EP3262232B1 - Beschichtungszusammensetzung mit hydrolysierten weizenproteinen - Google Patents

Beschichtungszusammensetzung mit hydrolysierten weizenproteinen Download PDF

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Publication number
EP3262232B1
EP3262232B1 EP16707224.8A EP16707224A EP3262232B1 EP 3262232 B1 EP3262232 B1 EP 3262232B1 EP 16707224 A EP16707224 A EP 16707224A EP 3262232 B1 EP3262232 B1 EP 3262232B1
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EP
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Prior art keywords
paper
starch
composition according
wheat protein
kda
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EP16707224.8A
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English (en)
French (fr)
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EP3262232A1 (de
Inventor
Magalie PERALBA
Sofie Frederix
Vittorio Rivolta
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Tereos Starch and Sweeteners Belgium
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Tereos Starch and Sweeteners Belgium
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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
    • 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
    • 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
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/22—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
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/385—Oxides, hydroxides or carbonates
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/50—Proteins

Definitions

  • the present invention relates to a paper or paperboard coating composition comprising a modified starch and a hydrolyzed wheat protein as well as the method for obtaining such a composition.
  • the invention also relates to a process for coating or bluing paper or board using such a composition, the coated paper or board thus obtained.
  • the invention finally relates to the use of a hydrolysed wheat protein in the replacement of the latex in a paper or paperboard coating composition.
  • Coating also known as coating, is a finishing step for paper or board which makes it possible to give a sheet of paper or a cardboard a number of properties, such as opacity, gloss, whiteness or to improve printability for printing processes such as offset or gravure.
  • a composition called coating color is applied to the surface of the paper or board.
  • This composition generally comprises at least one inorganic filler or pigment, at least one binder and other additives such as in particular dispersants, rheology modifiers, lubricants, optical brighteners or anti-foams.
  • Latex typically synthetic styrene-butadiene type latex is the most widely used binder. Its function is to allow the cohesion between the different elements of the composition and to bind them to the fibers.
  • Synthetic latex is produced from petroleum resources that are by definition non-renewable. In order to reduce the number of chemicals used in this industry, to decrease the consumption of petroleum products as well as the costs, the replacement of the latex in the coating sauces represents a potential market but also a major technical challenge. Indeed, it is very difficult to maintain the performance of a coating color by reducing the proportion of synthetic latex used.
  • coating colors are intended to be applied to the surface of paper or cardboard in very thin layers and at very high speed. They are applied by means of a filamented blade or rod which exerts very large shear forces on the surface of the paper.
  • these shearing forces cause not only at the application zone, turbulences responsible for defects in the deposit called “baves” or “pearls” but also an increase the pressure exerted on the paper thus increasing the risk of breakage and therefore potentially production downtime.
  • the prior art proposes coating compositions having a low solids content.
  • the reduction of the dry matter of the composition (and therefore the increase in the water content) in order to reduce the viscosity is not an advantageous solution in the present application.
  • the coating color has a natural tendency to transfer all or part of the water and the water-soluble parts it contains into the paper sheet. This has several consequences, the first of which is the weakening of the paper or the cardboard which by the excess of water, can lose its integrity and cause a breakage of the produced paper and thus hours of stoppage of production. The second is loss of gloss of the paper observed following the migration of the water-soluble parts of the coating color into the paper.
  • This migration leads to a third consequence which is the weakening of the cohesion of the paper layer causing problems during printing. For example, there may be mentioned deposits of fibers or mineral fillers originating from the layer on the blankets during offset printing. The last consequence of this excess of water of the coating composition is the increase of the energy and / or the time necessary for drying the obtained paper or board.
  • the advantage of a coating color having both a high solids content and a low viscosity beyond the resolution of the above-mentioned problems is the low need for the coating color.
  • a coating of low viscosity coating would also have the advantage of allowing a very high speed coating which is a very clear industrial advantage.
  • coating composition of paper or cardboard is meant a composition particularly suitable for coating paper or paperboard. It is an aqueous formulation typically containing water, at least one mineral filler, one or more binders and various additives.
  • wheat protein refers to a water insoluble protein fraction, extracted from wheat flour wet and then dried, also called wheat gluten.
  • wheat proteins having an average molecular mass of between 7 and 1000 kDa are obtained by hydrolysis according to methods well known to those skilled in the art [ Anfinsen, CB Jr. (1965) Advances in Protein Chemistry: v.20. New York and London: Academic Press ].
  • the hydrolysis can be thermal, acidic or enzymatic. Enzymatic hydrolysis is preferred.
  • a wheat gluten particularly suitable for the present invention is SOLPRO® 508 marketed by TEREOS SYRAL
  • the hydrolysed wheat protein according to the invention has a weight average molecular weight of between 7 and 800 kDa, 5 and 500 kDa or 8 and 100 kDa, preferably between 9 and 80 kDa, more preferably between 10 and 70 kDa, even more preferably between 12 and and 50KDa, even more preferably between 13 and 40KDa.
  • binder is meant a compound having the function of bonding the inorganic filler particles (or pigments) together and keeping the layer on the surface of the paper.
  • the composition comprises a binding ratio / wheat protein of 1: 5 to 5: 1, preferably of 1: 3 to 3: 1, more preferably 1: 2 to 2: 1.
  • the binders are at least one modified starch and an adhesive such as a synthetic adhesive.
  • an adhesive such as a synthetic adhesive.
  • a modified starch / synthetic adhesive ratio of 1: 5 to 5: 1, preferably 1: 3 to 3: 1, more preferably 1: 2 to 2: 1.
  • modified starch in the sense of the present invention any starch that has been chemically or physically treated.
  • the modified starch molecules present in the present invention may be from a plant source such as cereals, tubers, roots, vegetables and fruits.
  • the starch (s) may come from a vegetable source selected from corn, peas, potato, sweet potato, banana, barley, wheat, rice, oats, sago, tapioca and sorghum.
  • Suitable modified starches include, but are not limited to, pregelatinized starches, low viscosity starches (e.g., dextrins, hydrolyzed starches, oxidized starches), stabilized starches (e.g., starch esters, ethers, and the like). starch), crosslinked starches and starches which have received a combination of treatments (e.g., crosslinking and gelatinization) and mixtures thereof.
  • Dextrins are the preferred modified starches.
  • the term " dextrin" means a modified starch obtained from native starch by dextrinisation, typically the dextrins according to the invention are not subjected to any other modification, in particular chemical modification.
  • the dextrins suitable for the present invention are, for example, white dextrins, generally obtained by transformation of the starch at temperatures often between 100 and 170 ° C., in the presence of chemical agent (s), in particular of acid, in relatively large amounts. Yellow dextrins, often obtained by transformation of the starch at higher temperatures, generally between 170 and 230 ° C, in the presence of chemical agent (s), especially acid.
  • a dextrin particularly suitable for the present invention is a dextrin wheat base typically dextrin MYLOFILM® 214 or MYLOFILM® 218commercialized by the company TEREOS SYRAL.
  • the modified modified starch has a weight-average molecular weight of between 20 and 300 kDa, preferably 30 and 250 kDa, more preferably between 35 and 233 kDa, still more preferably between 40 and 40 kDa. 200KDa, even more preferably between 42 and 150 kDa and / or a viscosity of between 50 and 400 mPa.s (brookfield, 70 ° C, 31% DS).
  • the brookfield viscometer measurement of the modified starch such as, for example, dextrin is carried out in solution and is carried out on an RVDV-E model, the measurement is made at a speed of 20 rpm with pin 3.
  • the measurements are made at 70 ° C.
  • the module is soaked in a modified starch composition suspended at 31% dry matter up to the pin indicator line, the value is read after 10 s turn.
  • average molecular weight is meant the weight average molecular weight.
  • this average molecular mass is measured by steric exclusion chromatography (SE-HPLC) coupled with a UV detector set at the wavelength of 214 nm.
  • Exclusion chromatography Steric is equipped with a pump circulating an eluent composed of a PBS phosphate buffer (0.1 M Na 2 HPO 4 -NaH 2 PO 4 with 0.1% SDS) at a flow rate of 0.7 ml / min in a TSKG4000SWx1 column. This measure is expressed in Dalton.
  • the preparation of a sample can be done by solubilizing the test product in an extraction phosphate buffer with 1% SDS followed by centrifugation to recover the supernatant.
  • the average molecular weight is expressed in Dalton and can be determined by those skilled in the art by steric exclusion chromatography coupled with a MALLS type detector (Multi Angle Laser Light Scattering).
  • the preparation of a sample may be carried out by solubilizing 50 mg of dry mass of a modified starch and in particular of dextrin in a solvent consisting of a mixture of 90% (v / v) of DMSO (dimethyl sulfoxide) in a solvent. deionized water containing 0.1% (w / v) sodium nitrate. After stirring overnight, the mixture is preheated for 1 hour at 105 ° C.
  • the adhesive is preferably synthetic.
  • An example of a synthetic adhesive suitable for the present invention is a latex, a vinyl acetate, polyvinyl alcohol, sodium carboxymethylcellulose and hydroxyethylcellulose.
  • latex refers to an aqueous polymer dispersion which corresponds to a colloidal dispersion of synthetic polymers in an aqueous phase, ie a dispersion of polymer microparticles suspended in an aqueous phase, sometimes also called suspension or emulsion of polymers.
  • examples of latex suitable for the present invention are chosen from the group consisting of styrene-butadiene latex, polyvinyl alcohol latex and latex acrylic copolymer preferentially, the styrene-butadiene type latex.
  • the introduced inorganic filler is conveyed in the form of an aqueous suspension.
  • this filler is a calcium carbonate suspended in water by means of a dispersing agent.
  • a mineral filler particularly suitable for a coating composition comprises a sufficient degree of whiteness (greater than 80% of the whiteness of the barium sulfate at 457 nm), a particle size distribution of 0 to 10 ⁇ m at the most, (the average particle size between 0.2 and 2 ⁇ m) and a minimum degree of agglomeration of the particles.
  • the inorganic filler may be selected from the group consisting of calcium carbonates, coating clay, calcined fine clay, alumina trihydrate, talc and titanium dioxide.
  • calcium carbonate includes ground calcium carbonate (GCC), that is, calcium carbonate obtained from natural sources, such as limestone, marble, calcite or lime.
  • GCC ground calcium carbonate
  • calcium carbonate obtained from natural sources, such as limestone, marble, calcite or lime.
  • calcium carbonate also includes precipitated calcium carbonate (PCC), that is a synthesized substance, generally obtained by precipitation following a reaction of carbon dioxide and calcium hydroxide (hydrated lime ) in an aqueous environment or by precipitation of a source of calcium and carbonate in water.
  • composition according to the invention may also comprise other agents such as one or more dispersing agents.
  • dispersing agent is meant an agent having the function of maintaining the inorganic filler particles in an electrostatic dispersion state.
  • the dispersing agent is chosen from the group consisting of sodium polyacrylate, tetrasodium polyphosphate, tetrasodium pyrophosphate, pentasodium tripolyphosphate, sodium tetraphosphate and sodium silicate.
  • composition may also comprise at least one lubricant, typically selected from the group consisting of sodium stearate, stearate of calcium, sulphonated oils, sulphated tall oil fatty acid and polyethylene emulsions
  • composition may further comprise at least one insolubilizing agent selected from the group consisting of urea resins, melamine resins, glyoxal, zinc compounds, formaldehyde and dimethylolurea.
  • insolubilizing agent selected from the group consisting of urea resins, melamine resins, glyoxal, zinc compounds, formaldehyde and dimethylolurea.
  • the step of depositing said composition on a paper or cardboard substrate can be carried out by means of a blade coating, a pencil coating, a filamented rod, a curtain size press or a press film or any other technique known to those skilled in the art.
  • the deposition step is carried out at a temperature between 25 and 60 ° C.
  • said composition is applied to at least one face of said paper or paperboard substrate in an amount of between 3 g / m 2 and 15 g / m 2 , preferably between 5 g / m 2 and 10 g / m 2 .
  • the invention also relates to a paper or cardboard coated with the composition according to the invention.
  • the invention further relates to the use of a hydrolysed wheat protein in the replacement of the latex in a paper or paperboard coating composition, preferably said hydrolysed wheat protein has an average molecular weight of between 7 and 1000 kDa.
  • the invention relates to the use of a combination of a hydrolysed wheat protein and a modified starch and more particularly a dextrin in the replacement of the latex, preferably in a ratio of modified starch / wheat protein of 1: 5 at 5: 1, preferably from 1: 3 to 3: 1, more preferably 1: 2 to 2: 1.
  • said wheat protein or said wheat protein combination with a modified starch, preferably a dextrin is used in the replacement of 1 to 40% of the latex of said composition, preferably 10 to 35%, more preferably 15 to 30%.
  • a coating color was prepared according to formulas R1 to R4 of Table 1 below. ⁇ i> ⁇ u> Table 1 ⁇ / u>: Coating compositions comprising dextrin as partial replacement for latex ⁇ / i> Calcium carbonate Synthetic binder Dextrin R1 100 3.5 3.5 R2 100 3 4 R3 100 2.5 4.5 R4 100 2 5
  • the recipes are given in number of shares (as usual in stationery).
  • the coating color is produced by means of an agitator (IKA type), firstly by suspending in water the 79.7% calcium carbonate (HYDROCARB® 90 supplied by OMYA). Then the synthetic binder (styrene butadiene latex DL930 from the company STYRON) and the dextrin dissolved as specified above are added to the calcium carbonate. The concentration is adjusted with water to obtain a solids content of 70%. The stirring speed is adjusted to 1500 rpm, the pH is then adjusted to 9. The coating color is thus stirred for 10 min. The coating colors of Table 1 were tested in coating tests. The viscosity of the coating colors is evaluated before coating the paper.
  • IKA type agitator
  • the brookfield viscometer coating is measured on a RVDV-E model, the measurement is made at a speed of 20 rpm with spindle 3. The measurements are made at 40 ° C. The module is dipped in the coating color to the pin marking, the value is read after 10 s turn.
  • the coating color is deposited on the paper at a height of 6 gr / m 2 on a single face thanks to a sleeping pilot DT coater coating blade allowing drying combining infrared radiation and hot air.
  • the coating speed is 20 m / min.
  • the paper used is a fine paper 80 g / m 2 supplied by the company FEDRIGONI.
  • the paper thus coated is then stored in a room conditioned in humidity and temperature (50% humidity, 23 ° C) for 24 hours before any test.
  • the dry tear measurement is done according to the method of IGT W31 (ISO 3783: 2006). This measurement makes it possible to evaluate the strength of the layer. Indeed, binders (synthetic or natural such as starch) are used to maintain the mineral fillers required for printing properties on paper. If the binding power is too low, the mineral fillers are torn off the paper during printing and are deposited on the ink roller resulting in frequent stops. The higher the dry IGT measurement, the more resistant the layer is to pulling.
  • Example 1 The coating colors were made as in Example 1 according to the formula in Table 3 in which the synthetic latex is replaced by proteins at 14% (R5), 30% (R6) and 43% (R7).
  • ⁇ / u> Coating compositions comprising dextrin and proteins as partial replacement of latex ⁇ / i> Calcium carbonate Synthetic binder Dextrin Protein R1 100 3.5 3.5 - R5 100 3 3.5 0.5 R6 100 2.5 3.5 1 R7 100 2 3.5 1.5
  • hydrolysed wheat and soy protein were tested on the basis of the proportions shown in Table 3.
  • the proteins are added to the coating color without prior dilution.
  • the coating coloring is carried out as in Example 1, using an agitator (IKA type) by suspending in water the 79.7% calcium carbonate (HYDROCARB® 90 supplied by OMYA). Then the synthetic binder (styrene butadiene latex DL930 from the company STYRON) as well as the dextrin dissolved in solution are added to the calcium carbonate as specified above.
  • the protein is incorporated at this stage into the sauce in the form of a solution or in powder form depending on the case.
  • the concentration is adjusted with water to obtain a solids content of 70%.
  • the stirring speed is adjusted to 1500 rpm, the pH is then adjusted to 9.
  • the coating color is thus stirred for 10 min.
  • hydrolysates of low molecular weight wheat protein have only a limited effect on the viscosity of the composition obtained but do not make it possible to compensate the reduction of latex by as much as 30%. In fact, at 30% replacement of the latex, a loss of tearing resistance is observed (from 0.45 IGT to 0% replacement, 0.5 to 14% replacement for 0.30 to 30% replacement).
  • composition R5 the partially hydrolysed wheat proteins allow a significant increase in the pull-out strength at 14% replacement of the latex (composition R5).
  • hydrolysed wheat proteins are that unlike soy proteins they are sufficiently soluble to be added directly to the coating color and do not require prior dilution adding a significant amount of water and thus reducing the dry matter of the coating, which allows to vary quite freely the dry matter of the composition.

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  • Paper (AREA)
  • Paints Or Removers (AREA)

Claims (15)

  1. Papier- oder Kartonbeschichtungszusammensetzung mit einer Trockenmasse im Bereich zwischen 45 und 80 %, vorzugsweise 50 und 78 %, umfassend
    • Bindemittel, die mindestens eine modifizierte Stärke und einen synthetischen Klebstoff enthalten,
    • ein hydrolysiertes Weizenprotein mit einem durchschnittlichen Molekulargewicht im Bereich zwischen 7 und 1.000 kDa, und
    • einen mineralischen Füllstoff.
  2. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, dass das hydrolysierte Weizenprotein ein durchschnittliches Molekulargewicht im Bereich zwischen 8 und 100 kDa, vorzugsweise zwischen 9 und 80 kDa aufweist.
  3. Zusammensetzung nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass sie je 100 Gewichtsteile mineralischem Füllstoff:
    - 1 bis 99 Teile Bindemittel, und
    - 1 bis 50 Gewichtsteile Weizenprotein umfasst.
  4. Zusammensetzung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass sie ein Verhältnis von modifizierter Stärke/synthetischem Klebstoff 1:5 bis 5:1 umfasst.
  5. Zusammensetzung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass sie ein Verhältnis von Bindemitteln/Weizenprotein 1:5 bis 5:1 umfasst.
  6. Zusammensetzung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die modifizierte Stärke ausgewählt ist aus einer vorgelierten Stärke, einem Dextrin, einer hydrolysierten Stärke, einer oxidierten Stärke, einem Stärkeester, einem Stärkeether, einer vernetzten Stärke und Mischungen davon, wobei die modifizierte Stärke vorzugsweise ein Dextrin ist.
  7. Zusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Dextrin eine Molekülmasse im Bereich zwischen 20 und 300 kDa, und/oder eine Viskosität im Bereich zwischen 50 und 400 mPa.s aufweist.
  8. Zusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der synthetische Klebstoff ausgewählt ist aus der Gruppe bestehend aus Latex, Vinylacetaten, Polyvinylalkohol, Natriumcarboxymethylcellulose und Hydroxyethylcellulose.
  9. Zusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der synthetische Klebstoff ein Latex ist, vorzugsweise ausgewählt aus der Gruppe bestehend aus StyrolButadien-Latex, Polyvinylalkohollatex und Copolyacrylat-Latex.
  10. Verfahren zur Herstellung der Zusammensetzung nach einem der Ansprüche 1 bis 9, umfassend die folgenden Schritte:
    - Mischen eines mineralischen Füllstoffs und Bindemitteln, darunter mindestens eine modifizierte Stärke und ein synthetischer Klebstoff, wobei die modifizierte Stärke vorzugsweise einem Wärmebehandlungsschritt unterzogen wurde,
    - Zugeben unter Rühren zur erhaltenen Mischung eines hydrolysierten Weizenproteins, das eine mittlere Molekülmasse im Bereich zwischen 7 und 1.000 kDa aufweist, wobei das hydrolysierte Weizenprotein vorzugsweise in Pulverform vorliegt,
    - Zugeben unter Rühren von Wasser, um eine Zusammensetzung zu erhalten, die eine Trockenmasse im Bereich zwischen 45 und 80 % aufweist, wobei die Zugabe von Wasser in der Regel mit dem mineralischen Füllstoff und/oder der modifizierten Stärke und/oder dem hydrolysierten Protein durchgeführt wird.
  11. Verfahren zum Beschichten oder Aufhellen von Papier oder Karton, wobei das Verfahren die folgenden Schritte umfasst
    (a) Bereitstellen einer Zusammensetzung nach einem der Ansprüche 1 bis 9,
    (b) Auftragen der Zusammensetzung auf einem Substrat aus Papier oder Karton.
  12. Papier oder Karton, das/der mit der Zusammensetzung nach einem der Ansprüche 1 bis 9 beschichtet ist oder durch das Verfahren nach Anspruch 11 erhalten wird.
  13. Verwendung eines hydrolysierten Weizenproteins beim Ersetzen des Latex in einer Beschichtungszusammensetzung für Papier oder Karton, wobei das hydrolysierte Weizenprotein vorzugsweise eine durchschnittliche Molekülmasse im Bereich zwischen 7 und 1.000 kDa aufweist.
  14. Verwendung nach Anspruch 13, dadurch gekennzeichnet, dass die Zusammensetzung umfasst
    • Bindemittel, darunter mindestens eine modifizierte Stärke und einen vorzugsweise synthetischen Klebstoff,
    • ein hydrolysiertes Weizenprotein mit einem durchschnittlichen Molekulargewicht im Bereich zwischen 7 und 1.000 kDa, und
    • einen mineralischen Füllstoff.
  15. Verwendung nach einem der Ansprüche 13 und 14, dadurch gekennzeichnet, dass das Verhältnis von Bindemitteln/Weizenprotein 1:5 bis 5:1 beträgt.
EP16707224.8A 2015-02-23 2016-02-23 Beschichtungszusammensetzung mit hydrolysierten weizenproteinen Active EP3262232B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1500337A FR3032979B1 (fr) 2015-02-23 2015-02-23 Composition de couchage comprenant des proteines de ble hydrolysees
PCT/IB2016/050969 WO2016135625A1 (fr) 2015-02-23 2016-02-23 Composition de couchage comprenant des protéines de blé hydrolysées

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EP3262232A1 EP3262232A1 (de) 2018-01-03
EP3262232B1 true EP3262232B1 (de) 2019-04-03

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US (1) US20180044858A1 (de)
EP (1) EP3262232B1 (de)
JP (1) JP2018511712A (de)
CN (1) CN107532390A (de)
BE (1) BE1023282B1 (de)
BR (1) BR112017015729A2 (de)
CA (1) CA2975499A1 (de)
FR (1) FR3032979B1 (de)
WO (1) WO2016135625A1 (de)

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US11440269B2 (en) * 2020-03-14 2022-09-13 Kurtis Zhang Process of making a gluten-based biodegradable material

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CA2975499A1 (fr) 2016-09-01
JP2018511712A (ja) 2018-04-26
FR3032979A1 (fr) 2016-08-26
US20180044858A1 (en) 2018-02-15
EP3262232A1 (de) 2018-01-03
BE1023282B1 (nl) 2017-01-20
BR112017015729A2 (pt) 2018-03-13
WO2016135625A1 (fr) 2016-09-01
BE1023282A1 (nl) 2017-01-20
FR3032979B1 (fr) 2017-02-10
CN107532390A (zh) 2018-01-02

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