US3924644A

US3924644A - Smoking mixtures

Info

Publication number: US3924644A
Application number: US415427A
Authority: US
Inventors: Robert Craig Anderson; James Andrew Gibson
Original assignee: Imperial Chemical Industries Ltd
Current assignee: Imperial Group PLC
Priority date: 1972-12-04
Filing date: 1973-11-13
Publication date: 1975-12-09
Anticipated expiration: 1992-12-09
Also published as: IE38487B1; LU68909A1; BE807936A; IE38487L; NL7315988A; DE2356706A1; GB1398177A; JPS4993596A; CA997644A; FR2212745A5

Abstract

A smoking mixture characterized by having the general flavor of flue cured Virginia tobacco is formulated from a mixture of nicotine, a modified (thermally degraded) carbohydrate and flue cured Virginia tobacco. The mixture includes as a necessary flavorant isovaleric or Beta -methyl valeric acids and/or mixtures thereof in amounts from 0.02% to 0.2% by weight of the mixture.

Description

United States Patent [191 Anderson et al.

[451 Dec. 9, 1975 SMOKING MIXTURES [73] Assignee: Imperial Chemical Industries Limited, England [22] Filed: Nov. 13, 1973 [21] Appl. No.: 415,427

[30] Foreign Application Priority Data Dec. 4, 1972 United Kingdom 55833/72 [52] US. Cl 131/17 R; 131/2; 131/144 [51] Int. C1. A24B 3/12; A24B 15/04 [58] Field of Search 131/2, 9, 17, 144, 15

[56] References Cited I UNITED STATES PATENTS 2,171,986 5/1939 Poetsohke 131/15 R 2,766,145 10/1956 Jones 131/15 R 3,125,098 3/1964 Osborne I. 131/17 R 3,461,879 8/1969 Kirkland 131/2 3,545,448 12/1970 Mormon 131/2 FOREIGN PATENTS OR APPLICATIONS 908,439 10/1962 United Kingdom 131/17 687,507 3/1967 Belgium 1,900,491 11/1969 Germany 131/2 OTHER PUBLICATIONS Tobacco Flavoring For Smoking Products-Leffingeell, Yound and Bemasek (Text) pub by the R. J. Reynolds Co. of Winston Salem North Carolina (Aug.

1972) pp. 13 and 14 cited.

Primary Examiner-Melvin D. Rein Attorney, Agent, or Firm-Cushman, Darby & Cushman [57] ABSTRACT A smoking mixture characterized by having the general flavor of flue cured Virginia tobacco is formulated from a mixture of nicotine, a modified (thermally degraded) carbohydrate and flue cured Virginia tobacco. The mixture includes as a necessary flavorant isovaleric or B-methyl valeric acids and/or mixtures thereof in amounts from 0.02% to 0.2% by weight of the mixture.

7 Claims, No Drawings SMOKING MIXTURES This invention relates to smoking mixtures.

It is known from U.S. Pat. No. 3,180,380 that isovaleric and B-methyl valeric acids together impart a Turkish tobacco flavour to flue-cured Virginia tobacco (also called bright or FCV tobacco). A Turkish flavour is not generally favoured by regular smokers of FCV tobacco which has a distinctive flavour of its own.

It has now been found, quite surprisingly that certain carboxylic acids impart to modified carbohydrates a flavour of such character that considerable quantities can be blended with FCV tobacco without disturbing the general flavour of the tobacco. The flavourant effect of these carboxylic acids is particularly good when nicotine is also present.

The invention therefore provides a smoking mixture comprising a modified carbohydrate as smoke-producing fuel, nicotine, and as a flavourant isovaleric acid, B-methylvaleric acid, butyric acid or a mixture of at least two of the said acids.

The term modified means chemically modified and implies that the original carbohydrate has undergone a change of a chemical nature.

The modified carbohydrate used as smoke-producing fuel may desirably comprise a thermally degraded car bohydrate, especially thermally degraded cellulose, prepared for example as described and claimed in our United Kingdom Patent No. 1,113,979 by subjecting carbohydrate to a catalysed degradation process at a temperature of 100250C until the weight of degraded material is less than 90% of the dry weight of the original carbohydrate.

The modified carbohydrate used as smoke-producing fuel may also comprise a solid condensate prepared by acid or base catalysed condensation of a compound of the formula RCO CI-I .CH COR (or a precursor thereof) wherein R and R which may be the same or different, each represents a hydrogen atom, or an alkyl, hydroxyalkyl or formyl group. Such condensates in fabricated form are described and claimed in our United Kingdom Patent No. 1,298,354.

Further examples of modified carbohydrates which may be used as smoke-producing fuel are oxidised cellulose (see for example Kenyon et a1. Industrial and Engineering Chemistry, Volume 41, page 2 et seq and cellulose ethers, particularly carboxymethylcellulose or its salts.

The preferred acids for use in the invention are isovaleric and B-methylvaleric, and mixtures of these (for example in a ratio by weight of from 4:1 to 0.25:1 of the former to the latter) are especially effective.

The aforesaid acids (or mixtures thereof) are effective even when present in very small proportions. Thus for example proportions even as low as 0.02% by weight of the smoking mixture are effective. Higher proportions may be used if desired, but when more than about 0.2% is used an adverse flavour effect becomes noticeable.

The smoking mixtures of the invention may contain other ingredients to impart desired physical properties and burning characteristics. Such ingredients may for example, comprise:

Inorganic fillers By suitable choice of inorganic compounds high proportions of filler may be incorporated while maintaining an acceptable burning rate.

Binders, particularly film forming agents, e.g. methyl cellulose, sodium carboxymethylcellulose, pectins, gums.

Humectants e.g. glycerol, glycols.

Glow controlling catalysts e.g. potassium citrate.

Colouring matters.

Ash cohesion agents e.g. citric acid, bentonite.

Substances producing acidic matter in the smoke in order to counteract the ,chokiness of the nicotine, e.g. volatile acids, neutral substances pyrrolysing to volatile acids, or weak base salts. The use of such substances in nicotine-fortified smoking mixtures is described and claimed in our United Kingdom Patent No. 1,339,144 (Application No. 41921/71).

Carbohydrate materials e.g. cellulose, alginate, starch or sugar, or comminuted tobacco to improve physical properties. Such materials would generally be present in minor proportion only so as not to increase unduly the amount of harmful constituents in the smoke. I 5

Besides the aforesaid acids other flavouring agents may also be present in the smoking compositions if desired. In particular the smoking compositions may additionally contain a protein and this is a further feature of the invention.

Our copending United Kingdom Pat. No. 1,312,483 describes a smoking mixture comprising a modified carbohydrate as smoke producing fuel and protein as flavourant, (the amount of protein relative to smokeproducing fuel being in the range 1:1 to 1:60, preferably 1:8 to 1:30).

We have found that when such a mixture is fortified by nicotine to increase the satisfaction experienced by the smoker, the flavour effect of the protein is less marked. However, the presence of protein remains desirable for this stabilises the nicotine and also improves the delivery of nicotine in the smoke from the mixture. It is found that when protein is incorporated in the smoking compositions of the present invention the carboxylic acids, even when used in very low proportions restore or enhance the flavourant effect of the protein so that the mixture has a tobacco-like smoke flavour.

The protein in the preferred smoking mixtures of the invention is desirably fat-free in the commercial sense, that is to say any residual fat should preferably have been removed from the protein, for example by extraction with a commercial solvent. It is not, however, necessary for the protein to be completely free of fat in an analytical sense, and the expression fat-free refers to proteins of such purity as to be acceptable commercially under this designation.

The preferred proteins are casein, soyabean protein or zein but other proteins can be used, for example other animal proteins e.g. albumin, gelatin, peptone, haemoglobin or wool protein, or vegetable proteins e.g. proteins from wheat (glutin and gliadin) or groundnut. Partial hydrolysis products from protein are also suitable, for example the peptide-containing products known as protein acid hydrolysates and protein enzyme hydrolysates, particularly casein acid hydrolysate and casein enzyme hydrolysate.

The smoking mixture of the invention is preferably in a fabricated form simulating tobacco or in a form from which tobacco-simulating material can be produced. Conveniently the smoking mixture may be in sheet form. Known techniques of fabrication may be used. Thus if the modified carbohydrate is already in sheet form it may be convenient merely to treat the sheet so as to introduce the other ingredients, particularly the nicotine and the alkyl or hydroxyalkyl carboxylic acids. These may for example be applied to the sheet from a solution, by spraying or by means of printers rollers. (Application No. 48573/71). Alternatively when the modified carbohydrate is in powder form all the ingredients of the smoking mixture may be mixed with water to form a slurry which can then be spread on to a flat surface and dried to form a film.

The smoking mixtures may if desired be blended with tobacco, particularly flue-cured Virginia tobacco, and

blends so produced form a further feature of the invention. Because the smoking mixtures contain nicotine together with an effective combination of flavourants they may be blended in high proportions with tobacco, particularly flue-cured Virginia tobacco, to produce blends which are acceptable to the smoker in all applications where the tobacco itself would normally be used, e.g. as fillings for cigarettes, cigarillos, cigars or pipes. The blending of high proportions of the smoking mixtures with flue-cured Virginia tobacco, for example to give blends containing from 30 to 70% by weight of the said smoking mixtures, does not materially disturb the flavour of the tobacco.

The invention is illustrated but not limited by the following Examples in which the parts and percentages are by weight.

EXAMPLE 1 98 parts of a material prepared by heat treating acellulose in the presence of ammonium sulphamate was mixed with 1600 parts of water and ground in a disintegrator, 22.0 parts of glycerol followed by 12.0 parts of lactic acid in 200 parts of water aere added to the mixture. A dry mixture consisting of 58.8 parts of calcium carbonate, 6.0 parts casein, 18.4 parts of bentonite and 8.0 parts of ammonium sulphate was then added followed by 54.4 parts of sodium carboxymethylcellulose, and 104.4 parts of magnesite. The resultant slurry was stirred for one hour and then cast on a drier to give a film with a dry basic weight of 48-52 gm/sq.metre.

The film was shredded and 300 parts of the shred sprayed with 0.03 parts of isovaleric acid and 0.06 parts of B-methyl valeric acid in 300 parts of ether. Thus the shred contained 0.03% by weight of the flavourant acids. The shred was then blended with equal parts of flue-cured (FCV) tobacco and made into cigarettes. These cigarettes were flavour assessed by a statistically designed Preference Test procedure on two separate occasions against an otherwise identical 50:50 blend containing no casein, isovaleric or B-methyl valeric acid. The flavoured cigarette was preferred with 90 and 79% confidence.

EXAMPLE 2 1130 parts of a material prepared by heat treating a-cellulose in the presence of ammonium sulphamate was mixed with 16160 parts of water and ground in a disintegrator. 254.1 parts of glycerol followed by 204.2 parts of lactic acid, 1362 parts of nicotine, 0.7 part of isovaleric acid and 1.3 parts of B-methyl valeric acid in 3000 parts of water were added to the mixture. A dry mixture consisting of 680.7 parts of calcium carbonate, 213 parts of bentonite and 90.8 parts of ammonium sulphate was then added followed by 6262 parts of sodium carboxymethyl cellulose and 1202.5 parts of magnesite. The resultant slurry was stirred for 1 hour and then cast on a drier to give film with a dry basis weight of 48-52 grams per sq.metre. This film contained 0.04% of the flavourant acids.

The film was shredded and blended with an equal part of flue-cured (FCV) tobacco and made into cigarettes.

These cigarettes were flavour assessed by a statistically designed Preference Test procedure on two separate occasions against an otherwise identical 50/50 blend containing no isovaleric or B-methyl valeric acid. The flavoured cigarette was preferred on both occasions with greater than 99% confidence.

EXAMPLE 3 1061.9 parts of the material prepared by heat treating a-cellulose in the presence of ammonium sulphamate was mixed with 16160 parts of water and ground in a disintegrator. 254.1 parts of glycerol followed by 204.2 parts of lactic acid, 136.2 parts of nicotine, 0.7 parts of isovaleric acid and 1.3 parts of B-methyl valeric acid in 3000 parts of water were added to the mixture. A dry mixture consisting of 680.7 parts of calcium carbonate, 213 parts of bentonite, 68.1 parts of casein and 90.8 parts of ammonium sulphate was then added followed by 626.2 parts of sodium carboxymethyl cellulose and 1202.5 parts of magnesite. The resultant slurry was stirred for 1 hour and then cast on a drier to give a film with a dry basis weight of 48-52 grams per sq.metre.

The film was shredded and blended with an equal part of flue-cured '(FCV) tobacco and made into cigarettes. These cigarettes were flavour assessed by a statistically designed Preference Test procedure against an otherwise identical 50/50 blend containing no casein, isovaleric acid or B-methyl valeric acid. The flavoured cigarette was preferred with greater than 99% confidence.

EXAMPLE 4 Example 2 was repeated, using 0.35 parts of isovaleric acid and 0.65 parts of B-methyl valeric acid, thus producing a'film containing 0.02% of the flavourant acids instead of 0.04%.

The film was shredded and blended with an equal part of flue-cured (FCV) tobacco and made into cigarettes. These cigarettes were flavour assessed by statistically designed Preference Test procedure against an otherwise identical 50/50 blend containing no isovaleric or ,B-methyl valeric acid. The flavoured cigarette was preferred with greater than confidence.

EXAMPLE 5 25.5 parts of a material prepared by heat treating a-cellulose in the presence of ammonium sulphamate was mixed with 300 parts of water and ground in a disintegrator. 5.7 parts of glycerol, 2 parts of nicotine, 3 parts of lactic acid and 0.03 parts of isovaleric acid in parts of water were added to the mixture. A dry mixture consisting of 15.7 parts of calcium carbonate,

4.7 parts of bentonite and 1.9 parts of ammonium sulphate was then added followed by 14.2 parts of sodium carboxymethyl cellulose and 27.2 parts of magnesite. The resultant slurry was stirred for 1 hour then cast on a drier to give a film with a dry basis weight of 48-52 gm per sq.metre.

The film was shredded and blended with an equal part of flue cured tobacco and made into cigarettes. These cigarettes were flavour assessed against an otherwise identical 50/50 blend containing no isovaleric acid. The flavoured cigarette waspreferred, showing an improvement in flue-cured character.

EXAMPLE 6 25.5 parts of a material prepared by.heat treating a-cellulose in the presence of ammonium sulphamate was mixed with 300 parts of water and ground in a disintegrator. 5.7 parts of glycerol, 2-parts of nicotine, 3 parts of lactic acid and'0.03 partsof B-methyl valeric acid in 150 parts of water were added to the mixture. A dry mixture consisting of 15.7; parts of calcium carbonate, 4.7 parts of bentonite and 1.9 parts of ammonium v sulphate was; then added followed by 14.2 parts of sodium carboxymethyl cellulose and 27.2 parts of magnesite. The resultant slurry was stirred for-1 hour then cast on a drier to give a film with a dry basis weight of 48-52 gm. per sq.metre.

The film was shredded and blended with an equal part of flue-cured tobacco and made into cigarettes. These cigarettes were flavour assessed against an otherwise identical 50/50 blend containing no B-methyl valeric acid. The flavoured cigarette was preferred showing an improvement in flue-cured character.

EXAMPLE 7 25.5 parts of a material prepared by heat treating a-cellulose in the presence of ammonium sulphamate was mixed with 300 parts of water and ground in a disintegrator. 5.7 parts of glycerol, 2.0 parts of nicotine, 3.0 parts of lactic acid, 0.01 parts of isovaleric acid and 0.04 parts of B-methyl valeric acid in 150 parts of water were added to the mixture. A dry mixture consisting of 15.7 parts of calcium carbonate, 4.7 parts of bentonite and 1.9 parts of ammonium sulphate was then added followed by 14.2 parts of sodium carboxymethyl cellulose and 27.2 parts of magnesite. The resultant slurry was stirred for I hour then cast on a drier to give a film with a dry basis weight of 48-52 gm per sq.metre.

The film was shredded and blended with an equal part of flue-cured tobacco and made into cigarettes. These cigarettes were flavour assessed against an otherwise identical 50/50 blend containing no isovaleric acid or fl-methyl valeric acid. The flavoured cigarette was preferred, showing an improvement in flue-cured character.

EXAMPLE 8 25.5 parts of a material prepared by heat treating a-cellulose in the presence of ammonium sulphamatea was mixed with 300 parts of water and ground in a disintegrator. 5.7 parts of glycerol, 2.0 parts of nicotine, 3.0 parts of lactic acid, 0.02 parts of isovaleric acid and 0.005 parts of B-methyl valeric acid in 150 parts of water were added to the mixture. A dry mixture consisting of 15.7 parts of calcium carbonate, 4.7 parts of bentonite and 1.9 parts of ammonium sulphate was then added followed by 14.2 parts of sodium carboxymethyl cellulose and 27.2 parts of magnesite. The resultant slurry was stirred for 1 hour then cast on a drier to give a film with a dry basis weight of 48-52 gm per sq.metre.

The film was shredded and blended with an equal part of flue-cured tobacco and made into cigarettes. These cigarettes were flavour assessed against an otherwise identical 50/50 blend containing no isovaleric acid or fl-methyl valeric acid.'The flavoured cigarette was preferred, showing an improvement in flue-cured character.

EXAMPLE 9 25.0 parts of a material prepared by heat treating a-cellulose in the presence of ammonium sulphamate was mixed with 300 parts of water and ground in a disintegrator. 5.6 parts of glycerol, 2 parts of nicotine, 3 parts of lactic acid, 0.01 parts of isovaleric acid and 0.02 parts of B-methyl valeric acid in parts of water were' added to the mixture. A dry mixture consisting of 15.4 parts of calcium carbonate, 4.6 parts of bentonite, 2.0 parts of soya protein and 1.9 parts of ammonium sulphate was then added followed by 13.8 parts of sodium carboxymethyl cellulose and 26.7 parts of magnesite. The resultant slurry was stirred for 1 hour then cast on a drier to give a film with a dry basis weight of 48-52 gm per sq.metre.

The film was shredded and blended with an equal part of flue-cured tobacco and made into cigarettes. These cigarettes were flavour assessed against an otherwise identical 50/50 blend containing no soya protein, isovaleric acid or B-me thyl valeric acid. The flavoured cigarette was preferred, showing an improvement in flue-cured character.

- EXAMPLE 10 25.5 parts of a material prepared by heat treating a-cellulose in the presence of ammonium sulphamate was mixed with 300 parts of water and ground in a disintegrator. 5.7 parts of glycerol, 2 parts of nicotine, 3 parts of lactic acid and 0.3 parts of butyric acid in 150 parts of water were added to the mixture. A dry mixture consisting of 15.7 parts of calcium carbonate, 4.7 parts of bentonite and 1.9 parts of ammonium sulphate was then added followed by 14.2 parts of sodium carboxymethyl cellulose and 27.2 parts of magnesite. The resultant slurry was stirred for 1 hour then cast on a drier to give a film with a dry basis weight of 48-52 gm per sq.metre.

The film was shredded and blended with an equal part of flue-cured tobacco and made into cigarettes. These cigarettes were flavour assessed against an otherwise identical 50/50 blend containing no butyric acid. The flavoured cigarette was preferred, showing an improvement in flue-cured character.

EXAMPLE 11 25.5 parts of a material prepared by heat treating a-cellulose in the presence of ammonium sulphamate was mixed with 300 parts of water and ground in a disintegrator. 5.6 parts of glycerol, 2 parts of nicotine, 3 parts of lactic acid, 0.0] parts of isovaleric acid and 0.02 parts of B-methyl valeric acid in 150 parts of water were added to the mixture. A dry mixture consisting of 15.4 parts of calcium carbonate, 4.6 parts of bentonite, 2.0 parts of zein protein and 1.9 parts of ammonium sulphate was then added followed by 13.8 parts of sodium carboxymethyl cellulose and 26.7 parts of magnesite. The resultant slurry was stirred for 1 hour then 1 cast on a drier to give a film with a dry basis weight of cured character.

EXAMPLE l2 25.0 parts of oxidised cellulose (the commercially available product Oxycel) was mixed with 300 parts of water and ground in a disintegrator. 5.6 parts of glycerol, 2.0 parts of nicotine, 3 parts of lactic acid, 0.01 parts of isovaleric acid and 0.02 parts of B-methyl valeric acid in 150 parts of water were added to the mixture. A dry mixture consisting of 15.4 parts of calcium carbonate, 4.6 parts of bentonite, 2.0 parts of casein and 1.9 parts of ammonium sulphate was then added followed by 13.8 parts of sodium carboxymethyl cellulose and 26.7 parts of magnesitesThe resultant slurry was stirred for 1 hour then cast on a drier to give a film with a dry basis weight of 48-52 gm per sq.meter.

The film was shredded and blended with an equal part of flue-cured tobacco and made into cigarettes. These cigarettes were flavour assessed against an otherwise identical 50/50 blend containing no casein, isovaleric acid or B-methyl valeric acid. The flavoured cigarette wasp'referred, showing an improvement in fluecured character.

We claim: I

l. A smoking blend characterized generally by the flavour of flue-cured Virginia tobacco, said blend comprising a mixture of a modified carbohydrate as smokeproducing fuel, nicotine, and as a flavourant, a member 8 of the group consisting the said acids, the modified carbohydrate comprising a thermally degraded carbohydrate prepared by subjecting the carbohydrate to catalyzed degradationxat a temperature of at least- 100C untilthe weight of degraded material is less'than of the dry weight of the original carbohydrate and the proportion of flavourant acids, comprising from 0.02% to 0.2 by weight,

of the smoking mixture; said mixture being blended with from 30-70% by weight thereof, flue-cured Virginia tobacco. i

2. A smoking blend according to claim 1 whereinthe modified carbohydrate is thermally degraded cellulose.

proteinis casein, ,soya bean protein .or zein.

of I isovaleric acid, B-methyl valeric acid, butyric acid and mixtures of at least two of I B-methyl vale-

Claims

1. A SMOKING BLEND CHARACTERIZED GENERALLY BY THE FLAVOUR OF FLUE-CURED VIRGINIA TOBACCO, SAID BLEND COMPRISING A MIXTURE OF A MODIFIED CARBOHYDRATE AS SMOKE-PRODUCING FUEL, NICOTINE, AND AS A FLAVOURANT, A MEMBER OF THE GROUP CONSISTING OF ISOVALERIC ACID, B-METHYL VALERIC ACID, BUTYRIC ACID AND MIXTURES OF AT LEAST TWO OF THE SAID ACIDS, THE MODIFIED CARBOHYDROATE COMPRISING A THERMALLY DEGRADED CARBOHYDRATE PREPARED BY SUBJECTING THE CARBOHYDRATE TO CATALYZED DEGRADATION AT A TEMPERATURE OF AT LEAST 100*C UNTIL THE WEIGHT OF DEGRADED MATERIAL IS LESS THAN 90% OF THE DRY WEIGHT OF THE ORIGINAL CARBOHYDRATE AND THE PROPORTION OF FLAVOURANT ACIDS, COMPRISING FROM 0.02% TO 0.2% BY WEIGHT, OF THE SMOKING MIXTURE; SAID MIXTURE BEING BLENDED WITH FROM 30-70% BY WEIGHT THEREOF, FLUE-CURED VIRGINIA TOBACCO.

2. A smoking blend according to claim 1 wherein the modified carbohydrate is thermally degraded cellulose.

3. A smoking blend according to claim 1 wherein the flavourant is a mixture of isovaleric and Beta -methyl valeric acids.

4. A smoking blend according to claim 3 wherein the ratio by weight of isovaleric to Beta -methyl valeric acids is from 4:1 to 0.25:1.

5. A smoking blend according to claim 1 containing protein as a flavourant.

6. A smoking blend according to claim 5 wherein the protein is fat free.

7. A smoking blend according to claim 5 wherein the protein is casein, soya bean protein or zein.