Cellulose wrapping, method of obtaining the same and product embedded in said wrapping

BR112021021623B1Active Publication Date: 2026-09-15VISCOFAN SA
View PDF 0 Cites 0 Cited by

Patent Information

Application Number
BR112021021623
Authority / Receiving Office
BR · BR
Patent Type
Patents
Current Assignee / Owner
Publication Date
2026-09-15

Smart Images

  • Figure 00000033_0000
    Figure 00000033_0000
  • Figure 00000034_0000
    Figure 00000034_0000
  • Figure 00000035_0000
    Figure 00000035_0000
Patent Text Reader

Abstract

Cellulose casing, method of obtaining the same and product embedded in said casing. The present invention relates to cellulose casings, reinforced or not, capable of transferring color to the product embedded in them. These casings contain a food coloring that can be transferred to the sausage during its processing. The present invention also relates to the method of obtaining the casing and the product embedded in said casing.
Need to check novelty before this filing date? Find Prior Art

Description

1 / 29 DESCRIPTIVE REPORT “CELLULOSE WRAPPING, METHOD OF OBTAINING THE SAME AND PRODUCT EMBEDDED IN SAID WRAPPING” DESCRIPTION

[001] The present invention relates to cellulose casings, reinforced or not, capable of transferring color to the encased product inside. These casings contain a food coloring that can be transferred to the encased product during processing. The present invention also relates to the method of obtaining the casing and to the product encased in said casing. BACKGROUND OF THE INVENTION

[002] Manufacturers of sausages and other processed meats need to give their products an attractive appearance for consumers. Color is a very important aspect, and in sausages the resulting color will depend on the type of emulsion and meat used, the processing conditions, and whether or not it has been subjected to a smoking treatment.

[003] For example, sausages are traditionally colored by applying natural smoke in gaseous form, or also by spraying or immersing them in liquid smoke from wood. Depending on the conditions and type of smoking, sausages with a brown color are obtained, ranging from very light beige tones to very dark, almost black tones.

[004] In some markets, it is customary to color the surface of sausages by applying food colorings. For example, in the Philippines, the consumption of sausages with a very intense red color is widespread, achieved by applying the synthetic dye Allura Red (E-129). In addition to red, in other markets, such as the USA and Australia, orange sausages are also produced by applying the synthetic dye Sunset Yellow (E-110). But one of the main disadvantages of using synthetic dyes is that, after being transferred to the surface of the sausage, they tend to penetrate the sausage and migrate from the surface to the center. This migration is undesirable, as the customer prefers that only the skin be colored. Petition 870210099373, dated 10 / 28 / 2021, pp. 92 / 132 2 / 29 of the coagulated protein surface is colored, not the interior of the sausage. Furthermore, when mixtures of these synthetic dyes are used, this migration can occur at different speeds and to varying degrees, thus producing a chromatographic effect where the cross-section of the sausage may exhibit rings of different colors. Another limitation of the use of these synthetic dyes is that, in many countries, their use is not authorized for coloring meat products.

[005] On the other hand, in Brazil it is very popular to dip cooked and peeled sausages in a solution of annatto in its water-soluble form (norbixin) to obtain a reddish-orange color. The color obtained will depend on the concentration of dye, the immersion time and the temperature. This water-soluble dye adheres to the surface of the sausage after a second immersion in an acidic medium, usually in a phosphoric acid solution.

[006] This method has many disadvantages, such as the need to reverse the facilities for applying the dye (tanks, conveyor belts, filters, among others), maintenance and energy costs, to which must be added the consumption of annatto and other ingredients, and the cost of treating wastewater containing dye residues. In addition, the sausages show easily noticeable color differences due to the difficulty of ensuring the same residence time and coloring capacity from one day to the next.

[007] Similarly, in Chile, a type of sausage called "Surena" is sold, which also exhibits a reddish-orange color, but in this case, due to the addition of water-soluble annatto to the meat emulsion, which gives an undesirable color to the inside of the sausage. This coloring of the entire meat emulsion leads to a higher cost than the superficial coloring of the sausage, as it requires the application of a much larger quantity of annatto, which, in addition, gives the product an undesirable flavor. Another negative point of this practice is that the sausage has a very unnatural appearance, since the entire interior of the sausage has an artificial color that causes distrust and displeases consumers. Petition 870210099373, dated 10 / 28 / 2021, pp. 93-132 3 / 29 consumers.

[008] Finally, it should be noted that in the most developed markets consumers show a strong propensity to avoid the use of synthetic dyes, and replace them with dyes of natural origin such as, for example, annatto, which is a dye extracted from the seeds of the annatto tree, and which has been used since ancient times by Native Americans.

[009] Several patents describe procedures for coloring sausage casings, which are subsequently able to transfer said dye to the surface of the sausage during the stuffing and cooking processes.

[010] The most common procedure for producing the aforementioned colored wrappers is the impregnation of the cellulose gel by passing it through a tank containing a dye solution. As described in US patents 2,477,767 and 2,477,768 (Remer et al.). This methodology presented problems of dye impregnation heterogeneity, as described in US patent 2,521,101 (Thor et al.). US patent 2,521,101 proposes obtaining a uniformly colored wrapper with a simple method that improves production yield, such as applying dye and glycerin in a bath with a pH adjusted to 7.5-9.5 before drying the cellulose gel. To avoid yield losses when it is necessary to produce transparent wrappers again, it is proposed to use a glycerin tank prior to the glycerin and dye tank, which is a mobile container that would only be installed when there is a need to produce colored wrappers.In this way, it is not necessary to empty the glycerin and dye tank, clean it, and add clean glycerin when transparent wrappers are to be produced, thus saving production time. When it is necessary to produce colored wrappers, the mobile glycerin and dye tank is again installed between the glycerin tank and the dryer. Even if the color is more uniform, the color variations that occur with pH in most dyes must be taken into account, which is why an appropriate mixture that imparts the desired color to the pH of the tank must be used. The patent provides examples of orange and colored wrappers. Petition 870210099373, dated 10 / 28 / 2021, pp. 94 / 132 4 / 29 cherry-colored, which transfers color to the sausage evenly.

[011] This procedure was later improved by the invention of US patent 3,438,071 (Clark et al.) which describes a simple system for controlling the level of the tank containing the dye and glycerin. For this, an additional storage tank is installed, which is connected to the tank through which the cellulose gel passes, and which automatically feeds it in response to a drop in level. This allows the production of casings with a more uniform color tone.

[012] But this cellulose gel impregnation procedure is not suitable when the intention is to apply the natural annatto dye, either in its oil-soluble form (bixin) or in its water-soluble form (norbixin). Either due to lack of chemical affinity or its high molecular size, the cellulose gel does not substantially absorb the aforementioned forms of annatto dye, or if it does absorb them, their transfer to the sausage is very difficult.Therefore, when planning to apply annatto to a cellulose casing, it is common to use a methodology called "bubbling" or "slug coating" to coat the inside of the casings.

[013] Both dyes (norbixin and bixin), when used separately to coat cellulosic casings internally, do not offer good results.

[014] This discovery is disclosed in patent ES 2075813 B1 (Gato et al.), which describes cellulosic casings internally coated with a coating formed by the water-soluble annatto dye, norbixin, and another oil-soluble component (which may be bixin, the other annatto dye), which is transferred uniformly during the processing of sausages made with these casings. The patent claims both the casings obtained and the method that uses them to impart a reddish-orange color to sausages and similar meat products. In this case, the coating is a step that must be carried out off-line within the usual processes for obtaining casings, which is supposedly not an economical method.

[015] US patent 5,955,126 (Jon et al) describes compositions of bixin, a water-soluble film-forming agent (preferably hydroxypropylcellulose), a Petition 870210099373, dated 10 / 28 / 2021, pp. 95 / 132 5 / 29 polyphosphate and optionally an antioxidant, as well as wrappers coated with said composition. In addition to the preferred application by the “bubbling” or “slug coating” method, they describe the possibility of applying the coloring composition by internal spraying during the wrapping stage. Their US division 6,143,344 (Jon et al.) claims the coloring composition, defined as a dispersion of bixin in a water-soluble and / or alcohol-soluble film-forming agent, with a “grid fineness” (measure of the degree of dye dispersion) of 3 microns or less as defined in ASTM method D-1316-87. Both application methods are also described in patent application EP 1250853 A1 (DuCharme et al.). In this case, the bixin is applied as a coating; this coating is obtained because the composition contains a film-forming agent. In all its forms, the intention is to obtain the bixin on the inner surface that is in contact with the sausage.

[016] US patent application 2003 / 0039724 A1 (DuCharme et al.) describes the manufacture of cellulose casings colored with a reddish smoky color, by coating with liquid smoke and / or natural red dyes such as bixin, optionally antioxidants and, optionally, a peeling agent. In this case, the preferred application method is also “bubbling” or “slug coating”. The application mentions the possibility of applying the coloring composition of the invention to the viscose immediately before the extrusion step. Although it is expected that the dyes will adhere to the casing and therefore not be transferred to the sausage, it is believed that liquid smokes and some suitable natural red dyes located on the surface of the casing may be transferred to the sausage when in contact with the surface of the casing if subjected to high temperatures.

[017] Finally, patent CA 713510 (AH Cameron) mentions a method of spraying a caramel coloring solution that is applied to the inside of the casing once it has been pleated, before embedding.

[018] Despite the different inventions described above, the market Petition 870210099373, dated 10 / 28 / 2021, pp. 96 / 132 6 / 29 currently lacks a cellulose casing capable of transferring annatto dye, in any of its forms, to the sausage. The spraying procedure of the coloring composition carried out during the plying process causes a very heterogeneous distribution of color, since the dye accumulates in the pleats, resulting in more intense marks on the surface of the sausage.

[019] Regarding products prepared by the “bubbling” or “slug coating” method, they also present the same problem of heterogeneity of the transferred color, even if to a lesser extent. But the main problem with this technology is its high application cost, especially in gauges smaller than 50 mm, as they require an “off-line” application as shown in Figure 1 of US Patent 5,955,126.

[020] This is why, as mentioned earlier, there is no commercial cellulose casing product capable of transferring annatto dye to the sausage in a homogeneous manner, despite strong demand from sausage manufacturers. DESCRIPTION OF THE INVENTION

[021] Annatto or bija is a dye obtained from annatto or orellana (Bixa orellana L), a species originally from the Amazon basin. It is obtained from the reddish pulp surrounding the seeds and is used to color many foods such as cheeses, margarine, butter, rice, and smoked fish. Annatto is the name given to the crude extract, which contains two edible pigments: norbixin, which is water-soluble and therefore the most abundant in water-soluble annatto extracts, and oil-soluble annatto dyes that contain bixin as the main dye. Both are carotenoid pigments and therefore can be affected by light and oxygen, which can alter their conjugated double bond structure. Bixin is the monomethyl ester of norbixin, so norbixin can be obtained from bixin by alkaline saponification. Petition 870210099373, dated 10 / 28 / 2021, pp. 97 / 132 7 / 29 HOOC COOCH3 Bixin formula Norbixin formula

[022] The objective of the present invention is to overcome the shortcomings of the cellulose casings with annatto-based inner coating that have been mentioned. In contrast to the prior art casings that are coated with annatto, the present invention provides a cellulose casing whose inner layer is intimately impregnated with annatto, and which is capable of transferring color to the meat encased within said casing in a substantially uniform manner.

[023] The inner layer of the casing containing the annatto may have a different thickness and / or concentration of annatto, which will cause it to acquire various shades after transfer to the sausage. When the amount of annatto in this layer is low, the color transfer will also be low, and the resulting color will be a light brown or beige tone, similar to that obtained when the sausage is subjected to gentle smoking. When this concentration is increased, the transfer increases and the sausage's tone will be substantially reddish-orange. The final color of the sausage will depend, among other factors, on the composition of the meat emulsion and the cooking conditions.

[024] The annatto in the packaging of the present invention is distributed throughout the inner layer. Petition 870210099373, dated 10 / 28 / 2021, pp. 98 / 132 8 / 29

[025] The first aspect of the invention relates to a sausage casing comprising two layers of cellulose: an inner layer whose composition comprises: regenerated cellulose and annatto, the annatto comprising norbixin; and an outer layer comprising regenerated cellulose, concentric to the inner layer; the casing comprises norbixin and between 50% and 100% by weight of the annatto is distributed in the inner half of the zone comprised by said inner and outer layers of the casing.

[026] In the present invention, the term “inner layer” refers to any layer situated between two layers of the casing or between a layer and the embedded material.

[027] In the present invention, the term “regenerated cellulose” refers to cellulose obtained from a solution of some cellulose derivative such as, for example, cellulose xanthate. The solution of a given cellulose derivative is transformed into viscose by any of the methods known in the art, and the viscose is extracted to obtain the regenerated cellulose.

[028] In the present invention, the term “annatto” refers to the combination of the bixin compound and the norbixin compound; when referring to a percentage of annatto, it refers to the sum of the percentages of the bixin compound and the norbixin compound in the husk. In the case where the hydrolysis of bixin is complete, annatto refers only to norbixin.

[029] In the present invention, the term pTceiuiose refers to the total weight of regenerated cellulose in the envelope, specifically in all layers present in the envelope.

[030] A second aspect of the invention is the procedure for obtaining the envelope of the invention.

[031] In the invention procedure, the different layers of regenerated cellulose are obtained by extruding viscose. An oily solution of bixin is added to one of the inner layers, and this bixin is hydrolyzed in a step. Petition 870210099373, dated 10 / 28 / 2021, pp. 99 / 132 9 / 29 posterior.

[032] The present invention avoids the problem of mixing viscose with norbixin, since the mixture undergoes severe dehydration during coagulation, and the water can carry away a large portion of the water-soluble dye. Possible subsequent washings if norbixin is included in the mixture would also cause further dye loss, so that the amount of dye remaining in the final casing is insufficient to impart sufficient color to the sausage. Furthermore, the dye heavily contaminates the process liquids.

[033] Bixin in an oily solution, which is not water-soluble, does not contaminate the washing water. On the other hand, its conversion to norbixin is preferable so that, during the cooking process of the meat encased in the casing, the water-soluble dye migrates efficiently and transfers a sufficient amount of color for the purpose of the present invention. Surprisingly, although the invention procedure transforms bixin into norbixin during the manufacturing process, either completely or partially, it remains attached to the inner layer of the casing and does not significantly contaminate either the coagulation-regeneration bath or the washing water.

[034] Therefore, a second aspect of the invention relates to a procedure for obtaining the envelope defined in the invention, comprising the steps of: a) add an oily solution of bixin to the viscose; b) Extrude the product from step a) in the inner circuit and viscose in the outer circuit using an extruder with a head comprising at least two concentric circuits: c) hydrolyze bixin into norbixin after step a) or after step b).

[035] In the present invention, the term “bixin oily solution” refers to bixin oily solutions or solutions, suspensions or emulsions. These bixin oily solutions comprise between 0.1% and 20% bixin.

[036] In the present invention (p / pViscose), the relationship between the weight of the bixin oily solution and the weight of viscose used to form the layer is mentioned. Petition 870210099373, dated 10 / 28 / 2021, pp. 100 / 132 10 / 29 with bixin.

[037] In step b) of the present invention comprising at least two concentric circuits, it is understood that the head has two, three, four or five or more concentric circuits.

[038] A further aspect of the invention is an embedded casing obtainable by the procedure defined in the invention.

[039] Another aspect of the invention is the use of the casing of the invention in the production of sausages.

[040] Another aspect of the invention is a product embedded in the casing of the invention. A final aspect is the method of obtaining the product embedded in the casing of the invention, which comprises the steps of: a) embedding a sausage mixture in the casing of the invention; b) cooking the embedded mixture; c) removing the casing. BRIEF DESCRIPTION OF THE DRAWINGS

[041] Figure 1 shows a cross-section of the multilayer envelope wall obtained in example 1. The left part is the uncolored outer layer which has a thickness of 9.9 pm, the middle part is the annatto-colored inner layer which has a thickness of 4.9 pm, and the right part is the uncolored inner layer which has a thickness of 9.9 pm.

[042] Figure 2 shows a cross-section of the wall of a bilayer type envelope. The left part is the uncolored outer layer with a thickness of 18 pm, and the right part is the colored inner layer with a thickness of 6.9 pm.

[043] Figure 3 shows an absorption spectrum of the transferable dye from two regenerated cellulose envelopes: (1) Control (2) treatment of cellulosic gel with 2% KOH according to example 4. DESCRIPTION OF A PREFERRED REALIZATION

[044] As stated above, the first aspect of the invention relates to a sausage casing comprising two layers of cellulose: Petition 870210099373, dated 10 / 28 / 2021, pp. 101 / 132 11 / 29 an inner layer whose composition comprises: regenerated cellulose and annatto, the annatto comprising norbixin; and an outer layer comprising regenerated cellulose, concentric to the inner layer; the outer layer comprising norbixin and between 50% and 100% by weight of the annatto being distributed in the inner half of the zone comprised by said inner and outer layers of the outer layer.

[045] In a preferred embodiment, annatto is comprised between 0.05% (w / wTceiuiose) and 20% (w / wTceiuiose), more preferably between 0.2% (w / wTceiuiose) and 5% (w / wTcellulose).

[046] Preferably, the wrapper does not have an inner coating of annatto.

[047] In a preferred embodiment, the regenerated cellulose is reinforced regenerated cellulose. In the present invention, the term “reinforced regenerated cellulose” refers to regenerated cellulose reinforced with natural or synthetic cellulose-based fibers, or with regenerated cellulose-based fibers treated with agents that improve mechanical properties. In a preferred embodiment, the cellulose is reinforced with paper. In a particular embodiment, the wrapper has three concentric layers: an inner layer of viscose, an intermediate layer of broad-fiber paper, and a third outer layer also of viscose. In particular, the broad-fiber paper is abaca.

[048] In a preferred embodiment, the number of layers of the envelopes of the invention is chosen between two and three.

[049] As already mentioned, a second aspect of the invention relates to a procedure for obtaining the envelope defined in the invention, which comprises the steps of: a) add an oily solution of bixin to the viscose; b) Extrude in an extruder with a head comprising at least two concentric circuits, the product of step a) in the inner circuit and viscose in the outer circuit: Petition 870210099373, dated 10 / 28 / 2021, pp. 102 / 132 12 / 29 c) hydrolyze bixin into norbixin after step a) or after step b).

[050] In a preferred embodiment, the amount of bixin oil solution that is added to the viscose in step a) is between 0.05% (w / wViscose) and 25% (w / wViscose). In a more preferred embodiment, the amount of bixin oil solution that is added to the viscose in step a) is between 5% (w / wViscose) and 20% (w / wViscose).

[051] In a preferred embodiment, the hydrolysis step of bixin into norbixin is carried out after step a) in a step prior to step b) of extrusion; in this new step, the bixin is mixed with the viscose for a time between 0.5 minutes and 24 hours. More preferably, between 30 minutes and six hours. More preferably, the mixing is carried out in a uniform manner by a mechanical mixer system in a static or dynamic manner.

[052] In another preferred embodiment, the hydrolysis step of bixin to norbixin is carried out after step b), subjecting the product obtained in step b) to treatment with an alkaline compound. More preferably, the treatment is a bath in a solution of an alkaline compound in a concentration range by weight between 0.1% and 10%. More preferably, the alkaline compound is NaOH, KOH, amines or ammonium hydroxide, more preferably the solution is comprised of 0.1% to 10% concentration by weight of NaOH or KOH. More preferably, the time is between 0.5 and 5 minutes and the temperature between 40 °C and 70 °C. In particular, it is a 2% KOH solution for a time between 1 and 5 minutes at a temperature between 40 °C and 90 °C.

[053] In the present invention, the term “alkaline compound” refers to a hydroxide, a carbonate or a bicarbonate of an alkali or alkaline earth metal, an ammonium hydroxide or salts thereof, or an amine. Preferably, the alkaline compound is selected from: NaOH, KOH, methylamine, dimethylamine, trimethylamine, ethylamine, among others, and NH4OH. In particular, it is KOH.

[054] Step a) of the procedure occurs significantly at temperature Petition 870210099373, dated 10 / 28 / 2021, pp. 103 / 132 13 / 29 below 40 °C, preferably between 20 °C and 40 °C, with a temperature of 20 °C to 25 °C being most preferable.

[055] The amount of bixin oily solution in step a) is preferably in an amount of 0.05% to 25%. More preferably, between 0.05% and 3% if the intention is to obtain a beige or light brown color in the sausage embedded in said casing, from 3% to 8% if the intention is a yellowish-orange color or from 8% to 25% if the intention is to obtain a more reddish-orange tone.

[056] Preferably, the procedure comprises in any embodiment of the invention a final step of passing through a plasticizing bath. Preferably, the plasticizing bath contains glycerin.

[057] In a preferred embodiment, the hydrolysis step is carried out after step b) before the plasticizing bath step by bathing the product obtained in step b) in a bath of a hydrolytic enzyme. In particular, the enzyme is a lipase enzyme. Preferably, the enzyme is between 2 g / l and 10 g / l. More preferably, between 3 g / l and 5 g / l. Preferably, the bath lasts between 30 minutes and 180 minutes. Preferably, the bath is at a temperature between 30 °C and 40 °C.

[058] In general, in the procedures for obtaining casings there is a step of folding or corrugating the casing. During this step, it is usual to spray internally an aqueous solution that carries ingredients that increase the plasticity of the casing or that also facilitate the subsequent peeling and separation of the casing from the sausage, such as carboxymethylcellulose or CMC.

[059] In the present invention, in a particular embodiment, said pleating compositions may incorporate an alkaline compound, preferably selected from: KOH, NaOH, amines or NH4OH, which will hydrolyze the bixin present in the inner layer of the invention's wrapper into water-soluble norbixin. The corrugated wrappers may be stored at temperatures up to 90 °C to accelerate said reaction, but preferably are stored at temperatures between 20 and 40 °C, for a time that may be from several minutes to Petition 870210099373, dated 10 / 28 / 2021, pp. 104 / 132 14 / 29 several months. The concentration of the alkaline compound in these folding compositions can vary from 0.1% to 10% by weight, more preferably between 0.5% and 3%.

[060] As already mentioned, another aspect of the invention is the use of the casing of the invention in the production of sausages, and a final aspect of the invention is a product embedded in the casing of the invention. In both cases, in particular, the sausage is a sausage.

[061] In a final particular embodiment of the method for obtaining the stuffed product, the unwrapped sausage, after removing the casing, is immersed in an acidic solution, preferably in a phosphoric acid solution. Preferably, for between 30 seconds and 5 minutes. Preferably, the phosphoric acid solution is at a concentration by weight of between 5% and 10%. t

[062] The following examples are merely illustrative of the present invention and should not be interpreted in a limiting sense.

[063] In all examples, the methods for quantifying the color transmission capacity in the prepared samples are indicated below. METHODS

[064] The following methods were used to quantify the color transmission capacity of the samples prepared in the examples of the invention. TEST L,A,B

[065] The Hunter L,a,b values ​​are a conventional procedure for quantifying the color scale of a product. This procedure shows differences in brightness, hue, and color saturation. The L parameter indicates the lightness of the color, with the value 100 corresponding to white, and the value zero to black. The a parameter indicates the gradient from red to green, representing a redder color as a increases. The b parameter indicates the gradient from yellow to blue, and its increase indicates that the color is more yellow. Petition 870210099373, dated 10 / 28 / 2021, pp. 105 / 132 15 / 29

[066] In the examples of the invention, the Hunter L,a,b color scale is used to measure the color of cellulose casings and sausages from which the casing has been removed to quantify the color that said casing transmitted to them. In the case of the casings, the measurement was performed on two overlapping layers placed on a white tile. In the case of the sausages, they were covered with a transparent plastic film, and the measurement was performed by placing the colorimeter directly on them. The plastic film prevents contamination and the adhesion of dirt to the colorimeter. The value obtained was the average of 5 measurements. A model C162S colorimeter from the X-rite brand was used. EXTRACTABLE COLOR

[067] This method allows quantifying the color transmission capacity of a cellulose wrapper. In the examples of the invention, this method was used to determine the color transmission capacity of regenerated viscose films and cellulose wrappers. The procedure consists of placing the sample in an Erlenmeyer flask with 250 ml of 0.008% w / v KOH, which was prepared by diluting one gram of 2% KOH solution to 250 ml. Subsequently, the Erlenmeyer flask is placed on a heating plate until boiling, and is maintained for 5 minutes. After cooling, the sample is removed and the absorbance of the supernatant is measured at 480 nm. In the measurements of the examples of the invention, a Perkin Elmer US / VIS Lambda 365 spectrophotometer was used. The higher the absorbance, the higher the concentration of annatto and, therefore, the higher the color transmission capacity of the sample. EXAMPLE 1

[068] In this example, a colored wrapper was prepared with an extruder as described in patent ES 2160091 B1 (by García et al.).

[069] Cellulose was regenerated from viscose. The viscose had an alkali content equivalent to 6% NaOH.

[070] A three-layer envelope was produced in which bixin was injected into the viscose of an inner layer of the envelope, in this case the central layer. Petition 870210099373, dated 10 / 28 / 2021, pp. 106 / 132 16 / 29

[071] For this example, bixin dispersion in oil from the brand Imbarex annatto oil suspension 10% AOS was chosen. 10.

[072] The dye is injected into the viscose which is extruded through the center layer of the extruder. For this, an Iwaki EWNB11VCER diaphragm pump and a dynamic mixer were used.

[073] The amount of viscose injected was 18.4% by weight in relation to the viscose of the central layer, and 3.68% in relation to the total viscose that constitutes 4.84% of annatto over the total cellulose. The injection was carried out 15 minutes before the time of extrusion.

[074] To the naked eye, it was not detected that the process liquids inside the casing had been contaminated with the dye.

[075] The resulting casing was filled with a typical meat emulsion for making “hot dogs”, cooked in a cycle without smoking, as described in Table 1, and subsequently the sausages were peeled and, surprisingly, it was observed that there was some color transfer from the casing to the sausage, resulting in sausages with a beige surface color, similar to that obtained with light smoking. TABLE 1. DESCRIPTION OF THE COOKING PROCESS FOR "HOT DOGS". Step t min °C HR% drying 15 60 0 Ctrl HR 1 15 70 40-50 Ctrl HR 2 20 85 70-80 Brine bath 3 0 -

[076] This result shows that the color transmission phenomenon does not occur only through surface contact between the casing and the meat emulsion, but that some Petition 870210099373, dated 10 / 28 / 2021, pp. 107 / 132 17 / 29 Another phenomenon, hitherto unknown, is involved. In order to investigate this phenomenon, a cross-section was made in the wall of the envelope, and the structure was studied with optical microscopy. In Figure 1, the presence of three concentric layers is noted: an outer layer (left side of the image) without color, 9.9 pm thick; a central colored layer, 4.9 pm thick; and an inner layer (right side of the image), 9.9 pm thick.

[077] Additionally, it is observed that the annatto was not confined to the central layer, which would be expected, since bixin is oil-soluble, but there is color diffusion to the inner and outer layers of dye, which could only be annatto in water-soluble form (norbixin) to be able to migrate through a matrix as hydrophilic as regenerated cellulose is. EXAMPLE 2

[078] In the present example, the aim is to maximize color transfer by extruding a bilayer casing, i.e., one that has two concentric layers, an outer layer without annatto dye and an inner layer with annatto, which will transmit the color to the sausage. Figure 2 shows a cross-section of the casing wall under a microscope, where an uncolored outer layer of 18 µm thickness (left side) and a colored inner layer of 6.9 µm thickness (right side) can be observed. In addition, different casings with different concentrations of bixin in the inner layer were prepared.

[079] The bixin selected for this example was Imbarex annatto oil suspension 10% AOS. 10, the same as in example 1. The dye was injected into the viscose which is extracted through the inner layer of the extruder, using the same pumping and mixing equipment as in example 1.

[080] The injected quantity contains 6%, 8%, 10%, 12%, 15% and 18% by weight relative to the viscose extruded by the inner layer, and 0.36%, 0.48%, 0.60%, 0.72%, 0.90% and 1.08% relative to the total viscose extruded, which constitute 0.47%, 0.63%, 0.79%, 0.95%, 1.18% and 1.42% respectively of the bixin in the total cellulose. The contact time of the bixin with the viscose was increased to 30 minutes. Petition 870210099373, dated 10 / 28 / 2021, pp. 108 / 132 18 / 29

[081] As in example 1, the wrapper can be rolled up without problems, resulting in a compact coil, and after corrugation a manageable product was obtained, similar in properties to that obtained with non-colored wrappers. And as in example 1, it was not detected, with the naked eye, that the process liquids inside the wrapper had been contaminated with the dye.

[082] The 6 casings obtained and one colorless casing (negative control) were stuffed with a typical meat emulsion for the manufacture of “hot dogs”, then the sausages were peeled, and the L,a,b color was measured as described in the Methods section.

[083] Table 2 shows the results obtained. TABLE 2. L,A,B VALUES OF "HOT DOGS" FILLED WITH TWO-LAYER CASINGS WITH DIFFERENT BIXIN CONCENTRATIONS IN THE INNER LAYER. Percentage of Bixin in relation to the viscose weight of the inner layer L ab 0% 67.2 6.7 19.3 6% 62.1 23.4 46.6 8% 62.2 23.7 47.4 10% 62.4 23.9 46.7 12% 61.2 26.8 55.9 15% 59.2 29.9 61.8 18% 58 30.8 64.9

[084] Significant color transfer is observed in relation to the negative control, and the intensity of this color increases with increasing injected concentration. Petition 870210099373, dated 10 / 28 / 2021, pp. 109 / 132 19 / 29 of bixin in the inner layer of the casing. The higher the concentration, the lower the L value, the darker the sausage; the higher the a value, the redder the sausage; and the higher the b value, which indicates that the sausage is more yellow. The simultaneous increase in the a and b values ​​indicates that, overall, the sausage is more orange the higher the concentration of the dye.

[085] Subsequently, a procedure was applied that allows increasing the red tone of the sausages prepared with the casings of the present invention. For this, peeled sausages that had been prepared with 18% bixin of the present example were chosen, which were immersed in a 5% phosphoric acid solution at 20 °C for one minute (for the preparation of the solution, 85% phosphoric acid from PANREAC was used). The action of the acid causes the sausage to redden, a coloration that is preferred by some consumers.

[086] The L,a,b color of the sausages was measured as described in the Methods section. Table 3 shows the results obtained. TABLE 3. L,A,B VALUES OF "HOT DOGS" FILLED WITH THE CASINGS OF THE PRESENT EXAMPLE WITH 18% ANNATTO BIX IN THE INNER LAYER. Sample Treatment with 5% phosphoric acid (s) L a B 1 0 58.0 30.8 64.9 2 60 58.5 32.4 62.2

[087] Treating the sausage with phosphoric acid does not significantly alter the L value, i.e., the sausage maintains its brightness, but it causes an increase in the a value, the sausage is redder, and a decrease in the b value, which indicates that the sausage is less yellow, and, considering these values ​​together, the sausage prepared with sample 2 exhibits a more reddish color. EXAMPLE 3 Petition 870210099373, dated 10 / 28 / 2021, pp. 110 / 132 20 / 29

[088] In the present example, the sample from Example 2, which contained 12% bixin relative to the viscose weight of the inner layer, was taken and “hot dogs” were prepared with a typical emulsion, to which 0.06% 25% L-OD carmine from the supplier Sensient was added to provide a more pinkish tone. Sample 1 was prepared with an uncolored casing, samples 2 and 3 with the previously mentioned casing from Example 2, but in the case of sample 3, it was turned over so that the uncolored outer layer of the casing was in direct contact with the meat emulsion. The sausages were cooked in an oven cycle without smoking, but with higher relative humidity in order to increase the diffusion of the dye, as described in Table 4. TABLE 4. DESCRIPTION OF THE COOKING PROCESS FOR "HOT DOGS". Step t min °C HR% drying 15 60 0 Ctrl HR 30 85 100% brine bath 3 0 -

[089] Subsequently, the L,a,b color of the sausages was measured as described in the Methods section. The results obtained are presented in Table 5. TABLE 5. L,A,B VALUES OF “HOT DOGS” WITH CASINGS (1) WITHOUT COLORING, (2) WITH 12% ANNATTO BIXIN IN THE INNER LAYER AND (3] ENVELOPE (2), BUT TURNED OVER. Sample Treatment L to B 1 No dye 60.9 14.2 18.9 2 12% bixin in the inner layer 55.0 19.9 44.5 3 12% bixin in the outer layer 56.7 16.4 28.8 Petition 870210099373, dated 10 / 28 / 2021, pp. 111 / 132 21 / 29 Sample Treatment L to B inner layer and turned

[090] It is observed that in samples 2 and 3 the dye is transferred to the casing, and that this is much less in the case where the casing was stuffed inside out due to the difficulty the dye encounters in migrating through the uncolored cellulose layer. This difference in color transmission would indicate that the most efficient casing for the purpose of the invention is the one that has most of the dye in the inner half of the casing. EXAMPLE 4

[091] The cellulose wrappers prepared in this example 4 exhibit different contact times between the bixin and the viscose. In this example, the selected bixin was Bixinex oil soluble 10% Liquid (NBX 36) from the manufacturer Pronex. The dye was injected into the viscose, which is extruded through the inner layer of the extruder. In sample 1, the bixin was injected into the viscose 15 minutes before extrusion, and the amount injected was 14% relative to the viscose of the inner layer by weight and 0.98% relative to the total extruded viscose, which constitutes 1.29% bixin of the total dry cellulose. In sample 2, the bixin dye was injected into the viscose 4.5 hours before extrusion, and the amount injected was 13.2% relative to the viscose of the inner layer by weight and 0.94% relative to the total extruded viscose, which constitutes 1.23% of the total regenerated cellulose bixin.As in the previous examples, it was not detected with the naked eye that the process liquids inside the casing had been contaminated with the dye.

[092] Both casings were filled with a typical meat emulsion for the manufacture of “hot dogs”, and subsequently the sausages were peeled and the L,a,b color was measured as described in the Methods section. A Petition 870210099373, dated 10 / 28 / 2021, pages 112 / 132 22 / 29 Table 6 shows the results obtained. TABI EMBUTIDOS C TEMPOS DE C ELA 6. VALORES ΪOM ENVOLTÓRIOS ONTATO COM VISCC L,A,B DE “CACHORO-QUENTES” DOGS DO BICAMADA COM DIFERENTES >SE ALCÁLINE. Amostra Tempo de contato do urucum com a viscose (h) L a B 1 0.25 61.0 26.0 44.0 2 4.5 60.1 29.4 57.9

[093] An increase in color transfer capacity is observed with sample 2, which was in contact with the viscose for a longer period of time. The longer contact time decreases the L value, the sausage is darker, increases the a value, the sausage is redder, and the b value, which indicates that the sausage is more yellow, and, considering these values ​​together, the sausage prepared with sample 2 exhibits a more orange color. EXAMPLE 5

[094] In the present example, the effect of a post-extrusion treatment with KOH solution was studied.

[095] In this example, the selected bixin annatto was Imbarex annatto oil suspension 10% AOS.10. The dye was injected into the viscose which is extruded through the inner layer of the extruder.

[096] Two samples were prepared, and in both, bixin was injected into the viscose 10 minutes before extrusion. The injected amount was 12% by weight of the inner layer viscose and 1.2% of the total extruded viscose, which constitutes 1.58% of the total dry cellulose bixin. Sample 1, or the control, was passed through the different process tanks in a conventional manner. On the other hand, sample 2 was passed through an additional tank, which Petition 870210099373, dated 10 / 28 / 2021, pages 113 / 132 Sample 23 / 29 was installed in a position prior to the plasticizing tank. This tank contained a 2% by weight KOH solution at a temperature of 65 °C. The passage time of the cellulosic gel was 2 to 3 minutes. After undergoing this alkaline treatment, it was passed through a water tank to eliminate excess KOH and then through the plasticizing tank. To the naked eye, it was observed that the resulting envelope had a more orange tone than the control. Similar to the previous examples, in neither of the two samples was it detected to the naked eye that the process liquids inside the envelope had been contaminated with the dye.

[097] 25 cm of film was removed from the wrapper, which was cut along one of its sides in the longitudinal direction and placed in an Erlenmeyer flask with 250 ml of 0.008% w / v KOH. The Erlenmeyer flask was boiled for 5 minutes and, after cooling the supernatant, the spectrum was measured in visible light. The result shows that the wrapper that was subjected to treatment in a tank with KOH (sample 2) underwent a transformation that caused an increase in absorbance in the 400-600 nm wavelength range, which indicates that said wrapper has a greater capacity for color transmission (Figure 3).

[098] Both casings were filled with a typical meat emulsion for the manufacture of “hot dogs”. Subsequently, the sausages were peeled and their L,a,b color was measured as described in the Methods section. Table 7 shows the results obtained. TABLE 7. L,A,B VALUES OF "HOT DOGS" FILLED WITH CONVENTIONAL TWO-LAYER CASINGS AND WITH CELLULOSIC GEL TREATMENT WITH 2% KOH. Sample Treatment with 2% KOH tank gel (s) L a B 1 0 59.5 25.2 49.2 2 150 58.2 29.2 58.8 Petition 870210099373, dated 10 / 28 / 2021, pp. 114 / 132 24 / 29

[099] An increase in color transfer capacity is observed with sample 2, which was subjected to treatment with 2% KOH solution at 65 °C for 150 s. This treatment causes a decrease in the L value, i.e., the sausage is darker, an increase in the a value, the sausage is redder, and in the b value, which indicates that the sausage is more yellow, and, considering these values ​​together, the sausage prepared with sample 2 exhibits a more orange color. EXAMPLE 6

[0100] From the casing of sample 1 of example 5, pleated samples were prepared with 4 different additives according to known procedures in the art. Pleating additives are compositions that are sprayed inside the casing during the pleating operation. Their main function is to give the casing greater plasticity and thus overcome the pleating stage without suffering a considerable deterioration of its mechanical properties. In addition, it is common in the art to apply pleating additives that also give the casing greater ease of separation of the sausage during the peeling stage, called "easy-peeling" additives. These compositions usually have carboxymethylcellulose (CMC) as the main agent that favors the peeling of the sausage. Table 8 shows the type of pleating compositions used in this example. TABLE 8. DESCRIPTION OF THE COMPOSITION OF THE CREAMING ADDITIVES. "Easy Peeling" Folding Additive KOH 1a No 0 1B No 0.5% 2a Yes 0 Petition 870210099373, dated 10 / 28 / 2021, pp. 115 / 132 25 / 29 KOH 2B Easy Peeling Folding Additive 0.5%

[0101] Additive 1 is a composition devoid of CMC, and which does not have the function of promoting the peeling of the sausage, and is normally used in casings whose purpose is to be peeled by the end consumer, not by the sausage manufacturer. The composition of additive 1A contains 30% propylene glycol and 70% water, as described in example IX of US patent 3,981,046 by H. Chiu. In composition B, said additive KOH was added until a concentration of 0.5% was reached. On the other hand, additive 2 is a typical composition containing CMC to promote the mechanical peeling of sausages by the sausage manufacturer. The composition of additive 2A contains 1.42% CMC, 1.5% polysorbate 80, 57.08% propylene glycol, and 40% water, as described in Example III of US Patent 3,898,348 by H. Chiu. Similarly, the aforementioned additive KOH was added to composition B until a concentration of 0.5% was reached.

[0102] The folding conditions with the four additives were conventional, and no differences in performance were observed in the folding operation or in the properties of the resulting corrugated product. The samples were packaged and stored at room temperature.

[0103] Two weeks after being folded, the four casings were filled with a typical meat emulsion for the manufacture of “hot dogs” as described in Example 1, then the sausages were peeled, and the L,a,b color was measured as described in the Methods section. Table 9 shows the results obtained. TABLE 9. L,A,B VALUES OF "HOT DOGS" WRAPPED WITH BILAYER PLEATED CASINGS WITH DIFFERENT PLEATING ADDITIVES: CONVENTIONAL (1A AND 2A) AND Petition 870210099373, dated 10 / 28 / 2021, pp. 116 / 132 26 / 29 WITH 0.5% KOH (1BE2B). Sample L to B 1A 61.3 20.8 52.4 1B 60.7 21.5 55.5 2A 60.7 20.3 55 2B 60.0 23.1 57.9

[0104] Compared to their respective control, an increase in the color transfer capacity of samples 1B and 2B is observed, whose folding composition contained 0.5% KOH. These compositions cause a decrease in the L value, i.e., the sausage is darker, an increase in the a value, the sausage is redder, and in the b value, which indicates that the sausage is more yellow, and, considering these values ​​together, the sausages prepared with samples 1B and 2B show a more orange color. EXAMPLE 7

[0105] In the present example, the effect of the hydrolytic enzyme on the envelope was studied. Lipase enzymes (hydrolytic enzymes) are tested for their ability to hydrolyze ester groups and cause the transformation of bixin into norbixin. In this example, the selected bixin was Imbarex annatto oil suspension 10% AOS.10. The dye was injected into the viscose, which is extruded through the inner layer of the extruder. Two samples were prepared, and in both, the bixin dye was injected into the viscose 15 minutes before extrusion, with the injected quantity being 14% relative to the viscose of the inner layer by weight and 1.4% relative to the total extruded viscose, which constitutes 1.84% of the bixin in the total dry cellulose. Sample 1, or the control, was passed through the different tanks of the process in a conventional manner. On the other hand, sample 2 was passed through an additional tank, which was installed in a position prior to the plasticizing tank. This Petition 870210099373, dated 10 / 28 / 2021, pp. 117 / 132 Tank 27 / 29 contained a lipase enzyme solution at a concentration of 5 g / L and a temperature of 35 °C. The treatment time for the cellulosic gel was 120 minutes. After subjecting the gel to this enzymatic treatment, it was passed through a water tank to wash away any remaining lipase enzymes and then through the plasticizing tank. The resulting wrapper showed a more orange hue than the control. As in the previous examples, in none of the samples was it detected, with the naked eye, that the process liquids inside the wrapper had been contaminated with the dye.

[0106] Both casings were filled with a typical meat emulsion for the manufacture of “hot dogs”, and subsequently the sausages were peeled and the L,a,b color was measured as described in the Methods section. Table 10 shows the results obtained. TABLE 10. L,A,B VALUES OF "HOT DOGS" WRAPPED WITH CONVENTIONAL BILAYER CASINGS AND WITH CELLULOSIC GEL TREATMENT WITH LIPASE ENZYMES (ENZYME HYDROLYTIC), AT A CONCENTRATION OF 5 G / L. Sample Enzymatic treatment of cellulosic gel (min) L ab 1 0 58.9 21.8 47.6 2 120 57.6 22.9 49.7

[0107] An increase in the ability to transfer color is observed with sample 2, the casing that was subjected to enzymatic treatment with a 5 g / l solution of lipases at 35 °C for 120 minutes. This treatment causes a decrease in the L value, i.e., the sausage is darker, an increase in the a value, the sausage is redder, and in the b value, which indicates that the sausage is more yellow, and, considering these values ​​together, the sausage prepared with sample 2 exhibits a more orange color. Petition 870210099373, dated 10 / 28 / 2021, pp. 118 / 132 28 / 29 EXAMPLE 8

[0108] In the present example, a paper-reinforced cellulose casing, commonly referred to as "Fibrous," was prepared. Typically, these casings have three concentric layers: an inner layer of viscose, an intermediate layer of long-fiber paper, usually abaca, and an outer layer also of viscose. In the extrusion process, the paper is shaped into a tubular form, and the outer and inner viscose that impregnate the paper are extruded. After impregnation with viscose, the tube is passed through coagulation-regeneration tanks, washing and plasticizing tanks, and finally dried and rolled into reels. This product can be supplied to the sausage manufacturer directly in reels or corrugated. In this example, the selected annatto bixin was Bixinex oil soluble 10% Liquid (NBX 36) from the manufacturer Pronex. A tubular abaca paper supplied by the manufacturer Ahlstrom was impregnated with inner and outer viscose.12.5% ​​of the total viscose constituted the inner layer and the remaining 87.5% the outer layer of the casing. Bixin was injected into the viscose of the inner layer 45 minutes before extrusion, and the amount injected was 10% by weight of the viscose in said inner layer and 1.25% of the total extruded viscose, which constitutes 1.64% of the total regenerated cellulose bixin.

[0109] Subsequently, a conventional casing and / or casing obtained in the present example was filled with a typical mortadella meat emulsion. The sausages were cooked in a non-smoking cycle, then peeled, and it was observed whether color transmission from the casing to the mortadella had occurred. The L,a,b color of the mortadellas was measured as described in the Methods section. Table 11 shows the results obtained. TABLE 11. L,A,B VALUES OF MORTADELLA FILLED WITH CONVENTIONAL “FIBROUS” CASINGS AND WITH INJECTION OF ANNATTO BIXINA IN THE INNER VISCOSE LAYER. Petition 870210099373, dated 10 / 28 / 2021, pp. 119 / 132 29 / 29 Sample Fibrous LAB 1 Conventional 72.5 4.6 21.8 2 Test 58.8 30.2 67.0

[0110] A significant color transfer is observed in relation to the conventional “Fibrous” casing, reflected in the decrease in the L value, and the increase in the a and b values. The mortadella had an attractive orange color on its surface. As in all previous examples, no migration of the annatto dye into the interior of the sausage was detected, remaining on the surface throughout the product's shelf life. Petition 870210099373, dated 10 / 28 / 2021, pages 120 / 132

Claims

1 / 3 CLAIMS 1. Sausage casing characterized by comprising two layers of cellulose: an inner layer whose composition comprises: regenerated cellulose and annatto, wherein the annatto comprises norbixin; and an outer layer comprising regenerated cellulose, concentric to the inner layer; the casing comprises norbixin and between 50% and 100% by weight of the annatto are distributed in the inner half of the zone comprised by said inner and outer layers of the casing.

2. A casing, according to claim 1, characterized in that the annatto content is between 0.05% (w / wTceiuiose) and 20% (w / wTceiuiose).

3. A casing, according to claim 1 or 2, characterized in that the regenerated cellulose is reinforced regenerated cellulose.

4. Procedure for obtaining the casing, as defined in any one of claims 1 to 3, characterized by comprising the steps of: a) adding an oily solution of bixin to the viscose; b) extruding in an extruder with a head comprising at least two concentric circuits the product of step a) in the inner circuit and viscose in the outer circuit; c) hydrolyzing the bixin to norbixin after step a) or after step b).

5. Procedure according to claim 4, characterized in that, in step a), an oily solution of bixin is added in an amount between 0.05% (w / w viscose) and 25% (w / w viscose).

6. Procedure according to claim 5, characterized in that the bixin solution is in a range between 0.05% (w / w viscose) and 3% (w / w viscose).

7. Procedure, as defined in claim 3, characterized in that the bixin solution is in a range between 3% (w / w viscose) and 8% (w / w viscose). Petition 870260072300, dated 07 / 21 / 2026, page 12 / 14 2 / 3 8. Procedure, as defined in claim 3, characterized in that the bixin solution is in a range between 8% (w / w viscose) and 25% (w / w viscose).

9. Procedure, as defined in any one of claims 3 to 8, characterized in that step c) of hydrolysis is carried out after step b), by subjecting the product obtained in step b) to a bath in a solution of 0.1% to 10% weight concentration of an alkaline compound.

10. Procedure according to claim 9, characterized in that the alkaline compound is selected from between: NaOH and KOH.

11. Procedure, as defined in any one of claims 3 to 8, characterized in that step c) of hydrolysis is carried out after step a) in a step prior to step b) of extrusion in which bixin is mixed with viscose for a time ranging from 0.5 minutes to 24 hours.

12. Procedure according to claim 11, characterized in that the mixing time is between 30 minutes and six hours.

13. Procedure, as defined in any one of claims 3 to 8, characterized by comprising a final step of passing through a plasticizing bath.

14. Procedure according to claim 13, characterized in that the hydrolysis step is carried out after step b) before the plasticizing bath step by means of bathing the product obtained in step b) in a bath of a hydrolytic enzyme.

15. Procedure according to claim 14, characterized in that the hydrolytic enzyme is comprised between 2 g / l and 10 g / l.

16. Procedure, as defined in any one of claims 3 to 8, characterized by a folding or corrugating step of the envelope and the hydrolysis step being carried out after step b) in the folding step by applying a folding composition comprising an alkaline compound at a concentration between 0.1% and 10% by weight. Petition 870260072300, dated 21 / 07 / 2026, pp. 13 / 14 3 / 3 17. Procedure according to claim 16, characterized in that the alkaline compound is selected from between KOH and NaOH.

18. Embedded casing characterized by being obtainable by the procedure as defined in any of claims 3 to 17. Petition 870260072300, dated 07 / 21 / 2026, page 14 / 14