JP2011227066A - Labeled additive for food product, medicine or feed, manufacturing method for same labeled additive, and identification method of food product, medicine or feed - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a labeled additive for a food product, medicine, or feed, capable of identifying a food product, medicine, or feed, a manufacturing method for the same labeled additive, and an identification method of a food product, medicine, or feed.SOLUTION: After washing unburnt shell, an organic substrate is carbonized and ashed in a primary heat-treatment in air within 400°C-600°C. Then, the shell cooled to about room temperature is pulverized, and a secondary heat-treatment is carried out in CO2 atmosphere in 800°C-900°C, whereby shell powder is obtained. The intensity ratio of three light emission bands of a light emission spectrum of the shell powder, is used to assign an identification number, and calcium carbonate obtained from the shell is used as a main component, by the labeled additive for a food product, medicine, or feed. By adding the labeled additive to a food product, calcium fortification and quality improvement is provided, and by measuring the light emission spectrum of a sample remaining after ashing this food product, the food product, medicine, or feed is capable of easily being identified.

Description

  The present invention belongs to existing additives in the classification of food additives, and when added to foods, medicines or feeds, has the function of easily distinguishing (or distinguishing) these foods or medicines or The present invention relates to a labeled additive for feed, a method for producing the labeled additive, and a method for identifying food, medicine, or feed.

In recent years, consumers' awareness of food safety and security has increased. This originates from the BSE problem of beef, and news that threatens food safety and security, such as fraudulent production of ingredients and falsification of the shelf life of food, is communicated to consumers through various media, and consumers This is thought to be due to the greater interest in security.
As a countermeasure against such a problem, a method of identifying the food material itself, such as DNA analysis in beef traceability, is effective. On the other hand, falsification of the shelf life of food cannot be identified by DNA analysis, and another simple identification method is desired.

  As a method for identifying a material using an additive, there has been proposed a method of identifying a material by using three types of phosphors and changing the addition amount of each phosphor (see Patent Document 1). However, the additive (phosphor) in the present invention is not edible by humans, and therefore, the materials to be identified include industrial materials such as plastics and metals. The above-mentioned problems related to food cannot be solved.

  On the other hand, there is a proposal of a method for identifying foods, feeds, and pharmaceuticals using an additive labeled with a stable isotope (see Patent Document 2), but in this case, an expensive and rare stable isotope is required. There is a problem of application to food additives that are required to be inexpensive and abundant.

By the way, the amount of scallops in Japan is about 500,000 tons per year, and the amount of shells after eating scallops is about 250,000 tons every year. Since most scallops are stripped by fisheries processing companies in the area where they are landed, a large amount of shells that are no longer needed continue to be generated in the area.
In this way, a part of the shells that continue to be generated in a large amount in a specific area have been recycled as soil conditioners, culvert materials, and so on.

  However, the utilization rate of scallop shells is still low, and the rest is stored or disposed of as industrial waste. In particular, Hokkaido scallops are the number one in the country, but scallop shells that are no longer needed are the number one fishery by-products and waste in Hokkaido, and their effective use is required.

  Based on such a background, the present inventors have proposed that a phosphor is manufactured by firing scallop shells at a temperature exceeding 100 ° C. (see Patent Document 3). This invention was a novel invention at that time, but it was completed at the level of simply burning a shell to produce a phosphor, and it was added to a food, medicine or feed for labeling. I did not come up with the idea.

  Starting from Patent Document 3 above, the present inventors report that the shell changes phase with calcium carbonate, calcium oxide, and calcium hydroxide, and the intensity of fluorescence varies with the firing temperature of the scallop shell. (See Non-Patent Document 1).

In addition, the present inventors have reported that the water resistance of a shell phosphor can be improved (suppression of weathering and quenching) by firing calcium carbonate in a carbon dioxide (CO ₂ ) atmosphere (non-patented). Reference 2).
Furthermore, the present inventors have clarified the emission center of a phosphor using a scallop shell and reported that the presence of an organic substrate contained in the shell is important (see Non-Patent Document 3).

  However, the contents reported in these documents are the contents of the basic research level related to the method of manufacturing phosphors from shells and the physical properties (such as optical properties) of the manufactured ones. The idea of labeling was not reached.

  On the other hand, baked and unfired shell powder has been conventionally used as a food additive for the purpose of calcium fortification, for example, and there is a disclosure relating to a method for producing edible scallop shell powder (see Patent Document 4). However, since the shell powder produced by this method does not exhibit fluorescence, it cannot be added to food and labeled.

JP 2003-248790 A Special table 2009-501120 JP 2004-359923 A JP 2002-272421 A

"Fluorescence characteristics of scallop shells fired" Journal of Ceramic Society of Japan, 2004 112 [3], pages 184-188 "Fluorescence characteristics of scallop shells fired in a carbon dioxide atmosphere" Journal of Ceramic Society of Japan, 2006 114 [4], pages 341-346 “Study on luminescent center of phosphor using scallop shell” Journal of Ceramic Society of Japan, Supplement, 2009 117 [4], S5-S10

  The present invention relates to a calcined shellfish powder used as a food additive, and is added to food, medicine or feed to enhance calcium and improve quality, and remains after ashing the food, medicine or feed. By measuring the emission spectrum of the sample, it is possible to easily identify the food, drug, or feed. It is an object of the present invention to obtain a manufacturing method and a method for identifying food, medicine, or feed.

In view of the above problems, the present application provides the following inventions.
1) Powdered food, medicine or feed additive mainly composed of calcium carbonate obtained from shells, which emits light when excited energy is added thereto, for food, medicine or feed Labeled additive The above "luminescence" is used as a synonym for luminescence, which is a general term for fluorescence and phosphorescence.
2) The labeled additive according to 1) above, wherein the emission spectrum comprises one or more emission bands.
3) The label according to any one of 1) or 2) above, wherein the peak wavelength of the emission band is any one or more of 420 ± 5 nm, 490 ± 5 nm, and 580 ± 5 nm. Additive.
4) The labeled additive as described in 3) above, wherein the optimum excitation wavelength of each emission band is 250 ± 5 nm.
5) Light emission by adding one or more selected from ammonium chloride (NH ₄ Cl), calcium chloride (CaCl ₂ ), and sodium chloride (NaCl) to a powder mainly composed of calcium carbonate obtained from shells. The labeled additive according to any one of 1) to 4) above, wherein the intensity ratio of the emission band of the spectrum is changed.
6) One or two kinds selected from copper chloride (CuCl ₂ ) and manganese chloride (MnCl ₂ ) are added to the powder mainly composed of calcium carbonate obtained from the shell, and the intensity ratio of the emission band of the emission spectrum is increased. The labeled additive as described in 5) above, which is changed.
7) The labeled additive according to any one of 1) to 6) above, wherein a scallop shell is used.
8) The labeled additive according to any one of 1) to 7) above, which is a mixture of a plurality of powders having different emission band intensity ratios.
9) A labeled additive in which two or more kinds of the labeled additive according to any one of 1) to 8) above are mixed to change the intensity ratio of the emission band of the emission spectrum.

The present invention also provides the following inventions.
10) After washing the unfired shell, the organic substrate is carbonized and incinerated by primary heat treatment in the range of 400 ° C to 600 ° C in the atmosphere, and then the shell cooled to near room temperature is pulverized, and then in a CO ₂ atmosphere. A food mainly composed of calcium carbonate obtained from shells characterized in that secondary heat treatment is performed at 800 ° C. to 900 ° C., and an identification number is given from the intensity ratio of the emission band of the emission spectrum of shell powder obtained thereby. Or the manufacturing method of the labeled additive for pharmaceutical products or feed.
11) One or more additives selected from ammonium chloride (NH ₄ Cl), calcium chloride (CaCl ₂ ), and sodium chloride (NaCl) are added to the shell powder subjected to the primary heat treatment, and the emission band of the emission spectrum 10. The method for producing a labeled additive as described in 10) above, wherein the intensity ratio is changed.
₁₂₎ NH 4 Cl, upon CaCl _2, or the addition of NaCl, NH _{4 NH} 4 Cl in advance a predetermined concentration, thereby preparing a CaCl ₂ and NaCl aqueous solution, relative to the weight of the shell powder subjected to the primary heat treatment 11. The method for producing a labeled additive as described in 11) above, wherein the additive is added so that the concentration of one or more selected from Cl, CaCl ₂ and NaCl is 0.3% to 3%.
13) One or two additives selected from copper chloride (CuCl ₂ ) and manganese chloride (MnCl ₂ ) are added to the shell powder subjected to the primary heat treatment to change the intensity ratio of the emission band of the emission spectrum. 11. The method for producing a labeled additive as described in 11) or 12) above.
14) Upon the addition of CuCl ₂ or MnCl _2, with making CuCl ₂ and or MnCl ₂ aqueous solution in advance a predetermined concentration, the concentration of CuCl ₂ and or MnCl ₂ relative to the weight of the shell powder subjected to the primary heat treatment 13. The method for producing a labeled additive as described in 13) above, wherein the additive is added so as to be 1 ppm to 100 ppm.

The present invention also provides the following inventions.
15) The labeled additive according to any one of 1) to 9) above is added to food, medicine, or feed, both of which are incinerated at 500 ° C to 600 ° C, and then after incineration A method for identifying food, medicine or feed, characterized in that the identification is performed based on the intensity ratio of the emission bands of the emission spectrum of the sample.
16) The labeled additive obtained by the production method according to any one of 10) to 14) above is added to food, medicine, or feed, and both of these are incinerated at 500 ° C to 600 ° C. And then identifying the food or pharmaceutical product or feed according to the intensity ratio of the emission band of the emission spectrum of the sample after ashing.

According to the present invention, it belongs to the existing additives in the classification of food additives, and calcium addition and quality improvement are made by adding to foods, and the ashed sample before adding to foods and after adding to foods According to the intensity ratio of the emission bands of the emission spectrum, it has an excellent effect of having a function of easily identifying food. In this way, for example, by adding the additive of the present invention to the crushed food material, even in the food material in which the shape (form) is not known, it is used as a mark for certifying its own product and its expiration date. There is a remarkable effect that can be.
Further, the present invention has an excellent effect that it can be applied not only to the above-mentioned food additives but also to the identification of medicines and feeds, since shells with experience of eating are used as raw materials.

It is a figure which shows the emission spectrum of the additive A before adding to the foodstuff shown in Example 1. FIG. 2 is a graph showing an emission spectrum of an additive A after ashing treatment shown in Example 1. FIG. It is a figure which shows the emission spectrum of the additive B before adding to the foodstuff shown in Example 2. FIG. 6 is a graph showing an emission spectrum of an additive B after ashing treatment shown in Example 2. FIG. It is a figure which shows the emission spectrum of the additive C before adding to the foodstuff shown in Example 3. FIG. 6 is a diagram showing an emission spectrum of an additive C after ashing treatment shown in Example 3. FIG. It is a figure which shows the emission spectrum of the additive D before adding to the foodstuff shown in Example 4. FIG. It is a figure which shows the emission spectrum of the additive D after the ashing process shown in Example 4. FIG. It is a figure which shows the flow for demonstrating the content of the present Examples 1-4.

  In the production of the labeled additive for food or medicine or feed of the present invention, first, unfired shells are used as a raw material. A typical example of the shell is a scallop shell that is cultivated in large quantities for food.

  First, after the raw shell as a raw material is washed, a primary heat treatment is performed for the purpose of carbonizing and ashing the organic substrate. Here, the primary heat treatment condition is suitably 400 ° C. to 600 ° C. in the atmosphere. Those subjected to the primary heat treatment at less than 400 ° C. in the atmosphere have insufficient carbonization and ashing of the organic substrate. In addition, when subjected to primary heat treatment at a temperature exceeding 600 ° C. in the atmosphere, a phase change from calcium carbonate to calcium oxide occurs, and the water resistance performance as a phosphor is significantly lowered. The primary heat treatment is performed using a heat treatment furnace such as a muffle furnace.

Then, it cools to room temperature vicinity and grind | pulverizes using the electric mill etc. of a grind blade rotation type. Next, a secondary heat treatment is performed for the purpose of imparting light emission characteristics to the shells as raw materials. Here, the secondary heat treatment condition is suitably 800 ° C. to 900 ° C. in a CO ₂ atmosphere. Those subjected to secondary heat treatment at less than 800 ° C. in a CO ₂ atmosphere have remarkably weak emission intensity. In addition, in the case where the secondary heat treatment is performed at a temperature exceeding 900 ° C. in a CO ₂ atmosphere, a phase change from calcium carbonate to calcium oxide occurs, and the water resistance performance as a phosphor is significantly lowered.

The secondary heat treatment is performed using a heat treatment furnace such as a gas replacement tubular furnace. Here, after putting the sample in the tubular furnace, the furnace pressure is once lowered to 5 Pa or less, and then CO ₂ gas having a purity of 99.5% or more is introduced until the pressure reaches 0.1 MPa.
After the secondary heat treatment, the sample can be pulverized using an agate mortar and classified with a sieve (opening diameter of about 100 μm) to complete a labeled food additive. The emission spectrum of the shell powder thus obtained was measured and used as a reference emission spectrum made from a shell containing no additive.

  When measuring the emission spectrum of shellfish powder, the excitation / emission spectrum is measured using a spectrofluorometer (or fluorescence spectrophotometer). Here, when the excitation spectrum is measured, the optical system on the light receiving side is fixed at the peak wavelength of the emission spectrum, and when the emission spectrum is measured, the optical system on the irradiation light side is fixed at the peak wavelength of the excitation spectrum. Measure with

  FIG. 1 shows a typical emission spectrum of a phosphor produced using a shell as a raw material. The emission spectrum consists of three emission bands having peaks at 420 ± 5 nm, 490 ± 5 nm, and 580 ± 5 nm. The optimum excitation wavelength for each emission band is 250 ± 5 nm. Here, the reason for setting the peak wavelength of each emission band and the optimum excitation wavelength of each emission band to be in the range of ± 5 nm is that the excitation wavelength depends on the variation due to individual differences in natural shells, the measurement reproduction accuracy of the spectrofluorometer, etc. This is because there is a possibility that an appropriate wavelength cannot be grasped unless the range is included.

As described above, the shell alone can be an additive for labeled food or medicine or feed. However, as this, ammonium chloride (NH ₄ Cl), which is a designated additive for food, calcium chloride (CaCl ₂ ), which is also a designated additive for food, sodium chloride (NaCl), which is a seasoning, A plurality of these may be added. That is, as the first additive, one or two or more additives selected from NH ₄ Cl, CaCl ₂ , and NaCl are added to the shell powder that has been subjected to the primary heat treatment, and then subjected to the secondary heat treatment to emit light of the emission spectrum. The intensity ratio of the band can be changed.

When adding the above NH ₄ Cl, CaCl ₂ , or NaCl, an aqueous NH ₄ Cl, CaCl ₂ and NaCl solution having a predetermined concentration is prepared in advance, and the shell powder subjected to the primary heat treatment in a magnetic crucible is weighed. In addition, by adding one or more selected from NH ₄ Cl, CaCl ₂ , NaCl at a predetermined concentration to this, food having an emission band intensity ratio different from that of shells alone, Alternatively, labeled additives for pharmaceuticals or feed can be produced.
Here, the concentration of the first additive is suitably 0.3% to 3%. When the first additive was added in an amount of less than 0.3%, the intensity ratio change in the emission band of the emission spectrum was insufficient. Moreover, the intensity | strength of the emission spectrum fell that what added the 1st additive exceeding 3%.

When the additive is mixed with the shell powder subjected to the primary heat treatment in the magnetic crucible, pure water is added and stirred, and then put into a dryer and dried at 100 to 120 ° C. If necessary, this is crushed using an agate mortar or the like.
Next, as described above, secondary heat treatment is performed at 800 ° C. to 900 ° C. in a CO ₂ atmosphere. The emission spectrum of the shell powder thus obtained is measured. Thereby, the intensity ratio of the emission band of the emission spectrum different from the case of the shell alone can be changed.

Further, as the second additive, one or two additives selected from copper chloride (CuCl ₂ ) and manganese chloride (MnCl ₂ ) are added to the shell powder subjected to the primary heat treatment together with the first additive, and light emission The intensity ratio of the emission band of the spectrum can be changed. In this case, when adding CuCl ₂ or MnCl ₂ , a CuCl ₂ and / or MnCl ₂ aqueous solution having a predetermined concentration is prepared in advance, and the shell powder subjected to the primary heat treatment in a magnetic crucible is weighed in the same manner as described above. And adding the second additive CuCl ₂ and / or MnCl ₂ at a predetermined concentration together with the first additive, the intensity ratio of the emission band of the emission spectrum different from that of the shell alone and the first additive is obtained. It is possible to produce a labeled food or medicine or feed additive.

  Here, the concentration of the second additive is suitably 1 ppm to 100 ppm. In the case where 0.5 ppm of the second additive was added, the intensity ratio change in the emission band of the emission spectrum was insufficient. In addition, in the case where 100 ppm of the second additive was added, the intensity of the emission spectrum was significantly reduced by concentration quenching.

As described above, in the case of a shell alone, when the first additive is added, or when the first additive and the second additive are used in combination, the thickness is 420 ± 5 nm, 490 ± 5 nm, and 580 ± 5 nm. A labeled food additive consisting of three emission bands with peaks can be produced. The chemical formula of the fired shell can be expressed as CaCO ₃ : Cu, Mn, Cl, following the chemical formula in which the matrix and the emission center are connected by a colon in the phosphor.

  The features of the present invention will be specifically described below. The following description is intended to facilitate understanding of the present invention, and is not limited thereto. That is, all modifications, other embodiments, and other examples based on the technical idea of the present invention are included in the present invention.

Example 1
Using only shells as raw materials, the intensity ratio of the three emission bands of the emission spectra having peaks at 420 ± 5 nm, 490 ± 5 nm, and 580 ± 5 nm according to the production method described above is the identification number 046 of additive A in Table 1. The additive for foodstuffs, a pharmaceutical, or a feed so that it might become intensity | strength ratio shown in FIG.

Here, how to obtain the identification number will be described. In accordance with the measurement method described above, the emission spectrum of the product of the present invention was measured while irradiating with excitation light, and the intensity values N ₁ , N ₂ , and N ₃ of the _three emission bands were determined from the obtained emission spectra.
Next, the sum of the intensity of the three emission bands is N = N ₁ + N ₂ + N _3, and the intensity of each emission band is divided by the sum of the intensity of the three emission bands, n ₁ = 10 × N ₁ / N, n ₂ = 10 × N ₂ / N, n ₃ = 10 × N ₃ / N is determined, and the first decimal place is rounded off to an integer, and the sum of the three is 10 (= n ₁ + n ₂ + n ₃ ). The number indicated by the three digits n ₁ n ₂ n ₃ was used as the identification number. The method for obtaining the identification number from the intensity values N ₁ , N ₂ , and N _{3 of the three} light emission bands is based on a mathematical calculation method, and is not limited to the method described here.

Next, using the produced identification number 046 and the recorded additive A, the result when this was added to food is shown. In the present Example 1, rice flour (made by A company) was used as a foodstuff.
Here, the reason why rice flour was selected as the food was selected because it is similar in color and shape to the labeled food additive of the product of the present invention, and is difficult to distinguish visually before and after the addition. Additive A was mixed with this rice flour, and water was added and kneaded well to obtain an appropriate softness to prepare a dumpling dough. The dough was boiled in boiling water for several minutes, then transferred to cold water to cool, and well drained with a straw.

Here, when the rice powder to which the additive A is added is irradiated with excitation light, the food material also emits fluorescence, and this fluorescence becomes noise when reading the identification number. In order to solve such a problem, the ashing treatment of the food to which the additive A was added was performed.
The food to which additive A was added was placed in a porcelain crucible and dried as much as possible with a 105 ° C dryer. Thereafter, the food was carefully carbonized using a hot plate. The sample thus treated was heated for 5-6 hours until an off-white ash was obtained at 500-600 ° C. After completion of ashing, heating was stopped and the mixture was allowed to cool to obtain an ashed sample.

The emission spectrum of the sample after ashing produced in this way was measured according to the measurement method described above. An outline of the flow of the above steps is shown in FIG. In the following examples, the emission spectrum was examined with the same flow.
The emission spectrum of the additive A before being added to the food is shown in FIG. 1, and the emission spectrum of the additive A after the ashing treatment is shown in FIG. The emission spectrum was composed of three emission bands having peaks at 420 ± 5 nm, 490 ± 5 nm, and 580 ± 5 nm, and the optimum excitation wavelength of each emission band was 250 ± 5 nm.

  Table 1 shows the intensity ratio of the three emission bands of the additive A before the ashing treatment, and Table 2 shows the intensity ratio of the three emission bands of the additive A after the ashing treatment. The intensity ratios of the three emission bands are both represented by three digits of 046, and the identification number of the additive A before the ashing treatment and the identification number of the additive A after the ashing treatment are the same. From this, it was shown that the present invention can be used as a food additive in which an identification number is recorded.

(Example 2)
Addition of the intensity ratio of three emission bands having peaks at 420 ± 5 nm, 490 ± 5 nm, and 580 ± 5 nm according to the above-mentioned production method using shellfish powder added with 1% ammonium chloride as the first additive A food additive having an intensity ratio indicated by the identification number 316 of the object B was prepared, and the fluorescence intensity ratio was measured while irradiating excitation light according to the above-described physical property measurement. The optimum excitation wavelength for each emission band was about 250 nm.

Next, the results when the identification number 316 thus prepared and the recorded additive B are added to food (in this example, rice flour (manufactured by B company) is used) are shown.
Here, the same ashing treatment was performed for the reason described in Example 1. The fluorescence intensity ratio of the emission spectrum of the sample after ashing was measured while irradiating excitation light according to the physical property measurement of the present invention.

  The emission spectrum of the additive B before being added to food is shown in FIG. 3, and the emission spectrum of the invention product after ashing is shown in FIG. The emission spectrum was composed of three emission bands having peaks at 420 ± 5 nm, 490 ± 5 nm, and 580 ± 5 nm, and the optimum excitation wavelength of each emission band was 250 ± 5 nm.

  Table 1 shows the intensity ratio of the three emission bands of the additive B before the ashing treatment, and Table 2 shows the intensity ratio of the three emission bands of the additive B after the ashing treatment. Since the intensity ratios of the three emission bands are both represented by three digits 316, and the identification number of the additive B before the ashing treatment matches the identification number of the additive B after the ashing treatment, the present invention is distinguished. It was shown that it could be used as a food additive with a recorded number.

(Example 3)
Using shellfish powder containing 2% calcium chloride as the first additive, 10 ppm copper chloride and 10 ppm manganese chloride as the second additive, and adjusting to 420 ± 5 nm, 490 ± 5 nm, and 580 ± 5 nm in accordance with the manufacturing method described above. A food additive was prepared so that the intensity ratio of the three emission bands having peaks was the intensity ratio indicated by the identification number 523 of additive C in Table 1, and the fluorescence intensity was applied while irradiating the excitation light according to the physical property measurement described above. The ratio was measured. The optimum excitation wavelength for each emission band was about 250 nm.

  Next, using the identification number 523 produced in this way and the recorded additive C, the result when added to food (in this example, rice flour (made by Company C)) was used in the same manner as in Example 1. Show. Here, the same ashing treatment was performed for the reason described in Example 1. The fluorescence intensity ratio of the emission spectrum of the sample after ashing was measured while irradiating excitation light according to the physical property measurement of the present invention.

  The emission spectrum of the additive C before being added to food is shown in FIG. 5, and the emission spectrum of the invention product after the ashing treatment is shown in FIG. The emission spectrum was composed of three emission bands having peaks at 420 ± 5 nm, 490 ± 5 nm, and 580 ± 5 nm, and the optimum excitation wavelength of each emission band was 250 ± 5 nm.

  Table 1 shows the intensity ratio of the three emission bands of the additive C before the ashing treatment, and Table 2 shows the intensity ratio of the three emission bands of the additive C after the ashing treatment. Since the intensity ratios of the three emission bands are both displayed as three digits 523, and the identification number of the additive C before the ashing treatment matches the identification number of the additive C after the ashing treatment, the present invention is distinguished. It was shown that it could be used as a food additive with a recorded number.

Example 4
Using shellfish powder containing 3% sodium chloride as the first additive, 10 ppm copper chloride and 10 ppm manganese chloride as the second additive, and adjusting to 420 ± 5 nm, 490 ± 5 nm, and 580 ± 5 nm according to the manufacturing method described above. A food additive is prepared such that the intensity ratio of the three emission bands having peaks is the intensity ratio indicated by the identification number 163 of additive D in Table 1, and the fluorescence intensity is applied while irradiating the excitation light according to the physical property measurement described above. The ratio was measured. The optimum excitation wavelength for each emission band was about 250 nm.

Next, using the identification number 163 thus prepared and the recorded additive D, the result when added to food (in this example, rice flour (made by D company)) was added as in Example 1. Show.
Here, the same ashing treatment was performed for the reason described in Example 1. The fluorescence intensity ratio of the emission spectrum of the sample after ashing was measured while irradiating excitation light according to the physical property measurement of the present invention.

  The emission spectrum of the additive D before being added to the food is shown in FIG. 7, and the emission spectrum of the invention product after the ashing treatment is shown in FIG. The emission spectrum was composed of three emission bands having peaks at 420 ± 5 nm, 490 ± 5 nm, and 580 ± 5 nm, and the optimum excitation wavelength of each emission band was 250 ± 5 nm.

  Table 1 shows the intensity ratio of the three emission bands of the additive D before the ashing treatment, and Table 2 shows the intensity ratio of the three emission bands of the additive D after the ashing treatment. The intensity ratios of the three emission bands are both displayed as three digits 163, and the identification number of the additive D before the ashing treatment matches the identification number of the additive D after the ashing treatment. It was shown that it could be used as a food additive with a recorded number.

  Although the general rice flour was used in Examples 1-4, it is not limited to this, and it goes without saying that it can be used for identification of other foods. In other words, when the food material is subjected to processing such as pulverization or is heated, the original figure is lost, and the product according to the present invention with a different identification number is added to the food material. .

It can be easily understood that it can be applied to pharmaceuticals and feeds. In fact, even when applied to pharmaceuticals and feeds, it was possible to easily identify them by following the steps of the above-described embodiment.
In the above embodiment, NH ₄ Cl, CaCl ₂ , and NaCl are added so that the concentration is 1% to 3%. It could be confirmed. Therefore, this invention includes these.

  The present invention belongs to existing additives in the classification of food additives, and has the function of being able to easily identify foods when added to foods, with calcium fortification and quality improvement being made. . That is, the focus is on calcined shell powder, which has heretofore been mainly aimed at enhancing calcium and improving the quality of food, and further proposes a food additive having an unprecedented function of identifying food. Thereby, for example, the identification becomes possible by adding the additive of the present invention to a food that has been crushed and whose shape (form) is not known.

  Moreover, it can be applied not only to the above-mentioned foods but also to pharmaceuticals and feeds, and it focuses on calcined shell powders that were mainly aimed at enhancing calcium and improving the quality of foods. It proposes functional medicines and feed additives. Thereby, for example, the identification can be performed by adding the additive of the present invention to a pharmaceutical or feed that has been crushed and whose shape (shape) is not known.

  As an example of industrial use of the product of the present invention, for example, by adding the product of the present invention to food, medicine or feed, it can be used as a mark for certifying the company's product. It becomes possible to protect from damage. In addition, by adding the product of the present invention to food, medicine, or feed, it can be used as a mark for proving the production lot number assigned to products with different production dates.

  Furthermore, by adding the product of the present invention to food, medicine or feed, the identification number of the added product of the present invention is added to the quality assurance certificate describing the origin of the material used in the product, the inspection method and the inspection result, etc. By writing together, it can be used as a mark to prove the identity of the product and the quality assurance certificate.

  With the recent increase in consumer awareness of food safety and security, the products of the present invention are highly likely to be used industrially for the above-mentioned purposes. Furthermore, the present invention is an unprecedented new invention that effectively utilizes low-utility shells that remain after eating scallops as a material for high-value-added products. The uplift is believed to boost the industrial applicability of the present invention.

Claims (16)

  Labeling for food, medicine or feed, which is an additive for powdered food, medicine or feed mainly composed of calcium carbonate obtained from shells, and which emits light when excitation energy is added to it. Additive   2. A labeled additive according to claim 1, wherein the emission spectrum consists of one or more emission bands.   The labeled wavelength according to any one of claims 1 and 2, wherein the peak wavelength of the emission band is any one or more of 420 ± 5 nm, 490 ± 5 nm, and 580 ± 5 nm. Additive.   4. The labeled additive according to claim 3, wherein the optimum excitation wavelength for each emission band is 250 ± 5 nm. One or more kinds selected from ammonium chloride (NH ₄ Cl), calcium chloride (CaCl ₂ ), and sodium chloride (NaCl) are added to a powder containing calcium carbonate as a main component obtained from a shell, and an emission spectrum of The labeled additive according to any one of claims 1 to 4, wherein the intensity ratio of the luminescent band is changed. One or two kinds selected from copper chloride (CuCl ₂ ) and manganese chloride (MnCl ₂ ) are added to the powder mainly composed of calcium carbonate obtained from the shell, and the intensity ratio of the emission band of the emission spectrum is changed. The labeled additive according to claim 5.   The labeled additive according to claim 1, wherein a scallop shell is used.   Labeled additive according to any one of the preceding claims, characterized in that it is a mixture of a plurality of powders with different emission band intensity ratios.   The labeled additive which mixed 2 or more types of the labeled additive as described in any one of Claims 1-8, and changed the intensity ratio of the emission band of the emission spectrum. After washing the unfired shells, the organic substrate is carbonized and incinerated by primary heat treatment in the range of 400 ° C to 600 ° C in the atmosphere, and then the shells cooled to near room temperature are pulverized, and then 800 ° C in a CO ₂ atmosphere. A food or medicine mainly composed of calcium carbonate obtained from shells characterized in that it is subjected to secondary heat treatment at ˜900 ° C. and given an identification number from the intensity ratio of emission bands of the emission spectrum of shell powder obtained thereby. Or the manufacturing method of the labeled additive for feed. One or more additives selected from ammonium chloride (NH ₄ Cl), calcium chloride (CaCl ₂ ), and sodium chloride (NaCl) are added to the shell powder subjected to the primary heat treatment, and the intensity of the emission band of the emission spectrum. The method for producing a labeled additive according to claim 10, wherein the ratio is changed. NH ₄ Cl, upon the addition of CaCl _2, or NaCl, previously given concentration _NH 4 of Cl, along with making a CaCl ₂ and NaCl solution, _NH 4 Cl by weight of the shell powder subjected to the primary heat treatment, the method according to claim 11 labeled additive according to one or more kinds of concentrations were selected from CaCl _2, NaCl is characterized by adding to a 0.3% to 3%. One or two additives selected from copper chloride (CuCl ₂ ) and manganese chloride (MnCl ₂ ) are added to the shell powder subjected to the primary heat treatment, and the intensity ratio of the emission band of the emission spectrum is changed. 13. A method for producing a labeled additive according to claim 11 or 12. Upon addition of CuCl ₂ or MnCl _2, advance a predetermined concentration with making CuCl ₂ and or MnCl ₂ aqueous solution, the concentration of CuCl ₂ and or MnCl ₂ relative to the weight of the shell powder subjected to the primary heat treatment 1ppm~ 14. The method for producing a labeled additive according to claim 13, wherein the additive is added so as to be 100 ppm.   The labeled additive according to any one of claims 1 to 9 is added to food, medicine or feed, both of which are incinerated at 500 ° C to 600 ° C, and then the sample after incineration is performed. A method for identifying food, medicine, or feed, characterized in that it is identified by an intensity ratio of emission bands of an emission spectrum.   After the labeled additive obtained by the production method according to any one of claims 10 to 14 is added to food, medicine or feed, and both of these are incinerated at 500C to 600C, A method for identifying food, medicine, or feed, characterized by identifying the intensity ratio of the emission band of the emission spectrum of the sample after ashing.