IL36421A - Smoking mixture - Google Patents
Smoking mixtureInfo
- Publication number
- IL36421A IL36421A IL36421A IL3642171A IL36421A IL 36421 A IL36421 A IL 36421A IL 36421 A IL36421 A IL 36421A IL 3642171 A IL3642171 A IL 3642171A IL 36421 A IL36421 A IL 36421A
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- mixture
- smoking mixture
- smoking
- parts
- calcium
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Classifications
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- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
- A24B15/10—Chemical features of tobacco products or tobacco substitutes
- A24B15/16—Chemical features of tobacco products or tobacco substitutes of tobacco substitutes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Tobacco Products (AREA)
- Cigarettes, Filters, And Manufacturing Of Filters (AREA)
- Toys (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
IMPROVED SMOKING MIXTURE ]it?'y!? msrjB nanyn N2263^ This invention relates to smoking mixtures and to methods of producing such mixtures.
Smoking mixtures are systems by which desirable flavours and drugs are conveniently distilled or aerosoled to the mouth during the smoking action. Being of natural origin, tobacco contains many chemical species which, although necessary for the growth and survival of the plant, contribute nothing to the smoking enjoyment and may unfortunately be the precursors of chemicals which are injurious to health.
There have been many attempts to lessen the health hazard from tobacco smoking by adding to the tobacco, chemicals which are reputed to favourably change the chemical composition and biological activity of the smoke.
More recently, substitutes for tobacco have been claimed. See British Patents I!os. 1,055,473 and 1,143,500 and U.S. Patent No. 3,106,209 in which cellulose, oxidised cellulose and lettuce leaves are used. In these compositions, pretreatment and additives are claimed to affect the smoke so that it is acceptable tastewise and is less hazardous to health.
The ideal smoking substitute would be a material or 'fuel' ■which burns harmlessly to r:ive the energy to distil, aerosol or pyrolytically produce and distill only the necessary amounts of those components required for taste and drug effects.
Unfortunately, fuels which burn to give only harmless products are difficult to find. The most obvious fuel would be elemental carbon which should combust to harmless carbon dioxide. Unfortunately again, N22632¾ the commercially available forms of carbon, e.g. carbon black, are prolific producers when smoked of pol aroma ic hydrocjdrbons . A large part of these hydrocarbons may, of course, come from the impurities produced in the manufacture of these carbons.
An object of the present invention is to provide a smoking composition which is suitable for aerosoling flavours and drugs but which contains a minimum amount Of combustible organic material or smoke-producing fuel which on burning inevitably rives rise to some harmful products.
According to the present invention there is provided a smoking mixture comprising an organic combustible material or fuel, a harmless inorganic filler and a binder, the inorganic filler being present in quantities such as to considerably reduce the amount of harmful products produced on combustion of the mixture and the composition of the filler having been selected by ion balancing to impart a commercially acceptable burning rate to the smoking mixture.
The organic combustible material or fuel may comprise 15 to 80$ by weight of the smoking mixture, preferably 20-30 by weight.
The harmless inorganic filler may comprise 15 to 65$ by weight Of the smoking mixture, preferably 40-60$ by weight.
The mixture may also contain a plasticiser/humectant in addition to the binder.
From another aspect, the present invention is a method of manufacturing said smoking mixture comprising preselecting a specific organic combustible material as smoke-producin fuel and preselecting N22632*^ the proportion by weight of said combustible material to be incorporated in the smoking mixture, admixing said c ombustible material with a predetermined amount of harmless inorganic filler, the ionic content of which has been balanced to impart a commercially acceptable burning rate to said preselected amount of organic combustible material and finally forming a shaped article of the mixture utilising a binder.
The shaped article is preferably a film, extruded filament or tape.
For the purpose of this invention the term "harmless inorganic filler is intended to include inorganic salts of some relatively simple organic acids. For example, formates, ' oxalates, tartrates and citrates can be used as "harmless inorganic fillers" but these are less satisfactory than the preferred completely inorganic materials on account of some undesirable pyrolytic decomposition. This decomposition becomes potentia more harmful as the size of the organic molecule increases.
The inorganic filler preferably comprises a mixture of two or more such "inorganic" salts admixed in quantities such as to obtain the balance of anions and cations most appropriate f or imparting the desirable rate of combustion to the preselected amount of the specific organic combustible material incorporated in the smoking mixture.
By way of example, an acceptable rate of combustion f or the smoking mixture of the invention can be correlated to the puff number of 10-12 of a machine-made standard Class B British cigarette containing 1.1 g. tobacco, where each puff is of 25 ml. volume in two seconds, followed by a 58 second rest or smouldering period and where the 70 mm. cigarette is smoked to a butt length of 20 mm.
N2253.2 The smoking mixture of the invention is intended to be used as a comparatively safe neutral substrate which burns at a correct i rate and has a low content of relatively harmless organic fuel and a high content of harmless inorganic filler. Flavourants, ■' drugs, medicaments, materials to improve ash coherence and colour and other additives, including tobacco, can be incorporated as desired to produce the final product sold to the smoker.
The smoking mixture containing such a high content of harmless inorganic material can advantageously be produced by a process similar to reconstituted tobacco processes which utilise film-forming agents or binders. Such a film-forming process enables a relatively large proportion of inorganic materials to be incorporated into the smoking mixture.
The film-forming agent or binder and the plasticiser/humectant incorporated in the' mixture are also organic in nature but they may have an inorganic content and they can be carefully chosen from materials known to burn to produce lesser amounts of harmful products than tobacco.
Preferred binders include carboxymethyl cellulose and its salts and other carboxylated carbohydrates. Where the amount of binder employed is very small other less satisfactory binder materials such as natural gums, guar gums, locust bean gums and other synthetic binders such as methyl and other ethers of cellulose may be used.
Preferred plasticiser/humectants include glycerol, ethylene glycol and polyethylene glycol.
Organic combustible materials suitable as smoke-producing fuel in the mixtures of the invention include carbohydrates, modified carbohydrates and certain aldol condensation products . Carbon samples which produce lower amounts of polycyclic aromatic hydrocarbons can also be used.
The smoke-producing carbohydrate may advantageously comprise cellulos e, cellulose derivatives, sugars, starch, alginate, pectin, natural gum, glucuronic acid or polygalacturonic acid.
The modified carbohydrate may advantageously be prepared as U. K. I, 113, 979 disclosed in our /Patent No. 1Γ11 ,·9·7 by subjecting it to a catalysed degradation process at a temperature of 100-250°C until the weight of the degraded material is less than 90$6 of the dry weight of the original carbohydrate.
Pref erred degradation catalysts inc lude sulphuric acid, sulphamic acid and ammonium sulphamate. The modified carbohydrate may be oxidised cellulose.
The aldol condensation products may advantageously be prepared Israel No. 34410 as described in our -UvK . Patent -Applieati-oii- He ? -2-2-270/69 by acid or catalysed condensation of a compound of the formula 2 2 R'COCI^CI^COR ( i) ( or a precursor thereof ) wherein R' and R , which may be t; e same or different, eac represent a hydrogen atom, or a alkyl, hydroxyalkyl or for my 1 group.
Preferably, the aldol condensation product comprises the condensate from succinaldehyde, acetonyl acetone or the condensate from a precursor of ( i) which is a compound containing a furan ring structure. Ν22$2 A further object of the present invention is to utilise the combustion modifying properties of knovm inorganic fillers to reduce the quantity of health hazard chemicals in smoking compositions, this object being attained by reducing the amount of organic fuel in the smoking mixtures and making up the weight with said inert fillers.
The choice of the inert inorganic fillers to be incorporated in the smoking mixture determines the rate of combustion or how many normal puffs can be had from a riven weight of the mixture.
The art of making an acceptable burning composition involves choosing the correct proportions of fillers which relatively promote or retard the combustion.
Earlier publications in the tobacco substitute field have suggested that burning control of tobacco substitutes is exerted through "hydratcd metal salts". The u: e of such materials as alkali nitrates to improve the "fireholding" of tobacco blends is well known. It has also been suggested that potassium is an essential constituent for the proper burning of tobacco. It is our experience that the water content of tobacco substitutes has only a relatively small effect on the number of puffs given by a particular weight of cigarette but may determine .hether a composition is glowproofed or burns satisfactorily. Hydrated and non-hydrated versions of the same salt can be used. On the other hand, we have found that burning control is strongly influenced by the nature of the combination of cations and anions present. This does not imply that the combustion rate is uninfluenced by other considerations such as fuel particle size or texture of the N22632 smoking material.
The art of retarding combustion without making a composition glowproof yet obtaining the correct puff count from a given weight ■ of smoking mixture by the use of these inert fillers is another key to the success of the present invention. Combustion accelerators are combined with combustion retardants in proportions which give a desirable rate of combustion for a specific organic fuel and a particular amount thereof in .the mixtures. Whilst tids principle of the invention is described and illustrated herein with reference to comr.only available inert fillers, this principle can be applied to any inorganic material which proves to be a safe filler for use in a smoking mixture.
It is impossible to specify that some ionic species retard while i others accelerate glow combustion since some fuels do not susLain combustion in isolation. It suffices to say that we have found that with a number of fuels a number of commonly available acidic anions influence combustion rate and that the order of the retarding ability of a selection of them is formate< oxalate ¾ silicate- carbonate chlorides/sulphate phosphate< borate. Isolated exceptions to these orders indicated can, however, be found. Amongst the cations the order is sodium ¾ potassium This implies, for example, that in smoking mixtures which are identical except that A contains sodium sulphate and B contains the same proportion by weight of magnesium sulphate, A will burn away more quickly.
N22632 Similarly, in two compositions identical except that A contains calcium carbonate and B contains calcium borate, Composition A will '.irn away more quickly than Composition B.
The fillers chosen should not have the power to retain excessive quantities of water, otherwise glowproofing will result.
It is preferable, but not essential, that the fillers should be insoluble in water. . Calcium carbonate has been found to be a most useful agent for use as a combustion accelerator balanced against combustion retarding agents such as calcium orthophosphate (CaHPO^^HgO), magnesite (MgCO^), light basic raa-nosiun carbonate (3M C03.Mg.( OH)2.3H20) , and calcium sulphate (CaSO^.-siLjO) · Using these and other inorganic materials, films can be made which give shred with filling powers comparable to tobacco shred.
Although the above description and the Examples which follow illustrate the required balance of ions being obtained by varying the respective amounts of two inorganic salts, it is possible that a suitable rate of combustion for a smoking mixture could be attained using an optimum amount of a single inorganic salt as inert filler.
The main advantages of the smoking mixtures of the invention compared with earlier synthetic products and, of course, tobacco, are as follows (a) The lower amounts of organic materials present mean that proportionately lower amounts of the harmful smoke products are formed v/hilst maintaining a desirable rate of combustion for the mixture. In this connection, tests carried out on smoking mixtures N22632 of the invention show a reduction in the benzpyrene content of the smoke and a reduction in other chemical species known or suspected to be harmful because of the reduced organic fuel content. Furthermore, the mixtures of the invention advantageously have the same burning characteristics as tobacco based smoking mixtures. They keep lit and continue to burn and they have the same rate of combustion as tobacco. (b) The lower amounts of organic materials present gave rise to lower amounts of any "odour off notes" which may arise from smoking these materials (e.g. the burnt paper note of cellulose).
Lower amounts of added masking agents are required in these instances. (c) The process of the invention permits the use of fuels which wore previously impossible to use on account of their physical properties, e.g. the high solubility and non-fibrous nature of sucrose, -l cose and glucuronic acid. The high inorganic content (Ives "body" to the films of these materials which were previously unusable in smokin. mixtures.
The principle of ion balancing of the inert fillers is illustrated in the f ollowing tables. According to this principle the specific fuel and the amount thereof to be used in the mixture are first selected and then ion balance tests are effected to determine the composition having the most desirable rate of combustion. As can be seen from the tables the ions are investigated separately to ascertain their relative suitabilities for the selected fuel.
Tables 1 to 5 illustrate the comparative retarding powers of 2263? cations of various inert fillers when added to a smoking mixture of the following composition:- i o by weight Thermally degraded cellulose* 53 SCMC 10 Glycerol 14 Calcium carbonate 5 Citric acid 4 Potassium citrate 5 Ammonium sulphate 4 * The thermally degraded cellulose was prepared as follows and in accordance with the method described in our British Patent N22632 Speci ication No. 1 , 13 ,979. 1 .0 part by weight of sheeted alpha-cellulose was immersed in a 5.0 o aqueous solution of ammonium sulphamate and the pulp compressed between rolls to leave 1 .0 part of solution in the pulp. The pulp was air-dried at 45°C and then heated at 240°C so that the pulp became black and the weight of the degraded material was 7 of the original weight of alpha-cellulose plus ammonium sulphamate . The black pulp sheet was allowed to cool and was then ground to a powder passing a 120 BSS sieve .
In each case the inorganio filler constituted 5% of the total weight of the smoking mixture. The effect of the basicity of the cation is clearl indicated in each table.
Table 1 Table 2 Table 3 Table Table 5 Tables 6 to 8 illustrate the retardant properties of different anions. The same basic smoking mixture of Tables 1 to 5 was used in the tests for Tables 6 to 8, N22632 Table 6 Na2C03 5 properties 10.4 Na„SiO, 5 9.4 N22¾ Table 8 Λ second smoking mixture was prepared of similar composition to that utilised for the tests of Tables 1 to 8 but with 53 parts by weight thermally degraded cellulose replaced by 53 parts by weight carbon black as fuel. Tests similar to those of Tables 1 to 8 were carried out on the carbon black based smoking mixture and the results are indicated in the following Tables 1a, 2a, a, 6a and 8a which correspond respectively to Tables 1, 2, 4, 6 and 8. No Tables corresponding to Tables 3, 5 and 7 were produced.
Table 1a Filler added Basicity of cation Puff number MgS0 .7H20 5 11.7 CaSO^.^O 5 10.0 xncreasing Na2S0^ 5 8.5 K2SO '5 8.3 Table- 2a Table a Table 6a Table 8a The followin Tables 9 and 9a illustrate the effect of the ratio of % CaCO^ : CaHP0^.2H20 on the puff number respectively of thermally degraded cellulose based smoking mixtures and carbon black based smoking mixtures. In the case of Table 9 it is to be noted that -17 is the correct puff number for hand rolled cigarettes made with commercial^ available hand rolling paper in contrast to machine made cigarettes which have a puff number of 12.
N22632" Table 9 % thermally degraded : cellulose 28 : 28 . 28 28 28 28 % SCMC 10 10 10 10 10 10 \ Glycerol 14 14 : 14 14 14 14 fo CaC03 10 12 14 16 18 . 20 fo CaHP0 .2H20 25 : 23 21 19 17 15 K citrate 4 4 4 4 i 4 4 Citric acid 4 4 : 4 4 4 4 : • (NH )2S0 5 5 5 5 5 5 :Ratio CaCO, : Ο ΗΡ0^.2Η2° 1:2.5 1:1.92 1:1.5 1 :1.19 1:0.94 1:0.75 :Puff number - 17-18 : 16-17 1 -16 14-15 13-14 Glow- Correct 0 llff too low : proofed numbers puff number : The smoking mixtures above were hand rolled with paper commercially :available in Britain for this purpose. For comparison purposes 1.1 g. :hand rolled tobacco cigarettes give 15-17 puffs. 1.1 g. machine made rcigarettes with the more porous paper used by United Kingdom cigarette manufacturers give 10— ) 2 puffs.
N22632 Table 9a The five compositions indicated in Table 9 and Table 9a as having a correct puff number constituted the first five Examples of smoking mixtures of the invention. Tables 9 and thus serve to illustrate how the ion balancing principle of the present invention is applied.
Applying the principle illustrated in Tables 9 and 9a and utilising the information given in the earlier tables a further seven examples of smoking mixtures according to the invention were prepared, the compositions and preparations of which are illustrated in Examples 6 to 23 below.
In Examples 6 to 9 the organic fuel is thermally degraded cellulose prepared according to the method previously described with regard to Tables 1 to 9· In Examples 10 to 1 the organic fuels are respectively sucrose, glucose, alpha-cellulose and polygalacturonic acid.
In each of Examples 6 to 13 the final composition as aforesaid was reached after tests similar to those indicated in Tables 9 and 9a had been effected. The compositions actually "illustrated in Examples 6 to 13 are those having the best puff numbers. Examples 1 to 23 illustrate further variations in the parameters of the invention.
Example 6 .38 parts thermally degraded cellulose powder, 4,26 parts powdered chalk, 7.10 parts powdered magnesium carbonate and 60 parts water were stirred together. 1.34 parts glycerol and 20 parts water were stirred together then added to the previous mixture.
The whole was paddle-stirred together for 30 minutes.
The mixture was transferred to a Probst & Class mill and at a gap setting of 2 , milled for 5 minutes. The gap was reduced to setting zero and the mixture milled for a further 5 minutes. At the end of this period, 1.92 parts SCMC were added quickly into the centre, of the vortex and the slurry immediately discharged into a clean container then paddle-stirred for 15 minutes. Sufficient water was then added to reduce the viscosity to 55»000 cps.
Film material was made by spreading the slurry at 0.020 in. on a band-drier and drying by means of hot air at 150°C» The band speed was 19 ft.
The film material was shredded and processed satisfactorily on cigarette making machinery. 1.1 g. cigarettes gave 10 standard puffs. The smoke was mild to taste.
Dry weight composition of Example 6 :- Thermally degraded cellulose 26.9 SCC 9.6 Glycerol 6.7 CaCO 21.3 MgCO. 35.5 Example 7 .38 parts thermally degraded cellulose powder, 3 ·8 - parts powdered chalk, 6.72 parts powdered light basic magnesium carbonate and 60 parts water were stirred together. 1.36 parts glycerol, 0.78 part potassium citrate and 20.0 parts water were stirred together, then added to the previous mixture. The whole was paddle-stirred together for 30 minutes.
The mixture was transferred to a Probst & Class mill and at a gap setting of 2, stirred for 5 minutes. The gap was reduced to zero and the mixture milled for a further minutes. At the end of this time, 1.92 parts SCMC were added quickly into the vortex and the slurry immediately discharged into a clean container. The slurry was paddle-stirred for 15 minutes. Sufficient water was then added to reduce the viscosity to 50,000 cps.
Film material was made by spreading the slurry at 0.020 in. on a band-drier and dried by hot air at 150°C. The band speed was 1 ft. min.
The film material was shredded and processed satisfactorily on cigarette making machinery. 1.1 g. cigarettes gave 10 standard puffs. The smoke was to taste.
Dry weight composition of Example Thermally degraded cellulose 26.9 SC D 9.6 Glycerol 6.7 CaCO^ 19.3 3. gC03.Mg(0H) 2. H20 33.6 K Citrate 3.9 Example 8 .08 parts thermally degraded cellulose powder, 4.32 parts powdered chalk, 5»75 parts calcium hydrogen orthophosphate and 60 parts water were stirred together. 2.33 parts glycerol, 0.57 part potassium citrate, 0.72 part citric acid, 0.57 part ammonium sulphate and 20 parts water v/ere stirred together then added to the previous mixture. The whole was stirred together for 30 minutes.
The mixture was transferred to a Probst &. Class mill and at a gap setting of 2 milled for minutes. The gap was reduced to zero and the mixture milled for a further 5 minutes. At the end of this period 1.76 parts SCMC were quickly added into the centre of the vortex and the slurry immediately discharged into a clean container, then paddle-stirred for 15 minutes. The viscosity w3s 4 ^000 6ps.
Film material was made by spreading the slurry at 0.010 in. on a band-drier and drying by means of hot air at 150°C. The band speed was 22 ft. min.
The film material was shredded and processed satisfactorily on cigarette making machinery. 1,1 g. cigarettes gave 10 standard puffs. The smoke was mild to taste.
Dry weight composition of Example 8:- Thermally degraded cellulose 20.18 SCMD 8.33 Glycerol 11.67 CaCO^ 21.62 CaHPO..2Ho0 28.83 K Citrate 2.88 Citric acid 3»6l (NH )2S0 2.88 Example 9 50 parts thermally degraded cellulose powder, 3.2 parts powdered chalk, 5.7 parts powdered magnesium carbonate, 0.95 part powdered, bentonite and 70.0 parts water were stirred together. 1.25 parts glycerol, 0.7 part potassium citrate and 11.5 parts water were stirred together and then added to the previous mixture. The whole was stirred together for 15 minutes.
The mixture was transferred to a Probst & Class mill and at a gap setting of 2 milled for 5 minutes. The gap was now reduced to zero and the mixture milled for a further 5 minutes. At the end of this time, 1.7 parts 9CMC were added quickly into the centre of the vortex and the slurry immediately discharged into a clean container.
The slurry was paddle-stirred for 15 minutes and at the end of this period sufficient water was added to reduce the viscosity to 60,000 cps.
Film material was made by spreading the slurry at 0.020 in. on a band-drier and drying by means of hot air at 150°C. The band speed was 16 ft. min The film material was shredded and processed satisfactorily on cigarette making machinery. 1.1 g. cigarettes gave 11 standard puffs. The smoke was mild to taste.
The dry weight composition of Kxample 9 was:- % Thermally degraded cellulose 26.9 SCMC 9.6 Glycerol 6.7 CaCO, 3 17.3 gC03 30.6 Bentonite 5.0 Citrate 3.9 Kxample 10 .6 parts sucrose, 7.8 parts calcium carbonate, 2.0 parts light basic magnesium carbonate, 0.8 part potassium citrate, 1.1 parts citric acid and 0.8 part ammonium sulphate were stirred for half an hour with 68.6 parts of water. The mixture was transferred to a Probst & Class mill and at a gap setting of 2 milled for minutes. The gap was reduced to setting zero and the mixture milled for a further 5 minutes. At the end of this time 2.0 parts SCivC were added quickly and the slurry discharged immediately into a container and paddle-stirred for 15 minutes. 11.3 parts of water were added to reduce the viscosity to 56 ,000 cps.
Film material was prepared by spreading the slurry at 0.018 in. on a band-drier and drying by means of air at 60°C. The band speed was 9 ft./min.
The film material was very sensitive to moisture. It could, however, be satisfactorily shredded and processed by cigarette making macMnery if the relative humidity of the atmosphere was maintained at 58-60 RH and 60°P. Under these conditions the equilibrium moisture content of the shred was 6.3-6.8%, 1.1 g. cigarettes gave 10 puffs. The smoke from the cigarettes was mild to taste.
The dry weight composition of Example 10 was:- Sucrose 28 SCMC 10 CaCO^ 39 Light basic Mg carbonate 10 K citrate 1+ Citric acid Example 11 .5 parts glucose, 7 »6 parts calcium carbonate, 2.0 parts light basic magnesium carbonate, 0.75 part potassium citrate, 0.75 part ammonium sulphate end 1,0 part citric acid were stirred for half an hour with 67,2 parts of water. The mixture was transferred to a Probst & Class mill and at a gap setting of 2 milled for 5 minutes. The gap was reduced to setting zero and the mixture milled for a further 5 minutes. At the end of this time 20 parts SCMC were added quickly and the slurry discharged immediately into a container and paddle-stirred for 15 minutes. 13.3 parts of water were added to reduce the viscosity to 60,000 cps.
Film material was prepared by spreading the slurry at 0,020 in, on a band drier and drying by means of air at 150°C. The band speed The film material was very sensitive to moisture. It could, however, be satisfactorily shredded and processed by cigarette making machinery if the relative humidity of the atmosphere was maintained at 53-55% RH and 60°F, Under these conditions the equilibrium moisture content of the shred was 5~6¾/Ό, 1,1 g, cigarettes gave 10 puffs. The smoke from the cigarettes was mild to taste.
Dry weight composition of Example 11:- Glucose SCMC CaCO 3 Light basic Mg carbonate K citrate C trate acid (M1 )2S0 • Example 12 4.5 parts alpha-cellulose powder, 3.5 parts chalk, 5.1 parts calcium hydrogen orthophosphate, 2.5 parts glycerol, 0.8 part citric acid, 0.7 part ammonium sulphate, 0.7 part potassium citrate and 71 parts water were stirred together for half an hour. The mixture was transferred to a Probst & Class mill and at a gap setting of 2 milled for 5 minutes. The gap was reduced to setting zero and the mixture milled for a further 5 minutes. At the end of this period 1.7 parts of SCMC were added quickly and the slurry discharged immediately into a container and paddle-stirred for 1 minutes. 9.5 parts of water were added to reduce the viscosity to 46 ,000 cps.
Film material was made by spreading the slurry at 0.012 in. on a band-drier and drying by means of hot air at 150°C. The band speed was 20 ft./min.
The film material was shredded and processed satisfactorily on cigarette making machinery. 1,1 g. cigarettes gave 10 standard puffs. The smoke from the cigarettes was mild. .
The dry weight composition of Example 12 was:- % Alpha-cellulose 24.35 SCMC 8.7 Glycerol 12.3 CaCO 17.4 3 CaHPO, .2H 0 26.0 226 K citrate 3.5 Citric acid . 5 (NH )2so 3.5 Example 13 18 5.93 4.24 1.65· parts glycerol, --.£ parts calcium carbonate, - *95 partsCaHP0.2H O ■HiagHes-i-te- and O.J? part potassium citrate were stirred for 10 minutes 70 69 with 65-.-?- arts of water. 1.65-parts SCIC were added and stirred 75 for half an hour, then 2+..$ parts of polygalacturonic acid were added and stirring continued for a further half -an- hour. The slurry was milled for 10 minutes at setting 2 on Probst & Class mill and then the at setting zero for/same length of time. The slurry was then discharged and the viscosity reduced to 5 >000 cps. by the addition of 18gi parts of water.
Film-forming v/as carried out on a band-drier using hot air at 150°C and band speed of 15-16 ft./min. with slurry spread at 0.020 in.
The film material was satisfactorily shredded and processed by cigarette making machinery. 1.1 g. cigarettes gave 10 puffs. The smoke from the cigarettes was mild to taste.
The dry weight composition of Example 13 was:- % Polygalacturonic acid 23.73 SCMC 8.47 Glycerol 5.93 CaCO^ 29.66 N22632 21.19 3-39 3.39 4.24 N226¾£ Example 14 2.04 parts of glycerol and 1.17 parts of potassium citrate were dissolved in 150 mis. of water. 2.88 parts of SCKC were then added to the solution and stirred for 15 minutes. 8.07 parts of starch, 10.08 parts of magnesium carbonate and 5.76 parts powdered chalk were mixed together in the dry state then added to the previous mixture. The whole was stirred for 1 hour.
Film material was made by spreading the slurry at 0.020 inches on {class plates and left to dry. The film material was humidified and shredded. Ten cigarettes were hand rolled with Imperial Verge paper. 1.1 g. cigarettes gave 10 standard puffs. The smoke was mild to taste.
Dry weight coinposition:- Starch 26.9 SCMC 9.6 Glycerol 6.8 CaCO, 19.2 3 MgC03 33.6 Potassium Citrate 3·9 Example 15 2.04 parts of glycerol and 1.17 parts potassium citrate were dissolved in 250 mis. of water. 2.88 parts of SCMC were then added to the solution and stirred for 15 minutes. 8.07 parts of alginic acid, 10.08 parts of magnesium carbonate and 5.76 parts powdered chalk were mixed together in the dry state, then added to the previous mixture. The whole was stirred for 1 hour.
Film material was made by spreading the slurry at 0.02 inches on glass plates and left to dry. The film material was humidified and shredded. Ten cigarettes were hand rolled with Imperial Verge paper. 1.1 g. cigarettes gave 11 standard puffs. The smoke was mild to taste.
Dry weight composition:- % Alginic acid 26.9 Glycerol 6.8 SCMC 9.
CaC03 19.2 MgCOj 33.6 Potassium Citrate 3.9 Example 16 2.04 parts of glycerol and 1.17 parts of potassium citrate were dissolved in 150 mis. of water. 2.88 parts of SCMC were then added to the solution and stirred for 15 minutes. 8.07 parts of thermally degraded sucrose, 10.08 parts of magnesium carbonate and 5.76 parts of powdered chalk were mixed together in the dry state then added to the previous mixture. The whole was stirred for 1 hour.
Film eiaterial was made by spreading the slurry at 0.02 inches on glass plates and left to dry. The film material was humidified and shredded. Ten cigarettes were hand rolled with Imperial Verge paper. 1.1 g. cigarettes gave 10 standard puffs.
Dry weight composition:- % Thermally degraded sucrose 26.5 Glycerol 6.8 SCMC 9.6 CaCOj 1 .2 Potassium Citrate 3.9 Ma nesite 33.6 Example 17 2.04 parts of glycerol and 1.17 parts of potassium citrate were dissolved in 150 nils, of water. 2.08 parts of sodium alginate were then added to the solution and stirred for 15 minutes. 8.07 parts of thermally degraded cellulose, 11.8b parts of magnesium carbonate and 3. 6 parts powdered chalk were mixed together in the dry state then added to the previous mixture. The whole was stirred for 1 hour.
Film material was made by spreading the slurry at 0.02 inches on glass plates and left to dry. The film material was humidified and shredded. Ten cigarettes were hand rolled with Imperial Verge paper. 1.1 g. cigarettes gave 10 standard puffs. The smoke was mild to taste.
Dry weight composition:- % Thermally degraded cellulose 26.9 Glycerol 6.8 Sodium Alginate 9.6 Potassium citrate 3.9 39.6 Example 18 2.C4 parts of glycerol and 1.17 parts of potassium citrate were dissolved in 75 mis. of water. 2.88 parts locust bean gum were then added to the solution and stirred for 15 minutes. 8.07 parts of thermally degraded cellulose, 12.66 parts magnesium carbonate and 3.18 parts powdered chalk were mixed together in the dry state then added to the previous mixture. The whole was stirred for 1 hour.
Film material was made by spreading the slurry at 0.02 inches on ; Glycerol 6.8 Locust Bean Gum 9.
Potassium Citrate 3.9: MgCO, 42.2 Example 1 2.04 parts glycerol and 1.17 parts potassium citrate were dissolved in 150 mis. of water. 2.80 parts methyl cellulose were then added to the solution and stirred for 15 minutes. 8.07 parts thermally degraded cellulose; 12.66 parts magnesium carbonate and 3.18 parts powdered chalk were mixed together in the dry state, then added to the previous mixture. The whole was stirred for 1 hour.
Film material was made by spreading the slurry at 0.02 inches on glass plates and left. to dry. The film material was humidified and shredded. Ten cigarettes were hand rolled with Imperial Verge pape . 1.1 g. cigarettes 'i gave 11 standard puffs. The smoke was mild to taste.
Dry weight composition:- Thermally degraded cellulose 26.9 Glycerol 6.8 Methyl Cellulose 9-6 CaCO., 10.6 3 Potassium Citrate 3.9 IlgCO, t 42.2.
Example 20 2.02+. parts glycerol and 1.17 parts potassium citrate were dissolved in 150 mis. of water. 2.88 parts SC1 were then added to the solution and stirred for 15 minutes. 8.07 parts thermally degraded cellulose, 5.76 parts ferrous sulphate and 10.08 parts magnesium carbonate were mixed together in the dry state, then added to the previous mixture. The whole was stirred for 1 hour.
Film material was made by spreading the slurry at 0.02 inches on glass plates and left to dry. The film material was humidified and shredded. Ten cigarettes were hand rolled with Imperial Verge paper. 1.1 g. cigarettes gave 11 standard puffs. The smoke was mild to taste.
Dry weight composition:- % Thermally degraded cellulose 26.9 Glycerol 6.8 Potassium citrate 3.9 SCMC 9.6 PeSO, 19,2 4- gCO, 33.6 Example 21 2.04 parts glycerol and 1.17 parts potassium citrate were dissolved in 150 mis. of water. 2.88 parts SCMC were then added to the solution and stirred for 15 minutes. 8.07 parts thermally degraded cellulose, 10.08 parts aluminium hydroxide and .76 parts powdered chalk were mixed together in the dry state, then added to the previous mixture. The whole was stirred for 1 hour.
Film material was made by spreading the slurry at 0.02 inches on glass plates and left to dry. The film material was humidified and shredded. Ten cigarettes were hand rolled with Imperial Verge paper, 1.1 g. cigarettes gave 12 standard puffs. The smoke was mild to taste.
Dry weight composition:- % Thermally degraded cellulose 26.9 Glycerol 6.8 Potassium citrate 3.9 SC1C 9.6 CaCO^ 19.2 AL(OH), 33.6 Example 22 2.04 parts glycerol and 1.17 parts potassium citrate were dissolved in 150 mis. of water. 2.88 parts SCMC were then added to the solution and stirred for 15 minutes. 8.07 parts thermally degraded cellulose, 7.56 parts magnesium carbonate and 8.16 parts titanium dioxide were mixed together in the dry state, then added to the previous mixture. The whole was stirred for 1 hour.
Film material was made by spreading the slurry at 0.02 inches on glass plates and left to dry. The film material was humidified and shredded. Ten cigarettes were hand rolled with Imperial Verge paper. 1.1 g. cigarettes gave 10 standard puffs. The smoke was mild to taste.
Dry weight composition % Thermally degraded cellulose 26.9 Glycerol 6.8 SCMC 9.6 Potassium citrate 3 ·9 Titanium dioxide 27.2 Magnesium carbonate 25.2 Example 23 2,04 parts glycerol and 1.17 parts potassium citrate were dissolved in 150 mis. of water. 2.88 parts SCMC were then added to the solution and stirred for 15 minutes. 8.07 parts thermally degraded cellulose, 11.28 parts magnesium carbonate and .56 parts alumino-silicate were mixed together in the dry state , then added to the previous mixture. The whole was stirred for 1 hour.
Film material was made by spreading the s lurry at 0.02 inches on glass plates and left to dry. The film material was humidified and shredded. Ten cigarettes were hand rolled with Imperial Verge paper. 1.1 g. cigarettes gave 12 standard puffs. The smoke was mild to taste.
Dry weight composition:- Thermally degraded cellulose 26.9 Glycerol 6.8 SCMC 9.6 Potassium citrate 3.9 Aluminosilicate 15«2 Magnesium carbonate 37.6
Claims (23)
1. A smoking mixture comprising (a) as smoke -producing fuel a solid organic combustible material other than tobacco. (b) a harmless inorganic filler in which the anions comprise formate, oxalate, citrate, tartrate, silicate, carbonate, chloride, sulphate, phosphate, borate, oxide, dioxide or aluminate and the cations compris sodium, potassium, calcium, magnesium, iron or titanium. (c) sufficient binder to enable the mixture to be fabricated said filler being present in a proportion of 40 to 65% by weight of the mixture and the combination of cations and anions in the filler being as to impart a commercially acceptable burning rate to the mixture.
2. A smoking mixture as claimed in claim 1 wherein the inorganic filler comprises a plurality of inorganic salts admixed in quantities such as to obtain the balance of anions and cations most appropriate for imparting an acceptable rate of combustion to the smoking mixture.
3. A smoking mixture as claimed in claim 1 wherein the inorganic filler comprises a single inorganic salt present in an amount such as to obtain an acceptable rate of combustion for the smoking mixture.
4. A smoking mixture as claimed in any one of the previous claims wherein the inorganic filler comprises calcium carbonate, calcium borate, sodium borate, calcium, orthophosphate, calcium oxalate, iron sulphate, titanium dioxide, magnesium carbonate, sodium alum inosilic ate, bentonite or aluminium hydroxide. 5 -7» A smoking mixture as claimed in any one of the preceding claims wherei-n the organic combustible material or fuel comprises carbohydrate.
5
6. S-r A smoking mixture as claimed in Claim fp wherein said carbohydrate comprises cellulose, cellulose derivatives, sugars, starch, alginate, 5 pectin, natural gum, glucuronic acid or polygalacturonic acid. 4
7. A smoking mixture as claimed in any one of Claims 1 to & wherein the organic combustible or fuel comprises modified carbohydrate. 7
8. 1-r A smoking mixture as claimed in Claim Φ wherein the modified ο carbohydrate is oxidised cellulose. 7 10 9. 44»- A smoking mixture as claimed*in Claim # wherein the modified carbohydrate is thermally degraded carbohydrate prepared as disclosed in U.K. Patent No. 1,113»979 by subjecting carbohydrate material to a catalysed degradation process at a temperature of 100-250°C until the weight of the degraded material is less than 0¾ of the dry weight of 15 the original carbohydrate.
9
10. †2v A smoking mixture as claimed in Claim -Ή -wherein the modified carbohydrate is thermally degraded cellulose. 4
11. -1-3» A smoking mixture as claimed in any one of Claims 1 to & wherein the organic combustible material is solid condensate produced by acid or 20 based catalysed condensation of a compound of the formula R COC^CrLjCQiT(I) 1 2 (or a precursor thereof) wherein R and R , which may be the eame or different, each represent a hydrogen atom, or an alkyl, hydroxyalkyl or formyl group. 11
12. A smoking mixture as claimed in Claie £5 wherein said organic combustible material comprises the cond^pate from succinaldehyde, ac acetone or the condensate from a precursor of (1> which is a compound containing a furan ring structure. 4 _ *
13. §» A smoking mixture as claimed in any one Claims 1 to & in which the smoke-producing fuel comprises a carbon sample which produces low amounts of polycyclic aromatic hydrocarbons.
14. H>. A smoking mixture as claimed in any one of the preceding claims comprising a plasticiser/humecta t in addition to the binder.
15. A smoking mixture as claimed in Claim l wherein the plasticiser/ humectant comprises glycerol, ethylene glycol or polyethylene glycol.
16. -1-&» A smoking mixture as claimed in any one of the preceding claims wherein the binder comprises carboxymethyl cellulosd and its salts, other carboxylated carbohydrates, natural gum, guar gum, locust bean gum or cellulose ethers.
17. It?. -19·» smoking mixture as claimed in any one of the preceding claims comprising tobacco as part of the smoke-producing fuel.
18. -20. A smoking mixture as claimed in any one of the preceding claims 15 comprising medicaments, flavourants, drugs and other known additives.
19. -2-1·, A smoking mixture substantially as hereinbefore described with reference to the Examples.
20. -22-. A method of manufacturing a smoking mixture comprising mixing the O ingredients (a) (b) and (c) specified in claim 1 and forming a shaped 20 article of the mixture. 20
21. -2->. A method as claimed in Claim 22-wherein the shaped article is a film, extruded filament or tape. 20 21
22. ^. A method as claimed in claim 22-or Claim -2-5" comprising combining an inorganic filler which is a combustion accelerator with an inorganic 25 filler which is a combustion retarder in proportions which impart a combustion commercially acceptable rate of eera&u-s-ion to the mixture. ·
23. 25»- method as claimed in any one of Claims--1- to 2¾^-wherein the anion of the inorganic filler comprises formate, oxalate, citrate, tartrate, silicate, carbonate, chloride, sulphate, phosphate, borate, oxide, dioxide 30-1.? ! / 2 or aluminate and the cation of the inorganic filler comprises sodium, potassium, calcium, magnesium, iron or titanium 19 23 -26-. A method as claimed in any one of Claims 21 to -2^- wherein the inorganic filler comprises calcium carbonate, calcium borate, sodium fcorate, calcium orthophosphate, calcium oxalate, iron sulphate, titanium dioxide, magnesium carbonate, sodium aluminosilicate, bentonite, or aluminium hydroxide or mixture thereof. -2?.- A method of manufacturing a smoking mixture substantially as hereinbefore described. -2-8-. A smoking mixture prepared according to the method of any one of 20 25 Claims-2-i- to -2-7, AGENTS FOR APPLICANTS -43 _ FES/JB
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB03860/70A GB1299296A (en) | 1970-03-23 | 1970-03-23 | Improved smoking mixture |
Publications (2)
Publication Number | Publication Date |
---|---|
IL36421A0 IL36421A0 (en) | 1971-05-26 |
IL36421A true IL36421A (en) | 1973-07-30 |
Family
ID=10030702
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
IL36421A IL36421A (en) | 1970-03-23 | 1971-03-16 | Smoking mixture |
Country Status (19)
Country | Link |
---|---|
US (1) | US3885574A (en) |
JP (1) | JPS5233200B1 (en) |
BE (1) | BE764732A (en) |
CA (1) | CA923006A (en) |
CH (1) | CH568027A5 (en) |
CS (1) | CS154323B2 (en) |
DE (1) | DE2114084C3 (en) |
FI (1) | FI51036C (en) |
FR (1) | FR2109564A5 (en) |
GB (1) | GB1299296A (en) |
IE (1) | IE35236B1 (en) |
IL (1) | IL36421A (en) |
IT (1) | IT1043835B (en) |
LU (1) | LU62830A1 (en) |
NL (1) | NL150319B (en) |
NO (1) | NO126416B (en) |
SE (1) | SE383953B (en) |
TR (1) | TR16940A (en) |
ZA (1) | ZA711889B (en) |
Families Citing this family (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4033359A (en) * | 1970-03-23 | 1977-07-05 | Imperial Chemical Industries Limited | Smoking mixture |
GB1495941A (en) * | 1974-02-21 | 1977-12-21 | Imp Group Ltd | Smoking product |
GB1447918A (en) * | 1974-07-05 | 1976-09-02 | Ici Ltd | Smoking mixture |
US4147172A (en) * | 1974-07-16 | 1979-04-03 | Imperial Chemical Industries Limited | Smoking mixtures |
US4109664A (en) * | 1975-03-05 | 1978-08-29 | Brown & Williamson Tobacco Corporation | Smoking materials |
US4793365A (en) * | 1984-09-14 | 1988-12-27 | R. J. Reynolds Tobacco Company | Smoking article |
US5042509A (en) * | 1984-09-14 | 1991-08-27 | R. J. Reynolds Tobacco Company | Method for making aerosol generating cartridge |
GB2181034A (en) * | 1985-01-04 | 1987-04-15 | Yasumasa Morita | Medicinal tobacco |
US5076297A (en) * | 1986-03-14 | 1991-12-31 | R. J. Reynolds Tobacco Company | Method for preparing carbon fuel for smoking articles and product produced thereby |
US4732168A (en) * | 1986-05-15 | 1988-03-22 | R. J. Reynolds Tobacco Company | Smoking article employing heat conductive fingers |
US4893639A (en) * | 1986-07-22 | 1990-01-16 | R. J. Reynolds Tobacco Company | Densified particulate materials for smoking products and process for preparing the same |
US5074321A (en) * | 1989-09-29 | 1991-12-24 | R. J. Reynolds Tobacco Company | Cigarette |
US4981522A (en) * | 1988-07-22 | 1991-01-01 | Philip Morris Incorporated | Thermally releasable flavor source for smoking articles |
US4991606A (en) * | 1988-07-22 | 1991-02-12 | Philip Morris Incorporated | Smoking article |
US5345951A (en) * | 1988-07-22 | 1994-09-13 | Philip Morris Incorporated | Smoking article |
US4966171A (en) * | 1988-07-22 | 1990-10-30 | Philip Morris Incorporated | Smoking article |
US4920990A (en) * | 1988-11-23 | 1990-05-01 | R. J. Reynolds Tobacco Company | Cigarette |
US5092353A (en) * | 1989-01-18 | 1992-03-03 | R. J. Reynolds Tobacco Company | Cigarette |
US4942888A (en) * | 1989-01-18 | 1990-07-24 | R. J. Reynolds Tobacco Company | Cigarette |
US5129408A (en) * | 1990-08-15 | 1992-07-14 | R. J. Reynolds Tobacco Company | Cigarette and smokable filler material therefor |
US5105836A (en) * | 1989-09-29 | 1992-04-21 | R. J. Reynolds Tobacco Company | Cigarette and smokable filler material therefor |
US5101839A (en) * | 1990-08-15 | 1992-04-07 | R. J. Reynolds Tobacco Company | Cigarette and smokable filler material therefor |
US5007440A (en) * | 1989-11-14 | 1991-04-16 | R. J. Reynolds Tobacco Company | Process for providing smokable material |
US5188130A (en) * | 1989-11-29 | 1993-02-23 | Philip Morris, Incorporated | Chemical heat source comprising metal nitride, metal oxide and carbon |
US5512306A (en) * | 1992-06-19 | 1996-04-30 | Pharmica Ab | Smoking substitute |
US5722432A (en) * | 1990-07-02 | 1998-03-03 | British-American Tobacco Company Limited | Smoking articles |
US5396911A (en) * | 1990-08-15 | 1995-03-14 | R. J. Reynolds Tobacco Company | Substrate material for smoking articles |
US5415186A (en) * | 1990-08-15 | 1995-05-16 | R. J. Reynolds Tobacco Company | Substrates material for smoking articles |
US5148821A (en) * | 1990-08-17 | 1992-09-22 | R. J. Reynolds Tobacco Company | Processes for producing a smokable and/or combustible tobacco material |
US5203355A (en) * | 1991-02-14 | 1993-04-20 | R. J. Reynolds Tobacco Company | Cigarette with cellulosic substrate |
US5263500A (en) * | 1991-04-12 | 1993-11-23 | Philip Morris Incorporated | Cigarette and wrapper with controlled puff count |
US5161551A (en) * | 1991-04-12 | 1992-11-10 | Philip Morris Incorporated | Paper wrapper having improved ash characteristics |
GB9218063D0 (en) * | 1992-08-25 | 1992-10-14 | Rothmans Int Tobacco | Process for enhancing the perceived strength of tobacco smoke |
US6637439B2 (en) | 2001-08-31 | 2003-10-28 | Philip Morris Incorporated | Tobacco smoking mixture for smoking articles such as cigarettes |
US6817365B2 (en) * | 2001-11-15 | 2004-11-16 | Philip Morris Usa Inc. | Cigarette paper having heat-degradable filler particles, and cigarette comprising a cigarette paper wrapper having heat-degradable filler particles |
US20060086367A1 (en) | 2004-10-25 | 2006-04-27 | Philip Morris Usa Inc. | Additives for tobacco cut filler |
CN115215713A (en) * | 2021-04-19 | 2022-10-21 | 重庆中烟工业有限责任公司 | Smoke agent and preparation method and application thereof |
CN117509614B (en) * | 2024-01-04 | 2024-03-19 | 河北宝力工程装备股份有限公司 | Preparation method of carbon material for rubber engineering equipment |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2809904A (en) * | 1954-11-17 | 1957-10-15 | Raymar Company | Smoking product |
US2914072A (en) * | 1955-01-31 | 1959-11-24 | Tyrer Daniel | Process of improving the smoking qualities of tobacco |
US3106210A (en) * | 1957-11-18 | 1963-10-08 | Reynolds Metals Co | Smoking tobacco |
US3003895A (en) * | 1957-12-06 | 1961-10-10 | Heinr Borgwaldt | Tobacco product and method of making the same |
US2930720A (en) * | 1958-05-07 | 1960-03-29 | Erb Tobacco Products Co Inc | Smoking composition |
US3112754A (en) * | 1961-10-30 | 1963-12-03 | Robert Harper J | Method of making a tobacco substtute |
GB1113979A (en) * | 1966-05-19 | 1968-05-15 | Ici Ltd | Modified carbohydrate material for smoking mixtures |
US3459195A (en) * | 1966-06-16 | 1969-08-05 | Philip Morris Inc | Reinforced reconstituted tobacco sheet |
US3461879A (en) * | 1967-06-30 | 1969-08-19 | Celanese Corp | Oxidized cellulose tobacco substitute composition |
DE1900491C3 (en) * | 1968-01-10 | 1981-04-02 | Celanese Corp., 10036 New York, N.Y. | Tobacco substitute material |
US3608560A (en) * | 1968-11-07 | 1971-09-28 | Sutton Res Corp | Smokable product of oxidized cellulosic material |
US3529602A (en) * | 1969-02-27 | 1970-09-22 | Philip Morris Inc | Tobacco substitute sheet material |
-
1970
- 1970-03-23 GB GB03860/70A patent/GB1299296A/en not_active Expired
-
1971
- 1971-03-16 IL IL36421A patent/IL36421A/en unknown
- 1971-03-18 US US125872A patent/US3885574A/en not_active Expired - Lifetime
- 1971-03-18 NO NO1046/71A patent/NO126416B/no unknown
- 1971-03-22 TR TR16940A patent/TR16940A/en unknown
- 1971-03-22 SE SE7103675A patent/SE383953B/en unknown
- 1971-03-22 IE IE363/71A patent/IE35236B1/en unknown
- 1971-03-22 IT IT22091/71A patent/IT1043835B/en active
- 1971-03-22 NL NL717103799A patent/NL150319B/en not_active IP Right Cessation
- 1971-03-22 FI FI710811A patent/FI51036C/en active
- 1971-03-22 LU LU62830D patent/LU62830A1/xx unknown
- 1971-03-23 JP JP46016262A patent/JPS5233200B1/ja active Pending
- 1971-03-23 ZA ZA711889A patent/ZA711889B/en unknown
- 1971-03-23 CS CS210171A patent/CS154323B2/cs unknown
- 1971-03-23 FR FR7110230A patent/FR2109564A5/fr not_active Expired
- 1971-03-23 CH CH420971A patent/CH568027A5/xx not_active IP Right Cessation
- 1971-03-23 BE BE764732A patent/BE764732A/en unknown
- 1971-03-23 DE DE712114084A patent/DE2114084C3/en not_active Expired
- 1971-03-23 CA CA108538A patent/CA923006A/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
CH568027A5 (en) | 1975-10-31 |
IE35236B1 (en) | 1975-12-24 |
DE2114084C3 (en) | 1979-03-01 |
FI51036B (en) | 1976-06-30 |
LU62830A1 (en) | 1971-03-24 |
CA923006A (en) | 1973-03-20 |
IL36421A0 (en) | 1971-05-26 |
IE35236L (en) | 1971-09-23 |
DE2114084B2 (en) | 1978-06-29 |
BE764732A (en) | 1971-09-23 |
GB1299296A (en) | 1972-12-13 |
NL7103799A (en) | 1971-09-27 |
IT1043835B (en) | 1980-02-29 |
US3885574A (en) | 1975-05-27 |
FR2109564A5 (en) | 1972-05-26 |
CS154323B2 (en) | 1974-03-29 |
FI51036C (en) | 1976-10-11 |
TR16940A (en) | 1973-11-01 |
DE2114084A1 (en) | 1971-12-23 |
NL150319B (en) | 1976-08-16 |
ZA711889B (en) | 1972-11-29 |
SE383953B (en) | 1976-04-12 |
NO126416B (en) | 1973-02-05 |
JPS5233200B1 (en) | 1977-08-26 |
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