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WO2024205475A1 - Matériau de mélange de protéines avec de la zéine et une deuxième protéine végétale, et procédé de production d'un film ou d'une mousse absorbante à partir du matériau - Google Patents

Matériau de mélange de protéines avec de la zéine et une deuxième protéine végétale, et procédé de production d'un film ou d'une mousse absorbante à partir du matériau Download PDF

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Publication number
WO2024205475A1
WO2024205475A1 PCT/SE2024/050278 SE2024050278W WO2024205475A1 WO 2024205475 A1 WO2024205475 A1 WO 2024205475A1 SE 2024050278 W SE2024050278 W SE 2024050278W WO 2024205475 A1 WO2024205475 A1 WO 2024205475A1
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WIPO (PCT)
Prior art keywords
protein
zein
weight
foam
film
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PCT/SE2024/050278
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English (en)
Inventor
Marco SABINO
Richard Olsson
Björn BIRDSONG
Mercedes BETELLI
Liliana HURTADO
Antonio CAPEZZA
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Individual
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Publication of WO2024205475A1 publication Critical patent/WO2024205475A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H1/00—Macromolecular products derived from proteins
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/32—Proteins, polypeptides; Degradation products or derivatives thereof, e.g. albumin, collagen, fibrin, gelatin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/425—Porous materials, e.g. foams or sponges
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07K—PEPTIDES
    • C07K14/00—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
    • C07K14/415—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from plants
    • C07K14/425—Zeins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/84—Accessories, not otherwise provided for, for absorbent pads
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2089/00—Use of proteins, e.g. casein, gelatine or derivatives thereof, as moulding material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/026—Crosslinking before of after foaming
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/03—Extrusion of the foamable blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2389/00—Characterised by the use of proteins; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2489/00—Characterised by the use of proteins; Derivatives thereof

Definitions

  • PROTEIN BLEND MATERIAL METHOD OF PRODUCING A PROTEIN BLEND MATERIAL AND ABSORBENT ARTICLE COMPRISING PROTEIN BLEND MATERIAL FIELD OF THE INVENTION
  • the present invention relates to the field of absorbent articles constructed with materials comprising proteins, thereby providing alternatives to conventional petroleum based absorbent articles.
  • BACKGROUND OF THE INVENTION A wide range of personal hygiene products use absorbent and porous materials to absorb, distribute and retain large amounts of water, blood or other body fluids.
  • Disposable absorbent articles such as diapers, incontinence pads, sanitary pads, breastfeeding pads, band aids, absorbent protection bedsheets and the like require not only a high absorption capacity but also a high absorption under load.
  • diapers, incontinence pads and sanitary pads use absorbent and porous materials that are petroleum based and constructed from so called superabsorbent polymers, such as based on poly(acrylic acid), and non-woven fibers, such as polyethylene and polypropylene. Furthermore, diapers, incontinence, and sanitary pads are consumables intended as single-use products and must be disposed of after respective liquid uptake.
  • the conventional materials employed are not biodegradable and their disposal contributes to municipal solid waste as well as the risk of accumulation of microplastics in nature. Due to the dependency on petroleum feedstocks, the short product life and the liability of their disposal, there is a demand to develop biodegradable new materials for absorbent articles from biomass feedstocks.
  • conventional diapers, incontinence pads and sanitary pads are assembled with petroleum based films and porous films encapsulating the absorbent material, which further contributes to problems with disposal and accumulation of microplastics.
  • Naturally sourced polymeric materials, such as proteins, have been considered for use in foams and films for absorbent articles.
  • Wheat gluten constitutes a source of material that is obtained as a co-product from wheat starch extraction and bioethanol production.
  • a problem with the adoption of wheat gluten is that it requires addition of toxic cross- linkers such as glutaraldehyde and plasticizers to stabilize the materials, prevent phase separation of mixtures, and prevent the collapse of the material accompanied with drying.
  • wheat gluten has a risk of cross-linking to itself in processes that are difficult to control as well as resulting in materials difficult to process into homogeneous porous structures.
  • wheat gluten is also rapidly attacked by microorganisms, such as mold, thereby limiting the shelf life of gluten based materials.
  • wheat gluten requires processing prior to material production, such as acylation.
  • these additional processes influence the cost of the materials.
  • the objective of the present invention is to overcome the drawback of the prior art and to present a material based on protein blends.
  • the present inventors found that a material comprising a plasticizer, a first protein, wherein the first protein is zein, and a second protein, wherein the second protein is selected from a group consisting of glutenin, gliadin, secalin, hordein, avenin or a combination thereof, resulted in a material that demonstrated an ability to form porous extrudates, porous films or films from the same formulation.
  • the present invention relates to a material comprising i) A first protein, wherein the first protein is zein, ii) A second protein selected from a group consisting of glutenin, gliadin, secalin, hordein, avenin or a combination thereof, and iii) A plasticizer, wherein the material has a weight ratio between zein and the second protein between 1:1 and 4:1, preferably between 1:1 and 3:1.
  • the present invention relates to a method for producing a film, a porous film or a foam, wherein the method comprises a. Providing zein b.
  • Providing a second protein wherein the second protein is selected from a group consisting of glutenin, gliadin, secalin, hordein, avenin or a combination thereof, c.
  • Providing a plasticizer wherein the plasticizer is selected from a group consisting of glycerol, water, sorbitol, propylene glycol, diethanolamine, and triethanolamine or a combination thereof, and d.
  • a crosslinking agent selected from a group consisting of genipin, genipin oil, aglycone, dialdehydes, polycarboxylic acids, phenolic compounds, epoxy compounds or a combination thereof, e.
  • the filler is preferably one or more potato proteins, wheat bran, cereal husks, cereal straws or a combination thereof, wherein the filler is more preferably patatin, and wherein the film is produced by performing steps A1 and A2 A1.
  • Extruding the mixture to a film wherein the porous film or foam is produced either by performing steps B1, B2 and B3 B1.
  • the foaming agent is selected from a group consisting of bicarbonate and water or a combination thereof, preferably sodium bicarbonate, and B2.
  • the foaming agent is selected from a group consisting of bicarbonate and water or a combination thereof, preferably sodium bicarbonate, and B2.
  • the plasticizer, optionally the crosslinking agent, optionally the filler and the foaming agent to form a mixture, wherein the weight ratio between zein and the second protein is between 1:1 and 4:1, preferably between 1:1 and 3:1, and B3.
  • Extruding the mixture to a porous film or a foam the porous film or foam is produced by performing steps C1 and C1.
  • the present invention relates to an absorbent article comprising a film, an absorbent member comprising the foam according to the first aspect of the invention, and a porous film. All embodiments disclosed herein may be combined and relates to all aspects of the present invention unless stated otherwise.
  • Figure 1 illustrates an embodiment of the method according to an aspect of the technology proposed herein.
  • Figure 2 shows photographs of extruded foams according to example 1, prior to and after immersion in water for 24 hours.
  • Figure 3 illustrates water swelling results for extruded foams according to example 1.
  • Figure 4 illustrates free swelling capacities in saline solution for foam samples according to example 1.
  • Figure 5 illustrates centrifuge retention capacities in saline solution for samples according to example 1.
  • Figure 6 shows a photograph of absorbent articles assembled according to example 2.
  • Figure 7 shows a foam sample molded according to example 3.
  • Figure 8 illustrates visual absorption test in defibrinated sheep blood of samples according to example 3.
  • Figure 9 shows photographs of samples according to example 5.
  • Figure 10 illustrates weight loss results of samples according to example 6.
  • Figure 11 illustrates photographs of samples according to example 7.
  • Figure 12 illustrates a photograph of a sample according to example 8.
  • Genipin oil The oil is the product of the extraction of oleic substances (such as genipin) contained in the fruit of the Rubiaceae trees family such as Genipa Americana.
  • the oil is a liquid dispersion containing natural non-toxic crosslinkers such as at least 10% of genipin.
  • Water swelling capacity Determined by completely immersing samples of 1 cm long pieces of the foam in water for 24 hours. After removing the samples from the liquid, excess liquid was removed by placing the samples on tissue paper for 10 seconds.
  • Centrifuge retention capacity A measure of the fluid retention of samples, determined by swelling samples in 0.9 weight-% NaCl aqueous solution for 30 min, followed by centrifugation of samples kept inside bags for 3 minutes at 1250 rpm.
  • Centrifuge retention capacity is calculated according to the equation below ⁇ ⁇ where Wc denotes the weight of the centrifuged sample in the bag, W0 denotes the weight of the dry bag used, W d denotes the weight of the sample, and W b denotes the correction factor.
  • W S denotes the weight of the W is the weight of the dry bag.
  • the material comprises a first protein wherein the first protein is zein and a second protein, wherein the material has a weight ratio between zein and the second protein between 1:1 and 4:1, preferably between 1:1 and 3:1.
  • the second protein is selected from a group consisting of glutenin, gliadin, secalin, hordein, avenin or a combination thereof.
  • the material comprises a plasticizer.
  • the zein can be obtained as a by-product from the industrial starch extraction from corn or as a by-product from the industrial corn fiber extraction.
  • the second protein can for example be obtained as a by-product from the industrial starch extraction from wheat, barley, rye, oat. These by-products may not, due to residues of other non-protein compounds, be used in food applications without further treatment.
  • the present invention found that these by-products can serve as feedstocks to produce a cheap material according to the present invention. Accordingly, the technology proposed herein is based on the realization that a material comprising a plasticizer as well as zein and a second protein, in a weight ratio as specified above, yields a material with the ability to form continuous porous extrudates, porous films and films from the same composition, without the addition of toxic crosslinking agents such as glutaraldehyde.
  • the sum of zein and the second protein is at least 50 weight-% with respect to the total weight of the material, preferably 60 weight-%.
  • An increased content of zein and the second protein is accompanied with an increased water swelling capacity for foams of the material, as well as increase the rate of biodegradation. Additionally, zein increase the shelf life of the material as it results in a material that is less susceptible to growth of mold.
  • the material comprises 20-40 weight-% plasticizer.
  • the plasticizer is selected from the group consisting of glycerol, water, sorbitol, propylene glycol, diethanolamine, and triethanolamine or a combination thereof.
  • the amount of plasticizer affects the mechanical properties of the material as well as the porosity of the material when extruded into a film, foam or a porous film.
  • the plasticizers are soluble in water, and may dissolve during absorption use thus jeopardizing the integrity of the material.
  • the amount of plasticizer is between 25-35 weight-%.
  • the material is at least partly biodegradable, preferably wherein at least 50 weight-% of the material is biodegradable within 2 weeks in soil comprising farmland and compost at a weight ratio of 2:1, at room temperature and 70-80% relative humidity.
  • the material may also be at least partly cross-linked, to further improve the strength of the material. Crosslinking may be obtained by inclusion of crosslinking agents.
  • the material comprises 0.05 – 5 weight-% crosslinking agent, preferably 0.5-1.5 weight-%.
  • the crosslinking agent is selected from genipin, genipin oil, aglycone, dialdehydes, polycarboxylic acids, phenolic compounds, epoxy compounds, or a combination thereof.
  • the addition of crosslinking agent increases the mechanical stability of the material, and for a foam of the material it prevents pores from collapsing as well as promotes formation of uniform and spherical pores.
  • the addition of crosslinking agent delays hydrolysis of the proteins in humid conditions, thereby increasing the stability of the material.
  • Genipin is aglycones derived from an iridoid glycoside or geniposide.
  • Genipin oil is the product of the extraction of oelic substances contained in the fruit of the Rubiaceae trees family, such as from Genipa Americana.
  • Genipin oil is a liquid dispersion containing genipin.
  • Genipin and genipin oil are natural and non-toxic crosslinking agents.
  • the addition of genipin or genipin oil results in a black material, which is a preferred color for materials used in black sanitary products, such as sanitary pads.
  • the crosslinking agent is genipin oil.
  • Genipin oil promotes the expansion of the material in the form of a foam.
  • Genipin oil comprises genipin as well as lipids and phenolic compounds, without being bound by theory these lipids and phenolic compounds are believed to be involved in the formation of bonds between the prolamin groups in the proteins thereby promoting the expansion of the material, and the lipids may additionally act as lubricant during material processing such as extrusion. Additionally, genipin oil can be a significantly cheaper alternative to genipin, since genipin requires additional purification steps after extraction.
  • the material comprises 5-15 weight-% filler, wherein the filler is preferably one or more potato proteins, wheat bran, cereal husks, cereal straws or a combination thereof wherein the filler is more preferably patatin.
  • the filler is preferably potato proteins.
  • the material comprises a crosslinking agent the potato proteins are also involved in crosslinking and thereby contributes to the mechanical properties and porosity of the material.
  • the addition of 0.05-5 weight-% crosslinking agent results in higher water swelling capacities.
  • the addition of 0.05-5 weight-% crosslinking agent results in lower water swelling capacities.
  • the material is in the form of a foam, film or a porous film.
  • a foam of the present invention is a material with a porous structure capable of absorbing at least 6 g of saline solution (0.9 weight-% NaCl in water) per gram of the material after 10 minutes and has a centrifuge retention capacity of at least 2 g of said saline solution per gram of material after centrifugation at 1250 rpm for 3 minutes.
  • the absorption capacity for blood is at least 4 g of blood per gram of material.
  • the present invention relates to a method of producing a film, a porous film or a foam.
  • the second protein in the method is a protein selected from a group consisting of glutenin, gliadin, secalin, hordein, avenin or a combination thereof.
  • the plasticizer is preferably selected from glycerol, water, sorbitol, propylene glycol, diethanolamine, triethanolamine or a combination thereof.
  • the optional crosslinking agent in the method is selected from a group consisting of genipin, genipin oil, dialdehydes, epoxy compounds or a combination thereof.
  • the optional filler in the method is selected from a group consisting of one or more potato proteins, wheat bran, cereal husks, cereal straws, or a combination thereof wherein the filler is more preferably patatin.
  • the foaming agent in the method is selected from a group consisting of bicarbonate, water or a combination thereof, preferably sodium bicarbonate.
  • Figure 1 is an illustration of the method according to this aspect. Referring now to figure 1.
  • a method for producing a film comprises the steps of providing zein (1), providing a second protein selected from glutenin, gliadin, secalin, hordein, avenin or a combination thereof (2), providing a plasticizer, wherein the plasticizer is preferably selected from a group consisting of glycerol, water, sorbitol, propylene glycol, diethanolamine, triethanlamine or a combination thereof (3), optionally providing a crosslinking agent selected from a group consisting of genipin, genipin oil, aglycones, dialdehydes, polycarboxylic acids, phenolic compounds, epoxy compounds or a combination thereof (4), optionally providing a filler, wherein the filler is preferably one or more potato proteins, wheat bran, cereal husk, cereal straws, or a combination thereof, wherein the filler is more preferably patatin (5).
  • a method for producing a porous film comprises the steps of providing zein (1), providing a second protein selected from glutenin, gliadin, secalin, hordein, avenin or a combination thereof (2), providing a plasticizer, wherein the plasticizer is preferably selected from a group consisting of glycerol, water, sorbitol, propylene glycol, diethanolamine, triethanolamine or a combination thereof (3), optionally providing a crosslinking agent selected from a group consisting of genipin, genipin oil, aglycones, dialdehydes, polycarboxylic acids, phenolic compounds, epoxy compounds or a combination thereof (4), optionally providing a filler, wherein the filler is preferably one or more potato proteins, wheat bran, cereal husk, cereal straws, or a combination thereof wherein the filler is more preferably patatin (5), providing a foaming agent selected from a group consisting of bicarbonate, water or a combination thereof
  • a method for producing a porous film comprises the steps of providing zein (1), providing a second protein selected from glutenin, gliadin, secalin, hordein, avenin or a combination thereof (2), providing a plasticizer, wherein the plasticizer is preferably selected from a group consisting of glycerol, water, sorbitol, propylene glycol, diethanolamine, triethanolamine or a combination thereof (3), optionally providing a crosslinking agent selected from a group consisting of genipin, genipin oil, aglycones, dialdehydes, polycarboxylic acids, phenolic compounds, epoxy compounds or a combination thereof (4), optionally providing a filler, wherein the filler is preferably one or more potato proteins, wheat bran, cereal husk, cereal straws, or a combination thereof wherein the filler is more preferably patatin (5).
  • a method for producing a foam comprises the steps of providing zein (1), providing a second protein selected from glutenin, gliadin, secalin, hordein, avenin or a combination thereof (2), providing a plasticizer, wherein the plasticizer is preferably selected from a group consisting of glycerol, water, sorbitol, propylene glycol, diethanolamine, triethanolamine or a combination thereof (3), optionally providing a crosslinking agent selected from a group consisting of genipin, genipin oil, aglycones, dialdehydes, polycarboxylic acids, phenolic compounds, epoxy compounds or a combination thereof (4), optionally providing a filler, wherein the filler is preferably one or more potato proteins, wheat bran, cereal husk, cereal straws, or a combination thereof wherein the filler is more preferably patatin (5), providing a foaming agent selected from a group consisting of bicarbonate, water or a combination thereof,
  • a method for producing a foam comprises the steps of providing zein (1), providing a second protein selected from glutenin, gliadin, secalin, hordein, avenin or a combination thereof (2), providing a plasticizer, wherein the plasticizer is preferably selected from a group consisting of glycerol, water, sorbitol, propylene glycol, diethanolamine, triethanolamine or a combination thereof (3), optionally providing a crosslinking agent selected from a group consisting of genipin, genipin oil, aglycones, dialdehydes, polycarboxylic acids, phenolic compounds, epoxy compounds or a combination thereof (4), optionally providing a filler, wherein the filler is preferably one or more potato proteins, wheat bran, cereal husk, cereal straws, or a combination thereof wherein the filler is more preferably patain (5).
  • Extruded foams of the present invention are obtained by employing dies well known in the art, preferably by employing circular dies of 2-3 mm in diameter or the like. The inventors found that foams of the material of the present invention was capable of being further processed into the desired shape.
  • the extruded foam is initially cut into pellets. Subsequently, the pellets were distributed in a mold, pressed at 150 ⁇ C and 150 kN for 5 minutes, followed by 5 minutes in the mold at 150 ⁇ C without applying pressure. Homogeneous materials, shaped according to the mold, were obtained for materials with an amount of 0.9 g/cm 3 .
  • the present invention relates to an absorbent article comprising a film, an absorbent member comprising the foam according to the first aspect of the invention, and a porous film.
  • the absorbent member is disposed between a first, porous layer, conventionally referred to as “top sheet” and a second layer, conventionally referred to as “back sheet”.
  • the top sheet and the back sheet of the article may be sealed together encompassing the absorbent member.
  • the absorbent member may comprise the foam according to the present invention as the only liquid absorbing component or may include additional liquid absorbing components to form the absorbent member.
  • the top sheet is a porous film that is liquid permeable, and may be any material or combination of materials suitable for this purpose, including but not limited to fibrous nonwovens, apertured plastic films and textile materials, that allows body fluids to be transported through the layer and get in contact with the absorbent member.
  • the top sheet is the porous film according to the present invention.
  • the back sheet may be of any material or combination of materials suitable for this purpose, including but not limited to non-wovens and plastic films.
  • the back sheet may be liquid impermeable to prevent leakage of body fluids.
  • the back sheet may be vapour permeable, to allow vapour to pass through.
  • the back sheet is the film according to the present invention.
  • the top sheet is welded to the back sheet by employing an impulse sealer or the like. Wherein the top sheet and the back sheet completely enclose the absorbent member.
  • the absorbent article is biodegradable in soil comprising farmland and compost at a weight ratio of 2:1, at room temperature and 70-80% relative humidity within 30 days. In one embodiment, the absorbent article exhibit no mold growth after 3 weeks exposure to 100% relative humidity at 25 ⁇ C. It is to be understood that the absorbent member comprising the foam according to the present invention may be the foam as obtained after extrusion, grinded particles of the foam, or the foam molded in a desired shape.
  • Example 1 Foams constructed from zein, wheat gluten and potato protein 1.1
  • Wheat gluten concentrate WG was obtained as a coproduct from the industrial wheat starch production/extraction, with protein content of 86.3 ⁇ 0.3%, determined by the Dumas method, NMLK 6:2003.
  • Potato protein concentrate (PP) from the production/extraction of potato starch was used, with a protein content of 82 ⁇ 2%, determined by the Dumas method.
  • Zein (Z) C-zein, CAS number: 9010-66-6, product number Z3625
  • Sigma-Aldrich Co. Sigma-Aldrich Co. (St Louis, MO, USA).
  • Genipin (GEN) (HPLC grade ⁇ 98%) was purchased from Zhixin Biotechnology, China.
  • Genipin oil (OIL) was obtained as the liquid product collected by extraction of oelic substances (such as genipin) contained in the fruit of the Rubiaceae trees family.
  • samples were prepared without a crosslinking agent, with the addition of 2.5 g of GEN per 100 g of proteins as a crosslinking agent, as well as with the addition of 2.5 g of OIL per 100 g of proteins as the crosslinking agent, respectively.
  • the powders were mixed with an electric mixer for 30 seconds, followed by the addition of 50 g of glycerol per 100 g of proteins as a plasticizer, followed by mixing with an electric mixer for another 30 seconds.
  • the mixtures were immediately transferred to a conical, fully intermeshing, and co- rotating double-screw extruder (DSM Xplore 5 cc, The Netherlands).
  • the extruder contained a screw with an L/D ratio of 8 and a compression ratio of 3.3.
  • Figure 3 shows water swelling capacities of samples according to Table 1.
  • Samples 75Z/0PP, 75Z/0PP GEN , 75Z/0PP OIL , 60Z/15PP, 60Z/15PP GEN , 60Z/15PP OIL exhibited water swelling capacities of 333%, 471%, 356%, 252%, 288%, and 280%, respectively, as seen in Figure 3.
  • the water swelling capacity decreased with increasing filler content in the material.
  • Table 2 Water swelling capacity of selected samples 7 L 3 Free swelling capacities were determined according to Non-woven Standard Procedure (NWSP) 240.0.R2, also known as the “teabag” test, and in accordance with International Standard ISO 17190-5 (2020).
  • NWSP Non-woven Standard Procedure
  • the highest FSC after 1 minute were obtained for 60Z/15PP OIL and 60Z/15PP GEN with approximately 8 g of saline per gram of material.
  • the lowest FSC after 1 minute were obtained for 25Z/50PP OIL with 5 g of saline per gram of material.
  • the highest FSC after 24 hours was obtained for 60Z/15PP OIL with 11 g of saline solution per gram of material, followed by 75Z/0PP, 75Z/0PP GEN , 75Z/0PP OIL , and 60Z/15PP, all with approximately 10 g/g, followed by 60Z/15PP GEN with 9 g/g.
  • the lowest FSC after 24 hours was obtained for samples with the highest portion of PP, i.e.
  • 25Z/50PP, 25Z/50PP GEN , and 25Z/50PP OIL with 7 g/g, 6 g/g, and 8 g/g, respectively.
  • Example 2 Absorbent article with protein blend materials 2.1Materials Wheat gluten concentrate (WG) was obtained as a coproduct from the industrial wheat starch production/extraction, with a protein content present in the WG was 86%, determined by the Dumas method, NMLK 6:2003. Zein (Z) (C-zein, CAS number: 9010-66-6, product number Z3625) was purchased from Sigma-Aldrich Co. (St Louis, MO, USA).
  • Glycerol (ACS ⁇ 99.5% reagent) and sodium bicarbonate (SBC) (NaHCO 3 , >99.7%) were purchased from Fischer Scientific and Sigma-Aldrich (Stockholm, Sweden), respectively.
  • SBC sodium bicarbonate
  • the extruder contained a screw with an L/D ratio of 8 and a compression ratio of 3.3. All heating zones of the extruder were set to the temperature of 100 ⁇ C, a screw speed of 60 rpm was set, and a flat sheet die of 0.2 mm was used during extrusion.
  • the mixtures were immediately transferred to a conical, fully intermeshing, and co- rotating double-screw extruder (DSM Xplore 5 cc, The Netherlands).
  • the extruder contained a screw with an L/D ratio of 8 and a compression ratio of 3.3. All heating zones of the extruder were set to the temperature of 100 ⁇ C, a screw speed of 60 rpm was set, and a flat sheet die of 0.2 mm was used during extrusion.
  • the dry Z and WG Prior to extruding, the dry Z and WG were mixed at a weight ratio of 3:1 with an electric mixer for 30 seconds, followed by the addition of 50 g of glycerol per 100 g of proteins as a plasticizer as well as 5 g of SBC per 100 g of proteins as foaming agent and 5 g of water per 100 g of protein as plasticizer and/or foaming agent, followed by mixing with an electric mixer for another 30 seconds.
  • the mixtures were immediately transferred to a conical, fully intermeshing, and co- rotating double-screw extruder (DSM Xplore 5 cc, The Netherlands).
  • the extruder contained a screw with an L/D ratio of 8 and a compression ratio of 3.3.
  • All heating zones of the extruder were set to the temperature of 100 ⁇ C, a screw speed of 60 rpm was set, and a circular die with a diameter of 4 mm was used during extrusion.
  • 2.5Absorbent article assembly Foam extrudate was cut into 0.5 cm pellets. The pellets were put in a pre-heated aluminum mold. The mold was placed between anti-adhesion Telfon® paper and top and bottom plates preheated to 150 ⁇ C. The pellets were pressed at 150 ⁇ C and 150 kN for 5 minutes, followed by 5 minutes at 150 ⁇ C without applied pressure.0.9 g/cm 3 of material with respect to volume of the mold was used. The molded pad was stored in desiccator.
  • Absorbent articles were assembled with conventional materials as well as with protein based materials, summarized in table 3 below.
  • the foam was sealed between a back sheet of a film and a top sheet of a porous film by using an impulse sealer (PFS-400).
  • PFS-400 Protein based film, porous film and foam are disclosed in section 2.2, 2.4, and 2.3 above, respectively.
  • FIG. 6 illustrates a photograph of absorbent articles, from left to right i) polypropylene/polyethylene nonwoven film and porous film with polyurethane foam, ii) polypropylene/polyethylene nonwoven film and porous film with protein based foam, iii) protein based film, protein based porous film and polyurethane foam, iv) protein based film, protein based porous film with protein based foam.
  • Example 3 Blood absorption capacity 3.1 Film, foam and porous film preparation Films, foams, and porous films were prepared according to example 2.
  • a filament was prepared according to the same manner as the foam, but without the addition of foaming agent. That is by prior to extrusion, mixing the dry Z and WG at a weight ratio of 3:1 with an electric mixer for 30 seconds, followed by the addition of 50 g of glycerol per 100 g of proteins as a plasticizer, followed by mixing with an electric mixer for another 30 seconds. The mixtures were immediately transferred to a conical, fully intermeshing, and co- rotating double-screw extruder (DSM Xplore 5 cc, The Netherlands). The extruder contained a screw with an L/D ratio of 8 and a compression ratio of 3.3.
  • Figure 7 illustrates photographs of the “hot pressed sample” shaped as a conventional sanitary pad, before bending (left), arched by hand (center), as well as after bending (right).
  • “Particle samples” were prepared by cryogenic grinding. Two types of absorbent articles were prepared; with polypropylene/polyethylene film, hot pressed sample as foam, and polypropylene/polyethylene porous film, or with protein based film, hot pressed sample as foam, and protein based porous film.
  • 3.4 Blood absorption capacity A visual absorption test was employed to assess the blood absorption capacity. Defibrinated sheep blood was added to the material until saturation was reached.
  • Figure 8 illustrates photographs of the visual absorption test of a) hot pressed sample, b) particle sample, c) an absorbent article with polypropylene/polyethylene film and porous film, and d) an absorbent article with protein based film and porous film according to the sample preparation described in section 3.2.
  • the blood absorption capacity of the hot pressed samples was 4.2 g/g.
  • the blood absorption capacity of the particle samples was 4 g/g.
  • the absorbent article assembled with polypropylene/polyethylene film and porous film did not spread the blood adequately, and the droplet stayed on the material’s surface. The same behavior was observed on a commercial sanitary product.
  • the absorbent article assembled with protein based film and porous film with a hot pressed sample as foam exhibited a blood absorption capacity of 0.7 g/g.
  • the blood absorption capacity of the filament sample was 0.4 g/g.
  • Example 4 – Absorption under load 4.1 Foam The foam was prepared according to example 2. 4.2 Absorption under load The capacity of the material to absorb liquid under a constant load was determined by the absorption under load (AUL) test following the NWSP 242.0.R2 standard. The sample was placed in a cylinder having a metal grid at the bottom and a piston was placed on top of the sample.
  • AUL absorption under load
  • the piston had a weight of 0.5 kg and a diameter of 6 cm, leaving a pressure of approximately 1.76 kPa (0.25 psi, equivalent to a new born baby).
  • the setup was placed on top of a porous ceramic plate, in a glass petri dish. Saline solution (0.9 weight-% NaCl) was added to the petri dish, contacting the sample via the metal grid. The sample was left under load for 1 hour. The foam exhibited an absorption under load of 0.6 ⁇ 0.1 g/g.
  • Example 5 – Biodegradation 5.1 Foam The foam was prepared according to example 1. 5.2 Biodegradation The biodegradation of the material was evaluated by monitoring the disintegration of the sample in soil over time.
  • the hydrolytic degradation of the samples was evaluated at 25 ⁇ C and in three degradation systems: an acid pH 4 buffer solution (sodium acetate/acetic acid), a neutral pH 7 buffer solution (PBS), and a basic pH 9 buffer solution (ammonium chloride/ammonia).
  • the time of degradation was of one, three and five weeks.
  • Degradation monitoring was done by monitoring weight changes, pH variation of the degradation medium and morphological changes by scanning electron microscopy. For all samples, 33% of the weight loss is attributed to the leaching of plasticizer, i.e. glycerol, within the first week. Weight loss above 33% is attributed to hydrolysis of proteins in the material followed by dissolution of the hydrolysis products from the samples.
  • FIG. 10 depicts weight loss of samples after 1, 3, and 5 weeks in pH 7.38 buffer solution, without crosslinking agent (top), with genipin as crosslinking agent (middle), and with genipin oil as crosslinking agent (bottom).
  • the line at 33% highlight the weight loss attributed to leaching of plasticizer.
  • samples without crosslinking agent exhibited weight loss ranging from 45% to 53%
  • samples with crosslinking agent GEN or OIL
  • Example 7- Mold resistance test 7.1 Foam The foams were prepared according to example 1. 7.2 Mold resistance test A visual test was used to evaluate the mold resistance of samples in powder form as well as extruded foams. 0.5 g of samples were placed in culture dishes in an airtight container with at 25 ⁇ C and 100% relative humidity. Photographs of the samples were taken after 0, 1, 3, and 5 weeks. Figure 11 depicts photographs of extruded foam and grounded foam of samples a) 40Z/35PP, b) 40Z/35PP GEN , and c) 40Z/35PP OIL prior to as well as after 1, 3 and 5 weeks. As seen in Figure 11, no presence of mold was found on the powder sample and extruded foam sample of 40Z/35PP and 40Z/35PP GEN .
  • Example 8 Material without second protein 8.1 Materials Materials were used according to example 1. 8.2 Extrusion of material Dry Z and SBC (as a foaming agent) in the ratio of 5 g per 100 g of Z were mixed with an electric mixer for 30 seconds, followed by the addition of 50 g of glycerol (as a plasticizer) per 100 g of Z, followed by mixing with an electric mixer for another 30 seconds.
  • the mixture was immediately transferred to a conical, fully intermeshing, and co- rotating double-screw extruder (DSM Xplore 5 cc, The Netherlands).
  • the extruder contained a screw with an L/D ratio of 8 and a compression ratio of 3.3. All heating zones of the extruder were set to the temperature of 100 ⁇ C, a screw speed of 60 rpm was set, and a circular die with a diameter of 3.8 mm was used during extrusion.
  • 8.3 Material characterization Figure 12 shows a photograph of the extruded material. The sample was very brittle, tacky during extrusion, and it contains a non-continuous pore microstructure which is partially collapsed.
  • Example 9 Foam preparation Two samples were prepared.
  • the dry Z and WG Prior to extrusion, the dry Z and WG were mixed at a weight ratio of 3:1 or 1:1, respectively, with an electric mixer for 30 seconds, followed by the addition of 50 g of glycerol per 100 g of proteins as a plasticizer as well as 5 g of SBC per 100 g of proteins as foaming agent and 5 g of water per 100 g of protein as plasticizer and/or foaming agent, followed by mixing with an electric mixer for another 30 seconds.
  • the Z and WG mixtures were immediately transferred to a conical, fully intermeshing, and co-rotating double-screw extruder (DSM Xplore 5 cc, The Netherlands).
  • the extruder contained a screw with an L/D ratio of 8 and a compression ratio of 3.3.
  • Mold resistance of samples of example 9 A visual test was used to evaluate the mold resistance. 0.5 g of the samples were placed in culture dishes in an airtight container with at 25 ⁇ C and 100% relative humidity. The samples exhibited mold resistance up to 2 months. Blood absorption of samples of example 9 A visual absorption test was employed to assess the blood absorption capacity. Defibrinated sheep blood was added to the material until saturation was reached. Additionally, the amount of blood was measured by mass and normalized with respect to the dry sample weight. The samples exhibited a blood absorption of at least 1 g of blood per gram of dry material in 10 min. Saline solution absorption of samples of example 9 A visual absorption test was employed to assess the saline solution absorption capacity.
  • Saline solution (0.9 weight-% NaCl in water) was added to the material until saturation was reached. Additionally, the amount of saline solution was measured by mass and normalized with respect to the dry sample weight. The samples exhibited a saline solution absorption of at least 3 g of saline solution per gram of dry material.

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Abstract

La présente invention concerne le domaine des articles absorbants construits avec des matériaux comprenant des protéines, fournissant ainsi des alternatives aux articles absorbants à base de pétrole classiques. L'invention concerne un matériau comprenant une première protéine, une deuxième protéine et un plastifiant, la première protéine étant la zéine, et la deuxième protéine étant choisie dans un groupe constitué de la gluténine, la gliadine, la sécaline, la hordéine, l'avénine ou une combinaison de celles-ci. L'invention concerne en outre des procédés de production d'un film, d'un film poreux et d'une mousse du matériau et un article absorbant comprenant le matériau.
PCT/SE2024/050278 2023-03-28 2024-03-27 Matériau de mélange de protéines avec de la zéine et une deuxième protéine végétale, et procédé de production d'un film ou d'une mousse absorbante à partir du matériau Pending WO2024205475A1 (fr)

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Citations (5)

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Publication number Priority date Publication date Assignee Title
WO1997019988A1 (fr) * 1995-11-29 1997-06-05 Midwest Grain Products, Inc. Articles solides biodegradables a base de proteine granulaire et procede de formage
CN101580595A (zh) * 2009-06-18 2009-11-18 沈阳农业大学 一种可食性复合蛋白膜的制备方法
CN102964848A (zh) * 2012-12-21 2013-03-13 青岛海尔软件有限公司 一种蛋白/多糖复合型可食用膜及其制备方法
CN108102391A (zh) * 2018-01-16 2018-06-01 镇江市荣发塑料制品有限公司 g-C3N4复合型可食用抗菌膜及其制备方法
WO2020249214A1 (fr) * 2019-06-13 2020-12-17 Essity Hygiene And Health Aktiebolag Article absorbant avec matériau absorbant à base d'une protéine végétale

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WO1997019988A1 (fr) * 1995-11-29 1997-06-05 Midwest Grain Products, Inc. Articles solides biodegradables a base de proteine granulaire et procede de formage
CN101580595A (zh) * 2009-06-18 2009-11-18 沈阳农业大学 一种可食性复合蛋白膜的制备方法
CN102964848A (zh) * 2012-12-21 2013-03-13 青岛海尔软件有限公司 一种蛋白/多糖复合型可食用膜及其制备方法
CN108102391A (zh) * 2018-01-16 2018-06-01 镇江市荣发塑料制品有限公司 g-C3N4复合型可食用抗菌膜及其制备方法
WO2020249214A1 (fr) * 2019-06-13 2020-12-17 Essity Hygiene And Health Aktiebolag Article absorbant avec matériau absorbant à base d'une protéine végétale

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WANG JING JING, WANG YIXIANG, WANG QIYANG, YANG JINGQI, HU SONG-QING, CHEN LINGYUN: "Mechanically Strong and Highly Tough Prolamin Protein Hydrogels Designed from Double-Cross-Linked Assembled Networks", ACS APPLIED POLYMER MATERIALS, vol. 1, no. 6, 14 June 2019 (2019-06-14), pages 1272 - 1279, XP093219637, ISSN: 2637-6105, DOI: 10.1021/acsapm.9b00066 *

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