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
  • C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
  • C08J11/08—Recovery or working-up of waste materials of polymers without chemical reactions using selective solvents for polymer components
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
  • B29B17/02—Separating plastics from other materials
• • 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
  • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/04—Acids; Metal salts or ammonium salts thereof
  • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• • 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
  • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
• • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions 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; Compositions of derivatives of such polymers
  • C08L33/02—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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions 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; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions 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; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/10—Homopolymers or copolymers of methacrylic 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
  • 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
  • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
  • B29B17/02—Separating plastics from other materials
  • B29B2017/0203—Separating plastics from plastics
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
  • B29B17/02—Separating plastics from other materials
  • B29B2017/0213—Specific separating techniques
  • B29B2017/0293—Dissolving the materials in gases or liquids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
  • B29B17/02—Separating plastics from other materials
  • B29B2017/0213—Specific separating techniques
  • B29B2017/0293—Dissolving the materials in gases or liquids
  • B29B2017/0296—Dissolving the materials in aqueous alkaline solutions, e.g. NaOH or KOH
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2007/00—Flat articles, e.g. films or sheets
  • B29L2007/007—Narrow strips, e.g. ribbons, tapes, bands
• • 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
• • 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
  • C08J2333/02—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
  • C08J2333/04—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 esters
  • C08J2333/06—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 esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2312/00—Crosslinking
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
  • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2433/00—Presence of (meth)acrylic polymer
• • 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 water-soluble polymer.
• the present invention also relates to methods of making water-absorbing polymers.
• the invention also relates to water-soluble polymers.
• the present invention also relates to water-absorbing polymers.
• a method for producing such a hydrophilic polymer for example, a technique for producing a hydrophilic polymer by heating a monomer to about 175° C. in the presence of a catalyst to polymerize it has been reported (Patent Document 1).
• Patent Document 1 it is necessary to select extremely high temperature conditions exceeding 150°C, and there is a limit to improving the production efficiency of the hydrophilic polymer.
• hydrophilic polymers such as water-soluble polymers and water-absorbing polymers, which have a wide range of industrial applications, can be recycled from waste under mild conditions, which will greatly contribute to the reduction of environmental load. In this case, it would be very favorable if the waste, which can be generated in large quantities, can be utilized.
• An object of the present invention is to provide a method for producing a water-soluble polymer capable of producing a water-soluble polymer from an adhesive under mild conditions, a method for producing a water-absorbing polymer capable of producing a water-absorbing polymer from an adhesive under mild conditions, and a method for producing a water-absorbing polymer from an adhesive.
• the object of the present invention is to provide a water-soluble polymer that can be made from a pressure-sensitive adhesive.
• a method for producing a water-soluble polymer according to an embodiment of the present invention comprises: An adhesive treatment liquid containing a liquid having a Hansen solubility parameter value of 31 or less and an alkali compound, wherein the concentration of the alkali compound in the adhesive treatment liquid is 0.001% by weight to 20% by weight. is brought into contact with the adhesive.
• the liquid has a Hansen solubility parameter value of 15 or more and 25 or less, and the liquid contains a lower alcohol.
• the adhesive is composed of an acrylic adhesive.
• the concentration of the alkaline compound in the treatment liquid is 0.01% by weight to 10% by weight.
• a water-soluble polymer according to an embodiment of the present invention is a water-soluble polymer obtained by a method for producing a water-soluble polymer according to an embodiment of the present invention, comprising a structural unit (1) represented by the following formula and and a structural unit (2).
• R 1 represents a hydrogen atom or a methyl group.
• R 2 represents an alkyl group having 1 to 12 carbon atoms.
• M represents a hydrogen atom or a cation.
• the method for producing a water-absorbing polymer according to the embodiment of the present invention reacts the water-soluble polymer obtained by the method for producing a water-soluble polymer according to the embodiment of the present invention with a cross-linking agent.
• a method for producing a water-absorbent polymer according to an embodiment of the present invention is an adhesive treatment liquid containing a liquid having a Hansen solubility parameter value of 31 or less and an alkaline compound, wherein the concentration of the alkaline compound in the adhesive treatment liquid is 0. 001% to 20% by weight of the adhesive treatment liquid, the cross-linking agent, and the adhesive are brought into contact with each other.
• the water-absorbing polymer according to the embodiment of the present invention comprises a structural unit (1) represented by the following formula, a structural unit (2) represented by the following formula, and a structural unit (1) and / or a structural unit (2) and crosslinked and a crosslinked structure formed by reaction with the agent.
• R 1 represents a hydrogen atom or a methyl group.
• R 2 represents an alkyl group having 1 to 12 carbon atoms.
• M represents a hydrogen atom or a cation.
• a method for producing a water-soluble polymer capable of producing a water-soluble polymer from an adhesive under mild conditions a method for producing a water-absorbing polymer capable of producing a water-absorbing polymer from an adhesive under mild conditions, and a method for producing a water-absorbing polymer from an adhesive It is possible to provide a water-soluble polymer that can be used and a water-absorbing polymer that can be produced from an adhesive.
• weight When the term “weight” is used in this specification, it may be read as “mass”, which is commonly used as an SI unit indicating weight.
• (meth) acrylic when used in this specification, it means “acrylic and/or methacrylic", and when the expression “(meth) acrylate” is used, “acrylate and/or methacrylate ", and the expression “(meth)allyl” means “allyl and/or methallyl”, and the expression “(meth)acrolein” means “acrolein and/or methacrolein”. means rain.
• Adhesive Any appropriate pressure-sensitive adhesive may be employed as the pressure-sensitive adhesive used as a raw material for the water-soluble polymer as long as the effects of the present invention are not impaired.
• Such adhesives typically include adhesives as waste, for example, adhesives contained in adhesive tapes collected after use, and adhesives from adherends to which the adhesive tape is attached. Adhesive that remains on the adherend when the tape is peeled off, and adhesive that adheres to an adhesive manufacturing apparatus.
• a pressure-sensitive adhesive tape typically includes an adhesive layer and a substrate made of an adhesive.
• the pressure-sensitive adhesive layer may consist of only one layer, or may consist of two or more layers.
• adherends examples include silicon wafers, semiconductor circuit boards, electronic devices such as ceramic capacitors, and optical materials such as optical films and optical glass. What is done is mentioned.
• Adhesive manufacturing equipment includes, for example, polymerization tanks, compounding equipment, and coating machines.
• the adhesive is in the form of an adhesive layer contained in the adhesive tape, in the form of an adhesive residue on the adherend, or in the form of an adhesive that adheres to manufacturing equipment such as polymerization tanks, blending equipment, and coating machines. Since it is in the form of an adhesive, it has various sizes and shapes. For example, if it is in the form of an adhesive layer contained in an adhesive tape, the thickness of the adhesive tape is preferably 1 ⁇ m to 2000 ⁇ m in that the effect of the present invention can be more expressed.
• the adhesive is preferably composed of at least one selected from the group consisting of acrylic adhesives, urethane adhesives, rubber adhesives, and silicone adhesives, more preferably acrylic adhesives and urethane adhesives. It is composed of at least one selected from the group consisting of a pressure-sensitive adhesive composition and a silicone-based pressure-sensitive adhesive composition, more preferably an acrylic pressure-sensitive adhesive.
• the adhesive can be formed by any suitable method.
• a method for example, at least one selected from the group consisting of an adhesive composition (acrylic adhesive composition, urethane adhesive composition, rubber adhesive composition, silicone adhesive composition ) is applied to any appropriate substrate, heated and dried as necessary, and cured as necessary to form an adhesive (specifically, an adhesive layer) on the substrate.
• coating methods include gravure roll coaters, reverse roll coaters, kiss roll coaters, dip roll coaters, bar coaters, knife coaters, air knife coaters, spray coaters, comma coaters, direct coaters, roll brush coaters, A method such as a die coater can be used.
• An acrylic pressure-sensitive adhesive is formed from an acrylic pressure-sensitive adhesive composition.
• the acrylic pressure-sensitive adhesive composition preferably contains an acrylic polymer and a cross-linking agent from the viewpoint that the effects of the present invention can be expressed more effectively.
• the acrylic polymer can be called a so-called base polymer in the field of acrylic adhesives. Only one type of acrylic polymer may be used, or two or more types may be used.
• the content of the acrylic polymer in the acrylic pressure-sensitive adhesive composition is preferably 50% to 100% by weight, more preferably 60% to 100% by weight, and still more preferably 70% by weight in terms of solid content. % to 100% by weight, particularly preferably 80% to 100% by weight, most preferably 90% to 100% by weight.
• Any appropriate acrylic polymer can be adopted 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 from 100,000 to 3,000,000, more preferably from 150,000 to 2,000,000, from the viewpoint that the effects of the present invention can be exhibited more, More preferably 200,000 to 1,500,000, and particularly preferably 250,000 to 1,000,000.
• the acrylic polymer is preferably (component a) an alkyl (meth)acrylate having 4 to 12 carbon atoms in the alkyl group of the alkyl ester moiety, (b Component) An acrylic polymer formed by polymerization from a composition (A) containing at least one member selected from the group consisting of (meth)acrylic acid esters having an OH group and (meth)acrylic acid.
• Component a) and (Component b) may each independently be one kind or two or more kinds.
• Examples of the (meth)acrylic acid alkyl ester (component a) in which the alkyl group of the alkyl ester moiety has 4 to 12 carbon atoms include n-butyl (meth)acrylate, isobutyl (meth)acrylate, and (meth)acrylate.
• s-butyl acrylate t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-(meth)acrylate Ethylhexyl, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate etc.
• n-butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are preferred, and n-butyl acrylate and acrylic are more preferred, in that the effects of the present invention can be more expressed.
• At least one (component b) selected from the group consisting of (meth)acrylic acid esters having an OH group and (meth)acrylic acid includes, for example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, Examples thereof include (meth)acrylic acid esters having an OH group such as hydroxybutyl (meth)acrylate, and (meth)acrylic acid.
• hydroxyethyl (meth)acrylate and (meth)acrylic acid are preferred, and hydroxyethyl acrylate and acrylic acid are more preferred, from the viewpoint that the effects of the present invention can be exhibited more.
• the composition (A) may contain copolymerizable monomers other than the components (a) and (b).
• the number of copolymerizable monomers may be one, or two or more.
• Such copolymerizable monomers include, for example, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, acid anhydrides thereof (for example, acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride).
• a polyfunctional monomer can also be employed as a copolymerizable monomer.
• a polyfunctional monomer refers to a monomer having two or more ethylenically unsaturated groups in one molecule.
• any suitable ethylenically unsaturated group can be adopted as long as the effects of the present invention are not impaired.
• Such ethylenically unsaturated groups include, for example, 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, and neopentyl glycol.
• (Meth)acrylic acid alkoxyalkyl esters may also be employed as copolymerizable monomers.
• Examples of (meth)acrylic acid alkoxyalkyl esters include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, and 3-(meth)acrylate. methoxypropyl, 3-ethoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, 4-ethoxybutyl (meth)acrylate and the like.
• the (meth)acrylic acid alkoxyalkyl ester may be used alone or in combination of two or more.
• the content of the (meth)acrylic acid alkyl ester (ingredient a) in which the alkyl group of the alkyl ester portion has 4 to 12 carbon atoms is the monomer constituting the acrylic polymer in that the effect of the present invention can be expressed more.
• the total amount of components (100% by weight) it is preferably 50% by weight or more, more preferably 60% by weight to 100% by weight, still more preferably 70% by weight to 100% by weight, particularly preferably 80% by weight. % to 100% by weight.
• the content of at least one (component b) selected from the group consisting of (meth)acrylic acid esters having an OH group and (meth)acrylic acid is such that the effects of the present invention can be more expressed, and the acrylic polymer is It is preferably 0.1% by weight or more, more preferably 1.0% to 50% by weight, still more preferably 1.5% to 40% by weight, based on the total amount (100% by weight) of the constituent monomer components. % by weight, particularly preferably 2.0% to 30% by weight.
• the sum of the above (component a), the above (component b) and a carboxyl group-containing monomer is preferably 5% to 95% by weight, more preferably 10% to 95% by weight, more preferably 15% to 95% by weight, more preferably 20% to 95% by weight, more preferably 25% to 95% by weight, more preferably 30% by weight % to 95% by weight, particularly preferably 35% to 90% by weight, most preferably 40% to 90% by weight.
• composition (A) may contain any appropriate other component within a range that does not impair the effects of the present invention.
• Such other components include, for example, polymerization initiators, chain transfer agents, solvents and the like. Any appropriate content can be adopted as the content of these other components as long as the effects of the present invention are not impaired.
• a thermal polymerization initiator or a photopolymerization initiator can be used as the polymerization initiator. Only one polymerization initiator may be used, or two or more polymerization initiators may be used.
• a thermal polymerization initiator can preferably be employed when obtaining an acrylic polymer by solution polymerization.
• thermal polymerization initiators include azo polymerization initiators, peroxide polymerization initiators (eg, dibenzoyl peroxide, tert-butyl permaleate, etc.), redox polymerization initiators, and the like.
• the azo initiators disclosed in JP-A-2002-69411 are particularly preferred.
• Such an azo polymerization initiator is preferable in that the decomposition product of the polymerization initiator is less likely to remain in the acrylic polymer as a portion that causes the generation of heat-generated gas (outgas).
• azo polymerization initiator 2,2'-azobisisobutyronitrile (hereinafter sometimes referred to as AIBN), 2,2'-azobis-2-methylbutyronitrile (hereinafter referred to as AMBN) ), 2,2′-azobis(2-methylpropionate)dimethyl, 4,4′-azobis-4-cyanovaleric acid, and the like.
• AIBN 2,2'-azobisisobutyronitrile
• AMBN 2,2'-azobis-2-methylbutyronitrile
• 2,2′-azobis(2-methylpropionate)dimethyl 4,4′-azobis-4-cyanovaleric acid
• the amount of the azo polymerization initiator used is preferably 0.01 to 5.0 parts by weight, more preferably 0.05 parts by weight, relative to the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer. 0.15 to 3.0 parts by weight, most preferably 0.1 to 3.0 parts by weight, more preferably 0.1 to 3.0 parts by weight. 20 parts by
• a photopolymerization initiator can preferably be employed when obtaining an acrylic polymer by active energy ray polymerization.
• photopolymerization initiators include benzoin ether-based photopolymerization initiators, acetophenone-based photopolymerization initiators, ⁇ -ketol-based photopolymerization initiators, aromatic sulfonyl chloride-based photopolymerization initiators, and photoactive oxime-based photopolymerization initiators.
• benzoin-based photopolymerization initiators benzyl-based photopolymerization initiators, benzophenone-based photopolymerization initiators, ketal-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, and the like.
• benzoin ether-based photopolymerization initiators examples include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethan-1-one, and anisole. and methyl ether.
• Acetophenone-based photopolymerization initiators include, for example, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 4-phenoxydichloroacetophenone, and 4-(t-butyl). and dichloroacetophenone.
• Examples of ⁇ -ketol photopolymerization initiators include 2-methyl-2-hydroxypropiophenone, 1-[4-(2-hydroxyethyl)phenyl]-2-methylpropan-1-one, and the like.
• Examples of aromatic sulfonyl chloride photopolymerization initiators include 2-naphthalenesulfonyl chloride.
• Examples of photoactive oxime-based photopolymerization initiators include 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime.
• Benzoin-based photopolymerization initiators include, for example, benzoin.
• Examples of benzyl-based photopolymerization initiators include benzyl.
• benzophenone-based photopolymerization initiators examples include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, ⁇ -hydroxycyclohexylphenylketone, and the like.
• ketal-based photopolymerization initiators examples include benzyl dimethyl ketal.
• Thioxanthone-based photopolymerization initiators include, for example, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and dodecylthioxanthone.
• the amount of the photopolymerization initiator used is preferably 0.01 to 3.0 parts by weight, more preferably 0.015 parts by weight, relative to the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer. parts to 2.0 parts by weight, more preferably 0.02 parts to 1.5 parts by weight, particularly preferably 0.025 parts to 1.0 parts by weight, most preferably 0.03 parts by weight. parts by weight to 0.50 parts by weight.
• the acrylic pressure-sensitive adhesive composition may contain a cross-linking agent.
• a cross-linking agent By using a cross-linking agent, the cohesive force of the acrylic pressure-sensitive adhesive can be improved, and the effects of the present invention can be exhibited more.
• the number of cross-linking agents may be one, or two or more.
• cross-linking agents examples include polyfunctional isocyanate-based cross-linking agents, epoxy-based cross-linking agents, melamine-based cross-linking agents, peroxide-based cross-linking agents, urea-based cross-linking agents, metal alkoxide cross-linking agents, metal chelate-based cross-linking agents, and metal salts.
• cross-linking agents carbodiimide-based cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, amine-based cross-linking agents, and the like.
• at least one (component c) selected from the group consisting of polyfunctional isocyanate-based cross-linking agents and epoxy-based cross-linking agents is preferable in that the effects of the present invention can be exhibited more effectively.
• Polyfunctional isocyanate-based cross-linking agents include, for example, lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate; cyclopentylene diisocyanate, cyclohexylene diisocyanate, Alicyclic polyisocyanates such as isophorone diisocyanate, hydrogenated tolylene diisocyanate and hydrogenated xylene diisocyanate; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate and aromatic polyisocyanates.
• lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate
• Polyfunctional isocyanate-based cross-linking agents include, for example, trimethylolpropane/tolylene diisocyanate adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate L”), trimethylolpropane/hexamethylene diisocyanate adduct (Nippon Polyurethane Industry Co., Ltd. company, trade name "Coronate HL”), trade name "Coronate HX” (Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane/xylylene diisocyanate adduct (manufactured by Mitsui Chemicals, trade name "Takenate 110N”), etc. A commercial item is also mentioned.
• epoxy-based cross-linking agents include N,N,N',N'-tetraglycidyl-m-xylenediamine, diglycidylaniline, 1,3-bis(N,N-diglycidylamino methyl)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, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane polyglycidyl ether,
• any appropriate content can be adopted for the content of the cross-linking agent in the acrylic pressure-sensitive adhesive composition, as long as the effects of the present invention are not impaired.
• a content is, for example, preferably 0.1 parts by weight to 5.0 parts by weight with respect to the solid content (100 parts by weight) of the acrylic polymer in terms of more expressing the effects of the present invention. , more preferably 0.2 parts by weight to 4.5 parts by weight, still more preferably 0.3 parts by weight to 4.0 parts by weight, particularly preferably 0.4 parts by weight to 3.5 parts by weight Department.
• the acrylic pressure-sensitive adhesive composition may contain any appropriate other component within a range that does not impair the effects of the present invention.
• Such other components include, for example, polymer components other than acrylic polymers, cross-linking accelerators, cross-linking catalysts, silane coupling agents, tackifying resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), Antiaging agents, inorganic fillers, organic fillers, metal powders, colorants (pigments, dyes, etc.), foils, 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 and the like.
• any suitable silicone-based pressure-sensitive adhesive such as known silicone-based pressure-sensitive adhesives described in JP-A-2014-047280 can be employed as long as the effects of the present invention are not impaired. . These may be of only one type, or may be of two or more types.
• the silicone-based pressure-sensitive adhesive may contain any appropriate component within a range that does not impair the effects of the present invention.
• a urethane-based pressure-sensitive adhesive is formed from a urethane-based pressure-sensitive adhesive composition.
• the urethane-based pressure-sensitive adhesive composition preferably contains at least one selected from the group consisting of urethane prepolymers and polyols, and a cross-linking agent, in order to make the effects of the present invention more manifest.
• At least one selected from the group consisting of urethane prepolymers and polyols can be called a so-called base polymer in the field of urethane pressure-sensitive adhesives. Only one type of urethane prepolymer may be used, or two or more types may be used. Only one kind of polyol may be used, or two or more kinds thereof may be used.
• the urethane prepolymer is preferably a polyurethane polyol, more preferably polyester polyol (a1) or polyether polyol (a2), each alone or in a mixture of (a1) and (a2) in the presence of a catalyst. It is obtained by reacting with an organic polyisocyanate compound (a3) under or without a catalyst.
• polyester polyol Any appropriate polyester polyol can be used as the polyester polyol (a1).
• polyester polyols (a1) include polyester polyols obtained by reacting an acid component and a glycol component.
• acid components include terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, and trimellitic acid.
• glycol components include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3′-dimethylolheptane, polyoxyethylene glycol, Examples include polyoxypropylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, and polyol components such as glycerin, trimethylolpropane, and pentaerythritol.
• Polyester polyols (a1) also include polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, poly( ⁇ -methyl- ⁇ -valerolactone) and polyvalerolactone.
• the molecular weight of the polyester polyol (a1) can range from low molecular weight to high molecular weight.
• the number average molecular weight is preferably 100 to 100,000 from the viewpoint that the effects of the present invention can be exhibited more effectively. If the number average molecular weight is less than 100, the reactivity becomes high and gelation may easily occur. If the number average molecular weight exceeds 100,000, the reactivity may become low, and furthermore, the cohesive strength of the polyurethane polyol itself may become small.
• the amount of the polyester polyol (a1) to be used is preferably 0 mol % to 90 mol % of the polyols constituting the polyurethane polyol, from the point of view that the effects of the present invention can be exhibited more effectively.
• any appropriate polyether polyol can be used as the polyether polyol (a2).
• examples of such polyether polyols (a2) include water, propylene glycol, ethylene glycol, glycerin, trimethylolpropane, and other low-molecular-weight polyols as initiators, and ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, and the like.
• Examples include polyether polyols obtained by polymerizing oxirane compounds.
• Specific examples of such polyether polyols (a2) include polyether polyols having two or more functional groups, such as polypropylene glycol, polyethylene glycol, and polytetramethylene glycol.
• the molecular weight of the polyether polyol (a2) can range from low molecular weight to high molecular weight.
• the number average molecular weight is preferably 100 to 100,000 from the viewpoint that the effects of the present invention can be exhibited more. If the number average molecular weight is less than 100, the reactivity becomes high and gelation may easily occur. If the number average molecular weight exceeds 100,000, the reactivity may become low, and furthermore, the cohesive strength of the polyurethane polyol itself may become small.
• the amount of the polyether polyol (a2) to be used is preferably 0 mol % to 90 mol % of the polyols constituting the polyurethane polyol, from the point of view that the effects of the present invention can be exhibited more effectively.
• polyether polyol (a2) Part of the polyether polyol (a2), if necessary, glycols such as ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane, pentaerythritol, It can be used in combination with polyvalent amines such as ethylenediamine, N-aminoethylethanolamine, isophoronediamine, xylylenediamine, and the like.
• glycols such as ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane, pentaerythritol
• polyvalent amines such as ethylenediamine, N-aminoethylethanolamine, isophoronediamine, xy
• polyether polyol (a2) only a bifunctional polyether polyol may be used, or a polyether having a number average molecular weight of 100 to 100,000 and at least 3 or more hydroxyl groups in one molecule. Part or all of the polyol may be used.
• polyether polyol (a2) when a polyether polyol having a number average molecular weight of 100 to 100,000 and having at least 3 or more hydroxyl groups in one molecule is used in whole or in part, the effects of the present invention are further exhibited. In addition, the balance between adhesive strength and releasability can be improved.
• the number average molecular weight of such a polyether polyol is less than 100, the reactivity becomes high and there is a possibility that gelation is likely to occur. Moreover, in such a polyether polyol, if the number average molecular weight exceeds 100,000, the reactivity may be lowered, and the cohesive strength of the polyurethane polyol itself may be lowered.
• the number average molecular weight of such a polyether polyol is more preferably 100 to 10,000 in terms of making the effects of the present invention more manifest.
• organic polyisocyanate compound (a3) Any appropriate organic polyisocyanate compound can be used as the organic polyisocyanate compound (a3).
• organic polyisocyanate compounds (a3) include aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, and alicyclic polyisocyanates.
• aromatic polyisocyanates examples include 1,3-phenylene diisocyanate, 4,4'-diphenyldiisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6 - tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanatotoluene, 1,3,5-triisocyanatobenzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4', 4′′-triphenylmethane triisocyanate and the like.
• aliphatic polyisocyanates examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and the like.
• araliphatic polyisocyanates include ⁇ , ⁇ '-diisocyanate-1,3-dimethylbenzene, ⁇ , ⁇ '-diisocyanate-1,4-dimethylbenzene, ⁇ , ⁇ '-diisocyanate-1,4-diethylbenzene , 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.
• alicyclic polyisocyanates include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2 ,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), 1,4-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane and the like. be done.
• organic polyisocyanate compound (a3) a trimethylolpropane adduct, a water-reacted biuret form, a trimer having an isocyanurate ring, and the like can be used in combination.
• Any suitable catalyst can be used as the catalyst that can be used in obtaining the polyurethane polyol.
• Examples of such catalysts include tertiary amine compounds and organometallic compounds.
• tertiary amine compounds include triethylamine, triethylenediamine, and 1,8-diazabicyclo(5,4,0)-undecene-7 (DBU).
• organometallic compounds examples include tin-based compounds and non-tin-based compounds.
• tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin Tin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate and the like.
• DBTDL dibutyltin dilaurate
• dibutyltin diacetate dibutyltin sulfide, tributyltin sulfide, tributyltin oxide
• non-tin compounds include titanium compounds such as dibutyl titanium dichloride, tetrabutyl titanate, and butoxy titanium trichloride; lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate.
• titanium compounds such as dibutyl titanium dichloride, tetrabutyl titanate, and butoxy titanium trichloride
• lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate.
• iron-based compounds such as iron 2-ethylhexanoate and iron acetylacetonate
• cobalt-based compounds such as cobalt benzoate and cobalt 2-ethylhexanoate
• zinc-based compounds such as zinc naphthenate and zinc 2-ethylhexanoate
• zirconium-based compounds such as zirconium naphthenate
• a catalyst When a catalyst is used to obtain a polyurethane polyol, in a system in which two kinds of polyols, a polyester polyol and a polyether polyol, are present, gelation or a reaction solution may occur in a single catalyst system due to the difference in reactivity. The problem of turbidity is likely to occur. Therefore, by using two kinds of catalysts when obtaining a polyurethane polyol, the reaction rate, the selectivity of the catalyst, etc. can be easily controlled, and these problems can be solved. Combinations of such two types of catalysts include, for example, tertiary amine/organometallic, tin/non-tin, and tin/tin, preferably tin/tin, and more preferably.
• tin 2-ethylhexanoate is a combination of dibutyltin dilaurate and tin 2-ethylhexanoate.
• the weight ratio of tin 2-ethylhexanoate/dibutyltin dilaurate is preferably less than 1, more preferably 0.2 to 0.6. If the compounding ratio is 1 or more, gelation may tend to occur due to the balance of catalytic activity.
• the amount of the catalyst used is preferably 0.01 with respect to the total amount of the polyester polyol (a1), the polyether polyol (a2) and the organic polyisocyanate compound (a3). % to 1.0% by weight.
• the reaction temperature is preferably less than 100°C, more preferably 85°C to 95°C. If the temperature is 100° C. or higher, it may become difficult to control the reaction rate and the crosslinked structure, and it may become difficult to obtain a polyurethane polyol having a predetermined molecular weight.
• a catalyst may not be used when obtaining polyurethane polyol.
• the reaction temperature is preferably 100° C. or higher, more preferably 110° C. or higher.
• Methods for obtaining polyurethane polyol include, for example, 1) a method of charging a polyester polyol, a polyether polyol, a catalyst, and an organic polyisocyanate into a volumetric flask, and 2) a method of charging a polyester polyol, a polyether polyol, and a catalyst into a flask to produce an organic polyisocyanate.
• a method of adding the As a method for obtaining a polyurethane polyol, the method 2) is preferable from the viewpoint of controlling the reaction.
• Any suitable solvent can be used to obtain the polyurethane polyol.
• suitable solvents include methyl ethyl ketone, ethyl acetate, toluene, xylene and acetone. Among these solvents, toluene is preferred.
• Polyols preferably include, for example, polyester polyols, polyether polyols, polycaprolactone polyols, polycarbonate polyols, and castor oil-based polyols.
• the polyol is more preferably polyether polyol.
• a polyester polyol can be obtained, for example, by an esterification reaction between a polyol component and an acid component.
• Polyol components include, for example, ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1 ,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl -1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexanetriol, polypropylene glycol and the like.
• acid components include succinic acid, methylsuccinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, dimer acid, 2-methyl-1, 4-cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, acid anhydrides thereof etc.
• polyether polyols examples include water, low-molecular-weight polyols (propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.), bisphenols (bisphenol A, etc.), dihydroxybenzenes (catechol, resorcinol, hydroquinone, etc.). is used as an initiator, polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide. Specific examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like.
• polycaprolactone polyols examples include caprolactone-based polyester diols obtained by ring-opening polymerization of cyclic ester monomers such as ⁇ -caprolactone and ⁇ -valerolactone.
• Polycarbonate polyols include, for example, polycarbonate polyols obtained by subjecting the above polyol component and phosgene to a polycondensation reaction; Polycarbonate polyols obtained by subjecting carbonic acid diesters such as propylene carbonate, diphenyl carbonate and dibenzyl carbonate to transesterification condensation; copolymerized polycarbonate polyols obtained by combining two or more of the above polyol components; various polycarbonate polyols and carboxyl groups above.
• Polycarbonate polyol obtained by esterification reaction with the containing compound Polycarbonate polyol obtained by etherification reaction of the above various polycarbonate polyols and hydroxyl group-containing compounds; Obtained by transesterifying the above various polycarbonate polyols and ester compounds.
• Polycarbonate polyols obtained by transesterification of various polycarbonate polyols and hydroxyl group-containing compounds Polyester-based polycarbonate polyols obtained by polycondensation reaction of various polycarbonate polyols and dicarboxylic acid compounds;
• castor oil-based polyols examples include castor oil-based polyols obtained by reacting castor oil fatty acids with the above polyol components. Specific examples include castor oil-based polyols obtained by reacting castor oil fatty acids with polypropylene glycol.
• the number average molecular weight Mn of the polyol is preferably from 300 to 100,000, more preferably from 400 to 75,000, even more preferably from 450 to 50,000, and particularly preferably 500, from the viewpoint that the effects of the present invention can be more expressed. ⁇ 30,000.
• the polyol preferably contains a polyol (A1) having three OH groups and a number-average molecular weight Mn of 300 to 100,000, in order to further express the effects of the present invention. Only one kind of polyol (A1) may be used, or two or more kinds thereof may be used.
• the content of the polyol (A1) in the polyol is preferably 5% by weight or more, more preferably 25% by weight to 100% by weight, and still more preferably 50% by weight, from the viewpoint that the effects of the present invention can be further expressed. % to 100% by weight.
• the number average molecular weight Mn of the polyol (A1) is preferably 1,000 to 100,000, more preferably more than 1,000 and 80,000 or less, still more preferably 1,100 to 70,000, in terms of being able to further express the effects of the present invention. , more preferably 1,200 to 60,000, more preferably 1,300 to 50,000, still more preferably 1,400 to 40,000, still more preferably 1,500 to 35,000, particularly preferably 1,700 to 32,000, most preferably 2000-30000.
• the polyol may contain a polyol (A2) having 3 or more OH groups and a number average molecular weight Mn of 20000 or less. Only one kind of polyol (A2) may be used, or two or more kinds thereof may be used.
• the number average molecular weight Mn of the polyol (A2) is preferably from 100 to 20,000, more preferably from 150 to 10,000, still more preferably from 200 to 7,500, and particularly Preferably 300-6000, most preferably 300-5000.
• the polyol (A2) is preferably a polyol having 3 OH groups (triol), a polyol having 4 OH groups (tetraol), or 5 OH groups, in that the effects of the present invention can be further expressed. and polyols (hexaols) having six OH groups.
• the total amount of the polyol (tetraol) having 4 OH groups, the polyol (pentaol) having 5 OH groups, and the polyol (hexaol) having 6 OH groups as the polyol (A2) is From the viewpoint that the effect can be expressed more, the content in the polyol is preferably 70% by weight or less, more preferably 60% by weight or less, still more preferably 40% by weight or less, and particularly preferably 30% by weight. % or less.
• the content of the polyol (A2) in the polyol is preferably 95% by weight or less, more preferably 0% by weight to 75% by weight, from the viewpoint that the effects of the present invention can be more expressed.
• the content of the polyol having 4 or more OH groups and a number average molecular weight Mn of 20000 or less is preferably 70 wt. %, more preferably 60% by weight or less, still more preferably 50% by weight or less, particularly preferably 40% by weight or less, and most preferably 30% by weight or less.
• the urethane pressure-sensitive adhesive composition preferably contains a cross-linking agent so that the effects of the present invention can be exhibited more.
• Urethane prepolymers and polyols as base polymers can each be a component of a urethane-based pressure-sensitive adhesive composition in combination with a cross-linking agent.
• a polyfunctional isocyanate-based cross-linking agent is preferable in that the effects of the present invention can be further expressed.
• any appropriate polyfunctional isocyanate-based cross-linking agent that can be used in the urethanization reaction can be adopted as the poly-functional isocyanate-based cross-linking agent.
• Examples of such a polyfunctional isocyanate-based cross-linking agent include the polyfunctional isocyanate-based cross-linking agents described in the above ⁇ Acrylic pressure-sensitive adhesive>.
• the urethane-based pressure-sensitive adhesive composition may contain any appropriate other component within a range that does not impair the effects of the present invention.
• Such other components include, for example, polymer components other than urethane prepolymers and polyols, cross-linking accelerators, cross-linking 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, coloring agents (pigments, dyes, etc.), foil products, anti-degradation agents, chain transfer agents, plasticizers, softeners, surfactants, antistatic agents, conductive agents, stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.
• the urethane-based pressure-sensitive adhesive composition preferably contains an anti-degradation agent in that it can further exhibit the effects of the present invention. Only one kind of anti-degradation agent may be used, or two or more kinds thereof may be used.
• the anti-degradation agent preferably includes an antioxidant, an ultraviolet absorber, and a light stabilizer, in that the effects of the present invention can be further expressed.
• antioxidants examples include radical chain inhibitors and peroxide decomposers.
• radical chain inhibitors examples include phenol antioxidants and amine antioxidants.
• phenolic antioxidants include monophenolic antioxidants, bisphenolic antioxidants, and polymeric phenolic antioxidants.
• monophenol antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearin- ⁇ -( 3,5-di-t-butyl-4-hydroxyphenyl)propionate and the like.
• bisphenol antioxidants examples include 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4' -thiobis(3-methyl-6-t-butylphenol), 4,4′-butylidenebis(3-methyl-6-t-butylphenol), 3,9-bis[1,1-dimethyl-2-[ ⁇ -( 3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane and the like.
• polymeric phenolic antioxidants examples include 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4, 6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis-[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane , bis[3,3′-bis-(4′-hydroxy-3′-t-butylphenyl)butyric acid]glycol ester, 1,3,5-tris(3′,5′-di-t-butyl -4′-Hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione, tocopherol and the like.
• peroxide decomposers examples include sulfur-based antioxidants and phosphorus-based antioxidants.
• sulfur-based antioxidants include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and distearyl 3,3'-thiodipropionate.
• Phosphorus antioxidants include, for example, triphenylphosphite, diphenylisodecylphosphite, and phenyldiisodecylphosphite.
• ultraviolet absorbers examples include benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, oxalic acid anilide-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and triazine-based ultraviolet absorbers. be done.
• Benzophenone-based UV absorbers include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2' -dihydroxy-4-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis(2-methoxy-4-hydroxy-5-benzoylphenyl ) methane and the like.
• Benzotriazole-based UV absorbers include, for example, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-( 2′-hydroxy-3′,5′-di-tert-butylphenyl)benzotriazole, 2-(2′-hydroxy-3′-tert-butyl-5′-methylphenyl)-5-chlorobenzotriazole, 2 -(2'-hydroxy-3',5'-di-tert-butylphenyl)5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole, 2-[2'-hydroxy-3'-(3'',4'',5'',6'',-tetrahydrophthalimido
• salicylic acid-based ultraviolet absorbers examples include phenyl salicylate, p-tert-butylphenyl salicylate, and p-octylphenyl salicylate.
• cyanoacrylate-based ultraviolet absorbers examples include 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate and ethyl-2-cyano-3,3'-diphenyl acrylate.
• Examples of light stabilizers include hindered amine light stabilizers and UV stabilizers.
• Examples of hindered amine light stabilizers include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl -1,2,2,6,6-pentamethyl-4-piperidyl sebacate and the like.
• UV stabilizers include, for example, nickel bis(octylphenyl) sulfide, [2,2′-thiobis(4-tert-octylphenolate)]-n-butylamine nickel, nickel complex-3,5-di-tert- Butyl-4-hydroxybenzyl-phosphate monoethylate, benzoate-type quenchers, nickel-dibutyldithiocarbamate, and the like.
• urethane-based polymer formed from urethane-based adhesive composition containing urethane prepolymer and polyfunctional isocyanate-based cross-linking agent Only one type of urethane prepolymer may be used, or two or more types may be used. Only one type of polyfunctional isocyanate-based cross-linking agent may be used, or two or more types may be used.
• any method of producing a urethane polymer using a so-called "urethane prepolymer" as a raw material may be used.
• any appropriate manufacturing method can be adopted.
• the number average molecular weight Mn of the urethane prepolymer is preferably 3,000 to 1,000,000 in that the effects of the present invention can be further exhibited.
• the equivalent ratio of NCO groups to OH groups in the urethane prepolymer and the polyfunctional isocyanate-based cross-linking agent is preferably 5.0 or less as NCO groups/OH groups, in terms of allowing the effects of the present invention to be exhibited more, More preferably 0.01 to 4.75, still more preferably 0.02 to 4.5, particularly preferably 0.03 to 4.25, most preferably 0.05 to 4.0 be.
• the content of the polyfunctional isocyanate-based cross-linking agent is preferably 0.01 to 30 parts by weight with respect to 100 parts by weight of the urethane prepolymer, in that the effects of the present invention can be more expressed. parts by weight, more preferably 0.05 to 25 parts by weight, still more preferably 0.1 to 20 parts by weight, particularly preferably 0.5 to 17.5 parts by weight and most preferably 1 to 15 parts by weight.
• the equivalent ratio of the NCO group to the OH group in the polyol and the polyfunctional isocyanate-based cross-linking agent is preferably 5.0 or less as NCO group/OH group, and more preferably 5.0 or less, from the viewpoint that the effects of the present invention can be further expressed. is 0.1 to 3.0, more preferably 0.2 to 2.5, particularly preferably 0.3 to 2.25, most preferably 0.5 to 2.0.
• the content of the polyfunctional isocyanate cross-linking agent is preferably 1.0 to 30 parts by weight with respect to 100 parts by weight of the polyol, in that the effects of the present invention can be further expressed. , more preferably 1.5 to 27 parts by weight, still more preferably 2.0 to 25 parts by weight, particularly preferably 2.3 to 23 parts by weight, most preferably is 2.5 to 20 parts by weight.
• the urethane-based polymer formed from the urethane-based pressure-sensitive adhesive composition containing a polyol and a polyfunctional isocyanate-based cross-linking agent is preferably a urethane-based pressure-sensitive adhesive composition containing a polyol and a polyfunctional isocyanate-based cross-linking agent. It is formed by curing an object.
• a method for forming a urethane-based polymer by curing a urethane-based pressure-sensitive adhesive composition containing a polyol and a polyfunctional isocyanate-based cross-linking agent the effect of the present invention, such as a urethanization reaction method using bulk polymerization or solution polymerization, etc. Any appropriate method can be adopted as long as it does not impair the
• a catalyst is preferably used to cure the urethane-based pressure-sensitive adhesive composition containing a polyol and a polyfunctional isocyanate-based cross-linking agent.
• catalysts include organometallic compounds and tertiary amine compounds.
• organometallic compounds include iron-based compounds, tin-based compounds, titanium-based compounds, zirconium-based compounds, lead-based compounds, cobalt-based compounds, and zinc-based compounds.
• iron-based compounds and tin-based compounds are preferable in terms of reaction speed and pot life of the pressure-sensitive adhesive layer.
• iron-based compounds include iron acetylacetonate, iron 2-ethylhexanoate, and Nasem ferric iron.
• tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin maleate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, tributyltin methoxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, dioctyltin dilaurate, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate and the like.
• titanium-based compounds examples include dibutyl titanium dichloride, tetrabutyl titanate, and butoxy titanium trichloride.
• zirconium-based compounds include zirconium naphthenate and zirconium acetylacetonate.
• lead-based compounds examples include lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate.
• cobalt-based compounds examples include cobalt 2-ethylhexanoate and cobalt benzoate.
• Examples of zinc-based compounds include zinc naphthenate and zinc 2-ethylhexanoate.
• tertiary amine compounds include triethylamine, triethylenediamine, 1,8-diazabisic-(5,4,0)-undecene-7, and the like.
• the amount of the catalyst is preferably 0.005 parts by weight to 1.00 parts by weight, more preferably 0.01 parts by weight to 100 parts by weight of the polyol, in order to further express the effects of the present invention. It is 0.75 parts by weight, more preferably 0.01 to 0.50 parts by weight, and particularly preferably 0.01 to 0.20 parts by weight.
• Adhesive treatment liquid contains a liquid having a Hansen solubility parameter value of 31 or less and an alkaline compound, and the concentration of the alkaline compound is 0.001% by weight to 20% by weight.
• the "liquid” referred to in the present invention is liquid at normal temperature and normal pressure, and generally includes water, alcohol, and various other solvents.
• the number of liquids having a Hansen solubility parameter value of 31 or less in the adhesive treatment liquid may be one, or two or more.
• the number of alkaline compounds in the adhesive treatment liquid may be one, or two or more.
• the adhesive treatment liquid contains a liquid having a Hansen solubility parameter value of 31 or less and an alkaline compound. It can be manufactured smoothly under the conditions.
• the "Hansen Solubility Parameter Value” divides the Hildebrand solubility parameter value into three components: the dispersion term ( ⁇ D ), the polar term ( ⁇ p), and the hydrogen bonding term ( ⁇ H ). It is a parameter value considering polarity, and is sometimes abbreviated as HSP value. Dispersion terms (terms for van der Waals forces), polar terms (terms for dipole moments), and hydrogen bonding terms (terms for hydrogen bonding) can be expressed in three-dimensional coordinates.
• the Hansen Solubility Parameter value of a mixture of two or more liquids can be obtained as the weighted average value m of the HSP values of each solvent by the following formula (1).
• ⁇ 1 and ⁇ 2 are HSP values of each liquid component
• ⁇ 1 and ⁇ 2 are volume fractions of each liquid component.
• m ⁇ 1 ⁇ 1+ ⁇ 2 ⁇ 2 (1)
• the Hansen solubility parameter value of the liquid contained in the adhesive treatment liquid is 31 or less, preferably 30 or less, more preferably 29 or less, still more preferably 28 or less, and particularly preferably 25 or less.
• the lower limit of the Hansen solubility parameter value of the liquid contained in the adhesive treatment liquid is preferably 7 or more, more preferably 10 or more, still more preferably 13 or more, and particularly preferably 15 or more. If the Hansen solubility parameter value of the liquid contained in the adhesive treatment liquid is within the above range, preferably 10 or more and 30 or less, more preferably 15 or more and 25 or less, the water-soluble polymer can be stably removed from the adhesive under mild conditions. can be manufactured.
• the Hansen solubility parameter value of the liquid contained in the adhesive treatment liquid exceeds 31, the permeability of the adhesive treatment liquid to the adhesive may deteriorate, and the production efficiency of the water-soluble polymer may decrease.
• the Hansen solubility parameter value of the liquid contained in the adhesive treatment liquid is less than 7, although not as much as when it exceeds 31, the permeability of the adhesive treatment liquid to the adhesive may similarly deteriorate. There is a possibility that the production efficiency of the water-soluble polymer may decrease.
• Liquids having a Hansen solubility parameter value of 31 or less as a single liquid contained in the adhesive treatment liquid typically include the following liquids.
• liquids may be used alone or in combination of two or more.
• mixed liquids having a Hansen solubility parameter value of 31 or less according to the above formula (1) as a mixed liquid in which a plurality of liquids are combined can be used.
• m 30.76.
• a liquid having a Hansen solubility parameter value of 31 or less preferably contains an alcohol, more preferably a lower alcohol, from the viewpoint of the solubility of alkaline compounds.
• Lower alcohols include not only primary alcohols, but also secondary alcohols such as 2-propanol, propylene glycol monopropyl ether and propylene glycol monoethyl ether, and tertiary alcohols such as t-butyl alcohol.
• the lower alcohol preferably contains a lower alcohol having 1 to 5 carbon atoms (typically, at least one selected from methanol, ethanol, 1-propanol, 2-propanol, butanol, and 1-pentanol), More preferably, it contains a lower alcohol having 1 to 4 carbon atoms (typically, at least one selected from methanol, ethanol, 1-propanol, 2-propanol, butanol), more preferably 1 to 3 carbon atoms. of lower alcohols (typically, at least one selected from methanol, ethanol, 1-propanol, 2-propanol), particularly preferably lower alcohols having 1 to 2 carbon atoms (at least selected from methanol and ethanol 1 type).
• a lower alcohol having 1 to 5 carbon atoms typically, at least one selected from methanol, ethanol, 1-propanol, 2-propanol, butanol, and 1-pentanol
• a lower alcohol having 1 to 4 carbon atoms typically, at least one selected from
• a liquid having a Hansen solubility parameter value of 31 or less preferably contains organic solvents other than alcohols in addition to alcohols.
• Organic solvents other than alcohols may be used alone or in combination of two or more.
• Organic solvents other than alcohols are, for example, the above ethers and the above hydrocarbons, preferably at least one selected from toluene, cyclopentylmethyl ether and tetrahydrofuran, more preferably toluene and cyclopentylmethyl It is at least one selected from ethers.
• the liquid having a Hansen Solubility Parameter value of 31 or less is a mixed solvent of an alcohol and an organic solvent (preferably at least one selected from ethers and hydrocarbons), the pressure-sensitive adhesive treatment liquid to the pressure-sensitive adhesive.
• the permeability can be improved, and the production efficiency of the water-soluble polymer can be improved.
• the organic solvent and the alcohol volume ratio is preferably 10:90 to 99:1, more preferably 20:80 to 95:5, still more preferably 30:70 to 90:10, Especially preferred is 40:60 to 90:10, most preferred is 60:40 to 80:20. If the volume ratio of the organic solvent to the alcohol is within the above range, the penetration of the adhesive treatment liquid into the adhesive can be further improved, and the production efficiency of the water-soluble polymer can be stably improved. can be planned.
• alkaline compound contained in the adhesive treatment liquid within the range that 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, calcium hydroxide, sodium methoxide, sodium ethoxide, potassium Metal alkoxides such as t-butoxide, preferably at least one selected from the group consisting of potassium hydroxide, sodium hydroxide and sodium ethoxide.
• the concentration of the alkaline compound in the adhesive treatment liquid is preferably 0.001 wt% to 20 wt%, more preferably 0.01 wt% to 10 wt%, still more preferably 0.01 wt% to 8% by weight, particularly preferably 0.01% to 5% by weight, most preferably 0.5% to 1.5% by weight. If the concentration of the alkali compound in the adhesive treatment liquid is within the above range, the water-soluble polymer can be more stably produced from the adhesive under mild conditions.
• the concentration of the alkaline compound in the adhesive treatment liquid exceeds 20% by weight, the alkaline compound is difficult to dissolve in the treatment solvent (liquid having a Hansen solubility parameter value of 31 or less), and in the form of an adhesive tape, Not only the adhesive but also the substrate may be adversely affected.
• the adhesive treatment liquid may contain other additives.
• any suitable additives can be adopted as long as they do not impair the effects of the present invention.
• examples of such additives include various known additives such as ionic surfactants, nonionic surfactants, chelating agents, solubilizers, slurrying agents, and antifoaming agents.
• Adhesive processing process In the method for producing a water-soluble polymer according to an embodiment of the present invention, typically, the above-described adhesive is impregnated with the above-described adhesive treatment liquid. As a result, the water-soluble polymer can be smoothly produced from the adhesive under mild conditions.
• impregnation method can be appropriately adopted as the method for impregnating the adhesive with the adhesive treatment liquid, depending on the type of scale and adhesive.
• impregnating the adhesive with the adhesive treatment liquid means to impregnate the adhesive with the adhesive treatment liquid.
• at least a part of the adhesive is For example, it may be immersed in an adhesive treatment liquid. This is because, if at least part of the adhesive is immersed in the adhesive treatment liquid, the adhesive will soak into the adhesive treatment liquid.
• stirring is performed in a state in which the adhesive is impregnated with the adhesive treatment liquid.
• the state in which the pressure-sensitive adhesive is impregnated with the pressure-sensitive adhesive treatment liquid is a state in which the pressure-sensitive adhesive is impregnated with the pressure-sensitive adhesive treatment liquid.
• a state of being immersed in an agent treatment liquid is exemplified. This is because, if at least part of the adhesive is immersed in the adhesive treatment liquid, the adhesive will soak into the adhesive treatment liquid.
• any appropriate stirring method can be appropriately adopted as the stirring method, depending on the type of scale and adhesive.
• one preferred embodiment performs ultrasonic treatment while the adhesive is impregnated with the adhesive treatment liquid.
• a water-soluble polymer can be more smoothly produced from the adhesive by performing ultrasonic treatment in a state in which the adhesive is impregnated with the adhesive treatment liquid.
• any appropriate ultrasonic treatment method can be appropriately adopted as the ultrasonic treatment method, depending on the type of scale and adhesive.
• the temperature of the pressure-sensitive adhesive impregnated with the pressure-sensitive adhesive treatment liquid is preferably 20°C or higher, more preferably 25°C. more preferably 30° C. or higher, more preferably 35° C. or higher, still more preferably 40° C. or higher, particularly preferably 45° C. or higher, and the upper limit is preferably 120° C. or lower. It is preferably 100° C. or lower, and still more preferably 80° C. or lower. If the temperature of the pressure-sensitive adhesive impregnated with the pressure-sensitive adhesive treatment liquid is within the above range, the water-soluble polymer can be easily and smoothly produced from the pressure-sensitive adhesive under mild conditions.
• a water-soluble polymer is produced from an adhesive of an adhesive tape containing a base material and an adhesive. More specifically, a physical method can also be applied as a method of separating the base material and the adhesive from the adhesive tape. Specifically, the adhesive is scraped off from the adhesive tape using an abrasive cloth, an abrasive belt, an abrasive paper, an abrasive brush, or the like to separate the substrate and the adhesive. The separated adhesive is impregnated with an adhesive treatment liquid.
• the adhesive is swollen by the adhesive treatment liquid, and is hydrolyzed by the liquid having a Hansen solubility parameter value of 31 or less and the alkaline compound contained in the adhesive treatment liquid. (including a saponification reaction in which a salt and an alcohol are produced by a reaction between an ester and a base) and the like are presumed to proceed.
• a water-soluble polymer can be efficiently produced by causing a reaction centering on a saponification reaction. Since the activation energy required for saponification is higher than the activation energy for transesterification, the reaction can be appropriately controlled by performing the reaction at a temperature within the above range (preferably 20°C to 120°C). Become.
• adhesive-derived water-soluble polymer can be recovered as a solution or dispersion by further treating with a solvent as necessary.
• the water-soluble polymer is dissolved in an aqueous solvent. It can be recovered as a diluted solution.
• aqueous solvents include water, alcohols, mixed solvents thereof, and mixed solvents of these and organic solvents.
• the "adhesive-derived water-soluble polymer” means a water-soluble polymer having a structure derived from the main polymer (also referred to as the base polymer) used in the composition of the adhesive, specifically, For example, at least part of the functional groups (e.g., carboxyl groups and ester groups) present at the side chain terminals of the main polymer (sometimes referred to as base polymer) that constitutes the adhesive is contained in the adhesive treatment liquid. It means a water-soluble polymer having a structure hydrolyzed (including a saponification reaction in which a salt and an alcohol are produced by a reaction between an ester and a base) by a liquid and an alkaline compound having a solubility parameter value of 31 or less.
• a water-soluble polymer can be easily obtained from an adhesive under mild conditions. This is because according to the method for producing a water-soluble polymer according to the embodiment of the present invention, the hydrolysis of the adhesive (including the saponification reaction in which a salt and an alcohol are produced by the reaction between an ester and a base) can be easily carried out under mild conditions. It is presumed that this is because the reaction progresses and as a result, a water-soluble polymer is obtained.
• the adhesive in order to hydrolyze an adhesive (including a saponification reaction in which a salt and an alcohol are produced by a reaction between an ester and a base), the adhesive is subjected to the above reaction under conditions of high temperature and high pressure. It is necessary to design the composition to a limited composition. According to the method for producing a water-soluble polymer according to the embodiment of the present invention, it is possible to easily perform under mild conditions without using high temperature and high pressure conditions and without designing the composition of the adhesive to a limited composition. , good hydrolysis of the adhesive (including saponification reactions in which salts and alcohols are produced by reaction of esters and bases) can be performed.
• a water-soluble polymer obtained by a method for producing a water-soluble polymer according to an embodiment of the present invention typically contains a structural unit (1) represented by the following formula and a structural unit (2) represented by the following formula: .
• R 1 represents a hydrogen atom or a methyl group.
• R 2 represents an alkyl group having 1 to 12 carbon atoms.
• M represents a hydrogen atom or a cation.
• a water-soluble polymer typically contains a plurality of each of the structural unit (1) and the structural unit (2).
• the structural units (1) and (2) are typically randomly arranged.
• R 1 represents a hydrogen atom or a methyl group, preferably a hydrogen atom. In a plurality of structural units (1), R 1 may be the same or different. In structural unit (1) and structural unit (2), R 1 may be the same or different.
• the structural unit (1) in the water-soluble polymer the glass transition temperature of the water-soluble polymer is lowered and the flexibility at room temperature is improved. Since the water-soluble polymer has the structural unit (2), the water-soluble polymer is soluble in water.
• the water-soluble polymer can be an excellent raw material for a water-soluble pressure-sensitive adhesive.
• the alkyl group represented by R 2 is preferably an alkyl group having 1 to 10 carbon atoms, more preferably a methyl group, an ethyl group, an n-butyl group, and A 2-ethylhexyl group can be mentioned.
• R 2 may be the same or different.
• the cation represented by M is preferably an alkali metal cation or an alkaline earth metal cation, more preferably an alkali metal cation, still more preferably a potassium cation, Sodium cations are mentioned.
• M may be the same or different.
• the content of the structural unit (1) in the water-soluble polymer is preferably 1% by weight or more, more preferably 3% by weight or more, still more preferably 5% by weight or more, and particularly preferably 10% by weight.
• the upper limit is preferably 95% by weight or less, more preferably 90% by weight or less, still more preferably 85% by weight or less, and particularly preferably 80% by weight or less.
• the content of the structural unit (2) in the water-soluble polymer is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 15% by weight or more, and particularly preferably 20% by weight.
• the upper limit is preferably 95% by weight or less, more preferably 90% by weight or less, still more preferably 87% by weight or less, and particularly preferably 85% by weight or less.
• the content of the structural unit (1) with respect to the total sum of the structural units (1) and (2) is preferably 5% by weight or more, more preferably 7% by weight or more, and still more preferably 10% by weight.
• the upper limit is preferably 95% by weight or less, more preferably 90% by weight or less, still more preferably 93% by weight or less, and particularly preferably 90% by weight or less.
• the content ratio of the constituent units can be measured by, for example, the FT-IR method, NMR method, and titration method.
• the water-soluble polymer according to the embodiment of the present invention can be appropriately employed as a raw material for various industrial products.
• a water-soluble polymer according to an embodiment of the present invention can be suitably used as a raw material for a pressure-sensitive adhesive or a raw material for a water-absorbing polymer.
• production method A a method for producing a water-absorbing polymer using a water-soluble polymer obtained by a method for producing a water-soluble polymer according to an embodiment of the present invention
• production method B a method of directly producing a water-absorbing polymer from a waste adhesive
• the cross-linking agent is an internal cross-linking agent that can react with the constituent units of the water-soluble polymer.
• the amount of the cross-linking agent used is preferably 0.1 to 200 parts by weight, more preferably 1 to 150 parts by weight, still more preferably 1 part by weight, relative to 100 parts by weight of the water-soluble polymer. ⁇ 100 parts by weight.
• the cross-linking agent includes, for example, a polymerizable cross-linking agent, a reactive cross-linking agent, and a cross-linking agent combining them.
• the polymerizable cross-linking agent can react with the ethylenically unsaturated double bonds contained in the water-soluble polymer.
• Specific examples of the polymerizable cross-linking agent include N,N'-methylenebisacrylamide, (poly)ethylene glycol di(meth)acrylate, (polyoxyethylene) trimethylolpropane tri(meth)acrylate, poly( Compounds having at least two polymerizable double bonds in the molecule such as meta)allyloxyalkanes can be mentioned.
• the reactive cross-linking agent is capable of reacting with the carboxyl group (more specifically, the -COOM group in the structural unit (2) above) contained in the water-soluble polymer.
• reactive cross-linking agents include covalent cross-linking agents such as polyglycidyl ethers (ethylene glycol diglycidyl ether, etc.), polyhydric alcohols (ethylene glycol, polyethylene glycol, propanediol, glycerin, sorbitol, etc.).
• ion-bonding cross-linking agents which are polyvalent metal compounds such as aluminum, melamine resin-based cross-linking agents, amino resin-based cross-linking agents, peroxide-based cross-linking agents, and the aforementioned polyfunctional isocyanate-based cross-linking agents.
• the cross-linking agent may be used alone or in combination of two or more.
• the cross-linking agent preferably includes a reactive cross-linking agent, and more preferably includes ethylene glycol and polyethylene glycol.
• a cross-linking agent is added to a water-soluble polymer solution (or water-soluble polymer dispersion).
• the water-soluble polymer solution (or water-soluble polymer dispersion) is stirred after the cross-linking agent is added.
• any appropriate stirring method can be appropriately adopted.
• the water-soluble polymer and the cross-linking agent are combined with the above-described adhesive treatment liquid (a liquid having a Hansen solubility parameter value of 31 or less and an alkali compound, the concentration of the alkali compound being 0.001% by weight). ⁇ 20% by weight of the adhesive treatment solution).
• the polymer and the cross-linking agent can be reacted while the hydrolysis (including the saponification reaction) of the water-soluble polymer is further progressed, and the water-absorbent polymer can be produced smoothly.
• the pressure-sensitive adhesive treatment liquid suitably used for the production of the water-absorbing polymer (hereinafter referred to as the treatment liquid for producing the water-absorbing polymer) is preferably 1% by volume or more and 90% by volume or less, more preferably 1% by volume or more and 80% by volume. % or less, more preferably 1% to 70% by volume, more preferably 1% to 60% by volume, particularly preferably 1% to 50% by volume, most preferably 1% to 40% by volume of alcohol.
• the pressure-sensitive adhesive treatment liquid contains an alcohol, the saponification reaction and the transesterification reaction of the alcohol can proceed in the production of the water-absorbing polymer, and the reactivity of the polymer to the cross-linking agent can be adjusted appropriately.
• the treatment liquid for producing a water-absorbing polymer preferably has a liquid Hansen solubility parameter value of 10 or more and 29 or less and an alkali compound concentration of 0.01% or more and 8% or less by weight, more preferably The liquid has a Hansen solubility parameter value of 13 or more and 25 or less, and an alkali compound concentration of 0.5% or more and 5% or less by weight.
• the Hansen solubility parameter value of the liquid and the concentration of the alkaline compound in the treatment liquid for producing the water-absorbent polymer are within the above ranges, the saponification reaction and the transesterification reaction can proceed in a well-balanced manner, and the water-absorbent polymer can be stably produced. can do.
• the saponification reaction may excessively dominate the transesterification reaction.
• the reaction between the cross-linking agent and the polymer (or adhesive) may converge on the surface of the polymer (or adhesive), making it impossible to produce the water-absorbent polymer.
• the temperature during the reaction between the water-soluble polymer and the cross-linking agent in the adhesive treatment liquid is preferably 15° C. or higher, more preferably 20° C. or higher, and still more preferably 25° C. ° C. or higher, more preferably 30 ° C. or higher, particularly preferably 35 ° C. or higher, most preferably 40 ° C. or higher, and the upper limit is preferably 80 ° C. or lower, more preferably 70 ° C. or lower. and more preferably 60° C. or less.
• the reaction temperature of the water-soluble polymer and the cross-linking agent in the adhesive treatment liquid is within the above range, the water-absorbing polymer can be easily and smoothly produced from the water-soluble polymer and the cross-linking agent under mild conditions.
• a water-absorbing polymer can be produced efficiently by causing a reaction centering on transesterification. Since the activation energy required for the transesterification reaction is lower than the activation energy for saponification, the reaction can be appropriately controlled by performing the reaction at a temperature within the above range (preferably 15°C to 80°C). Become.
• a water-absorbing polymer can be obtained easily under mild conditions from a pressure-sensitive adhesive as waste through a water-soluble polymer.
• the water-soluble polymer in particular, the —COOM group in the structural unit (2)
• the cross-linking agent proceed easily under mild conditions. and as a result, a water-absorbent polymer is obtained.
• Method B for producing a water-absorbing polymer according to another embodiment of the present invention includes the above-described adhesive treatment liquid (a liquid having a Hansen solubility parameter value of 31 or less and an alkaline compound, and the concentration of the alkaline compound is 0.001 % to 20% by weight of the adhesive treatment liquid), the cross-linking agent, and the adhesive are brought into contact with each other.
• adhesive treatment liquid a liquid having a Hansen solubility parameter value of 31 or less and an alkaline compound, and the concentration of the alkaline compound is 0.001 % to 20% by weight of the adhesive treatment liquid
• any suitable form of contact may be adopted as long as the effects of the present invention are not impaired.
• a contact form includes, for example, a form in which a cross-linking agent is added to the adhesive treatment liquid, then the adhesive is added, and they are brought into contact, and a cross-linking agent and an adhesive are simultaneously added to the adhesive treatment liquid.
• Examples include a form in which the adhesive is added and brought into contact therewith, and a form in which the adhesive is added to the adhesive treatment liquid and then the cross-linking agent is added and they are brought into contact.
• the water-absorbent polymer can be obtained directly from the adhesive as a waste product under mild conditions.
• the above-described treatment liquid for producing a water-absorbing polymer is preferably used as the adhesive treatment liquid.
• the amount of the cross-linking agent added is preferably 0.1 to 200 parts by weight, more preferably 1 to 150 parts by weight, still more preferably 1 to 100 parts by weight with respect to 100 parts by weight of the adhesive. Department.
• the temperature range during contact between the adhesive treatment liquid, the cross-linking agent, and the adhesive is, for example, the same as the temperature range during the reaction of the water-soluble polymer and the cross-linking agent in the adhesive treatment liquid.
• the water-absorbing polymer can be easily obtained from the adhesive under mild conditions.
• the hydrolysis of the adhesive including the saponification reaction in which a salt and an alcohol are formed by the reaction between an ester and a base
• the carboxyl groups generated by the hydrolysis more specifically, It is presumed that this is because the reaction between the —COOM group in the structural unit (2) and the cross-linking agent progresses to obtain a water-absorbent polymer.
• the water-absorbent polymer according to the embodiment of the present invention typically includes a structural unit (1) represented by the following formula, a structural unit (2) represented by the following formula, and a structural unit (1) represented by the following formula and/or a crosslinked structure formed by reaction of the structural unit (2) and the above-described crosslinking agent.
• the crosslinked structure is preferably formed by reacting a structural unit (2) represented by the following formula with the above-described crosslinking agent.
• R 1 represents a hydrogen atom or a methyl group.
• R 2 represents an alkyl group having 1 to 12 carbon atoms.
• M represents a hydrogen atom or a cation.
• R 1 , R 2 and M in the structural unit (1) and the structural unit (2) R 1 , R 2 and M in the structural unit (1) and the structural unit (2) in the water-soluble polymer can be referred to.
• the above description of the content ratio of the structural unit (1) in the water-soluble polymer can be used.
• the content of the crosslinked structure in the water-absorbing polymer is preferably 1% by weight or more, more preferably 3% by weight or more, still more preferably 5% by weight or more, and particularly preferably 7% by weight or more.
• the upper limit is preferably 90% by weight or less, more preferably 85% by weight or less, still more preferably 80% by weight or less, and particularly preferably 75% by weight or less.
• the content of the structural unit (1) with respect to the total sum of the structural units (1) and (2) is preferably 3% by weight or more, more preferably 5% by weight or more, and still more preferably 7% by weight. above, particularly preferably 10% by weight or more, and the upper limit is preferably 95% by weight or less, more preferably 90% by weight or less, still more preferably 85% by weight or less, and particularly preferably 80% by weight or less.
• the water-absorbing polymer according to the embodiment of the present invention can be obtained by any suitable method as long as the effects of the present invention are not impaired. Such methods include, for example, methods of making water-absorbing polymers according to embodiments of the present invention.
• Examples 30 and 31 (0.01 g) were added and stirred at 50° C. for 12 hours at a stirring speed of 600 rpm. As a result, a water-absorbing polymer was deposited. The solvent was then removed by decantation, and the water-absorbing polymer was dried at 120° C. for 1.5 hours. Next, the dried water-absorbing polymer was ground in a mortar and evaluated for water absorption according to JIS K 7223-1996 (tea bag method). Table 3 shows the results.
• O Water absorption rate is 10 times or more.
• x The water absorption rate is less than 10 times.
• the method for producing a water-soluble polymer and the method for producing a water-absorbing polymer according to the embodiments of the present invention can produce water-soluble polymers and water-absorbing polymers from various types of pressure-sensitive adhesives under mild conditions. It can be suitably used for recycling of adhesive waste generated in the process.

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• 2022
  • 2022-06-28 US US18/574,409 patent/US20240336760A1/en active Pending
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