Two-part curable adhesive, laminate, and packaging material

Abstract

Provided is a two-part curable adhesive which, even when used as a solvent-free adhesive in producing a barrier substrate, is less likely to cause a poor appearance.　The two-part curable adhesive comprises a polyisocyanate composition (X) including polyisocyanate compounds (A) and an isocyanate-reactive composition (Y) including a polyol compound (B), wherein the polyisocyanate compounds (A) comprise a polyurethane polyisocyanate (A1), which is a reaction product of toluene diisocyanate and a polyol, and a hexamethylene diisocyanate derivative (A2) and the polyisocyanate composition (X) has a diisocyanate monomer content of 1.0 mass% or less.

Description

Two-component curing adhesives, laminates, packaging materials

[0001] The present invention relates to a two-component curing adhesive, a laminate, and a packaging material.

[0002] Multilayer composites of metal foils such as aluminum foil or metal-deposited films and plastic films such as polyethylene, polypropylene, vinyl chloride, polyester, and nylon are used as packaging materials for foods, medical products, cosmetics, and daily necessities. These laminates are made by appropriately combining various plastic films, metal-deposited films, or metal foils according to the required properties of each application and bonding them together with an adhesive. The adhesive generally used is a two-component curing adhesive consisting of a polyol composition and a polyisocyanate composition (see, for example, Patent Document 1).

[0003] JP 2014-101422 A

[0004] As a two-component curing adhesive, so-called solventless adhesives, which do not contain solvents, are also being investigated and introduced. Solventless adhesives have many advantages, such as no drying process and no solvent emissions, and no concern about solvent remaining in the laminate after bonding plastic films together or after bonding a plastic film to a metal foil or metal vapor deposition layer. On the other hand, when solventless adhesives are used to laminate high-gas barrier substrates (hereinafter also referred to as barrier substrates) that have a metal vapor deposition layer such as aluminum or a transparent vapor deposition layer of an inorganic oxide such as silica or alumina on the film, they are prone to poor appearance. This problem becomes more pronounced as the lamination speed increases.

[0005] The present invention has been made in view of the above problems, and an object of the present invention is to provide a two-component curing adhesive that suppresses poor appearance even when used as a solvent-free adhesive in the production of a barrier substrate.

[0006] That is, the present invention relates to a two-component curing adhesive comprising a polyisocyanate composition (X) containing a polyisocyanate compound (A) and an isocyanate-reactive composition (Y) containing a polyol compound (B), wherein the polyisocyanate compound (A) contains a polyurethane polyisocyanate (A1) which is a reaction product of toluene diisocyanate and a polyol, and a hexamethylene diisocyanate derivative (A2), and the content of diisocyanate monomer in the polyisocyanate composition (X) is 1.0 mass% or less.

[0007] According to the present invention, it is possible to provide a two-component curing adhesive that suppresses poor appearance even when used as a solvent-free adhesive in the production of a barrier substrate.

[0008] <Two-component curing adhesive> The adhesive of the present invention is a two-component curing adhesive containing a polyisocyanate composition (X) and a polyol composition (Y).

[0009] (Polyisocyanate composition (X)) (Polyisocyanate compound (A)) The polyisocyanate composition (X) contains, as an essential component, a polyisocyanate compound (A) having a plurality of isocyanate groups. The polyisocyanate compound (A) also contains a polyurethane polyisocyanate (A1) and a hexamethylene diisocyanate derivative (A2).

[0010] The polyurethane polyisocyanate (A1) is a reaction product of toluene diisocyanate and polyol. The toluene diisocyanate may be either 2,4'-toluene diisocyanate, 2,6'-toluene diisocyanate, or both.

[0011] Examples of polyols that can be used in the synthesis of polyurethane polyisocyanate (A1) include glycols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol;

[0012] Trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, pentaerythritol, and 1,3,5-tris(2-hydroxyethyl)isocyanurate; bisphenols such as bisphenol A, bisphenol F, hydrogenated bisphenol A, and hydrogenated bisphenol F; dimer diol;

[0013] 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;

[0014] Polyester polyols (1) are reaction products of polyesters obtained by ring-opening polymerization of cyclic ester compounds such as propiolactone, butyrolactone, ε-caprolactone, σ-valerolactone, β-methyl-σ-valerolactone, and polyhydric alcohols such as the glycols, glycerin, trimethylolpropane, and pentaerythritol; polyester polyols (2) are obtained by reacting bifunctional polyols such as the glycols, dimer diols, or bisphenols with polycarboxylic acids; polyester polyols (3) are obtained by reacting trifunctional or tetrafunctional aliphatic alcohols with polycarboxylic acids; polyester polyols (4) are obtained by reacting bifunctional polyols, trifunctional or tetrafunctional aliphatic alcohols, and polycarboxylic acids; polyester polyols (5) are polymers of hydroxyl acids such as dimethylolpropionic acid and castor oil fatty acid;

[0015] a polyether polyurethane polyol obtained by polymerizing the polyether polyol with an isocyanate compound; a polyester polyether polyurethane polyol obtained by reacting at least one of polyester polyols (1) to (5), a polyether polyol, and an isocyanate compound; a polyester polyurethane polyol obtained by polymerizing polyester polyols (1) to (5) with an isocyanate compound;

[0016] Examples include castor oil-based polyols such as castor oil, dehydrated castor oil, hydrogenated castor oil which is a hydrogenated castor oil, and castor oil-based polyols such as 5 to 50 mol alkylene oxide adducts of castor oil, and mixtures thereof, and these may be used alone or in combination of two or more.

[0017] Examples of the polymerization initiator for polyether polyol include glycols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and triethylene glycol;

[0018] trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, pentaerythritol, and triols of polypropylene glycol;

[0019] Examples thereof include primary or secondary alkylamines such as ethylamine and diethylamine, amine compounds having a plurality of amino groups such as methylenediamine and ethylenediamine, and amine compounds having an active hydrogen group such as primary or secondary alkanolamines such as monoethanolamine and diethanolamine.

[0020] Examples of polycarboxylic acids used in the synthesis of the polyester polyols (2) to (4) include aromatic polybasic acids such as orthophthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride, naphthalic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid, benzophenonetetracarboxylic acid, benzophenonetetracarboxylic dianhydride, 5-sodium sulfoisophthalic acid, tetrachlorophthalic anhydride, and tetrabromophthalic anhydride; and methyl esters of aromatic polybasic acids such as dimethyl terephthalic acid and dimethyl 2,6-naphthalenedicarboxylate.

[0021] Aliphatic polybasic acids such as malonic acid, succinic acid, succinic anhydride, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, maleic anhydride, and itaconic acid; alkyl esters of aliphatic polybasic acids such as dimethyl malonate, diethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, diethyl pimelate, diethyl sebacate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, and diethyl maleate;

[0022] Examples of the alicyclic polybasic acids include 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-1,2-anhydride, himic acid anhydride, and HET acid anhydride, and these may be used alone or in combination of two or more.

[0023] The polyol used in the synthesis of polyurethane polyol (A1) preferably has a molecular weight of 50 g / mol or more and 4000 g / mol or less. This makes it possible to suppress poor appearance even when the adhesive of the present invention is used as a solventless adhesive to bond substrates with high gas barrier properties. The polyol used in the synthesis of polyurethane polyol (A1) more preferably has a molecular weight of 50 g / mol or more and 2000 g / mol or less, more preferably 50 g / mol or more and 1000 g / mol or less, more preferably 50 g / mol or more and 800 g / mol or less, and even more preferably 50 g / mol or more and 500 g / mol or less. The molecular weight in this application is a value calculated from the following formula (1):

[0024]

[0025] The effects of the present invention are more readily achieved when the polyol used in synthesizing the polyurethane polyisocyanate (A1) contains a polyol with a relatively low molecular weight, preferably 20% by mass or more of a polyol with a molecular weight of 50 g / mol or less and 500 g / mol or less, and more preferably 20% by mass or more of a polyol with a molecular weight of 50 g / mol or less and 300 g / mol or less.

[0026] The polyol used in the synthesis of the polyurethane polyisocyanate (A1) preferably contains at least one selected from glycols, polyether polyols, and polyester polyols. The polyol used in the synthesis of the polyurethane polyisocyanate (A1) preferably contains at least one selected from glycols, polyether polyols, and polyester polyols in an amount of 50% by mass or more, more preferably 70% by mass or more, and more preferably 90% by mass or more. The total amount of the polyol used in the synthesis of the polyurethane polyisocyanate (A1) may be at least one selected from glycols, polyether polyols, and polyester polyols.

[0027] The polyurethane polyisocyanate (A1) is obtained by reacting toluene diisocyanate with a polyol under conditions in which the isocyanate groups of the toluene diisocyanate are in excess relative to the hydroxyl groups of the polyol. The equivalent ratio of isocyanate groups to hydroxyl groups, [NCO] / [hydroxyl groups], can be appropriately adjusted, but is, for example, 2.0 to 20.0.

[0028] Examples of the hexamethylene diisocyanate derivative (A2) include 1,6-hexamethylene diisocyanate biuret (A2-1), nurate (A2-2), adduct (A2-3), allophanate (A2-4), carbodiimide-modified (A2-5), uretdione-modified (A2-6), iminooxadiazinedione (A2-7), and polyurethane polyisocyanate (A2-7) other than the polyurethane polyisocyanate (A1), and these may be used alone or in combination of two or more. The hexamethylene diisocyanate derivative (A2) preferably includes 1,6-hexamethylene diisocyanate nurate (A2-2).

[0029] The polyol used in the synthesis of the polyurethane polyisocyanate (A2-7) may be the same as those exemplified as those usable in the synthesis of the polyurethane polyisocyanate (A1), and is preferably at least one selected from glycols, polyether polyols, and polyester polyols.

[0030] The polyisocyanate composition (X) may contain, as the polyisocyanate compound (A), an isocyanate derivative (A3) other than the polyurethane polyisocyanate (A1) and the hexamethylene diisocyanate derivative (A2). Examples of the isocyanate derivative (A3) include conventionally known aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and biuret derivatives (A3-1), nurate derivatives (A3-2), adduct derivatives (A3-3), allophanate derivatives (A3-4), carbodiimide-modified derivatives (A3-5), uretdione-modified derivatives (A3-6), iminooxadiazinedione derivatives (A3-7), and polyurethane polyisocyanates (A3-7) other than the polyurethane polyisocyanates (A1) and (A2-7). These may be used alone or in combination of two or more.

[0031] Examples of aromatic diisocyanates include 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (also known as MDI), polymethylene polyphenyl polyisocyanate (also known as polymeric MDI or crude MDI), 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate (also known as PPDI), and 2,4-toluene. Examples of the diisocyanate include, but are not limited to, 2,6-toluene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, tolidine diisocyanate (also known as TODI), dianisidine diisocyanate, naphthalene diisocyanate (also known as NDI), 4,4'-diphenyl ether diisocyanate, and 4,4',4"-triphenylmethane triisocyanate.

[0032] The araliphatic diisocyanate means an aliphatic isocyanate having one or more aromatic rings in the molecule, and examples thereof include, but are not limited to, m- or p-xylylene diisocyanate (also known as XDI), α,α,α',α'-tetramethylxylylene diisocyanate (also known as TMXDI), and the like.

[0033] Examples of aliphatic diisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate (also known as PDI), 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate (also known as LDI), but are not limited to these.

[0034] Examples of alicyclic diisocyanates include 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'-methylenebiscyclohexyl isocyanate (also known as hydrogenated MDI or HMDI), 1,3-bis(isocyanatomethyl)cyclohexane (also known as hydrogenated XDI or HXDI), hydrogenated TMXDI, and norbornane diisocyanate (also known as NBDI), but are not limited to these.

[0035] The polyol used in the synthesis of the polyurethane polyisocyanate (A3-7) may be the same as those exemplified as those usable in the synthesis of the polyurethane polyisocyanate (A1), and is preferably at least one selected from glycols, polyether polyols, and polyester polyols.

[0036] The molecular weight of the polyol used in the synthesis of polyurethane polyisocyanate (A3-7) can be adjusted as appropriate, but is, for example, 50 g / mol to 4000 g / mol. The molecular weight of the polyol can be calculated in the same manner as for the raw material polyol of polyurethane polyol (A1).

[0037] The polyurethane polyisocyanate (A3-7) can be obtained by reacting an isocyanate with a polyol under conditions in which the isocyanate groups of the isocyanate are in excess relative to the hydroxyl groups of the polyol, and then removing unreacted diisocyanate monomers as needed under the same conditions as those for the polyurethane polyisocyanate (A1). The equivalent ratio of isocyanate groups to hydroxyl groups [NCO] / [hydroxyl groups] can be appropriately adjusted, but is, for example, from 2.0 to 20.0.

[0038] The content of the polyurethane polyisocyanate (A1) in the polyisocyanate compound (A) (the total of the polyurethane polyisocyanate (A1), the hexamethylene diisocyanate derivative (A2), the isocyanate derivative (A3), and the isocyanate monomer described below) can be adjusted appropriately depending on the desired performance. For example, it is 50% by mass or more and 95% by mass or less, more preferably 70% by mass or more and 95% by mass or less.

[0039] When the polyisocyanate composition (X) contains the isocyanate derivative (A3), the content of the isocyanate derivative (A3) in the polyisocyanate compound (A) can be appropriately adjusted depending on the desired performance, and is, for example, 30 mass% or less.

[0040] The polyisocyanate composition (X) used in the present invention has a content of diisocyanate monomers, i.e., diisocyanate monomers such as aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates, which are exemplified as raw materials for the isocyanate derivative (A3), of 1.0 mass% or less. It is also preferable that the content of diisocyanate monomers in the polyisocyanate composition (X) is reduced to 0.5 mass% or less, and further preferably to 0.1 mass% or less.

[0041] When a laminate for food packaging is manufactured using a two-component curing adhesive containing an aromatic isocyanate prepolymer, unreacted aromatic isocyanate monomer may remain in the adhesive layer. The isocyanate monomer reacts with surrounding water to form primary aromatic amine (PAA), which may migrate through the film and leach into the contents (food). Due to concerns about the harmfulness of PAA to the human body, various regulations have been established, including the European Commission's detection limit for PAA in its regulations on food contact plastic materials and articles.

[0042] Because PAA reacts with unreacted aromatic isocyanate present in the vicinity, the concentration of PAA gradually decreases even when aromatic isocyanate remains in the adhesive layer. Although it eventually falls below the detection limit, from the viewpoint of the manufacturing efficiency of laminates for food packaging, it is preferable that the initial value of aromatic isocyanate monomer remaining in the adhesive layer is low. By removing the diisocyanate monomer in advance, a two-component curing adhesive with excellent manufacturing efficiency can be obtained.

[0043] Furthermore, from the viewpoint of occupational safety and health, there is a movement to restrict the use of isocyanate monomers, and the European Commission has adopted the REACH regulation, which prohibits the marketing of products containing 0.1% by mass or more of isocyanate monomers unless certain requirements are met. If unreacted diisocyanate monomers are removed until the amount of diisocyanate monomers in the polyisocyanate composition is 0.1% by mass or less, a product that complies with such regulations can be obtained.

[0044] The diisocyanate monomer can be removed by distilling the diisocyanate monomer under reduced pressure using a short-path distillation apparatus, a thin-film distillation apparatus, etc. The degree of reduced pressure and the distillation temperature are appropriately adjusted depending on the diisocyanate monomer to be removed, and are, for example, 0.1 mbar or less and 120° C. to 190° C. The diisocyanate monomer removal step may be carried out multiple times.

[0045] The content of diisocyanate monomer can be measured by gas chromatography using an internal standard, for example, in accordance with ASTM D 3432. Alternatively, it can also be measured by liquid chromatography under the following conditions.

[0046] Equipment: Waters Corporation "ACQUITY UPLC H-Class" Data processing: Waters Corporation "Empower-3" Column: Waters Corporation "ACQUITY UPLC HSS T3" (100 mm x 2.1 mmφ, 1.8 μm) 40°C Eluent: Ammonium formate aqueous solution / methanol, 0.3 mL / min Detector: PDA Sample preparation: 1. Dissolve 100 mg of appropriately blocked sample in 10 ml of THF (for LC) 2. Vortex for 30 seconds 3. Dilute appropriately with eluent (mobile phase) 4. Pass through a 0.2 μm filter to prepare the measurement sample. Calculation of area ratio: Calculate using the maximum absorption wavelength for the target substance.

[0047] The NCO % of the polyisocyanate composition (X) can be adjusted appropriately depending on the purpose, but is preferably 7% or more and 21% or less, for example.

[0048] When the adhesive of the present invention is used as a solventless adhesive, the viscosity of the polyisocyanate composition (X) is adjusted to a range suitable for the non-solvent lamination method. For example, the viscosity at 60°C is adjusted to be in the range of 100 to 20,000 mPas, more preferably 500 to 10,000 mPas. The viscosity of the polyisocyanate composition (X) can be measured, for example, using a rotational viscometer with a cone and plate diameter of 1° x 50 mm and a shear rate of 100 sec. －１ , can be measured at 60°C ± 1°C.

[0049] When the adhesive of the present invention is used as a solvent-based adhesive, the viscosity of the polyisocyanate composition (X) can be adjusted by diluting it with a solvent.

[0050] (Isocyanate-reactive composition (Y)) (Polyol compound (B)) The isocyanate-reactive composition (Y) contains a polyol compound (B) having a plurality of hydroxyl groups. Examples of the polyol compound (B) include polyester polyols (B1), polyether polyols (B2), vegetable oil polyols (B3), polyurethane polyols (B4), sugar alcohols (B5), and acrylic polyols (B6), and these can be used alone or in combination of two or more.

[0051] Examples of the polyester polyol (B1) include polyester polyols which are reaction products of polyhydric alcohols and polycarboxylic acids, and lactone-based polyester polyols obtained by polycondensation reaction of aliphatic polyols and various lactones such as ε-caprolactone. It is preferable to use polyester polyols which are reaction products of polyhydric alcohols and polycarboxylic acids.

[0052] Examples of polyhydric alcohols include aliphatic diols such as ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,2,2-trimethyl-1,3-propanediol, 2,2-dimethyl-3-isopropyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-bis(hydroxymethyl)cyclohexane, and 2,2,4-trimethyl-1,3-pentanediol;

[0053] aliphatic polyols having three or more functional groups, such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, and pentaerythritol;

[0054] Bisphenols such as bisphenol A and bisphenol F; alkylene oxide adducts of bisphenols obtained by adding ethylene oxide, propylene oxide, or the like to bisphenols such as bisphenol A and bisphenol F;

[0055] Examples of such polyether polyols include polyether polyols obtained by ring-opening polymerization of an aliphatic diol or polyol with various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether. These polyether polyols may be used alone or in combination of two or more.

[0056] Examples of polycarboxylic acids include aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, and 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid; and anhydrides or ester-forming derivatives of these aliphatic or dicarboxylic acids; and polybasic acids such as p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid, and ester-forming derivatives of these dihydroxycarboxylic acids, and dimer acid, and these may be used alone or in combination of two or more.

[0057] The polyester polyol (B1) preferably has a molecular weight of 250 g / mol to 20,000 g / mol, more preferably 500 g / mol to 10,000 g / mol, and a hydroxyl value of 5 mg KOH / g to 500 mg KOH / g.

[0058] Examples of the polyether polyol (B2) include those obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexylene in the presence of a polymerization initiator.

[0059] Examples of the polymerization initiator include glycols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and triethylene glycol;

[0060] trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, pentaerythritol, and triols of polypropylene glycol;

[0061] Examples thereof include primary or secondary alkylamines such as ethylamine and diethylamine, amine compounds having a plurality of amino groups such as methylenediamine and ethylenediamine, and amine compounds having an active hydrogen group such as primary or secondary alkanolamines such as monoethanolamine and diethanolamine.

[0062] The molecular weight of the polyether polyol (B2) can be adjusted appropriately, but is preferably 100 g / mol or more and 8000 g / mol or less, for example. The hydroxyl value of the polyether polyol (B2) can be adjusted appropriately, but is preferably 10 mgKOH / g or more and 1200 mgKOH / g or less, for example.

[0063] Examples of the vegetable oil polyol (B3) include castor oil, dehydrated castor oil, hardened castor oil which is a hydrogenated castor oil, and an adduct of 5 to 50 moles of alkylene oxide with castor oil.

[0064] The polyurethane polyol (B4) is a reaction product of a low-molecular-weight or high-molecular-weight polyol and a polyisocyanate compound. The low-molecular-weight or high-molecular-weight polyol may be the same as the polyhydric alcohols exemplified as raw materials for the polyester polyol (B1). The polyisocyanate compound may be the same as the polyhydric alcohols exemplified as raw materials for the isocyanate derivative (A3).

[0065] Examples of the sugar alcohol (B5) include pentaerythritol, sucrose, xylitol, sorbitol, isomalt, lactitol, maltitol, and mannitol.

[0066] The acrylic polyol (B6) is obtained by copolymerizing a (meth)acrylic acid ester having a hydroxyl group as an essential component with a polymerizable unsaturated monomer as needed. In this specification, (meth)acrylic acid means methacrylic acid or acrylic acid. Examples of the (meth)acrylic acid ester having a hydroxyl group include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate, and these can be used alone or in combination of two or more.

[0067] Examples of the polymerizable unsaturated monomer include alkyl (meth)acrylates having an alkyl group having 1 to 22 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate; aralkyl (meth)acrylates, such as benzyl (meth)acrylate and 2-phenylethyl (meth)acrylate; cycloalkyl (meth)acrylates, such as cyclohexyl (meth)acrylate and isobornyl (meth)acrylate; ω-alkoxyalkyl (meth)acrylates, such as 2-methoxyethyl (meth)acrylate and 4-methoxybutyl (meth)acrylate; polyfunctional (meth)acrylates such as ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and dipentaerythritol hexa(meth)acrylate;

[0068] (Meth)acrylic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, 4-methylcyclohex-4-ene-1,2-dicarboxylic anhydride, bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride, 1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic anhydride, 2-octa-1,3-diketospiro[4.4]non-7-ene, bicyclo[ Examples of suitable polymerizable unsaturated monomers include polymerizable unsaturated monomers having an acid group, such as methyl-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, maleopimaric acid, tetrahydrophthalic anhydride, methyl-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, methyl-norbornen-5-ene-2,3-dicarboxylic anhydride, norborn-5-ene-2,3-dicarboxylic anhydride, sulfonated styrene, and vinylbenzenesulfonamide; vinyl carboxylic acid vinyl esters, such as vinyl acetate, vinyl propionate, vinyl pivalate, and vinyl benzoate; alkyl esters of crotonic acid, such as methyl crotonate and ethyl crotonate; and dialkyl esters of unsaturated dibasic acids, such as dimethyl maleate, di-n-butyl maleate, dimethyl fumarate, and dimethyl itaconate. These may be used alone or in combination of two or more.

[0069] (Isocyanate-reactive compound (C)) The isocyanate-reactive composition (Y) may contain an isocyanate-reactive compound (C) other than the polyol compound (B). The isocyanate-reactive compound (C) refers to a compound having a functional group reactive with an isocyanate group, and examples thereof include an amine compound (C1) and a monool compound (C2). These may be used alone or in combination of two or more.

[0070] The amine compound (C1) is a compound having an amino group. In this specification, the amino group is defined as an NH ２ group or NHR group (R is an alkyl group or aryl group which may have a functional group).

[0071] As the amine compound (C1), known compounds can be used without any particular limitation, and examples thereof include methylenediamine, ethylenediamine, isophoronediamine, 3,9-dipropanamine-2,4,8,10-tetraoxaspirodoundecane, lysine, 2,2,4-trimethylhexamethylenediamine, hydrazine, piperazine, 2-hydroxyethylethylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, poly(propylene glycol)diamine, poly(propylene glycol)triamine, poly(propylene glycol)tetraamine, 1,2-diaminopropane, 1,3-diaminopropane,

[0072] 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, nonaethylenedecamine, trimethylhexamethylenediamine, tetra(aminomethyl)methane, tetrakis(2-aminoethylaminomethyl)methane, 1,3-bis(2'-aminoethylamino)propane, triethylene-bis(trimethylene)hexamine, bis(3-aminoethyl)amine, bishexamethylenetriamine, 1,4-cyclohexanediamine, 4,4'-methylenebiscyclohexylamine, 4,4'-isopropylidenebiscyclohexylamine, norbornadiamine,

[0073] amine compounds (C1-1) having a plurality of amino groups, such as bis(aminomethyl)cyclohexane, diaminodicyclohexylmethane, isophoronediamine, menthenediamine, bis(cyanoethyl)diethylenetriamine, 1,4-bis-(8-aminopropyl)-piperazine, piperazine-1,4-diazacycloheptane, 1-(2'-aminoethylpiperazine), 1-[2'-(2"-aminoethylamino)ethyl]piperazine, tricyclodecanediamine, and polyureaamines which are reaction products of the above-mentioned various polyamines with the above-mentioned various isocyanate components;

[0074] primary or secondary alkanolamines (C1-2) such as monoethanolamine, monoisopropanolamine, monobutanolamine, N-methylethanolamine, N-ethylethanolamine, N-methylpropanolamine, diethanolamine, and diisopropanolamine;

[0075] Examples include primary or secondary amines (C1-3) such as ethylamine, octylamine, laurylamine, myristylamine, stearylamine, oleylamine, diethylamine, dibutylamine, and distearylamine.

[0076] The amount of the amine compound (C1) to be added can be adjusted appropriately depending on the purpose. As an example, it is preferably added so that the amine value of the isocyanate-reactive composition (Y) is 20 to 70 mgKOH / g, more preferably 25 to 50 mgKOH / g.

[0077] In this specification, the amine value refers to the number of milligrams of KOH equivalent to the amount of HCl required to neutralize 1 g of sample, and is not particularly limited and can be calculated using known methods. When the chemical structure of the amine compound (E7) and, if necessary, the average molecular weight, etc. are known, the amine value can be calculated from (number of amino groups per molecule / average molecular weight) x 56.1 x 1000. When the chemical structure, average molecular weight, etc. of the amine compound are unknown, the amine value can be measured according to known amine value measurement methods, for example, JIS K7237-1995.

[0078] Examples of the monool compound (C2) include compounds having one alcoholic hydroxyl group. The main chain of the monool compound (C2) is not particularly limited, and examples thereof include vinyl resins, acrylic resins, polyesters, epoxy resins, and urethane resins having one hydroxyl group. Aliphatic alcohols, alkyl alkylene glycols, and the like can also be used. The main chain of the monool compound (C2) may be linear or branched. The bonding position of the hydroxyl group is not particularly limited, but it is preferably present at the terminal of the molecular chain.

[0079] Specific examples of the monool compound (C2) include aliphatic monools such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, lauryl alcohol, myristyl alcohol, pentadecanol, cetyl alcohol, heptadecanol, stearyl alcohol, nonadecanol, other alkanols (C20 to C50), oleyl alcohol, and isomers thereof;

[0080] Cyclohexanol, methylcyclohexanol, 4-butylcyclohexanol, 4-pentylcyclohexanol, 4-hexylcyclohexanol, cyclodecanol, cyclododecanol, cyclopentadecanol, 4-isopropylcyclohexanol, 3,5,5-trimethylcyclohexanol, menthol, 2-norbornanol, borneol, 2-adamantanol, dicyclohexylmethanol, decitol, 2-cyclohexylcyclohexanol, 4-cyclohexylcyclohexanol, 4-(4-propylcyclohexyl)cyclohexanol, 4-(4-pentylcyclohex cyclohexanol, α-ambrinol, desoxycorticosterone, 11-dehydrocorticosterone, cholesterol, β-sitosterol, campesterol, stigmasterol, brassicasterol, lanosterol, ergosterol, β-cholestanol, testosterone, estrone, digitoxigenin, dehydroepiandrosterone, coprostanol, pregnenolone, epicholestanol, 7-dehydrocholesterol, estradiol benzoate, tigogenin, hecogenin, methandienone, cortisone acetate, stenolone, and isomers thereof;

[0081] aromatic aliphatic monools such as benzyl alcohol,

[0082] Examples of the polyoxyalkylene monool include polyoxyalkylene monools obtained by ring-opening addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran using an alkyl compound containing one active hydrogen as an initiator.

[0083] When the adhesive of the present invention is provided in a solventless form, the viscosity of the isocyanate-reactive composition (Y) is adjusted to a range suitable for the non-solvent lamination method. For example, the viscosity at 40°C is adjusted to be in the range of 100 to 50,000 mPas, more preferably 100 to 20,000 mPas.

[0084] (Other Components of the Adhesive) The two-component curing adhesive of the present invention may contain components other than those described above. The other components may be contained in either or both of the polyisocyanate composition (X) and the isocyanate-reactive composition (Y), or may be prepared separately from these and mixed with the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) immediately before application of the adhesive. Each component will be described below.

[0085] (Catalyst) Examples of the catalyst include metal catalysts, amine catalysts, aliphatic cyclic amide compounds, and quaternary ammonium salts.

[0086] Examples of the metal catalyst include metal complex catalysts, inorganic metal catalysts, and organic metal catalysts. Examples of the metal complex catalyst 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.

[0087] Examples of inorganic metal catalysts include those selected from Sn, Fe, Mn, Cu, Zr, Th, Ti, Al, Co, and the like.

[0088] Examples of the organometallic catalyst 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; titanium compounds such as tetraisopropyloxytitanate, dibutyltitanium dichloride, tetrabutyltitanium, butoxytitanium trichloride, aliphatic diketones, aromatic diketones, and titanium chelate complexes having at least one of alcohols having 2 to 10 carbon atoms as a ligand.

[0089] Examples of the amine catalyst 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-hydroxyethyl)propanediamine, bis(dimethylaminopropyl)amine, bis(dimethylaminopropyl)isopropyl propanolamine, 3-quinuclidinol, N,N,N',N'-tetramethylguanidine, 1,3,5-tris(N,N-dimethylaminopropyl)hexahydro-S-triazine, 1,8-diazabicyclo[5.4.0]undecene-7, N-methyl-N'-(2-dimethylaminoethyl)piperazine, N,N'-dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, 1-methylimidazole, 1 , 2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethylaminopropylimidazole, N,N-dimethylhexanolamine, N-methyl-N'-(2-hydroxyethyl)piperazine, 1-(2-hydroxyethyl)imidazole, 1-(2-hydroxypropyl)imidazole, 1-(2-hydroxyethyl)-2-methylimidazole, 1-(2-hydroxypropyl)-2-methylimidazole, and the like.

[0090] Examples of the aliphatic cyclic amide compound include δ-valerolactam, ε-caprolactam, ω-enantholactam, η-capryllactam, β-propiolactam, etc. Among these, ε-caprolactam is more effective in accelerating curing.

[0091] Examples of quaternary ammonium salts include hydroxy salts of alkyl ammonium, aromatic ammonium, etc., alkyl acid salts, halide salts, etc. Examples include, but are not limited to, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltriethylammonium chloride, hexadecyltrimethylammonium bromide, etc.

[0092] (Coupling Agent) Examples of the coupling agent include silane coupling agents, titanate-based coupling agents, and aluminum-based coupling agents.

[0093] Examples of the silane coupling agent include aminosilanes such as γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, and bis[3-(triethoxysilyl)propyl]amine; epoxysilanes such as β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane; vinylsilanes such as vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane; and hexamethyldisilazane and γ-mercaptopropyltrimethoxysilane.

[0094] Examples of titanate coupling agents include tetraisopropoxytitanium, tetra-n-butoxytitanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, titanium lactate, and tetrastearoxytitanium.

[0095] Examples of aluminum-based coupling agents include acetoalkoxyaluminum diisopropylate.

[0096] (Pigment) The pigment is not particularly limited, and examples thereof include organic pigments and inorganic pigments such as extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments, green pigments, blue pigments, metal powder pigments, luminescent pigments, and pearlescent pigments listed in the Paint Raw Materials Handbook 1970 Edition (compiled by the Japan Paint Manufacturers Association), as well as plastic pigments.

[0097] Examples of extender pigments include precipitated barium sulfate, powdered barium sulfate, precipitated calcium carbonate, calcium bicarbonate, kansui stone, alumina white, silica, hydrous fine powdered silica (white carbon), ultrafine powdered anhydrous silica (aerosil), silica sand, talc, precipitated magnesium carbonate, bentonite, clay, kaolin, and yellow ochre.

[0098] Specific examples of organic pigments include various insoluble azo pigments such as Benzidine Yellow, Hansa Yellow, and Lake 4R; soluble azo pigments such as Lake C, Carmine 6B, and Bordeaux 10; various (copper) phthalocyanine pigments such as Phthalocyanine Blue and Phthalocyanine Green; various chlorine dye lakes such as Rhodamine Lake and Methyl Violet Lake; various mordant dye pigments such as Quinoline Lake and Fast Sky Blue; various vat dye pigments such as Anthraquinone pigments, Thioindigo pigments, and Perinone pigments; various quinacridone pigments such as Synchasia Red B; various dioxazine pigments such as Dioxazine Violet; various condensed azo pigments such as Chromophtal; and aniline black.

[0099] Examples of inorganic pigments include various chromates such as yellow lead, zinc chromate, and molybdate orange; various ferrocyanide compounds such as iron blue; various metal oxides such as titanium oxide, zinc white, 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, and the like.

[0100] Examples of plastic pigments include "Grandol PP-1000" and "PP-2000S" manufactured by DIC Corporation.

[0101] The pigment to be used may be selected appropriately depending on the purpose. For example, inorganic oxides such as titanium oxide and zinc oxide are preferably used as white pigments because they have excellent durability, weather resistance, and design properties, and carbon black is preferably used as black pigments.

[0102] The blending amount of the pigment is, for example, 1 to 400 parts by mass per 100 parts by mass of the total amount of nonvolatile components of the polyisocyanate composition (X) and the isocyanate-reactive composition (Y), and is more preferably 10 to 300 parts by mass in order to improve adhesion and blocking resistance.

[0103] (Acid Anhydride) Examples of the acid anhydride include alicyclic acid anhydrides, aromatic acid anhydrides, unsaturated carboxylic acid anhydrides, etc., and can be used alone or in combination of two or more. More specifically, for example, maleic acid anhydride, phthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, benzophenonetetracarboxylic acid anhydride, dodecenylsuccinic acid anhydride, polyadipic acid anhydride, polyazelaic acid anhydride, polysebacic acid anhydride, poly(ethyloctadecanedioic acid) anhydride, poly(phenylhexadecanedioic acid) anhydride, tetrahydrophthalic acid anhydride, methyltetrahydrophthalic acid anhydride, methylhexahydrophthalic acid anhydride, hexahydrophthalic acid anhydride, methylhimic acid anhydride, trialkyltetrahydrophthalic acid anhydride, anhydride, methylcyclohexene dicarboxylic acid anhydride, methylcyclohexene tetracarboxylic acid anhydride, ethylene glycol bistrimellitate dianhydride, HET acid anhydride, Nadic acid anhydride, methylnadic acid anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexane-1,2-dicarboxylic acid anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride, and the like.

[0104] The acid anhydride may be any of the above compounds modified with glycol. Examples of glycols that can be used for modification 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. Furthermore, copolymer polyether glycols of two or more of these glycols and / or polyether glycols may also be used.

[0105] Alternatively, among the compounds mentioned above as acid anhydrides, a homopolymer or copolymer of a compound having a polymerizable unsaturated group, such as maleic anhydride, may be used. Examples of compounds copolymerizable with a compound having an acid anhydride group and a polymerizable unsaturated group include α-olefins such as ethylene, propylene, 1,3-butadiene, and cyclopentylethylene; vinyl compounds having an aromatic ring, such as styrene, 1-ethynyl-4-methylbenzene, divinylbenzene, 1-ethynyl-4-methylethylbenzene, benzonitrile, acrylonitrile, p-tert-butylstyrene, 4-vinylbiphenyl, 4-ethynylbenzyl alcohol, 2-ethynylnaphthalene, and phenanthrene-9-ethynyl; and fluoroolefins such as vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, and chlorotrifluoroethylene. These compounds may be used alone or in combination of two or more. It is preferable to use styrene and p-tert-butylstyrene, which are vinyl compounds having an aromatic ring.

[0106] (Phosphoric Acid Derivatives) Examples of phosphoric acid derivatives include phosphoric acid, pyrophosphoric acid, triphosphoric acid, methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, dibutyl phosphate, 2-ethylhexyl acid phosphate, bis(2-ethylhexyl) phosphate, isododecyl acid phosphate, butoxyethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, polyoxyethylene alkyl ether phosphate, etc. Phosphoric acid, pyrophosphoric acid, triphosphoric acid, and butyl acid phosphate are preferred.

[0107] When a phosphoric acid derivative is contained, its content can be appropriately adjusted, but for example, it is 10 ppm or more and 5000 ppm or less, more preferably 50 ppm or more, and more preferably 1000 ppm or less, of the solid content of the polyisocyanate composition (X).

[0108] Examples of plasticizers include phthalic acid-based plasticizers, fatty acid-based plasticizers, aromatic polycarboxylic acid-based plasticizers, phosphoric acid-based plasticizers, polyol-based plasticizers, epoxy-based plasticizers, polyester-based plasticizers, and carbonate-based plasticizers.

[0109] Examples of the phthalic acid plasticizer 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, butylbenzyl phthalate, dicyclohexyl phthalate, octyldecyl phthalate, dimethyl isophthalate, di-(2-ethylhexyl) isophthalate, and diisooctyl isophthalate; and tetrahydrophthalic acid ester plasticizers such as di-(2-ethylhexyl) tetrahydrophthalate, di-n-octyl tetrahydrophthalate, and diisodecyl tetrahydrophthalate.

[0110] Examples of the fatty acid plasticizer include 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 and di-(2 Sebacic acid plasticizers such as di-n-butyl maleate, di-(2-ethylhexyl) sebacate, and diisononyl sebacate; maleic acid plasticizers such as dimethyl maleate, diethyl maleate, di-n-butyl maleate, and di-(2-ethylhexyl) maleate; fumaric acid plasticizers such as di-n-butyl fumarate and di-(2-ethylhexyl) fumarate; monomethyl itaconate, monobutyl itaconate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, Examples of suitable plasticizers include itaconic acid-based plasticizers such as itaconate and di-(2-ethylhexyl)itaconate; stearic acid-based plasticizers such as n-butyl stearate, glycerin monostearate, and diethylene glycol distearate; oleic acid-based plasticizers such as butyl oleate, glyceryl monooleate, and diethylene glycol monooleate; citric acid-based plasticizers such as triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tributyl citrate, and acetyl tri-(2-ethylhexyl) citrate; ricinoleic acid-based plasticizers such as methyl acetyl ricinoleate, butyl acetyl ricinoleate, glyceryl monoricinoleate, and diethylene glycol monoricinoleate; and other fatty acid-based plasticizers such as diethylene glycol monolaurate, diethylene glycol dipelargonate, and pentaerythritol fatty acid esters.

[0111] Examples of 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.

[0112] 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.

[0113] Examples of polyol-based plasticizers 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.

[0114] Examples of 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.

[0115] Examples of polyester plasticizers include adipic acid polyesters, sebacic acid polyesters, and phthalic acid polyesters.

[0116] Examples of carbonate plasticizers include propylene carbonate and ethylene carbonate.

[0117] Examples of the plasticizer 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.

[0118] The amount of the plasticizer to be added can be adjusted appropriately depending on the target viscosity, but, as an example, it is preferable to keep the amount of the plasticizer to 30 mass % or less of the solid content of the polyisocyanate composition (X). The polyisocyanate composition (X) does not necessarily need to contain a plasticizer.

[0119] (Adhesive Form) The two-component curing adhesive of the present invention can be suitably used for bonding substrates with high gas barrier properties even in a solvent-free form, but can also be used in a solvent-based form. In this specification, a "solvent-based" adhesive refers to a form used in a so-called dry lamination 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 bonded to another substrate. Either or both of the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) contain an organic solvent capable of dissolving (diluting) the components of the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) used in the present invention.

[0120] Examples of organic solvents include esters such as ethyl acetate, butyl acetate, cellosolve acetate, etc., ketones such as acetone, methyl ethyl ketone, isobutyl ketone, cyclohexanone, etc., ethers such as tetrahydrofuran, dioxane, etc., aromatic hydrocarbons such as toluene, xylene, etc., halogenated hydrocarbons such as methylene chloride, ethylene chloride, etc., dimethyl sulfoxide, dimethyl sulfamide, etc. The organic solvent used as a reaction medium during production of the components of the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) may also be used as a diluent during coating.

[0121] In this specification, a "solventless" adhesive refers to a form of adhesive in which the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) are substantially free of esters such as ethyl acetate, butyl acetate, cellosolve acetate, etc.; ketones such as acetone, methyl ethyl ketone, isobutyl ketone, cyclohexanone, etc.; ethers such as tetrahydrofuran, dioxane, etc.; aromatic hydrocarbons such as toluene, xylene, etc.; halogenated hydrocarbons such as methylene chloride, ethylene chloride, etc.; highly soluble organic solvents such as dimethyl sulfoxide, dimethyl sulfamide, in particular ethyl acetate or methyl ethyl ketone; and which is used in a method in which the adhesive is applied to a substrate and then bonded to another substrate without going through a step of heating in an oven or the like to volatilize the solvent, i.e., a so-called non-solvent lamination method. If the organic solvent used as a reaction medium during the production of the components of polyisocyanate composition (X) or isocyanate-reactive composition (Y) or the raw materials thereof cannot be completely removed, and trace amounts of organic solvent remain in polyisocyanate composition (X) or isocyanate-reactive composition (Y), it is considered to be substantially free of organic solvent. Furthermore, if isocyanate-reactive composition (Y) contains a low-molecular-weight alcohol, the low-molecular-weight alcohol reacts with polyisocyanate composition (X) to become part of the coating film, and therefore does not need to be volatilized after coating. Therefore, such a form is also treated as a solventless adhesive, and the low-molecular-weight alcohol is not considered an organic solvent.

[0122] The two-component curing adhesive of the present invention is preferably used by blending the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) so that the ratio [NCO] / [isocyanate-reactive functional group] of the number of moles of isocyanate groups [NCO] to the number of moles of functional groups reactive with isocyanate [isocyanate-reactive functional group] is 0.5 to 5.0, more preferably 1.0 to 3.0. This allows for appropriate curing properties to be obtained without depending on the environmental humidity at the time of application.

[0123] <Laminate> The laminate of the present invention can be obtained, for example, by a method including a two-liquid mixing step of applying the adhesive of the present invention (a mixture of polyisocyanate composition (X) and isocyanate-reactive composition (Y)) to a first substrate, subsequently laminating a second substrate on the applied surface, and curing the adhesive layer, or by a method including a two-liquid separate coating step of applying the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) separately to a first substrate and a second substrate, subsequently contacting and pressing the applied surfaces of the substrates together to laminate the first substrate and the second substrate, and subsequently curing the adhesive layer. There are no particular restrictions on the substrate used, and it can be selected appropriately depending on the application.

[0124] Examples of films for food packaging include polyethylene terephthalate (PET) films, polystyrene films, polyamide films, polyacrylonitrile films, polyethylene films (LLDPE: low-density polyethylene film, HDPE: high-density polyethylene film, MDOPE: uniaxially oriented polyethylene film, BOPE: biaxially oriented polyethylene film), polypropylene films (CPP: unoriented polypropylene film, OPP: biaxially oriented polypropylene film), polyolefin films such as gas-barrier heat-sealable films in which an olefin-based heat-sealable resin layer is provided on one or both sides of a resin having gas-barrier properties such as an ethylene-vinyl alcohol copolymer or polyvinyl alcohol, polyvinyl alcohol film, and ethylene-vinyl alcohol copolymer film.

[0125] It is also preferable to use biomass films, biodegradable films, and recycled plastic films formed from materials containing biomass-derived components, biodegradable components, or recycled components. Biomass films, biodegradable films, and recycled plastic films are sold by various companies, and films certified in various countries can also be used, such as film sheets listed in the list of biomass-certified products listed by the Japan Organics Recycling Association, films listed in the list of Eco Mark-certified products listed by the Japan Environment Association, and films bearing the symbol mark designated by the Japan Bioplastics Association.

[0126] The film may be one that has been subjected to a stretching treatment. A typical stretching method involves melt-extruding a resin into a sheet using an extrusion film-forming method or the like, followed by simultaneous biaxial stretching or sequential biaxial stretching. In the case of sequential biaxial stretching, it is common to first perform longitudinal stretching and then transverse stretching. Specifically, a method that combines longitudinal stretching utilizing the speed difference between rolls and transverse stretching using a tenter is often used.

[0127] The film surface may be subjected to various surface treatments such as flame treatment and corona discharge treatment as necessary so that an adhesive layer without defects such as film breakage or repellency is formed.

[0128] Alternatively, 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 of polyvinyl alcohol, an ethylene-vinyl alcohol copolymer, vinylidene chloride, etc. Use of such a film can provide a laminate with barrier properties against water vapor, oxygen, alcohol, inert gases, volatile organic compounds (fragrances), etc.

[0129] The paper can be made from any known paper base material without any particular limitations. Specifically, it is produced using natural fibers for papermaking, such as wood pulp, on a known papermaking machine, but the papermaking conditions are not particularly specified. Examples of 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 pulp obtained by chemically modifying these pulps. Examples of pulp that can be used include chemical pulp produced by sulfate cooking, acidic, neutral, or alkaline sulfite cooking, soda cooking, ground pulp, chemi-ground pulp, and thermomechanical pulp. Various commercially available fine paper, coated paper, lined paper, impregnated paper, cardboard, and paperboard can also be used.

[0130] More specific laminate configurations include: (1) substrate 1 / adhesive layer 1 / sealant film (2) substrate 1 / adhesive layer 1 / metal-deposited unstretched film (3) substrate 1 / adhesive layer 1 / metal-deposited stretched film (4) transparent vapor-deposited stretched film / adhesive layer 1 / sealant film (5) substrate 1 / adhesive layer 1 / substrate 2 / adhesive layer 2 / sealant film (6) transparent vapor-deposited stretched film / adhesive layer 1 / substrate 1 / adhesive layer 2 / sealant film (7) substrate 1 / adhesive layer 1 / metal-deposited stretched film / adhesive layer 2 / sealant film (8) substrate 1 / adhesive layer 1 / transparent vapor-deposited stretched film / adhesive layer 2 / sealant film (9) substrate 1 / adhesive layer 1 / metal layer / adhesive layer 2 / sealant film (10) substrate 1 / adhesive layer 1 / substrate 2 / adhesive layer 2 / metal layer / adhesive layer 3 / sealant film (11) Examples include, but are not limited to, substrate 1 / adhesive layer 1 / metal layer / adhesive layer 2 / substrate 2 / adhesive layer 3 / sealant film.

[0131] Examples of the substrate 1 used in structure (1) include MDOPE film, BOPE film, OPP film, PET film, nylon film, and paper. The substrate 1 may also be coated to improve gas barrier properties or ink receptivity when a printing layer (described later) is provided. Commercially available coated substrate films 1 include K-OPP film, K-PET film, and K-nylon film. The adhesive layer 1 is a cured coating of the adhesive of the present invention. Examples of sealant films include CPP film, LLDPE film, easy-open heat seal film, and gas barrier heat seal film. A printing layer may be provided on the surface of the substrate 1 facing the adhesive layer 1 (when a coated substrate film 1 is used, the surface of the coating layer facing the adhesive layer 1) or on the surface opposite 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 a common printing method conventionally used for printing on polymer films and paper.

[0132] Examples of the substrate 1 used in structures (2) and (3) include an MDOPE film, a BOPE film, an OPP film, a PET film, and paper. The adhesive layer 1 is a cured coating of the adhesive of the present invention. Examples of metal-vapor-deposited unstretched films include a CPP film, an LLDPE film, and a VM-CPP film or a VM-LLDPE film, which is a gas-barrier heat-seal film that has been subjected to metal vapor deposition with aluminum or the like. Examples of metal-vapor-deposited stretched films include a VM-MDOPE film, a VM-BOPE film, or a VM-OPP film, which is a MDOPE film, a BOPE film, or an OPP film that has been subjected to metal vapor deposition with aluminum or the like. As with structure (1), a printed layer may be provided on either side of the substrate 1.

[0133] Examples of transparent vapor-deposited stretched films used in structure (4) include films obtained by depositing silica or alumina on MDOPE film, BOPE film, OPP film, PET film, nylon film, etc. A film with a coating applied to the vapor-deposited inorganic layer of silica or alumina may also be used for the purpose of protecting the layer. An anchor coat layer may be provided between the vapor-deposited layer and the substrate on which the vapor-deposited layer is provided for the purpose of improving adhesion of the vapor-deposited layer or improving barrier properties. The adhesive layer 1 is a cured coating film of the adhesive of the present invention. Examples of sealant films include those similar to those in structure (1). A printed layer may be provided on the surface of the transparent vapor-deposited stretched film facing the adhesive layer 1 (when a film with a coating applied to the inorganic vapor-deposited layer is used, the surface of the coating layer facing the adhesive layer 1). The method for forming the printed layer is the same as in structure (1).

[0134] Examples of the substrate 1 used in structure (5) include PET film and paper. Examples of the substrate 2 include nylon film. 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. Examples of the sealant film include those similar to those in structure (1). As in structure (1), a printed layer may be provided on either side of the substrate 1.

[0135] Examples of the transparent vapor-deposited stretched film used in structure (6) include those similar to those in structure (4). Examples of the substrate 1 used in structure (6) include a PET film and a nylon film. 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 the surface of the transparent vapor-deposited stretched film on the adhesive layer 1 side (when a film having a coating applied to an 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 structure (1).

[0136] Examples of the substrate 1 in structure (7) include those similar to those in structures (2) and (3). Examples of metal-vapor-deposited stretched films include VM-MDOPE films, VM-BOPE films, VM-OPP films, and VM-PET films, which are MDOPE films, BOPE films, OPP films, and PET films that have been subjected to metal vapor deposition of aluminum 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. Examples of the sealant film include those similar to those in structure (1). As in structure (1), a printed layer may be provided on either side of the substrate 1.

[0137] Examples of the substrate 1 in structure (8) include PET film, paper, etc. Examples of the transparent vapor-deposited 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). As in structure (1), a printed layer may be provided on either side of the substrate 1.

[0138] Examples of the substrate 1 in structure (9) include PET film and paper. Examples of the metal layer include aluminum foil. 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). As in structure (1), a printed layer may be provided on either side of the substrate 1.

[0139] Examples of the substrate 1 in structures (10) and (11) 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 those similar to those in structure (1). As in structure (1), a printed layer may be provided on either side of the substrate 1.

[0140] The adhesive of the present invention can provide a laminate in which defects in appearance are suppressed, even when used to laminate a substrate with high gas barrier properties, which has a film on which a vapor-deposited metal layer or a vapor-deposited inorganic oxide layer is provided (hereinafter also referred to as a barrier substrate).For this reason, the adhesive can be suitably used in the production of structures (2) to (4) and (6) to (11), particularly structures (4), (6), and (8), in which defects in appearance are easily visible.

[0141] Furthermore, when a laminate produced using an adhesive containing a large amount of aromatic diisocyanate monomer as the polyisocyanate composition (X) is used to produce packaging materials that undergo retort or boiling treatment, there is a risk that PAA (primary aromatic amine) derived from the aromatic polyisocyanate compound will migrate from the adhesive layer to the contents. The PAA in the adhesive layer decreases over time as it reacts with moisture, and retort or boiling treatment cannot be performed until its content falls below a specified value. The adhesive of the present invention exhibits physical properties even with a small amount of aromatic diisocyanate monomer in the polyisocyanate composition (X), so the above-mentioned concerns are eliminated and retort or boiling treatment can be performed quickly. Therefore, the adhesive of the present invention is also preferably used to produce laminates for packaging materials that require boiling or retort treatment.

[0142] More specific configurations of the packaging laminate used in boiling treatment and retort treatment include, for example, PET film / adhesive layer / CPP film, PET film / adhesive layer / aluminum foil / adhesive layer / CPP film, PET film / adhesive layer / Ny film / adhesive layer / CPP film, PET film / adhesive layer / transparent vapor-deposited Ny film / adhesive layer / CPP film, PET film / adhesive layer / aluminum foil / adhesive layer / Ny film / adhesive layer / CPP film, PET film / adhesive layer / Ny film / adhesive layer / aluminum foil / adhesive layer / CPP film, transparent vapor-deposited PET film / adhesive layer / CPP film, transparent vapor-deposited PET film / adhesive layer / Ny film / adhesive layer / CPP film, OPP film / adhesive layer / CPP film, OPP film / adhesive layer / transparent vapor-deposited OPP film / adhesive layer / CPP film, transparent vapor-deposited OPP film / adhesive layer / CPP film, Examples include transparent vapor-deposited OPP film / adhesive layer / OPP film / adhesive layer / CPP film, transparent vapor-deposited OPE film / adhesive layer / CPP film, transparent vapor-deposited OPE film / adhesive layer / LLDPE film, Ny film / adhesive layer / CPP film, transparent vapor-deposited Ny film / adhesive layer / CPP film, and gas-barrier polyolefin film / adhesive layer / CPP film.

[0143] In these configurations, it is preferable to use heat-resistant grade OPP film, transparent vapor-deposited OPP film, CPP film, and LLDPE film (those that are less susceptible to heat shrinkage during boiling or retort processing). The adhesive of the present invention is used to form an adhesive layer that is located on the inner side of the contents when the bag is made. When the laminate has multiple adhesive layers, the other adhesive layers may or may not be cured coating films of the adhesive of the present invention. When the laminate has multiple adhesive layers and at least one of the films other than the sealant film has a transparent vapor-deposited layer, it is preferable that all of the multiple adhesive layers are cured coating films of the adhesive of the present invention.

[0144] Other preferred configuration examples include OPE film / adhesive layer / LLDPE film, MDOPE film / adhesive layer / LLDPE film, HDPE film / adhesive layer / LLDPE film, gas barrier polyolefin film / adhesive layer / LLDPE film, OPP film / adhesive layer / LLDPE film, PET film / adhesive layer / LLDPE film, Ny film / adhesive layer / LLDPE film, PET film / adhesive layer / Ny film / adhesive layer / LLDPE film, etc. In the configurations exemplified above, the LLDPE film may be colored white.

[0145] When the adhesive of the present invention is a solvent-based adhesive, the adhesive of the present invention is applied to a film material 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 a laminate of the present invention. After lamination, it is preferable to perform an aging treatment. The aging temperature is preferably room temperature to 80°C, and the aging time is preferably 12 to 240 hours.

[0146] When 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 a film material serving as a substrate using a roll such as a gravure roll, and then the other substrate is immediately laminated to obtain a laminate of the present invention. After lamination, it is preferable to perform an aging treatment. The aging temperature is preferably room temperature to 70°C, and the aging time is preferably 6 to 240 hours.

[0147] The amount of adhesive to be applied is adjusted as appropriate. For example, in the case of a solvent-based adhesive, the solid content is 1 g / m. ２ 10g / m or more ２ Preferably 2 g / m or less ２ 5g / m or more ２ In the case of a solvent-free adhesive, the amount of adhesive applied is adjusted to, for example, 1 g / m ２ 5g / m or more ２ Preferably 1 g / m or less ２ 3g / m or more ２ The following is the result.

[0148] The laminate of the present invention may further include other films or substrates in addition to the above-described configurations (1) to (11). As the other substrates, in addition to the above-described stretched films, unstretched films, and transparent vapor-deposited films, porous substrates such as paper, wood, and leather, which will be described later, can also be used. The adhesive used to bond the other substrates may or may not be the adhesive of the present invention.

[0149] 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, or the like in order to improve adhesion when laminated with other materials.

[0150] The laminate of the present invention can be suitably used for a variety of applications, such as packaging materials for food, medicines, and daily necessities; lid materials; paper tableware such as paper straws, paper napkins, paper spoons, paper plates, and paper cups; barrier materials; roofing materials; solar cell panel materials; battery packaging materials; window materials; outdoor flooring materials; lighting protection materials; automotive components; signs; stickers and other outdoor industrial applications; decorative sheets used in simultaneous injection molding decoration methods; and packaging materials for liquid laundry detergents, liquid kitchen detergents, liquid bath detergents, liquid bath soaps, liquid shampoos, liquid conditioners, and the like.

[0151] <Packaging Material> The laminate of the present invention can be used as a multilayer packaging material for protecting foods, medicines, etc. When used as a multilayer packaging material, the layer structure can be changed depending on the contents, the environment of use, and the form of use. In addition, the packaging of the present invention may be appropriately provided with an easy-open treatment or a resealable means.

[0152] An example of a specific embodiment of the packaging material of the present invention is a packaging material obtained by forming a bag from the above-described laminate. The laminate is folded or overlapped, with the inner layer surfaces (the surfaces of the sealant film) facing each other, and the peripheral edges are heat-sealed to form a bag. Examples of bag-making methods include heat-sealing methods using a side seal, two-sided seal, three-sided seal, four-sided seal, envelope seal, flared seal, flat-bottom seal, square-bottom seal, gusset seal, or other heat seal types. The packaging material of the present invention can take various forms depending on the contents, usage environment, and usage pattern. Self-standing packaging materials (standing pouches) are also possible. Examples of heat-sealing methods include known methods such as bar seal, rotary roll seal, belt seal, impulse seal, high-frequency seal, and ultrasonic seal.

[0153] The packaging material of the present invention is filled with contents through its opening, and then the opening is heat-sealed to produce a product using the packaging material of the present invention. Examples of contents to be filled include foods such as rice crackers, bean snacks, nuts, biscuits, cookies, wafer snacks, marshmallows, pies, semi-dried cakes, candies, and snacks; staple foods such as bread, snack noodles, instant noodles, dried noodles, pasta, aseptically packaged cooked rice, porridge, rice porridge, packaged rice cakes, and cereal foods; processed agricultural products such as pickles, boiled beans, natto, miso, frozen tofu, tofu, nametake mushrooms, konjac, processed wild vegetables, jams, peanut cream, salads, frozen vegetables, and processed potatoes; processed livestock products such as ham, bacon, sausages, processed chicken, and corned beef; and processed fish ham and meat products. Examples of such foods include processed seafood products such as sausages, fish paste products, kamaboko, nori seaweed, tsukudani (simmered foods in soy sauce), bonito flakes, salted fish, smoked salmon, and spicy mentaiko; fruit pulp such as peaches, mandarin oranges, pineapples, apples, pears, and cherries; vegetables such as corn, asparagus, mushrooms, onions, carrots, radishes, and potatoes; cooked foods such as frozen and chilled prepared dishes, including hamburgers, meatballs, fried seafood, gyoza, and croquettes; dairy products such as butter, margarine, cheese, cream, instant creamy powder, and infant formula; liquid seasonings, retort curry, and pet food.

[0154] In addition, the present invention can also be used as a packaging material for various non-food products, such as cigarettes, disposable body 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 emulsion, vacuum insulation materials, batteries, etc.

[0155] <Recycled Plastics> The laminate and packaging material of the present invention can be used as raw materials for recycled plastics. The recycled plastics of the present invention are produced by recycling the laminate and packaging material of the present invention as raw materials. There are no particular limitations on the method for recycling the laminate and packaging material, and known methods can be used. Examples include a method in which the laminate and packaging material are crushed, melt-kneaded, and then pelletized and molded, and a method in which, without melt-kneading or pelletizing, crushed laminate and packaging material are directly fed into an extrusion molding machine and melt-kneaded in the heating barrel of the molding machine to form a molding raw material.

[0156] The laminate and packaging material can be crushed using a known crusher. There are no particular limitations on the crusher, and examples include methods using a jaw crusher, impact crusher, cutter mill, stamp mill, ring mill, roller mill, jet mill, or hammer mill. The size of the fragments of the printed matter or laminate is preferably 1 mm to 40 mm in side length, more preferably 8 mm to 20 mm.

[0157] The crushed laminate and packaging material are preferably washed before being subjected to heat melting. Examples of the washing method include a batch method and a continuous method, and water, detergent, neutralizing agent, and alkaline aqueous solution may be used. The washed laminate and packaging material are preferably dehydrated and dried. A centrifugal dehydration method is suitable for the dehydration method, and a hot air drying method is suitable for the drying method.

[0158] Dehydration and drying can adjust the moisture content of the laminate to be heated and melted. This prevents foaming during the production of recycled plastics. If bubbles form during pellet production, the pressure in the cylinder changes, causing the extrusion volume and extrusion pressure to fluctuate, potentially resulting in irregular pellet shapes and dimensions. Furthermore, when using the pellets to produce molded products through secondary molding, unevenness is likely to occur on the surface, potentially deteriorating the surface condition of the molded product.

[0159] In one embodiment, dehydration and drying are carried out until the moisture content of the laminate to be used in the production of recycled plastic is 3% by mass or less, preferably 2% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less, based on the total mass of the laminate.

[0160] The crushed laminate and packaging material are heated to melt at 120 to 280°C and then kneaded. The temperature at which the laminate and packaging material are melted can be adjusted taking into consideration the glass transition temperature and melting temperature of the laminate or packaging material, the shape to be pelletized, and the pressure to be applied in the molding process. The screw rotation speed during kneading is, for example, 50 to 1000 RPM.

[0161] The melt-kneaded laminate and packaging material are cooled and shredded into pellets. Examples of pelletizing methods include, but are not limited to, hot-cut and strand-cut methods. To prevent foreign matter from being mixed into the pellets, it is preferable that a screen mesh be provided at the discharge port of the melt-kneaded laminate and packaging material. Examples of screen mesh include plain weave, twill weave, plain dutch weave, and twill dutch weave, as well as punched metal types. Taking into consideration the pressure and clogging of the discharge port, the screen mesh size is preferably 40 mesh or larger, more preferably 80 mesh or larger, and even more preferably 120 mesh or larger. Examples of cooling methods include air cooling, wind cooling, and water cooling. In the present invention, a water cooling step is preferably included. Cooling to 20°C to 80°C is preferable, and cooling to 30°C to 60°C is more preferable.

[0162] When the multiple base materials constituting the laminate are made of the same resin type, the laminate of the present invention can be directly used for the production of recycled plastics as described above, but it may also be used for the production of recycled plastics after being immersed in a release agent (for example, an alkaline solution such as an aqueous sodium hydroxide solution) for a certain period of time to peel off each layer of the laminate.

[0163] When the multiple substrates constituting the laminate of the present invention are made of different resin types, it is preferable to immerse the laminate in a release agent for a certain period of time to peel off each layer of the laminate, and then separate the laminate by resin type for use in the production of recycled plastics. Conventionally known release agents can be used.

[0164] The printed layer may be removed before use in the production of recycled plastics. The printed layer can be removed by a known method. The printed layer itself may be formed using a printing ink that is easily peeled from the substrate by immersion in a release agent, or a release layer may be formed between the printed layer and the substrate by applying a coating agent containing a resin that is easily peeled from the substrate by immersion in a release agent, and the printed layer may be provided on the release layer.

[0165] The recycled plastic of the present invention may contain known additives, such as at least one antioxidant selected from the group consisting of phenolic and phosphorus-based additives, at least one lubricant selected from the group consisting of fatty acid amides, alkylene fatty acid amides, metal soaps, and esters, a hindered amine weather stabilizer, a wax having an acid value of 5 mg KOH / g or less, and at least one antistatic agent selected from the group consisting of fatty acid sulfonates and fatty acid esters.

[0166] The recycled plastic of the present invention may contain virgin plastic as a raw material in addition to the laminate or packaging material of the present invention. The virgin plastic to be added is of the same resin type as the substrate used in the laminate of the present invention. The virgin plastic may be added when pelletizing the laminate or packaging material of the present invention, or when molding the pelletized recycled plastic of the present invention. The virgin plastic may be added both when pelletizing and when molding the recycled plastic. The amount of virgin plastic used in combination when pelletizing the laminate or packaging material of the present invention is, for example, in a laminate or packaging material:virgin plastic ratio of 100:0 to 25:75 (mass ratio). The amount of virgin plastic used when molding the pelletized recycled plastic of the present invention is, for example, in a recycled plastic:virgin plastic ratio of 100:0 to 25:75 (mass ratio).

[0167] The recycled plastic of the present invention can be used as a raw material for various plastic products. Examples of plastic products include, but are not limited to, automobile parts such as bumpers and interior materials, components for home appliances, transportation pallets and containers, containers such as bottles, hangers, stationery, pots and cups, disposable cutlery, and play equipment. The recycled plastic can also be recycled as a film, or the recycled film can be molded and used, for example, as a cushioning material for transporting fruit, but this is not limited to this. The recycled plastic of the present invention can be converted into a film by known methods such as T-die molding, inflation molding, solution casting molding, and calendar molding. The recycled film can be molded by known methods such as vacuum molding and hot press molding.

[0168] The present invention will be described in more detail below with reference to specific synthesis examples and examples, but the present invention is not limited to these examples. In the following examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively, unless otherwise specified.

[0169] <Preparation of Polyisocyanate Composition (X)> (Synthesis Example 1) Polyurethane Polyisocyanate (A1-1) 774.5 parts of toluene diisocyanate (TDI) was added to a reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, and condenser, and the mixture was heated to 40°C while stirring under a nitrogen gas stream. 225.5 parts of bifunctional polyethylene glycol having a molecular weight of 200 was then added, taking care not to generate heat, and the mixture was then heated to 60°C. The reaction was continued at 60°C until the NCO% no longer changed, and 1.0 part of polyphosphoric acid was added to terminate the reaction. Next, using a thin-film distillation apparatus, the mixture was purified at a pressure of approximately 0.02 Torr and a temperature of 160°C until the TDI in the urethane prepolymer, the reaction product of TDI, was reduced to 0.05% by mass of solids, thereby obtaining polyurethane polyisocyanate (A1-1). The NCO% of polyurethane polyisocyanate (A1-1) was 14.5%.

[0170] (Synthesis Example 2) Polyurethane Polyisocyanate (A1-2) 822.8 parts of toluene diisocyanate (TDI) was added to a reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, and condenser, and the mixture was heated to 40°C while stirring under a nitrogen gas stream. Subsequently, 177.2 parts of bifunctional polyethylene glycol having a molecular weight of 150 was added while taking care not to generate heat, and the mixture was then heated to 60°C. The reaction was continued at 60°C until the NCO% no longer changed, and 1.0 part of polyphosphoric acid was added to terminate the reaction. Next, using a thin-film distillation apparatus, the mixture was purified at a pressure of approximately 0.02 Torr and a temperature of 160°C until the TDI in the urethane prepolymer, the reaction product of TDI, was reduced to 0.05% by mass of solids, thereby obtaining polyurethane polyisocyanate (A1-2). The NCO% of polyurethane polyisocyanate (A1-2) was 16.2%.

[0171] (Synthesis Example 3) Polyurethane Polyisocyanate (A1-3) 635.3 parts of toluene diisocyanate (TDI) was added to a reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, and condenser, and the mixture was heated to 40°C while stirring under a nitrogen gas stream. Subsequently, 364.7 parts of bifunctional polyethylene glycol having a molecular weight of 400 was added while taking care not to generate heat, and the mixture was then heated to 60°C. The reaction was continued at 60°C until the NCO% no longer changed, and 1.0 part of polyphosphoric acid was added to terminate the reaction. Next, using a thin-film distillation apparatus, the mixture was purified at a pressure of approximately 0.02 Torr and a temperature of 160°C until the TDI in the urethane prepolymer, the reaction product of TDI, was reduced to 0.05% by mass of solids, thereby obtaining polyurethane polyisocyanate (A1-3). The NCO% of polyurethane polyisocyanate (A1-3) was 11.2%.

[0172] (Synthesis Example 4) Polyurethane Polyisocyanate (A1-4) 410.6 parts of toluene diisocyanate (TDI) was added to a reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, and condenser, and the mixture was heated to 40°C while stirring under a nitrogen gas stream. Subsequently, 589.4 parts of bifunctional polyethylene glycol having a molecular weight of 1000 was added while taking care not to generate heat, and the mixture was then heated to 60°C. The reaction was continued at 60°C until the NCO% no longer changed, and 1.0 part of polyphosphoric acid was added to terminate the reaction. Next, using a thin-film distillation apparatus, the mixture was purified at a pressure of approximately 0.02 Torr and a temperature of 160°C until the TDI in the urethane prepolymer, the reaction product of TDI, was reduced to 0.05% by mass of solids, thereby obtaining polyurethane polyisocyanate (A1-4). The NCO% of polyurethane polyisocyanate (A1-4) was 6.2%.

[0173] (Synthesis Example 5) Polyurethane Polyisocyanate (A1-5) 7 parts of ethylene glycol and 35 parts of diethylene glycol were charged into a flask equipped with a stirrer, thermometer, nitrogen gas inlet tube, rectifying tube, water separator, etc., and heated to 80 ° C. while stirring under a nitrogen gas stream. 36 parts of adipic acid and 22 parts of isophthalic acid were further charged into the reaction vessel with stirring, and the reaction vessel was gradually heated so that the temperature at the top of the rectifying tube did not exceed 100 ° C. The internal temperature was maintained at 250 ° C., and an esterification reaction was carried out. When the acid value reached 12.0 mg KOH / g or less, the temperature was increased to 240 ° C., and the pressure inside the reaction vessel was gradually reduced. The reaction was carried out at 40 Torr or less, yielding a polyester polyol having an acid value of 1.0 mg KOH / g and a hydroxyl value of 84 mg KOH / g and having hydroxyl groups at both ends.

[0174] To a reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, and condenser, 342.8 parts of toluene diisocyanate (TDI) was added, and the mixture was heated to 40°C while stirring under a nitrogen gas stream. Subsequently, 657.2 parts of the polyester polyol synthesized above was added, taking care not to generate heat, and then the mixture was heated to 60°C. The reaction was continued at 60°C until the NCO% no longer changed, and 1.0 part of polyphosphoric acid was added to terminate the reaction. Next, using a thin-film distillation apparatus, the mixture was purified at a pressure of approximately 0.02 Torr and a temperature of 160°C until the TDI in the urethane prepolymer, the reaction product of TDI, was reduced to 0.05% by mass of solids, thereby obtaining a polyurethane polyisocyanate (A1-5). The NCO% of the polyurethane polyisocyanate (A1-5) was 4.8%.

[0175] (Synthesis Example 6) Polyurethane Polyisocyanate (A1-6) 582.2 parts of toluene diisocyanate (TDI) was added to a reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, and condenser, and the mixture was heated to 40°C while stirring under a nitrogen gas stream. Thereafter, 278.5 parts of bifunctional polyethylene glycol having a molecular weight of 400 and 139.3 parts of bifunctional polypropylene glycol having a molecular weight of 1000 were added while taking care not to generate heat, and the mixture was then heated to 60°C. The reaction was continued at 60°C until the NCO% no longer changed, and 1.0 part of polyphosphoric acid was added to terminate the reaction. Next, using a thin-film distillation apparatus, the mixture was purified at a pressure of approximately 0.02 Torr and a temperature of 160°C until the TDI in the urethane prepolymer, the reaction product of TDI, was reduced to 0.05% by mass of solids, thereby obtaining polyurethane polyisocyanate (A1-6). The NCO% of polyurethane polyisocyanate (A1-6) was 9.4%.

[0176] Synthesis Example 7 Polyurethane Polyisocyanate (A'1) 7 parts of ethylene glycol and 35 parts of diethylene glycol were charged into a flask equipped with a stirrer, thermometer, nitrogen gas inlet tube, rectifying tube, water separator, etc., and heated to 80°C while stirring under a nitrogen gas stream. 36 parts of adipic acid and 22 parts of isophthalic acid were further charged into the reaction vessel with stirring, and the reaction vessel was gradually heated so that the temperature at the top of the rectifying tube did not exceed 100°C, while the internal temperature was maintained at 250°C, and an esterification reaction was carried out. When the acid value reached 12.0 mgKOH / g or less, the temperature was increased to 240°C, and the pressure inside the reaction vessel was gradually reduced. The reaction was carried out at 40 Torr or less, yielding a polyester polyol having an acid value of 1.0 mgKOH / g and a hydroxyl value of 84 mgKOH / g and having hydroxyl groups at both ends.

[0177] A flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube was charged with 54 parts of a mixture of 2,2-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, and 4,4'-diphenylmethane diisocyanate, and the mixture was heated to 60°C while stirring under a nitrogen gas stream. 23 parts of the polyester polyol synthesized above and 23 parts of polypropylene glycol having a number average molecular weight of 1,000 were added dropwise in several batches, and the mixture was further heated and maintained at an internal temperature of 70°C for 4 hours to carry out a urethanization reaction, yielding a polyurethane polyisocyanate (A'1) having an NCO group content of 14.7%.

[0178] (Preparation of Polyisocyanate Composition (X)) Polyurethane polyisocyanates (A1-1) to (A1-6), (A'1), and hexamethylene diisocyanate derivatives (A2-1) to (A2-3) (referred to as HDI derivatives (A2-1) to (A2-3) in the tables) were mixed in the formulations shown in Tables 1 and 2 to prepare polyisocyanate compositions (X) of the Examples and Comparative Examples. The hexamethylene diisocyanate derivatives (A2-1) to (A2-3) used were as follows:

[0179] (Hexamethylene diisocyanate derivative (A2-1)) Desmodur N3300 (nurate form of hexamethylene diisocyanate, hexamethylene diisocyanate content: 0.2% by mass), manufactured by Covestro. (Hexamethylene diisocyanate derivative (A2-2)) Desmodur N3200A (bouret form of hexamethylene diisocyanate, hexamethylene diisocyanate content: 0.7% by mass), manufactured by Covestro. (Hexamethylene diisocyanate derivative (A2-3)) Takenate D178NL (allophanate form of hexamethylene diisocyanate, hexamethylene diisocyanate content: 0.5% by mass), manufactured by Mitsui Chemicals, Inc.

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[0181]

[0182] <Preparation of Isocyanate-Reactive Composition (Y)> (Isocyanate-Reactive Composition (Y-1)) 31.4 parts of diethylene glycol, 9.6 parts of glycerin, 19.9 parts of isophthalic acid, 39.1 parts of adipic acid, and 0.01 parts of titanium tetraisopropoxide were added to a polyester reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, rectification tube, etc., and an esterification reaction was carried out at an internal temperature of 220 ° C. After the dehydration reaction, a polyester polyol having an acid value of 1.5 mg KOH / g was obtained. 20 parts of polypropylene triol (Excenol 430 manufactured by AGC, molecular weight 400, trifunctional, hydroxyl value 400 mg KOH / g) was added to 80 parts of this polyester polyol, to obtain an isocyanate-reactive composition (Y-1).

[0183] (Isocyanate-reactive composition (Y-2)) 80 parts of polypropylene glycol (Excenol 420 manufactured by AGC, molecular weight 400, bifunctional, hydroxyl value 280 mg KOH / g) and 20 parts of polypropylene triol (Excenol 430 manufactured by AGC, molecular weight 400, trifunctional, hydroxyl value 400 mg KOH / g) were mixed to obtain an isocyanate-reactive composition (Y-2). The hydroxyl value of the isocyanate-reactive composition (Y-2) was 305 mg KOH / g.

[0184] (Isocyanate-reactive composition (Y-3)) A reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, rectification tube, water separator, etc. was charged with 400 parts by mass of propylene glycol, 80 parts by mass of trimethylolpropane, 700 parts by mass of adipic acid, and 0.1 parts by mass of titanium tetraisopropoxide under nitrogen gas introduction, and the mixture was gradually heated so that the temperature at the top of the rectification tube did not exceed 100°C, and the internal temperature was maintained at 250°C. When the acid value reached 1 mgKOH / g or less, the esterification reaction was terminated to obtain a polyester polyol. The polyester polyol had a hydroxyl value of 185 mgKOH / g. 6% by mass of an amine-initiated polypropylene polyol (manufactured by ADEKA Corporation, EDP-450, molecular weight 450, hydroxyl value 505 mgKOH / g) was added to this polyester polyol to obtain an isocyanate-reactive composition (Y-3). The hydroxyl value of the isocyanate-reactive composition (Y-3) was 220 mgKOH / g.

[0185] (Isocyanate-reactive composition (Y-4)) 203.4 parts of ethylene glycol, 257.5 parts of neopentyl glycol, and 21.0 parts of trimethylolpropane were added to a polyester reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, rectification tube, etc., and heated to 80°C with stirring under a nitrogen gas stream. 384.7 parts of adipic acid and 243.3 parts of isophthalic acid were further added with stirring, and the mixture was gradually heated so that the temperature at the top of the rectification tube did not exceed 100°C, while the internal temperature was maintained at 240°C, and an esterification reaction was carried out. After the reaction, a polyester polyol having hydroxyl groups at both ends and having an acid value of 1 mgKOH / g and a hydroxyl value of 196 mgKOH / g was obtained. 80 parts of this polyester polyol and 20 parts of polypropylene triol (Excenol 430 manufactured by AGC, molecular weight 400, trifunctional, hydroxyl value 400 mgKOH / g) were mixed to obtain an isocyanate-reactive composition (Y-4). The hydroxyl value of the isocyanate-reactive composition (Y-4) was 240 mgKOH / g.

[0186] <Preparation of Adhesive> The polyisocyanate composition (X) and the isocyanate-reactive composition (Y) were mixed in the formulations shown in Tables 3 to 5 to prepare adhesives for the Examples and Comparative Examples.

[0187] <Production of Laminate> (Laminate 1) The prepared adhesive was applied in an amount of 2.5 g / m to a transparent vapor-deposited polyester film (GL-ARH, manufactured by TOPPAN) having a thickness of 12 μm. ２ (solid content), and the laminate was laminated to a nylon film (Emblem ONBC RT, manufactured by Unitika Ltd.) having a thickness of 15 μm. Subsequently, the same adhesive was applied to the nylon film surface of the laminate in an amount of 2.5 g / m. ２ (solid content), and the laminate was laminated to a 70 μm-thick unstretched polypropylene film for retort pouches (Toray Film Processing Co., Ltd., Torayfan No. ZK207). The laminate was aged at 40° C. for 2 days to obtain Laminate 1.

[0188] (Laminate 2) An anchor coating agent containing a mixture of a silane coupling agent, an acrylic polyol, and an isocyanate curing agent was applied to one side of a biaxially oriented polypropylene film having a thickness of 20 μm to form an anchor coating layer having a thickness of 0.3 μm. After that, an aluminum oxide layer having a thickness of 15 nm was formed using an electron beam heating method, thereby obtaining a biaxially oriented polypropylene film having a transparent vapor deposition layer.

[0189] The prepared adhesive was applied to a biaxially stretched polypropylene film (Toyobo Co., Ltd., Pylen EXTOP XP610) with a thickness of 20 μm at a coating amount of 2.5 g / m ２ (solid content), and the laminate was laminated to the transparent vapor-deposited layer of the transparent vapor-deposited biaxially oriented polypropylene film. Subsequently, the same adhesive was applied to the transparent vapor-deposited biaxially oriented polypropylene film of the laminate in an amount of 2.5 g / m. ２ (solid content), and the laminate was laminated to a 70 μm-thick unstretched polypropylene film for retort pouches (Toray Film Processing Co., Ltd., Torayfan No. ZK207). The laminate was aged at 40° C. for 2 days to obtain Laminate 2.

[0190] (Laminate 3) The prepared adhesive was applied in an amount of 2.5 g / m to a nylon film (Emblem ONBC RT, manufactured by Unitika Ltd.) having a thickness of 15 μm. ２ (solid content), and the adhesive-coated surface of this film was laminated with an unstretched polypropylene film for retort pouches (Toray Film Processing Co., Ltd., Torayfan No. ZK207) using a laminator. After aging at 40°C for 2 days, Laminate 3 was obtained.

[0191] <Evaluation> (Retort resistance) Test pieces were cut out from Laminates 1 and 2, folded with the unstretched polypropylene film for retort facing inward, and heat-sealed at three sides excluding the fold at a width of 10 mm. 1 / 1 / 1 sauce (meat sauce: vegetable oil: vinegar = 1:1:1) was added as the contents. The filled pouches were retorted in a shower-type retort sterilizer at 121°C for 30 minutes. The presence or absence of delamination in the retort-treated pouches was confirmed. Evaluation was performed according to the following criteria, and the results are summarized in Tables 3 to 5. 5: No delamination 1: Delamination

[0192] (Adhesion Strength After Retort Treatment (Laminate 1)) The contents were removed from the retort-treated pouch, and a 15 mm wide test piece was cut from the pouch. Using a tensile tester, the adhesive strength (N / 15 mm) between the nylon film and the unstretched polypropylene film for retort was measured using a T-peel method at a peel rate of 300 mm / min. Evaluation was performed according to the following criteria, and the results are summarized in Tables 3 to 5. 5: 7 N / 15 mm or more 4: 5 N / 15 mm or more and less than 7 N / 15 mm 3: 4 N / 15 mm or more and less than 5 N / 15 mm 2: 3 N / 15 mm or more and less than 4 N / 15 mm 1: Less than 3 N / 15 mm

[0193] (Adhesion Strength After Retort Treatment (Laminate 2)) The contents were removed from the retort-treated pouch, and a 15 mm wide test piece was cut from the pouch. Using a tensile tester, the adhesive strength (N / 15 mm) between the transparent vapor-deposited biaxially oriented polypropylene film and the unoriented polypropylene film for retort was measured using a T-peel method at a peel rate of 300 mm / min. Evaluation was performed according to the following criteria, and the results are summarized in Tables 3 to 5. 5: 2.5 N / 15 mm or more 4: 2 N / 15 mm or more and less than 2.5 N / 15 mm 3: 1.5 N / 15 mm or more and less than 2 N / 15 mm 2: 1 N / 15 mm or more and less than 1.5 N / 15 mm 1: Less than 1 N / 15 mm

[0194] (PAA elution amount) Each of the laminates 1, 2, and 3 was cut into a size of 120 mm x 220 mm, folded so that the unstretched polypropylene film for retort pouches was on the inside, and heat-sealed in three directions with a width of 10 mm at 1 atm, 180°C, and 1 second. ２ A pouch was prepared that was in contact with the surface of the pouch. The pouch was filled with a 3% acetic acid vinegar solution and retorted at 121°C for 30 minutes, after which PAA was measured by LC / MS / MS. The results were evaluated according to the following criteria and are summarized in Tables 3 to 5. 5: PAA elution amount is less than 2 ppb; 3: PAA elution amount is 2 ppb or more but less than 10 ppb; 1: PAA elution amount is 10 ppb or more.

[0195] (Processing appearance) At a processing speed of 100 m / min, the prepared adhesive was applied in an amount of 2.0 g / m to a transparent vapor-deposited polyester film (GL-ARH, manufactured by TOPPAN Co., Ltd.) having a film thickness of 12 μm.２ (solid content), and the laminate was laminated to a nylon film (Emblem ONBC RT, manufactured by Unitika Ltd.) with a thickness of 15 μm. Subsequently, the same adhesive was applied to the nylon film surface of the laminate in an amount of 2.0 g / m at a processing speed of 100 m / min. ２ (solids content), and laminated to a 70 μm-thick unstretched polypropylene film for retort pouches (Toray Film Processing Co., Ltd., Torayfan No. ZK207), followed by aging at 40° C. for 2 days to obtain Laminate 4. Laminates were obtained in the same manner as Laminate 4, except that the processing speeds were 150 m / min, 180 m / min, and 200 m / min. The presence or absence of air bubbles remaining in the laminate after aging was confirmed, and the processing speed range in which no air bubbles remained was investigated. Evaluation was performed according to the following criteria, and the results are summarized in Tables 3 to 5. 5: No air bubbles remaining even at processing speeds of 200 m / min or more 4: No air bubbles remaining at 180 m / min 3: No air bubbles remaining at 150 m / min 2: No air bubbles remaining at 100 m / min 1: Air bubbles remaining at 100 m / min

[0196]

[0197]

[0198]

Claims

1. A two-component curing adhesive comprising a polyisocyanate composition (X) containing a polyisocyanate compound (A) and an isocyanate-reactive composition (Y) containing a polyol compound (B), wherein the polyisocyanate compound (A) contains a polyurethane polyisocyanate (A1) which is a reaction product of toluene diisocyanate and a polyol, and a hexamethylene diisocyanate derivative (A2), and the content of diisocyanate monomer in the polyisocyanate composition (X) is 1.0 mass% or less.

2. The two-component curing adhesive according to claim 1, wherein the polyurethane polyisocyanate (A1) is a reaction product of toluene diisocyanate and a polyol having a molecular weight of 50 g / mol or more and 4000 g / mol or less.

3. The two-component curing adhesive according to claim 1, wherein the polyurethane polyisocyanate (A1) is a reaction product of toluene diisocyanate and a polyol containing 20% ​​by mass or more of a polyol having a molecular weight of 50 g / mol or more and 500 g / mol or less.

4. The two-component curing adhesive according to claim 1, wherein the polyol contains at least one selected from the group consisting of glycol, polyether polyol, and polyester polyol.

5. The two-component curing adhesive according to claim 1, wherein the hexamethylene diisocyanate derivative (A2) includes a nurate form of hexamethylene diisocyanate (A2-2).

6. A two-component curing adhesive according to claim 1, wherein the content of polyurethane polyisocyanate (A1) in the polyisocyanate compound (A) is 50% by mass or more and 95% by mass or less.

7. The two-component curing adhesive according to claim 1, wherein the polyol compound (B) contains a polyester polyol (B1).

8. The two-component curing adhesive according to claim 2, wherein the polyol compound (B) contains a polyether polyol (B2).

9. The two-component curing adhesive according to claim 1, which contains at least one selected from the group consisting of a urethane catalyst, a phosphoric acid derivative, a plasticizer, and an acid anhydride.

10. The two-component curing adhesive according to claim 1, which is a solvent-free type.

11. A laminate comprising a first substrate, a second substrate, and a first adhesive layer disposed between the first substrate and the second substrate, wherein the first adhesive layer is a cured coating film of the two-component curing adhesive according to any one of claims 1 to 10.

12. The laminate according to claim 11, wherein the first substrate has a vapor-deposited layer of an inorganic oxide.

13. The laminate according to claim 11, further comprising a third substrate and a second adhesive layer disposed between the second substrate and the third substrate, the second adhesive layer being a cured coating film of the two-component curing adhesive according to any one of claims 1 to 10.

14. A laminate comprising a first substrate, a second substrate, and a first adhesive layer disposed between the first substrate and the second substrate, wherein the first substrate and the second substrate are bonded together via the adhesive, and the laminate is aged at 40°C for two days, and then retort-treated at 121°C for 30 minutes, and the amount of PAA elution from the laminate is less than 10 ppb.

15. The laminate according to claim 14, wherein the first substrate has a vapor-deposited layer of an inorganic oxide.

16. A packaging material comprising the laminate of claim 11.

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