PHOSPHATE ADHESION PROMOTERS

Abstract

A first aspect of the present invention is an adhesive composition comprising one or more polyisocyanates and one or more phosphate-functional polyols. A second aspect of the present invention is a method of bonding two substrates together to form a bonded article, said method comprising the steps of applying a layer of the composition of the first aspect to one of said substrates, contacting said layer of the composition of claim 1 to a second substrate, and curing or allowing to cure the composition of claim 1. A third aspect of the present invention is a bonded article formed by the method of the second aspect.

Claims

1. An adhesive composition comprising one or more polyisocyanates and one or more phosphate-functional polyols.

2. The adhesive composition of claim 1, wherein said phosphate functional polyol is a phosphate ester of a precursor polyol.

3. The adhesive of claim 2, wherein said precursor polyol is either an alkyl triol or alkoxylated alkyl triol.

4. The adhesive of claim 2, wherein said precursor polyol is either glycerol or alkoxylated glycerol.

5. The adhesive of claim 2, wherein said precursor polyol is a propoxylated glycerol.

6. A method of bonding two substrates together to form a bonded article, said method comprising the steps of applying a layer of the composition of claim 1 to one of said substrates, contacting said layer of the composition of claim 1 to a second substrate, and curing or allowing to cure the composition of claim 1.

7. A bonded article formed by the method of claim 6.

8. The bonded article of claim 6, wherein said bonded article is a laminate.

Description

EXAMPLE 1

[0106] ADCOTE™ 577 (available from Dow Chemical Company) is an isocyanate functional prepolymer comprised of about 72-74% polyurethane resin, 2-3% methylenebis (4-phenylisocyanate) and 23-25% ethyl acetate. Typical viscosity (Technical Data Sheet) is 3900 mPa*s.

EXAMPLE 2. POLYESTER-POLYETHER POLYOL

[0107] The method described in WO 2013/053555 was used. 2011.0 g (7.89 mol) of VORANOL™ CP260 triol polyether polyol, 1520.4 g (10.25 mol) phthalic anhydride and 0.20 g of 2-Ethyl-4-Methyl-Imidazole (EMI, 41 ppm based on the weight of product) were mixed with stirring at 50 rpm in 5 L stainless steel alkoxylation reactor. The reaction mixture was flushed 10 times with 600 kPa (6 bar) nitrogen (N.sub.2) pressure. The reactor was thermostated at 130° C. with 600 kPa (6 bar) of N.sub.2 pressure. The obtained slurry gradually dissolved in the reactor, becoming mainly liquid after 0.5 h at this temperature. The stirring rate was gradually increased from 50 to 200 rpm. The reactor content was stirred for an additional 1.5 h. The N.sub.2 pressure in the reactor was reduced to 1.0 bar, and the stirring rate was increased to 300 rpm. PO (1246.0 g, 21.46 mol) was fed to the reactor at a feed rate of 15 g/min over 85 min. The immediate reaction start was accompanied by an exotherm. At the completion of the feed the total pressure in the reactor had reached 490 kPa (4.9 bar). 3.0 h of additional digestion time was allowed. The total pressure in the reactor decreased to 430 kPa (4.3 bar). The reactor temperature was decreased to 100° C. 6.80 g of a 10% solution of triflic acid (TFA, 142 ppm based on the weight of product) in ethanol was injected into the reactor with the help of a pressurized stainless steel bomb, connected to the reactor Immediate pressure drop in the reactor and an exotherm were observed, 30 min of additional digestion time was allowed. Residual nitrogen pressure was vented off, the reaction mixture was flushed 10 times with 600 kPa (6 bar) N.sub.2 pressure. Potassium hydroxide (7.16 g, 0.5 mol/1 solution in ethanol) was injected into the reactor with the help of a pressurized stainless steel bomb, connected to the reactor, in order to neutralize the remaining triflic acid. The product was then stripped in vacuum for 1 h at 120° C. A colorless viscous liquid was obtained.

[0108] The produced hybrid polyester-polyether polyol had the following properties: OHN: 276 mg KOH/g; Cone and Plate Viscosity (40 mm diameter, 0.5° cone, 10 sec.sup.−1) at 25° C.: 31700 mPa*s (Density at 25° C.: 1.156 g/cm.sup.3; pH: 5.9; Mn=460 g/mol, Mw/Mn=1.17.

EXAMPLE 3

[0109] MOR-FREE™ C411 (Dow Chemical Company) is a solvent free blend containing polyester polyol with typical viscosity reported as 1100 mPa*s

EXAMPLE 4. PREPARATION OF POLYETHER PHOSPHATES

[0110] Reactant quantities are shown in the table below. A 1 L multi-neck round bottom flask was dried in an oven, flushed with dry N.sub.2 for 30 minutes, then charged with polyether polyol and placed under an N.sub.2 sweep of 70 mL/min A syringe was loaded with 115% Polyphosphoric acid (PPA) from ALDRICH CHEMICAL Company. PPA was added dropwise from the syringe to the polyether polyol with strong agitation. A minimal rise in temperature was noted. The reactor contents were then heated to 100° C. for 1 hour, cooled (significant increase in viscosity was observed), and the clear and colorless product was packaged.

[0111] For comparison, sample 4F was prepared by adding 100% phosphoric acid (PA) crystals to VORANOLTMCP 450. The mixture was warmed to 50° C. and stirred until the crystals were completely dissolved.

[0112] Results:

TABLE-US-00001 Precursor polyol PPA PA Example Precursor polyol type amount (g) (g) (g) 4A VORNAOL ™ CP 450 polyol.sup.(1) 180 20 4B VORNAOL ™CP 450 polyol.sup.(1) 192 8 4C VORNAOL ™CP 450 polyol.sup.(1) 196 4 4D POLY-G ® 30-240 polyol.sup.(2) 196 4 4E VORANOL ™ CP 1055 polyol.sup.(3) 196 4 4F VORNAOL ™CP 450 polyol.sup.(1) 196 4 .sup.(1)The Dow Chemical Company, average molecular weight = 450 .sup.(2)The ARCH Chemical Company, average molecular weight = 700 .sup.(3)The Dow Chemical Company, average molecular weight = 1055

TABLE-US-00002 Example VISC (mPa * s) OHN AV 4A 6700 402 45.2 4B 820 393 25.8 4C 550 387 9.7 4D 415 240 11.1 4E 460 159 12.3 4F 369 18.5

EXAMPLE 5: PREPARATION OF URETHANE-POLYETHER PHOSPHATE

[0113] Reactant quantities are in the table below. A 1 L multi-neck round bottom flask was dried in an oven, flushed with dry N.sub.2 for 30 minutes, then charged with VORANOL™ CP 450 polyether polyol and placed under an N.sub.2 sweep of 70 mL/min A syringe was loaded with 115% Polyphosphoric acid (PPA) from ALDRICH CHEMICAL Co. The PPA was added dropwise to the polyether polyol with strong agitation. A minimal temperature increase was observed. The reactor contents were heated to 100° C. for 1 hour, then cooled to 45° C. ISONATE™ 125M polyisocyanate was added. The temperature rose to about 95° C. from the heat of reaction. Also, there was an increase in viscosity and development of a yellow color. The reactor was then brought to 65° C., and ethyl acetate was added to cut viscosity and improve stirring. After 1 hour, the reactor was cooled and the content was packaged.

TABLE-US-00003 Ethyl VORNAOL ™ PPA Acetate ISONATE ™ Example CP 450 (g) (g) (g) 125M (g) VISC 5 150 4 40 50 42,750 mPa * s

EXAMPLE 6: TESTING ADHESIVES

[0114] Samples in the following tables were prepared by combining the polyol portion of the adhesive with the additives shown the tables followed by addition of solvent to obtain the desired final concentration, then adding the isocyanate functional portion and mixing for about 15 minutes.

[0115] The tables below summarize T-peel test results for PET-Al/Pliant 808.24 laminates. Adhesive coat weight (dry) was approximately 3.26 g/m.sup.2 (2.0 lbs/ream). T-peel results are shown at various times. Also shown are the results of the boil in bag test with the 1:1:1 sauce (blend of equal parts by weight of vinegar, oil and ketchup). The data show that the most of the laminates made with phosphate-functional polyol gave cured bonds comparable with the control adhesive but green bonds (that is, T-peel values at short time) were significantly better than the controls. Higher green bonds are desirable because this simplifies the lamination process and helps avoid defects that may result from the two films moving before the laminate has cured. Once the adhesive has cured, the desired mode of failure is film stretch (FS) or film tear (FT). The control adhesive was made with the isocyante functional prepolymer of Example 1 as one component and the coreactant ADCOTE™577B polyol (herein “polyol CON”) as the second component. ADCOTE™577B is a blend containing polyester and polyether polyols and 28-30% ethyl acetate with a typical viscosity (Technical Data Sheet) of 130 mPa*s. It is available from Dow Chemical Company.

[0116] Samples made with VORANOL™ CP 1055 polyol gave poor green bonds due to limited miscibility of the CP 1055 polyether with Example 1 prepolymer. For all of the samples 4A-4E, T-peel bonds after the boil in bag tests were as good as or better than the control adhesive and better than the comparative examples without PPA Some defects (“blisters”) were seen in some samples with higher concentrations (4-10%) of PPA in VORANOL™ CP 450 (e.g. 4A and 4B). “Blisters” refers to small bubbles that appear in the laminate surface after exposure to boil in bag testing. Table 5 shows that 100% phosphoric acid (PA) does not give the benefit of resistance to the 1/1/1 sauce that is observed with the polyols reacted with PPA. “Tunneling” refers to channels that form from areas of delamination where the two films have separated during the test. This is a major defect. The following tables 1-9 show results of laminates of PET-Al prelam (primary substrate) with Pliant 808.24 (secondary substrate).

TABLE-US-00004 TABLE 1A Formulations Control 59-5 59-6 69-5 69-6 Name Wt. (g) Wt. (g) Wt. (g) Wt. (g) Wt. (g) Example 1 14.77 15.52 15.46 15.32 15.14 polyol CON 1.30 Example 4A 0.08 0.16 Example 4B 0.37 Example 4C 0.61 DPG 0.28 0.25 0.15 0.04 EtAc 13.93 14.12 14.13 14.16 14.21

TABLE-US-00005 TABLE 1B T-Peel Results (grams per 2.54 cm (g/inch)) Control 59-5 59-6 T-peel FM T-peel FM T-peel FM Green 156 AS 385 AS 425 AS  1 Day 1260 FS 1792 FS 1654 FS  7 Day 1551 FT/FS 1834 FS 1697 FS 14 Day 1692 FS 1839 FS 1739 FT/FS BB 1:1:1 790 AT 1859 FS/FT 1287 FS/AS Comment No Defect Blisters No Defect

TABLE-US-00006 TABLE 1C Further T-Peel Results (grams per 2.54 cm (g/inch)) 69-5 69-6 T-peel FM T-peel FM Green 340 AS 335 AS  1 Day 1495 FS/FT 1556 FS  7 Day 1719 FS 1678 FS 14 Day 1830 FS 1805 FS/FT BB 1:1:1 1763 FS 1766 FS comment Slight Blistering Slight Blistering

TABLE-US-00007 TABLE 2A Formulations Control 59-3 59-4 69-3 69-4 Name Wt. (g) Wt. (g) Wt. (g) Wt. (g) Wt. (g) Example 1 14.77 14.91 14.91 15.00 15.06 polyol CON 1.30 Example 3 0.75 0.67 0.38 0.11 Example 4A 0.075 0.15 Example 4B 0.38 Example 4C 0.60 EtAc 13.93 14.27 14.27 14.24 14.23

TABLE-US-00008 TABLE 2B T-Peel Results (grams per 2.54 cm (g/inch)) Control 59-3 59-4 T-peel FM T-peel FM T-peel FM Green 156 AS 319 AS 377 AS  1 Day 1260 FS 1878 FS/FT 1762 FS  7 Day 1551 FT/FS 1748 FS 1758 FS/FT 14 Day 1692 FS 1974 FT/FS 1860 FS BB 1:1:1 790 AT 1673 FT/FS 1842 FS comment No Defect Blisters No Defect

TABLE-US-00009 TABLE 2C Further T-Peel Results (grams per 2.54 cm (g/inch)) 69-3 69-4 T-peel FM T-peel FM Green 347 AS 356 AS  1 Day 1600 FS 1593 FS  7 Day 1743 FS 1636 FS/FT 14 Day 1857 FT/FS 1806 FS BB 1:1:1 1907 FS 1805 FS comment No Defect No Defect

TABLE-US-00010 TABLE 3A Formulations Control Comparative 91-10-1 91-10-2 Name Wt. (g) Wt. (g) Wt. (g) Example 1 14.77 15.09 15.09 polyol CON 1.30 Example 4C 0.679 VORANOL ™ 0.68 CP 450 EtAc 13.93 14.23 14.23

TABLE-US-00011 TABLE 3B T-Peel Results (grams per 2.54 cm (g/inch)) Comparative Control 91-10-1 91-10-2 T-peel FM T-peel FM T-peel FM Green 156 AS 344 AS 340 AS  1 Day 1260 FS 1788 FS 1966 FS  7 Day 1551 FT/FS 1784 FS 1906 FS 14 Day 1692 FS 1548 FS 1637 FS/FT BB 1:1:1 790 AT 1233 AS 1577 FS comment No Defect Slight No tunneling Defect

TABLE-US-00012 TABLE 4A Formulations Control 58-59-1 58-59-2 58-69-1 58-69-2 Name Wt. (g) Wt. (g) Wt. (g) Wt. (g) Wt. (g) Example 1 14.77 14.81 14.81 14.86 14.95 polyol CON 1.30 Example 4A 0.07 0.15 Example 4B 0.19 Example 4C 0.37 Example 2 0.81 0.74 0.67 0.41 EtAc 13.93 14.30 14.30 14.28 14.27

TABLE-US-00013 TABLE 4B T-Peel Results (grams per 2.54 cm (g/inch)) Control 58-59-1 58-59-2 T-peel FM T-peel FM T-peel FM Green 156 AS 513 AS 498 AS  1 Day 1260 FS 1798 FS/FT 1789 FS  7 Day 1551 FT/FS 1775 FS 1790 FS 14 Day 1692 FS 1857 FS/FT 2036 FS BB 1:1:1 790 AT 1812 FS/FT 1631 FS comment No Defect No Defect Blisters

TABLE-US-00014 TABLE 4C Further T-Peel Results (grams per 2.54 cm (g/inch)) 58-69-1 58-69-2 T-peel FM T-peel FM Green 363 AS 353.7 AS  1 Day 1613 FS 1614 FS  7 Day 1772 FS/FT 1783 FT 14 Day 1823 FS/FT 1722 FS BB 1:1:1 1850 FS 1853 FS comment Slight Blistering No Defect

TABLE-US-00015 TABLE 5A Formulations 22-1 22-2 22-3 22-4 Name Wt. (g) Wt. (g) Wt. (g) Wt. (g) Example 1 15.09 15.09 15.19 15.00 Example 4F 0.68 0.30 0.53 0.45 CP 450 0.38 DPG 0.08 Example 2 0.30 EtAc 14.23 14.23 14.20 14.25

TABLE-US-00016 TABLE 5B T-Peel Results (grams per 2.54 cm (g/inch)) 91-22-1 91-22-2 91-22-3 91-22-4 T-peel FM T-peel FM T-peel FM T-peel FM Green 325 AS 326 AS 360 AS 324 AS  1 Day 1462 FS 1300 FS/AS 1456 FS 929 AS  7 Day 1659 FS 1687 FS/FT 1662 FS 1739 FS/FT 14 Day 1697 FS 1590 FS 1817 FS 1603 FS BB 1:1:1 509 AS 763 AS 913 AS 822 AS comment Tunneling Tunneling Tunneling Tunneling

TABLE-US-00017 TABLE 6A Formulations 91-21-1 91-21-2 91-21-3 91-21-4 Name Wt. (g) Wt. (g) Wt. (g) Wt. (g) Example 1 14.19 14.43 14.76 14.56 Example 5 1.63 0.94 0.96 0.95 CP 450 0.29 DPG 0.13 Example 2 0.40 EtAc 14.18 14.23 14.15 14.20

TABLE-US-00018 TABLE 6B T-Peel Results (grams per 2.54 cm (g/inch)) 91-21-1 91-21-2 91-21-3 91-21-4 T-peel FM T-peel FM T-peel FM T-peel FM Green 369 AS 387 AS 351 AS 337 AS  1 Day 1650 FS 1534 FS 1423 FS 1438 FS  7 Day 1600 FS 1648 FS 1605 FS 1636 FS 14 Day 1497 FS 1628 FS 1530 FS/FT 1651 FS/FT BB 1:1:1 1645 FS 1747 FS 1473 FS 1688 FS comment No No No No Defect Defect Defect Defect

TABLE-US-00019 TABLE 7A Formulations 91-20-2 91-20-3 Name Wt. (g) Wt. (g) Example 1 13.95 13.87 Example 4E 1.53 0.83 CP 1055 0.76 EtAc 14.52 14.54

TABLE-US-00020 TABLE 7B T-Peel Results (grams per 2.54 cm (g/inch)) 91-20-2 91-20-3 T-peel FM T-peel FM Green.sup.(4) 11.3 Phase Sep..sup.(4) 6 Phase Sep..sup.(4)  1 Day 659 AS 519 AS  7 Day 1743 FS/FT 1777 FS 14 Day 1569 FS 1571 FS BB 1:1:1 1610 FS 1657 FS comment No Defect.sup.(4) No Defect.sup.(4) .sup.(4)Laminate showed some defects prior to BB 1:1:1 test because it was difficult to make good laminates with such low green bonds. But, no new defects appeared during the BB 1:1:1 test.

TABLE-US-00021 TABLE 8A Formulations 91-20-4 91-20-5 91-20-6 Name Wt. (g) Wt. (g) Wt. (g) Example 1 14.29 14.65 14.46 CP 450 0.29 Example 4E 0.86 0.88 0.87 DPG 0.13 Example 2 0.43 EtAc 14.42 14.34 14.38

TABLE-US-00022 TABLE 8B T-Peel Results (grams per 2.54 cm (g/inch)) 91-20-4 91-20-5 91-20-6 T-peel FM T-peel FM T-peel FM Green.sup.(5) 4.7 Phase 5.3 Phase 4 Phase Sep..sup.(5) Sep..sup.(5) Sep..sup.(5).  1 Day 822 AS 621 AS 725 AS  7 Day 1799 FS 1722 FS 1785 FS/FT 14 Day 1689 FS 1652 FS 1554 FS BB 1:1:1 1742 FS 1634 FS 1853 FS comment No No No Tunnel Tunnel Tunnel .sup.(5)Example is not fully miscible with Voranol ™ CP 1055 polyol. This is responsible for the poor green bonds.

TABLE-US-00023 TABLE 9A Formulations 29-1 29-2 29-3 Name Wt. (g) Wt. (g) Wt. (g) Example 1 14.63 14.55 14.63 Example 4D 1.0 0.65 0.66 PolyG ™ 30-240 0.44 SP11-33 Ex 0.37 EtAc 14.35 14.36 14.34

TABLE-US-00024 TABLE 9B T-Peel Results (grams per 2.54 cm (g/inch)) 91-20-4 91-20-5 91-20-6 T-peel FM T-peel FM T-peel FM Green.sup.(5) 12 Phase 5 Phase 45 Phase Sep..sup.(6) Sep..sup.(6) Sep..sup.(6)  1 Day 1782 FS 1696 FS 1508 FS  7 Day 1676 FS 1663 FS 1805 FS 14 Day 1847 FS 1721 FS 1702 FS BB 1:1:1 1578 FS 1499 FS 1569 FS comment No No No Defect Defect Defect .sup.(6)Example is not fully miscible with Voranol ™ CP 1055 polyol. This is responsible for the poor green bonds.

EXAMPLE 7

[0117] ADCOTE™795 is the Hydroxyl Component of a Two Part Polyurethane adhesive. It is a blend containing hydroxyl functional polyester and hydroxyl functional acrylic polymers (70-80%), glycols (1-5%) and ethyl acetate 20-25%. It is available from Dow Chemical Company. Typical viscosity (from data sheet) 825 mPa*s.

EXAMPLE 8: PREPARATION OF ISOCYANATE-FUNCTIONAL PREPOLYMER

[0118] The ingredients were as follows:

TABLE-US-00025 Item Monomer/Intermediate Charge (g) 1 4,4′-Diphenylmethane diisocyanate 200.0 (ISONATE ™ 125M) 2 Propoxylated Glycerine, Mw 450 7.46 (Voranol ™ CP450) 3 Polypropylene glycol, Mw 430 97.4 (Voranol ™ 220-260) 4 Benzoyl chloride 0.10

[0119] Item 1 was charged to a dry reactor at 50° C. The reactor was kept under an atmosphere of dry nitrogen throughout the process. Item 2 was charged to the reactor and the resin mixture was heated to 80° C. Item 3 was added over 30 min at a rate to maintain the temperature at 80-85° C. The resin mixture was held at 80° C. for 2 hours. The % NCO was monitored until it was 15.0±0.3%. The resin was cooled to 50° C.-60° C., item 4 was added; the solution was mixed well, then packaged.

[0120] The final resin had the following properties: 14.8% NCO. Cone and plate viscosity (40 mm diameter, 0.5° cone, 10 sec.sup.−1) results are shown in the table below.

TABLE-US-00026 Temp (° C.) 25 35 45 55 65 75 80 VISC (mPa * s) 20,070 6875 2475 1225 650 400 325
Dry ethyl acetate (30 g) was added to 170 g of the resin. The resin dissolved with stirring to give a solution with 85% solid resin and a viscosity of 325 mPa*s at 25°

EXAMPLE 9: PREPARATION OF GLYCERINE PHOSPHATE

[0121] Polyphosphoric acid (40 grams of 115% from Aldrich Chemical Co.) was placed in a three neck flask with stirrer, thermometer and nitrogen inlet/outlet. A slow stream of dry nitrogen was passed through the reactor throughout the reaction time. Glycerin (69.4 grams, Aldrich) was added with stirring. The heat of reaction caused the temperature to rise from 24° C. to 69° C. within 10 minutes. The solution was held at 60-70° C. for 45 minutes. The clear, colorless, viscous liquid product was cooled and packaged in a glass container.

EXAMPLE 10

[0122] Adhesive formulations were prepared by adding phosphate esters to Example 7 and combining this with the isocyanate functional coreactant (Example 8). Laminates were made from these blends as described earlier. Results were as follows. For each laminate, the first substrate listed was the primary substrate.

TABLE-US-00027 TABLE 10A Formulations 99-4 99-6C.sup.(7) Name pbw pbw Example 7 polyol 100 100 Example 8 polyisocyanate 22.5 24 Example 9 glycerine phosphate 0.25 .sup.(7)Comparative sample, (no phosphate functional polyol)

TABLE-US-00028 TABLE 10B T-Peel Results (grams of force per 2.54 cm (g/inch)) 99-4 T-peel FM 99-6C.sup.(8) Initial PET-Al/808.24 119 AS 238 AS PET-Al/PET 56 AS 125 AS PET/GF 19 126 AS 279 AS 24 hr PET-Al/808.24 1387 FS 1389 FS PET-AL/PET 725 FT 293 AT PET/GF 19 1116 FT 353 AT 7 day PET-Al/808.24 1543 FS 1415 FS PET-Al/PET 722 FT 556 AT PET/GF 19 1138 FS 1129 FT .sup.(8)Comparative sample, (no phosphate functional polyol)

TABLE-US-00029 TABLE 10C Further Results (g/2.54 cm) 99-4 99-6C.sup.(9) T-peel FM T-peel FM Water soak PET-Al/808.24 887 AT 78 AT PET-Al/PET 577 AT 229 AT PET/GF 19 951 FT 1129 FT Boil Bag water 782 AT 289 AT Boil Bag 1, 1, 1 471 AT 282 AT Heat seal (N/25.4 mm) 70.92 FT 71.71 FT .sup.(9)Comparative Samples (no phosphate functional polyol)

EXAMPLE 11: PREPARATION OF ISOCYANATE-FUNCTIONAL PREPOLYMER

[0123]

TABLE-US-00030 Item Monomer/Intermediate Charge (g) 1 4,4′-Diphenylmethane diisocyanate 577.7 (ISONATE ™ 125M) 2 Propoxylated Glycerine, Mw 450 135.6 (Voranol ™ CP450) 3 Polypropylene glycol, Mw 430 148.9 (Voranol ™ 220-260) 4 Benzoyl chloride 0.10

[0124] Item 1 was charged to a dry reactor at 50° C. The reactor was kept under an atmosphere of dry nitrogen throughout the process. Item 2 was charged to the reactor and the resin mixture was heated to 80° C. Item 3 was added over 30 min at a rate to maintain the temperature at 80-85° C. The resin mixture was held at 80° C. for 2 hours. The % NCO was monitored until it was 15.0±0.3%. The resin was cooled to 50° C.-60° C., item 4 was added; the solution was mixed well, then packaged (12.4% NCO, Brookfield viscosity 810 mPa*s).

EXAMPLE 12. PREPOLYMER WITH POLYCARBODIIMIDE MODIFIED MDI

[0125]

TABLE-US-00031 Item Monomer/Intermediate Charge (g) 1 4,4′-Diphenylmethane diisocyanate 78.5 (ISONATE ™ 125M) 2 ISONATE ™ 143L polycarbodiimide-modified 160.3 diphenylmethane diisocyanate 3 Propoxylated Glycerine, Mw 450 31.1 (Voranol ™ CP450) 4 Polypropylene glycol, Mw 430 68.9 (Voranol ™ 220-260) 5 85% Phosphoric Acid 0.08 6 Ethyl Acetate 59

[0126] Charged items 1-6 with stirring. Gradually heated to 50-55° C. over 30 minutes. Continued heating to 75° C. over 30 minutes. Held at 73-77 C for 90 minutes. Collected light yellow product: 12.3% NCO; Brookfield viscosity 1620 mPa*s (#5 spindle at 20 rpm).

EXAMPLE 13. PREPARATION OF POLYESTER RESIN

[0127]

TABLE-US-00032 Item Monomer/Intermediate Weight % e 1 Phthalic Anhydride 42.86 2 Diethylene Glycol 33.35 3 FASCAT 9100 (Hydroxybutyltin oxide) 0.07 4 Ethyl acetate 23.72

[0128] Items 1-3 were charged to a reactor equipped with a stirrer, thermocouple, nitrogen inlet, a steam jacketed fractionating column and a condenser for collecting water that distilled from the reactor. A very slow stream of nitrogen was passed through the head space of the reactor throughout the time of the reaction.

[0129] The heterogeneous mixture was heated to 100-120° C. The external heat was reduced and the heat of reaction carried the temperature to about 130° C. The temperature was held at 120-130° C. for 0.25-0.50 Hrs.

[0130] The resin mixture was heated gradually to 225° C. At about 190° C. water began to distill. After 85-95% of the theoretical amount of water was collected, samples were periodically drawn from the reactor and tested for viscosity (cone & plate at 100° C.) and acid number. When the acid number was less than 20 mg KOH/g sample, vacuum was applied and the distillation continued under reduced pressure. Initially the pressure was set at 450 torr. The vacuum was gradually decreased to about 25 torr. Pressure was held at about 20-30 torr and the temperature maintained at 225° C. until the acid number was less than 2.0 mg KOH/g sample.

[0131] The product was cooled and combined with the ethyl acetate. The resin had the following properties: 74.7% solids, OHN 24 mg KOH/g; acid value 1.4, OHN 24; viscosity (C&P) 814 mPa*s at 25° C.

EXAMPLE 14: ADHESIVE FORMULATIONS

[0132] Samples in the following tables were prepared by combining the polyol portion of the adhesive with the additives, mixing thoroughly and allowing the resulting solution to stand for at least 24 hours at room temperature. When preparing laminates, the polyol blend was combined with the coreactant (NCO terminated prepolymer) in the proportion shown in the tables. Ethyl acetate was added to the blends in sufficient quantity to obtain a solution with 35-40% solids and laminates were prepared and tested as described previously. For all samples in table 14, the ratio of NCO equivalents/OH equivalents was about 1.4.

TABLE-US-00033 TABLE 14A Formulations 66-1A 66-1C 66-2A 66-2B pbw pbw pbw pbw Polyol Portion Example 13 Polyester 100 100 97 97 Example 4C (2% PPA CP 450) 3 3 Isocyanate Coreactant Portion Example 11 23 32 Example 12 24 32

TABLE-US-00034 TABLE 14B Results 66-1A 66-1C 66-2A 66-2B T-Peel FM T-Peel FM T-Peel FM T-Peel FM Initial 396 AS 592 AS 305 AS 292 AS  1 day 1790 FS 1437 FS 1876 FS 1720 FS  7 day 1803 FS 1450 FS 1947 FS 1834 FS 14 day 1836 FS 1879 FS 1976 FS 2006 FS BB 1:1:1 1560 FS 499 PFS Comment Delam Delam

[0133] Both 66-1A and 66-2B use Example 12 as the polyisocyanate. Sample 66-1A shows delamination in the BB 1:1:1 test, while sample 66-2B does not. Both 66-1C and 66-2A use Example 11 as the polyisocyanate. Sample 66-1C shows delamination in the BB 1:1:1 test, while sample 66-2A does not. These results demonstrate the benefit of the phosphate functional polyol, which is only present in samples 66-2A and 66-2B.