EPOXY PHOSPHATE ESTER

Abstract

Provided is a composition comprising one or more epoxy phosphate esters wherein the structure comprises two or more polyester linkages. Also provided is a method of making the epoxy phosphate esters that comprises reacting one or more epoxy-terminated polyesters with one or more phosphoric acids. Further provided is an adhesive composition that comprises one or more epoxy phosphate esters, one or more multifunctional isocyanate prepolymers, and one or more multifunctional isocyanate-reactive compounds.

Claims

1. A composition comprising one or more epoxy phosphate esters having structure (I) ##STR00011## wherein each of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 is independently hydrogen or an organic group, wherein p is 0 to 3, wherein each PEST has structure (II) ##STR00012## wherein each R.sup.5 and each R.sup.6 is an organic group, wherein n is 2 or greater, wherein each EPOX has structure (III) ##STR00013## and wherein each Q.sup.1 is an organic group.

2. The composition of claim 1 wherein each of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 is hydrogen.

3. The composition of claim 1 wherein Q.sup.2 is an aliphatic group.

4. A method of making the composition of claim 1, wherein the method comprises reacting one or more epoxy-terminated polyesters with one or more phosphoric acids.

5. An adhesive composition comprising one or more multi-functional isocyanate prepolymers, one or more multifunctional isocyanate-reactive compounds, and one or more composition of claim 1.

6. The adhesive composition of claim 5 wherein structure 1 is present in an amount of 2% or less by weight based on the total weight of the adhesive composition.

7. The adhesive composition of claim 5, wherein the adhesive composition is in the form of two separate packs consisting of a) Pack A, which comprises all of the isocyanate-reactive compounds in the adhesive composition and all of the epoxy phosphate esters in the adhesive composition, and b) Pack B, which comprises all of the isocyanate compounds in the adhesive composition.

8. A method of making a laminate comprising A) applying a layer of the adhesive composition of claim 5 to a first face of a first film, B) bringing a first face of a second film into contact with the layer of the adhesive composition of claim 5, C) curing the layer of the adhesive composition of claim 5.

9. A laminate formed by the method of claim 8.

Description

Pre-example 1: Preparation of Carboxylic Acid Terminated Polyester

[0095]

TABLE-US-00003 Item Ingredient Charge (g) 1 Isophthalic Acid 1158.60 2 Diethylene Glycol 720.90 3 Ethylene Glycol 398.30 4 Fascat 9100 (Hydroxybutyltin oxide) 0.4089 5 Adipic Acid 1525.85

[0096] Charged Items 1 through 4 to the reactor at ambient temperature (approximately 25-30° C.). The reaction mixture was heated slowly to 100° C. under Nitrogen with stirring. The reaction temperature was then increased to 225° C. and held at 225° C. When approximately 50% of theoretical water has evolved, the AV and In-Process viscosity was monitored. The reactor was maintained at 225° C. until AV was less than approximately 80 mg KOH/gram. The resin was cooled to less than 125° C. and then Item 5 was added, the resin mixture was maintained at 125-130° C. for 0.50 hrs. The reactor temperature was slowly increased to 225° C. and then maintained at 225° C., vacuum at approximately 435 mm Hg was applied as needed to decrease AV to final target property. The AV and In-Process Viscosity were monitored; reaction was maintained at 225° C. until AV was less than approximately 160 mg KOH/g. Cooled resin to about 150° C., filtered and packaged.

[0097] The final resin had the following properties: Acid Value (AV) 153 mg KOH/g, M.sub.n 650 g/mol, M.sub.w 1550 g/mol, M.sub.z 2650 g/mol, Viscosity (as measured by Brookfield CAP 2000+viscometer) at 25° C. of 173,750 mPa*s.

Pre-example 2: Preparation of Epoxy Terminated Polyester

[0098]

TABLE-US-00004 Monomer/Intermediate Charge (g) Carboxylic acid terminated polyester of Pre-example 1 931.64 D.E.R. ® 731 696.70 Sodium Acetate 0.6033 Ethyl Acetate 877.00

[0099] Diglycidyl ether of 1,4-butanediol (D.E.R.® 731 or Erisys® GE-21), the carboxylic acid terminated polyester of Pre-example 1 and catalyst were charged to the reactor. The resin mixture was slowly heated to 135-140° C. The reaction was maintained at 135-140° C. for approximately 0.50 hrs. and then heated to 150-155° C. and maintained at 150-155° C. for approximately 1.5 to 2 Hrs and then monitored AV and In-Process Viscosity. The reaction was maintained at 150-155° C. and monitored AV and In-Process Viscosity until AV was less than 1.0 mg KOH/g. The resin was cooled to approximately 80° C. and Ethyl Acetate was added and then continued cooling to approximately 55-60° C. and then transferred and packaged.

[0100] The product had the final properties: AV less than 0.1 mg KOH/g. In-Process Viscosity @ 25° C. 288.67 mPa*s, EEW 1353.6 g/mol, OH number 79.6 mg KOH/g, SEC Analysis: M.sub.n 1,850 g/mol, M.sub.w 30,000 g/mol, M.sub.z 186,550 g/mol, Polydispersity 16.2.

Example 3(a) and Pre-example 3(b): Preparation of Different Types of Epoxy Phosphate Esters

[0101] A 1L multi-neck round bottom flask was placed in a 70° C. oven for drying overnight. A designated amount of epoxy terminated polyester of Pre-example 2 was charged to the flask and maintained at 25-30° C. Under continuous nitrogen flow and strong agitation, the phosphorous-containing compound as shown in Table 1 was slowly added to the flask at the desired amount. The reaction temperature was monitored and necessary cooling procedures were taken to keep the temperature below 50° C. After the exotherm has subsided, the reaction was left to carry on at 30-35° C. for overnight under continuous nitrogen flow and strong agitation. The acid value was monitored during the reaction until it stabilized at a certain value, and the product was poured out from the flask, completely dried in a vacuum oven at 45° C. for 4-5 days to remove all ethyl acetate and residual water and used for later investigation.

TABLE-US-00005 TABLE 1 Recipe of epoxy phosphate esters Ingredient Pre-example 3(a) Pre-example 3(b) Epoxy Terminated Polyester 200 g 200 g of Pre-example 2 Ortho-phosphoric acid 39.44 g — (85% aqueous solution) Dibutyl phosphate — 3.96 g

Comparative Example 4: Preparation of a Comparative Phosphate Ester Adhesion Promoter (not an Epoxy Phosphate Ester)

[0102] A polyether polyol was reacted with polyphosphoric acid (PPA) and a diisocyanate. The product had the following properties: 100% Solids, AV 24 mg KOH/g, OH number of 270 mg KOH/g, Viscosity at 25° C. of 17,820 mPa-s, SEC Analysis of M.sub.n 780 g/mol, M.sub.w 1415 g/mol, M.sub.z 2325 g/mol, Polydispersity of 1.82.

[0103] Adhesive formulations in which the multifunctional isocyanate reactive compound (polyol) is a blend of VORANOL™ CP 755 and VORANOL™ CP 1055 and adhesion promoter.

[0104] VORANOL™ CP 755 and VORANOL™ CP 1055 were first blended at a 70:30 weight ratio to make the base co-reactant. Promoters were then added to the CP 755/CP 1055 polyol mixture at the concentrations as listed in Table 2A, to make pack B. The blends were mixed using a Flacktek high speed mixer at a speed of 3000 rpm for 1 minute. The performance of promoter Pre-example 3(a) was directly compared with that of Pre-example 3(b).

[0105] Preparation of multifunctional isocyanate prepolymer for pack A

[0106] Pre-example 5: Preparation of Polyester Resin to be used in making a multifunctional isocyanate prepolymer:

TABLE-US-00006 Item Ingredient Charge (grams) 1 Propylene Glycol 432.0 2 1,6-Hexanediol 735.3 3 Diethylene Glycol 187.7 4 Adipic Acid 1937.7 5 75% Phosphoric Acid 2.07

[0107] Items 1 through 5 were charged to a 5-Liter reactor equipped with condenser, mechanical stirrer, nitrogen purge and vacuum capabilities. The reaction mixture was heated slowly to 145-155° C. at atmospheric conditions and maintained at 145-155° C. for 1 hour and then slowly ramped to 225-230° C. When water evolution at 225-230° C. decreased at atmospheric conditions, vacuum was applied to the reactor (approximately 250-300 mm Hg) and AV was monitored until it was less than or equal to 2.5 mg KOH/g. When AV was less than or equal to 2.5 mg KOH/g, the resin was cooled to approximately 150-160° C., filtered and packaged.

[0108] The polyester had an AV of approximately 2.0 mg KOH/g and OH Number of 57.5 mg KOH/g.

[0109] Pre-example 6: Preparation of Polyester Resin to be used in making a multifunctional isocyanate prepolymer:

TABLE-US-00007 Item Ingredient Charge (grams) 1 Diethylene Glycol 1396.2 2 Isophthalic Acid 564.3 3 Adipic Acid 1042.5 4 Tyzor TPT 0.06

[0110] Items 1 through 3 were charged to a 5-Liter reactor equipped with condenser, mechanical stirrer, nitrogen purge and vacuum capabilities. The reaction mixture was heated slowly to 145-155° C. under atmospheric conditions and maintained at 145-155° C. for 1 hour and then slowly ramped to 225-230° C. When water evolution at 225-230° C. decreased at atmospheric conditions vacuum was applied to the reactor (approximately 250-300 mm Hg) and AV was monitored; when AV was less than or equal to 10.0 mg KOH/g, Item 4 was added to reactor. The reactor was maintained at 225-230° C. with a vacuum of approximately 200-250 mm Hg until AV was less than or equal to 2.0 mg KOH/g. When AV was less than or equal to 2.5 mg KOH/g the resin was cooled to approximately 150-160° C., filtered and packaged.

[0111] The polyester has an AV of approximately 1.8 mg KOH/g and OHN of 111 mg KOH/g.

[0112] Pre-example 7: Preparation of the MDI Terminated Polyurethane Prepolymer (i.e., multifunctional isocyanate prepolymer) for use in pack B of the adhesive composition.

TABLE-US-00008 Item Ingredient Charge (grams) 1 Polyester of Pre-example 5 861.3 2 Polyester Resin of Pre-example 6 559.7 3 Castor oil 14.5 4 ISONATE ™ 125M 1171.6 5 ISONATE ™ 143L 292.9

[0113] A 5-Liter reactor equipped with mechanical stirrer, condenser and Nitrogen purge was charged with Item 4 at 50° C. and then Item 1 was charged to reactor at 50° C., the reaction mixture exothermed to approximately 60-65° C. After approximately 1 hr, when the reaction mixture was stable at 60-65° C. Item 2 and 3 were added to the reactor and reaction mixture exothermed to approximately 85-90° C. and then was maintained at 85C for 3 hours. After the 3 hours hold at 85° C., Item 5 was added to the reactor and maintained at 85° C. for 2 hours. The resin was cooled to less than or equal to 60° C., filtered and packaged.

[0114] The product had the following properties: 100% Solids, NCO % 13.4%, Viscosity (as measured by Brookfield DV-ae+with spindle #27 at 20 rpm) at 25° C. of 9780 mPa s.

TABLE-US-00009 TABLE 2A Compositions of adhesive compositions based on CP 755/CP 1055. Amounts shown are in grams. Comparative Example Example Example Example 8 9 10 11 Prepolymer of Pre-example 7 150 150 150 150 VORANOL ™ CP 755 70 70 70 70 VORANOL ™ CP 1055 30 30 30 30 promoter: Pre-example 3(a) 0 0.54 1.26 0 promoter: Pre-example 3(b) 0 0 0 11.2 Promoter concentration in the 0 0.21 0.50 4.03 full formulation (wt. %)

TABLE-US-00010 TABLE 2B Viscosity versus time. The results shown are viscosity at 40° C., as measured as described above in the definition of the Pot Life testing. Units are mPa*s. Comparative Example Example Example minutes Example 8 9 10 11 0 1375 1150 1650 1350 10 925 1100 1100 950 20 1050 1370 1375 1100 30 1244 1710 1800 1375 40 1463 2110 2325 1675 60 2019 3160 3725 2425 80 2769 4590 5775 3500 100 3788 6550 — 4675 120 5040 — — 6250

TABLE-US-00011 TABLE 2C Pot life results Comparative Example Example Example Example 8 9 10 11 Pot Life (min) 112 79 69 98
Examples 9, 10, and 11 all have pot life of greater than 40 minutes and less than 100 minutes, which is acceptable. Comparative example 8 had pot life of 112 minutes, which is undesirably long.

[0115] The mixtures of Comparative Example 8 and Examples 9-11 were then applied on the Prelam A1 Foil (foil side) or the 92LBT (PET) film with a coating weight of 1.05 lbs/ream (1.71 g/m.sup.2), followed by laminating it with GF-19 (PE) film using a Nordmeccanica LaboCombi laminator. Laminates were tested for the bond strength after 4 hours, one day, seven days, boil-in-bag and chemical aging. Results are listed in Tables 3A and 3B.

[0116] In Tables 3A and 3B, Example 9 and Example 10 evidently show that on the prelam A1//GF-19 structure, the bond strength and the boil-in-bag resistance have been significantly enhanced with the use of the epoxy phosphate ester of Pre-example 3(a), and the improvement strongly depends on the promoter concentration. Also, the bond strength after chemical aging has been doubled due to the addition of epoxy phosphate ester of Pre-example 3(a). On the other hand, Example 11 shows some improvement in the dry bond, boil-in-bag and aging performance over the comparative Example 8 on prelam A1//GF-19, but the improvement is somewhat limited. It suggests that the epoxy phosphate ester of Pre-example 3(a) exhibits much better adhesion promoting effects compared to the Pre-example 3(b). In addition, on the 92LBT (PET)//GF-19 structure, as shown in Table 3B, the dry bond strength has also been improved significantly with the use of either Pre-example 3(a) or Pre-example 3(b).

[0117] In the boil-in-bag and chemical aging tests, Examples 9, 10, and 11 performed acceptably well, showing performance slightly worse than, but comparable to, the performance of Comparative Example 8.

[0118] In the dry bond testing, it should be noted that the mode of failure for PET/GF-19 structures with the phosphate epoxy esters is Film Tear (FT) in comparison to the Control Example 8 without the phosphate epoxy esters which exhibits Adhesive Split (AS) prior to boil-in-bag testing. In dry bond testing, FT failure mode is considered to show excellent performance of the adhesive composition.

TABLE-US-00012 TABLE 3A Dry bond performance for the laminates prepared with Comparative Example 8 and Examples 9 to 11 on foil//PE structures. Dry bond was measured at various intervals after formation of the sample. Results are reported in grams of force per 2.54 cm of width of sample (g/in), along with the failure mode. Comp. Example Example Example Example 8 9 10 11 4 hour dry bond 284 (AS) 322 (AS) 351 (AS) 323 (AS) 1 day dry bond 368 (AS) 718 (AS) 778 (AT) 404 (AS) 7 day dry bond 352 (AS) 585 (AS) 714 (FT) 338 (AS) Boil-in-bag 278 (AS) 736 (AS) 682 (AS) 341 (AS) Aging 18 (AS) 31 (AS) 33 (AS) 27 (AS)

TABLE-US-00013 TABLE 3B Boil-in-bag and chemical aging performance for the laminates prepared with Comparative Example 8 and Examples 9 to 11 on PET//PE structures. Quantities and units are the same as those in Table 3A. Comp. Example Example Example Example 8 9 10 11 4 hour dry bond 402 (AS) 484 (AS) 503 (AS) 423 (AS) 1 day dry bond 678 (AS) 1075 (FT) 904 (FT/FS) 668 (AS) 7 day dry bond 765 (AS) 1051 (FT) 994 (FT) 1075 (FT) Boil-in-bag 381 (AS) 359 (AT) 333 (AS) 339 (AT) Aging 441 (AT/AS) 682 (AT/AS) 490 (AT/AS) 522 (AT/AS)

[0119] Adhesive compositions using MOR-FREE™ C-411 as a multifunctional isocyanate-reactive component (in pack A).

[0120] Adhesive compositions using MOR-FREE™ C-411 as a multifunctional isocyanate-reactive component (in pack A) and using MOR-FREE™ L75-164 as a multifunctional isocyanate prepolymer (in pack B).

[0121] Adhesive compositions were applied at a coating weight of 1.74 g/m.sup.2 (1.07 pound/ream).

[0122] Promoters were added to the MOR-FREE™ C-411 polyol at the concentrations as listed in Table 4. The promoters being tested were the epoxy phosphate ester of Pre-example 3(a) at two different loading levels. Also, the polyphosphoric acid (115 grade) (PP acid) was tested as the Comparative Example 15, and it was maintained at the same level of phosphorous element as Example 14 below. The blends were mixed using a Flacktek high speed mixer at a speed of 3000 rpm for 1 minute.

TABLE-US-00014 TABLE 4 Compositions of co-reactant blends in Comparative Example 12, Examples 13-14, and Comparative Example 15. The amounts shown are in grams. Promoter conc. is weight % based on the weight of the complete adhesive composition. Promoter C-411 Pre-ex. 3(a) PP acid conc. Comparative Example 12 50 — — 0 Example 13 50 0.35 — 0.20 Example 14 50 0.91 — 0.51 Comparative Example 15 50 — 0.11 0.06

[0123] 40 parts (by weight) of the polyol blends were mixed with 100 parts (by weight) of the MOR-FREE™ L75-164 isocyanate prepolymer. The mixture was then applied on the Prelam film with a coating weight of 1.07 lbs/ream (1.74 g/m.sup.2), followed by laminating it with GF-19 film using Nordmeccanica LaboCombi laminator. Laminates were tested for the bond strength after 3 hours, one day, seven days, boil in bag and chemical aging. Results are listed in Table 5 as below.

[0124] It can be seen that the dry bond strength (1 day and 7 day) as well as the bond strength after the boil in bag could be improved significantly with the use of promoters. The Control Example 12 has very low bond strength after the boil-in-bag test, whereas the samples with epoxy phosphate ester of Pre-example 3(a) have exceptional bond strength and the value increased significantly with the phosphate concentration. In addition, the bond strength after the chemical aging test also improved significantly with the use of higher concentration of epoxy phosphate as shown in Example 14 vs. Example 13. On the other hand, the bond strength after the boil-in-bag and chemical aging test with the polyphosphoric acid (Comparative Example 15) is much less compared to values obtained in Example 14.

TABLE-US-00015 TABLE 5 Dry bond, boil-in-bag and chemical aging performance for the laminates prepared with formulations of Comparative Example 12, Examples 13- 14, and Comparative Example 15 on the foil//PE structure. Dry bond was tested at time intervals after the formation of the sample. All values are in units of grams per 2.54 cm of sample width (g/in). Comparative Example Example Comparative Example 12 13 14 Example 15 3 hour dry bond 210 (AS) 225 (AS) 295 (AS) 323 (AS) 1 day dry bond 557 (AT) 1114 (AT/FS) 1188 (AT/FS) 762 (AT) 7 day dry bond 372 (AT) 1091 (AT/FS) 1143 (AT/FS) 804(AT) Boil-in-bag 75 (AT) 536 (AT) 784 (AT) 485 (AT) Aging 31 (AS) 38 (AS) 106 (AS) 44 (AS)

[0125] Adhesive compositions using MOR-FREE™ C-411 as a multifunctional PGP isocyanate-reactive component (in pack A) and using MOR-FREE™ L75-164 as the multifunctional isocyanate prepolymer (in pack B). Adhesive compositions were applied at a coating weight of 2.22 g/m.sup.2 (1.7 pound/ream).

[0126] Promoters were added to the MOR-FREE™ C-411 polyol at the concentrations as listed in Table 6. The promoters being tested were the epoxy phosphate ester of Pre-example 3(a) at two different loading levels. Also, the epoxy terminated-polyester of Pre-example 2, the ortho-phosphoric acid (85% aqueous solution) (OPA), and the phosphate ester of Pre-example 4 were evaluated as comparative examples. The Comparative Examples 19-21 were maintained at the same level of phosphorous element as Example 18 below. The blends were mixed using a Flacktek high speed mixer at a speed of 3000 rpm for 1 minute.

TABLE-US-00016 TABLE 6 Composition of co-reactant blends in Comparative Example 16, Examples 17-18, and Comparative Example 19-21. Amounts shown are in grams. Prom. conc. is weight percent of promoter based on the total weight of the adhesive composition. Pre- Pre- Pre- Prom. C-411 ex. 3(a) ex. 2 OPA ex. 4 conc. Comp. Ex. 16 50 — — — — 0 Example 17 50 0.35 — — — 0.20 Example 18 50 0.91 — — — 0.51 Comp. Ex. 19 50 — 0.80 — — 0.45 Comp. Ex. 20 50 — — 0.09 — 0.05 Comp. Ex. 21 50 — — — 4.40 2.31

[0127] 40 parts (by weight) of the polyol blends were mixed with a 100 parts (by weight) of the MOR-FREE™ L75-164 isocyanate prepolymer. The mixture was then tested for pot life, with the results shown in Table 7. The mixture was also applied on the Prelam film with a coating weight of 1.7 lbs/ream (2.77 g/m.sup.2), followed by laminating it with GF-19 film using Nordmeccanica LaboCombi laminator. Laminates were tested for the bond strength after 3 hours, one day, seven days, boil in bag and chemical aging. Results are listed in Tables 8A and 8B below.

TABLE-US-00017 TABLE 7A Viscosity versus time in minutes (“min.”). Results shown are viscosity at 40° C. as measured as described above in the definition of the Pot Life testing. Units are mPa*s. 0 10 20 30 40 60 min min min min min min Comparative Example 16 1638 1238 1713 2412 3238 5413 Example 17 1663 1513 2475 3912 5850 — Example 18 1950 2025 3295 7163 — — Comparative Example 19 1550 1275 1850 2625 3575 6000 Comparative Example 20 1850 2000 4013 7463 — — Comparative Example 21 1800 1913 2625 6450 — —

TABLE-US-00018 TABLE 7B Pot-life of adhesive compositions of Example 17-18 and Comparative Examples 16 and 19-21. Example Pot Life (minutes) Comparative Example 16 53 Example 17 34 Example 18 22 Comparative Example 19 49 Comparative Example 20 22 Comparative Example 21 24

[0128] For this type of adhesive composition, using this polyol and this isocyanate prepolymer, Examples 17 and 18 show acceptable pot life.

[0129] As shown in Tables 8A and 8B, on both Prelam//GF-19 and Prelam A1//CPP structures, the dry bond strength (1 day and 7 day) as well as the bond strength after the boil-in-bag could be improved significantly with the use of all types of promoters (both examples of the present invention and comparative examples), except for the case of Comparative Example 19 where the epoxy-terminated polyester of Pre-example 2 was directly applied as an additive in the formulation. It can be seen that the epoxy-terminated polyester (which is different from the epoxy phosphate ester of the present invention) by itself alone is not an effective performance promoting additive.

[0130] The Control Example 16 has very low bond strength after the boil-in-bag test, whereas the samples with epoxy phosphate ester of Pre-example 3(a) have exceptional bond strength and the value increased significantly with the phosphate concentration as shown in Example 17 vs. Example 18. Although applied at the same level of phosphorous element, the ortho-phosphoric acid (Comparative Example 20) and Phosphate ester of Pre-example 4 (Comparative Example 21) did not boost the performance as efficiently as the epoxy phosphate ester of Pre-example 3(a). In addition, the bond strength after the chemical aging test also improved significantly with the use of higher concentration of epoxy phosphate ester as in Example 17 vs. Example 18. On the other hand, the bond strength after the chemical aging test with ortho-phosphoric acid (Comparative Example 20) and Phosphate ester of Pre-example 4 (Comparative Example 21) is much less compared to values obtained in Example 18.

[0131] On the Prelam A1//CPP structure, after the retort test, the laminates prepared with the Control Example 16 and with the one modified by the epoxy terminated polyester of Pre-example 2 (Comparative Example 19) completely delaminated. As a comparison, the laminates made with the epoxy phosphate ester of Pre-example 3(a), ortho-phosphoric acid and Phosphate ester of Pre-example 4 modified formulations can still retain a very decent bond strength, and the epoxy phosphate ester of Pre-example 3(a) gave the optimal results. PGP-50 T2

TABLE-US-00019 TABLE 8A Dry bond, boil-in-bag, and chemical aging performance for the laminates prepared with formulations in Comparative Example 16, Examples 17-18, and Comparative Examples 19-21 Prelam A1//GF-19 structures. Results are reported in grams of force per 2.54 cm of width of sample (g/2.54 cm or g/inch), along with the failure mode. Com. Com. Com. Com. Ex. 16 Ex. 17 Ex. 18 Ex. 19 Ex. 20 Ex. 21 4 hour 214 (AS) 310 (AS) 389 (AS) 244 (AS) 207 (AS) 216 (AS) 1 day 493 (AT) 1561 (AT/FS) 1462 (FT) 456 (AT) 718 (AT) 740 (AT) 7 day 462 (AT) 1117 (FT/AT) 1177 (FT/AT) 482 (AT) 673 (AT) 740 (AT) Boil- 127 (AT) 672 (AT) 924 (FS/AT) 246 (AT) 338 (AT) 483 (AT) in-bag Aging  16 (DL) 363 (AS) 909 (FS/AS)  18 (DL) 340 (AS) 254 (AS)

TABLE-US-00020 TABLE 8B Dry bond, boil-in-bag, chemical aging and retort performance for the laminates prepared with formulations in Comparative Example 16, Examples 17-18, and Comparative Examples 19-21 on A1//3 mil CPP structures. Results are reported in grams of force per 2.54 cm of width of sample (g/2.54 cm or g/inch), along with the failure mode. Com.Ex. Ex. Com.Ex. Com.Ex. Com.Ex. 16 18 19 20 21 4 hour 41 (AS) 82 (AS) 41 (AS) 51 (AS) 43 (AS) 1 day 905 (AT) 1311 (AT) 915 (AT) 1083 (AT) 1175 (AT) 7 day 919 (AT) 1362 (AT) 971 (AT) 1086 (AT) 1175 (AT) Boil-in-bag 10 (DL) 791 (AT) 20 (DL) 212 (AT) 691 (AT) Aging 38 (AS) 745 (AS) 34 (AS) 352 (AS) 568 (AS) Retort DL 1056 (AT/AS) DL 614 (AS/DL) 934 (AT/AS)