the same manner as in Examples 1-1 to 1-8 and Comparative examples 1-1 to 1-5 except that no ionic liquid was added. The composition was applied on a release-treated surface of a polyethylene terephthalate separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc.), the surface of which was subjected to a release treatment, using an applicator so as to have a uniform thickness. Next, heating and drying were performed at 130 ° C. for 3 minutes to obtain a 30 μm-thick ionic liquid-free pressure-sensitive adhesive layer. Then, after leaving the obtained ionic liquid-free pressure-sensitive adhesive layer in an environment of 22 ° C. and 20% RH for 3 days, the relative permittivity of the pressure-sensitive adhesive layer at a frequency of 100 kHz is determined according to JIS K 6911 as follows. It was measured under the conditions.
(Measurement condition)
Measurement method: volumetric method (apparatus: using Agilent Technologies 4294A Precision Impedance Analyzer)
Electrode configuration: 12.1 mmΦ, 0.5 mm thick aluminum plate Counter electrode: 3 oz copper plate Measurement environment: 23 ± 1 ° C., 52 ± 1% RH
<電気剥離型粘着剤層の含水率の測定>
各例の粘着剤組成物を用いて、上記と同様にして得られた電気剥離型粘着剤層を、22℃20%RHの環境下で3日間放置した後に、該粘着剤層の含水率をカールフィッシャー水分気化-電量滴定法(JIS K 0113:2005)により測定した。具体的には平沼産業株式会社製の平沼微量水分測定装置AQ-2100を用い、200℃、30分間の加熱気化により生じた水分量を測定し、加熱前の試料重量に対する割合を含水率とした。すなわち、下記式により含水率を求めた。なお、表1中の「‐」は未測定を意味する。
含水率(%)=(カールフィッシャー測定水分量/測定前の試料全重量)×100
<Measurement of the water content of the electrically peelable pressure-sensitive adhesive layer>
After leaving the electrically peelable pressure-sensitive adhesive layer obtained in the same manner as described above using the pressure-sensitive adhesive composition of each example for 3 days in an environment of 22 ° C. and 20% RH, the water content of the pressure-sensitive adhesive layer was measured. It was measured by Karl Fischer moisture vaporization-coulometric titration (JIS K 0113: 2005). Specifically, the amount of water generated by heating and vaporizing at 200 ° C. for 30 minutes was measured using a Hiranuma trace moisture analyzer AQ-2100 manufactured by Hiranuma Sangyo Co., Ltd., and the ratio to the sample weight before heating was defined as the water content. . That is, the water content was determined by the following equation. In addition, "-" in Table 1 means unmeasured.
Water content (%) = (water content measured by Karl Fischer / total weight of sample before measurement) × 100
<評価>
(初期接着力)
各例の粘着剤組成物を、表面が剥離処理されたポリエチレンテレフタレートセパレーター(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、130℃で3分間の加熱乾燥を行い、厚み30μmの電気剥離型粘着剤層(粘着シート)を得た。
次いで、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、セパレーターのない面に、基材として金属層付きフィルム(商品名「BR1075」、東レフィルム加工(株)社製、厚み25μm、サイズ10mm×100mm)の金属層面を貼り合わせ、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セパレーターを剥がし、剥がした面に被着体としてアルミニウム板(A5052P H32(JIS H4000:2014))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。その後、剥離試験機(商品名「変角度ピール試験機YSP」、旭精工(株)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た。測定結果を表1に示す。
<Evaluation>
(Initial adhesive strength)
The pressure-sensitive adhesive composition of each example was applied to a release-treated surface of a polyethylene terephthalate separator (trade name “MRF38”, manufactured by Mitsubishi Plastics, Inc.), the surface of which was subjected to release treatment, so as to have a uniform thickness using an applicator. Applied. Next, heating and drying were performed at 130 ° C. for 3 minutes to obtain an electrically-peelable pressure-sensitive adhesive layer (pressure-sensitive adhesive sheet) having a thickness of 30 μm.
Next, the obtained electrically peelable pressure-sensitive adhesive layer (pressure-sensitive adhesive sheet) was formed into a sheet having a size of 10 mm × 80 mm, and a film having a metal layer as a substrate (trade name “BR1075”, Toray Film Processing Co., Ltd.) ) Co., Ltd., 25 μm thick, size 10 mm × 100 mm) metal layer surface was bonded to obtain a single-sided pressure-sensitive adhesive sheet with a substrate. The separator of the single-sided pressure-sensitive adhesive sheet with the base material was peeled off, and an aluminum plate (A5052P H32 (JIS H4000: 2014)) was adhered to the peeled surface so that one end of the pressure-sensitive adhesive sheet protruded about 2 mm from the adherend, Pressed back and forth with a 2 kg roller once, and allowed to stand for 30 minutes in an environment of 23 ° C., from the
(電圧印加中の接着力)
2kgのローラーで1往復押圧した後に、22℃、20%RHの環境下で3日間放置した点、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10V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、ピールした点以外は上記の初期接着力測定と同様にして、電圧印加中の接着力を測定した。測定結果を表1に示す。
(Adhesive force during voltage application)
After pressing back and forth with a 2 kg roller for one round, left for 3 days in an environment of 22 ° C. and 20% RH, and before the peel, the minus pole of the DC current machine was placed at the positions α and β in FIG. And a positive electrode were attached, and a voltage was applied at a voltage of 10 V for 30 seconds. While applying the voltage as it was, the adhesive force during the application of the voltage was measured in the same manner as in the initial adhesive force measurement except that the peeling was performed. It was measured. Table 1 shows the measurement results.
(接着力低下率)
上記の方法で測定した初期接着力及び電圧印加中の接着力を用いて、下記式(C)により電圧印加による接着力低下率を求めた。結果を表1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)
(Adhesive strength decrease rate)
Using the initial adhesive force measured by the above method and the adhesive force during application of a voltage, the rate of decrease in adhesive force due to the application of a voltage was determined by the following equation (C). Table 1 shows the results.
Adhesive strength reduction rate (%) = {1− (adhesive strength during application of voltage / initial adhesive strength)} × 100 (C)
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により粘着剤層を形成し、該粘着剤層を22℃、20%RHの環境下で3日間放置した後の、該粘着剤層の周波数100Hzにおける比誘電率が5以上である実施例1-1~1-8の粘着剤組成物は、いずれも電圧印加による接着力低下率が大きかった。 After forming a pressure-sensitive adhesive layer with a composition comprising components other than the ionic liquid among the components contained in the pressure-sensitive adhesive composition, and leaving the pressure-sensitive adhesive layer at 22 ° C. and 20% RH for 3 days, In the pressure-sensitive adhesive compositions of Examples 1-1 to 1-8 in which the relative permittivity of the pressure-sensitive adhesive layer at a frequency of 100 Hz was 5 or more, the rate of decrease in the adhesive force due to voltage application was large.
[実施例2-1~2-11、比較例2-1~2-3]
<ポリマー溶液の作成>
(アクリル系ポリマー6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):90質量部、アクリル酸(AA):10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6溶液を得た。
[Examples 2-1 to 2-11, Comparative Examples 2-1 to 2-3]
<Preparation of polymer solution>
(Preparation of
N-butyl acrylate (BA): 90 parts by mass as a monomer component, acrylic acid (AA): 10 parts by mass, and ethyl acetate: 150 parts by mass as a polymerization solvent were charged into a separable flask, and nitrogen gas was introduced. While stirring for 1 hour. After removing oxygen in the polymerization system in this manner, 0.2 parts by mass of 2,2′-azobisisobutyronitrile (AIBN) as a polymerization initiator was added, and the temperature was raised to 63 ° C. for 6 hours. Reacted. Thereafter, ethyl acetate was added to obtain an
(アクリル系ポリマー7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):90質量部、4-ヒドロキシブチルアクリレート(4HBA):7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30質量%のアクリル系ポリマー7溶液を得た。
(Preparation of Acrylic Polymer 7 Solution)
As monomer components, 90 parts by mass of n-butyl acrylate (BA), 7 parts by mass of 4-hydroxybutyl acrylate (4HBA), 3 parts by mass of acrylic acid (AA), and 150 parts by mass of ethyl acetate as a polymerization solvent. , And stirred for one hour while introducing nitrogen gas. After removing oxygen in the polymerization system in this manner, 0.2 parts by mass of 2,2′-azobisisobutyronitrile (AIBN) as a polymerization initiator was added, and the temperature was raised to 63 ° C. for 6 hours. Reacted. Thereafter, ethyl acetate was added to obtain an acrylic polymer 7 solution having a solid content concentration of 30% by mass.
(アクリル系ポリマー8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):94質量部、4-ヒドロキシブチルアクリレート(4HBA):3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30質量%のアクリル系ポリマー8溶液を得た。
(Preparation of Acrylic Polymer 8 Solution)
As a monomer component, n-butyl acrylate (BA): 94 parts by mass, 4-hydroxybutyl acrylate (4HBA): 3 parts by mass, acrylic acid (AA): 3 parts by mass, and ethyl acetate: 150 parts by mass as a polymerization solvent. , And stirred for one hour while introducing nitrogen gas. After removing oxygen in the polymerization system in this manner, 0.2 parts by mass of 2,2′-azobisisobutyronitrile (AIBN) as a polymerization initiator was added, and the temperature was raised to 63 ° C. for 6 hours. Reacted. Thereafter, ethyl acetate was added to obtain an acrylic polymer 8 solution having a solid content concentration of 30% by mass.
(アクリル系ポリマー9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):77質量部、2-メトキシエチルアクリレート(MEA):20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9溶液を得た。
(Preparation of Acrylic Polymer 9 Solution)
As monomer components, n-butyl acrylate (BA): 77 parts by mass, 2-methoxyethyl acrylate (MEA): 20 parts by mass, acrylic acid (AA): 3 parts by mass, and ethyl acetate: 150 parts by mass as a polymerization solvent. , And stirred for one hour while introducing nitrogen gas. After removing oxygen in the polymerization system in this manner, 0.2 parts by mass of 2,2′-azobisisobutyronitrile (AIBN) as a polymerization initiator was added, and the temperature was raised to 63 ° C. for 6 hours. Reacted. Thereafter, ethyl acetate was added to obtain an acrylic polymer 9 solution having a solid content concentration of 40% by mass.
(アクリル系ポリマー10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10溶液を得た。
(Preparation of Acrylic Polymer 10 Solution)
As monomer components, n-butyl acrylate (BA): 87 parts by mass, 2-methoxyethyl acrylate (MEA): 10 parts by mass, acrylic acid (AA): 3 parts by mass, and ethyl acetate: 150 parts by mass as a polymerization solvent. , And stirred for one hour while introducing nitrogen gas. After removing oxygen in the polymerization system in this manner, 0.2 parts by mass of 2,2′-azobisisobutyronitrile (AIBN) as a polymerization initiator was added, and the temperature was raised to 63 ° C. for 6 hours. Reacted. Thereafter, ethyl acetate was added to obtain an acrylic polymer 10 solution having a solid content concentration of 40% by mass.
<粘着剤組成物の作製>
上記で得られたアクリル系ポリマー溶液や先述のポリマー、架橋剤、イオン液体、添加剤、または、下記のイオン液体、腐食防止剤を加えて撹拌、混合し、実施例2-1~2-11及び比較例2-1~2-3の粘着剤組成物を得た。表2に各成分の配合量を示す。
(イオン液体)
1-ヘキシル-ピリジニウム-ビス(トリフルオロスルホニル)イミド
(腐食防止剤、添加剤、架橋剤)
Irgamet30:N,N-ビス(2-エチルヘキシル)-1,2,4-トリアゾール-1-イルメタンアミン、商品名「Irgamet30」、BASF社製
IrgacorDSSG:セバシン酸二ナトリウム、商品名「IrgametDSSG」、BASF社製
AminO:イミダゾリン誘導体、商品名「Amin O」、BASF社製
PEG400:ポリエチレングリコール、商品名「PEG400」、東京化成工業社製
コロネートL:イソシアネート化合物、商品名「コロネートL」、東ソー株式会社製
<Preparation of pressure-sensitive adhesive composition>
The acrylic polymer solution obtained above, the above-mentioned polymer, cross-linking agent, ionic liquid, additive, or the following ionic liquid, corrosion inhibitor were added, and the mixture was stirred and mixed. Examples 2-1 to 2-11 And the pressure-sensitive adhesive compositions of Comparative Examples 2-1 to 2-3 were obtained. Table 2 shows the amount of each component.
(Ionic liquid)
1-hexyl-pyridinium-bis (trifluorosulfonyl) imide (corrosion inhibitor, additive, crosslinking agent)
Irgamet 30: N, N-bis (2-ethylhexyl) -1,2,4-triazol-1-ylmethanamine, trade name “Irgamet 30”, manufactured by BASF IrgacorDSSG: disodium sebacate, trade name “IrgametDSSG”, BASF AminO: imidazoline derivative, trade name "Amin O", PEG400: polyethylene glycol, trade name "PEG400", trade name "PEG400", Tokyo Chemical Industry Co., Ltd. Coronate L: isocyanate compound, trade name "Coronate L", manufactured by Tosoh Corporation
<粘着剤層のイオン伝導率及び単位面積あたりのキャパシタンスの測定>
各例の粘着剤組成物を用いて以下のように測定用サンプル(複合体サンプル)を作成し、以下の方法で接着界面のキャパシタンス及び粘着剤層のイオン伝導度を求めた。結果を表2に示す。
<Measurement of ionic conductivity and capacitance per unit area of adhesive layer>
Using the pressure-sensitive adhesive composition of each example, a measurement sample (composite sample) was prepared as follows, and the capacitance at the adhesive interface and the ionic conductivity of the pressure-sensitive adhesive layer were determined by the following methods. Table 2 shows the results.
(測定用サンプル(複合体サンプル)の製造)
まず、アルミ蒸着PETフィルム100(商品名「メタルミーTS」東レフィルム加工社製)のアルミ蒸着面側に粘着剤組成物を均一に塗布した。なお、この際アルミ蒸着面に電極を接触させるために、部分的に粘着剤組成物が塗布されない部分を設けた。次いで、130℃で3分間加熱乾燥を行い粘着剤層200を形成し、粘着シートサンプルを得た。
その後、得られた粘着シートサンプルの粘着面をアルミニウム板300(A5052P H32(JIS H4000:2014))に貼り付け、図5及び6に示すような形状の接合体サンプル400を得た。なお、図5は側面図、図6は上面図である。
(Production of measurement sample (composite sample))
First, the pressure-sensitive adhesive composition was uniformly applied to the aluminum-deposited surface side of an aluminum-deposited PET film 100 (trade name “Metal Me TS” manufactured by Toray Film Processing Co., Ltd.). At this time, in order to bring the electrode into contact with the aluminum-deposited surface, a part to which the adhesive composition was not applied was partially provided. Then, the
Thereafter, the adhesive surface of the obtained adhesive sheet sample was attached to an aluminum plate 300 (A5052P H32 (JIS H4000: 2014)) to obtain a joined
(キャパシタンス及びイオン伝導度の測定)
キャパシタンス及びイオン伝導度の測定には、LCRメーター(例えば、日置電機株式会社製IM3533)を使用した。
まず、LCRメーターを用いてアルミニウム板300とアルミ蒸着PETフィルム100のアルミ蒸着面の間に0.5Vの交流電圧を印加し、周波数を0.5Hzから200kHzまで変化させてcole-coleプロットを得た。
(Measurement of capacitance and ionic conductivity)
For the measurement of the capacitance and the ionic conductivity, an LCR meter (for example, IM3533 manufactured by Hioki Electric Co., Ltd.) was used.
First, an alternating voltage of 0.5 V was applied between the
次に、粘着剤層200のバルクを抵抗成分Radhと静電容量成分Cadhとの並列回路、粘着剤層200の界面を抵抗成分Rpと静電容量成分Cdlとの並列回路とみなし、接合体サンプルの等価回路を図7に示すように設定し、得られたcole-coleプロットを下記式(A)によりフィッティングした。なお、抵抗成分R0は配線抵抗である。
なお、式(A)において、ωは角周波数である。 Ω In the equation (A), ω is an angular frequency.
得られたCdlを粘着剤層200の粘着面の面積Aで割ることにより、粘着剤層200とアルミニウム板300の界面の単位面積あたりのキャパシタンスを求めた。
The capacitance per unit area of the interface between the
次いで、式(A)より求められた粘着剤層200のバルクの抵抗成分Radhを用いて下記式(B)を用いて粘着剤層のイオン伝導度σを求めた。
Next, the ionic conductivity σ of the pressure-sensitive adhesive layer was determined using the following equation (B) using the bulk resistance component Radh of the pressure-
なお、式(B)において、lは粘着剤層の厚み、Aは粘着剤層200の粘着面の面積である。
In the formula (B), l is the thickness of the pressure-sensitive adhesive layer, and A is the area of the pressure-sensitive adhesive surface of the pressure-
<評価>
(初期接着力)
各例の粘着剤組成物について、基材としてアルミ蒸着PETフィルム(商品名「メタルミーTS」東レフィルム加工社製)を用いて、アルミ蒸着面に粘着剤層を形成したこと以外は実施例1-1~1-8及び比較例1-1~1-5と同様にして初期接着力を測定した。測定結果を表2に示す。
<Evaluation>
(Initial adhesive strength)
The pressure-sensitive adhesive composition of each example was prepared in the same manner as in Example 1 except that the pressure-sensitive adhesive layer was formed on the aluminum-deposited surface using an aluminum-deposited PET film (trade name “Metal Me TS” manufactured by Toray Film Processing Co., Ltd.) as a substrate. The initial adhesive strength was measured in the same manner as in Examples 1 to 1-8 and Comparative Examples 1-1 to 1-5. Table 2 shows the measurement results.
(22℃、20%RHの環境下で3日間保存後の、電圧印加中の接着力)
2kgのローラーで1往復押圧した後に、22℃、20%RHの環境下で3日間放置した点、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10V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、ピールした点以外は上記の初期接着力測定と同様にして、電圧印加中の接着力を測定し、以下の基準で電気剥離性を評価した。測定結果を表2に示す。
○:接着力低下率が60%以上。
×:接着力低下率が60%未満。
(Adhesive force during voltage application after storage for 3 days in an environment of 22 ° C. and 20% RH)
After pressing back and forth with a 2 kg roller for one round, left for 3 days in an environment of 22 ° C. and 20% RH, and before the peel, the minus pole of the DC current machine was placed at the positions α and β in FIG. And a positive electrode were attached, and a voltage was applied at a voltage of 10 V for 30 seconds. While applying the voltage as it was, the adhesive force during the application of the voltage was measured in the same manner as in the initial adhesive force measurement except that the peeling was performed. It measured and evaluated the electrical peelability by the following criteria. Table 2 shows the measurement results.
:: Adhesion reduction rate is 60% or more.
X: The adhesive strength reduction rate is less than 60%.
(22℃、15%RHの環境下で7日間保存後の、電圧印加中の接着力)
2kgのローラーで1往復押圧した後に、22℃、15%RHの環境下で7日間放置した点、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10Vにて10秒間電圧印加を行い、そのまま電圧を印加しながら、ピールした点以外は上記の初期接着力測定と同様にして、電圧印加中の接着力を測定した。測定結果を表2に示す。
(Adhesive force during voltage application after storage for 7 days in an environment of 22 ° C. and 15% RH)
After pressing back and forth with a 2 kg roller once, leaving it in an environment of 22 ° C. and 15% RH for 7 days, and before peeling, the minus pole of the DC current machine was placed at the positions α and β in FIG. And the positive electrode were attached, and a voltage was applied at a voltage of 10 V for 10 seconds. While applying the voltage as it was, the adhesive force during the voltage application was measured in the same manner as in the initial adhesive force measurement described above except for the peeling. It was measured. Table 2 shows the measurement results.
(接着力低下率)
上記の方法で測定した初期接着力及び22℃、15%RHの環境下で7日間保存後の電圧印加中の接着力を用いて、下記式(C)により電圧印加による接着力低下率を求めた。
結果を表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)
(Adhesive strength decrease rate)
Using the initial adhesive force measured by the above method and the adhesive force during voltage application after storage for 7 days in an environment of 22 ° C. and 15% RH, the adhesive force decrease rate by voltage application is determined by the following formula (C). Was.
Table 2 shows the results.
Adhesive strength reduction rate (%) = {1− (adhesive strength during application of voltage / initial adhesive strength)} × 100 (C)
粘着剤組成物により粘着剤層を形成してJIS H4000:2014におけるA5052P H32からなるアルミニウム板に貼付し、22℃、15%RHの環境下で7日間放置した後の、該粘着剤層と該アルミニウム板の界面の単位面積あたりのキャパシタンスが0.9μF/cm2以上、該粘着剤層のイオン伝導度が10μS/m以上である実施例2-1~2-11の粘着剤組成物は、いずれも電圧印加による接着力低下率が大きかった。 A pressure-sensitive adhesive layer was formed from the pressure-sensitive adhesive composition, attached to an aluminum plate made of A5052P H32 according to JIS H4000: 2014, and allowed to stand at 22 ° C. and 15% RH for 7 days. The pressure-sensitive adhesive compositions of Examples 2-1 to 2-11 in which the capacitance per unit area of the interface of the aluminum plate is 0.9 μF / cm 2 or more and the ionic conductivity of the pressure-sensitive adhesive layer is 10 μS / m or more, In each case, the rate of decrease in the adhesive force due to the application of the voltage was large.
[実施例3-1~3-5]
<ポリマー溶液の作成>
(アクリル系ポリマー11溶液の作製)
モノマー成分として、2-メトキシエチルアクリレート(MEA):95質量部、4-ヒドロキシブチルアクリレート(4HBA):5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30質量%のアクリル系ポリマー11溶液を得た。
[Examples 3-1 to 3-5]
<Preparation of polymer solution>
(Preparation of Acrylic Polymer 11 Solution)
As a monomer component, 95 parts by mass of 2-methoxyethyl acrylate (MEA) and 5 parts by mass of 4-hydroxybutyl acrylate (4HBA) were charged into a separable flask and stirred for 1 hour while introducing nitrogen gas. After removing oxygen in the polymerization system in this manner, 0.2 parts by mass of 2,2′-azobisisobutyronitrile (AIBN) as a polymerization initiator was added, and the temperature was raised to 63 ° C. for 6 hours. Reacted. Thereafter, ethyl acetate was added to obtain an acrylic polymer 11 solution having a solid content concentration of 30% by mass.
<粘着剤組成物の作製>
上記で得られたアクリル系ポリマー溶液や先述のポリマー、架橋剤、イオン液体、添加
剤、または、下記の添加剤を加えて撹拌、混合し、実施例3-1~3-5の粘着剤組成物を得た。表3に各成分の配合量を示す。
(添加剤)
・EMIM-MeSO3:イオン性添加剤、イミダゾリウム塩、東京化成工業社製。
・エポミン200:ポリエチレンイミン、日本触媒製。
<Preparation of pressure-sensitive adhesive composition>
The acrylic polymer solution obtained above, the above-mentioned polymer, cross-linking agent, ionic liquid, additives, or the following additives are added, and the mixture is stirred and mixed, and then the pressure-sensitive adhesive composition of Examples 3-1 to 3-5 is added. I got something. Table 3 shows the amount of each component.
(Additive)
EMIM-MeSO 3 : ionic additive, imidazolium salt, manufactured by Tokyo Chemical Industry Co., Ltd.
Epomin 200: polyethyleneimine, manufactured by Nippon Shokubai.
<粘着剤層のイオン伝導率及び単位面積あたりのキャパシタンスの測定、及び評価>
実施例2-1~2-11及び比較例2-1~2-3と同様にして、初期接着力、22℃20%RHの環境下で3日間保存後の電圧印加中の接着力及び接着力低下率、22℃15%RHの環境下で7日間保存後の電圧印加中の接着力及び接着力低下率を測定した。また、実施例2-1~2-11及び比較例2-1~2-3と同様にして、測定用サンプル(複合体サンプル)を作成し、接着界面のキャパシタンス及び粘着剤層のイオン伝導度を求めた。結果を表3に示す。
<Measurement and evaluation of ionic conductivity and capacitance per unit area of pressure-sensitive adhesive layer>
In the same manner as in Examples 2-1 to 2-11 and Comparative examples 2-1 to 2-3, the initial adhesive force, the adhesive force during application of voltage after storage for 3 days in an environment of 22 ° C. and 20% RH, and the adhesiveness The rate of decrease in force, the adhesive force during voltage application after storage for 7 days in an environment of 22 ° C. and 15% RH, and the rate of decrease in adhesive force were measured. In the same manner as in Examples 2-1 to 2-11 and Comparative examples 2-1 to 2-3, measurement samples (composite samples) were prepared, and the capacitance at the adhesive interface and the ionic conductivity of the pressure-sensitive adhesive layer were measured. I asked. Table 3 shows the results.
粘着剤組成物により粘着剤層を形成してJIS H4000:2014におけるA5052P H32からなるアルミニウム板に貼付し、22℃、15%RHの環境下で7日間放置した後の、該粘着剤層と該アルミニウム板の界面の単位面積あたりのキャパシタンスが0.9μF/cm2以上、該粘着剤層のイオン伝導度が10μS/m以上である実施例3-1~3-5の粘着剤組成物は、いずれも電圧印加による接着力低下率が大きかった。 A pressure-sensitive adhesive layer was formed from the pressure-sensitive adhesive composition, attached to an aluminum plate made of A5052P H32 according to JIS H4000: 2014, and allowed to stand at 22 ° C. and 15% RH for 7 days. The pressure-sensitive adhesive compositions of Examples 3-1 to 3-5 in which the capacitance per unit area of the interface of the aluminum plate is 0.9 μF / cm 2 or more and the ionic conductivity of the pressure-sensitive adhesive layer is 10 μS / m or more, In each case, the rate of decrease in the adhesive force due to the application of the voltage was large.
以上、本発明の好ましい実施の形態について説明したが、本発明は、上述した実施の形態に制限されるものではなく、本発明の範囲を逸脱しない範囲において、上述した実施の形態に種々の変形及び置換を加えることができる。
なお、本出願は、2018年9月3日出願の日本特許出願(特願2018-164545)、2019年3月28日出願の日本特許出願(特願2019-065065)、および2019年8月29日出願の日本特許出願(特願2019-157325)に基づくものであり、その内容は本出願の中に参照として援用される。
Although the preferred embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments, and various modifications may be made to the above-described embodiments without departing from the scope of the present invention. And substitutions can be added.
This application is based on Japanese Patent Application filed on September 3, 2018 (Japanese Patent Application No. 2018-164545), Japanese Patent Application filed on March 28, 2019 (Japanese Patent Application No. 2019-065065), and August 29, 2019. It is based on Japanese Patent Application (Japanese Patent Application No. 2019-157325) filed on the Japanese Patent Application, the contents of which are incorporated herein by reference.
X1,X2,X3 粘着シート
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
100 アルミ蒸着PETフィルム
200 粘着剤層
300 アルミニウム板
400 接合体サンプル
X1, X2, X3
Claims (12)
前記粘着剤組成物に含まれる成分のうち前記イオン液体以外の成分からなる組成物により粘着剤層を形成し、該粘着剤層を22℃、20%RHの環境下で3日間放置した後の、該粘着剤層の周波数100Hzにおける比誘電率が5以上である粘着剤組成物。 An adhesive composition comprising a polymer and an ionic liquid,
After forming a pressure-sensitive adhesive layer with a composition comprising components other than the ionic liquid among the components contained in the pressure-sensitive adhesive composition, and after allowing the pressure-sensitive adhesive layer to stand in an environment of 22 ° C. and 20% RH for 3 days, A pressure-sensitive adhesive composition, wherein the pressure-sensitive adhesive layer has a relative dielectric constant of 5 or more at a frequency of 100 Hz.
前記粘着剤組成物により粘着剤層を形成してJIS H4000:2014におけるA5052P H32からなるアルミニウム板に貼付し、22℃、15%RHの環境下で7日間放置した後の、該粘着剤層と該アルミニウム板の界面の単位面積あたりのキャパシタンスが0.9μF/cm2以上、該粘着剤層のイオン伝導度が10μS/m以上である粘着剤組成物。 An adhesive composition comprising a polymer and an ionic liquid,
The pressure-sensitive adhesive layer was formed from the pressure-sensitive adhesive composition, attached to an aluminum plate made of A5052P H32 according to JIS H4000: 2014, and allowed to stand at 22 ° C. and 15% RH for 7 days. An adhesive composition wherein the capacitance per unit area of the interface of the aluminum plate is 0.9 μF / cm 2 or more, and the ionic conductivity of the adhesive layer is 10 μS / m or more.
前記ポリマー100質量部に対して、前記イオン液体0.5~30質量部と、イオン性固体0.5~10質量部とを含む粘着剤組成物。 Including a polymer and an ionic liquid,
A pressure-sensitive adhesive composition comprising 0.5 to 30 parts by mass of the ionic liquid and 0.5 to 10 parts by mass of an ionic solid based on 100 parts by mass of the polymer.
前記ポリマー100質量部に対して、前記イオン液体0.5~30質量部を含み、前記ポリマーにはイオン性ポリマーが0.05~2質量部含まれる粘着剤組成物。 Including a polymer and an ionic liquid,
An adhesive composition containing 0.5 to 30 parts by mass of the ionic liquid with respect to 100 parts by mass of the polymer, wherein the polymer contains 0.05 to 2 parts by mass of the ionic polymer.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310680383.0A CN116536005A (en) | 2018-09-03 | 2019-08-30 | Adhesive composition, adhesive sheet, and joined body |
| CN201980057389.4A CN112639045B (en) | 2018-09-03 | 2019-08-30 | Adhesive composition, adhesive sheet, and joined body |
| US17/272,958 US12104100B2 (en) | 2018-09-03 | 2019-08-30 | Adhesive composition, adhesive sheet, and adhered body |
| KR1020217006251A KR102803368B1 (en) | 2018-09-03 | 2019-08-30 | Adhesive composition, adhesive sheet and joint |
| EP19857048.3A EP3848434A4 (en) | 2018-09-03 | 2019-08-30 | Adhesive composition, adhesive sheet and bonded body |
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| JP2018164545 | 2018-09-03 | ||
| JP2018-164545 | 2018-09-03 | ||
| JP2019-065065 | 2019-03-28 | ||
| JP2019065065 | 2019-03-28 | ||
| JP2019-157325 | 2019-08-29 | ||
| JP2019157325A JP7651255B2 (en) | 2018-09-03 | 2019-08-29 | Pressure-sensitive adhesive composition, pressure-sensitive adhesive sheet, and bonded body |
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| WO2020050169A1 true WO2020050169A1 (en) | 2020-03-12 |
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| PCT/JP2019/034143 Ceased WO2020050169A1 (en) | 2018-09-03 | 2019-08-30 | Adhesive composition, adhesive sheet and bonded body |
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| JP (2) | JP2025061947A (en) |
| CN (1) | CN116536005A (en) |
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| WO2021200054A1 (en) * | 2020-03-30 | 2021-10-07 | 日東電工株式会社 | Pressure-sensitive adhesive composition, pressure-sensitive adhesive sheet, and bonded object |
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| US9810622B2 (en) * | 2015-04-09 | 2017-11-07 | Gen-Probe Incorporated | Sample testing systems and methods with automated cleaning |
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Also Published As
| Publication number | Publication date |
|---|---|
| TWI867744B (en) | 2024-12-21 |
| TW202402995A (en) | 2024-01-16 |
| TW202020086A (en) | 2020-06-01 |
| TWI819084B (en) | 2023-10-21 |
| CN116536005A (en) | 2023-08-04 |
| JP2025061948A (en) | 2025-04-11 |
| JP2025061947A (en) | 2025-04-11 |
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