Polyurethane polyisocyanate, method for producing polyurethane polyisocyanate, polyisocyanate composition, adhesive, laminate, packaging material

Abstract

Provided is a polyurethane polyisocyanate which undergoes little coloration even if the content of unreacted isocyanate monomer is reduced by means of distillation.　A polyisocyanate composition (X) contains: a polyurethane polyisocyanate (A1) that is a product of a reaction between a diisocyanate monomer (l) and a polyol compound (m); 0.1 mass% or less of a diisocyanate monomer (l'); sodium; and magnesium. The content of sodium is 100-700 ppb in the polyurethane polyisocyanate (A1). The content of magnesium is 10-500 ppb in the polyurethane polyisocyanate (A1). The mass ratio of sodium and magnesium (Na / Mg) is 2-70.

Description

[Technical field]

[0001] The present invention relates to a polyurethane polyisocyanate, a method for producing the polyurethane polyisocyanate, an isocyanate composition containing the polyurethane polyisocyanate, an adhesive containing the isocyanate composition, and a laminate and a packaging material produced using the adhesive. [Background technology]

[0002] Laminates used for various packaging materials, labels, etc., are imparted with design, functionality, storage stability, convenience, transport resistance, etc. by laminating a wide variety of substrates such as plastic films, metal foils, and paper. Packaging materials obtained by forming such laminates into bags are used as packaging materials in various fields, including food, medicines, detergents, etc. Urethane reactive two-component adhesives (hereinafter sometimes referred to as two-component curing adhesives or reactive adhesives) have been widely used to manufacture such laminates.

[0003] Some urethane reactive two-component curing adhesives use ingredients that contain a certain amount of isocyanate monomer, such as isocyanate prepolymers, but there is a movement to restrict the use of isocyanate monomer from the viewpoint of occupational safety and health. The European Commission has adopted the REACH regulation, which prohibits the marketing of products that contain 0.1% or more by mass of isocyanate monomer unless certain requirements are met.

[0004] There are other concerns about isocyanate monomers. When two-part curing adhesives containing aromatic isocyanate prepolymers are used to manufacture laminates for food packaging, unreacted aromatic isocyanate monomers may remain in the adhesive layer. The isocyanate monomers react with surrounding water to become primary aromatic amines (PAA), which can migrate through the film and leach into the contents (food). There are concerns that PAA may be harmful to the human body, and various regulations have been put in place, including the European Commission's detection limit in its regulations on plastic materials and articles intended for food contact.

[0005] Since PAA reacts with unreacted aromatic isocyanate in the vicinity, the concentration of PAA will gradually decrease even if aromatic isocyanate remains in the adhesive layer. Although it will eventually fall below the detection limit, from the viewpoint of the manufacturing efficiency of laminates for food packaging, it is preferable that the initial value of aromatic isocyanate monomer remaining in the adhesive layer is low.

[0006] Methods for reducing the content of isocyanate monomers have been studied in the past. For example, Patent Document 1 discloses a method for forming an isocyanate-functional prepolymer having a low residual isocyanate content, comprising: (a) reacting a polyol selected from the group consisting of polyether polyols, polyester polyols, polyester polyether polyols, acrylic polyols, glycols, and mixtures thereof with an isocyanate monomer to form a reaction mixture containing a prepolymer having an NCO content of 2.5 to 11.5% by weight and an average NCO functionality in the range of 2.0 to 3.0; and (b) passing the reaction mixture containing the prepolymer and unreacted isocyanate through a short-path evaporator to remove the unreacted isocyanate to an amount of less than 0.15% by weight. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2002-265552 A Summary of the Invention [Problem to be solved by the invention]

[0008] When residual isocyanate monomer is removed from an isocyanate-functional prepolymer by such a method, there is a problem that the resulting isocyanate-functional prepolymer is colored yellow or brown.

[0009] The present invention has been made in view of the above circumstances, and provides a polyurethane polyisocyanate that is less colored even when the content of unreacted isocyanate monomer is removed by distillation, and a method for producing such a polyurethane polyisocyanate. [Means for solving the problem]

[0010] That is, the present invention relates to a polyisocyanate composition (X) comprising a polyurethane polyisocyanate (A1) which is a reaction product of a diisocyanate monomer (l) and a polyol compound (m), 0.1 mass % or less of a diisocyanate monomer (l'), sodium, and magnesium, in which the sodium content of the polyurethane polyisocyanate (A1) is 100 ppb or more and 700 ppb or less, the magnesium content of the polyurethane polyisocyanate (A1) is 10 ppb or more and 50 ppb or less, and the mass ratio of sodium to magnesium, Na / Mg, is 2 or more and 70 or less. Effect of the Invention

[0011] According to the present invention, even when the content of unreacted isocyanate monomer is removed by distillation, a polyurethane polyisocyanate with little coloration can be obtained. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] <Polyurethane polyisocyanate (A1)> (Polyurethane polyisocyanate (A1)) The polyurethane polyisocyanate (A1) of the present invention can be obtained through a step (1) of reacting a diisocyanate monomer (l) with a polyol compound (m) in the presence of specific amounts of a sodium-containing compound and a magnesium-containing compound to obtain a composition containing the polyurethane polyisocyanate (A1) and a diisocyanate monomer (l'), and a step (2) of distilling off the diisocyanate monomer (m') from the composition obtained in the step (1).

[0013] As the diisocyanate monomer (l), known aromatic, araliphatic, aliphatic and alicyclic diisocyanates can be used alone or in combination of two or more.

[0014] Examples of aromatic diisocyanates include 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (also called MDI), polymethylene polyphenyl polyisocyanate (also called polymeric MDI or crude MDI), 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate (also called PPDI), 2,4-tolylene diisocyanate, and the like. Examples of the isocyanate include, but are not limited to, 2,6-tolylene diisocyanate (also known as TDI), 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, tolidine diisocyanate (also known as TODI), dianisidine diisocyanate, naphthalene diisocyanate (also known as NDI), 4,4'-diphenyl ether diisocyanate, and 4,4',4"-triphenylmethane triisocyanate.

[0015] The araliphatic diisocyanate means an aliphatic isocyanate having one or more aromatic rings in the molecule, and examples thereof include, but are not limited to, m- or p-xylylene diisocyanate (also known as XDI), α,α,α',α'-tetramethylxylylene diisocyanate (also known as TMXDI), and the like.

[0016] 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, and lysine diisocyanate (also known as LDI).

[0017] Examples of alicyclic diisocyanates include, but are not limited to, 3-isocyanatemethyl-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(isocyanatemethyl)cyclohexane (also known as hydrogenated XDI or HXDI), hydrogenated TMXDI, and norbornane diisocyanate (also known as NBDI).

[0018] As the polyol (m), a conventionally known one can be used, such as glycols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol;

[0019] Trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, and pentaerythritol; Bisphenols such as bisphenol A, bisphenol F, hydrogenated bisphenol A, and 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, and cyclohexylene in the presence of a polymerization initiator such as glycol, trifunctional or tetrafunctional aliphatic alcohol, etc.;

[0020] polyester polyols (1), which are reaction products of polyesters obtained by ring-opening polymerization of cyclic ester compounds such as propiolactone, butyrolactone, ε-caprolactone, σ-valerolactone, β-methyl-σ-valerolactone, etc., with polyhydric alcohols such as the above-mentioned glycols, glycerin, trimethylolpropane, pentaerythritol, etc.; Polyester polyol (2) obtained by reacting a difunctional polyol such as glycol, dimer diol, or bisphenol with a polycarboxylic acid: (3) a polyester polyol obtained by reacting a trifunctional or tetrafunctional aliphatic alcohol with a polycarboxylic acid; (4) a polyester polyol obtained by reacting a difunctional polyol with a trifunctional or tetrafunctional aliphatic alcohol and a polycarboxylic acid; Polyester polyols (5), which are polymers of hydroxyl acids such as dimethylolpropionic acid and castor oil fatty acid;

[0021] (1) a polyurethane polyol obtained by polymerizing at least one selected from a difunctional polyol, a trifunctional or a tetrafunctional aliphatic alcohol with an isocyanate compound; Polyether urethane polyol (2) obtained by further increasing the molecular weight of polyether polyol with an isocyanate compound; A polyester polyurethane polyol (3) obtained by polymerizing the polyester polyols (1) to (5) with an isocyanate compound; A polyester polyether polyurethane polyol (4) obtained by reacting at least one of the polyester polyols (1) to (5), a polyether polyol, and an isocyanate compound;

[0022] Examples of the polyol include castor oil-based polyols such as castor oil, dehydrated castor oil, hydrogenated castor oil, and 5 to 50 mole alkylene oxide adducts of castor oil, and mixtures of these polyols. These polyols can be used alone or in combination of two or more kinds.

[0023] Examples of the polyvalent carboxylic acid used in the synthesis of the polyester polyols (2) to (4) include aromatic polybasic acids such as orthophthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride, naphthalic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid, benzophenonetetracarboxylic acid, benzophenonetetracarboxylic dianhydride, 5-sodium sulfoisophthalic acid, tetrachlorophthalic anhydride, and tetrabromophthalic anhydride; Methyl esters of aromatic polybasic acids such as dimethyl terephthalic acid and dimethyl 2,6-naphthalenedicarboxylate;

[0024] Aliphatic polybasic acids such as malonic acid, succinic acid, succinic anhydride, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, maleic anhydride, and itaconic acid; Alkyl esters of aliphatic polybasic acids, such as dimethyl malonate, diethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, diethyl pimelate, diethyl sebacate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, and diethyl maleate;

[0025] Alicyclic 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, himic anhydride, and HET acid anhydride; and the like, and these can be used alone or in combination of two or more kinds.

[0026] As the isocyanate compound used in the synthesis of the polyurethane polyols (1) to (4), the same compounds as the diisocyanate monomer (m) exemplified above can be used.

[0027] The polyol compound (m) is preferably a polyether polyol, and more preferably a polyether polyol obtained by addition polymerization of at least one alkylene oxide selected from ethylene oxide, propylene oxide, and butylene oxide in the presence of a polymerization initiator such as glycol, or a trifunctional or tetrafunctional aliphatic alcohol.

[0028] In step (1), diisocyanate monomer (l) and polyol compound (m) are reacted under conditions in which the isocyanate groups contained in polyisocyanate monomer (l) are in excess relative to the active hydrogen groups contained in polyol compound (m), to obtain a composition containing polyurethane polyisocyanate (A1) and diisocyanate monomer (l'). The equivalent ratio of isocyanate groups to active hydrogen groups [NCO] / [active hydrogen groups] can be appropriately adjusted, and is, for example, 2.0 or more and 20.0 or less. Diisocyanate monomer (l') is the diisocyanate monomer (l) that remains after the reaction without reacting with the active hydrogen groups.

[0029] The urethane reaction between the diisocyanate monomer (l) and the polyol compound (m) is carried out in the presence of a sodium-containing compound and a magnesium-containing compound. The sodium-containing compound and the magnesium-containing compound are used in such a range that the sodium content of the polyurethane polyisocyanate (A1) calculated from the amount of the polyol compound (m) used is 100 ppb to 700 ppb, the magnesium content of the polyurethane polyisocyanate (A1) calculated from the amount of the polyol compound (m) used is 10 ppb to 50 ppb, and the mass ratio Na / Mg of sodium to magnesium is 2 to 70. The polyurethane polyisocyanate (A1) is calculated assuming that 1 mole of the diisocyanate monomer (l) reacts with 1 mole of the active hydrogen group of the polyol compound (m) (for example, when the polyol compound (m) is a compound having two active hydrogen groups, 1 molecule of the polyol compound (m) reacts with 2 molecules of the diisocyanate monomer (l) to form the polyurethane polyisocyanate (A1)).

[0030] Therefore, the polyurethane polyisocyanate (A1) of the present invention contains the sodium-containing compound and the magnesium-containing compound in the above-mentioned ranges. The sodium and magnesium contents in the polyurethane polyisocyanate (A1) may be calculated from the amounts of the diisocyanate monomer (l), the polyol compound (m), the sodium-containing compound and the magnesium-containing compound before the reaction, or may be measured by inductively coupled plasma mass spectrometry (ICP-MS) under the following conditions, for example.

[0031] Sample solution: Dilute 1000 times with 2 wt / vol% nitric acid aqueous solution Measurement equipment: Agilent 8900 ICP-MS Standard solution: SPEX XSTC-622B 10ppm 5% nitric acid and other aqueous solution Detection conditions: Select the optimum conditions (MS mode, gas type) Detection limit: 10ppb

[0032] Sodium-containing compounds include sodium hydroxide, sodium chloride, sodium oxide, etc. Magnesium-containing compounds include, but are not limited to, magnesium hydroxide, magnesium chloride, magnesium oxide, etc.

[0033] The sodium-containing compound and the magnesium-containing compound may be contained in either the diisocyanate monomer (l) or the polyol compound (m), or may be contained in both the diisocyanate monomer (l) and the polyol compound (m).

[0034] In the urethanization reaction in the step (1), organic zinc compounds such as zinc octylate, zinc neodecanoate, and zinc naphthenate; organic tin compounds such as stannous diacetate, stannous dioctoate, stannous dioleate, stannous dilaurate, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin oxide, and dibutyltin dichloride; organic nickel compounds such as nickel octylate and nickel naphthenate; organic cobalt compounds such as cobalt octylate and cobalt naphthenate; organic bismuth compounds such as bismuth octylate, bismuth neodecanoate, and bismuth naphthenate; organic metal catalysts such as titanium-based compounds such as tetraisopropyloxytitanate, dibutyltitanium dichloride, tetrabutyltitanium, butoxytitanium trichloride, aliphatic diketones, aromatic diketones, and titanium chelate complexes having at least one alcohol having 2 to 10 carbon atoms as a ligand;

[0035] Triethylenediamine, 2-methyltriethylenediamine, quinuclidine, 2-methylquinuclidine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N”,N”-pentamethyldiethylenetriamine, N,N,N',N”,N”-pentamethyl-(3-aminopropyl)ethylenediamine, N,N,N',N”,N”-pentamethyldipropylenetriamine, N,N,N',N'-tetramethylhexamethylenediamine, bis(2-dimethylaminoethyl)ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol, N,N-dimethyl-N'-(2-hydroxyethyl)ethylenediamine, N,N-dimethyl-N'-(2-hydroxyethyl)propanediamine, bis(dimethylaminopropyl)amine, bis(dimethylaminopropyl)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-Dimethyl Amine catalysts such as imidazole, 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, and 1-(2-hydroxypropyl)-2-methylimidazole are not used.

[0036] These compounds are often used as catalysts to promote the urethanization reaction, but if the step (2) is carried out with the urethanization catalyst remaining, side reactions may occur, causing problems such as the resulting polyurethane polyisocyanate being colored yellow or brown, the NCO% being lower than the designed value, and the viscosity increasing. Therefore, in the present invention, the step (1) is carried out in the absence of these urethanization catalysts.

[0037] On the other hand, if the above-mentioned urethanization catalyst is simply not present, it takes a long time to complete the urethanization reaction. However, the synthesis of the polyurethane polyisocyanate (A1) of the present invention is carried out in the presence of specific amounts of a sodium-containing compound and a magnesium-containing compound, so that such a problem can be suppressed.

[0038] A known method can be used for step (1), but one example is a method in which polyol compound (m) is dropped into diisocyanate monomer (l) heated to 30°C to 60°C under a nitrogen stream, and then the temperature is raised to 65°C to 85°C to perform urethane formation. Step (1) is performed until NCO% does not change substantially (until the difference from NCO% one hour before is within ±0.5%). The urethane formation reaction is determined to be complete when NCO% does not change substantially.

[0039] In step (2), the diisocyanate monomer (l') is removed from the composition obtained in step (1). The diisocyanate monomer is removed by distilling the diisocyanate monomer (l') under reduced pressure using a short-path distillation apparatus, a thin-film distillation apparatus, or the like. The degree of reduced pressure and the distillation temperature are appropriately adjusted depending on the diisocyanate monomer (l') to be removed, and are, for example, 0.1 mbar or less and 120°C to 190°C. Step (2) is performed until the content of the diisocyanate monomer (l') in the total amount of the polyurethane polyisocyanate (A1) and the diisocyanate monomer (l') is 0.1 mass% or less. This makes it possible to obtain a polyurethane polyisocyanate (A1) in which coloring and viscosity increase are suppressed.

[0040] The content of diisocyanate monomer (l') can be measured, for example, by gas chromatography using an internal standard according to ASTM D 3432. Alternatively, it can also be measured by liquid chromatography according to the following conditions.

[0041] Equipment: Waters Corporation "ACQUITY UPLC H-Class" Data processing: Waters Corporation "Empower-3" Column: Waters Corporation "ACQUITY UPLC HSS T3" (100 mm x 2.1 mmφ, 1.8 μm) 40°C Eluent: ammonium formate aqueous solution / methanol, 0.3 mL / min Detector: PDA Sample preparation: 1. Dissolve 100 mg of appropriately blocked sample in 10 ml of THF (for LC) 2. Vortex for 30 seconds. 3. Dilute appropriately with eluent (mobile phase) 4. The solution was passed through a 0.2 μm filter to prepare a measurement sample. Calculation of area ratio: Calculate using the maximum absorption wavelength for the target substance.

[0042] <Polyisocyanate composition> The polyisocyanate composition of the present invention contains the polyurethane polyisocyanate (A1) obtained by the above-mentioned method. The polyisocyanate composition may also contain a polyisocyanate compound (A2) other than the polyurethane polyisocyanate (A1). Examples of the polyisocyanate compound (A2) include biuret compounds, nurate compounds, allophanate compounds, carbodiimide-modified compounds, and uretdione-modified compounds of at least one diisocyanate selected from aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates. The polyisocyanate compound (A2) can be used alone or in combination of two or more.

[0043] The aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates may be the same as those exemplified as the diisocyanate monomer (l).

[0044] The polyisocyanate composition has a diisocyanate monomer content of 0.1 mass % or less.

[0045] The polyisocyanate composition of the present invention can be used as a two-liquid curing composition in combination with an isocyanate-reactive composition containing a compound reactive with isocyanate. Examples of the compound reactive with isocyanate include polyether polyol, polyester polyol, polyester polyether polyol, polyurethane polyol, polyester polyurethane polyol, polyether polyurethane polyol, vegetable oil polyol, sugar alcohol, polycarbonate polyol, acrylic polyol, hydroxyl group-containing olefin resin, hydroxyl group-containing fluororesin, (poly)alkanolamine, etc.

[0046] Such two-component curing compositions can be used, for example, as adhesives, coatings, sealants, elastomers, and the like.

[0047] <Adhesive> The adhesive of the present invention is a two-component curing adhesive containing a polyisocyanate composition (X) and a polyol composition (Y).

[0048] (Polyisocyanate composition (X)) The polyisocyanate composition (X) contains the polyurethane polyisocyanate (A1). The polyisocyanate composition (X) may contain a polyisocyanate compound (A2) other than the polyurethane polyisocyanate (A1). Examples of the polyisocyanate compound (A2) include biuret compounds, nurate compounds, allophanate compounds, carbodiimide-modified compounds, and uretdione-modified compounds of at least one diisocyanate selected from aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates. The polyisocyanate compounds (A2) can be used alone or in combination of two or more.

[0049] When the polyisocyanate composition (X) contains the polyisocyanate compound (A2) in addition to the polyurethane polyisocyanate (A1), the content thereof can be appropriately adjusted. As an example, the proportion of the polyurethane polyisocyanate (A1) in the total amount of the polyurethane polyisocyanate (A1) and the polyisocyanate compound (A2) is 50 mass% or more.

[0050] The polyisocyanate composition (X) used in the adhesive of the present invention has a content of diisocyanate monomers such as aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates, which are exemplified as raw materials for the polyurethane polyisocyanate (A1), of 0.1 mass % or less.

[0051] When the adhesive of the present invention is used as a solventless two-component curing adhesive, the viscosity of the polyisocyanate composition (X) is adjusted to a range suitable for the non-solvent lamination method. For example, the viscosity at 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 a polyisocyanate compound (A2) in combination. The viscosity of the polyisocyanate composition (X) is measured, for example, using a rotational viscometer with a cone and plate of 1°×diameter 50 mm and a shear rate of 100 sec. -1 , can be measured at 40°C±1°C.

[0052] (Polyol composition (Y)) The polyol composition (Y) contains a polyol compound (B) having multiple hydroxyl groups. The polyol compound (B) is not particularly limited, and any polyol compound typically used in a urethane reaction type two-component curing adhesive can be used.

[0053] Specific examples of the polyol compound (B) include polyether polyols, polyester polyols, polyester polyether polyols, polyurethane polyols, polyester polyurethane polyols, polyether polyurethane polyols, vegetable oil polyols, sugar alcohols, polycarbonate polyols, acrylic polyols, hydroxyl group-containing olefin resins, and hydroxyl group-containing fluororesins.

[0054] Examples of polyether polyols 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 such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and triethylene glycol; and trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, pentaerythritol, and polypropylene glycol triols. It is preferable to use polypropylene polyol.

[0055] The polyester polyol is a reaction product of a polyhydric alcohol and a polycarboxylic 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. In addition, the diol may be a polyester polyether polyol using the polyether polyol described above, or a polyester polyurethane polyol using a polyurethane polyol described below. Examples of diols include aliphatic diols such as ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,2,2-trimethyl-1,3-propanediol, 2,2-dimethyl-3-isopropyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-bis(hydroxymethyl)cyclohexane, and 2,2,4-trimethyl-1,3-pentanediol;

[0056] Ether glycols such as polyoxyethylene glycol and polyoxypropylene glycol; Modified polyether diols obtained by ring-opening polymerization of aliphatic diols with various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether;

[0057] Lactone-based polyester polyols obtained by polycondensation reaction of aliphatic diols with various lactones such as lactonoids and ε-caprolactone;

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

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

[0060] The tri- or higher functional polyols include aliphatic polyols such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, and pentaerythritol;

[0061] Modified polyether polyols obtained by ring-opening polymerization of aliphatic polyols with various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether;

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

[0063] Examples of polyvalent carboxylic acids used in the synthesis of polyester polyols include aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, and 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid; and anhydrides or ester-forming derivatives of these aliphatic or dicarboxylic acids; polybasic acids such as p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid, and ester-forming derivatives of these dihydroxycarboxylic acids, and dimer acid.

[0064] Examples of the vegetable oil polyol include castor oil, dehydrated castor oil, hardened castor oil which is a hydrogenated castor oil, and an alkylene oxide 5 to 50 mole adduct of castor oil.

[0065] Polyurethane polyol 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 polyhydric alcohols as those exemplified as the raw material of the polyester polyol can be used. As the high-molecular-weight polyol, polyether polyol, polyester polyol, etc. can be exemplified. As the polyisocyanate compound, the same ones as those exemplified as the diisocyanate monomer (l) or those exemplified as the polyisocyanate compound (A2) can be used.

[0066] Examples of sugar alcohols include pentaerythritol, sucrose, xylitol, sorbitol, isomalt, lactitol, maltitol, and mannitol.

[0067] The polyisocyanate composition (X) of the present invention has an extremely low content of diisocyanate monomer, so there is little concern about PAA, and coloring is also suppressed. Therefore, the adhesive of the present invention can be suitably used in the manufacture of packaging laminates used in food packaging, etc. When the adhesive of the present invention is used for such purposes, it is preferable that the polyol compound (B) contains at least one selected from polyether polyols, polyester polyols, polyester polyether polyols, polyurethane polyols, polyester polyurethane polyols, polyether polyurethane polyols, vegetable oil polyols, and sugar alcohols.

[0068] The content of these polyol compounds (B) can be appropriately adjusted depending on the purpose, and is, for example, 50 mass % or more of the solid content of the polyol composition (Y).

[0069] (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 amine compound having an NH 2 or NHR group (R is an alkyl group or aryl group which may have a functional group).

[0070] As the amine compound (C), known compounds can be used without any particular limitation, and examples thereof include methylenediamine, ethylenediamine, isophoronediamine, 3,9-dipropanamine-2,4,8,10-tetraoxaspirodoundecane, lysine, 2,2,4-trimethylhexamethylenediamine, hydrazine, piperazine, 2-hydroxyethylethylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, poly(propylene glycol)diamine, poly(propylene glycol)triamine, poly(propylene glycol)tetraamine, 1,2-diaminopropane, 1,3-diaminopropane,

[0071] 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, nonaethylenedecamine, trimethylhexamethylenediamine, tetra(aminomethyl)methane, tetrakis(2-aminoethylaminomethyl)methane, 1,3-bis(2'-aminoethylamino)propane, triethylene-bis(trimethylene)hexamine, bis(3-aminoethyl)amine, bishexamethylenetriamine, 1,4-cyclohexanediamine, 4,4'-methylenebiscyclohexylamine, 4,4'-isopropylidenebiscyclohexylamine, norbornadiamine,

[0072] amine compounds (C1) having a plurality of amino groups, such as bis(aminomethyl)cyclohexane, diaminodicyclohexylmethane, isophoronediamine, menthenediamine, bis(cyanoethyl)diethylenetriamine, 1,4-bis-(8-aminopropyl)-piperazine, piperazine-1,4-diazacycloheptane, 1-(2'-aminoethylpiperazine), 1-[2'-(2"-aminoethylamino)ethyl]piperazine, tricyclodecanediamine, and polyureaamines which are reaction products of the above-mentioned various polyamines and the above-mentioned various isocyanate components;

[0073] Primary or secondary alkanolamines (C2), such as monoethanolamine, monoisopropanolamine, monobutanolamine, N-methylethanolamine, N-ethylethanolamine, N-methylpropanolamine, diethanolamine, and diisopropanolamine;

[0074] Examples of the amines include primary or secondary amines (C3) such as ethylamine, octylamine, laurylamine, myristylamine, stearylamine, oleylamine, diethylamine, dibutylamine, and distearylamine.

[0075] The amount of the amine compound (C) blended is preferably such that the amine value of the polyol composition (Y) is 20 to 70 mgKOH / g, more preferably 25 to 50 mgKOH / g.

[0076] In this specification, the amine value means the number of milligrams of KOH equivalent to the amount of HCl required to neutralize 1 g of sample, and is not particularly limited and can be calculated using a known method. When the chemical structure of the amine compound (C) and, if necessary, the average molecular weight, etc. are known, the amine value can be calculated from (number of amino groups per molecule / average molecular weight) x 56.1 x 1000. When the chemical structure, average molecular weight, etc. of the amine compound are unknown, the amine value can be measured according to a known amine value measurement method, for example, JIS K7237-1995.

[0077] (Monool compound (D)) The polyol composition (Y) may contain a mono-ol compound (D) having one alcoholic hydroxyl group. The main chain of the mono-ol compound (D) is not particularly limited, and examples thereof include vinyl resins, acrylic resins, polyesters, epoxy resins, and urethane resins having one hydroxyl group. Aliphatic alcohols and alkyl alkylene glycols can also be used. The main chain of the mono-ol compound (D) may be linear or branched. The bonding position of the hydroxyl group is not particularly limited, but it is preferable that the hydroxyl group is present at the end of the molecular chain.

[0078] Specific examples of the monool compound (D) include aliphatic monools such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, lauryl alcohol, myristyl alcohol, pentadecanol, cetyl alcohol, heptadecanol, stearyl alcohol, nonadecanol, other alkanols (C20 to C50), oleyl alcohol, and isomers thereof;

[0079] Cyclohexanol, methylcyclohexanol, 4-butylcyclohexanol, 4-pentylcyclohexanol, 4-hexylcyclohexanol, cyclodecanol, cyclododecanol, cyclopentadecanol, 4-isopropylcyclohexanol, 3,5,5-trimethylcyclohexanol, menthol, 2-norbornanol, borneol, 2-adamantanol, dicyclohexylmethanol, decitol, 2-cyclohexylcyclohexanol, 4-cyclohexylcyclohexanol, 4-(4-propylcyclohexyl)cyclohexanol, 4-(4-pentylcyclohex cyclohexanol, α-ambrinol, desoxycorticosterone, 11-dehydrocorticosterone, cholesterol, β-sitosterol, campesterol, stigmasterol, brassicasterol, lanosterol, ergosterol, β-cholestanol, testosterone, estrone, digitoxigenin, dehydroepiandrosterone, coprostanol, pregnenolone, epicholestanol, 7-dehydrocholesterol, estradiol benzoate, tigogenin, hecogenin, methandienone, cortisone acetate, stenolone, and isomers thereof, and other alicyclic monools;

[0080] aromatic aliphatic monools such as benzyl alcohol;

[0081] Examples of the polyoxyalkylene monool include polyoxyalkylene monools obtained by ring-opening addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran using an alkyl compound containing one active hydrogen as an initiator.

[0082] When the two-component curing adhesive of the present invention is used as a solventless 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) or a plasticizer described below. When adjusting the skeleton of the polyol compound (B), the viscosity can be reduced by using, for example, polypropylene glycol or a polyester polyol obtained by reacting an aliphatic carboxylic acid with a polyol. Alternatively, the viscosity can be increased by using a polyester polyol obtained by reacting an aromatic carboxylic acid with a polyol.

[0083] (Other components of adhesive) The two-component curing adhesive of the present invention may contain components other than those mentioned above. The other components may be contained in either or both of the polyisocyanate composition (X) and the polyol composition (Y), or may be prepared separately from these and mixed with the polyisocyanate composition (X) and the polyol composition (Y) immediately before application of the adhesive. Each component will be described below.

[0084] (catalyst) Examples of the catalyst include metal catalysts, amine catalysts, aliphatic cyclic amide compounds, and quaternary ammonium salts.

[0085] Examples of the metal catalyst include metal complex catalysts, inorganic metal catalysts, and organic metal catalysts. Examples of the metal complex catalyst include acetylacetonate salts of metals selected from the group consisting of Fe (iron), Mn (manganese), Cu (copper), Zr (zirconium), Th (thorium), Ti (titanium), Al (aluminum), and Co (cobalt), such as iron acetylacetonate, manganese acetylacetonate, copper acetylacetonate, and zirconia acetylacetonate.

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

[0087] Examples of the organometallic catalyst include organozinc compounds such as zinc octylate, zinc neodecanoate, and zinc naphthenate; organotin compounds such as stannous diacetate, stannous dioctoate, stannous dioleate, stannous dilaurate, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin oxide, and dibutyltin dichloride; organonickel compounds such as nickel octylate and nickel naphthenate; organocobalt compounds such as cobalt octylate and cobalt naphthenate; organobismuth compounds such as bismuth octylate, bismuth neodecanoate, and bismuth naphthenate; titanium compounds such as tetraisopropyloxytitanate, dibutyltitanium dichloride, tetrabutyltitanium, butoxytitanium trichloride, aliphatic diketones, aromatic diketones, and titanium chelate complexes having at least one of alcohols having 2 to 10 carbon atoms as a ligand.

[0088] Examples of the amine catalyst include triethylenediamine, 2-methyltriethylenediamine, quinuclidine, 2-methylquinuclidine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N',N",N"-pentamethyl-(3-aminopropyl)ethylenediamine, N,N,N',N",N"-pentamethyldipropylenetriamine, N,N,N',N'-tetramethylhexamethylenediamine, bis(2-dimethylaminoethyl)ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol, N,N-dimethyl-N'-(2-hydroxyethyl)ethylenediamine, N,N-dimethyl-N'-(2-hydroxyethyl)propanediamine, bis(dimethylaminopropyl)amine, bis(dimethylaminopropyl)isopropanediamine, and the like. lopanolamine, 3-quinuclidinol, N,N,N',N'-tetramethylguanidine, 1,3,5-tris(N,N-dimethylaminopropyl)hexahydro-S-triazine, 1,8-diazabicyclo[5.4.0]undecene-7, N-methyl-N'-(2-dimethylaminoethyl)piperazine, N,N'-dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, 1-methylimidazole, 1 ,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethylaminopropylimidazole, N,N-dimethylhexanolamine, N-methyl-N'-(2-hydroxyethyl)piperazine, 1-(2-hydroxyethyl)imidazole, 1-(2-hydroxypropyl)imidazole, 1-(2-hydroxyethyl)-2-methylimidazole, 1-(2-hydroxypropyl)-2-methylimidazole, and the like.

[0089] Examples of the aliphatic cyclic amide compound include δ-valerolactam, ε-caprolactam, ω-enantholactam, η-capryllactam, β-propiolactam, etc. Among these, ε-caprolactam is more effective in promoting hardening.

[0090] Examples of quaternary ammonium salts include hydroxy salts of alkyl ammonium, aromatic ammonium, etc., alkyl acid salts, halide salts, etc. Examples include, but are not limited to, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltriethylammonium chloride, hexadecyltrimethylammonium bromide, etc.

[0091] (acid anhydride) Examples of the acid anhydride include cyclic aliphatic acid anhydrides, aromatic acid anhydrides, and unsaturated carboxylic acid anhydrides, and one or more of them may be used in combination. More specifically, for example, maleic acid anhydride, phthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, benzophenonetetracarboxylic acid anhydride, dodecenylsuccinic acid anhydride, polyadipic acid anhydride, polyazelaic acid anhydride, polysebacic acid anhydride, poly(ethyloctadecanedioic acid) anhydride, poly(phenylhexadecanedioic acid) anhydride, tetrahydrophthalic acid anhydride, methyltetrahydrophthalic acid anhydride, methylhexahydrophthalic acid anhydride, hexahydrophthalic acid anhydride, methylhimic acid anhydride, trialkyltetrahydrophthalic acid anhydride, methyl ... anhydride, methylcyclohexene dicarboxylic anhydride, methylcyclohexene tetracarboxylic anhydride, ethylene glycol bistrimellitate dianhydride, HET anhydride, Nadic anhydride, methylnadic 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.

[0092] In addition, the above-mentioned compounds may be modified with glycol as the acid anhydride. Examples of glycols that can be used for modification include alkylene glycols such as ethylene glycol, propylene glycol, and neopentyl glycol; and polyether glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. Furthermore, copolymer polyether glycols of two or more of these glycols and / or polyether glycols may be used.

[0093] Alternatively, among the above-mentioned compounds, a homopolymer or copolymer of a compound having a polymerizable unsaturated group such as maleic anhydride may be used as the acid anhydride (B). Examples of compounds that can be copolymerized with a compound having an acid anhydride group and a polymerizable unsaturated group include α-olefins such as ethylene, propylene, 1,3-butadiene, and cyclopentylethylene; vinyl compounds having an aromatic ring such as styrene, 1-ethynyl-4-methylbenzene, divinylbenzene, 1-ethynyl-4-methylethylbenzene, benzonitrile, acrylonitrile, p-tert-butylstyrene, 4-vinylbiphenyl, 4-ethynylbenzyl alcohol, 2-ethynylnaphthalene, and phenanthrene-9-ethynyl; and fluoroolefins such as vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, and chlorotrifluoroethylene. These 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.

[0094] (Coupling Agent) Examples of the coupling agent include a silane coupling agent, a titanate-based coupling agent, and an aluminum-based coupling agent.

[0095] Examples of the silane coupling agent include aminosilanes such as γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, and bis[3-(triethoxysilyl)propyl]amine; epoxysilanes such as β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane; vinylsilanes such as vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane; and hexamethyldisilazane and γ-mercaptopropyltrimethoxysilane.

[0096] Examples of titanate coupling agents include tetraisopropoxytitanium, tetra-n-butoxytitanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, titanium lactate, and tetrastearoxytitanium.

[0097] An example of the aluminum-based coupling agent is acetoalkoxyaluminum diisopropylate.

[0098] (Pigments) The pigment is not particularly limited, and examples thereof include organic pigments and inorganic pigments such as extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments, green pigments, blue pigments, metal powder pigments, luminescent pigments, and pearlescent pigments listed in the Paint Raw Materials Handbook 1970 Edition (compiled by the Japan Paint Manufacturers Association), as well as plastic pigments.

[0099] Examples of extender pigments include precipitated barium sulfate, powdered gourd, precipitated calcium carbonate, calcium bicarbonate, kansui stone, alumina white, silica, hydrous fine silica (white carbon), ultrafine anhydrous silica (aerosil), silica sand, talc, precipitated magnesium carbonate, bentonite, clay, kaolin, and yellow earth.

[0100] Specific examples of organic pigments include various insoluble azo pigments such as Benzidine Yellow, Hansa Yellow, Lake 4R, etc.; soluble azo pigments such as Lake C, Carmine 6B, Bordeaux 10, etc.; various (copper) phthalocyanine pigments such as Phthalocyanine Blue, Phthalocyanine Green, etc.; various chlorine dyeing lakes such as Rhodamine Lake, Methyl Violet Lake, etc.; various mordant dye pigments such as Quinoline Lake, Fast Sky Blue, etc.; various vat dye pigments such as Anthraquinone pigments, Thioindigo pigments, Perinone pigments, etc.; various quinacridone pigments such as Synchasia Red B, etc.; various dioxazine pigments such as Dioxazine Violet, etc.; various condensed azo pigments such as Chromophtal, etc.; aniline black, etc.

[0101] Examples of inorganic pigments include various chromates such as yellow lead, zinc chromate, and molybdate orange; various ferrocyanide compounds such as Prussian blue; various metal oxides such as titanium oxide, zinc oxide, mapico yellow, iron oxide, red iron oxide, chrome oxide green, and zirconium oxide; various sulfides or selenides such as cadmium yellow, cadmium red, and mercury sulfide; various sulfates such as barium sulfate and lead sulfate; various silicates such as calcium silicate and ultramarine; various carbonates such as calcium carbonate and magnesium carbonate; various phosphates such as cobalt violet and manganese purple; various metal powder pigments such as aluminum powder, gold powder, silver powder, copper powder, bronze powder, and brass powder; flake pigments of these metals, mica flake pigments; metallic pigments and pearl pigments such as mica flake pigments coated with metal oxides and micaceous iron oxide pigments; graphite, carbon black, and the like.

[0102] Examples of plastic pigments include "Grandol PP-1000" and "PP-2000S" manufactured by DIC Corporation.

[0103] The pigment to be used may be appropriately selected depending on the purpose. For example, it is preferable to use inorganic oxides such as titanium oxide and zinc oxide as white pigments because they have excellent durability, weather resistance, and design properties, and it is preferable to use carbon black as a black pigment.

[0104] The amount of the pigment is, for example, 1 to 400 parts by mass per 100 parts by mass of the total amount of the non-volatile content of the polyol composition (X) and the polyisocyanate composition (Y), and more preferably 10 to 300 parts by mass to improve adhesion and blocking resistance.

[0105] (Plasticizer) Examples of the plasticizer include phthalic acid plasticizers, fatty acid plasticizers, aromatic polycarboxylic acid plasticizers, phosphoric acid plasticizers, polyol plasticizers, epoxy plasticizers, polyester plasticizers, and carbonate plasticizers.

[0106] Examples of the phthalic acid plasticizer include phthalic acid ester plasticizers such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, diheptyl phthalate, di-(2-ethylhexyl) phthalate, di-n-octyl phthalate, dinonyl phthalate, diisononyl phthalate, didecyl phthalate, diisodecyl phthalate, ditridecyl phthalate, diundecyl phthalate, dilauryl phthalate, distearyl phthalate, diphenyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, dicyclohexyl phthalate, octyl decyl phthalate, dimethyl isophthalate, di-(2-ethylhexyl) isophthalate, and diisooctyl isophthalate; and tetrahydrophthalic acid ester plasticizers such as di-(2-ethylhexyl) tetrahydrophthalate, di-n-octyl tetrahydrophthalate, and diisodecyl tetrahydrophthalate.

[0107] 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; and di-n-butyl sebacate, di-(2 Sebacic acid plasticizers such as di-n-ethylhexyl) sebacate and diisononyl sebacate; maleic acid plasticizers such as dimethyl maleate, diethyl maleate, di-n-butyl maleate and di-(2-ethylhexyl) maleate; fumaric acid plasticizers such as di-n-butyl fumarate and di-(2-ethylhexyl) fumarate; monomethyl itaconate, monobutyl itaconate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, Examples of the plasticizer include itaconic acid-based plasticizers such as luitaconate and di-(2-ethylhexyl) itaconate; stearic acid-based plasticizers such as n-butyl stearate, glycerol monostearate, and diethylene glycol distearate; oleic acid-based plasticizers such as butyl oleate, glyceryl monooleate, and diethylene glycol monooleate; citric acid-based plasticizers such as triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tributyl citrate, and acetyl tri-(2-ethylhexyl) citrate; ricinoleic acid-based plasticizers such as methyl acetyl ricinoleate, butyl acetyl ricinoleate, glyceryl monoricinoleate, and diethylene glycol monoricinoleate; and other fatty acid-based plasticizers such as diethylene glycol monolaurate, diethylene glycol dipelargonate, and pentaerythritol fatty acid esters.

[0108] Examples of aromatic polycarboxylic acid plasticizers include trimellitic acid plasticizers such as tri-n-hexyl trimellitate, tri-(2-ethylhexyl) trimellitate, tri-n-octyl trimellitate, triisooctyl trimellitate, triisononyl trimellitate, tridecyl trimellitate, and triisodecyl trimellitate; and pyromellitic acid plasticizers such as tetra-(2-ethylhexyl) pyromellitate and tetra-n-octyl pyromellitate.

[0109] Examples of the phosphoric acid plasticizer include triethyl phosphate, tributyl phosphate, tri-(2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, octyl diphenyl phosphate, cresyl diphenyl phosphate, cresyl phenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris(chloroethyl) phosphate, tris(chloropropyl) phosphate, tris(dichloropropyl) phosphate, and tris(isopropylphenyl) phosphate.

[0110] Examples of polyol-based plasticizers include glycol-based plasticizers such as diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, triethylene glycol di-(2-ethylbutyrate), triethylene glycol di-(2-ethylhexoate), and dibutylmethylene bisthioglycolate; and glycerin-based plasticizers such as glycerol monoacetate, glycerol triacetate, and glycerol tributyrate.

[0111] Examples of epoxy plasticizers include epoxidized soybean oil, epoxy butyl stearate, di-2-ethylhexyl epoxy hexahydrophthalate, diisodecyl epoxy hexahydrophthalate, epoxy triglyceride, epoxidized octyl oleate, and epoxidized decyl oleate.

[0112] Examples of polyester plasticizers include adipic acid polyesters, sebacic acid polyesters, and phthalic acid polyesters.

[0113] Examples of carbonate plasticizers include propylene carbonate and ethylene carbonate.

[0114] Other examples of the plasticizer include partially hydrogenated terphenyls, adhesive plasticizers, and polymerizable plasticizers such as diallyl phthalate, acrylic monomers and oligomers, etc. These plasticizers can be used alone or in combination of two or more kinds.

[0115] (Phosphate Compounds) Examples of the phosphoric acid compound 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, and polyoxyethylene alkyl ether phosphate.

[0116] (Adhesive Form) The two-component curing adhesive of the present invention may be in the form of either a solvent-based or solventless type. In this specification, the term "solvent-based" adhesive refers to a form used in a 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 laminated to another substrate, that is, a so-called dry lamination method. Either the polyisocyanate composition (X) or the polyol composition (Y), or both, contain an organic solvent capable of dissolving (diluting) the constituent components of the polyisocyanate composition (X) and the polyol composition (Y) used in the present invention.

[0117] Examples of the organic solvent include esters such as ethyl acetate, butyl acetate, cellosolve acetate, etc., ketones such as acetone, methyl ethyl ketone, isobutyl ketone, cyclohexanone, etc., ethers such as tetrahydrofuran, dioxane, etc., aromatic hydrocarbons such as toluene, xylene, etc., halogenated hydrocarbons such as methylene chloride, ethylene chloride, etc., dimethyl sulfoxide, dimethyl sulfamide, etc. The organic solvent used as a reaction medium during the production of the components of the polyisocyanate composition (X) and the polyol composition (Y) may also be used as a diluent during coating.

[0118] In this specification, a "solvent-free" adhesive refers to a form of adhesive used in a non-solvent lamination method in which the polyisocyanate composition (X) and the polyol composition (Y) are substantially free of esters such as ethyl acetate, butyl acetate, cellosolve acetate, etc., ketones such as acetone, methyl ethyl ketone, isobutyl ketone, cyclohexanone, etc., ethers such as tetrahydrofuran, dioxane, etc., aromatic hydrocarbons such as toluene, xylene, etc., halogenated hydrocarbons such as methylene chloride, ethylene chloride, etc., highly soluble organic solvents such as dimethyl sulfoxide, dimethyl sulfamide, in particular ethyl acetate or methyl ethyl ketone, and in which the adhesive is applied to a substrate and then bonded to another substrate without going through a step of heating in an oven or the like to volatilize the solvent. When the organic solvent used as a reaction medium in the manufacture of the components of the polyisocyanate composition (X) or the polyol composition (Y) or the raw materials thereof cannot be completely removed and a trace amount of organic solvent remains in the polyisocyanate composition (X) or the polyol composition (Y), it is considered that the composition does not substantially contain an organic solvent. In addition, when the polyol composition (Y) contains a low molecular weight alcohol, the low molecular weight alcohol reacts with the polyisocyanate composition (X) and becomes part of the coating film, so 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 considered to be an organic solvent.

[0119] The two-component curing adhesive of the present invention is preferably used by mixing the polyisocyanate composition (X) so that the ratio [NCO] / [OH] of the number of moles of isocyanate groups [NCO] contained in the polyol composition (Y) to the number of moles of hydroxyl groups [OH] is 0.5 to 5.0, more preferably 1.0 to 3.0. This allows for appropriate curing properties to be obtained without depending on the environmental humidity during coating.

[0120] <Laminate> The laminate of the present invention can be obtained, for example, by a method having a two-liquid mixing step in which the polyisocyanate composition (X) and the polyol composition (Y) are mixed in advance, then coated on a first substrate, the second substrate is laminated on the coated surface, and the adhesive layer is cured, or by a method having a two-liquid separate coating step in which the polyisocyanate composition (X) and the polyol composition (Y) are separately coated on a first substrate and a second substrate, the coated surfaces of the first substrate and the second substrate are brought into contact with each other and pressed together to laminate the first substrate and the second substrate, and the adhesive layer is cured. There is no particular restriction on the film to be used, and a film can be appropriately selected according to the application.

[0121] Examples of films for food packaging include polyethylene terephthalate (PET) films, polystyrene films, polyamide films, polyacrylonitrile films, polyethylene films (LLDPE: low-density polyethylene film, HDPE: high-density polyethylene film, MDOPE: uniaxially oriented polyethylene film, OPE: biaxially oriented polyethylene film), polypropylene films (CPP: unoriented polypropylene film, OPP: biaxially oriented polypropylene film), polyolefin films such as gas barrier heat seal films in which an olefin-based heat sealable resin layer is provided on one or both sides of a resin having gas barrier properties such as an ethylene-vinyl alcohol copolymer or polyvinyl alcohol, polyvinyl alcohol film, and ethylene-vinyl alcohol copolymer film.

[0122] It is also preferable to use a biomass film, a biodegradable film, or a recycled plastic film formed from a material containing a biomass-derived component, a biodegradable component, or a recycled component. Biomass films, biodegradable films, and recycled plastic films are sold by various companies. In addition, it is also possible to use films certified in each country, such as film sheets such as those listed in the list of biomass certified products listed by the Japan Organics Resources Association, films such as those listed in the list of Eco Mark certified products listed by the Japan Environment Association, and films bearing the symbol mark designated by the Japan Bioplastics Association.

[0123] (Biomass film) Specifically, well-known biomass films include those using ethylene glycol derived from biomass as a raw material. Biomass-derived ethylene glycol is made from ethanol (biomass ethanol) produced from biomass as a raw material. For example, biomass-derived ethylene glycol can be obtained by a method of producing ethylene glycol from biomass ethanol via ethylene oxide using a conventionally known method. In addition, commercially available biomass ethylene glycol may be used, and for example, biomass ethylene glycol commercially available from India Glycoal Limited can be suitably used.

[0124] For example, as an alternative to conventional polyethylene terephthalate films using petroleum-based raw materials, films containing biomass polyesters and biomass polyethylene terephthalate, which have biomass-derived ethylene glycol as the diol unit and fossil fuel-derived dicarboxylic acids as the dicarboxylic acid units, are known.

[0125] The dicarboxylic acid unit of the biomass polyester uses a dicarboxylic acid derived from a fossil fuel. As the dicarboxylic acid, an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, and a derivative thereof can be used without limitation. In addition to the above diol component and dicarboxylic acid component, the copolymer polyester may be a copolymer polyester containing a copolymer component as a third component, such as a bifunctional oxycarboxylic acid or at least one polyfunctional compound selected from the group consisting of a trifunctional or higher functional polyhydric alcohol, a trifunctional or higher functional polycarboxylic acid and / or its anhydride, and a trifunctional or higher functional oxycarboxylic acid, in order to form a crosslinked structure.

[0126] In addition, for example, as an alternative to conventional polyolefin films using petroleum-based raw materials, biomass polyolefin films such as biomass polyethylene films and biomass polyethylene-polypropylene films, which contain polyethylene resins made from biomass-derived ethylene glycol, are also known. The polyethylene resin is not particularly limited except that ethylene glycol derived from biomass is used as part of the raw material. Examples of the polyethylene resin include ethylene homopolymers and copolymers of ethylene and α-olefins with ethylene as the main component (ethylene-α-olefin copolymers containing 90% by mass or more of ethylene units). These may be used alone or in combination of two or more.

[0127] The α-olefin constituting the copolymer of ethylene and α-olefin is not particularly limited, and examples thereof include α-olefins having 4 to 8 carbon atoms, such as 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene. Known polyethylene resins, such as low-density polyethylene resin, medium-density polyethylene resin, and linear low-density polyethylene resin, can be used. Among them, linear low-density polyethylene resin (LLDPE) (a copolymer of ethylene and 1-hexene, or a copolymer of ethylene and 1-octene) is preferred from the viewpoint of making damage such as holes and tears even less likely to occur even when films are rubbed against each other, and has a density of 0.910 to 0.925 g / cm. 3 More preferred is a linear low density polyethylene resin in which

[0128] Biomass films made from biomass raw materials classified by the biomass plastic degree specified by ISO16620 or ASTM D6866 are also on the market. Radioactive carbon-14C exists in the atmosphere at a ratio of 1 in 1012 particles, and this ratio does not change with atmospheric carbon dioxide, so this ratio does not change even in plants that fix this carbon dioxide through photosynthesis. For this reason, the carbon in plant-derived resins contains radioactive carbon-14C. In contrast, the carbon in fossil fuel-derived resins contains almost no radioactive carbon-14C. Therefore, by measuring the concentration of radioactive carbon-14C in the resin with an accelerator mass spectrometer, the proportion of plant-derived resin in the resin, i.e., the biomass plastic degree, can be determined.

[0129] Examples of plant-derived low-density polyethylene, which is a biomass plastic having a biomass plastic content of 80% or more, preferably 90% or more as specified by ISO16620 or ASTM D6866, include Braskem products under the trade names "SBC818", "SPB608", "SBF0323HC", "STN7006", "SEB853", and "SPB681", and films using these as raw materials can be preferably used.

[0130] In addition, films and sheets containing starch, a biomass raw material, or polylactic acid are also known. These can be selected and used appropriately depending on the application.

[0131] The biomass film may be a laminate of multiple biomass films, or a laminate of a conventional petroleum-based film and a biomass film. These biomass films may be unstretched or stretched films, and the manufacturing method thereof is not limited.

[0132] (Biodegradable film) Specifically, well-known biodegradable films include those made from commonly available biodegradable resins. For example, polycaprolactone, polyvinyl alcohol, polyamide, cellulose ester, lactic acid-based polyester resins, aliphatic polyester resins, or aliphatic aromatic polyester resins may be used. These biodegradable resins may 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 aliphatic diols and aliphatic dicarboxylic acids. Examples of the aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol. These may be used alone or in mixtures. Of these, it is preferable to use 1,4-butanediol. Examples of the aliphatic dicarboxylic acids include oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, suberic acid, and dodecanedioic acid, and acid anhydrides that are derivatives of these may also be used. Of these, succinic acid or succinic anhydride, or a mixture of these with adipic acid, is preferable. Specific examples include polybutylene succinate (PBS) obtained from 1,4-butanediol and succinic acid (eg, BioPBS manufactured by PPT MCC Biochem), and polybutylene succinate adipate (PBSA) obtained by copolymerizing PBS with adipic acid.

[0133] Examples of the aliphatic aromatic polyester resin include copolymers containing an aliphatic dicarboxylic acid unit, an aromatic dicarboxylic acid unit, and a chain aliphatic and / or alicyclic diol unit. The diol component that gives 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 these, diols having 2 to 4 carbon atoms are preferred, and ethylene glycol and 1,4-butanediol are preferred, and 1,4-butanediol is more preferred. The dicarboxylic acid component that gives 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 these, succinic acid or adipic acid is preferred. Examples of aromatic dicarboxylic acid components that give aromatic dicarboxylic acid units include terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid. Of these, terephthalic acid and isophthalic acid are preferred, with terephthalic acid being more preferred. Specifically, PBAT (for example, Ecoflex manufactured by BASF), which is a copolymer of 1,4-butanediol, adipic acid, and terephthalic acid, can be mentioned.

[0134] Other examples include poly(3-hydroxyalkanoates) which are aliphatic polyester copolymers obtained from hydroxyalkanoic acids and polycarboxylic acids (particularly, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) (e.g., Aonilex manufactured by Kaneka Corporation) and polylactic acid (PLA) (e.g., REVODE manufactured by Kaisei Biomaterials, and Ingeo manufactured by Natureworks).

[0135] The biodegradable film may be a laminate of a plurality of biodegradable films, or a laminate of a conventional petroleum-based film and a biodegradable film. These biodegradable films may be unstretched or stretched films, and the manufacturing method thereof is not limited.

[0136] The film may be one that has been subjected to a stretching treatment. As a stretching method, a typical method is to melt-extrude a resin into a sheet shape by an extrusion film forming method or the like, and then perform simultaneous biaxial stretching or sequential biaxial stretching. In the case of sequential biaxial stretching, it is common to first perform longitudinal stretching and then transverse stretching. Specifically, a method is often used in which longitudinal stretching utilizing the speed difference between rolls and transverse stretching using a tenter are combined.

[0137] The film surface may be subjected to various surface treatments such as flame treatment and corona discharge treatment as necessary so that an adhesive layer free from defects such as film breakage and repellency is formed.

[0138] Alternatively, a film having a vapor-deposited layer of a metal such as aluminum or a metal oxide such as silica or alumina, or a barrier film containing a gas barrier layer such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, vinylidene chloride, etc. can be used in combination. By using such a film, a laminate having a barrier property against water vapor, oxygen, alcohol, inert gas, volatile organic compounds (fragrances), etc. can be obtained.

[0139] The paper can be made of any known paper base material without any particular limitation. Specifically, the paper is made by a known paper 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, ground pulp, chemi-ground pulp, thermomechanical pulp, etc., made by sulfate cooking method, acidic / neutral / alkaline sulfite cooking method, soda salt cooking method, etc., can be used. In addition, various commercially available wood-free papers, coated papers, backing papers, impregnated papers, cardboard, paperboard, etc. can also be used.

[0140] More specifically, the laminate has the following structure: (1) Substrate 1 / adhesive layer 1 / sealant film (2) Substrate 1 / adhesive layer 1 / metal-deposited unstretched film (3) Substrate 1 / adhesive layer 1 / metal-deposited stretched film (4) Transparent vapor-deposited stretched film / adhesive layer 1 / sealant film (5) Substrate 1 / adhesive layer 1 / substrate 2 / adhesive layer 2 / sealant film (6) Substrate 1 / adhesive layer 1 / metal-deposited stretched film / adhesive layer 2 / sealant film (7) Substrate 1 / adhesive layer 1 / transparent vapor-deposited stretched film / adhesive layer 2 / sealant film (8) Substrate 1 / adhesive layer 1 / metal layer / adhesive layer 2 / sealant film (9) Substrate 1 / adhesive layer 1 / substrate 2 / adhesive layer 2 / metal layer / adhesive layer 3 / sealant film (10) Substrate 1 / adhesive layer 1 / metal layer / adhesive layer 2 / substrate 2 / adhesive layer 3 / sealant film These include, but are not limited to, the following:

[0141] Examples of the substrate 1 used in the configuration (1) include MDOPE film, OPE film, OPP film, PET film, nylon film, paper, etc. In addition, the substrate 1 may be coated with a coating for the purpose of improving the gas barrier property or the ink receptivity when providing a printing layer described later. Examples of commercially available substrate films 1 with coatings 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 sealant films include CPP film, LLDPE film, easy-to-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 adhesive layer 1 side (when a substrate film 1 with coating is used, the surface of the coating layer on the adhesive layer 1 side) or on the surface opposite to the adhesive layer 1. The printing layer is formed by a general printing method that has been used for printing on polymer films and paper using various printing inks such as gravure ink, flexo ink, offset ink, stencil ink, and inkjet ink.

[0142] Examples of the substrate 1 used in the structures (2) and (3) include MDOPE film, OPE film, OPP film, PET film, paper, etc. The adhesive layer 1 is a cured coating of the adhesive of the present invention. Examples of the metal-vapor-deposited unstretched film include a CPP film, an LLDPE film, and a VM-CPP film or a VM-LLDPE film obtained by subjecting a gas-barrier heat seal film to metal vapor deposition such as aluminum, and examples of the metal-vapor-deposited stretched film include a VM-MDOPE film, a VM-OPE film, or a VM-OPP film obtained by subjecting an MDOPE film, an OPE film, or an OPP film to metal vapor deposition such as aluminum. A printed layer may be provided on either side of the substrate 1 in the same manner as in the structure (1).

[0143] Examples of the transparent vapor-deposited stretched film used in the structure (4) include films obtained by vapor-depositing silica or alumina on MDOPE film, OPE film, OPP film, PET film, nylon film, etc. For the purpose of protecting the inorganic vapor-deposited layer of silica or alumina, a film with a coating on the vapor-deposited layer may be used. The adhesive layer 1 is a cured coating of the adhesive of the present invention. Examples of the sealant film include the same as those in the structure (1). A printed layer may be provided on the surface of the transparent vapor-deposited stretched film on the adhesive layer 1 side (when a film with a coating on the inorganic vapor-deposited layer is used, the surface of the coating layer on the adhesive layer 1 side). The method of forming the printed layer is the same as in the structure (1).

[0144] Examples of the substrate 1 used in the structure (5) include PET film and paper. Examples of the substrate 2 include nylon film. At least one of the adhesive layer 1 and the adhesive layer 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those in the structure (1). As in the structure (1), a printed layer may be provided on either side of the substrate 1.

[0145] The substrate 1 in the structure (6) may be the same as those in the structures (2) and (3). Metal-vapor-deposited stretched films include VM-MDOPE films, VM-OPE films, VM-OPP films, and VM-PET films obtained by subjecting MDOPE films, OPE films, OPP films, and PET films to metal vapor deposition such as aluminum. 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. The sealant film may be the same as those in the structure (1). A printed layer may be provided on either side of the substrate 1 in the same manner as in the structure (1).

[0146] Examples of the substrate 1 in the structure (7) include PET film, paper, etc. Examples of the transparent vapor deposition stretched film include those similar to those in the structure (4). At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those in the structure (1). As in the structure (1), a printed layer may be provided on either side of the substrate 1.

[0147] The substrate 1 in the structure (8) may be a PET film, paper, or the like. The metal layer may be an aluminum foil, or the like. At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. The sealant film may be the same as that in the structure (1). A printed layer may be provided on either side of the substrate 1 in the same manner as in the structure (1).

[0148] Examples of the substrate 1 in the structures (9) and (10) include PET film, paper, etc. Examples of the substrate 2 include nylon film, etc. Examples of the metal layer include aluminum foil, etc. At least one layer of the adhesive layers 1, 2, and 3 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those in the structure (1). As in the structure (1), a printed layer may be provided on either side of the substrate 1.

[0149] When the laminate of the present invention contains at least one of a metal vapor deposition film, a transparent vapor deposition film, and a metal layer, the adhesive layer in contact with the metal vapor deposition layer, the transparent vapor deposition layer, and the metal layer is preferably a cured coating film of the adhesive of the present invention.

[0150] When the adhesive of the present invention is used as an adhesion promoter, the adhesion promoter of the present invention is applied to a film material serving as a substrate using a roll such as a gravure roll, the organic solvent is evaporated by heating in an oven or the like, and then a molten polymer material is laminated using an extruder to obtain the laminate of the present invention.

[0151] The laminate of the present invention may further include other films and substrates in addition to the above-mentioned configurations (1) to (10). As the other substrates, in addition to the above-mentioned stretched films, unstretched films, and transparent vapor deposition films, porous substrates such as paper, wood, and leather, which will be described later, can also be used. The adhesive used when bonding the other substrates may be the adhesive of the present invention or may not be the adhesive.

[0152] The "other layer" may contain known additives or stabilizers, such as antistatic agents, adhesion enhancing coating agents, plasticizers, lubricants, antioxidants, etc. Furthermore, the "other layer" may be a film whose surface has been pretreated with corona treatment, plasma treatment, ozone treatment, chemical treatment, solvent treatment, etc., in order to improve adhesion when laminated with other materials.

[0153] The laminate of the present invention can be suitably used for various applications, such as packaging materials for food, medicines, and daily necessities; paper tableware such as lid materials, paper straws, paper napkins, paper spoons, paper plates, and paper cups; wall materials, roofing materials, solar cell panel materials, packaging materials for batteries, window materials, outdoor flooring materials, lighting protection materials, automotive parts, signs, stickers, and other outdoor industrial applications; decorative sheets used in simultaneous injection molding decoration methods, and packaging materials for liquid laundry detergents, liquid kitchen detergents, liquid bath detergents, liquid bath soaps, liquid shampoos, liquid conditioners, and the like.

[0154] <Packaging material> The laminate of the present invention can be used as a multi-layer packaging material for protecting foods, medicines, etc. When used as a multi-layer packaging material, the layer structure can be changed depending on the contents, the environment of use, and the form of use. In addition, the package of the present invention may be appropriately provided with an easy-opening treatment or a resealable means.

[0155] An example of a specific embodiment of the packaging material of the present invention is a packaging material obtained by making a bag from a laminate having a sealant film, such as the laminate configuration examples (1), (4) to (10) described above. The laminate is folded or overlapped so that the inner layer surface (sealant film surface) faces each other, and the peripheral edge is heat-sealed to form a bag. Examples of the bag-making method include heat-sealing methods using a side seal type, a two-sided seal type, a three-sided seal type, a four-sided seal type, an envelope seal type, a grooving seal type, a pleated seal type, a flat bottom seal type, a square bottom seal type, a gusset type, and other heat seal types. The packaging material of the present invention can take various forms depending on the contents, the environment of use, and the form of use. A self-supporting packaging material (standing pouch) is also possible. Examples of the heat-sealing method include known methods such as bar seal, rotary roll seal, belt seal, impulse seal, high frequency seal, and ultrasonic seal.

[0156] The packaging material of the present invention is filled with contents through its opening, and the opening is then heat-sealed to produce a product using the packaging material of the present invention. The contents to be filled include, for example, foods such as rice crackers, bean snacks, nuts, biscuits, cookies, wafers, marshmallows, pies, semi-dried cakes, candies, snacks, and other confectioneries, bread, snack noodles, instant noodles, dried noodles, pasta, aseptically packaged cooked rice, porridge, porridge, packaged rice cakes, and cereal foods, and other staple foods, pickles, boiled beans, natto, miso, frozen tofu, tofu, nametake mushrooms, konjac, wild vegetable processed products, jams, peanut cream, salads, frozen vegetables, and potato processed products, livestock processed products such as hams, bacon, sausages, chicken processed products, and corned beef, and fish hams, These include processed seafood products such as sausages, fish paste products, kamaboko, nori, tsukudani, bonito flakes, shiokara, smoked salmon, and spicy cod roe; fruit pulp such as peaches, mandarin oranges, pineapples, apples, pears, and cherries; vegetables such as corn, asparagus, mushrooms, onions, carrots, radishes, and potatoes; cooked foods such as hamburger steaks, meatballs, seafood fries, gyoza, croquettes, and other frozen and chilled prepared foods; dairy products such as butter, margarine, cheese, cream, instant creamy powder, and infant formula; liquid seasonings, retort curry, and pet food.

[0157] In addition, the composition can be used as a packaging material for various non-food items, such as tobacco, disposable hand warmers, medicines such as infusion packs, liquid laundry detergent, liquid kitchen detergent, liquid bath detergent, liquid bath soap, liquid shampoo, liquid conditioner, cosmetics such as lotion and milky lotion, vacuum insulation materials, batteries, etc. EXAMPLES

[0158] The present invention will be described in more detail below with reference to specific synthesis examples and examples, but the present invention is not limited to these examples. In the following examples, "parts" and "%" respectively represent "parts by mass" and "% by mass" unless otherwise specified.

[0159] <Polyurethane polyisocyanate (A1)> Example 1 (Polyurethane polyisocyanate (A1-1)) (Process (1)) 827.59 g of tolylene diisocyanate (TDI), 0.22 mg of sodium hydroxide, 0.029 mg of magnesium hydroxide, 327.59 g of bifunctional polypropylene glycol having a molecular weight of 400 (AGC EXCENOL 420) (hereinafter referred to as PPG400D), and 327.59 g of bifunctional polypropylene glycol having a molecular weight of 2000 (DOW VORANOL2120) (hereinafter referred to as PPG2000D) were reacted under a nitrogen stream at 80°C until the NCO% did not change, to obtain a composition containing polyurethane polyisocyanate (A1-1) and unreacted TDI.

[0160] (Process (2)) The resulting composition was transferred to a thin-film distillation apparatus and purified under conditions of a pressure of about 0.02 Torr and a temperature of 160° C. until the TDI in the composition was 0.05% by mass, thereby obtaining a polyisocyanate composition (X-1). The calculated sodium atom content of polyurethane polyisocyanate (A1-1) was 125 ppb, the magnesium atom content was 12 ppb, and the mass ratio of both atoms, Na / Mg, was 10.4.

[0161] (Example 2) to (Example 12) (Polyurethane polyisocyanates (A1-2) to (A1-12)) Polyurethane polyisocyanates (A1-2) to (A1-12) were obtained in the same manner as for polyurethane polyisocyanate (A1-1), except that the raw materials, sodium content, and magnesium content were changed to those shown in Tables 1 and 2.

[0162] (Comparative Example 1) to (Comparative Example 12) (Polyurethane polyisocyanates (A1'-1) to (A1'-12)) Polyurethane polyisocyanates (A1'-1) to (A1'-12) were obtained in the same manner as for polyurethane polyisocyanate (A1-1), except that the raw materials, sodium content, and magnesium content were changed to those shown in Tables 3 and 4.

[0163] The details of the compounds in Tables 1 to 4 are as follows. TDI: Tolylene diisocyanate HDI: Hexamethylene diisocyanate MDI50: Diphenylmethane diisocyanate (mixture of 4,4'-MDI- and 2,4'-MDI isomers) PPG400D: Difunctional polypropylene glycol with a molecular weight of 400 PPG1000D: Bifunctional polypropylene glycol with a molecular weight of 1000 PPG2000D: Bifunctional polypropylene glycol with a molecular weight of 2000 PEG1000D: Bifunctional polyethylene glycol with a molecular weight of 1000 NaOH: Sodium hydroxide Mg(OH) 2 : Magnesium hydroxide

[0164] [Table 1]

[0165] [Table 2]

[0166] [Table 3]

[0167] [Table 4]

[0168] <Evaluation> (Reaction time) In the synthesis of the polyurethane polyisocyanate (A1) in the Examples and Comparative Examples, the time until the end of step (1) (until the NCO% stopped changing) was evaluated on a three-point scale according to the following criteria, and the results are summarized in Tables 5 to 8. ○: Less than 8 hours △: 8 hours or more, less than 10 hours ×: 10 hours or more

[0169] (Gardner color) The composition after step (1) and the polyurethane polyisocyanate (A1) after step (2) were each placed in a flat-bottomed colorless hard glass test tube with an inner diameter of 10.75±0.1 mm and a length of 112±1 mm, and the Gardner color was measured using a TZ-6000 manufactured by Nippon Denshoku Industries Co., Ltd. The results were evaluated on a four-point scale according to the following criteria, and the results are summarized in Tables 5 to 8. ○: Less than 3 △: 3 or more, less than 4 ×: 4 or more, less than 6 ××:6 or more

[0170] (NCO%) 5g of sample was weighed into a clean, dry 300mL stoppered Erlenmeyer flask, and 15mL of dehydrated ethyl acetate was added to it using a measuring cylinder to dissolve the sample. After complete dissolution, 10mL of 1mol / l di-n-butylamine toluene solution was added using a whole pipette and mixed well. After leaving it at room temperature for 20 minutes or more, about 30mL of methanol was added using a measuring cylinder. 7-8 drops of bromophenol blue indicator were added and titrated with 0.5mol / l hydrochloric acid solution. The end point was when the color changed from purple to yellow. A blank test was also performed at the same time, and the NCO% (measured value) was calculated using the following formula, and the measured value was obtained by rounding off to the nearest tenth of a decimal point.

[0171]

number

[0172] In addition, the NCO% (theoretical value) was calculated on the assumption that an equimolar amount of isocyanate reacted with the hydroxyl group of the polyol from the amount of isocyanate and the amount of polyol used in the synthesis of the polyurethane polyisocyanate (A1) (since the reaction was carried out in a system in which an excess amount of isocyanate groups existed relative to the hydroxyl groups, the reaction in which the polyol forms a urethane bond at the terminal of the isocyanate did not occur). The NCO% (measured value) and NCO% (theoretical value) were compared and evaluated on a three-point scale according to the following evaluation criteria, and the results are summarized in Tables 5 to 8. ○: The difference between the theoretical value and the measured value is less than 0.2% △: The difference between the theoretical value and the measured value is 0.2% or more and less than 0.4% ×: The difference between the theoretical value and the measured value is 0.4% or more.

[0173] [Table 5]

[0174] [Table 6]

[0175] [Table 7]

[0176] [Table 8]

[0177] (Color of laminate) The polyurethane polyisocyanate (A1-1) was used as the polyisocyanate composition (X-1), and a trifunctional polypropylene glycol having a molecular weight of 400 (AGC Exenol 430) was used as the polyol composition (Y) were mixed in the compounding ratio shown in Table 9 to prepare the two-component curing adhesive of Example 1.

[0178] The adhesives of Examples 2 to 12 and Comparative Examples 1 to 12 were prepared in the same manner as in Example 1, except that the polyurethane polyisocyanates (A1-2) to (A1-12) and (A1'-1) to (A1'-12) were replaced by polyisocyanate compositions (X-2) to (X-12) and (X'-1) to (X'-12), respectively.

[0179] The prepared adhesive was applied to a plain oriented polypropylene film at a coating weight of 2.0 g / m using a laminator set at a lamination speed of 150 m / min. 2 The coating was applied so that the coating became approximately 100% pure, and then the coating was laminated with a non-oriented polypropylene film and aged at 40° C. for 3 days to prepare a laminate for evaluation.

[0180] The laminate was cut into a 15 cm x 15 cm rectangular piece and fixed to a white copy paper (Nippon Paper Industries, CHW-A4) with adhesive tape. The color was evaluated visually, and the results are summarized in Tables 9 to 12. 〇: Colorless △: Slightly yellowish ×: Yellowish ××: Dark yellow

[0181] [Table 9]

[0182] [Table 10]

[0183] [Table 11]

[0184] [Table 12]

Claims

1. A polyurethane polyisocyanate (A1) which is a reaction product of a diisocyanate monomer (l) and a polyol compound (m) synthesized in the presence of a sodium-containing compound and a magnesium-containing compound; 0.1% by weight or less of a diisocyanate monomer (l'); Sodium, Magnesium, The sodium content of the polyurethane polyisocyanate (A1) is 100 ppb or more and 700 ppb or less, the magnesium content of the polyurethane polyisocyanate (A1) is 10 ppb or more and 50 ppb or less, a mass ratio (Na / Mg) of the sodium to the magnesium is 2 or more and 70 or less; The polyisocyanate composition (X) wherein the sodium-containing compound is selected from sodium hydroxide, sodium chloride, and sodium oxide, and the magnesium-containing compound is selected from magnesium hydroxide, magnesium chloride, and magnesium oxide.

2. The polyisocyanate composition (X) according to claim 1, wherein the polyol compound (m) is a polyether polyol.

3. The polyurethane polyisocyanate composition (X) according to claim 1, which contains at least one polyisocyanate (A2) selected from the group consisting of a biuret, a nurate, an allophanate, a carbodiimide-modified product, and a uretdione-modified product of at least one diisocyanate selected from the group consisting of aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates.

4. A two-component curing composition comprising the polyisocyanate composition (X) according to claim 1 and an isocyanate-reactive composition containing a compound reactive with isocyanate.

5. A two-component curing adhesive comprising the polyisocyanate composition (X) according to claim 1 and a polyol composition (Y) containing a polyol compound (B).

6. 6. A laminate comprising a first substrate, a second substrate, and an adhesive layer that bonds the first substrate and the second substrate, the adhesive layer being a cured coating film of the two-component curing adhesive according to claim 5.

7. A packaging material comprising the laminate according to claim 6.

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