Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J11/00—Recovery or working-up of waste materials
  • C08J11/04—Recovery or working-up of waste materials of polymers
  • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J11/00—Recovery or working-up of waste materials
  • C08J11/04—Recovery or working-up of waste materials of polymers
  • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
  • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
  • C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
  • C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
  • C07C31/02—Monohydroxylic acyclic alcohols
  • C07C31/12—Monohydroxylic acyclic alcohols containing four carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/12—Hydrolysis
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J11/00—Recovery or working-up of waste materials
  • C08J11/02—Recovery or working-up of waste materials of solvents, plasticisers or unreacted monomers
• • 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
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/141—Feedstock
  • Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W30/00—Technologies for solid waste management
  • Y02W30/50—Reuse, recycling or recovery technologies
  • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

• the present invention relates to a method for producing a hydrophilic polymer.
• the present invention also relates to a method for producing an alcohol.
• Adhesive tape is used in large quantities for attaching labels to items and packaging materials, wrapping packaging materials, use in the manufacturing process of electronic and optical components, masking, etc. In recent years in particular, its use in the manufacturing process of electronic and optical components has increased, resulting in the generation of large amounts of waste adhesive tape at manufacturing sites and other locations.
• Waste adhesive tape is usually disposed of by incineration or by being taken to a waste disposal site. However, from the perspective of reducing the environmental impact and recycling resources, this type of disposal is not desirable.
• One possible way to reduce the waste disposal of adhesive tape is to recycle the material used in adhesive tape. If recycling technology for adhesive tape materials can be established, it is expected to have a significant effect on solving the problem of climate change, for example, by reducing the amount of CO2 emissions associated with the mining of fossil resources.
• Typical materials for adhesive tapes include an adhesive and a substrate.
• adhesive tapes are obtained by dissolving a polymer (sometimes called a base polymer) and additives such as a crosslinking agent, depending on the purpose, in a solvent to form an adhesive composition, which is then applied to a substrate, and heated and dried as necessary to promote a crosslinking reaction, forming an adhesive on the substrate (see, for example, Patent Document 1).
• Acrylic adhesives a typical adhesive, have a crosslinked structure in which the main chain and side chains are intricately entangled. This makes them difficult to handle and process when reused. Therefore, the present inventors have recently been studying the production of recycled acrylic polymers that can be used as raw materials for recycled adhesives as a technology for reusing acrylic adhesives, and as one of the techniques, they have been studying the hydrolysis of side chains using alkaline compounds. In order to advance this hydrolysis, it is necessary to relax the entangled molecular chains and increase the probability that the reaction points and the alkaline compounds will meet. To relax such molecular chains, a method of swelling the adhesive using an organic solvent that has a high affinity with hydrophobic acrylic adhesives is considered.
• the alkaline compounds required for hydrolysis are hydrophilic and therefore insoluble in organic solvents. Therefore, in order to swell the adhesive, it is important to select a treatment liquid that can dissolve the alkaline compounds and be miscible with organic solvents.
• the object of the present invention is to provide a method for producing a hydrophilic polymer as a recycled acrylic polymer that can be used as a raw material for recycled adhesives, and an alcohol as a by-product of the hydrolysis reaction, from an acrylic adhesive, without substantially using a treatment liquid such as a solvent.
• the inventors came up with the idea of adopting a physical approach as a technical means for relaxing the molecular chains. They then used a device that can efficiently apply high shear forces to the adhesive, such as a planetary mixer or kneader, to cause a solid-phase reaction between the acrylic adhesive and the alkaline compound without substantially using a treatment liquid such as a solvent, thereby solving the above problems.
• a device that can efficiently apply high shear forces to the adhesive, such as a planetary mixer or kneader, to cause a solid-phase reaction between the acrylic adhesive and the alkaline compound without substantially using a treatment liquid such as a solvent, thereby solving the above problems.
• this type of solid-phase reaction can physically increase the probability that the reaction points of the hydrolysis reaction and the alkaline compound will come into contact with each other, and it is presumed that the alkaline compound comes into direct contact with the reaction points of the hydrolysis reaction in a high concentration state.
• the hydrolysis reaction time can be dramatically shortened and that the yield of the hydrophilic polymer obtained as the recycled acrylic polymer is high.
• the alcohol produced together with the hydrophilic polymer can be obtained in high yield.
• a method for producing a hydrophilic polymer according to an embodiment of the present invention is a method for producing a hydrophilic polymer from an acrylic adhesive, and includes a reaction step of reacting the acrylic adhesive with an alkaline compound in a solid phase.
• the solid-phase reaction may be carried out by kneading the acrylic pressure-sensitive adhesive and the alkaline compound while applying a shear force.
• an alcohol may be produced by the reaction step.
• the method for producing a hydrophilic polymer according to any one of the above [1] to [3] may further include an alcohol recovery step of recovering an alcohol produced in the reaction step.
• the alcohol recovery step may be a step of recovering alcohol produced in the above reaction step under reduced pressure.
• an impurity separation step of separating impurities may be included.
• the method for producing a hydrophilic polymer according to any one of the above [1] to [6] may further include a drying step of drying the hydrophilic polymer.
• the acrylic pressure-sensitive adhesive may be an acrylic pressure-sensitive adhesive in a swollen gel state containing an organic solvent.
• the acrylic pressure-sensitive adhesive in a swollen gel state may have an organic solvent content of 50 wt % or less.
• a method for producing an alcohol according to an embodiment of the present invention is a method for producing an alcohol from an acrylic adhesive, and includes a reaction step of reacting the acrylic adhesive with an alkali compound in a solid phase.
• the solid-phase reaction may be carried out by kneading the acrylic pressure-sensitive adhesive and the alkali compound while applying a shear force.
• the acrylic pressure-sensitive adhesive may be an acrylic pressure-sensitive adhesive in a swollen gel state containing an organic solvent.
• the acrylic pressure-sensitive adhesive in a swollen gel state may have an organic solvent content of 50 wt % or less.
• a method for producing a hydrophilic polymer as a recycled acrylic polymer that can be used as a raw material for a recycled adhesive and an alcohol as a by-product of a hydrolysis reaction from an acrylic adhesive can be provided without substantially using a treatment liquid such as a solvent.
• the probability that the reaction point of the hydrolysis reaction and the alkaline compound physically meet can be improved, and therefore, it is presumed that the alkaline compound comes into direct contact with the reaction point of the hydrolysis reaction in a high concentration state, and as a result, the effect of dramatically shortening the reaction time of the hydrolysis and the effect of a high yield of the obtained hydrophilic polymer can be achieved, and the effect of a high yield of the alcohol produced together with the hydrophilic polymer can also be achieved.
• the alcohol is also produced by hydrolysis, and by recovering this (preferably under reduced pressure), the effect of highly efficient production of a high-purity alcohol can be achieved.
• the hydrolysis reaction which is an equilibrium reaction, becomes favorable toward the production of a hydrophilic polymer due to Le Chatelier's principle, and the effect of a higher yield of the hydrophilic polymer as a recycled acrylic polymer can be achieved.
• weight Whenever the term “weight” appears in this specification, it may be read as “mass,” which is the commonly used SI unit for indicating weight.
• (meth)acrylic means “acrylic and/or methacrylic
• the term “(meth)acrylate” means “acrylate and/or methacrylate
• the term “(meth)allyl” means “allyl and/or methallyl”
• the term “(meth)acrolein” means "acrolein and/or methacrolein”.
• a method for producing a hydrophilic polymer according to an embodiment of the present invention is a method for producing a hydrophilic polymer from an acrylic adhesive, and includes a reaction process for reacting an acrylic adhesive with an alkaline compound in a solid phase.
• Acrylic adhesives are obtained by a crosslinking reaction between an acrylic polymer as a base polymer and an acrylic adhesive composition containing a crosslinking agent, and have a crosslinked structure in which the main chain and side chains are intricately entangled.
• the method for producing a hydrophilic polymer according to an embodiment of the present invention by carrying out a solid-phase reaction between such an acrylic adhesive and an alkaline compound, the cleavage and hydrolysis reaction of the crosslinked structure of the crosslinked polymer, which is the main polymer component contained in the acrylic adhesive, proceeds extremely smoothly, and a hydrophilic polymer having a carboxyl group in the side chain can be produced without a significant decrease in molecular weight compared to the base polymer.
• the use of a solid-phase reaction can improve the probability that the reaction point of the hydrolysis reaction and the alkaline compound will physically come into contact with each other. Therefore, it is presumed that the alkaline compound comes into direct contact with the reaction point of the hydrolysis reaction in a high concentration state, which can result in the effects of dramatically shortening the hydrolysis reaction time and increasing the yield of the resulting hydrophilic polymer.
• Acrylic adhesive As the acrylic adhesive used in the method for producing a hydrophilic polymer according to the embodiment of the present invention, any suitable acrylic adhesive may be adopted as long as it does not impair the effects of the present invention.
• Representative examples of such acrylic adhesives include waste acrylic adhesives (sometimes referred to as "waste acrylic adhesives"). Examples of waste acrylic adhesives include acrylic adhesives contained in acrylic adhesive tapes collected after use, acrylic adhesives that remain on adherends when the acrylic adhesive tape is peeled off from the adherend to which the acrylic adhesive tape is attached, acrylic adhesives attached to an acrylic adhesive production device, and acrylic adhesives of scraps that do not become acrylic adhesive tape products after cutting into a predetermined product width.
• the acrylic adhesive may be formed by any suitable method.
• Such methods include, for example, a method of forming from an acrylic adhesive composition, and more specifically, a method of applying the acrylic adhesive composition to any suitable substrate, heating and drying as necessary, and curing as necessary to form an adhesive (specifically, an adhesive layer) on the substrate.
• application methods include, for example, a gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, air knife coater, spray coater, comma coater, direct coater, roll brush coater, die coater, etc.
• the acrylic adhesive composition preferably contains an acrylic polymer and a crosslinking agent, in that the effects of the present invention can be more effectively achieved.
• the acrylic polymer is what can be called a base polymer in the field of acrylic adhesives.
• the acrylic polymer may be of only one type, or may be of two or more types.
• the content of the acrylic polymer in the acrylic adhesive composition is preferably 50% by weight to 100% by weight, more preferably 60% by weight to 100% by weight, even more preferably 70% by weight to 100% by weight, particularly preferably 80% by weight to 100% by weight, and most preferably 90% by weight to 100% by weight, calculated as solid content.
• Any suitable acrylic polymer may be used as the acrylic polymer as long as it does not impair the effects of the present invention.
• the weight average molecular weight of the acrylic polymer is preferably 100,000 to 3,000,000, more preferably 150,000 to 2,000,000, even more preferably 200,000 to 1,500,000, and particularly preferably 250,000 to 1,000,000.
• the Tg (glass transition temperature) of the acrylic polymer is preferably -100°C to 30°C, more preferably -95°C to 20°C, even more preferably -90°C to 10°C, and particularly preferably -80°C to 0°C.
• the acrylic polymer is, for example, an acrylic polymer formed by polymerization from a composition (A) containing (component a) an alkyl (meth)acrylate ester in which the alkyl group in the alkyl ester moiety has 1 to 12 carbon atoms, and (component b) at least one selected from the group consisting of an ester of (meth)acrylate having an OH group and (meth)acrylic acid.
• component a) and (component b) may each independently be one type or two or more types.
• Examples of (meth)acrylic acid alkyl esters (component a) in which the alkyl group in the alkyl ester portion has 1 to 12 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl
• n-butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are preferred, and n-butyl acrylate and 2-ethylhexyl acrylate are more preferred, as they can better demonstrate the effects of the present invention.
• the at least one (b) selected from the group consisting of (meth)acrylic acid esters having an OH group and (meth)acrylic acid includes, for example, (meth)acrylic acid esters having an OH group, such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate, and (meth)acrylic acid.
• (meth)acrylic acid esters having an OH group such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate
• (meth)acrylic acid Among these, hydroxyethyl (meth)acrylate and (meth)acrylic acid are preferred, and hydroxyethyl acrylate and acrylic acid are more preferred, in terms of being able to more effectively exert the effects of the present invention.
• Composition (A) may contain a copolymerizable monomer other than components (a) and (b).
• the copolymerizable monomer may be of only one type, or of two or more types.
• Examples of such copolymerizable monomers include carboxyl group-containing monomers (excluding (meth)acrylic acid) such as itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, and acid anhydrides thereof (e.g., acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride); (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N-butyl ...
• Amide group-containing monomers such as acrylamide; amino group-containing monomers such as aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and t-butylaminoethyl (meth)acrylate; epoxy group-containing monomers such as glycidyl (meth)acrylate and methylglycidyl (meth)acrylate; cyano group-containing monomers such as acrylonitrile and methacrylonitrile; N-vinyl-2-pyrrolidone, (meth)acryloylmorpholine, N-vinylpiperidone, N-vinylpiperazine, N-vinylpyrrole, N-vinylimino Heterocyclic vinyl monomers such as vinyl oxazole, vinyl pyridine, vinyl pyrimidine, and vinyl oxazole; sulfonic acid group-containing monomers such as sodium vinyl sulfonate; phosphoric acid group-containing monomers such
• a polyfunctional monomer may also be used.
• a polyfunctional monomer is a monomer having two or more ethylenically unsaturated groups in one molecule.
• the ethylenically unsaturated group any appropriate ethylenically unsaturated group may be used as long as it does not impair the effects of the present invention.
• examples of such ethylenically unsaturated groups include radically polymerizable functional groups such as vinyl groups, propenyl groups, isopropenyl groups, vinyl ether groups (vinyloxy groups), and allyl ether groups (allyloxy groups).
• polyfunctional monomers examples include hexanediol di(meth)acrylate, butanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, allyl (meth)acrylate, vinyl (meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, etc.
• Such polyfunctional monomers may be used alone or in combination of two or more kinds.
• (meth)acrylic acid alkoxyalkyl esters may also be used.
• (meth)acrylic acid alkoxyalkyl esters include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, 3-methoxypropyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, and 4-ethoxybutyl (meth)acrylate. Only one type of (meth)acrylic acid alkoxyalkyl ester may be used, or two or more types may be used.
• the content of the (meth)acrylic acid alkyl ester (component a) in which the alkyl group in the alkyl ester portion has 1 to 12 carbon atoms is preferably 50% by weight or more, more preferably 60% to 100% by weight, even more preferably 70% to 100% by weight, and particularly preferably 80% to 100% by weight, based on the total amount (100% by weight) of the monomer components constituting the acrylic polymer, in order to further exert the effects of the present invention.
• the content of at least one selected from the group consisting of (meth)acrylic acid esters having an OH group and (meth)acrylic acid (component b) is preferably 0.1% by weight or more, more preferably 1.0% by weight to 50% by weight, even more preferably 1.5% by weight to 40% by weight, and particularly preferably 2.0% by weight to 30% by weight, based on the total amount (100% by weight) of the monomer components constituting the acrylic polymer, in order to further exert the effects of the present invention.
• Composition (A) may contain any appropriate other components as long as the effects of the present invention are not impaired.
• examples of such other components include a polymerization initiator, a chain transfer agent, and a solvent.
• the content of these other components may be any appropriate content as long as the effects of the present invention are not impaired. There may be only one type of such other components, or two or more types.
• the acrylic adhesive composition may contain a crosslinking agent.
• a crosslinking agent By using a crosslinking agent, the cohesive strength of the acrylic adhesive can be improved, and the effects of the present invention can be more effectively achieved.
• the crosslinking agent may be of only one type, or of two or more types.
• Crosslinking agents include polyfunctional isocyanate-based crosslinking agents, epoxy-based crosslinking agents, melamine-based crosslinking agents, peroxide-based crosslinking agents, as well as urea-based crosslinking agents, metal alkoxide-based crosslinking agents, metal chelate-based crosslinking agents, metal salt-based crosslinking agents, carbodiimide-based crosslinking agents, oxazoline-based crosslinking agents, aziridine-based crosslinking agents, and amine-based crosslinking agents.
• at least one selected from the group consisting of polyfunctional isocyanate-based crosslinking agents and epoxy-based crosslinking agents is preferred in terms of being able to further exert the effects of the present invention.
• polyfunctional isocyanate crosslinking agents include lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate; alicyclic polyisocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated xylene diisocyanate; and aromatic polyisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and xylylene diisocyanate.
• lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate
• alicyclic polyisocyanates such as cyclopen
• polyfunctional isocyanate crosslinking agents include commercially available products such as trimethylolpropane/tolylene diisocyanate adduct (manufactured by Mitsui Chemicals, Inc., product name "Takenate D101A”), trimethylolpropane/hexamethylene diisocyanate adduct (manufactured by Tosoh Corporation, product names "Coronate HL” and “Coronate HX”), and trimethylolpropane/xylylene diisocyanate adduct (manufactured by Mitsui Chemicals, Inc., product name "Takenate 110N”).
• trimethylolpropane/tolylene diisocyanate adduct manufactured by Mitsui Chemicals, Inc., product name "Takenate D101A
• trimethylolpropane/hexamethylene diisocyanate adduct manufactured by Tosoh Corporation, product names "Coronate HL” and “Coronate
• Epoxy crosslinking agents include, for example, N,N,N',N'-tetraglycidyl-m-xylylenediamine, diglycidylaniline, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether,
• Examples of epoxy crosslinking agents include glycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether,
• the content of the crosslinking agent in the acrylic adhesive composition may be any appropriate content within the range that does not impair the effects of the present invention.
• the content is preferably 0.1 to 20 parts by weight, more preferably 0.3 to 10 parts by weight, even more preferably 0.5 to 8.0 parts by weight, and particularly preferably 1.0 to 6.0 parts by weight, relative to the solid content (100 parts by weight) of the acrylic polymer.
• the acrylic adhesive composition may contain any other appropriate components as long as the effects of the present invention are not impaired.
• other components include polymer components other than acrylic polymers, crosslinking accelerators, crosslinking catalysts, silane coupling agents, tackifying resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), anti-aging agents, inorganic fillers, organic fillers, metal powders, colorants (pigments, dyes, etc.), foil-like materials, UV absorbers, antioxidants, light stabilizers, chain transfer agents, plasticizers, softeners, surfactants, antistatic agents, conductive agents, stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts, etc.
• polymer components other than acrylic polymers include crosslinking accelerators, crosslinking catalysts, silane coupling agents, tackifying resins (rosin derivatives, polyterpene resins, petroleum resins,
• alkali compound any suitable solid alkali compound may be used as long as it does not impair the effects of the present invention.
• alkali compounds include hydroxides and carbonates of alkali metals or alkaline earth metals, such as potassium hydroxide, sodium hydroxide, and calcium hydroxide, and metal alkoxides, such as sodium methoxide, sodium ethoxide, and potassium t-butoxide, and preferably at least one selected from the group consisting of potassium hydroxide, sodium hydroxide, and sodium ethoxide.
• reaction process In the reaction step, the acrylic adhesive and the alkaline compound are reacted in a solid phase.
• the amount of alkali compound used for the acrylic adhesive should be set to the amount required for hydrolysis of the acrylic adhesive. If a large amount of unreacted alkali is present in the product, post-treatment is required to deal with it.
• the amount of alkali compound used for the acrylic adhesive is typically preferably 0.5 to 1.2 molar equivalents, more preferably 0.8 to 1.1 molar equivalents, and even more preferably 0.9 to 1.1 molar equivalents, per 1 molar equivalent of the acrylic adhesive base polymer.
• a solid-state reaction is a reaction in which an acrylic adhesive and an alkali compound (typically a solid alkali compound) are reacted in a solid state without substantially using any liquid such as a solvent.
• an acrylic adhesive and an alkali compound typically a solid alkali compound
• any liquid such as a solvent.
• "without substantially using” here means that no liquid is intentionally added from the outside for the purpose of involving it in the reaction, and the unintentional and unavoidable mixing of liquid into the reaction system, for example, the mixing of water due to moisture from the reaction atmosphere, is included in the above "without substantially using.”
• liquids such as solvents that may be originally contained in the acrylic adhesive to the extent that they do not inhibit its solid state are not considered to fall under the above-mentioned "substantially using a treatment liquid such as a solvent.”
• the acrylic adhesive to be reacted with the alkali compound in the solid-state reaction is an acrylic adhesive in a swollen gel state containing an organic solvent.
• the content of the organic solvent in the acrylic adhesive in a swollen gel state may be any appropriate content ratio as long as it can express a swollen gel state.
• the content of the organic solvent in such an acrylic adhesive in a swollen gel state is preferably 50% by weight or less.
• the content of the organic solvent in the acrylic adhesive in a swollen gel state may be treated as the same ratio as the ratio of the amount of the organic solvent added to the total amount of the acrylic adhesive before the organic solvent is added and the organic solvent added.
• any appropriate organic solvent can be used as long as it does not impair the effects of the present invention.
• the organic solvent may be one type or two or more types.
• alcohols are preferable.
• any appropriate alcohol can be used as long as it does not impair the effects of the present invention. Examples of such alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, cyclohexanol, benzyl alcohol, 1-heptanol, 1-octanol, and 2-ethylhexanol.
• organic solvents other than alcohols can also be used as the organic solvent.
• an organic solvent for example, a solvent that has high affinity with the acrylic adhesive, such as a hydrocarbon solvent (hexane, heptane, octane, nonane, decane, toluene, methylcyclohexane, etc.), a ketone solvent (acetone, methyl ethyl ketone, etc.), or an ether solvent (diethyl ether, cyclopentyl methyl ether, etc.), can be selected.
• a hydrocarbon solvent hexane, heptane, octane, nonane, decane, toluene, methylcyclohexane, etc.
• a ketone solvent acetone, methyl ethyl ketone, etc.
• an ether solvent diethyl ether, cyclopentyl methyl ether, etc.
• the organic solvents that can be added to the acrylic adhesive are not limited to these.
• waste acrylic adhesive (sometimes referred to as "waste acrylic adhesive").
• waste acrylic adhesive include acrylic adhesive contained in acrylic adhesive tape collected after use, acrylic adhesive remaining on an adherend when the acrylic adhesive tape is peeled from the adherend to which the acrylic adhesive tape is attached, and acrylic adhesive attached to an acrylic adhesive manufacturing device.
• acrylic adhesive is used as is, without substantially using a liquid such as a solvent.
• the solid-phase reaction can be carried out by any suitable method as long as it can be carried out in a solid state without substantially using a liquid such as a solvent, so long as the effect of the present invention is not impaired.
• the solid-phase reaction is preferably carried out by applying a shear force to the acrylic adhesive and the alkaline compound and kneading them.
• One preferable index for selecting a means for kneading by applying a shear force is to use a kneading device capable of applying a shear force [Pa] equivalent to the storage modulus [Pa] of the acrylic pressure-sensitive adhesive (typically, 10 3 Pa to 10 9 Pa).
• kneading devices include a planetary mixer, a kneader, a kneadex, a single-screw extruder, and a twin-screw extruder.
• Another preferred selection index for the means for kneading by applying a shear force is to use a kneading device with a high stirring intensity [kW/m 3 ].
• a stirring intensity [kW/m 3 ] is preferably 25 kW/m 3 or more, more preferably 40 kW/m 3 or more, even more preferably 60 kW/m 3 or more, and particularly preferably 80 kW/m 3 or more.
• Examples of kneading devices having such stirring intensity include a planetary mixer, a kneader, a kneadex, a single-screw extruder, and a twin-screw extruder.
• the stirring strength is also calculated from the ratio of the rated current value [A] of the device and the material capacity [L].
• Such a stirring strength is preferably 0.9 A/L or more, more preferably 1.0 A/L or more, even more preferably 1.1 A/L or more, and particularly preferably 1.2 or more.
• Examples of kneading devices having such a stirring strength include planetary mixers, kneaders, kneadex, single-screw extruders, and twin-screw extruders.
• the acrylic adhesive and the alkaline compound are preferably added to the kneading device as described above and kneaded.
• the order of adding the acrylic adhesive and the alkaline compound to the kneading device may be either first or simultaneously.
• the order of adding the acrylic adhesive and the alkaline compound to the kneading device is preferably such that the acrylic adhesive is added to the kneading device and then the alkaline compound is added, and more preferably, the acrylic adhesive is added to the kneading device and pre-mixed, and then the alkaline compound is added to the kneading device.
• the pre-mixing time may be set to any appropriate time within a range that does not impair the effects of the present invention.
• the pre-mixing time is preferably 10 seconds to 30 minutes, more preferably 30 seconds to 20 minutes, and even more preferably 1 minute to 10 minutes.
• the alkaline compound may be pulverized before being added to the kneading device.
• a hydrolysis reaction takes place within the reaction system (typically within a kneading device), producing alcohol as a liquid or its vapor, and a solid mixture containing a hydrophilic polymer.
• a hydrolysis reaction progresses within the reaction system (typically within a kneading device) due to a solid-phase reaction between the acrylic adhesive and the alkaline compound, producing alcohol as a liquid or its vapor, and obtaining a solid mixture containing a hydrophilic polymer.
• the method for producing a hydrophilic polymer according to the embodiment of the present invention may include an alcohol recovery step of recovering the alcohol produced in the reaction step.
• the alcohol produced in the reaction process is recovered.
• Any appropriate method may be adopted as the method for recovering the alcohol, provided that the effects of the present invention are not impaired.
• One such method that can further enhance the effects of the present invention is reduced pressure recovery.
• such a reduced pressure recovery method involves reducing the pressure in the reaction system (typically in the kneading device) to trap and recover the alcohol generated in the reaction system (typically in the kneading device).
• the alcohol can be forcibly removed from the reaction system (typically from the kneading device).
• This makes the hydrolysis reaction, which is an equilibrium reaction, more favorable for the production of hydrophilic polymers due to Le Chatelier's principle, which can have the effect of increasing the yield of hydrophilic polymers.
• the method for producing a hydrophilic polymer according to the embodiment of the present invention may include an impurity separation step of separating impurities.
• impurities are separated from the solid mixture containing the hydrophilic polymer obtained in the reaction step. Any appropriate method may be adopted as a method for separating impurities from a solid mixture containing a hydrophilic polymer, as long as it does not impair the effects of the present invention.
• Examples of such methods that can further express the effects of the present invention include (1) a method in which the solid mixture containing the hydrophilic polymer is dissolved in any appropriate liquid (typically water), and the remaining alkaline compounds are neutralized with an acid (e.g., acetic acid) as necessary, and then the impurities are separated by centrifugation, and (2) a method in which the solid mixture containing the hydrophilic polymer is washed with any appropriate washing liquid (e.g., ethyl acetate/methanol mixed solvent) to separate the impurities.
• any appropriate washing liquid e.g., ethyl acetate/methanol mixed solvent
• the impurities are separated from the solid mixture containing the hydrophilic polymer by the impurity separation process, and the hydrophilic polymer is obtained.
• the method for producing a hydrophilic polymer according to the embodiment of the present invention may include a drying step of drying the hydrophilic polymer.
• the hydrophilic polymer obtained in the impurity separation step is dried.
• Any appropriate drying conditions may be adopted as long as they do not impair the effects of the present invention.
• Such conditions include, for example, a drying temperature of 80°C to 150°C and a drying time of 0.5 hours to 20 hours.
• the method for producing an alcohol according to the embodiment of the present invention may include any appropriate other step as long as the effect of the present invention is not impaired.
• Alcohol production method ⁇ In the method for producing a hydrophilic polymer according to the embodiment of the present invention, as described above, alcohol is produced by hydrolysis. Therefore, the method for producing a hydrophilic polymer according to the embodiment of the present invention can be considered as a method for producing alcohol from an acrylic adhesive, and includes a reaction step of reacting the acrylic adhesive with an alkali compound in a solid phase.
• Acrylic adhesives are obtained by a crosslinking reaction between an acrylic polymer as a base polymer and an acrylic adhesive composition containing a crosslinking agent, and have a crosslinked structure in which the main chain and side chains are intricately entangled.
• the cleavage and hydrolysis reaction of the crosslinked structure of the crosslinked polymer, which is the main polymer component contained in the acrylic adhesive proceeds extremely smoothly, and alcohol can be produced.
• the use of a solid-phase reaction can improve the probability that the reaction point of the hydrolysis reaction and the alkaline compound will physically come into contact with each other. Therefore, it is presumed that the alkaline compound comes into direct contact with the reaction point of the hydrolysis reaction in a high concentration state, which can result in the effects of dramatically shortening the hydrolysis reaction time and increasing the yield of the produced alcohol.
• Acrylic adhesive used in the alcohol production method according to the embodiment of the present invention, the explanation in ⁇ 1-1. Acrylic adhesive> may be used.
• Alkaline compounds used in the alcohol production method according to the embodiment of the present invention, the explanation in ⁇ 1-2. Alkaline compounds> may be used.
• reaction steps in the alcohol production method according to an embodiment of the present invention the explanation in ⁇ 1-3. Reaction steps> may be used.
• the method for producing alcohol according to an embodiment of the present invention may include an alcohol recovery process for recovering the alcohol produced by the reaction process.
• an alcohol recovery process for recovering the alcohol produced by the reaction process.
• the explanation in ⁇ 1-4. Alcohol recovery process> may be used.
• the method for producing alcohol according to the embodiment of the present invention may include any other appropriate steps as long as they do not impair the effects of the present invention.
• the carboxylation rate was calculated from the ratio of the peak intensities of (meth)acrylic acid and (meth)acrylic acid ester in the product in 13 C-NMR.
• an acrylic pressure-sensitive adhesive (A) was produced as follows. A four-neck flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a cooler was charged with 95 parts by weight of butyl acrylate (BA) and 5 parts by weight of acrylic acid (AA) as monomers, 0.2 parts by weight of 2,2'-azobisisobutyronitrile as a polymerization initiator, and 233 parts by weight of ethyl acetate. Nitrogen gas was introduced while gently stirring, and the mixture was heated to 60°C.
• BA butyl acrylate
• AA acrylic acid
• AA 2,2'-azobisisobutyronitrile
• An acrylic pressure-sensitive adhesive composition was obtained by mixing 100 parts by weight (solid content) of an acrylic polymer (a), 5 parts by weight of an isocyanate compound (Takenate D101A, manufactured by Mitsui Chemicals, Inc.) as a crosslinking agent, and 0.03 parts by weight of EMBIRIZER OL-1 (manufactured by Tokyo Fine Chemicals Co., Ltd.) as a catalyst, and diluting with ethyl acetate to a total solid content of 20% by weight.
• an isocyanate compound Takenate D101A, manufactured by Mitsui Chemicals, Inc.
• EMBIRIZER OL-1 manufactured by Tokyo Fine Chemicals Co., Ltd.
• the obtained acrylic pressure-sensitive adhesive composition was applied to a polyethylene terephthalate film (product name "T100", thickness 50 ⁇ m, manufactured by Mitsubishi Chemical Corporation) so as to give a thickness of 10 ⁇ m after drying, and cured and dried under conditions of a drying temperature of 130° C. and a drying time of 30 seconds to produce an acrylic pressure-sensitive adhesive (A).
• a polyethylene terephthalate film product name "T100", thickness 50 ⁇ m, manufactured by Mitsubishi Chemical Corporation
• an acrylic pressure-sensitive adhesive (B) was produced as follows. A four-neck flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a cooler was charged with the following monomers: 64 parts by weight of ethyl acrylate (EA), 28 parts by weight of 2-ethylhexyl acrylate (2EHA), 5 parts by weight of methyl methacrylate (MMA), 4 parts by weight of hydroxyethyl acrylate (HEA), and 0.2 parts by weight of benzoyl peroxide and 233 parts by weight of ethyl acetate as polymerization initiators.
• EA ethyl acrylate
• 2EHA 2-ethylhexyl acrylate
• MMA methyl methacrylate
• HOA hydroxyethyl acrylate
• benzoyl peroxide and 233 parts by weight of ethyl acetate as polymerization initiators.
• An acrylic pressure-sensitive adhesive composition was obtained by mixing 100 parts by weight (solid content) of an acrylic polymer (b), 1.45 parts by weight of an isocyanate compound (Takenate D101A, manufactured by Mitsui Chemicals, Inc.) as a crosslinking agent, and 0.053 parts by weight of EMBIRIZER OL-1 (manufactured by Tokyo Fine Chemicals Co., Ltd.) as a catalyst, and diluting with ethyl acetate so that the total solid content became 20% by weight.
• solid content solid content
• an acrylic polymer (b) 1.45 parts by weight of an isocyanate compound (Takenate D101A, manufactured by Mitsui Chemicals, Inc.) as a crosslinking agent
• EMBIRIZER OL-1 manufactured by Tokyo Fine Chemicals Co., Ltd.
• the obtained acrylic pressure-sensitive adhesive composition was applied to a release-treated polyethylene terephthalate film (product name "Diafoil MRF", thickness 38 ⁇ m, manufactured by Mitsubishi Chemical Corporation) so that the thickness after drying would be 10 ⁇ m, and cured and dried under conditions of a drying temperature of 130° C. and a drying time of 30 seconds to produce an acrylic pressure-sensitive adhesive (B).
• a release-treated polyethylene terephthalate film product name "Diafoil MRF", thickness 38 ⁇ m, manufactured by Mitsubishi Chemical Corporation
• Example 1 100 g of the acrylic pressure sensitive adhesive (A) obtained in Production Example 1 was prepared and charged into a planetary mixer (Hivis Dispermix 3D-2 model, manufactured by Primix Corporation) as a reaction apparatus, and pre-mixing was carried out for 5 minutes. Subsequently, 54 g of pulverized potassium hydroxide (KOH, purity 85%) was added, and stirring was continued for 0.5 hours while increasing the stirring speed. As the reaction proceeded, steam and liquid were generated in the reactor, and the pressure in the reactor was reduced, and the generated steam and liquid were collected under reduced pressure in a trap can cooled with chiller water at 5°C. The weight of the collected liquid was 50 g.
• KOH pulverized potassium hydroxide
• Example 2 3.5 kg of the acrylic pressure sensitive adhesive (A) obtained in Production Example 1 was prepared and charged into a twin-arm kneader (TK5-2 type, manufactured by Toshin Co., Ltd.) as a reaction apparatus, and pre-mixed for 5 minutes. Subsequently, 1.87 kg of pulverized potassium hydroxide (KOH, purity 85%) was added, and stirring was continued for 0.5 hours while increasing the stirring speed. As the reaction proceeded, steam and liquid were generated in the reactor, and the pressure in the reactor was reduced, and the generated steam and liquid were collected under reduced pressure in a trap can cooled with chiller water at 5°C. The weight of the collected liquid was 1.7 kg.
• KOH pulverized potassium hydroxide
• Example 3 3.5 kg of the acrylic pressure sensitive adhesive (A) obtained in Production Example 1 was prepared and charged into a Trimix (manufactured by Inoue Seisakusho, equivalent to a planetary mixer) as a reaction apparatus, and pre-mixing was carried out for 5 minutes. Subsequently, 1.17 kg of pulverized sodium hydroxide (NaOH, purity 97%) was added, and stirring was continued for 0.9 hours while increasing the stirring speed. As the reaction proceeded, steam and liquid were generated in the reactor, and the pressure in the reactor was reduced, and the generated steam and liquid were collected under reduced pressure in a trap can cooled with chiller water at 5°C. The weight of the collected liquid was 1.7 kg.
• Trimix manufactured by Inoue Seisakusho, equivalent to a planetary mixer
• Example 4 3.5 kg of the acrylic pressure sensitive adhesive (A) obtained in Production Example 1 was prepared and charged into a Trimix (manufactured by Inoue Seisakusho, equivalent to a planetary mixer) as a reaction apparatus, and pre-mixing was carried out for 5 minutes. Subsequently, 1.87 kg of pulverized potassium hydroxide (KOH, purity 85%) was added, and stirring was continued for 0.5 hours while increasing the stirring speed. As the reaction proceeded, steam and liquid were generated in the reactor, and the pressure in the reactor was reduced, and the generated steam and liquid were collected under reduced pressure in a trap can cooled with chiller water at 5°C. The weight of the collected liquid was 1.7 kg.
• KOH pulverized potassium hydroxide
• Example 5 3 kg of the acrylic pressure sensitive adhesive (B) obtained in Production Example 2 was prepared and charged into a Trimix reactor (TX-15, manufactured by Inoue Seisakusho) and pre-mixed for 5 minutes. Subsequently, 1.6 kg of pulverized potassium hydroxide (KOH, purity 85%) was added, and stirring was continued for 5 hours while increasing the stirring speed. As the reaction proceeded, steam and liquid were generated in the reactor, and the pressure in the reactor was reduced, and the generated steam and liquid were collected under reduced pressure in a solvent recovery device (COVEX, CA103) cooled with chiller water at 15°C. The weight of the collected liquid was 0.1 kg.
• TX-15 Trimix reactor
• KOH pulverized potassium hydroxide
• Example 6 5 kg of the acrylic adhesive (A) obtained in Production Example 1 was prepared and charged in portions into a planetary mixer (PLM-15, manufactured by Inoue Seisakusho) as a reaction device, and stirring was continued while charging 2.5 kg of 1-butanol as a viscosity modifier in portions, until the mixture was mixed uniformly. As a result, the acrylic adhesive (A) was swelled by the 1-butanol, and became an acrylic adhesive in a swollen gel state. Subsequently, 2.8 kg of pulverized potassium hydroxide (KOH, purity 85%) was added, and stirring was continued for 3 hours while increasing the stirring speed.
• KOH pulverized potassium hydroxide
• the generated alcohol dissolved in the solution.
• the structure of the main component of the generated alcohol was confirmed by NMR (AVANCEIII-600 with Cryo Probe, manufactured by Bruker Biospin), and it was confirmed to be 1-butanol.
• the precipitate was washed with ethyl acetate and then dried at 130° C. for 2 hours to obtain polyacrylic acid, a hydrophilic polymer.
• the structure of the obtained polyacrylic acid was analyzed by NMR (AVANCEIII-600 with Cryo Probe, manufactured by Bruker Biospin). The results are shown in Table 1.
• the generated alcohol dissolved in the solution.
• the structure of the main component of the generated alcohol was confirmed by NMR (AVANCEIII-600 with Cryo Probe, manufactured by Bruker Biospin), and it was confirmed to be 1-butanol.
• the precipitate was washed with ethyl acetate and then dried at 130° C. for 2 hours to obtain polyacrylic acid, a hydrophilic polymer.
• the structure of the obtained polyacrylic acid was analyzed by NMR (AVANCEIII-600 with Cryo Probe, manufactured by Bruker Biospin). The results are shown in Table 1.
• hydrophilic polymer manufacturing method and alcohol manufacturing method according to the embodiment of the present invention can be suitably used, for example, in recycling technology for adhesive tape materials.

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• 2023
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