Coating compositions and laminates

Abstract

This coating composition contains a polyisocyanate component and a polyol component. The polyisocyanate component contains an aromatic ring-containing isocyanate. The polyol component contains an acrylic polyol. The acrylic polyol is a polymer of a monomer composition that contains a hydroxyl group-containing polymerizable monomer and a carboxyl group-containing polymerizable monomer, but does not contain (meth)acrylonitrile.

Description

[Technical field]

[0001] The present invention relates to coating compositions and laminates. [Background technology]

[0002] Conventionally, in the field of various packaging materials, various functions such as gas barrier properties, retort resistance (hot water resistance), etc., have been required. Therefore, as packaging materials, for example, laminates in which a plurality of films having various functions are laminated are used.

[0003] More specifically, a laminate including a substrate, a resin coating film obtained from a primer, an ink layer, an adhesive layer, and a sealant layer has been proposed as a laminate. Also, as a primer for forming a resin coating film, for example, a primer has been proposed in which methyl methacrylate (MMA), acrylonitrile (AN), β-hydroxyethyl methacrylate (β-HEMA), styrene (St), butyl acrylate (BA), and methacrylic acid (MAA) are copolymerized to prepare a base solution, and a trimethylolpropane adduct of xylylene diisocyanate (XDI-TMP) as a curing agent is mixed into the obtained base solution (for example, see Patent Document 1 (Comparative Example Primer 4)).

[0004] It has also been proposed to further incorporate 5-(1,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride into the above primer (see, for example, Patent Document 1 (Primer 4 in Example)).

[0005] Furthermore, it has also been proposed to use a mixed solvent of methyl ethyl ketone, ethyl acetate, and propylene glycol monomethyl ether as the solvent in the above-mentioned primer (see, for example, Patent Document 1 (each of the Examples and Comparative Examples)). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2010 / 038643 Summary of the Invention [Problem to be solved by the invention]

[0007] On the other hand, in the field of coatings, there is a demand for the use of alkyl esters alone as solvents in order to improve handling and workability.

[0008] However, since the above primer does not have sufficient solubility in alkyl esters, a mixed solvent containing alkyl esters and other solvents is used as the solvent, which results in poor handling and workability.

[0009] Furthermore, laminates obtained using such primers are required to have further improved gas barrier properties and retort resistance (hot water resistance).

[0010] The present invention relates to a coating composition that is excellent in handleability and workability and that can efficiently produce a laminate that is excellent in gas barrier properties and retort resistance (hot water resistance), and a laminate obtained by using the coating composition. [Means for solving the problem]

[0011] The present invention [1] includes a coating composition comprising a polyisocyanate component and a polyol component, the polyisocyanate component comprising an aromatic ring-containing isocyanate, the polyol component comprising an acrylic polyol, the acrylic polyol comprising a hydroxyl group-containing polymerizable monomer and a carboxyl group-containing polymerizable monomer, and being a polymer of a monomer composition not comprising (meth)acrylonitrile.

[0012] The present invention [2] includes the coating composition according to the above [1], in which the aromatic ring-containing isocyanate includes xylylene diisocyanate and / or a derivative thereof.

[0013] The present invention [3] includes the coating composition according to the above [1] or [2], wherein the monomer composition contains an aromatic vinyl monomer.

[0014] The present invention [4] includes the coating composition according to any one of the above [1] to [3], wherein the equivalent ratio (NCO / OH) of the isocyanate groups of the polyisocyanate component to the hydroxyl groups of the polyol component is 1.2 or more and 6.0 or less.

[0015] The present invention [5] is a method for producing a hydroxyl group-containing monomer composition comprising the steps of: Polymerizable The ratio of the carboxylate to the monomer content R group-containing Polymerizable Mass ratio of monomer content (carboxy R group-containing Polymerizable Monomer / Hydroxyl Group-Containing Polymerizable The coating composition according to any one of the above [1] to [4], wherein the ratio of the monomer to the total monomer content is 0.03 or more and 0.1 or less.

[0016] The present invention [6] is a method for producing a carboxylate copolymer comprising the steps of: R group-containing Polymerizable The coating composition according to any one of the above [1] to [5], in which the content of the monomer is 0.1 parts by mass or more and 5.0 parts by mass or less, is included.

[0017] The present invention [7] includes the coating composition according to any one of the above [1] to [6], wherein the acrylic polyol has a glass transition temperature of -25°C or higher and 80°C or lower.

[0018] The present invention 8 The number average molecular weight of the acrylic polyol is 6000 or more. 7

[0023] The coating composition according to any one of claims 1 to 7,

[0019] The present invention 9

[0023] comprises a resin film, an inorganic thin film layer disposed on one side of the resin film in a thickness direction, a polyurethane layer disposed on one side of the inorganic thin film layer in a thickness direction, an adhesive layer disposed on one side of the polyurethane layer in a thickness direction, and a sealant layer disposed on one side of the adhesive layer in a thickness direction, 8

[0023] The present invention also includes a laminate comprising a cured product of the coating composition according to any one of the above items.

[0020] The present invention 10 The inorganic thin film layer contains aluminum oxide and / or silicon oxide. 9 The laminate includes the laminate described in the above.

[0021] The present invention 11 The resin film contains a polyester resin and / or a polyolefin resin. 9 ]or[ 10 The laminate includes the laminate described in the above. Effect of the Invention

[0022] In the coating composition of the present invention, the monomer composition, which is the raw material of the acrylic polyol, does not contain (meth)acrylonitrile, and therefore the coating composition of the present invention has excellent solubility in alkyl esters, and as a result, is excellent in handleability and workability.

[0023] The coating composition of the present invention contains an aromatic ring-containing isocyanate as a polyisocyanate component, and a polymer of a monomer composition containing a hydroxyl group-containing polymerizable monomer and a carboxyl group-containing polymerizable monomer as an acrylic polyol.

[0024] Therefore, the coating composition of the present invention can provide a laminate having excellent gas barrier properties and retort resistance (hot water resistance).

[0025] The laminate of the present invention can be obtained using the above-mentioned coating composition, and therefore can be obtained with good workability and has excellent gas barrier properties and retort resistance. [Brief description of the drawings]

[0026] [Figure 1] FIG. 1 is a schematic diagram showing an embodiment of the laminate of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] The coating composition of the present invention comprises a polyisocyanate component and a polyol component.

[0028] The polyisocyanate component contains an isocyanate compound as an active ingredient.

[0029] The isocyanate compound contains an aromatic ring-containing isocyanate as an essential component.

[0030] The aromatic ring-containing isocyanate is a polyisocyanate that contains an aromatic ring in the molecular skeleton.

[0031] Examples of aromatic ring-containing isocyanates include aromatic ring-containing isocyanate monomers and derivatives of aromatic ring-containing isocyanate monomers (hereinafter referred to as aromatic ring-containing isocyanate derivatives).

[0032] Examples of the aromatic ring-containing isocyanate monomer include aromatic polyisocyanates and araliphatic polyisocyanates.

[0033] Examples of aromatic polyisocyanates include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), toluidine diisocyanate (TODI), paraphenylene diisocyanate, and naphthalene diisocyanate (NDI), and preferably tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI). Examples of tolylene diisocyanates include 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate. Examples of diphenylmethane diisocyanates include 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and 2,2'-diphenylmethane diisocyanate.

[0034] Examples of aromatic aliphatic polyisocyanates include xylylene diisocyanate (XDI), tetramethyl xylylene diisocyanate (TMXDI), etc. Examples of xylylene diisocyanates include 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, etc. Examples of tetramethyl xylylene diisocyanates include 1,3-tetramethyl xylylene diisocyanate, 1,4-tetramethyl xylylene diisocyanate, etc.

[0035] These aromatic ring-containing isocyanate monomers can be used alone or in combination of two or more kinds.

[0036] As the aromatic ring-containing isocyanate monomer, preferably, aromatic polyisocyanate and araliphatic polyisocyanate are used, more preferably, tolylene diisocyanate and xylylene diisocyanate are used, and further preferably, xylylene diisocyanate is used.

[0037] Examples of the aromatic ring-containing isocyanate derivative include modified products obtained by modifying the above-mentioned aromatic ring-containing isocyanate monomers by known methods.

[0038] More specific examples of aromatic ring-containing isocyanate derivatives include polymers, allophanate-modified products, polyol-modified products, biuret-modified products, urea-modified products, oxadiazinetrione-modified products, and carbodiimide-modified products.

[0039] Examples of the polymer include a dimer, a trimer, a pentamer, a heptamer, etc. Examples of the trimer include an isocyanurate modified product, an iminooxadiazinedione modified product, etc.

[0040] Examples of the allophanate modified product include those produced by reacting the above-mentioned aromatic ring-containing isocyanate monomer with a monohydric alcohol or a dihydric alcohol.

[0041] The polyol modified product may, for example, be an alcohol adduct produced by reacting the above-mentioned aromatic ring-containing isocyanate monomer with a trihydric or higher alcohol.

[0042] Examples of the biuret modified product include biuret modified products produced by reacting the above-mentioned aromatic ring-containing isocyanate monomer with water and / or amines.

[0043] Examples of the urea modified product include the urea modified product produced by reacting the above-mentioned aromatic ring-containing isocyanate monomer with a diamine.

[0044] Examples of the oxadiazinetrione modified product include the oxadiazinetrione modified product produced by reacting the above-mentioned aromatic ring-containing isocyanate monomer with carbon dioxide gas.

[0045] Examples of the carbodiimide modified product include the carbodiimide modified product produced by the decarboxylation condensation reaction of the above-mentioned aromatic ring-containing isocyanate monomer.

[0046] Examples of aromatic ring-containing isocyanate derivatives include uretdione modified products, uretonimine modified products, and polymethylene polyphenylene polyisocyanates (crude MDI, polymeric MDI).

[0047] These aromatic ring-containing isocyanate derivatives can be used alone or in combination of two or more kinds.

[0048] As the aromatic ring-containing isocyanate derivative, preferably, a derivative of tolylene diisocyanate or a derivative of xylylene diisocyanate is used, more preferably, a derivative of xylylene diisocyanate is used, and further preferably, a derivative of 1,3-xylylene diisocyanate is used.

[0049] As the derivative, preferably, an isocyanurate modified product and a polyol modified product (alcohol adduct) are used, more preferably, a polyol modified product (alcohol adduct) is used, and particularly preferably, a trimethylolpropane adduct is used.

[0050] These aromatic ring-containing isocyanates can be used alone or in combination of two or more kinds.

[0051] As the aromatic ring-containing isocyanate, preferably, xylylene diisocyanate and / or a derivative thereof is used, more preferably, a derivative of xylylene diisocyanate is used, further preferably, a polyol-modified product (alcohol adduct) of xylylene diisocyanate is used, and particularly preferably, a trimethylolpropane adduct of xylylene diisocyanate is used.

[0052] Furthermore, the isocyanate compound may contain, as an optional component, an isocyanate having no aromatic ring, within a range that does not impair the excellent effects of the present invention.

[0053] The non-aromatic ring-containing isocyanate is a polyisocyanate that does not contain an aromatic ring in the molecular skeleton.

[0054] Examples of the aromatic ring-free isocyanate include an aromatic ring-free isocyanate monomer and a derivative of an aromatic ring-free isocyanate monomer (hereinafter referred to as an aromatic ring-free isocyanate derivative).

[0055] Examples of the non-aromatic ring-containing isocyanate monomer include aliphatic polyisocyanates.

[0056] Examples of aliphatic polyisocyanates include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), octamethylene diisocyanate, nonamethylene diisocyanate, 2,2'-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecamethylene triisocyanate, and 1,3,6-hexamethylene triisocyanate. nate, 1,8-diisocyanato-4-isocyanatomethyloctane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane, bis(isocyanatoethyl)carbonate, bis(isocyanatoethyl)ether, 1,4-butylene glycol dipropyl ether-ω,ω'-diisocyanate, lysine isocyanatomethyl ester, lysine triisocyanate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2-isocyanatopropyl-2,6-diisocyanatohexanoate, bis(4-isocyanato-n-butylidene)pentaerythritol, 2,6-diisocyanatomethyl caproate, and the like.

[0057] Additionally, the aliphatic polyisocyanate includes an alicyclic polyisocyanate.

[0058] Examples of alicyclic polyisocyanates include isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (H 12 MDI), bis(isocyanatomethyl)cyclohexane (H6XDI), 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-bis(isocyanatoethyl)cyclohexane, 1,4-bis(isocyanatoethyl)cyclohexane, methylcyclohexane diisocyanate, 2,2'-dimethyldicyclohexylmethane diisocyanate, dimer acid diisocyanate, 2,5-diisocyanatomethylbicyclo[2,2,1]-heptane, 2,6-diisocyanatomethylbicyclo[2,2,1]-heptane (NBDI), 2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-isocyanatomethylbicyclo-[2,2,1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl) 2-isocyanatomethyl 3-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)-bicyclo-[2,2,1]-heptane, 2-isocyanatomethyl 3-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo-[2,2,1]-heptane, 2-isocyanatomethyl 2-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)-bicyclo-[2,2,1]-heptane, 2-isocyanatomethyl 2-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo-[2,2,1]-heptane, and the like are preferably isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (H 12 MDI), and bis(isocyanatomethyl)cyclohexane (H6XDI).

[0059] These non-aromatic ring-containing isocyanate monomers can be used alone or in combination of two or more kinds.

[0060] As the aromatic ring-free isocyanate derivative, a modified product obtained by modifying the above-mentioned aromatic ring-free isocyanate monomer by a known method can be mentioned.

[0061] More specific examples of the aromatic ring-free isocyanate derivatives include polymers, allophanate-modified products, polyol-modified products, biuret-modified products, urea-modified products, oxadiazinetrione-modified products, and carbodiimide-modified products.

[0062] These non-aromatic ring-containing isocyanate derivatives can be used alone or in combination of two or more kinds.

[0063] These non-aromatic ring-containing isocyanates can be used alone or in combination of two or more kinds.

[0064] The content of the non-aromatic ring-containing isocyanate is appropriately set depending on the purpose and application.

[0065] More specifically, from the viewpoint of adhesion and gas barrier properties, the content of the non-aromatic ring-containing isocyanate is, for example, 30 parts by mass or less, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and particularly preferably 0 part by mass, relative to 100 parts by mass of the total amount of the polyisocyanate compounds (aromatic ring-containing isocyanate and non-aromatic ring-containing isocyanate).

[0066] In other words, the content of the aromatic ring-containing isocyanate is, for example, 70 parts by mass or more, preferably 80 parts by mass or more, more preferably 90 parts by mass or more, and particularly preferably 100 parts by mass, relative to 100 parts by mass of the total amount of the polyisocyanate compound.

[0067] That is, the isocyanate compound preferably does not contain an isocyanate having no aromatic ring.

[0068] In other words, the isocyanate compound preferably contains only an aromatic ring-containing isocyanate, more preferably contains only an aromatic ring-containing isocyanate derivative, and further preferably contains only a xylylene diisocyanate derivative.

[0069] The polyisocyanate component may also contain an organic solvent.

[0070] That is, the above-mentioned isocyanate compound can be diluted with an organic solvent.

[0071] The organic solvent may be an alkyl ester, such as methyl acetate, ethyl acetate, butyl acetate, or isobutyl acetate.

[0072] These organic solvents can be used alone or in combination of two or more kinds.

[0073] As the organic solvent, from the viewpoint of handling and workability, preferably, an alkyl ester is used, and more preferably, ethyl acetate is used.

[0074] When the polyisocyanate component contains an isocyanate compound and an organic solvent, the solids concentration is appropriately set depending on the purpose and application.

[0075] More specifically, the solids concentration of the polyisocyanate component (the content ratio of the isocyanate compound) is, for example, 5 mass % or more, preferably 10 mass % or more, and for example, 100 mass % or less, preferably 80 mass % or less.

[0076] The polyol component contains a polyol compound as an active ingredient.

[0077] The polyol compound contains an acrylic polyol as an essential component.

[0078] The acrylic polyol is a macropolyol. The macropolyol is an organic compound having two or more hydroxyl groups and a number average molecular weight of 400 or more, preferably 500 or more, for example, 100,000 or less.

[0079] The acrylic polyol is a polymer of a monomer composition which contains a hydroxyl group-containing polymerizable monomer and a carboxyl group-containing polymerizable monomer, but does not contain (meth)acrylonitrile.

[0080] In addition, (meth)acrylonitrile refers to acrylonitrile and / or methacrylonitrile, (meth)acrylic refers to acrylic and / or methacrylic, and (meth)acrylate refers to acrylate and / or methacrylate.

[0081] If the monomer composition, which is the raw material of the acrylic polyol, does not contain (meth)acrylonitrile, the solubility of the acrylic polyol in the alkyl ester can be improved, and as a result, a coating composition with excellent handleability and workability can be obtained.

[0082] Examples of hydroxyl group-containing polymerizable monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, and 12-hydroxylauryl (meth)acrylate.

[0083] These hydroxyl group-containing polymerizable monomers can be used alone or in combination of two or more kinds.

[0084] As the hydroxyl group-containing polymerizable monomer, from the viewpoints of gas barrier property and retort resistance, preferably, 2-hydroxyethyl (meth)acrylate is used, and more preferably, 2-hydroxyethyl acrylate is used.

[0085] Examples of the carboxyl group-containing polymerizable monomer include monocarboxylic acid, dicarboxylic acid, and salts thereof. Examples of the monocarboxylic acid include (meth)acrylic acid. Examples of the dicarboxylic acid include itaconic acid, maleic acid, fumaric acid, itaconic anhydride, maleic anhydride, and fumaric anhydride.

[0086] These carboxyl group-containing polymerizable monomers can be used alone or in combination of two or more kinds.

[0087] As the carboxy group-containing polymerizable monomer, preferably, (meth)acrylic acid and itaconic acid are used, more preferably, (meth)acrylic acid is used, and further preferably, acrylic acid is used.

[0088] The monomer composition may also contain a copolymerizable monomer that is copolymerizable with the hydroxyl group-containing polymerizable monomer and / or the carboxyl group-containing polymerizable monomer.

[0089] Examples of the copolymerizable monomer include (meth)acrylic acid esters, aromatic vinyl monomers, amino group-containing polymerizable monomers, glycidyl group-containing polymerizable monomers, sulfonic acid group-containing polymerizable monomers, acetoacetoxy group-containing polymerizable monomers, phosphoric acid group-containing compounds, vinyl esters, heterocyclic vinyl compounds, vinylidene halide compounds, α-olefins, and dienes.

[0090] Examples of (meth)acrylic acid esters include alkyl esters of (meth)acrylic acid having 1 to 12 carbon atoms. More specific examples include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-amyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, and benzyl (meth)acrylate.

[0091] These (meth)acrylic acid esters can be used alone or in combination of two or more kinds.

[0092] As the (meth)acrylic acid ester, preferably, methyl (meth)acrylate and n-butyl (meth)acrylate are used, and more preferably, methyl methacrylate and n-butyl acrylate are used.

[0093] Examples of aromatic vinyl monomers include styrene and α-methylstyrene.

[0094] These aromatic vinyl monomers can be used alone or in combination of two or more kinds.

[0095] As the aromatic vinyl monomer, preferably, styrene is used.

[0096] Examples of the amino group-containing polymerizable monomer include 2-aminoethyl (meth)acrylate, 2-(N-methylamino)ethyl (meth)acrylate, and 2-(N,N-dimethylamino)ethyl (meth)acrylate.

[0097] These amino group-containing polymerizable monomers can be used alone or in combination of two or more kinds.

[0098] An example of the glycidyl group-containing polymerizable monomer is glycidyl (meth)acrylate.

[0099] These glycidyl group-containing polymerizable monomers can be used alone or in combination of two or more kinds.

[0100] Examples of sulfonic acid group-containing polymerizable monomers include allyl sulfonic acid, methallyl sulfonic acid, and acrylamido t-butyl sulfonic acid. Examples of the salts include alkali metal salts such as sodium salts and potassium salts of the sulfonic acid group-containing polymerizable monomers, and ammonium salts. Specific examples include sodium allyl sulfonate, sodium methallyl sulfonate, and ammonium methallyl sulfonate.

[0101] These sulfonic acid-containing polymerizable monomers can be used alone or in combination of two or more kinds.

[0102] An example of the acetoacetoxy group-containing polymerizable monomer is acetoacetoxyethyl (meth)acrylate.

[0103] These acetoacetoxy group-containing polymerizable monomers can be used alone or in combination of two or more kinds.

[0104] An example of the phosphate group-containing compound is 2-methacryloyloxyethyl acid phosphate.

[0105] These phosphate group-containing compounds can be used alone or in combination of two or more kinds.

[0106] Examples of vinyl esters include vinyl acetate and vinyl propionate.

[0107] These vinyl esters can be used alone or in combination of two or more kinds.

[0108] An example of the N-substituted unsaturated carboxylic acid amide is N-methylol (meth)acrylamide.

[0109] These N-substituted unsaturated carboxylic acid amides can be used alone or in combination of two or more kinds.

[0110] An example of the heterocyclic vinyl compound is vinylpyrrolidone.

[0111] These heterocyclic vinyl compounds can be used alone or in combination of two or more kinds.

[0112] Examples of the vinylidene halide compound include vinylidene chloride and vinylidene fluoride.

[0113] These vinylidene halide compounds can be used alone or in combination of two or more kinds.

[0114] Examples of the α-olefins include ethylene and propylene.

[0115] These α-olefins can be used alone or in combination of two or more kinds.

[0116] An example of the dienes is butadiene.

[0117] These dienes can be used alone or in combination of two or more kinds.

[0118] These copolymerizable monomers can be used alone or in combination of two or more kinds.

[0119] As the copolymerizable monomer, preferably, a (meth)acrylic acid ester and an aromatic vinyl monomer are used.

[0120] That is, the monomer composition preferably contains a hydroxyl group-containing polymerizable monomer, a carboxyl group-containing polymerizable monomer, a (meth)acrylic acid ester and / or an aromatic vinyl monomer, and more preferably contains a hydroxyl group-containing polymerizable monomer, a carboxyl group-containing polymerizable monomer, a (meth)acrylic acid ester and an aromatic vinyl monomer.

[0121] In the monomer composition, the content of the hydroxyl group-containing polymerizable monomer is, from the viewpoint of the adhesion and gas barrier properties of the polyurethane layer described below, for example, 1 part by mass or more, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more, relative to 100 parts by mass of the total amount of the monomer composition; and from the viewpoint of the handleability of the acrylic polyol, for example, 99.99 parts by mass or less, preferably 60 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 23 parts by mass or less.

[0122] In addition, in the monomer composition, the content of the carboxy group-containing polymerizable monomer is, from the viewpoints of gas barrier property, retort resistance, handleability and workability, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 0.7 parts by mass or more, relative to 100 parts by mass of the total amount of the monomer composition, and is for example, 99 parts by mass or less, preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less.

[0123] In addition, hydroxyl group-containing Polymerizable Carboxylic acid monomer content R group-containing Polymerizable Mass ratio of monomer content (carboxy R group-containing Polymerizable Monomer / Hydroxyl Group-Containing Polymerizable Monomer) is, from the viewpoint of handleability and workability, for example, 0.01 or more, preferably 0.03 or more, and for example, 0.2 or less, preferably 0.1 or less.

[0124] In addition, when the monomer composition contains a (meth)acrylic acid ester, the content ratio of the (meth)acrylic acid ester is appropriately set so that the glass transition temperature of the acrylic polyol falls within the range described below. For example, the content ratio (total amount) of the (meth)acrylic acid ester is, for example, 1 part by mass or more, preferably 5 parts by mass or more, and for example, 70 parts by mass or less, preferably 50 parts by mass or less, relative to 100 parts by mass of the total amount of the monomer composition, from the viewpoint of blocking resistance and adhesion.

[0125] In addition, when the monomer composition contains an aromatic vinyl monomer, the content ratio of the aromatic vinyl monomer is appropriately set so that the glass transition temperature of the acrylic polyol is within the range described below.For example, the content ratio of the aromatic vinyl monomer is, for example, 1 part by mass or more, preferably 20 parts by mass or more, and for example, 50 parts by mass or less, preferably 40 parts by mass or less, based on 100 parts by mass of the total amount of the monomer composition.

[0126] The acrylic polyol can be obtained, for example, by mixing the above-mentioned monomer composition with a polymerization initiator in a solvent and polymerizing the monomer composition.

[0127] The solvent is not particularly limited, but examples thereof include the above-mentioned alkyl esters. A preferred example of the solvent is ethyl acetate.

[0128] The polymerization initiator is not particularly limited, but examples thereof include water-soluble initiators, oil-soluble initiators, and redox initiators, and preferably water-soluble initiators and oil-soluble initiators.

[0129] Examples of the water-soluble initiator include persulfates, hydrogen peroxide, organic hydroperoxides, and 4,4'-azobis(4-cyanovaleric acid).

[0130] Examples of the oil-soluble initiator include benzoyl peroxide and azobisisobutyronitrile.

[0131] These polymerization initiators can be used alone or in combination of two or more kinds.

[0132] The mixing ratio of the polymerization initiator is appropriately set depending on the purpose and application.

[0133] The amount of the polymerization initiator relative to 100 parts by mass of the total amount of the monomer composition is, for example, 0.05 parts by mass or more, and for example, 10 parts by mass or less, preferably 5 parts by mass or less.

[0134] The polymerization conditions are appropriately set depending on the purpose and application.

[0135] For example, under normal pressure, the polymerization temperature is, for example, 30° C. or more, preferably 50° C. or more, and for example, 95° C. or less, preferably 85° C. or less.

[0136] The polymerization time is, for example, 1 hour or more, preferably 2 hours or more, and for example, 30 hours or less, preferably 20 hours or less.

[0137] In the polymerization of the polymer composition, known additives may be added from the viewpoint of improving the production stability.

[0138] Examples of the additives include a pH adjuster, a metal ion sequestering agent, a molecular weight regulator (chain transfer agent), and a neutralizing agent.

[0139] The amount of additive and the timing of addition are appropriately determined depending on the purpose and application.

[0140] As a result, an acrylic polyol is obtained as a polymer of the monomer composition.

[0141] The acrylic polyol may also be obtained as a solution in the above solvent.

[0142] When the acrylic polyol is obtained as a solution, the solids concentration of the solution is, for example, 3 mass % or more, preferably 5 mass % or more, and for example, less than 100 mass %, preferably 90 mass % or less.

[0143] The glass transition temperature of the acrylic polyol (solid content) is, from the viewpoint of the blocking resistance of the polyurethane layer described later, for example, -50°C or higher, preferably -25°C or higher, more preferably 0°C or higher, even more preferably 20°C or higher, and particularly preferably 40°C or higher, and from the viewpoint of the handleability and workability of the acrylic polyol, for example, 100°C or lower, preferably 90°C or lower, more preferably 80°C or lower, and even more preferably 70°C or lower.

[0144] The glass transition temperature of the acrylic polyol is calculated by a known method based on the formulation of the monomer composition and the FOX equation.

[0145] In addition, the number average molecular weight of the acrylic polyol (solid content) is, from the viewpoints of gas barrier property, retort resistance, handleability and workability, for example, 2000 or more, preferably 6000 or more, and more preferably 10000 or more, and for example, 100000 or less, preferably 50000 or less, and more preferably 20000 or less.

[0146] The number average molecular weight of the acrylic polyol is calculated as a standard polystyrene equivalent molecular weight by gel permeation chromatography (GPC).

[0147] Furthermore, the polyol compound may contain other macropolyols and low molecular weight polyols as optional components within the range that does not impair the excellent effects of the present invention.

[0148] The other macropolyols are macropolyols other than acrylic polyols.

[0149] Other macropolyols include, for example, polyether polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, and polymerizable monomer-modified polyols.

[0150] These other macropolyols can be used alone or in combination of two or more kinds.

[0151] The low molecular weight polyol is an organic compound having two or more hydroxyl groups in the molecule and having a molecular weight of 50 or more and 400 or less, preferably 300 or less.

[0152] Examples of low molecular weight polyols include dihydric alcohols and trihydric alcohols. Examples of dihydric alcohols include 1,2-ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and neopentyl glycol. Examples of trihydric alcohols include glycerin and trimethylolpropane.

[0153] These low molecular weight polyols can be used alone or in combination of two or more kinds.

[0154] The content of the optional components is appropriately set depending on the purpose and application.

[0155] For example, from the viewpoint of gas barrier properties, the content ratio of other macropolyols is, for example, less than 50 parts by mass, preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and particularly preferably 0 parts by mass, per 100 parts by mass of the total amount of polyol compounds.

[0156] In addition, from the viewpoint of adhesion, the content of the low molecular weight polyol is, for example, less than 50 parts by mass, preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and particularly preferably 0 parts by mass, per 100 parts by mass of the total amount of the polyol compounds.

[0157] In other words, the content of the acrylic polyol is, for example, more than 50 parts by mass, preferably 60 parts by mass or more, more preferably 70 parts by mass or more, and particularly preferably 100 parts by mass, relative to 100 parts by mass of the total amount of the polyol compounds.

[0158] That is, the polyol component does not contain other macropolyols and low molecular weight polyols as active ingredients, but contains only the above acrylic polyol.

[0159] The polyol component may also contain an organic solvent.

[0160] That is, the above polyol compound can be diluted with an organic solvent.

[0161] The organic solvent may be any of the organic solvents described above. These organic solvents may be used alone or in combination of two or more kinds.

[0162] As the organic solvent, from the viewpoint of handling and workability, preferably, an alkyl ester is used, and more preferably, ethyl acetate is used.

[0163] When the polyol component contains an organic solvent, the solids concentration is appropriately set depending on the purpose and application.

[0164] More specifically, the solids concentration of the polyol component (the content ratio of the polyol compound) is, for example, 5 mass % or more, preferably 10 mass % or more, and for example, 100 mass % or less, preferably 80 mass % or less.

[0165] The coating composition may further include additives.

[0166] Examples of additives include phosphorus oxyacids or derivatives thereof, silane coupling agents, defoamers, epoxy resins, catalysts, coatability improvers, leveling agents, stabilizers (antioxidants, ultraviolet absorbers, etc.), plasticizers, surfactants, pigments, fillers, organic or inorganic fine particles, and antifungal agents.

[0167] These additives can be used alone or in combination of two or more kinds.

[0168] The additives may be added, for example, to either or both of the polyisocyanate component and the polyol component, or may be blended separately from the polyisocyanate component and / or the polyol component.

[0169] The amount of the additives to be added is appropriately determined depending on the purpose and application.

[0170] In the coating composition, the content ratio of the polyisocyanate component and the polyol component is adjusted, for example, as the equivalent ratio (NCO / OH) of the isocyanate group of the polyisocyanate component to the hydroxyl group of the polyol component.

[0171] More specifically, the equivalent ratio (NCO / OH) of the isocyanate groups of the polyisocyanate component to the hydroxyl groups of the polyol component is, from the viewpoint of gas barrier property, for example, 0.9 or more, preferably exceeds 1.0, more preferably 1.1 or more, even more preferably 1.2 or more, even more preferably 2.0 or more, and particularly preferably 2.5 or more, and from the viewpoint of retort resistance, for example, 10.0 or less, preferably 8.0 or less, more preferably 6.5 or less, even more preferably 6.0 or less, even more preferably 5.0 or less, and particularly preferably 4.5 or less.

[0172] The coating composition is prepared, for example, as a two-component curing coating agent or a one-component curing coating agent.

[0173] In the two-component curing coating agent, the above-mentioned polyol component is prepared as the base agent, and the above-mentioned polyisocyanate component is prepared as the curing agent. Then, the base agent and the curing agent are mixed in the above-mentioned ratio when used.

[0174] An example of a one-component curing coating agent is a moisture-curing adhesive that cures with moisture or steam (such as amine vapor). Such a one-component curing coating agent contains a urethane prepolymer having an isocyanate group at the molecular end, which is obtained by reacting, for example, a polyisocyanate component and the above-mentioned polyol component in the above-mentioned ratio.

[0175] The urethane prepolymer used as a one-component curing coating agent has an isocyanate group at the molecular end, and the isocyanate group reacts with moisture or vapor (such as amine vapor) in the air to cure.

[0176] The coating agent preferably contains the above-mentioned organic solvent.

[0177] As the organic solvent, from the viewpoint of handling and workability, preferably, an alkyl ester is used, and more preferably, ethyl acetate is used.

[0178] As described above, the organic solvent may be blended in the polyisocyanate component and / or the polyol component, or may be blended separately when the polyisocyanate component and the polyol component are mixed.

[0179] In the coating composition, the content ratio of the organic solvent is appropriately set so that the total amount of solids (resin solids) of the polyisocyanate component and the polyol component is a predetermined ratio.

[0180] The solids concentration of the coating composition (the total amount of the polyisocyanate component and the polyol component. Note that, in the case where an organic solvent is separately blended when the polyisocyanate component and the polyol component are mixed, the organic solvent is included) is, from the viewpoint of handleability and workability, for example, 5 mass% or more, preferably 10 mass% or more, and more preferably 20 mass% or more, and for example, 50 mass% or less, preferably 40 mass% or less, and more preferably 30 mass% or less.

[0181] In addition, in such a coating composition, the monomer composition, which is a raw material of the acrylic polyol, does not contain (meth)acrylonitrile, and therefore the coating composition has excellent solubility in alkyl esters, and as a result, is excellent in handleability and workability.

[0182] The coating composition contains an aromatic ring-containing isocyanate as a polyisocyanate component, and contains a polymer of a monomer composition containing a hydroxyl group-containing polymerizable monomer and a carboxyl group-containing polymerizable monomer as an acrylic polyol.

[0183] Therefore, the above coating composition can provide a laminate having excellent gas barrier properties and retort resistance (hot water resistance).

[0184] FIG. 1 is a schematic diagram of a laminate film as a laminate obtained using the above coating composition.

[0185] The laminate film 1 comprises a resin film 2, an inorganic thin film layer 3 arranged on one thickness-wise side of the resin film 2, a polyurethane layer 4 arranged on one thickness-wise side of the inorganic thin film layer 3, an adhesive layer 5 arranged on one thickness-wise side of the polyurethane layer 4, and a sealant layer 6 arranged on one thickness-wise side of the adhesive layer 5.

[0186] Such a laminate film 1 is formed, for example, by bonding a first film 10 having a resin film 2, an inorganic thin film layer 3 and a polyurethane layer 4 to a second film 11 having a sealant layer 6 via an adhesive layer 5.

[0187] The first film 10 is formed, for example, by laminating a polyurethane layer 4 on the surface of an inorganic thin film layer 3 that is laminated on a resin film 2.

[0188] The resin film 2 may be, for example, a plastic film containing a thermoplastic resin.

[0189] Examples of the thermoplastic resin include polyolefin resin, polyester resin, polyamide resin, and polyvinyl resin.

[0190] These thermoplastic resins can be used alone or in combination of two or more kinds.

[0191] As the thermoplastic resin, preferably, a polyolefin resin or a polyester resin is used.

[0192] In other words, the resin film 2 preferably contains a polyolefin resin and / or a polyester resin.

[0193] Examples of polyolefin resins include polyethylene (PE), polypropylene (PP), polyethylene-polypropylene copolymers (random copolymers and block copolymers), etc. Examples of polyester resins include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polylactic acid, etc.

[0194] When the resin film 2 contains two or more types of thermoplastic resins, the resin film 2 may be a coextruded film, or may be a composite film in which a plurality of thermoplastic resin films are adhered together.

[0195] Furthermore, the resin film 2 may be subjected to a surface treatment, if necessary. Examples of the surface treatment include a corona discharge treatment and a primer treatment.

[0196] The resin film 2 may be an unstretched film, or may be a uniaxially or biaxially stretched film.

[0197] These resin films 2 can be used alone or in combination of two or more kinds.

[0198] The resin film 2 is preferably a plastic film made of a polyester resin or a plastic film made of a polyolefin resin, more preferably a plastic film made of a polyester resin, and even more preferably a plastic film made of polyethylene terephthalate.

[0199] The thickness of the resin film 2 is not particularly limited, but is, for example, 5 μm or more, preferably 10 μm or more, and for example, 200 μm or less, preferably 100 μm or less.

[0200] The inorganic thin film layer 3 is disposed on one side in the thickness direction of the resin film 2, and more specifically, is laminated on the surface of one side of the resin film 2.

[0201] The inorganic thin film layer 3 is a thin film made of an inorganic material.

[0202] Examples of inorganic materials include inorganic substances, inorganic oxides, and inorganic nitrogen oxides.

[0203] Examples of inorganic substances include magnesium, calcium, barium, titanium, zirconium, aluminum, indium, silicon, germanium, and tin.

[0204] Examples of inorganic oxides include magnesium oxide, titanium oxide, aluminum oxide, indium oxide, silicon oxide, and tin oxide.

[0205] An example of the inorganic nitrogen oxide is silicon oxynitride.

[0206] These inorganic materials can be used alone or in combination of two or more kinds.

[0207] As the inorganic material, from the viewpoint of gas barrier properties, preferably, aluminum, silicon, aluminum oxide, and silicon oxide are used, and more preferably, aluminum oxide and silicon oxide are used.

[0208] In other words, the inorganic thin film layer 3 preferably contains aluminum oxide and / or silicon oxide.

[0209] The inorganic thin film layer 3 is formed on one surface of the resin film 2 by a known method.

[0210] Examples of methods for forming the inorganic thin film layer 3 include deposition methods (vacuum deposition, EB deposition, etc.), sputtering, ion plating, lamination, and plasma vapor phase growth methods (CVD, etc.).

[0211] As a method for forming the inorganic thin film layer 3, from the viewpoint of production efficiency, a vapor deposition method is preferable, and a vacuum vapor deposition method is more preferable.

[0212] In other words, the inorganic thin film layer 3 is preferably an inorganic vapor deposition layer.

[0213] The thickness of the inorganic thin film layer 3 is not particularly limited, but is, for example, 1 nm or more, preferably 2 nm or more, and for example, 500 nm or less, preferably 300 nm or less.

[0214] The sum of the thickness of the resin film 2 and the thickness of the inorganic thin film layer 3 is, for example, 5 μm or more, preferably 10 μm or more, and for example, 200 μm or less, preferably 100 μm or less.

[0215] Furthermore, a composite film (hereinafter sometimes referred to as a substrate film) in which an inorganic thin film layer 3 is laminated on the surface of a resin film 2 can also be obtained as a commercially available product.

[0216] Examples of such commercially available products include the Barrierox (registered trademark, manufactured by Toray Advanced Film Co., Ltd., alumina-vapor-deposited polyethylene terephthalate film) series and Techbarrier (registered trademark, manufactured by Mitsubishi Chemical Corporation, silica-vapor-deposited polyethylene terephthalate film).

[0217] The polyurethane layer 4 contains the cured product of the above-mentioned coating composition.

[0218] The polyurethane layer 4 is formed, for example, by applying the above-mentioned coating composition to the inorganic thin film layer 3, and then drying and curing (curing).

[0219] More specifically, the polyisocyanate component (curing agent) and the polyol component (main component) are mixed in the above-mentioned ratio, and the mixture (coating composition) is applied to the inorganic thin film layer 3.

[0220] The application temperature of the coating composition is, for example, 5°C or more, preferably 10°C or more, and for example, 50°C or less, preferably 40°C or less.

[0221] The coating amount of the coating composition is, for example, 0.1 g / m 2 More than 0.3 g / m 2 For example, 10 g / m 2 Preferably, 5 g / m or less 2 The following is the result.

[0222] The drying temperature of the coating composition is, for example, 60° C. or more, preferably 80° C. or more, and for example, 200° C. or less, preferably 150° C. or less. The drying time is, for example, 10 seconds or more, preferably 30 seconds or more, and for example, 1 hour or less, preferably 30 minutes or less.

[0223] The curing temperature (curing temperature) is, for example, 5° C. or more, preferably 10° C. or more, and for example, 50° C. or less, preferably 40° C. or less. The curing time is, for example, 10 hours or more, preferably 20 hours or more, and for example, 200 hours or less, preferably 100 hours or less.

[0224] As a result, a polyurethane layer 4 as a cured product of the coating composition is laminated on the inorganic thin film layer 3.

[0225] The thickness of the polyurethane layer 4 is not particularly limited, but is, for example, 5 μm or more, preferably 10 μm or more, and for example, 200 μm or less, preferably 100 μm or less.

[0226] As a result, a first film 10 comprising the resin film 2, the inorganic thin film layer 3 and the polyurethane layer 4 is obtained.

[0227] The thickness of the first film 10 is not particularly limited, but is, for example, 50 μm or more, preferably 100 μm or more, and for example, 2000 μm or less, preferably 1000 μm or less.

[0228] The second film 20 includes, and preferably consists of, a sealant layer 6 .

[0229] The sealant layer 6 is a heat seal layer that imparts heat sealability to the laminate film 1.

[0230] The sealant layer 6 may be, for example, a thermoplastic polyolefin film.

[0231] More specifically, examples of the thermoplastic polyolefin film include a polyethylene film and a non-oriented polypropylene film (CPP film).

[0232] These thermoplastic polyolefin films can be used alone or in combination of two or more kinds.

[0233] As the thermoplastic polyolefin film, preferably, a non-oriented polypropylene film (CPP film) is used.

[0234] The second film 20 (sealant layer 6) has a thickness of, for example, 10 μm or more, preferably 20 μm or more, and for example, 200 μm or less, preferably 150 μm or less.

[0235] Furthermore, the second film 20 (sealant layer 6) may be surface-treated as necessary. Examples of surface treatments include corona discharge treatment and primer treatment.

[0236] The adhesive layer 5 is a layer that is interposed between the polyurethane layer 4 of the first film 10 and the sealant layer 6 of the second film 20, and bonds the first film 10 and the second film 20 together.

[0237] The adhesive layer 5 is obtained by applying and drying a known laminating adhesive.

[0238] Examples of the laminating adhesive include polyolefin-based adhesives, acrylic-based adhesives, polyester-based adhesives, phenolic resin-based adhesives, epoxy-based adhesives, polyurethane-based adhesives, rubber-based adhesives, and silicone-based adhesives.

[0239] These laminating adhesives can be used alone or in combination of two or more kinds.

[0240] The method for forming the adhesive layer 5 is not particularly limited, but for example, a laminating adhesive is applied to one thickness-wise surface of the polyurethane layer 4 of the first film 10 and / or the other thickness-wise surface of the sealant layer 6 of the second film 20, the first film 10 and the second film 20 are bonded together, and then dried and cured.

[0241] More specifically, for example, first, a lamination adhesive is applied to one surface in the thickness direction of either first film 10 or second film 20.

[0242] Preferably, a laminating adhesive is applied to one surface in the thickness direction of the first film 10 (ie, the surface of the polyurethane layer 4).

[0243] The application temperature of the laminating adhesive is, for example, 35° C. or more, preferably 40° C. or more, and for example, 100° C. or less, preferably 90° C. or less, more preferably 85° C. or less.

[0244] The amount of the laminate adhesive applied is, for example, 0.5 g / m 2 More than 1 g / m 2 For example, 5 g / m 2 Less than 4.5 g / m 2 The following is the result.

[0245] As the laminating device in which the laminating adhesive is used, either a forward transfer type coating device or a reverse transfer type coating device (reverse coater) can be used.

[0246] Next, the coated surface is attached to the other film (preferably the second film 20) and cured (aged) at room temperature or under heating. The curing conditions for the laminating adhesive are appropriately set depending on the purpose and application.

[0247] As a result, an adhesive layer 5 is obtained as a cured product of the laminating adhesive.

[0248] The adhesive layer 5 has a thickness of, for example, 10 μm or more, preferably 20 μm or more, and for example, 200 μm or less, preferably 150 μm or less.

[0249] This results in a laminate film 1 comprising a resin film 2, an inorganic thin film layer 3 arranged on one thickness-wise side of the resin film 2, a polyurethane layer 4 arranged on one thickness-wise side of the inorganic thin film layer 3, an adhesive layer 5 arranged on one thickness-wise side of the polyurethane layer 4, and a sealant layer 6 arranged on one thickness-wise side of the adhesive layer 5.

[0250] The laminate film 1 has a thickness of, for example, 20 μm or more, preferably 30 μm or more, and for example, 180 μm or less, preferably 150 μm or less.

[0251] Such a laminate film 1 can be obtained using the above-mentioned coating composition, and therefore can be obtained with good workability and has excellent gas barrier properties and retort resistance.

[0252] Therefore, such a laminate film 1 is suitable for use as a packaging material in various industrial fields such as food, beverages, medicines, and quasi-drugs. EXAMPLES

[0253] Next, the present invention will be described based on examples and comparative examples, but the present invention is not limited to the following examples. Note that "parts" and "%" are based on mass unless otherwise specified. In addition, the specific numerical values ​​of the blending ratio (content ratio), physical property values, parameters, etc. used in the following description can be replaced with the upper limit value (numerical value defined as "less than or equal to" or "less than") or lower limit value (numerical value defined as "more than or equal to" or "exceeding") of the corresponding blending ratio (content ratio), physical property values, parameters, etc. described in the above "Form for carrying out the invention".

[0254] Reference example 1 An acrylic polyol was prepared according to the formulation shown in Table 1.

[0255] That is, the monomer composition prepared according to the recipe shown in Table 1 was dispersed in ethyl acetate, and 1.0 part by mass of azobisisobutyronitrile (AIBN) was added as a polymerization initiator, followed by reaction for 10 hours at 60° C. As a result, an acrylic polyol (polyol compound) was obtained.

[0256] This also resulted in an ethyl acetate solution of acrylic polyol (polyol component (hereinafter referred to as acrylic polyol solution)).

[0257] Next, ethyl acetate was further added to the acrylic polyol solution to adjust the solid content concentration to 50%.

[0258] The glass transition temperature (Tg) of the obtained acrylic polyol was calculated from the formulation of the monomer composition and the FOX equation. The number average molecular weight (Mn) of the acrylic polyol was calculated as a standard polystyrene equivalent molecular weight by gel permeation chromatography.

[0259] Next, 0.5 g of the obtained acrylic polyol solution (solid concentration 50%) and 8.5 g of ethyl acetate were mixed, and then 1.0 g of Takenate D-110N (manufactured by Mitsui Chemicals, Inc., trimethylolpropane adduct of XDI (isocyanate compound), solid concentration 75%, ethyl acetate solution (polyisocyanate component)) was mixed to prepare a transparent coating composition.

[0260] On the other hand, an alumina-deposited PET film (alumina-deposited polyethylene terephthalate film) was prepared as a substrate film having a resin film and an inorganic thin film layer.

[0261] Next, the above coating composition was applied to the inorganic thin film layer (alumina side) to a dry thickness of 0.5 g / m 2 The coating was performed using a bar coater so that the coating became as shown in FIG. 1, and the coating was then placed in a drying oven set at 110°C, dried for 1 minute, and aged at 40°C for 2 days.

[0262] This resulted in the formation of a polyurethane layer.

[0263] Next, a mixture of Takelac A-310 (manufactured by Mitsui Chemicals) and Takenate A-3 (manufactured by Mitsui Chemicals) (Takelac A-310 / Takenate A-3 = 10 / 1 (mass ratio)) was applied to the polyurethane layer as a dry lamination adhesive to a dry thickness of 3 g / m 2 The coating was applied using a bar coater so that the coating became smooth, and then dried using a dryer.

[0264] Thereafter, an unstretched polypropylene film (Tocello CP RXC-22 (CPP film, #60), manufactured by Mitsui Chemicals Tocello Co., Ltd.) was laminated onto the surface of the adhesive as a sealant layer, and the resulting mixture was cured at 40° C. for 3 days.

[0265] As a result, a laminate film was obtained as a laminate.

[0266] Examples 2, 6, 8 to 13, Comparative Examples 1, 2 and 5 An acrylic polyol solution (solid concentration 50%) was prepared according to the recipe shown in Tables 1 to 3. In addition, 0.7 g of the acrylic polyol solution (solid concentration 50%) was mixed with 8.4 g of ethyl acetate, and then 0.9 g of Takenate D-110N (manufactured by Mitsui Chemicals, trimethylolpropane adduct of XDI, solid concentration 75%, ethyl acetate solution) was mixed. Others were Reference example The coating composition and laminate film were obtained in the same manner as in 1.

[0267] Example 3 An acrylic polyol solution (solid concentration 50%) was prepared according to the recipe shown in Table 1. In addition, 1.0 g of the acrylic polyol solution (solid concentration 50%) was mixed with 8.3 g of ethyl acetate, and then 0.7 g of Takenate D-110N (manufactured by Mitsui Chemicals, trimethylolpropane adduct of XDI, solid concentration 75%, ethyl acetate solution) was mixed. Others were: Reference example The coating composition and laminate film were obtained in the same manner as in 1.

[0268] Reference example 4 An acrylic polyol solution (solid concentration 50%) was prepared according to the recipe shown in Table 1. In addition, 1.3 g of the acrylic polyol solution (solid concentration 50%) was mixed with 8.2 g of ethyl acetate, and then 0.5 g of Takenate D-110N (manufactured by Mitsui Chemicals, trimethylolpropane adduct of XDI, solid concentration 75%, ethyl acetate solution) was mixed. Others were: Reference example The coating composition and laminate film were obtained in the same manner as in 1.

[0269] Example 5 An acrylic polyol solution (solid concentration 50%) was prepared according to the recipe shown in Table 1. In addition, 1.0 g of the acrylic polyol solution (solid concentration 50%) was mixed with 8.3 g of ethyl acetate, and then 0.7 g of Takenate D-110N (manufactured by Mitsui Chemicals, trimethylolpropane adduct of XDI, solid concentration 75%, ethyl acetate solution) was mixed. Others were: Reference example The coating composition and laminate film were obtained in the same manner as in 1.

[0270] Example 7 An acrylic polyol solution (solid concentration 50%) was prepared according to the recipe shown in Table 1. In addition, 0.9 g of the acrylic polyol solution (solid concentration 50%) was mixed with 8.4 g of ethyl acetate, and then 0.7 g of Takenate D-110N (manufactured by Mitsui Chemicals, trimethylolpropane adduct of XDI, solid concentration 75%, ethyl acetate solution) was mixed. Others were: Reference example The coating composition and laminate film were obtained in the same manner as in 1.

[0271] Example 14 An acrylic polyol solution (solid concentration 50%) was prepared according to the recipe in Table 2. In addition, 0.5 g of the acrylic polyol solution (solid concentration 50%) was mixed with 8.4 g of ethyl acetate, and then 0.7 g of Takenate D-110N (manufactured by Mitsui Chemicals, trimethylolpropane adduct of XDI, solid concentration 75%, ethyl acetate solution) and 0.2 g of Takenate T-50 (manufactured by Mitsui Chemicals, XDI monomer) were mixed. The other ingredients were: Reference exampleThe coating composition and laminate film were obtained in the same manner as in 1.

[0272] Example 15 An acrylic polyol solution (solid concentration 50%) was prepared according to the recipe shown in Table 2. In addition, 0.7 g of the acrylic polyol solution (solid concentration 50%) was mixed with 8.4 g of ethyl acetate, and then 0.9 g of Takenate D-131N (manufactured by Mitsui Chemicals, isocyanurate modified XDI, solid concentration 75%, ethyl acetate solution) was mixed. Others were: Reference example The coating composition and laminate film were obtained in the same manner as in 1.

[0273] Example 16 An acrylic polyol solution (solid concentration 50%) was prepared according to the recipe shown in Table 2. In addition, 0.7 g of the acrylic polyol solution (solid concentration 50%) was mixed with 8.5 g of ethyl acetate, and then 0.8 g of Takenate D-103H (manufactured by Mitsui Chemicals, Inc., trimethylolpropane adduct of TDI, solid concentration 75%, ethyl acetate solution) was mixed. Others were: Reference example The coating composition and laminate film were obtained in the same manner as in 1.

[0274] Comparative Examples 3 and 4 An acrylic polyol solution (solid content concentration: 50%) was prepared according to the formulation shown in Table 3.

[0275] However, when 0.7 g of the acrylic polyol solution (solid content concentration: 50%) and 8.4 g of ethyl acetate were mixed, the acrylic polyol did not dissolve in the ethyl acetate, and a coating composition could not be obtained.

[0276] Comparative Example 6 An acrylic polyol solution (solid concentration 50%) was prepared according to the recipe shown in Table 3. In addition, 0.7 g of the acrylic polyol solution (solid concentration 50%) was mixed with 8.4 g of ethyl acetate, and then 0.9 g of Takenate D-160 (manufactured by Mitsui Chemicals, Inc., HDI trimethylolpropane adduct, solid concentration 75% ethyl acetate solution) was mixed. Others were: Reference exampleThe coating composition and laminate film were obtained in the same manner as in 1.

[0277] Example 17 and Comparative Examples 7 to 10 A coating composition and a laminate film were obtained in the same manner as in Example 2, Comparative Examples 1-2, and Comparative Examples 5-6, except that a silica-vapor-deposited PET film (silica-vapor-deposited polyethylene terephthalate film) was used as the base film instead of an alumina-vapor-deposited PET film (alumina-vapor-deposited polyethylene terephthalate film).

[0278] Example 18 and Comparative Examples 11 to 14 A coating composition and a laminate film were obtained in the same manner as in Example 2, Comparative Examples 1-2, and Comparative Examples 5-6, except that a silica-vapor-deposited BOPP film (silica-vapor-deposited biaxially oriented polypropylene film) was used instead of an alumina-vapor-deposited PET film (alumina-vapor-deposited polyethylene terephthalate film) as the base film.

[0279] <Evaluation> (1) Retort processing The laminate film was subjected to hot water sterilization (retort treatment) at 120° C. for 30 minutes under a pressure of 0.2 MPa.

[0280] (2) Measurement of oxygen permeability Using an oxygen permeability measuring device (OX-TRAN2 / 20, manufactured by MOCON), the oxygen permeability of each laminate film before and after hot water sterilization was measured at 20°C and 80% relative humidity (80% RH) for 1 m 2 , oxygen transmission rate per day and atmosphere (OTR: cc / m 2 -24hr.atm) was measured.

[0281] In addition, the OTR reduction rate due to the retort treatment was calculated based on the oxygen transmission amount before and after the retort treatment according to the following formula.

[0282] OTR reduction rate = oxygen permeability before retort treatment / oxygen permeability after retort treatment

[0283] (3) Measurement of adhesion (lamination strength) The lamination strength (N) between the inorganic thin film layer and the polyurethane layer of each laminate film was measured by a T-peel test (15 mm width) in accordance with JIS K 6854 (1999) at a peel speed of 300 mm / min.

[0284] (4) Blocking property The polyurethane layer and the resin film are in contact (area 20 cm 2 ) and stored at 40°C for 24 hours.

[0285] Next, the polyurethane layer and the resin film were peeled off in the shear direction at a speed of 300 mm / min using a tensile tester.

[0286] The blocking property was evaluated based on the following criteria. ◯: The strength was 1N or less. △: The strength was 1N or more and it could be easily peeled off by hand. ×: The strength was 2N or more.

[0287] [Table 1]

[0288] [Table 2]

[0289] [Table 3]

[0290] [Table 4]

[0291] Details of the abbreviations in the table are given below.

[0292] AA: Acrylic acid St: styrene MMA: Methyl methacrylate BA: n-butyl acrylate AN: Acrylonitrile HEA: 2-hydroxyethyl acrylate HEMA: 2-hydroxyethyl methacrylate OTR: Oxygen Transmission Rate D-110N: Takenate D-110N, trimethylolpropane adduct of XDI, solids concentration 75%, ethyl acetate solution, manufactured by Mitsui Chemicals D-131N: Takenate D-131N, isocyanurate modified XDI, solids concentration 75%, ethyl acetate solution, manufactured by Mitsui Chemicals T-50: Takenate T-50, XDI monomer, manufactured by Mitsui Chemicals D-103H: Takenate D-103H, trimethylolpropane adduct of TDI, solids concentration 75%, ethyl acetate solution, manufactured by Mitsui Chemicals AlOxPET: Alumina-deposited polyethylene terephthalate film SiOxPET: Silica-deposited polyethylene terephthalate film SiOxBOPP: Silica-deposited biaxially oriented polypropylene film MF: Substrate cut (substrate film breakage)

[0293] The above invention is provided as an exemplary embodiment of the present invention, but this is merely an example and should not be interpreted as being limited. Modifications of the present invention that are obvious to those skilled in the art are included in the scope of the following claims. [Industrial Applicability]

[0294] The coating composition and laminate of the present invention are suitably used in the fields of food packaging materials, beverage packaging materials, pharmaceutical packaging materials, and quasi-drug packaging materials. [Explanation of symbols]

[0295] 1. Laminating film 2. Resin film 3. Inorganic thin film layer 4 Polyurethane Layer 5 Adhesive layer 6 Sealant Layer

Claims

1. Contains a polyisocyanate component, a polyol component, and an organic solvent, The polyisocyanate component includes an aromatic ring-containing isocyanate, The polyol component includes an acrylic polyol, The acrylic polyol is a polymer of a monomer composition containing a hydroxyl group-containing polymerizable monomer and a carboxyl group-containing polymerizable monomer, but not containing (meth)acrylonitrile; The organic solvent contains an alkyl ester, The equivalent ratio (NCO / OH) of the isocyanate group of the polyisocyanate component to the hydroxyl group of the polyol component is 1.2 or more and 6.0 or less. A coating composition comprising:

2. The aromatic ring-containing isocyanate is Contains xylylene diisocyanate and / or its derivatives The coating composition according to claim 1 .

3. The monomer composition comprises an aromatic vinyl monomer. The coating composition according to claim 1 .

4. In the monomer composition, a mass ratio of the content of the carboxyl group-containing polymerizable monomer to the content of the hydroxyl group-containing polymerizable monomer (carboxyl group-containing polymerizable monomer / hydroxyl group-containing polymerizable monomer) is 0.03 or more and 0.1 or less. The coating composition according to claim 1 .

5. The content of the carboxyl group-containing polymerizable monomer is 0.1 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the total amount of the monomer composition. The coating composition according to claim 1 .

6. The glass transition temperature of the acrylic polyol is −25° C. or higher and 80° C. or lower. The coating composition according to claim 1 .

7. The number average molecular weight of the acrylic polyol is 6000 or more. The coating composition according to claim 1 .

8. A resin film; an inorganic thin film layer disposed on one side of the resin film in a thickness direction; a polyurethane layer disposed on one side of the inorganic thin film layer in a thickness direction; an adhesive layer disposed on one side of the polyurethane layer in a thickness direction; a sealant layer disposed on one side of the adhesive layer in a thickness direction; It is equipped with the polyurethane layer comprises a cured product of a coating composition, The coating composition comprises: Contains a polyisocyanate component and a polyol component, The polyisocyanate component includes an aromatic ring-containing isocyanate, The polyol component includes an acrylic polyol, The acrylic polyol is a polymer of a monomer composition containing a hydroxyl group-containing polymerizable monomer and a carboxyl group-containing polymerizable monomer, but not containing (meth)acrylonitrile. A laminate comprising:

9. The inorganic thin film layer contains aluminum oxide and / or silicon oxide.

9. The laminate according to claim 8.

10. The resin film contains a polyester resin and / or a polyolefin resin.

9. The laminate according to claim 8.

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