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

Abstract

Provided is a novel polyisocyanate composition suitable for a two-component curable composition such as a two-component curable adhesive or a two-component curable coating agent. A polyisocyanate composition (X) containing a polyurethane polyisocyanate (A1) that is a reaction product of a xylylene diisocyanate (a) and a diol (b) having a molecular weight of 65-300 (inclusive), a two-component curable composition containing the polyisocyanate composition (X) and an isocyanate-reactive composition (Y), a coating agent, and an adhesive. The present invention also relates to a two-component curable composition containing the polyisocyanate composition (X) and an isocyanate-reactive composition (Y), a coating agent, and an adhesive. The polyisocyanate composition (X) contains a polyurethane polyisocyanate (A1) that is a reaction product of the xylylene diisocyanate (a) and the diol (b) having a molecular weight of 65-300 (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] Polyurethane resins are typically manufactured by reacting polyisocyanates with compounds containing active hydrogen groups. They are widely used in various industries as coating agents, adhesives, binders, elastomers, rigid foams, flexible foams, and bonding agents. Furthermore, among products utilizing this polyurethane resin, there are known so-called two-component cured products where the polyisocyanate and active hydrogen compound are mixed just before use.

[0003] As polyisocyanates, diisocyanate monomers such as hexamethylene diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate are sometimes used. However, for the purpose of improving the physical properties of polyurethane resins, suppressing vapor pressure, and ensuring the safety of operators, oligomers of diisocyanate monomers and urethane-type polyisocyanates derived from diisocyanates and polyols are sometimes used.

[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

[0008] Patent Document 3: Japanese Patent Application Publication No. 2017-210519 Summary of the Invention

[0009] The problem the invention aims to solve

[0010] The purpose of this invention is to provide novel polyisocyanate compositions suitable for two-component curable compositions such as two-component curable adhesives and two-component curable coatings.

[0011] Solution for solving the problem

[0012] That is, the present invention relates to a polyisocyanate composition (X) comprising: a polyurethane polyisocyanate (A1) as a reaction product of phenyl dimethyl diisocyanate (a) and a diol (b) with a molecular weight of 65 or more and 300 or less.

[0013] The effects of the invention

[0014] According to the present invention, novel polyisocyanate compositions suitable for two-component curable compositions such as two-component curable adhesives and two-component curable coatings can be provided. Detailed Implementation

[0015] <Polyisocyanate Composition (X)>

[0016] (Polyurethane polyisocyanate (A1))

[0017] The polyisocyanate composition (X) of the present invention comprises a polyisocyanate compound (A) having a plurality of isocyanate groups, wherein the polyisocyanate compound (A) comprises a polyurethane polyisocyanate (A1) as a reaction product of phenyl dimethyl diisocyanate (a) and a diol (b) having a molecular weight of 65 or more and 300 or less.

[0018] As for the diol (b) used in the synthesis of polyurethane polyisocyanate (A1), conventionally known diols can be used without particular restrictions, as long as the molecular weight is 65 or higher and 300 or lower.

[0019] The diol (b) preferably comprises at least one of a diol (b1) having an alkyl side chain with 1 or more and 4 or fewer carbon atoms and a diol (b2) having an ether bond. As diol (b), a diol having the characteristics of both diol (b1) and diol (b2) can be used.

[0020] Examples of diols (b1) having alkyl side chains with 1 or more but less than 4 carbon atoms include 1,2-propanediol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 1,3-butanediol, 2-methyl-1,3-butanediol, 2-ethyl-1,3-butanediol, 2-propyl-1,3-butanediol, 2-butyl-1,3-butanediol, 2-pentyl-1,3-butanediol, and 2-propanediol. -(1-Methylethyl)-1,3-butanediol, 2,2-dimethyl-1,3-butanediol, 2,3-dimethyl-1,3-butanediol, 2-ethyl-2-methyl-1,3-butanediol, 3-methyl-1,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 2,4-pentanediol, 2-methyl-1,3-pentanediol, 2-ethyl-1,3-propanediol, 2-propyl-1,3-butanediol -Propylene glycol, 4-methyl-1,3-pentanediol, 2,4-dimethyl-1,3-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-methyl-2,4-pentanediol, 3-methyl-2,4-pentanediol, 3-ethyl-2,4-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 2-methyl-1,3-hexanediol, 2-ethyl-1,3-hexanediol, 4-methyl-1, 3-Hexanediol, 5-methyl-1,3-hexanediol, 2,4-hexanediol, 1,3-heptanediol, 2-methyl-1,3-methyl-heptanediol, 4-methyl-1,3-heptanediol, 5-methyl-1,3-heptanediol, 6-methyl-1,3-heptanediol, 2,4-heptanediol, 2,4-octanediol, 3,5-octanediol, 2,4-nonanediol, 3,5-nonanediol, 4,6-nonanediol, etc.

[0021] Examples of diols (b2) containing ether bonds include diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol, 4-methoxy-1,3-butanediol, 5-methoxy-1,3-pentanediol, and 5-ethoxy-1,3-pentanediol.

[0022] Diol (b) can be used alone as one of the compounds exemplified above, or in combination of two or more. When two or more diols (b) are used in combination, for example, multiple diols possessing the characteristics of diol (b1) can be used in combination, such as in the combination of neopentyl glycol and 2-butyl-2-ethyl-1,3-propanediol; or multiple diols possessing the characteristics of diol (b2) can be used in combination, such as in the combination of dipropylene glycol, tripropylene glycol, and tetrapropylene glycol. Multiple diols possessing the characteristics of diol (b1) and diols possessing the characteristics of diol (b2) can also be used in combination, such as in the combination of 2-butyl-2-ethyl-1,3-propanediol and diethylene glycol or triethylene glycol.

[0023] The content of diols (b1) and (b2) in diol (b) (where the content of either (b1) or (b2) may be 0) is preferably 20% by mass or more, more preferably 40% by mass or more. Alternatively, the total amount of diol (b) may be selected from at least one of diols (b1) and (b2).

[0024] Polyurethane polyisocyanate (A1) is obtained by reacting phenyl dimethyl diisocyanate (a) with a polyol (b) under conditions where the isocyanate group of phenyl dimethyl diisocyanate (a) is in excess relative to the hydroxyl group of the polyol (b). The equivalent ratio of isocyanate group to hydroxyl group [NCO] / [hydroxyl] can be appropriately adjusted, and for example, it is 2.0 or more and 20.0 or less.

[0025] The polyisocyanate composition (X) used in this invention preferably has a content of diisocyanate monomers, such as aromatic diisocyanates, aromatic aliphatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates, which are exemplified as raw materials for the isocyanate derivative (A2) described later, reduced to 1.0% by mass or less, more preferably reduced to 0.1% by mass or less.

[0026] 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.

[0027] Furthermore, when using two-component curing adhesives containing aromatic isocyanate prepolymers to manufacture laminates for food packaging, 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 manufacture for food contact.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] Device: "ACQUITY UPLC H-Class" manufactured by Waters Corporation

[0032] Data processing: Waters Corporation, "Empower-3"

[0033] Column: "ACQUITY UPLC HSS T3" manufactured by Waters Corporation (100 mm×2.1 mmφ, 1.8 μm) 40°C

[0034] Eluent: Ammonium formate aqueous solution / methanol, 0.3 mL / min

[0035] Detector: PDA

[0036] Sample preparation: 1. Dissolve 100 mg of appropriately blocked sample in 10 ml of THF (for LC).

[0037] 2. Stir with a vortex for 30 seconds.

[0038] 3. Dilute appropriately with elution buffer (mobile phase)

[0039] 4. Pass the liquid through a 0.2μm filter to prepare the test sample.

[0040] Calculation of area ratio: Calculated using the maximum absorption wavelength for the target object.

[0041] (Isocyanate derivative (A2))

[0042] To improve the storage stability, coatability, and flexibility of the coating film when used as a two-component curable composition (described later), the polyisocyanate composition (X) may contain an isocyanate derivative (A2) other than a polyurethane polyisocyanate (A1). Examples of isocyanate derivatives (A2) include conventionally known aromatic diisocyanates, aromatic aliphatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and biuret bodies (A2-1), ureates (A2-2), adducts (A2-3), urea carbamates (A2-4), carbodiimide modifiers (A2-5), urea diketone modifiers (A2-6), and polyurethane polyisocyanates (A2-7) other than polyurethane polyisocyanates (A1). One or more of these derivatives may be used.

[0043] 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.

[0044] 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.

[0045] 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).

[0046] 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.

[0047] Examples of polyols used in the synthesis of polyurethane polyisocyanates (A2-7) 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.

[0048] Trifunctional or tetrafunctional aliphatic alcohols such as glycerol, trimethylolpropane, pentaerythritol, and 1,3,5-tris(2-hydroxyethyl)isocyanurate;

[0049] Bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, and other bisphenols;

[0050] Dimer Diol;

[0051] 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.

[0052] 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.

[0053] Polyester polyols (2) obtained by reacting the above-mentioned diols, dimer diols, or the above-mentioned bisphenols and other difunctional polyols with polycarboxylic acids:

[0054] Polyester polyols obtained by reacting trifunctional or tetrafunctional aliphatic alcohols with polycarboxylic acids (3).

[0055] Polyester polyols (4) are obtained by reacting difunctional polyols with the above-mentioned trifunctional or tetrafunctional aliphatic alcohols and polycarboxylic acids.

[0056] Polyester polyols that are polymers of hydroxy acids such as dimethylolpropionic acid and castor oil fatty acids (5).

[0057] The polyether polyols described above are obtained by increasing the molecular weight of the polyether polyols using isocyanate compounds;

[0058] 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.

[0059] Polyester polyols (1) to (5) were obtained by increasing the molecular weight of polyester polyols using isocyanate compounds;

[0060] 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.

[0061] 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.

[0062] Methyl esters of aromatic polybasic acids such as dimethyl terephthalate and dimethyl 2,6-naphthalenedicarboxylate;

[0063] 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;

[0064] 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.

[0065] 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.

[0066] The molecular weight of the polyols used in the synthesis of these polyurethane polyisocyanates (A2-7) can be appropriately adjusted, for example, to be above 50 g / mol and below 4000 g / mol.

[0067] Polyurethane polyisocyanates (A2-7) are obtained by reacting isocyanates with polyols under conditions where the isocyanate groups of the isocyanate are in excess relative to the hydroxyl groups of the polyol, and then removing unreacted diisocyanate monomers under the same conditions as polyurethane polyisocyanates (A1), as needed. 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.

[0068] When the polyisocyanate composition (X) contains an isocyanate derivative (A2), the content of polyurethane polyisocyanate (A1) in the polyisocyanate compound (A) (the total of polyurethane polyisocyanate (A1), isocyanate derivative (A2), and isocyanate monomer) can be appropriately adjusted according to the target performance. As an example, it is preferably 20% by mass or more, and more preferably 50% by mass or more. Alternatively, the total amount of polyisocyanate compound (A) may be polyurethane polyisocyanate (A1).

[0069] The NCO% of the polyisocyanate composition (X) can be adjusted appropriately according to the purpose, and as an example, it is preferably 7% or more and 21% or less.

[0070] The polyisocyanate composition (X) may contain components other than polyisocyanate compounds. Examples of such components include solvents (B), phosphoric acid derivatives (C), plasticizers (D), etc., but are not limited thereto.

[0071] (Solvent (B))

[0072] Examples of suitable esters include ethyl acetate, butyl acetate, and acetic acid cellosol; ketones include acetone, methyl ethyl ketone, isobutyl ketone, and cyclohexanone; ethers include tetrahydrofuran and dioxane; aromatic hydrocarbons include toluene and xylene; halogenated hydrocarbons include dichloromethane and dichloroethane; and dimethyl sulfoxide and dimethyl sulfonamide. One type or two or more types can be used in combination.

[0073] (Phosphate derivative (C))

[0074] Examples of phosphoric acid derivatives (C) 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.

[0075] When the polyisocyanate composition (X) of the present invention contains a phosphoric acid derivative (C), its content can be appropriately adjusted. As an example, it is 10 ppm or more and 5000 ppm or less of the solid component of the polyisocyanate composition (X). More preferably, it is 50 ppm or more, and even more preferably, it is 1000 ppm or less.

[0076] (Plasticizer (D))

[0077] Examples of plasticizers (D) 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.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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), dibutylmethylene dimercaptoacetate, and other diol-based plasticizers; as well as glycerol-based plasticizers such as glyceryl monoacetate, glyceryl triacetate, and glyceryl tributyrate.

[0083] 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.

[0084] Examples of polyester plasticizers include adipic acid-based polyesters, sebacic acid-based polyesters, and phthalic acid-based polyesters.

[0085] Examples of carbonate-based plasticizers include propylene carbonate and ethylene carbonate.

[0086] In addition, other examples of plasticizers (D) 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.

[0087] The amount of plasticizer (D) can be adjusted appropriately according to the target viscosity; for example, it is preferably kept below 30% by mass of the solid content of the polyisocyanate composition (X). The polyisocyanate composition (X) may be free of plasticizer (D).

[0088] <Two-component cured composition>

[0089] 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.

[0090] Such two-component curable compositions can be used, for example, in adhesives, coatings, sealants, elastomers, etc.

[0091] Two-component curing coating agent

[0092] The two-component curable coating agent of the present invention comprises the above-mentioned polyisocyanate composition (X) and isocyanate reactive composition (Y). The coating agent of the present invention is suitable for various applications, including coating agents for metal substrates such as aluminum and steel plates, outer coatings for films containing aluminum pigments and metal particles, coverings for electrical components, and electrical insulation. Furthermore, by selecting appropriate substances as the isocyanate reactive composition (Y), a coating agent with excellent gas barrier properties can be produced. Gas barrier coating agents are, for example, suitable for manufacturing laminates with gas barrier properties.

[0093] The isocyanate reactive composition (Y) comprises compounds (E) having multiple functional groups that are reactive with isocyanates, such as polyester polyols (E1), polyether polyols (E2), vegetable oil polyols (E3), polyurethane polyols (E4), sugar alcohols (E5), acrylic polyols (E6), amine compounds (E7), and epoxy compounds (E8) (hereinafter also referred to as isocyanate reactive compounds (E)). One isocyanate reactive compound (E) may be used, or two or more may be used in combination.

[0094] Examples of polyester polyols (E1) 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.

[0095] 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.

[0096] Trimethylolethane, trimethylolpropane, glycerol, hexanetriol, pentaerythritol, and other trifunctional or higher aliphatic polyols;

[0097] Bisphenol A, bisphenol F, and other bisphenols;

[0098] Bisphenol alkyl oxide adducts are obtained by adding ethylene oxide, propylene oxide, etc. to bisphenols such as bisphenol A and bisphenol F;

[0099] 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.

[0100] 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.

[0101] 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

[0102] These are aliphatic or dicarboxylic acid anhydrides or esterifying derivatives;

[0103] 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.

[0104] The molecular weight of the polyester polyol (E1) 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.

[0105] The preferred hydroxyl value of the polyester polyol (E1) is above 5 mg KOH / g and below 500 mg KOH / g.

[0106] Examples of polyether polyols (E2) 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.

[0107] 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.

[0108] Trifunctional or tetrafunctional aliphatic alcohols such as glycerol, trimethylolpropane, pentaerythritol, and triols of polypropylene glycol;

[0109] 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.

[0110] The molecular weight of the polyether polyol (E2) can be adjusted appropriately. For example, it is preferably 100 g / mol or more and 8000 g / mol or less.

[0111] The hydroxyl value of the polyether polyol (E2) can be adjusted appropriately. For example, it is preferably 10 mg KOH / g or more and 1200 mg KOH / g or less.

[0112] Examples of vegetable oil polyols (E3) include castor oil, dehydrated castor oil, hydrogenated castor oil as a hydride of castor oil, and 5-50 molar adducts of castor oil epoxides.

[0113] Polyurethane polyol (E4) is a reaction product of a low-molecular-weight or high-molecular-weight polyol and a polyisocyanate compound. The same polyol used as the example polyol used as a raw material for polyester polyol (E1) can be used as the low-molecular-weight or high-molecular-weight polyol. The same compound used as the example compound used as a raw material for isocyanate derivative (A2) can be used as the polyisocyanate compound.

[0114] Examples of sugar alcohols (E5) include pentaerythritol, sucrose, xylitol, sorbitol, isomaltitol, lactitol, maltitol, and mannitol.

[0115] As an acrylic polyol (E6), 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.

[0116] 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.

[0117] 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.

[0118] Benzyl methacrylate, 2-phenylethyl methacrylate, and other aralkyl methacrylates;

[0119] Cyclohexyl methacrylate, isobornyl methacrylate, and other cycloalkyl methacrylates;

[0120] 2-Methoxyethyl ester of (meth)acrylate, 4-Methoxybutyl ester of (meth)acrylate, and other ω-alkoxyalkyl esters of (meth)acrylate;

[0121] Polyfunctional (meth)acrylates such as ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and dipentaerythritol hexa(meth)acrylate;

[0122] (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.

[0123] Vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and other vinyl carboxylic acid esters;

[0124] Alkyl esters of crotonic acid, such as methyl crotonate and ethyl crotonate;

[0125] 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.

[0126] Amine compounds (E7) 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).

[0127] As the amine compound (E7), 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.

[0128] 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,

[0129] amine compounds containing multiple amino groups, such as 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 (E7-1), are included.

[0130] Monoethanolamine, monoisopropanolamine, monobutanolamine, N-methylethanolamine, N-ethylethanolamine, N-methylpropanolamine, diethanolamine, diisopropanolamine, and other primary or secondary alkanolamines (E7-2).

[0131] Primary or secondary amines (E7-3), such as ethylamine, octylamine, laurylamine, myristicamine, stearylamine, oleylamine, diethylamine, dibutylamine, and distearate.

[0132] The amount of amine compound (E7) 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.

[0133] 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.

[0134] As an epoxy compound (E8), 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.

[0135] 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;

[0136] Aromatic epoxy resins such as glycidyl ether phenolic varnish resin, cresol phenolic varnish resin, and phenolic varnish type epoxy resin.

[0137] 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.

[0138] 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.

[0139] 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;

[0140] Diepoxy resins of hydrocarbon dienes such as butadiene, hexadiene, octadiene, dodecadiene, cyclooctadiene, α-pinene or vinylcyclohexene;

[0141] Epoxy resins of diene polymers such as polybutadiene or polyisoprene;

[0142] Glycidylamine type epoxy resins include tetraglycidyl diaminodiphenylmethane, triglycidyl p-aminophenol, tetraglycidyl diaminomethylcyclohexane, diglycidyl aniline, and tetraglycidyl m-phenylenediamine.

[0143] Triazine, hydantoin, and other heterocyclic epoxy resins.

[0144] They can be used individually or in combination of two or more.

[0145] The isocyanate reactive compound (E) preferably contains 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 (E) can be appropriately adjusted according to the purpose; for example, it may be 80°C or lower.

[0146] In a preferred embodiment of the coating agent of the present invention, the isocyanate reactive compound (E) may include at least one selected from polyester polyols (E1-1) obtained by polycondensation of a polycarboxylic acid containing an ortho-oriented polycarboxylic acid with a polyol, polyester polyols having an isocyanurate ring (E1-2), and polyester polyols having polymerizable carbon-carbon double bonds (E1-3). The polyisocyanate composition (X) of the present invention, when used in combination with an isocyanate reactive composition (Y) containing such an isocyanate reactive compound (E), can produce a coating agent with excellent gas barrier properties.

[0147] Examples of ortho-oriented polycarboxylic acids used in the synthesis of polyester polyols (E1-1) include phthalic acid or its anhydride, naphthalene-2,3-dicarboxylic acid or its anhydride, naphthalene-1,2-dicarboxylic acid or its anhydride, anthraquinone-2,3-dicarboxylic acid or its anhydride, and 2,3-anthracarboxylic acid or its anhydride. These compounds may have substituents on any carbon atom of the aromatic ring. Examples of such substituents include chloro, bromo, methyl, ethyl, isopropyl, hydroxy, methoxy, ethoxy, phenoxy, methylthio, phenylthio, cyano, nitro, amino, phthalimide, carboxyl, carbamoyl, N-ethylcarbamoyl, phenyl, or naphthyl, and one or more may be used in combination.

[0148] The polycarboxylic acid may include polycarboxylic acids other than ortho-oriented polycarboxylic acids. As such a polycarboxylic acid, the same polycarboxylic acid as the example polycarboxylic acid used as a raw material for polyester polyol (E1) can be used. When the polycarboxylic acid includes polycarboxylic acids other than ortho-oriented polycarboxylic acids, the proportion of the ortho-oriented polycarboxylic acid in the total amount of polycarboxylic acid is preferably 40 to 100% by mass.

[0149] The polyol used in the synthesis of polyester polyol (E1-1) preferably includes at least one selected from the group consisting of ethylene glycol, propylene glycol, butanediol, neopentyl glycol, and cyclohexanediol, and more preferably includes ethylene glycol. In addition to these, other polyols that are examples of raw materials for polyester polyol (E1) may also be used. Examples include glycerol, 1,3,5-tris(2-hydroxyethyl)isocyanuric acid, and trimethylolpropane.

[0150] When a polyester polyol (E1-1) has three or more hydroxyl groups (referred to as polyester polyol (e1-1) for convenience), a portion of the hydroxyl groups can be modified with acid groups. Such a polyester polyol will also be referred to as polyester polyol (E1-1') below. Polyester polyol (E1-1') is obtained by reacting a polyester polyol (e1-1) with a polycarboxylic acid or its anhydride. The proportion of hydroxyl groups modified with the polycarboxylic acid is preferably less than 1 / 3 of the hydroxyl groups present in the polyester polyol (e1-1). Examples of polycarboxylic acids used for modification include succinic anhydride, maleic acid, maleic anhydride, fumaric acid, 1,2-cyclohexanedicarboxylic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, phthalic anhydride, 2,3-naphthalenedicarboxylic anhydride, trimellitic anhydride, oleic acid, and sorbic acid, but are not limited to these.

[0151] Polyester polyols (E1-2) are obtained, for example, by reacting a triol having an isocyanurate ring with a polycarboxylic acid containing an ortho-oriented aromatic polycarboxylic acid and a polyol. Examples of triols having an isocyanurate ring include alkyl oxide adducts of isocyanuric acids such as 1,3,5-tris(2-hydroxyethyl)isocyanuric acid and 1,3,5-tris(2-hydroxypropyl)isocyanuric acid. The ortho-oriented aromatic polycarboxylic acid, polycarboxylic acid, and polyol can be the same substances as those used in polyester polyols (E1-1).

[0152] As a triol compound having an isocyanurate ring, 1,3,5-tris(2-hydroxyethyl) isocyanuric acid or 1,3,5-tris(2-hydroxypropyl) isocyanuric acid is preferred. As an ortho-oriented aromatic polycarboxylic acid, phthalic anhydride is preferred. As a polyol, ethylene glycol is preferred.

[0153] Polyester polyols (E1-3) are obtained by using components with polymerizable carbon-carbon double bonds as polycarboxylic acids and polyols.

[0154] Examples of polycarboxylic acids with polymerizable carbon-carbon double bonds include maleic anhydride, maleic acid, fumaric acid, 4-cyclohexene-1,2-dicarboxylic acid and its anhydride, and 3-methyl-4-cyclohexene-1,2-dicarboxylic acid and its anhydride. It is speculated that the fewer the number of carbon atoms, the less flexible the molecular chain will be, thus reducing oxygen permeability. Therefore, maleic anhydride, maleic acid, and fumaric acid are preferred.

[0155] Examples of polyols with polymerizable carbon-carbon double bonds include 2-buten-1,4-diol.

[0156] In addition to the above, polycarboxylic acids and polyols that do not have polymerizable carbon-carbon double bonds may also be used. Such polycarboxylic acids and polyols may be the same substances as polyester polyols (E1-1) and (E1-2). The polycarboxylic acid is preferably at least one selected from the group consisting of succinic acid, 1,3-cyclopentanedicarboxylic acid, phthalic acid, phthalic acid anhydrides, and isophthalic acid; more preferably, at least one selected from phthalic acid and its anhydrides. The polyol is preferably at least one selected from the group consisting of ethylene glycol, propylene glycol, butanediol, neopentyl glycol, and cyclohexanediol; more preferably, ethylene glycol.

[0157] When polyester polyols such as (E1-1), (E1-2), and (E1-3) are used for the purpose of gas barrier properties, the amount used can be adjusted appropriately according to the degree of target gas barrier properties. As an example, it is preferable to use 50% by mass or more of the isocyanate reactive compound (E), more preferably 60% by mass or more. Alternatively, the total amount of the isocyanate reactive compound (E) may be at least one selected from polyester polyols (E1-1), (E1-2), and (E1-3).

[0158] When using polyester polyols such as (E1-1), (E1-2), and (E1-3) as the isocyanate reactive compound (E), the hydroxyl value can be appropriately adjusted. For example, from the perspective of ease of solubility in solvents, a hydroxyl value of 20 mg KOH / g or higher is preferred. Furthermore, from the perspective of minimizing adhesion, a hydroxyl value of 400 mg KOH / g or lower is preferred.

[0159] When the polyester polyols (E1-1), (E1-2), and (E1-3) have acid groups, the acid value is preferably below 200 mg KOH / g. This allows for the moderate suppression of the reaction between the polyisocyanate composition (X) and the isocyanate reactive composition (Y), resulting in a coating agent with excellent coating adaptability.

[0160] Polyester polyols (E1-1), (E1-2), and (E1-3) with molecular weights ranging from 300 g / mol to 5000 g / mol exhibit an excellent balance between sealing and gas barrier properties, and are therefore preferred. A more preferred molecular weight is 350 g / mol to 3000 g / mol. The molecular weight is calculated based on the obtained hydroxyl value and the number of functional groups in the designed hydroxyl groups.

[0161] The coating agent of the present invention may or may not contain a solvent. The same solvent as that used in the example solvent (C) can be used as the solvent.

[0162] 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.

[0163] 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.

[0164] The coating amount of the coating agent can be adjusted appropriately according to the intended use, etc. For example, it is 0.1 g / m². 2 Above and 100g / m 2 the following.

[0165] 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.

[0166] Two-component curing adhesive

[0167] The two-component curing adhesive of the present invention comprises the above-mentioned polyisocyanate composition (X) and isocyanate reactive composition (Y).

[0168] 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 70°C is adjusted to a range of 100-20000 mPas, more preferably 500-10000 mPas. For example, the viscosity of the polyisocyanate composition (X) can be adjusted by the structure of the polyurethane polyisocyanate (A1) (the diol (b) used) and / or by the isocyanate compound (A2) used as needed. The viscosity of the polyisocyanate composition (X) can be, for example, measured 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 70℃±1℃.

[0169] 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 solvent dilution.

[0170] (Isocyanate reactive composition (Y))

[0171] The isocyanate reactive composition (Y) comprises an isocyanate reactive compound (E). As the isocyanate reactive compound (E), one substance identical to that used in the above-described coating agent or a combination of two or more substances can be used.

[0172] The isocyanate reactive compound (E) preferably contains 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 (E) can be appropriately adjusted according to the intended use; for example, it may be -50°C or higher.

[0173] Similarly to the coating agent described above, an adhesive with excellent gas barrier properties can be prepared by combining it with an isocyanate reactive composition (Y) comprising at least one of the following as an isocyanate reactive compound (E): polyester polyol (E1-1) obtained by polycondensation of a polycarboxylic acid containing an ortho-oriented polycarboxylic acid with a polyol, polyester polyol having an isocyanurate ring (E1-2), and polyester polyol having a polymerizable carbon-carbon double bond (E1-3).

[0174] When polyester polyols such as (E1-1), (E1-2), and (E1-3) are used for the purpose of gas barrier properties, the amount used can be adjusted appropriately according to the degree of target gas barrier properties. As an example, it is preferable to use 40% by mass or more of the isocyanate reactive compound (E), and more preferably 50% by mass or more. Alternatively, the total amount of the isocyanate reactive compound (E) may be at least one selected from polyester polyols (E1-1), (E1-2), and (E1-3).

[0175] When using polyester polyols such as (E1-1), (E1-2), and (E1-3) as the isocyanate reactive compound (E), a hydroxyl value of 20 mg KOH / g or higher is preferred in order to produce an adhesive with excellent coating adaptability even when used, for example, as a solvent-free adhesive. Furthermore, to ensure that the cured coating of the adhesive is flexible and exhibits good adhesion to flexible substrates, a hydroxyl value of 400 mg KOH / g or lower is preferred.

[0176] When the polyester polyols (E1-1), (E1-2), and (E1-3) have acid groups, the acid value is preferably below 200 mg KOH / g. This allows for the moderate suppression of the reaction between the polyisocyanate composition (X) and the isocyanate reactive composition (Y), resulting in an adhesive with excellent coating adaptability.

[0177] Polyester polyols (E1-1), (E1-2), and (E1-3) with molecular weights ranging from 300 g / mol to 5000 g / mol exhibit an excellent balance between adhesion and gas barrier properties, and are therefore preferred. A molecular weight of 350 g / mol to 3000 g / mol is more preferred. The molecular weight is calculated based on the obtained hydroxyl value and the number of functional groups in the designed hydroxyl groups.

[0178] (Monohydric alcohol compound (F))

[0179] The isocyanate reactive composition (Y) may comprise a monohydric alcohol compound (F) having one alcoholic hydroxyl group. The main chain of the monohydric alcohol compound (F) 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 (F) 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.

[0180] Specific examples of monohydric alcohol compounds (F) 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.

[0181] 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.

[0182] Aromatic aliphatic monohydric alcohols such as benzyl alcohol;

[0183] 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.

[0184] 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 (E) and / or by plasticizers, as described later.

[0185] (Other components of the adhesive)

[0186] 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.

[0187] (catalyst)

[0188] Examples of catalysts include metal-based catalysts, amine-based catalysts, aliphatic cyclic amide compounds, and quaternary ammonium salts.

[0189] 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.

[0190] Catalysts selected from inorganic metal systems include Sn, Fe, Mn, Cu, Zr, Th, Ti, Al, and Co.

[0191] 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.

[0192] 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.

[0193] 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.

[0194] 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.

[0195] (Coupled agent)

[0196] Examples of coupling agents include silane coupling agents, titanate coupling agents, and aluminum coupling agents.

[0197] As silane coupling agents, examples include amino silanes such as γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, bis[3-(triethoxysilyl)propyl]amine; epoxy silanes such as β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane; vinyl silanes such as vinyl tris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane; hexamethyldisilazane, γ-mercaptopropyltrimethoxysilane, etc.

[0198] As titanate coupling agents, for example, examples include tetra-isopropoxy titanium, tetra-n-butoxy titanium, butyl titanate dimer, tetra-stearyl titanate, titanium acetylacetonate, titanium lactate, tetra-octylene glycol titanate, titanium lactate, tetra-stearyloxy titanium, etc.

[0199] As aluminum coupling agents, for example, examples include acetylalkoxydipropanol aluminum, etc.

[0200] (Pigment)

[0201] As pigments, there is no particular limitation, and examples include extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments, green pigments, blue pigments, metallic powder pigments, luminescent pigments, pearlescent pigments, etc., such as organic pigments, inorganic pigments, and furthermore plastic pigments, as described in the Paint Raw Material Handbook, 1970 Edition (edited by the Japan Paint Industry Association).

[0202] As extender pigments, for example, examples include precipitated barium sulfate, lead white (Japanese: ご粉), precipitated calcium carbonate, calcium bicarbonate, gypsum, alumina white, silica, hydrated micropowder silica (white carbon), ultrafine anhydrous silica (Aerosil), silica sand (silicon dioxide sand), talc, precipitated magnesium carbonate, bentonite, clay, kaolin, loess, etc.

[0203] 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 maroon 10; various phthalocyanine (copper) pigments such as phthalocyanine blue and phthalocyanine green; various chlorine-containing dye lakes such as rhodamine lake and methyl violet lake; various mordant dye pigments such as quinoline lake and strong sky blue; various vat dye pigments such as anthraquinone pigments, thioindigo pigments, and perinone pigments; various quinacridone pigments such as Cinquasia Red B; various dioxazine pigments such as dioxazine violet; various condensed azo pigments such as Cromophtal; aniline black; etc.

[0204] 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 dioxide, zinc white, Mapico Yellow, iron oxide, iron oxide red, chrome oxide green, and zirconium oxide; various sulfides and even selenides such as cadmium yellow, cadmium red, and mercuric 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 and flake pigments of mica; flake pigments of mica covered with metal oxides, mica-like iron oxide pigments, and other metal pigments and pearlescent pigments; graphite and carbon black, etc.

[0205] As a plastic pigment, examples include "GRANDOLL PP-1000" and "PP-2000S" manufactured by DIC Corporation.

[0206] Regarding the pigments used, appropriate selection can be made according to the purpose. For example, considering factors such as durability, weather resistance, and excellent design, inorganic oxides such as titanium dioxide and zinc white are preferred as white pigments, while carbon black is preferred as a black pigment.

[0207] As an example, the amount of pigment mixed is 1 to 400 parts by mass relative to 100 parts by mass of the total amount of non-volatile components of the polyisocyanate composition (X) and the isocyanate reactive composition (Y), and is more preferably 10 to 300 parts by mass to improve adhesion and anti-blocking properties.

[0208] (acid anhydride)

[0209] 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 methyl hymic acid), trialkyl... Tetrahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, methylcyclohexene tetracarboxylic anhydride, ethylene glycol dipremetyl tricarboxylate dianhydride, chlorobridged anhydride, norbornyl anhydride, methyl norbornyl 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.

[0210] 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.

[0211] 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.

[0212] (Other ingredients)

[0213] The adhesive may contain a phosphate derivative (C) and a plasticizer (D). They may be the same substances as those used in the examples above as components of the polyisocyanate composition (X).

[0214] (Form of adhesive)

[0215] 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.

[0216] Examples of organic solvents include esters such as ethyl acetate, butyl acetate, and acetic acid solvents; 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. 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.

[0217] 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 acetic acid cellosol, 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.

[0218] 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.

[0219] <Layered Body>

[0220] The laminate of the present invention is obtained, for example, by preparing a coating agent by mixing the polyisocyanate composition (X) of the present invention with an isocyanate reactive composition (Y), applying the coating agent to a substrate and curing it.

[0221] Alternatively, it can be obtained by the following methods: a two-component mixing process in which the polyisocyanate composition (X) and the isocyanate reactive composition (Y) of the present invention are mixed in advance to prepare an adhesive, which is then applied to a first substrate, followed by laminating a second substrate on the coated surface and curing the adhesive layer; and a two-component separate coating process in which the polyisocyanate composition (X) and the isocyanate reactive composition (Y) are respectively applied to a first substrate and a second substrate, and the respective coated surfaces are brought into contact and pressed together, thereby laminating the first substrate and the second substrate and curing the adhesive layer. There are no particular limitations on the substrate used, and it can be appropriately selected according to the application.

[0222] For example, as 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, BOPE: 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.

[0223] In addition, biomass films, biodegradable films, and recycled plastic films formed from materials containing biomass-derived components, biodegradable components, or recycled components are preferred.

[0224] 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.

[0225] (Biomass film)

[0226] 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.

[0227] 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.

[0228] 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.

[0229] 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.

[0230] 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.

[0231] 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.

[0232] 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.

[0233] 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.

[0234] 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".

[0235] 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.

[0236] 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.

[0237] (Biodegradable film)

[0238] 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.

[0239] 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.

[0240] 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.

[0241] 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.

[0242] Specifically, examples include PBAT, which is a copolymer of 1,4-butanediol, adipic acid, and terephthalic acid (e.g., Ecoflex manufactured by BASF Corporation).

[0243] 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.).

[0244] 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.

[0245] 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.

[0246] 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.

[0247] 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.

[0248] 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.

[0249] Examples of more specific structures for laminates manufactured using the coating agent of the present invention include:

[0250] (1) Coating layer / substrate

[0251] (2) Coated layer / metal vapor deposited unstretched film

[0252] (3) Coating layer / metal vapor deposition stretch film

[0253] (4) Coating layer / transparent vapor-deposited stretched film

[0254] (5) Substrate / Coating / Metal Evaporation Layer

[0255] (6) Substrate / Coating layer / Transparent vapor deposition layer

[0256] etc., but not limited to this.

[0257] Examples of substrates used in composition (1) include MDOPE film, BOPE film, OPP film, PET film, nylon film, paper, K-OPP film, K-PET film, and K-nylon film. A printing layer may be provided on either side of the substrate (the side of the substrate facing the coating layer or the side of the substrate opposite to the coating layer) or on the coating layer (the side of the coating layer opposite to the substrate). The printing layer is formed using various printing inks such as gravure ink, flexographic ink, offset ink, stencil ink, and inkjet ink, through conventional printing methods previously used in printing polymer films and / or paper.

[0258] Examples of metal vapor-deposited unstretched films used in composition (2) include CPP films, LLDPE films, VM-CPP films and VM-LLDPE films in which metal vapor deposition of aluminum or the like is applied to a gas barrier heat-sealing film.

[0259] Examples of metal vapor-deposited stretched films used in composition (3) include VM-MDOPE films, VM-BOPE films, VM-OPP films, and VM-PET films, which are formed by metal vapor deposition of aluminum or the like on MDOPE films, BOPE films, OPP films, and PET films.

[0260] Examples of transparent vapor-deposited stretch films used in composition (4) include films in which silicon dioxide or aluminum oxide has been vapor-deposited onto MDOPE films, BOPE films, OPP films, PET films, nylon films, etc.

[0261] Similar to composition (1), the printing layer can be placed at any position.

[0262] Examples of substrates used in components (5) and (6) include MDOPE film, BOPE film, OPP film, PET film, CPP film, LLDPE film, gas barrier heat-sealing film, and paper. The metal vapor deposition layer is a vapor deposition layer of metals such as aluminum.

[0263] When the coating agent of the present invention is a gas barrier coating agent (when the isocyanate reactive composition (Y) contains at least one selected from polyester polyols (E1-1), (E1-2), (E1-3),), a laminate with better gas barrier properties can be produced by providing a coating layer formed by the coating agent of the present invention on a metal vapor deposition layer or a transparent vapor deposition layer as configured in (2) to (4).

[0264] Examples of more specific structures of laminates manufactured using the adhesive of the present invention include:

[0265] (1) Substrate 1 / Adhesive layer 1 / Sealing film

[0266] (2) Substrate 1 / Adhesive layer 1 / Metal vapor-deposited unstretched film

[0267] (3) Substrate 1 / Adhesive layer 1 / Metal vapor-deposited stretched film

[0268] (4) Transparent vapor-deposited stretch film / adhesive layer 1 / sealing film

[0269] (5) Substrate 1 / Adhesive layer 1 / Substrate 2 / Adhesive layer 2 / Sealing film

[0270] (6) Substrate 1 / Adhesive layer 1 / Metal vapor-deposited stretched film / Adhesive layer 2 / Sealing film

[0271] (7) Substrate 1 / Adhesive layer 1 / Transparent vapor-deposited stretch film / Adhesive layer 2 / Sealing film

[0272] (8) Substrate 1 / Adhesive layer 1 / Metal layer / Adhesive layer 2 / Sealing film

[0273] (9) Substrate 1 / Adhesive layer 1 / Substrate 2 / Adhesive layer 2 / Metal layer / Adhesive layer 3 / Sealing film

[0274] (10) Substrate 1 / Adhesive Layer 1 / Metal Layer / Adhesive Layer 2 / Substrate 2 / Adhesive Layer 3 / Sealing Film

[0275] etc., but not limited to this.

[0276] Examples of substrate 1 used in composition (1) include MDOPE film, BOPE 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.

[0277] Examples of substrate 1 used in configurations (2) and (3) include MDOPE film, BOPE 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-BOPE film, and VM-OPP film, which have undergone metal deposition of aluminum or the like on MDOPE film, BOPE film, and OPP film, can be used. Similar to configuration (1), a printing layer can be provided on any surface of substrate 1.

[0278] 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, BOPE 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).

[0279] 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.

[0280] 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-BOPE 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, BOPE 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.

[0281] 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.

[0282] 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.

[0283] 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.

[0284] When the adhesive of the present invention is a gas-barrier adhesive (where the isocyanate reactive composition (Y) comprises at least one selected from polyester polyols (E1-1), (E1-2), and (E1-3), if the adhesive of the present invention is used when manufacturing a laminate containing a metal vapor-deposited layer or a transparent vapor-deposited layer as configured in (2) to (4), (6), and (7), a laminate with superior gas barrier properties can be produced. In this case, it is preferable to use the adhesive of the present invention to form an adhesive layer in contact with the metal vapor-deposited layer or the transparent vapor-deposited layer.

[0285] 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.

[0286] "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.

[0287] 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.

[0288] Packaging Materials

[0289] 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.

[0290] 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.

[0291] 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.

[0292] 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.

[0293] Example

[0294] 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.

[0295] <Preparation of Polyisocyanate Composition (X)>

[0296] (Polyisocyanate composition (X-1))

[0297] 838.6 parts of phenyl dimethyl diisocyanate (XDI) 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, 161.4 parts of 2,2,4-trimethyl-1,3-pentanediol were added while monitoring the heat, and the mixture was heated to 60°C. The reaction was continued at 60°C until the NCO% no longer changed, and 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 XDI in the urethane prepolymer, which is the reaction product of XDI, reached 0.05% by mass in the solids composition, thus obtaining a polyisocyanate composition (X-1). The NCO% of the polyisocyanate composition (X-1) was 14.1%.

[0298] (Polyisocyanate composition (X-2))

[0299] 849.6 parts of phenyl dimethyl diisocyanate (XDI) 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, 150.4 parts of dipropylene glycol were added while monitoring the heat, and the mixture was heated to 60°C. The reaction was continued at 60°C until the NCO% no longer changed, and 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 XDI in the urethane prepolymer, which is the reaction product of XDI, reached 0.05% by mass in the solids composition, thus obtaining the polyisocyanate composition (X-2). The NCO% of the polyisocyanate composition (X-2) was 13.7%.

[0300] (Polyisocyanate composition (X-3))

[0301] 825.5 parts of phenyl dimethyl diisocyanate (XDI) 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, 174.5 parts of 2-butyl-2-ethyl-1,3-propanediol were added while monitoring the heat, and the mixture was heated to 60°C. The reaction was continued at 60°C until the NCO% no longer changed, and 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 XDI in the urethane prepolymer, which is the reaction product of XDI, reached 0.05% by mass in the solids composition, thus obtaining a polyisocyanate composition (X-3). The NCO% of the polyisocyanate composition (X-3) was 12.7%.

[0302] (Polyisocyanate composition (X-4))

[0303] 834.7 parts of phenyl dimethyl diisocyanate (XDI) 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, 165.3 parts of triethylene glycol were added while monitoring the heat, and the mixture was heated to 60°C. The reaction was continued at 60°C until the NCO% no longer changed, and 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 XDI in the urethane prepolymer, which is the reaction product of XDI, reached 0.05% by mass in the solids composition, thus obtaining a polyisocyanate composition (X-4). The NCO% of the polyisocyanate composition (X-4) was 13.5%.

[0304] (Polyisocyanate composition (X-5))

[0305] 877.3 parts of phenyl dimethyl diisocyanate (XDI) 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, 122.7 parts of diethylene glycol were added while monitoring the heat, and the mixture was heated to 60°C. The reaction was continued at 60°C until the NCO% no longer changed, and 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 XDI in the urethane prepolymer, which is the reaction product of XDI, reached 0.05% by mass in the solids composition, thus obtaining a polyisocyanate composition (X-5). The NCO% of the polyisocyanate composition (X-5) was 14.3%.

[0306] (Polyisocyanate composition (X'-1))

[0307] 924.3 parts of phenyl dimethyl diisocyanate (XDI) 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, 75.7 parts of ethylene glycol were added while monitoring the heat, and the mixture was heated to 60°C. The reaction was continued at 60°C until the NCO% no longer changed, and 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 XDI in the urethane prepolymer, which is the reaction product of XDI, reached 0.05% by mass in the solids composition, thus obtaining the polyisocyanate composition (X'-1). The NCO% of the polyisocyanate composition (X'-1) was 18.5%.

[0308] <Preparation of Isocyanate Reactive Composition (Y)>

[0309] (Isocyanate reactive composition (Y-1))

[0310] In a polyester reaction vessel equipped with a stirrer, thermometer, nitrogen inlet pipe, and distillation tube, 92.0 parts of ethylene glycol, 118.5 parts of phthalic anhydride, 29.2 parts of adipic acid, and 0.01 parts of tetraisopropyl titanate were added, and an ester reaction was carried out at an internal temperature of 220°C. After dehydration, a polyester polyol with an acid value of 1 mg KOH / g was obtained. 50.0 parts of triacetin were then added to this polyol to obtain an isocyanate reactive composition (Y-1).

[0311] Evaluation of the polyisocyanate composition (X)

[0312] (Storage stability of polyisocyanate composition (X))

[0313] Fill 15 mL glass bottles with the polyisocyanate composition (X) and store at room temperature for a certain period of time. Visually evaluate the turbidity of the appearance according to the following criteria on a two-level scale, and summarize the results in Table 1.

[0314] ○: No crystallization after 7 days

[0315] ×: Crystallization within 7 days

[0316] [Table 1]

[0317]

[0318] (Viscosity of polyisocyanate composition (X))

[0319] Using a rotational viscometer, at a cone plate: 1° × 50mm diameter, and a shear rate of 100sec... -1 Viscosity (mPa·s) was measured at 70℃±1℃. Evaluations were conducted on a two-tiered basis according to the following criteria, and the results are summarized in Table 2.

[0320] Evaluation 0: Below 40000 mPa·s

[0321] Evaluation ×: Above 40000 mPa·s

[0322] [Table 2]

[0323]

[0324] <Evaluation of Adhesives>

[0325] The adhesive of the example was prepared by mixing the polyisocyanate composition (X) and the polyol composition (Y) according to the formulations shown in Table 3. It should be noted that the polyisocyanate composition (X'-1) underwent crystallization, and therefore was not evaluated as an adhesive.

[0326] The solid content of a 40 μm thick stretched polyethylene film (BOPE film) is 3 g / m. 2 The prepared adhesive was coated and laminated onto a 60 μm thick chain-like low-density polyethylene (LLDPE) film. The film was then cured at 40°C for 72 hours to obtain a laminated film.

[0327] (Lamination strength)

[0328] Test pieces were cut from the laminate with a width of 15 mm. The bond strength (N / 15 mm) at a 90-degree peel was measured using a tensile testing machine at an ambient temperature of 25°C and a peel speed of 100 mm / min. The results were evaluated according to the following criteria and summarized in Table 3.

[0329] 〇:1.0N / 15mm or more

[0330] ×: Less than 1.0N / 15mm

[0331] (Oxygen permeability)

[0332] The laminated film was adjusted to a size of 10cm × 10cm, and the oxygen permeability (cc / m³) was measured using an OX-TRAN2 / 21 (MOCON: oxygen permeability measuring device) at 23°C and 50%RH according to JIS-K7126 (isobaric method). 2 (day atm), the results are summarized in Table 3. The oxygen permeability of the BOPE membrane used at this time was 2012 cc / m. 2 The oxygen permeability of the LLDPE film is 1676 cc / m·day·atm.2 • day • atm. It should be noted that RH indicates humidity. Evaluation is as follows.

[0333] 〇: Below 600cc / m 2 ·day·atm

[0334] ×:600cc / m 2 ·day·atm and above

[0335] [Table 3]

[0336]

Claims

1. A polyisocyanate composition (X) comprising a polyisocyanate compound (A) having a plurality of isocyanate groups, said polyisocyanate compound (A) comprising a polyurethane polyisocyanate (A1) as a reaction product of phenyl dimethyl diisocyanate (a) and a diol (b) having a molecular weight of 65 or more and 300 or less.

2. The polyisocyanate composition (X) according to claim 1, wherein, The diol (b) comprises a diol (b1) having an alkyl side chain having 1 or more and 4 or fewer carbon atoms.

3. The polyisocyanate composition (X) according to claim 1, wherein, The diol (b) comprises a diol (b2) having an ether bond.

4. The polyisocyanate composition (X) according to claim 1, wherein, The polyurethane polyisocyanate (A1) accounts for more than 20% by mass in the polyisocyanate compound (A).

5. The polyisocyanate composition (X) according to claim 1, wherein, The isocyanate monomer content in the polyisocyanate composition (X) is less than 1.0% by mass.

6. A two-component curable composition comprising the polyisocyanate composition (X) of claim 1, and comprising an isocyanate reactive composition (Y).

7. A two-component curable coating agent comprising the polyisocyanate composition (X) of claim 1, and comprising an isocyanate reactive composition (Y). The isocyanate reactive composition (Y) comprises an isocyanate reactive compound (E).

8. The two-component curable coating agent according to claim 7, wherein, The isocyanate reactive compound (E) comprises at least one selected from polyester polyol (E1), polyether polyol (E2), vegetable oil polyol (E3), polyurethane polyol (E4), sugar alcohol (E5), acrylic polyol (E6), amine compound (E7), and epoxy compound (E8).

9. The two-component curable coating agent according to claim 7, wherein, The isocyanate reactive compound (E) comprises at least one selected from polyester polyols (E1-1) obtained by polycondensation of a polycarboxylic acid containing an ortho-oriented polycarboxylic acid with a polyol, polyester polyols having an isocyanurate ring (E1-2), and polyester polyols having polymerizable carbon-carbon double bonds (E1-3).

10. A two-component curing adhesive comprising the polyisocyanate composition (X) of claim 1, and comprising an isocyanate reactive composition (Y). The isocyanate reactive composition (Y) comprises an isocyanate reactive compound (E).

11. The two-component curing adhesive according to claim 10, wherein, The isocyanate reactive compound (E) comprises at least one selected from polyester polyol (E1), polyether polyol (E2), vegetable oil polyol (E3), polyurethane polyol (E4), sugar alcohol (E5), acrylic polyol (E6), amine compound (E7), and epoxy compound (E8).

12. The two-component curing adhesive according to claim 10, wherein, The isocyanate reactive compound (E) comprises at least one selected from polyester polyols (E1-1) obtained by polycondensation of a polycarboxylic acid containing an ortho-oriented polycarboxylic acid with a polyol, polyester polyols having an isocyanurate ring (E1-2), and polyester polyols having polymerizable carbon-carbon double bonds (E1-3).

13. A laminate comprising a substrate and a coating layer disposed on the substrate, the coating layer being a cured coating film of the two-component curable coating agent of claim 7.

14. 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 10.

15. A packaging material formed from the laminate as described in claim 13 or 14.

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