WO2018031387A1 - Carton compostable presentant une résistance à l'huile, à la graisse et à l'humidité - Google Patents

Carton compostable presentant une résistance à l'huile, à la graisse et à l'humidité Download PDF

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Publication number
WO2018031387A1
WO2018031387A1 PCT/US2017/045412 US2017045412W WO2018031387A1 WO 2018031387 A1 WO2018031387 A1 WO 2018031387A1 US 2017045412 W US2017045412 W US 2017045412W WO 2018031387 A1 WO2018031387 A1 WO 2018031387A1
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WO
WIPO (PCT)
Prior art keywords
paperboard
coated paperboard
binder
coating
coated
Prior art date
Application number
PCT/US2017/045412
Other languages
English (en)
Inventor
Jiebin Pang
Natasha MELTON
Original Assignee
Westrock Mwv, Llc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from US15/230,896 external-priority patent/US9670621B2/en
Application filed by Westrock Mwv, Llc filed Critical Westrock Mwv, Llc
Priority to ES17751962T priority Critical patent/ES2969258T3/es
Priority to EP17751962.6A priority patent/EP3497282B1/fr
Priority to CN201780062264.1A priority patent/CN109790686B/zh
Priority to BR112019002654-1A priority patent/BR112019002654B1/pt
Publication of WO2018031387A1 publication Critical patent/WO2018031387A1/fr

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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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • 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
    • D21H19/50—Proteins
    • 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
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • 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
    • D21H27/10—Packing paper

Definitions

  • This disclosure relates to paperboard substrates having good oil and
  • Oil and grease resistance is one of the top needs for paperboard packages in food and food service industries.
  • Several technologies including specialty chemical (wax, fluorochemicals, starch, polyvinyl alcohol (PVOH), sodium alginate, etc.) treatment, polymer extrusion coating (polyethylene, etc.) have been employed to provide oil and grease resistance of paperboard packaging.
  • the paper or paperboard treated with wax or coated with polyethylene which is currently used in oil and grease resistant packaging, has difficulties in repulping and is not as easily recyclable as conventional paper or paperboard.
  • Paper or paperboard treated with specialty chemicals such as fluorochemicals has potential health, safety and environmental concerns, and scientists have called for a stop to non-essential use of fluorochemicals in common consumer products including packaging materials.
  • Aqueous coating is one of the promising solutions to achieve these goals.
  • blocking the tendency of layers in a roll of paperboard to stick to one another
  • blocking is also a major technical hurdle for on-machine application of aqueous barrier coatings.
  • most aqueous barrier coatings are not fully repulpable.
  • certain inventive coatings that have barrier properties have achieved the ASTM compostability standard, at least for paperboard that is 12 caliper (.012") or higher. With lower caliper paperboards, the coating(s) typically contribute a larger share of the total weight, with the result that the non-biodegradable organic constituent in the coatings becomes more than 1 % of such lower-caliper paperboard.
  • the general purpose of the invention is to coat the 'barrier' side of a paperboard with at least one layer of aqueous coating containing a renewable natural material (modified starch) and a specialty synthetic binder, resulting in the coated oil and grease resistant paperboard (i.e. , 12 pt. caliper and above) meeting the ⁇ 1 % nonbiodegradable composition requirement for the compo stability standard.
  • the coating can either be applied on a paper machine or by an off-line coater, and can be applied in two coating steps (or two passes) for further enhanced barrier properties.
  • Paperboard coated according to the invention provides resistance to oil and grease, does not have any tendency to block, is compliant to safety and environmental regulations, is fully repulpable, is compostable, and can be produced at a low cost.
  • a coated paperboard which includes a paperboard substrate; a coating in contact with the paperboard substrate, the coating including binder and pigment, the coating containing substantially no fluorochemical or wax; wherein the coated paperboard has a caliper of at least 0.010"; wherein the coated paperboard provides barrier properties to at least one of oil, grease, and moisture; and wherein the coated paperboard is compostable according to the ASTM D6868-11 standard for compostability.
  • a method of treating paperboard including providing a paperboard substrate; applying to the paperboard substrate a coating comprising binder and pigment, and containing substantially no fluorochemical or wax; wherein the binder comprises starch; wherein the coated paperboard has a caliper of at least 0.010"; wherein the coated paperboard is compostable according to the ASTM D6868-11 standard for compo stability; wherein the coated paperboard has a 3M kit test value of at least 3; and wherein the coated paperboard is repulpable to the extent that after repulping the percentage accepts is at least 99%.
  • FIG. 1 illustrates a method for producing a base stock on a paperboard machine
  • FIG. 2 illustrates a method for treating the base stock from FIG. 1 by applying coatings to both sides on a paperboard machine
  • FIG. 3 illustrates a method for treating the base stock from FIG. 1 by applying coatings to one side on a paperboard machine
  • FIG. 4 illustrates a method for treating the base stock from FIG. 1 by applying coatings to one side on an off-machine coater
  • FIG. 5 illustrates a device for measuring blocking of paperboard
  • FIG. 6 is a graph of oil/grease resistance (3M kit level) vs. coat weight for several coatings
  • FIG. 7 is a graph of oil resistance (Cobb) vs. coat weight for several coatings.
  • FIG. l and FIG 2 illustrate an exemplary on-paper machine method for coating a paperboard web with one or more layers of aqueous coating.
  • a forming wire 1 10 in the form of an endless belt passes over a breast roll 115 that rotates proximate to a headbox 120.
  • the headbox provides a fiber slurry in water with a fairly low consistency (for example, about 0.5% solids) that passes onto the moving forming wire 1 10.
  • a first distance 230 water drains from the slurry and through the forming wire 1 10, forming a web 300 of wet fibers.
  • the slurry during distance 130 may yet have a wet appearance as there is free water on its surface. At some point as drainage continues the free water may disappear from the surface, and over distance 231 , water may continue to drain although the surface appears free from water.
  • the web is carried by a transfer felt or press felt through one or more pressing devices such as press rolls 130 that help to further dewatering the web, usually with the application of pressure, vacuum, and sometimes heat.
  • the still relatively wet web 300 is dried, for example using dryer or drying sections 401, 402 to produce a dry web ("raw stock") 310 which may then be run through a size press 510 that applies a surface sizing to produce a sized "base stock” 320 which may then be run through additional dryer sections 403 and (on FIG. 2) smoothing steps such as calendar 520.
  • the base stock 320 may then be run through one or more coaters.
  • coater 530 may apply a first coat ("BC") to a first side ("CI") of the web, and the first coat may be dried in one or more dryer sections 404.
  • Coater 540 may apply a second coat ("TC") to the first side of the web, and the second coat may be dried in one or more dryer sections 405.
  • coater 550 may apply a first coat to the second side ("C2") of the web, and this coat may be dried in one or more dryer sections 406.
  • Coater 560 may apply a second coat to the second side of the web, and this coat may be dried in one or more dryer sections 407.
  • the order of coaters 540, 550 may be swapped, so that both sides CI and C2 are first given a first coat, and then one side or both sides are given a second coat. In some instances, only one side will be coated as shown in FIG. 3, or only a first coat may be applied. In some instances, a third coat may be applied to one side.
  • coating may be applied by an off-machine coater as shown in Fig. 4.
  • the paperboard having been produced on the paper machine and wound onto reel 572 may then be transported (as a reel or as smaller rolls) to an off-machine coater 600, where the paperboard is unwound from reel 572, given a first coating by coater 610, dried in dryer(s) 601, given an optional second coating by coater 620, dried in dryer(s) 602, optionally given further treatment (such as gloss calendaring) and then wound onto reel 573.
  • An off-machine coater could instead apply a single coat to one side of the paperboard, or could apply a single coat to each side, or could apply more than one coat to either or both sides. Alternately some coating may be done on the paper machine, with additional coating done on an off-machine coater.
  • FIGs. 2 4 are devices where a coating is held in a pan, transferred by a roll to the lower surface of the web (which may be either the first side or the second side depending on the web path), and then the excess coating scraped off by a blade as the web wraps partially around a backing roll.
  • coater types including but not limited to curtain coater, air knife coater, rod coater, film coater, short-dwell coater, spray coater, and metering film size press.
  • the particular materials used in the coatings may be selected according to the desired properties of the finished paperboard.
  • one side e.g. CI may be given coating(s) that provide desired printability, while the other side e.g. C2 may be given barrier coating(s) that provide oil and grease resistance (OGR).
  • the printability coating may be applied before the OGR coating, or, the OGR coating may be applied before the printability coating.
  • barrier coatings give paperboard a tendency to 'block' (the layers stick together) either in the reel 570, 571 , 572, 573 or after it is rewound into rolls.
  • the reel 570 there may be residual heat from the dryers, which may dissipate quite slowly because of the large mass of the reel. Higher temperatures may increase the tendency toward blocking.
  • binder amounts in conventional printability coatings can range from 15-25 parts per 100 parts of pigment by weight for base coatings, and 10-20 parts per 100 parts pigment by weight for top coatings. Printing grades would tend to be in the lower half of these ranges. Limiting the binder amount in the top coating may allow printing inks or adhesives to absorb readily into the printability coating. Simply increasing the binder to improve barrier properties eventually interferes with printability and causes additional problems, including blocking and repulpability problems.
  • inventive coatings disclosed in the present application provide easy repulping, meet the composition requirement for the ASTM compostability standard, do not block at elevated temperature and pressure, and show good barrier properties, while using conventional pigments and synthetic and natural binders that are low-cost and readily available as coating materials for the paper or paperboard industry.
  • pigments are used in the present invention and may include, but are not limited to, kaolin clay, calcium carbonate, etc. Pigments used in the examples herein are given the following 'shorthand' designations: "Clay-1 " kaolin clay, for example, a No. 1 ultrafine clay
  • Synthetic polymer binders may include, but are not limited to, styrene acrylate copolymer (SA), polyvinyl acetate (PVAc), and styrene-butadiene copolymer (SB), etc.
  • Natural binders may include, but are not limited to, starch, alginate, protein, etc.
  • Pen-cote® D Conventional styrene acrylate binder (SA, PHOPLEX® C-340, available from Dow Chemical Company), acrylic polymer binder (Basonal® X400AL, available from BASF Corporation), starch binder (Pen-cote® D UHV, available from Ingredion Incorporated), or a blend of Pen-cote® D with SA or Basonal®, are used in examples described herein. Benefits of using Pen-cote® D include its being directly dispersible into the formulation, increasing the coating formulation solids, and possibly being able to eliminate other thickeners. The choice of binder in the examples is not meant to be limiting in any way.
  • Coatings including control coatings in the present invention were prepared according to the formulations shown in Table 1, which provides a list of major constituents in dry parts of the aqueous coating (C - Control, CF - Compostable Formulation) formulations used to achieve the oil and grease resistance, and to meet the composition requirement for the ASTM compostability standard, without blocking or repulpability problems.
  • Table 1 provides a list of major constituents in dry parts of the aqueous coating (C - Control, CF - Compostable Formulation) formulations used to achieve the oil and grease resistance, and to meet the composition requirement for the ASTM compostability standard, without blocking or repulpability problems.
  • Tables 3 and 4 The test results are shown in Tables 3 and 4.
  • substantially no fluorochemical was used in the coatings.
  • substantially no fluorochemical is meant that fluorochemicals were not deliberately utilized, and that any amount present would have been at most trace amounts.
  • fluorochemicals can be excluded in lab experiments, trace amounts of such materials might be present in some paper machine systems due to making various grades of product, or might be introduced into a papermaking system through recycling processes.
  • substantially no wax was used in the coatings.
  • the total binder to pigment ratio (parts of binder, by weight, to 100 parts of pigment) of the formulations shown in Table 1 ranges from 30 to 35. This is more than the binder to pigment ratio for typical printability coatings (where rapid absorption of ink is desired) and less than the binder to pigment ratio of typical barrier coatings. Thus, it appears that an effective binder to pigment ratio may be from about 25 to about 40 parts binder per 100 parts pigment (by weight), or from 30 to 35 parts binder per 100 parts pigment. However, perhaps acceptable results (good 3M kit test, no blocking, and good repulpability) might be achieved with a slightly greater range.
  • Blending starch (such as Pen-cote® D), a natural biodegradable material, into the formulation helps meet the ⁇ % non-biodegradable composition requirement for the ASTM compostability standard while maintaining the barrier performance.
  • the Pen- cote® D starch was added at up to 5 parts in the final formulations.
  • Paperboard samples were made using solid bleached sulphate (SBS) substrate with a caliper of 18 pt. (0.018").
  • the samples were coated on one side (herein termed the "barrier side") using a pilot blade coater with a one-layer coating.
  • the pilot results are expected to be representative of results that might be achieved on a production paper machine or a production off-machine coater.
  • OGR oil and grease resistance
  • oil absorptiveness was used to quantify and compare the OGR performance (oil and grease resistance), which measures the mass of oil absorbed in a specific time, e.g., 30 minutes, by 1 square meter of coated paperboard.
  • OGR performance oil and grease resistance
  • the sample was cut to provide two pieces each 6 inch x 6 inch square.
  • Each square sample was weighed just before the test. Then a 4 inch x 4 inch (area of 16 square inches or 0.0103 square meters) square of blotting paper saturated with peanut oil was put on the center of the test specimen (barrier side) and pressed gently to make sure the full area of oily blotting paper was contacting the coated surface.
  • Moisture resistance of the coatings was evaluated by WVTR (water vapor transmission rate at 38°C and 90% relative humidity; TAPPI Standard T464 OM-12) and water Cobb (TAPPI Standard T441 om-04). All the formulations (CFl-4, Table 3) containing Basonal® and Pen cote® D starch showed similar water Cobb and WVTR values compared to both control formulations (CI or C2), while all of them met the ASTM compostability standard.
  • FIG. 5 A simplified illustration of the blocking test is shown in FIG. 5.
  • the paperboard was cut into 2" x 2" square samples.
  • Several duplicates were tested for each condition, with each duplicate evaluating the blocking between a pair of samples 752, 754. (For example, if four duplicates were test, four pairs - eight pieces - would be used.)
  • Each pair was positioned with the 'barrier-coated' side of one piece 752 contacting the uncoated side of the other piece 754.
  • the pairs were placed into a stack 750 with a spacer 756 between adjacent pairs, the spacer being foil, release paper, or even copy paper.
  • the entire sample stack was placed into the test device 700 illustrated in FIG. 5.
  • the test device 700 includes a frame 710. An adjustment knob 712 is attached to a screw 714 which is threaded through the frame top 716. The lower end of screw 714 is attached to a plate 718 which bears upon a heavy coil spring 720. The lower end of the spring 720 bears upon a plate 722 whose lower surface 724 has an area of one square inch. A scale 726 enables the user to read the applied force (which is equal to the pressure applied to the stack of samples through the one-square-inch lower surface 724).
  • the stack 750 of samples is placed between lower surface 724 and the frame bottom 728.
  • the knob 712 is tightened until the scale 726 reads the desired force of 100 lbf (100 psi applied to the samples).
  • the entire device 700 including samples is then placed in an oven at 50°C for 24 hours.
  • the device 700 is then removed from the test environment and cooled to room temperature. The pressure is then released and the samples removed from the device.
  • samples 752(0)/754(0) might be representative of a "0" blocking (no blocking).
  • the circular shape in the samples indicates an approximate area that was under pressure, for instance about one square inch of the overall sample.
  • Samples 752(3 )/754(3) might be representative of a "3" blocking rating, with up to 25% fiber tear in the area that was under pressure, particularly in the uncoated surface of sample 754(3).
  • Samples 752(4 )/754(4) might be representative of a "4" blocking rating with more than 25% fiber tear, particularly in the uncoated surface of sample 754(4).
  • the depictions in FIG. 5 are only meant to approximately suggest the percent damage to such test samples, rather than showing a realistic appearance of the samples.
  • Repulpability was tested using an AMC Maelstom repulper. 1 10 grams of coated paperboard, cut into l "xl " squares, was added to the repulper containing 2895 grams of water (pH of 6.5 ⁇ 0.5, 50°C), soaked for 15 minutes, and then repulped for 30 minutes. 300 mL of the repulped slurry was then screened through a Vibrating Flat Screen (0.006" slot size). Rejects (caught by the screen) and fiber accepts were collected, dried and weighed. The percentage of accepts was calculated based on the weights of accepts and rejects, with 100% being complete repulpability.
  • paperboard CF1, CF2, CF3, CF4 are for coatings blending the Basonal® binder with Pen-cote® D, a modified starch made by Ingredion Incorporated. These paperboards all meet the compostability definition.
  • Gloss was measured on a Technidyne Model T 480A Glossmeter according to TAPPI standard T480.
  • GE Brightness was measured on a Technidyne Brightimeter Micro S-5 according to TAPPI standard T452.
  • CIE Whiteness was measured the Technidyne Brightimeter Micro S-5 according to TAPPI standard T562.
  • Basonal® binder or a blend of Basonal® binder with Pen-cote® D starch showed similar or slightly higher gloss of the coating than using SA binder, but with slightly lower brightness and whiteness and slightly higher b-color value.
  • Barrier properties are the focus of the inventive coatings, however, if there is a need to adjust the color or shade, food contact compliant dyes can be used in the formulations.
  • the Basonal® X 400 AL binder made by BASF Corporation contains about 30% natural polymer component.
  • a natural polymer component refers to one grown and found in nature, which for example, can be any protein or polysaccharide or their derivatives.
  • the idea of using the Basonal® X 400 AL binder along with some additional natural polymer (such as starch) in the present invention was that the natural component in the Basonal® binder would promote the compatibility of the additional starch with the Basonal® binder. Compatibility of the different ingredients is important for a barrier coating.
  • Tables 3 and 4 thus show that the combined use of Pen-cote® D specialized starch with Basonal® binder provides improved barrier performance, especially, achieving a 3M kit level of 5+, while meeting the compostability standard, being fully repulpable, and not having blocking problems. 53] As another way to visualize the test results, the data were plotted as shown in FIGs. 6 and 7. Some of the data on the graphs comes from Tables 3 and 4. Other data are also included. FIG. 6 shows 3M kit level vs. coat weight. The kit value generally increases (improves) as coat weight increases. None of the control samples (using SA binder) were compostable in the coat weight range of 6-12 lbs / 3msf.
  • FIG. 7 shows oil Cobb vs. coat weight for the selected samples as in FIG.
  • the oil Cob generally decreases (improves) as coat weight increases.
  • the compostability (or lack thereof) has already been described.
  • the test samples using (combined) Basonal® and Pen-cote® D gave oil Cobb tests equal or better (lower) than the test samples using styrene-acrylate binder.
  • compostable paperboard with full repulpability and moderate grease resistance is achieved by replacing standard binders (such as styrene acrylate) with a binder such as Basonal® X400AL in combination with small amounts of Pen-cote® D specialized starch.
  • standard binders such as styrene acrylate
  • Basonal® X400AL in combination with small amounts of Pen-cote® D specialized starch.
  • the paperboard product meets the composition requirements of the ASTM compostability standard, at least for paperboards of caliper 12 pt. and higher.
  • the compostability standard involves calculations of how much of each non-biodegradable organic constituent is used in the product. It is hypothesized that by adjusting the coating, or the paperboard basis weight, compostability according to the ASTM standard might be achieved with somewhat lower calipers, such as 10 pt. (0.010").

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Abstract

L'invention porte sur un carton revêtu qui comprend un revêtement ne contenant sensiblement pas de composé fluorochimique ni de cire, présentant une bonne résistance à l'huile et à la graisse, aucune tendance au blocage, le carton revêtu étant totalement repulpable ainsi que compostable.
PCT/US2017/045412 2016-08-08 2017-08-04 Carton compostable presentant une résistance à l'huile, à la graisse et à l'humidité WO2018031387A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
ES17751962T ES2969258T3 (es) 2016-08-08 2017-08-04 Cartón compostable resistente a los aceites, grasas y la humedad
EP17751962.6A EP3497282B1 (fr) 2016-08-08 2017-08-04 Carton compostable presentant une résistance à l'huile, à la graisse et à l'humidité
CN201780062264.1A CN109790686B (zh) 2016-08-08 2017-08-04 具有耐油、耐油脂和耐湿性的可堆肥纸板
BR112019002654-1A BR112019002654B1 (pt) 2016-08-08 2017-08-04 Papelão revestido e método de tratar papelão

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US15/230,896 US9670621B2 (en) 2015-02-11 2016-08-08 Compostable paperboard with oil, grease, and moisture resistance
US15/230,896 2016-08-08

Publications (1)

Publication Number Publication Date
WO2018031387A1 true WO2018031387A1 (fr) 2018-02-15

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EP (1) EP3497282B1 (fr)
CN (1) CN109790686B (fr)
BR (1) BR112019002654B1 (fr)
ES (1) ES2969258T3 (fr)
WO (1) WO2018031387A1 (fr)

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EP3497282C0 (fr) 2024-01-10
CN109790686A (zh) 2019-05-21
BR112019002654A2 (pt) 2019-05-28
EP3497282B1 (fr) 2024-01-10
ES2969258T3 (es) 2024-05-17
EP3497282A1 (fr) 2019-06-19
BR112019002654B1 (pt) 2023-04-11
CN109790686B (zh) 2022-03-15

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