阅读说明：本技术 一种香味缓释层状材料及其制备和在加热不燃烧烟草制品中的应用 (Aroma slow-release layered material, preparation thereof and application thereof in heating non-combustible tobacco products ) 是由 崔雨琪 郑聪慧 杨华武 邓昌健 丁莎 邓婷 吴榆 周建良 刘建福 于 2019-11-13 设计创作，主要内容包括：本发明属于新型烟草缓释加香技术领域,具体涉及一种用于加热不燃烧烟草制品的香味缓释层状材料,包括纤维纸基材,以及复合在纤维纸基材表面的聚合物缓释层；聚合物缓释层包括聚合物基底,以及复合在聚合物基底中的活性炭@香料复合物；所述的活性炭@香料复合物包括活性炭以及吸附在活性炭孔隙内的挥发性香料。本发明还提供了所述的香味缓释层状材料的制备以及应用。本发明技术方案,能够显著提升高挥发性香料的负载率,增强香气逐口释放均匀性,延长留香时间,改善抽吸感官质量,并赋予HNB产品稳定的质量风格特征。该发明为彰显加热不燃烧烟草制品表香香精的香气品质、传承常规卷烟品牌的质量风格特征提供了重要技术手段。(The invention belongs to the technical field of novel tobacco slow-release flavoring, and particularly relates to a flavor slow-release layered material for heating a non-combustible tobacco product, which comprises a fiber paper base material and a polymer slow-release layer compounded on the surface of the fiber paper base material; the polymer sustained release layer comprises a polymer substrate and an activated carbon @ perfume compound compounded in the polymer substrate; the activated carbon @ perfume complex comprises activated carbon and a volatile perfume adsorbed in pores of the activated carbon. The invention also provides the preparation and application of the aroma slow-release layered material. According to the technical scheme, the loading rate of the high-volatility perfume can be remarkably improved, the fragrance release uniformity by mouth is enhanced, the fragrance retention time is prolonged, the smoking sensory quality is improved, and stable quality and style characteristics are endowed to HNB products. The invention provides an important technical means for showing the aroma quality of the surface aroma essence of the non-burning tobacco products by heating and inheriting the quality style characteristics of conventional cigarette brands.)

1. A flavour-releasing layered material for heating non-combustible smoking articles, characterized in that: comprises a fiber paper substrate and a polymer slow-release layer compounded on the surface of the fiber paper substrate;

the polymer sustained release layer comprises a polymer substrate and an activated carbon @ perfume compound compounded in the polymer substrate; the activated carbon @ perfume complex comprises activated carbon and a volatile perfume adsorbed in pores of the activated carbon.

2. A flavour release layered material according to claim 1, wherein: the iodine value of the activated carbon is more than or equal to 400 mg/g.

3. A flavour release layered material according to claim 2, wherein: the iodine value of the activated carbon is more than or equal to 800 mg/g.

4. A flavour release layered material according to claim 2, wherein: the active carbon is at least one of coconut shell active carbon, anthracite columnar active carbon, shell active carbon, coal active carbon, wood active carbon and tar active carbon.

5. A flavour release layered material according to claim 1, wherein: in the aroma slow-release layered material, the mass percentage of the active carbon is more than or equal to 1 percent.

6. A flavour release layered material according to claim 5, wherein: in the aroma slow-release layered material, the mass percentage of the active carbon is 1-30%.

7. A flavour release layered material according to claim 1, wherein: the volatile spice is high-volatility spice with the boiling point less than 200 ℃.

8. A flavour release layered material according to claim 7, wherein: the volatile perfume comprises N-containing heterocyclic perfume and/or lower ester perfume.

9. A flavour release layered material according to claim 8, wherein: the N heterocyclic spice is at least one of 2, 3, 5-trimethyl pyrazine, 2, 5-dimethyl pyrazine and 3-ethyl pyridine.

10. A flavour release layered material according to claim 8, wherein: the lower ester perfume is at least one of ethyl acetate, ethyl propionate and ethyl isovalerate.

11. A flavour release layered material according to claim 1, wherein: the mass percentage content of the volatile spice is less than or equal to 50 percent.

12. A flavour release layered material according to claim 1, wherein: the active carbon @ perfume compound is obtained by adsorbing active carbon and volatile perfume.

13. A flavour release layered material according to claim 12, wherein: the adsorption is liquid phase adsorption or gas phase adsorption.

14. A flavour release layered material according to claim 13, wherein: liquid phase adsorption is to put the activated carbon into liquid volatile flavor for adsorption and then separate to obtain the activated carbon @ flavor complex.

15. A flavour release layered material according to claim 13, wherein: gas phase adsorption is adsorption by placing activated carbon in an atmosphere of perfume, followed by the activated carbon @ perfume complex.

16. A flavour release layered material according to claim 12, wherein: the adsorption time is not less than 10 h.

17. A flavour release layered material according to claim 16, wherein: the adsorption time is not within 24 h.

18. A flavour release layered material according to claim 13, wherein: the adsorption temperature is less than or equal to 50 ℃.

19. A flavour release layered material according to claim 1, wherein: the fiber paper substrate is wood pulp fiber and/or tobacco fiber paper.

20. A flavour release layered material as claimed in claim 19, wherein: the fiber paper base material is prepared by taking wood pulp fiber and/or tobacco fiber as raw materials and adopting a paper making method or a thick pulp method.

21. A flavour release layered material as claimed in claim 19, wherein: the wet strength of the fiber paper substrate is more than 0.2 KN/m.

22. A flavour release layered material according to claim 1, wherein: the fibrous paper substrate contains tobacco dust.

23. A flavour release layered material according to claim 1, wherein: the surface of the fibrous paper substrate is coated with tobacco extract.

24. A flavour release layered material according to claim 1, wherein: the polymer of the polymer sustained-release layer is water-soluble or alcohol-soluble high molecular material with film-forming property.

25. A flavour release layered material as claimed in claim 24, wherein: the polymer substrate is made of one or more of methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose, polylactic acid, polyvinyl alcohol and polyvinylpyrrolidone.

26. A flavour release layered material according to claim 1, wherein: the molecular weight of the material of the polymer substrate is 1-150 ten thousand.

27. A flavour release layered material according to claim 1, wherein: in the aroma slow-release layered material, the weight percentage of the polymer substrate is 2-90%.

28. A flavour release layered material as claimed in claim 27, wherein: in the aroma slow-release layered material, the weight percentage of the polymer substrate is 10-50%.

29. A flavour release layered material according to claim 1, wherein: the polymer slow release layer is compounded on any surface of the fiber paper substrate.

30. A method of preparing a flavour release layered material according to any one of claims 1 to 29, characterised in that: preparing the fiber paper substrate, then compounding the membrane liquid containing the polymer and the activated carbon @ spice compound on the surface of the fiber paper substrate, and drying to obtain the fiber paper substrate.

31. A method of preparing a flavour release layered material according to claim 30, wherein: the fiber paper base material is prepared by taking wood pulp fiber or tobacco fiber as a raw material and adopting a paper making method or a thick pulp method.

32. A method of preparing a flavour release layered material according to claim 30, wherein: the preparation process of the activated carbon @ perfume compound comprises the following steps: and (2) carrying out liquid phase adsorption or gas phase adsorption on the activated carbon and the volatile spice to prepare the activated carbon @ spice compound.

33. A process for preparing a flavour release layered material according to claim 32, wherein: pretreating the activated carbon in advance before liquid phase adsorption or gas phase adsorption;

the pretreatment comprises the following steps:

washing the activated carbon, performing reflux treatment on the activated carbon aqueous solution, performing solid-liquid separation and drying treatment.

34. A method of preparing a flavour release layered material according to claim 30, wherein: the solvent in the membrane liquid is a solvent capable of dissolving the polymer substrate.

35. A method of preparing a flavour release layered material according to claim 30, wherein: and compounding the membrane liquid on the fiber paper substrate by adopting a coating method.

36. A process for preparing a flavour release layered material according to claim 35, wherein: the coating is knife coating, roll coating or spray coating.

37. Use of a flavour release layered material according to any one of claims 1 to 29, or a flavour release layered material prepared by the preparation method according to any one of claims 30 to 36, wherein: it is used for preparing a tobacco product which does not burn when heated.

38. Use of a flavour release layered material according to claim 37, wherein: it is used for preparing a heating rod for heating a non-combustible tobacco product.

39. Use of a flavour release layered material according to claim 38, wherein: cutting, mixing with tobacco material, and making into heating rod.

40. Use of a flavour release layered material according to claim 38, wherein: it is used for preparing a cigarette holder rod of a heating non-combustible tobacco product.

41. Use of a flavour release layered material according to claim 40, wherein: cutting, folding or curling the cigarette to obtain the cigarette holder rod.

42. A fragrance slow-release heating rod for heating a non-combustible tobacco product is characterized in that: comprises a tobacco material; the fragrance slow-release layered material also comprises the fragrance slow-release layered material as described in any one of claims 1 to 29 or the fragrance slow-release layered material prepared by the preparation method as described in any one of claims 30 to 36.

43. The aroma-releasing heating rod for heating a non-combustible tobacco product according to claim 42, wherein: is a unit rod or a multi-component composite rod.

44. A fragrance slow-release cigarette holder rod for heating a non-combustible tobacco product is characterized in that: comprises the fragrance slow-release layered material as defined in any one of claims 1 to 29 or the fragrance slow-release layered material prepared by the preparation method as defined in any one of claims 30 to 36.

45. A heat non-combustible smoking article, comprising: comprises the fragrance slow-release layered material as defined in any one of claims 1 to 29 or the fragrance slow-release layered material prepared by the preparation method as defined in any one of claims 30 to 36.

46. The heat-not-burn tobacco product of claim 45, wherein: comprises the aroma slow-release heating rod of any one of claims 42 to 43 and/or comprises the aroma slow-release heating rod of claim 44.

Technical Field

The invention relates to a high-volatility spice slow-release material for heating a non-combustible tobacco product and a preparation method thereof, belonging to the technical field of novel tobacco product fragrance slow release.

Background

A heating non-combustible tobacco product (also called low-temperature tobacco, HNB) is a novel tobacco product with the flavor characteristics closest to that of the traditional cigarette, and the harmful chemical components and the biological toxicity of the smoke are lower. However, the HNB tobacco material part is continuously in a "high temperature environment" of about 180-. Particularly, some high-volatility aroma components such as low-grade esters and N-heterocyclic aroma materials generally have the characteristics of low boiling point, extremely high volatility and the like, and have extremely poor uniformity of mouth-to-mouth release during smoking, and the aroma materials are often key components of surface aroma essence and play an important role in endowing HNB products with characteristic aroma styles. Therefore, the slow release problem of the high-volatility perfume is solved, the practical requirement that a fragrance mixer plays a fragrance mixing role in HNB products is met, the key point for realizing stable quality and style characteristics of the HNB products is realized, and the development of the HNB products with various fragrance styles, different tastes and distinct style characteristics is facilitated, so that the requirements of consumers are better met.

At present, some researches are carried out on the aspect of traditional cigarette flavor slow-release control technology at home and abroad, and the main methods comprise: (1) adding fragrance precursor, and heating at high temperature or burning for cracking to generate fragrance substance. (2) The microcapsules are added. The coating of the essence is realized by coating and other technical means, and the essence are released by the rupture or degradation of the capsule wall. (3) Adding an adsorbent, and adsorbing the essence and the spice by utilizing the porous structure of the adsorbent. (4) The essence is prepared or aged to generate new fragrant substance, which is decomposed under heating and cracking condition to release volatile fragrant components.

However, the above-mentioned flavor-release methods are not fully applicable to HNB products, and in particular, the controlled release of highly volatile fragrances at the operating temperature of HNBs cannot be achieved. As mentioned above, the HNB tobacco material part is always in a continuous heating state as a whole, and the heating temperature is far lower than the combustion temperature of the traditional cigarette, so that some aroma precursors cannot be cracked to generate aroma substances, or the aroma substances wrapped in the microcapsule wall materials cannot be released because the pyrolysis temperature of the microcapsule wall materials cannot be reached, or the aroma substances, especially the high-volatility aroma substances, cannot be released slowly and uniformly only by virtue of the adsorption capacity of the adsorbent and the weak coordination effect of the metal.

In the technical field of HNB flavor slow release, related research reports are few, and most of the research reports are directed at monomer perfumes with boiling points of more than 200 ℃ and certain special structures, such as menthol, beta-ionone and the like, and the technical means are very limited. No slow release technical research aiming at high-volatility perfumes containing N heterocycles or lower esters with the boiling points below 200 ℃ or even below 100 ℃ is seen. Therefore, it is urgently needed to develop a high-volatility perfume slow-release system, which can increase the perfume loading rate, reduce the volatile loss in the process and achieve the effects of continuous, slow and uniform release in the HNB product.

Disclosure of Invention

In order to solve the problem of the uniformity of the mouth-to-mouth release of highly volatile spices (i.e. spices with a boiling point of not higher than 200 ℃) in a tobacco product which is not combusted by heating, the invention innovatively provides a highly volatile spice slow-release layered material, and aims to solve the defects of low perfuming efficiency of the highly volatile spices, easy loss of the spices, poor mouth-to-mouth release uniformity in a smoking process, poor smoking taste and the like.

The second purpose of the invention is to provide a preparation method of the aroma slow-release layered material, which aims to reduce the loss of highly volatile aroma in the processing process and prepare the aroma slow-release layered material which has good storage stability and can effectively avoid burst aroma release in the smoking process.

The third purpose of the invention is to provide a method for applying the aroma slow-release layered material in a non-burning tobacco product by heating.

The fourth object of the present invention is to provide a heating rod for a non-combustible tobacco product, to which the flavor-releasing layered material is added.

The fifth purpose of the invention is to provide a cigarette holder rod of a non-burning tobacco product by heating, which is added with the aroma slow-release layered material.

A sixth object of the present invention is to provide a tobacco product which does not burn when heated, to which the flavor-releasing layered material is added.

The inventor researches the field of flavor slow release of a heating non-combustible tobacco product for many years, and discovers in a very early stage that a certain slow release effect can be achieved by compounding volatile spices in a polymer. However, with the continuous and intensive research, the inventors of the present invention found that, in the early research, the perfume and the adsorbent are respectively dispersed in the polymer substrate, and the binding force of the adsorbing material to the perfume is weak, the adsorbing amount is small, and the adsorbing material is easy to volatilize along with the solvent in the preparation process, and furthermore, there are places to be improved, such as the processing difficulty is large, the sustained release performance of the sustained release material needs to be improved, and the quality stability is not ideal, and based on this, the inventors of the present invention have further researched and proposed the following improvement schemes:

a fragrance slow-release layered material for heating a non-combustible tobacco product comprises a fiber paper substrate and a polymer slow-release layer compounded on the surface of the fiber paper substrate;

the polymer sustained release layer comprises a polymer substrate and an activated carbon @ perfume compound compounded in the polymer substrate; the activated carbon @ perfume complex comprises activated carbon and a volatile perfume adsorbed in pores of the activated carbon.

Unlike conventional perfumes, highly volatile perfumes are difficult to handle and are difficult to effectively circumvent the problems of processing and storage loss and poor uniformity of the mouth-to-mouth release during the pumping process. To this end, the invention innovatively defines the perfume in the pores of the activated carbon in a physical and chemical manner to obtain the activated carbon @ perfume compound; the active carbon @ perfume compound is embedded in the polymer substrate, and the action of the fiber paper substrate is further matched, so that the problem of perfume loss in the processing and storing processes can be effectively solved, the slow release performance of the prepared slow release layered material can be effectively improved, and the problem of too fast release of high-volatility perfume during the slow release and temperature control period is improved. According to the technical scheme, the loading rate of the high-volatility perfume can be remarkably improved, the fragrance release uniformity by mouth is enhanced, the fragrance retention time is prolonged, the smoking sensory quality is improved, and stable quality and style characteristics are endowed to HNB products.

The key points of the invention are as follows: (1) the activated carbon is innovatively used for loading high-volatility perfume, and then the perfume is embedded in the polymer, so that the perfume is difficult to overflow from staggered pore channels under the action of high adsorption capacity and strong adsorption force of the activated carbon, and the perfuming efficiency is effectively improved; on the basis, the initial release temperature of the perfume can be further increased by utilizing the coating effect of the film material, so that the release behavior can be effectively regulated, the release temperature interval can be regulated, and the problem of the mouth-to-mouth release uniformity of the high-volatility perfume can be solved; (2) the polymer layer and the fiber paper base material are compounded with each other to form a layered structure, so that the strength, the hardness, the slow release effect and other properties of the slow release material are further improved, and the slow release material is easier to produce and apply.

Based on the innovation of the invention, the inventor further researches and discovers that the slow release performance of the aroma slow release layered material can be further improved by further controlling the iodine value of the activated carbon and the type of the activated carbon.

Preferably, the method comprises the following steps: the iodine value of the activated carbon is more than or equal to 400 mg/g; more preferably not less than 800 mg/g; more preferably 900 to 3000 mg/g.

The research of the invention unexpectedly discovers that different types of activated carbon influence the physical and chemical limiting behaviors of the perfume, and further influence the perfume slow-release layered material.

Preferably, the method comprises the following steps: the active carbon is at least one of coconut shell active carbon, anthracite columnar active carbon, shell active carbon, coal active carbon, wood active carbon and tar active carbon; further preferably, a columnar activated carbon of smokeless coal is used. The research of the invention finds that the preferred aroma slow-release layered material of the activated carbon has better slow-release performance.

Preferably, the method comprises the following steps: in the aroma slow-release layered material, the mass percentage of the active carbon is more than or equal to 1 percent; more preferably 1 to 30%. Under the active carbon with the form, the content of the active carbon is further controlled, which is beneficial to further improving the slow release performance of the aroma slow release layered material.

The technical scheme of the invention can be applied to heating any volatile spice which can be obtained by technicians in the tobacco product industry and can not be combusted, and the volatile spice is hydrophilic, hydrophobic, strong in volatility or moderate in volatility.

Preferably, the volatile perfume is a high volatile perfume with a boiling point < 200 ℃. The research finds that the technical scheme of the invention has more obvious advantages when being used for the strong-volatility spice which is difficult to process in the prior art in the industry.

Preferably, the volatile perfume comprises a heterocyclic N-containing perfume and/or a lower ester perfume.

The N heterocyclic perfume is at least one of 2, 3, 5-trimethyl pyrazine, 2, 5-dimethyl pyrazine and 3-ethyl pyridine.

The lower ester perfume is at least one of ethyl acetate, ethyl propionate and ethyl isovalerate.

According to the technical scheme, the volatile perfume is limited in an activated carbon structure in a physical and chemical mode, and the activated carbon @ perfume compound is obtained.

Preferably, said activated carbon @ perfume complex is obtained by adsorption of activated carbon and a volatile perfume.

The adsorption is liquid phase adsorption or gas phase adsorption.

Preferably, the liquid phase adsorption is carried out by placing the activated carbon in a liquid volatile flavor, adsorbing and subsequently separating to obtain the activated carbon @ flavor complex.

Preferably, the gas phase adsorption is adsorption by subjecting the activated carbon to an atmosphere of perfume, followed by the activated carbon @ perfume complex.

Preferably, the adsorption time is less than or equal to 7 days.

Preferably, the method comprises the following steps: the adsorption time is preferably within 24 hours.

Preferably, the method comprises the following steps: the adsorption temperature is less than or equal to 50 ℃.

In the invention, the content of the volatile perfume in the fragrance slow-release layered material can be adjusted according to the use requirement.

Preferably, the content of the volatile perfume is less than or equal to 50 percent by mass, and preferably less than or equal to 35 percent by mass.

Preferably, the method comprises the following steps: the polymer of the polymer sustained-release layer is water-soluble or alcohol-soluble high molecular material with film-forming property.

Further preferably: the polymer substrate is made of one or more of methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose, polylactic acid, polyvinyl alcohol and polyvinylpyrrolidone.

Preferably, the method comprises the following steps: the molecular weight of the material of the polymer substrate is 1-150 ten thousand.

Preferably, the method comprises the following steps: in the aroma sustained-release layered material, the weight percentage of the polymer substrate is 2-90 percent; more preferably 10 to 50%. The research finds that the preferable content of the polymer is beneficial to further improving the slow release performance and the slow release behavior of the aroma.

According to the invention, the polymer slow release layer is matched with the fiber paper substrate, so that the slow release behavior is further regulated and controlled, and the slow release performance is further improved.

Preferably, the method comprises the following steps: the fiber paper base material is prepared by taking wood pulp fiber and/or tobacco fiber as raw materials and adopting a paper making method or a thick pulp method. For example, the fibrous paper substrate may be a tobacco sheet, or a paper made from wood pulp fibers.

Preferably, the method comprises the following steps: the wet strength of the fiber paper base material is more than or equal to 0.2 KN/m.

Preferably, the method comprises the following steps: the fibrous paper substrate contains tobacco dust.

Preferably, the method comprises the following steps: the surface of the fibrous paper substrate is coated with tobacco extract.

Preferably, the method comprises the following steps: the polymer slow release layer is compounded on any surface of the fiber paper substrate.

The preparation method of the aroma slow-release layered material comprises the steps of preparing the fiber paper substrate, then compounding a membrane liquid containing a polymer and an active carbon @ spice compound on the surface of the fiber paper substrate, and drying to obtain the aroma slow-release layered material.

The invention innovatively discovers that the volatile spice is pre-absorbed and limited by using the high-adsorption-capacity and strong-adsorption activated carbon, the membrane material is added on the basis and uniformly mixed, and then the mixture is coated on the surface of a paper base material, so that an adsorption system can be more fully embedded, and the fragrance slow-release layered material prepared after the solvent is removed can effectively prevent the high-volatility spice from rapidly volatilizing, and the heating end or the mouth rod end of the tobacco product which is not burnt by heating can be added, so that the technical problems that the first mouth of the tobacco product is too strong in fragrance, the second mouth of the tobacco product is basically volatilized completely, the specific quality and style characteristics of the product are difficult to endow with and the like in the direct perfuming process can be solved, and the development of the heated non-combustible tobacco product with good sensory quality.

Preferably, the fiber paper base material is prepared by taking wood pulp fiber or tobacco fiber as a raw material and adopting a paper making method or a thick pulp method. The research of the invention finds that the paper base material obtained by papermaking and the polymer slow-release layer are matched, thereby being beneficial to further regulating and controlling the slow-release behavior of the material and further improving the performance of the material.

The fiber paper substrate can be prepared by adopting the conventional papermaking equipment and method.

Preferably, the process for preparing the activated carbon @ perfume complex is: and (2) carrying out liquid phase adsorption or gas phase adsorption on the activated carbon and the volatile spice to prepare the activated carbon @ spice compound.

Preferably, the method comprises the following steps: pretreating the activated carbon in advance before liquid phase adsorption or gas phase adsorption;

the pretreatment comprises the following steps:

washing the activated carbon, performing reflux treatment on the activated carbon aqueous solution, performing solid-liquid separation and drying treatment.

The research finds that the pretreatment of the activated carbon helps to further improve the physical and chemical effects of the volatile perfume, regulate the slow release behavior of the volatile perfume, and regulate the slow release temperature period, thereby helping to obtain the efficient perfume slow release layered material.

In the invention, the obtained activated carbon @ perfume complex is placed in a solution of a polymer substrate to obtain the membrane liquid.

Preferably, the solvent in the film liquid is a solvent that can dissolve the polymer base material.

In the invention: and compounding the membrane liquid on the fiber paper substrate by adopting a coating method.

Preferably, the method comprises the following steps: the coating is knife coating, roll coating or spray coating.

The preferable preparation method comprises the following specific steps:

(1) the paper base material is prepared by taking wood pulp fiber or tobacco fiber as a raw material and adopting a paper making method or a thick stock method through the working procedures of pulping, drying, coating and the like.

(2) Screening activated carbon with high adsorption capacity and strong adsorbability, and sequentially carrying out ash treatment in the steps of washing, boiling, drying and the like, wherein the specific process is as follows: weighing appropriate amount of activated carbon, grinding into powder, and boiling with distilled water for 30 min. And cooling to room temperature, washing with distilled water for 2-3 times, boiling for 30min again, and repeating the same operation once. After the pretreatment, the mixture is placed in a constant-temperature oven at 130 ℃ until the weight of the activated carbon is not changed any more.

(3) And (3) weighing a proper amount of the activated carbon pretreated in the step (2) to adsorb the high-volatility perfume. The adsorption method can be liquid phase adsorption or gas phase adsorption, the liquid phase adsorption is to directly soak activated carbon in high volatility perfume for adsorption, and the gas phase adsorption is to spread the activated carbon on filter paper for adsorption of volatile perfume gas. The adsorption method preferably adopts liquid phase adsorption. The adsorption temperature is less than or equal to 50 ℃, and the adsorption time is less than or equal to 7 d.

(4) Dissolving a film material by adopting a proper amount of solvent, adding the dissolved film material into the adsorption system formed in the step (3) to form viscous liquid, uniformly stirring, loading the viscous liquid on any surface of the paper base material in a blade coating, roller coating or spraying manner, and removing the solvent to prepare the slow-release material.

The invention also provides an application of the aroma slow-release layered material, which is used for preparing a tobacco product which is not combusted by heating; preferably it is used for the preparation of a heating rod for heating a non-combustible smoking article; further preferably, the cut tobacco is mixed with a tobacco material to prepare a heating rod.

The invention also provides an application of the aroma slow-release layered material, which is used for preparing a tobacco product which is not combusted by heating; it is preferably cut, folded or crimped for use in making a cigarette holder rod for a heat-not-burn tobacco product.

The aroma slow-release layered material can be cut into any shape and size used for heating non-combustible cigarettes by adopting the existing method.

The high volatility flavor slow release material can be cut or folded into various shapes for application to the heated end or the mouth end of a heated non-combustible smoking article, including but not limited to filaments, tablets, granules. The invention also provides a fragrance slow-release heating rod for heating non-burning tobacco products, which comprises the fragrance slow-release layered material and tobacco raw materials. The tobacco raw material can be cut tobacco and/or tobacco powder.

Preferably, the aroma slow-release heating rod for heating the non-burning tobacco products is a unit rod or a multi-element rod.

The invention also provides a fragrance slow-release cigarette holder rod of a heating non-combustion tobacco product, which comprises the fragrance slow-release layered material. In the aroma slow-release cigarette holder rod, the addition amount of the aroma slow-release layered material can be adjusted according to needs, and is 10-50 percent for example.

Preferably, the aroma slow-release heating rod for heating the non-burning tobacco products is a unit rod or a multi-element rod. In the aroma slow-release heating rod, the addition amount of the aroma slow-release layered material can be adjusted according to needs, and is 0.1-20% for example.

The invention also provides a heating non-combustion tobacco product, which comprises the aroma slow-release layered material; preferably comprises the aroma slow-release heating rod and/or the aroma slow-release cigarette holder rod.

Has the advantages that:

1. the invention creatively utilizes physical and chemical modes to pre-limit the perfume in the pores of the activated carbon to obtain the activated carbon @ perfume compound; the active carbon @ perfume compound is embedded in a polymer substrate, and the action of the fiber paper substrate is further matched, so that the problem of perfume loss in the processing and storing processes can be effectively solved, the slow release performance of the prepared slow release layered material can be effectively improved, and the burst release problem can be improved during the regulation and control of the slow release temperature. Moreover, the slow-release layered material provided by the invention has the advantages that the perfume is not dispersed in the polymer substrate, the properties are not matched with those of the polymer, and the universality is stronger.

2. The invention selects the active carbon with better adsorption performance as the adsorption material, effectively improves the loading capacity of the high-volatility spice and the perfuming efficiency by utilizing the loose porous structure and the larger specific surface area of the adsorption material, and has low price of the active carbon and no peculiar smell in sensory evaluation.

3. The paper base material with better adsorbability is used as a supporting material, the loose porous structure on the surface of the paper base material is utilized, the adsorption capacity of the activated carbon on the high-volatility spice is combined, and the film material is further coated, so that the quick volatilization of the spice can be further prevented, and the storage and the transportation of the spice are facilitated. The membrane material can not be combusted and cracked to generate peculiar smell at the working temperature (300 ℃) of the heating non-combustion tobacco product, and can be gradually softened along with the rise of the temperature in the smoking process, so that the spice is slowly and uniformly released, the technical foundation is laid for the high-volatility spice to be used for flavoring the heating non-combustion tobacco product, and an important technical means is provided for HNB products to show the aroma quality of the surface aroma essence and inherit the quality and style characteristics of conventional cigarette brands.

4. The slow release material has the advantages of simple manufacturing method, cheap and easily obtained raw materials, various application forms at the heating end or the mouth rod end of the heating non-combustible tobacco product, stronger practicability and convenient process realization.

Drawings

FIG. 1 is a TG plot of the composite of example 1 and comparative example 1;

FIG. 2 is a curve of the adsorption amount of trimethyl pyrazine by different activated carbon under liquid phase adsorption conditions with time

FIG. 3 is a thermogravimetric curve of a trimethyl pyrazine perfume raw material

FIG. 4 is a thermogravimetric curve of the liquid phase adsorption anthracite activated carbon @ trimethylpyrazine adsorption system in example 2

Fig. 5 is SEM images of the paper substrate a of example 2 (fig. 5A) and the trimethylpyrazine slow release material of example 2 (fig. 5B);

FIG. 6 is a thermogravimetric plot of DL-polylactic acid

FIG. 7 is the thermogravimetric curve of the paper substrate A and the trimethylpyrazine slow-release material (anthracite activated carbon as adsorbent) in example 2

FIG. 8 is a thermogravimetric curve of a trimethylpyrazine sustained-release material (diatomite is used as an adsorbent) in comparative example 2

The specific implementation scheme is as follows:

the invention is further described with reference to specific examples. The following examples are intended to illustrate the invention without further limiting it.

Example 1

The preparation method of the active carbon @ perfume compound by gas phase adsorption comprises the following specific steps:

according to the scheme, the immobilization and sustained release effects of coconut shell activated carbon, anthracite columnar activated carbon, shell activated carbon, coal activated carbon, wood activated carbon and tar activated carbon on trimethyl pyrazine (with the boiling point of 171 ℃) are investigated. The specific implementation method comprises the following steps:

(1) weighing a proper amount of anthracite columnar activated carbon, coconut shell activated carbon, coal activated carbon, wood activated carbon and tar activated carbon for water purification, respectively grinding the anthracite columnar activated carbon, coconut shell activated carbon, coal activated carbon, wood activated carbon and tar activated carbon into powder, sieving the powder with a 100-mesh sieve, boiling the powder with distilled water for 30min, cooling the powder to room temperature, washing the powder with distilled water for 2-3 times, boiling the powder for 30min again, repeating the same operation before one time, and then placing the powder in a constant-temperature oven at 130 ℃ for drying;

(2) an adsorption test of trimethyl pyrazine (2, 3, 5-trimethyl pyrazine) was carried out by a gas phase adsorption method. Fixing filter paper on a culture dish, dripping 1g of trimethyl pyrazine on the bottom of the culture dish respectively, weighing 5g of activated carbon subjected to ash treatment in the step (1) correspondingly, uniformly paving the activated carbon on the upper surface of the filter paper, sealing the whole adsorption device by using a preservative film, placing the adsorption device in a 35 ℃ oven, adsorbing the activated carbon in a gas phase for 24 hours, and weighing the activated carbon;

the adsorption amount of the activated carbon is the mass of the activated carbon after loading-the mass of the activated carbon before loading. The adsorption amounts per unit mass of the activated carbon are shown in table 1.

TABLE 1 iodine values of different kinds of activated carbon and their adsorption amounts to trimethyl pyrazine under gas phase adsorption conditions

As can be seen from the table, the adsorption amount of the anthracite activated carbon to the trimethyl pyrazine is the largest, so 1g of polylactic acid (with the molecular weight of 20 ten thousand) as a membrane material is added into the adsorption system (namely, the material subjected to gas phase adsorption at the temperature of 35 ℃ for 24 hours, namely, the anthracite activated carbon @ trimethyl pyrazine), and the specific method comprises the steps of firstly dissolving the polylactic acid by using ethyl acetate to form viscous liquid, then adding the activated carbon-perfume adsorption system, uniformly stirring, coating, and removing the solvent to obtain the high-volatility perfume slow-release composite membrane.

Comparative example 1:

compared with example 1, the difference is only that the anthracite activated carbon is replaced by diatomite (namely, the anthracite activated carbon @ trimethyl pyrazine is replaced by diatomite @ trimethyl pyrazine).

The TG comparative analysis of the high volatile perfume slow release composite membranes of example 1 and comparative example 1 is shown in fig. 1. As can be seen from fig. 1, the slow release composite membrane prepared by using diatomite as the adsorbing material has a very low loading amount (< 4%) of trimethyl pyrazine in the final membrane material due to the weak adsorbing force of the diatomite with high volatility perfume, and in contrast, the slow release composite membrane prepared by using activated carbon as the adsorbing material has a loading amount of trimethyl pyrazine increased by more than one time (11%), and the quality slowly and uniformly decreases between 50 ℃ and 300 ℃, corresponding to the gradual release of trimethyl pyrazine. The better adsorption performance of the anthracite columnar activated carbon is utilized to effectively reduce the volatility loss of high-volatility perfume in the preparation process of the composite membrane and improve the loading capacity of the perfume in the composite membrane.

Example 2

The liquid phase adsorption preparation method of the active carbon @ perfume compound comprises the following specific steps:

in order to further improve the adsorption amount of the fragrance raw material, in this example, on the basis of example 1, the gas phase adsorption was changed to liquid phase adsorption, the temperature in the adsorption process was 35 ℃, and the activated carbon was weighed after 24 hours, and the adsorption amount is shown in table 2.

TABLE 2 adsorption amounts of different kinds of activated carbon to trimethylpyrazine under liquid phase adsorption conditions

Comparing table 1 and table 2, it can be seen that the adsorption amount of the perfume by the liquid phase adsorption method is larger than that by the gas phase adsorption method, and as can be seen from fig. 2, the adsorption amount of trimethyl pyrazine by the activated carbon is substantially constant within 7d, so that the adsorption balance is reached, which indicates that the adsorption and fixation ability of the activated carbon to the highly volatile perfume is stronger, and therefore, the liquid phase adsorption method should be preferred in the selection of the adsorption method.

In addition, the scheme also considers the change curve of the adsorption quantity of different types of activated carbon to the trimethyl pyrazine along with the time under the liquid phase adsorption condition. As can be seen from FIG. 2, the adsorption performance of different activated carbons is different, wherein the adsorption amount of the anthracite activated carbon (with an iodine value of 1300mg/g) to trimethyl pyrazine is the largest, and the adsorption time can reach 881mg/g for 24 h.

In order to further characterize the change condition of the mass of the trimethyl pyrazine in the anthracite activated carbon along with the temperature, thermogravimetric analysis is respectively carried out on the trimethyl pyrazine aromatic raw material and an adsorption system. As can be seen from the analysis of fig. 3 and 4, the trimethyl pyrazine raw material is very volatile when heated, the quality is rapidly reduced from 40 ℃, and the trimethyl pyrazine raw material is completely volatile at 90 ℃. In contrast, the mass of the activated carbon (anthracite activated carbon) adsorption system is in the process of rapidly decreasing at the temperature of programmed temperature of 40-350 ℃ and then slowly decreasing, the weight loss rate at 350 ℃ is 46%, and at the moment, trimethyl pyrazine in the activated carbon is completely volatilized.

In order to further prevent the volatilization of the spice, improve the slow release effect of the fragrance and endow the slow release material with more natural tobacco flavor, the scheme takes the paper base material A containing the tobacco powder as a coating base material, and on the basis of an anthracite activated carbon-trimethyl pyrazine adsorption system, a membrane material DL-polylactic acid (same as the embodiment 1) is added for membrane coating treatment. The specific implementation steps are as follows: (1) papermaking of the paper base material A: taking northern wood pulp and tobacco powder as raw materials, and manufacturing a paper base material A by adopting a paper-making method sheet production method; (2) preparation of coating liquid: 2g of DL-polylactic acid (with a molecular weight of 20 ten thousand) is weighed, dissolved into a viscous liquid by ethyl acetate, and added into an adsorption system (obtained in example 2) which is in adsorption balance for 24 hours in example 2 (anthracite activated carbon + trimethylpyrazine), so that the mass ratio of the trimethylpyrazine to the activated carbon to the polylactic acid is 0.881:1: 2. (3) After the coating liquid is uniformly stirred, the coating liquid is coated on the surface of the paper base material A by adopting a blade coating method, and the paper base material A is dried at normal temperature to remove the solvent, so that the slow-release material (anthracite activated carbon @ trimethyl pyrazine @ paper base material A; also called trimethyl pyrazine slow-release material in the case) is prepared. Analyzing the surface performance of the sustained-release material by adopting SEM, as shown in figure 5, the fiber of the paper base material A is in a porous structure (figure 5A), and the trimethyl pyrazine sustained-release material is shown in figure 5B; therefore, a layer of film is formed on the surface of the coated activated carbon, the activated carbon (anthracite activated carbon @ trimethyl pyrazine) adsorbing the spices is uniformly distributed in the film material, and most of particles are completely coated by the film material, so that the spices are prevented from being rapidly volatilized at normal temperature.

The sustained-release material is cut into filaments with the diameter of 1mm by 5mm by a shredder, the filaments are blended into tobacco materials of fine-branch heating non-burning cigarettes according to the proportion of 2 percent, sensory evaluation test is carried out, and thermogravimetric analysis is carried out on the sustained-release material.

The result of the test of the suction test shows that: the method is characterized in that trimethyl pyrazine is directly injected to a heating end of a heating non-combustible tobacco product by adopting a perfuming injection instrument, a first mouth has strong baking characteristic aroma, a second mouth is obviously lightened, later mouths basically cannot feel aroma, the aroma is released from mouth to mouth with poor uniformity, and the taste difference before and after smoking is large; after the trimethyl pyrazine slow-release material is added, the fragrance is good in persistence and uniformity in mouth-to-mouth release, and obvious fragrance can be sensed from the first mouth to the seventh mouth and the eighth mouth. Studies have also found that the higher the perfume content, the more lost the process and the lower the efficiency of use. When the amount of the added perfume is large, the aroma characteristics are prominent. The specific addition ratio depends on the application, and when the other fragrances are modified, the ratio may be less than 1% or even lower.

Thermogravimetric analysis results: the thermogravimetric curve of DL-polylactic acid is shown in FIG. 6, which shows that the mass of polylactic acid is constant below 300 deg.C, and the mass is rapidly reduced between 300 deg.C and 380 deg.C, corresponding to the cracking of polylactic acid. The thermogravimetric curves of the paper base material A and the trimethyl pyrazine slow-release material (anthracite activated carbon is used as an adsorbent) are shown in fig. 7, and comparing fig. 3 with fig. 4, it can be known that the slow-release material has stable quality below 100 ℃, the initial release temperature of trimethyl pyrazine is remarkably increased, the quality is slowly and continuously reduced between programmed temperature rise of 100 ℃ and 300 ℃, the weight loss rate is 16.8% corresponding to uniform release of trimethyl pyrazine.

Comparative example 2:

compared with example 2, the difference is only that the anthracite activated carbon in the diatomite is replaced by the diatomite.

Fig. 8 is a thermogravimetric curve of an original trimethylpyrazine slow-release material prepared by using diatomite as an adsorbent, the slow-release temperature interval of the perfume is 100-200 ℃, the loading rate (weight loss rate) of the trimethylpyrazine is 9.2%, and comparison shows that the slow-release material prepared by using activated carbon such as anthracite activated carbon as the adsorbent has stronger solid-carrying capacity on the high-volatility perfume, larger perfume loading rate and wider slow-release temperature interval.

Example 3

According to the scheme, the paper base material B is used as a coating base material, the shell activated carbon (with an iodine value of 1000mg/g) is used as an adsorbent, the methyl cellulose is used as a membrane material to prepare the high-volatility perfume slow-release material, and the immobilization and slow-release effects on the ethyl propionate are examined. The specific implementation method comprises the following steps:

(1) papermaking of the paper base material B: taking northern wood pulp and tobacco powder as raw materials, manufacturing a paper base material B by a paper-making method sheet production method, and loading 20% of tobacco extract on the surface of the paper base material B in a dip-coating mode to enable the color of the paper base material B to be closer to the natural color of tobacco;

(2) weighing 1g of ash-treated shell activated carbon, performing an adsorption test on ethyl propionate by adopting a liquid phase adsorption method, dropwise adding 1g of ethyl propionate into the activated carbon, and uniformly mixing (the adsorption temperature is 35 ℃ and the time is 24 hours).

(3) Weighing 3g of methylcellulose, adding a proper amount of water to dissolve the methylcellulose to form viscous liquid, mixing the viscous liquid with an activated carbon-spice adsorption system (obtained in the step (2)), uniformly stirring the viscous liquid and the activated carbon-spice adsorption system, coating the viscous liquid on the paper base material B prepared in the step (1) in a roller transfer mode, and drying the paper base material B at a low temperature of 50 ℃ to remove the solvent to prepare the slow-release material.

(4) Evaluation of sustained release effect: the slow release material is cut into filaments with the diameter of 1mm by 5mm by a filament cutter, the filaments are blended into tobacco materials of fine count HNB cigarettes according to the proportion of 2 percent, sensory evaluation test is carried out, and thermogravimetric analysis is carried out on ethyl propionate fragrant raw materials and the slow release material.

The result of the smoke panel test and the thermogravimetric analysis shows that the ethyl propionate fragrant raw material is very easy to volatilize when being heated, the quality is rapidly reduced from the beginning, and the ethyl propionate fragrant raw material is completely volatilized at 55 ℃. Compared with the prior art, the ethyl propionate slow-release material prepared by the scheme can achieve the effect of slow and uniform weight loss at the temperature of 80-200 ℃, the weight loss rate is 9.3%, the ethyl propionate slow-release material can continuously release seven or eight tastes of distinct fruity fragrance characteristic fragrance of ethyl propionate when a heating end of a thin cigarette which is not combusted is added, and the uniformity of mouth-by-mouth release is obviously improved.

Example 4

In this example, referring to the preparation method of example 2, a paper substrate a is used as a coating substrate, coconut activated carbon (with an iodine value of 860mg/g) is used as an adsorbent, and polyvinyl alcohol (1788 type, molecular weight of 17 ten thousand)/polyvinylpyrrolidone (K90 type, molecular weight of 36 ten thousand) is used as a membrane material to prepare an ethyl isovalerate slow release material. The specific implementation method comprises the following steps:

(1) the adsorption test was carried out by a liquid phase adsorption method: weighing 1g of coconut shell activated carbon after ash treatment, adding 1g of ethyl isovalerate, and uniformly mixing (the adsorption temperature is 35 ℃ and the time is 24 hours).

(2) Weighing 1g of polyvinyl alcohol and 1g of polyvinylpyrrolidone, adding a proper amount of water to dissolve the polyvinyl alcohol and the polyvinylpyrrolidone to form viscous liquid, mixing the viscous liquid with the activated carbon-spice adsorption system (obtained in the step (1)), uniformly stirring the viscous liquid, spraying the viscous liquid on the front side and the back side of the paper base material B, and drying the paper base material B at a low temperature of 50 ℃ to obtain the slow-release material.

(3) Evaluation of sustained release effect: cutting the slow-release material into particles of 2mm x 2mm, adding the particles into a cooling section of the HNB cigarette filter tip rod, carrying out sensory evaluation test, and carrying out thermogravimetric analysis on the ethyl isovalerate fragrant raw material and the slow-release material.

The result of the smoke panel test and the thermogravimetric analysis shows that the raw material of the ethyl isovalerate is extremely easy to volatilize when being heated, the quality is rapidly reduced from 40 ℃, and the raw material is completely volatilized at 70 ℃. Compared with the prior art, the ethyl isovalerate slow-release material prepared by the scheme can achieve the effect of slow and uniform weight loss at the temperature of 100-250 ℃, the weight loss rate is 13.6%, the cooling end of the tip rod of the cigarette is added, the characteristic fruit fragrance of ethyl isovalerate can be continuously released by more than nine times, and the uniformity of release by one time is remarkably improved.

Meanwhile, the slow release effects of a directly-fragrant heating non-combustion cigarette control sample and an experimental sample added with a slow release material are compared by adopting a real-time online smoke analysis platform, and the result shows that the GC/MS detection signal of ethyl isovalerate in the directly-fragrant control sample is 1.5 x 10⁵The volatility loss is huge, which is equivalent to ineffective perfuming; the signal value of the control ethyl isovalerate added with the slow release material is 1.2 x 10⁷Compared with direct fragrance spraying, the fragrance is two orders of magnitude higher, which shows that the high volatility can be obviously improvedThe perfuming efficiency of the perfume prevents the perfume from volatilizing rapidly.

Example 5

In this embodiment, a paper substrate B is used as a coating substrate, anthracite activated carbon (with an iodine value of 1300mg/g) is used as an adsorbent, hydroxypropyl methylcellulose (model HG50Y, north chemical industry) is used as a membrane material to prepare a slow release material of a tobacco top flavor a, wherein the flavor a contains some high-volatility flavors such as ethyl acetate, ethyl propionate, isoamyl isovalerate, 3-ethylpyridine, and the like. The specific implementation method comprises the following steps:

(1) the adsorption test was carried out by a liquid phase adsorption method: weighing 10g of anthracite activated carbon after ash treatment, sieving by a 200-mesh sieve, adding 20g of essence A, and uniformly mixing (the adsorption temperature is 25 ℃ and the time is 12 hours).

(2) Weighing 50g of hydroxypropyl methyl cellulose, dissolving the hydroxypropyl methyl cellulose by using 75% ethanol to form viscous liquid, mixing the viscous liquid with the activated carbon-spice adsorption system (prepared in the step (1)) in the step (1), uniformly stirring to prepare a coating liquid, uniformly coating the coating liquid on the surface of the paper substrate B by using a scraper coater, wherein the thickness of a wet material to be coated is 1mm, the coating speed is 10cm/min, and drying at a low temperature of 50 ℃ to remove a solvent, so that a layer of film is formed on the surface of the paper substrate B.

(3) Shredding the slow release material prepared in the step (2), mixing the shredded slow release material with cut tobacco in a proportion of 5%, rolling into a heating non-combustion cigarette, and comparing the cigarette with the heating non-combustion cigarette prepared by directly spraying fragrance for sensory evaluation.

The result of smoke panel tests shows that the cigarette control sample prepared by directly spraying fragrance and heated without burning has strong fragrance in the first mouth, heavy chemical smell, less elegant fragrance, obviously reduced fragrance in the second mouth, light fragrance in the third mouth and no obvious additional apparent fragrance characteristic in subsequent mouths. Compared with the prior art, the cigarette is not combusted by heating with the slow release material, the aroma release durability and the mouth-by-mouth uniformity are obviously improved, the aroma characteristics can last for more than eight mouths, the aroma is elegant, fine and soft, and the smoking sensory quality is obviously better than that of a control sample.