Casing for sausages with starch or starch and the method of its preparation

 

(57) Abstract:

The invention relates to casings for sausages and method of their manufacture. According to the invention, seamless, tubular sheath formed in a surface ratio of 1:2 to 1:10 by blow-extrusion molding made of a thermoplastic mixture. A thermoplastic composition includes (a) thermoplastic starch and/or thermoplastic krahmaloprodukt and (b) at least one other polymer obtained by polycondensation or polyprionidae and selected from the group consisting of Homo - or copolymers with links hydroxycarbonic acid, polyetherurethane (with a complex of essential blocks), polyetherurethane (ether blocks), polyvinyl acetate and polyalkylacrylate formula[CHR1-CHR2-O-CO-O)nwhere R1and R2independently from each other represent a hydrogen atom or (C1-C4) alkyl residue, and n is an integer from 10 to 5000, and the weight ratio a):b) is in the range from 90:10 to 10:90. Thermoplastic mixture may also contain a plasticizer, softening agent, fibers, fillers, and/or a crosslinking agent. This shell is particularly suitable as an artificial marketing materials this is biologically destructive or, at least, compostable. 2 S. and 9 C.p. f-crystals.

The invention relates to casings for sausage products from mixtures of thermoplastic starch or starch with a biodegradable, hydrophilic, softening polymers, and other suitable fillers and, if necessary, cross-linking agents.

Most casings for sausage is made from natural gut, as well as the reinforced fibers of regenerated cellulose, collagen or synthetic polymers. Although cellulose and collagen and are of natural origin, however, the preparation of casings for sausage products is costly and harmful to the environment. Shell of another material, for example, made of coated protein or acrylate tissue, have, on the contrary, only a small value.

From the known shells full range of applications cover only the shell of the hydrate-cellulose. Shell of collagen have for many uses too high a permeability to water vapor or oxygen. Shell of synthetic polymers unsuitable for the manufacture of sausages long-term storage. Although they feature the shells of hydrate-cellulose and collagen, they are not biologically destructively.

Although described in EP-A 0709030 made by extrusion of thermoplastic starch casing for sausages and is biologically destructive, but she still finds shortcomings. In particular, it is not sustainable in boiling water and becomes brittle (fragile) after treatment with water or as a result of loss of plasticizer (softener).

Therefore, as before, the goal was to develop a wrapper for food products that can be made from natural - vegetable origin raw materials simple and preserving the environment of ways - by way of extrusion and is both biologically destructive or, at least, compostable. This shell must be sufficiently permeable and is applicable to virtually all types of sausages, including also for the production of cooked sausages, and smoked sausage.

This problem is solved using a mixture (Blend) of thermoplastic starch or thermoplastic starch and one or more synthetic Polow, which is formed in the surface ratio of from 1:2 to 1:10 by blow-extrusion molding made of a thermoplastic mixture, wherein the mixture comprises (a) thermoplastic starch and/or thermoplastic krahmaloprodukt and (b) at least one other polymer obtained by polycondensation or polyprionidae and selected from the group consisting of Homo - or copolymers with links hydroxycarbonic acid, polyetherurethane (with a complex of essential blocks), polyetherurethane (ether blocks), polyvinyl acetate and polyalkylacrylate formula

-[CHR1-CHR2-O-CO-O]n,

where R1and R2independently from each other represent a hydrogen atom or a (C1-C4)alkyl residue, a n is an integer from 10 to 5000, and the weight ratio a):b) is in the range from 90:10 to 10:90.

Preferred thermoplastic krakhmaloproduktam is an ester of starch, which is described in detail in DE-A 19515477. The acid component in this complex ester is usually (WITH the2-C10) albanova acid, which is preferably unbranched or only slightly branched. Especially preferred and inexpensive ancrene, from 1.5 to 2.4. Unlike the starch esters of starch, such as starch acetate, are thermoplastic themselves and not have to first plastifitsirovanie. Esters of starch with a longer alkyl chain, for example, hexanoate, octanoate or decanoate starch, cause changes pliability and toughness, and the permeability of wrappers of food. By combining various esters of starch can be produced membranes with highly specific properties. Suitable thermoplastic starch products which exhibit cationic quaternion side groups with hydrophobic (C2-C18) alkyl groups, preferably (C2-C12) alkyl groups.

It turned out that the casings for food products, which consist of thermoplastic starch and/or thermoplastic starch, yet to find the desired degree of elasticity (elasticity, strength, toughness, pliability, but above all stability against hot or boiling water. Properties of the shell cannot be improved significantly even if thermoplastic starch or thermoplastic and fillers. It has been unexpectedly discovered that a significant improvement comes only when thermoplastic starch or krahmaloprodukt mixed with other polymers obtained by polycondensation or polyprionidae, which is absolutely suitable as food packaging.

Obtained by polycondensation polymer is preferably a Homo - or copolymer with links hydroxycarbonate acid. Especially preferred are polylactide, poly(3-hydroxypropionic acid), poly(3-hydroxipropionic acid), poly(4-hydroxipropionic acid), polycaprolactone, polyetherurethane (with a complex of essential blocks), polyetherurethane (ether blocks) and polyetherurethane (complex and simple radio units), polyalkylacrylate formula[CHR1-CHR2-O-CO-O]nwhere R1and R2independently from each other represent a hydrogen atom or a (C1-C4) alkyl residue and n is an integer from 10 to 5000. Especially suitable polyalkylacrylate are polietilensorbit (R1=R2=N) and polypropenkarbonat, and mixtures thereof. Polyalkylacrylate described, for example, in WO 96/35746. The preferred polymer, which can p to be obtained synthetically by known methods. Usually they are unstitched or very slightly crosslinked. Their average molecular mass Mwis usually 20000-2000000, preferably 100000-1000000. It is assumed that these polycondensate form a matrix type, which are uniformly distributed thermoplastic and thereby destructively starch or krahmaloprodukt.

The weight ratio of components a):b) is preferably 20:80-80:20, particularly preferably 40:60-60:40.

Along with the components (a) and (b) thermoplastic mixture may contain additional low - or high-molecular ingredients, which are, in particular, as plasticizers or softeners, or improve the compatibility of the components with each other. With the help of additional ingredients can be, if necessary, to further enhance the homogeneity or the flowing extrudable thermoplastic mixture. As a particularly suitable plasticizer glycerin, diglycerin, sorbitol, polyethylene glycol (PEG), tritely ester of citric acid, tritely aired acetylamino acid triacetate glycerol ester of phthalic acid (in particular, dimethylphthalate, diethylphthalate and dibutyl phthalate), as well as complex mono - and W of sorbitol. Termoplastici mixture. The softeners, which improves the homogeneity of thermoplastic mixture, are, in particular, of vegetable fats or oils, synthetic triglycerides, lecithin, ethoxylated fatty alcohols or waxes. The proportion of softener is up to 12 wt.%, preferably 2-6 wt.%, particularly preferably 3-6 wt.%, calculated on the total weight of the mixture.

Shell, according to this invention, may finally be reinforced with fibers. Typically, these fibers are relatively short (on average, about 0.1 to 3 mm, preferably 0.2 to 1.5 mm). In order for the shell remained biologically destructive and thereby compostable, especially suitable fibers from cotton fluff (lint), wood pulp, regenerated cellulose ("restored, the hydrated cellulose fibers, hemp, flax, sisal agave (sisal-hemp or jute. The proportion of fibers can be up to 25 wt.%. Preferably, the proportion of fibers is up to 2-15, in particular, 5-15 wt.%, calculated on the total weight of the mixture. Fibers are distributed uniformly in thermoplastic compound, or it made of an extrudable melt.

The shell may contain, instead of fibers or other fillers. As the order is can be up to 12 wt.%, but preferably it is 2-8 wt.%, particularly preferably 4-8 wt.%, calculated on the total weight of thermoplastic mixture.

For shells with a particularly high stability against hot or boiling water turned out to be a favorable addition to thermoplastic mixture is even and a crosslinking agent (structuring agent). Suitable crosslinking agents are, for example, dicarboxylic acids, di - or triisocyanate (especially hexamethylenediisocyanate), dialdehyde (especially glyoxal), diepoxide, diimine or silanes or siloxanes with a vinyl group (or groups), for example, vinyltrimethylsilane. A crosslinking agent mainly add only when the other components of the mixture already melted. The proportion of crosslinking agent (agents) up to 20 wt.%, preferably 0.5 to 10 wt.%, particularly preferably 1-5 wt.%, calculated on the total weight of thermoplastic mixture.

The preparation is suitable for thermoplastic processing of starch is known and described in WO 90/05161 and 90/10019. When the plasticizing helical structure of native starch increases. The starch is then in the amorphous state. Plasticization is carried out usually by heating and supply of mechanical energy is signed extruder. In order for the starch melted at a temperature below the point of decomposition, necessary additives, such as water, 1,3-butanediol, glycerin, diglycerin, N,N-dimethylation, sorbitol or citrate. By plasticization with water, add about 20-25 wt.% water, preferably about 17 wt.% water, based on the weight of native starch. When this temperature is approximately 100-130°C. by plasticization with glycerin favorable was the proportion of 0.5-20 wt.%, preferably 8-16 wt.%, again, based on the weight of native starch, and a temperature of 150-170C. Through this processing, the proportion of crystalline starch is reduced to 5 wt.% or even lower.

This thermoplastic mixture can be prepared in conventional installations, for example, in a twin-screw kneading machine of the above-mentioned components. For the formation of homogeneous thermoplastic melt from this mixture was favorable temperature from 90 to 200°C., preferably from 120 to 180°C. the Melt can be ekstradiroval, after cooling, grind and leave with the aim of maturing the mixture in the form of a granulate or with the same success also immediately be processed into the shell for food. Then made of the melt tube is blown in is from 1:2 to 1:10, preferably 1:3-1:5. Only by stretching the tube gain optimum strength, elongation, maintaining the caliber and shrinkage. How pronounced each of these properties depends primarily on the composition of thermoplastic mixture. Thus, wrappers for food products can be tailored by carefully selecting the components of thermoplastic mixtures and type of additional processing to meet the different requirements. If necessary made of blow-molded shell may also partially thermophysiology.

In the next stage of the method of the tubular sheath can be prepared (pre-treated) inside and/or outside to make them even better suited for different applications as casings for sausages. This can be used most of the liquid preparation of the compositions (preparations), which are also common finishing tetrathalon shells, corresponding to the appropriate concentration. Thus, a particularly favorable is the coating on the inner surface of the shell, intended for smoked sausage, protein (preferably casein, gelatin, soy protein or white add a dividing means for protein/aldehyde may be regulated by the ability of the separation membrane sausages. The clutch shell with sausage stuffing can be reduced by known recipes to strong separating steps (what, for example, in the case of the Thuringian blood sausage).

Suitable external preparation composition also famous for cellulose casing. By processing the outer surface of the shell of this drug can be adjusted, in particular, planetologist, the surface roughness and the suitability for printing.

Wrapper for food products of this invention may in its properties vary so widely that it corresponds to the pulp or synthetic membrane. It can be prepared using simple and not burdening the environment of ways. Its good properties of swelling and shrinkage ensure that it at any time tightly to the sausage filling and also slow drying not folds. By selecting components, you can regulate the permeability of membranes to water, water vapor and oxygen. Surprisingly, the membrane permeable even to smoke, so that it can be well adapted for smoked varieties of sausages (e.g., salami). Used for the manufacture of the Oia.

Shell according to this invention can be, finally, also surrounded by a net, preferably with large holes, which gives the finished product a particularly pleasant appearance. It is known to superimpose on sausage grid in the form of a tube, which is suitable to the circumference of the tube carrier. The starch must be at least ... mm, so that the network is clearly distinguished. Apply various forms of grid cells: triangular, hexagonal, square, diamond-shaped, round or oval. The holes are formed from separate or intertwined threads and usually consist of textile yarn, preferably from a material that is similar to the pipe-bearer. In contrast to known from DE-A-3907951 the grid does not require any adhesive because the shell according to this invention attached to the net structure and thus provides the desired adhesion.

In the following examples, percentages are to be understood as% by weight, if there are no other instructions.

Example 1:

a) Preparation of thermoplastic starch

100 kg of potato starch under reduced pressure was dried until the water content less than 0.3% in vacuum and melted and well peremeshalas maintained for approximately 2 h at 170°C. Then the melt was extrudible and was granulated. During subsequent storage of the granules remained in amorphous starch and, therefore, a thermoplastic condition.

b) Preparation of unreinforced seamless casings for food products:

75 kg described in (a) granulate (50 kg starch + 25 kg of glycerol) were mixed with 50 kg of polycaprolactone, 3 kg of sunflower oil and 3 kg of hexamethylenediisocyanate. Uniformly mixed with each other components are melted in the extruder at 150°C. Then, the melt was extrudible through the ring forming the hole. The diameter of the ring forming the holes was chosen so that after the blow molded in a surface ratio of 1:10 were receiving tube with a diameter of 60 mm (= the caliber 60) and a wall thickness of 80 μm.

Tubes are constantly in the water, but swell in her and again shrink when drying. They can be worn on the boot device in the form of tied from one side of the segments or planted in the form of so-called "caterpillars". They are suitable in particular as casings for sausages long-term storage (i.e. smoked sausage with a particularly high level of maturity).

In irrigated condition axis 68-76 mm. Shell filled with ground meat salami. Sticking to the stuffing was small (the ability to separate the shell after 2 weeks: "1" rheological scale from 1 to 6, and "1" means "very easy to clean" and "6" means "too strong adhesion, membrane cannot be removed without tearing").

Therefore, to improve the adhesion with meat inflicted internal preparation composition protein(casein)/glyoxal, which is common to the tubes of the hydrate-cellulose.

Example 2:

Preparing a mixture of 50 kg of starch acetate with a degree of substitution of 2.2 and the molar weight of 580 g/mol, which was mixed with 50 kg of polietilensorbit with molecular weightw, 500000 and connected with 15 kg teeterboro ester of citric acid. This mixture was mixed with 8 kg of thermoplastic starch, 5 kg of 1,2;5,6-diepoxyoctane (hexamethylenediamine) and 5 kg of ethoxylated octadecanol (stearyl alcohol), with an average of 12 ethyleneoxide units.

This mixture was melted in a twin screw extruder at 150-170°C, well promaseal and then extrudible through the ring forming the hole, the size of which was chosen so that after the blow molded in a surface ratio of 1:8 was obtained TRU is; she was swollen in water and again gave the shrinkage during drying.

In irrigated condition was achieved, the pressure tearing from 38 to 42 kPa. Static stretching at 15 kPa internal pressure was at 76-80 mm

Tied or gathered on one side segments were suitable for the manufacture of sausages long-term storage or sausage. Cleanability the shell was good in both varieties of sausage (rating: 2).

Example 3 (Preparation of reinforced fiber shell):

A mixture of 50 kg of starch acetate, 15 kg teeterboro ester of citric acid and 50 kg of polietilensorbit was mixed with 10 kg of flax fibers ranging in length from 0.2 to 1.5 mm uniformly in the melt. At 160-180°C, the melt was extrudible through the ring forming the hole and was shaped extrusion-blowing molding (surface ratio of 1:6), so I got the tube of the gauge 60. Flooded tube has reached the pressure tearing from 60 to 65 kPa, and static stretching at 21 kPa internal pressure was kept at 65-70 mm

These shells were applicable for sausage and sausage long-term storage. They reached caliber filling 66-68 mm and they can be easily cleaned from the shell.

In irrigated condition was achieved, the pressure tearing from 60 to 68 kPa and static stretching at 21 kPa internal pressure when 56-62 mm

The caliber of the content was in the case of sausage or sausage long-term storage in the range 57-62 mm Cleanability from the shell was good.

1. Seamless tubular casing for food products, which is formed in the surface ratio of from 1:2 to 1:10 by blow-extrusion molding made of a thermoplastic mixture, wherein the mixture comprises (a) thermoplastic starch and/or thermoplastic krahmaloprodukt and (b) at least one other polymer obtained by polycondensation or polyprionidae and selected from the group consisting of Homo - or copolymers with links hydroxycarbonic acid, polyetherurethane (with a complex of essential blocks), polyetherurethane (ether blocks), polyvinyl acetate and polyalkylacrylate formula[CHR1-CHR2-O-CO-O)nwhere R

2. Shell food p. 1, characterized in that thermoplastic krahmaloprodukt is an ester of starch, preferably alkanoic starch, particularly preferably starch acetate.

3. Wrapper for food products under item 1 or 2, characterized in that obtained by the polycondensation polymer is preferably a homopolymer with links hydroxycarbonic acid, preferably polylactide, poly(3-hydroxypropionic acid), poly(3-hydroxybutiric acid), poly(4-hydroxybutiric acid), polycaprolactone.

4. Casing for food products according to one of paragraphs.1-3, characterized in that the weight ratio a):b) ranges from 20:80 to 80:20, preferably in the range of from 40:60 to 60:40.

5. Casing for food products according to one of paragraphs.1-4, characterized in that thermoplastic mixture contains at least one plasticizer, preferably glycerol, diglycerin, sorbitol, polyethylene glycol, tritely ester of citric acid, tritely aired acetylamino acid triacetate glycerol ester of phthalic kislota to 15 wt.%, calculated on the total weight of thermoplastic mixture.

6. Casing for food products according to one of paragraphs.1-5, characterized in that thermoplastic mixture contains at least one softening agent, preferably vegetable fat or vegetable oil, synthetic triglyceride, lecithin, ethoxylated fatty alcohol or wax, and the proportion of the softening agent (softeners) up to 12 wt.%, preferably 2-6 wt.%, particularly preferably 3-6 wt.% calculated on the total weight of thermoplastic mixture.

7. Casing for food products according to one of paragraphs.1-6, characterized in that thermoplastic mixture is mixed with fibers, preferably fibers of cotton fluff (lint), wood pulp, regenerated cellulose hydrate-cellulose), hemp, sisal or jute, with the proportion of fibers is up to 25 wt.%, preferably 2 to 15, particularly preferably 5-15 wt.% calculated on the total weight of the mixture.

8. Casing for food products according to one of paragraphs.1-7, characterized in that thermoplastic mixture contains a filler, preferably calcium carbonate, talc, kaolin or anhydrite, the percentage of filler is up to 12 wt.%, preferably 2-8 wt.%, particularly preferably 4-8 wt.% in calc is moplastic mixture contains, at least one crosslinking agent, preferably a dicarboxylic acid, di - or triisocyanate, dialdehyde, diepoxide, Diemen, or silane, or siloxane with vinyl group (or groups), with the share of cross-linking agent (agents) up to 20 wt.%, preferably 0.5 to 10 wt.%, particularly preferably 1-5 wt.% calculated on the total weight of the mixture.

10. Casing for food products according to one of paragraphs.1-9, characterized in that it has an internal and/or external preparation composition.

11. Method of preparation of membranes for food in one of the paragraphs.1-9, characterized in that thermoplastic mixture ekstragiruyut ring forming a hole and molded extrusion-blowing molding surface ratio from 1:2 to 1:10.

 

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