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    • 专利摘要:
    Cellulose casing, method of obtaining it and product stuffed in said casing. The present invention relates to cellulose casings, whether reinforced or not, capable of transferring color to the product embedded therein. These casings contain a food coloring that is transferable to the sausage during processing. The present invention also relates to the method of obtaining the casing and the product stuffed in said casing. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2791063A1
    申请号:ES201930380
    申请日:2019-04-30
    公开日:2020-10-30
    发明作者:Martínez Ion Iñaki García；Ongay Alfonso Razquin；Fuentes Joana Jiménez；Areso Carlos María Longo
    申请人:Viscofan SA；
    IPC主号:
    专利说明:

    [0002] Cellulose casing, method of obtaining the same and product stuffed in said casing
    [0004] The present invention relates to cellulose casings, whether reinforced or not, capable of transferring color to the product embedded therein. These casings contain a food coloring that is transferable to the sausage during processing. The present invention also relates to the method of obtaining the casing and the product stuffed in said casing.
    [0006] Background of the invention
    [0008] Manufacturers of sausages and other sausages have a need to give their products an attractive appearance to consumers. Color is an aspect of great importance, and in sausages the resulting color will depend on the type of emulsion and meat used, on the processing conditions and on whether or not it has undergone a smoking treatment.
    [0010] For example, traditionally sausages have been colored by applying natural smoke in gaseous form, or also by spraying or immersion in liquid smoke from wood. Depending on the conditions and type of smoking, sausages are obtained with a brown color, ranging from very light beige tones, to very dark, almost black tones.
    [0012] In some markets it is customary to color the surface of the sausage by applying food coloring. For example, in the Philippines the consumption of sausages with a very intense red color is very widespread, which is achieved by applying the synthetic dye Allura Red (E-129). In addition to the red color, in other markets such as the USA and Australia, orange-colored sausages are also obtained by applying the synthetic dye Sunset Yellow (E-110). But one of the main disadvantages of using synthetic colorants is that upon transfer to the surface of a sausage, they have a tendency to penetrate the surface and migrate from the surface towards the center of the sausage. Such migration is undesirable, because the customer prefers that only the skin of the coagulated protein surface be colored, and not the interior of the sausage. Furthermore, when mixtures of these synthetic colorants are used, such migration can occur at different speeds and to different degrees, thus producing a chromatographic effect where the sausage in the cross section can present different colored rings. Another limitation of the use of these synthetic colorants is that in many countries their use for the coloration of meat products is not authorized.
    [0014] On the other hand, in Brazil it is very popular to submerge the sausages once cooked and peeled in a solution of annatto in its water-soluble form (norbixin), in order to obtain a red-orange color. The coloration obtained will depend on the concentration of the colorant, the immersion time and the temperature. This water-soluble colorant is fixed to the surface of the sausage by a second immersion in an acid medium, usually in a solution of phosphoric acid.
    [0016] This method has many disadvantages, such as the need to make an investment in the facilities to apply the colorant (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 with traces of colorant. In addition, the sausages present easily perceptible color differences, due to the difficulty in ensuring the same residence time and coloring capacity from one day to the next.
    [0018] Similarly, in Chile a type of sausage is marketed, called "Sureña", which also has a red-orange color, but in this case by adding the water-soluble annatto to the meat emulsion, which leads to an unwanted coloration of the inside of the sausage . This coloring of the entire meat emulsion entails a higher cost than the superficial coloring of the sausage, because it is necessary to apply a much greater quantity of annatto, which also gives the product an undesirable taste. Another negative point of this practice is that it gives it a very unnatural appearance to the sausage, since the entire interior of the sausage presents an artificial color that causes distrust and displeases consumers.
    [0020] Finally, it should be noted that there is a strong trend among consumers in the more developed markets to avoid the use of synthetic colorants, and substitute them with colorants of natural origin, such as annatto, which is a colorant that is extracted from the seeds of annatto. , and that has been used since time immemorial by Native Americans.
    [0021] Several patents describe procedures for coloring sausage casings, which are subsequently capable of transferring said colorant to the surface of the sausage during the stuffing and cooking processes.
    [0023] The most common procedure to produce said coloring envelopes is the impregnation of the cellulosic gel by passing it through a tank containing a solution of the coloring. As described in patents US2,477,767 and US2,477,768 (Remer et al.). This methodology had problems of dye impregnation heterogeneity as described in patent US2,521,101 (Thor et al.). Patent US2,521,101 proposes to obtain a uniformly colored casing with a simple method that improves production performance, such as applying the dye and glycerin in a bath adjusted to pH 7.5-9.5 before drying the gel. cellulosic. To avoid yield losses when it is necessary to produce transparent casings again, it is proposed to use a glycerin tank prior to the glycerin and dye tank, which is a movable container, which would be placed only when colored casings are to be produced. That way, it is not necessary to empty the glycerin and dye tank, clean it and add clean glycerin when producing transparent casings, thus saving production time. When colored casings are to be produced, the mobile glycerin and dye tank is again placed between the glycerin tank and the dryer. Although the color is more uniform, it is necessary to take into account the color variations that occur with the pH in most colorants, so use a suitable mixture that gives the desired color to the pH of the tank. Examples of orange and cherry casings are given in the patent, which transfer the color to the sausage evenly.
    [0025] This procedure was later improved by the invention of patent US3,438,071 (Clark et al.) Which describes a simple system to control the level of the tank containing the dye and glycerin. For this, it places an additional storage tank to which the tank through which the cellulosic gel passes is connected, and which feeds it automatically in response to a drop in level. This allows to obtain casings with a more uniform color tone.
    [0027] But this process for impregnating the cellulosic gel 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 a lack of chemical affinity, or due to its high molecular size, the cellulosic gel does not substantially absorb these forms of the annatto dye, or if it absorbs it, it then has a hard time releasing it to the sausage. Thus, When trying to apply annatto to a cellulose casing, the so-called "bubble" or "slug coating" methodology has been commonly used to internally coat the casings.
    [0029] Both dyes (norbixin and bixin) separately, if used to internally coat cellulosic casings, do not give good results.
    [0031] 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 anatto dye, norbixin, and another oil-soluble component (which can be bixin, the other dye of the annato), which is transferred uniformly during the processing of the sausages made with these casings. Both the casings obtained and the method that uses them to give red-orange coloring to sausages and similar meat products are claimed in the patent. In this case the coating is a step that must be done offline within the usual processes for obtaining casings, which means that it is not an economical method.
    [0033] Patent US 5,955,126 (Jon et al) describes compositions of bixin, a water-soluble film-forming agent (preferably hydroxypropylcellulose), a polyphosphate and optionally an antioxidant, as well as casings coated with said composition. In addition to the preferred application by means of the "bubble" or "slug coating" method, they describe the possibility of applying the coloring composition by means of an internal spray during the pleating stage of the envelope. Its division US 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 dispersion of the colorant) of 3 microns or less as defined in the ASTM D-1316-87 method. 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 has a film-forming agent, and in all its embodiments it is intended to obtain bixin on the internal surface that is in contact with the sausage.
    [0035] The patent application US 2003/0039724 A1 (DuCharme et al.) Describes the manufacture of cellulose casings colored in 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 "bubble" or "slug coating". The request mentions the possibility of applying the coloring composition of the invention on the viscose just before the extrusion step. Although it is expected that the colorants will be trapped in the casing, and therefore not transferred to the sausage, they believe that liquid fumes and some appropriate natural red colorants that are located on the surface of the casing, can be transferred to the sausage if, being in contact with the surface of the casing, they are subjected to high temperature.
    [0037] Finally, patent CA 713510 (A.H. Cameron) mentions a method of spraying a coloring solution with caramel that is applied to the inside of the casing once it has been pleated, at the previous moment of stuffing.
    [0039] Despite the various inventions described above, to date there is no cellulose casing on the market, capable of transferring the annatto dye in any of its forms, to the sausage. The process of spraying the coloring composition carried out during the pleating process leads to a very heterogeneous color distribution, due to the fact that the colorant accumulates in the pleat folds, giving rise to more intense marks on the surface of the sausage.
    [0041] As for the products prepared by the "bubble" or "slug coating" method, they also present the same problem of heterogeneity of the transferred color, although to a lesser extent. But the main problem with this technology is its high application cost. especially in gauges below 50 mm, since they require an "off-line" application such as that represented in Figure 1 of US Patent 5,955,126.
    [0043] That is why, as mentioned above, there is no commercial cellulose casing product capable of transferring annatto dye to sausage in a homogeneous manner, despite strong demand from sausage manufacturers.
    [0045] Description of the invention
    [0047] Annatto or bija is a colorant obtained from annatto or orellana ( Bixa orellana L.), a species originally native to the Amazon basin. It is obtained from the reddish pulp that surrounds the seeds, and is used to color many foods, such as cheeses, margarine, butter, rice, smoked fish. Annatto is the name given to the crude extract, which contains two edible pigments: norbixin, which is water-soluble and is therefore the most abundant in water-soluble extracts of annatto, and oil-soluble annatto colorants containing bixin as the main colorant. Both are carotenoid pigments and therefore can be affected by light and oxygen, which can alter their conjugated double bond structure. Bixin is the monomethylester of norbixin, so norbixin can be obtained from bixin by alkaline saponification.
    [0049]
    [0052] Norbixin formula
    [0054] The aim of the present invention is to overcome the deficiencies presented by the cellulose casings with inner coating of annatto compositions mentioned above. In contrast to prior art casings which are covered 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 stuffed within said casing, in a substantially uniform.
    [0056] The inner layer of the casing containing the annatto may have different thickness and / or concentration of annatto, which will make it acquire different shades after transfer to the sausage. When the amount of annatto in said layer is low, the transfer of color will also be low, and the color obtained will be a light brown or beige tone, similar to that obtained by subjecting the sausage to light smoking. When this concentration is increased, the transfer increases and the tone of the sausage will be substantially oranged Red. The final color resulting from the sausage will depend, among other factors, on the composition of the meat emulsion and the cooking conditions.
    [0058] The annatto in the casing of the present invention is distributed throughout the inner layer.
    [0060] The first aspect of the invention refers to a sausage casing comprising two layers of cellulose:
    [0061] an inner layer whose composition comprises: regenerated cellulose and annatto, where the annatto comprises norbixin; and an outer layer comprising regenerated cellulose, concentric to the inner layer; where the casing comprises norbixin and between 50% and 100% by weight of the annatto is distributed in the inner half of the area comprised by said inner and outer layer of the casing.
    [0063] In the present invention the term "inner layer" refers to any layer that lies between two layers of the casing or between one layer and the sausage.
    [0065] In the present invention, the term "regenerated cellulose" refers to the cellulose obtained from the solution of some cellulose derivative such as cellulose xanthate. The solution of some cellulose derivative is transformed into viscose by any of the methods known in the state of the art and the viscose is extruded to obtain regenerated cellulose.
    [0067] In the present invention the term "annatto" refers to the set of the bixin compound and the norbixin compound, when it refers to a percentage of annatto it refers to the sum of the percentages of the bixin compound and the norbixin compound in the shell. in case the hydrolysis of bixin is total, annatto refers only to norbixin.
    [0069] In the present invention the term pTcellulose refers to the total weight of regenerated cellulose in the casing, in particular in all the layers that are present in the casing.
    [0071] A second aspect of the invention is the process for obtaining the wrapping of the invention.
    [0073] In the process of the invention the different layers of regenerated cellulose are obtained by extrusion of the viscose. To one of the internal layers an oily solution of bixin, bixin that is hydrolyzed at a later stage.
    [0075] The present invention avoids the problem of mixing viscose with norbixin, since the mixture undergoes severe dehydration during coagulation, with the water being able to carry a large part of the water-soluble dye. Possible subsequent washings in the case of including norbixin in the mixture would also cause additional loss of the colorant, so that the amount of colorant that would remain in the final casing is insufficient for the purpose of transmitting sufficient color to the sausage. Furthermore, the colorant strongly contaminates the process liquids.
    [0077] Bixin in oily solution, which is not soluble in water, does not pollute the washing water. On the other hand, its conversion into norbixin is preferred so that during the cooking process of the meat stuffed in the casing, the water-soluble dye efficiently migrates and transfers a sufficient amount of color for the purpose of this invention. Surprisingly, despite the fact that the process of the invention transforms bixin into norbixin during the manufacturing process, either totally or partially, it is trapped in the inner layer of the casing and does not significantly contaminate the coagulation bath. regeneration, nor washing waters.
    [0079] Therefore, a second aspect of the invention refers to a process for obtaining the envelope defined in the invention that comprises the steps of:
    [0080] a) adding an oily solution of bixin to viscose;
    [0081] b) extrude in an extruder with a head comprising at least two concentric circuits, the product from stage a) in the inner circuit and viscose in the outer circuit: c) hydrolyze the bixin to norbixin after stage a) or after stage b).
    [0083] In the present invention the term "bixin oil solution" refers to bixin oil solutions or solutions, suspensions or emulsions These bixin oil solutions comprise between 0.1% and 20% bixin.
    [0085] In the present invention (w / pviscose) refers to the ratio between the weight of the oily solution of bixin and the weight of viscose that is used to form the bixin layer.
    [0087] In step b) in 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. Another aspect of the invention is a sausage casing obtainable by the procedure defined in the invention.
    [0089] Another aspect of the invention is the use of the casing of the invention in the production of sausages.
    [0091] Another aspect of the invention is a product stuffed in the casing of the invention. A last aspect is the method of obtaining the stuffed product in the casing of the invention, which comprises the steps of: a) stuffing a mixture of stuffed meat into the casing of the invention; b) cooking the stuffed mixture; c) remove the wrapping.
    [0093] Brief description of the drawings
    [0095] Figure 1 shows a cross section of the wall of the multilayer envelope obtained in example 1. The left part is the uncolored outer layer having a thickness of 9.9. ^ M, the central part is the inner layer colored with annatto and which has a thickness of 4.9. ^ m, and the right part is the uncolored inner layer which has a thickness of 9.9. ^ m.
    [0097] Figure 2 shows a cross section of the wall of a bilayer casing. The left part is the uncolored outer layer with a thickness of 18. ^ M, and the right part is the colored inner layer with a thickness of 6.9. ^ M.
    [0099] Figure 3 shows an absorption spectrum of the transferable dye of two regenerated cellulose shells: (1) Control (2) Treatment of cellulosic gel with KOH 2% according to example 4.
    [0101] Description of a preferred embodiment
    [0103] As mentioned above, the first aspect of the invention refers to a sausage casing comprising two layers of cellulose:
    [0104] an inner layer whose composition comprises: regenerated cellulose and annatto, where the annatto comprises norbixin; and an outer layer comprising regenerated cellulose, concentric to the inner layer; where the casing comprises norbixin and between 50% and 100% by weight of the annatto is distributed in the inner half of the area comprised by said inner and outer layer of the casing.
    [0106] In a preferred embodiment, the annatto is comprised between 0.05% (w / pTcellulose) and 20% (w / pTceiuiosa), more preferably between 0.2% (w / pTceiuiosa) and 5% (w / pTceiuiosa).
    [0108] Preferably the casing does not have an inner annatto coating.
    [0110] 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 wrapping has three concentric layers, an inner viscose, an intermediate long-fiber paper, and a third outer layer also of viscose.In particular, the long-fiber paper is abacá.
    [0112] In a preferred embodiment, the number of layers of the wraps of the invention is selected from two to three.
    [0114] As has been said, a second aspect of the invention refers to a procedure for obtaining the envelope defined in the invention that comprises the steps of:
    [0115] a) adding an oily solution of bixin to viscose;
    [0116] b) extrude in an extruder with a head comprising at least two concentric circuits, the product from stage a) in the inner circuit and viscose in the outer circuit: c) hydrolyze the bixin to norbixin after stage a) or after stage b).
    [0118] In a preferred embodiment, the amount of the oily bixin solution that is added to the viscose in step a) is between 0.05% (w / pviscose) and 25% (w / pviscose). In a more preferred embodiment, the amount of the oily bixin solution that is added to the viscose in step a) is between 5% (w / pviscose) and 20% (w / pviscose).
    [0120] In a preferred embodiment, the step of hydrolyzing the bixin to norbixin is carried out after step a) in a step prior to step b) of extrusion; In this new stage, 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 done in a uniform manner by a mechanical mixing system, either statically or dynamically.
    [0122] In another preferred embodiment, the step of hydrolyzing the bixin to norbixin is carried out after step b) subjecting the product obtained in step b) to a 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.
    [0124] In the present invention the term "alkaline compound" refers to a hydroxide, to a carbonate or bicarbonate of an alkali or alkaline earth metal, to an ammonium hydroxide or salts thereof or to an amine. Preferably the alkaline compound is selected from among : NaOH, KOH, methylamine, dimethylamine, trimethylamine, ethylamine, among others and NH4OH, in particular it is KOH.
    [0126] Process step a) takes place significantly at a temperature below 40 ° C, preferably between 20 ° C and 40 ° C, with a temperature of 20 ° C to 25 ° C being more preferable.
    [0128] The amount of the oily bixin solution in step a) is preferably in an amount of 0.05% to 25%. More preferably between 0.05% to 3% if it is intended to obtain a beige or light brown color in the sausage stuffed in said casing, from 3% to 8% if a yellowish orange color is desired or from 8% to 25%, if it is intended to obtain a more red-orange tone.
    [0130] Preferably, the process comprises in any of the embodiments of the invention a final step of passing through a plasticizing bath. Preferably the plasticizing bath comprises glycerin.
    [0132] 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. The enzyme is preferably 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.
    [0134] In general, in the processes for obtaining casings there is a step of pleating or corrugated the casing. During this stage it is usual to internally spray an aqueous solution containing ingredients that increase the plasticity of the casing or also facilitate the subsequent peeling and separation of the casing from the sausage, such as carboxymethylcellulose or CMC.
    [0136] In the present invention, in a particular embodiment, said pleating compositions can incorporate an alkaline compound, preferably selected from: KOH, NaOH, amines or NH4OH that will hydrolyze the bixin present in the inner layer of the inventive envelope in water-soluble norbixin . Corrugated casings can be stored at temperatures up to 90 ° C to accelerate said reaction, but preferably they are stored at temperatures between 20 and 40 ° C, for a time that can be from several minutes to several months. The concentration of the alkaline compound in these pleating compositions can vary from 0.1% to 10% by weight, more preferably between 0.5 to 3%.
    [0138] As has been said, another aspect of the invention is the use of the casing of the invention in the production of sausages and a last aspect of the invention is a product stuffed in the casing of the invention. In both cases in a particular way the sausage is sausage.
    [0140] In a last particular embodiment of the method of obtaining the sausage product, the sausage without casing, after removing the casing, is immersed in an acid solution, preferably in a phosphoric acid solution. Preferably between 30 seconds and 5 minutes. Preferably, the phosphoric acid solution is at a concentration by weight of between 5% and 10%.
    [0142] EXAMPLES
    [0144] The following examples are only illustrative of this invention, and should not be construed in a limiting sense thereof.
    [0146] In all examples the methods for quantifying the color transmission ability in the prepared samples are as follows.
    [0147] METHODS
    [0149] The following methods have been used for the quantification of the color transmission capacity of the samples prepared in the examples of the invention.
    [0151] L, a, b Test
    [0153] Hunter L, a, b values are a standard procedure for quantifying the color scale of a product. This procedure shows the differences in brightness, hue, and color saturation. The L parameter indicates the brightness of the color, the value 100 corresponding to white, and the value zero to black. The parameter a indicates the gradient from red to green, representing a redder color as a increases. The parameter b indicates the gradient from yellow to blue, and as it increases it indicates that the color is more yellow.
    [0155] In the examples of the invention, the Hunter L, a, b color scale was used to measure the color of cellulose casings and sausages from which the casing has been removed, to quantify the color that said casing has transmitted. In the case of the casings, the measurement was carried out on two superimposed layers and placed on a white tile. In the case of the sausages, they have been covered with a transparent plastic film, and the measurement was made by placing the colorimeter directly on them. The plastic film prevents contamination and fouling of the colorimeter. The value obtained was the mean value of 5 measurements. A colorimeter model Ci62S from the X-rite brand was used.
    [0157] Removable color
    [0159] This method allows us to quantify the color transmission capacity of a cellulose casing. In the examples of the invention, this method was used to determine said color transmission capacity of regenerated viscose films and cellulose casings. The procedure consists of placing the sample in an Erlenmeyer flask with 250 ml of 0.008% weight / volume KOH, which has been prepared by diluting one gram of 2% KOH solution to 250 ml. Subsequently, the Erlenmeyer flask is placed on a hot plate until boiling, and is kept for 5 minutes. After allowing to cool, the sample is removed and the absorbance of the supernatant at 480 nm is measured. In the measurements of the examples of the invention, a spectrophotometer model US / VIS Lambda 365 from the Perkin Elmer brand was used. The higher the absorbance, the higher the annatto concentration, and therefore the higher the sample color transmission.
    [0161] Example 1
    [0163] In this example, a colored casing was prepared with an extruder as described in patent ES 2160091 B1 (de García et al.).
    [0165] The cellulose was regenerated from viscose. The viscose had an alkali content equivalent to 6% NaOH.
    [0167] A three-layer wrap was made in which bixin was injected into the viscose of an inner layer of the wrap, in this case the center layer.
    [0169] To carry out this example, bixin in dispersion in oil of the brand Imbarex annatto oil suspension 10% AOS.10 was selected.
    [0171] The dye was injected into the viscose that is extruded through the center layer of the extruder. For this, an Iwaki diaphragm pump model EWNB11VCER and a dynamic mixer were used.
    [0173] The amount injected into viscose was 18.4% by weight with respect to the viscose of the central layer, and 3.68% with respect to the total viscose that constitutes 4.84% of annatto on total cellulose. The injection was carried out 15 minutes before the moment of extrusion.
    [0175] The process liquids inside the casing were not detected with the naked eye to be contaminated with the colorant.
    [0177] The casing obtained was stuffed with a typical meat emulsion for the manufacture of "hot dogs", they were cooked in a cycle without smoking, as described in Table 1, and subsequently the sausages were peeled and it was observed that surprisingly a certain transmission of color from the casing to the sausage, obtaining sausages with a beige surface color, similar to that obtained with slightly intense smoking.
    [0179] Table 1. Description of the "hot dogs" cooking process.
    [0184] This result shows that the phenomenon of color transmission is not only due to surface contact of the casing and the meat emulsion, but that some other phenomenon hitherto unknown is involved. In order to investigate this phenomenon, a transverse section of the envelope wall was made and the structure was studied with light microscopy. Figure 1 shows the presence of three concentric layers, an outer (left side of the image) non-colored 9.9 ^ m thick, a central colored 4.9 ^ m thick, and an inner (side right of image) 9.9 ^ m thick.
    [0186] In addition, it is observed that the annatto has not been confined in the central layer, since it is what would be expected of bixin because it is oil soluble, but there is diffusion of color 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.
    [0188] Example 2
    [0190] In the present example, the aim is to maximize the transfer of color by extruding a bilayer casing, that is, it has two concentric layers, an exterior without annatto dye and an interior with annatto, which will transmit the color to the sausage. Figure 2 shows A cross section of the envelope wall under the microscope, showing an uncolored outer layer 18. ^ m thick (left part) and a colored inner layer 6.9. ^ m thick (right part). In addition, different casings have been prepared with different concentrations of bixin in the inner layer. The bixin selected for this example was Imbarex annatto oil suspension 10% AOS.10, the same as that of example 1. The dye was injected into the viscose that is extruded through the inner layer of the extruder, using the same equipment pumping and mixing than Example 1.
    [0192] The injected amount comprises from 6%, 8%, 10%, 12%, 15% and 18% by weight with respect to the viscose extruded by the inner layer, and from 0.36%, 0.48%, 0.60% , 0.72%, 0.90% and 1.08% with respect to the total extruded viscose and which constitute 0.47%, 0.63%, 0.79%, 0.95%, 1.18% and 1 , 42% respectively of bixin on total cellulose. The contact time of the bixin with the viscose was increased to 30 minutes.
    [0193] As in Example 1, the casing could be rolled up without problems, giving rise to a compact coil, and after the corrugation a manageable product was obtained, similar in properties to that obtained with non-colored casings. And like example 1, it was not detected with the naked eye that the process liquids inside the casing were contaminated with the colorant.
    [0195] The 6 casings obtained and one more without coloring (negative control), were stuffed with a typical meat emulsion for the manufacture of "hot dogs" and later the sausages were peeled and the color L, a, b was measured as described in the Methods section.
    [0197] Table 2 shows the results obtained.
    [0198] Table 2. L, a, b values of "hot dogs" stuffed with bilayer casings with different concentration of bixin in the inner layer.
    [0203] A significant color transfer is observed with respect to the negative control, and the intensity of said color increases as the injected concentration of bixin increases in the inner layer of the envelope. The higher the concentration, the L value decreases, the sausage is darker, the a value increases, the sausage is redder, and 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 dye.
    [0205] Subsequently, a procedure was applied that allows us to increase the red tone of the sausages prepared with the casings of the present invention. For this, the peeled sausages that had been prepared with 18% bixin from the present example were taken and immersed in a 5% phosphoric acid solution at 20 ° C for one minute (for the preparation of the solution, acid phosphoric 85% of PANREAC). The action of Acid causes a reddening of the sausage, a coloration that is preferred by some consumers.
    [0207] The color L, a, b of the sausages was measured as described in the Methods section. Table 3 shows the results obtained.
    [0209] Table 3. L, a, b values of "hot dogs" stuffed with the casings of the present example with 18% bixin annatto in the inner layer.
    [0214] The treatment of the sausage with phosphoric acid does not significantly alter the L value, that is, the sausage maintains its brightness, but 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 taking these values together, that the sausage prepared with sample 2 shows a more reddish color.
    [0216] Example 3
    [0218] In the present example, the sample from Example 2 containing 12% bixin relative to the weight of the viscose of the inner layer was taken and hot dogs were prepared with a typical emulsion to which 0.06% of Carmine 25% L-OD from the supplier Sensient, in order to give it a more rosy hue.Sample 1 was prepared with a dye-free casing, samples 2 and 3 with the aforementioned casing from Example 2, but in the case of the sample 3 had been turned over, so that the non-colored 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.
    [0220] Table 4. Description of the "hot dogs" cooking process.
    [0224] Subsequently, the color L, a, b of the sausages was measured as described in the Methods section. The results obtained are shown in Table 5.
    [0226] Table 5. L, a, b values of "hot dogs" stuffed with casings (1) without coloring, (2) with 12% bixin annatto in the inner layer and (3) casing (2) but turned over.
    [0231] It is observed that in samples 2 and 3 the transfer of colorant to the sausage takes place, and that this is much less in the case in which the casing has been stuffed upside down, due to the difficulty encountered by the colorant to migrate through the cellulose layer not colored. This difference in color transmission would indicate that the most efficient wrapper for the purpose of the invention is the one that presents most of the colorant in the inner half of the wrapper.
    [0233] Example 4
    [0235] The cellulose casings prepared in the present example 4 have different contact times between bixin and viscose. In this example, the selected bixin has been Bixinex oil soluble 10% Liquid (NBX 36) from the manufacturer Pronex. The dye was injected into the viscose that is extruded through the inner layer of the extruder. In sample 1 the bixin was injected into the viscose 15 minutes before the moment of extrusion and the injected amount was 14% with respect to the viscose of the inner layer by weight and 0.98% with respect to the whole of the extruded viscose. which constitutes 1.29% of bixin on total dry cellulose. In sample 2, the dye bixin was injected into the viscose 4.5 hours before the moment of extrusion and the injected amount was 13.2% with respect to the viscose of the inner layer by weight and 0.94% with respect to to the whole extruded viscose that constitutes 1.23% of bixin on total regenerated cellulose. As in previous examples, no With the naked eye, the process liquids inside the casing will be contaminated with the colorant.
    [0237] Both casings were stuffed with a typical meat emulsion for the manufacture of "hot dogs", and subsequently the sausages were peeled and their color L, a, b measured as described in the Methods section. Table 6 shows the results obtained.
    [0239] Table 6. L, a, b values of "hot dogs" stuffed with bilayer casings with different contact time with alkaline viscose.
    [0244] An increase in the ability to transfer color is observed with sample 2, which has been in contact with the viscose for a longer period of time. The longer the contact time the L value decreases, the sausage is darker, the a value increases, the sausage is redder, and the b value, which indicates that the sausage is more yellow, and taking these values together, that the Sausage prepared from Sample 2 shows a more orange color.
    [0246] Example 5
    [0248] In the present example, the effect of a post-extrusion treatment with a KOH solution has been studied.
    [0250] In this example, the selected annatto bixin was Imbarex annatto oil suspension 10% AOS.10. The dye was injected into the viscose that is extruded through the inner layer of the extruder.
    [0252] Two samples were prepared and in both the bixin was injected into the viscose 10 minutes before the moment of extrusion, the amount injected being 12% with respect to the viscose of the inner layer by weight and 1.2% with respect to the whole of the extruded viscose that constitutes 1.58% bixin on total dry cellulose. Sample 1, or control, was passed through the different process tanks in a standard way. Instead, sample 2 was passed through an additional tank, which was positioned prior to the plasticizing tank. Said tank it 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 subjecting this alkaline treatment, it was passed through a tank with water, to eliminate the excess KOH, and then through the plasticizing tank. With the naked eye it was observed that the resulting envelope had a more orange hue than the control. As in previous examples, neither of the two samples was detected with the naked eye that the process liquids inside the shell were contaminated with the colorant.
    [0254] 25 cm of wrapping film was taken, it was cut on one of its sides in the longitudinal direction and it was placed in an Erlenmeyer flask with 250 ml of 0.008% weight / volume KOH. The Erlenmeyer flask was boiled for 5 minutes and after cooling the supernatant the spectrum in visible light was measured. The result shows that the envelope that was subjected to the treatment in a KOH tank (sample 2) underwent a transformation that caused an increase in absorbance in the wavelength range of 400-600 nm, which indicates that said envelope has greater color transmission capacity (Figure 3).
    [0256] Both casings were stuffed with a typical meat emulsion for the manufacture of "hot dogs." Subsequently, the sausages were peeled and the color L, a, b measured as described in the Methods section. Table 7 shows the results obtained.
    [0258] Table 7. L, a, b values of "hot dogs" stuffed with standard bilayer casings and with cellulosic gel treatment with 2% KOH.
    [0263] An increase in the ability to transfer color is observed with sample 2, which has been subjected to a treatment with a 2% KOH solution at 65 ° C for 150 s. Said treatment results in a decrease in the L value, that is, the sausage is darker, an increase in the a value, the sausage is redder, and the b value, which indicates that the sausage is more yellow, and taking these values in overall, that the sausage prepared with sample 2 shows a more orange color.
    [0265] Example 6
    [0266] From the envelope of sample 1 of example 5, pleated samples were prepared with 4 different additives according to procedures known in the art. Pleating additives are compositions that are sprayed into the wrap during the pleating operation. Its main function is to provide the envelope with greater plasticity and thus overcome the pleating stage without suffering an appreciable deterioration of its mechanical properties. In addition, it is common in the art to apply pleating additives that also make the casing easier to separate from the sausage in the peeling stage, known as "easy peeling" additives. These compositions usually include carboxymethylcellulose (CMC) as an agent. main that favors the peeling of the sausage Table 8 shows the type of pleating compositions used in the present example.
    [0268] Table 8. Description of the composition of the pleating additives.
    [0273] Additive 1 is a composition that does not have CMC, and that does not have the function of promoting the peeling of the sausage, and that is normally used in casings whose purpose is to be peeled by the end consumer, not by the manufacturer of the sausage. The composition of additive 1A comprises 30% propylene glycol and 70% water, as described in Example IX of US Patent 3,981,046 by H. Chiu. In composition B, KOH was added to said additive until reaching a concentration of 0.5%. On the contrary, additive 2 is a typical composition that CMC presents to favor the mechanical peeling of the sausages by the sausage manufacturer. The composition of additive 2A comprises 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. Likewise, in composition B KOH was added to said additive until reaching a concentration of 0.5%.
    [0275] The pleating conditions with the four additives were standard, not observing differences in performance in the pleating operation, nor in the properties of the resulting corrugated product. The samples were packaged and stored at room temperature.
    [0276] Two weeks after being pleated, the four casings were stuffed with a typical meat emulsion for the manufacture of "hot dogs" as described in example 1, and subsequently the sausages were peeled and the color L was measured, at , b as described in the Methods section Table 9 shows the results obtained.
    [0278] Table 9. L, a, b values of "hot dogs" stuffed with pleated bilayer casings with different pleating additives: standard (1A and 2A) and with 0.5% KOH (1B and 2B).
    [0283] When comparing with their respective control, an increase in the ability to transfer color of samples 1B and 2B is observed, whose pleating composition contained 0.5% KOH. Said compositions give rise to a decrease in the L value, that is, the sausage is darker, an increase in the a value, the sausage is redder, and the b value, which indicates that the sausage is more yellow, and taking these values in overall, that the sausages prepared with samples 1B and 2B show a more orange color.
    [0285] Example 7
    [0287] In the present example the effect of the hydrolytic enzyme on the envelope has been studied. Lipase enzymes (hydrolytic enzyme) are tested for their ability to hydrolyze ester groups, and cause the transformation of bixin into norbixin. In this example, the selected bixin has been Imbarex annatto oil suspension 10% AOS.10. The dye was injected into the viscose that is extruded through the inner layer of the extruder. Two samples were prepared and in both the dye bixin was injected into the viscose 15 minutes before the moment of extrusion, the injected amount being 14% with respect to the viscose of the inner layer by weight and 1.4% with respect to the set of the extruded viscose that constitutes 1.84% of bixin on total dry cellulose. Sample 1, or control, was passed through the different process tanks in a standard way. Instead, sample 2 was passed through an additional tank, which was positioned prior to the plasticizing tank. Said tank contained a lipase enzyme solution in a concentration of 5 g / L and a temperature of 35 ° C. The treatment time of the cellulosic gel was 120 minutes. After subjecting the gel to this enzymatic treatment, it was passed through a tank with water, to wash the remains of lipase enzymes, and then through the plasticizing tank. The resulting wrapper had a more orange hue than the control. As in previous examples, neither of the two samples was detected with the naked eye that the process liquids inside the shell were contaminated with the colorant.
    [0289] Both casings were stuffed with a typical meat emulsion for the manufacture of "hot dogs", and subsequently the sausages were peeled and their color L, a, b measured as described in the Methods section. Table 10 shows the results obtained.
    [0291] Table 10. L, a, b values of "hot dogs" stuffed with standard bilayer casings and with cellulosic gel treatment with lipase enzymes (hydrolytic enzyme), at a concentration of 5 g / L.
    [0296] An increase in the ability to transfer color is observed with sample 2, an envelope that has been subjected to an enzymatic treatment with a solution of 5 g / L of lipases at 35 ° C for 120 minutes. Said treatment results in a decrease in the L value, that is, the sausage is darker, an increase in the a value, the sausage is redder, and the b value, which indicates that the sausage is more yellow, and taking these values in overall, that the sausage prepared with sample 2 shows a more orange color.
    [0298] Example 8
    [0300] In the present example, a paper-reinforced cellulose casing has been prepared, commonly referred to as "Fibrous." These casings normally have three concentric layers, an inner viscose, an intermediate long-fiber paper, usually abaca, and a third The outer layer is also made of viscose. In the extrusion process, the paper is formed into a tubular shape, and the outer and inner viscose that impregnate said paper are extruded. After impregnation with the viscose, the tube is passed through the coagulation-regeneration tanks , washing and plasticizing tanks, and finally it is dried and rolled into reels. This product can be supplied to the manufacturer of sausages directly on reels or corrugated. In this example the annatto bixin selected has been Bixinex oil soluble 10% Liquid ( NBX 36) from the manufacturer Pronex. Abaca tubular paper provided by the manufacturer Ahlstrom was impregnated with inner and outer viscose. 12.5% of the total viscose made up the inner layer and the remaining 87.5% the outer layer of the wrap. The bixin was injected into the viscose of the inner layer 45 minutes before the moment of extrusion and the amount injected was 10% with respect to the viscose of said inner layer by weight and 1.25% with respect to the whole of the extruded viscose which constitutes 1.64% of bixin on total regenerated cellulose.
    [0301] Subsequently, a standard casing and the casing obtained in the present example were stuffed with a typical meat emulsion of mortadella. The sausages were cooked on a cycle without smoking, and subsequently peeled and it was observed whether color transmission had taken place from the casing to the mortadella. The color L, a, b of the mortadelas was measured as described in the Methods section. Table 11 shows the results obtained.
    [0303] Table 11. L, a, b values of mortadella stuffed with standard “Fibrous” casings and with injection of annatto bixin in the inner viscose layer.
    [0308] A significant color transfer is observed with respect to the standard "Fibrous" envelope, reflected in the decrease of the L value, and the increase of the a and b values. The mortadella had an attractive orange color on its surface. As in all the previous examples, no migration of the annatto dye into the sausage is detected, but rather it remains on the surface throughout the useful life of the product.
    权利要求:
    Claims (20)
    [1]
    1. A sausage casing comprising two layers of cellulose:
    an inner layer whose composition comprises: regenerated cellulose and annatto, where the annatto comprises norbixin; and an outer layer comprising regenerated cellulose, concentric to the inner layer; where the casing comprises norbixin and between 50% and 100% by weight of the annatto is distributed in the inner half of the area comprised by said inner and outer layer of the casing.
    [2]
    2. A casing according to claim 1 wherein the annatto is comprised between 0.05% (w / pTcellulose) and 20% (w / pTcellulose).
    [3]
    3. Casing according to claim 1 or 2, wherein the regenerated cellulose is reinforced regenerated cellulose.
    [4]
    4. A method for obtaining the envelope defined in any of claims 1 to 3 comprising the steps of:
    a) adding an oily solution of bixin to viscose;
    b) extrude in an extruder with a head comprising at least two concentric circuits, the product from stage a) in the inner circuit and viscose in the outer circuit: c) hydrolyze the bixin to norbixin after stage a) or after stage b).
    [5]
    5. A process according to claim 4 wherein in step a) an oily solution of bixin is added in an amount comprised between 0.05% (w / pviscose) and 25% (w / pviscose).
    [6]
    6. The method according to claim 5 characterized in that the bixin solution is in a range comprised between 0.05% (w / pviscose) and 3% (w / pviscose).
    [7]
    The method according to claim 3 characterized in that the bixin solution is in a range between 3% (w / pviscose) and 8% (w / pviscose).
    [8]
    8. The method according to claim 3 characterized in that the bixin solution is in a range between 8% (w / pviscose) and 25% (w / pviscose).
    [9]
    9. Process according to 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% concentration by weight of an alkaline compound.
    [10]
    10. Process according to claim 9 characterized in that the alkaline compound is selected from: NaOH and KOH.
    [11]
    11. Process according to any one of claims 3 to 8, characterized in that stage c) of hydrolysis is carried out after stage a) in a stage prior to stage b) of extrusion where the bixin is mixed with the viscose for a time comprised between 0.5 minutes and 24 hours.
    [12]
    12. Process according to claim 11 characterized in that the mixing time is between 30 minutes and six hours.
    [13]
    13. The process according to any of claims 3 to 8, characterized in that it comprises a final step of passing through a plasticizing bath.
    [14]
    14. Process according to claim 13, characterized in that 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.
    [15]
    15. The method of claim 14 characterized in that the hydrolytic enzyme is between 2 g / l and 10 g / l.
    [16]
    16. Process according to claims 3 to 8 characterized by a pleating or corrugated stage of the casing and wherein the hydrolysis stage is carried out after stage b) in the pleating stage by applying a pleating composition comprising a alkaline compound in a concentration between 0.1% and 10% by weight.
    [17]
    17. Process according to claim 16 characterized in that the alkaline compound is selected from KOH and NaOH.
    [18]
    18. A sausage casing obtainable by the method defined according to any one of claims 3 to 17.
    [19]
    19. Product embedded in the casing of claims 1 to 2 or 17.
    [20]
    Sausage product according to claim 19 wherein the product is a sausage.
    Ċ
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    同族专利:
    公开号 | 公开日
    ES2791063B2|2021-05-11|
    IL287678D0|2021-12-01|
    AR118798A1|2021-11-03|
    AU2020265114A1|2021-11-25|
    WO2020221947A1|2020-11-05|
    EP3964072A1|2022-03-09|
    UY38679A|2021-07-30|
    CA3138445A1|2020-11-05|
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