EP2445362B1 - Filmbildende zusammensetzung zum aufbringen auf zigarettenpapier - Google Patents

Filmbildende zusammensetzung zum aufbringen auf zigarettenpapier Download PDF

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Publication number
EP2445362B1
EP2445362B1 EP10729799.6A EP10729799A EP2445362B1 EP 2445362 B1 EP2445362 B1 EP 2445362B1 EP 10729799 A EP10729799 A EP 10729799A EP 2445362 B1 EP2445362 B1 EP 2445362B1
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EP
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Prior art keywords
film
weight
forming
composition
content
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EP10729799.6A
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German (de)
English (en)
French (fr)
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EP2445362A1 (de
Inventor
Dietmar Volgger
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Delfortgroup AG
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Delfortgroup AG
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Priority to PL10729799T priority Critical patent/PL2445362T3/pl
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    • 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
    • A24D1/02—Cigars; Cigarettes with special covers
    • A24D1/025—Cigars; Cigarettes with special covers the covers having material applied to defined areas, e.g. bands for reducing the ignition propensity
    • 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
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • 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
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/067—Use of materials for tobacco smoke filters characterised by functional properties
    • A24D3/068—Biodegradable or disintegrable
    • 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
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/08—Use of materials for tobacco smoke filters of organic materials as carrier or major constituent
    • A24D3/10—Use of materials for tobacco smoke filters of organic materials as carrier or major constituent of cellulose or cellulose derivatives

Definitions

  • the present invention relates to a composition having two or three film formers with mutually different average molecular weights for application to cigarette paper.
  • the present invention further relates to a cigarette paper to which the composition is applied in discrete areas, the areas being characterized by a value for diffusivity, and a cigarette comprising the cigarette paper which is characterized by values for self-solution.
  • the present invention also relates to a method for producing the cigarette paper and the cigarette.
  • the self - extinguishment (SE) value is determined by law (USA, Canada, Australia) using the standardized test in ASTM E2187-04.
  • the legal requirements require that an SE value of 75% or more (for 40 tested cigarettes, ie 30 must be extinguished) can be achieved. This is the lower limit of acceptable levels.
  • cigarette manufacturers need to ensure that the cigarettes, when tested by authorities, reach the SE> 75% threshold with very high probability. For the cigarette producers, therefore, a value of at least 85% is usually preferred.
  • the optimal goal that a manufacturer of cigarettes would like to achieve is to completely extinguish the cigarettes in the Ignition Strength test according to ASTM E2817-04, ie the SE value is 100%, but nevertheless no cigarette emanates from the ashtray during the normal smoking process. the FB value is also 100%. In practice, this goal is very difficult to achieve, which is why the limits for legally and technically acceptable values for SE and FB are lower.
  • compositions with film-forming substances are applied in discrete areas of the cigarette paper.
  • film formers film formers
  • the film-forming substances close the pores in the treated areas and thus reduce the access of oxygen to the cone of ember.
  • the application of the aqueous or non-aqueous solutions or suspensions is usually carried out by means of conventional printing processes, especially gravure or flexographic printing. Devices for applying the printing solutions can be integrated into the paper machine.
  • the printing solution also adds adjuvants to increase the opacity of the printed areas on the paper so that they are not visible on the cigarette.
  • white, inert powders with an average particle size between 0.5 and 3 ⁇ m are selected.
  • carbonates and oxides are used particularly frequently calcium carbonate (CaCO 3), aluminum hydroxide (Al (OH) 3), magnesium oxide (MgO) and magnesium carbonate (MgCO 3).
  • the extinction properties depend i.a. the pattern and extent of the treated areas. In particular, the fine adjustment of the self-extinguishing is done by the amount of film-forming substances that is applied: the larger the order amount, the more pores are closed.
  • a measure of the permeability of the treated areas is diffusivity, a transfer coefficient for gas concentration through the paper. While the values for SE and FB are properties of the finished cigarette, the diffusivity is a characteristic of the cigarette paper.
  • the diffusivity is directly related to the SE and FB values (Eitzinger, Bernhard and Harald Giener, The Effect of Thermal Decomposition of Banded Cigarette Paper on Ignition Strength Test Results.) Presentation CORESTA Congress, Abstract SSPT23, Shanghai, China, November 2 -7, 2008).
  • the amount applied can be easily increased by increasing the content of film-forming substances in the printing solution. As a result, the viscosity of the printing solution increases. The viscosity itself in turn affects the amount of film-forming substances that can be applied to the cigarette paper, so that there is a complicated relationship between the content of film-forming substances in the printing solution and the application quantity.
  • the viscosity of the printing solution significantly affects its processability in the printing process.
  • the application rate of the film-forming substances can not be readily increased without having to make an adjustment of the printing device if necessary.
  • a higher solids content also means less solvent in the printing solution, so that the drying capacity of the printing device must also be adjusted if necessary.
  • the US 2009/0120450 A1 discloses a cigarette paper having discrete areas treated with a film-forming composition, the film-forming composition containing a film former, in particular an alginate, and a polysaccharide, in particular a starch.
  • the US 2008/0115794 A1 discloses a cigarette paper on which a first and second material is applied.
  • the first material is a poliol, corn oil or corn syrup
  • the second material is at least one film-forming material.
  • the film-forming material may be hydroxypropylcellulose, hydroxypropylmethylcellulose, an alginate or a combination thereof.
  • it is proposed to mix an alginate having a comparatively low molecular weight with an alginate having a relatively high molecular weight, which acts as a thickening agent.
  • Such a thickener gives printing pastes having high viscosities between 15,000 and 100,000 centipoise, preferably 20,000 30,000 centipoise.
  • the object of the present invention is achieved by a film-forming composition for application to cigarette paper, comprising a solvent and two or three film formers selected from the group consisting of the film formers A, B and C, whose molecular weight distributions are statistically significantly different from each other, said The content of each film former in the composition is chosen to be such that the total content of the film formers in the composition is 15 to 30% by weight, preferably 22 to 27% by weight, and the viscosity of the composition is 13 to 22 s, preferably 17 , 5 to 19.5 s, measured with a flow cup DIN 4 at 70 ° C, is.
  • the content of each film former in the composition is selected to match the diffusivity in one or more discrete areas of the cigarette paper in which the composition is applied. 0.08 to 0.5 cm / s, preferably 0.2 to 0.4 cm / s, more preferably 0.25 to 0.35 cm / s, measured after heating the paper for 30 minutes at 230 ° C.
  • the film-forming composition comprises two film formers A and B or A and C or B and C.
  • the film-forming composition comprises three film formers A, B and C.
  • the film former A has an average molecular weight of 200,000 ⁇ 50,000 g / mol, preferably 200,000 ⁇ 30,000 g / mol, particularly preferably 200,000 ⁇ 10,000 g / mol.
  • the film former B has an average molecular weight of 600,000 ⁇ 150,000 g / mol, preferably 600,000 ⁇ 90,000 g / mol, particularly preferably 600,000 ⁇ 30,000 g / mol.
  • the film former C has an average molecular weight of 100,000 ⁇ 25,000 g / mol, preferably 100,000 ⁇ 15,000 g / mol, particularly preferably 100,000 ⁇ 5,000 g / mol.
  • the content of film former A is up to 25% by weight, preferably 5 to 15% by weight.
  • the content of film former B is up to 25% by weight, preferably 15 to 22% by weight.
  • the content of film former C is up to 20 wt .-%, preferably 2 to 15 wt .-%, particularly preferably 2 to 8 wt .-%.
  • the film formers A, B and / or C are independently selected from the group consisting of starch and starch degradation products, alginate, guar gum, pectin, polyvinyl alcohol and cellulose and derivatives thereof.
  • the film former A may be an alginate and the film former B may be a starch or a starch degradation product.
  • the film formers A and B or A and C or B and C or A, B and C are the same.
  • both film formers may be a starch or a starch degradation product or a derivative thereof.
  • all three film formers may be a starch or a starch degradation product or a derivative thereof.
  • the film formers A and / or B are a potato starch or a derivative thereof, preferably a carboxylated potato starch or a derivative thereof, and the solvent is an aqueous solvent or water.
  • the film former C is a degraded starch or a derivative thereof, preferably a maltodextrin or a derivative thereof, and the solvent is an aqueous solvent or water.
  • degraded starch or maltodextrin has the advantage of improving film formation. The addition of degraded starch or maltodextrin ensures that the film does not crack even after intensive drying. Cracks would promote the access of oxygen to the cone and are therefore disadvantageous.
  • the film-forming composition further comprises at least one or more adjuvants selected from the group consisting of carbonates and oxides, preferably from the group consisting of calcium carbonate, aluminum hydroxide, magnesium oxide and magnesium carbonate.
  • the content of auxiliaries is up to 15% by weight, preferably 5 to 10% by weight.
  • the total solids content comprising the film formers and optionally at least one adjuvant, is 15 to 45% by weight, preferably 22 to 37% by weight.
  • the object of the present invention is further achieved by a cigarette paper comprising one or more discrete regions in which a film-forming composition of the invention is applied, the diffusivity of the discrete regions being 0.08 to 0.5 cm / s, preferably 0, 2 to 0.4 cm / s, more preferably 0.25 to 0.35 cm / s, measured after heating the paper for 30 minutes at 230 ° C, is.
  • the application rate of the film-forming composition is 2.5 to 6 g / m 2 , preferably 3 to 4.5 g / m 2 , particularly preferably 4 g / m 2 .
  • the values for the application amount in g / m 2 refer to the area of the cigarette paper to which the film-forming composition has been applied.
  • the diffusivity of the areas where no film-forming composition is applied is 0.1 to 3 cm / s measured at room temperature.
  • the cigarette paper further comprises one or more brominated salts selected from the group consisting of citrates, malates, tartrates, acetates, nitrates, succinates, fumarates, gluconates, glycates, lactates, oxylates, salicylates, ⁇ -hydroxycaprylates and phosphates, preferably selected from the group consisting of sodium citrate and tripotassium citrate, wherein the content is particularly preferably up to 4 wt .-%.
  • the object of the present invention is further achieved by a cigarette comprising a cigarette paper of the invention.
  • the self- extinguishing value is more than 75%, preferably at least 85%, more preferably at least 95%, and the value measured in the free burn test is more than 50%, preferably at least 70%, more preferably at least 80%.
  • the term "statistically significant different” should be understood as follows. Two or more substances have statistically significantly different molecular weight distributions from each other when the ⁇ 2 homogeneity test applied to these molecular weight distributions shows that they are not identical with a significance level of 95%.
  • the ⁇ 2 homogeneity test is a standard statistical method that allows one to test the hypothesis that two or more distributions are identical. It belongs to the non-parametric tests and therefore does not require any prerequisites about the type of distribution.
  • the invention consists in using a mixture of two or three film-forming substances having different average molecular weights from each other, more specifically, having molecular weight distributions that differ statistically significantly from each other. It is known that the molecular weight of a substance affects the viscosity of its solution, but the relationship between solids content and viscosity is complicated even with individual substances and even more so with mixtures difficult to predict. It has now surprisingly been found that a solution can be prepared by the mixture of a high molecular weight starch and a low molecular weight starch and occasionally a medium molecular weight, the total content of film-forming substances and their viscosity can be adjusted independently by selecting the proportion of individual starches.
  • the properties of the film formed in the discrete regions can be specifically adapted without having to change the viscosity of the film-forming composition, the amount applied or the total content of film formers in the printing solution. This ensures proper processing by the applicator device without changing the settings. For example, for a given printing cylinder by varying the composition of the printing solution, a wide range of cigarette papers can be printed with the desired result.
  • the cigarette comprises a tobacco blend that smolders particularly fast and intense.
  • the principle also applies in reverse, i. to increase the diffusivity, less high molecular weight and more low molecular weight film forming substance should be used.
  • Starch A and B are carboxylated potato starch powders
  • the starch MD is an enzymatically degraded potato starch powder (maltodextrin).
  • the solvent used was water.
  • the printing solution also contained calcium carbonate, which is usually added to make the printed ribbons less visible.
  • the film-forming composition was applied in the form of tapes.
  • the printed bands were 6 mm wide and the center to center distance was 27 mm.
  • the bands were arranged at right angles to the running direction of the paper web.
  • the imprint was done with the help of a gravure printing unit. This is the preferred, technically frequently implemented variant, but any other desired printing geometry can also be used.
  • the cigarettes made from the cigarette paper had the following characteristics: length 84 mm scope 24.6 mm total weight 920 mg tobacco weight 650 mg tobacco blend American blend
  • the percentage means the proportion of the respective substance in percent by weight (wt .-%), based on the ready-made printing solution.
  • the printing solution of Experiment 1 consists of 5% by weight of starch MD, 22% by weight of starch B and 5% by weight of calcium carbonate (lime).
  • the starch content is therefore 27% by weight in total, the total solids content is 32% by weight, and it is supplemented with water to 100% by weight.
  • the viscosity is determined with an outlet cup DIN 4. The time is measured in seconds, which requires a defined volume of the pressure solution to escape through an opening in the bottom of the standard outlet cup. The viscosity is measured on the finished printing solution at 70 ° C.
  • the order quantity is the mass additionally present in the bands on the paper after drying in g / m 2 per printed unit area.
  • the measurement is carried out by weighing.
  • the diffusivity refers to the resistance to gas exchange due to a concentration difference in the area of the printed bands. It is closely related to the diffusion constant.
  • the diffusivity as indicated in Table 1, thus corresponds to the diffusion constant divided by the thickness of the paper.
  • the diffusivity thus describes how easily (high value) or how heavy (low value) oxygen can reach the ember cone through the cigarette paper. If the value is sufficiently low, then the cigarette will automatically extinguish. However, the cigarette paper is already subjected to thermal stress in the area of the glow cone when smoldering. It has therefore been shown that the informative value of this measured value can be significantly increased if the papers are previously heated. Therefore, the paper will be on for 30 minutes 230 ° C in a drying oven, for example in a drying cabinet ED53 from Binder, heated. The changes in the paper and also in the printed ribbons are irreversible, which is why the paper can first be allowed to cool down to determine the diffusibility in the area of the ribbons.
  • the SE value is the result of the standardized Ignition Strength Test according to ASTM E2187-04. In this test, a smoldering cigarette is placed on a pad of 10 layers of Whatman # 2 filter paper and it is determined if the cigarette is out. The percentage indicates how many cigarettes a sample of 40 pieces came from.
  • the FB value refers to the result of a non-standard test in which a smoldering cigarette is fixed in a horizontal position in a holder so that air can pass from all sides to the cigarette. So the cigarette is not on a surface.
  • This test simulates the glow of the cigarette in the ashtray. The percentage indicates how many cigarettes in a sample of 40 pieces will NOT go out in this test.
  • paper B differs from paper A in all its essential characteristics.
  • Table 2 ⁇ / u> printing solution attempt Thickness MD [%] Strength A [%] Strength B [%] Total strength [%] Lime [%] Viscosity [s] Application amount [g / m 2] Diffusivity D * [cm / s] SE [%] FB [%] 4 0 5 17 22 5 19.0 4.20 0,250 100 80 5 5 0 17 22 5 17.5 4.45 0,280 97.5 100
  • experiment 5 the medium molecular weight A of experiment 4 was replaced by a low molecular weight MD. Accordingly, the diffusivity increases from 0.250 cm / s to 0.280 cm / s. The test results show that satisfactory and optimal results could be achieved for the SE and FB values.
  • D * should be the value with which the paper, i. more precisely, the printed areas that are characterized.
  • the table shows that when using paper D (80 CU, test 7) instead of paper C (60 CU, test 6) at the same pressure solution, the diffusivity increases from 0.210 cm / s to 0.232 cm / s. Increasing the proportion of medium molecular weight A in relation to the low molecular weight MD (experiment 8), almost the same diffusivity can be achieved as in experiment 6.
  • Example 4 Influence of the filler content of the cigarette paper
  • Example 5 Influence of the burn salts in the cigarette paper
  • the table shows that when changing from paper A to paper C at the same pressure solution, the diffusivity of 0.354 cm / s (experiment 13) increases to 0.435 cm / s (experiment 14). In parallel, the SE value drops from 87.5% to 62.5%, which is below the acceptable value of 75%. Of the This is because Brandsalze accelerate the thermal decomposition of the paper and thus increase the diffusivity after heating the paper.
  • a double-walled tank for example from ENCO Energy Components GmbH, can be used, which can be heated with steam.
  • the tank should be equipped with a stirrer, for example consisting of a dispersing disk and two propeller stirrers.
  • a defined amount of water is fed into the tank, and with stirring, an appropriate amount of calcium carbonate, for example, 5 or 11 wt .-% of the composition is added.
  • the calcium carbonate is dispersed for about 5 minutes.
  • the suspension is heated to 50 ° C, and it is added to the appropriate amount of a starch mixture.
  • the temperature of the final composition is maintained at 90 ° C for about 20 minutes; she is ready for action.
  • FIG. 1 shows Thermogravimetriekurven (TGA curves) of the two starches A and B.
  • the samples are heated in a nitrogen atmosphere at a rate ( heat rate ) of 5 ° C / min up to 500 ° C, and the mass change ( weight loss ,%) is determined by simultaneous weighing of the sample.
  • FIG. 1 It can be seen that the higher molecular weight starch B somewhat slower, ie at higher temperatures, decomposes as the low molecular weight A. This makes starch B is able to withstand a thermal load on the cigarette paper longer, whereby the film formed on the cigarette paper longer intact remains. Thus, the diffusivity of the printed areas of the paper when using starch B is lower than when using the starch A. Therefore, you will choose the proportion of starch B then higher if you want to reduce the diffusivity.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Paper (AREA)
  • Cigarettes, Filters, And Manufacturing Of Filters (AREA)
EP10729799.6A 2009-06-25 2010-06-23 Filmbildende zusammensetzung zum aufbringen auf zigarettenpapier Active EP2445362B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL10729799T PL2445362T3 (pl) 2009-06-25 2010-06-23 Kompozycja błonotwórcza do nanoszenia na bibułkę papierosową

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009030546A DE102009030546B3 (de) 2009-06-25 2009-06-25 Filmbildende Zusammensetzung zum Aufbringen auf Zigarettenpapier, Zigarettenpapier, Zigarette sowie Verfahren zum Herstellen eines Zigarettenpapiers
PCT/EP2010/003872 WO2010149380A1 (de) 2009-06-25 2010-06-23 Filmbildende zusammensetzung zum aufbringen auf zigarettenpapier

Publications (2)

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EP2445362A1 EP2445362A1 (de) 2012-05-02
EP2445362B1 true EP2445362B1 (de) 2017-11-08

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EP10729799.6A Active EP2445362B1 (de) 2009-06-25 2010-06-23 Filmbildende zusammensetzung zum aufbringen auf zigarettenpapier

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US (1) US10349673B2 (ko)
EP (1) EP2445362B1 (ko)
KR (1) KR101806568B1 (ko)
CN (1) CN102458163B (ko)
BR (1) BRPI1007566B1 (ko)
CA (1) CA2765295C (ko)
DE (1) DE102009030546B3 (ko)
ES (1) ES2656819T3 (ko)
MY (1) MY172461A (ko)
PL (1) PL2445362T3 (ko)
WO (1) WO2010149380A1 (ko)

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DE102013109386B3 (de) * 2013-08-29 2015-01-15 Delfortgroup Ag Effizient herstellbares Zigarettenpapier für selbstverlöschende Zigaretten, Verfahren zu seiner Herstellung sowie eine Zigarette
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PL2445362T3 (pl) 2018-03-30
KR101806568B1 (ko) 2017-12-07
CA2765295C (en) 2018-05-08
WO2010149380A1 (de) 2010-12-29
BRPI1007566A2 (pt) 2020-06-23
DE102009030546B3 (de) 2011-01-20
EP2445362A1 (de) 2012-05-02
US20120152266A1 (en) 2012-06-21
US10349673B2 (en) 2019-07-16
CA2765295A1 (en) 2010-12-29
KR20120038411A (ko) 2012-04-23
ES2656819T3 (es) 2018-02-28
CN102458163B (zh) 2015-09-30
MY172461A (en) 2019-11-26
CN102458163A (zh) 2012-05-16
BRPI1007566B1 (pt) 2021-03-02

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