Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
  • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09J133/08—Homopolymers or copolymers of acrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
  • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
  • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
  • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
  • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/80—Masked polyisocyanates
  • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
  • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
  • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
  • C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds
  • C08K5/19—Quaternary ammonium compounds
• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
  • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09J133/062—Copolymers with monomers not covered by C09J133/06
  • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/38—Pressure-sensitive adhesives [PSA]
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/38—Pressure-sensitive adhesives [PSA]
  • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C09J7/385—Acrylic polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
  • C09J9/02—Electrically-conducting adhesives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/001—Conductive additives
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
  • C09J2301/314—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive layer and/or the carrier being conductive
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
  • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
  • C09J2301/502—Additional features of adhesives in the form of films or foils characterized by process specific features process for debonding adherents
• • 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
  • C09J2471/00—Presence of polyether

Definitions

• the present invention relates to an electro-peeling adhesive composition.
• the present invention relates to an electro-peeling adhesive product.
• the present invention relates to a method for peeling an electro-peeling adhesive product.
• Adhesives and adhesive tapes that have adhesiveness to and releasability from adherends are used in various applications (for example, surface protection films, masking tapes for painting, peelable memos, etc.).
• a method for peeling the pressure-sensitive adhesive from the adherend besides the physical method, there are known methods such as peeling by stimulus such as light, heat, vibration, or electric current.
• Patent Document 1 describes that by using a polymer and an ionic liquid as an adhesive, it is possible to provide an adhesive that can be peeled off from an adherend by applying a voltage (electro-peeling adhesive).
• Patent Document 2 describes that it is possible to provide an electro-peelable pressure-sensitive adhesive that leaves no adhesive residue even when a low voltage is applied by studying conditions such as a migration promoter used together with a polymer or an ionic liquid.
• an object of the present invention is to provide an electro-peeling adhesive product that has excellent electro-peeling properties even when exposed to a high-temperature environment for a long time, in order to apply the electro-peeling adhesive to various products.
• the present inventors have found that by appropriately adjusting the amount of the ionic liquid/transfer promoter in the electro-peelable pressure-sensitive adhesive composition, an electro-peeling agent having excellent electro-peeling properties even when exposed to a high-temperature environment for a long time can be obtained.
• the present invention contains an acrylic polymer, an ionic liquid, and an alkyl ether of polyethylene glycol, and the content of the ionic liquid is more than 30 parts by weight and not more than 90 parts by weight with respect to 100 parts by weight of the acrylic polymer. and the content of the alkyl ether of polyethylene glycol is 5 to 45 parts by weight per 100 parts by weight of the acrylic polymer.
• the present invention is an electro-peeling adhesive comprising a substrate and an electro-peeling pressure-sensitive adhesive layer formed in contact with the substrate, wherein the electro-peeling pressure-sensitive adhesive layer contains the above-described electro-peeling pressure-sensitive adhesive composition. provide adhesive products.
• the present invention has a core material and two electro-releasable pressure-sensitive adhesive layers formed so as to be in contact with both sides of the core material.
• an electro-releasable adhesive product comprising:
• the above-described electro-peelable adhesive product is attached to a conductive object so that the adhesive layer is in contact with the adhesive layer, and then a voltage of 30 V or less is applied to the adhesive layer through the conductive object.
• a method of peeling an adhesive product from a conductive object to which it is directly attached, wherein the conductive object is a conductive adherend, a conductive auxiliary material, or a conductive fixing object, by electro-peeling To provide a method for removing adhesive products.
• an electro-peeling pressure-sensitive adhesive composition that exhibits excellent electro-peeling properties even when exposed to high temperature conditions.
• FIG. 1 is a diagram showing an example of a cross-section of an electro-releasable adhesive product in the form of a single-sided tape
• 1 is a diagram showing an example of a cross-section of an electro-releasable adhesive product in the form of a double-sided tape
• FIG. 2 is a diagram showing an example of a circuit that applies a voltage to a conductive adherend and a conductive base material to peel the conductive base material from the electro-peeling adhesive product. It is a figure which shows the example which applied the voltage and peeled the electroconductive base material.
• FIG. 1 is a diagram showing an example of a cross-section of an electro-releasable adhesive product in the form of a single-sided tape
• 1 is a diagram showing an example of a cross-section of an electro-releasable adhesive product in the form of a double-sided tape
• FIG. 2 is a diagram showing an example of a circuit that applies a voltage to a conductive adherend and
• FIG. 2 is a diagram showing an example of a circuit for applying a voltage to a conductive adherend and a conductive fixing object to separate the conductive fixing object from the electro-peeling adhesive product.
• FIG. 10 is a diagram showing an example in which a voltage is applied and a conductive fixed object is peeled off;
• FIG. 2 is a diagram showing an example of a circuit that applies a voltage to a conductive adherend and a conductive auxiliary material to peel off a non-conductive fixing object from an electro-peeling adhesive product.
• FIG. 10 is a diagram showing an example in which a voltage is applied to peel off a non-conductive fixed object;
• FIG. 3 is a diagram showing an example of a circuit for applying a voltage to a conductive auxiliary material and a conductive fixed object to separate the conductive fixed object from the electro-peeling adhesive product.
• FIG. 10 is a diagram showing an example in which a voltage is applied and a conductive fixed object is peeled off; A voltage is applied to the conductive auxiliary material adhered to the non-conductive adherend and the conductive auxiliary material adhered to the non-conductive fixed object, and the electrically peelable adhesive product is removed from the non-conductive fixed object. It is a figure which shows an example of the circuit which peels.
• FIG. 10 is a diagram showing an example in which a voltage is applied to peel off a non-conductive fixed object;
• x to y means x or more and y or less unless otherwise specified.
• the acrylic polymer of the present embodiment can be obtained by polymerizing an acrylic monomer in the presence of any polymerization initiator. Any acrylic polymer can be used as long as it can adhere to a conductive object.
• a conductive object refers to a conductive adherend, a conductive auxiliary material, a conductive base material, or a conductive fixing object (definition of these will be given later).
• the weight average molecular weight of the acrylic polymer is preferably 100,000 to 5,000,000, more preferably 200,000 to 4,000,000, and more preferably 300,000 to 3,000,000 from the viewpoint of adhesiveness.
• the weight average molecular weight refers to the weight average molecular weight in terms of polystyrene. Specifically, it may be a polystyrene-equivalent weight-average molecular weight calculated using Shodex's GPC (System 21) and using tetrahydrofuran as a mobile phase.
• the glass transition temperature (Tg) of the acrylic polymer is preferably 0°C or lower, more preferably -20°C or lower, and more preferably -40°C or lower.
• the above Tg can be calculated, for example, based on the following Fox formula.
• 1/Tg (W1/Tg1)+(W2/Tg2)+ ⁇ +(Wn/Tgn)
• the glass transition temperature can be measured, for example, by differential thermal analysis (DTA).
• the acrylic polymer may be crosslinked by using a crosslinking agent.
• cross-linking agents include isocyanate-based cross-linking agents such as toluene diisocyanate and methylenebisphenyl isocyanate.
• the amount of the cross-linking agent is preferably 1 to 10 parts by weight or less, more preferably 3 to 10 parts by weight, and preferably 5 to 10 parts by weight or less with respect to 100 parts by weight of the acrylic polymer. more preferred.
• Crosslinking the acrylic polymer can improve the creep resistance and/or shear resistance of the layer when the electropeeling pressure-sensitive adhesive composition is formed as a layer on a substrate.
• the above acrylic polymer more preferably contains a copolymer with an alkyl (meth)acrylate having an alkyl group of 1 to 8 carbon atoms, a carboxyl group-containing acrylic monomer and/or a hydroxyl group-containing acrylic monomer.
• an electro-peelable pressure-sensitive adhesive composition having excellent adhesive strength can be obtained.
• the acrylic monomer preferably contains an alkyl (meth)acrylate having an alkyl group of 1 to 14 carbon atoms as a main component (50% by weight or more).
• (Meth)acrylate means methacrylate or acrylate.
• alkyl (meth)acrylates having an alkyl group having 1 to 14 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl ( meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate and dodecyl ( meth)acrylate and the like.
• alkyl (meth)acrylates may be used alone or in combination of two or more.
• alkyl (meth)acrylates alkyl (meth)acrylates having an alkyl group having 1 to 8 carbon atoms are preferred, alkyl (meth)acrylates having an alkyl group having 1 to 4 carbon atoms are more preferred, and n-butyl (Meth)acrylates are more preferred, and n-butyl acrylate is more preferred.
• acrylic monomers include acrylic acid, methacrylic acid, carboxyl group-containing monomers such as carboxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate. , 6-hydroxyhexyl (meth)acrylate and (4-hydroxymethylcyclohexyl)-methylacrylate.
• carboxyl group-containing monomers such as carboxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate. , 6-hydroxyhexyl (meth)acrylate and (4-hydroxymethylcyclohexyl)-methylacrylate.
• acrylic monomers may be used alone or in combination of two or more.
• Other acrylic monomers preferably contain either carboxyl group-containing monomers or hydroxyl group-containing monomers, or both.
• the acrylic monomer may consist only of alkyl (meth)acrylate without using the other acrylic monomers described above.
• the other acrylic monomer is contained in an amount of 1% by weight or more and less than 50% by weight, and 5 to 30% by weight. more preferably 5 to 15% by weight.
• the total content of these two monomers is not particularly limited, but the total amount of monomers is 100 wt. When expressed as parts, it is preferably in the range of 1 to 20 parts by weight. By using both monomers in this range, adhesive properties can be improved. Furthermore, the total content of both monomers is more preferably in the range of 1 to 10 parts by weight.
• a vinyl-based monomer may be added to the (meth)acrylate, if necessary.
• vinyl monomers include itaconic acid, maleic acid, crotonic acid, maleic anhydride, itaconic anhydride, vinyl acetate, N-vinylpyrrolidone, N-vinylcarboxylic acid amides, styrene and N-vinylcaprolactam. be done. These vinyl-based monomers may be used alone or in combination of two or more.
• polymerization initiator examples include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylpropionamidine) disulfide, 2,2'-azobis(4 -methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis( cyclohexane-1-carbonitrile), 2,2'-azobis(2,4,4-trimethylpentane), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis[2 -methyl-N-(phenylmethyl)-propionamidine]dihydrochloride, 2,2'-azobis[2-(3,4,5,6-tetrahydropyrimidin-2-yl)propane]dihydrochloride and 2 Azo polymerization initiators such as ,2'-azobis[
• polymerization initiators may be used alone or in combination of two or more. Alternatively, ultraviolet irradiation or radiation irradiation may be performed.
• the polymerization initiator is preferably used in an amount of 0.005 parts by weight or more and 1 part by weight or less per 100 parts by weight of the acrylic monomer. By using the polymerization initiator within this range, an acrylic polymer having excellent adhesive properties can be formed.
• Ionic liquids are combinations of cations and anions that are liquid at room temperature, and are also called room temperature molten salts. Ionic liquids have properties such as non-flammability, non-volatility and chemical stability. When a voltage is applied to the ionic liquid, anions move to the anode side and cations move to the cathode side. The migration of anions and cations to the vicinity of the electrodes, or the oxidation-reduction reaction of the anions or cations at the interface between the electrodes and the electro-peeling adhesive composition weakens the adhesion of the electro-peeling adhesive composition. As a result, it is believed that the releasability is improved.
• the ionic conductivity of the ionic liquid is not particularly limited, it preferably has an ionic conductivity of 10 -7 S/cm or more, and preferably has an ionic conductivity of 10 -6 to 10 -1 S/cm. , more preferably 10 ⁇ 4 to 10 ⁇ 2 S/cm, more preferably 10 ⁇ 3 to 10 ⁇ 2 S/cm.
• Ionic conductivity can be measured, for example, by an AC impedance method.
• the ionic conductivity of an ionic liquid can be measured by the AC impedance method, for example, as follows.
• the ionic liquid is placed on stainless steel using a bipolar cell, and another stainless steel plate is placed on the ionic liquid to sandwich the ionic liquid between the stainless steel plates.
• a sample is obtained by controlling the disk shape of Bulk resistance ( ⁇ ) is obtained by applying a voltage to this sample and curve-fitting the Cole-Cole plot obtained when changing the frequency that defines the amplitude using an equivalent circuit.
• ionic liquids examples include combinations of cyclic cations and anions represented by the following formula (1).
• R 1 is a divalent hydrocarbon group having 2 to 8 carbon atoms which may contain a heteroatom, forms a ring together with N + in the formula
• R 2 and R 3 are the same or different is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (however, when the nitrogen atom forms a double bond with the adjacent carbon atom, R 3 does not exist)
• X- is Cl- , Br- , I- , AlCl4- , Al2Cl7- , NO3- , BF4- , PF6- , ClO4- , CH3COO- , CF3COO- , CF 3SO3- , ( CF3SO2 ) 2N- , ( FSO2 ) 2N- , ( CF3SO2 ) 3C- , AsF6- , SbF6- , NbF6- , F (HF ) n - , B ( C6H5 )
• the ring composed of R 1 and N + includes saturated alicyclic hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane and cyclooctane, cyclopropene, cyclobutene, cyclopentene and cyclohexene. , cycloheptene, cyclooctene, cyclopentadiene, and unsaturated cyclic hydrocarbons such as benzene.
• Heteroatoms include N, O, S, P and the like, preferably N.
• alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group.
• An alkyl group having 3 or more and 8 or less carbon atoms includes structural isomers.
• an ionic liquid is a combination of a cation and an anion represented by the following formula (2) or (3).
• R 4 to R 7 are the same or different, and are hydrogen atoms (provided that all of R 4 to R 7 are not hydrogen atoms) or having 1 to 20 carbon atoms, a linear, branched or cyclic alkyl group which may have a substituent (provided that when the nitrogen atom forms a double bond with the adjacent carbon atom, R 7 does not exist); the substituent is selected from the group consisting of a halogen atom, a hydroxy group, a nitro group and a cyano group;
• X- is Cl- , Br- , I- , AlCl4- , Al2Cl7- , NO3- , BF4- , PF6- , ClO4- , CH3COO- , CF3COO- , CF 3SO3- , ( CF3SO2 ) 2N- , ( FSO2 ) 2N- , ( CF3SO2 ) 3C-
• R 8 to R 10 may be the same or different and may have a hydrogen atom (provided that not all of R 8 to R 10 are hydrogen atoms) or a substituent having 1 to 20 carbon atoms. a linear, branched or cyclic alkyl group, wherein the substituent is selected from the group consisting of a halogen atom, a hydroxy group, a nitro group and a cyano group;
• X- is Cl- , Br- , I- , AlCl4- , Al2Cl7- , NO3- , BF4- , PF6- , ClO4- , CH3COO- , CF3COO- , CF 3SO3- , ( CF3SO2 ) 2N- , ( FSO2 ) 2N- , ( CF3SO2 ) 3C- , AsF6- , SbF6- , NbF6- , F (HF ) n -
• Cations in the ionic liquid preferably have a weight average molecular weight of 700 or less, more preferably have a weight average molecular weight of 50 to 600, and have a weight average molecular weight of 50 to 500. More preferably, it has a weight average molecular weight of 50-400.
• the upper limits of the weight average molecular weight of cations in the ionic liquid are, for example, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 150.
• the lower limits of the weight average molecular weight of cations in the ionic liquid are, for example, 30, 40, 50, 60, 70, 80, 90, 99, and 100.
• the weight average molecular weight referred to here refers to the weight average molecular weight in terms of polystyrene.
• the ionic liquid is preferably a combination of a cyclic cation and an anion represented by formula (1), and a cation selected from pyridinium cations, cycloaliphatic ammonium cations and imidazolium cations, and (FSO 2 ) more preferably in combination with an anion selected from 2N- , ( CF3SO2 ) 2N- and BF4- , a cation selected from imidazolium cations and ( FSO2 ) 2
• a combination with an anion selected from N-, (CF 3 SO 2 ) 2 N- and BF 4 - is more preferable from the viewpoint of improving peelability after voltage application.
• the ionic liquid is available from Daiichi Kogyo Seiyaku, Kanto Chemical, Koei Chemical Industry, etc.
• 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide EMI-FSI
• 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide EMI-TFSI
• 1-hexylpyridinium bis(trifluoromethanesulfonyl)imide N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide
• 1-ethyl-3-methylimidazolium tetrafluoroborate from Kanto Kagaku, Koei Chemical Industry
• IL-C3 1-ethyl-3-methylimidazolium hexafluorophosphate
• 1-butylpyridinium tetrafluorophosphate IL-C3
• the amount of the ionic liquid contained in the electro-peelable pressure-sensitive adhesive composition is 30 to 90 parts by weight, preferably more than 30 parts by weight and 90 parts by weight or less, with respect to 100 parts by weight of the acrylic polymer. It is more preferably more than 85 parts by weight and more preferably more than 30 parts by weight and not more than 80 parts by weight.
• the upper limit of the amount of the ionic liquid contained in the electro-peelable pressure-sensitive adhesive composition is, for example, 90 parts by weight, 89 parts by weight, 88 parts by weight, 87 parts by weight, 86 parts by weight, and 85 parts by weight with respect to 100 parts by weight of the acrylic polymer.
• the lower limits of the amount of the ionic liquid contained in the electro-peelable pressure-sensitive adhesive composition are, for example, 30 parts by weight, 30.1 parts by weight, 30.5 parts by weight, 31 parts by weight, 32 parts by weight, and 33 parts by weight with respect to 100 parts by weight of the acrylic polymer. 34 parts by weight, 35 parts by weight, 36 parts by weight, 37 parts by weight, 38 parts by weight, 39 parts by weight, and 40 parts by weight.
• the ionic liquid may be a combination of one cation and one anion, or a combination of multiple types of cations and anions.
• the composition exhibits excellent electro-peeling properties even when exposed to high temperatures.
• high temperature refers to a temperature of 50° C. or higher.
• the electro-peeling pressure-sensitive adhesive composition is exposed to high temperatures means that the electro-peeling pressure-sensitive adhesive composition is present in an environment where the composition itself can reach high temperatures.
• environments include, for example, a state in which the electro-peeling adhesive composition is in direct or indirect contact with a high-temperature object, and a state in which the electro-peeling adhesive composition is placed in a high-temperature space. , and both.
• the environment in which the electric peelable pressure-sensitive adhesive composition itself can reach a high temperature may be a constantly high-temperature environment or an environment in which the temperature rises for a predetermined period of time. Since the electro-peeling pressure-sensitive adhesive composition of the present invention has excellent electro-peeling properties even when exposed to high temperatures, even if the object itself to which it is attached can reach high temperatures, the electro-peeling pressure-sensitive adhesive composition It can be used even under conditions where the space in which objects are placed becomes hot.
• having excellent electro-peeling properties even when exposed to high temperatures means that the adhesive strength of the electro-peeling pressure-sensitive adhesive composition to which a voltage is applied after being exposed to high temperatures is reduced after being exposed to high temperatures.
• the rate of decrease in adhesive force calculated by the following formula (4) is 50% or more, that is, even if it is placed under high temperature conditions such as 80 ° C for 100 hours, it will stick by applying voltage. It means that the force can be reduced to less than half (the adhesive product, core material, conductive adherend and conductive fixing object in the formula will be described later).
• the reduction rate of adhesive strength is 50% or more, and may be 53% or more, 55% or more, 60% or more, 62% or more, or 65% or more. However, it may be 70% or more, 75% or more, 78% or more, or 80% or more.
• the adhesive strength of the adhesive product that has not been applied after heating means that the adhesive product is formed in the form of a double-sided tape with the electro-releasable adhesive composition as an adhesive layer, and the adhesive product is used to form an electrically conductive adhesive product. It refers to the adhesive force measured in accordance with JIS-Z-0237 (2009) after fixing a conductive adherend and a conductive fixing object and leaving it in a space of 80 ° C for 100 hours.
• the adhesive strength of the adhesive product after heating and application treatment is defined as follows: Refers to the adhesive strength measured in accordance with JIS-Z-0237 (2009) after applying a voltage of 10V for 60 seconds)
• the adhesive strength of the adhesive product that has not been applied after heating is in the form of a double-sided tape in which the electro-peeling adhesive composition is applied to the core material and the electro-peeling adhesive composition is used as the adhesive layer.
• a certain adhesive product is formed, a stainless steel plate and aluminum foil are fixed using the adhesive product, left to stand in a space of 80 ° C for 100 hours, and then pulled at a speed of 300 mm according to JIS-Z-0237 (2009).
• /min refers to the force (N/25mm) required to peel off the adhesive product from the adherend at an angle of 180°
• the adhesive strength of the adhesive product after heating and application treatment is obtained by fixing a stainless steel plate and aluminum foil using the adhesive product, leaving it in a space of 80 ° C for 100 hours, and then applying a voltage of 10 V for 60 seconds. JIS-Z-0237 (2009), the force (N/25mm) required to peel the adhesive product from the stainless steel plate at an angle of 180° at a pulling speed of 300mm/min)
• the electro-peelable pressure-sensitive adhesive composition of the present invention can reduce the adhesive force to a level sufficient for peeling by applying a voltage even when exposed to high temperatures. It is suitable for use under conditions where the space used may become hot.
• alkyl ethers of polyethylene glycol are used as migration enhancers.
• Alkyl ethers of polyethylene glycol include, for example, polyethylene glycol mono(di)methyl ether, polyethylene glycol mono(di)ethyl ether, polyethylene glycol mono(di)propyl ether, polyethylene glycol mono(di)isopropyl ether, polyethylene glycol mono( di)butyl ether, polyethylene glycol mono(di)isobutyl ether, polyethylene glycol mono(di)methyl ether, polyethylene glycol mono(di)pentyl ether and the like.
• polyethylene glycol mono(di)methyl ether is preferable, and is selected from tetraethylene glycol dimethyl ether (dimethyltetraglycol), diethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, dimethyltriglycol, and triethylene glycol monomethyl ether. More preferably selected from dimethyltetraglycol, diethylene glycol dibutyl ether, triethylene glycol butyl methyl ether.
• Alkyl ethers of polyethylene glycol are available from Nihon Nyukazai, Toho Chemical Industry and the like. The alkyl ether of polyethylene glycol to be used may be used alone or in combination of two or more.
• the alkyl ether of polyethylene glycol preferably has a weight average molecular weight of 120-600, more preferably 120-550, more preferably 120-500. and more preferably have a weight average molecular weight of 120-360.
• the upper limits of the weight average molecular weight of the alkyl ether of polyethylene glycol are, for example, , 420, 410, 400, 390, 380, 370, 360, 355, 350, 340.
• the lower limit of the weight average molecular weight of the alkyl ether of polyethylene glycol is 120, 125, 130, 135, 140, 145, 150, 155, 160, 170, for example.
• the weight average molecular weight referred to here refers to the weight average molecular weight in terms of polystyrene.
• the amount of transfer promoter contained in the electro-peeling adhesive composition is in the range of 5 to 45 parts by weight with respect to 100 parts by weight of the acrylic polymer.
• the upper limits of the transfer promoter contained in the electro-peeling adhesive composition are, for example, 45 parts by weight, 44 parts by weight, 43 parts by weight, 42 parts by weight, 41 parts by weight, and 40 parts by weight with respect to 100 parts by weight of the acrylic polymer. Department.
• the lower limit of the transfer accelerator contained in the electro-peelable pressure-sensitive adhesive composition is, for example, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, and 10 parts by weight with respect to 100 parts by weight of the acrylic polymer. Department.
• Organic solvent may be contained in the electrically peelable pressure-sensitive adhesive composition in order to easily apply the electrically peelable pressure-sensitive adhesive composition onto a release film or substrate.
• the organic solvent is not particularly limited, and includes known organic solvents that can be used for adhesives.
• a hydrophilic organic solvent or a hydrophobic organic solvent may be used as the organic solvent.
• hydrophilic organic solvents include methanol, ethanol, 1-propanol, 2-propanol, n-butyl alcohol, sec-butyl alcohol, isobutanol, tert-butyl alcohol, acetonitrile, acetone, and dimethylformamide. .
• hydrophobic organic solvents examples include aliphatic hydrocarbons such as hexane, heptane and isooctane; esters such as methyl acetate, ethyl acetate and propyl acetate; and aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene. , dichloromethane, 1,2-dichloroethane, chloroform, 1-chlorobutane, halogenated hydrocarbons such as chlorobenzene, ethers such as diethyl ether and t-butyl methyl ether, and ketones such as methyl ethyl ketone and methyl isobutyl ketone.
• aliphatic hydrocarbons such as hexane, heptane and isooctane
• esters such as methyl acetate, ethyl acetate and propyl acetate
• aromatic hydrocarbons such
• organic solvents may be used alone or in combination of two or more.
• an organic solvent it is preferable to adjust the usage ratio so that the solid content of the acrylic polymer is 10% by weight or more. Moreover, it is more preferable that the use ratio is adjusted so that the solid content is 20 to 50% by weight.
• the electro-peelable pressure-sensitive adhesive composition of the present embodiment contains additives such as a conductive material, a filler, a plasticizer, an antioxidant, a flame retardant, a colorant, a surfactant, or a pressure-sensitive adhesive other than the acrylic polymer. may be included.
• Carbon-based conductive materials include, for example, nanocarbon or carbon fiber [eg, vapor grown carbon fiber (VGCF) or carbon nanofiber], more specifically natural graphite, artificial graphite, acetylene black, and ketjen black. , furnace black and the like.
• metal-based conductive materials include metals such as Cu, Ni, Al, Ag, Au, Pt, Zn, and Mn, and alloys thereof. A single conductive material may be used, or a plurality of types may be used in combination.
• fillers include silica, diatomaceous earth, alumina, zinc oxide, magnesium oxide, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, calcium silicate, talc, mica, bentonite, activated clay, glass fiber, and aluminum nitride. mentioned.
• the filler may be used alone or in combination of multiple types.
• plasticizers include polyols such as glycerin, diglycerin, triglycerin, ethylene glycol, propylene glycol and polyethylene glycol; Aromatic polycarboxylic acid esters such as polycarboxylic acid esters, terephthalic acid esters, isophthalic acid esters, phthalic acid esters, trimellitic acid esters, and benzoic acid esters, and polyesters.
• the plasticizer may be used alone or in combination of multiple types.
• antioxidants examples include phenol-based antioxidants, amine-based antioxidants, lactone-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and the like. Antioxidants may be used alone or in combination of multiple types.
• flame retardants examples include phosphorus- and halogen-containing organic compounds, bromine- or chlorine-containing organic compounds, ammonium polyphosphate, aluminum hydroxide, antimony oxide, and other additive and reactive flame retardants.
• a flame retardant may be used independently and may be used in combination of multiple types.
• colorants include inorganic pigments such as carbon black, titanium oxide, zinc oxide, iron oxide and mica, and organic pigments such as coupling azo, condensed azo, anthraquinone, thioindigo, dioxazone and phthalocyanine pigments. A pigment etc. are mentioned. Colorants may be used alone or in combination of multiple types.
• surfactants examples include anionic surfactants such as alkylbenzene sulfonates, ⁇ -olefin sulfonates, and phosphate esters, amine salts (alkylamine salts, imidazoline, etc.), quaternary ammonium salts (dialkyldimethylammonium cationic surfactants such as salts, alkylbenzyldimethylammonium salts, pyridinium salts, benzethonium chloride, etc.), sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride, polyoxyethylene nonylphenyl ether, polyoxy Examples include nonionic surfactants such as ethylene dodecyl ether. Surfactants may be used alone or in combination of multiple types.
• Examples of adhesives other than the above acrylic polymers include silicone-based adhesives, polyester-based adhesives, urethane-based adhesives, and rubber-based adhesives.
• silicone-based adhesives include dimethylsiloxane-based and diphenylsiloxane-based adhesives.
• Examples of the polyester pressure-sensitive adhesive include polyester obtained by polycondensation of a carboxylic acid component having two or more functional groups and a diol component.
• Urethane-based adhesives include, for example, urethane-based polymers obtained by reacting polyols with polyisocyanate compounds.
• rubber adhesives examples include synthetic rubbers such as styrene-isoprene block copolymers, styrene-butadiene-styrene block copolymers, styrene-butadiene rubbers, polyisoprene rubbers, polyisobutylenes, and butyl rubbers, and natural rubbers.
• the amount of these adhesives other than the acrylic polymer is 40 parts by weight or less, preferably 35 parts by weight or less, more preferably 30 parts by weight or less, relative to 100 parts by weight of the acrylic polymer. Preferably, it is 20 parts by weight or less, more preferably 10 parts by weight or less, more preferably 5 parts by weight or less, more preferably 3 parts by weight or less, other than an acrylic polymer It is more preferable that no pressure-sensitive adhesive is included.
• the amount of these additives (excluding adhesives other than the acrylic polymer) contained in the electro-peeling adhesive composition is not particularly limited, but for example, 0.1 to 200 parts by weight per 100 parts by weight of the acrylic polymer. and can range from 1 to 100 parts by weight.
• the electro-peelable pressure-sensitive adhesive composition of this embodiment can be produced by stirring an acrylic polymer, an ionic liquid, a transfer accelerator, an optional cross-linking agent, and the like.
• the stirring method is not particularly limited, and a known stirring method can be used.
• an acrylic polymer, an ionic liquid, a migration accelerator, an optional cross-linking agent, and the like are stirred using a V-type mixer or mixer (dissolver, homomixer, planetary mixer, etc.). During stirring, the above additives may be added.
• the electro-peeling pressure-sensitive adhesive composition of this embodiment has excellent electro-peeling properties even when exposed to high temperature conditions. Therefore, it is suitable for use under conditions where the electrical peeling pressure-sensitive adhesive composition can reach high temperatures, in which the conventional electrical peeling pressure-sensitive adhesive composition could not be used due to the deterioration of the electrical peeling property.
• Such conditions include, for example, around the engine of a car, around the driving part of a home appliance, and during the manufacture of electronic parts and metal parts.
• the electro-peelable pressure-sensitive adhesive composition of the present embodiment is suitable for use under conditions that can reach high temperatures. Even under such conditions, it can be suitably used in the same manner as conventional electro-peeling pressure-sensitive adhesive compositions. That is, the electro-peelable pressure-sensitive adhesive composition of the present embodiment can be easily peeled off from a conductive object by applying a voltage without UV irradiation or heat treatment.
• the peelable pressure-sensitive adhesive composition can be suitably used for adhesively fixing non-transparent members that cannot be irradiated with UV rays, members that are vulnerable to heat, and the like.
• the parts are fixed with the electro-peeling adhesive composition of the present invention and then sold.
• the parts By collecting used home appliances, personal computers, etc. and applying a voltage to the fixed parts, the parts can be easily recollected.
• the ability to easily recollect parts and the like is also useful from the viewpoint of recycling and reuse.
• it can be suitably used for fixing members that require high processing accuracy, or members that are difficult to physically fix, such as thin metal plates and substrates.
• the electro-releasable pressure-sensitive adhesive composition can be used for temporary bonding of parts in the electronic component manufacturing process (for example, temporary bonding of wafers during dicing of LSI chips), and the temporary bonding of parts can be easily performed by applying a voltage. can be released.
• Other applications include bonding applications between sensors and conductive objects. Even in this application, the sensor can be easily recovered by peeling off the sensor by applying a low voltage, and the sensor can be used repeatedly, which is economical.
• the electro-peeling adhesive composition of the present embodiment recovers its adhesiveness over time after voltage application. Therefore, the electro-peelable pressure-sensitive adhesive composition after voltage application is reusable. This is because the anions and cations of the ionic liquid, which have moved in opposite directions due to voltage application, migrate uniformly in the electro-peelable pressure-sensitive adhesive composition over time. Therefore, the electro-peeling pressure-sensitive adhesive composition of the present embodiment can be used repeatedly as a pressure-sensitive adhesive, which is economical and useful from the viewpoint of recycling and reuse.
• the electro-peelable pressure-sensitive adhesive product of the present embodiment (hereinafter also simply referred to as the pressure-sensitive adhesive product) is composed of a substrate and an electro-peeling adhesive layer formed so as to be in contact with the substrate.
• Another form of the adhesive product is composed of a core material and two electro-releasable adhesive layers formed so as to be in contact with both sides of the core material.
• the electro-peeling adhesive layer of the adhesive product contains an electro-peeling adhesive composition.
• the adhesive product of this embodiment functions as a substance that fixes a substance to be fixed to an adherend by the adhesive product (referred to as a fixing target) to the adherend.
• the shape of the adhesive product is not particularly limited, but it can take an appropriate form, such as an adhesive tape or an adhesive sheet, depending on the application.
• the surface to be used of the electro-releasable pressure-sensitive adhesive layer may be protected until it is used with a release-treated polyethylene terephthalate film, release paper, or the like.
• the adherend of this embodiment refers to an object that provides a place to which an object to be fixed is fixed via the electro-peeling pressure-sensitive adhesive composition, electro-peeling pressure-sensitive adhesive layer or pressure-sensitive adhesive product of this embodiment.
• fixing includes direct fixing and indirect fixing
• direct fixing refers to the state in which the adherend or fixed object is in direct contact with the adhesive product
• adheresive and/or “fixed object” refers to a state in which the adherend and/or the object to be fixed are not in direct contact with the adhesive product but are in contact with each other through the conductive auxiliary material.
• the fixing method may be direct fixing or indirect fixing.
• the adherend may be an adherend having conductivity (conductive adherend) or an adherend having no conductivity (non-conductive adherend).
• conductive adherend When the adherend is a conductive adherend, the adhesive product may be directly attached to the adherend.
• non-conductive adherend it is essential to attach the conductive auxiliary material to the non-conductive adherend. Any adhesive such as a commercially available adhesive is used to attach the conductive auxiliary material.
• conductive adherends include metals such as iron, aluminum, copper, silver, and gold, metal plates made of alloys of these metals, metal products, and metal workbenches.
• Non-conductive adherends include, for example, wooden plywood, plastic products, non-metallic workbenches, and the like.
• the object to be fixed in this embodiment is not particularly limited, but as long as the object to be fixed has conductivity, the object to be fixed may be directly attached to the adhesive product. If the object to be fixed is non-conductive, it is essential to attach the electrically conductive auxiliary material to the object to be fixed and then to the adhesive product, as in the case of non-conductive adherends.
• Examples of conductive fixed objects include foils (thickness less than 100 ⁇ m) and plates (thickness 100 ⁇ m or more) made of metals such as iron, aluminum, copper, silver, and gold, or alloys of these metals. Mesh or cloth containing fibers mixed or coated with metals or alloys, resin sheets containing these metals or alloys, resin plates with layers containing these metals, alloys or conductive metal oxides, etc. be done. Examples of non-conductive fixed objects include resin, wood, plastic plates, and the like.
• the substrate of the present embodiment refers to a planar object to which the electro-peeling adhesive composition is applied.
• the substrate may be conductive or non-conductive.
• substrates used for adhesive products include foils or plates made of metals such as aluminum, copper, silver, and gold, or alloys of these metals, polyethylene terephthalate (PET) and polyimide films, carbon fibers, paper, A woven fabric or a non-woven fabric can be used, and the thickness is not particularly limited.
• PET polyethylene terephthalate
• non-conductive substrates used in adhesive products should be peeled off before use. These can be selected appropriately depending on the shape of the electro-peeling adhesive product to be used.
• the base material or core material may be one in which the applied electro-peelable pressure-sensitive adhesive composition adheres to the surface of the base material or core material as it is, or one that penetrates into the gaps between fibers of the base material or core material. There may be. Examples of such substrates include paper and non-woven fabrics.
• the electro-peelable pressure-sensitive adhesive layer may be formed not only on one side of the substrate but also on both sides.
• the base material is called the core material. It is essential that the core material allows the ionic liquid to pass between the layers of the electro-peeling adhesive on both sides when a voltage is applied. Since the core material is a material through which the ionic liquid can pass, the adhesive strength can be reduced by applying a voltage to the electro-peeling adhesive layers on both sides. By using the base material or the core material, the pressure-sensitive adhesive product can have strength, and workability during use can be improved.
• the conductive auxiliary material is not particularly limited as long as it has conductivity. Examples include metals such as aluminum, copper, silver, and gold, alloys of these metals, or conductive metal oxides (indium tin oxide: ITO, etc.) vapor-deposited films, cloth containing fibers mixed or coated with these metals or alloys, resin sheets containing these metals or alloys, these metals, alloys or conductive metal oxides A resin plate having a layer containing
• FIG. 1 shows an example of a cross section of an adhesive product in the form of a single-sided tape (the cross section of a tape stuck on a horizontal surface and cut vertically; the same shall apply hereinafter), and FIG. 2 shows an example of a cross section of an adhesive product in the form of a double-sided tape.
• FIGS. 3A to 7B show an example of a circuit when voltage is applied to the electro-peeling adhesive layer of these adhesive products via a conductive object, and an example of peeling after voltage application.
• the form of use of the adhesive product of the present invention is not limited to the following circuit examples and peeling examples. In the peeling examples below, the electro-peelable pressure-sensitive adhesive layer or adhesive product is left on the adherend. Peeling can be performed in such a way that a sticky product remains on the object.
• the side of the power supply on which the adhesive product remains depends on the composition of the adhesive product and is not particularly limited.
• 1 is an electrically exfoliating adhesive layer
• 2 is a base material or core material
• 3 is a conductive adherend
• 4 is a DC power supply
• 5 is a conductive fixing object
• 6 is a non-conductive fixing.
• An object, 7 means an arbitrary adhesive
• 8 means a conductive auxiliary material
• 9 means a non-conductive adherend.
• FIG. 3A shows an example of a cross section in which an adhesive product in the form of a single-sided tape is adhered to a conductive adherend 3 and a voltage is applied.
• the base material 2 here is a material having conductivity.
• a terminal is connected to the substrate 2 and the conductive adherend 3, and a voltage is applied to the electro-peeling adhesive layer 1 by forming a circuit with the DC power supply 4, and as shown in FIG. 3B.
• the adhered conductive substrate 2 can be peeled off from the conductive adherend 3 .
• FIG. 4A shows an example of a cross section in which a conductive fixing target 5 is adhered to a conductive adherend 3 using an adhesive product in the form of a double-sided tape and a voltage is applied.
• the double-sided tape has a core material 2 and an electro-releasable pressure-sensitive adhesive layer 1 formed on both sides thereof.
• a terminal is connected to a conductive fixing object 5 and a conductive adherend 3, and a voltage is applied to the electro-peeling adhesive layer 1 by forming a circuit with a DC power source 4.
• the adhered conductive fixing object 5 can be peeled off from the conductive adherend 3 as shown in 4B.
• FIG. 5A shows an example of a cross section in which a non-conductive fixed object 6 is adhered to a conductive adherend 3 using an adhesive product in the form of double-sided tape and a voltage is applied.
• an aluminum plate as a conductive auxiliary material 8 is attached to a non-conductive fixed object 6 using an arbitrary adhesive agent 7, and the non-conductive fixed object 6 and the conductive auxiliary are attached.
• the material 8 and the conductive adherend 3 are adhered using an adhesive product.
• a terminal was connected to the conductive auxiliary material 8 and the conductive adherend 3, and a voltage was applied to the electro-peeling adhesive layer 1 by forming a circuit with the DC power supply 4, and the adhesive was adhered as shown in FIG. 5B.
• the non-conductive fixing object 6 can be peeled off from the conductive adherend 3 . In this case, the conductive auxiliary material 8 attached to the non-conductive fixing object 6 remains on the non-conductive fixing object 6 .
• FIG. 6A shows an example of a cross section in which a conductive fixing object 5 is adhered to a non-conductive adherend 9 using an adhesive product in the form of double-sided tape and a voltage is applied.
• an aluminum plate as a conductive auxiliary material 8 is attached to a non-conductive adherend 9 using an arbitrary adhesive 7, and a conductive fixed object 5 and a conductive auxiliary are attached.
• the material 8 and the non-conductive adherend 9 are adhered using an adhesive product.
• a terminal was connected to the conductive fixing object 5 and the conductive auxiliary material 8 to form a circuit with the DC power source 4, thereby applying a voltage to the electro-peeling adhesive layer 1 and sticking it as shown in FIG. 6B.
• a conductive fixed object 5 can be separated from a non-conductive adherend 9 .
• FIG. 7A shows an example of a cross section in which a non-conductive fixing object 6 is adhered to a non-conductive adherend 9 using an adhesive product in the form of a double-sided tape and a voltage is applied.
• an aluminum plate as a conductive auxiliary material 8 is attached to each of the non-conductive fixing object 6 and the non-conductive adherend 9 using an arbitrary adhesive agent 7, and the non-conductive A conductive auxiliary material 8 to which a non-conductive object 6 is adhered and a conductive auxiliary material 8 to which a non-conductive adherend 9 is adhered are adhered using an adhesive product.
• Terminals are connected to each of the conductive auxiliary materials 8, a voltage is applied to the electrically peeling adhesive layer 1 by forming a circuit with the DC power supply 4, and a non-conductive fixed object is adhered as shown in FIG. 7B. 6 can be peeled from the non-conductive adherend 9 . In this case, the conductive auxiliary material 8 attached to the non-conductive fixing object 6 remains on the non-conductive fixing object 6 .
• each of the above peeling operations can be performed even by applying a low voltage of 30 V or less.
• the electro-peeling adhesive layer can be formed, for example, by applying an electro-peeling adhesive composition to a substrate or core material.
• the method of applying the electro-peelable pressure-sensitive adhesive composition is not particularly limited, but for example, a spin coater, gravure coater, applicator, multi-coater, die coater, bar coater, roll coater, blade coater, knife coater, or the like can be used. .
• the thickness of the electro-peelable pressure-sensitive adhesive layer is not particularly limited, but is preferably in the range of 1 to 200 ⁇ m, more preferably in the range of 1 to 100 ⁇ m, even more preferably in the range of 1 to 50 ⁇ m.
• the electrically-peeling pressure-sensitive adhesive layer may be heated to dry the electrically-peeling pressure-sensitive adhesive composition.
• the electro-peeling adhesive layer preferably has an adhesive strength of 25 N/25 mm or more, more preferably 30 N/25 mm or more, before voltage is applied.
• the adhesiveness of the electro-peeling adhesive composition recovers over time after voltage application. Therefore, the adhesive product after voltage application is reusable. Since the adhesive product of the present embodiment can be used repeatedly, it is economical and useful from the viewpoint of recycling and reuse.
• One embodiment of the present invention is a method of making an electropeeling adhesive product.
• Electrically-peeling adhesive products can be produced, for example, by coating an electrically-peeling adhesive composition on a substrate or a core material to form an electrically-peeling adhesive layer.
• the electro-peeling adhesive composition, the electro-peeling adhesive layer, the substrate, the electro-peeling adhesive product and the coating method are as described above.
• the thickness of the adhesive product is not particularly limited, but it is preferably in the range of 1 to 200 ⁇ m, more preferably in the range of 1 to 100 ⁇ m.
• the thickness of the electrically peelable pressure-sensitive adhesive layer and the pressure-sensitive adhesive product refers to values measured using a known thickness-measuring device such as a Peacock precision measuring device.
• the electro-peeling pressure-sensitive adhesive layer or pressure-sensitive adhesive product of the present embodiment can be obtained by applying a voltage after attaching the electro-peeling pressure-sensitive adhesive layer or pressure-sensitive adhesive product on a conductive object. It can be peeled off from a conductive object to which the adhesive product is directly attached.
• a peeling method for example, if the object to be fixed and the adherend are conductive, terminals are connected to the object to be fixed and the adherend, and a voltage is applied between the terminals to remove the electro-peeling adhesive.
• the layer or adhesive product can be peeled off from the fixed object or adherend. If the object to be fixed and/or the adherend is not conductive, fixing and peeling operations can be performed even if it is non-conductive by adhering an aluminum plate or the like as a conductive auxiliary material. These fixing and peeling operations are shown in the adhesive product peeling example above.
• the voltage to be applied is not particularly limited as long as it can peel off the electro-peeling adhesive layer or adhesive product.
• the applied voltage range is, for example, 690V, 650V, 600V, 550V, 500V, 480V, 450V, 415V, 400V, 380V, 350V, 347V, 300V, 250V, 240V, 230V, 220V, 210V, 208V , 200V, 180V , 160V, 150V, 130V, 125V, 120V, 115V, 110V, 105V, 100V, 90V, 80V, 70V, 60V, 50V, 40V and 30V up to 0.5V, 1V, 2V, 3V, 4V, 5V , 6V, 7V, 8V, 9V and 10V voltages can be selected and combined with lower limits.
• working with a voltage in the range of 1 to 30 V is particularly preferable from the standpoints of miniaturization of the application device, safety, and effects on fixed
• the electrically peelable pressure-sensitive adhesive layer and the pressure-sensitive adhesive product of the present embodiment can be peeled off from a conductive object even when the applied voltage is as low as several volts. be able to. This indicates that according to this embodiment, the peeling operation can be performed with a simple application device that is excellent in safety for the operator and can be carried around.
• the voltage application time is not particularly limited as long as the electro-releasable adhesive layer or adhesive product can be peeled off, but considering the effect on the fixed object, it is preferably within 10 minutes, more preferably within 5 minutes. It is preferably within 3 minutes, more preferably within 3 minutes.
• the temperature at which peeling is performed is not particularly limited, room temperature is preferable.
• the electrically peelable pressure-sensitive adhesive layer or pressure-sensitive adhesive product of the present embodiment can be peeled off from a conductive object at a low voltage and in a short time, so that the fixing object can be fixed with extremely little influence of heat. be able to.
• One embodiment of the present invention involves the use of an acrylic polymer, an ionic liquid, and an alkyl ether of polyethylene glycol for the manufacture of an electro-peeling adhesive composition.
• the content of the ionic liquid is 30 to 90 parts by weight with respect to 100 parts by weight of the acrylic polymer, and the content of the alkyl ether of polyethylene glycol is 5 to 45 parts by weight with respect to 100 parts by weight of the acrylic polymer.
• the electro-peeling pressure-sensitive adhesive composition can be produced by mixing so as to form a part, optionally adding a cross-linking agent, an additive, and the like, and stirring by a known method.
• the acrylic polymer, the ionic liquid, the alkyl ether of polyethylene glycol, the cross-linking agent and the additive are as described above.
• One embodiment of the present invention includes the use of an electro-peeling adhesive composition for the manufacture of an electro-peeling adhesive product.
• An electrically-peeling adhesive product can be produced by forming an electrically-peeling adhesive layer on a base material (or a core material) using an electrically-peeling adhesive composition.
• the electro-peeling adhesive composition, the electro-peeling adhesive layer, the substrate and the electro-peeling adhesive product are as described above.
• azobisisobutyronitrile AIBN, Junsei Chemical Company
• the obtained acrylic pressure-sensitive adhesive contained 35% by weight of an acrylic polymer (weight average molecular weight of about 800,000, Tg-46°C) and had a viscosity of 7,000 mPa ⁇ s.
• Electro-Peelable Adhesive Composition 100 parts by weight of the above acrylic adhesive (including 35 parts by weight of the acrylic polymer) was added with Coronate (registered trademark) L-55E (Tosoh Corporation) as an isocyanate cross-linking agent. ) 5.0 parts by weight, 14.0 parts by weight of Elexel (registered trademark) AS-110 (EMI-FSI: Daiichi Kogyo Seiyaku Co., Ltd.) as an ionic liquid, and 2.1 parts by weight of dimethyl tetraglycol (Nippon Emulsifier Co., Ltd.: molecular weight: about 220) as a migration promoter. parts by weight were added, stirred at room temperature for 10 minutes with a dissolver, and degassed by standing to obtain an electrically peelable pressure-sensitive adhesive composition.
• Coronate registered trademark
• L-55E Tosoh Corporation
• AS-110 EMI-FSI: Daiichi Kogyo Seiyaku Co.,
• the electro-peelable adhesive composition obtained in 2. was applied to a polyethylene terephthalate film having a silicone-treated surface and dried at 100° C. for 5 minutes.
• the surface of the dried film coated with the electro-peelable pressure-sensitive adhesive composition was adhered to a non-woven fabric [Milife (registered trademark) TY0503FE (ENEOS Techno Materials Co., Ltd.)].
• a polyethylene terephthalate film having a silicone-treated surface was coated with the electro-peelable pressure-sensitive adhesive composition and dried to prepare a film.
• the adhesive product of Example 1 double-sided tape, thickness 80 ⁇ m
• Comparative example 1 An adhesive product of Comparative Example 1 was obtained in the same manner as in Example 1, except that no transfer promoter was used.
• Comparative example 2 A pressure-sensitive adhesive product of Comparative Example 2 was obtained in the same manner as in Example 1, except that the amount of transfer accelerator was 1.05 parts by weight per 100 parts by weight of the acrylic pressure-sensitive adhesive.
• Example 2 A pressure-sensitive adhesive product of Example 2 was obtained in the same manner as in Example 1, except that the amount of transfer accelerator was 3.5 parts by weight per 100 parts by weight of the acrylic pressure-sensitive adhesive.
• Example 3 A pressure-sensitive adhesive product of Example 3 was obtained in the same manner as in Example 1, except that the amount of the transfer accelerator was 5.25 parts by weight per 100 parts by weight of the acrylic pressure-sensitive adhesive.
• Example 4 A pressure-sensitive adhesive product of Example 4 was obtained in the same manner as in Example 1, except that the amount of transfer accelerator was 7.0 parts by weight per 100 parts by weight of the acrylic pressure-sensitive adhesive.
• Example 5 A pressure-sensitive adhesive product of Example 5 was obtained in the same manner as in Example 1, except that the amount of the transfer accelerator was 10.5 parts by weight per 100 parts by weight of the acrylic pressure-sensitive adhesive.
• Example 6 A pressure-sensitive adhesive product of Example 6 was obtained in the same manner as in Example 1, except that the amount of transfer accelerator was 14.0 parts by weight per 100 parts by weight of the acrylic pressure-sensitive adhesive.
• Comparative Example 3 A pressure-sensitive adhesive product of Comparative Example 3 was obtained in the same manner as in Example 1, except that the amount of the transfer accelerator was 17.5 parts by weight per 100 parts by weight of the acrylic pressure-sensitive adhesive.
• Comparative Example 4 An adhesive product of Comparative Example 4 was obtained in the same manner as in Example 2 except that the amount of the ionic liquid was 7.0 parts by weight per 100 parts by weight of the acrylic adhesive.
• Example 7 An adhesive product of Example 7 was obtained in the same manner as in Example 2, except that the amount of the ionic liquid was 17.5 parts by weight with respect to 100 parts by weight of the acrylic adhesive.
• Example 8 An adhesive product of Example 8 was obtained in the same manner as in Example 2, except that the amount of the ionic liquid was 21.0 parts by weight per 100 parts by weight of the acrylic adhesive.
• Example 9 An adhesive product of Example 9 was obtained in the same manner as in Example 2, except that the amount of the ionic liquid was 24.5 parts by weight with respect to 100 parts by weight of the acrylic adhesive.
• Example 10 An adhesive product of Example 10 was obtained in the same manner as in Example 2, except that the amount of the ionic liquid was 28.0 parts by weight per 100 parts by weight of the acrylic adhesive.
• Example 11 Example except that Elexel (registered trademark) IL-210 (EMI-TFSI: Daiichi Kogyo Seiyaku Co., Ltd.) was used as the ionic liquid, and the amount of the transfer accelerator was 7.0 parts by weight with respect to 100 parts by weight of the acrylic pressure-sensitive adhesive.
• the adhesive product of Example 11 was obtained in the same manner as in Example 1.
• Example 12 EMI-TFSI was used as the ionic liquid, the amount of the ionic liquid was 17.5 parts by weight with respect to 100 parts by weight of the acrylic pressure-sensitive adhesive, and the amount of the transfer accelerator was 3.5 parts by weight.
• the adhesive product of Example 12 was obtained.
• Example 13 The amount of the ionic liquid was 17.5 parts by weight per 100 parts by weight of the acrylic adhesive, the transfer accelerator was diethylene glycol dibutyl ether [Hisolve BDB (Toho Chemical Industry Co., Ltd.)], and the amount of the transfer accelerator was 100 parts by weight of the acrylic adhesive.
• a pressure-sensitive adhesive product of Example 13 was obtained in the same manner as in Example 1 except that the content was 3.5 parts by weight.
• Example 14 The amount of the ionic liquid was 17.5 parts by weight per 100 parts by weight of the acrylic pressure-sensitive adhesive, the transfer accelerator was triethylene glycol butyl methyl ether [Hisolve BTM (Toho Chemical Industry Co., Ltd.)], and the amount of the transfer accelerator was an acrylic adhesive.
• An adhesive product of Example 14 was obtained in the same manner as in Example 1, except that the amount was 3.5 parts by weight per 100 parts by weight of the adhesive.
• a rubber roller weighing 2 kg was reciprocated once in the long side direction of the adhesive product at a speed of 300 mm/min to press the adherend, the adhesive product, and the object to be fixed to obtain an evaluation sample.
• each evaluation sample was placed in a constant temperature machine and allowed to stand in a high temperature environment at 80°C for 100 hours. After 100 hours, each evaluation sample was collected and left at room temperature for 2 hours. , and measured the force (adhesive strength: N/25mm) required to peel off the adhesive tape from the adherend at a 180° angle (hereinafter referred to as 180° peel) at a tensile speed of 300mm/min. The average value of the measured values was used as the measured value.
• each evaluation sample was placed in a constant temperature machine and allowed to stand in a high temperature environment at 80°C for 100 hours. After 100 hours had elapsed, each evaluation sample was collected and left at room temperature for 2 hours. Then, an electrode was attached so that the conductive adherend side of the evaluation sample was a positive electrode and the fixed object side was a negative electrode. A voltage of 10 V was applied to the evaluation sample for 60 seconds by using a DC power supply as a power supply and adjusting the voltage using a transformer. After voltage application, the force required to peel the adhesive tape from the adherend by 180° was measured in the same manner as described above.
• the decrease rate was calculated based on the following formula (6). When the rate of decrease is 50% or more, peeling by voltage application is easy. If it is lower than 50%, peeling is difficult.
• Table 1 shows the type and amount of ionic liquid used, the type and amount of transfer accelerator used, and the evaluation results of each adhesive product of Examples 1 to 14 and Comparative Examples 1 to 4.
• each usage amount is converted to the amount per 100 parts by weight of the acrylic polymer.
• IA is EMI-FSI
• IB is EMI-TFSI
• MA is dimethyltetraglycol
• MB is diethyleneglycoldibutylether
• MC is triethyleneglycolbutylmethylether.
• Electro-peeling adhesive layer 2 Base material or core material 3 Conductive adherend 4 DC power supply 5 Conductive object to be fixed 6 Non-conductive object to be fixed 7 Optional adhesive 8 Conductive auxiliary material 9 non-conductive adherends

Landscapes

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

Priority Applications (6)

Applications Claiming Priority (1)

Publications (1)

Family

ID=87563905

Family Applications (1)

Country Status (6)

Families Citing this family (3)

Citations (5)

Family Cites Families (7)

• 2022
  • 2022-02-10 JP JP2023579988A patent/JP7602292B2/ja active Active
  • 2022-02-10 KR KR1020247002175A patent/KR102919279B1/ko active Active
  • 2022-02-10 US US18/293,973 patent/US12584047B2/en active Active
  • 2022-02-10 WO PCT/JP2022/005471 patent/WO2023152911A1/ja not_active Ceased
  • 2022-02-10 EP EP22925932.0A patent/EP4365254A4/en active Pending
  • 2022-02-10 CN CN202280054348.1A patent/CN117795031A/zh active Pending

Patent Citations (5)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events