Classifications

• • 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
  • B65D65/42—Applications of coated or impregnated materials
• • 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
  • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
  • B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
  • B65D81/26—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators
  • B65D81/264—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators for absorbing liquids
• • 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
  • D21H11/14—Secondary fibres
• • 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
  • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
  • D21H13/36—Inorganic fibres or flakes
  • D21H13/46—Non-siliceous fibres, e.g. from metal oxides
  • D21H13/50—Carbon fibres
• • 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
• • 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
  • D21H17/20—Macromolecular organic compounds
  • D21H17/33—Synthetic macromolecular compounds
  • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• • 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
  • D21H17/20—Macromolecular organic compounds
  • D21H17/33—Synthetic macromolecular compounds
  • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
• • 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

• the present invention relates to a fiber product for packaging, in particular food packaging, comprising a first fiber layer.
• the present invention further relates to a method for producing a fiber product, a use of a fiber product for producing packaging, and the use of activated carbon in a fiber layer of a fiber product for packaging.
• Fiber products such as cardboard, carton, and/or paper.
• Fiber products also known as fiber-based products, are not only used for packaging but have a broad range of applications. Examples of other products made from fiber products include paper plates, paper cups, and the like. Fiber products contain at least one layer of fibers.
• the fibers in a fiber layer can be cellulose fibers or virgin fibers, waste paper fibers or recycled fibers, or a mixture of both fiber types.
• Fiber products made from paper or cardboard are typically manufactured on paper machines or board machines, where an aqueous fiber suspension is first created in a vat, to which further components can be added.
• the fiber suspension is then usually passed over a forming section, where most of the water is removed, forming a fiber web.
• a forming unit or former is typically used in the forming section.
• the fiber web is often transferred to a press felt and further dewatered by pressure. After the press section...
• the further dried fiber web typically passes through a drying section and, if necessary, a calender.
• An important factor for efficient fiber web formation (also referred to as "sheet formation") is the chemical oxygen demand (COD).
• COD chemical oxygen demand
• the COD in the vat is often above 4,000 mg/L or even 5,000 mg/L. Since sheet formation is not always optimal at these COD levels, additives are frequently added to the fiber suspension before the wire section to lower the COD.
• a problem with the use of recycled fibers is the high proportion of newsprint in waste paper, which is generally printed with mineral oil-based inks.
• the recycled fibers are cleaned and treated before reuse, fiber products made from recycled fibers still contain an unavoidable amount of mineral oil hydrocarbons. Examples of such fiber products can have a mineral oil hydrocarbon concentration of approximately 100 ppm to 1500 ppm.
• the prior art proposes a solution to the problem by providing the manufactured fiber product with an additional protective layer in a subsequent processing step.
• the US 5,153,061 A A fiber product with a protective layer, such as a polymer coating or an aluminum layer. This protective layer is located on the inside of the packaging.
• the EP 3 260 597 A1 Describes a fibrous product with reduced migration behavior of aromatic hydrocarbons and/or saturated mineral oil hydrocarbons for packaging food products compared to fibrous products based on recycled fibers, wherein the fibrous product consists of two or more fibrous layers, wherein at least one fibrous layer or an intermediate layer of the fibrous product arranged between two fibrous layers comprises a mineral filter material selected from the group of bentonites and/or saponins.
• a disadvantage of the fibrous product is... EP 3 260 597 A1 The problem is that the effectiveness of bentonites and saponins is limited.
• the present invention aims to provide a fiber product that can be manufactured efficiently and in which the migration of mineral oil hydrocarbons from the fiber product into another product is sufficiently reduced.
• a fiber product for packaging in particular food packaging, comprising a first fiber layer, wherein the first fiber layer has cellulose-containing fibers and is permeated with activated carbon in such a way that the migration of mineral oil hydrocarbons, in particular from the fiber product, into a foodstuff in contact with the fiber product is reduced, wherein the fiber product has a chemical oxygen demand of 50 to 1,500 mg/L.
• the chemical oxygen demand (COD) can be determined, in particular, using a cuvette test.
• a cuvette test In this test, the sample to be measured is placed in a detection solution, heated, and analyzed photometrically. Suitable standardized cuvette tests are known and commercially available.
• cuvettes from Hach Lange GmbH, Düsseldorf can be used in a so-called Hach-LCK cuvette test. These cuvettes are designed for... Different ranges of chemical oxygen demand are available.
• the corresponding cuvettes from Hach Lange GmbH are specifically designed to comply with the DIN 38409-H41-H44 standard (sometimes also referred to as DIN 38409-41 to DIN 38409-44). The measurement is performed by removing a fresh cuvette and shaking it to disperse any sediment.
• the fiber product can be comminuted in water, and then a sample of the resulting fiber suspension or a filtrate thereof can be analyzed.
• a crusher operating at 3000 rpm can be used to comminute the fiber product.
• the fiber suspension can have a concentration in the range of 3 to 5 wt%, preferably 4 wt%, based on the total weight of the suspension.
• the chemical oxygen demand is referred to in particular as COD or COD value.
• fiber products according to the invention which have a chemical oxygen demand (COD) of 50 to 1,500 mg/L, can be produced efficiently and effectively reduce the migration of mineral oil hydrocarbons through the fiber product.
• COD value of the fiber suspension which is often in the range of over 4,000 mg/L or over 5,000 mg/L, is lowered by the addition of additives to improve leaf formation.
• additives are known to reduce the COD's ability to reduce COD levels. to reduce the migration of mineral oil hydrocarbons by activated carbon. Therefore, it was surprising that the demanding fiber product could be manufactured efficiently and, despite the usually necessary addition of additives to adjust the COD value, could simultaneously reduce the migration of mineral oil hydrocarbons effectively.
• activated carbon appears to be less impaired in its function in a demanding fiber product.
• activated carbon seems to be less clogged or otherwise hindered by the fibers and any other ingredients, especially the additives.
• the fiber products could be manufactured efficiently, which was particularly evident in the good retention.
• a crucial parameter of migrating mineral oils is their chain length.
• Short-chain mineral oil hydrocarbons (approximately C1 to C9 ) are generally unproblematic. Without adhering to any scientific theory, it is assumed that they are removed during paper and cardboard production.
• Very long-chain mineral oil hydrocarbons (approximately above a chain length of C35 ) are also less problematic due to their generally reduced migration capacity.
• Mineral oil hydrocarbons with a chain length of C16 to C20 or C16 to C25 are particularly problematic.
• the migration of mineral oil hydrocarbons with a chain length of C16 to C20 and/or C16 to C25 into a food product in contact with the fiber product can be reduced in the fiber product as described.
• the migration value can be determined, in particular, according to DIN SPEC 5010:2018-05.
• the migration test can be carried out in accordance with DIN SPEC 5010:2018-05, in particular using poly(2,3-diphenyl-p-phenylene oxide) (MPPO) as a simulant. MPPO is also frequently referred to as Tenax.
• the migration test is carried out for a period of 10 days at a temperature of 40°C.
• C ⁇ sub>x ⁇ /sub> for example C ⁇ sub> 16 ⁇ /sub> and C ⁇ sub>25 ⁇ /sub> , denotes in particular the number x of carbon atoms in n-alkanes, whose respective retention times during gas chromatographic separation serve as integration limits for the evaluation of the chromatograms.
• the integration of the n-alkanes is preferably carried out by including the signal maximum.
• the migration of MOSH with a chain length of C 16 to C 20 can be reduced, in particular, to a migration value of 1.5 mg/kg food or less, preferably 1.0 mg/kg food or less, more preferably 0.6 mg/kg food or less. Furthermore, with the fiber product according to the invention, the migration of MOSH with a chain length of C 16 to C 20 can be reduced, in particular, to a migration value of 0.3 mg/ dm2 or less, preferably 0.2 mg/ dm2 or less, more preferably 0.1 mg/ dm2 or less.
• the fiber product according to the invention can reduce the migration of MOAH with a chain length of C 16 to C 25 , in particular to a migration value of 0.3 mg/kg food or less, preferably 0.2 mg/kg food or less, and more preferably 0.15 mg/kg food or less.
• the fiber product according to the invention can reduce the migration of MOAH with a chain length of C 16 to C 25 , in particular to a migration value of 0.05 mg/ dm2 or less, preferably 0.04 mg/ dm2 or less, more preferably 0.03 mg/ dm2 or less, and most preferably 0.025 mg/ dm2 or less.
• the so-called EU cube For converting values in mg/ dm2 to mg/kg of food, the so-called EU cube can be used as a basis, according to which 1 mg/ dm2 corresponds to 6 mg/kg of food after conversion.
• the EU cube is familiar to those skilled in the art.
• the food item can be, in particular, a dry food.
• the fiber product can consist of a first fiber layer.
• the fiber product can comprise further layers, in particular additional fiber layers.
• the fiber product has eight additional fiber layers.
• the additional fiber layers can also contain activated carbon or be substantially free of activated carbon.
• the fiber product can have two or three fiber layers impregnated with activated carbon and two or three fiber layers that are substantially free of activated carbon.
• the fiber product has six fiber layers impregnated with activated carbon and three fiber layers that are substantially free of activated carbon.
• the chemical oxygen demand set in the inventive method is the chemical oxygen demand of the activated carbon-containing fiber suspension.
• the chemical oxygen demand is determined as described above for the fiber product.
• the fiber suspension, which is then applied to the former, serves as the sample. is used.
• autofiltrate was used if necessary.
• the chemical oxygen demand (COD) can be adjusted in various ways known to those skilled in the art. In particular, it can be adjusted by adding additives, especially COD additives.
• suitable COD additives include glues, glue fixatives, polymer compounds, stickies, starch, calcium carbonate, potassium carbonate, and kaolin.
• glues include alkyl ketene dimers.
• polymer compounds include polyacrylamides and polyethyleneimine.
• Other examples of COD additives include drying agents, retention polymers, and aldehydes.
• COD additives can be added in varying amounts.
• COD additives can be added in an amount of 0.1 to 5 wt.%, preferably 0.5 to 4.5 wt.%, more preferably 1.0 to 4.0 wt.%, and particularly preferably 2.0 to 4.0 wt.%, based on the dry weight of the cellulose-containing fibers.
• the fiber product contains 0.1 to 15 wt.%, preferably 0.5 to 10 wt.%, more preferably 1 to 8 wt.%, and particularly preferably 1 to 5 wt.%, activated carbon, in each case based on the dry weight of the fiber product.
• the dry weight of the fiber product is the air-dry dry weight. "Air-dry” here stands for “air-dry.”
• the residual moisture content at air-dry dry weight is 7 to 9 wt.%.
• the fiber product may also contain other additives.
• additives include dyes or pigments.
• the fiber product can have a protective layer.
• a protective layer particularly in the form of a coating, is a layer that forms a barrier. This barrier can serve to at least reduce the migration of unwanted substances into an adjacent product.
• a plastic coating and/or a metal coating can be provided.
• An additional protective layer can further improve safety. Even though, in principle, the incorporation of activated carbon into the fiber product is sufficient to reduce and, in particular, almost completely prevent the migration of mineral oil substances into another product, it is advantageous to provide an additional protective layer. If, for example, a production error occurs and the fiber product is not impregnated with activated carbon, the fiber product can still be used without concern due to the additional protective layer.
• the protective layer can be arranged at any position on the fiber product.
• a simple and particularly efficient embodiment exists when the fiber product has an outer layer, which is specifically designed as a protective layer.
• An outer protective layer can be applied to the top or bottom surface.
• the layer of the fiber product intended for contact with the product to be packaged can be designed as a protective layer.
• the protective layer can comprise suitable plastic and/or metallic materials that at least reduce the amount of migrating mineral oil hydrocarbons from the fiber product.
• the protective layer can also be designed to prevent the release of activated carbon from a fiber layer.
• the fiber product according to the invention does not have a protective layer.
• the invention also relates to the use of a fiber product according to the invention for the production of packaging, in particular food packaging, with reduced migration of Mineral oil hydrocarbons in a food product that comes into contact with the fiber product.
• the aforementioned problem is further solved according to the invention by the use of activated carbon in a fiber product for packaging to reduce the migration of mineral oil hydrocarbons, in particular from the fiber product, into a foodstuff in contact with the fiber product, wherein the fiber product has a chemical oxygen demand of 50 to 1,500 mg/L.
• the fiber product is preferably a fiber product according to the invention.
• the activated carbon has an iodine value of 800 mg/g or more, preferably 1,000 mg/g or more, and more preferably 1,200 mg/g or more.
• Activated carbon with such iodine values has a high specific surface area and is therefore particularly suitable for reducing mineral oil hydrocarbons.
• Activated carbon with an iodine value below 800 mg/g can also be used for the invention; however, this is disadvantageous because additional amounts of activated carbon must then be used to achieve a sufficient reduction in the migration of mineral oils through the fiber product.
• the iodine value of activated carbon can be determined, in particular, according to the standard ASTM D:4607-2014.
• the invention relates to a food packaging comprising a fiber product according to the invention.
• the food packaging is made from the fiber product according to the invention.
• the food packaging is preferably for dry foods.
• the food is preferably in contact with the food packaging.
• the fiber product has a cationic requirement of 0.1 to 3 mL, preferably 0.5 to 3 mL, more preferably 0.5 to 2.5 mL, and particularly preferably 1 to 2.4 mL.
• the cationic requirement refers to the amount of polyDADMAC titration solution.
• a cationic polyDADMAC solution with a known concentration of, for example, 20% w/v or 0.001 N, or preferably 0.001 N, polyDADMAC in water is used as the titration solution.
• PolyDADMAC stands for polydiallyldimethylammonium chloride.
• the cationic requirement is determined as the amount of polyDADMAC solution needed to neutralize a suspension of the fiber product in water.
• the titration can be performed, for example, using the Mütek PCD-05 instrument from BTG Instruments AB, poleffle, Sweden. A 300-mesh sieve from BTG Instruments AB is preferably used for sample preparation.
• a sample volume of 10 mL is preferably used.
• Titration solutions from BTG Instruments AB are preferably used.
• the cationic requirement of the fiber product or fiber suspension or activated carbon-containing fiber suspension specified herein refers in particular to a measurement using a titration solution of 0.001 N, PolyDADMAC in water on a sample of 10 mL.
• the fiber product can be comminuted in water, and then a sample of the resulting fiber suspension or a filtrate thereof can be analyzed.
• the sample preparation is carried out as described for the determination of the COD value.
• the fiber suspension can have a concentration in the range of 3 to 5 wt%, preferably 4 wt%, based on the total weight of the suspension.
• the fiber product has a basis weight of 50 to 1,000 g/ m2 , preferably of 80 to 800 g/ m2 , more preferably of 80 to 600 g/ m2 .
• the basis weight is preferably between 100 and 500 g/ m2 .
• the basis weight is preferably determined according to DIN EN ISO 536, in particular DIN EN ISO 536:2020-05.
• the basis weight is preferably the lutes basis weight.
• the individual fiber layers preferably each have a basis weight of 30 to 150 g/ m2 .
• Fiber layers impregnated with activated carbon can, in particular, have a basis weight of 80 to 150 g/ m2 .
• the fiber products according to the invention have the advantage that they sufficiently prevent the migration of mineral oil hydrocarbons even at a low basis weight of 50 g/ m2 . Furthermore, by using activated carbon, the migration of mineral oil hydrocarbons can also be sufficiently reduced in fiber products with a basis weight of up to 1,000 g/ m2 , even with a required COD value.
• the cellulose-containing fibers in the fiber product have a zeta potential of -8 to -22 mV, preferably -10 to -21 mV, more preferably -11 to -20 mV, and particularly preferably -12 to -19 mV.
• the fiber product can be pulverized in water and then a sample can be taken.
• the resulting fiber suspension or a filtrate thereof is to be examined.
• the sample preparation is carried out as described for the determination of the COD value.
• the fiber suspension can have a concentration in the range of 3 to 5 wt%, preferably 4 wt%, based on the total weight of the suspension.
• the zeta potential can be determined, in particular, using the Mütek SZP-06 instrument from BTG Instruments AB, poleffle, Sweden.
• the measurement is preferably carried out with a 500 mL sample.
• the sample preferably has a consistency of 3 to 5 wt%, preferably 4 wt%, optionally diluted with its own filtrate if the consistency is higher.
• the conductivity can be measured in parallel.
• the fiber product has a chemical oxygen demand of 50 to 1,200 mg/L, preferably 100 to 1,000 mg/L, more preferably 200 to 900 mg/L, and particularly preferably 300 to 800 mg/L.
• the fiber product can be in various forms.
• the fiber product is cardboard, carton, and/or paper.
• the cellulose-containing fibers comprise or consist of virgin fibers, recycled paper fibers, or a mixture of virgin fibers and recycled paper fibers.
• Waste paper fibers also called recycled fibers, can be made from waste paper. It is understood that the waste paper fibers may have been cleaned. While cleaning the waste paper fibers reduces the mineral oil content, it does so insufficiently. Only the addition of activated carbon and the treatment of the fibers according to the invention ensure that the migration of mineral oil hydrocarbons can be sufficiently reduced.
• Virgin fibers are, for example, fibers made from cellulose.
• the first fiber layer can consist exclusively of virgin fibers, exclusively of recycled paper fibers, or of both types of fibers in a predefined ratio.
• the cellulose-containing fibers comprise 20 wt.% or more, preferably 40 wt.% or more, more preferably 60 wt.% or more, even more preferably 80 wt.% or more, and particularly preferably 95 wt.% or more, recycled paper fibers, based on the total weight of the cellulose-containing fibers.
• the use of higher recycled fiber content is particularly advantageous from an environmental perspective.
• the chemical oxygen demand of the fiber suspension is reduced to a value of 1,800 to 3,000 immediately before the former. mg/L, more preferably 2,000 to 3,000 mg/L, particularly preferably 2,000 to 2,800 mg/L, adjusted.
• the cationic requirement of the activated carbon-containing fiber suspension is adjusted to a value of 0.01 to 3 mL, preferably 0.10 to 2.5 mL, more preferably 0.5 to 2 mL, immediately before the former.
• the cationic requirement is determined as described above for the fiber product.
• the fiber suspension, which is then applied to the former, is used as a sample. If necessary, autofiltrate was used to adjust the concentration to 4 wt%.
• the cationic requirement of the fiber product can be adjusted in various ways known to those skilled in the art. For example, it can be adjusted by adding activated carbon. Furthermore, the cationic requirement can be adjusted by adding fixatives. Examples of suitable fixatives are alum, aluminum sulfate, polyethyleneimine, polyDADMAC, silica, starch (cationic or native), and sizing agents, such as alkyl ketene dimer glue (AKD glue), alkyl succinic anhydride glue (ASA glue), or adhesive glue.
• suitable fixatives are alum, aluminum sulfate, polyethyleneimine, polyDADMAC, silica, starch (cationic or native), and sizing agents, such as alkyl ketene dimer glue (AKD glue), alkyl succinic anhydride glue (ASA glue), or adhesive glue.
• the aforementioned fixing agents can be added at various points in the fiber product manufacturing process.
• the fixing agents can be added to the fiber suspension in the vat. If activated carbon is added to the fiber suspension, the fixing agents can be added before and/or after the activated carbon, particularly in the vat. Furthermore, fixing agents can also be added after the vat, for example, immediately before the former.
• Fixatives can be added in varying amounts.
• fixatives can be added in amounts ranging from 0.01% to 5% by weight, particularly 0.1% to 4%. % by weight, added, based on the dry weight of the cellulose-containing fibers of the first fiber layer.
• the zeta potential in the activated carbon-containing fiber suspension is adjusted immediately before the former such that the cellulose-containing fibers have a zeta potential of -15 to -1 mV, preferably -12 to -2 mV, more preferably -10 to -3 mV, and particularly preferably -8 to -4 mV.
• the zeta potential is determined as described above for the fiber product.
• the fiber suspension, which is then applied to the former, is used as the sample. If necessary, autofiltrate was used to adjust the concentration to 4 wt%.
• the zeta potential of the activated carbon mixture can be adjusted by adding zeta additives.
• suitable zeta additives are the same as those used to meet cationic requirements.
• Zeta additives can be added in varying amounts.
• zeta additives can be added in amounts ranging from 0.01 to 5 wt%, particularly 0.1 to 4 wt%, based on the dry weight of the cellulose-containing fibers.
• an adhesive is added to the fiber suspension or the activated carbon-containing fiber suspension.
• the adhesive may be selected from the group consisting of resin adhesives, synthetic adhesives such as alkyl ketene dimer adhesives (AKD adhesives) or alkyl succinic anhydride adhesives (ASA adhesives).
• resin adhesives synthetic adhesives such as alkyl ketene dimer adhesives (AKD adhesives) or alkyl succinic anhydride adhesives (ASA adhesives).
• ASA adhesives alkyl succinic anhydride adhesives
• the fiber product can be produced with a retention of 45% or more, preferably 50% or more.
• the retention is calculated, in particular, as the percentage ratio of the mass of the obtained fiber product to the amount of raw material, additives, and fixing agents used.
• Example 1 Reduction of mineral oil migration in a fiber product with a set chemical oxygen demand
• Cardboard for food packaging was manufactured as a fiber product.
• This cardboard consisted of nine fiber layers, six of which were inner layers impregnated with activated carbon and bonded together. These six inner fiber layers with activated carbon are referred to below as the core.
• the cardboard also had a top layer, a protective layer, and a back layer, each free of activated carbon.
• Various cardboard types were produced, with only the core being varied.
• the fiber layers that did not form the core were produced from a fiber suspension without activated carbon in a manner known to those skilled in the art, using standard additives and auxiliaries.
• the cardboard had a basis weight of 350 g/ m2 according to DIN EN ISO 536:2020-05.
• the front side had two pigment coatings, and the back side had one pigment coating.
• the pigment coating consisted of a commercially available carbonate/kaolin mixture.
• the insoles were manufactured as follows. First, a fiber suspension was prepared in a separate tub for each insole, which It comprised cellulose-containing fibers and water. The cellulose-containing fibers in the fiber suspension for both the ply and the cover, protective, and backing layers were each mixed recycled paper fibers.
• an aqueous suspension containing activated carbon with an iodine value of approximately 1050 mg/g was added in varying amounts, as shown in Table 1 below, based on the dry weight of the cardboard, including fiber products as a control that did not contain activated carbon.
• one or more additives were added to the various fiber suspensions.
• the chemical oxygen demand (COD) of the fiber suspension in the vat was approximately 4500 mg/L.
• one or more of the following additives were used: alum, aluminum sulfate, polyacrylamide, polyvinylamine, polyethyleneimine, polyDADMAC, starch, calcium carbonate, potassium carbonate, kaolin, silica, AKD glue, and ASA glue.
• Polyacrylamide and polyvinylamine were the most commonly used.
• the layers of the insert were produced from the mixtures, with the COD value of the activated carbon-containing fiber suspension being adjusted to approximately 2,500 mg/L by adding polyacrylamide immediately before the former. The respective inserts were then bonded with the remaining layers to form a nine-layer cardboard unit.
• the COD value was determined using the Hach LCK cuvette test, employing LCK014 cuvettes from Hach Lange GmbH, Düsseldorf. A fresh cuvette was removed and shaken to suspend any sediment. Then, 2.0 mL of the sample was slowly added to the cuvette using a piston-stroke pipette.
• the cuvette was then sealed, thoroughly cleaned on the outside, swirled, and heated in a thermostat at 148°C for two hours.
• the hot cuvette was then removed, swirled twice, and cooled to room temperature in a cuvette rack. Afterward, the cuvette was thoroughly cleaned on the outside and analyzed using a Hach photometer, ensuring that any sediment had completely settled before measurement.
• the cardboard was dried and then tested for migration according to DIN SPEC 5010:2018-05.
• MPPO was used as a food simulant for the migration test.
• the migration test was carried out for 10 days at a temperature of 40°C.
• the detection and, where necessary, separation of MOSH and MOAH was performed according to DIN SPEC 5010:2018-05 using online-coupled HPLC-GC-FID and for the Chain lengths of the n-alkanes C16 to C20 and C16 to C25 were determined, with the integration of the n-alkanes including the signal maxima.
• the determined migration values for MOSH compounds and MOAH compounds were calculated separately and are listed in Table 1.
• Table 1 Migration values and COD values sample COD value [mg/L] Percentage of activated carbon b [wt.%] Retention c [%] MOSH d [mg/kg food] MOAH e [mg/kg food] 1 490 1 55 1.5 0.49 2 600 2 50 0.6 or less 0.15 or less V1 f 530 0 57 40 51 V2 f 1970 2 30 0.6 or less 0.15 or less Explanations for Table 1: a - Determined chemical oxygen demand of the carton; b - Determined proportion of activated carbon in the carton, based on the dry weight (lutro) of the carton; c - Retention of the insert, based on the amount of raw material used, as well as additives and fixatives; d - Migration value for MOSH with a chain length of C16-C20, determined as described above using Tenax; e - Migration value for MOAH with a chain length of C16-C25, determined as described above using Tenax; f
• the experiment shows that fiber products according to the invention, which have a chemical oxygen demand of 50 to 1,500 mg/L, reduce the migration of mineral oils such as MOSH and MOAH more effectively than conventional fiber products with an oxygen demand outside this range and can be manufactured well at the same time.
• Example 2 Reduction of mineral oil migration in a fiber product with a set cationic demand
• a cardboard fiber product was manufactured according to the process described in Example 1, with the exception that the cationic requirements of the fiber product were also adjusted.
• polyacrylamide or polyvinylamine was added to the various fiber suspensions.
• an alternative fixing agent can be selected from alum, aluminum sulfate, polyethyleneimine, polyDADMAC, starch, calcium carbonate, potassium carbonate, kaolin, silica, AKD glue, or ASA glue.
• the cationic requirements of the activated carbon-containing fiber suspension were adjusted to a value of 1 mL to 3 mL by adding polyacrylamide.
• the cationic demand of the fiber product was determined by titration using a 0.001 N PolyDADMAC solution from BTG Instruments AB until neutralization.
• a 4% fiber suspension was prepared from the cardboard, following the same procedure as described in Example 1 for determining the COD value of the cardboard.
• This suspension was then filtered using a 300-mesh sieve from BTG Instruments AB.
• the filtrate was subsequently analyzed as a sample of the fiber product.
• the titration was performed using a Mütek PCD-05 instrument from BTG Instruments AB, poleffle, Sweden. A sample volume of 10 mL was used.
• Example 2 The migration test described in Example 1 was performed on the cardboard. Migration values for MOSH compounds and MOAH compounds were determined separately and are listed in Table 2.
• Table 2 Cationic demand and migration values sample Cationic requirement a [mL] Percentage of activated carbon b [wt.%] Retention c [%] MOSH d [mg/kg food] MOAH e [mg/kg food] 3 1.3 1 55 1.5 0.49 4 1.0 2 50 0.6 or less 0.15 or less V3 f 1.5 0 57 40 51 V4 f 3.5 2 40 0.6 or less 0.15 or less Explanations for Table 2: a - Determined cationic requirement of the carton; b - Determined proportion of activated carbon in the carton, based on the dry weight (lutro) of the carton; c - Retention of the insert, based on the amount of raw material used as well as additives and fixatives; d - Migration value for MOSH with a chain length of C16-C20, determined as described
• Example 3 Reduction of mineral oil migration in a fiber product with a set zeta potential
• a cardboard fiber product was manufactured according to the process described in Example 1, with the exception that the zeta potential of the fiber product was also adjusted.
• at least one zeta additive was selected from alum, aluminum sulfate, polyacrylamide, or polyvinylamine for the various fiber suspensions, depending on the raw material of the cellulose-containing fibers. Polyethyleneimine, polyDADMAC, starch, calcium carbonate, potassium carbonate, kaolin, silica, AKD glue, or ASA glue were added. Polyacrylamide or polyvinylamine was usually added as well. Immediately before the former, the zeta potential of the cellulose-containing fibers in the activated carbon-containing fiber suspension was adjusted to a value of -8 to -4 mV by adding polyacrylamide.
• the zeta potential of the fiber product was determined using the Mütek SZP-06 instrument from BTG Instruments AB, poleffle, Sweden.
• a 4% fiber suspension was prepared from the cardboard, following the same procedure as described in Example 1 for determining the COD value of the cardboard.
• the sample was not filtered. Instead, 500 mL of the 4% fiber suspension was used. If necessary, the sample was diluted with filtrate from the fiber suspension.
• Example 1 The migration test described in Example 1 was performed on the cardboard. Migration values for MOSH compounds and MOAH compounds were determined separately and are listed in Table 3. Table 3: Zeta potential and migration values sample Zeta potential a [mV] Percentage of activated carbon b [wt.%] Retention c [%] MOSH d [mg/kg food] MOAH e [mg/kg food] 5 -13 1 55 3.60 0.25 6 -17 2 50 2.5 0.50 V5 f -13.3 0 57 40 51 V6 f -23 2 41 0.6 or less 0.15 or less Explanations for Table 3: a - Determined zeta potential of the cardboard; b - Determined proportion of activated carbon in the cardboard, based on the dry weight (lutro) of the cardboard; c - Retention of the insert, based on the amount of raw material used, as well as additives and fixatives; d - Migration value for MOSH with a chain length of C16-C20, determined as described

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