WO2012133268A1 - Emulsion adhesive composition and re-peelable adhesive sheet - Google Patents

Emulsion adhesive composition and re-peelable adhesive sheet Download PDF

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Publication number
WO2012133268A1
WO2012133268A1 PCT/JP2012/057692 JP2012057692W WO2012133268A1 WO 2012133268 A1 WO2012133268 A1 WO 2012133268A1 JP 2012057692 W JP2012057692 W JP 2012057692W WO 2012133268 A1 WO2012133268 A1 WO 2012133268A1
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WO
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Prior art keywords
sensitive adhesive
pressure
emulsion
adhesive composition
resin
Prior art date
Application number
PCT/JP2012/057692
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French (fr)
Japanese (ja)
Inventor
正憲 山岸
文徳 池田
Original Assignee
リンテック株式会社
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Publication date
Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to JP2013507544A priority Critical patent/JP5937570B2/en
Priority to CN201280016208.1A priority patent/CN103534324B/en
Priority to KR1020137025114A priority patent/KR101880420B1/en
Publication of WO2012133268A1 publication Critical patent/WO2012133268A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • 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
    • C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J193/00—Adhesives based on natural resins; Adhesives based on derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J193/00—Adhesives based on natural resins; Adhesives based on derivatives thereof
    • C09J193/04—Rosin
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/334—Applications of adhesives in processes or use of adhesives in the form of films or foils as a label
    • 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

Definitions

  • the present invention relates to an emulsion-type pressure-sensitive adhesive composition suitably used for producing tire display labels and the like and a releasable pressure-sensitive adhesive sheet using the pressure-sensitive adhesive composition.
  • the product display label is attached to the product or the like in order to convey the product name or other information.
  • pressure-sensitive adhesive sheets having a pressure-sensitive adhesive layer on a substrate have been widely used as such product display labels.
  • Such a pressure-sensitive adhesive sheet is required to have a high pressure-sensitive adhesive force at the time of distribution of goods, but finally has a characteristic that it can be peeled relatively easily and no adhesive residue is generated. Therefore, in pressure-sensitive adhesive sheets that require these characteristics, various studies have been made so far regarding pressure-sensitive adhesives and adhesives constituting the pressure-sensitive adhesive sheet.
  • Patent Document 1 discloses a specific pressure-sensitive adhesive composition composed of an acrylic emulsion polymer, an anionic emulsifier and a nonionic emulsifier, and this composition has excellent adhesiveness and attachment / detachment performance. It is described as showing.
  • Patent Document 2 discloses an acrylic emulsion type pressure-sensitive polymer containing an acrylic emulsion obtained by emulsion polymerization of a specific acrylic ester, acrylonitrile and ⁇ , ⁇ -unsaturated carboxylic acid in the presence of an anionic reactive emulsifier. An adhesive is disclosed, and it is described that this adhesive hardly causes adhesive residue on an adherend.
  • the performance of the pressure-sensitive adhesive and pressure-sensitive adhesive sheet has been improved so far.
  • the pressure-sensitive adhesive force may not be sufficient with a normal pressure-sensitive adhesive sheet.
  • a tire display label includes a manufacturer name, a brand name, a size, and the like, and is affixed to the tread surface of the tire. Since there is a beard-like projection called “Spoo” formed due to the air vent of the mold used at the time of molding the tire, the bonding area becomes considerably small.
  • Spoo beard-like projection
  • Such a tire-specific shape greatly reduces the pressure-sensitive adhesive strength of the pressure-sensitive adhesive sheet. Therefore, when a pressure-sensitive adhesive sheet using the adhesive described in the above document is attached to the tread surface of the tire, the pressure-sensitive adhesive force is not sufficient and is easily peeled off. There was a problem.
  • Patent Document 3 discloses a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer obtained by blending a liquid tackifier resin with a specific acrylic resin and crosslinking it.
  • both the pressure-sensitive adhesive sheet and the pressure-sensitive adhesive layer have a low cohesive force in order to increase the adhesive force to the rough surface, and have a problem of adhesive residue.
  • the present inventors include 2-ethylhexyl acrylate, butyl acrylate, and ethylenically unsaturated carboxylic acid, and the mass ratio of 2-ethylhexyl acrylate to butyl acrylate is within a specific range.
  • the pressure-sensitive adhesive composition was found to have a high adhesive force with respect to a rough surface and a sufficient cohesive force, and the present invention was completed.
  • the following emulsion type pressure-sensitive adhesive compositions (1) to (6) are provided.
  • Acrylic copolymer (A) obtained by emulsion polymerization of a monofunctional monomer mixture containing 2-ethylhexyl acrylate, butyl acrylate and ethylenically unsaturated carboxylic acid, and a polyfunctional monomer, and
  • the following releasable pressure-sensitive adhesive sheets (7) to (9) are provided.
  • the releasable pressure-sensitive adhesive sheet using the emulsion-type pressure-sensitive adhesive composition of the present invention has a high adhesive force even on a rough surface, it is also used for an adherend having a rough surface that is difficult to stick, such as a tire. can do.
  • the releasable pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer obtained using the pressure-sensitive adhesive composition of the present invention. Since the pressure-sensitive adhesive layer obtained using the pressure-sensitive adhesive composition of the present invention has sufficient cohesive force, the re-peelable pressure-sensitive adhesive sheet of the present invention is less likely to have adhesive residue after peeling.
  • the pressure-sensitive adhesive composition does not adhere to a cutter of a cutting machine, a guide of a printing machine or the like during label processing, and the pressure-sensitive adhesive sheet or the like is not contaminated.
  • an emulsion-type pressure-sensitive adhesive composition and 2) a re-peelable pressure-sensitive adhesive sheet.
  • adhesive composition capable of forming a pressure-sensitive adhesive layer having high adhesive strength is referred to as “adhesive composition having high adhesive strength”, and “adhesive capable of forming a pressure-sensitive adhesive layer having high cohesive strength”.
  • Adhesive composition may be abbreviated as “adhesive composition having high cohesive strength”.
  • other characteristics may be omitted as well.
  • Emulsion-type pressure-sensitive adhesive composition comprises a monofunctional monomer mixture containing 2-ethylhexyl acrylate, butyl acrylate and ethylenically unsaturated carboxylic acid, and a polyfunctional monomer.
  • An emulsion-type pressure-sensitive adhesive composition comprising an acrylic copolymer (A) obtained by emulsion polymerization and a tackifier resin (B), wherein the mass ratio of 2-ethylhexyl acrylate to butyl acrylate (2-ethylhexyl acrylate) Content / butyl acrylate content) is 0.6 to 2.5, and the softening point of the tackifying resin (B) is 130 to 180 ° C.
  • the emulsion-type pressure-sensitive adhesive composition of the present invention is a dispersion liquid in which an acrylic copolymer (A) and a tackifier resin (B) are dispersed in an aqueous solvent described later.
  • the acrylic copolymer (A) used in the present invention is obtained by emulsion polymerization of a monofunctional monomer mixture containing 2-ethylhexyl acrylate, butyl acrylate and ethylenically unsaturated carboxylic acid and a polyfunctional monomer. It is what
  • the acrylic copolymer (A) used in the present invention is obtained by using 2-ethylhexyl acrylate and butyl acrylate in combination, and the pressure-sensitive adhesive composition containing these has adhesive strength, cohesive strength, and re-peeling. Excellent balance of sex.
  • the mass ratio of 2-ethylhexyl acrylate to butyl acrylate is 0.6 to 2.5, and ranges from 1.6 to 1.9. preferable.
  • the total content of 2-ethylhexyl acrylate and butyl acrylate is not particularly limited, but is preferably 80 to 99.8% by mass, and 90 to 99.8% by mass based on the total monofunctional monomer mixture. More preferred.
  • An ethylenically unsaturated carboxylic acid is a compound having at least one carboxyl group and one polymerizable unsaturated bond in one molecule.
  • acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid and the like can be mentioned.
  • acrylic acid and methacrylic acid are preferable from the viewpoint of availability and polymerizability.
  • An ethylenically unsaturated carboxylic acid can be used individually by 1 type or in combination of 2 or more types.
  • the content of the ethylenically unsaturated carboxylic acid is not particularly limited, but is preferably in the range of 0.3 to 0.8% by mass, and 0.35 to 0.75% by mass with respect to the entire monofunctional monomer mixture. Is more preferable.
  • a pressure-sensitive adhesive composition having a more excellent cohesive force can be obtained, and as a result, a pressure-sensitive adhesive sheet can be obtained that adheres to the tread portion of the tire without any adhesive residue.
  • the adhesive composition excellent in mechanical stability and coating property can be obtained because it is 0.8 mass% or less.
  • the monofunctional monomer mixture may contain other ethylenically unsaturated monomers other than these monomers as long as the effects of the present invention are not impaired.
  • a monomer may be contained.
  • other ethylenically unsaturated monomers are also included in the monofunctional monomer mixture.
  • Examples of the other ethylenically unsaturated monomers include (meth) acrylic acid esters other than 2-ethylhexyl acrylate and butyl acrylate, (meth) acrylic acid esters containing a hydroxyl group, vinyl acetate, and styrene.
  • Examples of (meth) acrylic acid esters other than 2-ethylhexyl acrylate and butyl acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl methacrylate, hexyl (meth) acrylate, and octyl (meth) acrylate.
  • (meth) acrylic acid ester containing a hydroxyl group examples include hydroxymethyl (meth) acrylate and hydroxylethyl (meth) acrylate.
  • (meth) acrylate means acrylate or methacrylate.
  • the content of other ethylenically unsaturated monomers is preferably 0 to 20% by mass and more preferably 0 to 10% by mass with respect to the total monofunctional monomer mixture.
  • the polyfunctional monomer is a compound having two or more polymerizable groups, and a compound having two or more polymerizable unsaturated groups (carbon-carbon double bonds) is preferable.
  • polyfunctional monomers (poly) ethylene glycol di (meth) acrylate, methylenebisacrylamide, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) Examples thereof include acrylate and divinylbenzene. Among these, pentaerythritol tri (meth) acrylate is preferable because an adhesive composition having excellent cohesive force can be obtained.
  • a polyfunctional monomer can be used individually by 1 type or in combination of 2 or more types.
  • the content of the polyfunctional monomer is preferably 0.01 to 2%, preferably 0.05 to 0.5%, based on the total monomer mixture composed of the monofunctional monomer mixture and the polyfunctional monomer. Is more preferable.
  • the content is 0.01% or more, a pressure-sensitive adhesive composition having excellent cohesive force is obtained, and when the content is 2% or less, a pressure-sensitive adhesive composition having excellent adhesive strength is obtained.
  • the method for emulsion polymerization of the monofunctional monomer mixture and the polyfunctional monomer is not particularly limited, and a normal emulsion polymerization method can be employed.
  • a method in which the monofunctional monomer mixture and the polyfunctional monomer are emulsion-polymerized in an aqueous solvent in the presence of a surfactant and a polymerization initiator is not particularly limited, and a normal emulsion polymerization method can be employed.
  • a method in which the monofunctional monomer mixture and the polyfunctional monomer are emulsion-polymerized in an aqueous solvent in the presence of a surfactant and a polymerization initiator.
  • the surfactant to be used is not particularly limited, and examples thereof include an anionic emulsifier, a nonionic emulsifier, and a reactive emulsifier.
  • the anionic emulsifier include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, and the like.
  • nonionic emulsifiers include polyoxyethylene alkyl ether and polyoxyethylene alkylphenyl ether.
  • the reactive emulsifier is not particularly limited as long as it is an emulsifier having a reactive group such as a propenyl group or an acryloyl group.
  • a reactive group such as a propenyl group or an acryloyl group.
  • an anionic reactive emulsifier and a nonionic reactive emulsifier are mentioned.
  • anionic reactive emulsifier examples include “Adekalia Soap SE-20N”, “Adekalia Soap SE-10N”, “Adekalia Soap PP-70”, “Adekalia Soap PP-710”, “Adekalia Soap SR-”.
  • Nonionic reactive emulsifiers include “Adekalia Soap NE-10”, “Adekalia Soap NE-20”, “Adekalia Soap NE-30”, “Adekalia Soap NE-40”, “Adekalia Soap ER— 10 ”,“ Adekaria soap ER-20 ”,“ Adekaria soap ER-30 ”,“ Adekaria soap ER-40 ”(manufactured by Asahi Denka Kogyo Co., Ltd.),“ Aquaron RN-10 ”,“ Aquaron RN- ”
  • Commercial products such as “20”, “AQUALON RN-30”, “AQUALON RN-50” (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). These surfactants can be used alone or in combination of two or more.
  • the addition amount of the surfactant is preferably 0.4 to 1.2 parts by mass, more preferably 0.4 to 1.0 part by mass with respect to 100 parts by mass of the monofunctional monomer mixture.
  • the adhesive composition which is excellent in adhesive force and has favorable mechanical stability and coating property can be obtained.
  • it is 1.2 mass parts or less, and can obtain the adhesive composition which is excellent in mechanical stability and coating property, and has sufficient adhesive force.
  • Examples of the polymerization initiator used include azo polymerization initiators, persulfate polymerization initiators, peroxide polymerization initiators, and redox polymerization initiators.
  • Examples of the azo polymerization initiator include 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis (2-amidinopropane) dihydrochloride, and the like.
  • Examples of the persulfate-based polymerization initiator include potassium persulfate and ammonium persulfate.
  • Examples of peroxide polymerization initiators include benzoyl peroxide, t-butyl hydroperoxide, and hydrogen peroxide.
  • redox polymerization initiator examples include a combination of persulfate and sodium hydrogen sulfite, a combination of peroxide and sodium ascorbate, and the like. These polymerization initiators can be used singly or in combination of two or more.
  • the addition amount of the polymerization initiator is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the monofunctional monomer mixture.
  • the aqueous solvent is a mixed solvent composed of water or water and an organic solvent miscible with water.
  • the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms such as methanol, ethanol, propanol and isopropanol, and these can be used alone or in combination of two or more.
  • the amount of the aqueous solvent used is preferably 50 to 200% by mass, more preferably 50 to 150% by mass, based on the total monomer mixture.
  • the emulsion polymerization may be performed in the presence of a tackifier resin (B) and / or another tackifier resin.
  • a tackifier resin (B) and / or another tackifier resin contributes to the improvement of the adhesive strength of the pressure-sensitive adhesive composition and also serves to control the polymerization reaction.
  • the tackifier resin (B) and other tackifier resins will be described later.
  • additives may be present in the polymerization reaction system.
  • chain transfer agents antiseptics, fungicides, thickeners, wetting agents, antifoaming agents, plasticizers, pH adjusting agents and the like can be mentioned.
  • additives can also be added after the completion of emulsion polymerization.
  • chain transfer agent examples include thioglycolic acid, butyl mercaptan, octyl mercaptan, dodecyl mercaptan, lauryl mercaptan, 2-ethylhexyl thioglycolate, 2-mercaptoethanol and the like.
  • a chain transfer agent can be used individually by 1 type or in combination of 2 or more types.
  • the addition amount of the chain transfer agent is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the monofunctional monomer mixture.
  • Emulsion polymerization is usually performed by replacing the interior of the reactor with an inert gas and then raising the temperature to a predetermined temperature while stirring the entire volume.
  • the polymerization temperature is preferably about 40 to 100 ° C, more preferably 50 to 80 ° C.
  • the reaction time is usually about 1 to 8 hours, preferably 2 to 5 hours after the start of temperature increase. After completion of the reaction, if desired, by adding ammonia water or the like to the reaction solution and adjusting the pH of the reaction solution (for example, adjusting the pH of the reaction solution to about 8), an acrylic copolymer (A Can be obtained.
  • the tackifier resin (B) used in the present invention has a softening point of 130 to 180 ° C, preferably 140 to 160 ° C.
  • a pressure-sensitive adhesive composition having an excellent adhesive force even to an adherend such as a tread portion of a tire.
  • the peel strength of the obtained pressure-sensitive adhesive layer may be lowered.
  • tackifying resins having a temperature exceeding 180 ° C. are difficult to obtain.
  • the kind of the tackifier resin (B) is not particularly limited as long as it has a softening point in the above range.
  • examples thereof include rosin resins, petroleum resins, terpene resins, alkylphenol resins, coumarone resins, coumarone indene resins, styrene resins, xylene resins, and the like.
  • the rosin resin refers to rosin or a rosin derivative.
  • the rosin include gum rosin, wood rosin, tall oil rosin and the like.
  • the rosin derivative include polymerized rosin, disproportionated rosin, hydrogenated rosin, reinforced rosin, rosin ester, polymerized rosin ester, and rosin phenol.
  • the polyhydric alcohol used for esterification ethylene glycol, diethylene glycol, glycerin, pentaerythritol and the like can be used.
  • Examples of the petroleum resins include C5 petroleum resins, C9 petroleum resins, C5-C9 copolymer petroleum resins, pure monomer resins, dicyclopentadiene petroleum resins, and hydrides thereof.
  • Examples of the terpene resin include terpene polymers, ⁇ -pinene polymers, terpene phenol resins, and aromatic modified terpene polymers.
  • These tackifier resins (B) can be used singly or in combination of two or more.
  • a rosin resin is preferable because a pressure-sensitive adhesive composition having particularly excellent adhesive strength can be obtained.
  • the addition amount of the tackifier resin (B) is preferably 1 to 15 parts by mass, more preferably 3 to 10 parts by mass in terms of solid content with respect to 100 parts by mass of the monofunctional monomer mixture.
  • the adhesive composition which has the outstanding adhesive force also to the to-be-adhered body like a tread part of a tire can be obtained, and it is coating by being 15 mass parts or less.
  • An adhesive composition having excellent stability can be obtained.
  • the pressure-sensitive adhesive composition of the present invention may further contain another tackifying resin in addition to the tackifying resin (B).
  • another tackifying resin By containing other tackifying resins, it is possible to obtain a pressure-sensitive adhesive composition having further excellent tackiness, and when other tackifying resins are present in the polymerization reaction system in advance, the polymerization reaction is controlled. can do.
  • tackifying resins include tackifying resins other than the tackifying resin (B).
  • tackifying resins other than the tackifying resin (B).
  • rosin resins petroleum resins, terpene resins, alkylphenol resins, coumarone resins, coumarone indene resins, styrene resins, Examples include xylene resins.
  • Other tackifier resins can be used singly or in combination of two or more. Among these, as other tackifying resins, terpene resins are preferable, and terpene resins having a softening point of 100 to 130 ° C. are more preferable.
  • the addition amount of the other tackifying resin is preferably 0 to 15 parts by mass, more preferably 3 to 10 parts by mass in terms of solid content with respect to 100 parts by mass of the monofunctional monomer mixture.
  • the resin itself may be used as it is, or a pre-emulsified one may be used.
  • the emulsion-type pressure-sensitive adhesive composition can contain other additives as long as the effects of the present invention are not hindered.
  • Additives used include antiseptics, fungicides, thickeners, wetting agents, antifoaming agents, plasticizers, pH adjusters, pigments, dyes and the like. These additives may be added to the emulsion polymerization reaction solution of the acrylic copolymer (A), or may be added in advance to the emulsion polymerization system when the acrylic copolymer (A) is produced. Good.
  • the method for producing the emulsion-type pressure-sensitive adhesive composition of the present invention is not particularly limited.
  • a predetermined amount of the tackifier resin (B) and, if desired, another emulsified tackifier resin is mixed into the polymerization reaction liquid produced by the emulsion polymerization method of the acrylic copolymer (A), and the emulsion type A method for producing an adhesive composition
  • a method for producing an adhesive composition (Iii) When the acrylic copolymer (A) is produced, another tackifying resin is preliminarily present in the emulsion polymerization system to conduct emulsion polymerization, and after the polymerization reaction is completed, the emulsified tackifying resin (B) And a method of producing an emulsion-type pressure-sensitive adhesive composition.
  • the method (iii) is preferable because the polymerization reaction can be controlled and the characteristics of the tackifier resin (B) are not lost.
  • the emulsion-type pressure-sensitive adhesive composition of the present invention has a sufficient cohesive force, the adhesive residue remains after peeling of the pressure-sensitive adhesive sheet, unlike the conventional pressure-sensitive adhesive sheet that reduces the cohesive force of the pressure-sensitive adhesive layer and improves the followability to the rough surface. Is unlikely to occur.
  • the pressure-sensitive adhesive composition does not adhere to the cutter of the cutting machine, the guide of the printing machine, or the like during label processing, and the pressure-sensitive adhesive sheet or the like is not contaminated.
  • the re-peelable pressure-sensitive adhesive sheet of the present invention is a re-peelable pressure-sensitive adhesive sheet having at least a base material and a pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer comprises the acrylic copolymer (A). And an emulsion-type pressure-sensitive adhesive composition containing the tackifying resin (B).
  • the releasable pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet that can be re-peeled from an adherend after it is adhered to the adherend via an adhesive layer.
  • the substrate used in the present invention is not particularly limited, and a known plastic film, paper, synthetic paper or the like can be used. Especially, since it is excellent in mechanical strength and can prevent destruction of the base material at the time of peeling, it is preferably a plastic film or synthetic paper.
  • the material of the plastic film include polyolefin such as polyethylene and polypropylene; polyester such as polyethylene terephthalate; polyamide such as nylon; polystyrene;
  • the synthetic paper include single-layer or multi-layer synthetic paper having voids formed inside after melt-mixing a synthetic resin, a filler, and an additive and then extruding the film.
  • the base material preferably has a metal layer.
  • a metal layer an aluminum vapor deposition layer etc. are mentioned, for example.
  • the components of the tire such as amine-based anti-aging agents and aromatic oils, pass through the pressure-sensitive adhesive layer and migrate to the base material.
  • the surface opposite to the side in contact with the agent layer may be blackened, the presence of the metal layer prevents the migration of the component and prevents blackening of the substrate surface. Therefore, it is preferable that the metal layer is provided on the side of the substrate that contacts the pressure-sensitive adhesive layer.
  • the substrate surface may be provided with an easy-adhesion layer to facilitate the formation of a printed layer, and a receiving layer to enable recording such as thermal transfer recording and ink jet recording, protecting the surface.
  • An overcoat or overlaminate may be performed.
  • the thickness of the substrate is not particularly limited, but is preferably 10 to 150 ⁇ m, more preferably 10 to 120 ⁇ m. When the thickness is less than 10 ⁇ m, handling may become difficult, wrinkles may occur during pasting, and the substrate may be destroyed during peeling. On the other hand, when it exceeds 150 ⁇ m, the flexibility to the tire and the rough surface such as a tire may be lowered, and the releasable pressure-sensitive adhesive sheet may be easily peeled off.
  • the thickness of said preferable base material is the whole thickness including these layers, when it has a metal layer, an easily bonding layer, a receiving layer, etc.
  • the pressure-sensitive adhesive layer is formed using the emulsion-type pressure-sensitive adhesive composition of the present invention.
  • the thickness of the pressure-sensitive adhesive layer is usually 1 to 50 ⁇ m, preferably 5 to 40 ⁇ m. By setting the thickness of the pressure-sensitive adhesive layer to 1 ⁇ m or more, necessary adhesive force and cohesive force (holding force) can be secured, and by setting it to 50 ⁇ m or less, the cost is prevented and the pressure-sensitive adhesive layer has an end portion. It can be prevented from protruding.
  • the gel fraction of the pressure-sensitive adhesive layer is preferably 40 to 65% by mass, and more preferably 45 to 60% by mass. When it is 40% by mass or more, sufficient cohesive force can be obtained, and when it is 65% by mass or less, high adhesive force can be obtained.
  • Said gel fraction represents the ratio of the insoluble part with respect to the ethyl acetate of the dry film of an adhesive, and can be calculated
  • the material of the release material to be used is not particularly limited, and examples thereof include paper base materials such as high-quality paper, glassine paper, and laminate paper, polyesters such as polyethylene terephthalate and polyethylene naphthalate; polyolefins such as polypropylene and polyethylene; The film base material is mentioned.
  • the release material one obtained by subjecting one side or both sides of the base material to release treatment with a release agent is usually used.
  • the release agent to be used include fluorine resins, silicone resins, and long-chain alkyl group-containing carbamates.
  • the thickness of the release material is not particularly limited, but is usually 10 to 250 ⁇ m, preferably 20 to 200 ⁇ m.
  • the re-peelable pressure-sensitive adhesive sheet of the present invention is a method of (i) applying the emulsion-type pressure-sensitive adhesive composition of the present invention to the surface of a substrate, drying the obtained coating film, and laminating the release material on the coating film Or (ii) The emulsion-type pressure-sensitive adhesive composition of the present invention is applied to the surface of the release material, and the obtained coating film is dried, and then formed by a method of laminating a substrate on the coating film.
  • Gravure coating method bar coating method, spray coating method, spin coating method, roll coating method, die coating method, knife coating method, air knife coating method as a method of applying the emulsion-type pressure-sensitive adhesive composition to the substrate or release material surface
  • conventionally known coating methods such as curtain coating.
  • the temperature for drying the coating film of the emulsion-type pressure-sensitive adhesive composition is usually 80 to 120 ° C., preferably 90 to 110 ° C., and the drying time is usually 30 seconds to 15 minutes, preferably about 3 to 7 minutes. is there.
  • the pressure-sensitive adhesive layer of the releasable pressure-sensitive adhesive sheet of the present invention has a high adhesive force with respect to a rough surface. Therefore, it is preferably used as a releasable pressure-sensitive adhesive sheet for attaching a tire, and particularly preferably used as a removable pressure-sensitive adhesive sheet for attaching a tread portion of a tire.
  • the pressure-sensitive adhesive layer obtained using the pressure-sensitive adhesive composition of the present invention has a sufficient cohesive force, no adhesive residue is likely to occur after the pressure-sensitive adhesive sheet is peeled off.
  • the pressure-sensitive adhesive composition adheres to a cutter of a cutting machine, a guide of a printing machine, and the like, and does not contaminate the pressure-sensitive adhesive sheet or the like.
  • MMA Pentaerythritol triacrylate: manufactured by Daicel-Cytec, Inc., trade name “PETIA” ⁇ Chain transfer agent: Lauryl mercaptan ⁇ Anionic surfactant: Daiichi Kogyo Seiyaku Co., Ltd., trade name “New Frontier A-229E” -Terpene phenol resin: Arakawa Chemical Industries, trade name “Tamanol 901”, softening point 125 ° C. ⁇ Rosin resin 1: Rosin ester tackifier, manufactured by Harima Kasei Co., Ltd., trade name “Harry Star SK-816E”, softening point 145 ° C.
  • Rosin resin 2 Rosin ester tackifier, manufactured by Arakawa Chemical Industries, trade name “Superester E-720”, softening point 100 ° C.
  • Rosin resin 3 Rosin-modified ester tackifier, manufactured by Harima Kasei Co., Ltd., trade name “Harry Star SK-385NS”, softening point 85 ° C.
  • Example 1 To 100 parts by mass of the monofunctional monomer mixture obtained in Production Example 1, 0.3 part by mass of pentaerythritol triacrylate, 8 parts by mass of terpene phenol resin, and 0.018 part by mass of lauryl mercaptan were added and mixed. The obtained mixture was put into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, and stirred and dissolved for 30 minutes while maintaining at about 30 ° C.
  • rosin-based resin 1 5 parts by mass was added as a tackifier resin (B) to obtain an emulsion-type pressure-sensitive adhesive composition 1.
  • Emulsion-type pressure-sensitive adhesive compositions 2 to 8 were produced in the same manner as in Example 1 except that the raw materials listed in Table 2 were used.
  • Examples 5 to 8, Comparative Examples 5 to 8 Each of the emulsion-type pressure-sensitive adhesive compositions 1 to 8 obtained in Examples 1 to 4 and Comparative Examples 1 to 4 is a release paper (manufactured by Lintec Corporation, manufactured by Lintec Co., Ltd.). SP-8EA ivory ”) was coated to a thickness of 30 ⁇ m after drying, and dried at 90 ° C. for 2 minutes to form an adhesive layer.
  • an aluminum vapor deposition layer of a white coat polyethylene terephthalate film [white coat (including ethylene vinyl acetate resin and titanium oxide) 1 ⁇ m / polyethylene terephthalate film 12 ⁇ m / aluminum vapor deposition layer] provided with an aluminum vapor deposition layer was obtained.
  • the obtained pressure-sensitive adhesive layer was bonded to obtain pressure-sensitive adhesive sheets 1 to 8.
  • Example 9 A pressure-sensitive adhesive sheet 9 was obtained in the same manner as in Example 5 except that a biaxially stretched white polypropylene film having a thickness of 60 ⁇ m was used as the surface substrate.
  • Example 3 From the pressure-sensitive adhesive sheets 1 to 9 obtained in Examples 5 to 9 and Comparative Examples 5 to 8, small pieces of 10 cm ⁇ 10 cm were cut out, and the pressure-sensitive adhesive layer and the substrate were partially removed in a size of 1 cm ⁇ 10 cm. A test piece having the shape shown in FIG. 1 was prepared.
  • FIG. 1 (a) is the figure which looked at the test piece from the top, (b) is the figure which looked at the test piece from the horizontal direction.
  • 1 is a release film, 2 is an adhesive layer, and 3 is a substrate.
  • the test piece was allowed to stand for 24 hours under a pressure of 20 kN / 60 cm 2 at 40 ° C., and the protrusion of the adhesive at the end was observed and evaluated according to the following criteria. The evaluation results are shown in Table 3.
  • the pressure-sensitive adhesive sheets of Examples 5 to 9 were 23 ° C. (50% RH), 40 ° C., and 40 ° C. (50% RH) as compared with the pressure-sensitive adhesive sheets of Comparative Examples 5 to 8. ) In the environment of) and excellent in adhesive residue. Further, almost no protrusion was observed in the protrusion test.

Abstract

The present invention provides: an emulsion adhesive composition that contains an acrylic copolymer (A) obtained by emulsion polymerization of a polyfunctional monomer and a monofunctional monomer mixture containing 2-ethylhexyl acrylate, butyl acrylate, and an unsaturated ethylene carboxylic acid, and a tackifying resin (B), and that is characterized by the mass ratio of the 2-ethylhexyl acrylate and the butyl acrylate (2-ethylhexyl acrylate/butyl acrylate) being 0.6-2.5 and the softening point of the tackifying resin (B) being 130-180°C; and a re-peelable adhesive sheet that uses the adhesive composition. By means of the present invention, provided are: an adhesive composition having sufficient cohesion and a high adhesive strength even to rough surfaces; and a re-peelable adhesive sheet that uses the adhesive composition.

Description

エマルション型粘着剤組成物及び再剥離性粘着シートEmulsion type adhesive composition and releasable adhesive sheet
　本発明は、タイヤの表示ラベル等を製造する際に好適に用いられるエマルション型粘着剤組成物及び当該粘着剤組成物を用いる再剥離性粘着シートに関する。 The present invention relates to an emulsion-type pressure-sensitive adhesive composition suitably used for producing tire display labels and the like and a releasable pressure-sensitive adhesive sheet using the pressure-sensitive adhesive composition.
　商品表示ラベルは、商品名やその他の情報を伝えるために商品等に付されるものである。従来、かかる商品表示ラベルとして、基材上に粘着剤層等を有する粘着シートが広く利用されている。
　このような粘着シートには、商品の流通時においては高い粘着力が求められるが、最終的には比較的容易に剥離でき、糊残りが生じないという特性が求められる。
　従って、これらの特性が要求される粘着シートにおいては、粘着シートを構成する粘着剤や接着剤などについて、これまでにも様々な検討が行われてきた。 The product display label is attached to the product or the like in order to convey the product name or other information. Conventionally, pressure-sensitive adhesive sheets having a pressure-sensitive adhesive layer on a substrate have been widely used as such product display labels.
Such a pressure-sensitive adhesive sheet is required to have a high pressure-sensitive adhesive force at the time of distribution of goods, but finally has a characteristic that it can be peeled relatively easily and no adhesive residue is generated.
Therefore, in pressure-sensitive adhesive sheets that require these characteristics, various studies have been made so far regarding pressure-sensitive adhesives and adhesives constituting the pressure-sensitive adhesive sheet.
　例えば、特許文献１には、特定の、アクリル系乳化重合体、陰イオン乳化剤及び非イオン乳化剤から構成される感圧接着剤組成物が開示され、この組成物は優れた接着性と着脱性能を示すと記載されている。
　また特許文献２には、特定の、アクリル酸エステル、アクリロニトリル及びα，β－不飽和カルボン酸をアニオン性反応性乳化剤の存在下で乳化重合して得られるアクリルエマルションを含有するアクリルエマルション型感圧接着剤が開示され、この接着剤は被着体への糊残りが生じにくいと記載されている。 For example, Patent Document 1 discloses a specific pressure-sensitive adhesive composition composed of an acrylic emulsion polymer, an anionic emulsifier and a nonionic emulsifier, and this composition has excellent adhesiveness and attachment / detachment performance. It is described as showing.
Patent Document 2 discloses an acrylic emulsion type pressure-sensitive polymer containing an acrylic emulsion obtained by emulsion polymerization of a specific acrylic ester, acrylonitrile and α, β-unsaturated carboxylic acid in the presence of an anionic reactive emulsifier. An adhesive is disclosed, and it is described that this adhesive hardly causes adhesive residue on an adherend.
　このように、これまでにも粘着剤や粘着シートの性能向上が図られてきたが、被着体の種類によっては、通常の粘着シートでは粘着力が十分ではないことがあった。
　例えば、タイヤの表示ラベルは、メーカー名、ブランド名、サイズ等が記載され、タイヤのトレッド面に貼付されるが、タイヤのトレッド面には非常に大きな凹凸があることと、タイヤのトレッド面には、タイヤ成形時に使用される金型の空気抜き口が原因で形成される「スピュー」と呼ばれるヒゲ状突起物が存在するため、接着面積はかなり小さくなる。このようなタイヤ特有の形状は、粘着シートの粘着力を大きく低下させるため、上記文献に記載の接着剤を用いる粘着シートをタイヤのトレッド面に貼付した場合、粘着力が十分でなく剥がれ易いという問題があった。 As described above, the performance of the pressure-sensitive adhesive and pressure-sensitive adhesive sheet has been improved so far. However, depending on the type of adherend, the pressure-sensitive adhesive force may not be sufficient with a normal pressure-sensitive adhesive sheet.
For example, a tire display label includes a manufacturer name, a brand name, a size, and the like, and is affixed to the tread surface of the tire. Since there is a beard-like projection called “Spoo” formed due to the air vent of the mold used at the time of molding the tire, the bonding area becomes considerably small. Such a tire-specific shape greatly reduces the pressure-sensitive adhesive strength of the pressure-sensitive adhesive sheet. Therefore, when a pressure-sensitive adhesive sheet using the adhesive described in the above document is attached to the tread surface of the tire, the pressure-sensitive adhesive force is not sufficient and is easily peeled off. There was a problem.
　従来、タイヤ貼付用の粘着シートにおいては、ゴム溶剤系粘着剤が多く用いられてきた。しかしながら、ゴム溶剤系粘着剤を用いる粘着シートは、有機溶剤を使用することが多いため環境に負荷をかけるという問題があった。また、タイヤに対する粘着力を高めるために粘着剤を多量に使用し、粘着剤層の凝集力を低くしたものであったため、剥離後の糊残りの問題もあった。さらには、粘着シートにラベル加工を施す際、切断機のカッターや印刷機のガイド等に粘着剤が付着し、粘着シート等を汚染するという問題もあった。この汚染の問題は、全面塗布方法から部分塗布方法（切断予定箇所には粘着剤が存在しないように、部分的に塗布する方法）に代えることで解消できるが、この場合、生産効率が大きく低下することになる。 Conventionally, rubber solvent-based pressure-sensitive adhesives have often been used in pressure-sensitive adhesive sheets for attaching tires. However, the pressure-sensitive adhesive sheet using the rubber solvent-based pressure-sensitive adhesive has a problem of placing an burden on the environment because an organic solvent is often used. Further, since a large amount of pressure-sensitive adhesive was used to increase the pressure-sensitive adhesive force on the tire and the cohesive force of the pressure-sensitive adhesive layer was lowered, there was a problem of adhesive residue after peeling. Furthermore, when labeling the pressure sensitive adhesive sheet, there is also a problem that the pressure sensitive adhesive adheres to the cutter of the cutting machine, the guide of the printing machine, etc., and contaminates the pressure sensitive adhesive sheet. This problem of contamination can be solved by replacing the whole surface coating method with a partial coating method (a method of partially coating so that no adhesive is present at the planned cutting site), but in this case, the production efficiency is greatly reduced. Will do.
　また、近年においては、ゴム溶剤系粘着剤に代わる新たな粘着剤を用いるタイヤ貼付用の粘着シートも提案されている。例えば、特許文献３には、特定のアクリル系樹脂に液状粘着付与樹脂を配合し、架橋させてなる粘着剤層を有する粘着シートが開示されている。しかしながら、この粘着シートも、粘着剤層も粗面に対する粘着力を高めるために凝集力を低くしたものであり、糊残りの問題を有するものであった。 In recent years, a pressure-sensitive adhesive sheet for attaching a tire using a new pressure-sensitive adhesive instead of a rubber solvent-based pressure-sensitive adhesive has also been proposed. For example, Patent Document 3 discloses a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer obtained by blending a liquid tackifier resin with a specific acrylic resin and crosslinking it. However, both the pressure-sensitive adhesive sheet and the pressure-sensitive adhesive layer have a low cohesive force in order to increase the adhesive force to the rough surface, and have a problem of adhesive residue.
特開平１１－７１５６３号公報Japanese Patent Laid-Open No. 11-71563 特開２０００－１１９６１７号公報JP 2000-119617 A 特開２０００－３１９６１８号公報JP 2000-319618 A
　タイヤのトレッド面のような粗面に対する粘着力を高めるためには、特許文献３に記載されるように粘着剤層の凝集力を低くする方法が考えられる。しかしながら、このような粘着シートは、剥離後の糊残りの問題や製造時における汚染の問題を引き起こしやすい。したがって、粘着剤層の凝集力を低くすることなく、粗面に対しても高い粘着力を有する粘着シートや、このような粘着シートの粘着剤層を形成できる粘着剤組成物が望まれていた。
　本発明はこのような実情に鑑みてなされたものであり、粗面に対しても高い粘着力を有し、かつ、十分な凝集力を有する粘着剤組成物と、この粘着剤組成物を用いる再剥離性粘着シートを提供することを目的とする。 In order to increase the adhesive force to a rough surface such as a tread surface of a tire, a method of reducing the cohesive force of the pressure-sensitive adhesive layer as described in Patent Document 3 can be considered. However, such a pressure-sensitive adhesive sheet tends to cause a problem of adhesive residue after peeling and a problem of contamination during production. Therefore, there has been a demand for a pressure-sensitive adhesive sheet having a high pressure-sensitive adhesive force even on a rough surface without reducing the cohesive force of the pressure-sensitive adhesive layer, and a pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive layer of such a pressure-sensitive adhesive sheet. .
This invention is made | formed in view of such a situation, has a high adhesive force also with respect to a rough surface, and has sufficient cohesive force, and uses this adhesive composition. It aims at providing a releasable adhesive sheet.
　本発明者らは、上記課題を解決すべく鋭意研究した結果、２－エチルヘキシルアクリレート、ブチルアクリレート及びエチレン性不飽和カルボン酸を含み、２－エチルヘキシルアクリレートとブチルアクリレートの質量比が特定範囲内にある単官能単量体混合物と多官能単量体とを乳化重合して得られるアクリル系共重合体（Ａ）、及び、特定範囲内の軟化点を有する粘着付与樹脂（Ｂ）を含有するエマルション型粘着剤組成物は、粗面に対して高い粘着力を有し、かつ、十分な凝集力を有することを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors include 2-ethylhexyl acrylate, butyl acrylate, and ethylenically unsaturated carboxylic acid, and the mass ratio of 2-ethylhexyl acrylate to butyl acrylate is within a specific range. An emulsion type containing an acrylic copolymer (A) obtained by emulsion polymerization of a monofunctional monomer mixture and a polyfunctional monomer, and a tackifying resin (B) having a softening point within a specific range The pressure-sensitive adhesive composition was found to have a high adhesive force with respect to a rough surface and a sufficient cohesive force, and the present invention was completed.
　かくして本発明の第１によれば、下記（１）～（６）のエマルション型粘着剤組成物が提供される。
（１）２－エチルヘキシルアクリレート、ブチルアクリレート及びエチレン性不飽和カルボン酸を含む単官能単量体混合物と、多官能単量体とを乳化重合して得られるアクリル系共重合体（Ａ）、並びに、粘着付与樹脂（Ｂ）を含むエマルション型粘着剤組成物であって、２－エチルヘキシルアクリレートとブチルアクリレートの質量比（２－エチルヘキシルアクリレートの含有量／ブチルアクリレートの含有量）が０．６～２．５であり、前記粘着付与樹脂（Ｂ）の軟化点が１３０～１８０℃であることを特徴とするエマルション型粘着剤組成物。 Thus, according to the first aspect of the present invention, the following emulsion type pressure-sensitive adhesive compositions (1) to (6) are provided.
(1) Acrylic copolymer (A) obtained by emulsion polymerization of a monofunctional monomer mixture containing 2-ethylhexyl acrylate, butyl acrylate and ethylenically unsaturated carboxylic acid, and a polyfunctional monomer, and An emulsion-type pressure-sensitive adhesive composition containing a tackifying resin (B), wherein the mass ratio of 2-ethylhexyl acrylate to butyl acrylate (content of 2-ethylhexyl acrylate / content of butyl acrylate) is 0.6 to 2 An emulsion-type pressure-sensitive adhesive composition, wherein the tackifying resin (B) has a softening point of 130 to 180 ° C.
（２）２－エチルヘキシルアクリレートとブチルアクリレートの質量比（２－エチルヘキシルアクリレート含有量／ブチルアクリレート含有量）が１．６～１．９である（１）に記載のエマルション型粘着剤組成物。
（３）前記多官能単量体の含有量が、単官能単量体混合物と多官能単量体からなる全単量体混合物に対して、０．０１～２質量％である（１）に記載のエマルション型粘着剤組成物。
（４）粘着付与樹脂（Ｂ）が軟化点が１４０～１６０℃の樹脂である（１）に記載のエマルション型粘着剤組成物。
（５）粘着付与樹脂（Ｂ）がロジン系樹脂である（１）に記載のエマルション型粘着剤組成物。
（６）さらに、テルペン系樹脂を含有する（１）に記載のエマルション型粘着剤組成物。 (2) The emulsion-type pressure-sensitive adhesive composition according to (1), wherein the mass ratio of 2-ethylhexyl acrylate to butyl acrylate (2-ethylhexyl acrylate content / butyl acrylate content) is 1.6 to 1.9.
(3) The content of the polyfunctional monomer is 0.01 to 2% by mass with respect to the total monomer mixture composed of the monofunctional monomer mixture and the polyfunctional monomer. The emulsion-type pressure-sensitive adhesive composition described.
(4) The emulsion-type pressure-sensitive adhesive composition according to (1), wherein the tackifying resin (B) is a resin having a softening point of 140 to 160 ° C.
(5) The emulsion-type pressure-sensitive adhesive composition according to (1), wherein the tackifier resin (B) is a rosin resin.
(6) The emulsion-type pressure-sensitive adhesive composition according to (1), further comprising a terpene resin.
　本発明の第２によれば、下記（７）～（９）の再剥離性粘着シートが提供される。
（７）基材と粘着剤層とを有する再剥離性粘着シートであって、前記粘着剤層が（１）～（６）のいずれかに記載のエマルション型粘着剤組成物を用いて得られたものであることを特徴とする再剥離性粘着シート。
（８）タイヤ貼付用の（７）に記載の再剥離性粘着シート。
（９）タイヤのトレッド部貼付用の（７）に記載の再剥離性粘着シート。 According to the second aspect of the present invention, the following releasable pressure-sensitive adhesive sheets (7) to (9) are provided.
(7) A releasable pressure-sensitive adhesive sheet having a substrate and a pressure-sensitive adhesive layer, wherein the pressure-sensitive adhesive layer is obtained using the emulsion-type pressure-sensitive adhesive composition according to any one of (1) to (6). A re-peelable pressure-sensitive adhesive sheet characterized by being
(8) The releasable pressure-sensitive adhesive sheet according to (7) for tire application.
(9) The releasable pressure-sensitive adhesive sheet according to (7), which is used for attaching a tread part of a tire.
　本発明のエマルション型粘着剤組成物を用いる再剥離性粘着シートは、粗面に対しても高い粘着力を有するため、タイヤのような粘着しにくい粗面を有する被着体に対しても使用することができる。
　本発明の再剥離性粘着シートは、本発明の粘着剤組成物を用いて得られる粘着剤層を有する。本発明の粘着剤組成物を用いて得られる粘着剤層は、十分な凝集力を有するものであるため、本発明の再剥離性粘着シートは、剥離した後に糊残りが生じにくいものである。また、本発明の再剥離性粘着シートによれば、ラベル加工時に切断機のカッターや印刷機のガイド等に粘着剤組成物が付着し、粘着シート等を汚染することがない。 Since the releasable pressure-sensitive adhesive sheet using the emulsion-type pressure-sensitive adhesive composition of the present invention has a high adhesive force even on a rough surface, it is also used for an adherend having a rough surface that is difficult to stick, such as a tire. can do.
The releasable pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer obtained using the pressure-sensitive adhesive composition of the present invention. Since the pressure-sensitive adhesive layer obtained using the pressure-sensitive adhesive composition of the present invention has sufficient cohesive force, the re-peelable pressure-sensitive adhesive sheet of the present invention is less likely to have adhesive residue after peeling. Moreover, according to the releasable pressure-sensitive adhesive sheet of the present invention, the pressure-sensitive adhesive composition does not adhere to a cutter of a cutting machine, a guide of a printing machine or the like during label processing, and the pressure-sensitive adhesive sheet or the like is not contaminated.
実施例の（はみ出し試験）で用いた試験片の形状を示す図である。It is a figure which shows the shape of the test piece used by the (projection test) of the Example.
　以下、本発明を、１）エマルション型粘着剤組成物、及び、２）再剥離性粘着シートに項分けして説明する。
　なお、以下の説明において、「高い粘着力を有する粘着剤層を形成できる粘着剤組成物」を「高い粘着力を有する接着剤組成物」、「高い凝集力を有する粘着剤層を形成できる粘着剤組成物」を「高い凝集力を有する接着剤組成物」のように省略して記載することがある。また、他の特性についても同様に省略して記載することがある。 Hereinafter, the present invention will be described in terms of 1) an emulsion-type pressure-sensitive adhesive composition and 2) a re-peelable pressure-sensitive adhesive sheet.
In the following description, “adhesive composition capable of forming a pressure-sensitive adhesive layer having high adhesive strength” is referred to as “adhesive composition having high adhesive strength”, and “adhesive capable of forming a pressure-sensitive adhesive layer having high cohesive strength”. “Adhesive composition” may be abbreviated as “adhesive composition having high cohesive strength”. In addition, other characteristics may be omitted as well.
１）エマルション型粘着剤組成物
　本発明のエマルション型粘着剤組成物は、２－エチルヘキシルアクリレート、ブチルアクリレート及びエチレン性不飽和カルボン酸を含む単官能単量体混合物と、多官能単量体とを乳化重合して得られるアクリル系共重合体（Ａ）、並びに、粘着付与樹脂（Ｂ）を含むエマルション型粘着剤組成物であって、２－エチルヘキシルアクリレートとブチルアクリレートの質量比（２－エチルヘキシルアクリレートの含有量／ブチルアクリレートの含有量）が０．６～２．５であり、前記粘着付与樹脂（Ｂ）の軟化点が１３０～１８０℃であることを特徴とする。
　本発明のエマルション型粘着剤組成物は、アクリル系共重合体（Ａ）及び粘着付与樹脂（Ｂ）が、後述する水系溶媒中に分散されてなる分散液である。 1) Emulsion-type pressure-sensitive adhesive composition The emulsion-type pressure-sensitive adhesive composition of the present invention comprises a monofunctional monomer mixture containing 2-ethylhexyl acrylate, butyl acrylate and ethylenically unsaturated carboxylic acid, and a polyfunctional monomer. An emulsion-type pressure-sensitive adhesive composition comprising an acrylic copolymer (A) obtained by emulsion polymerization and a tackifier resin (B), wherein the mass ratio of 2-ethylhexyl acrylate to butyl acrylate (2-ethylhexyl acrylate) Content / butyl acrylate content) is 0.6 to 2.5, and the softening point of the tackifying resin (B) is 130 to 180 ° C.
The emulsion-type pressure-sensitive adhesive composition of the present invention is a dispersion liquid in which an acrylic copolymer (A) and a tackifier resin (B) are dispersed in an aqueous solvent described later.
［アクリル系共重合体（Ａ）］
　本発明に用いるアクリル系共重合体（Ａ）は、２－エチルヘキシルアクリレート、ブチルアクリレート及びエチレン性不飽和カルボン酸を含む単官能単量体混合物と、多官能単量体とを乳化重合して得られるものである。 [Acrylic copolymer (A)]
The acrylic copolymer (A) used in the present invention is obtained by emulsion polymerization of a monofunctional monomer mixture containing 2-ethylhexyl acrylate, butyl acrylate and ethylenically unsaturated carboxylic acid and a polyfunctional monomer. It is what
　本発明に用いるアクリル系共重合体（Ａ）は、２－エチルヘキシルアクリレートとブチルアクリレートとを併用して得られるものであり、これらを含有する粘着剤組成物は、粘着力、凝集力及び再剥離性のバランスに優れる。この観点から、２－エチルヘキシルアクリレートとブチルアクリレートの質量比（２－エチルヘキシルアクリレートの含有量／ブチルアクリレートの含有量）　　　　　　　　　　　　　　　　は０．６～２．５であり、１．６～１．９の範囲が好ましい。また、２－エチルヘキシルアクリレートとブチルアクリレートとの合計含有量は、特に限定されないが、単官能単量体混合物全体に対して、８０～９９．８質量％が好ましく、９０～９９．８質量％がより好ましい。 The acrylic copolymer (A) used in the present invention is obtained by using 2-ethylhexyl acrylate and butyl acrylate in combination, and the pressure-sensitive adhesive composition containing these has adhesive strength, cohesive strength, and re-peeling. Excellent balance of sex. From this point of view, the mass ratio of 2-ethylhexyl acrylate to butyl acrylate (content of 2-ethylhexyl acrylate / content of butyl acrylate) is 0.6 to 2.5, and ranges from 1.6 to 1.9. preferable. The total content of 2-ethylhexyl acrylate and butyl acrylate is not particularly limited, but is preferably 80 to 99.8% by mass, and 90 to 99.8% by mass based on the total monofunctional monomer mixture. More preferred.
　エチレン性不飽和カルボン酸は、１分子中に少なくとも１つのカルボキシル基と１つの重合性不飽和結合を有する化合物である。例えば、アクリル酸、メタクリル酸、イタコン酸、マレイン酸、クロトン酸等が挙げられる。
　これらの中でも、入手容易性、重合性の観点から、アクリル酸、メタクリル酸が好ましい。
　エチレン性不飽和カルボン酸は一種単独で、あるいは二種以上を組み合わせて用いることができる。 An ethylenically unsaturated carboxylic acid is a compound having at least one carboxyl group and one polymerizable unsaturated bond in one molecule. For example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid and the like can be mentioned.
Among these, acrylic acid and methacrylic acid are preferable from the viewpoint of availability and polymerizability.
An ethylenically unsaturated carboxylic acid can be used individually by 1 type or in combination of 2 or more types.
　エチレン性不飽和カルボン酸の含有量は、特に限定されないが、単官能単量体混合物全体に対して、０．３～０．８質量％の範囲が好ましく、０．３５～０．７５質量％がより好ましい。０．３質量％以上であることで、より優れた凝集力を有する粘着剤組成物が得られ、結果として、タイヤのトレッド部に糊残りなく貼付する粘着シートを得ることができる。また、０．８質量％以下であることで、機械的安定性および塗工性により優れた粘着剤組成物を得ることができる。 The content of the ethylenically unsaturated carboxylic acid is not particularly limited, but is preferably in the range of 0.3 to 0.8% by mass, and 0.35 to 0.75% by mass with respect to the entire monofunctional monomer mixture. Is more preferable. When the content is 0.3% by mass or more, a pressure-sensitive adhesive composition having a more excellent cohesive force can be obtained, and as a result, a pressure-sensitive adhesive sheet can be obtained that adheres to the tread portion of the tire without any adhesive residue. Moreover, the adhesive composition excellent in mechanical stability and coating property can be obtained because it is 0.8 mass% or less.
　前記単官能単量体混合物は、２－エチルヘキシルアクリレート、ブチルアクリレート及びエチレン性不飽和カルボン酸に加えて、本発明の効果を妨げない限り、これらの単量体以外の他のエチレン性不飽和単量体を含有してもよい。本明細書においては、他のエチレン性不飽和単量体も、単官能単量体混合物の中に含めるものとする。 In addition to 2-ethylhexyl acrylate, butyl acrylate and ethylenically unsaturated carboxylic acid, the monofunctional monomer mixture may contain other ethylenically unsaturated monomers other than these monomers as long as the effects of the present invention are not impaired. A monomer may be contained. In the present specification, other ethylenically unsaturated monomers are also included in the monofunctional monomer mixture.
　前記他のエチレン性不飽和単量体としては、２－エチルヘキシルアクリレート及びブチルアクリレート以外の、（メタ）アクリル酸エステル、水酸基を含有する（メタ）アクリル酸エステル、酢酸ビニル、スチレン等が挙げられる。
　２－エチルヘキシルアクリレートとブチルアクリレート以外の（メタ）アクリル酸エステルとしては、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、ブチルメタクリレート、ヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、２－エチルヘキシルメタクリレート等が挙げられる。
　水酸基を含有する（メタ）アクリル酸エステルとしては、ヒドロキシメチル（メタ）アクリレート、ヒドロキシルエチル（メタ）アクリレート等が挙げられる。
　なお、本明細書において、（メタ）アクリレートとは、アクリレート又はメタクリレートを意味する。
　これらの他のエチレン性不飽和単量体は、一種単独で、あるいは二種以上を組み合わせて用いることができる。
　他のエチレン性不飽和単量体の含有量は、単官能単量体混合物全体に対して、０～２０質量％が好ましく、０～１０質量％がより好ましい。 Examples of the other ethylenically unsaturated monomers include (meth) acrylic acid esters other than 2-ethylhexyl acrylate and butyl acrylate, (meth) acrylic acid esters containing a hydroxyl group, vinyl acetate, and styrene.
Examples of (meth) acrylic acid esters other than 2-ethylhexyl acrylate and butyl acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl methacrylate, hexyl (meth) acrylate, and octyl (meth) acrylate. And 2-ethylhexyl methacrylate.
Examples of the (meth) acrylic acid ester containing a hydroxyl group include hydroxymethyl (meth) acrylate and hydroxylethyl (meth) acrylate.
In the present specification, (meth) acrylate means acrylate or methacrylate.
These other ethylenically unsaturated monomers can be used singly or in combination of two or more.
The content of other ethylenically unsaturated monomers is preferably 0 to 20% by mass and more preferably 0 to 10% by mass with respect to the total monofunctional monomer mixture.
　多官能単量体は、２以上の重合性基を有する化合物であり、２以上の重合性不飽和基(炭素－炭素二重結合)を有する化合物が好ましい。
　多官能単量体としては、（ポリ）エチレングリコールジ（メタ）アクリレート、メチレンビスアクリルアミド、１，６－ヘキサンジオールジ（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、ジビニルベンゼン等が挙げられる。
　これらの中でも、凝集力に優れる粘着剤組成物が得られることから、ペンタエリスリトールトリ（メタ）アクリレートが好ましい。
　多官能単量体は、一種単独で、あるいは二種以上を組み合わせて用いることができる。 The polyfunctional monomer is a compound having two or more polymerizable groups, and a compound having two or more polymerizable unsaturated groups (carbon-carbon double bonds) is preferable.
As polyfunctional monomers, (poly) ethylene glycol di (meth) acrylate, methylenebisacrylamide, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) Examples thereof include acrylate and divinylbenzene.
Among these, pentaerythritol tri (meth) acrylate is preferable because an adhesive composition having excellent cohesive force can be obtained.
A polyfunctional monomer can be used individually by 1 type or in combination of 2 or more types.
　多官能単量体の含有量は、単官能単量体混合物と多官能単量体からなる全単量体混合物に対して、０．０１～２％が好ましく、０．０５～０．５％がより好ましい。０．０１％以上であることで凝集力に優れる粘着剤組成物が得られ、２％以下であることで粘着力に優れる粘着剤組成物が得られる。 The content of the polyfunctional monomer is preferably 0.01 to 2%, preferably 0.05 to 0.5%, based on the total monomer mixture composed of the monofunctional monomer mixture and the polyfunctional monomer. Is more preferable. When the content is 0.01% or more, a pressure-sensitive adhesive composition having excellent cohesive force is obtained, and when the content is 2% or less, a pressure-sensitive adhesive composition having excellent adhesive strength is obtained.
　前記単官能単量体混合物と多官能単量体とを乳化重合する方法は特に制限されず、通常の乳化重合法を採用することができる。例えば、水系溶媒中、界面活性剤及び重合開始剤の存在下に、前記単官能単量体混合物と多官能単量体とを乳化重合させる方法が挙げられる。 The method for emulsion polymerization of the monofunctional monomer mixture and the polyfunctional monomer is not particularly limited, and a normal emulsion polymerization method can be employed. For example, a method in which the monofunctional monomer mixture and the polyfunctional monomer are emulsion-polymerized in an aqueous solvent in the presence of a surfactant and a polymerization initiator.
　用いる界面活性剤は、特に制限されず、例えば、アニオン系乳化剤、ノニオン系乳化剤、反応性乳化剤等が挙げられる。
　アニオン系乳化剤としては、例えば、ラウリル硫酸ナトリウム、ラウリル硫酸アンモニウム、ドデシルベンゼンスルホン酸ナトリウム、ポリオキシエチレンアルキルエーテル硫酸ナトリウム、ポリオキシエチレンアルキルフェニルエーテル硫酸ナトリウム等が挙げられる。
　ノニオン系乳化剤としては、例えば、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル等が挙げられる。 The surfactant to be used is not particularly limited, and examples thereof include an anionic emulsifier, a nonionic emulsifier, and a reactive emulsifier.
Examples of the anionic emulsifier include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, and the like.
Examples of nonionic emulsifiers include polyoxyethylene alkyl ether and polyoxyethylene alkylphenyl ether.
　反応性乳化剤としては、プロペニル基やアクリロイル基等の反応性基を有する乳化剤であれば、特に限定されない。例えば、アニオン型反応性乳化剤やノニオン型反応性乳化剤が挙げられる。 The reactive emulsifier is not particularly limited as long as it is an emulsifier having a reactive group such as a propenyl group or an acryloyl group. For example, an anionic reactive emulsifier and a nonionic reactive emulsifier are mentioned.
　アニオン型反応性乳化剤としては、「アデカリアソープＳＥ－２０Ｎ」、「アデカリアソープＳＥ－１０Ｎ」、「アデカリアソープＰＰ－７０」、「アデカリアソープＰＰ－７１０」、「アデカリアソープＳＲ－１０」、「アデカリアソープＳＲ－２０」〔以上、旭電化工業社製〕、「エレミノールＪＳ－２」、「エレミノールＲＳ－３０」〔以上、三洋化成工業社製〕、「ラテムルＥ－１１８Ｂ」、「ラテムルＳ－１８０Ａ」、「ラテムルＳ－１８０」、「ラテムルＰＤ－１０４」〔以上、花王社製〕、「アクアロンＢＣ－０５」、「アクアロンＢＣ－１０」、「アクアロンＢＣ－２０」、「アクアロンＨＳ－０５」、「アクアロンＨＳ－１０」、「アクアロンＨＳ－２０」、「ニューフロンティアＳ－５１０」、「アクアロンＫＨ－０５」、「アクアロンＫＨ－１０」〔以上、第一工業製薬社製〕、「フォスフィノールＴＸ」〔東邦化学工業社製〕等の市販品が挙げられる。 Examples of the anionic reactive emulsifier include “Adekalia Soap SE-20N”, “Adekalia Soap SE-10N”, “Adekalia Soap PP-70”, “Adekalia Soap PP-710”, “Adekalia Soap SR-”. 10 ”,“ Adekaria Soap SR-20 ”(manufactured by Asahi Denka Kogyo Co., Ltd.),“ Eleminol JS-2 ”,“ Eleminol RS-30 ”(manufactured by Sanyo Kasei Kogyo Co., Ltd.),“ Latemul E-118B ” “Latemul S-180A”, “Latemul S-180”, “Latemul PD-104” (manufactured by Kao Corporation), “Aqualon BC-05”, “Aqualon BC-10”, “Aqualon BC-20”, “Aqualon HS-05”, “Aquaron HS-10”, “Aquaron HS-20”, “New Frontier S-510”, “Aquaron KH-0” "," Aqualon KH-10 "[manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.]," phosphinothricin Nord TX "[manufactured by Toho Chemical Industry Co., Ltd. A commercially available products, and the like.
　ノニオン型反応性乳化剤としては、「アデカリアソープＮＥ－１０」、「アデカリアソープＮＥ－２０」、「アデカリアソープＮＥ－３０」、「アデカリアソープＮＥ－４０」、「アデカリアソープＥＲ－１０」、「アデカリアソープＥＲ－２０」、「アデカリアソープＥＲ－３０」、「アデカリアソープＥＲ－４０」〔以上、旭電化工業社製〕、「アクアロンＲＮ－１０」、「アクアロンＲＮ－２０」、「アクアロンＲＮ－３０」、「アクアロンＲＮ－５０」〔以上、第一工業製薬社製〕等の市販品が挙げられる。
　これらの界面活性剤は、一種単独で、あるいは二種以上を組み合わせて用いることができる。 Nonionic reactive emulsifiers include “Adekalia Soap NE-10”, “Adekalia Soap NE-20”, “Adekalia Soap NE-30”, “Adekalia Soap NE-40”, “Adekalia Soap ER— 10 ”,“ Adekaria soap ER-20 ”,“ Adekaria soap ER-30 ”,“ Adekaria soap ER-40 ”(manufactured by Asahi Denka Kogyo Co., Ltd.),“ Aquaron RN-10 ”,“ Aquaron RN- ” Commercial products such as “20”, “AQUALON RN-30”, “AQUALON RN-50” (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).
These surfactants can be used alone or in combination of two or more.
　界面活性剤の添加量は、単官能単量体混合物１００質量部に対して、０．４～１．２質量部が好ましく、０．４～１．０質量部がより好ましい。０．４質量部以上であることで、粘着力に優れ、かつ、良好な機械的安定性及び塗工性を有する粘着剤組成物を得ることができる。また、１．２質量部以下であることで、機械的安定性及び塗工性に優れ、かつ、十分な粘着力を有する粘着剤組成物を得ることができる。 The addition amount of the surfactant is preferably 0.4 to 1.2 parts by mass, more preferably 0.4 to 1.0 part by mass with respect to 100 parts by mass of the monofunctional monomer mixture. By being 0.4 mass part or more, the adhesive composition which is excellent in adhesive force and has favorable mechanical stability and coating property can be obtained. Moreover, it is 1.2 mass parts or less, and can obtain the adhesive composition which is excellent in mechanical stability and coating property, and has sufficient adhesive force.
　用いる重合開始剤としては、アゾ系重合開始剤、過硫酸塩系重合開始剤、過酸化物系重合開始剤、レドックス系重合開始剤等が挙げられる。
　アゾ系重合開始剤としては、例えば、２，２’－アゾビス（２－メチルプロピオンアミジン）二塩酸塩、２，２’－アゾビス（２－アミジノプロパン）ジヒドロクロライド等が挙げられる。
　過硫酸塩系重合開始剤としては、過硫酸カリウム、過硫酸アンモニウム等が挙げられる。
　過酸化物系重合開始剤としては、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、過酸化水素等が挙げられる。
　レドックス系重合開始剤としては、過硫酸塩と亜硫酸水素ナトリウムとの組み合わせや、過酸化物とアスコルビン酸ナトリウムとの組み合わせ等が挙げられる。
　これらの重合開始剤は一種単独で、あるいは二種以上を組み合わせて用いることができる。 Examples of the polymerization initiator used include azo polymerization initiators, persulfate polymerization initiators, peroxide polymerization initiators, and redox polymerization initiators.
Examples of the azo polymerization initiator include 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis (2-amidinopropane) dihydrochloride, and the like.
Examples of the persulfate-based polymerization initiator include potassium persulfate and ammonium persulfate.
Examples of peroxide polymerization initiators include benzoyl peroxide, t-butyl hydroperoxide, and hydrogen peroxide.
Examples of the redox polymerization initiator include a combination of persulfate and sodium hydrogen sulfite, a combination of peroxide and sodium ascorbate, and the like.
These polymerization initiators can be used singly or in combination of two or more.
　重合開始剤の添加量は、単官能単量体混合物１００質量部に対して、０．０１～５質量部が好ましく、０．０１～３質量部がより好ましい。 The addition amount of the polymerization initiator is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the monofunctional monomer mixture.
　水系溶媒は、水、又は水及び水と混和性の有機溶媒からなる混合溶媒である。水と混和性の有機溶媒としては、メタノール、エタノール、プロパノール、イソプロパノール等の炭素数１～３のアルコールが挙げられ、これらは一種単独で、あるいは二種以上を組み合わせて用いることができる。
　水系溶媒の使用量は、全単量体混合物に対して、５０～２００質量％が好ましく、５０～１５０質量％がより好ましい。 The aqueous solvent is a mixed solvent composed of water or water and an organic solvent miscible with water. Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms such as methanol, ethanol, propanol and isopropanol, and these can be used alone or in combination of two or more.
The amount of the aqueous solvent used is preferably 50 to 200% by mass, more preferably 50 to 150% by mass, based on the total monomer mixture.
　また、乳化重合は、粘着付与樹脂（Ｂ）及び／又は他の粘着付与樹脂の存在下で行ってもよい。重合反応系内に粘着付与樹脂が存在することで、粘着剤組成物の粘着力向上に寄与するとともに、重合反応の制御にも役立つ。粘着付与樹脂（Ｂ）及び他の粘着付与樹脂については後述する。 Further, the emulsion polymerization may be performed in the presence of a tackifier resin (B) and / or another tackifier resin. The presence of the tackifier resin in the polymerization reaction system contributes to the improvement of the adhesive strength of the pressure-sensitive adhesive composition and also serves to control the polymerization reaction. The tackifier resin (B) and other tackifier resins will be described later.
　さらに、重合反応系内には、他の各種添加剤が存在していてもよい。例えば、連鎖移動剤、防腐剤、防カビ剤、増粘剤、濡れ剤、消泡剤、可塑剤、ｐＨ調整剤等が挙げられる。なお、これらの添加剤は、乳化重合終了後に添加することもできる。 Furthermore, various other additives may be present in the polymerization reaction system. For example, chain transfer agents, antiseptics, fungicides, thickeners, wetting agents, antifoaming agents, plasticizers, pH adjusting agents and the like can be mentioned. These additives can also be added after the completion of emulsion polymerization.
　連鎖移動剤としては、例えば、チオグリコール酸、ブチルメルカプタン、オクチルメルカプタン、ドデシルメルカプタン、ラウリルメルカプタン、２－エチルヘキシルチオグリコレート、２－メルカプトエタノール等が挙げられる。連鎖移動剤は、一種単独で、あるいは二種以上を組み合わせて用いることができる。
　連鎖移動剤の添加量は、単官能単量体混合物１００質量部に対して、０．０１～１質量部が好ましい。 Examples of the chain transfer agent include thioglycolic acid, butyl mercaptan, octyl mercaptan, dodecyl mercaptan, lauryl mercaptan, 2-ethylhexyl thioglycolate, 2-mercaptoethanol and the like. A chain transfer agent can be used individually by 1 type or in combination of 2 or more types.
The addition amount of the chain transfer agent is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the monofunctional monomer mixture.
　乳化重合は、通常、反応器内を不活性ガスで置換した後、全容を撹拌しながら所定温度まで昇温して行う。重合温度は４０～１００℃程度が好ましく、５０～８０℃であることがより好ましい。反応時間は、通常、昇温開始後１～８時間程度、好ましくは２～５時間である。
　反応終了後は、所望により、反応液にアンモニア水等を添加して、反応液のｐＨを調整する（例えば、反応液のｐＨを８程度に調整する）ことにより、アクリル系共重合体（Ａ）を含有するエマルションを得ることができる。 Emulsion polymerization is usually performed by replacing the interior of the reactor with an inert gas and then raising the temperature to a predetermined temperature while stirring the entire volume. The polymerization temperature is preferably about 40 to 100 ° C, more preferably 50 to 80 ° C. The reaction time is usually about 1 to 8 hours, preferably 2 to 5 hours after the start of temperature increase.
After completion of the reaction, if desired, by adding ammonia water or the like to the reaction solution and adjusting the pH of the reaction solution (for example, adjusting the pH of the reaction solution to about 8), an acrylic copolymer (A Can be obtained.
［粘着付与樹脂（Ｂ）］
　本発明に用いる粘着付与樹脂（Ｂ）は、１３０～１８０℃、好ましくは１４０～１６０℃の軟化点を有するものである。粘着付与樹脂（Ｂ）を含有させることで、タイヤのトレッド部のような被着体に対しても優れた粘着力を有する粘着剤組成物を得ることができる。また、軟化点が１３０℃を下回る粘着性付与樹脂を用いると、得られる粘着剤層の剥離強度が低下するおそれがある。一方、１８０℃を超えるような粘着性付与樹脂は入手が困難である。 [Tackifying resin (B)]
The tackifier resin (B) used in the present invention has a softening point of 130 to 180 ° C, preferably 140 to 160 ° C. By including the tackifier resin (B), it is possible to obtain a pressure-sensitive adhesive composition having an excellent adhesive force even to an adherend such as a tread portion of a tire. Moreover, when the tackifying resin having a softening point lower than 130 ° C. is used, the peel strength of the obtained pressure-sensitive adhesive layer may be lowered. On the other hand, tackifying resins having a temperature exceeding 180 ° C. are difficult to obtain.
　粘着付与樹脂（Ｂ）は、上記範囲の軟化点を有する限り、その種類は特に制限されない。例えば、ロジン系樹脂、石油系樹脂、テルペン系樹脂、アルキルフェノール樹脂、クマロン樹脂、クマロンインデン樹脂、スチレン樹脂、キシレン樹脂等が挙げられる。 The kind of the tackifier resin (B) is not particularly limited as long as it has a softening point in the above range. Examples thereof include rosin resins, petroleum resins, terpene resins, alkylphenol resins, coumarone resins, coumarone indene resins, styrene resins, xylene resins, and the like.
　ロジン系樹脂は、ロジン又はロジン誘導体をいう。ロジンとしては、例えば、ガムロジン、ウッドロジン、トール油ロジン等が挙げられる。
　ロジン誘導体としては、例えば、重合ロジン、不均化ロジン、水素化ロジン、強化ロジン、ロジンエステル、重合ロジンエステル、ロジンフェノール等が挙げられる。なお、エステル化に使用する多価アルコールとしてはエチレングリコール、ジエチレングリコール、グリセリン、ペンタエリスリトール等が使用できる。
　石油系樹脂としては、例えば、Ｃ５系石油樹脂、Ｃ９系石油樹脂、Ｃ５－Ｃ９共重合系石油樹脂、ピュアモノマー樹脂、ジシクロペンタジエン系石油樹脂及びこれらの水素化物等が挙げられる。
　テルペン系樹脂としては、例えば、テルペン重合体、β－ピネン重合体、テルペンフェノール樹脂及び芳香族変性テルペン重合体等が挙げられる。
　これらの粘着付与樹脂（Ｂ）は一種単独で、あるいは二種以上を組み合わせて用いることができる。
　なかでも、特に優れた粘着力を有する粘着剤組成物を得ることができることから、ロジン系樹脂が好ましい。 The rosin resin refers to rosin or a rosin derivative. Examples of the rosin include gum rosin, wood rosin, tall oil rosin and the like.
Examples of the rosin derivative include polymerized rosin, disproportionated rosin, hydrogenated rosin, reinforced rosin, rosin ester, polymerized rosin ester, and rosin phenol. As the polyhydric alcohol used for esterification, ethylene glycol, diethylene glycol, glycerin, pentaerythritol and the like can be used.
Examples of the petroleum resins include C5 petroleum resins, C9 petroleum resins, C5-C9 copolymer petroleum resins, pure monomer resins, dicyclopentadiene petroleum resins, and hydrides thereof.
Examples of the terpene resin include terpene polymers, β-pinene polymers, terpene phenol resins, and aromatic modified terpene polymers.
These tackifier resins (B) can be used singly or in combination of two or more.
Among these, a rosin resin is preferable because a pressure-sensitive adhesive composition having particularly excellent adhesive strength can be obtained.
　粘着付与樹脂（Ｂ）の添加量は、単官能単量体混合物１００質量部に対して、固形分換算で、１～１５質量部が好ましく、３～１０質量部がより好ましい。１質量部以上であることで、タイヤのトレッド部のような被着体に対しても優れた粘着力を有する粘着剤組成物を得ることができ、１５質量部以下であることで、塗工安定性に優れる粘着剤組成物を得ることができる。 The addition amount of the tackifier resin (B) is preferably 1 to 15 parts by mass, more preferably 3 to 10 parts by mass in terms of solid content with respect to 100 parts by mass of the monofunctional monomer mixture. By being 1 mass part or more, the adhesive composition which has the outstanding adhesive force also to the to-be-adhered body like a tread part of a tire can be obtained, and it is coating by being 15 mass parts or less. An adhesive composition having excellent stability can be obtained.
［粘着剤組成物］
　本発明の粘着剤組成物は、粘着付与樹脂（Ｂ）に加えて、さらに他の粘着付与樹脂を含有していてもよい。他の粘着付与樹脂を含有することで、さらに優れた粘着力を有する粘着剤組成物を得ることができ、また、他の粘着付与樹脂をあらかじめ重合反応系内に存在させる場合は重合反応を制御することができる。 [Adhesive composition]
The pressure-sensitive adhesive composition of the present invention may further contain another tackifying resin in addition to the tackifying resin (B). By containing other tackifying resins, it is possible to obtain a pressure-sensitive adhesive composition having further excellent tackiness, and when other tackifying resins are present in the polymerization reaction system in advance, the polymerization reaction is controlled. can do.
　他の粘着付与樹脂としては、粘着付与樹脂（Ｂ）以外の粘着付与樹脂であり、例えば、ロジン系樹脂、石油系樹脂、テルペン系樹脂、アルキルフェノール樹脂、クマロン樹脂、クマロンインデン樹脂、スチレン樹脂、キシレン樹脂等が挙げられる。
　他の粘着付与樹脂は一種単独で、あるいは二種以上を組み合わせて用いることができる。
　これらの中でも、他の粘着付与樹脂としては、テルペン系樹脂が好ましく、軟化点が１００～１３０℃のテルペン系樹脂がより好ましい。
　他の粘着付与樹脂の添加量は、単官能単量体混合物１００質量部に対して、固形分換算で、０～１５質量部が好ましく、３～１０質量部がより好ましい。なお、上記のいずれの粘着付与樹脂においても、樹脂自体をそのまま用いてもよいし、予め乳化したものを用いてもよい。 Other tackifying resins include tackifying resins other than the tackifying resin (B). For example, rosin resins, petroleum resins, terpene resins, alkylphenol resins, coumarone resins, coumarone indene resins, styrene resins, Examples include xylene resins.
Other tackifier resins can be used singly or in combination of two or more.
Among these, as other tackifying resins, terpene resins are preferable, and terpene resins having a softening point of 100 to 130 ° C. are more preferable.
The addition amount of the other tackifying resin is preferably 0 to 15 parts by mass, more preferably 3 to 10 parts by mass in terms of solid content with respect to 100 parts by mass of the monofunctional monomer mixture. In any of the above tackifying resins, the resin itself may be used as it is, or a pre-emulsified one may be used.
　また、エマルション型粘着剤組成物は、本発明の効果を妨げない限りにおいて、その他の添加剤を含有することができる。用いる添加剤としては、防腐剤、防カビ剤、増粘剤、濡れ剤、消泡剤、可塑剤、ｐＨ調整剤、顔料、染料等が挙げられる。
　これらの添加剤は、アクリル系共重合体（Ａ）の乳化重合反応液に添加してもよいし、アクリル系共重合体（Ａ）を製造する際に乳化重合系内にあらかじめ添加してもよい。 The emulsion-type pressure-sensitive adhesive composition can contain other additives as long as the effects of the present invention are not hindered. Additives used include antiseptics, fungicides, thickeners, wetting agents, antifoaming agents, plasticizers, pH adjusters, pigments, dyes and the like.
These additives may be added to the emulsion polymerization reaction solution of the acrylic copolymer (A), or may be added in advance to the emulsion polymerization system when the acrylic copolymer (A) is produced. Good.
　本発明のエマルション型粘着剤組成物を製造する方法は特に限定されず、例えば、
（ｉ）アクリル系共重合体（Ａ）を乳化重合法により製造した重合反応液に、粘着付与樹脂（Ｂ）及び所望により他の乳化された粘着付与樹脂の所定量を混合して、エマルション型粘着剤組成物を製造する方法、
（ｉｉ）アクリル系共重合体（Ａ）を製造する際に乳化重合系内にあらかじめ粘着付与樹脂（Ｂ）及び所望により他の粘着付与樹脂を存在させ、そのまま乳化重合を行うことにより、エマルション型粘着剤組成物を製造する方法、
（ｉｉｉ）アクリル系共重合体（Ａ）を製造する際に乳化重合系内にあらかじめ他の粘着付与樹脂を存在させて乳化重合を行い、重合反応終了後に、乳化された粘着付与樹脂（Ｂ）を混合してエマルション型粘着剤組成物を製造する方法等が挙げられる。
　これらの中で、重合反応を制御することができ、また、粘着付与樹脂（Ｂ）の特性が失われることもないことから、上記の（ｉｉｉ）の方法が好ましい。 The method for producing the emulsion-type pressure-sensitive adhesive composition of the present invention is not particularly limited. For example,
(I) A predetermined amount of the tackifier resin (B) and, if desired, another emulsified tackifier resin, is mixed into the polymerization reaction liquid produced by the emulsion polymerization method of the acrylic copolymer (A), and the emulsion type A method for producing an adhesive composition,
(Ii) When the acrylic copolymer (A) is produced, an emulsion type is obtained by preliminarily containing a tackifying resin (B) and optionally another tackifying resin in the emulsion polymerization system, and performing emulsion polymerization as it is. A method for producing an adhesive composition,
(Iii) When the acrylic copolymer (A) is produced, another tackifying resin is preliminarily present in the emulsion polymerization system to conduct emulsion polymerization, and after the polymerization reaction is completed, the emulsified tackifying resin (B) And a method of producing an emulsion-type pressure-sensitive adhesive composition.
Among these, the method (iii) is preferable because the polymerization reaction can be controlled and the characteristics of the tackifier resin (B) are not lost.
　本発明のエマルション型粘着剤組成物は十分な凝集力を有するため、粘着剤層の凝集力を低下させて粗面に対する追従性を高めた従来の粘着シートと異なり、粘着シートの剥離後に糊残りが生じにくいものである。
　また、ラベル加工時に切断機のカッターや印刷機のガイド等に粘着剤組成物が付着し、粘着シート等を汚染することがない。 Since the emulsion-type pressure-sensitive adhesive composition of the present invention has a sufficient cohesive force, the adhesive residue remains after peeling of the pressure-sensitive adhesive sheet, unlike the conventional pressure-sensitive adhesive sheet that reduces the cohesive force of the pressure-sensitive adhesive layer and improves the followability to the rough surface. Is unlikely to occur.
In addition, the pressure-sensitive adhesive composition does not adhere to the cutter of the cutting machine, the guide of the printing machine, or the like during label processing, and the pressure-sensitive adhesive sheet or the like is not contaminated.
２）再剥離性粘着シート
　本発明の再剥離性粘着シートは、少なくとも基材と粘着剤層とを有する再剥離性粘着シートであって、前記粘着剤層が、前記アクリル系共重合体（Ａ）と粘着付与樹脂（Ｂ）を含有するエマルション型粘着剤組成物を用いて得られたものであることを特徴とする。
　本発明の再剥離性粘着シートは、粘着剤層を介して被着体に粘着させた後、被着体から再剥離可能な粘着シートである。 2) Re-peelable pressure-sensitive adhesive sheet The re-peelable pressure-sensitive adhesive sheet of the present invention is a re-peelable pressure-sensitive adhesive sheet having at least a base material and a pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer comprises the acrylic copolymer (A). And an emulsion-type pressure-sensitive adhesive composition containing the tackifying resin (B).
The releasable pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet that can be re-peeled from an adherend after it is adhered to the adherend via an adhesive layer.
［基材］
　本発明に用いる基材としては、特に限定されるものではなく、公知のプラスチックフィルムや紙、合成紙等を使用することができる。なかでも、機械的強度に優れ、剥離時における基材の破壊を有効に防止できることから、プラスチックフィルム又は合成紙であることが好ましい。
　プラスチックフィルムの材質としては、ポリエチレン、ポリプロピレン等のポリオレフィン；ポリエチレンテレフタレート等のポリエステル；ナイロン等のポリアミド；ポリスチレン；等が挙げられる。
　合成紙としては、例えば、合成樹脂と充填剤及び添加剤を溶融混合後、押出しして成膜された内部にボイドを有する単層又は複層の合成紙等が挙げられる。 [Base material]
The substrate used in the present invention is not particularly limited, and a known plastic film, paper, synthetic paper or the like can be used. Especially, since it is excellent in mechanical strength and can prevent destruction of the base material at the time of peeling, it is preferably a plastic film or synthetic paper.
Examples of the material of the plastic film include polyolefin such as polyethylene and polypropylene; polyester such as polyethylene terephthalate; polyamide such as nylon; polystyrene;
Examples of the synthetic paper include single-layer or multi-layer synthetic paper having voids formed inside after melt-mixing a synthetic resin, a filler, and an additive and then extruding the film.
　また、前記基材は金属層を有することが好ましい。金属層としては、例えば、アルミニウム蒸着層等が挙げられる。金属層が存在しない場合、タイヤの成分であるアミン系老化防止剤や芳香族系オイル等が、粘着剤層を通過して基材まで移行し、それが原因となって、基材表面（粘着剤層と接する側の反対面）が黒色化する場合があるが、金属層を存在させることで当該成分の移行を妨げ、基材表面の黒色化を防止することができる。そのため金属層は、基材の粘着剤層と接する側に設けられることが好ましい。 The base material preferably has a metal layer. As a metal layer, an aluminum vapor deposition layer etc. are mentioned, for example. In the absence of a metal layer, the components of the tire, such as amine-based anti-aging agents and aromatic oils, pass through the pressure-sensitive adhesive layer and migrate to the base material. Although the surface opposite to the side in contact with the agent layer may be blackened, the presence of the metal layer prevents the migration of the component and prevents blackening of the substrate surface. Therefore, it is preferable that the metal layer is provided on the side of the substrate that contacts the pressure-sensitive adhesive layer.
　さらに、基材表面には、印刷層を形成しやすくするための易接着層や、熱転写記録やインキジェット記録などの記録を可能にするための受理層を設けてもよく、それらの表面を保護するためのオーバーコートもしくはオーバーラミネートを行ってもよい。 In addition, the substrate surface may be provided with an easy-adhesion layer to facilitate the formation of a printed layer, and a receiving layer to enable recording such as thermal transfer recording and ink jet recording, protecting the surface. An overcoat or overlaminate may be performed.
　基材の厚みは特に限定されないが、１０～１５０μｍが好ましく、１０～１２０μｍがより好ましい。１０μｍ未満になると、取り扱いが困難になったり、貼り付け時にシワになったり、剥離時に基材が破壊する場合がある。一方、１５０μｍを超えると、柔軟性が低下するのに伴い、タイヤ等の粗面への追従性が低下し、再剥離性粘着シートが剥がれやすくなる場合がある。なお、上記の好ましい基材の厚さは、金属層、易接着層、受理層等を有する場合は、これらの層を含めた全体の厚さである。 The thickness of the substrate is not particularly limited, but is preferably 10 to 150 μm, more preferably 10 to 120 μm. When the thickness is less than 10 μm, handling may become difficult, wrinkles may occur during pasting, and the substrate may be destroyed during peeling. On the other hand, when it exceeds 150 μm, the flexibility to the tire and the rough surface such as a tire may be lowered, and the releasable pressure-sensitive adhesive sheet may be easily peeled off. In addition, the thickness of said preferable base material is the whole thickness including these layers, when it has a metal layer, an easily bonding layer, a receiving layer, etc.
［粘着剤層］
　粘着剤層は、本発明のエマルション型粘着剤組成物を用いて形成されたものである。
　粘着剤層の厚みは、通常、１～５０μｍ、好ましくは、５～４０μｍである。粘着剤層の厚みを１μｍ以上とすることにより、必要な粘着力及び凝集力（保持力）を確保することができ、５０μｍ以下とすることにより、コストアップを防ぐとともに、粘着剤層が端部からはみ出すのを防止することができる。 [Adhesive layer]
The pressure-sensitive adhesive layer is formed using the emulsion-type pressure-sensitive adhesive composition of the present invention.
The thickness of the pressure-sensitive adhesive layer is usually 1 to 50 μm, preferably 5 to 40 μm. By setting the thickness of the pressure-sensitive adhesive layer to 1 μm or more, necessary adhesive force and cohesive force (holding force) can be secured, and by setting it to 50 μm or less, the cost is prevented and the pressure-sensitive adhesive layer has an end portion. It can be prevented from protruding.
　粘着剤層のゲル分率は、４０～６５質量％が好ましく、４５～６０質量％がより好ましい。４０質量％以上であることで、十分な凝集力が得られ、６５質量％以下であることで高い粘着力が得られる。
　上記のゲル分率は、粘着剤の乾燥被膜の酢酸エチルに対する不溶解分の比率を表し、後述する測定により求めることができる。 The gel fraction of the pressure-sensitive adhesive layer is preferably 40 to 65% by mass, and more preferably 45 to 60% by mass. When it is 40% by mass or more, sufficient cohesive force can be obtained, and when it is 65% by mass or less, high adhesive force can be obtained.
Said gel fraction represents the ratio of the insoluble part with respect to the ethyl acetate of the dry film of an adhesive, and can be calculated | required by the measurement mentioned later.
［剥離材］
　本発明の再剥離性粘着シートの粘着剤層の片面は、剥離材で保護されていることが好ましい。用いる剥離材の材質は、特に限定されるものではなく、例えば、上質紙、グラシン紙、ラミネート紙等の紙基材や、ポリエチレンテレフタレート、ポリエチレンナフタレート等のポリエステル；ポリプロピレン、ポリエチレン等のポリオレフィン；等のフィルム基材が挙げられる。
　剥離材としては、通常、上記基材の片面または両面を剥離剤で剥離処理を施したものを使用する。
　用いる剥離剤としては、フッ素系樹脂、シリコーン系樹脂、長鎖アルキル基含有カルバメート等が挙げられる。
　剥離材の厚みは特に限定されないが、通常１０～２５０μｍ、好ましくは２０～２００μｍである。 [Peeling material]
One side of the pressure-sensitive adhesive layer of the releasable pressure-sensitive adhesive sheet of the present invention is preferably protected with a release material. The material of the release material to be used is not particularly limited, and examples thereof include paper base materials such as high-quality paper, glassine paper, and laminate paper, polyesters such as polyethylene terephthalate and polyethylene naphthalate; polyolefins such as polypropylene and polyethylene; The film base material is mentioned.
As the release material, one obtained by subjecting one side or both sides of the base material to release treatment with a release agent is usually used.
Examples of the release agent to be used include fluorine resins, silicone resins, and long-chain alkyl group-containing carbamates.
The thickness of the release material is not particularly limited, but is usually 10 to 250 μm, preferably 20 to 200 μm.
［再剥離性粘着シート］
　本発明の再剥離性粘着シートは、（ｉ）本発明のエマルション型粘着剤組成物を基材表面に塗布し、得られた塗膜を乾燥後、この塗膜上に剥離材を貼り合わせる方法、又は、（ｉｉ）本発明のエマルション型粘着剤組成物を剥離材表面に塗布し、得られた塗膜を乾燥後、この塗膜上に基材を貼り合わせる方法により形成することができる。 [Removable adhesive sheet]
The re-peelable pressure-sensitive adhesive sheet of the present invention is a method of (i) applying the emulsion-type pressure-sensitive adhesive composition of the present invention to the surface of a substrate, drying the obtained coating film, and laminating the release material on the coating film Or (ii) The emulsion-type pressure-sensitive adhesive composition of the present invention is applied to the surface of the release material, and the obtained coating film is dried, and then formed by a method of laminating a substrate on the coating film.
　基材又は剥離材表面にエマルション型粘着剤組成物を塗布する方法としては、グラビアコート法、バーコート法、スプレーコート法、スピンコート法、ロールコート法、ダイコート法、ナイフコート法、エアナイフコート法、カーテンコート法等の従来公知の塗工方法が挙げられる。 Gravure coating method, bar coating method, spray coating method, spin coating method, roll coating method, die coating method, knife coating method, air knife coating method as a method of applying the emulsion-type pressure-sensitive adhesive composition to the substrate or release material surface And conventionally known coating methods such as curtain coating.
　エマルション型粘着剤組成物の塗膜を乾燥させる温度は、通常８０～１２０℃、好ましくは９０～１１０℃であり、乾燥時間は、通常、３０秒から１５分、好ましくは３～７分程度である。 The temperature for drying the coating film of the emulsion-type pressure-sensitive adhesive composition is usually 80 to 120 ° C., preferably 90 to 110 ° C., and the drying time is usually 30 seconds to 15 minutes, preferably about 3 to 7 minutes. is there.
　本発明の再剥離性粘着シートの粘着剤層は、粗面に対して高い粘着力を有する。したがって、タイヤ貼付用の再剥離性粘着シートとして好ましく利用され、特にタイヤのトレッド部貼付用の再剥離性粘着シートとして好ましく利用される。
　また、本発明の粘着剤組成物を用いて得られる粘着剤層は十分な凝集力を有するため、粘着シートを剥離した後に糊残りが生じにくい。
　さらに、ラベル加工を施す際、切断機のカッターや印刷機のガイド等に粘着剤組成物が付着し、粘着シート等を汚染することがない。 The pressure-sensitive adhesive layer of the releasable pressure-sensitive adhesive sheet of the present invention has a high adhesive force with respect to a rough surface. Therefore, it is preferably used as a releasable pressure-sensitive adhesive sheet for attaching a tire, and particularly preferably used as a removable pressure-sensitive adhesive sheet for attaching a tread portion of a tire.
In addition, since the pressure-sensitive adhesive layer obtained using the pressure-sensitive adhesive composition of the present invention has a sufficient cohesive force, no adhesive residue is likely to occur after the pressure-sensitive adhesive sheet is peeled off.
Furthermore, when label processing is performed, the pressure-sensitive adhesive composition adheres to a cutter of a cutting machine, a guide of a printing machine, and the like, and does not contaminate the pressure-sensitive adhesive sheet or the like.
　以下、実施例により本発明を更に詳細に説明する。但し、本発明は以下の実施例により何ら限定されるものではない。
　実施例及び比較例において用いた試薬は、次の通りである。
・アクリル酸２－エチルヘキシル：三菱化学社製（第１表中、「２ＥＨＡ」と表す。）
・アクリル酸ブチル：三菱化学社製（第１表中、「ＢＡ」と表す。）
・アクリル酸：三菱化学社製（第１表中、「ＡＡ」と表す。）
・メタクリル酸メチル：三菱レイヨン社製（第１表中、「ＭＭＡ」と表す。）
・ペンタエリスリトールトリアクリレート：ダイセル・サイテック社製、商品名「ＰＥＴＩＡ」
・連鎖移動剤：ラウリルメルカプタン
・アニオン系界面活性剤：第一工業製薬社製、商品名「ニューフロンティアＡ－２２９Ｅ」
・テルペンフェノール樹脂：荒川化学工業社製、商品名「タマノル９０１」、軟化点１２５℃
・ロジン系樹脂１：ロジンエステル系粘着付与剤、ハリマ化成社製、商品名「ハリエスターＳＫ－８１６Ｅ」、軟化点１４５℃
・ロジン系樹脂２：ロジンエステル系粘着付与剤、荒川化学工業社製、商品名「スーパーエステルＥ－７２０」、軟化点１００℃
・ロジン系樹脂３：ロジン変性エステル系粘着付与剤、ハリマ化成社製、商品名「ハリエスターＳＫ－３８５ＮＳ」、軟化点８５℃ Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
The reagents used in the examples and comparative examples are as follows.
2-ethylhexyl acrylate: manufactured by Mitsubishi Chemical Corporation (in Table 1, represented as “2EHA”)
-Butyl acrylate: manufactured by Mitsubishi Chemical Corporation (represented as "BA" in Table 1)
Acrylic acid: manufactured by Mitsubishi Chemical Corporation (in Table 1, represented as “AA”)
-Methyl methacrylate: Mitsubishi Rayon Co., Ltd. (in Table 1, "MMA")
Pentaerythritol triacrylate: manufactured by Daicel-Cytec, Inc., trade name “PETIA”
・ Chain transfer agent: Lauryl mercaptan ・ Anionic surfactant: Daiichi Kogyo Seiyaku Co., Ltd., trade name “New Frontier A-229E”
-Terpene phenol resin: Arakawa Chemical Industries, trade name “Tamanol 901”, softening point 125 ° C.
・ Rosin resin 1: Rosin ester tackifier, manufactured by Harima Kasei Co., Ltd., trade name “Harry Star SK-816E”, softening point 145 ° C.
Rosin resin 2: Rosin ester tackifier, manufactured by Arakawa Chemical Industries, trade name “Superester E-720”, softening point 100 ° C.
・ Rosin resin 3: Rosin-modified ester tackifier, manufactured by Harima Kasei Co., Ltd., trade name “Harry Star SK-385NS”, softening point 85 ° C.
（製造例１～３）
　第１表に記載の質量部で単量体を混合し、単官能単量体混合物を調製した。 (Production Examples 1 to 3)
Monomers were mixed in the parts by mass shown in Table 1 to prepare a monofunctional monomer mixture.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
（実施例１）
　製造例１で得た単官能単量体混合物１００質量部に、ペンタエリスリトールトリアクリレート０．３質量部、テルペンフェノール樹脂８質量部、及び、ラウリルメルカプタン０．０１８質量部を加え混合した。得られた混合物を、攪拌機、温度計、還流冷却器及び滴下ロートを備えた反応容器に投入し、約３０℃に保ちながら、３０分間攪拌して溶解させた。
　次いで、アニオン系界面活性剤０．６質量部をイオン交換水５７質量部に分散させた分散液を、約３０℃で加え、全容を３０分間攪拌して単量体混合物等を含む乳化物を調製した。 Example 1
To 100 parts by mass of the monofunctional monomer mixture obtained in Production Example 1, 0.3 part by mass of pentaerythritol triacrylate, 8 parts by mass of terpene phenol resin, and 0.018 part by mass of lauryl mercaptan were added and mixed. The obtained mixture was put into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, and stirred and dissolved for 30 minutes while maintaining at about 30 ° C.
Next, a dispersion in which 0.6 part by weight of an anionic surfactant is dispersed in 57 parts by weight of ion exchange water is added at about 30 ° C., and the whole volume is stirred for 30 minutes to obtain an emulsion containing a monomer mixture and the like. Prepared.
　別途、攪拌機、還流冷却器、温度計、窒素導入管及び滴下ロートを備えた反応容器に脱イオン水４０質量部を投入し、窒素を流入させながら、反応容器内の温度を８０℃まで昇温させ、濃度が５質量％になるように過硫酸カリウムを仕込んで溶解させた。この中に、前記単量体混合物等を含む乳化物を８０～８３℃に保ちながら３時間かけて滴下した。また、乳化物の滴下と並行して濃度５質量％の過硫酸カリウム水溶液４質量部を滴下して、反応容器内の温度を８０～８３℃に保持しながら３時間攪拌して乳化重合を行なった。さらに、前記過硫酸カリウム水溶液の滴下終了後、１時間目及び２時間目に、それぞれ過硫酸カリウム１質量部ずつ添加して重合を完結させ、同温度で３時間熟成させた。反応終了後、室温に冷却して、反応液に２５質量％アンモニア水を加えてｐＨが８．０となるように調整し、アクリル系共重合体（Ａ）を含有するエマルションを得た。 Separately, 40 parts by mass of deionized water is put into a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen introduction tube and a dropping funnel, and the temperature in the reaction vessel is raised to 80 ° C. while flowing nitrogen. Then, potassium persulfate was charged and dissolved so that the concentration became 5% by mass. Into this, an emulsion containing the monomer mixture and the like was added dropwise over 3 hours while maintaining at 80 to 83 ° C. In parallel with the dropping of the emulsion, 4 parts by mass of a potassium persulfate aqueous solution having a concentration of 5% by mass was dropped, and emulsion polymerization was carried out by stirring for 3 hours while maintaining the temperature in the reaction vessel at 80 to 83 ° C. It was. Furthermore, after completion of the dropwise addition of the potassium persulfate aqueous solution, 1 part by mass of potassium persulfate was added at 1 hour and 2 hours respectively to complete the polymerization, and the mixture was aged at the same temperature for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and 25% by mass ammonia water was added to the reaction solution to adjust the pH to 8.0, thereby obtaining an emulsion containing the acrylic copolymer (A).
　上記のエマルションに、粘着付与樹脂（Ｂ）として、ロジン系樹脂１を５質量部添加して、エマルション型粘着剤組成物１を得た。 To the above emulsion, 5 parts by mass of rosin-based resin 1 was added as a tackifier resin (B) to obtain an emulsion-type pressure-sensitive adhesive composition 1.
（実施例２～４、比較例１～４）
　第２表に記載の原料を用いたことを除き、実施例１と同様にしてエマルション型粘着剤組成物２～８を製造した。 (Examples 2 to 4, Comparative Examples 1 to 4)
Emulsion-type pressure-sensitive adhesive compositions 2 to 8 were produced in the same manner as in Example 1 except that the raw materials listed in Table 2 were used.
　［ゲル分率の測定］
　上記の方法で得られたエマルション型粘着剤組成物１～８のそれぞれを、乾燥後の膜厚が０．３ｍｍとなるようにガラス板上に塗工し、２５℃で２４時間乾燥した後、ガラス板から剥離し、更に１００℃で５分間乾燥したものを５０ｍｍ角に切り取り、試料とした。
　次いで、上記試料の質量（Ｇ１）を測定し、次に、試料を酢酸エチル中に常温で２４時間浸漬し、不溶解分を３００メッシュ金網を用いて濾過して分離した。１１０℃で１時間乾燥した後の残渣の質量（Ｇ２）を測定し、以下の式に従って、ゲル分率を算出した。
　測定結果を第２表に示す。 [Measurement of gel fraction]
Each of the emulsion-type pressure-sensitive adhesive compositions 1 to 8 obtained by the above method was coated on a glass plate so that the film thickness after drying was 0.3 mm, and dried at 25 ° C. for 24 hours. A sample peeled from the glass plate and further dried at 100 ° C. for 5 minutes was cut into a 50 mm square and used as a sample.
Next, the mass (G1) of the sample was measured, and then the sample was immersed in ethyl acetate at room temperature for 24 hours, and the insoluble matter was separated by filtration using a 300 mesh wire net. The mass (G2) of the residue after drying at 110 ° C. for 1 hour was measured, and the gel fraction was calculated according to the following formula.
The measurement results are shown in Table 2.
Figure JPOXMLDOC01-appb-M000002
Figure JPOXMLDOC01-appb-M000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
（実施例５～８、比較例５～８）
　実施例１～４及び比較例１～４で得られたエマルション型粘着剤組成物１～８のそれぞれを、ポリエチレンをラミネートした上質紙の片面に剥離処理を施した剥離紙（リンテック社製、「ＳＰ－８ＥＡアイボリー」）上に、乾燥後に３０μｍの厚さになるように塗工し、９０℃で２分間乾燥することで粘着剤層を形成した。次いで、表面基材として、アルミニウム蒸着層を備えた白コートポリエチレンテレフタレートフィルム［白コート（エチレン酢酸ビニル樹脂及び酸化チタンを含む）１μｍ／ポリエチレンテレフタレートフィルム１２μｍ／アルミニウム蒸着層］のアルミニウム蒸着層と、得られた粘着剤層とを貼り合わせ、粘着シート１～８を得た。 (Examples 5 to 8, Comparative Examples 5 to 8)
Each of the emulsion-type pressure-sensitive adhesive compositions 1 to 8 obtained in Examples 1 to 4 and Comparative Examples 1 to 4 is a release paper (manufactured by Lintec Corporation, manufactured by Lintec Co., Ltd.). SP-8EA ivory ") was coated to a thickness of 30 μm after drying, and dried at 90 ° C. for 2 minutes to form an adhesive layer. Next, as a surface substrate, an aluminum vapor deposition layer of a white coat polyethylene terephthalate film [white coat (including ethylene vinyl acetate resin and titanium oxide) 1 μm / polyethylene terephthalate film 12 μm / aluminum vapor deposition layer] provided with an aluminum vapor deposition layer was obtained. The obtained pressure-sensitive adhesive layer was bonded to obtain pressure-sensitive adhesive sheets 1 to 8.
（実施例９）
　表面基材に厚さ６０μｍの二軸延伸白色ポリプロピレンフィルムを用いたことを除き、実施例５と同様にして、粘着シート９を得た。 Example 9
A pressure-sensitive adhesive sheet 9 was obtained in the same manner as in Example 5 except that a biaxially stretched white polypropylene film having a thickness of 60 μm was used as the surface substrate.
（実貼り評価試験）
　実施例５～９及び比較例５～８で得られた粘着シート１～９から、５ｃｍ×１０ｃｍの小片を切り出して、剥離紙を剥離した後、それをラジアルタイヤ（ブリヂストン社製、Ｐｌａｙｚ）に対して、２３℃（５０％ＲＨ）、４０℃、及び４０℃（５０％ＲＨ）の環境下でそれぞれ貼り付けた。そのまま７２時間それぞれ放置した後、タイヤから粘着シートを手で引き剥がし、以下の基準によって剥離強度を評価した。また、ラジアルタイヤのトレッド部を観察し、糊残り性を評価した。評価結果を第３表に示す。 (Actual evaluation test)
From the adhesive sheets 1 to 9 obtained in Examples 5 to 9 and Comparative Examples 5 to 8, a 5 cm × 10 cm piece was cut out, and the release paper was peeled off. Then, it was applied to a radial tire (Playz made by Bridgestone). On the other hand, it affixed in the environment of 23 degreeC (50% RH), 40 degreeC, and 40 degreeC (50% RH), respectively. After leaving as it is for 72 hours, the pressure-sensitive adhesive sheet was peeled off from the tire by hand, and the peel strength was evaluated according to the following criteria. Further, the tread portion of the radial tire was observed to evaluate the adhesive residue. The evaluation results are shown in Table 3.
｛剥離強度の評価｝
◎：十分な接着強度を有する。
○：やや接着強度が劣るものの実用上問題ないレベルである。
△：接着強度が弱く簡単に剥がれる。
×：ほとんど接着強度がない。 {Evaluation of peel strength}
(Double-circle): It has sufficient adhesive strength.
○: Although the adhesive strength is slightly inferior, it is a level that causes no problem in practical use.
Δ: Adhesive strength is weak and easily peels off.
X: Almost no adhesive strength.
｛糊残り性の評価｝
◎：糊残りがない。
○：一部糊残りがある。
△：全面に糊残りがある。
×：全面に転着している。 {Evaluation of adhesive residue}
A: There is no adhesive residue.
○: Some glue residue remains.
Δ: There is adhesive residue on the entire surface.
X: Transferred to the entire surface.
（はみ出し評価試験）
　実施例５～９及び比較例５～８で得られた粘着シート１～９から、１０ｃｍ×１０ｃｍの小片を切り出し、さらに粘着剤層と基材を１ｃｍ×１０ｃｍの大きさで部分的に除去し、図１に記載の形状を有する試験片を作製した。図１において、（ａ）は試験片を上から見た図であり、（ｂ）は試験片を横方向から見た図である。図１中、１は剥離フィルム、２は粘着剤層、３は基材をそれぞれ示す。
　この試験片を、４０℃、２０ｋＮ／６０ｃｍ２の圧力下に２４時間静置し、このときの端部の粘着剤のはみ出しを観察し、以下の基準によって評価した。評価結果を第３表に示す。 (Extrusion evaluation test)
From the pressure-sensitive adhesive sheets 1 to 9 obtained in Examples 5 to 9 and Comparative Examples 5 to 8, small pieces of 10 cm × 10 cm were cut out, and the pressure-sensitive adhesive layer and the substrate were partially removed in a size of 1 cm × 10 cm. A test piece having the shape shown in FIG. 1 was prepared. In FIG. 1, (a) is the figure which looked at the test piece from the top, (b) is the figure which looked at the test piece from the horizontal direction. In FIG. 1, 1 is a release film, 2 is an adhesive layer, and 3 is a substrate.
The test piece was allowed to stand for 24 hours under a pressure of 20 kN / 60 cm 2 at 40 ° C., and the protrusion of the adhesive at the end was observed and evaluated according to the following criteria. The evaluation results are shown in Table 3.
｛はみ出しの評価｝
◎：はみ出しがない。
○：１ｍｍ以下のはみ出しがある。
△：１ｍｍ超、３ｍｍ以下のはみ出しがある。
×：３ｍｍ超、５ｍｍ以下のはみ出しがある。 {Evaluation of protrusion}
A: There is no protrusion.
○: There is a protrusion of 1 mm or less.
Δ: Overhang of more than 1 mm and 3 mm or less.
X: The protrusion of more than 3 mm and 5 mm or less exists.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　第３表に示されるように、実施例５～９の粘着シートは、比較例５～８の粘着シートに比して、２３℃（５０％ＲＨ）、４０℃、及び４０℃（５０％ＲＨ）の環境下での剥離強度及び糊残り性に優れていた。また、はみ出し試験でのはみ出しもほとんど認められなかった。 As shown in Table 3, the pressure-sensitive adhesive sheets of Examples 5 to 9 were 23 ° C. (50% RH), 40 ° C., and 40 ° C. (50% RH) as compared with the pressure-sensitive adhesive sheets of Comparative Examples 5 to 8. ) In the environment of) and excellent in adhesive residue. Further, almost no protrusion was observed in the protrusion test.
　１・・・剥離フィルム
　２・・・粘着剤層
　３・・・基材 DESCRIPTION OF SYMBOLS 1 ... Release film 2 ... Adhesive layer 3 ... Base material

Claims (9)

  1. 　２－エチルヘキシルアクリレート、ブチルアクリレート及びエチレン性不飽和カルボン酸を含む単官能単量体混合物と、多官能単量体とを乳化重合して得られるアクリル系共重合体（Ａ）、並びに、粘着付与樹脂（Ｂ）を含むエマルション型粘着剤組成物であって、
    ２－エチルヘキシルアクリレートとブチルアクリレートの質量比（２－エチルヘキシルアクリレートの含有量／ブチルアクリレートの含有量）が０．６～２．５であり、
    前記粘着付与樹脂（Ｂ）の軟化点が１３０～１８０℃である
    ことを特徴とするエマルション型粘着剤組成物。     Acrylic copolymer (A) obtained by emulsion polymerization of a monofunctional monomer mixture containing 2-ethylhexyl acrylate, butyl acrylate and ethylenically unsaturated carboxylic acid and a polyfunctional monomer, and tackifying An emulsion-type pressure-sensitive adhesive composition containing a resin (B),
    The mass ratio of 2-ethylhexyl acrylate to butyl acrylate (content of 2-ethylhexyl acrylate / content of butyl acrylate) is 0.6 to 2.5,
    An emulsion-type pressure-sensitive adhesive composition, wherein the tackifying resin (B) has a softening point of 130 to 180 ° C.
  2. 　２－エチルヘキシルアクリレートとブチルアクリレートの質量比（２－エチルヘキシルアクリレート含有量／ブチルアクリレート含有量）が１．６～１．９である
    請求項１に記載のエマルション型粘着剤組成物。     The emulsion-type pressure-sensitive adhesive composition according to claim 1, wherein the mass ratio of 2-ethylhexyl acrylate to butyl acrylate (2-ethylhexyl acrylate content / butyl acrylate content) is 1.6 to 1.9.
  3. 　前記多官能単量体の含有量が、単官能単量体混合物と多官能単量体からなる全単量体混合物に対して、０．０１～２質量％である
    請求項１に記載のエマルション型粘着剤組成物。     The emulsion according to claim 1, wherein the content of the polyfunctional monomer is 0.01 to 2% by mass with respect to the total monomer mixture composed of the monofunctional monomer mixture and the polyfunctional monomer. Type pressure-sensitive adhesive composition.
  4. 　粘着付与樹脂（Ｂ）が軟化点が１４０～１６０℃の樹脂である
    請求項１に記載のエマルション型粘着剤組成物。     The emulsion-type pressure-sensitive adhesive composition according to claim 1, wherein the tackifying resin (B) is a resin having a softening point of 140 to 160 ° C.
  5. 　粘着付与樹脂（Ｂ）がロジン系樹脂である
    請求項１に記載のエマルション型粘着剤組成物。     The emulsion-type pressure-sensitive adhesive composition according to claim 1, wherein the tackifying resin (B) is a rosin resin.
  6. 　さらに、テルペン系樹脂を含有する
    請求項１に記載のエマルション型粘着剤組成物。     Furthermore, the emulsion-type adhesive composition of Claim 1 containing a terpene resin.
  7. 　基材と粘着剤層とを有する再剥離性粘着シートであって、
    前記粘着剤層が請求項１～６のいずれか１項に記載のエマルション型粘着剤組成物を用いて得られたものであることを特徴とする再剥離性粘着シート。     A releasable pressure-sensitive adhesive sheet having a base material and a pressure-sensitive adhesive layer,
    A re-peelable pressure-sensitive adhesive sheet, wherein the pressure-sensitive adhesive layer is obtained using the emulsion-type pressure-sensitive adhesive composition according to any one of claims 1 to 6.
  8. 　タイヤ貼付用の請求項７に記載の再剥離性粘着シート。 The re-peelable pressure-sensitive adhesive sheet according to claim 7 for attaching tires.
  9. 　タイヤのトレッド部貼付用の請求項７に記載の再剥離性粘着シート。 The re-peelable pressure-sensitive adhesive sheet according to claim 7 for attaching a tread part of a tire.
PCT/JP2012/057692 2011-03-30 2012-03-26 Emulsion adhesive composition and re-peelable adhesive sheet WO2012133268A1 (en)

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JP2013507544A JP5937570B2 (en) 2011-03-30 2012-03-26 Emulsion type adhesive composition and releasable adhesive sheet
CN201280016208.1A CN103534324B (en) 2011-03-30 2012-03-26 Emulsion Adhesive composition and releasable adhesive sheet
KR1020137025114A KR101880420B1 (en) 2011-03-30 2012-03-26 Emulsion adhesive composition and re-peelable adhesive sheet

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WO2013141111A1 (en) * 2012-03-22 2013-09-26 日東電工株式会社 Label and pressure-sensitive adhesive sheet for tire
JP2016035023A (en) * 2014-08-04 2016-03-17 東洋インキＳｃホールディングス株式会社 Aqueous adhesive and adhesive sheet
WO2020158237A1 (en) * 2019-01-31 2020-08-06 横浜ゴム株式会社 Tire rubber composition and pneumatic tire using same
JP2020122109A (en) * 2019-01-31 2020-08-13 横浜ゴム株式会社 Rubber composition for tire, and pneumatic tire using the same
JP2020122110A (en) * 2019-01-31 2020-08-13 横浜ゴム株式会社 Rubber composition for tire and pneumatic tire using the same
JP2021020986A (en) * 2019-07-25 2021-02-18 マクセルホールディングス株式会社 Repeelable adhesive composition and adhesive tape
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JP7031633B2 (en) * 2018-03-28 2022-03-08 荒川化学工業株式会社 Adhesive-imparting resin emulsion and water-based adhesive / adhesive composition

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JP2016035023A (en) * 2014-08-04 2016-03-17 東洋インキＳｃホールディングス株式会社 Aqueous adhesive and adhesive sheet
WO2020158237A1 (en) * 2019-01-31 2020-08-06 横浜ゴム株式会社 Tire rubber composition and pneumatic tire using same
JP2020122109A (en) * 2019-01-31 2020-08-13 横浜ゴム株式会社 Rubber composition for tire, and pneumatic tire using the same
JP2020122110A (en) * 2019-01-31 2020-08-13 横浜ゴム株式会社 Rubber composition for tire and pneumatic tire using the same
JP2021020986A (en) * 2019-07-25 2021-02-18 マクセルホールディングス株式会社 Repeelable adhesive composition and adhesive tape
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Also Published As

Publication number Publication date
CN103534324A (en) 2014-01-22
KR20140012687A (en) 2014-02-03
JPWO2012133268A1 (en) 2014-07-28
KR101880420B1 (en) 2018-08-16
CN103534324B (en) 2015-12-23
JP5937570B2 (en) 2016-06-22

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