LOW DP FOOD CASING FROM HIGH SOLIDS VISCOSE

Abstract: A tubular food casing of a tubular cellulose film precipitated from a viscose solution having a viscosity of from about 55 to about 90 ball seconds, where the ball has a density of 8g/cc and a radius of 0.316 centimeters at a drop of 20 centimeters, and where the solution contains at least eight and one-half percent of cellulose. The cellulose has a DPv of from about 300 to about 525 and the cellulose film has a dry film thickness of from about 0.015 mm to about 0.040 mm, a dry burst pressure in excess of 40 cm Hg, per 0.01 mm of dry film thickness, and a rewet burst pressure in excess of 5 cm Hg per 0.01 mm of rewet film thickness.

Description: LOW DP FOOD CASING FROM HIGH SOLIDS VISCOSE BACKGROUND OF THE INVENTION The present invention relates to tubular food casings from cellulose films and more particularly relates to tubular food casings formed by extrusion of a solution of cellulose followed by precipitation of the cellulose to, form a tubular cellulose film. In order to obtain a film that is strong enough and tough enough to be used as a food casing, e.g. for sausage casings, it has traditionally been believed that the cellulose had to have a relatively high molecular weight, e.g. as represented by its degree of polymerization (DP) . The degree of polymerization that was believed to be required for a food casing of sufficient strength and toughness for commercial use was at least 560. In the prior art, in order to dissolve cellulose, it was almost always first treated with sodium hydroxide to reduce the strength of hydrogen bonds and to expand it to permit the solvent to work more easily. Cellulose of sufficient DP to make a food casing, having good enough physical properties to be practical, still could not be dissolved to any significant degree in sodium hydroxide solution alone. However, there are no practical solvents for cellulose that function alone and such practical solvents, as do exist, usually require an alkali metal hydroxide as a cosolvent. Cellulose, for example, will not dissolve in aqueous carbon disulfide, or tertiary amine oxide, to any significant extent unless the cellulose is first expanded (steeped) in sodium hydroxide and the solution itself contains alkali metal hydroxide, preferably sodium hydroxide. BRIEF DESCRIPTION OF THE INVENTION The invention is a tubular food casing of a tubular cellulose film precipitated from a viscose solution having a viscosity of from about 55 to about 90 ball seconds, where the ball has a density of 8g/cc and a radius of 0.316cm, and where the solution contains at least eight and one-half weight percent of cellulose, said cellulose having a DPv of from about 300 to about 525. The cellulose film has a dry film thickness of from about 0.015mm to about 0.040mm, a dry burst pressure in excess of 40cm Hg, per 0.01mm of dry film thickness, and a rewet burst pressure in excess of 5cm Hg per 0.01mm of rewet film thickness. The cellulose may be precipitated from solution of non- derivatized cellulose, e.g. from aqueous tertiary amine oxide solution or may be regenerated from a solution of derivatized cellulose, e.g. a solution of cellulose xanthate . The invention also includes a method for making the cellulose film by. a) preparing a viscose solution, containing at least eight and one-half weight percent of cellulose having a DPv of about 300 to about 525, and having a solution viscosity of from about 55 to about 90 ball seconds, where the ball has a density of 8g/cc and a radius of 0.316cm. b) extruding the solution into the shape of a tube; and c) precipitating cellulose from the extruded solution to form a tubular film having a dry film thickness of from about 0.015mm to about 0.040mm, a dry burst pressure in excess of 40cm Hg, per 0.01mm of dry film thickness, and a rewet burst pressure in excess of 5cm Hg per 0.01mm of rewet film thickness. DETAILED DESCRIPTION OF THE INVENTION The cellulose used in accordance with the invention has a low DPv, e.g. from about 300 to about 525 and usually from about 400 to about 475. The viscose (xanthate or traditional viscose) may be a derivatized cellulose, e.g. xanthanated with carbon disulfide, dissolved in caustic at a concentration of from about 4.5 to about 6.5 weight percent. The viscose total sulfur concentration is usually from about 1.8 to about 2.5 weight percent and to form a cellulose film, the cellulose is precipitated and regenerated from the xanthate by passing extruded viscose through a bath comprising a strong acid and a salt. The viscose may also be a solution comprising non-derivatized cellulose in a solvent comprising tertiary a ine oxide and water (amine oxide viscose) obtained by forming a dilute solution of about 300 to about 525 DPv, preferably about 400 to about 475 DPv, cellulose and removing water by vaporization. The cellulose is precipitated by extruding the viscose and passing the extruded viscose through a wash bath containing water to remove tertiary amine oxide. The viscose may also be a solution of non-derivatized cellulose in aqueous alkali. It has been surprisingly found that solutions of cellulose having low DPv can be obtained by dissolving specially prepared low DPv cellulose in dilute concentration in aqueous alkali followed by removing water, e.g. by vaporization under a partial vacuum, to obtain a cellulose solution in alkali (alkali viscose) having a high cellulose concentration, e.g. in excess of eight weight percent. In such a case, the viscose is obtained by forming a dilute solution of about 300 to about 525 DPv cellulose and removing the water by vaporization where the cellulose is obtained by treating higher DPv cellulose with acid or steam expansion to reduce the DPv. Tubular cellulose film food casings made in accordance with the present invention have surprisingly good properties when compared with traditional cellulose film food casings made from high DPv cellulose. In particular such films may have a dry film thickness of from about 0.015mm to about 0.040mm, a dry burst pressure in excess of 40cm Hg, per 0.01mm of dry film thickness, and a rewet burst pressure in excess of 5cm Hg per 0.01mm of rewet film thickness. Tubular food casings of the present invention may also include fiber reinforced films where the viscose is applied to a fiber web, e.g. a fiber paper or where fibers are blended into the viscose. Such tubular food casings are usually thicker and larger than unreinforced tubular film food casings. The following examples serve to illustrate and not limit the present invention. Unless otherwise indicated, all parts and percentages are by total weight . Examples 1-6 Cellulose having a degree of polymerization (DPv) of about 350 was dissolved at a concentration of about 9 percent in an aqueous solution of from about 5.3 to about 5.6 percent caustic and sufficient CS 2 to provide a xanthate sulfur value of from about 1.1 to about 1.5 percent by weight of cellulose with a total sulfur content of from about 1.95 to about 2 percent. The above cellulose solution (viscose) had a ball viscosity of from about 21 to about 39 seconds using a ball having a density of 8g/cc, a radius of 0.316cm and a drop of 20cm. The unripened viscose had an adjusted maturity index of from about 10.2 to about 10.9. "Maturity index" is the number of ml of 10% acetic acid required to congeal the viscose. "Adjusted maturity index" is (viscose caustic wt. %-6.3) x 0.3 + measured maturity index. The unripened viscose (once filtered through a 10 micron filter) had a filterability K value of from about 2.54 to about .55 while viscose that had been ripened (allowed to stand) and de-aerated under vacuum at 25°C for more than about 24 hours and filtered twice had an adjusted ripened maturity of 7.9 and a K value of about 1.21. This was the ripened viscose used to form tubular film of the invention and is referred to in . the examples as "low DP viscose". "K value" = 1000 x [ [ (T 2 - T - (W 2 - W ] /T 2 - 3. ] where T is the time of weighing of an 8 ounce sample ( j . ) prior to filtering through a 4 ounce muslin filter cloth at a pressure of 60 psig. T 2 is the time of second weighing after filtration and 2 is the weight of viscose at the second weighing. The viscose at the high cellulose concentration of 8.9 to 9.2 percent surprisingly had a viscosity that was from about 1/3 to about 1/2 of the viscosity of standard viscose used to form tubular films. Such standard viscose is a solution of cellulose having a DPv of about 575 at a cellulose concentration of about 7.7 percent, a caustic concentration of about 6.3 percent, a xanthate sulfur concentration of about 1.15 and a total sulfur concentration of about 2.1. The standard viscose thus has a higher waste sulfur problem, a higher waste caustic problem, and a higher viscosity per percentage of dissolved cellulose than the viscose used in accordance with the invention, all of which result in processing advantages of using the low DPv viscose in accordance with the invention as opposed to standard high DPv viscose. Viscose was extruded through a ring die having an internal ring diameter of about 25mm and a die gap of about 0.35mm, referred to herein as a code 27 die, to form tubular cellulose film food casings. Both low DP and standard 575 DPv viscoses were used for purposes of comparison. Further various longitudinal stretches were used by varying uptake speed of extruded tubular film. Inflation with air at the pressure shown in Tables 1 and 2 was used to obtain transverse stretch. Viscose flow was adjusted so as to obtain a relatively uniform quantity of extruded cellulose for each of the food casings, i.e. flow for low DPv viscose through the die was about 956 grams (19.8g/10 meters) , while the flow for standard viscose, at lower solids, was about 813 grams per minute to obtain about the same quantity of cellulose solids in the film per unit area. The extruded cellulose films were regenerated in baths containing a mixture of sodium sulfate and sulfuric acid. The concentrations were about 10.5% sulfuric acid and about 20% sodium sulfate. Less acid was consumed in the regeneration bath for low DP viscose than in the regeneration bath for standard viscose. The differences result because of higher solids concentration in the low DP viscose and lower sulfur and caustic loading in the low DP viscose. Conditioned X-Y' s means that the casing was conditioned at 80% relative humidity. "X-Y" refers to the plot of tube diameter against pressure. "RSD" means recommended stuffing diameter. The results are shown in Tables 1-11. Example 7 A low DPv cellulose (about 350 DPv) was made by subjecting a high DPv cellulose (about 575 DPv) to a mineral acid. The acid was washed from the cellulose and the cellulose was dissolved in a caustic solution at a cellulose concentration of about 5 percent . Water is then removed from the cellulose solution under a vacuum to form a cellulose solution of about 8 percent. The resulting alkali viscose solution is then extruded to form a cellulose gel tubular film that is washed to remove alkali to form a tubular cellulose food casing. Example 8 Example 7 is repeated except that the DPv of the cellulose is reduced by enzymatic treatment with cellulase . An extrudable caustic solution of the resulting low DPv cellulose is then prepared as in Example 7 to prepare a tubular food casing. Example 9 Example 7 is repeated except that the DPv of the cellulose is reduced by treatment with concentrated sodium hydroxide solution. The resulting low DPv cellulose does not dissolve in the caustic solution to an extent sufficient to permit formation of an extrudable viscose. Example 10 Example 7 is repeated except that the resulting viscose is extruded upon a cellulose fiber web rolled to form a tube to obtain a tubular fiber reinforced food casing. The foregoing examples demonstrate that a low DPv cellulose can be used to make a practical tubular cellulose food casing without use of as much CS 2 as required in the known art and further that more readily available low DPv cellulose can be practically used. The invention further demonstrates that surprisingly CS 2 can be eliminated altogether when caustic is not used in prior treatment of cellulose to lower its DPv. This is entirely unexpected since traditional knowledge held that cellulose could not be dissolved in caustic alone in sufficient concentration to form an extrudable viscose. This misconception was due to the fact that cellulose was almost always treated with caustic prior to dissolution. Table 1 Average Rewet X-Y's Code 27 Table 2 Average Conditioned X-Y's Code 27 Table 3 Average Rewet Longitudinal Tnstron Values Table 4 Average Rewet Transverse Instron Values Table 5 Average Conditioned Longitudinal Instron Values Table 6 Average Conditioned Transverse Instron Values Table 7 Dryer Stretch Line Birefringence BDG DPv Gel Check Glycerine Total Sulfur (ppm) Example Sample Description, i Low DPv Viscose-Not -2.5% 140 0.0077 21.6 310 Nc Gck 25.50 1S02 Filtered Low DPv Viscosc-10 u -2.5% 140 0.0072 21.4 396 No Gels 26.20 1434 Filtered Filtered Low DPv 10.0% 140 0.0115 20.0 385 No Gels 26.28 1472 Viscose 21.8 308 No Gels 24.81 1527 Filtered Low DPv -2.5% 140 0.0071 Viscose Std Regular Production -2.5% 139 0.0092 22.1 577 No Gels 20.37 1748 Viscose 0.0139 20.6 575 Regular Production 10.0% 139 No Gels 20.81 1740 Viscose 21J 585 Standard or Typical Values Table 8 Table 9 Table 10 Table 11 omments: ♦Evaluate casing produced on PM 10 '/- with standard viscose and with (high viscose cellulose and low DPv) Low DPv viscose in standard dryer stretch & T400 mode. *100% Chicken, 25% water (based on chicken weight); 12.5% corn starch (based on chicken weight), with Heller Seasonings (9.6 lbs). *Cook cycle: 150 F DB/0 F WB for 15 m n; 158 F DB/158 F WB for 30 min; 167 F DB/167 F WB for 30 min; 172 F DB/172 F WB for 15 min; 176 F DB/176 F WB for 7 min; 176 F DB/0 F WB for 1 min; tap water shower with door open 6" until 111 F int. temp is reached; vary staging time 0, 45 & 90 min; then 7 min chilled bath.

Claims: What is Claimed is: 1. A tubular food casing comprising a tubular cellulose film precipitated from a viscose solution having a viscosity of from about 55 to about 90 ball seconds, where the ball has a density of 8g/cc and a radius of 0.316 centimeters at a drop of 20 centimetres, and where the solution contains at least eight and one-half weight percent of cellulose, said cellulose having a DPv of from about 300 to about 525, said cellulose film having a dry film thickness of from about 0.015mm to about 0.040mm, a dry burst pressure in excess of 40cm Hg, per 0.01mm of dry film thickness, and a rewet burst pressure in excess of 5cm Hg per 0.01mm of rewet film thickness . 2. The food casing of claim 1 wherein the cellulose has a DPv of about 400 to about 475. 3. The food casing of claim 1 wherein the viscose is a xanthate viscose containing a caustic concentration of from about 4.5 to about 6.5 weight percent and a viscose total sulfur concentration of from about 1.8 to about 2.5 weight percent and the cellulose is precipitated by passing extruded viscose through a bath comprising a strong acid and a salt. . The food casing of claim 1 wherein the viscose is a solution comprising non-derivatized cellulose in a solvent comprising tertiary amine oxide and water obtained by forming a dilute solution of about 300 to about 525 DPv cellulose and removing water by vaporization and the cellulose is precipitated by passing extruded viscose through a wash bath comprising water to remove tertiary amine oxide. 5. The food casing of claim 4 wherein the water is removed in a partial vacuum. 6. The food casing of claim 1 wherein the viscose comprises a non-derivatized cellulose in a solvent comprising water and sodium hydroxide obtained by forming a dilute solution of about 300 to about 525 DPv cellulose and removing the water by vaporization where the cellulose is obtained by treating higher DPv cellulose with acid to reduce the DPv. 7. The food casing of claim 6 wherein the water is removed in a partial vacuum. 8. The food casing of claim 6 wherein the cellulose is precipitated by passing extruded viscose through a wash bath comprising water to remove sodium hydroxide. 9. A method for making the tubular food casing of claim 1 which comprises : a) preparing a viscose solution, containing at least eight and one-half weight percent of cellulose having a DPv of about 300 to about 525, and having a solution viscosity of from about 55 to about 90 ball seconds, where the ball has a density of 8 grams per cubic centimeter and a radius of 0.316cm, at a drop of 20 centimetres; b) extruding the solution into the shape of a tube; and c) precipitating cellulose from the extruded solution to form a tubular film having a dry film thickness of from about 0.015mm to about 0.040mm, a dry burst pressure in excess of 40cm Hg, per 0.01mm of dry film thickness, and a rewet burst pressure in excess of 5cm Hg per 0.01mm of rewet film thickness. 10. The method of claim 9 wherein the cellulose has a DPv of about 425 to less than 500. 11. The method of claim 9 wherein the viscose is a xanthate viscose containing a caustic concentration of from about 4.5 to about 6.5 weight percent and a viscose total sulfur concentration of from about 1.8 to about 2.5 weight percent and the cellulose is precipitated by passing extruded viscose through an aqueous bath comprising acid and a salt. 12. The method of claim 9 wherein the viscose is a solution comprising non-derivatized cellulose in a solvent comprising tertiary amine oxide and water obtained by forming a dilute solution of about 300 to about 525 DPv cellulose and removing water by vaporization and the cellulose is precipitated by passing extruded viscose through a wash bath comprising water to remove tertiary amine oxide . 13. The method of claim 12 wherein the water is removed in a partial vacuum. 1 . The method of claim 9 wherein the viscose comprises a non-derivatized cellulose in a solvent comprising water and sodium hydroxide obtained by forming a dilute solution of about 300 to about 525 DPv cellulose and removing the water by vaporization. 15. The method of claim 14 wherein the water is removed in a partial vacuum. 16. The method of claim 15 wherein the cellulose is precipitated by passing extruded viscose through a wash bath comprising water to remove sodium hydroxide. 17. A method for the preparation of a regenerated cellulose food casing comprising the steps of : a) dissolving cellulose having a DP of less than 400 in a solvent at a concentration of greater than 8.5 percent by weight to obtain a viscose having a viscosity of less than about 90 ball seconds at a ball density of 8 grams per cc, a ball radius of 0.316cm and a ball drop of 20 centimeters; b) extruding the viscose to form a tubular gel film containing sufficient cellulose to form a dry film having a film thickness of less than 0.05mm; c) removing solvent from the tubular gel film; and d) drying the resulting film to form tubular cellulose film food casing. 18. The method of claim 17 where the viscose is a solution of cellulose xanthate formed using a solution of sodium hydroxide and carbon disulfide to dissolve cellulose and the solvent is removed by washing in an acid solution of a water soluble sulfate salt to regenerate the cellulose. 19. The method of claim 17 wherein the viscose is an alkali solution of cellulose formed from a higher DPv cellulose by steam. 20. The method of claim 17 wherein the viscose is an alkali solution of cellulose formed from a higher DPv cellulose by treatment with acid.

Inventors: HALFTOWN JOHN JEFF, VAN DER BLEEK MARK DREWES, VERELLEN MICHAEL, HALFTOWN, JOHN, JEFF, VAN DER BLEEK, MARK, DREWES, VERELLEN, MICHAEL
Applicants: MACDOUGALL DONALD CARMICHAEL, TEEPAK INVESTMENTS INC, MACDOUGALL, DONALD, CARMICHAEL, TEEPAK INVESTMENTS, INC.
Application year: 2001
Main classification: A22C13
IPC codes: A22C13