Polyisocyanate compositions, two-component curing compositions, two-component curing coating agents, two-component curing adhesives, laminates, packaging materials

Abstract

The present invention provides a two-component curing adhesive having an excellent balance between reactivity and storage stability, and a polyisocyanate composition suitable for such an adhesive. A polyisocyanate composition (X) containing a polyurethane polyisocyanate (A1) which is a reaction product of hexamethylene diisocyanate and a polyol having 5 to 10 hydroxyl groups, and a phosphoric acid derivative (B), the content of the phosphoric acid derivative (B) being 10 ppm or more and 5,000 ppm or less; and a two-component curing adhesive containing such a polyisocyanate composition (X).

Description

[Technical field]

[0001] The present invention relates to a polyisocyanate composition, a two-component curing composition, a two-component curing coating agent, a two-component curing adhesive, a laminate, and a packaging material. [Background technology]

[0002] Laminates used for various packaging materials, labels, etc. are imparted with design, functionality, storage stability, convenience, transport resistance, etc. by laminating a wide variety of substrates such as plastic films, metal foils, paper, etc. Packaging materials obtained by forming such laminates into bags are used as packaging materials in various fields including food, medicines, detergents, etc.

[0003] Conventionally, laminate films have mainly been produced by a dry lamination method in which a two-component curing adhesive in which a polyisocyanate compound and a polyol compound are dissolved in a volatile organic solvent is applied to a film, the organic solvent is evaporated during the process of passing through an oven, and another film is laminated. In recent years, from the viewpoint of reducing the environmental load and improving the work environment, interest has been focused on two-component curing solventless adhesives in which the polyisocyanate compound and the polyol compound do not contain volatile organic solvents (Patent Document 1, Patent Document 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2014-159548 A [Patent Document 2] JP 2001-172602 A Summary of the Invention [Problem to be solved by the invention]

[0005] In order to improve productivity, there is a demand for improving the reactivity of such two-component curing adhesives. On the other hand, polyisocyanate compounds, which are one component of two-component curing adhesives, react with moisture in the air, so if the reactivity is too high, there is a risk of reducing storage stability. In addition, if the reaction progresses rapidly immediately after mixing the two components, the adhesion between the bonded material and the adhesive tends to decrease.

[0006] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a two-component curing adhesive that has an excellent balance between reactivity and storage stability, and a polyisocyanate composition that is suitable for such an adhesive. [Means for solving the problem]

[0007] That is, the present invention relates to a polyisocyanate composition (X) which contains a polyurethane polyisocyanate (A1) which is a reaction product of hexamethylene diisocyanate and a polyol having 5 to 10 hydroxyl groups, and a phosphoric acid derivative (B), and the content of the phosphoric acid derivative (B) is 10 ppm or more and 5,000 ppm or less, and a two-component curing adhesive which contains such a polyisocyanate composition (X). Effect of the Invention

[0008] According to the present invention, it is possible to provide a two-component curing adhesive having an excellent balance between reactivity and storage stability, and a polyisocyanate composition suitable for such an adhesive. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] <Polyisocyanate composition (X)> (Polyurethane polyisocyanate (A1)) The polyisocyanate composition (X) of the present invention contains a polyurethane polyisocyanate (A1) which is a reaction product of hexamethylene diisocyanate and a polyol having 5 to 10, and more preferably 5 to 8, hydroxyl groups.

[0010] Examples of polyols having 5 to 10 hydroxyl groups used in the synthesis of the polyurethane polyisocyanate (A1) include low molecular weight polyols having 5 to 10 hydroxyl groups, such as xylitol, triglycerol, sorbitol, dipentaerythritol, mannitol, sucrose, and polyglycerol, and polyether polyols obtained by addition polymerization of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexylene, using these low molecular weight polyols as initiators. These polyols can be used alone or in combination of two or more.

[0011] It is preferable to use a polyether polyol obtained by addition polymerization of an alkylene oxide to a low molecular weight polyol having from 5 to 10 hydroxyl groups, or a polyglycerin having from 5 to 10 hydroxyl groups, because a flexible coating film can be formed and, for example, when the polyisocyanate composition (X) of the present invention is made into a two-component curing adhesive described later, the adhesive can have excellent adhesion. 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, and tetrahydrofuran to sorbitol, and a polyglycerin having from 5 to 10 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 and propylene oxide to sorbitol, and a polyglycerin having from 5 to 10 hydroxyl groups.

[0012] The polyol to be used preferably has a molecular weight of 200 g / mol or more and 3000 g / mol or less, more preferably 400 g / mol or more and 3000 g / mol or less, and even more preferably 440 g / mol or more and 2000 g / mol or less.

[0013] The polyurethane polyisocyanate (A1) is obtained by reacting hexamethylene diisocyanate with a polyol under conditions in which the isocyanate groups of hexamethylene diisocyanate are in excess relative to the hydroxyl groups of the polyol. The equivalent ratio of isocyanate groups to hydroxyl groups [NCO] / [hydroxyl groups] can be appropriately adjusted, but is, for example, 2.0 to 20.0.

[0014] The polyisocyanate composition (X) used in the present invention preferably has a content of diisocyanate monomers, i.e., diisocyanate monomers such as aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates, which are exemplified as raw materials for the isocyanate derivative (A3) described later, reduced to 1.0 mass % or less, more preferably 0.1 mass % or less.

[0015] From the viewpoint of occupational safety and health, there is a movement to restrict the use of isocyanate monomers, and the European Commission has adopted the REACH regulation, which prohibits the placing on the market of products containing 0.1% or more by mass of isocyanate monomers unless certain requirements are met. If unreacted diisocyanate monomers are removed until the amount of diisocyanate monomers in the polyisocyanate composition is 0.1% or less by mass, a product that complies with such regulations can be made.

[0016] In addition, when a laminate for food packaging is manufactured using a two-component curing adhesive containing a significant amount of residual aromatic diisocyanate, which is made from aromatic diisocyanate as the isocyanate derivative (A3) described later, unreacted aromatic isocyanate monomer may remain in the adhesive layer. The isocyanate monomer reacts with the surrounding water to become a primary aromatic amine (PAA), which may migrate through the film and leach into the contents (food). There are concerns about the harmfulness of PAA to the human body, and various regulations have been established, such as the European Commission's determination of its detection limit in its regulations on plastic materials and articles for food contact.

[0017] Since PAA reacts with unreacted aromatic isocyanate in the vicinity, the concentration of PAA will gradually decrease even if aromatic isocyanate remains in the adhesive layer. Eventually it will fall below the detection limit, but from the viewpoint of the manufacturing efficiency of laminates for food packaging, it is preferable that the initial value of aromatic isocyanate monomer remaining in the adhesive layer is low. By removing the diisocyanate monomer in advance, it is possible to create a two-component curing adhesive with excellent manufacturing efficiency.

[0018] The diisocyanate monomer can be removed by distilling the diisocyanate monomer under reduced pressure using a short-path distillation apparatus, a thin-film distillation apparatus, etc. The degree of reduced pressure and the distillation temperature are appropriately adjusted depending on the diisocyanate monomer to be removed, and are, for example, 0.1 mbar or less and 120° C. to 190° C. The diisocyanate monomer removal step may be carried out multiple times.

[0019] The content of diisocyanate monomers can be measured, for example, by gas chromatography using an internal standard according to ASTM D 3432. Alternatively, it can be measured by liquid chromatography according to the following conditions.

[0020] Equipment: Waters Corporation "ACQUITY UPLC H-Class" Data processing: Waters Corporation "Empower-3" Column: Waters Corporation "ACQUITY UPLC HSS T3" (100 mm x 2.1 mmφ, 1.8 μm) 40℃ Eluent: ammonium formate aqueous solution / methanol, 0.3 mL / min Detector: PDA Sample preparation: 1. Dissolve 100 mg of appropriately blocked sample in 10 ml of THF (for LC) 2. Vortex for 30 seconds. 3. Dilute appropriately with eluent (mobile phase) 4. The solution was passed through a 0.2 μm filter to prepare a measurement sample. Calculation of area ratio: Calculate using the maximum absorption wavelength for the target substance.

[0021] (Polyurethane polyisocyanate (A2)) It is also preferred that the polyisocyanate composition (X) contains a polyurethane polyisocyanate (A2) which is a reaction product of hexamethylene diisocyanate and a bifunctional polyol. This allows the polyisocyanate composition (X) to have a better balance of reactivity, storage stability, and coatability. In addition, when used as a two-component curing composition described later, it is possible to form a coating film having appropriate flexibility, and when applied to a flexible substrate, it is possible to improve adhesion to the substrate.

[0022] Examples of the bifunctional polyol used in the synthesis of the polyurethane polyisocyanate (A2) include aliphatic diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol, and polyether diols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexylene using these aliphatic diols as initiators, and these can be used alone or in combination of two or more.

[0023] The molecular weight of the bifunctional polyol is, for example, 8000 g / mol or less, and more preferably 100 g / mol or more and 4000 g / mol or less.

[0024] When the polyisocyanate composition (X) contains a polyurethane polyisocyanate (A2), the blending amount thereof can be appropriately adjusted. 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 mass% or more.

[0025] When the polyisocyanate composition (X) contains a polyurethane polyisocyanate (A2), the polyurethane polyisocyanate (A1) and the polyurethane polyisocyanate (A2) may be mixed after being synthesized separately, or hexamethylene diisocyanate, a polyol having 5 to 10 hydroxyl groups, and a bifunctional polyol may be reacted under conditions in which the isocyanate groups of hexamethylene diisocyanate are in excess relative to the hydroxyl groups of the polyol, and then unreacted diisocyanate monomers may be removed as necessary to obtain a mixture of polyurethane polyisocyanate (A1) and polyurethane polyisocyanate (A2). The equivalent ratio of isocyanate groups to hydroxyl groups [NCO] / [hydroxyl groups] may be appropriately adjusted, and is, for example, 2.0 to 20.0.

[0026] When polyurethane polyisocyanate (A2) is synthesized separately, it is obtained by reacting hexamethylene diisocyanate with a bifunctional polyol under conditions in which the isocyanate groups of hexamethylene diisocyanate are in excess relative to the hydroxyl groups of the bifunctional polyol, and then removing unreacted diisocyanate monomers as necessary. The equivalent ratio of isocyanate groups to hydroxyl groups [NCO] / [hydroxyl groups] can be appropriately adjusted, but is, for example, 2.0 to 20.0.

[0027] (Isocyanate derivative (A3)) The polyisocyanate composition (X) may contain an isocyanate derivative (A3) other than the polyurethane polyisocyanate (A1) and polyurethane polyisocyanate (A2) in order to improve the storage stability and coatability of the polyisocyanate composition (X) and to improve the flexibility of the coating film when used as a two-component curing composition described later. Examples of the isocyanate derivative (A3) include conventionally known aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and biuret, nurate, adduct, allophanate, carbodiimide-modified, uretdione-modified, and polyurethane polyisocyanates other than (A1) and (A2), and one or more of them may be used in combination.

[0028] Examples of aromatic diisocyanates include 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (also called MDI), polymethylene polyphenyl polyisocyanate (also called polymeric MDI or crude MDI), 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate (also called PPDI), 2,4-tolylene diisocyanate, and the like. Examples of the isocyanate include, but are not limited to, 2,6-tolylene diisocyanate (also known as TDI), 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, tolidine diisocyanate (also known as TODI), dianisidine diisocyanate, naphthalene diisocyanate (also known as NDI), 4,4'-diphenyl ether diisocyanate, and 4,4',4"-triphenylmethane triisocyanate.

[0029] The araliphatic diisocyanate means an aliphatic isocyanate having one or more aromatic rings in the molecule, and examples thereof include, but are not limited to, m- or p-xylylene diisocyanate (also known as XDI), α,α,α',α'-tetramethylxylylene diisocyanate (also known as TMXDI), and the like.

[0030] Examples of aliphatic diisocyanates include, but are not limited to, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate (also known as PDI), 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate (also known as LDI).

[0031] Examples of alicyclic diisocyanates include, but are not limited to, 3-isocyanatemethyl-3,5,5-trimethylcyclohexyl isocyanate, isophorone diisocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebiscyclohexyl isocyanate (also known as hydrogenated MDI or HMDI), 1,3-bis(isocyanatemethyl)cyclohexane (also known as hydrogenated XDI or HXDI), hydrogenated TMXDI, and norbornane diisocyanate (also known as NBDI).

[0032] Examples of polyols that can be used in the synthesis of polyurethane polyisocyanates other than (A1) and (A2) include glycols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol;

[0033] Trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, and pentaerythritol; Bisphenols such as bisphenol A, bisphenol F, hydrogenated bisphenol A, and hydrogenated bisphenol F; Dimer diol;

[0034] Polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexylene in the presence of a polymerization initiator such as the above-mentioned glycols and trifunctional or tetrafunctional aliphatic alcohols;

[0035] polyester polyols (1), which are reaction products of polyesters obtained by ring-opening polymerization of cyclic ester compounds such as propiolactone, butyrolactone, ε-caprolactone, σ-valerolactone, β-methyl-σ-valerolactone, etc., with polyhydric alcohols such as the above-mentioned glycols, glycerin, trimethylolpropane, pentaerythritol, etc.; Polyester polyol (2) obtained by reacting a difunctional polyol such as the glycol, dimer diol, or bisphenol with a polycarboxylic acid: (3) a polyester polyol obtained by reacting a trifunctional or tetrafunctional aliphatic alcohol with a polycarboxylic acid; (4) a polyester polyol obtained by reacting a difunctional polyol with the above-mentioned trifunctional or tetrafunctional aliphatic alcohol and a polycarboxylic acid; Polyester polyols (5), which are polymers of hydroxyl acids such as dimethylolpropionic acid and castor oil fatty acid;

[0036] a polyether polyurethane polyol obtained by polymerizing the polyether polyol with an isocyanate compound; a polyester polyether polyurethane polyol obtained by reacting at least one of the polyester polyols (1) to (5), a polyether polyol, and an isocyanate compound; A polyester polyurethane polyol obtained by polymerizing the polyester polyols (1) to (5) with an isocyanate compound;

[0037] Examples of the polyol include castor oil-based polyols such as castor oil, dehydrated castor oil, hydrogenated castor oil, and 5 to 50 mole alkylene oxide adducts of castor oil, and mixtures of these polyols. These polyols can be used alone or in combination of two or more kinds.

[0038] Examples of the polyvalent carboxylic acid used in the synthesis of the polyester polyols (2) to (4) include aromatic polybasic acids such as orthophthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride, naphthalic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid, benzophenonetetracarboxylic acid, benzophenonetetracarboxylic dianhydride, 5-sodium sulfoisophthalic acid, tetrachlorophthalic anhydride, and tetrabromophthalic anhydride; Methyl esters of aromatic polybasic acids such as dimethyl terephthalic acid and dimethyl 2,6-naphthalenedicarboxylate;

[0039] Aliphatic polybasic acids such as malonic acid, succinic acid, succinic anhydride, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, maleic anhydride, and itaconic acid; Alkyl esters of aliphatic polybasic acids, such as dimethyl malonate, diethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, diethyl pimelate, diethyl sebacate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, and diethyl maleate;

[0040] Examples of the polybasic acids include alicyclic polybasic acids such as 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, himic anhydride, and HET acid anhydride. These may be used alone or in combination of two or more.

[0041] When the polyisocyanate composition (X) contains an isocyanate derivative (A3), the content of the polyurethane polyisocyanate (A1) in the total amount of the polyurethane polyisocyanate (A1) and the isocyanate derivative (A3) is preferably 40 mass % or more.

[0042] (Phosphate derivative (B)) Examples of the phosphoric acid derivative (B) include phosphoric acid, pyrophosphoric acid, triphosphoric acid, methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, dibutyl phosphate, 2-ethylhexyl acid phosphate, bis(2-ethylhexyl)phosphate, isododecyl acid phosphate, butoxyethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, polyoxyethylene alkyl ether phosphoric acid, etc. Phosphoric acid, pyrophosphoric acid, triphosphoric acid, and butyl acid phosphate are preferred.

[0043] The content of the phosphoric acid derivative (B) in the polyisocyanate composition (X) of the present invention is 10 ppm or more and 5000 ppm or less. This makes it possible to obtain a polyisocyanate composition (X) excellent in reactivity and storage stability. 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.

[0044] The phosphoric acid derivative (B) is preferably added after the completion of the urethanization of the polyurethane polyisocyanate (A1). When the polyurethane polyisocyanate is produced through a step of removing unreacted isocyanate monomers, the phosphoric acid derivative (B) may be added after the completion of the urethanization reaction of the polyurethane polyisocyanate (A1) and before removing the unreacted isocyanate monomers, or may be added after removing the isocyanate monomers.

[0045] <Two-component curable composition> The polyisocyanate composition (X) of the present invention can be used as a two-liquid curing composition in combination with an isocyanate-reactive composition containing a compound reactive with isocyanate. Examples of the compound reactive with isocyanate include 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, etc.

[0046] Such two-component curing compositions can be used, for example, as adhesives, coatings, sealants, elastomers, and the like.

[0047] <Two-component curing coating agent> The two-component curing coating agent of the present invention contains the above-mentioned polyisocyanate composition (X) and isocyanate-reactive composition (Y). The coating agent of the present invention can be suitably used for various applications, but since it has excellent adhesion to metal materials, it is particularly suitable for use as a coating agent for metal substrates such as aluminum and steel plates, as an overcoat for coating films containing aluminum pigments or metal particles, as a coating agent for electrical parts, and as an electrical insulator.

[0048] The isocyanate-reactive composition (Y) contains a compound (C) having a plurality of functional groups reactive 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), epoxy compound (C8), etc. The isocyanate-reactive compound (C) can be used alone or in combination of two or more kinds.

[0049] Examples of the polyester polyol (C1) include polyester polyols which are reaction products of polyhydric alcohols and polycarboxylic acids, and lactone-based polyester polyols obtained by polycondensation reaction of aliphatic polyols and various lactones such as ε-caprolactone. It is preferable to use polyester polyols which are reaction products of polyhydric alcohols and polycarboxylic acids.

[0050] Examples of polyhydric alcohols include aliphatic diols such as ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,2,2-trimethyl-1,3-propanediol, 2,2-dimethyl-3-isopropyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-bis(hydroxymethyl)cyclohexane, and 2,2,4-trimethyl-1,3-pentanediol;

[0051] aliphatic polyols having three or more functional groups, such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, and pentaerythritol;

[0052] Bisphenols such as bisphenol A and bisphenol F; Alkylene oxide adducts of bisphenols obtained by adding ethylene oxide, propylene oxide, etc. to bisphenols such as bisphenol A and bisphenol F;

[0053] Examples of such polyether polyols include polyether polyols obtained by ring-opening polymerization of an aliphatic diol or polyol with various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether. These polyether polyols can be used alone or in combination of two or more kinds.

[0054] Examples of polycarboxylic acids include aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid; Aromatic dicarboxylic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, and 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid; and anhydride or ester forming derivatives of these aliphatic or dicarboxylic acids; Examples of the acid include p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid, and ester-forming derivatives of these dihydroxycarboxylic acids, and polybasic acids such as dimer acid. These can be used alone or in combination of two or more kinds.

[0055] The molecular weight of the polyester polyol (C1) is preferably 250 g / mol or more and 20,000 g / mol or less, and more preferably 500 g / mol or more and 10,000 g / mol or less. The polyester polyol (C1) preferably has a hydroxyl value of 5 mgKOH / g or more and 500 mgKOH / g or less.

[0056] Examples of the polyether polyol (C2) include those obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexylene in the presence of a polymerization initiator.

[0057] Examples of the polymerization initiator include glycols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and triethylene glycol;

[0058] Trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, pentaerythritol, and triols of polypropylene glycol;

[0059] Examples of the amine compounds include primary or secondary alkylamines such as ethylamine and diethylamine, amine compounds having a plurality of amino groups such as methylenediamine and ethylenediamine, and amine compounds having an active hydrogen group such as primary or secondary alkanolamines such as monoethanolamine and diethanolamine.

[0060] The molecular weight of the polyether polyol (C2) can be appropriately adjusted, but is preferably, for example, from 100 g / mol to 8000 g / mol. The hydroxyl value of the polyether polyol (C2) can be appropriately adjusted, but is preferably, for example, from 10 mgKOH / g to 1200 mgKOH / g.

[0061] Examples of the vegetable oil polyol (C3) include castor oil, dehydrated castor oil, hardened castor oil which is a hydrogenated castor oil, and an alkylene oxide 5 to 50 mole adduct of castor oil.

[0062] 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 polyhydric alcohols as those exemplified as the raw material of the polyester polyol (C1) can be used. As the polyisocyanate compound, the same compounds as those exemplified as the raw material of the isocyanate derivative (A3) can be used.

[0063] Examples of sugar alcohols (C5) include pentaerythritol, sucrose, xylitol, sorbitol, isomalt, lactitol, maltitol, and mannitol.

[0064] The acrylic polyol (C6) is obtained by copolymerizing a (meth)acrylic acid ester having a hydroxyl group as an essential component and, if necessary, a polymerizable unsaturated monomer. In this specification, (meth)acrylic acid means methacrylic acid or acrylic acid. Examples of the (meth)acrylic acid ester having a hydroxyl group include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate, and one or more of them can be used in combination.

[0065] Examples of the polymerizable unsaturated monomer include alkyl (meth)acrylates having an alkyl group having 1 to 22 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate; Aralkyl (meth)acrylates such as benzyl (meth)acrylate and 2-phenylethyl (meth)acrylate; cycloalkyl (meth)acrylates such as cyclohexyl (meth)acrylate and isobornyl (meth)acrylate; ω-alkoxyalkyl (meth)acrylates such as 2-methoxyethyl (meth)acrylate and 4-methoxybutyl (meth)acrylate; polyfunctional (meth)acrylates such as ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and dipentaerythritol hexa(meth)acrylate;

[0066] (Meth)acrylic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, 4-methylcyclohex-4-ene-1,2-dicarboxylic anhydride, bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride, 1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic anhydride, 2-octa-1,3-diketospiro[4.4]non-7-ene, bicyclo[ 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-norbornene-5-ene-2,3-dicarboxylic anhydride, norborn-5-ene-2,3-dicarboxylic anhydride, sulfonated styrene, vinylbenzenesulfonamide, and other polymerizable unsaturated monomers having an acid group; Vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl pivalate, and vinyl benzoate; Alkyl esters of crotonic acid such as methyl crotonate and ethyl crotonate; Examples of the dialkyl esters of unsaturated dibasic acids include, but are not limited to, dimethyl maleate, di-n-butyl maleate, dimethyl fumarate, dimethyl itaconate, etc. These may be used alone or in combination of two or more.

[0067] The amine compound (C7) is a compound having an amino group. In this specification, the amino group refers to an NH group or an NHR group (R is an alkyl group or an aryl group which may have a functional group).

[0068] As the amine compound (C7), known compounds can be used without any particular limitation, and examples thereof include methylenediamine, ethylenediamine, isophoronediamine, 3,9-dipropanamine-2,4,8,10-tetraoxaspirodoundecane, lysine, 2,2,4-trimethylhexamethylenediamine, hydrazine, piperazine, 2-hydroxyethylethylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, poly(propylene glycol)diamine, poly(propylene glycol)triamine, poly(propylene glycol)tetraamine, 1,2-diaminopropane, 1,3-diaminopropane,

[0069] 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, nonaethylenedecamine, trimethylhexamethylenediamine, tetra(aminomethyl)methane, tetrakis(2-aminoethylaminomethyl)methane, 1,3-bis(2'-aminoethylamino)propane, triethylene-bis(trimethylene)hexamine, bis(3-aminoethyl)amine, bishexamethylenetriamine, 1,4-cyclohexanediamine, 4,4'-methylenebiscyclohexylamine, 4,4'-isopropylidenebiscyclohexylamine, norbornadiamine,

[0070] amine compounds (C7-1) having a plurality of amino groups, such as bis(aminomethyl)cyclohexane, diaminodicyclohexylmethane, isophoronediamine, menthenediamine, bis(cyanoethyl)diethylenetriamine, 1,4-bis-(8-aminopropyl)-piperazine, piperazine-1,4-diazacycloheptane, 1-(2'-aminoethylpiperazine), 1-[2'-(2"-aminoethylamino)ethyl]piperazine, tricyclodecanediamine, and polyureaamines which are reaction products of the above-mentioned various polyamines and the above-mentioned various isocyanate components;

[0071] Primary or secondary alkanolamines (C7-2) such as monoethanolamine, monoisopropanolamine, monobutanolamine, N-methylethanolamine, N-ethylethanolamine, N-methylpropanolamine, diethanolamine, and diisopropanolamine;

[0072] Examples of the amines include primary or secondary amines (C7-3) such as ethylamine, octylamine, laurylamine, myristylamine, stearylamine, oleylamine, diethylamine, dibutylamine, and distearylamine.

[0073] The amount of the amine compound (C7) to be blended can be adjusted appropriately depending on the purpose. As an example, it is preferable to blend it so that the amine value of the isocyanate-reactive composition (Y) is 20 to 70 mg KOH / g, more preferably 25 to 50 mg KOH / g.

[0074] In this specification, the amine value means the number of milligrams of KOH equivalent to the amount of HCl required to neutralize 1 g of sample, and is not particularly limited and can be calculated using a known method. When the chemical structure of the amine compound (E7) and, if necessary, the average molecular weight, etc. are known, the amine value can be calculated from (number of amino groups per molecule / average molecular weight) x 56.1 x 1000. When the chemical structure, average molecular weight, etc. of the amine compound are unknown, the amine value can be measured according to a known amine value measurement method, for example, JIS K7237-1995.

[0075] The epoxy compound (C8) is not particularly limited as long as it is a compound having an epoxy group in the molecule, and examples thereof include polyglycidyl ether type epoxy resins of aliphatic polyols such as ethylene glycol, propylene glycol, hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol, glycerin, diglycerin, sorbitol, spiroglycol, or hydrogenated bisphenol A; Bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD ​​type epoxy resin, etc.;

[0076] Aromatic epoxy resins such as novolac-type epoxy resins, which are glycidyl ethers of phenol novolac resins and cresol novolac resins; Polyglycidyl ethers of polyols, which are ethylene oxide or propylene oxide adducts of aromatic polyhydroxy compounds such as bisphenol A, bisphenol F, bisphenol S, and bisphenol AD; Polyglycidyl ether type epoxy resins of polyether polyols such as polyethylene glycol, polypropylene glycol, or polytetramethylene glycol; cyclic aliphatic type polyepoxy resins such as bis(3,4-epoxycyclohexylmethyl)adipate and 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate;

[0077] Polyglycidyl ester type epoxy resins of polycarboxylic acids such as propanetricarboxylic acid, butanetetracarboxylic acid, adipic acid, phthalic acid, terephthalic acid, and trimellitic acid; Bisepoxy resins of hydrocarbon dienes such as butadiene, hexadiene, octadiene, dodecadiene, cyclooctadiene, α-pinene or vinylcyclohexene; Epoxy resins of diene polymers such as polybutadiene or polyisoprene; glycidylamine-type epoxy resins such as tetraglycidyldiaminodiphenylmethane, triglycidyl paraaminophenol, tetraglycidylbisaminomethylcyclohexane, diglycidylaniline, and tetraglycidylmeta-xylylenediamine; Examples of the epoxy resin include those containing a heterocycle such as triazine or hydantoin. These may be used alone or in combination of two or more.

[0078] The isocyanate-reactive compound (C) preferably contains a bifunctional compound. This improves the flexibility of the cured coating film and provides a coating agent with better adhesion to the substrate. The content of the bifunctional compound in the isocyanate-reactive compound (C) can be appropriately adjusted, and is, for example, 50% by mass or more, and 80% by mass or more. The entire amount of the isocyanate-reactive compound (C) may be a bifunctional compound.

[0079] The isocyanate-reactive compound (C) preferably contains one having a glass transition temperature (Tg) of 15° C. or more. This makes it possible to obtain a coating agent in which blocking is suppressed. The upper limit of the glass transition temperature of the isocyanate-reactive compound (C) can be appropriately adjusted depending on the purpose, and is, for example, 80° C. or less.

[0080] The coating agent of the present invention may contain a solvent. Examples of the solvent that can be used in the coating agent of the present invention include esters such as ethyl acetate, butyl acetate, and cellosolve acetate, ketones such as acetone, methyl ethyl ketone, isobutyl ketone, and cyclohexanone, ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, dimethyl sulfoxide, and dimethyl sulfamide, and can be used alone or in combination of two or more.

[0081] The coating agent of the present invention may contain additives such as a urethanization catalyst, an organic filler, an inorganic filler, an organic pigment, an inorganic pigment, an extender pigment, a clay mineral, a wax, a surfactant, a stabilizer, a flow adjuster, a leveling agent, a rheology control agent, an ultraviolet absorber, an antioxidant, a plasticizer, etc. As the urethanization catalyst and pigment, the same ones as those used in the two-component curing adhesive described later can be used.

[0082] The method of applying the coating agent is not particularly limited, and any conventionally known method can be used. Examples include various coating methods such as spray coating, direct gravure coating, gravure kiss reverse coating, offset gravure coating, flexo coating, offset coating, bar coating, roll kiss coating, positive rotation roll coating, reverse roll coating, slot die coating, vacuum die coating, (micro)chamber doctor coating, air doctor coating, blade coating, knife coating, spin coating, and dipping coating.

[0083] The amount of coating agent applied can be adjusted as appropriate. For example, the amount is 10 g / m 2 More than 100g / m 2 The following is the result.

[0084] The two-component curing coating agent of the present invention is preferably used by mixing the polyisocyanate composition (X) with the molar number [NCO] of the isocyanate group contained in the isocyanate-reactive composition (Y) so that the ratio [NCO] / [isocyanate-reactive functional group] of the molar number of functional groups reactive with isocyanate contained in the isocyanate-reactive composition (Y) is 0.5 to 5.0, more preferably 1.0 to 3.0. This allows for appropriate curing properties to be obtained without depending on the environmental humidity during coating.

[0085] <Two-component curing adhesive> The two-component curing adhesive of the present invention contains the above-mentioned polyisocyanate composition (X) and an isocyanate-reactive composition (Y).

[0086] When the adhesive of the present invention is used as a solventless adhesive, the viscosity of the polyisocyanate composition (X) is adjusted to a range suitable for the non-solvent lamination method. For example, the viscosity at 40°C is adjusted to be in the range of 100 to 50,000 mPas, more preferably 500 to 20,000 mPas. The viscosity of the polyisocyanate composition (X) can be adjusted, for example, by the structure of the polyurethane polyisocyanate (A1) (the polyol used). The viscosity of the polyisocyanate composition (X) is measured, for example, using a rotational viscometer with a cone and plate of 1°×diameter 50 mm and a shear rate of 100 sec. -1 , can be measured at 40°C±1°C.

[0087] When the adhesive of the present invention is used as a solvent-based adhesive, the viscosity of the polyisocyanate composition (X) can be adjusted by diluting it with a solvent described below.

[0088] (Isocyanate-reactive composition (Y)) The isocyanate-reactive composition (Y) contains an isocyanate-reactive compound (C). As the isocyanate-reactive compound (C), one or more of the compounds similar to those used in the above-mentioned coating agent can be used in combination.

[0089] The isocyanate-reactive compound (C) preferably contains a bifunctional compound. This improves the flexibility of the cured coating film of the adhesive, and makes it possible to obtain an adhesive with superior adhesion and adhesion to the substrate. The content of the bifunctional compound in the isocyanate-reactive compound (C) can be appropriately adjusted, and is, for example, 50% by mass or more, and 80% by mass or more. The entire amount of the isocyanate-reactive compound (C) may be a bifunctional compound.

[0090] The isocyanate-reactive compound (C) preferably contains one having a glass transition temperature (Tg) of 40° C. or less. This makes it possible to obtain an adhesive with excellent adhesiveness. The lower limit of the glass transition temperature of the isocyanate-reactive compound (C) can be appropriately adjusted depending on the purpose, and is, for example, −50° C. or more.

[0091] (Monool compound (D)) The isocyanate-reactive composition (Y) may contain a mono-ol compound (D) having one alcoholic hydroxyl group. The main chain of the mono-ol compound (D) is not particularly limited, and examples thereof include vinyl resins, acrylic resins, polyesters, epoxy resins, and urethane resins having one hydroxyl group. Aliphatic alcohols and alkyl alkylene glycols can also be used. The main chain of the mono-ol compound (D) may be linear or branched. The bonding position of the hydroxyl group is not particularly limited, but it is preferable that the hydroxyl group is present at the end of the molecular chain.

[0092] Specific examples of the monool compound (D) include aliphatic monools such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, lauryl alcohol, myristyl alcohol, pentadecanol, cetyl alcohol, heptadecanol, stearyl alcohol, nonadecanol, other alkanols (C20 to C50), oleyl alcohol, and isomers thereof;

[0093] Cyclohexanol, methylcyclohexanol, 4-butylcyclohexanol, 4-pentylcyclohexanol, 4-hexylcyclohexanol, cyclodecanol, cyclododecanol, cyclopentadecanol, 4-isopropylcyclohexanol, 3,5,5-trimethylcyclohexanol, menthol, 2-norbornanol, borneol, 2-adamantanol, dicyclohexylmethanol, decitol, 2-cyclohexylcyclohexanol, 4-cyclohexylcyclohexanol, 4-(4-propylcyclohexyl)cyclohexanol, 4-(4-pentylcyclohex cyclohexanol, α-ambrinol, desoxycorticosterone, 11-dehydrocorticosterone, cholesterol, β-sitosterol, campesterol, stigmasterol, brassicasterol, lanosterol, ergosterol, β-cholestanol, testosterone, estrone, digitoxigenin, dehydroepiandrosterone, coprostanol, pregnenolone, epicholestanol, 7-dehydrocholesterol, estradiol benzoate, tigogenin, hecogenin, methandienone, cortisone acetate, stenolone, and isomers thereof, and other alicyclic monools;

[0094] aromatic aliphatic monools such as benzyl alcohol;

[0095] Examples of the polyoxyalkylene monool include polyoxyalkylene monools obtained by ring-opening addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran using an alkyl compound containing one active hydrogen as an initiator.

[0096] When the adhesive of the present invention is provided in a solventless form, the viscosity of the isocyanate-reactive composition (Y) is adjusted to a range suitable for the non-solvent lamination method. For example, the viscosity at 40°C is adjusted to be in the range of 100 to 50,000 mPas, more preferably 100 to 20,000 mPas. The viscosity of the isocyanate-reactive composition (Y) can be adjusted by the skeleton of the isocyanate-reactive compound (C) or the plasticizer described below.

[0097] (Other components of adhesive) The two-component curing adhesive of the present invention may contain components other than those mentioned above. The other components may be contained in either or both of the polyisocyanate composition (X) and the isocyanate-reactive composition (Y), or may be prepared separately from these and mixed with the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) immediately before application of the adhesive. Each component will be described below.

[0098] (catalyst) Examples of the catalyst include metal catalysts, amine catalysts, aliphatic cyclic amide compounds, and quaternary ammonium salts.

[0099] Examples of the metal catalyst include metal complex catalysts, inorganic metal catalysts, and organic metal catalysts. Examples of the metal complex catalyst include acetylacetonate salts of metals selected from the group consisting of Fe (iron), Mn (manganese), Cu (copper), Zr (zirconium), Th (thorium), Ti (titanium), Al (aluminum), and Co (cobalt), such as iron acetylacetonate, manganese acetylacetonate, copper acetylacetonate, and zirconia acetylacetonate.

[0100] Examples of inorganic metal catalysts include those selected from Sn, Fe, Mn, Cu, Zr, Th, Ti, Al, Co, etc.

[0101] Examples of the organometallic catalyst include organozinc compounds such as zinc octylate, zinc neodecanoate, and zinc naphthenate; organotin compounds such as stannous diacetate, stannous dioctoate, stannous dioleate, stannous dilaurate, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin oxide, and dibutyltin dichloride; organonickel compounds such as nickel octylate and nickel naphthenate; organocobalt compounds such as cobalt octylate and cobalt naphthenate; organobismuth compounds such as bismuth octylate, bismuth neodecanoate, and bismuth naphthenate; titanium compounds such as tetraisopropyloxytitanate, dibutyltitanium dichloride, tetrabutyltitanium, butoxytitanium trichloride, aliphatic diketones, aromatic diketones, and titanium chelate complexes having at least one of alcohols having 2 to 10 carbon atoms as a ligand.

[0102] Examples of the amine catalyst include triethylenediamine, 2-methyltriethylenediamine, quinuclidine, 2-methylquinuclidine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N',N",N"-pentamethyl-(3-aminopropyl)ethylenediamine, N,N,N',N",N"-pentamethyldipropylenetriamine, N,N,N',N'-tetramethylhexamethylenediamine, bis(2-dimethylaminoethyl)ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol, N,N-dimethyl-N'-(2-hydroxyethyl)ethylenediamine, N,N-dimethyl-N'-(2-hydroxyethyl)propanediamine, bis(dimethylaminopropyl)amine, bis(dimethylaminopropyl)isopropanediamine, and the like. lopanolamine, 3-quinuclidinol, N,N,N',N'-tetramethylguanidine, 1,3,5-tris(N,N-dimethylaminopropyl)hexahydro-S-triazine, 1,8-diazabicyclo[5.4.0]undecene-7, N-methyl-N'-(2-dimethylaminoethyl)piperazine, N,N'-dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, 1-methylimidazole, 1 ,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.

[0103] Examples of the aliphatic cyclic amide compound include δ-valerolactam, ε-caprolactam, ω-enantholactam, η-capryllactam, β-propiolactam, etc. Among these, ε-caprolactam is more effective in promoting hardening.

[0104] Examples of quaternary ammonium salts include hydroxy salts of alkyl ammonium, aromatic ammonium, etc., alkyl acid salts, halide salts, etc. Examples include, but are not limited to, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltriethylammonium chloride, hexadecyltrimethylammonium bromide, etc.

[0105] (Coupling Agent) Examples of the coupling agent include a silane coupling agent, a titanate-based coupling agent, and an aluminum-based coupling agent.

[0106] Examples of the silane coupling agent include aminosilanes such as γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, and bis[3-(triethoxysilyl)propyl]amine; epoxysilanes such as β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane; vinylsilanes such as vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane; and hexamethyldisilazane and γ-mercaptopropyltrimethoxysilane.

[0107] Examples of titanate coupling agents include tetraisopropoxytitanium, tetra-n-butoxytitanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, titanium lactate, and tetrastearoxytitanium.

[0108] An example of the aluminum-based coupling agent is acetoalkoxyaluminum diisopropylate.

[0109] (Pigments) The pigment is not particularly limited, and examples thereof include organic pigments and inorganic pigments such as extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments, green pigments, blue pigments, metal powder pigments, luminescent pigments, and pearlescent pigments listed in the Paint Raw Materials Handbook 1970 Edition (compiled by the Japan Paint Manufacturers Association), as well as plastic pigments.

[0110] Examples of extender pigments include precipitated barium sulfate, powdered gourd, precipitated calcium carbonate, calcium bicarbonate, kansui stone, alumina white, silica, hydrous fine silica (white carbon), ultrafine anhydrous silica (aerosil), silica sand, talc, precipitated magnesium carbonate, bentonite, clay, kaolin, and yellow earth.

[0111] Specific examples of organic pigments include various insoluble azo pigments such as Benzidine Yellow, Hansa Yellow, Lake 4R, etc.; soluble azo pigments such as Lake C, Carmine 6B, Bordeaux 10, etc.; various (copper) phthalocyanine pigments such as Phthalocyanine Blue, Phthalocyanine Green, etc.; various chlorine dyeing lakes such as Rhodamine Lake, Methyl Violet Lake, etc.; various mordant dye pigments such as Quinoline Lake, Fast Sky Blue, etc.; various vat dye pigments such as Anthraquinone pigments, Thioindigo pigments, Perinone pigments, etc.; various quinacridone pigments such as Synchasia Red B, etc.; various dioxazine pigments such as Dioxazine Violet, etc.; various condensed azo pigments such as Chromophtal, etc.; aniline black, etc.

[0112] Examples of inorganic pigments include various chromates such as yellow lead, zinc chromate, and molybdate orange; various ferrocyanide compounds such as Prussian blue; various metal oxides such as titanium oxide, zinc oxide, mapico yellow, iron oxide, red iron oxide, chrome oxide green, and zirconium oxide; various sulfides or selenides such as cadmium yellow, cadmium red, and mercury sulfide; various sulfates such as barium sulfate and lead sulfate; various silicates such as calcium silicate and ultramarine; various carbonates such as calcium carbonate and magnesium carbonate; various phosphates such as cobalt violet and manganese purple; various metal powder pigments such as aluminum powder, gold powder, silver powder, copper powder, bronze powder, and brass powder; flake pigments of these metals, mica flake pigments; metallic pigments and pearl pigments such as mica flake pigments coated with metal oxides and micaceous iron oxide pigments; graphite, carbon black, and the like.

[0113] Examples of plastic pigments include "Grandol PP-1000" and "PP-2000S" manufactured by DIC Corporation.

[0114] The pigment to be used may be appropriately selected depending on the purpose. For example, it is preferable to use inorganic oxides such as titanium oxide and zinc oxide as white pigments because they have excellent durability, weather resistance, and design properties, and it is preferable to use carbon black as a black pigment.

[0115] The amount of the pigment is, for example, 1 to 400 parts by mass per 100 parts by mass of the total amount of the non-volatile content of the polyol composition (X) and the polyisocyanate composition (Y), and more preferably 10 to 300 parts by mass to improve adhesion and blocking resistance.

[0116] (Plasticizer) Examples of the plasticizer include phthalic acid plasticizers, fatty acid plasticizers, aromatic polycarboxylic acid plasticizers, phosphoric acid plasticizers, polyol plasticizers, epoxy plasticizers, polyester plasticizers, and carbonate plasticizers.

[0117] Examples of the phthalic acid plasticizer include phthalic acid ester plasticizers such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, diheptyl phthalate, di-(2-ethylhexyl) phthalate, di-n-octyl phthalate, dinonyl phthalate, diisononyl phthalate, didecyl phthalate, diisodecyl phthalate, ditridecyl phthalate, diundecyl phthalate, dilauryl phthalate, distearyl phthalate, diphenyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, dicyclohexyl phthalate, octyl decyl phthalate, dimethyl isophthalate, di-(2-ethylhexyl) isophthalate, and diisooctyl isophthalate; and tetrahydrophthalic acid ester plasticizers such as di-(2-ethylhexyl) tetrahydrophthalate, di-n-octyl tetrahydrophthalate, and diisodecyl tetrahydrophthalate.

[0118] Examples of fatty acid plasticizers include adipic acid plasticizers such as di-n-butyl adipate, di-(2-ethylhexyl) adipate, diisodecyl adipate, diisononyl adipate, di(C6-C10 alkyl) adipate, and dibutyl diglycol adipate; azelaic acid plasticizers such as di-n-hexyl azelate, di-(2-ethylhexyl) azelate, and diisooctyl azelate; and di-n-butyl sebacate, di-(2 Sebacic acid plasticizers such as di-n-ethylhexyl) sebacate and diisononyl sebacate; maleic acid plasticizers such as dimethyl maleate, diethyl maleate, di-n-butyl maleate and di-(2-ethylhexyl) maleate; fumaric acid plasticizers such as di-n-butyl fumarate and di-(2-ethylhexyl) fumarate; monomethyl itaconate, monobutyl itaconate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, Examples of the plasticizer include itaconic acid-based plasticizers such as luitaconate and di-(2-ethylhexyl) itaconate; stearic acid-based plasticizers such as n-butyl stearate, glycerol monostearate, and diethylene glycol distearate; oleic acid-based plasticizers such as butyl oleate, glyceryl monooleate, and diethylene glycol monooleate; citric acid-based plasticizers such as triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tributyl citrate, and acetyl tri-(2-ethylhexyl) citrate; ricinoleic acid-based plasticizers such as methyl acetyl ricinoleate, butyl acetyl ricinoleate, glyceryl monoricinoleate, and diethylene glycol monoricinoleate; and other fatty acid-based plasticizers such as diethylene glycol monolaurate, diethylene glycol dipelargonate, and pentaerythritol fatty acid esters.

[0119] Examples of aromatic polycarboxylic acid plasticizers include trimellitic acid plasticizers such as tri-n-hexyl trimellitate, tri-(2-ethylhexyl) trimellitate, tri-n-octyl trimellitate, triisooctyl trimellitate, triisononyl trimellitate, tridecyl trimellitate, and triisodecyl trimellitate; and pyromellitic acid plasticizers such as tetra-(2-ethylhexyl) pyromellitate and tetra-n-octyl pyromellitate.

[0120] Examples of the phosphoric acid plasticizer include triethyl phosphate, tributyl phosphate, tri-(2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, octyl diphenyl phosphate, cresyl diphenyl phosphate, cresyl phenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris(chloroethyl) phosphate, tris(chloropropyl) phosphate, tris(dichloropropyl) phosphate, and tris(isopropylphenyl) phosphate.

[0121] Examples of polyol-based plasticizers include glycol-based plasticizers such as diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, triethylene glycol di-(2-ethylbutyrate), triethylene glycol di-(2-ethylhexoate), and dibutylmethylene bisthioglycolate; and glycerin-based plasticizers such as glycerol monoacetate, glycerol triacetate, and glycerol tributyrate.

[0122] Examples of epoxy plasticizers include epoxidized soybean oil, epoxy butyl stearate, di-2-ethylhexyl epoxy hexahydrophthalate, diisodecyl epoxy hexahydrophthalate, epoxy triglyceride, epoxidized octyl oleate, and epoxidized decyl oleate.

[0123] Examples of polyester plasticizers include adipic acid polyesters, sebacic acid polyesters, and phthalic acid polyesters.

[0124] Examples of carbonate plasticizers include propylene carbonate and ethylene carbonate.

[0125] Other examples of the plasticizer include partially hydrogenated terphenyls, adhesive plasticizers, and polymerizable plasticizers such as diallyl phthalate, acrylic monomers and oligomers, etc. These plasticizers can be used alone or in combination of two or more kinds.

[0126] (acid anhydride) Examples of the acid anhydride include cyclic aliphatic acid anhydrides, aromatic acid anhydrides, and unsaturated carboxylic acid anhydrides, and one or more of them may be used in combination. More specifically, for example, maleic acid anhydride, phthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, benzophenonetetracarboxylic acid anhydride, dodecenylsuccinic acid anhydride, polyadipic acid anhydride, polyazelaic acid anhydride, polysebacic acid anhydride, poly(ethyloctadecanedioic acid) anhydride, poly(phenylhexadecanedioic acid) anhydride, tetrahydrophthalic acid anhydride, methyltetrahydrophthalic acid anhydride, methylhexahydrophthalic acid anhydride, hexahydrophthalic acid anhydride, methylhimic acid anhydride, trialkyltetrahydrophthalic acid anhydride, methyl ... anhydride, methylcyclohexene dicarboxylic anhydride, methylcyclohexene tetracarboxylic anhydride, ethylene glycol bistrimellitate dianhydride, HET anhydride, Nadic anhydride, methylnadic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexane-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.

[0127] The acid anhydride may be a compound modified with glycol. Examples of glycols that can be used for modification include alkylene glycols such as ethylene glycol, propylene glycol, and neopentyl glycol; and polyether glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. Furthermore, copolymer polyether glycols of two or more of these glycols and / or polyether glycols may be used.

[0128] Alternatively, among the above-mentioned compounds, a homopolymer or copolymer of a compound having a polymerizable unsaturated group such as maleic anhydride may be used as the acid anhydride. Examples of compounds that can be copolymerized with a compound having an acid anhydride group and a polymerizable unsaturated group include α-olefins such as ethylene, propylene, 1,3-butadiene, and cyclopentylethylene; vinyl compounds having an aromatic ring such as styrene, 1-ethynyl-4-methylbenzene, divinylbenzene, 1-ethynyl-4-methylethylbenzene, benzonitrile, acrylonitrile, p-tert-butylstyrene, 4-vinylbiphenyl, 4-ethynylbenzyl alcohol, 2-ethynylnaphthalene, and phenanthrene-9-ethynyl; and fluoroolefins such as vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, and chlorotrifluoroethylene. These can be used alone or in combination of two or more. It is preferable to use styrene and p-tert-butylstyrene, which are vinyl compounds having an aromatic ring.

[0129] (Phosphate Compounds) Examples of the phosphoric acid compound include phosphoric acid, pyrophosphoric acid, triphosphoric acid, methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, dibutyl phosphate, 2-ethylhexyl acid phosphate, bis(2-ethylhexyl)phosphate, isododecyl acid phosphate, butoxyethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, polyoxyethylene alkyl ether phosphoric acid, etc. In the adhesive of the present invention, since the polyisocyanate composition (X) contains a phosphoric acid compound, it is not necessary to add a phosphoric acid compound when preparing the adhesive.

[0130] (Adhesive Form) The two-component curing adhesive of the present invention may be in the form of either a solvent-based or solventless type. In this specification, the term "solvent-based" adhesive refers to a form used in a method in which the adhesive is applied to a substrate, heated in an oven or the like to volatilize the organic solvent in the coating film, and then laminated to another substrate, that is, a so-called dry lamination method. Either the polyisocyanate composition (X) or the isocyanate-reactive composition (Y), or both, contain an organic solvent capable of dissolving (diluting) the components of the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) used in the present invention.

[0131] Examples of the organic solvent include esters such as ethyl acetate, butyl acetate, cellosolve acetate, etc., ketones such as acetone, methyl ethyl ketone, isobutyl ketone, cyclohexanone, etc., ethers such as tetrahydrofuran, dioxane, etc., aromatic hydrocarbons such as toluene, xylene, etc., halogenated hydrocarbons such as methylene chloride, ethylene chloride, etc., dimethyl sulfoxide, dimethyl sulfamide, etc. The organic solvent used as a reaction medium during the production of the components of the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) may also be used as a diluent during coating.

[0132] In this specification, a "solventless" adhesive refers to a form of adhesive used in a non-solvent lamination method in which the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) are substantially free of esters such as ethyl acetate, butyl acetate, cellosolve acetate, etc., ketones such as acetone, methyl ethyl ketone, isobutyl ketone, cyclohexanone, etc., ethers such as tetrahydrofuran, dioxane, etc., aromatic hydrocarbons such as toluene, xylene, etc., halogenated hydrocarbons such as methylene chloride, ethylene chloride, etc., highly soluble organic solvents such as dimethyl sulfoxide, dimethyl sulfamide, in particular ethyl acetate or methyl ethyl ketone, and in which the adhesive is applied to a substrate and then bonded to another substrate without going through a process of heating in an oven or the like to volatilize the solvent. In the case where the organic solvent used as a reaction medium in the manufacture of the components of the polyisocyanate composition (X) or the isocyanate-reactive composition (Y) or the raw materials thereof cannot be completely removed and a trace amount of organic solvent remains in the polyisocyanate composition (X) or the isocyanate-reactive composition (Y), it is considered that the composition does not substantially contain an organic solvent. In addition, when the isocyanate-reactive composition (Y) contains a low molecular weight alcohol, the low molecular weight alcohol reacts with the polyisocyanate composition (X) and becomes part of the coating film, so there is no need to volatilize it after coating. Therefore, such a form is also treated as a solventless adhesive, and the low molecular weight alcohol is not considered to be an organic solvent.

[0133] The two-component curing adhesive of the present invention is preferably used by mixing the polyisocyanate composition (X) with the molar number [NCO] of the isocyanate group contained in the isocyanate-reactive composition (Y) so that the ratio [NCO] / [isocyanate-reactive functional group] of the molar number of functional groups reactive with isocyanate contained in the isocyanate-reactive composition (Y) is 0.5 to 5.0, more preferably 1.0 to 3.0. This allows for appropriate curing properties to be obtained without depending on the environmental humidity during coating.

[0134] <Laminate> The laminate of the present invention can be obtained, for example, by a method having a two-liquid mixing step in which the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) are mixed in advance, then coated on a first substrate, the second substrate is laminated on the coated surface, and the adhesive layer is cured, or by a method having a two-liquid separate coating step in which the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) are separately coated on a first substrate and a second substrate, the coated surfaces of the substrates are brought into contact with each other and pressed together to laminate the first substrate and the second substrate, and the adhesive layer is cured. There is no particular restriction on the film used, and a film can be appropriately selected according to the application.

[0135] Examples of films for food packaging include polyethylene terephthalate (PET) films, polystyrene films, polyamide films, polyacrylonitrile films, polyethylene films (LLDPE: low-density polyethylene film, HDPE: high-density polyethylene film, MDOPE: uniaxially oriented polyethylene film, OPE: biaxially oriented polyethylene film), polypropylene films (CPP: unoriented polypropylene film, OPP: biaxially oriented polypropylene film), polyolefin films such as gas barrier heat seal films in which an olefin-based heat sealable resin layer is provided on one or both sides of a resin having gas barrier properties such as an ethylene-vinyl alcohol copolymer or polyvinyl alcohol, polyvinyl alcohol film, and ethylene-vinyl alcohol copolymer film.

[0136] It is also preferable to use a biomass film, a biodegradable film, or a recycled plastic film formed from a material containing a biomass-derived component, a biodegradable component, or a recycled component. Biomass films, biodegradable films, and recycled plastic films are sold by various companies. In addition, it is also possible to use films certified in each country, such as film sheets such as those listed in the list of biomass certified products listed by the Japan Organics Resources Association, films such as those listed in the list of Eco Mark certified products listed by the Japan Environment Association, and films bearing the symbol mark designated by the Japan Bioplastics Association.

[0137] (Biomass film) Specifically, well-known biomass films include those using ethylene glycol derived from biomass as a raw material. Biomass-derived ethylene glycol is made from ethanol (biomass ethanol) produced from biomass as a raw material. For example, biomass-derived ethylene glycol can be obtained by a method of producing ethylene glycol from biomass ethanol via ethylene oxide using a conventionally known method. In addition, commercially available biomass ethylene glycol may be used, and for example, biomass ethylene glycol commercially available from India Glycoal Limited can be suitably used.

[0138] For example, as an alternative to conventional polyethylene terephthalate films using petroleum-based raw materials, films containing biomass polyesters and biomass polyethylene terephthalate, which have biomass-derived ethylene glycol as the diol unit and fossil fuel-derived dicarboxylic acids as the dicarboxylic acid units, are known.

[0139] The dicarboxylic acid unit of the biomass polyester uses a dicarboxylic acid derived from a fossil fuel. As the dicarboxylic acid, an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, and a derivative thereof can be used without limitation. In addition to the above diol component and dicarboxylic acid component, the copolymer polyester may be a copolymer polyester containing a copolymer component as a third component, such as a bifunctional oxycarboxylic acid or at least one polyfunctional compound selected from the group consisting of a trifunctional or higher functional polyhydric alcohol, a trifunctional or higher functional polycarboxylic acid and / or its anhydride, and a trifunctional or higher functional oxycarboxylic acid, in order to form a crosslinked structure.

[0140] In addition, for example, as an alternative to conventional polyolefin films using petroleum-based raw materials, biomass polyolefin films such as biomass polyethylene films and biomass polyethylene-polypropylene films, which contain polyethylene resins made from biomass-derived ethylene glycol, are also known. The polyethylene resin is not particularly limited except that ethylene glycol derived from biomass is used as part of the raw material. Examples of the polyethylene resin include ethylene homopolymers and copolymers of ethylene and α-olefins with ethylene as the main component (ethylene-α-olefin copolymers containing 90% by mass or more of ethylene units). These may be used alone or in combination of two or more.

[0141] The α-olefin constituting the copolymer of ethylene and α-olefin is not particularly limited, and examples thereof include α-olefins having 4 to 8 carbon atoms, such as 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene. Known polyethylene resins, such as low-density polyethylene resin, medium-density polyethylene resin, and linear low-density polyethylene resin, can be used. Among them, linear low-density polyethylene resin (LLDPE) (a copolymer of ethylene and 1-hexene, or a copolymer of ethylene and 1-octene) is preferred from the viewpoint of making damage such as holes and tears even less likely to occur even when films are rubbed against each other, and has a density of 0.910 to 0.925 g / cm. 3 More preferred is a linear low density polyethylene resin in which

[0142] Biomass films made from biomass raw materials classified by the biomass plastic degree specified by ISO16620 or ASTM D6866 are also on the market. Radioactive carbon-14C exists in the atmosphere at a ratio of 1 in 1012 particles, and this ratio does not change with atmospheric carbon dioxide, so this ratio does not change even in plants that fix this carbon dioxide through photosynthesis. For this reason, the carbon in plant-derived resins contains radioactive carbon-14C. In contrast, the carbon in fossil fuel-derived resins contains almost no radioactive carbon-14C. Therefore, by measuring the concentration of radioactive carbon-14C in the resin with an accelerator mass spectrometer, the proportion of plant-derived resin in the resin, i.e., the biomass plastic degree, can be determined.

[0143] Examples of plant-derived low-density polyethylene, which is a biomass plastic having a biomass plastic content of 80% or more, preferably 90% or more as specified by ISO16620 or ASTM D6866, include Braskem products under the trade names "SBC818", "SPB608", "SBF0323HC", "STN7006", "SEB853", and "SPB681", and films using these as raw materials can be preferably used.

[0144] In addition, films and sheets containing starch, a biomass raw material, or polylactic acid are also known. These can be selected and used appropriately depending on the application.

[0145] The biomass film may be a laminate of multiple biomass films, or a laminate of a conventional petroleum-based film and a biomass film. These biomass films may be unstretched or stretched films, and the manufacturing method thereof is not limited.

[0146] (Biodegradable film) Specifically, well-known biodegradable films include those made from commonly available biodegradable resins. For example, polycaprolactone, polyvinyl alcohol, polyamide, cellulose ester, lactic acid-based polyester resins, aliphatic polyester resins, or aliphatic aromatic polyester resins may be used. These biodegradable resins may be used alone or in combination of two or more. Among them, aliphatic polyester resins or aliphatic aromatic polyester resins are preferably used. Examples of the aliphatic polyester resin include aliphatic polyesters obtained by polycondensation reaction of aliphatic diols and aliphatic dicarboxylic acids. Examples of the aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol. These may be used alone or in mixtures. Of these, it is preferable to use 1,4-butanediol. Examples of the aliphatic dicarboxylic acids include oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, suberic acid, and dodecanedioic acid, and acid anhydrides that are derivatives of these may also be used. Of these, succinic acid or succinic anhydride, or a mixture of these with adipic acid, is preferable. Specific examples include polybutylene succinate (PBS) obtained from 1,4-butanediol and succinic acid (eg, BioPBS manufactured by PPT MCC Biochem), and polybutylene succinate adipate (PBSA) obtained by copolymerizing PBS with adipic acid.

[0147] Examples of the aliphatic aromatic polyester resin include copolymers containing an aliphatic dicarboxylic acid unit, an aromatic dicarboxylic acid unit, and a chain aliphatic and / or alicyclic diol unit. The diol component that gives the diol unit usually has 2 to 10 carbon atoms, and examples thereof include ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,4-cyclohexanedimethanol. Among these, diols having 2 to 4 carbon atoms are preferred, and ethylene glycol and 1,4-butanediol are preferred, and 1,4-butanediol is more preferred. The dicarboxylic acid component that gives the dicarboxylic acid unit usually has 2 to 10 carbon atoms, and examples thereof include succinic acid, adipic acid, suberic acid, sebacic acid, and dodecanedioic acid. Among these, succinic acid or adipic acid is preferred. Examples of aromatic dicarboxylic acid components that give aromatic dicarboxylic acid units include terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid. Of these, terephthalic acid and isophthalic acid are preferred, with terephthalic acid being more preferred. Specifically, PBAT (for example, Ecoflex manufactured by BASF), which is a copolymer of 1,4-butanediol, adipic acid, and terephthalic acid, can be mentioned.

[0148] Other examples include poly(3-hydroxyalkanoates) which are aliphatic polyester copolymers obtained from hydroxyalkanoic acids and polycarboxylic acids (particularly, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) (e.g., Aonilex manufactured by Kaneka Corporation) and polylactic acid (PLA) (e.g., REVODE manufactured by Kaisei Biomaterials, and Ingeo manufactured by Natureworks).

[0149] The biodegradable film may be a laminate of a plurality of biodegradable films, or a laminate of a conventional petroleum-based film and a biodegradable film. These biodegradable films may be unstretched or stretched films, and the manufacturing method thereof is not limited.

[0150] The film may be one that has been subjected to a stretching treatment. As a stretching method, a typical method is to melt-extrude a resin into a sheet shape by an extrusion film forming method or the like, and then perform simultaneous biaxial stretching or sequential biaxial stretching. In the case of sequential biaxial stretching, it is common to first perform longitudinal stretching and then transverse stretching. Specifically, a method is often used in which longitudinal stretching utilizing the speed difference between rolls and transverse stretching using a tenter are combined.

[0151] The film surface may be subjected to various surface treatments such as flame treatment and corona discharge treatment as necessary so that an adhesive layer free from defects such as film breakage and repellency is formed.

[0152] Alternatively, a film having a vapor-deposited layer of a metal such as aluminum or a metal oxide such as silica or alumina, or a barrier film containing a gas barrier layer such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, vinylidene chloride, etc. can be used in combination. By using such a film, a laminate having a barrier property against water vapor, oxygen, alcohol, inert gas, volatile organic compounds (fragrances), etc. can be obtained.

[0153] The paper can be made of any known paper base material without any particular limitation. Specifically, the paper is made by a known paper machine using natural fibers for papermaking such as wood pulp, but the papermaking conditions are not particularly specified. Examples of natural fibers for papermaking include wood pulp such as softwood pulp and hardwood pulp, non-wood pulp such as Manila hemp pulp, sisal hemp pulp, and flax pulp, and pulp obtained by chemically modifying these pulps. As the type of pulp, chemical pulp, ground pulp, chemi-ground pulp, thermomechanical pulp, etc., made by sulfate cooking method, acidic / neutral / alkaline sulfite cooking method, soda salt cooking method, etc., can be used. In addition, various commercially available wood-free papers, coated papers, backing papers, impregnated papers, cardboard, paperboard, etc. can also be used.

[0154] More specifically, the laminate has the following structure: (1) Substrate 1 / adhesive layer 1 / sealant film (2) Substrate 1 / adhesive layer 1 / metal-deposited unstretched film (3) Substrate 1 / adhesive layer 1 / metal-deposited stretched film (4) Transparent vapor-deposited stretched film / adhesive layer 1 / sealant film (5) Substrate 1 / adhesive layer 1 / substrate 2 / adhesive layer 2 / sealant film (6) Substrate 1 / adhesive layer 1 / metal-deposited stretched film / adhesive layer 2 / sealant film (7) Substrate 1 / adhesive layer 1 / transparent vapor-deposited stretched film / adhesive layer 2 / sealant film (8) Substrate 1 / adhesive layer 1 / metal layer / adhesive layer 2 / sealant film (9) Substrate 1 / adhesive layer 1 / substrate 2 / adhesive layer 2 / metal layer / adhesive layer 3 / sealant film (10) Substrate 1 / adhesive layer 1 / metal layer / adhesive layer 2 / substrate 2 / adhesive layer 3 / sealant film These include, but are not limited to, the following:

[0155] Examples of the substrate 1 used in the configuration (1) include MDOPE film, OPE film, OPP film, PET film, nylon film, paper, etc. In addition, the substrate 1 may be coated with a coating for the purpose of improving the gas barrier property or the ink receptivity when providing a printing layer described later. Examples of commercially available substrate films 1 with coatings include K-OPP film, K-PET film, K-nylon film, etc. The adhesive layer 1 is a cured coating film of the adhesive of the present invention. Examples of sealant films include CPP film, LLDPE film, easy-to-open heat seal film, gas barrier heat seal film, etc. A printing layer may be provided on the surface of the substrate 1 on the adhesive layer 1 side (when a substrate film 1 with coating is used, the surface of the coating layer on the adhesive layer 1 side) or on the surface opposite to the adhesive layer 1. The printing layer is formed by a general printing method that has been used for printing on polymer films and paper using various printing inks such as gravure ink, flexo ink, offset ink, stencil ink, and inkjet ink.

[0156] Examples of the substrate 1 used in the structures (2) and (3) include MDOPE film, OPE film, OPP film, PET film, paper, etc. The adhesive layer 1 is a cured coating of the adhesive of the present invention. Examples of the metal-vapor-deposited unstretched film include a CPP film, an LLDPE film, and a VM-CPP film or a VM-LLDPE film obtained by subjecting a gas-barrier heat seal film to metal vapor deposition such as aluminum, and examples of the metal-vapor-deposited stretched film include a VM-MDOPE film, a VM-OPE film, or a VM-OPP film obtained by subjecting an MDOPE film, an OPE film, or an OPP film to metal vapor deposition such as aluminum. A printed layer may be provided on either side of the substrate 1 in the same manner as in the structure (1).

[0157] Examples of the transparent vapor-deposited stretched film used in the structure (4) include films obtained by vapor-depositing silica or alumina on MDOPE film, OPE film, OPP film, PET film, nylon film, etc. For the purpose of protecting the inorganic vapor-deposited layer of silica or alumina, a film with a coating on the vapor-deposited layer may be used. The adhesive layer 1 is a cured coating of the adhesive of the present invention. Examples of the sealant film include the same as those in the structure (1). A printed layer may be provided on the surface of the transparent vapor-deposited stretched film on the adhesive layer 1 side (when a film with a coating on the inorganic vapor-deposited layer is used, the surface of the coating layer on the adhesive layer 1 side). The method of forming the printed layer is the same as in the structure (1).

[0158] Examples of the substrate 1 used in the structure (5) include PET film and paper. Examples of the substrate 2 include nylon film. At least one of the adhesive layer 1 and the adhesive layer 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those in the structure (1). As in the structure (1), a printed layer may be provided on either side of the substrate 1.

[0159] The substrate 1 in the structure (6) may be the same as those in the structures (2) and (3). Metal-vapor-deposited stretched films include VM-MDOPE films, VM-OPE films, VM-OPP films, and VM-PET films obtained by subjecting MDOPE films, OPE films, OPP films, and PET films to metal vapor deposition such as aluminum. At least one of the adhesive layer 1 and the adhesive layer 2 is a cured coating film of the adhesive of the present invention. The sealant film may be the same as those in the structure (1). A printed layer may be provided on either side of the substrate 1 in the same manner as in the structure (1).

[0160] Examples of the substrate 1 in the structure (7) include PET film, paper, etc. Examples of the transparent vapor deposition stretched film include those similar to those in the structure (4). At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those in the structure (1). As in the structure (1), a printed layer may be provided on either side of the substrate 1.

[0161] The substrate 1 in the structure (8) may be a PET film, paper, or the like. The metal layer may be an aluminum foil, or the like. At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. The sealant film may be the same as that in the structure (1). A printed layer may be provided on either side of the substrate 1 in the same manner as in the structure (1).

[0162] Examples of the substrate 1 in the structures (9) and (10) include PET film, paper, etc. Examples of the substrate 2 include nylon film, etc. Examples of the metal layer include aluminum foil, etc. At least one layer of the adhesive layers 1, 2, and 3 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those in the structure (1). As in the structure (1), a printed layer may be provided on either side of the substrate 1.

[0163] The laminate of the present invention may further include other films and substrates in addition to the above-mentioned configurations (1) to (10). As the other substrates, in addition to the above-mentioned stretched films, unstretched films, and transparent vapor deposition films, porous substrates such as paper, wood, and leather, which will be described later, can also be used. The adhesive used when bonding the other substrates may be the adhesive of the present invention or may not be the adhesive.

[0164] The "other layer" may contain known additives or stabilizers, such as antistatic agents, adhesion enhancing coating agents, plasticizers, lubricants, antioxidants, etc. Furthermore, the "other layer" may be a film whose surface has been pretreated with corona treatment, plasma treatment, ozone treatment, chemical treatment, solvent treatment, etc., in order to improve adhesion when laminated with other materials.

[0165] The laminate of the present invention can be suitably used for various applications, such as packaging materials for food, medicines, and daily necessities; paper tableware such as lid materials, paper straws, paper napkins, paper spoons, paper plates, and paper cups; wall materials, roofing materials, solar cell panel materials, packaging materials for batteries, window materials, outdoor flooring materials, lighting protection materials, automotive parts, signs, stickers, and other outdoor industrial applications; decorative sheets used in simultaneous injection molding decoration methods, and packaging materials for liquid laundry detergents, liquid kitchen detergents, liquid bath detergents, liquid bath soaps, liquid shampoos, liquid conditioners, and the like.

[0166] <Packaging material> The laminate of the present invention can be used as a multi-layer packaging material for protecting foods, medicines, etc. When used as a multi-layer packaging material, the layer structure can be changed depending on the contents, the environment of use, and the form of use. In addition, the package of the present invention may be appropriately provided with an easy-opening treatment or a resealable means.

[0167] An example of a specific embodiment of the packaging material of the present invention is a packaging material obtained by making a bag from a laminate having a sealant film, such as the laminate configuration examples (1), (4) to (10) described above. The laminate is folded or overlapped so that the inner layer surface (sealant film surface) faces each other, and the peripheral edge is heat-sealed to form a bag. Examples of the bag-making method include heat-sealing methods using a side seal type, a two-sided seal type, a three-sided seal type, a four-sided seal type, an envelope seal type, a grooving seal type, a pleated seal type, a flat bottom seal type, a square bottom seal type, a gusset type, or other heat seal type. The packaging material of the present invention can take various forms depending on the contents, the environment of use, and the form of use. A self-supporting packaging material (standing pouch) is also possible. Examples of the heat-sealing method include known methods such as bar seal, rotary roll seal, belt seal, impulse seal, high frequency seal, and ultrasonic seal.

[0168] The packaging material of the present invention is filled with contents through its opening, and the opening is then heat-sealed to produce a product using the packaging material of the present invention. The contents to be filled include, for example, foods such as rice crackers, bean snacks, nuts, biscuits, cookies, wafers, marshmallows, pies, semi-dried cakes, candies, snacks, and other confectioneries, bread, snack noodles, instant noodles, dried noodles, pasta, aseptically packaged cooked rice, porridge, porridge, packaged rice cakes, and cereal foods, and other staple foods, pickles, boiled beans, natto, miso, frozen tofu, tofu, nametake mushrooms, konjac, wild vegetable processed products, jams, peanut cream, salads, frozen vegetables, and potato processed products, livestock processed products such as hams, bacon, sausages, chicken processed products, and corned beef, and fish hams, These include processed seafood products such as sausages, fish paste products, kamaboko, nori, tsukudani, bonito flakes, shiokara, smoked salmon, and spicy cod roe; fruit pulp such as peaches, mandarin oranges, pineapples, apples, pears, and cherries; vegetables such as corn, asparagus, mushrooms, onions, carrots, radishes, and potatoes; cooked foods such as hamburger steaks, meatballs, seafood fries, gyoza, croquettes, and other frozen and chilled prepared foods; dairy products such as butter, margarine, cheese, cream, instant creamy powder, and infant formula; liquid seasonings, retort curry, and pet food.

[0169] In addition, the composition can be used as a packaging material for various non-food items, such as tobacco, disposable hand warmers, medicines such as infusion packs, liquid laundry detergent, liquid kitchen detergent, liquid bath detergent, liquid bath soap, liquid shampoo, liquid conditioner, cosmetics such as lotion and milky lotion, vacuum insulation materials, batteries, etc. EXAMPLES

[0170] The present invention will be described in more detail below with reference to specific synthesis examples and examples, but the present invention is not limited to these examples. In the following examples, "parts" and "%" respectively represent "parts by mass" and "% by mass" unless otherwise specified.

[0171] <Preparation of polyisocyanate composition (X)> (Polyisocyanate composition (X-1)) 744.5 parts of hexamethylene diisocyanate (HDI) was added to a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a condenser, and the mixture was heated to 60°C while stirring under a nitrogen gas stream. Then, 255.5 parts of polyoxypropylene sorbitol ether (Sanyo Chemical Industries, Sannix SP-750) was charged while being careful of heat generation, and then the mixture was heated to 80°C. The reaction was continued at 80°C until the NCO% did not change, and 0.2 parts of butyl acid phosphate was added to terminate the reaction. Next, a thin-film distillation apparatus was used to purify the urethane prepolymer, which is a reaction product of HDI and polyol, at a pressure of about 0.02 Torr and a temperature of 160°C until the HDI in the urethane prepolymer was 0.05% by mass in the solid content, thereby obtaining a polyisocyanate composition (X-1). The NCO% of the polyisocyanate composition (X-1) was 12.1%.

[0172] (Polyisocyanate composition (X-2)) In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a condenser, 836.1 parts of hexamethylene diisocyanate (HDI) was added, and the mixture was heated to 60°C while stirring under a nitrogen gas stream. Then, 163.9 parts of polyoxypropylene sorbitol ether (Sanyo Chemical Industries, Sannix SP-750) was added while being careful of heat generation, and then the mixture was heated to 100°C. The reaction was further carried out at 100°C for 10 hours, and 0.2 parts of polyphosphoric acid was added to terminate the reaction. Next, a thin-film distillation apparatus was used to purify the urethane prepolymer, which is a reaction product of HDI and polyol, at a pressure of about 0.02 Torr and a temperature of 160°C until the HDI in the urethane prepolymer was 0.05 mass% of the solid content, thereby obtaining a polyisocyanate composition (X-2). The NCO% of the polyisocyanate composition (X-2) was 12.1%.

[0173] (Polyisocyanate composition (X-3)) 712.9 parts of hexamethylene diisocyanate (HDI) was added to a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a condenser, and heated to 60°C while stirring under a nitrogen gas stream. Then, 186.6 parts of polyoxypropylene sorbitol ether (Sanyo Chemical Industries, Sannix SP-750) and 100.5 parts of bifunctional polyethylene glycol with a molecular weight of 400 were charged while being careful of heat generation, and then heated to 80°C. The reaction was continued at 80°C until the NCO% did not change, and 0.2 parts of butyl acid phosphate was added to terminate the reaction. Next, a thin-film distillation apparatus was used to purify the urethane prepolymer, which is the reaction product of HDI, at a pressure of about 0.02 Torr and a temperature of 160°C until the HDI in the urethane prepolymer was 0.05% by mass in the solid content, thereby obtaining a polyisocyanate composition (X-3). The NCO% of the polyisocyanate composition (X-3) was 11.2%.

[0174] (Polyisocyanate composition (X-4)) 802.8 parts of hexamethylene diisocyanate (HDI) was added to a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a condenser, and the mixture was heated to 60°C while stirring under a nitrogen gas stream. Then, 197.2 parts of polyoxypropylene sucrose ether (Sanyo Chemical Industries, Sannix HS-209) was added while being careful of heat generation, and the mixture was then heated to 100°C. The reaction was further carried out at 100°C for 10 hours, and 1.0 part of polyphosphoric acid was added to terminate the reaction. Next, a thin-film distillation apparatus was used to purify the urethane prepolymer, which is the reaction product of HDI, at a pressure of about 0.02 Torr and a temperature of 160°C until the HDI in the urethane prepolymer was 0.05 mass% of the solid content, thereby obtaining a polyisocyanate composition (X-4). The NCO% of the polyisocyanate composition (X-4) was 12.9%.

[0175] (Polyisocyanate composition (X'-5)) 1000.0 parts of hexamethylene diisocyanate (HDI) was added to a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a condenser, and the mixture was heated to 60°C while stirring. 0.5 parts of a quaternary ammonium salt was added dropwise thereto, and when a predetermined refractive index was reached, a deactivator was appropriately added to terminate the reaction. Next, using a thin-film distillation apparatus, the mixture was purified at a pressure of about 0.02 Torr and a temperature of 160°C until the HDI in the nurate body, which is the reaction product of HDI, was 0.05 mass% of the solid content, thereby obtaining a polyisocyanate composition (X'-5). The NCO% of the polyisocyanate composition (X'-5) was 21.8%.

[0176] (Polyisocyanate composition (X'-6)) 712.9 parts of hexamethylene diisocyanate (HDI) was added to a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a condenser, and heated to 60°C while stirring under a nitrogen gas stream. Then, 186.6 parts of polyoxypropylene sorbitol ether (Sanyo Chemical Industries, Sannix SP-750) and 100.5 parts of bifunctional polyethylene glycol with a molecular weight of 400 were charged while being careful of heat generation, and then heated to 100°C. The reaction was further carried out at 100°C for 10 hours, and 10.0 parts of polyphosphoric acid was added to terminate the reaction. Next, a thin-film distillation apparatus was used to purify the urethane prepolymer, which is a reaction product of HDI and polyol, at a pressure of about 0.02 Torr and a temperature of 160°C until the HDI in the urethane prepolymer was 0.05 mass% of the solid content, thereby obtaining a polyisocyanate composition (X'-6). The NCO% of the polyisocyanate composition (X'-6) was 11.1%.

[0177] (Polyisocyanate composition (X'-7)) 896.1 parts of hexamethylene diisocyanate (HDI) was added to a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a condenser, and the mixture was heated to 60°C while stirring under a nitrogen gas flow. Then, 103.9 parts of polyglycerin 10 (a polymer of 10 glycerins) was added while being careful of heat generation, and then the mixture was heated to 100°C. The reaction was further carried out at 100°C for 10 hours, and 1.0 part of polyphosphoric acid was added to terminate the reaction. Next, a thin-film distillation apparatus was used to purify the urethane prepolymer, which is a reaction product of HDI and polyol, at a pressure of about 0.02 Torr and a temperature of 160°C until the HDI in the urethane prepolymer was 0.05 mass% of the solid content, thereby obtaining a polyisocyanate composition (X'-7). The NCO% of the polyisocyanate composition (X'-7) was 15.8%.

[0178] <Preparation of Isocyanate-Reactive Composition (Y)> (Isocyanate-reactive composition (Y-1)) A polyester reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, a rectifying tube, etc. was charged with 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, and the ester reaction was carried out at an internal temperature of 250 ° C. After the dehydration reaction, an intermediate polyester polyol with an acid value of 1 mgKOH / g was obtained. This was dissolved and diluted with ethyl acetate to obtain a solution with a non-volatile content of 65% by mass. Furthermore, 4 parts of isophorone diisocyanate were added to 100 parts of the intermediate polyester polyol solid content obtained, and the mixture was heated to 80 ° C. to carry out a urethane reaction until the free NO group was substantially eliminated, and an isocyanate-reactive composition (Y-1) with a non-volatile content of 65% by mass and a hydroxyl value of 6 was obtained.

[0179] <Evaluation> (Storage Stability of Polyisocyanate Composition (X)) The polyisocyanate compositions (X-1) to (X-4) and (X'-5) to (X'-7) were filled into 15 ml glass bottles, respectively, and stored at room temperature for a certain period of time. The state of the polyisocyanate composition (X) after storage was evaluated on a two-point scale according to the following criteria, and the results are summarized in Table 1. 〇: Did not solidify for more than 30 days ×: Solidified within 30 days

[0180] [Table 1]

[0181] (Preparation of adhesive) Adhesives of the Examples and Comparative Examples were prepared by mixing the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) in the proportions shown in Table 2. Note that the polyisocyanate composition (X'-7) was not evaluated as an adhesive because it solidified.

[0182] (Heat seal strength) A two-component curing adhesive (solid content 3 g / m2) was prepared by mixing a biaxially oriented nylon film with a thickness of 15 μm and a linear low-density polyethylene film (LLDPE film) with a thickness of 30 μm as a sealant film in the combination of the examples and the comparative examples. 2 ) and aging was performed at 40°C for 6 hours to obtain a laminated film.

[0183] The sealant film surfaces of the laminated films are joined together and sealed at 180℃ 1kgf / cm with a 1cm wide seal bar. 2 The specimen was heat sealed for 1 second and cut into a 15mm width. A tensile tester was used, with the ambient temperature set at 25°C and the peel speed at 300mm / min, and both ends of the specimen were pulled to measure the peak tensile strength, which was taken as the heat seal strength (N / 15mm). Evaluation was performed according to the following criteria, and the results are shown in Table 2. ○:30N / 15mm or more ×: Less than 30N / 15mm

[0184] (Laminate strength) A two-component curing adhesive (solid content 3 g / m2) was prepared by mixing a biaxially oriented PET film with a thickness of 50 μm and an aluminum foil with a thickness of 30 μm in the Examples and Comparative Examples. 2 ) and aging was performed at 40° C. for 72 hours to obtain a laminated film.

[0185] Test pieces with a width of 15 mm were cut from the laminated film, and adhesive strength (N / 15 mm) was measured using a tensile tester at an atmospheric temperature of 25° C., a peel speed of 300 mm / min, and 180° peeling. Evaluation was performed according to the following criteria, and the results are summarized in Table 2. 〇: 5.0N / 15mm or more ×: Less than 5.0N / 15mm

[0186] [Table 2]

Claims

1. A polyurethane polyisocyanate (A1) which is a reaction product of hexamethylene diisocyanate and a polyol having 5 to 10 hydroxyl groups; A phosphoric acid derivative (B), The polyisocyanate composition (X), wherein the content of the phosphoric acid derivative (B) is 10 ppm or more and 5,000 ppm or less.

2. The polyisocyanate composition (X) according to claim 1, wherein the molecular weight of the polyol is 200 g / mol or more and 3000 g / mol or less.

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

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

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

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

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

8. The polyisocyanate composition (X) according to claim 5, wherein the molecular weight of the bifunctional polyol is 100 g / mol or more and 4000 g / mol or less.

9. The polyisocyanate composition (X) according to claim 5, wherein the content of the polyurethane polyisocyanate (A2) in the polyisocyanate composition (X) is 10% by mass or more and 60% by mass or less.

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

11. The polyisocyanate composition (X) according to any one of claims 1 to 10, and an isocyanate-reactive composition (Y) containing an isocyanate-reactive compound (C).

12. The polyisocyanate composition (X) according to any one of claims 1 to 10, and an isocyanate-reactive composition (Y) containing an isocyanate-reactive compound (C).

13. The polyisocyanate composition (X) according to any one of claims 1 to 10, and an isocyanate-reactive composition (Y) containing 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 the group consisting of 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, the adhesive layer being a cured coating film of the two-component curing adhesive according to claim 13.

16. A packaging material comprising the laminate according to claim 15.

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