EP4127312A1 - Umhüllungspapier für rauchartikel mit verbessertem aschebild - Google Patents
Umhüllungspapier für rauchartikel mit verbessertem aschebildInfo
- Publication number
- EP4127312A1 EP4127312A1 EP21715827.8A EP21715827A EP4127312A1 EP 4127312 A1 EP4127312 A1 EP 4127312A1 EP 21715827 A EP21715827 A EP 21715827A EP 4127312 A1 EP4127312 A1 EP 4127312A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- wrapping paper
- calcium carbonate
- carbonate particles
- loaded
- mass
- 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.)
- Granted
Links
- 230000000391 smoking effect Effects 0.000 title claims abstract description 56
- 230000015572 biosynthetic process Effects 0.000 title description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 291
- 239000002245 particle Substances 0.000 claims abstract description 153
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 142
- 229920003043 Cellulose fiber Polymers 0.000 claims abstract description 88
- 239000000835 fiber Substances 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 32
- 239000011248 coating agent Substances 0.000 claims description 31
- 238000000576 coating method Methods 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 24
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims description 21
- 239000000945 filler Substances 0.000 claims description 21
- 235000019504 cigarettes Nutrition 0.000 claims description 19
- 230000035699 permeability Effects 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 11
- 239000000443 aerosol Substances 0.000 claims description 9
- 229920002472 Starch Polymers 0.000 claims description 8
- 235000019698 starch Nutrition 0.000 claims description 8
- 239000008107 starch Substances 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- 229940088417 precipitated calcium carbonate Drugs 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011121 hardwood Substances 0.000 claims description 6
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 244000004281 Eucalyptus maculata Species 0.000 claims description 4
- 229920000433 Lyocell Polymers 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- -1 oxides Chemical class 0.000 claims description 4
- 235000018185 Betula X alpestris Nutrition 0.000 claims description 3
- 235000018212 Betula X uliginosa Nutrition 0.000 claims description 3
- 240000000731 Fagus sylvatica Species 0.000 claims description 3
- 235000010099 Fagus sylvatica Nutrition 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000001508 potassium citrate Substances 0.000 claims description 3
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 235000015870 tripotassium citrate Nutrition 0.000 claims description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 3
- 229940038773 trisodium citrate Drugs 0.000 claims description 3
- OMDQUFIYNPYJFM-XKDAHURESA-N (2r,3r,4s,5r,6s)-2-(hydroxymethyl)-6-[[(2r,3s,4r,5s,6r)-4,5,6-trihydroxy-3-[(2s,3s,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxan-2-yl]methoxy]oxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)[C@H](O)[C@H](O)[C@H](O)O1 OMDQUFIYNPYJFM-XKDAHURESA-N 0.000 claims description 2
- JKRDADVRIYVCCY-UHFFFAOYSA-N 2-hydroxyoctanoic acid Chemical class CCCCCCC(O)C(O)=O JKRDADVRIYVCCY-UHFFFAOYSA-N 0.000 claims description 2
- 244000215068 Acacia senegal Species 0.000 claims description 2
- 244000198134 Agave sisalana Species 0.000 claims description 2
- 244000025254 Cannabis sativa Species 0.000 claims description 2
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 2
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical class [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 claims description 2
- 240000000491 Corchorus aestuans Species 0.000 claims description 2
- 235000011777 Corchorus aestuans Nutrition 0.000 claims description 2
- 235000010862 Corchorus capsularis Nutrition 0.000 claims description 2
- 229920000742 Cotton Polymers 0.000 claims description 2
- 229920000926 Galactomannan Polymers 0.000 claims description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical class OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 2
- 244000299507 Gossypium hirsutum Species 0.000 claims description 2
- 229920000084 Gum arabic Polymers 0.000 claims description 2
- 240000006240 Linum usitatissimum Species 0.000 claims description 2
- 235000004431 Linum usitatissimum Nutrition 0.000 claims description 2
- 229920000881 Modified starch Polymers 0.000 claims description 2
- 240000000907 Musa textilis Species 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 241000218657 Picea Species 0.000 claims description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims description 2
- 241000018646 Pinus brutia Species 0.000 claims description 2
- 235000011613 Pinus brutia Nutrition 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920000297 Rayon Polymers 0.000 claims description 2
- 239000000205 acacia gum Substances 0.000 claims description 2
- 235000010489 acacia gum Nutrition 0.000 claims description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
- 235000010443 alginic acid Nutrition 0.000 claims description 2
- 229920000615 alginic acid Polymers 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 235000009120 camo Nutrition 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 235000010980 cellulose Nutrition 0.000 claims description 2
- 235000005607 chanvre indien Nutrition 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims description 2
- 150000001860 citric acid derivatives Chemical class 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-L fumarate(2-) Chemical class [O-]C(=O)\C=C\C([O-])=O VZCYOOQTPOCHFL-OWOJBTEDSA-L 0.000 claims description 2
- 239000011487 hemp Substances 0.000 claims description 2
- 239000003906 humectant Substances 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 150000003893 lactate salts Chemical class 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 150000004701 malic acid derivatives Chemical class 0.000 claims description 2
- 235000019426 modified starch Nutrition 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 239000004627 regenerated cellulose Substances 0.000 claims description 2
- 150000003873 salicylate salts Chemical class 0.000 claims description 2
- 150000004760 silicates Chemical class 0.000 claims description 2
- 239000011122 softwood Substances 0.000 claims description 2
- 150000003890 succinate salts Chemical class 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 150000003892 tartrate salts Chemical class 0.000 claims description 2
- 244000061176 Nicotiana tabacum Species 0.000 claims 1
- 239000002956 ash Substances 0.000 description 40
- 241000208125 Nicotiana Species 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 241000218631 Coniferophyta Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 238000003703 image analysis method Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/675—Oxides, hydroxides or carbonates
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
- A24D1/00—Cigars; Cigarettes
- A24D1/02—Cigars; Cigarettes with special covers
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
- A24D1/00—Cigars; Cigarettes
- A24D1/20—Cigarettes specially adapted for simulated smoking devices
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H15/00—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
- D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/385—Oxides, hydroxides or carbonates
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/54—Starch
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
Definitions
- the invention relates to a wrapping paper for smoking articles which contains cellulose fibers loaded with filler particles which give the paper particularly favorable properties.
- the ashes of a smoking article made from this wrapping paper have a better appearance.
- a common smoking article comprises a cylindrical tobacco rod containing an aerosol forming material, typically tobacco or a tobacco-based material, encased in a wrapping material.
- the wrapping material comprises a paper, that is to say a web-like material which contains cellulose fibers.
- a smoking article can comprise a filter that is wrapped in a filter wrapping paper, and a tipping paper that wraps around the filter and part of the tobacco rod at the same time and thus connects the filter and the tobacco rod to one another.
- the aerosol-forming material When the smoking article is used, the aerosol-forming material is heated or burned so that an aerosol is formed which, when the smoking article is used, flows through the smoking article and is inhaled by the consumer.
- the smoking article can also comprise components that convey the aerosol or cool the aerosol, and are typically arranged between the tobacco rod and the filter.
- the wrapping paper of the tobacco rod is thermally degraded.
- the wrapping paper can discolor and it partially loses its mechanical stability, which is why the optical appearance of the smoking article changes.
- This appearance of a used or in use smoking article and in particular its tobacco rod is referred to as an ash image. From the consumer's point of view, it is a sign of a high quality of the smoking article if it has a good ash appearance, that is, if the tobacco rod essentially retains its cylindrical shape after being burned or heated, of a uniform white color and no dark particles, for example tobacco particles or their ashes, protrude through the wrapping material.
- the basis weight of the wrapping paper can be increased or fire salts such as trisodium citrate or tripotassium citrate can be added or their content increased.
- these possibilities have the disadvantage that they increase the proportion of non-tobacco materials in the smoking article and thus can negatively change the taste of the smoking article.
- wrapping paper should be understood to mean any paper that wraps the smoking article or at least one of its components.
- the invention is based on the object of providing a wrapping paper for smoking articles available that gives the smoking article a good ash appearance without the need to increase the mass of the wrapping paper significantly or add unusual components to the wrapping paper.
- the wrapping paper contains cellulose fibers which are loaded with calcium carbonate particles.
- Cellulose fibers and calcium carbonate particles are common components of wrapping papers for smoking articles, however, in the prior art, the calcium carbonate particles are not connected to the cellulose fibers, but are only arranged between the cellulose fibers.
- Such calcium carbonate particles are referred to as “free calcium carbonate particles” in order to distinguish them from the calcium carbonate particles with which the cellulose fibers are loaded, that is, they are connected.
- Such cellulose fibers loaded with calcium carbonate particles can be for example, by precipitation of the calcium carbonate with the simultaneous presence of the cellulose fibers with appropriate guidance of the precipitation process.
- the wrapping paper according to the invention comprises cellulose fibers loaded with calcium carbonate particles, the mass of the cellulose fibers loaded with calcium carbonate particles being at least 1% of the weight of the wrapping paper and the calcium carbonate particles in the cellulose fibers loaded with calcium carbonate particles at least 5% and at most 80% of the mass of the calcium carbonate particles loaded Make up pulp fibers.
- the inventor assumes that the calcium carbonate particles connected to the cellulose fibers form a framework that remains after the thermal degradation of the cellulose fibers and thus ensures the stability of the thermally degraded wrapping paper and thus prevents, for example, ash particles of the aerosol-forming material from penetrating the wrapping paper can. In this way, the overall ash appearance of the smoking article is improved.
- the free calcium carbonate particles do not form such framework-like structures and therefore do not contribute to the same extent to improving the ash structure. Therefore, with a comparable ash pattern, the mass of calcium carbonate particles in the wrapping paper can be reduced by using pulp fibers loaded with calcium carbonate particles, or the mass of the wrapping paper can be reduced overall. This also reduces the influence of the wrapping paper on the taste of the smoking article.
- the wrapping paper according to the invention offers particular advantages if it has a high level of air permeability.
- a conventional wrapping paper with high air permeability has more and larger pores and is therefore even more difficult to form a mechanically stable framework during thermal degradation, which is why the ash appearance is often unacceptable. This effect can be largely compensated for by the cellulose fibers loaded with calcium carbonate particles in the wrapping paper according to the invention.
- all of the pulp fibers in the wrapping paper are loaded with calcium carbonate particles.
- the wrapping paper contains not only the cellulose fibers loaded with calcium carbonate particles but also cellulose fibers that are not loaded with calcium carbonate particles.
- the proportion of such cellulose fibers is preferably at least 1% and at most 95%, particularly preferably at least 10% and at most 80% and very particularly preferably at least 20% and at most 70%, each based on the mass of the wrapping paper.
- Both the cellulose fibers and the cellulose fibers loaded with calcium carbonate particles can be made from coniferous woods such as spruce, pine or fir, from hardwoods such as eucalyptus tus, birch or beech, or from other plants such as hemp, flax, jute, sisal, abaca or cotton.
- the cellulose fibers can also be obtained from regenerated cellulose, such as viscose fibers, modal fibers, Lyocell® or Tencel®. Mixtures of cellulose fibers of various origins can be used.
- the wrapping paper according to the invention contains at least i% pulp fibers loaded with calcium carbonate particles.
- the wrapping paper can be uncoated or coated.
- the pulp fibers loaded with calcium carbonate particles can be in the bulk of the wrapping paper or in an optional coating on the wrapping paper. If there are cellulose fibers loaded with calcium carbonate particles in the mass of the wrapping paper, the proportion of cellulose fibers loaded with calcium carbonate particles is preferably higher and is at least 5% and at most 80% and particularly preferably at least 30% and at most 70%, each based on the mass of the Wrapping paper. If the cellulose fibers loaded with calcium carbonate particles are exclusively in the optional coating of the wrapping paper, then the proportion of cellulose fibers loaded with calcium carbonate particles is preferably at least 1% and at most 30% and particularly preferably at least 2% and at most 25%, each based on the mass of the wrapping paper.
- a high proportion of cellulose fibers loaded with calcium carbonate particles makes it possible to reduce the proportion of free calcium carbonate particles and at the same time to improve the ash structure. It is even possible that, through the use of the cellulose fibers loaded with calcium carbonate particles, the total content of the calcium carbonate particles in the wrapping paper can be reduced without deteriorating the ash appearance.
- the cellulose fibers loaded with calcium carbonate particles form fewer hydrogen bonds, however, so that the tensile strength of the wrapping paper can decrease overall. Therefore, the amount of pulp fibers loaded with calcium carbonate particles in the wrapping paper cannot be chosen arbitrarily high, especially when the pulp fibers are loaded with a large amount of calcium carbonate particles.
- the cellulose fibers loaded with calcium carbonate particles are preferably obtained from hardwoods such as eucalyptus, birch or beech. These cellulose fibers are generally less mechanically stressed during the production of the wrapping paper, for example during grinding, so that fewer calcium carbonate particles can be lost in the production process.
- the calcium carbonate particles of the cellulose fibers loaded with calcium carbonate particles are preferably precipitated calcium carbonate particles and particularly preferably precipitated calcium carbonate particles with a rhombohedral structure. These structures can be produced particularly well on the cellulose fibers in a precipitation process.
- the mass of the calcium carbonate particles based on the mass of the pulp fibers loaded with calcium carbonate particles is at least 5% and at most 80% in the wrapping paper according to the invention. However, it is preferably at least 10% and at most 70% and very particularly preferably at least 20% and at most 60%. In the preferred intervals, there is a particularly favorable compromise between the desired improvement in the ash pattern and the undesired reduction in tensile strength.
- the wrapping paper can also contain free fillers that are not associated with the pulp fibers.
- the proportion of free fillers is preferably at least 1% and at most 40%, particularly preferably at least 5% and at most 35% and very particularly preferably at least 10% and at most 30%, each based on the mass of the wrapping paper.
- These fillers can serve to influence the whiteness, opacity and pore structure of the wrapping paper.
- a high content of free fillers reduces the tensile strength of the wrapping paper. With the free fillers there is also the risk that they will settle as dust in further processing processes, for example when producing a smoking article from the wrapping paper, and thus shorten the necessary cleaning intervals for the machines. In the preferred intervals, the advantages of using free fillers predominate.
- the free fillers in the wrapping paper are preferably carbonates, oxides, hydroxides and silicates.
- Particularly preferred fillers are calcium carbonate, magnesium carbonate, magnesium oxide, magnesium hydroxide, aluminum hydroxide, titanium dioxide, talc, kaolin, calcined kaolin and mixtures thereof. Precipitated calcium carbonate is very particularly preferred.
- the ratio between the mass of calcium carbonate particles contained in the pulp fibers loaded with calcium carbonate particles and the mass of free filler particles in the wrapping paper can be important for adjusting the ash appearance in relation to other properties such as whiteness, opacity and tensile strength.
- the ratio of the mass of calcium carbonate particles contained in the pulp fibers loaded with calcium carbonate particles and the mass of free filler particles in the wrapping paper is preferably 5:95 to 100: 0, particularly preferably 10:90 to 80:20 and whole it is particularly preferably 10:90 to 50:50.
- the wrapping paper can also contain fire salts.
- the fire salts influence the rate of thermal degradation of the wrapping paper and can also help to improve the ash appearance, because they sometimes act as an adhesive or as a sintering aid between the free filler particles and thus improve the mechanical stability of the thermally degraded wrapping paper.
- Fire salts are preferably used in each wrapping paper that wraps the tobacco rod.
- the proportion of fire salts in the wrapping paper can be chosen variably, the proportion preferably being at least 0.3% and at most 7%, particularly preferably at least 0.5% and at most 5% and very particularly preferably at least 0.5% and at most 3% carries, each based on the mass of the wrapping paper.
- the fire salts can preferably be selected from the group consisting of citrates, malates, tartrates, acetates, nitrates, succinates, fumarates, gluconates, glycolates, lactates, oxyalates, salicylates, ⁇ -hydroxycaprylates, phosphates, chlorides and hydrogen carbonates, and mixtures thereof and particularly preferably from the group consisting of trisodium citrate, tripotassium citrate and mixtures thereof.
- the wrapping paper is essentially provided over its entire surface with a coating that contains free calcium carbonate particles and / or cellulose fibers loaded with calcium carbonate particles.
- “Coated over the entire area” means that a full-area coating is intended or at least 95% of the area is coated.
- a suitably selected coating can further improve the ash appearance without adding unusual components to the wrapping paper.
- the coating increases the content of calcium carbonate particles on the paper surface, so that a stable framework can be formed more easily, which ensures the mechanical stability of the wrapping paper after its thermal degradation.
- the coating can be carried out by applying a composition using methods known from the prior art, such as, for example, in a size press or a film press of a paper machine, in coating or coating units or by means of a printing machine, in particular a gravure printing machine.
- a composition suitable for producing the coating comprises a solvent, preferably water, and calcium carbonate particles or cellulose fibers loaded with calcium carbonate particles.
- Such calcium carbonate particles which do not belong to the calcium carbonate particles of the loaded cellulose fibers, are referred to as free calcium carbonate particles, as is the case with the wrapping paper itself.
- the proportion of free calcium carbonate particles in the composition can preferably be at least 0% and at most 40%, particularly preferably at least 5% and at most 30%, each based on the mass of the composition.
- the proportion of cellulose fibers loaded with calcium carbonate particles can preferably be at least 0% and at most 10%, particularly preferably at least 1% and at most 7%, in each case based on the mass of the composition.
- the above-mentioned coating corresponds to the applied composition in the dried state, ie when, in particular, the solvent has volatilized.
- the composition should contain a binder in order to fix the free calcium carbonate particles to the wrapping paper. This binder then also remains in the coating formed by the application of the composition.
- a binding agent is not absolutely necessary, but is also preferable for better fixation.
- the binder is particularly preferably selected from the group consisting of starch, starch derivatives, carboxymethyl cellulose, cellulose derivatives, polyvinyl alcohol, galactomannan, gum arabic, alginates and mixtures thereof.
- the starch is very particularly preferably a mechanically fragmented and chemically crosslinked starch because it is not soluble in water in the chemical sense and therefore penetrates less into the paper structure and thus less reduces the air permeability of the wrapping paper.
- the person skilled in the art can choose the amount of binder from experience, in particular with regard to the requirements of the application process.
- the composition can comprise further components which the person skilled in the art can suitably choose, including, for example, fire salts, dyes, flavorings, humectants, such as glycerol or propylene glycol, or substances for influencing the viscosity.
- the composition can be applied to one or both sides of the wrapping paper. However, the composition is preferably applied to the side that is on the outside of the smoking article made therefrom. This side is generally already known in the manufacture of the wrapping paper and in most cases the side facing away from the wire of the paper machine. The composition is therefore preferably applied to the side of the wrapping paper facing away from the wire of the paper machine, which side is also referred to as the top side.
- the mass per unit area of the coating is preferably at least 0.5 g / m 2 and at most 10 g / m 2 , particularly preferably at least 1 g / m 2 and at most 5 g / m 2 .
- the mass of the free calcium carbonate particles and the calcium carbonate particles of the loaded cellulose fibers in the coating taken together is at least 1% and at most 20%, particularly preferably at least 2% and at most 15% of the mass of the coated wrapping paper.
- the wrapping paper preferably also contains pulp fibers loaded with calcium carbonate particles, the mass of the pulp fibers loaded with calcium carbonate particles in the wrapping paper without the coating preferably at least 1% and at most 70%, particularly preferably at least 1% and at most 60% of the mass of the wrapping paper piers, and the calcium carbonate particles in the calcium carbonate particles NEN cellulose fibers make up at least 10% and at most 6o% of the mass of the cellulose fibers loaded with calcium carbonate particles.
- the wrapping paper according to the invention can also be part of a laminate, particularly preferably a laminate with a further material with a thermal conductivity that exceeds that of the wrapping paper by a factor of at least two, preferably at least four.
- the further material of the laminate is formed by an aluminum foil.
- Such laminates can primarily be used in smoking articles in which the aerosol-forming material is only heated but not burned in order to prevent the smoking article from being lit and smoked like an ordinary cigarette.
- the smoking article is a cigarette and the wrapping paper additionally has patterns or structures, particularly preferably bands printed in the circumferential direction, in order to reduce the tendency of the smoking article to ignite measured in accordance with ISO 12863: 2010.
- the basis weight of the wrapping paper according to the invention is preferably at least 15 g / m 2 and at most 150 g / m 2 , particularly preferably at least 20 g / m 2 and at most 120 g / m 2 , very particularly preferably at least 20 g / m 2 and at most 40 g / m 2 .
- the basis weight of the wrapping paper can be determined according to ISO 536: 2019, whereby a coating, if present, counts as part of the basis weight.
- the thickness of the wrapping paper according to the invention is preferably at least 10 ⁇ m and at most 200 ⁇ m, preferably at least 15 ⁇ m and at most 120 ⁇ m and very particularly preferably at least 30 ⁇ m and at most 100 ⁇ m.
- the thickness can be determined according to ISO 534: 2011 on a single layer of the wrapping paper.
- a coating if present, is part of the thickness of the wrapping paper.
- the mechanical properties of the wrapping paper according to the invention can be important for the production of a smoking article from this wrapping paper.
- the essential mechanical properties include tensile strength, elongation at break and energy absorption capacity, all of which can be determined according to ISO 1924-2: 2008.
- the tensile strength of the wrapping paper is preferably at least 7 N / 15 mm, particularly preferably at least 8 N / 15 mm and very particularly preferably at least 10 N / 15 mm. Since the expenditure of material and energy in papermaking to increase the tensile strength is high, it is advantageous if the tensile strength is at most 100 N / 15 mm, preferably at most 80 N / 15 mm and particularly preferably at most 70 N / 15 mm.
- the tensile strength can be increased above all by increasing the weight per unit area and increasing the proportion of cellulose fibers, as well as by more intensive grinding of the cellulose fibers.
- the wrapping paper has a certain stretchability.
- the elongation at break of the wrapping paper according to the invention is preferably at least 0.9% and at most 3%, particularly preferably at least 1% and at most 2%.
- the energy absorption capacity describes how much energy is required to tear the paper.
- the energy absorption capacity is at least 3 J / m 2 and at most 50 J / m 2 and very particularly preferably at least 3.5 J / m 2 and at most 35 J / m 2 .
- the whiteness (ISO brightness) of the wrapping paper can be important for its visual appearance and also for the ash appearance. It is measured in accordance with ISO 2470-1: 2016. In general, white wrapping papers are preferred for optical reasons, so that the whiteness of the wrapping paper according to the invention is at least 80% and particularly preferably at least 90%.
- the whiteness can be influenced, for example, by choosing the free fillers; in particular, the whiteness can be increased considerably with titanium dioxide.
- the opacity of the wrapping paper is also important for the visual appearance.
- a high opacity is generally favorable because components of the smoking article are then not visible through the wrapping paper.
- the opacity is measured according to ISO 2471: 2008.
- the opacity of the wrapping paper is preferably at least 70% and particularly preferably at least 80%.
- the opacity can also be increased by increasing the amount of free fillers in the wrapping paper.
- its air permeability is important. In such applications, for example, when using the smoking article, air should flow through the wrapping paper into the smoking article in order to dilute the aerosol.
- the air permeability can be measured according to ISO 2965: 2019.
- the air permeability of the wrapping paper according to the invention is preferably at least 0 cm 3 / (cm 2 -min-kPa) and at most 300 cm 3 / (cm 2 -min-kPa), particularly preferably at least 10 cm 3 / (cm 2 -min-kPa ) and at most 250 cm 3 / (cm 2 -min-kPa) and very particularly preferably at least 20 cm 3 / (cm 2 -min-kPa) and at most 150 cm 3 / (cm 2 -min-kPa).
- the wrapping paper is coated, its air permeability is lower and carries at most 120 cm 3 / (cm 2 -min-kPa), particularly preferably at most 100 cm 3 / (cm 2 -min-kPa) and very particularly preferably at most 80 cm 3 / (cm 2 -min-kPa).
- the wrapping paper according to the invention comprises pulp fibers loaded with calcium carbonate particles, the mass of the pulp fibers loaded with calcium carbonate particles being at least 10% of the mass of the wrapping paper and the calcium carbonate particles in the pulp fibers loaded with calcium carbonate particles being at least 20% and at most 80% of the Make up the mass of the cellulose fibers loaded with calcium carbonate particles and the wrapping paper has an air permeability according to ISO 2965: 2019 of at least 50 cm 3 / (cm 2 -min-kPa) and at most 300 cm 3 / (cm 2 -min-kPa).
- a smoking article according to the invention comprises an aerosol-forming material and the wrapping paper according to the invention.
- the aerosol-forming material comprises tobacco and said wrapping paper wraps the aerosol-forming material.
- the smoking article is a smoking article according to the invention in which the aerosol-forming material is only heated but not burned.
- the smoking article is a cigarette and the wrapping paper is a cigarette paper.
- FIGURES 1 shows an example of an electron microscope image of coarse
- Calcium carbonate particles loaded cellulose fibers the calcium carbonate particles making up about 20% of the mass of the cellulose fibers loaded with calcium carbonate particles.
- Calcium carbonate particles loaded cellulose fibers the calcium carbonate particles making up about 20% of the mass of the cellulose fibers loaded with calcium carbonate particles.
- Fig. 3 shows the ash picture of three filter cigarettes made from a wrapping paper not according to the invention.
- FIG. 4 shows the ash pattern of three filter cigarettes made from a wrapping paper according to the invention.
- a total of 14 wrapping papers according to the invention labeled A to K and X to Z, were produced, the composition of the wrapping papers being given in Table 1.
- "SW” in% means the proportion of pulp fibers from coniferous woods
- "HW” in% the proportion of pulp fibers from hardwoods
- "CF” in% the proportion of pulp fibers loaded with calcium carbonate particles
- "FI” in% the proportion free fillers. The percentages are based on the weight of the wrapping paper.
- the pulp fibers from softwood and hardwood are standard products available on the market.
- the cellulose fibers loaded with calcium carbonate particles were obtained from Schaefer Kalk. All of the free filler was formed by precipitated calcium carbonate particles.
- the mass of the calcium carbonate particles in the pulp fibers loaded with calcium carbonate particles is indicated in table 1 under “CCP” in%, based on the mass of the cellulose fibers loaded with calcium carbonate particles.
- the size of these particles is also specified as “fine” or “coarse”.
- FIG. 1 shows an electron microscope image of pulp fibers loaded with coarse calcium carbonate particles
- FIG. 2 shows an electron microscope image of cellulose fibers loaded with fine calcium carbonate particles, as they were both used to produce some wrapping papers according to the invention.
- the mass fraction of calcium carbonate particles in the cellulose fibers loaded with calcium carbonate particles from FIGS. 1 and 2 was about 17.3%.
- the pulp fibers were formed by pulp fibers from eucalyptus.
- the wrapping paper X was identical to the wrapping paper REF, and the wrapping papers Y and Z were identical to the wrapping paper G.
- the wrapping paper Y was coated over the entire surface with a composition of 89% water, 5.5% mechanically fragmented and chemically crosslinked starch and 5.5% free calcium carbonate particles, the percentages being based on the mass of the composition.
- the wrapping papers X and Z were completely coated with a composition of 95.5% water, 1% mechanically fragmented and chemically crosslinked starch and 3.5% fibers loaded with calcium carbonate particles, the percentages being based on the mass of the composition. After the composition had been applied and dried, a mass of about 2 g / m 2 remained on each of the wrapping papers.
- the mechanically fragmented, chemically crosslinked starch can be obtained, for example, from Emsland-Starke GmbH.
- smoking articles in the form of filter cigarettes with a diameter of about 7.8 mm and a length of 83 mm were produced.
- the tobacco used was an American blend and the wrapping papers each wrapped the tobacco.
- the ash appearance of these smoking articles was evaluated by an image analysis method. In doing so, three of each cigarette were lit in a vertical position and the tobacco had to be completely smoldered. A digital image was then taken of each cigarette under constant light conditions in front of a neutral background. Image analysis software then determined the proportion of non-white areas in the area of the smoldered tobacco rod.
- the proportion of these non-white areas in relation to the total area of the smoldered tobacco rod is expressed as a percentage and referred to as the “ash index”, with an average value being formed from the images of three cigarettes in each case.
- FIG. 3 shows the ash pattern of three filter cigarettes made from the wrapping paper REF, which is not according to the invention.
- FIG. 4 shows the ash pattern of three filter cigarettes which were manufactured from the wrapping paper K according to the invention. Even without quantifying the ash pattern by image analysis, the difference is already clearly visible.
- wrapping papers A to K according to the invention was to achieve properties that were as similar as possible to the wrapping paper REF not according to the invention in order to be able to clearly show the positive effect of the cellulose fibers loaded with calcium carbonate particles.
- the examples are therefore not to be understood as a restriction of the invention and the person skilled in the art is able to produce wrapping papers according to the invention with, for example, different composition, different weight per unit area, different thickness, different air permeability or other mechanical or optical properties in the claimed range.
- the wrapping papers A to K according to the invention are very similar to the wrapping paper REF not according to the invention in terms of weight per unit area, thickness, elongation at break, whiteness and opacity.
- the tensile strength and thus also the energy absorption capacity of the wrapping papers A to K are somewhat smaller than in the case of the wrapping paper REF, which is not according to the invention. This is caused by the cellulose fibers loaded with calcium carbonate particles, since the calcium carbonate particles on the cellulose fibers prevent the formation of hydrogen bonds between the cellulose fibers and thus reduce the tensile strength of the wrapping paper.
- the air permeability of the wrapping papers A to K is higher than that of the wrapping paper not according to the invention. Despite this higher air permeability, the cigarettes made from the wrapping papers A to K have a better ash pattern than the cigarettes made from the wrapping paper REF. This shows that with high air permeability the use of cellulose fibers loaded with calcium carbonate particles offers a very special advantage.
- the person skilled in the art can of course reduce the air permeability of the wrapping papers A to K, for example by more intensive grinding of the cellulose fibers, and thus set the same value as for the wrapping paper REF. It is to be expected that the ash index will then decrease even further and thus the ash structure will improve even further.
- the coated wrapping papers X, Y and Z all show an improvement in the ash image.
- the papers X to Z also all have a higher tensile strength than the wrapping paper REF not according to the invention and than the uncoated wrapping papers A to K according to the invention, which is a further advantage of these embodiments.
- the wrapping papers according to the invention can achieve a significant improvement in the ash appearance without adversely affecting the other properties of the wrapping paper and without significantly increasing the mass of the wrapping paper or adding unusual components to the wrapping paper.
Abstract
Description
Claims
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DE102020108071.9A DE102020108071A1 (de) | 2020-03-24 | 2020-03-24 | Umhüllungspapier für Rauchartikel mit verbessertem Aschebild |
PCT/EP2021/057574 WO2021191277A1 (de) | 2020-03-24 | 2021-03-24 | Umhüllungspapier für rauchartikel mit verbessertem aschebild |
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US (1) | US20230136404A1 (de) |
EP (1) | EP4127312B1 (de) |
JP (1) | JP2023520152A (de) |
KR (1) | KR20220151691A (de) |
CN (1) | CN115315555A (de) |
BR (1) | BR112022017585A2 (de) |
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US5588446A (en) * | 1993-06-02 | 1996-12-31 | R. J. Reynolds Tobacco Company | Cigarette with improved cellulosic substrate |
DE10033979A1 (de) * | 2000-07-13 | 2002-01-24 | Voith Paper Patent Gmbh | Verfahren zum Beladen von Fasern mit Calciumcarbonat |
JP2003129399A (ja) | 2001-10-26 | 2003-05-08 | Oji Paper Co Ltd | たばこ用巻紙 |
JP2003155696A (ja) | 2001-11-16 | 2003-05-30 | Oji Paper Co Ltd | たばこ用巻紙 |
DE10325688A1 (de) | 2003-06-06 | 2004-12-23 | Voith Paper Patent Gmbh | Verfahren zum Beladen einer Faserstoffsuspension mit Kalziumkarbonat und Anordnung zur Durchführung des Verfahrens |
DE10351292A1 (de) * | 2003-10-31 | 2006-02-02 | Voith Paper Patent Gmbh | Verfahren zum Beladen einer Faserstoffsuspension und Anordnung zur Durchführung des Verfahrens |
DE102004045089A1 (de) * | 2004-09-17 | 2006-03-23 | Voith Paper Patent Gmbh | Verfahren und Vorrichtung zum Beladen einer Faserstoffsuspension |
CN101208476A (zh) * | 2005-07-12 | 2008-06-25 | 沃依特专利有限责任公司 | 用于在纤维料悬浮液中包含的纤维装填的方法 |
US8808503B2 (en) * | 2009-02-02 | 2014-08-19 | John Klungness | Fiber loading improvements in papermaking |
US9220297B2 (en) | 2009-08-07 | 2015-12-29 | R. J. Reynolds Tobacco Company | Materials, equipment, and methods for manufacturing cigarettes |
DE102013109386B3 (de) | 2013-08-29 | 2015-01-15 | Delfortgroup Ag | Effizient herstellbares Zigarettenpapier für selbstverlöschende Zigaretten, Verfahren zu seiner Herstellung sowie eine Zigarette |
US10112844B2 (en) * | 2014-03-31 | 2018-10-30 | Nippon Paper Industries Co., Ltd. | Calcium carbonate microparticles and processes for preparing them |
DE102015105882B4 (de) * | 2015-04-17 | 2017-06-08 | Delfortgroup Ag | Umhüllungspapier mit hohem Kurzfaseranteil und Rauchartikel |
EP3098202A1 (de) | 2015-05-28 | 2016-11-30 | Omya International AG | Verfahren zur erhöhung der opazität von gefälltem calciumcarbonat |
CN104957755B (zh) * | 2015-07-09 | 2016-11-30 | 川渝中烟工业有限责任公司 | 一种提高造纸法再造烟叶中碳酸钙留着率的方法 |
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JP2023520152A (ja) | 2023-05-16 |
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DE102020108071A1 (de) | 2021-09-30 |
US20230136404A1 (en) | 2023-05-04 |
BR112022017585A2 (pt) | 2022-10-18 |
KR20220151691A (ko) | 2022-11-15 |
CN115315555A (zh) | 2022-11-08 |
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