Polyisocyanate composition, two-part curable adhesive, laminate, and packaging material

Abstract

The present invention provides: a packaging material which is excellent in terms of breaking resistance and easy tearability; a polyisocyanate composition which is suitable for the manufacturing of this packaging material; and an adhesive.　The present invention specifically provides a polyisocyanate composition (X) which contains a polyisocyanate compound (A), wherein: the polyisocyanate compound (A) contains 60 mass% or more of a bifunctional polyisocyanate compound (A1) that is derived from a non-aromatic diisocyanate; a polyol mixture contains 70 ± 1 mass% of a polypropylene diol that has a hydroxyl value-based number average molecular weight of 415 ± 20 and 30 ± 1 mass% of a polypropylene triol that has a number average molecular weight of 415 ± 35; a coating film, which is obtained by curing with the molar ratio [NCO] / [OH] of the isocyanate groups of the polyisocyanate compound (A) to the hydroxyl groups of the polyol mixture being 1.3 ± 0.1, has an elongation at break of 30% or more as determined at a tensile rate of 200 mm / minute at 25°C and a humidity of 40%.

Description

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

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

[0002] Laminates used for various packaging materials, labels, etc. are imparted with design, functionality, storage stability, convenience, transport durability, etc. by laminating a wide variety of substrates such as plastic films, metal foils, paper, etc. The laminates are laminated using a urethane-based two-component curing adhesive, and packaging materials formed by molding the laminates into bags are used as packaging materials for foods, medicines, detergents, etc. (Patent Document 1).

[0003] Japanese Patent Application Laid-Open No. 2014-159548

[0004] Such packaging materials may require tear resistance to prevent the packaging material from tearing and spilling the contents if dropped while filled with contents. Packaging materials often have slits to make them easier for consumers to open. By tearing along the slit, the packaging material can be opened without using a blade. The present invention aims to provide a packaging material that has excellent tear resistance and easy tearing properties, as well as a polyisocyanate composition and an adhesive suitable for producing such a packaging material.

[0005] That is, the present invention provides a polyisocyanate composition (X) containing a polyisocyanate compound (A), wherein the polyisocyanate compound (A) contains a bifunctional polyisocyanate compound (A1) derived from a non-aromatic diisocyanate, and the content of the polyisocyanate compound (A1) in the polyisocyanate compound (A) is 60 mass % or more, and the polyisocyanate composition (X) is a mixture of 70 mass % polypropylene diol having a hydroxyl value number average molecular weight of 415 ± 20 and 70 mass % polypropylene diol having a number average molecular weight of 415 ± 20. The polyisocyanate composition (X) relates to a coating film obtained by curing a polyol mixture containing 30±1 mass% of a 15±35 polypropylene triol (wherein the total of the polypropylene diol and the polypropylene triol is 100 mass%) at a molar ratio [NCO] / [OH] of the isocyanate groups in the polyisocyanate compound (A) to the hydroxyl groups in the polyol mixture of 1.3±0.1, wherein the coating film has an elongation at break of 30% or more at a tensile speed of 200 mm / min, at 25°C, and at a humidity of 40%.

[0006] According to the present invention, it is possible to provide a packaging material that is excellent in resistance to bag rupture and ease of tearing, as well as a polyisocyanate composition, adhesive, and laminate that are suitable for producing the packaging material.

[0007] <Polyisocyanate Composition (X)> (Polyisocyanate Compound (A)) The polyisocyanate composition (X) of the present invention contains a polyisocyanate compound (A). The polyisocyanate compound (A) also contains, as an essential component, a bifunctional polyisocyanate compound (A1) derived from a non-aromatic diisocyanate. Specific examples of the polyisocyanate compound (A1) include biuret compounds, adduct compounds, allophanate compounds, carbodiimide-modified compounds, and uretdione-modified compounds of non-aromatic diisocyanates, and these compounds can be used alone or in combination.

[0008] Examples of non-aromatic diisocyanates include aromatic aliphatic diisocyanates (aliphatic isocyanates having one or more aromatic rings in the molecule) such as m- or p-xylylene diisocyanate (also known as XDI) and α,α,α',α'-tetramethylxylylene diisocyanate (also known as TMXDI), and aliphatic diisocyanates such as 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). isocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, isophorone diisocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebiscyclohexyl isocyanate (also known as hydrogenated MDI or HMDI), 1,3-bis(isocyanatomethyl)cyclohexane (also known as hydrogenated XDI or HXDI), norbornane diisocyanate (also known as NBDI), and other alicyclic diisocyanates, which may be used alone or in combination.

[0009] Examples of polyols used in the synthesis of adducts include glycols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3propanediol, 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; bisphenols such as bisphenol A, bisphenol F, hydrogenated bisphenol A, and hydrogenated bisphenol F; dimer diol;

[0010] Polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexylene using the glycols as polymerization initiators; polyether urethane polyols obtained by further increasing the molecular weight of polyether polyols with an isocyanate compound;

[0011] Polyester polyols (1) are reaction products of the glycols with polyesters obtained by ring-opening polymerization of cyclic ester compounds such as propiolactone, butyrolactone, ε-caprolactone, σ-valerolactone, and β-methyl-σ-valerolactone; and polyester polyols (2) are reaction products of bifunctional polyols such as the glycols, dimer diols, or bisphenols with bifunctional carboxylic acids.

[0012] Examples of the polyurethane polyol include: a polyurethane polyol obtained by reacting a bifunctional polyol such as the glycol, dimer diol, or bisphenol with a bifunctional isocyanate; a polyether urethane polyol obtained by further increasing the molecular weight of the polyether polyol with an isocyanate compound; and a polyester polyurethane polyol obtained by reacting polyester polyols (1) to (2) with a bifunctional isocyanate.

[0013] Examples of the bifunctional carboxylic acid used in the synthesis of the polyester polyol (2) 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, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid, 5-sodiumsulfoisophthalic acid, tetrachlorophthalic anhydride, and tetrabromophthalic anhydride; methyl esters of aromatic polybasic acids such as dimethylterephthalic acid and dimethyl 2,6-naphthalenedicarboxylate;

[0014] 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;

[0015] 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-1,2-anhydride, himic anhydride, and HET acid anhydride can be mentioned, and these can be used alone or in combination of two or more.

[0016] As the bifunctional isocyanate used in the synthesis of polyurethane polyol, a non-aromatic diisocyanate or a derivative thereof is preferably used.

[0017] The molecular weight of the polyol used in synthesizing the adduct can be adjusted as appropriate, but is, for example, 50 g / mol or more and 4000 g / mol or less.

[0018] The adduct can be obtained by reacting a non-aromatic diisocyanate with a polyol under conditions in which the isocyanate groups of the isocyanate are in excess relative to the hydroxyl groups of the polyol, and then removing unreacted diisocyanate monomers as necessary. The equivalent ratio of isocyanate groups to hydroxyl groups [NCO] / [hydroxyl group] can be appropriately adjusted, but is, for example, 2.0 to 20.0.

[0019] The polyisocyanate composition (X) of the present invention may contain a polyisocyanate compound (A2) other than the polyisocyanate compound (A1). Examples of the polyisocyanate compound (A2) include monofunctional or tri- or higher functional polyisocyanate compounds derived from non-aromatic diisocyanates, and polyisocyanate compounds derived from aromatic diisocyanates. From the viewpoint of bag rupture resistance and tearability, the content of the polyisocyanate compound (A2) is 40% by mass or less of the polyisocyanate compound (A). In other words, the content of the polyisocyanate compound (A1) in the polyisocyanate compound (A) is 60% by mass or more. The content of the polyisocyanate compound (A1) in the polyisocyanate compound (A) may be 70% by mass or more, 80% by mass or more, or 90% by mass or more. The polyisocyanate compound (A) does not necessarily contain the polyisocyanate compound (A2).

[0020] The polyisocyanate composition (X) used in the present invention may contain a diisocyanate monomer, i.e., a diisocyanate monomer such as a non-aromatic diisocyanate exemplified as a raw material for the polyisocyanate compound (A1), or an aromatic diisocyanate such as toluene diisocyanate or diphenylmethane diisocyanate. There are concerns about the harmfulness of diisocyanate monomers to the human body, and from the viewpoint of occupational safety and health, the content thereof is preferably 5% by mass or less of the polyisocyanate composition (X), and is also preferably reduced to 0.1% by mass or less.

[0021] From the viewpoint of occupational safety and health, there is a movement to restrict the use of isocyanate monomers, and the European Commission has adopted the REACH regulation, which prohibits the marketing of products containing 0.1% by mass or more of isocyanate monomers unless certain requirements are met. Products that comply with this regulation can be made by removing unreacted diisocyanate monomers until the amount of diisocyanate monomer in the polyisocyanate composition is 0.1% by mass or less.

[0022] The diisocyanate monomer can be removed by distilling the diisocyanate monomer under reduced pressure using a short-path distillation apparatus, a thin-film distillation apparatus, etc. The degree of reduced pressure and the distillation temperature are appropriately adjusted depending on the diisocyanate monomer to be removed, and are, for example, 0.1 mbar or less and 120° C. to 190° C. The diisocyanate monomer removal step may be carried out multiple times.

[0023] The content of diisocyanate monomer can be measured by gas chromatography using an internal standard, for example, in accordance with ASTM D 3432. Alternatively, it can also be measured by liquid chromatography under the following conditions.

[0024] Equipment: Waters Corporation "ACQUITY UPLC H-Class" Data processing: Waters Corporation "Empower-3" Column: Waters Corporation "ACQUITY UPLC HSS T3" (100 mm x 2.1 mmφ, 1.8 μm) 40°C Eluent: Ammonium formate aqueous solution / methanol, 0.3 mL / min Detector: PDA Sample preparation: 1. Dissolve 100 mg of appropriately blocked sample in 10 ml of THF (for LC) 2. Vortex for 30 seconds 3. Dilute appropriately with eluent (mobile phase) 4. Pass through a 0.2 μm filter to prepare the measurement sample. Calculation of area ratio: Calculate using the maximum absorption wavelength for the target substance.

[0025] The polyisocyanate composition (X) may contain components other than the polyisocyanate compound, such as, but not limited to, a solvent (B), a phosphoric acid derivative (C), a plasticizer (D), and the like.

[0026] (Solvent (B)) Examples of the 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., and these can be used alone or in combination of two or more. The polyisocyanate composition (X) of the present invention can also be used as a so-called solventless type that does not contain a solvent (B).

[0027] (Phosphoric Acid Derivative (C)) Examples of the phosphoric acid derivative (C) include phosphoric acid, pyrophosphoric acid, triphosphoric acid, methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, dibutyl phosphate, 2-ethylhexyl acid phosphate, bis(2-ethylhexyl) phosphate, isododecyl acid phosphate, butoxyethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, polyoxyethylene alkyl ether phosphate, etc. Phosphoric acid, pyrophosphoric acid, triphosphoric acid, and butyl acid phosphate are preferred.

[0028] When the polyisocyanate composition (X) of the present invention contains the phosphoric acid derivative (C), its content can be appropriately adjusted, but is, for example, 10 ppm or more and 5000 ppm or less, more preferably 50 ppm or more, and more preferably 1000 ppm or less, of the solid content of the polyisocyanate composition (X).

[0029] (Plasticizer (D)) Examples of the plasticizer (D) include phthalic acid-based plasticizers, fatty acid-based plasticizers, aromatic polycarboxylic acid-based plasticizers, phosphoric acid-based plasticizers, polyol-based plasticizers, epoxy-based plasticizers, polyester-based plasticizers, and carbonate-based plasticizers.

[0030] Examples of the phthalic acid plasticizer include phthalic acid ester plasticizers such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, diheptyl phthalate, di-(2-ethylhexyl) phthalate, di-n-octyl phthalate, dinonyl phthalate, diisononyl phthalate, didecyl phthalate, diisodecyl phthalate, ditridecyl phthalate, diundecyl phthalate, dilauryl phthalate, distearyl phthalate, diphenyl phthalate, dibenzyl phthalate, butylbenzyl phthalate, dicyclohexyl phthalate, octyldecyl phthalate, dimethyl isophthalate, di-(2-ethylhexyl) isophthalate, and diisooctyl isophthalate; and tetrahydrophthalic acid ester plasticizers such as di-(2-ethylhexyl) tetrahydrophthalate, di-n-octyl tetrahydrophthalate, and diisodecyl tetrahydrophthalate.

[0031] Examples of the fatty acid plasticizer include adipic acid plasticizers such as di-n-butyl adipate, di-(2-ethylhexyl) adipate, diisodecyl adipate, diisononyl adipate, di(C6-C10 alkyl) adipate, and dibutyl diglycol adipate; azelaic acid plasticizers such as di-n-hexyl azelate, di-(2-ethylhexyl) azelate, and diisooctyl azelate; and di-n-butyl sebacate and di-(2 Sebacic acid plasticizers such as di-n-butyl maleate, di-(2-ethylhexyl) sebacate, and diisononyl sebacate; maleic acid plasticizers such as dimethyl maleate, diethyl maleate, di-n-butyl maleate, and di-(2-ethylhexyl) maleate; fumaric acid plasticizers such as di-n-butyl fumarate and di-(2-ethylhexyl) fumarate; monomethyl itaconate, monobutyl itaconate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, Examples of suitable plasticizers include itaconic acid-based plasticizers such as itaconate and di-(2-ethylhexyl)itaconate; stearic acid-based plasticizers such as n-butyl stearate, glycerin monostearate, and diethylene glycol distearate; oleic acid-based plasticizers such as butyl oleate, glyceryl monooleate, and diethylene glycol monooleate; citric acid-based plasticizers such as triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tributyl citrate, and acetyl tri-(2-ethylhexyl) citrate; ricinoleic acid-based plasticizers such as methyl acetyl ricinoleate, butyl acetyl ricinoleate, glyceryl monoricinoleate, and diethylene glycol monoricinoleate; and other fatty acid-based plasticizers such as diethylene glycol monolaurate, diethylene glycol dipelargonate, and pentaerythritol fatty acid esters.

[0032] 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.

[0033] Examples of phosphoric acid plasticizers include triethyl phosphate, tributyl phosphate, tri-(2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, octyl diphenyl phosphate, cresyl diphenyl phosphate, cresyl phenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris(chloroethyl) phosphate, tris(chloropropyl) phosphate, tris(dichloropropyl) phosphate, and tris(isopropylphenyl) phosphate.

[0034] 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.

[0035] 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.

[0036] Examples of polyester plasticizers include adipic acid polyesters, sebacic acid polyesters, and phthalic acid polyesters.

[0037] Examples of carbonate plasticizers include propylene carbonate and ethylene carbonate.

[0038] Other examples of the plasticizer (D) include partially hydrogenated terphenyls, adhesive plasticizers, and polymerizable plasticizers such as diallyl phthalate, acrylic monomers and oligomers, etc. These plasticizers can be used alone or in combination of two or more.

[0039] The amount of the plasticizer (D) to be added can be adjusted appropriately depending on the target viscosity, but, as an example, it is preferable to keep it at 30 mass % or less of the solid content of the polyisocyanate composition (X). The polyisocyanate composition (X) does not necessarily need to contain the plasticizer (D).

[0040] (Elongation at Break) The polyisocyanate composition (X) of the present invention is prepared by curing a polyol mixture containing 70±1 mass% of a polypropylene diol having a hydroxyl value number-average molecular weight of 415±20 and 30±1 mass% of a polypropylene triol having a number-average molecular weight of 415±35 (wherein the total of the polypropylene diol and the polypropylene triol is 100 mass%) at a molar ratio [NCO] / [OH] of the isocyanate groups in the polyisocyanate compound (A) to the hydroxyl groups in the polyol mixture of 1.3±0.1, and forming a coating film having a thickness of 100 μm to 200 μm, the coating film has an elongation at break of 30% or more at a tensile speed of 200 mm / min, at 25°C, and at a humidity of 40%. When such a polyisocyanate composition (X) is used, for example, as one component of an adhesive described below, a flexible coating film can be obtained, and even when used to bond soft substrates such as olefin resins, a laminate can be produced that has excellent adhesion and conformability, as well as excellent bag-breaking resistance and easy tearing properties.

[0041] The elongation at break is measured after aging under conditions of 40°C and 40% humidity, and after the reaction between the polyisocyanate composition (X) and the polyol mixture has been completed. Whether the reaction between the polyisocyanate composition (X) and the polyol mixture has been completed can be determined by infrared absorption spectroscopy. The infrared absorption spectroscopy is measured, and the reaction between the polyisocyanate composition (X) and the polyol mixture is considered to have been completed when no change in the intensity of the absorption peak of the isocyanate group is observed (even if there is a change, it is within the range of measurement error), using as a reference the absorption peak of a wavelength at which absorption does not increase or decrease due to the reaction between the polyisocyanate composition (X) and the polyol mixture.

[0042] Furthermore, the elongation at break depends on the film thickness of the coating film, but there is no particular effect on the measurement results if the thickness is within the range of 100 μm to 200 μm. When the polyisocyanate composition (X) does not contain the solvent (B), the polyisocyanate composition (X) and a polyol mixture are mixed, a coating film of 100 to 200 μm is formed on a film (for example, an untreated CPP film or a Teflon sheet) with an applicator, another film (for example, an untreated CPP film or a Teflon sheet) is placed on the coating film, and after aging at 40°C and a humidity of 40%, the coating film is peeled off from the film to obtain a test specimen.

[0043] When the polyisocyanate composition (X) contains a solvent (B), for example, the polyisocyanate composition (X) and a polyol mixture are mixed, a coating film is formed on a film (e.g., an untreated CPP film or a Teflon sheet) with an applicator to a thickness of 100 to 200 μm, the solvent (B) is volatilized, and the mixture is aged at 40°C and 40% humidity, after which the coating film is peeled off from the film to obtain a test piece. Alternatively, the polyisocyanate composition (X) and a polyol mixture are mixed, poured into a Teflon petri dish, the solvent (B) is volatilized, and the mixture is aged at 40°C and 40% humidity, after which the coating film is removed from the petri dish to obtain a test piece.

[0044] The breaking elongation of the polyisocyanate composition (X) measured under the above conditions can be adjusted, for example, by the structure of the polyisocyanate compound (A1). Alternatively, it can be adjusted by the presence or absence of the plasticizer (D). The breaking elongation of the polyisocyanate composition (X) measured under the above conditions is more preferably 100% or more. The upper limit of the breaking elongation is not particularly limited, but is, for example, 2000%.

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

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

[0047] <Two-component curing adhesive> The two-component curing adhesive of the present invention contains the above-described polyisocyanate composition (X) and isocyanate-reactive composition (Y).

[0048] When the adhesive of the present invention is used as a solventless adhesive, the viscosity of the polyisocyanate composition (X) is adjusted to a range suitable for the non-solvent lamination method. For example, the viscosity at 40°C is adjusted to a range of 100 to 20,000 mPas, more preferably 500 to 10,000 mPas. The viscosity of the polyisocyanate composition (X) can be adjusted, for example, by the structure of the polyisocyanate compound (A) or the plasticizer (D). The viscosity of the polyisocyanate composition (X) can be measured, for example, using a rotational viscometer with a cone and plate of 1° x 50 mm diameter and a shear rate of 100 sec. －１, can be measured at 40°C ± 1°C.

[0049] When the adhesive of the present invention is used as a solvent-based adhesive, the viscosity of the polyisocyanate composition (X) can be adjusted by diluting it with the solvent (B).

[0050] (Isocyanate-reactive composition (Y)) The isocyanate-reactive composition (Y) contains a compound (E) having a plurality of functional groups reactive with isocyanate (hereinafter also referred to as an isocyanate-reactive compound (E)), such as a polyester polyol (E1), a polyether polyol (E2), a vegetable oil polyol (E3), a polyurethane polyol (E4), a sugar alcohol (E5), or an amine compound (E6). The isocyanate-reactive compound (E) can be used alone or in combination of two or more.

[0051] Examples of the polyester polyol (E1) include polyester polyols which are reaction products of polyhydric alcohols and polycarboxylic acids, and lactone-based polyester polyols obtained by polycondensation reaction of aliphatic polyols and various lactones such as ε-caprolactone. It is preferable to use polyester polyols which are reaction products of polyhydric alcohols and polycarboxylic acids.

[0052] Examples of polyhydric alcohols include aliphatic diols such as ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,2,2-trimethyl-1,3-propanediol, 2,2-dimethyl-3-isopropyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-bis(hydroxymethyl)cyclohexane, and 2,2,4-trimethyl-1,3-pentanediol;

[0053] aliphatic polyols having three or more functional groups, such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, and pentaerythritol;

[0054] Bisphenols such as bisphenol A and bisphenol F; alkylene oxide adducts of bisphenols obtained by adding ethylene oxide, propylene oxide, or the like to bisphenols such as bisphenol A and bisphenol F;

[0055] Examples of such polyether polyols include polyether polyols obtained by ring-opening polymerization of an aliphatic diol or polyol with various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether. These polyether polyols may be used alone or in combination of two or more.

[0056] The polyhydric alcohol preferably contains at least one selected from the group consisting of ethylene glycol, diethylene glycol, dipropylene glycol, 1,6-hexanediol, neopentyl glycol, trimethylolpropane, 1,2-propanediol, 2-methyl-1,3-propanediol, and 3-methyl-1,5-pentanediol. The proportion of these compounds in the polyhydric alcohol is preferably 70% by mass or more, and more preferably 90% by mass or more.

[0057] Examples of polycarboxylic acids include aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, and 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid; and anhydrides or ester-forming derivatives of these aliphatic or dicarboxylic acids; and polybasic acids such as p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid, and ester-forming derivatives of these dihydroxycarboxylic acids, and dimer acid, and these may be used alone or in combination of two or more.

[0058] The polycarboxylic acid preferably contains at least one selected from the group consisting of isophthalic acid, terephthalic acid, orthophthalic acid, adipic acid, sebacic acid, and dimer acid. The proportion of these compounds in the polycarboxylic acid is preferably 70% by mass or more, and more preferably 90% by mass or more.

[0059] The polyester polyol (E1) preferably has a molecular weight of 250 g / mol to 20,000 g / mol, more preferably 500 g / mol to 20,000 g / mol, and a hydroxyl value of 5 mg KOH / g to 500 mg KOH / g.

[0060] Examples of the polyether polyol (E2) include those obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexylene in the presence of a polymerization initiator.

[0061] Examples of the polymerization initiator include glycols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and triethylene glycol;

[0062] trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, pentaerythritol, and triols of polypropylene glycol;

[0063] Examples thereof include primary or secondary alkylamines such as ethylamine and diethylamine, amine compounds having a plurality of amino groups such as methylenediamine and ethylenediamine, and amine compounds having an active hydrogen group such as primary or secondary alkanolamines such as monoethanolamine and diethanolamine.

[0064] The molecular weight of the polyether polyol (E2) can be adjusted appropriately, but is preferably 100 g / mol or more and 8000 g / mol or less, for example. The hydroxyl value of the polyether polyol (E2) can be adjusted appropriately, but is preferably 10 mgKOH / g or more and 1200 mgKOH / g or less, for example.

[0065] Examples of the vegetable oil polyol (E3) include castor oil, dehydrated castor oil, hardened castor oil which is a hydrogenated castor oil, and an alkylene oxide 5 to 50 mole adduct of castor oil.

[0066] The polyurethane polyol (E4) is a reaction product of a low-molecular-weight or high-molecular-weight polyol and a polyisocyanate compound. The low-molecular-weight or high-molecular-weight polyol may be the same as the polyhydric alcohols exemplified as raw materials for the polyester polyol (E1). The polyisocyanate compound may be the same as the polyhydric alcohols exemplified as raw materials for the isocyanate derivative (A2).

[0067] Examples of the sugar alcohol (E5) include pentaerythritol, sucrose, xylitol, sorbitol, isomalt, lactitol, maltitol, and mannitol.

[0068] The amine compound (E6) is a compound having an amino group. In this specification, the amino group is defined as an NH ２ group or NHR group (R is an alkyl group or aryl group which may have a functional group).

[0069] As the amine compound (E6), 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,

[0070] 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,

[0071] amine compounds (E6-1) having multiple amino groups such as bis(aminomethyl)cyclohexane, diaminodicyclohexylmethane, isophoronediamine, menthenediamine, bis(cyanoethyl)diethylenetriamine, 1,4-bis-(8-aminopropyl)-piperazine, piperazine-1,4-diazacycloheptane, 1-(2'-aminoethylpiperazine), 1-[2'-(2"-aminoethylamino)ethyl]piperazine, tricyclodecanediamine, and polyureaamines which are reaction products of the above-mentioned various polyamines with the above-mentioned various isocyanate components;

[0072] primary or secondary alkanolamines (E6-2) such as monoethanolamine, monoisopropanolamine, monobutanolamine, N-methylethanolamine, N-ethylethanolamine, N-methylpropanolamine, diethanolamine, and diisopropanolamine;

[0073] Examples include primary or secondary amines (E6-3) such as ethylamine, octylamine, laurylamine, myristylamine, stearylamine, oleylamine, diethylamine, dibutylamine, and distearylamine.

[0074] The amount of the amine compound (E6) to be added can be adjusted appropriately depending on the purpose. As an example, it is preferably added so that the amine value of the isocyanate-reactive composition (Y) becomes 20 to 70 mgKOH / g, more preferably 25 to 50 mgKOH / g.

[0075] The amine value in this specification refers to the number of milligrams of KOH equivalent to the amount of HCl required to neutralize 1 g of sample, and is not particularly limited and can be calculated using known methods. When the chemical structure of the amine compound (E6) and, if necessary, the average molecular weight, etc. are known, the amine value can be calculated from (number of amino groups per molecule / average molecular weight) x 56.1 x 1000. When the chemical structure, average molecular weight, etc. of the amine compound are unknown, the amine value can be measured according to known methods for measuring amine value, for example, JIS K7237-1995.

[0076] The isocyanate-reactive compound (E) may contain a compound (E7) other than those described above, but the proportion of such a compound is preferably less than 30 mass % of the isocyanate-reactive compound, and more preferably less than 15 mass %. In other words, the total amount of the above (E1) to (E6) in the isocyanate-reactive compound (E) is preferably 70 mass % or more, and more preferably 85 mass % or more. The isocyanate-reactive compound (E) may not contain a compound (E7) other than those described above.

[0077] (Monool Compound (F)) The isocyanate-reactive composition (Y) may contain a monool compound (F) having one alcoholic hydroxyl group. The main chain of the monool compound (F) is not particularly limited, and examples thereof include vinyl resins, acrylic resins, polyesters, epoxy resins, and urethane resins having one hydroxyl group. Aliphatic alcohols, alkyl alkylene glycols, and the like can also be used. The main chain of the monool compound (F) may be linear or branched. The bonding position of the hydroxyl group is not particularly limited, but it is preferably present at the terminal of the molecular chain.

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

[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;

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

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

[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, and the like.

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

[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)isopropyl propanolamine, 3-quinuclidinol, N,N,N',N'-tetramethylguanidine, 1,3,5-tris(N,N-dimethylaminopropyl)hexahydro-S-triazine, 1,8-diazabicyclo[5.4.0]undecene-7, N-methyl-N'-(2-dimethylaminoethyl)piperazine, N,N'-dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, 1-methylimidazole, 1 , 2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethylaminopropylimidazole, N,N-dimethylhexanolamine, N-methyl-N'-(2-hydroxyethyl)piperazine, 1-(2-hydroxyethyl)imidazole, 1-(2-hydroxypropyl)imidazole, 1-(2-hydroxyethyl)-2-methylimidazole, 1-(2-hydroxypropyl)-2-methylimidazole, and the like.

[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 accelerating curing.

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

[0092] 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.

[0093] 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.

[0094] Examples of aluminum-based coupling agents include acetoalkoxyaluminum diisopropylate.

[0095] (Pigment) The pigment is not particularly limited, and examples thereof include organic pigments and inorganic pigments such as extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments, green pigments, blue pigments, metal powder pigments, luminescent pigments, and pearlescent pigments listed in the Paint Raw Materials Handbook 1970 Edition (compiled by the Japan Paint Manufacturers Association), as well as plastic pigments.

[0096] Examples of extender pigments include precipitated barium sulfate, powdered barium sulfate, precipitated calcium carbonate, calcium bicarbonate, kansui stone, alumina white, silica, hydrous fine powdered silica (white carbon), ultrafine powdered anhydrous silica (aerosil), silica sand, talc, precipitated magnesium carbonate, bentonite, clay, kaolin, and yellow ochre.

[0097] Specific examples of organic pigments include various insoluble azo pigments such as Benzidine Yellow, Hansa Yellow, and Lake 4R; soluble azo pigments such as Lake C, Carmine 6B, and Bordeaux 10; various (copper) phthalocyanine pigments such as Phthalocyanine Blue and Phthalocyanine Green; various chlorine dye lakes such as Rhodamine Lake and Methyl Violet Lake; various mordant dye pigments such as Quinoline Lake and Fast Sky Blue; various vat dye pigments such as Anthraquinone pigments, Thioindigo pigments, and Perinone pigments; various quinacridone pigments such as Synchasia Red B; various dioxazine pigments such as Dioxazine Violet; various condensed azo pigments such as Chromophtal; and aniline black.

[0098] Examples of inorganic pigments include various chromates such as yellow lead, zinc chromate, and molybdate orange; various ferrocyanide compounds such as iron blue; various metal oxides such as titanium oxide, zinc white, mapico yellow, iron oxide, red iron oxide, chrome oxide green, and zirconium oxide; various sulfides or selenides such as cadmium yellow, cadmium red, and mercury sulfide; various sulfates such as barium sulfate and lead sulfate; various silicates such as calcium silicate and ultramarine; various carbonates such as calcium carbonate and magnesium carbonate; various phosphates such as cobalt violet and manganese purple; various metal powder pigments such as aluminum powder, gold powder, silver powder, copper powder, bronze powder, and brass powder; flake pigments of these metals, mica flake pigments; metallic pigments and pearl pigments such as mica flake pigments coated with metal oxides and micaceous iron oxide pigments; graphite, carbon black, and the like.

[0099] Examples of plastic pigments include "Grandol PP-1000" and "PP-2000S" manufactured by DIC Corporation.

[0100] The pigment to be used may be selected appropriately depending on the purpose. For example, inorganic oxides such as titanium oxide and zinc oxide are preferably used as white pigments because they have excellent durability, weather resistance, and design properties, and carbon black is preferably used as black pigments.

[0101] The blending amount of the pigment is, for example, 1 to 400 parts by mass per 100 parts by mass of the total amount of nonvolatile components of the polyisocyanate composition (X) and the isocyanate-reactive composition (Y), and is more preferably 10 to 300 parts by mass in order to improve adhesion and blocking resistance.

[0102] (Acid Anhydride) Examples of the acid anhydride include alicyclic acid anhydrides, aromatic acid anhydrides, unsaturated carboxylic acid anhydrides, etc., and can be used alone or in combination of two or more. More specifically, for example, maleic acid anhydride, phthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, benzophenonetetracarboxylic acid anhydride, dodecenylsuccinic acid anhydride, polyadipic acid anhydride, polyazelaic acid anhydride, polysebacic acid anhydride, poly(ethyloctadecanedioic acid) anhydride, poly(phenylhexadecanedioic acid) anhydride, tetrahydrophthalic acid anhydride, methyltetrahydrophthalic acid anhydride, methylhexahydrophthalic acid anhydride, hexahydrophthalic acid anhydride, methylhimic acid anhydride, trialkyltetrahydrophthalic acid anhydride, anhydride, methylcyclohexene dicarboxylic acid anhydride, methylcyclohexene tetracarboxylic acid anhydride, ethylene glycol bistrimellitate dianhydride, HET acid anhydride, Nadic acid anhydride, methylnadic acid anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexane-1,2-dicarboxylic acid anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride, and the like.

[0103] The acid anhydride may be any of the above compounds modified with glycol. Examples of glycols that can be used for modification include alkylene glycols such as ethylene glycol, propylene glycol, and neopentyl glycol; and polyether glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. Furthermore, copolymer polyether glycols of two or more of these glycols and / or polyether glycols may also be used.

[0104] Alternatively, among the compounds mentioned above as acid anhydrides, a homopolymer or copolymer of a compound having a polymerizable unsaturated group, such as maleic anhydride, may be used. Examples of compounds copolymerizable with a compound having an acid anhydride group and a polymerizable unsaturated group include α-olefins such as ethylene, propylene, 1,3-butadiene, and cyclopentylethylene; vinyl compounds having an aromatic ring, such as styrene, 1-ethynyl-4-methylbenzene, divinylbenzene, 1-ethynyl-4-methylethylbenzene, benzonitrile, acrylonitrile, p-tert-butylstyrene, 4-vinylbiphenyl, 4-ethynylbenzyl alcohol, 2-ethynylnaphthalene, and phenanthrene-9-ethynyl; and fluoroolefins such as vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, and chlorotrifluoroethylene. These compounds may be used alone or in combination of two or more. It is preferable to use styrene and p-tert-butylstyrene, which are vinyl compounds having an aromatic ring.

[0105] (Other Components) The adhesive may contain a phosphoric acid derivative (C) and a plasticizer (D). These may be the same as those exemplified above as components of the polyisocyanate composition (X).

[0106] (Form of Adhesive) The two-component curing adhesive of the present invention may be either a solvent-based or solventless type. In this specification, a "solvent-based" adhesive refers to a form used in a so-called dry lamination method, in which the adhesive is applied to a substrate, heated in an oven or the like to volatilize the organic solvent in the coating, and then bonded to another substrate. Either or both of the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) contain an organic solvent capable of dissolving (diluting) the components of the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) used in the present invention.

[0107] Examples of organic solvents include esters such as ethyl acetate, butyl acetate, cellosolve acetate, etc., ketones such as acetone, methyl ethyl ketone, isobutyl ketone, cyclohexanone, etc., ethers such as tetrahydrofuran, dioxane, etc., aromatic hydrocarbons such as toluene, xylene, etc., halogenated hydrocarbons such as methylene chloride, ethylene chloride, etc., dimethyl sulfoxide, dimethyl sulfamide, etc. The organic solvent used as a reaction medium during production of the components of the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) may also be used as a diluent during coating.

[0108] In this specification, a "solventless" adhesive refers to a form of adhesive in which the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) are substantially free of esters such as ethyl acetate, butyl acetate, cellosolve acetate, etc.; ketones such as acetone, methyl ethyl ketone, isobutyl ketone, cyclohexanone, etc.; ethers such as tetrahydrofuran, dioxane, etc.; aromatic hydrocarbons such as toluene, xylene, etc.; halogenated hydrocarbons such as methylene chloride, ethylene chloride, etc.; highly soluble organic solvents such as dimethyl sulfoxide, dimethyl sulfamide, in particular ethyl acetate or methyl ethyl ketone; and which is used in a method in which the adhesive is applied to a substrate and then bonded to another substrate without going through a step of heating in an oven or the like to volatilize the solvent, i.e., a so-called non-solvent lamination method. If the organic solvent used as a reaction medium during the production of the components of polyisocyanate composition (X) or isocyanate-reactive composition (Y) or the raw materials thereof cannot be completely removed, and trace amounts of organic solvent remain in polyisocyanate composition (X) or isocyanate-reactive composition (Y), it is considered to be substantially free of organic solvent. Furthermore, if isocyanate-reactive composition (Y) contains a low-molecular-weight alcohol, the low-molecular-weight alcohol reacts with polyisocyanate composition (X) to become part of the coating film, and therefore does not need to be volatilized after coating. Therefore, such a form is also treated as a solventless adhesive, and the low-molecular-weight alcohol is not considered an organic solvent.

[0109] Generally, solvent-free adhesives are required to be able to be applied at a thickness of several micrometers under relatively low temperature conditions (approximately 40 to 50°C) without diluting with an organic solvent, and the molecular weight of the components must be smaller than that of the components of solvent-based adhesives. As a result, the cured coating film of the adhesive has a high urethane bond concentration and is relatively hard. Packaging materials produced using such adhesives tend to be prone to tearing. However, the adhesive of the present invention has excellent extensibility in the cured coating film, and can provide laminates and packaging materials with excellent tearing resistance even when used in a solvent-free form, so it is also preferable to use it as a solvent-free adhesive.

[0110] The two-component curing adhesive of the present invention is preferably used by blending the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) so that the ratio [NCO] / [isocyanate-reactive functional group] of the number of moles of isocyanate groups [NCO] to the number of moles of functional groups reactive with isocyanate [isocyanate-reactive functional group] is 0.5 to 5.0, more preferably 1.0 to 3.0. This allows for appropriate curing properties to be obtained without depending on the environmental humidity at the time of application.

[0111] In the two-component curing adhesive of the present invention, in order to fully utilize the physical properties of the polyisocyanate composition (X), the solids mass ratio of the polyisocyanate composition (X) to the polyol composition (Y) is preferably 0.5:10 to 100:10, and more preferably 0.5:10 to 60:10. This ensures that the cured coating film of the adhesive of the present invention has excellent elongation, and laminates produced using the adhesive of the present invention have excellent bag rupture resistance and easy tearing properties, for example.

[0112] <Laminate> The laminate of the present invention can be obtained, for example, by mixing the polyisocyanate composition (X) of the present invention with the isocyanate-reactive composition (Y) to prepare a coating agent, which is then applied to a substrate and cured. Alternatively, the laminate can be obtained by a two-liquid mixing process in which the polyisocyanate composition (X) of the present invention and the isocyanate-reactive composition (Y) are mixed in advance to prepare an adhesive, which is then applied to a first substrate, and then a second substrate is laminated on the coated surface and cured to form an adhesive layer; or by a two-liquid separate coating process in which the polyisocyanate composition (X) and the isocyanate-reactive composition (Y) are separately applied to a first substrate and a second substrate, and then the coated surfaces of the first substrate and the second substrate are brought into contact and pressed together to laminate the first substrate and the second substrate, and the adhesive layer is cured to form an adhesive layer. There are no particular restrictions on the substrate used, and it can be selected appropriately depending on the application.

[0113] Examples of films for food packaging include polyethylene terephthalate (PET) films, polystyrene films, polyamide films, polyacrylonitrile films, polyethylene films (LLDPE: low-density polyethylene film, HDPE: high-density polyethylene film, MDOPE: uniaxially oriented polyethylene film, BOPE: biaxially oriented polyethylene film), polypropylene films (CPP: unoriented polypropylene film, OPP: biaxially oriented polypropylene film), barrier heat-sealable films in which an olefin-based heat-sealable resin layer is provided on one or both sides of a resin having barrier properties such as an ethylene-vinyl alcohol copolymer, polyvinyl alcohol, cyclic polyolefin resin, or cyclic olefin copolymer, polyolefin films such as white polyethylene film, polyvinyl alcohol film, and ethylene-vinyl alcohol copolymer film.

[0114] It is also preferable to use a film made of a material containing biomass-derived components. Biomass films are commercially available from various companies, and for example, sheets such as those listed in the list of biomass-certified products listed by the Japan Organics Resources Association can be used.

[0115] Specifically, well-known films are made from biomass-derived ethylene glycol. Biomass-derived ethylene glycol is made from ethanol (biomass ethanol) produced from biomass as a raw material. For example, biomass-derived ethylene glycol can be obtained by converting biomass ethanol into ethylene oxide by a conventionally known method to produce ethylene glycol. Alternatively, commercially available biomass ethylene glycol may be used; for example, biomass ethylene glycol commercially available from India Glycoal Limited can be suitably used.

[0116] Alternatively, products using biomass raw materials classified by the biomass plastic content specified in ISO 16620 or ASTM D6866 are also on the market. Radioactive carbon-14C exists in the atmosphere at a rate of 1 in 1012 particles, and this rate is the same for atmospheric carbon dioxide, so this rate remains the same even in plants that fix this carbon dioxide through photosynthesis. Therefore, the carbon in plant-derived resins contains radioactive carbon-14C. In contrast, the carbon in fossil fuel-derived resins contains almost no radioactive carbon-14C. Therefore, by measuring the concentration of radioactive carbon-14C in the resin using an accelerator mass spectrometer, the plant-derived resin content in the resin, i.e., the biomass plastic content, can be determined. Examples of plant-derived low-density polyethylene, which is a biomass plastic having a biomass plastic content of 80% or more, preferably 90% or more as specified by ISO 16620 or ASTM D6866, include products manufactured by Braskem under the trade names "SBC818," "SPB608," "SBF0323HC," "STN7006," "SEB853," and "SPB681," and films using these as raw materials can be suitably used.

[0117] The film may be one that has been subjected to a stretching treatment. A typical stretching method involves melt-extruding a resin into a sheet using an extrusion film-forming method or the like, followed by simultaneous biaxial stretching or sequential biaxial stretching. In the case of sequential biaxial stretching, it is common to first perform longitudinal stretching and then transverse stretching. Specifically, a method that combines longitudinal stretching utilizing the speed difference between rolls and transverse stretching using a tenter is often used.

[0118] The film surface may be subjected to various surface treatments such as flame treatment and corona discharge treatment as necessary so that an adhesive layer without defects such as film breakage or repellency is formed.

[0119] Alternatively, a film laminated with a vapor-deposited layer of a metal such as aluminum or a metal oxide such as silica or alumina, or a barrier film containing a gas barrier layer of polyvinyl alcohol, an ethylene-vinyl alcohol copolymer, vinylidene chloride, etc. Use of such a film can provide a laminate with barrier properties against water vapor, oxygen, alcohol, inert gases, volatile organic compounds (fragrances), etc.

[0120] The paper can be made from any known paper base material without any particular limitations. Specifically, it is produced using natural fibers for papermaking, such as wood pulp, on a known papermaking machine, but the papermaking conditions are not particularly specified. Examples of natural fibers for papermaking include wood pulp, such as softwood pulp and hardwood pulp; non-wood pulp, such as Manila hemp pulp, sisal hemp pulp, and flax pulp; and pulp obtained by chemically modifying these pulps. Examples of pulp that can be used include chemical pulp produced by sulfate cooking, acidic, neutral, or alkaline sulfite cooking, soda cooking, ground pulp, chemi-ground pulp, and thermomechanical pulp. Various commercially available fine paper, coated paper, lined paper, impregnated paper, cardboard, and paperboard can also be used.

[0121] Specific examples of laminate structures produced using the adhesive of the present invention include, but are not limited to, the following: (1) substrate 1 / adhesive layer 1 / sealant film (2) substrate 1 / adhesive layer 1 / metal-deposited unstretched film (3) substrate 1 / adhesive layer 1 / metal-deposited stretched film (4) transparent vapor-deposited stretched film / adhesive layer 1 / sealant film (5) substrate 1 / adhesive layer 1 / substrate 2 / adhesive layer 2 / sealant film (6) substrate 1 / adhesive layer 1 / metal-deposited stretched film / adhesive layer 2 / sealant film (7) substrate 1 / adhesive layer 1 / transparent vapor-deposited stretched film / adhesive layer 2 / sealant film (8) substrate 1 / adhesive layer 1 / metal layer / adhesive layer 2 / sealant film (9) substrate 1 / adhesive layer 1 / substrate 2 / adhesive layer 2 / metal layer / adhesive layer 3 / sealant film (10) substrate 1 / adhesive layer 1 / metal layer / adhesive layer 2 / substrate 2 / adhesive layer 3 / sealant film

[0122] Examples of the substrate 1 used in structure (1) include MDOPE film, BOPE film, OPP film, PET film, nylon film, and paper. The substrate 1 may also be coated to improve gas barrier properties or ink receptivity when a printing layer (described later) is provided. Commercially available coated substrate films 1 include K-OPP film, K-PET film, and K-nylon film. The adhesive layer 1 is a cured coating of the adhesive of the present invention. Examples of sealant films include CPP film, LLDPE film, easy-open heat seal film, and barrier heat seal film. A printing layer may be provided on the surface of the substrate 1 facing the adhesive layer 1 (when a coated substrate film 1 is used, the surface of the coating layer facing the adhesive layer 1) or on the surface opposite the adhesive layer 1. The printing layer is formed using various printing inks, such as gravure ink, flexographic ink, offset ink, stencil ink, and inkjet ink, using a common printing method conventionally used for printing on polymer films and paper.

[0123] Examples of the substrate 1 used in structures (2) and (3) include an MDOPE film, a BOPE film, an OPP film, a PET film, and paper. The adhesive layer 1 is a cured coating of the adhesive of the present invention. Examples of metal-vapor-deposited unstretched films include a CPP film, an LLDPE film, and a VM-CPP film or a VM-LLDPE film, which is a gas-barrier heat-seal film that has been subjected to metal vapor deposition with aluminum or the like. Examples of metal-vapor-deposited stretched films include a VM-MDOPE film, a VM-BOPE film, or a VM-OPP film, which is a MDOPE film, a BOPE film, or an OPP film that has been subjected to metal vapor deposition with aluminum or the like. As with structure (1), a printed layer may be provided on either side of the substrate 1.

[0124] Examples of transparent vapor-deposited stretched films used in structure (4) include films obtained by vapor-depositing silica or alumina onto MDOPE film, BOPE film, OPP film, PET film, nylon film, etc. A film with a coating applied to the vapor-deposited inorganic layer of silica or alumina may also be used for the purpose of protecting the vapor-deposited inorganic layer. The adhesive layer 1 is a cured coating of the adhesive of the present invention. Examples of sealant films include those similar to those in structure (1). A printed layer may be provided on the surface of the transparent vapor-deposited stretched film facing the adhesive layer 1 (when a film with a coating applied to the inorganic vapor-deposited layer is used, the surface of the coating layer facing the adhesive layer 1). The method of forming the printed layer is the same as in structure (1).

[0125] Examples of the substrate 1 used in structure (5) include PET film and paper. Examples of the substrate 2 include nylon film. At least one of the adhesive layer 1 and the adhesive layer 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those in structure (1). As in structure (1), a printed layer may be provided on either side of the substrate 1.

[0126] Examples of the substrate 1 in structure (6) include those similar to those in structures (2) and (3). Examples of metal-vapor-deposited stretched films include VM-MDOPE films, VM-BOPE films, VM-OPP films, and VM-PET films, which are MDOPE films, BOPE films, OPP films, and PET films that have been subjected to metal vapor deposition of aluminum or the like. At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those in structure (1). As in structure (1), a printed layer may be provided on either side of the substrate 1.

[0127] Examples of the substrate 1 in structure (7) include PET film, paper, etc. Examples of the transparent vapor-deposited stretched film include those similar to those in structure (4). At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those in structure (1). As in structure (1), a printed layer may be provided on either side of the substrate 1.

[0128] Examples of the substrate 1 in structure (8) include PET film and paper. Examples of the metal layer include aluminum foil. At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those in structure (1). As in structure (1), a printed layer may be provided on either side of the substrate 1.

[0129] Examples of the substrate 1 in structures (9) and (10) include PET film, paper, etc. Examples of the substrate 2 include nylon film, etc. Examples of the metal layer include aluminum foil, etc. At least one layer of the adhesive layers 1, 2, and 3 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those in structure (1). As in structure (1), a printed layer may be provided on either side of the substrate 1.

[0130] The cured coating film of the adhesive of the present invention has excellent elongation properties, so even in laminates made by bonding together olefin resin films, particularly polyethylene films, which are generally prone to tearing when filled with heavy objects, the adhesive of the present invention can be used to make the laminate have excellent resistance to tearing and ease of tearing.

[0131] Particularly preferred examples of the laminate of the present invention are those having the above structure (1), in which the substrate 1 is any one of a BOPE film, an MDOPE film, an HDPE film, a film obtained by multilayer extrusion of an ethylene vinyl alcohol resin with a polyethylene resin (low density polyethylene / ethylene-vinyl alcohol copolymer resin / low density polyethylene), and a film obtained by extruding a cyclic polyolefin copolymer with a polyethylene resin (low density polyethylene / cyclic polyolefin resin / low density polyethylene), and the sealant film is any one of a LLDPE film, a film obtained by multilayer extrusion of an ethylene vinyl alcohol resin with a polyethylene resin, a film obtained by extruding a cyclic polyolefin copolymer with a polyethylene resin, and a white polyethylene film;

[0132] In the above-mentioned configuration (4), when the transparent vapor-deposited stretched film is a film obtained by depositing silica or alumina on an MDOPE film or a BOPE film, and the sealant film is any one of an LLDPE film, a film obtained by multilayer extrusion of an ethylene vinyl alcohol resin with a polyethylene resin, a film obtained by extruding a cyclic polyolefin copolymer with a polyethylene resin, and a white polyethylene film,

[0133] In the above-mentioned configuration (1), when the substrate 1 is an OPP film and the sealant film is a CPP film or a film obtained by extruding a cyclic polyolefin copolymer with a polypropylene resin (polypropylene / cyclic polyolefin resin / polypropylene),

[0134] In the above configuration (4), when the transparent vapor-deposited stretched film is a film obtained by depositing silica or alumina on an OPP film, and the sealant film is a CPP film or a film obtained by extruding a cyclic polyolefin copolymer with a polypropylene resin (polypropylene / cyclic polyolefin resin / polypropylene),

[0135] In the above configuration (5), when the substrate 1 is any one of a BOPE film, an MDOPE film, an HDPE film, a film obtained by multilayer extrusion of an ethylene vinyl alcohol resin with a polyethylene resin, and a film obtained by extruding a cyclic polyolefin copolymer with a polyethylene resin, and the substrate 2 is any one of a BOPE film, an MDOPE film, an HDPE film, a film obtained by multilayer extrusion of an ethylene vinyl alcohol resin with a polyethylene resin, and a film obtained by extruding a cyclic polyolefin copolymer with a polyethylene resin, and the sealant film is any one of a LLDPE film, a film obtained by multilayer extrusion of an ethylene vinyl alcohol resin with a polyethylene resin, a film obtained by extruding a cyclic polyolefin copolymer with a polyethylene resin, and a white polyethylene film,

[0136] In a configuration similar to the above configuration (5), when the substrate 1 is a film obtained by depositing silica or alumina on an MDOPE film or a BOPE film, the substrate 2 is any one of a BOPE film, an MDOPE film, an HDPE film, a film obtained by multilayer extrusion of an ethylene vinyl alcohol resin with a polyethylene resin, and a film obtained by extruding a cyclic polyolefin copolymer with a polyethylene resin, and the sealant film is any one of a LLDPE film, a film obtained by multilayer extrusion of an ethylene vinyl alcohol resin with a polyethylene resin, a film obtained by extruding a cyclic polyolefin copolymer with a polyethylene resin, and a white polyethylene film,

[0137] In the above configuration (7), when the substrate 1 is any one of a BOPE film, an MDOPE film, an HDPE film, a film obtained by multilayer extrusion of an ethylene vinyl alcohol resin with a polyethylene resin, and a film obtained by extruding a cyclic polyolefin copolymer with a polyethylene resin, the transparent vapor-deposited stretched film is a film obtained by vapor-depositing silica or alumina on an MDOPE film or a BOPE film, and the sealant film is any one of an LLDPE film, a film obtained by multilayer extrusion of an ethylene vinyl alcohol resin with a polyethylene resin, a film obtained by extruding a cyclic polyolefin copolymer with a polyethylene resin, and a white polyethylene film,

[0138] In the above configuration (5), when the substrate 1 and the substrate 2 are OPP films and the sealant film is a CPP film or a film obtained by extruding a cyclic polyolefin copolymer with a polypropylene resin (polypropylene / cyclic polyolefin resin / polypropylene),

[0139] In a configuration similar to the above configuration (5), the substrate 1 is a film obtained by depositing silica or alumina on an OPP film, the substrate 2 is an OPP film, and the sealant film is a CPP film or a film obtained by extruding a cyclic polyolefin copolymer with a polypropylene resin (polypropylene / cyclic polyolefin resin / polypropylene),

[0140] In the above configuration (7), examples include the case where the substrate 1 is an OPP film, the transparent vapor-deposited stretched film is an OPP film to which silica or alumina has been vapor-deposited, and the sealant film is a CPP film or a film obtained by extruding a cyclic polyolefin copolymer with a polypropylene resin (polypropylene / cyclic polyolefin resin / polypropylene).

[0141] The laminate of the present invention may further include other films or substrates in addition to the above-described configurations (1) to (10). As the other substrates, in addition to the above-described stretched films, unstretched films, and transparent vapor-deposited films, porous substrates such as paper, wood, and leather, which will be described later, can also be used. The adhesive used to bond the other substrates may or may not be the adhesive of the present invention.

[0142] The "other layer" may contain known additives or stabilizers, such as antistatic agents, adhesion-enhancing coating agents, plasticizers, lubricants, antioxidants, etc. Furthermore, the "other layer" may be a film whose surface has been pretreated with corona treatment, plasma treatment, ozone treatment, chemical treatment, solvent treatment, or the like in order to improve adhesion when laminated with other materials.

[0143] The laminate of the present invention can be suitably used for a variety of applications, such as packaging materials for food, medicines, and daily necessities; lid materials; paper tableware such as paper straws, paper napkins, paper spoons, paper plates, and paper cups; barrier materials; roofing materials; solar cell panel materials; battery packaging materials; window materials; outdoor flooring materials; lighting protection materials; automotive components; signs; stickers and other outdoor industrial applications; decorative sheets used in simultaneous injection molding decoration methods; and packaging materials for liquid laundry detergents, liquid kitchen detergents, liquid bath detergents, liquid bath soaps, liquid shampoos, liquid conditioners, and the like.

[0144] <Packaging Material> The laminate of the present invention can be used as a multilayer packaging material for protecting foods, medicines, etc. When used as a multilayer packaging material, the layer structure can be changed depending on the contents, the environment of use, and the form of use. In addition, the packaging of the present invention may be appropriately provided with an easy-open treatment or a resealable means.

[0145] A specific example of the packaging material of the present invention is a packaging material obtained by forming a bag from a laminate having a sealant film, such as the laminate configuration examples (1), (4), and (10) described above. The laminate is folded or overlapped so that the inner layer surfaces (the surfaces of the sealant film) face each other, and the peripheral edges are heat-sealed to form a bag. Examples of bag-making methods include heat-sealing methods using a side seal, two-sided seal, three-sided seal, four-sided seal, envelope seal, flared seal, flat-bottom seal, square-bottom seal, gusset seal, or other heat seal types. The packaging material of the present invention can take various forms depending on the contents, usage environment, and usage pattern. Self-standing packaging materials (standing pouches) are also possible. Examples of heat-sealing methods include known methods such as bar seal, rotary roll seal, belt seal, impulse seal, high-frequency seal, and ultrasonic seal.

[0146] The packaging material of the present invention is filled with contents through its opening, and then the opening is heat-sealed to produce a product using the packaging material of the present invention. Examples of contents to be filled include foods such as rice crackers, bean snacks, nuts, biscuits, cookies, wafer snacks, marshmallows, pies, semi-dried cakes, candies, and snacks; staple foods such as bread, snack noodles, instant noodles, dried noodles, pasta, aseptically packaged cooked rice, porridge, rice porridge, packaged rice cakes, and cereal foods; processed agricultural products such as pickles, boiled beans, natto, miso, frozen tofu, tofu, nametake mushrooms, konjac, processed wild vegetables, jams, peanut cream, salads, frozen vegetables, and processed potatoes; processed livestock products such as ham, bacon, sausages, processed chicken, and corned beef; and processed fish ham and meat products. Examples of such foods include processed seafood products such as sausages, fish paste products, kamaboko, nori seaweed, tsukudani (simmered foods in soy sauce), bonito flakes, salted fish, smoked salmon, and spicy mentaiko; fruit pulp such as peaches, mandarin oranges, pineapples, apples, pears, and cherries; vegetables such as corn, asparagus, mushrooms, onions, carrots, radishes, and potatoes; cooked foods such as frozen and chilled prepared dishes, including hamburgers, meatballs, fried seafood, gyoza, and croquettes; dairy products such as butter, margarine, cheese, cream, instant creamy powder, and infant formula; liquid seasonings, retort curry, and pet food.

[0147] In addition, the present invention can also be used as a packaging material for various non-food products, such as cigarettes, disposable body warmers, medicines such as infusion packs, liquid laundry detergent, liquid kitchen detergent, liquid bath detergent, liquid bath soap, liquid shampoo, liquid conditioner, cosmetics such as lotion and emulsion, vacuum insulation materials, batteries, etc.

[0148] The present invention will be described in more detail below with reference to specific synthesis examples and examples, but the present invention is not limited to these examples. In the following examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively, unless otherwise specified.

[0149] <Preparation of Polyisocyanate Composition (X)> (Polyisocyanate Composition (X-1)) 150 parts by mass of hexamethylene diisocyanate (HDI) was charged into a flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube, and the mixture was stirred under nitrogen gas and heated to 60°C. 100 parts by mass of polypropylene glycol (hereinafter abbreviated as "PPG") having a number average molecular weight of 400 was added dropwise in several portions, and the mixture was stirred for 5 to 6 hours to complete the urethanization reaction. Next, using a thin-film distillation apparatus, the mixture was purified at a pressure of approximately 0.02 Torr and a temperature of 140°C until the HDI in the urethane prepolymer, the reaction product of HDI, accounted for 1% by mass of the solids, thereby obtaining polyisocyanate composition (X-1). The NCO group content of polyisocyanate composition (X-1) was 9%.

[0150] (Polyisocyanate Composition (X-2)) 90 parts by mass of hexamethylene diisocyanate (HDI) was charged into a flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube, and the mixture was stirred under nitrogen gas and heated to 60°C. 100 parts by mass of polytetramethylene ether glycol (hereinafter abbreviated as "PTMG") having a number average molecular weight of 650 was added dropwise in several portions, and the mixture was stirred for 5 to 6 hours to complete the urethanization reaction. Next, a thin-film distillation apparatus was used to generate a urethane prepolymer, the reaction product of HDI, at a pressure of approximately 0.02 Torr and a temperature of 140°C until the HDI in the urethane prepolymer accounted for 1% by mass of the solids, thereby obtaining polyisocyanate composition (X-2). The resulting polyisocyanate composition (X-2) had an NCO group content of 8%.

[0151] (Polyisocyanate Composition (X-3)) A flask equipped with a stirrer, thermometer, and nitrogen gas inlet tube was charged with 100 parts by mass of hexamethylene diisocyanate (HDI), stirred under nitrogen gas, and heated to 60°C. 26 parts by mass of Polylite MX-2921 (DIC Corporation, polyester polyol of diethylene glycol and orthophthalic acid), followed by 100 parts by mass of PPG with a number average molecular weight of 400, were added dropwise in several portions, and the mixture was stirred for 5 to 6 hours to complete the urethanization reaction. Next, a thin-film distillation apparatus was used to generate the urethane prepolymer, a reaction product of HDI, at a pressure of approximately 0.02 Torr and a temperature of 140°C until the HDI in the urethane prepolymer accounted for 1% by mass of the solids, thereby obtaining polyisocyanate composition (X-3). The NCO group content of the resulting polyisocyanate was 11%.

[0152] (Polyisocyanate Composition (X-4)) A polyester reaction vessel equipped with a stirrer, a nitrogen gas inlet tube, a Snyder tube, and a condenser was charged with 51.06 parts of ethylene glycol and 63.30 parts of phthalic anhydride, and the mixture was gradually heated so that the temperature at the top of the distillation tube did not exceed 100° C., and the internal temperature was maintained at 220° C. When the acid value reached 1 mgKOH / g or less, the esterification reaction was terminated and 0.01 parts of phosphoric acid was added, yielding an intermediate polyester polyol 1 having a number average molecular weight of 340 and a hydroxyl value of 331.0 mgKOH / g.

[0153] Next, 100 parts by mass of Duranate D101 (manufactured by Asahi Kasei Corporation, hexamethylene diisocyanate derivative, bifunctional) was charged into a flask equipped with a stirrer, thermometer, and nitrogen gas inlet tube, and the mixture was stirred under nitrogen gas and heated to 60°C. 26 parts by mass of intermediate polyester polyol 1 was added dropwise in several batches, and the mixture was stirred for 5 to 6 hours to complete the urethanization reaction. Subsequently, 620 parts by mass of polyisocyanate composition (X-1) was charged and stirred to obtain polyisocyanate composition (X-4). The NCO group content of polyisocyanate composition (X-4) was 10%.

[0154] (Polyisocyanate Composition (X-5)) 100 parts by mass of Duranate D101 (manufactured by Asahi Kasei Corporation, hexamethylene diisocyanate derivative, bifunctional) was charged into a flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube, and the mixture was stirred under nitrogen gas and heated to 60°C. 24 parts by mass of Polylite MX-2921 (manufactured by DIC Corporation, polyester polyol of diethylene glycol and orthophthalic acid) was added dropwise in several portions, and the mixture was stirred for 5 to 6 hours to complete the urethanization reaction, thereby obtaining polyisocyanate composition (X-5). The NCO group content of polyisocyanate composition (X-5) was 12.5%.

[0155] (Polyisocyanate Composition (X-6)) A polyester reaction vessel equipped with a stirrer, a nitrogen gas inlet tube, a Snyder tube, and a condenser was charged with 92.00 parts of ethylene glycol, 118.50 parts of phthalic anhydride, 29.23 parts of adipic acid, and 0.01 parts of titanium tetraisopropoxide, and the mixture was gradually heated so that the temperature at the top of the distillation tube did not exceed 100° C., and the internal temperature was maintained at 220° C. When the acid value reached 1 mgKOH / g or less, the esterification reaction was terminated, yielding an intermediate polyester polyol 2 having a number average molecular weight of 500 and a hydroxyl value of 225.

[0156] Subsequently, 71.45 parts of xylylene diisocyanate and 46.26 parts of Millionate MN (a mixture of 4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate) were placed in a flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube, and the mixture was stirred while heated to 60°C, and 92.28 parts of intermediate polyester polyol 2 were added dropwise in several portions, and the mixture was stirred for 5 to 6 hours to complete the urethanization reaction, thereby obtaining polyisocyanate composition (X'-1). The NCO group content of the obtained polyisocyanate was 15%.

[0157] (Polyisocyanate composition (X-7)) Burnock DN-992S (manufactured by DIC Corporation, non-aromatic diisocyanate derivative, nurate type prepolymer, trifunctional) was used as polyisocyanate composition (X-7). The NCO group content of polyisocyanate composition (X-7) was 14%.

[0158] (Polyisocyanate composition (X-8)) Desmodur N-3300 (manufactured by Covestro Corporation, nurate form of hexamethylene diisocyanate, trifunctional) was used as polyisocyanate composition (X-8). The NCO group content of polyisocyanate composition (X-8) was 22%.

[0159] (Polyisocyanate composition (X-9)) Polyisocyanate composition (X-1) and polyisocyanate composition (X-8) were mixed in a mass ratio of 1:1 to prepare polyisocyanate composition (X-9). The NCO group content of polyisocyanate composition (X-9) was 15%.

[0160] <Preparation of Isocyanate-Reactive Composition (Y)> (Synthesis of Polyester Polyol (E1-1)) A reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, a rectifying tube, a water separator, and the like was charged with 54.0 parts of 3-methylpentanediol, 30.0 parts of trimethylolpropane, 60.0 parts of adipic acid, and 0.01 parts of titanium tetraisopropoxide under nitrogen gas introduction, and the mixture was gradually heated so that the temperature at the top of the rectifying tube did not exceed 100° C., and the internal temperature was maintained at 220° C. When the acid value reached 1 mgKOH / g or less, the esterification reaction was terminated, and a polyester polyol (E1-1) having a number average molecular weight of 500 and a hydroxyl value of 337 was obtained.

[0161] (Synthesis of Polyester Polyol (E1-2)) A reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, a rectifying tube, a water separator, etc. was charged with 54.0 parts of 3-methylpentanediol, 46.0 parts of isophthalic acid, and 0.01 parts of titanium tetraisopropoxide under nitrogen gas introduction, and the inside temperature was maintained at 250° C. by gradually heating so that the temperature at the top of the rectifying tube did not exceed 100° C. When the acid value reached 1 mgKOH / g or less, the esterification reaction was terminated, and a polyester polyol (E1-2) having a number average molecular weight of 500 and a hydroxyl value of 224 was obtained.

[0162] (Preparation of Isocyanate-Reactive Composition (Y)) Polyol compositions (Y-1) and (Y-2) were prepared according to the formulations in Table 1. The unit of amine value is mgKOH / g. Details of the compounds in the table other than polyester polyol (E1) are as follows:

[0163] Polyether polyol (E2-1): Actocol T-1000 (manufactured by Mitsui Chemicals, Inc., number average molecular weight 1000, trifunctional polypropylene polyol) Polyether polyol (E2-2): Polypropylene polyol (manufactured by AGC, Exenol 420 (molecular weight = 400, hydroxyl value = 280)) Polyether polyol (E2-3): Polypropylene polyol (manufactured by AGC, Exenol 430 (molecular weight Mw = 400, hydroxyl value = 400)) Polyether polyol (E2-4): Sannix HD-402 (manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight 600, tetrafunctional polypropylene polyol) Polyamine (E6-1): Polyoxypropylene triamine (manufactured by Huntsman, Jeffamine T-403, molecular weight = 440, amine value = 355 mg KOH / g)

[0164]

[0165] <Evaluation> (Elongation at Break of Polyisocyanate Composition (X)) A polyol mixture was prepared by mixing 70 parts of a bifunctional polypropylene polyol (manufactured by AGC, Exenol 420 (molecular weight = 400, hydroxyl value = 280)) and 30 parts of a trifunctional polypropylene polyol (manufactured by AGC, Exenol 430 (molecular weight Mw = 400, hydroxyl value = 400)).

[0166] The polyisocyanate composition (X) was mixed with the polyol mixture so that the molar ratio [NCO] / [OH] of the isocyanate groups in the polyisocyanate composition and the hydroxyl groups in the polyol mixture was 1.3±0.1. A 100-200 μm coating film was formed on an untreated CPP film using an applicator, and another untreated CPP film was then placed on top of the coating film. The coating film was aged for 5 days at 40°C and 40% humidity, after which the coating film was peeled off from the untreated CPP film, and a 2 cm x 0.5 cm wide test piece was cut out. A tensile test was performed at 200 mm / min to measure the elongation at break of the coating film. Evaluation was performed according to the following criteria, and the results are summarized in Tables 2 and 3. ◯: Breaking elongation rate is 100% or more. △: Breaking elongation rate is 30% or more but less than 100%. ×: Breaking elongation rate is less than 30%.

[0167]

[0168] (Preparation of adhesive) Adhesives of the examples and comparative examples were prepared by mixing polyisocyanate composition (X) and isocyanate-reactive composition (Y) in the combinations shown in Tables 3 and 4 so that the ratio [NCO] / [isocyanate-reactive functional group] of the number of moles of isocyanate groups [NCO] contained in polyisocyanate composition (X) to the number of moles of functional groups reactive with isocyanate [isocyanate-reactive functional group] contained in isocyanate-reactive composition (Y) was the value shown in Tables 3 and 4. In the tables, [NCO] / [reactive functional group] means [NCO] / [isocyanate-reactive functional group].

[0169] (Preparation of Laminate) The prepared adhesive was applied to a stretched polyethylene film (BOPE film) having a thickness of 50 μm at a solid content of 3 g / m ２ The laminate was then laminated to a linear low-density polyethylene film (LLDPE film) having a thickness of 110 μm, and aged at 40° C. for 72 hours to obtain a laminate.

[0170] (Bag Breakage Resistance) A 30 cm x 65 cm test piece was cut from the laminate and heat-sealed at 150°C for 1 second to create a three-sided bag with the short side as the bottom. 6 kg of DIC Styrene XC-535 (polystyrene pellets, manufactured by DIC Corporation) was filled into the bag, and the top of the bag was heat-sealed under the same conditions. Multiple evaluation samples were prepared for each of the adhesives in the Examples and Comparative Examples. The prepared samples were dropped three times from a height of 1 m, and the bag breakage rate (broken samples / prepared sample) was measured and evaluated according to the following criteria. The results are summarized in Tables 4 and 5. ◯: Bag breakage rate is 10% or less △: Bag breakage rate is more than 10% but not more than 30% ×: Bag breakage rate is more than 30%

[0171] (Easy Tear Property) A test piece measuring 75 mm x 63 mm was cut from the laminate, and a 20 mm incision was made to prepare an evaluation sample. The tear strength (N / cm) per sheet in the MD direction of the evaluation sample was measured using an Elmendorf tear tester. The evaluation was performed according to the following criteria, and the results are summarized in Tables 4 and 5. ◯: Tear strength is less than 1000 N / cm; ×: Tear strength is 1000 N / cm or more.

[0172]

[0173]

Claims

1. A polyisocyanate composition (X) containing a polyisocyanate compound (A), wherein the polyisocyanate compound (A) contains a bifunctional polyisocyanate compound (A1) derived from a non-aromatic diisocyanate, and the content of the polyisocyanate compound (A1) in the polyisocyanate compound (A) is 60 mass% or more; The polyisocyanate composition (X) is cured with a polyol mixture containing 70±1 mass% of a polypropylene diol having a hydroxyl value number-average molecular weight of 415±20 and 30±1 mass% of a polypropylene triol having a number-average molecular weight of 415±35 (provided that the total of the polypropylene diol and the polypropylene triol is 100 mass%) at a molar ratio [NCO] / [OH] of the isocyanate groups in the polyisocyanate compound (A) to the hydroxyl groups in the polyol mixture of 1.3±0.1, to form a coating film, the coating film having an elongation at break of 30% or more at a tensile speed of 200 mm / min at 25°C and a humidity of 40%.

2. The polyisocyanate composition (X) according to claim 1, wherein the content of the diisocyanate monomer is 5% by mass or less.

3. The polyisocyanate composition according to claim 1, wherein the content of the polyisocyanate compound (A1) in the polyisocyanate compound (A) is 60 mass% or more.

4. The polyisocyanate composition (X) according to claim 1, wherein the elongation at break is 100% or more.

5. The polyisocyanate composition (X) according to claim 1, further comprising at least one selected from the group consisting of a solvent (B), a phosphoric acid derivative (C), and a plasticizer (D).

6. A two-component curing adhesive comprising the polyisocyanate composition (X) according to claim 1 and an isocyanate-reactive composition (Y) containing an isocyanate-reactive compound (E), wherein the isocyanate-reactive compound (E) contains at least one selected from the group consisting of polyester polyol (E1), polyether polyol (E2), vegetable oil polyol (E3), polyurethane polyol (E4), sugar alcohol (E5), and amine compound (E6).

7. A two-component curing adhesive comprising the polyisocyanate composition (X) according to claim 4 and an isocyanate-reactive composition (Y) containing an isocyanate-reactive compound (E), wherein the isocyanate-reactive compound (E) contains at least one selected from the group consisting of polyester polyol (E1), polyether polyol (E2), vegetable oil polyol (E3), polyurethane polyol (E4), sugar alcohol (E5), and amine compound (E6).

8. The two-component curing adhesive according to claim 4, wherein the polyester polyol (E1) is a polyester polyol that is a reaction product of a polyhydric alcohol and a polycarboxylic acid, the polyhydric alcohol comprises at least one selected from ethylene glycol, diethylene glycol, dipropylene glycol, 1,6-hexanediol, neopentyl glycol, trimethylolpropane, 1,2-propanediol, 2-methyl-1,3-propanediol, and 3-methyl-1,5-pentanediol, and the proportion of this compound in the polyhydric alcohol is 70% by mass or more, and the polycarboxylic acid comprises at least one selected from isophthalic acid, terephthalic acid, orthophthalic acid, adipic acid, sebacic acid, and dimer acid, and the proportion of this compound in the polycarboxylic acid is 70% by mass or more.

9. The two-component curing adhesive according to claim 6, wherein the isocyanate-reactive compound (E) comprises the amine compound (E6), and the amine value of the isocyanate-reactive composition (Y) is 20 to 70 mg KOH / g.

10. The two-component curing adhesive according to claim 6, wherein the total amount of (E1) to (E6) in the isocyanate-reactive compound (E) is 70 mass % or more.

11. The two-component curing adhesive according to claim 6, wherein the ratio [NCO] / [isocyanate-reactive functional group] of the number of moles of isocyanate groups contained in the polyisocyanate composition (X) to the number of moles of functional groups reactive with isocyanate contained in the isocyanate-reactive composition (Y) is 0.5 to 5.

0.

12. The two-component curing adhesive according to claim 6, wherein the mass ratio of the solid content of the polyisocyanate composition (X) to the isocyanate composition (Y) is 5:10 to 100:

10.

13. The two-component curing adhesive according to claim 6, which is a solvent-free type.

14. A laminate comprising a first substrate, a second substrate, and an adhesive layer disposed between the first substrate and the second substrate, the adhesive layer being a cured coating film of the two-component curing adhesive described in any one of claims 6 to 13.

15. The laminate according to claim 14, wherein the first substrate and the second substrate comprise a polyolefin resin.

16. The laminate of claim 14, wherein the first substrate and the second substrate comprise polyethylene.

17. A packaging material obtained by forming a bag from the laminate according to claim 14.

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