WO2020100097A1 - Procédé pour rendre hydrophobe un substrat de cellulose à l'aide d'un halogénure d'acide gras - Google Patents

Procédé pour rendre hydrophobe un substrat de cellulose à l'aide d'un halogénure d'acide gras Download PDF

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Publication number
WO2020100097A1
WO2020100097A1 PCT/IB2019/059825 IB2019059825W WO2020100097A1 WO 2020100097 A1 WO2020100097 A1 WO 2020100097A1 IB 2019059825 W IB2019059825 W IB 2019059825W WO 2020100097 A1 WO2020100097 A1 WO 2020100097A1
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WO
WIPO (PCT)
Prior art keywords
fatty acid
substrate
acid halide
cellulose substrate
cellulose
Prior art date
Application number
PCT/IB2019/059825
Other languages
English (en)
Inventor
Susanne HANSSON
Raija BÅDENLID
Carl-Magnus BRANDÉN
Original Assignee
Stora Enso Oyj
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
Application filed by Stora Enso Oyj filed Critical Stora Enso Oyj
Priority to KR1020217018373A priority Critical patent/KR20210100635A/ko
Priority to US17/293,987 priority patent/US20220010493A1/en
Priority to CN201980085643.1A priority patent/CN113227495A/zh
Priority to EP19885957.1A priority patent/EP3880886A4/fr
Priority to JP2021526611A priority patent/JP2022507555A/ja
Publication of WO2020100097A1 publication Critical patent/WO2020100097A1/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
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/04—Physical treatment, e.g. heating, irradiating
    • D21H25/06—Physical treatment, e.g. heating, irradiating of impregnated or coated paper
    • 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
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/11—Halides
    • 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
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/14—Carboxylic acids; Derivatives thereof
    • 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
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • 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
    • D21H19/80—Paper comprising more than one coating
    • 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
    • D21H19/80—Paper comprising more than one coating
    • D21H19/84—Paper comprising more than one coating on both sides of the substrate
    • 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
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/32—Addition to the formed paper by contacting paper with an excess of material, e.g. from a reservoir or in a manner necessitating removal of applied excess material from the paper
    • D21H23/42—Paper being at least partly surrounded by the material on both sides
    • D21H23/44—Treatment with a gas or vapour
    • 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
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/50—Spraying or projecting
    • 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
    • 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
    • D21H5/00—Special paper or cardboard not otherwise provided for
    • D21H5/26—Special paper or cardboard manufactured by dry method; Apparatus or processes for forming webs by dry method from mainly short-fibre or particle material, e.g. paper pulp
    • 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
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/66—Treating discontinuous paper, e.g. sheets, blanks, rolls
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21J—FIBREBOARD; MANUFACTURE OF ARTICLES FROM CELLULOSIC FIBROUS SUSPENSIONS OR FROM PAPIER-MACHE
    • D21J1/00—Fibreboard
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21J—FIBREBOARD; MANUFACTURE OF ARTICLES FROM CELLULOSIC FIBROUS SUSPENSIONS OR FROM PAPIER-MACHE
    • D21J1/00—Fibreboard
    • D21J1/08—Impregnated or coated fibreboard

Definitions

  • substrate comprises a first side and an opposite second side.
  • Paper- and paperboard are usually treated with sizing agents to enhance certain qualities, above all to increase the resistance to penetration of water and other liquids into the paper or paperboard.
  • sizing agents There are two types of sizing: internal and surface sizing.
  • chemicals are added to the pulp at the wet end, e.g. ASA, AKD or rosin size.
  • Common surface sizing agents include e.g. starch or acrylic co polymers .
  • US4107426 discloses a method for imparting water-repellent characteristics to a surface of a cellulose substrate. The process comprising the steps of exposing the surface to a vapour phase consisting essentially of aliphatic acid
  • a drawback with this method is that mainly the surface of a substrate that becomes hydrophobic and not the interior of the substrate. This causes problem with edge wicking, i.e.
  • W02017002005 a method is described where a vaporized fatty acid halide is arranged to penetrate the cellulose substrate.
  • the equipment required to perform the method according to W02017002005 occupies a lot of space and is therefore difficult to implement at an existing production site .
  • An object with the present invention is to provide an improved method for increasing the hydrophobicity of materials with a cellulose substrate that e.g. enhances the water repellency and resistance against edge wick penetration of a cellulose substrate .
  • the inventive method for hydrophobizing a cellulose substrate comprising the following steps:
  • Treating a cellulose substrate according to the method of the present invention leads to an increase of the hydrophobicity of the material, not only at the surface but also at its core, and to enhanced water resistance thereof, as well as
  • -the device for applying the vaporized fatty acid halide onto the substrate can be aimed in differently defined directions, -the reagent (i.e. fatty acid halide) will have an even distribution over the surface even if the surface is rough, -calibration of dosage enables for avoiding unwanted surplus of reagent on substrate,
  • the amount of reagent can be easily controlled by adjusting the pressure or the number of spray units, and
  • spray form means in the form of a plurality of liquid droplets or particles, and that the fatty acid halide in spray form may be delivered by means of a precision device for dispersion of freely flowing liquid fatty acid halide into said spray form.
  • the droplets or particles may be in micro scale with sizes ranging from 1-900 pm in diameter .
  • the vaporized fatty acid halide is guided to contact also the second side of the cellulose substrate, and at least partially penetrate the cellulose substrate. This may be accomplished by means of vacuum suction.
  • the cellulose substrate can be in the form of paper- or paperboard web, paperboard application, textiles made from cellulose fibres, or three-dimensional cellulose-based
  • thermoforming products e.g. produced by means of thermoforming.
  • the paper- or paperboard web may be a single- or multilayer web .
  • Conversion of the fatty acid halide spray into vaporized form may be accomplished by applying thermal energy, i.e. heating the spray droplets to a point where they enter gaseous state.
  • heating of the spray can be performed by IR heating.
  • Other heating devices are conceivable, such as e.g. a hot cylinder, microwaves or similar. Vaporizing of fatty acid halide in spray form requires lower energy consumption
  • the equipment for converting the spray into gas can be made space efficient and therefore be fitted at an existing productions line.
  • said guiding of the fatty acid halide is performed by vacuum sucking at the second side of the cellulose substrate, such that the fatty acid penetrates the cellulose substrate in a predetermined direction through the cellulose substrate.
  • vacuum suction can be generated by means of a vacuum box, a rotating vacuum cylinder or any other suitable vacuum generating equipment. Thanks to the method according to the invention, the covalent degree can be more even throughout the thickness of the material compared to e.g. conventional roll coating of freely flowing reagents onto a running substrate.
  • the covalent degree is the ratio between the grafted fatty acids and the total fatty acids in the substrate, where the grafted corresponds to the reagent that has reacted and the total amount is this part together with the free fatty acids that only has been physically absorbed to the substrate.
  • said guiding of the vaporized fatty acid halide is performed by vacuum sucking at the first side of the cellulose substrate, so that the vaporized fatty acid is guided along the surface of the first side of the cellulose substrate in a predetermined direction in such a way that the fatty acid is brought into contact with the cellulose substrate.
  • "along the surface” means that the vaporized fatty acid is brought to move
  • the fatty acid halide is mixed with at least one solvent before it is sprayed and vaporized.
  • said solvent is selected from the group comprising: acetone, ethyl acetate and methyl ethyl ketone. It is preferred that the solvent (or mixture of solvents) does not contain any OH-groups, and also that it is miscible with the fatty acid halide, which will help against clogging and promote the cleaning of the application system.
  • the utilization of a solvent also makes it possible to
  • the boiling point of the solvent shall preferably not be too high to ensure that there will be no residual solvent in the product, preferably it is below 200 degrees C, more preferably below 150 degrees C, and even more preferably below 100 degrees C.
  • Acetone has a boiling point at 59 degrees C; ethyl acetate has a boiling point at 77 degrees C and methyl ethyl ketone has a boiling point at below 59 degrees C.
  • Addition of a solvent to the fatty acid halide may lead to the advantage that vaporization of the spray is facilitated and also that the penetration of the reagent into the substrate is improved.
  • the mixture of fatty acid halide and solvent comprises 0.1-20wt%, preferably 0.1- 10wt%, more preferably 0.1-5wt% solvent of the total weight of the mixture. If the solvent amount is too high, the reagent can be too diluted to form an even coverage and distribution upon application, and thereby increasing the need of increased application units. This can also result in a higher risk of residual solvent molecules in the final product. If the applied amount of reagent becomes too low, it can have a negative impact on the desirable material properties.
  • the dry content of the cellulose substrate is above 80%, preferably above 85%, even more preferably above 90%. The higher dry content, the better will the result of the subsequent
  • hydrophobation be This is due to that the fatty acid halide has a high reactivity towards water. Therefore, presence of water can lead to the undesired formation of too high amounts of fatty acids that are not attached to the substrate.
  • the fatty acid halide to be vaporized comprises an aliphatic chain length of between 10 - 22 carbon atoms.
  • Said fatty acid is preferably selected from palmitoyl chloride (C16), stearoyl chloride (C18) or mixtures thereof.
  • the method further comprises a step of heating the cellulose substrate, before and/or after adding the fatty acid halide.
  • Figure 1 shows a schematic view of the invention according to a first embodiment, where a fatty acid halide in spray form is applied onto a substrate
  • Figure 2 shows a schematic view of the invention according to a second embodiment, where a fatty acid halide in vaporized form is applied onto a substrate;
  • Figures 3a-b show schematic views of the invention according to a third and fourth embodiments, wherein both the first and second sides of a substrate are subjected to a fatty acid halide ;
  • Figure 4 shows a schematic view of the invention according to a fifth embodiment, where a fatty acid halide in vaporized form is applied onto a substrate;
  • Figure 5 illustrates in a schematic way hydrophobation of a cellulose substrates, where such substrates are in the form of three-dimensional cellulose-based products.
  • a cellulose substrate 1 comprising a first side and a second side, is generally referred to as "1".
  • the substrate is in the form of a
  • cellulose-based web such as a paper- or paperboard web.
  • the second side of said substrate 1 faces away from the first side.
  • the cellulose substrate e.g. a paper- or paperboard web 1
  • the drying is performed by any conventional drying methods suitable for drying a cellulose substrate.
  • a cellulose substrate of a paper- or paperboard web may for example be dried by drying cylinders.
  • the cellulose substrate 1 has a dry content above 80%, preferably above 85% and most preferably above 90%. A higher dry content can give better results of the subsequent
  • the cellulose substrate 1 may thereafter be further dried and heated.
  • the heating is preferably performed in a pre-treatment step by IR heating 2 as illustrated in Figs. 1-3.
  • the pre treatment heating step has several advantages. It will minimize unwanted condensation of the gas upon contact with the substrate, and also lead to that the subsequent
  • hydrophobizing agent will penetrate better through the
  • any remaining water residues can be further dried; the substrate 1 may possibly be dried even up to 95% dry content.
  • the first side of the dried and heated substrate 1 is then treated with a fatty acid halide, in spray form or in gas- phase, to hydrophobize the substrate, such that the substrate becomes hydrophobic.
  • a device 5 also referred to as "spray device” 5 for dispersing liquid fatty acid halide into a spray 50, which spray may contact the substrate directly or become vaporized into gas phase where such gas contacts the substrate.
  • Said spray device 5 may be in the form of a spray nozzle used for atomizing the liquid.
  • Spray atomization here means the transformation of a liquid into a spray of fine particles by mixing the liquid with compressed air.
  • a spray nozzle generates the atomized spray when being passed through an opening at high pressure and in a controlled manner, A higher pressure will create smaller liquid droplets and a finer spray.
  • Different spray devices 5 are conceivable.
  • Another example is electrospraying whereby electrical forces are utilized on a liquid that flows from a nozzle, which can have various shapes and conformation, and thereafter fine, uniform and charged droplets are formed, due to that the electrical force exceeds the surface tension force. It can also be due to mechanical distortions.
  • the general advantages of the electrospraying process are that it can be performed as one step at low cost, low energy input and with a good
  • the applied fatty acid halide will at least partially penetrate the cellulose of said substrate 1 and bind covalently to the cellulose therein, increasing the water repellency of the material.
  • the second side of the substrate can be subjected to a vacuum suction, simultaneously, during the hydrophobation of the substrate, such that the spray or gas is transported in a predetermined direction through the substrate. This enhances the hydrophobicity of the surface as well as the core of the substrate, so that the substrate will be more resistant against in-plane edge penetration.
  • the fatty acid halide is any halide that can be vaporized, however palmitoyl chloride, C16 has, in tests, shown to be particularly suitable. During tests a covalent degree of above 40% and even above 60% has been achieved, compared to
  • gas/vaporization for applying the fatty acid halide is that it is very position specific and hydrophobicity is only achieved where the spray or gas can access the substrate.
  • the reagent will react with the available hydroxyl groups forming HC1 as a by-product.
  • the reagent is also highly reactive towards water and the reaction requires dry substrates. Nevertheless, there will always be some presence of water whereupon the
  • Figure 1 illustrates an exemplary way of performing the method according to the invention.
  • a dried and heated cellulose substrate 1 in the form of a paper- or paperboard is
  • IR heating additionally heated and dried with IR heating from an IR heating box 2.
  • the additional IR heating is optional.
  • Liquid fatty acid halide is stored in a separate tank 3 wherefrom it is ejected through a device 5 for dispersing the liquid into a spray 50.
  • a spray device 5 can for instance be in the form of a spray nozzle used for atomizing the liquid, i.e. breaking up the fluid into droplets 50.
  • the droplets are sprayed by means of the device 5 onto a first side la of the underlying, running substrate 1.
  • Said first side laside of the substrate 1 is at the same time in contact with a downstream rotating cylinder 6, for instance a heated cylinder that heats the droplets into gas whereby the atomized fatty acid molecules react more efficiently with the cellulose of the substrate.
  • a downstream rotating cylinder 6 for instance a heated cylinder that heats the droplets into gas whereby the atomized fatty acid molecules react more efficiently with the cellulose of the substrate.
  • multiple spraying units positioned after each other in sequences in connection to the running substrate, where each such unit can comprise one or a
  • a rotating vacuum cylinder with holes (not shown) is arranged in connection with a second side lb of the substrate and downstream of the spray device 5, arranged to vacuum sucking droplets or vaporized fatty acid halide in a predetermined direction through the cellulose substrate 1.
  • the substrate 1 is arranged to enter between two nip rolls (not shown) , preferably where at least one of the rolls is a heated nip roll, and that the fatty acid halide spray is directed into the nip roll junction whereby the spray droplets are converted into gaseous phase by means of the heated roll/s.
  • the spray may also be directed to contact the heated nip roll immediately upstream of the nip roll junction, whereby the fatty acid halide is vaporised by the heat of the roll and directly thereafter, i.e. within seconds or milliseconds, applied onto the substrate.
  • Yet another arrangement for applying the fatty acid halide is that the fatty acid halide is sprayed directly onto a heating roll arranged to immediately, i.e. within seconds or
  • the heated roll provides several functions: the function of bringing the fatty acid halide into contact with the substrate, the function of vaporizing the fatty acid halide into gas phase and the function of promoting the chemical reaction to covalent bind the fatty acid halide to the substrate.
  • Vaporization of the fatty acid halide can be arranged to occur before the heated roll contacts the substrate, or simultaneously with that the heated roll contacts the substrate depending on where on the heated roll the spray is applied. E.g. if the spray is
  • palmitoyl chloride and/or unbound Cl 6 can be removed and collected for handling.
  • a second embodiment according to the present invention is schematically shown.
  • a dried and heated cellulose substrate 1 in the form of a paper- or paperboard is optionally further heated and dried with IR heating from an IR heating box 2, as also previously described in connection with Fig. 1.
  • Liquid fatty acid halide is stored in a separate tank 3 wherefrom it is transferred e.g. via a tube 4 (or other transferring means) to a device 5 for dispersing the liquid into a spray 50.
  • a device 5 can for instance be in the form of a spray nozzle used for atomizing the liquid, i.e. breaking up the fluid into droplets 50.
  • the droplets are sprayed via the device 5 into a heating chamber 7 such as a pressurized heating tank 7.
  • the spray droplets are heated inside said tank 7 to vaporize into gas-phase, and said gas 70 is thereafter ejected or deposited through a gas spreading device 71 onto the first surface of said substrate 1.
  • Said first side of the substrate is at the same time in contact with a rotating cylinder 6.
  • Yet another rotating cylinder of vacuum type may be arranged at the second side lb of the substrate for sucking the gas in a predetermined direction through the cellulose substrate 1.
  • the cellulose substrate 1 can be hydrophobized through the
  • HC1 by-product and possibly unreacted e.g. palmitoyl chloride and/or unbound C16 can be removed and collected for handling.
  • the usage of two or more spray units can be placed in such way that the minimum amount of space is needed and fitted to the existing equipment. By utilizing a plurality of units, it can also be possible to run the machine at an increased speed.
  • Figures 3a-b show a third and fourth embodiment, respectively, wherein both the first and second side of a substrate 1 are subjected to hydrophobation by means of application of a fatty acid halide in spray form.
  • the substrate 1 is firstly subjected to pre-treatment 2 in the form of heating, e.g. IR heating.
  • a device 5 for dispersing liquid into spray is positioned downstream of the pre-treatment 2 at the second side lb of the substrate, adjacent to a rotating cylinder 6 and arranged to direct a spray 50 of fatty acid halide onto the surface of the cylinder 6 which, upon rotating further, will deliver the fatty acid halide onto the surface of the second side lb of the substrate 1.
  • the rotating cylinder 6 may be heated, also to such extent that the sprayed droplet transform into gas before touching the substrate.
  • a vacuum box 8 is arranged at the first side la of the substrate 1 to draw the reagent into the cellulose structure.
  • the substrate 1 is further hydrophobized in a subsequent downstream step, wherein fatty acid halide 50' is applied also onto the first side la of the substrate 1.
  • a second device 5' for dispersing liquid into spray 50' is positioned adjacent to a second rotating cylinder 6' , said device 5' being arranged to direct a spray 50' of fatty acid halide onto the surface of the cylinder 6 which, upon rotating further, will deliver the fatty acid halide onto the surface of the first side la of the substrate 1.
  • the rotating cylinder 6 may be heated.
  • a vacuum box 8' is arranged in close proximity of the rotating
  • Fig. 3b serving the same purpose as in Fig. 3a, namely to treat both sides of a substrate 1 to increase the hydrophobicity thereof.
  • the substrate 1 is guided through two subsequent hydrophobation steps wherein fatty acid halide is applied firstly onto the second side lb of the substrate, and secondly onto the first side la thereof.
  • a spray device 5 is positioned adjacent to a second side lb of the running
  • a vacuum box 8 is arranged at the first side la of the substrate, opposing the spray device 5, said vacuum box 8 being arranged to draw the fatty acid halide to at least partially penetrate the
  • a downstream rotating cylinder 6 may be provided, preferably a heated cylinder, to promote the binding of reagent to the cellulose substrate 1.
  • a corresponding, second hydrophobation step is arranged
  • heating of the substrate 1 is performed in a pre-treatment step e.g. by IR heating 2.
  • the subsequently applied vaporized fatty acid halide 70 is guided to contact the substrate 1 by vacuum sucking 8 at the first side la of the cellulose substrate, so that the vaporized fatty acid 70 is brought to be transferred along the surface of the first side la of the cellulose substrate 1 in a
  • the vaporized fatty acid is thereby brought to move substantially parallel with the first side of the substrate.
  • Fig. 5 illustrates in a schematic way the method according to the invention where the substrate 10 is a three-dimensional cellulose based product.
  • a conveyor belt 9 is
  • dimensional products 11 may be e.g. pre-produced paper trays, mugs or containers, or other types of 3D-shaped objects made from cellulose. After having passed through the unit 11 wherein vaporized fatty acid halide is brought to contact the cellulose substrate, and at least partially penetrated its thickness, the exiting product 10' has acquired hydrophobic properties .
  • contact angle measurement was utilized to qualitatively analyze how much the cellulose substrate has been hydrophobized by the method.
  • An un-treated cellulose substrate had before a contact angle around 40° and after treatment of the inventive method a contact angle of 110-130° on both the first side and the second side of the substrate, despite only one surface was in direct contact with the reagent.
  • Contact angles greater than 90° generally means that wetting of the surface is unfavourable, so the fluid will minimize contact with the surface and form a compact liquid droplet.

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  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

La présente invention concerne un procédé pour rendre hydrophobe un substrat de cellulose (1) qui comprend un premier côté et un second côté qui est opposé au premier côté, le procédé comprenant les étapes consistant à : sécher le substrat de cellulose jusqu'à obtention d'une teneur en matière sèche supérieure à 80 %, de préférence supérieure à 85 % ; fournir un halogénure d'acide gras sous forme pulvérisée ; convertir ledit halogénure d'acide gras sous forme pulvérisée en halogénure d'acide gras vaporisé ; et guider ledit halogénure d'acide gras vaporisé pour qu'il entre en contact avec le premier côté du substrat de cellulose, et pénètre au moins partiellement dans le substrat de cellulose.
PCT/IB2019/059825 2018-11-16 2019-11-15 Procédé pour rendre hydrophobe un substrat de cellulose à l'aide d'un halogénure d'acide gras WO2020100097A1 (fr)

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KR1020217018373A KR20210100635A (ko) 2018-11-16 2019-11-15 지방산 할로겐화물 사용에 의한 셀룰로스 기재 소수성화 방법
US17/293,987 US20220010493A1 (en) 2018-11-16 2019-11-15 Method for hydrophobizing a cellulose substrate by utilizing a fatty acid halide
CN201980085643.1A CN113227495A (zh) 2018-11-16 2019-11-15 通过利用脂肪酰卤使纤维素基底疏水化的方法
EP19885957.1A EP3880886A4 (fr) 2018-11-16 2019-11-15 Procédé pour rendre hydrophobe un substrat de cellulose à l'aide d'un halogénure d'acide gras
JP2021526611A JP2022507555A (ja) 2018-11-16 2019-11-15 脂肪酸ハロゲン化物を利用することによりセルロース基材を疎水化するための方法

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SE1851430A SE543029C2 (en) 2018-11-16 2018-11-16 Method for hydrophobizing a cellulose substrate by utilizing a fatty acid halide
SE1851430-7 2018-11-16

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PCT/IB2019/059825 WO2020100097A1 (fr) 2018-11-16 2019-11-15 Procédé pour rendre hydrophobe un substrat de cellulose à l'aide d'un halogénure d'acide gras

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US (2) US20220010493A1 (fr)
EP (2) EP3880886A4 (fr)
JP (2) JP2022507536A (fr)
KR (2) KR20210100635A (fr)
CN (2) CN113227494A (fr)
SE (1) SE543029C2 (fr)
WO (2) WO2020100101A1 (fr)

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SE2050753A1 (en) * 2020-06-24 2021-12-25 Stora Enso Oyj Water-resistant paper or paperboard
SE2150063A1 (en) * 2021-01-21 2022-07-22 Stora Enso Oyj Coated cellulose-based substrate

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SE2050753A1 (en) * 2020-06-24 2021-12-25 Stora Enso Oyj Water-resistant paper or paperboard
WO2021260606A1 (fr) * 2020-06-24 2021-12-30 Stora Enso Oyj Matériau fibreux résistant à l'eau et son procédé de fabrication
SE544175C2 (en) * 2020-06-24 2022-02-22 Stora Enso Oyj Water-resistant paper or paperboard
SE2150063A1 (en) * 2021-01-21 2022-07-22 Stora Enso Oyj Coated cellulose-based substrate
WO2022157651A1 (fr) * 2021-01-21 2022-07-28 Stora Enso Oyj Substrat à base de cellulose revêtu

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EP3880884A1 (fr) 2021-09-22
CN113227495A (zh) 2021-08-06
EP3880886A4 (fr) 2022-07-27
US20220010493A1 (en) 2022-01-13
JP2022507536A (ja) 2022-01-18
EP3880884A4 (fr) 2022-08-10
WO2020100101A1 (fr) 2020-05-22
SE543029C2 (en) 2020-09-29
JP2022507555A (ja) 2022-01-18
SE1851430A1 (en) 2020-05-17
EP3880886A1 (fr) 2021-09-22
KR20210100635A (ko) 2021-08-17
US20220002949A1 (en) 2022-01-06
CN113227494A (zh) 2021-08-06
KR20210100636A (ko) 2021-08-17

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