EP2776512A1

EP2776512A1 - Method for producing milk protein gels, -hydrogels, -hydrocolloides and -superabsorbers (milk protein gels)

Info

Publication number: EP2776512A1
Application number: EP12799513.2A
Authority: EP
Inventors: Anke Domaske
Original assignee: QMILCH IP GmbH
Current assignee: QMILCH IP GmbH
Priority date: 2011-11-12
Filing date: 2012-11-12
Publication date: 2014-09-17
Also published as: US20140373748A1; WO2013068595A4; WO2013068595A1

Abstract

The invention relates to a milk protein hydrol gel, in which at least one protein which is obtained from milk and which can be thermally plasticized, is plasticized using a plasticizing agent, such as for example, water or glycerol at temperatures between room temperature and preferably up to 140 °C by means of mechanical stress and subsequently retreated according to a continuous or discontinuous process to form hydrogels.

Description

Process for the preparation of milk protein gels, hydrodoses. -Hydrocolloids and -

Superabsorbents (MP gels)

Methods for the preparation of polymeric hydrogels are described in the literature and known to the person skilled in the art. In the context of the present application, this hydrogel group also includes milk protein-containing gels, aqueous gels, hydrogels, hydrocolloids and superabsorbents.

A hydrogel is a water-containing but water-insoluble polymer whose molecules are chemically or physically linked to a three-dimensional network. Built-in hydrophilic polymer components swell them up in water with a considerable volume increase, but without losing their material cohesion.

Physical interactions between the polymers or the three-dimensional crosslinking of these polymers enable the formation of a gel. Polymer-based hydrogels can also be crosslinked by covalent addition of bifunctional agents with the proteins, to form a three-dimensional matrix and thus form a corresponding gel.

In the production of hydrogels and superabsorbents, 2-hydroxyethyl methacrylate, which is referred to as HEMA, poly (ethylene glycol) and poly (ethylene oxide), which are referred to as PEG and PEO, has heretofore been used. HEMA, PEG and PEO polymers are advantageous in the preparation of biomatrices because they are pH and temperature resistant. EM D'urso and G. Fortier made hydrogels formed by combining bovine serum albumin (BSA) with PEG in alkaline solution. Protein molecules serve as anchoring points and are cross-linked by the use of bifunctionalized PEG.

U.S. Patent No. 5,514,379 (Weissleder et al.) Teaches the synthesis of biocompatible, biodegradable hydrogels using proteins or polysaccharides with crosslinking agents, such as polyvalent derivatives of polyethylene or polyalkylene glycol. More specifically, the crosslinking agents are selected from the group consisting of: Bishydroxysuccinimide ester of polyalkylene glycol ("PAG") diacid, bishydroxysulfosuccinimide ester of PAG diacid, PAG diacid bisimidate, PAG diacid bisimitazolide, PAG bisimide, PAG bishalide, PAG bischlorothiazide Diacid, bis (n-aminoalkyl) of PAG and bis (polyoxyalkylene bis or bisbenzoxazolide of PAG) The reaction between the crosslinking agent and a protein such as BSA occurs in D SO solution.

U.S. Patent 5,733,563 (Fortier) teaches the basic solution preparation of bioartificial hydrogels consisting of a three-dimensional cross-linked mixture of bifunctionalized polyethylene oxide with an albumin-type protein. The bifunctionalized polyethylene oxide is preferably polyethylene glycol and the albumin type protein is selected from various sources such as BSA (bovine serum albumin), lactalbumin and ovalbumin. The patent includes a method of making the hydrogels, the description of the hydrogels, and various applications for the hydrogels.

The physical properties of hydrogels have led to their use in a number of ways, including as implant materials, contact lenses and wound dressings and as carriers for the controlled release of medications.

So far, the preparation of the described method was uneconomical, since a long reaction time was a prerequisite. Mass production was therefore unsuitable.

Although the buffer systems used (such as phosphate or borate buffers) allowed a controlled cross-linking reaction, the constant PH value inhibited the variations produced by different raw materials. In addition were the crosslinking reactions inhibited, which led to long reaction times and thus to an uneconomic production.

Recent patent specifications attempted to describe faster and more efficient methods. Among other things, German Patent 0001280849 (Bioartificial Gel Technologies Inc.) teaches preparation and qualitative characterization of PEG-casein hydrogel formulations. Disadvantage, however, is the PEG belongs to the allergens. In addition, PEG derivatives combine water and fats, and are used to cleanse or soothe the skin. Since they make the skin more permeable, active ingredients should be able to penetrate better. However, many PEG derivatives contain carcinogenic impurities, and so in addition to the desired agents also substances such. cancerous preservatives up to allergy substances in our skin. For the preparation of PEG and PEG derivatives ethylene oxide is used, with water, onoethylenglyco! or diethylene glycol can be used as a starting molecule. After reaching the desired molecular weight, the reaction is stopped by addition of an acid (eg lactic acid). Ethylene oxide is a very reactive substance and potentially carcinogenic. Also no industrial production is described. In addition, the premix must be kept warm for 24 hours before further processing takes place. This results in a process that is not economical. In addition, the hydrogels had weak mechanical properties.

British Patent 3639524 (Howes) discloses a preparation of crosslinked hydrogel polymers using (1) N-vinyl-2-pyrrolidones, (2) alkyl methacrylates. In the synthesis of NMP, γ-butyrolactone, previously comprised of formaldehyde and acetylene was generated catalytically via several intermediates, reacted with methylamine. NMP is considered toxic, hazardous to health and irritant. Again, the polymerization takes place over several hours, which excludes an economic result.

The German patent (PCT / EP2002 / 000825) describes the preparation of synthetic hydrogels based on poly (meth) acrylic acids, poly (meth) acrylates, poly (meth) acrylamides, polyurethanes, polyvinylpyrrolidones, polyvinyl alcohol, polyvinyl acetates or their copolymers and derivatives and mixtures thereof. Hydrogels may be based on natural polymers, where the natural polymer may be selected from the group of polysaccharides such as optionally modified starch and starch derivatives, dextrins, agaroses, agargar, curdlan, alginic acid and alginates, Chitosans, polypeptides such as gelatin, pectins and pectinates, carageenans and celluloses and cellulose derivatives such as carboxymethylcellulose, cellulose acetate, cellulose acetate butyrate and alkylcelluloses and mixtures thereof. However, no protein-based hydrogels are mentioned. Methacrylic acids are obtained industrially from petroleum synthesis.

US Pat. No. 10 / 801,232 (Plochocka) describes the preparation of a hydrogel by means of a polymer and an extruder, maleic anhydride being mentioned as a substantial claim. Maleic anhydride is obtained by partial oxidation of n-butane or the so-called "raffinate II" with the aid of a vanadium-phosphorus-oxide (VPO) catalyst. [4] "Raffinate II" is a part of the C4 process that occurs in steam cracking. Fraction and consists essentially of the isomeric n-butenes and n-butane. It is thus again a petroleum product. In addition, it is also hazardous to health and irritating. Maleic acid is produced industrially from maleic anhydride; in turn, the anhydride is synthesized by catalytic oxidation of benzene or butane. Also used as crosslinked ethoxylated amines, amino alcohols, amides and imides. Imide groups are obtained by the reaction with ammonia. Amides are also chemical compounds that formally derive from ammonia. Ethoxylamines are reactions with ethyoxide. The ethoxylation is the addition of ethylene oxide (oxirane) to compounds such as alcohols, phenols, amines or carboxylic acids. In addition, an alkyl vinyl ethers; Methyl vinyl ether, isobutyl vinyl ether, polyvinyl alcohol, olefin, ethylenes, butylenes, isobutylenes, and ethoxylated / propoxylated derivatives. In addition, it is described that the polymer which is crosslinked in the extrusion process is an ester or an amide or imide. Milk proteins do not fall under any of these definitions.

Carboxyl modified superabsorbent proteinaceous hydrogel, 0001263883 (damodaran), involves preparation with glutaraldehyde. It is highly toxic to aquatic organisms and causes severe eye, nose, shark and lung irritation associated with headache, drowsiness and dizziness. In addition, a fish protein is preferably used. The industrial production is also not described. The curing overnight is industrially uneconomical. Despite these known processes, it has hitherto not been possible to give polymer hydrogels, from renewable raw materials (above all protein-based), a cost-effectiveness without the addition of acrylates and fossil raw materials, which are essential for industrial utilization. The use of acrylates and fossil raw materials should be largely avoided for health reasons, if possible.

The invention is based on the invention to avoid the disadvantages mentioned above and hydrogels, from renewable resources (preferably protein-based) and preferably without the addition of acrylates and fossil raw materials a necessary water or. To impart moisture resistance.

The invention is intended in particular to reduce the processing time and the use of chemicals and to produce the hydrogels preferably and largely from renewable or biodegradable raw materials. At the same time, water and energy consumption are to be reduced and productivity increased.

The object is achieved by a method according to the claims.

The present invention is directed to hydrogels prepared by a continuous or discontinuous process with a composition comprising destructured milk proteins, biodegradable thermoplastic polymers and plasticizers.

In this case, at least one protein obtained from milk or a protein produced by bacteria is optionally plasticized together with a plasticizer at temperatures between room temperature and preferably up to 140 ° C under mechanical stress.

The invention is based on the finding that the milk proteins and in particular casein and its derivatives can be plasticized and polymerized in this way. It is envisaged that the plasticizing takes place at temperatures preferably up to 140 ° C. For an even more gentle treatment, the protein is intensively mixed or kneaded together with a plasticizer and subjected to mechanical stress. The required plasticizing temperature is significantly reduced by the plasticizer.

The milk protein is preferably casein or lactalbumin or soy protein.

The milk-derived protein can be produced in situ by precipitation from milk. For this purpose, according to a first procedure, the milk in mixture with rennet, other suitable enzymes or acid introduced directly as a flocculated mixture in the process or the pressed flocculated protein can be used wet. According to another possible method procedure, a separately previously obtained, possibly purified, pure or mixed protein, i. a protein fraction from milk are used, e.g. dried as a powder.

The protein fraction can also be produced by ultrafiltration or by cell cultures. In addition, the milk proteins, for example, with additional salts such as sodium, and potassium can be modified in further processing steps, so that a casein arises.

The milk protein used according to the invention can be mixed with other proteins in a proportion of preferably up to 70% by weight, based on the milk protein. For this example, other albumins, such as ovalbumin and vegetable proteins, in particular lupine protein, soy protein or wheat proteins, in particular gluten come into question.

The mixture of solvent and proteins is heated, usually under pressure conditions and shear, to accelerate the crosslinking process. Chemical or enzymatic agents can also be used to destructivate and crosslink the milk proteins, oxidize or derivatize, etherify, saponify, and esterify. Usually, milk proteins are destructured by dissolving the milk proteins in water. Fully destructed milk proteins result when there are no clumps that affect polymerisation. A plasticizer can be used in the present invention to destructivate the milk proteins and allow the milk proteins to flow, ie to produce thermoplastic milk proteins. The same plasticizer or other plasticizer can be used to increase melt processability, or two separate plasticizers can be used. The plasticizers can also improve the flexibility of the final products, believed to be due to the lowering of the glass transition temperature of the composition by the plasticizer. The plasticizers are substantially compatible with the polymeric components of the present invention so that the plasticizers can effectively modify the properties of the composition. As used herein, the term "substantially compatible" means that the plasticizer, when heated to a temperature above the softening and / or melting temperature of the composition, is capable of forming a substantially homogeneous mixture with milk proteins.

The plasticizer is preferably water, which is used in an amount between 20 and 80% based on the weight of the protein, preferably in an amount of about 40 to 50 wt .-% of the protein content.

Instead of the water or in a mixture with it, other plasticizers, in particular alcohols, polyalcohols, carbohydrates in aqueous solution and in particular aqueous polysaccharide solutions can be used.

Specifically, the following plasticizers and associated weight fractions are preferably hydrogen bridge-forming, organic compounds without hydroxyl group, eg urea and derivatives, animal proteins, eg gelatin, vegetable proteins such as cotton, soybeans, and sunflower proteins, esters of producing acids, which are biodegradable, eg, citric acid, adipic acid, stearic acid, oleic acid-hydrocarbon based acids, eg ethylene acrylic acid, ethylene maleic acid, butadiene acrylic acid, butadienemalic acid, propylene acrylic acid, propylene maleic acid, sugar, eg maltose, lactose, sucrose, fructose, maltodextrin, glycerine, pentaerythritol and sugar alcohols , for example, malite, mannitol, sorbitol, xylitol, - polyols, eg hexanetriol, glycols and the like, and mixtures and polymers, - anhydrides, eg sorbitan, - esters, such as glycerol acetate, {mono, - di, triacetate) dimethyl and Diethyl succinate and related esters, glycerol propionates, (mono, -di, - tripropionate) butanoates, stearates, phthalate esters. These are nonlimiting examples of hydroxyl plasticizers. Important factors are the affinity to the proteins, the amount of protein and the molecular weight. Glycerine and sugar alcohols are among the most important plasticizers. Parts by weight of plasticizers are, for example, 5% -55%, but may also be in the range of 2% -75%. Any of alcohols, polyols, esters and polyesters may be used in proportions by weight, preferably up to 30% in the polymer blend.

Of particular importance for the MP gel mixture are the Theological properties, so that a good processing is possible. Strain-strain solidification is necessary to form a stable polymer structure. The melting temperature is usually in a temperature range of 30 ° C to 190 ° C. Additional temperatures should be lowered with diluents and plasticizers.

The biodegradability of the hydrogels, i. their decomposition by living things and their enzymes is an important property of MP gels.

As the biodegradable thermoplastic polymer for this invention, for example, and preferably, polyvinyl alcohol and copolymers, aliphatic amide and ester copolymers composed of monomers such as e.g. Dialcohols (1, 4-butanediol, 1, 3-propanediol, 1, 6-hexanediol, etc.) or ethylene and diethylene glycol, aliphatic polyester, (aliphatic esters are formed with aliphatic amides} or by other reactions such as lactic acid with diamines and Dicarbonsauredichloriden, diols with carboxylic acids, caprolactone and caprolactam, or ester prepolymers with diisocyanates, dicarboxylic acids, especially succinic, oxalic and adipic acid and their esters, hydroxycarboxylic acids, lactones, amino alcohols (eg, ethanolamine, propanolamine), cyclic lactams, - aminocarboxylic acids (eg, aminocaproic acid), dicarboxylic acids and diamines {eg, salt mixtures of dicarboxylic acids) and mixtures thereof. Polyester such as e.g. Oligoesters can also be used.

Polybuylensuccinat / adipate copolymer; polyalkylene; Polypentamethylsuccinate; Polyhexamethylsuccinate; Polyheptamethylsuccinate; Polyoctamethylsuccinate; Polyalkylene oxalates such as polyethylene oxalate and polybutylene oxalate polyalkylene succinate Copolymers such as polyethylene succinate / adipate copolymer and; Polyalkylene oxalate copolymers such as polybutylene oxalate / succinate copolymer and polybutylene oxalate / adipate copolymer; Polybutylene oxalate / succinate / adipate terpolymers; and mixtures thereof are non-limiting examples of aliphatic polyesters of dibasic acids / diols prepared, for example, from polymerizations of acids and alcohols or ring-opening reactions and suitable for the production of a polymeric hydrogel.

Another possibility for use in the production of biodegradable polymeric hydrogels are aliphatic / aromatic copolyesters. These are derived from dicarboxylic acids (and derivatives) such as malonic, succinic, glutaric, adipic, pimelic, azelaic, sebacic, fumaric, 2,2-dimethylglutaric, suberic, 1,3-cyclopentanedicarboxylic , 1,4-Cyclohexanedicarboxylic, 1,3-cyclohexanedicarboxylic, diglycol, itaconic, maleic, 2,5-norbornanedicarboxylic, 1,4-terephthalic, 1,3-terephthalic, 2,6-naphthoic acid -, 1, 5-naphthoic acid, ester-forming derivatives and mixtures thereof and diols, eg Ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1, 6- Hexanediol, 2,2,4-trimethyl-1,6-hexanediol, thiodiethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl, 3-cyclobutanediol and combinations thereof, at one Condensation reaction formed. Examples of such aliphatic / aromatic copolyesters include blends of poly (tetramethylene glutarate-co-terephthalate), poly (tetramethylene glutarate-co-terephthalate), poly (tetramethylene glutarate-co-terephthalate), poly (tetramethylene glutarate-co-terephthalate), poly (tetramethylene glutarate). co-terephthalate-co-diglycolate), poly (ethylene glutarate-co-terephthalate), polyitetramethylene adipate-co-terephthalate), an 85/15 blend of poly (tetramethylene succinate-co-terephthalate), poly (tetramethylene-co-ethylene-glutarate-co-terephthalate ), Poly (tetramethylene-co-ethylene-glutarate-co-terephthalate).

The processability of the protein mass can be modified by other materials to influence the physical and mechanical properties of the protein mass, but also of the final product. Non-limiting examples include thermoplastic polymers, crystallization accelerators or inhibitors, odor masking agents, crosslinking agents, emulsifiers, salts, lubricants, surfactants, cyclodextrins, lubricants, other optical brighteners, antioxidants, processing aids, flame retardants, dyes, pigments, fillers, proteins and their alkali salts, waxes, Adhesive resins, extenders and mixtures thereof. These Excipients are bound to the protein matrix and influence their properties.

Salts can be added to the melt. Non-limiting examples of salts include sodium chloride, potassium chloride, sodium sulfate, ammonium sulfate, and mixtures thereof. Salts can affect the solubility of the protein in water, but also the mechanical properties. Salts can serve as binders between the protein molecules.

On the other hand, lubricants can affect the stability of the polymer. These can reduce the stickiness of the polymer and reduce the coefficient of friction. Polyethylene would be a non-limiting example.

The physical properties of the polymer composition can be influenced by other proteins, including without limitation, vegetable proteins, such as sunflower protein or animal, such as gelatin. Water-soluble polysaccharides and water-soluble synthetic polymers, such as polyacrylic acids, can also affect the mechanical properties.

Monoglycerides and diglycerides and phosphatides, as well as other animal and vegetable fats can influence and promote the flow properties of the biopolymer.

Inorganic fillers are also among the possible additives and can be used as processing agents. Possible examples, without limiting the use, are oxides, silicates, carbonates, lime, clay, limestone and kieselguhr and inorganic salts. Stearate-based salts and rosin can be used to modify the protein mixture.

Amino acids, the components of the proteins and peptides may be added to the polymeric hydrogel mass to enhance particular pleated sheet structures or mechanical properties. Without limitation, glutamic acid, histidine, trytophan, etc. are mentioned as examples.

Carbohydrates and polysaccharides, as well as amyloses, oligosaccharides and chenodeoxycholic acids can be used as further auxiliaries and additives. Salts, carboxylic acids, dicarboxylic acids and carbonates, as well as their anhydrides, salts and esters can also be used as additional crosslinkers. Hydroxyde, butyl ester, as well as aliphatic hydrocarbons are other ways to cross-link molecules and form macromolecules.

The addition of other substances is not excluded. In particular, additives and auxiliaries, such as lipophilic, hydrophobic, hydrophilic, hydroscopic additives, gloss modifiers and crosslinkers may be provided. The additives and auxiliaries should overall not exceed a proportion by weight of preferably about 30% by weight, based on the protein. As lipophilic additives, vegetable oils, alcohols, fats and can be chosen, which readily hydrophobicize the polymer composition during plasticizing. Furthermore, waxes and greases can be used which add strength to the polymer composition. As waxes, carnauba wax, beeswax, candelilla wax and other naturally derived waxes are preferred.

After formation of the polymeric hydrogel, the MP gel or bound can be further treated. A hydrophilic or hydrophobic surface treatment can be added to adjust the surface energy and chemical nature of the fabric. For example, hydrophobic MP gels or the polymeric hydrogel mass can be treated with wetting agents to facilitate the absorption of aqueous liquids. A bonded fabric may also be treated with a topical solution containing surfactants, pigments, lubricants, salt, enzymes, or other materials to further adjust the surface properties of the MP gel.

In order for the MP hydrogels to meet the increased requirements of improved properties for a particular purpose, they are prepared in previously known and described methods. For this purpose, the polymer composition having the required viscosity is prepared by the continuous or discontinuous process known from the literature and the skilled person, preferably by mixing or extruding a premix with the addition of additives or mixing the polymer composition by metering in the raw materials and additives during mixing or extrusion , The preparation of P-gels can be prepared by known methods z. B. by extrusion process or mixer, kneader or injection molding machine.

The process, which uses water as a solvent and plasticizer, prevents any labor law, toxicological and licensing difficulties.

Due to the plasticization, the polymer composition corresponds to a polymer in which the materials are converted by heating in a plastic state and thus deformed. The temperature exceeds the glass transition temperature of the protein, so that it passes from the amorphous to the rubbery plastic state.

After the exit of the polymer composition, e.g. from the extruder, this can be further processed directly, preferably to a hydrogel in the extrusion process.

Alternatively, the polymer composition may be further processed into a hydrogel immediately after exiting the die, or in at least one later processing step.

In a further development of the invention, the polymer composition can also pass through a bath prior to curing, this procedure is not particularly preferred and usually not required. Alternatively, the polymer composition may be subjected to a spray treatment after exiting the nozzle. Here, for example, smoothing agents, waxes, lipophilic or crosslinking agents can be applied to the surface of the polymer composition. In the case of crosslinkers, those given above are preferred, ie generally different salt solutions, preferably calcium chloride solution, dialdehyde starch solution, or aqueous lactic acid. An alternative to a gas treatment or an ice treatment or a drying and blowing treatment or an ion treatment or a UV treatment or an enzyme treatment, and a renaturation by salts or esterification, etherification, saponification or other crosslinking, and a needling and Wasserstrahlverfestigungsverfahren and the Kaladrieren etc be subjected to.

The multi-constituent hydrogels of the present invention can be in many different configurations. Ingredient, like here By definition, by definition, the chemical species or material is used. Hydrogels can have a monocomponent or multicomponent configuration. Component as used herein is defined as a separate part of the MP gel that is in spatial relationship with another part of the MP gel. The MP gel obtained can in turn be applied to a matrix.

The advantages achieved by the invention include the fact that in the production of hydrogels of the invention, the reduction of harmful substances and environmentally harmful substances during the process and on the hydrogels itself is made possible. In addition, the hydrogel is biodegradable.

In addition, significant resources of energy, water, time and manpower can be saved, which increases environmental protection and improves profitability. The particularly advantageous properties of MP gels are attributed to firming structural changes (textural structure) during plasticization.

The MP gels are preferably made by an extrusion process to allow the highest possible productivity. All methods of preparation of hydrogels described in the art and in the literature are possible without exception. Essential to the invention is the preparation of a homogeneously plasticized polymer, preferably a biogenic biopolymer, which is preferably biodegradable. Unfortunately, no hydrogels have been developed on this basis to date that are water resistant and sufficiently resistant. Preferably, the use of petroleum-based raw materials and / or organic solvents, especially in hydrogels for wound dressings, baby products and cosmetics, to name just a few examples, should be reduced or even ruled out.

The production of hydrogels, which are preferably made from renewable raw materials, with a proportion of milk proteins and with properties such as water resistance, sufficient mechanical properties, such as tensile strength, tensile strength, antibacterial and biodegradable, and the possibility exists, by changing the raw material additions correspond Purpose of use, to influence the properties of the MP gels.

The MP gels prepared by the process according to the invention and their Sheets can be used in a variety of applications and may be wholly or partially sheeted; preferred examples include, without limitation, drug delivery devices that could be used for systemic, intratumoral, subcutaneous, topical, transdermal, and rectal applications; Wound dressings or artificial skin; solid, humidified reaction media for diagnostic kits for use in basic research (PCR, RT-PCR, in situ hybridization, in situ labeling with antibodies or other markers such as peptides, DNA or RNA probes, drugs or hormones, etc.) etc.; Transport media for cells, tissues, organs, eggs, organisms, etc .; Tissue culture media, with or without drugs, for basic research or commercial and therapeutic applications; Electrode materials (with or without enzymes); lontophoresemembranen; protective moistened media for tissue sections (such as replacement coverslips for microscope slides); and matrices for the immobilization of enzymes or proteins for in vivo, in vitro or ex vivo use as therapeutic agents, bioreactors or biosensors; cosmeceutical applications, such as skin hydrating agents or moisturizers, as well as contact lenses, diapers and bandages, water or exudate absorbents in wound dressings, drug release, implants and coatings.

Examples

In the following the invention will be described in more detail with reference to an embodiment. The embodiment is for illustrative purposes only and is not intended to limit the invention. The person skilled in the art can find further possible embodiments by varying the parameters on the basis of this exemplary embodiment and with the aid of his specialist knowledge.

Example 1: Preparation of a milk protein polymer mass. The extrusion takes place with a twin-screw extruder type 30 E of the company. Collin with a diameter of 30 mm. The MP gel is produced by extrusion technology.

Heating takes place via 4 cylinder heating zones with the following temperature sequence 65 ° C, 74 ° C, 75 ° C, 60 ° C: Temperature 65 74 74 74 75 60 r

Function Material supply Water supply Plastic discharge head Nozzle zone zone

Heating zone I II II II III IV

The casein powder is added via a vibrating trough. A hose pump is used to add water. By further metering devices, the additives are added. The polymer composition is processed to a hydrogel by an extrusion process.

The extrusion process and the processing of the polymer composition into a hydrogel are additionally illustrated by FIG. About a metering device 1, the raw materials are added to the extruder 2 and mixed the polymer composition. From there, it is fed through a nozzle 3 to a post-treatment 4.

LIST OF REFERENCE NUMBERS

1 metering device

2 extruders

3 nozzle

4 post-treatment

Claims

claims:

1. A process for the preparation of milk protein gels, hydrogels, hydrocolioids and superabsorbents (MP gels) formed from a homogeneous polymer based on milk-derived proteins that are plasticized with the addition of heat and a plasticizer.

2. The method according to claim 1, characterized in that the polymer composition is output by means of an extruder.

3. The method according to claim 1 or 2, characterized in that the protein obtained from milk is either produced by precipitation from milk in situ or in the form of a previously separately recovered and optionally processed protein or a protein fraction is used.

4. The method according to any one of the preceding claims, characterized in that the proteins obtained from milk are obtained from bacteria.

5. The method according to any one of the preceding claims, characterized in that the proteins obtained from milk are obtained by gas treatment or filtration.

6. The method according to any one of the preceding claims, characterized in that the proteins obtained from milk are milk protein derivatives.

7. The method according to any one of the preceding claims, characterized in that the production process of the hydrogels or superabsorbent is carried out continuously.

8. The method according to any one of the preceding claims, characterized in that the preparation of the homogeneous polymer, consisting of macromolecular gels and / or - solutions by a continuous or discontinuous process under mechanical stress, wherein the polymer composition is preferably plasticized in a mixer, kneader, injection molding machine or extruder.

9. The method according to any one of the preceding claims, characterized in that the plasticizer is a component of the macromolecules.

10. The method according to any one of the preceding claims, characterized in that the proteins obtained from milk, in particular casein, lactalbumin, or soy protein, are obtained from goat's milk, sheep's milk, cow's milk or soy milk.

11. The method according to any one of the preceding claims, characterized in that the plasticizer is selected from the group: water, aqueous carbohydrate solution and in particular aqueous polysaccharides, proteins, alcohol, polyhydric alcohol, fats, acids, amino acid, peptides, salts, cations, enzymes or Mixtures of these agents, as well as their oxidation.

12. The method according to any one of the preceding claims, characterized in that to the plasticizing starting material further additives and auxiliaries are added, optionally by admixing before or during the plasticizing

13. The method according to any one of the preceding claims, characterized in that the MP gel, is substantially water resistant, elastic, antibacterial, biodegradable and has tissue-like mechanical properties.

14. A process for the preparation of MP gels according to any one of the preceding claims, characterized in that at least one milk-derived protein is plasticized together with a plasticizer under mechanical stress and preferably pressed through a nozzle.

15. The method according to any one of the preceding claims, characterized in that the plasticizing is carried out at temperatures up to 140 ° C.

16. The method according to any one of the preceding claims, characterized in that the MP gel is dried and after-treated, preferably by a Bath, spray treatment, gas treatment, ice treatment, drying and blowing treatment, ion treatment, UV treatment, infrared treatment, enzyme treatment, needling and hydroentangling process, and renaturation by salts or alcohols, esters and ethers, esterification, Saponification or etherification of a further crosslinking or coating, the calendering, etc. is subjected.

17. The method according to any one of the preceding claims, characterized in that the MP gel is destructured by chemical or enzymatic means, oxidized or derivatized.

18. The method according to any one of the preceding claims, characterized in that polymers and polysaccharides have funigicidal, antibacterial and antiviral properties and / or are considered natural remedies.

19. The method according to any one of the preceding claims, characterized in that carboxylic acids, dicarboxylic acids and carbonates, and their salts, esters, and fatty acids, preferably biodegradable, are used for the mixture.

20. The method according to any one of the preceding claims, characterized in that aliphatic esters and aliphatic amide copolymers, preferably biodegradable, are used for the mixture.

21. The method according to any one of the preceding claims, characterized in that the gel mass is destructured during or after the process by chemical or enzymatic means, oxidized, derivatized, etherified, esterified or saponified.

22. The method according to any one of the preceding claims, characterized in that amino acids are used for the mixture.

23. The method according to any one of the preceding claims, characterized in that the MP gel with protease inhibitors, in particular enzymes, surfactants, Acids, Serptnen, phenolic molecules from plants, or polysaccharides, added or post-treated.

24. The method according to any one of the preceding claims, characterized in that the protein starting material comes from any source, in particular animal, vegetable or microbial.

25 MP gel, comprising a thermo-mechanically plasticized milk protein, in particular produced by a method according to any one of claims 1 to 8.

26. Use of an MP gel according to claim 25 for application to materials without limitation, in particular textile fabrics, matrices and films, e.g. Woven goods such as woven fabrics, knits, knitted or crocheted fabrics or textile composites such as felt and nonwovens, but also as matrix itself or composite with other materials.