CN102835735B - Temperature-sensitive micro capsule as well as preparation method and application of temperature-sensitive micro capsule - Google Patents
Temperature-sensitive micro capsule as well as preparation method and application of temperature-sensitive micro capsule Download PDFInfo
- Publication number
- CN102835735B CN102835735B CN201210344080.3A CN201210344080A CN102835735B CN 102835735 B CN102835735 B CN 102835735B CN 201210344080 A CN201210344080 A CN 201210344080A CN 102835735 B CN102835735 B CN 102835735B
- Authority
- CN
- China
- Prior art keywords
- essence
- temperature
- preparation
- cigarette
- capsule
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a temperature-sensitive micro capsule as well as a preparation method and application of the temperature-sensitive micro capsule. The temperature-sensitive essence micro capsule consists of essence for cigarette as core materials and high-molecular materials as capsule materials, wherein the high-molecular materials consist of sodium alginate and polyethylene glycol. The preparation method comprises the following preparation steps that water solution of the sodium alginate and the polyethylene glycol is prepared, the stirring is carried out so that the uniform dispersion is realized, and air bubbles are removed; the prepared solution of essence for cigarette is extruded out from an inner pipe of a concentric material outlet, meanwhile, the water solution is extruded out from an outer pipe of the concentric material outlet, concentric linear fluid is cut through a rotary blade, fine particles are formed, and curing and drying are carried out in calcium ion salt solution. The temperature-sensitive micro capsule has the beneficial effects that the temperature-sensitive micro capsule has the advantages that the prepared essence for cigarette can be sealed in the capsule, and the essence is not released at the room temperature, so the essence can be stored for a long time without invalidation. The temperature-sensitive micro capsule has the advantages that the resources of used raw materials are wide, the price is low, and the preparation method is simple.
Description
Technical field
The invention belongs to technical field of cigarettes, be specifically related to a kind of essence microcapsule, also relate to the preparation method of this essence microcapsule.
Technical background
Essence and flavoring agent technology is one of core technology of cigarette industry.In cigarette, add essence and flavoring agent, can coordinate cigarette perfume (or spice), improve and inhale taste, increase the sense organ acceptance of cigarette.Conventional perfuming cigarette mode is in pipe tobacco, to add essence and flavoring agent at present.But due to essence and flavoring agent highly volatile and escaping, this has caused the change that the shelf life of cigarette product is shorter and inhale taste.For this reason, researcher has adopted various ways to improve.A kind of mode is the fragrance matter that adds low volatility in cigarette.US Patent No. Patent No.3312226 utilizes the latent Studies of The Aromatic Substances of the synthetic menthol of esterification, has reduced the volatility of menthol, and the latent Studies of The Aromatic Substances of these menthols joins in pipe tobacco, in the time of cigarette burning, cracking occurs, and discharges flavor component wherein.But the Studies of The Aromatic Substances of diving adds in pipe tobacco, need to participate in burning together with pipe tobacco, not only may lose due flavouring effect, also may cracking produce new harmful substance.Another perfuming mode is to utilize means perfumings in filter stick such as fragrant line, adsorbent, capsule.Chinese patent CN1099957A, using inorganic silicic acid aluminium or inorganic silicic acid aluminium salt as menthol adsorbent, adds in cigarette filter rod after absorption menthol, rolls into mentholated cigarette, when suction, can discharge strong minty note.But fragrant line and adsorbent are merely able to slow down the dispersion process of essence, the storage time is long, still can lose original effect.US Patent No. Patent No.4889144 has reported a kind of essence capsule, and this essence capsule adds cigarette filter rod and rolls into cigarette, before suction, utilizes External Force Acting to destroy capsule and discharges essence wherein.
Summary of the invention
Given this essence additive that, the object of the present invention is to provide a kind of at room temperature long storage time not lose efficacy.
For solving the problems of the technologies described above, technical scheme provided by the invention is, a kind of responsive to temperature essence microcapsule is provided, form by the flavouring essence for tobacco as core with as the macromolecular material of capsule material, described macromolecular material is made up of sodium alginate and polyethylene glycol, particle diameter is 0.1mm～1mm, and flavouring essence for tobacco content is 1%～50% of microcapsules weight, and capsule material thickness is 5 μ m～50 μ m.
Preferably, the part by weight of sodium alginate and polyethylene glycol is 1:10～20:1.
Preferably, the molecular weight of described polyethylene glycol is 400～2000kDa.
The present invention also provides the preparation method of above-mentioned responsive to temperature essence microcapsule, and concrete steps are as follows:
1), the aqueous solution of preparation sodium alginate and polyethylene glycol, stir it be uniformly dispersed, and remove after bubble stand-by;
2), deployed flavouring essence for tobacco solution is extruded from the inner tube of concentric discharging opening, the above-mentioned aqueous solution is extruded from concentric discharging opening outer tube simultaneously, formed concentric line style continuous fluid, skin is Polymer Solution, and internal layer is essence solution; , with rotating vane, concentric line style fluid is cut meanwhile, form fine particle, in calcium ion salts solution, solidify, after being dried, obtain responsive to temperature essence microcapsule.
Preferably, described rotating vane rotating speed is 50 revs/min～1000 revs/min.
Preferably, described calcium ion salts is calcium chloride or Dicalcium Phosphate.
The present invention also provides the application of above-mentioned responsive to temperature essence microcapsule, essence microcapsule is evenly inserted when the wire-beam forming, make the filter rod that contains microcapsules, with composite filter forming machine, the filter stick that contains microcapsules and common filter stick are combined into composite filter again, every cigarette adds essence microcapsule 1-30mg.When the composite tip stick that contains essence microcapsule is applied to after cigarette, when cigarette does not aspirate, essence in essence microcapsule is non-volatile, and in the time of cigarette smoking, main flume by time the variations in temperature brought will make microcapsules rupture, thereby discharge essence wherein, consumer can taste the cigarette perfume (or spice) of coordination.
Useful, responsive to temperature essence capsule of the present invention can be sealed in deployed flavouring essence for tobacco in capsule, does not discharge essence when room temperature, therefore can long storage time not lose efficacy; Add after cigarette filter rod, utilize main flume by the variations in temperature of bringing,, in the time of 37 DEG C～45 DEG C, essence capsule breaks, thereby discharges the wherein essence of parcel.The raw materials used wide material sources of the present invention, cheap, preparation method is simple, is easy to realize large-scale production.Be applied to cigarette industry and produce, can reduce essence consumption, cost-saving.
Essence microcapsule provided by the invention has certain temperature sensitivity, in the time of room temperature, can stablize and deposit, and therefore rolls into after cigarette, can effectively extend storage period and the shelf life of cigarette product.In the time of cigarette smoking, do not need External Force Acting, main flume can make microcapsules rupture through out-of-date variations in temperature, discharges the wherein essence of parcel.Compared with common microcapsules, under the temperature conditions passing through at main flume, essence discharges more homogeneous and fully.
Detailed description of the invention
Describe below in conjunction with concrete example.
Embodiment 1
Sodium alginate and the polyglycol solution 1L of preparation 0.5%, the molecular weight of polyethylene glycol is 400kDa, the weight ratio of sodium alginate and polyethylene glycol is 1:10.Be uniformly mixed and remove bubble, be placed in the container being connected with concentric discharging opening outer tube, stand-by.5.6g menthol is dissolved in 100mL glycerine, be placed in the container being connected with concentric discharging opening inner tube, menthol solutions and Polymer Solution are extruded from the inner and outer tubes of discharging opening respectively simultaneously, form concentric line style fluid, rotating vane cuts into fine particle with 100 revs/min by concentric line style fluid simultaneously, and solidify in 20% calcium chloride solution, after being dried, obtain menthol essence microcapsule.Gained Microcapsules Size is 1 millimeter, and capsule material thickness is 50 microns, and menthol content is 10%.
Above-mentioned 20g essence microcapsule, with in the tiling of 2mm thickness and glassware, under 30 DEG C of constant temperatures, is used to the menthol retention rate of its different time of gas chromatographic measurement.Result is as shown in table 1.
Table 1 essence microcapsule retains the ability of menthol
Above-mentioned 40g essence microcapsule, with in 2mm thickness tiling and 2 glasswares, is placed in respectively under 30 DEG C and 45 DEG C of constant temperatures to the menthol retention rate of its different time of use gas chromatographic measurement.Result is as shown in table 2.
Table 2 essence microcapsule is in the menthol reserve capability of different temperatures
| Time | 30min | 90min | 180min | 270min |
| 30 DEG C of retention rates | 99.6％ | 99.2％ | 98.9％ | 98.9％ |
| 45 DEG C of retention rates | 76.4％ | 62.9％ | 49.2％ | 38.7％ |
Embodiment 2
Sodium alginate and the polyglycol solution 1L of preparation 1%, the molecular weight of polyethylene glycol is 600kDa, the weight ratio of sodium alginate and polyethylene glycol is 1:1.Be uniformly mixed and remove bubble, be placed in the container being connected with concentric discharging opening outer tube, stand-by.0.8g osmanthus essential oil is dissolved in 500g vegetable oil, be placed in the container being connected with concentric discharging opening inner tube, osmanthus essential oil solution and Polymer Solution are extruded from the inner and outer tubes of discharging opening respectively simultaneously, form concentric line style fluid, rotating vane cuts into fine particle with 500 revs/min by concentric line style fluid simultaneously, and solidify in 30% calcium chloride solution, after being dried, obtain osmanthus essential oil essence microcapsule.Gained Microcapsules Size is 0.6 millimeter, and capsule material thickness is 20 microns, and osmanthus essential oil content is 3%.
Embodiment 3
Sodium alginate and the polyglycol solution 1L of preparation 4%, the molecular weight of polyethylene glycol is 2000kDa, the weight ratio of sodium alginate and polyethylene glycol is 10:1, is uniformly mixed and removes bubble, is placed in the container being connected with concentric discharging opening outer tube, stand-by.10g Tea Polyphenols is dissolved in 600g vegetable oil, be placed in the container being connected with concentric discharging opening inner tube, Tea Polyphenols solution and Polymer Solution are extruded from the inner and outer tubes of discharging opening respectively simultaneously, form concentric line style fluid, rotating vane cuts into fine particle with 800 revs/min by concentric line style fluid simultaneously, and solidify in 40% Dicalcium Phosphate solution, after being dried, obtain Tea Polyphenols essence microcapsule.Gained Microcapsules Size is 0.4 millimeter, and capsule material thickness is 10 microns, and polyphenol content is 30%.
Embodiment 4
Sodium alginate and the polyglycol solution 1L of preparation 0.5%, the molecular weight of polyethylene glycol is 1000kDa, the weight ratio of sodium alginate and polyethylene glycol is 20:1, is uniformly mixed and removes bubble, is placed in the container being connected with concentric discharging opening outer tube, stand-by.10g osmanthus essential oil is dissolved in 500g sunflower oil, be placed in the container being connected with concentric discharging opening inner tube, osmanthus essential oil solution and Polymer Solution are extruded from the inner and outer tubes of discharging opening respectively simultaneously, form concentric line style fluid, rotating vane cuts into fine particle with 1000 revs/min by concentric line style fluid simultaneously, and solidify in 10% calcium chloride solution, after being dried, obtain osmanthus essential oil essence microcapsule.Gained Microcapsules Size is 0.1 millimeter, and capsule material thickness is 5 microns, and osmanthus essential oil content is 50%.
Embodiment 5
The menthol essence microcapsule obtaining in embodiment 1 is evenly inserted when the wire-beam forming, make the filter rod that contains menthol essence microcapsule, with composite filter forming machine, the filter stick that contains microcapsules and common filter stick are combined into composite filter again, every cigarette adds essence particle 30mg.When the composite tip stick that contains menthol essence microcapsule is applied to after cigarette, when cigarette does not aspirate, menthol in essence microcapsule is non-volatile, and in the time of cigarette smoking, main flume by time the variations in temperature brought will make microcapsules rupture, thereby discharge menthol wherein, consumer can experience the refrigerant of peppermint.
By the mentholated cigarette in the present embodiment, aspirate above-mentioned cigarette according to standard conditions with Borgwaldt RM200A type smoking machine, collect flue gas with cambridge filter, measure the release rate of menthol in every mouthful of flue gas with gas chromatography-mass spectrography.Result is as shown in table 3.
The release rate of menthol in flue gas corresponding to the different puff numbers of table 3.
Embodiment 6
The osmanthus essential oil microcapsules that obtain in example 4 are evenly inserted when the wire-beam forming, make the filter rod that contains osmanthus essential oil microcapsules, with composite filter forming machine, the filter stick that contains microcapsules and common filter stick are combined into composite filter again, every cigarette adds essence particle 1mg.When the composite tip stick that contains osmanthus essential oil essence microcapsule is applied to after cigarette, when cigarette does not aspirate, osmanthus essential oil in microcapsules is non-volatile, and in the time of cigarette smoking, main flume by time the variations in temperature brought will make microcapsules rupture, thereby discharge osmanthus essential oil wherein, consumer can experience fresh and sweet fragrance, and cigarette quality gets a promotion.
Below be only the preferred embodiment of the present invention, it should be pointed out that above-mentioned preferred embodiment should not be considered as limitation of the present invention, protection scope of the present invention should be as the criterion with claim limited range.For those skilled in the art, without departing from the spirit and scope of the present invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (3)
1. the preparation method of a responsive to temperature essence microcapsule, this responsive to temperature essence microcapsule forms by the flavouring essence for tobacco as core with as the macromolecular material of capsule material, it is characterized in that, described macromolecular material is made up of sodium alginate and polyethylene glycol, particle diameter is 0.1mm～1mm, flavouring essence for tobacco content is 1%～50% of microcapsules weight, and capsule material thickness is 5 μ m～50 μ m; Sodium alginate and polyethylene glycol part by weight are 1:10～20:1; The molecular weight of described polyethylene glycol is 400～2000kDa, and the concrete steps of its preparation method are as follows:
1), the aqueous solution of preparation sodium alginate and polyethylene glycol, stir it be uniformly dispersed, and remove after bubble stand-by;
2), deployed flavouring essence for tobacco solution is extruded from the inner tube of concentric discharging opening, the above-mentioned aqueous solution is extruded from concentric discharging opening outer tube simultaneously, formed concentric line style continuous fluid, skin is Polymer Solution, and internal layer is essence solution; , with rotating vane, concentric line style fluid is cut meanwhile, form fine particle, in calcium ion salts solution, solidify, after being dried, obtain responsive to temperature essence microcapsule.
2. according to the preparation method of the responsive to temperature essence microcapsule described in claims 1, it is characterized in that, described rotating vane rotating speed is 50 revs/min～1000 revs/min.
3. according to the preparation method of the responsive to temperature essence microcapsule described in claims 1, it is characterized in that, described calcium ion salts is that calcium chloride is or/and Dicalcium Phosphate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210344080.3A CN102835735B (en) | 2012-09-17 | 2012-09-17 | Temperature-sensitive micro capsule as well as preparation method and application of temperature-sensitive micro capsule |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210344080.3A CN102835735B (en) | 2012-09-17 | 2012-09-17 | Temperature-sensitive micro capsule as well as preparation method and application of temperature-sensitive micro capsule |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102835735A CN102835735A (en) | 2012-12-26 |
| CN102835735B true CN102835735B (en) | 2014-08-20 |
Family
ID=47363668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210344080.3A Active CN102835735B (en) | 2012-09-17 | 2012-09-17 | Temperature-sensitive micro capsule as well as preparation method and application of temperature-sensitive micro capsule |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102835735B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103316616A (en) * | 2013-06-03 | 2013-09-25 | 吴江市利达上光制品有限公司 | Osmanthus essence nanocapsule and preparation method |
| CN103251131A (en) * | 2013-06-07 | 2013-08-21 | 安徽中烟工业有限责任公司 | Preparation method of perfuming filter stick with perfumed substance released slowly |
| CN105105334A (en) * | 2015-07-17 | 2015-12-02 | 云南中烟工业有限责任公司 | Spice slow-release filter tip additive with polymer covering film as well as preparation method and application thereof |
| CN105713329B (en) * | 2016-02-01 | 2017-09-19 | 威骏（湖北）高新实业股份有限公司 | A kind of preparation method of cinnamon essential oil spacetabs type functional ornamentation material |
| CN105876855A (en) * | 2016-07-06 | 2016-08-24 | 南通烟滤嘴有限责任公司 | Self-soluble capsule-containing filter stick and filter tip thereof |
| CN106235403B (en) * | 2016-08-31 | 2019-03-22 | 云南巴菰生物科技有限公司 | A kind of slow-release fragrance filter stick and preparation method thereof |
| US11224251B2 (en) | 2016-12-29 | 2022-01-18 | Philip Morris Products S.A. | Aerosol-generating article comprising a liquid delivery element |
| CN107723091B (en) * | 2017-11-29 | 2021-06-11 | 武汉黄鹤楼新材料科技开发有限公司 | Preparation method of mint essential oil blasting bead for cigarettes |
| CN109497612B (en) * | 2018-12-12 | 2021-03-16 | 湖北中烟工业有限责任公司 | Heating non-combustion cigarette holder rod with tea aroma |
| CN109497613B (en) * | 2018-12-12 | 2021-04-02 | 湖北中烟工业有限责任公司 | A filter tip for heating incombustible cigarette |
| CN109497609B (en) * | 2018-12-12 | 2021-02-02 | 湖北中烟工业有限责任公司 | Cigarette holder rod containing cooling agent and capable of being heated and not combusted |
| CN112143563A (en) * | 2020-08-28 | 2020-12-29 | 深圳波顿香料有限公司 | Essence for temperature-sensitive cigarette and preparation method thereof |
| CN115226730A (en) * | 2022-08-24 | 2022-10-25 | 合肥中龙神力动物药业有限公司 | Volatile disinfectant for animal house and preparation method thereof |
| CN117089405B (en) * | 2023-08-23 | 2024-03-12 | 广州科百欣香料有限公司 | Rose-type essence microcapsule for cigarettes and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1374338A (en) * | 2001-03-12 | 2002-10-16 | 中国科学院大连化学物理研究所 | Emulsifying and internal gelifying process of preparing calcium alginate gel beads |
| CN101049187A (en) * | 2007-05-18 | 2007-10-10 | 云南烟草科学研究院 | Composite filter tip of two layer molding paper containing additive |
| CN101810595A (en) * | 2009-02-25 | 2010-08-25 | 中国中化股份有限公司 | Preparation method of calcium alginate microcapsule |
| CN102068038A (en) * | 2010-12-31 | 2011-05-25 | 贵州中烟工业有限责任公司 | Method for preparing heat-sensitive moisture-retaining central line filter stick of cigarette |
| CN102140387A (en) * | 2011-01-20 | 2011-08-03 | 深圳市如烟生物科技有限公司 | Method for preparing microcapsule essence for cigarette |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005508648A (en) * | 2001-11-09 | 2005-04-07 | ベクター・タバコ・インコーポレーテッド | Composition and method for mentholization of charcoal filtered cigarettes |
| US7810507B2 (en) * | 2006-02-10 | 2010-10-12 | R. J. Reynolds Tobacco Company | Smokeless tobacco composition |
-
2012
- 2012-09-17 CN CN201210344080.3A patent/CN102835735B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1374338A (en) * | 2001-03-12 | 2002-10-16 | 中国科学院大连化学物理研究所 | Emulsifying and internal gelifying process of preparing calcium alginate gel beads |
| CN101049187A (en) * | 2007-05-18 | 2007-10-10 | 云南烟草科学研究院 | Composite filter tip of two layer molding paper containing additive |
| CN101810595A (en) * | 2009-02-25 | 2010-08-25 | 中国中化股份有限公司 | Preparation method of calcium alginate microcapsule |
| CN102068038A (en) * | 2010-12-31 | 2011-05-25 | 贵州中烟工业有限责任公司 | Method for preparing heat-sensitive moisture-retaining central line filter stick of cigarette |
| CN102140387A (en) * | 2011-01-20 | 2011-08-03 | 深圳市如烟生物科技有限公司 | Method for preparing microcapsule essence for cigarette |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102835735A (en) | 2012-12-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102835735B (en) | Temperature-sensitive micro capsule as well as preparation method and application of temperature-sensitive micro capsule | |
| WO2019201290A1 (en) | Method for preparing low-suction-resistance polylactic acid tow filter rod used for reducing temperature of cigarette vapor | |
| CN100401929C (en) | Improvements relating to smoking articles | |
| CN102839052B (en) | Tobacco flavoring essence temperature sensitive microcapsule, as well as preparation method and application thereof | |
| CN108308695B (en) | Smoking agent, preparation method thereof and cigarette containing smoking agent | |
| CN105595417A (en) | Linear composite gel fragrance controlled-release filter stick and preparation method and application thereof | |
| CN106387995A (en) | Controlled-release filter tip containing aroma-increasing and moisture-retaining sheets | |
| CN102150943B (en) | Mint tobacco flake threads and method for preparing mint tobacco flake threads | |
| CN110801049B (en) | Cigarette filter tip aroma sustained-release particles and preparation method thereof | |
| CN109123775A (en) | A kind of heating of the perfume (or spice) of solid-state containing herbal odor type pearl is not burnt cigarette and preparation method thereof | |
| CN104470384A (en) | Smoking article mouthpiece including aerogel | |
| CN106723341A (en) | Fragrance slow-release material composition and sustained release spices colloid and application thereof | |
| CN112545047B (en) | Plant polysaccharide aerogel heating non-combustion flavor smoke generating material and preparation method thereof | |
| CN105540073A (en) | Brittle capsule for cigarettes and preparation method thereof | |
| CN112716041A (en) | Aerosol-generating article of particulate construction | |
| CN108851215B (en) | Cigarette filter rod containing double solid flavor bead particles and preparation method thereof | |
| CN113331469A (en) | Multi-particle smoking-based smoking segment, cigarette comprising same and preparation method | |
| CN113412063B (en) | Special-shaped tobacco particles and preparation method thereof, tobacco product and preparation method thereof | |
| CN110754688A (en) | Fragrant bead capable of pinching and breaking hollow large-particle filter stick and preparation method thereof | |
| CN111053277A (en) | Product generated by heating non-combustible aerosol | |
| CN115039911A (en) | Natural plant essence carrier for cigarette, cigarette filter stick and cigarette cartridge | |
| CN108851192A (en) | The reconstituted tobacoo and production technology of the high porosity with minty note applied to low temperature cigarette | |
| CN108851208A (en) | A kind of cigarette filter rod and preparation method thereof | |
| CN102524960B (en) | A kind of preparation method of harm reduction cigarette filter | |
| CN115191644A (en) | Preparation method of tobacco original aroma sol generation matrix rod |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170112 Address after: Nanping Nan'an District of Chongqing City Road 400060 No. 2 Patentee after: CHONGQING CHINA TOBACCO INDUSTRIAL CO., LTD. Patentee after: CHINA TOBACCO SICHUAN INDUSTRIAL CO., LTD. Address before: 610017 Jackie Chan Road, Chengdu economic and Technological Development Zone, Longquanyi District, Sichuan, China, No. 2, No. Patentee before: China Tobacco Chuanyu Industry Co., Ltd. |