CA2041996C - Starch based natural adhesives used in cigarette manufacture - Google Patents
Starch based natural adhesives used in cigarette manufactureInfo
- Publication number
- CA2041996C CA2041996C CA002041996A CA2041996A CA2041996C CA 2041996 C CA2041996 C CA 2041996C CA 002041996 A CA002041996 A CA 002041996A CA 2041996 A CA2041996 A CA 2041996A CA 2041996 C CA2041996 C CA 2041996C
- Authority
- CA
- Canada
- Prior art keywords
- adhesive
- starch
- composition
- adhesive composition
- fluidity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
- C09J103/04—Starch derivatives
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24C—MACHINES FOR MAKING CIGARS OR CIGARETTES
- A24C5/00—Making cigarettes; Making tipping materials for, or attaching filters or mouthpieces to, cigars or cigarettes
- A24C5/14—Machines of the continuous-rod type
- A24C5/24—Pasting the seam
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
- C09J103/14—Amylose derivatives; Amylopectin derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
Abstract
An adhesive for use in cigarette manufacturing which is a natural based starch material having excellent flow or fluidity characteristics and viscosity stability and comprising a mixture of a crosslinked starch and a fluidity or converted starch, particularly an acid converted starch, the starches having an amylopectin content of at least 70% by weight and prepared by cooking at high temperature and pressure.
Description
2~4~
STARC~ BASED NA~URAL ADEESIVES USED IN
CI~-~R~TT~ MANUF~CTURE
BAC~GROUND OF ~.E lNV~llON
The present invention is directed to the use of selected modified starches, prepared by cooking at high temperature and pressure, as natural adhesives in the manufacture of cigarettes.
Cigarettes are generally comprised of a cigarette rod and mos~ often a filter or plug. The cigarette rod consists of a stream of tobacco wrapped in a paper tube, the paper tube being glued along one longitudinal edge with a suitable adhesive (side seam or lap seal). The filter or filter plug generally consists of a crimped textile tow of cellulose acetate fibers treated with a plasticizer and wrapped into a cylindrical form with paper.
The center of the paper is attached to the fibers using an adhesive (center-line adhes-ve) and the paper is then wrapped around the plug rod, overlapping and attaching itself with an adhesive (overlap adhesive) to form the cylindrical filter plug. The filter or plug is then attached to the cigarette rod by wrapping another paper (tipping paper) which contains an adhesive (tipping adhesive) around the plug and overlapping it with an aligned rod.
` - 2 - 204 1 996 .
Most cigarette manufacturing processes involve high speed operations (2000 - 12000 cigarettes per minute) where the adhesive i5 typically applied by nozzle (side seaming, center-line and overiap), paste wheel (side seaming) and by rollers (filter tipping). Adhesives used in the5e operations are generally synthetic emulsions but because of increasing interest and tobacco regulation requirements in different countries, natural type adhesives are being sought to replace the synthetics.
Starch has long been used as an adhesive material in various applications such as case and carton sealing, laminating, tube winding, pap~rm~k;ng, etc., as described in Starch: Chemistry and Technology, second edition by R. Whistler, J. Bemiller and ~. Paschall, 1984, pp. 593-610.
Dextrins and thin-boiling starches are disclosed as useful as side seam adhesives but generally at lower solids than being required at current high speed manufacturing operations.
The cooking of starch at high temperature and pressure in continuous operations is well known as disclosed in Whistler noted above. One such method disclosed in Japanese Patent No. 57-11579, published March 5, 198Z, involves continuous adhesive manufacturing of natural or synthetic adhesive materials using high pressure heating and forced stirring.
Despite continued developments and i~ ov~.l.ents for adhesive properties and technological advances in the manufacturing techniques for producing adhesives, there still is the need for a natural adhesive material which will satisfy the reguirements of current cigarette production. This has not been easy to accomplish particularly because of the d~n~; ng high speed operation and the reguired properties that adhesive materials used in these operations must posse~s including flow or fluidity, drying speed, cohesiveness, bonding strength, viscosity stability, machinability and other rheological characteristics.
STARC~ BASED NA~URAL ADEESIVES USED IN
CI~-~R~TT~ MANUF~CTURE
BAC~GROUND OF ~.E lNV~llON
The present invention is directed to the use of selected modified starches, prepared by cooking at high temperature and pressure, as natural adhesives in the manufacture of cigarettes.
Cigarettes are generally comprised of a cigarette rod and mos~ often a filter or plug. The cigarette rod consists of a stream of tobacco wrapped in a paper tube, the paper tube being glued along one longitudinal edge with a suitable adhesive (side seam or lap seal). The filter or filter plug generally consists of a crimped textile tow of cellulose acetate fibers treated with a plasticizer and wrapped into a cylindrical form with paper.
The center of the paper is attached to the fibers using an adhesive (center-line adhes-ve) and the paper is then wrapped around the plug rod, overlapping and attaching itself with an adhesive (overlap adhesive) to form the cylindrical filter plug. The filter or plug is then attached to the cigarette rod by wrapping another paper (tipping paper) which contains an adhesive (tipping adhesive) around the plug and overlapping it with an aligned rod.
` - 2 - 204 1 996 .
Most cigarette manufacturing processes involve high speed operations (2000 - 12000 cigarettes per minute) where the adhesive i5 typically applied by nozzle (side seaming, center-line and overiap), paste wheel (side seaming) and by rollers (filter tipping). Adhesives used in the5e operations are generally synthetic emulsions but because of increasing interest and tobacco regulation requirements in different countries, natural type adhesives are being sought to replace the synthetics.
Starch has long been used as an adhesive material in various applications such as case and carton sealing, laminating, tube winding, pap~rm~k;ng, etc., as described in Starch: Chemistry and Technology, second edition by R. Whistler, J. Bemiller and ~. Paschall, 1984, pp. 593-610.
Dextrins and thin-boiling starches are disclosed as useful as side seam adhesives but generally at lower solids than being required at current high speed manufacturing operations.
The cooking of starch at high temperature and pressure in continuous operations is well known as disclosed in Whistler noted above. One such method disclosed in Japanese Patent No. 57-11579, published March 5, 198Z, involves continuous adhesive manufacturing of natural or synthetic adhesive materials using high pressure heating and forced stirring.
Despite continued developments and i~ ov~.l.ents for adhesive properties and technological advances in the manufacturing techniques for producing adhesives, there still is the need for a natural adhesive material which will satisfy the reguirements of current cigarette production. This has not been easy to accomplish particularly because of the d~n~; ng high speed operation and the reguired properties that adhesive materials used in these operations must posse~s including flow or fluidity, drying speed, cohesiveness, bonding strength, viscosity stability, machinability and other rheological characteristics.
SUMMARY OF THE INVENTION
This invention relates to an adhesive for use in cigarette manufacturing which is a natural based starch material having excellent flow or fluidity characteristics as well as 5 viscosity stability and other needed rheological properties. This adhesive comprises a selected stabilized starch composition which contains a mixture of a crosslinked starch and a fluidity or converted starch, the starches having an amylopectin content of at least 70% by weight and prepared by cooking at high temperatures and pressure, said adhesive having a solids content of about 10 to 60% and a Brookfield viscosity of about 500 to 20,000 cps at 22.5C.
More particularly, this invention is directed to an adhesive for use in cigarette manufacturing comprising a starch composition which is a mixture of a crosslinked starch with an acid-converted starch, the weight ratio of the crosslinked starch to the fluidity or converted starch being from about 0.2:1 to 4:1, the starches having an amylopectin content of at least 70% by weight and prepared by cooking at a temperature of at least 100C using high 15 pressure of at least 30 psi, preferably jet cooking using steam injection, the starch adhesive having a solids content of about 10 to 60%, preferably 20 to 40, and a Brookf1eld viscosity of about 500 to 20,000 cps, preferably 800 to 5,000 at 22.5C.
This invention also involves the method of manufacturing cigarettes wherein the natural adhesive starch composition, defmed above, is used as the adhesive particularly in the 20 side se~ming and f1lter tipping operations.
DETAILED DESCRIPTION OF THE INVENTIQN
The starch composition prepared and used as an adhesive in cigarette manufacturing in accordance with this invention must satisfy the demands and requirements of high speed operations, typically greater than 6000 cigarettes per minute. In order to accomplish this, a 25 composition having a particular starch composition and method of preparation has been found.
~ ' The starch composition used in this invention includes a mixture or blend of selected modified starches, the starches having an amylopectin content of at least 70%, and preferably at least 75%, by weight. Starches of this type include waxy maize, waxy rice, tapioca, potato, maize (corn), wheat, arrowroot and sago. Preferred are waxy and root starches, especially waxy maize, tapioca and potato.
More particularly, the starch composition used in this invention is a mixture of a crosslinked starch with a fluidity or converted starch and derivatives thereof. The crosslinked starch is obtained by treatment with a multifunctional reagent in accordance with known conventional practice. Suitable cro~linking agents include mixed anhydrides of acetic and di-or tribasic acids, epichlorohydrin, phosphorous oxychloride, sodium metaphosphate and di- or polyepoxides with the mixed anhydrides being preferred. The degree of cro~linking may be varied depending on desired properties and conditions of cooking with light and moderate cros~linking typically being applied. Generally, this means cro~linkin~ with up to about 1.0% of a reagent based on the weight of starch, preferably up to about 0.2% and more preferably up to about 0.1%. More particularly crosslinking will vary from about 0.005 to 1% by weight of reagent based on the weight of starch and preferably from 0.005% to 0.2%, more preferably from about 0.01 to 0.1%.
The fluidity or converted starches are typically starches which are acid converted, although other chemical conversions such as enzyme conversion and oxidation may also be used. These starches are generally identified by their fluidity or WF (water fluidity) number which is an inverse viscosity measurement or measure of the degree of degradation of the starch. The higher the fluidity number (WF), the more degraded the starch and the thinner the viscosity. The measurement for "water fluidity" (WF) as described herein is made using a Thomas Rotational Shear-Type Viscometer (manufactured by Arthur ~ 204 1 996 H. Thomas Co., phil~phia, PA) in accordance with standard procedures such as disclosed in U.S. Pat. No. 4,499,116 issued February 12, 1985 to ~wiercan, et al. Useful acid-converted ~tarches will have a water fluidity (WF) of from about 40 to 90, preferably from abut 50 to 90 and more preferably from about 60 to 85. Preparation of acid-converted starches follow~ conventional techniques where the starch base is treated with an acid, such as hydrochloric or sulfuric acid at a temperature, e.g., 20 to 55 C for the length of time required to obtain the thinned starch that is sought.
The selected starches, i.e., crosslinked and acid converted, may be further modified to provide desired viscosity and flow properties as well as tack, stability and other physical and rheological properties necessary to satisfy the demands of high speed cigarette production as well as the high temperature, high pressure process by which the adhesives are prepared. Such modifications, include derivatized starches prepared by processes known in the art, e.g., etherification, esterification and oxidation. Particularly useful modifications of the starches of this invention are the hydroxyalkyl starches prepared by the etherification with alkylene oxides such as those cont~; n; ng 2 to 6, preferably 2 to 4 carbon atoms and especially ethylene and propylene oxide. Varying amounts of such compounds may be used depending on the properties desired with up to about 15~, and preferably up to about 10~, by weight, based on the weight of starch, generally being used.
Generally the blend or mixture of starches used can be varied and more particularly will comprise from about 0.2:1 to 4:1 parts of the crosslinked starch to the acid converted starch by weight and preferably from about 0.5:1 to 3:1.
~ 204 ~ 996 Preferred starches are the crosslinked waxy starches, especially those crosslinked with mixed acetic anhydride-adipic acid and the hydroxy propylated starches, especially the acid converted starches such as tapioca. While the crosslinked starch, as described above, may be used alone, mixtures with a fluidity or acid-converted starch are preferred.
The above described starch conversions and modifications, including crosslinking, acid conversion and etherification as well as other similar procedures are well known to those skilled in the art and described in publications such as ~andbook of Water-Soluble Gums and Resins, Robert L.
Davidson (Editor), Chapter 22: ~Starch and its Modifications~ by M. W.
Rutenberg, 1980 and in Starch Chemistry and Technology, Second Edition, edited by R. L. Whistler, et al., Chapters X and XVII, 1984.
While various thermal processes have been used in preparing starches, in order to prepare the starch adhesives of this invention having the required property characteristics, it is necessary to use z particular th~m~ 1 cooking process involving a high temperature, high pressure cooking operation. An advantageous and preferred method involves the use of a thermomechanical conversion or jet cooking operation wherein the starch is cooked at high pressure with an excess of steam via steam injection to a temperature high enough to thoroughly disperse and cook the starch. Typically a slurry of starch is pumped through a heater where high-pressure steam is injected to raise the temperature and impart ~ch~n;cal shear to the paste. While under pressure, the hot paste enters a retention chamber or coil to maintain the high temperature for a time period varying, depending on the design of the eguipment, from several seconds to several minutes. Using a back-pressure valve, the paste is flashed at atmospheric pressure, producing high turbulence and shear. Excess steam is separated and the product is collected.
~ 7 ~ 20~1~9~
The conditions used in preparing the starches are by cooking at high temperature and pressure, i.e., a temperature of at least 100C, more particularly from about 120 to 220C and pressure of greater than about 30 psi (0.21 MPa) and more particularly from about 50 to 220 psi (0.34 to 1.52 ~Pa~
and above.
The preferred conditions employed in preparing the starches are by jet cooking at temperatures of at least 100 C, more particularly from about 120 to 220 C and preferably from about 140 to 180 C, and pressures of greater than 100 psi (0.69 ~Pa), more particularly from about 120 to 200 psi (0.83 to 1.38 ~Pa) and above and preferably from about 140 to 180 psi (0.96 to 1.24 ~Pa).
While variations in the properties of the prepared adhesives will result by changing temperature and pressure conditions and controlling the excess steam, additional property variations can be obtained by using agents such as oxidizing agents. Particularly useful oxidizing agents are sodium perborate and ammonium persulfate. --The selected starch adhesives prepared as described above haveproperties m~king them particularly useful in manufacturing of cigarettes, especially those involved in high speed operations. These adhesives have a solids COntent of from about 10 to 60%, preferably from about 20 to 40~ and a Brookfield viscosity of from about 500 to 20,000 cps at 22.5C, preferably from about 800 to 5,000. The viscosity, as noted, is det~rm; n~d using a Brookfield viscometer at 20 rpm and 22.5C. The adhesives also have a pH of from about 3 to 9, preferably from about 5 to 7. Another important attribute of the adhesives of this invention is that they are viscosity stable, i.e., they avoid retrogradation and retain their original viscosity to a reasonable degree (i.e., within 10-20%) for a period of at least one month and preferably two or more months. This characteristic gives the adhesives the flexibility needed in satisfying cigarette manufacturing operations.
204 1 9~6 Several operations are involved in the manufacture of cigarettes as described previously and each of them involves the use of an adhesive.
Typically, different adhesive~ are used in the different manufacturing and assembling steps because of the different property requirements and especially in view of the currently increased production speeds, e.g., greater than 6,000 cigarettes per minute. The starch adhesives prepared in accordance with this invention may be used in any of the cigarette manufacturing steps. They have been found especially useful in the side seaming operations involved in preparing the cigarette rod where the tobacco is wrapped in overlapping paper and in filter tipping where the filter or plug is attached or joined to the cigarette rod by an overlapping paper which longitudinally extends over the filter tip and part of the rod. They also may be used in the formation of the filter plug as a centerline adhesive where the fibers are attached to the paper and as an overlap adhesive where the paper is wrapped around the plug 1~ rod attaching to itself in an overlapping manner and forming the cylindrical filter plug. ~-The invention can be further illustrated by the following examples ofpreferred embodiments thereof, although it will be understood that these examples are merely for the purposes of illustration and are not intended to limit the scope of the invention. All percents and parts are by weight and temperatures are degrees celsius unless otherwise indicated. The viscosities of the adhesive were determined using a Brookfield viscometer at 20 rpm and 22.5C.
E~AMPLE 1 An adhesive starch composition was prepared using a mixture of 24.5%
hyd~o~yyr~y-lated tapioca starch (5% hyd~ox~Lo~yl), 10.5~ of waxy maize starch crosslin~ed with mixed acetic anhydride/adipic acid and 64.0% of water were added to a jet cooker along with 1.0% of sodium perborate. A preservative (blend of halogenated hydrocarbons), (0.5%) was post added to the cooled adhesive. The added material was cooked in a steam injected jet cooker at a temperature of 160 to 165 C, a pressure of about 150 psi and retained in the cooker for 45 seconds.
The prepared product had a solids content of 35~, a Brookfield viscosity of 900 cps at 22.5C, was viscosity stable over two months and had good flow and tack properties.
E~MPLE 2 Another adhesive starch composition was prepared in a m~nn~r similar to Example 1 using an equal mixture of hydroxypropylated tapioca starch (5%
- ~ hydroxypropyl) and waxy maize starch crosslinked with mixed anhydride/adipic acid.
The prepared product had a solids content of 35%,--a Brookfield viscosity of 3,400 centipoise at 22.5C, was viscosity stable over several weeks and had good flow and tack properties.
E~MPLE 3 In order to demonstrate the usefulness of the starch adhesive compositions in cigarette manufacturing, particularly high speed operations, the composition of Example 1 was tested on a Hauni Protos cigarette making m~Chin~ as a side seaming adhesive. Runs were made which produced cigarette products at speeds of up to about 8,500 cigarettes per minute.
A similar test was made using the starch product of Example 2 and equally satisfactory results were attained at m~chine speeds of nearly 9,000 cigarettes per minute.
- 10 - ~l~4199 ~
E~A~PLE 4 The commercial utilization of a starch adhesive having the composition of Example 2 wa~ demonstrated further by its testing on a Hauni SE 80 Rn~m~k~r, The machine's nozzle side seam applicator was modified by fitting a heated jacket around it. With a jacket temperature of 40-45C cigarettes were produced up to 10,000 cigarettes per minute, which was the machines capacity.
E~AMPLE 5 The starch adhesive composition prepared in Example 2 was tested on a Hauni Max 80 tipping machine to further demonstrate the usefulness of such compositions as tipping adhesives in cigarette manufacture. Acceptable cigarette products were made at speeds of up to about 6,500 cigarettes per minute.
This invention relates to an adhesive for use in cigarette manufacturing which is a natural based starch material having excellent flow or fluidity characteristics as well as 5 viscosity stability and other needed rheological properties. This adhesive comprises a selected stabilized starch composition which contains a mixture of a crosslinked starch and a fluidity or converted starch, the starches having an amylopectin content of at least 70% by weight and prepared by cooking at high temperatures and pressure, said adhesive having a solids content of about 10 to 60% and a Brookfield viscosity of about 500 to 20,000 cps at 22.5C.
More particularly, this invention is directed to an adhesive for use in cigarette manufacturing comprising a starch composition which is a mixture of a crosslinked starch with an acid-converted starch, the weight ratio of the crosslinked starch to the fluidity or converted starch being from about 0.2:1 to 4:1, the starches having an amylopectin content of at least 70% by weight and prepared by cooking at a temperature of at least 100C using high 15 pressure of at least 30 psi, preferably jet cooking using steam injection, the starch adhesive having a solids content of about 10 to 60%, preferably 20 to 40, and a Brookf1eld viscosity of about 500 to 20,000 cps, preferably 800 to 5,000 at 22.5C.
This invention also involves the method of manufacturing cigarettes wherein the natural adhesive starch composition, defmed above, is used as the adhesive particularly in the 20 side se~ming and f1lter tipping operations.
DETAILED DESCRIPTION OF THE INVENTIQN
The starch composition prepared and used as an adhesive in cigarette manufacturing in accordance with this invention must satisfy the demands and requirements of high speed operations, typically greater than 6000 cigarettes per minute. In order to accomplish this, a 25 composition having a particular starch composition and method of preparation has been found.
~ ' The starch composition used in this invention includes a mixture or blend of selected modified starches, the starches having an amylopectin content of at least 70%, and preferably at least 75%, by weight. Starches of this type include waxy maize, waxy rice, tapioca, potato, maize (corn), wheat, arrowroot and sago. Preferred are waxy and root starches, especially waxy maize, tapioca and potato.
More particularly, the starch composition used in this invention is a mixture of a crosslinked starch with a fluidity or converted starch and derivatives thereof. The crosslinked starch is obtained by treatment with a multifunctional reagent in accordance with known conventional practice. Suitable cro~linking agents include mixed anhydrides of acetic and di-or tribasic acids, epichlorohydrin, phosphorous oxychloride, sodium metaphosphate and di- or polyepoxides with the mixed anhydrides being preferred. The degree of cro~linking may be varied depending on desired properties and conditions of cooking with light and moderate cros~linking typically being applied. Generally, this means cro~linkin~ with up to about 1.0% of a reagent based on the weight of starch, preferably up to about 0.2% and more preferably up to about 0.1%. More particularly crosslinking will vary from about 0.005 to 1% by weight of reagent based on the weight of starch and preferably from 0.005% to 0.2%, more preferably from about 0.01 to 0.1%.
The fluidity or converted starches are typically starches which are acid converted, although other chemical conversions such as enzyme conversion and oxidation may also be used. These starches are generally identified by their fluidity or WF (water fluidity) number which is an inverse viscosity measurement or measure of the degree of degradation of the starch. The higher the fluidity number (WF), the more degraded the starch and the thinner the viscosity. The measurement for "water fluidity" (WF) as described herein is made using a Thomas Rotational Shear-Type Viscometer (manufactured by Arthur ~ 204 1 996 H. Thomas Co., phil~phia, PA) in accordance with standard procedures such as disclosed in U.S. Pat. No. 4,499,116 issued February 12, 1985 to ~wiercan, et al. Useful acid-converted ~tarches will have a water fluidity (WF) of from about 40 to 90, preferably from abut 50 to 90 and more preferably from about 60 to 85. Preparation of acid-converted starches follow~ conventional techniques where the starch base is treated with an acid, such as hydrochloric or sulfuric acid at a temperature, e.g., 20 to 55 C for the length of time required to obtain the thinned starch that is sought.
The selected starches, i.e., crosslinked and acid converted, may be further modified to provide desired viscosity and flow properties as well as tack, stability and other physical and rheological properties necessary to satisfy the demands of high speed cigarette production as well as the high temperature, high pressure process by which the adhesives are prepared. Such modifications, include derivatized starches prepared by processes known in the art, e.g., etherification, esterification and oxidation. Particularly useful modifications of the starches of this invention are the hydroxyalkyl starches prepared by the etherification with alkylene oxides such as those cont~; n; ng 2 to 6, preferably 2 to 4 carbon atoms and especially ethylene and propylene oxide. Varying amounts of such compounds may be used depending on the properties desired with up to about 15~, and preferably up to about 10~, by weight, based on the weight of starch, generally being used.
Generally the blend or mixture of starches used can be varied and more particularly will comprise from about 0.2:1 to 4:1 parts of the crosslinked starch to the acid converted starch by weight and preferably from about 0.5:1 to 3:1.
~ 204 ~ 996 Preferred starches are the crosslinked waxy starches, especially those crosslinked with mixed acetic anhydride-adipic acid and the hydroxy propylated starches, especially the acid converted starches such as tapioca. While the crosslinked starch, as described above, may be used alone, mixtures with a fluidity or acid-converted starch are preferred.
The above described starch conversions and modifications, including crosslinking, acid conversion and etherification as well as other similar procedures are well known to those skilled in the art and described in publications such as ~andbook of Water-Soluble Gums and Resins, Robert L.
Davidson (Editor), Chapter 22: ~Starch and its Modifications~ by M. W.
Rutenberg, 1980 and in Starch Chemistry and Technology, Second Edition, edited by R. L. Whistler, et al., Chapters X and XVII, 1984.
While various thermal processes have been used in preparing starches, in order to prepare the starch adhesives of this invention having the required property characteristics, it is necessary to use z particular th~m~ 1 cooking process involving a high temperature, high pressure cooking operation. An advantageous and preferred method involves the use of a thermomechanical conversion or jet cooking operation wherein the starch is cooked at high pressure with an excess of steam via steam injection to a temperature high enough to thoroughly disperse and cook the starch. Typically a slurry of starch is pumped through a heater where high-pressure steam is injected to raise the temperature and impart ~ch~n;cal shear to the paste. While under pressure, the hot paste enters a retention chamber or coil to maintain the high temperature for a time period varying, depending on the design of the eguipment, from several seconds to several minutes. Using a back-pressure valve, the paste is flashed at atmospheric pressure, producing high turbulence and shear. Excess steam is separated and the product is collected.
~ 7 ~ 20~1~9~
The conditions used in preparing the starches are by cooking at high temperature and pressure, i.e., a temperature of at least 100C, more particularly from about 120 to 220C and pressure of greater than about 30 psi (0.21 MPa) and more particularly from about 50 to 220 psi (0.34 to 1.52 ~Pa~
and above.
The preferred conditions employed in preparing the starches are by jet cooking at temperatures of at least 100 C, more particularly from about 120 to 220 C and preferably from about 140 to 180 C, and pressures of greater than 100 psi (0.69 ~Pa), more particularly from about 120 to 200 psi (0.83 to 1.38 ~Pa) and above and preferably from about 140 to 180 psi (0.96 to 1.24 ~Pa).
While variations in the properties of the prepared adhesives will result by changing temperature and pressure conditions and controlling the excess steam, additional property variations can be obtained by using agents such as oxidizing agents. Particularly useful oxidizing agents are sodium perborate and ammonium persulfate. --The selected starch adhesives prepared as described above haveproperties m~king them particularly useful in manufacturing of cigarettes, especially those involved in high speed operations. These adhesives have a solids COntent of from about 10 to 60%, preferably from about 20 to 40~ and a Brookfield viscosity of from about 500 to 20,000 cps at 22.5C, preferably from about 800 to 5,000. The viscosity, as noted, is det~rm; n~d using a Brookfield viscometer at 20 rpm and 22.5C. The adhesives also have a pH of from about 3 to 9, preferably from about 5 to 7. Another important attribute of the adhesives of this invention is that they are viscosity stable, i.e., they avoid retrogradation and retain their original viscosity to a reasonable degree (i.e., within 10-20%) for a period of at least one month and preferably two or more months. This characteristic gives the adhesives the flexibility needed in satisfying cigarette manufacturing operations.
204 1 9~6 Several operations are involved in the manufacture of cigarettes as described previously and each of them involves the use of an adhesive.
Typically, different adhesive~ are used in the different manufacturing and assembling steps because of the different property requirements and especially in view of the currently increased production speeds, e.g., greater than 6,000 cigarettes per minute. The starch adhesives prepared in accordance with this invention may be used in any of the cigarette manufacturing steps. They have been found especially useful in the side seaming operations involved in preparing the cigarette rod where the tobacco is wrapped in overlapping paper and in filter tipping where the filter or plug is attached or joined to the cigarette rod by an overlapping paper which longitudinally extends over the filter tip and part of the rod. They also may be used in the formation of the filter plug as a centerline adhesive where the fibers are attached to the paper and as an overlap adhesive where the paper is wrapped around the plug 1~ rod attaching to itself in an overlapping manner and forming the cylindrical filter plug. ~-The invention can be further illustrated by the following examples ofpreferred embodiments thereof, although it will be understood that these examples are merely for the purposes of illustration and are not intended to limit the scope of the invention. All percents and parts are by weight and temperatures are degrees celsius unless otherwise indicated. The viscosities of the adhesive were determined using a Brookfield viscometer at 20 rpm and 22.5C.
E~AMPLE 1 An adhesive starch composition was prepared using a mixture of 24.5%
hyd~o~yyr~y-lated tapioca starch (5% hyd~ox~Lo~yl), 10.5~ of waxy maize starch crosslin~ed with mixed acetic anhydride/adipic acid and 64.0% of water were added to a jet cooker along with 1.0% of sodium perborate. A preservative (blend of halogenated hydrocarbons), (0.5%) was post added to the cooled adhesive. The added material was cooked in a steam injected jet cooker at a temperature of 160 to 165 C, a pressure of about 150 psi and retained in the cooker for 45 seconds.
The prepared product had a solids content of 35~, a Brookfield viscosity of 900 cps at 22.5C, was viscosity stable over two months and had good flow and tack properties.
E~MPLE 2 Another adhesive starch composition was prepared in a m~nn~r similar to Example 1 using an equal mixture of hydroxypropylated tapioca starch (5%
- ~ hydroxypropyl) and waxy maize starch crosslinked with mixed anhydride/adipic acid.
The prepared product had a solids content of 35%,--a Brookfield viscosity of 3,400 centipoise at 22.5C, was viscosity stable over several weeks and had good flow and tack properties.
E~MPLE 3 In order to demonstrate the usefulness of the starch adhesive compositions in cigarette manufacturing, particularly high speed operations, the composition of Example 1 was tested on a Hauni Protos cigarette making m~Chin~ as a side seaming adhesive. Runs were made which produced cigarette products at speeds of up to about 8,500 cigarettes per minute.
A similar test was made using the starch product of Example 2 and equally satisfactory results were attained at m~chine speeds of nearly 9,000 cigarettes per minute.
- 10 - ~l~4199 ~
E~A~PLE 4 The commercial utilization of a starch adhesive having the composition of Example 2 wa~ demonstrated further by its testing on a Hauni SE 80 Rn~m~k~r, The machine's nozzle side seam applicator was modified by fitting a heated jacket around it. With a jacket temperature of 40-45C cigarettes were produced up to 10,000 cigarettes per minute, which was the machines capacity.
E~AMPLE 5 The starch adhesive composition prepared in Example 2 was tested on a Hauni Max 80 tipping machine to further demonstrate the usefulness of such compositions as tipping adhesives in cigarette manufacture. Acceptable cigarette products were made at speeds of up to about 6,500 cigarettes per minute.
Claims (19)
1. An adhesive starch composition for use in cigarette manufacturing comprising a mixture of:
a) a crosslinked starch, and b) a fluidity or converted starch having a water fluidity of 40 to 90, the weight ratios of the crosslinked starch to fluidity or converted starch being from 0.2:1 to 4:1, the starches having an amylopectin content of at least 70% by weight and the composition being prepared by cooking at a high temperature of at least 100°C and pressure of at least 30 psi, the adhesive composition having a solids content of 10 to 60% and a Brookfield viscosity of 500 to 20,000 cps at 22.5°C.
a) a crosslinked starch, and b) a fluidity or converted starch having a water fluidity of 40 to 90, the weight ratios of the crosslinked starch to fluidity or converted starch being from 0.2:1 to 4:1, the starches having an amylopectin content of at least 70% by weight and the composition being prepared by cooking at a high temperature of at least 100°C and pressure of at least 30 psi, the adhesive composition having a solids content of 10 to 60% and a Brookfield viscosity of 500 to 20,000 cps at 22.5°C.
2. The adhesive composition of Claim 1, wherein the starches used in the composition are selected from the group consisting of waxy maize, waxy rice, tapioca, potato, maize, wheat, arrowroot and sago.
3. The adhesive composition of Claim 2, wherein the fluidity starch is an acid converted starch having a fluidity of from about 40 to 90 WF.
4. The adhesive composition of Claim 3, wherein the starch is jet cooked at a temperature of from about 120 to 220°C and a pressure of from about 120 to 200 psi.
5. The adhesive composition of Claim 4, wherein the crosslinked starch is a starch modified with a mixed anhydride of acetic acid and di- or tribasic carboxylic acids.
6. The adhesive composition of Claim 5, wherein the crosslinked starch is waxy maize.
7. The adhesive composition of Claim 6 comprising a mixture of from about 0.2:1 to 4:1 parts by weight of crosslinked starch to acid converted starch.
8. The adhesive composition of Claim 7 having a solids content of about 20 to 40% and a Brookfield viscosity of about 800 to 5000 cps at 22.5°C.
9. The adhesive of Claim 8, wherein an oxidizing agent is used during the jet cooking operation and wherein the adhesive composition has a pH of about 3 to 9.
10. The adhesive composition of Claim 9 comprising a mixture of a waxy maize starch crosslinked with mixed acetic anhydride/adipic acid and an hydroxypropylated acid converted tapioca starch.
11. In the method of manufacturing cigarettes the improvement comprising the use of the adhesive composition of Claim 1 as the adhesive.
12. The method of Claim 11, wherein the adhesive is used as the side seaming adhesive.
13. The method of Claim 11, wherein the adhesive is used as the filter tipping adhesive.
14. In the method of manufacturing cigarettes the improvement comprising the use of the adhesive composition of Claim 3 as the adhesive.
15. The method of Claim 14, wherein the adhesive is used as the side seaming adhesive.
16. The method of Claim 14, wherein the adhesive is used as the filter tipping adhesive.
17. In the method of manufacturing cigarettes the improvement comprising using the adhesive composition of Claim 10 as the adhesive.
18. The method of Claim 17, wherein the adhesive is used as the side seaming adhesive.
19. The method of Claim 17, wherein the adhesive is used as the filter tipping adhesive.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/526,205 | 1990-05-21 | ||
US07/526,205 US5085228A (en) | 1990-05-21 | 1990-05-21 | Starch based natural adhesives used in cigarette manufacture |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2041996A1 CA2041996A1 (en) | 1991-11-22 |
CA2041996C true CA2041996C (en) | 1995-10-03 |
Family
ID=24096371
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002041996A Expired - Lifetime CA2041996C (en) | 1990-05-21 | 1991-05-07 | Starch based natural adhesives used in cigarette manufacture |
Country Status (7)
Country | Link |
---|---|
US (1) | US5085228A (en) |
EP (1) | EP0458233B1 (en) |
JP (1) | JP2544028B2 (en) |
AU (1) | AU635639B2 (en) |
CA (1) | CA2041996C (en) |
DE (1) | DE69103675T2 (en) |
ES (1) | ES2060242T3 (en) |
Families Citing this family (53)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4125122C2 (en) * | 1991-07-30 | 1994-06-23 | Henkel Kgaa | Starch ether-based glue stick |
US5329004A (en) * | 1991-12-12 | 1994-07-12 | National Starch And Chemical Investment Holding Corporation | Method of manufacturing cigarettes using high amylopectin starch phosphate material as an adhesive |
US5490875A (en) * | 1993-07-13 | 1996-02-13 | American Maize Technology, Inc. | Adhesive composition for cigarette seams |
US6451121B2 (en) | 1993-07-30 | 2002-09-17 | National Starch And Chemical Investment Holding Corporation | Thermally-inhibited non-pregelatinized granular starches and flours and process for their preparation |
US5932017A (en) * | 1993-07-30 | 1999-08-03 | National Starch And Chemical Investment Holding Corporation | Thermally-inhibited non-pregelatinized granular starches and flours and process for their preparation |
US6221420B1 (en) | 1993-07-30 | 2001-04-24 | National Starch And Chemical Investment Holding Corporation | Foods containing thermally-inhibited starches and flours |
US5490876A (en) * | 1993-11-18 | 1996-02-13 | Reichhold Chemicals, Inc. | Starch-based adhesive |
US5498224A (en) * | 1994-07-20 | 1996-03-12 | National Starch And Chemical Investment Holding Corporation | Starch based hot melt adhesives for cigarettes |
US5718770A (en) * | 1994-08-25 | 1998-02-17 | National Starch And Chemical Investment Holding Corporation | Thermally-inhibited pregelatinized granular starches and flours and process for their production |
US5830884A (en) * | 1995-01-18 | 1998-11-03 | National Starch And Chemical Investment Holding Corporation | Pharmaceutical products containing thermally-inhibited starches |
EP0804140A2 (en) * | 1995-01-18 | 1997-11-05 | National Starch and Chemical Investment Holding Corporation | Cosmetics containing thermally-inhibited starches |
CA2210455A1 (en) * | 1995-01-24 | 1996-08-01 | National Starch And Chemical Investment Holding Corporation | Water-based adhesives containing thermally-inhibited starches |
US5753468A (en) * | 1996-08-05 | 1998-05-19 | National Starch And Chemical Investment Holding Corporation | Stable high viscosity starch based adhesive and method of preparation |
US5851959A (en) * | 1997-01-03 | 1998-12-22 | Chemstar Products Company | High temperature stable modified starch polymers and well drilling fluids employing same |
US6133203A (en) * | 1998-04-02 | 2000-10-17 | Halliburton Energy Services, Inc. | Drilling fluids and additives therefor |
ATE297452T1 (en) * | 1998-07-23 | 2005-06-15 | Avebe Coop Verkoop Prod | ADHESIVE COMPOSITION |
US6447615B2 (en) * | 1999-08-10 | 2002-09-10 | National Starch And Chemical Investment Holding Corporation | Sago fluidity starch and use thereof |
US7275548B2 (en) * | 2001-06-27 | 2007-10-02 | R.J. Reynolds Tobacco Company | Equipment for manufacturing cigarettes |
US7073514B2 (en) * | 2002-12-20 | 2006-07-11 | R.J. Reynolds Tobacco Company | Equipment and methods for manufacturing cigarettes |
US7448390B2 (en) * | 2003-05-16 | 2008-11-11 | R.J. Reynolds Tobacco Company | Equipment and methods for manufacturing cigarettes |
US20040238136A1 (en) * | 2003-05-16 | 2004-12-02 | Pankaj Patel | Materials and methods for manufacturing cigarettes |
US20030129210A1 (en) * | 2002-01-09 | 2003-07-10 | Economy Mud Products Company | Uses of flaked cationic potato starch |
EP1352939A1 (en) * | 2002-04-12 | 2003-10-15 | Remy Industries N.V. | Starch-based glue paste compositions |
US7234471B2 (en) * | 2003-10-09 | 2007-06-26 | R. J. Reynolds Tobacco Company | Cigarette and wrapping materials therefor |
US7195019B2 (en) * | 2002-12-20 | 2007-03-27 | R. J. Reynolds Tobacco Company | Equipment for manufacturing cigarettes |
US7077145B2 (en) * | 2002-12-20 | 2006-07-18 | R.J. Reynolds Tobacco Company | Equipment and methods for manufacturing cigarettes |
US20040122547A1 (en) * | 2002-12-20 | 2004-06-24 | Seymour Sydney Keith | Equipment and methods for manufacturing cigarettes |
US7117871B2 (en) * | 2002-12-20 | 2006-10-10 | R.J. Reynolds Tobacco Company | Methods for manufacturing cigarettes |
US7281540B2 (en) * | 2002-12-20 | 2007-10-16 | R.J. Reynolds Tobacco Company | Equipment and methods for manufacturing cigarettes |
US7275549B2 (en) * | 2002-12-20 | 2007-10-02 | R.J. Reynolds Tobacco Company | Garniture web control |
US7276120B2 (en) * | 2003-05-16 | 2007-10-02 | R.J. Reynolds Tobacco Company | Materials and methods for manufacturing cigarettes |
US7047982B2 (en) * | 2003-05-16 | 2006-05-23 | R.J. Reynolds Tobacco Company | Method for registering pattern location on cigarette wrapping material |
WO2005047385A1 (en) * | 2003-11-07 | 2005-05-26 | Cargill, Incorporated | Starch compositions and use in cellulosic webs and coatings |
US20060254738A1 (en) * | 2005-05-16 | 2006-11-16 | Anderson Kevin R | Cationic crosslinked starch containing compositions and use thereof |
US20060254737A1 (en) * | 2005-05-16 | 2006-11-16 | Anderson Kevin R | Cationic crosslinked starch containing starch compositions and use thereof |
US8925556B2 (en) | 2006-03-31 | 2015-01-06 | Philip Morris Usa Inc. | Banded papers, smoking articles and methods |
CN101485897B (en) | 2008-01-14 | 2015-05-20 | 纪欣 | Biocompatible hemostatic, antiblocking, healing-promoting and surgical wound-closing modified starch material |
US8701682B2 (en) * | 2009-07-30 | 2014-04-22 | Philip Morris Usa Inc. | Banded paper, smoking article and method |
US9220297B2 (en) * | 2009-08-07 | 2015-12-29 | R. J. Reynolds Tobacco Company | Materials, equipment, and methods for manufacturing cigarettes |
US11707082B2 (en) | 2010-12-13 | 2023-07-25 | Altria Client Services Llc | Process of preparing printing solution and making patterned cigarette wrapper |
PL3287016T3 (en) | 2010-12-13 | 2022-02-21 | Altria Client Services Llc | Process of preparing printing solution and making patterned cigarette wrappers |
EP2709471A4 (en) | 2011-05-16 | 2015-05-27 | Altria Client Services Inc | Alternating patterns in cigarette wrapper, smoking article and method |
EP4140323A1 (en) | 2012-05-16 | 2023-03-01 | Altria Client Services LLC | Novel banded cigarette wrapper with opened area bands |
CA2873533A1 (en) | 2012-05-16 | 2013-11-21 | Altria Client Services Inc. | Cigarette wrapper with novel pattern |
EP2849586A4 (en) | 2012-05-16 | 2015-07-29 | Altria Client Services Inc | Cigarette wrapper with novel pattern |
CN103773268B (en) * | 2012-10-20 | 2016-03-16 | 中国烟草总公司郑州烟草研究院 | A kind of novel starch matter cigarette glue containing modified-cellulose |
CN103773267B (en) * | 2012-10-20 | 2016-05-04 | 中国烟草总公司郑州烟草研究院 | A kind of starchiness cigarette glue based on degraded class-gelatinized starch and etherificate class-gelatinized starch |
US9732163B2 (en) * | 2013-01-03 | 2017-08-15 | Archer Daniels Midland Co. | High viscosity crosslinked ethoxy-starch |
CN109485739B (en) * | 2018-11-06 | 2020-06-23 | 浙江新和成股份有限公司 | Preparation method of octenyl succinic acid starch ester |
CN109517079B (en) * | 2018-11-06 | 2020-06-23 | 浙江新和成股份有限公司 | Method for preparing starch octenyl succinate and application thereof |
CN110003817A (en) * | 2019-02-25 | 2019-07-12 | 朱东洋 | A kind of starch type cigarette glue and preparation method thereof |
EP3912485A1 (en) | 2020-05-18 | 2021-11-24 | Del-Vis Sp. z o.o. | Cigarette product and a method for manufacturing the product |
CN112080235A (en) * | 2020-08-27 | 2020-12-15 | 重庆中烟工业有限责任公司 | Method for improving taste of cigarette lap adhesive |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB532044A (en) * | 1938-08-13 | 1941-01-16 | Vanderbilt Co R T | Improvements in adhesives and paper sizings |
JPS5221064B2 (en) * | 1972-05-10 | 1977-06-08 | ||
US3912531A (en) * | 1972-06-21 | 1975-10-14 | Anheuser Busch | Corrugating adhesive composition |
JPS4930427A (en) * | 1972-07-05 | 1974-03-18 | ||
FR2414533A1 (en) * | 1978-01-12 | 1979-08-10 | Roquette Freres | DEXTRIN GLUES |
DE3018712A1 (en) * | 1980-05-16 | 1981-11-26 | Deutsche Itt Industries Gmbh, 7800 Freiburg | DEFLECTION CIRCUIT FOR CATHODE RAY TUBES |
JPS6084370A (en) * | 1983-10-17 | 1985-05-13 | Oji Koonsutaac Kk | Adhesive for production of corrugated cardboard |
DD274018A1 (en) * | 1988-07-11 | 1989-12-06 | Freiberg Bergakademie | PROCESS FOR OBTAINING KCL AND MGCL DEEP 2 HIGH X 4 H DEEP 2 HIGH O FROM CARNALLITIC ROHSALZEN |
-
1990
- 1990-05-21 US US07/526,205 patent/US5085228A/en not_active Expired - Lifetime
-
1991
- 1991-05-07 CA CA002041996A patent/CA2041996C/en not_active Expired - Lifetime
- 1991-05-09 AU AU76465/91A patent/AU635639B2/en not_active Ceased
- 1991-05-18 DE DE69103675T patent/DE69103675T2/en not_active Expired - Lifetime
- 1991-05-18 EP EP91108122A patent/EP0458233B1/en not_active Expired - Lifetime
- 1991-05-18 ES ES91108122T patent/ES2060242T3/en not_active Expired - Lifetime
- 1991-05-20 JP JP3114902A patent/JP2544028B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
EP0458233A2 (en) | 1991-11-27 |
US5085228A (en) | 1992-02-04 |
EP0458233A3 (en) | 1992-01-15 |
EP0458233B1 (en) | 1994-08-31 |
ES2060242T3 (en) | 1994-11-16 |
AU7646591A (en) | 1991-11-21 |
JP2544028B2 (en) | 1996-10-16 |
CA2041996A1 (en) | 1991-11-22 |
DE69103675T2 (en) | 1995-01-12 |
JPH04227981A (en) | 1992-08-18 |
DE69103675D1 (en) | 1994-10-06 |
AU635639B2 (en) | 1993-03-25 |
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