KR20080114798A - Collagen powder and collagen-based thermoplastic composition por preparing conformed articles - Google Patents

Abstract

The invention provides a new collagen based technology. The invention provides a dry collagen powder as a precursor for the preparation of an homogeneous thermoplastic collagen-based composition, which may further comprise additives. The present invention relates also the use of said composition in the manufacturing of solid articles conformed according to plastic technology, and to the articles. ® KIPO & WIPO 2009

Description

Collagen-based thermoplastic compositions for making collagen powders and formed products. {COLLAGEN POWDER AND COLLAGEN-BASED THERMOPLASTIC COMPOSITION POR PREPARING CONFORMED ARTICLES}

The present invention relates to the use of precursors in the production of new collagen-based technologies, in particular homogeneous collagen-based compositions which are carried out in the same manner as new collagen-based precursors, processes for their preparation and thermoplastics. have. The present invention also relates to articles with solid shapes formed from the thermoplastic compositions and to processes for the manufacture of the articles.

Collagen is one of the most successfully applied proteins, among other fields, as a biodegradable membrane used in the food industry as a membrane forming protein that yields flat or tubular food products and / or as a packaging material in food packaging. Is one of. Collagen is a general term for a family of proteins, representing them that can be found in multicellular organisms. To date, more than 20 different types of collagen have been described in the literature. For industrial purposes, there is a source of collagen which is particularly advantageous for recovery of collagen from the standpoint of effectiveness, tissue structure and economy. One such source is bovine hide.

One of the most prominent current collagen-based techniques involves the manufacture of sausage casings based on collagen. Since a great deal of processing success and the mechanical properties of the resulting collagen tubular or flat membranes depend on their fibrillar structure, this technique strives strongly to prevent collagen fibers from losing their native molecular structure. Thus, the main purpose of this technique is to preserve the fiber collagen structure during all industrial steps of extracting and refining collagen from raw animal tissue, such as cow skin and porcine skin. Carefully designed processes therefore exist in the state of the art, where a dough of highly hydrated, basically inert acid expanded collagen fibers is obtained, which can be extruded into a flat or tubular membrane. Temperature control during collagen dough production and in extrusion is a very important factor that prevents collagen fibers from hydrolysis and thus gelatinization.

Although the acid swollen aqueous dough of fibrous collagen shows excellent properties in forming membranes by extrusion at low temperatures, even at low solids (collagen) concentrations, the enormous dough viscosity indicates that these materials do not exhibit rheological properties. The dough viscosity will allow the dough to be easily processed by conventional extrusion equipment known to process plastics. For example, patents US 3,123,482 and US 3,346,402 can give an idea of what complex and specialized extrusion equipment and conditions are used to make collagen packaging.

In addition, after passing through an orifice at the exit of the extrusion head, the tubular or flat membrane formed from the collagen dough must be stabilized by coagulation and drying, which means that large amounts of water have a high energy cost. It must be removed from the gel. Within this process, the collagen fibers are crosslinked to obtain a three-dimensional matrix having a reticulated structure of microfibers that is physically oriented and inverted in many cases on-line or in subsequent chemical treatments. On the other hand, this represents a loss in which the product obtained by this kind of technique cannot be recovered in repeating the process and cannot be reused. In addition, any other shaped three-dimensional article that differs from those obtained by extrusion into a membrane, tube or thread, although they are not intended as a collagen soft fishing feed and soft hydration product such as lure or optical lenses, During drying and in the curing process, the molded three-dimensional products shrink dramatically until they lose their original shape, and thus cannot be performed. Furthermore, although useful in conventional forms of application, the highly hydrated dispersion of fibrous collagen does not risk hydro-thermally dispensing collagen to the extent that it provides a very sparse gelatin solution. It does not have properties that may be suitable for forming three-dimensional solid products by conventional thermoplastic process techniques such as thermal extrusion and injection molding. As a result, solid collagen-based molded products with low water contents have not yet been successfully achieved.

Thus, although it can be performed like a thermoplastic, a collagen-derived hydrogel does not have the structure, stability or strength to perform as a solid molded product; Even when the hydrogel is dried, with the resulting consumption, the hydrogel will not run stably under wet conditions.

Another collagen-based technique is characterized by the degradation of collagen with gelatin, animal glue and hydrolysates. Depending on the degree of hydrolysis, these hydrolysis products derived from collagen are used in a wide variety of industries as foods, cosmetic ingredients and animal glues. According to this technique, collagen molecules are hydrolyzed by heat treatment of acidic or alkaline dispersions of microfiber collagen in water or attack of enzymes until the basic structural units are destroyed to obtain gelatin. The average molecular weight of this new pepsin product is variable and is always below 500 kD. In practice, a major feature of gelatin is its ability to generate physical hydrogels, even at very low solid concentrations, which are heat-reversible at temperatures of about 40 ° C. This capability entails certain advantages in processing and shaping the process because the gelatin hydrogel can be heated above the melting point to be poured or injected into the mold and then solidified by cooling. However, the gel toughness and strength of gelatin hydrogels is low and depends on the water content and the degree of crosslinking. In attempts to form shaped products, technical problems also result from large scale shrinkage that occurs during drying of the hydrated product. Processing of molded articles consisting of gelatin or gelatin hydrolysates with an average molecular weight of less than 3 kD is not possible.

Some new processes involve powdered gelatin by adding water, plasticizing it in an extrusion apparatus and subjecting it to high temperatures and shear forces, thus drawing-off from the slotted die of the extruder, It has been proposed to convert gelatin into a product, such as thermoplastic, for forming articles, by generating a flowable homogeneous melt that can be converted (see patent US 4,992,100 and US 5,316,717). Particulates can be treated like products such as thermoplastics, which have the advantage of operating at low water content and preserving some gelatinous properties, whereas shrinkage of molded articles made from such particulates is very slight, e.g. plasticizers It can be set by the addition of an additive, such as. Nevertheless, gelatin is the first product produced from collagen at the inevitable cost of preparation and acquisition. In addition, the molecular structure of the gelatin entails a lack of behavior during aging of the molded product or under wet conditions, which in fact has led to our knowledge that no industrial application has been found in the molded product.

In order to reduce the process of preparing gelatin and glue precursors (also called gelatinous materials), another process has been proposed in DE 19712400. This process has the potential to avoid both wet and thermo-chemical, time consuming, cost-operated and previously required steps by starting from a collagen-rich feedstock and taking the following steps: a) Collagen feedstock fibers Grinding with; b) bringing the material to a water content of 5% to 40%; c) When the fibers lose their inherent three-dimensional structure, together with the major components having an average molecular weight of at least 500 kD and up to essentially homogeneous hydroplastic masses that can be wholly or partially soluble in water at least 45 ° C. Introducing heat and applying shear force to the wet material for up to 60 minutes; d) treating the hydroplastic masses to form granulates, strands or sheets which are likely to be treated directly with gelatin or glue. These materials are considered as precursors of gelatin and glue and they have a hard and brittle persistence, are soluble in some warm water and will form soft membranes and products that can replace the performance of existing collagen membranes. Can not.

One important advance in the investigation of new industrial applications of collagen as a biodegradable and (principle) edible material is a new technique for molding products, starting from inherent collagen without requiring pre-production of gelatin. To achieve this. Thus, significant advances in the production of collagen-based products, such as extruded tubular or flat membranes and molded solid products, have led to the advance of plasticized “wet” chunks based on acid- or alkaline-expanded aqueous dispersions of collagen fibers. It would be the development of a process that would avoid the step of making. This type of gel-like dispersion is difficult due to the high manufacturing cost, low flowability (high viscosity), as a result of which the process is difficult and the water needs to be removed after molding and / or extrusion.

In light of the above, there is a need for alternative collagen-based techniques for the production of collagen-based products of different shapes, including flat or tubular membranes, and three-dimensional products of different shapes and sizes. Advantageously, the technique must on the one hand avoid the preparation of gelatin intermediates associated with time consuming and expensive processes. On the other hand the technique should also avoid the losses associated with the use of the native collagen described above and the losses associated with the aqueous dispersion of collagen fibers that are difficult to process as mentioned above.

There is therefore a need for the highest technical level of new collagen-precursors that can be used in the preparation of collagen-based compositions that perform with thermoplastics.

Also advantageously, there is a need for alternative collagen-based compositions that can be processed by conventional plastics techniques known in the art, and are suitable for being formed into an edible, biodegradable solid shaped product. Moreover, the product is thermosealable and, among others, exhibits improved properties on collagen-based products known to the highest technical levels such as water resistance, tensile strength, minimal shrinkage of the formed product.

The first object of the present invention is therefore the provision of collagen precursors for use in new collagen-based techniques. The inventors have surprisingly found that it is possible to produce dry collagen powders, such as collagen precursors. When such dry collagen powder is mixed with water and subjected to suitable conditions of shear force, temperature and pressure, a homogeneous collagen composition is obtained which advantageously acts as a thermoplastic. Such compositions can thus be treated according to common plastics processes and formed into improved solid products. Therefore, another object of the present invention is a process for preparing the collagen precursor, which is a dry collagen powder.

The first object of the present invention is therefore the provision of collagen precursors for use in new collagen-based techniques. The inventors have surprisingly found that it is possible to produce dry collagen powders, such as collagen precursors. When such dry collagen powder is mixed with water and subjected to suitable conditions of shear force, temperature and pressure, a homogeneous collagen composition is obtained which advantageously acts as a thermoplastic. Such compositions can thus be treated according to common plastics processes and formed into improved solid products. Therefore, another object of the present invention is a process for preparing the collagen precursor, which is a dry collagen powder.

Another object is to provide a homogeneous plastic collagen-based composition which is mixed from dry collagen powder for use in the manufacture of solid shaped articles.

Another object is a product with a solid shape formed from a homogeneous thermoplastic collagen-based composition.

Yet another object of the invention is to provide a process for preparing the homogeneous thermoplastic collagen-based composition of the invention. Yet another object is to provide a process for the manufacture of a product with a solid shape.

The present invention provides dry collagen powder as a precursor suitable for the production of homogeneous thermoplastic collagen-based compositions. Such dry collagen powder, hereinafter, the dried collagen powder, is based on modified or partially modified microfiber forming collagen, has an average molecular weight of at least 500 kD, a solubility of greater than or equal to 25% in water at 60 ° C. and 30 μm. Average particle size included between 350 μm is shown. In a preferred embodiment, the dry collagen powder of the invention exhibits an average particle size 0 comprised between 50 μm and 100 μm.

The term “filbril forming collagen” includes collagen type (I), type (II), type (III), type (V), type (IX) and mixtures thereof.

The term “partially denatured” as used in this description means the degree of collagen denaturation of at least 30%, more preferably greater than 70%, and most preferably greater than 90%. Degeneration is carried out by differential scanning calorimetry (DSC), by hydration of the collagen specimen overnight with water; It can be easily determined by the introduction of a tightly sealed product, obtained by a DSC pan, and by the recording of DSC with a heating rate of 5 Km / min. For fully native collagen, the peak is observed in the DSC plot at about 60 ° C., while for fully denatured collagen, the peak is not observed close to 60 ° C. and there is no peak between 25 ° C. and 40 ° C. Not found or only small peaks are found. In the relative region below the peak near 60 ° C., an assessment of the degree of denaturation of the collagen specimen can be made.

As used in the description, the term “dry” is comprised between 3% and 15% by weight, preferably between 6% and 10% by weight, expressed as a weight percent suitable for the total weight of the dry collagen powder. , Water content.

The dry collagen powder of the invention is obtained by the following process, which is also another object of the present invention. The process includes the following steps:

a) mincing the collagen raw material into cylindrical particles;

b) drying the cylindrical particles at a temperature equal to or higher than the denaturation temperature of collagen until the complete cross section of the individual particles is dry and brittle;

c) milling the particles obtained either in step b);

d) obtaining the dry collagen powder of the invention.

Collagen feedstock is "based on microfiber forming collagen", regardless of the origin of the tissue from which it is recovered. According to the invention, the collagen feedstock comprises native collagen and microfiber forming collagen chemically or modified by enzymes. Collagen feedstocks suitable for practicing the present invention are derived from animals including cattle, pigs, calves, lambs, sheeps, goats, horses, kangaroos, camels, chickens, ostrichs, crocodiles and fish such as salmon and herring. It can be obtained from a suitable source of collagen, including tissues such as skin, leather, bone-derived bone protein (ossein), tendons, viscera and cartilage. In a preferred embodiment, hides or leathers are used for industrial purposes in particular suitable for the recovery of collagen in terms of utility, tissue structure and economics, which are known in the state of the art. In a preferred embodiment, the tissue is selected from cow leather and pig leather.

Collagen sources are generally pretreated by processes known in the art to obtain collagen raw materials. In this respect, the collagen source is not used directly as in this collagen industry, but the sources are first purified by mechanical and / or chemical treatments known in the art. In certain embodiments, the mechanical and / or chemical treatments are those typically applied in tannery. One example of a simple mechanical purification step is the splitting of swine leather to remove the highly fat-loaded inner part of the pig leather, as described in patent application WO 2004/073407. Another example of a typical applied chemical treatment is a combination of alkali and acidic process steps applied to a split of bovine hide during depuration or hair loss of bovine hide for use in making edible sausage packages as described in DE 972854. To be done in the tannery.

The degree required for the purification of the collagen feedstock achieved by these mechanical and / or chemical treatments will depend on the requirements related to further processing of the collagen feedstock. According to the present invention, the degree of purification of the collagen raw material will depend on the necessity associated with collagen based on the product with the solid shape obtained, as will be described in more detail below.

Preferred collagen raw materials are unlimed leather, limed leather pieces, cattle pelts and pieces of pig leather.

In a more preferred embodiment of the present invention, the collagen raw material is a piece of lime leather, such as those used in the manufacture of collagen sausage packaging or in the gelatin industry, which is readily available from the tannery.

Step a) of the process as defined above comprises the step of compacting the collagen raw material into cylindrical particles.

The term "cylindrical particle" refers to a worm shaped strand having a diameter of about 2 mm in cross section.

This step a) is typically carried out using suitable equipment known to those skilled in the art, such as used in the manufacture of collagen sausage packages. In a particular embodiment, the equipment is a grinder, such as a Wolfking grinder.

In a particular embodiment, step a) comprises soaking a piece of limehide leather or fur as collagen material in water at room temperature in a tanning drum until the collagen material is completely saturated; Draining the immersion water; Chopping the collagen raw material rehydrated into pieces having a diameter of about 10 mm; Passing the material through a series of plates with holes under high pressure to obtain a final disc with holes of 2 mm diameter; Recovering the resulting compacted material consisting of cylindrical particles. The cooling of the equipment is controlled so that the temperature of the collagen material does not exceed about 50 ° C.

Step b) is carried out at a temperature high enough to denature or partially denature the collagen material by suitable heating means known in the art. It is known in the art that the denaturation temperature of collagen, which is generally above about 65 ° C., depends on factors such as water content, the presence or absence of hydrotropic additives such as calcium chloride, urea, and the like, and the degree of natural crosslinking. have. According to this step b), the collagen is denatured or partially denatured to at least 30%, preferably higher than 70% and more preferably higher than 90%. In a particular embodiment, step b) is performed by air drying the cylindrical particles obtained from step a) at a temperature comprised between 60 ° C. and 80 ° C. Appropriate equipment can be used in step b). In a more particular embodiment, step b) is performed in a furnace, such as a hearth-type furnace. Typically the cylindrical particles are dried at 80 ° C. in a furnace after 16 hours, as described in Example 1. Step b) provides conditions for providing dry, brittle, complete cross-section cylindrical particles having a water content of between 3% and 15% by weight, preferably between 4% and 8% by weight of water content. Is carried out under.

The inventor surprisingly found that the particles undergoing step b) reached a suitable brittleness, which according to the invention shows a particle size comprised between 30 μm and 350 μm, preferably between 50 μm and 100 μm. It has been found that it is a prerequisite for grinding cylindrical particles into sufficiently finely ground collagen powder. On the other hand, the inventors also found that the particles dried under suitable conditions, such as at ambient temperature, still show collagen non-denaturated microfiber structure and do not achieve the required brittleness, so that the powders together with particles of the desired size It was found to be more ground.

As a result, step c) of the process is obtained from step b) to obtain a dry collagen powder of the invention having an average particle size comprised between 30 μm and 350 μm, preferably between 50 μm and 100 μm. Drying and brittle particles are pulverized finely. The milling step can be carried out by suitable equipment known in the art, such as a turbo rotor mill (TMR, Gorgens Company, Germany). The particle size distribution of the dry collagen powder can be varied by setting different rotational speeds of the turbo rotor. In a particular embodiment, at a flow-rate from 200 g / min through the mill and at a rotational speed of 4221 rpm of the turbo axis of rotation, the average particle size of the powder is found to be less than 60 μm.

In a particular embodiment of the process for the preparation of the dry collagen powder of the present invention, before step a), the collagen raw material may be pretreated to effect denaturation or partial denaturation of the collagen. Thus, the collagen raw material is washed before another processing and the denaturation or partial denaturation of the raw material is washed by conventional heating or at a temperature above the denaturation temperature of the collagen, for example for a time typically comprised between 10 and 120 minutes. It is achieved by microwave oven heating. The obtained collagen material is then finely chopped and dried until the cylindrical particles turn brittle and ground according to the process described above. For the process for producing the dried collagen powder of the present invention, it is important that the collagen raw material is modified or partially modified to achieve a suitable brittleness as mentioned above in connection with step b). Such denaturation may occur before or during step b).

The dry collagen powder of the invention, prepared according to the process described above, can then be stored under suitable conditions, such as in a suitable storage tank. Under storage, the dry collagen powder of the invention can absorb water. For example, under typical storage conditions of 22 ° C./60% relative humidity and for 48 hours, the dry collagen powder absorbs about 7% by weight of water. As a rule, dry collagen powder can be further used directly in the production of homogeneous collagen-based thermoplastic compositions, which is another object of the present invention.

Thus, another object of the present invention is the use of the dry collagen powder of the invention in the preparation of homogeneous thermoplastic collagen-based compositions. In this regard, the inventors have found that dry collagen powder, which surprisingly exhibits an average particle size of 350 μm or less, is required to produce homogeneous collagen-based thermoplastic compositions.

Another object of the present invention is a homogeneous thermoplastic collagen-based composition comprising the inventive dry collagen powder and water, hereinafter the composition of the invention. As used herein and unless stated otherwise, the percentages of ingredients are expressed in weight and referred to as the weight of the total composition of the invention. In certain embodiments, the inventive composition comprises from about 20% to about 95% by weight of the inventive dry collagen powder and from about 5% to about 80% by weight of water, preferably from about 50% to about 85% Wt% dry dry collagen powder of the invention and about 15 wt% to about 50 wt% water and more preferably from about 60 wt% to about 75 wt% inventive dry collagen powder and about 25 wt% to about 40% by weight of water.

In a preferred embodiment, the composition of the invention further comprises an additive which is a plasticizer. Plasticizers useful in the compositions of the invention include, for example, polyols and high molecular weight alcohols, which are, for example, glycerol, propylene glycol, sorbitol, butanediol, ethylene glycol, diethylene glycol, triethylene glycol, low molecular polyethylene glycols and polypropylene glycols, and mixtures thereof. It includes, but is not limited to. In a more preferred embodiment, the plasticizer is glycerol. In certain embodiments of the invention, the plasticizer is present in an amount comprised between about 5% and about 50% by weight.

In general, plasticizers can function as water-linked humectants in the compositions of the invention that prevent the composition from drying out during the treatment and storage of the composition in open air. However, some plasticizers can act as a plasticizer as well as act as a wetting agent to provide certain properties such as plasticity, flexibility, processability and elasticity to the compositions of the invention and / or to articles formed from the compositions of the invention.

Plasticizers that act as water-binding wetting agents can prevent the solid shaped product obtained from the composition of the present invention from drying below the desired water content, as described further below. Generally, the dryer the product with the solid shape based on the composition of the present invention, the less flexible and more brittle it is. Thus, by adjusting the water content of the composition in question, the mechanical properties of the solid shaped product can be significantly affected. One way to achieve such control is to add the correct amount of water to the composition of the invention, and after preparing the product with a solid shape, then packaging the product in a vapor impermeable package to avoid water loss if necessary. Another possibility is to introduce an effective amount of plasticizer into the inventive composition that acts as a humectant, leaving the desired solid content in the obtained solid shape to prevent the product from drying out.

In a preferred embodiment, the inventive composition comprises: (i) about 40% to about 65% by weight of the inventive collagen powder; About 20% to about 40% by weight of water; And from about 10% to about 20% by weight plasticizer. In a more preferred embodiment, the plasticizer is glycerol.

Compositions of the invention include proteins, biodegradable polymers, blowing agents, modifiers, fillers, lubricants, crosslinkers, preservatives, colorants, rheology improvers, flavoring agents and scents, nutritional agents and It may further comprise one or more other additives selected from the group of mixtures thereof. The additives may be added to alter or control the properties of the solid shaped product of the invention, which is further described below.

Suitable proteins are selected from animal derived proteins, plant derived proteins, microbial proteins and mixtures thereof. In a particular embodiment of the invention, the collagen powder content of the inventive composition, referred to as total protein content, is between about 30% to about 100% by weight, preferably between about 50% to about 90% by weight. Included. In a preferred embodiment, the dry collagen powder content is at least 50% by weight of the total protein content. Animal derived proteins include, but are not limited to, casein or whey protein derived from milk, albumin derived from blood or eggs, egg whites, gelatin, keratin, elastin and mixtures thereof. Plant-derived proteins include, but are not limited to, soybeans, gluten, gliadine, glutenine, zein, legume proteins, alfalfa proteins, peas, cotton seeds, sunflower seeds, lupinseed, and the like. Protein, grain-derived protein and mixtures thereof. In a preferred embodiment, gluten is used. In addition, the microbial protein is suitable for being an additive of the composition of the invention. In certain embodiments, yeast proteins are added to the compositions of the invention.

Biodegradable polymers may be added to the compositions of the invention to control the mechanical or degradable properties of the solid articles of the invention described further below. Suitable biodegradable polymers include polyhydroxyalkanoates, polyalkylene esters, polylactic acid (PLA), polylac, such as copolymers such as polyhydroxybutyrate (PHB) or polyhydroxybutyrate-valerate (PHBV). Natural or synthetic thermoplastics, including tide (PLLA), poly-ε-caprolactone (PCL), polyvinyl esters, polyvinyl alcohol, and mixtures thereof.

Blowing agents are also suitable for use in the compositions of the invention. Blowing agents may be added to the compositions of the invention to form low proportions of expanded bubbles in articles having a solid shape, described further below. Water can act as the primary blowing agent, but physical and chemical blowing agents are preferably used as auxiliary blowing agents. Physical blowing agents include inert gases such as nitrogen, carbon dioxide or rare gas; And agents having low boiling points and liquids at ambient temperature, such as alcohols such as ethanol, hydrocarbons such as 2-propanol, butane or combinations thereof. Chemical blowing agents are generally more difficult to control than physical formulations, so that the physical formulations are preferably used in the process. Such chemical agents include, but are not limited to, ammonium carbonate, sodium bicarbonate, sodium azide and combinations of acids and carbonates known to those skilled in the art. In certain embodiments, the blowing agent is a compressed gas that is mixed and dispersed in the composition of the invention. In a particular embodiment, the agent is carbon dioxide. Preferred concentrations of carbon dioxide are from about 0.2% to about 5% by weight based on the weight of the composition of the invention. Carbon dioxide is soluble in the composition of the invention.

Modifiers can be added to the compositions of the invention and used to improve the specific mechanical properties of the solid shaped articles of the invention, such as elasticity, tear strength and other properties related to the characteristics of tissues and sensory organs. In certain embodiments, modifiers are added in the case of some edible or chewable solid shapes formed from the compositions of the invention to increase animal acceptance. Modifiers can also be used to improve some process properties, such as bubbling performance. Typical modifiers that can be used in the compositions of the invention include, but are not limited to, synthetic polymers such as polyvinylalcohol, polylactic acid, poly (caprolactone), poly (esteramide), natural polymers such as gum and other hydrocolloids. Contains raw polymers.

Fillers may be added to provide structural reinforcement and improve mechanical properties of solid shaped articles formed from the compositions of the invention as further described below. In general, fillers reduce manufacturing costs. In certain embodiments, the composition comprises about 1 wt% to about 25 wt% filler, preferably about 5 wt% to about 20 wt%, more preferably about 10 wt% to 15 wt% filler. Preferably, the filler comprises cellulose derivatives, microfibers, crosslinked collagen, cellulose fibers; Natural starch, chemically or physically modified starches, inorganic materials such as calcium carbonate and silicon dioxide and mixtures thereof.

When the composition of the invention is formed into a product having the desired solid shape, for example by helping to release a solid shaped product formed from a mold, the lubricant has a mold- or pigment-lubricating effect. It may be added in an effective amount to provide. Water-insoluble lubricants can also increase the water-resistance of products with solid shapes of the invention. Examples of suitable lubricants that can be used in the compositions are those skilled in the art in the prior art such as soybean oil, rapeseed oil, sunflower oil, palm oil, phospholipids such as lecithin, mono- and diglycerides of fatty acids, preferably saturated fatty acids. Known compounds; Preferably, but not limited to, hydrogenated, vegetable oils, phosphoric acid-derivatives of esters of polyhydroxy compounds, animal fats, mineral oils, etc., and preferably mixtures thereof, preferably hydrogenated to prevent oxidation. Preferred lubricants are soybean oil and lecithin. In certain embodiments, the amount of lubricant included in the compositions of the invention is from about 0.1% to about 10% by weight, preferably from about 0.5% to about 5% by weight.

The crosslinker can provide a high degree of mechanical properties to a solid shaped product made from the composition of the invention. Examples of useful crosslinking agents ("curing agents"), which may be added in amounts from about 0.05 to about 5% by weight, include, but are not limited to, dialdehydes such as formaldehyde, glutadialdehyde, or glyoxal, dialdehyde starch, conventionally Molecules with multiple aldehyde functions known to those skilled in the art, diisocyanates, such as hexamethylene diisocyanate, carbodiimides, such as N, N- (3-dimethylaminopropyl) -N'-carbodiimide hydrochloride, cyanide Polyglycidyl ethers such as 1,4-butanediol diglycidyl ether, reducing sugars such as ribose, polyepoxy compounds, dicarboxylic acids, dimethyl suberimidate, diphenyl phosphoryl azide, Chlorotriazine, genipin and acrolein. Crosslinking can also be accomplished with enzymes, for example using transglutaminase or other suitable enzymes known to those skilled in the art.

Preservatives may also be included in the compositions of the invention. Compatible antimicrobial agents, such as fungicides or fungicides, may also be included in amounts effective to prevent the growth of microorganisms in the compositions of the invention and in products with solid shapes formed from the compositions of the invention. Examples of useful preservatives include, but are not limited to, propionic acid, sorbic acid and their sodium or potassium salts, parabens, benzoic acid and / or benzoate, acetic acid, vinegar, sodium diacetate, lactic acid known in the state of the art. acid) and mixtures thereof. The composition may comprise about 0.05 to about 0.3 weight percent of preservative. The composition of the invention may further comprise a coloring agent.

Suitable colorants for use in the present compositions include, but are not limited to, synthetic dyes such as Bismarck Brown 2R and Direct Green B; Chlorophyll, xanthophyll, carotene, saffron, kermes, curcuma, cochenille and indigo, anatoto, carmin, erythrosine ), Typical food colorants such as tartrazine, allura red, sunset yellow and metal oxides such as iron and titanium oxides. In certain embodiments, from about 0.01% to about 10%, preferably from about 0.5% to about 3% by weight of colorant is included in the composition of the invention.

Fluidity improvers such as organic acids such as citric acid may also be added. These further influence the rheological properties of the inventive compositions prepared under shear forces, pressure and temperature conditions, as described further below. The effect on rheological properties is interpreted as on-line acidic partial hydrolysis of proteins present in the composition of the invention, and in certain embodiments, from about 0.1% to about 10% by weight, preferably from about 0.5% to 5% by weight of citric acid Is added.

Flavors and scents and mixtures thereof may be added to the compositions of the invention, including, but not limited to, fruit extracts such as cocoa, vanillin, strawberries and bananas, smoked pigments caramel, bacon and Same edible flavoring agents. These improve the taste of the edible composition of the invention. In certain embodiments, colorants suitable for flavoring agents are used. The composition of the invention may comprise a nutrient for example as a vitamin or mineral.

Preferred compositions of the invention comprise about 56% by weight of dry collagen powder; About 24% water; About 17.5 weight percent glycerin; And about 2.5 weight percent citric acid.

Another preferred composition of the invention comprises about 50% by weight dry collagen powder; About 25% water; About 15% glycerin; It consists of about 5 wt% cochinyl powder and about 5 wt% ethanol. Another preferred composition of the invention comprises about 50% by weight dry collagen powder; About 25% water; About 15% glycerin; About 5% wheat gluten; About 2% by weight cochinyl powder; About 2% by weight vanilla flavoring; And about 1 weight percent citric acid.

Another preferred composition of the invention is a dry collagen powder; About 15% water, including about 10% colorant caramel based on water; About 10% fragrance bacon based on water; And about 6% by weight fragrance smoked pigment caramel based on water; About 20% glycerin; And about 2.5% citric acid.

Another preferred composition of the invention comprises about 50% by weight dry collagen powder; About 25% water; About 20% glycerin; And about 5% ethanol by weight.

Another aspect of the invention relates to a process for the preparation of a composition of the invention. Depending on the process, the compositions of the invention can be prepared in the form of lumps or in the form of solid pellets. The process includes the following steps:

(i) mixing the dry collagen powder of the invention with water;

(ii) subjecting the mixture obtained in step (i) of dry collagen powder and water to shear force, temperature and pressure conditions until the components are converted to a homogeneous thermoplastic collagen-based composition present in the form of agglomerates; And optionally

(iii) converting the homogeneous thermoplastic collagen-based composition in lump form into pellets.

The dry collagen powder obtained according to the process described above in step (i) is contacted and mixed with water by suitable means. The amount of water is calculated to achieve the weight percent of the inventive composition, taking into account that the dry collagen powder may contain the remaining water or may absorb water upon storage, and in certain embodiments the dry collagen powder and water are first It is contacted and mixed manually, then transferred to a rapid laboratory mixer, where the dry collagen powder and water are further mixed until a grainy agglomerate is obtained (see examples 2 and 3a). The granule aggregates can then be further processed according to step (ii) to obtain the homogeneous thermoplastic collagen-based composition of the present invention. In step (ii), the mixture of dry collagen powder and water obtained in step (i) is subjected to shear forces under suitable conditions of temperature and pressure, so that the mixture is converted into a homogeneous thermoplastic collagen-based composition in the form of agglomerates. Treatment conditions can be easily altered to achieve conversion into a homogeneous thermoplastic collagen basis in effective mixing and lump form by those skilled in the art.

The process for the preparation of the composition of the invention optionally comprises the step (iii) of converting the homogeneous thermoplastic collagen-based composition into pellets, which is solid in the form of agglomerates. The composition mass is thus extruded through an outlet or die into air or another gaseous medium. The extrudate is then split into pellets of the desired size, allowed to dry or to match its moisture content, or, if necessary, cooled and stored for later use. The extruded mixture solidifies within minutes, depending, for example, on the size of the extruded portion, the components of the composition of the invention, the temperature of the composition and other factors. In a particular embodiment, the myriad strands of the mass are extruded through one or several slotted dies, preferably through a die having a circular cross section, provided on an extruder and, after cooling in airflow, The same or different pellet sizes are pelletized by granulators or strand granulators into pellets commonly used in the state of the art for processing plastic materials. Pellet sizes typically include between about 0.1 and 10 mm, preferably at least 1 mm and more preferably at least 2 mm. Thus, the solid pellets can be stored and subsequently formed into a product having a solid shape. In a preferred embodiment, the pellets are stored in a sealed sealed bag.

The process for the preparation of the composition of the invention can be carried out by a suitable high shear kneader system. In a preferred embodiment, the process is carried out in an extruder selected from a single screw extruder and a twin screw extruder, preferably in a twin screw extruder. Suitable twin screw extruders are idling twin screw extruders such as Krupp Werner & Pfleiderer ZSK25 or AVP twin screw extruder Type MP 19 TC. With a single screw type, an extruder such as Rheomex 302 can be used.

Processes for the preparation of the compositions of the invention include plasticizers, proteins, biodegradable polymers, blowing agents, modifiers, fillers, lubricants, crosslinkers, preservatives, colorants, rheology modifiers, flavoring agents and fragrances, nutrients and mixtures thereof as described above. It may further comprise the addition of one or more additives selected from. The choice of additive or additives and the amount added can be varied depending on the desired properties of the product having a solid shape to be formed from the composition of the invention.

The additives or additives may be added simultaneously or separately during the process of the invention or at any time before the process. In this respect, before the additive or additives are contacted in step (i), the additive or additives may already be added to the dry collagen powder or may be added to water. The additive may be added in step (i) together with the dry collagen powder and water or may be added later during step (ii) at any time. The additives are uniformly integrated into the homogeneous thermoplastic collagen-based composition which can be obtained in the form of agglomerates or in the form of pellets as in Examples 3b), 3c) and 4). One or more additives may be added independently at different stages and in different ways as described above.

In a particular embodiment, the components of the composition of the invention comprising dry collagen powder, water and optionally one or more additives are mixed before feeding the components into a single screw extruder.

In another specific embodiment, the dry collagen powder is fed to an twin screw extruder equipped with a side feed hopper that allows for the discrete addition of as much variable amount of water and one or more additives as desired. In another particular embodiment, the desired amount of the selected additive may be mixed into the dry collagen powder at a particular metering location. Other additives may be fed to the extruder from individual hoppers in a predetermined portion of the twin screw extruder. In certain embodiments, the process is performed in a continuous mixing system.

As mentioned above, with respect to the process for the preparation of the dry collagen powder of the invention, the dry collagen powder may be stored in a suitable storage tank after the preparation. Thus, in certain embodiments, the dry collagen powder is then conveyed from the storage tank to the high shear mixing system, preferably to the extruder, at a constant delivery rate. In the region adjacent to the supply of dry collagen powder, water is added in an appropriate proportion to achieve the desired amount of water by means of a metering pump controlled in the flow of dry collagen powder.

Depending on the amount selected and the components selected to be treated in accordance with the process of the invention, different treatment times are necessary to prepare the homogeneous thermoplastic composition of the invention. In certain embodiments, the mixture of components is typically processed in an extruder for a period comprised between 2 seconds and 5 minutes, preferably between 5 seconds and 3 minutes.

Suitable operating temperatures are comprised between 30 ° C and 160 ° C, preferably between 75 ° C and 90 ° C. During conversion to the thermoplastic composition, pressures of 20 bar and 350 bar, preferably from 30 bar to 100 bar, are applied on the mixture.

In general, process conditions such as temperature distribution, depending on the extruder, pressure, screw speed and form, dry collagen powder, feed rate of water and additives, and throughput rate, can be readily controlled by one skilled in the art. The compositions of the invention exhibit similar behavior to thermoplastics and adequate fluidity to be formed or molded into articles by conventional thermoplastic processing techniques such as extrusion and injection molding.

Depending on the additive of the composition of the invention, the composition may be edible when it contains only food-grade ingredients. Thus, the compositions of the invention are suitable for the manufacture of various food products. In addition, the compositions of the invention may be suitably also used to obtain biodegradable and / or renewable and thus various low cost formed products.

Thus, another object of the present invention is the use of the inventive composition in the manufacture of products with a solid shape. The compositions of the invention obtained in the form of agglomerates may be followed by their preparation, which is another process directly for forming a solid shaped product by molding techniques known from the prior art. In an alternative embodiment, the solid pellets obtained in step (iii) can be used to form a product with a solid shape. This alternative represents the advantage that the pellet can be stored and later formed into a product.

Thus, another object of the invention is a product with a solid shape formed from the compositions of the invention in very different shapes, sizes and scales where numerous applications can be seen in various fields. Solid shaped products are not limited, but may include outdoor sports products such as golf tees; Sheet; Envelopes such as garbage bags; Trays; bottle; pipe; Tableware, including cups, plates, plates; Flatware or another food utensil including a knife, fork, cutlery; Pet-toys; Pet-chew; Food products including candy, sweets, snack foods; Animal feed; Flat membrane; Tubular membrane; Fishing lures, fishing lure; Wine gum type product; Foamed products; Packaging materials for other products; Loss-filled packing pellets; Food packaging materials and containers. In a particular embodiment, the pet-chew is a dog-chew formed from a composition of the invention comprising an additive that makes a product with a solid shape attractive to dogs. In a preferred embodiment, the composition of the invention comprises an additive selected from caramels as a colorant smoked as a scent and bacon as a flavor and mixtures thereof, and the composition is preferably formed in the shape of a bone.

In a particular embodiment, the shaped solid product is a flat or tubular membrane that is heat sealable, ie particularly useful for heat sealing by conventional thermo-sealing machines. Since heat sealing capacity is a poor nature of collagen membranes prepared according to classical collagen processing techniques, the potential of heat sealing membranes made from the compositions of the invention has been found to be particularly beneficial. This can be seen in Comparative Example 12, wherein the tubular membrane formed from the thermoplastic composition according to the present invention is heat sealable, while the commercially available collagen membrane "Coffi" (Naturin GmbH & Co. KG, Germany) Is not weldable.

In a preferred embodiment, the solid shaped product is a foamed product formed from the composition of the invention, comprising blowing agents of various shapes, dimensions and sizes suitable for different applications.

Advantageously, the solids of the invention when formed in a composition of the invention consisting solely of food-grade ingredients that can be consumed at non-toxic levels by animals, such as mammals, including humans, The shaped product is edible and thus the solid product of the invention can be safely consumed. The resulting edible product is, for example, candy, sweets and the like, and in the state of the art, the product is generally based on gelatin and hydrocolloid mixtures, sugars and flavors and / or flavoring agents. Such edible compositions of the invention are food products for consumption by other animals or humans, such as, for example, simple food or household pets or other animal feeds and the like; It is useful for making packaged products that can be consumed by the user, along with package contents, plates and silver cutlery, which can be consumed after a meal. According to the present invention, products with a solid shape may comprise edible flavoring agents such as cocoa, vanillin, fruit extracts such as strawberries and bananas and the like and colorants which can be adapted to taste in order to enhance the flavor of the edible product. have. The composition may also be nutritionally fortified, such as by inclusion of vitamins or minerals.

Products with the solid form of the invention are biodegradable. Thus products such as containers, bags such as trash bags, food utensils, pet toys, golf tees and other products can be discarded without environmental pollution or damage. In addition, solid shaped products, such as used food packaging materials and containers, can thus be collected and pasteurized, ground and pelleted for animal feed, such as fish feed. Since the composition within the scope of the present invention has a high content of organic nitrogen, the product of the invention can be added to the soil to improve or fertilize the soil.

Another object of the present invention is a process for producing a shaped solid product comprising the step of forming a composition of the invention. In a particular embodiment, the inventive composition in the form of agglomerates as obtained in step (ii) is then formed into a product having the desired solid shape in a so-called single-step process. In an alternative embodiment, the process for producing a shaped solid product comprises forming pellets as obtained in step (iii).

The solid shaped articles of the present invention can be produced by methods of formation known to those skilled in the art, relating to plastic materials. Such methods include, but are not limited to, compression molding, blown film extrusion, blown membrane co-extrusion, blow molding, rotational molding, transfer molding, extrusion molding, co-extrusion molding, vacuum Molding, pressure forming, expansion molding and injection molding. In a preferred embodiment, the forming method is injection molding. After the composition of the invention in the form of a lump has cooled and solidified, the molding apparatus is opened and a solid product having the shape of a mold cavity is obtained.

In certain embodiments, low-ratio expanded foam articles formed from the inventive compositions are made using counter-rotating twin screw extruders mounted with foam dies. The twin screw extruder performs both the process and foam extrusion function for the preparation of the inventive composition. Useful single extruders suitable for the production of low ratio expanded foam are standard single screw and bubble die, Rheomax 302 extruders with an L / D of 30: 1. Foamed products may be formed by molding techniques or extruded to provide foamed products such as packaging materials, lossy fills, foamed dishes and cups, and the like. In certain embodiments, water present in the compositions of the invention can be suitably used as blowing agent. According to another particular embodiment of the process, the carbon dioxide is pumped to a flow regulating zone of a co-rotating twin screw extruder, such as AVP type MP 19 TC, under a pressure of about 30 bar to 90 bar. Carbon dioxide is soluble in the composition of the invention. Generally preferred concentrations of carbon dioxide are from about 0.2% to 5% by weight, based on the composition of the invention.

In a particular embodiment, the composition of the invention is formed into a flat membrane, the manufacturing process comprising the steps of: (i) pressing and unrolling the composition through a slotted die; (ii) obtaining a primary membrane; (iii) drawing the primary membrane out of the heated calendar system until the desired wall thickness and membrane width are achieved. In another specific embodiment, the composition of the invention is formed into a tubular membrane, wherein the manufacturing process comprises the steps of: (i) pressing and unrolling the composition through an annular die; And (ii) forming the tubular membrane by blown membrane extrusion. The tubular membrane thus obtained can be oriented in a single or two axes by techniques known in the manufacture of plastic tubes by those skilled in the art, such as in the production of sausage packages from polyamide based membranes. In another particular embodiment, the composition of the invention is formed into a tape, wherein the manufacturing process includes (i) pressing down the composition through a flat die and forming a tape. In another particular embodiment, the composition of the invention is formed into a hollow body, wherein the manufacturing process comprises the steps of: (i) pressing and stretching the composition through a parison die; And (ii) blowing it into the shape of a hollow body. In another particular embodiment, the composition of the invention is formed by co-extrusion of two or more overlapping flat or tubular films, which may be formed differently in color, composition, and / or other chemical and / or Or can be imparted with physical properties to produce a multilayered flat or tubular film. In turn, the tubular membrane may enclose an interior having the same or different properties that were simultaneously extruded through the central orifice of the multilayer blown membrane die. Multilayer co-extruded membranes of thermoplastic compositions can be obtained by combining layers of different compositions of the invention, or by combining layers of the compositions of the invention with other layers made of natural or synthetic polymeric materials.

In addition, after the shaped solid product has been produced, it may be subjected to a curing atmosphere or curing bath known in the art, optionally including a chemical crosslinking agent. Typical crosslinking agents used in hardening baths include, but are not limited to, certain polyvalent irons such as formaldehyde, bifunctional aldehydes, transglutaminase, carbodiimide, Fe ³⁺ , Cr ³⁺ , Al ³⁺ . Typical curing atmospheres include gas crosslinkers, such as acrolein. This curing process can impart different properties to the solid shaped articles formed from the compositions of the invention, such as, for example, reduced swelling force, increased water resistance, and alteration of physical and / or mechanical properties, making them insoluble.

Advantageously, a product with a solid shape formed from a composition of the invention that exhibits high water resistance can tolerate exposure to water over a long period of time. Products made from the compositions of the invention may degrade over time exposed to moisture, resulting from immersion in the contents enclosed by the product, such as meat or meat emulsions, or in water or other direct contact with water, for example. However, the product remains in a trace amount substantially undamaged or undisassembled for a sufficiently extended period of time. The time may be pre-determined depending on the selective curing treatment of the product and the formulation of the composition of the invention selected to form a product with a solid shape.

Products of the invention exhibit high levels of tensile strength and elongation, high tear strength, high compressive strength, and good resilience. In a particular embodiment, the article made by injection molding exhibits a high tensile strength of about 20 Mpa and a percentage of elongation at break of about 200%. The shrinkage of the product with the obtained shaped solid shape is very slight and can be controlled through the addition of additives, for example an effective amount of crosslinking agent and / or plasticizer. Another advantage of the solid shaped product of the invention may be that the products have the desired bright color for consumer products. After use, the solid shaped products of the invention, such as household products, dishes and containers, etc., can also be collected and pasteurized, ground, and, among others, made into products such as animal feed, soil conditioners, etc. Can be. The above is an illustration of the present invention. However, this invention is not limited to the following specific examples described herein, but includes all equivalent modifications within the scope of the following claims.

Example 1: Preparation of Dry Collagen Powder

A 10 kg piece of limeskin hide is soaked in 30 liters of water at room temperature in a tannery drum. The material is completely wet in 24 hours. The soaking water is then slowly drained and the rehydrated collagen raw material is cut into pieces having a diameter of about 10 mm in the first chopping step. To achieve this degree of pre-comminution, the rehydrated collagen stock is processed in the cutter for 1 minute. The pre-chopped collagen raw material discharged from the cutter is transferred to a passing machine equipped with a crusher plate having a hole of 2 mm diameter. The resulting finely chopped material is a worm shaped thread having a cross-sectional diameter of about 2 mm.

The obtained cylindrical particles are then stacked in a layer of 3 cm on a plate and placed in a furnace-type furnace at 80 ° C. After 16 hours, the complete cross section of the stacked particles is dry, with a residual water content of less than 7% by weight. This dry material is brittle, which is a prerequisite for grinding the dry material into fine collagen powder. Through the twin-screw feeder, brittle particles are fed to the hopper of a turbo rotor mill (TRM; Gorgens Company, Germany). The particle size distribution can be altered by adjusting the different rotational speeds of the turbo rotor. At a flow rate from 200 g / min through the mill and at a rotational speed of the turbo rotor at 4221 rpm, the average particle size of the powder is found to be less than 60 μm.

When stored under ambient conditions (22 ° C./60% relative humidity / 48 hours), the dry collagen powder absorbs about 7% by weight of water.

Example 2: Preparation of Granular Aggregates Starting from Fine Dry Collagen Powder and Water

700 g of dry collagen powder (with 7% by weight of residual water content) and 300 g of water obtained according to Example 1 are added to the vessel and briefly mixed together by hand. The resulting mixture is then delivered to a rapid laboratory mixer (MSHK 25, Plasthtech Company, Grits). The knife rotates at 3000 rpm at the bottom of the rapid laboratory mixer and causes efficient mixing of the components. After 15 seconds, the vessel is cleared through the discharge orifice at the bottom of the mixer. The result of the mixing process is a granular aggregate, which can be further processed according to step (ii) of the process for the production of the homogeneous thermoplastic composition of the invention.

Example 3a: Preparation of coarse granule aggregates starting from fine dry collagen powder, water and plasticizer

An aqueous plasticizer solution is prepared by mixing 300 g of water and 175 g of glycerol in a container. Next, 700 g of dry collagen powder (with 7% by weight of residual water content) prepared according to Example 1 are added to the aqueous plasticizer solution and all the components are briefly mixed together by hand. The resulting mixture is then transferred to a rapid laboratory mixer (MSHK 25, Plasthtech Company, Grits). The knife rotates at 3000 rpm at the bottom of the mixer and causes efficient mixing of the components. After 15 seconds, the vessel is cleared through the discharge orifice at the bottom of the mixer. The result of the mixing process is a coarse granule aggregate. The aggregates obtained are stored in a sealed sealed bag to prevent loss of water.

This coarse granular aggregate is optionally further introduced into the extruder and further processed according to step (ii) of the process for the preparation of the thermoplastic composition of the invention in the form of pellets.

Example 3b Preparation of Inventive Compositions Based on Dry Collagen Powder, Water and Plasticizers by Mixing the Individual Components in a Single Screw Extruder

The dry collagen powder (p) (having 7% by weight of residual water content) and liquid components such as water (w) and glycerol (g) prepared according to Example 1 were prepared using a single screw extruder (HAAKE RHEOMEX 302 single screw type). Feed to the hopper of the extruder (L / D = 30). The components are introduced at a relative flow p / w / g = 55% / 30% / 15% by weight at a total flow rate of 1 kg / h.

The individual components are mixed together by conveying the components through the mixing zone along the extruder barrel. The homogenization section at the end of the screw results in an efficient mixing process. All heating zones along the barrel are set at 90 ° C. The mixture is extruded through a pelletizing die into strands having a diameter of about 2 mm. The extruded strand is processed into pellets by a strand pellet maker (Modell Nr. 8 812 01, Brabender Company). The extrusion pressure during the process is 150 bar. The pellets obtained are stored in a sealed sealed bag to prevent loss of water.

Example 3c Preparation of Inventive Compositions Based on Dry Collagen Powder, Water and Plasticizer by Mixing Individual Components in a Twin Screw Extruder

Dry collagen powder (p) prepared according to example 1 (with a residual water content of 7% by weight) is fed to the hopper of a twin screw extruder (APV twin screw extruder type MP19TC (L / D = 40: 1)) . Water (w) and glycerol (g) are laterally fed via gear pumps in adjacent areas. The components are introduced at a relative flow rate of p / w / g = 55% / 30% / 15% by weight at a total flow rate of 1 kg / h.

The individual components are mixed together by conveying the components through the mixing zone along the extruder barrel. The mixing component of the twin screw in the flow regulating area results in an efficient mixing process. All heating zones along the tub are set at 90 ° C. The mixture is extruded through a pelletizing die into strands having a diameter of about 2 mm. The extruded strand is processed into pellets by a strand pellet maker (Modell Nr. 8 812 01, Brabender Company). The extrusion pressure during the process is 180 bar. The obtained pellets are stored in a sealed sealed bag to prevent loss of water.

Example 4: Preparation of Pellets

One preferred composition of pellets is the following:

50 wt% dry collagen powder (prepared according to example 1)

25% by weight water

15 wt% glycerol

5 wt% wheat gluten

2 wt% cochineal powder (as colorant)

2 wt% vanilla spice (as flavor)

1% by weight citric acid (in mass form to control the flow properties of the composition of the invention

Pellets are made using a twin screw extruder. The dry collagen powder prepared according to Example 1 and all other solid ingredients (wheat gluten, cochinyl powder, vanilla flavor and citric acid) were twin screw extruders (APV twin screw extruder type MP19TC (L / D = 40: 1)). It is fed to the hopper from the feed section of the. Water and glycerol are laterally fed through the gear pump in adjacent areas so that all components are mixed and transformed into thermoplastic mass in one continuous process. The temperature along the barrel and the die temperature are set at 90 ° C. during the deformation and extrusion process into the thermoplastic mass. The rotational speed of the screws is set at 70 rpm. The extrusion pressure during the process is 180 bar. The mixture is extruded through a pelletizing die into strands having a diameter of about 2 mm. The extruded strands are pelleted by a strand pellet maker (Modell Nr. 8 812 01, Brabender Company). The pellets obtained are stored in a sealed sealed bag to prevent loss of water.

Example 5 Use of Citric Acid to Control Flow Properties of agglomerates

Example 5a: Citric Acid-Free Test

Pellets having the following compositions are prepared according to one of the methods described in Examples 3 or 4:

56% by weight of dry collagen powder (prepared according to example 1)

24% by weight of water

20% by weight of glycerol.

The pellets obtained are then introduced into the hopper of a single screw extruder (HAAKE RHEOMEX 302 single screw extruder (L / D = 30)) at a flow-rate of 1 kg / h. Single screw extruders operate under steady state conditions. The temperature along the barrel and the die temperature are set at 90 ° C. during the extrusion process. The rotation speed of the screw is set at 70 rpm. The conveyed thermoplastic mass is extruded into tape through a flat die (cross section of die: 70 mm x 0.8 mm). With this setting, the extrusion pressure measured at the end of the extruder barrel is 350 bar.

Example 5b: Test with Citric Acid

Pellets having the following compositions are prepared according to one of the methods described in Examples 3 or 4:

56% by weight of dry collagen powder (prepared according to example 1)

24% by weight of water

17.5 wt% glycerol

2.5% citric acid.

The pellets obtained are then introduced into the hopper of a single screw extruder (HAAKE RHEOMEX 302 single screw extruder (L / D = 30)) at a flow-rate of 1 kg / h. Single screw extruders operate under steady state conditions. The temperature along the barrel and the die temperature are set at 90 ° C. during the extrusion process. The rotation speed of the screw is set at 70 rpm. The thermoplastic mass is extruded to tape through a flat die (cross section of die: 70 mm x 0.8 mm). With this setting, the extrusion pressure measured at the end of the extruder barrel is only 150 bar.

The presence of citric acid causes a lower viscosity of the thermoplastic mass during the extrusion process. The change in flow properties due to the reduced viscosity of the mass is represented by the reduced extrusion pressure as compared to Example 5a.

Example 6 Preparation of Dog Bone from Thermoplastic Compositions According to the Invention by Injection Molding

Example 6a: Production of Dog Bone by Extrusion of Thermoplastic Lumps and Direct Transfer of Pellets to the Hopper of an Injection Molding Apparatus

The collagen powder prepared according to Example 1 is fed to the hopper of a twin screw extruder (APV twin screw extruder type MP19TC (L / D = 40: 1)). In the adjacent area along the extruder barrel additionally liquid and solid components can be fed sideways to the flow of collagen powder.

The individual components are mixed together by conveying the components through the mixing zone along the extruder barrel. The mixing component of the twin screw in the flow regulating area results in an efficient mixing process. All heating zones along the tub are set at 90 ° C. The rotation speed of the screw is set at 80 rpm.

In the first side feed zone, premixed water, colorant "caramel" (10% by weight based on water); Spice "bacon" (10% by weight in water) and fragrance "smoked" (6% by weight in water) are added to the flow of powder at a rate of 15% by weight (based on powder) via a gear pump. Likewise, 20% by weight (based on powder) of glycerin in another adjacent side feed zone is added to the stream of dry collagen powder. The extrusion pressure during the process is 180 bar. The thermoplastic mass is extruded through the pelletizing die into strands having a diameter of about 2 mm. The extruded strands are pelleted by a strand pellet maker (Modell Nr. 8 812 01, Brabender Company). The pellets are led to the hopper of a direct injection molding machine (ARBURG Allrounder 221 M 350-55). The temperature and die temperature are set at 90 ° C along the tub. In an injection molding apparatus, pellets are converted into thermoplastic masses and inserted into molds to obtain products formed in the shape of dog-bones. After the thermoplastic mass is cooled and solidified, the forming apparatus is opened and a product having the shape of the mold cavity is obtained.

At the start of the injection phase the tool temperature is set at 70 ° C. The cavity of the frame has a volume of 140 cm 3. After injection, the apparatus is cooled to 30 ° C., which takes 15 minutes. Once the instrument has reached a temperature of 30 ° C., the molded dog bone is discharged.

Setting of the injection molding unit (ARBURG Allrounder 221 M 350-55):

Barrel Temperature: 90 ℃

Die temperature: 90 ℃

Injection volume: 140 cm3

Pressure: 800 bar

Speed: 80cm3 / s

3 cm storage volume

Holding pressure 150 bar

Retention pressure time 3 seconds

Total cycle time: 15 minutes

Notably, shorter circulation times could be obtained using intrusion units instead of devices for injection molding.

Example 6b: Preparation of dog bone by conveying the prepared pellets to the hopper of the injection molding apparatus

Although made according to either of the methods described in Examples 3 and 4, the pellets having the composition of Example 5b are conveyed to the hopper of an injection molding machine. The temperature and die temperature are set at 90 ° C along the tub. The pupil of the mold has a negative phase of dog bone with a volume of 140 cm 3. At the start of the injection bed the instrument temperature is set at 70 ° C.

After the injection phase the instrument is cooled to 30 ° C., which takes 15 minutes. Once the instrument has reached a temperature of 30 ° C., the molded dog bone is discharged.

Setting of the injection molding unit (ARBURG Allrounder 221 M 350-55):

Barrel Temperature: 90 ℃

Die temperature: 90 ℃

Injection volume: 140 cm3

Pressure: 800 bar

Speed: 80cm3 / s

3 cm storage volume

Holding pressure 150 bar

Retention pressure time 3 seconds

Total cycle time: 15 minutes

Notably, shorter cycle times could be obtained using intrusion devices instead of devices for injection molding.

Example 7 Formation of Flat Films from Thermoplastic Compositions According to the Invention by Calendering

Although prepared according to any of the methods described in Examples 3 and 4, the pellets having the composition of Example 5b were prepared at twin flow extruder (APV twin screw extruder type MP19TC (L / D = 40: It is supplied to the hopper of 1)).

The temperature along the barrel and the die temperature are set at 90 ° C. during the extrusion process. The rotation speed of the screw is set at 70 rpm. The thermoplastic mass is extruded into tape through a flat die (cross section of die: 70 mm x 0.8 mm).

Notably, the dry collagen powder and citric acid prepared according to Example 1 are fed to the hopper at the feed. Water and glycerol are laterally fed through a gear pump in adjacent areas so that the powder, citric acid, water and glycerol are mixed and converted into thermoplastic mass in one continuous process. The temperature along the barrel and the die temperature are set at 90 ° C. during the conversion and extrusion process into the thermoplastic mass. The rotation speed of the screw is set at 70 rpm. Again, the composition in the form of agglomerates is extruded into tape through a flat die (cross section of die: 70 mm x 0.8 mm). The extrusion pressure during the process is 250 bar.

The extruded tape produced according to either of the aforementioned methods is then subjected to a nip between the heated rolls (Chill-Roll 136/350 (H), Colin Company) of the polishing stack ( 0.03 mm).

Except for the chill roll, the roll temperature of the abrasive lamination is set to 60 ° C. Due to the pressure in the nip, the extruded tape is calendered into a flat membrane having a thickness of less than 10 μm and a width of 150 mm. The calendared membrane is led over a chill roll and eventually wound on a wind-up device.

Example 8 Formation of Tubular Membranes from Thermoplastic Compositions According to the Invention by Blown Membrane Extrusion

Although prepared according to any of the methods described in Examples 3 and 4, the pellets having the composition of Example 5b were prepared at twin flow extruder (APV twin-screw extruder type MP19TC (L / D = 40) at a flow rate of 1 kg / h. (1)) is supplied to the hopper. The temperature along the barrel and the die temperature are set at 90 ° C. during the extrusion process. The rotation speed of the screw is set at 70 rpm.

Notably, the dry collagen powder and citric acid prepared according to Example 1 are fed to the hopper at the feed. Water and glycerol are laterally fed through a gear pump in adjacent areas so that the powder, citric acid, water and glycerol are mixed and converted into thermoplastic mass in one continuous process. The temperature along the barrel and the die temperature are set at 90 ° C. during the conversion and extrusion process. The rotation speed of the screw is set at 70 rpm.

The thermoplastic mass produced according to either of the aforementioned methods is extruded into the tube through a blown membrane die (nominal diameter: 30 mm, nominal annular spacing: 0.8 mm). The inflating air forms a membrane bubble and later maintains its form. The extrusion pressure during the process is 260 bar.

The extruded tubular membrane is led onto a pinch roll with a wind up device.

Example 9 Formation of Foam Product from Thermoplastic Compositions According to the Invention

The thermoplastic composition based on the collagen is produced in a twin screw extruder (APV twin screw extruder type MP19TC (L / D = 40: 1)) which is treated as follows:

The dry collagen powder, cochinyl powder and citric acid produced according to Example 1 are fed to the feed to the first hopper. The plasticizer solution based on water and glycerol is laterally fed through the gear pump in the adjacent feed zone so that the powder and plasticizer solution are mixed and converted into thermoplastic mass in one continuous process. Ethanol is laterally fed to the third feed zone by a gear pump. The temperature along the barrel and the die temperature are set at 90 ° C. during the conversion and extrusion process. The rotation speed of the screw is set at 70 rpm. The total flow rate of the thermoplastic collagen-based composition is 1 kg / h. The composition of the mass is as follows:

50% by weight of the dried collagen powder prepared according to Example 1

25% by weight of water

15 weight percent glycerol

5 wt% cochineal powder

5% by weight of ethanol as blowing agent.

A foaming temperature of at least 80 ° C. must be reached in the flow rate regulating region. The released ethanol vapor is uniformly dispersed by a pair of screws mounted with a kneading disc in the flow regulating zone.

The mass is extruded through a die having a circular cross section with a diameter of 3 mm. During the process, the extrusion pressure is 230 bar. The extruded red cylindrical strands foam while leaving the die due to the expansion of the exiting gas. The diameter of the foamed strand is 8 mm.

Example 10 Preparation of Bottle-shaped Products from Thermoplastic Compositions According to the Invention by Blow Molding

Although prepared according to any of the methods described in Examples 3 and 4, the pellets having the composition of Example 5b were fed into the hopper of a twin screw extruder (APV twin screw extruder type MP19TC (L / D = 40: 1)). It is introduced at a flow rate of 1 kg / h. The die temperature is set to 90 ° C. during the extrusion process and along the barrel. The rotation speed of the screw is set at 70 rpm.

The thermoplastic mass carried through the extruder is extruded into a tube through a parison die (nominal diameter: 30 mm, nominal annular spacing: 1.0 mm). The extrusion pressure during the process is 210 bar.

The extruded tubular parison is held by closed blow molding and blown into a bottle shape by compressed air provided through a blow mandrel. The blow molded bottle has a height of 150 mm and a diameter of 80 mm. The temperature of blow molding is set to 20 ° C. The pressure of the compressed air is 6 bar. After the parison blows back to its original state, the blow molding opens and the bottle is ejected. The wall thickness of the blow molded bottle is 300 μm.

Example 11: Use of Pellets Prepared Similarly to Example 3 (or 3a) to Form Foamed Product by Injection Molding

Pellets with a certain amount of physical blowing agent are made similar to Example 3 or 3a. (If pellets are made similar to Examples 3b, 3c, or 4, the extrusion temperature must be set below the boiling point of the physical blowing agent.)

The composition of the pellets with physical blowing agent is as follows:

50% by weight of dry collagen powder prepared according to Example 1

25% by weight of water

20% by weight glycerol

5 wt% ethanol as blowing agent

The pellets are conveyed to the hopper of the injection molding machine. The temperature and die temperature are set at 110 ° C along the tub. The instrument temperature is set at 20 ° C. The pupil of the frame has the shape of a plate having a dimension of 180 mm x 80 mm x 8 mm. The pupil fills the mass due to the expansion of the gas (the ethanol and water vapors) that is completely expelled. The mass cools due to contact with the walls of the mold for a period of 120 seconds. The molded foam plate is discharged after the injection phase.

Setting of the injection molding machine (ARBURG Allrounder 221 M 350-55):

Barrel Temperature: 110 ℃

Die temperature: 110 ℃

Appliance temperature: 20 ℃

Injection volume: 105 cm3

Injection pressure: 800 bar

Speed: 80 cm3 / s

Cycle time: 120 seconds

It is to be understood that the formulations described above are merely illustrative of the application of the principles of the invention. Countless other combinations can be readily devised by those skilled in the art to embody the principles of the invention and to fall within the spirit and scope of the invention.

Comparative Example 12: Contact welding compared by use of a welding press

A piece of air dried tubular membrane having a flat width of 150 mm and a wall thickness of 100 μm, formed from the thermoplastic collagen composition according to Example 8, obtained by blown film extrusion, is used to prepare the envelope by heat sealing. Heat sealing is carried out on the welding press type SP3, the joke company. The welding press has two sealing bars and its contact area is 250 mm x 3 mm. The temperature of the upper seal bar is adjusted to 100 ° C. The low PTFE covered sealing bar is not heated. One open end of the tubular membrane is introduced between the gaps of the sealing bars. During the welding process the top heated sealing bar is lowered to a PTFE covered bar. The welding pressure is adjusted to 300N, and the welding time is 2 seconds. Thereafter, the heated bar is discharged. The weld strength of the seam reaches a tensile strength of at least 100% of the membrane material.

The same kind of test was performed using a commercially available air dried collagen membrane ("Kopy", membrane made by Naturin GmbH & Co. KG, Germany), where the collagen component of the membrane was intact (unique) , Microfibers) collagen. Such membranes are not weldable.

The invention provides a new collagen based technique. The invention provides dry collagen powder as precursor for the production of homogeneous thermoplastic collagen-based compositions, which may further comprise additives. The present invention also relates to the use of the compositions and articles in the manufacture of solid articles formed according to plasticity techniques.

Claims (38)

Dry collagen based on modified or partially modified microfiber forming collagen, exhibiting an average molecular weight of at least 500 kD, 25% greater or the same solubility in water at 60 ° C., and an average particle size comprised between 30 μm and 350 μm. powder. 2. The dry collagen powder according to claim 1, which is an average particle size comprised between 50 µm and 100 µm. Process for the preparation of the dry collagen powder according to any one of the preceding claims, comprising: a) chopping the collagen raw material into cylindrical particles; b) drying said cylindrical particles at or above the denaturation temperature of collagen until the complete cross section of the individual particles is dry and brittle; c) milling the particles obtained from step b); d) obtaining dry collagen powder. The process of claim 3 wherein the particles are dried at a temperature comprised between 60 ° C. and 80 ° C. in step b). 4. The method of claim 3, wherein the collagen raw material is selected from cows, pigs, calves, lambs, sheep, goats, horses, kangaroos, camels, chickens, ostrichs, crocodiles, salmon and herrings. Obtained from tissues selected from bone proteins (ossein), tendons, intestines and cartilage derived from bone, preferably from cowhide and pig leather, preferably unlimed leather, lime leather A process characterized in that it is selected from limed leather pieces, pelts of leather and pieces of pig leather, and more preferably lime leather pieces. 4. Process according to claim 3, wherein the collagen raw material is modified or partially modified by conventional heating means, prior to step a). Use of a dry collagen powder according to any of the preceding claims in the preparation of a homogeneous thermoplastic collagen-based composition. A homogeneous thermoplastic collagen-based composition comprising the dry collagen powder according to claim 1 or water. The homogeneous thermoplastic collagen-based composition of claim 8 comprising: (i) 20% to 95% dry collagen powder; And (ii) 5% to 80% by weight of water. 10. The homogeneous thermoplastic collagen-based composition of any one of claims 8 or 9, further comprising a plasticizer. The homogeneous thermoplastic collagen-based composition according to any one of claims 8 to 10, comprising between 5% and 50% by weight plasticizer. 12. The homogeneous thermoplastic collagen-based composition according to any one of claims 8 to 11, further comprising: (i) 40% to 65% dry collagen powder; (ii) 20% -40% water; And (iii) 10% to 20% by weight of plasticizer. 13. The homogeneous thermoplastic collagen-based composition according to any one of claims 10 to 12, wherein the plasticizer is glycerin. The method of claim 8, wherein the protein, biodegradable polymer, blowing agent, modifier, filler, lubricant, crosslinking agent, preservative, colorant, rheology improver, flavoring agent and scent, nutrient and their A homogeneous thermoplastic collagen-based composition, further comprising an additive selected from the group of the mixture. 15. The homogeneous thermoplastic collagen-based composition of claim 14, wherein the protein is selected from animal derived proteins, plant derived proteins, microbial proteins and mixtures thereof. 16. The homogeneous thermoplastic collagen-based composition according to claim 15, wherein the dry collagen powder content is at least 30% by weight of the total protein content. The method according to claim 14, wherein the biodegradable polymer is polyhydroxyalkanoate, polyalkylene ester, polylactic acid, polylactide, poly-ε-caprolactone, polyvinyl ester, polyvinyl alcohol and mixtures thereof A homogeneous thermoplastic collagen-based composition, characterized in that it is a natural or synthetic thermoplastic selected from the group consisting of: 15. The method of claim 14, comprising 56% by weight of dry collagen powder; 24 weight percent water; 17.5 weight percent glycerin; And 2.5% by weight citric acid. 15. The method of claim 14 further comprising: 50% by weight of dry collagen powder; 25% water by weight; 15 weight percent glycerin; A homogeneous thermoplastic collagen-based composition, characterized by consisting of 5% by weight cochinyl powder and 5% by weight ethanol. 15. The method of claim 14 further comprising: 50% by weight of dry collagen powder; 25% water by weight; 15 weight percent glycerin; 5% wheat gluten; 2 weight percent cochineal powder; 2 weight percent vanilla flavoring; And 1% by weight citric acid. 15. The method of claim 14, further comprising: dry collagen powder; 15 weight% water including 10 weight% pigmented caramel based on water; 10% by weight fragrance bacon based on water; And 6% by weight fragrance smoked pigment caramel based on water; 20% by weight glycerin; And 2.5% by weight citric acid. 15. The method of claim 14 further comprising: 50% by weight of dry collagen powder; 25% water by weight; 20% by weight glycerin; And 5% by weight of ethanol. A process for obtaining a homogeneous thermoplastic collagen-based composition according to any one of claims 8 to 22, comprising the following steps: (i) mixing the dry collagen powder with water; (ii) the mixture of dry collagen powder and water obtained in step (i) of shear force at a pressure comprised between 20 and 350 bar and at 30 and 160 ° C. until the components are converted into a homogeneous thermoplastic collagen-based composition. Placing at a temperature comprised in between; And optionally (iii) converting the homogeneous thermoplastic collagen-based composition in lump form into pellets. The method of claim 23, further comprising the addition of one or more additives to the dry collagen powder, to water, to step (i), or to step (ii), simultaneously or separately, wherein the additive is in the form of agglomerates. And homogeneously incorporated into the homogeneous thermoplastic collagen-based composition or pellet obtained. The process of claim 23, wherein the process is performed in a continuous mixing system. Use of a homogeneous thermoplastic collagen-based composition according to any one of claims 8 to 22 for the production of shaped solid products. 23. A solid product having a shape formed from the homogeneous thermoplastic collagen-based composition according to any one of claims 8 to 22. 28. The system of claim 27, further comprising: outdoor sports products; Sheet; envelope; tray; bottle; pipe; Tableware, including cups, plates, plates; Flatware or another food appliance including a knife, fork, cutlery; Pet toys; Pet chewing cookies; Food products including candy, sweets, snack foods; Animal feed; Flat membrane; Tubular membrane; Fishing lures, fishing lure; Wine gum type product; Foamed products; Packaging materials for other products; Loss-filled packing pellets; A solid product with a shape, characterized in that it is selected from food packaging materials and containers. 29. The solid product of claim 28, wherein the animal chew cookie is a dog-chew. A process for producing a solid product shaped in accordance with claim 27 comprising forming a homogeneous thermoplastic collagen-based composition. 31. The method of claim 30 comprising forming a pellet as obtained in step (iii) according to claim 23 or subsequently forming a homogeneous thermoplastic collagen-based composition in lump form obtained in step (ii). Process for producing a solid product having a shape, characterized in that. The method of claim 30 or 31, wherein the compression molding, blown film extrusion, blown membrane co-extrusion, blow molding, rotational molding, transfer molding, extrusion molding, A process for producing shaped solid products characterized by a forming method selected from co-extrusion molding, vacuum forming, pressure forming, expansion molding and injection molding. 33. The process of claim 32, wherein the forming method is injection molding. 32. The method of claim 31, further comprising: (i) pressing down the homogeneous thermoplastic collagen-based composition through a slotted die, (ii) obtaining a primary membrane; (iii) drawing the primary membrane out of the heated calender system until the desired wall thickness and membrane width are achieved. 32. The method of claim 31, further comprising the steps of: (i) pressing down on the homogeneous thermoplastic collagen-based composition through an annular die; And (ii) forming the tubular membrane by blown membrane extrusion. 32. The process of claim 31, comprising: (i) pressing through the flat die to spread the homogeneous thermoplastic collagen-based composition and forming a tape. 32. The method of claim 31, further comprising the steps of: (i) pressing down on the homogeneous thermoplastic collagen-based composition through a parison die; And (ii) blowing the composition into the shape of a hollow body. 38. A solid product having a shape obtained by the process according to any one of claims 30 to 37, which is further subjected to a curing bath or a curing atmosphere.