JP2002069051A - Method for producing solution of methionine-zinc complex - Google Patents

Abstract

PROBLEM TO BE SOLVED: To process a composition comprising a methionine-zinc complex and an amino acid so as to provide an easy-to-use shape when using the composition as a catalyst or a biochemical catalyst in various kinds of industry such as agriculture, forestry and fishing. SOLUTION: The solution of the methionine-zinc complex in the very easy- to-use shape is produced by heating 1 mol 4-8C higher amino acid and 1-5 mol 2-3C lower amino acid in water or a polyol to provide a solution, bringing the methionine into contact with a zinc salt in the resultant solution, and making the resultant mixture a homogeneous solution to produce the objective solution of the methionine-zinc complex in the very easy-to-use shape.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a methionine zinc complex solution useful as a catalyst or a biochemical catalyst. The methionine zinc complex solution of the present invention has particularly wide applications among methionine derivatives, and is also useful as a biochemical catalyst. That is, a therapeutic agent for zinc (mineral) deficiency, a liver function protecting agent, a diabetes preventing agent, a cataract preventing agent, a growth promoting agent, a feed additive,
It can be used as a flower activator, aquatic plant activator, and the like. In addition, the methionine zinc complex solution can be dehydrated and desolventized to form crystals or powder of the methionine zinc complex in some cases.

[0002]

2. Description of the Related Art Compounds containing methionine and zinc include a sparingly soluble double salt of methionine methylsulfonium chloride and zinc chloride, a methionine zinc normal salt formed at low temperature from an aqueous methionine alkali salt solution and zinc chloride, There is a methionine zinc chelate made by reacting methionine and zinc acetate in water. Each of these compounds has unique properties and taste. For example, the above methionine methylsulfonium chloride zinc chloride double salt is a strong salty powder having no odor peculiar to methionine sulfonium salt, methionine zinc normal salt is a crystal having a metallic salty taste, and a methionine zinc chelate complex Is a relatively pale salty and metallic astringent, poorly water soluble white crystal. The present inventors have already conducted detailed research on methionine derivatives of alkaline earth metals and transition metals, but have further studied and finally completed the present invention.

[0003]

Among the zinc methionine derivatives, a compound which is relatively stable in chemical or biochemical properties is a chelate complex, but this compound is hardly soluble in water and has a relatively low melting point. Since it was found by the present inventors to be high, it was difficult to adapt it to various uses without using a pure compound. The present inventors have focused on research to solve the difficulties of such a methionine zinc chelate complex, finally found a solvent necessary for utilizing it, and found that it can be produced at low cost by the method of the present invention. Revealed.

[0004]

Means for Solving the Problems That is, the present inventors have:
In a solvent obtained by heating 1 mol of a higher amino acid having 4 to 8 carbon atoms and 1 to 5 mol of a lower amino acid having 2 to 3 carbon atoms in water or (and) a polyol. It has been found that when a uniform solution is prepared by contacting methionine with a zinc salt, a methionine zinc complex solution is advantageously obtained. After the methionine is brought into contact with the zinc salt, if necessary, the methionine zinc complex solution containing little or no acid is obtained by further passing through a membrane or layer for deoxidation, or by deoxidizing under reduced pressure. It was found that it could be obtained.

[0005] The zinc salt used in the present invention is zinc formate,
Zinc acetate, zinc propionate, zinc carbonate, zinc chloride, zinc nitrate, and at least one compound selected from the group consisting of zinc sulfate. Among these, for example, zinc sulfate is a food additive, and zinc carbonate Is a white powder easily obtained from zinc sulfate and sodium carbonate.

[0006] Higher amino acids having 4 to 8 carbon atoms include aminobutyric acid, aminoisobutyric acid, valine, norvaline, leucine, norleucine, isoleucine, threonine, methionine, phenylalanine, lysine, arginine, ornithine, titrulline, proline, It is at least one amino acid (D, L-form, L-form, D-form) selected from oxyproline, aspartic acid, glutamic acid, oxyglutamic acid, asparagine, and glutamine, and industrially important amino acids are glutamic acid and lysine. ,
Aspartic acid, asparagine and the like. The presence of such higher amino acids in the amino acid mixture, umami as an additive of the methionine zinc complex solution of the present invention,
It enhances the expression of sweetness and nutritional value.

[0007] The lower amino acid having 2 to 3 carbon atoms means at least one amino acid (D, L-form, L-form) selected from glycine, α-alanine, β-alanine, sarcosine, serine and taurine. And D-forms), all of which are well known as industrially important lower amino acids.

1 mole of higher amino acid, 1-5 lower amino acids
Heating the moles in water or (and) polyol means performing the following operation. In the laboratory, for example, 150 g (2 mol) of glycine, 14 g of L-glutamic acid were placed in a flask equipped with a reflux condenser and a stirrer.
7 g (1 mol) and 500-1000 ml of water
Stir for about 20 hours and bring to a completely clear solution. 140-150 ° C in an autoclave under pressure, 3 ~
Even if the reaction is performed for 5 hours, a clear solution is obtained. Such an amino acid mixture is a transparent liquid having sourness and umami from amino acids, and has a pH of about 6 (test paper).
In this method, a polyol can be used instead of water. Examples of the polyol include ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, isoprene glycol, glycerin, triethylolpropane, trimethylolpropane, and pentaerythritol. These may be used by mixing with water. In addition, saccharides (eg, glucose, sucrose, fructose, etc.) can be used as the polyol component together with water.

[0009] In the above example, a mixture of 150 g of glycine, 147 g of L-glutamic acid and 500 ml of water is boiled for about 20 hours to form a clear liquid, but when a part of L-glutamic acid is replaced with D, L-methionine. , A clear liquid can be obtained by boiling for about 30 to 40 hours. Also, part of glycine is D, L-α-alanine, β
-When changing to alanine or the like, the boiling time does not need to be changed much, but when a part of glycine is changed to taurine, it is difficult to react, and boiling for a considerably long time is required. When using glycerin or saccharides as a polyol, dilute with a considerable amount of water and take care not to overheat and touch the air to prevent color decomposition and side reactions. It is necessary.

The ratio of the higher amino acid to the lower amino acid is selected from the range of 1: 1 to 5 (molar ratio), but industrially, it is desirable to increase the use ratio of the lower amino acid as much as possible. The solution containing the amino acid mixture thus obtained is a good solvent for the methionine derivative or the amino acid salt, and may be dissolved by 10% or more when heated. The main component of the methionine derivative referred to in the present invention is a methionine zinc chelate complex and contains almost no zinc divalent compound. The present inventors have already clarified that a concentrated amino acid mixture as shown in the present invention is required in order to uniformly dissolve a methionine zinc chelate complex. If the amount of the lower amino acid is out of the above range, it tends to be difficult to exert a sufficient dissolving power. The amino acid mixture of the present invention itself is a nutrient component for animals, and in some cases, improves palatability.

The amino acid mixture prepared as described above contains the following compounds, unlike a mere mixture of amino acids. That is, higher amino acid salts of lower amino acids, lower amino acid salts of lower amino acids, lower amino acid salts of higher amino acids, higher amino acid salts of higher amino acids, dipeptides, tripeptides, various amino acid monomers, hydrates of these (clathrates) Aqueous mixtures of amino acids, food additives in which the racemic forms of amino acids, dipeptides and tripeptides are intimately mixed and cause an extreme melting point drop, are conveniently made at -20 ° C. ~
It is mainly liquid between + 200 ° C and is also used for seasoning food soups. However, when this liquid is treated with alcohol, a precipitate precipitates, but it is not easy to completely determine the structure of the precipitate. However, the present inventors have recognized that this liquid is very effective for use as a mixed solution of amino acids and as a solvent for various organic substances or as a seasoning.

The methionine zinc complex solution obtained in the present invention is usually a transparent solution in a homogeneous state. For example, when methionine is brought into contact with an aqueous zinc sulfate solution,
The solution is sour due to sulfuric acid and salty due to the presence of amino acid sulfate, but umami is considerably strong due to the large amount of amino acids. Here, if acidity or saltiness due to sulfuric acid is disliked, an operation for removing sulfate ions is required.

[0013] For this purpose, it is sometimes preferable that the solution obtained by bringing methionine into contact with an aqueous solution of zinc sulfate (or an aqueous solution of an inorganic zinc acid) is passed through a deoxidizing film or a deoxidizing layer to remove sulfuric acid. . For deoxidation, an alkaline adsorbent layer (eg, basic activated alumina, basic activated silica,
(Barium hydroxide, calcium hydroxide, soda lime, kali lime) or a layer containing an ion-exchange resin to achieve its purpose. Sulfuric acid can also be removed. By using a membrane material developed today in the food industry and the polymer chemical industry, it is possible to industrially more advantageously remove acid components. If it is a volatile organic acid, it may be deoxidized under reduced pressure. The same applies to the deacidification when a zinc salt of a volatile acid other than zinc sulfate is used.

For example, it is used for the electrodialysis method used for the decitric acid of citrus juice, the electrodialysis method used for the detartaric acid from processed grape, the decitric acid and the demalic acid of the plum seasoning liquid. By applying the technology of the electrodialysis method to the present invention, only the acid component can be removed. Reverse osmosis filtration, microfiltration, ultrafiltration, and nanofiltration all use pressure as driving force. On the other hand, in the electrodialysis method, a potential difference is used as a driving force, and the function is performed using an anion exchange membrane, a cation exchange membrane, and a bipolar membrane according to functions.

As the anion exchange group of the hydrocarbon-based anion exchange membrane, one having a structure of a quaternary ammonium salt or a quaternary pyridium salt is used. Sulfonic acid type groups are used. Actually, deoxidation is performed in consideration of the electrical characteristics (electrical resistance, transport number, water movement) and physical properties (membrane strength, dimensional stability, surface condition) of commercially available electrodialysis membranes. Be done. When ions move through the membrane, they are usually hydrated, and the water of hydration moves with the ions. Such water is called electroosmotic water, the amount of which depends on the physical properties of the ion exchange membrane,
When the density of the membrane is low, the amount of electroosmotic water generally increases. In the case of the present invention, it is natural that an ion exchange membrane is appropriately selected and used so as to increase the yield of the amino acid mixture and the methionine zinc complex, and it is also desirable to perform electrodialysis economically.

It is convenient to design a general method for preparing a methionine zinc complex solution in anticipation that the zinc content is, for example, Zn = 1%. Here is an example. Glycine 150 g (2 mol), L-glutamic acid 147 g (1 mol) and water 5
00 ml is stirred and maintained at 100 ° C. for 20 hours to prepare a clear amino acid mixture (about 37.3% amino acid).
300 ml of this amino acid mixture, D, L-methionine 45
g (0.3 mol) and 500 ml of water,
Heat to 90 ° C to form a clear solution, which contains zinc sulfate 1
150 ml of a molar solution (161.4 g of zinc sulfate dissolved in 1 liter of water) is added, the mixture is kept at 70 to 80 ° C. for 10 minutes, and then placed in a 1 liter plastic bottle and allowed to cool. This solution contains 9.8 g of zinc, and the solution 10
The zinc content in 0 ml was analyzed to be 1.14 g. This is in line with expectations of about 1% (10000 ppm). This solution is not desulfated, but can be desulfated by electrodialysis if necessary. When this is dispersed in a compound feed having a weight of about 200 times, feed containing 50 ppm of zinc for animals (for insects, birds, livestock, etc.) or for marine animals (for crustaceans, shellfish, fish, etc.) Become feed.

The present inventors have conducted a number of experiments on the method as described above to clarify the superiority of the present invention. However, in order to further explain the technical contents of the present invention, typical examples have been described. Some examples are extracted and shown below as examples. Therefore, the method of the present invention should not be construed as being limited to only the examples described below, but may be arbitrarily modified in the embodiments without departing from the spirit and the spirit of the present invention. Of course, what can be done.

[0018]

Example 1 150 g (2 mol) of glycine, 147 g (1 mol) of L-glutamic acid and 500 ml of water were stirred in a flask equipped with a reflux condenser and kept at 100 ° C. for 20 hours to produce a transparent amino acid mixture. Keep it. 300 ml of this amino acid mixture, 45 g (0.3 mol) of L-methionine and 500 ml of water were mixed and heated to 90 ° C., and a 1 mol solution of zinc sulfate (161.4 g of zinc sulfate) was added thereto.
Was dissolved in 1 liter of water) and 150 ml was added to the mixture at 80 ° C.
After contact for 10 minutes, put in a plastic bottle and allow to cool. This solution contained 9.8 g of zinc, and the zinc analysis value was 1.05 to 1.10%.
When it is desired to form a zinc chelate complex crystal from this solution, the resulting solution is poured into a 10-fold amount of anhydrous alcohol and cooled to obtain a white plate-like crystal of zinc L-methionine complex (melting point 270 to 272). ° C, decomposition) in a yield of 82%. The analysis results of the dried product are as follows. Calculated value as composition formula C ₁₀ H ₂₀ N ₂ O ₄ S ₂ Zn: C: 33.20%, H: 5.57%, N: 7.
74%, Zn: 18.07% Measurement value C: 32.85%, H: 5.50%, N: 7.
62%, Zn: 17.95%

A mixture prepared by mixing and mixing 500 g of the above L-methionine zinc complex solution with 100 kg of a mixture of 50% fish meal, 15% soybean oil cake, 15% beer yeast, 10% meat bone meal and 10% corn gluten meal. Then, water in which a small amount of guar gum is dissolved as a binder is added and further mixed, and a pellet for fish feed is prepared by a pelletizer. This pellet contains roughly 45% crude protein,
It contains about 15% crude fat, about 10% ash, about 5% braided fiber, and about 5% carbohydrates. This is a general-purpose soft dry pellet for yellowtail, which is used for marine aquaculture and has a large thickness increasing effect, and improves poor growth caused by methionine deficiency.

[0020]

Example 2 Zinc acetate Z in place of zinc sulfate of Example 1
1 mol of n (OCOCH ₃ ) ₂ .2H ₂ O (219.5)
When 150 ml of a hot aqueous solution containing g) is added and kept at 100 ° C. for a while, a homogeneous solution containing 1% of zinc is obtained. However, since the acetic acid smell of this solution is considerably strong, the solution is concentrated under reduced pressure on a hot water bath until the crystals do not precipitate, and deoxidized. However, if this concentration is carried out until crystals precipitate, and it is separated,
L-methionine zinc complex (calculated value of Zn 18.07%,
Although a measured value of Zn of 18.02%, a melting point of 270 to 272 ° C., and decomposition can be obtained, it is convenient to use the deoxidized liquid as it is without depositing crystals in consideration of the subsequent use.

The liquid of the above-described deoxidized vacuum concentrate is diluted with a 10-fold amount of water to obtain an insect breeding mat additive. That is, 50 parts of white chips obtained by inoculating oyster mushrooms on chip wood of Kunugi and 50 parts of chip powder of waste wood of Shiitake mushroom wood are mixed, and the above deoxidized liquid is increased by 10 times. After spraying 30 to 40 parts of the diluted solution, further mixing and sterilizing the mixture, the mixture is placed in a 1-liter wide-mouth plastic bottle for bacterial cells, pressed with a pestle and packed so as to form a relatively firm bacterial bed. When the upper mouth of the bottle was slightly pushed down and dented, the second instar larvae of the stag beetle (Volks cruvidens) were set one by one in a bottle, covered with a fine mesh lid, and placed in a humid dark room. Breed. The breeding temperature is about 25 ° C in summer, about 10-13 ° C (hibernation temperature) between October and March, and kept at 20-25 ° C after April. Large stag beetles, when they are third instar larvae, are greatly ingested and enlarged. By the end of the year, carefully replace the plastic bottle twice with a new one so that you can obtain a giant larva (the larva tends to temporarily shrink after replacing the bottle with a new one, Soon bloated).
The terminal larva pupates several days later (approximately 3 weeks) and evolves after another 3 weeks (the contact is absolutely impossible for about 1 month after the emergence because the body is not solidified). The size of the large stag beetle and the degree of branching of the jaw depend on the nutritional status of the terminal larva and the presence or absence of any external stimulus or vibration during pupation and emergence. Care should be taken to minimize environmental impact. Those bred in this manner, when using a breeding mat containing zinc, 75-78 mm for males,
In the case of female worms, the size was 45 to 48 mm, which was much better than the case where a breeding mat containing no zinc was used.

[0022]

Example 3 150 g (2 mol) of glycine, 294 g (2 mol) of L-glutamic acid and 1 l of water were kept at 150 ° C. for 3 hours while stirring in an autoclave to prepare a transparent amino acid mixture (n _D ²⁵ 1.380). Make it. 300 ml of this mixed amino acid mixture, 45 g of D, L-methionine
(0.3 mol) and 500 ml of water were mixed, and 19 g (0.15 mol) of zinc carbonate was added thereto. The mixture was maintained at 100 ° C. for 2 hours while being vigorously stirred, and insoluble materials were filtered off. The zinc content in the filtrate is about 1%) and collected as a feed additive. The content of feed for laying hens in Japan is for spring and autumn, for summer,
Although slightly different from winter use, zinc content as mineral is 100
The addition amount is 40 mg per g, and the above-mentioned filtrate is significantly used. In addition, according to the Japanese Housing Standards (1984, 1987) of the Agriculture, Forestry and Fisheries Technology Council, the required amount of minerals for livestock (mg) and the poisoning level (mg) of zinc in 1 kg of feed (dry matter) Are 30 and 500 for beef cattle, 40 and 500 for dairy cows, respectively.
50-100 and 2000 for pigs, 30-65 for chickens
And 1500. In these cases, the use of the methionine zinc complex solution as the corresponding zinc component was very effective, and the additive component was superior to other compounds.

[0023]

Example 4 150 g (2 mol) of glycine, 75 g (0.5 mol) of D, L-methionine, 74 L-glutamic acid
g (0.5 mol) and 500 ml of water are stirred and maintained at 100 ° C. for 45 hours to give a clear amino acid mixture (about 3 amino acids).
7.4%). This amino acid mixture 300m
1,45 g (0.3 mol) of D, L-methionine and 500 ml of water were mixed and heated to 100 ° C. to obtain a transparent liquid, and 200 ml of a hot solution in which 20 g (0.15 mol) of zinc chloride was dissolved. And further warmed for 1 hour, then cooled and stored. When this solution is passed through a layer filled with soda lime and dehydrochlorinated, about 1000 ml of an additive liquid (Zn content is about 1%) containing a zinc D, L-methionine complex is obtained.

In a juice mixer, 20 g of white fish meal, 10 g of soybean oil cake, 10 g of gluten meal,
5 g sucrose, 5 g seaweed powder, 5 g egg yolk powder, 5 casein
g, 5 g of liver oil and 10 g of the above-mentioned additive solution were mixed vigorously to prepare a fine powder feed, and a breeding test of prawns was performed. Kuruma prawns (Pinaeus japonics) were used during the early mitosis period, and were fed with a fine powder feed of 125 μm in size until they changed to benthic organisms during the post-larva period.
They were dosed twice a day in the morning and evening at a dose of about mg / tail / time and reared for about 2 weeks. The results showed that the survival rate was 98% or more.
A 12% increase was observed.

[0025]

Example 5 Fish meal 30%, soybean oil cake 25%, corn gluten meal 11%, potato starch 9%, mineral mixture powder (Ca, P, K, Na, Mg, Fe, Mn, Cr,
Co, Cu-containing 2%, vitamin mixture (A, B)
_{1, B 6, B 12,} C, E, those containing K) 3%, liver 15
% Extruder pellets (about 45% crude protein, about 20% crude fat, about 15% crude sugar, about 10% crude ash, and about 10% moisture) containing the As a result of feeding 35 g of juvenile red sea bream (Pagulus majo) once a day for three months and rearing it, the rate of increase in the thickness of the fish reached 240%. When preparing this extruder pellet, 5 parts of the additive liquid containing the D, L-methionine zinc complex (Zn content: about 1%) shown in Example 4 was used.
When a breeding test was performed using pellets obtained by adding the amount in%, the rate of meat increase reached 260%, and the excellence was obvious.

[0026]

Embodiment 6 The additive liquid containing the zinc D, L-methionine complex shown in Example 4 and added with guar gum or sodium alginate of several percent or less to increase the viscosity stimulates the smell and taste of saltwater fish. However, extruder pellets made with this were suitable for aquaculture feed for hamachi and yellowtail (Seriola quinquela deiata). Furthermore, for example, beer yeast 60%, soybean oil cake 1
0%, corn gluten meal 10%, wheat flour 5%, rice bran 5%, amino acid mixture 5 containing the above methionine zinc complex 5
% And guar gum 5% can be widely used for the culture of salmonid trout (Oncorinx maso). It was found that the effect of the zinc complex activates fish movement and contributes to the growth promoter of fish and the prevention of cataract.

[0027]

Example 7 D, L-α-alanine 180 g (2 mol), L-glutamic acid 74 g (0.5 mol), D, L
-Methionine 45 g (0.5 mol), D, L-lysine 1
4.6 g (0.1 mol) and 700 ml of water are stirred in a flask equipped with a reflux condenser for 40 hours at 100 ° C.
To make a clear amino acid mixture. 300 ml of this amino acid mixture, 45 g of D, L-methionine (0.3
Mol) and 400 ml of water, and the mixture was kept at 100 ° C., and a hot aqueous solution containing 34 g (0.3 mol) of zinc chloride was added thereto, followed by cooling. This solution contains about 1% zinc
include. When anhydrous methanol is added to the aqueous solution and the mixture is cooled, white plate-like crystals of D, L-methionine zinc complex (melting point: 269 to 270 ° C, decomposition) are obtained in a yield of about 85%. The analysis result of the dried product is as follows. Calculated value as composition formula C ₁₀ H ₂₀ N ₂ O ₄ S ₂ Zn: C: 33.20%, H: 5.57%, N: 7.
74%, Zn: 18.07% Measurement value C: 33.10%, H: 5.60%, N: 7.
65%, Zn: 17.97%

The amino acid mixture containing the D, L-methionine zinc complex obtained above is diluted 100-fold with water to prepare a seaweed dipping solution containing 0.01% zinc. The freshly collected alame is bundled and immersed at 15 to 16 ° C for 5 to 6 hours. The immersed seaweed feed is bundled into a suitable size (about 1 kg), placed in a plastic basket having an internal volume of 18 liters, and then a black abalone (Hariotis discus) larva (having a shell diameter of about 3 cm) is prepared. After about 30 shells were attached to a plastic film, they were transferred into a basket, the lid was closed, a slight drop was applied, and then a depth of about 10 m (15 to 19 ° C) below the sea surface with tidal currents Hang it on. The alame in the cage is replaced every two days with a new one soaked in the seaweed soaking solution, and the black abalone is bred for six months. In this method, larvae become 6 to 8 cm in one year, and the growth rate is 1.5 to 2.0 times larger than when only ordinary larvae, scallops or wakame are used as feed, and the immersion effect of seaweed feed Was clearly shown.

[0029]

Example 8 180 g (2 mol) of β-alanine, 75 g (1 mol) of glycine, 74 g (0.5 mol) of L-glutamic acid
Mol) and 500 ml of water are stirred and boiled in a flask equipped with a reflux condenser for 20 hours to prepare an amino acid mixture. 300 ml of this amino acid mixture, 45 g (0.3 mol) of D, L-methionine and 300 ml of water were mixed to give 1
100 ° C., and 99 g of zinc nitrate hexahydrate (0.3 g
Mol) is added with a hot aqueous solution containing
Those diluted to 1 to 0.001% can be used for the propagation of zooplankton, and this seawater is used for cultivation of Gokai (Ninenses Japonica) and Isogokai (Perinereis Nuncia).

[0030]

Example 9 150 g (2 mol) of glycine, 89 g (1 mol) of sarcosine, 120 g of D, L-threonine (0.
1 mol) and 500 ml of water, and the mixture is stirred and boiled for 15 hours to form a homogeneous aqueous solution. This amino acid mixture 300m
l, D, L-methionine (45 g, 0.3 mol) and water (500 ml) were mixed and heated to 90 ° C., to which zinc chloride (20 g, 0.15 mol) and zinc carbonate (19 g) were added.
(0.15 mol) of the mixed fine powder, and the mixture was stirred vigorously, and the reaction solution was filtered to obtain a uniform transparent filtrate. The transparent filtrate was heated to 60 ° C., and 2 g of guar gum and 2 g of ammonium alginate were added thereto and stirred with a homogenizer. The mixture was useful as a binder and a palatability improver for a general powdered feed mixture for fish. It is.

[0031]

[Embodiment 10] The method for producing a methionine zinc complex solution and the method for using the solution have been described above. However, a methionine transition metal complex other than zinc may be required in some cases due to its properties as a feed additive. Commonly used transition metals are copper,
Cobalt and manganese are often used in combination with a methionine zinc complex as a methionine complex. Next, a method for producing a complex solution containing copper which is shared with zinc will be described.
Glycine 75 g (1.0 mol), L-glutamic acid 74
g (0.5 mol) and 500 ml of water are boiled for 25 hours to form a transparent amino acid mixture. This amino acid mixture 100m
l, 15 g (0.1 mol) of D, L-methionine was added and dissolved by heating, and zinc acetate Zn (OCOCH ₃ ) ₂ was added thereto.
· 2H ₂ O 9 g copper acetate _{Cu (OCOCH 3) 2 · H} 2 O
If 1 g of the mixed hot aqueous solution is added, stirred and then cooled, about 1
A methionine zinc complex solution containing 0% copper is obtained. In the living body, copper antagonizes zinc, so the effect of zinc as a growth promoter is somewhat reduced.However, as a crustacean feed additive always suffering from a shortage of copper, the above-mentioned zinc methionine zinc is used as an additive. Complex solutions are useful. In particular, a chelating agent containing a small amount of copper is very effective for the color development of shrimp after cooking. In addition, when a methionine zinc complex solution and inositol are used in combination as feed additives for crustaceans, growth and molting are accelerated.

[0032]

Industrial Applicability The methionine zinc complex solution of the present invention is widely used as a catalyst or a biochemical catalyst. Particularly, a therapeutic agent for zinc (mineral) deficiency, a therapeutic agent for liver function, a preventive agent for diabetes, a preventive agent for cataract, It can be used as a growth promoter, feed additive, flower activator, aqueous plant activator, and the like. Therefore, it is believed that the present invention will greatly contribute to the feed industry, the agriculture, forestry and fisheries industry, the food industry, the biochemical industry, and the like.

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) // A23K 1/16 301 A23K 1/16 301F A61K 31/315 A61K 31/315 A61P 3/00 A61P 3/00 (72 ) Inventor Mitsuhiko Sano 3-2-28 Atago-cho, Uwajima-shi, Ehime (72) Inventor Masahiro Matsuda 149-38, Nakatsu, Kakogawa-cho, Kakogawa-shi, Hyogo (72) Inventor Masayuki Takada Nakagane Buddha Town 211 Nuver Heights 502 F-term (Reference) 2B150 DA06 DA32 DA44 DA49 DA76 DH09 4C206 AA03 JA27 JB02 MA04 NA03 ZA33 ZA75 ZC21 ZC35 ZC61 4H006 AA01 AA03 AB06 AB10 AB20 AC90 AD19 BB14 BB19 BB31 BC01 BC03 BC06 CA03 CB11 CD03 DA13 DC05 4H048 AA02 AA03 AB06 AB10 AB20 AC90 AD19 BB14 BB19 BB31 BC14 BC52 BE62 BE90 VA20 VA30 VA40 VA66 VB10

Claims (3)

[Claims] 1 mole of a higher amino acid having 4 to 8 carbon atoms and 1 mole of a lower amino acid having 2 to 3 carbon atoms.
A method for producing a methionine zinc complex solution, comprising contacting methionine with a zinc salt in a solution obtained by heating 5 mol of methionine in water or (and) a polyol, and then forming a uniform solution. 2. The zinc methionine complex according to claim 1, wherein the zinc salt is at least one compound selected from the group consisting of zinc formate, zinc acetate, zinc propionate, zinc carbonate, zinc chloride, zinc nitrate and zinc sulfate. The method of producing the solution. 3. The method for producing a methionine zinc complex solution according to claim 1, wherein after the methionine is brought into contact with the zinc salt, the methionine is further passed through a membrane or layer for deacidification or deoxidized under reduced pressure.