Classifications

• • 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
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
  • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
  • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
  • C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols
• • 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
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • 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
• • 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
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3203—Polyhydroxy compounds
  • C08G18/3206—Polyhydroxy compounds aliphatic
• • 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
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
  • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
  • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
  • C08G18/4219—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from aromatic dicarboxylic acids and dialcohols in combination with polycarboxylic acids and/or polyhydroxy compounds which are at least trifunctional
• • 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
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
  • C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
  • C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether groups
• • 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
  • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
• • 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
  • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
  • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
• • 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
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
  • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
  • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
• • 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
  • C08G18/80—Masked polyisocyanates
  • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
  • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
  • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
  • C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
  • C08G18/8025—Masked aliphatic or cycloaliphatic polyisocyanates
• • 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
  • C08G18/80—Masked polyisocyanates
  • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
  • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
  • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
  • C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
  • C08G18/8029—Masked aromatic polyisocyanates
• • 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
• • 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
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/716—Degradable
  • B32B2307/7163—Biodegradable
• • 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
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/748—Releasability

Definitions

• the present invention relates to a two-component curing adhesive for lamination, and to laminates and packaging materials that are biodegradable and can be recycled using an alkaline treatment liquid.
• a known two-component curing adhesive for lamination consisting of a biodegradable polyol composition and a polyisocyanate composition, is, for example, an adhesive containing a polyester polyol (AB) which is a reaction product of a hydroxyl group component (A) containing a diol (a) having a branched structure and a carboxylic acid component (B) containing an aliphatic dicarboxylic acid (b) having 2 to 12 carbon atoms and has a specific number average molecular weight, and a polyester polyol which is a polymer of lactide (C) and a cyclic monomer (D) (see, for example, Patent Document 2).
• AB polyester polyol
• the problem that the present invention aims to solve is to provide a two-component curing adhesive for lamination that has sufficient performance as a lamination adhesive for packaging materials, while also having excellent biodegradability and releasability when immersed in an alkaline aqueous solution, and to provide a laminate and packaging material that are obtained using the adhesive and have biodegradability and can be recycled using an alkaline treatment solution.
• the inventors have discovered that a two-component curing adhesive containing a polyol composition (X) containing a specific polyester polyol compound (A) and a polyisocyanate composition (Y) containing a polyisocyanate compound (B) can solve the above problems.
• the present invention provides a two-component curing adhesive comprising a polyol composition (X) containing a polyester polyol compound (A) and a polyisocyanate composition (Y) containing a polyisocyanate compound (B), in which the number average molecular weight of the polyester polyol compound (A) is in the range of 500 to 20,000, and either or both of the polyester polyol compound (A) and the polyisocyanate compound (B) are reaction products of aliphatic alcohols having a quaternary carbon atom and a trivalent or higher hydroxyl group.
• the present invention also provides a laminate comprising a first substrate, a second substrate, and an adhesive layer disposed between the first substrate and the second substrate, the adhesive layer being a cured coating film of the two-component curing adhesive described above.
• the present invention also provides a packaging material that uses the laminate described above.
• the present invention also provides a method for recycling a laminate, the method comprising the steps of immersing a laminate, which includes a first substrate, a second substrate, and an adhesive layer disposed between the first substrate and the second substrate, the adhesive layer being a cured coating film of the two-component curing adhesive described above, in a stripping liquid to separate the laminate into individual layers, and recovering each of the separated layers.
• the present invention provides a two-component curing adhesive for lamination that has sufficient performance as a lamination adhesive for packaging materials, while also exhibiting excellent biodegradability and release properties when immersed in an alkaline aqueous solution, and it is also possible to provide a laminate obtained by using the adhesive that is biodegradable and can be recycled using an alkaline treatment solution.
• the adhesive of the present invention is a two-component curing adhesive comprising a polyol composition (X) containing a polyester polyol compound (A) and a polyisocyanate composition (Y) containing a polyisocyanate compound (B), in which the number average molecular weight of the polyester polyol (A) is in the range of 500 to 20,000, and either or both of the polyester polyol compound and the polyisocyanate compound (B) are reaction products of aliphatic alcohols having a quaternary carbon atom and a trivalent or higher hydroxyl group.
• the adhesive of the present invention will be described in detail below.
• Polyol Composition (X) (Polyester polyol compound (A))
• the polyol composition (X) used in the adhesive of the present invention contains a polyester polyol compound (A).
• the polyester polyol compound (A) has a number average molecular weight in the range of 500 to 20,000. This range provides excellent decomposition properties under composting conditions. A range of 2,000 to 10,000 is particularly preferred. In this specification, the number average molecular weight 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
• polyester polyol compound (A) used in the present invention examples include the following.
• Polyester polyols (1) which are reaction products of polyesters obtained by ring-opening polymerization of cyclic ester compounds such as propiolactone, butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone, and ⁇ -methyl- ⁇ -valerolactone with aliphatic polyhydric alcohols such as glycol, glycerin, trimethylolpropane, and pentaerythritol;
• Polyester polyol (2) obtained by reacting a difunctional polyol such as glycol, dimer diol, or bisphenol with a polycarboxylic acid as raw materials: (3) a polyester polyol obtained by reacting a trifunctional or tetrafunctional aliphatic polyhydric alcohol with a polycarboxylic acid; (4) a polyester polyol obtained by reacting a bifunctional polyol, the trifunctional or tetrafunctional aliphatic polyalcohol
• polyester polyether polyurethane polyol obtained by reacting at least one of these polyester polyols (1) to (5) with a polyether polyol and an isocyanate compound; Polyester polyurethane polyols obtained by polymerizing the polyester polyols (1) to (5) with an isocyanate compound.
• the polyester polyol compound (A) may be used alone or in combination of two or more.
• the polyols used as the raw material for the polyester polyol compound (A) include, for example, glycols such as ethylene glycol, 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, 1,2-nonanediol, 1,2-decanediol, 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,
• Trifunctional or tetrafunctional polyhydric aliphatic alcohols such as glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol; Bisphenols such as bisphenol A, bisphenol F, hydrogenated bisphenol A, and hydrogenated bisphenol F; dimer diols; 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 polyhydric alcohols; Polyether urethane polyol obtained by further increasing the molecular weight of a polyether polyol with an isocyanate compound; Examples of the polyol include castor oil, dehydrated castor oil, hydrogenated castor oil which is a hydrogenated product of castor oil,
• polyvalent carboxylic acid used as a raw material for the polyester polyol compound (A) examples 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 an
• 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; dimer acid (a liquid fatty acid containing monobasic and tribasic acids as well as C36 dibasic acid produced by dimerization of C18 unsaturated fatty acids made from vegetable oils and fats); Alkyl esters of aliphatic polybasic acids such as dimethyl malonate, diethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipicate, 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.
• polyester polyols obtained by reacting an aliphatic polyol with an aliphatic polycarboxylic acid are preferably used because they have superior biodegradability.
• 1,2-alkanediols are preferred, including the above-mentioned 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, 1,2-nonanediol, and 1,2-decanediol.
• adipic acid is preferable as the aliphatic polycarboxylic acid.
• the combinations of diethylene glycol and adipic acid, 1,2-propanediol and adipic acid, 1,2-butanediol and adipic acid, and 1,2-pentanediol and adipic acid are particularly excellent in biodegradability.
• the aliphatic polyol and the aliphatic polycarboxylic acid are preferably used in such an amount that their total weight is 50 to 100% by weight based on the total weight of the polyester polyol.
• the hydroxyl value of the polyester polyol compound (A) is preferably in the range of 5 to 250 mgKOH/g, more preferably 5 to 100 mgKOH/g or more, and even more preferably 5 to 50 mgKOH/g or less.
• the hydroxyl value can be measured by the method described in JIS-K0070.
• the polyol composition (X) may contain various polyols other than the polyester polyol compound (A).
• various polyols include polymer polyols selected from polyether polyols, polyurethane polyols, polyether (polyurethane) polyols, acrylic polyols, polycarbonate polyols, polyhydroxyl alkanes, castor oil, and mixtures thereof.
• polyether polyols examples include polyether polyols obtained by polymerizing oxirane compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran using low molecular weight polyols such as water, ethylene glycol, propylene glycol, trimethylolpropane, and glycerin as an initiator.
• polyether ester polyols examples 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 dialkyl esters thereof, or mixtures thereof.
• the polyurethane polyol is a polyol that has a urethane bond in one molecule, such as a reaction product of a polyether polyol having a number average molecular weight of 200 to 20,000 and an organic polyisocyanate, with an NCO/OH ratio of preferably less than 1, and more preferably 0.9 or less.
• the organic polyisocyanate may be a polyisocyanate compound, particularly a diisocyanate compound, as described below.
• 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 viscosity of the polyol composition (X) is adjusted to a range suitable for the non-solvent lamination method.
• the viscosity is adjusted to be in the range of 100 to 5000 mPas, more preferably 100 to 3000 mPas at 30 to 80°C.
• the viscosity of the polyol composition (X) can be adjusted by the skeleton of the polyester polyol compound (A) or a plasticizer, which will be described later.
• the viscosity can be reduced by using, for example, polypropylene glycol or a polyester polyol obtained by reacting an aliphatic carboxylic acid with a polyol.
• the viscosity can be increased by using a polyester polyol obtained by reacting an aromatic carboxylic acid with a polyol.
• the viscosity of the polyol composition (X) is adjusted to a viscosity suitable for coating by diluting it with a solvent.
• polyester polyol compound (A) used in the present invention is a reaction product of an aliphatic alcohol having a quaternary carbon atom and a trivalent or higher hydroxyl group
• examples of the aliphatic alcohol having a quaternary carbon atom and a trivalent or higher hydroxyl group include trifunctional or tetrafunctional polyhydric alcohols such as trimethylolpropane, trimethylolethane, trimethylolbutane, and pentaerythritol.
• polyester polyol compound (A) which is a reaction product of an aliphatic alcohol having a quaternary carbon atom and a trivalent or higher hydroxyl group
• polyester polyol compound (A) which is a reaction product of an aliphatic alcohol having a quaternary carbon atom and a trivalent or higher hydroxyl group
• ⁇ Polyester polyol compound which is a reaction product of trimethylolpropane, diethylene glycol, and adipic acid ⁇ Polyester polyol compound which is a reaction product of trimethylolpropane, diethylene glycol, adipic acid, isophthalic acid, and trimellitic anhydride.
• Polyester polyol compound which is a reaction product of trimethylolpropane, diethylene glycol, adipic acid, isophthalic acid, and pyromellitic anhydride.
• Polyol compounds Polyester polyol compounds which are reaction products of trimethylolpropane, diethylene glycol, adipic acid, isophthalic acid and succinic acid. Polyester polyol compounds which are reaction products of trimethylolpropane, 1,2 propanediol and adipic acid.
• Polyester polyol compounds which are reaction products of trimethylolpropane, 1,2 propanediol, adipic acid and isophthalic acid are reaction products of trimethylolpropane, 1,2 propanediol, adipic acid, isophthalic acid and trimellitic anhydride.
• Polyester polyol compounds which are reaction products of trimethylolpropane, 1,2 propanediol, adipic acid, isophthalic acid and pyromellitic anhydride
• Polyester polyol compounds which are reaction products of trimethylolpropane, 1,2 propanediol, adipic acid, isophthalic acid, and phthalic anhydride Polyester polyol compounds which are reaction products of trimethylolpropane, 1,2 propanediol, adipic acid, isophthalic acid, and succinic anhydride; Polyester polyol compounds which are reaction products of trimethylolpropane, diethylene glycol, 1,2 propanediol, and adipic acid; Polyester polyol compounds which are reaction products of trimethylolpropane, diethylene glycol, 1,2 propanediol, adipic acid, and isophthalic acid; polyester polyol compound which is a reaction product of glycerol, 1,2 propanediol, adipic acid, isophthalic acid, and trimellitic anhydride; polyester polyol compound which is a reaction product of trimethylolpropane, diethylene glycol, 1,2 propanediol, a
• the polyester polyol compound (A) is preferably acid-modified, and shows better biodegradability.
• the acid-modified polyester polyol compound (A) is a polyol having an acidic group in the polyol molecule.
• the acidic group include a carboxyl group and a phosphoric acid group, and among them, a carboxyl group is preferred from the viewpoint of ease of production.
• the method for producing the acid-modified polyester polyol compound (A) is not particularly limited, but the method of adding an acid anhydride-containing compound to the hydroxyl group of various polyols to introduce carboxyl groups is preferably used.
• the acid anhydride-containing compound added to various polyols includes trimellitic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, etc., and among them, trimellitic anhydride is preferably used.
• trimellitic anhydride is preferably used.
• the acid value of the polyester polyol compound (A) is not particularly limited, but is preferably 5 to 50 mg KOH/g, and more preferably 10 to 30 mg KOH/g. If the acid value is within this range, biodegradability is further improved.
• the acid value can be measured by the method described in JIS-K0070.
• polyester polyol compound (A) which is a reaction product of an aliphatic alcohol having a quaternary carbon atom and a trivalent or higher hydroxyl group
• a specific preferred embodiment of the polyester polyol compound (A) is, for example, polyester polyol (A) made from diethylene glycol, adipic acid, and phthalic acid as reaction raw materials.
• the polyisocyanate composition (Y) contains a polyisocyanate compound (B) having a plurality of isocyanate groups.
• the polyisocyanate compound (B) is not particularly limited, and examples thereof include aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and biuret, nurate, adduct, allophanate, carbodiimide-modified, polymeric, 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 may be the same as those exemplified as polyol composition (X). It is preferable to use at least one of polyalkylene glycol or polyester polyol, since this allows the adhesive to have a low viscosity while increasing the adhesive strength.
• the polyalkylene glycol preferably has a number average molecular weight in the range of 200 to 6,000.
• the polyester polyol is preferably obtained by reacting a polyalkylene glycol with an aliphatic polycarboxylic acid having 2 to 30 carbon atoms.
• the polyester polyol may use, as its raw alcohol component, a trifunctional or higher alcohol such as glycerin, trimethylolpropane, or pentaerythritol in a proportion of 10 mass% or less of the polyol component.
• polyisocyanates obtained by reacting aromatic polyisocyanates with polyalkylene glycols having a number average molecular weight in the range of 200 to 6,000, and polyisocyanates obtained by reacting aromatic polyisocyanates with polyester polyols having a number average molecular weight in the range of 200 to 3,000 are preferred because they can impart appropriate flexibility to the cured product.
• Polyisocyanates with an isocyanate content of 5 to 20% by mass as determined by titration method (using di-n-butylamine) are preferred because they provide appropriate resin viscosity and excellent coatability.
• polyisocyanates obtained by reacting aromatic polyisocyanates with polyester polyols having a number average molecular weight in the range of 200 to 3,000 are preferred because of their excellent adhesive strength.
• polyisocyanates obtained by reacting aromatic polyisocyanates with a mixture of polyester polyols having a number average molecular weight in the range of 200 to 3,000 and polyalkylene glycols having a number average molecular weight in the range of 200 to 6,000 are preferred because of their excellent adhesive strength.
• Those with an isocyanate content of 5 to 20% by mass according to the standard method (using di-n-butylamine) are also preferred because they have an appropriate resin viscosity and excellent coatability.
• the equivalent ratio [NCO]/[OH] of the isocyanate groups and hydroxyl groups used in the reaction is in the range of 1.2 to 10.0, since this brings the viscosity of the adhesive into an appropriate range and improves the coatability.
• the viscosity of the polyisocyanate composition (Y) is adjusted to a range suitable for the non-solvent lamination method.
• the viscosity at 30 to 80°C is adjusted to be in the range of 500 to 5000 mPas, more preferably 500 to 3000 mPas.
• the viscosity of the polyisocyanate composition (Y) can be adjusted, for example, by the amount of urethane prepolymer or the amount of low molecular weight isocyanate compound.
• the viscosity of the polyisocyanate composition (Y) is adjusted to a viscosity suitable for coating by diluting it with a solvent.
• the polyisocyanate compound (B) used in the present invention is a reaction product of an aliphatic alcohol having a quaternary carbon atom and a trivalent or higher hydroxyl group
• examples of the aliphatic alcohol having a quaternary carbon atom and a trivalent or higher hydroxyl group include trimethylolpropane, trimethylolethane, trimethylolbutane, pentaerythritol, etc.
• polyisocyanate compound (B) which is a reaction product of an aliphatic alcohol having a quaternary carbon atom and a trivalent or higher hydroxyl group
• polyisocyanate compound (B) which is a reaction product of an aliphatic alcohol having a quaternary carbon atom and a trivalent or higher hydroxyl group
• a polyisocyanate compound which is a reaction product of trimethylolpropane and hexamethylene diisocyanate (2)
• the polyester polyol compound (A) and the polyisocyanate compound (B) are reaction products of aliphatic alcohols having a quaternary carbon atom and a hydroxyl group with three or more valences.
• the polyisocyanate compound (B) is a reaction product of aliphatic alcohols having a quaternary carbon atom and a hydroxyl group with three or more valences, since better biodegradability can be obtained.
• the polyol composition (X) and/or the polyisocyanate composition (Y) which are components of the adhesive contain an aromatic ring and/or an aliphatic ring.
• a method for introducing these aromatic rings and/or aliphatic rings into the adhesive composition for example, a method of using the polyol or the polycarboxylic acid having an aromatic ring and/or an aliphatic ring as the raw material of the polyester polyol compound (A) can be mentioned.
• polyester polyol compound (A) is a polyester polyurethane polyol
• a polyisocyanate having an aromatic ring and/or an aliphatic ring can be used as the polyisocyanate used in the urethanization reaction, and there is no particular limitation.
• the polyisocyanate compound (B) a polyisocyanate having an aromatic ring and/or an aliphatic ring can also be used.
• the content of the aromatic rings and/or aliphatic rings is preferably 0.63 to 2.8 meq/g, and most preferably 0.65 to 2.0 meq/g, relative to the total mass of the adhesive of the present invention.
• the content of the aromatic rings and/or aliphatic rings is calculated by the following formula.
• Aromatic ring and aliphatic ring content in total mass of adhesive (aromatic ring (eq)+aliphatic ring (eq))/(weight (solid content) (g) of polyol composition (X)+weight (solid content) (g) of polyisocyanate composition (Y)) ⁇ 1000
• the total concentration of urethane bonds and urea bonds relative to the total mass (solid content) of the adhesive of the present invention is preferably 0.1 to 2.0 meq/g, and the total concentration of urethane bonds and urea bonds is more preferably 0.2 to 1.0 meq/g.
• the urethane bond concentration and the urea bond concentration are values calculated by the following formula: where OH represents a hydroxyl group, and NCO represents an isocyanate group.
• NCO(eq) (NCO%(solids)/4202) ⁇ (weight(solids) of polyisocyanate composition (Y))
• the "amount of the aliphatic alcohol having a quaternary carbon atom and a trivalent or higher hydroxyl group in the total mass of the adhesive (mmol/g)" is a value calculated by the following formula, and the adhesive of the present invention preferably contains 0.05 to 1.0 mmol/g, and most preferably contains 0.1 to 0.5 mmol/g, of the total mass of the adhesive.
• the present invention it is preferable to balance the content of the aromatic rings and/or aliphatic rings in the total mass of the adhesive of the present invention, the urethane bond concentration, and the amount of the aliphatic alcohol having a quaternary carbon atom and a trivalent or higher hydroxyl group.
• the adhesive of the present invention may contain components other than the above-mentioned components.
• the other component (D) may be contained in either or both of the polyol composition (X) and the polyisocyanate composition (Y), or may be prepared separately from these and mixed with the polyol composition (X) and the polyisocyanate composition (Y) immediately before application of the adhesive. Each component will be described below.
• the adhesive of the present invention may contain a compound produced by intramolecular dehydration condensation of a molecule having a hydroxyl group and a carboxyl group (hydroxycarboxylic acid).
• examples of such compounds include lactones and lactides.
• lactide is preferably used because it can impart good biodegradability.
• lactones include cyclic lactone compounds such as ⁇ -caprolactone, ⁇ -butyrolactone, ⁇ -valerolactone, and ⁇ -valerolactone.
• Lactide is a cyclic compound having two ester bonds in a molecule formed by dehydration condensation of the hydroxyl group and the carboxyl group of two molecules of hydroxy acid.
• lactides derived from lactic acid may be optically active substances, and include L-lactide, D-lactide, and meso-lactide.
• L-lactide and meso-lactide are preferred because they are not only easily available, but also derived from plants, and therefore can increase not only biodegradability but also biomass degree.
• Polyesters having a lactic acid skeleton are decomposed by enzymes secreted by microorganisms in soil, and therefore can be made to have a small load on the environment.
• the content of the dehydrated condensate (C) of hydroxy acid is preferably 1 to 10% by mass based on the total solid content of the adhesive of the present invention, and within this range, biodegradability can be achieved.
• the content is more preferably 2 to 5% by mass. If the amount of lactide added is too large, it is undesirable because it leads to a decrease in adhesive performance.
• the dehydration condensate (C) of a hydroxy acid may be contained in either the polyol composition (X) or the polyisocyanate composition (Y), or in both of them. From the viewpoint of storage stability, however, it is preferable that it is contained in the polyol composition.
• the adhesive of the present invention may contain a catalyst such as a metal catalyst, an amine catalyst, or an aliphatic cyclic amide compound.
• Metal catalysts 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.
• the adhesive of the present invention may contain, as the acid anhydride, a cyclic aliphatic acid anhydride, an aromatic acid anhydride, an unsaturated carboxylic acid anhydride, etc., and may be used alone or in combination of two or more.
• phthalic anhydride trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, dodecenylsuccinic anhydride, polyadipic anhydride, polyazelaic anhydride, polysebacic anhydride, poly(ethyloctadecanedioic) anhydride, poly(phenylhexadecanedioic) 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 dianhydride, H
• 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.
• the adhesive of the present invention may contain a coupling agent such as a silane coupling agent, a titanate-based coupling agent, or an aluminum-based coupling agent.
• a coupling agent such as a silane coupling agent, a titanate-based coupling agent, or 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 adhesive of the present invention is not particularly limited as to the pigment, and may contain organic pigments or 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, as well as plastic pigments, etc., as described in the 1970 edition of the Paint Raw Materials Handbook (compiled by the Japan Paint Manufacturers Association).
• 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 pigments used may be selected appropriately depending on the purpose, but for example, inorganic oxides such as titanium oxide and zinc oxide are preferably used as white pigments because of their excellent durability, weather resistance, and design properties, and carbon black is preferably used as black pigments.
• the amount of pigment to be blended is, for example, 1 to 400 parts by mass per 100 parts by mass of the total solid content of the polyol composition (X) and the polyisocyanate composition (Y), and it is more preferable to use 10 to 300 parts by mass to improve adhesion and blocking resistance.
• the adhesive of the present invention can contain a plasticizer such as a phthalic acid-based plasticizer, a fatty acid-based plasticizer, an aromatic polycarboxylic acid-based plasticizer, a phosphoric acid-based plasticizer, a polyol-based plasticizer, an epoxy-based plasticizer, a polyester-based plasticizer, or a carbonate-based plasticizer.
• a plasticizer such as a phthalic acid-based plasticizer, a fatty acid-based plasticizer, an aromatic polycarboxylic acid-based plasticizer, a phosphoric acid-based plasticizer, a polyol-based plasticizer, an epoxy-based plasticizer, a polyester-based plasticizer, or a carbonate-based plasticizer.
• 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 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 polyol composition (X) and the polyisocyanate composition (Y) contain an organic solvent capable of dissolving (diluting) the components of the polyol composition (X) and the components of the polyisocyanate composition (Y) used in the present invention.
• 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 polyol composition (X) and the polyisocyanate 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 polyol composition (X) is substantially free of organic solvent.
• the polyol composition (X) contains a low molecular weight alcohol, the low molecular weight alcohol reacts with the polyisocyanate composition (Y) to become part of the coating film, and therefore there is no need 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 (Y) to the number of moles of hydroxyl groups contained in the polyol composition (X) [OH] is 0.8 to 5.0, preferably 1.0 to 5.0.
• the two-component curing adhesive of the present invention exhibits biodegradability.
• the biodegradability is a value determined by a method in accordance with JIS K6953 1:2011. Specifically, the biodegradability is evaluated at an incubation temperature of 58° C. for an incubation period of 28 days. Under these conditions, the compost decomposition rate of the two-component curing adhesive of the present invention under composting conditions is more preferably 20% or more, even more preferably 30% or more, and particularly preferably 40% or more.
• 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
• 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.
• 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.
• biodegradable films are also preferred. Films and sheets containing starch, the aforementioned biomass raw material, and polylactic acid are known to be biodegradable. These can be selected and used appropriately depending on the application.
• 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, or various biodegradable substrates, such as paper or cellophane film.
• 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, gas barrier heat seal films, and various biodegradable substrates, such as polybutylene succinate and polylactic acid.
• a printing layer may be provided on the surface of the substrate 1 on the adhesive layer 1 side (when a substrate film 1 with a coating is used, the surface of the coating layer on the adhesive layer 1 side) or on the surface opposite to the adhesive layer 1.
• the printing layer is formed using various printing inks such as gravure ink, flexographic ink, offset ink, stencil ink, and inkjet ink, using the general printing methods that have traditionally been used for printing on polymer films and paper.
• 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 used in configuration (5) may be a PET film, paper, or the like.
• the substrate 2 may be a nylon film, 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 configuration (1).
• a printed layer may be provided on either side of the substrate 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 usually used as a two-liquid adhesive. Therefore, it is preferable to mix the polyol composition (X) and the polyisocyanate composition (Y) immediately before use. As described above, it is preferable to mix and use them so that the ratio [NCO]/[OH] of the number of moles of isocyanate groups contained in the polyisocyanate composition (Y) to the number of moles of hydroxyl groups contained in the polyol composition (X) [NCO] is 0.8 to 5.0, preferably 1.0 to 5.0.
• 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 printing layer is a layer on which characters, figures, symbols, and other desired patterns are printed.
• the printing method or printing ink there is no particular limitation on the printing method or printing ink, and any known printing method or printing ink can be used.
• Printing inks using gravure printing, flexographic printing, lithographic offset printing, inkjet recording printing, and the like are often used for the film used as the substrate.
• Printing inks that combine these printing methods with a method of curing with active energy rays such as ultraviolet rays (UV), LEDs, and electron beams (EB), or a method of curing with heat, etc. are also used.
• active energy rays such as ultraviolet rays (UV), LEDs, and electron beams (EB), or a method of curing with heat, etc.
• UV ultraviolet rays
• EB electron beams
• heat heat
• gravure printing ink and flexographic printing ink in some industries, gravure printing ink and flexographic printing ink are referred to as liquid printing ink
• UV-curable ink for lithographic offset printing in some industries, gravure printing ink and flexographic printing ink are referred to as liquid printing ink
• electron beam curable ink for lithographic offset printing in some industries, UV-curable ink for inkjet recording and printing
• electron beam curable ink for inkjet recording and printing include electron beam curable ink for inkjet recording and printing.
• 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, porous substrates such as paper, wood, and leather, which will be described later, can also be used.
• 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 processed seafood products such as sausages, fish paste products, kamaboko, nori, tsukudani (food boiled in soy sauce), dried bonito flakes,
• 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 laminate of the present invention and packaging materials using the laminate can be separated into the respective base materials and recovered by a treatment using an alkaline solution, which is currently the most widely used recycling treatment.
• the laminate can be separated and recovered by a recycling method having a step of separating the laminate into layers by immersing the laminate in a stripping solution such as an alkaline solution while heating and stirring the laminate at 20 to 90° C., and a step of recovering each separated layer.
• the alkaline solution used in the separation and recovery method is preferably an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution.
• the aqueous sodium hydroxide solution or the aqueous potassium hydroxide solution has a concentration of preferably 0.5% to 10% by mass, and more preferably 1% to 5% by mass.
• the pH is preferably 10 or higher.
• the alkaline solution may contain a water-soluble organic solvent.
• water-soluble organic solvents include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (cellosolve), ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol dibutyl ether, diethylene glycol monomethyl ether (methyl carbitol), diethylene glycol dimethyl ether, diethylene glycol monoethyl ether (carbitol), diethylene glycol diethyl ether (diethyl carbitol), diethylene glycol monobutyl ether (butyl carbitol), diethylene glycol dibutyl ether, and triethylene glycol.
• Examples include ethylene glycol monomethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, methylene dimethyl ether (methylal), propylene glycol monobutyl ether, tetrahydrofuran, acetone, diacetone alcohol, acetonylacetone, acetylacetone, ethylene glycol monomethyl ether acetate (methyl cellosolve acetate), diethylene glycol monomethyl ether acetate (methyl carbitol acetate), diethylene glycol monoethyl ether acetate (carbitol acetate), ethyl hydroxyisobutyrate and ethyl lactate, which may be used alone or in combination of two or more.
• the content of the water-soluble organic solvent in the alkaline solution is preferably 30% to 70% by mass, and more preferably 40% to 60% by mass.
• the alkaline solution may contain a water-insoluble organic solvent.
• water-insoluble organic solvents include alcohol-based solvents such as n-butanol, 2-butanol, isobutanol, and octanol; aliphatic hydrocarbon-based solvents such as hexane, heptane, and normal paraffin; aromatic hydrocarbon-based solvents such as benzene, toluene, xylene, and alkylbenzene; halogenated hydrocarbon-based solvents such as methylene chloride, 1-chlorobutane, 2-chlorobutane, 3-chlorobutane, and carbon tetrachloride; ester-based solvents such as methyl acetate, ethyl acetate, and butyl acetate; ketone-based solvents such as methyl isobutyl ketone, methyl ethyl ketone, and cyclohexanone; and ether-based solvent
• the alkaline solution may contain a surfactant.
• the surfactant include various anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants, and among these, anionic surfactants and nonionic surfactants are preferred.
• anionic surfactants include alkylbenzenesulfonates, alkylphenylsulfonates, alkylnaphthalenesulfonates, higher fatty acid salts, sulfate ester salts of higher fatty acid esters, sulfonates of higher fatty acid esters, sulfate ester salts and sulfonates of higher alcohol ethers, higher alkyl sulfosuccinates, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, and polyoxyethylene alkyl ether phosphates.
• dodecylbenzenesulfonates include dodecylbenzenesulfonates, isopropylnaphthalenesulfonates, monobutylphenylphenol monosulfonates, monobutylbiphenylsulfonates, and dibutylphenylphenol disulfonates.
• nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, fatty acid alkylol amides, alkyl alkanol amides, acetylene glycol, oxyethylene adducts of acetylene glycol, polyethylene glycol polypropylene glycol block copolymers, and the like.
• polyoxyethylene nonylphenyl ether polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid alkylol amides, acetylene glycol, oxyethylene adducts of acetylene glycol, and polyethylene glycol polypropylene glycol block copolymers are preferred.
• surfactants that can be used include silicone surfactants such as polysiloxane oxyethylene adducts; fluorosurfactants such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and oxyethylene perfluoroalkyl ethers; and biosurfactants such as spiculisporic acid, rhamnolipids, and lysolecithin.
• silicone surfactants such as polysiloxane oxyethylene adducts
• fluorosurfactants such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and oxyethylene perfluoroalkyl ethers
• biosurfactants such as spiculisporic acid, rhamnolipids, and lysolecithin.
• surfactants can be used alone or in combination of two or more.
• the amount added is preferably in the range of 0.001 to 2 mass % of the total amount of the alkaline solution, more preferably 0.001 to 1.5 mass %, and even more preferably 0.01 to 1 mass %.
• the alkaline solution preferably contains a terpene compound.
• the terpene compound include monoterpenes such as ⁇ -pinene, ⁇ -pinene, limonene, ⁇ -phellandrene, ⁇ -terpinene, ⁇ -terpinene, aucimene, myrcene, camphene, terpinolene, sylvestrene, sabinene, carene, tricyclene, and fenthene; sesquiterpenes such as longifolene, caryophyllene, bizabolene, santalene, zingiberene, curcumene, cadinene, sesquibenihen, and cedrene; and diterpenes such as campholene, podocarpulene, myrene, phyllocladene, and totarene.
• Monoterpene alcohols such as ⁇ -citronellol, geraniol, nerol, linalool, terpineol, carpeol, thuyl alcohol, pinocampheol, and fenchyl alcohol; sesquiterpene alcohols such as farnesol, nerolidol, casinol, eudesmol, guayol, baturyl alcohol, carotol, lanceol, and kessoglycol; terpene alcohols such as diterpene alcohols such as phytol, sclareol, manol, hinokitiol, ferruginol, and totarol;
• Terpene aldehydes such as citronellal, citral, cyclocitral, safranal, ferrandolal, and perillaldehyde,
• monoterpene ketones such as dagetone, ionone, irone, carbomentone, carbotanacetone, piperitenone, thujone, and calone; sesquiterpene ketones such as cyperone, eremophilone, and zerumbone; and terpene ketones such as sugiol and ketomanoyl oxide.
• terpene hydrocarbons and it is more preferable to use limonene.
• the content of the terpene compound can be adjusted as appropriate, but as an example, it is preferably 0.1% by mass or more and 90% by mass or less of the alkaline solution, more preferably 1% by mass or more, and even more preferably 5% by mass or more. It is also more preferable that the content of the terpene compound is 50% by mass or less of the alkaline solution.
• the laminate is immersed in an alkaline solution heated to 20 to 90°C in a treatment tank.
• an alkaline solution heated to 20 to 90°C heated to 20 to 90°C in a treatment tank.
• 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.
• Ultrasonic vibrations may be applied during immersion.
• a method can be used in which an ultrasonic vibrator is attached to the treatment tank and ultrasonic vibrations are applied to the alkaline solution.
• the alkaline solution is preferably stirred when the laminate is immersed in it.
• Stirring methods include mechanically stirring the dispersion of the laminate 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. These methods may be used in combination to efficiently peel off the laminate.
• the time for which the laminate is immersed in the alkaline solution depends on the composition of the laminate, but is generally in the range of 2 minutes to 48 hours. If the immersion time is less than 2 minutes, there is a risk that the adhesive layer will not completely peel off from the laminate and some of it will remain.
• the laminate may be immersed in the alkaline solution once or in several separate sessions.
• the laminate has a printed ink layer to display the product name and the like and to add decorativeness, in addition to the adhesive, but the printed ink layer can also be peeled off or dissolved by immersing the laminate in an alkaline solution.
• the laminate may have a metal foil or vapor deposition film such as aluminum laminated on it, but in the present invention, the metal foil or vapor deposition film can also be peeled off or dissolved.
• the alkaline solution used in the separation and recovery method is presumed to act on the interface between the laminate and the adhesive or printing ink, significantly reducing the adhesive strength, causing interfacial peeling between the laminate and the adhesive or printing ink.
• cross-linked coatings of reactive adhesives and the like hardly dissolve in any solution, but in the present invention, they are not dissolved but rather cause interfacial peeling, which is presumed to enable efficient separation and recovery in a short time.
• Each substrate obtained by separating and recovering laminates or packages using the two-component curing adhesive of the present invention using the above-described separation and recovery method can be processed using various known recycled plastic processing methods to produce recycled plastics.
• a laminate or package using the two-component curing adhesive of the present invention can be processed directly using any of a variety of known recycled plastic processing methods to produce recycled plastic.
• recycled plastic can be obtained by a manufacturing method that includes a process for recovering the laminate of the present invention by separating it into its respective base materials, or a process for crushing the laminate or packaging of the present invention, a process for melt-kneading the crushed film pieces, and a process for pelletizing the melt-kneaded mixture.
• the crusher used for crushing is not particularly limited and any known crusher may be used.
• the crushed film pieces are physically blended by melt kneading, solvent cast blending, latex blending, polymer complex, etc.
• the melt kneading method is common.
• kneading devices include a tumbler, a Henschel mixer, a rotary mixer, a super mixer, a ribbon tumbler, a V blender, etc.
• the film pieces are melt kneaded by such a kneading device and then pelletized.
• a single-screw or multi-screw extruder is generally used for melt kneading pelletization, and the film pieces may be charged as they are or may be charged after being compressed and reduced in volume with or without heating.
• a Banbury mixer, a roller, a co-kneader, a blast mill, a Prabender blastograph, etc. can also be used, which are operated batchwise or continuously.
• the film pieces may be used as molding resins and melt kneaded in the heating cylinder of a molding machine without melt kneading.
• Polyester polyols A-2 to A-4 and A-6 to A-11 were obtained in the same manner as in Synthesis Example 1 or Synthesis Example 2, except that the blending amounts were changed as shown in Table 1.
• the raw materials and physical properties of the polyols are shown in Table 1. Note that blanks indicate that no polyol was added.
• Method 1 A two-component curing adhesive (solid content 3 g/ m2 ) formulated in the combination of the Examples or Comparative Examples was applied onto a polyethylene terephthalate film and aged for 72 hours at 50°C to obtain a coating film for evaluating biodegradability.
• the adhesive alone was highly tacky and could not maintain the shape of the coating, so it was evaluated as a thin film on the polyethylene terephthalate film.
• Compost decomposition was measured by a method in accordance with JIS K6953-1:2011.
• Method 2 The compost decomposition properties of the adhesives of Examples 3 and 5 to 10 were measured in the same manner as in the compost biodegradability evaluation method 1, except that the polyethylene terephthalate film was replaced with one-side gloss bleached kraft paper (Nippon Paper Industries, Capital Wrap).
• Method 3 The compost decomposition of the adhesives of Examples 1, 3, and 5 to 10 was measured in the same manner as in the compost biodegradability evaluation method 1, except that the polyethylene terephthalate film was replaced with a biodegradable sealant film: polybutylene succinate film (Mitsubishi Chemical Corporation, BioPBS TM FD92).
• a biaxially oriented polypropylene film (P2161 OPP film, manufactured by Toyobo Co., Ltd.) and a non-oriented polypropylene film (P1128 CPP film, manufactured by Toyobo Co., Ltd.) were coated with a two-component curing adhesive (solid content 3 g/ m2 ) formulated in the combination of the examples or comparative examples, and bonded together to obtain a laminate.
• the laminate obtained above was cut into a size of 20 mm x 20 mm to prepare a test piece.
• the test piece was immersed in a release agent heated to 70°C and stirred at 400 rpm.
• the release solution used was a mixture of 48 parts water and 50 parts ethanol, with 2 parts sodium hydroxide dissolved in it. A (best): peeled area is 100% B (Excellent): Peeled area is less than 90-100% C (Good): Peeled area is less than 80-90% D (Acceptable): Peeled area is less than 70-79% E (Unacceptable): Peeled area is less than 70%
• Method 1 A cellophane film (manufactured by Futamura Corporation; NATUREFLEX NP 23 ⁇ m) and a PBS film (manufactured by Mitsubishi Chemical Corporation; BioPBS film 30 ⁇ m) as a sealant film were bonded together with a two-component curing adhesive (solid content 3 g/ m2 ) formulated in the combination of the examples or comparative examples, and aged at 50°C for 72 hours to obtain a laminate.
• a two-component curing adhesive solid content 3 g/ m2
• Adhesive strength is 2.0N or more
• Method 2 The adhesive strength of the laminate was measured in the same manner as in Method 1 for evaluating adhesive strength, except that the cellophane film was replaced with one-sided gloss bleached kraft paper (Capital Wrap, Nippon Paper Industries Co., Ltd.) and the two-component curing adhesive was applied in an amount of 5 g/ m2 (solid content).
• HDI-TMP Sumidur HT manufactured by Covestro (an adduct of hexamethylene diisocyanate (HDI) and trimethylolpropane (TMP).
• Trimethylolpropane is an aliphatic alcohol having a quaternary carbon atom and a hydroxyl group with three or more valences).
• TDI-TMP Desmodur L-75 manufactured by Covestro (a trimethylolpropane (TMP) adduct of toluene diisocyanate (TDI).
• TMP trimethylolpropane
• TDI trimethylolpropane
• Trimethylolpropane is an aliphatic alcohol having a quaternary carbon atom and a hydroxyl group of three or more valences.
• HDI-nurate Sumidur N3300 manufactured by Covestro (nurate of hexamethylene diisocyanate (HDI))
• HDI-Biuret Duranate 24A-100 (biuret form of hexamethylene diisocyanate (HDI)) manufactured by Asahi Kasei Corporation
• Comparative Examples 1 to 3 are examples in which neither the polyester polyol compound (A) nor the polyisocyanate compound (B) is a reaction product of an aliphatic alcohol having a quaternary carbon atom and a trivalent or higher hydroxyl group, but they exhibited poor compost biodegradability and delamination properties.

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