Polyisocyanate composition, two-component curable composition, two-component curable coating agent, two-component curable adhesive, laminate, and packaging material

Abstract

Provided are: a two-component curable adhesive having an excellent balance between reactivity and storage stability; and a polyisocyanate composition suitable for such an adhesive. A polyisocyanate composition (X), which contains a polyurethane polyisocyanate (A1) that is a reaction product of a hexamethylene diisocyanate and a polyol having a hydroxyl group of 5-10 (inclusive), and also contains a phosphoric acid derivative (B), and a two-component curable adhesive containing such a polyisocyanate composition (X), which is characterized in that: the polyurethane polyisocyanate (A1) is a reaction product of a hexamethylene diisocyanate and a polyol having a hydroxyl group of 5-10 (inclusive); the content of the phosphoric acid derivative (B) is from 10 ppm to 5000 ppm (inclusive).

Description

TECHNICAL FIELD

[0001] The present application relates to a polyisocyanate composition, a two-component curable composition, a two-component curable coating agent, a two-component curable adhesive, a laminate, a packaging material. BACKGROUND

[0002] A laminate used in various packaging materials, labels, and the like is given designability, functionality, storability, convenience, transport resistance, and the like by lamination of various and diverse plastic films, metal foils, paper, and the like substrates. A packaging material formed by molding the laminate into a bag shape is used as a packaging material for various fields typified by food, pharmaceuticals, detergents, and the like.

[0003] In the past, in laminated films, the mainstream has been laminated films obtained by a dry lamination method in which a two-component curable adhesive in which a polyisocyanate compound, a polyol compound are dissolved in a volatile organic solvent is coated on a film, the organic solvent is volatilized in the course of passing through an oven, and the other film is attached. In recent years, from the viewpoint of reducing environmental load and improving the working environment, a two-component curable solventless adhesive of a polyisocyanate compound and a polyol compound that does not contain a volatile organic solvent has been attracting attention (Patent Document 1, Patent Document 2).

[0004] PRIOR ART DOCUMENTS

[0005] PATENT DOCUMENTS

[0006] Patent Document 1: Japanese Patent Application Publication No. 2014-159548

[0007] Patent Document 2: Japanese Patent Application Publication No. 2001-172602 SUMMARY

[0008] PROBLEMS TO BE SOLVED BY THE INVENTION

[0009] In order to improve productivity, it is required to improve the reactivity of such a two-component curable adhesive. On the other hand, a polyisocyanate compound, which is one component of a two-component curable adhesive, reacts with moisture in the air, and therefore if the reactivity is too high, the storage stability can decrease. In addition, if the reaction proceeds sharply immediately after the two components are mixed, there is a tendency that the adhesion of the adherend to the adhesive decreases.

[0010] The present application was completed in view of such circumstances, and aims to provide a two-component curable adhesive in which the balance between reactivity and storage stability is excellent, and a polyisocyanate composition suitable for such an adhesive.

[0011] MEANS FOR SOLVING THE PROBLEMS

[0012] That is, the present application relates to a polyisocyanate composition (X) comprising a polyurethane polyisocyanate (Al) which is a reaction product of hexamethylene diisocyanate and a polyol having 5 or more and 10 or less hydroxyl groups, and a phosphoric acid derivative (B), the content of the phosphoric acid derivative (B) being 10 ppm or more and 5000 ppm or less, and a two-component curable adhesive comprising such polyisocyanate composition (X).

[0013] Effects of the Invention

[0014] According to the present application, it is possible to provide a two-component curable adhesive in which the balance between reactivity and storage stability is excellent, and a polyisocyanate composition suitable for such adhesive. DETAILED DESCRIPTION

[0015] < Polyisocyanate composition (X) >

[0016] (Polyurethane polyisocyanate (Al))

[0017] The polyisocyanate composition (X) of the present application comprises a polyurethane polyisocyanate (Al) which is a reaction product of hexamethylene diisocyanate and a polyol having 5 or more and 10 or less hydroxyl groups, more preferably 5 or more and 8 or less.

[0018] As the polyol having 5 or more and 10 or less hydroxyl groups used in the synthesis of the polyurethane polyisocyanate (Al), there can be mentioned xylitol, triglycerol, sorbitol, dipentaerythritol, mannitol, sucrose, polyglycerol and the like low-molecular-weight polyols having 5 or more and 10 or less hydroxyl groups, and / or polyether polyols and the like obtained by addition polymerization of an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, cyclohexene oxide and the like onto these low-molecular-weight polyols as an initiator, one kind or two or more kinds in combination can be used.

[0019] From the viewpoint of being able to form a soft coating film, for example, when the polyisocyanate composition (X) of the present application is made into a two-component curable adhesive described later, it is preferable to use a polyether polyol obtained by addition polymerization of an alkylene oxide onto a low-molecular-weight polyol having 5 or more and 10 or less hydroxyl groups, and / or a polyglycerol having 5 or more and 10 or less hydroxyl groups, it is preferable to use at least one selected from a polyether polyol obtained by addition polymerization of at least one selected from ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran onto sorbitol, and a polyglycerol having 5 or more and 10 or less hydroxyl groups, and it is preferable to use at least one selected from a polyether polyol obtained by addition polymerization of at least one selected from ethylene oxide, propylene oxide onto sorbitol, and a polyglycerol having 5 or more and 10 or less hydroxyl groups.

[0020] The polyol is preferably a polyol having a molecular weight of 200 g / mol or more and 3000 g / mol or less, preferably a polyol having a molecular weight of 400 g / mol or more and 3000 g / mol or less, and more preferably a polyol having a molecular weight of 440 g / mol or more and 2000 g / mol or less.

[0021] The polyurethane polyisocyanate (A1) is obtained by reacting hexamethylene diisocyanate with a polyol under conditions in which the isocyanate groups of the hexamethylene diisocyanate are in excess relative to the hydroxyl groups of the polyol. The equivalent ratio of isocyanate groups to hydroxyl groups [NCO] / [hydroxyl] can be appropriately adjusted, and is, for example, 2.0 or more and 20.0 or less.

[0022] The polyisocyanate composition (X) used in the present application is also preferably reduced in the content of diisocyanate monomers, i.e., diisocyanate monomers exemplified as raw materials of the isocyanate derivative (A3) described later, such as aromatic diisocyanates, aromatic aliphatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, to 1.0% by mass or less, and more preferably to 0.1% by mass or less.

[0023] From the viewpoint of labor safety and hygiene, there is a trend of restricting the use of isocyanate monomers, and the European Commission has adopted the REACH regulation that prohibits the marketing of products containing 0.1% by mass or more of isocyanate monomers without satisfying certain requirements. If the unreacted diisocyanate monomers are removed until the amount of diisocyanate monomers in the polyisocyanate composition becomes 0.1% by mass or less, an article that complies with such a regulation can be produced.

[0024] In addition, in the case where a laminated body for food packaging is produced using a two-component curable adhesive containing a material that uses an aromatic diisocyanate as a raw material of the isocyanate derivative (A3) described later and that has a substantial amount of the aromatic diisocyanate remaining, unreacted aromatic isocyanate monomers can remain in the adhesive layer. The isocyanate monomers react with water present in the surroundings to become an aromatic primary amine (PAA), and there is a concern that it will move in the film and be eluted into the contents (food). There is a concern about the harmfulness of PAA to the human body, and the European Commission has set various regulations, such as a detection limit, in the rules relating to plastic materials and articles for food contact.

[0025] The PAA concentration gradually decreases even in the case where aromatic isocyanate remains in the adhesive layer because the PAA reacts with the unreacted aromatic isocyanate present in the surroundings. The concentration is lower than the detection limit, but from the viewpoint of the manufacturing efficiency of the laminate for food packaging, it is preferable that the initial value of the aromatic isocyanate monomer remaining in the adhesive layer be low. By removing the diisocyanate monomer in advance, a two-component curable adhesive having excellent manufacturing efficiency can be produced.

[0026] The removal of the diisocyanate monomer can be performed by a method of distilling the diisocyanate monomer under reduced pressure using a short path distillation device, a thin film distillation device, or the like. The degree of reduction in pressure and the distillation temperature are appropriately adjusted depending on the diisocyanate monomer to be removed, and are, for example, 0.1 mbar or less and 120°C to 190°C. The removal process of the diisocyanate monomer can be performed multiple times.

[0027] The content of the diisocyanate monomer can be determined, for example, by gas chromatography using an internal standard according to ASTM D 3432. Alternatively, it can be determined by liquid chromatography under the following conditions.

[0028] Apparatus: "ACQUITY UPLC H-Class" by Waters Corporation

[0029] Data processing: "Empower-3" by Waters Corporation

[0030] Column: "ACQUITY UPLC HSS T3" (100 mm x 2.1 mmφ, 1.8 μm) by Waters Corporation, 40°C

[0031] Eluent: ammonium formate aqueous solution / methanol, 0.3 mL / minute

[0032] Detector: PDA

[0033] Sample adjustment: 1. Dissolve 100 mg of the sample appropriately blocked in THF (for LC) 10 mL

[0034] 2. Stir for 30 seconds with vortex

[0035] 3. Dilute appropriately with the eluent (mobile phase)

[0036] 4. Pass through a 0.2 μm filter to prepare a measurement sample.

[0037] Calculation of area ratio: Calculate using the maximum absorption wavelength for the target.

[0038] (Polyurethane polyisocyanate (A2))

[0039] The polyisocyanate composition (X) also preferably contains a polyurethane polyisocyanate (A2) which is a reaction product of hexamethylene diisocyanate and a 2-functional polyol. Thereby, a polyisocyanate composition (X) which is more excellent in the balance of reactivity, storage stability, and coatability can be produced. Also, when used as a two-component curable composition described later, a coating film having moderate flexibility can be formed, and the adhesion to a substrate when applied to a substrate having flexibility can be improved.

[0040] As the 2-functional polyol used in the synthesis of the polyurethane polyisocyanate (A2), 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, bis-hydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and the like aliphatic diols, and / or polyether diols obtained by addition polymerization of an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, cyclohexene oxide, and the like using these aliphatic diols as initiators can be used, alone or in combination of two or more.

[0041] As an example, the molecular weight of the 2-functional polyol is 8000 g / mol or less. More preferably, it is 100 g / mol or more and 4000 g / mol or less.

[0042] When the polyisocyanate composition (X) contains the polyurethane polyisocyanate (A2), the blending amount thereof can be appropriately adjusted, and as an example, the content of the polyurethane polyisocyanate (A1) in the total amount of the polyurethane polyisocyanate (A1) and the polyurethane polyisocyanate (A2) is preferably 40% by mass or more.

[0043] When the polyisocyanate composition (X) contains the polyurethane polyisocyanate (A2), the polyurethane polyisocyanate (A1) and the polyurethane polyisocyanate (A2) can be mixed by separately synthesizing the substances, or a mixture of the polyurethane polyisocyanate (A1) and the polyurethane polyisocyanate (A2) can be obtained by reacting hexamethylene diisocyanate with a polyol having 5 or more and 10 or less hydroxyl groups and a 2-functional polyol under conditions in which the isocyanate groups of hexamethylene diisocyanate are in excess with respect to the hydroxyl groups of the polyol, and removing the unreacted diisocyanate monomer as necessary. The equivalent ratio of the isocyanate groups to the hydroxyl groups [NCO] / [hydroxyl] can be appropriately adjusted, and as an example, it is 2.0 or more and 20.0 or less.

[0044] In the case of additionally synthesizing the polyurethane polyisocyanate (A2), hexamethylene diisocyanate is reacted with a 2-functional polyol under conditions where the isocyanate groups of the hexamethylene diisocyanate are in excess relative to the hydroxyl groups of the 2-functional polyol, and then unreacted diisocyanate monomers are removed as necessary to obtain. The equivalent ratio of isocyanate groups to hydroxyl groups [NCO] / [hydroxyl] can be adjusted as appropriate, and is 2.0 or greater and 20.0 or less as an example.

[0045] (Isocyanate derivative (A3))

[0046] To improve the storage stability, coatability of the polyisocyanate composition (X), and the softness of the coating film when used as a two-component curable composition as described later, the polyisocyanate composition (X) can include an isocyanate derivative (A3) other than the polyurethane polyisocyanate (A1) and the polyurethane polyisocyanate (A2). As the isocyanate derivative (A3), the conventionally known aromatic diisocyanate, aromatic aliphatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, and the biuret, urethane, adduct, allophanate, carbodiimide-modified product, uretdione-modified product, polyurethane polyisocyanate other than (A1) and (A2) can be cited, and one or two or more kinds in combination can be used.

[0047] As the aromatic diisocyanate, for example, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (alias: MDI), polymethylene polyphenyl polyisocyanate (also referred to as polymeric MDI or crude MDI), 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate (alias: PPDI), 2,4-toluene diisocyanate, 2,6-toluene diisocyanate (alias: TDI), 4,4'-toluidine diisocyanate, 2,4,6-triisocyanatotoluene, 1,3,5-triisocyanatobenzene, o-tolidene diisocyanate (alias: TODI), dianisidine diisocyanate, naphthalene diisocyanate (alias: NDI), 4,4'-diphenyl ether diisocyanate, 4,4',4"-triphenylmethane triisocyanate, and the like can be cited, but are not limited to these.

[0048] The aromatic aliphatic diisocyanate refers to an aliphatic isocyanate having one or more aromatic rings in the molecule, and m-xylylene diisocyanate or p-xylylene diisocyanate (alias: XDI), α,α,α',α'-tetramethylxylylene diisocyanate (alias: TMXDI), and the like can be cited, but are not limited to these.

[0049] As the aliphatic diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (alias: HDI), pentamethylene diisocyanate (alias: PDI), 1,2- propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate (alias: LDI), and the like can be given, but are not limited to these.

[0050] As the alicyclic diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, isophorone diisocyanate (alias: 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'-methylene bis cyclohexyl isocyanate (alias: hydrogenated MDI or HMDI), 1,3-bis(isocyanatomethyl)cyclohexane (alias: hydrogenated XDI or HXDI), hydrogenated TMXDI, norbornane diisocyanate (alias: NBDI), and the like can be given, but are not limited to these.

[0051] As the polyol used in the synthesis of the polyurethane polyisocyanate other than (A1), (A2), 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, dimethyl butanediol, butyl ethyl propanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bis-hydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and the like diols;

[0052] Glycerin, 3-functional or 4-functional aliphatic alcohol such as trimethylolpropane, pentaerythritol, and the like;

[0053] Bisphenol such as bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, and the like;

[0054] Dimer diol;

[0055] Polyether polyol obtained by addition polymerization of an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, cyclohexene oxide, and the like in the presence of a polymerization initiator such as the above diol, 3-functional or 4-functional aliphatic alcohol, and the like;

[0056] 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 diol, glycerin, trimethylolpropane, pentaerythritol, etc. mentioned above;

[0057] Polyester polyol (2) which is a reaction product of a 2-functional polyol such as the above diol, dimer diol or the above bisphenol and a polycarboxylic acid;

[0058] Polyester polyol (3) which is a reaction product of a 3- or 4-functional aliphatic alcohol and a polycarboxylic acid;

[0059] Polyester polyol (4) which is a reaction product of a 2-functional polyol and a 3- or 4-functional aliphatic alcohol and a polycarboxylic acid;

[0060] Polyester polyol (5) which is a polymer of a hydroxy acid such as dimethylolpropionic acid, castor oil fatty acid, etc.;

[0061] Polyether urethane polyol obtained by high-molecular-weightizing the above polyether polyol with an isocyanate compound;

[0062] Polyester polyether urethane polyol obtained by reacting at least one of polyester polyols (1) to (5) and a polyether polyol with an isocyanate compound;

[0063] Polyester urethane polyol obtained by high-molecular-weightizing polyester polyols (1) to (5) with an isocyanate compound;

[0064] Castor oil, dehydrated castor oil, hydrogenated castor oil which is a hydrogenated product of castor oil, alkylene oxide 5 to 50 mole adduct of castor oil, etc., and the like, and mixtures thereof, etc. can be used, either singly or in combination of two or more.

[0065] As the polycarboxylic acid used in the synthesis of polyester polyols (2) to (4), there can be mentioned: phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, 1,4-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic anhydride, naphthalene dicarboxylic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, diphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid, benzophenone tetracarboxylic acid, benzophenone tetracarboxylic dianhydride, m-phthalic acid-5-sodium sulfonate, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, etc. aromatic polycarboxylic acid;

[0066] Methyl ester compound of an aromatic polycarboxylic acid such as dimethyl terephthalate, dimethyl 2,6-naphthalene dicarboxylate, etc.;

[0067] 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, itaconic acid, and the like;

[0068] alkyl esters of aliphatic polybasic acids such as dimethyl malonate, diethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, diethyl pimelate, diethyl sebacate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, and the like;

[0069] cycloaliphatic polybasic acids such as 1,1-cyclopentane dicarboxylic acid, 1,2-cyclopentane dicarboxylic acid, 1,3-cyclopentane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, tetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, cyclohexane-1,2,4-tricarboxylic-1,2-anhydride, nadic anhydride, chlorendic anhydride, and the like, and the like, and one or two or more kinds thereof can be used in combination.

[0070] In the case where the polyisocyanate composition (X) contains the isocyanate derivative (A3), the content of the polyurethane polyisocyanate (Al) in the total amount of the polyurethane polyisocyanate (Al) and the isocyanate derivative (A3) is preferably 40% by mass or more.

[0071] (Phosphoric acid derivative (B))

[0072] As the phosphoric acid derivative (B), phosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, acid phosphoric acid methyl ester, acid phosphoric acid ethyl ester, acid phosphoric acid butyl ester, acid phosphoric acid dibutyl ester, acid phosphoric acid 2-ethylhexyl ester, bis(2-ethylhexyl)phosphate, acid phosphoric acid isododecyl ester, acid phosphoric acid butoxyethyl ester, acid phosphoric acid oleyl ester, acid phosphoric acid tetracosyl ester, 2-hydroxyethyl methacrylate acid phosphoric acid ester, polyoxyethylene alkyl ether phosphoric acid ester, and the like can be given. Phosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, acid phosphoric acid butyl ester are preferable.

[0073] The content of the phosphoric acid derivative (B) in the polyisocyanate composition (X) of the present application is 10 ppm or more and 5000 ppm or less. Thereby, a polyisocyanate composition (X) having reactivity and storage stability can be produced. The content of the phosphoric acid derivative (B) in the polyisocyanate composition (X) is more preferably 50 ppm or more, and more preferably 1000 ppm or less.

[0074] The phosphoric acid derivative (B) is preferably added after the urethane reaction of the polyurethane polyisocyanate (Al) is completed. In the case of production through a process for removing unreacted isocyanate monomers, the phosphoric acid derivative (B) can be added after the urethane reaction of the polyurethane polyisocyanate (Al) is completed and before the removal of unreacted isocyanate monomers, or can be added after the removal of the isocyanate monomers.

[0075] <two-component curable composition>

[0076] The polyisocyanate composition (X) of the present application can be used in the form of a two-component curable composition in combination with an isocyanate-reactive composition containing a compound having reactivity with isocyanate. As the compound having reactivity with isocyanate, polyether polyol, polyester polyol, polyester polyether polyol, polyurethane polyol, polyester polyurethane polyol, polyether polyurethane polyol, vegetable oil polyol, sugar alcohol, polycarbonate polyol, acrylic polyol, hydroxyl group-containing olefin resin, hydroxyl group-containing fluororesin, (poly)alkanolamine, and the like can be given.

[0077] Such a two-component curable composition can be used, for example, in adhesives, coating agents, sealants, elastomers, and the like.

[0078] <two-component curable coating agent>

[0079] The two-component curable coating agent of the present application contains the above-described polyisocyanate composition (X) and an isocyanate-reactive composition (Y). The coating agent of the present application can be suitably used for various uses, and can be particularly suitably used as a coating agent for a metal substrate such as aluminum, steel sheet, and the like, an outer coating for a coating film containing aluminum pigment, metal particles, an electrical component covering, and an electrical insulation.

[0080] The isocyanate-reactive composition (Y) contains a compound (C) having a plurality of functional groups having reactivity with isocyanate (hereinafter also referred to as isocyanate-reactive compound (C)), such as polyester polyol (C1), polyether polyol (C2), vegetable oil polyol (C3), polyurethane polyol (C4), sugar alcohol (C5), acrylic polyol (C6), amine compound (C7), and epoxy compound (C8). One or two or more kinds in combination can be used as the isocyanate-reactive compound (C).

[0081] As the polyester polyol (C1), a polyester polyol which is a reaction product of a polyol and a polycarboxylic acid, a lactone-based polyester polyol which is obtained by polycondensation reaction of an aliphatic polyol and various lactones such as ε-caprolactone, and the like can be given. It is preferable to use a polyester polyol which is a reaction product of a polyol and a polycarboxylic acid.

[0082] As the polyhydric alcohol, aliphatic diols such as ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,2,2-trimethyl-l,3-propanediol, 2,2-dimethyl-3-isopropyl-l,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-l,3-butanediol, 1,5-pentanediol, 3-methyl-l,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-bis(hydroxymethyl)cyclohexane, 2,2,4-trimethyl-l,3-pentanediol, and the like;

[0083] Aliphatic polyhydric alcohols having 3 or more functions such as trimethylol ethane, trimethylol propane, glycerol, hexanetriol, pentaerythritol, and the like;

[0084] Bisphenols such as bisphenol A, bisphenol F, and the like;

[0085] Alkylene oxide adducts of bisphenols such as bisphenol A, bisphenol F, and the like, obtained by adding ethylene oxide, propylene oxide, and the like to the bisphenols;

[0086] Polyether polyols such as those obtained by ring-opening polymerization of aliphatic diols or polyhydric alcohols with ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, and the like various compounds containing a cyclic ether bond, and the like, can be used singly or in combination of two or more.

[0087] As the polybasic carboxylic acid, aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, maleic anhydride, fumaric acid, 1,3-cyclopentane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, and the like;

[0088] Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, naphthalene dicarboxylic acid, diphenic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid, and the like; and

[0089] Anhydrides or ester-forming derivatives of these aliphatic or dicarboxylic acids;

[0090] Polybasic acids such as p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid, ester-forming derivatives of these dihydroxy carboxylic acids, dimer acid, and the like, can be used singly or in combination of two or more.

[0091] The molecular weight of the polyester polyol (C1) is preferably 250 g / mol or more and 20,000 g / mol or less, more preferably 500 g / mol or more and 10,000 g / mol or less.

[0092] The hydroxyl value of the polyester polyol (C1) is preferably 5 mgKOH / g or more and 500 mgKOH / g or less.

[0093] As the polyether polyol (C2), a substance obtained by addition polymerization of an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, or cyclohexene oxide in the presence of a polymerization initiator can be given.

[0094] As the polymerization initiator, a diol 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, bis-hydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, triethylene glycol, or the like can be given.

[0095] A 3-functional or 4-functional aliphatic alcohol such as glycerin, trimethylolpropane, pentaerythritol, triol of polypropylene glycol, or the like;

[0096] A primary or secondary alkylamine such as ethylamine or diethylamine, an amine compound having multiple amino groups such as methylenediamine or ethylenediamine, a primary or secondary alkanolamine such as monoethanolamine or diethanolamine, an amine compound having a reactive hydrogen group, or the like.

[0097] The molecular weight of the polyether polyol (C2) can be appropriately adjusted, and as an example, is preferably 100 g / mol or more and 8000 g / mol or less.

[0098] The hydroxyl value of the polyether polyol (C2) can be appropriately adjusted, and as an example, is preferably 10 mgKOH / g or more and 1200 mgKOH / g or less.

[0099] As the vegetable oil polyol (C3), castor oil, dehydrated castor oil, hydrogenated castor oil which is a hydrogenated product of castor oil, an alkylene oxide 5 to 50 mole addition product of castor oil, or the like can be given.

[0100] The polyurethane polyol (C4) is a reaction product of a low-molecular-weight or high-molecular-weight polyol and a polyisocyanate compound. As the low-molecular-weight or high-molecular-weight polyol, the same substances as exemplified as the raw material of the polyester polyol (C1) can be used. As the polyisocyanate compound, the same compounds as exemplified as the raw material of the isocyanate derivative (A3) can be used.

[0101] As the sugar alcohol (C5), pentaerythritol, sucrose, xylitol, sorbitol, isomalt, lactitol, maltitol, mannitol, or the like can be given.

[0102] As the acrylic polyol (C6), a (meth)acrylate having a hydroxyl group is essential, and copolymerization with a polymerizable unsaturated monomer as needed is performed. Note that, in the present specification, (meth)acrylic acid refers to either methacrylic acid or acrylic acid.

[0103] As the (meth)acrylate having a hydroxyl group, a (meth)acrylate such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and the like can be given, and one or two or more kinds thereof can be used in combination.

[0104] As the polymerizable unsaturated monomer, (meth)acrylic acid alkyl esters having an alkyl group having a carbon number of 1 to 22 such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, and the like can be given;

[0105] (meth)acrylic acid benzyl ester, 2-phenylethyl (meth)acrylate, and the like (meth)acrylic acid aralkyl esters;

[0106] (meth)acrylic acid cyclohexyl ester, isobornyl (meth)acrylate, and the like (meth)acrylic acid cycloalkyl esters;

[0107] (meth)acrylic acid 2-methoxyethyl ester, 4-methoxybutyl (meth)acrylate, and the like (meth)acrylic acid ω-alkoxyalkyl esters;

[0108] polyfunctional (meth)acrylic acid esters such as ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like;

[0109] (meth)acrylic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, 4-methylcyclohex-4-ene-1,2-dicarboxylic anhydride, bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride, 1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic anhydride, 2-octyl-1,3-diketospiro[4.4]non-7-ene, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, maleopimaric acid, tetrahydrophthalic anhydride, methyl-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, methyl-norborn-5-ene-2,3-dicarboxylic anhydride, norborn-5-ene-2,3-dicarboxylic anhydride, sulfonated styrene, vinylbenzene sulfonamide, and the like polymerizable unsaturated monomers having an acid group;

[0110] vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and the like vinyl carboxylates;

[0111] alkyl esters of crotonic acid such as methyl crotonate and ethyl crotonate;

[0112] dialkyl esters of unsaturated dibasic acids such as dimethyl maleate, di-n-butyl maleate, dimethyl fumarate, and dimethyl itaconate, and the like, but are not limited thereto. They can be used singly as one kind or in combination of two or more kinds.

[0113] The amine compound (C7) is a compound having an amino group. Note that, in the present specification, the amino group refers to an NH2group or an NHR group (R is an alkyl group or an aryl group which can have a functional group).

[0114] As the amine compound (C7), a publicly known amine compound can be used without particular limitation, and examples thereof can include methylenediamine, ethylenediamine, isophorone diamine, 3,9-dipropylamine-2,4,8,10-tetraoxaspirodecan, lysine, 2,2,4-trimethylhexamethylenediamine, hydrazine, piperazine, 2-hydroxyethyl ethylenediamine, di-2-hydroxyethyl ethylenediamine, di-2-hydroxyethyl propylenediamine, 2-hydroxypropyl ethylenediamine, di-2-hydroxypropyl ethylenediamine, polypropyleneglycol diamine, polypropyleneglycol triamine, polypropyleneglycol tetraamine, 1,2-diaminopropane, 1,3-diaminopropane,

[0115] 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, nonaethylenedecamine, trimethylhexamethylenediamine, tetra(amino methyl)methane, tetra(2-aminoethylaminomethyl)methane, 1,3-bis(2'-aminoethylamino)propane, triethylen-bis(trimethyl)hexamine, bis(3-aminoethyl)amine, bis-hexamethylenetriamine, 1,4-cyclohexanediamine, 4,4'-methylenebiscyclohexylamine, 4,4'-isopropylidenebiscyclohexylamine, norbornanediamine,

[0116] bis(aminomethyl)cyclohexane, diaminodicyclohexylmethane, isophorone diamine, menthane diamine, bis(cyanoethyl)diethylenetriamine, 1,4-bis-(8-aminopropyl)-piperazine, piperazine-1,4-diazepane, 1-(2'-aminoethylpiperazine), 1-[2'-(2"-aminoethylamino)ethyl]piperazine, tricyclodecane diamine, amine compounds (C7-1) having multiple amino groups which belong to reaction products of the aforementioned various polyamines and the aforementioned various isocyanate components, and the like.

[0117] monoethanolamine, monoiso-propanolamine, monobutanolamine, N-methylethanolamine, N-ethylethanolamine, N-methylpropanolamine, diethanolamine, diisopropanolamine, and the like primary or secondary alkanolamines (C7-2),

[0118] ethylamine, octylamine, laurylamine, myristylamine, stearylamine, oleylamine, diethylamine, dibutylamine, distearylamine, and the like primary or secondary amines (C7-3), and the like.

[0119] The compounding amount of the amine compound (C7) can be appropriately adjusted according to the purpose, and as an example, it is preferable to be compounded in a manner such that the amine value of the isocyanate-reactive composition (Y) becomes 20 to 70 mgKOH / g, and more preferably 25 to 50 mgKOH / g.

[0120] Note that the amine value in the present specification refers to the amount of HCl required to neutralize 1 g of a sample as the number of milligrams of KOH, and is not particularly limited, and can be calculated using a publicly known method. In the case where the chemical structure of the amine compound (E7) is known, and further the average molecular weight is known as necessary, it can be calculated from (the number of amino groups per 1 molecule / average molecular weight) × 56.1 × 1000. In the case where the chemical structure, average molecular weight, and the like of the amine compound are not clear, it can be measured in accordance with a publicly known amine value measurement method, for example, JIS K 7237-1995.

[0121] As the epoxy compound (C8), there is no particular limitation as long as it is a compound having an epoxy group in the molecule, and for example, polyglycidyl ether-type epoxy resins of aliphatic polyols such as ethylene glycol, propylene glycol, hexanediol, neopentyl glycol, trimethylol ethane, trimethylol propane, pentaerythritol, glycerol, diglycerol, sorbitol, spiroglycol, or hydrogenated bisphenol A;

[0122] bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, bisphenol AD-type epoxy resins, and the like bisphenol-type epoxy resins;

[0123] phenol novolak-type epoxy resins such as glycidyl ethers of phenol novolak resins and cresol novolak resins, and the like aromatic epoxy resins;

[0124] polyglycidyl ether-type epoxy resins of polyols that are oxirane or oxetane adducts of aromatic polyhydroxy compounds such as bisphenol A, bisphenol F, bisphenol S, bisphenol AD, and the like;

[0125] polyglycidyl ether-type epoxy resins of polyether polyols such as polyethylene glycol, polypropylene glycol, or polytetramethylene glycol; and cyclic aliphatic-type polyepoxy resins such as bis(3,4-epoxycyclohexylmethyl) adipate and 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexyl carboxylate;

[0126] Polyglycidyl ester type epoxy resins of polycarboxylic acids such as propane tricarboxylic acid, butane tetracarboxylic acid, adipic acid, phthalic acid, terephthalic acid, or trimellitic acid;

[0127] Bisepoxy resins of hydrocarbon-based dienes such as butadiene, hexadiene, octadiene, dodecadiene, cyclooctadiene, a-pinene, or vinyl cyclohexene;

[0128] Epoxy resins of diene polymers such as polybutadiene or polyisoprene;

[0129] Glycidyl amine type epoxy resins such as tetraglycidyl diaminodiphenyl methane, triglycidyl p-aminophenol, tetraglycidyl bisaminomethylcyclohexane, diglycidyl aniline, tetraglycidyl m-xylylenediamine;

[0130] Heterocycle-containing epoxy resins such as triazine or hydantoin.

[0131] They can be used alone or in combination with two or more.

[0132] The isocyanate-reactive compound (C) preferably contains a 2-functional compound. Thereby, the flexibility of the cured coating film can be improved, and a coating agent with more excellent adhesion to a substrate can be produced. The content of the 2-functional compound in the isocyanate-reactive compound (C) can be appropriately adjusted, and as an example, it is 50% by mass or more, 80% by mass or more. The total amount of the isocyanate-reactive compound (C) can be the 2-functional compound.

[0133] The isocyanate-reactive compound (C) preferably contains a compound with a glass transition temperature (Tg) of 15°C or higher. Thereby, a coating agent with inhibited blocking can be produced. The upper limit of the glass transition temperature of the isocyanate-reactive compound (C) can be appropriately adjusted according to the purpose, and as an example, it is 80°C or lower.

[0134] The coating agent of the present application can contain a solvent. As the solvent usable in the coating agent of the present application, esters such as ethyl acetate, butyl acetate, and cellulose 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 dichloromethane and dichloroethane; and dimethyl sulfoxide and dimethyl sulfonamide can be used, and one kind or two or more kinds in combination can be used.

[0135] The coating agent of the present application can contain a urethanization catalyst, an organic filler, an inorganic filler, an organic pigment, an inorganic pigment, a body pigment, a clay mineral, a wax, a surfactant, a stabilizer, a flow adjusting agent, a leveling agent, a rheology control agent, an ultraviolet absorber, an antioxidant, a plasticizer, and the like. As the urethanization catalyst and the pigment, the same substances as those used in the two-component curable adhesive described later can be used.

[0136] The coating method as a coating agent is not particularly limited, and a conventionally known method can be used. As one example, various coating methods such as spray coating, direct gravure coating, reverse gravure coating, offset gravure coating, flexographic coating, offset coating, bar coating, kiss roll coating, forward rotation roll coating, reverse rotation roll coating, slot die coating, vacuum die coating, (micro)cavity blade coating, air knife coating, blade coating, knife coating, spin coating, dip coating, and the like can be cited.

[0137] The coating amount of the coating agent can be appropriately adjusted, and as one example, 10 g / m 2 or less and 100 g / m 2 or more.

[0138] The two-component curable coating agent of the present application is preferably compounded and used in such a manner that the ratio [NCO] / [isocyanate-reactive functional group] of the number of moles of isocyanate groups [NCO] contained in the polyisocyanate composition (X) to the number of moles of functional groups reactive with isocyanate [isocyanate-reactive functional group] contained in the isocyanate-reactive composition (Y) becomes 0.5 to 5.0, more preferably 1.0 to 3.0. Thereby, appropriate curability can be obtained without depending on the environmental humidity at the time of coating.

[0139] [Two-component curable adhesive]

[0140] The two-component curable adhesive of the present application contains the above-described polyisocyanate composition (X) and the isocyanate-reactive composition (Y).

[0141] In the case where the adhesive of the present application is used as a solventless adhesive, the viscosity of the polyisocyanate composition (X) is adjusted to a range suitable for a solventless lamination method. As one example, the adjustment is performed in such a manner that the viscosity at 40°C becomes in the range of 100 to 50,000 mPas, more preferably 500 to 20,000 mPas. As one example, the viscosity of the polyisocyanate composition (X) can be adjusted by the structure (polyol used) of the polyurethane polyisocyanate (Al). The viscosity of the polyisocyanate composition (X) can be measured, for example, using a rotational viscometer at a cone plate: 1° x diameter 50 mm, shear rate: 100 sec -1 -1 °C under 40 °C.

[0142] In the case where the adhesive of the present application is used as a solvent-type adhesive, the viscosity of the polyisocyanate composition (X) can be adjusted by dilution with a solvent described later.

[0143] (Isocyanate-reactive composition (Y))

[0144] The isocyanate-reactive composition (Y) contains an isocyanate-reactive compound (C). As the isocyanate-reactive compound (C), the same substance as used in the above-described coating agent or two or more kinds in combination can be used.

[0145] The isocyanate-reactive compound (C) preferably contains a 2-functional compound. Thereby, the softness of the cured coating film of the adhesive can be improved, and an adhesive having more excellent adhesiveness and adhesion to a substrate can be produced. The content of the 2-functional compound in the isocyanate-reactive compound (C) can be appropriately adjusted, and is, for example, 50% by mass or more, 80% by mass or more. The total amount of the isocyanate-reactive compound (C) can be the 2-functional compound.

[0146] The isocyanate-reactive compound (C) preferably contains a compound having a glass transition temperature (Tg) of 40°C or lower. Thereby, an adhesive having excellent adhesiveness can be produced. The lower limit of the glass transition temperature of the isocyanate-reactive compound (C) can be appropriately adjusted according to the purpose, and is, for example, -50°C or higher.

[0147] (Mono-alcohol compound (D))

[0148] The isocyanate-reactive composition (Y) can contain a mono-alcohol compound (D) having one alcoholic hydroxyl group. The main chain of the mono-alcohol compound (D) is not particularly limited, and examples include a vinyl resin, an acrylic resin, a polyester, an epoxy resin, a polyurethane resin, and the like having one hydroxyl group. In addition, an aliphatic alcohol, an alkyl alkylene glycol, or the like can also be used. The main chain of the mono-alcohol compound (D) can be linear or branched. The bonding position of the hydroxyl group is not particularly limited, and is preferably present at the terminal of the molecular chain.

[0149] As specific examples of the mono-alcohol compound (D), aliphatic mono-alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, lauryl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, nonadecyl alcohol, other alkyl alcohols (C20-50), oleyl alcohol, and isomers thereof, and the like can be given.

[0150] cyclohexanol, methylcyclohexanol, 4-butylcyclohexanol, 4-pentylcyclohexanol, 4-hexylcyclohexanol, cyclodecanol, cyclododecanol, cyclopentadecanol, 4-isopropylcyclohexanol, 3,5,5-trimethylcyclohexanol, menthol, 2-norbornanol, borneol, 2-adamantanol, dicyclohexylmethanol, (6-isopropyl-2-decahydronaphthol), 2-cyclohexylcyclohexanol, 4-cyclohexylcyclohexanol, 4-(4-propylcyclohexyl)cyclohexanol, 4-(4-pentylcyclohexyl)cyclohexanol, α-ambrinol, deoxycorticosterone, 11-dehydrocorticosterone, cholestanol, β-sitostanol, campestanol, stigmastanol, lanostanol, ergostanol, β-cholane, testosterone, estrone, digitoxigenin, dehydroepiandrosterone, coprostanol, pregnenolone, epicholstanol, 7-dehydrocholestanol, estradiol benzoate, tigogenin, hecogenin, dihydrotestosterone, cortisone acetate, stanolone, and isomers thereof, and the like alicyclic monohydric alcohols;

[0151] aromatic aliphatic monohydric alcohols such as benzyl alcohol;

[0152] polyoxyalkylene monohydric alcohols obtained by ring-opening addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, and the like, using an alkyl compound having 1 active hydrogen or the like as an initiator.

[0153] In the case where the adhesive of the present application is supplied in a solventless form, the viscosity of the isocyanate-reactive composition (Y) is adjusted to a range suitable for solventless lamination. As an example, the viscosity at 40°C is adjusted to a range of 100 to 50,000 mPas, more preferably 100 to 20,000 mPas. The viscosity of the isocyanate-reactive composition (Y) can be adjusted by the skeleton of the isocyanate-reactive compound (C) and / or a plasticizer or the like described later.

[0154] (Other components of the adhesive)

[0155] The two-component curable adhesive of the present application can contain components other than the above components. The other components can be contained in either or both of the polyisocyanate composition (X) and the isocyanate-reactive composition (Y), or can be prepared separately from them in advance and used by mixing with the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) immediately before the adhesive is applied. Hereinafter, each component is described.

[0156] (catalyst)

[0157] As the catalyst, metal-based catalysts, amine-based catalysts, aliphatic cyclic amide compounds, quaternary ammonium salts, and the like can be exemplified.

[0158] As the metal-based catalyst, a metal complex-based, an inorganic metal-based, or an organic metal-based catalyst can be given. As the metal complex-based catalyst, acetylacetone 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) can be exemplified, such as acetylacetone iron, acetylacetone manganese, acetylacetone copper, acetylacetone zirconium, and the like.

[0159] As the inorganic metal-based catalyst, a catalyst selected from Sn, Fe, Mn, Cu, Zr, Th, Ti, Al, Co, and the like can be given.

[0160] As the organic metal-based catalyst, an organic zinc compound such as zinc octoate, zinc neodecanoate, zinc naphthenate, a stannous diacetate, a stannous dioctoate, a stannous dioleate, a stannous dilaurylate, a dibutyltin diacetate, a dibutyltin dilaurylate, a dioctyltin dilaurylate, a dibutyltin oxide, a dibutyltin dichloride, an organic tin compound, an organic nickel compound such as nickel octoate, nickel naphthenate, an organic cobalt compound such as cobalt octoate, cobalt naphthenate, an organic bismuth compound such as bismuth octoate, bismuth neodecanoate, bismuth naphthenate, a titanium compound such as tetraisopropoxy titanate, dibutyltitanium dichloride, tetrabutyl titanate, butoxytitanium trichloride, a titanium chelate complex having at least one of an aliphatic diketone, an aromatic diketone, and an alcohol having 2 to 10 carbon atoms as a ligand, and the like can be given.

[0161] As the amine-based catalyst, 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)propylenediamine, bis(dimethylaminopropyl)amine, bis(dimethylaminopropyl)isopropanolamine, 3-quinuclidinol, N,N,N',N'-tetramethylguanidine, 1,3,5-tris(N,N-dimethylaminopropyl)hexahydro-s-triazine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N-methyl-N'-(2-dimethylaminoethyl)piperazine, N,N'-dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethylaminopropylimidazole, N,N-dimethylhexanolamine, N-methyl-N'-(2-hydroxyethyl)piperazine, 1-(2-hydroxyethyl)imidazole, 1-(2-hydroxypropyl)imidazole, 1-(2-hydroxyethyl)-2-methylimidazole, 1-(2-hydroxypropyl)-2-methylimidazole, and the like can be given.

[0162] As the aliphatic cyclic amide compound, δ-valerolactam, ε-caprolactam, ω-enantholactam, η-caprylolactam, β-propiolactam, and the like can be given. Among these, ε-caprolactam is more effective for promoting curing.

[0163] As the quaternary ammonium salt, hydroxyl salts, alkyl acid salts, halide salts, and the like of alkyl ammonium, aromatic ammonium, and the like can be given. As examples, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltriethylammonium chloride, hexadecyltrimethylammonium bromide, and the like can be given, but are not limited to these.

[0164] (Coupling agent)

[0165] As the coupling agent, silane coupling agents, titanate-based coupling agents, aluminum-based coupling agents, and the like can be given.

[0166] As the silane coupling agent, there can be mentioned, for example, aminosilane 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, bis[3-(triethoxysilyl)propyl]amine, and the like; epoxysilane such as β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and the like; vinylsilane such as vinyltri(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and the like; hexamethyldisilazane, γ-mercaptopropyltrimethoxysilane, and the like.

[0167] As the titanate coupling agent, there can be mentioned, for example, tetraisopropoxytitanium, tetra-n-butoxytitanium, butyl titanate dimer, tetra-stearyltitanate, titanium acetylacetonate, titanium lactate, tetraoctyleneglycol titanate, titanium lactate, tetra-stearyloxytitanium, and the like.

[0168] As the aluminum coupling agent, there can be mentioned, for example, acetoalkoxydiisopropylaluminum, and the like.

[0169] (Pigment)

[0170] As the pigment, there is no particular limitation, and there can be mentioned, for example, organic pigments, inorganic pigments, further plastic pigments, and the like, which are described in "Paint Raw Material Handbook 1970 Edition" (edited by Japan Paint Manufacturers Association), such as extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments, green pigments, blue pigments, metallic powder pigments, luminescent pigments, pearl color pigments, and the like.

[0171] As the extender pigment, there can be mentioned, for example, precipitated barium sulfate, whiting, precipitated calcium carbonate, calcium bicarbonate, calcite, alumina white, silica, hydrous fine powder silica (white carbon), ultrafine powder anhydrous silica (Aerosil), silica sand, talc, precipitated magnesium carbonate, bentonite, clay, kaolin, loess, and the like.

[0172] As specific examples of the organic pigment, various insoluble azo pigments such as benzidine yellow, Hansa yellow, and lake red 4R; soluble azo pigments such as lake red C, carmine 6B, and bordeaux 10; various phthalocyanine (copper) pigments such as phthalocyanine blue and phthalocyanine green; various chlorine-containing dye lakes such as rhodamine lake and methyl violet lake; various mordant dye pigments such as quinoline lake and fast sky blue; various vat dye pigments such as anthraquinone pigments, sulfur indigo pigments, and perinone pigments; various quinacridone pigments such as Cinquasia Red B; various dioxazine pigments such as dioxazine violet; various condensed azo pigments such as Cromophtal; aniline black; and the like can be given.

[0173] As the inorganic pigment, various chromates such as chrome yellow, zinc chromate, and molybdate orange; various ferrocyanides such as Prussian blue; various metal oxides such as titanium oxide, zinc white, Mapico Yellow, iron oxide, iron oxide red, chromium oxide green, and zirconium oxide; various sulfides such as cadmium yellow, cadmium red, and mercury sulfide, and even selenides; 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 violet; various metal powder pigments such as aluminum powder, gold powder, silver powder, copper powder, bronze powder, and brass powder; flaky pigments of these metals and mica flaky pigments; metal pigments such as mica flaky pigments covered with metal oxides, mica-like iron oxide pigments, and pearl pigments; graphite; and carbon black can be given.

[0174] As the plastic pigment, for example, "GRANDOLL PP-1000", "PP-2000S", and the like manufactured by DIC Corporation can be given.

[0175] As for the pigment used, it can be appropriately selected depending on the purpose, and for example, from the viewpoint of durability, weather resistance, and designability, as the white pigment, an inorganic oxide such as titanium oxide and zinc white is preferably used, and as the black pigment, carbon black is preferably used.

[0176] As an example, the compounding amount of the pigment is 1 to 400 parts by mass with respect to 100 parts by mass of the total amount of the nonvolatile components of the polyol composition (X) and the polyisocyanate composition (Y), and it is more preferable to be 10 to 300 parts by mass in order to make the adhesiveness and the blocking resistance better.

[0177] (Plasticizer)

[0178] As the plasticizer, for example, phthalic acid-based plasticizers, fatty acid-based plasticizers, aromatic polycarboxylic acid-based plasticizers, phosphoric acid-based plasticizers, polyol-based plasticizers, epoxy-based plasticizers, polyester-based plasticizers, carbonate-based plasticizers, and the like can be given.

[0179] As the phthalic acid-based plasticizer, for example, 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, dibenzyl phthalate, butyl benzyl phthalate, dicyclohexyl phthalate, octyl decyl phthalate, dimethyl isophthalate, di(2-ethylhexyl) isophthalate, diisooctyl isophthalate, and the like can be given. As the tetrahydrophthalic acid-based plasticizer, for example, di(2-ethylhexyl) tetrahydrophthalate, di-n-octyl tetrahydrophthalate, diisodecyl tetrahydrophthalate, and the like can be given.

[0180] As the fatty acid-based plasticizer, for example, di-n-butyl adipate, di(2-ethylhexyl) adipate, diisodecyl adipate, diisononyl adipate, di(C6-C10 alkyl) adipate, dibutyl diethylene glycol adipate, and the like can be given as the adipic acid-based plasticizer. As the azelaic acid-based plasticizer, for example, di-n-hexyl azelate, di(2-ethylhexyl) azelate, diisooctyl azelate, and the like can be given. As the sebacic acid-based plasticizer, for example, di-n-butyl sebacate, di(2-ethylhexyl) sebacate, diisononyl sebacate, and the like can be given. As the maleic acid-based plasticizer, for example, dimethyl maleate, diethyl maleate, di-n-butyl maleate, di(2-ethylhexyl) maleate, and the like can be given. As the fumaric acid-based plasticizer, for example, di-n-butyl fumarate, di(2-ethylhexyl) fumarate, and the like can be given. As the itaconic acid-based plasticizer, for example, monomethyl itaconate, monobutyl itaconate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, di(2-ethylhexyl) itaconate, and the like can be given. As the stearic acid-based plasticizer, for example, n-butyl stearate, glycerol monostearate, diethylene glycol distearate, and the like can be given. As the oleic acid-based plasticizer, for example, butyl oleate, glycerol monooleate, diethylene glycol monooleate, and the like can be given. As the citric acid-based plasticizer, for example, triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tributyl citrate, acetyl tri(2-ethylhexyl) citrate, and the like can be given. As the ricinoleic acid-based plasticizer, for example, methyl acetyl ricinoleate, butyl acetyl ricinoleate, glycerol monoricinoleate, diethylene glycol monoricinoleate, and the like can be given. As the other fatty acid-based plasticizer, for example, diethylene glycol monolaurate, diethylene glycol dinonanoate, pentaerythritol fatty acid ester, and the like can be given.

[0181] Examples of aromatic polycarboxylic acid plasticizers include: tri-n-hexyl trimellitate, tri(2-ethylhexyl) trimellitate, tri-n-octyl trimellitate, triisooctyl trimellitate, triisononyl trimellitate, tridecyl trimellitate, triisodecyl trimellitate, etc.; and pyromellitic acid plasticizers such as tetra(2-ethylhexyl) pyromellitic acid and tetra-n-octyl pyromellitic acid.

[0182] Examples of phosphoric acid-based plasticizers include: triethyl phosphate, tributyl phosphate, tri(2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, octyl diphenyl phosphate, toluyl diphenyl phosphate, toluyl phenyl phosphate, tricresyl phosphate, tri(xylyl) phosphate, tri(chloroethyl) phosphate, tri(chloropropyl) phosphate, tri(dichloropropyl) phosphate, and tri(isopropylphenyl) phosphate.

[0183] Examples of polyol-based plasticizers include: diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, triethylene glycol di-(2-ethylbutyrate), triethylene glycol di-(2-ethylhexanoate), dibutyl methylene bis(thioglycolic acid) ester, and glycerol-based plasticizers such as glyceryl monoacetate, glyceryl triacetate, and glyceryl tributyrate.

[0184] Examples of epoxy-based plasticizers include: epoxidized soybean oil, epoxidized butyl stearate, epoxidized di-2-ethylhexyl phthalate, epoxidized diisodecyl phthalate, epoxidized triglyceride, epoxidized octyl oleate, and epoxidized decyl oleate.

[0185] Examples of polyester plasticizers include adipic acid-based polyesters, sebacic acid-based polyesters, and phthalic acid-based polyesters.

[0186] Examples of carbonate-based plasticizers include propylene carbonate and ethylene carbonate.

[0187] In addition, other examples of plasticizers include partially hydrogenated terphenyl, adhesive plasticizers, diallyl phthalate, acrylic monomers, oligomers, and other polymeric plasticizers. These plasticizers can be used alone or in combination of two or more.

[0188] (acid anhydride)

[0189] As the acid anhydride, a cyclic aliphatic acid anhydride, an aromatic acid anhydride, an unsaturated carboxylic acid anhydride, or the like can be given, and one kind or two or more kinds in combination can be used. More specifically, for example, maleic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetra carboxylic anhydride, dodecenyl succinic anhydride, polyadipic anhydride, polynonanoic anhydride, polysebacic anhydride, poly(ethyloctadecandioic acid) anhydride, poly(phenylhexadecandioic acid) anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, methylcyclohexene tetra carboxylic anhydride, ethylene glycol bis-trimellitate dianhydride, chloro-bridged anhydride, norbornene diacid anhydride, methyl norbornene diacid anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, and the like can be given.

[0190] As the acid anhydride, a compound modified with a diol from the above compounds can also be used. As the diol that can be used for the modification, an alkylene glycol such as ethylene glycol, propylene glycol, neopentyl glycol, and the like; a polyether glycol such as polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and the like; and the like can be given. Further, a copolyether glycol of two or more kinds of diols and / or polyether glycols from among them can also be used.

[0191] Alternatively, as the acid anhydride, a homopolymer or a copolymer of a compound having a polymerizable unsaturated group such as maleic anhydride from the above compounds can also be used. As the compound that can be copolymerized with a compound having an acid anhydride group and a polymerizable unsaturated group, an α-olefin such as ethylene, propylene, 1,3-butadiene, cyclopentyl ethylene, and the like; a vinyl compound 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-ethynyl naphthalene, 9-ethynylphenanthrene, and the like; a fluoroolefin such as vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, and the like; and the like can be given, and one kind or two or more kinds in combination can be used. It is preferable to use styrene and p-tert-butylstyrene that belong to the vinyl compounds having an aromatic ring.

[0192] (Phosphoric acid compound)

[0193] As the phosphoric acid compound, there can be mentioned phosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, acid methyl phosphate, acid ethyl phosphate, acid butyl phosphate, dibutyl phosphate, acid 2-ethylhexyl phosphate, bis (2-ethylhexyl) phosphate, acid isododecyl phosphate, acid butoxyethyl phosphate, acid oleyl phosphate, acid tetracosyl phosphate, 2-hydroxyethyl methacrylate acid phosphate, polyoxyethylene alkyl ether phosphate, and the like. In the adhesive of the present application, the polyisocyanate composition (X) contains a phosphoric acid compound, and therefore, it is not necessary to add a phosphoric acid compound when the adhesive is produced.

[0194] (Form of adhesive)

[0195] The two-component curable adhesive of the present application can be in any form of solvent type or solventless type. Note that, in the present specification, the "solvent type" of the adhesive refers to a form used in a so-called dry lamination method, which is a method in which the adhesive is applied to a substrate, and after heating in an oven or the like to volatilize organic solvents in the coating film, the other substrate is bonded thereto. Either or both of the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) contain an organic solvent capable of dissolving (diluting) the components of the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) used in the present application.

[0196] As the organic solvent, there can be mentioned, for example, esters such as ethyl acetate, butyl acetate, cellulose acetate solvent, ketones such as acetone, methyl ethyl ketone, isobutyl ketone, cyclohexanone, ethers such as tetrahydrofuran, dioxane, aromatic hydrocarbons such as toluene, xylene, halogenated hydrocarbons such as dichloromethane, dichloroethane, dimethyl sulfoxide, dimethyl sulfone, and the like. The organic solvent used as a reaction medium when the components of the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) are produced is sometimes further used as a diluent at the time of coating.

[0197] In the present specification, the "solventless type" of adhesive refers to the form of adhesive used in so-called solventless lamination, which is a method in which the adhesive is applied to a substrate and then laminated to another substrate without a process of heating in an oven or the like to volatilize the solvent, and in which the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) are substantially free of 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 dichloromethane and dichloroethane, and highly soluble organic solvents such as dimethyl sulfoxide and dimethyl sulfoneamide, and in particular, substantially free of ethyl acetate or methyl ethyl ketone. In the case where the organic solvent used as a reaction medium in the production of the constituent components of the polyisocyanate composition (X) or the isocyanate-reactive composition (Y) or the raw materials thereof is not completely removed and a small amount of the organic solvent remains in the polyisocyanate composition (X) or the isocyanate-reactive composition (Y), it is considered that the organic solvent is substantially free. In addition, in the case where the isocyanate-reactive composition (Y) contains a low-molecular-weight alcohol, the low-molecular-weight alcohol reacts with the polyisocyanate composition (X) to become a part of the coating film, and thus does not need to be volatilized after application. Therefore, such a form is also handled as a solventless type of adhesive, and the low-molecular-weight alcohol is not considered to be an organic solvent.

[0198] The two-component curable adhesive of the present application is preferably compounded and used in such a manner that the ratio [NCO] / [isocyanate-reactive functional group] of the number of moles of isocyanate groups contained in the polyisocyanate composition (X) [NCO] to the number of moles of functional groups reactive with isocyanate contained in the isocyanate-reactive composition (Y) [isocyanate-reactive functional group] becomes 0.5 to 5.0, and more preferably 1.0 to 3.0. Thereby, appropriate curability can be obtained regardless of the environmental humidity at the time of application.

[0199] <laminate>

[0200] The laminate of the present application is obtained, for example, by the following methods: a two-component mixing process method in which the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) are mixed in advance, and then applied to a first substrate, and then a second substrate is laminated on the applied surface, and the adhesive layer is cured; and a two-component separate application process method in which the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) are applied to a first substrate and a second substrate, respectively, and then the applied surfaces are brought into contact and pressed, thereby laminating the first substrate and the second substrate, and the adhesive layer is cured. The film used is not particularly limited, and a film appropriate for the use can be appropriately selected.

[0201] For example, as food packaging, polyethylene terephthalate (PET) film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film (LLDPE: low-density polyethylene film, HDPE: high-density polyethylene film, MDOPE: monoaxially stretched polyethylene film, OPE: biaxially stretched polyethylene film), polypropylene film (CPP: unstretched polypropylene film, OPP: biaxially stretched polypropylene film), gas barrier heat-seal film in which an olefin-based heat-sealable resin layer is provided on one side or both sides of a resin having gas barrier properties such as ethylene-vinyl alcohol copolymer, polyvinyl alcohol, and the like, polyolefin film, polyvinyl alcohol film, ethylene-vinyl alcohol copolymer film, and the like can be given.

[0202] In addition, it is also preferable to use a biomass film, a biodegradable film, or a recycled plastic film formed of a material containing a biomass-derived component, a biodegradable component, or a recycled component.

[0203] The biomass film, the biodegradable film, and the recycled plastic film can be used, in addition to being sold by each company, for example, a film sheet listed in the biomass certified product list described in the General Incorporated Association, Japan Organic Resources Association, a film listed in the environmental protection mark certified product list described in the Public Interest Incorporated Association, Japan Environmental Association, a film having a symbol mark prescribed by the Japan Bio-Plastic Association, and the like, which are certified by each country.

[0204] (Biomass Film)

[0205] As a specific well-known biomass film, a film using biomass-derived ethylene glycol as a raw material can be given. The biomass-derived ethylene glycol is ethylene glycol using ethanol (biomass ethanol) manufactured using biomass as a raw material as a raw material. For example, the biomass-derived ethylene glycol can be obtained by a method of generating ethylene glycol from biomass ethanol using a method well known in the past, and the like. In addition, commercially available biomass ethylene glycol can be used, and for example, biomass ethylene glycol sold by India Glycols Limited can be suitably used.

[0206] For example, as a substitute for a conventional polyethylene terephthalate film using a petroleum-based raw material, a film containing a biomass polyester using biomass-derived ethylene glycol as a diol unit and a fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit, a biomass polyethylene terephthalate, and the like are known.

[0207] The dicarboxylic acid unit of the biomass polyester uses a fossil fuel-derived dicarboxylic acid. As the dicarboxylic acid, an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, and a derivative thereof can be used without limitation.

[0208] Further, a copolymer polyester obtained by adding, as a third component, a copolymer component of a 2-functional hydroxycarboxylic acid and / or at least one multifunctional compound selected from the group consisting of a 3-functional or higher polyhydric alcohol, a 3-functional or higher polycarboxylic acid and / or anhydride thereof, and a 3-functional or higher hydroxycarboxylic acid, in addition to the above-mentioned diol component and dicarboxylic acid component, can also be used.

[0209] Further, for example, as a substitute for the conventional polyolefin-based film using a petroleum-based raw material, a biomass polyethylene-based film, a biomass polyethylene-polypropylene-based film, and the like, which contain a polyethylene-based resin using a biomass-derived ethylene glycol as a raw material, are known.

[0210] The polyethylene-based resin is not particularly limited except that a biomass-derived ethylene glycol described above is used in a part of the raw material, and a homopolymer of ethylene, a copolymer of ethylene and an α-olefin (an ethylene-α-olefin copolymer containing 90% by mass or more of ethylene units) in which ethylene is a main component, and the like can be mentioned, and one kind thereof can be used alone or two or more kinds thereof can be used in combination.

[0211] Note that the α-olefin constituting the copolymer of ethylene and an α-olefin is not particularly limited, and α-olefins having 4 to 8 carbon atoms such as 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene can be mentioned. Known polyethylene resins such as a low-density polyethylene resin, a medium-density polyethylene resin, and a linear low-density polyethylene resin can be used. Among them, from the viewpoint that damage such as a hole or a crack is less likely to occur even when the films are rubbed against each other, a linear low-density polyethylene resin (LLDPE) (a copolymer of ethylene and 1-hexene, or a copolymer of ethylene and 1-octene) is preferred, and a linear low-density polyethylene resin having a density of 0.910 to 0.925 g / cm 3 is more preferred.

[0212] As a biomass film, a film using a biomass raw material classified by a biomass plasticity degree prescribed in ISO 16620 or ASTM D6866 is also circulated. Radioactive carbon 14C exists at a proportion of 1 in 1012 in the atmosphere, and this proportion is not changed in carbon dioxide in the atmosphere, and therefore, in a plant in which this carbon dioxide is fixed by photosynthesis, the proportion is not changed. Therefore, radioactive carbon 14C is contained in the carbon of a plant-derived resin. In contrast, the carbon of a resin derived from a fossil fuel hardly contains radioactive carbon 14C. Therefore, by measuring the concentration of radioactive carbon 14C in a resin with an accelerator mass spectrometer, the proportion of a plant-derived resin, that is, the biomass plasticity degree in the resin can be found.

[0213] As the biomass plastic of which the biomass plasticity as defined in ISO 16620 or ASTM D6866 is 80% or more, preferably 90% or more, a low-density polyethylene of plant origin, for example, the trade names "SBC818", "SPB608", "SBF0323HC", "STN7006", "SEB853", "SPB681", etc. manufactured by Braskem Co. can be cited, and can be suitably used as a film using them as a raw material.

[0214] Further, a film, a sheet, etc. compounded with starch, polylactic acid as a biomass raw material are also known. They can be suitably selected and used according to the use.

[0215] The biomass film can be a laminate of a plurality of biomass films, or a laminate of a conventional petroleum-based film and a biomass film. Further, these biomass films can be an unstretched film, or a stretched film, and the production method thereof is not limited.

[0216] (Biodegradable film)

[0217] A specifically known biodegradable film can be a biodegradable film using a biodegradable resin generally available as a raw material. For example, polycaprolactone, polyvinyl alcohol, polyamide, cellulose ester, lactic acid-based polyester resin, aliphatic polyester resin, or aliphatic-aromatic polyester resin, etc. can be cited. These biodegradable resins can be used singly, or two or more kinds in combination. Among them, an aliphatic polyester resin or an aliphatic-aromatic polyester resin is preferably used.

[0218] As the aliphatic polyester resin, an aliphatic polyester obtained by polycondensation of an aliphatic diol and an aliphatic dicarboxylic acid can be cited. As the aliphatic diol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol can be cited. They can be used singly, or a mixture thereof can be used. Among them, 1,4-butanediol is preferably used. As the aliphatic dicarboxylic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, suberic acid, dodecanedioic acid, or an acid anhydride belonging to a derivative thereof can be cited. Among them, succinic acid or succinic anhydride, or a mixture of them with adipic acid is preferable.

[0219] Specifically, polybutylene succinate (PBS) obtained from 1,4-butanediol and succinic acid (for example, BioPBS manufactured by PPT MCC Biochem), polybutylene succinate adipate (PBSA) in which adipic acid is copolymerized in PBS, etc. can be cited.

[0220] As the aliphatic-aromatic polyester-based resin, a copolymer containing an aliphatic dicarboxylic acid unit, an aromatic dicarboxylic acid unit, and a chain aliphatic and / or alicyclic diol unit can be given. The number of carbon atoms of the diol component providing the diol unit is usually 2 to 10, and for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol, and the like can be given. Among them, a diol having a number of carbon atoms of 2 to 4 is preferred, and ethylene glycol, 1,4-butanediol is preferred, and 1,4-butanediol is further preferred. The number of carbon atoms of the dicarboxylic acid component providing the dicarboxylic acid unit is usually 2 to 10, and for example, succinic acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, and the like can be given. Among them, succinic acid or adipic acid is preferred. As the aromatic dicarboxylic acid component providing the aromatic dicarboxylic acid unit, for example, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, and the like can be given. Among them, terephthalic acid, isophthalic acid is preferred, and terephthalic acid is further preferred.

[0221] Specifically, PBAT (for example, Ecoflex manufactured by BASF Corporation) which is a copolymer of 1,4-butanediol, adipic acid, and terephthalic acid, and the like can be given.

[0222] As others, for example, poly(3-hydroxyalkanoate) of an aliphatic polyester copolymer obtained from a hydroxyalkanoic acid and a polycarboxylic acid can be given (among them, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) (for example, AONILEX manufactured by Kaneka Corporation), polylactic acid (PLA) (for example, REVODE manufactured by Zhejiang Hisunny Biomatierials Co., Ltd., Ingeo manufactured by Nature Works LLC.).

[0223] The biodegradable film can be a laminate in which a plurality of biodegradable films are stacked, or a laminate of a conventional petroleum-based film and a biodegradable film. In addition, these biodegradable films can be unstretched films, or stretched films, and the production method thereof is not limited.

[0224] The film can be a film subjected to a stretching treatment. As a stretching treatment method, generally, after a resin is melt-extruded into a sheet shape by an extrusion film production method or the like, simultaneous biaxial stretching or sequential biaxial stretching is performed. In the case of sequential biaxial stretching, generally, longitudinal stretching treatment is first performed, and then transverse stretching is performed. Specifically, a method in which longitudinal stretching using a speed difference between rollers is combined with transverse stretching using a tenter is often used.

[0225] Various surface treatments such as flame treatment, corona discharge treatment, and the like can be performed on the surface of the film as needed to form an adhesive layer having no defects such as film breakage, shrinkage, and the like.

[0226] Alternatively, a thin film in which an evaporation layer of a metal such as aluminum, a metal oxide such as silicon dioxide and / or aluminum oxide is laminated, a barrier thin film containing polyvinyl alcohol and / or ethylene-vinyl alcohol copolymer, vinylidene chloride, and the like can also be used. By using such a thin film, a laminate having barrier properties against water vapor, oxygen, alcohol, non-reactive gas, volatile organic compounds (flavor), and the like can be produced.

[0227] As the paper, there is no particular limitation, and a publicly known paper base material can be used. Specifically, a paper base material is manufactured using a publicly known papermaking machine using a natural fiber for papermaking such as wood pulp, but the papermaking conditions are not particularly specified. As the natural fiber for papermaking, wood pulp such as coniferous tree pulp, broad-leaved tree pulp, non-wood pulp such as abaca pulp, sisal hemp pulp, flax pulp, and the like, and pulp obtained by subjecting these pulps to chemical modification can be given. As the type of pulp, chemical pulp based on the sulfite digestion method, acid / neutral / alkali sulfite digestion method, sodium salt digestion method, and the like, ground pulp, chemically ground pulp, thermomechanical pulp, and the like can be used. In addition, various high-quality paper, art paper, backing paper, impregnated paper, thick paper, paperboard, and the like available on the market can also be used.

[0228] As a more specific configuration of the laminate, the following can be given:

[0229] (1) Base material 1 / adhesive layer 1 / sealing film

[0230] (2) Base material 1 / adhesive layer 1 / metal evaporation unstretched film

[0231] (3) Base material 1 / adhesive layer 1 / metal evaporation stretched film

[0232] (4) Transparent evaporation stretched film / adhesive layer 1 / sealing film

[0233] (5) Base material 1 / adhesive layer 1 / base material 2 / adhesive layer 2 / sealing film

[0234] (6) Base material 1 / adhesive layer 1 / metal evaporation stretched film / adhesive layer 2 / sealing film

[0235] (7) Base material 1 / adhesive layer 1 / transparent evaporation stretched film / adhesive layer 2 / sealing film

[0236] (8) Base material 1 / adhesive layer 1 / metal layer / adhesive layer 2 / sealing film

[0237] (9) Base material 1 / adhesive layer 1 / base material 2 / adhesive layer 2 / metal layer / adhesive layer 3 / sealing film

[0238] (10) Base material 1 / adhesive layer 1 / metal layer / adhesive layer 2 / base material 2 / adhesive layer 3 / sealing film

[0239] and the like, but is not limited thereto.

[0240] As the base material 1 used in the configuration (1), MDOPE film, OPE film, OPP film, PET film, nylon film, paper, and the like can be given. In addition, as the base material 1, a base material on which coating is performed for the purpose of improving gas barrier properties, ink receiving properties at the time of providing a print layer described later, and the like can also be used. As a commercially available product of the base material film 1 on which coating is performed, K-OPP film, K-PET film, K-nylon film, and the like can be given. The adhesive layer 1 is a cured coating film of the adhesive of the present application. As the sealing film, CPP film, LLDPE film, easy-to-open heat-seal film, gas barrier heat-seal film, and the like can be given. A print layer can be provided on the surface of the base material 1 on the side of the adhesive layer 1 (in the case where a base material film on which coating is performed is used as the base material film 1, on the surface of the coating layer on the side of the adhesive layer 1) or on the surface on the side opposite to the adhesive layer 1. The print layer is formed by a general printing method conventionally used in printing on a polymer film and / or paper using various printing inks such as gravure ink, flexographic ink, offset ink, hole block ink, and inkjet ink.

[0241] As the base material 1 used in the configurations (2) and (3), MDOPE film, OPE film, OPP film, PET film, paper, and the like can be given. The adhesive layer 1 is a cured coating film of the adhesive of the present application. As the metal vapor deposition unstretched film, VM-CPP film, VM-LLDPE film, and the like on which metal vapor deposition of aluminum or the like is performed on CPP film, LLDPE film, gas barrier heat-seal film can be used, and as the metal vapor deposition stretched film, VM-MDOPE film, VM-OPE film, VM-OPP film, and the like on which metal vapor deposition of aluminum or the like is performed on MDOPE film, OPE film, OPP film can be used. As with the configuration (1), a print layer can be provided on any surface of the base material 1.

[0242] As the transparent vapor deposition stretched film used in the configuration (4), a film on which vapor deposition of silicon dioxide, aluminum oxide is performed on MDOPE film, OPE film, OPP film, PET film, nylon film, and the like can be given. For the purpose of protection of the inorganic vapor deposition layer of silicon dioxide, aluminum oxide, and the like, a film on which coating is performed on the vapor deposition layer can be used. The adhesive layer 1 is a cured coating film of the adhesive of the present application. The sealing film can be the same sealing film as in the configuration (1). A print layer can be provided on the surface of the transparent vapor deposition stretched film on the side of the adhesive layer 1 (in the case where a transparent vapor deposition stretched film on which coating is performed on the inorganic vapor deposition layer is used, on the surface of the coating layer on the side of the adhesive layer 1). The print layer can be formed in the same manner as in the configuration (1).

[0243] As the substrate 1 of the configuration (5), a PET film, paper, or the like can be given. As the substrate 2, a nylon film or the like can be given. At least one of the adhesive layer 1 and the adhesive layer 2 is a cured coating film of the adhesive of the present application. The sealing film can be the same sealing film as that of the configuration (1). As with the configuration (1), a print layer can be provided on an arbitrary surface of the substrate 1.

[0244] As the substrate 1 of the configuration (6), the same substrate as that of the configurations (2) and (3) can be given. As the metal vapor deposition stretched film, a VM-MDOPE film, a VM-OPE film, a VM-OPP film, and a VM-PET film, to which metal vapor deposition of aluminum or the like has been performed, can be given to the MDOPE film, the OPE film, the OPP film, and the PET film. At least one of the adhesive layer 1 and the adhesive layer 2 is a cured coating film of the adhesive of the present application. The sealing film can be the same sealing film as that of the configuration (1). As with the configuration (1), a print layer can be provided on an arbitrary surface of the substrate 1.

[0245] As the substrate 1 of the configuration (7), a PET film, paper, or the like can be given. As the transparent vapor deposition stretched film, the same film as that of the configuration (4) can be given. At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present application. The sealing film can be the same sealing film as that of the configuration (1). As with the configuration (1), a print layer can be provided on an arbitrary surface of the substrate 1.

[0246] As the substrate 1 of the configuration (8), a PET film, paper, or the like can be given. As the metal layer, an aluminum foil or the like can be given. At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present application. The sealing film can be the same sealing film as that of the configuration (1). As with the configuration (1), a print layer can be provided on an arbitrary surface of the substrate 1.

[0247] As the substrate 1 of the configurations (9) and (10), a PET film, paper, or the like can be given. As the substrate 2, a nylon film or the like can be given. As the metal layer, an aluminum foil or the like can be given. At least one of the adhesive layers 1, 2, and 3 is a cured coating film of the adhesive of the present application. The sealing film can be the same sealing film as that of the configuration (1). As with the configuration (1), a print layer can be provided on an arbitrary surface of the substrate 1.

[0248] The laminate of the present application can include other films, substrates, in addition to the above-described configurations (1) to (10). As the other substrates, in addition to the above-described stretched film, unstretched film, and transparent vapor deposition film, a porous substrate such as paper, wood, leather, or the like described later can be used. The adhesive used when the other substrate is attached can be the adhesive of the present application or can not be the adhesive of the present application.

[0249] The "other layer" can contain publicly known additives, stabilizers such as antistatic agents, easy-adhesion coating agents, plasticizers, lubricants, antioxidants, and the like. In addition, the "other layer" can also be one that has been subjected to a surface treatment such as a corona treatment, a plasma treatment, an ozone treatment, a chemical treatment, a solvent treatment, or the like as a pretreatment to improve adhesion when laminated with other materials.

[0250] The laminate of the present application can be suitably used as a packaging material for food, pharmaceuticals, household goods, a cover material, a paper drinking straw, paper napkins, paper spoons, paper plates, paper cups, and the like, a paper tableware, a defense material, a roofing material, a solar cell panel material, a packaging material for a battery, a window material, an outdoor flooring material, a lighting protection material, an automobile component, a signboard, a sticker, and the like, a decorative sheet used in outdoor industrial applications, an injection molding simultaneous decoration method, and the like, a packaging material for liquid detergents for washing, liquid detergents for kitchen use, liquid detergents for bathing, liquid soaps for bathing, liquid shampoos, liquid hair conditioners, and the like.

[0251] <Packaging material>

[0252] The laminate of the present application can be used as a multilayer packaging material for the purpose of protecting food, pharmaceuticals, and the like. When used as a multilayer packaging material, the layer constitution can be changed depending on the content, the use environment, and the use form. In addition, an easy-opening treatment, a resealing mechanism, and the like can be appropriately provided on the packaging body of the present application.

[0253] As a specific example of the packaging material of the present application, for example, a packaging material formed by bagging a laminate having a sealing film such as the constitution examples (1), (4) to (10) of the laminate described above can be given. The laminate is folded or overlapped so that the faces of the inner layers (the faces of the sealing films) are opposed to each other, and the peripheral end portions are heat-sealed to form a bag shape. As a bagging method, a method in which heat-sealing is performed in a form such as a side-seal type, a two-side seal type, a three-side seal type, a four-side seal type, an envelope-stick seal type, a clamper-stick seal type, a seal type with a fold, a flat-bottom seal type, a square-bottom seal type, a gusset bag type (gazette), and other heat-seal types can be given. The packaging material of the present application can take various forms depending on the content, the use environment, and the use form. It can also be a self-supporting packaging material (a self-supporting bag), and the like. As a heat-sealing method, publicly known methods such as a rod seal, a rotary roll seal, a tape seal, a pulse seal, a high-frequency seal, an ultrasonic seal, and the like can be given.

[0254] In the packaging material of the present application, after the opening portion is filled with contents, the opening portion is heat-sealed, and an article using the packaging material of the present application is manufactured. As the contents to be filled, for example, as food, there can be mentioned snack foods such as rice crackers, bean snacks, nuts, cookies, wafers, gummy candies, pies, half-baked cakes, candies, snack foods, bread, snack noodles, instant noodles, dried noodles, pasta, aseptic packed rice, chowmein, porridge, packed sticky rice, cereals, pickles, boiled beans, natto, miso, frozen tofu, tofu, chestnut mushrooms, konjak, processed vegetables, jams, peanut butter, salads, frozen vegetables, processed potatoes, ham, bacon, sausages, processed chicken, salted beef, fish ham / sausages, processed fish paste, fish cakes, seaweed, sweet boiled seafood, dried bonito, salted fish, smoked salmon, spicy tuna, fruit pulp such as peaches, oranges, pineapples, apples, pears, cherries, corn, asparagus, mushrooms, onions, carrots, radishes, potatoes, cooked foods such as hamburgers, meatballs, seafood deep-fried foods, dumplings, crepes, cooked foods, butter, margarine, cheese, cream, instant cream powder, baby formula milk, liquid seasonings, steamed curry, pet foods, and the like.

[0255] In addition, as non-foods, various packaging materials for cigarettes, medical supplies such as disposable heat packs, infusion bags, liquid detergents for washing, liquid detergents for kitchens, liquid detergents for baths, liquid soaps for baths, liquid shampoos, liquid hair conditioners, tonics, emulsions, vacuum heat insulating materials, batteries, and the like can be used.

[0256] Examples

[0257] Hereinafter, the present application will be described in more detail by citing specific synthesis examples and examples, but the present application is not limited to these examples. Note that in the following examples, unless otherwise specified, "parts" and "%" respectively mean "mass parts" and "mass %".

[0258] Preparation of the polyisocyanate composition (X)

[0259] (Polyisocyanate composition (X-1))

[0260] In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a condenser, 744.5 parts of hexamethylene diisocyanate (HDI) was charged, and heated to 60°C under a stream of nitrogen while stirring. Then, 255.5 parts of polyoxypropylene sorbitol ether (SANNIX SP-750 manufactured by Sanyo Chemical Industries, Ltd.) was added while paying attention to heat generation, and then heated to 80°C. Further, the reaction was continued at 80°C until NCO% did not change, 0.2 parts of acid phosphorus butyl ester was added, and the reaction was terminated. Subsequently, purification was performed using a thin film distillation apparatus at a pressure of about 0.02 Torr and a temperature of 160°C until HDI in the urethane prepolymer, which was a reaction product of HDI and a polyol, became 0.05 mass% in solid content, whereby a polyisocyanate composition (X-1) was obtained. The NCO% of the polyisocyanate composition (X-1) was 12.1%.

[0261] (Polyisocyanate composition (X-2))

[0262] In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a condenser, 836.1 parts of hexamethylene diisocyanate (HDI) was charged, and heated to 60°C under a stream of nitrogen while stirring. Then, 163.9 parts of polyoxypropylene sorbitol ether (SANNIX SP-750 manufactured by Sanyo Chemical Industries, Ltd.) was added while paying attention to heat generation, and then heated to 100°C. Further, the reaction was continued at 100°C for 10 hours, 0.2 parts of polyphosphoric acid was added, and the reaction was terminated. Subsequently, purification was performed using a thin film distillation apparatus at a pressure of about 0.02 Torr and a temperature of 160°C until HDI in the urethane prepolymer, which was a reaction product of HDI and a polyol, became 0.05 mass% in solid content, whereby a polyisocyanate composition (X-2) was obtained. The NCO% of the polyisocyanate composition (X-2) was 12.1%.

[0263] (Polyisocyanate composition (X-3))

[0264] In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a condenser, 712.9 parts of hexamethylene diisocyanate (HDI) was charged, and heated to 60°C under a stream of nitrogen while stirring. Then, 186.6 parts of polyoxypropylene sorbitol ether (SANNIX SP-750 manufactured by Sanyo Chemical Industries, Ltd.) and 100.5 parts of 2-functional polyethylene glycol having a molecular weight of 400 were added while paying attention to heat generation, and then heated to 80°C. Further, the reaction was continued at 80°C until NCO% did not change, 0.2 parts of butyl acid phosphate was added, and the reaction was terminated. Subsequently, purification was performed using a thin film distillation apparatus at a pressure of about 0.02 Torr and a temperature of 160°C until the content of HDI in the urethane prepolymer as a reaction product of HDI became 0.05 mass% in the solid content, whereby a polyisocyanate composition (X-3) was obtained. The NCO% of the polyisocyanate composition (X-3) was 11.2%.

[0265] (Polyisocyanate composition (X-4))

[0266] In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a condenser, 802.8 parts of hexamethylene diisocyanate (HDI) was charged, and heated to 60°C under a stream of nitrogen while stirring. Then, 197.2 parts of polyoxypropylene sucrose ether (SANNIX HS-209 manufactured by Sanyo Chemical Industries, Ltd.) was added while paying attention to heat generation, and then heated to 100°C. Further, the reaction was continued at 100°C for 10 hours, 1.0 parts of polyphosphoric acid was added, and the reaction was terminated. Subsequently, purification was performed using a thin film distillation apparatus at a pressure of about 0.02 Torr and a temperature of 160°C until the content of HDI in the urethane prepolymer as a reaction product of HDI became 0.05 mass% in the solid content, whereby a polyisocyanate composition (X-4) was obtained. The NCO% of the polyisocyanate composition (X-4) was 12.9%.

[0267] (Polyisocyanate composition (X'-5))

[0268] In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a condenser, 1000.0 parts of hexamethylene diisocyanate (HDI) was charged, and heated to 60°C while stirring. To this, 0.5 parts of a quaternary ammonium salt was added dropwise, and after reaching a prescribed refractive index, an inactivator was added as appropriate, and the reaction was terminated. Subsequently, purification was performed using a thin film distillation apparatus at a pressure of about 0.02 Torr and a temperature of 160°C until the content of HDI in the urea ester body as a reaction product of HDI became 0.05 mass% in the solid content, whereby a polyisocyanate composition (X'-5) was obtained. The NCO% of the polyisocyanate composition (X'-5) was 21.8%.

[0269] (Polyisocyanate composition (X'-6))

[0270] In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introducing tube, and a condenser, hexamethylene diisocyanate (HDI) 712.9 parts was charged, and heated to 60°C under a stream of nitrogen while stirring. Then, polyoxypropylene sorbitol ether (Sankyo Kasei Co., Ltd. SANNIX SP-750) 186.6 parts, 2-functional polyethylene glycol having a molecular weight of 400 100.5 parts were added while paying attention to heat generation, and then heated to 100°C. Further, the reaction was carried out at 100°C for 10 hours, and then polyphosphoric acid 10.0 parts was added to terminate the reaction. Subsequently, purification was carried out using a thin film distillation apparatus at a pressure of about 0.02 Torr and a temperature of 160°C until the content of HDI in the urethane prepolymer as a reaction product of HDI and polyol became 0.05 mass% in the solid content, whereby a polyisocyanate composition (X'-6) was obtained. The NCO% of the polyisocyanate composition (X'-6) was 11.1%.

[0271] (Polyisocyanate composition (X'-7))

[0272] In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introducing tube, and a condenser, hexamethylene diisocyanate (HDI) 896.1 parts was charged, and heated to 60°C under a stream of nitrogen while stirring. Then, polyglycerol 10 (a polymer of 10 glycerols) 103.9 parts was added while paying attention to heat generation, and then heated to 100°C. Further, the reaction was carried out at 100°C for 10 hours, and then polyphosphoric acid 1.0 parts was added to terminate the reaction. Subsequently, purification was carried out using a thin film distillation apparatus at a pressure of about 0.02 Torr and a temperature of 160°C until the content of HDI in the urethane prepolymer as a reaction product of HDI and polyol became 0.05 mass% in the solid content, whereby a polyisocyanate composition (X'-7) was obtained. The NCO% of the polyisocyanate composition (X'-7) was 15.8%.

[0273] <Preparation of isocyanate-reactive composition (Y)>

[0274] (Isocyanate-reactive composition (Y-1))

[0275] In a polyester reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube, a rectifying tube, and the like, 130 parts of terephthalic acid, 130 parts of isophthalic acid, 150 parts of adipic acid, 50 parts of dimer acid, 70 parts of ethylene glycol, 65 parts of diethylene glycol, 65 parts of neopentyl glycol, and 60 parts of 1,6-hexanediol were added, and esterification was performed at an internal temperature of 250°C. After dehydration, an intermediate polyester polyol having an acid value of 1 mgKOH / g was obtained. This was dissolved and diluted with ethyl acetate to prepare a 65 mass% nonvolatile component solution. Further, with respect to 100 parts of the obtained intermediate polyester polyol solid component, 4 parts of isophorone diisocyanate was added, heated to 80°C, and carbamatic acid esterification was performed until the free NO group substantially disappeared, to obtain an isocyanate-reactive composition (Y-1) having a nonvolatile component of 65 mass% and a hydroxyl value of 6.

[0276] [Assessment]

[0277] [Storage stability of polyisocyanate composition (X)]

[0278] Glass bottles having a capacity of 15 ml were filled with the prepared polyisocyanate compositions (X-1) to (X-4), (X'-5) to (X'-7), respectively, and stored at room temperature for a fixed period. The state of the polyisocyanate compositions (X) after storage was evaluated in two stages according to the following criteria, and the results are summarized in Table 1.

[0279] O: not cured for 30 days or more

[0280] X: cured within 30 days

[0281] [Table 1]

[0282]

[0283] [Preparation of adhesive]

[0284] The polyisocyanate compositions (X) and the isocyanate-reactive compositions (Y) were mixed in the formulation shown in Table 2 to prepare the adhesives of the examples and comparative examples. Note that the polyisocyanate composition (X'-7) had cured, and thus evaluation as an adhesive was not performed.

[0285] [Heat seal strength]

[0286] A biaxially-stretched nylon film having a film thickness of 15 μm was bonded to a 30-μm straight-chain low-density polyethylene film (LLDPE film) as a sealing film using a two-component curable adhesive (3 g / m 2 ) prepared by compounding the components of the examples or comparative examples, and was aged at 40°C for 6 hours to obtain a laminated film.

[0287] The sealing film faces of the laminated film were brought together, and heat-sealed with a 1 cm wide sealing bar at 180°C · 1 kgf / cm 2 · 1 second, and the test piece was cut to 15 mm in width. Using a tensile testing machine, the peak value of the tensile strength when stretching both ends of the test piece was measured with the atmospheric temperature set to 25°C and the peeling speed set to 300 mm / min, and this was taken as the heat-seal strength (N / 15 mm). Evaluation was performed according to the following criteria, and the results are summarized in Table 2.

[0288] O: 30 N / 15 mm or more

[0289] X: less than 30 N / 15 mm

[0290] (Laminating strength)

[0291] A biaxially-stretched PET film having a film thickness of 50 μm and a 30 μm aluminum foil were bonded using the two-component curable adhesive (3 g / m 2 of solid content) compounded in the combinations of the examples or comparative examples, and were allowed to stand at 40°C for 72 hours, to obtain a laminated film.

[0292] A test piece was cut from the laminated film at a width of 15 mm, and the adhesive strength (N / 15 mm) at 180 degree peeling was measured using a tensile testing machine at an atmospheric temperature of 25°C and a peeling speed of 300 mm / min. Evaluation was performed according to the following criteria, and the results are summarized in Table 2.

[0293] O: 5.0 N / 15 mm or more

[0294] X: less than 5.0 N / 15 mm

[0295] [Table 2]

[0296]

Claims

1. A polyisocyanate composition (X) comprising a polyurethane polyisocyanate (A1) as a reaction product of hexamethylene diisocyanate and a polyol having 5 or more and 10 or less hydroxyl groups, and comprising a phosphate derivative (B). The content of the phosphate derivative (B) is above 10 ppm and below 5000 ppm.

2. The polyisocyanate composition (X) according to claim 1, wherein, The polyol has a molecular weight of 200 g / mol or higher and 3000 g / mol or lower.

3. The polyisocyanate composition (X) according to claim 1, wherein, The polyol is selected from: polyether polyols obtained by modifying at least one of xylitol, triglycerides, sorbitol, dipentaerythritol, mannitol, sucrose, and polyglycerol with at least one of ethylene oxide, propylene oxide, butane oxide, and tetrahydrofuran, and at least one of polyglycerol.

4. The polyisocyanate composition (X) according to claim 1, wherein, The polyol is selected from: polyether polyols obtained by modifying sorbitol with at least one selected from ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran, and at least one selected from polyglycerol.

5. The polyisocyanate composition (X) according to claim 1, further comprising a polyurethane polyisocyanate (A2) as a reaction product of hexamethylene diisocyanate and a difunctional polyol.

6. The polyisocyanate composition (X) according to claim 5, wherein, The dual-functional polyol is at least one selected from diethylene glycol and polyether glycol.

7. The polyisocyanate composition (X) according to claim 5, wherein, The difunctional polyol is polyethylene glycol.

8. The polyisocyanate composition (X) according to claim 5, wherein, The molecular weight of the difunctional polyol is above 100 g / mol and below 4000 g / mol.

9. The polyisocyanate composition (X) according to claim 5, wherein, The polyurethane polyisocyanate (A2) accounts for more than 10% by mass and less than 60% by mass in the polyisocyanate composition (X).

10. The polyisocyanate composition (X) according to claim 1, wherein, The content of diisocyanate monomer is less than 0.1% by mass.

11. A two-component curable composition comprising the polyisocyanate composition (X) according to any one of claims 1 to 10, and comprising the isocyanate reactive composition (Y). The isocyanate reactive composition (Y) comprises an isocyanate reactive compound (C).

12. A two-component curable coating agent comprising the polyisocyanate composition (X) according to any one of claims 1 to 10, and comprising the isocyanate reactive composition (Y). The isocyanate reactive composition (Y) comprises an isocyanate reactive compound (C).

13. A two-component curing adhesive comprising the polyisocyanate composition (X) according to any one of claims 1 to 10, and comprising the isocyanate reactive composition (Y). The isocyanate reactive composition (Y) comprises an isocyanate reactive compound (C).

14. The two-component curing adhesive according to claim 13, wherein, The isocyanate reactive compound (C) comprises at least one selected from polyester polyols (C1), polyether polyols (C2), vegetable oil polyols (C3), polyurethane polyols (C4), sugar alcohols (C5), acrylic polyols (C6), amine compounds (C7), and epoxy compounds (C8).

15. A laminate comprising a first substrate, a second substrate, and an adhesive layer disposed between the first substrate and the second substrate, wherein the adhesive layer is a cured coating of the two-component curable adhesive of claim 13.

16. A packaging material formed from the laminate of claim 15.

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