Two-pack curable composition, two-pack curable coating agent, two-pack curable adhesive, laminate, and packaging material

Abstract

The present invention provides: a two-pack curable composition capable of imparting oxygen barrier properties when used as a laminate adhesive or a coating agent; and a laminate and a packaging material that are manufactured by using said composition.　Provided are: a two-pack curable composition that contains a polyol composition (X) containing a polyol compound (A), and contains a polyisocyanate composition (Y) containing a polyisocyanate compound (B), the polyol composition (X) containing a polyester polyol (A1), which is the reaction product of a composition containing a multivalent alcohol and a multivalent carboxylic acid; and a laminate and a packaging material that are manufactured by using said two-pack curable composition.

Description

Two-component curing compositions, two-component curing coatings, two-component curing adhesives, laminates, packaging materials

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

[0002] Packaging materials used for food and daily necessities typically consist of a laminate formed by bonding a heat-sealable film, such as polyethylene film or polypropylene film, with a resin film that has excellent heat resistance and strength, such as polyester film or nylon film, using an adhesive (Patent Documents 1 and 2). As an adhesive used for such laminates, a two-component polyurethane adhesive consisting of polyol and isocyanate is known.

[0003] Meanwhile, in recent years, with the growing demand for a circular economy, attempts have been made to recycle and reuse packaging materials. However, laminates made by bonding different types of resin films together, as described above, are difficult to separate by type and are not suitable for recycling. For this reason, attempts are being made to make material recycling easier by using the same type of resin for the film used in the manufacture of the laminate (monomaterialization). Olefin resins such as polypropylene and polyethylene are being considered as resin types.

[0004] Japanese Patent Publication No. 2014-004799 Japanese Patent Publication No. 2004-238050

[0005] However, since polyethylene and polypropylene films have poor oxygen barrier properties, packaging materials made using only these films are more susceptible to oxidation of their contents compared to conventional packaging materials. There is a need for a method to impart oxygen barrier properties to laminates without compromising recyclability (i.e., without limiting the proportion of the same type of resin in the laminate to a certain level).

[0006] This invention has been made in view of these circumstances, and aims to provide a two-component curable composition that can impart oxygen barrier properties when used as a laminating adhesive or coating agent.

[0007] In other words, the present invention relates to a two-component curable composition comprising a polyol composition (X) containing a polyol compound (A) and a polyisocyanate composition (Y) containing a polyisocyanate compound (B), wherein the polyol composition (X) contains a polyester polyol (A1) which is a reaction product of a composition containing a polyhydric alcohol and a polyhydric carboxylic acid.

[0008] According to the present invention, it is possible to provide a two-component curable composition that can impart oxygen barrier properties when used as a laminating adhesive or coating agent.

[0009] <Two-component curable composition> The two-component curable composition of the present invention comprises a polyol composition (X) containing a polyol compound (A) and a polyisocyanate composition (Y) containing a polyisocyanate compound (B). The two-component curable composition of the present invention will be described in detail below.

[0010] (Polyol composition (X)) Polyol composition (X) comprises polyol compound (A), which is a reaction product of a composition containing a polycarboxylic acid and a polyhydric alcohol, and includes polyester polyol (A1) having excellent oxygen barrier properties.

[0011] In a preferred embodiment of the adhesive of the present invention, polyester polyol (A1) is a reaction product of a polycarboxylic acid and a polyhydric alcohol, wherein the polycarboxylic acid includes isophthalic acid and the polyhydric alcohol is polyester polyol (A1-1) which includes at least one selected from diethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol.

[0012] The polycarboxylic acid used in the synthesis of polyester polyol (A1-1) may be entirely isophthalic acid, or it may further contain at least one selected from terephthalic acid, adipic acid, and succinic acid in addition to isophthalic acid. Examples of the polyester polyol (A1-1) include those in which the entire polycarboxylic acid is isophthalic acid, those using isophthalic acid and adipic acid, those using isophthalic acid and succinic acid, those using isophthalic acid and terephthalic acid, those using isophthalic acid, adipic acid and terephthalic acid, and those using isophthalic acid, succinic acid and terephthalic acid.

[0013] When the polycarboxylic acid contains polycarboxylic acids other than isophthalic acid, the content of isophthalic acid in the polycarboxylic acid is preferably 50% by mass or more, and more preferably 70% by mass or more. When the polycarboxylic acid contains adipic acid, the content of adipic acid in the polycarboxylic acid is preferably 5% by mass or more, and more preferably 30% by mass or less. When the polycarboxylic acid contains succinic acid, the content of succinic acid in the polycarboxylic acid is preferably 5% by mass or more, and more preferably 30% by mass or less. When the polycarboxylic acid contains terephthalic acid, the content of terephthalic acid in the polycarboxylic acid is preferably 1% by mass or more, and more preferably 20% by mass or less.

[0014] The polycarboxylic acid used in the synthesis of polyester polyol (A1-1) may include polycarboxylic acids other than isophthalic acid, adipic acid, succinic acid, and terephthalic acid (referred to here as "other carboxylic acids"). The content of other carboxylic acids in the polycarboxylic acid is, for example, 30% by mass or less, for another example, 20% by mass or less, and for yet another example, 10% by mass or less.

[0015] Other carboxylic acids include aliphatic polycarboxylic acids such as oxalic acid, malonic acid, ethyl malonic acid, dimethyl malonic acid, dimethyl succinic acid, maleic acid, fumaric acid, sebacic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-cyclohexenedicarboxylic acid, and 3-methyl-4-cyclohexene-1,2-dicarboxylic acid, as well as their anhydrides and methyl esters; Examples include aromatic polybasic acids such as orthophthalic acid, phthalic anhydride, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid anhydride, naphthalic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid, benzophenonetetracarboxylic acid, benzophenonetetracarboxylic acid dianhydride, 5-sodium sulfoisophthalic acid, tetrachlorophthalic anhydride, and tetrabromophthalic anhydride; and methyl esters of aromatic polybasic acids such as dimethylterephthalic acid and dimethyl 2,6-naphthalenedicarboxylic acid. If it is necessary to avoid the formation of cyclic oligomers that are difficult to hydrolyze as by-products, it is preferable to avoid using ortho-directing aromatic dicarboxylic acids, their anhydrides, and alkyl esters.

[0016] The polyhydric alcohol used in the synthesis of polyester polyol (A1-1) can be a combination of two or more selected from diethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol, but it is also preferable to use only one of them. However, "only one" here means that only one can be selected from this group, and may include glycerin and other alcohols as described later. It is preferable to use diethylene glycol or 1,2-propanediol.

[0017] The polyhydric alcohol used in the synthesis of polyester polyol (A1-1) may also preferably contain glycerin. The amount of glycerin can be adjusted as appropriate depending on the desired physical properties, but as an example, it is preferably 10% by mass or less of the polyhydric alcohol used in the synthesis of polyester polyol (A1-1).

[0018] The polyhydric alcohol used in the synthesis of polyester polyol (A1-1) may contain other polyhydric alcohols (referred to here as "other alcohols"), the proportion of which is, for example, 10% by mass or less. The polyhydric alcohol used in the synthesis of polyester polyol (A1-1) does not have to contain other alcohols.

[0019] Other alcohols include, but are not limited to, glycols such as ethylene glycol, 1,5-pentanediol, dimethylbutanediol, butylethylpropanediol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol; and trifunctional or tetrafunctional aliphatic alcohols such as trimethylolpropane and pentaerythritol.

[0020] In another preferred embodiment of the adhesive of the present invention, polyester polyol (A1) is a reaction product of a polycarboxylic acid and a polyhydric alcohol, wherein the polycarboxylic acid comprises terephthalic acid and at least one selected from adipic acid and succinic acid, and the polyhydric alcohol comprises ethylene glycol, forming polyester polyol (A1-2).

[0021] Examples of the polyester polyol (A1-2) include those in which the polycarboxylic acid contains terephthalic acid and adipic acid, and those in which it contains terephthalic acid and succinic acid.

[0022] When a polycarboxylic acid contains adipic acid, the adipic acid content in the polycarboxylic acid is, for example, 5% by mass or more, for another example, 15% by mass or more, for another example, 25% by mass or more, for one example, 95% by mass or less, for another example, 85% by mass or less, and for another example, 75% by mass or less. When a polycarboxylic acid contains succinic acid, the succinic acid content in the polycarboxylic acid is, for example, 5% by mass or more, for another example, 15% by mass or more, for another example, 25% by mass or more, for one example, 95% by mass or less, for another example, 85% by mass or less, and for another example, 75% by mass or less. The terephthalic acid content in the polycarboxylic acid is, for example, 5% by mass or more, for another example, 15% by mass or more, for another example, 25% by mass or more, for one example, 95% by mass or less, for another example, 85% by mass or less, and for another example, 75% by mass or less.

[0023] The polycarboxylic acid used in the synthesis of polyester polyol (A1-2) may include polycarboxylic acids other than terephthalic acid, adipic acid, and succinic acid (referred to here as "other carboxylic acids"). The content of other carboxylic acids in the polycarboxylic acid is, for example, 30% by mass or less, for another example, 20% by mass or less, and for yet another example, 10% by mass or less.

[0024] Other carboxylic acids include those similar to those exemplified as other carboxylic acids for polyester polyol (A1-1), as well as isophthalic acid. If it is necessary to avoid the formation of hydrolyzable cyclic oligomers as by-products, it is preferable to avoid using ortho-directing aromatic dicarboxylic acids, their anhydrides, and alkyl esters.

[0025] The polyhydric alcohol used in the synthesis of polyester polyol (A1-2) preferably also contains glycerin in addition to ethylene glycol. The amount of glycerin can be adjusted as appropriate depending on the desired physical properties, but as an example, it is preferably 10% by mass or less of the polyhydric alcohol used in the synthesis of polyester polyol (A1-2).

[0026] The polyhydric alcohol used in the synthesis of polyester polyol (A1-2) may contain other polyhydric alcohols (referred to here as "other alcohols"), but it is preferable that their proportion be kept to 10% by mass or less. The polyhydric alcohol used in the synthesis of polyester polyol (A1-2) does not have to contain other alcohols.

[0027] Other alcohols that can be used are the same polyhydric alcohols used in the synthesis of polyester polyol (A1-1).

[0028] The hydroxyl value of polyester polyol (A1) can be adjusted as appropriate, but as an example, it is 10 mg KOH / g or more, as another example, 100 mg KOH / g or more, as another example, 500 mg KOH / g or less, as yet another example, 450 mg KOH / g or less, and as yet another example, 300 mg KOH / g or less. The hydroxyl value can be measured by the method described in JIS-K0070.

[0029] The acid value of polyester polyol (A1) can be adjusted as appropriate, but in one embodiment of polyester polyol (A1), the acid value may be 0.5 mg KOH / g or more and 90 mg KOH / g or less. The acid value can be measured by the method described in JIS-K0070.

[0030] Polyester polyols (A1) having an acid value can be obtained by methods such as adjusting the proportions of polyhydric alcohol and polycarboxylic acid used in synthesis, terminating the esterification reaction when the acid value is within the above range, or modifying some of the hydroxyl groups of the polyester polyol with a compound having multiple acid groups, such as a polycarboxylic acid.

[0031] The compounds having acidic groups used for modification are not particularly limited as long as they have a functional group that can react with a hydroxyl group and can introduce an acidic group to the end of the polyester polyol after the reaction. More specifically, succinic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, dodecenyl succinic anhydride, polyadipic anhydride, polyazelaic anhydride, polysebacic anhydride, poly(ethyloctadecanediic acid) anhydride, poly(phenylhexadecanedioic acid) anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylhymic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexendical Examples include acid anhydrides such as bonic acid anhydride, methylcyclohexenetetracarboxylic acid anhydride, ethylene glycol bistrimellitate dianhydride, hetic 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-naphthalenesuccinic acid dianhydride, and 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dianhydride, as well as compounds obtained by modifying these acid anhydrides with glycol.

[0032] Examples of glycols that can be used to modify acid anhydrides 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 can also be used.

[0033] The polyol compound (A) may contain polyol compounds other than the polyester polyol (A1-1) and the polyester polyol (A1-2). Examples of other polyol compounds that can be used as the polyol compound (A) include polyester polyols (A2) other than the polyester polyols (A1-1) and (A1-2), polyether polyols (A3), vegetable oil polyols (A4), polyurethane polyols (A5), sugar alcohols (A6), acrylic polyols (A7), etc. (hereinafter, these are also simply referred to as polyol compounds (A2) to (A7)).

[0034] Examples of the polyester polyol (A2) include polyester polyols that are reaction products of polyhydric alcohols and polyvalent carboxylic acids, and lactone-based polyester polyols obtained by polycondensation reactions of aliphatic polyols and various lactones such as ε-caprolactone. It is preferable to use a polyester polyol that is a reaction product of a polyhydric alcohol and a polyvalent carboxylic acid.

[0035] Examples of the polyhydric alcohol include aliphatic diols such as ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,2,2-trimethyl-1,3-propanediol, 2,2-dimethyl-3-isopropyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-bis(hydroxymethyl)cyclohexane, 2,2,4-trimethyl-1,3-pentanediol;

[0036] trifunctional or higher-functional aliphatic polyols such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, pentaerythritol;

[0037] bisphenols such as bisphenol A and bisphenol F; alkylene oxide adducts of bisphenols obtained by adding ethylene oxide, propylene oxide, etc. to bisphenols such as bisphenol A and bisphenol F;

[0038] Examples include polyether polyols obtained by ring-opening polymerization of aliphatic diols or polyols with various cyclic ether-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, and these can be used individually or in combination of two or more.

[0039] 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 acids, which can be used individually or in combination of two or more. If it is necessary to avoid the formation of cyclic oligomers that are difficult to hydrolyze as by-products, it is preferable to avoid using ortho-directing aromatic dicarboxylic acids, their anhydrides, and alkyl esters.

[0040] The molecular weight of polyester polyol (A2) is preferably 250 g / mol or more and 20,000 g / mol or less, and more preferably 500 g / mol or more and 10,000 g / mol or less. The hydroxyl value of polyester polyol (A2) is preferably 5 mg KOH / g or more and 500 mg KOH / g or less.

[0041] Examples of polyether polyols (A3) 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.

[0042] Polymerization initiators 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;

[0043] Trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, pentaerythritol, and triol compounds of polypropylene glycol;

[0044] Examples include primary or secondary alkylamines such as ethylamine and diethylamine, amine compounds having multiple amino groups such as methylenediamine and ethylenediamine, and amine compounds having active hydrogen groups such as primary or secondary alkanolamines such as monoethanolamine and diethanolamine.

[0045] The molecular weight of the polyether polyol (A3) can be adjusted as appropriate, but as an example, it is preferably between 100 g / mol and 8000 g / mol. The hydroxyl value of the polyether polyol (A3) can be adjusted as appropriate, but as an example, it is preferably between 10 mg KOH / g and 1200 mg KOH / g.

[0046] Examples of vegetable oil polyols (A4) include castor oil, dehydrated castor oil, hydrogenated castor oil (a hydrogenated product of castor oil), and castor oil alkylene oxide adducts of 5 to 50 moles.

[0047] Polyurethane polyols (A5) are reaction products of low-molecular-weight or high-molecular-weight polyols and polyisocyanate compounds. Low-molecular-weight polyols can be the same as those used as the polyhydric alcohols exemplified as raw materials for polyester polyols (A2). High-molecular-weight polyols can include polyester polyols (A2), polyether polyols (A3), vegetable oil polyols (A4), sugar alcohols (A6), acrylic polyols (A7), etc. Polyisocyanate compounds can be the same as those exemplified as polyisocyanate compounds (B) described later.

[0048] Examples of sugar alcohols (A6) include pentaerythritol, sucrose, xylitol, sorbitol, isomalt, lactitol, maltitol, and mannitol.

[0049] Acrylic polyol (A7) is required to be a (meth)acrylic acid ester having a hydroxyl group, and can be obtained by copolymerization with a polymerizable unsaturated monomer as needed. In this specification, (meth)acrylic acid means methacrylic acid or acrylic acid. Examples of (meth)acrylic acid esters having a hydroxyl group include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, etc., and can be used one or in combination of two or more.

[0050] Polymerizable unsaturated monomers include alkyl(meth)acrylates having alkyl groups with 1 to 22 carbon atoms, such as methyl(meth)acrylate, ethyl(meth)acrylate, n-propyl(meth)acrylate, n-butyl(meth)acrylate, isobutyl(meth)acrylate, tert-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and lauryl(meth)acrylate; aralkyl(meth)acrylates such as benzyl(meth)acrylate and 2-phenylethyl(meth)acrylate; cycloalkyl(meth)acrylates such as cyclohexyl(meth)acrylate and isobornyl(meth)acrylate; and ω-alkoxyalkyl(meth)acrylates such as 2-methoxyethyl(meth)acrylate and 4-methoxybutyl(meth)acrylate. Polyfunctional (meth)acrylates such as ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and dipentaerythritol hexa(meth)acrylate;

[0051] (meth)acrylic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, 4-methylcyclohexe-4-ene-1,2-dicarboxylic acid anhydride, bicyclo[2.2.2]octo-5-ene-2,3-dicarboxylic acid anhydride, 1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic acid anhydride, 2-octa-1,3-diketospiro[4.4]non-7-ene, bicyclo[ Examples of polymerizable unsaturated monomers having acid groups, such as hept-5-ene-2,3-dicarboxylic acid anhydride, maleopimaric acid, tetrahydrophthalic acid anhydride, methyl-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid anhydride, methyl-norbornene-5-ene-2,3-dicarboxylic acid anhydride, norbornne-5-ene-2,3-dicarboxylic acid anhydride, sulfonated styrene, and vinylbenzenesulfonamide; vinyl carboxylate esters such as vinyl acetate, vinyl propionate, vinyl pivalate, and vinyl benzoate; alkyl esters of crotonic acid such as methyl crotate and ethyl crotate; dialkyl esters of unsaturated dibasic acids such as dimethyl malate, di-n-butyl malate, dimethyl fumarate, and dimethyl itaconate; and others. These may be used individually or in combination of two or more.

[0052] If polyol compound (A) contains polyol compounds (A2) to (A7), it is preferable that their content be 10% by mass or less of polyol compound (A). In other words, it is preferable that the content of polyester polyol (A1) in polyol compound (A) be 90% by mass or more. Polyol compound (A) does not have to contain polyol compounds (A2) to (A7).

[0053] (Polyisocyanate composition (Y)) The polyisocyanate composition (Y) comprises a polyisocyanate compound (B) having a plurality of isocyanate groups. The polyisocyanate compound (B) can be any conventionally known compound without particular limitation, and examples include aromatic diisocyanates, aromatic aliphatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and the biuret, nurate, adduct, allophanate, carbodiimide modified, uretdione modified, iminooxadiazinedione, polyurethane polyisocyanates, etc., and one or more of these can be used in combination.

[0054] Examples of aromatic diisocyanates include 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (also known as MDI), polymethylene polyphenyl polyisocyanate (also called polymeric MDI or crude MDI), 1,3-phenylenediisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylenediisocyanate (also known as PPDI), and 2,4-toluene. Examples include, but are not limited to, diisocyanates, 2,6-toluene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, toidine diisocyanate (also known as TODI), dianisidine diisocyanate, naphthalene diisocyanate (also known as NDI), 4,4'-diphenyl ether diisocyanate, and 4,4',4''-triphenylmethane triisocyanate.

[0055] Aromatic aliphatic diisocyanates refer to aliphatic isocyanates having one or more aromatic rings in their molecule, and include, but are not limited to, m- or p-xylylene diisocyanate (also known as XDI) and α,α,α',α'-tetramethylxylylene diisocyanate (also known as TMXDI).

[0056] Examples of aliphatic diisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate (also known as PDI), 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate (also known as LDI), but are not limited to these.

[0057] Examples of alicyclic diisocyanates include, but are not limited to, 3-isocyanate-methyl-3,5,5-trimethylcyclohexyl isocyanate, isophorone diisocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebiscyclohexyl isocyanate (also known as hydrogenated MDI or HMDI), 1,3-bis(isocyanate-methyl)cyclohexane (also known as hydrogenated XDI or HXDI), hydrogenated TMXDI, norbornane diisocyanate (also known as NBDI), etc.

[0058] Compounds used in the synthesis of adducts include low molecular weight active hydrogen compounds such as ethylene glycol, propylene glycol, metaxylylene alcohol, 1,3-bishydroxyethylbenzene, 1,4-bishydroxyethylbenzene, trimethylolpropane, glycerol, pentaerythritol, erythritol, sorbitol, 1,3,5-tris(2-hydroxyethyl) isocyanurate, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, and metaxylylenediamine.

[0059] For the synthesis of polyurethane polyisocyanates, the same polyols as those exemplified as polyol compound (A) can be used. The molecular weight of the polyol used in the synthesis of polyurethane polyisocyanates can be adjusted as appropriate, but as an example, it is between 50 g / mol and 4000 g / mol.

[0060] In particular, isocyanate compounds having a skeleton derived from xylylene diisocyanate, hydrogenated xylylene diisocyanate, toluene diisocyanate, or diphenylmethane diisocyanate are preferred because they provide good gas barrier properties, and it is preferable to use at least one selected from the polyisocyanate compounds (B1) to (B7) described later.

[0061] Polyisocyanate compound (B1) is a polyurethane polyisocyanate, which is a reaction product of a diisocyanate and a polyol having an ether linkage with a molecular weight of 65 to 300. The diisocyanate used in the synthesis of polyisocyanate compound (B1) is at least one selected from xylylene diisocyanate and toluene diisocyanate. The toluene diisocyanate may be either 2,4'-toluene diisocyanate, 2,6'-toluene diisocyanate, or both.

[0062] Examples of polyols having ether links with a molecular weight of 65 to 300 include diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripylene glycol, tetrapropylene glycol, polypropylene glycol, 4-methoxy-1,3-butanediol, 5-methoxy-1,3-pentanediol, 5-ethoxy-1,3-pentanediol, etc., and can be used individually or in combination of two or more.

[0063] Polyisocyanate compound (B1) is obtained by reacting a diisocyanate with a polyol under conditions in which the isocyanate groups of the diisocyanate are in excess of the hydroxyl groups of the polyol. The equivalent ratio of isocyanate groups to hydroxyl groups [NCO] / [hydroxyl groups] can be adjusted as appropriate, but as an example, it is between 2.0 and 20.0.

[0064] The polyisocyanate compound (B1) preferably contains as little diisocyanate as possible that was used in its synthesis. More specifically, it is preferable that the diisocyanate content is reduced to 1.0% by mass or less, and more preferably to 0.1% by mass or less.

[0065] Diisocyanate can be removed by distilling it under reduced pressure using a short-pass distillation apparatus or a thin-film distillation apparatus. The degree of reduced pressure and distillation temperature are adjusted as appropriate, but as an example, they are 0.1 mbar or less and 120°C to 190°C. The diisocyanate removal process may be performed multiple times.

[0066] The diisocyanate content can be measured by gas chromatography using an internal standard, for example, according to ASTM D 3432. Alternatively, it can be measured by liquid chromatography under the following conditions.

[0067] Apparatus: Waters Corporation "ACQUITY UPLC H-Class" Data processing: Waters Corporation "Empower-3" Column: Waters Corporation "ACQUITY UPLC HSS T3" (100 mm × 2.1 mmφ, 1.8 μm) 40℃ 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. Stir with a vortex for 30 seconds 3. Dilute appropriately with the eluent (mobile phase) 4. Pass through a 0.2 μm filter to obtain the measurement sample. Calculation of area ratio: Calculated using the maximum absorption wavelength for the target substance.

[0068] Polyisocyanate compound (B2) is a polyurethane polyisocyanate, which is the reaction product of a diisocyanate and a diol having an alkyl side chain with a molecular weight of 65 to 300 and 1 to 4 carbon atoms. The diisocyanate used in the synthesis of polyisocyanate compound (B2) is at least one selected from xylylene diisocyanate and toluene diisocyanate. Toluene diisocyanate may be either 2,4'-toluene diisocyanate, 2,6'-toluene diisocyanate, or both.

[0069] Diols having an alkyl side chain with 1 to 4 elementary atoms include 1,2-propanediol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 1,3-butanediol, 2-methyl-1,3-butanediol, 2-ethyl-1,3-butanediol, 2-propyl-1,3-butanediol, 2-butyl-1,3-butanediol, 2-pentyl-1,3-butanediol, and 2-(1-methylethyl)-1,3-butanediol. 2,2-dimethyl-1,3-butanediol, 2,3-dimethyl-1,3-butanediol, 2-ethyl-2-methyl-1,3-butanediol, 3-methyl-1,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 2,4-pentanediol, 2-methyl-1,3-pentanediol, 2-ethyl-1,3-propanediol, 2-propyl-1,3-propanediol, 4-methyl-1,3-pentanediol, 2,4-di Methyl-1,3-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-methyl-2,4-pentanediol, 3-methyl-2,4-pentanediol, 3-ethyl-2,4-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 2-methyl-1,3-hexanediol, 2-ethyl-1,3-hexanediol, 4-methyl-1,3-hexanediol, 5-methyl-1,3-hexanediol, 2,4-hex Examples include sanediol, 1,3-heptanediol, 2-methyl-1,3-methylheptanediol, 4-methyl-1,3-heptanediol, 5-methyl-1,3-heptanediol, 6-methyl-1,3-heptanediol, 2,4-heptanediol, 2,4-octanediol, 3,5-octanediol, 2,4-nonanediol, 3,5-nonanediol, 4,6-nonanediol, etc., and one or more of these can be used in combination.

[0070] Polyisocyanate compound (B2) can be synthesized in the same manner as polyisocyanate compound (B1). Furthermore, similar to polyisocyanate compound (B1), it is preferable that the diisocyanate content of polyisocyanate compound (B2) is reduced to 1.0% by mass or less, more preferably to 0.1% by mass or less. The diisocyanate can be removed in the same manner as with polyisocyanate compound (B1).

[0071] Polyisocyanate compound (B3) is a polyester polyurethane polyisocyanate, which is a reaction product of diisocyanate and polyester polyol.

[0072] The diisocyanate used in the synthesis of the polyisocyanate compound (B3) is at least one selected from xylylene diisocyanate, hydrogenated xylylene diisocyanate, 2,4'-diphenylmethane diisocyanate, and 4,4'-diphenylmethane diisocyanate, and preferably at least one selected from xylylene diisocyanate, 2,4'-diphenylmethane diisocyanate, and 4,4'-diphenylmethane diisocyanate.

[0073] The polyester polyol used in the synthesis of polyisocyanate compounds (B3) is obtained by polycondensation of a polycarboxylic acid containing an ortho-directing aromatic polycarboxylic acid with a polyhydric alcohol.

[0074] Examples of ortho-directing polycarboxylic acids include orthophthalic acid or its acid anhydride, naphthalene 2,3-dicarboxylic acid or its acid anhydride, naphthalene 1,2-dicarboxylic acid or its acid anhydride, anthraquinone 2,3-dicarboxylic acid or its acid anhydride, and 2,3-anthracenecarboxylic acid or its acid anhydride. These compounds may have substituents on any carbon atom of the aromatic ring. Examples of substituents include chloro group, bromo group, methyl group, ethyl group, i-propyl group, hydroxyl group, methoxy group, ethoxy group, phenoxy group, methylthio group, phenylthio group, cyano group, nitro group, amino group, phthalimide group, carboxyl group, carbamoyl group, N-ethylcarbamoyl group, phenyl group, or naphthyl group, and one or more of these can be used in combination.

[0075] The polycarboxylic acid may contain polycarboxylic acids other than ortho-directing polycarboxylic acids. Such polycarboxylic acids can be those similar to those exemplified as raw materials for polyester polyol (A2). When the polycarboxylic acid contains polycarboxylic acids other than ortho-directing polycarboxylic acids, it is preferable that the proportion of ortho-directing polycarboxylic acids to the total amount of polycarboxylic acid is 40 to 100% by mass.

[0076] The polyhydric alcohol preferably contains at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol, and more preferably contains ethylene glycol. In addition, other polyhydric alcohols may be used in combination. Examples include glycerin, 1,3,5-tris(2-hydroxyethyl)isocyanuric acid, and trimethylolpropane.

[0077] The molecular weight of the polyester polyol used in the synthesis of polyisocyanate compound (B3) can be adjusted as appropriate, but one example is 300 g / mol to 5000 g / mol, and another example is 350 g / mol to 3000 g / mol. The molecular weight is calculated from the obtained hydroxyl value and the number of functional groups of hydroxyl groups in the design.

[0078] Polyisocyanate compound (B3) is obtained by reacting diisocyanate with a polyester polyol under conditions in which the isocyanate groups of diisocyanate are in excess of the hydroxyl groups of the polyester polyol. The equivalent ratio of isocyanate groups to hydroxyl groups [NCO] / [hydroxyl groups] can be adjusted as appropriate, but as an example, it is between 2.0 and 20.0.

[0079] The polyisocyanate compound (B3) may contain excess diisocyanate used in its synthesis.

[0080] Polyisocyanate compound (B4) is a polyester polyurethane polyisocyanate, which is a reaction product of a diisocyanate and a polyester polyol having an isocyanuric ring.

[0081] The diisocyanate used in the synthesis of the polyisocyanate compound (B4) is preferably at least one selected from xylylene diisocyanate, hydrogenated xylylene diisocyanate, 2,4'-diphenylmethane diisocyanate, and 4,4'-diphenylmethane diisocyanate, and is preferably at least one selected from xylylene diisocyanate, 2,4'-diphenylmethane diisocyanate, and 4,4'-diphenylmethane diisocyanate.

[0082] Polyester polyols used in the synthesis of polyisocyanate compounds (B4) can be obtained, for example, by reacting a polyol having an isocyanuric ring with a polycarboxylic acid and a polyhydric alcohol.

[0083] Examples of polyols having an isocyanuric ring include alkylene oxide adducts of isocyanuric acid such as 1,3,5-tris(2-hydroxyethyl)isocyanuric acid and 1,3,5-tris(2-hydroxypropyl)isocyanuric acid.

[0084] As the polycarboxylic acid, the same type as those exemplified as the raw material for polyester polyol (A2) can be used. It is preferable to use an ortho-directing polycarboxylic acid. As the ortho-directing aromatic polycarboxylic acid, the same type as those exemplified as the raw material for polyisocyanate compound (B3) can be used.

[0085] As the polyhydric alcohol, the same as those exemplified as raw materials for polyester polyol (A2) can be used. Preferably, it contains at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol, and more preferably contains ethylene glycol.

[0086] As the polyol having an isocyanuric ring, it is preferable to use 1,3,5-tris(2-hydroxyethyl)isocyanuric acid or 1,3,5-tris(2-hydroxypropyl)isocyanuric acid. As the ortho-directing aromatic polycarboxylic acid, it is preferable to use orthophthalic anhydride. As the polyhydric alcohol, it is preferable to use ethylene glycol.

[0087] The molecular weight of the polyester polyol used in the synthesis of polyisocyanate compounds (B4) can be adjusted as appropriate, but one example is 300 g / mol to 5000 g / mol, and another example is 350 g / mol to 3000 g / mol. The molecular weight is calculated from the obtained hydroxyl value and the number of functional groups of hydroxyl groups in the design.

[0088] Polyisocyanate compound (B4) is obtained in the same manner as polyisocyanate compound (B3). Polyisocyanate compound (B4) may contain excess diisocyanate used in the synthesis.

[0089] Polyisocyanate compound (B5) is a polyester polyurethane polyisocyanate, which is a reaction product of diisocyanate and polyester polyol having a polymerizable carbon-carbon double bond.

[0090] The diisocyanate used in the synthesis of the polyisocyanate compound (B5) is preferably at least one selected from xylylene diisocyanate, hydrogenated xylylene diisocyanate, 2,4'-diphenylmethane diisocyanate, and 4,4'-diphenylmethane diisocyanate, and is preferably at least one selected from xylylene diisocyanate, 2,4'-diphenylmethane diisocyanate, and 4,4'-diphenylmethane diisocyanate.

[0091] Polyester polyols used in the synthesis of polyisocyanate compounds (B5) are obtained by using a component having a polymerizable carbon-carbon double bond in at least one of a polyhydric carboxylic acid and a polyhydric alcohol as a raw material.

[0092] Examples of polycarboxylic acids having polymerizable carbon-carbon double bonds include maleic anhydride, maleic acid, fumaric acid, 4-cyclohexene-1,2-dicarboxylic acid and its acid anhydride, and 3-methyl-4-cyclohexene-1,2-dicarboxylic acid and its acid anhydride. Maleic anhydride, maleic acid, and fumaric acid are preferred because it is presumed that the fewer carbon atoms there are, the less the molecular chain becomes excessively flexible and therefore less permeable to oxygen. Examples of polyhydric alcohols having polymerizable carbon-carbon double bonds include 2-butene-1,4-diol.

[0093] The polyester polyol used in the synthesis of the polyisocyanate compound (B5) may also contain polycarboxylic acids and polyhydric alcohols that do not have polymerizable carbon-carbon double bonds as raw materials. Such polycarboxylic acids and polyhydric alcohols can be the same as those exemplified as raw materials for polyester polyol (A2).

[0094] The polycarboxylic acid that does not have a polymerizable carbon-carbon double bond is preferably at least one selected from the group consisting of succinic acid, 1,3-cyclopentanedicarboxylic acid, orthophthalic acid, acid anhydride of orthophthalic acid, and isophthalic acid, and more preferably at least one of orthophthalic acid and its acid anhydride.

[0095] As a polyhydric alcohol that does not have a polymerizable carbon-carbon double bond, it is preferable to use at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol, and it is more preferable to use ethylene glycol.

[0096] The molecular weight of the polyester polyol used in the synthesis of polyisocyanate compounds (B5) can be adjusted as appropriate, but one example is 300 g / mol to 5000 g / mol, and another example is 350 g / mol to 3000 g / mol. The molecular weight is calculated from the obtained hydroxyl value and the number of functional groups of hydroxyl groups in the design.

[0097] Polyisocyanate compound (B5) is obtained in the same manner as polyisocyanate compound (B3). Polyisocyanate compound (B5) may contain excess diisocyanate used in the synthesis.

[0098] Polyisocyanate compound (B6) is a polyester polyurethane polyisocyanate, which is a reaction product of diisocyanate and polyester polyol. The polyester polyol used in the synthesis of polyisocyanate compound (B6) has a skeleton similar to that of the polyester polyol (A1) described above.

[0099] The diisocyanate used in the synthesis of the polyisocyanate compound (B6) is preferably at least one selected from xylylene diisocyanate, hydrogenated xylylene diisocyanate, 2,4'-diphenylmethane diisocyanate, and 4,4'-diphenylmethane diisocyanate, and is preferably at least one selected from xylylene diisocyanate, 2,4'-diphenylmethane diisocyanate, and 4,4'-diphenylmethane diisocyanate.

[0100] The hydroxyl value of the polyester polyol used in the synthesis of the polyisocyanate compound (B6) can be adjusted as appropriate, but as an example, it is 10 mg KOH / g or more, as another example, 100 mg KOH / g or more, as another example, 500 mg KOH / g or less, as yet another example, 450 mg KOH / g or less, and as yet another example, 300 mg KOH / g or less.

[0101] Polyisocyanate compound (B6) is obtained in the same manner as polyisocyanate compound (B3). Polyisocyanate compound (B6) may contain excess diisocyanate used in the synthesis, or the amount may be reduced to 1.0% by mass or less, more preferably to 0.1% by mass or less. The diisocyanate can be removed in the same manner as polyisocyanate compound (B1).

[0102] Examples of polyisocyanate compounds (B7) include adducts of at least one diisocyanate selected from xylylene diisocyanate, hydrogenated xylylene diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate. Adducts of xylylene diisocyanate and trimethylolpropane are preferred.

[0103] The polyisocyanate compound (B) may contain two or more polyisocyanate compounds selected from (B1) to (B7). The total amount of polyisocyanate compounds (B1) to (B7) in the polyisocyanate compound (B) is, for example, 70% by mass or more. The total amount of polyisocyanate compound (B) may be at least one polyisocyanate compound selected from (B1) to (B7). If it is necessary to avoid the formation of cyclic oligomers that are difficult to hydrolyze as by-products, it is preferable to avoid using polyester polyurethane polyisocyanates made from ortho-directing aromatic dicarboxylic acids, their anhydrides, or alkyl esters as raw materials.

[0104] The NCO% of the polyisocyanate composition (Y) can be adjusted as appropriate depending on the purpose, but as an example, it is preferably 7% to 21%.

[0105] (Additive (C)) The two-component curable composition may contain additive (C). Examples of additive (C) include, but are not limited to, phosphoric acid derivatives (C1), plasticizers (C2), urethane catalysts (C3), coupling agents (C4), pigments (C5), and acid anhydrides (C6). The additive may be included in either or both of the polyol composition (X) and the polyisocyanate composition (Y), or it may be prepared separately and mixed with the polyol composition (X) and the polyisocyanate composition (Y) immediately before coating the two-component curable composition. The following describes each component.

[0106] Examples of phosphate derivatives (C1) include phosphoric acid, pyrophosphate, triphosphate, 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, pyrophosphate, triphosphate, and butyl acid phosphate are preferred.

[0107] When the two-component curable composition of the present invention contains a phosphoric acid derivative (C1), its content can be adjusted as appropriate, but as an example, it is preferably 0.005 to 10% by mass of the solid content of the two-component curable composition, and more preferably 0.01 to 1% by mass.

[0108] Examples of plasticizers (C2) include phthalate-based plasticizers, fatty acid-based plasticizers, aromatic polycarboxylic acid-based plasticizers, phosphate-based plasticizers, polyol-based plasticizers, epoxy-based plasticizers, polyester-based plasticizers, and carbonate-based plasticizers.

[0109] Examples of phthalate-based plasticizers include phthalate 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, as well as tetrahydrophthalate ester plasticizers such as di-(2-ethylhexyl)tetrahydrophthalate, di-n-octyltetrahydrophthalate, and diisodecyltetrahydrophthalate.

[0110] Examples of fatty acid-based plasticizers include adipic acid-based plasticizers such as di-n-butyl adipate, di-(2-ethylhexyl) adipate, diisodecyl adipate, diisononyl adipate, di(C6-C10 alkyl) adipate, and dibutyldiglycol adipate; azelaic acid-based plasticizers such as di-n-hexyl azelate, di-(2-ethylhexyl) azelate, and diisooctyl azelate; and di-n-butyl sebacate, di-(2 Sebacate-based plasticizers such as -ethylhexyl) sebacate and diisononyl sebacate; maleic acid-based plasticizers such as dimethyl maleate, diethyl maleate, di-n-butyl maleate, and di-(2-ethylhexyl) maleate; fumaric acid-based plasticizers such as di-n-butyl fumarate and di-(2-ethylhexyl) fumarate; monomethyl itaconate, monobutyl itaconate, dimethyl itaconate, diethyl itaconate, dibutyrate Examples include itaconic acid-based plasticizers such as ruitaconate 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; citrate-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 methylacetyl ricinoleate, butylacetyl ricinoleate, glyceryl monoricinoleate, and diethylene glycol monoricinoleate; and other fatty acid-based plasticizers such as diethylene glycol monolaurate, diethylene glycol diperargonate, and pentaerythritol fatty acid esters.

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

[0112] Examples of phosphate-based plasticizers include triethyl phosphate, tributyl phosphate, tri-(2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, octyldiphenyl phosphate, cresyldiphenyl phosphate, cresylphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris(chloroethyl) phosphate, tris(chloropropyl) phosphate, tris(dichloropropyl) phosphate, and tris(isopropylphenyl) phosphate.

[0113] Examples of polyol-based plasticizers include glycol-based plasticizers such as diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, triethylene glycol di-(2-ethyl butyrate), triethylene glycol di-(2-ethylhexoate), and dibutylmethylene bisthioglycolate, as well as glycerin-based plasticizers such as glycerol monoacetate, glycerol triacetate, and glycerol triphyalate.

[0114] Examples of epoxy plasticizers include epoxidized soybean oil, epoxybutyl stearate, di-2-ethylhexyl epoxyhexahydrophthalate, diisodecyl epoxyhexahydrophthalate, epoxy triglycerides, octyl epoxidized oleate, and decyl epoxidized oleate.

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

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

[0117] Other examples of plasticizers (C2) include partially hydrogenated terphenyl, adhesive plasticizers, and polymerizable plasticizers such as diallyl phthalate, acrylic monomers, and oligomers. These plasticizers can be used individually or in combination of two or more.

[0118] The amount of plasticizer (C2) can be adjusted as appropriate depending on the desired viscosity, but as an example, it is preferable to limit it to 30% by mass or less of the two-component curable composition.

[0119] Examples of urethane catalysts (C3) include metal catalysts, amine catalysts, aliphatic cyclic amide compounds, and quaternary ammonium salts.

[0120] Examples of metal catalysts include metal complex catalysts, inorganic metal catalysts, and organometallic catalysts. Examples of metal complex catalysts 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.

[0121] Examples of inorganic metal catalysts include those selected from Sn, Fe, Mn, Cu, Zr, Th, Ti, Al, Co, and the like.

[0122] Examples of organometallic catalysts include organozinc compounds such as zinc octoate, zinc neodecanoate, and zinc naphthenate; organotin compounds such as stanus diacetate, stanus dioctoate, stanus dioleate, stanus dilaurate, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin oxide, and dibutyltin dichloride; organonickel compounds such as nickel octoate and nickel naphthenate; organocobalt compounds such as cobalt octoate and cobalt naphthenate; organobismuth compounds such as bismuth octoate, bismuth neodecanoate, and bismuth naphthenate; tetraisopropyloxytitanate, dibutyltitanium dichloride, tetrabutyltitanium trichloride, butoxytitanium trichloride; aliphatic diketones; aromatic diketones; and titanium compounds such as titanium chelate complexes with at least one alcohol having 2 to 10 carbon atoms as a ligand.

[0123] Amine-based catalysts include triethylenediamine, 2-methyltriethylenediamine, quinuclidine, 2-methylquinuclidine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N'',N''-pentamethyldiethylenetriamine, N,N,N',N'',N''-pentamethyl-(3-aminopropyl)ethylenediamine, N,N,N',N'',N''-pentamethyldipropylenetriamine, N,N,N',N'-tetramethylhexamethylenediamine, bis(2-dimethylaminoethyl) ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol, N,N-dimethyl-N'-(2-hydroxyethyl)ethylenediamine, N,N-dimethyl-N'-(2-hydroxyethyl)propanediamine, bis(dimethylaminopropyl)amine, bis(dimethylaminopropyl)isopropanediamine Lopanolamine, 3-Quinuclidinol, N,N,N',N'-Tetramethylguanidine, 1,3,5-Tris(N,N-dimethylaminopropyl)hexahydro-S-triazine, 1,8-Diazabicyclo[5.4.0]undecene-7, N-Methyl-N'-(2-dimethylaminoethyl)piperazine, N,N'-Dimethylpiperazine, Dimethylcyclohexylamine, N-Methylmorpholine, N-Ethylmorpholine, 1-Methylimidazole, 1 Examples include 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, and 1-(2-hydroxypropyl)-2-methylimidazole.

[0124] Examples of aliphatic cyclic amide compounds include δ-valerolactam, ε-caprolactam, ω-enanthollactam, η-capryllactam, and β-propiolactam. Among these, ε-caprolactam is more effective in accelerating curing.

[0125] Examples of quaternary ammonium salts include alkylammonium, aromatic ammonium, hydroxy salts, alkylates, and halide salts. 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, and hexadecyltrimethylammonium bromide.

[0126] When the two-component curable composition of the present invention contains a urethane catalyst (C3), the amount of the catalyst can be adjusted as appropriate, but as an example, it is preferably 5% by mass or less of the solid content of the two-component curable composition, and preferably 0.001% by mass or more and 3% by mass or less.

[0127] Examples of coupling agents (C4) include silane coupling agents, titanate coupling agents, and aluminum coupling agents.

[0128] Examples of silane coupling agents include aminosilanes such as γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, and bis[3-(triethoxysilyl)propyl]amine; 3-isocyanatetopropyltrimethoxysilane, 3-isocyanatetopropyltrimethoxysilane. Examples include isocyanate silanes such as natepropyltriethoxysilane; 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.

[0129] Examples of titanate-based coupling agents include tetraisopropoxytitanium, tetra-n-butoxytitanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, titanium lactate, and tetrastearoxititanium.

[0130] Examples of aluminum-based coupling agents include acetalkoxyaluminum diisopropylate.

[0131] When the two-component curable composition of the present invention contains a coupling agent, the amount of the coupling agent can be adjusted as appropriate, but as an example, it is preferably 5% by mass or less of the total solid content of the two-component curable composition, and preferably 0.1% by mass or more and 3% by mass or less.

[0132] There are no particular restrictions on pigments (C5), and examples include organic 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, pearlescent pigments, and even plastic pigments, as listed in the 1970 edition of the Paint Raw Materials Handbook (compiled by the Japan Paint Manufacturers Association).

[0133] Examples of extender pigments include precipitated barium sulfate, granite powder, precipitated calcium carbonate, calcium bicarbonate, limestone, alumina white, silica, hydrated fine silica (white carbon), ultrafine anhydrous silica (Aerosil), silica sand, talc, precipitated magnesium carbonate, bentonite, clay, kaolin, and yellow ochre.

[0134] Specific examples of organic pigments include various insoluble azo pigments such as Benzidine Yellow, Hansa Yellow, and Laked 4R; soluble azo pigments such as Laked C, Carmine 6B, and Bordeaux 10; various (copper) phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; various chlorinated dye lakes such as rhodamine lake and methyl violet lake; various mordant dyes such as quinoline lake and fast sky blue; various vat dyes such as anthraquinone pigments, thioindigo pigments, and perinone pigments; various quinacridone pigments such as Syncasia Red B; various dioxazine pigments such as dioxazine violet; various condensed azo pigments such as chromophthal; and aniline black.

[0135] Inorganic pigments include various chromates such as lead yellow, zinc chromate, and molybdate orange; various ferrocyanide compounds such as Prussian blue; various metal oxides such as titanium dioxide, zinc oxide, mapo yellow, iron oxide, red iron oxide, chrome green oxide, 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; these metal flake pigments and mica flake pigments; metallic pigments and pearl pigments such as mica flake pigments coated with metal oxides and mica-like iron oxide pigments; graphite, carbon black, and the like.

[0136] Examples of plastic pigments include "Grandeur PP-1000" and "PP-2000S" manufactured by DIC Corporation.

[0137] The pigments used can be selected appropriately depending on the purpose, but for example, inorganic oxides such as titanium dioxide and zinc oxide are preferred as white pigments because they have excellent durability, weather resistance, and design properties, and carbon black is preferred as a black pigment.

[0138] The amount of pigment (C5) is, for example, 1 to 400 parts by mass per 100 parts by mass of the total non-volatile content of the polyol composition (X) and the polyisocyanate composition (Y), and is more preferably 10 to 300 parts by mass to improve adhesion and blocking resistance.

[0139] Examples of acid anhydrides (C6) include cyclic aliphatic acid anhydrides, aromatic acid anhydrides, and unsaturated carboxylic acid anhydrides, and one or more can be used in combination. More specifically, examples include maleic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, dodecenylsuccinic anhydride, polyadipic anhydride, polyazelaic anhydride, polysebacic anhydride, poly(ethyloctadecanediic acid) anhydride, poly(phenylhexadecanedioic acid) anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylhymic anhydride, and trialkyltetrahydrophthalic acid Examples include anhydrides, methylcyclohexenedicarboxylic acid anhydride, methylcyclohexenetetracarboxylic acid anhydride, ethylene glycol bistrimellitate dianhydride, hetic 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-naphthalenesuccinic acid dianhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dianhydride, and the like.

[0140] As the acid anhydride (C6), the above-mentioned compound modified with glycol may be used. Examples of glycols that can be used for modification include alkylene glycols such as ethylene glycol, propylene glycol, and neopentyl glycol; and polyether glycols such as polyethylene glycol, polypropylene glycol, and butyltetramethylene ether glycol. Furthermore, copolymer polyether glycols of two or more of these glycols and / or polyether glycols can also be used.

[0141] Alternatively, as the acid anhydride (C6), a homopolymer or copolymer of a compound having a polymerizable unsaturated group, such as maleic anhydride, from among the compounds mentioned above may be used. Compounds that can copolymerize with a compound having an acid anhydride group and a polymerizable unsaturated group include α-olefins such as ethylene, propylene, 1,3-butadiene, and cyclopentylethylene; vinyl compounds having an aromatic ring such as styrene, 1-ethynyl-4-methylbenzene, divinylbenzene, 1-ethynyl-4-methylethylbenzene, benzonitrile, acrylonitrile, ptert-butylstyrene, 4-vinylbiphenyl, 4-ethynylbenzyl alcohol, 2-ethynylnaphthalene, and phenanthrene-9-ethynyl; and fluoroolefins such as vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, and chlorotrifluoroethylene. These can be used individually 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.

[0142] When the two-component curable composition of the present invention contains an acid anhydride (C6), the amount of the acid anhydride can be adjusted as appropriate, but as an example, it is preferably 5% by mass or less of the total solid content of the two-component curable composition, and preferably 0.1% by mass or more.

[0143] (Form) The two-component curable composition of the present invention may be in either a solvent-type or solvent-free form. In this specification, a "solvent-type" two-component curable composition means that either or both of the polyol composition (X) and the polyisocyanate composition (Y) contain an organic solvent capable of dissolving (diluting) the components of the polyol composition (X) and polyisocyanate composition (Y) used in the present invention.

[0144] Examples of organic solvents include esters such as ethyl acetate, butyl acetate, and cellosolve acetate; ketones such as acetone, methyl ethyl ketone, isobutyl ketone, and cyclohexanone; ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and ethylene chloride; dimethyl sulfoxide; and dimethyl sulfamide. In some cases, the organic solvent used as a reaction medium in the production of the components of the polyol composition (X) and the isocyanate reactive composition (Y) may also be used as a diluent during painting.

[0145] In this specification, a "solvent-free" two-component curable composition refers to an adhesive form in which the polyol composition (X) and polyisocyanate composition (Y) substantially do not contain esters such as ethyl acetate, butyl acetate, and cellosolve acetate, ketones such as acetone, methyl ethyl ketone, isobutyl ketone, and cyclohexanone, ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, and highly soluble organic solvents such as dimethyl sulfoxide and dimethyl sulfamide, particularly ethyl acetate or methyl ethyl ketone, and which is used without a step of heating in an oven or the like to volatilize the solvent after coating the two-component curable composition onto a substrate. If trace amounts of organic solvent remain in the polyol composition (X) or polyisocyanate composition (Y) due to incomplete removal of organic solvents used as reaction media during the manufacture of the components of the polyol composition (X) or polyisocyanate composition (Y) or their raw materials, it is understood that the composition is substantially free of organic solvents. Furthermore, if the polyol composition (X) contains a low molecular weight alcohol, the low molecular weight alcohol reacts with the polyisocyanate composition (Y) to become part of the coating film, so it does not need to be volatilized after coating. Therefore, this form is also treated as a solvent-free type, and the low molecular weight alcohol is not considered an organic solvent.

[0146] The two-component curable composition of the present invention is preferably formulated so that the ratio [NCO] / [isocyanate-reactive functional groups] between the number of moles of isocyanate groups [NCO] contained in the polyisocyanate composition (Y) and the number of moles of functional groups that are reactive with isocyanate [isocyanate-reactive functional groups] contained in the polyol composition (X) is 0.5 to 5.0, more preferably 1.0 to 3.0. This makes it possible to obtain appropriate curability regardless of the ambient humidity during coating.

[0147] The two-component curing composition of the present invention can be used, for example, as an adhesive, coating agent, sealant, elastomer, etc.

[0148] <Two-component curing adhesive> The two-component curing composition of the present invention can be suitably used as a two-component curing adhesive comprising a polyol composition (X) and a polyisocyanate composition (Y). Because the adhesive of the present invention has excellent oxygen barrier properties, when used for laminating olefin resin films together, it can improve the oxygen barrier properties of the laminate without impairing recyclability. The applications of the adhesive of the present invention are not limited to this, and it can also be suitably used for laminating different types of resin films.

[0149] (Polyol composition (X)) The polyol composition (X), which is a component of the adhesive of the present invention, is the same as the polyol composition (X) in the two-component curing type composition described above.

[0150] In this embodiment, it is preferable that the polyester polyol (A1) includes a polyester polyol (A1) with a glass transition temperature (Tg) of 40°C or lower. This makes it possible to create an adhesive with excellent adhesion. The lower limit of the glass transition temperature of the polyester polyol (A1) can be adjusted as appropriate depending on the purpose, but as an example, it is -50°C or higher.

[0151] When the adhesive of the present invention is used as a solvent-free adhesive, the viscosity of the polyol composition (X) is adjusted to a range suitable for the non-solvent laminating method. For example, the viscosity at 40°C is adjusted to be in the range of 100 to 50,000 mPas, more preferably 100 to 20,000 mPas. The viscosity of the polyol composition (X) can be adjusted by the backbone of the polyol compound (A) used in combination with the polyester polyol (A1), or by a plasticizer, etc. When the adhesive of the present invention is used as a solvent-type adhesive, the viscosity of the polyol composition (X) can be adjusted by diluting it with a solvent.

[0152] (Polyisocyanate composition (Y)) The polyisocyanate composition (Y), which is one component of the adhesive of the present invention, is the same as the polyisocyanate composition (Y) in the two-component curing type composition described above.

[0153] When the adhesive of the present invention is used as a solvent-free adhesive, the viscosity of the polyisocyanate composition (Y) is adjusted to a range suitable for the non-solvent laminating method. For example, the viscosity at 70°C is adjusted to be in the range of 100 to 20,000 mPas, more preferably 500 to 10,000 mPas. The viscosity of the polyisocyanate composition (Y) can be adjusted by a polyisocyanate compound (B) used as an example. The viscosity of the polyisocyanate composition (Y) can be measured, for example, using a rotational viscometer with a cone-plate of 1° × 50 mm in diameter and a shear rate of 100 sec. －１ It can be measured at 70°C ± 1°C. When the adhesive of the present invention is used as a solvent-type adhesive, the viscosity of the polyisocyanate composition (Y) can be adjusted by diluting it with a solvent.

[0154] (Form) The two-component curing adhesive of the present invention is preferably used by formulating the two components such that the ratio [NCO] / [isocyanate-reactive functional groups] of the number of moles of isocyanate groups [NCO] contained in the polyisocyanate composition (Y) to the number of moles of functional groups that are reactive with isocyanate [isocyanate-reactive functional groups] contained in the polyol composition (X) is 0.5 to 5.0, more preferably 1.0 to 3.0. This makes it possible to obtain appropriate curing properties without depending on the ambient humidity during coating.

[0155] <Two-component curable coating agent> The two-component curable composition of the present invention can be used as a two-component curable coating agent comprising a polyol composition (X) and a polyisocyanate composition (Y). The coating agent of the present invention has excellent oxygen barrier properties and can improve the oxygen barrier properties of films and laminates with a coating film of several micrometers.

[0156] (Polyol composition (X)) The polyol composition (X), which is one component of the coating agent of the present invention, is the same as the polyol composition (X) in the two-component curable composition described above.

[0157] In this embodiment, it is preferable that the polyester polyol (A1) includes one having a glass transition temperature (Tg) of 15°C or higher. This allows for a coating agent with suppressed blocking. The upper limit of the glass transition temperature of the polyester polyol (A1) can be appropriately adjusted depending on the purpose, but as an example, it is 80°C or lower.

[0158] When the adhesive of the present invention is used as a solvent-free coating agent, the viscosity of the polyol composition (X) is adjusted, for example, to be in the range of 100 to 50,000 mPas, more preferably 100 to 20,000 mPas, at 40°C. The viscosity of the polyol composition (X) can be adjusted by the backbone of the polyol compound (A) used in combination with the polyester polyol (A1), or by a plasticizer, etc. When the coating agent of the present invention is used as a solvent-type coating agent, the viscosity of the polyol composition (X) can be adjusted by diluting it with a solvent.

[0159] (Polyisocyanate composition (Y)) The polyisocyanate composition (Y), which is one component of the coating agent of the present invention, is the same as the polyisocyanate composition (Y) in the two-component curable composition described above.

[0160] When the coating agent of the present invention is used as a solvent-free coating agent, the viscosity of the polyisocyanate composition (Y) is adjusted, for example, to be in the range of 100 to 20,000 mPas, more preferably 500 to 10,000 mPas, at 70°C. The viscosity of the polyisocyanate composition (Y) can be adjusted by the polyisocyanate compound (B) used as an example. The viscosity of the polyisocyanate composition (Y) can be determined, for example, using a rotational viscometer with a cone-plate of 1° × 50 mm in diameter and a shear rate of 100 sec. －１ It can be measured at 70°C ± 1°C. When the coating agent of the present invention is used as a solvent-type coating agent, the viscosity of the polyisocyanate composition (Y) can be adjusted by diluting it with a solvent.

[0161] (Additives) In addition to those exemplified as additives (C) that the two-component curing composition may contain, the coating agent of the present invention may further contain additives such as plate-like inorganic compounds, compounds having active hydrogen groups, gas scavenging components, anti-skinning agents, drying aids, waxes, surfactants, stabilizers, flow regulators, leveling agents, rheology control agents, ultraviolet absorbers, and antioxidants.

[0162] Examples of platy inorganic compounds include hydrated silicates (phyllosilicate minerals, etc.), kaolin, kaolinite-serpentine clay minerals (haloysite, kaolinite, endelite, dickite, nacrite, etc., antigorite, chrysotile, etc.), pyrophyllite-talc group (pyrophyllite, talc, kerolite, etc.), smectite group clay minerals (montmorillonite, beidelite, nontronite, saponite, hectorite, souconite, stevensite, etc.), vermiculite group clay minerals (vermiculite, etc.), mica or mica group clay minerals (muscovite, phlogopite, etc., margalite, tetrasilicic mica, teniolite, etc.), chlorite group (cuquerite, sudoite, clinochlore, chamosite, nimite, etc.), hydrotalcite, platy barium sulfate, boehmite, and polyaluminum phosphate. These minerals may be natural or synthetic clay minerals. The plate-like inorganic compounds are used individually or in combination of two or more. There are no particular restrictions on the aspect ratio, content within the coating agent, particle size, and particle size distribution of these plate-like inorganic compounds, as long as they provide barrier-enhancing functionality and blocking resistance.

[0163] The amount of plate-like inorganic compound blended is preferably 5% by mass or more and 80% by mass or less relative to the non-volatile components of the coating agent. More preferably 10% to 60%, and even more preferably 20% to 50%.

[0164] As the compound having an active hydrogen group, it is preferable to use one with a molecular weight of 100 or more and 250 or less, or a solubility parameter of 29.5 or less.

[0165] Compounds having a hydroxyl group as an active hydrogen group include alkanols such as octanol and decanol, aliphatic diols such as 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2,2-trimethylpentanediol, 3,3-dimethylolheptane, octanediol, and decanediol, alicyclic alcohols such as 1,3- or 1,4-cyclohexanedimethanol and 1,3- or 1,4-cyclohexanediol, aromatic alcohols such as salicylic alcohol and vanillyl alcohol, hydrogenated bisphenol A, and 1,4-dihydroxy-2 Examples include dihydric alcohols such as butene, 2,6-dimethyl-1-octen-3,8-diol, bisphenol A, diethylene glycol, triethylene glycol, and dipropylene glycol; trihydric alcohols such as glycerin, trimethylolpropane, and triisopropanolamine; tetrahydric alcohols such as tetramethylolmethane (pentaerythritol) and diglycerin; pentahydric alcohols such as xylitol; hexahydric alcohols such as sorbitol, mannitol, allitol, isitol, dalcitol, althritol, inositol, and dipentaerythritol; and heptahydric alcohols such as perceitol.

[0166] Compounds having an amino group as an active hydrogen group include aliphatic amines such as octylamine, decaneamine, 1,8-diaminooctane, and 1,10-diaminodecane; alicyclic amines such as isophoronediamine, norbornenediamine, bis(aminomethyl)cyclohexane, cyclohexanediamine, diaminodicyclohexylmethane, and methylenebis(methylcyclohexaneamine); and aromatic amines such as 1-xylylenediamine, N-benzylethylenediamine, phenylenediamine, diaminodiphenylmethane, diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene, toluenediamine, and diethyltoluenediamine.

[0167] Compounds having an SH group as an active hydrogen group include hexyl mercaptan, heptyl mercaptan, octyl mercaptan, nonyl mercaptan, decyl mercaptan, undecyl mercaptan, dodecyl mercaptan, tridecyl mercaptan, tetradecyl mercaptan, pentadecyl mercaptan, mercaptophenol, mercaptopropionic acid, mercaptobutyric acid, 1,4-butanedithiol, 2-mercaptobenzothiazole, and 3-mercapto Examples include to-1,2-propanediol, mercaptomethylbutanol, 3-mercapto-2-methylpentanol, 3-mercapto-3-methylbutanol, 4-ethoxy-2-methyl-2-butanethiol, hexanethiol, dimethylthiophenol, 1,4-bis(3-mercaptobutyryloxy)butane, trimethylolpropanetris(3-mercaptobutyrate), pentaerythritoltetrakis(3-mercaptobutyrate), etc.

[0168] These may be used individually or in combination. It is preferable to use compounds having a hydroxyl group as the active hydrogen group, and isosorbide, tris(2-hydroxyethyl) isocyanurate, trimethylolpropane, dipentaerythritol, and 1,4-cyclohexanedimethanol are preferred.

[0169] The amount of the compound having an active hydrogen group is preferably 0.5% by mass or more and 20% by mass or less relative to the non-volatile components of the coating agent. Within this range, it is expected that winding blocking during coating will be prevented, good adhesion to the substrate and improved gas barrier properties of the coating film will be achieved. The amount is preferably 1% by mass or more and 15% by mass or less, and preferably 2% by mass or more and 8% by mass or less.

[0170] Examples of gas-capturing components include components with oxygen-capturing capabilities and components with water vapor-capturing capabilities. Specific examples of oxygen-capturing components include low-molecular-weight organic compounds that react with oxygen, such as hindered phenols, vitamin C, vitamin E, organophosphorus compounds, gallic acid, and pyrogallol, as well as transition metal compounds such as cobalt, manganese, nickel, iron, and copper. Specific examples of water vapor-capturing components include silica gel, zeolite, activated carbon, and calcium carbonate. Other target gas-capturing components can also be used as gas-capturing components.

[0171] As the anti-skinning agent, an organic solvent with a higher boiling point than the organic solvent used in the coating agent of the present invention and high solubility of polyester polyol (A1) is used. By including the anti-skinning agent, the surface of the coating film of the coating agent dries before the organic solvent evaporates from within the coating film, preventing the evaporation of the organic solvent from being hindered. Specific examples of anti-skinning agents include propylene glycol monomethyl ether, ethyl cellosolve, propyl acetate, and butyl acetate.

[0172] The drying aid has the function of promoting the volatilization of the organic solvent used in the coating agent of the present invention. Examples of drying aids include isosorbide, isomannide, isoidide, and triacetin. It is preferable to use isosorbide. Generally, organic solvents tend not to volatilize easily from compositions containing polyester polyol and organic solvents, but in particular, while coating agents using the above-mentioned polyester polyol (A1) can form a coating film with excellent gas barrier properties, this excellent gas barrier property tends to hinder the volatilization of the organic solvent. By including a drying aid, the organic solvent volatilizes more easily during the drying process, the coating agent has excellent drying properties, and organic solvents are less likely to remain in the cured coating film.

[0173] Furthermore, it is preferable that the drying aid has hydroxyl groups. This allows it to react with the polyisocyanate compound (B) and be incorporated into the cured coating film. Unlike additives without functional groups, there is no risk of it migrating from the coating layer to other layers over time, and it has little effect on the physical properties of the coating layer over time. The drying process referred to here is the process of mixing the polyol composition (X) and the polyisocyanate composition (Y), applying it to the substrate, and then passing it through an oven to volatilize the organic solvent contained in the coating film of the coating agent.

[0174] Furthermore, it is preferable that the hydroxyl groups in the drying aid are secondary hydroxyl groups. Because they have lower reactivity with the polyisocyanate compound (B) compared to primary hydroxyl groups, they effectively prevent the reaction with the polyisocyanate compound (B) before the drying process.

[0175] (Form) The two-component curable coating agent of the present invention is preferably used by blending the polyisocyanate composition (Y) and polyol composition (X) such that the ratio of the number of moles of isocyanate groups [NCO] to the number of moles of isocyanate-reactive functional groups [isocyanate-reactive functional groups] is 0.5 to 5.0, more preferably 1.0 to 3.0. This makes it possible to obtain appropriate curability without depending on the ambient humidity during coating.

[0176] <Laminate> The laminate of the present invention can be obtained, for example, by applying and curing the two-component curable coating agent of the present invention to a substrate. Alternatively, the laminate of the present invention can be obtained by a method having a two-component mixing step, in which the two-component curable adhesive of the present invention is applied to a first substrate, then a second substrate is laminated onto the applied surface, and the adhesive layer is cured; or by a method having a two-component fractional coating step, in which the polyol composition (X) of the two-component curable adhesive of the present invention is applied to a first substrate, and the polyisocyanate composition (Y) is applied to a second substrate, and then the first substrate and the second substrate are laminated by bringing the applied surface of the polyol composition (X) into contact with the applied surface of the polyisocyanate composition (Y) and pressing them together, and the adhesive layer is cured. There are no particular restrictions on the substrate used, and it can be appropriately selected according to the application.

[0177] For example, for food packaging, examples include polyethylene terephthalate (PET) film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film (LLDPE: low-density polyethylene film, HDPE: high-density polyethylene film, MDOPE: uniaxially oriented polyethylene film, BOPE: biaxially oriented polyethylene film), polypropylene film (CPP: unoriented polypropylene film, OPP: biaxially oriented polypropylene film), ethylene vinyl alcohol copolymer, and gas barrier heat-seal films such as polyolefin films, polyvinyl alcohol films, and ethylene-vinyl alcohol copolymer films, which have an olefin-based heat-sealable resin layer on one or both sides of a gas barrier resin such as polyvinyl alcohol.

[0178] Furthermore, it is also preferable to use biomass films, biodegradable films, or recycled plastic films made from materials containing biomass-derived components, biodegradable components, or recycled components. Biomass films, biodegradable films, and recycled plastic films are sold by various companies, and in addition, films certified in each country can be used, such as film sheets listed in the biomass certified product list of the Japan Organic Resources Association, films listed in the Eco Mark certified product list of the Japan Environment Association, and films bearing the symbol mark set by the Japan Bioplastics Association.

[0179] (Biomass Film) A well-known example of a biomass film is one made from biomass-derived ethylene glycol. Biomass-derived ethylene glycol is made from ethanol produced from biomass (biomass ethanol). For example, biomass-derived ethylene glycol can be obtained by conventionally known methods, such as a method of producing ethylene glycol via ethylene oxide from biomass ethanol. Alternatively, commercially available biomass ethylene glycol may be used, and for example, biomass ethylene glycol commercially available from India Glycol can be suitably used.

[0180] For example, as an alternative to conventional polyethylene terephthalate films using petroleum-based raw materials, films containing biomass polyesters, biomass polyethylene terephthalate, etc., which use biomass-derived ethylene glycol as the diol unit and fossil fuel-derived dicarboxylic acid as the dicarboxylic acid unit are known.

[0181] The dicarboxylic acid units of the biomass polyester use dicarboxylic acids derived from fossil fuels. Aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and their derivatives can be used without restriction as the dicarboxylic acids. Furthermore, in addition to the above-mentioned diol and dicarboxylic acid components, copolymer polyesters may also be formed by adding a copolymer component as a third component, such as a bifunctional oxycarboxylic acid or at least one polyfunctional compound selected from the group consisting of trifunctional or more polyhydric alcohols, trifunctional or more polyhydric acids and / or their anhydrides, and trifunctional or more oxycarboxylic acids, in order to form a crosslinking structure.

[0182] Furthermore, as an alternative to conventional polyolefin films using petroleum-based raw materials, biomass polyolefin films such as biomass polyethylene films and biomass polyethylene-polypropylene films containing polyethylene resins made from biomass-derived ethylene glycol are also known. The polyethylene resin is not particularly limited except for the use of biomass-derived ethylene glycol as part of the raw materials, and examples include ethylene homopolymers and copolymers of ethylene and α-olefins with ethylene as the main component (ethylene-α-olefin copolymers containing 90% by mass or more of ethylene units), and these can be used individually or in combination of two or more.

[0183] The α-olefin constituting the copolymer of ethylene and α-olefin is not particularly limited, and examples include α-olefins having 4 to 8 carbon atoms, such as 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene. Known polyethylene resins such as low-density polyethylene resin, medium-density polyethylene resin, and linear low-density polyethylene resin can be used. Among these, linear low-density polyethylene resin (LLDPE) (a copolymer of ethylene and 1-hexene, or a copolymer of ethylene and 1-octene) is preferred from the viewpoint of further reducing damage such as punctures and tears even when the films rub against each other, and has a density of 0.910 to 0.925 g / cm³. ３ A linear low-density polyethylene resin is more preferable.

[0184] As for biomass films, those made from biomass raw materials that are distinguished by their biomass plasticity as defined by ISO 16620 or ASTM D6866 are also on the market. Radioactive carbon-14C exists in the atmosphere at a rate of 1 in 10¹² atoms, and this rate does not change even in atmospheric carbon dioxide, so this rate does not change even in plants that fix this carbon dioxide through photosynthesis. For this reason, the carbon in plant-derived resins contains radioactive carbon-14C. In contrast, the carbon in fossil fuel-derived resins contains almost no radioactive carbon-14C. Therefore, by measuring the concentration of radioactive carbon-14C in the resin using an accelerator mass spectrometer, the proportion of plant-derived resin in the resin, i.e., the biomass plasticity, can be determined.

[0185] Examples of plant-derived low-density polyethylene (PDI) biomass plastics with a biomass plastic content of 80% or more, preferably 90% or more, as defined by ISO 16620 or ASTM D6866, include Braskem's product names "SBC818," "SPB608," "SBF0323HC," "STN7006," "SEB853," and "SPB681," and films made from these materials can be suitably used.

[0186] Films and sheets containing biomass raw materials such as starch and polylactic acid are also known. These can be selected and used as appropriate depending on the application.

[0187] The biomass film may be a laminate formed by stacking multiple biomass films, or it may be a laminate formed by combining a conventional petroleum-based film with a biomass film. Furthermore, these biomass films may be unstretched or stretched films, and their manufacturing method is not limited.

[0188] (Biodegradable Films) Specifically, well-known biodegradable films include those made from biodegradable resins that are generally available. Examples include polycaprolactone, polyvinyl alcohol, polyamide, cellulose ester, lactic acid-based polyester resin, aliphatic polyester resin, or aliphatic aromatic polyester resin. These biodegradable resins may be used individually or in combination of two or more. Among these, aliphatic polyester resins or aliphatic aromatic polyester resins are preferably used. Examples of aliphatic polyester resins include aliphatic polyesters obtained by the polycondensation reaction of aliphatic diols and aliphatic dicarboxylic acids. Examples of aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol. These may be used individually or in mixtures thereof. Among these, 1,4-butanediol is preferred. Examples of aliphatic dicarboxylic acids include oxalic acid, succinic acid, glutanoic acid, adipic acid, sebacic acid, suberic acid, and dodecanedioic acid, and their derivatives, such as acid anhydrides, may also be used. In particular, succinic acid or succinic anhydride, or a mixture of these with adipic acid, is preferred. Specifically, examples include polybutylene succinate (PBS) obtained from 1,4-butanediol and succinic acid (for example, BioPBS from PPT MCC Biochem), and polybutylene succinate adipate (PBSA) obtained by copolymerizing PBS with adipic acid.

[0189] Aliphatic aromatic polyester resins include copolymers containing aliphatic dicarboxylic acid units, aromatic dicarboxylic acid units, and linear aliphatic and / or alicyclic diol units. The diol component that provides the diol units usually has 2 to 10 carbon atoms, and examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,4-cyclohexanedimethanol. Among these, diols with 2 to 4 carbon atoms are preferred, with ethylene glycol and 1,4-butanediol being preferred, and 1,4-butanediol being even more preferred. The dicarboxylic acid component that provides the dicarboxylic acid units usually has 2 to 10 carbon atoms, and examples include succinic acid, adipic acid, suberic acid, sebacic acid, and dodecanedioic acid. Among these, succinic acid or adipic acid are preferred. Examples of aromatic dicarboxylic acid components that provide aromatic dicarboxylic acid units include terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid. Among these, terephthalic acid and isophthalic acid are preferred, with terephthalic acid being even more preferred. Specifically, examples include PBAT (for example, Ecoflex manufactured by B.A.S.F.), which is a copolymer of 1,4-butanediol, adipic acid, and terephthalic acid.

[0190] Other examples include aliphatic polyester copolymers obtained from hydroxyalkanoic acid and polycarboxylic acid, such as poly(3-hydroxyalkanoate) (especially poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) (e.g., Aonirex manufactured by Kaneka Corporation) and polylactic acid (PLA) (e.g., REVODE manufactured by Kaisei Biomaterials Co., Ltd., Ingeo manufactured by NatureWorks Inc.).

[0191] The biodegradable film may be a laminate formed by stacking multiple biodegradable films, or a laminate formed by combining a conventional petroleum-based film with a biodegradable film. Furthermore, these biodegradable films may be unstretched or stretched films, and their manufacturing method is not limited.

[0192] The film may be stretched. A common stretching method involves melting and extruding the resin into a sheet using methods such as extrusion film formation, followed by simultaneous biaxial stretching or sequential biaxial stretching. In the case of sequential biaxial stretching, it is common to first perform longitudinal stretching, followed by transverse stretching. Specifically, a method combining longitudinal stretching using the speed difference between rolls and transverse stretching using a tenter is frequently used.

[0193] Various surface treatments, such as flame treatment or corona discharge treatment, may be applied to the film surface as needed to ensure that an adhesive layer free from defects such as film breakage or repulsion is formed.

[0194] Alternatively, a barrier film containing a gas barrier layer such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, or vinylidene chloride may be used in combination. This film can be used to create a laminate that provides barrier properties against water vapor, oxygen, alcohol, inert gases, volatile organic compounds (fragrances), etc.

[0195] As for the paper, any known paper substrate can be used without particular limitation. Specifically, it is manufactured using natural fibers for papermaking such as wood pulp and manufactured on a known paper 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 pulps that have been chemically modified. As for the type of pulp, chemical pulps produced by sulfate pulping, acidic, neutral, and alkaline sulfite pulping, soda salt pulping, etc., as well as gland pulp, chemigland pulp, thermomechanical pulp, etc. can be used. In addition, various commercially available fine papers, coated papers, backing papers, impregnated papers, cardboard, and paperboard can also be used.

[0196] More specific configurations of laminates manufactured using the coating agent of the present invention include, but are not limited to, (1) coating layer / substrate, (2) coating layer / metal vapor-deposited unstretched film, (3) coating layer / metal vapor-deposited stretched film, (4) coating layer / transparent vapor-deposited stretched film, (5) substrate / coating layer / metal vapor-deposited layer, (6) substrate / coating layer / transparent vapor-deposited layer, etc.

[0197] Examples of substrates used in composition (1) include MDOPE film, BOPE film, OPP film, PET film, nylon film, paper, K-OPP film, K-PET film, K-nylon film, etc. The printing layer may be provided on either side of the substrate (the side of the substrate facing the coating layer or the side of the substrate opposite the coating layer) or on the coating layer (the side of the coating layer opposite the substrate). The printing layer is formed using various printing inks such as gravure ink, flexographic ink, offset ink, stencil ink, and inkjet ink, using general printing methods that have been conventionally used for printing on polymer films and paper.

[0198] Examples of metal-deposited unstretched films used in configuration (2) include CPP film, LLDPE film, VM-CPP film, VM-LLDPE film, etc., which are gas barrier heat-seal films with metal deposition such as aluminum. Examples of metal-deposited stretched films used in configuration (3) include VM-MDOPE film, VM-BOPE film, VM-OPP film, VM-PET film, etc., which are MDOPE film, BOPE film, OPP film, or PET film with metal deposition such as aluminum. Examples of transparent metal-deposited stretched films used in configuration (4) include films with silica or alumina deposition on MDOPE film, BOPE film, OPP film, PET film, nylon film, etc. A printed layer may be provided at any position, similar to configuration (1).

[0199] Examples of substrates used in components (5) and (6) include MDOPE film, BOPE film, OPP film, PET film, CPP film, LLDPE film, gas barrier heat seal film, and paper. The metal vapor deposition layer is a vapor-deposited layer of a metal such as aluminum.

[0200] By providing a coating layer made of the coating agent of the present invention on a metal vapor deposition layer or a transparent vapor deposition layer as in configurations (2) to (4), a laminate with even better gas barrier properties can be obtained.

[0201] The method of applying the coating agent is not particularly limited, and conventionally known methods can be used. Examples of various coating methods include spray coating, direct gravure coating, gravure kiss reverse coating, offset guavia coating, flexo coating, offset coating, bar coating, roll kiss coating, forward rotation roll coating, reverse roll coating, slot die coating, vacuum die coating, (micro) chamber doctor coating, air doctor coating, blade coating, knife coating, spin coating, and dipping coating.

[0202] The amount of coating agent applied can be adjusted as appropriate depending on the application, but one example is 0.1 g / m². ２ More than 100g / m ２ The following describes how the laminate of the present invention can be obtained: For example, by applying a coating agent to a substrate, drying the solvent contained in the coating agent as needed, and aging it at room temperature to 70°C for 6 to 240 hours.

[0203] More specific laminate configurations manufactured using the adhesive of the present invention include: (1) Substrate 1 / Adhesive layer 1 / Sealant film (2) Substrate 1 / Adhesive layer 1 / Metal vapor-deposited unstretched film (3) Substrate 1 / Adhesive layer 1 / Metal vapor-deposited stretched film (4) Transparent vapor-deposited stretched film / Adhesive layer 1 / Sealant film (5) Substrate 1 / Adhesive layer 1 / Substrate 2 / Adhesive layer 2 / Sealant film (6) Transparent vapor-deposited stretched film / Adhesive layer 1 / Substrate 1 / Adhesive layer 2 / Sealant film (7) Substrate 1 / Adhesive layer 1 / Metal vapor-deposited stretched film / Adhesive layer 2 / Sealant film (8) Substrate 1 / Adhesive layer 1 / Transparent vapor-deposited stretched film / Adhesive layer 2 / Sealant film (9) Substrate 1 / Adhesive layer 1 / Metal layer / Adhesive layer 2 / Sealant film (10) Substrate 1 / Adhesive layer 1 / Substrate 2 / Adhesive layer 2 / Metal layer / Adhesive layer 3 / Sealant film (11) Examples include, but are not limited to, the base material 1 / adhesive layer 1 / metal layer / adhesive layer 2 / base material 2 / adhesive layer 3 / sealant film, etc.

[0204] Examples of substrates 1 used in configuration (1) include MDOPE film, BOPE film, OPP film, PET film, nylon film, and paper. Alternatively, a substrate 1 coated with a coating for purposes such as improving gas barrier properties or ink receptivity when providing the printing layer described later may be used. Commercially available coated substrate films 1 include K-OPP film, K-PET film, and K-nylon film. The adhesive layer 1 is a cured coating of the adhesive of the present invention. Examples of sealant films include CPP film, LLDPE film, easy-open heat-seal film, and gas-barrier heat-seal film. The printing layer may be provided on the side of the substrate 1 facing the adhesive layer 1 (or, if a coated substrate film 1 is used, on the side of the coating layer facing the adhesive layer 1) or on the side opposite to 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 general printing methods conventionally used for printing on polymer films and paper.

[0205] Examples of substrates 1 used in configurations (2) and (3) include MDOPE film, BOPE film, OPP film, PET film, paper, etc. The adhesive layer 1 is a cured coating of the adhesive of the present invention. Examples of unstretched metal-deposited films include CPP film, LLDPE film, VM-CPP film, VM-LLDPE film, etc., which are gas barrier heat seal films with metal deposition such as aluminum. Examples of stretched metal-deposited films include VM-MDOPE film, VM-BOPE film, VM-OPP film, etc., which are MDOPE film, BOPE film, OPP film with metal deposition such as aluminum. A printed layer may be provided on any surface of the substrate 1 in the same manner as in configuration (1).

[0206] Examples of transparent vapor-deposited stretched films used in configuration (4) include films obtained by vapor-depositing silica or alumina onto MDOPE film, BOPE film, OPP film, PET film, nylon film, etc. Films with a coating applied to the vapor-deposited layer may also be used for purposes such as protecting the inorganic vapor-deposited layer of silica or alumina. An anchor coat layer may be provided between the vapor-deposited layer and the substrate on which the vapor-deposited layer is provided for the purpose of improving the adhesion of the vapor-deposited layer or improving barrier properties. The adhesive layer 1 is a cured coating film of the adhesive of the present invention. Examples of sealant films are the same as those in configuration (1). A printed layer may be provided on the side of the transparent vapor-deposited stretched film that faces the adhesive layer 1 (or, if a film with a coating applied to the inorganic vapor-deposited layer is used, on the side of the coating layer that faces the adhesive layer 1). The method for forming the printed layer is the same as in configuration (1).

[0207] Examples of substrate 1 used in configuration (5) include PET film and paper. Examples of substrate 2 include nylon film. At least one of adhesive layer 1 and adhesive layer 2 is a cured coating film of the adhesive of the present invention. Examples of sealant film are the same as those in configuration (1). A printed layer may be provided on any surface of substrate 1 in the same manner as in configuration (1).

[0208] Examples of transparent vapor-deposited stretched film used in configuration (6) include those similar to those in configuration (4). Examples of substrate 1 used in configuration (6) include PET film and nylon film. At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. Examples of sealant film include those similar to those in configuration (1). A printing layer may be provided on the side of the transparent vapor-deposited stretched film facing the adhesive layer 1 (or, if a film with a coating applied to an inorganic vapor-deposited layer is used, on the side of the coating layer facing the adhesive layer 1). The method for forming the printing layer is the same as in configuration (1).

[0209] The base material 1 of configuration (7) is the same as that of configurations (2) and (3). Examples of metal vapor-deposited stretched films include VM-MDOPE film, VM-BOPE film, VM-OPP film, and VM-PET film, which are obtained by vapor deposition of aluminum or the like on MDOPE film, BOPE film, OPP film, or PET film. At least one of adhesive layer 1 and adhesive layer 2 is a cured coating film of the adhesive of the present invention. Examples of sealant films are the same as those of configuration (1). A printing layer may be provided on any surface of the base material 1 in the same manner as in configuration (1).

[0210] Examples of the substrate 1 in configuration (8) include PET film and paper. Examples of the transparent vapor-deposited stretched film include those the same as in configuration (4). At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those the same as in configuration (1). A printed layer may be provided on any surface of the substrate 1 in the same manner as in configuration (1).

[0211] Examples of the base material 1 in configuration (9) 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 are the same as those in configuration (1). A printed layer may be provided on any surface of the base material 1 in the same manner as in configuration (1).

[0212] As the base materials 1 of the structures (10) and (11), a PET film, paper, etc. may be mentioned. As the base material 2, a nylon film, etc. may be mentioned. As the metal layer, an aluminum foil, etc. may be mentioned. At least one of the adhesive layers 1, 2, and 3 is a cured coating film of the adhesive of the present invention. The sealant film is the same as that of the structure (1). Similar to the structure (1), a printing layer may be provided on any surface of the base material 1.

[0213] When the adhesive of the present invention is used in the production of a laminate including a metal vapor deposition layer or a transparent vapor deposition layer as in the structures (2) to (4), (6) to (8), a laminate having more excellent gas barrier properties can be obtained. At this time, it is preferable to form the adhesive layer in contact with the metal vapor deposition layer or the transparent vapor deposition layer using the adhesive of the present invention.

[0214] When the adhesive of the present invention is a solvent type, the adhesive of the present invention is applied to the film material serving as the base material using a roll such as a gravure roll, and after volatilizing the organic solvent by heating in an oven or the like, the other base material is laminated to obtain the laminate of the present invention. It is preferable to perform an aging treatment after lamination. The aging temperature is preferably room temperature to 80°C, and the aging time is preferably 12 to 240 hours.

[0215] When the adhesive of the present invention is a solvent-free type, the adhesive of the present invention heated to about 40°C to 100°C in advance is applied to the film material serving as the base material using a roll such as a gravure roll, and then the other base material is immediately laminated to obtain the laminate of the present invention. It is preferable to perform an aging treatment after lamination. The aging temperature is preferably room temperature to 70°C, and the aging time is preferably 6 to 240 hours.

[0216] The coating amount of the adhesive is adjusted as appropriate. In the case of a solvent type adhesive, as an example, the solid content is 1 g / m ２ or more and 10 g / m ２ or less, preferably 2 g / m ２ or more and 5 g / m ２ or less. In the case of a solvent-free type adhesive, the coating amount of the adhesive is, as an example, 1 g / m ２ or more and 5 g / m ２ or less, preferably 1 g / m ２ or more and 3 g / m ２ or less.

[0217] In addition to the above-described configurations (1) to (11), the laminate of the present invention may further include other films or substrates. As other substrates, in addition to the stretched film, unstretched film, and transparent vapor-deposited film described above, porous substrates such as paper, wood, and leather, as described later, may also be used. The adhesive used when bonding the other substrates may be the adhesive of the present invention or not.

[0218] The "other layer" may contain known additives and stabilizers, such as antistatic agents, easy-adhesion coating agents, plasticizers, lubricants, and antioxidants. The "other layer" may also have its surface pretreated by corona treatment, plasma treatment, ozone treatment, chemical treatment, solvent treatment, etc., to improve adhesion when laminated with other materials.

[0219] The laminate of the present invention can be suitably used in a variety of applications, such as packaging materials for food, pharmaceuticals, and household goods; lids; paper tableware such as paper straws, paper napkins, paper spoons, paper plates, and paper cups; protective wall materials; roofing materials; solar 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 injection molding simultaneous decoration methods; and packaging materials for laundry detergents, kitchen detergents, bath detergents, bath soaps, liquid shampoos, liquid conditioners, and the like.

[0220] <Packaging Material> The laminate of the present invention can be used as a multilayer packaging material for the purpose of protecting food, pharmaceuticals, and the like. When used as a multilayer packaging material, the layer configuration may change depending on the contents, usage environment, and usage form. Furthermore, the packaging material of the present invention may be provided with an easy-open treatment or resealing means as appropriate.

[0221] As an example of a specific embodiment of the packaging material of the present invention, a packaging material made by forming a bag from the laminate described above can be cited. The laminate is folded or overlapped so that the inner layers (sealant film surfaces) face each other, and the peripheral edges are heat-sealed to form a bag. Methods for forming the bag include heat sealing methods such as side seal type, two-side seal type, three-side seal type, four-side seal type, envelope seal type, gusset seal type, pleated seal type, flat-bottom seal type, square-bottom seal type, gusset type, and other heat-seal types. The packaging material of the present invention can take various forms depending on the contents, usage environment, and usage method. Self-standing packaging materials (standing pouches) are also possible. Known heat sealing methods include bar seal, rotary roll seal, belt seal, impulse seal, high-frequency seal, and ultrasonic seal.

[0222] Products using the packaging material of the present invention are manufactured by filling the packaging material with contents through its opening and then heat-sealing the opening. Examples of contents that can be filled include, for example, food products such as rice crackers, bean snacks, nuts, biscuits / cookies, wafers, marshmallows, pies, semi-baked cakes, candies, and snack foods; staple foods such as bread, instant noodles, dried noodles, pasta, aseptically packaged rice, rice porridge, packaged mochi, and cereal foods; processed agricultural products such as pickles, boiled beans, natto, miso, frozen tofu, tofu, enoki mushrooms, konjac, processed wild vegetables, jams, peanut cream, salads, frozen vegetables, and processed potato products; processed livestock products such as ham, bacon, sausages, processed chicken products, and corned beef; and fish ham. Examples of processed seafood products include sausages, processed seafood products, fish cakes, seaweed, preserved foods, dried bonito flakes, salted seafood, smoked salmon, and spicy cod roe; fruits such as peaches, oranges, pineapples, apples, pears, and cherries; vegetables such as corn, asparagus, mushrooms, onions, carrots, radishes, and potatoes; frozen and chilled prepared foods such as hamburgers, meatballs, fried seafood, dumplings, and croquettes; dairy products such as butter, margarine, cheese, cream, instant creamy powder, and infant formula; liquid seasonings; retort curry; and pet food.

[0223] Furthermore, as a non-food product, it can be used as a packaging material for various items such as cigarettes, disposable hand warmers, pharmaceuticals such as intravenous fluid packs, liquid laundry detergent, liquid dish soap, liquid bath detergent, liquid bath soap, liquid shampoo, liquid conditioner, cosmetics such as lotions and emulsions, vacuum insulation materials, and batteries.

[0224] <Recycled Plastics> The laminates and packaging materials of the present invention can be used as raw materials for recycled plastics. The recycled plastics of the present invention are recycled using the laminates and packaging materials of the present invention as raw materials. The method for recycling the laminates and packaging materials is not particularly limited, and known methods can be used. Examples include crushing the laminates and packaging materials, melting and kneading them, then pelletizing and molding them, or directly feeding the crushed laminates and packaging materials into an extrusion molding machine and melting and kneading them in the heating cylinder of the molding machine to use them as molding raw materials without melting and kneading or pelletizing.

[0225] Laminates and packaging materials can be crushed using known crushers. The crusher is not particularly limited and examples include using a jaw crusher, impact crusher, cutter mill, stamp mill, ring mill, roller mill, jet mill, or hammer mill. The size of the fragments of the printed material or laminate is preferably 1 mm to 40 mm in side length, and more preferably 8 mm to 20 mm.

[0226] It is preferable that the crushed laminates and packaging materials are washed before being subjected to heating and melting. Washing methods include batch or continuous washing, and water, detergent, neutralizing agent, or alkaline aqueous solution may be used. Furthermore, it is preferable that the washed laminates and packaging materials are dehydrated and dried. Centrifugal dehydration is preferred as the dehydration method, and hot air drying is preferred as the drying method.

[0227] Dehydration and drying allow for adjustment of the moisture content of the laminate subjected to heating and melting. This helps to avoid foaming during the production of recycled plastics. If air bubbles occur during pellet production, the pressure in the cylinder changes, causing the extrusion amount and pressure to be inconsistent, which may result in irregular pellet shapes and dimensions. Furthermore, when manufacturing molded products using the produced pellets through secondary molding, surface irregularities are likely to occur, potentially degrading the surface condition of the molded product.

[0228] In one embodiment, dehydration and drying are carried out until the moisture content of the laminate used for the production of recycled plastic is 3% by mass or less, preferably 2% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less, based on the total mass of the laminate.

[0229] The crushed laminates and packaging materials are heated and melted at 120-280°C and then kneaded. The temperature at which the laminates and packaging materials are melted can be adjusted considering the glass transition temperature and melting temperature of the laminates or packaging materials, the shape when pelletized, and the pressure applied during the molding process. The screw rotation speed during kneading is, for example, 50-1000 RPM.

[0230] The laminate and packaging material thus melt-kneaded are cooled and shredded to form pellets. Examples of pelletizing methods include hot-cutting and strand-cutting methods, but are not particularly limited. To prevent foreign matter from being mixed into the pellets, it is preferable to provide a screen mesh at the discharge section of the melt-kneaded laminate and packaging material. Examples of screen meshes include woven types such as plain weave, twill weave, plain tatami weave and twill tatami, and perforated metal types. The size of the screen mesh is preferably 40 mesh or more, more preferably 80 mesh or more, and even more preferably 120 mesh or more, taking into consideration the pressure at the discharge section and clogging. Examples of cooling methods include air cooling, wind cooling, and water cooling. In the present invention, it is preferable to include a water cooling step. It is preferable to cool to 20°C to 80°C, and more preferably to 30°C to 60°C.

[0231] The laminate of the present invention can be used as is in the production of recycled plastics if the multiple base materials constituting the laminate are made of the same type of resin. Alternatively, it may be used in the production of recycled plastics after being immersed in a release agent (for example, an alkaline solution such as an aqueous sodium hydroxide solution) for a certain period of time to separate each layer of the laminate.

[0232] If the multiple substrates constituting the laminate of the present invention are made of different resin types, it is preferable to immerse them in a release agent for a certain period of time to separate each layer of the laminate, and then separate them by resin type for use in the production of recycled plastics. Conventional known release agents can be used.

[0233] The material may be used in the manufacture of recycled plastic after the printed layer has been removed. The printed layer can be removed by known methods. The printed layer itself may be formed using a printing ink that is easily peeled off from the substrate by immersion in a release agent, or a delamination layer may be formed by applying a coating agent containing a resin that is easily peeled off from the substrate by immersion in a release agent between the printed layer and the substrate, and the printed layer may be provided on the delamination layer.

[0234] The recycled plastic of the present invention may contain known additives. Examples of such additives include at least one antioxidant selected from the group consisting of phenolic and phosphorus-based agents; at least one lubricant selected from the group consisting of fatty acid amides, alkylene fatty acid amides, metal soaps, and esters; hindered amine-based weather stabilizers; waxes with an acid value of 5 mg KOH / g or less; and at least one antistatic agent selected from the group consisting of fatty acid sulfons and fatty acid esters.

[0235] The recycled plastic of the present invention may contain virgin plastic as a raw material in addition to the laminate and packaging material of the present invention. The virgin plastic added shall be of the same resin type as the base material used in the laminate of the present invention. The virgin plastic may be added when pelletizing the laminate and packaging material of the present invention, or when molding the pelletized recycled plastic of the present invention. It may also be added both when pelletizing and when molding the recycled plastic. As an example, the amount of virgin plastic used in combination when pelletizing the laminate and packaging material of the present invention is in the range of laminate / packaging material:virgin plastic of 100:0 to 25:75 (mass ratio). As an example, the amount of virgin plastic used when molding the pelletized recycled plastic of the present invention is in the range of recycled plastic:virgin plastic of 100:0 to 25:75 (mass ratio).

[0236] The recycled plastic of the present invention can be used as a raw material for various plastic products. Examples of plastic products include, but are not limited to, automobile parts such as bumpers and interior materials, components for home appliances, containers such as pallets and containers for transport, bottles, hangers, stationery, pots and cups, disposable cutlery, and toys. It can also be recycled as a film, or the recycled film can be molded and used as cushioning material when transporting fruits, etc., but is not limited to these uses. As a method for turning the recycled plastic of the present invention into a film to produce a recycled film, known methods such as T-die molding, inflation molding, solution casting molding, and calendering can be used. As a method for molding the recycled film, known methods such as vacuum forming and hot press molding can be used.

[0237] The present invention will be described in more detail below with reference to specific synthesis examples and embodiments, but the present invention is not limited to these embodiments. In the following examples, "parts" and "%" represent "parts by mass" and "mass%", respectively, unless otherwise specified.

[0238] <Preparation of Polyol Composition (X)> (Synthesis Example 1) 787.4 parts of diethylene glycol, 780.8 parts of isophthalic acid, and 0.04 parts of titanium tetraisopropoxide (TIPT) were added to a polyester reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, rectification tube, etc., and an esterification reaction was carried out at an internal temperature of 240°C. After the dehydration reaction, a polyester polyol (A1-1-1) with an acid value of 1.5 mg KOH / g and a hydroxyl value of 200.5 mg KOH / g was obtained.

[0239] (Synthesis Examples 2-8) The esterification reaction was carried out in the same manner as in (Synthesis Example 1), except that the raw materials and temperature conditions shown in Table 1 were used. The acid value and hydroxyl value of the obtained polyester polyols are shown in Table 1. In addition, HA-233B manufactured by DIC Corporation was used as the polyether polyol (A3).

[0240]

[0241] <Preparation of Polyisocyanate Composition (Y)> (Synthesis Example 9) 774.5 parts of toluene diisocyanate (TDI) were added to a reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, and condenser, and heated to 40°C while stirring under a nitrogen gas stream. Then, 225.5 parts of bifunctional polyethylene glycol with a molecular weight of 200 were added carefully, taking care to avoid exothermic reactions, and the mixture was heated to 60°C. The reaction was continued at 60°C until the NCO% no longer changed, and 1.0 part of polyphosphate was added to terminate the reaction. Next, using a thin-film distillation apparatus, the TDI in the urethane prepolymer, which is the reaction product of TDI, was purified to 0.05% by mass of the solid content at a pressure of approximately 0.02 Torr and a temperature of 160°C to obtain polyisocyanate compound (B1). The NCO% of polyisocyanate compound (B1) was 14.5%.

[0242] (Synthesis Example 10) In a flask equipped with a stirrer, thermometer, and nitrogen gas inlet tube, 22.6 parts of 2,2'-diphenylmethane diisocyanate, a mixture of 2,4'-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate, and 34.9 parts of xylylene diisocyanate were charged and heated to 50°C while stirring under a nitrogen gas stream. 42.5 parts of the polyester polyol obtained in Synthesis Example 8, with an acid value of 1.0 mg KOH / g and a hydroxyl value of 223.5 mg KOH / g, were added dropwise in several portions, and the mixture was further heated and maintained at an internal temperature of 70°C for 4 hours to carry out the urethane reaction, yielding a urethane prepolymer (polyisocyanate compound (B3)) having isocyanate groups at both ends and an NCO group content of 15.7%.

[0243] (Synthesis Example 11) 63.0 parts of a mixture of 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and 4,4'-diphenylmethane diisocyanate were charged into a flask equipped with a stirrer, thermometer, and nitrogen gas inlet tube, and heated to 50°C while stirring under a nitrogen gas stream. 37.0 parts of the polyester polyol obtained in Synthesis Example 1, with an acid value of 1.5 mg KOH / g and a hydroxyl value of 200.5 mg KOH / g, were added dropwise in several portions, and the mixture was further heated and maintained at an internal temperature of 70°C for 4 hours to carry out the urethane reaction, yielding a urethane prepolymer (polyisocyanate compound (B6)) having isocyanate groups at both ends and an NCO group content of 15.5%.

[0244] Furthermore, as the polyisocyanate compound (B7), an adduct of toluene diisocyanate and trimethylolpropane was used. As the polyisocyanate compound (B-1) that does not fall under polyisocyanate compounds (B1) to (B7), 2K-SF-220A manufactured by DIC Corporation was used.

[0245] <Preparation of Adhesives> The polyol compound (A) prepared above was used as the polyol composition (X), and the polyisocyanate compound (B) was used as the polyisocyanate composition (Y), and the adhesives for the examples and comparative examples were prepared using the combinations shown in Tables 2 and 3. At this time, the ratio [NCO] / [isocyanate-reactive functional groups] between the number of moles of isocyanate groups [NCO] contained in the polyisocyanate compound (A) and the number of moles of functional groups that are reactive with isocyanate [isocyanate-reactive functional groups] contained in the polyol compound (B) was adjusted to 1.5.

[0246] <Manufacturing of Laminate> A 20 μm thick OPP film (Toyobo Co., Ltd. "P2161") is coated with a coating amount of 3.0 g / m². ２ Adhesive was applied in this manner, and then a 30 μm thick VMCPP film (Toray Film Processing Co., Ltd. "2703") was bonded to the adhesive-coated surface. The laminate was then aged at 40°C for 3 days to obtain a laminate for evaluation.

[0247] <Evaluation> (Adhesive Strength) Test pieces were cut from the aged laminate in 15 mm widths, and the adhesive strength (N / 15 mm) between the OPP / VMCPP films was measured using a tensile testing machine at a peeling speed of 300 mm / min and T-type peeling. The results were evaluated according to the following criteria and summarized in Tables 2 and 3. A: Adhesive strength of 2.0 N or more B: Adhesive strength of 1.0 N or more and less than 2.0 N C: Adhesive strength of 0.5 N or more and less than 1.0 N D: Adhesive strength less than 0.5 N

[0248] (Oxygen Permeability) After aging, the laminate was adjusted to a size of 10 cm x 10 cm, and the oxygen permeability was measured using an OX-TRAN2 / 21 (Mokon Co., Ltd.: oxygen permeability measuring device) in accordance with JIS-K7126 (isobaric method) under an atmosphere of 23°C, 0% RH, and 90% RH. The results were evaluated according to the following criteria and summarized in Tables 2 and 3. Note that RH represents relative humidity. A: Oxygen permeability of 1 cc / m ２ B: Oxygen permeability less than / day / atm ２ / day / atm or more, 3cc / m ２ Less than / day / atm C: Oxygen permeability of 3 cc / m ２ / day / atm or more, 6cc / m ２Less than / day / atm D: Oxygen permeability of 6 cc / m ２ / day / atm or more, 10cc / m ２ Less than / day / atm E: Oxygen permeability of 10 cc / m ２ / day / atm or more

[0249]

[0250]

[0251] As is clear from the above, the adhesive of the present invention has an excellent balance of adhesive strength and gas barrier properties. On the other hand, in Comparative Example 1, the polyester polyol (A2-1) turned white and could not be evaluated as an adhesive. Furthermore, the adhesives of Comparative Examples 2 and 3 did not exhibit sufficient gas barrier properties.

Claims

1. A two-component curable composition comprising a polyol composition (X) containing a polyol compound (A) and a polyisocyanate composition (Y) containing a polyisocyanate compound (B), wherein the polyol composition (X) contains a polyester polyol (A1) which is a reaction product of a composition containing a polyhydric alcohol and a polyhydric carboxylic acid.

2. The two-component curable composition according to claim 1, wherein the polycarboxylic acid comprises isophthalic acid, and the polyhydric alcohol comprises at least one selected from diethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol.

3. The two-component curable composition according to claim 2, wherein the polyhydric alcohol comprises diethylene glycol or 1,2-propanediol.

4. The two-component curable composition according to claim 2, wherein the polycarboxylic acid further comprises at least one selected from adipic acid and succinic acid.

5. The two-component curable composition according to claim 2, wherein the polycarboxylic acid further comprises terephthalic acid.

6. The two-component curable composition according to claim 2, wherein the polyol further comprises glycerin.

7. The two-component curable composition according to claim 1, wherein the polycarboxylic acid comprises terephthalic acid and the polyol comprises ethylene glycol.

8. The two-component curable composition according to claim 7, wherein the polycarboxylic acid further comprises at least one selected from adipic acid and succinic acid.

9. The two-component curable composition according to claim 7, wherein the polyol further comprises glycerin.

10. The two-component curable composition according to claim 1, wherein the hydroxyl value of the polyester polyol (A1) is 10 mg KOH / g or more and 450 mg KOH / g or less.

11. The two-component curable composition according to claim 1, wherein the acid value of the polyester polyol (A1) is 0.5 mg KOH / g or more and 90 mg KOH / g or less.

12. The two-component curable composition according to claim 1, wherein some of the hydroxyl groups of the polyester polyol (A1) are modified with a compound having acidic groups.

13. The two-component curable composition according to claim 1, used as a two-component curable adhesive.

14. The two-component curable composition according to claim 1, used as a two-component curable coating agent.

15. A laminate comprising a first substrate, a second substrate, and an adhesive layer disposed between the first substrate and the second substrate, wherein the adhesive layer is a cured coating film of the two-component curing adhesive described in claim 13.

16. A laminate comprising a substrate and a coating layer disposed on the substrate, wherein the coating layer is a cured coating film of the two-component curable coating agent described in claim 14.

17. A packaging material comprising the laminate according to claim 15 or 16.

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