Adhesive composition

Abstract

Provided is a two-part composition comprising A) An epoxy terminated polyester having the structure ##STR00001## wherein R.sup.1 is ##STR00002## G- is ##STR00003## j is 0 to 5, R.sup.2 is a divalent organic group, R.sup.22 is a divalent alkyl group, and R.sup.22 is a divalent alkyl group, and B) one or more epoxy curing agent, each molecule of which comprises two or more active hydrogen atoms that are each capable of reacting with an epoxy group.

Claims

1. A two-part composition comprising A) an epoxy terminated polyester having the structure ##STR00029## wherein R.sup.1 is ##STR00030## G- is ##STR00031## j is 0 to 5, R.sup.2 is ##STR00032## wherein said R.sup.3 and R.sup.4 and R.sup.5 is each independently a divalent organic group, and wherein said p is 0 to 20, wherein said R.sup.3 is either (CH.sub.2).sub.q or ##STR00033## wherein q is 1 to 8, and wherein R.sup.21 is a divalent alkyl group, and R.sup.22 is a divalent alkyl group, and B) one or more epoxy curing agent, each molecule of which comprises two or more active hydrogen atoms that are each capable of reacting with an epoxy group.

2. The composition of claim 1, wherein each of said active hydrogen atoms is part of a primary or secondary amine group.

3. The composition of claim 1, wherein said curing agent is selected from the group consisting of phenalkamines, Mannich bases, phenalkamides, amine terminated amide resins, aminoimidazolines, and mixtures thereof.

4. The composition of claim 1, wherein said curing agent has number-average molecular weight of 750 or greater, and wherein the amount of said curing agent having molecular weight of less than 500 is 25% or less by weight based on the weight of said curing agent.

5. The composition of claim 1, wherein said R.sup.21 has 3 carbon atoms and every R.sup.22 has 3 carbon atoms.

6. The composition of claim 5, wherein at least one R.sup.22 has the structure selected from ##STR00034##

7. The composition of claim 1, wherein said R.sup.4 is either CH.sub.2CH.sub.2 or CH.sub.2CH.sub.2OCH.sub.2CH.sub.2.

8. The composition of claim 1, wherein said R.sup.21 has 5 or fewer carbon atoms, and every said R.sup.22 has 5 or fewer carbon atoms.

Description

EXAMPLE 1

Preparation of Epoxy Resin 1

(1) TABLE-US-00001 Item Monomer/Intermediate Charge 1 Isophthalic Acid 1023.35 2 Diethylene Glycol 572.30 3 Ethylene Glycol 315.60 4 Fascat 9100 (Hydroxybutyltin oxide) 0.5842 5 Adipic Acid 1349.81

(2) Charged Items 1-4 to vessel at Ambient Temperature (25-30 C.). Heated resin to 100 C. under Nitrogen with stirring. Heated resin to 225 C. and hold at 225 C., When ca.50% of theoretical water was off. Monitored AV and In-Process Viscosity. Maintained at 225 C. until AV<ca. 80. Cooled Resin to <125 C. Added Item 5; Maintained at 125-135 C. for 0.50 Hrs. Increased Temp to 225 C. and Maintained at 225 C. Monitored AV and Visc; Maintained at 225 C. until AV<ca. 200. Cooled Resin to about 150 C.; Filtered and Packaged. The final resin had the following properties: Acid Value (AV) 199, Mn 650, Mw 1250, Mz 2050, Wt. Fraction500 Daltons 22.3%, Wt. Fraction1000 Daltons 49.5%,Viscosity at 24.5 C. of 515,000 mPa*s.

EXAMPLE 2

Polyester Preparation

(3) TABLE-US-00002 Item Ingredient Charge (g) 1 Isophthalic Acid 451.50 2 Diethylene Glycol 1081.30 3 Fascat 9100 (Hydroxybutyltin oxide) 0.5543 4 Adipic Acid 1600.78

(4) Charged Items 1-3 to vessel at Ambient Temperature (25-30 C.). Heated resin to 100 C. under Nitrogen with stirring. Heated resin to 225 C. and held at 225 C., When ca.50% of theoretical water was off. Monitored AV and In-Process Viscosity. Maintained at 225 C. until AV <ca. 75. Cooled Resin to <125 C. Add Item 4; Maintained at 125-135 C. for 0.50 Hrs. Increased Temp to 225 C. and Maintained at 225 C.; Applied Vacuum at 400 mm as needed as to decrease AV to final target property. Monitored AV and Visc; Maintained at 225 C. until AV <ca. 155. Cooled Resin to about 150 C.; Filtered and Packaged. The final resin had the following properties: Acid Value (AV) 149.73, Mn 950, Mw 1750, Mz 2550, Wt. Fraction 500 Daltons 10.6%, Wt. Fraction 1000 Daltons 32.1%, Viscosity at 25 C. of 29500 mPa*s.

EXAMPLE 3

Polyester Preparation

(5) TABLE-US-00003 Item Ingredient Charge (g) 1 Isophthalic Acid 451.94 2 Diethylene Glycol 567.80 3 Ethylene Glycol 316.34 4 Fascat 9100 (Hydroxybutyltin oxide) 0.6028 5 Adipic Acid 1601.83

(6) Charged Items 1-4 to vessel at Ambient Temperature (25-30 C.). Heated resin to 100 C. under Nitrogen with stirring. Heated resin to 225 C. and hold at 225 C., When ca.50% of theoretical water was off. Monitored AV and In-Process Viscosity. Maintained at 225 C. until AV <ca. 75. Cooled Resin to <125 C. Added Item 5; Maintained at 125-135 C. for 0.50 Hrs. Increased Temp to 225 C. and Maintained at 225 C.; Applied Vacuum at 436 mm as needed as to decrease AV to final target property. Monitored AV and Visc; Maintained at 225 C. until AV <ca. 155. Cooled Resin to about 150 C.; Filtered and Packaged. The final resin had the following properties: Acid Value (AV) 157, Mn 750, Mw 1500, Mz 2350, Wt. Fraction 500 Daltons 18.1%, Wt. Fraction 1000 Daltons 41.3%, Viscosity at 25 C. of 22,175 mPa*s.

EXAMPLE 4

Polyester Preparation

(7) TABLE-US-00004 Item Ingredient Charge (g) 1 Isophthalic Acid 940.17 2 Diethylene Glycol 572.60 3 Ethylene Glycol 316.00 4 Fascat 9100 (Hydroxybutyltin oxide) 0.3169 5 Adipic Acid 1238.98

(8) Charged Items 1-4 to vessel at Ambient Temperature (25-30 C.). Heated resin to 100 C. under Nitrogen with stirring. Heated resin to 225 C. and hold at 225 C., When ca.50% of theoretical water was off. Monitored AV and In-Process Viscosity. Maintained at 225 C. until AV <ca. 80. Cooled Resin to <125 C. Added Item 5; Maintained at 125-135 C. for 0.50 Hrs. Increased Temp to 225 C. and Maintained at 225 C. Monitored AV and Visc; Maintained at 225 C. until AV <ca. 165. Cooled Resin to about 150 C.; Filtered and Packaged. The final resin had the following properties: Acid Value (AV) 169, Mn 950, Mw 2000, Mz 3250, Wt. Fraction 500 Daltons 12.5%, Wt. Fraction 1000 Daltons 31.0%, Viscosity at 25 C. of 221,750 mPa*s.

EXAMPLE 5

Polyester Preparation

(9) TABLE-US-00005 Item Ingredient Charge (g) 1 Isophthalic Acid 908.62 2 Diethylene Glycol 1126.80 3 Fascat 9100 (Hydroxybutyltin oxide) 0.5730 4 Adipic Acid 1198.87

(10) Charged Items 1-3 to vessel at Ambient Temperature (25-30 C.). Heated resin to 100 C. under Nitrogen with stirring. Heated resin to 225 C. and hold at 225 C., When ca.50% of theoretical water was off. Monitored AV and In-Process Viscosity. Maintained at 225 C. until AV <ca. 75. Cooled Resin to <125 C. Added Item 4; Maintained at 125-135 C. for 0.50 Hrs. Increased Temp to 225 C. and Maintained at 225 C.; Applied Vacuum at 394 mm as needed as to decrease AV to final target property. Monitored AV and Visc; Maintained at 225 C. until AV <ca. 135. Cooled Resin to about 150 C.; Filtered and Packaged. The final resin had the following properties: Acid Value (AV) 158, Mn 1150, Mw 2350, Mz 3750, Wt. Fraction 500 Daltons 8.5%, Wt. Fraction 1000 Daltons 23.6%, Viscosity at 25 C. of 175,000 mPa*s.

EXAMPLE 6

Polyester Preparation

(11) TABLE-US-00006 Item Ingredient Charge (g) 1 Isophthalic Acid 942.70 2 Diethylene Glycol 654.60 3 Ethylene Glycol 362.20 4 Fascat 9100 (Hydroxybutyltin oxide) 0.3168 5 Adipic Acid 1239.19

(12) Charged Items 1-4 to vessel at Ambient Temperature (25-30 C.). Heated resin to 100 C. under Nitrogen with stirring. Heated resin to 225 C. and hold at 225 C., When ca.50% of theoretical water was off. Monitored AV and In-Process Viscosity. Maintained at 225 C. until AV <ca. 80. Cooled Resin to <125 C. Added Item 5; Maintained at 125-135 C. for 0.50 Hrs. Increased Temp to 225 C. and Maintained at 225 C.; Applied Vacuum at 327 mm as needed as to decrease AV to final target property. Monitored AV and Visc; Maintained at 225 C. until AV <ca. 105. Cooled Resin to about 150 C.; Filtered and Packaged. The final resin had the following properties: Acid Value (AV) 98, Mn 1200, Mw 2450, Mz 3900, Wt. Fraction 500 Daltons 7.6%, Wt. Fraction 1000 Daltons 22.2%, Viscosity at 25 C. of 271,500 mPa*s.

EXAMPLE 7

Polyester Preparation

(13) TABLE-US-00007 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

(14) Charged Items 1-4 to vessel at Ambient Temperature (25-30 C.). Heated resin to 100 C. under Nitrogen with stirring. Heated resin to 225 C. and hold at 225 C., When ca.50% of theoretical water was off. Monitored AV and In-Process Viscosity. Maintained at 225 C. until AV <ca. 80. Cooled Resin to <125 C. Added Item 5; Maintained at 125-135 C. for 0.50 Hrs. Increased Temp to 225 C. and Maintained at 225 C.; Applied Vacuum at 435 mm as needed as to decrease AV to final target property. Monitored AV and Visc; Maintained at 225 C. until AV <ca. 160. Cooled Resin to about 150 C.; Filtered and Packaged. The final resin had the following properties: Acid Value (AV) 153, Mn 650, Mw 1550, Mz 2650, Wt. Fraction 500 Daltons 19.2%, Wt. Fraction 1000 Daltons 42.8%, Viscosity at 25 C. of 173,750 mPa*s.

EXAMPLES 8-26

Preparations of Epoxide Terminated Polyester Resins

(15) The preparations in Examples 8-26 were similar. Diepoxide, one or more diacid, and catalyst were charged to the reactor. Slowly Heated to 135-140 C. Maintained at 135-140 C. for ca. 0.50 Hrs and then heated to 150-155 C. and maintained at 150-155 C. for ca. 1.5 to 2 Hrs and then monitored AV and Viscosity. Maintained at 150-155 C. and monitored AV and Visc until AV <1.0. Transferred Resin and Package.

(16) TABLE-US-00008 TABLE 1 Example Number: 8 9 10 11 12 13 14 Ingredient (g) DER 736 425.36 426.94 600.93 503.22 1593.93 1900.35 1900.42 Isophthalic Acid 92.92 93.00 348.83 333.00 299.80 Adipic Acid 114.00 29.24 Polyester Resin of Ex. 1 373.19 EthylTriphenyl- 0.2486 0.2575 0.3061 0.3640 0.9532 0.7590 0.4035 phosphonium Iodide Properties EEW 544.71 482.29 472.88 771.14 487.37 416.73 411.51 Acid Value 0.11 0.05 0.05 0.05 0.1 0.09 0.07 Mn 1000 550 1200 1950 1400 1150 1050 Mw 3800 1400 3100 4400 4400 3750 3850 Mz 9600 2850 6350 7600 10500 9500 10350 Wt. Fraction 500 (%) 16.8 28.8 13.0 4.8 10.1 15.6 17.4 Wt. Fraction 1000 (%) 28.0 54.2 24.2 11.1 20.9 27.6 28.9 Viscosity at 25 C. (mPa*s) 18425 16300 3850 30400 18500 5025 6100 Viscosity at 70 C. (mPa*s) 535.0 467.5 345.0(a) 1665.0(a) 900.0(a) 365.0(a) 430.0(a) (a)Viscosity at 60 C.

(17) TABLE-US-00009 TABLE 2 Example Number: 15 16 17 18 19 20 Ingredient (g) DER 736 1953.00 1041.90 1002.17 1008.19 784.08 792.79 Isophthalic Acid 427.40 Polyester Resin of Ex. 2 839.04 770.69 Polyester Resin of Ex. 3 753.53 Polyester Resin of Ex. 4 655.66 Polyester Resin of Ex. 5 780.42 EthylTriphenylphosphonium 1.4638 0.5199 0.5067 Iodide Benzyltrimethylammonium 0.5630 Chloride Sodium Carbonate 0.5571 Sodium Acetate 0.5346 Properties EEW 482.29 492.53 598.00 634.90 802.95 694.54 Acid Value 0.04 0.04 0.06 0.05 0.04 0.03 Mn 1600 1500 1550 1550 2100 2000 Mw 5500 4750 4800 4700 13400 10100 Mz 14050 9000 8950 8700 44500 26900 Wt. Fraction 500 (%) 7.5 10.9 10.5 10.4 6.9 7.6 Wt. Fraction 1000 (%) 20.1 19.2 17.1 17.6 13.2 15.1 Viscosity at 25 C. (mPa*s) 18325 6512 6100 6000 23025 21800 Viscosity at 70 C. (mPa*s) 700.0(a) 320.0 342.5 345.0 1025 890.0 (a)Viscosity at 65 C.

(18) TABLE-US-00010 TABLE 3 Example Number: 21 22 23 24 25 26 Ingredient (g) DER 736 775.25 763.54 679.89 600.32 1021.77 738.40 Polyester Resin of Ex. 4 520.90 Polyester Resin of Ex. 5 917.33 Polyester Resin of Ex. 6 923.08 1010.75 Polyester Resin of Ex. 7 762.94 918.60 Sodium Acetate 0.5677 0.5467 0.3591 0.5156 0.5338 0.5217 Properties EEW 847.66 759.98 656.16 1244.17 665.79 1417.64 Acid Value 0.04 <0.1 <0.1 <0.1 <0.1 <0.1 Mn 2150 1700 1400 3200 850 3050 Mw 13250 10000 7600 23450 5550 48200 Mz 39550 31500 23000 82350 17150 248300 Wt. Fraction 500 (%) 6.5 9.6 12.0 3.4 19.5 3.6 Wt. Fraction 1000 (%) 12.2 15.6 20.4 8.0 28.4 8.3 Viscosity at 25 C. (mPa*s) 58125 38550 21875 272500 13275 776667 Viscosity at 70 C. (mPa*s) 1862 1328 805.0 6150 565.0 15000

EXAMPLE 27

Preparation of Amine Curative

(19) TABLE-US-00011 Item Monomer/Intermediate Charge 1 Unidyme 22 435.94 2 Aminoethylpiperazine 242.56

(20) Charged Item 1 and 2 to reactor, slowly heated to 200 C. Maintained at 200 C. for 2 Hr; monitor water evolution, the final resin is transferred and packaged. The final resin had the following properties: Amine Value of 217.15, Viscosity at 25 C. of 51100 mPa*s.

EXAMPLE 28

Preparation of Amine Curative

(21) TABLE-US-00012 Item Monomer/Intermediate Charge 1 Amine Curative of Example 6 200.84 2 POLYPOX P370 70.01

(22) Charged Item 1 and 2 to reactor, slowly heated to 50 C., maintain at 50 C. for 4 Hrs. The resin is transferred and packaged. The final resin had the following properties: Amine Value of 185.58, Viscosity at 25 C. of 10488 mPa*s.

EXAMPLE 29

Preparation of Amine Curative

(23) TABLE-US-00013 Item Monomer/Intermediate Charge 1 Epikure 3140 252.23 2 POLYPOX P370 84.35

(24) Charged Item 1 and 2 to reactor, slowly heated to 50 C., maintain at 50 C. for 4 Hrs. The resin is transferred and packaged. The final resin had the following properties: Amine Value of 377.45, Viscosity at 25 C. of 4825 mPa*s.

EXAMPLE 30

Preparation of Amine Curative

(25) TABLE-US-00014 Item Ingredient Charge (g) 1 Unidyme 22 877.12 2 Aminoethylpiperazine 488.24

(26) Charged Item 1 and 2 to reactor, slowly heated to 200 C. Maintained at 200 C. for 2 Hr; monitor water evolution, the final resin is transferred and packaged. The final resin had the following properties: Amine Value of 238.9, Viscosity at 25 C. of 49000 mPa*s.

EXAMPLE 31

Preparation of Amine Curative

(27) TABLE-US-00015 Item Ingredient Charge (g) 1 Unidyme 22 810.77 2 Triethylenetetramine (TETA) 488.71

(28) Charged Item 1 and 2 to reactor, slowly heated to 200 C. Maintained at 200 C. for 2 Hr; monitor water evolution, the final resin is transferred and packaged. The final resin had the following properties: Amine Value 169.64, Viscosity at 25 C. 54625 mPa*s.

(29) The adhesion properties of the polyester-polyols and polyols were evaluated with Amine based resins using a series of laminate constructions. These two part adhesive systems were evaluated via a solvent hand casting method and laminator.

(30) The following abbreviations are used to describe test results: as: adhesive split; ftr: film tear; fstr: film stretch; fsl: film sliver; at: adhesive transfer; sec: secondary; zip: zippery bond; pmt: partial metal transfer. Adhesion bond strengths were determined on a 15 mm wide strip of laminate on a Thwing-Albert Tensile Tester (Model QC-3A) with a 50 Newton load cell at a 10.0 cm/min rate.

(31) Examples 32-61 were performed as follows: An epoxy terminated polyester was mixed with a curing agent at the mix ratio shown below, in ethyl acetate at 50% concentration by weight. The solution was coated on a first substrate to yield a dry coating weight of 1.6276 g/m.sup.2 (1.0 lb/ream). A second substrate was applied to the dried coating and the resulting laminate was cured at room temperature (approximately 25 C.). The bond strength was examined as a function of curing time and is reported below. The Mix ratio is the weight ratio of epoxy resin to curing agent, expressed as 100:X. In the column labeled laminate structure, the first substrate is listed, followed by the second substrate.

(32) As an example, in the table below, Example number 32 was a mixture of epoxy resin made in Example 8, mixed with curing agent POLYPDX H015, at a weight ratio of epoxy resin to curing agent of 100:13.8. The bond strength on substrates CoexPP (75SLP)/CoexPP (70SPW) at 7 days was 3.19 Newton for a width of 15 mm, and the failure mode was film tear

(33) TABLE-US-00016 TABLE 4 Example Number 32 33 34 Epoxy Resin from Ex. No. 8 8 9 Curing agent POLYPOX H015 Epikure 3140 Curing Agent Ex. 27 Mix Ratio 100:13.8 100:17.4 100:45.0 Bond Strength (N/15 mm) Laminate Structure 7 Days 14 Days 7 Days 14 Days 7 Days 14 Days CoexPP (75SLP)/CoexPP (70SPW) 3.19, ftr 2.05, ftr 2.26, ftr 2.02, ftr 4.84, ftr 3.83, ftr CoexPP (75SLP)/PE (GF-19) 1.65, as 1.75, as 1.16, as 2.76, ftr 6.54, ftr 6.00, ftr PET/PE (GF-19) 2.09, as 1.85, as 1.39, as 1.67, as 2.46, as 3.55, as Nylon/PE (GF-19) 1.39, as 1.81, as 1.66, as 1.39, as 6.49, ftr 5.29, ftr PET-Met/PE (GF-19) 1.26, as 1.35, as 1.18, as 1.19, as 2.59, ftr 2.90, ftr OPP-Met/PE (GF-19) 1.96, as 2.06, as 2.88, as 3.55, ftr 4.16, as 4.58, as OPP-Met/CoexPP (70SPW) 1.85, as 2.10, as 2.49, as 2.08, ftr 1.34, as 2.61, ftr Backed Foil/Nylon 0.50, at, sec 0.70, at, sec 0.16, as 0.21, as 1.99, as 0.70, as Backed Foil/PET (92LBT) 0.69, at, sec 0.83, at, sec 0.22, as 0.22, as 2.21, as 2.42, as Backed Foil/PE (GF-19) 1.02, at, sec 1.07, at, sec 0.96, as 0.68, as 2.98, as 2.95, as

(34) TABLE-US-00017 TABLE 5 Example Number 35 36 37 Epoxy Resin from Ex. No. 9 9 10 Curing agent POLYPOX P370 Curing Agent Ex. 28 Curing Agent Ex. 28 Mix Ratio 100:20.0 100:38.5 100:39.2 Bond Strength (N/15 mm) Laminate Structure 7 Days 14 Days 7 Days 14 Days 7 Days 14 Days CoexPP (75SLP)/CoexPP (70SPW) 2.22, ftr 2.59, ftr 2.42, ftr 2.76, ftr 2.58, ftr 1.73, ftr CoexPP (75SLP)/PE (GF-19) 2.66, ftr 2.89, ftr 3.39, ftr 3.23, ftr 4.84, ftr 3.43, ftr PET/PE (GF-19) 2.38, as 2.36, as 2.73, as 2.30, as 1.40, as 2.00, as Nylon/PE (GF-19) 2.81, ftr 3.09, ftr 3.95, ftr 2.98, ftr 2.13, as 2.16, as PET-Met/PE (GF-19) 1.17, as 1.85, as 2.46, as 1.90, ftr 1.25, as 1.22, as OPP-Met/PE (GF-19) 1.21, as 2.03, as 2.57, as 3.08, as 2.95, as 3.46, as OPP-Met/CoexPP (70SPW) 1.14, as 1.21, as 2.47, as 2.32, ftr 1.43, as 1.73, as Backed Foil/Nylon 0.25, as 0.00, as 0.94, as 0.56, as 0.46, as 0.09, as Backed Foil/PET (92LBT) 0.15, as 0.00, as 0.97, as 0.36, as 0.28, as 0.16, as Backed Foil/PE (GF-19) 0.42, as 0.57, as 2.30, as 2.23, as 0.78, as 1.12, as

(35) TABLE-US-00018 TABLE 6 Example Number 38 39 40 Epoxy Resin from Ex. No. 10 11 11 Curing agent Curing Agent Ex. 27 Curing Agent Ex. 28 Curing Agent Ex. 27 Mix Ratio 100:45.9 100:24.1 100:28.2 Bond Strength (N/15 mm) Laminate Structure 7 Days 14 Days 7 Days 14 Days 7 Days 14 Days CoexPP (75SLP)/CoexPP (70SPW) 2.45, ftr 1.82, ftr 2.38, as 2.52, ftr 2.37, as 2.11, as CoexPP (75SLP)/PE (GF-19) 3.11, as 3.29, ftr 2.34, as 2.17, as 2.17, as 2.00, as PET/PE (GF-19) 2.18, as 2.35, as 3.31, as 2.63, as 2.19, as 2.76, as Nylon/PE (GF-19) 1.72, as 2.23, as 2.28, as 2.59, as 3.63, as 2.86, as PET-Met/PE (GF-19) 1.37, as 1.30, as 1.59, as 2.29, as 4.40, as 3.82, as OPP-Met/PE (GF-19) 2.42, as 3.11, as 2.50, as 3.00, as 2.25, as 3.06, as OPP-Met/CoexPP (70SPW) 2.88, as 2.86, as 2.20, as 2.56, as 2.75, as 1.80, as Backed Foil/Nylon 1.23, as 1.29, as 0.00, as 0.71, as 1.06, as 0.61, as Backed Foil/PET (92LBT) 0.52, as 1.21, as 1.31, as 0.97, as 1.27, as 1.23, as Backed Foil/PE (GF-19) 1.20, as 1.46, as 2.18, as 1.75, as 2.34, as 2.11, as

(36) TABLE-US-00019 TABLE 7 Example Number 41 42 43 Epoxy Resin from Ex. No. 13 13 16 Curing agent Epikure 3140 Curing Agent Ex 27 Curing Agent Ex 30 Mix Ratio 100:22.8 100:22.8 100:48.4 Bond Strength (N/15 mm) Laminate Structure 7 Days 14 Days 7 Days 14 Days 7 Days 14 Days CoexPP (75SLP)/CoexPP (70SPW) 3.11, ftr 3.59, ftr 1.52, as 2.37, ftr 1.88, ftr 2.27, ftr CoexPP (75SLP)/PE (GF-19) 2.23, as 2.46, as 1.93, as 1.99, as 3.52, as 2.99, as PET/PE (GF-19) 2.08, as 3.02, as 2.17, as 2.31, as 2.84, as 3.51, as Nylon/PE (GF-19) 1.39, as 1.64, as 1.54, as 1.45, as 4.97, as 1.92, as PET-Met/PE (GF-19) 0.38, as 0.40, as 2.12, as 0.25, as 0.87, as 1.33, as OPP-Met/PE (GF-19) 0.52, as 0.57, as 0.68, as 0.38, as 1.06, as 1.18, as OPP-Met/CoexPP (70SPW) 0.48, as 0.70, as 1.09, as 0.38, as 1.12, as 0.97, as Backed Foil/Nylon 0.83, as 0.69, as 0.91, as 0.46, as 1.89, as 1.62, as Backed Foil/PET (92LBT) 0.36, as 0.37, as 0.93, as 0.25, as 1.51, as 1.91, as Backed Foil/PE (GF-19) 1.33, as 1.92, as 1.72, as 1.65, as 2.51, as 2.05, as

(37) TABLE-US-00020 TABLE 8 Example Number 44 45 46 Epoxy Resin from Ex. No. 16 17 17 Curing agent Curing Agent Ex 31 Curing Agent Ex 30 Curing Agent Ex 31 Mix Ratio 100:34.4 100:39.9 100:28.4 Bond Strength (N/15 mm) Laminate Structure 7 Days 14 Days 7 Days 14 Days 7 Days 14 Days CoexPP (75SLP)/CoexPP (70SPW) 1.87, ftr 2.95, ftr 1.93, as 1.05, as 1.70, ftr 1.40, ftr CoexPP (75SLP)/PE (GF-19) 3.84, ftr 4.03, ftr 1.55, as 0.73, as 1.99, as 2.18, as PET/PE (GF-19) 1.24, as 0.91, as 1.67, as 1.64, as 1.36, as 1.52, as Nylon/PE (GF-19) 1.65, as 1.71, as 1.36, as 1.37, as 0.31, as 1.40, as PET-Met/PE (GF-19) 0.43, as 0.33, as 0.97, as 1.17, as 0.40, as 0.61, as OPP-Met/PE (GF-19) 0.58, as 0.39, as 0.89, as 0.75, as 0.42, as 0.77, as OPP-Met/CoexPP (70SPW) 0.49, as 0.64, as 1.10, as 0.98, as 0.49, as 0.42, as Backed Foil/Nylon 0.76, as 0.69, as 0.36, as 0.94, as 0.27, as 0.32, as Backed Foil/PET (92LBT) 0.90, as 0.17, as 0.46, as 0.79, as 0.26, as 0.22, as Backed Foil/PE (GF-19) 1.18, as 1.21, as 1.55, as 1.89, as 0.77, as 1.31, as

(38) TABLE-US-00021 TABLE 9 Example Number 47 48 49 Epoxy Resin from Ex. No. 18 18 19 Curing agent Curing Agent Ex 30 Curing Agent Ex 31 Curing Agent Ex 30 Mix Ratio 100:37.6 100:26.7 100:29.7 Bond Strength (N/15 mm) Laminate Structure 7 Days 14 Days 7 Days 14 Days 7 Days 14 Days CoexPP (75SLP)/CoexPP (70SPW) 1.42, as 1.03, as 1.79, as 1.77, ftr 1.11, as 1.06, as CoexPP (75SLP)/PE (GF-19) 0.93, as 1.41, as 1.65, as 2.10, as 1.10, as 1.54, as PET/PE (GF-19) 1.34, as 1.60, as 1.59, as 1.41, as 1.84, as 1.74, as Nylon/PE (GF-19) 0.88, as 1.30, as 1.42, as 1.20, as 2.11, as 1.58, as PET-Met/PE (GF-19) 0.94, as 0.50, as 0.48, as 0.43, as 0.69, as 1.08, as OPP-Met/PE (GF-19) 0.29, as 0.37, as 0.38, as 0.59, as 0.80, as 0.72, as OPP-Met/CoexPP (70SPW) 0.41, as 0.62, as 0.48, as 0.46, as 0.87, as 1.26, as Backed Foil/Nylon 1.18, as 1.85, as 0.66, as 0.79, as 1.13, as 1.83, as Backed Foil/PET (92LBT) 0.68, as 1.17, as 0.64, as 0.73, as 0.59, as 1.41, as Backed Foil/PE (GF-19) 0.81, as 0.98, as 1.05, as 0.97, as 1.41, as 2.03, as

(39) TABLE-US-00022 TABLE 10 Example Number 50 51 52 Epoxy Resin from Ex. No. 19 15 20 Curing agent Curing Agent Ex 31 Curing Agent Ex 31 Curing Agent Ex 30 Mix Ratio 100:21.1 100:35.2 100:34.3 Bond Strength (N/15 mm) Laminate Structure 7 Days 14 Days 7 Days 14 Days 7 Days 14 Days CoexPP (75SLP)/CoexPP (70SPW) 1.10, as 1.23, as 1.65, ftr 2.35, ftr 0.30, as 0.30, as CoexPP (75SLP)/PE (GF-19) 2.13, ftr 1.54, as 3.09, ftr 2.06, ftr 0.42, as 0.42, as PET/PE (GF-19) 1.39, as 1.37, as 2.31, as 2.28, as 0.37, as 0.37, as Nylon/PE (GF-19) 1.23, as 1.28, as 1.16, as 1.71, as 0.23, as 0.23, as PET-Met/PE (GF-19) 0.54, as 0.71, as 0.25, as 0.33, as 0.58, as 0.58, as OPP-Met/PE (GF-19) 0.79, as 0.86, as 0.48, as 0.54, as 0.64, as 0.64, as OPP-Met/CoexPP (70SPW) 0.76, as 0.79, as 0.47, as 0.57, as 0.35, as 0.35, as Backed Foil/Nylon 0.90, as 0.81, as 0.63, as 0.60, as 0.76, as 0.76, as Backed Foil/PET (92LBT) 0.80, as 0.70, as 0.35, as 0.33, as 0.52, as 0.52, as Backed Foil/PE (GF-19) 1.00, as 1.06, as 0.85, as 1.22, as 0.90, as 0.90, as

(40) TABLE-US-00023 TABLE 11 Example Number 53 54 55 Epoxy Resin from Ex. No. 20 22 22 Curing agent Curing Agent Ex 31 Curing Agent Ex 30 Curing Agent Ex 31 Mix Ratio 100:24.4 100:31.4 100:22.3 Bond Strength (N/15 mm) Laminate Structure 7 Days 14 Days 7 Days 14 Days 7 Days 14 Days CoexPP (75SLP)/CoexPP (70SPW) 0.94, as 2.29, ftr 0.52, as 0.82, as 0.92, as 1.96, fsl CoexPP (75SLP)/PE (GF-19) 1.25, as 2.57, fsl 0.82, as 1.01, as 1.15, as 1.82, as PET/PE (GF-19) 1.56, as 1.87, as 0.76, as 0.87, as 1.11, as 1.45, as Nylon/PE (GF-19) 1.11, as 1.31, as 0.67, as 0.83, as 0.86, as 1.46, as PET-Met/PE (GF-19) 0.29, as 0.29, as 0.72, as 0.62, as 0.28, as 0.35, as OPP-Met/PE (GF-19) 0.52, as 0.47, as 0.92, as 0.80, as 0.46, as 0.47, as OPP-Met/CoexPP (70SPW) 0.50, as 0.51, as 0.79, as 0.80, as 0.49, as 0.54, as Backed Foil/Nylon 0.72, as 0.80, as 1.04, as 1.08, as 0.86, as 0.90, as Backed Foil/PET (92LBT) 0.36, as 0.42, as 1.05, as 1.23, as 0.53, as 0.52, as Backed Foil/PE (GF-19) 0.89, as 0.91, as 0.94, as 0.85, as 0.87, as 1.05, as

(41) TABLE-US-00024 TABLE 12 Example Number 56 57 58 Epoxy Resin from Ex. No. 23 23 25 Curing agent Curing Agent Ex 30 Curing Agent Ex 31 Curing Agent Ex 30 Mix Ratio 100:36.3 100:25.9 100:37.6 Bond Strength (N/15 mm) Laminate Structure 7 Days 14 Days 7 Days 14 Days 7 Days 14 Days CoexPP (75SLP)/CoexPP (70SPW) 1.26, as 1.14, as 1.09, as 2.06, fsl 0.54, as 0.90, as CoexPP (75SLP)/PE (GF-19) 1.63, as 1.35, as 1.68, as 3.27, ftr 1.49, as 1.70, as PET/PE (GF-19) 1.60, as 1.41, as 1.25, as 1.77, as 1.19, as 0.72, as Nylon/PE (GF-19) 1.15, as 1.64, as 1.61, as 2.56, as 1.17, as 1.19, as PET-Met/PE (GF-19) 0.50, as 0.61, as 0.25, as 0.36, as 0.56, as 0.52, as OPP-Met/PE (GF-19) 0.71, as 0.76, as 0.44, as 0.49, as 0.60, as 0.64, as OPP-Met/CoexPP (70SPW) 0.73, as 0.85, as 0.43, as 0.51, as 0.69, as 0.51, as Backed Foil/Nylon 1.42, as 1.14, as 0.67, as 0.79, as 0.83, as 1.14, as Backed Foil/PET (92LBT) 1.12, as 1.16, as 0.31, as 0.44, as 0.52, as 0.80, as Backed Foil/PE (GF-19) 1.11, as 1.12, as 0.85, as 1.10, as 0.94, as 1.03, as

(42) TABLE-US-00025 TABLE 13 Example Number 59 60 61 Epoxy Resin from Ex. No. 25 15 15 Curing agent Curing Agent Ex 31 PRIAMINE 1071 JEFFAMINE D400 Mix Ratio 100:26.7 100:40.2 100:23.8 Bond Strength (N/15 mm) Laminate Structure 7 Days 14 Days 7 Days 14 Days 7 Days 14 Days CoexPP (75SLP)/CoexPP (70SPW) 1.46, ftr 2.28, ftr 1.87, ftr 2.91, ftr 1.13, as 0.89, as CoexPP (75SLP)/PE (GF-19) 1.13, as 1.33, as 2.62, ftr 2.56, ftr 1.36, as 2.07, as PET/PE (GF-19) 1.23, as 1.79, as 0.78, as 1.07, as 1.29, as 1.26, as Nylon/PE (GF-19) 0.83, as 0.30, as 1.45, as 1.49, ftr 1.04, as 0.67, as PET-Met/PE (GF-19) 0.25, as 0.00, as 0.23, as 0.00, as 0.00, as 0.17, as OPP-Met/PE (GF-19) 0.41, as 0.22, as 0.51, as 0.22, as 0.00, as 0.27, as OPP-Met/CoexPP (70SPW) 0.41, as 0.42, as 0.39, as 0.24, as 0.38, as 0.25, as Backed Foil/Nylon 0.49, as 0.66, as 0.00, as 0.00, as 0.00, as 0.00, as Backed Foil/PET (92LBT) 0.00, as 0.00, as 0.00, as 0.00, as 0.00, as 0.00, as Backed Foil/PE (GF-19) 0.78, as 0.75, as 0.74, as 0.65, as 0.27, as 0.78, as