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WO2023031915A1 - Hydrogel comestible, procédé de production et ses utilisations - Google Patents

Hydrogel comestible, procédé de production et ses utilisations Download PDF

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Publication number
WO2023031915A1
WO2023031915A1 PCT/IL2022/050933 IL2022050933W WO2023031915A1 WO 2023031915 A1 WO2023031915 A1 WO 2023031915A1 IL 2022050933 W IL2022050933 W IL 2022050933W WO 2023031915 A1 WO2023031915 A1 WO 2023031915A1
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WO
WIPO (PCT)
Prior art keywords
hydrogel
edible
car
native
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/IL2022/050933
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English (en)
Inventor
Shmuel ITTAH
Jonathan HAUSNER
Yael PRIGAT GOLDFRIEND
Moran Cohen
Daniel Dikovsky
Nissim DAVID
Eshchar BEN-SHITRIT
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Redefine Meat Ltd
Original Assignee
Redefine Meat Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Redefine Meat Ltd filed Critical Redefine Meat Ltd
Priority to EP22797124.9A priority Critical patent/EP4395556A1/fr
Publication of WO2023031915A1 publication Critical patent/WO2023031915A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
    • A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/20—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
    • A23L29/206—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin
    • A23L29/256—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin from seaweeds, e.g. alginates, agar or carrageenan
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23C—DAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING OR TREATMENT THEREOF
    • A23C20/00—Cheese substitutes
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23J—PROTEIN COMPOSITIONS FOR FOODSTUFFS; WORKING-UP PROTEINS FOR FOODSTUFFS; PHOSPHATIDE COMPOSITIONS FOR FOODSTUFFS
    • A23J3/00—Working-up of proteins for foodstuffs
    • A23J3/22—Working-up of proteins for foodstuffs by texturising
    • A23J3/225—Texturised simulated foods with high protein content
    • A23J3/227—Meat-like textured foods
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2250/00—Food ingredients
    • A23V2250/50—Polysaccharides, gums
    • A23V2250/502—Gums
    • A23V2250/5036—Carrageenan
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2250/00—Food ingredients
    • A23V2250/50—Polysaccharides, gums
    • A23V2250/502—Gums
    • A23V2250/5036—Carrageenan
    • A23V2250/50364—Kappa-carrageenan

Definitions

  • the technology relates to the food industry.
  • Xi Lang discusses the classification and properties of food polysaccharides and their use in improving the textural attributes of a wide range of food products, including emulsion-based foods, low calorie foods, restructured foods, gelatin free foods, breaded or battered foods, and frozen foods as well as wheaten foods.
  • KR20120015783 describes a non-edible hydrogel composition for transdermal absorption and administration that provides adhesion and high tensile strength and provides skin moisturizing and skin hydration.
  • the hydrogel comprises galactomannan gum, carrageenan gum and tackifiers.
  • the amount of carrageenan gum is between 0.5% to 10% by weight based on the total amount of the hydrogel composition.
  • WO2014/176304 describes a method of forming a non-edible hybrid physically and chemically cross-linked double-network hydrogel with recoverable and mechanical properties in a single-pot synthesis.
  • the hydrogel comprises, inter alia, a polysaccharide selected from agar, gelatin, sodium alginate, carrageenan, and others.
  • the hydrogel exhibited high stiffness (elastic modulus of 123kPa), strength (failure compression stress of 38MPa and failure tensile stress of l.OMPa) dissipated energy (9 MJ/m 3 ), extensibility (15-20 times longer relative to its initial length), and a free-shapeable property (formation of many complex geometrical shapes).
  • WO0248199 describes processes for preparing carrageenan-containing products from processed seaweed using shear stress.
  • Films can be formed, for example, by casting a carrageenan containing solution on a cooled rotating drum.
  • the carrageenan- containing film can be fed through a series of rollers to counter rotating dies which form, cut, and fill capsules of various sizes.
  • US2004/0052839 describes a method of producing a non-gelatin film, the method includes combining at least one non-gelatin hydrocolloid, water, and at least one plasticizer into a substantially homogeneous film-forming composition comprising at least about 40% water by weight. The method further includes extracting a portion of the water from the film-forming composition to form a dried portion having a water content of less than or equal to about 25% by weight. The method also includes forming the dried portion of the film-forming composition into a film. The film exhibited a tensile strength at rupture of at least about 5 N at room temperature, a percent elongation of at least about 50 percent at rupture at room temperature.
  • W001/03677 describes compositions comprising modified starch and carrageenan, especially iota-carrageenan, the compositions being suitable for use in manufacturing soft capsules.
  • WO20 18/227656 describes an edible film forming liquid and preparation thereof.
  • the edible film comprising marine polysaccharides fish collagen protein and glycerol.
  • CN112430290 describes kappa-carrageenan-based high strength crosslinked hydrogel.
  • an edible hydrogel comprising carrageenan (CAR) and an aqueous carrier comprising water; wherein said water constitutes up to 80wt% out of a total volume of the hydrogel; and wherein, when said hydrogel has between 50wt% and 80wt% water content, the hydrogel is characterized by
  • CAR content of at least 5wt% out of a total volume of the hydrogel; storage modulus (G 1 ) of at least lOKPa within a temperature range of 25°C-70°C; and tensile strength at least 600kPa as determined at 25°C; and tensile strain at break of at least 15% as determined at 25°C.
  • a method of producing an edible hydrogel comprises treating a native hydrogel comprising at least 5wt% CAR within an aqueous medium, said treatment comprises subjecting the native hydrogel to a dehydration process until obtaining a dehydrated hydrogel with up to 50wt% liquid content; and rehydrating the dehydrated hydrogel by exposing the dehydrated hydrogel to a rehydrating medium.
  • a further method of producing an edible hydrogel comprises treating a native hydrogel comprising at least 5wt% CAR and an aqueous medium, said treatment comprises subjecting the native hydrogel to an anti-solvent system to obtain a solidifying native hydrogel; and subjecting the solidifying native hydrogel to a dehydration process until obtaining a dehydrated hydrogel with up to 50wt% liquid content.
  • the dehydrated hydrogel can be stored and subjected to rehydration, as presently disclosed, prior to intended consumption.
  • the present disclosure also provides, in accordance with a fourth aspect of the presently disclosed subject matter, an edible hydrogel obtained or obtainable by the method of the second aspect of the presently disclosed subject matter.
  • a food product comprising the edible hydrogel disclosed herein.
  • Figure l is a Thermogravimetric Analysis (TGA) of different carrageenan-based films.
  • the present disclosed subject matter is based on the realization by the inventors that there is a need to enrich meat analogue products with texture enhancers in addition to or as alternative to texturized proteins hitherto used (e.g. texturized vegetable proteins (TVP), high moisture extruded (HME) proteins, fibrous gluten), so as to improve the toughness and chewiness experience by the individuals when eating the meat analogues.
  • texturized proteins hitherto used e.g. texturized vegetable proteins (TVP), high moisture extruded (HME) proteins, fibrous gluten
  • an edible hydrogel comprising carrageenan (hereinbelow “CAR”) and an aqueous carrier comprising water, wherein said water constitutes up to 80wt% out of a total volume of the hydrogel; and wherein when said hydrogel has between about 50wt% and about 80wt% water, the hydrogel is characterized by
  • CAR content of at least 5wt% out of a total volume of the hydrogel; a storage modulus (G 1 ) of at least lOKPa within a temperature range of 25°C- 70°C; a tensile strength of at least 600KPa as determined 25°C by a tensile strength test, a tensile strain at break of at least 15% as determined by a tensile test at 25°C
  • storage modulus of a sample can be determined in a test performed on discs of 40mm in diameter and 1mm thick, and analyzed by Rheometer (Discovery HR20, TA) using 40mm stainless steel, sandblasted parallel plates, during which each film was subjected to Grips axial force (IN), oscillation strain of 10%, and frequency of 10Hz.
  • the tested temperature range can be 25°C-70°C.
  • tensile properties can be determined using TAI Series Texture Analysis machine (LLOYD TAI), using a load cell of 100N with TG74: adjustable Rear Face Vice Grip 5kN-l 1241bf. Test speed was 20mm/sec.
  • sample Type 1 The test was applied on different film samples (CAR, Gellan, Agar, Alginate), each containing different concentrations of the hydrogel polymer in water (e.g. 3%, 5%, 7%, 9%, as examples only), the film having either a height of 100mm (50mm gauge), a width of 20mm and a thickness of 1mm (referred to herein as Sample Type 1) or on a sample prepared according to ASTM D638 Type 1 (Sample Type 2).
  • an edible hydrogel when referring to an edible hydrogel it is to be understood as including only edible components, i.e. components that are or could be recognized as food or acceptably used in food products, and/or acceptable as food safe. In other words, the edible hydrogel cannot include substances that may be considered toxic or unsafe for human consumption.
  • the edible hydrogel can have different levels of water.
  • the hydrogel is a dehydrated hydrogel.
  • the edible hydrogel comprises up to 50wt% liquid, preferably water; at times the dehydrated hydrogel comprises up to 40wt% or at times up to 30wt%; at times between about 5wt% and 40wt%; at times, between about 5wt% and about 35wt%. It is to be understood, in the context of the presently disclosed subject matter, that the dehydrated hydrogel comprises some amount of liquid, i.e. it cannot be completely (0%) without water.
  • the edible hydrogel is a rehydrated hydrogel, comprising at least 50wt% water but not more than 80wt%.
  • the amount of liquid (e.g. a rehydration medium/composition) in the rehydrated hydrogel cannot return to the level that could have been present in the hydrogel before dehydration.
  • the rehydrated hydrogel is semi-solid, having a pliable, dough-like texture.
  • the hydrogel comprises, at minimum, carrageenan (CAR) and an aqueous medium, typically water based.
  • CAR carrageenan
  • aqueous medium typically water based.
  • the hydrogel is dehydrated or rehydrated, may comprise minerals, salts, polymers and other components, in addition to the CAR and water, some of which may be considered as insignificant/inert impurities.
  • the additional components may originate from the source of the CAR and/or be introduced to the hydrogel during its production as will be further explained below.
  • the hydrogel comprises other hydrogel forming agents, in addition to CAR.
  • the other hydrogel forming agent is selected from agar, gelatin, sodium alginate, Gellan Gum, Pectin, Xanthan Gum, Guar Gum, Methylcellulose, Starch, Konjac, Locust Bean Gum, Tara Gum, Curdlan and Chitosan and combinations of same.
  • the CAR constitutes at least 5wt% out of the total hydrogel, irrespective of the amount of the other hydrogel forming agents present in the hydrogel.
  • the addition included a combination of the at least 5% CAR with glycerin.
  • the addition included a combination of the at least 5% CAR with Gellan. In some examples, the addition included a combination of the at least 5% CAR with glycerin and Gellan.
  • the hydrogel consists essentially or consists of only CAR as the hydrogel forming agent.
  • the hydrogel of the presently disclosed subject matter comprises at least CAR.
  • Carrageenan refers to a family of hydrophilic biopolymers made up of P-(l,3) sulfated o-galactose and a-(l,4)-3,6-anhydro-o-galactose residues. These are linear sulfated polysaccharides. There are three basic naturally occurring carrageenan types: Iota Carrageenan (r-Carrageenan), Kappa Carrageenan (K-Carrageenan) and Lambda Carrageenan (X-Carrageenan).
  • CAR when referring to CAR, it is to be understood to encompass at least K-CAR or a K-CAR functional analogue.
  • CAR functional analogue it is to be understood to encompass a hydrophilic sulfated polysaccharide that is capable of being formed into a hydrogel.
  • CAR functional analogue comprises galactose as the monosaccharide unit.
  • the CAR functional analogue is a modified form of a naturally occurring CAR, the modification being exhibited by a different location or amount of ester sulfated groups along the polysaccharide molecule.
  • the CAR functional analogue is one that is cross linked with other polymers e.g. other polysaccharides.
  • the edible hydrogel comprises more than 50% K-CAR out of the total amount of hydrogel forming agents. In some examples, the edible hydrogel comprises more than 60% K-CAR out of the total amount of hydrogel forming agents. In some examples, the edible hydrogel comprises more than 70% K-CAR out of the total amount of hydrogel forming agents. In some examples, the edible hydrogel comprises more than 80% K-CAR out of the total amount of hydrogel forming agents. In some examples, the edible hydrogel comprises more than 90% K-CAR out of the total amount of hydrogel forming agents. In some examples, the edible hydrogel comprises essentially only K-CAR out of the total amount of hydrogel forming agents therein.
  • the hydrogel comprises at least 5wt% CAR out of the total weight of the hydrogel.
  • the hydrogel comprises at least 6wt% CAR out of the total weight of the hydrogel. In some examples, the hydrogel comprises at least 7wt% CAR out of the total weight of the hydrogel. In some examples, the hydrogel comprises at least 8wt% CAR out of the total weight of the hydrogel. In some examples, the hydrogel comprises at least 9wt% CAR out of the total weight of the hydrogel. In some examples, the hydrogel comprises at least 10wt% CAR out of the total weight of the hydrogel. In some examples, the hydrogel comprises at least 1 lwt% CAR out of the total weight of the hydrogel. In some examples, the hydrogel comprises at least 12wt% CAR out of the total weight of the hydrogel. In some examples, the hydrogel comprises at least 13wt% CAR out of the total weight of the hydrogel. In some examples, the hydrogel comprises at least 14wt% CAR out of the total weight of the hydrogel.
  • the hydrogel comprises at most about 15wt% CAR out of the total weight of the hydrogel. In some examples, the hydrogel comprises at most about 14wt% CAR out of the total weight of the hydrogel. In some examples, the hydrogel comprises at most about 13wt% CAR out of the total weight of the hydrogel. In some examples, the hydrogel comprises at most about 12wt% CAR out of the total weight of the hydrogel. In some examples, the hydrogel comprises at most about 10wt% CAR out of the total weight of the hydrogel.
  • the hydrogel comprises between 5wt% and 15wt% CAR out of the total weight of the hydrogel. In some examples, the hydrogel comprises between 6wt% and 15wt% CAR out of the total weight of the hydrogel. In some examples, the hydrogel comprises between 7wt% and 15wt% CAR out of the total weight of the hydrogel. In some examples, the hydrogel comprises between 8wt% and 15wt% CAR out of the total weight of the hydrogel. In some examples, the hydrogel comprises between 9wt% and 15wt% CAR out of the total weight of the hydrogel.
  • the hydrogel comprises an aqueous carrier.
  • the aqueous carrier comprises water and at least one additional component, the additional component being any one of salt, mineral, polymer, low molecular weight compound and combinations of same.
  • the aqueous carrier comprises water, the latter constituting up to 80wt% out of the total weight of the hydrogel.
  • the remainder of the aqueous carrier comprising one of or combination of salts, minerals and/or polymers and optionally inert impurities.
  • the aqueous carrier comprises said water and at least one cationic mineral.
  • the cationic mineral comprises any one of combination of calcium and/or potassium.
  • the cationic mineral can originate from the CAR, i.e. inherently present within the CAR powder from which the hydrogel is formed or can ne externally added to the CAR, at any stage during the formation of the hydrogel or after the hydrogel is formed.
  • the cationic mineral is present or added in an amount that would initiate or promote hydrogel formation.
  • the aqueous carrier comprises a water-soluble polyol(s).
  • the polyol is selected from the group consisting of glycerol, Maltitol, sorbitol, xylitol, erythritol, and isomalt and combinations of same.
  • the polyol is or comprises at least glycerol
  • the hydrogel comprises a cross linking agent.
  • the cross-linking agent can be a cationic mineral, as discussed hereinabove.
  • the aqueous carrier comprises water.
  • the aqueous carrier comprises water and a bulking agent.
  • the aqueous carrier comprises water, a bulking agent and protein. In some examples, the amount of water in the aqueous carrier is at least 50wt% out of the total volume of the hydrogel.
  • the aqueous carrier of the final hydrogel is the same as the rehydrating composition/medium.
  • the edible hydrogel can be provided in any physical form.
  • the edible hydrogel is in a form of a film.
  • a film it is to be understood to define also the physical shape of the hydrogel having at least one dimension that is twice greater than at least one other dimension of the physical shape.
  • the film is in a form of a layer, having a length (longitudinal dimension/direction) and/or width (being perpendicular to the length and defining with the length the film's plane) that are greater than the thickness or height thereof (perpendicular to the film's plane).
  • the "film” can be defined by a Cartesian coordinate system (X - length, Y- width, defining together the films horizontal plane, Z - thickness) and excludes any amorphous shapes.
  • the edible film has a thickness of at most 5mm; at times, at most 4mm; at times at most 3mm; at times at most 2mm; at times at most 1mm; at times at most 1mm; at times at most 0.9mm; at most 0.8mm; at most 0.7mm; at most 0.6mm; at most 0.5mm; at most 0.4mm; at most 0.3mm; at most 0.2mm; at most 0.1mm; at times, at most 0.05mm or even at most 0.01mm.
  • the edible film has a thickness of between about 0.01mm and 5mm; at times, between 0.05mm and 5mm; at times, between 0.05mm and 5mm; at times, between 0.05 and 4mm; at times, between 0.05mm and 3mm; at times between 0.1mm and 5mm; at times between abut 0.1mm and 4mm; at time between about 0.1mm and 3mm; at times between about 0.1mm and 2mm; at times between 0.2mm and 5mm; at times between 0.3mm and 3mm; at times, within any range between 0.5mm and 5mm. Any range within the range of about 0.01mm and about 5mm also forms part of the presently disclosed subject matter.
  • the edible film has a length of at least 10mm; at times, at least about 50mm; at times, at least about 10cm; at times, at least about 20cm; at times, at least about 30cm; at times, at least about 40cm; at times, at least about 50cm; at least about 60cm; at least about 70cm; at least about 80cm; at least about 90cm; In fact, the edible film can even reach a length of meters.
  • the hydrogel is in particulate form, this including spherical forms, amorphous particulates, flakes, and the like.
  • the presently disclosed hydrogel is uniquely strong and/or thermally stable. These physical properties are exhibited when the hydrogel comprises between about 50wt% water and 80wt% aqueous liquid.
  • the hydrogel, with this liquid content, is characterized by one or more of the following features:
  • Storage Modulus (G') - The hydrogel exhibits a storage modulus of at least lOKPa within a wide temperature range as shown in Table 2 and Table 5A of the below non-limiting Examples. Storage modulus is a measure of how much force must be put into the sample in order to distort it.
  • Storage Modulus can be determined using a rotational rheometer (e.g. texture analyzer being the same or similar to TAI HR 20 Discovery Hybrid Rheometer, ARES-G2, Advanced Peltier System (APS)) using 40mm stainless steel, sandblasted plates and a strain range of l%-10%, preferably about 10%, Axial force within a range of about IN to about 10N, preferably about IN, and frequency of 10Hz.
  • a rotational rheometer e.g. texture analyzer being the same or similar to TAI HR 20 Discovery Hybrid Rheometer, ARES-G2, Advanced Peltier System (APS)
  • APS Advanced Peltier System
  • a hydrogel having a storage modulus of at least lOKPa would be understood to be solid, and stiff/hard.
  • the presently disclosed hydrogel has a storage modulus of at least 20KPa, at times of at least 30KPa; at times of at least 40KPa; at times of at least 50KPa; at times of at least 60KPa; at times of at least 70KPa; at times of at least 80KPa when measured at a temperature of 50°C.
  • the presently disclosed hydrogel has a storage modulus of between lOKPa and l,000KPa, when measured at a temperature range of 25°C and 70°C; at times, within a range of 20KPa and l,000KPa, when determined at a temperature range of about 25°C and about 50°C; or at times, within a range of 80KPa and l,000KPa, at a temperature range of about 25°C and about 50°C.
  • Tensile Strength tensile stress at break
  • the hydrogel exhibits a tensile strength (ultimate tensile strength) of at least 600KPa, and preferably at least 2MPa or at least 3MPa, i.e.
  • Tensile strength and tensile strain at break were determined by TAI series texture analyzer with the test conditions including a load cell of 100N and a speed test of 20mm/sec with a sample having dimensions of about 100mm*20mm and thickness of about 1.0mm (herein Sample Type 1) or with a sample prepared according to ASTM D638 Type 1 (herein Sample Type 2).
  • the hydrogel has a tensile strength of at least 600KPa; at least 700KPa; at least 800KPa; at least 900KPa; at least IMPa; at least l. IMPa; at least
  • the hydrogel has a tensile strength of at least about 3MPa.
  • the hydrogel has a tensile strength of up to 30MPa, or up to 20MPa or up to lOMPa.
  • Tensile Strain (strain at break, %) -
  • the hydrogel exhibits a tensile strain at break of at least 15% at 25°C; at times, of at least 16%, or even at least 17% at said temperature.
  • the values that were obtained with the CAR based hydrogel were much higher than that obtained with the other exemplified hydrogel forming polymers, such as Agar, and Alginate.
  • the presently disclosed subject matter is further supported by the non-limiting examples that show that the properties of the hydrogel are not limited to a specific CAR concentration and/or treatment duration and in fact using CAR content that is above 5% and/or shorter dehydration times provided edible hydrogels with the same advantageous physical properties.
  • the presently disclosed subject matter also provides a method for obtaining the presently disclosed hydrogel.
  • the presently disclosed method comprises exposing or treating a native hydrogel comprising at least 5wt% CAR in an aqueous medium to a dehydration process until obtaining a dehydrated hydrogel with up to 50% liquid content i.e. not more than 50% water remaining in the hydrogel, preferably not more than 45% water remaining in the hydrogel; or even preferably not more than 40% water remining in the hydrogel; or even not more than 35% water remaining in the hydrogel or even not more than 30% water remaining in the hydrogel; or even not more than 25% water remining in the hydrogel).
  • the dehydrated hydrogel is then subjected to a rehydration process by exposing the dehydrated hydrogel to a rehydration medium.
  • native hydrogel when referring to native hydrogel it is to be understood to denote the hydrogel per se comprising the hydrogel forming agent (be it a single agent or a combination of hydrogel forming agents, as described above with respect to the presently disclosed edible hydrogel) and the aqueous medium holding the hydrogel forming agents.
  • the native hydrogel is typically at a gel state.
  • processing steps applied onto the native hydrogel it is to be understood to also encompass processing steps applied onto the hydrogel after being exposed to the anti-solvent treatment. For example, dehydration can be performed on the native hydrogel (the hydrogel forming material and water per se) as well as to the native hydrogel, after being exposed to an anti-solvent system.
  • the native hydrogel is to be understood to refer to the product of mixing the hydrogel forming agent(s) in an aqueous medium. Such mixing typically results in the formation of a gel.
  • the native hydrogel may be in a form of a semi-solid, i.e. before the gel is completely formed or fully solidifies.
  • the native hydrogel comprising at least 5wt% CAR in an aqueous medium, it is to be understood to encompass a mixture in any degree of gelation.
  • prior to exposing the hydrogel to a dehydration process it is subjected to an anti-solvent treatment prior to exposing the hydrogel to a dehydration process.
  • the anti- solvent treatment is not mandatory and yet was found to improve the properties of the resulting rehydrated hydrogel.
  • the dehydration process it is to be understood to refer to a process that is applied onto the native hydrogel or on the native hydrogel after being subjected to the anti-solvent treatment, as further described below.
  • the dehydration step can be performed by any technique available in the art.
  • dehydration is by heating the hydrogel (native or after anti-solvent treatment).
  • the dehydration is by heating at a temperature of at least 40°C; or even at least 45°C; or about 50°C, but not more than 70°C for a time sufficient to reduce the liquid (mainly water) content to below 50%.
  • the dehydration is under conditions causing reduction of the liquid content to below 45%.
  • the dehydration is under conditions causing reduction of the liquid content to below 40%.
  • the dehydration is under conditions causing reduction of the liquid content to below 35%.
  • the dehydration is under conditions causing reduction of the liquid content to below 30%.
  • Dehydration can be achieved by placing the hydrogel within a drying oven set at a temperature of not more than 70°C, at times, not more than 60°C, at times, not more than 55°C, at times, about 50°C.
  • the dehydration involves circulation of air, to remove humidity.
  • the dehydration is for at least several hours, e.g. about 1 to 15 hours, about 2 to 12 hours, about 3 to 14 hours, about 5 to 13 hours, about 6 to 12 hours or for any time within the time window of 1 to 15 hours.
  • hydrogel film When requiring a hydrogel film, it can be formed on a film forming bed or in mold while controlling thickness (height dimension) of the hydrogel during the different treatment. This is achieved by pouring the native hydrogel, onto the film forming bed or placed as a thin laminate. The thickness of the hydrogel being formed would typically be equal or less than the eventually formed hydrogel film.
  • the heating of the gel can be before placing the gel in the mold or on the film forming bed, or after said placement.
  • these can be formed by either grinding/ chopping the dehydrated or rehydrated hydrogel film, or by a priori forming the native hydrogel in particulate form, e.g. as droplets on a bed, or by using an air jet nebulization of small sprayed droplets, or by the use of a mesh shaped mold.
  • the thus formed dehydrated hydrogel are then rehydrated within a rehydrating environment.
  • the dehydrated hydrogel can be defined/identified/characterized by the same tests used to characterize the hydrogel after rehydration. Specifically, the dehydrated hydrogel can be characterized by first transforming the dehydrated hydrogel into a hydrated state, i.e. into its rehydrated form (rehydration until the hydrogel holds between about 50wt% and about 80wt% water).
  • the hydrogel can be characterized by any one or combination of: a storage modulus (G 1 ) of at least lOKPa within a temperature range of 25 °C- 70°C; as determined by applying on a disc sample formed from the rehydrated hydrogel the disc having dimensions of 40mm* 1mm thick and analyzed by Rheometer (Discovery HR20, TA) when placed between 40mm stainless steel, sandblasted parallel plates, a strain in the range of about 1% and about 10%, preferably about 10%, an axial force in the range between about IN and about 10N, preferably about IN, and at a frequency of 10Hz a tensile strength of at least 600kPa as determined at 25°C on a strip sample of said edible hydrogel, having dimensions of about 100mm*20mm and thickness of about 1.0mm (referred to herein as Sample Type 1), or on a sample prepared according to ASTMD638 Type 1 (referred to herein as Sample Type 2), and a tensile strain at
  • the rehydrated hydrogel is characterized by at least two of the above characteristics, namely, at least two, at times all three of the storage modulus and/or the tensile strength and/or tensile strain.
  • the dehydrated hydrogel when the native hydrogel is subjected to an anti -solvent treatment, followed by dehydration, can be stored As Is until further use or it can be further processed by exposing the same to a rehydration composition, at least to form therefrom the rehydrated hydrogel.
  • a dehydrated hydrogel when referring to a dehydrated hydrogel it is to be understood to encompass a hydrogel containing up to 50wt% water; and preferably between 30wt% and 50wt% water; while when referring to hydrated hydrogel it is to be understood to encompass a hydrogel holding between 50wt% water and 80wt% water.
  • the edible hydrogel can also be a rehydrated hydrogel, namely, holding between 50wt% to 80wt% water.
  • the rehydrated hydrogel is obtained by placing the dehydrated hydrogel in a controlled humidity chamber.
  • the rehydrated hydrogel is obtained by placing the dehydrated hydrogel in a rehydrating composition made of dough or gel or moisture containing food mass. This may include, for example, placing the hydrogel between layers of the food product or mixed with other components of the food product, which it is needs to reinforce, as further discussed below.
  • the rehydrated hydrogel can also be obtained by exposing or soaking or infusing, immersing, impregnating, or saturating, the dehydrated hydrogel to a rehydrating composition.
  • the rehydrating composition or rehydrating environment can include any aqueous based medium that causes rehydration of the hydrogel.
  • the rehydrating composition is the same as the aqueous medium in which the CAR was initially dissolved (i.e. the aqueous medium in the native hydrogel).
  • the rehydrating composition is different from the aqueous medium in which the CAR was initially dissolved. Being the same or different, the aqueous medium and the rehydrating composition comprise at least water.
  • the aqueous medium and the rehydrating composition comprise a same or different cross-linking agent.
  • the cross-linking agent is a cationic mineral, as descried hereinabove.
  • the cross-linking agent comprises at least potassium, e.g. KC1.
  • the cross-linking agent e.g. KC1
  • KC1 is present within the hydrogel forming mixture and/or within the rehydrated hydrogel at a salt concentration of between 0.1M and IM, typically, although not exclusively, at a water volume of about 70%.
  • the cross-linking agent is present within the native hydrogel and/or within the rehydrated hydrogel at a salt concentration of between about 0.1M and 0.9M; at times, between 0.15M and 0.75M; at times, between 0.05M and 0.8M.
  • any one of the aqueous medium and the rehydrating composition comprise a polyol.
  • polyols that can be used as part of the solvent system include glycerol, Maltitol, sorbitol, xylitol, erythritol, and/or isomalt.
  • the aqueous medium and the rehydrating composition are different.
  • the rehydrated hydrogel is stored AS IS, or is further processed into an edible final product.
  • the native hydrogel can be subjected to an anti- solvent system.
  • an antisolvent of "anti-solvent system” it is to be understood to include any solvent that reduces solubility of the CAR within the aqueous medium in which it is held.
  • the adding or exposure of the native hydrogel to the anti-solvent initiates or promotes the conversion of the gel comprising the CAR in soluble form into a semi-solid (stiffer/harder/tougher) state.
  • the treatment with the anti-solvent system comprises soaking or saturating or immersing or otherwise bringing the native hydrogel (at least partially in a gel state) in contact with an anti-solvent system.
  • the exposure to an anti-solvent comprises saturating the native hydrogel to the anti-solvent system, in the presence of a cross-linking agent, e.g. the antisolvent comprises alcohol and the cross-linking agent, e.g. KC1.
  • cross linking agents can be added at any stage of the process of forming the hydrogel. It can be part of the CAR powder which is mixed with an aqueous medium (comprising or consisting of water), to thereby form the hydrogel forming mixture; it can be part of the aqueous medium; it can be added during the anti -solvent treatment/exposure; etc.
  • aqueous medium comprising or consisting of water
  • the anti-solvent comprises ethanol.
  • the alcohol treatment comprises exposing the native hydrogel to an ethanol system comprising a salt (as the cross linking, such as KC1).
  • a salt as the cross linking, such as KC1.
  • the salt or the KC1 is at a concentration of between about 0.01M and IM, at times, between about 0.05M and 0.75M, at times, between about 0.1M and 0.5M.
  • the alcohol treatment is for a time sufficient to initiate solidification of the native hydrogel.
  • the alcohol treatment is for a time period of 1 to several hours, e.g. l-5hours, or 1-4 hours or 1-3 hours.
  • the alcohol treatment of the anti solvent system takes place before the dehydration step.
  • the above treatment with the anti-solvent system can be performed in a container and after the anti-solvent is added, the solidifying mixture is placed on the bed or within the mold. In some other examples, the mixture is placed on the bed or within a mold during the anti-solvent treatment. In yet some other examples, the mixture is placed on the bed or within a mold during the dehydration process.
  • the resulting edible hydrogel can be it in dehydrated state or in its rehydrated state, can be subjected to additional processing steps.
  • the resulting hydrogel is subjected to mechanical processing.
  • the mechanical processing can comprise any one or combination of pressing, role pressing, drawing, spinning and the like.
  • the edible hydrogel of the presently disclosed subject matter can be used in various food products, as a strengthening element, due to its high physical strength, as disclosed herein.
  • the edible hydrogel is added as a reinforcing element within the food product.
  • the disclosed edible hydrogel is used for improving at least texture of food products.
  • the edible hydrogel is used for reinforcing/improving texture of non-animal derived alternative food products, e.g. plant based or cell based (cell cultured) alternative foods.
  • the hydrogel is in a form of a film, placed between layers of the protein mass of a food product, e.g. during additive manufacturing of the multi - layered food product.
  • the additive manufacturing comprises 3D printing of the food product.
  • the hydrogel film can thus be useful in reinforcing of whole meat slab analogues, steak analogues and the like.
  • the hydrogel is in particulate form, mixed with minced- like protein mass. This can be useful, e.g. in the manufacturing and reinforcing of plantbased hamburgers, kebabs, and the like.
  • the present disclosure also provides a food product comprising the edible hydrogel disclosed herein, in the form of films, particles and mixtures of same.
  • the food product is a meat analogue product.
  • the food product is a cheese analogue product.
  • the edible hydrogel disclosed herein is suitable for use as edible food packaging, such as for stuffed foods, e.g. sausages.
  • the disclosed edible hydrogel can also be used for changing the texture (e.g. toughening) of other foods, such as jams, tofu, noodles, dessert gels, jellies.
  • a salt includes one or more types of salts, e.g. for cross linking the hydrogel forming agent.
  • the term “comprising” is intended to mean that the composition include the recited components, i.e. at least CAR and water, but not excluding other elements, such as salts, mineral, polymers that may be inert or have a benefiiary effect on the formation of the hydrogel.
  • the term “consisting essentially of' is used to define hydrogels or other composioins which include the recited elements but exclude other elements that may have an essential significance on the formation of the hydrogel with the defined properties. "Consisting of' shall thus mean excluding more than trace elements of other elements. Embodiments defined by each of these transition terms are within the scope of this invention.
  • K-CAR (5%, CPKELCO WR-78) solution was prepared in a Thermomix device, heated to 90°C for 15 minutes.
  • the resulting "activated CAR” solution was poured over a clean surface and compressed with a heated metal surface to obtain a uniform film of 1mm thickness, referred to hereinbelow as the "Native" CAR.
  • the activated CAR solution is placed on top of a clean surface, heated to 90°C and the solution is then smeared on the surface using a roller. The distance between the surface and the roll will determine the thickness of the film.
  • films as thin as 0.01mm can be prepared.
  • the film was then segmented into sample films, and each segment was subjected to a different treatment as defined below:
  • Dehydration/Rehydration - Dehydration by heating the Native CAR to 50°C and then rehydration by soaking the dehydrated segmented sample film in rehydration compositions as detailed below.
  • the time needed for dehydration depended on the thickness of the film. For a film of 1mm, dehydration was for at least 12 hours.
  • Rehydration composition two types of rehydration compositions were used:
  • Rehydration composition A comprising about 55%-70% water, about 13%- 15% TVP soaked in water, about 25% other plant-based protein, about 1% Methylcellulose.
  • Rehydration composition B - comprising about 15% -25% TVP soaked in water, about 3%-8% plant-based oil, about 55%-70% water, about 3%-8% plant-based protein, about 3% Methylcellulose
  • the two rehydration compositions had a viscous, semi-solid texture, similar to dough, allowing the use of the same as in a form of pliable, layers.
  • Figure 1 shows the TGA of the different treated films.
  • Figure 1 shows that the Native film (i.e. no treatment) and the ethanol treated film, water is bound to the CAR molecules and evaporated at temperatures between 100°C and 150°C.
  • the Anti-Solvent/Dehydration film had approximately 10% water, as shown by the respective arrow.
  • Table 1 shows that in the Anti-solvent/Dehydrated film, the amount of water is about 10%, while after rehydration, the amount of water does not (and cannot) return to its level as in the Native film or after only the Anti-Solvent treatment. Rehydration of the dehydrated film allowed for up to 80% water content.
  • Temperature dependent storage modulus (Temperature Sweep Test) of different films were tested.
  • the Storage Modulus test was performed on discs of 40mm in diameter and 1mm thick, and analyzed by Rheometer (Discovery HR20, TA) using 40mm stainless steel, sandblasted parallel plates, during which each film was subjected to Grips axial force (IN), oscillation strain of 10%, and frequency of 10Hz.
  • the tested temperature range was 25°C-70°C, which also provided information regarding each films' melting temperature and plasticity.
  • Table 2 shows Temperature dependent Storage Modulus of the tested films.
  • Table 3 A The data presented in Table 3 A was obtained using a TAI Series Texture Analysis machine (LLOYD TAI), using a load cell of 100N with TG74: adjustable Rear Face Vice Grip 5kN-11241bf. Test speed was 20mm/sec. The test was applied on different film samples (CAR, Gellan, Agar, Alginate), each containing 5% of the hydrogel polymer in water, the film having a height of 100mm (50mm gauge), a width of 20mm and a thickness of 1mm.
  • CAR Gellan, Agar, Alginate
  • the Native "CAR" film was found to be the weakest amongst the CAR containing films, breaking already at a stress of approximately 200 KPa, All CAR films had a higher resistance to stress when compared to the films from other polymers. While the Anti-Solvent CAR film showed a tensile strength of between 600 KPa and 900kPa, being a bit higher than that of the Native CAR film, the CAR Dehydration/Rehydration film and CAR-Combined film were superior in terms of their tensile strength and breaking at stress of over 2000 KPa, for the Dehydration/Rehydration film (i.e.
  • the tested films were also analyzed for hydrogel forming material content and water content after the indicated treatment (rehydration composition A was used) and the results are provided in Table 4:
  • Example 4 Films with different CAR concentration
  • Table 5A provide Storage Modulus determined in a test performed on discs of 40mm in diameter and 1mm thick, and analyzed by Rheometer (Discovery HR20, TA) using 40mm stainless steel, sandblasted parallel plates, during which each film was subjected to Grips axial force (IN), oscillation strain of 10%, and frequency of 10Hz.
  • the tested temperature range can be 25°C-70°C.
  • Table 5B provide tensile strength results with films formed with rehydration composition B and tested using TPA apparatus, under the conditions described above, and with the test samples created according to ASTM D638 Type 1 (herein referred to as Sample Type 2).
  • Sample Type 2 the test samples created according to ASTM D638 Type 1 (herein referred to as Sample Type 2).
  • Sample Type 2 Table 5A - Storage Modulus of films formed with rehydration composition B

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Abstract

La présente divulgation concerne un hydrogel comestible comprenant du carraghénane (CAR) et un support aqueux comprenant de l'eau, ladite eau constituant jusqu'à 80 % en poids d'un volume total de l'hydrogel ; lorsque ledit hydrogel présente entre 50 % en poids et 80 % en poids de teneur en eau, l'hydrogel est caractérisé par (a) une teneur en CAR d'au moins 5 % en poids sur un volume total de l'hydrogel ; (b) un module de conservation (G1) d'au moins lOKPa dans une plage de température de 25 °C à 70 °C ; (c) une résistance à la traction d'au moins 600 kPa comme déterminé à 25 °C ; et (d) une contrainte de traction à la rupture d'au moins 15 % comme déterminé à 25 °C. L'invention concerne également des procédés d'obtention de l'hydrogel comestible et ses utilisations.
PCT/IL2022/050933 2021-08-30 2022-08-29 Hydrogel comestible, procédé de production et ses utilisations Ceased WO2023031915A1 (fr)

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