Two-component curing adhesives, laminates, and packaging materials

Abstract

The present invention provides a two-component curing adhesive that suppresses appearance defects even when used as a solvent-free adhesive in the manufacture of barrier substrates. 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) comprises 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% by mass or less.

Description

[Technical Field]

[0001] This invention relates to a two-component curing adhesive, a laminate, and a packaging material. [Background technology]

[0002] For packaging materials of food, medical products, cosmetics, and daily necessities, composite materials are used that are created by laminating multiple layers of metal foil such as aluminum foil or metal-deposited film with plastic films such as polyethylene, polypropylene, polyvinyl chloride, polyester, and nylon. These laminates are formed by appropriately combining various plastic films, metal-deposited films, or metal foils according to the required characteristics for each application, and bonding them together with adhesives. Generally, a two-component curing type adhesive consisting of a polyol composition and a polyisocyanate composition is used (for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2014-101422 [Overview of the project] [Problems that the invention aims to solve]

[0004] As a two-component curing adhesive, the study and introduction of so-called solvent-free adhesives, which do not contain solvents, are also progressing. Solvent-free adhesives have many advantages, such as the absence of a drying process and the elimination of solvent discharge, and the absence of concerns about solvent residue in laminates after bonding plastic films together, or in laminates after bonding plastic films to metal foils or metal vapor-deposited layers. On the other hand, when solvent-free adhesives are used to laminate highly gas-barrier substrates (hereinafter also referred to as barrier substrates) that have a metal vapor-deposited layer such as aluminum or a transparent vapor-deposited layer of inorganic oxides such as silica or alumina on the film, appearance defects are likely to occur. This problem becomes more pronounced as the lamination speed increases.

[0005] This invention has been made in view of these problems, and aims to provide a two-component curing adhesive that suppresses appearance defects even when used as a solvent-free adhesive in the manufacture of barrier substrates. [Means for solving the problem]

[0006] In other words, 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) comprises 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% by mass or less. [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a two-component curing adhesive that suppresses appearance defects even when used as a solvent-free adhesive in the manufacture of barrier substrates. [Modes for carrying out the invention]

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

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

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

[0011] Polyols 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 All;

[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] A polyester polyol (1) which is a reaction product of a polyester obtained by ring-opening polymerization of a cyclic ester compound such as propiolactone, butyrolactone, ε-caprolactone, σ-valerolactone, β-methyl-σ-valerolactone, etc. and a polyhydric alcohol such as the glycol, glycerin, trimethylolpropane, pentaerythritol, etc.; A polyester polyol (2) obtained by reacting a bifunctional polyol such as the glycol, dimer diol, or the bisphenol, etc. with a polyvalent carboxylic acid; A polyester polyol (3) obtained by reacting a trifunctional or tetrafunctional aliphatic alcohol with a polyvalent carboxylic acid; A polyester polyol (4) obtained by reacting a bifunctional polyol with the trifunctional or tetrafunctional aliphatic alcohol and a polyvalent carboxylic acid; A polyester polyol (5) which is a polymer of a hydroxyl acid such as dimethylolpropionic acid, castor oil fatty acid, etc.;

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

[0016] Examples include castor oil-based polyols such as castor oil, dehydrated castor oil, castor hardened oil which is a hydrogenated product of castor oil, an adduct of 5 to 50 moles of alkylene oxide to castor oil, etc., and mixtures thereof, etc. One kind or a combination of two or more kinds can be used.

[0017] Examples of polymerization initiators for polyether polyols 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 triol compounds of polypropylene glycol;

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

[0020] Polycarboxylic acids used in the synthesis of 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 acid 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; 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 pimephosphate, diethyl sebacate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, and diethyl maleate;

[0022] Examples 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 acid-1,2-anhydride, hymic anhydride, hettic anhydride, and other alicyclic polybasic acids, which can be used individually 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 appearance defects even when the adhesive of the present invention is used as a solvent-free adhesive for bonding 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 less and 800 g / mol or less, and more preferably 50 g / mol or less and 500 g / mol or less. The molecular weight in this application is the value obtained from the following formula (1).

[0024]

number

[0025] The polyol used in the synthesis of polyurethane polyisocyanate (A1) is more likely to exhibit the effects of this invention if it contains polyols with relatively low molecular weights. It is preferable to contain 20% by mass or more of polyols with a molecular weight of 50 g / mol or less and 500 g / mol or less, and more preferable to contain 20% by mass or more of polyols with a molecular weight of 50 g / mol or less and 300 g / mol or less.

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

[0027] Polyurethane polyisocyanate (A1) is obtained by reacting toluene diisocyanate with a polyol under conditions in which the isocyanate groups of toluene diisocyanate are in excess of the hydroxyl groups of the polyol. The equivalent ratio of isocyanate groups to hydroxyl groups [NCO] / [hydroxyl groups] can be adjusted as appropriate, but as an example, it is between 2.0 and 20.0.

[0028] Examples of hexamethylene diisocyanate derivatives (A2) include the biuret form (A2-1), nurate form (A2-2), adduct form (A2-3), allophanate form (A2-4), carbodiimide modified form (A2-5), uretdione modified form (A2-6), iminooxadiazinedione form (A2-7), and polyurethane polyisocyanates other than polyurethane polyisocyanate (A1) (A2-7), and can be used individually or in combination of two or more. It is preferable that the hexamethylene diisocyanate derivative (A2) includes the nurate form (A2-2) of 1,6-hexamethylene diisocyanate.

[0029] The polyol used in the synthesis of polyurethane polyisocyanate (A2-7) can be the same as those exemplified for use in the synthesis of polyurethane polyisocyanate (A1). Preferably, it is at least one selected from glycol, polyether polyol, and polyester polyol.

[0030] The polyisocyanate composition (X) may contain, as the polyisocyanate compound (A), isocyanate derivatives other than polyurethane polyisocyanate (A1) and hexamethylene diisocyanate derivatives (A2) (A3). Examples of isocyanate derivatives (A3) include conventionally known aromatic diisocyanates, aromatic aliphatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and their bilate (A3-1), nurate (A3-2), adduct (A3-3), allophanate (A3-4), carbodiimide modified (A3-5), uretdione modified (A3-6), iminooxadiazinedione (A3-7), polyurethane polyisocyanates (A1), and polyurethane polyisocyanates other than (A2-7) (A3-7), and can be used individually 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 called polymeric MDI or crude MDI), 1,3-phenylenediisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylenediisocyanate (also known as PPDI), and 2,4-toluene. Examples include, but are not limited to, diisocyanates, 2,6-toluene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, toridine 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] Aromatic aliphatic diisocyanates refer to aliphatic isocyanates having one or more aromatic rings in their molecule, and include, but are not limited to, m- or p-xylylene diisocyanate (also known as XDI) and α,α,α',α'-tetramethylxylylene diisocyanate (also known as TMXDI).

[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, but are not limited to, 3-isocyanate-methyl-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(isocyanate-methyl)cyclohexane (also known as hydrogenated XDI or HXDI), hydrogenated TMXDI, norbornane diisocyanate (also known as NBDI), etc.

[0035] The polyol used in the synthesis of polyurethane polyisocyanate (A3-7) can be the same as those exemplified for use in the synthesis of polyurethane polyisocyanate (A1). Preferably, it is at least one selected from glycol, polyether polyol, and polyester polyol.

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

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

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

[0039] When the polyisocyanate composition (X) contains an isocyanate derivative (A3), the content of the isocyanate derivative (A3) in the polyisocyanate compound (A) can be appropriately adjusted according to the desired performance, but as an example, it is 30% by 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, aromatic aliphatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates, which are exemplified as raw materials for the isocyanate derivative (A3) described above, of 1.0% by mass or less. It is also preferable that the content of diisocyanate monomers in the polyisocyanate composition (X) be reduced to 0.5% by mass or less, and even further to 0.1% by mass or less.

[0041] When manufacturing laminates for food packaging using a two-component curing adhesive containing aromatic isocyanate prepolymers, unreacted aromatic isocyanate monomers may remain in the adhesive layer. These isocyanate monomers react with surrounding water to form primary aromatic amines (PAAs), which may migrate through the film and leach into the contents (food). PAAs are a cause for concern due to their potential harmful effects on human health, and various regulations have been established, including the European Commission's regulations on plastic materials and products for food contact, which set detection limits for PAAs.

[0042] Since PAA reacts with unreacted aromatic isocyanates in the surrounding environment, the concentration of PAA gradually decreases even if aromatic isocyanates remain in the adhesive layer. Eventually, it falls below the detection limit, but from the viewpoint of manufacturing efficiency for laminates used in food packaging, it is preferable to have a low initial value of aromatic isocyanate monomers remaining in the adhesive layer. By removing diisocyanate monomers in advance, a two-component curing adhesive with excellent manufacturing efficiency can be produced.

[0043] Furthermore, from the perspective of occupational safety and health, there is a movement to regulate the use of isocyanate monomers, and the European Commission has adopted the REACH regulation, which prohibits the market placement of products containing 0.1% by mass or more of isocyanate monomers if certain requirements are not met. Products can be made compliant with such regulations by removing unreacted diisocyanate monomers until the amount of diisocyanate monomer in the polyisocyanate composition is 0.1% by mass or less.

[0044] The diisocyanate monomer can be removed by distilling it under reduced pressure using a short-pass distillation apparatus or a thin-film distillation apparatus. The degree of reduced pressure and distillation temperature are adjusted as appropriate depending on the diisocyanate monomer to be removed, but as an example, they are 0.1 mbar or less and 120°C to 190°C. The diisocyanate monomer removal process may be performed multiple times.

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

[0046] Equipment: Waters Corporation "ACQUITY UPLC H-Class" Data processing: Empower-3 manufactured by Waters Corporation Column: Waters Corporation "ACQUITY UPLC HSS T3" (100 mm × 2.1 mmφ, 1.8 μm) 40℃ 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 as appropriate with the eluent (mobile phase). The liquid was passed through a 4.0.2 μm filtration filter to obtain the measurement sample. Calculation of area ratio: Calculated using the maximum absorption wavelength for the target material.

[0047] The NCO% of the polyisocyanate composition (X) can be adjusted as appropriate depending on the purpose, but as an example, it is preferably 7% to 21%.

[0048] When the adhesive of the present invention is used as a solvent-free adhesive, the viscosity of the polyisocyanate composition (X) is adjusted to a range suitable for the non-solvent laminating 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) is determined, for example, using a rotational viscometer with a cone-plate: 1° × diameter 50 mm, shear rate: 100 sec. -1 It can be measured at 60℃±1℃.

[0049] When the adhesive of the present invention is used as a solvent-type 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 multiple hydroxyl groups. Examples of polyol compounds (B) include polyester polyols (B1), polyether polyols (B2), vegetable oil polyols (B3), polyurethane polyols (B4), sugar alcohols (B5), acrylic polyols (B6), etc., and one or more of these can be used in combination.

[0051] Examples of polyester polyols (B1) include polyester polyols obtained as reaction products of polyhydric alcohols and polycarboxylic acids, and lactone-based polyester polyols obtained by polycondensation reactions of aliphatic polyols with various lactones such as ε-caprolactone. It is preferable to use polyester polyols obtained as 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)cyclohesane, and 2,2,4-trimethyl-1,3-pentanediol;

[0053] Trimethylolethane, trimethylolpropane, glycerin, hexanetriol, pentaerythritol, and other trifunctional or greater aliphatic polyols;

[0054] Bisphenols such as bisphenol A and bisphenol F; bisphenol alkylene oxide adducts obtained by adding ethylene oxide, propylene oxide, etc., to bisphenols such as bisphenol A and bisphenol F;

[0055] Examples include polyether polyols obtained by ring-opening polymerization of aliphatic diols or polyols with various cyclic ether-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether, and these can be used individually 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; Examples include p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid and ester-forming derivatives of their dihydroxycarboxylic acids, and polybasic acids such as dimer acids, which can be used individually or in combination of two or more.

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

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

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

[0060] Trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, pentaerythritol, and triol compounds of polypropylene glycol;

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

[0062] The molecular weight of the polyether polyol (B2) can be adjusted as appropriate, but as an example, it is preferably between 100 g / mol and 8000 g / mol. The hydroxyl value of polyether polyol (B2) can be adjusted as appropriate, but as an example, it is preferably between 10 mg KOH / g and 1200 mg KOH / g.

[0063] Examples of vegetable oil polyols (B3) include castor oil, dehydrated castor oil, hydrogenated castor oil (a hydrogenated product of castor oil), and castor oil alkylene oxide adducts of 5 to 50 moles.

[0064] Polyurethane polyols (B4) are reaction products of low-molecular-weight or high-molecular-weight polyols and polyisocyanate compounds. As low-molecular-weight or high-molecular-weight polyols, those similar to the polyhydric alcohols exemplified as raw materials for polyester polyols (B1) can be used. As polyisocyanate compounds, those similar to those exemplified as raw materials for isocyanate derivatives (A3) can be used.

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

[0066] Acrylic polyol (B6) is required to be an (meth)acrylic acid ester having a hydroxyl group, and can be obtained by copolymerization with a polymerizable unsaturated monomer as needed. In this specification, (meth)acrylic acid means methacrylic acid or acrylic acid. Examples of (meth)acrylic acid esters having a hydroxyl group include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate, which can be used individually or in combination of two or more.

[0067] Polymerizable unsaturated monomers include alkyl(meth)acrylates having alkyl groups with 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-methylcyclohexe-4-ene-1,2-dicarboxylic acid anhydride, bicyclo[2.2.2]octo-5-ene-2,3-dicarboxylic acid anhydride, 1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic acid anhydride, 2-octa-1,3-diketospiro[4.4]non-7-ene, bicyclo[ 2.2.1]Hepto-5-ene-2,3-dicarboxylic acid anhydride, maleopimaric acid, tetrahydrophthalic acid anhydride, methyl-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxylic acid anhydride, methyl-norbornene-5-ene-2,3-dicarboxylic acid anhydride, norbornne-5-ene-2,3-dicarboxylic acid anhydride, sulfonated styrene, vinylbenzenesulfonamide, and other polymerizable unsaturated monomers having acid groups; Vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl pivalate, and vinyl benzoate; Alkyl esters of crotonic acid, such as methyl crotonic acid and ethyl crotonic acid; Examples include, but are not limited to, dialkyl esters of unsaturated dibasic acids such as dimethyl maleate, di-n-butyl maleate, dimethyl fumarate, and dimethyl itaconate. These may be used individually or in combination of two or more.

[0069] (Isocyanate-reactive compound (C)) The isocyanate-reactive composition (Y) may contain isocyanate-reactive compounds (C) other than the polyol compound (B). An isocyanate-reactive compound (C) is a compound having a functional group that is reactive with an isocyanate group, and examples include amine compounds (C1) and monool compounds (C2). These can be used individually 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 refers to an NH2 group or an NHR group (where R is an alkyl group or aryl group which may have a functional group).

[0071] As the amine compound (C1), any known compound can be used without particular limitation, including 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, tripylenetetramine, 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 multiple amino groups, such as bis(aminomethyl)cyclohexane, diaminodicyclohexylmethane, isophoronediamine, mensendiamine, bis(cyanoethyl)diethylenetriamine, 1,4-bis-(8-aminopropyl)-piperazine, piperazine-1,4-diazacycloheptane, 1-(2'-aminoethylpiperazine), 1-[2'-(2"-aminoethylamino)ethyl]piperazine, tricyclodecanediamine, and polyureamines which are reaction products of the above-mentioned polyamines and the above-mentioned isocyanate components,

[0074] Primary or secondary alkanolamines (C1-C2) such as monoethanolamine, monoisopropanolamine, monobutanolamine, N-methylethanolamine, N-ethylethanolamine, N-methylpropanolamine, diethanolamine, and diisopropanolamine,

[0075] Examples include primary or secondary amines (C1-C3) such as ethylamine, octylamine, laurylamine, myristylamine, stearylamine, oleylamine, diethylamine, dibutylamine, and distearylamine.

[0076] The amount of amine compound (C1) can be adjusted as appropriate depending on the purpose, but as an example, it is preferable that the amine value of the isocyanate reactive composition (Y) be 20 to 70 mg KOH / g, more preferably 25 to 50 mg KOH / 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 the sample. There are no particular restrictions, and it can be calculated using known methods. If the chemical structure of the amine compound (E7) and, if necessary, the average molecular weight are known, it can be calculated using the formula: (number of amino groups per molecule / average molecular weight) × 56.1 × 1000. If the chemical structure or average molecular weight of the amine compound is unknown, it can be measured according to known amine value measurement methods, such as JIS K7237-1995.

[0078] Examples of monool compounds (C2) include compounds having one alcoholic hydroxyl group. The main chain of the monool compound (C2) is not particularly limited and can be vinyl resins, acrylic resins, polyesters, epoxy resins, urethane resins, etc., that have one hydroxyl group. Aliphatic alcohols, alkylalkylene glycols, etc. can also be used. The main chain of the monool compound (C2) may be linear or branched. There are no particular limitations on the bonding position of the hydroxyl group, but it is preferable that it be located at the end of the molecular chain.

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

[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, decatol, 2-cyclohexylcyclohexanol, 4-cyclohexylcyclohexanol, 4-(4-propylcyclohexyl)cyclohexanol, 4-(4-pentylcyclohex Sil-cyclohexanol, α-ambrinol, deoxycorticosterone, 11-dehydrocorticosterone, cholesterol, β-sitosterol, campesterol, stigmasterol, brassicasterol, lanosterol, ergosterol, β-cholestanol, testosterone, estrone, digitoxygenin, dehydroepiandrosterone, coprostanol, pregnenolone, epicholestanol, 7-dehydrocholesterol, estradiol benzoate, tigogenin, hecogenin, methandienone, cortisone acetate, stenolone, and alicyclic monools such as their isomers.

[0081] Aromatic aliphatic monools such as benzyl alcohol,

[0082] Examples 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 atom as an initiator.

[0083] When the adhesive of the present invention is provided in a solvent-free form, the viscosity of the isocyanate reactive composition (Y) is adjusted to a range suitable for the non-solvent laminating 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. These other components may be included in either or both of the polyisocyanate composition (X) and the isocyanate reactive composition (Y), or they may be prepared separately 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 catalysts include metal catalysts, amine catalysts, aliphatic cyclic amide compounds, and quaternary ammonium salts.

[0086] Examples of metal catalysts include metal complex catalysts, inorganic metal catalysts, and organometallic catalysts. Examples of metal complex catalysts include acetylacetonate salts of metals selected from the group consisting of Fe (iron), Mn (manganese), Cu (copper), Zr (zirconium), Th (thorium), Ti (titanium), Al (aluminum), and Co (cobalt), such as iron acetylacetonate, manganese acetylacetonate, copper acetylacetonate, and zirconia acetylacetonate.

[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 organometallic catalysts include organozinc compounds such as zinc octoate, zinc neodecanoate, and zinc naphthenate; organotin compounds such as stanus diacetate, stanus dioctoate, stanus dioleate, stanus dilaurate, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin oxide, and dibutyltin dichloride; organonickel compounds such as nickel octoate and nickel naphthenate; organocobalt compounds such as cobalt octoate and cobalt naphthenate; organobismuth compounds such as bismuth octoate, bismuth neodecanoate, and bismuth naphthenate; tetraisopropyloxytitanate, dibutyltitanium dichloride, tetrabutyltitanium trichloride, butoxytitanium trichloride; aliphatic diketones; aromatic diketones; and titanium compounds such as titanium chelate complexes with at least one alcohol having 2 to 10 carbon atoms as a ligand.

[0089] Amine-based catalysts include triethylenediamine, 2-methyltriethylenediamine, quinuclidine, 2-methylquinuclidine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N',N",N"-pentamethyl-(3-aminopropyl)ethylenediamine, N,N,N',N",N"-pentamethyldipropylenetriamine, N,N,N',N'-tetramethylhexamethylenediamine, bis(2-dimethylaminoethyl) ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol, N,N-dimethyl-N'-(2-hydroxyethyl)ethylenediamine, N,N-dimethyl-N'-(2-hydroxyethyl)propanediamine, bis(dimethylaminopropyl)amine, bis(dimethylaminopropyl)isopropanediamine Lopanolamine, 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 Examples include 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, and 1-(2-hydroxypropyl)-2-methylimidazole.

[0090] Examples of aliphatic cyclic amide compounds include δ-valerolactam, ε-caprolactam, ω-enanthollactam, η-capryllactam, and β-propiolactam. Among these, ε-caprolactam is most effective in promoting curing.

[0091] Examples of quaternary ammonium salts include alkylammonium, aromatic ammonium, hydroxy salts, alkylates, and halide salts. 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, and hexadecyltrimethylammonium bromide.

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

[0093] Examples of silane coupling agents 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-based coupling agents include tetraisopropoxytitanium, tetra-n-butoxytitanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, titanium lactate, and tetrastearoxititanium.

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

[0096] (Pigment) There are no particular restrictions on the pigments used, and examples include organic 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, pearlescent pigments, and even plastic pigments, as listed in the 1970 edition of the Paint Raw Materials Handbook (compiled by the Japan Paint Manufacturers Association).

[0097] Examples of extender pigments include precipitated barium sulfate, granite, precipitated calcium carbonate, calcium bicarbonate, limestone, alumina white, silica, hydrated fine silica (white carbon), ultrafine 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 Laked 4R; soluble azo pigments such as Laked C, Carmine 6B, and Bordeaux 10; various (copper) phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; various chlorinated dye lakes such as rhodamine lake and methyl violet lake; various mordant dyes such as quinoline lake and fast sky blue; various vat dyes such as anthraquinone pigments, thioindigo pigments, and perinone pigments; various quinacridone pigments such as Syncasia Red B; various dioxazine pigments such as dioxazine violet; various condensed azo pigments such as chromophthal; and aniline black.

[0099] Inorganic pigments include various chromates such as lead yellow, zinc chromate, and molybdate orange; various ferrocyanide compounds such as Prussian blue; various metal oxides such as titanium dioxide, zinc oxide, mapo yellow, iron oxide, red iron oxide, chrome green oxide, 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; metal flake pigments and mica flake pigments; metallic pigments and pearl pigments such as mica flake pigments coated with metal oxides and mica-like iron oxide pigments; graphite, carbon black, etc.

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

[0101] The pigments used can be selected appropriately depending on the purpose, but for example, inorganic oxides such as titanium dioxide and zinc oxide are preferred as white pigments because they have excellent durability, weather resistance, and design properties, and carbon black is preferred as a black pigment.

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

[0103] (acid anhydride) Examples of acid anhydrides include cyclic aliphatic acid anhydrides, aromatic acid anhydrides, and unsaturated carboxylic acid anhydrides, and one or more can be used in combination. More specifically, examples include maleic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, dodecenyl succinic anhydride, polyadipic anhydride, polyazelaic anhydride, polysebacic anhydride, poly(ethyloctadecanediic acid) anhydride, poly(phenylhexadecanedioic acid) anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylhymic anhydride, and trialkyltetrahydrophthalic acid Examples include anhydrides, methylcyclohexenedicarboxylic acid anhydride, methylcyclohexenetetracarboxylic acid anhydride, ethylene glycol bistrimellitate dianhydride, hetic 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-naphthalenesuccinic acid dianhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dianhydride, etc.

[0104] As the acid anhydride, the above-mentioned compounds modified with glycol may be used. 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 butyltetramethylene ether glycol. Furthermore, copolymer polyether glycols of two or more of these glycols and / or polyether glycols can also be used.

[0105] Alternatively, as the acid anhydride, a homopolymer or copolymer of a compound having a polymerizable unsaturated group, such as maleic anhydride, from among the compounds mentioned above may be used. Compounds that can copolymerize 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 can be used individually 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] (Phosphate derivatives) Examples of phosphate derivatives include phosphoric acid, pyrophosphate, triphosphate, 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. Phosphate, pyrophosphate, triphosphate, and butyl acid phosphate are preferred.

[0107] If a phosphate derivative is included, its content can be adjusted as appropriate, but as an example, it is 10 ppm to 5000 ppm of the solid content of the polyisocyanate composition (X). It is more preferably 50 ppm or more, and even more preferably 1000 ppm or less.

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

[0109] Examples of phthalate-based plasticizers include phthalate 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, as well as tetrahydrophthalate ester plasticizers such as di-(2-ethylhexyl)tetrahydrophthalate, di-n-octyltetrahydrophthalate, and diisodecyltetrahydrophthalate.

[0110] Examples of fatty acid-based plasticizers include adipic acid-based plasticizers such as di-n-butyl adipate, di-(2-ethylhexyl) adipate, diisodecyl adipate, diisononyl adipate, di(C6-C10 alkyl) adipate, and dibutyldiglycol adipate; azelaic acid-based plasticizers such as di-n-hexyl azelate, di-(2-ethylhexyl) azelate, and diisooctyl azelate; and di-n-butyl sebacate, di-(2 Sebacate-based plasticizers such as -ethylhexyl) sebacate and diisononyl sebacate; maleic acid-based plasticizers such as dimethyl maleate, diethyl maleate, di-n-butyl maleate, and di-(2-ethylhexyl) maleate; fumaric acid-based plasticizers such as di-n-butyl fumarate and di-(2-ethylhexyl) fumarate; monomethyl itaconate, monobutyl itaconate, dimethyl itaconate, diethyl itaconate, dibutyrate Examples of plasticizers include itaconic acid-based plasticizers such as ruitaconate 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; citrate-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 methylacetyl ricinoleate, butylacetyl ricinoleate, glyceryl monoricinoleate, and diethylene glycol monoricinoleate; and other fatty acid-based plasticizers such as diethylene glycol monolaurate, diethylene glycol diperargonate, 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, as well as pyromellitic acid plasticizers such as tetra-(2-ethylhexyl) pyromelitate and tetra-n-octyl pyromelitate.

[0112] Examples of phosphate-based plasticizers include triethyl phosphate, tributyl phosphate, tri-(2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, octyldiphenyl phosphate, cresyldiphenyl phosphate, cresylphenyl 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-ethyl butyrate), triethylene glycol di-(2-ethylhexoate), and dibutylmethylene bisthioglycolate, as well as glycerin-based plasticizers such as glycerol monoacetate, glycerol triacetate, and glycerol tributyrate.

[0114] Examples of epoxy plasticizers include epoxidized soybean oil, epoxybutyl stearate, di-2-ethylhexyl epoxyhexahydrophthalate, diisodecyl epoxyhexahydrophthalate, epoxy triglycerides, octyl epoxidized oleate, and decyl epoxidized oleate.

[0115] Examples of polyester-based plasticizers include adipic acid-based polyesters, sebaciate-based polyesters, and phthalate-based polyesters.

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

[0117] Other examples of plasticizers include partially hydrogenated terphenyl, adhesive plasticizers, and polymerizable plasticizers such as diallyl phthalate, acrylic monomers, and oligomers. These plasticizers can be used individually or in combination of two or more.

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

[0119] (Form of adhesive) The two-component curing adhesive of the present invention can be suitably used for bonding substrates with high gas barrier properties even in its solvent-free form, but it can also be used in a solvent-based form. In this specification, "solvent-based" adhesive refers to a form used in a method in which the adhesive is applied to a substrate, heated in an oven or the like to volatilize the organic solvent in the coating film, and then bonded to another substrate, a method known as dry lamination. Either one 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 isocyanate reactive composition (Y) used in the present invention.

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

[0121] In this specification, "solvent-free" adhesive refers to an adhesive used in a method of bonding with another substrate without a step of heating in an oven or the like to volatilize the solvent after coating the substrate with the adhesive, in the so-called non-solvent laminating method. The polyisocyanate composition (X) and isocyanate reactive composition (Y) substantially do not contain esters such as ethyl acetate, butyl acetate, and cellosolve acetate, ketones such as acetone, methyl ethyl ketone, isobutyl ketone, and cyclohexanone, ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, and highly soluble organic solvents such as dimethyl sulfoxide and dimethyl sulfamide, especially ethyl acetate or methyl ethyl ketone. If trace amounts of organic solvent remain in the polyisocyanate composition (X) or isocyanate reactive composition (Y) due to incomplete removal of components or organic solvents used as reaction media during the manufacturing of their raw materials, it is considered that the composition is substantially free of organic solvents. Furthermore, if the isocyanate reactive composition (Y) contains low molecular weight alcohol, the low molecular weight alcohol reacts with the polyisocyanate composition (X) to become part of the coating film, and therefore does not need to be volatilized after coating. Consequently, this form is also treated as a solvent-free 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 formulated so that the ratio [NCO] / [isocyanate-reactive functional groups] between the number of moles of isocyanate groups [NCO] contained in the polyisocyanate composition (X) and the number of moles of functional groups that are reactive with isocyanate [isocyanate-reactive functional groups] contained in the isocyanate-reactive composition (Y) is 0.5 to 5.0, more preferably 1.0 to 3.0. This makes it possible to obtain appropriate curing properties regardless of the ambient humidity during coating.

[0123] <Laminate> The laminate of the present invention can be obtained, for example, by a method having a two-component mixing step, in which the adhesive of the present invention (a mixture of polyisocyanate composition (X) and isocyanate reactive composition (Y)) is applied to a first substrate, then a second substrate is laminated onto the applied surface, and the adhesive layer is cured; or by a method having a two-component fractional coating step, in which the polyisocyanate composition (X) and isocyanate reactive composition (Y) are applied separately to the first substrate and the second substrate, and then the first substrate and the second substrate are laminated by bringing the respective applied surfaces into contact and pressing them together, and the adhesive layer is cured. There are no particular restrictions on the substrate used, and it can be appropriately selected according to the application.

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

[0125] Furthermore, it is also preferable to use biomass films, biodegradable films, or 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. In addition, films certified in each country can be used, such as film sheets listed in the biomass certified product list of the Japan Organic Resources Association, films listed in the Eco Mark certified product list of the Japan Environment Association, and films bearing the symbol mark set by the Japan Bioplastics Association.

[0126] The film may be stretched. A common stretching method involves melting and extruding the resin into a sheet using methods such as extrusion film formation, followed by simultaneous biaxial stretching or sequential biaxial stretching. In the case of sequential biaxial stretching, it is common to first perform longitudinal stretching, followed by transverse stretching. Specifically, a method combining longitudinal stretching using the speed difference between rolls and transverse stretching using a tenter is frequently used.

[0127] Various surface treatments, such as flame treatment or corona discharge treatment, may be applied to the film surface as needed to ensure that an adhesive layer free from defects such as film breakage or repulsion is formed.

[0128] Alternatively, a film containing a vapor-deposited layer of metal such as aluminum, a metal oxide such as silica or alumina, or a barrier film containing a gas barrier layer such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, or vinylidene chloride may be used in combination. By using such films, a laminate can be made that has barrier properties against water vapor, oxygen, alcohol, inert gases, volatile organic compounds (fragrances), etc.

[0129] As for the paper, any known paper substrate can be used without particular limitation. Specifically, it is manufactured using known papermaking natural fibers such as wood pulp and papermaking machines, 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 pulps that have been chemically modified. As for the type of pulp, chemical pulps produced by sulfate pulping, acidic, neutral, and alkaline sulfite pulping, soda salt pulping, etc., as well as gland pulp, chemigland pulp, thermomechanical pulp, etc. can be used. In addition, various commercially available fine papers, coated papers, backing papers, impregnated papers, cardboard, and paperboard can also be used.

[0130] More specifically, the configuration of the laminate is as follows: (1) Substrate 1 / Adhesive layer 1 / Sealant film (2) Substrate 1 / Adhesive layer 1 / Metal vapor-deposited unstretched film (3) Substrate 1 / Adhesive layer 1 / Metal vapor-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 vapor-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) Substrate 1 / Adhesive layer 1 / Metal layer / Adhesive layer 2 / Substrate 2 / Adhesive layer 3 / Sealant film Examples include, but are not limited to, those listed above.

[0131] Examples of substrate 1 used in composition (1) include MDOPE film, BOPE film, OPP film, PET film, nylon film, and paper. Alternatively, a substrate 1 coated with a coating for purposes such as improving gas barrier properties or ink receptivity when providing the printing layer described later may be used. 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. The printing layer may be provided on the side of the substrate 1 facing the adhesive layer 1 (or, if a coated substrate film 1 is used, on the side of the coating layer facing the adhesive layer 1) or on the side opposite to the adhesive layer 1. The printing layer is formed using various printing inks such as gravure ink, flexographic ink, offset ink, stencil ink, and inkjet ink, using general printing methods conventionally used for printing on polymer films and paper.

[0132] Examples of substrate 1 used in configurations (2) and (3) include MDOPE film, BOPE film, OPP film, PET film, paper, etc. The adhesive layer 1 is a cured coating of the adhesive of the present invention. Examples of unstretched metal-deposited films include CPP film, LLDPE film, VM-CPP film, VM-LLDPE film, etc., which are gas barrier heat seal films with metal deposition of aluminum or the like. Examples of stretched metal-deposited films include VM-MDOPE film, VM-BOPE film, VM-OPP film, etc., which are MDOPE film, BOPE film, or OPP film with metal deposition of aluminum or the like. A printed layer may be provided on any surface of the substrate 1 in the same manner as in configuration (1).

[0133] Examples of transparent vapor-deposited stretched films used in configuration (4) include films obtained by vapor-depositing silica or alumina onto MDOPE film, BOPE film, OPP film, PET film, nylon film, etc. Films with a coating applied to the vapor-deposited layer may also be used for purposes such as protecting the inorganic vapor-deposited layer of silica or alumina. 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 the 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 are the same as those in configuration (1). A printed layer may be provided on the side of the transparent vapor-deposited stretched film that faces the adhesive layer 1 (or, if a film with a coating applied to the inorganic vapor-deposited layer is used, on the side of the coating layer that faces the adhesive layer 1). The method for forming the printed layer is the same as in configuration (1).

[0134] Examples of substrate 1 used in configuration (5) include PET film and paper. Examples of substrate 2 include nylon film. At least one of adhesive layer 1 and adhesive layer 2 is a cured coating film of the adhesive of the present invention. Examples of sealant film are the same as those in configuration (1). A printed layer may be provided on any surface of substrate 1 in the same manner as in configuration (1).

[0135] Examples of transparent vapor-deposited stretched film used in configuration (6) are the same as those used in configuration (4). Examples of substrate 1 used in configuration (6) are PET film and nylon film. At least one of the adhesive layers 1 and 2 is a cured coating of the adhesive of the present invention. Examples of sealant film are the same as those used in configuration (1). A printed layer may be provided on the side of the transparent vapor-deposited stretched film that faces the adhesive layer 1 (or, if a film with a coating applied to an inorganic vapor-deposited layer is used, on the side of the coating layer that faces the adhesive layer 1). The method for forming the printed layer is the same as in configuration (1).

[0136] The base material 1 of configuration (7) is the same as that of configurations (2) and (3). Examples of metal vapor-deposited stretched films include VM-MDOPE film, VM-BOPE film, VM-OPP film, and VM-PET film, which are obtained by vapor deposition of aluminum or other metal onto MDOPE film, BOPE film, OPP film, or PET film. At least one of adhesive layer 1 and adhesive layer 2 is a cured coating film of the adhesive of the present invention. The sealant film is the same as that of configuration (1). A printed layer may be provided on any surface of the base material 1 in the same manner as in configuration (1).

[0137] Examples of the substrate 1 in configuration (8) include PET film and paper. Examples of the transparent vapor-deposited stretched film include those the same as in configuration (4). At least one of the adhesive layers 1 and 2 is a cured coating of the adhesive of the present invention. Examples of the sealant film include those the same as in configuration (1). A printed layer may be provided on any surface of the substrate 1 in the same manner as in configuration (1).

[0138] Examples of the base material 1 in configuration (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 are the same as those in configuration (1). A printed layer may be provided on any surface of the base material 1 in the same manner as in configuration (1).

[0139] Examples of base material 1 in configurations (10) and (11) include PET film and paper. Examples of base material 2 include nylon film. Examples of metal layers include aluminum foil. At least one layer of adhesive layers 1, 2, and 3 is a cured coating of the adhesive of the present invention. Examples of sealant films are the same as those in configuration (1). A printed layer may be provided on any surface of base material 1 in the same manner as in configuration (1).

[0140] The adhesive of the present invention can provide a laminate in which appearance defects are suppressed even when used in lamination of a gas-barrier substrate (hereinafter also referred to as a barrier substrate) having a metal vapor-deposited layer or an inorganic oxide vapor-deposited layer on a film. For this reason, it can be suitably used in the manufacture of configurations (2) to (4), (6) to (11), and especially configurations (4), (6), and (8) in which appearance defects are easily visible.

[0141] Furthermore, when a laminate manufactured using an adhesive containing a large amount of aromatic diisocyanate monomer as the polyisocyanate composition (X) is used in the manufacture of packaging materials that undergo retort or boiling treatment, there is a risk that PAA (primary aromatic amine) derived from the aromatic polyisocyanate compound may migrate from the adhesive layer to the contents. Although the amount of PAA in the adhesive layer decreases over time due to reaction with moisture, retort or boiling treatment cannot be performed until the PAA content falls below a specified value. The adhesive of the present invention exhibits its physical properties even with a small amount of aromatic diisocyanate monomer in the polyisocyanate composition (X), thus eliminating the above concerns and allowing for rapid retort or boiling treatment. Therefore, the adhesive of the present invention is also preferable for use in the manufacture of laminates for packaging materials that require boiling or retort treatment.

[0142] A more specific example of the configuration of a laminated packaging material used in boiling or retorting processes is, 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 nylon 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, 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, Nylon film / adhesive layer / CPP film Transparent vapor-deposited nylon film / adhesive layer / CPP film, Examples include gas barrier polyolefin films, adhesive layers, and CPP films.

[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 do not shrink easily during boiling or retorting). The adhesive of the present invention is used to form an adhesive layer located in the inner layer when viewed from the contents after bag formation. When the laminate has multiple adhesive layers, the other adhesive layers may or may not be cured coatings 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 coatings of the adhesive of the present invention.

[0144] Other preferred configurations 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, Nylon film / adhesive layer / LLDPE film, Examples include PET film / adhesive layer / Ny film / adhesive layer / LLDPE film, etc. Also, in the configuration exemplified above, the LLDPE film may be colored white.

[0145] When the adhesive of the present invention is a solvent type, the adhesive of the present invention is applied to the film material serving as the base material using a roll such as a gravure roll, and after volatilizing the organic solvent by heating in an oven or the like, the other base material is laminated to obtain the laminate of the present invention. It is preferable to perform an aging treatment after lamination. The aging temperature is preferably from room temperature to 80°C, and the aging time is preferably from 12 to 24 (0) hours.

[0146] When the adhesive of the present invention is a solvent-free type, the adhesive of the present invention pre-heated to about 40°C to 100°C is applied to the film material serving as the base material using a roll such as a gravure roll, and then the other base material is immediately laminated to obtain the laminate of the present invention. It is preferable to perform an aging treatment after lamination. The aging temperature is preferably from room temperature to 70°C, and the aging time is preferably from 6 to 240 hours.

[0147] The coating amount of the adhesive is adjusted as appropriate. In the case of a solvent-based adhesive, for example, the solid content is 1 g / m 2 or more and 10 g / m 2 or less, preferably 2 g / m 2 or more and 5 g / m 2 or less. In the case of a solvent-free adhesive, the coating amount of the adhesive is, for example, 2 1 g / m 2 or more and 5 g / m 2 or less, preferably 1 g / m 2 or more and 3 g / m

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

[0149] The "other layer" may contain known additives and stabilizers, such as antistatic agents, easy-adhesion coating agents, plasticizers, lubricants, and antioxidants. The "other layer" may also have its surface pretreated by corona treatment, plasma treatment, ozone treatment, chemical treatment, solvent treatment, etc., to improve adhesion when laminated with other materials.

[0150] The laminate of the present invention can be suitably used in a variety of applications, such as packaging materials for food, pharmaceuticals, and household goods; lids; paper tableware such as paper straws, paper napkins, paper spoons, paper plates, and paper cups; protective wall materials; roofing materials; solar 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 injection molding simultaneous decoration methods; and packaging materials for laundry detergents, kitchen detergents, bath detergents, 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 the purpose of protecting food, pharmaceuticals, and other products. When used as a multilayer packaging material, the layer configuration may be changed depending on the contents, usage environment, and usage form. Furthermore, the packaging of the present invention may be appropriately provided with an easy-open treatment or resealing means.

[0152] As an example of a specific embodiment of the packaging material of the present invention, a packaging material made by forming a bag from the laminate described above can be mentioned. The laminate is folded or overlapped so that the inner layers (sealant film surfaces) face each other, and the peripheral edges are heat-sealed to form a bag. Methods for forming the bag include heat sealing methods such as side seal type, two-side seal type, three-side seal type, four-side seal type, envelope seal type, gusset seal type, pleated seal type, flat-bottom seal type, square-bottom seal type, gusset type, and other heat-seal types. The packaging material of the present invention can take various forms depending on the contents, usage environment, and usage method. Self-standing packaging materials (standing pouches) are also possible. Known heat sealing methods include bar seal, rotary roll seal, belt seal, impulse seal, high-frequency seal, and ultrasonic seal.

[0153] Products using the packaging material of the present invention are manufactured by filling the packaging material with contents through its opening and then heat-sealing the opening. Examples of contents that can be filled include, for example, food products such as rice crackers, bean snacks, nuts, biscuits / cookies, wafers, marshmallows, pies, semi-baked cakes, candies, and snack foods; staple foods such as bread, instant noodles, dried noodles, pasta, aseptically packaged rice, rice porridge, packaged mochi, and cereal foods; processed agricultural products such as pickles, boiled beans, natto, miso, frozen tofu, tofu, enoki mushrooms, konjac, processed wild vegetables, jams, peanut cream, salads, frozen vegetables, and processed potato products; processed livestock products such as ham, bacon, sausages, processed chicken products, and corned beef; and fish ham. Examples of processed seafood products include sausages, processed seafood products, fish cakes, seaweed, preserved foods, dried bonito flakes, salted seafood, smoked salmon, and spicy cod roe; fruits such as peaches, oranges, pineapples, apples, pears, and cherries; vegetables such as corn, asparagus, mushrooms, onions, carrots, radishes, and potatoes; frozen and chilled prepared foods such as hamburgers, meatballs, fried seafood, dumplings, and croquettes; dairy products such as butter, margarine, cheese, cream, instant creamy powder, and infant formula; liquid seasonings; retort curry; and pet food.

[0154] Furthermore, as a non-food product, it can be used as a packaging material for various items such as cigarettes, disposable hand warmers, pharmaceuticals such as intravenous fluid packs, liquid laundry detergent, liquid dish soap, liquid bath detergent, liquid bath soap, liquid shampoo, liquid conditioner, cosmetics such as lotions and emulsions, vacuum insulation materials, and batteries.

[0155] <Recycled plastic> The laminates and packaging materials of the present invention can be used as raw materials for recycled plastics. The recycled plastics of the present invention are recycled using the laminates and packaging materials of the present invention as raw materials. The method for recycling the laminates and packaging materials is not particularly limited, and known methods can be used. Examples include crushing the laminates and packaging materials, melting and kneading them, then pelletizing and molding them, or directly feeding the crushed laminates and packaging materials into an extrusion molding machine and melting and kneading them in the heating cylinder of the molding machine to use them as molding raw materials without melting and kneading or pelletizing.

[0156] Laminates and packaging materials can be crushed using known crushers. The crusher is not particularly limited and examples include 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 material or laminate is preferably 1 mm to 40 mm in side length, and more preferably 8 mm to 20 mm.

[0157] It is preferable that the crushed laminates and packaging materials are washed before being subjected to heating and melting. Washing methods include batch or continuous washing, and water, detergent, neutralizing agent, or alkaline aqueous solution may be used. Furthermore, it is preferable that the washed laminates and packaging materials are dehydrated and dried. Centrifugal dehydration is preferred as the dehydration method, and hot air drying is preferred as the drying method.

[0158] Dehydration and drying allow for adjustment of the moisture content of the laminate subjected to heating and melting. This helps to avoid foaming during the production of recycled plastics. If air bubbles occur during pellet production, the pressure in the cylinder changes, causing the extrusion amount and pressure to be inconsistent, which may result in irregular pellet shapes and dimensions. Furthermore, when manufacturing molded products using the produced pellets through secondary molding, surface irregularities are likely to occur, potentially degrading the surface condition of the molded product.

[0159] In one embodiment, dehydration and drying are carried out until the moisture content of the laminate used for 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 laminates and packaging materials are heated and melted at 120-280°C and then kneaded. The temperature at which the laminates and packaging materials are melted can be adjusted considering the glass transition temperature and melting temperature of the laminates or packaging materials, the shape when pelletized, and the pressure applied during the molding process. The screw rotation speed during kneading is typically 50-1000 RPM.

[0161] The laminate and packaging material thus melt-kneaded are cooled and shredded to form pellets. Examples of pelletizing methods include hot-cutting and strand-cutting methods, but are not particularly limited. To prevent foreign matter from being mixed into the pellets, it is preferable to provide a screen mesh at the discharge section of the melt-kneaded laminate and packaging material. Examples of screen meshes include woven types such as plain weave, twill weave, plain tatami weave and twill tatami, and perforated metal types. The size of the screen mesh is preferably 40 mesh or more, more preferably 80 mesh or more, and even more preferably 120 mesh or more, taking into consideration the pressure at the discharge section and clogging. Examples of cooling methods include air cooling, wind cooling, and water cooling. In the present invention, it is preferable to include a water cooling step. It is preferable to cool to 20°C to 80°C, and more preferably to 30°C to 60°C.

[0162] The laminate of the present invention can be used directly in the production of recycled plastics as described above if the multiple base materials constituting the laminate are made of the same type of resin. Alternatively, it may be used in 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 separate each layer of the laminate.

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

[0164] The material may be used in the manufacture of recycled plastic after the printed layer has been removed. The printed layer can be removed by known methods. The printed layer itself may be formed using a printing ink that is easily peeled off from the substrate by immersion in a release agent, or a delamination layer may be formed by applying a coating agent containing a resin that is easily peeled off from the substrate by immersion in a release agent between the printed layer and the substrate, and the printed layer may be provided on the delamination layer.

[0165] The recycled plastic of the present invention may contain known additives. Examples of such additives include at least one antioxidant selected from the group consisting of phenolic and phosphorus-based agents; at least one lubricant selected from the group consisting of fatty acid amides, alkylene fatty acid amides, metal soaps, and esters; a hindered amine-based weather stabilizer; a wax with an acid value of 5 mg KOH / g or less; and at least one antistatic agent selected from the group consisting of fatty acid sulfons 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 and packaging material of the present invention. The virgin plastic added shall be of the same resin type as the base material used in the laminate of the present invention. The virgin plastic may be added when pelletizing the laminate and packaging material of the present invention, or when molding the pelletized recycled plastic of the present invention. It may also be added both when pelletizing and when molding the recycled plastic. As an example, the amount of virgin plastic used in combination when pelletizing the laminate and packaging material of the present invention is in the range of laminate / packaging material:virgin plastic of 100:0 to 25:75 (mass ratio). As an example, the amount of virgin plastic used when molding the pelletized recycled plastic of the present invention is in the range of recycled plastic:virgin plastic 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, containers such as pallets and containers for transport, bottles, hangers, stationery, pots and cups, disposable cutlery, and toys. It can also be recycled as a film, or the recycled film can be molded and used as cushioning material when transporting fruits, etc., but is not limited to these uses. As a method for turning the recycled plastic of the present invention into a film to make a recycled film, known methods such as T-die molding, inflation molding, solution casting molding, and calendering can be used. As a method for molding the recycled film, known methods such as vacuum forming and hot press molding can be used. [Examples]

[0168] The present invention will be described in more detail below with reference to specific synthesis examples and embodiments, but the present invention is not limited to these embodiments. In the following examples, "parts" and "%" represent "parts by mass" and "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) were added to a reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, and condenser, and heated to 40°C while stirring under a nitrogen gas stream. Then, 225.5 parts of bifunctional polyethylene glycol with a molecular weight of 200 were added carefully to avoid exothermic reactions, and 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 polyphosphate was added to terminate the reaction. Next, using a thin-film distillation apparatus, the TDI in the urethane prepolymer, which was the reaction product of TDI, was purified to 0.05% by mass of the solid content at a pressure of approximately 0.02 Torr and a temperature of 160°C to obtain 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) were 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. Then, 177.2 parts of bifunctional polyethylene glycol with a molecular weight of 150 were added carefully to avoid exothermic reactions, and 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 polyphosphate was added to terminate the reaction. Next, using a thin-film distillation apparatus, the TDI in the urethane prepolymer, which was the reaction product of TDI, was purified to 0.05% by mass of the solid content at a pressure of approximately 0.02 Torr and a temperature of 160°C to obtain polyurethane polyisocyanate (A1-2). The NCO% of polyurethane polyisocyanate (A1-2) was 16.2%.

[0171] (Synthesis Example 3) Polyurethane polyisocyanate (A1-3) In a reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, and condenser, 635.3 parts of toluene diisocyanate (TDI) were added and heated to 40°C while stirring under a nitrogen gas stream. Then, 364.7 parts of bifunctional polyethylene glycol with a molecular weight of 400 were added carefully, taking care to avoid exothermic reactions, and 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 polyphosphate was added to terminate the reaction. Next, using a thin-film distillation apparatus, the TDI in the urethane prepolymer, which was the reaction product of TDI, was purified to 0.05% by mass of the solid content at a pressure of approximately 0.02 Torr and a temperature of 160°C until the TDI content was 0.05% by mass of the solid content, thereby obtaining polyurethane polyisocyanate (A1-3). The NCO% of polyurethane polyisocyanate (A1-3) was 11.2%.

[0172] (Synthesis Example 4) Polyurethane polyisocyanate (A1-4) In a reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, and condenser, 410.6 parts of toluene diisocyanate (TDI) were added and heated to 40°C while stirring under a nitrogen gas stream. Then, 589.4 parts of bifunctional polyethylene glycol with a molecular weight of 1000 were added carefully, taking care to avoid exothermic reactions, and 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 polyphosphate was added to terminate the reaction. Next, using a thin-film distillation apparatus, the TDI in the urethane prepolymer, which was the reaction product of TDI, was purified to 0.05% by mass of the solid content at a pressure of approximately 0.02 Torr and a temperature of 160°C until the TDI content was 0.05% by mass of the solid content, thereby obtaining polyurethane polyisocyanate (A1-4). The NCO% of polyurethane polyisocyanate (A1-4) was 6.2%.

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

[0174] In a reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, and condenser, 342.8 parts of toluene diisocyanate (TDI) were added and heated to 40°C while stirring under a nitrogen gas stream. Then, 657.2 parts of the polyester polyol synthesized above were added carefully, taking care to avoid exothermic reactions, and 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 polyphosphate was added to terminate the reaction. Next, using a thin-film distillation apparatus, the TDI in the urethane prepolymer, which was the reaction product of TDI, was purified to 0.05% by mass of the solid content at a pressure of approximately 0.02 Torr and a temperature of 160°C until the TDI content was 0.05% by mass of the solid content, thereby obtaining polyurethane polyisocyanate (A1-5). The NCO% of polyurethane polyisocyanate (A1-5) was 4.8%.

[0175] (Synthesis Example 6) Polyurethane polyisocyanate (A1-6) 582.2 parts of toluene diisocyanate (TDI) were 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. Then, 278.5 parts of bifunctional polyethylene glycol with a molecular weight of 400 and 139.3 parts of bifunctional polypropylene glycol with a molecular weight of 1000 were added, taking care to avoid exothermic reactions, 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 polyphosphate was added to terminate the reaction. Next, using a thin-film distillation apparatus, the TDI in the urethane prepolymer, which was the reaction product of TDI, was purified to 0.05% by mass of the solid content at a pressure of approximately 0.02 Torr and a temperature of 160°C to obtain polyurethane polyisocyanate (A1-6). The NCO% of polyurethane polyisocyanate (A1-6) was 9.4%.

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

[0177] In a flask equipped with a stirrer, thermometer, and nitrogen gas inlet tube, 54 parts of a mixture of 2,2-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, and 4,4'-diphenylmethane diisocyanate were charged and 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 with a number average molecular weight of 1000 were added dropwise in several portions. The mixture was further heated and maintained at an internal temperature of 70°C for 4 hours to carry out the urethane reaction, yielding polyurethane polyisocyanate (A'1) with an NCO group content of 14.7%.

[0178] (Preparation of polyisocyanate composition (X)) Polyisocyanate compositions (X) for the examples and comparative examples were prepared by mixing 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 table) in the formulations shown in Tables 1 and 2. The hexamethylene diisocyanate derivatives (A2-1) to (A2-3) used were as follows.

[0179] (Hexamethylene diisocyanate derivative (A2-1)) Covestro's Desmodule N3300 (Hexamethylene diisocyanate nurate, hexamethylene diisocyanate content 0.2% by mass) (Hexamethylene diisocyanate derivative (A2-2)) Covestro's Desmodule N3200A (Hexamethylene diisocyanate billet, hexamethylene diisocyanate content 0.7% by mass) (Hexamethylene diisocyanate derivatives (A2-3)) Takenate D178NL (allophanate derivative of hexamethylene diisocyanate, hexamethylene diisocyanate content 0.5% by mass), manufactured by Mitsui Chemicals, Inc.

[0180] [Table 1]

[0181] [Table 2]

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

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

[0184] (Isocyanate-reactive composition (Y-3)) In a reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, rectification tube, and moisture separator, 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 were charged under nitrogen gas introduction. 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. The esterification reaction was terminated when the acid value fell to 1 mg KOH / g or less, yielding a polyester polyol. The hydroxyl value of the polyester polyol was 185 mg KOH / g. To this polyester polyol, 6% by mass of amine-initiated polypropylene polyol (ADEKA, EDP-450, molecular weight 450, hydroxyl value 505 mg KOH / g) was added to obtain an isocyanate-reactive composition (Y-3). The hydroxyl value of the isocyanate-reactive composition (Y-3) was 220 mg KOH / g.

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

[0186] <Preparation of adhesive> Polyisocyanate composition (X) and 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] <Manufacturing of laminates> (Laminate 1) The prepared adhesive was applied at a rate of 2.5 g / m² to a transparent vapor-deposited polyester film (TOPPAN, GL-ARH) with a thickness of 12 μm. 2 The adhesive was applied to the laminated nylon film (Unitika Corporation, Emblem ONBC RT) with a thickness of 15 μm, and then bonded to it. Subsequently, the same adhesive was applied to the nylon film surface of the laminate at a rate of 2.5 g / m². 2 The mixture was coated to form a solid content layer and laminated with a 70 μm thick unstretched polypropylene film for retort processing (Toray Film Processing Co., Ltd., Trefan NO. ZK207). Laminate 1 was obtained by aging at 40°C for 2 days.

[0188] (Laminate 2) An anchor coating agent, a mixture of a silane coupling agent, an acrylic polyol, and an isocyanate curing agent, was applied to one side of a 20 μm thick biaxially oriented polypropylene film to form a 0.3 μm thick anchor coating layer. Then, a 15 nm thick aluminum oxide layer was formed by electron beam heating to obtain a biaxially oriented polypropylene film having a transparent vapor-deposited layer.

[0189] The prepared adhesive was applied at a rate of 2.5 g / m² to a 20 μm thick biaxially oriented polypropylene film (Toyobo Co., Ltd., Pyrene EXTOP XP610). 2 The adhesive was applied to the laminated transparent vapor-deposited biaxially oriented polypropylene film, and then bonded to the transparent vapor-deposited layer of the transparent vapor-deposited biaxially oriented polypropylene film described above. Subsequently, the same adhesive was applied to the transparent vapor-deposited biaxially oriented polypropylene film of the laminate at a rate of 2.5 g / m². 2 The mixture was coated to form a solid content layer and laminated with a 70 μm thick unstretched polypropylene film for retort processing (Toray Film Processing Co., Ltd., Trefan NO. ZK207). The laminate was aged at 40°C for 2 days to obtain laminate 2.

[0190] (Laminate 3) The prepared adhesive was applied to a 15 μm thick nylon film (Unitika Corporation, Emblem ONBC RT) at a rate of 2.5 g / m². 2The film was coated to form a solid (solid) layer, and the adhesive-coated surface of this film was laminated with an unstretched polypropylene film for retort processing (manufactured by Toray Film Processing Co., Ltd., Trefan NO ZK207). The laminate was then aged at 40°C for two days to obtain laminate 3.

[0191] <Rating> (Retort-resistant) Test pieces were cut from laminates 1 and 2, folded so that the unstretched polypropylene film for retort processing faced inward, and heat-sealed on three sides other than the fold with a width of 10 mm. A 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 retorted pouches was checked. The results were evaluated according to the following criteria and summarized in Tables 3 to 5. 5: No delamination 1: With delamination

[0192] (Adhesive strength after retort processing (Laminate 1)) The contents were removed from the retort-treated pouch, and 15 mm wide test pieces were cut from the pouch. The adhesive strength (N / 15 mm) between the nylon film and the unstretched polypropylene film for retort processing was measured using a tensile testing machine at a peeling speed of 300 mm / min and T-type peeling. The results were evaluated according to the following criteria and summarized in Tables 3-5. 5:7N / 15mm or more 4: 5N / 15mm or more, 7N / 15mm or less 3: 4N / 15mm or more, 5N / less than 15mm 2: 3N / 15mm or more, 4N / less than 15mm 1:3N / less than 15mm

[0193] (Adhesive strength after retort processing (Laminate 2)) The contents were removed from the retort-treated pouch, and 15 mm wide test pieces were cut from the pouch. Using a tensile testing machine, the adhesive strength (N / 15 mm) between the transparent vapor-deposited biaxially oriented polypropylene film and the unoriented polypropylene film for retort processing was measured at a peeling speed of 300 mm / min and using a T-type peeling method. The results were evaluated according to the following criteria and summarized in Tables 3-5. 5:2.5N / 15mm or more 4:2N / 15mm or more, 2.5N / less than 15mm 3: 1.5N / 15mm or more, 2N / 15mm or less 2:1N / 15mm or more, 1.5N / 15mm or less 1:1N / less than 15mm

[0194] (PAA elution amount) Cut each of the laminates 1, 2, and 3 to 120mm x 220mm, fold them so that the unstretched polypropylene film for retort is on the inside, and heat seal the three sides with a width of 10mm at 1atm, 180℃, and 1 second, until the contents are 2dm 2 Contact pouches were prepared. These pouches, filled with a 3% acetic acid solution, were retorted at 121°C for 30 minutes, and PAA was measured by LC / MS / MS. The results were evaluated according to the following criteria and summarized in Tables 3-5. 5: PAA elution amount is less than 2 ppb 3: PAA elution level between 2 ppb and 10 ppb 1: PAA elution amount is 10 ppb or more

[0195] (Processed appearance) At a processing speed of 100 m / min, a transparent vapor-deposited polyester film (TOPPAN, GL-ARH) with a thickness of 12 μm was coated with a prepared adhesive at a rate of 2.0 g / m². 2 The adhesive was applied to the laminated nylon film (Unitika Corporation, Emblem ONBC RT) with a thickness of 15 μm, and then bonded to it. Subsequently, the same adhesive was applied to the nylon film surface of the laminate at a processing speed of 100 m / min, with a quantity of 2.0 g / m². 2The material was coated to form a solid, and then laminated with a 70 μm thick unstretched polypropylene film for retort processing (Toray Film Processing Co., Ltd., Torayfan NO. ZK207). After aging at 40°C for 2 days, laminate 4 was obtained. Laminates were obtained in the same manner as laminate 4, except that the processing speed was 150 m / min, 180 m / min, and 200 m / min. The presence or absence of air bubbles remaining in the laminate after aging was checked, and the processing speed range in which no air bubbles remained was investigated. The evaluation was carried out according to the following criteria, and the results are summarized in Tables 3 to 5. No air bubbles remain even at processing speeds of 5:200 m / min or higher. No bubbles remaining at 4:180 m / min No bubbles remaining at 3:150 m / min No bubbles remaining at 2:100m / min Air bubbles remain at 1:100m / min

[0196] [Table 3]

[0197] [Table 4]

[0198] [Table 5]

Claims

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

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 with a molecular weight of 50 g / mol or less and 500 g / mol or less.

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

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

6. The 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) comprises a polyester polyol (B1).

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

9. A two-component curing adhesive according to claim 1, comprising at least one selected from a urethane catalyst, a phosphoric acid derivative, a plasticizer, and an acid anhydride.

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

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 a two-component curable 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, wherein the second adhesive layer is a cured coating film of a two-component curing adhesive according to any one of claims 1 to 10.

14. A packaging material comprising the laminate described in claim 11.