Two-Component Solvent-Based Adhesive Composition

Abstract

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 polyol component containing (i) a polyester-polycarbonate polyol and (ii) a phosphate-terminated polyol; and (iii) a solvent. The present disclosure also provides a method of forming a two-component solvent-based adhesive composition.

Claims

1. A two-component solvent-based adhesive composition comprising the reaction product of: (A) an isocyanate component; (B) a polyol component comprising (i) a polyester-polycarbonate polyol; (ii) a phosphate-terminated polyol; and (C) a solvent.

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

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

4. The two-component solvent-based adhesive composition of claim 1, wherein the polyester-polycarbonate polyol comprises the reaction product of adipic acid, 1,2-propanediol, neopentyl glycol, 1,6-hexanediol, and poly(1,4-butanediol-carbonate).

5. The two-component solvent-based adhesive composition of claim 1, wherein the phosphate-terminated polyol has the Structure (C) ##STR00006## wherein R.sup.4 is an ether group or a substituted ether group.

6. The two-component solvent-based 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.

7. The two-component solvent-based adhesive composition of claim 1, wherein the isocyanate component is an aromatic isocyanate prepolymer.

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-based 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 low density polyethylene film; and the laminate has a bond strength after the boil-in-bag test from 8.8 N/2.54 cm to 20.0 N/2.54 cm.

10. The laminate of claim 8, wherein the first substrate is a polyethylene terephthalate film and the second substrate is a polypropylene film; and the laminate has a bond strength after one day from 10.0 N/2.54 cm to 25.0 N/2.54 cm.

11. A method of forming a two-component solvent-based adhesive composition comprising: (A) providing a polyol component comprising (i) a polyester-polycarbonate polyol; (ii) a phosphate-terminated polyol; (B) providing an isocyanate component; (C) providing a solvent; and (D) reacting the polyol component with the isocyanate component in the presence of the solvent to form the two-component solvent-based adhesive composition.

Description

DETAILED DESCRIPTION

[0034] 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 polyol component containing (i) a polyester-polycarbonate polyol and (ii) a phosphate-terminated polyol; and (C) a solvent.

A. Isocyanate Component

[0035] The two-component solvent-based adhesive composition contains the reaction product of (A) an isocyanate component; (B) a polyol component; and (C) a solvent.

[0036] Nonlimiting examples of suitable isocyanate components include aromatic isocyanates, aliphatic isocyanates, carbodiimide modified isocyanates, polyisocyanate trimers, polyfunctional isocyanate, isocyanate prepolymers, and the combinations thereof.

[0037] 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) such as 4,4′-MDI, 2,4′-MDI, and 2,2′-MDI; modified MDI such as carbodiimide modified MDI orallophanate 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.

[0038] 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 tri isocyanate; 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-tri methylhexamethylene diisocyanate; 2,4,4-trimethylhexamethylene diisocyanate; norbornane diisocyanate; xylylene diisocyanate; isomers, dimers, and/or trimers thereof; and combinations thereof.

[0039] 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).

[0040] 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.

[0041] 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.

[0042] In an embodiment, the isocyanate is an aromatic isocyanate prepolymer. A nonlimiting example of a suitable aromatic isocyanate prepolymer is ADCOTE™577, available from The Dow Chemical Company.

[0043] The isocyanate component may comprise two or more embodiments disclosed herein.

B. Polyol Component

[0044] The two-component solvent-based adhesive composition contains the reaction product of (A) the isocyanate component; (B) a polyol component; and (C) a solvent. The polyol component contains (i) a polyester-polycarbonate polyol and (ii) a phosphate-terminated polyol.

Polyester-Polycarbonate Polyol

[0045] The polyol component contains (i) a polyester-polycarbonate polyol and (ii) a phosphate-terminated polyol.

[0046] A “polyester-polycarbonate polyol” (or “PE-PC”) is a compound that is a polyester, a polycarbonate, and a polyol. The PE-PC can be prepared from 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-hexa nediol (HDO), neopentyl glycol (NPG), and 1,2-propanediol (PDO)), and a carbonate monomer or polycarbonate (such as poly(1,4-butanediol-carbonate (BDO-PC)).

[0047] In an embodiment, the PE-PC is the reaction product of AA, PDO, NPG, HDO, and BDO-PC.

[0048] In an embodiment, the PE-PC has the Structure (A):

##STR00001##

wherein n is from 1, or 2 to 30; m is from 1, or 2 to 20;
R.sup.1 is selected from —(CH.sub.2).sub.2—, —(CH.sub.2).sub.4—, cis- or trans- —C═C—, —(CH.sub.2).sub.7—, —(CH.sub.2).sub.8—, Structure (S), Structure (T), Structure (U), and Structure (V);
R.sup.2 is selected from —(CH.sub.2).sub.2—, —(CH.sub.2).sub.2—O—(CH.sub.2).sub.2—, —(CH.sub.2).sub.2—O—(CH.sub.2).sub.2—O—(CH.sub.2).sub.2—, —(CH.sub.2).sub.2—O—(CH.sub.2).sub.2—O—(CH.sub.2).sub.2—O—(CH.sub.2).sub.2—, —CH.sub.2—CH(CH.sub.3)—, —(CH.sub.2).sub.4—, —(CH.sub.2).sub.6—, —CH.sub.2—CH(CH.sub.3)—O—CH.sub.2—CH(CH.sub.3)—, —CH.sub.2—CH(CH.sub.3)—CH.sub.2—, —CH.sub.2—CH(CH.sub.3).sub.2—CH.sub.2—, Structure (W), Structure (X), and Structure (Y);
R.sup.3 is selected from —(CH.sub.2).sub.4—, —(CH.sub.2).sub.6—, —(CH.sub.2).sub.2—O—(CH.sub.2).sub.2—, —CH.sub.2—CH(CH.sub.3)—CH.sub.2—, and —CH.sub.2—C(CH.sub.3).sub.2—CH.sub.2—.

[0049] As used herein, Structures (S)—(Y) are as follows:

##STR00002##

[0050] In an embodiment, R.sup.1 of Structure (A) is —(CH.sub.2).sub.4—; and R.sup.2 of Structure (A) is selected from —(CH.sub.2).sub.4—, Structure (T), and Structure (U).

[0051] In an embodiment, the PE-PC has a number average molecular weight, Mn, from 500 g/mol, or 1000 g/mol, or 1500 g/mol, or 1700 g/mol to 1900 g/mol, or 2000 g/mol, or 2500 g/mol, or 3000 g/mol, or 3500 g/mol, or 4000 g/mol, or 5000 g/mol, or 6000 g/mol, or 7000 g/mol, or 8000 g/mol. In another embodiment, the PE-PC has a Mn from 500 g/mol to 8000 g/mol, or from 10008/mol to 8000 g/mol, or from 1500 g/mol to 8000 g/mol, or from 1500 g/mol to 5000 g/mol, or from 1500 g/mol to 2000 g/mol.

[0052] In an embodiment, the PE-PC has a weight average molecular weight, Mw, from 5008/mol, or 1000 g/mol, or 2000 g/mol, or 3000 g/mol to 3500 g/mol, or 5000 g/mol, or 10000 g/mol. In another embodiment, the PE-PC has a Mw from 500 g/mol to 10000 g/mol, or from 3000 g/mol to 5000 g/mol.

[0053] In an embodiment, the PE-PC has a Mw/Mn from 1.5, or 1.6, or 1.7 to 1.9, or less than 2.0. In a further embodiment, the PE-PC has a Mw/Mn from 1.5 to less than 2.0, or from 1.7 to 1.9. Not wishing to be bound by any particular theory, it is believed that a PE-PC with a Mw/Mn less than 2.0, in combination with a Mw greater than 500 g/mol, or greater than 3000 g/mol, minimizes the amount of migration of low molecular weight species in cured laminating adhesives, which is advantageous in food packaging applications.

[0054] In an embodiment, the PE-PC has an acid value from 0.1 mg KOH/g, or 0.2 mg KOH/g to 0.9 mg KOH/g, or 1.0 mg KOH/g, or 2.0 mg KOH/g. In another embodiment, the PE-PC has an acid value from 0.1 mg KOH/g to 2.0 mg KOH/g, or from 0.2 mg KOH/g to 0.9 mg KOH/g.

[0055] In an embodiment, the PE-PC has an OH Number from 100 mg KOH/g, or 110 mg KOH/g to 140 mg KOH/g, or 145 mg KOH/g, or 150 mg KCH/g, or 175 mg KOH/g, or 200 mg KOH/g, or 250 mg KOH/g. In another embodiment, the PE-PC has an OH Number from 100 mg KOH/g to 250 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, or from 100 mg KOH/g to 140 mg KOH/g, or from 115 mg KOH/g to 135 mg KOH/g.

[0056] In an embodiment, the PE-PC has a glass transition temperature (Tg) from −90° C., or −85° C., or −80° C., or −75° C. to −65° C., or −60° C., or −55° C., or −50° C. In another embodiment, the PE-PC has a Tg from −90° C. to −50° C., or from −90° C. to −60° C., or from −90° C. to −65° C., or from −75° C. to −65° C.

[0057] In an embodiment, the PE-PC has a viscosity at 25° C. from 500 mPa.Math.s, or 750 mPa.Math.s, or 1000 mPa.Math.s, or 1500 mPa.Math.s to 1900 mPa.Math.s, or 2000 mPa.Math.s, or 2200 mPa.Math.s, or 2500 mPa.Math.s. In another embodiment, the PE-PC has a viscosity at 25° C. from 500 mPa.Math.s to 2500 mPa.Math.s, or from 1000 mPa.Math.s to 2200 mPa.Math.s, or from 1500 mPa.Math.s to 2000 mPa.Math.s.

[0058] In an embodiment, the PE-PC has a viscosity at 40° C. from 250 mPa.Math.s, or 300 mPa.Math.s, or 400 mPa.Math.s, or 500 mPa.Math.s, or 600 mPa.Math.s to 700 mPa.Math.s, or 720 mPa.Math.s, or 725 mPa.Math.s, or 730 mPa.Math.s. In another embodiment, the PE-PC has a viscosity at 40° C. from 250 mPa.Math.s to 730 mPa.Math.s, or from 300 mPa.Math.s to 720 mPa.Math.s, or from 600 mPa.Math.s to 700 mPa.Math.s.

[0059] Not wishing to be bound by any particular theory, it is believed that the PE-PC with (i) a viscosity at 40° C. of less than 730 mPa.Math.s and/or (ii) a viscosity at 25° C. of less than 2500 mPa.Math.s enables the two-component solvent-based adhesive composition to have a higher solids content (i.e., from 30 wt %, or 35 wt %, or 40 wt % to 45 wt %) than traditional solvent-based adhesive compositions, which is advantageous in solvent-based adhesive composition applications.

[0060] In an embodiment, the PE-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 less than 7 wt %, or less than 5 wt % species having a Mw less than 500 g/mol, based on the total weight of the PE-PC. In another embodiment, the PE-PC contains from 0 wt %, or 0.01 wt %, or 1 wt % to 5 wt %, or 7 wt %, or 10 wt %, or 15 wt %, or 20 wt %, or 30 wt %, or 40 wt %, or 50 wt %, or 55 wt % species having a Mw less than 500 g/mol, based on the total weight of the PE-PC. In a further embodiment, the PE-PC contains from 0 wt % to 5 wt % species having a Mw less than 500 g/mol, based on the total weight of the PE-PC.

[0061] In an embodiment, the PE-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 18 wt %, or less than 15 wt % species having a Mw less than 1000 g/mol, based on the total weight of the PE-PC. In another embodiment, the PE-PC contains from 0 wt %, or 0.01 wt %, or 1 wt % to 15 wt %, or 18 wt %, or 20 wt %, or 30 wt %, or 40 wt %, or 50 wt %, or 55 wt % species having a Mw less than 1000 g/mol, based on the total weight of the PE-PC. In a further embodiment, the PE-PC contains from 0 wt % to 15 wt % species having a Mw less than 1000 g/mol, based on the total weight of the PE-PC.

[0062] 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-PC minimizes the amount of migration of low molecular weight species in cured laminating adhesives, which is advantageous in food packaging applications.

[0063] In an embodiment, the PE-PC has one, some, or all of the following properties: (i) a Mn from 500 g/mol to 8000 g/mol, or from 1500 g/mol to 5000 g/mol, or from 1500 g/mol to 2000 g/mol; and/or (ii) a Mw from 500 g/mol to 10000 g/mol, or from 3000 g/mol to 5000 g/mol; and/or (iii) a Mw/Mn from 1.5 to less than 2.0, or from 1.7 to 1.9; and/or (iv) an acid value from 0.1 mg KOH/g to 2.0 mg KOH/g, or from 0.2 mg KOH/g to 0.9 mg KOH/g; and/or (v) an OH Number from 100 mg KOH/g to 250 mg KOH/g, or from 100 mg KOH/g to 150 mg KOH/g, or from 115 mg KOH/g to 135 mg KOH/g; and/or (vi) a Tg from −90° C. to −50° C., or from −90° C. to −60° C., or from −75° C. to −65° C.; and/or (vii) a viscosity at 25° C. from 500 mPa.Math.s to 2500 mPa.Math.s, or from 1500 mPa.Math.s to 2000 mPa.Math.s; and/or (viii) a viscosity at 40° C. from 250 mPa.Math.s to 730 mPa.Math.s, or from 600 mPa.Math.s to 700 mPa.Math.s; and/or (ix) from 0 wt % to 5 wt % species having a Mw less than 500 g/mol; and/or (x) from 0 wt % to 15 wt % species having a Mw less than 1000 g/mol, based on the total weight of the PE-PC. In an embodiment, the PE-PC has one, some, or all of the properties (i)-(x), and the PE-PC has the Structure (A). In a further embodiment, the PE-PC is the reaction product of AA, PDO, NPG, HDO, and BDO-PC.

[0064] A nonlimiting example of a suitable PE-PC is the PE-PC disclosed in International Publication No. WO 2017/003620, the entire contents of which are herein incorporated by reference.

[0065] The PE-PC may comprise two or more embodiments disclosed herein.

Phosphate-Terminated Polyol

[0066] The polyol component contains (i) the polyester-polycarbonate polyol and (ii) a phosphate-terminated polyol.

[0067] A “phosphate-terminated polyol” (“PT-PO”) is a polyol containing at least one phosphate group having the Structure (B):

##STR00003##

[0068] 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.

[0069] In an embodiment, the PT-PO has the Structure (C):

##STR00004##

wherein R.sup.4 is an ether group or a substituted ether group.

[0070] In an embodiment, R.sup.4 is a polyether. In another embodiment, R.sup.4 contains only carbon atoms, hydrogen atoms, optional oxygen atoms, and optional phosphorous atoms.

[0071] In an embodiment, R.sup.4 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.5 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.

[0072] In an embodiment, the PT-PO has an OH Number from 50 mg KOH/g, or 100 mg KOH/g, or 110 mg KOH/g to 115 mg KOH/g, or 120 mg KOH/g, or 130 mg KOH/g, or 140 mg KOH/g, or 150 mg KOH/g. In another embodiment, the PT-PO has an OH Number from 50 mg KOH/g to 150 mg KOH/g, or from 75 mg KOH/g to 125 mg KOH/g, or from 100 mg KOH/g to 120 mg KOH/g.

[0073] In an embodiment, the PT-PO has an acid value from 5 mg KOH/g, or 10 mg KOH/g, or 15 mg KOH/g, or 18 mg KOH/g to 19 mg KOH/g, or 20 mg KOH/g, or 25 mg KOH/g, or 30 mg KOH/g, or 50 mg KOH/g. In another embodiment, the PT-PO has an acid value from 5 mg KOH/g to 50 mg KOH/g, or from 10 mg KOH/g to 20 mg KOH/g, or from 15 mg KOH/g to 19 mg KOH/g.

[0074] In an embodiment, the PT-PO has a viscosity at 25° C. from 1000 mPa.Math.s, or 1200 mPa.Math.s, or 1500 mPa.Math.s, or 1600 mPa.Math.s to 1700 mPa.Math.s, or 1800 mPa.Math.s, or 1900 mPa.Math.s, or 2000 mPa.Math.s. In another embodiment, the PT-PO has a viscosity at 25° C. from 1000 mPa.Math.s to 2000 mPa.Math.s, or from 1200 mPa.Math.s to 1800 mPa.Math.s, or from 1600 mPa.Math.s to 1700 mPa.Math.s.

[0075] In an embodiment, the PT-PO has a Mn from 500 g/mol, or 750 g/mol, or 1000 g/mol, or 1250 g/mol, or 1500 g/mol, or 1600 g/mol, or 1700 g/mol to 1800 g/mol, or 1900 g/mol, or 2000 g/mol, or 3000 g/mol, or 4000 g/mol, or 5000 g/mol, or 6000 g/mol, or 7000 g/mol, or 8000 g/mol. In another embodiment, the PT-PO has a Mn from 500 g/mol to 8000 g/mol, or from 1000 g/mol to 5000 g/mol, or from 1500 g/mol to 2000 g/mol, or from 1600 g/mol to 1800 g/mol.

[0076] In an embodiment, the PT-PO has a Mw from 1000 g/mol, or 2000 g/mol, or 3000 g/mol, or 3500 g/mol, or 4000 g/mol, or 4100 g/mol to 4200 g/mol, or 4500 g/mol, or 5000 g/mol, or 6000 g/mol, or 7000 g/mol, or 8000 g/mol, or 9000 g/mol, or 10000 g/mol. In another embodiment, the PT-PO has a Mw from 1000 g/mol to 10000 g/mol, or from 2000 g/mol to 8000 g/mol, or from 2000 g/mol to 5000 g/mol, or from 4000 g/mol to 4500 g/mol.

[0077] In an embodiment, the PT-PO has a Mw/Mn from 1.5, or 2.0, or 2.2, or 2.4 to 2.5, or 2.6, or 2.8, or 3.0. In another embodiment, the PT-PO has a Mw/Mn from 1.5 to 3.0, or from 2.2 to 2.8.

[0078] In an embodiment, the PT-PO contains less than 20 wt %, or less than 15 wt %, or less than 10 wt %, or less than 8 wt %, or less than 5 wt % species having a Mw less than 500 g/mol, based on the total weight of the PT-PO. In another embodiment, the PT-PO contains from 0 wt %, or 0.01 wt %, or 1 wt % to 4.5 wt %, or 5 wt %, or 8 wt %, or 10 wt %, or 15 wt %, or 20 wt % species having a Mw less than 500 g/mol, based on the total weight of the PT-PO. In a further embodiment, the PT-PO contains from 0 wt % to 5 wt % species having a Mw less than 500 g/mol, based on the total weight of the PT-PO.

[0079] In an embodiment, the PT-PO contains less than 40 wt %, or less than 35 wt %, or less than 30 wt %, or less than 25 wt %, or less than 20 wt % species having a Mw less than 500 g/mol, based on the total weight of the PT-PO. In another embodiment, the PT-PO contains from 0 wt %, or 0.01 wt %, or 1 wt % to 16 wt %, or 20 wt %, or 25 wt %, or 30 wt %, or 35 wt %, or 40 wt % species having a Mw less than 1000 g/mol; or from 0 wt % to 20 wt % species having a Mw less than 1000 g/mol, based on the total weight of the PT-PO.

[0080] Not wishing to be bound by any particular theory, it is believed that (i) a low level (i.e., less than 20 wt %) of species having a Mw less than 500 g/mol and/or (ii) a low level (i.e., less than 40 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, which is advantageous in food packaging applications.

[0081] In an embodiment, the PT-PO has one, some, or all of the following properties: (i) an OH Number from 50 mg KOH/g to 150 mg KOH/g, or from 75 mg KOH/g to 125 mg KOH/g, or from 100 mg KOH/g to 120 mg KOH/g; and/or (ii) an acid value from 5 mg KOH/g to 50 mg KOH/g, or from 10 mg KOH/g to 20 mg KOH/g, or from 15 mg KOH/g to 19 mg KOH/g; and/or (iii) a viscosity at 25° C. from 1000 mPa.Math.s to 2000 mPa.Math.s, or from 1600 mPa.Math.s to 1700 mPa.Math.s; and/or (iv) a Mn from 500 g/mol to 8000 g/mol, or from 1600 g/mol to 1800 g/mol; and/or (v) a Mw from 1000 g/mol to 10000 g/mol, or from 4000 g/mol to 4500 g/mol; and/or (vi) a Mw/Mn from 1.5 to 3.0, or from 2.2 to 2.8; and/or (vii) from 0 wt % to 5 wt % species having a Mw less than 500 g/mol; and/or (viii) from 0 wt % to 20 wt % species having a Mw less than 1000 g/mol, based on the total weight of the PT-PO; (ix) has the Structure (C); and/or (x) is the reaction product of a polyether polyol and PPA.

[0082] 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.

[0083] The PT-PO may comprise two or more embodiments disclosed herein.

Optional Additive

[0084] In addition to (i) the polyester-polycarbonate polyol and (ii) the phosphate-terminated polyol, the polyol component may contain (iii) an optional additive.

[0085] Nonlimiting examples of suitable optional additives include polyols, adhesion promoters, chain extenders, catalysts, and combinations thereof.

[0086] 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-PC and (ii) the PT-PO. The polyol may be compositionally distinct and/or physically distinct from (i) the PE-PC and (ii) the PT-PO.

[0087] Nonlimiting examples suitable polyols include diols (which contain two hydroxyl groups), triols (which contain three hydroxyl 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).

[0088] 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.

[0089] 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.

[0090] Nonlimiting examples of suitable chain extenders include glycerine; trimethylol propane; DEG; propanediol; MPG; 3-methyl-1,5-pentanediol; and combinations thereof.

[0091] Nonlimiting examples of suitable catalysts include tetra-n-butyl titanate, titanium isoproxide, zinc sulphate, organo tin catalyst (e.g., dibutyltin di laurate), and combinations thereof.

[0092] In an embodiment, the reaction mixture excludes a chain extender.

[0093] The optional additive may comprise two or more embodiments disclosed herein.

[0094] In an embodiment, the polyol component contains, consists essentially of, or consists of (i) the PE-PC, (ii) the PT-PO, and (iii) optionally, an additive. The polyol component is a blend of (i) the PE-PC, (ii) the PT-PO, and (iii) the optional additive.

[0095] In an embodiment, the polyol component contains from 65 wt %, or 70 wt %, or 75 wt %, or 79 wt %, or 80 wt %, or 85 wt %, or 90 wt % to 95 wt %, or 98 wt %, or 99 wt %, or 99.5 wt % PE-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 21 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 79 wt % to 95 wt % PE-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 21 wt % PT-PO, based on the total weight of the polyol component.

[0096] In an embodiment, the polyol component has an OH Number from 50 mg KOH/g, or 100 mg KOH/g, or 110 mg KOH/g, or 115 mg KOH/g, or 119 mg KOH/g to 135 mg KOH/g, or 140 mg KOH/g, or 145 mg KOH/g. In another embodiment, the polyol component has an OH Number from 50 mg KOH/g to 145 mg KOH/g, or from 100 mg KOH/g to 140 mg KOH/g, or from 115 mg KOH/g to 135 mg KOH/g.

[0097] 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.

[0098] The polyol component may comprise two or more embodiments disclosed herein.

C. Solvent

[0099] The two-component solvent-based adhesive composition contains the reaction product of (A) the isocyanate component; (B) the polyol component; and (C) a solvent.

[0100] 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 components in the adhesive composition is dissolved and/or dispersed within. Nonlimiting examples of suitable solvents includes hydrocarbon solvents, polar solvents, and combinations thereof.

[0101] 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.

[0102] 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.

[0103] 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).

[0104] 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.

[0105] In an embodiment, the polar solvent is an ester. Nonlimiting examples of suitable esters include butyl acetate and ethyl acetate (EA).

[0106] In an embodiment, the solvent is selected from ethyl acetate, methyl ethyl ketone, and combinations thereof. In a further embodiment, the solvent is ethyl acetate (EA).

[0107] The solvent may comprise two or more embodiments disclosed herein.

D. Two-Component Solvent-Based Adhesive Composition

[0108] The two-component solvent-based adhesive composition contains the reaction product of (A) the isocyanate component; (B) the polyol component containing (i) the PE-PC and (ii) the PT-PO; and (C) the solvent.

[0109] The two-component solvent-based adhesive composition is formed by mixing (A) the isocyanate component, (B) the polyol component, and (C) the solvent under conditions suitable to react the—NCO groups of the isocyanate component with the hydroxyl groups of the polyol component. In an embodiment, (A) the isocyanate component, (B) the polyol component, and (C) the solvent 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 to 30 minutes. In an embodiment, (A) the isocyanate component, (B) the polyol component are completely dissolved, or substantially dissolved, in (C) the solvent.

[0110] The (C) solvent may be pre-mixed with the (A) isocyanate component and/or the (B) polyol component. In an embodiment, the (C) solvent is pre-mixed with the (B) polyol component. In other words, the polyol component is mixed with solvent before it contacts the isocyanate component. In an embodiment, the (C) solvent is pre-mixed with the (3) polyol 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 %, or 95 wt %, or 99 wt %.

[0111] In an embodiment, the two-component solvent-based adhesive composition includes (A) isocyanate component and (B) polyol component at an Isocyanate:Polyol Weight Ratio, based on dry weight, from 100:1, or 100:12, or 100:14 to 100:17, or 100:20. In another embodiment, the two-component solvent-based adhesive composition includes (A) isocyanate component and (B) polyol component at an Isocyanate:Polyol Weight Ratio, based on dry weight, from 100:1 to 100:20, or from 100:12 to 100:17, or from 100:14 to 100:17.

[0112] In an embodiment, the two-component solvent-based adhesive composition contains from 55 wt % to 60 wt %, or 65 wt %, or 70 wt % solvent, based on the total weight of the two-component solvent-based adhesive composition.

[0113] In an embodiment, the two-component solvent-based adhesive composition has a solids content from 30 wt %, or 35 wt %, or 40 wt % to 45 wt %, based on the total weight of the two-component solvent-based adhesive composition. In another embodiment, the two-component solvent-based adhesive composition has a solids content from 30 wt % to 45 wt %, or from 40 wt % to 45 wt %, based on the total weight of the two-component solvent-based adhesive composition.

[0114] In an embodiment, the two-component solvent-based adhesive composition contains, consists essentially of, or consists of, the reaction product of

[0115] (A) an isocyanate component comprising an aromatic isocyanate prepolymer;

[0116] (B) a polyol component containing, consisting essentially of, or consisting of [0117] (i) from 65 wt % to 99.5 wt %, or from 70 wt % to 99 wt %, or from 75 wt % to 95 wt %, or from 79 wt % to 95 wt % PE-PC, based on the total weight of the polyol component, the PE-PC having one, some, or all of the following properties: (a) a Mn from 500 g/mol to 8000 g/mol, or from 1500 g/mol to 2000 g/mol; and/or (b) a Mw from 500 g/mol to 10000 g/mol, or from 3000 g/mol to 5000 g/mol; and/or (c) a Mw/Mn from 1.5 to less than 2.0, or from 1.7 to 1.9; and/or (d) an acid value from 0.1 mg KOH/g to 2.0 mg KOH/g, or from 0.2 mg KOH/g to 0.9 mg KOH/g; and/or (e) an OH Number from 100 mg KOH/g to 250 mg KOH/g, or from 115 mg KOH/g to 135 mg KOH/g; and/or (f) a Tg from −90° C. to −50° C., or from −75° C. to −65° C.; and/or (g) a viscosity at 25° C. from 500 mPa.Math.s to 2500 mPa.Math.s, or from 1500 mPa.Math.s to 2000 mPa.Math.s; and/or (h) a viscosity at 40° C. from 250 mPa.Math.s to 730 mPa.Math.s, or from 600 mPa.Math.s to 700 mPa.Math.s; and/or (i) from 0 wt % to 5 wt % species having a Mw less than 500 g/mol; and/or (j) from 0 wt % to 15 wt % species having a Mw less than 1000 g/mol, based on the total weight of the PE-PC; and/or (k) has the Structure (A); and/or (I) is the reaction product of AA, PDO, NPG, HDO, and BDO-PC; [0118] (ii) 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 21 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 50 mg KOH/g to 150 mg KOH/g, or from 100 mg KOH/g to 120 mg KOH/g; and/or (b) an acid value from 5 mg KOH/g to 50 mg KOH/g, or from 15 mg KOH/g to 19 mg KOH/g; and/or (c) a viscosity at 25° C. from 1000 mPa.Math.s to 2000 mPa.Math.s, or from 1600 mPa.Math.s to 1700 mPa.Math.s; and/or (d) a Mn from 500 g/molto 8000 g/mol, or from 1600 g/mol to 1800 g/mol; and/or (e) a Mw from 1000 g/mol to 10000 g/mol, or from 4000 g/mol to 4500 g/mol; and/or (f) a Mw/Mn from 1.5 to 3.0, or from 2.2 to 2.8; and/or (g) from 0 wt % to 5 wt % species having a Mw less than 500 g/mol; and/or (h) from 0 wt % to 20 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
the polyol component has an OH Number from 50 mg KOH/g to 145 mg KOH/g, or from 100 mg KOH/g to 140 mg KOH/g, or from 115 mg KOH/g to 135 mg KOH/g;

[0119] (C) from 55 wt % to 70 wt %, or from 55 wt % to 60 wt % solvent, based on the total weight of the two-component solvent-based adhesive composition; and

[0120] (D) optionally, an additive; and

wherein the composition has one, some, or all of the following properties: (a) a solids content from 30 wt % to 45 wt %, or from 40 wt % to 45 wt %, based on the total weight of the two-component solvent-based adhesive composition; and/or (b) an Isocyanate:Polyol Weight Ratio, based on dry weight, from 100:1 to 100:20, or from 100:12 to 100:17, or from 100:14 to 100:17.

[0121] The two-component solvent-based adhesive composition may comprise two or more embodiments disclosed herein.

E. Laminate

[0122] 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.

[0123] The two-component solvent-based adhesive composition may be any two-component solvent-based adhesive composition disclosed herein.

[0124] The laminate includes a first substrate and a second substrate.

[0125] 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.

[0126] In an embodiment, the first substrate and the second substrate are compositionally distinct and/or structurally distinct from one another.

[0127] It is understood that the below description referring to a “substrate” refers to the first substrate and the second substrate, individually and/or collectively.

[0128] 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.

[0129] In an embodiment, the film is a monolayer film with one, and only one, layer.

[0130] 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 multi layer film may for formed from the same component, or from different components.

[0131] In an embodiment, the film includes a layer containing metal foil.

[0132] 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.

[0133] The substrate, and further the film, is a continuous structure with two opposing surfaces.

[0134] 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.

[0135] 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).

[0136] The first substrate may comprise two or more embodiments disclosed herein.

[0137] The second substrate may comprise two or more embodiments disclosed herein.

[0138] The two-component solvent-based adhesive composition is applied between the first substrate and the second substrate, such as with a Nordmeccanica Labo Combi laminator.

[0139] Nonlimiting examples of suitable application methods include brushing, pouring, spraying, coating, rolling, spreading, and injecting.

[0140] In an embodiment, the two-component solvent-based adhesive composition is applied between the first substrate and the second substrate at a coat weight from 3 grams per square meter (g/m.sup.2) to 4 g/m.sup.2.

[0141] 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.

[0142] 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 (D): [0143] First Substrate/Two-Component Solvent-Based Adhesive Composition Structure (D)

[0144] In an embodiment, the Structure (D) is dried to form an adhesive layer in direct contact with the first substrate. In an embodiment, the Structure (D) is dried by passing it through an oven at a temperature sufficient 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 (E): [0145] First Substrate/Adhesive Layer/Second Substrate Structure (E).

[0146] 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.

[0147] The adhesive layer of Structure (E) is formed from curing, or drying the two-component solvent-based adhesive corn position. The two-component solvent-based adhesive composition is formed from mixing and reacting the (A) isocyanate component and the (B) polyol component in the presence of (C) a solvent.

[0148] The laminate includes the first substrate in direct contact with the adhesive layer, and the second substrate in direct contact with the adhesive layer.

[0149] 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), and the laminate has one, some, or all of the following properties: (i) an initial bond strength (green bond) from 0.49 N/2.54 cm to 5.0 N/2.54 cm; and/or (ii) a bond strength after one day from 7.6 N/2.54 cm to 16.7 N/2.54 cm, or 20 N/2.54 cm; and/or (iii) a bond strength after seven days from 8.0 N/2.54 cm to 14.5 N/2.54 cm, or 20 N/2.54 cm; and/or (iv) a bond strength after the boil-in-bag test from 8.8 N/2.54 cm, or 9.0 N/2.54 cm to 17.0 N/2.54 cm, or 18.0 N/2.54 cm, or 20 N/2.54 cm; or from 8.8 N/2.54 cm to 20 N/2.54 cm; and/or (v) a bond strength after chemical aging from 0.3 N/2.54 cm to 3.5 N/2.54 cm, or 5.0 N/2.54 cm, or 10.0 N/2.54 cm; or from 0.3 N/2.54 cm to 10.0 N/2.54 cm.

[0150] 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), and the laminate has one, some, or all of the following properties: (i) an initial bond strength from 1.0 N/2.54 cm to 5.0 N/2.54 cm, or 7.0 N/2.54 cm; and/or (ii) a bond strength after one day from 10.0 N/2.54 cm, or 11.0 N/2.54 cm to 16.0 N/2.54 cm, or 20 N/2.54 cm; and/or (iii) a bond strength after seven days from 11.0 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 8.0 N/2.54 cm to 11.0 N/2.54 cm, or 15.00 N/2.54 cm; and/or (v) a bond strength after chemical aging from 1.0 N/2.54 cm to 10.0 N/2.54 cm, or 12.0 N/2.54 cm, or 15.0 N/2.54 cm.

[0151] 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), and the laminate has one, some, or all of the following properties: (i) an initial bond strength from 0.2 N/2.54 cm to 4.0 N/2.54 cm, or 5.0 N/2.54 cm; and/or (ii) a bond strength after one day from 14.0 N/2.54 cm to 30.0 N/2.54 cm, or 40.0 N/2.54 cm; and/or (iii) a bond strength after seven days from 13.0 N/2.54 cm, to 22.0 N/2.54 cm, or 25.0 N/2.54 cm; and/or (iv) a bond strength after the boil-in-bag test from 3.0 N/2.54 cm to 5.0 N/2.54 cm, or 8.0 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; and/or (v) a bond strength after chemical aging from 2.9 N/2.54 cm to 8.5 N/2.54 cm, or 10.0 N/2.54 cm, or 15.0 N/2.54 cm.

[0152] 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), and the laminate has one, some, or all of the following properties: (i) an initial bond strength from 0.2 N/2.54 cm to 4.0 N/2.54 cm, or 5.0 N/2.54 cm, or 10.0 N/2.54 cm; and/or (ii) a bond strength after one day from 10.0 N/2.54 cm, or 14.0 N/2.54 cm to 21.0 N/2.54 cm, or 25.0 N/2.54 cm; or from 10.0 N/2.54 cm to 25.0 N/2.54 cm, or from 14.0 N/2.54 cm to 21.0 N/2.54 cm; and/or (iii) a bond strength after seven days from 15.0 N/2.54 cm to 27.0 N/2.54 cm, or 30.0 N/2.54 cm; and/or (iv) a bond strength after the boil-in-bag test from 8.0 N/2.54 cm to 16.0 N/2.54 cm, or 18.0 N/2.54 cm, or 20.0 N/2.54 cm; or from 8.0 N/2.54 cm to 20.0 N/2.54 cm; and/or (v) a bond strength after chemical aging from 9.0 N/2.54 cm to 18.0 N/2.54 cm, or 20.0 N/2.54 cm.

[0153] The laminate may comprise two or more embodiments disclosed herein.

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

[0154] The present disclosure also provides a method of forming the two-component solvent-based adhesive composition.

[0155] In an embodiment, the method includes (A) providing a polyol component containing (i) a polyester-polycarbonate polyol (PE-PC) and (ii) a phosphate-terminated polyol (PT-PO); (B providing an isocyanate component; (C) providing a solvent; and (D) reacting the polyol component with the isocyanate component in the presence of the solvent to form the two-component solvent-based adhesive composition.

[0156] The polyol component, the PE-PC, the PT-PO, the isocyanate component, and the two-component solvent-based adhesive composition may be any respective polyol component, PE-PC, PT-PO, isocyanate component, and two-component solvent-based adhesive composition disclosed herein.

[0157] In an embodiment, the process includes forming the polyol component by mixing the PE-PC with the PT-PO.

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

[0159] The present disclosure also provides an article containing the laminate. Nonlimiting examples of suitable articles include packages, bags, pouches, deep-drawn cans, and containers.

[0160] In an embodiment, the laminate contacts a comestible. A “comestible” is an edible food item.

[0161] By way of example, and not limitation, some embodiments of the present disclosure will now be described in detail in the following Examples.

Examples

[0162] 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 ADCOTE ™ aromatic isocyanate prepolymer The Dow 577 composition solids content = 75 Chemical wt %; solvent = ethyl acetate (EA) Company ADCOTE ™ hydroxyl-terminated polyester/ The Dow 577B polyether polyol composition solids Chemical content = 71 wt %; solvent = ethyl Company acetate (EA) ADCOTE ™ hydroxyl-terminated polyol compo- The Dow L87-124 sition containing a phosphate ester Chemical additive dissolved in ethyl acetate (EA) Company CR86-139 hydroxyl-terminated polyol composition The Dow containing a phosphate ester additive Chemical dissolved in ethyl acetate (EA) Company VORANOL ™ glycerine propoxylated polyether The Dow CP 450 triol (polyether polyol) Chemical OH number = 370-396 mg KOH/g; Company acid number = 0.050 mg KOH/g ISONATE ™ MDI blend of 98 wt % 4,4′-diphenyl- The Dow 125M methane diisocyanate and 2 wt % 2,4′- Chemical diphenylmethane diisocyanate; Company NCO content = 33.2 wt % adipic acid (AA) aliphatic diacid monomer Aldrich 1,6-hexanediol diol monomer Aldrich (HDO) neopentyl glycol diol monomer Aldrich (NPG) 1,2-propanediol diol monomer Aldrich (PDO) 1,4-butanediol diol monomer Aldrich (BDO) dimethyl carbonate ester Aldrich carbonate (DMC)

A. Preparation of the Polyester-Polycarbonate Polyol

Preparation of Poly(1,4-Butanediol-Carbonate) (BDO-PC)

[0163] A 30 gallon 316L stainless steel vessel having an internal diameter of 20 inches is equipped with internal baffles, a variable speed 12-inch 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) 1,4-butanediol (BOO) 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. Dimethyl carbonate (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.1H-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.

[0164] A poly(1,4-butanediol-carbonate) (BDO-PC) is prepared that has an OH number of 54 mg KOH/g and a number average molecular weight (Mn) of 1960 g/mol.

Preparation of Polyester-Polycarbonate Polyols (PE-PC)

[0165] Polyester-polycarbonate polyols are synthesized according to the following general procedure, with detailed formulation compositions for each sample provided in Table 2.

[0166] 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 nitrogen 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 nitrogen 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 1,6-hexanediol (HDO), neopentyl glycol (NPG) and 1,2-propanediol (PDO). The mixture is vacuum degassed and nitrogen purged up to three times, and then slowly heated to less than 100° C. Adipic acid (AA) 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-PC 1 PE-PC 2 PE-PC 3 Polyester 4 adipic acid (AA).sup.1 42.92 42.93 43.13 43.48 1,2-propanediol (PDO).sup.1 18.68 18.67 19.49 19.15 neopentyl glycol (NPG).sup.1 11.62 11.62 12.00 11.75 1,6-hexanediol (HDO).sup.1 25.37 25.36 24.90 25.63 poly(1,4-butanediol- 1.42 1.42 0.57 0 carbonate) (BDO-PC).sup.1 Appearance liquid liquid liquid liquid Gardner-Color colorless colorless colorless White Acid Value (mg KOH/g) 0.23 0.82 0.32 0.49 OH Number (mg KOH/g) 120.2 131.0 118.6 150.8 Tg (° C.) −67.2 −73.6 −66.4 −63.6 Viscosity @ 25° C. 1597 1721 1824 2560 (mPa .Math. s) Viscosity @ 40° C. 652 685 699 733 (mPa .Math. s) Mn (g/mol) 1769 1882 1776 1363 Mw (g/mol) 3348 3378 3114 2729 Mz (g/mol) 5277 5220 4811 4309 Mw/Mn 1.89 1.80 1.75 2.00 wt % species with Mw 4.2 3.7 4.6 7.5 less than 500 g/mol wt % species with Mw 14.2 13.3 14.8 18.5 less than 1000 g/mol .sup.1mononner weight charges (%), based on the total amount of monomer charged

B. Preparation of the Phosphate-Terminated Polyol

[0167] A 1 liter multi-neck round bottom flask is dried in an oven, flushed with dry nitrogen for 30 minutes, and then charged with 150 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 4 grams 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 hour, and are then cooled to 45° C. 40 grams of ethyl acetate (EA) is added, followed by the slow addition of 50 grams of ISONATE™ 125 M (MDI blend). 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 hour, 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 76 wt %, an OH Number of 112 mg KOH/g, an acid value of 19.0 mg KOH/g, a viscosity at 25° C. of 1665 mPa.Math.s, a Mn of 1700 g/mol, a Mw of 4100 g/mol, and a Mw/Mn of 2.4. The PT-PO contains 4.4 wt % species with a Mw less than 500 g/mol, and 16.0 wt % species with a Mw less than 1000 g/mol.

C. Preparation of the Polyol Component

[0168] The PE-PC 1, PE-PC 2, PE-PC 3, and Polyester 4 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 (PC) are provided below in Table 3. In Table 3, “CS” refers to a comparative sample.

TABLE-US-00003 TABLE 3 Ex Ex Ex Ex Ex CS CS PC 1 PC 2 PC 3 PC 4 PC 5 PC 6 PC 7 PE-PC 1 95.0 90.0 — — — — — PE-PC 2 — — 80.0 — — — — PE-PC 3 — — — 95.0 79.9 — — Polyester 4 — — — — — 95.0 79.2 PT-PO 5.00 10.0 20.0 5.00 20.1 4.98 20.7 OH Number (mg KOH/g) 120.8 121.4 131.2 119.1 120.7 149.7 146.4 Appearance liquid liquid liquid liquid liquid liquid liquid Solids Content (wt %) 98.75 97.5 95.00 98.75 95.0 98.75 96.7 wt % in Table 3 is based on the total weight of the respective Polyol Component

[0169] As shown in Table 3, Ex PC 1-5 each exhibits an OH Number that is less than the OH Number of CS PC 6 and CS PC 7, which indicates that Ex PC 1-5 have a higher Mw than CS PC 6 and CS PC 7.

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

[0170] Two-component solvent-based adhesive compositions are prepared by mixing (A) ADCOTE™ 577 (aromatic isocyanate prepolymer) with (B) one of the Ex PC 1-5, CS PC 6-7, ADCOTE™ 577B (a hydroxyl-terminated polyol composition), ADCOTE™ L87-124 (a hydroxyl-terminated polyol composition), or CR86-139 (hydroxyl-terminated polyol composition) (C) EA, 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 Tables 4 and 5.

E. Formation of a Laminate

[0171] 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.).

[0172] A cast polypropylene film that is a monolayer film having a thickness of 3 mil is provided.

[0173] A poly(ethylene glycol-terephthalate) (PET) film that is a monolayer film having a thickness of 1 mil (24.5 μm) is provided (92LBT, available from DuPont).

[0174] 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): [0175] PET Film/ADCOTE™ 577:Coreactant F Adhesive Layer/Metal Foil Film Structure (I).

[0176] The example and comparative example adhesive compositions are loaded into a Nordmeccanica SDC Labo Combi pilot laminator. The laminator nip temperature is maintained at 60° C., the oven temperature is set at 80° C. for each zone, and the laminator is operated at a speed of 30 meters per minute (m/min). Each example and comparative example adhesive composition is maintained at the solids content of Tables 4 and 5 during lamination.

[0177] The adhesive composition is applied to either the Metal Foil Pre-Laminate (Prelam) or the PET film (92LBT) at a coat weight of 3-4 g/m.sup.2, to form the following Structure (II) and Structure (Ill):

##STR00005##

[0178] 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)).

[0179] Then, the Structure (II) and the Structure (Ill) is cured in a controlled room at a temperature of 25° C. and a relative humidity of 50% for a period of 7-14 days to evaporate all, or substantially all, of the solvent and form an adhesive layer. 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): [0180] Prelam/Adhesive Composition/LDPE Structure (IV) [0181] Prelam/Adhesive Composition/Cast Polypropylene Structure (V) [0182] PET/Adhesive Composition/LDPE Structure (VI) [0183] PET/Adhesive Composition/Cast Polypropylene Structure (VII)

[0184] The properties of each laminate example and comparative sample are provided in Tables 4 and 5. In Tables 4 and 5, “NM” indicates a value was not measured; “FS” indicates a film stretch failure mode; “FT” indicates a film tear or break failure mode; “DL” indicates a delamination failure mode; “AT” indicates an adhesive transfer failure mode, wherein adhesive is transferred to the second film; and “AS” indicates a cohesive failure or adhesive split failure mode, wherein adhesive is found on both films.

TABLE-US-00004 TABLE 4 Ex 1 Ex 2 Ex 3 Ex 4 Ex 5 Adhesive Composition (grams) ADCOTE ™ 577 1494.9 1505.3 1524.6 1489.1 1487.0 Ex PC 1  231.7 — — — — Ex PC 2 —  226.7 — — — Ex PC 3 — —  217.5 — — Ex PC 4 — — —  239.8 — Ex PC 5 — — — —  247.6 CS PC 6 — — — — — CS PC 7 — — — — — ADCOTE ™ 577B — — — — — ADCOTE ™ L87-124 — — — — — CR86-139 — — — — — ethyl acetate 1273.4 1269.0 1258.0 1276.5 1268.4 Adhesive Composition Properties Isocyanate:Polyol 100:15.5 100:15.1 100:14.3 100:16.1 100:16.7 Mixing Ratio Appearance liquid liquid liquid liquid liquid Solids Content (wt %)   45   45   45   45   45 Prelam/Adhesive Layer/LDPE Laminate Bond Strength (BS) (N/2.54 cm) Initial BS (Green Bond)    0.49.sup.AS    3.40.sup.AS    4.00.sup.AS    2.22.sup.AS    2.44.sup.AS BS after 1 day   11.32.sup.FS/FT   16.67.sup.FT   13.56.sup.FS/AT    8.18.sup.AT   12.29.sup.AT BS after 7 days   10.25.sup.FS/AT   12.82.sup.FS/FT   10.35.sup.FS/FT    8.18.sup.AS/AT   14.23.sup.FS/AT BS after Boil-in-Bag    9.82.sup.FS/AT   12.08.sup.FS/AT   16.61.sup.FS/AT    9.33.sup.AT   11.40.sup.FS/AT BS after Chemical Aging    0.31.sup.AS/DL    0.96.sup.AS    3.39.sup.AS    0.49.sup.AS/DL    1.91.sup.AS Prelam/Adhesive Layer/Cast Polypropylene Laminate Bond Strength (BS) (N/2.54 cm) Initial BS (Green Bond)    1.07.sup.AS    2.08.sup.AS    4.92.sup.AS    1.64.sup.AS    2.31.sup.AS BS after 1 day   14.21.sup.AT/FS   13.39.sup.AT   15.72.sup.AS   11.10.sup.AT   12.91.sup.AT BS after 7 days   14.13.sup.AT   14.77.sup.AT   13.85.sup.AT   12.19.sup.AT   14.60.sup.AS BS after Boil-in-Bag    9.13.sup.AT   10.75.sup.AT   10.89.sup.AS    8.15.sup.AT    9.90.sup.AS BS after Chemical Aging    1.00.sup.AS    4.82.sup.AS    9.13.sup.AS    2.86.sup.AS    6.97.sup.AS CS 6 CS 7 CS 8 CS 9 CS 10 Adhesive Composition (grams) ADCOTE ™ 577 1651.7 1630.5 1672.9 1556.0 1550.8 Ex PC 1 — — — — — Ex PC 2 — — — — — Ex PC 3 — — — — — Ex PC 4 — — — — — Ex PC 5 — — — — — CS PC 6 — — —  186.6 — CS PC 7 — — — —  198.8 ADCOTE ™ 577B  147.1 — — — — ADCOTE ™ L87-124 — —  107.1 — — CR86-139 —  184.2 — — — ethyl acetate 1201.2 1185.3 1220.0 1259.9 1260.8 Adhesive Composition Properties Isocyanate:Polyol 100:8.9 100:11.3 100:6.4 100:12.0 100:12.8 Mixing Ratio Appearance liquid liquid liquid liquid liquid Solids Content (wt %)   44.8   45.1   45   45   45 Prelam/Adhesive Layer/LDPE Laminate Bond Strength (BS) (N/2.54 cm) Initial BS (Green Bond)    3.68.sup.AS    4.12.sup.AS    4.35.sup.AS    0.47.sup.AS    1.13.sup.AS BS after 1 day   15.39.sup.FT/FS   17.54.sup.FT/FS   19.33.sup.FT    7.22.sup.AT   10.92.sup.AT BS after 7 days   15.02.sup.FT/FS   13.67.sup.FT/FS   18.81.sup.FT    7.07.sup.AT    8.82.sup.AT BS after Boil-in-Bag    8.51.sup.AS    7.41.sup.AS    8.05.sup.AS    8.71.sup.AT    8.03.sup.AT BS after Chemical Aging    0.82.sup.AS/AT    1.05.sup.AS    3.29.sup.AS    0.25.sup.AS/DL    1.44.sup.AS Prelam/Adhesive Layer/Cast Polypropylene Laminate Bond Strength (BS) (N/2.54 cm) Initial BS (Green Bond)    1.52.sup.AS    4.64.sup.AS    6.10.sup.AS    0.76.sup.AS    1.38.sup.AS BS after 1 day   17.03.sup.AT   24.16.sup.FT   18.52.sup.FT   12.72.sup.AT   12.14.sup.AT BS after 7 days   20.19.sup.FT   25.43.sup.FT   18.96.sup.FT   12.14.sup.AT   13.12.sup.AS/AT BS after Boil-in-Bag    9.75.sup.FT/AS    9.78.sup.FT/AS    9.80.sup.AS    7.48.sup.AT    8.97.sup.AT BS after Chemical Aging    3.39.sup.AS    2.58.sup.AS   10.16.sup.1AS    1.91.sup.AS    3.13.sup.AS

TABLE-US-00005 TABLE 5 Ex 1 Ex 2 Ex 3 Ex 4 Ex 5 Adhesive Composition (grams) ADCOTE ™ 577 1494.9 1505.3 1524.6 1489.1 1487.0 Ex PC 1  231.7 — — — — Ex PC 2 —  226.7 — — — Ex PC 3 — —  217.5 — — Ex PC 4 — — —  239.8 — Ex PC 5 — — — —  247.6 CS PC 6 — — — — — CS PC 7 — — — — — ADCOTE ™ 577B — — — — — ADCOTE ™ L87-124 — — — — — CR86-139 — — — — — ethyl acetate 1273.4 1269.0 1258.0 1276.5 1268.4 Adhesive Composition Properties Isocyanate:Polyol 100:15.5 100:15.1 100:14.3 100:16.1 100:16.7 Mixing Ratio Appearance liquid liquid liquid liquid liquid Solids Content (wt %)   45   45   45   45   45 PET/Adhesive Layer/LDPE Laminate Bond Strength (BS) (N/2.54 cm) Initial BS (Green Bond)    0.31.sup.AS    2.60.sup.AS    3.62.sup.AS    0.21.sup.AS    2.54.sup.AS BS after 1 day   28.78.sup.FT/FS   17.08.sup.FT   15.16.sup.FS   15.19.sup.FT/FS   16.97.sup.FT/FS BS after 7 days   20.88.sup.FT/FS   13.52.sup.FT/FS   18.52.sup.FT   19.47.sup.FT   21.34.sup.FT BS after Boil-in-Bag    4.03.sup.AS    3.99.sup.AS    4.35.sup.AS/AT    3.20.sup.AT    3.84.sup.AT BS after Chemical Aging    3.47.sup.AS    8.11.sup.AT    5.69.sup.AT    2.96.sup.AT    6.18.sup.AT PET/Adhesive Layer/Cast Polypropylene Laminate Bond Strength (BS) (N/2.54 cm) Initial BS (Green Bond)    0.23.sup.AS    2.32.sup.AS    3.36.sup.AS    0.27.sup.AS    1.99.sup.AS BS after 1 day   18.04.sup.FT   20.39.sup.FT   14.87.sup.FT   15.97.sup.FT   16.21.sup.FT BS after 7 days   25.98.sup.FT   18.88.sup.FT   16.06.sup.FT   16.54.sup.FT   15.66.sup.FT BS after Boil-in-Bag   12.06.sup.FT   10.73.sup.FT   15.69.sup.FT    8.20.sup.FT    9.57.sup.FT BS after Chemical Aging   17.27.sup.FT   10.86.sup.FT   10.03.sup.FT    9.22.sup.FT   10.14.sup.FT CS 6 CS 7 CS 8 CS 9 CS 10 Adhesive Composition (grams) ADCOTE ™ 577 1651.7 1630.5 1672.9 1556.0 1550.8 Ex PC 1 — — — — — Ex PC 2 — — — — — Ex PC 3 — — — — — Ex PC 4 — — — — — Ex PC 5 — — — — — CS PC 6 — — —  186.6 — CS PC 7 — — — —  198.8 ADCOTE ™ 577B  147.1 — — — — ADCOTE ™ L87-124 — —  107.1 — — CR86-139 —  184.2 — — — ethyl acetate 1201.2 1185.3 1220.0 1259.9 1260.8 Adhesive Composition Properties Isocyanate:Polyol 100:8.9 100:11.3 100:6.4 100:12.0 100:12.8 Mixing Ratio Appearance liquid liquid liquid liquid liquid Solids Content (wt %)   44.8   45.1   45   45   45 PET/Adhesive Layer/LDPE Laminate Bond Strength (BS) (N/2.54 cm) Initial BS (Green Bond)    1.61.sup.AS    3.00.sup.AS    4.46.sup.AS    0.39.sup.AS    0.68.sup.AS BS after 1 day   18.38.sup.FT   18.17.sup.FT   22.86.sup.FT    5.07.sup.AT    8.14.sup.AT BS after 7 days   17.04.sup.FT/FS   15.75.sup.FT/FS   23.41.sup.FT/FS    5.70.sup.AS/AT    6.22.sup.AT BS after Boil-in-Bag    3.38.sup.AS    2.82.sup.AS    3.81.sup.AS    3.53.sup.AT    3.71.sup.AT BS after Chemical Aging    3.51.sup.AS    3.19.sup.AS    4.80.sup.AS    3.70.sup.AT    3.79.sup.AT PET/Adhesive Layer/Cast Polypropylene Laminate Bond Strength (BS) (N/2.54 cm) Initial BS (Green Bond) NM NM NM    0.19.sup.AS    0.27.sup.AS BS after 1 day NM NM NM    7.55.sup.AT    9.69.sup.AT BS after 7 days NM NM NM   15.72.sup.FT   12.43.sup.FT BS after Boil-in-Bag NM NM NM    9.15.sup.FT    8.92.sup.FT BS after Chemical Aging NM NM NM   10.05.sup.FT   10.66.sup.FT

F. Results

[0185] As shown in Table 4, CS 6-10 each includes an adhesive layer formed from (A) an isocyanate component (ADCOTE™ 577), (B) a polyol component (ADCOTE™ 577B, CR86-139, ADCOTE™ L87-124, CS PC 6, and CS PC 7, respectively) that lacks a phosphate-terminated polyol (PT-PO), and (C) a solvent (ethyl acetate (EA)). The laminate structures of CS 6-10 having the Structure (IV) (i.e., Prelam/Adhesive Composition/LDPE) each exhibits a bond strength after the boil-in-bag test of less than 8.8 N/2.54 cm. Thus, CS 6-10 each exhibits insufficient bond strength after the boil-in-bag test.

[0186] As shown in Table 4, Ex 1-5 each includes an adhesive layer formed from (A) an isocyanate component (ADCOTE™ 577), (B) a polyol component (PC 1-5, respectively) containing (i) a polyester-polycarbonate polyol (PE-PC) and (li) a PT-PO, and (C) a solvent (EA). The laminate structures of Ex 1-5 having the Structure (IV) (i.e., Prelam/Adhesive Composition/LOPE) each exhibits a bond strength after the boil-in-bag test of greater than 8.8 N/2.54 cm. Thus, Ex 1-5 each exhibits sufficient bond strength after the boil-in-bag test.

[0187] As shown in Table 5, CS 6-10 each includes an adhesive layer formed from (A) an isocyanate component (ADCOTE™ 577), (B) a polyol component (ADCOTE™ 577B, CR86-139, ADCOTE™ L87-124, CS PC 6, and CS PC 7, respectively) that lacks a PT-PO, and (C) a solvent (EA). The laminate structures of CS 6-10 having the Structure (VII) (i.e., PET/Adhesive Composition/Cast Polypropylene) each exhibits a bond strength after one day of less than 10.0 N/2.54 cm. Thus, CS 6-10 each exhibits insufficient bond strength after one day.

[0188] As shown in Table 5, Ex 1-5 each includes an adhesive layer formed from (A) an isocyanate component (ADCOTE™ 577), (B) a polyol component (PC 1-5, respectively) containing (i) PE-PC and (ii) PT-PO, and (C) a solvent (EA). The laminate structures of Ex 1-5 having the Structure (VII) (i.e., PET/Adhesive Composition/Cast Polypropylene) each exhibits a bond strength after one day of greater than 10.0 N/2.54 cm. Thus, Ex 1-5 each exhibits sufficient bond strength after one day.

[0189] 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.