JPH0248216B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a smoke-colored and smoke-flavored filled food product. Tubular cellulose food casings are widely used to process a wide variety of meat products and other food products. These food casings are generally thin-walled tubes of various diameters made from reconstituted materials such as regenerated cellulose. Additionally, these cellulosic food casings can also be manufactured with a fibrous web embedded in their walls, and this type of casing is commonly referred to as a "fibrous food casing." The many different formulations and processing modes used by the processed food industry to suit different tastes and regional preferences generally require the use of food casings with different characteristics. In some cases,
For example, food casings need to have multifunctional uses, such as acting as containers for the processing of the foods packed therein and as protective packaging for the final product. However, food casings used in the processed meat industry, for example when producing a wide variety of meat products, such as different types of sausages (e.g. frankfurters, vologna, etc.), beef rolls, ham, etc., are often sliced removed from around the processed meat product before processing and/or final packaging. Surface appearance and flavor are important factors in the commercial and consumer acceptance of processed meat products, and common characteristics of many types of these products give them characteristic flavor and color. Includes the use of "smoked."
"Smoking" of food is generally performed by food processors and involves actually contacting the food with a gaseous or cloud of smoke. However, this kind of "smoked"
It is believed that the process is not completely satisfactory for a variety of reasons, including inefficiency and lack of uniformity in the "smoking" operation. Because of the various disadvantages experienced, many meat packers now use various types of aqueous solutions consisting of wood-sourced smoke components, commonly referred to as "liquid smoke solutions," which can be used in many different ways. It has been developed and is used commercially by food processors in the processing of meat products and other food products. For convenience, "liquid smoke solution" as purchased is often referred to herein as "as is" smoke solution. The use of "liquid smoke solution" on meat products is generally accomplished in a variety of ways, including spraying or immersing the filled food during its processing, or by incorporating the "liquid smoke solution" into its formulation. It will be done. The practical operation of "smoking" by spraying or immersion is not completely satisfactory because it does not treat the filled product uniformly, and the incorporation of "liquid smoke solution" into meat formulations is difficult because the smoked ingredients It is diluted and does not necessarily give the desired surface appearance. Furthermore, their inclusion in the formulation will reduce the stability of the meat emulsion and will adversely affect flavor when used in high concentrations. Also, the application of smoke liquid to the filled food product by the food processor, such as by spraying or dipping, creates undesirable contamination or equipment corrosion problems for the food processor. Furthermore, filled sausages that have been treated by applying smoke liquid during industrial processing have been tested to ensure uniform smoke coloring for each sausage or batch of sausages after peeling off the casing from the processed stuffed food. Bring on the chipped sausage. Particularly undesirable is the lack of color uniformity that often appears on the surface of the same sausage, including dark and light streaks and dark and light spots, especially uncolored spots that appear on the ends of the sausage. Additionally, a viscous liquid smoke solution may be applied to the inner surface of a tubular food casing that has been crimped by a food processor just prior to filling the casing with a sausage emulsion as disclosed, for example, in U.S. Pat. No. 3,330,669 to Hollenbeck. It has also been suggested that this process produces a processed food that exhibits a desirable color and smoked flavor after cooking and removal of the casing. However, Hollenbeck's method was found to be impractical and is not used industrially. The viscous liquid smoke solution disclosed by Hollenbeck coats casings in a high speed production line to produce coated casings which are then shirred by conventional methods and used as shirred casings in automatic filling equipment. is not practical. The high viscosity of the Hollenbeck coating solution limits the coating speed of the casing; for example, when coating the inside of the casing using conventional methods such as "slutting", also known as "bubble coating", the Hollenbeck viscous coating often It is necessary to cut open the casing to replenish the slug of coating material within the casing, which results in a short length of the casing and makes continuous shirring impossible. However, it has previously been discovered that providing casings that impart special treatment or structural characteristics to food products can be accomplished more uniformly and economically by casing manufacturers. This is particularly true with the emergence and widespread industrial use of automatic filling and processing equipment in the processed food industry. Several methods of applying coatings to the surface of food casings are known and described in the patent literature. For example, U.S. Pat. No. 3,451,827 discloses a spray method for applying various coating materials to the interior surfaces of small diameter casings. In U.S. Pat. No. 3,378,379 to Scheiner et al., a "slugging" method is used to apply coating material to the interior surface of a large diameter casing. These techniques have been used in the mass production of various coated food casings, including casings that use liquid smoke as an ingredient in the coating composition, and the casings produced thereby meet specific commercial requirements. To the best of applicant's knowledge, the disclosed conventional coated casings have been designed to provide sufficient levels of "smoked" flavor and color to the meat products processed therein. known not to do so. For example, US patent no.
No. 3,360,383 and U.S. Pat. Nos. 3,383,223 and 3,617,312 to Rose disclose compositions for coating various proteinaceous materials, such as gelatin, which are used to insolubilize the proteinaceous materials. Use the specific amount of liquid smoking solution required. Coated casings of this type have been disclosed to exhibit special adhesion properties necessary for dry sausage processing, properties which therefore limit their suitability for many other casing applications. Although prior patents teach applying smoke liquor to the internal surfaces of the casing, attempts to coat the casing internally during its manufacture are costly and slow in continuous high-speed production lines. was found to be limiting. July 1979 by Herman Shingyi Chuyu
One solution to this problem, as described in U.S. Pat. It is. In addition, chews may be highly acidic (PH2.0~
It has been found that the use of aqueous smoking liquors of 2.5) leads to the formation of tar-like deposits that accumulate on the carrier rolls and squeeze rolls of the smoking processing equipment, thus ultimately leading to forced shutdown of the processing equipment. It has been found that this problem can be overcome by at least partially neutralizing the neat smoke liquor to precipitate the tar and then treating the cellulosic gel material casing with a tar-removal smoke liquor. Chiu found that, unlike the knowledge of the prior art, the tar-removal smoke liquid surprisingly still has significant smoke coloring and flavoring ability, and this invention is the subject of his patent application ``Tar-Removal Smoking Liquid'', which is filed concurrently with the present application. In a US patent application titled "Removed Smoking Liquor and Processed Food Casings". One problem with the neutralization method for producing a low-tar aqueous smoke liquor composition in the Chu application cited above is that the coloring ability or "staining power" of the wood-sourced smoke liquor decreases with increasing pH or neutralization. It is. One object of the present invention is to provide a method for producing a tar-free smoke liquor from a tar-containing wood source smoke liquor without requiring its neutralization. Another object of the present invention is to provide a detarred aqueous liquid smoke solution that has a high capacity for imparting smoked color, odor and flavor to foods. Yet another object of the invention is to provide a detarred smoke coloring having a high capacity for imparting smoke color, odor and flavor to filled food products by treatment with the above solution produced by the above method. and to provide a flavored tubular food casing. Yet another object of the present invention is to provide a method for producing a smoke-colored and smoke-flavored food product in the above-mentioned detarred smoke-colored and smoke-flavored tubular food casing. Other objects and advantages of the invention will become apparent from the description below. In the present invention, a tar-containing aqueous liquid smoke solution having an absorption power (defined below) of at least about 0.25 at a wavelength of 340 nm is used to provide a tar-containing aqueous smoke solution having an absorption power (defined below) of at least about 2.
Provided is a method of making an aqueous smoke liquid composition comprising contacting an aqueous liquid smoke composition with a non-reactive or reactive organic liquid solvent having a hydrogen bond solubility parameter of and immiscible with the aqueous liquid smoke solution. . To be of use in the present invention, the organic liquid solvent that reacts with the smoke liquor must be immiscible in the liquid smoke solution and form a inducing liquid solvent that exhibits the above hydrogen bond solubility parameters in the smoke liquor environment. Nubananai. Contacting is performed at a volume ratio of liquid smoke solution to liquid solvent of about 1:1 to about 65:1. The contacting is conducted under extraction conditions that produce a tar-rich liquid solvent fraction and a detarred aqueous smoke liquor fraction, which fractions are separated to produce a tarred smoke liquor as an aqueous smoke liquor composition. . Additionally, the present invention includes a detarred, smoke colored and smoke flavored tubular casing. The casing provides a tar-containing aqueous wood smoking solution having an absorption power of at least about 0.25 at 340 nm and is a non-reactive, immiscible solution having a hydrogen bond solubility parameter of at least about 2.7 in the smoke solution environment. It is produced by a process of contacting with a synthetic organic liquid solvent. Alternatively, the organic liquid solvent may be immiscible in the liquid smoke solution and reactive with the smoke liquid if it produces a draw liquid solvent with a hydrogen bonding parameter of at least 2.7 in this environment. The contacting is conducted under extraction conditions that produce a tar-rich liquid solvent fraction and a tar-removed aqueous smoke liquor fraction at a liquid smoke solution to liquid solvent volume ratio of about 1:1 to about 65:1. These fractions are separated to produce the latter fraction as a detarring liquid. The surface of the tubular food casing is free from smoked coloring and flavoring components in the casing wall.
The casing is treated with a detarring liquid in an amount such that the casing exhibits an extinction coefficient (defined below) of at least about 0.2 at a wavelength of 340 nm. Further, the present invention provides at least about
contacting a tar-containing liquid smoke solution having an absorption capacity of 0.25 with a non-reactive organic liquid solvent that is immiscible with the aqueous liquid smoke solution and has a hydrogen bonding parameter of at least about 2.7 in the smoke liquid environment; Detarred aqueous liquid smoke solutions with smoke coloring, odor and flavoring capabilities manufactured by the Company. Alternatively, reactive organic liquid solvents can be used provided they meet the above criteria for the manufacturing process and processing casing. The contact is about 1:
A volume ratio of liquid smoking solution to liquid solvent of 1 to about 65:1 is used. Additionally, this contacting is conducted under extraction conditions that produce a tar-rich liquid solvent fraction and a tar-free aqueous smoke liquor fraction. These fractions are separated to provide a tar-free aqueous liquid smoke solution as a tar-free aqueous smoke liquid composition. Yet another aspect of the invention provides a method of smoking a smoke product comprising providing a tar-containing aqueous wood smoke solution comprising a mixture of smoke coloring, odor, and flavor components having an absorption power of at least about 0.25 at 340 nm. This invention relates to a method for producing food products that have color, odor, and flavor. The liquid smoke solution is contacted with a non-reactive organic liquid solvent that is immiscible in the aqueous liquid smoke solution and has a hydrogen bond solubility parameter of at least about 2.7 in the smoke liquid environment. Alternatively, the organic liquid solvent may be reactive with the liquid smoking solution, provided the above criteria are met. Contact is about 1:1 to approx.
A 65:1 volume ratio of liquid smoking solution to liquid solvent is used. This contacting is conducted under extraction conditions that produce a tar-rich liquid solvent fraction and a tar-free smoke liquor fraction, which are separated to provide a tar-free smoke liquor as an aqueous smoke composition. The surface of the tubular food casing is such that the casing is against the casing wall.
Treated with an amount of aqueous tarring smoke solution to develop an extinction coefficient of at least 0.2 at a wavelength of 340 nm. The thus-treated casing is filled with food, and the colored, odor, and flavor components of the smoked food are transferred from the casing to the filled food, thereby imparting the color, odor, and flavor of smoked food to the filled food. processed under conditions sufficient to Food casings suitable for use in the present invention are tubular casings, preferably tubular cellulosic casings, which are manufactured by any method well known in the art. Casings of this type are generally flexible, thin-walled, seamless tubes of various diameters made of regenerated cellulose, cellulose ethers such as hydroxyethyl cellulose, and the like. Furthermore, suitable are tubular cellulose casings with a fibrous reinforcing web embedded in the walls, commonly referred to as "fibrous food casings", and also cellulosic casings without fibrous reinforcement. , which is referred to herein as a "non-fibrous" cellulose casing. Casings conventionally known as "dry material casings" may also be used in the practice of the present invention. This type of casing generally has a moisture content ranging from about 5 to about 14% by weight for non-fibrous casings and from about 3 to about 3% for fibrous casings based on the total weight of the casing including water. Approximately 8% by weight
with a moisture content in the range of . Casings conventionally known as "gel material casings" are casings that have a higher moisture content because they have not been previously dried, and this type of casing can also be used in the practice of the present invention. Gel material casings, whether fibrous or non-fibrous, are of the type that exhibit the tarring problems described above when treated with as-purchased smoke liquor. Smoke coloring, odor, and flavor components suitable for use in the present invention are those commonly referred to as the color, odor, and flavor components of as-purchased liquid smoke. As used herein, the term "solution" refers to
It is meant to include homogeneous genuine solutions, emulsions, colloidal suspensions, etc. Liquid smoke is a solution of natural wood smoke components, often produced by burning wood, such as wood or maple, and capturing the natural smoke components in a liquid medium, such as water. Alternatively, the smoking liquid to be used can also be derived by decomposition distillation of the wood, ie by cracking or cracking the wood fibers into various compounds which are distilled off from the charcoal residue. Aqueous smoking liquids are generally very acidic, usually having a pH of 2.5 or less;
and has a titratable acidity of at least 3% by weight. As used throughout this specification with respect to the liquid smoke compositions and casings of the present invention, the term "smoke coloring, odor and flavoring ingredients" refers to smoke colorings derived from liquid smoke solutions in currently commercially available forms. , is intended and should be understood to mean odor and perfuming ingredients. The tar removal smoke liquid composition of the present invention is derived from natural wood smoke components. It is produced by contacting a tar-containing liquid smoke material with a suitable non-reactive or certain reactive organic solvent (described below) to extract the tar therefrom. Liquid smoke materials are generally produced by limited combustion of hard wood and absorption of the resulting smoke into an aqueous solution under controlled conditions. Limited combustion retains some undesirable hydrocarbon compounds or tars in insoluble form, thereby allowing these components to be removed from the final smoke liquor. Thus, by this method the wood components traditionally considered desirable by manufacturers of smoking liquids can be absorbed into the solution in harmonious proportions and undesirable components can be removed. The resulting liquid smoke solution still contains a significant concentration of tar. This is because manufacturers and users consider dark tar to be necessary in order to impart smoked color, odor, and flavor to foods. This smoke solution represents the full spectrum of smoke colors and flavors of available wood sources. Apparatus and methods for producing typical smoking liquids of the suitable type are fully described in US Pat. No. 3,106,473 to Hollenbeck and US Pat. No. 3,873,741 to Melser et al. As used herein, "at least partially neutralizes"
The term is intended to mean a liquid smoke composition having a PH of about 4 or higher, preferably a PH in the range of about 5 to about 9, more preferably a PH in the range of about 5 to about 6. It has been found that commercially available liquid smoke solutions are generally highly acidic, as discussed above, and therefore can inhibit the stripping properties of the casing when stripping aids such as carboxymethyl cellulose are used. To alleviate this problem, detarred and at least partially neutralized smoke liquors can be used in the practice of the present invention. The tar-containing smoke liquor can be applied to the external surface of the tubular casing by passing the casing through a bath of a tar-removal smoke liquor composition. The smoke liquor is allowed to contact the casing for a sufficient period of time to allow the casing to incorporate the desired amount of smoke coloring, odor, and flavoring components before passing the casing through a squeeze roll or wiper to remove excess smoke liquor. be able to. The step of passing the casing into a treatment bath is referred to in the art as a "dip bath" or "dip bath" and can also be referred to as a "dip step." Alternatively, the tar-removal smoke liquid composition can be prepared by methods other than dipping, such as spraying, brushing,
It can also be applied externally to the casing, such as by roll coating. Alternatively, the tar-removal smoke liquid composition may be applied to the interior surface of the casing by any of several well-known methods described in U.S. Pat. No. 4,171,381 to Chiu, the disclosure of which is hereby incorporated by reference. Quoted in These include slugging or bubble coating, spraying and coating with pleats. The slugging method for coating the inside of a casing involves filling a portion of the casing with coating material, i.e.
A slug of coating material is present at the bottom of a "U" shape formed by wrapping around two parallel rollers, and then a continuous infinite length of the casing is inserted into the casing, with the slug of coating material remaining occluded within the casing. the slug while passing the casing through the slug to coat its inner wall with the coating material contained within the slug. This can then be pleated in a conventional manner, or it can be dried and/or moistened before pleating to a moisture content suitable for pleating and/or other processing. Preferably,
The need for normal drying and/or humidification after treatment with an external detarring smoke liquor depends on the moisture content of the casing after treatment and the type of casing. If the casing is a non-fibrous casing, about 8% to about 18% by weight immediately before pleating.
A water level content in the range of
Moisture contents in the range of 35% by weight are typical, where % is based on the total weight of the casing including water. Various organic solvents were tested for their ability to extract tar from as-purchased smoke liquor. The procedure is as follows. Various ratios of smoke liquor to solvent were prepared and mixed thoroughly. The sample was allowed to stand overnight in order to separate the lower layer of solvent containing extracted tar from the upper layer of aqueous smoke liquor. After gravity separation, 1 ml of the tar-reduced aqueous smoked liquid layer was
ml of water and its turbidity (light transmittance at a wavelength of 590 nm) was measured using a spectrophotometer. The higher the transmittance reading, the lower the residual tar concentration in the aqueous smoking liquor. As used herein, the term "light transmittance" in an aqueous smoke liquor means that it exhibits an inherent light transmittance without the addition of substances that significantly affect the light transmittance. In the first series of solvent tests, four liquid solvents of halogen-substituted methane were tested, and Figure 4 is a series of graphs showing methylene chloride (solid line), bromochloromethane (long dashed line), and chloroform (double dashed line). Light transmission as a function of as-purchased smoke liquor to liquid solvent volume ratio for and bromoform (short dashed line). In each case, the smoking liquid was ``Royal, Smoked AA'' purchased from Grifif Labatrice. As can be seen in Figure 4, the highest level of light transmission is generally obtained at the highest amount of solvent to the smoke liquor. In a preferred embodiment of the invention, the reduced tar content of the aqueous smoke liquid composition is at least 50%
The method for producing a composition with a reduced tar content that has a light transmittance of be. As shown in Table T and Figure 13 (both described below), lower levels of light transmission may result in less tar removal from the as-purchased smoke liquor being achieved to a suitable degree. . Using this light transmittance criterion, it can be seen that the suitable range of liquid smoke/liquid solvent volume ratios depends on the particular liquid solvent and the total acid content/absorption capacity of the smoke liquid. Suitable solvents should be substantially immiscible with the smoking liquid with suitable extraction equipment. A clear layer separation of the two phases facilitates the actual gravitational separation. Furthermore, it will be appreciated that complete separation of aqueous smoke liquor and organic solvent is not possible and, depending on the degree of miscibility, small amounts of organic solvent may remain in the aqueous smoke liquor. By way of example, after removing the tar-containing fractions, about 1% by weight of methylene chloride remains in the aqueous smoking liquor. Other data show that no methylene chloride is detected in casings treated with the tar reduced composition according to the invention. FIG. 4 shows that when methylene chloride (CH ₂ Cl ₂ ) is used as the organic solvent, the volume ratio of liquid smoke solution to methylene chloride can be reduced to about 7:0 without significant transmission loss.
1 and at least 50%
It has been shown that ratios as high as about 17:1 can be achieved while maintaining a preferred level of transmittance. Additionally, Figure 4 shows that when using bromochloromethane (CH ₂ BrCl) as the organic solvent, the volume ratio of liquid smoking solution to bromochloromethane can be as high as about 15:1 without significant loss of transmittance. can be at least 50
approximately 25:1 while maintaining a favorable level of transmittance of %
It shows what is possible. Furthermore, as can be seen from FIG. 4, when chloroform (CHCl ₃ ) is used as the organic solvent, the transmittance decreases continuously from the maximum value as the smoke liquor/chloroform ratio increases. This volume ratio should range from about 1:1 to about 16:1 to achieve a preferred transmission of at least 50%. Figure 4 shows that when using bromoform (CHBr ₃ ), preferably at least 50%
This shows that very low capacitance ratios (about 1:1 to about 3:1) are required to achieve a transmittance of . For this liquid solvent and any other suitable liquid solvent, higher numbers were achieved using multiple liquid extraction steps. That is, the aqueous smoke liquor fraction from the first liquid solvent extraction step is mixed with additional liquid solvent and separated again into a tar-removed aqueous smoke liquor fraction and a tar-rich liquid solvent fraction. It will be appreciated that the practitioner may use as many liquid extraction steps as necessary to achieve the desired level of permeability. Furthermore, different suitable organic solvents can be used in the multi-solvent extraction process according to the invention, and the mixture of solvents has the above-mentioned requirements of hydrogen bonding parameter (at least 2.7) and immiscibility in the smoke liquor environment. It will be understood that solvent mixtures are then suitable. In a second series of solvent tests, other halogen-substituted hydrocarbon solvents were tested for their ability to remove tar by measuring the permeability of the smoked compositions obtained using the procedure described above. Mixtures of solvent and the same as-purchased smoke liquor at various concentrations were tested and the results were corrected by hydrogen bonding parameters. These tests are summarized in Table A.

[In the formula, H ₂₅ = heat of vaporization at 25°C, R = gas constant, T = temperature, d = density at 25°C, M = molecular weight]

It can be determined using the relationship. The total solubility parameter value is separated into its hydrogen bonded (δ _H ) or polar (δ _p ) and nonpolar (δ _op ) components. To determine the hydrogen bonding parameter value (δ _H ), the following relationship is useful: logα=3.39066T _b /T _c −0.15848−logM/d (2) [where α = agglomeration value T _b = Boiling point at absolute temperature T _c = Critical temperature at absolute temperature M = Molecular weight d = Density] Theoretical criteria for using solubility properties are described in the literature. Tables for parameters are from the study “Three-dimensional solubility parameters and solvent diffusion coefficients” by C.M. Hansen (Netherlands Technical Institute).
Press (Copenhagen 1967)). The hydrogen bond solubility parameters listed here were taken from Motpara K. L. Hui's book "Table of Solubility Parameters" (Union Carbide Corporation, 1975). It can also be obtained from Union Carbide Corporation, Chemicals and Plastics Division, River Road, Boundsburg, NY 08805. Using the spectrophotometric method described above, the optical transmittance was measured for various organic liquids with different hydrogen bond solubility parameters, in this case as-purchased Royal, Smoke AA at a volume ratio of smoke liquid to solvent of 1: It was used in 1. The results of these tests are shown in Table B
and summarized in the graph of FIG.

【table】

Table: As can be seen by examining Figure 6, there is a clear increase (almost vertical slope) in optical transmittance for the organic solvents tested as the hydrogen bond solubility parameter increases in the region of approximately 2.7. do. Although this phenomenon is not completely understood, it is believed to be based on a threshold type interaction between the solvent and the tar components that results in preferential solubility of these components. This solubility is related to the physicochemical properties of the solvent and can be predicted by measured hydrogen bonding parameter values if it is significantly higher than 2.7. For organic liquids with a hydrogen bond solubility parameter value of about 2.7, the solvent efficiency for extraction of liquid smoke tar is quite significant and should be determined experimentally. for example,
Table C (discussed below) is ethyl ether (δ _H 2.73)
Table A shows that 1,1-dichloroethane (δ _H 2.74) is not sufficient per se to be used in a single extraction step according to the invention. . Therefore, it appears that some anomalies in function and hydrogen bond solubility parameter values may occur at this threshold transition between acceptable and unacceptable solvents. Referring to Table B, one exception to the hydrogen bond solubility parameter-light transmittance relationship is isophorone, which has a low hydrogen bond parameter of 1.55 but a high light transmittance of 97.%. bring. A possible explanation is that in the acidic medium of Royal Smoke AA one would expect a significant concentration of enol due to equilibrium. Calculated using the above method, the hydrogen bond solubility parameter value for the enol is 4.8, so if the enol is present at 35 mol% (65 mol% isophorone), the hydrogen bonding parameter value for these two tautomers is is 2.7. Such enol concentrations are reasonable for this system. Further referring to Table B, another exception to the hydrogen bond solubility parameter - optical transmittance relationship is 2-ethylhexanoic acid, which has a high hydrogen bond parameter of 5.68 but a low optical transmittance of only 11.3%. have One possible explanation for this not working well is that it can dimerize in the acidic environment of the smoke liquor, given its high hydrogen bonding parameters. The hydrogen bonding parameters of such dimers are significantly lower than those reported for monomers. a required hydrogen bonding parameter of at least about 2.7 (and preferably a light transmission of at least 50% indicative of effective tar removal), one of which is miscible with the smoking liquor and has a hydrogen bonding parameter of greater than about 2.7; It has also been determined that this can be achieved by mixing at least two organic liquids, the other of which has an insufficiently low (or even negligible) hydrogen bonding parameter and is insoluble in the smoking liquid. As an example,
In the tests of Table B-Figure 6, methyl ethyl ketone (MEK) was found to be miscible with tar-containing smoke liquor at a 1:1 smoke liquor/solvent volume ratio. Additionally, toluene does not extract tar from the smoking liquor and has a hydrogen bonding parameter of 0.80. However, 50/50 (by weight) between MEK and toluene
The mixture has a calculated H-bond parameter of 2.71;
When extracted with this mixture, the light transmittance of the smoked liquid
It showed 74.8%. In yet another series of experiments, the organic liquors of the group in Table B were tested for light transmission at higher smoking liquor to solvent volume ratios by the same spectrophotometric method using as-purchased Royal Smoke AA. did. These smoking liquid to solvent volume ratios are 3:
1, 6:1, 12:1 and 24:1, and the results are summarized in Table C and the graph in FIG. As can be seen by examining Table C, for most solvents at a smoke liquid to solvent ratio (also referred to herein as extraction ratio) of 3:1, the light transmittance is equal to a 1:1 extraction ratio. or slightly lower. Generally, the suitability of the solvent for use in the present invention is the same for these two extraction ratios, i.e. the solvent has a suitable light transmittance of greater than 50% (for extracted smoke liquor) or about 2.7% for both ratios. Gives a suitable light transmission of less than 50% for both ratios defined by hydrogen bonding parameters. There are three exceptions to this generalization: propionaldehyde, ethyl ether, and MEK/2-ethylhexanol mixtures. Furthermore, as Table C shows, at smoke liquor to solvent ratios of 6:1 or higher, some of the solvents that are suitable at lower extraction ratios are no longer suitable, whereas others are still suitable. ing.
As an example, chloroform and methylene chloride are suitable at high extraction ratios, whereas ethyl acetate is 6:
At an extraction ratio of 1, it gives a light transmission of only 4.5%. One reason for this observed phenomenon is the solubility of the solvent in water and therefore its expected solubility in the smoking liquor; If large, it is defined by the sum of the hydrogen bond solubility parameter and the weight percent solvent solubility in water. More specifically, this sum must not exceed about 9, or the water solubility of the solvent is too high to practice the invention, as indicated by a light transmission of less than about 50%. Referring again to chloroform and methylene chloride, due to their low water solubility, the sums are 3.9 and 6.0 respectively;
It has high light transmittance values of 80.4% and 82.0% at an extraction ratio of 24:1. They are therefore suitable for carrying out the invention at high ratios. In contrast, ethyl acetate has a total of 12.4 due to its high water solubility and a low light transmission of only 4.5% at a 6:1 extraction ratio. Therefore, ethyl acetate is not suitable for carrying out the invention at high extraction ratios. FIG. 7 shows that the light transmission is relatively constant at very high levels of at least 85% for a sum of about 2.7 to about 7, and then decreases at an increasingly increasing rate up to at least 8. For sums greater than about 9, the light transmission decreases to less than about 50%, and solvents with this property are not suitable for practicing the present invention. For the sum of hydrogen bonding parameters plus water solubility as shown in Table C, five of the six alcohols exhibit this relationship, as can be seen by referring to the graph in Figure 5 for certain alcohol solvents. Satisfied, but not 2-ethylhexanol. Even if the total is only 5.9, this is 6:1
It shows an unacceptably low light transmittance of 44.8% at an extraction ratio of . The reason for this exception to the sum-extraction ratio relationship described above is not understood, but is likely due to steric relationships.

【table】

[Table] Figure 8 is a graph showing the light transmittance for the organic liquids of Tables B and C, which is the hydrogen bond solubility parameter plus weight percent solvent for an extraction ratio (smoking liquid to solvent volume ratio) of 1:1. Shown as a function of total solubility. For the hydrogen bonding parameters alone (FIG. 6), the light transmission increases almost vertically in total to about 2.7 and is at a very high level of about 90% for a total of at least 15 or so.
Unlike the graph for a 6:1 extraction ratio in FIG. 7, the light transmission for a 1:1 extraction ratio does not decrease for sums above about 7. Other groups of solvents were extracted for light transmittance by the same spectrophotometric method for light transmittance using extraction ratios of 1:1, 3:1 and/or 6:1 and as-purchased Royal Smoke AA. Tested. Data from these studies are summarized in Table D. As can be seen by examining Table D, most organic liquids have a combination of extraction ratio and hydrogen bond solubility parameter plus weight percent in water.
Extraction was achieved according to the above relationship with the total solubility.

[Table] Other requirements for an organic liquid suitable for use as a single component solvent in the present invention are that it be non-reactive and immiscible with tar-containing smoke liquors, or that it be reactive with tar-containing smoke liquors. is that the resulting inducing solvent is immiscible in tar-containing liquids and has the required criteria of a hydrogen bonding parameter value of at least about 2.7 in a smoke liquid environment. Two reactive solvents were included in the data in Tables C and D above. These are organic acids and amines. One group of organic liquids that are generally unsuitable for use in the present invention as single component solvents are the alkylamines. In the low PH environment of tar-containing smoke liquors, exothermic reactions of acid monobases occur and the resulting quaternary salts are generally more soluble than their precursors. Phase separation is lost and therefore extraction is not possible, as shown by tri-n-butylamine (Table C). However, when using certain amines, such as di-(2-ethylhexyl)amine, experimental observations indicate that there is no difference between the resulting derived quaternary salt solvent and the tar-containing liquid smoke solution. Indicates that miscibility remains high. Furthermore, since the hydrogen bonding capacity of quaternary salts is known to be higher than that of their precursors, the inducing solvent is higher than 2.35 (values in Table D for precursors) and often about 2.7
It is believed to have higher hydrogen bond solubility parameters. For these reasons, di-(2-ethylhexyl)amine quaternary salt-derived solvents are suitable single-component solvents in smoke liquor environments. When considering the use of reactive type solvents, the practitioner should ensure that the desired chemical balance of the smoking liquor is not upended by solvent reactions. Certain reactive solvents, while functionally suitable, can form derivatives that adversely affect the coloring and flavoring properties of the smoke liquor. For this reason, it is preferred to use non-reactive types of organic liquid solvents in the practice of this invention. One method of treating casings with the detarring smoke liquid of the present invention is shown in FIG. In FIG. 1, a flat tubular cellulose sausage casing 10 is externally coated with a detarring smoke liquid composition 12 as it passes through lower and upper guide rolls 13 into a dipping bath 11 containing a detarring smoke liquid composition 12. Process from After the casing exits the soaking tank, it passes through lower and upper guide rolls 14 and between squeeze rolls 20, which minimize excess carry-off of the liquid smoke composition. Casing 1
0 and the tar-removal smoking liquid composition 12 in the soaking tank 11
The total contact time with the excess liquid smoke composition during the passage of the casing with and through the guide rolls 14 before passing the casing through the squeeze rolls 20 is:
Determining the amount of smoke coloring, odor, and flavoring components of the tar removal smoke liquid composition that the casing incorporates. The total contact time is measured from point A to point B in FIG. After passing through the squeeze roll 20, the casing is passed through a guide roll 23 and wound onto a reel 24. The casing is then transferred to subsequent conventional processing, including conventional humidification and conventional pleating as required. In the specific example shown in FIG. 2, the casing after passing through the squeezing roll 20 is heated and
The embodiment differs from the embodiment shown in FIG. 1 in that it is transported into a container and dried therein to the appropriate moisture content. The casing is made with squeeze roll 2
This squeezing roll 20 due to the sealing action of 0 and 22
and 22 while being maintained in a relatively fixed position and inflated by the bubble. The heating chamber 21 can be any type of heating device, for example a circulating hot air chamber, which dries the sausage casings to the appropriate moisture content. After the casing leaves the heating chamber 21 and passes through the squeeze roll 22,
It is wound onto a reel 24 via a guide roll 23. The casing is then transferred to subsequent conventional processing, including normal humidification and normal pleating as required. The embodiment shown in FIG. 3 differs from the embodiment shown in FIG. 2 in that the casing is dried flat during its passage over guide rolls 25. It should be noted that the detarring smoke liquid coated on the casing surface, whether coated externally or internally, is not present only as a surface coating. The smoke coloring, odor and perfuming ingredients coated on the surface penetrate the cellulose structure of the casing as the cellulose absorbs moisture from the smoke solution. Inspection of a cross section of the casing wall will determine the degree of color across the casing wall, with the smoked surface having a darker color than the opposite surface of the casing wall. Therefore,
In this specification, the term "coated" is to be understood to mean that the casing wall is not only coated with smoked ingredients, but also impregnated with smoked ingredients. Furthermore, the tar removal smoke liquid composition of the present invention includes:
Other ingredients that may be suitably used in treating tubular food casings to which smoked ingredients are applied may also be included, such as glycerin and/or propylene glycol, which may be used as humectants or softeners. Other ingredients commonly used in the manufacture of food casings or in their treatment, such as cellulose ethers and mineral oils, can also be present in the casings if desired, and these can be used if treatment with a detarring smoke liquid is not used. It can be used in the same manner and in the same amount as For example, a release enhancer for casings from foods such as sausages (e.g. frankfurters, bolognas, etc.) may be applied before or after the tar-removal smoke liquid is externally applied to the casings.
Alternatively, the outer surface of the casing can be suitably coated before or during shirring. When applying the detarring smoke liquid to the internal surface of the casing, the stripping agent is preferably applied first. Release enhancers of this type include, but are not limited to, water-soluble cellulose ethers such as carboxymethylcellulose, the use of which is described in Chu et al.
No. 3,898,348, issued Aug. 5, 2005, the disclosure of which is hereby incorporated by reference. Additionally, it includes Herkyllies' registered trademark product Aquapel, which is an alkyl ketene dimer, and its use is also disclosed in U.S. Pat. No. 3,905,397, issued September 16, 1975 to , the disclosure of which is hereby incorporated by reference for reference, and also discloses that E. Ai. Dupont,
D. Nimoas. Company's registered trademark product "Quilon" is also included, and its use is further described in Dub. F. 1959 8 regarding Undoubted etc.
No. 2,901,358, issued May 25, 2013, the disclosure of which is hereby incorporated by reference. The release enhancer can be applied to the interior surface of the tubular food casing using any of a number of well known methods. For example, the release enhancer can be introduced into the tubular casing as a liquid "slug" in a manner similar to that disclosed in, for example, Scheiner et al., US Pat. No. 3,378,379. Passing the casing through the liquid slug coats its internal surface. Alternatively, release enhancers may be used, such as those described in U.S. Pat.
It can also be applied to the internal surface of the casing via a hollow mandrel that moves the casing, such as a shirring mandrel in a manner similar to that described in US Pat. No. 3,451,827. The casings produced using the method of the invention are furthermore suitable for the processing of food products commonly known in the art as "dry sausages". Unlike other types of non-fibrous and fibrous casings, which are preferably easily peeled from the food product by the food processor or by the consumer before being sold to the consumer, "dry sausage" casings are
Preferably, it adheres to the food during and after processing. “Kymene” [Hercules. It is a registered trademark product of Inc., Inc., and is a polyamide epichlorohydrin resin, the use of which is disclosed in U.S. Pat. [0013] The interior surface of a casing treated with a detarring smoke liquor according to the method of the present invention can optionally be internally coated with the casing to improve the adhesion of the casing to the processed food product. The invention will be explained in more detail by the following examples, which are given by way of illustration only and are not intended to limit the invention in any way. Unless otherwise specified, all parts and percentages are by weight; all casing percentages are based on the total weight of the casing. Example 1 This example illustrates the preparation of a liquid smoke composition of the present invention. to 0.47 gallons (1.8) of methylene chloride,
Add 4.7 gallons (18) of the as-purchased liquid smoking solution "A"("Royal Smoke AA" from Griffith Laboratories, Inc. with an absorption of approximately 0.6 at 340 nm) and then repeat the liquid in the container. Mix thoroughly by inversion. The tar-containing methylene chloride was separated from the smoke liquor by gravity, ie, the lower layer of tar-rich methylene chloride was drained until the upper layer of the tar-free smoke liquor appeared as detected by visual observation. The resulting aqueous smoke liquor composition contains little tar, as determined by qualitative water compatibility testing in which a sample of the smoke liquor is mixed with water and observed for tar precipitation or lack thereof. The PH of the aqueous smoke liquid composition portion was then adjusted to PH 5.0 by adding a sufficient amount of 50% NaOH solution to the smoke solution. The pH of the as-purchased smoked liquid sample was similarly adjusted to 5.0. The chemical compositions of the four liquid smoke solutions included in this Example 1 are shown in Table E. The total acid content was measured by the steam distillation-titration method described below. Determination of phenols and carbonyls in liquid smoked solutions was performed using the following procedure. Determination of the phenol and carbonyl content of smoked liquids During sample preparation, all samples were passed through Watzmann No. 2 paper or equivalent to avoid possible polymerization upon receiving or after preparing the preparation. Freeze until time of analysis. Use distilled water for all dilutions. Add 10ml of these samples to water.
Dilute in two steps starting with the amount of In the first step, the dilution is made to a total volume of 200 ml, and in the second step, the initial 10 ml of solution is further diluted to a total volume of 100 ml. To determine the phenols, 5 ml of the second solution are further diluted in a third step with distilled water to a total volume of 100 ml. For carbonyl determination, 1 ml of the second solution is further diluted with carbonyl-free methanol to a total volume of 10 ml. The reagents for measuring phenols are as follows: 1 Boric acid-potassium chloride buffer PH8.3. Dilute the indicated amount of solution to 1 with water. 125ml of 0.4M boric acid. 125ml of 0.4M potassium chloride. 40ml of 0.2M sodium hydroxide. 2 0.6% NaOH 3 Coloring reagent N-2,6-trichloro-p-benzoquinoneimine Stock solution: 0.25 g is dissolved in 30 ml of methanol and stored in the refrigerator. 4 2,6-dimethoxyphenol standard 1 to 7 μg of DMP in water for standard curve
Prepare a solution of ml. This method for phenol determination is I. Double. It is a modified Gibbs method based on the method described in "Determination of Phenols in Meat and Fat" by J.T. T. T. T., JACAC, XXV, 779 (1942). These reagents were mixed in the following order: 1st: 5 ml of PH 8.3 buffer. 2nd: Unknown dilution of smoked liquid or standard 2,6
-5 ml of dimethoxyphenol solution or 5 ml of water as a blank. Third: Adjust PH to 9.8 using 1 ml of 0.6% NaOH. 4th: Dilute 1 ml of the coloring reagent stock solution to 15 ml with water.
Add 1 ml of diluted coloring reagent. Adjust just before addition. 5th: Let the color develop for exactly 25 minutes at room temperature. 6th: 1 by Spectronic type 20 or equivalent
Measure the absorbance at a wavelength of 580 nm in a cm tube. Seventh: Create a standard curve using the horizontal axis as absorbance and the vertical axis as standard concentration. Extrapolate the concentration of DMP in the smoke liquid dilution from this curve. 8th: Calculate DMPmg/ml of smoked liquid using the following formula. ppmDMP (from standard curve) x (dilution factor) x 0.001mg
/μg=mgDMP/ml smoked liquid/ml initial smoked liquid sample To calculate mgDMP/g smoked liquid, divide the result of the above formula by the weight (g) of 1 ml of smoked liquid. The reagents for carbonyl determination are as follows: 1 Carbonyl-free methanol. Add 5 g of 2,4-dinitrophenylhydrazine and a few drops of concentrated hydrochloric acid to 500 ml of methanol. Reflux for 3 hours and then distill. 2 2,4-dinitrophenylhydrazine solution. The twice recrystallized product is used to prepare a saturated carbonyl-free solution in methanol. Store in the freezer and prepare freshly every two weeks. 3 KOH solution. Dissolve 10g in 20ml of distilled water,
Dilute to 100 ml with carbonyl-free methanol. 4 2-butanone standard. 100ml for standard curve
2- in methanol containing no carbonyl of
Prepare a solution of 3.0-10 mg of butanone. The procedure is described in the paper "Method for colorimetric measurement of trace amounts of carbonyl compounds", Analytical. Chemistry, No. 23
vol., pp. 541-542 (1959). The procedure is as follows: 1st: Into a 25 ml volumetric flask (prewarmed to ensure saturation) containing 1 ml of 2,4-dinitrophenylhydrazine reagent, add 1 ml of diluted liquid smoke solution or 1 ml of diluted liquid smoke solution or Add standard butanone solution or 1 ml methanol (as a reagent blank). 2nd: Add 0.05 ml of concentrated hydrochloric acid to all 25 ml flasks, mix the contents, and let stand in a water bath at 50°C for 30 minutes. Third: Cool to room temperature and add 5 ml to each
Add KOH solution. Fourth: Dilute the contents of each flask to 25 ml with carbonyl-free methanol. 5th: Measurement at 480 nm against a methanol blank set to absorbance 0 (Cuvette: 0.5 x 4
inch (10.2cm) or equivalent). Use a Spictronic model 20 or equivalent. Part 6: Absorbance vs. 2-butanone (MEK) concentration
Plot for standard curve as mg/100ml. Seventh: Create a standard curve using absorbance as the horizontal axis and standard concentration (mgMEK/100ml) as the vertical axis. Extrapolate the concentration of MEK in the smoke liquor dilution from this curve. 8th: Calculate mgMEK/100ml smoked liquid using the following formula: mgMEK (from standard curve) x dilution factor = m
To calculate gMEK/100ml smoked liquor/100ml mgMEK/g smoked liquor, divide the result of the above formula by the weight (g) of 100ml of smoked liquor.

Table E: Values are arithmetic averages of multiple measurements Table E shows the chemical properties of the aqueous smoke liquor compositions prepared according to the present invention that differ substantially from tar-containing aqueous smoke liquors as purchased. It shows that it has. On a weight basis, the tar removal compositions of Table E, Samples E ₂ and E ₄ , have less than about half the phenol content of the tar-containing aqueous smoke liquor composition from which they were derived (Sample No. E ₁ ). , which represents a preferred composition of the present invention. Although the data in Table E show that extraction substantially changes total acid content and carbonyl concentration, other experimental studies do not draw any conclusions from studies regarding the effect of extraction on total acid content or carbonyl concentration. This indicates that withdrawal is not possible. Although the practice of the present invention significantly reduces the concentration of phenolic components in smoke liquid compositions, this does not adversely affect the composition's protein staining (color) ability or its natural odor or flavor properties, as illustrated in the following examples. do not have. Furthermore, as can be seen by visual inspection of samples of the compositions of Table E, the compositions embodying the present invention have a significantly lighter color and therefore contain significantly less high molecular weight tar. Furthermore, they are entirely miscible in water. EXAMPLE 2 This example shows that a non-fibrous cellulose food casing according to the method of the invention was prepared with the smoking liquid component of Example 1 and a "Charsol ) C-10'', the latter being identified in Table F as Smoked B and Smoked Liquid Composition B. Smoked liquid composition B
Smoke B (Charsol C-10) was obtained by a solvent extraction method carried out in the same manner as the extraction in Example 1.
Created from. Neutralized (PH 5.0) aqueous smoke liquid composition E ₃ prepared in Example 1 by applying a liquid smoke solution to the external surface of the casing of several non-fibrous Frankfurter dimension gel material casings. and treated with _E4 . Similarly, gel material casings were treated by applying neutralized as-purchased smoke B and tar removal smoke composition B. The amount of smoke liquid added was in each case approximately 10 mg/in. ² (1.55 mg/cm ² ) to the casing surface. The applicator is a device that evenly distributes the aqueous liquid smoke solution around the casing and consists of two main parts: the smoke liquid applicator and the smoothing device. The smoke liquid applicator consisted of a stationary foam disc mounted so that the smoke liquid entered from the outer edge. A small flexible plastic tube guided the liquid to a central core that passed through the expansion casing. The foam disk is bent with the casing dimensions, making it suitable for a range of casing cross-sections. Since the application of the liquid smoke was not exactly uniform, a rotary smoothing device was used immediately after the applicator. It consisted of a rotating foam disk with core dimensions appropriate to the casing dimensions being processed. This disc was driven by an air motor at 200-250 rpm (1260-1570 min ^-1 ). Excess smoke liquid from the applicator and smoothing device was collected in a common reservoir and returned to the applicator inlet. The treated casings were transported via a supporting assembly to the drying section. Although the sheathing and casing transfer assemblies described above do not form part of the present invention, as described in the 1981
U.S. patent application cited above entitled "Liquid Coating Method and Apparatus" filed May 7,
No. 261457, appropriate portions of which are hereby cited. The treated casings were dried at 80°C to a moisture content of 12% by weight. The casing was then conventionally humidified to 14-18% water by weight and shirred. The levels of smoke composition, phenols, carbonyls and total acid content present in the treated casings are shown in Table F. The total acid content of the casing was measured by the steam distillation-titration method described below. The phenol and carbonyl contents in the smoked casing are measured by the same method described below.

[Table] * Values are arithmetic averages of multiple measurements. One specific example of the tar-removed smoke-colored and smoke-flavored casing of the present invention is the tar-containing aqueous smoke liquid composition from which the tar-removed aqueous smoke liquid was derived. The casing can be characterized as having a tar-removal smoke coating having less than half of the phenol content (based on the weight per unit area of the treated casing surface) of the casing when coated with a casing. The data in Table F is a special example;
In this case, the casings of the invention coated with the tar-removal smoke liquid composition A had only about 1/3 of the phenol content of the casings coated with the partially neutralized tar-containing liquid smoke solution A. Similarly, casings coated with tar-removal liquid smoke composition B have a phenol content that is approximately 1/2 that of casings coated with partially neutralized tar-containing liquid smoke solution B.
had a score of less than 4. Due to the nature of these experiments, the reduction in phenol in the smoke liquor (Table E) and in the coated casing (Table F) is not proportional. As in the case of Table F, no conclusions can be drawn therefrom regarding the effect of the invention on the carbonyl content or acid content of the casing. Examples 3 and 4 demonstrate the treatment of non-fibrous cellulose casings according to the method of the present invention using the substantially neutralized aqueous smoke liquid composition A of Example 1 and a release enhancer. . Example 3 Several non-fibrous frankfurter size casings were treated as in Example 2 (Royal
methylene chloride extracts of solutions and tars derived from smoked AA) with the exception of propylene glycol and mineral oil and polyoxyethylene sorbitan esters (commercially designated as "Tween 80" and purchased from Atlas Chemical Industries, Inc.). A solution containing 0.85% by weight of sodium carboxymethyl cellulose (“CMC”) is then applied onto the internal surface of the casing during pleating
The spray coating was applied at a feed rate of 0.54 mg/in ² (0.54 mg/cm ² ) of the casing surface to improve the release properties of the casing. The PH of the aqueous smoke liquor composition used in these experiments (smoke liquor composition A of Example 1) was adjusted by addition of 50% NaOH solution to a pH of 3.2 as shown in Table G.
Or even more.

TABLE The detarred and smoke colored casing samples of Table G were filled with a high collagen content meat emulsion having the composition of Table H. The filled casings were then processed through the conventional steps of cooking, cold water treatment and quenching, but without the usual steps of smoking. Processing conditions were sufficient to transfer smoke color, odor, and flavor components from the casing to the filled frankfurters. The casing is peeled off from the finished frankfurter in a high-speed Apollo ranger peeler, and the surface shows that the pH is at least
4.1 indicates that these casings were 100% peeled off. This means that all the frankfurters were separated from the casing without mechanically clogging the stripping device and without damaging the frankfurter surface at the stripping speed of the device. Additionally, the table shows that each of the samples generally has excellent colorimetric values compared to the comparative sample CMC-8. All samples showed excellent darkness (“L” value), but sample CMC-14
had a lower redness ('a' value) due to the relatively high solution pH of 7.0. Frankfurters treated according to the invention exhibited a suitable smoked flavor.

[Table] The colorimetric values in the table are standardized using a white board.
All of these were obtained using a Gardner XL-23 colorimeter with an aperture of cm and following standard operating procedures. Described in the instruction manual for the trichromatic stimulus colorimeter. Three locations were selected and measured for each of the 10 frankfurters obtained from each treatment. Measurements were taken approximately 1 inch (2.54 cm) from each end of the frankfurter and in the middle. Colorimetric "L" and "a" values were recorded.

【table】

EXAMPLE 4 A non-fibrous Frankfurter-sized gel material casing was treated with the tar-removal smoke liquid composition E ₂ of Example 1 and its internal surface was then coated with various release enhancers. The release enhancer was a variety of water-soluble methylcellulose ethers sold by the Dow Chemical Company. The specific methylcellulose ether used for each sample is shown in Table J. The casings were then filled with high collagen meat emulsion as in Example 3.
The filled casings were processed and stripped, and the resulting Frankfurter colorimetric and strippability data are summarized in the table as the "MC" sample. All samples showed relatively good colorimetric values. Additionally, these samples exhibited improved release properties compared to sample CMC-9, which was prepared without a release enhancer. The improved stripping properties of the low PH (2.4) tar removal smoke liquor may be related to the nonionic properties of the methylcellulose ether.

【table】

TABLE Summarizing Examples 3 and 4, the table shows that non-fibrous cellulose casings treated with a tar-removal aqueous smoke liquid composition according to the invention should be further treated with a release enhancer. . The table further shows that treated frankfurters in non-fibrous cellulose casings treated with a tar-removal aqueous smoke liquid composition according to the present invention are compared to untreated casings.
It shows a darker and redder surface than the frankfurters treated in CMC-8. A standard was used to compare the protein staining (coloring) ability of the tar-removed aqueous smoke liquor compositions of the present invention with the tar-containing smoke liquor from which the compositions of the present invention were derived. These criteria include the "dying power" applied to the liquid composition itself and the "dying factor" applied to the coating on the tubular food casing. In each case, the test embodiments of the present invention exhibited approximately the same dyeing performance as the original tar-containing smoke liquor, but the tar content was reduced to a level where the tar problems previously experienced were eliminated. . The staining factor is a reliable criterion for measuring the color development capacity in newly made casings of the invention, but should not be used for aged casings. The procedure used to measure staining power and staining coefficient is described below. Determination of dyeing power and dyeing coefficient This procedure is based on the reactions experienced in meat processing, where meat proteins react with smoke components to impart the desired dark smoke color to the product. To quantify this dyeing or darkening power, unknown smoke or smoke products are reacted with a specific amino acid (glycine) under acidic conditions at 70° C. for 30 minutes. The absorbance of the solution
Measured at 525nm. This procedure can be performed with reproducible results on liquid smoke or liquid smoke treated casings. The detailed procedure is as follows: Prepare a 2.5% solution of glycine in 95% acetic acid. (a) Dissolve 12.5 g of glycine in 25 ml of water in a 500 ml metering flask. Add sufficient glacial acetic acid to facilitate dissolution. (b) Dilute to the required level with glacial acetic acid. For smoked liquid analysis, weigh 15-20 mg (±0.1 mg) of the smoked liquid to be measured into a 15 ml test tube, or for smoked casing analysis,
Four double-thickness discs are punched out of the test casing to yield a casing area of 2.0 in ² (12.9 cm ² ) to yield 8 discs. (a) When pleating the casing, inflate the section with air at 10 psi (68,900 Pascals) to smooth the surface. This is stretched onto a hard surface to collapse the casing, the disks are punched out and these are added to the test tube. Add 5.0 ml of 2.5% glycine/acetic acid solution to the test tube containing either the smoking liquid or the treated casing. The test tube is capped, shaken by hand to ensure sample contact, and placed in a 70°C oven or constant temperature bath for 30 minutes. The absorbance of each solution is measured at 525 nm using glycine reagent as a blank. The absorbance is recorded as the staining power of the smoke or the staining coefficient of the smoked casing. The numbers for the staining factors summarized in Table K indicate the absorbance per 2 in ² (12.9 cm ² ) of casing surface. Staining power indicates the ability of an amount of smoked liquid to produce a given absorbance or color according to the procedure of staining coefficient, ie, units of absorbance per mg of liquid. In these tests, the amount of liquid smoke composition added onto the non-fibrous cellulose food casing per ^cm2 of casing surface was
It was 1.1 mg (6.9 mg/in ² ). Table E shows the staining power values.
The dyeing coefficients were determined for the coated casings shown in Table F. The results of these protein staining tests are summarized in Table K. It should be noted that in the experiments described above in which the tar-removal smoke liquid composition was neutralized after solvent extraction, the neutralization was carried out without controlling the temperature of the aqueous solution during the neutralization. The heat of the solution increases this temperature from the initial approx.
The temperature is raised substantially from around 20°C to a high level of around 55-60°C. The dyeing power of the resulting at least partially neutralized aqueous smoke liquor is slightly reduced due to the high temperature, and this reduction can be partially avoided by maintaining a temperature below about 40° C. during neutralization. was discovered. When neutralization is carried out at such controlled temperatures, the dyeing strength is not reduced to nearly the same extent, and this finding is covered in a patent filed concurrently with this application entitled ``Treatment of Food Casings with Tar-removal Smoking Liquor.'' It is stated in the application specification. Another advantage of the above application combining the present invention with controlled temperature neutralization is that the amount of solvent required may be minimized. That is, the as-purchased smoke liquor is first neutralized under conditions of controlled temperature to form a tar precipitate, and then the tar-removed supernatant is contacted with a solvent according to the invention to further remove tar. do. This sequence was used in experiments similar to those shown in Tables E and F, and the results are included in Table K as Sample K5 (detarring smoke liquor) and Sample K10 (casing treated with tar removal smoke liquor). As observed from Table K, the staining power and staining coefficient for these samples are the highest for the neutralized detarred samples and therefore the sequence of neutralization followed by solvent extraction at controlled temperature is in accordance with the present invention. A preferred specific example is shown below.

【table】

EXAMPLE 5 Another series of experiments was conducted to demonstrate the difference between the as-purchased tar-containing smoke liquor and the detarred smoke liquor of the present invention with respect to clouding of cellulose casings. Samples of casings mixed with various types of smoking liquid were immersed in water. During this period, the contaminated tar components are insolubilized by the water. For the tar-free samples, no incompatibility was measured, but for the tar-containing samples, the tar precipitated in or on the casing, and water incompatibility in the form of cloudiness on the casing was quantitatively measured. It was done. More specifically, Royal Smoke AA smoke liquid was applied in an amount of approximately 1.55 mg/cm ² (10 mg/in ² ) to a diameter 21 mm.
mm on the external surface of a cellulose casing, in this case the cellulose casing had carboxymethylcellulose ("CMC") based coating on the internal surface for improved peelability. For samples obtained by practicing the present invention, the as-purchased smoking liquid was first mixed with methylene chloride liquid solvent for 10 minutes.
The contact was made at a volume ratio of liquid smoke solution to liquid solvent of 1. After mixing, the solution is allowed to stand for 12-16 hours to form two layers, the separated upper layer of the detarred smoke liquid is partially neutralized to pH 5.0, and the outside of the cellulose casing is removed by the procedure of Example 3. Applied on the surface. The treated casing was crimped and 36-inch (91.4 cm) long samples were randomly taken from the de-crimped pieces, inflated with air to minimize pleat wrinkles, and immersed in 200 ml of deionized water. did. The soaking time was at least 1 hour and up to 3 hours, and the criterion was soaking for a sufficient period of time to achieve complete water penetration of the casing wall. After blotting and drying the sample, ASTM Method D-1003, Vol. 35,
"Fogging and light transmittance of transparent plastics" (1977)
Measurements were made using the general procedure described in . The results of these tests are summarized in Table L below.

[Table] Smoked products containing liquid tar 32 8.5−13.1% 10.7%
liquid
As can be seen from Table L, the average haze for cellulose casings treated with the as-purchased tar-containing smoke liquor is substantially higher than the average haze for cellulose casings treated with the tar-removal smoke liquor of the present invention. , the latter is only about
It is 61.6%. The average haze value increases with increasing diameter due to the increased thickness of the casing wall. The absolute value for the average haze further depends on the total acid content of the specific smoke (or absorption capacity, described below) and the amount of smoke mixed into the casing (or absorption coefficient, described below), but in general, The average haze for the inventive cellulose casings is substantially less than the average haze for cellulose casings treated with as-purchased smoke liquor, which is similar to their coloration on filled food products when manufactured under comparable conditions. This also applies to cases where the fragrance ability is almost the same. This relationship illustrates the chemical and functional differences between cellulose casings treated with the detarring smoke liquor of the present invention and casings treated with the as-purchased smoke liquor. This haze test is only useful in characterizing cellulose casings, not the fibrous casings of the present invention. This is because the fibrous casing is inherently opaque and has a very high average haze, for example about 97.5% for an untreated fibrous casing. Example 6 Regarding the aged casings of the present invention, the dyeing coefficient of the casings treated with the detarring smoke liquor is significantly reduced from that of the freshly prepared casings, but surprisingly the filled food products produced using the aged casings A series of tests were carried out which showed that in colorimetric values the smoked color was equal to the product made with the new casing. These aging tests included casings treated with the as-purchased tar-containing smoke liquor under practically identical conditions, but for these casings, the staining factor was the same as that of the tar-removal smoke liquor of the present invention. The dyeing coefficient for the casing did not decrease nearly as much as it did. This comparison shows the chemical differences between the two types of casing. In these tests, Royal Smoke AA
The smoking liquid was applied to the external surface of a 21 mm diameter cellulose casing with a CMC-based coating on the internal surface for improved peelability. For samples prepared in accordance with the present invention, as-purchased smoke liquor was first contacted with a methylene chloride liquid solvent at a 10:1 volume ratio of liquid smoke solution to liquid solvent. After mixing,
The solution was allowed to stand for 12-14 hours to form two layers. The top layer of the separated tar-free smoke liquor was partially neutralized to a pH of 5 and applied to the external surface of a cellulose casing according to the procedure of Example 3. Half of the casing is filled with a high collagen content frankfurter meat emulsion having a composition very similar to that shown in the table.
It was then processed using the conventional steps of cooking, cold water treatment, and quenching, but without the usual smoking treatment. The other half of the casings were aged as shown in Table M and then used to similarly make frankfurters. The results of these tests are summarized in Table M. Colorimetric values were obtained using the same equipment used in Example 3 and using the same procedures described in connection therewith. It should be understood that the data in Table M are not quantitatively comparable. This is because the initial staining index ("Fresh SI") was different and different aging conditions were used. However, this data supports the general relationship that filled foods made with aged casings have a smoked color that is unaffected by casing aging, despite the fact that the casing's dyeing coefficient decreases with aging. Qualitatively supported. Example 7 A further series of ultraviolet absorption spectroscopy tests were carried out using cellulosic food casings treated with a tar-removal smoke liquor according to the invention and a tar-containing as-purchased smoke liquor. These tests show substantial differences between the two types of casing. These tests were carried out using smoking liquors obtained from three different types of wood: Charsol;
C-12, Royal. Smoke AA and Royal.
Smoke B was included, but in each case the casing was a 21 mm diameter cellulose casing with a CMC-based coating on the internal surface for improved peelability. For Charsol C-12, first mix the smoked liquid as purchased with methylene chloride liquid solvent.
Contact was made at a volume ratio of liquid smoke solution to liquid solvent of 10:1 and then allowed to stand for 12-14 hours. For Royal Smoke AA, the as-purchased smoke solution was first contacted with methylene chloride liquid solvent at a 10:1 liquid smoke solution to liquid solvent volume ratio and then allowed to stand for 12-14 hours. Royal. For Smoke B, the as-purchased smoke solution was first contacted with a methylene chloride liquid solvent at a 15:1 liquid smoke solution to liquid solvent volume ratio and then allowed to stand for 12-14 hours. In each case, the two layers obtained were separated and the upper layer was a detarring smoke liquor with a pH of 2.4, which was used to treat the external surface of the cellulose casing as described in Example 3.
The same procedure was carried out using three as-purchased smoke liquors with the same pH of 2.4.

[Table] The liquid smoke treated casings were then subjected to the following procedure to obtain liquid samples suitable for obtaining ultraviolet absorption spectra in the range 350-210 nm: (a) 100 in ² (645 cm) of liquid smoke treated casings; ² )
The samples were immersed in 200 ml of absolute methanol for approximately 1 hour and then removed. (b) Depending on the amount of liquid smoke added, further dilution must be performed for compatibility with ultraviolet scanning devices. In these cases, the amount of smoked liquid added is 10mg/
in ² (1.55 mg/cm ² ) casing, and the solution used for scanning was 4.96 ml of methanol and 0.10 ml of extract.
It was composed of. (c) In the range of 350 to 210 nm by the following method:
UV spectra were recorded: 2 seconds reaction/2 mm slit, 10 nm/cm, chart, 50 nm/min. Scan rate, 0-200% transmittance scale. In order to measure the absorbance, which is mainly due to the tar present in the smoking liquor, the spectrophotometer was zeroed using the extraction solution with the lowest possible tar content. For any particular type of smoke liquor, this was an extracted sample of casings treated with extracted and neutralized (PH5.0) smoke liquor. Once zeroed in this way, other absorbances in the UV spectrum become quantitative measures of the tar component present. The results of these ultraviolet absorption tests are plotted on the graph in Figure 9, with the Charsol C-12 sample shown as a solid line and the Royal. Smoked AA samples are shown with dashed lines and royal. Smoke B sample is indicated by a dashed line. If the transmittance is greater than 0 shown in Figure 9,
This is a function of the device blank used in these specific experiments. As can be seen by examining these curves, the largest difference between the tar-free sample (upper curve) and the tar-containing sample (lower curve) is approximately
This occurs at a wavelength of 210 nm, although there are significant differences over the entire scanning range of wavelengths. UV absorbance and
The optical transmittance values at a wavelength of 210 nm are summarized in Table N. This shows that cellulose casings treated with the tar-removal smoke liquor of the present invention have a lower yield of at least 90
% at a wavelength of 210 nm.

EXAMPLE 8 Although all of the tubular food casing processing experiments described above were directed to non-fibrous cellulose casings, the present invention is also useful in processing fibrous cellulose casings. In this experiment, the tar removal smoke liquid was Royal. Smoked AA was prepared from an as-purchased liquid smoke solution by the methylene chloride solvent extraction method of Example 1, but without PH adjustment. The fibrous casing material, having a flat width of about 6.3 inches (16 cm), was then treated with a detarring liquid in substantially the manner illustrated in FIG.
The estimated amount of tar removal liquid smoke solution added to the casing was approximately 20 mg/in ² (3.1 mg/cm ² ) of the casing surface. Samples of casings treated with this liquid smoke were filled with Borogna meat emulsion and then processed in a conventional manner to produce finished Borogna, provided that no smoke was applied in the fumigation chamber. This Bologna exhibited good smoke color, odor and flavor when compared to a control Bologna which was treated in the same fumigation chamber at the same time with casings not treated with any smoking liquid. In a preferred embodiment of the invention, the tar-removal liquid smoke composition has a total acid content of at least about 7% by weight;
It is particularly preferably prepared from a tar-containing aqueous wood smoke liquor having a total acid content of at least about 9% by weight. Total acid content (also referred to as total acidity) is a qualitative measure of the tar content and staining power (as defined above) in the smoke liquor obtained from as-purchased wood smoke used by the manufacturer. in general,
Higher total acid content means higher tar content. The same is true for the total solids content of as-purchased liquid smoke. The procedure used by wood smoke liquor manufacturers to determine total acid content (total acidity) and total solids is as follows: Determination of total acid content for tar-containing smoke liquors 1 Accurately approx. 1 ml of smoking liquid (straighten if necessary)
Weigh out into a 250ml beaker. 2 Dilute with about 100ml of distilled water and make a standard 0.1N
Determine pH up to 8.15 with NaOH (PH meter). 3 Calculate the total acid content as weight percent of acetic acid, using the following conversion: 1 ml of 0.1000N NaOH = 6.0 mg of HAc Determination of Total Solids 1 Install a dry Watzmann No. 40 paper disc. Approx.
Pipette 0.5ml of smoked liquid and weigh accurately. The smoking liquid should be clear, and filtration is performed to ensure this condition. 2. Dry in a forced air oven at 105°C for 2 hours or in a regular oven at 105°C for 16 hours. 3 Cool to room temperature in a desiccator and weigh. 4 Calculate total solids as weight percent of liquid smoke. As discussed below, this dilution-titration method is also used to determine the total acid content of a detarring liquid smoke composition that is not at least partially neutralized. Table O lists the most commonly used and commercially available tar-containing aqueous wood smoking liquors and their total acid content (total acidity) as reported by the manufacturer.
It shows. The total solids content, dyeing power and light transmittance at 590 nm are also recorded for comparison. As can be seen from Table O, as-purchased wood smoking solutions with total acid content values of less than about 7% by weight have transmittance values higher than 50% and have low dyeing power. Since their tar content is extremely low, their water compatibility is high. Therefore, there is no need to remove tar from this type of wood smoking solution according to the invention. Moreover, their dyeing power is so low that they cannot perform the same smoke coloring and smoke flavoring functions as the tar-free aqueous smoke liquid compositions of the present invention. However, an as-purchased liquid smoke solution with a low tar content of this kind can be concentrated, for example by evaporation, and the liquid smoke solution thus concentrated can then be advantageously treated by the method of the invention. It should be understood that it may acquire the characteristics of a tar-containing smoke liquor. That is, this kind of concentrated tar-containing smoke liquor obtains higher total acid content, total solids and dyeing power.

【table】

[Table] The solvent extraction treatment of the aqueous smoking liquid of the present invention is approximately 1:1
It will be recalled that a liquid smoking solution to liquid solvent volume ratio of ˜65:1 is required. Figure 10 shows that this ratio is a function of the particular liquid solvent to be used to obtain a suitable light transmission of at least 50% at 590 nm. FIG. 10 shows that the practitioner needs to consider the specific type of as-purchased smoke liquid to achieve the desired light transmission. More specifically, FIG. 10 is a graph showing the light transmittance at 590 nm as a function of as-purchased smoke liquor to solvent volume ratio for several smoke liquors shown in Table O. Royal Smoke AA is shown with a broken line, Charsall C-3 is shown with a dotted line, Charsall C-12 is shown with a solid line, Royal Smoke B is shown with a dashed line, and Charsall C-10 is shown with a dashed line.
is shown by a two-dot dashed line. In all experiments summarized in Figure 10, the liquid solvent was methylene chloride, and the same general relationships exist for other liquid solvents suitable for practicing the invention. This figure shows that to achieve a particular level of light transmittance for a particular solvent, a practitioner must select a smoking liquor with a relatively high absorption capacity and total acid content, and use a relatively large amount (i.e., a relatively This indicates that lower smoking liquid to solvent ratios can be used. Alternatively, a smoke liquor with a relatively low absorption capacity and total acid content and a relatively small amount thereof (ie, a relatively high smoke liquor to solvent ratio) can be used. Additionally, this figure shows that for a given smoke liquor-to-solvent ratio (same volume of smoke liquor), a practitioner obtains a relatively high light transmittance for a smoke liquor with a relatively low absorption capacity and total acid content. It is shown that. Furthermore, Figure 10 shows that at 590nm at least 50%
To achieve a suitable standard of light transmittance of
0.3) and total acid content based on the ratio suitable for the smoking liquid. Of the smoke liquors included in the drawing, Royal Smoke B has the lowest tolerance and the curve shows a transmittance of about 50% at a smoke liquor to solvent ratio of about 65:1. Even more noteworthy, the curve of Charsol C-3 shows its high compatibility with water in the absence of solvent (light transmission 98%) and at all solvent ratios. Therefore, the present invention is not useful for neat Charsol C-3, which has low absorption capacity (0.12) and low total acid content (3.6%). Generally, if the neat liquid smoke solution has a total acid content of about 7 to 9% by weight, the liquid solvent selected will be effective at a liquid smoke solution to solvent volume ratio of about 30:1 to 65:1. be. Similarly, when the neat smoke solution has a total acid content of about 9 to 11.5% by weight, the solvent is effective at a liquid smoke solution to solvent volume ratio of about 15:1 to about 30:1. moreover,
When the neat smoke liquor has a total acid content greater than about 11.5, the volume ratio for effective extraction of tar is from about 7:1 to about 25:1 liquid smoke solution to solvent. Another series of experiments was conducted to provide the basis for a lower limit on the smoke liquor to liquid solvent volume ratio (approximately 1:1) in practicing the present invention. The solvent was methylene chloride and Figure 11 shows the effect of reducing the smoking liquid to solvent ratio for Royal Smoke AA (dashed line), Charsol C-12 (solid line) and Charsol C-10 (double dashed line). . These data indicate that at smoke liquor to solvent volume ratios of less than about 1:1 the staining power of the tar removal smoke liquor is reduced to unusefully low levels. Absorption Power It will be recalled that both the dyeing power and dyeing coefficient measuring procedures involve chemical reactions and for this reason the values measured at ambient temperature obviously decrease under hot aging conditions. As shown in Example 6, this reduction does not accurately indicate smoke color in filled foods using aged casings after detarring smoke liquor treatment. Under these circumstances, an additional measurement method that does not involve chemical reactions was used in the present invention to measure the coloring capacity of liquid smoke and liquid smoke treated casings. This method of measurement for liquid smoke is called "absorption capacity".
The measurement method for casings treated with liquid smoke is called the "absorption coefficient." In the procedure for determining the absorption capacity, 10 mg of smoke liquid (tar-containing smoke liquid or tar-free smoke liquid) are placed in a disposable container and 5 ml of methanol are added to this. These two components are mixed by inverting the container, and the ultraviolet absorption value of the mixture is then measured at 340 nm. This particular wavelength is chosen because spectrophotometric measurements for many smoked liquids exhibit maximum linearity in this wavelength range. Absorption measurements for various neat smoke liquids are shown in Table O. A plot of these absorbency measurements as a function of total acid content or total solids content is:
Shows an almost linear relationship. Although tar content makes a large contribution to absorbency measurements, it should be noted that tar makes only a small, if any, contribution to food staining. Therefore, in commercially available neat smoking liquids, the absorption capacity depends on the tar content and e.g.
Includes measurements with coloring components such as phenols and acids. This means that the absorbency of neat and detarred smoke liquors can be used to grade them by smoke coloring ability. However, the absorption capacity of the neat smoke liquor is not numerically comparable to the absorption capacity of the tar-removed smoke liquor of the present invention due to the tar absorption effect. Unlike dyeing power, smoking liquid absorption power does not decrease with age. Example 9 A series of absorption capacity measurements were carried out on various detarring smoke liquors of the present invention using methylene chloride as the solvent. In each case, the as-purchased smoke liquor was first neutralized by the addition of sodium hydroxide flakes and the neutralization temperature was maintained controlled at 10-15°C to remove the initial tar portion. The resulting smoke liquor with partially removed tar content was then contacted with methylene chloride to remove the second tar portion. The liquid extraction procedure was the same as described in Example 1, with a smoke liquid to solvent volume ratio of 10:1.
These measurements are summarized in Table P.

【table】

[Table] * Values in parentheses were obtained from different batches of smoking liquid.
Table P should be interpreted in light of the above discussion of the effect of tar content on smoke liquor absorption capacity. As can be seen by examining Table P, the absorbency of the tar-removed smoke liquor of the present invention is generally lower than the absorbency of the tar-containing neat smoke liquor from which it is obtained. Table P further provides that tar-containing smoke liquors useful in the practice of the present invention have an absorbency value of at least about 0.25;
Tar-containing smoke liquors, such as Charsol C-3, which are not useful in their raw form, have been shown to have an absorption capacity of less than 0.25. The absorbency of the tar-removal smoke liquid composition of the present invention must be at least about 0.15 to impart an acceptable smoke color to food products produced in the smoked casings of the present invention. . In preferred embodiments, the absorbency of the tar-removal smoke liquid composition is at least 0.25. Figure 10 shows that Charsol C-3 has an extremely high light transmittance of approximately 98% due to its low total acid content and low total solids and/or tar content; It will be recalled that this has been shown to have no significant effect on transmittance. Extinction Coefficient In the method of measuring extinction coefficient, 2in ² (12.9
cm ² ) of liquid smoke treated casings are cut out after drying and placed in 12 ml of methanol. 1
After a soaking period of 1 hour, the methanol extracts all the smoke components from the casing, and then the ultraviolet absorption value of the obtained methanol containing smoke components is measured at 340 nm. The wavelength of 340 nm was selected as in the absorption power measurement. This is because spectrophotometric measurements for many smoke liquid extracts from smoked casings show the greatest correlation with smoke loading in this region. Example 10 A series of extinction coefficient measurements were carried out on casings using three different tar removal smoke liquors prepared according to the invention and neutralized to a pH of 5.0. The smoking liquid was applied in different dosages to the external surface of a non-fibrous Frankfurter gel material casing in the manner described in Example 2. The results of these experiments are summarized in Figure 12, where the smoke liquid obtained from Royal Smoke AA is shown as a wavy line, the smoke liquid obtained from Charsol C-12 is shown as a solid line, and the smoke liquid obtained from Royal Smoke B is shown as a solid line. The liquid is indicated by a dotted line. This diagram shows that the practitioner first selects the desired smoke color and smoke type based on the extinction coefficient, then determines the required amount of a specific tar removal smoke liquid to the casing, and then determines the smoke color. make it possible to achieve. The correlation between smoked color and extinction coefficient is shown in Example 11 below. In Figure 12, 1 mg/in ² is
Equal to 0.155mg/ ^cm2 . EXAMPLE 11 A series of colorimetric tests were performed using frankfurters prepared according to the method of Example 3 on non-fibrous casings treated with various smoking liquors, including the basis of Example 10. The results of these tests are summarized in Table Q.

TABLE In an attempt to quantify the desired light intensity change required to ensure sufficient color development, values for L% were determined and included in Table Q. In this case, the meat emulsion is a mixture of 50% beef chuck and 50% regular pork trim and there is a 1.4 unit change in light intensity or less in the unsmoked control casing compared to the liquid smoked casing. The value of ΔL was considered too low if it occurred between the L values measured for frankfurters made with . Table Q shows that if the extinction coefficient is less than about 0.2, then the amount of smoke liquor added is 4.0 mg/in ² (0.62 mg/cm ² ) or less. This level of smoke liquor loading generally does not provide the desired reduction in light intensity to meat products. That is, color development is generally considered to be insufficient. Extrapolating from Samples No. 1 and 2, it is approximately 8.5 mg/in ² (1.32 mg/in 2 ) for the casing.
The average reduction in light intensity for frankfurters obtained with smoke liquor loadings of cm ² ) is quite sufficient for most end uses, so a corresponding extinction coefficient of at least 0.4 for the casing is preferred for the present invention. A specific example will be shown. Additionally, Table Q shows that embodiments of the present invention have approximately the same dyeing capacity as the original tar-containing smoke liquor. A comparison of samples No. 1 and 3 shows that the tar content of the smoking liquor has a very small influence on the dyeing ability of the smoking liquor. For practical purposes, a Frankfurter light intensity of 2.9 for casing sample No. 1 corresponds approximately to a Frankfurter light intensity of 3.4 for casing sample No. 3. It should be noted that many factors regarding the food emulsion and processing conditions can affect the background color and therefore the values of L and ΔL. For example, meat derives much of its color from myoglopin. It is known that the color associated with the myoglobin content of meat depends on the chemical reaction and aging of the myoglobin.
This is further influenced by processing conditions such as temperature, humidity, time and air velocity. Therefore, the values of ΔL in Table Q are only relevant for these specific tests. Regarding the extinction coefficient, all of the experiments described above were also performed on non-fibrous casings of the same diameter immediately after smoke liquor treatment and drying. Other tests showed that the extinction coefficient was not significantly affected by changes in casing thickness. Still other tests showed that the extinction coefficient values for fibrous casings treated with the tar-removal smoke liquor of the present invention were approximately the same as for non-fibrous cellulose casings with the same amount of smoke liquor coating. Ta. Therefore,
The wide requirements for the extinction coefficient of at least 0.2 and preferably at least 0.4 also apply to the fibrous casing. As an example, 10.1mg/in ² (1.57mg/in 2
An extinction coefficient of 0.43 was obtained for a 115 mm diameter fibrous cellulose casing treated with a tar-removal smoke liquor obtained from Royal Smoke AA at a dosage of cm ² ) outside the casing surface. The extinction coefficient for non-fibrous cellulose casing similarly treated with the same amount of smoking liquid was determined from other tests to be approximately 0.4. EXAMPLE 12 To demonstrate the small effect of high temperature aging on the extinction coefficient, a series of tests were conducted on tar-removed Frankfurter dimension cellulose casings. In these tests, the tar-containing raw smoke liquor was first neutralized to a pH of 5.0 by the addition of sodium hydroxide flakes, in which case the neutralization temperature was increased to 10
A controlled temperature of ~15°C was maintained. The liquid extraction procedure was the same as described in Example 1, and the smoke liquid to solvent ratio was
The ratio was set to 10:1. Extinction coefficient measurements were taken on casings treated with the detarring smoke liquor immediately after treatment and drying, and after 5 and 12 weeks of storage at room temperature. 100 other samples of the same casing
(38°C) and extinction coefficient measurements were taken at the same time intervals. These measurements are summarized in Table R. Table R Extinction coefficient of aged casing Time and temperature Extinction coefficient Initial, 21°C 0.52 5 weeks, 21°C 0.49 12 weeks, 21°C 0.49 5 weeks, 38°C 0.54 12 weeks, 38°C 0.59 Table R shows how aging changes the extinction coefficient This shows that it has no significant effect on It should be understood that the extinction coefficient requirements of the present invention are based on measurements at ambient temperature. In other preferred embodiments of the invention, the tar-removal aqueous smoke liquid composition has a total acid content of at least about 7% by weight, particularly preferably at least about 9% by weight.
It has a total acid content of Total acid content is a qualitative measure of the dyeing power (as defined above) not only for tar-containing smoke liquors, but also for tar-free smoke liquors produced therefrom by the solvent extraction method of the present invention. Although the present invention does not require at least partial neutralization of highly acidic tar-containing smoke liquors or of tar-removed smoke liquor compositions, at least partial neutralization is desirable. If the tar-removal smoke liquor composition is not neutralized for purposes of the present invention, its total acid content can be determined by the same dilution-titration method described above to determine the total acid content of the tar-containing (as is) smoke liquor composition. be measured. If the tar-free smoke liquid composition is at least partially neutralized, the total acid content is determined by steam distillation recovery-titration.
This method is theoretically capable of quantifying acids, such as acetic acid and formic acid, produced in an at least partially neutralized detarring smoke liquid composition. From a reaction point of view, the proportion of acid (in free or salt form) in the aqueous smoking liquor remains constant at least during partial neutralization. However, recovery of these acids is only about 70% because complete azeotropic recovery cannot be achieved within reasonable distillation volumes. At present, no method is readily available that provides quantitative recovery of total acidic compounds from detarring smoke liquors under any circumstances. Under these circumstances, the results obtained by the steam distillation recovery-titration method are multiplied by a factor of 1.4 to convert them to the same total acid content basis used for tar-containing smoke liquors. The total acid content, phenol content, and carbonyl content in the smoked casings were measured by the following procedure. Determination of total acid content for at least partially neutralized tar-removed smoke liquid and treated casings made therefrom. This measurement is performed to determine the amount of milliequivalents of acetic acid (HAc) distilled out during acidification of an at least partially neutralized tar-removal liquid smoke composition or treated casings made from this composition. This was done from the number of milliequivalents of sodium hydroxide (NaOH) to be used. The term "milliequivalent" means the weight (g) of a substance contained in 1 ml of a 1.0 normal solution. The steps are as follows: 1. Tare 800ml of exactly 5g of tar removal smoke liquid.
Weigh it into the Kjeldahl flask.
For the casing, accurately measure the casing surface area of 100in ² . 2 Zeolite and 100 ml of 2% (v/v) H ₂ SO ₄ are added to the flask and the reaction is as follows. 2NaAc+H ₂ SO ₄ →2HAc+Na ₂ SO ₄ 3 Place a 500 ml Erlenmeyer flask containing 100 ml of deionized water in an ice bath and use this water to collect the distillate. 4 Connect the Kjeldahl flask containing the sample to the steam distillation apparatus. 5 Distill the sample until the volume of distillate in the collection Erlenmeyer flask reaches 500 ml. 6. Titrate 100 ml of the distillate with 0.1N NaOH to a pH end point of 7.0. The reaction is as follows. HAc + NaOH → NaAC + H ₂ O 7 Add the measured acid content to 1 ml of 0.1N NaOH
is equal to 6.0 mg of HAc and is therefore calculated as the weight of acetic acid on the basis that the measured acid content (mg) = titration value ml x 6.0. 8 Total acid content = 1.4 x measured acid content (mg). 9 For liquid smoke, the value of total acid content (mg) is expressed as % by weight of the initial liquid smoke sample. For the casing, the value of the total acid content is expressed as mg of acid per 100 cm ² of casing surface area. The total acid content of several tar removal smoke liquid compositions of the present invention was determined by this steam distillation recovery-titration method and the results are shown in Table S. For comparison, the same procedure was used to measure the total acid content of the as-purchased tar-containing smoke liquor from which these compositions were obtained, and the results are also shown in Table S. It will be seen that for the same type of smoke liquid, whether it is tarred or detarred, the values are quite similar. For example, neat Royal Smoke AA smoke liquor has a total acid content of 11.1%, and in one experimental example, the detarred Royal Smoke AA smoke liquor has a total acid content of 11.7%. For further comparison, Table S also includes as-purchased Royal Smoke AA smoke liquor used by the manufacturer for tar-containing smoke liquors and measured by the dilution-titration method described herein. Ta. This value of 11.4% is also based on the steam distillation recovery-titration method.
This value is extremely close to that of AA.

[Table] Measurement of phenol and carbonyl content in casings treated with smoke liquor As described in the method for measuring total acid content, 200
Samples are prepared by measuring the casing external surface area of ~300 in ² (0.129-0.194 m ² ) and steam distilling. The reagent for phenol determination is prepared as follows with distilled water: 1 Color development solution: 100 mg of N-2,6-trichloro-p-benzoquinoneimine is dissolved in 25 ml of ethanol and frozen. For testing, dilute 2 ml to 30 ml with water. 2 Buffer, PH8.3: Dissolve 6.1845 g of boric acid in 250 ml of water. 250ml of 7.45g of potassium chloride
dissolves in water. Dissolve 0.64g NaOH in 80ml water. Mix these three solutions. 3 1.0% NaOH: Dissolve 1.0g of NaOH in water. Dilute to 100ml. 4 Standard solution: Dissolve 0.200 g of dimethoxy-phenol (DMP) in 2000 ml of water. Then,
Dilute some of this solution to 1ppm, 2ppm,
Provide standard solutions containing 4ppm, 6ppm and 8ppm DMP. Procedures for measuring phenol are provided by F.Wild,
This is the modified Gibbs method described in "Estimation of Organic Compounds", Vol. 143, pp. 90-94, Universal Press, Cambridge (1953). In this method, the order is as follows: 1st: Mix the four ingredients in a 25 ml flask in the following order. 5 ml buffer, PH 8.3 5 ml casing distillate, standard or water (blank) 1 ml 1% NaOH 1 ml diluted color reagent 2nd: shake, cover, and stand in the dark for 25 minutes do. 3rd: Measure the absorbance at 580 nm. Fourth: Create a standard curve with absorbance on the horizontal axis and standard concentration on the vertical axis. Extrapolate the concentration of DMP in the casing distillate from this curve. 5th: Calculate mgDMP/ ^100cm2 casing using the following formula: ppmDMP (from standard curve) x 500 (dilution) x 0.001mg/
μg×100 = mgDMP/100cm ² /area of the initial sample The reagents for carbonyl determination are as follows: 1 A saturated solution of recrystallized 2,4-dinitrophenylhydrazine (DNP) in carbonyl-free methanol. 2 Concentrated hydrochloric acid. 3 10% alcoholic KOH: 20ml of 10g KOH
Dissolve in distilled water and dilute to 100 ml with carbonyl-free methanol. 4 Standard solution: Dilute 1 ml of 2-butanone (methyl-ethyl-ketone) (MEK) to 2000 ml with distilled water. Then dilute some of this solution to
0.8ppm, 1.6ppm, 2.4ppm, 4.0ppm and
Provide a standard solution containing 8.0 ppm MEK. The method for carbonyl determination is the modified Latuppan-Clark method described in the article "Colorimetric Method for Determination of Trace Quantities of Carbonyl Compounds", Analytical Chemistry, Vol. 23, pp. 541-542 (1951). . In this method, the order is as follows. 1st: Mix the three ingredients in the following order in a 25 ml flask. 5 ml of 2,4DNP solution 5 ml of casing distillate, standard or water (blank) (Note: casing distillate needs to be further diluted) 1 drop of concentrated hydrochloric acid 2nd: Place the mixture in a 55°C water bath for 30 minutes To digest. Third: After rapidly cooling the digestion mixture to room temperature, add 5 ml of 10% alcoholic KOH, shake and let stand for 30 minutes. 4th: Measure the absorbance at 480 nm. Fifth: Create a standard curve with absorbance on the horizontal axis and standard concentration on the vertical axis. Extrapolate the concentration of MEK in the casing distillate from this curve. 6th: Calculate mgMEK/ ^100cm2 casing using the following formula: ppmMEK (from standard curve) x (dilution rate) x 0.001mg/
μg×100=mgMEK/100cm ² /Example Area of Initial Sample 13 The tar-removal smoke liquid composition of the present invention preferably has a substantial portion of its tar content removed to avoid taring during casing treatment. As an indication of this, it has been mentioned above that it has a light transmittance of at least 50%. This suitability is due to the Royal
This was demonstrated by a series of tests in which smoked AA was contacted with methylene chloride solvent under extraction conditions as described above at various liquid smoke solution to liquid solvent volume ratios. The tar-removed smoke liquor fraction was separated and its light transmittance was measured in the same manner as described above. The weight percent non-volatile matter (including tar) in this tar-removed smoke liquor fraction was determined. The data from these tests are summarized in Table T and in the graph of FIG.

A review of this data and FIG. 13 shows that light transmission is significantly affected by non-volatile (including tar) content in the 0 to about 50% light transmission range. That is, to progressively increase the light transmittance of a smoke liquor from 0 to about 50%, the tar content of the smoke liquor must be progressively reduced, for example, by practicing the present invention. Once enough tar has been removed to achieve a light transmission of at least about 50%, a plateau is reached and subsequent improvements in light transmission are not primarily dependent on subsequent tar removal. Although preferred embodiments of the invention have been described in detail, it is contemplated that various modifications thereof may be made and certain features may be used in their own right, all within the spirit and scope of the invention. It is. For example, as-purchased tar-containing smoke liquors that can be advantageously processed according to the present invention can be concentrated by well-known techniques prior to further processing or use according to the present invention. This may be desirable if the practitioner desires to apply a highly concentrated detarring smoke solution to the casing wall. Another variation contemplated from the above-described embodiments of the invention is the method of separating the mixture of tar-containing smoke liquor and liquid solvent into a tar-enriched liquid fraction and a tar-free smoke liquor fraction. In the example this was done in a single stage extraction by gravity decantation, but it will be understood by those skilled in the art that other methods may be used. These methods include single-stage and multi-stage contacting of two liquids, which can be carried out under room temperature conditions or under elevated temperature and pressure conditions. These extraction methods can be carried out in a variety of devices, such as liquid-liquid cyclones or centrifugal contactors. Multistage extractions can also be carried out using a plurality of these devices or using vertical countercurrent columns. Countercurrent columns include spray towers, packed columns, closed columns or modified bubble trays incorporating sheep trays, and columns with internal stirring, such as rotating disk columns. Treatment of the surface of a tubular food casing with a detarring smoke liquid according to the method of the invention is preferably carried out under controlled environmental conditions where the presence of small metal particles is minimal. This is an important requirement. This is because metal wear particles (primarily iron, copper, brass) that come into contact with the casing react with the smoke liquor coating, causing autoxidation, discoloration, and even cellulose deterioration of the treated casing. Discoloration and cellulose deterioration occur only in the intermediate zone of metal contamination, which rarely exceeds a size of 2 to 10 mm in diameter. Cellulose degradation can often be severe enough to result in casing failure during filling or processing.
Materials in the fabrication of processing equipment are an important factor in minimizing small metal particles. These materials are (1)
It should be highly abrasion resistant and (2) non-reactive to smoking liquids. It has been determined that certain metals and alloys meet these stringent requirements. These are: certain aluminum alloys,
Chrome, plating, tin alloys, and some types of stainless steel. Additionally, care must be taken in other steps of casing manufacturing and handling to minimize the presence of small metal particles. Example 14 Four samples of detarring smoke liquors were prepared using a solvent extraction method with varying values of light transmittance. The as-purchased liquid smoking solution used was "Charsol C-12", and at a wavelength of 340 nm, it was approximately
It had an absorption capacity of 0.5 and a pH of about 2. Each of the three samples was prepared in much the same manner as in Example 1, except that each sample was solvent extracted to give a different light transmittance value for each resulting detarred liquid smoke solution. To a given amount of methylene chloride approx.
3785 ml of neat smoke liquid was added and the liquid was mixed by stirring or shaking. The tar-containing methylene chloride was separated from the smoking liquor by decantation. Light transmittance was varied by varying the amount of methylene chloride used for extraction.
The light transmittance was measured by diluting 1 ml of the tar-removed smoke liquid with 10 ml of water and measuring the transmittance to water using a Hitachi model 100-60 spectrophotometer at a wavelength of 590 nm. The table shows the amount of methylene chloride (MeCl ₂ ) for each sample for solvent extraction of tar from as-purchased smoke liquor and the PH and light transmittance of the tar-removed smoke liquor product.

[Table] The sample prepared above was applied to a non-fibrous Frankfurter casing (dimension No. 25) of gel material per 1 m ² of casing surface area using the apparatus and method of Example 4.
The amount of smoked liquid added was 15.5g.
The casing was heated as in Example 4 to about 80°C to about
It was dried for 3 minutes at a drying temperature of 120°C. During the application of the tar-removal smoke liquor, the casing was observed for tar spots and the drying guide and squeeze rolls of the dryer were observed for tar accumulation. The results of these observations are summarized in the table.

[Table] Not sticky.
As can be seen from the above results, the problem due to the presence of tar in the tar removal liquid smoke solution as reflected by the lower light transmittance values increases as the tar content decreases or the light transmittance values increase. becomes smaller. In the case of a tar-removal smoke liquid with a light transmission of about 40%, the difficulties caused by tar, especially sticking on the squeeze rolls, render the coating process inoperable and this composition is therefore unacceptable. At light transmissions of approximately 50%, difficulties arise, such as the formation of tar spots on the casing after operating hours. However, during the initial run time, spot-free casings are produced and these are acceptable from a commercial point of view. Light transmittance is about 60
%, the operating time becomes longer before tar spots appear on the casing, and therefore the coating process becomes more practical. At a light transmittance of about 84%, long hours of operation can be achieved without spotting and tar accumulation problems. A tar-removal smoke liquid with high light transmission can be used in the coating process without encountering any problems including tar build-up or other related difficulties that would cause the coating process to stop.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram of an apparatus suitable for treating the external surface of a food casing with a detarring smoking liquid in accordance with one embodiment of the present invention. Figure 2 is an apparatus similar to and serving the same function as that of Figure 1, but with a chamber for partially drying casings treated with a detarring smoking liquor to a desired moisture content while under expansion conditions; This is a schematic diagram. FIG. 3 is a schematic representation of an apparatus similar to and serving the same function as that of FIG. 2, but with means for partially drying casings treated with a detarring smoking liquid while under flat conditions. FIG. 4 is a graph showing light transmittance as a function of as-purchased smoke liquor to liquid solvent volume ratio for several halogen-containing organic liquid solvents: methylene chloride, bromochloromethane, chloroform, and bromoform. FIG. 5 is a graph showing light transmission as a function of as-purchased smoke liquor to liquid solvent volume ratio for various non-halogenated alcohols. FIG. 6 is a graph showing light transmittance as a function of hydrogen bond solubility parameter at a 1:1 as-purchased smoke liquor to solvent volume ratio for various organic liquid solvents. Figure 7 is a graph showing light transmittance as a function of hydrogen bond solubility parameter plus the sum of % solvent solubility in water at a 6:1 as-purchased smoke liquor to solvent volume ratio for various organic liquid solvents. be. Figure 8 shows a 1:1 ratio for non-reactive and certain reactive organic liquid solvents.
2 is a graph showing light transmittance as a function of hydrogen bond solubility parameter plus the sum of % solvent solubility in water at the as-purchased smoke liquor to solvent volume ratio. Figure 9 shows the UV transmittance and UV absorbance of casing extracts at various wavelengths for both casings treated with as-purchased tar-containing smoke liquor and casings treated with the tar-removed smoke liquor of the present invention. This is a graph showing. Figure 10 shows the as-purchased liquid-to-solvent volume ratio and as a function of a wide range of volume ratios for several smoking liquids.
It is a graph showing light transmittance at 590 nm. FIG. 11 is a graph showing staining power as a function of volume ratio for relatively low smoke liquid to solvent volume ratios. FIG. 12 is a graph showing the ultraviolet absorption coefficient as a function of the fill amount of tar removal smoke liquid in a food casing. FIG. 13 is a graph showing the proportion of non-volatile substances (including tar) in the smoking liquor as a function of light transmission. 10...Casing, 11...Immersion tank, 12...
...Smoked composition, 13,14,20,22...Roll, 24...Reel, 27...Chamber.

Claims (1)

Claims: 1. A tar-containing aqueous liquid smoke solution comprising a mixture of smoke coloring and smoke flavoring ingredients having an absorption power of at least about 0.25 at a wavelength of 340 nm and immiscible in said liquid smoke solution. and an organic liquid solvent having a hydrogen bond solubility parameter of at least about 2.7 in a smoke liquid environment, wherein the liquid smoke solution and the liquid solvent are mixed at a ratio of about 1:1 to 65:1 liquid smoke solution to liquid solvent volume. a tar-rich liquid solvent fraction and a tar-removed smoke liquid fraction by contacting them under extraction conditions at a ratio of 100 to 200 ml, and separating the fractions to form the tar-removed smoke liquid as an aqueous smoke liquid composition; treating the surface of the casing with an amount of the tar-removal aqueous smoke liquid composition sufficient to provide the casing wall with an absorption coefficient of at least about 0.2 at a wavelength of 340 nm; A method for producing a smoke-colored and smoke-flavored food product, which comprises filling the filled food product with a casing and treating the resulting filled food product under conditions sufficient for the transfer of smoke-colored and smoke-flavored ingredients from the casing to the filled food product. . 2. The liquid solvents have a total hydrogen bond solubility parameter of about 2.7 to 9 plus weight percent solvent solubility in water, and the liquid smoke solution and the liquid solvent are combined at a ratio of at least about 6:1 liquid smoke solution to liquid solvent. A method for producing a smoked colored and smoked flavored food according to claim 1, wherein the food is supplied in a volume ratio. 3. A method for producing a smoke-colored and smoke-flavored food according to claim 1, which comprises at least partially neutralizing a tar-containing aqueous liquid smoke solution to a pH of at least about 4 or higher and contacting it with a liquid solvent. . 4. The method for producing a smoke-colored and smoke-flavoured food according to claim 3, wherein the temperature of the liquid smoke solution during at least partial neutralization is controlled so as not to rise above about 40°C. 5. A method for producing a smoke-colored and flavored food product according to claim 1, wherein the tar-containing aqueous liquid smoke solution has a total acid content of at least about 7% by weight. 6. Smoke coloring according to claim 1, wherein the treated casing wall has approximately half the phenol weight content of an identical casing wall treated in the same way with a tar-containing aqueous liquid smoke solution. and a method for producing smoked flavored food. 7. A method for producing a smoke-colored and smoke-flavoured food according to claim 1, wherein the contacting and separating are carried out in such a way that the tar-removal aqueous liquid smoke solution has a light transmittance of at least 50%. 8. The tar-containing aqueous liquid smoking solution has a total acid content of about 7% to about 9% by weight, and the liquid solvent has a total acid content of about 30% by weight.
2. The method of claim 1, wherein a liquid smoke solution to liquid solvent volume ratio of 1 to about 65:1 is provided. 9 Tar-containing aqueous liquid smoking solution is about 9 to about 11.5
wt% total acid content, and the liquid solvent is approx.
2. The method of claim 1, wherein a volume ratio of liquid smoke solution to liquid solvent is provided from 15:1 to about 30:1. 10. The tar-containing aqueous liquid smoke solution has a total acid content of greater than about 11.5% by weight, and the liquid solvent is provided in a liquid smoke solution to liquid solvent volume ratio of about 7:1 to about 25:1. A method for producing a smoked colored and smoked flavored food according to claim 1. 11 Claim 8, wherein the liquid solvent is a dihalogen-substituted or trihalogen-substituted methane liquid.
A method for producing a smoked colored and smoked flavored filled food as described in 2. 12 Claim 9, wherein the liquid solvent is a dihalogen-substituted or trihalogen-substituted methane liquid
A method for producing a smoked colored and smoked flavored filled food as described in 2. 13 Claim 1 in which the liquid solvent is a dihalogen-substituted or trihalogen-substituted methane liquid
A method for producing a smoked colored and smoked flavored filled food according to item 0. 14. The tar-containing aqueous liquid smoke solution has a total acid content of greater than about 11.5% by weight, and methylene dichloride is the liquid solvent, and the methylene dichloride is mixed in a liquid smoke solution of about 7:1 to about 25:1. 2. A method for producing a smoke-colored and smoke-flavored food according to claim 1, wherein the volume ratio of solution to methylene dichloride is provided. 15. A method for producing a smoke-colored and smoke-flavored food product according to claim 1, wherein the smoke-treated casing has an extinction coefficient of at least about 0.4.