CH635357A5 - Process for the preparation of liquid solutions of products of the reaction of solid organic compounds containing NH groups - Google Patents

Description

The present invention thus relates to a process for the preparation of liquid solutions of reaction products of solid, NH groups-containing, organic compounds, characterized by the liquefaction of solid, NH-group-containing, organic compounds by reaction thereof with glyoxal dissolved in water to form reaction products .

Such reaction products can be incorporated into a collagen mass in order to produce a molding compound which in turn can be used for the production of foils, in particular tubular foils for packaging sausages.

It has been shown that the reaction products obtainable according to the invention, consisting of an aqueous glyoxal solution and solid organic compounds containing NH groups, act as a hardening additive to collagen masses in small proportions and provide films or tubes with a wet strength not previously achieved. The reaction products can thus be added to animal skin fiber in small quantities as hardening agents.

The invention further relates to the use of a molding composition which contains a) animal skin fiber mass (collagen) and b) reaction products in which residues derived from solid organic compounds containing NH groups are bonded to residues derived from glyoxal and for the preparation thereof solid, Organic compounds containing NH groups have been reacted with glyoxal dissolved in water for the production of moldings, preferably tubular films, in particular sausage casings, by shaping and drying the molding composition. Component b) corresponds to the aminoplast precondensates in the molding composition according to CH-PS No. 606 248 and acts as a hardening agent. The molding compositions can be shaped in a manner known per se (for example by wet or dry extrusion) and the films obtained can be dried in a known manner and subjected to further treatments, such as curing and / or tanning and softening.

The process according to the invention can be carried out in a simple manner by mixing an aqueous solution of glyoxal, which is preferably 40% by weight, with the solid organic compound containing NH groups and then mixing until the abovementioned is completely dissolved Leaves connection. The dissolution process can be accelerated by heating and / or stirring.

It is advisable not to heat much higher than 100 ° C, since the solutions turn darker with increasing temperature. It is advantageous to heat to about 60 ° C, although the dissolution process takes a little longer. However, comparatively bright solutions are obtained for this.

The duration of the solution process depends on the material used, i.e. on the type of solid, NH groups-containing, organic compound, and on the other conditions, such as heating and / or stirring, and is usually about% to 3 hours.

Solid organic compounds containing NH groups include, for example Amines, amides, imines and also proteins in question. Solid, NH-containing organic high molecular materials with a molecular weight of at least 20,000, e.g. Proteins.

Examples of suitable solid organic compounds containing NH groups include gelatin, casein, collagen, keratin, horn, wool and silk, all of which can be liquefied according to the invention. Colloil can be in its most varied forms, e.g. in the form of skin bones, skin fiber masses, hardened skin fiber casings, but also in the form of leather or natural casings. Waste collagen, such as waste from hardened skin fiber casings and leather waste, can also be liquefied and used as a hardening component. Plant proteins such as soy casein and plant globulins are also suitable as solid organic compounds containing NH groups.

The crosslinking properties of the reaction products obtainable according to the invention can be varied even further by dissolving additional substances in them. The reaction products from an aqueous glyoxal solution and solid organic compound containing NH groups surprisingly show the ability to redissolve other substances. A large number of partially high-molecular organic substances (which may require heating) are dissolved, for example proteins such as gelatin, collagen, elastin, keratin, fibroin, serine (horn, wool, silk), and also Cel-30 lulose and cellulose derivatives, such as methyl cellulose, starch, wood (Iignin), plastics, such as polyamides, aminoplasts, polyester, polyurethane, polyamides (nylon 6, nylon 11,

Nylon 12), caprolactam etc.

An example of the extensive resolving power 35 of the reaction products obtainable according to the invention is the dissolution of a complete animal body [mole (Talpa europaea)] in a reaction product from an aqueous glyoxal solution and hardened skin fiber intestines. The animal's body completely dissolved, including skin and hair, claws, teeth, bones and innards.

In the process according to the invention, the glyoxal is preferably used in excess of the solid organic compound containing NH groups. Suitable mole ratios of glyoxal to the compound mentioned are in the range from 0.5 to 5.0, preferably 0.8 to 1.5 moles of glyoxal: 1.0 to 5.0, preferably 1.0 to 3.0 moles of Compound based on the amino group. The aqueous glyoxal solutions can vary in concentration from 25 to 80, preferably from 30 to 50% by weight. A concentration of about 40% by weight is preferred.

The solid organic compound to be liquefied, containing NH groups, is advantageously pre-swollen in water, better still in dilute acid, before the reaction with the 55 aqueous glyoxal solution. This speeds up the solution process.

The crosslinking of proteins such as gelatin, collagen etc. with aldehydes such as formaldehyde, glyoxal, methyl-60 glyoxal etc. is known. The reaction products obtainable according to the invention from an aqueous glyoxal solution and solid organic compounds containing NH groups, such as proteins, for example collagen, surprisingly have a higher crosslinking activity than the corresponding amount of glyoxal. The crosslinking activity of these reaction products increases with increasing reaction time at a constant reaction temperature (usually around 100 ° C). The networking continues

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activity of the reaction product in contrast to that of aldehydes with decreasing pH.

The use of the reaction products obtainable according to the invention as a hardening component in molding compound based on collagen offers, in addition to the already mentioned advantages of high wet strength and the possibility of also utilizing waste collagen, the further advantage that additional plasticizers, such as glycerol, sorbitol and others, are dispensed with can be avoided, the well-known disadvantage that additional plasticizers reduce the wet strength of collagen films.

As already mentioned, the reaction products obtainable according to the invention are effective in comparatively small amounts as a hardening component in collagen masses. Quantities of 0.1 are sufficient for this purpose. up to 5% by weight, based on dry collagen. As a rule, amounts of 0.2 to 4% by weight are used, with amounts of 1 to 3% by weight being preferred. Additions in these quantities do not affect the shelf life of the molding material produced in this way with regard to its extrusion properties. Collagen masses with dry contents of 2 to 15, preferably 6 to 15% by weight collagen are preferred. You can also add other additives. The incorporation can take place in a manner known per se.

The production of animal skin fiber mass is known to the person skilled in the art; e.g. in DRP 641 169 and 659 490 (Naturin). The reaction product of an aqueous glyoxal solution and solid organic compound containing NH groups is expediently kneaded into the collagen mass by means of any known mixing devices if the collagen masses have a comparatively high dry matter content of more than about 6% by weight (e.g. approx 8 to 14% by weight), which after extrusion do not need to be solidified by special coagulation baths. If collagen slurries with a lower dry matter content of collagen are used (e.g. in the order of magnitude of 0.5 to 4% by weight of dry collagen), such aqueous slurries can only be processed after wet spinning (for example described in DE-PS 1 444 997 and US Pat. No. 3,123,653) are deformed, the tube after the extrusion first having to be solidified in one or more coagulation baths before it can be subjected to further treatments such as drying, tanning and / or softening. The reaction product obtainable according to the invention can also be added directly to such aqueous slurries.

Other additives include foreign fibers such as cellulose, dyes, plasticizers such as glycerin, sorbitol or carboxymethyl cellulose, and / or fungistatic agents. The amounts of these other additives depend on the type of additive. Fibers are generally mixed in amounts of up to 25% by weight, preferably up to 15% by weight, plasticizers in smaller amounts up to about 10% by weight, dyes in amounts of up to about 4% by weight , each based on dry collagen. A binder for excess aldehyde, preferably urea and / or casein, can also be added to the collagen mass.

The molding compositions according to the invention can be prepared in a manner known per se, e.g. be deformed by wet or dry spinning, preferably to tubular films which are suitable as sausage casings. The deformation of collagen masses is also known. As already mentioned, collagen masses with higher solids contents of e.g. 10 to 15 wt .-% are extruded through ring slot nozzles of various types, whereupon the hose is dried. Such dry spinning "cools and diluted 1: 1 with water (solution II).

processes are described in the above-mentioned DRP 641 169 and 659 490 and the nozzle constructions used, for example in the DRP 694 902.

In the wet spinning process, it is known that aqueous collagen absorbments with a lower dry matter content are first extruded in coagulating baths to fix the tube shape before the tube is then further treated.

After the shaping, the tube is dried, where the collagen is hardened and cross-linking bridges are formed between the aminoplast and the collagen.

Further treatments known per se with hardening agents, plasticizers and the like can be applied to the drying treatment. Connect like. The finished hose 15 can be subjected to a conditioning treatment, whereupon it can be gathered or wound on transport rollers.

For the production of collagen masses and their deformation, reference is made to the book "Sausage Casing Technology" by 20 Karms, Noys Data Corporation, Park Ridge, New Jersey (1974).

The invention is illustrated by the following examples.

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example 1

100 g of granular gelatin are pre-swollen in 1000 ml of water at room temperature for 30 minutes and then heated to 100 ° C. Now 100 ml of glyoxal (40% by weight - 30% aqueous solution, d 1.29) are added and the mixture is further heated to 100 ° C. for one hour (solution I).

Properties of solution I:

Color dark brown

Viscosity 50 "Ford cup, 2 mm, 20 ° C 35 V (red / ox) - 120 mV pH 7.2

Gel time (TECAM gelation timer) 20 ° C 10% HCl (18% by weight) = 7 min.

Mixing skin fiber mass with solution I:

40 60 kg of skin fiber mass with 11% by weight of dry collagen are slowly added to 1200 ml of solution I in the Zeta kneader. The mixture is kneaded further for an hour. pH of the final mass 4.5.

In a conventional system for the production of 45 skin fiber casings (extruder) an intestinal tube is produced from the skin fiber mass produced as above, which does not undergo any additional treatments, is dried and is wound up at the end of the production line.

Bowel data after 21 days:

50 water absorption capacity 190% by weight

pH 4.5

Wet tensile strength 4.2 kp / mm2 modulus 9.5 kp / mm2 Washable with water approx. 1% by weight 55 Hot water shrinkability at 75 ° C approx. 48% by weight. The product proves to be suitable as a raw sausage casing and is very easy to clip.

60 Example 2

200 g of skin fiber intestine hardened with smoke distillate, pure ground, are swollen for 30 minutes in 500 ml of 1% by weight HCl at room temperature. The HCl can also be omitted; the response times are then a little longer. 200 ml of glyoxal (40% by weight aqueous solution, d 1.29) are added. The mixture is heated to 100 ° C and stirred at this temperature for 1 hour. The resulting dark brown solution is removed

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Properties of solution II:

Viscosity 56 "Ford beaker 2 mm, 20 ° C V (red / ox) -320 to -350 mV pH 5.0

There are no free amino acids in DC:

no hydrolyzate.

Mixture of skin fiber mass with solution ILIO ml of solution II per 500 g skin fiber mass with 11% by weight dry collagen, pH 3.0, are kneaded in a Zeta mixer and mixed for 1 hour.

Skin fiber mass:

Dry matter content 11.3% by weight

pH 3.5.

Films of about 0.1 mm layer thickness were produced from the skin fiber mass on a roller mill. After 48 hours, a water absorption capacity of 280% by weight and an unusually high wet tensile strength in this swelling state were achieved.

Example 3

50 g of old, chrome-tanned leather was cut into fine strips and 125 ml of HCl (2% by weight) were added. 50 ml of glyoxal (40% by weight aqueous solution, s d 1.29) were then added; the mixture was stirred at 100 ° C for 3.5 hours. The result was a dark brown solution with low sediment that can be filtered off with glass wool.

With a result similar to that in Example 2, the resulting solution was mixed into skin fiber mass; films were produced from this mass which showed a relatively high wet tensile strength after a short time.

Example 4

15 92 g Wiener sausages, cut into slices, were mixed with 5 ml HCl (36% by weight) and 100 ml glyoxal (40% by weight aqueous solution, d 1.29), heated to 100 ° C. and stirred at this temperature for 30 minutes. The result was a dark brown solution with small, undissolved 20 fat residues.

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Claims (3)

635357 1. A process for the preparation of liquid solutions of reaction products of solid, NH groups-containing, organic compounds, characterized by the liquefaction of solid, NH-group-containing, organic compounds by reacting them with glyoxal dissolved in water to form reaction products. 2. The method according to claim 1, characterized in that the reaction takes place with heating and / or stirring. 3. The method according to claim 1 or 2, characterized in that the reaction is heated to temperatures up to 100 ° C, preferably to about 60 ° C. 4. The method according to any one of claims 1 to 3, characterized in that the glyoxal is used as a 40% by weight aqueous solution. 5. The method according to any one of claims 1 to 4, characterized in that heating and / or stirring for 0.5 to 3 hours. 6. The method according to any one of claims 1 to 5, characterized in that amines, amides, imines and / or proteins are used as solid organic compounds containing NH groups. 7. The method according to any one of claims 1 to 6, characterized in that gelatin, casein, collagen, keratin, horn, wool and / or silk are used as solid organic compounds containing NH groups. 8. The method according to claim 7, characterized in that collagen in the form of skin bumps, skin fiber masses, hardened skin fiber casings, leather and / or natural casings is used as solid organic compounds containing NH groups. 9. The method according to claim 7, characterized in that one uses collagen waste. 10. The method according to any one of claims 1 to 9, characterized in that the solid, NH groups-containing organic compounds are allowed to swell in water and / or dilute acid, if appropriate with heating, before the reaction. 11. The method according to any one of claims 1 to 10, characterized in that in the resulting aqueous solution of reaction products high molecular weight organic substances, such as proteins, cellulose and / or plastics, such as linear and / or crosslinked polycondensation and polyaddition compounds, are dissolved . 12. Use of reaction products from an aqueous glyoxal solution and solid, NH groups-containing, organic compounds for the production of molding compositions, characterized in that the reaction product is incorporated into a collagen mass. 13. Use according to claim 12, characterized in that the reaction product is mixed into a collagen mass with a dry content of 2 to 15, preferably 6 to 15 wt .-% collagen. 14. Use according to claim 12 or 13 for the production of molding compositions which contain foreign fibers, such as cellulose, dyes, plasticizers, such as glycerol, sorbitol or carboxymethyl cellulose, and / or fungi-static agents as further additives. 15. Use according to claim 12, characterized in that reaction products from an aqueous glyoxal solution and collagen are incorporated. 16. Use according to claim 12, characterized in that one incorporates a reaction product dissolved in an aqueous glyoxal solution. 17. Use according to claim 12, characterized in that the solid, NH-containing organic compound is an amine, amide, imine and / or protein. 18. Use according to claim 12, characterized in that one uses a reaction product of an aqueous glyoxal solution and gelatin, casein, collagen, keratin, horn, wool and / or silk. 19. Use according to claim 12, characterized in that one uses a reaction product of an aqueous glyoxal solution and collagen in the form of skin bumps, hardened skin fiber casings, leather and / or natural casings. 20. Use according to claim 12, characterized in that the reaction product of aqueous glyoxal solution and solid, NH groups-containing organic compounds in amounts of 0.1 to 5, preferably 0.2 to 4, in particular 1 to 3 wt .-% , based on the dry content of collagen, incorporated. 21. Use of a molding composition which contains a) animal skin fiber composition and b) reaction products in which residues derived from solid organic compounds containing NH groups are bonded to residues derived from glyoxal and with organic organic compounds containing solid NH groups Glyoxal dissolved in water have been reacted to produce moldings, characterized in that that the molding compound is deformed and dried. 22. Use according to claim 21 for the production of tubular films for packaging sausages. 23. Use according to claim 21 for the production of films or threads. 24. Use according to one of claims 21 to 23, characterized in that after the shaping and drying, heating and / or treatment with plasticizers, curing agents and / or neutralizing agents. 25. Use according to claim 21, characterized in that the molding composition reaction products in which residues derived from solid, NH group-containing organic compounds are bound to residues derived from glyoxal, and for their preparation solid, NH group-containing organic compounds with in water , dissolved glyoxal have been reacted, in amounts of 0.1 to 5 wt .-%, based on dry collagen. 26. Use according to claim 21, characterized in that the molding composition as reaction products, in which residues derived from solid organic compounds containing NH groups are bound to residues derived from glyoxal, and organic compounds containing solid NH groups containing in for their preparation Water-dissolved glyoxal have been reacted, a reaction product of an aqueous glyoxal solution, a solid organic compound containing NH groups and a high molecular weight organic substance such as a protein, cellulose and / or a plastic such as linear and / or crosslinked polycondensation and polyaddition compounds , contains. The subject of CH-PS No. 606 248 is a molding composition for the production of films, in particular tubular films for packaging sausages, which is characterized in that it contains a) animal skin fiber mass and b) aminoplast precondensates of compounds containing free amino groups with aldehydes and optionally Contains polyhydroxy compounds. It can also contain other additives. The subject of CH-PS No. 606 248 is also a process for the preparation of these molding compositions and their Ver5 10th 15 20th 25th 30th 35 40 45 50 55 60 65 2nd PATENT CLAIMS 3rd 635357 Application for the production of moldings, in particular tubular films for packaging sausages. In the production of reaction products from an aqueous glyoxal solution and compounds containing amino groups, it has now surprisingly been found that that glyoxal is able to dissolve solid organic compounds containing NH groups, such as amines, amides, imines, even proteins. A method was thus found for liquefying solid organic compounds containing NH groups.