Two-Component Solvent-Based Adhesive Composition

Abstract

The present disclosure provides a two-component adhesive composition. The two-component solvent-based adhesive composition contains the reaction product of (A) an isocyanate component; (B) a dimer acid polyester polyol component containing the reaction product of a reaction mixture including (i) from 20 wt % to 60 wt % dimer acid, based on the total weight of the dimer acid polyester polyol component, (ii) a dicarboxylic acid, and (iii) a polyol; and (C) a solvent.

Claims

1. A two-component solvent-based adhesive composition comprising the reaction product of: (A) an isocyanate component; (B) a dimer acid polyester polyol component comprising the reaction product of a reaction mixture comprising (i) from 20 wt % to 60 wt % dimer acid, based on the total weight of the dimer acid polyester polyol component; (ii) a dicarboxylic acid; (iii) a polyol; and (C) a solvent.

2. The two-component solvent-based adhesive composition of claim 1, wherein the dicarboxylic acid is selected from the group consisting of phthalic acid, isophthalic acid, terephthalic acid, azelaic acid, sebacic acid, adipic acid, and combinations thereof.

3. The two-component solvent-based adhesive composition of claim 1, wherein the polyol is selected from the group consisting of 2-methyl-1, 3-propanediol, trimethylolpropane, 1, 4-butanediol, 1, 6-hexanediol, and neopentyl glycol (NPG), and combinations thereof.

4. The two-component solvent-based adhesive composition of claim 1, wherein the isocyanate is a multifunctional isocyanate.

5. The two-component solvent-based adhesive composition of claim 1, wherein the isocyanate component has an average NCO functionality from 2.2 to 5.0.

6. The two-component solvent-based adhesive composition of claim 1, wherein the two-component solvent-based adhesive composition has a Polyol:Isocyanate Weight Ratio from 100:5 to 100:35.

7. A laminate comprising a first substrate; a second substrate; and an adhesive layer between the first substrate and the second substrate, the adhesive layer formed from the two-component solvent-based adhesive composition of claim 1.

8. The laminate of claim 7, wherein the first substrate is a metal foil film and the second substrate is a polyethylene film; and the laminate has a bond strength after the boil-in-bag test from 4.0 N/15 mm to 15 N/15 mm; a bond strength after chemical aging from 2.0 N/15 mm to 10 N/15 mm.

9. The laminate of claim 8, wherein the laminate has a heat seal strength after the boil-in-bag test from 35 N/15 mm to 75 N/15 mm; and a heat seal strength after chemical aging from 35 N/mm to 75 N/15 mm.

10. A method of forming a two-component solvent-based adhesive composition comprising: (i) providing a dimer acid polyester polyol component comprising from 20 wt % to 60 wt % units derived from dimer acid; (ii) providing an isocyanate component; and (iii) reacting the dimer acid polyester polyol component with the isocyanate component to form the two-component solvent-based adhesive composition.

Description

DETAILED DESCRIPTION

[0038] The present disclosure provides a two-component solvent-based adhesive composition. The two-component solvent-based adhesive composition contains the reaction product of (A) an isocyanate component; (B) a dimer acid polyester polyol component containing the reaction product of a reaction mixture including (i) from 20 wt % to 60 wt % dimer acid, based on the total weight of the dimer acid polyester polyol component, (ii) a dicarboxylic acid, and (iii) a polyol; and (C) a solvent.

[0039] A. Isocyanate Component

[0040] The two-component solvent-based adhesive composition contains the reaction product of (A) an isocyanate component; (B) a dimer acid polyester polyol component; and (C) a solvent.

[0041] Nonlimiting examples of suitable isocyanate components include aromatic isocyanates, aliphatic isocyanates, carbodiimide modified isocyanates, polyisocyanate adducts, polyisocyanate trimers, and the combinations thereof.

[0042] An “aromatic isocyanate” is an isocyanate containing one or more aromatic rings. Nonlimiting examples of suitable aromatic isocyanates include isomers of methylene diphenyl dipolyisocyanate (MDI) such as 4,4′-MDI, 2,4′-MDI, and 2, 2′-MDI; modified MDI such as carbodiimide modified MDI or allophanate modified MDI; isomers of toluene-dipolyisocyanate (TDI) such as 2,4-TDI, and 2,6-TDI; isomers of naphthalene-dipolyisocyanate (NDI) such as 1, 5-NDI; isomers of phenylene dipolyisocyanate (PDI), such as 1,3-PDI and 1,4-PDI; and combinations thereof.

[0043] An “aliphatic isocyanate” is an isocyanate in which the isocyanate group (—NCO) is not directly bonded to an aromatic ring. In an embodiment, the aliphatic isocyanate is void of, or contains no, aromatic rings. Aliphatic isocyanates include cycloaliphatic isocyanate, in which the chemical chain is ring-structured. In an embodiment, the aliphatic isocyanate contains from 3, or 4, or 5, or 6 to 7, or 8, 10, 12, or 13, or 14, or 15, or 16 carbon atoms in the linear, branched, or cyclic alkylene residue. Nonlimiting examples of suitable aliphatic isocyanates include cyclohexane diisocyanate; methylcyclohexane diisocyanate; ethylcyclohexane diisocyanate; propylcyclohexane diisocyanate; methyldiethylcyclohexane diisocyanate; propane diisocyanate; butane diisocyanate; pentane diisocyanate; hexane diisocyanate; heptane diisocyanate; octane diisocyanate; nonane diisocyanate; nonane triisocyanate, such as 4-isocyanatomethyl-1,8-octane diisocyanate (TIN); decane di- and tri-isocyanate; undecane di- and tri-isocyanate; dodecane di- and tri-isocyanate; isophorone diisocyanate (IPDI); hexamethylene diisocyanate (HDI); diisocyanatodicyclohexylmethane (H12MDI); 2-methylpentane diisocyanate (MPDI); 2,2,4-trimethylhexamethylene diisocyanate; 2,4,4-trimethylhexamethylene diisocyanate; norbornane diisocyanate (NBDI); xylylene diisocyanate (XDI); tetramethylxylylene diisocyanate; isomers, dimers, and/or trimers thereof; and combinations thereof.

[0044] Nonlimiting examples of additional suitable isocyanates include 4-methyl-cyclohexane 1,3-diisocyanate; 2-butyl-2-ethylpentamethylene diisocyanate; 3(4)-isocyanatomethyl-1-methylcyclohexyl isocyanate; 2-isocyanatopropylcyclohexyl isocyanate; 2,4′-methylenebis (cyclohexyl) diisocyanate; 1,4-diisocyanato-4-methyl-pentane; and combinations thereof.

[0045] In an embodiment, the isocyanate is an oligomeric isocyanate that is the oligomeric reaction product of an isocyanate and a polyol.

[0046] A “polyisocyanate adduct” is the reaction product of an excess quantity of di-isocyanate with low molecular weight glycols and polyols having a molecular weight less than 400 g/mol (such trimethylolpropane, glycerin, 1,2-dihydroxy propane, and combinations thereof). A nonlimiting example of a suitable polyisocyanate adduct is the oligomeric reaction product of toluene di-isocyanate (TDI), 2,2′-oxydiethanol, and propylidenetrimethanol (said oligomeric isocyanate being available under CAS 53317-61-6).

[0047] A “polyisocyanate timer” is the reaction product prepared by trimerization of di-isocyanates in the presence of a catalyst. A nonlimiting example of a polyisocyanate trimer is 2,4-TDI trimer (said polyisocyanate trimer being available under CAS 26603-40-7).

[0048] In an embodiment, the isocyanate is a multifunctional isocyanate. In another embodiment, the multifunctional isocyanate is selected from a di-isocyanate, a tri-isocyanate, and combinations thereof. In a further embodiment, the multifunctional isocyanate is a di-isocyanate.

[0049] In an embodiment, the isocyanate is a multifunctional isocyanate with at least two isocyanate groups, or at least three isocyanate groups.

[0050] In an embodiment, the isocyanate is a multifunctional isocyanate having an average isocyanate (NCO) functionality from 2.2 to 5.0.

[0051] The isocyanate component may comprise two or more embodiments disclosed herein.

[0052] B. Dimer Acid Polyester Polyol Component

[0053] The two-component solvent-based adhesive composition contains the reaction product of (A) the isocyanate component; (B) a dimer acid polyester polyol component; and (C) a solvent. The dimer acid polyester polyol component (herein referred to as the “DAPP Component”) contains the reaction product of a reaction mixture including (i) from 20 wt % to 60 wt % dimer acid, based on the total weight of the DAPP Component, (ii) a dicarboxylic acid, and (iii) a polyol. Dimer Acid

[0054] The DAPP Component contains the reaction product of a reaction mixture including (i) from 20 wt % to 60 wt % dimer acid, based on the total weight of the DAPP Component, (ii) a dicarboxylic acid, and (iii) a polyol.

[0055] A “dimer acid” is a dicarboxylic acid compound obtained by allowing a fatty acid having from two to four ethylenic double bonds and from 14 to 22 carbon atoms (hereinafter referred to as “Unsaturated Fatty Acid A”), and a fatty acid having from one to four ethylenic double bonds and from 14 to 22 carbon atoms (hereinafter referred to as an “Unsaturated Fatty Acid B”), to react on double bonds in a dimerization reaction. In an embodiment, Unsaturated Fatty Acid A has two ethylenic double bonds and from 14 to 22 carbon atoms, and the Unsaturated Fatty Acid B has one or two ethylenic double bonds and from 14 to 22 carbon atoms. Nonlimiting examples of suitable Unsaturated Fatty Acid A include tetradecadienoic acids, hexadecadienoic acids, octadecadienoic acids (such as linoleic acid), eicosadienoic acids, docosadienoic acids, octadecatrienoic acids (such as linolenic acid), eicosatetraenoic acids (such as arachidonic acid), and combinations thereof. Nonlimiting examples of suitable Unsaturated Fatty Acid B include the above examples, as well as tetradecenoic acids (tsuzuic acid, physeteric acid, myristoleic acid), hexadecenoic acids (such as pa lmitoleic acid), octadecenoic acids (such as oleic acid, elaidic acid, and vaccenic acid), eicosenoic acids (such as gadoleic acid), and docosenoic acids (such as erucic acid, setoleic acid, and brassidic acid), and combinations thereof.

[0056] The obtained dimer acid is a mixture of dimer acids the structures of which differ according to the binding site or isomerization of a double bond. A nonlimiting example of a suitable dimer acid structure is the following Structure (A):

##STR00001##

[0057] In an embodiment, the dimer acid is a C.sub.36 dimer acid. In a further embodiment, the C.sub.36 dimer acid has the Structure (A).

[0058] In an embodiment, the obtained dimer acid includes from 0 wt % to 2 wt %, or 4 wt %, or 6 wt % monomer acid and/or from 0 wt % to 2 wt %, or 4 wt %, or 6 wt % polymer acid having a degree of polymerization greater than, or equal to, the degree of polymerization of a trimer acid.

[0059] In an embodiment, the dimer acid is unsaturated. An “unsaturated dimer acid” includes at least one carbon-carbon double bond. Structure (A) is an unsaturated dimer acid. A nonlimiting example of a suitable dimer acid is ATUREX™ 1001 (CAS 61788-89-4), available from Aturex Group.

[0060] In an embodiment, the dimer acid has an acid value from 150 mg KOH/g, or 160 mg KOH/g, or 170 mg KOH/g, or 180 mg KOH/g, or 190 mg KOH/g, or 194 mg KOH/g to 200 mg KOH/g, or 210 mg KOH/g, or 220 mg KOH/g, or 230 mg KOH/g, or 240 mg KOH/g, or 250 mg KOH/g. In another embodiment, the dimer acid has an acid value from 150 mg KOH/g to 250 mg KOH/g, or from 180 mg KOH/g to 220 mg KOH/g, or from 190 mg KOH/g to 200 mg KOH/g.

[0061] In an embodiment, the dimer acid has the Structure (A) and has an acid value from 150 mg KOH/g to 250 mg KOH/g, or from 180 mg KOH/g to 220 mg KOH/g, or from 190 mg KOH/g to 200 mg KOH/g. In a further embodiment, the dimer acid is ATUREX™ 1001 (CAS 61788-89-4), available from Aturex Group.

[0062] The dimer acid may comprise two or more embodiments disclosed herein.

[0063] Dicarboxylic Acid

[0064] The DAPP Component contains the reaction product of a reaction mixture including (i) the dimer acid, (ii) a dicarboxylic acid, and (iii) a polyol.

[0065] The (ii) dicarboxylic acid is not a dimer acid. In other words, the (ii) dicarboxylic acid is structurally distinct and/or compositionally distinct from the (i) dimer acid in the reaction mixture.

[0066] Nonlimiting examples of suitable dicarboxylic acids include aliphatic acids, aromatic acids, and combinations thereof. Nonlimiting examples of suitable aromatic dicarboxylic acids include phthalic acid, isophthalic acid, and terephthalic acid. Nonlimiting examples of suitable of suitable aliphatic dicarboxylic acids include hexahydrophthalic acid, cyclohexane dicarboxylic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, maleic acid, fumaric acid, itaconic acid, malonic acid, suberic acid, 2-methyl succinic acid, 3, 3-diethyl glutaric acid, 2, 2-dimethyl succinic acid, and trimellitic acid. As used herein, the term “acid” also includes any anhydrides of said acid. Saturated aliphatic and/or aromatic acids are also suitable, such as adipic acid or isophthalic acid.

[0067] In an embodiment, the dicarboxylic acid has from four, or five, or six to seven, or eight, or nine, or ten carbon atoms. In another embodiment, the dicarboxylic acid has from four to ten carbon atoms, or from six to eight carbon atoms. In a further embodiment, the dicarboxylic acid has eight carbon atoms.

[0068] In an embodiment, the dicarboxylic acid is selected from phthalic acid, isophthalic acid, terephthalic acid, azelaic acid, sebacic acid, adipic acid, and combinations thereof. In a further embodiment, the dicarboxylic acid is selected from phthalic acid, isophthalic acid, terephthalic acid, and combinations thereof. In another embodiment, the dicarboxylic acid is phthalic acid.

[0069] The dicarboxylic acid may comprise two or more embodiments disclosed herein.

[0070] Polyol

[0071] The DAPP Component contains the reaction product of a reaction mixture including (i) the dimer acid, (ii) the dicarboxylic acid, and (iii) a polyol.

[0072] Nonlimiting examples suitable polyols include diols (which contain two hydroxyl groups), triols (which contain three hydroxyl groups), and combinations thereof. In an embodiment, the polyol includes a diol and a triol.

[0073] Nonlimiting examples of suitable diols include 2-methyl-1, 3-propanediol (MPG); 3-methyl-1,5-pentanediol (MPD); ethylene glycol; butylene glycol; diethylene glycol (DEG); triethylene glycol; polyalkylene glycols, such as polyethylene glycol; 1, 2-propanediol; 1, 3-propanediol; 1, 3-butanediol; 1, 4-butanediol; 1, 6-hexanediol; and neopentyl glycol (NPG).

[0074] A nonlimiting example of a suitable triol is trimethylolpropane (TMP).

[0075] In an embodiment, the polyol is selected from 2-methyl-1, 3-propanediol (MPG), trimethylolpropane (TMP), 1, 4-butanediol, 1, 6-hexanediol, and neopentyl glycol (NPG), and combinations thereof.

[0076] In an embodiment, the polyol includes from 96.0 wt %, or 98.0 wt %, or 98.4 wt % to 98.7 wt %, or 99.0 wt % diol; and a reciprocal amount of triol; or from 1.0 wt %, or 1.3 wt % to 1.6 wt %, or 2.0 wt %, or 4.0 wt % triol, based on the total weight of polyol in the reaction mixture.

[0077] In an embodiment, the polyol includes from 98.0 wt %, or 98.4 wt % to 98.7 wt %, or 99.0 wt % MPG; and a reciprocal amount of TMP; or from 1.0 wt %, or 1.3 wt % to 1.6 wt %, or 2.0 wt % TMP, based on the total weight of polyol in the reaction mixture.

[0078] In an embodiment, the polyol includes a triol and a diol at a triol:diol weight ratio from 0.010:1, or 0.013:1 to 0.016:1, or 0.020:1, or 0.040:1. In another embodiment, the polyol includes a triol and a diol at a triol:diol weight ratio from 0.010:1 to 0.040:1, or from 0.010:1 to 0.020:1, or from 0.013:1 to 0.016:1.

[0079] In an embodiment, the polyol excludes polyalkylene glycols, such as polyethylene glycol (also known as polyether glycol).

[0080] The polyol may comprise two or more embodiments disclosed herein.

[0081] Optional Reaction Mixture Additive

[0082] In an embodiment, the DAPP Component contains the reaction product of a reaction mixture including (i) from 20 wt % to 60 wt % dimer acid, (ii) the dicarboxylic acid, (iii) the polyol, and (iv) an optional additive.

[0083] Nonlimiting examples of suitable optional additives include adhesion promoters, chain extenders, catalysts, and combinations thereof.

[0084] Nonlimiting examples of a suitable adhesion promoters include aminosilane, epoxy silane, phosphate ester, epoxy resin, and combination thereof.

[0085] Nonlimiting examples of suitable chain extenders include glycerine; trimethylol propane; diethylene glycol; propanediol; 2-methyl-1, 3-propanediol; 3-methyl-1, 5-pentanediol; and combinations thereof.

[0086] Nonlimiting examples of suitable catalysts include tetra-n-butyl titanate, zinc sulphate, organic tin catalyst, and combinations thereof.

[0087] In an embodiment, the reaction mixture excludes a chain extender.

[0088] The optional additive may comprise two or more embodiments disclosed herein.

[0089] Reaction Mixture

[0090] The DAPP Component contains the reaction product of a reaction mixture including (i) from 20 wt % to 60 wt % dimer acid, based on the total weight of the DAPP Component, (ii) the dicarboxylic acid, (iii) the polyol, and (iv) optionally, an additive.

[0091] In an embodiment, the reaction mixture includes from 20 wt %, or 25 wt %, or 30 wt %, or 35 wt %, or 40 wt %, or 41 wt % to 52 wt %, or 55 wt %, or 60 wt % dimer acid, based on the total weight of the reaction mixture. In another embodiment, the reaction mixture includes from 20 wt % to 60 wt %, or from 20 wt % to 50 wt %, or from 30 wt % to 60 wt %, or from 40 wt % to 55 wt %, or from 41 wt % to 52 wt % dimer acid, based on the total weight of the reaction mixture.

[0092] In an embodiment, the reaction mixture includes from 10 wt %, or 15 wt % to 25 wt %, or 30 wt %, or 35 wt %, or 40 wt %, or 45 wt %, or 50 wt % dicarboxylic acid, based on the total weight of the reaction mixture. In another embodiment, the reaction mixture includes from 10 wt % to 50 wt %, or from 10 wt % to 40 wt %, or from 10 wt % to 25 wt % dicarboxylic acid, based on the total weight of the reaction mixture.

[0093] In an embodiment, the reaction mixture includes from 15 wt %, or 20 wt % to 35 wt %, or 40 wt %, or 45 wt %, or 50 wt % polyol, based on the total weight of the reaction mixture. In another embodiment, the reaction mixture includes from 15 wt % to 50 wt %, or from 15 wt % to 40 wt %, or from 15 wt % to 35 wt % polyol, based on the total weight of the reaction mixture.

[0094] In an embodiment, the reaction mixture includes from 15 wt %, or 20 wt % to 35 wt %, or 40 wt %, or 49 wt % diol; and from 0.1 wt %, or 0.5 wt % to 1.0 wt %, or 2.0 wt %, or 5.0 wt % triol, based on the total weight of the reaction mixture.

[0095] In an embodiment, the reaction mixture includes, consists essentially of, or consists of, based on the total weight of the reaction mixture: (i) 20 wt % to 60 wt %, or from 20 wt % to 50 wt %, or from 30 wt % to 60 wt %, or from 40 wt % to 55 wt %, or from 41 wt % to 52 wt % dimer acid, based on the total weight of the DAPP Component; (ii) from 10 wt % to 50 wt %, or from 10 wt % to 40 wt %, or from 10 wt % to 25 wt % dicarboxylic acid; (iii) from 15 wt % to 50 wt %, or from 15 wt % to 40 wt %, or from 15 wt % to 35 wt % polyol; and (iv) optionally, from 0 wt %, or 0.001 wt % to 0.1 wt % catalyst, such as tetra-n-butyl titanate.

[0096] It is understood that the sum of the components in each of the components, mixtures, compositions, and layers disclosed herein, including the foregoing reaction mixture, yields 100 weight percent (wt %), based on the total weight of the respective component, mixture, composition, or layer.

[0097] The reaction mixture is reacted to form a reaction product that includes a dimer acid polyester polyol (a “DAPP”). The DAPP is the polycondensation reaction product of the reaction mixture. In the polycondensation reaction, the carboxyl groups of the dimer acid and the dicarboxylic acid react with the hydroxyl groups of the polyol. In an embodiment, the reaction mixture includes a catalyst, such as tetra-n-butyl titanate. The DAPP reaction product is a hydroxyl-terminated polyester with units derived from the dimer acid.

[0098] In an embodiment, the DAPP Component includes from 20 wt %, or 25 wt %, or 30 wt %, or 35 wt %, or 40 wt %, or 41 wt % to 52 wt %, or 55 wt %, or 60 wt % dimer acid, based on the total weight of the DAPP Component. In another embodiment, the DAPP Component includes from 20 wt % to 60 wt %, or from 20 wt % to 50 wt %, or from 30 wt % to 60 wt %, or from 40 wt % to 55 wt %, or from 41 wt % to 52 wt % dimer acid, based on the total weight of the DAPP Component. Not wishing to be bound by any particular theory, it is believed that a DAPP Component containing greater than 60 wt % dimer acid will exhibit (i) incompatibility, (ii) a weight average molecular weight (Mw) and/or (iii) a viscosity that is unsuitable for laminate applications. In contrast, a laminate having an adhesive layer formed from a two-component adhesive composition that is the reaction product of an isocyanate component and a DAPP Component containing less than 20 wt % dimer acid will not exhibit suitable adhesion after the boiling-in-bag test.

[0099] In an embodiment, the DAPP has a weight average molecular weight (Mw) from 5000 g/mol, or 10000 g/mol, or 20000 g/mol to 30000 g/mol, or 40000 g/mol, or 50000 g/mol.

[0100] In an embodiment, the DAPP has an acid value from 0 mg KOH/g, or 0.01 mg KOH/g to less than 5.0 mg KOH/g.

[0101] In an embodiment, the DAPP has a hydroxyl number from 5 mg KOH/g, or 10 mg KOH/g, or 13 mg KOH/g, or 13.5 mg KOH/g to 14 mg KOH/g, or 15 mg KOH/g, or 20 mg KOH/g. In another embodiment, the DAPP has a hydroxyl number from 5 mg KOH/g to 20 mg KOH/g, or from 10 mg KOH/g to 15 mg KOH/g, or from 13.5 mg KOH/g to 15 mg KOH/g.

[0102] In an embodiment, the DAPP has one, some, or all of the following properties: (i) from 20 wt % to 60 wt %, or from 20 wt % to 50 wt %, or from 30 wt % to 60 wt %, or from 40 wt % to 55 wt %, or from 41 wt % to 52 wt % dimer acid, based on the total weight of the DAPP Component; and/or (ii) has a weight average molecular weight (Mw) from 5000 g/mol, or 10000 g/mol, or 20000 g/mol to 30000 g/mol, or 40000 g/mol, or 50000 g/mol and/or (iii) has an acid value from 0 mg KOH/g, or 0.01 mg KOH/g to less than 5.0 mg KOH/g; and/or (iv) a hydroxyl number from 5 mg KOH/g to 20 mg KOH/g, or from 10 mg KOH/g to 15 mg KOH/g, or from 13.5 mg KOH/g to 15 mg KOH/g.

[0103] In an embodiment, the DAPP has 20 wt % to 60 wt %, or from 20 wt % to 50 wt %, or from 30 wt % to 60 wt %, or from 40 wt % to 55 wt %, or from 41 wt % to 52 wt % dimer acid, based on the total weight of the DAPP Component; and the DAPP has an acid value from 0 mg KOH/g to less than 5.0 mg KOH/g.

[0104] The reaction mixture may comprise two or more embodiments disclosed herein.

[0105] Optional DAPP Component Additive

[0106] In an embodiment, the DAPP Component contains the DAPP and an optional additive.

[0107] A nonlimiting example of a suitable optional additive is a polyol. The polyol may be any polyol disclosed herein, with the proviso that the optional polyol is different than the DAPP. The polyol may be compositionally distinct and/or physically distinct from the DAPP.

[0108] In an embodiment, the optional additive is a polyol that is a polyester polyol, a polyether polyol, or a combination thereof. Nonlimiting examples of suitable polyether polyols include polypropylene glycol (PPG), polyethylene glycol (PEG), polybutylene glycol, polytetramethylene ether glycol (PTMEG), and combinations thereof.

[0109] The DAPP may comprise two or more embodiments disclosed herein.

[0110] The DAPP Component may comprise two or more embodiments disclosed herein.

[0111] C. Solvent

[0112] The two-component solvent-based adhesive composition contains the reaction product of (A) the isocyanate component; (B) the DAPP Component; and (C) a solvent.

[0113] A “solvent” is a compound that is a liquid at 25° C., and is capable of providing a continuous medium in which each of the other component in the adhesive composition is dissolved and/or dispersed within.

[0114] Nonlimiting examples of suitable solvents includes hydrocarbon solvents, polar solvents, and combinations thereof.

[0115] A “hydrocarbon solvent” contains only hydrogen and carbon atoms, including branched or unbranched, saturated or unsaturated, cyclic, polycyclic or acyclic species, and combinations thereof. In an embodiment, the hydrocarbon solvent is selected from aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, and combinations thereof.

[0116] An “aromatic hydrocarbon” is a hydrocarbon that contains one or more benzene rings. Nonlimiting examples of aromatic hydrocarbon solvents include toluene and xylene. In an embodiment, the hydrocarbon solvent is an aromatic hydrocarbon solvent that is toluene.

[0117] An “aliphatic hydrocarbon” is a hydrocarbon that is an alkane, an alkene, an alkyne, or a derivative of an alkane, an alkene or an alkyne. Nonlimiting examples of aliphatic hydrocarbon solvents include hexene, cyclohexane and methylcyclohexane (MCH). In an embodiment, the hydrocarbon solvent is an aliphatic hydrocarbon solvent containing methylcyclohexane (MCH).

[0118] A “polar solvent” is a substance capable of dissolving another substance (solute) to form a uniformly dispersed mixture (solution) at the molecular or ionic level; the solvent composed of molecules in which positive and negative electrical charges are permanently separated, as opposed to nonpolar molecules in which the charges coincide. Nonlimiting examples of polar solvents include alcohols, ketones and esters. In an embodiment, the polar solvent is a ketone. Nonlimiting examples of suitable ketones include acetone, methyl ethyl ketone and cyclohexanone.

[0119] In an embodiment, the polar solvent is an ester. Nonlimiting examples of suitable esters include butyl acetate and ethyl acetate.

[0120] In an embodiment, the solvent is selected from ethyl acetate, methyl ethyl ketone, and combinations thereof.

[0121] The solvent may comprise two or more embodiments disclosed herein.

[0122] D. Two-Component Solvent-Based Adhesive Composition

[0123] The two-component solvent-based adhesive composition contains the reaction product of (A) the isocyanate component; (B) the DAPP Component containing the reaction product of a reaction mixture including (i) from 20 wt % to 60 wt % dimer acid, (ii) dicarboxylic acid, and (iii) polyol; and (C) the solvent.

[0124] The two-component solvent-based adhesive composition is formed by mixing (A) the isocyanate component, (B) the DAPP Component, and (C) the solvent under conditions suitable to react the —NCO groups of the isocyanate component with the hydroxyl groups of the DAPP Component. In an embodiment, (A) the isocyanate component, (B) the DAPP Component, and (C) the solvent are combined and mixed at a temperature from 15° C. to 45° C. for a period from 10 minutes to 30 minutes. In an embodiment, (A) the isocyanate component, (B) the DAPP Component are completely dissolved, or substantially dissolved, in (C) the solvent.

[0125] The (C) solvent may be pre-mixed with the (A) isocyanate component and/or the (B) DAPP Component.

[0126] In an embodiment, the (C) solvent is pre-mixed with the (A) isocyanate component. In other words, the isocyanate component is mixed with solvent before it contacts the DAPP Component.

[0127] In an embodiment, the (C) solvent is pre-mixed with the (B) DAPP Component. In other words, the DAPP Component is mixed with solvent before it contacts the isocyanate component. In an embodiment, the (C) solvent is pre-mixed with the (B) DAPP Component, and the pre-mix has a solids content from 25 wt %, or 50 wt %, or 70 wt %, or 75 wt % to 80 wt %, or 90 wt %. In another embodiment, the (C) solvent is pre-mixed with the (B) DAPP Component, and the pre-mix has a solids content from 25 wt % to 90 wt %, or from 50 wt % to 90 wt %, or from 50 wt % to 80 wt %, or from 70 wt % to 80 wt %, based on the combined weight of solvent and DAPP Component.

[0128] In an embodiment, the two-component solvent-based adhesive composition includes

[0129] (B) DAPP Component and (A) isocyanate component at a Polyol:Isocyanate Weight Ratio, based on dry weight, from 100:5, or 100:10, or 100:12 to 100:13, or 100:14, or 100:15, or 100:20, or 100:35. In another embodiment, the two-component solvent-based adhesive composition includes (B) DAPP Component and (A) isocyanate component at a Polyol:Isocyanate Weight Ratio from 100:5 to 100:35, or from 100:10 to 100:20, or from 100:10 to 100:15, or from 100:12 to 100:13.

[0130] In an embodiment, the two-component solvent-based adhesive composition contains from 10 wt %, or 20 wt %, or 30 wt %, or 40 wt %, or 50 wt % to 60 wt %, or 70 wt %, or 75 wt % solvent, based on the total weight of the two-component solvent-based adhesive composition.

[0131] In an embodiment, the two-component solvent-based adhesive composition contains, consists essentially of, or consists of, the reaction product of

[0132] (A) an isocyanate component comprising a multifunctional isocyanate;

[0133] (B) a dimer acid polyester polyol component containing, consisting essentially of, or consisting of, the reaction product of a reaction mixture including: (i) from 20 wt % to 60 wt %, or from 20 wt % to 50 wt %, or from 30 wt % to 60 wt %, or from 40 wt % to 55 wt %, or from 41 wt % to 52 wt % dimer acid having one, some, or all of the following properties: (1) an acid value from 150 mg KOH/g to 250 mg KOH/g, or from 180 mg KOH/g to 220 mg KOH/g, or from 190 mg KOH/g to 200 mg KOH/g; and/or (2) the Structure (A); and/or (3) is a C.sub.36 dimer acid; (ii) from 10 wt % to 50 wt %, or from 10 wt % to 40 wt %, or from 10 wt % to 25 wt % dicarboxylic acid, selected from phthalic acid, isophthalic acid, terephthalic acid, azelaic acid, sebacic acid, adipic acid, and combinations thereof, and (iii) from 15 wt % to 50 wt %, or from 15 wt % to 40 wt %, or from 15 wt % to 35 wt % polyol containing, consisting essentially of, or consisting of: (1) from 96.0 wt %, or 98.0 wt %, or 98.4 wt % to 98.7 wt %, or 99.0 wt % diol, based on the total weight of polyol in the reaction mixture; (2) from 1.0 wt %, or 1.3 wt % to 1.6 wt %, or 2.0 wt %, or 4.0 wt % triol, based on the total weight of polyol in the reaction mixture;

[0134] wherein the DAPP Component has one, some, or all, of the following properties: (i) includes from 20 wt % to 60 wt %, or from 20 wt % to 50 wt %, or from 30 wt % to 60 wt %, or from 40 wt % to 55 wt %, or from 41 wt % to 52 wt % dimer acid, based on the total weight of the DAPP Component; and/or (ii) a weight average molecular weight (Mw) from 5000 g/mol, or 10000 g/mol, or 20000 g/mol to 30000 g/mol, or 40000 g/mol, or 50000 g/mol; and/or (iii) an acid value from 0 mg KOH/g, or 0.01 mg KOH/g to less than 5.0 mg KOH/g;

[0135] (C) a solvent; and

[0136] (D) optionally, an additive;

[0137] wherein the two-component solvent-based adhesive composition has a Polyol:Isocyanate Weight Ratio from 100:5 to 100:35, or from 100:10 to 100:20, or from 100:10 to 100:15, or from 100:12 to 100:13.

[0138] The two-component solvent-based adhesive composition may comprise two or more embodiments disclosed herein.

[0139] E. Laminate

[0140] The present disclosure provides a laminate. The laminate includes a first substrate, a second substrate, and an adhesive layer between the first substrate and the second substrate. The adhesive layer is formed from the two-component solvent-based adhesive composition.

[0141] The two-component solvent-based adhesive composition may be any two-component solvent-based adhesive composition disclosed herein.

[0142] First Substrate and Second Substrate

[0143] The laminate includes a first substrate and a second substrate.

[0144] The first substrate and the second substrate may be the same or different. In an embodiment, the first substrate and the second substrate are the same, such that they have the identical compositions and identical structures.

[0145] In an embodiment, the first substrate and the second substrate are compositionally distinct and/or structurally distinct from one another.

[0146] It is understood that the below description referring to a “substrate” refers to the first substrate and the second substrate, individually and/or collectively.

[0147] A nonlimiting example of a suitable substrate is a film. The film may be a monolayer film or a multilayer film. The multilayer film contains two layers, or more than two layers. For example, the multilayer film can have two, three, four, five, six, seven, eight, nine, ten, eleven, or more layers. In an embodiment, the multilayer film contains only two layers, or only three layers.

[0148] In an embodiment, the film is a monolayer film with one, and only one, layer.

[0149] In an embodiment, the film includes a layer containing a component selected from ethylene-based polymer (PE), propylene-based polymer (PP), polyamide (such as nylon), polyester, ethylene vinyl alcohol (EVOH) copolymer, polyethylene terephthalate (PET), ethylene vinyl acrylate (EVA) copolymer, ethylene methyl acrylate copolymer, ethylene ethyl acrylate copolymer, ethylene butyl acrylate copolymer, ethylene acrylic acid copolymer, ethylene methacrylic acid copolymer, an ionomer of ethylene acrylic acid, an ionomer of methacylic acid, maleic anhydride grafted ethylene-based polymer, a polylactic acid (PLA), a polystyrene, a metal foil, a cellulose, cellophane, nonwoven fabric, and combinations thereof. A nonlimiting example of a suitable metal foil is aluminum foil. Each layer of a multilayer film may for formed from the same component, or from different components.

[0150] In an embodiment, the film includes a layer containing metal foil.

[0151] In an embodiment, the film is a monolayer film having a single layer that is an ethylene-based polymer layer. In a further embodiment, the film is a monolayer film having a single layer that is a polyethylene layer.

[0152] The substrate, and further the film, is a continuous structure with two opposing surfaces.

[0153] In an embodiment, the substrate has a thickness from 5 μm, or 10 μm, or 12 μm, or 15 μm, or 20 μm, or 21 μm to 23 μm, or 24 μm, or 25 μm, or 30 μm, or 35 μm, or 40 μm, or 45 μm, or 50 μm, or 100 μm, or 150 μm, or 200 μm, or 250 μm, or 300 μm, or 350 μm, or 400 μm, or 450 μm, or 500 rm.

[0154] In an embodiment, the substrate excludes cellulose-based substrates, such as paper and wood.

[0155] In an embodiment, the first substrate is a film having a layer that is a metal foil layer; and the second substrate is a monolayer film having a single layer that is a PE layer.

[0156] The film may comprise two or more embodiments disclosed herein.

[0157] The first substrate may comprise two or more embodiments disclosed herein.

[0158] The second substrate may comprise two or more embodiments disclosed herein.

[0159] The two-component solvent-based adhesive composition is applied between the first substrate and the second substrate, such as with a Nordmeccanica Labo Combi 400 laminator.

[0160] Nonlimiting examples of suitable application methods include brushing, pouring, spraying, coating, rolling, spreading, and injecting.

[0161] In an embodiment, the two-component solvent-based adhesive composition is applied between the first substrate and the second substrate at a coat weight, based on the dry weight, from 3.0 grams per square meter (g/m.sup.2), or 3.5 g/m.sup.2, or 4.0 g/m.sup.2 to 4.5 g/m.sup.2; or 5.0 g/m.sup.2. In another embodiment, the two-component solvent-based adhesive composition is applied between the first substrate and the second substrate at a coat weight from 3.0 g/m.sup.2 to 5.0 g/m.sup.2, or from 4.0 g/m.sup.2 to 4.5 g/m.sup.2.

[0162] In an embodiment, the two-component solvent-based adhesive composition is uniformly applied between on first substrate, the solvent is evaporated to form an adhesive layer, and then the adhesive layer is brought into contact with the second substrate. A “uniform application” is a layer of the composition that is continuous (not intermittent) across a surface of the substrate, and of the same, or substantially the same, thickness across the surface of the substrate. In other words, a composition that is uniformly applied to a substrate directly contacts the substrate surface, and the composition is coextensive with the substrate surface.

[0163] The two-component solvent-based adhesive composition and the first substrate are in direct contact with each other. The term “directly contacts,” as used herein, is a layer configuration whereby a substrate is located immediately adjacent to a two-component solvent-based adhesive composition, or an adhesive layer and no intervening layers, or no intervening structures, are present between the substrate and the two-component solvent-based adhesive composition, or the an adhesive layer. The two-component solvent-based adhesive composition directly contacts a surface of the first substrate. The structure containing the first substrate and the two-component solvent-based adhesive composition has the following Structure (B):

First Substrate/Two-Component Solvent-Based Adhesive Composition  Structure (B)

[0164] In an embodiment, the Structure (B) is dried to form an adhesive layer in direct contact with the first substrate. In an embodiment, the Structure (B) is dried by passing it through an oven at a temperature sufficient to to evaporate all, or substantially all, of the solvent from the two-component solvent-based adhesive composition. Then, the adhesive layer is contacted with the second substrate to form a laminate. The laminate has the following Structure (C):

First Substrate/Adhesive Layer/Second Substrate Structure  (C).

[0165] In an embodiment, the adhesive layer and the second substrate are in direct contact with each other. The adhesive layer directly contacts a surface of the second substrate.

[0166] The adhesive layer of Structure (B) is formed from curing, or drying the two-component solvent-based adhesive composition. The two-component solvent-based adhesive composition is formed from mixing and reacting the (A) isocyanate component and the (B) DAPP Component in the presence of (C) a solvent.

[0167] In an embodiment, the two-component solvent-based adhesive composition is cured in the absence, or in the substantial absence, of a photo-initiator.

[0168] In an embodiment, the two-component solvent-based adhesive composition is cured in the absence, or in the substantial absence, of water.

[0169] The laminate includes the first substrate in direct contact with the adhesive layer, and the second substrate in direct contact with the adhesive layer.

[0170] The laminate includes alternating substrate layers and adhesive layers. The laminate includes at least three total layers, total layers including the substrate layers and the adhesive layers. In an embodiment, the laminate includes from three to four, or five, or six, or seven, or eight, or nine, or ten total layers.

[0171] In an embodiment, the first substrate is a film having a layer that is a metal foil layer; and the second substrate is a monolayer film having a single layer that is a PE layer, and the laminate has an initial bond strength from 5 N/15 mm, or 9 N/15 mm, or 10 N/15 mm to 11 N/15 mm, or 12 N/15 mm, or 15 N/15 mm. In a further embodiment, the laminate has an initial bond strength from 10 N/15 mm to 15 N/15 mm, or from 10 N/15 mm to 12 N/15 mm. In another embodiment, the laminate has an initial bond strength greater than 5 N/15 mm, or greater than 9 N/15 mm, or greater than 10 N/15 mm.

[0172] In an embodiment, the first substrate is a film having a layer that is a metal foil layer; and the second substrate is a monolayer film having a single layer that is a PE layer, and the laminate has a bond strength after the boil-in-bag test from 4.0 N/15 mm, or 5.0 N/15 mm, or 6.0 N/15 mm to 8.0 N/15 mm, or 9.0 N/15 mm, or 10 N/15 mm, or 15 N/15 mm. In a further embodiment, the laminate has a bond strength after the boil-in-bag test from 4.0 N/15 mm to 15 N/15 mm, or from 5.0 N/15 mm to 10 N/15 mm, or from 6.0 N/15 mm to 8.0 N/15 mm. In another embodiment, the laminate has a bond strength after the boil-in-bag test greater than 4 N/15 mm, or greater than 5 N/15 mm, or greater than 6 N/15 mm.

[0173] In an embodiment, the first substrate is a film having a layer that is a metal foil layer; and the second substrate is a monolayer film having a single layer that is a PE layer, and the laminate has a bond strength retention after the boil-in-bag test of at least 50%, or at least 55%, or at least 60%, or at least 65%, or at least 68%. In another embodiment, the laminate has a bond strength retention after the boil-in-bag test from 50% to 100%, or from 60% to 100%, or from 65% to 100%.

[0174] In an embodiment, the first substrate is a film having a layer that is a metal foil layer; and the second substrate is a monolayer film having a single layer that is a PE layer, and the laminate has a bond strength after chemical aging from 2.0 N/15 mm, or 2.5 N/15 mm, or 3.0 N/15 mm, or 3.5 N/15 mm to 4.0 N/15 mm, or 5.0 N/15 mm, or 7.0 N/15 mm, or 10 N/15 mm. In a further embodiment, the laminate has a bond strength after chemical aging from 2.0 N/15 mm to 10 N/15 mm, or from 3.0 N/15 mm to 10 N/15 mm, or from 3.0 N/15 mm to 5.0 N/15 mm. In another embodiment, the laminate has a bond strength after chemical aging greater than 2 N/15 mm, or greater than 3 N/15 mm, or greater than 3.5 N/15 mm.

[0175] In an embodiment the first substrate is a film having a layer that is a metal foil layer; and the second substrate is a monolayer film having a single layer that is a PE layer, and the laminate has a bond strength retention after chemical aging of at least 25%, or at least 30%, or at least 35%. In another embodiment, the laminate has a bond strength retention after chemical aging from 25% to 100%, or from 30% to 100%, or from 35% to 100%.

[0176] In an embodiment, the first substrate is a film having a layer that is a metal foil layer; and the second substrate is a monolayer film having a single layer that is a PE layer, and the laminate has an initial heat seal strength from 30 N/15 mm, or 40 N/15 mm, or 45 N/15 mm, or 50 N/15 mm to 60 N/15 mm, or 70 N/15 mm, or 75 N/15 mm, or 100 N/15 mm. Ina further embodiment, the laminate has an initial heat seal strength from 30 N/15 mm to 100 N/15 mm, or from 40 N/15 mm to 75 N/15 mm, or from 45 N/15 mm to 75 N/15 mm. In another embodiment, the laminate has an initial heat seal strength greater than 30 N/15 mm, or greater than 40 N/15 mm, or greater than 50 N/15 mm.

[0177] In an embodiment, the first substrate is a film having a layer that is a metal foil layer; and the second substrate is a monolayer film having a single layer that is a PE layer, and the laminate has a heat seal strength after the boil-in-bag test from 35 N/15 mm, or 40 N/15 mm, or 45 N/15 mm, or 50 N/15 mm to 55 N/15 mm, or 60 N/15 mm, or 65 N/15 mm, or 70 N/15 mm, or 75 N/15 mm. In a further embodiment, the laminate has a heat seal strength after the boil-in-bag test from 35 N/15 mm to 75 N/15 mm, or from 40 N/15 mm to 75 N/15 mm, or from 50 N/15 mm to 75 N/15 mm. In another embodiment, the laminate has a heat seal strength after the boil-in-bag test greater than 35 N/15 mm, or greater than 40 N/15 mm, or greater than 50 N/15 mm.

[0178] In an embodiment, the first substrate is a film having a layer that is a metal foil layer; and the second substrate is a monolayer film having a single layer that is a PE layer, and the laminate has a heat seal strength retention after the boil-in-bag test of at least 80%, or at least 85%, or at least 90%, or at least 95%, or at least 100%.

[0179] In an embodiment, the first substrate is a film having a layer that is a metal foil layer; and the second substrate is a monolayer film having a single layer that is a PE layer, and the laminate has a heat seal strength after chemical aging from 35 N/15 mm, or 40 N/15 mm, or 41 N/15 mm to 45 N/15 mm, or 50 N/15 mm, or 60 N/15 mm, or 70 N/15 mm, or 75 N/15 mm. In a further embodiment, the laminate has a heat seal strength after chemical aging from 35 N/15 mm to 75 N/15 mm, or from 40 N/15 mm to 75 N/15 mm. In another embodiment, the laminate has a heat seal strength after chemical aging greater than 35 N/mm, or greater than 40 N/15 mm.

[0180] In an embodiment, the first substrate is a film having a layer that is a metal foil layer; and the second substrate is a monolayer film having a single layer that is a PE layer, and the laminate has a heat seal strength retention after chemical aging of at least 75%, or at least 80%, or at least 82%. In another embodiment, the laminate has a heat seal strength retention after chemical aging from 75% to 100%, or from 80% to 100%, or from 82% to 100%.

[0181] In an embodiment, the first substrate is a film having a layer that is a metal foil layer; and the second substrate is a monolayer film having a single layer that is a PE layer, and the laminate does not bubble after the boil-in-bag test.

[0182] In an embodiment, the first substrate is a film having a layer that is a metal foil layer; and the second substrate is a monolayer film having a single layer that is a PE layer, and the laminate does not delaminate after chemical aging.

[0183] In an embodiment, the first substrate is a film having a layer that is a metal foil layer; and the second substrate is a monolayer film having a single layer that is a PE layer, and the laminate has (A) a bond strength after the boil-in-bag test from 4.0 N/15 mm to 15 N/15 mm, or from 5.0 N/15 mm to 10 N/15 mm, or from 6.0 N/15 mm to 8.0 N/15 mm; and (B) a bond strength after chemical aging from 2.0 N/15 mm to 10 N/15 mm, or from 3.0 N/15 mm to 10 N/15 mm, or from 3.0 N/15 mm to 5.0 N/15 mm.

[0184] In an embodiment, the first substrate is a film having a layer that is a metal foil layer; and the second substrate is a monolayer film having a single layer that is a PE layer, and the laminate has (A) a heat seal strength after the boil-in-bag test from 35 N/15 mm to 75 N/15 mm, or from 40 N/15 mm to 75 N/15 mm, or from 50 N/15 mm to 75 N/15 mm; and (B) a heat seal strength after chemical aging from 35 N/mm to 75 N/15 mm, or from 40 N/15 mm to 75 N/15 mm.

[0185] In an embodiment, the laminate includes, consists essentially of, or consists of:

[0186] a first substrate that is a film having a layer that is a metal foil layer;

[0187] a second substrate that is a monolayer film having a single layer that is a PE layer; and

[0188] an adhesive layer between the first substrate and the second substrate, the adhesive layer formed from a two-component solvent-based adhesive composition containing, consisting essentially of, or consisting of the reaction product of:

[0189] (A) an isocyanate component comprising a multifunctional isocyanate;

[0190] (B) a dimer acid polyester polyol component containing, consisting essentially of, or consisting of, the reaction product of a reaction mixture including: (i) from 20 wt % to 60 wt %, or from 20 wt % to 50 wt %, or from 30 wt % to 60 wt %, or from 40 wt % to 55 wt %, or from 41 wt % to 52 wt % dimer acid, the dimer acid having one, some, or all of the following properties: (1) an acid value from 150 mg KOH/g to 250 mg KOH/g, or from 180 mg KOH/g to 220 mg KOH/g, or from 190 mg KOH/g to 200 mg KOH/g; and/or (2) the Structure (A); and/or (3) is a C.sub.36 dimer acid; (ii) from 10 wt % to 50 wt %, or from 10 wt % to 40 wt %, or from 10 wt % to 25 wt % dicarboxylic acid, selected from phthalic acid, isophthalic acid, terephthalic acid, azelaic acid, sebacic acid, adipic acid, and combinations thereof, and (iii) from 15 wt % to 50 wt %, or from 15 wt % to 40 wt %, or from 15 wt % to 35 wt % polyol containing, consisting essentially of, or consisting of: (1) from 96.0 wt %, or 98.0 wt %, or 98.4 wt % to 98.7 wt %, or 99.0 wt % diol, based on the total weight of polyol in the reaction mixture; (2) from 1.0 wt %, or 1.3 wt % to 1.6 wt %, or 2.0 wt %, or 4.0 wt % triol, based on the total weight of polyol in the reaction mixture;

[0191] wherein the DAPP Component includes from 20 wt % to 60 wt %, or from 20 wt % to 50 wt %, or from 30 wt % to 60 wt %, or from 40 wt % to 55 wt %, or from 41 wt % to 52 wt % units derived from dimer acid, based on the total weight of the DAPP, and the DAPP has one, or both, of the following properties: (i) a weight average molecular weight (Mw) from 5000 g/mol, or 10000 g/mol, or 20000 g/mol to 30000 g/mol, or 40000 g/mol, or 50000 g/mol; and/or (ii) an acid value from 0 mg KOH/g, or 0.01 mg KOH/g to less than 5.0 mg KOH/g;

[0192] (C) a solvent; and

[0193] (D) optionally, an additive;

[0194] wherein the two-component solvent-based adhesive composition has a Polyol:Isocyanate Weight Ratio from 100:10 to 100:15, or from 100:12 to 100:13;

[0195] wherein the laminate has one, some, or all of the following properties: (A) an initial bond strength from 10 N/15 mm to 15 N/15 mm, or from 10 N/15 mm to 12 N/15 mm; and/or (B) a bond strength after the boil-in-bag test from 4.0 N/15 mm to 15 N/15 mm, or from 5.0 N/15 mm to 10 N/15 mm, or from 6.0 N/15 mm to 8.0 N/15 mm; and/or (C) a bond strength retention after the boil-in-bag test from 50% to 100%, or from 60% to 100%, or from 65% to 100%; and/or (D) a bond strength after chemical aging from 2.0 N/15 mm to 10 N/15 mm, or from 3.0 N/15 mm to 10 N/15 mm, or from 3.0 N/15 mm to 5.0 N/15 mm; and/or (E) a bond strength retention after chemical aging from 25% to 100%, or from 30% to 100%, or from 35% to 100%; and/or (F) an initial heat seal strength from 30 N/15 mm to 100 N/15 mm, or from 40 N/15 mm to 75 N/15 mm, or from 45 N/15 mm to 75 N/15 mm; and/or (G) a heat seal strength after the boil-in-bag test from 35 N/15 mm to 75 N/15 mm, or from 40 N/15 mm to 75 N/15 mm, or from 50 N/15 mm to 75 N/15 mm; and/or (H) a heat seal strength retention after the boil-in-bag test of at least 80%, or at least 85%, or at least 90%, or at least 95%, or at least 100%; and/or (I) a heat seal strength after chemical aging from 35 N/15 mm to 75 N/15 mm, or from 40 N/15 mm to 75 N/15 mm; and/or (J) a heat seal strength retention after chemical aging from 75% to 100%, or from 80% to 100%, or from 82% to 100%; and/or (K) the laminate does not bubble after the boil-in-bag test; and/or (L) the laminate does not delaminate after chemical aging.

[0196] The laminate may comprise two or more embodiments disclosed herein.

[0197] F. Method of Forming a Two-Component Solvent-Based Adhesive Composition

[0198] The present disclosure also provides a method of forming the two-component solvent-based adhesive composition.

[0199] In an embodiment, the method includes (i) providing a DAPP Component containing from 20 wt % to 60 wt % units derived from dimer acid, based on the total weight of the DAPP Component; (ii) providing an isocyanate component, and (iii) reacting the DAPP Component with the isocyanate component to form the two-component solvent-based adhesive composition.

[0200] The DAPP Component, the isocyanate component, and the two-component solvent-based adhesive composition may be any respective DAPP Component, isocyanate component, and two-component solvent-based adhesive composition disclosed herein.

[0201] In an embodiment, the process includes forming the DAPP Component by (a) providing a reaction mixture containing from 20 wt % to 60 wt % dimer acid, a dicarboxylic acid, and a polyol; and (b) polycondensing the reaction mixture to form a dimer acid polyester polyol component.

[0202] The (C) solvent may be pre-mixed with the (A) isocyanate component and/or the (B) DAPP Component.

[0203] The method may comprise two or more embodiments disclosed herein.

[0204] The present disclosure also provides an article containing the laminate. Nonlimiting examples of suitable articles include packages, bags, and pouches.

[0205] In an embodiment, the laminate contacts a comestible. A “comestible” is an edible food item.

[0206] By way of example, and not limitation, some embodiments of the present disclosure will now be described in detail in the following Examples.

EXAMPLES

[0207] The materials used in the examples are provided in Table 1 below.

TABLE-US-00001 TABLE 1 Material Properties Source Coreactant F solvent-based polyisocyanate composition The Dow Chemical 75wt % polyisocyanate.sup.1; 25wt % ethyl acetate.sup.1 Company ATUREX ™ 1001 dimer acid (CAS 61788-89-4) having the Structure (A) Aturex Group greater than 98 wt % dimer; acid value = 194-200 mg KOH/g phthalic acid [00002] Sinopharm 2-methyl-1,3-propanediol (MPG) [00003] Sigma trimethylolpropane (TMP) [00004] Sinopharm TYZOR ™ TBT tetra-n-butyl titanate (catalyst) Sigma ethyl acetate solvent Sinopharm ADCOTE ™ 545S solvent-based polyester polyol composition The Dow Chemical 66.7 wt % polyol.sup.2; 33.3 wt % methyl ethyl ketone (solvent).sup.2 Company ADCOTE ™ 563EA solvent-based polyester polyol composition The Dow Chemical 80 wt % polyol.sup.2; 20 wt % ethyl acetate (solvent).sup.2 Company .sup.1Based on the total weight of the solvent-based polyisocyanate composition. .sup.2Based on the total weight of the solvent-based polyol composition.

[0208] A. Preparation of the Dimer Acid Polyester Polyol Component

[0209] Dimer Acid Polyester Polyol (DAPP) Component Examples 1-2 and Comparative Sample 3 each is prepared by placing the components of Table 2 in a Kettle equipped with an agitator and a glass condenser, and heating the Kettle to 100° C. until the reaction mixture turns to a liquid. The amounts provided in Table 2 are in grams (g). Once the reaction mixture is in a liquid form, the agitator is turned on and the reaction mixture is mixed while monitoring the temperature inside the Kettle and the temperature of the glass condenser, to ensure that the top temperature of the glass condenser is between 100° C. and 103° C. Once the reaction mixture temperature increases to 220° C. and the top temperature of the glass condenser decreases to less than 100° C., a vacuum is slowly started such that the vacuum reaches a pressure of 25-30 mm Hg within 30 minutes of the vacuum being started. A vacuum pressure of 25-30 mm Hg is maintained and the acid value of the reaction mixture is measured every 25-30 minutes. TYZOR™ TBT (catalyst) is incrementally added to the reaction mixture until the acid value of the reaction mixture is equal to less than 25 mg KOH/g. Then, vacuum pressure is reduced to less than 10 mm Hg, and an additional TYZOR™ TBT (catalyst) is incrementally added over the period of at least 1 hour, until the acid value of the reaction mixture is equal to less than 5 mg KOH/g and the hydroxyl value reaches the target hydroxyl value. Then, the reaction product (a dimer acid polyester polyol) is cooled to 60° C., and ethyl acetate (solvent) is added to the reaction product to achieve a solids content of 75 wt %.

TABLE-US-00002 TABLE 2 Dimer Acid Polyester Polyol Component Examples and Comparative Sample DAPP DAPP DAPP Component Component Comparative Example B1 Example B2 Example B3 Reaction Mixture ATUREX ™ 1001 (dimer 20.00 g 25.00 g 10.00 g acid) phthalic acid (dicarboxylic 20.00 g 15.00 g 30.00 g acid) MPG (diol) 26.10 g 22.78 g 32.70 g TMP (triol) 0.365 g 0.350 g 0.400 g TYZOR ™ TBT (catalyst) 0.008 g 0.008 g 0.008 g wt % Units Derived from 41 wt % 52 wt % 19 wt % Dimer Acid in Reaction Product Dimer Acid Polyester Polyol Component wt % dimer acid polyester 75 wt % 75 wt % 75 wt % polyol wt % ethyl acetate 25 wt % 25 wt % 25 wt % (solvent) hydroxyl value 13.7 13.6 13.3 (mg KOH/g)

[0210] B. Formation of Two-Component Solvent-Based Adhesive Compositions

[0211] Two-component solvent-based adhesive compositions are prepared by mixing (A) Coreactant F (a solvent-based polyisocyanate composition) with (B) one of the DAPP Component Examples B1-B2, the DAPP Component Comparative Sample B3, ADCOTE™ 545 S (a polyester polyol component formed without dimer acid) and ADCOTE™ 563 EA (a polyester polyol component formed without dimer acid), in a kettle at room temperature (23° C.) until a homogeneous mixture is achieved, forming a two-component solvent-based adhesive composition. The components of each example and comparative example adhesive composition are provided in Table 3.

[0212] C. Formation of a Laminate

[0213] A polyethylene (PE) film that is a monolayer film having a thickness of 60 μm is provided.

[0214] A metal foil film is provided. The metal foil film is a monolayer film having a thickness of 20 μm. The metal foil film is pre-laminated with a PET film using ADCOTE™ 545 S: Coreactant F (at a weight ratio of 100:11) (a solvent-based, 2-component polyurethane adhesive, commercially available from The Dow Chemical Company) to form a Metal Foil Pre-Laminate having the following Structure (I):PET Film/ADCOTE™ 545 S:Coreactant F Adhesive Layer/Metal Foil Film Structure (I).

[0215] The example and comparative example adhesive compositions are loaded into a Nordmeccanica SDC Labo Combi 400 laminator. The laminator nip temperature is maintained at 40° C., the oven temperature is set at 60° C./70° C./80° C. for each zone, and the laminator is operated at a speed of 100 meters per minute (m/min). The adhesive composition is applied to the Metal Foil Pre-Laminate at a coat weight of 4.0-4.5 grams per square meter (g/m.sup.2), based on the dry weight of the adhesive composition, to form the following Structure (II):

Metal Foil Pre-Laminate/Adhesive Composition  Structure (II).

[0216] In Structure (II), the adhesive composition directly contacts the surface of the metal foil film layer of the Metal Foil Pre-Laminate (having the Structure (I)).

[0217] Then, the Structure (II) is cured in an oven at a temperature of 50° C. for a period of two days to evaporate all, or substantially all, of the solvent and form an adhesive layer. The PE film is brought into contact with the adhesive layer to form a laminate having the Structure (III):

Metal Foil Pre-Laminate/Adhesive Layer/PE Film  Structure (III)

[0218] The properties of each laminate example and comparative sample are provided in Table 3.

[0219] D. Results

[0220] Comparative Sample 4 and Comparative Sample 5 each includes an adhesive layer formed from (A) an isocyanate component (Coreactant F) and (B) a polyester polyol component that is not formed with dimer acid (ADCOTE™ 545 S and ADCOTE™ 563 EA, respectively). The laminate structure of Comparative Sample 4 and Comparative Sample 5 each exhibits (i) bubbling after the boil-in-bag test; (ii) delamination after chemical aging; (iii) a bond strength after the boil-in-bag test of less than 4.0 N/15 mm (3.1 N/15 mm and 1.24 N/15 mm, respectively); (iv) a bond strength after chemical aging of less than 2.0 N/15 mm (0.68 N/15 mm and 0.42 N/15 mm, respectively); (v) a heat seal strength after the boil-in-bag test of less than 35 N/15 mm (30.2 N/15 mm and 21.2 N/15 mm, respectively); and (vi) a heat seal strength after chemical aging of less than 35 N/mm (32.34 N/15 mm and 27.2 N/15 mm, respectively). Thus, Comparative Sample 4 and Comparative Sample 5 each exhibits insufficient bond strength and heat seal strength after the boil-in-bag test, and after chemical aging.

TABLE-US-00003 TABLE 3 Comparative Comparative Comparative Example 1 Example 2 Sample 3 Sample 4 Sample 5 Adhesive Composition* Coreactant F (solvent-based 11.1 wt % 11.1 wt % 11.1 wt %  9.9 wt % 12.3 wt % polyisocyanate composition) DAPP Component Example B1 88.9 wt % — — — — DAPP Component Example B2 — 88.9 wt % — — — DAPP Component Comparative — — 88.9 wt % — — Example B3 ADCOTE ™ 545S (solvent- — — — 90.1 wt % — based polyester polyol component) ADCOTE ™ 563EA (solvent- — — — — 87.7 wt % based polyester polyol component) Adhesive Composition Properties Polyol:Isocyanate Weight Ratio 100:12.5 100:12.5 100:12.5 100:11 100:14 Polyol Component Dimer Acid   41 wt %   52 wt %   19 wt %   0 wt %   0 wt % Content (wt %) Adhesive Composition wt % Units   36 wt %   46 wt %   17 wt %   0 wt %   0 wt % Derived from Dimer Acid Laminate Properties Initial Bond Strength (N/15 mm) 10.74 10.14 8.79 9.62 3.6 Bond Strength after Boil-in-Bag 7.88 6.98 3.9 3.1 1.24 (N/15 mm) Bond Strength Retention after 73.4 68.8 44.4 32.2 34.4 Boil-in-Bag (%) Bond Strength after Chemical 3.76 3.98 1.06 0.68 0.42 Aging (N/15 mm) Bond Strength Retention after 35.0 39.3 12.1 7.1 11.7 Chemical Aging (%) Initial Heat Seal Strength 49.8 50.1 53.2 51.3 45.2 (N/15 mm) Heat Seal Strength after 50.12 51.25 38.2 30.2 21.2 Boil-in-Bag (N/15 mm) Heat Seal Strength Retention 100.6 102.3 71.8 58.9 46.9 after Boil-in-Bag (%) Heat Seal Strength after 42.44 41.2 38.56 32.34 28.2 Chemical Aging (N/15 mm) Heat Seal Strength Retention 85.2 82.2 72.5 63.0 62.4 after Chemical Aging (%) Appearance after Boil-in-Bag Good Good Bubble Bubble Bubble Appearance after Chemical Good Good Delamination Delamination Delamination Aging *wt % of the respective components is based on the total weight of the adhesive composition (including the isocyanate component, the polyol component, and the solvent)

[0221] Comparative Sample 3 includes an adhesive layer formed from (A) an isocyanate component (Coreactant F) and (B) a dimer acid polyester polyol component (DAPP Component Comparative Example B3) prepared with a reaction mixture containing less than 20 wt % dimer acid (19 wt %). The laminate structure of Comparative Sample 3 exhibits bubbling after the boil-in-bag test, and exhibits delamination after chemical aging. Moreover, the laminate structure of Comparative Sample 3 exhibits (i) a bond strength after the boil-in-bag test of less than 4.0 N/15 mm (3.9 N/15 mm); and (ii) a bond strength after chemical aging of less than 2.0 N/15 mm (1.06 N/15 mm). Thus, Comparative Sample 4 and Comparative Sample 5 each exhibits insufficient bond strength after the boil-in-bag test, and after chemical aging.

[0222] Example 1 and Example 2 each includes an adhesive layer formed from (A) an isocyanate component (Coreactant F) and (B) a dimer acid polyester polyol component (DAPP Component Examples B1 and B2, respectively) prepared with a reaction mixture containing 20-60 wt % dimer acid (36 wt % and 46 wt %, respectively). The laminate structure of Example 1 and Example 2 each exhibits a good appearance (i.e., no bubbling) after the boil-in-bag test, and each exhibits a good appearance (i.e., no delamination) after chemical aging. Moreover, the laminate structure of Example 1 and Example 2 each exhibits (i) a bond strength after the boil-in-bag test of at least 4.0 N/15 mm (7.88 N/15 mm and 6.98 N/15 mm, respectively); (ii) a bond strength after chemical aging of at least 2.0 N/15 mm (3.76 N/15 mm and 3.98 N/15 mm, respectively); (iii) a heat seal strength after the boil-in-bag test of at least 35 N/15 mm (50.12 N/15 mm and 51.25 N/15 mm, respectively); and (iv) a heat seal strength after chemical aging of at least 35 N/mm (42.44 N/15 mm and 41.2 N/15 mm, respectively). Thus, Example 1 and Example 2 each exhibits sufficient bond strength and heat seal strength after the boil-in-bag test, and after chemical aging.

[0223] It is specifically intended that the present disclosure not be limited to the embodiments and illustrations contained herein, but include modified forms of those embodiments including portions of the embodiments and combinations of elements of different embodiments as come within the scope of the following claims.