Classifications

• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/02—Physical, chemical or physicochemical properties
  • B32B7/027—Thermal properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • 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
• • 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 laminate with excellent recyclability, a packaging material using said laminate, and a method for recycling said laminate and packaging material.
• plastic waste including food packaging
• plastic waste including food packaging
• plastic waste including food packaging
• plastic waste including food packaging
• plastic waste including those made from synthetic resins such as polyethylene, polypropylene, polystyrene (styrofoam), polyethylene terephthalate, and polyvinyl chloride, as well as many laminated films made by layering these synthetic resin films with metal foils such as aluminum foil and then printing them with product names or other marks or decorations, and these types of waste are mixed together when they are collected as garbage.
• waste plastics that contain a mixture of thermoplastic and thermosetting resins can be recycled by separating them based on their specific gravity, but the ease of recovery varies depending on the resin.
• many packaging materials, including those used for food packaging are made by bonding different synthetic resins together with adhesives, making separation using this method difficult. It is generally believed that recycling thermosetting resins is difficult because they have low thermal decomposition rates. In laminated films that have been decorated with printing ink to indicate product names, etc., the printing ink cannot be completely separated during the recycling process, and recycled products may be discolored or have printed patterns remaining.
• Patent Document 1 discloses a method for separating and recovering composite plastic waste, which comprises the steps of using triethylene glycol as a separation solvent, adding an alkali metal hydroxide as a catalyst, heating the triethylene glycol to 250-280°C, which is close to the boiling point of 200°C or more, and melting component P1 that can melt in triethylene glycol, dissolving or depolymerizing component P2 that is difficult to melt under stirring in triethylene glycol heated to 250-280°C and discharging it together with the solvent, recovering the remaining meltable component P1 and reinforcing fiber F or metal component M, recovering non-melted component P2 and separation solvent, distilling the separation solvent under reduced pressure to separate it from non-melted component P2, and purifying and reusing it.
• the present invention was made in consideration of these circumstances, and aims to provide a laminate that can be peeled off under mild conditions, has excellent adhesive strength, and can be produced by a general-purpose method, a method for recycling said laminate, and recycled plastics obtained from said laminate.
• the present invention relates to a laminate comprising a first substrate, a second substrate, an adhesive layer disposed between the first substrate and the second substrate, and a first resin layer disposed between the first substrate and the adhesive layer, the first resin layer comprising a first vinyl alcohol-based polymer and a first polyalkyleneimine, the first vinyl alcohol-based polymer being soluble at 5% by mass or more in a 1:1 (mass ratio) solution of water and ethanol at 25°C, the viscosity of a solution in which the vinyl alcohol-based polymer is dissolved at 5% by mass in a 1:1 (mass ratio) solution of water and ethanol at 25°C being 200 mPa ⁇ s or less, and the glass transition temperature of the first resin layer being 40°C or higher and 80°C or lower.
• the present invention provides a laminate that can be peeled off under mild conditions, has excellent adhesive strength, and can be produced by a general-purpose method, a method for recycling said laminate, and recycled plastics obtained from said laminate.
• the laminate of the present invention includes a first substrate, a second substrate, an adhesive layer disposed between the first substrate and the second substrate, and a first resin layer disposed between the first substrate and the adhesive layer.
• the laminate of the present invention will be described in detail below.
• the first substrate can be any film or sheet (unless otherwise specified below, film is a general term for film and sheet) that has excellent chemical and physical strength, and can be used without any particular limitation.
• the first substrate include polyethylene terephthalate (PET) film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film (LLDPE: low density polyethylene film, HDPE: high density polyethylene film, MDOPE: uniaxially oriented polyethylene film, OPE: biaxially oriented polyethylene film), polypropylene film (CPP: non-oriented polypropylene film, OPP: biaxially oriented polypropylene film), polyolefin film such as a gas barrier film in which an olefin-based heat-sealable resin layer is provided on one or both sides of a resin having gas barrier properties such as an ethylene-vinyl alcohol copolymer or polyvinyl alcohol, a polyvinyl alcohol film, an ethylene-vinyl alcohol copo
• Biomass films are sold by various companies, and for example, sheets such as those listed in the list of biomass certified products listed by the Japan Organics Resources Association can be used.
• biomass-derived ethylene glycol is made from ethanol (biomass ethanol) produced from biomass.
• biomass-derived ethylene glycol can be obtained by a conventional method of producing ethylene glycol from biomass ethanol via ethylene oxide.
• Commercially available biomass ethylene glycol may also be used; for example, biomass ethylene glycol available from India Glycoal Limited can be suitably used.
• Radioactive carbon-14C exists in the atmosphere at a ratio of 1 in 1012 particles, and this ratio does not change with atmospheric carbon dioxide, so this ratio does not change even in plants that fix this carbon dioxide through photosynthesis. For this reason, the carbon in plant-derived resins contains radioactive carbon-14C. In contrast, the carbon in fossil fuel-derived resins contains almost no radioactive carbon-14C. Therefore, by measuring the concentration of radioactive carbon-14C in the resin with an accelerator mass spectrometer, the proportion of plant-derived resin in the resin, i.e., the biomass plastic degree, can be determined.
• plant-derived low-density polyethylene which is a biomass plastic with a biomass plastic content of 80% or more, preferably 90% or more as specified by ISO16620 or ASTM D6866
• plant-derived low-density polyethylene examples include Braskem's product names "SBC818”, “SPB608”, “SBF0323HC”, “STN7006”, “SEB853”, and “SPB681”, and films using these as raw materials can be suitably used.
• the film may be one that has been stretched.
• a typical stretching method involves melt-extruding a resin into a sheet using an extrusion film-making method or the like, followed by simultaneous biaxial stretching or sequential biaxial stretching.
• sequential biaxial stretching it is common to first perform longitudinal stretching, and then transverse stretching. Specifically, a method that combines longitudinal stretching using the speed difference between rolls and transverse stretching using a tenter is often used.
• the film surface may be subjected to various surface treatments such as flame treatment or corona discharge treatment to ensure that an adhesive layer is formed that is free of defects such as film breaks or repellency.
• inorganic vapor deposition films such as metal vapor deposition films with a vapor deposition layer of a metal such as aluminum, transparent vapor deposition films with a vapor deposition layer of a metal oxide such as silica or alumina, and barrier films containing a gas barrier layer such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, vinylidene chloride, etc. may be used.
• barrier films containing a gas barrier layer such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, vinylidene chloride, etc.
• the film thickness of the first substrate is not particularly limited, and may be appropriately selected in the range of 1 to 300 ⁇ m from the viewpoints of formability and transparency.
• the range is preferably 1 to 100 ⁇ m.
• the second substrate may be the same as the first substrate.
• the second substrate is a film (sealant film) having heat sealability that can be melted by heat and fused to each other, and the first substrate is a substrate not expected to play the role of a sealant film.
• the second substrate is a film in which a film without heat sealability and a resin layer (heat seal layer) having heat sealability are laminated, and the first substrate is a substrate not expected to play the role of a sealant film.
• resins with heat sealability include polyethylene, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-(meth)acrylic acid copolymer, ethylene-ethyl (meth)acrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, modified olefin resins obtained by modifying olefin resins such as polyethylene or polypropylene with acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, or other unsaturated carboxylic acids, terpolymers of ethylene-(meth)acrylic acid ester-unsaturated carboxylic acid, cyclic polyolefins, cyclic olefin copolymers, polyethylene terephthalate (PET), polyacrylonitrile (PAN), ethylene
• sealant film unstretched, uniaxially stretched, or biaxially stretched.
• a biaxially stretched film can be obtained by, for example, longitudinally stretching the film 2 to 4 times using a roll stretching machine at 50 to 100°C, then transversely stretching the film 3 to 5 times using a tenter stretching machine in an atmosphere at 90 to 150°C, and subsequently heat treating the film using the tenter stretching machine in an atmosphere at 100 to 240°C.
• films that have been simultaneously biaxially stretched or sequentially biaxially stretched may be used.
• an easily peelable sealant film As the sealant film, an easily peelable sealant film (easy peel film) may be used.
• an easily peelable sealant film any of the interfacial peeling type, cohesive peeling type, and interlayer peeling type described below can be applied, and can be appropriately selected depending on the type of packaging material and the required characteristics.
• the index of easy peelability is appropriately set depending on the type of packaging material and the required characteristics, and one example is a seal strength of 2 to 20 N/15 mm.
• easy peelability can be achieved by using a phase separation polymer blend that combines polypropylene with high-density polyethylene, low-density polyethylene, ethylene-vinyl acetate copolymer, etc.
• the second substrate is a film in which a film without heat-sealing properties and a resin layer with heat-sealing properties (heat-sealing layer) are laminated
• the second substrate can be, for example, a film without heat-sealing properties coated with a heat-sealing agent containing a resin with heat-sealing properties.
• Heat-sealable resins include, for example, thermoplastic resins such as shellacs, rosins, rosin-modified maleic acid resins, rosin-modified phenolic resins, nitrocellulose, cellulose acetate, cellulose acetyl propionate, cellulose acetyl butyrate, chlorinated rubber, cyclized rubber, vinyl chloride, vinylidene chloride, polyamide resins, vinyl chloride-vinyl acetate copolymers, polyester resins, ketone resins, butyral resins, chlorinated polypropylene resins, chlorinated polyethylene resins, chlorinated ethylene vinyl acetate resins, ethylene vinyl acetate resins, acrylic resins, urethane resins, ethylene-vinyl alcohol resins, styrene-maleic acid resins, casein, and alkyd resins, and these may be used alone or in combination of two or more.
• thermoplastic resins such as shellacs, ros
• Heat sealants may be in any form, such as a type in which these resins are dissolved in an organic solvent, a type in which they are dissolved in water or an aqueous organic solvent, or an emulsion type in which acrylic emulsions, urethane emulsions, polyvinyl alcohol resins, ethylene-vinyl alcohol emulsions, ethylene-methacrylic acid emulsions, polyolefin emulsions, ethylene vinyl acetate emulsions, etc. are dispersed in water or an aqueous organic solvent.
• organic solvent there are no particular limitations on the organic solvent, but examples include aromatic hydrocarbons such as toluene, xylene, Solvesso #100, Solvesso #150, etc.; aliphatic hydrocarbons such as hexane, heptane, octane, decane, etc.; and esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, amyl acetate, ethyl formate, butyl propionate, etc.
• aromatic hydrocarbons such as toluene, xylene, Solvesso #100, Solvesso #150, etc.
• aliphatic hydrocarbons such as hexane, heptane, octane, decane, etc.
• esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, amy
• Aqueous organic solvents include alcohols such as methanol, ethanol, propanol, and butanol; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; and glycol ethers such as ethylene glycol (mono, di)methyl ether, ethylene glycol (mono, di)ethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, monobutyl ether, diethylene glycol (mono, di)methyl ether, diethylene glycol (mono, di)ethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol (mono, di)methyl ether, propylene glycol (mono, di)methyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and dipropylene glycol (mono, di)methyl ether.
• a known method can be used to apply the heat sealant.
• a roll coater, gravure coater, flexo coater, air doctor coater, blade coater, air knife coater, squeeze coater, impregnation coater, transfer roll coater, kiss coater, curtain coater, cast coater, spray coater, die coater, offset printing machine, screen printing machine, etc. can be used.
• a drying process can be performed in an oven, etc.
• the thickness of the heat seal layer (the amount of heat sealant applied (solid content)) may be any thickness, and is, for example, 0.5 g/m 2 to 5 g/m 2 .
• the film thickness of the second substrate can be selected as desired, but for example, when applied to packaging materials as described below, it is selected in the range of 5 to 500 ⁇ m. 10 to 250 ⁇ m is more preferable, and 15 to 100 ⁇ m is even more preferable.
• the second substrate may have a metal vapor deposition layer such as aluminum, or an inorganic vapor deposition layer such as aluminum oxide or silica.
• the adhesive layer is a layer that bonds the first substrate and the second substrate via the first resin layer described below and any layer that is provided as necessary.
• the adhesive layer is, for example, (1) A two-component curing urethane adhesive containing a polyol composition and a polyisocyanate composition.
• the polyol composition of the adhesive (1) contains polyols such as polyester polyols, polyether polyols, vegetable oil polyols, polyurethane polyols, sugar alcohols, etc. These polyols may also be used in combination of two or more kinds.
• Polyester polyols include polyester polyols, which are reaction products of polyhydric alcohols and polycarboxylic acids, and lactone-based polyester polyols obtained by polycondensation reaction of aliphatic polyols and various lactones such as ⁇ -caprolactone. It is preferable to use polyester polyols, which are reaction products of polyhydric alcohols and polycarboxylic acids.
• Polyhydric alcohols include aliphatic diols such as ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,2,2-trimethyl-1,3-propanediol, 2,2-dimethyl-3-isopropyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-bis(hydroxymethyl)cyclohexane, and 2,2,4-trimethyl-1,3-pentanediol;
• Aliphatic polyols with three or more functional groups such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, and pentaerythritol;
• Examples include polyether polyols obtained by ring-opening polymerization of aliphatic diols or polyols with various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether, and these can be used alone or in combination of two or more.
• polyvalent carboxylic acids include aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid; Aromatic dicarboxylic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, and 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid; and anhydride or ester forming derivatives of these aliphatic or dicarboxylic acids; Examples of the dihydroxycarboxylic acid include p-hydroxybenzoic acid,
• the molecular weight of the polyester polyol is not particularly limited, but is, for example, from 250 g/mol to 20,000 g/mol.
• the hydroxyl value of the polyester polyol is not particularly limited, but is, for example, from 5 mgKOH/g to 500 mgKOH/g.
• Polyether polyols include those obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexylene in the presence of a polymerization initiator.
• alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexylene
• Polymerization initiators include glycols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and triethylene glycol;
• glycols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl
• Trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, pentaerythritol, and triols of polypropylene glycol;
• primary or secondary alkylamines such as ethylamine and diethylamine
• amine compounds with multiple amino groups such as methylenediamine and ethylenediamine
• amine compounds with active hydrogen groups such as primary or secondary alkanolamines such as monoethanolamine and diethanolamine.
• the molecular weight of the polyether polyol can be appropriately adjusted, but is, for example, from 100 g/mol to 8000 g/mol.
• the hydroxyl value of the polyether polyol can be appropriately adjusted, but is, for example, from 10 mgKOH/g to 1200 mgKOH/g.
• vegetable oil polyols examples include castor oil, dehydrated castor oil, hydrogenated castor oil, and 5-50 mole alkylene oxide adducts of castor oil.
• Polyurethane polyol is a reaction product between a low- or high-molecular-weight polyol and a polyisocyanate compound.
• a low- or high-molecular-weight polyol the same polyhydric alcohols exemplified as the raw material for polyester polyol can be used.
• the polyisocyanate compound the same polyisocyanates that can be contained in the isocyanate composition described below can be used.
• Sugar alcohols include pentaerythritol, sucrose, xylitol, sorbitol, isomalt, lactitol, maltitol, mannitol, etc.
• the polyisocyanate composition contains a polyisocyanate compound having a plurality of isocyanate groups.
• the polyisocyanate compound is not particularly limited, and examples thereof include aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and biuret, nurate, adduct, allophanate, carbodiimide-modified, and uretdione-modified products of these diisocyanates, and urethane prepolymers obtained by reacting these polyisocyanates with polyols, and these can be used alone or in combination.
• aromatic diisocyanates include, but are not limited to, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate (also called polymeric MDI or crude MDI), 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, and 4,4',4"-triphenylmethane triisocyanate.
• polymethylene polyphenyl polyisocyanate
• Aromatic aliphatic diisocyanates refer to aliphatic isocyanates that have one or more aromatic rings in the molecule, and examples include, but are not limited to, m- or p-xylylene diisocyanate (also known as XDI), ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylxylylene diisocyanate (also known as TMXDI), etc.
• Aliphatic diisocyanates include, but are not limited to, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate.
• trimethylene diisocyanate tetramethylene diisocyanate
• hexamethylene diisocyanate also known as HDI
• pentamethylene diisocyanate 1,2-propylene diisocyanate
• 2,3-butylene diisocyanate 1,3-butylene diisocyanate
• dodecamethylene diisocyanate dodecamethylene diisocyanate
• 2,4,4-trimethylhexamethylene diisocyanate 2,4,4-trimethylhexamethylene
• Alicyclic diisocyanates include, but are not limited to, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, isophorone diisocyanate (also known as IPDI), 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, etc.
• IPDI isophorone diisocyanate
• 1,3-cyclopentane diisocyanate 1,3-cyclohexane diisocyanate
• 1,4-cyclohexane diisocyanate 1,4-cyclohexane diisocyanate
• the polyol used in the synthesis of the urethane prepolymer can be the same as the polyhydric alcohols exemplified as the raw materials for the polyester polyols mentioned above, either alone or in combination of two or more. It is preferable to use at least one of polyalkylene glycols or polyester polyols with a molecular weight of 200 to 3000 g/mol.
• the adhesive (1) used in the present invention may be solvent-based or solventless.
• a solvent-based adhesive refers to a form in which the polyol composition and polyisocyanate composition contain highly soluble organic solvents such as esters such as ethyl acetate, butyl acetate, and cellosolve acetate, ketones such as acetone, methyl ethyl ketone, isobutyl ketone, and cyclohexanone, ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, dimethyl sulfoxide, and dimethyl sulfamide, and a solventless adhesive refers to a form that does not substantially contain these organic solvents.
• the polyol composition and polyisocyanate composition do not substantially contain organic solvent.
• the polyol composition contains a low molecular weight alcohol, the low molecular weight alcohol reacts with the polyisocyanate composition and becomes part of the coating film, so there is no need to volatilize it after coating. Therefore, this type is also treated as a solventless adhesive, and the low molecular weight alcohol is not considered an organic solvent.
• the adhesive (1) used in the present invention may contain components other than those mentioned above, such as a urethane catalyst, an acid anhydride, a coupling agent, a pigment, a plasticizer, a phosphoric acid derivative, etc. These components may be contained in either or both of the polyol composition and the polyisocyanate composition, or may be prepared separately from these and mixed with the polyol composition and the polyisocyanate composition immediately before application of the adhesive (1).
• the adhesive (1) is preferably used in a formulation in which the ratio [NCO]/[OH] of the number of moles of isocyanate groups [NCO] contained in the polyisocyanate composition (Y) to the number of moles of hydroxyl groups [OH] contained in the polyol composition (X) is 0.5 to 3.0.
• the adhesive layer is a cured coating of the adhesive (1).
• the adhesive is applied to either the first substrate or the second substrate directly or via a first resin layer or any other layer that is optionally provided, and then the substrate is laminated to the other substrate, and an aging treatment is performed to form the adhesive layer.
• the aging temperature is room temperature to 70°C
• the aging time is 6 to 240 hours.
• the amount of adhesive (1) applied is appropriately adjusted, and is, for example, 1 g/m2 or more and 5 g/ m2 or less.
• the fat or oil containing an acid anhydride group of the adhesive (2) can be obtained, for example, by adding a compound containing an acid anhydride group to fat or oil.
• Fat or oil containing an acid anhydride group is preferably obtained by introducing an acid anhydride group into fat or oil containing a double bond derived from an unsaturated fatty acid in its chemical structure.
• oils and fats containing double bonds derived from unsaturated fatty acids in their chemical structure are preferably drying oils (iodine value > 130) and/or semi-drying oils (iodine value 100-130).
• drying oils iodine value > 130
• semi-drying oils iodine value 100-130.
• vegetable oils include paulownia oil, linseed oil, perilla oil, safflower oil, dehydrated castor oil, safflower oil, soybean oil, rapeseed oil, sunflower oil, sesame oil, rice oil, cottonseed oil, corn oil, tall oil, poppy oil, walnut oil, and pine seed oil.
• animal oils include fish oils (sardine oil, pacific saury oil, herring oil, etc.).
• recycled vegetable oils that have been used for cooking such as tempura oil, and have been recovered/recycled can also be used.
• oils and fats paulownia oil, soybean oil, and linseed oil are preferably used because of their ease of acquisition.
• a compound having a double bond in the molecule can be used, such as maleic anhydride, citraconic anhydride, and tetrahydrophthalic anhydride, among which maleic anhydride is preferred due to its ease of introduction and the reactivity of the acid anhydride group.
• the amount of acid anhydride groups introduced into fats and oils can be adjusted as appropriate, but to explain the case of introducing maleic anhydride as an example, the amount of maleic anhydride introduced is 19 to 34 g (0.19 to 0.35 mol) per 100 g of fats and oils, and more preferably 22 to 29 g (0.22 to 0.30 mol).
• Hydroxycarboxylic acids such as citric acid, isocitric acid, malic acid, and tartaric acid, as well as various acids such as phosphoric acid, monoalkyl phosphate esters, dialkyl phosphate esters, acetic acid, alkyl (C2-18) monocarboxylic acids, and dimer acids may be used together with fats and oils containing an acid anhydride group. These may be added when the acid anhydride is added to the fats and oils, or may be added after the addition reaction is complete.
• Curing agents having reactive groups that can react with acid anhydride groups include nitrogen-containing compounds such as tertiary amine-containing polyols, amino alcohols, amide polyols, and polyamines, as well as compounds having hydroxyl groups.
• tertiary amine-containing polyols are preferred because they are easy to balance between the reactivity with oils and fats containing acid anhydride groups and the physical properties of the film that is formed.
• the tertiary amine-containing polyol has 2 to 6 hydroxyl groups. It is sufficient that the tertiary amine-containing polyol has one or more tertiary amino groups, but it is preferable that the tertiary amine-containing polyol has 1 to 2 tertiary amino groups. Specific examples include polypropylene glycol ethylenediamine ether, tri(1,2-polypropylene glycol)amine, N-ethyldiethanolamine, N-methyl-N-hydroxyethyl-N-hydroxyethoxyethylamine, pentakishydroxypropyldiethylenetriamine, and tetrakishydroxypropylethylenediamine.
• tertiary amine-containing polyols may be used. Examples include TE-360 (a tertiary amine-containing trifunctional polyol manufactured by Guodu Chemical Co., Ltd. (China)), TD-401 (a tertiary amine-containing tetrafunctional polyol manufactured by Guodu Chemical Co., Ltd. (China)), EDP-300, EDP-450 (all tertiary amine-containing tetrafunctional polyols manufactured by Adeka Corporation), etc.
• TE-360 a tertiary amine-containing trifunctional polyol manufactured by Guodu Chemical Co., Ltd. (China)
• TD-401 a tertiary amine-containing tetrafunctional polyol manufactured by Guodu Chemical Co., Ltd. (China)
• EDP-300, EDP-450 all tertiary amine-containing tetrafunctional polyols manufactured by Adeka Corporation
• Aminoalcohols that have both a primary or secondary amino group and a hydroxyl group in one molecule include monomethanolamine, N-methylmethanolamine, N-ethylmethanolamine, dimethanolamine, monoethanolamine, N-methylethanolamine, N-ethylethanolamine, diethanolamine, etc.
• amide polyols examples include polyesteramide polyols, and polyesteramide polyols obtained by using an aliphatic diamine having an amino group, such as ethylenediamine, propylenediamine, or hexamethylenediamine, as a raw material in the esterification reaction of the polyester polyol.
• the polyamine is not particularly limited, and any known polyamine having a primary and/or secondary amino group can be used.
• the polyamine may also contain a tertiary amine.
• alkylene diamines such as ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, and hexamethylenediamine
• aliphatic diamines having 2 to 18 carbon atoms such as polyalkylene diamines such as diethylenetriamine, iminobispropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine
• Alkyl (1-4 carbon atoms) or hydroxyalkyl (2-4 carbon atoms) substituted aliphatic diamines such as dialkylaminopropylamines with 1-3 carbon atoms, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-hexamethylenediamine, and methyliminobispropylamine,
• alicyclic diamines with 4 to 15 carbon atoms such as 1,3-diaminocyclohexane, isophoronediamine, menthenediamine, and 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline), and alicyclic or heterocyclic aliphatic diamines, such as piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, and 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5,5]undecane,
• Aromatic ring-containing aliphatic amines with 8 to 15 carbon atoms such as xylylenediamine and tetrachloro p-xylylenediamine,
• Unsubstituted aromatic diamines with 6 to 20 carbon atoms such as 1,2-, 1,3- or 1,4-phenylenediamine, 2,4'- and 4,4'-diphenylmethanediamine, crude diphenylmethanediamine (polyphenylpolymethylenepolyamine), diaminodiphenylsulfone, benzidine, thiodianiline, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4,4',4"-triamine and naphthylenediamine,
• Aromatic diamines having a nucleus-substituted alkyl group with 1 to 4 carbon atoms such as 2,4- or 2,6-tolylenediamine, crude tolylenediamine, diethyltolylenediamine, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-bis(o-toluidine), dianisidine, diaminoditolylsulfone, 1,3-dimethyl-2,4-diaminobenzene, 2,3-dimethyl-1,4-diaminonaphthalene, and 4,4'-diamino-3,3'-dimethyldiphenylmethane, and mixtures of these isomers in various ratios,
• Aromatic diamines having nuclear-substituted electron-withdrawing groups such as halogen atoms such as fluorine, chlorine, bromine, and iodine; alkoxy groups such as methoxy and ethoxy; nitro groups, etc.
• halogen atoms such as fluorine, chlorine, bromine, and iodine
• alkoxy groups such as methoxy and ethoxy; nitro groups, etc.
• methylenebis-o-chloroaniline 4-chloro-o-phenylenediamine, 2-chloro-1,4-phenylenediamine, 3-amino-4-chloroaniline
• Aromatic diamines having a secondary amino group such as 4,4'-di(methylamino)diphenylmethane and 1-methyl-2-methylamino-4-aminobenzene (wherein part or all of the -NH2 in the above aromatic diamines has been replaced with -NH-R'(R' is an alkyl group; for example, a lower alkyl group such as a methyl group or an ethyl group));
• Low molecular weight polyamide polyamines obtained by condensing dicarboxylic acids such as dimer acids with polyamines such as the above alkylenediamines and polyalkylene polyamines under conditions where there is an excess of amino groups relative to acid groups (2 moles or more of amino groups per mole of acid groups),
• polyether polyamines which are hydrogenated cyanoethylated polyether polyols such as polyalkylene glycols.
• polyamidoamines and polyetherpolyamines are preferably used because they can form coatings with excellent strength.
• polyamines can also be used. Examples of such commercially available products include Jeffamine T-403, Jeffamine D-230, and Jeffamine D-400 (all polyether polyamines manufactured by Huntsman (USA)).
• polyether polyamines those that are bifunctional or trifunctional and have a molecular weight of 200 to 5000, more preferably 200 to 1500, are preferably used.
• a compound containing a hydroxyl group for example, a compound containing an average of two or more hydroxyl groups in the molecule can be suitably used, and examples of such a compound include polymer polyols selected from polyester polyols, polyether polyols, polyurethane polyols, polyether ester polyols, polyester (polyurethane) polyols, polyether (polyurethane) polyols, acrylic polyols, polycarbonate polyols, polyhydroxyl alkanes, castor oil, and mixtures thereof.
• polymer polyols selected from polyester polyols, polyether polyols, polyurethane polyols, polyether ester polyols, polyester (polyurethane) polyols, polyether (polyurethane) polyols, acrylic polyols, polycarbonate polyols, polyhydroxyl alkanes, castor oil, and mixtures thereof.
• the polyester polyol may be the same as those exemplified as components of the polyol composition of adhesive (1), and preferably has a number average molecular weight of 400 to 2000 and a hydroxyl value of 60 to 300.
• polyether polyol and polyurethane polyol may be the same as those exemplified as components of the polyol composition of adhesive (1).
• polyether ester polyols include polyether ester polyols obtained by reacting the above polyether polyols with dibasic acids such as terephthalic acid, isophthalic acid, phthalic anhydride, adipic acid, azelaic acid, sebacic acid, and dimer acid, or their dialkyl esters, or mixtures of these.
• polycarbonate polyols include those obtained by reacting one or more glycols selected from ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, and hydrogenated bisphenol A with dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene, etc.
• glycols selected from ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanedi
• the acrylic polyol can be obtained by copolymerizing hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or the like, which contains one or more hydroxyl groups in one molecule, or the corresponding methacrylic acid derivatives thereof, with, for example, acrylic acid, methacrylic acid, or an ester thereof.
• the polyhydroxyalkane may be a liquid rubber obtained by copolymerizing butadiene or butadiene with acrylamide or the like.
• polyhydroxyalkanes examples include glycols (diols) such as ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol, as well as trihydric or tetrahydric alcohols such as glycerin, trimethylolpropane, and pentaerythritol.
• glycols diols
• propylene glycol diethylene glycol
• 1,4-butanediol 1,6-hexanediol
• trihydric or tetrahydric alcohols such as glycerin, trimethylolpropane, and pentaerythritol.
• a compound containing these hydroxyl groups it is preferable to use at least one type of polyester polyol, since the hydroxyl groups have high reactivity and can improve curing properties.
• the curing agent preferably contains at least one nitrogen-containing compound. Only one type of nitrogen-containing compound may be used, or multiple types may be used in combination.
• the nitrogen-containing compound not only contributes to the formation of a cured adhesive as a curing agent, but when the curing agent contains a hydroxyl group-containing oil compound, the nitrogen contained in the structure acts as a catalyst to promote the reaction between the acid anhydride group and the hydroxyl group, thereby improving the curing speed.
• the fat or oil containing an acid anhydride group and the hardener are preferably used in such a way that the molar ratio of the acid anhydride group in the fat or oil to the functional group in the hardener that can react with the acid anhydride group (acid anhydride group/functional group that can react with the acid anhydride group) is in the range of 0.5 to 1.5, more preferably 0.8 to 1.25.
• the amount of hardener used is preferably such that the molar ratio of the nitrogen in the nitrogen-containing compound to the acid anhydride group in the oil or fat (nitrogen/acid anhydride group) is in the range of 0.5 to 0.8, more preferably 0.5 to 0.65.
• Preferred combinations of fats and oils containing acid anhydride groups and hardeners include a combination of fats and oils containing maleic anhydride-modified tung oil with a hardener containing polyester polyol and tertiary amine-containing polyol, a combination of fats and oils containing maleic anhydride-modified soybean oil with a hardener containing polyester polyol and polyether polyamine, and a combination of fats and oils containing maleic anhydride-modified soybean oil and tung oil with a hardener containing polyester polyol, polyether polyamine, and tertiary amine-containing polyol.
• a polycarbodiimide compound may be used as the adhesive (2).
• the polycarbodiimide compound reacts with the carboxylic acid produced by the reaction between the oil containing an acid anhydride group and the hardener to form a denser hardened adhesive, thereby improving the adhesive strength.
• the polycarbodiimide compound is not particularly limited and any known polycarbodiimide compound can be used.
• the molecular weight of the polycarbodiimide compound, converted into number average molecular weight, is preferably in the range of 1,000 to 5,000, more preferably in the range of 2,000 to 4,000.
• Carbodiimide compounds can be obtained commercially, for example, Carbodilite V02B (solid concentration 100%, carbodiimide equivalent 600), Carbodilite V05 (solid concentration 100%, carbodiimide equivalent 262), Carbodilite V04PF (solid concentration 100%, carbodiimide equivalent 336), Carbodilite V05S (solid concentration 90% by mass, carbodiimide group equivalent 291 (solid equivalent 262) ), Carbodilite V07 (solid content concentration 50% by mass, carbodiimide group equivalent 404 (solid content equivalent 202)), Carbodilite V09GB (solid content concentration 70% by mass, carbodiimide group equivalent 298 (solid content equivalent 209) (all manufactured by Nisshinbo Chemical Inc.), etc. are included, and V02B and V05 are preferably used.
• the carbodiimide-containing component may be contained alone or in combination of two or more kinds.
• the adhesive (2) may contain components other than the above-mentioned oils and fats containing an acid anhydride group and the curing agent.
• Such components include, but are not limited to, catalysts, coupling agents, acid anhydrides, hydroxycarboxylic acids, oxygen scavengers, phosphoric acids, pigments, tackifiers, stabilizers (antioxidants, heat stabilizers, UV absorbers, etc.), plasticizers, antistatic agents, lubricants, antiblocking agents, colorants, crystal nucleating agents, defoamers, leveling agents, etc.
• These components may be contained in only one of the first composition and the second composition described below, or in both.
• the adhesive layer is a cured coating of the adhesive (2).
• the adhesive is applied to either the first substrate or the second substrate directly or via a first resin layer or any other layer that is optionally provided, and then the substrate is laminated to the other substrate, and an aging treatment is performed to form the adhesive layer.
• the aging temperature is room temperature to 70°C
• the aging time is 6 to 240 hours.
• the amount of adhesive (2) applied is appropriately adjusted, and is, for example, 1 g/m2 or more and 5 g/ m2 or less.
• olefin-based resin modified with an acid and/or a hydroxyl group used in the adhesive (3) examples include a copolymer of an olefin-based monomer with a polymerizable monomer having an acid group (or an acid anhydride group) and/or a hydroxyl group, and a resin obtained by graft-modifying an olefin resin with a polymerizable monomer having an acid group (or an acid anhydride group) and/or a hydroxyl group.
• olefin resins having acid groups and/or acid anhydride groups include copolymers of olefin monomers and ethylenically unsaturated carboxylic acids or ethylenically unsaturated carboxylic anhydrides, and resins in which polyolefins are graft-modified with ethylenically unsaturated carboxylic acids or ethylenically unsaturated carboxylic anhydrides.
• Olefin monomers include olefins having 2 to 8 carbon atoms, such as ethylene, propylene, isobutylene, 1-butene, 4-methyl-1-pentene, hexene, and vinylcyclohexane. Of these, olefins having 2 to 8 carbon atoms are preferred because they provide particularly good adhesive strength, and it is preferable to use ethylene, propylene, and 1-butene.
• ethylenically unsaturated carboxylic acids or ethylenically unsaturated carboxylic anhydrides used in copolymerization with olefin monomers include acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, 4-methylcyclohex-4-ene-1,2-dicarboxylic anhydride, bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride, 1,2,3,4,5,8,9,10-octahydronaphthalene.
• Suitable anhydrides include norbornene-2,3-dicarboxylic anhydride, 2-octa-1,3-diketospiro[4.4]non-7-ene, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, maleopimaric acid, tetrahydrophthalic anhydride, methyl-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, methyl-norbornene-5-ene-2,3-dicarboxylic anhydride, and norborn-5-ene-2,3-dicarboxylic anhydride.
• maleic anhydride is particularly preferred because it has excellent reactivity with olefin monomers, excellent reactivity of the acid anhydride after copolymerization, and because the molecular weight of the compound itself is small and the functional group concentration is high when copolymerized. These can be used alone or in combination of two or more.
• ethylenically unsaturated carboxylic acid or ethylenically unsaturated carboxylic acid anhydride
• other compounds having ethylenically unsaturated groups such as styrene, butadiene, isoprene, etc., may be used in combination.
• Polyolefins used when synthesizing acid-modified olefin resins by graft modification include homopolymers and copolymers of olefins having 2 to 8 carbon atoms, and copolymers of olefins having 2 to 8 carbon atoms with other monomers.
• polyethylenes such as high density polyethylene (HDPE), low density polyethylene (LDPE), and linear low density polyethylene resins, polypropylene, polyisobutylene, poly(1-butene), poly(4-methyl-1-pentene), polyvinylcyclohexane, ⁇ -olefin copolymers such as ethylene-propylene block copolymers, ethylene-propylene random copolymers, ethylene-1-butene copolymers, ethylene-4-methyl-1-pentene copolymers, and ethylene-hexene copolymers, ethylene-vinyl acetate copolymers, ethylene-methyl methacrylate copolymers, ethylene-vinyl acetate-methyl methacrylate copolymers, propylene-1-butene copolymers, and ethylene-propylene-1-butene copolymers.
• HDPE high density polyethylene
• LDPE low density polyethylene
• linear low density polyethylene resins polyprop
• homopolymers of olefins having 2 to 8 carbon atoms and copolymers of two or more types of olefins having 2 to 8 carbon atoms are preferred because they have particularly good adhesive strength, and ethylene-propylene copolymers, ethylene-1-butene copolymers, propylene-1-butene copolymers, and ethylene-propylene-1-butene copolymers are particularly preferred.
• the ethylenically unsaturated carboxylic acid or ethylenically unsaturated carboxylic anhydride used for graft modification with polyolefin may be the same as those exemplified above.
• Maleic anhydride is preferred because it has high reactivity of functional groups after graft modification and also because it increases the functional group concentration of the graft modified polyolefin. These may be used alone or in combination of two or more.
• the olefin resin having an acid group and/or anhydride group is preferably one having an acid value of 1 to 200 mg KOH/g.
• olefin resins having hydroxyl groups include copolymers of polyolefins with hydroxyl group-containing (meth)acrylic esters or hydroxyl group-containing vinyl ethers, and resins in which polyolefins are graft-modified with hydroxyl group-containing (meth)acrylic esters or hydroxyl group-containing vinyl ethers.
• the polyolefins that can be used are the same as those used in the synthesis of olefin resins having acid groups and/or acid anhydride groups.
• hydroxyl group-containing (meth)acrylic acid esters examples include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, glycerol (meth)acrylate, lactone-modified hydroxyethyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate.
• hydroxyl group-containing vinyl ethers examples include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, and 4-hydroxybutyl vinyl ether.
• an olefin resin having a hydroxyl group with a hydroxyl value of 1 to 200 mg KOH/g is preferable to use.
• the weight average molecular weight of the olefin resin modified with an acid and/or a hydroxyl group is preferably 40,000 or more and 250,000 or less.
• the melting point of the olefin resin modified with an acid and/or a hydroxyl group is preferably 40°C or higher, more preferably 50°C or higher, and even more preferably 60°C or higher.
• the melting point of the olefin resin (A) is preferably 120°C or lower, more preferably 90°C or lower, and even more preferably 85°C or lower.
• the adhesive (3) is preferably used in combination with a curing agent.
• a curing agent there are no particular limitations on the curing agent, and any compound that can crosslink acid groups, acid anhydride groups, and/or hydroxyl groups can be used.
• the curing agent it is preferable for the curing agent to be at least one compound selected from the group consisting of isocyanate compounds, epoxy compounds, carbodiimide compounds, silane coupling agents, and metal compounds.
• the isocyanate compound the same compounds as those exemplified for adhesive (1) can be used.
• the isocyanate compounds can be used alone or in combination of two or more kinds.
• the epoxy compound is not particularly limited as long as it is a compound having an epoxy group in the molecule, and examples thereof include polyglycidyl ether type epoxy resins of aliphatic polyols such as ethylene glycol, propylene glycol, hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol, glycerin, diglycerin, sorbitol, spiroglycol, or hydrogenated bisphenol A; Bisphenol type epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, and bisphenol AD type epoxy resins; Aromatic epoxy resins such as novolac type epoxy resins which are glycidyl ethers of phenol novolac resins and cresol novolac resins; Polyglycidyl ethers of polyols which are ethylene oxide or propylene oxide adducts of aromatic polyhydroxy compounds
• Carbodiimide compounds include N,N'-di-o-toluylcarbodiimide, N,N'-diphenylcarbodiimide, N,N'-di-2,6-dimethylphenylcarbodiimide, N,N'-bis(2,6-diisopropylphenyl)carbodiimide, N,N'-dioctyldecylcarbodiimide, N-triyl-N'-cyclohexylcarbodiimide, N,N'-di-2,2-tert.-butylphenylcarbodiimide, N-triyl-N'-phenylcarbodiimide, N,N'-di-p-aminophenylcarbodiimide, N,N'-di-p-hydroxyphenylcarbodiimide, N,N'-di-cyclohexylcarbodiimide, and N,N'-di-p-to
• Silane coupling agents include, for example, aminosilanes such as ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl)- ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl)- ⁇ -aminopropyltrimethyldimethoxysilane, and N-phenyl- ⁇ -aminopropyltrimethoxysilane; epoxysilanes such as ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, and ⁇ -glycidoxypropyltriethoxysilane; vinylsilanes such as vinyltris( ⁇ -methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, and ⁇ -me
• the metal compound can be used without any particular limitation as long as it forms an ionic crosslink with the olefin resin modified with an acid and/or a hydroxyl group.
• it is a compound containing a metal ion, and examples thereof include metal oxides, hydroxides, carbonates, bicarbonates, acetates, formates, methoxides, ethoxides, etc.
• the metal ion include monovalent ions such as Li + , Na + , K + , Ag + , and Cu + , and divalent ions such as Cu 2+ , Ba 2+ , Zn 2+ , and Fe 2+ . Two or more of these metal ions can be mixed and included as necessary.
• aziridine groups such as oxazoline and amino resins
• examples of compounds that contain an aziridine group include N,N'-hexamethylene-1,6-bis(1-aziridinecarboxamide), N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trimethylolpropane-tri- ⁇ -aziridinylpropionate), N,N'-toluene-2,4-bis(1-aziridinecarboxamide), triethylenemelamine, trimethylolpropane-tri- ⁇ (2-methylaziridine)propionate, bisisophthaloyl-1-2-methylaziridine, tri-1-aziridinylphosphine oxide, and tris-1-2-methylaziridinephosphine oxide.
• Amino resins include melamine resins, benzoguanamine resins, urea resins, etc.
• the amount of the hardener in the adhesive (3) is preferably 0.01 parts by mass or more per 100 parts by mass of the olefin resin modified with acid and/or hydroxyl groups, more preferably 0.1 parts by mass or more, and even more preferably 0.5 parts by mass or more.
• the amount of the hardener is preferably 50 parts by mass or less per 100 parts by mass of the olefin resin modified with acid and/or hydroxyl groups, more preferably 35 parts by mass or less, and even more preferably 25 parts by mass or less.
• the adhesive (3) can be blended with an organic solvent to ensure fluidity and develop appropriate coating properties.
• organic solvents are not particularly limited as long as they can be removed by volatilization through heating in the drying process when the adhesive is applied, and examples of such organic solvents include aromatic organic solvents such as toluene and xylene; aliphatic organic solvents such as n-hexane and n-heptane; alicyclic organic solvents such as cyclohexane and methylcyclohexane; halogenated organic solvents such as trichloroethylene, dichloroethylene, chlorobenzene and chloroform; ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ester-based solvents such as ethyl acetate and butyl acetate; ethanol, methanol, n-propanol, 2-propanol (isopropyl
• alcohol-based solvents such as diisopropyl ether, butyl cellosolve, tetrahydrofuran, dioxane, butyl carbitol, and other ether-based solvents
• glycol ether-based solvents such as diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, and propylene glycol monomethyl ether
• glycol ester-based solvents such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate, and the like. These may be used alone or in combination of two or more.
• the adhesive (3) may contain various additives as necessary, such as tackifiers, plasticizers, thermoplastic elastomers, reactive elastomers, phosphate compounds, silane coupling agents, adhesion promoters, catalysts, leveling agents, inorganic fine particles such as colloidal silica and alumina sol, polymethyl methacrylate-based organic fine particles, defoamers, anti-sagging agents, wetting and dispersing agents, viscosity adjusters, UV absorbers, metal deactivators, peroxide decomposers, flame retardants, reinforcing agents, lubricants, rust inhibitors, fluorescent brighteners, inorganic heat absorbers, flame retardants, antistatic agents, and dehydrating agents.
• the content of these additives may be adjusted as appropriate within a range that does not impair the functionality of the adhesive.
• the adhesive layer is a cured coating of such adhesive (3).
• the adhesive is applied to either the first substrate or the second substrate directly or via a first resin layer or any other layer that is optionally provided, and then the substrate is laminated to the other substrate, and an aging treatment is performed to form the adhesive layer.
• the aging temperature is room temperature to 70°C
• the aging time is 6 to 240 hours.
• the amount of adhesive (3) applied is appropriately adjusted, and is, for example, 1 g/m2 or more and 5 g/ m2 or less.
• the adhesive layer may be formed by an anchor coating agent (4) used in a general extrusion lamination method.
• anchor coating agents (4) include polyurethane-based, polyolefin-based, polyethyleneimine-based, or epoxy resin-based anchor coating agents.
• the anchor coating agent (4) can be applied by, for example, a coating method such as roll coating, gravure roll coating, or kiss coating, or by a printing method.
• the thickness of the adhesive layer formed by the anchor coating agent (4) is, for example, 0.05 ⁇ m or more and 3.0 ⁇ m or less, preferably 0.1 ⁇ m or more and 2.0 ⁇ m or less, and more preferably 0.2 ⁇ m or more and 1.0 ⁇ m or less.
• the first resin layer is a layer disposed between the first substrate and the adhesive layer, and contains a first vinyl alcohol-based polymer and a first polyalkyleneimine.
• the first vinyl alcohol polymer is a hydrolyzate of a vinyl ester homopolymer or copolymer, and one obtained by a known, commonly used method can be used.
• the vinyl alcohol polymer is a reaction product of a hydrolyzate of a vinyl ester homopolymer or copolymer with an aldehyde, and one obtained by a known, commonly used method can be used.
• Vinyl esters include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl palmitate, vinyl stearate, vinyl oleate, vinyl benzoate, etc., and may be used alone or in combination of two or more. It is preferable to use vinyl acetate.
• Polymerizable compounds that can be copolymerized with vinyl esters include ethylene, propene, 1-butene, isobutylene, 1,3-butadiene, isopropenyl acetate, 2-propenyl acetate, 3,4-diacetoxy-1-butene, 2,2-dialkyl-4-vinyl-1,3-dioxolane such as 2,2-dimethyl-4-vinyl-1,3-dioxolane, 3,4-dihydroxy-1-butene, 3,4-diacyloxy-1-butene, 3-acyloxy-4-hydroxy-1-butene, 4-acyloxy-3-hydroxy-1-butene, 3,4-diacyloxy-2-methyl-1-butene, 4,5-dihydroxy-1-pentene, 4,5-diacyloxy-1-pentene, 4,5 -dihydroxy-3-methyl-1-pentene, 4,5-diacyloxy-3-methyl-1-pentene, 5,6-dihydroxy
• the amounts of these used can be adjusted as appropriate, but as an example, the amount of polymerizable compound blended is 1 mol % to 40 mol % of the total amount of vinyl ester and polymerizable compound, as another example, 1 mol % to 20 mol %, and as another example, 1 mol % to 15 mol %.
• the first vinyl alcohol polymer may be acetalized.
• Aldehydes used for acetalization include aliphatic aldehydes such as formaldehyde, acetaldehyde, propylaldehyde, butylaldehyde, octylaldehyde, and dodecylaldehyde; alicyclic aldehydes such as cyclohexanecarbaldehyde; aromatic aldehydes such as benzaldehyde, naphthaldehyde, anthraldehyde, phenylacetaldehyde, tolualdehyde, dimethylbenzaldehyde, cuminaldehyde, and benzylaldehyde; cyclohexene aldehyde, dimethylcyclohexene aldehyde, acrylonitrile, and the like; Examples of such aldehydes include unsaturated aldehydes such as chlorine
• the acid catalyst used in the acetalization can be any conventional organic or inorganic acid, such as acetic acid, paratoluenesulfonic acid, nitric acid, sulfuric acid, or hydrochloric acid.
• the weight average molecular weight of the vinyl alcohol polymer is, for example, 3,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 80,000.
• the first vinyl alcohol polymer is one that is soluble in a 1:1 (mass ratio) solution of water and ethanol at 25°C at a concentration of 5% by mass or more, and has a viscosity of 200 mPa ⁇ s or less at 25°C when the 5% by mass solution of the vinyl alcohol polymer is dissolved in the 1:1 (mass ratio) solution of water and ethanol. If the vinyl alcohol polymer is dissolved in a 1:1 (mass ratio) solution of water and ethanol and allowed to stand at 25°C for one day, and no precipitate or gel-like matter is found, the vinyl alcohol polymer is deemed to have dissolved.
• vinyl alcohol-based polymers have excellent solubility in water, many of them have low solubility in low molecular weight alcohols such as ethanol, and such vinyl alcohol-based polymers are only slightly soluble in a cosolvent of water and ethanol.
• a polymer having excellent solubility in a cosolvent of water and ethanol is selected and used. This allows the coating agent used to form the first resin layer to have excellent coating suitability even if it has a high solid content, and a coating film of an appropriate thickness can be efficiently formed as the first resin layer. In addition, less energy is required to volatilize the solvent from the coating agent when forming the first resin layer, which reduces the burden on the environment.
• the solubility of vinyl alcohol-based polymers in low molecular weight alcohols can be adjusted, for example, by using ethylene or propylene together with vinyl ester to incorporate a skeleton that is highly soluble in alcohol into the main chain, or by using 3,4-diacetoxy-1-butene together with vinyl ester to introduce a hydroxyl group into the side chain, or by adjusting the molecular weight, butyralization, and degree of saponification of the vinyl alcohol-based polymer.
• the degree of saponification of the vinyl alcohol polymer can be adjusted as appropriate, but an example is 90% or more.
• the first polyalkyleneimine is a resin having a polyalkyleneimine skeleton, and is obtained by polymerizing one or more types of alkyleneimines (e.g., ethyleneimine, propyleneimine) by a conventional method.
• alkyleneimines e.g., ethyleneimine, propyleneimine
• the first polyalkyleneimine may be a linear polyalkyleneimine having a linear polyalkyleneimine chain, or may be a branched polyalkyleneimine having a branched polyalkyleneimine chain.
• polyalkyleneimines include polyethyleneimine and polypropyleneimine.
• the polyalkyleneimine may have a substituent (e.g., a hydroxypropyl group or a hydroxyethyl group) introduced into at least some of the nitrogen atoms of the polyalkyleneimine chain.
• Polyalkyleneimines modified with organometallic compounds such as tetraisopropyl titanate, tetranormalbutyl titanate, butyl titanate dimer, tetra(2-ethylhexyl) titanate, tetramethyl titanate, polyhydroxytitanium stearate, titanium bisacetylacetonate, titanium tetraacetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, titanium ethylacetoacetate, titanium lactate, titanium triethanolamine, and titanium stearate may be used, and two or more types of polyalkyleneimines may be used in combination.
• organometallic compounds such as tetraisopropyl titanate, tetranormalbutyl titanate, butyl titanate dimer, tetra(2-ethylhexyl) titanate, tetramethyl titanate, polyhydroxytitanium stearate,
• the first polyalkyleneimine is considered to contribute to improving the adhesion between the vinyl alcohol polymer and the olefin film through the amino group (NHR group, NH2 group) and the ethylene group, and since it is effective in improving adhesion, it is preferable that the polyalkyleneimine contains a branched polyalkyleneimine.
• the amount of the first polyalkylimine in the first resin layer is 1% by mass or more and 25% by mass or less of the total amount of the first vinyl alcohol polymer and the first polyalkylimine.
• the first resin layer may contain a resin other than the first vinyl alcohol polymer and the first polyalkylimine.
• resins include cellulose resin, polyester, polyurethane, vinyl resin such as homopolymer or copolymer of olefin or styrene, acrylic resin, epoxy resin, amide resin, natural rubber, and composites thereof (e.g., core-shell type resin).
• the content of these resins is preferably kept to 10% by mass or less of the total amount of the first vinyl alcohol polymer and the first polyalkyleneimine. It is more preferable that the content is 5% by mass or less, and even more preferable that the content is 1% by mass or less. It may be 0% by mass.
• the laminate of the present invention may have a layer other than the first substrate, the second substrate, the adhesive layer, and the first resin layer.
• An example of such a layer is a printed layer.
• the printed layer is a layer in which characters, figures, symbols, and other desired patterns are printed using printing ink between the first substrate and the adhesive layer, or on the surface of the first substrate opposite to the adhesive layer.
• the printed layer is disposed between the first substrate and the adhesive layer, it is preferable that the printed layer is disposed between the first resin layer and the adhesive layer. This makes it easy to remove the printed layer together with the peeling of the adhesive, and the recycled plastic described later has a higher purity.
• printing inks there are no particular limitations on the printing method or printing ink, and any known printing method or printing ink can be used.
• printing inks using methods such as gravure printing, flexographic printing, lithographic offset printing, and inkjet recording printing are often used.
• Printing inks that combine these printing methods with methods of curing using active energy rays such as ultraviolet light (UV), LED, and electron beam (EB), or methods of curing using heat, are also used.
• active energy rays such as ultraviolet light (UV), LED, and electron beam (EB), or methods of curing using heat
• the inks may be referred to as water-based inks or organic solvent-based inks.
• gravure printing ink examples include gravure printing ink, flexographic printing ink (in some industries, gravure printing ink and flexographic printing ink are called liquid ink), UV-curable ink for lithographic offset printing, electron beam curable ink for lithographic offset printing, UV-curable ink for inkjet recording and printing, and electron beam curable ink for inkjet recording and printing.
• Biomass inks made from biomass raw materials are also used as appropriate.
• the printing ink may contain resin, colorant, and solvent as essential ingredients, or it may be a so-called clear ink that contains resin and solvent but does not substantially contain colorant.
• the printing layer may be provided over the entire surface of the first substrate, or only on a portion of it.
• the resin used in the printing ink is not particularly limited, and examples include acrylic resin, polyester resin, styrene resin, styrene-maleic acid resin, maleic acid resin, polyamide resin, polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-acrylic copolymer resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, polyvinyl chloride resin, chlorinated polypropylene resin, cellulose-based resin, epoxy resin, alkyd resin, rosin-based resin, rosin-modified maleic acid resin, ketone resin, cyclized rubber, chlorinated rubber, butyral, petroleum resin, etc., and one or more types can be used in combination.
• Colorants used in printing inks include inorganic pigments such as titanium oxide, red iron oxide, antimony red, cadmium red, cadmium yellow, cobalt blue, Prussian blue, ultramarine, carbon black, and graphite; organic pigments such as soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, and condensed polycyclic pigments; and extender pigments such as calcium carbonate, kaolin clay, barium sulfate, aluminum hydroxide, and talc.
• inorganic pigments such as titanium oxide, red iron oxide, antimony red, cadmium red, cadmium yellow, cobalt blue, Prussian blue, ultramarine, carbon black, and graphite
• organic pigments such as soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, and condensed polycyclic pigments
• the organic solvent used in the printing ink preferably does not contain aromatic hydrocarbon organic solvents. More specifically, examples of such organic solvents include alcohol organic solvents such as methanol, ethanol, n-propanol, isopropanol, and butanol; ketone organic solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester organic solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; aliphatic hydrocarbon organic solvents such as n-hexane, n-heptane, and n-octane; and alicyclic hydrocarbon organic solvents such as cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, and cyclooctane. These organic solvents can be used alone or in combination of two or more.
• plant-derived raw materials include cellulose resins such as cellulose acetate propionate resin and nitrocellulose, polyamide resins using dimer acids or polymerized fatty acids derived from natural oils such as soybean oil, palm oil, and rice bran oil, polycarboxylic acids such as succinic acid, succinic anhydride, adipic acid, azelaic acid, sebacic acid, dimer acid, glutaric acid, malic acid, etc., polyols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, pentylene glycol, 1,10-dodecanediol, dimer diol, isosorbide, etc., and polyisocyanates such as 1,5-pentamethylene diisocyanate and dimer diisocyanate. Biomass polyurethanes synthesized from plant-derived raw materials, and rosin resins
• the second vinyl alcohol polymer may be the same as that described for the first vinyl alcohol polymer (dissolved at 5% by mass or more in a 1:1 (mass ratio) solution of water and ethanol at 25° C., and the viscosity of a solution in which the vinyl alcohol polymer is dissolved at 5% by mass in a 1:1 (mass ratio) solution of water and ethanol at 25° C. is 200 mPa ⁇ s or less).
• the second vinyl alcohol polymer may be the same as or different from the first vinyl alcohol polymer.
• the second polyalkyleneimine may be the same as the first polyalkyleneimine.
• the second polyalkyleneimine may be the same as the first polyalkyleneimine or may be different.
• the glass transition temperature of the second resin layer is more preferably 50° C. or higher and more preferably 70° C. or lower.
• the blending amount of the second polyalkylimine is preferably 1% by mass or more and 25% by mass or less of the total amount of the second vinyl alcohol polymer and the second polyalkylimine.
• the thickness of the second resin layer can be appropriately adjusted, but is, for example, from 0.1 ⁇ m to 2.0 ⁇ m.
• the laminate of the present invention may include a third substrate in addition to the first substrate and the second substrate.
• the third substrate may be the same as the first substrate.
• the second substrate is a film (sealant film) having heat sealability that can be melted by heat and fused to each other, and the first substrate and the third substrate are substrates that are not expected to play the role of a sealant film.
• the first substrate, the second substrate, and the third substrate are all substrates that are not expected to play the role of a sealant film.
• the laminate of the present invention includes a third substrate
• the third substrate is disposed between the first substrate and the second substrate, and the first substrate and the third substrate, and the third substrate and the second substrate are bonded together with an adhesive similar to that described above, either directly or via a first resin layer or other layers that are provided as necessary.
• the adhesive layer disposed between the first substrate and the third substrate and the adhesive layer disposed between the third substrate and the second substrate may be formed from the same adhesive or may be formed from different adhesives.
• a resin layer similar to the first resin layer may be provided between the third substrate and the adhesive layer on the surface of the third substrate facing the first substrate.
• a resin layer similar to the first resin layer (hereinafter also referred to as the fourth resin layer) may be provided between the third substrate and the adhesive layer on the surface of the third substrate facing the second substrate.
• the third and fourth resin layers each contain a vinyl alcohol-based polymer (that is soluble at 5% by mass or more in a 1:1 (mass ratio) solution of water and ethanol at 25°C, and the viscosity of a 5% by mass solution of the vinyl alcohol-based polymer in a 1:1 (mass ratio) solution of water and ethanol at 25°C is 200 mPa ⁇ s or less) similar to the components exemplified for the first resin layer, and a polyalkyleneimine, and have a glass transition temperature of 40°C or higher and 80°C or lower.
• the first substrate, the second substrate and the third substrate are easily peeled off in the detachment step described below, and the layers sandwiched between the first and third resin layers, such as the printing layer and the adhesive layer, and the layers sandwiched between the second and fourth resin layers, such as the adhesive layer, are not overly finely divided after being peeled off from the substrate and can be easily recovered. In other words, this is preferable because it allows for a laminate with excellent recyclability.
• the vinyl alcohol-based polymers used in the third resin layer and the fourth resin layer may be the same as or different from the first vinyl alcohol-based polymer and the second vinyl alcohol-based polymer, respectively.
• the polyalkyleneimines used in the third resin layer and the fourth resin layer may be the same as or different from the first polyalkyleneimine and the second polyalkyleneimine, respectively.
• the third resin layer and the fourth resin layer can be provided in the same manner as the first resin layer.
• the coating agent used to form the third resin layer and the fourth resin layer may be the same as that used to form the first resin layer, or may be different, for example, in the vinyl alcohol polymer and the content of the second polyalkyleneimine in the coating agent, the solvent used, the amount of coating agent applied, etc.
• the glass transition temperature of the third resin layer and the fourth resin layer is more preferably 50° C. or higher and more preferably 70° C. or lower.
• the blending amount of the polyalkylimine is preferably 1% by mass or more and 25% by mass or less of the total amount of the vinyl alcohol-based polymer and the polyalkylimine.
• the film thickness of the third resin layer and the fourth resin layer can be appropriately adjusted, but is, for example, 0.1 ⁇ m or more and 2.0 ⁇ m or less.
• the laminate of the present invention may include layers other than those described above.
• One example of such a layer is a barrier coat layer.
• the barrier coat layer is a layer that prevents the transmission of oxygen and water vapor, and can be provided at any position of the laminate of the present invention by applying and drying a barrier coat agent.
• barrier coating agent (1) that contains a vinyl alcohol polymer and an aqueous solvent.
• the aqueous solvent may be water or the same water-soluble organic solvents as those exemplified as those usable in preparing the coating agent used to form the first resin layer.
• the aqueous solvent may be used alone or in combination of two or more kinds.
• silicon compounds or hydrolysates of the silicon compounds include tetraalkoxysilanes such as tetraethylsilicate (Si( OC2H5 ) 4 ) (hereinafter sometimes referred to as TEOS) and tetramethylsilicate; trialkoxysilanes such as trimethoxymethylsilane, triethoxymethylsilane, trimethoxyvinylsilane; dialkoxysilanes such as dimethoxydimethylsilane, diethoxydimethylsilane; monoalkoxysilanes such as methoxytrimethylsilane, ethoxytrimethylsilane, or hydrolysates or partial hydrolysates thereof.
• TEOS tetraethylsilicate
• TEOS tetraethylsilicate
• trialkoxysilanes such as trimethoxymethylsilane, triethoxymethylsilane, trimethoxyvinylsilane
• meta-oriented polycarboxylic acids examples include isophthalic acid and 1,3-naphthalenedicarboxylic acid. These compounds may have the same substituents as those exemplified in the explanation of ortho-oriented polycarboxylic acids on any carbon atom of the aromatic ring.
• the polycarboxylic acid used in the synthesis of polyester polyol may contain a polycarboxylic acid other than an ortho-oriented polycarboxylic acid or a meta-oriented polycarboxylic acid.
• These polycarboxylic acids include aliphatic polycarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid; unsaturated bond-containing polycarboxylic acids such as maleic anhydride, maleic acid, and fumaric acid; alicyclic polycarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; terephthalic acid, pyromellitic acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid, 1,5-anthracenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxy
• aromatic polycarboxylic acids include helical dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 2,7-anthracene dicarboxylic acid, 1,8-anthracene dicarboxylic acid, 9,10-anthracene dicarboxylic acid, biphenyl dicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid, and anhydrides or ester-forming derivatives of these dicarboxylic acids, p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid, and ester-forming derivatives of these dihydroxycarboxylic acids, and the like.
• succinic acid, 1,3-cyclopentane dicarboxylic acid, and anhydrides thereof are preferred.
• the polycarboxylic acid contains a polycarboxylic acid other than an ortho-oriented polycarboxylic acid or a meta-oriented polycarboxylic acid
• the proportion of the ortho-oriented polycarboxylic acid or the meta-oriented polycarboxylic acid in the total amount of the polycarboxylic acid is 40 to 100 mass%.
• Polyhydric alcohols other than those mentioned above may be used in combination, and examples of such polyhydric alcohols include aliphatic diols such as 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol; trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, trimethylolethane, tris(2-hydroxyethyl)isocyanurate, 1,2,4-butanetriol, pentaerythritol, and dipentaerythritol; hydroquinone, resorcinol, catechol, naphthalenediol, biphenol, bisphenol A, hisphenol
• the polyester polyol has three or more hydroxyl groups
• some of the hydroxyl groups may be modified with a polycarboxylic acid or its acid anhydride.
• the ratio of hydroxyl groups modified with the polycarboxylic acid is preferably 1/3 or less of the hydroxyl groups in the polyester polyol.
• polycarboxylic acids used for modification include, but are not limited to, succinic anhydride, maleic acid, fumaric acid, 1,2-cyclohexanedicarboxylic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, phthalic anhydride, 2,3-naphthalenedicarboxylic anhydride, trimellitic anhydride, oleic acid, and sorbic acid.
• the polyester polyol may be a polyester polyurethane polyol with a number average molecular weight of 1,000 to 15,000, which has been made by urethane elongation through a reaction with a diisocyanate compound. Polyester polyol that has been urethane elongated contains components with molecular weights above a certain level and urethane bonds, so it has excellent gas barrier properties and excellent initial cohesion.
• the isocyanate compound used in the barrier coating agent (3) may be the same as the polyisocyanate compound in the adhesive (1). It is preferable to use one having an aromatic ring or an aliphatic ring.
• isocyanate compounds having an aromatic ring or an aliphatic ring include toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, or trimers of these isocyanate compounds, and adducts obtained by reacting an excess amount of these isocyanate compounds with low molecular weight active hydrogen compounds such as ethylene glycol, propylene glycol, metaxylylene alcohol, 1,3-bishydroxyethylbenzene, 1,4-bishydroxyethylbenzene, trimethylolpropane, glycerol, pentaerythritol
• a compound having an active hydrogen group in combination with the barrier coating agent (3).
• the active hydrogen group in the compound having active hydrogen include a hydroxyl group, an amino group, an imino group, a carboxylic acid, a urea group, and an SH group. Among these, a hydroxyl group, an amino group, and an SH group are preferred.
• the solubility parameter of the compound having active hydrogen is 29.5 or less, the compatibility between the polyester polyol and the isocyanate compound is improved, the compound having active hydrogen is uniformly present in the barrier coat layer, and the effect of improving the gas barrier properties can be expected.
• the solubility parameter is the ⁇ T value listed in the Hansen Solubility Parameter Calculation Software (HSPiP) or the ⁇ T value calculated using the SMILES notation.
• Examples of compounds having a hydroxyl group as an active hydrogen group include alkanols such as octanol and decanol, aliphatic diols such as 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2,2-trimethylpentanediol, 3,3-dimethylolheptane, octanediol, and decanediol, alicyclic alcohols such as 1,3- or 1,4-cyclohexanedimethanol and 1,3- or 1,4-cyclohexanediol, aromatic alcohols such as salicyl alcohol and vanillyl alcohol, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6- Dihydric alcohols such as dimethyl-1-octene-3,8-diol, bisphenol A, diethylene glycol,
• Examples of compounds having an amino group as an active hydrogen group include aliphatic amines such as octylamine, decane amine, 1,8-diaminooctane, and 1,10-diaminodecane; alicyclic amines such as isophorone diamine, norbornene diamine, bis(aminomethyl)cyclohexane, cyclohexane diamine, diaminodicyclohexylmethane, and methylene bis(methylcyclohexaneamine); and aromatic amines such as 1-xylylene diamine, N-benzylethylene diamine, phenylene diamine, diaminodiphenyl methane, diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene, toluene diamine, and diethyl toluene diamine.
• aliphatic amines such as octylamine, decane
• Examples of compounds having an SH group as an active hydrogen group include hexyl mercaptan, heptyl mercaptan, octyl mercaptan, nonyl mercaptan, decyl mercaptan, undecyl mercaptan, dodecyl mercaptan, tridecyl mercaptan, tetradecyl mercaptan, pentadecyl mercaptan, mercaptophenol, mercaptopropionic acid, mercaptobutyric acid, 1,4-butanedithiol, 2-mercaptobenzothiazole, 3- These include mercapto-1,2-propanediol, mercaptomethylbutanol, 3-mercapto-2-methylpentanol, 3-mercapto-3-methylbutanol, 4-ethoxy-2-methyl-2-butanethiol, hexanethiol, dimethylthiophenol, 1,
• Compounds having active hydrogen may be used alone or in combination.
• Isosorbide, tris(2-hydroxyethyl) isocyanurate, trimethylolpropane, dipentaerythritol, and 1,4-cyclohexanedimethanol are preferred.
• the barrier coating agent (3) may be diluted with an organic solvent.
• organic solvents include ester-based solvents such as ethyl acetate, propyl acetate, and butyl acetate, ketone-based solvents such as acetone and 2-butanone, ether-based solvents such as tetrahydrofuran, aliphatic solvents such as hexane and cyclohexane, and aromatic solvents such as toluene.
• the laminate of the present invention is used as a component of a packaging material for packaging contents
• the outermost substrate when a bag is made and filled with contents is a film with low heat resistance such as a polyethylene film or a polypropylene film
• a heat-resistant coating layer By providing a heat-resistant coating layer, such problems can be prevented.
• Such compounds include cellulose derivatives such as cellulose nitrate, cellulose acetate, cellulose propionate, and cellulose butyrate, polyester resins having a benzene ring such as phthalic acid, naphthalene dicarboxylic acid, and ethylene oxide (hereinafter sometimes referred to as EO) adducts of bisphenol A, and/or alicyclic skeletons such as cyclopentanediol and dimethyloltricyclodecane, or aromatic isocyanates such as diphenylmethane diisocyanate, toluene diisocyanate, xylene diisocyanate, and naphthalene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate and norbornene diisocyanate, and/or urethane resins in which isocyanuric triisocyanate is bonded to a polyol and/or tris(2-hydroxye)
• the heat-resistant coating agent preferably uses inorganic fine particles such as alumina, magnesia, titania, zirconia, and silica (quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, ultrafine amorphous silica, etc.) as aggregates, as these have excellent heat resistance.
• inorganic fine particles such as alumina, magnesia, titania, zirconia, and silica (quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, ultrafine amorphous silica, etc.
• boron nitride, aluminum nitride, alumina oxide, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, etc. are preferred, as they have excellent thermal conductivity.
• the inorganic fine particles may be used alone or in combination of multiple types.
• the shape of the silica microparticles is not particularly limited, and spherical, hollow, porous, rod-like, plate-like, fibrous, or amorphous shapes can be used.
• commercially available hollow silica microparticles such as Silinax manufactured by Nittetsu Mining Co., Ltd. can be used.
• the primary particle size of the inorganic fine particles is preferably in the range of 5 nm to 200 nm, and more preferably 10 nm to 100 nm.
• the inorganic fine particles can be blended in a ratio of 5 to 90% by weight based on the total solid content of the heat-resistant coating agent and the inorganic fine particles, and the blending amount may be changed as appropriate depending on the purpose. In particular, a blending amount of 20% by weight or more is preferable.
• the heat-resistant coating agent may be colored.
• the colorant include inorganic pigments, organic pigments, and dyes used in general inks, paints, and recording agents, such as those used in the printing layer described below.
• Waxes, silicon additives, and organic beads can be used in the heat-resistant coating agent.
• waxes such as amide wax, polypropylene wax, polyethylene wax, paraffin wax, carnauba wax, and rice wax, ethylene oxide (EO) adducts of dimethylsiloxane, silicon additives of silicon modifications, and organic beads made of acrylic, nylon, urethane, or epoxy can be added.
• EO ethylene oxide
• solvents used in the heat-resistant coating agent include water, aromatic hydrocarbon organic solvents such as toluene, xylene, Solvesso #100, Solvesso #150, etc., aliphatic hydrocarbon organic solvents such as hexane, methylcyclohexane, heptane, octane, decane, etc., and various ester-based organic solvents such as methyl acetate, ethyl acetate, isopropyl acetate, normal propyl acetate, butyl acetate, amyl acetate, ethyl formate, butyl propionate, etc.
• aromatic hydrocarbon organic solvents such as toluene, xylene, Solvesso #100, Solvesso #150, etc.
• aliphatic hydrocarbon organic solvents such as hexane, methylcyclohexane, heptane, octane, decane, etc.
• water-miscible organic solvents include alcohols such as methanol, ethanol, propanol, butanol, and isopropyl alcohol; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; and glycol ethers such as ethylene glycol (mono, di) methyl ether, ethylene glycol (mono, di) ethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, monobutyl ether, diethylene glycol (mono, di) methyl ether, diethylene glycol (mono, di) ethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol (mono, di) methyl ether, propylene glycol (mono, di) methyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and di
• heat-resistant coating agents can also be used. Examples include SUNSYS FS241 manufactured by Sun Chemical, DH-004/DH-HARDENER P-60 manufactured by DIC, and ThermaGloss 463 manufactured by Michaelman.
• the laminate of the present invention can be used as a multi-layer packaging material for protecting foods, medicines, etc.
• the layer structure can be changed depending on the contents, the environment of use, and the form of use.
• the packaging material of the present invention can be obtained, for example, by overlapping the heat seal layers of the laminate of the present invention so that they face each other, and then heat sealing the peripheral edges.
• Examples of the bag-making method include folding or overlapping the laminate of the present invention so that the surfaces of the inner layers (the surfaces of the sealant film) face each other, and heat sealing the peripheral edges, for example, by using a side seal type, two-sided seal type, three-sided seal type, four-sided seal type, envelope seal type, hem seal type, pleated seal type, flat bottom seal type, square bottom seal type, gusset type, or other heat seal type.
• the packaging material of the present invention can take various forms depending on the contents, the environment in which it is used, and the form in which it is used. Self-supporting packaging materials (standing pouches) are also possible. Heat sealing can be performed by known methods such as bar seal, rotary roll seal, belt seal, impulse seal, high frequency seal, and ultrasonic seal.
• the opening is heat-sealed to produce a product using the packaging material of the present invention.
• the contents that can be filled include confectioneries such as rice crackers, bean snacks, nuts, biscuits and cookies, wafer snacks, marshmallows, pies, semi-dried cakes, candies, and snack foods; staple foods such as bread, snack noodles, instant noodles, dried noodles, pasta, aseptically packaged cooked rice, porridge, porridge, packaged rice cakes, and cereal foods; agricultural processed products such as pickles, boiled beans, natto, miso, frozen tofu, tofu, nametake mushrooms, konjac, wild vegetable processed products, jams, peanut cream, salads, frozen vegetables, and potato processed products; livestock processed products such as hams, bacon, sausages, chicken processed products, and corned beef; and fish ham and sausages.
• Examples of the food products that can be used include processed fish products such as fish paste, fish paste products, kamaboko, nori, tsukudani, bonito flakes, shiokara, smoked salmon, and spicy cod roe; fruit pulp such as peaches, mandarin oranges, pineapples, apples, pears, and cherries; vegetables such as corn, asparagus, mushrooms, onions, carrots, radishes, and potatoes; prepared foods such as frozen and chilled prepared foods, including hamburger steaks, meatballs, seafood fries, gyoza dumplings, and croquettes; dairy products such as butter, margarine, cheese, cream, instant creamy powder, and infant formula; liquid seasonings, retort curry, and pet food.
• the packaging material of the present invention can also be used as a packaging material for cigarettes, disposable hand warmers, infusion packs, and other pharmaceuticals, cosmetics, and vacuum insulation materials.
• the laminate of the present invention and packaging materials made of the laminate have excellent recyclability and can be used as raw materials for recycled plastics.
• the recycled plastics of the present invention are regenerated using the laminate and packaging materials of the present invention as raw materials.
• the recycled plastics of the present invention can be obtained, for example, by peeling the laminate and packaging materials of the present invention onto their respective substrates (peeling step), separating them according to resin type (separation and recovery step), melt-kneading them, and then pelletizing them.
• the laminate and packaging material of the present invention can be immersed in a release agent for a certain period of time, whereby the adhesive or printing ink is peeled off from the substrate and separated into a single-layer film.
• the laminate and packaging material of the present invention can be easily peeled off in hot water of 55° C. or higher, so hot water may be used as the release agent, but in addition to water, various surfactants such as basic compounds, hydrophilic alcohols, anionic surfactants, nonionic surfactants, silicone surfactants, fluorine-based surfactants, and biosurfactants, or other additives may also be used as the release agent.
• the use of a release agent containing a basic compound is preferred because it dissolves these layers, making it easy to peel off the laminate, and also because it has little effect on the physical properties of the recycled pellets. Furthermore, even when such a substrate is used, if any of the first to fourth resin layers described above is formed in contact with the vapor deposition layer, the vapor deposition layer can be removed from the film even when hot water of 55°C or higher is used as a release agent.
• Water that can be used may be pure water such as tap water, ion-exchanged water, ultrafiltered water, reverse osmosis water, distilled water, or ultrapure water. From the viewpoint of long-term storage, it is preferable to use water that has been sterilized by ultraviolet irradiation or addition of hydrogen peroxide, etc., since this can prevent the growth of mold or bacteria.
• a stripping agent that contains a basic compound it is preferable to use water with a hardness of 120 ppm or less, and it is even more preferable to use water with a hardness of 80 ppm or less.
• Basic compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, calcium hydroxide, etc.
• concentration of the basic compound is preferably 0.01% by mass or more and 5% by mass or less. The basic compound is adjusted so that the pH of the stripping agent is about 10 to 14.
• Hydrophilic alcohols are aliphatic alcohols that can be mixed with water in any ratio. Examples of hydrophilic alcohols include methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, and glycerin. These can be used alone or in combination of two or more, and it is preferable to use ethanol.
• the stripping agent contains a hydrophilic alcohol, the content is preferably 1% by mass or more and less than 60% by mass of the stripping agent.
• the immersion time in the stripping agent is not particularly limited, but is, for example, from 10 minutes to less than 5 hours.
• the immersion process in the stripping agent may be performed only once, or may be performed multiple times. When the immersion process is performed multiple times, the stripping agents used may be the same or different.
• the peeling of the laminate and packaging material is preferably carried out by heating to 55° C. or more and 85° C. or less, and more preferably to 70° C. or more and 85° C. or less.
• heating method There are no particular limitations on the heating method, and known heating methods using heat rays, infrared rays, microwaves, etc. can be used.
• the treatment tank used for immersion in the stripping agent is preferably provided with a reflux condenser for refluxing the heated and evaporated stripping agent.
• the release agent When immersed in the release agent, it is preferable that the release agent is stirred.
• stirring methods include mechanically stirring the dispersion of the laminated film contained in the treatment tank with a stirring blade, water flow stirring with a water flow pump, and bubbling with an inert gas such as nitrogen gas. Several methods may be used in combination. This allows the laminate to be separated more efficiently.
• ultrasonic vibrations When immersed in the stripping agent, ultrasonic vibrations may be applied to the stripping solution.
• One method for applying ultrasonic vibrations is to attach an ultrasonic vibrator to the treatment tank.
• the release agent used in the peeling step of the laminate is recovered and reused after removing components other than the film pieces, such as adhesive layer pieces and printed layer pieces peeled off from the laminate.
• Examples of a method for removing components other than the film pieces include filtration.
• the recycled plastic of the present invention may contain known additives.
• additives include at least one antioxidant selected from the group consisting of phenols and phosphorus-based additives; at least one lubricant selected from the group consisting of fatty acid amides, alkylene fatty acid amides, metal soaps, and esters; a hindered amine weathering stabilizer; a wax having an acid value of 5 mg KOH/g or less; and at least one antistatic agent selected from the group consisting of fatty acid sulfonates and fatty acid esters.
• the PEI content in the table refers to the polyalkyleneimine content in the total amount of polyvinyl alcohol and polyalkyleneimine used in preparing the coating agent.
• Tg in the table refers to the glass transition temperature of the dried coating film of each coating agent.
• Viscosity in the table refers to the viscosity of each coating agent at 25°C. For coating agents 7, 8, and 9, polyvinyl alcohol precipitated, making it impossible to measure the viscosity.
• Example 1 The coating agent was applied to the first substrate in a solid form using a gravure printing machine equipped with a gravure plate with a plate depth of 22 ⁇ m so that the coating amount (solid content) was 0.5 g/ m2 , and the coating agent was dried by passing through an oven at 70°C, and then left at room temperature for one day to form a first resin layer.
• Example 2 A first resin layer was provided on a first substrate in the same manner as in Sample 1. Next, a urethane-based laminating ink (FINART R794 white, manufactured by DIC Corporation) was adjusted to 15 seconds (25° C.) using a Zahn Cup #3 manufactured by Rigo Co., Ltd., and printed solidly on the first resin layer using a gravure printing machine equipped with a gravure plate with a plate depth of 43 ⁇ m, and then dried or cured by passing through an oven at 70° C. to form a printed layer.
• a urethane-based laminating ink FINART R794 white, manufactured by DIC Corporation
• Example 3 In the same manner as in Sample 1, a first resin layer was provided on a first substrate.
• the coating agent was applied solidly to the second substrate using a gravure printing machine equipped with a gravure plate with a plate depth of 22 ⁇ m, and then the coating agent was passed through an oven at 70° C. to dry, after which the coating agent was left at room temperature for one day to form a second resin layer.
• Example 4 A first resin layer was provided on the first substrate, and a second resin layer was provided on the second substrate in the same manner as in Sample 3. A printed layer was provided on the first resin layer in the same manner as in Sample 2. An adhesive was applied onto the printed layer, which was then bonded to the surface of the second substrate on which the second resin layer was provided, and aged at 40° C. for 3 days to obtain Sample 4 of first substrate/first resin layer/printed layer/adhesive layer/second resin layer/second substrate.
• Samples 5 and 6 were prepared in the same manner as Samples 1 and 2, except that the first resin layer was not provided.
• the combinations of the first substrate, second substrate, coating agent, and adhesive used in the manufacture of samples 1 to 6 are shown in Tables 4 to 17. Details of the first substrate, second substrate, and adhesive in the tables are as follows. Coating agents 7 to 9 could not be applied using the method described above, and no evaluation samples were made.
• OPP Toyobo Co., Ltd., P2161 (film thickness 20 ⁇ m)
• PET Toyobo Co., Ltd., E5100 (film thickness 12 ⁇ m)
• CPP Toyobo Co., Ltd., P1128 (film thickness 30 ⁇ m)
• VMCPP Toray Film Processing Co., Ltd., 2203 (film thickness 25 ⁇ m)
• Adhesive 1 A mixture of 1 part of DIC DRY (registered trademark) LX-470EL and 1 part of SP-60, both manufactured by DIC Corporation, was diluted with ethyl acetate. The coating amount (solid content) was 2.5 g/ m2 , and after coating the adhesive, the solvent was dried with a dryer before bonding to the CPP film.
• Adhesive 2 A mixture of 60 parts of DIC DRY (registered trademark) LX-500 and 1 part of KW-75, both manufactured by DIC Corporation, was diluted with ethyl acetate. The coating amount (solid content) was 2.5 g/ m2 , and after coating the adhesive, the solvent was dried with a dryer before bonding to the CPP film.
• Adhesive 3 In a flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube, 800 parts of soybean oil, 225 parts of maleic anhydride, and 0.5 parts of phosphoric acid were charged and heated to 180° C. After reacting at 180° C. for 3 hours, the temperature was lowered to 100° C., and 200 parts of tung oil were added and reacted for another 3 hours to obtain an oil containing an acid anhydride group.
• a polyester reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, distillation tube, and water separator was charged with 220 parts of diethylene glycol, 344 parts of neopentyl glycol, 286 parts of adipic acid, 287 parts of isophthalic acid, and 0.1 parts of tetraisopropyl titanate, and gradually heated so that the temperature at the top of the distillation tube did not exceed 100°C, and the internal temperature was maintained at 240°C.
• the acid value reached 2.0 mhKOH/g or less the esterification reaction was completed, and a polyester polyol with a hydroxyl value of 180 mgKOH/g was obtained.
• Adeka Polyether EDP-450 manufactured by ADEKA CORPORATION, polypropylene glycol containing two tertiary amines in the molecule, molecular weight 450, hydroxyl value 500 mgKOH/g was used as adhesive 3.
• the coating amount (solid content) was 2.5 to 3.0 g/ m2 , and after coating the adhesive, it was laminated to a CPP film.
• Coating agents 1 to 6 were applied in a solid manner to an OPP film (P2161, manufactured by Toyobo Co., Ltd.) having a thickness of 20 ⁇ m using a gravure printing machine equipped with a gravure plate having a plate depth of 22 ⁇ m, and the film was dried by passing through an oven at 70° C., and then left at room temperature for one day to form a first resin layer.
• Evaluation sample 7 having a size of 5 cm x 5 cm was cut out from the OPP film having the first resin layer formed thereon.
• the untreated side of a 5 cm x 5 cm OPP film was placed on the first resin layer of evaluation sample 7, and a load of 0.5 kg/ cm2 was applied. After leaving the sample for 24 hours in an atmosphere of 40°C and 80% humidity, the evaluation sample and the OPP film were peeled off, and the condition was evaluated according to the following criteria. The results are shown in Table 3.

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