Two-Component Solvent-Less Adhesive Composition

Abstract

The present disclosure provides a two-component solvent-less adhesive composition. The two-component solvent-less adhesive composition contains the reaction product of (A) an isocyanate component and (B) a polyol component containing a poly-ester-amide polycarbonate polyol. The present disclosure also provides a method of forming a two-component solvent-less adhesive composition.

Claims

1. A two-component solvent-less adhesive composition comprising the reaction product of: (A) an isocyanate component; and (B) a polyol component comprising a polyester-amide polycarbonate polyol.

2. The two-component solvent-less adhesive composition of claim 1, wherein the polyol component further comprises a phosphate-terminated polyol.

3. The two-component solvent-less adhesive composition of claim 1, wherein the polyester-amide polycarbonate polyol has a number average molecular weight (Mn) from 500 g/mol to 8,000 g/mol.

4. The two-component solvent-less adhesive composition of claim 1, wherein the polyester-amide polycarbonate polyol comprises less than 55 wt % species having a weight average molecular weight (Mw) less than 500 g/mol.

5. The two-component solvent-less adhesive composition of claim 1, wherein the polyol component comprises from 0.5 wt % to 35 wt % phosphate-terminated polyol, based on the total weight of the polyol component.

6. The two-component solvent-less adhesive composition of claim 1, wherein the isocyanate component is an aliphatic isocyanate prepolymer.

7. The two-component solvent-less adhesive composition of claim 1, wherein the phosphate-terminated polyol has the Structure (C) ##STR00005## wherein R.sup.4 is selected from the group consisting of an ether group and a substituted ether group.

8. 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-less adhesive composition of claim 1.

9. The laminate of claim 8, wherein the first substrate is a metal foil film and the second substrate is a polypropylene film; and the laminate has a bond strength after chemical aging from 0.50 N/2.54 cm to 5.0 N/2.54 cm.

10. The laminate of claim 8, wherein the first substrate is a polyethylene terephthalate film; and the laminate has a bond strength after the boil-in-bag test from 3.5 N/2.54 cm to 10.0 N/2.54 cm.

11. A method of forming a two-component solvent-less adhesive composition comprising: (A) providing a polyol component comprising a polyester-amide polycarbonate polyol; (B) providing an isocyanate component; and (C) reacting the polyol component with the isocyanate component to form the two-component solvent-less adhesive composition.

12. The method of claim 11 comprising providing the polyol component comprising (i) the polyester-amide polycarbonate polyol; and (ii) a phosphate-terminated polyol.

Description

DETAILED DESCRIPTION

[0038] The present disclosure provides a two-component solvent-less adhesive composition. The two-component solvent-less adhesive composition contains the reaction product of (A) an isocyanate component; and (B) a polyol component containing a polyester-amide polycarbonate polyol.

A. Isocyanate Component

[0039] The two-component solvent-less adhesive composition contains the reaction product of (A) an isocyanate component (NCO Component); and (B) a polyol component.

[0040] Nonlimiting examples of suitable NCO Components include aromatic isocyanates, aliphatic isocyanates, carbodiimide modified isocyanates, polyisocyanate trimers, polyfunctional isocyanate, isocyanate prepolymers, and the combinations thereof.

[0041] An “aromatic isocyanate” (or “aromatic polyisocyanate”) is an isocyanate containing one or more aromatic rings. Nonlimiting examples of suitable aromatic isocyanates include isomers of methylene diphenyl dipolyisocyanate (MDI); modified MDI such as carbodiimide modified MDI or allophanate modified MDI; isomers of toluene-dipolyisocyanate (TDI); isomers of naphthalene-dipolyisocyanate (NDI); isomers of phenylene dipolyisocyanate (PDI); and combinations thereof.

[0042] An “aliphatic isocyanate ” (or “aliphatic polyisocyanate”) is an isocyanate that 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; decane di- and tri-isocyanate; undecane di- and tri-isocyanate; dodecane di- and tri-isocyanate; isophorone diisocyanate; hexamethylene diisocyanate; diisocyanatodicyclohexylmethane; 2-methylpentane diisocyanate; 2,2,4-trimethylhexamethylene diisocyanate; 2,4,4-trimethylhexamethylene diisocyanate; norbornane diisocyanate (NBDI); xylylene diisocyanate; isomers, dimers, and/or trimers thereof; and combinations thereof.

[0043] A “polyisocyanate trimer” 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).

[0044] In an embodiment, the isocyanate is a polyfunctional isocyanate. In another embodiment, the polyfunctional isocyanate is selected from a di-isocyanate, a tri-isocyanate, and combinations thereof. In a further embodiment, the polyfunctional isocyanate is a di-isocyanate.

[0045] An “isocyanate prepolymer” is the reaction product of a polyisocyanate and at least one polyol. The polyisocyanate bonds to a polyol in a chemical reaction to form the isocyanate prepolymer. Nonlimiting examples of suitable polyisocyanates include aromatic polyisocyanates, aliphatic polyisocyanates, carbodiimide modified polyisocyanates, and combinations thereof. Nonlimiting examples of suitable polyols used to form the isocyanate prepolymer include polyester polyols, polyether polyols, aliphatic polyols, and combinations thereof. In an embodiment, the isocyanate prepolymer is the reaction product of a polyisocyanate, a polyol, and an optional catalyst. Nonlimiting examples of suitable catalysts include dibutyltin dilaurate, zinc acetate, 2,2-dimorpholinodiethylether, and combinations thereof.

[0046] In an embodiment, the isocyanate is an aliphatic isocyanate prepolymer. A nonlimiting example of a suitable aliphatic isocyanate prepolymer is MOR-FREE™ C-33, available from The Dow Chemical Company.

[0047] The NCO Component may comprise two or more embodiments disclosed herein.

B. Polyol Component

[0048] The two-component solvent-less adhesive composition contains the reaction product of (A) the NCO Component and (B) a polyol component. The polyol component contains a polyester-amide polycarbonate polyol.

Polyester-Amide Polycarbonate Polyol

[0049] The polyol component contains a polyester-polycarbonate polyol.

[0050] A “polyester-amide polycarbonate polyol” (or “PE-A PC”) is a compound that is a polyester, an amide, a polycarbonate, and a polyol. The PE-A PC can be prepared by reacting aliphatic and aromatic diacid monomer(s) (such as adipic acid (AA) and isophthalic acid), diol monomer(s) including aliphatic diol monomer and polyether diol monomer (such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol (HDO), neopentyl glycol (NPG), and 1,2-propanediol (PDO)), a carbonate monomer or polycarbonate (such as poly(1,4-butanediol-carbonate (BDO-PC)), and an amide monomer (such as ethylenediamine (EDA), N,N′-dimethylethylenediamine (DMEDA), or ethanolamine).

[0051] In an embodiment, the PE-A PC is selected from (i) the reaction product of AA, PDO, NPG, HDO, BDO-PC, and EDA; (ii) the reaction product of AA, PDO, NPG, HDO, BDO-PC, and DMEDA; (iii) the reaction product of AA, isophthalic acid, PDO, NPG, HDO, BDO-PC, and EDA(iv) the reaction product of AA, isophthalic acid, PDO, NPG, HDO, BDO-PC, and DMEDA; (v) the reaction product of AA, PDO, NPG, HDO, BDO-PC, and ethanolamine; and (vi) combinations thereof.

[0052] In an embodiment, the PE-A PC has the Structure (A):

##STR00001## [0053] wherein n is from 1, or 2 to 5; p is from 1, or 2 to 30; m is from 1, or 2 to 20; [0054] R.sup.1 is selected from —(CH.sub.2).sub.4,

##STR00002## [0055] R.sup.2 is selected from —(CH.sub.2).sub.4— and —(CH.sub.2).sub.6—; [0056] R.sup.3 is selected from —(CH.sub.2).sub.2—, —(CH.sub.2).sub.4—, —(CH.sub.2).sub.6—, —(CH.sub.2).sub.2—O—(CH.sub.2).sub.2—, —CH.sub.2—C(CH.sub.3)—, —CH.sub.2—CH(CH.sub.3)—CH.sub.2—, and —CH.sub.2—C(CH.sub.3).sub.2—CH.sub.2—; [0057] R.sup.4 is selected from O, NH, NCH.sub.3, and NCH.sub.2CH.sub.3; [0058] R.sup.5 is selected from O, NH, NCH.sub.3, and NCH.sub.2CH.sub.3; with the proviso that R.sup.4 and R.sup.5 are not both O.

[0059] In an embodiment, the PE-A PC has a number average molecular weight, Mn, from 500 g/mol, or 1000 g/mol to 1700 g/mol, or 2000 g/mol, or 3000 g/mol, or 5000 g/mol, or 8000 g/mol; or from 500 g/mol to 8000 g/mol, or from 1000 g/mol to 5000 g/mol, or from 1000 g/mol to 2000 g/mol.

[0060] In an embodiment, the PE-A PC has a weight average molecular weight, Mw, from 500 g/mol, or 2000 g/mol to 3500 g/mol, or 5000 g/mol; or from 500 g/mol to 5000 g/mol, or from 2000 g/mol to 3500 g/mol.

[0061] In an embodiment, the PE-A PC has a Mw/Mn from 1.5, or 1.6 to 1.9, or 2.2, or 2.5; or from 1.5 to 2.5, or from 1.6 to 1.2.

[0062] In an embodiment, the PE-A PC has an acid value from 0.01 mg KOH/g to 1.6 mg KOH/g, or 2.0 mg KOH/g; or from 0.01 mg KOH/g to 2.0 mg KOH/g, or from 0.01 mg KOH/g to 1.6 mg KOH/g.

[0063] In an embodiment, the PE-A PC has an OH Number from 100 mg KOH/g to 150 mg KOH/g, or 200 mg KOH/g; or from 100 mg KOH/g to 200 mg KOH/g, or from 100 mg KOH/g to 150 mg KOH/g.

[0064] In an embodiment, the PE-A PC has a glass transition temperature (Tg) from −90° C., or −80° C., or −75° C. to −65° C., or −60° C., or −55° C., or −50° C.; or from −90° C. to −50° C., or from −80° C. to −55° C.

[0065] In an embodiment, the PE-A PC has a viscosity at 25° C. from 500 mPa.Math.s, or 1000 mPa.Math.s to 3000 mPa.Math.s, or 5000 mPa.Math.s; or from 500 mPa.Math.s to 5000 mPa.Math.s, or from 900 mPa.Math.s to 3000 mPa.Math.s.

[0066] In an embodiment, the PE-A PC has a viscosity at 40° C. from 300 mPa.Math.s, or 350 mPa.Math.s to 2000 mPa.Math.s, or 4000 mPa.Math.s; or from 300 mPa.Math.s to 4000 mPa.Math.s, or from 350 mPa.Math.s to 2000 mPa.Math.s.

[0067] In an embodiment, the PE-A PC contains less than 55 wt %, or less than 50 wt %, or less than 40 wt %, or less than 30 wt %, or less than 20 wt %, or less than 15 wt %, or less than 10 wt %; or from 0 wt %, or 0.01 wt %, or 1 wt % to 10 wt %, or 15 wt %, or 20 wt %, or 30 wt %, or 40 wt %, or 50 wt %, or 55 wt %; or from 0 wt % to 10 wt % species having a Mw less than 500 g/mol, based on the total weight of the PE-A PC. In an embodiment, the PE-A PC contains less than 55 wt %, or less than 50 wt %, or less than 40 wt %, or less than 30 wt %, or less than 26 wt %; or from 0 wt %, or 0.01 wt %, or 1 wt % to 26 wt %, or 30 wt %, or 40 wt %, or 50 wt %, or 55 wt %; or from 0 wt % to 30 wt % species having a Mw less than 1000 g/mol, based on the total weight of the PE-A PC. Not wishing to be bound by any particular theory, it is believed that (i) a low level (i.e., less than 55 wt %) of species having a Mw less than 500 g/mol and/or (ii) a low level (i.e., less than 55 wt %) of species having a Mw less than 1000 g/mol in the PE-A-PC minimizes the amount of migration of low molecular weight species in cured laminating adhesives, which is advantageous in food packaging applications.

[0068] In an embodiment, the PE-A PC has one, some, or all of the following properties: (i) a Mn from 500 g/mol to 8000 g/mol, or from 1000 g/mol to 2000 g/mol; and/or (ii) a Mw from 500 g/mol to 5000 g/mol, or from 2000 g/mol to 3500 g/mol; and/or (iii) a Mw/Mn from 1.5 to 2.5, or from 1.6 to 1.2; and/or (iv) an acid value from 0.01 mg KOH/g to 2.0 mg KOH/g, or from 0.01 mg KOH/g to 1.6 mg KOH/g; and/or (v) an OH Number from 100 mg KOH/g to 200 mg KOH/g, or from 100 mg KOH/g to 150 mg KOH/g; and/or (vi) a Tg from −90° C. to −50° C., or from −80° C. to −55° C.; and/or (vii) a viscosity at 25° C. from 500 mPa.Math.s to 5000 mPa.Math.s, or from 900 mPa.Math.s to 3000 mPa.Math.s; and/or (viii) a viscosity at 40° C. from 300 mPa.Math.s to 4000 mPa.Math.s, or from 350 mPa.Math.s to 2000 mPa.Math.s; and/or (ix) from 0 wt % to 10 wt % species having a Mw less than 500 g/mol; and/or (x) from 0 wt % to 30 wt % species having a Mw less than 1000 g/mol, based on the total weight of the PE-A PC; and/or (xi) has the Structure (A); and/or (xii) is selected from the reaction product of (a) AA, PDO, NPG, HDO, BDO-PC, and EDA; (b) AA, PDO, NPG, HDO, BDO-PC, and DMEDA; (c) AA, isophthalic acid, PDO, NPG, HDO, BDO-PC, and EDA; (d) AA, isophthalic acid, PDO, NPG, HDO, BDO-PC, and DMEDA; (e) AA, PDO, NPG, HDO, BDO-PC, and ethanolamine; and (f) combinations thereof.

[0069] The PE-A PC may comprise two or more embodiments disclosed herein.

Phosphate-Terminated Polyol

[0070] In addition to the PE-A PC, the polyol component may contain a phosphate-terminated polyol.

[0071] A “phosphate-terminated polyol” (“PT-PO”) is a polyol containing at least one phosphate group having the Structure (B):

##STR00003##

[0072] The PT-PO may be prepared by reacting a polyether polyol with a phosphoric-type acid. A “phosphoric-type acid” is an orthophosphoric acid, a compound made by the condensation of orthophosphoric by the elimination of water, or a combination thereof. Nonlimiting examples of suitable phosphoric-type acid include pyrophosphoric acid, tripolyphosphoric acid, and polyphosphoric acid (PPA). In an embodiment, the PT-PO is the reaction product of a polyether polyol and PPA.

[0073] In an embodiment, the PT-PO has the Structure (C):

##STR00004## [0074] wherein R.sup.6 is an ether group or a substituted ether group.

[0075] In an embodiment, R.sup.6 is a polyether. In another embodiment, R.sup.6 contains only carbon atoms, hydrogen atoms, optional oxygen atoms, and optional phosphorous atoms.

[0076] In an embodiment, R.sup.6 is selected from a C.sub.1-C.sub.120 ether group, or a C.sub.1-C.sub.50 ether group, or a C.sub.1-C.sub.24 ether group, or a C.sub.1-C.sub.8 ether group, or a C.sub.1-C.sub.6 ether group, each of which may optionally contain one or more pendant —OH groups and/or one or more pendant Structure (B) groups.

[0077] In an embodiment, the PT-PO has an OH Number from 200 mg KOH/g, or 250 mg KOH/g to 300 mg KOH/g, or350 mg KOH/g. In an embodiment, the PT-PO has an acid value from 5 mg KOH/g, or 10 mg KOH/g, or 20 mg KOH/g to 25 mg KOH/g, or 30 mg KOH/g, or 50 mg KOH/g.

[0078] In an embodiment, the PT-PO has a viscosity at 25° C. from 1000 mPa.Math.s, or 1500 mPa.Math.s, or 1700 mPa.Math.s to 1800 mPa.Math.s, or 2000 mPa.Math.s.

[0079] In an embodiment, the PT-PO has a Mn from 500 g/mol, or 750 g/mol to 1000 g/mol, or 1500 g/mol, or 2000 g/mol, or 5000 g/mol, or 8000 g/mol. In an embodiment, the PT-PO has a Mw from 1000 g/mol, or 1400 g/mol to 1500 g/mol, or 2000 g/mol, or 3000 g/mol, or 5000 g/mol, or 8000 g/mol.

[0080] In an embodiment, the PT-PO has a Mw/Mn from 1.5, or 1.8 to 2.0, or 2.5.

[0081] In an embodiment, the PT-PO contains less than 50 wt %, or less than 40 wt %, or less than 30 wt %, or less than 27 wt %; or from 0 wt %, or 0.01 wt %, or 1 wt % to 26 wt %, or 30 wt %, or 40 wt %, or 50 wt; or from 0 wt % to 30 wt % species having a Mw less than 500 g/mol, based on the total weight of the PT-PO. In an embodiment, the PT-PO contains less than 55 wt %, or less than 50 wt %, or less than 45 wt %, or less than 42 wt %; or from 0 wt %, or 0.01 wt %, or 1 wt % to 42 wt %, or 45 wt %, or 50 wt %, or 55 wt %; or from 0 wt % to 45 wt % species having a Mw less than 1000 g/mol, based on the total weight of the PT-PO. Not wishing to be bound by any particular theory, it is believed that (i) a low level (i.e., less than 50 wt %) of species having a Mw less than 500 g/mol and/or (ii) a low level (i.e., less than 55 wt %) of species having a Mw less than 1000 g/mol in the PT-PO minimizes the amount of migration of low molecular weight species in cured laminating adhesives.

[0082] In an embodiment, the PT-PO has one, some, or all of the following properties: (i) an OH Number from 200 mg KOH/g to 350 mg KOH/g, or from 250 mg KOH/g to 300 mg KOH/g; and/or (ii) an acid value from 5 mg KOH/g to 50 mg KOH/g, or from 20 mg KOH/g to 30 mg KOH/g; and/or (iii) a viscosity at 25° C. from 1000 mPa.Math.s to 2000 mPa.Math.s, or from 1700 mPa.Math.s to 1800 mPa.Math.s; and/or (iv) a Mn from 500 g/mol to 8000 g/mol, or from 750 g/mol to 1000 g/mol; and/or (v) a Mw from 1000 g/mol to 8000 g/mol, or from 1400 g/mol to 1500 g/mol; and/or (vi) a Mw/Mn from 1.5 to 2.5, or from 1.8 to 2.0; and/or (vii) from 0 wt % to 30 wt % species having a Mw less than 500 g/mol; and/or (viii) from 0 wt % to 45 wt % species having a Mw less than 1000 g/mol, based on the total weight of the PT-PO; and/or (viii) has the Structure (C); and/or (ix) is the reaction product of a polyether polyol and PPA.

[0083] A nonlimiting example of a suitable PT-PO is the PT-PO disclosed in U.S. Patent Publication No. 2017/0226391, the entire contents of which are herein incorporated by reference.

[0084] The PT-PO may comprise two or more embodiments disclosed herein.

Optional Additive

[0085] In addition to (i) the PE-A PC and (ii) the optional PT-PO, the polyol component may contain (iv) an optional additive.

[0086] Nonlimiting examples of suitable optional additives include polyols, adhesion promoters, chain extenders, catalysts, and combinations thereof.

[0087] 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 (i) the PE-A PC and (ii) the PT-PO. The polyol may be compositionally distinct and/or physically distinct from (i) the PE-A PC and (ii) the PT-PO.

[0088] Nonlimiting examples suitable polyols include diols (which contain two —OH groups), triols (which contain three —OH groups), and combinations thereof. Nonlimiting examples of suitable diols include 2-methyl-1,3-propanediol (MPG); 3-methyl-1,5-pentanediol; ethylene glycol; butylene glycol; diethylene glycol (DEG); triethylene glycol; polyalkylene glycols, such as polyethylene glycol (PEG); 1,2-propanediol; 1,3-propanediol; 1,3-butanediol; 1,4-butanediol; 1,6-hexanediol; and NPG. A nonlimiting example of a suitable triol is trimethylolpropane (TMP).

[0089] In an embodiment, the 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 PEG, polybutylene glycol, polytetramethylene ether glycol, and combinations thereof.

[0090] Nonlimiting examples of a suitable adhesion promoters include aminosilane (e.g., (3-aminopropyl)triethoxysilane and (3-aminopropyl)trimethoxysilane), epoxy silane (e.g., (3-glycidyloxypropyl)trimethoxysilane), phosphate ester (e.g., phosphate ester based on polypropylene glycol), epoxy resin (e.g., epoxy resin based on 1,4-butanediol diglycidyl ether), and combinations thereof.

[0091] Nonlimiting examples of suitable chain extenders include glycerine; trimethylol propane; DEG; propanediol; MPG; 3-methyl-1,5-pentanediol; and combinations thereof.

[0092] Nonlimiting examples of suitable catalysts include tetra-n-butyl titanate, titanium isoproxide, zinc sulphate, organo tin catalyst (e.g., dibutyltin dilaurate), and combinations thereof.

[0093] In an embodiment, the reaction mixture excludes a chain extender.

[0094] The optional additive may comprise two or more embodiments disclosed herein.

[0095] In an embodiment, the polyol component contains, consists essentially of, or consists of (i) PE-A PC, (ii) optionally, the PT-PO, and (iii) optionally, an additive.

[0096] In an embodiment, the polyol component contains from 65 wt %, or 85 wt %, or 90 wt % to 95 wt %, or 100 wt % PE-A PC, based on the total weight of the polyol component.

[0097] In an embodiment, the polyol component contains from 65 wt %, or 70 wt %, or 75 wt %, or 80 wt %, or 85 wt %, or 90 wt % to 95 wt %, or 98 wt %, or 99 wt %, or 99.5 wt % PE-A PC; and a reciprocal amount of PT-PO, or from 0.5 wt %, or 1 wt %, or 2 wt %, or 5 wt % to 10 wt %, or 15 wt %, or 20 wt %, or 25 wt %, or 30 wt %, or 35 wt % PT-PO, based on the total weight of the polyol component. In another embodiment, the polyol component contains from 65 wt % to 99.5 wt %, or from 70 wt % to 99 wt %, or from 75 wt % to 95 wt %, or from 85 wt % to 95 wt % PE-A PC; and from 0.5 wt % to 35 wt %, or from 1 wt % to 30 wt %, or from 1 wt % to 25 wt %, or from 5 wt % to 15 wt % PT-PO.

[0098] In an embodiment, the polyol component has an OH Number from 50 mg KOH/g, or 100 mg KOH/g to 160 mg KOH/g, or 200 mg KOH/g.

[0099] It is understood that the sum of the components in each of the components, mixtures, compositions, and layers disclosed herein, including the foregoing polyol component, yields 100 weight percent (wt %), based on the total weight of the respective component, mixture, composition, or layer.

[0100] The polyol component may comprise two or more embodiments disclosed herein.

C. Two-Component Solvent-Less Adhesive Composition

[0101] The two-component solvent-less adhesive composition contains the reaction product of (A) the NCO Component; and (B) the polyol component containing the PE-A PC and (ii) optionally, PT-PO.

[0102] The two-component solvent-less adhesive composition is formed by mixing (A) the NCO Component and (B) the polyol component under conditions suitable to react the —NCO groups of the NCO Component with the —OH groups of the polyol component. In an embodiment, (A) the NCO Component and (B) the polyol component are combined and mixed at a temperature from 15° C., or 20° C. to 23° C., or 25° C., or 45° C. for a period from 10 minutes to 30 minutes.

[0103] In an embodiment, the two-component solvent-less adhesive composition includes (A) NCO Component and (B) polyol component at an Isocyanate:Polyol Weight Ratio, based on dry weight, from 100:100, or 100:125, or 100:132 to 100:189, or 100:190, or 100:195, or 100:200; or from 100:100 to 100:200, or from 100:125 to 100:195, or from 100:133 to 100:189.

[0104] The two-component solvent-less adhesive composition is void of, or substantially void of, a solvent.

[0105] In an embodiment, the two-component solvent-less adhesive composition contains, consists essentially of, or consists of, the reaction product of [0106] (A) an NCO Component comprising an aliphatic isocyanate prepolymer; [0107] (B) a polyol component containing, consisting essentially of, or consisting of [0108] (i) from 65 wt % to 100 wt %, or 65 wt % to 99.5 wt %, or from 85 wt % to 95 wt % PE-A PC, based on the total weight of the polyol component, the PE-A PC having one, some, or all of the following properties: (a) a Mn from 500 g/mol to 8000 g/mol, or from 1000 g/mol to 2000 g/mol; and/or (b) a Mw from 500 g/mol to 5000 g/mol, or from 2000 g/mol to 3500 g/mol; and/or (c) a Mw/Mn from 1.5 to 2.5, or from 1.6 to 1.2; and/or (d) an acid value from 0.01 mg KOH/g to 2.0 mg KOH/g, or from 0.01 mg KOH/g to 1.6 mg KOH/g; and/or (e) an OH Number from 100 mg KOH/g to 200 mg KOH/g, or from 100 mg KOH/g to 150 mg KOH/g; and/or (f) a Tg from −90° C. to −50° C., or from −80° C. to −55° C.; and/or (g) a viscosity at 25° C. from 500 mPa.Math.s to 5000 mPa.Math.s, or from 900 mPa.Math.s to 3000 mPa.Math.s; and/or (h) a viscosity at 40° C. from 300 mPa.Math.s to 4000 mPa.Math.s, or from 350 mPa.Math.s to 2000 mPa.Math.s; and/or (i) from 0 wt % to 10 wt % species having a Mw less than 500 g/mol; and/or (j) from 0 wt % to 30 wt % species having a Mw less than 1000 g/mol, based on the total weight of the PE-A PC; and/or (k) has the Structure (A); and/or (I) is selected from the reaction product of (1) AA, PDO, NPG, HDO, BDO-PC, and EDA; (2) AA, PDO, NPG, HDO, BDO-PC, and DMEDA; (3) AA, isophthalic acid, PDO, NPG, HDO, BDO-PC, and EDA; (4) AA, isophthalic acid, PDO, NPG, HDO, BDO-PC, and DMEDA; (5) AA, PDO, NPG, HDO, BDO-PC, and ethanolamine; and (6) combinations thereof; [0109] (ii) optionally, from 0.5 wt % to 35 wt %, or from 5 wt % to 15 wt % PT-PO, based on the total weight of the polyol component, the PT-PO having one, some all of the following properties: (a) an OH Number from 200 mg KOH/g to 350 mg KOH/g, or from 250 mg KOH/g to 300 mg KOH/g; and/or (b) an acid value from 5 mg KOH/g to 50 mg KOH/g, or from 20 mg KOH/g to 30 mg KOH/g; and/or (c) a viscosity at 25° C. from 1000 mPa.Math.s to 2000 mPa.Math.s, or from 1700 mPa.Math.s to 1800 mPa.Math.s; and/or (d) a Mn from 500 g/mol to 8000 g/mol, or from 750 g/mol to 1000 g/mol; and/or (e) a Mw from 1000 g/mol to 8000 g/mol, or from 1400 g/mol to 1500 g/mol; and/or (f) a Mw/Mn from 1.5 to 2.5, or from 1.8 to 2.0; and/or (g) from 0 wt % to 30 wt % species having a Mw less than 500 g/mol; and/or (h) from 0 wt % to 45 wt % species having a Mw less than 1000 g/mol, based on the total weight of the PT-PO; and/or (i) has the Structure (C); and/or (j) is the reaction product of a polyether polyol and PPA; and [0110] (C) optionally, an additive;
wherein the two-component solvent-less adhesive composition has an Isocyanate:Polyol Weight Ratio, based on dry weight, from 100:100 to 100:200, or from 100:133 to 100:189.

[0111] The two-component solvent-less adhesive composition may comprise two or more embodiments disclosed herein.

D. Laminate

[0112] 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-less adhesive composition.

[0113] The two-component solvent-less adhesive composition may be any two-component solvent-less adhesive composition disclosed herein.

[0114] The laminate includes a first substrate and a second substrate. 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.

[0115] In an embodiment, the first substrate and the second substrate are compositionally distinct and/or structurally distinct from one another.

[0116] It is understood that the below description referring to a “substrate” refers to the first substrate and the second substrate, individually and/or collectively.

[0117] 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.

[0118] In an embodiment, the film is a monolayer film with one, and only one, layer.

[0119] In an embodiment, the film includes a layer containing a component selected from ethylene-based polymer, 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.

[0120] In an embodiment, the film includes a layer containing metal foil.

[0121] The substrate, and further the film, is a continuous structure with two opposing surfaces.

[0122] In an embodiment, the substrate has a thickness from 5 μm, or 10 μm, or 15 μm, or 20 μm to 25 μm, or 30 μm, or 40 μm, or 50 μm, or 100 μm, or 200 μm, or 300 μm, or 400 μm, or 500 μm.

[0123] 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 an ethylene-based polymer layer (such as low density polyethylene (LDPE)) or a propylene-based polymer layer (such as polypropylene).

[0124] The first substrate may comprise two or more embodiments disclosed herein.

[0125] The second substrate may comprise two or more embodiments disclosed herein.

[0126] The two-component solvent-less adhesive composition is applied between the first substrate and the second substrate, such as with a Nordmeccanica Labo Combi laminator.

[0127] Nonlimiting examples of suitable application methods include brushing, pouring, spraying, coating, rolling, spreading, and injecting.

[0128] In an embodiment, the two-component solvent-less adhesive composition is applied between the first substrate and the second substrate at a coat weight from 1.6 grams per square meter (g/m.sup.2) to 2.0 g/m.sup.2.

[0129] In an embodiment, the two-component solvent-less adhesive composition is uniformly applied between the first substrate and 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.

[0130] The two-component solvent-less 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-less adhesive composition, or an adhesive layer and no intervening layers, or no intervening structures, are present between the substrate and the two-component solvent-less adhesive composition, or the an adhesive layer. The two-component solvent-less adhesive composition directly contacts a surface of the first substrate.

[0131] The structure containing the first substrate, the second substrate, and the two-component solvent-less adhesive composition has the following Structure (H):

First Substrate/Two-Component Solvent-Less Adhesive Composition/Second Substrate   Structure (H).

[0132] The adhesive layer of Structure (H) is formed from curing the two-component solvent-less adhesive composition. The two-component solvent-less adhesive composition is formed from mixing and reacting the (A) NCO Component and the (B) polyol component.

[0133] In an embodiment, the two-component solvent-less adhesive composition is cured in an oven at a temperature from 30° C., or 35° C. to 40° C., or 45° C., or 50° C.

[0134] In an embodiment, the two-component solvent-less adhesive composition is cured at a temperature from 20° C. to 25° C. for a period of from 1 day to 2 days, or 4 days, or 7 days.

[0135] In an embodiment, the Structure (H) is cured to form an adhesive layer between the first substrate and the second substrate, thereby forming a laminate. The laminate has the following Structure (J): First Substrate/Adhesive Layer/Second Substrate Structure (J).

[0136] The laminate includes the first substrate in direct contact with the adhesive layer, and the second substrate in direct contact with the adhesive layer.

[0137] 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 an ethylene-based polymer (such as LDPE). In a further embodiment, the laminate has one, some, or all of the following properties after 25° C. curing: (i) a bond strength after two days from 1.5 N/2.54 cm, or 1.6 N/2.54 cm to 4.6 N/2.54 cm, or 9.0 N/2.54 cm; and/or (ii) a bond strength after four days from 2.0 N/2.54 cm, or 2.5 N/2.54 cm to 6.0 N/2.54 cm, or 9.0 N/2.54 cm; and/or (iii) a bond strength after seven days from 2.5 N/2.54 cm, or 2.6 N/2.54 cm to 4.2 N/2.54 cm, or 8.0 N/2.54 cm; and/or (iv) a bond strength after fourteen days from 2.0 N/2.54 cm, or 2.5 N/2.54 cm to 4.0 N/2.54 cm, or 60.0 N/2.54 cm; and/or (v) a bond strength after the boil-in-bag test from 1.5 N/2.54 cm, or 1.6 N/2.54 cm to 3.1 N/2.54 cm, or 8.0 N/2.54 cm; or from 1.5 N/2.54 cm to 8.0 N/2.54 cm. In another embodiment, the laminate has one, some, or all of the following properties after 45° C. curing: (i) a bond strength after one day from 3.0 N/2.54 cm to 4.5 N/2.54 cm, or 7.0 N/2.54 cm; and/or (ii) a bond strength after seven days from 2.9 N/2.54 cm to 6.0 N/2.54 cm, or 8.0 N/2.54 cm; and/or (iii) a bond strength after fourteen days from 2.5 N/2.54 cm to 4.0 N/2.54 cm, or 7.0 N/2.54 cm; and/or (iv) a bond strength after the boil-in-bag test from 1.4 N/2.54 cm to 5.5 N/2.54 cm, or 8.0 N/2.54 cm; and/or (v) a bond strength after chemical aging from 0.15 N/2.54 cm, or 0.19 N/2.54 cm to 0.50 N/2.54 cm, or 3.0 N/2.54 cm.

[0138] 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 propylene-based polymer (such as polypropylene, or further a cast polypropylene). In a further embodiment, the laminate has one, some, or all of the following properties after 25° C. curing: (i) a bond strength after two days from 0.01 N/2.54 cm, or 0.03 N/2.54 cm, or 1.0 N/2.54 cm to 5.5 N/2.54 cm, or 8.0 N/2.54 cm; and/or (ii) a bond strength after four days from 1.5 N/2.54 cm, or 2.0 N/2.54 cm to 6.3 N/2.54 cm, or 7.0 N/2.54 cm; and/or (iii) a bond strength after seven days from 2.0 N/2.54 cm, or 2.5 N/2.54 cm, or 5.0 N/2.54 cm to 6.0 N/2.54 cm, or 8.0 N/2.54 cm; and/or (iv) a bond strength after fourteen days from 2.5 N/2.54 cm, or 3.0 N/2.54 cm to 6.0 N/2.54 cm, or 8.0 N/2.54 cm; and/or (v) a bond strength after the boil-in-bag test from 0.5 N/2.54 cm, or 0.80 N/2.54 cm to 2.2 N/2.54 cm, or 5.0 N/2.54 cm; or from 0.50 N/2.54 cm to 5.0 N/2.54 cm; and/or (vi) a bond strength after chemical aging from 0.5 N/2.54 cm, or 0.80 N/2.54 cm to 2.0 N/2.54 cm, or 5.0 N/2.54 cm; or from 0.5 N/2.54 cm to 5.0 N/2.54 cm. In another embodiment, the laminate has one, some, or all of the following properties after 45° C. curing: (i) a bond strength after one day from 6.0 N/2.54 cm, or 6.4 N/2.54 cm to 8.5 N/2.54 cm, or 10.0 N/2.54 cm; and/or (ii) a bond strength after seven days from 5.5 N/2.54 cm, or 5.8 N/2.54 cm to 11.0 N/2.54 cm, or 13.0 N/2.54 cm; and/or (iii) a bond strength after fourteen days from 5.0 N/2.54 cm, or 5.50 N/2.54 cm to 8.0 N/2.54 cm, or 12.0 N/2.54 cm; and/or (iv) a bond strength after the boil-in-bag test from 1.0 N/2.54 cm to 5.0 N/2.54 cm, or 8.0 N/2.54 cm; and/or (v) a bond strength after chemical aging from 0.5 N/2.54 cm, or 0.8 N/2.54 cm to 1.1 N/2.54 cm, or 5.0 N/2.54 cm; or from 0.5 N/2.54 cm to 5.0 N/2.54 cm, or from 0.5 N/2.54 cm to 1.5 N/2.54 cm.

[0139] In an embodiment, the first substrate is a monolayer film having a single layer that is PET, and the second substrate is a monolayer film having a single layer that is an ethylene-based polymer (such as LDPE). In a further embodiment, the laminate has one, some, or all of the following properties after 25° C. curing: (i) a bond strength after two days from 1.0 N/2.54 cm, or 1.2 N/2.54 cm to 9.2 N/2.54 cm, or 10.0 N/2.54 cm; and/or (ii) a bond strength after four days from 4.0 N/2.54 cm, or 4.2 N/2.54 cm to 12.2 N/2.54 cm, or 15.0 N/2.54 cm; and/or (iii) a bond strength after seven days from 6.0 N/2.54 cm, or 10.0 N/2.54 cm to 12.5 N/2.54 cm, or 15.0 N/2.54 cm; and/or (iv) a bond strength after fourteen days from 6.0 N/2.54 cm, or 10.0 N/2.54 cm to 14.2 N/2.54 cm, or 17.0 N/2.54 cm; and/or (v) a bond strength after the boil-in-bag test from 3.0 N/2.54 cm, or 3.5 N/2.54 cm, or 4.0 N/2.54 cm to 4.6 N/2.54 cm, or 10.0 N/2.54 cm; or from 3.0 N/2.54 cm to 10.0 N/2.54 cm; or from 4.0 N/2.54 cm to 10.0 N/2.54 cm; and/or (vi) a bond strength after chemical aging from 2.5 N/2.54 cm, or 2.9 N/2.54 cm to 6.0 N/2.54 cm, or 10.0 N/2.54 cm; or from 2.5 N/2.54 cm to 10.0 N/2.54 cm. In another embodiment, the laminate has one, some, or all of the following properties after 45° C. curing: (i) a bond strength after one day from 13.0 N/2.54 cm to 20.0 N/2.54 cm, or 30.0 N/2.54 cm; and/or (ii) a bond strength after seven days from 12.0 N/2.54 cm, or 13.0 N/2.54 cm to 19.0 N/2.54 cm, or 20.0 N/2.54 cm; and/or (iii) a bond strength after fourteen days from 10.0 N/2.54 cm to 15.0 N/2.54 cm, or 18.0 N/2.54 cm; and/or (iv) a bond strength after the boil-in-bag test from 2.0 N/2.54 cm, or 3.5 N/2.54 cm, or 4.0 N/2.54 cm to 9.0 N/2.54 cm, or 10.0 N/2.54 cm; or from 2.0 N/2.54 cm to 10.0 N/2.54 cm; or from 4.0 N/2.54 cm to 10.0 N/2.54 cm; and/or (v) a bond strength after chemical aging from 2.5 N/2.54 cm to 5.0 N/2.54 cm, or 10.0 N/2.54 cm.

[0140] In an embodiment, the first substrate is a monolayer film having a single layer that is PET, and the second substrate is a monolayer film having a single layer that is a propylene-based polymer (such as polypropylene, or further a cast polypropylene). In a further embodiment, the laminate has one, some, or all of the following properties after 25° C. curing: (i) a bond strength after two days from 0.05 N/2.54 cm to 1.30 N/2.54 cm, or 2.00 N/2.54 cm; and/or (ii) a bond strength after four days from 3.0 N/2.54 cm, or 5.0 N/2.54 cm to 12.0 N/2.54 cm, or 20.0 N/2.54 cm; or from 3.0 N/2.54 cm to 20.0 N/2.54 cm; and/or (iii) a bond strength after seven days from 7.0 N/2.54 cm to 16.0 N/2.54 cm, or 20.0 N/2.54 cm; and/or (iv) a bond strength after fourteen days from 7.0 N/2.54 cm to 14.1 N/2.54 cm, or 18.0 N/2.54 cm; and/or (v) a bond strength after the boil-in-bag test from 3.5 N/2.54 cm, or 4.0 N/2.54 cm, or 4.3 N/2.54 cm to 6.0 N/2.54 cm, or 10.0 N/2.54 cm; or from 3.5 N/2.54 cm to 10.0 N/2.54 cm; and/or (vi) a bond strength after chemical aging from 6.0 N/2.54 cm, or 7.9 N/2.54 cm to 10.0 N/2.54 cm, or 15.0 N/2.54 cm; or from 6.0 N/2.54 cm to 15.0 N/2.54 cm. In another embodiment, the laminate has one, some, or all of the following properties after 45° C. curing: (i) a bond strength after one day from 9.0 N/2.54 cm to 15.0 N/2.54 cm, or 20.0 N/2.54 cm; and/or (ii) a bond strength after seven days from 9.0 N/2.54 cm, or 9.6 N/2.54 cm to 14.0 N/2.54 cm, or 20.0 N/2.54 cm; and/or (iii) a bond strength after fourteen days from 10.0 N/2.54 cm to 18.0 N/2.54 cm, or 20.0 N/2.54 cm; and/or (iv) a bond strength after the boil-in-bag test from 3.5 N/2.54 cm, or 4.0 N/2.54 cm, or 6.5 N/2.54 cm, or 8.0 N/2.54 cm to 9.0 N/2.54 cm, or 10.0 N/2.54 cm; or from 3.5 N/2.54 cm to 10.0 N/2.54 cm; and/or (v) a bond strength after chemical aging from 7.0 N/2.54 cm, or 7.5 N/2.54 cm to 9.0 N/2.54 cm, or 15.0 N/2.54 cm.

[0141] In an embodiment, the laminate includes a first substrate that is a metal foil film and a second substrate that is a polypropylene film, and the laminate has a bond strength after chemical aging from 0.5 N/2.54 cm to 5.0 N/2.54 cm, or from 0.90 N/2.54 cm to 5.0 N/2.54 cm.

[0142] In an embodiment, the laminate includes a first substrate that is a PET film and the laminate has a bond strength after the boil-in-bag test from 3.5 N/2.54 cm to 10.0 N/2.54 cm, or from 4.0 N/2.54 cm to 10.0 N/2.54 cm.

[0143] The laminate may comprise two or more embodiments disclosed herein.

E. Method of Forming a Two-Component Solvent-Less Adhesive Composition

[0144] The present disclosure also provides a method of forming the two-component solvent-less adhesive composition. In an embodiment, the method includes (A) providing a polyol component containing (i) a PE-A PC and (ii) optionally, a PT-PO; (B) providing an NCO Component; and (C) reacting the polyol component with the NCO Component to form the two-component solvent-less adhesive composition.

[0145] The polyol component, the PE-A PC, the PT-PO, the NCO Component, and the two-component solvent-less adhesive composition may be any respective polyol component, PE-A PC, PT-PO, NCO Component, and two-component solvent-less adhesive composition disclosed herein.

[0146] The method may comprise two or more embodiments disclosed herein.

[0147] The present disclosure also provides an article containing the laminate. Nonlimiting examples of suitable articles include packages, bags, pouches, deep-drawn cans, and containers.

[0148] In an embodiment, the laminate contacts a comestible. A “comestible” is an edible food item.

[0149] By way of example, and not limitation, some embodiments of the present disclosure will now be described in detail in the following Examples.

EXAMPLES

[0150] The materials used in the examples are provided in Table 1 below.

TABLE-US-00001 TABLE 1 Material Properties Source TYZOR ™ TPT tetra-isopropyl titanate (catalyst) Sigma FASCAT ™ 9100 hydroxybutyltin oxide (catalyst) PMC DER ™ 731 diglycidyl ether of 1,4-butanediol Olin Epoxy ADCOTE ™ 577 aromatic isocyanate prepolymer DCC MOR-FREE ™ C-33 aliphatic isocyanate prepolymer DCC MOR-FREE ™ L82-105 solvent-free hydroxyl-terminated polyol composition DCC MOR-FREE ™ 1390A solvent-free hydroxyl-terminated polyol composition DCC VORANOL ™ CP 450 glycerine propoxylated polyether triol (polyether polyol) DCC OH number = 370-396 mg KOH/g; acid number = 0.050 mg KOH/g ISONATE ™ 125M MDI blend of 98 wt % 4,4′-diphenylmethane diisocyanate DCC and 2 wt % 2,4′-diphenylmethane diisocyanate; NCO content = 33.2 wt % adipic acid (AA) aliphatic diacid monomer Aldrich isopthalic acid (IPA) aromatic diacid monomer TCl America 1,6-hexanediol (HDO) diol monomer Aldrich neopentyl glycol (NPG) diol monomer Aldrich 1,2-propanediol (PDO) diol monomer Aldrich 1,4-butanediol (BDO) diol monomer Aldrich N,N′-dimethylethylene amine monomer Aldrich diamine (DMEDA) ethylenediamine (EDA) amine monomer Aldrich ethanolamine amine monomer Aldrich dimethyl carbonate (DMC) carbonate ester Aldrich DCC = The Dow Chemical Company PMC = PMC Organometallix

A. Preparation of the Polyester-Polycarbonate Polyol

[0151] Preparation of Poly(1,4-Butanediol-Carbonate) (BDO-PC): A 30 gal. 316L stainless steel vessel having an internal diameter of 20 in. is equipped with internal baffles, a variable speed 12-in. turbine impeller, a sparge ring, a closed loop system with a mixed DOWTHERM™ system having independent hot and cold loops and a 24-inch packed column. To the reactor, 67958.0 grams (g) BDO is added and heated to 150° C. while sweeping with N.sub.2 to inert the reactor and remove water present in the BDO. TYZOR™ TPT catalyst (21.6 g) is added and the line is flushed with 600.0 g BDO previously purged from the reactor. DMC (102864.0 g) is added from a weight pot using a flow meter and control valve over a period of 6 to 8 hrs, while maintaining the temperature in the column at 65° C. Upon completion of the DMC addition, the temperature is increased to 195° C., and the progress of the reaction is tracked by OH number and .sup.1H-NMR for end-group analysis. After 8 hrs at 195° C., the OH number is found to be 30.7 with 25% carbonate end-groups by .sup.1-NMR. The temperature is decreased to 150° C. and 4.1 pounds (lbs) of BDO is added to the reaction. The temperature is brought up to 195° C. and after 8 hrs, the OH number is found to be 54 mg KOH/g with less than 1% carbonate end-groups. A poly(1,4-butanediol-carbonate) (BDO-PC) is prepared that has an OH number of 54 mg KOH/g and a Mn of 1960 g/mol.

[0152] Preparation of Polyester-Amide Polycarbonate Polyols (PE-A PC): Polyester-polycarbonate polyols are synthesized according to the following general procedure, with detailed formulation compositions for each sample provided in Table 2. The reaction is run in a glass reactor with a 1000 mL three neck flask equipped with a thermocouple inlet port. One neck of the reactor contains a gas inlet adapter that contains a 29/42 neck with a stopper attached. The gas inlet is fed with N.sub.2 regulated by an adjustable flow meter. The second neck of the reactor contains a custom mechanical stirring shaft adapter modified to allow for a vacuum use. The third neck of the reactor contains an offset adapter attached to a 12-inch long column leading to distillation head and a condenser with a three neck bottom drain collection flask at a bottom of condenser. The collection flask has one line leading to a J-KEM™ vacuum regulator, and another line leading to a N.sub.2 bubbler. The 12-inch column off of the offset adapter is packed with 5 mm glass beads. The column is heated by way of a heating tape controlled by a variac with a thermocouple monitoring column surface temperature. Heating for the reactor is supplied by a heating mantle fed from a control box with over-temp shut-off. Mechanical stirring is achieved using a custom ¼ inch stainless steel paddle and shaft. The reactor is charged with HDO, NPG, PDO, and amine mononer. The mixture is vacuum degassed and N.sub.2 purged up to three times, and then slowly heated to less than 100° C. Adipic acid (or adipic acid and isophthalic acid) is added and the mixture and allowed to stir for approximately one hour. The temperature is then increased to 150° C. and titanium isopropoxide (supplied by Aldrich) is injected. The temperature of the reaction is raised incrementally, as distillate begins to slow, up to 210° C. Moderate vacuum pressure is applied to drive the reaction to completion. The acid value is monitored to determine the end-point of the reaction. When the acid value is lower than 1.0, the polyester component is deemed complete. Then, the BDO-PC prepared as described above and HDO (equimolar to BDO-PC) are added to the polyester component, at room temperature, and the solution is heated to 210° C. for four hours.

TABLE-US-00002 TABLE 2 PE-A PE-A PE-A PE-A PE-A PE-A PE-A PE-A PE-A PE-A Polyester PC 1 PC 2 PC 3 PC 4 PC 5 PC 6 PC 7 PC 8 PC 9 PC 10 11 adipic acid.sup.1 34.47 34.20 40.68 34.36 34.53 30.23 25.49 25.78 34.62 35.09 45.61 isophthalic acid.sup.1 — — — — — 5.05 10.12 10.13 — — — PDO.sup.1 10.73 10.67 12.64 10.67 10.75 10.62 11.24 10.5 10.46 10.36 13.86 NPG.sup.1 9.07 9.74 10.70 9.05 9.62 8.97 8.80 8.87 9.58 9.57 11.66 HDO.sup.1 22.11 21.90 25.07 22.00 18.92 21.88 21.36 21.71 21.49 21.91 28.85 BDO-PC.sup.1 22.90 22.73 10.09 22.86 22.81 22.55 22.20 22.30 22.31 22.33 — DMEDA.sup.1 — — — 1.06 3.38 — — — — — — EDA.sup.1 0.71 0.75 0.83 — — 0.71 0.80 0.71 — — — ethanolannine.sup.1 — — — — — — — — 1.54 0.74 — Acid Value.sup.2 1.00 0.13 0.01 0.25 NM 0 0 0 1.54 0.74 0.49 OH Number.sup.2 148.6 140.6 135.6 137.1 115.2 118.3 147.4 112.1 131.7 102.9 150.8 Tg (° C.) −66.2 −72.3 −65.3 −67.9 −65.6 −62.2 −61.7 −56.5 −68.2 −67.7 −63.6 Viscosity @ 25° C..sup.3 1852 2800 2481 1150 1118 2325 1689 4061 972 1994 2560 Viscosity @ 40° C..sup.3 705 1081 834 463 434 791 605 1270 385 764 733 Mn (g/mol) 1584 1626 1622 1537 1162 1164 1131 1354 1055 1445 1363 Mw (g/mol) 2881 2784 2749 2587 2111 2160 2038 2734 2121 3063 2729 Mz (g/mol) 4554 4264 4206 4036 3252 3327 3107 4333 3407 4945 4309 Mw/Mn 1.82 1.71 1.70 1.68 1.82 1.85 1.80 2.02 2.01 2.12 2.00 wt % species with 4.8 4.6 4.7 4.9 8.4 7.0 7.7 5.5 9.0 5.7 7.5 Mw <500 g/mol wt % species with 17.3 17.4 17.6 19.0 25.2 20.1 25.2 16.6 25.8 15.8 18.5 Mw <1000 g/mol .sup.1monomer weight charges (%), based on the total amount of monomer charged NM = not measured .sup.2Acid Vale and OH Number are measured in mg KOH/g. .sup.3Viscosity is measured in mPa .Math. s.

B. Preparation of the Phosphate-Terminated Polyol

[0153] A 1 liter multi-neck round bottom flask is dried in an oven, flushed with dry nitrogen for 30 min., and charged with 149.96 grams of VORANOL™ CP 450 (polyether polyol) and is placed under an N.sub.2 sweep of 70 mL/min. A syringe is loaded with 3.395 g of 115% polyphosphoric acid (PPA) (supplied by Sigma Aldrich). The PPA is added dropwise to the VORANOL™ CP 450 with strong agitation. A minimal temperature increase is observed. The reactor contents are heated to 100° C. for 1 hr, and are then cooled to 45° C. 21.65 g ISONATE™125M (MDI blend) is slowly added to the reactor. A significant exotherm is controlled with the application of an ice bath to keep the reaction pot below 75° C. The development of a yellow to amber color is observed. The reactor is then maintained at 65° C. for 1 hr, at which point the content is cooled and packaged. The prepared phosphate-terminated polyol (PT-PO) does not contain excess, or free, MDI. The PT-PO has a solids content of 100 wt %, an OH Number of 270 mg KOH/g, an acid value of 24.0 mg KOH/g, a viscosity at 25° C. of 17,820 mPa.Math.s, a Mn of 780 g/mol, a Mw of 1415 g/mol, a Mz of 2325 g/mol, and a Mw/Mn of 1.82. The PT-PO contains 26.0 wt % species with a Mw less than 500 g/mol, and 41.3 wt % species with a Mw less than 1000 g/mol.

C. Preparation of the Polyol Component

[0154] The PE-A PC 1-10, and Polyester 11 prepared as described above are mixed with the PT-PO to form sample polyol components. The composition and the properties of each sample polyol component are provided in Table 3. In the tables, “CS” refers to a comparative sample.

D. Preparation of Two-Component Solvent-Less Adhesive Compositions

[0155] Two-component solvent-less adhesive compositions are prepared by mixing (A) MOR-FREE™ C-33 (aliphatic isocyanate prepolymer) with (B) one of the Example Polyol Components (Ex PC) 1-4 or 8-13, Comparative Sample Polyol Components (CS PC) 5-7, MOR-FREE L82-105, or MOR-FREE 1390A, in a kettle at room temperature (23° C.) until a homogeneous mixture is achieved, forming a two-component solvent-less adhesive composition. The components of each example and comparative example adhesive composition are provided in Tables 4 and 5.

TABLE-US-00003 TABLE 3 Ex PC Ex PC Ex PC Ex PC CS PC CS PC CS PC Ex PC Ex PC Ex PC Ex PC Ex PC Ex PC 1 2 3 4 5 6 7 8 9 10 11 12 13 PE-A PC 1 94.8 — — — — — — — — — — — — PE-A PC 2 — 90.0 85.0 — — — — — — — — — — PE-A PC 3 — — — 95.0 — — — — — — — — — PE-A PC 5 — — — — — — — 95.0 — — — — — PE-A PC 6 — — — — — — — — 95.0 — — — — PE-A PC 7 — — — — — — — — — 94.8 — — — PE-A PC 8 — — — — — — — — — — 94.9 — — PE-A PC 9 — — — — — — — — — — — 95.0 — PE-A PC 10 — — — — — — — — — — — — 94.9 Polyester 11 — — — — 95.0 89.9 85.3 — — — — — — PT-PO 5.2 10.0 15.0  5.0 5.0 10.1 14.7  5.0  5.0 5.2  5.1  5.0  5.1 OH Number 153.9 152.9  157.8  141.6  156.0 161.2 166.4 122.2  125.1  152.8 119.3  137.9  110.5  (mg KOH/g) wt % in Table 3 is based on the total weight of the respective Polyol Component (PC)

E. Formation of a Laminate

[0156] A low density polyethylene (LDPE) film containing a slip agent that is a monolayer film having a thickness of 1.5 mils is provided (GF-19, available from Berry Plastics Corp.).

[0157] A cast polypropylene film that is a monolayer film having a thickness of 3 mil is provided.

[0158] A poly(ethylene glycol-terephtha late) (PET) film that is a monolayer film having a thickness of 1 mil (24.5 μm) is provided (92LBT, available from DuPont).

[0159] A metal foil film is provided (aluminum foil). The metal foil film is a monolayer film having a thickness of 1.5 mils (38.1 μm). The metal foil film is pre-laminated with a PET film (having a thickness of 12 μm, 48 gauge) using ADCOTE™ 577: Coreactant F (a solvent-based, 2-component polyurethane adhesive, commercially available from The Dow Chemical Company) at a coat weight of 3.26 g/m.sup.2 (2.00 lbs/ream) to form a Metal Foil Pre-Laminate (Prelam) having the following Structure (I):

PET Film/ADCOTE™ 577:Coreactant F Adhesive Layer/Metal Foil Film Structure (I).

[0160] The example and comparative example adhesive compositions are loaded into a Nordmeccanica Labo Combi pilot laminator. The laminator nip temp. is maintained at 60° C., the oven temp. is set at 25° C. for each zone, and the laminator is operated at a speed of 30 meters per minute.

[0161] The adhesive composition is applied to either the Metal Foil Pre-Laminate (Prelam) or the PET film (92LBT), to form the following Structure (II) and Structure (III):

Prelam/Adhesive Composition   Structure (II)

PET/Adhesive Composition   Structure (III)

[0162] 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)).

[0163] The LDPE film or the cast polypropylene film is brought into contact with the adhesive layer to form a laminate having the Structure (IV), the Structure (V), the Structure (VI), or the Structure (VII):

Prelam/Adhesive Composition/LDPE   Structure (IV)

Prelam/Adhesive Composition/Cast Polypropylene   Structure (V)

PET/Adhesive Composition/LDPE   Structure (VI)

PET/Adhesive Composition/Cast Polypropylene   Structure (VII)

[0164] Two samples of each example and comparative example laminate are formed. One sample is cured at 25° C. and 50% relative humidity, as shown in Table 4. The other sample is cured at 45° C. in an isotherm oven at a relative humidity of 30%, as shown in Table 5. The properties of each laminate example and comparative sample are provided in Tables 4 and 5. In Tables 4 and 5, “FS” indicates a film stretch failure mode (FM); “FT” indicates a film tear or break FM; “DL” indicates a delamination FM; “AT” indicates an adhesive transfer FM, with adhesive transferred to the second film; “AS” indicates a cohesive failure or adhesive split FM, with adhesive found on both films; “CDL” indicates complete delamination, wherein bond strength not measurable; and “NM” indicates a value was not measured.

F. Results

[0165] As shown in Table 4, CS 10-11 each includes an adhesive layer formed from (A) an NCO Component (MOR-FREE C-33) and (B) a polyol component (MOR-FREE L82-105 and CS PC 5, respectively) that lacks a PE-A PC. The laminate structures of CS 10 and CS 11 that have the Structures (VI) and (VI) (i.e., that contain the PET film) and are cured at 25° C. and 50% relative humidity (RH) each exhibits a bond strength after the boil-in-bag test of less than 3.5 N/2.54 cm. Thus, CS 10 and CS 11 each exhibits insufficient bond strength after the boil-in-bag test.

[0166] As shown in Table 4, Ex 1-9 each includes an adhesive layer formed from (A) an NCO Component (MOR-FREE C-33) and (B) a polyol component (PC 1, PC 3, PC 4, PC 8, PC 9, PC 10, PC 11, PC 12, and PC 13, respectively) containing a PE-A PC. The laminate structures of Ex 1-9 that have the Structures (VI) and (VI) (i.e., that contain the PET film) and are cured at 25° C. and 50% RH each exhibits a bond strength after the boil-in-bag test of greater than 3.5 N/2.54 cm. Thus, Ex 1-9 each exhibits sufficient bond strength after the boil-in-bag test.

TABLE-US-00004 TABLE 4 25° C. Curing Temperature Ex 1 Ex 2 Ex 3 Ex 4 Ex 5 Ex 6 Ex 7 Ex 8 Ex 9 CS 10 CS 11 Adhesive Composition (grams) MOR-FREE C-33 47.0 64.7 62.8 56.0 57.0 63.5 55.0 60.0 54.0 100 64.3 MOR-FREE L82-105 — — — — — — — — — 60 — Ex PC 1 63.4 — — — — — — — — — — Ex PC 3 — 85.4 — — — — — — — — — Ex PC 4 — — 89.3 — — — — — — — — CS PC 5 — — — — — — — — — — 85.7 Ex PC 8 — — — 94.5 — — — — — — — Ex PC 9 — — — — 93.7 — — — — — — Ex PC 10 — — — — — 86.7 — — — — — Ex PC 11 — — — — — — 95.6 — — — — Ex PC 12 — — — — — — — 90.2 — — — Ex PC 13 — — — — — — — — 98.1 — — Isocyanate:Polyol Mixing Ratio 100:135 100:132 100:147 100:170 100:166 100:136 100:175 100:151 100:189 100:60 100:133 Prelann/Adhesive Layer/LDPE Laminate Bond Strength (BS) (N/2.54 cm) BS after 2 days 1.68.sup.AS 2.37.sup.AS 1.66.sup.AS 3.43.sup.AS 3.44.sup.AS 4.37.sup.AS 4.52.sup.AS 3.23.sup.AS NM 2.81.sup.AT 2.01.sup.AS BS after 4 days 2.50.sup.AT 4.57.sup.AT 3.08.sup.AT 3.44.sup.AT 3.93.sup.AT 5.94.sup.AT 4.45.sup.AT 4.12.sup.AT NM 2.74.sup.AT 2.30.sup.AT BS after 7 days 2.65.sup.AT 3.72.sup.AT 2.73.sup.AT 3.21.sup.AT 3.34.sup.AT 4.18.sup.AT 3.25.sup.AT 3.13.sup.AT NM 2.64.sup.AT 2.75.sup.AT BS after 14 days 2.53.sup.AT 3.98.sup.AT 3.10.sup.AT 3.13.sup.AT 3.57.sup.AT 3.98.sup.AT 2.93.sup.AT 2.99.sup.AT NM 2.53.sup.AT 2.44.sup.AT BS Boil-in-Bag 2.62.sup.AT 3.07.sup.AT 1.69.sup.AT 2.19.sup.AT 2.39.sup.AT 2.72.sup.AT 2.16.sup.AT 2.06.sup.AT NM 0.79.sup.AT 0.98.sup.AT Prelann/Adhesive Layer/Cast Polypropylene Laminate Bond Strength (BS) (N/2.54 cm) BS after 2 days 0.03.sup.AS 1.06.sup.AS 0.08.sup.AS 5.26.sup.AS 5.22.sup.AS 5.39.sup.AS 4.85.sup.AS 4.67.sup.AS 4.55.sup.AS 3.53.sup.AS 0.63.sup.AS BS after 4 days 2.03.sup.AT 6.25.sup.AT 4.35.sup.AT 5.33.sup.AT 5.61.sup.AT 6.28.sup.AT 5.44.sup.AT 5.36.sup.AT 5.79.sup.AT 4.06.sup.AT 2.91.sup.AT BS after 7 days 2.54.sup.AT 5.67.sup.AT 3.49.sup.AT 5.23.sup.AT 5.30.sup.AT 5.95.sup.AT 4.78.sup.AT 4.43.sup.AT 3.69.sup.AT 4.41.sup.AT 3.26.sup.AT BS after 14 days 2.94.sup.AT 5.95.sup.AT 4.39.sup.AT 5.28.sup.AT 5.55.sup.AT 5.74.sup.AT 4.52.sup.AT 4.29.sup.AT 3.70.sup.AT 4.68.sup.AT 3.63.sup.AT BS Boil-in-Bag 0.82.sup.AT 2.11.sup.AT 0.99.sup.AT 1.13.sup.AT 1.16.sup.AT 1.34.sup.AT 1.13.sup.AT 1.13.sup.AT 1.00.sup.AT 0.35.sup.AS/DL 0.37.sup.AS/DL BS Chennical Aging 1.12.sup.AS 1.78.sup.AS 0.89.sup.AS 1.06.sup.AS 0.98.sup.AS 1.10.sup.AS 0.91.sup.AS 1.09.sup.AS 0.96.sup.AS 0.90.sup.AS 0.82.sup.AS PET/Adhesive Layer/LDPE Laminate Bond Strength (BS) (N/2.54 cm) BS after 2 days 2.71.sup.AS 3.75.sup.AS 1.29.sup.AS 3.80.sup.AS 5.88.sup.AS 9.151.sup.FS/AS 5.55.sup.AS 4.23.sup.AS NM NM 1.86.sup.AS BS after 4 days 5.99.sup.AS 10.81.sup.FT 4.23.sup.AS 6.87.sup.AS/AT 9.89.sup.FT 11.59.sup.FS/FT 12.13.sup.FT 6.58.sup.AT NM NM 4.77.sup.AS BS after 7 days 6.27.sup.AT/AS 11.13.sup.FT 11.22.sup.FT/AT 10.81.sup.FT 10.95.sup.FT 12.44.sup.FT 10.17.sup.FT 12.29.sup.FT NM NM 7.18.sup.AT BS after 14 days 6.29.sup.AT 12.94.sup.FT 14.13.sup.FT 11.25.sup.FT 11.73.sup.FT 12.37.sup.FT 10.87.sup.FT 12.07.sup.FT NM NM 7.20.sup.AT BS Boil-in-Bag 4.51.sup.AT 4.34.sup.AT 4.03.sup.AT 3.98.sup.AT 3.99.sup.AT 4.41.sup.AT 4.09.sup.AT 3.99.sup.AT NM NM 2.38.sup.AS BS Chennical Aging 5.61.sup.AS 5.63.sup.AS 2.93.sup.AS 4.76.sup.AS 4.92.sup.AS 4.45.sup.AS 4.57.sup.AS 4.29.sup.AS NM NM 2.09.sup.AS PET/Adhesive Layer/Cast Polypropylene Laminate Bond Strength (BS) (N/2.54 cm) BS after 2 days 0.15.sup.AS 1.24.sup.AS 0.07.sup.AS NM NM NM NM NM NM NM 0.16.sup.AS BS after 4 days 5.22.sup.AT 11.20.sup.AT 6.31.sup.AT NM NM NM NM NM NM NM 2.39.sup.AT BS after 7 days 7.11.sup.FT 15.54.sup.FT 8.93.sup.FT NM NM NM NM NM NM NM 8.75.sup.FT BS after 14 days 7.05.sup.FT 14.01.sup.FT 8.44.sup.FT NM NM NM NM NM NM NM 9.96.sup.FT BS Boil-in-Bag 4.39.sup.AT 5.25.sup.AT 5.44.sup.AT NM NM NM NM NM NM NM 3.27.sup.AT BS Chennical Aging 8.26.sup.AT 9.33.sup.FT/AT 7.94.sup.FT NM NM NM NM NM NM NM 5.36.sup.FT/AT

TABLE-US-00005 TABLE 5 45° C. Curing Temperature Ex 12 Ex 13 CS 14 CS 15 CS 16 Adhesive Composition (grams) MOR-FREE C-33 63.5 64.7 100 65.5 66.6 MOR-FREE 1390A — — 100 — — Ex PC 2 86.8 — — — — Ex PC 4 — 85.4 — — — CS PC 7 — — — 84.3 — CS PC 9 — — — — 83.4 lsocyanate:Polyol Mixing Ratio 100:137 100:132 100:100 10:129 100:125 Prelam/Adhesive Layer/LDPE Laminate Bond Strength (BS) (N/2.54 cm) BS after 1 day 4.34.sup.AT 3.59.sup.AT 2.87.sup.AT 3.08.sup.AT 3.65.sup.AT BS after 7 days 5.62.sup.AT 4.86.sup.AT 4.04.sup.AT 3.54.sup.AT 3.33.sup.AT BS after 14 days 3.52.sup.AT 3.28.sup.AT 2.92.sup.AT 3.09.sup.AT 3.24.sup.AT BS Boil-in-Bag 5.17.sup.AT 4.89.sup.AT 1.99.sup.AT 1.59.sup.AT 1.99.sup.AT BS Chemical Aging 0.19.sup.AS/DL 0.35.sup.AS/DL 0.28.sup.AS/DL 0.18.sup.AS/DL 0.22.sup.AS/DL Prelam/Adhesive Layer/Cast Polypropylene Laminate Bond Strength (BS) (N/2.54 cm) BS after 1 day 8.00.sup.AT 7.58.sup.AT 6.04.sup.AT 6.47.sup.AT 6.96.sup.AT BS after 7 days 10.12.sup.AT 9.73.sup.AT 7.44.sup.AT 7.00.sup.AT 7.52.sup.AT BS after 14 days 7.42.sup.AT 6.86.sup.AT 4.63.sup.AT 6.10.sup.AT 7.34.sup.AT BS Boil-in-Bag 1.45.sup.AT 4.64.sup.AT CDL 1.44.sup.AT 1.60.sup.AT BS Chemical Aging 0.92.sup.AS 0.91.sup.AS 0.25.sup.AS/DL 0.33.sup.AS/DL 0.37.sup.AS/DL PET/Adhesive Layer/LDPE Laminate Bond Strength (BS) (N/2.54 cm) BS after 1 day 19.32.sup.FT 13.95.sup.FT 13.15.sup.FT 9.14.sup.FT 10.31.sup.FT BS after 7 days 16.46.sup.FT 18.46.sup.FT 15.91.sup.FT 9.65.sup.FT 10.43.sup.FT BS after 14 days 14.35.sup.FT 11.44.sup.FT 15.11.sup.FT 10.20.sup.FT 9.98.sup.FT BS Boil-in-Bag 8.62.sup.FT/AS 4.67.sup.AT 3.12.sup.AS 1.48.sup.AT 1.41.sup.AT BS Chemical Aging 3.11.sup.AT 4.60.sup.AT 3.65.sup.AS 0.83.sup.AT 0.89.sup.AS PET/Adhesive Layer/Cast Polypropylene Laminate Bond Strength (BS) (N/2.54 cm) BS after 1 day 12.99.sup.FT 9.01.sup.FT 12.63.sup.FT 11.64.sup.FT 13.66.sup.FT BS after 7 days 10.90.sup.FT 11.98.sup.FT 10.02.sup.FT 10.89.sup.FT 12.66.sup.FT BS after 14 days 12.27.sup.FT 17.71.sup.FT 12.53.sup.FT 9.66.sup.FT 12.47.sup.FT BS Boil-in-Bag 8.81.sup.FT 8.37.sup.FT 7.98.sup.FT 3.44.sup.AT 4.66.sup.AT BS Chemical Aging 7.70.sup.FT 8.64.sup.FT 7.95.sup.FT 1.54.sup.AT 1.56.sup.AT

[0167] As shown in Table 5, CS 14-16 each includes an adhesive layer formed from (A) an NCO Component (MOR-FREE C-33) and (B) a polyol component (MOR-FREE 1390A, CS PC 6, and CS PC 7, respectively) that lacks a PE-A PC. The laminate structures of CS 14-16 that have the Structure (V) (i.e., Prelam/Adhesive Composition/Cast Polypropylene) and are cured at 45° C. in an isotherm oven at a RH of 30% each exhibits a bond strength after the chemical aging of less than 0.5 N/2.54 cm. Thus, CS 14-16 each exhibits insufficient bond strength after chemical aging.

[0168] A shown in Table 5, Ex 12-13 each includes an adhesive layer formed from (A) an NCO Component (MOR-FREE C-33) and (B) a polyol component (PC 2 and PC 3, respectively) containing a PE-A PC. The laminate structures of Ex 12-13 that have the Structure (V) (i.e., Prelam/Adhesive Composition/Cast Polypropylene) and are cured at 45° C. in an isotherm oven at a RH of 30% each exhibits a bond strength after the chemical aging of greater than 0.50 N/2.54 cm. Thus, Ex 12-13 each exhibits sufficient bond strength after chemical aging.

[0169] 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.