Polyisocyanate composition, two-component curable composition, two-component curable adhesive, laminate, packaging material

Abstract

The present invention provides: a polyisocyanate composition that is suitable for a two-part curable composition which requires adhesiveness with a metal base material; and an adhesive which, even when a plastic film and a base material having a metal foil such as aluminum foil or a metal vapor deposition layer of aluminum or the like are to be bonded together, suppresses a decrease in adhesiveness between the adhesive layer and the metal foil or metal vapor deposition film.　Provided is a polyisocyanate composition comprising a polyurethane polyisocyanate (A1) and an isocyanate compound (A2) which is a reaction product of an aliphatic hydroxycarboxylic acid and a diisocyanate. Also provided is a two-part curable adhesive using the polyisocyanate composition.

Description

Technical Field

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

Background Art

[0002] Laminates used for various packaging materials, labels, etc. are provided with designability, functionality, storage stability, convenience, transport resistance, etc. by laminating various substrates such as various plastic films, metal foils, and papers. Packaging materials formed by molding the laminate into a bag shape are used as packaging materials in various fields including foods, pharmaceuticals, detergents, and the like.

[0003] Conventionally, for laminate films, a two-component curable adhesive in which a polyisocyanate compound and a polyol compound are dissolved in a volatile organic solvent is applied to the film, the organic solvent is volatilized in the process of passing through an oven, and another film is laminated. The dry lamination method is the mainstream. In recent years, from the viewpoints of reducing the environmental load and improving the working environment, a two-component curable solventless adhesive in which a polyisocyanate compound and a polyol compound do not contain a volatile organic solvent has attracted attention (Patent Document 1, Patent Document 2).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] When bonding a metal foil such as aluminum foil or a substrate having a metal vapor deposition layer such as aluminum to a plastic film using such a two-component curable adhesive, the adhesion between the adhesive layer and the metal foil or metal vapor deposition film may decrease over time.

[0006] The present invention has been made in view of such circumstances, and an object thereof is to provide an adhesive in which a decrease in adhesion between an adhesive layer and a metal foil or a metal vapor deposition film is suppressed even when bonding a metal foil such as aluminum foil or a substrate having a metal vapor deposition layer such as aluminum to a plastic film. Another object of the present invention is to provide a polyisocyanate composition suitable for a two-component curable composition that requires adhesion to a metal substrate.

Means for Solving the Problems

[0007] That is, the present invention relates to a polyisocyanate composition containing a polyurethane polyisocyanate (A1) and an isocyanate compound (A2) which is a reaction product of an aliphatic hydroxycarboxylic acid and a diisocyanate, and a two-component curable adhesive using the same.

Effects of the Invention

[0008] According to the present invention, even when bonding a metal foil such as aluminum foil or a substrate having a metal vapor deposition layer such as aluminum to a plastic film, it is possible to provide an adhesive in which a decrease in adhesion between the adhesive layer and the metal foil or metal vapor deposition film is suppressed. Moreover, it is possible to provide a polyisocyanate composition suitable for a two-component curable composition that requires adhesion to a metal substrate.

Modes for Carrying Out the Invention

[0009] <Polyisocyanate Composition> The polyisocyanate composition of the present invention contains a polyurethane polyisocyanate (A1) which is a reaction product of a diisocyanate monomer and a polyol, and an isocyanate compound (A2) which is a reaction product of an aliphatic hydroxycarboxylic acid and a diisocyanate monomer.

[0010] (Polyurethane polyisocyanate (A1)) As the diisocyanate monomer used for the synthesis of the polyurethane polyisocyanate (A1), known aromatic, araliphatic, aliphatic, and alicyclic diisocyanates can be used alone or in combination of two or more.

[0011] Examples of the aromatic diisocyanate include, but are not limited to, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (alias: MDI), polymethylene polyphenyl polyisocyanate (also referred to as polymeric MDI or crude MDI), 1,3-phenylene diisocyanate, 4,4'-diphenyldiisocyanate, 1,4-phenylene diisocyanate (alias: PPDI), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate (alias: TDI), 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, tolidine diisocyanate (alias: TODI), dianisidine diisocyanate, naphthalene diisocyanate (alias: NDI), 4,4'-diphenyl ether diisocyanate, 4,4',4''-triphenylmethane triisocyanate, etc.

[0012] 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 (alias: XDI), α,α,α',α'-tetramethylxylylene diisocyanate (alias: TMXDI), etc.

[0013] Examples of aliphatic diisocyanates include, but are not limited to, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate (also known as PDI), 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate (also known as LDI), etc.

[0014] Examples of alicyclic diisocyanates include, but are not limited to, 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, norbornane diisocyanate (also known as NBDI), etc.

[0015] Conventionally known polyols can be used as the polyol used in the synthesis of the polyurethane polyisocyanate (A1). For example, 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, 1,4-cyclohexanedimethanol;

[0016] Trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, pentaerythritol; Bisphenols such as bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F; Dimer diol; Polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, cyclohexylene in the presence of polymerization initiators such as glycols, trifunctional or tetrafunctional aliphatic alcohols;

[0017] Polyester polyol (1) which is a reaction product of a polyester obtained by ring-opening polymerization reaction of cyclic ester compounds such as propiolactone, butyrolactone, ε-caprolactone, σ-valerolactone, β-methyl-σ-valerolactone and a polyhydric alcohol such as the above-mentioned glycol, glycerin, trimethylolpropane, pentaerythritol; Polyester polyol (2) obtained by reacting a bifunctional polyol such as glycol, dimer diol, or bisphenol with a polyvalent carboxylic acid; Polyester polyol (3) obtained by reacting a trifunctional or tetrafunctional aliphatic alcohol with a polyvalent carboxylic acid; Polyester polyol (4) obtained by reacting a bifunctional polyol, a trifunctional or tetrafunctional aliphatic alcohol, and a polyvalent carboxylic acid; Polyester polyol (5) which is a polymer of a hydroxyl acid such as dimethylolpropionic acid, castor oil fatty acid;

[0018] Polyurethane polyol (1) obtained by polymerizing at least one selected from bifunctional polyols, trifunctional or tetrafunctional aliphatic alcohols with an isocyanate compound; Polyether urethane polyol (2) obtained by further polymerizing a polyether polyol with an isocyanate compound; Polyester polyol (3) obtained by polymerizing polyester polyols (1) to (5) with an isocyanate compound; Polyester polyether polyurethane polyol (4) obtained by reacting at least one of polyester polyols (1) to (5), a polyether polyol, and an isocyanate compound;

[0019] Examples include castor oil, dehydrated castor oil, castor hardened oil which is a hydrogenated product of castor oil, castor oil-based polyols such as 5 to 50 mol adducts of alkylene oxide to castor oil, and mixtures thereof, and one or more of these can be used in combination.

[0020] Examples of the polybasic carboxylic acids used in the synthesis of polyester polyols (2) to (4) include aromatic polybasic acids such as orthophthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride, naphthalic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid, benzophenonetetracarboxylic acid, benzophenonetetracarboxylic dianhydride, 5-sodium sulfoisophthalic acid, tetrachlorophthalic anhydride, and tetrabromophthalic anhydride; Methyl esterified products of aromatic polybasic acids such as dimethyl terephthalic acid and dimethyl 2,6-naphthalenedicarboxylate;

[0021] Aliphatic polybasic acids such as malonic acid, succinic acid, succinic anhydride, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, and dimer acid; Alkyl esterified products 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;

[0022] Aliphatic polybasic acids such as 1,1 - cyclopentanedicarboxylic acid, 1,2 - cyclopentanedicarboxylic acid, 1,3 - cyclopentanedicarboxylic acid, 1,2 - cyclohexanedicarboxylic acid, 1,3 - cyclohexanedicarboxylic acid, 1,4 - cyclohexanedicarboxylic acid, tetrahydrophthalic anhydride, 4 - methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, cyclohexane - 1,2,4 - tricarboxylic acid - 1,2 - anhydride, hymic anhydride, het acid, etc.; and the like can be mentioned, and one kind or a combination of two or more kinds can be used.

[0023] As the isocyanate compound used for the synthesis of polyurethane polyols (1) to (4), the same ones as those exemplified above can be used as the diisocyanate monomer used for the synthesis of polyurethane polyol (A1).

[0024] The polyol preferably contains a polyol having 3 or more functional groups. The blending amount of the polyol having 3 or more functional groups can be appropriately adjusted. As an example, it is preferably used at a ratio such that the average number of functional groups of the polyol used for the synthesis of polyurethane polyisocyanate (A1) is 2.1 or more and 3.5 or less, and more preferably 2.2 or more and 3.0 or less.

[0025] Polyurethane polyisocyanate (A1) is obtained by reacting a diisocyanate monomer and a polyol under conditions where the isocyanate groups contained in the diisocyanate monomer are in excess with respect to the active hydrogen groups contained in the polyol. The equivalent ratio [NCO] / [active hydrogen group] of the isocyanate groups to the active hydrogen groups can be appropriately adjusted. As an example, it is 2.0 or more and 20.0 or less.

[0026] The polyurethane polyisocyanate (A1) may contain unreacted diisocyanate monomer used in its synthesis, or the unreacted diisocyanate monomer may be removed by purification. When removing the unreacted diisocyanate monomer, the degree can be adjusted as appropriate. As an example, it is preferable to remove it until the content of the diisocyanate monomer becomes 0.1% by mass or less of the polyisocyanate composition.

[0027] From the perspective of occupational safety and health, there is a movement to regulate the use of isocyanate monomers. The European Commission has adopted the REACH regulation that prohibits the marketing of products containing 0.1% by mass or more of isocyanate monomers if certain requirements are not met. If the unreacted diisocyanate monomer is removed until the amount of diisocyanate monomer in the polyisocyanate composition becomes 0.1% by mass or less, a product that complies with such regulations can be obtained.

[0028] Also, when manufacturing a laminate for food packaging using a two-component curable adhesive containing an aromatic isocyanate prepolymer, unreacted aromatic isocyanate monomer may remain in the adhesive layer. The isocyanate monomer reacts with water present in the surroundings to become a primary aromatic amine (PAA), and there is a risk of migrating into the film and eluting into the contents (food). PAA is a concern for its harmfulness to the human body, and various regulations have been established, such as the European Commission setting its detection limit in the regulations regarding plastic materials and products for food contact.

[0029] Since PAA reacts with unreacted aromatic isocyanate present in the surroundings, even when aromatic isocyanate remains in the adhesive layer, the concentration of PAA gradually decreases. Eventually, it falls below the detection limit, but from the perspective of the manufacturing efficiency of the laminate for food packaging, it is preferable that the initial value of the aromatic isocyanate monomer remaining in the adhesive layer is lower. By removing the diisocyanate monomer in advance, a two-component curable adhesive with excellent manufacturing efficiency can be obtained.

[0030] The removal of diisocyanate monomer can be carried out 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 according to the diisocyanate monomer to be removed. As an example, they are 0.1 mbar or less and 120°C to 190°C. The removal step of the diisocyanate monomer may be carried out multiple times.

[0031] The content of the 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 according to the following conditions.

[0032] Apparatus: "ACQUITY UPLC H-Class" manufactured by Waters Corporation Data processing: "Empower-3" manufactured by Waters Corporation Column: "ACQUITY UPLC HSS T3" (100 mm × 2.1 mmφ, 1.8 μm) manufactured by Waters Corporation, 40°C Eluent: Ammonium formate aqueous solution / methanol, 0.3 mL / min Detector: PDA Sample preparation: 1. Dissolve 100 mg of the appropriately blocked sample in 10 ml of THF (for LC). 2. Stir for 30 seconds with vortexing. 3. Dilute appropriately with the eluent (mobile phase). 4. Pass through a 0.2 μm filtration filter to obtain the measurement sample. Calculation of area ratio: Calculate using the maximum absorption wavelength for the target substance.

[0033] (Isocyanate compound (A2)) The isocyanate compound (A2) is a reaction product of an aliphatic hydroxycarboxylic acid and a diisocyanate. As the diisocyanate used in the synthesis of the isocyanate compound (A2), the same ones as exemplified as those used in the synthesis of the polyurethane polyisocyanate (A1) can be used. It is preferable to use an aliphatic hydroxycarboxylic acid having a melting point of 80°C or lower.

[0034] As the aliphatic hydroxycarboxylic acid, conventionally known ones can be used and are not particularly limited. As an example, glycolic acid, lactic acid, glyceric acid, hydroxybutyric acid, tartronic acid, malic acid, tartaric acid, citric acid, dimethylolpropionic acid, dimethylolbutanoic acid, ricinoleic acid, 12-hydroxystearic acid, etc. can be mentioned, and one kind or a combination of two or more kinds can be used. It is preferable to use ricinoleic acid.

[0035] The isocyanate compound (A2) may contain a compound (A2-1) having an isocyanate group to which an aliphatic hydroxycarboxylic acid is bonded only at one terminal of the diisocyanate, and a compound (A2-2) to which an aliphatic hydroxycarboxylic acid is bonded at both terminals of the diisocyanate. The isocyanate compound (A2) preferably contains 50% by mass or more of the compound (A2-1), and more preferably 80% by mass or more. The entire amount of the isocyanate compound (A2) may be the compound (A2-1).

[0036] Such an isocyanate compound (A2-1) can be obtained, for example, by reacting a diisocyanate monomer with an aliphatic hydroxycarboxylic acid under conditions where the isocyanate groups contained in the diisocyanate monomer are in excess relative to the hydroxyl groups contained in the aliphatic hydroxycarboxylic acid to obtain a composition containing an isocyanate compound (A2) and unreacted diisocyanate monomer, and then, if necessary, removing the unreacted diisocyanate monomer. The equivalent ratio [NCO] / [hydroxyl group] of the isocyanate groups to the hydroxyl groups can be adjusted as appropriate, but as an example, it is 2.0 or more and 20.0 or less. The unreacted diisocyanate monomer can be removed by the same method and conditions as in the synthesis of the polyurethane polyisocyanate (A1). Similar to the polyurethane polyisocyanate (A1), it is preferable to perform the removal step until the amount of the diisocyanate monomer in the isocyanate compound (A2) becomes 0.1% by mass or less.

[0037] The content of the isocyanate compound (A2) can be adjusted as appropriate, but as an example, it is preferably 0.05% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 3% by mass or less, of the total amount of the polyurethane polyisocyanate (A1) and the isocyanate compound (A2).

[0038] (Isocyanate compound (A3)) The polyisocyanate composition of the present invention may contain an isocyanate compound (A3) other than the polyurethane polyisocyanate (A1) and the isocyanate compound (A2). Examples of the polyisocyanate compound (A3) include burette bodies, nurate bodies, allophanate bodies, carbodiimide-modified bodies, uretdione-modified bodies, etc. of at least one diisocyanate selected from aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates. The polyisocyanate compound (A3) can be used alone or in combination of two or more.

[0039] Aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates can be the same as the diisocyanate monomers exemplified as the raw materials for the polyurethane polyisocyanate (A1).

[0040] When the content of the diisocyanate monomer in the polyisocyanate composition of the present invention is 0.1% by mass or less, it is preferable to use the isocyanate compound (A3) also having a diisocyanate monomer content of 0.1% by mass or less.

[0041] When the polyisocyanate composition of the present invention contains the isocyanate compound (A3), its content can be appropriately adjusted. As an example, it is 10% by mass or more and 90% by mass or less of the total amount of the polyurethane polyisocyanate (A1), the isocyanate compound (A2), and the isocyanate compound (A3).

[0042] The polyisocyanate composition of the present invention may or may not contain an organic solvent. Examples of the organic solvent that the polyisocyanate composition of the present invention can contain 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, dimethyl sulfonamide, and the like.

[0043] The polyisocyanate composition of the present invention may contain any components within a range that does not inhibit the object of the present invention in addition to the above-described components.

[0044] <Two-component curable composition> The polyisocyanate composition of the present invention can be used as a two-component curable composition in combination with an isocyanate-reactive composition containing a compound having reactivity with isocyanate. Examples of the compound having reactivity 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 the like.

[0045] Such two-component curable compositions can be used, for example, as adhesives, coating agents, sealants, elastomers, and the like. The two-component curable composition using the polyisocyanate composition of the present invention is excellent in adhesion to a metal substrate and can be suitably used for such applications, but is not limited thereto.

[0046] <Adhesive> The polyisocyanate composition of the present invention can be suitably used as one component of a two-component curable adhesive. The two-component curable adhesive of the present invention contains a polyisocyanate composition (X) and a polyol composition (Y).

[0047] (Polyisocyanate composition (X)) The polyisocyanate composition (X) contains the above-described polyisocyanate composition and can contain other components as necessary.

[0048] When the adhesive of the present invention is used as a solvent-free two-component curable adhesive, the viscosity of the polyisocyanate composition (X) is adjusted to a range suitable for the non-solvent lamination method. As an example, the viscosity at 40 °C is adjusted to be in the range of 100 to 50,000 mPas, more preferably 500 to 20,000 mPas. The viscosity of the polyisocyanate composition (X) can be adjusted, for example, by adjusting the structure of the polyurethane polyisocyanate (A1) (the polyol used) or by using the polyisocyanate compound (A3) in combination. The viscosity of the polyisocyanate composition (X) can be measured, for example, using a rotational viscometer with a cone-plate: 1° × diameter 50 mm and a shear rate: 100 sec -1 , and can be measured at 40 °C ± 1 °C.

[0049] When the adhesive of the present invention is used as a solvent-based two-component curable adhesive, the viscosity of the polyisocyanate composition (X) can be adjusted to a viscosity suitable for coating by diluting with an organic solvent.

[0050] (Polyol composition (Y)) The polyol composition (Y) contains a polyol compound (B) having a plurality of hydroxyl groups. There is no particular limitation on the polyol compound (B), and any polyol compound that is usually used in a urethane reaction type two-component curable adhesive can be used.

[0051] Specific examples of the polyol compound (B) include, for example, polyether polyol (B1), polyol (B2) having a tertiary amino group, polyester polyol (B3), polyester polyether polyol (B4), polyurethane polyol (B5), polyester polyurethane polyol (B6), polyether polyurethane polyol (B7), vegetable oil polyol (B8), sugar alcohol (B9), polycarbonate polyol (B10), acrylic polyol (B11), hydroxyl group-containing olefin resin (B12), hydroxyl group-containing fluororesin (B13), and the like.

[0052] Examples of the polyether polyol (B1) 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 such as glycols like 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, triethylene glycol; and trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, pentaerythritol, and triol forms of polypropylene glycol.

[0053] Examples of the polyol (B2) having a tertiary amino group include those obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexylene using an amine compound having an active hydrogen group as a polymerization initiator. As the amine compound, conventionally known ones can be used. Examples include primary or secondary alkylamines such as ethylamine and diethylamine, amine compounds having a plurality of amino groups such as methylenediamine and ethylenediamine, and primary or secondary alkanolamines such as monoethanolamine and diethanolamine.

[0054] Specific examples of the polyol (B2) having such a tertiary amino group include, for example, polypropylene glycol ethylene diamine ether, tri(1,2-polypropylene glycol)amine, N-ethyldiethanolamine, N-methyl-N-hydroxyethyl-N-hydroxyethoxyethylamine, pentakis hydroxypropyl diethylenetriamine, tetrakis hydroxypropyl ethylenediamine, etc., but are not limited thereto. The polyol (B2) having a tertiary amino group can be used alone or in combination of two or more. It is preferable to use a polyol (B2) having a secondary hydroxyl group.

[0055] The polyester polyol (B3) is a reaction product of a polyhydric alcohol and a polyvalent carboxylic acid. The polyhydric alcohol used in the synthesis of the polyester polyol may be a diol or a polyol having three or more functional groups. Further, a polyester polyether polyol using the polyether polyol as the diol, or a polyester polyurethane polyol using the polyurethane polyol described below may also be used. Examples of the diol 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, 2,2,4-trimethyl-1,3-pentanediol;

[0056] ether glycols such as polyoxyethylene glycol and polyoxypropylene glycol; A modified polyether diol obtained by ring-opening polymerization of an aliphatic diol and various compounds containing a cyclic ether bond such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, etc.;

[0057] A lactone-based polyester polyol obtained by polycondensation reaction of an aliphatic diol and various lactones such as lactanoid, ε-caprolactone, etc.;

[0058] Bisphenols such as bisphenol A and bisphenol F;

[0059] Examples include alkylene oxide adducts of bisphenols obtained by adding ethylene oxide, propylene oxide, etc. to bisphenols such as bisphenol A and bisphenol F.

[0060] Polyols with three or more functional groups include aliphatic polyols such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, pentaerythritol, etc.;

[0061] A modified polyether polyol obtained by ring-opening polymerization of an aliphatic polyol and various compounds containing a cyclic ether bond such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, etc.;

[0062] Examples include lactone-based polyester polyols obtained by polycondensation reaction of an aliphatic polyol and various lactones such as ε-caprolactone, etc.

[0063] Examples of the polycarboxylic acids used for synthesizing the polyester polyol (B3) include aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3 - cyclopentanedicarboxylic acid, 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, 1,2 - bis(phenoxy)ethane - p,p’ - dicarboxylic acid; and anhydrides or ester - forming derivatives of these aliphatic or dicarboxylic acids; polybasic acids such as p - hydroxybenzoic acid, p-(2 - hydroxyethoxy)benzoic acid and ester - forming derivatives of these dihydroxycarboxylic acids, dimer acid, etc.

[0064] The polyurethane polyol (B5) is a reaction product of a low - molecular - weight or high - molecular - weight polyol and a polyisocyanate compound. As the low - molecular - weight polyol, the same ones as the polyhydric alcohols exemplified as raw materials for the polyester polyol can be used. Examples of the high - molecular - weight polyol include polyether polyol, polyester polyol, etc. As the polyisocyanate compound, the same ones as those exemplified as the diisocyanate monomer (l) and those exemplified as the polyisocyanate compound (A2) can be used.

[0065] Examples of the vegetable oil polyol (B8) include castor oil, dehydrated castor oil, hydrogenated castor oil which is a hydrogenated product of castor oil, and an adduct of 5 - 50 moles of alkylene oxide to castor oil, etc.

[0066] Examples of the sugar alcohol (B9) include pentaerythritol, sucrose, xylitol, sorbitol, isomalt, lactitol, maltitol, mannose sugar, etc.

[0067] The adhesive of the present invention can be suitably used for the production of a laminate for packaging materials used in food packaging and the like. When the adhesive of the present invention is used for such applications, the polyol compound (B) preferably contains at least one selected from polyether polyol (B1), polyol having a tertiary amino group (B2), polyester polyol (B3), polyester polyether polyol (B4), polyurethane polyol (B5), polyester polyurethane polyol (B6), polyether polyurethane polyol (B7), vegetable oil polyol (B8), and sugar alcohol (B9).

[0068] The content of these polyol compounds (B) can be appropriately adjusted according to the purpose, but as an example, it is 50% by mass or more in the solid content of the polyol composition (Y).

[0069] The hydroxyl value of the polyol compound (B) can be appropriately adjusted, but as an example, it is 1 mgKOH / g or more and 300 mgKOH / g or less. When the adhesive of the present invention is used as a solvent-free adhesive, the polyol compound (B) preferably has a hydroxyl value of 20 mgKOH / g or more and 300 mgKOH / g or less. When the adhesive of the present invention is used as a solvent-based adhesive, the polyol compound (B) preferably has a hydroxyl value of 1 mgKOH / g or more and 50 mgKOH / g or less. The hydroxyl value of the polyol compound (B) can be calculated from the average functionality and molecular weight of the polyol compound.

[0070] (Amine compound (C)) The polyol composition (Y) may contain an amine compound (C) having an amino group. In this specification, the amino group refers to an NH 2 group or an NHR group (R is an alkyl group or an aryl group which may have a functional group).

[0071] As the amine compound (C), known ones can be used without particular limitation, such as methylenediamine, ethylenediamine, isophoronediamine, 3,9-dipropaneamine-2,4,8,10-tetraoxaspiro[5.5]undecane, lysine, 2,2,4-trimethylhexamethylenediamine, hydrazine, piperazine, 2-hydroxyethylethylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropyl ethylenediamine, di-2-hydroxypropyl ethylenediamine, poly(propylene glycol) diamine, poly(propylene glycol) triamine, poly(propylene glycol) tetraamine, 1,2-diaminopropane, 1,3-diaminopropane,

[0072] 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, norbornad diamine,

[0073] Bis(aminomethyl)cyclohexane, diaminodicyclohexylmethane, isophoronediamine, menthylenediamine, bis(cyanoethyl)diethylenetriamine, 1,4-bis-(8-aminopropyl)-piperazine, piperazine-1,4-diazacycloheptane, 1-(2'-aminoethylpiperazine), 1-[2'-(2”-aminoethylamino)ethyl]piperazine, tricyclodecane diamine, an amine compound (C1) having a plurality of amino groups such as a polyureaamine which is a reaction product of the above-described various polyamines and the above-described various isocyanate components,

[0074] Monoethanolamine, monoisopropanolamine, monobutanolamine, N-methylethanolamine, N-ethylethanolamine, N-methylpropanolamine, diethanolamine, diisopropanolamine and other primary or secondary alkanolamines (C2),

[0075] Primary or secondary amines (C3) such as ethylamine, octylamine, laurylamine, myristylamine, stearylamine, oleylamine, diethylamine, dibutylamine, distearylamine and the like can be mentioned.

[0076] The blending amount of the amine compound (C) is preferably blended so that the amine value of the polyol composition (Y) is 20 to 70 mgKOH / g, more preferably 25 to 50 mgKOH / g.

[0077] In addition, the amine value in this specification means the number of milligrams of KOH equivalent to the amount of HCl required to neutralize 1 g of the sample, and there is no particular limitation, and it can be calculated using a known method. When the chemical structure of the amine compound (C), and further, if necessary, the average molecular weight, etc. are known, it can be calculated from (the number of amino groups per molecule / average molecular weight) × 56.1 × 1000. When the chemical structure, average molecular weight, etc. of the amine compound are unknown, it can be measured according to a known amine value measurement method, for example, JIS K7237-1995.

[0078] (Monoalcohol compound (D)) The polyol composition (Y) may contain a monoalcohol compound (D) having one alcoholic hydroxyl group. The main chain of the monoalcohol compound (D) is not particularly limited, and examples thereof include vinyl resins, acrylic resins, polyesters, epoxy resins, urethane resins, etc. having one hydroxyl group. Further, aliphatic alcohols, alkyl alkylene glycols, etc. can also be used. The main chain of the monoalcohol compound (D) may be linear or branched. The bonding position of the hydroxyl group is not particularly limited, but it is preferably present at the end of the molecular chain.

[0079] Specific examples of the monoalcohol compound (D) include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, lauryl alcohol, myristyl alcohol, pentadecanol, cetyl alcohol, heptadecanol, stearyl alcohol, nonadecanol, other alkanols (C20 - 50), oleyl alcohol, and aliphatic monoalcohols such as isomers thereof.

[0080] Cyclohexanol, methylcyclohexanol, 4-butylcyclohexanol, 4-pentylcyclohexanol, 4-hexylcyclohexanol, cyclodecanol, cyclododecanol, cyclopentadecanol, 4-isopropylcyclohexanol, 3,5,5-trimethylcyclohexanol, menthol, 2-norbornanol, borneol, 2-adamantanol, dicyclohexylmethanol, decatol, 2-cyclohexylcyclohexanol, 4-cyclohexylcyclohexanol, 4-(4-propylcyclohexyl)cyclohexanol, 4-(4-pentylcyclohexyl)cyclohexanol, α-ambrinol, desoxycorticosterone, 11-dehydrocorticosterone, cholesterol, β-sitosterol, campesterol, stigmasterol, brassicasterol, lanosterol, ergosterol, β-cholestanol, testosterone, estrone, digitoxigenin, dehydroepiandrosterone, coprostanol, pregnenolone, epicoprostanol, 7-dehydrocholesterol, estradiol benzoate, tigogenin, hecogenin, methandienone, cortisone acetate, stenolone, and alicyclic monohydric alcohols such as isomers thereof,

[0081] Aromatic aliphatic monohydric alcohols such as benzyl alcohol,

[0082] Examples thereof include polyoxyalkylene monohydric alcohols 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 atom or the like as an initiator.

[0083] When the two-component curable adhesive of the present invention is used as a solvent-free type, the viscosity of the polyol composition (Y) is adjusted to a range suitable for the non-solvent lamination method. As an example, the viscosity at 40 ° C is adjusted to be in the range of 100 to 50,000 mPas, more preferably 100 to 20,000 mPas. The viscosity of the polyol composition (Y) can be adjusted by the skeleton of the polyol compound (B) and plasticizers and the like described later. When adjusting with the skeleton of the polyol compound (B), for example, the viscosity can be reduced by using polypropylene glycol or a polyester polyol obtained by the reaction of an aliphatic carboxylic acid and a polyol. Alternatively, the viscosity can be increased by using a polyester polyol obtained by the reaction of an aromatic carboxylic acid and a polyol.

[0084] (Other components of the adhesive) The two-component curable adhesive of the present invention may contain components other than the above-described components. The other components may be contained in either or both of the polyisocyanate composition (X) and the polyol composition (Y), or may be adjusted separately and mixed with the polyisocyanate composition (X) and the polyol composition (Y) immediately before coating the adhesive. Hereinafter, each component will be described.

[0085] (Catalyst) Examples of the catalyst include metal-based catalysts, amine-based catalysts, aliphatic cyclic amide compounds, quaternary ammonium salts, and the like.

[0086] Examples of the metal-based catalyst include metal complex-based, inorganic metal-based, and organometallic-based catalysts. Examples of the metal complex-based 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, zirconia acetylacetonate, and the like.

[0087] Examples of the inorganic metal catalysts include those selected from Sn, Fe, Mn, Cu, Zr, Th, Ti, Al, Co, etc.

[0088] Examples of the organometallic catalysts include organozinc compounds such as zinc octylate, zinc neodecanoate, zinc naphthenate; organotin compounds such as stannous diacetate, stannous dioctoate, stannous dioleate, stannous dilaurate, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin oxide, dibutyltin dichloride; organonickel compounds such as nickel octylate, nickel naphthenate; organocobalt compounds such as cobalt octylate, cobalt naphthenate; organobismuth compounds such as bismuth octylate, bismuth neodecanoate, bismuth naphthenate; titanium compounds such as tetraisopropyl titanate, dibutyltitanium dichloride, tetrabutyl titanate, butoxytitanium trichloride, titanium chelate complexes having at least one kind of alcohol having 2 to 10 carbon atoms as a ligand, etc.

[0089] 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)propylenediamine, bis(dimethylaminopropyl)amine, bis(dimethylaminopropyl)isopropanolamine, 3-quinuclidinol, N,N,N’,N’-tetramethylguanidine, 1,3,5-tris(N,N-dimethylaminopropyl)hexahydro-S-triazine, 1,8-diazabicyclo[5.4.0]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, etc.

[0090] Examples of the aliphatic cyclic amide compound include δ-valerolactam, ε-caprolactam, ω-enantholactam, η-capryllactam, β-propiolactam, etc. Among these, ε-caprolactam is effective for promoting curing.

[0091] Examples of the quaternary ammonium salts include hydroxy salts such as alkylammonium and aromatic ammonium, alkyl acid salts, halide salts, and the like. 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, and the like.

[0092] (Acid anhydride) Examples of the acid anhydrides include cyclic aliphatic acid anhydrides, aromatic acid anhydrides, unsaturated carboxylic acid anhydrides, and the like, and one or more of them can be used in combination. More specifically, for example, maleic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, dodecenyl succinic anhydride, polyadipic anhydride, polyazelaic anhydride, polysebacic anhydride, poly(ethyl octadecanedioic acid) anhydride, poly(phenyl hexadecanedioic acid) anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hymic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexenedicarboxylic anhydride, methylcyclohexenetetracarboxylic anhydride, ethylene glycol bistrimellitate dianhydride, het acid anhydride, nadic anhydride, methyl nadic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, and the like.

[0093] Alternatively, a compound obtained by modifying the above-described compound as an acid anhydride with glycol may be used. Examples of glycols that can be used for modification include alkylene glycols such as ethylene glycol, propylene glycol, and neopentyl glycol; polyether glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. Furthermore, a copolymerized polyether glycol of two or more of these glycols and / or polyether glycols can also be used.

[0094] Alternatively, a homopolymer or copolymer of a compound having a polymerizable unsaturated group such as maleic anhydride among the above-described compounds as an acid anhydride may be used. Examples of compounds that can copolymerize 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; (meth)acrylic monomers such as (meth)acrylic acid and (meth)acrylic acid esters; 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; fluoroolefins such as vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, and chlorotrifluoroethylene. These can be used alone or in combination of two or more. It is preferable to use styrene and p-tert-butylstyrene, which are vinyl compounds having an aromatic ring.

[0095] (Coupling agent) Examples of the coupling agent include silane coupling agents, titanate-based coupling agents, and aluminum-based coupling agents.

[0096] Examples of silane coupling agents include aminosilanes such as γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, and bis[3-(triethoxysilyl)propyl]amine; epoxysilanes such as β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane; vinylsilanes such as vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane; and hexamethyldisilazane, γ-mercaptopropyltrimethoxysilane, etc.

[0097] Examples of titanate coupling agents include, for example, tetraisopropoxytitanium, tetra-n-butoxytitanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, titanium lactate, tetrastearoxytitanium, etc.

[0098] Examples of aluminum coupling agents include, for example, acetalkoxyaluminum diisopropylate, etc.

[0099] (Pigment) There are no particular restrictions on the pigment, and examples include extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments, green pigments, blue pigments, metallic powder pigments, luminescent pigments, pearl pigments, and other organic and inorganic pigments, as well as plastic pigments, etc., described in the Paint Raw Materials Handbook 1970 Edition (edited by the Japan Paint Industry Association).

[0100] Examples of extender pigments include precipitated barium sulfate, rice powder, precipitated calcium carbonate, calcium bicarbonate, gypsum, alumina white, silica, hydrated fine silica (white carbon), ultrafine anhydrous silica (aerosil), silica sand, talc, precipitated magnesium carbonate, bentonite, clay, kaolin, loess, and the like.

[0101] Specific examples of organic pigments include various insoluble azo pigments such as benzidine yellow, Hansa yellow, and Lake Red 4R; soluble azo pigments such as Lake C, Carmine 6B, and Bordeaux 10; various (copper) phthalocyanine-based pigments such as phthalocyanine blue and phthalocyanine green; various chlorine-based dyed lakes such as rhodamine lake and methyl violet lake; various mordant dye-based pigments such as quinoline lake and Fast Sky Blue; various vat dye-based pigments such as anthraquinone-based pigments, thioindigo-based pigments, and perinone-based pigments; various quinacridone-based pigments such as Cincassia Red B; various dioxazine-based pigments such as dioxazine violet; various condensed azo pigments such as chromophthal; and aniline black.

[0102] Examples of inorganic pigments include various chromates such as lead yellow, zinc chromate, and molybdate orange; various ferrocyanide compounds such as ultramarine; various metal oxides such as titanium oxide, zinc white, Mapico yellow, iron oxide, red iron oxide, chromium 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 violet; various metal powder pigments such as aluminum powder, gold powder, silver powder, copper powder, bronze powder, and brass powder; flake pigments of these metals, mica flake pigments; 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.

[0103] Examples of the plastic pigment include "Grandol PP-1000", "PP-2000S", etc. manufactured by DIC Corporation.

[0104] The pigment to be used may be appropriately selected according to the purpose. For example, since it is excellent in durability, weather resistance, and design, it is preferable to use inorganic oxides such as titanium oxide and zinc white as the white pigment, and it is preferable to use carbon black as the black pigment.

[0105] As an example, the blending amount of the pigment is 1 to 400 parts by mass with respect to 100 parts by mass of the total non-volatile content of the polyol composition (X) and the polyisocyanate composition (Y), and it is more preferably 10 to 300 parts by mass in order to make the adhesiveness and blocking resistance better.

[0106] (Plasticizer) Examples of the plasticizer 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, carbonate-based plasticizers, etc.

[0107] Examples of the phthalic acid-based plasticizer include phthalic acid ester-based plasticizers such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, diheptyl phthalate, di-(2-ethylhexyl) phthalate, di-n-octyl phthalate, dinonyl phthalate, diisononyl phthalate, didecyl phthalate, diisodecyl phthalate, ditridecyl phthalate, diundecyl phthalate, dilauryl phthalate, distearyl phthalate, diphenyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, dicyclohexyl phthalate, octyl decyl phthalate, dimethyl isophthalate, di-(2-ethylhexyl) isophthalate, diisooctyl isophthalate, etc., and tetrahydrophthalic acid ester-based plasticizers such as di-(2-ethylhexyl) tetrahydrophthalate, di-n-octyl tetrahydrophthalate, diisodecyl tetrahydrophthalate, etc.

[0108] Examples of fatty acid plasticizers include adipic acid plasticizers such as di-n-butyl adipate, di-(2-ethylhexyl) adipate, diisodecyl adipate, diisononyl adipate, di(C6-C10 alkyl) adipate, and dibutyl diglycol adipate; azelaic acid plasticizers such as di-n-hexyl azelate, di-(2-ethylhexyl) azelate, and diisooctyl azelate; sebacic acid plasticizers such as di-n-butyl sebacate, 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; itaconic acid plasticizers such as monomethyl itaconate, monobutyl itaconate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, and di-(2-ethylhexyl) itaconate; stearic acid plasticizers such as n-butyl stearate, glycerin monostearate, and diethylene glycol distearate; oleic acid plasticizers such as butyl oleate, glyceryl monooleate, and diethylene glycol monooleate; citric acid plasticizers such as triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tributyl citrate, and acetyl tri-(2-ethylhexyl) citrate; ricinoleic acid plasticizers such as methyl acetyl ricinoleate, butyl acetyl ricinoleate, glyceryl monoricinoleate, and diethylene glycol monoricinoleate; and other fatty acid plasticizers such as diethylene glycol monolaurate, diethylene glycol diperargonate, and pentaerythritol fatty acid ester.

[0109] Examples of the 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, triisodecyl trimellitate, etc.; and pyromellitic acid plasticizers such as tetra-(2-ethylhexyl) pyromellitate, tetra-n-octyl pyromellitate, etc.

[0110] Examples of the phosphoric acid plasticizers include triethyl phosphate, tributyl phosphate, tri-(2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, octyldiphenyl phosphate, cresyldiphenyl phosphate, cresylphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris(chloroethyl) phosphate, tris(chloropropyl) phosphate, tris(dichloropropyl) phosphate, tris(isopropylphenyl) phosphate, etc.

[0111] Examples of the polyol plasticizers include glycol plasticizers such as diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, triethylene glycol di-(2-ethylbutyrate), triethylene glycol di-(2-ethylhexoate), dibutyl methylene bisthioglycolate, etc.; and glycerin plasticizers such as glycerol monoacetate, glycerol triacetate, glycerol tributyrate, etc.

[0112] Examples of the epoxy plasticizers include epoxidized soybean oil, epoxy butyl stearate, epoxy di-2-ethylhexyl hexahydrophthalate, epoxy diisodecyl hexahydrophthalate, epoxy triglyceride, epoxy octyl oleate, epoxy decyl oleate, etc.

[0113] Examples of polyester plasticizers include adipic acid-based polyesters, sebacic acid-based polyesters, phthalic acid-based polyesters, and the like.

[0114] Examples of carbonate plasticizers include propylene carbonate and ethylene carbonate.

[0115] In addition, other plasticizers include partially hydrogenated terphenyl, adhesive plasticizers, and polymerizable plasticizers such as diallyl phthalate, acrylic monomers, and oligomers. These plasticizers can be used alone or in combination of two or more.

[0116] (Phosphate compound) Examples of phosphate compounds 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, and the like.

[0117] (Form of the adhesive) The two-component curable adhesive of the present invention may be in either a solvent-based or solvent-free form. In this specification, the "solvent-based" adhesive refers to a form used in the 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 film, and then bonded to another substrate. Either one or both of the polyisocyanate composition (X) and the polyol composition (Y) contain an organic solvent capable of dissolving (diluting) the components of the polyisocyanate composition (X) and the polyol composition (Y) used in the present invention.

[0118] Examples of the organic solvent 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, dimethyl sulfonamide, and the like. The organic solvent used as a reaction medium during the production of the components of the polyisocyanate composition (X) and the polyol composition (Y) may also be used as a diluent during coating.

[0119] As used herein, the "solventless" adhesive refers to a form of adhesive used in the so-called non-solvent lamination method, which is a method of bonding to another substrate without going through a step of heating with an oven or the like to volatilize the solvent after applying the adhesive to the substrate, without substantially containing 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; highly soluble organic solvents such as dimethyl sulfoxide and dimethyl sulfonamide, particularly ethyl acetate or methyl ethyl ketone. When a trace amount of organic solvent remains in the polyisocyanate composition (X) and the polyol composition (Y) because the components of the polyisocyanate composition (X) or the polyol composition (Y) and the organic solvent used as a reaction medium during the production of their raw materials cannot be completely removed, it is regarded as substantially free of organic solvent. Also, when the polyol composition (Y) contains a low molecular weight alcohol, since the low molecular weight alcohol reacts with the polyisocyanate composition (X) to become a part of the coating film, there is no need to volatilize it after coating. Therefore, such a form is also treated as a solventless adhesive, and the low molecular weight alcohol is not regarded as an organic solvent.

[0120] A decrease in the adhesion between the adhesive layer and the metal foil or metal vapor deposition film over time is likely to occur when the adhesive is a solvent-free type. Therefore, the present invention exhibits a more remarkable effect when the adhesive is a solvent-free type.

[0121] The two-component curable adhesive of the present invention is preferably formulated and used such that the ratio [NCO] / [OH] of the number of moles [NCO] of the isocyanate groups contained in the polyisocyanate composition (X) to the number of moles [OH] of the hydroxyl groups contained in the polyol composition (Y) is 0.5 to 5.0, more preferably 1.0 to 3.0. Thereby, appropriate curability can be obtained without depending on the environmental humidity during coating.

[0122] <Laminate> The laminate of the present invention can be obtained, for example, by a method having a two-component mixing step of premixing the polyisocyanate composition (X) and the polyol composition (Y), then applying the mixture to a first substrate, then laminating a second substrate on the coated surface, and curing the adhesive layer, or by a method having a two-component separate coating step of separately applying the polyisocyanate composition (X) and the polyol composition (Y) to the first substrate and the second substrate, then bringing the coated surfaces into contact with each other and pressing them to laminate the first substrate and the second substrate, and curing the adhesive layer. There is no particular limitation on the film to be used, and a film suitable for the application can be appropriately selected.

[0123] For example, for food packaging, there are polyethylene terephthalate (PET) films, polystyrene films, polyamide films, polyacrylonitrile films, polyethylene films (LLDPE: low-density polyethylene film, HDPE: high-density polyethylene film, MDOPE: uniaxially stretched polyethylene film, OPE: biaxially stretched polyethylene film), polypropylene films (CPP: unstretched polypropylene film, OPP: biaxially stretched polypropylene film), ethylene-vinyl alcohol copolymers, and polyolefin films such as gas barrier heat-seal films obtained by providing an olefin-based heat-sealing resin layer on one or both sides of a resin having gas barrier properties such as polyvinyl alcohol, as well as polyvinyl alcohol films, ethylene-vinyl alcohol copolymer films, etc.

[0124] Also, it is also preferable to use biomass films, biodegradable films, or recycled plastic films formed from materials containing biomass-derived components, biodegradable components, or recycled components. Biomass films, biodegradable films, and recycled plastic films are not only sold by various companies, but also, for example, film sheets such as those listed in the biomass-certified product list described by the Japan Organic Resources Association, films such as those listed in the eco-mark certified product list described by the Japan Environmental Association, and films having a symbol mark defined by the Japan Bioplastics Association. Films certified in various countries can be used.

[0125] (Biomass film) Specifically well-known biomass films include those made from ethylene glycol derived from biomass. Ethylene glycol derived from biomass is made from ethanol (biomass ethanol) produced from biomass as a raw material. For example, ethylene glycol derived from biomass can be obtained by a method such as generating ethylene glycol via ethylene oxide from biomass ethanol by a conventionally known method. Also, commercially available biomass ethylene glycol may be used, and for example, biomass ethylene glycol commercially available from Indiaglycol can be preferably used.

[0126] For example, as an alternative to polyethylene terephthalate films using conventional petroleum-based raw materials, films containing biomass polyesters, biomass polyethylene terephthalate, etc., which use ethylene glycol derived from biomass as the diol unit and dicarboxylic acids derived from fossil fuels as the dicarboxylic acid unit, are known.

[0127] The dicarboxylic acid unit of the biomass polyester uses dicarboxylic acids derived from fossil fuels. As the dicarboxylic acid, aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and their derivatives can be used without limitation. In addition to the above diol component and dicarboxylic acid component, a copolymer polyester obtained by adding a copolymerization component as a third component, such as at least one polyfunctional compound selected from the group consisting of bifunctional oxycarboxylic acids, polyhydric alcohols having three or more functional groups, polycarboxylic acids having three or more functional groups and / or their anhydrides, and oxycarboxylic acids having three or more functional groups for forming a crosslinked structure, may also be used.

[0128] Also, for example, as an alternative to polyolefin-based films using conventional petroleum-based raw materials, biomass polyolefin-based films such as biomass polyethylene-based films containing polyethylene-based resins made from ethylene glycol derived from biomass, and biomass polyethylene - polypropylene-based films are known. The polyethylene resin is not particularly limited except that a part of the raw materials uses the ethylene glycol derived from the biomass described above. Examples include a homopolymer of ethylene, a copolymer of ethylene and an α-olefin with ethylene as the main component (ethylene-α-olefin copolymer containing 90% by mass or more of ethylene units), etc. These can be used alone or in combination of two or more.

[0129] In addition, the α-olefin constituting the copolymer of ethylene and an α-olefin is not particularly limited, and examples include α-olefins having 4 to 8 carbon atoms such as 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene. Known polyethylene resins such as low-density polyethylene resin, medium-density polyethylene resin, and linear low-density polyethylene resin can be used. Among them, from the viewpoint of making it even less likely to cause damage such as perforation or breakage even when the films rub against each other, linear low-density polyethylene resin (LLDPE) (a copolymer of ethylene and 1-hexene, or a copolymer of ethylene and 1-octene) is preferred, and a linear low-density polyethylene resin with a density of 0.910 to 0.925 g / cm 3 and a linear low-density polyethylene resin is more preferred.

[0130] As for the biomass film, those using biomass raw materials classified by the biomass plastic degree defined in ISO16620 or ASTM D6866 are also in circulation. In the atmosphere, radioactive carbon 14C exists at a ratio of 1 in 1012, and this ratio does not change even in carbon dioxide in the atmosphere. Therefore, this ratio does not change even in plants that have fixed this carbon dioxide through photosynthesis. For this reason, the carbon of plant-derived resins contains radioactive carbon 14C. In contrast, the carbon of 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 content ratio of plant-derived resins in the resin, that is, the biomass plastic degree, can be determined.

[0131] Examples of plant-derived low-density polyethylene, which is a biomass plastic with a biomass plastic content of 80% or more, preferably 90% or more, as defined by ISO 16620 or ASTM D6866, include products named "SBC818", "SPB608", "SBF0323HC", "STN7006", "SEB853", "SPB681", etc. manufactured by Braskem. Films using these as raw materials can be preferably used.

[0132] In addition, films and sheets blended with starch, which is a biomass raw material, or polylactic acid are also known. These can be appropriately selected and used according to the application.

[0133] 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 unoriented films or oriented films, and their manufacturing methods are not limited.

[0134] (Biodegradable Film) Specifically, well-known biodegradable films generally include those made from biodegradable resins that are commonly available. Examples include polycaprolactone, polyvinyl alcohol, polyamide, cellulose ester, lactic acid-based polyester resins, aliphatic polyester resins, or aliphatic aromatic polyester resins. These biodegradable resins can be used alone or in combination of two or more. Among them, aliphatic polyester resins or aliphatic aromatic polyester resins are preferably used. Examples of the aliphatic polyester resin include aliphatic polyesters obtained by polycondensation reaction of an aliphatic diol and an aliphatic dicarboxylic acid. Examples of the aliphatic diol 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 as a mixture thereof. Among them, it is preferable to use 1,4-butanediol. Examples of the aliphatic dicarboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, suberic acid, and dodecanedioic acid, and acid anhydrides which are derivatives thereof may also be used. Among them, it is preferable that they are succinic acid or succinic anhydride, or a mixture of these and adipic acid. Specifically, examples thereof include polybutylene succinate (PBS) obtained from 1,4-butanediol and succinic acid (for example, BioPBS manufactured by PPT MCC Biochem), polybutylene succinate adipate (PBSA) obtained by copolymerizing adipic acid with PBS, and the like.

[0135] Examples of the aliphatic aromatic polyester resin include copolymers containing an aliphatic dicarboxylic acid unit, an aromatic dicarboxylic acid unit, and a linear aliphatic and / or alicyclic diol unit. The diol component that provides the diol unit usually has 2 to 10 carbon atoms, and examples thereof include ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,4-cyclohexanedimethanol. Among them, diols having 2 to 4 carbon atoms are preferable, ethylene glycol and 1,4-butanediol are preferable, and 1,4-butanediol is more preferable. The dicarboxylic acid component that provides the dicarboxylic acid unit usually has 2 to 10 carbon atoms, and examples thereof include succinic acid, adipic acid, suberic acid, sebacic acid, and dodecanedioic acid. Among them, succinic acid or adipic acid is preferable. Examples of the aromatic dicarboxylic acid component that provides the aromatic dicarboxylic acid unit include terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid. Among them, terephthalic acid and isophthalic acid are preferable, and terephthalic acid is more preferable. Specifically, examples include PBAT which is a copolymer of 1,4-butanediol, adipic acid, and terephthalic acid (for example, Ecoflex manufactured by BASF).

[0136] Other examples include poly(3-hydroxyalkanoate) which is an aliphatic polyester copolymer obtained from hydroxyalkanoic acid and polyvalent carboxylic acid. Among them, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) (for example, Aonilex manufactured by Kaneka), polylactic acid (PLA) (for example, REVODE manufactured by Hisun Biomaterials Co., Ltd., Ingeo manufactured by NatureWorks) can be mentioned.

[0137] The biodegradable film may be a laminate of a plurality of biodegradable films, or may be a laminate of a conventional petroleum-based film and a biodegradable film. These biodegradable films may be unoriented films or oriented films, and their manufacturing methods are not limited.

[0138] The film may be subjected to an orientation treatment. As the orientation treatment method, it is common to melt-extrude the resin into a sheet shape by an extrusion film-forming method and then perform simultaneous biaxial orientation or sequential biaxial orientation. In the case of sequential biaxial orientation, it is common to first perform a longitudinal orientation treatment and then a transverse orientation. Specifically, a method combining longitudinal orientation using the speed difference between rolls and transverse orientation using a tenter is often used.

[0139] If necessary, various surface treatments such as flame treatment or corona discharge treatment may be performed on the film surface so that an adhesive layer without defects such as film breakage or repulsion is formed.

[0140] Alternatively, a film laminated with a vapor deposition layer of a metal such as aluminum or a metal oxide such as silica or alumina, or a barrier film containing a gas barrier layer such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, or vinylidene chloride may be used in combination. By using such a film, a laminate having barrier properties against water vapor, oxygen, alcohol, inert gas, volatile organic compounds (scents), etc. can be obtained.

[0141] As the paper, a known paper base material can be used without particular limitation. Specifically, it is manufactured by a known paper-making machine using natural fibers for papermaking such as wood pulp, but the papermaking conditions are not particularly specified. Examples of natural fibers for papermaking include wood pulp such as softwood pulp and hardwood pulp, non-wood pulp such as Manila hemp pulp, sisal hemp pulp, and flax pulp, and pulp obtained by chemically modifying these pulps. As the type of pulp, chemical pulp such as kraft sulfate pulping method, acidic / neutral / alkaline sulfite pulping method, and soda salt pulping method, ground pulp, chemiground pulp, thermomechanical pulp, etc. can be used. Also, various commercially available high-quality papers, coated papers, backing papers, impregnated papers, cardboard, and paperboard can be used.

[0142] As a more specific configuration of the laminate, (1) Substrate 1 / Adhesive layer 1 / Sealant film (2) Substrate 1 / Adhesive layer 1 / Metal vapor-deposited non-stretched film (3) Substrate 1 / Adhesive layer 1 / Metal vapor-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 vapor-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 Examples include, but are not limited to, the following.

[0143] Examples of the substrate 1 used in Configuration (1) include MDOPE film, OPE film, OPP film, PET film, nylon film, paper, etc. Further, as the substrate 1, a coated one may be used for the purpose of improving gas barrier properties and ink receptivity when providing a printing layer described later. Commercially available products of the coated substrate film 1 include K-OPP film, K-PET film, K-nylon film, etc. The adhesive layer 1 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include CPP film, LLDPE film, easy-open heat-seal film, gas-barrier heat-seal film, etc. A printing layer may be provided on the surface of the substrate 1 on the side of the adhesive layer 1 (when using a coated one as the substrate film 1, the surface of the coating layer on the side of the adhesive layer 1) or on the surface opposite to the adhesive layer 1. The printing layer is formed by a general printing method conventionally used for printing on polymer films and paper using various printing inks such as gravure ink, flexo ink, offset ink, screen ink, inkjet ink, etc.

[0144] Examples of the substrate 1 used in Configuration (2) and (3) include MDOPE film, OPE film, OPP film, PET film, paper, etc. The adhesive layer 1 is a cured coating film of the adhesive of the present invention. As the metal-deposited non-stretched film, CPP film, LLDPE film, VM-CPP film obtained by depositing a metal such as aluminum on a gas-barrier heat-seal film, VM-LLDPE film, etc. can be used. As the metal-deposited stretched film, VM-MDOPE film, VM-OPE film, VM-OPP film obtained by depositing a metal such as aluminum on MDOPE film, OPE film, OPP film can be used. Similar to Configuration (1), a printing layer may be provided on any surface of the substrate 1.

[0145] Examples of the transparent vapor-deposited stretched film used in Configuration (4) include films obtained by vapor-depositing silica or alumina on an MDOPE film, an OPE film, an OPP film, a PET film, a nylon film, etc. A film with a coating applied on the vapor-deposited layer may be used for the purpose of protecting the inorganic vapor-deposited layer of silica or alumina. The adhesive layer 1 is a cured coating film of the adhesive of the present invention. Examples of the sealant film are the same as those in Configuration (1). A printing layer may be provided on the surface of the transparent vapor-deposited stretched film on the side of the adhesive layer 1 (in the case of using a film with a coating applied on the inorganic vapor-deposited layer, the surface of the coating layer on the side of the adhesive layer 1). The method of forming the printing layer is the same as that in Configuration (1).

[0146] Examples of the base material 1 used in Configuration (5) include a PET film, paper, etc. Examples of the base material 2 include a nylon film, etc. 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 are the same as those in Configuration (1). Similar to Configuration (1), a printing layer may be provided on either surface of the base material 1.

[0147] Examples of the base material 1 in Configuration (6) are the same as those in Configurations (2) and (3). Examples of the metal vapor-deposited stretched film include VM-MDOPE film, VM-OPE film, VM-OPP film, and VM-PET film obtained by vapor-depositing a metal such as aluminum on an MDOPE film, an OPE film, an OPP film, or a PET film. At least one of the adhesive layer 1 and the adhesive layer 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film are the same as those in Configuration (1). Similar to Configuration (1), a printing layer may be provided on either surface of the base material 1.

[0148] Examples of the base material 1 in Configuration (7) include a PET film, paper, etc. Examples of the transparent vapor-deposited stretched film are the same as those in Configuration (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 are the same as those in Configuration (1). Similar to Configuration (1), a printing layer may be provided on either surface of the base material 1.

[0149] Examples of the base material 1 of the structure (8) include a PET film, paper, etc. Examples of the metal layer include an aluminum foil, etc. 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 are the same as those of the structure (1). Similar to the structure (1), a printing layer may be provided on either surface of the base material 1.

[0150] Examples of the base material 1 of the structures (9) and (10) include a PET film, paper, etc. Examples of the base material 2 include a nylon film, etc. Examples of the metal layer include an 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 are the same as those of the structure (1). Similar to the structure (1), a printing layer may be provided on either surface of the base material 1.

[0151] The adhesive of the present invention is excellent in adhesion to a metal base material or a metal vapor deposition layer, and the decrease in adhesion is suppressed even during long-term storage. Therefore, it is particularly preferably used in the production of the structures (2), (3), (6), (8) to (10). Among these structures, it is preferable that the adhesive layer in contact with the metal base material or the metal vapor deposition layer is a cured coating film of the adhesive of the present invention.

[0152] When the adhesive of the present invention is used as an adhesion auxiliary agent, the adhesion auxiliary agent of the present invention is applied to the film material serving as the base material using a roll such as a gravure roll, and after volatilizing the organic solvent by heating in an oven or the like, the polymer material melted by an extruder is laminated to obtain the laminate of the present invention.

[0153] In addition to the above-described structures (1) to (10), the laminate of the present invention may further include other films or base materials. As other base materials, in addition to the above-described stretched film, unstretched film, and transparent vapor deposition film, porous base materials such as paper, wood, and leather described later can also be used. The adhesive used when laminating other base materials may or may not be the adhesive of the present invention.

[0154] The "other layer" may contain known additives and stabilizers, such as antistatic agents, easy-adhesion coating agents, plasticizers, lubricants, antioxidants, etc. Also, the "other layer" may be one obtained by subjecting the surface of the film to corona treatment, plasma treatment, ozone treatment, chemical treatment, solvent treatment, etc. as a pretreatment in order to improve the adhesion when laminated with other materials.

[0155] The laminate of the present invention can be suitably used for various applications, such as packaging materials for foods, pharmaceuticals, 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, outdoor industrial applications such as signboards and stickers, decorative sheets used in injection molding simultaneous decoration methods, packaging materials for liquid detergents for laundry, liquid detergents for kitchens, liquid detergents for baths, liquid soaps for baths, liquid shampoos, and liquid conditioners.

[0156] <Packaging material> The laminate of the present invention can be used as a multilayer packaging material for protecting foods, pharmaceuticals, etc. When used as a multilayer packaging material, the layer structure can vary depending on the contents, usage environment, and usage form. Also, an easy-opening treatment or resealing means may be appropriately provided on the package of the present invention.

[0157] As an example of a specific embodiment of the packaging material of the present invention, for example, a packaging material formed by bagging a laminate having a sealant film, such as the above-described laminate configuration examples (1), (4) to (10), can be mentioned. 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 shape. Examples of the bag-making method include heat-sealing by forms such as side-sealing type, two-side sealing type, three-side sealing type, four-side sealing type, envelope sticking seal type, palm sticking seal type, pleat sticking seal type, flat-bottom seal type, corner-bottom seal type, gusset type, and other heat-sealing types. The packaging material of the present invention can take various forms according to the contents, usage environment, and usage form. A self-supporting packaging material (standing pouch) or the like is also possible. Examples of the heat-sealing method include known methods such as bar sealing, rotary roll sealing, belt sealing, impulse sealing, high-frequency sealing, and ultrasonic sealing.

[0158] After filling the contents into the packaging material of the present invention through its opening, the opening is heat-sealed to produce a product using the packaging material of the present invention. As the contents to be filled, for example, as foods, there are confectioneries such as rice confectioneries, bean confectioneries, nuts, biscuits & cookies, wafers confectioneries, marshmallows, pies, semi-baked cakes, candies, snack confectioneries, etc.; staples such as bread, snack noodles, instant noodles, dried noodles, pasta, aseptically packaged rice, congee, oatmeal, packaged mochi, cereal foods, etc.; processed agricultural products such as pickles, boiled beans, natto, miso, frozen tofu, tofu, shiitake mushrooms, konnyaku, processed wild vegetables, jams, peanut creams, salads, frozen vegetables, processed potato products, etc.; processed livestock products such as hams, bacon, sausages, processed chicken products, corned beef, etc.; processed fishery products such as fish ham & sausage, fishery processed products, kamaboko, nori, tsukudani, katsuobushi, salted fish, smoked salmon, spicy cod roe, etc.; fruits such as peaches, oranges, pineapples, apples, pears, cherries, etc.; vegetables such as corn, asparagus, mushrooms, onions, carrots, daikon radishes, potatoes, etc.; cooked foods such as frozen ready-to-eat foods, chilled ready-to-eat foods represented by hamburgers, meatballs, fish fries, gyoza, croquettes, etc.; dairy products such as butter, margarine, cheese, cream, instant creamy powder, formula milk for baby care, etc.; food products such as liquid seasonings, retort curries, pet foods, etc.

[0159] Also, as non-foods, there are pharmaceuticals such as cigarettes, disposable hand warmers, infusion packs, etc.; liquid detergents for laundry, liquid detergents for kitchen use, liquid detergents for bathing, liquid soaps for bathing, liquid shampoos, liquid conditioners, cosmetics such as lotions and emulsions, vacuum insulation materials, batteries, etc., and can also be used as various packaging materials.

Example

[0160] Hereinafter, the present invention will be described in more detail with 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 "mass%" respectively unless otherwise specified.

[0161] <Polyisocyanate Composition (X)> (Polyisocyanate Composition (X-1)) A polyurethane polyisocyanate (A1-1) of polypropylene polyol (average functionality 3, hydroxyl value 168 mg KOH / g) and toluene diisocyanate, and a mixture with a compound (A2-1-1) having an isocyanate group to which ricinoleic acid is bonded only at one end of toluene diisocyanate were used as the polyisocyanate composition (X-1). The content of toluene diisocyanate in the polyisocyanate composition (X-1) was 0.04% by mass, and the content of the compound (A2-1-1) was 1.0% by mass. The NCO% of the polyisocyanate composition (X-1) was 8.29%.

[0162] (Polyisocyanate Composition (X-2)) A polyurethane polyisocyanate (A1-1) of polypropylene polyol (average functionality 3, hydroxyl value 168 mg KOH / g) and toluene diisocyanate, and a mixture with a compound (A2-1-1) having an isocyanate group to which ricinoleic acid is bonded only at one end of toluene diisocyanate were used as the polyisocyanate composition (X-2). The content of toluene diisocyanate in the polyisocyanate composition (X-2) was 0.04% by mass, and the content of the compound (A2-1-1) was 0.1% by mass. The NCO% of the polyisocyanate composition (X-2) was 8.28%.

[0163] (Polyisocyanate Composition (X-3)) A polyurethane polyisocyanate (A1-1) of polypropylene polyol (average functionality 3, hydroxyl value 168 mg KOH / g) and toluene diisocyanate, and a mixture with a compound (A2-1-1) having an isocyanate group to which ricinoleic acid is bonded only at one end of toluene diisocyanate were used as the polyisocyanate composition (X-3). The content of toluene diisocyanate in the polyisocyanate composition (X-3) was 0.04% by mass, and the content of the compound (A2-1-1) was 5.0% by mass. The NCO% of the polyisocyanate composition (X-3) was 8.31%.

[0164] (Polyisocyanate Composition (X-4)) A polyurethane polyisocyanate (A1-1) of polypropylene polyol (average functionality 3, hydroxyl value 168 mg KOH / g) and toluene diisocyanate, and a compound (A2-1-2) having an isocyanate group to which 12-hydroxystearic acid is bonded only at one end of toluene diisocyanate were used as a polyisocyanate composition (X-4). The content of toluene diisocyanate in the polyisocyanate composition (X-4) was 0.04% by mass, and the content of the compound (A2-1-2) was 1.0% by mass. The NCO% of the polyisocyanate composition (X-4) was 8.29%.

[0165] (Polyisocyanate Composition (X-5)) A polyurethane polyisocyanate (A1-1) of polypropylene polyol (average functionality 3, hydroxyl value 168 mg KOH / g) and toluene diisocyanate, and a compound (A2-1-3) having an isocyanate group to which lactic acid is bonded only at one end of toluene diisocyanate were used as a polyisocyanate composition (X-5). The content of toluene diisocyanate in the polyisocyanate composition (X-5) was 0.04% by mass, and the content of the compound (A2-1-3) was 1.0% by mass. The NCO% of the polyisocyanate composition (X-5) was 8.36%.

[0166] (Polyisocyanate Composition (X-6)) A polyurethane polyisocyanate (A1-2) of refined castor oil (average functionality 2.6, hydroxyl value 160 mg KOH / g) and toluene diisocyanate, and a compound (A2-1-1) having an isocyanate group to which ricinoleic acid is bonded only at one end of toluene diisocyanate were used as a polyisocyanate composition (X-6). The content of toluene diisocyanate in the polyisocyanate composition (X-6) was 0.04% by mass, and the content of the compound (A2-1-1) was 1.0% by mass. The NCO% of the polyisocyanate composition (X-6) was 8.02%.

[0167] (Polyisocyanate Composition (X-7)) A polyurethane polyisocyanate (A1-3) of refined castor oil (average functionality 2.6, hydroxyl value 160 mg KOH / g) and hexamethylene diisocyanate, and a mixture with a compound (A2-1-4) having an isocyanate group to which ricinoleic acid is bonded only at one end of hexamethylene diisocyanate were used as the polyisocyanate composition (X-7). The content of hexamethylene diisocyanate in the polyisocyanate composition (X-7) was 0.04% by mass, and the content of the compound (A2-1-4) was 1.0% by mass. The NCO% of the polyisocyanate composition (X-7) was 8.11%.

[0168] (Polyisocyanate Composition (X-8)) A polyurethane polyisocyanate (A1-4) of polypropylene glycol (average functionality 2, hydroxyl value 112 mg KOH / g) and toluene diisocyanate, and a mixture with a compound (A2-1-1) having an isocyanate group to which ricinoleic acid is bonded only at one end of toluene diisocyanate were used as the polyisocyanate composition (X-8). The content of toluene diisocyanate in the polyisocyanate composition (X-8) was 0.04% by mass, and the content of the compound (A2-1-1) was 1.0% by mass. The NCO% of the polyisocyanate composition (X-8) was 6.26%.

[0169] (Polyisocyanate Composition (X'-1)) A polyurethane polyisocyanate (A1-1) of polypropylene polyol (average functionality 3, hydroxyl value 168 mg KOH / g) and toluene diisocyanate was used as the polyisocyanate composition (X'-1). The content of toluene diisocyanate in the polyisocyanate composition (X'-1) was 1.0% by mass. The NCO% of the polyisocyanate composition (X'-1) was 8.70%.

[0170] <Polyol Composition (Y)> (Polyol Composition (Y-1)) Polypropylene polyol (average functionality 3, hydroxyl value 168 mgKOH / g) was used as the polyol composition (Y-1).

[0171] (Polyol composition (Y-2)) A mixture of polypropylene glycol (average functionality 2, hydroxyl value 280 mgKOH / g): 40.0 parts, refined castor oil (average functionality 2.6, hydroxyl value 160 mgKOH / g): 45.3 parts, and Jeffamine T403: 7.8 parts was used as the polyol composition (Y-2).

[0172] (Production of evaluation samples) (Example 1) 1.4 parts of the polyisocyanate composition (X-1) and 0.6 parts of the polyol composition (Y-1) were stirred and mixed to prepare the adhesive of Example 1. The adhesive of Example 1 was applied to an OPP film (P2126 manufactured by Toyobo Co., Ltd.) at 2.0 g / m 2 and laminated with a VMCPP film (2703 manufactured by Toray Film Processing Co., Ltd.) using a nip roll (50°C). It was aged at 40°C for 3 days to obtain an OPP / VMCPP laminate.

[0173] (Examples 2 to 5, 7, 8, Comparative Example 1) Laminates were obtained in the same manner as in Example 1, except that the polyisocyanate composition (X) and the polyol composition (Y) used were changed to those described in Tables 1 and 2.

[0174] (Example 6) The heated polyisocyanate composition (X) was applied to the OPP film, and the heated polyol composition (Y) was applied to the VMCPP film. The PET film and the VMCPP film were laminated using a nip roll (50°C) and aged at 40°C for 3 days to obtain an OPP / VMCPP laminate. The coating amount of the polyisocyanate composition (X) was 1.4 g / m 2 , and the coating amount of the polyol composition (Y) was 0.6 g / m 2 .

[0175] (Evaluation) (Initial laminate strength) The laminated body after aging was cut into pieces with a length of 300 mm and a width of 15 mm. Using a tensile testing machine manufactured by Instron, the T-peel strength between OPP / VMCPP was measured at a peel rate of 300 mm / min in an environment of 25°C. This test was conducted 5 times, and the average value was obtained and evaluated according to the following criteria. The results are summarized in Tables 1 and 2. 5: 1.5 N / 15 mm or more 4: 1.0 N / 15 mm or more and less than 1.5 N / 15 mm 3: 0.5 N / 15 mm or more and less than 1.0 N / 15 mm 2: 0.2 N / 15 mm or more and less than 0.5 N / 15 mm 1: Less than 0.2 N / 15 mm

[0176] (Lamination strength after 6 months of storage) The laminated body after aging was further stored at room temperature for 6 months. Except for this, the lamination strength after 6 months of storage was measured in the same manner as the measurement of the initial lamination strength. The results are summarized in Tables 1 and 2.

[0177]

Table 1

[0178]

Table 2

Claims

1. A polyisocyanate composition (X) and a polyol composition (Y), The polyisocyanate composition (X) contains a polyurethane polyisocyanate (A1) and an isocyanate compound (A2) which is a reaction product of an aliphatic hydroxycarboxylic acid and a diisocyanate, The polyol composition (Y) comprises a polyol compound (B).

2. The two-component curing composition according to claim 1, wherein the aliphatic hydroxycarboxylic acid has a melting point of 80° C. or lower.

3. The two-component curing composition according to claim 1, wherein the aliphatic hydroxycarboxylic acid is at least one selected from the group consisting of glycolic acid, lactic acid, glyceric acid, hydroxybutyric acid, tartronic acid, malic acid, tartaric acid, citric acid, dimethylolpropionic acid, dimethylolbutanoic acid, ricinoleic acid, and 12-hydroxystearic acid.

4. The two-component curing composition according to claim 1 , wherein the polyurethane polyisocyanate (A1) is a reaction product of a polyol and a diisocyanate, and the polyol includes a tri- or higher functional polyol.

5. The two-component curing composition according to claim 4 , wherein the polyol has an average functionality of 2.1 or more and 3.5 or less.

6. The two-component curing composition according to claim 1, wherein a proportion of the isocyanate compound (A2) in the total amount of the polyurethane polyisocyanate (A1) and the isocyanate compound (A2) is 0.05 mass % or more and 10 mass % or less.

7. The two-component curing composition according to claim 1, wherein the content of diisocyanate monomer in the polyisocyanate composition (X) is 0.1 mass% or less.

8. The two-component curing composition according to any one of claims 1 to 7, which is a two-component curing adhesive.

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