JPS5918018B2 - Production method for fat and oil sorbic acid preparations - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an oil and fat sorbic acid preparation suitable for use as a preservative in the production of meat paste products such as kamaboko and sausages, and a method for producing the same.

(Prior Art) As part of the method for improving the shelf life of paste products, the pH of the paste product is lowered using sorbic acid or other acidic substances,
An attempt to prevent the proliferation of bacteria thereby was published by Mr. Mori et al. [Magazine [New Food Industry] Vol. 8, No. 8, Page 29 (published August 1, 1966)].

However, they predicted that significantly lowering the pH during the crushing of raw meat would have a negative impact on flavor and other important properties, even if the preservation quality was improved, and as a solution, they first decided to use pH-lowering agents. Second, the pH lowering agent should be treated in a pharmaceutical manner so that the pH does not drop during the crushing of raw meat, and the pH lowering agent should be treated in a pharmaceutical manner so that the pH does not drop during the subsequent heating process.
An idea was proposed to lower the pH of the meat by dissolving the H-lowering agent.

In the 45th year of the Special Publication, there was an invention considered to be an embodiment of this idea.
- Invention of No. 14104 (amended after publication) (inventor: Ryuzo Ueno and two others).

In the following description, this invention will be abbreviated as the invention of Shiki Ueno et al.

). The invention of Ueno Shiki et al. is a preservative product with a particle size of 300 to 50μ that does not dissolve at room temperature and is coated with a coating agent that is 1.5 times the amount or more and whose main ingredient is hydrogenated oil with a melting point of 40 to 90°C. It has been patented as a sorbic acid preparation for use.

Although the specification of Ueno Shiki et al.'s invention does not separately explain the meaning of fine grains, in order to conveniently coat sorbic acid, which tends to form needle-shaped crystals, it is recommended that the length of the crystals be made as small as possible. It can be inferred that this would be advantageous, and in the examples, sorbic acid pulverized to 10 μm or less is used.

In addition, regarding the amount of coating agent (hardened oil) for sorbic acid, from the standpoint of sufficiently covering the sorbic acid and preventing the elution of Turbig at room temperature, it is thought that a larger amount of coating agent will serve the purpose. .

In addition, Ueno Shiki et al.
300 to 5 in the written opinion submitted in
It is stated that in order to achieve a particle size of 0μ for the preparation, the melting point of the coating agent (hardened oil) must be specified and the amount thereof must be at least 1.5 times that of finely divided sorbic acid.

In addition, US Patent No. 2,997,394 describes about 120 to
A composition in which sorbic acid is incorporated into a fat having a melting point of 160'F, wherein the sorbic acid accounts for about 5 to 50% by weight of the composition.
30% (Claim No. 4) is stated.

(Purpose of the invention) As mentioned above, conventional fat and oil sorbic acid preparations contain a large amount of solid fat compared to sorbic acid, but this fat is completely useless for its original purpose as a preservative. Since this impairs the original taste of the paste product, it is desirable that the amount of fat be as small as possible as long as it acts to prevent the elution of sorbic acid at room temperature.

Therefore, the present invention provides oil and fat sorbic acid that contains a small amount of unnecessary fat, contains a large amount of sorbic acid as an active ingredient, and has excellent non-eluting properties at room temperature, which is a desired property for adding to meat paste products. It is an object of the present invention to provide a formulation and a method for manufacturing the formulation.

(Structure of the Invention) As a result of many years of dedicated research into technical means for solving the above-mentioned problems, the present inventors have surprisingly found that the Even with the use of sorbic acid with a much larger average viscosity range of around 50μ, it is possible to produce sorbic acid formulations with low fat content via slurries containing high concentrations of sorbic acid in melted fat. They discovered what could be done and completed the present invention.

That is, the features of the present invention are as follows.

(1) In sorbic acid preparations in which fine particles of sorbic acid are coated with solid fat, the particle size of sorbic acid is mainly 20 to 8.
0μ, and the weight ratio of sorbic acid to solid fat is about 0.75 to 1.2:1.

(2) In the method of manufacturing fat and oil sorbic acid preparations by melting fat that is solid at room temperature and dispersing sorbic acid therein into granules, and then cooling and solidifying the slurry, the particle size of sorbic acid is is mainly 20-80
μ range, with a weight ratio of sorbic acid to fat of approximately 0.7
5 to 1.2:1, and the temperature of the slurry subjected to granulation is about 85 to 110°C.

(Viscosity of sorbic acid) During the research process, the present inventors first prepared a slurry by adding pulverized sorbic acid to a particle size of 10μ or less into a melt of hardened beef tallow oil, and investigated its granulation potential. Tested.

As a result, it was found that among the physical properties of this slurry, viscosity was particularly problematic.

That is, at a temperature around 80°C, which is considered suitable in the prior art, as the ratio of fine powder sorbic acid suspended in molten hardened oil increases from 0.25° to 0.49 to 0.82, , the viscosity of the slurry is 13,30,
The slurry rapidly increases to 120 voids, and if the concentration is made higher than this, the viscosity of the slurry becomes so high that viscosity measurement is impossible.

As described above, if the sorbic acid viscosity in the prior art was followed, an increase in the sorbic acid concentration would lead to higher viscosity of the slurry, making granulation difficult and making it impossible to produce the desired formulation.

Therefore, according to general technical knowledge, it is possible to raise the temperature in order to lower the viscosity of the slurry, and in fact, the viscosity of the slurry consisting of fine powdered sorbic acid and molten hardened oil decreases at high temperatures. The run shows a tendency to decrease.

However, in the specification of the invention by Uenohi et al., the temperature when adding fine powdered sorbic acid to molten hydrogenated oil is 90°C.
When the temperature exceeds C, sorbic acid begins to dissolve in hydrogenated oil, and 12
It is stated that sorbic acid completely dissolves at 0°C, and if the dispersion is left at a high temperature, the ratio of hydrogenated oil to sorbic acid will change due to volatilization of sorbic acid, so the temperature should be set at 90°C. It is necessary to maintain the
As can be seen from the fact that it is said that it is preferable to adjust the temperature between 0 and 85°C, the decrease in viscosity due to temperature rise was abandoned as being inappropriate, and as a result, oils and fats were
．． It is surmised that an unsatisfactory solution was adopted, using more than five times as much.

In addition, in the invention of Uenohi et al., they argued that changes in temperature cause the sorbic acid particles dispersed in the hydrogenated oil to grow, making it impossible to obtain a good product. has been done.

In view of this fact, it is clear that the prior art required that sorbic acid be in fine powder form.

Based on the above-mentioned technical background, the present inventors boldly took on the problem of the particle size of sorbic acid from a completely new perspective, without being bound by the prior art, and conducted various studies.

That is, the physical properties of a slurry made by using sorbic acid with a larger particle size than the sorbic acid used in the prior art and dispersing it in molten fat, whether or not the slurry can be granulated, and the room temperature dissolution properties of the resulting preparation. As a result of a detailed study of other properties, we found that, surprisingly, if sorbic acid in the range of 20 to 80μ is used and specific production conditions are followed, the oil content is small and the room-temperature dissolution property is also minimal. They discovered that it is possible to create sorbic acid preparations.

In short, one of the core aspects of the present invention is the use of larger sorbic acid particles than those used in the prior art.

However, excessively large grains (e.g. 100-200μ)
), the viscosity of the slurry decreases, but the sedimentation rate of sorbic acid in the slurry increases, which impairs the stability of the slurry and makes it difficult to handle, and the particle size of the sorbic acid preparation is inappropriate. Then,
Quality also decreases.

From this point of view, in the present invention, the particle size range of sorbic acid was mainly selected to be 20 to 80 microns.

Here, the particle size of sorbic acid will be explained.

Since sorbic acid itself is a crystalline substance, it almost never takes a spherical shape.

Depending on the crystallization conditions, it is possible to produce sorbic acid in the form of rice grains, but in most cases it is in the form of elongated needle-like crystals.

Accordingly, in the present invention, the dimension representing the particle size of sorbic acid (i.e. 20-80μ) is the equivalent diameter.

Although the value of the equivalent diameter may vary slightly depending on the measurement method, the particle size range defined in the present invention is determined using the equivalent diameter determined by the sedimentation method, which is a common measurement method. I can do it.

However, other measurement methods can also be used.

In other words, the particles passing through a 200-mesh sieve are
It can be safely assumed that the upper limit of the main particle size of 80μ is satisfied.

It is also possible to determine the main viscosity based on the size of the image in the micrograph.

In addition, the particle size of 20 to 80μ mainly refers to 20 to 80μ.
For example, 18% of particles with a size of 80μ or more, 10-20μ
There is no problem even if a small amount of particles outside the range of 20 to 80 microns are mixed in, such as about 13% of the particles having a particle size of 20 to 80 microns, and about 4% of particles having a particle size of less than 10 microns.

However, it is not preferable that the particles outside this range are extremely biased to one side, and it is preferable that particles less than 10 μm and particles exceeding 80 μm each account for 30% or less.

Those having an average particle size of about 50μ can usually be used.

Sorbic acid mainly has a particle size range of 20-80μ,
For example, it can be easily obtained by recrystallization, which is commonly used as a purification method for sorbic acid.

That is, among the crystals obtained according to the operating conditions normally carried out in the recrystallization method of sorbic acid, relatively small particles are mainly obtained in the particle size range of 20 to 80 microns.

Further, by adjusting the cooling rate, crystal growth time, etc. in the recrystallization method, crystals of 20 to 80 μm can be obtained as the main product.

Furthermore, by crushing coarse crystals, it is possible to obtain sorbic acid in the range of 20 to 80μ, but during crushing, fine powder of sorbic acid tends to scatter, which irritates the mucous membranes of the human body. Therefore, measures must be taken to prevent the scattering of fine powder.

Incidentally, sorbic acid with a particle size of 10 μm or less, which is used in the prior art, is difficult to obtain under normal recrystallization conditions, so it is usually obtained by pulverization.

(Fat) The solid fat used in the present invention is an edible fat that is solid at room temperature and melts into liquid at the temperature of the slurry, that is, 85 to 110°C, and at the heating temperature of the dough.

Typical examples include hydrogenated beef tallow oil and hydrogenated rapeseed oil, but animal and vegetable fats used in the prior art described above can also be used.

Preferred are fats with a melting temperature around 60°C.

(Mixing Ratio) The weight ratio of sorbic acid to fat is an important component of the present invention, as is the particle size of sorbic acid, and is approximately 0.75.
:1 to 1.2:1, and the preferred range is about 0.75:1 to 1:1.

From the purpose of the present invention, it is preferable that the weight ratio of sorbic acid to fat in the slurry be as large as possible; however, from the viewpoint of difficulty in granulation, increasing the content of sorbic acid too much increases the viscosity of the slurry. , which in turn makes granulation difficult.

For example, when the weight ratio of sorbic acid to fat was 1.5, it was possible to raise the temperature of the slurry to 120°C and barely granulate it, but the yield of the formulation was low, so this was not an industrial advantage. It is inappropriate in some respects.

(Slurry) In the method for producing an oil-fat sorbic acid preparation of the present invention, a slurry, which is an intermediate product, is produced by adding and suspending sorbic acid having a particle size of 20 to 80 μm to melted fat.

In the prior art described above, it is necessary to maintain the temperature of the slurry at 90°C or less in consideration of the solubility of sorbic acid in fat and the volatility of sorbic acid, but in the present invention. The temperature of the slurry is 90℃.
There is no need to limit it to the following, and the purpose can be achieved within the range of about 85 to 110°C, especially about 85 to 100°C.
A range of °C is preferred.

In the present invention, the fat content is much lower than that employed in the prior art (4 times the amount of sorbic acid in the example), and as a result, the disturbances associated with the dissolution of sorbic acid in fat are significantly reduced. Therefore, the slurry can now be handled without problems even at high temperatures, which were considered inappropriate in the prior art.

However, the temperature of the slurry is excessively high (for example, 12
0°C or higher), not only does the amount of sorbic acid dissolved in fat rapidly increase, but also the vapor pressure of sorbic acid increases, making it easier to volatilize, and furthermore, problems such as deterioration of the quality of sorbic acid itself occur. This is not desirable because it causes

Further, if the temperature of the slurry is excessively lowered, the viscosity of the slurry increases, making it unsuitable for granulation operation (usually a spray granulation operation using a rotating disk type device).

Examples of the relationship between temperature and viscosity are mainly 2.
Sorbic acid with a particle size of 0 to 80 μ is added to 0.0 μm of hardened beef tallow oil.
The slurry containing 82 times (by weight) had a viscosity of 11 poise at 100°C and 13 poise at 90°C, a viscosity suitable for granulation operations, whereas that employed in the prior art When fine powder sorbic acid with a size of 10 μm or less was used 0.82 times (by weight) as hardened beef tallow oil, the viscosity of the slurry was as high as 70 poise at 100° C., making granulation difficult.

(Granulation/Cooling) In order to granulate the slurry and cool the formulation particles, ordinary granulation techniques such as the spraying method and the fluidization method can be applied.

For granulation, means such as a pressurized nozzle, a normal pressure nozzle, or a rotating disk can be used.

However, in the present invention, the particles contained in the slurry are mainly 20 to 80μ, which is slightly larger.
Slurry tends to become highly viscous when cooled, so pressure nozzles tend to clog.

Therefore, a normal pressure nozzle or a rotating disk method is more suitable.

In any case, when the slurry is divided into small pieces, it becomes granular due to the action of surface tension, is cooled by air at room temperature or low temperature, and solidifies to become the fat-and-oil sorbic acid preparation of the present invention.

(Properties of the preparation) Oil-fat sorbic acid preparations used as preservatives for meat paste products such as kamaboko contain sorbic acid in a predetermined ratio. It is necessary that sorbic acid not be eluted at room temperature (at room temperature), but sorbic acid should be eluted in the heating step following the crushing.

As described above, in order to satisfy this requirement, a fat having a melting temperature lower than the heating temperature of the paste product (for example, around 60° C.) is selected and used as a coating agent.

The present inventors adopted the following test method in order to measure the non-elution property of fat and oil sorbic acid preparations at room temperature.

That is, the fat-and-oil sorbic acid preparation was thoroughly stirred with water containing a surfactant, and the sorbic acid dissolved in the water was titrated to evaluate the dissolution rate of sorbic acid.

The reason why a surfactant is used in this case is to ensure that the oil/fat sorbic acid preparation is sufficiently dispersed in water.

The fat-and-oil sorbic acid preparation of the present invention is completely different from known fat-and-oil sorbic acid preparations in the particle size of the raw sorbic acid and the composition ratio of sorbic acid in the preparation, but the particle size of the preparation is different from known ones. There is no big difference, and it is about 40 to 350μ.

Therefore, it is inferred that the internal structure of a formulation consisting of sorbic acid crystals and fat that envelops or binds them is significantly different from that of known formulations.

In the present invention, much larger grains of raw sorbic acid are used than in known oil/fat sorbic acid formulations, so
If a part of the large crystals of sorbic acid are exposed on the surface of the preparation, the dissolution rate at room temperature will increase.
It must be said that it is not suitable for the purpose of use.

However, although the sorbic acid preparation of the present invention uses much larger particles of sorbic acid and a much smaller amount of coating agent than the known preparations, surprisingly, the sorbic acid preparation is superior to the known preparations in terms of non-elution at room temperature. It is something that has gender.

In other words, as shown in the Examples below, a slurry with a weight ratio of sorbic acid to fat of 0.82:1 yields a preparation with a room temperature dissolution rate of only about 1%, and a weight ratio of sorbic acid to fat of 0.82:1. Even when the ratio is increased to about 1:1, the dissolution rate at room temperature is about 4%, making it an extremely excellent preservative to be added to paste products.

On the other hand, the formulation according to the invention of Mr. Ueno et al. has a room temperature dissolution rate of about 6 to 11%, according to the experimental report submitted in the trial proceedings.

As mentioned above, it was completely unexpected that using a small amount of fat, approximately the same amount as sorbic acid, the much larger sorbic acid crystals were almost completely coated than in the prior art. The objectives of the present invention to provide a formulation with improved efficacy, increased content of active ingredients, and excellent quality have been fully achieved.

According to the production method of the present invention, the yield of the preparation is almost quantitative with respect to the raw materials charged.

EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to the Examples below, and includes various embodiments in addition to these Examples.

All parts in the examples mean parts by weight.

Example 1 The particle size of sorbic acid from which coarse particles were removed using a 200° mesh sieve (sieve spacing 74 μm) was confirmed using a microscope, and was found to be mainly 30 to 60 μm.

Melt hardened beef tallow oil with a melting temperature of 55 to 60°C,
While stirring 550 parts of the molten liquid maintained at 5 to 90°C, 450 parts of the above sorbic acid was added and sufficiently dispersed to obtain a uniform slurry.

This slurry had a viscosity of about 14 poise (measured with a B-type viscometer), and almost no non-uniformity due to sedimentation was observed even after it was allowed to stand for about 1 hour.

This slurry was pulverized into fine particles using a granulator equipped with a rotating disc-type spraying mechanism, and cooled while descending in the air at a height of 20 to 30' to obtain a fat-and-oil sorbic acid preparation.

The particle size of the preparation measured by the sieve method is 40-35.
The average value was 180μ in the range of 0μ.

1 part of the above formulation was added to 200 parts of water at 20°C containing 0.1% nonionic surfactant, stirred for 10 minutes, filtered, and the P solution was reduced to 0.1%. The amount of eluted acid was determined by titration with a sodium hydroxide solution of IN, and the dissolution rate relative to the amount of sorbic acid contained in the formulation was determined to be only 1.2%.

For comparison, a preparation was prepared in the same manner from a slurry obtained by dispersing 300 parts of sorbic acid, which had been ground to a size of 5 to 10 microns, in 600 parts of melted hardened tallow oil.
20'C! When the elution rate was measured, it was 6.5%.
This was a high rate.

Example 2 Coarse particles of sorbic acid were pulverized and sieved, and 520 parts of sorbeans with an average particle size of 45 μ by the sedimentation method were prepared from 102 to
A uniform slurry was obtained by dispersing it in 500 parts of hardened beef tallow oil kept at 105°C.

This was granulated using a granulator equipped with a normal pressure nozzle type spray mechanism and cooled with cold air.

The particle size of the obtained sorbic acid preparation was 140μ on average, and the dissolution rate measured by the same method as in Example 1 was 4.2%.

Example 3 Sorbic acid soog, whose particle size is mainly 30 to 70μ as measured by the sedimentation method, was added to 500 parts of rapeseed hydrogenated oil heated and melted at 95 to 100°C, stirred to sufficiently disperse it, and made into a uniform slurry. I got it.

This slurry was spray granulated in the same manner as in Example 1 to obtain 970 parts of an oil/fat sorbic acid preparation with an average particle size of 140 μm.

The room temperature dissolution rate of this formulation was 2.5%.

Application Example 25 parts of common salt and 300 parts of ice water were added to 1000 parts of frozen surimi of kamaboko raw material and crushed for 40 minutes.

A liquid prepared by mixing 13 parts of seasoning, 50 parts of starch, 2 parts of sugar, and 6 parts of the oil/fat sorbic acid preparation obtained in Example 1 in 100 parts of water was added to the kamaboko raw material, and further 1
It was crushed for 0 minutes.

The pH before the addition of the oil/fat sorbic acid preparation was 6.90, but the pH after the addition was 6.80, so it can be said that it was almost neutral.

Subsequently, it was attached to a board, allowed to sit for 2 hours, and then steamed for 30 minutes.

Since the pH of the obtained kamaboko was 6.33, it was confirmed that sorbic acid was eluted by heating.

The elasticity of this kamaboko was equivalent to that of kamaboko to which no preservative was added.

Kamaboko with sorbic acid added instead of fat and oil sorbic acid preparation (pH after crushing is 5.80, pH after steaming is 6)
．． 30) had significantly poor elasticity.

The preservative effect of kamaboko according to this example was tested with kamaboko to which potassium sorbate was added instead of the fat-and-fat sorbic acid preparation (pH after steaming was 7.03) and kamaboko to which no preservative was added (pH after steaming was 7.0). As a result of comparison, the antiseptic effect of the oil/fat sorbic acid formulation of the present invention was excellent.

The following comparative experiment was also conducted separately.

(Experiment method) Frozen walleye surimi IK7, salt 30g, and water 10
After mixing and crushing 0g for 40 minutes, add 3011 cold water, 3g sugar, 1 seasoning 7.5. ! 9. 15 g of Ajirin and 40.9 g of Katakuri powder were added, and the mixture was further crushed for 5 minutes.

Take 100g of the kamaboko raw material obtained in this way, mix well with the preservative listed in the table below, place in a petri dish,
The mixture was steamed at a temperature of ~95°C for about 20 minutes and cooled to serve as a culture medium.

The bacteria listed in the table below were inoculated into this medium and cultured at a temperature of 30°C for 24 hours, and then the results were determined based on whether the presence of colonies was observed.

The bacteria used are as follows.

DCB-11 Escherichia coli DCB-12 Staphylococcus DCB-14 Bacillus subtilis (Experimental result) (note) 1. The product of the present invention is the oil of Example 1. It is a fat sorbic acid preparation.

2. Commercially available preparations are sorbic acid anti-lipid Fat and oil sorbitol with a fat weight ratio of 0.521 It is an acid preparation.

3. In 10 cases, the existence of a colony was recognized. - indicates the existence of a colony. Indicates that it was not approved.

Claims (1)

[Claims] 1. In a method for producing fat and oil sorbic acid preparations by melting fat that is solid at room temperature, dispersing sorbic acid therein to form a slurry, granulating this slurry, and solidifying it by cooling, the particle size of sorbic acid is is primarily in the range of 20 to 80μ, the weight ratio of sorbic acid to fat is from about 0.75:1 to about 1.2:1, and the temperature of the slurry subjected to granulation is from about 85 to 110μ.
A method for producing an oil-fat sorbic acid preparation, characterized in that the temperature is °C.