Use of biodegradable, bio-based thermoplastic materials having a brittle fracture mechanism as shells for eggs or egg substitute products, and vegan substitute products coated with such shells

Abstract

The present invention relates to the use of a material produced by extrusion consisting of (A) one or more biodegradable and thermoplastic processable biopolymers and (B) one or more inorganic, organic or sparingly soluble salts as a shell for an egg replacer product, and to an egg replacer product comprising vegan-based egg white and egg yolk coated with such a shell.

Description

[Technical field]

[0001] The present invention relates to the use of a material based on a biodegradable bio-based polymer, which is formulated with additives in a suitable manner, for producing shells for eggs or egg replacer products from it by a thermoplastic production process. The target application is therefore a novel packaging material for eggs and egg replacer products. [Background technology]

[0002] The chicken reproductive cells, consisting of the yolk and the egg white, are surrounded by two fibrous membranes and a calcified, partly crystalline shell. The structure of the eggshell serves to protect the egg from mechanical damage, microbial contamination, and drying, as well as to regulate the exchange of gases and water. The eggshell is composed of 95-97% calcium carbonate crystals stabilized by matrix proteins. This matrix also plays an important role in the calcification process. The crystals grow upwards along this in a palisade-like manner, forming a porous shell (see Figure 1). This complex structure cannot be reproduced artificially. Chicken eggs can be 40-50 mm in diameter, and the shell reaches a wall thickness of 340-410 μm. The maximum tensile stress of the chicken eggshell (measured along the long axis) is about 18.3-29.9 MPa. The strength of the eggshell decreases with the size of the egg, i.e. less force is required to break the egg. The reason for this is speculated to be a proportional increase in the number and size of defects in the shell microstructure [Reference 2]. The elastic modulus of the eggshell is 18-27.5 GPa. Due to its porous structure and the associated functions, the eggshell must not restrict the material exchange of the developing chick and must not be a significant gas barrier [Reference 3].

[0003] Naturally occurring organic or inorganic hybrid materials such as eggshells, snail shells, corals and bones are characterized by high strength or stiffness, as well as light weight and material economy in their design. Their outstanding mechanical properties result from a hierarchical structure of individual components, including inorganic components and organic matrices, which are difficult to copy and engineer. However, sporadically, researchers have already succeeded in developing materials on a laboratory scale that bear a striking similarity to natural paradigms. For example, bacterially produced CaCO 3 By alternately precipitating nacre and bacterially produced polyglutamic acid (PGA), they succeeded in producing a nacre-like material [Reference 4]. The hardness and fracture behavior were similar to those of natural nacre, and accordingly superior to those of crystalline calcite.

[0004] However, most of the technically mature manufacturing methods belong to the field of thermoplastic processing. The compounding step allows the addition of additives to the polymer or the adaptation of the particle size distribution. Such compounding steps are often carried out in twin-screw extruders [Ref. 5] with the aim of pretreating, granulating, filling or reinforcing the plastic. The resulting granules are suitable for the subsequent thermoplastic processing into the final presentation of the material, e.g. by extrusion, injection molding or spray molding [Ref. 6].

[0005] The literature describes a wide variety of combinations of biopolymers and fillers, as well as the expected properties, often mechanical properties, where the type of polymer and filler, their concentrations, and the temperature conditions during processing influence the final mechanical properties of the composite.

[0006] Cinelli et al. [Reference 7] used polyhydroxyalkanoates (PHBV with a 5% valerate fraction) with a biodegradable biobased softener (acetyl tributyl citrate, 10%) and 5% CaCO 3and 10-30% lignocellulosic fibers (pea fiber, wood fiber) at 170 °C for use in injection molded rigid food packaging. It has been observed that with increasing fiber content, the modulus increases, whereas the tensile strength and elongation at break decrease. Chen et al. [Ref. 8] studied the crystallization kinetics of PHBV / Clay nanocomposites. The addition of a small amount of organically modified montmorillonite (OMMT) improved the crystallization kinetics of PHBV as well as its tensile strength and modulus, whereas the reverse occurred when too much OMMT was used. A similar effect was also observed by Duangphet et al. [Ref. 9], where PHBV (3% valerate fraction) was blended with 5-20% calcium carbonate and the crystallization behavior was investigated. A small amount (5%) of CaCO 3 The addition of CaCO increases the crystallization rate of PHBV. 3 (20%) has the opposite effect, increasing the crystallite size and CaCO 3 This was associated with enhanced particle aggregation. Cabedo et al. [Reference 10] investigated the effect of processing conditions on the degradation of PHBV / Clay systems. Kaolin was reported to have no effect on PHBV degradation, whereas montmorillonite (MMT) induces degradation through the release of bound water from the clay surface at elevated temperatures, which is activated in MMT by surface modifiers. Ding et al. [Reference 11] investigated the effect of processing conditions on the degradation of PHBV / Clay systems. Kaolin was reported to have no effect on PHBV degradation, whereas montmorillonite (MMT) induces degradation through the release of bound water from the clay surface at elevated temperatures, which is activated in MMT by surface modifiers. 3 The thermal stability of P3 / 4HB was investigated using a P(3HB-4HB) compound containing 5 mol% CaCO 3 It decreased with increasing CaCO content. 3 With increasing content, the elongation at break, tensile strength, and impact toughness also decreased; whereas the elastic modulus increased. The crystallization rate of P(3HB-4HB) was 3 The maximum crystallinity is observed at 40% CaCO 3 This was achieved at a concentration of PHBV / CaCO3 Besides the mechanical properties of the compounds, Kirboga et al. [Reference 12] also investigated other properties relevant to packaging, such as oxygen barrier and water vapor barrier. 3 The improvement of stiffness (dynamic modulus by DMA) as well as oxygen and water vapor barriers was achieved by adding 0.1% CaCO 3 Xiong et al. [Reference 13] reported that the effect of adding 10–30% CaCO 3 and (CaCO 3 PBS containing up to 3% aluminate-based, silane-based, and titanate-based compatibilizers (relative to CaCO 3 The purpose of the addition was to reduce costs by using less PBS. The addition of the compatibilizer improved tensile strength and ultimate elongation. Compounds consisting of PLA / PBAT in a 3:1 ratio with 2% talc powder and up to 20% crushed shell powder were described by Gigante et al. [Reference 14], in which the modulus improved with increasing loading, but the tensile strength decreased slightly. The compounds were suitable for injection molding applications.

[0007] Biodegradable polymers in combination with inorganic or organic sparingly soluble fillers have also been studied and used in medical applications, e.g. for bone tissue engineering, cartilage formation, vascular grafts, and other implantable biomedical devices. A review by Sathiyavimal et al. [Reference 15] provides an overview of materials based on naturally occurring non-thermoplastic polymers, such as collagen, gelatin, chitosan, fibrin, cellulose, alginate, with inorganic components, e.g. hydroxylapatite. Additional functions, such as the release of active substances or antibacterial activity, can also already be realized. Similarly, thermoplastic polymers such as polyhydroxyalkanoates, PCL, PLA, PVAc, PEO, and their compounds with inorganic sparingly soluble fillers, e.g. hydroxylapatite, calcium phosphate, bioactive glass, or wollastonite, have already been used in implants as biocompatible and biodegradable materials [Reference 16]. Rodriguez-Contreras's overview paper [Reference 17] describes the medical suitability of PHB, PHBV, and P(3HB-4HB) based on their biocompatibility, biodegradability, and non-toxicity, as suture materials, for valves, as bone graft substitutes in tissue engineering, as cartilage, as stents for nerve repair, and as cardiovascular plasters.

[0008] In the biomedical field, there are complementary methods for the preparation of composites. For example, Chernozem et al. [Reference 18] reported that PHB and PHBV (12% valerate fraction) were electrospun into fibers in chloroform. 2 CO 3 and CaCl 2 By precipitation reaction with CaCO 3was deposited on the fibers and inorganic filler substances were injected into them by ultrasonication. Since the aim of this work was to create bone tissue for regenerative medicine, bone-forming cells (osteoblasts) were stimulated to anchor and grow on the surface, which results in subsequent biomineralization (formation of apatite). In his doctoral thesis, Jagoda [Ref. 19] described the creation of a bone substitute material consisting of poly[R]-3-hydroxy-10-undecenoate (PHUE) and a representative of medium-chain PHA, which was deposited as a monolayer material on calcium phosphate. Due to its elastomeric properties, this polymer forms a flexible matrix for calcium phosphate crystals, similar to collagen in bone. Degli Esposti et al. [Ref. 20] described a method to create a porous material from PHB and hydroxylapatite that mimics natural bone material. PHB was dissolved in dioxane and mixed with up to 8% hydroxylapatite nanoparticles, or hydroxylapatite was prepared in situ by a sol-gel process in the presence of dissolved PHB. Temperature-dependent decomposition produced a porous structure.

[0009] US Pat. No. 5,399,433 [Reference 21] describes the production of an egg envelope consisting of two combined rotationally symmetric half-shells (i.e. the separation plane runs perpendicular to the long axis or axis of rotational symmetry of the egg) which are hermetically closed after filling with egg yolk. The lower half-shell has an opening through which the egg white is finally added, whereby the egg is filled as a whole, with the egg yolk floating in the egg white. Finally, the filling opening of the eggshell is further hermetically closed. In the embodiment described in US Pat. No. 5,399,433, the shell, which has the same breaking properties as a natural egg, may have gas permeability and a translucent visual appearance, for example consisting of "styrene maleic anhydride (SMA)". This material may be biologically degradable after production, at least by the addition of "oxobiodegradable" additives. The subject of US Pat. No. 5,399,433 [Reference 22], filed in 2003, is a flexible, breathable polymer film and a corresponding manufacturing method. The film described is flexible and breathable, and has funnel-shaped expanding pores in the surface area. Taking the natural ostrich egg as an example, the intention is to create a porous material that best embodies photocatalysis, to be produced by a sol-gel process. However, a substitute eggshell with a similar fracture behavior to that of a natural chicken egg cannot be produced by the polymer films described in this document. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] US2019 / 263557 specification [Patent Document 2] DE 10301984 A1 Summary of the Invention [Problem to be solved by the invention]

[0011] The task of the present invention was to develop a material that has properties similar to those of mineral composites present in the living world in terms of color, strength, fracture behavior and biological degradability, and that maintains its shape and tightness in boiling water. Furthermore, the material developed should have a barrier against microorganisms, oxygen, water and water vapor, which is a prerequisite for food packaging materials to achieve product protection. This material should also be able to withstand a wide range of environmental conditions (heat and H2O). 2 O 2 The composition may be pasteurizable (by oxidizing agents such as ethylhexyl ether) and is therefore primarily intended for application in egg replacer products. [Means for solving the problem]

[0012] This problem is solved by the features of claims 1 and 9. Preferred embodiments emerge from the dependent claims.

[0013] The materials or material mixtures, hereinafter also referred to as "compounds", comprise one or more biodegradable, thermoplastically processable biopolymers (A) in association with one or more inorganic or organic sparingly soluble fillers or additives (B).

[0014] The biodegradability of the base material (A) used according to the present invention is determined according to various standards: biodegradability is determined by achieving at least 90% degradation within 180 days, a decomposition level of less than 10% dry mass after 12 weeks for particles larger than 2 mm, passing biotoxicity analysis involving plant growth, and - under (semi-)industrial composting conditions (e.g. according to OK compost-EN 13432), - preferably under home composting conditions (e.g. according to OK compost home-TUeV Austria, Belgium), particularly preferably under freshwater or marine degradation conditions (for example according to ISO 22403 or ASTM D6691-17), This corresponds to compliance with limits on heavy metals.

[0015] As biopolymer component (A) the following preferably come into consideration: - one or more polyhydroxyalkanoates and / or polyhydroxyalkanoate-copolymers, preferably poly(3-hydroxypropionate) PHP, poly(3-hydroxybutyrate) PHB / PH3B, poly(3-hydroxyvalerate) PHV, poly(3-hydroxyhexanoate) PHHx, poly(3-hydroxyheptanoate) PHH, poly(3-hydroxyoctanoate) PHO, poly(3-hydroxynonanoate) PHN, poly(3-hydroxydecanoate) PHD, poly(3-hydroxyundecanoate) PHUD, poly(3-hydroxydodecanoate) PHDD, poly(3-hydroxytetradecanoate) PHTD, poly(3-hydroxypentadecano ... poly(3-hydroxyhexadecanoate) PHPD, poly(3-hydroxypropionate-co-3-hydroxybutyrate) (P3HP-3HB), poly(3-hydroxypropionate-co-4-hydroxybutyrate) (P3HP-4HB), poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P(3HB-4HB)), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHB-HHx), poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyhexanoate) (PHBV-HHx), C 3 -C 11 Medium chain PHA (mcl-PHA) with a side chain length of C 12 and long-chain PHAs (Icl-PHAs) having a side chain length greater than 3, preferably PH3B, PHBV, PHB-HHx, or (P(3HB-4HB)). - Polylactide: Amorphous and crystalline variations of poly(L-lactide) PLLA, poly(D-lactide) PDLA, stereocomplex-(polylactide) sc-PLA, and stereoblock-(polylactide) sb-PLA

[0016] As filler substances or additives (B) there come into consideration one or more inorganic or organic salts, preferably the following: - sparingly soluble salts: carboxylates, sulfates, hydrogen sulfates, sulfides, phosphates, hydrogen phosphates, oxides, hydroxides, citrates, oxalates of earth-alkali elements or transition metals or aluminium, preferably CaCO 3 , CaSO 4 , Ca 3 (PO 4 ) 2 , MgCO 3 , BaSO 4 , Calcium citrate, Calcium oxalate, Fe 2 O 3 , Al 2 O 3 . - stoichiometric and non-stoichiometric double salts and hydrates as well as silicates, preferably CaCO 3 *MgCO 3 (Dolomite), CaSO 4 *2H 2 O (gypsum), CaSiO 3 (wollastonite), clay minerals (e.g. montmorillonite, kaolinite, bentonite, talcum), hydroxylapatite, and SiO in various manifestations. 2 (e.g. silicic acid, bioactive glass, SiO 2 based nanoparticles, etc.).

[0017] The mass proportion of the filler or additive (B) in the biopolymer matrix is ​​1-50%, preferably 5-45%, particularly preferably 30-45%.

[0018] The powdered or granular biopolymer component is preferably dehydrated by pre-drying for 6 to 48 hours at a temperature of 50 to 80° C. The inorganic or organic sparingly soluble filler material is preferably dehydrated by pre-drying for 6 to 48 hours at a temperature of 70 to 120° C.

[0019] The weight proportions of each component in the compound can be adjusted by premixing the powdered components in the correct ratio and preferably subsequently applying an extrusion or other thermoplastic manufacturing process, or by feeding components of different bulk density separately to the processing equipment, e.g. an extruder.

[0020] The temperature profile of the extruder should be adjusted to avoid thermal degradation of the components, which requires keeping the processing temperature within the melting point of the polymer, typically 10-20°C or lower (to account for the additional heat contribution from the mechanical energy input) or 10-20°C or higher (to reduce viscosity and achieve improved homogeneous mixing).

[0021] For PHBV (melting point 170-175°C depending on type) as the substrate polymer, the temperature profile may be, for example, a lower range of 40-50°C and an upper range of 130-160°C, particularly 45-140-150-150-150°C. For PLA (melting point 150-200°C depending on type) as the substrate polymer, the temperature profile may be, for example, a lower range of 50-70°C and an upper range of 140-200°C, particularly 60-160-190-190-145-145-145°C.

[0022] After leaving the extrusion nozzle, the compound is rapidly cooled, preferably by a water bath or dry ice, and the finished compound can subsequently be pelletized for further use.

[0023] The preferred combinations are as follows: (A) Polyhydroxyalkanoates and polyhydroxyalkanoate copolymers, in particular PH3B, PHBV, PHB-HHx or (P(3HB-4HB)), or polylactides, in particular PLLA or PLLA with a low D-isomer proportion, including: (B) Calcium salts, especially CaCO 3, CaSO 4 , Ca 3 (PO 4 ) 2 , or calcium citrate

[0024] Surprisingly, thin layers (<1 mm) of this type of compound showed fracture properties comparable to those of naturally occurring chicken eggshells. The brittleness or elastic modulus of the compound ranges from 3 to 8 GPa, typically 4 to 6 GPa, and can be adjusted through the concentration of inorganic or organic sparingly soluble fillers. Despite the use of thermoplastics, the compound had sufficient strength when cooked in hot water at 100°C. Furthermore, no dissolution behavior of the compound could be observed over a 20-minute period even in boiling water. No statistically significant dissolution behavior could be observed in water at room temperature and 4°C, in 1% aqueous sodium alginate solution at room temperature and 4°C, and in other aqueous media at room temperature and 4°C.

[0025] The compound is preferably molded by an injection molding process into two rotationally symmetric half shells of the same height (see FIG. 4). Before the thermoplastic processing, the compound is dried at 50-80°C, preferably at 60-70°C, for 6-48 hours, preferably 12-24 hours. The temperature profile in the injection molder-extruder complies with that of the preceding compounding process, depending on the durability and viscosity of the melt, but can be chosen slightly higher if necessary. To ensure a proper material and heat distribution in the injection mold, the geometry of the injection point can be selectively configured centrally or equatorially. The volume of the ovoid hollow body resulting from the combination of both half shells corresponds to the volume of a relatively large chicken egg and is 50-70 ml, preferably 60-65 ml. The resulting shell thickness of the injection molded half shells corresponds approximately to the thickness of a chicken egg and is 0.5-1 mm, preferably 0.6-0.75 mm. The surface of the outer covering of the eggshell can be made selectively smooth or rough - this can be achieved by suitable machining (milling, etching, etc.) of the inner surface of the mould. Both half-shells have a plug-in mechanism that allows them to be joined together precisely along the equator. In the area of ​​the plug-in joint, the shell thickness is slightly increased, approximately by a factor of 2, in order to ensure a higher mechanical stability there. One of the two half-shells, ideally the upper half-shell, is slightly tapered towards the tip than the other and has openings, typically 2-6 mm, best 3-5 mm, located laterally in the upper third or in the centre of the axis of rotation, which are moulded together during the injection moulding process. These openings allow the filling of the hollow body resulting from the fixed joining of both eggshell halves with one or more flowable and transportable components (egg white and egg yolk).

[0026] The following describes coatings for egg substitute products. Egg substitute products are vegan-based products that contain egg white and egg yolk separated from each other like natural animal eggs and can be structured or utilized like eggs. Both egg white and egg yolk contain (a) vegetable proteins derived from legumes, oil seeds, grains, and / or algae, and (b) a combination of at least two hydrocolloids that behave differently under temperature changes. Depending on whether it is egg white or egg yolk, additional ingredients are added.

[0027] "Vegan-based" means free of animal ingredients or components derived from animals.

[0028] The percentages given below are all by weight.

[0029] Hereinafter, the terms "egg white" and "egg albumen" will be used synonymously.

[0030] For example, vegan-based egg white substitute products include: (a) drinking water; (b) one or more proteins derived from legumes, oilseeds, grains, microorganisms, and / or algae; (c) a combination of one or more thermogelling hydrocolloids with one or more reverse gelling hydrocolloids; (d) one or more salts and the ratio of the combination of the one or more reversible thermogelling hydrocolloids and the one or more reversible gelling hydrocolloids is 0.25 to 5.00% by weight.

[0031] Suitable protein sources are vegetable raw materials from the group of legumes, cereals, oilseeds, microorganisms and (micro)algae, preferably peas (Pisum sativum), chickpeas (Cicer arientinum), kidney beans (Phaseolus vulgaris), fava beans (also called "wild beans"; Vicia faba), lupin beans (Lupinus), lentils (Lens culinaris), corn (Zea mays), hemp (Cannabis sativa), sweet potato (Ipomoea batatas), cassava (Manihot esculenta), potato (Solanum tuberosum), pumpkin (Cucurbita), flax (Linum usitatissimum), rapeseed (Brassica napus), soybean (Glycine max), oat (Avena sativa), bacteria (e.g. Lactobacillus spp., Streptococcus spp., and Bifidobacterium spp.), yeasts (e.g. Saccharomyces cerevisiae), filamentous fungi (e.g. Aspergillus spp., Mucor spp., and Rhizopus spp.), seaweed and / or wakame algae, with particular preference being given to proteins from pea, chickpea, lupin, hemp, pumpkin, and mung bean. As protein sources, it is possible to use (raw and / or hydrolyzed and / or fermented) husk flours, protein concentrates, protein isolates, and / or any combination thereof, which can be obtained from the plants and plant parts themselves, their seeds, bulbs, and / or fruits of the above-mentioned raw materials. The processing and nutritional engineering suitability of plants and the respective plant parts is well known to those skilled in the art of food technology.

[0032] According to the invention, a transparent white product is provided, produced from the above-mentioned proteins derived from one or more vegetable protein sources. The solubility of the respective proteins is higher in a salt solution than in pure water. Therefore, in order to dissolve the proteins in a solution consisting of drinking water and edible inorganic salts, a salt solution, preferably a sodium chloride-(NaCl)-solution, is prepared in which the protein source is dispersed. In principle, however, it is possible to dissolve the proteins in a solution consisting of drinking water and edible inorganic salts, preferably a sodium chloride-(NaCl)-solution, in which the protein source is dispersed. 2 PO 4 ), disodium hydrogen phosphate (Na 2 HPO 4 ), Trisodium Phosphate (Na 3 PO 4 ), Sodium pyrophosphate (Na 4 P 2 O 7 ), and even other salts such as potassium chloride (KCl) are suitable. Of course, it is also possible to disperse the protein source and the salt simultaneously in the drinking water. In some embodiments, the salt concentration, preferably the NaCl concentration, is higher than 0.05%, preferably higher than 0.10%, higher than 0.15%, higher than 0.20%, higher than 0.30%, higher than 0.40%, or higher than 0.50%. In some embodiments, the salt concentration, preferably the NaCl concentration, is between 0.05% and 0.80%, preferably between 0.10% and 0.70%, between 0.20% and 0.60%, or between 0.4% and 0.6%.

[0033] To produce an aroma similar to egg, kala namak (black salt) or other salts with a proportion of sulfur compounds and / or natural aromas can be used. Sulfur-containing compounds, especially kala namak salt, can be used with salt in the salt solution, preferably with NaCl, to obtain the same concentration. Alternatively, lesser, greater or equal amounts can be used.

[0034] The amount of dissolved protein is preferably greater than 0.1%. In some embodiments, the amount of dissolved protein is greater than 1.0%, preferably greater than 2.5%, greater than 4.0%, greater than 5.0%, greater than 8.0%, greater than 10.0%, or greater than 12%. In some embodiments, the amount of dissolved protein in the egg white replacer product according to the present invention is between 0.5% and 15.0%, preferably between 1.0% and 12.0%, between 1.5% and 10.0%, or between 2.0% and 5.0%.

[0035] For the adjustment of the desired viscosity and for solidification on heating, the egg white replacer product contains hydrocolloids. Here, it has been found that a combination of one or more thermogelling hydrocolloids with one or more reversibly gelling hydrocolloids is preferred, both types differing in terms of their behavior on temperature change. Hydrocolloids that gel rapidly on increasing the temperature to >40°C are called "thermogelling" or "thermoreversibly gelling" and are preferably modified celluloses, preferably methylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose (HPMC) and / or hydroxypropylcellulose. However, the gelling caused by them is only temporary; on cooling to <40°, the gel transforms again into the original viscous solution. In order for thermogelling to occur, there should be a certain minimum concentration of thermogelling hydrocolloid, which in the case of methylcellulose is approximately 1.5 g / l. The determination of the minimum concentration for other thermogelling hydrocolloids is possible for the skilled person without significant experimental costs. Below such a concentration, gelling does not occur on heating of the aqueous solution. Reversible gelling hydrocolloids form gels at room temperature (about 20° C.) which, unlike thermogelling hydrocolloids, melt when heated within a certain thermal interval, i.e. liquefy to form a viscous solution, which regels after cooling to or below the gelling temperature. As reverse gelling hydrocolloids, those derived from algae are used, preferably those derived from carrageenan and / or agar. To adjust the desired consistency and to promote sustained solidification of the vegan egg white, other hydrocolloids are used, preferably gellan gum, locust bean husk flour, guar husk flour, alginates, and / or xanthan. According to the present invention, the amount of hydrocolloid in the egg white is less than 5.00% (e.g., less than 4.75%, 4.50%, 4.25%, 4.50%, 4.25%, 4.00%, 3.75%, 3.50%, 3.25%, 3.00%, 2.75%, 2.50%, 2.25%, 2.00%, 1.75%, 1.50%, 1.00%, 0.75%, or equal to or less than 0.50%).In some embodiments, the amount of hydrocolloid in the egg yolk replacer product is 0.10% to 4.5% (e.g., 0.20% to 4.00%, 0.25% to 3.00%, 0.50% to 2.50%, or 0.75% to 2.00%). The split between the thermal gelling hydrocolloid and the reverse gelling hydrocolloid is preferably 50:50, preferably 25:75, 30:70, or 40:60, or 75:25, 70:30, or 60:40. Amounts of hydrocolloid lower than 5.00% allow for the provision of a liquid raw egg replacer, while acting for stability and texture comparable to chicken eggs upon cooking.

[0036] In some embodiments, transglutaminase can be optionally added to improve the texture of the protein solution or emulsion. The effect of transglutaminase on texture is its ability to promote cross-linking of proteins under certain temperature and time conditions. The amount of transglutaminase is preferably 0.001% to 3.00%, more preferably 0.01% to 1.5%, and even more preferably 0.1% to 1.0%. Transglutaminase is activated while the protein solution or emulsion is heated to a temperature between 40°C and 60°C for at least 15 minutes, preferably 30 minutes, 60 minutes, 90 minutes, or 120 minutes. Transglutaminase may or may not be microencapsulated and can be inactivated by Pasteur or UHT treatment (above 75°C to 120°C), preferably during the production of the egg replacer product.

[0037] In some embodiments, the mixture can optionally contain vegetable oil, preferably in an amount of 0.1% to 4%, preferably 0.5 to 2.0%. Suitable vegetable oils are, for example, olive oil, palm oil, linseed oil, walnut oil, safflower oil, or peanut oil; however, neutral taste lipids such as rapeseed oil, sunflower oil, coconut fat, and / or corn germ oil (corn oil), as well as any combination thereof, are preferred.

[0038] A small amount of sugar is preferably added to the product to cause browning of the product when heated, e.g., when frying "fried eggs", which occurs by the so-called Maillard reaction. The sugar is preferably a monosaccharide (e.g., dextrose, fructose, and / or galactose) and / or a disaccharide (e.g., lactose and / or maltose). In some embodiments, the amount of sugar in the egg white is less than 1.00%, preferably less than 0.75%, less than 0.50%, less than 0.25%, or less than 0.10%. In some embodiments, the amount of sugar in the egg white is between 0.10% and 1.00%, preferably between 0.25% and 0.75%, between 0.50% and 0.50%, or between 0.75% and 0.25%.

[0039] Furthermore, the egg white replacer product may contain additional minor components in minor amounts (less than 10.0%, preferably less than 5%, 3%, or 2%). These may be emulsifiers, aroma compounds (especially those containing sulfur compounds), spices, natural colorants, preservatives, thickeners, or health-promoting additives. By way of example, iodine, vitamins (e.g., vitamin B12, vitamin B2, vitamin B6, vitamin B7, vitamin B8, vitamin B9, vitamin B10, vitamin B12, vitamin B13, vitamin B14, vitamin B15, vitamin B26, vitamin B16, vitamin B17, vitamin B18, vitamin B20, vitamin B19, vitamin B21, vitamin B30, vitamin B40, vitamin B50, vitamin B60, vitamin B12, vitamin B21, vitamin B14, vitamin B16, vitamin B22, vitamin B16, vitamin B18, vitamin B22, vitamin B16, vitamin B18, vitamin B22, vitamin B12, vitamin B16, vitamin B16, vitamin B22, vitamin B16 ...16, vitamin B16, vitamin B16, vitamin B16, vitamin B16, vitamin B16, vitamin B16, vitamin B22, vitamin 1 , B 2、 B 3 , B 5 , B 7 , B 9 , B 12 , C, D 3 , or E), minerals (e.g. Ca or Mg), and / or vegetable lecithin (which also acts as an emulsifier).

[0040] The egg white replacer product is substantially free or free of carotenoids.

[0041] A protein source / multiple protein sources and salt are dispersed in drinking water. The pH value is determined by adding sodium hydroxide (NaOH), potassium phosphate (K 3 PO 4 ), or sodium citrate (Na 3 C 6 H5 O 7 The pH is adjusted to 6-9, preferably higher than 8.0, very preferably around 8.5, by a pH food regulator such as ethanolamine. The solution is stirred, preferably for at least 1 minute, more preferably for 5-10 minutes, even more preferably for 15 minutes, in order to improve the swelling of the proteins. It is preferred, but not essential, to separate the proteins after swelling by a suitable separation method, preferably by centrifugation, decanting or diaphragm filtration. Such a separation results in a supernatant containing the dissolved proteins and a pellet containing the insoluble proteins. Depending on the salt concentration in the solution used, the dissolved proteins are mainly globulins and albumins. The supernatant solution (solution (A)) is used for the subsequent egg white production, whereas the residue or pellet can be used for the production of another product, for example a vegan egg yolk substitute product.

[0042] According to the invention, the protein source is dispersed in water or an aqueous salt solution (solution (A)). Solution (A) can be divided into two parts ((A1) and (A2)). Alternatively, it is possible to prepare two solutions (A1) and (A2) independently of each other: (A1) can be an aqueous protein solution or a protein-salt solution, and (A2) can be a solution of another protein or water only. Optionally, 0.001% to 2.00% transglutaminase can be added to solution (A1). If non-encapsulated transglutaminase is used, the solution should be kept at 50° C. for less than 120 minutes. Solution (B) is prepared by heating solution (A1) to at least 40° C., preferably to 50° C., but not more than 60° C., and adding one or more thermogelling hydrocolloids (e.g. modified cellulose, methylcellulose, and / or hydroxypropylcellulose). The thermal effect results in an improved dispersion of the hydrocolloids. Before or after the dispersion of the hydrocolloid, oil (optionally containing 0.01% to 50% emulsifier), optionally a calcium ion source, natural colorants, and optionally other additives are mixed into solution (B). Solution (C) is prepared by mixing one or more reversible gelling hydrocolloids into solution (A2) at a temperature below 30°C, preferably below 20°C, 15°C, or 10°C. In addition to this, further natural taste substances, aroma preparations, oils, and (encapsulated) transglutaminase, or other additives, can be mixed into solution (C). Once all the components of solutions (B) and (C) are completely dispersed, solutions (B) and (C) are mixed, preferably below 30°C, thereby resulting in the finished egg white solution (solution (D)). Each of the above-described solutions and dispersions is prepared in a standard mixing vessel by applying well-known dispersion techniques.

[0043] In a second alternative embodiment, rather than dividing solution (A), one / several reverse gelling hydrocolloids and optionally additives such as sugar and salt are added to solution (A). The mixture is heated to 40° C., preferably to 50° C., and then the thermogelling hydrocolloid is added with stirring until completely dispersed. The mixture is cooled to room temperature to obtain the egg white replacer product according to the invention.

[0044] The second component of vegan eggs is (a) drinking water; (b) one or more proteins derived from legumes, oilseeds, grains, algae, or microorganisms; (c) a vegetable oil, optionally containing at least one emulsifier; (d) a combination of one or more reversible thermogelling hydrocolloids with one or more reverse gelling hydrocolloids; (e) at least one carotenoid-containing food and / or natural coloring substance; (f) optionally an at least partially pregelatinized starch, and (g) Salt An egg yolk is created comprising the one or more reversible thermogelling hydrocolloids in a combination of one or more reversibly gelling hydrocolloids in a proportion of 0.5-5.0% by weight.

[0045] The product according to the invention has in particular a protein content of 1% to 35%, preferably of 3% to 25% or 20%, very preferably of 4% to 15%, particularly preferably of 5% to 12%. Suitable protein sources are vegetable raw materials from the group of legumes, cereals, oilseeds, (micro)algae and microorganisms, preferably peas (Pisum sativum), chickpeas (Cicer arientinum), kidney beans (Phaseolus vulgaris), faba beans (Vicia faba), lupin beans (Lupinus), lentils (Lens culinaris), corn (Zea mays), hemp (Cannabis sativa), sweet potato (Ipomoea batatas), cassava (Manihot esculenta), potato (Solanum tuberosum), pumpkin (Cucurbita), flax (Linum usitatissimum), rapeseed (Brassica napus), soybean (Glycine max), oat (Avena sativa), bacteria (e.g. Lactobacillus spp., Streptococcus spp., and Bifidobacterium spp.), yeasts (e.g. Saccharomyces cerevisiae), filamentous fungi (e.g. Aspergillus spp., Mucor spp., and Rhizopus spp.), seaweed and / or wakame algae, with particular preference being given to pea, lupin, potato, chickpea, and faba bean proteins. As protein sources, it is possible to use (raw and / or hydrolyzed and / or fermented) husk flours, protein concentrates, protein isolates, and / or any combination thereof, which can be obtained from the plants and plant parts themselves, their seeds, bulbs, and / or fruits of the above-mentioned raw materials. The processing and nutritional suitability of plants and the respective plant parts can be well known to those skilled in the art of food technology.

[0046] In some embodiments, transglutaminase can be optionally added to improve the texture of the protein solution or emulsion. The effect of transglutaminase on texture is its ability to promote cross-linking of proteins under certain temperature and time conditions. The amount of transglutaminase is preferably 0.001% to 3.00%, more preferably 0.01% to 1.5%, and even more preferably 0.1% to 1.0%. Transglutaminase is activated while the protein solution or emulsion is heated to a temperature between 40°C and 60°C for at least 15 minutes, preferably 30 minutes, 60 minutes, 90 minutes, or 120 minutes. Transglutaminase may or may not be microencapsulated and can be inactivated by Pasteur or UHT treatment (above 75°C to 120°C), preferably during the production of the egg replacer product.

[0047] The fat content is preferably 1% to 50%, preferably 5% to 30%, very preferably 10% to 25%, particularly preferably 12% to 18%. Vegetable oils, such as olive oil, palm oil, linseed oil, walnut oil, safflower oil or peanut oil, are suitable as the fat component; however, neutral-tasting fats such as rapeseed oil, sunflower oil, coconut fat and / or corn germ oil, as well as any combinations thereof, are preferred. An emulsifier may be added to the lipid component, preferably up to 50%, preferably 5 to 40%, more preferably 10 to 30%, relative to the proportion of the fat component. These are, for example, lecithin (or components thereof, such as phosphatidylcholine, phosphatidylserine, phosphatidylethanolamine, or phosphatidylinositol), ascorbyl dipalmitate, sodium phosphate, sodium pyrophosphate, potassium phosphate, propylene glycol alginate, polyoxyethylene stearate, ammonium salts of phosphatidic acid, monoglyceride acetate, monoglyceride lactate, monoglyceride citrate, monoglyceride tartrate, stearyl tartrate, or sorbitan monostearate.

[0048] To give the egg yolk substitute product a suitable color, at least one carotenoid-containing food and / or natural coloring agent is added as a further ingredient. Suitable preparations are from fruits, vegetables, and bulbs, preferably from bulbous vegetables and root vegetables, such as carrots, apricots, tomatoes, peppers, pumpkins, fennel, and / or sweet potatoes. These are preferably boiled and then processed into jams or finely chopped. In some embodiments, the amount of carotenoid-containing food in the egg yolk is less than 15.0% (e.g. less than 12.0%, less than 8.00%, less than 4.00%, less than 2.00%, less than 1.50%, or less than 0.50%). In some embodiments, the amount of carotenoid-containing food in the egg yolk is 0.01% to 10.0% (e.g., 0.50% to 9.50%, 2.50% to 7.50%, or 3.00% to 5.50%). The use of sweet potato as the carotenoid-containing food has surprisingly been found to lead to the formation of a texture and color similar to that of traditional chicken egg yolk, and the use of sweet potato also promotes the protein and fiber content, while bringing a starch component to the mixture, which has a favorable effect on the texture. The sweet potato is preferably boiled and then processed into jam or finely (finely) chopped. The amount of sweet potato may be 3% to 10%, preferably 5% to 8%. In the case where sweet potato is included as the carotenoid-containing food, other additions of at least partially pregelatinized starch are not necessary (0%) or can be reduced to a small amount lower than 0.5%. If not, the addition of at least one (partially) pregelatinized starch is recommended, preferably in an amount of 0.5% to 4%, more preferably 1.0% to 3.0%. The (partially) gelatinized starch is preferably obtained from corn starch, potato starch or rice starch by mechanical processing in the presence of water with or without the application of heat, during which some or all of the starch particles are ruptured. The powder is subsequently dried. The gelatinized starch exists as a white to yellowish white powder and swells in cold water.It has good flow properties and is suitable as a binder.

[0049] Further suitable preparations derived from fruits, vegetables and bulbs can be used to adjust the texture, mouthfeel and color. In addition, additives, preferably fat-soluble natural colorants, such as carotenoids (e.g., beta-carotene, lycopene, zeaxanthin), carrot extract, curcumin, and poorly water-soluble colorants, such as riboflavin, are suitable for best color adjustment. These can be used alone or in combination to obtain the desired color tone. In some embodiments, the amount of natural colorants in the egg yolk is lower than 2.00% (e.g., lower than 1.50%, lower than 1.00%, lower than 0.75%, or lower than 0.25%). In some embodiments, the amount of natural colorants in the egg yolk is between 0.01% and 2.00% (e.g., between 0.25% and 1.75%, between 1.00% and 0.50%, or between 1.75% and 0.25%). The color of the egg yolk may range from yellow to dark orange in the L*a*b* color space: lightness (L*) may range from 70 to 85, preferably from 75 to 80; red-green (a*) may range from 15 to 30, preferably from 19 to 25; yellow-blue (b*) may be from 60 to 95, preferably from 70 to 90, particularly preferably from 75 to 88.

[0050] Salts are added to produce an aroma similar to that of chicken eggs. NaCl, KCl, NaH 2 PO 4 , Na 2 HPO 4 , Na-citrate or K-citrate, CaCl 2 , Na 3 PO 4 and / or kala namak (black salt) or salts comparable to kala namak, preferably having a proportion of sulfur compounds. To this end, in some embodiments the amount of salt, preferably the amount of kala namak salt, is less than 2.00%, for example less than 0.75%, less than 0.50%, less than 0.25%, or less than 0.10%.

[0051] Furthermore, the egg yolk replacer product may contain minor amounts (less than 10.0%, preferably less than 5%, 3%, or 2%) of additional minor ingredients, which may be aroma preparations, spices, dried vegetables or fruits, sugar, preservatives, thickeners, or health-promoting additives. By way of example, iodine, vitamins (e.g., vitamin B 1 , B 2 , B 3 , B 5 , B 7 , B 9 , B 12 , C, D 3 , or E), and / or minerals (e.g., Ca or Mg).

[0052] For the adjustment of the desired viscosity and for solidification on heating, the egg yolk substitute product contains hydrocolloids. Here, it has been found that a combination of one or more thermogelling hydrocolloids with one or more reversibly gelling hydrocolloids is preferred, both types differing in terms of their behavior on temperature change. Hydrocolloids that gel rapidly on increasing the temperature to >40°C are called "thermogelling" or "thermoreversibly gelling" and are preferably modified celluloses, preferably methylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose (HPMC) and / or hydroxypropylcellulose. However, the gelling caused by them is only temporary; on cooling to <40°, the gel transforms again into the original viscous solution. In order for thermogelling to occur, there should be a certain minimum concentration of thermogelling hydrocolloid, which in the case of methylcellulose is approximately 1.5 g / l. The determination of the minimum concentration for other thermogelling hydrocolloids is possible for the skilled person without significant experimental costs. Below such a concentration, gelling does not occur on heating of the aqueous solution. Reversible gelling hydrocolloids form gels at room temperature (about 20° C.) which, unlike thermogelling hydrocolloids, melt when heated within a certain thermal interval, i.e. liquefy to form a viscous solution, which regels after cooling to or below the gelling temperature. As reverse gelling hydrocolloids, those derived from algae, preferably carrageenan and / or agar, are used. To adjust the desired consistency and to promote sustained solidification of the vegan egg yolk, other hydrocolloids are used, preferably gellan gum, locust bean husk flour, guar husk flour, alginates, and / or xanthan. In some embodiments, the amount of hydrocolloid in the egg yolk is less than 5.00% (e.g., less than 4.75%, 4.50%, 4.25%, 4.50%, 4.25%, 4.00%, 3.75%, 3.50%, 3.25%, 3.00%, 2.75%, 2.50%, 2.25%, 2.00%, 1.75%, 1.50%, 1.00%, 0.75%, or equal to or less than 0.50%).In some embodiments, the amount of hydrocolloid in the egg yolk replacer product is 0.10% to 4.5% (e.g., 0.20% to 4.00%, 0.25% to 3.00%, 0.50% to 2.50%, or 0.75% to 2.00%). The split between the thermal gelling hydrocolloid and the reverse gelling hydrocolloid is preferably 50:50, preferably 25:75, 30:70, or 40:60, or 75:25, 70:30, or 60:40. Amounts of hydrocolloid lower than 5.00% allow for the provision of a liquid raw egg replacer, while acting for stability and texture comparable to chicken eggs upon cooking.

[0053] In a preferred embodiment, the egg yolk replacer mixture is surrounded by a coating consisting of a highly cross-linked hydrocolloid or consisting of a thermo-reversible gelling hydrocolloid, preferably consisting of calcium alginate or k-carrageenan.

[0054] According to the invention, a protein source is dispersed in water or an aqueous salt solution (solution (A)). Solution (A) can be divided into two parts ((A1) and (A2)). Alternatively, it is possible to prepare two solutions (A1) and (A2) independently of each other: (A1) can be an aqueous protein solution or a protein-salt solution, and (A2) can be a solution of another protein or water only. Optionally, 0.001% to 2.00% transglutaminase can be added to solution (A1). If non-encapsulated transglutaminase is used, the solution should be kept at 50° C. for less than 120 minutes. Solution (B) is prepared by heating solution (A1) to at least 40° C., preferably to 50° C., but not exceeding 60° C., and adding one or more thermogelling hydrocolloids (e.g. modified cellulose, methylcellulose, and / or hydroxypropylcellulose). The thermal effect results in an improved dispersion of the hydrocolloids. Before or after the dispersion of the hydrocolloid, oil (optionally containing 0.01% to 50% emulsifier), optionally a calcium ion source, a carotenoid-containing food or natural colorant, and optionally other additives are mixed into solution (B). Solution (C) is prepared by mixing one or more reversibly gelling hydrocolloids into solution (A2) at a temperature below 30°C, preferably below 20°C, 15°C, or 10°C. In addition to this, further natural taste substances, aroma preparations, oils, and (encapsulated) transglutaminase, or other additives, can be mixed into solution (C). As soon as all the components of solutions (B) and (C) are completely dispersed, solutions (B) and (C) are mixed, preferably below 30°C, thereby resulting in the finished egg yolk solution (solution (D)). Each of the above-described solutions and dispersions is prepared in a standard mixing vessel by applying well-known dispersion techniques.

[0055] To achieve a perfect fine distribution of the oil particles, the mixture (solution (D) can be homogenized. Surprisingly, this not only improves the texture, so that it is no longer perceived as rough on the tongue, but also improves the brightness, so that less coloring agent is required for coloring and the product has a stronger gloss. For homogenization, a pressure of 5 bar to 300 bar, preferably 25 bar to 225 bar, particularly preferably 50 bar to 250 bar, can be applied. The homogenization can be in one or two stages. The individual solutions and their mixing are preferably, but not necessarily, carried out under vacuum treatment. The vacuum prevents the formation of air bubbles in the egg yolk.

[0056] According to the invention, each of the solutions ((A), (B), (C) and / or (D)) can be Pasteurized or sterilized. The Pasteurization / sterilization can be supplemented by other techniques such as, for example, UV light and / or high pressure processing. These methods are standard techniques within the skill of the art and well documented in the literature.

[0057] For the formation of egg yolk spheres, the following four methods are preferably suitable:

[0058] Method 1: For sphere formation (encapsulation), a soluble calcium salt (e.g. calcium lactate or calcium chloride) is introduced into solution (B) and / or (C) as part of the filling material, and solution (B) and / or (C) are further treated in the same way as described above for solution (D). Solution (D) containing the calcium salt is preferably dosed into an aqueous solution of a highly cross-linked hydrocolloid, preferably sodium alginate, as spherical as possible, and kept in contact with this solution for a maximum of 5 minutes, preferably less than 4 minutes, more preferably less than 3 minutes, so that the filling (solution (D)) remains liquid. Solution (D) can be partially or completely frozen in a spherical shape beforehand, and then placed in a lukewarm bath of highly cross-linked hydrocolloid for capsule formation. The diffusion of potassium ions from solution (D) into the solution of highly cross-linked hydrocolloid forms an outer coating, which encapsulates the egg yolk (=solution (D)) by cross-linking with the potassium ions. In other words, a surface layer forms around solution (D), which gives rise to a shape that closely resembles the well-known animal egg yolk. To stop the cross-linking reaction, the encapsulated egg yolk should be washed with water as soon as possible. The amount of hydrocolloid surrounding solution (D) does not exceed 1% of the total weight of the egg yolk to be encapsulated.

[0059] In a preferred embodiment of method 1, the liquid "egg yolk" (solution (D)) is metered into a hydrocolloid (preferably sodium alginate) solution as a spherical continuum (weight: 5-20 g) using a nozzle and contacted with the hydrocolloid (preferably sodium alginate) solution for a time period shorter than 300 seconds, preferably shorter than 240 seconds, 120 seconds, or 60 seconds. The encapsulated egg yolk can then be washed in a deionized water bath to remove excess alginate, thereby ensuring that the "egg yolk" does not harden during storage and remains liquid inside. Surprisingly, the liquid product remains very stable within its encapsulation, so that it can be transferred intact to a dish / pan where it remains curved and the liquid contents can only be released by stirring / properly breaking the coating.

[0060] Method 2: For sphere formation (encapsulation), highly cross-linked hydrocolloids (e.g. sodium alginate) are placed in solution (B and / or C) as part of the filling material, and solutions (B) and / or (C) are further treated in the same way as described above for solution (D). The solution (D) containing the highly cross-linked hydrocolloids is preferably dosed as spherical as possible into an aqueous solution of a calcium salt (e.g. calcium lactate or calcium chloride) and kept in contact with this solution for a maximum of 5 minutes, preferably less than 4 minutes, and more preferably less than 3 minutes, so that the filling (solution (D)) remains liquid. Solution (D) can be partially or completely frozen in a spherical shape beforehand and then placed in a lukewarm bath of calcium salt for capsule formation. An outer coating is formed by the diffusion of calcium ions from the calcium salt solution, and the highly cross-linked hydrocolloids encapsulate the egg yolk (= solution (D)) by cross-linking with potassium ions. In other words, a surface layer is formed around solution (D), which gives rise to a shape very similar to the well-known animal egg yolk. To stop the cross-linking reaction, it is advisable to rinse the encapsulated egg yolk with water as soon as possible. Surprisingly, the liquid product remains very stable within its encapsulation, so that it can be transferred intact to a dish / pan where it remains curved and the liquid contents can only be released by stirring / determining the coating. The amount of calcium salt surrounding solution (D) does not exceed 1% of the total weight of the encapsulated egg yolk.

[0061] Method 3: For the formation of spherical shapes, the above-mentioned egg yolk preparation (solution (D)) is flash-frozen in a suitable form made of silicone rubber, plastic, special steel, etc., at a temperature of <0°C, typically at or below -18°C. The resulting spheres or hemispheres of frozen solution (D), with a diameter of 1-4 cm, ideally around 2-3 cm, are subsequently further frozen with liquid nitrogen (boiling point -196°C) until no noticeable gas bubbling occurs on the surface of the sphere (reaching thermodynamic equilibrium). A previously prepared solution of thermoreversible gelling hydrocolloid, typically sodium alginate and / or k-carrageenan, is dissolved in water at a temperature above 35°C to obtain a 1-2% clear solution. This solution is subsequently cooled to a temperature of 35°C-50°C, ideally within the range of 45-50°C. The flash-cooled spheres of solution D are subsequently immersed in a solution of hydrocolloid, so that a gel layer forms on the surface upon cooling. The thickness of the gel layer can be adjusted by the immersion time, the sphere size and the amount of hydrocolloid solution provided, and is between 1 and 5 mm, typically around 1 to 2 mm. In other words, a surface layer is formed around the solidified solution (D), which results in an overall shape that is very similar to the well-known animal egg yolk. Surprisingly, after melting, the liquid product remains very stable in its encapsulation, so that it can be transferred intact to a dish / pan, where it remains curved, and the liquid contents can only be released by stirring / determined breaking of the covering. The amount of thermoreversible gelling hydrocolloid surrounding the solution (D) does not exceed 1% of the total weight of the egg yolk to be encapsulated.

[0062] Method 4: For the formation of spherical shapes, the above-mentioned egg yolk preparation (solution (D) without calcium ion source) is flash-frozen in a suitable form made of silicone rubber, plastic, special steel, etc. at a temperature of <0°C, typically at or below -18°C. Optionally, the resulting sphere or hemisphere made of frozen solution (D) with a diameter of 1-4 cm, ideally around 2-3 cm, is subsequently further frozen with liquid nitrogen (boiling point -196°C) until no noticeable gas bubbling occurs on the surface of the sphere (reaching thermodynamic equilibrium). Calcium ions can be sprayed onto the surface of the sphere or hemisphere so that the ions are attached to the frozen surface. A previously prepared solution of thermoreversible gelling hydrocolloid, typically sodium alginate and / or k-carrageenan, is dissolved in water at a temperature above 35°C to obtain a 1-3% clear solution. This solution is subsequently cooled to a temperature of 35°C to 50°C, ideally within the range of 45-50°C. The rapidly cooled spheres of solution D, ideally with a uniform layer of calcium ions on the surface, are subsequently immersed in a solution of hydrocolloid so that upon cooling a gel layer forms on the surface. The thickness of the gel layer can be adjusted by the immersion time, the sphere size and the amount of hydrocolloid solution provided, and is between 1 and 5 mm, typically around 1 to 2 mm. In other words, a surface layer forms around the solidified solution (D), which results in an overall shape that is very similar to the well-known animal egg yolk. Surprisingly, after melting, the liquid product remains very stable in its encapsulation, so that it can be transferred intact to a dish / pan, where it remains curved, and the liquid contents can only be released by stirring / determining the covering. The amount of thermoreversible gelling hydrocolloid surrounding solution (D) does not exceed 1% of the total weight of the egg yolk to be encapsulated.

[0063] The encapsulated egg yolk can be stored in a preservative and / or buffer solution containing, for example, NaCl, calcium salts, benzoic acid, and / or ascorbic acid.

[0064] Further details regarding the structure and manufacturing method of the egg white replacer product and egg yolk replacer product can be found in the application documents having application numbers 10 2021 130 963.8 and 10 2021 130 974.3, the disclosures of which are incorporated herein by reference.

[0065] For filling the above-described shells, preferably produced by injection molding, with egg white and yolk replacers, two different methods are in principle suitable: (I) filling with externally molded egg yolk bodies and (II) in situ molding of egg yolk bodies. Filling embodiment (I) is characterized in that it presupposes an egg yolk mixture coated with a crosslinked hydrocolloid, preferably with calcium alginate. The mass of the formed egg yolk body is typically 20-30 g, ideally 25-29 g. The coating formed allows the egg yolk body to be positioned in a half shell (see example 3) that does not have an additional filling hole. A second half shell is positioned thereon by a plug-in connection, resulting in a hollow body with the egg yolk body inside. A suitable joining method is applied to join the half shells together along the equator in a liquid-tight and gas-tight manner, which can be carried out a) by localized supply of thermal energy (heat sealing, friction welding, laser pulse welding, etc.) or b) by chemical or physical bonding of a suitable sealing medium (food-compatible and optionally biologically degradable sealing lacquer or sealing adhesive inside the plug-in connection; external application of a food-compatible and optionally biologically degradable bonding layer, e.g. strip seal or spray lacquer). After both half shells have been form-fittingly and irreversibly joined together in this way, the second component (vegan egg white) is metered in by a metering system through an additional filling hole. The maximum filling height of the egg white depends on the position of the filling hole and can be further adapted by changing the position of the egg body (e.g. tilting). The filling hole of the filled egg is liquid-tight and air-tight closed by a suitable closing material, for example by an adhesive or sealing sheet made of the same or a different material as the shell.

[0066] The filling embodiment (II) is characterized by the premise of a liquid egg yolk mixture and a liquid egg white mixture. Both half shells (see example 3) are joined in the empty state by a suitable joining method, liquid-tight and air-tight along the equatorial plane as described above. A highly cross-linked polysaccharide solution (e.g. alginic acid) not intended for final consumption is then dosed into the hollow body through the filling hole. The intended amount of egg yolk preparation is injected therein, whereby a thin edible artificial vitelline membrane is generated at the interface between the egg yolk and the polysaccharide solution (in-situ molding). Once the desired membrane thickness is reached, the remaining polysaccharide solution is removed by pouring it out through the filling hole or, alternatively, by sucking it out, and is optionally re-washed with sterile water. The subsequent work steps (dosing of the egg white, closing of the filling hole) are carried out as described above for the filling embodiment (I).

[0067] The present invention will now be described with reference to the drawings. [Brief description of the drawings]

[0068] [Figure 1] This is the structure of a chicken eggshell viewed under a microscope (taken from reference [1]). [Diagram 2] Water vapor and oxygen permeability of various polymers (adapted from reference

[23] ). [Diagram 3] Tensile strength and stiffness (elastic modulus) of various polymers (adapted from reference

[23] ). [Figure 4] FIG. 13 is an exemplary diagram showing a completed eggshell. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0069] The following examples should be understood as possible embodiments, and are not intended to be strictly limited to these embodiments. EXAMPLES

[0070] Example 1: PHBV and CaCO 3 Creating a compound consisting of PHBV, which has a melting point of 175°C, was cooled to 50°C, and CaCO 3 The powders were mixed in a ratio of 7:3, dried overnight at 100°C, and compounded and granulated under a temperature profile of 45-140-150-150-150°C. A pressed film of approximately 240 μm thickness was prepared from the light brown granules. Gas permeability measurements showed that the 1.8 gm- 2 d' 1 (Normalized to 100μm: 4.4gm 2 d -1 The water vapor permeability (WVTR, 85->0% relative humidity, 23°C) of 10.5 cm 3 m 2 d -1 (Normalized to 100 μm: 67.2 cm 3 m 2 d -1 An oxygen permeability (OTR, 23°C / 50% relative humidity) of 2.0 GPa was obtained. Mechanical tensile testing yielded a tensile strength of 21.6 MPa, an ultimate elongation of 1.1%, and an elastic modulus of 2.9 GPa.

[0071] Example 2: PLLA and CaCO 3 Creating a compound consisting of PLLA containing a small proportion of D isomer (melting point 160°C) at 60°C and CaCO 3 The powders were mixed in a ratio of 8:2, compounded and granulated under a temperature profile of 60-160-190-190-145-145-145°C. A pressed film of about 200 μm thickness was prepared from the whitish granules. Gas permeability measurements showed that the 11 gm -2 d -1 (Normalized to 100μm: 22gm 2 d -1 ) vapor permeability (WVTR, 85->0% relative humidity, 23°C) was obtained, as well as 3 m 2 d -1 Oxygen permeability (normalized to 100 μm: 150 cm 3 m 2 d -1Mechanical tensile testing revealed a tensile strength of 40 MPa, an ultimate elongation of 1.0%, and an elastic modulus of 4 GPa.

[0072] Figures 2 and 3 show the achieved permeability and mechanical properties of the compounds of Examples 1 and 2 in comparison with commonly used polymers for food packaging.

[0073] Example 3: Shell properties and formation The compound of Example 1 was molded by injection molding into two rotationally symmetric half shells of the same height (see FIG. 4). Before thermoplastic processing, the compound was dried at 50-80°C for 6-48 hours. The temperature profile in the injection molder-extruder corresponds to the compounding process described above, and can be chosen slightly higher if necessary, depending on the durability and viscosity of the melt. The geometry of the injection point can be selectively configured centrally or equatorially to ensure a proper material and heat distribution in the injection mold. The volume of the ovoid hollow body resulting from the combination of both half shells corresponds to the volume of a relatively large chicken egg, i.e. 60-65 ml. The resulting shell thickness of the injection molded half shells corresponds approximately to the thickness of a chicken egg, i.e. about 0.6-0.75 mm. Both half shells have a plug mechanism that allows them to be joined together precisely in a fitted manner along the equator. In the region of the plug-in connection, the shell thickness is increased slightly, approximately by a factor of 2, in order to ensure higher mechanical stability there. One of the two half-shells, ideally the upper one, is slightly tapered towards the tip than the other and has openings of 3-5 mm on the sides of the upper third or in the center of the rotation axis, which are molded together during the injection molding process. These openings make it possible to fill the hollow body resulting from the fixed joining of both eggshell halves with one or more flowable and transportable components (egg white and optionally egg yolk).

[0074] Reference list: 1.Arias,J.L.,et al.,Eggshell Growth and Matrix Macromolecules.Handbook of Biomineralization,2008. 2.Hahn,E.N.,et al.,Nature’s technical ceramic:the avian eggshell.Journal of the Royal Society Interface,2017.14(126). 3.Lomholt,J.P.,The Development of the Oxygen Permeability of the Avian Egg Shell and Its Membranes during Incubation.Journal of Experimental Zoology,1976.198(2):p.177-184. 4.Spiesz,E.M.,et al.,Bacterially Produced,Nacre-Inspired Composite Materials. Small,2019.15(22):p.1805312. 5.Jost,V.,Effect of additives on the mechanical and permeation properties of biopolymer films from alginate and PHBV PhD,2019.TU Muenchen:Freising 6.Hochrein,T.and I.Alig,Prozessmesstechnik in der Kunststoffaufbereitung.2011 ,Wuerzburg:Vogel Buchverlag. 7.Cinelli,P.,et al.,Biocomposites Based on Polyhydroxyalkanoates and Natural Fibres from Renewable Byproducts.Applied Food Biotechnology,2019.6(1):p.35-43. 8.Chen,G.X.,et al.,Crystallization kinetics of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) / clay nanocomposites.Journal of Applied Polymer Science,2004. 93(2):p.655-661. 9.Duangphet,S.,et al.,Effect of Calcium Carbonate on Crystallization Behavior and Morphology of Poly(3-Hydroxybutyrate-co-3-Hydroxyvalerate).Key Engineering Materials,2017.751:p.242-251. 10.Cabedo,L,et al.,Studying the degradation of polyhydroxybutyrate-co-valerate during processing with clay-based nanofillers.Journal of Applied Polymer Science,2009.112(6):p.3669-3676. 11.Ding,Y.,et al.,Mechanical properties,thermal stability,and crystallization kinetics of poly(3-hydroxybutyrate-co-4-hydroxybutyrate) / calcium carbonate composites.Polymer Composites,2011.32(7):p.1134-1142. 12.Kirboga,S.and M.Oener,The properties of PHBV / CaCO 3 composites prepared by melt processing,in 6th International Conference on New Trends in Chemistry.2020.virtual. 13.Xiong,L,et al.,Preparation of PBS and CaCO 3 Composite Degradable Materials based on Melt Blending.IOP Conference Series:Materials Science and Engineering,2020.730:p.012012. 14.G igante,V.,et al .,Evaluation of Mussel Shells Powder as Reinforcement for PLA-Based Biocomposites.International Journal of Molecular Sciences,2020.21(15). 15.Sathiyavimal,S.,et al.,Natural organic and inorganic-hydroxyapatite biopolymer composite for biomedical applications.Progress in Organic Coatings,2020.147:p.105858. 16.Misra,S.K.,et al.,Polyhydroxyalkanoate(PHA) / lnorganic Phase Composites for Tissue Engineering Applications.Biomacromolecules,2006.7(8):p.2249-2258. 17.Rodriguez-Contreras,A.,Recent Advances in the Use of Polyhydroyalkanoates in Biomedicine.Bioengineering,2019.6(3). 18.Chernozem,R.V.,et al.,Piezoelectric 3-D Fibrous Poly(3-hydroxybutyrate)-Based Scaffolds Ultrasound-Mineralized with Calcium Carbonate for Bone Tissue Engineering:Inorganic Phase Formation,Osteoblast Cell Adhesion,and Proliferation.ACS Applied Materials & Interfaces,2019.11(21):p.19522-19533. 19.Jagoda,A.,Polyhydroxyalkanoate-based thin films:characterization and optimization for calcium phosphate crystallization PhD,2013.Universitaet Basel:Basel 20.Degli Esposti,M.,et al.,Highly porous PHB-based bioactive scaffolds for bone tissue engineering by in situ synthesis ofHydroxyapatite.Materials Science and Engineering:C,2019.100:p.286-296. 21.Kulman,D.,Imitation egg product 2019.US20190263557A1. 22.Fink,D.,et al.,Flexible,atmungsaktive Polymerfolie und Verfahren zu derenHerstellung 2003.DE10301984A1. 23.Detzel,A.,et al.,Biobasierte Kunststoffe als Verpackung von LebensmittelnHeidelberg,Freising,Berlin,2018.

Claims

1. (A) one or more biodegradable, thermoplastic processable biopolymers; (B) one or more inorganic, organic, or sparingly soluble salts; 1. Use of a material consisting of:

2. 2. The use according to claim 1, wherein the material is made from components (A) and (B) by extrusion.

3. 3. The use according to claim 1 or 2, wherein the biopolymer (A) is characterized by a degradation rate of at least 90% within 180 days, a degradation level of less than 10% of the dry mass after 12 weeks for particles larger than 2 mm, and / or passing an ecotoxicity analysis involving plant growth.

4. The use according to claim 1 or 2, wherein the biopolymer (A) is a polyhydroxyalkanoate, a polyhydroxyalkanoate copolymer, or a polylactide.

5. 3. The use according to claim 1 or 2, wherein the salt (B) is a carbonate, sulfate, hydrogen sulfate, sulfite, sulfide, phosphate, hydrogen phosphate, oxide, hydroxide, citrate, or oxalate of an alkaline earth element, a transition metal, or aluminum.

6. The salt (B) is CaCO ３ , CaSO ４ , Ca ３ (P.O. ４ ) ２ , MgCO ３ , BaSO ４ , calcium citrate, calcium oxalate, Fe ２ O ３ , or Al ２ O ３ 3. The use according to claim 1 or 2, wherein

7. The polyhydroxyalkanoates and / or polyhydroxyalkanoate copolymers may be selected from the group consisting of poly(3-hydroxypropionate), poly(3-hydroxybutyrate), poly(3-hydroxyvalerate), poly(3-hydroxyhexanoate), poly(3-hydroxyheptanoate), poly(3-hydroxyoctanoate), poly(3-hydroxynonanoate), poly(3-hydroxydecanoate), poly(3-hydroxyundecanoate), poly(3-hydroxydodecanoate), poly(3-hydroxytetradecanoate), poly(3-hydroxybut ... poly(3-hydroxypentadecanoate), poly(3-hydroxyhexadecanoate); poly(3-hydroxypropionate-co-3-hydroxybutyrate), poly(3-hydroxypropionate-co-4-hydroxybutyrate), poly(3-hydroxybutyrate-co-4-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyhexanoate, C ３ ~C １１ or a medium chain PHA having a side chain length of C １２ The use according to claim 4, wherein the PHA is a long-chain PHA having a side chain length greater than

8. 5. The use according to claim 4, wherein the polylactide is an amorphous or crystalline variation of poly(L-lactide) PLLA, poly(D-lactide) PDLA, stereocomplex-(polylactide) sc-PLA, stereoblock-(polylactide) sb-PLA.

9. 1. An egg replacer product comprising a vegan-based egg white and egg yolk coated with a shell made of a material produced by extrusion, the shell comprising (A) one or more biodegradable, thermoplastically processable biopolymers and (B) one or more inorganic, organic, or sparingly soluble salts, wherein both the egg white and the egg yolk (a) comprise plant proteins derived from legumes, oil seeds, grains, and / or algae, and (b) comprise a combination of at least two hydrocolloids that each exhibit different behavior under temperature changes.

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