Adhesive, laminate, method for manufacturing laminate, packaging material

Abstract

The present invention provides a solvent-free 2-liquid curing adhesive having excellent initial cohesiveness and suppressed reduction in cohesiveness over time, and the adhesive. The above-mentioned 2-liquid curing adhesive comprises: an isocyanate composition (X) containing a polyisocyanate compound (A); and a polyol composition (Y) containing a polyester polyol (B), a compound (C) containing a polyoxyalkylene chain and a hydroxyl group, and a polyamine (D), the polyester polyol (B) being at least one selected from a polyester polyol (B1) which is a reaction product of a polycarboxylic acid and a polyhydric alcohol, and a polycaprolactone polyol (B2), 90% by mass or more of the above-mentioned polyhydric alcohol being an aliphatic diol having an alkyl chain of 4 or more and 10 or less carbon atoms between two hydroxyl groups, the total amount of the polyester polyol (B), the compound (C), and the polyamine (D) being 90% by mass or more in the solid content of the polyol composition (Y).

Description

Technical Field

[0001] This invention relates to a two-component curing adhesive, a laminate, a method for manufacturing the laminate, and packaging materials. Background Technology

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

[0003] Previously, the mainstream method for laminates used in packaging materials was to dry-laminate the substrate by applying an adhesive dissolved in a volatile organic solvent (sometimes called a solvent-based laminating adhesive), evaporating the organic solvent during the drying process, and then bonding it to other substrates. However, in recent years, from the perspective of reducing environmental impact and improving the working environment, the demand for reactive two-component laminating adhesives that do not contain volatile organic solvents (hereinafter referred to as solvent-free adhesives) has been increasing (Patent Document 1).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2014-159548 Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] Solvent-free adhesives use polyisocyanate and polyol compounds that differ from solvent-based adhesives. They must achieve a viscosity that allows for application even without dilution with organic solvents, necessitating a lower molecular weight. However, reducing the molecular weight of polyisocyanate and polyol compounds also decreases initial cohesion, leading to residual air bubbles in the adhesive and a deterioration in the finished appearance of the laminate.

[0009] To mitigate this adverse effect, it was considered to use polyamine compounds, which exhibit higher reactivity with polyisocyanate compounds than with polyol compounds, as components of the adhesive. The inventors studied such adhesives and found that, for adhesives stored for a certain period, the initial cohesive strength decreased compared to when they were first prepared.

[0010] The present invention was made in view of the following circumstances, and its object is to provide a solvent-free two-component curing adhesive with excellent initial cohesiveness and suppressed degradation over time, a laminate obtained using the adhesive, a method for manufacturing the laminate, and a packaging material.

[0011] Methods for solving problems

[0012] This invention relates to a two-component curing adhesive comprising: an isocyanate composition (X) containing a polyisocyanate compound (A); and a polyol composition (Y) containing a polyester polyol (B), a compound (C) containing a polyoxyalkylene chain and hydroxyl groups, and a polyamine (D), wherein the polyester polyol (B) is at least one selected from polyester polyol (B1) and polycaprolactone polyol (B2), wherein the polyester polyol (B1) is a reaction product of a polycarboxylic acid and a polyvalent alcohol, and wherein at least 90% by mass of the polyvalent alcohol is an aliphatic diol with 4 or more and 10 or less carbon atoms in the alkyl chain connecting two hydroxyl groups, and the total amount of the polyester polyol (B), compound (C), and polyamine (D) accounts for at least 90% by mass of the solid component of the polyol composition (Y).

[0013] Invention Effects

[0014] According to the present invention, an adhesive can be provided that maintains excellent initial cohesion even after a certain period of storage and can suppress the deterioration of the processed appearance. Detailed Implementation

[0015] <Adhesive>

[0016] The adhesive of the present invention is a two-component curing adhesive comprising a polyisocyanate composition (X) and a polyol composition (Y). The adhesive of the present invention will be described in detail below.

[0017] (Polyisocyanate composition (X))

[0018] (Polyisocyanate compound (A))

[0019] The polyisocyanate composition (X) comprises a polyisocyanate compound (A) having a plurality of isocyanate groups. The polyisocyanate compound (A) is not particularly limited, and examples include aromatic diisocyanates, aromatic aliphatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and biuret forms, ureates, adducts, urea carbamates, carbodiimide-modified forms, urea diketone-modified forms, and urethane prepolymers obtained by reacting these polyisocyanates with polyols, etc., which may be used alone or in combination.

[0020] Examples of aromatic diisocyanates include, but are not limited to, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate (also known as polymeric MDI or crude MDI), 1,3-phenyl diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenyl diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, o-anisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, and 4,4',4”-triphenylmethane triisocyanate.

[0021] Aromatic aliphatic diisocyanates refer to aliphatic isocyanates having one or more aromatic rings in their molecules. Examples include meta- or terephthalic diisocyanate (also known as XDI) and α,α,α',α'-tetramethylphenyldiisocyanate (also known as TMXDI), but are not limited to these.

[0022] Examples of aliphatic diisocyanates include, but are not limited to, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate, 1,2-propylidene diisocyanate, 2,3-butylidene diisocyanate, 1,3-butylidene diisocyanate, dodecamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate.

[0023] Examples of alicyclic diisocyanates include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, isophorone diisocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), and 1,4-bis(isocyanate methyl)cyclohexane, but are not limited to these.

[0024] Examples of polyols used in the synthesis of urethane prepolymers include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentanediol, methylpentanediol, dimethylbutanediol, butyl ethyl propylene glycol, 1,4-cyclohexanediol, and alkylene glycols.

[0025] Bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, and other bisphenols;

[0026] Dimer diol;

[0027] Dihydroxyethoxybenzene;

[0028] Diethylene glycol, triethylene glycol, other polyethylene glycols, polypropylene glycol, polybutylene glycol and other polyalkylene glycols;

[0029] Polyether polyols containing urethane bonds are obtained by further increasing the molecular weight of polyalkylene glycols with aromatic or aliphatic polyisocyanates.

[0030] Polyester polyols are obtained by reacting the above-mentioned alkylene glycols or polyalkylene glycols with at least one of the following aliphatic dicarboxylic acids with 2 to 13 carbon atoms: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, octanoic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, etc., as well as aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.

[0031] Polyester polyols are products of the reaction of polyesters obtained by the ring-opening polymerization of cyclic ester compounds such as proprolactone, butyrolactone, ε-caprolactone, σ-valerolactone, and β-methyl-σ-valerolactone with polyvalent alcohols such as glycols, glycerol, trimethylolpropane, and pentaerythritol.

[0032] The polyisocyanate compound (A) preferably comprises a urethane prepolymer as a reaction product of a diisocyanate and at least one selected from polyester polyols and polyether polyols. The diisocyanate preferably comprises an aromatic diisocyanate, more preferably 2,4'-diphenylmethane diisocyanate and / or 4,4'-diphenylmethane diisocyanate. The number average molecular weight of the polyester polyol is preferably 300 or more and 3000 or less. The number average molecular weight of the polyether polyol is preferably 300 or more and 3000 or less.

[0033] Alternatively, the polyisocyanate compound (A) is preferably a ureate body comprising an aliphatic diisocyanate or an alicyclic diisocyanate.

[0034] The isocyanate composition (X) preferably has a viscosity of 300 mPa·s or more and 10,000 mPa·s or less at 50°C, and more preferably 450 mPa·s or more and 8,000 mPa·s or less. This facilitates the provision of laminates with superior appearance. It should be noted that the viscosity of the polyisocyanate composition (X) in this application is measured using a rotational viscometer at a cone / plate angle of 1° × diameter of 50 mm and a shear rate of 100 sec. -1 The values ​​were determined under conditions of 50℃±1℃. The viscosity of the isocyanate composition (X) can be adjusted by the polyisocyanate compound (A1) used and its formulation amount.

[0035] (Polyol Composition (Y))

[0036] The polyol composition (Y) comprises: a polyester polyol (B), a compound comprising a polyoxyalkylene chain and hydroxyl groups (C), and a polyamine (D).

[0037] (Polyester Polyol (B))

[0038] Polyester polyol (B) comprises at least one selected from polyester polyol (B1) and polycaprolactone polyol (B2), wherein the polyester polyol (B1) is a reaction product of a polyvalent alcohol and a polycarboxylic acid. At least 90% by mass of the polyvalent alcohol used as a raw material for synthesizing polyester polyol (B1) is an aliphatic diol with 4 or more but less than 10 carbon atoms in the alkyl chain connecting the two hydroxyl groups. The total amount of the polyvalent alcohol can be such an aliphatic diol. It should be noted that the number of carbon atoms in the alkyl chain connecting the two hydroxyl groups does not include the number of carbon atoms in the side chain.

[0039] Examples of aliphatic diols used in the synthesis of polyester polyols (B1) that have 4 or more but less than 6 carbon atoms in the alkyl chain connecting two hydroxyl groups include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and 1,9-nonanediol, but are not limited to these. One type can be used alone, or two or more can be used in combination.

[0040] The polyols used as raw materials for polyester polyols (B 1) can include polyols other than the aliphatic diols mentioned above. Such polyols can be diols or polyols with three or more functions. Examples of diols include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,2,2-trimethyl-1,3-propanediol, 2,2-dimethyl-3-isopropyl-1,3-propanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, neopentyl glycol, 1,4-bis(hydroxymethyl)cyclohexane, and 2,2,4-trimethyl-1,3-pentanediol, among other aliphatic diols.

[0041] Polyoxyethylene glycol, polyoxypropylene glycol and other ether glycols;

[0042] Modified polyether diols are obtained by ring-opening polymerization of aliphatic diols with various compounds containing cyclic ether bonds, such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether.

[0043] Lactone-based polyester polyols are obtained through the polycondensation reaction of aliphatic diols with various lactones such as lactol and ε-caprolactone.

[0044] Bisphenol A, bisphenol F, and other bisphenols;

[0045] Bisphenol alkyl oxide adducts obtained by adding bisphenol A, bisphenol F and other bisphenols to ethylene oxide, propylene oxide and other compounds.

[0046] Examples of polyols with three or more functions include aliphatic polyols such as trimethylolethane, trimethylolpropane, glycerol, hexanetriol, and pentaerythritol.

[0047] Modified polyether polyols are obtained by ring-opening polymerization of aliphatic polyols with various compounds containing cyclic ether bonds, such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether.

[0048] Lactone-based polyester polyols are obtained through the polycondensation reaction of aliphatic polyols with various lactones such as ε-caprolactone.

[0049] Examples of aliphatic dicarboxylic acids used in the synthesis of polyester polyols (B) include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid; aliphatic polycarboxylic acids such as dimer acids; and anhydrides or ester-forming derivatives of these aliphatic polycarboxylic acids.

[0050] Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalenedicarboxylic acid, biphenyl dicarboxylic acid, and 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid; aromatic polycarboxylic acids such as trimellitic acid and pyromellitic acid; and anhydrides or ester-forming derivatives of these aromatic polycarboxylic acids.

[0051] The number-average molecular weight of the polyester polyol (B1) is not particularly limited, but as an example, it is preferably 300 or more and 4000 or less. It should be noted that the number-average molecular weight in this specification is a value determined using gel permeation chromatography (GPC) under the conditions described below.

[0052] Measurement apparatus: HLC-8320GPC manufactured by Tosoh Corporation

[0053] Column: TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel1000HXL manufactured by Tosoh Corporation

[0054] Detector: RI (Differential Refractometer)

[0055] Data processing: MultiStation GPC-8020modelII manufactured by Tosoh Corporation

[0056] Measurement conditions: Column temperature 40℃

[0057] solvent tetrahydrofuran

[0058] Flow rate 0.35 ml / min

[0059] Standard: Monodisperse polystyrene

[0060] Sample: 100 μl of a tetrahydrofuran solution (converted to 0.2% by mass based on resin solids) obtained by filtering it through a microfilter.

[0061] Polycaprolactone polyol (B2) is obtained by polycondensation reaction of aliphatic diols or polyols with ε-caprolactone.

[0062] There is no particular limitation on the number average molecular weight of polycaprolactone polyols, but as an example, it is preferred to be 300 or more and 4000 or less.

[0063] The viscosity of the polyester polyol (B) at 50°C is preferably 50 mPa·s or more and 10,000 mPa·s or less, more preferably 100 mPa·s or more and 5,000 or less.

[0064] Examples of compounds (C) that contain polyoxyalkylene chains and hydroxyl groups include polyether polyols (C1) and polyoxyalkylene monools (C2).

[0065] Examples of polyether polyols (C1) include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentanediol, methylpentanediol, dimethylbutanediol, butylethyl propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dihydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanediol, and triethylene glycol. These are substances obtained by addition polymerization of ethylene oxide, propylene oxide, butane oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, cyclohexene, and other epoxides in the presence of polymerization initiators such as glycerol, trimethylolpropane, pentaerythritol, and triols of polypropylene glycol. Polypropylene polyols are preferred.

[0066] The number average molecular weight of polyether polyols (C1) is not particularly limited, but as an example, it is preferably 300 or more and 4000 or less.

[0067] Examples of polyoxyalkylene monools (C2) include substances obtained by using alkyl compounds containing one active hydrogen atom as initiators to perform ring-opening addition polymerization on ethylene oxide, propylene oxide, butane oxide, tetrahydrofuran, and other epoxides.

[0068] (Polyamine(D))

[0069] Polyamines (D) have multiple amino groups (NH2 group or NHR group (R is an alkyl or aryl group that may have functional groups)). As the polyamine (D), known polyamines can be used without particular restriction, including methyldiamine, ethylenediamine, isophorone diamine, 3,9-dipropylamine-2,4,8,10-tetraoxaspiroundecane, lysine, phenylenediamine, 2,2,4-trimethylhexamethylenediamine, toluenediamine, hydrazine, piperazine, hexamethylenediamine, propylenediamine, dicyclohexylmethane-4,4-diamine, 2-hydroxyethylethylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine or di-2-hydroxypropylethylenediamine, polyoxyethylenediamine, polyoxyethylenetriamine, polyoxyethylenetetramine, polyoxypropylenediamine, polyoxypropylenetriamine, polyoxypropylenetetramine and other polyoxyalkylene polyamines, 1,2-diaminopropane, 1,3-diaminopropane, etc.

[0070] 1,4-Diaminobutane, 1,5-Diaminopentane, 1,6-Diaminohexane, 1,7-Diaminoheptane, 1,8-Diaminooctane, 1,9-Diaminononane, 1,10-Diaminodecane, etc.; benzylamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentethylenehexamine, nonaethylenedecamine, trimethylhexamethylenediamine, etc.; tetra(aminomethyl)methane, tetra(2-aminoethylaminomethyl)methane, 1,3-bis(2'-aminoethylamino)propane, triethylene-bis(triethylene)hexamine, bis(3-aminoethyl)amine, bishexamethylenetriamine, etc.; 1,4-cyclohexanediamine, 4,4'-methylenebicyclohexylamine, 4,4'-isopropylidenebicyclohexylamine, norbornenediamine, etc.

[0071] bis(aminomethyl)cyclohexane, diaminodicyclohexylmethane, isophorone diamine, menthene diamine, etc., bis(aminoalkyl)benzene, bis(aminoalkyl)naphthalene, bis(cyanoethyl)diethylenetriamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, phenylenediamine, naphthylenediamine, diaminodiphenylmethane, diaminodiethylphenylmethane, 2,2-bis(4-aminophenyl)propane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 2,2'-dimethyl-4,4'-diaminodiphenyl Methane, 2,4'-diaminobiphenyl, 2,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, bis(aminomethyl)naphthalene, bis(aminoethyl)naphthalene, N-methylpiperazine, morpholine, 1,4-bis-(8-aminopropyl)piperazine, piperazine-1,4-diazacycloheptane, 1-(2'-aminoethylpiperazine), 1-[2'-(2”-aminoethylamino)ethyl]piperazine, tricyclodecanediamine, and polyurea, which are the reaction products of the above-mentioned polyamines and the above-mentioned isocyanate components, and other amine compounds having multiple amino groups, may be used in combination with one or more of them.

[0072] From the viewpoint of balancing adhesion to the metal substrate, the appearance of the laminate, and the pot life, the amount of polyamine (D) is preferably adjusted so that the amine value of the newly formulated polyol composition (Y) is 1 mg KOH / g or more and 100 mg KOH / g or less, and preferably 10 mg KOH / g or more and 80 mg KOH / g or less. This allows for the production of adhesives with superior processing appearance.

[0073] It should be noted that the amine value in this specification refers to the number of milligrams of KOH equivalent to the amount of HCl required to neutralize 1g of sample. There are no particular limitations, and it can be calculated using known methods. When the chemical structure of the polyamine (D) is known, and the required average molecular weight is obtained, it can be calculated using (number of amino groups per molecule / average molecular weight) × 56.1 × 1000. When the chemical structure and average molecular weight of the polyamine (D) are unknown, it can be determined according to known methods for amine value determination, such as JIS K7237-1995.

[0074] In the adhesive of the present invention, the total amount of polyester polyol (B), polyether polyol (C), and polyamine (D) accounts for 90% or more of the solid components of the polyol composition (Y). Therefore, an adhesive with excellent processing appearance and sustained performance after a certain period of storage can be produced.

[0075] From the perspective of becoming an adhesive with excellent processing appearance and lamination strength, the amount of polyester polyol (B) in the solid component of the polyol composition (Y) is preferably 10% by mass or more and 80% by mass or less. The amount of polyether polyol (C) in the solid component of the polyol composition (Y) is preferably 15% by mass or more and 80% by mass or less.

[0076] The polyol composition (Y) may contain compounds (E) with active hydrogen groups other than polyester polyols (B), polyether polyols (C), and polyamines (D). Examples of such active hydrogen compounds include polyester polyols (E1) other than polyester polyols (B), vegetable oil polyols (E2), and amine compounds (E3) having multiple hydroxyl groups. However, the proportion of compound (E) in the polyol composition (Y) is less than 10% by mass. The polyol composition may not contain these compounds (E) with active hydrogen groups.

[0077] The polyvalent alcohols and polycarboxylic acids used as raw materials for polyester polyols (E1) can be the same substances as those exemplified as raw materials for polyester polyols (B).

[0078] Examples of vegetable oil polyols (E2) include castor oil, dehydrated castor oil, hydrogenated castor oil as a hydride of castor oil, and 5-50 molar adducts of castor oil epoxides.

[0079] Examples of amine compounds (E3) having multiple hydroxyl groups include polypropylene glycol ethylenediamine ether, propylene oxide adducts of triethanolamine, N-ethyldiethanolamine, N-methyl-N-hydroxyethyl-N-hydroxyethoxyethylamine, pentahydroxypropyl diethylenetriamine, tetrahydroxypropyl ethylenediamine, N,N,N',N'-tetra(2-hydroxypropyl)ethylenediamine, triethanolamine, and amino-containing aspartic acid esters. The hydroxyl groups in the amine compound (E3) having multiple hydroxyl groups are preferably secondary or tertiary hydroxyl groups.

[0080] The viscosity of the polyol composition (Y) at 50°C is preferably 50 mPa·s or higher and 500 mPa·s or lower.

[0081] (Other components of the adhesive)

[0082] The adhesive of the present invention may contain components other than those described above. Other components may be included in any one or both of the polyisocyanate composition (X) and polyol composition (Y), or may be prepared separately in advance and mixed with the polyisocyanate composition (X) and polyol composition (Y) before the adhesive is applied. The components will be described below.

[0083] (Carbamate catalyst)

[0084] Examples of urethane esterification catalysts include metal-based catalysts, amine-based catalysts, and aliphatic cyclic amide compounds.

[0085] Examples of metal-based catalysts include metal complex-based, inorganic metal-based, and organometallic catalysts. Examples of metal complex-based catalysts include acetylacetone salts of metals selected from Fe (iron), Mn (manganese), Cu (copper), Zr (zirconium), Th (thorium), Ti (titanium), Al (aluminum), and Co (cobalt), such as iron acetylacetone, manganese acetylacetone, copper acetylacetone, and zirconium oxide acetylacetone.

[0086] Examples of inorganic metal catalysts include substances selected from Sn, Fe, Mn, Cu, Zr, Th, Ti, Al, and Co.

[0087] Examples of organometallic catalysts include organozinc compounds such as zinc octanoate, zinc neodecanoate, and zinc naphthenate; organotin compounds such as stannous diacetate, stannous dioctanoate, stannous dioleate, stannous dilaurate, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin oxide, and dibutyltin dichloride; organonitrile compounds such as nickel octanoate and nickel naphthenate; organocobalt compounds such as cobalt octanoate and cobalt naphthenate; organobismuth compounds such as bismuth octanoate, bismuth neodecanoate, and bismuth naphthenate; titanium compounds such as tetraisopropyl titanate, dibutyltitanium dichloride, tetrabutyl titanate, butoxytitanium trichloride, and titanium chelates that use at least one of aliphatic diketones, aromatic diketones, or alcohols with 2 to 10 carbon atoms as ligands.

[0088] Examples of amine catalysts include triethylenediamine, 2-methyltriethylenediamine, quinine ring, 2-methylquinine ring, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropanediamine, N,N,N',N”,N”-pentamethyldiethylenetriamine, N,N,N',N”,N”-pentamethyl-(3-aminopropyl)ethylenediamine, N,N,N',N”,N”-pentamethyldipropylenetriamine, N,N,N',N’-tetramethylhexamethylenediamine, bis(2-dimethylaminoethyl) ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol, N,N-dimethyl-N'-(2-hydroxyethyl)ethylenediamine, N,N-dimethyl-N'-(2-hydroxyethyl)propanediamine, bis(dimethylaminopropyl)amine, and bis(dimethyl... (N,N,N',N'-tetramethylguanidine, 1,3,5-tris(N,N-dimethylaminopropyl)hexahydro-triazine, 1,8-diazabicyclo[5.4.0]undecene-7, N-methyl-N'-(2-dimethylaminoethyl)piperazine, N,N'-dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, 1-methylimidazolium, 1,2-dimethylimidazolium, 1-isobutyl-2-methylimidazolium, 1-dimethylaminopropylimidazolium, N,N-dimethylhexanolamine, N-methyl-N'-(2-hydroxyethyl)piperazine, 1-(2-hydroxyethyl)imidazolium, 1-(2-hydroxypropyl)imidazolium, 1-(2-hydroxyethyl)imidazolium, 1-(2-hydroxypropyl)imidazolium, 1-(2-hydroxyethyl)-2-methylimidazolium, 1-(2-hydroxypropyl)-2-methylimidazolium, etc.

[0089] Examples of aliphatic cyclic amide compounds include δ-valeramide, ε-caprolactam, ω-heptanolactam, η-octanolactam, and β-propiolactam. Among these, ε-caprolactam is more effective at promoting curing.

[0090] Organometallic catalysts are preferably used, and at least one selected from organozinc compounds, organotin compounds, and organobismuth compounds is preferred, with organotin compounds being the most common. The amount of the organometallic catalyst is preferably 0.005% by mass or more and 1.0% by mass or less of the total binder. When the organometallic catalyst is an organozinc compound, its amount is preferably 0.05% by mass or more and 1.0% by mass or less of the total binder. When the organometallic catalyst is an organotin compound, its amount is preferably 0.005% by mass or more and 0.5% by mass or less of the total binder. When the organometallic catalyst is an organobismuth compound, its amount is preferably 0.05% by mass or more and 1.0% by mass or less of the total binder.

[0091] (acid anhydride)

[0092] As the acid anhydride, cyclic aliphatic acid anhydrides, aromatic acid anhydrides, unsaturated carboxylic acid anhydrides, etc. can be cited, and one kind or two or more kinds in combination can be used. More specifically, for example, phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, dodecenyl succinic anhydride, polyadipic anhydride, polynonanoic anhydride, sebacic anhydride, poly(ethyl octadecanedioic) anhydride, poly(phenyl hexadecanedioic) anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methyl humic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, methylcyclohexene tetracarboxylic anhydride, ethylene glycol bis(trimellitate) dianhydride, chlorendic anhydride, nadic anhydride, methyl nadic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, etc. can be cited.

[0093] In addition, as the acid anhydride, a substance obtained by modifying the above compound with a diol can also be used. As the diol that can be used for modification, alkylene diols such as ethylene glycol, propylene glycol, and neopentyl glycol can be cited; polyether diols such as polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol can be cited, etc. In addition, a copolymer polyether diol of two or more kinds of diols and / or polyether diols among them can also be used.

[0094] (Coupling agent)

[0095] As the coupling agent, silane coupling agents, titanate coupling agents, aluminum coupling agents, etc. can be cited.

[0096] As the silane coupling agent, amino silanes such as γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane can be cited; epoxy silanes such as β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane can be cited; vinyl silanes such as vinyl tris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane can be cited; hexamethyldisilazane, γ-mercaptopropyltrimethoxysilane, etc.

[0097] As the titanate coupling agent, for example, tetraisopropoxy titanium, tetra-n-butoxy titanium, titanium butoxide dimer, tetra-stearoyl titanate, titanium acetylacetonate, titanium lactate, tetraoctyldiol titanate, titanium lactate, tetra-stearoxytitanium, etc. can be cited.

[0098] As an aluminum-based coupling agent, examples include aluminum acetylalkoxydipropanol, etc.

[0099] (Pigment)

[0100] As the pigment, there is no particular limitation, and examples include extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments, green pigments, blue pigments, metallic powder pigments, luminous pigments, pearlescent pigments, etc., such as organic pigments, inorganic pigments, and plastic pigments described in the Paint Raw Material Handbook 1970 Edition (edited by the Japan Paint Industry Association).

[0101] As extender pigments, examples include precipitated barium sulfate, white pigment (original Japanese: ご粉), precipitated calcium carbonate, calcium hydrogen carbonate, gypsum, alumina white, silica, hydrated micropowder silica (white carbon), ultramicropowder anhydrous silica (AEROSIL), silica sand (silicon dioxide sand), talc, precipitated magnesium carbonate, bentonite, clay, kaolin, loess, etc.

[0102] Specific examples of organic pigments include various insoluble azo pigments such as benzidine yellow, Hansa yellow, and lake red 4R; soluble azo pigments such as lake red C, carmine 6B, and bordeaux 10; various (copper) phthalocyanine-based pigments such as phthalocyanine blue and phthalocyanine green; various basic dye lakes such as rhodamine lake and methyl violet lake; various mordant dye-based pigments such as quinoline lake and fast sky blue; various vat dye-based pigments such as anthraquinone-based pigments, thioindigo-based pigments, and violanthrone-based pigments; various quinacridone-based pigments such as Cinquasia Red B; various dioxazine-based pigments such as dioxazine purple; various condensed azo pigments such as Cibanone; and aniline black, etc.

[0103] As inorganic pigments, examples include various chromates such as chrome yellow, zinc chromate, and molybdenum orange; various ferrocyanides such as Prussian blue; various metal oxides such as titanium oxide, zinc white, brown 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 metallic 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; mica / flake pigments in the form of being coated with metal oxides, and metallic pigments and pearlescent pigments such as micaceous iron oxide pigments; graphite, carbon black, etc.

[0104] As plastic pigments, examples include "GRANDOLL PP-1000", "PP-2000S", etc. manufactured by DIC Corporation.

[0105] Regarding the pigments used, appropriate selection can be made according to the purpose. For example, considering factors such as durability, weather resistance, and excellent design, inorganic oxides such as titanium dioxide and zinc white are preferred as white pigments, while carbon black is preferred as a black pigment.

[0106] Regarding the amount of pigment, as an example, it is 1 to 400 parts by mass relative to 100 parts by mass of the total amount of non-volatile components of the polyol composition (X) and the polyisocyanate composition (Y), and more preferably 10 to 300 parts by mass in order to improve adhesion and anti-blocking properties.

[0107] (Plasticizer)

[0108] Examples of plasticizers include phthalic acid-based plasticizers, fatty acid-based plasticizers, aromatic polycarboxylic acid-based plasticizers, phosphoric acid-based plasticizers, polyol-based plasticizers, epoxy-based plasticizers, polyester-based plasticizers, and carbonate-based plasticizers.

[0109] Examples of phthalic acid-based plasticizers include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, di-n-octyl phthalate, dinonyl phthalate, diisononyl phthalate, didecyl phthalate, diisodecyl phthalate, di(tridecyl) phthalate, di(undecyl) phthalate, and phthalic acid phthalate. Phthalate ester plasticizers include dilaurate formate, distearate phthalate, diphenyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, dicyclohexyl phthalate, octyl decyl phthalate, dimethyl isophthalate, di(2-ethylhexyl) isophthalate, and diisooctyl isophthalate, as well as tetrahydrophthalate ester plasticizers such as di(2-ethylhexyl) tetrahydrophthalate, di-n-octyl tetrahydrophthalate, and diisodecyl tetrahydrophthalate.

[0110] Examples of fatty acid-based plasticizers include di-n-butyl adipate, di(2-ethylhexyl) adipate, diisodecyl adipate, diisononyl adipate, di(C6-C10) alkyl adipate, and di(butyl diethylene glycol) adipate (Japanese original: ジブチルジグリコールアジペート), as well as di-n-hexyl azelate and di(2-ethylhexyl) azelate. Azelaic acid-based plasticizers, such as diisooctyl azelate; sebacate-based plasticizers, such as di-n-butyl sebacate, di(2-ethylhexyl) sebacate, and diisononyl sebacate; maleic acid-based plasticizers, such as dimethyl maleate, diethyl maleate, di-n-butyl maleate, and di(2-ethylhexyl) maleate; and fumarate-based plasticizers, such as di-n-butyl fumarate and di(2-ethylhexyl) fumarate. Examples of plasticizers include: itaconic acid-based plasticizers such as monomethyl itaconic acid, monobutyl itaconic acid, dimethyl itaconic acid, diethyl itaconic acid, dibutyl itaconic acid, and di(2-ethylhexyl) itaconic acid; stearic acid-based plasticizers such as n-butyl stearate, glyceryl monostearate, and diethylene glycol distearate; oleic acid-based plasticizers such as butyl oleate, glyceryl monooleate, and diethylene glycol monooleate; citric acid-based plasticizers such as triethyl citrate, tri-n-butyl citrate, triethyl acetyl citrate, tributyl acetyl citrate, and tri(2-ethylhexyl) acetyl citrate; ricinoleic acid-based plasticizers such as methyl acetyl ricinoleate, butyl acetyl ricinoleate, glyceryl monoricinoleate, and diethylene glycol monoricinoleate; and other fatty acid-based plasticizers such as diethylene glycol monolaurate, diethylene glycol dinonanoate, and pentaerythritol fatty acid esters.

[0111] Examples of aromatic polycarboxylic acid plasticizers include trimellitic acid plasticizers such as tri-n-hexyl trimellitate, tri(2-ethylhexyl) trimellitate, tri-n-octyl trimellitate, triisooctyl trimellitate, triisononyl trimellitate, tridecyl trimellitate, and triisodecyl trimellitate; and pyromellitic acid plasticizers such as tetra(2-ethylhexyl) pyromellitic acid and tetra-n-octyl pyromellitic acid.

[0112] Examples of phosphoric acid-based plasticizers include triethyl phosphate, tributyl phosphate, tri(2-ethylhexyl) phosphate, tri(butoxyethyl) phosphate, triphenyl phosphate, octyl diphenyl phosphate, tolyl diphenyl phosphate, tolyl phenyl phosphate, tri(tolyl) phosphate, tri(xyl) phosphate, tri(chloroethyl) phosphate, tri(chloropropyl) phosphate, tri(dichloropropyl) phosphate, and tri(isopropylphenyl) phosphate.

[0113] Examples of polyol-based plasticizers include diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, triethylene glycol di(2-ethylbutyrate), triethylene glycol di(2-ethylhexanoate), dibutyl methylene dithioglycolate, and glycerol-based plasticizers such as glyceryl monoacetate, glyceryl triacetate, and glyceryl tributyrate.

[0114] Examples of epoxy-based plasticizers include epoxidized soybean oil, epoxidized butyl stearate, epoxidized di(2-ethylhexyl) phthalate, epoxidized diisodecyl phthalate, epoxidized triglyceride, epoxidized octyl oleate, and epoxidized decyl oleate.

[0115] Examples of polyester plasticizers include adipic acid-based polyesters, sebacic acid-based polyesters, and phthalic acid-based polyesters.

[0116] Examples of carbonate-based plasticizers include propylene carbonate and ethylene carbonate.

[0117] In addition, other plasticizers include partially hydrogenated terphenyl, adhesive plasticizers, diallyl phthalate, acrylic monomers, oligomers, and other polymeric plasticizers. These plasticizers can be used alone or in combination of two or more.

[0118] (Phosphoric acid compounds)

[0119] Examples of phosphoric acid compounds include phosphoric acid, pyrophosphate, triphosphate, methyl phosphate, ethyl phosphate, butyl phosphate, dibutyl phosphate, 2-ethylhexyl phosphate, bis(2-ethylhexyl) phosphate, isododecyl phosphate, butoxyethyl phosphate, alkenyl phosphate, tetradecyl phosphate, 2-hydroxyethyl methacrylate, polyoxyethylene alkyl ether phosphate, etc.

[0120] (Hydroxycarboxylic acid)

[0121] From the perspective of improving adhesion to the metal substrate, it is also preferable to include at least one selected from 2,2-dimethylolacetic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, and 2,2-dimethylolvalerate. The amount of the hydroxycarboxylic acid is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, more preferably 10% by mass or less, and more preferably 2.5% by mass or less of the polyol composition (Y).

[0122] (Adhesive method)

[0123] The adhesive of the present invention can be used in a solvent-free manner. It should be noted that, in this specification, "solvent-free" adhesive refers to the adhesive used in the following method, namely the so-called solvent-free lamination method: the polyisocyanate composition (X) and the polyol composition (Y) are substantially free of esters such as ethyl acetate, butyl acetate, and cellosol acetate; ketones such as acetone, methyl ethyl ketone, isobutyl ketone, and cyclohexanone; ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane and dichloroethane; and highly soluble organic solvents such as dimethyl sulfoxide and dimethyl sulfonamide, especially ethyl acetate or methyl ethyl ketone. After the adhesive is applied to the substrate, it is bonded to other substrates without a process of heating in an oven or the like to evaporate the solvent. When trace amounts of organic solvent used as a reaction medium in the manufacture of the components of the polyisocyanate composition (X) or the polyol composition (Y) are not completely removed, and thus remain in the polyisocyanate composition (X) or the polyol composition (Y), it can be understood that the composition is substantially free of organic solvents. Furthermore, if the polyol composition (Y) contains a low molecular weight alcohol, the low molecular weight alcohol reacts with the polyisocyanate composition (X) to become part of the coating film; therefore, it does not need to evaporate after application. Thus, this method is also used as a solvent-free adhesive, and the low molecular weight alcohol is not considered an organic solvent.

[0124] The adhesive of the present invention is preferably used in a formulation in which the molar ratio of the isocyanate groups [NCO] contained in the polyisocyanate composition (X) to the molar amount of the active hydrogen groups (hydroxyl, amino) contained in the polyol composition (Y) [NCO] / [OH+NH] is 1.0 to 3.0. This allows for appropriate curing properties regardless of the ambient humidity at the time of application.

[0125] <Layered Body>

[0126] The adhesive of the present invention is suitable for use in the manufacture of laminates. Such laminates are obtained by bonding multiple substrates (films or papers) using the above-described adhesive.

[0127] There are no particular restrictions on the type of film used; films appropriate for the intended use can be selected. For example, for food packaging, examples include polyethylene terephthalate (PET) film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film (LLDPE: low-density polyethylene film, HDPE: high-density polyethylene film, MDOPE: uniaxially stretched polyethylene film, OPE: biaxially stretched polyethylene film), polypropylene film (CPP: non-stretched polypropylene film, OPP: biaxially stretched polypropylene film), and gas barrier films such as polyolefin films, polyvinyl alcohol films, and ethylene-vinyl alcohol copolymer films, which are obtained by setting an olefin-based heat-sealing resin layer on one or both sides of a gas barrier resin such as ethylene-vinyl alcohol copolymer or polyvinyl alcohol.

[0128] In addition, biofilms made from materials containing components derived from biomass are preferred. Besides being sold by individual companies, biofilms can also be sheets listed in the Biomass Certified Products List kept by the Japan Organic Resources Foundation.

[0129] As a known specific example of a biomass membrane, one can cite a biomass membrane using ethylene glycol derived from biomass as a raw material. Ethylene glycol derived from biomass uses ethanol (biomass ethanol) produced from biomass as a raw material. For example, for biomass ethanol, ethylene glycol derived from biomass can be obtained using conventionally known methods, such as methods for producing ethylene glycol from ethylene oxide. Alternatively, commercially available biomass ethylene glycol can be used, for example, biomass ethylene glycol sold by India Glycols Co., Ltd. is suitable.

[0130] For example, as a replacement for conventional polyethylene terephthalate membranes that use petroleum-based raw materials, membranes containing biomass polyesters and biomass polyethylene terephthalate are known to contain ethylene glycol from biomass as diol units and dicarboxylic acid from fossil fuels as dicarboxylic acid units.

[0131] The dicarboxylic acid units of biomass polyesters use dicarboxylic acids derived from fossil fuels. Aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and their derivatives can be used without restriction as dicarboxylic acids.

[0132] Alternatively, it can be a copolyester obtained by adding, in addition to the diol and dicarboxylic acid components mentioned above, at least one polyfunctional compound selected from difunctional hydroxycarboxylic acids, polyvalent alcohols with three or more functions for forming crosslinking structures, polycarboxylic acids with three or more functions and / or their anhydrides, and hydroxycarboxylic acids with three or more functions as a copolymer component as a third component.

[0133] In addition, as alternatives to conventional polyolefin membranes that use petroleum-based raw materials, biomass polyolefin membranes such as biomass polyethylene membranes and biomass polyethylene-polypropylene membranes are also known.

[0134] Polyethylene resins are not particularly limited except for the use of ethylene glycol derived from biomass in part of the raw materials. Examples include homopolymers of ethylene, copolymers of ethylene and α-olefins with ethylene as the main component (ethylene-α-olefin copolymers containing more than 90% by mass of ethylene units), etc. One of these can be used alone, or two or more can be used in combination.

[0135] It should be noted that the α-olefin constituting the copolymer of ethylene and α-olefin is not particularly limited, and examples include α-olefins with 4 to 8 carbon atoms such as 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene. Known polyethylene resins such as low-density polyethylene resin, medium-density polyethylene resin, and linear low-density polyethylene resin can be used. From the viewpoint that even if the films rub against each other, further damage such as openings and cracks is less likely to occur, linear low-density polyethylene resin (LLDPE) (a copolymer of ethylene and 1-hexene, or a copolymer of ethylene and 1-octene) is preferred, and a density of 0.910 to 0.925 g / cm³ is more preferred. 3 Linear low-density polyethylene resin.

[0136] Regarding biofilms, biofilms made from biomass raw materials differentiated according to the bioplasticity specified in ISO 16620 or ASTM D6866 are also in circulation. Radioactive carbon-14C exists in the atmosphere at a ratio of 1 in 10¹², a ratio that remains unchanged even in atmospheric carbon dioxide, and therefore also remains unchanged in plants that fix carbon dioxide through photosynthesis. Therefore, the carbon in resins derived from plants contains radioactive carbon-14C. In contrast, the carbon in resins derived from fossil fuels contains almost no radioactive carbon-14C. Therefore, by measuring the concentration of radioactive carbon-14C in resins using an accelerator mass analyzer, the proportion of plant-derived resin in the resin, i.e., the bioplasticity, can be determined.

[0137] Low-density polyethylene derived from plants, which is a biomass plastic with a biomass plasticity of 80% or more, preferably 90% or more, as specified in ISO 16620 or ASTM D6866, such as the trade names "SBC818", "SPB608", "SBF0323HC", "STN7006", "SEB853", and "SPB681" manufactured by Braskem, can be used as suitable raw materials for the production of membranes.

[0138] In addition, films and sheets made by combining starch and polylactic acid as biomass raw materials are also known. They can be selected and used appropriately depending on the application.

[0139] Biomass membranes can be laminates composed of multiple biomass membranes, or they can be laminates of conventional petroleum-based membranes and biomass membranes. Furthermore, these biomass membranes can be unstretched or stretched membranes, and their manufacturing method is not limited.

[0140] The film can be a film that has undergone stretching treatment. As a stretching treatment method, resin is typically melted and extruded into a sheet using methods such as extrusion film forming, followed by simultaneous biaxial stretching or successive biaxial stretching. In the case of successive biaxial stretching, longitudinal stretching is usually performed first, followed by transverse stretching. Specifically, a method combining longitudinal stretching utilizing the speed difference between rollers with transverse stretching using a tenter frame is often used.

[0141] In order to form an adhesive layer without defects such as film rupture or uneven coating, various surface treatments such as flame treatment and corona discharge treatment can be applied to the film surface as needed.

[0142] Alternatively, inorganic vapor-deposited films such as metal vapor-deposited films with metal layers such as aluminum, transparent vapor-deposited films with vapor-deposited layers of metal oxides such as silicon dioxide and aluminum oxide, or barrier films containing gas barrier layers such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, and vinylidene chloride can be used. By using such films, it is possible to produce laminates that have barrier properties against water vapor, oxygen, alcohols, inactive gases, and volatile organic compounds (fragrances).

[0143] As for paper, there are no particular limitations, and known paper substrates can be used. Specifically, it can be manufactured using natural papermaking fibers such as wood pulp and using known papermaking machines, but the papermaking conditions are not particularly specified. Examples of natural papermaking fibers include wood pulps such as softwood pulp and hardwood pulp, non-wood pulps such as Manila hemp pulp, sisal pulp, and flax pulp, as well as pulps obtained by chemically modifying these pulps. As for the type of pulp, chemical pulps based on sulfate hydrolysis, acid / neutral / alkaline sulfite hydrolysis, sodium salt hydrolysis, etc., milled pulps, chemi-milled pulps, thermomechanical pulps, etc., can be used. In addition, various commercially available high-quality papers, coated papers, lining papers, impregnated papers, cardboard, paperboard, etc., can also be used.

[0144] Examples of the construction of a stacked body include:

[0145] (1) Substrate 1 / Adhesive layer 1 / Sealing film

[0146] (2) Substrate 1 / Adhesive layer 1 / Metal vapor-deposited unstretched film

[0147] (3) Substrate 1 / Adhesive layer 1 / Metal vapor-deposited stretch film

[0148] (4) Transparent vapor-deposited stretch film / adhesive layer 1 / sealing film

[0149] (5) Substrate 1 / Adhesive Layer 1 / Substrate 2 / Adhesive Layer 2 / Sealing Film

[0150] (6) Substrate 1 / Adhesive Layer 1 / Metal Vapor Deposited Stretch Film / Adhesive Layer 2 / Sealing Film

[0151] (7) Substrate 1 / Adhesive Layer 1 / Transparent Vapor Deposited Stretch Film / Adhesive Layer 2 / Sealing Film

[0152] (8) Substrate 1 / Adhesive Layer 1 / Metal Layer / Adhesive Layer 2 / Sealing Film

[0153] (9) Substrate 1 / Adhesive Layer 1 / Substrate 2 / Adhesive Layer 2 / Metal Layer / Adhesive Layer 3 / Sealing Film

[0154] (10) Substrate 1 / Adhesive layer 1 / Metal layer / Adhesive layer 2 / Substrate 2 / Adhesive layer 3 / Sealing film, etc., but not limited to these.

[0155] Examples of substrate 1 used in composition (1) include MDOPE film, OPE film, OPP film, PET film, nylon film, and paper. Alternatively, substrate 1 may be a material that has been coated to improve gas barrier properties and ink receptivity when the printing layer described later is applied. Commercially available examples of coated substrate films 1 include K-OPP film and K-PET film. Adhesive layer 1 is a cured coating of the adhesive of the present invention. Examples of sealing films include CPP film, LLDPE film, and gas barrier heat-sealing film. The printing layer may be provided on the adhesive layer 1 side of substrate 1 (or the adhesive layer 1 side of the coated layer when using a coated material as substrate film 1) or on the side opposite to adhesive layer 1. The printing layer is formed using various printing inks such as gravure ink, flexographic ink, offset ink, stencil ink, and inkjet ink, and by conventional printing methods used for printing on polymer films and paper.

[0156] Examples of substrate 1 used in configurations (2) and (3) include MDOPE film, OPE film, OPP film, PET film, and paper. The adhesive layer 1 is a cured coating of the adhesive of the present invention. As a metal-deposited unstretched film, VM-CPP film and VM-LLDPE film, obtained by metal vapor deposition of aluminum or the like onto CPP film, LLDPE film, or gas barrier heat-sealing film, can be used. As a metal-deposited stretched film, VM-MDOPE film, VM-OPE film, and VM-OPP film, obtained by metal vapor deposition of aluminum or the like onto MDOPE film, OPE film, or OPP film, can be used. A printing layer may also be provided on any surface of substrate 1, similar to configuration (1).

[0157] As the transparent vapor-deposited stretch film used in configuration (4), examples include films obtained by vapor deposition of silicon dioxide and aluminum oxide on MDOPE films, OPE films, OPP films, PET films, nylon films, etc. Films obtained by coating an inorganic vapor-deposited layer with silicon dioxide or aluminum oxide for the purpose of protection can also be used. Adhesive layer 1 is a cured coating of the adhesive of the present invention. Sealing film can be the same as that in configuration (1). A printing layer can be provided on the adhesive layer 1 side of the transparent vapor-deposited stretch film (or the adhesive layer 1 side of the coating layer when a material obtained by coating an inorganic vapor-deposited layer is used). The method for forming the printing layer is the same as in configuration (1).

[0158] Examples of substrate 1 used in configuration (5) include PET film and paper. Examples of substrate 2 include nylon film. At least one of adhesive layer 1 and adhesive layer 2 is a cured coating of the adhesive of the present invention. Examples of sealing film are the same as those in configuration (1). A printing layer can be provided on any surface of substrate 1 in the same manner as in configuration (1).

[0159] As the substrate 1 of configuration (6), examples of substrates similar to those in configurations (2) and (3) can be given. As a metal vapor-deposited stretched film, examples of VM-MDOPE film, VM-OPE film, VM-OPP film, and VM-PET film obtained by metal vapor deposition of aluminum or the like on MDOPE film, OPE film, OPP film, and PET film can be given. At least one of adhesive layer 1 and adhesive layer 2 is a cured coating of the adhesive of the present invention. Examples of sealing films are the same as those in configuration (1). A printing layer can be provided on any surface of substrate 1, similar to configuration (1).

[0160] Examples of substrate 1 in component (7) include PET film and paper. Examples of transparent vapor-deposited stretch film include the same transparent vapor-deposited stretch film as in component (4). At least one of adhesive layers 1 and 2 is a cured coating of the adhesive of the present invention. Examples of sealing film include the same sealing film as in component (1). A printing layer may be provided on any surface of substrate 1, similar to component (1).

[0161] Examples of substrate 1 in component (8) include PET film and paper. Examples of metal layers include aluminum foil. At least one of adhesive layers 1 and 2 is a cured coating of the adhesive of the present invention. Examples of sealing films are the same as those in component (1). A printed layer can be provided on any surface of substrate 1 in the same manner as in component (1).

[0162] Examples of substrate 1 in components (9) and (10) include PET film and paper. Examples of substrate 2 include nylon film. Examples of metal layer include aluminum foil. At least one of adhesive layers 1, 2, and 3 is a cured coating of the adhesive of the present invention. Examples of sealing film are the same as those in component (1). A printing layer can be provided on any surface of substrate 1 in the same manner as in component (1).

[0163] The adhesive of the present invention exhibits excellent initial cohesive strength, and its degradation over time is suppressed. Because the aggregation of bubbles caused by low initial cohesive strength is suppressed, a laminate with excellent processing appearance can be obtained. Poor processing appearance is prone to occur when at least one of the substrates to be bonded is a relatively hard substrate such as a PET film or Ny film, or when a laminate is manufactured by bonding a substrate with a vapor-deposited layer or metal foil. Therefore, the adhesive of the present invention is particularly suitable for the manufacture of such laminates.

[0164] As specific examples of such a layered structure, the following can be cited:

[0165] PET film / adhesive layer / LLDPE film

[0166] PET film / adhesive layer / CPP film

[0167] PET film / adhesive layer / aluminum vapor-deposited CPP film

[0168] Transparent vapor-deposited PET film / adhesive layer / CPP film

[0169] Ny membrane / adhesive layer / LLDPE membrane, etc.

[0170] Examples include Ny film / adhesive layer / CPP film.

[0171] OPP film / adhesive layer / aluminum vapor-deposited CPP film

[0172] Transparent vapor-deposited OPP film / adhesive layer / CPP film

[0173] Transparent vapor-deposited OPE film / adhesive layer / CPP film

[0174] Transparent vapor-deposited Ny film / adhesive layer / CPP film

[0175] Gas barrier polyolefin film / adhesive layer / CPP film

[0176] Gas barrier polyolefin film / adhesive layer / LLDPE film

[0177] Ny film / Aluminum vapor-deposited PET film / LLDPE film

[0178] PET film / Aluminum vapor-deposited PET film / LLDPE film

[0179] PET film / Aluminum vapor-deposited PET film / Ny film / LLDPE film

[0180] PET film / Ny film / LLDPE film

[0181] PET film / aluminum foil / CPP film

[0182] PET film / aluminum foil / LLDPE film

[0183] Aluminum foil / PET film / LLDPE film

[0184] PET film / AL / PET film / LLDPE film

[0185] OPP film / Aluminum vapor-deposited PET film / Aluminum vapor-deposited EVOH film / LLDPE film

[0186] Antistatic Ny film / Ny film / aluminum foil / LLDPE film, etc.

[0187] In the configuration illustrated above, the LLDPE film can be colored white.

[0188] <Method for manufacturing laminates>

[0189] The laminate of the present invention can be obtained, for example, by a method having a two-liquid mixing step (solvent-free lamination) or a method having a two-liquid separate coating step. In the two-liquid mixing step, a polyisocyanate composition (X) and a polyol composition (Y) are pre-mixed and coated onto a first substrate, and then a second substrate is laminated on the coated surface. The adhesive layer is then cured to obtain a laminate. In the two-liquid separate coating step, a polyisocyanate composition (X) and a polyol composition (Y) are respectively coated onto a first substrate and a second substrate, and then their respective coated surfaces are brought into contact and pressed together, thereby laminating the first substrate and the second substrate, and curing the adhesive layer to obtain a laminate.

[0190] As another method of applying the two liquids separately, a mixture of a polyisocyanate composition (X) and a compound with active hydrogen groups can be applied to one substrate, and a polyol composition (Y) can be applied to another substrate. The coated surfaces of the two substrates are then brought into contact and pressed together, thereby stacking the substrates and curing the adhesive layer.

[0191] When the laminate of the present invention is manufactured by a method having a two-liquid mixing step, the coating amount of the adhesive (a mixture of polyisocyanate composition (X) and polyol composition (Y)) is, for example, 0.5 to 5.0 g / m³. 2 When manufacturing the laminate of the present invention by means of a two-component coating process, the coating amounts of the polyisocyanate composition (X) and the polyol composition (Y) are preferably 0.3 to 3.0 g / m². 2 More preferably, 0.3–2.0 g / m 2 Use it in a left-right manner.

[0192] The preferred pressing method is to bond the laminating rollers by passing them between two rollers (lamination rollers) while using the pressure between the rollers. The temperature of the lamination rollers is preferably around room temperature to 80°C, and the pressure is preferably around 0.05 to 0.5 MPa.

[0193] Regardless of the method used, when using the two-component curing adhesive of the present invention, after lamination, the adhesive is cured at room temperature (20-25°C) or under heating, more specifically at 15-50°C, for 12-72 hours, exhibiting practical properties.

[0194] The adhesive of this invention has high reactivity and excellent initial cohesion, but on the other hand, its pot life tends to be short. Therefore, it is preferable to apply it to a two-component coating process that is less prone to such problems.

[0195] Packaging Materials

[0196] The aforementioned laminated body is suitable for use as packaging material, especially for food packaging. Regarding the packaging material, it is produced by shaping the laminated body into a bag shape and then heat-sealing it. Various packaging materials are available, including three-side sealed bags, four-side sealed bags, corner-supported bags, pillow-shaped bags, gable-top bottomed containers, Tetra Pak cartons, brick-shaped bags, tube containers, paper cups, and lids. Furthermore, easy-opening and resealing mechanisms can be appropriately incorporated into the packaging material.

[0197] The packaging material of this invention is primarily intended for food use, but it is also suitable for use as packaging material for filling detergents and pharmaceuticals. Specific applications include, as detergents and pharmaceuticals, liquid washing detergents, kitchen detergents, bath detergents, liquid soaps, liquid shampoos, liquid conditioners, pharmaceutical tablets, IV drips, blood transfusion bags, syringes and other medical devices, batteries, vacuum insulation materials, silicon wafers and other precision components. Additionally, it can also be used as secondary packaging material for packaging the aforementioned containers.

[0198] Example

[0199] The present invention will be described in more detail below with specific examples of synthesis and embodiments, but the present invention is not limited to these embodiments. It should be noted that, in the following examples, unless otherwise specified, "parts" and "%" represent "parts by mass" and "% by mass", respectively.

[0200] <Preparation of Polyisocyanate Composition (X)>

[0201] (Polyisocyanate composition (X-1))

[0202] In a flask equipped with a stirrer, thermometer, and nitrogen inlet, 40.2 parts of 4,4-diphenylmethane diisocyanate (hereinafter referred to as "MDI") and 10.0 parts of hexamethylene diisocyanate ureate (hereinafter referred to as "HDI ureate") were added to a reaction vessel and stirred under nitrogen atmosphere, then heated to 60°C. Further, 37.9 parts of difunctional polypropylene glycol (hereinafter referred to as "PPG") with a number average molecular weight of 1000 and 2.0 parts of 2,2,4-trimethyl-1,3-pentanediol were mixed and added dropwise to the flask in fractions. The mixture was stirred at 80°C for 5–6 hours to carry out a carbamate reaction, thereby obtaining a polyisocyanate. The obtained polyisocyanate was mixed with 10.0 parts of carbodiimide-modified isocyanate to obtain a polyisocyanate composition (X-1). The polyisocyanate composition (X-1) has an NCO% of 13.0% and a viscosity of 1500 mPa·s at 50°C.

[0203] (Polyisocyanate composition (X-2))

[0204] In a polyester reaction vessel equipped with a stirrer, nitrogen inlet pipe, Snyder tube, and condenser, 92.00 parts of ethylene glycol, 118.50 parts of phthalic anhydride, 29.23 parts of adipic acid, and 0.01 parts of tetraisopropoxide titanium were added. The mixture was slowly heated to maintain an internal temperature of 220°C, ensuring the temperature at the top of the distillation tube did not exceed 100°C. The esterification reaction was terminated when the acid value reached below 1 mg KOH / g, yielding polyester intermediate B1' with a number average molecular weight of 500.

[0205] In a reaction vessel equipped with a stirrer, nitrogen inlet pipe, Snyder tube, cooling condenser, and dropping funnel, 71.45 parts of phenylene diisocyanate and 46.26 parts of Millionate MN (a mixture of 4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate) were added. The mixture was heated to 70°C while stirring. Using a dropping funnel, 92.28 parts of polyester intermediate B1' were added dropwise over 2 hours. The mixture was further stirred for 4 hours to obtain a polyisocyanate composition (X-2). The NCO% was 15.1%, and the viscosity at 50°C was 2900 mPa·s.

[0206] (Polyisocyanate composition (X-3))

[0207] In a reaction vessel equipped with a stirrer, thermometer, and nitrogen inlet, 80.0 parts of hexamethylene diisocyanate ureate (Sumika Covestro Urethane, Sumidur N3300) and 20.0 parts of isophorone diisocyanate ureate (EVONIK, VESTANAT T1890 / 100) were added, and the mixture was heated to 130°C while stirring. Stirring continued at 130°C until the contents became transparent. The mixture was then cooled upon becoming transparent, thus obtaining the polyisocyanate composition (X-1). The polyisocyanate composition (X-3) had an NCO% of 20.9% and a viscosity of 2150 mPa·s at 50°C.

[0208] <Preparation of polyol composition (Y)>

[0209] Polyester polyols (B1-1)~(B1-3) and (E1-1)~(E1-3) were obtained as follows.

[0210] (Synthesis of polyester polyol (B1-1))

[0211] In a reaction vessel equipped with a stirrer, thermometer, nitrogen inlet pipe, distillation tube, and moisture separator, 54.0 parts of 3-methylpentane, 30.0 parts of trimethylolpropane, 60.0 parts of adipic acid, and 0.01 parts of tetraisopropoxide titanium were added under nitrogen atmosphere. The mixture was slowly heated to maintain an internal temperature of 220°C, ensuring the temperature at the top of the distillation tube did not exceed 100°C. The esterification reaction was terminated when the acid value fell below 1 mg KOH / g, yielding a polyester polyol (B1-2) with a number average molecular weight of 500 and a hydroxyl value of 337.

[0212] (Synthesis of polyester polyol (B1-2))

[0213] In a reaction vessel equipped with a stirrer, thermometer, nitrogen inlet pipe, distillation tube, and moisture separator, 54.0 parts of 3-methylpentanediol, 46.0 parts of isophthalic acid, and 0.01 parts of tetraisopropoxide titanium were added under nitrogen atmosphere. The mixture was slowly heated so that the temperature at the top of the distillation tube did not exceed 100°C, maintaining the internal temperature at 250°C. The esterification reaction was terminated when the acid value fell below 1 mg KOH / g, yielding a polyester polyol (B1-1) with a number average molecular weight of 500 and a hydroxyl value of 224.

[0214] (Synthesis of polyester polyol (B1-3))

[0215] In a reaction vessel equipped with a stirrer, thermometer, nitrogen inlet pipe, distillation tube, and moisture separator, 25.0 parts of 1,4-butanediol, 25.0 parts of 1,6-hexanediol, 58.0 parts of adipic acid, and 0.01 parts of tetraisopropoxide titanium were added under nitrogen atmosphere. The mixture was slowly heated to maintain an internal temperature of 220°C, ensuring the temperature at the top of the distillation tube did not exceed 100°C. The esterification reaction was terminated when the acid value fell below 1 mg KOH / g, yielding a polyester polyol (B1-3) with a number average molecular weight of 1000 and a hydroxyl value of 112.

[0216] (Synthesis of polyester polyol (E1-1))

[0217] In a reaction vessel equipped with a stirrer, thermometer, nitrogen inlet pipe, distillation tube, and moisture separator, 45.0 parts of diethylene glycol, 50.0 parts of adipic acid, and 0.01 parts of tetraisopropoxide titanium were added under nitrogen atmosphere. The mixture was slowly heated to maintain an internal temperature of 220°C, ensuring the temperature at the top of the distillation tube did not exceed 100°C. The esterification reaction was terminated when the acid value fell below 1 mg KOH / g, yielding a polyester polyol (B1-3) with a number average molecular weight of 1000 and a hydroxyl value of 112.

[0218] (Synthesis of polyester polyol (E1-2))

[0219] In a reaction vessel equipped with a stirrer, thermometer, nitrogen inlet pipe, distillation tube, and moisture separator, 7.2 parts by mass of ethylene glycol, 15.8 parts by mass of diethylene glycol, 22.5 parts by mass of neopentyl glycol, 21.9 parts by mass of adipic acid, 4.6 parts by mass of sebacic acid, and 28.0 parts by mass of isophthalic acid were added under nitrogen atmosphere. The mixture was slowly heated, keeping the temperature at the top of the distillation tube below 100°C, and the internal temperature was maintained at 240°C. The esterification reaction was terminated when the acid value fell below 1 mg KOH / g, yielding a polyester polyol (E1-2) with a number average molecular weight of 700 and a hydroxyl value of 159.0 mg KOH / g.

[0220] (Synthesis of polyester polyol (E1-3))

[0221] In a reaction vessel equipped with a stirrer, thermometer, nitrogen inlet pipe, distillation tube, and moisture separator, 92.0 parts by mass of ethylene glycol, 118.5 parts by mass of phthalic anhydride, 29.2 parts by mass of adipic acid, and 0.01 parts by mass of tetraisopropoxide titanium were added under nitrogen atmosphere. The mixture was slowly heated so that the temperature at the top of the distillation tube did not exceed 100°C, and the internal temperature was maintained at 250°C. The esterification reaction was terminated when the acid value became below 1 mg KOH / g, yielding a polyester polyol (E1-3) with a number average molecular weight of 500 and a hydroxyl value of 224.

[0222] Polyol compositions (Y-1) to (Y-10) and (Y'-1) to (Y'-6) were prepared according to the formulations in Tables 1 to 3. The amine value is expressed in mgKOH / g. Details of the compounds in the tables are as follows.

[0223] Polyester polyol (B2-1): Polycaprolactone polyol (manufactured by Daicel, PLACEL 205U (molecular weight 530, hydroxyl value 212)).

[0224] Polyether polyol (C1-1): Polypropylene polyol (manufactured by AGC, EXCENOL 1030 (molecular weight = 1000, hydroxyl value = 160))

[0225] Polyether polyols (C1-2): Polypropylene polyol (manufactured by AGC, EXCENOL 420 (molecular weight = 400, hydroxyl value = 280))

[0226] Polyether polyols (C1-3): Polypropylene polyol (manufactured by AGC, EXCENOL 430 (molecular weight = 400, hydroxyl value = 400))

[0227] Polyether polyols (C1-4): Polypropylene polyol (manufactured by Sanyo Chemical Co., Ltd., SANNIX HD-402 (molecular weight = 600, hydroxyl value = 404)

[0228] Polyamine (D-1): Polyoxypropylene triamine (Huntsman Corporation, JEFFAMINET-403, molecular weight = 440, amine value = 355 mg KOH / g)

[0229] Polyamine (D-2): Polyoxypropylene diamine (manufactured by Huntsman, JEFFAMINE D-2000, molecular weight = 2000, amine value = 56 mg KOH / g)

[0230] [Table 1]

[0231] Y-1 Y-2 Y-3 Y-4 Y-5 Polyester polyol (B1-1) 25.00 25.00 25.00 8.00 30.00 Polyester polyol (B1-2) 30.00 Polyester polyols (B1-3) Polyester polyol (B2-1) Polyether polyols (C1-1) 13.70 13.00 20.00 13.00 Polyether polyols (C1-2) 40.00 37.30 45.30 54.30 10.00 Polyether polyols (C1-3) 12.90 Polyether polyols (C1-4) 9.50 4.90 4.90 4.90 Polyamines (D-1) 9.00 17.00 2.00 17.00 17.00 Polyamine (D-2) Dimethylolpropionic acid 0.90 0.90 0.90 0.90 ε-caprolactam 0.90 0.90 0.90 0.90 Dibutyltin dilaurate 0.10 Zinc neodecanoate 0.50 0.50 0.50 0.50 Bismuth neodecanoate 0.50 0.50 0.50 0.50 3-Epoxypropoxypropyltrimethoxysilane 3-Aminopropyltriethoxysilane total 100.00 100.00 100.00 100.00 100.00 Amine value (mgKOH / g) 32.1 60.7 7.1 60.7 60.7

[0232] [Table 2]

[0233] Y-6 Y-7 Y-8 Y-9 Y-10 Polyester polyol (B1-1) Polyester polyol (B1-2) 30.00 30.00 30.00 Polyester polyols (B1-3) 30.00 Polyester polyol (B2-1) 30.00 Polyether polyols (C1-1) Polyether polyols (C1-2) 40.00 40.00 40.00 40.00 23.00 Polyether polyols (C1-3) 10.20 10.90 1030 10.90 10.90 Polyether polyols (C1-4) Polyamines (D-1) 17.00 17.00 17.00 17.00 Polyamine (D.2) 34.00 Dimethylolpropionic acid 0.90 ε-caprolactam 0.90 Dibutyltin dilaurate 0.10 0.10 0.10 0.10 Zinc neodecanoate 0.50 Bismuth neodecanoate 0.50 3-Epoxypropoxypropyltrimethoxysilane 1.00 1.00 1.00 1.00 3-Aminopropyltriethoxysilane 1.00 1.00 1.00 1.00 total 100.00 100.00 100.00 100.00 100.00 Amine value (mgKOH / g) 60.7 60.7 60.7 60.7 19.0

[0234] [Table 3]

[0235] Y′-1 Y′-2 Y′-3 Y′-4 Y′-5 Y′-6 Polyester polyol (B1-1) 25.00 Polyester polyol (E1-1) 30.00 Polyester polyols (E1-2) 30.00 Polyester polyols (E1-3) 30.00 30.00 Castor oil (E2) 46.00 Polyether polyols (C1-1) 23.00 Polyether polyols (C1-2) 42.60 40.00 40.00 40.00 23.00 40.00 Polyether polyols (C1-3) 12.90 12.90 12.90 12.90 Polyether polyols (C1-4) 10.00 Polyamines (D-1) 9.00 17.00 17.00 17.00 Polyamine (D-2) 34.00 Dimethylolpropionic acid ε-caprolactam 0.90 0.90 Dibutyltin dilaurate 0.10 0.10 0.10 0.10 Zinc neodecanoate 1.00 0.50 Bismuth neodecanoate 3-Epoxypropoxypropyltrimethoxysilane 0.50 3-Aminopropyltriethoxysilane 0.60 total 100.00 100.00 100.00 100.00 100.00 100.00 Amine value (mgKOH / g) 32.1 60.7 60.7 60.7 19.0 0.0

[0236] <The manufacture of printed materials>

[0237] The urethane-based laminating ink (Finart R794 White G3; manufactured by DIC Corporation) was adjusted to 15 seconds (25°C) using the Zein Cup #3 manufactured by the clutch company. The ink was printed on a corona-treated PET (polyethylene terephthalate) film (Toyobo ESTER Film E5102#12) at a printing speed of 150 m / min using a gravure printing press with a 43 μm plate depth. The film was then dried and cured in a 70°C oven to form a printed layer on the PET film.

[0238] <Evaluation>

[0239] (Processed appearance (use of items before storage))

[0240] A polyisocyanate composition (X-1) was coated on the surface of the printed layer of a PET film, and a polyol composition (Y-1) was coated on the aluminum vapor-deposited surface of an aluminum vapor-deposited polypropylene film (VMCPP, manufactured by TORAY ADVANCED FILM Co., Ltd., 2703, 25 μm). The PET film and VMCPP film were then pressed together using clamping rollers (50°C) to obtain the evaluation sample of Example 1, consisting of a PET film / adhesive layer / VMCPP film. The coating amounts of the polyisocyanate composition (X-1) and the polyol composition (Y-1) were 1.3 g / m², respectively. 2 0.7g / m 2 The application speed for the polyisocyanate composition (X-1) and the polyol composition (Y-1) was set to 250 m / min.

[0241] The application speeds of the polyisocyanate composition (X-1) and the polyol composition (Y-1) were changed to 200 m / min, 150 m / min, and 100 m / min, respectively. Otherwise, the same procedure was followed to prepare the evaluation samples of Example 1.

[0242] The polyisocyanate composition (X), polyol composition (Y), and coating amount used were changed as shown in Tables 4-6. Otherwise, the same procedure as in Example 1 was followed to obtain the evaluation samples for the examples and comparative examples.

[0243] The vapor-deposited surface is visually observed through the printed and adhesive layers from the PET film side of the evaluation sample, and the evaluation is carried out according to the following criteria.

[0244] 5: Even when the adhesive was applied at a speed of 250 m / min, no air bubbles with a maximum diameter of 0.1 mm or larger were detected.

[0245] 4: Even when the adhesive was applied at a speed of 200 m / min, no air bubbles with a maximum diameter of 0.1 mm or larger were detected.

[0246] 3: Even when the adhesive was applied at a speed of 150 m / min, no air bubbles with a maximum diameter of 0.1 mm or larger were detected.

[0247] 2: Even when the adhesive was applied at a speed of 100 m / min, no air bubbles with a maximum diameter of 0.1 mm or larger were detected.

[0248] 1: Even when the adhesive is applied at a speed of 100 m / min, air bubbles with a maximum diameter of 0.1 mm or more were detected.

[0249] (Processed appearance (use of items after storage and preservation))

[0250] The polyol composition (Y) was sealed in a container under nitrogen atmosphere and stored at 50°C for 4 weeks. The stored polyol composition (Y) was then used to prepare and evaluate samples under the same conditions as the processed appearance (using the sample before storage).

[0251] (Lamination strength)

[0252] A polyisocyanate composition (X-1) was coated on the surface of the printed layer of a PET film, and a polyol composition (Y-1) was coated on the aluminum vapor-deposited surface of an aluminum vapor-deposited polypropylene film (VMCPP, manufactured by TORAY ADVANCED FILM Co., Ltd., 2703, 25 μm). The PET film and VMCPP film were then pressed together using clamping rollers (50°C) to obtain the evaluation sample of Example 1, consisting of a PET film / adhesive layer / VMCPP film. The coating amounts of the polyisocyanate composition (X-1) and the polyol composition (Y-1) were 1.3 g / m², respectively. 2 0.7g / m 2 The application speed for the polyisocyanate composition (X-1) and the polyol composition (Y-1) was set to 250 m / min.

[0253] The polyisocyanate composition (X), polyol composition (Y), and coating amount used were changed as shown in Tables 4-6. Otherwise, the same procedure as in Example 1 was followed to obtain the evaluation samples for the examples and comparative examples.

[0254] The evaluation samples were cut into 300 mm long and 15 mm wide sections. Using an Instron tensile testing machine at 25°C, tensile strength was measured at a peel speed of 300 mm / min, with the T-peel strength measured across a 15 mm width. This test was performed five times, and the average value was calculated. The results were then evaluated according to the following criteria.

[0255] 5: 1.5N / 15mm or more

[0256] 4: 1.0N / 15mm or more but less than 1.5N / 15mm

[0257] 3: 0.5N / 15mm or more but less than 1.0N / 15mm

[0258] 2: 0.2N / 15mm or more and less than 0.5N / 15mm

[0259] 1: Less than 0.2N / 15mm

[0260] [Table 41]

[0261] Example 1 Example 2 Example 3 Example 4 Example 5 Polyisocyanate composition (X-1) 1.3 1.3 1.3 1.3 1.3 Polyisocyanate composition (X-2) Polyisocyanate composition (X-3) Polyol composition (Y-1) 0.7 Polyol composition (Y-2) 0.7 Polyol composition (Y-3) 0.7 Polyol composition (Y-4) 0.7 Polyol composition (Y-5) 0.7 Appearance after processing (before storage) 4 5 3 5 5 Appearance after processing (after storage) 4 5 3 5 5 Lamination strength 5 5 5 4 4

[0262] [Table 5]

[0263] Example 6 Example 7 Example 8 Example 9 Example 10 Polyisocyanate composition (×-1) Polyisocyanate composition (X-2) 1.4 1.4 Polyisocyanate composition (X-3) 1.2 1.2 1.2 Polyol composition (Y-6) 0.6 Polyol composition (Y-7) 0.8 Polyol composition (Y-8) 0.8 Polyol composition (Y-9) 0.8 Polyol composition (Y-10) 0.8 Appearance after processing (before storage) 5 5 5 5 4 Appearance after processing (after storage) 5 5 5 5 4 Lamination strength 5 5 5 5 5

[0264] [Table 6]

[0265] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Polyisocyanate composition (X-1) 1.3 1.3 1.4 1.4 1.3 1.3 Polyisocyanate composition (X-2) Polyisocyanate composition (X-3) Polyol composition (Y′-1) 0.7 Polyol composition (Y′-2) 0.7 Polyol composition (Y′-3) 0.6 Polyol composition (Y′-4) 0.6 Polyol composition (Y′-5) 0.7 Polyol composition (Y′-6) 0.7 Appearance after processing (before storage) 3 5 5 5 4 1 Appearance after processing (after storage) 1 1 1 1 1 1 Lamination strength 3 5 5 5 5 5

Claims

1. A two-component curing adhesive, comprising: An isocyanate composition (X) comprising a polyisocyanate compound (A); and A polyol composition (Y) comprising a polyester polyol (B), a compound comprising a polyoxyalkylene chain and hydroxyl groups (C), and a polyamine (D), The polyester polyol (B) is at least one selected from polyester polyol (B1) and polycaprolactone polyol (B2), wherein the polyester polyol (B1) is a reaction product of a polycarboxylic acid and a polyvalent alcohol, and wherein more than 90% by mass of the polyvalent alcohol is an aliphatic diol with 4 or more and 10 or fewer carbon atoms in the alkyl chain connecting the two hydroxyl groups. The total amount of the polyester polyol (B), the compound (C), and the polyamine (D) accounts for more than 90% by mass of the solid components of the polyol composition (Y).

2. The two-component curing adhesive according to claim 1, wherein, The amine value of the polyol composition (Y) is above 1 mg KOH / g and below 100 mg KOH / g.

3. The two-component curing adhesive according to claim 1, wherein, The polyester polyol (B) accounts for 10% to 80% by mass of the solid components of the polyol composition (Y).

4. The two-component curing adhesive according to claim 1, wherein, The compound (C) accounts for 15% to 80% by mass of the solid component of the polyol composition (Y).

5. The two-component curing adhesive according to claim 1, wherein, The viscosity of the polyol composition (Y) at 50°C is above 50 mPa·s and below 500 mPa·s.

6. The two-component curing adhesive according to claim 1, wherein, The isocyanate composition (X) has a viscosity of 300 mPa·s or more and 10000 mPa·s or less at 50°C.

7. The two-component curing adhesive according to claim 1, wherein, The adhesive contains an organometallic catalyst, wherein the amount of the organometallic catalyst is more than 0.005% by mass and less than 1.0% by mass of the total amount of the adhesive.

8. A laminate having a first substrate, a second substrate, and an adhesive layer for bonding the first substrate and the second substrate, wherein the adhesive layer is a cured coating of a two-component curable adhesive as described in any one of claims 1 to 7.

9. A packaging material comprising the laminate of claim 8.