CN103347408A

CN103347408A - Smoking articles

Info

Publication number: CN103347408A
Application number: CN2012800092089A
Authority: CN
Inventors: D.迪特里希; P.布兰顿; M.贝万
Original assignee: British American Tobacco Co Ltd
Current assignee: British American Tobacco Investments Ltd
Priority date: 2011-02-17
Filing date: 2012-02-16
Publication date: 2013-10-09
Also published as: EP2675302A1; BR112013020509A2; NZ612998A; JP3201449U; KR20140004754A; US20140020699A1; WO2012110819A1; CA2824731C; MX2013009504A; RU2013142175A; AR085295A1; TW201247115A; JP2014506470A; AU2012219223A1; CL2013002357A1; AU2012219223B2; CA2824731A1

Abstract

A smoking article comprising at least two of: (a) a tobacco blend comprising one or more tobaccos or tobacco grades with low TSNA and/or metal content; (b) a tobacco blend that has been treated to remove polyphenols and/or peptides; (c) a tobacco substitute sheet comprising a non-combustible inorganic filler, a binder and an aerosol generating means; (d) a high activity carbon comprising a polymer-derived carbon material; and (e) an amine-functionalised chelating resin.

Description

Tobacco product

Technical field

The present invention relates to tobacco product, relate to such tobacco product particularly, it combines two or more technology that can reduce special component in the mainstream smoke separately or become the machine of grouping to measure productive rate and uses.

Background of invention

Tobacco smoke is a kind of complexity, greater than 5000 kinds of dynamic mixtures of having determined compositions, wherein about 150 kinds have been recited as by document and do not make us expecting.This composition is present in the mainstream smoke (MS) that is sucked by the smoker, and also discharges between cigarette flatly as the composition of sidestream smoke (SS).

Reported at calendar year 2001 Institute of Medicine (IOM), because the disease that smoking is relevant is relevant with dosage, with because epidemiological study shows in the risk of stopping inhaling back smoking relevant disease to be reduced, therefore may reduce the smoking relevant risk by the product (PREP) of the potential exposure minimizing of exploitation.They are defined as: (1) causes the obviously product that is exposed to one or more tobacco poisonous substances of minimizing; (2) if the low-risk of begging to surrender, then be reasonably to expect the product that reduces one or more specified diseases or other disadvantageous health effects people such as (, 2001) Stratton.Up to now, also do not have flammable tobacco product to show and satisfy this general requirement that IOM proposes.

IOM and its hetero-organization (Life Sciences Research Office (LSRO) 2007; The World Health Organization (WHO) 2007) described many active stages, the tobacco product that it is flammable be considered to PREP may require; But, provide the required detailed protocol of related data and stage still not to reach an agreement in scientific circles.For example, some organize the MS productive rate restriction that has proposed specific smog composition, and its hetero-organization suggestion biological monitoring should play a role in this evaluation.

Carry out many research in recent years and reduced specific MS composition.Scheme is at the different piece of tobacco product.For example attempted by genetic engineering or by mix specific tobacco reduce parent material some compound level or remove them.Tobacco is handled and once attempted to reduce or remove compound before being blended into tobacco product from tobacco-containing material.Dissimilar diluents or filler have been attempted using, the different modes of the tobacco in the pipe tobacco post of next " dilution " tobacco product.Other schemes comprise the ventilation of tobacco product, wherein will dilute MS in the surrounding air suction tobacco product.Filtering is another field obviously, has wherein carried out a large amount of work and has come to strengthen the rate of removing of MS composition when the MS composition passes the filter tip section of tobacco product.All these single means all are useful, but they have mostly just solved the sub-fraction problem.

Another problem to be solved is the importance of producing the product of accepting for the consumer.A lot of organoleptic effects of conventional smoke goods are based on the composition of MS.The potential possibility that provides unsatisfied smoking to experience for the smoker is provided some of removing in them.

So a challenge provides the tobacco product of the obvious reduction that shows all MS composition dischargings that are considered to not expect.But the single means that reduce some composition often cause other compositions not reduce and in some cases, even cause the increase of the level of other compositions.

Comprehensive reduction of the poisonous substance productive rate that smoking machine is measured can be diluted smog by the cigarette paper that uses filter tip ventilation or use high permeability and be realized, with under the situation of the poisonous substance mutually relevant with the particle of smog, realize by improving filter-tip filter efficiency.For many years, the different local governments in the whole world and publilc health department think that the cigarette that produces lower ISO tar is to reduce not a kind of approach of those smokers' of smoking cessation smoking health risk.But this product change scheme is endured to the fullest extent recently and is censured.Tobacco product regulations (TobReg) research group of the World Health Organization has proposed a kind of Managed Solution recently, and it will limit the productive rate of selected group specific smog composition.This research group is also recommended should be based on measured with strong smoking machine mode and limit their productive rate based on the productive rate of every milligram of determined composition of nicotine.

The scheme that the tar of measuring with respect to machine and nicotine productive rate selectively reduce specific smog composition depends on the physicochemical property of this single composition very much.Conventional design of cigarettes parameter is being limited in scope that the relative reduction of smog composition provides.For example by improving the conventional filter-tip filter efficiency of cellulose acetate (CA), the particle phase constituent reduces with tar and nicotine, and selective the reduction seldom or not taken place.And because the cellulose acetate filter tip does not almost have for volatile ingredient or not effect, therefore improving filter efficiency has increased their productive rate with respect to the ratio of tar and nicotine.

Improve the filter tip ventilation and have different effects for the smog composition.All the absolute yield of smog composition reduces, but with respect to tar or nicotine, the productive rate of most of particle phase constituent does not become or even can improve.The productive rate of some volatile ingredients such as ammonia and carbon monoxide is with respect to tar and the two reduction of nicotine, and the relative productive rate of some semi-volatility components such as phenol increases.

Many volatility gaseous components such as volatile aldehyde and hydrogen cyanide can use sorbent material such as activated carbon or some resin selectively to reduce in filter tip.But permanent gases such as carbon monoxide and nitric oxide do not adsorb in room temperature, and the poisonous substance of particle in mutually can not be by filtering and selective the reduction, because they mainly are attached in the aerosol particle.

Since nineteen fifties, attempted from smoke from cigarette, selectively removing or reducing composition.Adsorbing by porous adsorbent is a kind of possible means of removing some volatile ingredients from smog.Activated carbon (AC) is a kind of non-selective adsorbent, and it is widely used in the cigarette filter, and can significantly reduce the volatility smog composition of wide region via physical absorption.But, should not underestimate the difficulty of this challenge.Use the smoke from cigarette adsorbent, need be in conditions of high flow rate (for typical machine smoking condition, being about 1 L/mm) operation down, so between smog composition and filter tip adsorbent, exist very short time of contact (Millisecond).Adsorbent also need gas-solid interface (that is, not being in solution) with in the presence of thousands of kinds of gas phases and particle other chemicals mutually, work.The smog aerosol particle that adsorbent surface also is easy to be condensed stops up.Have been found that for permanent gases and environment temperature has the smog composition of high vapour pressure such as formaldehyde, acetaldehyde or HCN physical absorption be not too effective, need the route that substitutes.

Smoke from cigarette comprises many volatile aldehydes, existing saturated compounds such as formaldehyde, and acetaldehyde, propionic aldehyde and butyraldehyde have unsaturated compound such as methacrylaldehyde and crotonaldehyde again.Carbonyl in the smoke from cigarette is mainly produced by many tobacco components (major part is carbohydrate) burning.Particularly, carbohydrate is considered to the main source of formaldehyde in the smoke from cigarette.It is the main precursor of mainstream smoke acetaldehyde that cellulose is shown.Some data show that glycerine (a kind of sometimes as the material in the NMF adding tobacco-containing material) is another precursor of methacrylaldehyde.Though the boiling point of formaldehyde is lower than environment, leave in the mainstream smoke of cigarette with filter tip 30% formaldehyde be retained in particle mutually in and can not be used for the selective filter of room temperature thus.Because the formaldehyde in the existence of water vapour, smoke particle mutually is the form A H as hydration ₂(OH) ₂And exist.Acetaldehyde (one of composition of maximum output in the smoke from cigarette) the boiling point of its environment temperature or about exist, and therefore have very high steam pressure.The combination of these two kinds of factors makes that removing most acetaldehyde by additive for filter tip from smog stream becomes a very big challenge.

Realization is to change tobacco from a kind of promising scheme of the obvious specific reduction of the particulate composition of the cigarette of conventional structure.Substituting different tobacco varieties can exert an influence to the productive rate of several smog compositions in mixture.For example be higher than from flue-cured tobacco or east tobacco from the productive rate of the nitrogenous smog composition of uncle Lay taro leaf (burley) tobacco, and the productive rate of the formaldehyde of flue-cured tobacco and catechol is higher.But a kind of composition or is formed the reduction that divides and is often offset by the rising of other compositions.For fear of this, usefully can from tobacco leaf, differentiate and remove the precursor of smog composition.

Except metal ingredient (chromium, nickel, arsenic, selenium, cadmium, mercury and lead) and the distinctive nitrosamine of some tobaccos (TSNA) (it directly shifts from tobacco leaf), as NAT and NAB,, most smog composition generates by high temperature and is formed by the leaf component.Therefore, the main precursor of volatile carbonyl thing, benzo (a) pyrene, carbon monoxide, benzene and toluene is for example colloid and cellulose and sugar of structural carbohydrate.Nitrogenous smog composition is to be formed by the nitrogen precursor that contains in the leaf, and Health Canada listOn have a large amount of evidences to show that the burning of protein and amino acid has caused producing several nitrogenous smog compositions.Protein and amino acid it is reported it is the precursor of hydrogen cyanide, pyridine and quinoline, 2-ammonia naphthalene and 4-aminobphenyl.Protein tobacco also with the formation of the heterocyclic amine of induced mutation and in TA98 Ames detects the mutagenicity of formed smog condensate obviously relevant.

Polyphenol in the tobacco is the main precursor of phenol aerosolization compound.Chlorogenic acid (in the flue-cured tobacco the abundantest polyphenol) is the main precursor of phenol, catechol and alternative catechol, and has reported that hydroquinones is the chlorogenic acid thermal decomposition product.Rutin sophorin and caffeic acid have also produced the catechol of catechol and replacement by pyrolysis, but because their low concentration and because their lower pyrolysis productive rates in tobacco, the catechol that they form in flue-cured tobacco smog is far fewer than chlorogenic acid.Resorcinol is known to be the primary product of rutin sophorin pyrolysis.

Describe in detail

The invention provides the combination of customized tobacco composition and customized absorbent filtering mouth additive, it has produced the tobacco product of the obvious reduction with the mainstream smoke composition that is considered to not expect.

More specifically, the invention provides a kind of tobacco product, comprise following at least two kinds:

(a) tobacco composition, it comprises one or more tobaccos with low TSNA and/or tenor or tobacco grade;

(b) tobacco composition, it has removed polyphenol and/or peptide (soluble and insoluble) through handling;

(c) tobacco substitute sheet, it comprises non-flammable inorganic filler, adhesive and aerogel generating agent (aerosol generating means);

(d) high-activity carbon, it comprises the material with carbon element in polymer source; With

(e) amine-functionalized chelating resin.

In a kind of embodiment preferred, tobacco product of the present invention has and has reduced at least 75% of mainstream smoke, and preferably at least 90% and more preferably all key components, as herein defined.

" key component " of so-called MS refer in the present invention in the literature by differentiate for be do not make us expecting (referring to for example The Scientific Basis of Tobacco Product Regulation:Report of a WHO Study Group (2007) WHO Technical Report Series 945, Geneva) and/or those smog compositions (referring to for example table 6,7 and 8) of analyzing in the data that here provide of its productive rate.

Described reduction preferably one of smoking machine condition of listing of use table 3 is determined.The productive rate of preferred this reduction is measured under Health Canada Intense smoking machine condition.

The reduction of key component productive rate preferably at least 5% or at least 10% or higher.

Preferably, when tobacco product of the present invention comprises under the tobacco composition situation of (it comprises one or more tobaccos with low TSNA and/or tenor or tobacco grade), they further comprise two or more listed in (b)-(e) other technologies.

Description of drawings

In order more fully to understand the present invention, its aspect and embodiment will be described with reference to the accompanying drawings, these only are non-limiting embodiment, wherein:

Fig. 1 has shown table 2, has showed the cigarette structure details.

Fig. 2 has shown table 4, has showed the main component productive rate of cigarettes tested when using different smoking machine conditions.

Fig. 3 has shown table 5, has showed hybrid metal and tobacco-distinctive content of nitrosamines.

Fig. 4 has shown table 6, has showed the metal measured under Health Canada Intense smoking machine condition and the MS productive rate of TSNA.

Fig. 5 A, 5B and 5C have shown table 7, have showed the MS productive rate of other smog compositions of measuring under Health Canada Intense smoking machine condition.

Fig. 6 has shown table 8, has showed the carbonyl compound in tester and three-stage filtration mouth EC measured under Health Canada Intense smoking machine condition and the MS productive rate of various volatility and vapor phase smog composition.

Fig. 7 has shown table 9, has showed the carbonyl compound in tester and double-filtration mouth EC measured under Health Canada Intense smoking machine condition and the MS productive rate of various volatility and vapor phase smog composition.

Fig. 8 has shown table 10, has showed the sidestream smoke productive rate under ISO smoking machine condition.

Fig. 9 has shown from the HCI machine poisonous substance productive rate of EC (1mg ISO) and those comparison from disclosed data source.

Figure 10 has shown from the HCI machine poisonous substance productive rate of EC (6mg ISO) and those comparison from disclosed data source.

Figure 11 has shown the comparison of the total poisonous substance productive rate (TTY) between EC productive rate and the disclosed HCI productive rate data.

Figure 12 has shown the comparison of the gross production rate from child group poisonous substance (TSY) between EC productive rate and the disclosed HCI productive rate data.

Figure 13 has shown the comparison of the cumulative correction poisonous substance productive rate (NTT) between EC and the disclosed HCI productive rate data.

Figure 14 has shown the summary of the method for the carbon that the preparation highly reactive polymer is originated.

Figure 15 has shown table 15, has showed with contrast cigarette and has compared the smog of test products and the variation of biomarker.

Figure 16 has shown in vivo research and design.

Figure 17 and 18 has shown in vivo result of study.

Figure 19 has shown the tobacco product design according to a kind of embodiment of the present invention.

With two kinds low poisonous substance tobacco compositions (being characterised in that tobacco substitute sheet (TSS) or tobacco composition processing (BT)) and the filter tip combination that contains amine-functionalized resin material (CR20L) and/or high-activity carbon adsorbent (HAC), produce three kinds of experiment cigarettes (EC).The mainstream smoke of smog composition (MS) productive rate is to determine under four kinds of different smoking machine conditions.For the nicotine free dry particulate matter with for most of smog composition of measuring, Health Canada Intense (HCI) machine smoking condition has produced the highest MS productive rate.Will from the composition productive rate of EC with from two kinds of commercially available relatively things ( Commercial comparator) (CC) those of public data of cigarette, three kinds of science contrast (SC) cigarettes and 120 kinds of commercial cigaretteses compare.Find that EC has produced some the minimum machine productive rates from the composition of cigarette, for it, has HCI smog chemistry; Therefore these contrasts have confirmed that comparing EC with commercial cigarettes has produced the MS machine composition productive rate that reduces.

Phase I in the cigarette base PREP design relates to the technology that exploitation reduces smog composition productive rate.To test cigarette (EC) and use these technology assemblings, use their composition productive rate of smoking machine assessment then; Shown that with relevant contrast with reference to the contrast of product design of cigarettes is in the effectiveness that produces the composition yield aspects that reduces.Those EC that are found to compare with the reference sample productive rate that the smoking machine that reduced the smog composition measures are known as " the machine productive rate prototype of reduction " (RMYP).

The inventor has described the single process program of the composition in the different reduction smoke from cigarettes, one of them relates to selects the tobacco composition component with the mixture of known precursors content that the smog composition of not expecting with reduction is provided, and wherein two have changed tobacco and also have two to change cigarette filter.Tobacco composition (TB), tobacco substitute sheet material (TSS) and tobacco composition are handled (BT) and have been reduced the generation of composition in the burning cigarette in the source.Two kinds of filter tip technology are removed volatile materials the smog stream of the carbon adsorbent (HAC) in amine-functionalized resin material (CR20L) and highly reactive polymer source after forming.These technology discuss (in 2.1 joints) below in more detail.

Tobacco composition

This relates to the precursor that option table reveals the smog composition of not expecting of low content, for example TSNA and metal, the tobacco composition component.For example the level of TSNA can be as the reduction of getting off: use specific (for example lighter) tobacco composition and select the tobacco plant part of protonitrate (a kind of precursor of TSNA).Those skilled in the art know and regulate blending technology in the mode of tobacco composition that the performance with these expectations is provided.

This tobacco composition can also comprise expanded tobacco, and it is pipe tobacco, has expanded to reduce the quality of the tobacco of burning in cigarette.This expanding method is similar to for generation of those of puffed rice snack.Used a kind of method is known as dry-ice expanding tobacco (DIET), and relates to before heating and soak into the tobacco leaf structure with liquid CO 2.Formed carbon dioxide forces expanding tobacco.Some have the commercially available tobacco brand of low ISO tar yield and used a certain proportion of expanding tobacco in whole mixtures.

Tobacco composition is handled

Here described the tobacco composition of handling, it is handled by such method, and this method makes it possible to remove deproteinize and polyphenol from tobacco, and smog poisonous substance productive rate is had useful effect.This tobacco is handled and carries out at the flue-cured tobacco silk, and comprises that water extracts tobacco, handles with aqueous solution of protease subsequently.With the sorbent treatment tobacco extract with after concentrating, DDGS is administered to again on the tobacco of extraction.The tobacco of this processing has kept the structure of initial tobacco, and uses conventional cigarette producing device to make cigarette, does not need to make again sheet material.

The tobacco substitute sheet

The another program that reduces smog poisonous substance productive rate is to dilute smog with glycerine, and has proposed to comprise in cigarette glycerinated " tobacco substitute " sheet up to 60%.Analysis to the mainstream smoke of such experiment cigarette shows that except some volatile materials, the productive rate of most of composition of measuring reduces.

Amine-functionalized resin material

Have been found that chemisorption can remove high volatile volatile aldehyde and HCN from the main flow smoke from cigarette.The cigarette filter additive is differentiated and be evaluated as to a kind of alkalescent macropore polystyrene resin (ps) with divinyl benzene crosslinked (having surperficial amine degree of functionality).This material (being made by Mitsubishi Chemical Corporation) normally is provided in the aqueous environment with the pearl form, and sells down at trade (brand) name Diaion CR20 (hereinafter being called CR20).The potentiality that this material provides from mainstream smoke nucleophilic to catch aldehyde, and because its alkalescent, it also can be used for removing HCN from MS.

This amine-functionalized chelating resin material can be incorporated in the filter tip of tobacco product, in chamber or disperse in (Dalmatia (dalmation) style) filtering material (for example cellulose acetate) in whole or one section filter tip.

High-activity carbon

The high activity material (Von Bhicher and the De Ruiter2004 that prepare the spheric granules of the carbon that comprises the polymer source by suitable method; People 2006 such as Von Blucher; Bohringer and Fichtner2008), and can be available from Blucher GmbH (Germany).Compare with the carbon in the coconut husk source that is generally used for present carbon cigarette with filter tip product, the material in this polymer source is being removed aspect the volatility smoke from cigarette poisonous substance normally about twice of efficient.The carbon in this polymer source all shows on ISO and HCI smoking state well, and has cigarette rule and littler girth.Also observe restriction removing under the high flow velocities smoking condition of acetaldehyde.

This high-activity carbon can be blended in the filter tip of tobacco product, in chamber or disperse in (Dalmatia's style) filtering material (for example cellulose acetate) in whole or one section filter tip.

The EC that the invention provides the described mixture of use and filter tip technical combinations and make.Whether the target of studying these EC is to estimate these technology can be combined in the prototype, compares with the commercially available prod, and described prototype has reduced the machine productive rate of poisonous substance, and has reduce the potentiality that the smoker is exposed to poisonous substance in people's smoking.

This EC of test under multiple smoking machine condition, and based on each cigarette with as the productive rate of analyzing the smog composition based on the ratio of every milligram nicotine productive rate, this makes it possible to compare with relevant commercially available relatively thing cigarette, and compares with the product of the wide region of bibliographical information.It is feasible that the result who presents in this work has confirmed to develop flammable RMYP.

2. material and method

2.1 the design of experiment, contrast and contrast device cigarette

This EC is that it develops to reduce smog poisonous substance or their precursors (table 1) in tobacco of particular chemical kind by the constituting of mixture and filter tip technology.For each EC, single tobacco grade and the mixing having selected to have low TSNA and tenor think that the experiment design of cigarettes provides low poisonous substance starting point.

Table 1. is used for the technology of structure experiment cigarette (EC).

Technology is used	The cigarette member	Explanation	Potential reduction
				Tobacco composition (TB)	Mixture	Option table reveals the tobacco composition component of the low precursor level of not expecting the smog composition	Some TSNA and metal
Tobacco substitute sheet (TSS)	Mixture	The tobacco substitute sheet, it has reduced tobacco combustible and the glycerine dilution that has produced smog	Whole smog
				Tobacco composition is handled (BT)	Mixture	The tobacco that Protease Treatment is crossed has reduced protein nitrogen and the polyphenol in the mixture	Nitrogen based component: arylamine, NAB, NAT, NNK, NNN; Phenol
Amine-functionalized resin bead (CR20L)	Filter tip	The amido functionalized resins that comprises in the filter tip level	HCN, HCHO, acetaldehyde and other carbonyl compounds
				High-activity carbon (HAC)	Filter tip	The spherical carbon pearl in the polymer source that comprises in the filter tip level	Gas phase composition

。

Tobacco composition is handled

Briefly, make this tobacco composition carry out moisture extraction step, make extract pass double-filtration subsequently and remove polyphenol and soluble peptide.With residual solid tobacco with Protease Treatment to remove insoluble protein.Clean and enzyme deactivation after, the water extract that contains of solid tobacco and filtration is reconfigured.This processing method has caused the reduction of the smog productive rate of phenol, arylamine, HCN and many other nitrogenous smog compositions; But, also exist the raising of formaldehyde and isoprene productive rate.

This tobacco-containing material to be extracted can be bar, silk, tobacco chopping or that grind.In a kind of embodiment preferred, this tobacco is the tobacco of chopping.But other forms of tobacco also can use method described herein to extract.

Tobacco-containing material can form slurry with the extraction solvent.This solvent can add in the tobacco-containing material with following weight ratio: 10:1 is to 50:1, preferably 20:1 to 40:1 and most preferably 25:1 to 30:1.In a kind of particularly preferred embodiment, solvent is to add tobacco-containing material with the weight ratio of 27:1.

This solvent can be organic solution, but the preferably aqueous solution or water.In extracting method at the beginning, this solvent is water normally, but it also can comprise alcohol, and as ethanol or methyl alcohol, perhaps it can comprise surfactant.Can also use other solvents, this depends on treats the concrete composition that extracts from tobacco.

This extraction can and preferably be carried out at 65 ℃ at 15-85 ℃.The preferred described slurry of continuous stirring in leaching process is so that tobacco keeps suspending.Extraction should be carried out 15 minutes to 2 hours.In a kind of embodiment preferred, extract and carried out about 20 minutes.

In leaching process, the solubility tobacco ingredient is removed from tobacco-containing material, and enters solution.They comprise nicotine, sugar, some protein, amino acid, colloid, polyphenol and flavouring agent.Initial tobacco weight up to about 55% may be dissolved.Importantly the colloid in the baccy fiber extract and processing method whole in maintenance crosslinked, with the fibre structure of maintenance tobacco.Therefore, can be to the solvent that is used for the extraction tobacco with to being used for adding calcium in any solution of downstream procedure.

After extraction, can discharge slurry and leach thing (" female filter liquor ") to collect liquid.Simultaneously, insoluble tobacco residue can further extract by the adverse current cleaning when it transmits, in order to soluble component as much as possible is removed from tobacco.

Fresh solvent can put on tobacco, and collects filter liquor (" cleaning filter liquor ").This cleaning filter liquor can recycle by put on the tobacco residue that enters that transmits at conveyer belt at the upstream point.Clean the collection of filter liquor and upstream and be applied to the tobacco residue that enters again and can repeat repeatedly, preferred three, four or even five times.Thus, the final cleaning filter liquor of collecting in the conveyer belt foremost can be the solubility tobacco component that those tobacco residues of enrichment are therefrom removed when filter length is transmitted.Final cleaning filter liquor can form the tobacco slurry by joining, prepare for extracting in the new tobacco, further recycle.For example final cleaning filter liquor can join in the tobacco mixing channel, forms the tobacco slurry here before extracting.Therefore this extracting method can be a kind of continuous method, and wherein new tobacco is to use the cleaning filter liquor of recirculation to extract.Only when this extracting method begins, extract tobacco with novel solvent.In case extracting method begins, in extraction, just do not re-use novel solvent, and solvent only is made of the cleaning filter liquor of recirculation.

Along with extracting method continues, the extract tobacco component of enrichment solubility more that becomes thus.These compositions are included in those (forming this mother's filter liquor) that enter solution in the extraction tank in the primary extraction process, and those (form and clean filter liquor) of entering solution in the secondary leaching process on level band filter.

Final filter liquor therefore comprise female filter liquor and clean filter liquor the two.Do like this, the tobacco residue that obtains after the filtration lacks those at the soluble composition of solvent that is used for extracting.Can when filtering end, push the tobacco of this extraction, therefrom to remove any excess liquid.Therefore the tobacco that derives from the extraction of level band filter is the form of dehydrated mat usually.

Final filter liquor (hereinafter being called tobacco extract) can process to remove those compositions of not expecting subsequently in final tobacco product.The composition of not expecting comprises protein, polypeptide, amino acid, polyphenol, nitrate, amine, nitrosamine and pigment compound.But the level of the composition that is considered to expect (as sugar and nicotine) can remain unaffected, so that the fragrance of the tobacco of extracting and smoking performance can be suitable with those of original material.

In a kind of embodiment preferred, handle this tobacco extract to remove deproteinize, polypeptide and/or amino acid.The protein of the height to 60% that comprises in the initial tobacco-containing material can use insoluble adsorbent (as hydroxyapatite) or fuller earth mineral (as attapulgite or bentonite) to remove.This tobacco extract is preferably handled with bentonite, therefrom to remove polypeptide.Bentonite can join in the extract with the amount of the 2-4% of the tobacco weight that accounts for initial extraction.Perhaps, this tobacco extract input can be contained in the groove of the slurry of bentonite in water.Suitable slurry is included in the about 7kg bentonite (amount hourly) in about 64 kg water, for example the 7.13 kg bentonites (amount hourly) in 64.18 kg water.In any case, should be the enough high protein content with obvious reduction tobacco extract of bentonite concentration, but not high to absorbing nicotine additionally from tobacco extract.Bentonite is handled also can remove pigment compound effectively from tobacco extract, if do not remove, it then tends to make the extract deepening after concentrating.When using enough bentonites to handle extract, the pigment compound amount of this reduction can cause the not product of excessive deepening of outward appearance.

After bentonite was handled, this tobacco extract can be by centrifugation and/or the described slurry of filtering and removing.This tobacco extract can be also, or alternatively, handled to remove polyphenol wherein.

Polyvinyl polypyrrole alkane ketone (PVPP) is a kind of insoluble adsorbent of polyphenol, and it is used for brewing industry traditionally and removes polyphenol in the beer.PPVP can be joined in the extract with the amount of the 5-10% of the tobacco weight of initial extraction.The PVPP of this amount can remove the polyphenol of 50-90% in the solution.Be used for it is believed that by the best pH that PVPP removes polyphenol from tobacco extract and be about 3.Therefore the adsorption efficiency of PVPP can improve by the pH that adds suitable acid (example hydrochloric acid) reduction extract.

Substitute as using PVPP to absorb a kind of of polyphenol, one or more enzymes can be added the polyphenol of degrading in the tobacco extract wherein.Suitable enzyme is laccase (urushiol oxidase).But, only the invention is not restricted to from tobacco the method except deproteinize and/or polyphenol.Can use alternative or extra enzyme, reagent or adsorbent to come from tobacco extract, to remove the tobacco component that other are not expected.The example of the other tobacco component of not expecting that can remove from extract comprises nitrate, amine and nitrosamine.

If plan from tobacco extract, to remove a plurality of compositions, then can the many grooves of arranged in series, each groove comprises different enzymes, reagent or adsorbent, removes the composition that does not make us expecting optionally to replenish.Perhaps, single groove can comprise plurality of enzymes, reagent or adsorbent, so that the composition of not expecting can be removed in single step.For example bentonite or PVPP holding tank can comprise one or more other enzymes, reagent or adsorbent, with not only from tobacco except deproteinize or phenol, but also remove one or more other compositions of not expecting.

Handling tobacco extract with after removing the selected composition of not expecting, preferably this extract is concentrated to the solid concentration of 20-50 weight %.It is high to 10% solid concentration to use counter-infiltration to realize most effectively.Can rely on falling film evaporator to realize to further concentrating of about 40% solid content.Can use other method for concentration, and will be well known by persons skilled in the art.The tobacco extract that should concentrate can reconfigure with the tobacco of extracting subsequently.

But the tobacco of having extracted in the aqueous solution as mentioned above is preferred further extracts, and with before reconfiguring with the tobacco extract that concentrates, removes one or more other compositions of not expecting.The enzyme that the further extraction of tobacco can use special selection to be used for removing selected composition carries out.In a kind of embodiment preferred, this enzyme is for the proteolytic enzyme that removes deproteinize from tobacco.This enzyme is bacterium or fungal enzyme preferably, and is more preferably commercial enzyme for food and detergent industry.This enzyme can be selected from Savinase, Neutrase, and Enzobake and Alcalase, it is all available from Novozymes A/S.This proteolytic enzyme preferably joins in the tobacco with the amount of the 0.1-5 weight % of tobacco-containing material.For example Savinase can join in the tobacco with the amount of about 1 weight %.This tobacco can slurrying again in selected enzyme solutions.In the slurry weight rate of water and tobacco should be 10:1 to 50:1, preferred 20:1 to 40:1 and most preferably 25:1 to 30:1.In a kind of particularly preferred embodiment, the weight ratio of water and tobacco is 27:1.

The pH of tobacco/enzymatic mixture should be the pH that promotes best enzymatic activity.Therefore, provable is that dehydration tobacco pad is supplied in the groove that pH wherein for example regulates by adding alkali (as NaOH) easily.The tobacco that this can have been regulated pH then supplies to enzyme and throws in the groove (dosing tank), to mix with selected enzyme.This tobacco/enzymatic mixture can feed in the plug flow reactor subsequently, carries out enzyme therein and extracts.This enzyme extracts and should carry out in the temperature that promotes best enzymatic activity.Preferably should adopt narrow temperature range, as 30-40 ℃, to avoid enzyme denaturation.When Savinase was selected enzyme, best operating condition was 57 ℃ and pH9-11.This enzyme extracts and should carry out at least 45 minutes; Any shorter duration it is believed that be not enough for proteolytic enzyme degrading tobacco protein.

Certainly, if from tobacco, remove a plurality of compositions, then can carry out a plurality of enzymes and extract.They can be connected and carry out or a plurality of enzyme can add in the tobacco in single treatment step.

Also possible is that enzyme is included in the extraction step that begins most in the processing method, but not constitutes independent extraction step subsequently.

After enzyme extracts, can preferably clean with sodium chloride solution with this insoluble tobacco residue of washed with saline solution, it is flushed to no enzyme.Salt flushing can with in succession, reflux type carries out.

But salt and water flushing may be not enough to remove enzymes all in the tobacco.After Yan Heshui flushing, also can handle the tobacco of this cleaning so that be retained in any residual enzyme deactivation in the tobacco.This can finish to being enough to make enzyme deactivation still not have too much tobacco to lose its fibers form by the steam treatment tobacco.In one embodiment, steam treatment was carried out 4 minutes at 98 ℃, but if desired, this time of staying can extend to about 10 minutes.Perhaps, can this tobacco of heat treatment make enzyme deactivation, for example by heating using microwave or bake tobacco and carry out.In another embodiment, can make enzyme deactivation by chemical modification; But, should take steps from tobacco, to remove this chemicals.

The tobacco of this processing can reconfigure with the tobacco extract that concentrates then.The extract of handling is added back to guaranteed the water dissolvable aroma constituent of tobacco and the reservation of nicotine in the final products in the tobacco of extracting.Reconfigured so produced such tobacco product, it has and the similar physical form of original material and outward appearance, taste and smoking performance, but has the content of protein, polyphenol or selected other compositions of obvious reduction.Reconfigure and to realize by tobacco extract is sprayed on the tobacco.The amount of the original extract of the tobacco reorganization for the treatment of and processing depends in the extraction processing removes the amount that loses in the selected composition process, and is different between dissimilar tobaccos.

Before reconfiguring with the tobacco extract of handling, among or afterwards, can come the dry tobacco that should handle with the standard drying means.The normally about 70-80% of the initial water capacity of the tobacco of handling.In a kind of embodiment preferred, dried water capacity should be about 14%.Can use the drying machine of heating, as band drier, the initial water capacity of tobacco is reduced to about 30%.Can use the drying machine of second heating then, as dried-air drier, come further water capacity to be reduced to about 14%.

Final dry products can be processed into final form subsequently, and as sheet, it can constitute all or part of cigarette filler after chopping.But, since extract and the processing method process in from wherein having removed up to the initial composition of 30% tobacco, compare with original material, in final products, based on the tobacco of Unit Weight, the raising of the concentration of all the other compositions.These compositions comprise cellulose, and when when burning, it can produce for example acetaldehyde and the formaldehyde in the smog of harmful volatile material with sugar and starch.

The tobacco substitute sheet

(TSS) incorporates the amount of tobacco that has reduced cigarette in the tobacco composition into the tobacco substitute sheet, reduced the whole potential of cigarette generation poisonous substance thus.This TSS also comprises glycerine, and when when heating, this TSS is discharged into glycerine in the smog stream, and the total amount of particle smog is had contribution, and it is that dry particulate matter (NFDPM is also referred to as " tar ") as nicotine-free is measured.Therefore because most of cigarette being designed satisfied specific NFDPM yield value, glycerine is blended into and causes the result of combustion of tobacco product to the contribution reduction of whole NFDPM value in the smog stream effectively: this method is known as " dilution ".TSS is blended into and causes widely the smog composition to reduce in the cigarette, comprise particle and gas phase poisonous substance the two.In vitro toxotest shows that reduction and their glycerol content of smoke particle activity are proportional.The human body of nicotine exposes according to filtration studies mensuration and has on average reduced by 18%, and the urine biomarker analysis of using 24 hours has reduced by 14%.Smoke particle exposes and has on average reduced by 29% in filtration studies, has reduced similar amount based on the concentration determination of urinating 4-(methyl nitroso)-1-(3-pyridine radicals)-1-butanols.These results show that it is possible using the tobacco substitute sheet to reduce to the exposure of some smog poisonous substances.

According to the present invention, can prepare tobacco product, it comprises the tobacco substitute sheet material that contains non-flammable inorganic filling material, alginic acid adhesive and aerogel generating agent.

Advantageously, this tobacco substitute sheet material comprises non-flammable inorganic filler, adhesive and the aerogel generating agent as its key component, and these three kinds of components preferably account at least 85 weight % of tobacco substitute sheet material together, preferably account for tobacco substitute sheet material weight greater than 90% and further more preferably altogether about 94% or bigger.These three kinds of components can or even the tobacco substitute sheet material 100%.All the other components preferably for example in colouring agent, fiber (as wood pulp) or the flavouring agent one or more.Other accessory constituent materials are well known by persons skilled in the art.Therefore this tobacco substitute sheet material is very simple sheet aspect its composition.

As what use herein, term " tobacco substitute sheet material " expression can be used in the material in the tobacco product.It not necessarily represent this material itself will be keep the burning necessary.This tobacco substitute sheet material is normally produced as sheet, chopping then.This tobacco substitute sheet material can mix to produce then and can burn and suck filler with other materials.

The present invention further provides tobacco product, it comprises the burnt and sucked packing material post of wrapping, this can burn and suck packing material and be made up of a kind of mixture, incorporated the tobacco substitute sheet material that comprises non-flammable inorganic filler, alginic acid adhesive and aerogel generating agent in this mixture into, the aerosol transfer efficiency ratio of this tobacco product is greater than 4.0.As what use herein, the aerosol transfer efficiency is recently to measure divided by the aerosol percentage that can burn and suck in the packing material as the aerosol percentage in the smog.Preferred this aerosol transfer efficiency is greater than 5, more preferably greater than 6.

Used burnt and sucked packing material can comprise the mixture that contains the tobacco substitute sheet material that is not more than 75 weight % in the tobacco product of the present invention.

The exist scope of preferred this inorganic filling material in final sheet material is 60-90% and more preferably greater than 70%.Advantageously, the amount of this inorganic filling material in final sheet material is about 74 weight %, but also can be in higher amount, for example is 80%, 85% or 90% weight of final sheet material.

This non-flammable filler advantageously comprises the material that a certain proportion of particle mean size is 500 μ m-75 μ m.The particle mean size of preferred this inorganic filler is 400 μ m-100 μ m and greater than 125 μ m, is preferably greater than 150 μ m.Advantageously, this particle mean size is about 170 μ m or 170 μ m, and can be 170 μ m-200 μ m.This granularity forms contrast with the granularity (that is the granularity of about 2-3 μ m) that conventional being used for substitutes the food-grade inorganic filling material of tobacco product.From each single inorganic filler, particle size range can be 1 μ m-1mm (1000 μ m).This inorganic filling material can grind, mills or be deposited to the granularity of expectation.

Advantageously, this inorganic filling material is following one or more: perlite, aluminium oxide, diatomite, calcium carbonate (chalk), vermiculite, magnesia, magnesium sulfate, zinc oxide, calcium sulfate (gypsum), iron oxide, float stone, titanium dioxide, calcium aluminate or other insoluble aluminates, or other inorganic filling materials.The density range of described material is 0.1-5.7g/cm suitably ³Advantageously, the density of this inorganic filling material is less than 3g/cm ³Preferably less than 2.5g/cm ³, be more preferably less than 2.0g/cm ³Further be more preferably less than 1.5g/cm ³Density is less than 1g/cm ³Inorganic filler make us expecting.More low-density inorganic filler has reduced the density of product, has therefore improved the ash content characteristic.

If use the combination of multiple inorganic filling material, then one or more filler can suitably be small grain size, and another kind of can be than coarsegrain, the ratio of each filler is suitable for realizing the particle mean size expected.The required static combustion rate of final tobacco product can use the suitable mixture of tobacco and tobacco substitute sheet material to realize can burning and sucking in the packing material.

Preferably, this inorganic filling material is not aggregate form.Before use, except possible size grading, this inorganic filling material should need preliminary treatment hardly.The scope that exists of preferred this adhesive is about 5-13%, is more preferably less than 10% and further be more preferably less than 8%, based on the weight of final packing material.Advantageously, this adhesive is about 7.5 weight % or lower of final sheet material.Advantageously, if adhesive is the mixture of alginates and non-alginate binder, then preferred this adhesive comprises at least 50% alginates, preferred at least 60% alginates and further more preferably at least 70% alginates.When using non-alginate binder, the amount of the adhesive of required combination can suitably reduce.The amount of alginates in binder combination advantageously along with the combination adhesive amount reduction and improve.Suitable alginate binder comprises the solubility alginates, for example ammonium alginate, mosanom, calcium sodium alginate, calcium alginate ammonium, potassium alginate, alginic acid magnesium, alginic acid three ethanol-amine and propylene glycol alginate.Other organic bonds such as cellulosic binders, natural gum or gel also can be used for making up with alginate binder.Suitable cellulosic binders comprises cellulose and cellulose derivative, for example sodium carboxymethylcellulose, methylcellulose, hydroxypropyl cellulose, hydroxyethylcellulose or cellulose ether.Suitable natural gum comprises gum arabic, and lid is carried natural gum (gum ghatti), bassora gum, karaya, locust bean, gum arabic, guar gum, warm cypress seed or xanthans.Suitable gel comprises agar, agarose, Irish moss, fucoidin (furoidan) and furcellaran.Starch also can be used as organic bond.Other suitable natural gum can reference manual Industrial Gums for example, E.Whistler (Academic Press) selects.Be the alginic acid adhesive as the major part of adhesive very preferably.Alginates are because the neutral taste characteristic in its when burning and be preferred in the present invention.

The scope that exists of preferred this aerogel generating agent is 5-20%, is more preferably less than 15%, further more preferably greater than 7% with further more preferably greater than 10%.Preferred this aerogel generating agent is less than 13%.Most preferably this aerosol agent propellant is 11%-13% and can be advantageously about 11.25% or 12.5%, based on the weight of final sheet material.Suitably, the amount of aerogel generating agent is to select in conjunction with this amount that comprises the tobacco-containing material in the mixture that can burn and suck filtering material that will be present in tobacco product.For example in the mixture of the tobacco-containing material that comprises a high proportion of sheet material and low ratio, this sheet material may need the aerogel generating agent of lower load level therein.Perhaps, in the mixture of the sheet material that comprises low ratio and a high proportion of tobacco-containing material, this sheet material can need the aerogel generating agent of higher load level therein.

Suitable aerogel generating agent comprises that being selected from following aerosol forms means: polyalcohol, and as glycerine, propane diols and triethylene glycol; The ester class, as triethyl citrate or glyceryl triacetate, high boiling hydrocarbon, or non-polyalcohol, as dihydroxylic alcohols, D-sorbite or lactic acid.Can use the combination of aerogel generating agent.

Another effect of aerogel generating agent is the described sheet material of plasticising.Suitable other plasticizer comprises water.This sheet material can suitably be inflated.The curtain coating slurry forms the sheet material with born of the same parents' cell structure thus.

Advantageously, this or a certain proportion of this aerogel generating agent can be encapsulated, preferred microencapsulation, or stable in certain other modes.Under such situation, the amount of aerogel generating agent can be higher than given scope.

Advantageously, this cigarette material comprises colouring agent and makes this material deepening and/or flavouring agent give special fragrance.Suitable fragrance or colorant materials (obedience local statues) can comprise for example cocoa power, Radix Glycyrrhizae, caramel, chocolate or taffy.Also can use tobacco fine lapping, granular or homogenizing.Also can use the food color of industry approval, El50a (caramel) for example, El51 (bright black BN), El53 (plant carbon) or El55 (brown HT).Suitable flavouring agent comprises for example menthol and vanillic aldehyde.Other packaging material ( Casing materials) also can be suitable.In replacement scheme, the existence of vermiculite or other inorganic filling materials can give the tobacco substitute sheet material darker color.The amount of preferred colouring agent is 0-10 weight % and can be up to 5-7 weight %, based on final tobacco substitute sheet material.Advantageously this colouring agent is less than 7%, preferably less than 6% be more preferably less than 5%, based on final tobacco substitute sheet material.It is most preferred that the consumption of colouring agent less than 4%, less than 3% with less than 2%.The scope that exists that cocoa power is suitable is 0-5%, and the scope that exists of Radix Glycyrrhizae can be 0-4%, based on the weight of final tobacco substitute sheet material.When this colouring agent for example was cocoa power or Radix Glycyrrhizae, the minimum of cocoa power that obtains the sheet color of expectation was about 3%, was about 2% for Radix Glycyrrhizae, based on the weight of final tobacco substitute sheet material.Similarly, the suitable scope that exists of caramel can be 0-5 weight %, preferably less than about 2 weight %, based on final tobacco substitute sheet material and more preferably about 1.5 weight %.Other suitable colouring agents comprise molasses, malt extract, coffee-extract, tea tree smectic thing, St.John's Bread, prune extract or tobacco extract.Also can use the mixture of colouring agent.

If local statues allow, then also can add taste and the fragrance characteristic that flavouring agent changes the tobacco substitute sheet material.Advantageously, if used food dye in replacement scheme, then its amount is 0.5 weight % or lower of final tobacco substitute sheet material.This colouring agent also can spread in described after the sheet manufacturing.

Can add fiber, as cellulose fibre, for example wood pulp, flax, hemp or bast come for this sheet material provides higher intensity, one or more in lower density or the higher filling value.Adding fashionablely, the amount of fiber can be the 0.5-10% of final sheet material, preferably less than 5% with further be more preferably less than about 3% weight.Advantageously, in sheet material (cellulosic or other), there is not fibrous material.

Advantageously, this tobacco substitute sheet material is the non-sheet that contains tobacco.Should be appreciated that the combustibility of mixture is poor when comprising high-caliber sheet material (for example greater than 75 weight % of mixture level) in the mixture.This can be for example be blended in the tobacco substitute sheet material by the granulated carbon with the low content of maximum 5-10% and overcomes.This carbon preferably is not the carbonaceous material of assembling, that is, this carbon is not pretreated by mixing to produce aggregation with another material.

Preferably this tobacco substitute sheet material is mixed to provide with tobacco-containing material and can burn and suck packing material.This tobacco-containing material component is high-quality leaf-level in the preferred mixture.Advantageously, most of this tobacco-containing material is pipe tobacco.This tobacco-containing material can comprise the expanding tobacco of the high-grade expanding method (for example DIET) of 20-100%.The filling capacity of such material is generally 6-9cc/g (referring to for example GB1484536 or US4340073).

Preferred this mixture comprises＜other blending ingredients except blade of 30%, and these other blending ingredients are stalk (WTS) or the stalk (STS) of steam treatment or tobaccos of reproducing of stem (CRS), water treatment.Preferred these other ingredients constitute tobacco-containing material final weights＜20%, more preferably＜10% and further more preferably＜5%.

Suitably, tobacco product of the present invention comprises the tobacco-containing material of handling with aerogel generating agent.This tobacco-containing material can be handled with aerogel generating agent, but the mixture of this not every tobacco-containing material and sheet material is all essential.

The amount that joins the aerogel generating agent in the tobacco is the 2-6 weight % of tobacco.After processing, the total amount of aerogel generating agent advantageously can burn and suck the 4-12 weight % of material in the mixture of tobacco-containing material and sheet material, preferably less than 10 weight % be preferably greater than weight 5%.

High-activity carbon

The high-activity carbon particle that is used for the polymer source of two-stage and three-stage filtration mouth has and is different from the commercial cigarettes pore structure on used carbon ground (it derives from coconut husk usually) usually.As a result, has excellent characterization of adsorption its volatility smog poisonous substance in certain limit.

The carbon in the polymer source of spheric granules shape is (Von Blucher and De Ruiter2004, people 2006 such as Von Blucher, Bohrmger and the Fichtner2008) by suitable method preparation, as shown in figure 14.The activated carbon in this polymer source is to use batch processes, with the revolving burner of indirect, produces under decompression in inert atmosphere.After having prepared the spherical polymer raw material, it is thermally-stabilised to use excessive oleum to carry out material.Subsequently, this material slowly is heated to 500 ℃, causes being mainly SO ₂And H ₂The release of O and the carbonization of polymer.Formed carbon has the initial apertures system, and it is untouchable for typical absorbate.In order to produce the porous system that can be used in absorption, this material further is heated to 900-1000 ℃, to activate with oxidant (steam).This has set up mainly by hole dimension is the pore system that the micropore of 0.7-3nm is formed.Use CO subsequently ₂Activation causes forming prevailing bigger mesoporous in the 3-80nm scope.In conjunction with steam and CO ₂Activation step provides the more flexible strategies that produces the pore property of expectation.

The carbon (it is synthetic material) in this polymer source have the much accurate spherical form that to limit, and have more uniform granularity.The material in this polymer source has lower density, and has lower content of ashes, and it has reflected and has compared the synthesising property of this polymer raw material as the natural coconut husk of the parent material that is used for carbonization method.

Compare with the coconut carbon of activation, the carbon that most of smog composition can be aggregated the thing source more effectively absorbs under the ISO condition, and observes the reduced rate of the 80-95% magnitude of the smog composition except formaldehyde, acetaldehyde, hydrogen cyanide (HCN) and toluene (50-60% reduced rate).Under the HCI condition, the cigarette with conventional coconut carbon provides the reduced rate of 25-45% magnitude for the most of smog compositions except acetaldehyde (16%).This cigarette that comprises the carbon in polymer source has been reduced 60-90% with the productive rate of the most of smog compositions except acetaldehyde and HCN (15-30%).

Amine-functionalized resin bead

DIAION CR20 is a kind of amine-functionalized resin bead of commercially available type, and it can be used among the present invention and (is made by Mitsubishi Chemical Corporation).It has the polyamines group as cheland, and it is bonded on the highly porous crosslinked polystyrene substrate.CR20 has shown the big affinity with transition metal ions.Definite type by the functionalized amido that produces can't accurately be controlled, and can have several different types on described resin.

When having been found that in being blended into cigarette, the CR20 of commercially available grade (hereinafter being called CR20C) has and the inconsistent characteristic odor of the acceptable smoke from cigarette character of the consumer of routine.But, by the improvement of Mitsubishi to synthesis condition, obviously reduced the intensity of this smell, produced the CR20 (hereinafter being called CR20L) of " low smell " level.In this article, unless indication is arranged in addition, all results that obtain refer to CR20L.This material has the bead size of 600mm, and density is 0.64g/cm ³, the water content of 15 weight % and 0.92meq/cm ³Total exchange capacity.

The CR20 of different other types is made by Mitsubishi Chemical Corporation, comprises CR20D and CR20HD.All ion exchange resin dissimilar or grade all are included among the term CR20 that herein uses.

Number of C R20 pearl provides in water, so that it is applicable in the cigarette filter applications that it may be essential removing at least some water.In one embodiment, except anhydrating, and described material is dried to about 15% or lower water capacity.In a kind of alternative embodiment, higher water capacity may be acceptable in smoking article filter.

CR20 (clearly comprising CR20L) can be blended in the cigarette filter.Compare with the filter tip that contains conventional carbon, CR20L provides the reduced rate of HCN, formaldehyde and acetaldehyde excellence.But carbon is more effective than CR20L remove other volatile ingredients from smog stream aspect.

Experiment cigarette

Use these technical construction target be to make that ISO NFDPM (tar) productive rate is 1 and the cigarette of 6mg.

Three kinds of science contrast cigarettes have also been made, in order to can estimate the filter tip technology for the contribution from the reduction of the smog composition of EC.Two kinds of commercially available relatively thing cigarettes: 1mg ISO design and 6mg ISO design also are used for these researchs.Carried out the contrast with commercially available brand, because need real contrast cigarette estimate the success that different smog composition reductions technology can be brought for (coherent) and the acceptable design of cigarettes of consumer of unanimity together.Equally, the use commercial cigarettes can check with respect to the cigarette of real world and the non-science tester, the degree that the composition that can realize reduces.At last, use is commercially available can mankind's exposure acceptable to sense organ and under real world uses carry out relevant contrast with reference to product.

These commercially available relatively produce product with take the lead brand in August, 2007 from the market of the 1mg of Germany and 6mg (ISO) and have similar machine smoking composition productive rate.Selection BAT group compares thing cigarette, but not the leading brand in actual market, purpose is can obtain about full detail and the permission of mixture and design of cigarettes feature human sense organ and exposure assessment to be carried out the product shielding.Therefore made two kinds of commercial cigarettes samples specially and be used for these researchs, and do not had trade mark or other signs, purpose is to support human smoking research.

2.2 test, compare the specification of thing and contrast cigarette

Used common trait in the design of EC: all be configured to identical basic size, be 84mm cigarette length (57mm pipe tobacco post adds the 27mm filter tip), 24.6mm girth, and filter tip is all based on cellulose acetate (CA) fiber with triethyl citrate plasticising.Differentiated the tobacco grade with low TSNA and tenor, and combination is used in the used tobacco composition of these prototypes.Prepared three kinds of different experiment cigarettes, gathered the design feature of three kinds of EC, and with table 2 (being presented among Fig. 1) in and the contrast cigarette that is described below and commercially available relatively thing compare.

Experiment cigarette BT1, combine Virginia and contain tobacco composition (the Virginia tobacco of 75.4% processing of the Virginia style of the tobacco that BT handled, with 4.3% east tobacco and 20.3% untreated Virginia tobacco), and contain CR20 level (to reduce formaldehyde, acetaldehyde and HCN productive rate) and contain the filter tip of the high-activity carbon filtration grade (to reduce the productive rate of isoprene and other volatile poisons) in polymer source.The target NFDPM productive rate of this cigarette is 1mg under ISO machine smoking condition.Experiment cigarette TSS1 also designs the NFDPM that produces 1mg under ISO smoking machine condition, and the mixture based on the US style, it contains TSS (mixture of a kind of Virginia, uncle Lay taro leaf and east tobacco, and comprise about 20% TSS and be used for the identical filter tip of experiment cigarette BT1).Experiment cigarette TSS6 has also used 20% TSS in a kind of mixture of different US style, and design comes to produce the NFDPM productive rate of 6mg under ISO machine smoking condition.A kind of different filter tips structure is used to this cigarette: a kind of two sections filter tips, it contains the high-activity carbon that is dispersed in the 80mg in the CA fiber adjacent with the pipe tobacco post, and at the mouth end CA section is arranged.

Commercially available relatively thing cigarette CC1 comprises the tobacco that US mixes style, comprises some Maryland tobaccos.Commercially available relatively thing cigarette CC6 also is a kind of typical US cigarette of mixing, but has the mixture that is different from CC1.The design feature that in table 2, has gathered three kinds of EC, and compare [being presented among Fig. 1] with contrast cigarette and commercially available relatively thing.Two kinds of commercially available relatively thing cigarettes have been used single-stage cellulose acetate filter tip.Three kinds " science contrast " (SC) cigarette has and relevant experiment cigarette BT1, TSS1 and TSS6 identical construction, and difference is that used filter tip is single-stage 27mm CA filter tip in each contrast cigarette, does not have other filter tip adsorbent medium.

Table 2 shows that the cigarette structure of BT1 and CC1 is very similar, has filter tip ventilation and the paper permeability of fine coupling.Fall at density of tobacco and filter tip pressure and to exist slight difference (resistance to suction or for the impedance of filter tip circulation), two parameters of BT1 all are higher than CC1.The cigarette structure of TSS1 and CC1 is very similar.Fall from the filter tip pressure of TSS1 and to be higher than commercially available tester, the two is all higher for CC1 but density of tobacco and filter tip pressure fall.For TSS6 and CC6, used than the filter tip ventilation still less of 1mg (ISO) product.Relatively two 6mg (ISO) product shows, TSS6 has high slightly density of tobacco, pressure drop values and low slightly filter tip ventilation.

2.3 smog chemical analysis

Before the smog chemical analysis, according to ISO3402,1999 explanation is regulated with cigarette.According to ISO4387,2000 (that is, and smoking 35ml in per 60 seconds, the duration is 2 seconds, is abbreviated as 35/2/60) and ISO3308,2000 (its exploitation is used for NFDPM and nicotine analysis) smoking condition of regulation is carried out routine chemical analysis.

About 150 kinds of smog compositions have been described to poisonous substance, and several administrative department has required the productive rate data of the child group (about 40 kinds) based on them.For in these poisonous substances some productive rate restriction (Burns has been proposed, D., Deng people (2008) Mandated Lowering of Toxicants in cigarette smoke:a description of the World Health Organization TobReg proposal. Tob. Control 17,132-141) and their biosurveillance scheme (Hecht, S.S. wait people (2010) Applying tobacco carcinogen and toxicants biomarker in product regulation and cancer prevention. Chem. Res. Toxicol. 23,1001-1008).Owing to these reasons with in order to characterize EC more accurately, measured the MS productive rate of the smog composition of expanded scope (47 kinds of analytes).Other about 100 kinds of poisonous substances that do not check in this work do not have to measure owing to lacking available effective analytical method.The yield value of benzo (a) pyrene is to come twice acquisition by direct measurement and as the part of a series of polycyclic aromatic hydrocarbons (PAH).

Need change to be used for measuring other analytes a little to ISO smoking parameter, and present method is available from BAT, (www.batscience.com/groupms/sites/BAT_7AWFH3.nsf/ vwPagesWebLive/DO7AXLPY opendocument﹠amp; SKN=1).Measurement does not have simulating human smoking productive rate from the productive rate of the smog composition of smoking machine, so all RTP are that different smoking machine in certain limit arranges test down, can assess machine productive rate performance under the possible smoking condition of wide region.The smoking condition of these changes is described in the table 3.

Table 3. smoking machine parameter.

Smoking is described	Abbreviation	Draw volume (ml)	The suction duration (s)	Suction is (s) at interval	Filter tip ventilation blocking rate (%)
						ISO3308/4387	ISO	35	2	60	0
Health Canada Intense	HCI		55	2	30							100
						Health Canada Intense-Filter Vents Open	HCI-VO	55	2	30	0
ISO WG9 Intense Option B	WG9B		60	2	30							50

。

Also as Health Canada, 1999 described sidestream smoke (SS) productive rates of having measured, but only produce under the parameter and at the smog composition of wide region more at ISO smog.The SS test is undertaken by Labstat International ULC.

2.4 statistical analysis

Between different cigarette types, the smog productive rate that used two tails (two-tailed), unpaired, student t test (t-test) statistical comparison, it carries out with Minitab v16.Demonstrate the significance level of P＜0.01 and P＜0.05,〉any P value of 0.05 shows as insignificant (NS).

For the single smog composition productive rate in the comparative studies, use Anderson Darling statistics, checked mean value (Health Canada, 2004 from the public data group; People such as Counts, 2005; Department of Health Australia, 2002) normal distribution.The percentage point that uses the experience cumulative distribution among the Minitab vl6 to analyze to calculate in the poisonous substance data distributes.

3. result and discussion

Carried out the test of EC by quantification MS composition and specific poisonous substance productive rate under many machine smoking conditions, with the actual performance from mixture and smog chemistry aspect inspection EC.

Also used ISO smoking curved measurement from the SS of EC discharging.This test be based on two kinds of commercial cigaretteses and three kinds of science contrast cigarettes to recently carrying out.At last, with previously disclosed from several national cigarettes the contrast of MS productive rate data and estimate the overall performance of EC as concrete poisonous substance productive rate and nicotine productive rate than the two.

3.1 mainstream smoke composition productive rate

Table 4 (being presented among Fig. 2) has shown under four kinds of smoking machine conditions, most of smog composition (NFDPM, nicotine and CO) and glycerol yield.The glycerine measured value is included in this table, and this is because it has been blended in the used tobacco substitute sheet of EC TSS1 and TSS6, dilutes smoke particle other smog compositions in mutually.

Table 4 shows that BT1 and CC1 MS NFDPM and nicotine productive rate under four kinds of smoking conditions mate well, but BT1 has the CO productive rate lower than CC1.TSS1 and CC1 NFDPM and nicotine productive rate under four kinds of smoking conditions mate well, but TSS1 has the CO productive rate lower than CC1.Higher glycerine productive rate from TSS1 is consistent with the desired dilution effect of the glycerol content of TSS.TSS6 and CC6 MS NFDPM and the nicotine productive rate under four kinds of smoking conditions mates well, but the CO productive rate of CC6 is higher and the glycerine productive rate of the TSS6 of expection is higher.

For these main smog analytes, measured productive rate meets identical ordering: ISO＜HCI-VO＜WG9B＜HCI based on the smoking machine condition.For the productive rate difference between the different condition, the 1mg product is obviously greater than the 6mg product, because the influence that the ventilation of ventilation higher level and WG9B and HCI condition is blocked is for the 1mg product so more obvious.For the 6mg product, the difference that main smog is measured (NFDPM, nicotine and CO) between some conditions is less (magnitude of 5-10%).

47 kinds of poisonous substances that in this work, quantize also under all the smoking machine conditions shown in the table 3, have been measured, but be not collected in the data of EC TSS1 and BT1 under the ISO machine smoking condition, be lower than the LOQ of described method because preliminary operation shows the productive rate of many compositions.The machine smoking productive rate of these poisonous substances meets the ordering that is used for NFDPM, nicotine and CO shown in the table 4 usually, and therefore, for the remainder of this paper, has only described the productive rate that obtains under the HCI condition.Observed the exception of some unanimity of common productive rate trend.For all products, Volatile Phenols, quinoline and fluorenes do not have systematically to improve along with the raising of the productive rate of the intensity of smoking condition and the measurement of most of smog; The measurement of benzo (a) pyrene of arsenic, phenanthrene and PAH series also shows this behavior for most of product.Particularly, the productive rate of these materials is bigger under than HCI condition under the WG9B condition, though the HCI condition has produced bigger whole amount of smoke.Be known that Volatile Phenols can selectively remove by the cellulose acetate filter tip; Here the behavior of viewed unanimity may represent some variation of the filter efficiencies of these materials between WG9B and HCI condition.Perhaps, it may represent when high strength smoking condition, and some of measuring method are analyzed weakness.For some analytes, observe similar variation (the 1,3-butadiene productive rate of CC1 is lower than the expection of the trend that other five kinds of products find under all smoking conditions) more by accident; When between different smoking conditions, producing the NFDPM of similar quantity, find that the 6mg product is more especially like this, and these find probably owing to analytical error, or reflected the limitation of identification capability in the analytical technology.

In this work, use HCI smoking condition to represent EC and the commercially available relatively the strictest test of thing cigarette.Though these smoking conditions make that the used design feature (filter tip ventilation) of EC and commercial cigarettes is ineffective, they have solved the criticism to the machine yield value of ventilation cigarette.

3.1.1 metal and TSNA productive rate

Two groups of poisonous substances that are included in the rules tabulation are metal and the distinctive nitrosamine of tobacco material (TSNA).These two groups of poisonous substances mainly are subjected to the influence of the used tobacco composition of cigarette producers, and therefore careful mixture selection is the principal element that causes them to reduce in smog.The chemical analysis of hybrid metal and TSNA is described in the table 5 and (is presented among Fig. 3), and their MS productive rates under HCI smoking machine condition are presented in the table 6 and (are presented among Fig. 4).This productive rate will be discussed at each EC in the 3.1.2.1-3.1.2.3 joint below.

3.1.2 other poisonous substance productive rates

Table 7 (being presented among Fig. 5) has shown under HCI smoking machine condition, the smog composition productive rate contrast between EC and commercially available tester.This productive rate will be discussed at each EC in the 3.1.2.1-3.1.2.3 joint below.

3.1.2.1?BT1

The measurement (table 5) of mixture chemistry shown the mixture arsenic of BT1 and chromium content on statistics apparently higher than commercial cigarettes CC1; And the lead of BT1 mixture and nickel content are lower.The MS productive rate of the metal of BT1 and the productive rate of CC1 quite or lower, but arsenic and mercury productive rate are higher.Higher arsenic productive rate can be explained by the higher mixture content of this metal, but the mercury productive rate can not be explained by mixture content, and may represent a kind of illusion, because the mixture mercury content of BT1 and CC1 quite or lower, are lower than LOQ (table 5) for this metal.

The mixture content of nitrosamines of BT1 is lower than US and mixes commercially available relatively thing CC1, and this can see from the comparison of front Virginia and US cigarette of mixing.The MS productive rate expection BT1 of nitrogen containing component is lower than CC1, and reason has two: the first, and tobacco is handled the precursor that has reduced nitrogenous aerosolization compound; Typically produced than the US smoking mixture nitrogenous smog composition of low-yield more with the second, Virginia style tobacco.The measurement of nitrogen-containing compound productive rate has shown that productive rate BT1 on statistics of desired difference: TSNA is starkly lower than CC1 (83-96%) (table 6); Arylamine productive rate BT1 is than the low 26-57% of CC1 (table 7); Also be starkly lower than the productive rate separately (low 82%, the NO of HCN is low by 79%, and ammonia is low by 75%, and pyridine is low by 97%, quinoline low 67% and acrylonitrile low 69%) (table 7) of CC1 with the productive rate of other nitrogen-containing compounds of BT1.These data acknowledgements the use (under the situation of HCN productive rate, in filter tip, having sneaked into CR20) of mixture selection, BT method produced the more low toxicity produce rate of the EC of expection.

This BT method has also reduced mixture polyphenol level, so the reduction of MS phenol productive rate will be expected; But, expect that usually the phenol productive rate of Virginia style product is higher than the US product mix, and this tobacco type difference will alleviate any reduction from the BT method.The phenol that has relatively shown mixed result: BT1 between the phenolic compounds productive rate of CC1 and BT1, paracresol and resorcinol productive rate are lower, and the metacresol of BT1, catechol and hydroquinones productive rate higher (table 7).

The BT method does not influence benzo (a) pyrene productive rate, and the analysis of the PAH in present research has shown that the productive rate of BT1 and CC1 is suitable for fluorenes, phenanthrene, pyrene and benzo (a) pyrene.The carbonyl compound productive rate of cigarette BT1 lower (low 26-74%), but except the formaldehyde, BT1 shows higher (41%) formaldehyde productive rate.When comparing with the composition productive rate separately of CC1, the volatile hydrocarbon productive rate of BT1 is lower, is 21-78% for isoprene, benzene, toluene and naphthalene; But, the height of the 1,3-butadiene productivity ratio CC1 of BT1 35%.It is low that the 1,3-butadiene productivity ratio of CC1 is expected under the HCI condition, so this discovery may be insecure.Viewed most of difference on the volatile ingredient productive rate is consistent with the use of effective vapor phase adsorbent in the BT1 filter tip.The formaldehyde productive rate partly is subjected to ordering about of sugar level, and it is higher than the US mixture usually in the Virginia mixture.The formaldehyde productive rate also improves by the mixture process method.Therefore based on the knowledge of formaldehyde generation in the cigarette, the higher formaldehyde productive rate of BT1 is understandable.Obvious higher 1 of BT1,3-butadiene productive rate may be because the error in the measurement of CC1 productive rate, there is not tangible mechanical factor to support that (this method for treatment of tobacco does not cause 1 to this species diversity because do not exist, the obvious statistics variations of 3-butadiene productive rate, and the use of vapor phase adsorbent in the BT1 filter tip should cause 1, the 3 butadiene productive rate of BT1 lower).Used mixture and selective filter mouth are discussed in 3.2 joints for the contribution that the integral body of smog poisonous substance reduces among the BT1, and this result be with table 7 in viewed because the higher formaldehyde yield value that the mixed chemical factor causes is consistent.

3.1.2.2?TSS1

In TSS1, the whole mixt tenor is higher than among the CC1 for some metals (arsenic, chromium and nickel), and cadmium content is then low, and what difference (table 5) other metals then do not have.This TSS has comprised a high proportion of chalk, and it will constitute the hybrid metal of a part.The analysis of TSS has shown than the higher levels of chromium of TSS1 mixture and metal suitable or lower level other measurements.Therefore, the chromium content most probable that TSS1 is higher than CC1 has reflected and has comprised the TSS material in the mixture; And higher arsenic and the horizontal most probable of nickel are owing to different tobacco type used in the mixture.The metal transfer that should be noted in the discussion above that TSS will be not necessarily takes place with the efficient identical with tobacco, the possible difference of this chemical species owing to the trace metal in chalk and the tobacco (with therefore volatility).Therefore, as TSS1 and CC1 relatively the time (table 6), the metal productive rate under HCI smoking machine condition among the MS is lower or be not visibly different on the statistics.The mixture content of nitrosamines of TSS1 is than CC1 low (23-72%) (table 5), correspondingly the MS productivity ratio CC1 low (17-69%) (table 6) of the TSNA of TSS1 under HCI machine smoking condition.

Have been found that with CC1 and compare that obviously productive rate is lower on statistics for following most of material for TSS1: phenol (29-57%), carbonyl compound (44-86%), PAH (8-71%) and various volatile ingredient (27-94%); Though for catechol, hydroquinones and benzo (a) pyrene, these differences do not reach statistical significance (table 7).These data acknowledgements for whole analyte classifications that check, therefore the poisonous substance productive rate of TSS1 is lower, and has supported such expection, that is, TSS and three-stage filtration mouth should play the effect that produces the whole MS poisonous substance productive rate that reduces in EC.

3.1.2.3?TSS6

The hybrid metal content of TSS6 and CC6 is similarly, except statistics among the TSS6 goes up obviously higher chromium and cadmium mix level.As mentioned above, the horizontal most probable of higher chromium is owing to the high inorganic content of TSS; And higher cadmium content most probable has reflected the difference of tobacco type used between two kinds of mixtures.Compare with CC6, the MS productive rate of cadmium and chromium (measuring under HCI smoking machine condition) does not improve (table 6) in TSS6, it has supported such argument equally, namely, the chemical species of these metals is different between EC and commercially available comparison thing, and unlikely transfers to MS.

Those lower (39-54%) (tables 5) that the mixture content of nitrosamines of TSS6 is more measured than CC6 mixture.Equally, this lower mixture content of nitrosamines changes into the MS productive rate (table 6) of these TSNA of low 37-50% under HCI smoking machine condition.

For the every other chemical species (arylamine of measuring (13-20%), phenol (8-32%), carbonyl compound (35-85%), PAH (18-81%) and various volatile poison (41-96%)) the MS productive rate of TSS6 all is starkly lower than the productive rate of CC6 on statistics, except 1-and 2-amino naphthalenes with-and p-Cresol (wherein said value does not have obvious different) and except ammonia (wherein higher productive rate (13%) statistical obviously different with there is no of CC6) (table 7).These data have been reconfirmed the reduction in the poisonous substance of all kinds of measuring, therefore the TSS reduction that can produce whole MS poisonous substance productive rate as expected in EC obviously.

3.2 filter tip contrast

From the MS productive rate data shown in the table 7, all EC have produced the ratio commercially available lower carbonyl compound of thing cigarette and the productive rate of vapor phase composition of comparing separately, except the formaldehyde and 1,3-butadiene productive rate of BT1.In order to understand mixture used among the EC and selective filter mouth better for the contribution of the whole reduced rate of these smog compositions, at EC and contrast cigarette (SC-BT1, SC-TSS1 and SC-TSS6) directly compare between (all the EC with suitable is identical in all respects for it, except the single-stage CA filter tip that uses no adsorbent).Table 8 and 9 (being presented at respectively in Fig. 6 and 7) has shown for carbonyl compound and other vapor phase compositions, the comparison of the productive rate of EC and contrast cigarette.

Can obviously find out from these data, by the existence of the three-stage filtration mouth that contains CR20L and high-activity carbon used among EC BT1 and the TSS1, the productive rate of carbonyl compound and other vapor phase compositions all be reduced (table 8).For all measured volatile ingredients of BT1, the mean change of MS productive rate is compared with contrast cigarette SC-BT1 and has been reduced by 50%, the reduction by 79% of scope from the reduction by 23% of acetaldehyde to crotonaldehyde.TSS1 has obtained very similarly to reduce, and compares it with SC-TSS1 and has produced 50% average rate of decrease, and scope reduces by the 10% productive rate reduction by 79% to crotonaldehyde from the productive rate of formaldehyde.

From table 9, can obviously find out, the carbon that contains other polymer source, but the double-filtration mouth (used as TSS6) that does not have the CR20L resin has also reduced by 48% with the productive rate of vapor phase smog composition, and scope reduces by the 11% productive rate reduction by 79% to crotonaldehyde from the productive rate of acetaldehyde.These data have confirmed that together used selective filter mouth has been removed the volatility smog composition of main amount among the EC from cigarette MS, and this has confirmed the research of front to the filter tip adsorbent.For all EC, the two MS productive rate of formaldehyde and 1,3-butadiene is lower than the measured productive rate of science contrast cigarette.The CR20L resin can be found out by the bigger reduced rate of formaldehyde productive rate than the excellent properties of high-activity carbon remove formaldehyde from MS aspect: the higher initial value (53g/ cigarette or 53%) from the BT1/SC-BT1 pairing is compared with 1.9 μ g/ cigarette reduced rates (10%) in the TSS1/SC-TSS1 pairing.Therefore, obviously, the bigger formaldehyde productive rate of seeing when comparing BT1 and commercial cigarettes CC1 (table 7) must be owing to the difference in the mixture between these cigarettes.Similarly more also confirmed to compare with CC1 the higher 1,3-butadiene productive rate of BT1 most likely because the analytical error in the measurement of 1,3 butadiene of CC1.

3.3 the comparison of those of EC poisonous substance productive rate and disclosed cigarette branding data

This paper concentrates on comparison EC poisonous substance productive rate and two kinds of commercially available relatively productive rates of thing cigarette.But, in order to establish fully, compare with the commercial cigarettes of routine, whether EC provides the machine productive rate that reduces, and those of the cigarette of their productive rate and wide region more must be compared.The absolute yield value of EC described herein can compare i.e.: (1) (Health Canada (2004) with other public datas that obtain under HCI smoking condition Constituents and emissions reported for cigarettes sold in CanadaHttp:// www.hc-sc.gc.ca/hc-ps/alt_formats/hecs-sesc/pdf/tobactab ac/legislation/ reg/indust/constitu-eng.pdf (the visit date: in November, 2010); The data of asking for from .TRR_RRRT@hc-sc.gc.ca; (2) Counts, people such as M.E. (2005) Smoke composition and predicting relationships for international commercial cigaiettes smoked with three machine-smoking conditions.Regul.Toxicol.Pharmacol.41,185-227; (3); Department of Health Australia and Ageing:http: //www.health.gov.au/internet/main/publishing.nsf/Content/t obacco-emis, (the visit date: in November, 2010).But, be noted that the difficulty that causes owing to the known limited standardization based between the laboratory of analyzing the smog composition except NFDPM, nicotine and CO,, must carefully handle such comparison.

Three kinds of top data sources are assembled into a data group, the reference group of global cigarette productive rate data is provided, the poisonous substance productive rate of the EC described in itself and this research is compared.With all data groups as the abreviation of getting off: at first, from the data group, remove arsenic, MEK, nickel and selenium productive rate, because not all three sources all provide these productive rates; Secondly as if, remove many brands from the data group, this is owing to incomplete, that repeat or wrong data (toluene of two brands and styrene productive rate vicious (exchange) in HC data group; In the HC of Gitanes KS data group, do not provide tar, nicotine and CO productive rate, and in HC data group, observed multiplephase productive rate data together).At last, from the data group, remove with reference to product and guarantee only to comprise commercially available brand.This has produced the data group of 120 cigarette brands that cover 16 countries.Though a lot, this data group unlikely represents the tobacco product scope of global marketing fully, no matter is aspect the design feature scope, still be as the representative sample of global brand.Though but it is very limited in these areas, it has constituted the effective ratio of the poisonous substance productive rate that is used for these EC really than the thing group.

Whether described data inspection is observed it is normal distribution; Though in the data group (particularly nitrogenous poisonous substance, as TSNA and arylamine) of the most of and Non-Gaussian Distribution of many poisonous substances.Therefore, the comparable data group is carried out the analysis of experience cumulative distribution, the percentage point that has produced in the poisonous substance productive rate distributes.Productive rate and experience cumulative distribution with EC compares then, determines to compare with commercially available brand the position (Fig. 8 and 9) of these productive rates.These relatively in, the productive rate of EC described herein drops to the lower end of numerous poison ranges, and often produces than any product of commercially available branding data group low value all for specific poisonous substance.Exception is the catechol productive rate of BT1 and NO and the TSNA productive rate of TSS1 and TSS6, and wherein said productive rate approximately equivalent is in the intermediate value of commercially available prod data group.On the contrary, the productive rate of commercially available relatively thing cigarette CC1 and CC6 is distributed on the productive rate scope of commercially available data group usually.

Carried out other comparison, it has checked total level of poisons of each commercially available prod of EC and data group.This carries out in three kinds of modes.First method is the productive rate summation with 39 kinds of poisonous substances of each cigarette, to provide total poisonous substance productive rate (TTY) of each brand.The purposes of this scheme is limited, because the TTY value of each brand is dominated by tar, CO and nicotine, many other poisonous substances are to not obviously contribution of total value.Second method is with the productive rate of whole poisonous substances of each cigarette (but not comprising tar, nicotine and CO productive rate) summation, to provide the summation (TSY) of poisonous substance group productive rate.The third, method for normalizing provided the bigger of the contribution of whole poisonous substances seen clearly, and wherein calculated the intermediate value of every kind of poisonous substance in the commercially available data group.To every kind of poisonous substance, with this intermediate value normalizing to 100, and with the poisonous substance productive rate with respect to this value of 100 convert (scale).All the summation of the scaled value of poisonous substance has provided the poisonous substance total value (NTT) of the normalizing of every kind of brand.The value of all brands in TTY, the TSY of EC and the commercially available data group among NTT value and Figure 10-12 is compared and sort.This comparison shows that for every kind of method, EC is in the lower end of ordering.Each following 1mg EC three kinds of methods has minimum total poisonous substance productive rate, and the TSY of 6mg EC and NTT also are lower than any commercially available brand.In TTY analyzed, two kinds in 120 kinds of commercially available prod had the TTY value lower than TSS6, and this is owing to their lower tar and nicotine value.It also is quite low that total poisonous substance value of commercially available relatively thing cigarette CC1 and CC6 is compared with the data group of commercially available brand, falls near the approximately lower quartile numerical value.

These are analyzed and show some minimum cigarette machine poisonous substance productive rates that EC provides disclosed HCI smog chemistry to obtain together; Therefore these contrasts have confirmed, compare with the known level of commercial cigarettes, and EC has produced the machine poisonous substance productive rate that reduces.

3.4 as with the comparison of the EC productive rate of the ratio of nicotine productive rate

Above-mentioned analysis is limited to the machine productive rate of estimating poisonous substance.But existing people proposes, and compares with independent MS yield value, and the ratio of the smog poisonous substance of cigarette and MS nicotine productive rate has provided the better prediction that the smoker is exposed to poisonous substance.So, calculated MS composition productive rate measured in this research and the ratio (all under HCI smoking machine condition, measuring) of MS nicotine productive rate, and table (table 10, Fig. 8 A and 8B) provides as a supplement.Under Health Canada Intense machine smoking condition, the NFDPM productive rate of BT1, TSS1 and CC1 is suitable, but compares with CC1, high slightly and nicotine productive rate TSS1 low slightly (table 4 and 7) of the nicotine productive rate of BT1.When the yield value of EC is as calculating with the ratio of nicotine productive rate and when those of CC1 and CC6 are compared, the identical trend of finding when they follow productive rate with each cigarette relatively, but the lower value of BT1 is more obvious when comparing with CC1, and the lower value of TSS1 is a little not too obvious when comparing with CC1.

3.5 sidestream smoke productive rate

In order to finish the chemical analysis from the smog emission thing of EC, under ISO smoking parameter, measured the SS productive rate of the smog composition tabulation of expansion.Selected ISO smoking parameter, because they can produce the SS productive rate higher than any other smoking condition.Usually under any smoking condition, the amount of sidestream smoke can be expected the amount of tobacco that the static combustion that depends on cigarette smoking or the stage of smouldering consume.The SS yield results provides in table 10 as the contrast between EC BT1 and TSS1 and the commercial cigarettes CC1.

Have been found that BT1 has than obvious higher productive rate on the CC1 statistics: effluent NFDPM (21%) and several components such as benzo (a) pyrene (28%), phenol (28-77%), carbonyl compound (22-63%) and volatile hydrocarbon (20-24%) composition.Opposite BT1 compares with CC1 has lower productive rate: nitrogenous SS smog composition such as TSNA (31-82%), HCN (47%), arylamine (21-40%) nitrogen oxide, pyridine and quinoline (19-35%).People such as (, 2010) Liu before changing, described most these, still, and higher SS phenol productive rate and compare with the TSNA productive rate of the expection of BT1 and lowlyer to have shown that the chemical differences between Virginia and the US smoking mixture also influences the SS productive rate of single composition.At last, the tobacco weight ratio CC1 high 13% of BT1 also will contribute for viewed improvement all sidedly.

Many SS smog composition productive rates of EC cigarette TSS1 are lower than CC1.In TSNA, observed maximum SS productive rate numeral difference, the low 28-52% of the ratio CC1 of TSS1; These discoveries are consistent with the trend of observing in the MS of these materials productive rate.The reduction most probable of this wide region has reflected the decline by the minimizing of sneaking into the tobacco quality in the cigarette that TSS produces and the smog total amount that produces thus.It is formaldehyde (high 19%) that TSS1 has that composition that statistics goes up obviously higher effluent productive rate than CC1.Higher SS formaldehyde productive rate is also found among the higher levels of TSS included in mixture people such as (, 2010) McAdam, and this shows that formaldehyde may be the accessory substance of organic material burning used during TSS makes.

4. conclusion

Three kinds of EC are to use the combination of technical scheme to make, and the test chemical under four kinds of different machine smoking parameters verified the integral body of MS poisonous substance productive rate of EC reduce.When with the open value of the MS poisonous substance productive rate of conventional cigarette relatively the time, though BT1 has the formaldehyde productive rate of rising, the performance of these EC looks better, even they are based on nicotine than sorting.The data that this research institute proposes have supported these EC are appointed as the machine-productive rate prototype of reduction, and use the aforesaid data of the EC of TSS scheme manufacturing to show that when being used by the smoker these RMYP can realize the lower biomarker that is exposed to the MS poisonous substance.

Although have available from the low whole machine productive rate of the poisonous substance of present RMYP and their performance with respect to commercially available relatively thing and other disclosed poisonous substance productive rate data, but still need a large amount of science data (comprising the biomarker of exposure and the biomarker of biological effect) to determine whether such product can be relevant with lower health risk, therefore uncertain these RMYP will satisfy the IOM definition of PREP.

But we believe that the result of this research is enough to encourage further work, comprise further application and the improvement of technology used in the human biomarker research of these RMYP and their manufacturing.

5. prototype tobacco product

Three kinds of prototype RTP tobacco products constructed in accordance.These cigarettes are super form (king size format), the long 27mm of filter tip and pipe tobacco column length 56mm.These prototypes have the pipe tobacco post of the mixture that comprises tobacco leaf, expanded tobacco and non-tobacco sheet or modification tobacco.Use conventional cigarette paper to form the pipe tobacco post and guarantee to realize burn rate and suction number subsequently.

Being used for wherein, the filter tip of two kinds of prototypes is three-stage filtration mouths, it comprises CA mouth end section (7mm long), contains the CA central segment (10mm is long) of CR20HD ion exchange resin and contains the dalmation style tobacco end section (10mm grows) of the carbon pearl of the micro-structural with design.The filter tip that is used for the third prototype is the double-filtration mouth, and it comprises CA mouth end section (15mm is long) and contains the dalmation style tobacco end section (12mm is long) of the carbon pearl in highly active polymer source.

Make the ISO NFDPM productive rate that this prototype cigarette produces 1 (T562 and H671) and 6mg (F752).The specification of this prototype cigarette is more detailed description in table 11-13.

Table 11. tobacco composition specification

Prototype	T562(1mg)	H671(1mg)	F752(6mg)
				Tobacco leaf (%wwb)	40	12.5	55.0
Expanding tobacco ^a(%wwb)	40	12.5	-
				Expanding tobacco ^b(%wwb)	-	-	25.0
The modification tobacco ^c(%wwb)	-	75	-
				Non-tobacco sheet ^d(%wwb)	20	-	20
The head fragrant (AOLSA) that adds (%wwb)	0.8	0.8	0.8

^aAurora-100% flue-cured tobacco

^bSCB-50% flue-cured tobacco, 50% uncle's Lay taro leaf

^cThe tobacco of using the tobacco composition processing to cross

^dThis non-tobacco sheet is the TSS with following specification: chalk (78.5%), Kelvis alginates (7.5%), glycerine (12.5%) and caramel color (1.5%) (manufacturer; Deli-HTL).

Table 12. cigarette specification

Prototype	T562(1mg)	H671(1mg)	F752(6mg)
				Girth (mm)	24.6	24.6	24.6
Length overall (mm)	83	83	83
				Pipe tobacco column length (mm)	56	56	56
Cigarette paper	CP50-23 VGM2.0KCM	CP50-23 VGM2.0KCM	CP50-23 VGM2.0KCM
				The ventilation type	OML	OML	OML
Ventilation amounts to (ST+OML) (%)	80	80	46
				Density (mg/cc)	216	247	235
(mmWG) falls in cigarette pressure	97	91	109
				Cigarette solidness (%)	TBC	TBC	TBC
Tar (NFDPM) (mg)	1.0	1.2	5.3
				Nicotine (mg)	0.08	0.10	0.43
Carbon monoxide (mg)	1.0	1.0	4.9

Table 13. filter tip specification

Code name	T562(1mg)	H671(1mg)	F752(6mg)
				The filter tip code name (Filtrona, USA)	SAM013108-031	SAM013108-031	SAM020608-040
Length overall (mm)	27	27	27
				Mouth end segment length (mm)	7	7	15
Central segment length (mm)	10	10	-
				Tobacco segment length (mm)	10	10	12
Mouth end section fibre	Mono CA	Mono CA	Mono CA
				The central segment fiber ^a	CA+20mg CR20 HD	CA+20mg CR20 HD	-
The tobacco end section fibre ^b	CA+60mg Blucher carbon	CA+60mg Blucher carbon	CA+80mg Blucher carbon
				Total filter tip PD (mmWG)	150	142	114
The filter stick coil paper ^c	PW600043	PW600043	PW600043

^aThe amine-functionalized resin of CR20HD=(manufacturer: Mitsubishi)

^bBlucher carbon=spherical carbon pearl (manufacturer: Adsor Tech.)

^cThe filter stick coil paper is used for two or three filter tips of finished product

6. the smog poisonous substance exposes research

The evaluation of poisonous substance exposure (BoE) of (he changes to prototype (RTP) cigarette that poisonous substance of the present invention reduces from conventional cigarette) biomarker in the smoker has been paid close attention in this research.

With a combined 6mg and two the 1mg ISO tar yield RTP of producing of the technology that is discussed in detail above, provide in detail as following table 14.

Table 14: the raw product of test

* ISO condition=35mL draw volume, 2 second duration, 60 seconds are at interval, and filter tip ventilation 100% is open

#HCI (Health Canada Intense) condition=55mL draw volume, 2 second duration, 30 seconds at interval, filter tip ventilation 100% sealing

The smog chemistry shows that compare with the contrast cigarette of conventional design, poisonous substance has substantial degradation, referring to table 15 (Figure 15).

Carried out the switching research that is monocentric, single blind, STOCHASTIC CONTROL in six weeks, and clinical confinement has once in a while been arranged, as shown in figure 16.Recruited the adult tested person person of 301 health altogether in the research; The smoker of 100 6-7mg ISO tar yield cigarettes (being assigned to the 6mg group), the smoker of 151 1-2mg ISO tar yield cigarettes (being assigned to the 1mg group) and 50 non-smokers.The smoker who recruits is assigned randomly to control group or test group in their the tar scope, every group about 50.All the smoker sucks 2 weeks of reference product of supply, carries out 14 days base line measurement thereafter.The control group smoker continues to suck 4 weeks of reference product again, and test group smoker switches to RTP and carried out for 4 weeks.Under every kind of situation, measure in the 28th day (2 week) and the 41st day (4 week).Non-smoker's group provides the indication about the biomarker background level.

In three (smokers) and two clinical confinement processes of (non-smoker) short-term, collect twenty-four-hour urine sample (referring to Figure 16), and assess to the exposure of some smog compositions by the level of analyzing the urine biomarker that exposes.The exposure analysis of biomarker is to use effective LC-MS/MS method to realize.

When RTP smog chemistry was compared with contrast cigarette, most of poisonous substance of measuring was significantly lower (10-96%), and real standard depends on design and poisonous substance (referring to table 15).Unique productive rate is higher a kind of product (BT1), and it has transmitted nicotine and the 35% above 1,3-butadiene more than 16%, though this also is to show the product that whole largest global of other poisonous substances reduces.The direction of the variation of corresponding biomarker and relative value are mainly abideed by the variation (table 15 and Figure 17 and 18) of smog chemistry, though the reduction of smog is accompanied by the raising of biomarker (be nicotine and NNK for TSS1) under rare cases, perhaps improve in the smog but biomarker (be 1,3-butadiene for BT1) reduces.The reason of these differences is unknown, but may relate to analytical variance or smoker's behavior.

Figure 17 has shown the biomarker result who changes to the group 2 of cigarettes tested TSS6 (the 41st day) from contrast cigarette CC6 (the 14th day).* represent significant difference (p≤0.01) on the 14th and 41 day statistics between the result.Shown that non-smoker's biomarker level is as reference.All non-smoker's level all is starkly lower than the 14th day value.

Figure 18 shown and organized 4 and group 5 biomarker result, and group 4 is changed to cigarettes tested TSS1 (the 41st day) from contrast cigarette CC1 (the 14th day), and group 5 is changed to cigarettes tested BT1 (the 41st day) from contrast cigarette CC1 (the 14th day).

This discovers that on average, the cigarette smoking person group of changing to the prototype cigarette of poisonous substance reduction exposes the level that has reduction in (BoE) at corresponding biomarker.These comprise the BoE of particle and vapor phase poisonous substance.Different prototypes has caused the difference reduction level of BoE, reduces in some cases significantly greater than 50%, and this depends on and has adopted which type of technical combinations.Common most biomarker level is tangible after being reduced in two weeks of switching.Under all scenario, average biomarker level is lower in non-smoker's group.

This research has confirmed for the first time after the prototype cigarette of changing to poisonous substance reduction of the present invention from conventional cigarette, the obvious reduction of the BoE scope of tobacco smoke poisonous substance among the smoker.

Figure 19 has shown the tobacco product design according to a kind of embodiment of the present invention.Tobacco product 1 comprises pipe tobacco post 2 and filter tip 3.This pipe tobacco post comprises can burn and suck the material post, and its composition is the tobacco that crosses of 75% mixture process, 12.5% leaf and 12.5% expanding tobacco.

The tobacco that this mixture process is crossed is the tobacco with protein and polyphenol content of reduction, and it is available from following method: (i) water extracts tobacco; (ii) make water extract pass clay and resin; (iii) handle this fiber and inactivation with enzyme; (iv) this extract is combined again with fiber, and dry.Described leaf is the used tobacco of conventional commercial cigarettes.This expanding tobacco is the supercritical CO that has used for the commercial cigarettes of routine ₂Method has been carried out expanded tobacco.

Filter tip 3 is connected on the pipe tobacco post 2 by tipping paper (it is non-porous paper).

Filter tip 3 constitutes by three sections, shown in illustration.Adjacent with pipe tobacco styletable section 4 long 10mm, and comprise the synthetic carbon of 60mg.This is a kind of carbon form with loose structure of design.Interlude 5 long 10mm, and (that is, CR20HD 2mg/mm), a kind of water content are the amino-functionalization resin of 12-17% to comprise 20mg.The filter tip section 6 long 7mm of mouth end joint.It can comprise used cellulose acetate fibre in for example conventional commercial cigarettes.

In the possible variant of tobacco product design shown in Figure 19, can burn and suck material and can comprise the tobacco substitute sheet in addition.The tobacco substitute sheet is the sheet that contains the chalk base of glycerine, and glycerine has reduced the amount of tobacco in the cigarette in being blended into tobacco composition the time.This tobacco substitute sheet can partly or entirely replace constituting some or all of arbitrary or all different materials of the burnt and sucked material of above-mentioned tobacco product design.

Another variant can be to use CR20D in filter tip.CR20D is a kind of amine-functionalized resin, and water content is 0-5%.For example CR20D can partially or completely replace CR20HD used in the above-mentioned design.

Aforementioned specification and embodiment only only providing is used for explanation the present invention but not is intended to restriction.Because embodying the body that changes of the described embodiment of spirit of the present invention and essence may be that those skilled in the art can expect, so the present invention should broadly be interpreted as being included in all variants within additional claim and the equivalent scope thereof.

Claims

1. tobacco product, it comprises following at least two kinds:

(b) tobacco composition, it has removed polyphenol and/or peptide through handling;

(c) tobacco substitute sheet, it comprises non-flammable inorganic filler, adhesive and aerogel generating agent;

(e) amine-functionalized chelating resin.

2. the tobacco product of claim 1, it comprises can burn and suck the material post, and described post comprises maximum 60% tobacco substitute sheet.

3. the tobacco product of claim 2, it comprises can burn and suck the material post, and described post comprises 20% tobacco substitute sheet and 80% tobacco.

4. the tobacco product of aforementioned each claim wherein joins glycerine in the mixture of described tobacco substitute sheet and tobacco subsequently.

4 .The tobacco product of claim 1, it comprises can burn and suck the material post, and described post comprises the tobacco composition of maximum 100% processing.

5. the tobacco product of claim 4, it comprises can burn and suck the material post, and described post comprises the tobacco composition of 75% processing and 25% tobacco.

6. the tobacco product of aforementioned each claim, it comprises the filter tip with three sections: comprise the mouth end section of cellulose acetate, comprise the interlude of cellulose acetate and amine-functionalized chelating resin and comprise cellulose acetate and the tobacco end section of high-activity carbon.

7. the tobacco product of claim 6, wherein said interlude comprises the amine-functionalized chelating resin of 20mg.

8. claim 6 or 7 tobacco product, wherein said tobacco end section comprises the carbon of 60mg.

9. each tobacco product of claim 1-3, it comprises the filter tip with two sections: comprise the mouth end section of cellulose acetate and comprise the tobacco end section of cellulose acetate and carbon.

10. the tobacco product of claim 9, wherein said tobacco end section comprises the carbon of 80mg.

11. each tobacco product of claim 6-9, wherein said carbon are the high-activity carbon pearls that comprises the material with carbon element in polymer source.

12. each tobacco product of claim 6-9, wherein said amine-functionalized chelating resin is CR20.

13. the tobacco product of claim 1, it comprises and is selected from (a) and (b) and (c) at least a and is selected from (d) and (e) at least a.

14. the tobacco product of claim 13, it comprises (c) and (e).

15. the tobacco product of aforementioned each claim, all mainstream smoke compositions that are considered to not expect that it has obvious reduction.