JP2001231461A - Feed additive for fishes and shellfish and feed for fishes and shellfishes containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a feed additive for fishes and shellfishes capable of solving many problem such as water pollution in crawl culture, frequent occurrence of fish diseases and adhesion of malodor and feed for fishes and shellfishes mainly composed of vegetable proteins and strengthened by using the above additive. SOLUTION: This feed additive for fishes and shellfishes comprises an amino acid salt or an amino acid condensate obtained by binding at least one alkaline earth metal ion selected from the group consisting of magnesium, calcium and zinc to a 2-11C amino acid or a condensation product of the above amino acid with glycine or alanine. This feed for fishes and shellfishes is obtained by compounding the feed additive with a vegetable protein.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a feed additive for fish and shellfish and a feed for fish and shellfish containing the same, wherein the feed additive for shellfish and shellfish according to the present invention is blended with a material mainly composed of vegetable protein. The resulting fish and shellfish feed can be supplied to the market in large quantities and easily.

[0002]

2. Description of the Related Art The present inventors have disclosed Japanese Patent Application Laid-Open No. 7-330503.
As disclosed in Japanese Patent Application Publication No. JP-A-2005-122, 1 to 25 parts by weight of a lower amino acid having 2 to 3 carbon atoms and a higher amino acid having 4 or more carbon atoms in a poorly water-soluble nonionic polymer matrix support A behavioral effect material for aquatic animals containing 1 part by weight of an amino acid mixture was announced, and then, as shown in Japanese Patent Application Laid-Open No. 9-121783, a microbial fermentation product of plant juice or a crushed product thereof was used. Amino acid A having 2 to 3 carbon atoms in a matrix material containing
And a higher amino acid B having 4 or more carbon atoms in a molar ratio of A / B = 1 to 40.

A method for producing good soybean oil cake as a feed for fish farming is disclosed in Japanese Patent Application Laid-Open No. 5-2688 / 1993.
No. 1 discloses that soybean oil cake contains microorganisms (molds, yeasts,
A method of removing small sugars (fish growth inhibitory factor) contained in the lees by the action of bonito koji) has been announced, and the soybean lees thus produced is used only for cultured fish (eg, hamachi). It is supposed to be feed.

[0004] Furthermore, proteins ingested by the animal are absorbed in the form of amino acids, dipeptides or tripeptides (generally called oligopeptides) in the animal, and are designated as feed additives in Japan. As peptide minerals (amino acid chelating minerals), four types of peptide iron, peptide manganese, peptide zinc and peptide copper are known, and these are also known as IFN No. 57,147, Metal Amino Acid C
registered under the name "hate".

[0005]

By the way, in order to use a vegetable protein as a feed for fish and shellfish, a sufficient study of the protein component is carried out, and a feed for fish and shellfish which can further enhance the deficient active ingredient is used. Must be developed, and the developed seafood feed additive and the seafood feed containing the same must be industrially manufactured, and must be able to be marketed in large quantities and easily.

More specifically, unlike terrestrial animals, simple feeds containing vegetable protein as a main component are often unsuitable for aquatic animals such as fish and shellfish. In the case where is used, it is used as a compound feed in which a considerable part thereof is replaced with animal protein. As animal protein, dried fish meal, raw fish meat and the like are mainly used. In such a case, these prices are always a problem, and in the case of fish cages, there is concern about water pollution and the occurrence of fish disease. Often has a negative effect on the sales of

The present inventors have developed a novel feed additive for fish and shellfish which can eliminate such disadvantages of the conventional compound feed as much as possible, and contain a vegetable protein fortified using the additive as a main component. The technical task is to provide a stable supply of fish and shellfish feed to the market.

[0008] The present inventors have proposed that an amino acid having 2 to 11 carbon atoms or a condensate of the amino acid and glycine or alanine is added to at least one alkaline earth selected from the group consisting of magnesium, calcium and zinc. In addition to finding feed additives for fish and shellfish containing amino acid salts or amino acid condensate salts to which metal ions are bound,
The technical problem has been achieved by clarifying the method of use and providing a feed for fish and shellfish in which this additive is blended with a material mainly composed of vegetable protein.

[0009]

The above technical objects can be achieved by the present invention as described below.

That is, according to the present invention, the number of carbon atoms is 2 to 1;
A feed additive for fish and shellfish comprising an amino acid salt in which at least one alkaline earth metal ion selected from the group consisting of magnesium, calcium and zinc is bound to one amino acid. 1).

The present invention also relates to a condensate of an amino acid having 2 to 11 carbon atoms with glycine or alanine, wherein at least one alkaline earth metal ion selected from the group consisting of magnesium, calcium and zinc is added. It is a feed additive for fish and shellfish characterized by containing a bound amino acid condensate salt (Claim 2).

Further, the present invention relates to an amino acid having 2 to 11 carbon atoms, wherein glycine, alanine, valine, leucine, isoleucine, serine, threonine, cysteine, taurine, methionine, aspartic acid, asparagine, glutamic acid, glutamine. And at least one compound selected from the group consisting of lysine, lysine, arginine, histidine, proline, hydroxyproline, phenylalanine, tyrosine, and tryptophan. Item 3).

[0013] Further, according to the present invention, the feed additive for fish and shellfish according to any one of claims 1 to 3 comprises guar gum (galactomannan), tara gum (galactomannan), locust bean gum (galactomannan), Macromolecules containing at least one D-mannan selected from the group consisting of Hemanbana mannan (glucomannan), konjac mannan (glucomannan), elegans mannan (glucomannan), zalepmannan (glucomannan) and microbial mannan It is a feed additive for fish and shellfish containing a paste (claim 4).

Further, the present invention is a feed for fish and shellfish, wherein the additive for feed for fish and shellfish according to any one of claims 1 to 4 is blended with a vegetable protein (claim 5).

The configuration of the present invention will be described in more detail together with the operation as follows.

First, the number of carbon atoms in the present invention is 2 to 1
One amino acid is glycine, alanine, valine,
At least one compound selected from the group consisting of leucine, isoleucine, serine, threonine, cysteine, taurine, methionine, aspartic acid, asparagine, glutamic acid, glutamine, lysine, arginine, histidine, proline, hydroxyproline, tyrosine, phenylalanine and tryptophan It is.

Most of such amino acids having 2 to 11 carbon atoms are naturally occurring L-forms, most of which are said to be essential amino acids, while those chemically synthesized are D-forms. , L-form (racemic form), for example, D, L
-Alanine, D, L-methionine, D, L-glutamic acid, D, L-tryptophan and the like. Also, L-body,
G-glycine, taurine,
β-alanine and the like. Such amino acids are glycine or alanine (α-L form, α-D form, racemic form and β form).
Condensates in the form of a condensation reaction with (-)) include oligopeptides, ie, dipeptides, tripeptides, tetrapeptides and the like.

Since cystine differs from other amino acids and has very poor reactivity and solubility, it is omitted from the amino acids of the present invention.

Next, vegetable proteins to which the present invention is applied include beans, seeds, sucrose, proteins separated from ground seed crushed powder, processed products of vegetable isolated proteins, fu, gluten meal, sake lees, and sake lees. At least one material selected from the group consisting of refuse, beer lees, yeast, powder of fermented foods, crushed frozen tofu, yuba or equivalents. Aerobic fermentation and converted to high protein material, with 20% protein content
It is preferable to use the above.

More specifically, practical vegetable proteins include defatting methods from beans, seeds, and sucrose.
It is manufactured through an extraction method, an oil pressing method, or the like, or manufactured by a fermentation method in which microorganisms act on plant juice residue or plant waste. These plant proteins contain water, lipids, carbohydrates (sugar, fiber, starch, pectin), and ash (inorganic) as components other than proteins. The protein content is 33-36% for whole-grain soybeans and 40-46% for defatted soybeans, and rapeseed oil cake (crude protein 30-35%), cottonseed oil cake (crude protein 35-45%), Linseed oil cake (crude protein 28 ~
35%) and copra meal (about 20% of crude protein). Fermentation products include sake lees (crude protein 12-15%) and dried yeast (crude protein 20-50%).

In the case of terrestrial animals, considerable growth can be expected by using these plant proteins as feeds. However, in the case of aquatic animals and shellfishes, only such plant protein feeds can be used in special cases. In addition to not being able to expect sufficient growth, the behavior of eating seafood also slows down,
Eventually, these also cause water pollution and fish disease.

Conventionally, animal protein feed has been mainly used in the aquaculture industry, and it has often been attempted to substitute a part of it with vegetable protein feed.
Substitution of animal protein with plant protein is limited to a level that does not adversely affect the growth of fish and shellfish, and is usually about 20% or less. In addition, the effect may be influenced by the fish species, the season, the water quality, and the water temperature. The present inventors have conducted various studies to overcome such difficulties, and as a result, have finally completed the present invention.

It has been clarified that plant proteins are significantly different from animal proteins in foods, and proposed by FAO (United Nations Food and Agriculture Organization) / WHO (United Nations World Health Organization) in 1965, 1973 and 1985. It seems to be good to think according to the amino acid score given. As a result, the amino acids lacking in plant proteins are firstly sulfur-containing amino acids (methionine, cysteine, taurine),
In addition, histidine, lysine, threonine, isoleucine, tryptophan, fanylalanine, tyrosine and the like are slightly insufficient. On the other hand, animal proteins contain essential amino acids including sulfur-containing amino acids, etc., whereas plant proteins are often nutritionally inferior, and feeds for fish and shellfish which require large amounts of animal proteins Is unsuitable as it is.

Therefore, the present inventors have proposed that the carbon atom has 2 to 1 carbon atoms.
A feed additive for fish and shellfish comprising an amino acid salt obtained by binding at least one alkaline earth metal ion selected from the group consisting of magnesium (Mg), calcium (Ca) and zinc (Zn) to one amino acid; Condensates of amino acids having 2 to 11 carbon atoms with glycine or alanine include magnesium (Mg), calcium (C
The present invention has developed a feed additive for fish and shellfish comprising an amino acid condensate salt having at least one alkaline earth metal ion selected from the group consisting of a) and zinc (Zn).

Although it is not easy to formally define a concept similar to valence that can be used uniformly throughout chemistry, it is generally possible to express the positive charge on a metal ion by the term valence, The coordination number can be represented by the number of nearest neighbors that are associated with the ion. Neutral salts, acidic salts, basic salts, peptide salts (double salts, complex salts, etc.) are formed in the salt in which at least one alkaline earth metal ion selected from the group consisting of magnesium, calcium and zinc is bound. Although it is possible, the easiness of crystallization from an aqueous solution generally tends to be in the order of Zn salt> Ca salt ≧ Mg salt, but generally, water-soluble one is important.

The alkaline earth metal salt of an amino acid or a condensate of the amino acid with glycine or alanine does not require that all of the contained amino acid or condensate form a salt. Preliminary experiments by the present inventors have shown that even when 5% to 50% of the salt is formed, it is preferred to seafood.

An α-amino acid having 2 to 11 carbon atoms [RCH (NH ₂ ) COOH] and glycine [H ₂ NC
H ₂ COOH] or α-alanine [CH ₃ CH (N
Examples of the condensate with (H ₂ ) COOH] are basically the following dipeptides (a) to (d), and then the same reaction is repeated to form the condensate as a tripeptide or tetrapeptide. It becomes an oligopeptide such as a peptide, and the manner of extension of the peptide chain varies depending on the type of reagents and raw materials, the synthesis method, reaction conditions, and the like.

(A) RCH (NH ₂ ) CONHCH ₂ C
OOH, (b) RCH (NHCOCH ₂ NH ₂ ) COO
H, (c) RCH (NH ₂ ) CONHCH (CH ₃ ) C
OOH, (d) RCH [NHCOCH (CH ₃₎ N
H _2] COOH.

(A) to (d) show the case where the reaction is carried out equimolarly by taking the product in the case of a single α-amino acid as an example. However, in practice, a mixed amino acid is used or each reacting reagent is used. Since the molar ratio is different, a complicated mixed reaction product is obtained. The cause of this will be described with reference to an example in which glycine reacts with an α-amino acid. NHCO formed by reacting α-amino acid NH ₂ with glycine COOH
With (A) bond, α-amino acid COOH and glycine N
CONH formed by reacting with H ₂ is converted to (C)
When 1 mol of α-amino acid and 1 mol of glycine react as a bond, if there is no side reaction, (A)
A compound containing four types of bonds (A), (A) (C), (C) (A), (C) and (C) is obtained.
When moles and 2 moles of glycine react, (A)
(A) (A), (A) (A) (C), (A) (C)
(A), (A) (C) (C), (C) (A) (A),
(C) (A) (C), (C) (C) (A), (C)
(C) A compound containing eight kinds of bonds of (C) is obtained. Of course, in the reactions in which these can be performed, side reactions such as racemization by thermal reaction, Walden inversion by catalytic reaction and cyclization by dehydration are not taken into consideration, and precipitation due to polypeptide formation is not taken into account. When the above-mentioned glycine is changed to α-alanine, the reaction product becomes an amino acid condensate (oligopeptide) which is a mixture of many compounds. The analysis of these reaction products is revealed by chromatograph-mass spectrum analysis, amino acid sequencer analysis and the like.

Therefore, when an equimolar condensate of the amino acids corresponding to (a) to (d) is to be synthesized with high synthetic chemistry, the reaction can be carried out by reacting a chloroacetylated amino acid with ammonia or by α By reaction of amino acid chlorides or α-amino acid esters with amino acids. These methods are useful when used for the synthesis of optically pure peptides.

The simplest industrial method for condensing amino acids is to react the starting amino acids in a suitable medium-boiling solvent to form a mixture as described above. As the medium boiling point solvent, water, a lower alcohol or a medium boiling point organic solvent is used. When a catalyst is used, it is advantageous to use a metal oxide, an ion-exchange resin, or a metal salt that facilitates separation of an unnecessary catalyst from the reaction mixture after the reaction.

The reaction without a catalyst has the widest application range and can be carried out at 80 to 200 ° C. with heating. For example, when heating two or more amino acids using water as a solvent, boiling in a relatively small amount of water for a long time,
The purpose is achieved by heating at 0-200 ° C. The amino acid condensate obtained by such a method becomes a mixture having a structure selected from (a) to (d), but there is no disadvantage in practical use.

When the animal component is a feed component, the main component that stimulates the olfaction of fish and shellfish is an animal extract, which can be broadly divided into amino acids, peptides, and other compounds (betaine, trimethylamine, Creatine, lipids, etc.), of which amino acids and oligopeptides are particularly important. On the other hand, it is carbohydrates that account for about 3/4 of the dry matter in the vegetable component,
Among these, the main component that stimulates the taste of fish and shellfish seems to be only sugars that show sweetness.

The present inventors' previous studies show that amino acids serve as attractant reactants. Eels are glycine and alanine, carp is alanine and lysine, and funa is isoleucine, arginine, lysine and asparagine. To glutamic acid, catfish to alanine, methionine, medaka to alanine, histidine, glycine, and valine, burdock to phenylalanine, gangam to proline, alanine, glycine, flounder to glycine, alanine, methionine, asparagine, glutamic acid, leucine, Red sea bream is glycine, leucine, isoleucine, valine, glutamine, methionine, alanine, and serine, locust is glycine, tocobushi is alanine, clams are valine,
Histidine reacts with leucine, abalone reacts with glutamine, arginine and phenylalanine, and thistle reacts with glutamine. In carrying out the present invention,
It is preferable that such an attraction reactant or a growth promoting substance such as methionine is contained in a feed as a feed additive for fish and shellfish in the form of the above-mentioned amino acid salt or amino acid condensate.

It is not easy to know what kind of smell and taste the amino acid or the alkaline earth metal salt of the amino acid exhibits for fish and shellfish, but for humans, the metal taste is slightly sweet. It exhibits astringent to bitter tastes based on the salty taste coming from ions, and particularly in the case of zinc salt, it is a taste in which a metallic taste is added to this astringent taste.

The alkaline earth metal magnesium (M
g), calcium (Ca) and zinc (Zn) ions are minerals necessary for the growth of fish and shellfish. In particular, zinc is often lacking in feeds. Is preferably blended in the additive.

Calcium, potassium, sodium and magnesium are essential components of the minerals required for growth of fish and shellfish, and iron, manganese, copper, zinc and molybdenum are minor components. is there. Among them, non-toxic or less toxic alkaline earth metal ions include Ca, Mg, Zn,
These all have the characteristic that they form a salt with the amino acid or amino acid condensate referred to in the present invention, and most of them are water-soluble or water-soluble. In addition, such an amino acid, an amino acid condensate, or a salt thereof forms a stable water-soluble molecular compound in water with a polymer material containing D-mannan, and gives a mucus, sol, or gel thereof.

Further, there is an advantage that a compound feed molded article or the like which is not separated from the feed body and is formed integrally can be processed into solid feed (crumb feed, pellet feed, floating feed) or kneaded feed of appropriate hardness. The polymeric paste containing D-mannan and the amino acid or amino acid condensate salt form a stable matrix in water. D-mannan-free polymer pastes (for example, starch and pectin) and synthetic polymer pastes (for example, polyvinyl alcohol and carboxymethylcellulose sodium salt) contain amino acids or amino acid condensate salts with stable mucus, sol, It is difficult to form a gel-like material, which causes the sedimentation and precipitation of the active ingredient, and in some cases, it is difficult to form a stable compound feed molded article unless care is taken.

The polymer paste containing D-mannan according to the present invention does not have a cis-secondary hydroxyl group at the 2,3-position such as a glucose ring in an aqueous solution state. A hydrated sol or hydrated gel is formed with an amino acid salt or an amino acid condensed salt that is too powerful for a non-mannan type polymer to perform. This is a phenomenon that was not known at all even among researchers of sugars and amino acids.

Those useful as polymer paste containing D-mannan used for the purpose of the present invention include guar gum (galactomannan), tara gum (galactomannan), locust bean gum (galactomannan), and gangan mannan ( Glucomannan), konjac mannan (glucomannan), elegans mannan (glucomannan), zalepmannan (glucomannan), microbial mannan and the like.

The term "fish and shellfish" as used in the present invention is a generic term for a marine animal, and generally refers to freshwater and marine aquatic animals including fish, shrimp and shellfish. However, aquatic insects, amphibians, reptiles, water birds, and mammals are not included. The feed for fish and shellfish varies depending on the size, growth degree, water temperature, etc. of the fish and shellfish. Generally, fish are planktonic fish during the larval age. It is known that the shape and size of the feed change in accordance with the growth, and that the taste, that is, the odor and taste, also increases in accordance with the growth.

Naturally, the amino acids, vitamins, lipids, etc. necessary for growth of fish and shellfish also change according to their growth, and the types of additives containing these as nutrients are also taken into consideration. It is desirable.

The plant protein referred to in the present invention is a very important functional component for maintaining the life of the animal and producing the animal, and is produced by the plant. According to their physiological characteristics, they are classified into simple proteins, complex proteins, and denatured proteins. A typical protein is 50-55% carbon, 6 hydrogen.
5 to 7.5%, nitrogen 15.5 to 18.0%, oxygen 21.
5 to 23.5%, sulfur 0.2 to 2.0%, phosphorus 0.0
In many cases, it is composed of an element of up to 1.5%.

It is known that animals do not digest and utilize all amino acids ingested as proteins. Particularly, in the case of vegetable oil cakes, the efficiency (effective rate) of amino acids such as lysine varies depending on the degree of heating during processing. Have been. The effective rate is said to be about 80 to 90%, and the effective rate tends to gradually decrease as the intake of protein in the feed increases.

The condensation reaction between the α-amino acid and glycine or alanine is carried out by either a normal pressure method or a pressure method.

An example of the normal pressure method is described for the case of L-glutamic acid and glycine.
6 g (1.5 mol) and 73.6 g of L-glutamic acid
(0.5 mol) was placed in a 1-liter flask and boiled at 100 ° C. for 40 to 50 hours with stirring under a reflux condenser to give a colorless, transparent and slightly viscous reaction mixture, which was cooled on ice. No crystals are deposited.

On the other hand, in the pressure method, the above reaction mixture is placed in a 1-liter autoclave at 130 to 180 ° C.
And the reaction mixture is kept for about 4 to 10 hours to obtain a substantially similar reaction mixture.

Mixtures obtained by these reactions were each taken out of 100 ml of the solution and mixed with the same amount of ethanol.
When cooled to 0 ° C., a large amount of white crystals precipitate. The crystals are separated by filtration, washed with 50% ethanol, and dried under reduced pressure. The obtained white powder was subjected to LC-MS manufactured by Hitachi, Ltd.
(1200AP-ES type) When analyzed by an analyzer, the white crystals were found to be a mixture of glycylglutamic acid and glutamoylglycine.

The alkaline earth metal salts are reacted with the white crystals by reacting hydroxides, oxides, carbonates, chlorides, sulfates, nitrates, organic acid salts, alcoholates, acetylacetonates, etc. of the alkaline earth metals. Although they can be formed, they can be made into practical, highly palatable seafood feed additives by using relatively small amounts (e.g., using 5-50%) below the calculated amount. .

The thus obtained feed additive for fish and shellfishes containing an alkaline earth metal salt may be an aqueous solution, a dispersion, a viscous liquid or a paste in which a part of solids are about to be deposited, or a solid or crystalline powder. Either. In the case of a solid or crystalline powder, it is generally a colorless to white to pale yellow substance which is often soluble in water, and is added to a vegetable protein feed as an aqueous solution by mixing with an adhesive described below.

The above-mentioned reaction product of glutamic acid and glycine or alanine or an alkaline earth metal salt thereof can be uniformly prepared by using a polymer paste containing D-mannan as an adhesive when blended with vegetable protein. Dispersion and adhesion are achieved.

As the high-molecular substance containing D-mannan, there are the various substances described above, but the most useful ones are guar gum (galactomannan), locust bean gum (galactomannan), and konjac mannan (glucomannan). In general, guar gum 1 to
A 5% aqueous solution is convenient for compounding, and it is also convenient to use when the feed is formed into pellets by a pelletizer.

Prior to final shaping as a feed, naturally, in addition to the composition of plant protein as a feed component, necessary lipids, phospholipids, carbohydrates,
Vitamin, minerals (ash), etc., should be formulated into a compound feed suitable for the target fish and shellfish.

Next, an example in which D, L-methionine is used as an α-amino acid and glycine is reacted with glycine at normal pressure will be described.

D, L-methionine 74.6 g (0.5 mol), glycine 112.6 g (1.5 mol), water 500
ml into a flask, with a reflux condenser and stirring.
Boiling at 0 ° C. for 40-50 hours results in a clear solution. After cooling, 500 ml of ethanol is added to this solution to precipitate crystals. The white crystals are washed with 50% ethanol and dried under reduced pressure. This crystal is LC-MS manufactured by Hitachi, Ltd.
(1200AP-ES type), it was found that it was a mixture of glycylmethionine, methionylglycine, and methionyldiglycine.

Further, an example in which L-glutamic acid, D, L-methionine and glycine are reacted under pressure as α-amino acids will be described.

36.8 g (0.25 mol) of L-glutamic acid, 37.3 g (0.25 mol) of D, L-methionine, 112.6 g (1.5 mol) of glycine, 500 parts of water
The resulting mixture was heated in an autoclave at 150 ° C. for 8 hours with stirring to give a clear, slightly viscous solution. After cooling, 500 ml of methanol is added to this solution to precipitate crystals. It is collected by filtration, washed with 70% methanol, and dried under reduced pressure. This crystal was used for LC-MS (1200AP-ES) manufactured by Hitachi, Ltd.
Analysis) revealed a mixture of glycylmethionine, glutamylmethionine, glutamylmethionylglycine or methionylglutamoylglycine.

In the above condensation reaction of an α-amino acid and glycine, the cyclic glycine anhydrides 2,5,
- piperazine dione _{(C 4 H 6 N 2 O} 2) Izu almost-product, glycine seemed acts as a neutralizing agent for glutamic acid and methionine as a weak base, various dipeptide mixtures containing glycine is made . In addition, an experiment using L-α-alanine instead of glycine results in almost the same mixture of water-soluble peptides. These water-soluble peptides can be used as feed additives as they are, but changing some or all of them to magnesium salts, calcium salts, zinc salts or mixed salts thereof is better as an additive.

It is recommended that a polymer paste containing D-mannan be added to these warm aqueous solutions to be impregnated and attached to a vegetable protein feed and then used as a feed for fish and shellfish as a molded product.

In the case where vegetable juice and plant waste are used as plant proteins, microorganisms are allowed to act on them.
It is better to increase the protein by fermentation.

The main ingredients of the vegetable juice residue are citrus juice residue, fruit juice squeezed residue, coffee bean extract residue,
This is because it is extracted slag of various teas and sugar squeezed lees, and the main plant waste is processed vegetable waste, but it is not a favorite of seafood as it is.

[0062] Fermentation by the action of microorganisms refers to the use of aerobic microorganisms (yeast, filamentous fungi, basidiomycetes,
Bacteria, etc.) are propagated in the air stream to assimilate carbohydrates into proteins. In the case of yeast, Hansenula Capsulator, Saccharomyces roxy or Rhodotorlaglutinis etc. are used to convert mannan into yeast. A protein is produced as a by-product, but of course, it is also preferable to separately prepare and add a polymer paste containing D-mannan without considering such a matter.

The fermentation method is carried out in either a liquid phase or a solid phase. In general, the liquid phase method has a higher content of the produced protein, and in many cases, a protein content of 30 to 60% is obtained. In the case of the solid phase method, about half of this value is often obtained.

Next, an example of preparing a feed for fish and shellfish which contains a condensate of an α-amino acid and glycine by using a polymer paste containing D-mannan and is effective for preservation will be described.

Water 500 ml, glycine 112.6 g
(1.5 mol) and 73.6 g of L-glutamic acid
(0.5 mol) in a flask equipped with a reflux condenser.
Boil at 50 ° C. for 50 hours to form a clear solution. This solution is
While heating to 00 ° C., 5 g of the purified guar gum fine powder was charged, and 12000 r. p. m, to form a transparent gel, which is immediately put in a polyethylene bag, sealed and cooled to -20 ° C. The content becomes a rather hard rubbery gel but remains colorless and transparent.
This was molded into a string with an extruder and cut into small pellets (10 g). Separately, 50 g of a 5% aqueous solution of zinc taurine [(H ₂ NCH ₂ CH ₂ SO ₃ ) ₂ Zn] was prepared. Dissolve and use as feed additive. This solution is sprayed onto 250 g of soybean oil cake powder, sprinkled and mixed well, and then the mixture is extruded into a string form from a nozzle, dried and granulated to obtain a feed for carp that is well preserved.

[0066]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, as a typical embodiment of the present invention, a feed additive and a feed containing the same can be produced using a reaction product of L-glutamic acid and glycine. Is specifically shown.

When the grapefruit (citrus paradise) fruit is washed and squeezed using a squeezing machine, a sap and a squeezed scum are obtained approximately by half. This squeezed residue is ground with a juice mixer and lime milk is added so that the pH becomes 5.3. Since pectin and the like are separated from the water, if this is drained using a filter press or a centrifugal separator, a liquid corresponding to about 20% of the first grapefruit is obtained. When this liquid is allowed to stand, limonene is separated into an upper layer. When the liquid is separated and distilled, limonene is recovered. When the lower aqueous solution is concentrated under reduced pressure, the sugar content becomes 37%.
% Citrus molasses having a sweetness of pH 5.3. When citrus molasses is fermented while adding air to the liquid phase and adding air to the medium, the crude protein is reduced to 45 to 55%.
% Yeast powder (for example, Candida utilis, Hansenula anomala or Saccharomyces cerevisiae). On the other hand, squeezed sap (citrus pulp), which is a solid substance dewatered using a filter press or a centrifuge, is dried, finely pulverized, and an aqueous solution containing a culture component is added. , A brown powder having a crude protein content of 30 to 50% is obtained.

After the yeast powder and brown powder obtained here are heat-sterilized, fish meal, wheat gluten, cod liver oil, mineral components, vitamins and an aqueous solution of paste are added, kneaded, and extruded from a nozzle to form a fish cage for sea-cultured fish. Feed can be made.

The growth of microorganisms is generally performed in a liquid or solid medium. The optimum growth temperature of microorganisms is generally 35 to 50 ° C. for bacteria, and 20 to 35 ° C. for yeasts and molds, and the following components and water are required as medium components.

For acetic acid bacteria, for example, glucose 3
0 g, yeast extract 5 g, peptone 5 g, KH ₂ PO _{2
6g, MgSO 4 · 7H 2 O} 0.6g, MnSO 4
・ 7H ₂ O 0.3g, CH ₃ COONa ・ 3H ₂ O
A mixture of 25 g, 1 ml of glacial acetic acid and 1000 ml of water (pH
5.4) is useful. As for yeast, for example, glucose 30 g, yeast extract 5 g, peptone
5 g, KH ₂ PO ₄ 2 g, MgSO ₄ .7H ₂ O
A mixture of 3 g, 1000 ml of water (pH 7.0) is preferred.

When soluble carbohydrates or sugars are present as in the residue of citrus juice or vegetable juice, it is preferable that proteins can be formed by directly adding assimilating microorganisms (for example, yeast). In the case of the prepared yeast protein, it has a relatively hard cell shell on the outside, and it is important to break this shell and use it as feed.

The action of amino acids on fish and shellfish is L-form,
It depends on the D-form and the D, L-form. Optically inactive lower amino acids include glycine, taurine, and β-alanine, and these have a mild attractive effect on many fishes and shellfishes. Generally, the taste of fish and shellfish is in the order of L-form> D, L-form> D-form, and this order does not always coincide with the order of amino acid sweetness. Amino acids form various salts with alkaline earth metal ions under appropriate conditions, of which the magnesium, calcium and zinc salts, as well as the corresponding free amino acids, are those preferred by fish and shellfish.

In the sap of citrus juice (especially citrus pulp), a large amount of calcium remains due to the juice production process, and the calcium residue is reduced to 0 in the form of calcium pectate, calcium acid carbonate and calcium citrate. .
Since 2 to 2.0% of CaO is mixed, when an assimilating protein is produced from a raw material containing these, calcium amino acid is generated and mixed into the vegetable protein. In such cases, the presence of calcium may have an adverse effect on fermentation.On the other hand, calcium amino acids and oligopeptide calcium, which are products, should not be a concern in fish and shellfish feed. It is also recognized from the inventors' preliminary experiments.

The metal ions contained in what is generally called vegetable protein are Na, K, Mg, C
a, Zn, etc., the content of which is found to be K≫Mg> C
a> Na≫Zn in many cases. These metal ions form partial salts with amino acids, dipeptides, tripeptides, and tetrapeptides if they exist in the material, and it is very difficult for them to be contained in such forms in fish and shellfish feeds. It is preferred.

[0075]

EXAMPLES The present inventors have carried out a number of experiments on the present invention, and among them, representative examples sufficient to explain the technical contents of the present invention are shown below. The present invention should not be construed as being limited to only the examples described below, and it is to be understood that the embodiments can be arbitrarily modified and carried out without departing from the spirit and spirit of the present invention. .

Example 1: The fruit of Unshu mandarin orange (citrus aurantium) was washed with water and squeezed with a pressing machine. The juice (a mixture containing a small amount of D-limonene in the fruit juice) and the squeezed residue And about half each. This squeezed residue contains about 80% of water and 0.5 to several% of D-limonene, etc., and dried carbohydrate contains 15 to 2 carbohydrates.
0%, crude fiber 1.5-2.0%, crude fat about 0.2
%, Crude protein about 1.0%, and ash 0.5-1.0%. It contains organic acids and pectin, and it is difficult to separate water.
0 to 4.5) and added with milk of lime to mix and neutralize (pH 5.5).
After 0-5.5), if it is compressed again, it is drained to obtain a liquid of about 20% of the raw fruit. The liquid is separated and the aqueous layer is concentrated under reduced pressure at 50-60 ° C.
~ 25%, sugar content 35-40%, sucrose 12-20%,
Total nitrogen content 0.5-0.6%, ash content 0.2-1.0
%, PH 5.0-5.5.

On the other hand, the medium composition was 85% H ₃ PO ₄
3.2 g / l, KOH 1.2 g / l, NaOH
_{0.2g / l, MgSO 4 · 7H} 2 O 1.0g / l,
FeCl ₃ .6H ₂ O 15 mg / l, CuSO ₄ .5H
₂ O 0.1 mg / l, KI 0.2 mg / l, MnSO _{4
· H 2 O 1.5mg / l,} ZnSO 4 · 6H 2 O 1.
A solution containing 5 mg / l, (NH ₄ ) ₂ SO ₄ total 16 g / l (divided addition but total amount), and (NH ₄ ) ₂ CO total 8 g / l (divided addition but total amount) (pH 5.5 to 5.5) 6.
6) Prepare 1.2 liters, mix this with 200 g of Citrus molasses, and use Candida utilis 1 as yeast.
When 0 g is added and fermentation is carried out at 25 to 35 ° C. while blowing air vigorously, citrus yeast precipitates after about 50 hours.
If this is collected by filtration and dried, about 50 g of dried tangerine yeast
Get. This is about 4.5% moisture, about 55% crude protein,
It contains about 0.5% fat, about 20% carbohydrates and about 2.5% ash, and about 60% of this ash is CaO + MgO +
The powder, which is ZnO and which is obtained by adding 0.3 times the weight of glycine to the citrus yeast and thoroughly squeezing in a mortar in the presence of moisture, has become a feed that shows a remarkable attraction effect on locusts and hai in the dark. .

Example 2: Brazilian fruit of Valencia orange (Citrus sinensis) was washed with water and squeezed to obtain citrus molasses and squeezed juice (citrus pulp) in the same manner as in Example 1. . This citrus molasses contains about 78.9% water, about 0.3% fat, and about 2.0 protein.
%, Ash 1.1%, carbohydrates about 17.7%, calcium 170mg / 100g, pectin (as calcium pectate) 172mg / 100g, glucose 3.3%, fructose 4.2%, sucrose 4.7% And citrus pulp has 2.3% fat, 5.4% ash, and 13.5% fiber
%, Fructose 2.0%, glucose 1.8%, sucrose 3.4%
including.

On the other hand, 1 liter of the same medium composition solution as in Example 1 was prepared, mixed with 200 g of the above-mentioned Citrus molasses, and 7 g of Hansenura anomala, which was separated from fresh wakayama mandarin skin and cultured. In addition, the cells are cultured for 70 hours while blowing vigorously air, filtered, and dried to obtain 60 g of pale brown Valencia orange yeast powder. This contains about 55% of crude protein, but is slightly inferior to fish meal in terms of components. More preferably, it is fortified with a peptide comprising glutamic acid, methionine and glycine prepared as follows. There is a need.

That is, in a 1-liter autoclave, water 5
When 100 ml, 36.8 g of glutamic acid, 37.3 g of D, L-methionine and 112.6 g of glycine are added and reacted at 160 to 170 ° C. for 3 to 4 hours, a transparent and slightly viscous aqueous solution is obtained. 15 ml of this solution was separated and 10%
Calcium acetate solution 5ml, 2% guar gum aqueous solution 6ml
To make a mixed solution, spray it on the above Valencia orange yeast powder, mix and dry with hot air,
When crushed, it became a feed for cultured fish with high attraction to freshwater fish such as goldfish, crucian carp, carp and catfish.

Example 3 A dried product of the citrus pulp shown in Example 2 was placed in a small pulverizer and finely pulverized into a 300 mesh powder. To 100 g of this powder, 500 ml of the same medium composition as in Example 1 and 10 g of Aspergillus oryzae were added, mixed well, and mixed at pH 6.0 in a jar fermenter.
The fungus is allowed to grow for 24 hours with sufficient aeration at 0. Then, Saccharomyces cerevisiae 10 g
And 1.5 l of the same medium composition as in Example 1
Fermentation at 5 to 30 ° C. for 70 hours gives a brown precipitate. After cooling, this is filtered off, washed with water and dried to obtain 55 g of a powder having a characteristic yeast smell. After adding 10 ml of an aqueous solution containing 10% magnesium taurine and 20 ml of a 3% glucomannan aqueous solution separately prepared to the powder and kneading well,
It is extruded from a nozzle, formed into a string, semi-dried, crushed, and dried at 100 ° C. for 2 hours to obtain a crumble feed.
The feed obtained here is classified using a sieve to become a juvenile feed for crucian carp, goldfish and tropical fish.

A soft crumble type of feed for ayu culture is preferred. In this case, it is necessary to pay attention to the size and shape of the feed, the feeding method, and the water flow so as not to cause water pollution due to feeding loss. There is.

Example 4: Feed for eel farming is divided into fry (shirasu) and fodder, but it is convenient to make and feed a dough containing fishmeal and yeast. For eel farming, petroleum protein and soybean oil cake have been compared before,
The latter seemed to be superior because the content of methionine, lysine, etc. was small. However, since the yeast crust was hard and indigestible, it had to be heated and crushed so as to crack the crust. On the other hand, the present inventors performed an electron beam irradiation treatment on Valencia orange yeast from Citrus molasses obtained in
35% yeast powder crushed to 00 mesh, 35 North Sea fish meal
%, A supplement of L-glutamic acid, D, L-methionine and glycine shown in Example 2 with calcium acetate and guar gum added for 5%, fish liver powder 5%,
5% of skim milk powder, 3% of mixed vitamins and 2% of minerals were blended, and water was added to obtain a dough. The eel was a fish with a strong preference for amino acids, and gathered well in the above dough, and the dough seemed to prefer softer ones. When the water temperature is maintained at 20 to 25 ° C for eel fattening feed, the above-mentioned dough shows better cultivation results when raw sardine or saury bait is used, and the meat quality of eel is also good. Was.

Example 5: Soybean oil lees as a vegetable protein
In order to make gluten meal, soy protein products, etc. into fish and shellfish feeds, it is necessary to select effective fortifying additives. For this purpose, alkaline earth metal salts of amino acids or amino acid condensates must be added separately as shown below. It is better to synthesize and use.For example, taurine and an alkaline earth metal oxide or hydroxide are neutralized in water to form a corresponding taurine salt, and the filtered aqueous solution is concentrated to crystallize. Is precipitated, and the crystals are dried to obtain a product having a high purity, which can be mixed as a fortifying agent into a conventional fish and shellfish feed.

Example 6 When an equimolar amount of an alkaline earth metal acetate is added to a concentrated aqueous solution of monosodium L-glutamate, an alkaline earth metal L-glutamate hydrate is formed, and ethanol is added thereto. The crystals are precipitated by precipitation, collected by filtration and dried at 150 ° C. to obtain the corresponding anhydrous L-glutamic acid alkaline earth metal salt as a white powder. Instead of sodium L-glutamate, D, L-methionine sodium, L-
Monosodium aspartate, sodium glycine,
When sodium D, L-alanine is used, the corresponding alkaline earth metal salts are obtained. Since these are easily obtained as hydrated crystals, the precipitated crystals are separated by filtration and then filtered at 120 to 130.
Dried at ℃ and stored as anhydrous. The anhydrous powder was blended and used for strengthening soybean oil lees or rapeseed oil lees used as fish feed.

Example 7: Various amino acids are dissolved in dimethylformamide, and chloroacetic acid chloride is reacted with the chloracetylated amino acid. The resulting glycated amino acid is reacted with concentrated aqueous ammonia to obtain the following glycyl amino acid (dipeptide). .

That is, glycyl-L-α-alanine (mp 218 ° C., decomposed), glycyl-D, L-serine (mp 218 ° C., decomposed), glycyl-D, L-leucine (mp 257 ° C., decomposed), glycyl-L -Isoleucine (mp 242 ° C., decomposed) is obtained, all of which are water-soluble. An alkaline earth metal hydroxide emulsion is added to this aqueous solution to neutralize the solution, and ethanol is added to the solution to precipitate the corresponding dipeptide alkaline earth metal salt. The precipitate is separated by filtration and dried at 130 to 140 ° C. to obtain a dipeptide alkaline earth metal salt (for example, calcium salt).
Is obtained as a white powder.

Calcium salt of the dipeptide mixture (mixture of glycyl-D, L-leucine 50%, glycyl-L-isoleucine 50%) 10 g, soybean oil cake 40 g, krill powder 15 g, sucrose powder 40 g, 4 g vegetable oil, 6 g silkworm oil cake, 5 g calcium phosphate,
A small amount of water was added to a mixture of 10 g of 5% guar gum sol and 5 g of dextrin, kneaded and press-molded, and dried with hot air to obtain a general-purpose feed for adult fish.

Example 8: Crustacean larvae and shellfish larvae
Even if a yeast microparticle feed is prepared, it is currently very difficult to grow it alone. However, in general, compounds such as krill extract, chicken egg, skim milk, squid extract, clam extract, and liver oil have been practically well tested.
What has been developed as an additive to such larvae feed is a yeast fortifying additive comprising L-glutamic acid, methionine, α-alanine, glycine and alkaline earth metal.

That is, 0.5 mol of L-glutamic acid,
When 0.5 mol of D, L-methionine, 1.0 mol of α-D, L-alanine and 2.0 mol of glycine are reacted in water at 180 ° C. for 3 hours in an autoclave, glycylmethionine and α-alanylmethionine are obtained. , Glutamoylmethionine, glutamoylmethionylglycine, etc. are obtained. A solution obtained by neutralizing this aqueous solution with calcium hydroxide was found to have an effect of considerably attracting crustaceans and shellfish larvae. Therefore, 150 g of dry powder of brewer's yeast (Saccharomyces cerevisiae) and 100 g of this mixed aqueous solution were used. Was sprayed, kneaded, dried and pulverized, and used as feed for crustacean larvae and shellfish larvae.

Example 9: When a large amount of raw food such as sardine, mackerel, saury and the like is used in aquaculture, feed-induced liver injury is caused by lipid peroxide generated during storage of the raw food. The disease becomes chronic and mortality increases. As a solution to this, use of glutathione (γ-L-glutamine-L-cystinyl-glycine) as a liver injury preventive agent (JP-A-60-1563)
No. 49) or use of a feed containing glutathione disulfide, γ-L-glutamine-L-cystine, and γ-L-glutamyl-L-cystidisulfide (Japanese Unexamined Patent Publication No. 2-3).
No. 12554) is recommended, but this alone is not enough to improve the liver function of fish, and it is basically preferable to change to use plant protein as the main component of feed. In this case, the methionine component becomes remarkably insufficient compared with the raw food. Therefore, L in the second embodiment
-To a slightly viscous reaction solution of glutamic acid, D, L-methionine and glycine (786.7 g), magnesium oxide (40.3 g) was added and neutralized to obtain a hot solution, and 2 g of guar gum was added. 6 using a homogenizer
000r. p. m was mixed with 3 kg of purified soybean protein (frozen tofu fine powder) and 3 kg of commercially available brewer's yeast powder, kneaded, and then pelletized by an extruder and dried at 100 ° C. to form a molded feed. And
It was found to be quite widely used as feed for crabs of hamachi, Thailand, flounder and marine.

Example 10: Dry squeezed residue obtained by squeezing the fruit of Citrus unshiu (citrus aurantium) (15 to 20% of carbohydrate, 1.5 to 2.0% of crude fiber, approximately 0 to crude fat) 0.2%, crude protein about 0.1%, total nitrogen content about 1.0%, ash content 0.5-1.0%, pH 4.0-5.0).
Finely pulverize to 0 mesh. 500 g of water is added to 500 g of this powder.
ml (containing KH ₂ PO ₄ and NH ₄ NO ₃ ), kneaded and sterilized at 120 ° C., cooled to 30 ° C., added with 10 g of Aspergillus olise, made into a plate, and heated at 25-30 ° C. to 70 ° C.
When the fermentation is carried out under air circulation for ~ 80 hours, about 500-600 g of brown powder (20-30% moisture, about 1 crude protein)
5-20%). When 20 g of fresh Hansenula anomala yeast is added to this powder and fermented at 30 ° C. for an additional 70 hours while blowing air, a feed powder containing about 30% crude protein is obtained. 400 g of this powder, 50 g of wheat gluten, 50 g of bonito oil, mixed mineral powder 10
g, mixed vitamin 5g and guar gum powder 5g
Is mixed with a slightly viscous aqueous solution (786.7 g) of L-glutamic acid, D, L-methionine and glycine in Example 2, and 50 g of finely powdered calcium carbonate is further added and mixed vigorously. A kneaded product obtained by dispensing and adding 1/10 of the mixed slurry was pelletized by an extruder, and dried at 100 ° C. to obtain a molded feed. This is hamachi, flatfish, red sea bream,
It was very good as a cultivated feed for locusts.

Example 11: α-Amino acids having a benzene nucleus in the molecule (phenylalanine, tyrosine and tryptophan) are important amino acids in proteins, but the isolated ones are relatively unstable and soluble in water. Poor and difficult to process into feed additives for fish and shellfish. Then, these synthetic products (D, L-form) were reacted with chloroacetic acid chloride by the method shown in Example 7 to obtain chloroacetylated amino acids, and then reacted with concentrated aqueous ammonia to obtain glycyl-D, L-phenylalanine, glycyl-D, L-tyrosine and glycyl-D, L-tryptophan were synthesized.

Next, each of these glycated products was added in 0.1 g.
1 mol of L-cysteine and 0.1 mol of glycine per mol.
200 ml of an aqueous solution containing 3 mol was added, and the mixture was placed in an autoclave and reacted at 180 to 185 ° C.
0.05 mol of white powder of zinc taurine prepared by the above method is added and mixed. 3% for each of the three mixtures obtained
Add locust bean gum aqueous sol and stir to finish as an emulsion. These emulsions were incorporated into soybean oil cake feed or rapeseed oil cake feed, respectively, and used as feed for freshwater fish propagation, and far better results were obtained than those without the additive.

Example 12: L-lysine, L-arginine, L-histidine, L-proline and L-hydroxypurine contain 0.1 mol of calcium chloride in an aqueous solution containing 0.2 mol of each hydrochloride When a methanol solution is added and the mixture is concentrated under reduced pressure, a double salt of calcium chloride of each amino acid is obtained. For the purpose of using these as feed additives, there is no particular need to purify, and the obtained paste-like or crystalline matter is appropriately dissolved in water, and this amino acid calcium salt solution is sprayed on soybean oil cake feed or dried yeast. After drying under reduced pressure, the mixture was kneaded as in Example 4 and used as feed for eel fattening. As a result, far better cultivation results were obtained than when no amino acid calcium salt was added.

Example 13: When 0.5 mol of D, L-methionine and 1.5 mol of glycine are reacted by boiling in water (500 ml), the mixture is cooled to -10 ° C after completion of the reaction. Until no crystals were precipitated, it was examined whether the presence of the catalyst (the following each used in an amount of 7 g each) added to the reaction mixture affected the reduction of the reaction time. After completion of the reaction, the added catalyst was removed by filtration, and the reaction mixture was analyzed by LC-MS (1200AP-ES type), Hitachi, Ltd.

The relationship between the type of the catalyst and the reaction time is as follows.
(20-30 hr), SnO (30-40 hr), strongly acidic ion exchange resin (10-20 hr), Sb ₂ O ₃ (2
0-30 hr), no catalyst (40-50 hr),
The effect was recognized for each of the catalysts. When about 100 ml of water evaporating from the middle of the reaction was distilled off, the above reaction time was further shortened.

[0098]

The present invention relates to an amino acid having 2 to 11 carbon atoms or a condensate of the amino acid with glycine or alanine, and at least one alkaline earth metal selected from the group consisting of magnesium, calcium and zinc. The present invention relates to a feed additive for fish and shellfish, which comprises an amino acid salt or an amino acid condensate salt to which ions are bound.

[0099] Conventionally, as a feed for fish and shellfish, one containing fishmeal or raw fish and shellfish as a main component has been used. To improve this, it was necessary to change the main component of the feed to vegetable protein. We have:
Research was conducted to further enhance the content of the component, which is a weak point of plant protein, and the present invention was completed to solve the problems.

Therefore, it is believed that the present invention greatly contributes to the feed industry, the fishery industry, the cultured fish and shellfish industry, and the food industry.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A23K 1/18 102 A23K 1/18 102B (72) Inventor Masahiro Matsuda 149-38 Nakatsu, Kakogawa-cho, Kakogawa-shi, Hyogo Prefecture F-term (reference) 2B005 GA01 GA02 GA03 GA04 GA06 GA07 MA01 MA05 MC04 MC06 2B150 AA07 AA08 AB04 AB05 AB20 AE31 AE33 AE44 BB01 CA06 CA22 DA44 DA45 DA46 DA47 DA48 DA49 DC14 DH04 DH05 DH09

Claims (5)

[Claims] 1. An amino acid salt comprising an amino acid having 2 to 11 carbon atoms and at least one alkaline earth metal ion selected from the group consisting of magnesium, calcium and zinc. Feed additive for seafood. 2. A condensate of an amino acid having 2 to 11 carbon atoms with glycine or alanine, wherein magnesium,
A feed additive for fish and shellfish comprising an amino acid condensate salt to which at least one alkaline earth metal ion selected from the group consisting of calcium and zinc is bound. 3. The amino acid having 2 to 11 carbon atoms is glycine, alanine, valine, leucine, isoleucine, serine, threonine, cysteine, taurine, methionine, aspartic acid, asparagine, glutamic acid, glutamine, lysine, arginine. The feed additive for fish and shellfish according to claim 1 or 2, which is at least one compound selected from the group consisting of histidine, proline, hydroxyproline, phenylalanine, tyrosine, and tryptophan. 4. The feed additive for seafood according to any one of claims 1 to 3, wherein the feed additive for marine products is guar gum (galactomannan), tara gum (galactomannan), locust bean gum (galactomannan), or giganbana mannan (glucose). Mannan), konjac mannan (glucomannan), elegans mannan (glucomannan), zalep mannan (glucomannan) and a microbial mannan, comprising a polymeric paste containing at least one D-mannan. Feed additive for seafood. 5. A feed for fish and shellfish, wherein the additive for feed for seafood and shellfish according to any one of claims 1 to 4 is blended with a vegetable protein.