PAPER COATED WITH A FUNCTIONAL POLYOLEFIN FILM

Abstract

The present invention relates to an article and a method for its preparation; the article comprises a cured polymeric film superposing paper or paperboard. The polymeric film is derived from a dispersion which comprises: a) a dispersant which is a copolymer with an acid value of 130 or less, comprising structural units of ethylene and a carboxylic acid monomer, wherein the copolymer has a melt flow index in the range of from 50 to 2000 g/10 min at 190° C./2.16 kg; wherein the weight-to-weight ratio of structural units of ethylene to carboxylic acid monomer is in the range of from 95:5 to 70:30; and wherein the dispersant has a concentration in the range of from 9 to 50 weight percent based on the weight of polymer solids in the dispersion; b) a base polymer comprising non-functionalized ethylene-co-alkene copolymers, wherein the weight-to-weight ratio of the structural units of ethylene to alkene is in the range of from 99.8:0.2 to 50:50; and c) a neutralizing agent which is a hard base and excludes an organic base having a boiling point of less than 250° C.; wherein the concentration of the neutralizing agent is sufficient to neutralize at least half of the carboxylic acid groups associated with the dispersion composition.

The article of the present invention is useful as a barrier to a wide range of hydrophobic and hydrophilic materials.

Claims

1. A process for preparing an omniphobic single layered coating onto paper or paperboard comprising the steps of: a) applying onto paper or paperboard a dispersion composition comprising water, a dispersant, a base polymer, and a neutralizing agent; and b) heating the composition to produce a cured film having a thickness in the range of 1 to 20 g/m.sup.2; wherein the sum of the dispersant and the base polymer comprise from 10 to 100 percent of the weight of polymer solids in the dispersion; wherein the dispersant is a copolymer with an acid value of 130 or less, comprising structural units of ethylene and a carboxylic acid monomer, wherein the copolymer has a melt flow index in the range of from 50 to 2000 g/10 min at 190° C./2.16 kg; wherein the weight-to-weight ratio of structural units of ethylene to carboxylic acid monomer is in the range of from 95:5 to 70:30; and wherein the dispersant has a concentration in the range of from 9 to 50 weight percent based on the weight of polymer solids in the dispersion, provided that the concentration of the dispersant in the composition is sufficient to form a cured film with a Cobb value of less than 18 g/m.sup.2 and oil contamination of less than 25 percent; the base polymer comprises non-functionalized ethylene-co-alkene copolymers, wherein the weight-to-weight ratio of the structural units of ethylene to alkene is in the range of from 99.8:0.2 to 50:50; and wherein the neutralizing agent is a hard base and excludes an organic base having a boiling point of less than 250° C.; wherein the concentration of the neutralizing agent is sufficient to neutralize at least half of the carboxylic acid groups present in the dispersion composition.

2. The process of claim 1 wherein the cured film has a thickness in the range of from 2 to 12 g/m.sup.2; wherein the dispersant is a copolymer of ethylene and methacrylic acid; the base polymer is ethylene-co-octene, ethylene-co-hexene, ethylene-co-butene copolymers, or mixtures thereof; and the neutralizing agent is potassium hydroxide.

3. The process of claim 2 wherein the cured film has a thickness in the range of from 4 to 10 g/m.sup.2, wherein the concentration of structural units of ethylene to structural units of methacrylic acid in the dispersant is in the range of from 99.5:0.5 to 75:25; the concentration of the dispersant in the composition is in the range of from 10 to 40 percent based on the weight of polymer solids in the dispersion; and wherein the concentration of the base polymer in the composition is in the range of from 50 to 90 percent based on the weight of polymer solids in the dispersion.

4. The process of claim 1 wherein the concentration of base polymer is sufficient to form a cured film with a Cobb value of less than 10 g/m.sup.2 and oil contamination of less than 5%.

5. The process of claim 4 wherein the concentration of base polymer is in the range of from 2 to 75 weight percent, based on the weight of polymer solids in the dispersion.

6. The process of claim 1 wherein the composition further comprises from 5 to 10 weight percent of a polymeric coupling agent, based on the weight of polymer solids in the dispersion.

7. The process of claim 5 wherein the base polymer of the composition has no copolymer comprising structural units of ethylene and a C.sub.1-C.sub.12-alkyl acrylate or methacrylate.

8. The process of claim 5 wherein the composition further comprises up to 5 weight percent of a wax, based on the weight of polymer solids in the dispersion.

9. An article made according to the process of claim 1.

Description

EXAMPLES

Example 1

Preparation of an Aqueous Dispersion of Amplify™ EA103 Base Polymer, Dispersant, Polymeric Coupling Agent, Wax and Engage™ 8401 Base Polymer at a 5:15:10:1.5:68.5 w/w/w/w/w Ratio

[0030] Amplify™ EA103 (5 weight percent of polymer solids), Nucrel™ 960 (15 weight percent of polymer solids), MA-g-PE (10 weight percent of polymer solids), Acrawax™ C (1.5 weight percent of polymer solids) and Engage™ 8401 (68.5 weight percent of polymer solids) were fed individually and concurrently from separate hoppers at the specified relative weights at a rate of 10 lbs/h (4.5 kg/h) into a 25 mm Bersdorff™ ZE25 UTX extruder with 48 L/D (rotating at 450 rpm). The extruder temperature profile was ramped to 150° C. prior to the introduction, through ISCO pumps, of water (21.3 mL/min at 123° C. and 346 psi) and

[0031] 30 wt % KOH (3.4 mL/min) separately and concurrently. Dilution water (80 mL/min at 123° C. and 550 psi) was then added and the mixture was cooled to 97° C. at the extruder outlet. A back-pressure regulator was used at the extruder outlet to adjust the pressure in the extruder barrel to reduce steam formation. The resulting dispersion was cooled and filtered through a 200-μm filter and deemed good quality based on low grit retention (<100 ppm), colloidal stability (no phase separation with 48 hours of production), dispersion solids (close to percent solids added to extruder) and particle size (<3 μm, as determined using a Coulter LS320 particle size analyzer or comparable tool)).

Example 2

Preparation of an Aqueous Dispersion of Base Polymer and Dispersant at a 80/20 w/w Ratio

[0032] ENGAGE™ 8200 (80 weight percent of polymer solids) and experimental copolymer B-X74 (20 weight percent of polymer solids) were fed individually and concurrently from separate hoppers at the specified relative weights at a rate of 10 lbs/h (4.5 kg/h) into a 25 mm Bersdorff™ ZE25 UTX extruder with 48 L/D (rotating at 450 rpm). The extruder temperature profile was ramped to 140° C. prior to the introduction, through ISCO pumps, of water (17.5 mL/min at 117° C. and 211 psi) and 30 wt % KOH (3.27 mL/min) separately and concurrently. Dilution water (100 mL/min at 127° C. and 86 psi) was then added. A back-pressure regulator was used at the extruder outlet to adjust the pressure in the extruder barrel to reduce steam formation. The resulting dispersion was cooled and filtered through a 200-μm filter.

[0033] Example 3 utilizes the procedure of Example 1, but without Amplify™ EA103 and with the components as shown in Table 1. Examples 4-6 utilize the procedure of Example 2 with the components as shown in Table 1.

Example 7

Preparation of an Aqueous Dispersion of Base Polymer and Dispersant at a 60/40 w/w Ratio

[0034] AFFINITY™ EG8200G (60 weight percent of polymer solids) and NUCREL™ 960 (40 weight percent of polymer solids) were fed individually and concurrently from separate hoppers at the specified relative weights at a rate of 600 lbs/h (272 kg/h) into a 58 mm Coperion™ ZSK extruder with 48 L/D (rotating at 1110 rpm). The extruder temperature profile was ramped to 150° C. prior to the introduction, through ISCO pumps, of water (2.55 L/min at 113° C. and 310 psi) and 30 wt % KOH (0.35 L/min) separately and concurrently. Dilution water (5.12 L/min at 117° C. and 310 psi) was then added and the mixture was cooled to 101° C. at the extruder outlet. A back-pressure regulator was used at the extruder outlet to adjust the pressure in the extruder barrel to reduce steam formation. The resulting dispersion was then further cooled to 34° C. through an in line cooler.

Example 8

Preparation of an Aqueous Dispersion of Base Polymer and Dispersant at a 85/15 w/w Ratio

[0035] AFFINITY™ EG8200G (85 weight percent of polymer solids) and experimental copolymer A (15 weight percent of polymer solids) were fed individually and concurrently from separate hoppers at the specified relative weights at a rate of 10 lbs/h (4.5 kg/h) into a 25 mm Bersdorff™ ZE25 UTX extruder with 48 L/D (rotating at 450 rpm). The extruder temperature profile was ramped to 140° C. prior to the introduction, through ISCO pumps, of water (10.65 mL/min at 94° C. and 210 psi) and 30 wt % KOH (3.26 mL/min) separately and concurrently. Dilution water (100 mL/min at 86° C. and 500 psi) was then added. A back-pressure regulator was used at the extruder outlet to adjust the pressure in the extruder barrel to reduce steam formation. The resulting dispersion was cooled and filtered through a 200-μm filter.

[0036] Examples 9-12 utilize the procedure of Example 7 with the components as shown in Table 1.

[0037] Example 13—Preparation of an Aqueous Dispersion of Amplify™ EA103 Base Polymer, Dispersant, Polymeric Coupling Agent, Wax and Engage™ 8401 Base Polymer at a 5:8:10:1.5:75.5 w/w/w/w/w Ratio EA103 (5 weight percent of polymer solids), PRIMACOR™ 5980i (8 weight percent of polymer solids), MA-g-PE (10 weight percent of polymer solids), Acrawax™ C (1.5 weight percent of polymer solids) and 8401 (75.5 weight percent of polymer solids) were fed individually and concurrently from separate hoppers at the specified relative weights at a rate of 10 lbs/h (4.5 kg/h) into a 25 mm Bersdorff™ ZE25 UTX extruder with 48 L/D (rotating at 450 rpm). The extruder temperature profile was ramped to 150° C. prior to the introduction, through ISCO pumps, of water (7.7 mL/min at 115° C. and 250 psi) and 30 wt % KOH (3.1 mL/min) separately and concurrently. Dilution water (80 mL/min at 104° C. and 550 psi) was then added and the mixture was cooled to 97° C. at the extruder outlet. A back-pressure regulator was used at the extruder outlet to adjust the pressure in the extruder barrel to reduce steam formation. The resulting dispersion was cooled and filtered through a 200-μm filter.

[0038] Examples 14-17 utilize the procedure of Example 13 with the components as shown in Table 1.

Example 18

Preparation of an Aqueous Dispersion of Base Polymer and Dispersant at a 60/40 w/w Ratio

[0039] AFFINITY™ EG8200 (60 weight percent of polymer solids) and PRIMACOR™ 5980 (40 weight percent of polymer solids) were fed individually and concurrently from separate hoppers at the specified relative weights at a rate of 600 lbs/h (272 kg/h) into a 58 mm Coperion™ ZSK extruder with 48 L/D (rotating at 1110 rpm). The extruder temperature profile was ramped to 150° C. prior to the introduction, through ISCO pumps, of water (0.79 L/min at 109° C. and 312 psi) and 30 wt % KOH (0.64 L/min) separately and concurrently. Dilution water (5.24 L/min at 106° C. and 312 psi) was then added and the mixture was cooled to 101° C. at the extruder outlet. A back-pressure regulator was used at the extruder outlet to adjust the pressure in the extruder barrel to reduce steam formation. The resulting dispersion was then further cooled to 37C through an in line cooler.

Example 19

Preparation of an Aqueous Dispersion of Amplify™ EA 103 Base Polymer, Dispersant, Polymeric Coupling Agent, Wax and Engage™ 8401 Base Polymer at a 5:15:10:1.5:68.5 w/w/w/w/w Ratio

[0040] Amplify™ EA103 (5 weight percent of polymer solids), Nucrel™ 960 (15 weight percent of polymer solids), MA-g-PE (10 weight percent of polymer solids), Acrawax™ C (1.5 weight percent of polymer solids) and Engage™ 8401 (68.5 weight percent of polymer solids) were fed individually and concurrently from separate hoppers at the specified relative weights at a rate of 10 lbs/h (4.5 kg/h) into a 25 mm Bersdorff™ ZE25 UTX extruder with 48 L/D (rotating at 450 rpm). The extruder temperature profile was ramped to 130° C. prior to the introduction, through ISCO pumps, of water (13.85 mL/min at 28° C. and 501 psi) and 100 wt % DMEA (3.88 mL/min) separately and concurrently. Dilution water (110 mL/min at 21° C. and 600 psi) was then added. A back-pressure regulator was used at the extruder outlet to adjust the pressure in the extruder barrel to reduce steam formation. The resulting dispersion was cooled and filtered through a 200-μm filter. This filtration operation proceeded much more slowly than the other examples, and 18% of the added solids was removed during the filtration. Both of these results are indicative of a very poor quality dispersion. The quality of all previous dispersion examples could be described as good.

[0041] Example 20 utilizes the procedure of Example 19 with the components as shown in Table 1. As with Example 19, filtration proceeded very slowly, but there was no corresponding removal of large amounts of polymer solids. This dispersion was considered poor in quality due to high levels of grit (>100 ppm), dispersion solids (25% lower than solids added to extruder) and particle size (>10 μm).

[0042] Table 1 illustrates a summary of the sample compositions

TABLE-US-00001 TABLE 1 Sample Compositions Dispersant Dispersant Dispersant Ex. Components Composition Base DoN Comonomer Acid value Wt. % 1 Engage 8401/ 68.5/5/10/15/1.5 KOH 90% EMAA 98 15 Amplify EA103/ Licocene 431/ Nucrel 960/ Acrawax C 2 Engage 8200/ 80/20 KOH 85% EMAA 98 20 B-X74 3 Engage 8401/ 68.5/10/20/1.5 KOH 90% EMAA 98 20 Licocene 431/ Nucrel 960/ Acrawax C 4 Engage 8200/ 75/25 KOH 85% EMAA 98 25 B-X74 5 Engage 8200/ 70/30 KOH 85% EMAA 98 30 B-X74 6 Engage 8200/ 65/35 KOH 85% EMAA 98 35 B-X74 7 Affinity EG8200/ 60/40 KOH 85% EMAA 98 40 Nucrel 960 8 Affinity EG8200/ 85/15 KOH 85% EMAA 130 15 A-2030 9 Affinity EG8200/ 80/20 KOH 85% EMAA 130 20 A-2030 10 Affinity EG8200/ 75/25 KOH 85% EMAA 130 25 A-2030 11 Affinity EG8200/ 70/30 KOH 85% EMAA 130 30 A-2030 12 Affinity EG8200/ 60/40 KOH 85% EMAA 130 40 A-2030 13 Engage 8401/ 75.5/5/10/8/1.5 KOH 90% EAA 155 8 Amplify EA103/ Licocene 431/ PRIMACOR 5980i/ Acrawax C 14 Engage 8401/ 73/5/10/10/1.5 KOH 90% EAA 155 10 Amplify EA103/ Licocene 431/ PRIMACOR 5980i/ Acrawax C 15 Engage 8401/ 71/5/10/12.5/1.5 KOH 90% EAA 155 12.5 Amplify EA103/ Licocene 431/ PRIMACOR 5980i/ Acrawax C 16 Engage 8401/ 68.5/5/10/15/1.5 KOH 90% EAA 155 15 Amplify EA103/ Licocene 431/ PRIMACOR 5980i/ Acrawax C 17 Engage 8401/ 45.5/18/10/25/1.5 KOH 80% EAA 155 25 Amplify EA103/ Licocene 431/ PRIMACOR 5980i/ Acrawax C 18 Affinity EG8200/ 60/40 KOH 85% EAA 155 40 PRIMACOR 5980i 19 Engage 8401/ 68.5/5/10/15/1.5 DMEA 150%  EMAA 98 15 Amplify EA103/ Licocene 431/ Nucrel 960/ Acrawax C 20 Engage 8401/ 68.5/5/10/15/1.5 DMEA 90% EMAA 98 15 Amplify EA103/ Licocene 431/ Nucrel 960/ Acrawax C DoN means Degree of Neutralization

Water Uptake and Oil/Grease Resistance Testing

[0043] All samples were cured at 100° C. for 2 min. All Cobb data was generated at 90° C. water for 2 min. The target Cobb value for water uptake was <10 g/m.sup.2. The target value for oil uptake was <15 g/m.sup.2 and the target value for contamination was 0%. Table 2 illustrates the coat weights, Cobb values, oil uptake values and contamination percentage results for all the samples.

TABLE-US-00002 TABLE 2 Water Uptake and Oil/Grease Resistance Results Coat Wt Cobb Cobb OGR OGR % Ex g/m2 Pass/Fail g/m2 Pass/Fail contamination 1 11 Pass 7 Pass 0% 2 7 Pass 6 Pass 0% 3 11 Pass 4 Pass 0% 4 8 Pass 7 Pass 0% 5 8 Pass 7 Pass 0% 6 10 Pass 6 Pass 0% 7 8 Pass 5 Pass 0% 8 8 Pass 7 Pass 0% 9 8 Pass 10 Pass 0% 10 6 Fail 27 Pass 0% 11 9 Fail 50 Pass 0% 12 19 Fail 94 Pass 0% 13 11 Pass 12 Fail 100%  14 12 Pass 10 Fail 100%  15 12 Fail 49 Fail 100%  16 10 Fail 82 Fail 67%  17 8 Fail 160 Pass 0 18 8 Fail 209 Pass 6.3%.sup.  19 11 Pass 4.2 Fail 63%  20 14 Pass 5.7 Fail 100% 

[0044] Examples 1, 19 and 20 results show that the use of KOH in place of DMEA in the dispersion improves performance characteristics of the coated paperboard. Table 1 shows the importance of the dispersant acid value and the total amount of acid in the dispersion on properties of the coated paperboard.