Classifications

• • 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
  • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
  • B65D65/38—Packaging materials of special type or form
  • B65D65/40—Applications of laminates for particular packaging purposes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
  • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
  • C09J175/06—Polyurethanes from polyesters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
  • C09J175/08—Polyurethanes from polyethers

Definitions

• the present invention relates to an adhesive, a laminate obtained using the adhesive, and a packaging material.
• composites made by multilayer lamination of metal foils such as aluminum foil or metal-deposited films with plastic films such as polyethylene, polypropylene, vinyl chloride, polyester, and nylon are used. These laminates are made by appropriately combining various plastic films, metal-deposited films, or metal foils according to the required characteristics of each application, and bonding them together with an adhesive.
• the adhesive generally used is a two-component curing type made of a polyol composition and a polyisocyanate composition (for example, Patent Documents 1 and 2).
• Laminates for packaging materials are used in a bag-like state, where heat-sealed layers of polyethylene or polypropylene are thermally pressed together (heat sealed). For this reason, the adhesive used to manufacture the laminate must harden under certain aging conditions and have sufficient heat-seal strength.
• laminates are sometimes manufactured by bonding films having a metal vapor deposition layer such as aluminum or a vapor deposition layer of an inorganic oxide such as silica or alumina with an adhesive.
• a metal vapor deposition layer such as aluminum
• a vapor deposition layer of an inorganic oxide such as silica or alumina
• peeling can occur not between the vapor deposition layer and the adhesive layer, but between the vapor deposition layer and the film, which is known as vapor deposition peeling.
• the present invention has been made in consideration of these circumstances, and aims to provide a two-component curing adhesive that has excellent vapor deposition peel resistance and heat seal strength, as well as a laminate and packaging material obtained using said adhesive.
• the present invention relates to a two-component curing adhesive comprising a polyisocyanate composition (X) containing a polyisocyanate compound (A) and a polyol composition (Y) containing a polyol (B), in which the polyisocyanate compound (A) contains a polyurethane polyisocyanate (A1) which is a reaction product of an aromatic polyisocyanate (a) and a polyol (b), and an adduct (A2) of a diisocyanate (c) and a polyol (d), and the polyol (b) contains a polyester polyol (b1) and a polyether polyol (b2).
• the present invention further relates to a laminate including a first substrate, a second substrate, and an adhesive layer that bonds the first substrate and the second substrate, the adhesive layer being a cured coating film of the above-mentioned two-component curing adhesive, and a packaging material comprising the laminate.
• the present invention provides a two-component curing adhesive with excellent heat seal strength and vapor deposition peel resistance, as well as a laminate and packaging material obtained using the adhesive.
• the adhesive of the present invention is a two-component curing adhesive comprising a polyisocyanate composition (X) and a polyol composition (Y).
• X polyisocyanate composition
• Y polyol composition
• the polyisocyanate composition (X) used in the adhesive of the present invention contains a polyurethane polyisocyanate (A1) which is a reaction product of an aromatic polyisocyanate (a) and a polyol (b), a diisocyanate (c), a polyol (d), and an adduct (A2).
• the polyol (b) contains a polyester polyol (b1) and a polyether polyol (b2).
• an adhesive By using a combination of polyester polyol (b1) and polyether polyol (b2) as polyol (b), an adhesive can be obtained that has excellent adhesion to metal substrates, metal vapor deposition layers, and inorganic oxide vapor deposition layers, resistance to vapor deposition peeling, and excellent appearance after processing.
• Aromatic polyisocyanates (a) used in the synthesis of polyurethane polyisocyanate (A1) include, for example, 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,
• Examples of the isocyanate include, but are not limited to, 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 diisocyan
• the polyol (b) used in the synthesis of the polyurethane polyisocyanate (A1) includes a polyester polyol (b1) and a polyether polyol (b2).
• Polyester polyol (b1) is a reaction product of a polyhydric alcohol and a polycarboxylic acid.
• polyhydric alcohols include glycols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol;
• Ether glycols such as polyoxyethylene glycol and polyoxypropylene glycol
• Modified polyether diols obtained by ring-opening polymerization of an aliphatic diol 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;
• Lactone-based polyester polyols obtained by polycondensation reaction of aliphatic diols with various lactones such as lactonoids and ⁇ -caprolactone;
• Bisphenols such as bisphenol A and bisphenol F;
• Examples include alkylene oxide adducts of bisphenols obtained by adding ethylene oxide, propylene oxide, etc. to bisphenols such as bisphenol A and bisphenol F.
• Polyols with three or more functionalities include aliphatic polyols such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, and pentaerythritol;
• Modified polyether polyols obtained by ring-opening polymerization of aliphatic 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;
• Lactone-based polyester polyols obtained by polycondensation reaction of aliphatic polyols with various lactones such as ⁇ -caprolactone;
• the polyol include castor oil, dehydrated castor oil, hydrogenated castor oil which is a hydrogenated product of castor oil, and castor oil-based polyols such as an alkylene oxide 5 to 50 mole adduct of castor oil, and mixtures of these.
• the polycarboxylic acids used in the synthesis of polyester polyol (b1) 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; aliphatic polycarboxylic acids such as dimer acid; anhydrides or ester-forming derivatives of these aliphatic polycarboxylic acids;
• 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; aromatic polycarboxylic acids such as trimellitic acid and pyromellitic acid; and anhydrides or ester-forming derivatives of these aromatic polycarboxylic acids.
• the polycarboxylic acid used in the synthesis of polyester polyol (b1) preferably contains an aliphatic polycarboxylic acid.
• the amount of aliphatic polycarboxylic acid in the polycarboxylic acid is preferably 50 mass% or more, and more preferably 70 mass% or more.
• the total amount of the polycarboxylic acid may be an aliphatic polycarboxylic acid. It is preferable to use adipic acid as the aliphatic carboxylic acid.
• the number average molecular weight of polyester polyol (b1) is not particularly limited, but is, for example, from 300 to 4000, and preferably from 1000 to 3000. This can impart appropriate flexibility to the cured coating film of the adhesive, and even when a laminate is produced using a film having a vapor deposition of a metal or inorganic oxide, it can more reliably prevent problems such as suppressing peeling between the vapor deposition layer and the film (vapor deposition peeling).
• the number average molecular weight in this specification is a value measured by gel permeation chromatography (GPC) under the following conditions.
• Measuring device Tosoh Corporation HLC-8320GPC Column: TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL manufactured by Tosoh Corporation Detector: RI (differential refractometer)
• Data processing Multistation GPC-8020 model II manufactured by Tosoh Corporation Measurement conditions: Column temperature: 40°C Solvent: tetrahydrofuran Flow rate: 0.35 ml/min Standard: monodisperse polystyrene Sample: 100 ⁇ l of a tetrahydrofuran solution containing 0.2% by mass of resin solids filtered through a microfilter
• polyether polyols (b2) 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 such as 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-cyclohexy
• the number average molecular weight of the polyether polyol (b2) is not particularly limited, but is, for example, from 300 to 4000, and preferably from 1000 to 3000. This allows the cured coating film of the adhesive to have an appropriate degree of flexibility, and even when a laminate is produced using a film having a vapor deposition of a metal or inorganic oxide, it is possible to more reliably prevent problems such as peeling between the vapor deposition layer and the film (vapor deposition peeling).
• polyester polyol (b1) and polyether polyol (b2) can be adjusted as appropriate, but is, for example, 30:70 to 70:30.
• Polyol (b) may contain a polyol (b3) other than polyester polyol (b1) and polyether polyol (b2), but the amount of polyol (b3) is preferably kept to 10% by mass or less of the total amount of polyester polyol (b1) and polyether polyol (b2).
• Polyurethane polyisocyanate (A1) is obtained by reacting aromatic polyisocyanate (a) with polyol (b) in a ratio of the number of moles of isocyanate groups [NCO] to the number of moles of hydroxyl groups [OH], [NCO]/[OH], in the range of 1.0 to 5.0.
• the diisocyanate (c) used in the synthesis of the adduct (A2) may be any of those known in the art, such as 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 Aromatic diisocyanates such as 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"-tripheny
• Aromatic aliphatic diisocyanates such as m- or p-xylylene diisocyanate (also known as XDI), ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylxylylene diisocyanate (also known as TMXDI),
• Aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate,
• Alicyclic diisocyanates such as 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), and 1,4-bis(isocyanatomethyl)cyclohexane are included.
• IPDI isophorone diisocyanate
• 1,3-cyclopentane diisocyanate 1,3-cyclohexane diisocyanate
• 1,4-cyclohexane diisocyanate 1,4-cyclohexane diisocyanate
• polyols (d) examples 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; and trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, pentaerythritol, and triols of polypropylene
• adduct (A2) it is preferable to use an adduct of an aromatic diisocyanate and trimethylolpropane, and it is more preferable to use an adduct of tolylene diisocyanate and trimethylolpropane.
• the mixing ratio (by mass) of polyurethane polyisocyanate (A1) and adduct (A2) can be adjusted as appropriate, but is preferably 75:25 to 95:5, and more preferably 80:20 to 90:10.
• the isocyanate composition (X) may contain a polyisocyanate (A3) other than the polyurethane polyisocyanate (A1) and the adduct (A2).
• the polyisocyanate (A3) include the aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates exemplified as the diisocyanate (c), as well as biuret, nurate, allophanate, carbodiimide-modified, polymeric, and uretdione-modified products of these diisocyanates, and urethane prepolymers obtained by reacting these diisocyanates and/or polyisocyanates with polyols, and these can be used alone or in combination.
• the amount of polyisocyanate (A3) is preferably 5% by weight or less of the total amount of polyurethane polyisocyanate (A1) and adduct (A2).
• the polyurethane polyisocyanate (A1) may contain an aromatic polyisocyanate (b) that is unreacted with the polyol (b).
• the modified product of the polyisocyanate (A3) may also contain an unreacted diisocyanate.
• the adhesive of the present invention preferably contains these diisocyanate monomers in an amount of 5 mass% or less of the solid content of the polyisocyanate composition (X). This allows the adhesive coating to have an appropriate degree of flexibility, and even when a laminate is produced using a film having a vapor deposition of a metal or inorganic oxide, problems such as the suppression of peeling between the vapor deposition layer and the film can be prevented.
• the polyol composition (Y) contains a polyol (B).
• the polyol compound (B) is not particularly limited, and examples thereof include glycols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol;
• Trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, and pentaerythritol; Bisphenols such as bisphenol A, bisphenol F, hydrogenated bisphenol A, and hydrogenated bisphenol F; Dimer diol; Castor oil-based polyols such as castor oil, dehydrated castor oil, hydrogenated castor oil, and 5 to 50 mole alkylene oxide adducts of castor oil, and mixtures thereof; polyether polyols 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, such as the glycols or trifunctional or tetrafunctional aliphatic alcohols; Polyether urethane polyol obtained by further increasing the molecular weight of a polyether polyol with
• Polyester polyols (1) which are reaction products of polyesters obtained by ring-opening polymerization of cyclic ester compounds such as propiolactone, butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone, ⁇ -methyl- ⁇ -valerolactone, etc., with polyhydric alcohols such as the above-mentioned glycols, glycerin, trimethylolpropane, pentaerythritol, etc.; Polyester polyol (2) obtained by reacting a difunctional polyol such as the glycol, dimer diol, or bisphenol with a polycarboxylic acid: (3) a polyester polyol obtained by reacting a trifunctional or tetrafunctional aliphatic alcohol with a polycarboxylic acid; (4) a polyester polyol obtained by reacting a difunctional polyol with the trifunctional or tetrafunctional aliphatic alcohol and a polycarboxylic acid; Polyester polyols (5), which are poly
• polyester polyether polyurethane polyol obtained by reacting at least one of the polyester polyols (1) to (5), a polyether polyol, and an isocyanate compound;
• a polyester polyurethane polyol obtained by polymerizing the polyester polyols (1) to (5) with an isocyanate compound;
• Polyurethane polyols which are reaction products of these polyols with polyisocyanates;
• a polyurethaneurea polyol which is a reaction product of a composition containing the polyol, a polyisocyanate and an amine compound; etc.
• Amine compounds used in the synthesis of polyurethane urea polyol include diamines such as ethylenediamine, propylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, and dimer diamine, alkanolamines such as 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, monoethanolamine, 2-methylaminoethanol, 2-ethylaminoethanol, 3-amino-1-propanol, diethanolamine, and 3-amino-1,2-propanediol, and mixtures thereof.
• diamines such as ethylenediamine, propylenediamine, hexamethylene
• the polyisocyanates used in the synthesis of these polyols include the aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates exemplified as diisocyanate (c), as well as biuret, nurate, adduct, allophanate, carbodiimide-modified, polymeric, and uretdione-modified products of these diisocyanates, and urethane prepolymers obtained by reacting these diisocyanates and/or polyisocyanates with polyols, and these can be used alone or in combination.
• Examples of the polyvalent carboxylic acid used in the synthesis of the polyester polyols (2) to (4) include aromatic polybasic acids such as orthophthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride, naphthalic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid, benzophenonetetracarboxylic acid, benzophenonetetracarboxylic dianhydride, 5-sodium sulfoisophthalic acid, tetrachlorophthalic anhydride, and tetrabromophthalic
• Aliphatic polybasic acids such as malonic acid, succinic acid, succinic anhydride, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, maleic anhydride, and itaconic acid;
• Alkyl esters of aliphatic polybasic acids such as dimethyl malonate, diethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, diethyl pimelate, diethyl sebacate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, and diethyl maleate;
• Alicyclic polybasic acids such as 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, hymic anhydride, and HET acid anhydride; etc. can be used alone or in combination of two or more.
• the polyol (B) it is preferable to use a polyurethane urea polyol.
• a polyurethane urea polyol When such a compound is used as the polyol (B), an adhesive with high initial cohesive strength can be obtained due to urea bonds.
• the polyol (e) used as the raw material for the polyurethane urea polyol preferably contains at least one selected from the group consisting of polyester polyol (e1) and polyether polyol (e2). Since this results in an adhesive with superior heat seal strength, vapor deposition peel resistance, and processing appearance, it is more preferable that the polyol (e) contains polyester polyol (e1) and polyether polyol (e2).
• polyester polyol (e1) and polyether polyol (e2) are used in combination as the polyol (e), the mass ratio thereof can be appropriately adjusted, and is, for example, 9:1 to 1:9.
• the polyol (e) used as a raw material for the polyurethane urea polyol may contain a polyol (e3) other than the polyester polyol (e1) and the polyether polyol (e2).
• the amount of the polyol (e3) may be appropriately adjusted, and is, for example, 10% by mass or less of the polyol (e).
• the raw material of the polyurethane urea polyol may contain an active hydrogen group-containing compound (f) such as a polyvalent carboxylic acid or a hydroxycarboxylic acid in addition to the polyol (e).
• the amount of the compound can be appropriately adjusted, but as an example, it is 5 parts by mass or less when the polyol (e) is 100 parts by mass.
• the amount of the amine compound in the raw material of the polyurethaneurea polyol can be appropriately adjusted, but as an example, it is 1 to 20 parts by mass when the polyol (e) is 100 parts by mass.
• the number average molecular weight of polyol (B) is not particularly limited, but as an example, it is preferably 300 or more and 4000 or less.
• the adhesive of the present invention may contain components other than the above-mentioned components.
• the other component (C) may be contained in either or both of the polyisocyanate composition (X) and the polyol composition (Y), or may be prepared separately from these and mixed with the polyisocyanate composition (X) and the polyol composition (Y) immediately before application of the adhesive. Each component will be described below.
• Catalyst (C1) examples include metal catalysts, amine catalysts, and aliphatic cyclic amide compounds.
• Examples of the metal catalyst (C1) include metal complex, inorganic metal, and organic metal catalysts.
• metal complex catalysts include acetylacetonate salts of metals selected from the group consisting of Fe (iron), Mn (manganese), Cu (copper), Zr (zirconium), Th (thorium), Ti (titanium), Al (aluminum), and Co (cobalt), such as iron acetylacetonate, manganese acetylacetonate, copper acetylacetonate, and zirconia acetylacetonate.
• Inorganic metal catalysts include those selected from Sn, Fe, Mn, Cu, Zr, Th, Ti, Al, Co, etc.
• Organometallic catalysts include organic zinc compounds such as zinc octylate, zinc neodecanoate, and zinc naphthenate; organic tin compounds such as stannous diacetate, stannous dioctoate, stannous dioleate, stannous dilaurate, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin oxide, and dibutyltin dichloride; organic nickel compounds such as nickel octylate and nickel naphthenate; organic cobalt compounds such as cobalt octylate and cobalt naphthenate; organic bismuth compounds such as bismuth octylate, bismuth neodecanoate, and bismuth naphthenate; and titanium compounds such as tetraisopropyloxytitanate, dibutyltitanium dichloride, tetra
• Amine catalysts include triethylenediamine, 2-methyltriethylenediamine, quinuclidine, 2-methylquinuclidine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N',N",N"-pentamethyl-(3-aminopropyl)ethylenediamine, N,N,N',N",N"-pentamethyldipropylenetriamine, N,N,N',N'-tetramethylhexamethylenediamine, bis(2-dimethylaminoethyl)ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol, N,N-dimethyl-N'-(2-hydroxyethyl)ethylenediamine, N,N-dimethyl-N'-(2-hydroxy
• Aliphatic cyclic amide compounds include ⁇ -valerolactam, ⁇ -caprolactam, ⁇ -enantholactam, ⁇ -capryllactam, and ⁇ -propiolactam. Among these, ⁇ -caprolactam is more effective at promoting hardening.
• Acid Anhydride (C2) examples include cyclic aliphatic acid anhydrides, aromatic acid anhydrides, and unsaturated carboxylic acid anhydrides, and can be used alone or in combination of two or more.
• phthalic anhydride trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid anhydride, dodecenylsuccinic anhydride, polyadipic anhydride, polyazelaic anhydride, polysebacic anhydride, poly(ethyloctadecanedioic acid) anhydride, poly(phenylhexadecanedioic acid) anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylhimic anhydride, trialkyltetrahydrophthalic anhydride,
• the anhydride include methylcyclohexene dicarboxylic anhydride, methylcyclohexene tetracarboxylic anhydride, ethylene glycol bistrimellitate dianhydr
• glycols examples include alkylene glycols such as ethylene glycol, propylene glycol, and neopentyl glycol; and polyether glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol.
• alkylene glycols such as ethylene glycol, propylene glycol, and neopentyl glycol
• polyether glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol.
• copolymer polyether glycols of two or more of these glycols and/or polyether glycols may also be used.
• Coupled Agent (C3) examples include a silane coupling agent, a titanate-based coupling agent, and an aluminum-based coupling agent.
• Silane coupling agents include 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 ⁇ -methacryloxyprop
• Titanate coupling agents include, for example, tetraisopropoxytitanium, tetra-n-butoxytitanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, titanium lactate, and tetrastearoxytitanium.
• aluminum-based coupling agents examples include acetoalkoxyaluminum diisopropylate.
• the pigment (C4) is not particularly limited, and examples thereof include organic pigments and inorganic pigments such as extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments, green pigments, blue pigments, metal powder pigments, luminescent pigments, and pearlescent pigments described in the Paint Raw Materials Handbook 1970 Edition (compiled by the Japan Paint Manufacturers Association), as well as plastic pigments.
• organic pigments and inorganic pigments such as extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments, green pigments, blue pigments, metal powder pigments, luminescent pigments, and pearlescent pigments described in the Paint Raw Materials Handbook 1970 Edition (compiled by the Japan Paint Manufacturers Association), as well as plastic pigments.
• extender pigments include precipitated barium sulfate, powdered gourd, precipitated calcium carbonate, calcium bicarbonate, kansui stone, white alumina, silica, finely powdered hydrous silica (white carbon), ultrafine anhydrous silica (aerosil), silica sand, talc, precipitated magnesium carbonate, bentonite, clay, kaolin, and yellow earth.
• organic pigments include various insoluble azo pigments such as Benzidine Yellow, Hansa Yellow, Lake 4R, etc.; soluble azo pigments such as Lake C, Carmine 6B, Bordeaux 10, etc.; various (copper) phthalocyanine pigments such as Phthalocyanine Blue, Phthalocyanine Green, etc.; various chlorine dyeing lakes such as Rhodamine Lake, Methyl Violet Lake, etc.; various mordant dye pigments such as Quinoline Lake, Fast Sky Blue, etc.; various vat dye pigments such as Anthraquinone pigments, Thioindigo pigments, Perinone pigments, etc.; various quinacridone pigments such as Synchasia Red B, etc.; various dioxazine pigments such as Dioxazine Violet, etc.; various condensed azo pigments such as Chromophtal, etc.; aniline black, etc.
• insoluble azo pigments such as Benzidine Yellow, Hansa Yellow, Lake 4R, etc.
• Inorganic pigments include various chromates such as yellow lead, zinc chromate, and molybdate orange; various ferrocyanide compounds such as Prussian blue; various metal oxides such as titanium oxide, zinc oxide, mapico yellow, iron oxide, red iron oxide, chrome oxide green, and zirconium oxide; various sulfides or selenides such as cadmium yellow, cadmium red, and mercury sulfide; various sulfates such as barium sulfate and lead sulfate; various silicates such as calcium silicate and ultramarine; various carbonates such as calcium carbonate and magnesium carbonate; various phosphates such as cobalt violet and manganese purple; various metal powder pigments such as aluminum powder, gold powder, silver powder, copper powder, bronze powder, and brass powder; flake pigments of these metals, mica flake pigments; metallic pigments and pearl pigments such as mica flake pigments coated with metal oxides and micaceous iron oxide pigments; graphite, carbon black, etc.
• plastic pigments examples include "Grandol PP-1000" and “PP-2000S” manufactured by DIC Corporation.
• the pigment (C4) used may be selected appropriately depending on the purpose, but for example, it is preferable to use inorganic oxides such as titanium oxide and zinc oxide as white pigments, as they have excellent durability, weather resistance, and design properties, and it is preferable to use carbon black as a black pigment.
• the amount of pigment (C4) is, for example, 1 to 400 parts by mass per 100 parts by mass of the total solid content of polyisocyanate composition (X) and polyol composition (Y), and it is more preferable to use 10 to 300 parts by mass to improve adhesion and blocking resistance.
• plasticizer examples include phthalic acid plasticizers, fatty acid plasticizers, aromatic polycarboxylic acid plasticizers, phosphoric acid plasticizers, polyol plasticizers, epoxy plasticizers, polyester plasticizers, and carbonate plasticizers.
• phthalic acid plasticizers include phthalic acid ester plasticizers such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, diheptyl phthalate, di-(2-ethylhexyl) phthalate, di-n-octyl phthalate, dinonyl phthalate, diisononyl phthalate, didecyl phthalate, diisodecyl phthalate, ditridecyl phthalate, diundecyl phthalate, dilauryl phthalate, distearyl phthalate, diphenyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, dicyclohexyl phthalate, octyl decyl phthalate, dimethyl isophthalate, di-(2-ethylhexyl) isophthalate, and di
• Fatty acid plasticizers include, for example, adipic acid plasticizers such as di-n-butyl adipate, di-(2-ethylhexyl) adipate, diisodecyl adipate, diisononyl adipate, di(C6-C10 alkyl) adipate, and dibutyl diglycol adipate; azelaic acid plasticizers such as di-n-hexyl azelate, di-(2-ethylhexyl) azelate, and diisooctyl azelate; and di-n-butyl sebacate, di-( Sebacic acid plasticizers such as diisononyl sebacate and diisononyl sebacate; maleic acid plasticizers such as dimethyl maleate, diethyl maleate, di-n-butyl maleate and di-(2-ethylhexyl) maleate; fumaric acid plastic
• aromatic polycarboxylic acid plasticizers include trimellitic acid plasticizers such as tri-n-hexyl trimellitate, tri-(2-ethylhexyl) trimellitate, tri-n-octyl trimellitate, triisooctyl trimellitate, triisononyl trimellitate, tridecyl trimellitate, and triisodecyl trimellitate, and pyromellitic acid plasticizers such as tetra-(2-ethylhexyl) pyromellitate and tetra-n-octyl pyromellitate.
• Examples of phosphoric acid plasticizers include triethyl phosphate, tributyl phosphate, tri-(2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, octyl diphenyl phosphate, cresyl diphenyl phosphate, cresyl phenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris(chloroethyl) phosphate, tris(chloropropyl) phosphate, tris(dichloropropyl) phosphate, and tris(isopropylphenyl) phosphate.
• polyol-based plasticizers examples include glycol-based plasticizers such as diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, triethylene glycol di-(2-ethylbutyrate), triethylene glycol di-(2-ethylhexoate), and dibutylmethylene bisthioglycolate, and glycerin-based plasticizers such as glycerol monoacetate, glycerol triacetate, and glycerol tributyrate.
• glycol-based plasticizers such as diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, triethylene glycol di-(2-ethylbutyrate), triethylene glycol di-(2-ethylhexoate), and dibutylmethylene bisthioglycolate
• glycerin-based plasticizers such as glycerol monoacetate, glycerol
• epoxy plasticizers include epoxidized soybean oil, epoxy butyl stearate, di-2-ethylhexyl epoxy hexahydrophthalate, diisodecyl epoxy hexahydrophthalate, epoxy triglyceride, epoxidized octyl oleate, and epoxidized decyl oleate.
• polyester plasticizers examples include adipic acid polyesters, sebacic acid polyesters, and phthalic acid polyesters.
• Carbonate plasticizers include propylene carbonate and ethylene carbonate.
• plasticizers include partially hydrogenated terphenyls, adhesive plasticizers, and polymerizable plasticizers such as diallyl phthalate, acrylic monomers and oligomers. These plasticizers can be used alone or in combination of two or more.
• the adhesive of the present invention may contain leveling agents, defoamers, anti-sagging agents, wetting and dispersing agents, viscosity adjusters, ultraviolet absorbers, metal deactivators, peroxide decomposers, flame retardants, reinforcing agents, lubricants, rust inhibitors, fluorescent brightening agents, inorganic heat ray absorbers, flame retardants, antistatic agents, dehydrating agents, known and commonly used thermoplastic elastomers, tackifiers, phosphate compounds, melamine resins, reactive elastomers, etc.
• the amounts of these additives added are appropriately adjusted within a range that does not impair the desired properties of the adhesive of the present invention.
• the adhesive of the present invention may be in the form of either a solvent-based or solventless type.
• the "solvent-based" adhesive of the present invention refers to a form used in a method in which the adhesive is applied to a substrate, heated in an oven or the like to volatilize the organic solvent in the coating film, and then laminated to another substrate, that is, a so-called dry lamination method.
• Either or both of the polyisocyanate composition (X) and the polyol composition (Y) contain an organic solvent capable of dissolving (diluting) the components of the polyisocyanate composition (X) and the components of the polyol composition (Y) used in the present invention.
• the adhesive of the present invention is preferably used in the form of a solvent-based type, since the organic solvent is unlikely to remain in the cured coating film of the adhesive.
• organic solvents examples include esters such as methyl acetate, ethyl acetate, butyl acetate, dimethyl carbonate, 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.
• esters such as methyl acetate, ethyl acetate, butyl acetate, dimethyl carbonate, and cellosolve acetate
• ketones such as acetone, methyl ethyl ketone, isobutyl ketone, and cyclohexanone
• ethers such as tetrahydrofuran and diox
• solvent-free adhesive refers to an adhesive form used in a method in which the polyisocyanate composition (X) and the polyol composition (Y) are substantially free of the highly soluble organic solvents described above, particularly ethyl acetate or methyl ethyl ketone, and the adhesive is applied to a substrate and then laminated to another substrate without a process of volatilizing the solvent by heating in an oven or the like, which is known as a non-solvent lamination method.
• the adhesive is substantially free of organic solvent.
• the polyisocyanate composition (X) contains a low molecular weight alcohol
• the low molecular weight alcohol reacts with the polyol composition (Y) to become part of the coating film, and therefore it is not necessary to volatilize it after application. Therefore, such a form is also treated as a solvent-free adhesive, and the low molecular weight alcohol is not considered to be an organic solvent.
• the adhesive of the present invention is preferably used in a formulation in which the ratio [NCO]/[OH] of the number of moles of isocyanate groups contained in the polyisocyanate composition (X) to the number of moles of hydroxyl groups contained in the polyol composition (Y) is 0.5 to 5.0.
• the laminate of the present invention is obtained by laminating a plurality of substrates (films or papers) using the adhesive of the present invention by a dry lamination method or a non-solvent lamination method.
• a film can be appropriately selected according to the application.
• polyolefin films such as 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) and polypropylene film (CPP: non-oriented polypropylene film, OPP: biaxially oriented polypropylene film), polyvinyl alcohol film, ethylene-vinyl alcohol copolymer film, etc.
• PET polyethylene terephthalate
• HDPE high density polyethylene film
• MDOPE uniaxially oriented polyethylene film
• OPE biaxially oriented polyethylene film
• CPP non-oriented polypropylene film
• OPP biaxially oriented polypropylene film
• polyvinyl alcohol film ethylene-vinyl alcohol copolymer film, etc.
• 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 films include those that use biomass-derived ethylene glycol as a raw material.
• Biomass-derived ethylene glycol is made from ethanol (biomass ethanol) produced from biomass as a raw material.
• biomass-derived ethylene glycol can be obtained by converting biomass ethanol into ethylene oxide using a conventionally known method to produce ethylene glycol.
• Commercially available biomass ethylene glycol may also be used; for example, biomass ethylene glycol available from India Glycoal Limited can be suitably used.
• films containing biomass polyester, biomass polyethylene terephthalate, etc. in which biomass-derived ethylene glycol is used as the diol unit and fossil fuel-derived dicarboxylic acid is used as the dicarboxylic acid unit, are known.
• the dicarboxylic acid unit of the biomass polyester uses a dicarboxylic acid derived from a fossil fuel.
• a dicarboxylic acid an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, and a derivative thereof can be used without limitation.
• the copolymer polyester may be a copolymer polyester containing a copolymer component as a third component, such as a bifunctional oxycarboxylic acid or at least one polyfunctional compound selected from the group consisting of a trifunctional or higher functional polyhydric alcohol, a trifunctional or higher functional polycarboxylic acid and/or anhydride thereof, and a trifunctional or higher functional oxycarboxylic acid, in order to form a crosslinked structure.
• a copolymer component as a third component, such as a bifunctional oxycarboxylic acid or at least one polyfunctional compound selected from the group consisting of a trifunctional or higher functional polyhydric alcohol, a trifunctional or higher functional polycarboxylic acid and/or anhydride thereof, and a trifunctional or higher functional oxycarboxylic acid, in order to form a crosslinked structure.
• biomass polyolefin films such as biomass polyethylene films containing polyethylene resins made from biomass-derived ethylene glycol and biomass polyethylene-polypropylene films are also known.
• the polyethylene-based resin is not particularly limited except that ethylene glycol derived from biomass is used as a part of the raw material.
• examples of the polyethylene-based resin include an ethylene homopolymer and a copolymer of ethylene and an ⁇ -olefin containing ethylene as a main component (ethylene- ⁇ -olefin copolymer containing 90% by mass or more of ethylene units), and these can be used alone or in combination of two or more.
• the ⁇ -olefin constituting the copolymer of ethylene and ⁇ -olefin is not particularly limited, and examples thereof include ⁇ -olefins having 4 to 8 carbon atoms, such as 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene.
• Known polyethylene resins such as low-density polyethylene resins, medium-density polyethylene resins, and linear low-density polyethylene resins, can be used.
• linear low-density polyethylene resins (LLDPE) (copolymers of ethylene and 1-hexene, or copolymers of ethylene and 1-octene) are preferred, and linear low-density polyethylene resins having a density of 0.910 to 0.925 g/cm 3 are more preferred.
• Biomass films that use biomass raw materials and are classified according to the biomass plastic degree specified by ISO 16620 or ASTM D6866 are also on the market.
• Radioactive carbon-14C exists in the atmosphere at a ratio of 1 in 1012 particles, and this ratio is the same for atmospheric carbon dioxide, so this ratio remains the same even in plants that fix this carbon dioxide through photosynthesis.
• the carbon in plant-derived resins contains radioactive carbon-14C.
• 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
• examples of plant-derived low-density polyethylene include products manufactured by Braskem under the trade names "SBC818”, “SPB608”, “SBF0323HC”, “STN7006”, “SEB853”, and “SPB681”, and films using these as raw materials can be suitably used.
• films and sheets containing starch, a biomass raw material, and polylactic acid are also known. These can be selected and used as appropriate depending on the application.
• the biomass film may be a laminate of multiple biomass films, or a laminate of a conventional petroleum-based film and a biomass film. These biomass films may be unstretched or stretched films, and there are no limitations on the manufacturing method.
• 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.
• a film laminated with a vapor-deposited layer of a metal such as aluminum or a metal oxide such as silica or alumina, or a barrier film containing a gas barrier layer such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, or vinylidene chloride may be used.
• a laminate can be made that has barrier properties against water vapor, oxygen, alcohol, inert gases, volatile organic compounds (fragrances), etc.
• the paper can be made from any known paper base material without any particular limitations.
• the paper is made from natural fibers for papermaking such as wood pulp using a known papermaking machine, but the papermaking conditions are not particularly regulated.
• natural fibers for papermaking include wood pulp such as softwood pulp and hardwood pulp, non-wood pulp such as Manila hemp pulp, sisal hemp pulp, and flax pulp, and pulps obtained by chemically modifying these pulps.
• Types of pulp that can be used include chemical pulp made by sulfate cooking, acidic/neutral/alkaline sulfite cooking, soda cooking, etc., ground pulp, chemi-ground pulp, thermomechanical pulp, etc.
• various commercially available fine papers, coated papers, backing papers, impregnated papers, cardboard, and paperboard can also be used.
• the laminate has the following structure: (1) Base film 1/adhesive layer 1/sealant film (2) Base film 1/adhesive layer 1/metal-vapor-deposited unstretched film (3) Base film 1/adhesive layer 1/metal-vapor-deposited stretched film (4) Transparent vapor-deposited stretched film/adhesive layer 1/sealant film (5) Base film 1/adhesive layer 1/base film 2/adhesive layer 2/sealant film (6) Base film 1/adhesive layer 1/metal-vapor-deposited stretched film/adhesive layer 2/sealant film (7) Base film 1/adhesive layer 1/transparent vapor-deposited stretched film/adhesive layer 2/sealant film (8) Base film 1/adhesive layer 1/metal layer/adhesive layer 2/sealant film (9) Base film 1/adhesive layer 1/base film 2/adhesive layer (9)
• the substrate 1 used in the structure (1) may be an MDOPE film, an OPE film, an OPP film, a PET film, a nylon film, paper, or the like.
• the substrate 1 may be coated with a coating for the purpose of improving the gas barrier properties or the ink receptivity when a printing layer is provided, as described below.
• Examples of commercially available substrate films 1 with coatings include K-OPP films and K-PET films.
• the adhesive layer 1 is a cured coating of the adhesive of the present invention.
• sealant films include CPP films, LLDPE films, and gas barrier heat seal films.
• a printing layer may be provided on the adhesive layer 1 side of the substrate 1 (when a substrate film 1 with coating is used, the adhesive layer 1 side of the coating layer) or on the side opposite to the adhesive layer 1.
• the printing layer is formed by a general printing method that has been used for printing on polymer films and paper using various printing inks such as gravure ink, flexo ink, offset ink, stencil ink, and inkjet ink.
• the substrate 1 used in the structures (2) and (3) may be an MDOPE film, an OPE film, an OPP film, a PET film, paper, or the like.
• the adhesive layer 1 is a cured coating of the adhesive of the present invention.
• metal-vapor-deposited unstretched films CPP films, LLDPE films, VM-CPP films and VM-LLDPE films obtained by depositing a metal such as aluminum on a gas-barrier heat seal film, or the like may be used.
• metal-vapor-deposited stretched films VM-MDOPE films, VM-OPE films and VM-OPP films obtained by depositing a metal such as aluminum on an MDOPE film, OPE film or OPP film may be used.
• a printed layer may be provided on either side of the substrate 1.
• Examples of the transparent vapor-deposited stretched film used in configuration (4) include films obtained by vapor-depositing silica or alumina on MDOPE film, OPE film, OPP film, PET film, nylon film, etc.
• a film with a coating on the vapor-deposited layer may be used.
• the adhesive layer 1 is a cured coating of the adhesive of the present invention.
• Examples of the sealant film include the same as those in configuration (1).
• a printed layer may be provided on the surface of the transparent vapor-deposited stretched film on the adhesive layer 1 side (when a film with a coating on the inorganic vapor-deposited layer is used, the surface of the coating layer on the adhesive layer 1 side). The method of forming the printed layer is the same as in configuration (1).
• the substrate 1 in structure (6) may be the same as those in structures (2) and (3).
• Metal-vapor-deposited stretched films include VM-MDOPE film, VM-OPE film, VM-OPP film, and VM-PET film, which are MDOPE film, OPE film, OPP film, and PET film that have been subjected to metal vapor deposition of aluminum or the like.
• At least one of the adhesive layer 1 and the adhesive layer 2 is a cured coating film of the adhesive of the present invention.
• the sealant film may be the same as those in structure (1).
• a printed layer may be provided on either side of the substrate 1.
• Examples of the substrate 1 in structure (7) include PET film, paper, etc.
• Examples of the transparent vapor deposition stretched film include those similar to those in structure (4).
• At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention.
• Examples of the sealant film include those similar to those in structure (1).
• a printed layer may be provided on either side of the substrate 1.
• the substrate 1 in structure (8) may be a PET film, paper, or the like.
• the metal layer may be an aluminum foil, or the like.
• At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention.
• the sealant film may be the same as that in structure (1).
• a printed layer may be provided on either side of the substrate 1.
• examples of the substrate 1 include PET film, paper, etc.
• examples of the substrate 2 include nylon film, etc.
• Examples of the metal layer include aluminum foil, etc.
• At least one layer of the adhesive layers 1, 2, and 3 is a cured coating film of the adhesive of the present invention.
• examples of the sealant film include the same as in structure (1).
• a printed layer may be provided on either side of the substrate 1.
• the adhesive of the present invention is a solvent-based adhesive
• the adhesive of the present invention is applied to a film material that serves as a substrate using a roll such as a gravure roll, and the organic solvent is evaporated by heating in an oven or the like, and then the other substrate is laminated to obtain the laminate of the present invention.
• a roll such as a gravure roll
• the organic solvent is evaporated by heating in an oven or the like
• the other substrate is laminated to obtain the laminate of the present invention.
• After lamination it is preferable to carry out an aging treatment.
• the aging temperature is preferably room temperature to 80°C
• the aging time is preferably 12 to 240 hours.
• the adhesive of the present invention is a solventless type
• the adhesive of the present invention which has been preheated to about 40°C to 100°C, is applied to the film material that will serve as the substrate using a roll such as a gravure roll, and the other substrate is immediately laminated to obtain the laminate of the present invention.
• a roll such as a gravure roll
• the other substrate is immediately laminated to obtain the laminate of the present invention.
• an aging treatment is preferably room temperature to 70°C, and the aging time is preferably 6 to 240 hours.
• the amount of adhesive applied is adjusted appropriately.
• the amount of solids is adjusted to, for example, 1 g/ m2 to 10 g/ m2 , preferably 2 g/ m2 to 5 g/ m2 .
• the amount of adhesive applied is, for example, 1 g/ m2 to 5 g/ m2 , preferably 1 g/ m2 to 3 g/ m2 .
• the laminate of the present invention may further include other films and substrates in addition to the above-mentioned configurations (1) to (10).
• the other substrates in addition to the above-mentioned stretched films, unstretched films, and transparent vapor deposition films, it is also possible to use porous substrates such as paper, wood, and leather, which will be described later.
• the adhesive used when bonding the other substrates may or may not be the adhesive of the present invention.
• the “other layer” may contain known additives or stabilizers, such as antistatic agents, adhesion enhancing coating agents, plasticizers, lubricants, antioxidants, etc. Furthermore, the “other layer” may be a film whose surface has been pretreated with corona treatment, plasma treatment, ozone treatment, chemical treatment, solvent treatment, etc., in order to improve adhesion when laminated with other materials.
• the packaging material of the present invention is obtained by forming the above-mentioned laminate into a bag shape and heat sealing it to obtain the form of the packaging material.
• the packaging material may be in the form of a three-side sealed bag, a four-side sealed bag, a gusseted packaging bag, a pillow packaging bag, a Goebel Top type bottomed container, a Tetra Classic, a Brueck type, a tube container, a paper cup, a lid, etc.
• the packaging material of the present invention may also be appropriately provided with an easy-opening treatment or a resealable means.
• the packaging material of the present invention can be used industrially as a packaging material for mainly filling food, detergents, and pharmaceuticals.
• the contents to be filled include, for example, foods 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 ham, bacon, sausages, chicken processed products, and corned beef; and fish ham, These include sausages, fish paste products, fish cakes, nori, tsukudani (food boiled in soy sauce), dried bonito flakes, shiokara (salted
• non-food items including tobacco, disposable hand warmers, medicines such as infusion packs, liquid laundry detergent, liquid kitchen detergent, liquid bath detergent, liquid bath soap, liquid shampoo, liquid conditioner, cosmetics such as lotion and milky lotion, vacuum insulation materials, batteries, etc.
• the reaction vessel was gradually depressurized, and the reaction was carried out at 1 mmHg or less and 240 ° C. for 2 hours to obtain a polyester polyol (b1-1) with an acid value of 0.8 mg KOH / g, a number average molecular weight of 2000, and a hydroxyl value of about 56 mg KOH / g.
• TMP trimethylolpropane
• the reaction vessel was gradually depressurized, and the reaction was carried out for 2 hours at 1 mmHg or less and 240 ° C. to obtain a polyester polyol (b1-2) with an acid value of 0.8 mg KOH / g, a number average molecular weight of about 2000, and a hydroxyl value of about 56 mg KOH / g.
• TMP trimethylolpropane
• the sealant film surfaces of the two laminated films were placed together and heat-sealed with a 1 cm wide seal bar at 180°C, 1 kgf/ cm2 , 1 second to prepare a sample for measuring heat seal strength.
• a Shimadzu tensile tester was used to set the peel speed to 300 mm/min, and both ends of the heat seal strength measurement sample were pulled to measure the peak tensile strength, which was taken as the heat seal strength.
• the unit of heat seal strength is N/15 mm. Evaluation ⁇ : 60N/15mm or more Evaluation ⁇ : Less than 60N/15mm
• PET film polyethylene terephthalate film
• VMPET aluminum vapor-deposited polyethylene terephthalate
• a PET film and VMCPP (aluminum-deposited non-oriented polypropylene) were bonded together with a two-component curing adhesive (solid content: 3 g/m 2 ) formulated in the combination of the examples or comparative examples, and aged at 40° C. for 72 hours to obtain a laminated film.
• a test piece with a width of 15 mm was cut from the laminated film, and a tensile tester was used to measure whether the deposition was peeled off from the CPP by T-peel at a peeling speed of 300 mm/min.
• ⁇ No deposition peeling
• ⁇ Deposition peeling

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• 2023
  • 2023-11-16 JP JP2024524442A patent/JP7632752B2/ja active Active
  • 2023-11-16 WO PCT/JP2023/041195 patent/WO2024122292A1/ja not_active Ceased

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