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

Abstract

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

Description

Technical Field

[0001] This invention relates to polyisocyanate compositions, two-component curable compositions, two-component curable coatings, two-component curable adhesives, laminates, and packaging materials. Background Technology

[0002] Laminated materials used in various packaging materials and labels are endowed with design features, functionality, preservation properties, convenience, and transport resistance through the lamination of a wide variety of substrates such as plastic films, metal foils, and paper. Packaging materials formed from these laminates into bags are used in various fields, including food, pharmaceuticals, and detergents.

[0003] Previously, the mainstream method for producing laminated films was dry lamination. This dry lamination method involves coating a film with a two-component curable adhesive containing polyisocyanate and polyol compounds dissolved in a volatile organic solvent. The organic solvent evaporates during the drying process in an oven, and other films are then bonded together. In recent years, from the perspective of reducing environmental impact and improving the working environment, solvent-free two-component curable adhesives containing polyisocyanate and polyol compounds that do not contain volatile organic solvents have attracted attention (Patent Document 1, Patent Document 2).

[0004] Existing technical documents

[0005] Patent documents

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

[0007] Patent Document 2: Japanese Patent Application Publication No. 2001-172602 Summary of the Invention

[0008] The problem the invention aims to solve

[0009] To improve productivity, it is necessary to improve the reactivity of such two-component curing adhesives. On the other hand, the polyisocyanate compound, which is one component of two-component curing adhesives, reacts with moisture in the air; therefore, if the reactivity is too high, storage stability may be reduced. In addition, if the reaction proceeds rapidly immediately after the two components are mixed, there is a tendency for the adhesion between the bonded components and the adhesive to decrease.

[0010] The present invention was made in view of the following circumstances, and its object is to provide a two-component curing adhesive with an excellent balance between reactivity and storage stability, and a polyisocyanate composition suitable for such an adhesive.

[0011] Solution for solving the problem

[0012] That is, the present invention relates to a polyisocyanate composition (X) and a two-component curable adhesive comprising such a polyisocyanate composition (X), wherein the polyisocyanate composition (X) comprises a polyurethane polyisocyanate (A1) as a reaction product of toluene diisocyanate and a polyol having 5 or more and 10 or less hydroxyl groups, and comprises a phosphate derivative (B) in an amount of 10 ppm or more and 5000 ppm or less.

[0013] The effects of the invention

[0014] According to the present invention, a two-component curing adhesive with an excellent balance between reactivity and storage stability can be provided, and a polyisocyanate composition suitable for such an adhesive can be provided. Detailed Implementation

[0015] <Polyisocyanate Composition (X)>

[0016] (Polyurethane polyisocyanate (A1))

[0017] The polyisocyanate composition (X) of the present invention comprises a polyurethane polyisocyanate (A1), which is a reaction product of toluene diisocyanate and a polyol having 5 or more and 10 or less, more preferably 5 or more and 8 or less hydroxyl groups. The toluene diisocyanate may be any one or both of 2,4'-toluene diisocyanate and 2,6'-toluene diisocyanate.

[0018] Examples of polyols with 5 or more but less than 10 hydroxyl groups used in the synthesis of polyurethane polyisocyanates (A1) include low molecular weight polyols with 5 or more but less than 10 hydroxyl groups such as xylitol, triglycerides, sorbitol, dipentaerythritol, mannitol, sucrose, and polyglycerol, and / or polyether polyols formed by addition polymerization of ethylene oxide, propylene oxide, butane oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, cyclohexene oxide, etc., using these low molecular weight polyols as initiators. One type or two or more types can be used.

[0019] From the perspective of being able to form a soft coating film, and for example, to improve adhesion when the polyisocyanate composition (X) of the present invention is formulated into a two-component curable adhesive as described later, it is preferable to use polyether polyols formed by addition polymerization of epoxides onto low molecular weight polyols having 5 or more and 10 or less hydroxyl groups, and / or polyglycerols having 5 or more and 10 or less hydroxyl groups. It is preferable to use at least one of polyether polyols formed by addition polymerization of at least one of ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran onto sorbitol, and polyglycerols having 5 or more and 10 or less hydroxyl groups. It is preferable to use at least one of polyether polyols formed by addition polymerization of at least one of ethylene oxide and propylene oxide onto sorbitol, and polyglycerols having 5 or more and 10 or less hydroxyl groups.

[0020] The polyols used are preferably polyols with a molecular weight of 200 g / mol or more and 3000 g / mol or less, more preferably polyols with a molecular weight of 400 g / mol or more and 3000 g / mol or less, and even more preferably polyols with a molecular weight of 440 g / mol or more and 2000 g / mol or less.

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

[0022] The polyisocyanate composition (X) used in this invention preferably has a content of diisocyanate monomers, i.e., aromatic diisocyanate, aromatic aliphatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, etc., which are examples of raw materials for the isocyanate derivative (A3) described later, reduced to 1.0% by mass or less, more preferably reduced to 0.1% by mass or less.

[0023] From an occupational safety and health perspective, there is a trend towards restricting the use of isocyanate monomers. The European Commission has adopted the REACH regulation, which prohibits the marketation of products containing more than 0.1% by mass of isocyanate monomers unless certain conditions are met. Articles that comply with this regulation can be made if unreacted diisocyanate monomers are removed until the amount of diisocyanate monomers in the polyisocyanate composition is less than 0.1% by mass.

[0024] Furthermore, when using a two-component curing adhesive containing a substance derived from an aromatic diisocyanate (A3, described later) and having a substantial amount of that aromatic diisocyanate remaining, unreacted aromatic isocyanate monomers may remain in the adhesive layer. These isocyanate monomers react with surrounding water to form aromatic primary amines (PAAs), raising concerns about their migration within the film and leaching into the contents (food). Due to concerns about the potential harm of PAAs to human health, the European Commission has established various regulations, including detection limits, in its rules concerning plastic materials and articles of contact with food.

[0025] PAA reacts with unreacted aromatic isocyanates present in the surrounding environment, so even if aromatic isocyanates remain in the adhesive layer, the concentration of PAA gradually decreases. All values ​​are below the detection limit, but from the viewpoint of manufacturing efficiency of laminates for food packaging, a low initial value of residual aromatic isocyanate monomers in the adhesive layer is preferred. By pre-removing diisocyanate monomers, a two-component curing adhesive with excellent manufacturing efficiency can be produced.

[0026] Diisocyanate monomer removal can be achieved by distilling the diisocyanate monomer under reduced pressure using short-path distillation apparatus, thin-film distillation apparatus, etc. The reduced pressure and distillation temperature are adjusted appropriately according to the diisocyanate monomer to be removed; for example, it is below 0.1 mbar and 120℃~190℃. The diisocyanate monomer removal process can be repeated multiple times.

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

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

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

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

[0031] Eluent: Ammonium formate aqueous solution / methanol, 0.3 mL / min

[0032] Detector: PDA

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

[0034] 2. Stir with a vortex for 30 seconds.

[0035] 3. Dilute appropriately with elution buffer (mobile phase)

[0036] 4. Pass the liquid through a 0.2μm filter to prepare the test sample.

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

[0038] (Polyurethane polyisocyanate (A2))

[0039] The polyisocyanate composition (X) preferably includes a polyurethane polyisocyanate (A2) as a reaction product of toluene diisocyanate and a difunctional polyol. This allows for the preparation of a polyisocyanate composition (X) with a superior balance of reactivity, storage stability, and coatability. Furthermore, when used as a two-component curable composition as described later, it forms a coating film with moderate flexibility, improving adhesion to flexible substrates. The toluene diisocyanate can be any one or both of 2,4'-toluene diisocyanate and 2,6'-toluene diisocyanate.

[0040] Examples of difunctional polyols used in the synthesis of polyurethane polyisocyanates (A2) include 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, neopentanediol, dimethylbutanediol, butyl ethyl propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dihydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanediethanol, and other aliphatic diols, and / or polyether diols formed by addition polymerization of ethylene oxide, propylene oxide, butane oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, cyclohexene oxide, and other epoxides using these aliphatic diols as initiators. One or more of these polyols may be used.

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

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

[0043] When the polyisocyanate composition (X) includes polyurethane polyisocyanate (A2), polyurethane polyisocyanate (A1) and polyurethane polyisocyanate (A2) can be mixed separately synthesized substances. Alternatively, toluene diisocyanate can be reacted with a polyol having 5 or more and 10 or less hydroxyl groups and a difunctional polyol under conditions where the isocyanate groups of toluene diisocyanate are in excess relative to the hydroxyl groups of the polyol. Then, unreacted diisocyanate monomers are removed as needed to obtain a mixture of polyurethane polyisocyanate (A1) and polyurethane polyisocyanate (A2). The isocyanate group to hydroxyl equivalent ratio [NCO] / [hydroxyl] can be appropriately adjusted, and for example, is 2.0 or more and 20.0 or less.

[0044] In the case of synthesizing polyurethane polyisocyanate (A2), toluene diisocyanate is reacted with a difunctional polyol under conditions where the isocyanate group of the toluene diisocyanate is in excess relative to the hydroxyl group of the difunctional polyol. Unreacted diisocyanate monomers are then removed as needed. The isocyanate group to hydroxyl equivalent ratio [NCO] / [hydroxyl] can be appropriately adjusted; for example, it is 2.0 or more and 20.0 or less.

[0045] (Isocyanate derivative (A3))

[0046] To improve the storage stability, coatability, and film flexibility of the polyisocyanate composition (X) when used as a two-component curable composition as described later, the polyisocyanate composition (X) may include isocyanate derivatives (A3) other than polyurethane polyisocyanate (A1) and polyurethane polyisocyanate (A2). Examples of isocyanate derivatives (A3) include conventionally known aromatic diisocyanates, aromatic aliphatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and biuret bodies, ureates, adducts, urea carbamate bodies, carbodiimide modifiers, urea diketone modifiers, and polyurethane polyisocyanates other than (A1) and (A2). One or more of these derivatives may be used.

[0047] Examples of aromatic diisocyanates include 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (also known as MDI), polymethylene polyphenyl polyisocyanate (also known as polymeric MDI or crude MDI), 1,3-phenyl diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenyl diisocyanate (also known as PPDI), and 2,4-toluene diisocyanate. Isocyanates, 2,6-toluene diisocyanate (also known as TDI), 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, o-toluene diisocyanate (also known as TODI), bi-anisidine diisocyanate, naphthalene diisocyanate (also known as NDI), 4,4'-diphenyl ether diisocyanate, 4,4',4"-triphenylmethane triisocyanate, etc., but not limited to these.

[0048] Aromatic aliphatic diisocyanates refer to aliphatic isocyanates with one or more aromatic rings in their molecules. Examples include m-phenylenedimethyl diisocyanate or p-phenylenedimethyl diisocyanate (also known as XDI), α,α,α',α'-tetramethylphenylenedimethyl diisocyanate (also known as TMXDI), etc., but are not limited to these.

[0049] 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-propylidene diisocyanate, 2,3-butylidene diisocyanate, 1,3-butylidene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate (also known as LDI).

[0050] Examples of alicyclic diisocyanates include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, isophorone diisocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylene dicyclohexyl isocyanate (also known as hydrogenated MDI or HMDI), 1,3-bis(isocyanate methyl)cyclohexane (also known as hydrogenated XDI or HXDI), hydrogenated TMXDI, norbornane diisocyanate (also known as NBDI), etc., but are not limited to these.

[0051] Examples of polyols used in the synthesis of polyurethane polyisocyanates other than (A1) and (A2) include 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, neopentanediol, dimethylbutanediol, butyl ethyl propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dihydroxyethoxybenzene, 1,4-cyclohexanediol, and 1,4-cyclohexanediethanol.

[0052] Trifunctional or tetrafunctional aliphatic alcohols such as glycerol, trimethylolpropane, and pentaerythritol;

[0053] Bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, and other bisphenols;

[0054] Dimer Diol;

[0055] Polyether polyols are obtained by addition polymerization of ethylene oxide, propylene oxide, butane oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, cyclohexene oxide, and other epoxides in the presence of polymerization initiators such as the above-mentioned diols, trifunctional or tetrafunctional aliphatic alcohols.

[0056] Polyester polyol (1) is a reaction product of polyester obtained by ring-opening polymerization of cyclic ester compounds such as propiolactone, butyrolactone, ε-caprolactone, σ-valerolactone, and β-methyl-σ-valerolactone with the aforementioned diols, glycerol, trimethylolpropane, pentaerythritol and other polyols.

[0057] Polyester polyols (2) obtained by reacting the above-mentioned diols, dimer diols, or the above-mentioned bisphenols and other difunctional polyols with polycarboxylic acids:

[0058] Polyester polyols obtained by reacting trifunctional or tetrafunctional aliphatic alcohols with polycarboxylic acids (3).

[0059] Polyester polyols (4) are obtained by reacting difunctional polyols with the above-mentioned trifunctional or tetrafunctional aliphatic alcohols and polycarboxylic acids.

[0060] Polyester polyols that are polymers of hydroxy acids such as dimethylolpropionic acid and castor oil fatty acids (5).

[0061] The polyether polyols described above are obtained by increasing the molecular weight of the polyether polyols using isocyanate compounds;

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

[0063] Polyester polyols (1) to (5) are obtained by increasing the molecular weight of polyester polyols by using isocyanate compounds;

[0064] Castor oil, dehydrated castor oil, hydrogenated castor oil as a hydrogenation of castor oil, castor oil-based polyols such as 5-50 molar adducts of castor oil epoxides, and mixtures thereof, may be used in one or more combinations.

[0065] Examples of polycarboxylic acids used in the synthesis of polyester polyols (2) to (4) include: phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, 1,4-naphthalic acid, 2,5-naphthalic acid, 2,6-naphthalic acid, 2,3-naphthalic anhydride, naphthalic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, biphenyl acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid, benzophenone tetracarboxylic acid dianhydride, benzoyl-5-sulfonate sodium isophthalate, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, etc.

[0066] Methyl esters of aromatic polybasic acids such as dimethyl terephthalate and dimethyl 2,6-naphthalenedicarboxylate;

[0067] Malic acid, succinic acid, succinic anhydride, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, and other aliphatic polyacids;

[0068] Alkyl esters of aliphatic polyacids such as dimethyl malonate, diethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, diethyl heptaate, diethyl sebacate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, and diethyl maleate.

[0069] Alicyclic polyacids 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, nadic anhydride, and chlorobridged anhydride can be used, either one or two or more in combination.

[0070] When the polyisocyanate composition (X) contains an isocyanate derivative (A3), the content of polyurethane polyisocyanate (A1) in the total amount of polyurethane polyisocyanate (A1) and isocyanate derivative (A3) is preferably 40% by mass or more.

[0071] (Phosphate derivative (B))

[0072] Examples of phosphoric acid derivatives (B) include: phosphoric acid, pyrophosphate, tripolyphosphate, methyl phosphate, ethyl phosphate, butyl phosphate, dibutyl phosphate, 2-ethylhexyl phosphate, bis(2-ethylhexyl) phosphate, isododecyl phosphate, butoxyethyl phosphate, oleyl phosphate, tetracosyl phosphate, 2-hydroxyethyl methacrylate, polyoxyethylene alkyl ether phosphate, etc. Phosphoric acid, pyrophosphate, tripolyphosphate, and butyl phosphate are preferred.

[0073] The content of phosphoric acid derivative (B) in the polyisocyanate composition (X) of the present invention is 10 ppm or more and 5000 ppm or less. Therefore, a polyisocyanate composition (X) with excellent reactivity and storage stability can be prepared. More preferably, the content of phosphoric acid derivative (B) in the polyisocyanate composition (X) is 50 ppm or more, and more preferably 1000 ppm or less.

[0074] The phosphate derivative (B) is preferably added after the urethane esterification of the polyurethane polyisocyanate (A1). In the case where the polyurethane polyisocyanate (A1) is manufactured by removing unreacted isocyanate monomers, it can be added after the urethane esterification reaction of the polyurethane polyisocyanate (A1) and before the removal of unreacted isocyanate monomers, or it can be added after the removal of isocyanate monomers.

[0075] <Two-component cured composition>

[0076] The polyisocyanate composition (X) of the present invention can be used in combination with an isocyanate reactive composition containing a compound that is reactive with isocyanates to form a two-component cured composition. Examples of compounds that are reactive with isocyanates include polyether polyols, polyester polyols, polyester polyether polyols, polyurethane polyols, polyester polyurethane polyols, polyether polyurethane polyols, vegetable oil polyols, sugar alcohols, polycarbonate polyols, acrylic polyols, hydroxyl-containing olefin resins, hydroxyl-containing fluoropolymers, (poly)alkanolamines, etc.

[0077] Such two-component curable compositions can be used, for example, in adhesives, coatings, sealants, elastomers, etc.

[0078] Two-component curing coating agent

[0079] The two-component curable coating agent of the present invention comprises the above-mentioned polyisocyanate composition (X) and an isocyanate reactive composition. The coating agent of the present invention is suitable for various applications, and is particularly suitable for use as a coating agent for metal substrates such as aluminum and steel plates, for use as an outer coating for coatings containing aluminum pigments and metal particles, for covering electrical components, and for electrical insulation, due to its excellent adhesion to metal materials.

[0080] The isocyanate reactive composition (Y) comprises compounds (C) having multiple functional groups that are reactive with isocyanates, such as 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) (hereinafter also referred to as isocyanate reactive compounds (C)). One isocyanate reactive compound (C) may be used, or two or more may be used in combination.

[0081] Examples of polyester polyols (C1) include polyester polyols that are reaction products of polyols and polycarboxylic acids, and lactone-based polyester polyols obtained by polycondensation reactions of aliphatic polyols with various lactones such as ε-caprolactone. Polyester polyols that are reaction products of polyols and polycarboxylic acids are preferred.

[0082] Examples of polyols include 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, neopentanediol, 1,6-hexanediol, 1,4-bis(hydroxymethyl)cyclohexane, and 2,2,4-trimethyl-1,3-pentanediol, among other aliphatic diols.

[0083] Trimethylolethane, trimethylolpropane, glycerol, hexanetriol, pentaerythritol, and other trifunctional or higher aliphatic polyols;

[0084] Bisphenol A, bisphenol F, and other bisphenols;

[0085] Bisphenol alkyl oxide adducts are obtained by adding ethylene oxide, propylene oxide, etc. to bisphenols such as bisphenol A and bisphenol F;

[0086] Polyether polyols obtained by ring-opening polymerization of aliphatic diols or polyols with various compounds containing cyclic ether bonds, such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, etc., may use one or more types in combination.

[0087] Examples of aliphatic dicarboxylic acids include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanoic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid.

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

[0089] These are aliphatic or dicarboxylic acid anhydrides or esterifying derivatives;

[0090] p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid and their dihydroxycarboxylic acid derivatives, dimer acids and other polybasic acids may be used in one or in combination of two or more.

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

[0092] The preferred hydroxyl value of the polyester polyol (C1) is above 5 mg KOH / g and below 500 mg KOH / g.

[0093] Examples of polyether polyols (C2) include substances obtained by addition polymerization of ethylene oxide, propylene oxide, butane oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, cyclohexene oxide, and other epoxides in the presence of a polymerization initiator.

[0094] Examples of polymerization initiators include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentanediol, methylpentanediol, dimethylbutanediol, butyl ethyl propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dihydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanediol, and triethylene glycol.

[0095] Trifunctional or tetrafunctional aliphatic alcohols such as glycerol, trimethylolpropane, pentaerythritol, and triols of polypropylene glycol;

[0096] Amine compounds containing multiple amino groups, such as ethylamine, diethylamine, etc., primary or secondary alkylamines, methylenediamine, ethylenediamine, etc., and amine compounds containing active hydrogen groups, such as monoethanolamine, diethanolamine, etc., primary or secondary alkylolamines, etc.

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

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

[0099] Examples of vegetable oil polyols (C3) include castor oil, dehydrated castor oil, hydrogenated castor oil as a hydride of castor oil, and 5-50 molar adducts of castor oil epoxides.

[0100] Polyurethane polyols (C4) are reaction products of low- or high-molecular-weight polyols and polyisocyanate compounds. The same polyols used as examples of polyester polyols (C1) can be used as low- or high-molecular-weight polyols. The same compounds used as examples of isocyanate derivatives (A3) can be used as polyisocyanate compounds.

[0101] Examples of sugar alcohols (C5) include pentaerythritol, sucrose, xylitol, sorbitol, isomaltitol, lactitol, maltitol, and mannitol.

[0102] As an acrylic polyol (C6), it is essential to have (meth)acrylates with hydroxyl groups, obtained by copolymerization with polymerizable unsaturated monomers as needed. It should be noted that in this specification, (meth)acrylate refers to methacrylic acid or acrylic acid.

[0103] Examples of (meth)acrylates containing hydroxyl groups include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate, and one or more of these can be used in combination.

[0104] Examples of polymerizable unsaturated monomers include alkyl methacrylates having alkyl groups with 1 to 22 carbon atoms, such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, and lauryl methacrylate.

[0105] Benzyl methacrylate, 2-phenylethyl methacrylate, and other aralkyl methacrylates;

[0106] Cyclohexyl methacrylate, isobornyl methacrylate, and other cycloalkyl methacrylates;

[0107] 2-Methoxyethyl ester of (meth)acrylate, 4-Methoxybutyl ester of (meth)acrylate, and other ω-alkoxyalkyl esters of (meth)acrylate;

[0108] Polyfunctional (meth)acrylates such as ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and dipentaerythritol hexa(meth)acrylate;

[0109] (Meth)acrylic acid, maleic acid, itaconic acid, citraconic acid, medoconic acid, maleic anhydride, 4-methylcyclohexyl-4-ene-1,2-dicarboxylic anhydride, bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride, 1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic anhydride, 2-octyl-1,3-dionespiro[4.4]non-7-ene, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, maleopimaric acid Polymerizable unsaturated monomers with acid groups, such as tetrahydrophthalic anhydride, methyl-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, methyl-norborn-5-ene-2,3-dicarboxylic anhydride, norborn-5-ene-2,3-dicarboxylic anhydride, sulfonated styrene, and vinylbenzene sulfonamide.

[0110] Vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and other vinyl carboxylic acid esters;

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

[0112] Dialkyl esters of unsaturated dicarboxylic acids, such as dimethyl maleate, di-n-butyl maleate, dimethyl fumarate, and dimethyl itaconic acid, are included, but not limited to these. They can be used alone or in combination of two or more.

[0113] Amine compounds (C7) are compounds containing an amino group. It should be noted that, in this specification, amino refers to an NH2 group or an NHR group (R is an alkyl or aryl group that may have a functional group).

[0114] As the amine compound (C7), known amine compounds can be used without particular limitation, including methylenediamine, ethylenediamine, isophoronediamine, 3,9-dipropylamine-2,4,8,10-tetraoxaspirocycloundecane, lysine, 2,2,4-trimethylhexamethylenediamine, hydrazine, piperazine, 2-hydroxyethylethylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropanediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, poly(propylene glycol)diamine, poly(propylene glycol)triamine, poly(propylene glycol)tetraamine, 1,2-diaminopropane, 1,3-diaminopropane, etc.

[0115] 1,4-Diaminobutane, 1,5-Diaminopentane, 1,6-Diaminohexane, 1,7-Diaminoheptane, 1,8-Diaminooctane, 1,9-Diaminononane, 1,10-Diaminodecane, Diethylenetriamine, Dipropylenetriamine, Triethylenetetramine, Tripropylenetetramine, Tetraethylenepentamine, Tetrapropylenepentamine, Pentylethylenehexamine, Nonadexethylenedeamine, Trimethylhexamethylenediamine, Tetra(aminomethyl)methane, Tetra(2-aminoethylaminomethyl)methane, 1,3-bis(2'-aminoethylamino)propane, Triethylene-bis(trimethylene)hexamine, Bis(3-aminoethyl)amine, Bishexamethylenetriamine, 1,4-Cyclohexanediamine, 4,4'-Methylenebicyclohexylamine, 4,4'-Isopropylidenebicyclohexylamine, Norbornenediamine,

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

[0117] Monoethanolamine, monoisopropanolamine, monobutanolamine, N-methylethanolamine, N-ethylethanolamine, N-methylpropanolamine, diethanolamine, diisopropanolamine, and other primary or secondary alkanolamines (C7-2).

[0118] Primary or secondary amines (C7-3) such as ethylamine, octylamine, laurylamine, myristicamine, stearylamine, oleylamine, diethylamine, dibutylamine, and distearate.

[0119] The amount of amine compound (C7) can be adjusted appropriately according to the purpose. For example, it is preferred to mix the isocyanate reactive composition (Y) so that the amine value is 20-70 mg KOH / g, more preferably 25-50 mg KOH / g.

[0120] It should be noted that the amine value in this specification refers to the number of milligrams of KOH equivalent to the amount of HCl required to neutralize 1g of the sample. There are no particular limitations, and it can be calculated using known methods. When the chemical structure of the amine compound (E7) is known, and consequently, the average molecular weight is known as needed, it can be calculated by (number of amino groups per molecule / average molecular weight) × 56.1 × 1000. When the chemical structure and average molecular weight of the amine compound are unknown, it can be determined according to known methods for amine value determination, such as JIS K7237-1995.

[0121] As an epoxy compound (C8), there are no particular limitations as long as it is a compound with an epoxy group in the molecule. Examples include polyglycidyl ether type epoxy resins of aliphatic polyols such as ethylene glycol, propylene glycol, hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol, diglycerol, sorbitol, spirodiol, or hydrogenated bisphenol A.

[0122] Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD ​​type epoxy resin, and other bisphenol type epoxy resins;

[0123] Aromatic epoxy resins such as glycidyl ether phenolic varnish resin, cresol phenolic varnish resin, and phenolic varnish type epoxy resin;

[0124] Polyglycidyl ethers are polyols that are adducts of ethylene oxide or propylene oxide of aromatic polyhydroxy compounds such as bisphenol A, bisphenol F, bisphenol S, and bisphenol AD.

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

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

[0127] Diepoxy resins of hydrocarbon dienes such as butadiene, hexadiene, octadiene, dodecadiene, cyclooctadiene, α-pinene or vinylcyclohexene;

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

[0129] Glycidylamine type epoxy resins include tetraglycidyl diaminodiphenylmethane, triglycidyl p-aminophenol, tetraglycidyl diaminomethylcyclohexane, diglycidyl aniline, and tetraglycidyl m-phenylenediamine.

[0130] Triazine, hydantoin, and other heterocyclic epoxy resins.

[0131] They can be used individually or in combination of two or more.

[0132] The isocyanate reactive compound (C) preferably contains a difunctional compound. This improves the flexibility of the cured coating film and produces a coating agent with superior adhesion to the substrate. The content of the difunctional compound in the isocyanate reactive compound (C) can be appropriately adjusted; for example, it is 50% by mass or more, or 80% by mass or more. The total amount of the isocyanate reactive compound (C) can be a difunctional compound.

[0133] The isocyanate reactive compound (C) preferably comprises a compound with a glass transition temperature (Tg) of 15°C or higher. This allows for the preparation of a coating agent that inhibits adhesion. The upper limit of the glass transition temperature of the isocyanate reactive compound (C) can be appropriately adjusted according to the purpose; for example, it may be 80°C or lower.

[0134] The coating agent of the present invention may contain a solvent. Examples of solvents that can be used in the coating agent of the present invention include esters such as ethyl acetate, butyl acetate, and cellosol acetate; ketones such as acetone, methyl ethyl ketone, isobutyl ketone, and cyclohexanone; ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane and dichloroethane; and dimethyl sulfoxide and dimethylsulfonamide. One or more solvents may be used in combination.

[0135] The coating agent of the present invention may contain additives such as urethane esterification catalysts, organic fillers, inorganic fillers, organic pigments, inorganic pigments, extender pigments, clay minerals, waxes, surfactants, stabilizers, flow modifiers, leveling agents, rheology control agents, ultraviolet absorbers, antioxidants, and plasticizers. The same substances used as those used in the two-component curing adhesives described later can be used as urethane esterification catalysts and pigments.

[0136] There are no particular limitations on the coating method used as the coating agent; conventionally known methods can be used. As examples, various coating methods can be cited, such as spraying, direct gravure coating, reverse gravure coating, offset gravure coating, flexographic coating, offset coating, bar coating, roller coating, forward rotary roller coating, reverse rotary roller coating, slot die coating, vacuum die coating, (micro)cavity doctor blade coating, air knife coating, blade coating, knife coating, spin coating, dip coating, etc.

[0137] The coating amount of the coating agent can be adjusted appropriately according to the application, etc. For example, it is 10g / m². 2 Above and 100g / m 2 the following.

[0138] The two-component curable coating agent of the present invention is preferably prepared by mixing and using a ratio of [NCO] to [isocyanate reactive functional groups] of the isocyanate reactive composition (Y) with a ratio of [NCO] / [isocyanate reactive functional groups] of 0.5 to 5.0, more preferably 1.0 to 3.0. This allows for appropriate curing properties regardless of the ambient humidity during coating.

[0139] Two-component curing adhesive

[0140] The two-component curing adhesive of the present invention comprises the above-mentioned polyisocyanate composition (X) and polyol composition (Y).

[0141] When the adhesive of the present invention is used as a solvent-free adhesive, the viscosity of the polyisocyanate composition (X) is adjusted to a range suitable for solvent-free lamination. As an example, the viscosity at 40°C is adjusted to a range of 100-50000 mPas, more preferably 500-20000 mPas. As an example, the viscosity of the polyisocyanate composition (X) can be adjusted by the structure of the polyurethane polyisocyanate (A1) (the polyol used). The viscosity of the polyisocyanate composition (X) can be measured, for example, using a rotational viscometer at a cone plate of 1° × diameter 50 mm and a shear rate of 100 sec. -1 The determination was carried out at 40℃±1℃.

[0142] 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 the solvent described later.

[0143] (Isocyanate reactive composition (Y))

[0144] The isocyanate reactive composition (Y) comprises an isocyanate reactive compound (C). As the isocyanate reactive compound (C), one substance identical to that used in the above-described coating agent or a combination of two or more substances can be used.

[0145] The isocyanate reactive compound (C) preferably contains a difunctional compound. This improves the flexibility of the cured adhesive film, resulting in an adhesive with superior adhesion and bonding to the substrate. The content of the difunctional compound in the isocyanate reactive compound (C) can be appropriately adjusted; for example, it is 50% by mass or more, or 80% by mass or more. The total amount of the isocyanate reactive compound (C) can be a difunctional compound.

[0146] The isocyanate reactive compound (C) preferably comprises a compound with a glass transition temperature (Tg) of 40°C or lower. This allows for the production of adhesives with excellent adhesion. The lower limit of the glass transition temperature of the isocyanate reactive compound (C) can be appropriately adjusted according to the intended use; for example, it may be -50°C or higher.

[0147] (Monohydric alcohol compound (D))

[0148] The isocyanate reactive composition (Y) may comprise a monohydric alcohol compound (D) having one alcoholic hydroxyl group. The main chain of the monohydric alcohol compound (D) is not particularly limited, and examples include vinyl resins, acrylic resins, polyesters, epoxy resins, and polyurethane resins having one hydroxyl group. Aliphatic alcohols and alkylalkylene glycols may also be used. The main chain of the monohydric alcohol compound (D) may be linear or branched. The bonding position of the hydroxyl group is not particularly limited, but it is preferably located at the end of the molecular chain.

[0149] Specific examples of monohydric alcohol compounds (D) include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, lauryl alcohol, myristol, pentadecanol, cetyl alcohol, heptadecanol, stearyl alcohol, nonadecanol, other alkanols (C20~50), oleyl alcohol, and their isomers, etc., aliphatic monohydric alcohols;

[0150] Cyclohexanol, methylcyclohexanol, 4-butylcyclohexanol, 4-pentylcyclohexanol, 4-hexylcyclohexanol, cyclodecyl alcohol, cyclododecanol, cyclopentadecanol, 4-isopropylcyclohexanol, 3,5,5-trimethylcyclohexanol, menthol, 2-norborneol, borneol, 2-adamantaneol, dicyclohexylmethanol, (6-isopropyl-2-decahydronaphthol), 2-cyclohexylcyclohexanol, 4-cyclohexylcyclohexanol, 4-(4-propylcyclohexyl)cyclohexanol, 4-(4-pentylcyclohexyl)cyclohexanol, α-ambrinol Deoxycorticosterone, 11-dehydrocorticosterone, cholesterol, β-sitosterol, campesterol, stigmasterol, campesterol, lanosterol, ergosterol, β-cholestanol, testosterone, estrogenone, digitoxigenin, dehydroepiandrosterone, coprostadanol, pregnenolone, epicholestanol, 7-dehydrocholestanol, estradiol benzoate, tigogenin, hecoside, dehydromethyltestosterone, cortisone acetate, dihydrotestosterone, and their isomers are all alicyclic monohydric alcohols.

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

[0152] Polyoxyalkylene monohydric alcohols are obtained by using alkyl compounds containing one active hydrogen atom as initiators to induce ring-opening addition polymerization of ethylene oxide, propylene oxide, butane oxide, tetrahydrofuran, and other epoxides; etc.

[0153] When the adhesive of the present invention is supplied in a solvent-free form, the viscosity of the isocyanate reactive composition (Y) is adjusted to a range suitable for solvent-free lamination. As an example, the viscosity at 40°C is adjusted to a range of 100-50000 mPas, more preferably 100-20000 mPas. The viscosity of the isocyanate reactive composition (Y) can be adjusted by the backbone of the isocyanate reactive compound (C) and / or by plasticizers, as described later.

[0154] (Other components of the adhesive)

[0155] The two-component curable adhesive of the present invention may contain components other than those described above. These other components may be included in any one or both of the polyisocyanate composition (X) and the isocyanate reactive composition (Y), or they may be prepared separately beforehand and mixed together with the polyisocyanate composition (X) and the isocyanate reactive composition (Y) just before the adhesive is applied. The components will be described below.

[0156] (catalyst)

[0157] Examples of catalysts include metal-based catalysts, amine-based catalysts, aliphatic cyclic amide compounds, and quaternary ammonium salts.

[0158] Examples of metal-based catalysts include metal complex catalysts, inorganic metal-based catalysts, and organometallic catalysts. Examples of metal complex catalysts include acetylacetone salts of metals selected from the group consisting of Fe (iron), Mn (manganese), Cu (copper), Zr (zirconium), Th (thorium), Ti (titanium), Al (aluminum), and Co (cobalt), such as iron acetylacetone, manganese acetylacetone, copper acetylacetone, and zirconium acetylacetone.

[0159] Catalysts selected from inorganic metal systems include Sn, Fe, Mn, Cu, Zr, Th, Ti, Al, and Co.

[0160] Examples of organometallic catalysts include: organozinc compounds such as zinc octanoate, zinc neodecanoate, and zinc naphthenate; organotin compounds such as stannous diacetate, stannous dioctanoate, stannous dioleate, stannous dilaurate, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin oxide, and dibutyltin dichloride; organonitrile compounds such as nickel octanoate and nickel naphthenate; organocobalt compounds such as cobalt octanoate and cobalt naphthenate; organobismuth compounds such as bismuth octanoate, bismuth neodecanoate, and bismuth naphthenate; titanium compounds such as tetraisopropoxy titanate, dibutyltitanium dichloride, tetrabutyl titanate, butoxytitanium trichloride, and titanium chelate complexes with at least one of aliphatic diketones, aromatic diketones, and alcohols with 2 to 10 carbon atoms as ligands.

[0161] Examples of amine catalysts include: triethylenediamine, 2-methyltriethylenediamine, quinine ring, 2-methylquinine ring, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropanediamine, 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(di... Methylaminopropyl)isopropanolamine, 3-quinol, N,N,N',N'-tetramethylguanidine, 1,3,5-tris(N,N-dimethylaminopropyl)hexahydro-triazine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N-methyl-N'-(2-dimethylaminoethyl)piperazine, N,N'-dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, 1-methylimidazolium, 1,2-dimethylimidazolium, 1-isobutyl-2-methylimidazolium, 1-dimethylaminopropylimidazolium, N,N-dimethylhexanolamine, N-methyl-N'-(2-hydroxyethyl)piperazine, 1-(2-hydroxyethyl)imidazolium, 1-(2-hydroxypropyl)imidazolium, 1-(2-hydroxyethyl)imidazolium, 1-(2-hydroxypropyl)imidazolium, 1-(2-hydroxyethyl)-2-methylimidazolium, 1-(2-hydroxypropyl)-2-methylimidazolium, etc.

[0162] Examples of aliphatic cyclic amide compounds include δ-valeramide, ε-caprolactam, ω-heptanolactam, η-octanolactam, and β-propiolactam. Among these, ε-caprolactam is more effective in promoting curing.

[0163] Examples of quaternary ammonium salts include hydroxyl salts, alkyl salts, and halide salts of alkylammonium and aromatic ammonium. Examples include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltriethylammonium chloride, and hexadecyltrimethylammonium bromide, but these are not the only examples.

[0164] (Coupled agent)

[0165] Examples of coupling agents include silane coupling agents, titanate coupling agents, and aluminum coupling agents.

[0166] Examples of silane coupling agents include aminosilanes such as γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, and bis[3-(triethoxysilyl)propyl]amine; epoxysilanes such as β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-epoxypropoxypropyltrimethoxysilane, and γ-epoxypropoxypropyltriethoxysilane; vinylsilanes such as vinyltri(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, and γ-methacryloyloxypropyltrimethoxysilane; and hexamethyldisilazane and γ-mercaptopropyltrimethoxysilane.

[0167] Examples of titanate-based coupling agents include tetraisopropoxy titanium, tetra-n-butoxy titanium, tetrabutyl titanate dimer, tetrastearate titanate, acetylacetone titanium, lactate titanium, tetraoctyl glycol titanate, lactate titanium, and tetrastearoxy titanium.

[0168] Examples of aluminum-based coupling agents include aluminum acetylalkoxydiisopropoxide.

[0169] (pigment)

[0170] As for pigments, there are no particular restrictions. Examples include extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments, green pigments, blue pigments, metallic pigments, luminescent pigments, pearl pigments, and other organic, inorganic, and even plastic pigments, as listed in the 1970 edition of the Coating Raw Materials Handbook (edited by the Japan Coatings Industry Association).

[0171] As extender pigments, examples include precipitated barium sulfate, lead white (Japanese: gofun), precipitated calcium carbonate, calcium hydrogen carbonate, gypsum, aluminum oxide white, silicon dioxide, hydrated fine silica powder (white carbon), ultrafine anhydrous silica (Aerosil), silica sand (silicon dioxide sand), talc, precipitated magnesium carbonate, bentonite, clay, kaolin, and loess, etc.

[0172] Specific examples of organic pigments include: various insoluble azo pigments such as benzidine yellow, Hansa yellow, and lake red 4R; soluble azo pigments such as lake red C, carmine 6B, and bordeaux 10; various phthalocyanine (copper) - based pigments such as phthalocyanine blue and phthalocyanine green; various chlorine - containing dye lakes such as rhodamine lake and methyl violet lake; various mordant dye - based pigments such as quinoline lake and fast sky blue; various vat dye - based pigments such as anthraquinone - based pigments, thioindigo - based pigments, and perinone - based pigments; various quinacridone - based pigments such as Cinquasia Red B; various dioxazine - based pigments such as dioxazine purple; various condensed azo pigments such as Cromophtal; aniline black; etc.

[0173] Examples of inorganic pigments include: various chromates such as chrome yellow, zinc chromate, and molybdenum orange; various ferrocyanides such as Prussian blue; various metal oxides such as titanium oxide, zinc white, Mapico Yellow, iron oxide, iron oxide red, chromium oxide green, and zirconium oxide; various sulfides and 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 violet; 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; metal pigments and pearlescent pigments such as mica flake pigments covered with metal oxides and micaceous iron oxide pigments; graphite, carbon black, etc.

[0174] Examples of plastic pigments include "GRANDOLL PP - 1000", "PP - 2000S", etc. manufactured by DIC Corporation.

[0175] Regarding the pigments used, they can be appropriately selected according to the purpose. For example, from the aspects of excellent durability, weather resistance, and designability, as white pigments, inorganic oxides such as titanium oxide and zinc white are preferably used, and as black pigments, carbon black is preferably used.

[0176] As an example, the compounding amount of the pigment is 1 - 400 parts by mass with respect to 100 parts by mass of the total non - volatile components of the polyol composition (X) and the polyisocyanate composition (Y). In order to make the adhesiveness and anti - blocking property better, it is more preferably set to 10 - 300 parts by mass.

[0177] (Plasticizer)

[0178] Examples of plasticizers include phthalic acid-based plasticizers, fatty acid-based plasticizers, aromatic polycarboxylic acid-based plasticizers, phosphoric acid-based plasticizers, polyol-based plasticizers, epoxy-based plasticizers, polyester-based plasticizers, and carbonate-based plasticizers.

[0179] Examples of phthalic acid-based plasticizers include: 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, di(tridecyl) phthalate, di(undecyl) phthalate, and phthalic acid phthalate. Dilaurate phthalate, distearate phthalate, diphenyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, dicyclohexyl phthalate, octyl decyl phthalate, dimethyl isophthalate, di(2-ethylhexyl) isophthalate, diisooctyl isophthalate, and other phthalate ester plasticizers; for example, di(2-ethylhexyl) tetrahydrophthalate, di-n-octyl tetrahydrophthalate, diisodecyl tetrahydrophthalate, and other tetrahydrophthalate ester plasticizers.

[0180] Examples of fatty acid-based plasticizers include: dibutyl adipate, di(2-ethylhexyl) adipate, diisodecyl adipate, diisononyl adipate, di(C6-C10) alkyl adipate, dibutyl diglycol adipate, and other adipic acid-based plasticizers; and di(2-ethylhexyl) azelaate, di(2-ethylhexyl) azelaate, diisooctyl azelaate, and other azelaic acid-based plasticizers. Examples of sebacate-based plasticizers include dibutyl sebacate, di(2-ethylhexyl) sebacate, and diisononyl sebacate; maleic acid-based plasticizers include dimethyl maleate, diethyl maleate, dibutyl maleate, and di(2-ethylhexyl) maleate; fumarate-based plasticizers include dibutyl fumarate and di(2-ethylhexyl) fumarate; and monomethyl itaconic acid and monobutyl itaconic acid are also mentioned. Itaconic acid plasticizers, such as esters, dimethyl itaconic acid, diethyl itaconic acid, dibutyl itaconic acid, and di(2-ethylhexyl) itaconic acid; stearic acid plasticizers, such as n-butyl stearate, glyceryl monostearate, and diethylene glycol distearate; oleic acid plasticizers, such as butyl oleate, glyceryl monooleate, and diethylene glycol monooleate; citric acid plasticizers, such as triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tributyl citrate, and acetyl tri(2-ethylhexyl) citrate; ricinoleic acid plasticizers, such as methyl acetylacetonate, butyl acetylacetonate, glyceryl monoricinoleate, and diethylene glycol monoricinoleate; and other fatty acid plasticizers, such as diethylene glycol monolaurate, diethylene glycol dinonanoate, and pentaerythritol fatty acid esters.

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

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

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

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

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

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

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

[0188] (acid anhydride)

[0189] Examples of acid anhydrides include cyclic aliphatic anhydrides, aromatic anhydrides, and unsaturated carboxylic acid anhydrides. One type or a combination of two or more can be used. More specifically, examples include: maleic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, dodecenyl succinic anhydride, polyadipic anhydride, polyazelic anhydride, polysaccharide anhydride, poly(ethyl octadecanoic acid) anhydride, poly(phenyl hexadecanoic acid) anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, hexahydrophthalic anhydride, methyl nadic anhydride (anhydrous form of methyl hymic acid), trialkyl Tetrahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, methylcyclohexene tetracarboxylic anhydride, ethylene glycol dipreptyltrimethyl ester dianhydride, chlorobrittle anhydride, norbornyl edyl anhydride, methyl norbornyl edyl anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthous succinic anhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthous succinic anhydride, etc.

[0190] As an acid anhydride, compounds modified with diols as described above can also be used. Examples of diols 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, copolymers of two or more of these diols and / or polyether glycols can also be used.

[0191] Alternatively, homopolymers or copolymers of compounds with polymerizable unsaturated groups, such as maleic anhydride mentioned above, can be used as acid anhydrides. Examples of compounds capable of copolymerizing with compounds having both anhydride and polymerizable unsaturated groups include α-olefins such as ethylene, propylene, 1,3-butadiene, and cyclopentylethylene; vinyl compounds with aromatic rings 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 9-ethynylphenanthrene; and fluoroolefins such as vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, and trifluorochloroethylene. One or more of these compounds can be used alone or in combination. Styrene and p-tert-butylstyrene, which are vinyl compounds with aromatic rings, are preferred.

[0192] (Phosphoric acid compounds)

[0193] Examples of phosphoric acid compounds include: phosphoric acid, pyrophosphate, tripolyphosphate, methyl phosphate, ethyl phosphate, butyl phosphate, dibutyl phosphate, 2-ethylhexyl phosphate, bis(2-ethylhexyl) phosphate, isododecyl phosphate, butoxyethyl phosphate, oleyl phosphate, tetradecyl phosphate, 2-hydroxyethyl methacrylate phosphate, and polyoxyethylene alkyl ether phosphate. In the adhesive of the present invention, the polyisocyanate composition (X) contains a phosphoric acid compound, therefore, the phosphoric acid compound can be omitted when preparing the adhesive.

[0194] (Form of adhesive)

[0195] The two-component curable adhesive of the present invention can be in any form, either solvent-based or solvent-free. It should be noted that, in this specification, "solvent-based" adhesive refers to the form used in a so-called dry lamination method, which involves applying the adhesive to a substrate, heating it in an oven or similar environment to evaporate the organic solvent in the coating, and then bonding it to other substrates. Either or both of the polyisocyanate composition (X) and the isocyanate reactive composition (Y) contain an organic solvent capable of dissolving (diluting) the constituent components of the polyisocyanate composition (X) and the isocyanate reactive composition (Y) used in the present invention.

[0196] Examples of organic solvents include: esters such as ethyl acetate, butyl acetate, and cellosol acetate; ketones such as acetone, methyl ethyl ketone, isobutyl ketone, and cyclohexanone; ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane and dichloroethane; dimethyl sulfoxide; and dimethyl sulfonamide. Organic solvents used as reaction media in the manufacture of polyisocyanate compositions (X) and isocyanate reactive compositions (Y) are sometimes further used as diluents during coating processes.

[0197] In this specification, "solvent-free" adhesive refers to the form of adhesive used in a so-called solvent-free lamination method, which is a method of bonding adhesive to other substrates without heating in an oven or similar process to evaporate the solvent. In the adhesive, the polyisocyanate composition (X) and the isocyanate reactive composition (Y) are substantially free of esters such as ethyl acetate, butyl acetate, and cellosol acetate; ketones such as acetone, methyl ethyl ketone, isobutyl ketone, and cyclohexanone; ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane and dichloroethane; and highly soluble organic solvents such as dimethyl sulfoxide and dimethyl sulfonamide, and in particular, substantially free of ethyl acetate or methyl ethyl ketone. If trace amounts of organic solvent remain in the polyisocyanate composition (X) or isocyanate reactive composition (Y) because the organic solvent used as a reaction medium during the manufacture of its components or raw materials was not completely removed, it is considered substantially solvent-free. Furthermore, if the isocyanate reactive composition (Y) contains a low molecular weight alcohol, the low molecular weight alcohol reacts with the polyisocyanate composition (X) to become part of the coating film, and therefore does not need to evaporate after coating. Therefore, this form is also treated as a solvent-free adhesive, and the low molecular weight alcohol is not considered an organic solvent.

[0198] The two-component curable adhesive of the present invention is preferably prepared by mixing and using a ratio of [NCO] to [isocyanate reactive functional groups] of the polyisocyanate composition (X) to the isocyanate reactive composition (Y) in which the ratio [NCO] / [isocyanate reactive functional groups] is 0.5 to 5.0, more preferably 1.0 to 3.0. This allows for appropriate curing properties that are independent of the ambient humidity during application.

[0199] <Layered Body>

[0200] The laminate of the present invention is obtained, for example, by the following methods: a two-component mixing step in which a polyisocyanate composition (X) and an isocyanate reactive composition (Y) are premixed, coated onto a first substrate, and then a second substrate is laminated on the coated surface, and an adhesive layer is cured; and a two-component separate coating step in which a polyisocyanate composition (X) and an isocyanate reactive composition (Y) are respectively coated onto a first substrate and a second substrate, and then the coated surfaces are brought into contact and pressed together, thereby laminating the first substrate and the second substrate, and the adhesive layer is cured. There are no particular limitations on the film used; a film suitable for the application can be appropriately selected.

[0201] For example, for food packaging, examples include: polyethylene terephthalate (PET) film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film (LLDPE: low-density polyethylene film, HDPE: high-density polyethylene film, MDOPE: uniaxially stretched polyethylene film, OPE: biaxially stretched polyethylene film), polypropylene film (CPP: unstretched polypropylene film, OPP: biaxially stretched polypropylene film), and gas-barrier heat-sealing films such as polyolefin films, polyvinyl alcohol films, and ethylene-vinyl alcohol copolymer films, which have an olefin-based heat-sealing resin layer on one or both sides of a gas-barrier resin such as ethylene-vinyl alcohol copolymer or polyvinyl alcohol.

[0202] In addition, biomass films, biodegradable films, and recycled plastic films formed from materials containing biomass-derived components, biodegradable components, or recycled components are preferred.

[0203] In addition to being sold by individual companies, biomass films, biodegradable films, and recycled plastic films can also be certified by various countries, such as those listed in the list of biomass certified products recorded in the Japan Organic Resources Association, those listed in the list of eco-label certified products recorded in the Japan Environment Association, and those bearing the symbols and markings stipulated by the Japan Bioplastics Association.

[0204] (Biomass film)

[0205] As a well-known example of biomass film, one can cite films made from biomass-derived ethylene glycol. Biomass-derived ethylene glycol is ethylene glycol produced from biomass-based ethanol (biomass ethanol). For example, biomass-derived ethylene glycol can be obtained by using conventionally known methods, such as methods for producing ethylene glycol from biomass ethanol via ethylene oxide. Alternatively, commercially available biomass ethylene glycol can be used; for example, biomass ethylene glycol commercially available from IndiaGlycols Limited is suitable.

[0206] For example, as alternatives to conventional polyethylene terephthalate films that use petroleum-based raw materials, films containing biomass polyesters and biomass polyethylene terephthalate are known.

[0207] The dicarboxylic acid units of biomass polyesters use dicarboxylic acids derived from fossil fuels. Aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and their derivatives can be used without restriction as dicarboxylic acids.

[0208] Alternatively, the copolyester can be obtained as follows: in addition to the diol and dicarboxylic acid components mentioned above, a difunctional hydroxycarboxylic acid and / or at least one polyfunctional compound selected from the group consisting of a polyol with three or more functions, a polycarboxylic acid with three or more functions and / or its anhydride and a hydroxycarboxylic acid with three or more functions as a third component for forming a crosslinking structure.

[0209] In addition, as alternatives to conventional polyolefin films that use petroleum-based raw materials, biomass polyolefin films containing polyethylene resins made from biomass-derived ethylene glycol and biomass polyethylene-polypropylene films are also known.

[0210] Polyethylene resins are not particularly limited except for the use of ethylene glycol from the aforementioned biomass source in part of the raw materials. Examples include homopolymers of ethylene, copolymers of ethylene and α-olefins with ethylene as the main component (ethylene-α-olefin copolymers containing more than 90% by mass of ethylene units), etc. They can be used alone or in combination of two or more.

[0211] It should be noted that the α-olefin constituting the copolymer of ethylene and α-olefin is not particularly limited, and examples include α-olefins with 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. From the viewpoint that even if the films rub against each other, damage such as openings and cracks is less likely to occur, linear low-density polyethylene resin (LLDPE) (a copolymer of ethylene and 1-hexene, or a copolymer of ethylene and 1-octene) is preferred, and a density of 0.910 to 0.925 g / cm³ is more preferred. 3 Linear low-density polyethylene resin.

[0212] As biomass films, films made from biomass raw materials, categorized by biomass plasticity as specified in ISO 16620 or ASTM D6866, are also in circulation. Radioactive carbon-14 (C14C) exists in the atmosphere at a ratio of 1 in 10¹², a ratio that remains constant in atmospheric carbon dioxide and therefore also remains constant in plants that fix this carbon dioxide through photosynthesis. Therefore, plant-derived resins contain C14C. In contrast, fossil fuel-derived resins contain almost no C14C. Therefore, by determining the concentration of C14C in the resin using an accelerator mass spectrometer, the proportion of plant-derived resin in the resin, i.e., the biomass plasticity, can be determined.

[0213] Low-density polyethylene (LDPE) derived from plants, as specified in ISO 16620 or ASTM D6866, has a biomass plasticity of 80% or more, preferably 90% or more. Examples of suitable biomass plastics are those manufactured by Braskem under trade names such as "SBC818", "SPB608", "SBF0323HC", "STN7006", "SEB853", and "SPB681".

[0214] In addition, films and sheets containing starch and polylactic acid as biomass raw materials are also known. They can be selected and used appropriately according to their intended use.

[0215] Biomass films can be laminates of multiple biomass films, or they can be laminates of conventional petroleum-based films and biomass films. Furthermore, these biomass films can be unstretched or stretched films, and there are no limitations on their manufacturing method.

[0216] (Biodegradable film)

[0217] Specific examples of well-known biodegradable films include those made from commonly available biodegradable resins. Examples include polycaprolactone, polyvinyl alcohol, polyamide, cellulose esters, lactic acid polyester resins, aliphatic polyester resins, and aliphatic aromatic polyester resins. These biodegradable resins can be used alone or in combination of two or more. Aliphatic polyester resins or aliphatic aromatic polyester resins are preferred.

[0218] Examples of aliphatic polyester resins include aliphatic polyesters obtained through the polycondensation reaction of aliphatic diols with aliphatic dicarboxylic acids. Examples of aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, and 1,4-cyclohexanediol. They can be used alone or in mixtures. 1,4-Butanediol is preferred. Examples of aliphatic dicarboxylic acids include oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, octanoic acid, and dodecanoic acid; anhydrides derived from these can also be used. Succinic acid or succinic anhydride, or mixtures thereof with adipic acid, are preferred.

[0219] Specifically, examples include polybutylene succinate (PBS) obtained from 1,4-butanediol and succinic acid (e.g., BioPBS prepared by PPT MCC Biochem) and polybutylene adipate succinate (PBSA) copolymerized with adipic acid in PBS.

[0220] Examples of aliphatic aromatic polyester resins include copolymers comprising aliphatic dicarboxylic acid units, aromatic dicarboxylic acid units, and chain-like aliphatic and / or alicyclic diol units. The diol component providing the diol unit typically has 2 to 10 carbon atoms, and examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,4-cyclohexanediol. Diols with 2 to 4 carbon atoms are preferred, with ethylene glycol and 1,4-butanediol being more preferred, and 1,4-butanediol being even more preferred. The dicarboxylic acid component providing the dicarboxylic acid unit typically has 2 to 10 carbon atoms, and examples include succinic acid, adipic acid, octanoic acid, sebacic acid, and dodecanoic acid. Succinic acid or adipic acid is preferred. Examples of aromatic dicarboxylic acid components providing the aromatic dicarboxylic acid unit include terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid. Among them, terephthalic acid and isophthalic acid are preferred, and terephthalic acid is even more preferred.

[0221] Specifically, examples include PBAT, which is a copolymer of 1,4-butanediol, adipic acid, and terephthalic acid (e.g., Ecoflex manufactured by BASF Corporation).

[0222] Other examples include: poly(3-hydroxyalkanoates) of aliphatic polyester copolymers obtained from hydroxyalkanoates and polycarboxylic acids (wherein, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) (e.g., AONILEX manufactured by Kaneka Corporation), and polylactic acid (PLA) (e.g., REVODE manufactured by Hisun Biomaterials Co., Ltd., and Ingeo manufactured by Nature Works LLC.).

[0223] Biodegradable films can be laminates of multiple biodegradable films, or laminates of conventional petroleum-based films and biodegradable films. Furthermore, these biodegradable films can be unstretched or stretched films, and their manufacturing methods are not limited.

[0224] The film can be a film that has undergone stretching treatment. As a stretching treatment method, resin is typically melted and extruded into a sheet using methods such as extrusion film forming, followed by simultaneous biaxial stretching or successive biaxial stretching. In the case of successive biaxial stretching, longitudinal stretching is usually performed first, followed by transverse stretching. Specifically, a combination of longitudinal stretching utilizing the speed difference between rollers and transverse stretching using a tenter frame is often used.

[0225] Various surface treatments, such as flame treatment and corona discharge treatment, can be applied to the film surface as needed to form an adhesive layer without defects such as film breakage and shrinkage.

[0226] Alternatively, a barrier film containing vapor-deposited layers of metals such as aluminum, silicon dioxide, and / or metal oxides such as alumina, or a gas barrier layer containing polyvinyl alcohol and / or ethylene-vinyl alcohol copolymer, vinylidene chloride, etc., can be used. By using such films, it is possible to produce a laminate that provides barrier properties against water vapor, oxygen, alcohols, inactive gases, volatile organic compounds (fragrances), etc.

[0227] As for paper, there are no particular limitations, and known paper base materials can be used. Specifically, it can be manufactured using natural papermaking fibers such as wood pulp using known papermaking machines, but the papermaking conditions are not particularly specified. Examples of natural papermaking fibers include: wood pulps such as softwood pulp and hardwood pulp; non-wood pulps such as Manila hemp pulp, sisal pulp, and flax pulp; and pulps obtained by chemically modifying these pulps; etc. As for the type of pulp, chemical pulps, milled pulps, chemically milled pulps, thermomechanical pulps, etc., based on sulfate hydrolysis, acid / neutral / alkaline sulfite hydrolysis, sodium salt hydrolysis, etc., can be used. In addition, various commercially available high-quality papers, coated paper, lining paper, impregnated paper, thick paper, paperboard, etc., can also be used.

[0228] As a more specific example of the composition of a stacked body, the following can be cited:

[0229] (1) Substrate 1 / Adhesive layer 1 / Sealing film

[0230] (2) Substrate 1 / Adhesive layer 1 / Metal vapor-deposited unstretched film

[0231] (3) Substrate 1 / Adhesive layer 1 / Metal vapor-deposited stretched film

[0232] (4) Transparent vapor-deposited stretch film / adhesive layer 1 / sealing film

[0233] (5) Substrate 1 / Adhesive layer 1 / Substrate 2 / Adhesive layer 2 / Sealing film

[0234] (6) Substrate 1 / Adhesive layer 1 / Metal vapor-deposited stretched film / Adhesive layer 2 / Sealing film

[0235] (7) Substrate 1 / Adhesive layer 1 / Transparent vapor-deposited stretch film / Adhesive layer 2 / Sealing film

[0236] (8) Substrate 1 / Adhesive layer 1 / Metal layer / Adhesive layer 2 / Sealing film

[0237] (9) Substrate 1 / Adhesive layer 1 / Substrate 2 / Adhesive layer 2 / Metal layer / Adhesive layer 3 / Sealing film

[0238] (10) Substrate 1 / Adhesive Layer 1 / Metal Layer / Adhesive Layer 2 / Substrate 2 / Adhesive Layer 3 / Sealing Film

[0239] etc., but not limited to this.

[0240] Examples of substrate 1 used in component (1) include MDOPE film, OPE film, OPP film, PET film, nylon film, and paper. Alternatively, substrate 1 may be a substrate coated to improve gas barrier properties and ink receptivity when the printing layer described later is applied. Commercially available examples of coated substrate films 1 include K-OPP film, K-PET film, and K-nylon film. Adhesive layer 1 is a cured coating of the adhesive of the present invention. Examples of sealing films include CPP film, LLDPE film, easy-open heat-sealable film, and gas-barrier heat-sealable film. The printing layer may be applied to the adhesive layer 1 side of substrate 1 (or the adhesive layer 1 side of the coated layer when using a coated substrate film as substrate film 1) or the side opposite to adhesive layer 1. The printed layer is formed using various printing inks such as gravure ink, flexographic ink, offset ink, screen printing ink, and inkjet ink, through conventional printing methods previously used in printing polymer films and / or paper.

[0241] Examples of substrate 1 used in configurations (2) and (3) include MDOPE film, OPE film, OPP film, PET film, and paper. Adhesive layer 1 is a cured coating of the adhesive of the present invention. As a metal-deposited unstretched film, VM-CPP film and VM-LLDPE film, which have undergone metal deposition of aluminum or the like on CPP film, LLDPE film, and gas-barrier heat-sealing film, can be used. As a metal-deposited stretched film, VM-MDOPE film, VM-OPE film, and VM-OPP film, which have undergone metal deposition of aluminum or the like on MDOPE film, OPE film, and OPP film, can be used. Similar to configuration (1), a printing layer can be provided on any surface of substrate 1.

[0242] Examples of transparent vapor-deposited stretch films used in configuration (4) include films in which silicon dioxide or aluminum oxide has been vapor-deposited onto MDOPE films, OPE films, OPP films, PET films, nylon films, etc. For purposes such as protecting the inorganic vapor-deposited layers of silicon dioxide or aluminum oxide, films coated on the vapor-deposited layers can be used. Adhesive layer 1 is a cured coating of the adhesive of the present invention. Sealing film can be the same as that in configuration (1). A printing layer can be provided on the adhesive layer 1 side of the transparent vapor-deposited stretch film (in the case of using a transparent vapor-deposited stretch film coated on an inorganic vapor-deposited layer, the adhesive layer 1 side of the coating layer). The method for forming the printing layer is the same as in configuration (1).

[0243] Examples of substrate 1 used in configuration (5) include PET film and paper. Examples of substrate 2 include nylon film. At least one of adhesive layer 1 and adhesive layer 2 is a cured coating of the adhesive of the present invention. Examples of sealing film are the same as those in configuration (1). Similar to configuration (1), a printing layer can be provided on any surface of substrate 1.

[0244] As the substrate 1 of configuration (6), examples of substrates similar to those in configurations (2) and (3) can be given. As a metal vapor-deposited stretched film, examples of VM-MDOPE film, VM-OPE film, VM-OPP film, and VM-PET film are given, which are formed by metal vapor deposition of aluminum or the like on MDOPE film, OPE film, OPP film, and PET film. At least one of adhesive layer 1 and adhesive layer 2 is a cured coating of the adhesive of the present invention. Examples of sealing films are the same as those in configuration (1). Similar to configuration (1), a printing layer can be provided on any surface of substrate 1.

[0245] Examples of substrate 1 in component (7) include PET film and paper. Examples of transparent vapor-deposited stretch film include the same film as in component (4). At least one of adhesive layers 1 and 2 is a cured coating of the adhesive of the present invention. Examples of sealing film include the same sealing film as in component (1). Similar to component (1), a printing layer can be provided on any surface of substrate 1.

[0246] Examples of substrate 1 in configuration (8) include PET film and paper. Examples of metal layers include aluminum foil. At least one of adhesive layers 1 and 2 is a cured coating of the adhesive of the present invention. Examples of sealing films are the same as those in configuration (1). Similar to configuration (1), a printing layer can be provided on any surface of substrate 1.

[0247] Examples of substrate 1 in components (9) and (10) include PET film and paper. Examples of substrate 2 include nylon film. Examples of metal layer include aluminum foil. At least one of adhesive layers 1, 2, and 3 is a cured coating of the adhesive of the present invention. Examples of sealing film are the same as those in component (1). Similar to component (1), a printing layer can be provided on any surface of substrate 1.

[0248] In addition to the above-described components (1) to (10), the laminate of the present invention may also include other films and substrates. As other substrates, in addition to the stretched film, unstretched film, and transparent vapor-deposited film described above, porous substrates such as paper, wood, and leather, which will be described later, may also be used. The adhesive used when bonding other substrates may be the adhesive of the present invention, or it may not be the adhesive of the present invention.

[0249] "Other layers" may include known additives and stabilizers, such as antistatic agents, easy-to-apply coating agents, plasticizers, lubricants, antioxidants, etc. In addition, "other layers" may also be those for which the surface of the film has undergone pretreatment such as corona treatment, plasma treatment, ozone treatment, chemical treatment, solvent treatment, etc., to improve the adhesion when laminated with other materials.

[0250] The laminate of the present invention can be used for various purposes, such as packaging materials for food, medicine, and daily necessities; lids; paper straws, napkins, paper spoons, paper plates, paper cups, and other paper tableware; defensive materials; roofing materials; solar panel materials; battery packaging materials; window materials; outdoor flooring materials; lighting protection materials; automotive components; signs; stickers, and other outdoor industrial applications; decorative sheets used in injection molding and decoration methods; and packaging materials for liquid detergents, kitchen liquid detergents, bath liquid detergents, bath liquid soaps, liquid shampoos, liquid conditioners, etc.

[0251] Packaging Materials

[0252] The laminated body of the present invention can be used as a multi-layer packaging material for the purpose of protecting food, pharmaceuticals, etc. When used as a multi-layer packaging material, its layer composition can be varied according to the contents, the usage environment, and the usage pattern. In addition, easy-opening and resealing mechanisms can be appropriately provided on the packaging body of the present invention.

[0253] As an example of a specific packaging material of the present invention, a packaging material made by forming a bag with a sealing film, as described in the above-mentioned examples of the structure of the laminate (1), (4) to (10), is provided. The laminate is bent or overlapped so that the inner surfaces (the surfaces of the sealing film) face each other, and its peripheral ends are heat-sealed to form a bag. As a bag-making method, heat-sealing methods can be described by side-sealing, two-side-sealing, three-side-sealing, four-side-sealing, envelope adhesive sealing, folded adhesive sealing, pleated sealing, flat-bottom sealing, square-bottom sealing, folded bag type, and other heat-sealing methods. The packaging material of the present invention can take various forms depending on the contents, the usage environment, and the usage form. It can also be a self-standing packaging material (stand-up pouch), etc. As a heat-sealing method, known methods such as rod sealing, rotary roller sealing, strip sealing, pulse sealing, high-frequency sealing, and ultrasonic sealing can be described.

[0254] In the packaging material of the present invention, after filling the contents through its opening, the opening is heat-sealed to manufacture an article using the packaging material of the present invention. Examples of the contents to be filled, for example, as food products, include: rice crackers, bean-based snacks, nuts, biscuits / cookies, wafers, fruit gummies, pies, semi-baked cakes, candies, snacks, bread, snack noodles, instant noodles, dried noodles, pasta, aseptically packaged rice, mixed porridge, porridge, packaged sticky rice cakes, cereal foods, etc., staple foods, pickled vegetables, boiled beans, natto, miso, frozen tofu, tofu, chestnut mushrooms, konjac, processed wild vegetables, jams, peanut butter, salads, frozen vegetables, processed potato products, etc., processed agricultural products such as ham, cured meat, sausages, processed chicken, and corned beef. Animal products such as processed meats, fish, ham / sausages, aquatic porridge products, fish cakes, seaweed, sweet seafood, dried bonito, salted fish, smoked salmon, spicy mentaiko and other processed aquatic products, fruits and meats such as peaches, citrus fruits, pineapples, apples, pears, cherries, corn, asparagus, mushrooms, onions, carrots, radishes, potatoes and other vegetables, frozen home-cooked dishes such as hamburger patties, meatballs, fried seafood, dumplings, croquettes and other cooked foods, dairy products such as butter, margarine, cheese, cream, instant cream powder, infant formula and other food products, liquid seasonings, steamed curry, pet food and other food products.

[0255] In addition, as a non-food product, it can be used as packaging material for various products such as cigarettes, disposable hand warmers, infusion bags and other pharmaceuticals, liquid detergents for washing, liquid detergents for kitchen use, liquid detergents for bathing, liquid soaps for bathing, liquid shampoos, liquid conditioners, lotions and other cosmetics, vacuum insulation materials, and batteries.

[0256] Example

[0257] The present invention will be described in more detail below with specific examples of synthesis and embodiments, but the present invention is not limited to these embodiments. It should be noted that, in the following examples, unless otherwise stated, "parts" and "%" represent "parts by mass" and "% by mass", respectively.

[0258] <Preparation of Polyisocyanate Composition (X)>

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

[0260] Toluene diisocyanate (TDI) 720.0 parts were added to a reaction vessel equipped with a stirrer, thermometer, nitrogen inlet pipe, and condenser. The mixture was heated to 40°C under a nitrogen atmosphere with stirring. Then, while monitoring the heating process, 182.0 parts of polyoxypropylene sorbitol ether (SANNIX SP-750, manufactured by Sanyo Chemicals) and 98.0 parts of difunctional polyethylene glycol with a molecular weight of 400 were added, and the mixture was heated to 60°C. The reaction was continued at 60°C until the NCO% no longer changed. Then, 0.2 parts of butyl phosphate were added to terminate the reaction. Next, purification was carried out using a thin-film distillation apparatus at a pressure of approximately 0.02 Torr and a temperature of 160°C until the TDI in the urethane prepolymer, the product of the reaction between TDI and the polyol, reached 0.05% by mass in the solids composition. This was dissolved and diluted with ethyl acetate to prepare a solution with 80% by mass of non-volatile components, thereby obtaining the polyisocyanate composition (X-1). The NCO% of the polyisocyanate composition (X-1) is 10.5%.

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

[0262] Toluene diisocyanate (TDI) of 819.1 parts was added to a reaction vessel equipped with a stirrer, thermometer, nitrogen inlet pipe, and condenser. The mixture was heated to 40°C under a nitrogen flow while stirring. Then, while monitoring the heating process, 180.9 parts of polyoxypropylene sorbitol ether (SANNIX SP-750, manufactured by Sanyo Chemicals) were added, and the mixture was heated to 60°C. The reaction was further carried out at 60°C for 4 hours, and then 1.0 part of polyphosphoric acid was added to terminate the reaction. Next, purification was performed using a thin-film distillation apparatus at a pressure of approximately 0.02 Torr and a temperature of 160°C until the TDI in the urethane prepolymer, which is the product of the reaction of TDI and polyol, reached 0.05% by mass in the solids composition. This was dissolved and diluted with ethyl acetate to prepare a solution with 76% by mass of non-volatile components, thereby obtaining the polyisocyanate composition (X-2). The NCO% of the polyisocyanate composition (X-2) was 10.5%.

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

[0264] Toluene diisocyanate (TDI) of 788.7 parts was added to a reaction vessel equipped with a stirrer, thermometer, nitrogen inlet pipe, and condenser. The mixture was heated to 40°C under a nitrogen flow while stirring. Then, while monitoring the heating process, 147.9 parts of polyoxypropylene sucrose ether (SANNIX HS-209, manufactured by Sanyo Chemicals) and 63.4 parts of difunctional polyethylene glycol with a molecular weight of 400 were added, followed by heating to 60°C. The reaction was further carried out at 60°C for 4 hours, and then 0.2 parts of butyl phosphate were added to terminate the reaction. Next, purification was performed using a thin-film distillation apparatus at a pressure of approximately 0.02 Torr and a temperature of 160°C until the TDI in the urethane prepolymer, the product of the reaction between TDI and the polyol, reached 0.05% by mass in the solids composition, thus obtaining the polyisocyanate composition (X-3). The NCO% of the polyisocyanate composition (X-3) was 12.9%.

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

[0266] 500.0 parts of toluene diisocyanate (TDI) were added to a reaction vessel equipped with a stirrer, thermometer, nitrogen inlet pipe, and condenser, and heated to 60°C under a nitrogen flow while stirring. Then, 657.6 parts of difunctional polypropylene glycol (AGC EXCENOL 420) were added while monitoring the heat, and the mixture was heated to 80°C and reacted at 80°C for 2 hours. Next, purification was carried out using a thin-film distillation apparatus at a pressure of approximately 0.02 Torr and a temperature of 160°C until the TDI in the urethane prepolymer, which is the reaction product of TDI and polypropylene glycol, reached 0.05% by mass in the solids composition, thus obtaining the polyisocyanate composition (X'-4). The NCO% of the polyisocyanate composition (X'-4) was 8.9%.

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

[0268] 500.0 parts of toluene diisocyanate (TDI) were added to a reaction vessel equipped with a stirrer, thermometer, nitrogen inlet pipe, and condenser, and heated to 40°C under a nitrogen flow while stirring. Then, 657.6 parts of difunctional polypropylene glycol (AGC EXCENOL 420) were added while monitoring the heat, and the mixture was heated to 60°C. The reaction was further carried out at 60°C for 4 hours, and then 1.0 part of polyphosphoric acid was added to terminate the reaction. Next, purification was carried out using a thin-film distillation apparatus at a pressure of approximately 0.02 Torr and a temperature of 160°C until the TDI in the urethane prepolymer, which is the product of the reaction of TDI and polypropylene glycol, reached 0.05% by mass in the solids composition, thereby obtaining the polyisocyanate composition (X'-5). The NCO% of the polyisocyanate composition (X'-5) was 9.0%.

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

[0270] Toluene diisocyanate (TDI) 720.0 parts were added to a reaction vessel equipped with a stirrer, thermometer, nitrogen inlet pipe, and condenser. The mixture was heated to 40°C under a nitrogen atmosphere with stirring. Then, while monitoring the heating process, 182.0 parts of polyoxypropylene sorbitol ether (SANNIX SP-750, manufactured by Sanyo Chemicals) and 98.0 parts of difunctional polyethylene glycol with a molecular weight of 400 were added, followed by heating to 60°C. The reaction was further carried out at 60°C for 4 hours, and then 10.0 parts of polyphosphoric acid were added to terminate the reaction. Next, purification was performed using a thin-film distillation apparatus at a pressure of approximately 0.02 Torr and a temperature of 160°C until the TDI in the urethane prepolymer, the product of the reaction between TDI and the polyol, reached 0.05% by mass in the solids composition. This was dissolved and diluted with ethyl acetate to prepare a solution with 80% by mass of non-volatile components, thereby obtaining the polyisocyanate composition (X'-6). The NCO% of the polyisocyanate composition (X'-6) was 10.4%.

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

[0272] Toluene diisocyanate (TDI) 899.4 parts were added to a reaction vessel equipped with a stirrer, thermometer, nitrogen inlet pipe, and condenser, and heated to 40°C under a nitrogen flow while stirring. Then, while monitoring the heat, 100.6 parts of polyglycerol 10 (a polymer of 10 glycerols) were added, and the mixture was heated to 60°C. The reaction was further carried out at 60°C for 4 hours, and then 1.0 part of polyphosphoric acid was added to terminate the reaction. Next, purification was carried out using a thin-film distillation apparatus at a pressure of approximately 0.02 Torr and a temperature of 160°C until the TDI in the urethane prepolymer, which is the product of the reaction of TDI and polyol, reached 0.05% by mass in the solids component. This was dissolved and diluted with ethyl acetate to prepare a 75% by mass solution of non-volatile components, thereby obtaining the polyisocyanate composition (X'-7). The NCO% of the polyisocyanate composition (X'-7) was 12.0%.

[0273] <Preparation of Isocyanate Reactive Composition (Y)>

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

[0275] In a polyester reaction vessel equipped with a stirrer, thermometer, nitrogen inlet pipe, and distillation tube, 130 parts of terephthalic acid, 130 parts of isophthalic acid, 150 parts of adipic acid, 50 parts of dimer acid, 70 parts of ethylene glycol, 65 parts of diethylene glycol, 65 parts of neopentyl glycol, and 60 parts of 1,6-hexanediol were added, and an esterification reaction was carried out at an internal temperature of 250°C. After dehydration, an intermediate polyester polyol with an acid value of 1 mg KOH / g was obtained. This was dissolved and diluted with ethyl acetate to prepare a solution with a non-volatile component of 65% by mass. Then, relative to 100 parts of the solid component of the intermediate polyester polyol, 4 parts of isophorone diisocyanate were added, and the mixture was heated to 80°C to carry out a carbamate esterification reaction until the free NO groups substantially disappeared, yielding an isocyanate reactive composition (Y-1) with a non-volatile component of 65% by mass and a hydroxyl value of 6.

[0276] <Evaluation>

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

[0278] The prepared polyisocyanate compositions (X-1) to (X-3) and (X'-4) to (X'-7) were filled with 15 ml glass bottles and stored at room temperature for a period of time. The state of the polyisocyanate composition (X) after storage was evaluated in two stages according to the following criteria, and the results are summarized in Table 1.

[0279] 〇: Not cured after more than 30 days

[0280] ×: Curing within 30 days

[0281] [Table 1]

[0282]

[0283] (Preparation of adhesive)

[0284] The adhesives of the Examples and Comparative Examples were prepared by mixing the polyisocyanate composition (X) and the isocyanate reactive composition (Y) as shown in Table 2. It should be noted that the polyisocyanate compositions (X'-7) underwent curing and therefore were not evaluated as adhesives.

[0285] (Heat seal strength)

[0286] A 15 μm thick biaxially stretched nylon film and a 30 μm thick linear low-density polyethylene film (LLDPE film) as a sealing film were mixed using a two-component curable adhesive (solid content 3 g / m²) as described in the examples or comparative examples. 2 The layers are bonded together and cured at 40°C for 6 hours to obtain a laminated film.

[0287] The sealing film surfaces of the laminated films are joined together, and a 1cm wide sealing rod is used at 180℃ and 1kgf / cm. 2 • Perform heat sealing for 1 second, then cut the test piece into 15mm wide pieces. Using a tensile testing machine, set the atmosphere temperature to 25℃ and the peel speed to 300mm / min. The peak tensile strength measured at both ends of the test piece is taken as the heat seal strength (N / 15mm). Evaluate according to the following criteria, and summarize the results in Table 2.

[0288] ○:50N / 15mm or more

[0289] ×: Less than 50N / 15mm

[0290] (Lamination strength)

[0291] A 50 μm thick biaxially stretched PET film and a 30 μm thick aluminum foil were bonded together using a two-component curable adhesive (solid content 3 g / m²) formulated as described in the examples or comparative examples. 2 The layers are bonded together and cured at 40°C for 72 hours to obtain a laminated film.

[0292] Test pieces were cut from the laminated film at a width of 15 mm. The adhesive strength (N / 15 mm) under 180-degree peel at a peel speed of 300 mm / min and an ambient temperature of 25°C was measured using a tensile testing machine. The results were evaluated according to the following criteria and are summarized in Table 2.

[0293] 〇:5.0N / 15mm or more

[0294] ×: Less than 5.0N / 15mm

[0295] [Table 2]

[0296]

Claims

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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