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

Abstract

To provide a new polyisocyanate composition suitable for a two-component curable composition such as a two-component curable adhesive or a two-component curable coating agent.　Provided is a polyisocyanate composition (X) containing a polyisocyanate compound (A) having a plurality of isocyanate groups, the polyisocyanate compound (A) containing a polyurethane polyisocyanate (A1) which is a reaction product of a toluene diisocyanate (a) and a diol (b) having a molecular weight of 65-300. Also provided are: a two-component curable composition containing the polyisocyanate composition (X) and an isocyanate-reactive composition (Y); a coating agent; and an adhesive.

Description

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

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

[0002] Polyurethane resins are usually produced by reacting polyisocyanate with an active hydrogen group-containing compound, and are widely used in various industrial fields as coating agents, adhesives, pressure-sensitive adhesives, elastomers, rigid foams, flexible foams, binders, etc. Among the products using such urethane resins, so-called two-component curing products are known, in which polyisocyanate and an active hydrogen compound are mixed together immediately before use.

[0003] As the polyisocyanate, diisocyanate monomers such as hexamethylene diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate may be used, but oligomers of diisocyanate monomers or urethane polyisocyanates derived from diisocyanates and polyols may also be used in order to improve the physical properties of the polyurethane resin and to ensure the safety of workers who handle them by suppressing their vapor pressure.

[0004] JP 2014-159548 A JP 2001-172602 A JP 2017-210519 A

[0005] An object of the present invention is to provide a novel polyisocyanate composition suitable for two-component curing compositions such as two-component curing adhesives and two-component curing coating agents.

[0006] That is, the present invention relates to a polyisocyanate composition (X) containing a polyisocyanate compound (A) having a plurality of isocyanate groups, wherein the polyisocyanate compound (A) contains a polyurethane polyisocyanate (A1) which is a reaction product of toluene diisocyanate (a) and a diol (b) having a molecular weight of 65 or more and 300 or less.

[0007] According to the present invention, it is possible to provide a novel polyisocyanate composition that is suitable for two-component curing compositions such as two-component curing adhesives and two-component curing coating agents.

[0008] <Polyisocyanate Composition (X)> (Polyurethane Polyisocyanate (A1)) The polyisocyanate composition (X) of the present invention contains a polyisocyanate compound (A) having a plurality of isocyanate groups, and the polyisocyanate compound (A) contains a polyurethane polyisocyanate (A1) that is a reaction product of toluene diisocyanate (a) and diol (b) having a molecular weight of 65 or more and 300 or less. The toluene diisocyanate (a) may be either or both of 2,4'-toluene diisocyanate and 2,6'-toluene diisocyanate.

[0009] The diol (b) used in the synthesis of the polyurethane polyisocyanate (A1) is not particularly limited and any conventionally known diol can be used as long as it has a molecular weight of 65 to 300. By using a diol (b) having a molecular weight of 65 or more, a polyisocyanate composition (X) with excellent storage stability can be obtained. By using a diol having a molecular weight of 300 or less, the reaction with the isocyanate-reactive composition (Y) described below proceeds smoothly, and a two-component curing composition with rapid development of physical properties can be obtained.

[0010] The diol (b) preferably contains at least one of a diol (b1) having an alkyl side chain containing 1 to 4 carbon atoms and a diol (b2) having an ether bond. The diol (b) may have the characteristics of both the diol (b1) and the diol (b2).

[0011] Examples of the diol (b1) having an alkyl side chain containing 1 to 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, 2-(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-propanediol, 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, and 4,6-nonanediol.

[0012] Examples of the diol (b2) having an ether bond 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.

[0013] The diol (b) may be a single compound exemplified above, or a combination of two or more compounds. When a combination of two or more compounds is used as the diol (b), a combination of two or more compounds having the characteristics of the diol (b1) may be used, such as a combination of neopentyl glycol and 2-butyl-2-ethyl-1,3-propanediol, or a combination of two or more compounds having the characteristics of the diol (b2) may be used, such as a combination of dipropylene glycol, tripropylene glycol, and tetrapropylene glycol. A combination of two or more compounds having the characteristics of the diol (b1) and two or more compounds having the characteristics of the diol (b2) may be used, such as a combination of 2-butyl-2-ethyl-1,3-propanediol and diethylene glycol or triethylene glycol.

[0014] The content of the diols (b1) and (b2) in the diol (b) (here, the content of either (b1) or (b2) may be 0) is preferably 20% by mass or more, more preferably 40% by mass or more. The total amount of the diol (b) may be at least one selected from the diols (b1) and (b2).

[0015] The polyurethane polyisocyanate (A1) is obtained by reacting toluene diisocyanate (a) with polyol (b) under conditions in which the isocyanate groups of toluene diisocyanate (a) are in excess relative to the hydroxyl groups of polyol (b). The equivalent ratio of isocyanate groups to hydroxyl groups [NCO] / [hydroxyl groups] can be appropriately adjusted, but is, for example, 2.0 or more and 20.0 or less.

[0016] The polyisocyanate composition (X) used in the present invention preferably has a content of diisocyanate monomers, i.e., diisocyanate monomers such as aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates, which are exemplified as raw materials for the isocyanate derivative (A2) described later, reduced to 1.0% by mass or less, more preferably 0.1% by mass or less.

[0017] From the viewpoint of occupational safety and health, there is a movement to restrict the use of isocyanate monomers, and the European Commission has adopted the REACH regulation, which prohibits the marketing of products containing 0.1% by mass or more of isocyanate monomers unless certain requirements are met. Products that comply with this regulation can be made by removing unreacted diisocyanate monomers until the amount of diisocyanate monomer in the polyisocyanate composition is 0.1% by mass or less.

[0018] Furthermore, when a laminate for food packaging is manufactured using a two-component curing adhesive containing an aromatic isocyanate prepolymer, unreacted aromatic isocyanate monomer may remain in the adhesive layer. The isocyanate monomer reacts with surrounding water to form primary aromatic amine (PAA), which may migrate through the film and leach into the contents (food). Due to concerns about the harmfulness of PAA to the human body, various regulations have been established, including the European Commission's detection limit for PAA in its regulations on food contact plastic materials and articles.

[0019] Because PAA reacts with unreacted aromatic isocyanate present in the vicinity, the concentration of PAA gradually decreases even when aromatic isocyanate remains in the adhesive layer. Although it eventually falls below the detection limit, from the viewpoint of the manufacturing efficiency of laminates for food packaging, it is preferable that the initial value of aromatic isocyanate monomer remaining in the adhesive layer is low. By removing the diisocyanate monomer in advance, a two-component curing adhesive with excellent manufacturing efficiency can be obtained.

[0020] The diisocyanate monomer can be removed by distilling the diisocyanate monomer under reduced pressure using a short-path distillation apparatus, a thin-film distillation apparatus, etc. The degree of reduced pressure and the distillation temperature are appropriately adjusted depending on the diisocyanate monomer to be removed, and are, for example, 0.1 mbar or less and 120° C. to 190° C. The diisocyanate monomer removal step may be carried out multiple times.

[0021] The content of diisocyanate monomer can be measured by gas chromatography using an internal standard, for example, in accordance with ASTM D 3432. Alternatively, it can also be measured by liquid chromatography under the following conditions.

[0022] Equipment: Waters Corporation "ACQUITY UPLC H-Class" Data processing: Waters Corporation "Empower-3" Column: Waters Corporation "ACQUITY UPLC HSS T3" (100 mm x 2.1 mmφ, 1.8 μm) 40°C Eluent: Ammonium formate aqueous solution / methanol, 0.3 mL / min Detector: PDA Sample preparation: 1. Dissolve 100 mg of appropriately blocked sample in 10 ml of THF (for LC) 2. Vortex for 30 seconds 3. Dilute appropriately with eluent (mobile phase) 4. Pass through a 0.2 μm filter to prepare the measurement sample. Calculation of area ratio: Calculate using the maximum absorption wavelength for the target substance.

[0023] (Isocyanate Derivative (A2)) The polyisocyanate composition (X) may contain an isocyanate derivative (A2) other than the polyurethane polyisocyanate (A1) in order to improve the storage stability and coatability of the polyisocyanate composition (X) and to improve the flexibility of the coating film when used as a two-component curing composition described below. Examples of the isocyanate derivative (A2) include conventionally known aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and biuret derivatives (A2-1), nurate derivatives (A2-2), adducts (A2-3), allophanate derivatives (A2-4), carbodiimide-modified derivatives (A2-5), uretdione-modified derivatives (A2-6), and polyurethane polyisocyanates other than the polyurethane polyisocyanate (A1) (A2-7), and the like. One or more of these may be used in combination.

[0024] 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-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate (also known as PPDI), and 2,4-toluene. Examples of the diisocyanate include, but are not limited to, 2,6-toluene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, tolidine diisocyanate (also known as TODI), dianisidine diisocyanate, naphthalene diisocyanate (also known as NDI), 4,4'-diphenyl ether diisocyanate, and 4,4',4"-triphenylmethane triisocyanate.

[0025] The araliphatic diisocyanate means an aliphatic isocyanate having one or more aromatic rings in the molecule, and examples thereof include, but are not limited to, m- or p-xylylene diisocyanate (also known as XDI), α,α,α',α'-tetramethylxylylene diisocyanate (also known as TMXDI), and the like.

[0026] Examples of aliphatic diisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate (also known as PDI), 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate (also known as LDI), but are not limited to these.

[0027] Examples of alicyclic diisocyanates include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, isophorone diisocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebiscyclohexyl isocyanate (also known as hydrogenated MDI or HMDI), 1,3-bis(isocyanatomethyl)cyclohexane (also known as hydrogenated XDI or HXDI), hydrogenated TMXDI, and norbornane diisocyanate (also known as NBDI), but are not limited to these.

[0028] Examples of polyols that can be used in the synthesis of polyurethane polyisocyanate (A2-7) include glycols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol;

[0029] Trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, pentaerythritol, and 1,3,5-tris(2-hydroxyethyl)isocyanurate; bisphenols such as bisphenol A, bisphenol F, hydrogenated bisphenol A, and hydrogenated bisphenol F; dimer diol;

[0030] polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexylene in the presence of a polymerization initiator such as the above-mentioned glycols and trifunctional or tetrafunctional aliphatic alcohols;

[0031] Polyester polyols (1) are reaction products of polyesters obtained by ring-opening polymerization of cyclic ester compounds such as propiolactone, butyrolactone, ε-caprolactone, σ-valerolactone, β-methyl-σ-valerolactone, and polyhydric alcohols such as the glycols, glycerin, trimethylolpropane, and pentaerythritol; polyester polyols (2) are obtained by reacting bifunctional polyols such as the glycols, dimer diols, or bisphenols with polycarboxylic acids; polyester polyols (3) are obtained by reacting trifunctional or tetrafunctional aliphatic alcohols with polycarboxylic acids; polyester polyols (4) are obtained by reacting bifunctional polyols, trifunctional or tetrafunctional aliphatic alcohols, and polycarboxylic acids; polyester polyols (5) are polymers of hydroxyl acids such as dimethylolpropionic acid and castor oil fatty acid;

[0032] a polyether polyurethane polyol obtained by polymerizing the polyether polyol with an isocyanate compound; a polyester polyether polyurethane polyol obtained by reacting at least one of polyester polyols (1) to (5), a polyether polyol, and an isocyanate compound; a polyester polyurethane polyol obtained by polymerizing polyester polyols (1) to (5) with an isocyanate compound;

[0033] Examples include castor oil-based polyols such as castor oil, dehydrated castor oil, hydrogenated castor oil which is a hydrogenated castor oil, and castor oil-based polyols such as 5 to 50 mol alkylene oxide adducts of castor oil, and mixtures thereof, and these may be used alone or in combination of two or more.

[0034] Examples of polycarboxylic acids used in the synthesis of the polyester polyols (2) to (4) include aromatic polybasic acids such as orthophthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride, naphthalic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid, benzophenonetetracarboxylic acid, benzophenonetetracarboxylic dianhydride, 5-sodium sulfoisophthalic acid, tetrachlorophthalic anhydride, and tetrabromophthalic anhydride; and methyl esters of aromatic polybasic acids such as dimethyl terephthalic acid and dimethyl 2,6-naphthalenedicarboxylate.

[0035] Aliphatic polybasic acids such as malonic acid, succinic acid, succinic anhydride, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, maleic anhydride, and itaconic acid; alkyl esters of aliphatic polybasic acids such as dimethyl malonate, diethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, diethyl pimelate, diethyl sebacate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, and diethyl maleate;

[0036] Examples of the alicyclic polybasic acids include 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, cyclohexane-1,2,4-tricarboxylic-1,2-anhydride, himic acid anhydride, and HET acid anhydride, and these may be used alone or in combination of two or more.

[0037] The molecular weight of the polyol used in the synthesis of these polyurethane polyisocyanates (A2-7) can be adjusted as appropriate, but is, for example, 50 g / mol or more and 4000 g / mol or less.

[0038] The polyurethane polyisocyanate (A2-7) can be obtained by reacting an isocyanate with a polyol under conditions in which the isocyanate groups of the isocyanate are in excess relative to the hydroxyl groups of the polyol, and then removing unreacted diisocyanate monomers as needed under the same conditions as those for the polyurethane polyisocyanate (A1). The equivalent ratio of isocyanate groups to hydroxyl groups [NCO] / [hydroxyl groups] can be appropriately adjusted, but is, for example, from 2.0 to 20.0.

[0039] When the polyisocyanate composition (X) contains the isocyanate derivative (A2), the content of the polyurethane polyisocyanate (A1) in the polyisocyanate compound (A) (the total of the polyurethane polyisocyanate (A1), the isocyanate derivative (A2), and the isocyanate monomer) can be appropriately adjusted depending on the desired performance, but is, for example, preferably 20% by mass or more, more preferably 50% by mass or more. The entire amount of the polyisocyanate compound (A) may be the polyurethane polyisocyanate (A1).

[0040] The NCO % of the polyisocyanate composition (X) can be adjusted appropriately depending on the purpose, but is preferably 7% or more and 21% or less, for example.

[0041] The polyisocyanate composition (X) may contain components other than the polyisocyanate compound, such as, but not limited to, a solvent (B), a phosphoric acid derivative (C), a plasticizer (D), and the like.

[0042] (Solvent (B)) Examples of the solvent (B) include esters such as ethyl acetate, butyl acetate, and cellosolve acetate; ketones such as acetone, methyl ethyl ketone, isobutyl ketone, and cyclohexanone; ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and ethylene chloride; dimethyl sulfoxide; and dimethyl sulfamide. These may be used alone or in combination of two or more.

[0043] (Phosphoric Acid Derivative (C)) Examples of the phosphoric acid derivative (C) include phosphoric acid, pyrophosphoric acid, triphosphoric acid, methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, dibutyl phosphate, 2-ethylhexyl acid phosphate, bis(2-ethylhexyl) phosphate, isododecyl acid phosphate, butoxyethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, polyoxyethylene alkyl ether phosphate, etc. Phosphoric acid, pyrophosphoric acid, triphosphoric acid, and butyl acid phosphate are preferred.

[0044] When the polyisocyanate composition (X) of the present invention contains the phosphoric acid derivative (C), its content can be appropriately adjusted, but is, for example, 10 ppm or more and 5000 ppm or less, more preferably 50 ppm or more, and more preferably 1000 ppm or less, of the solid content of the polyisocyanate composition (X).

[0045] (Plasticizer (D)) Examples of the plasticizer (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.

[0046] Examples of the phthalic acid plasticizer include phthalic acid ester plasticizers such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, diheptyl phthalate, di-(2-ethylhexyl) phthalate, di-n-octyl phthalate, dinonyl phthalate, diisononyl phthalate, didecyl phthalate, diisodecyl phthalate, ditridecyl phthalate, diundecyl phthalate, dilauryl phthalate, distearyl phthalate, diphenyl phthalate, dibenzyl phthalate, butylbenzyl phthalate, dicyclohexyl phthalate, octyldecyl phthalate, dimethyl isophthalate, di-(2-ethylhexyl) isophthalate, and diisooctyl isophthalate; and tetrahydrophthalic acid ester plasticizers such as di-(2-ethylhexyl) tetrahydrophthalate, di-n-octyl tetrahydrophthalate, and diisodecyl tetrahydrophthalate.

[0047] Examples of the fatty acid plasticizer include adipic acid plasticizers such as di-n-butyl adipate, di-(2-ethylhexyl) adipate, diisodecyl adipate, diisononyl adipate, di(C6-C10 alkyl) adipate, and dibutyl diglycol adipate; azelaic acid plasticizers such as di-n-hexyl azelate, di-(2-ethylhexyl) azelate, and diisooctyl azelate; and di-n-butyl sebacate and di-(2 Sebacic acid plasticizers such as di-n-butyl maleate, di-(2-ethylhexyl) sebacate, and diisononyl sebacate; maleic acid plasticizers such as dimethyl maleate, diethyl maleate, di-n-butyl maleate, and di-(2-ethylhexyl) maleate; fumaric acid plasticizers such as di-n-butyl fumarate and di-(2-ethylhexyl) fumarate; monomethyl itaconate, monobutyl itaconate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, Examples of suitable plasticizers include itaconic acid-based plasticizers such as itaconate and di-(2-ethylhexyl)itaconate; stearic acid-based plasticizers such as n-butyl stearate, glycerin monostearate, and diethylene glycol distearate; oleic acid-based plasticizers such as butyl oleate, glyceryl monooleate, and diethylene glycol monooleate; citric acid-based plasticizers such as triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tributyl citrate, and acetyl tri-(2-ethylhexyl) citrate; ricinoleic acid-based plasticizers such as methyl acetyl ricinoleate, butyl acetyl ricinoleate, glyceryl monoricinoleate, and diethylene glycol monoricinoleate; and other fatty acid-based plasticizers such as diethylene glycol monolaurate, diethylene glycol dipelargonate, and pentaerythritol fatty acid esters.

[0048] Examples of aromatic polycarboxylic acid plasticizers include trimellitic acid plasticizers such as tri-n-hexyl trimellitate, tri-(2-ethylhexyl) trimellitate, tri-n-octyl trimellitate, triisooctyl trimellitate, triisononyl trimellitate, tridecyl trimellitate, and triisodecyl trimellitate; and pyromellitic acid plasticizers such as tetra-(2-ethylhexyl) pyromellitate and tetra-n-octyl pyromellitate.

[0049] Examples of phosphoric acid plasticizers include triethyl phosphate, tributyl phosphate, tri-(2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, octyl diphenyl phosphate, cresyl diphenyl phosphate, cresyl phenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris(chloroethyl) phosphate, tris(chloropropyl) phosphate, tris(dichloropropyl) phosphate, and tris(isopropylphenyl) phosphate.

[0050] Examples of polyol-based plasticizers include glycol-based plasticizers such as diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, triethylene glycol di-(2-ethylbutyrate), triethylene glycol di-(2-ethylhexoate), and dibutylmethylene bisthioglycolate; and glycerin-based plasticizers such as glycerol monoacetate, glycerol triacetate, and glycerol tributyrate.

[0051] Examples of epoxy plasticizers include epoxidized soybean oil, epoxy butyl stearate, di-2-ethylhexyl epoxy hexahydrophthalate, diisodecyl epoxy hexahydrophthalate, epoxy triglyceride, epoxidized octyl oleate, and epoxidized decyl oleate.

[0052] Examples of polyester plasticizers include adipic acid polyesters, sebacic acid polyesters, and phthalic acid polyesters.

[0053] Examples of carbonate plasticizers include propylene carbonate and ethylene carbonate.

[0054] Other examples of the plasticizer (D) include partially hydrogenated terphenyls, adhesive plasticizers, and polymerizable plasticizers such as diallyl phthalate, acrylic monomers and oligomers, etc. These plasticizers can be used alone or in combination of two or more.

[0055] The amount of the plasticizer (D) to be added can be adjusted appropriately depending on the target viscosity, but, as an example, it is preferable to keep it at 30 mass % or less of the solid content of the polyisocyanate composition (X). The polyisocyanate composition (X) does not necessarily need to contain the plasticizer (D).

[0056] <Two-component curing composition> The polyisocyanate composition (X) of the present invention can be used as a two-component curing composition in combination with an isocyanate-reactive composition containing a compound reactive with isocyanate. Examples of the compound reactive with isocyanate include polyether polyol, polyester polyol, polyester polyether polyol, polyurethane polyol, polyester polyurethane polyol, polyether polyurethane polyol, vegetable oil polyol, sugar alcohol, polycarbonate polyol, acrylic polyol, hydroxyl group-containing olefin resin, hydroxyl group-containing fluororesin, (poly)alkanolamine, and epoxy resin.

[0057] Such two-component curing compositions can be used, for example, as adhesives, coating agents, sealants, elastomers, and the like.

[0058] <Two-component curing coating agent> The two-component curing coating agent of the present invention comprises the above-described polyisocyanate composition (X) and isocyanate-reactive composition (Y). The coating agent of the present invention can be suitably used for various applications, such as coating agents for metal substrates such as aluminum and steel plates, overcoats for coating films containing aluminum pigments or metal particles, coatings for electrical components, and electrical insulation. Furthermore, by selecting an appropriate isocyanate-reactive composition (Y), a coating agent with excellent gas barrier properties can be obtained. The gas barrier coating agent can be suitably used, for example, in the production of laminates with gas barrier properties.

[0059] The isocyanate-reactive composition (Y) contains a compound (E) having a plurality of functional groups reactive with isocyanate (hereinafter also referred to as an isocyanate-reactive compound (E)), such as polyester polyol (E1), polyether polyol (E2), vegetable oil polyol (E3), polyurethane polyol (E4), sugar alcohol (E5), acrylic polyol (E6), amine compound (E7), epoxy compound (E8), etc. The isocyanate-reactive compound (E) can be used alone or in combination of two or more.

[0060] Examples of the polyester polyol (E1) include polyester polyols which are reaction products of polyhydric alcohols and polycarboxylic acids, and lactone-based polyester polyols obtained by polycondensation reaction of aliphatic polyols and various lactones such as ε-caprolactone. It is preferable to use polyester polyols which are reaction products of polyhydric alcohols and polycarboxylic acids.

[0061] Examples of polyhydric alcohols include aliphatic diols such as ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,2,2-trimethyl-1,3-propanediol, 2,2-dimethyl-3-isopropyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-bis(hydroxymethyl)cyclohexane, and 2,2,4-trimethyl-1,3-pentanediol;

[0062] aliphatic polyols having three or more functional groups, such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, and pentaerythritol;

[0063] Bisphenols such as bisphenol A and bisphenol F; alkylene oxide adducts of bisphenols obtained by adding ethylene oxide, propylene oxide, or the like to bisphenols such as bisphenol A and bisphenol F;

[0064] Examples of such polyether polyols include polyether polyols obtained by ring-opening polymerization of an aliphatic diol or polyol with various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether. These polyether polyols may be used alone or in combination of two or more.

[0065] Examples of polycarboxylic acids include aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, and 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid; and anhydrides or ester-forming derivatives of these aliphatic or dicarboxylic acids; and polybasic acids such as p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid, and ester-forming derivatives of these dihydroxycarboxylic acids, and dimer acid, and these may be used alone or in combination of two or more.

[0066] The polyester polyol (E1) preferably has a molecular weight of 250 g / mol to 20,000 g / mol, more preferably 500 g / mol to 10,000 g / mol, and a hydroxyl value of 5 mg KOH / g to 500 mg KOH / g.

[0067] Examples of the polyether polyol (E2) include those obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexylene in the presence of a polymerization initiator.

[0068] Examples of the polymerization initiator include glycols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and triethylene glycol;

[0069] trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, pentaerythritol, and triols of polypropylene glycol;

[0070] Examples thereof include primary or secondary alkylamines such as ethylamine and diethylamine, amine compounds having a plurality of amino groups such as methylenediamine and ethylenediamine, and amine compounds having an active hydrogen group such as primary or secondary alkanolamines such as monoethanolamine and diethanolamine.

[0071] The molecular weight of the polyether polyol (E2) can be adjusted appropriately, but is preferably 100 g / mol or more and 8000 g / mol or less, for example. The hydroxyl value of the polyether polyol (E2) can be adjusted appropriately, but is preferably 10 mgKOH / g or more and 1200 mgKOH / g or less, for example.

[0072] Examples of the vegetable oil polyol (E3) include castor oil, dehydrated castor oil, hardened castor oil which is a hydrogenated castor oil, and an alkylene oxide 5 to 50 mole adduct of castor oil.

[0073] The polyurethane polyol (E4) is a reaction product of a low-molecular-weight or high-molecular-weight polyol and a polyisocyanate compound. The low-molecular-weight or high-molecular-weight polyol may be the same as the polyhydric alcohols exemplified as raw materials for the polyester polyol (E1). The polyisocyanate compound may be the same as the polyhydric alcohols exemplified as raw materials for the isocyanate derivative (A2).

[0074] Examples of the sugar alcohol (E5) include pentaerythritol, sucrose, xylitol, sorbitol, isomalt, lactitol, maltitol, and mannitol.

[0075] The acrylic polyol (E6) is obtained by copolymerizing a (meth)acrylic acid ester having a hydroxyl group as an essential component with a polymerizable unsaturated monomer as needed. In this specification, (meth)acrylic acid means methacrylic acid or acrylic acid. Examples of the (meth)acrylic acid ester having a hydroxyl group include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate, and these can be used alone or in combination of two or more.

[0076] Examples of the polymerizable unsaturated monomer include alkyl (meth)acrylates having an alkyl group having 1 to 22 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate; aralkyl (meth)acrylates, such as benzyl (meth)acrylate and 2-phenylethyl (meth)acrylate; cycloalkyl (meth)acrylates, such as cyclohexyl (meth)acrylate and isobornyl (meth)acrylate; ω-alkoxyalkyl (meth)acrylates, such as 2-methoxyethyl (meth)acrylate and 4-methoxybutyl (meth)acrylate; polyfunctional (meth)acrylates such as ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and dipentaerythritol hexa(meth)acrylate;

[0077] (Meth)acrylic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, 4-methylcyclohex-4-ene-1,2-dicarboxylic anhydride, bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride, 1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic anhydride, 2-octa-1,3-diketospiro[4.4]non-7-ene, bicyclo[ Examples of suitable polymerizable unsaturated monomers include polymerizable unsaturated monomers having an acid group, such as methyl-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, maleopimaric acid, tetrahydrophthalic anhydride, methyl-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, methyl-norbornen-5-ene-2,3-dicarboxylic anhydride, norborn-5-ene-2,3-dicarboxylic anhydride, sulfonated styrene, and vinylbenzenesulfonamide; vinyl carboxylic acid vinyl esters, such as vinyl acetate, vinyl propionate, vinyl pivalate, and vinyl benzoate; alkyl esters of crotonic acid, such as methyl crotonate and ethyl crotonate; and dialkyl esters of unsaturated dibasic acids, such as dimethyl maleate, di-n-butyl maleate, dimethyl fumarate, and dimethyl itaconate. These may be used alone or in combination of two or more.

[0078] The amine compound (E7) is a compound having an amino group. In this specification, the amino group is defined as an NH ２ group or NHR group (R is an alkyl group or aryl group which may have a functional group).

[0079] As the amine compound (E7), known compounds can be used without any particular limitation, and examples thereof include methylenediamine, ethylenediamine, isophoronediamine, 3,9-dipropanamine-2,4,8,10-tetraoxaspirodoundecane, lysine, 2,2,4-trimethylhexamethylenediamine, hydrazine, piperazine, 2-hydroxyethylethylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, poly(propylene glycol)diamine, poly(propylene glycol)triamine, poly(propylene glycol)tetraamine, 1,2-diaminopropane, 1,3-diaminopropane,

[0080] 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, nonaethylenedecamine, trimethylhexamethylenediamine, tetra(aminomethyl)methane, tetrakis(2-aminoethylaminomethyl)methane, 1,3-bis(2'-aminoethylamino)propane, triethylene-bis(trimethylene)hexamine, bis(3-aminoethyl)amine, bishexamethylenetriamine, 1,4-cyclohexanediamine, 4,4'-methylenebiscyclohexylamine, 4,4'-isopropylidenebiscyclohexylamine, norbornadiamine,

[0081] amine compounds (E7-1) having multiple amino groups such as bis(aminomethyl)cyclohexane, diaminodicyclohexylmethane, isophoronediamine, menthenediamine, bis(cyanoethyl)diethylenetriamine, 1,4-bis-(8-aminopropyl)-piperazine, piperazine-1,4-diazacycloheptane, 1-(2'-aminoethylpiperazine), 1-[2'-(2"-aminoethylamino)ethyl]piperazine, tricyclodecanediamine, and polyureaamines which are reaction products of the above-mentioned various polyamines with the above-mentioned various isocyanate components;

[0082] primary or secondary alkanolamines (E7-2) such as monoethanolamine, monoisopropanolamine, monobutanolamine, N-methylethanolamine, N-ethylethanolamine, N-methylpropanolamine, diethanolamine, and diisopropanolamine;

[0083] Examples include primary or secondary amines (E7-3) such as ethylamine, octylamine, laurylamine, myristylamine, stearylamine, oleylamine, diethylamine, dibutylamine, and distearylamine.

[0084] The amount of the amine compound (E7) to be added can be adjusted appropriately depending on the purpose. As an example, it is preferably added so that the amine value of the isocyanate-reactive composition (Y) becomes 20 to 70 mgKOH / g, more preferably 25 to 50 mgKOH / g.

[0085] In this specification, the amine value refers to the number of milligrams of KOH equivalent to the amount of HCl required to neutralize 1 g of sample, and is not particularly limited and can be calculated using known methods. When the chemical structure of the amine compound (E7) and, if necessary, the average molecular weight, etc. are known, the amine value can be calculated from (number of amino groups per molecule / average molecular weight) x 56.1 x 1000. When the chemical structure, average molecular weight, etc. of the amine compound are unknown, the amine value can be measured according to known amine value measurement methods, for example, JIS K7237-1995.

[0086] The epoxy compound (E8) is not particularly limited as long as it is a compound having an epoxy group in the molecule, and examples thereof include polyglycidyl ether type epoxy resins of aliphatic polyols such as ethylene glycol, propylene glycol, hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol, glycerin, diglycerin, sorbitol, spiroglycol, and hydrogenated bisphenol A; bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol AD ​​type epoxy resin;

[0087] Aromatic epoxy resins such as novolac-type epoxy resins which are glycidyl ethers of phenol novolac resins and cresol novolac resins; polyglycidyl ethers of polyols which are ethylene oxide or propylene oxide adducts of aromatic polyhydroxy compounds such as bisphenol A, bisphenol F, bisphenol S, and bisphenol AD; polyglycidyl ether-type epoxy resins of polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; cycloaliphatic polyepoxy resins such as bis(3,4-epoxycyclohexylmethyl)adipate and 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate;

[0088] Examples of suitable epoxy resins include polyglycidyl esters of polycarboxylic acids such as propanetricarboxylic acid, butanetetracarboxylic acid, adipic acid, phthalic acid, terephthalic acid, and trimellitic acid; bisepoxy resins of hydrocarbon dienes such as butadiene, hexadiene, octadiene, dodecadiene, cyclooctadiene, α-pinene, and vinylcyclohexene; epoxy resins of diene polymers such as polybutadiene and polyisoprene; glycidylamine epoxy resins such as tetraglycidyldiaminodiphenylmethane, triglycidyl paraaminophenol, tetraglycidyl bisaminomethylcyclohexane, diglycidylaniline, and tetraglycidyl metaxylylenediamine; and epoxy resins containing heterocycles such as triazine and hydantoin. These may be used alone or in combination of two or more.

[0089] The isocyanate-reactive compound (E) preferably contains one having a glass transition temperature (Tg) of 15°C or higher. This makes it possible to obtain a coating agent in which blocking is suppressed. The upper limit of the glass transition temperature of the isocyanate-reactive compound (E) can be appropriately adjusted depending on the purpose, but is, for example, 80°C or lower.

[0090] In a preferred embodiment of the coating agent of the present invention, the isocyanate-reactive compound (E) includes at least one selected from polyester polyols (E1-1) obtained by polycondensation of a polycarboxylic acid, including an ortho-orienting polycarboxylic acid, with a polyhydric alcohol, polyester polyols (E1-2) having an isocyanuric ring, and polyester polyols (E1-3) having a polymerizable carbon-carbon double bond. The polyisocyanate composition (X) of the present invention can be used in combination with an isocyanate-reactive composition (Y) containing such an isocyanate-reactive compound (E) to provide a coating agent with excellent gas barrier properties.

[0091] Examples of ortho-oriented polycarboxylic acids used in the synthesis of polyester polyol (E1-1) include orthophthalic 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-anthracene carboxylic acid or its anhydride. These compounds may have a substituent on any carbon atom of the aromatic ring. Examples of such substituents include chloro, bromo, methyl, ethyl, i-propyl, hydroxyl, methoxy, ethoxy, phenoxy, methylthio, phenylthio, cyano, nitro, amino, phthalimido, carboxyl, carbamoyl, N-ethylcarbamoyl, phenyl, and naphthyl groups. These may be used alone or in combination of two or more.

[0092] The polycarboxylic acid may contain a polycarboxylic acid other than the ortho-oriented polycarboxylic acid. As such a polycarboxylic acid, the same polycarboxylic acids as those exemplified as raw materials for the polyester polyol (E1) can be used. When the polycarboxylic acid contains a polycarboxylic acid other than the ortho-oriented polycarboxylic acid, the proportion of the ortho-oriented polycarboxylic acid in the total amount of the polycarboxylic acid is preferably 40 to 100 mass%.

[0093] The polyhydric alcohol used in the synthesis of polyester polyol (E1-1) preferably contains at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol, and more preferably contains ethylene glycol. Furthermore, the polyhydric alcohol may be used in combination with other polyhydric alcohols listed as examples of raw materials for polyester polyol (E1). Examples of such polyhydric alcohols include glycerin, 1,3,5-tris(2-hydroxyethyl)isocyanuric acid, and trimethylolpropane.

[0094] When the polyester polyol (E1-1) has three or more hydroxyl groups (referred to as polyester polyol (e1-1) for convenience), some of the hydroxyl groups may be modified with acid groups. Such polyester polyols are also referred to as polyester polyols (E1-1') below. The polyester polyol (E1-1') is obtained by reacting the polyester polyol (e1-1) with a polycarboxylic acid or its acid anhydride. The proportion of hydroxyl groups modified with the polycarboxylic acid is preferably ⅓ or less of the hydroxyl groups in the polyester polyol (e1-1). Examples of polycarboxylic acids used for modification include, but are not limited to, succinic anhydride, maleic acid, 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.

[0095] The polyester polyol (E1-2) can be obtained, for example, by reacting a triol having an isocyanuric ring with a polycarboxylic acid including an ortho-oriented aromatic polycarboxylic acid and a polyhydric alcohol. Examples of the triol having an isocyanuric ring include alkylene oxide adducts of isocyanuric acid 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 polyhydric alcohol can be the same as those used for the polyester polyol (E1-1).

[0096] As the triol compound having an isocyanuric ring, 1,3,5-tris(2-hydroxyethyl)isocyanuric acid or 1,3,5-tris(2-hydroxypropyl)isocyanuric acid is preferably used. As the ortho-oriented aromatic polycarboxylic acid, orthophthalic anhydride is preferably used. As the polyhydric alcohol, ethylene glycol is preferably used.

[0097] The polyester polyol (E1-3) can be obtained by using a component having a polymerizable carbon-carbon double bond as a polycarboxylic acid or a polyhydric alcohol.

[0098] Examples of polycarboxylic acids having a polymerizable carbon-carbon double bond include maleic anhydride, maleic acid, fumaric acid, 4-cyclohexene-1,2-dicarboxylic acid and its acid anhydride, and 3-methyl-4-cyclohexene-1,2-dicarboxylic acid and its acid anhydride. It is believed that the fewer the number of carbon atoms, the less flexible the molecular chain and the less oxygen permeates, so maleic anhydride, maleic acid, and fumaric acid are preferred. Examples of polyhydric alcohols having a polymerizable carbon-carbon double bond include 2-butene-1,4-diol.

[0099] In addition to the above, polycarboxylic acids and polyhydric alcohols not having a polymerizable carbon-carbon double bond may be used in combination. Examples of such polycarboxylic acids and polyhydric alcohols include those similar to those used in 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, orthophthalic acid, orthophthalic acid anhydride, and isophthalic acid, and more preferably at least one of orthophthalic acid and its acid anhydride. The polyhydric alcohol is preferably at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol, and more preferably ethylene glycol.

[0100] When polyester polyols (E1-1), (E1-2), and (E1-3) are used for the purpose of gas barrier property, the amount used can be adjusted appropriately depending on the desired level of gas barrier property, but as an example, the amount used is preferably 50% by mass or more, more preferably 60% by mass or more, of the isocyanate-reactive compound (E). 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).

[0101] When polyester polyols (E1-1), (E1-2), and (E1-3) are used as the isocyanate-reactive compound (E), the hydroxyl value can be appropriately adjusted, but is preferably 20 mgKOH / g or more in view of ease of solubility in solvents, and is preferably 400 mgKOH / g or less in view of the reduced likelihood of blocking.

[0102] When the polyester polyols (E1-1), (E1-2), and (E1-3) have an acid group, the acid value is preferably 200 mgKOH / g or less, which can appropriately suppress the reaction between the polyisocyanate composition (X) and the isocyanate-reactive composition (Y), thereby providing a coating agent with excellent applicability.

[0103] The molecular weight of polyester polyols (E1-1), (E1-2), and (E1-3) is preferably 300 g / mol to 5000 g / mol, as this provides an excellent balance between adhesion and gas barrier properties. It is more preferably 350 g / mol to 3000 g / mol. The molecular weight is calculated from the obtained hydroxyl value and the number of functional hydroxyl groups in the design.

[0104] The coating agent of the present invention may or may not contain a solvent. As the solvent, the same solvents as those exemplified as the solvent (C) can be used.

[0105] The coating agent of the present invention may contain additives such as a urethanization catalyst, an organic filler, an inorganic filler, an organic pigment, an inorganic pigment, an extender pigment, a clay mineral, a wax, a surfactant, a stabilizer, a flow adjuster, a leveling agent, a rheology control agent, an ultraviolet absorber, an antioxidant, a plasticizer, etc. The urethanization catalyst and pigment may be the same as those used in the two-component curing adhesive described below.

[0106] The method for applying the coating agent is not particularly limited, and any conventionally known method can be used, including, for example, various coating methods such as spray coating, direct gravure coating, gravure kiss reverse coating, offset gravure coating, flexographic coating, offset coating, bar coating, roll kiss coating, forward rotation roll coating, reverse roll coating, slot die coating, vacuum die coating, (micro)chamber doctor coating, air doctor coating, blade coating, knife coating, spin coating, and dipping coating.

[0107] The amount of coating agent applied can be adjusted appropriately depending on the application, etc., but as an example, ２ More than 100g / m ２ The following is the result.

[0108] The two-component curing coating agent of the present invention is preferably used by blending the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) so that the ratio [NCO] / [isocyanate-reactive functional group], where [NCO] is the number of moles of isocyanate groups contained in the polyisocyanate composition (X) and [isocyanate-reactive functional group] is 0.5 to 5.0, more preferably 1.0 to 3.0. This allows for appropriate curing properties to be obtained without being dependent on the environmental humidity during coating.

[0109] <Two-component curing adhesive> The two-component curing adhesive of the present invention contains the above-described polyisocyanate composition (X) and isocyanate-reactive composition (Y).

[0110] When the adhesive of the present invention is used as a solventless adhesive, the viscosity of the polyisocyanate composition (X) is adjusted to a range suitable for the non-solvent lamination method. For example, the viscosity at 70°C is adjusted to be in the range of 100 to 20,000 mPas, more preferably 500 to 10,000 mPas. The viscosity of the polyisocyanate composition (X) can be adjusted, for example, by the structure of the polyurethane polyisocyanate (A1) (the diol (b) used) or the isocyanate compound (A2) used in combination as needed. The viscosity of the polyisocyanate composition (X) can be measured, for example, using a rotational viscometer with a cone and plate of 1° x 50 mm diameter and a shear rate of 100 sec. －１ , can be measured at 70°C ± 1°C.

[0111] When the adhesive of the present invention is used as a solvent-based adhesive, the viscosity of the polyisocyanate composition (X) can be adjusted by diluting it with a solvent.

[0112] (Isocyanate-reactive composition (Y)) The isocyanate-reactive composition (Y) contains an isocyanate-reactive compound (E). As the isocyanate-reactive compound (E), the same compounds as those used in the above-mentioned coating agent can be used alone or in combination of two or more.

[0113] The isocyanate-reactive compound (E) preferably contains one having a glass transition temperature (Tg) of 40°C or less. This makes it possible to obtain an adhesive with excellent adhesive properties. The lower limit of the glass transition temperature of the isocyanate-reactive compound (E) can be appropriately adjusted depending on the purpose, but is, for example, -50°C or higher.

[0114] As with the coating agent described above, an adhesive with excellent gas barrier properties can be obtained by using the isocyanate-reactive compound (E) in combination with an isocyanate-reactive composition (Y) containing at least one selected from polyester polyol (E1-1) obtained by polycondensing a polycarboxylic acid containing an ortho-orienting polycarboxylic acid with a polyhydric alcohol, polyester polyol (E1-2) having an isocyanuric ring, and polyester polyol (E1-3) having a polymerizable carbon-carbon double bond.

[0115] When polyester polyols (E1-1), (E1-2), and (E1-3) are used for the purpose of gas barrier property, the amount used can be adjusted appropriately depending on the desired level of gas barrier property, but as an example, the amount used is preferably 40% by mass or more, more preferably 50% by mass or more, of the isocyanate-reactive compound (E). 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).

[0116] When polyester polyols (E1-1), (E1-2), and (E1-3) are used as the isocyanate-reactive compound (E), the hydroxyl value is preferably 20 mgKOH / g or more, since this allows the adhesive to have excellent coating suitability even when used as a solventless adhesive. Furthermore, the hydroxyl value is preferably 400 mgKOH / g or less, since this allows the cured coating film of the adhesive to be flexible and allows the adhesive to exhibit good adhesion to flexible substrates.

[0117] When the polyester polyols (E1-1), (E1-2), and (E1-3) have an acid group, the acid value is preferably 200 mgKOH / g or less, which can appropriately suppress the reaction between the polyisocyanate composition (X) and the isocyanate-reactive composition (Y), thereby providing an adhesive with excellent coatability.

[0118] The molecular weight of polyester polyols (E1-1), (E1-2), and (E1-3) is preferably 300 g / mol to 5000 g / mol, as this provides an excellent balance between adhesiveness and gas barrier properties. It is more preferably 350 g / mol to 3000 g / mol. The molecular weight is calculated from the obtained hydroxyl value and the number of functional hydroxyl groups in the design.

[0119] (Monool Compound (F)) The isocyanate-reactive composition (Y) may contain a monool compound (F) having one alcoholic hydroxyl group. The main chain of the monool compound (F) is not particularly limited, and examples thereof include vinyl resins, acrylic resins, polyesters, epoxy resins, and urethane resins having one hydroxyl group. Aliphatic alcohols, alkyl alkylene glycols, and the like can also be used. The main chain of the monool compound (F) may be linear or branched. The bonding position of the hydroxyl group is not particularly limited, but it is preferably present at the terminal of the molecular chain.

[0120] Specific examples of the monool compound (F) include aliphatic monools such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, lauryl alcohol, myristyl alcohol, pentadecanol, cetyl alcohol, heptadecanol, stearyl alcohol, nonadecanol, other alkanols (C20 to C50), oleyl alcohol, and isomers thereof;

[0121] Cyclohexanol, methylcyclohexanol, 4-butylcyclohexanol, 4-pentylcyclohexanol, 4-hexylcyclohexanol, cyclodecanol, cyclododecanol, cyclopentadecanol, 4-isopropylcyclohexanol, 3,5,5-trimethylcyclohexanol, menthol, 2-norbornanol, borneol, 2-adamantanol, dicyclohexylmethanol, decitol, 2-cyclohexylcyclohexanol, 4-cyclohexylcyclohexanol, 4-(4-propylcyclohexyl)cyclohexanol, 4-(4-pentylcyclohex cyclohexanol, α-ambrinol, desoxycorticosterone, 11-dehydrocorticosterone, cholesterol, β-sitosterol, campesterol, stigmasterol, brassicasterol, lanosterol, ergosterol, β-cholestanol, testosterone, estrone, digitoxigenin, dehydroepiandrosterone, coprostanol, pregnenolone, epicholestanol, 7-dehydrocholesterol, estradiol benzoate, tigogenin, hecogenin, methandienone, cortisone acetate, stenolone, and isomers thereof;

[0122] aromatic aliphatic monools such as benzyl alcohol,

[0123] Examples of the polyoxyalkylene monool include polyoxyalkylene monools obtained by ring-opening addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran using an alkyl compound containing one active hydrogen as an initiator.

[0124] When the adhesive of the present invention is provided in a solventless form, the viscosity of the isocyanate-reactive composition (Y) is adjusted to a range suitable for the non-solvent lamination method. For example, the viscosity at 40°C is adjusted to a range of 100 to 50,000 mPas, more preferably 100 to 20,000 mPas. The viscosity of the isocyanate-reactive composition (Y) can be adjusted by the skeleton of the isocyanate-reactive compound (E) or the plasticizer described below.

[0125] (Other Components of the Adhesive) The two-component curing adhesive of the present invention may contain components other than those described above. The other components may be contained in either or both of the polyisocyanate composition (X) and the isocyanate-reactive composition (Y), or may be prepared separately from these and mixed with the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) immediately before application of the adhesive. Each component will be described below.

[0126] (Catalyst) Examples of the catalyst include metal catalysts, amine catalysts, aliphatic cyclic amide compounds, and quaternary ammonium salts.

[0127] Examples of the metal catalyst include metal complex catalysts, inorganic metal catalysts, and organic metal catalysts. Examples of the metal complex catalyst include acetylacetonate salts of metals selected from the group consisting of Fe (iron), Mn (manganese), Cu (copper), Zr (zirconium), Th (thorium), Ti (titanium), Al (aluminum), and Co (cobalt), such as iron acetylacetonate, manganese acetylacetonate, copper acetylacetonate, and zirconia acetylacetonate.

[0128] Examples of inorganic metal catalysts include those selected from Sn, Fe, Mn, Cu, Zr, Th, Ti, Al, Co, and the like.

[0129] Examples of the organometallic catalyst include organic zinc compounds such as zinc octylate, zinc neodecanoate, and zinc naphthenate; organic tin compounds such as stannous diacetate, stannous dioctoate, stannous dioleate, stannous dilaurate, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin oxide, and dibutyltin dichloride; organic nickel compounds such as nickel octylate and nickel naphthenate; organic cobalt compounds such as cobalt octylate and cobalt naphthenate; organic bismuth compounds such as bismuth octylate, bismuth neodecanoate, and bismuth naphthenate; titanium compounds such as tetraisopropyloxytitanate, dibutyltitanium dichloride, tetrabutyltitanium, butoxytitanium trichloride, aliphatic diketones, aromatic diketones, and titanium chelate complexes having at least one of alcohols having 2 to 10 carbon atoms as a ligand.

[0130] Examples of the amine catalyst include triethylenediamine, 2-methyltriethylenediamine, quinuclidine, 2-methylquinuclidine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N',N",N"-pentamethyl-(3-aminopropyl)ethylenediamine, N,N,N',N",N"-pentamethyldipropylenetriamine, N,N,N',N'-tetramethylhexamethylenediamine, bis(2-dimethylaminoethyl)ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol, N,N-dimethyl-N'-(2-hydroxyethyl)ethylenediamine, N,N-dimethyl-N'-(2-hydroxyethyl)propanediamine, bis(dimethylaminopropyl)amine, bis(dimethylaminopropyl)isopropyl propanolamine, 3-quinuclidinol, N,N,N',N'-tetramethylguanidine, 1,3,5-tris(N,N-dimethylaminopropyl)hexahydro-S-triazine, 1,8-diazabicyclo[5.4.0]undecene-7, N-methyl-N'-(2-dimethylaminoethyl)piperazine, N,N'-dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, 1-methylimidazole, 1 , 2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethylaminopropylimidazole, N,N-dimethylhexanolamine, N-methyl-N'-(2-hydroxyethyl)piperazine, 1-(2-hydroxyethyl)imidazole, 1-(2-hydroxypropyl)imidazole, 1-(2-hydroxyethyl)-2-methylimidazole, 1-(2-hydroxypropyl)-2-methylimidazole, and the like.

[0131] Examples of the aliphatic cyclic amide compound include δ-valerolactam, ε-caprolactam, ω-enantholactam, η-capryllactam, β-propiolactam, etc. Among these, ε-caprolactam is more effective in accelerating curing.

[0132] Examples of quaternary ammonium salts include hydroxy salts of alkyl ammonium, aromatic ammonium, etc., alkyl acid salts, halide salts, etc. Examples include, but are not limited to, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltriethylammonium chloride, hexadecyltrimethylammonium bromide, etc.

[0133] (Coupling Agent) Examples of the coupling agent include silane coupling agents, titanate-based coupling agents, and aluminum-based coupling agents.

[0134] Examples of the silane coupling agent include aminosilanes such as γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, and bis[3-(triethoxysilyl)propyl]amine; epoxysilanes such as β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane; vinylsilanes such as vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane; and hexamethyldisilazane and γ-mercaptopropyltrimethoxysilane.

[0135] Examples of titanate coupling agents include tetraisopropoxytitanium, tetra-n-butoxytitanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, titanium lactate, and tetrastearoxytitanium.

[0136] Examples of aluminum-based coupling agents include acetoalkoxyaluminum diisopropylate.

[0137] (Pigment) The pigment is not particularly limited, and examples thereof include organic pigments and inorganic pigments such as extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments, green pigments, blue pigments, metal powder pigments, luminescent pigments, and pearlescent pigments listed in the Paint Raw Materials Handbook 1970 Edition (compiled by the Japan Paint Manufacturers Association), as well as plastic pigments.

[0138] Examples of extender pigments include precipitated barium sulfate, powdered barium sulfate, precipitated calcium carbonate, calcium bicarbonate, kansui stone, alumina white, silica, hydrous fine powdered silica (white carbon), ultrafine powdered anhydrous silica (aerosil), silica sand, talc, precipitated magnesium carbonate, bentonite, clay, kaolin, and yellow ochre.

[0139] Specific examples of organic pigments include various insoluble azo pigments such as Benzidine Yellow, Hansa Yellow, and Lake 4R; soluble azo pigments such as Lake C, Carmine 6B, and Bordeaux 10; various (copper) phthalocyanine pigments such as Phthalocyanine Blue and Phthalocyanine Green; various chlorine dye lakes such as Rhodamine Lake and Methyl Violet Lake; various mordant dye pigments such as Quinoline Lake and Fast Sky Blue; various vat dye pigments such as Anthraquinone pigments, Thioindigo pigments, and Perinone pigments; various quinacridone pigments such as Synchasia Red B; various dioxazine pigments such as Dioxazine Violet; various condensed azo pigments such as Chromophtal; and aniline black.

[0140] Examples of inorganic pigments include various chromates such as yellow lead, zinc chromate, and molybdate orange; various ferrocyanide compounds such as iron blue; various metal oxides such as titanium oxide, zinc white, mapico yellow, iron oxide, red iron oxide, chrome oxide green, and zirconium oxide; various sulfides or selenides such as cadmium yellow, cadmium red, and mercury sulfide; various sulfates such as barium sulfate and lead sulfate; various silicates such as calcium silicate and ultramarine; various carbonates such as calcium carbonate and magnesium carbonate; various phosphates such as cobalt violet and manganese purple; various metal powder pigments such as aluminum powder, gold powder, silver powder, copper powder, bronze powder, and brass powder; flake pigments of these metals, mica flake pigments; metallic pigments and pearl pigments such as mica flake pigments coated with metal oxides and micaceous iron oxide pigments; graphite, carbon black, and the like.

[0141] Examples of plastic pigments include "Grandol PP-1000" and "PP-2000S" manufactured by DIC Corporation.

[0142] The pigment to be used may be selected appropriately depending on the purpose. For example, inorganic oxides such as titanium oxide and zinc oxide are preferably used as white pigments because they have excellent durability, weather resistance, and design properties, and carbon black is preferably used as black pigments.

[0143] The blending amount of the pigment is, for example, 1 to 400 parts by mass per 100 parts by mass of the total amount of nonvolatile components of the polyisocyanate composition (X) and the isocyanate-reactive composition (Y), and is more preferably 10 to 300 parts by mass in order to improve adhesion and blocking resistance.

[0144] (Acid Anhydride) Examples of the acid anhydride include alicyclic acid anhydrides, aromatic acid anhydrides, unsaturated carboxylic acid anhydrides, etc., and can be used alone or in combination of two or more. More specifically, for example, maleic acid anhydride, phthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, benzophenonetetracarboxylic acid anhydride, dodecenylsuccinic acid anhydride, polyadipic acid anhydride, polyazelaic acid anhydride, polysebacic acid anhydride, poly(ethyloctadecanedioic acid) anhydride, poly(phenylhexadecanedioic acid) anhydride, tetrahydrophthalic acid anhydride, methyltetrahydrophthalic acid anhydride, methylhexahydrophthalic acid anhydride, hexahydrophthalic acid anhydride, methylhimic acid anhydride, trialkyltetrahydrophthalic acid anhydride, anhydride, methylcyclohexene dicarboxylic acid anhydride, methylcyclohexene tetracarboxylic acid anhydride, ethylene glycol bistrimellitate dianhydride, HET acid anhydride, Nadic acid anhydride, methylnadic acid anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexane-1,2-dicarboxylic acid anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride, and the like.

[0145] The acid anhydride may be any of the above compounds modified with glycol. Examples of glycols that can be used for modification include alkylene glycols such as ethylene glycol, propylene glycol, and neopentyl glycol; and polyether glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. Furthermore, copolymer polyether glycols of two or more of these glycols and / or polyether glycols may also be used.

[0146] Alternatively, among the compounds mentioned above as acid anhydrides, a homopolymer or copolymer of a compound having a polymerizable unsaturated group, such as maleic anhydride, may be used. Examples of compounds copolymerizable with a compound having an acid anhydride group and a polymerizable unsaturated group include α-olefins such as ethylene, propylene, 1,3-butadiene, and cyclopentylethylene; vinyl compounds having an aromatic ring, such as styrene, 1-ethynyl-4-methylbenzene, divinylbenzene, 1-ethynyl-4-methylethylbenzene, benzonitrile, acrylonitrile, p-tert-butylstyrene, 4-vinylbiphenyl, 4-ethynylbenzyl alcohol, 2-ethynylnaphthalene, and phenanthrene-9-ethynyl; and fluoroolefins such as vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, and chlorotrifluoroethylene. These compounds may be used alone or in combination of two or more. It is preferable to use styrene and p-tert-butylstyrene, which are vinyl compounds having an aromatic ring.

[0147] (Other Components) The adhesive may contain a phosphoric acid derivative (C) and a plasticizer (D). These may be the same as those exemplified above as components of the polyisocyanate composition (X).

[0148] (Form of Adhesive) The two-component curing adhesive of the present invention may be either a solvent-based or solventless type. In this specification, a "solvent-based" adhesive refers to a form used in a so-called dry lamination method, in which the adhesive is applied to a substrate, heated in an oven or the like to volatilize the organic solvent in the coating, and then bonded to another substrate. Either or both of the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) contain an organic solvent capable of dissolving (diluting) the components of the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) used in the present invention.

[0149] Examples of organic solvents include esters such as ethyl acetate, butyl acetate, cellosolve acetate, etc., ketones such as acetone, methyl ethyl ketone, isobutyl ketone, cyclohexanone, etc., ethers such as tetrahydrofuran, dioxane, etc., aromatic hydrocarbons such as toluene, xylene, etc., halogenated hydrocarbons such as methylene chloride, ethylene chloride, etc., dimethyl sulfoxide, dimethyl sulfamide, etc. The organic solvent used as a reaction medium during production of the components of the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) may also be used as a diluent during coating.

[0150] In this specification, a "solventless" adhesive refers to a form of adhesive in which the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) are substantially free of esters such as ethyl acetate, butyl acetate, cellosolve acetate, etc.; ketones such as acetone, methyl ethyl ketone, isobutyl ketone, cyclohexanone, etc.; ethers such as tetrahydrofuran, dioxane, etc.; aromatic hydrocarbons such as toluene, xylene, etc.; halogenated hydrocarbons such as methylene chloride, ethylene chloride, etc.; highly soluble organic solvents such as dimethyl sulfoxide, dimethyl sulfamide, in particular ethyl acetate or methyl ethyl ketone; and which is used in a method in which the adhesive is applied to a substrate and then bonded to another substrate without going through a step of heating in an oven or the like to volatilize the solvent, i.e., a so-called non-solvent lamination method. If the organic solvent used as a reaction medium during the production of the components of polyisocyanate composition (X) or isocyanate-reactive composition (Y) or the raw materials thereof cannot be completely removed, and trace amounts of organic solvent remain in polyisocyanate composition (X) or isocyanate-reactive composition (Y), it is considered to be substantially free of organic solvent. Furthermore, if isocyanate-reactive composition (Y) contains a low-molecular-weight alcohol, the low-molecular-weight alcohol reacts with polyisocyanate composition (X) to become part of the coating film, and therefore does not need to be volatilized after coating. Therefore, such a form is also treated as a solventless adhesive, and the low-molecular-weight alcohol is not considered an organic solvent.

[0151] The two-component curing adhesive of the present invention is preferably used by blending the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) so that the ratio [NCO] / [isocyanate-reactive functional group] of the number of moles of isocyanate groups [NCO] to the number of moles of functional groups reactive with isocyanate [isocyanate-reactive functional group] is 0.5 to 5.0, more preferably 1.0 to 3.0. This allows for appropriate curing properties to be obtained without depending on the environmental humidity at the time of application.

[0152] <Laminate> The laminate of the present invention can be obtained, for example, by mixing the polyisocyanate composition (X) of the present invention with the isocyanate-reactive composition (Y) to prepare a coating agent, which is then applied to a substrate and cured. Alternatively, the laminate can be obtained by a two-liquid mixing process in which the polyisocyanate composition (X) of the present invention and the isocyanate-reactive composition (Y) are mixed in advance to prepare an adhesive, which is then applied to a first substrate, and then a second substrate is laminated on the coated surface and cured to form an adhesive layer; or by a two-liquid separate coating process in which the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) are separately applied to a first substrate and a second substrate, and then the coated surfaces of the first substrate and the second substrate are brought into contact and pressed together to laminate the first substrate and the second substrate, and the adhesive layer is cured to form an adhesive layer. There are no particular restrictions on the substrate used, and it can be selected appropriately depending on the application.

[0153] Examples of films for food packaging include polyethylene terephthalate (PET) films, polystyrene films, polyamide films, polyacrylonitrile films, polyethylene films (LLDPE: low-density polyethylene film, HDPE: high-density polyethylene film, MDOPE: uniaxially oriented polyethylene film, BOPE: biaxially oriented polyethylene film), polypropylene films (CPP: unoriented polypropylene film, OPP: biaxially oriented polypropylene film), polyolefin films such as gas-barrier heat-sealable films in which an olefin-based heat-sealable resin layer is provided on one or both sides of a resin having gas-barrier properties such as an ethylene-vinyl alcohol copolymer or polyvinyl alcohol, polyvinyl alcohol film, and ethylene-vinyl alcohol copolymer film.

[0154] It is also preferable to use biomass films, biodegradable films, and recycled plastic films formed from materials containing biomass-derived components, biodegradable components, or recycled components. Biomass films, biodegradable films, and recycled plastic films are sold by various companies, and films certified in various countries can also be used, such as film sheets listed in the list of biomass-certified products listed by the Japan Organics Recycling Association, films listed in the list of Eco Mark-certified products listed by the Japan Environment Association, and films bearing the symbol mark designated by the Japan Bioplastics Association.

[0155] (Biomass Film) Specific examples of well-known biomass films include those made from biomass-derived ethylene glycol. Biomass-derived ethylene glycol is made from ethanol (biomass ethanol) produced from biomass as a raw material. For example, biomass-derived ethylene glycol can be obtained by converting biomass ethanol into ethylene oxide by a conventionally known method to produce ethylene glycol. Alternatively, commercially available biomass ethylene glycol may be used; for example, biomass ethylene glycol commercially available from India Glycoal Limited can be suitably used.

[0156] For example, as an alternative to conventional polyethylene terephthalate films made from petroleum-based raw materials, films containing biomass polyesters and biomass polyethylene terephthalates, which have biomass-derived ethylene glycol as the diol unit and fossil fuel-derived dicarboxylic acids as the dicarboxylic acid units, are known.

[0157] The dicarboxylic acid units of the biomass polyester use dicarboxylic acids derived from fossil fuels. Aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and their derivatives can be used without limitation as dicarboxylic acids. Furthermore, the biomass polyester may be a copolymer polyester containing, in addition to the diol and dicarboxylic acid components, a bifunctional oxycarboxylic acid or a third copolymer component, such as at least one polyfunctional compound selected from the group consisting of a trifunctional or higher polyhydric alcohol, a trifunctional or higher polycarboxylic acid and / or its anhydride, and a trifunctional or higher oxycarboxylic acid, to form a crosslinked structure.

[0158] Also, for example, as an alternative to conventional polyolefin films using petroleum-based raw materials, biomass polyolefin films such as biomass polyethylene films and biomass polyethylene-polypropylene films containing polyethylene resins made from biomass-derived ethylene glycol are known. The polyethylene resin is not particularly limited except that the biomass-derived ethylene glycol is used as part of the raw material, and examples include ethylene homopolymers and copolymers of ethylene and α-olefins containing ethylene as the main component (ethylene-α-olefin copolymers containing 90% by mass or more of ethylene units), and these can be used alone or in combination of two or more.

[0159] The α-olefin constituting the copolymer of ethylene and α-olefin is not particularly limited, and examples thereof include α-olefins having 4 to 8 carbon atoms, such as 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene. Known polyethylene resins such as low-density polyethylene resin, medium-density polyethylene resin, and linear low-density polyethylene resin can be used. Among these, linear low-density polyethylene resin (LLDPE) (a copolymer of ethylene and 1-hexene, or a copolymer of ethylene and 1-octene) is preferred from the viewpoint of further reducing the risk of damage such as holes and tears even when films are rubbed against each other, and has a density of 0.910 to 0.925 g / cm. ３ More preferred is a linear low density polyethylene resin in which

[0160] Biomass films made from biomass raw materials classified by the biomass plastic content specified in ISO 16620 or ASTM D6866 are also on the market. Radioactive carbon-14C exists in the atmosphere at a rate of 1 in 10 particles, and this rate is the same for atmospheric carbon dioxide, so this rate remains the same even in plants that fix carbon dioxide through photosynthesis. Therefore, the carbon in plant-derived resins contains radioactive carbon-14C. In contrast, the carbon in fossil fuel-derived resins contains almost no radioactive carbon-14C. Therefore, by measuring the concentration of radioactive carbon-14C in the resin using an accelerator mass spectrometer, the plant-derived resin content in the resin, i.e., the biomass plastic content, can be determined.

[0161] Examples of plant-derived low-density polyethylene, which is a biomass plastic having a biomass plastic content of 80% or more, preferably 90% or more as specified by ISO 16620 or ASTM D6866, include products manufactured by Braskem under the trade names "SBC818," "SPB608," "SBF0323HC," "STN7006," "SEB853," and "SPB681," and films using these as raw materials can be suitably used.

[0162] Films and sheets containing starch, a biomass material, or polylactic acid are also known. These can be selected and used appropriately depending on the application.

[0163] The biomass film may be a laminate of multiple biomass films or a laminate of a conventional petroleum-based film and a biomass film. These biomass films may be unstretched or stretched, and their manufacturing method is not limited.

[0164] (Biodegradable Films) Specific examples of well-known biodegradable films include those made from commonly available biodegradable resins. Examples include polycaprolactone, polyvinyl alcohol, polyamide, cellulose ester, lactic acid-based polyester resins, aliphatic polyester resins, and aliphatic aromatic polyester resins. These biodegradable resins may be used alone or in combination. Among these, aliphatic polyester resins or aliphatic aromatic polyester resins are preferred. Examples of aliphatic polyester resins include aliphatic polyesters obtained by polycondensation of an aliphatic diol and an aliphatic dicarboxylic acid. 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-cyclohexanedimethanol. These may be used alone or in mixtures. Of these, 1,4-butanediol is preferred. Examples of aliphatic dicarboxylic acids include oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, suberic acid, and dodecanedioic acid, and acid anhydrides derived from these may also be used. Among these, succinic acid or succinic anhydride, or a mixture of these with adipic acid, is preferred. Specific examples include polybutylene succinate (PBS) obtained from 1,4-butanediol and succinic acid (e.g., BioPBS manufactured by PPT MCC Biochem), and polybutylene succinate adipate (PBSA) obtained by copolymerizing PBS with adipic acid.

[0165] Aliphatic aromatic polyester resins include copolymers containing aliphatic dicarboxylic acid units, aromatic dicarboxylic acid units, and linear aliphatic and / or alicyclic diol units. The diol component that provides the diol units typically has 2 to 10 carbon atoms, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,4-cyclohexanedimethanol. Among these, diols with 2 to 4 carbon atoms are preferred, with ethylene glycol and 1,4-butanediol being preferred, and 1,4-butanediol being even more preferred. The dicarboxylic acid component that provides the dicarboxylic acid units typically has 2 to 10 carbon atoms, such as succinic acid, adipic acid, suberic acid, sebacic acid, and dodecanedioic acid. Of these, succinic acid or adipic acid is preferred. Examples of aromatic dicarboxylic acid components that provide aromatic dicarboxylic acid units include terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid. Among these, terephthalic acid and isophthalic acid are preferred, and terephthalic acid is more preferred.Specific examples include PBAT, which is a copolymer of 1,4-butanediol, adipic acid, and terephthalic acid (for example, Ecoflex manufactured by BASF Co., Ltd.).

[0166] Other examples include poly(3-hydroxyalkanoates) which are aliphatic polyester copolymers obtained from hydroxyalkanoic acids and polycarboxylic acids (particularly, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) (e.g., Aonilex manufactured by Kaneka Corporation), and polylactic acid (PLA) (e.g., REVODE manufactured by Kaisei Biomaterials Co., Ltd., and Ingeo manufactured by NatureWorks).

[0167] The biodegradable film may be a laminate of multiple biodegradable films or a laminate of a conventional petroleum-based film and a biodegradable film. These biodegradable films may be unstretched or stretched, and there are no limitations on the manufacturing method.

[0168] The film may be one that has been subjected to a stretching treatment. A typical stretching method involves melt-extruding a resin into a sheet using an extrusion film-forming method or the like, followed by simultaneous biaxial stretching or sequential biaxial stretching. In the case of sequential biaxial stretching, it is common to first perform longitudinal stretching and then transverse stretching. Specifically, a method that combines longitudinal stretching utilizing the speed difference between rolls and transverse stretching using a tenter is often used.

[0169] The film surface may be subjected to various surface treatments such as flame treatment and corona discharge treatment as necessary so that an adhesive layer without defects such as film breakage or repellency is formed.

[0170] Alternatively, a film laminated with a vapor-deposited layer of a metal such as aluminum or a metal oxide such as silica or alumina, or a barrier film containing a gas barrier layer of polyvinyl alcohol, an ethylene-vinyl alcohol copolymer, vinylidene chloride, etc. Use of such a film can provide a laminate with barrier properties against water vapor, oxygen, alcohol, inert gases, volatile organic compounds (fragrances), etc.

[0171] The paper can be made from any known paper base material without any particular limitations. Specifically, it is produced using natural fibers for papermaking, such as wood pulp, on a known papermaking machine, but the papermaking conditions are not particularly specified. Examples of natural fibers for papermaking include wood pulp, such as softwood pulp and hardwood pulp; non-wood pulp, such as Manila hemp pulp, sisal hemp pulp, and flax pulp; and pulp obtained by chemically modifying these pulps. Examples of pulp that can be used include chemical pulp produced by sulfate cooking, acidic, neutral, or alkaline sulfite cooking, soda cooking, ground pulp, chemi-ground pulp, and thermomechanical pulp. Various commercially available fine paper, coated paper, lined paper, impregnated paper, cardboard, and paperboard can also be used.

[0172] More specific examples of the structure of a laminate produced using the coating agent of the present invention include, but are not limited to, (1) coating layer / substrate; (2) coating layer / metal-deposited unstretched film; (3) coating layer / metal-deposited stretched film; (4) coating layer / transparent-deposited stretched film; (5) substrate / coating layer / metal-deposited layer; and (6) substrate / coating layer / transparent-deposited layer.

[0173] Examples of substrates used in configuration (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 surface of the substrate facing the coating layer or the surface of the substrate opposite the coating layer) or on the coating layer (the surface of the coating layer opposite the substrate). The printing layer is formed using various printing inks such as gravure ink, flexographic ink, offset ink, stencil ink, and inkjet ink by a general printing method that has traditionally been used for printing on polymer films and paper.

[0174] Examples of metal-vapor-deposited unstretched films used in structure (2) include CPP films, LLDPE films, and VM-CPP films and VM-LLDPE films, which are gas-barrier heat-sealable films vapor-deposited with a metal such as aluminum. Examples of metal-vapor-deposited stretched films used in structure (3) include VM-MDOPE films, VM-BOPE films, VM-OPP films, and VM-PET films, which are MDOPE films, BOPE films, OPP films, and PET films vapor-deposited with a metal such as aluminum. Examples of transparent vapor-deposited stretched films used in structure (4) include MDOPE films, BOPE films, OPP films, PET films, nylon films, and the like vapor-deposited with silica or alumina. As with structure (1), a printed layer may be provided at any position.

[0175] Examples of the substrate used in the structures (5) and (6) include an MDOPE film, a BOPE film, an OPP film, a PET film, a CPP film, an LLDPE film, a gas barrier heat seal film, paper, etc. The metal vapor deposition layer is a vapor deposition layer of a metal such as aluminum.

[0176] 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), and (E1-3)), a laminate with even better gas barrier properties can be obtained by providing a coating layer of the coating agent of the present invention on a metal vapor-deposited layer or a transparent vapor-deposited layer as in structures (2) to (4).

[0177] Specific examples of laminate structures produced using the adhesive of the present invention include, but are not limited to, the following: (1) substrate 1 / adhesive layer 1 / sealant film (2) substrate 1 / adhesive layer 1 / metal-deposited unstretched film (3) substrate 1 / adhesive layer 1 / metal-deposited stretched film (4) transparent vapor-deposited stretched film / adhesive layer 1 / sealant film (5) substrate 1 / adhesive layer 1 / substrate 2 / adhesive layer 2 / sealant film (6) substrate 1 / adhesive layer 1 / metal-deposited stretched film / adhesive layer 2 / sealant film (7) substrate 1 / adhesive layer 1 / transparent vapor-deposited stretched film / adhesive layer 2 / sealant film (8) substrate 1 / adhesive layer 1 / metal layer / adhesive layer 2 / sealant film (9) substrate 1 / adhesive layer 1 / substrate 2 / adhesive layer 2 / metal layer / adhesive layer 3 / sealant film (10) substrate 1 / adhesive layer 1 / metal layer / adhesive layer 2 / substrate 2 / adhesive layer 3 / sealant film

[0178] Examples of the substrate 1 used in structure (1) include MDOPE film, BOPE film, OPP film, PET film, nylon film, and paper. The substrate 1 may also be coated to improve gas barrier properties or ink receptivity when a printing layer (described later) is provided. Commercially available coated substrate films 1 include K-OPP film, K-PET film, and K-nylon film. The adhesive layer 1 is a cured coating of the adhesive of the present invention. Examples of sealant films include CPP film, LLDPE film, easy-open heat seal film, and gas barrier heat seal film. A printing layer may be provided on the surface of the substrate 1 facing the adhesive layer 1 (when a coated substrate film 1 is used, the surface of the coating layer facing the adhesive layer 1) or on the surface opposite the adhesive layer 1. The printing layer is formed using various printing inks, such as gravure ink, flexographic ink, offset ink, stencil ink, and inkjet ink, using a common printing method conventionally used for printing on polymer films and paper.

[0179] Examples of the substrate 1 used in structures (2) and (3) include an MDOPE film, a BOPE film, an OPP film, a PET film, and paper. The adhesive layer 1 is a cured coating of the adhesive of the present invention. Examples of metal-vapor-deposited unstretched films include a CPP film, an LLDPE film, and a VM-CPP film or a VM-LLDPE film, which is a gas-barrier heat-seal film that has been subjected to metal vapor deposition with aluminum or the like. Examples of metal-vapor-deposited stretched films include a VM-MDOPE film, a VM-BOPE film, or a VM-OPP film, which is a MDOPE film, a BOPE film, or an OPP film that has been subjected to metal vapor deposition with aluminum or the like. As with structure (1), a printed layer may be provided on either side of the substrate 1.

[0180] Examples of transparent vapor-deposited stretched films used in structure (4) include films obtained by vapor-depositing silica or alumina onto MDOPE film, BOPE film, OPP film, PET film, nylon film, etc. A film with a coating applied to the vapor-deposited inorganic layer of silica or alumina may also be used for the purpose of protecting the vapor-deposited inorganic layer. The adhesive layer 1 is a cured coating of the adhesive of the present invention. Examples of sealant films include those similar to those in structure (1). A printed layer may be provided on the surface of the transparent vapor-deposited stretched film facing the adhesive layer 1 (when a film with a coating applied to the inorganic vapor-deposited layer is used, the surface of the coating layer facing the adhesive layer 1). The method of forming the printed layer is the same as in structure (1).

[0181] Examples of the substrate 1 used in structure (5) include PET film and paper. Examples of the substrate 2 include nylon film. At least one of the adhesive layer 1 and the adhesive layer 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those in structure (1). As in structure (1), a printed layer may be provided on either side of the substrate 1.

[0182] Examples of the substrate 1 in structure (6) include those similar to those in structures (2) and (3). Examples of metal-vapor-deposited stretched films include VM-MDOPE films, VM-BOPE films, VM-OPP films, and VM-PET films, which are MDOPE films, BOPE films, OPP films, and PET films that have been subjected to metal vapor deposition of aluminum or the like. At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those in structure (1). As in structure (1), a printed layer may be provided on either side of the substrate 1.

[0183] Examples of the substrate 1 in structure (7) include PET film, paper, etc. Examples of the transparent vapor-deposited stretched film include those similar to those in structure (4). At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those in structure (1). As in structure (1), a printed layer may be provided on either side of the substrate 1.

[0184] Examples of the substrate 1 in structure (8) include PET film and paper. Examples of the metal layer include aluminum foil. At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those in structure (1). As in structure (1), a printed layer may be provided on either side of the substrate 1.

[0185] Examples of the substrate 1 in structures (9) and (10) include PET film, paper, etc. Examples of the substrate 2 include nylon film, etc. Examples of the metal layer include aluminum foil, etc. At least one layer of the adhesive layers 1, 2, and 3 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those in structure (1). As in structure (1), a printed layer may be provided on either side of the substrate 1.

[0186] When the adhesive of the present invention is a gas barrier adhesive (when the isocyanate-reactive composition (Y) contains at least one selected from polyester polyols (E1-1), (E1-2), and (E1-3)), using the adhesive of the present invention in the production of a laminate containing a metal vapor deposition layer or a transparent vapor deposition layer as in structures (2) to (4), (6), and (7) can result in a laminate with even better gas barrier properties. In this case, it is preferable to form the adhesive layer in contact with the metal vapor deposition layer or the transparent vapor deposition layer using the adhesive of the present invention.

[0187] The laminate of the present invention may further include other films or substrates in addition to the above-described configurations (1) to (10). As the other substrates, in addition to the above-described stretched films, unstretched films, and transparent vapor-deposited films, porous substrates such as paper, wood, and leather, which will be described later, can also be used. The adhesive used to bond the other substrates may or may not be the adhesive of the present invention.

[0188] The "other layer" may contain known additives or stabilizers, such as antistatic agents, adhesion-enhancing coating agents, plasticizers, lubricants, antioxidants, etc. Furthermore, the "other layer" may be a film whose surface has been pretreated with corona treatment, plasma treatment, ozone treatment, chemical treatment, solvent treatment, or the like in order to improve adhesion when laminated with other materials.

[0189] The laminate of the present invention can be suitably used for a variety of applications, such as packaging materials for food, medicines, and daily necessities; lid materials; paper tableware such as paper straws, paper napkins, paper spoons, paper plates, and paper cups; barrier materials; roofing materials; solar cell 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 simultaneous injection molding decoration methods; and packaging materials for liquid laundry detergents, liquid kitchen detergents, liquid bath detergents, liquid bath soaps, liquid shampoos, liquid conditioners, and the like.

[0190] <Packaging Material> The laminate of the present invention can be used as a multilayer packaging material for protecting foods, medicines, etc. When used as a multilayer packaging material, the layer structure can be changed depending on the contents, the environment of use, and the form of use. In addition, the packaging of the present invention may be appropriately provided with an easy-open treatment or a resealable means.

[0191] A specific example of the packaging material of the present invention is a packaging material obtained by forming a bag from a laminate having a sealant film, such as the laminate configuration examples (1), (4), and (10) described above. The laminate is folded or overlapped so that the inner layer surfaces (the surfaces of the sealant film) face each other, and the peripheral edges are heat-sealed to form a bag. Examples of bag-making methods include heat-sealing methods using a side seal, two-sided seal, three-sided seal, four-sided seal, envelope seal, flared seal, flat-bottom seal, square-bottom seal, gusset seal, or other heat seal types. The packaging material of the present invention can take various forms depending on the contents, usage environment, and usage pattern. Self-standing packaging materials (standing pouches) are also possible. Examples of heat-sealing methods include known methods such as bar seal, rotary roll seal, belt seal, impulse seal, high-frequency seal, and ultrasonic seal.

[0192] The packaging material of the present invention is filled with contents through its opening, and then the opening is heat-sealed to produce a product using the packaging material of the present invention. Examples of contents to be filled include foods such as rice crackers, bean snacks, nuts, biscuits, cookies, wafer snacks, marshmallows, pies, semi-dried cakes, candies, and snacks; staple foods such as bread, snack noodles, instant noodles, dried noodles, pasta, aseptically packaged cooked rice, porridge, rice porridge, packaged rice cakes, and cereal foods; processed agricultural products such as pickles, boiled beans, natto, miso, frozen tofu, tofu, nametake mushrooms, konjac, processed wild vegetables, jams, peanut cream, salads, frozen vegetables, and processed potatoes; processed livestock products such as ham, bacon, sausages, processed chicken, and corned beef; and processed fish ham and meat products. Examples of such foods include processed seafood products such as sausages, fish paste products, kamaboko, nori seaweed, tsukudani (simmered foods in soy sauce), bonito flakes, salted fish, smoked salmon, and spicy mentaiko; fruit pulp such as peaches, mandarin oranges, pineapples, apples, pears, and cherries; vegetables such as corn, asparagus, mushrooms, onions, carrots, radishes, and potatoes; cooked foods such as frozen and chilled prepared dishes, including hamburgers, meatballs, fried seafood, gyoza, and croquettes; dairy products such as butter, margarine, cheese, cream, instant creamy powder, and infant formula; liquid seasonings, retort curry, and pet food.

[0193] In addition, the present invention can also be used as a packaging material for various non-food products, such as cigarettes, disposable body warmers, medicines such as infusion packs, liquid laundry detergent, liquid kitchen detergent, liquid bath detergent, liquid bath soap, liquid shampoo, liquid conditioner, cosmetics such as lotion and emulsion, vacuum insulation materials, batteries, etc.

[0194] The present invention will be described in more detail below with reference to specific synthesis examples and examples, but the present invention is not limited to these examples. In the following examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively, unless otherwise specified.

[0195] <Preparation of Polyisocyanate Composition (X)> (Polyisocyanate Composition (X-1)) 826.8 parts of toluene diisocyanate (TDI) was added to a reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, and condenser, and the mixture was heated to 40°C while stirring under a nitrogen gas stream. Subsequently, 173.2 parts of 2,2,4-trimethyl-1,3-pentanediol was added, taking care to avoid heat generation, and the mixture was then heated to 60°C. The reaction was continued at 60°C until the NCO% no longer changed, and 0.2 parts of butyl acid phosphate was added to terminate the reaction. Next, using a thin-film distillation apparatus, the mixture was purified at a pressure of approximately 0.02 Torr and a temperature of 160°C until the TDI in the urethane prepolymer, the reaction product of TDI, was reduced to 0.05% by mass of the solids, thereby obtaining polyisocyanate composition (X-1). The NCO% of polyisocyanate composition (X-1) was 16.3%.

[0196] (Polyisocyanate Composition (X-2)) 822.7 parts of toluene diisocyanate (TDI) was added to a reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, and condenser, and the mixture was heated to 40°C while stirring under a nitrogen gas stream. Subsequently, 177.3 parts of triethylene glycol was added, taking care not to generate heat, and the mixture was then heated to 60°C. The reaction was continued at 60°C until the NCO% no longer changed, and 0.2 parts of butyl acid phosphate was added to terminate the reaction. Next, using a thin-film distillation apparatus, the mixture was purified at a pressure of approximately 0.02 Torr and a temperature of 160°C until the TDI in the urethane prepolymer, the reaction product of TDI, was reduced to 0.05% by mass of the solids, thereby obtaining polyisocyanate composition (X-2). The NCO% of polyisocyanate composition (X-2) was 16.4%.

[0197] (Polyisocyanate Composition (X-3)) 867.9 parts of toluene diisocyanate (TDI) was added to a reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, and condenser, and the mixture was heated to 40°C while stirring under a nitrogen gas stream. Subsequently, 132.1 parts of diethylene glycol was added while taking care not to generate heat, and the mixture was then heated to 60°C. The reaction was continued at 60°C until the NCO% no longer changed, and 0.2 parts of butyl acid phosphate was added to terminate the reaction. Next, using a thin-film distillation apparatus, the mixture was purified at a pressure of approximately 0.02 Torr and a temperature of 160°C until the TDI in the urethane prepolymer, the reaction product of TDI, was reduced to 0.05% by mass of the solids, thereby obtaining polyisocyanate composition (X-3). The NCO% of polyisocyanate composition (X-3) was 17.8%.

[0198] (Polyisocyanate Composition (X-4)) 774.5 parts of toluene diisocyanate (TDI) was added to a reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, and condenser, and the mixture was heated to 40°C while stirring under a nitrogen gas stream. Subsequently, 225.5 parts of bifunctional polyethylene glycol having a molecular weight of 200 was added while taking care not to generate heat, and the mixture was then heated to 60°C. The reaction was continued at 60°C until the NCO% no longer changed, and 1.0 part of polyphosphoric acid was added to terminate the reaction. Next, using a thin-film distillation apparatus, the mixture was purified at a pressure of approximately 0.02 Torr and a temperature of 160°C until the TDI in the urethane prepolymer, the reaction product of TDI, was reduced to 0.05% by mass of the solids, thereby obtaining polyisocyanate composition (X-4). The NCO% of polyisocyanate composition (X-4) was 14.5%.

[0199] (Polyisocyanate Composition (X-5)) 774.5 parts of toluene diisocyanate (TDI) was added to a reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, and condenser, and the mixture was heated to 40°C while stirring under a nitrogen gas stream. Subsequently, 225.5 parts of bifunctional polyethylene glycol having a molecular weight of 200 was added while taking care not to generate heat, and the mixture was then heated to 60°C. The reaction was continued at 60°C until the NCO% no longer changed, and 0.5 parts of phosphoric acid was added to terminate the reaction. Next, using a thin-film distillation apparatus, the mixture was purified at a pressure of approximately 0.02 Torr and a temperature of 160°C until the TDI in the urethane prepolymer, the reaction product of TDI, was reduced to 0.05% by mass of the solids, thereby obtaining polyisocyanate composition (X-5). The NCO% of polyisocyanate composition (X-5) was 14.3%.

[0200] (Polyisocyanate Composition (X-6)) 699.0 parts of toluene diisocyanate (TDI) was added to a reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, and condenser, and the mixture was heated to 40°C while stirring under a nitrogen gas stream. Thereafter, 301.0 parts of bifunctional polyethylene glycol having a molecular weight of 300 was added while taking care not to generate heat, and the mixture was then heated to 60°C. The reaction was further continued at 60°C until the NCO% no longer changed, and 1.0 part of polyphosphoric acid was added to terminate the reaction. Next, using a thin-film distillation apparatus, the mixture was purified at a pressure of approximately 0.02 Torr and a temperature of 160°C until the TDI in the urethane prepolymer, the reaction product of TDI, was reduced to 0.05% by mass of the solids, thereby obtaining polyisocyanate composition (X-6). The NCO% of polyisocyanate composition (X-6) was 13.2%.

[0201] (Polyisocyanate Composition (X-7)) 774.5 parts of toluene diisocyanate (TDI) was added to a reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, and condenser, and the mixture was heated to 40°C while stirring under a nitrogen gas stream. Thereafter, 225.5 parts of bifunctional polyethylene glycol having a molecular weight of 200 was added while taking care not to generate heat, and the mixture was then heated to 60°C. The reaction was further continued at 60°C until the NCO% no longer changed, and 1.0 part of polyphosphoric acid was added to terminate the reaction. Next, using a thin-film distillation apparatus, the mixture was purified at a pressure of approximately 0.2 Torr and a temperature of 140°C until the TDI in the urethane prepolymer, the reaction product of TDI, was reduced to 5.0% by mass of the solids, thereby obtaining polyisocyanate composition (X-7). The NCO% of polyisocyanate composition (X-7) was 16.1%.

[0202] (Polyisocyanate Composition (X'-1)) 1,000.0 parts of toluene diisocyanate (TDI) was added to a reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, and condenser, and the mixture was heated to 60°C with stirring. 0.5 parts of a quaternary ammonium salt was added dropwise thereto, and when the predetermined refractive index was reached, a deactivator was added appropriately to terminate the reaction. Next, using a thin-film distillation apparatus, the mixture was purified at a pressure of approximately 0.02 Torr and a temperature of 160°C until the TDI in the nurate, the reaction product of TDI, was reduced to 0.05% by mass of the solids. This was dissolved and diluted with ethyl acetate to give a solution with a 50% by mass nonvolatile content, thereby obtaining polyisocyanate composition (X'-1). The NCO% of polyisocyanate composition (X'-1) was 7.9%.

[0203] (Polyisocyanate Composition (X'-2)) 918.2 parts of toluene diisocyanate (TDI) was added to a reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, and condenser, and the mixture was heated to 40°C while stirring under a nitrogen gas stream. 81.8 parts of ethylene glycol was then added, taking care to avoid heat generation, and the mixture was then heated to 60°C. The reaction was continued at 60°C until the NCO% no longer changed, and 0.2 parts of butyl acid phosphate was added to terminate the reaction. Next, using a thin-film distillation apparatus, the mixture was purified at a pressure of approximately 0.02 Torr and a temperature of 160°C until the TDI in the urethane prepolymer, the reaction product of TDI, was reduced to 0.05% by mass of the solids, thereby obtaining polyisocyanate composition (X'-2). The NCO% of polyisocyanate composition (X'-2) was 20.4%.

[0204] (Polyisocyanate Composition (X'-3)) 410.6 parts of toluene diisocyanate (TDI) was added to a reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, and condenser, and the mixture was heated to 40°C while stirring under a nitrogen gas stream. Subsequently, 589.4 parts of bifunctional polypropylene glycol having a molecular weight of 1,000 was added, taking care not to generate heat, and the mixture was then heated to 60°C. The reaction was continued at 60°C until the NCO% no longer changed, and 1.0 part of polyphosphoric acid was added to terminate the reaction. Next, using a thin-film distillation apparatus, the mixture was purified at a pressure of approximately 0.02 Torr and a temperature of 160°C until the TDI in the urethane prepolymer, the reaction product of TDI, was reduced to 0.05% by mass of the solids, thereby obtaining polyisocyanate composition (X'-3). The NCO% of polyisocyanate composition (X'-3) was 6.2%.

[0205] <Preparation of Isocyanate-Reactive Composition (Y)> (Isocyanate-Reactive Composition (Y-1)) 92.0 parts of ethylene glycol, 118.5 parts of phthalic anhydride, 29.2 parts of adipic acid, and 0.01 parts of titanium tetraisopropoxide were added to a polyester reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, a rectification tube, and the like, and an esterification reaction was carried out at an internal temperature of 220°C. After the dehydration reaction, a polyester polyol with an acid value of 1 mgKOH / g was obtained. 50.0 parts of triacetin was added to this to obtain an isocyanate-reactive composition (Y-1).

[0206] (Isocyanate-reactive composition (Y-2)) To a polyester reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, a rectifying tube, etc., 120.0 parts of diethylene glycol, 100.0 parts of 2-methyl-1,3-propanediol, 25.0 parts of trimethylolpropane, and 265.0 parts of adipic acid were added, and an esterification reaction was carried out at an internal temperature of 220° C. After the dehydration reaction, a polyol composition (Y-2) having an acid value of 1 mgKOH / g and a hydroxyl value of 165 mgKOH / g was obtained.

[0207] <Evaluation of Polyisocyanate Composition (X)> (Storage Stability of Polyisocyanate Composition (X)) A 15 mL glass bottle was filled with the polyisocyanate composition (X) and stored at room temperature for a certain period of time. The appearance of the composition was visually evaluated for cloudiness according to the following two-level criteria, and the results are summarized in Table 1. ○: No crystallization occurred for 7 days or more ×: Crystallization occurred within 7 days

[0208]

[0209] <Evaluation of adhesive> Adhesives of the examples and comparative examples were prepared by mixing the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) in the formulations shown in Table 2. The values ​​in the table are solid contents. Polyisocyanate composition (X'-2) crystallized, so it was not evaluated as an adhesive.

[0210] (Heat seal strength) A two-component curing adhesive (solid content 3 g / m) was prepared by blending a 15 μm biaxially oriented nylon film and a 60 μm linear low-density polyethylene film (LLDPE film) as a sealant film in the combination of Examples and Comparative Examples.２ ) and aging was carried out at 40°C for 48 hours to obtain a laminate.

[0211] The sealant film surfaces of the two laminates were placed together and sealed with a 1 cm wide seal bar at 180°C and 1 kgf / cm ２ - Heat sealing was performed for 1 second, and a test piece was cut out in a width of 15 mm to be used as a sample for measuring heat seal strength. Using a tensile tester at an ambient temperature of 25°C, the peeling speed was set to 300 mm / min, and both ends of the heat seal strength measurement sample were pulled and measured. The peak tensile strength was taken as the heat seal strength (N / 15 mm). Evaluation was made as follows: ◯: 50 N / 15 mm or more ×: Less than 50 N / 15 mm

[0212] (Lamination strength) A two-component curing adhesive (solid content 3 g / m) was prepared by blending a uniaxially oriented polyethylene film (MDOPE film) with a thickness of 25 μm and a linear low-density polyethylene film (LLDPE film) with a thickness of 60 μm in the combination of Examples and Comparative Examples. ２ ) and aging was carried out at 40°C for 72 hours to obtain a laminate.

[0213] Test pieces of 15 mm width were cut from the laminate, and the adhesive strength (N / 15 mm) was measured using a tensile tester at an ambient temperature of 25°C, a peel rate of 100 mm / min, and a T-peel test. The evaluation was as follows: ◯: 1.0 N / 15 mm or more ×: less than 1.0 N / 15 mm

[0214] (Oxygen permeability) A two-component curing adhesive (solid content 3 g / m) was prepared by blending a uniaxially oriented polyethylene film (MDOPE film) with a thickness of 25 μm and a linear low-density polyethylene film (LLDPE film) with a thickness of 60 μm in the combination of Examples and Comparative Examples. ２ ) and aging was carried out at 40°C for 72 hours to obtain a laminate.

[0215] The resulting laminate was cut into a size of 10 cm x 10 cm, and the oxygen permeability (cc / m) was measured in an atmosphere of 23°C and 50% RH using an OX-TRAN2 / 21 (oxygen permeability measuring device manufactured by Mocon Co., Ltd.) in accordance with JIS-K7126 (constant pressure method). ２The oxygen permeability of the MDOPE film used was 2810 cc / m ２ · day · atm, the oxygen permeability of LLDPE film is 1676 cc / m ２ The humidity was 300 cc / m. The RH stands for humidity. The evaluation was as follows: ２ ・Day・Less than atm 〇: 300cc / m ２ ・day・atm or more 600cc / m ２ Less than 600cc / m ２ ・day・atm or more 900cc / m ２ Less than day atm ×: 900cc / m ２ ・day・atm or more

[0216]

[0217]

Claims

1. A polyisocyanate composition (X) includes a polyisocyanate compound (A) having a plurality of isocyanate groups and a phosphoric acid derivative (C), wherein the polyisocyanate compound (A) includes a polyurethane polyisocyanate (A1) that is a product obtained by reacting toluene diisocyanate (a) with a diol (b) having a molecular weight of 65 or more and 300 or less in the absence of a catalyst.

2. The polyisocyanate compound (X) according to claim 1, wherein the phosphoric acid derivative (C) is at least one selected from phosphoric acid, pyrophosphoric acid, triphosphoric acid, methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, dibutyl phosphate, 2-ethylhexyl acid phosphate, bis(2-ethylhexyl) phosphate, isododecyl acid phosphate, butoxyethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, and polyoxyethylene alkyl ether phosphate.

3. The polyisocyanate composition (X) according to claim 1, wherein the diol (b) comprises a diol (b1) having an alkyl side chain having from 1 to 4 carbon atoms.

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

5. The polyisocyanate composition (X) according to claim 1, wherein the content of the polyurethane polyisocyanate (A1) in the polyisocyanate compound (A) is 20 mass% or more.

6. The polyisocyanate composition (X) according to claim 1, wherein the content of the isocyanate monomer in the polyisocyanate composition (X) is 1.0 mass% or less.

7. A two-component curing composition comprising the polyisocyanate composition (X) according to claim 1 and an isocyanate-reactive composition (Y).

8. The polyisocyanate composition (X) according to claim 1; and an isocyanate-reactive composition (Y) containing an isocyanate-reactive compound (E).

9. 9. The two-component curing coating agent according to claim 8, wherein the isocyanate-reactive compound (E) comprises at least one selected from the group consisting of 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).

10. The two-component curing coating agent according to claim 8, wherein the isocyanate-reactive compound (E) comprises at least one selected from the group consisting of a polyester polyol (E1-1) obtained by polycondensation of a polycarboxylic acid including an ortho-orienting polycarboxylic acid with a polyhydric alcohol, a polyester polyol (E1-2) having an isocyanuric ring, and a polyester polyol (E1-3) having a polymerizable carbon-carbon double bond.

11. A two-component curing coating agent according to claim 8, wherein the glass transition temperature (Tg) of the polyisocyanate-reactive compound (E) is 15°C or higher and 80°C or lower.

12. The polyisocyanate composition (X) according to claim 1; and an isocyanate-reactive composition (Y) containing an isocyanate-reactive compound (E).

13. 13. The two-component curing adhesive according to claim 12, wherein the isocyanate-reactive compound (E) comprises at least one selected from 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).

14. The two-component curing adhesive according to claim 12, wherein the isocyanate-reactive compound (E) comprises at least one selected from the group consisting of a polyester polyol (E1-1) obtained by polycondensation of a polycarboxylic acid including an ortho-orienting polycarboxylic acid with a polyhydric alcohol, a polyester polyol (E1-2) having an isocyanuric ring, and a polyester polyol (E1-3) having a polymerizable carbon-carbon double bond.

15. The two-component curing adhesive according to claim 12, wherein the glass transition temperature (Tg) of the polyisocyanate-reactive compound (E) is −50° C. or higher and 40° C. or lower.

16. A laminate comprising a substrate and a coating layer disposed on the substrate, the coating layer being a cured film of the two-component curing coating agent according to claim 8.

17. 13. 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 film of the two-component curing adhesive according to claim 12.

18. A packaging material comprising the laminate according to claim 16 or 17.