JPH0286738A - Feed granulated with extruder - Google Patents

Abstract

PURPOSE:To obtain the subject feed capable of sufficiently keeping the activity of vitamin C in a feed and reducing the free inorganic phosphoric acid in the feed by adding L-ascorbic acid pyrophosphate (salt) to a feed. CONSTITUTION:The objective feed for cattle, pig, chicken, pets, fish, shellfish, crustacean, etc., can be produced by adding preferably 5-5,000mg of an L- ascorbic acid 2-pyrophosphate (salt) to 1kg of a feed.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to granulated feed produced using an extruder granulator, and particularly relates to extruder feed that exhibits high 7-ascorbic acid activity for animals. This relates to Ruder granulated feed.

[Conventional technology]

Extruder granulated feed is made by applying high heat, moisture, and pressure to feed ingredients using a granulator called an extruder.
- Granulated feed (also called pelleted feed or simply pere-soto) made by starch, and is considered to be one of the special granulated feed products. (Isao Miyazono, Special issue on aquaculture, 23@, No. 12, P110~, 1986
There are two types of this extruder granulated feed based on its shape: one is porous feed (Expans).
ion Pe1let feed or simply EP feed. ) is a porous feed pellet called
The other is a solid, hard granulated feed that is not porous or porous. The former generally has a specific gravity of less than l and floats on water (or
It is also called floating bait because it floats in the water. These extruder granulated feeds are characterized by high stability in water, from porous to hard types.
It is said to be highly digestible for animals and waste less feed.

The stability of extruder granulated feed in water is different from that of regular feed, and even if it is left in water for a long time, it will absorb water and increase its volume, but its shape will not change and it will not pollute the water. In addition, because it contains a large amount of alpha starch powder, it is highly digestible and absorbable within the animal body, and has a lower powdering rate than regular feed, so there is less powdering during transportation, so there is less feed wastage. It is attracting attention as an ideal feed.

In addition, in recent years, as aquaculture and other industries have become larger and more dense,
As water pollution caused by eutrophication from feed is becoming a social issue, demand for extruder granulated feed that does not pollute water is increasing.

This is because the high stability of the extruder feed in water can minimize contamination by eutrophication of the aquatic environment.

However, the production of feed under high temperature and high pressure degrades vitamins that are relatively sensitive to heat, especially L-ascorbic acid. A method has been used in which L-ascorbic acid is adsorbed into granulated feed together with vitamins, fats and oils, etc. after granulation.

By the way, the addition of L-ascorbic acid to feed is nutritionally essential, but because L-ascorbic acid is extremely easily oxidized and unstable, more stabilized ascorbic acid is used than ever before. It has been proposed and applied to feed.

For example, application of L-ascorbic acid-2-sulfate ester salt to veterinary drugs (JP-A-51-125756).

Application of L-ascorbic acid-2-phosphate ester salt to animal feed (JP-A-62-198615. JP-A-62-2
85759). In addition, a simple synthesis method has been reported for new ascorbic acid derivatives such as L-ascorbic acid-2-triphosphate salt and L-ascorbic acid-polyphosphate salt (JP-A-63-500
240).

In addition, in recent years, L-ascorbic acid coated with oil and fat has also been used as a feed additive.

Regarding the monoascorbic acid-2-pyrophosphates related to the present invention, a method for producing the same was reported in 1969 (Nomura, Chem, PharBull).
,, Japan, Vol. 17, P. 381, 1969), and has not attracted any particular attention since then.

Many studies have been conducted on the physiological activity of these stabilized compounds as monoascorhinic acid in living organisms, but there are considerable differences in the presence or absence of activity depending on the type of living organism.

For example, the activity of L-ascorbic acid-2-sulfate esters has been confirmed in certain fish and crustaceans (J, E, 1lalver, N, Y).

Acad, Sei, Volume 258, P81, 1975)
, reported to have no physiological activity as L-ascorbic acid in guinea pigs and monkeys (L, J.

Machlin, Am, J., Cl1n, Nutr, 2
Volume 9, P825, 1976). L-ascorbic acid-
The activity of 2-phosphate ester has been confirmed in monkeys, humans, guinea pigs, etc. (L, J
, Machlin.

etc,, Am, J, clin, NuLr, vol. 32, P
325, 1979 and Fuyuki Mima et al., Vitamin, Vol. 41, No. 6, P2S5. 1970). The activity of L-ascorbic acid-2-triphosphate has been confirmed in guinea pigs (Japanese Unexamined Patent Publication No. 63-500240).

As for ascorbic acid coated with fats and oils, because the digestive capacity such as the ability of the stomach differs depending on the type of animal, the presence or absence of its activity may vary depending on the individual species of the animal, even for the same coated product. ing.

[Invention or problem to be solved]

As mentioned above, L-ascorbic acid is unstable, so even if L-ascorbic acid is added to feed ingredients and granulated with an extruder, the ascorbic acid in the granulated feed will not be absorbed in the granulator. Most of it is inactivated by the added heat and pressure. The temperature inside the extruder varies depending on the type of feed made with the extruder, but generally it is 90% in the presence of 5 to 50% moisture.
The temperature will be over 'C. In particular, when porous feed is produced using an extruder, the feed material is heated to a temperature of 100 to 140° C. in the presence of 5 to 50% moisture. At these temperatures, even if L-ascorbic acid is added to the feed, most of it will decompose and become inactive.
Animals fed diets made by extruder granulation suffer from vitamin C deficiencies as well as vitamin C deficiencies.
Serious problems could occur, such as dead fish due to bacterial infection due to deficiency, and delayed regeneration and healing of wounded skin.

In order to alleviate these problems, recently, after drying the feed granulated with an extruder, it is passed through a crumbler, and L-ascorbic acid dissolved or dispersed in an appropriate solvent is added to the feed together with the solvent. In the process of adsorbing and re-drying if necessary, L is added to the feed.
- Ascorbic acid was added.

For this reason, there is a problem in that the manufacturing process is extremely complicated and time-consuming, and the manufacturing efficiency is also reduced. In addition, ascorbic acid is adsorbed after granulation by a solvent using this method.As ascorbic acid is present in large quantities on the surface of the feed, it is susceptible to air oxidation and requires long drying conditions at low temperatures after granulation. There was a problem that it was inefficient and decomposed over time during the distribution process. Furthermore, when put into water, ascorbin easily comes into contact with water and decomposes, and most of it is eluted and diffused into the water, and is not ultimately absorbed by the organisms that prey on it. There was a problem in that the activity efficiency of the acid was significantly reduced. For this reason, when animals are raised using conventional extruder silviculture feed, L-ascorbic acid becomes insufficient.
As a result, there were major problems such as a large number of deaths and frequent occurrence of diseases and malformations.

Conventional extruder silviculture feeds had these problems, and as a result, the use of extruder silviculture feeds, which do not degrade the aquatic environment and are said to have good feed efficiency, is extremely limited, and as a result, the aquatic environment deteriorates. There were also problems such as delays in purification. In order to solve such problems, the present inventors have conducted repeated research on adding stabilized ascorbic acid derivatives that are not decomposed even by extruder granulation to feed raw materials for granulation.

For example, already known stabilized derivatives of mono-ascorbic acid, mono-ascorbic acid-2-sulfate esters and L
-We tried a method of adding ascorbic acid-2-phosphate esters to feed materials and granulating them with an extruder granulator, and the internal temperature of the extruder was 100℃ to 140℃.
Porous feed was granulated using a method and the residual rate in the feed after granulation was measured, but the residual rate did not stabilize at 5 to 45%, and the problem was that only feed with a low residual rate was obtained. was there.

This is caused by the decomposition of mono-ascorbic acid derivatives due to the high heat in the extruder (100-140°C) and the sulfate ester degrading enzyme and phosphate ester degrading enzyme group remaining in the feed materials derived from flour and other natural products. It has become clear that the stabilized derivative of L-ascorbic acid is converted into unstable mono-ascorbic acid by being degraded by these enzymes before granulation. In addition, when extruder granulated feed was manufactured using feed materials to which L-ascorbic acid-2-triphosphate and L-ascorbic acid-2-polyphosphate were added, tapeworms were affected by the high temperature and pressure inside the extruder. It has become clear that phosphoric acid is liberated due to the moisture contained (the feed material was granulated with a moisture content of 25%), and inorganic phosphoric acid for tapeworms is produced in the feed.

As a property of L-ascorbic acid-2-polyphosphate esters, it has been recognized that as the number of phosphoric acids per molecule increases, phosphoric acid tends to be easily liberated with less energy and accumulate in feed. It was done. The release of a large amount of inorganic phosphoric acid in these feeds is not desirable in terms of purifying the aquatic environment, and in recent years efforts have been made to purify the aquatic environment, especially to reduce the concentration of phosphoric acid in water. However, the addition of polyphosphoric acid esters, which tend to release phosphoric acid, to feed has been problematic.

The present invention has been made in view of the above circumstances, and aims to provide an extruder granulated feed that does not decompose at high temperatures, is simple to manufacture, and has high ascorbic acid activity. .

[Means to solve the problem]

As a result of repeated research to achieve the above object, the present inventors have found that when L-ascorbic acid-2-pyrophosphate esters are added to feed materials and feed is produced using an extruder granulation material, the extruder Inside temperature is 100℃~40℃
It has been found that even under severe manufacturing conditions where the eye height is 0, a high percentage of the physiological activity of the residual L-ascorbic acid in the feed after granulation remains.

That is, in the present invention, L is added to the extruder granulation feed f1.
- Contains salts of ascorbic acid-2-pyrophosphate esters.

Mono-ascorbic acid-2-pyrophosphate (hereinafter abbreviated as AP) according to the present invention has the following general formula.

In the above formula, X and Y are different and are -14 and OA s, respectively.
From the group consisting of.

A3. A t , A s , A 4. As
, A s are taken from the group consisting of hydrogen and salt-forming cations. Normally when AP forms a salt, A + , A t
, A 3 , A a consists of a salt-forming cation, and A
Generally, s and Ae consist of hydrogen, but are not particularly limited to this.

As a representative example of AP according to the present invention, shi-ascorbic acid-2-pyrophosphate sodium salt,! 7-ascorbic acid-2-pyrophosphate magnesium salt,
L-ascorbic acid-2-pyrophosphate ester calcium salts include, but are not limited to, AP may form salts with all salt-forming cations, such as, for example, alkali metal, alkaline earth metal, ammonium salts. Be able to do it.

The extruder granulated feed of the present invention is a granulated feed made under high temperature and high pressure using a granulator called an extruder, and the granulation conditions are such that the temperature inside the screw press is 50°C. ~200°C1 The pressure applied to the feed in the granulator is 10~10000Kg/cII2. It is a feed that is mixed, kneaded, and granulated under high temperature and high pressure conditions with a moisture content in the range of 1 to 70%.

The extruder granulator used to produce the extruder granulated feed according to the present invention is one that is commercially available and is generally called an extruder shoeking extruder or an extrusion pelleter. For example, US 11enger M
manufacturing company (714 Main Street)
et P, O, BOX 130,5abetha,
There is a model X-185 shoeking extruder manufactured by Kansas, U.S.A.

The basic structure of an extruder granulator is a raw material input section called a feeder, a humidity control section called a couture or conditioner, a pressurized kneading section called a screw press, and a feed molding section called a molding gui. Consists of departments. Furthermore, depending on the model, a cutting device called a cutter and a cooling device for cooling the extruder may be installed, facing the molding guide. Generally, in the extruder granulation process, after feed raw materials are supplied to the feeder, the moisture content of the feed raw materials is adjusted to 1 to 70% using steam, hot water, or water in the extruder. Mixing, compression, and kneading are forcibly performed using a shaped screw. The pressure applied to the feed can reach hundreds to thousands of kg/cff at high places.The feed ingredients reach a high temperature of 90 to 150 degrees Celsius due to the high pressure and frictional heat, and are released into the atmosphere through a molding opening called a molding goo. This extruded rod-shaped feed is cut into appropriate lengths by a cutter located opposite the goo to become feed pellets.

In the production of such extruder granulated feed,
The most important and characteristic process is that feed ingredients containing moisture are
The point is that it is mixed and compressed under high temperature and high pressure conditions. This is because, with an ordinary granulator, the granulation temperature and pressure cannot provide sufficient granulation conditions to decompose most of the L-ascorbic acid.

General extruder granulated feed is granulated with an extruder, cut into appropriate sizes, and processed through processes such as drying, high-temperature steam treatment, and separation into final products. There are no particular limitations on the subsequent processing. The final product of granulated feed produced by an extruder granulator is of various types depending on the purpose of the feed, and one representative example is what is called porous feed. Porous feed is feed that is granulated by applying high temperature and pressure in an extruder granulator, and is then rapidly released into the atmosphere to expand and granulate the feed into pellets with a specific gravity of 1 or less. This is a special feed that does not sink to the bottom of the water when placed in water, but floats on the water surface or in the water for a long time. When manufacturing such porous feed, the inside of the extruder is generally operated at a high temperature of 100°C to 140°C in order to gelatinize the starch during extruder granulation. .

Another typical example of feed that is granulated using an extruder is hard feed that has increased stability in water. Porous feed also falls under this category of feed because it exhibits high stability in water, but hard feed is generally porous because it has a specific gravity of 1 or more, is heavier than water, and has the property of sinking to the bottom of the water. It is distinguished from quality feed. This hard feed is stable on the bottom of the water for a long time and does not lose its shape, so it is useful as feed for animals that feed mainly on the bottom, such as crustaceans such as shrimp and crabs, and shellfish.

These feeds can maintain their shape for a long time at the bottom of the water without dissolving, so they can be fed for a longer period of time than regular feeds.

In the method for producing extruder granulated feed to which AP is added according to the present invention, it is sufficient that AP and raw materials in the pond are uniformly dispersed in the screw press section of the extruder granulator, and other steps are not required. There are no particular limitations, and a feed manufacturing method using a numerical extruder is applicable.

In particular, the drying temperature and drying time, which have been problematic in conventional methods, are not particularly limited as long as the conditions do not cause decomposition and alteration of nutritional components other than AP in the feed.

AP can be uniformly dispersed in the raw material by using a mixer with other vitamins in the pre-process of extruder granulation, but it is preferable to mix and disperse AP with other vitamins in the extruder granulation machine. Suitable for dissolving AP in water or hot water for humidity control in a part of the kutuka, and adding AP to the feed during humidity control in a part of the kutuka to disperse AP more uniformly in the feed. ing.

The insects added to the AP extruder granulated feed are selected depending on the type of AP salt, the type of feed, and the target animal. AP equivalent to 1 to 10 times the number of moles is added. Specifically, in the case of ascorbic acid-2 pyrophosphate tetrasodium salt, feed IK
What is necessary is just to add 5-5000 mg with respect to g.

The target animals for the extruder afforestation feed containing AP of the present invention include not only feed for terrestrial animals such as cows, pigs, chickens, and bed animals, but also feed for aquaculture animals such as seafood and crustaceans. Useful.

In particular, sweetfish, rainbow trout, yellowtail, sea bream, and carp, which are cultivated at high density in water and have a high need for ascorbic acid,
It is extremely useful as feed for eel, salmon, horse mackerel, flounder, tilapia, catfish, tiger prawns, beef prawns, abalone, scallops, etc.

[Effect]

The thermal stability of AP is extremely high, and it does not decompose even under the high temperature and high pressure inside the extruder granulator, and the amount of remaining AP in the feed after granulation is maintained at a high level.

These remaining APs are stable against heat, but when they are taken into the body along with feed and absorbed, AP is quickly converted to L-ascorbic acid by phosphatase in the body and converted into vitamin C. activity can be expressed.

The reason why L-ascorbic acid-2-sulfuric acid esters and L-ascorbic acid-2-phosphoric acid esters are relatively easily decomposed in the extruder is because the monoester groups of phosphoric acid and sulfuric acid are in the extruder. In the case of AP, the reason why it is stable under the same conditions is due to the chemical bond energy bonded to L-ascorbic acid, or because it cannot withstand the high pressure and high liter filling conditions of AP. Since the bepyrophosphate ester bond is more stable, it is presumed that AP remains stable under high temperature and high pressure conditions.

AP exhibits extremely high stability as described above, but it is rapidly degraded to L-ascorbic acid in the enzymatic hydrolysis reaction mediated by phosphatase in vivo, so AP is not produced. It can fully express its activity as monoascorbic acid in the body.

In addition, a comparison of the thermal stability of AP, L-ascorbic acid-2-sulfuric acid esters, and L-ascorbic acid-2-phosphate esters and the conversion of AP to ascorbic acid in the body are described in Examples. This will be explained later.

The extruder granulated feed containing AP of the present invention will be explained in more detail in the following examples, but the present invention is not limited to these examples.

(Example 1) As one specific example of the extruder granulated feed containing AP of the present invention, porous feed for sweetfish will be explained as an example.

Porous feed is one of the representative examples of extruder granulated feed.

101 kg of raw materials with the composition shown in Table 1 are crushed using a crusher, and passed through an electric sieve to yield 100 kg of feed raw material powder of 24 mesh passes.
I got it. Next, the raw material powder was mixed uniformly with a stirring mixer at 6° rpm for 20 minutes. 40g of L-ascorbic acid-2-pyrophosphate tetrasodium salt was dissolved in 5Of2 of water, and this solution was heated to 90°C, and this was used as a humidity control liquid for an extruder.

Stomach Enger Manufacturing X-1
A model 85 extruder was operated in a conventional manner using the moisture conditioning solution to obtain a porous feed having a moisture content of 27%, a diameter of 4 mm, a length of 5 mm, and a specific gravity of 0.7.

Next, the feed was dried using a hot air dryer at 70°C for 2 hours to obtain 90 kg of porous feed for sweetfish.

This feed 109 was crushed with agate bees to make 300 mesh baths. Accurately weighed 0.2 g of this crushed feed, put it in a 15 cc test tube together with 10 cc of water and starch degrading enzymes o and ot9, and shook it thoroughly. Mix, leave at 37°C for 10 minutes, shake for 5 minutes using a test tube shaker, centrifuge at 1000 rpm for 10 minutes, transfer the liquid phase with a pipette to another test tube, and use this 20
μQ was analyzed using high-performance liquid chromatography in the ultraviolet region at 258 nm.
It was confirmed that 93% of the theoretical addition amount of tetrasodium ascorbic acid 2-pyrophosphate remained.

Margin table below! (Example 2) The following experiment was conducted to examine the stability of L-ascorbic acid-2-pyrophosphate and other ascorbic acids.

0.08 of each of the ascorbic acids shown in Table-2
Make an aqueous solution of 50σ by weight%, and add this solution to 10
Aliquot 5 cc into each cc test tube, then add 0.0 cc of this solution.
The p
59626),
An enzymatic reaction was performed. After reacting at 37°C for 30 minutes,
In order to measure the residual amount of 7-ascorbic acid, 20 μQ of each solution was analyzed by high performance liquid chromatography to measure the residual ascorbic acid m, which was set as 8.

On the other hand, porous feed for sweetfish was produced by the method shown in Example 1 using about 5Of2 of each of the solutions of ascorbic acids shown in Table 2 as a humidity control liquid for the extruder. Next, an extract was made from this feed using the method shown in Example 1, and 5 cc of this extract was taken into another test tube, and the same enzyme reaction as above was carried out at 37°C at pH 5.0 for 30 minutes. ,L-
After conversion to ascorbic acid, 20 μQ of each solution was analyzed by high performance liquid chromatography to measure the amount of residual ascorbic acid, which was designated as B.

Take the ratio B/A for each ascorbic acid and calculate the value of A, /B, which is the reciprocal of the ratio B, /A, of L-ascorbic acid-2-pyrophosphate tetrasodium salt, and each ascorbic acid. The amount of residual ascorbic acid was compared by taking the product of the B/A values, and the results are summarized in Table 2.

Margin Table-2 Below: From this experiment, compared to other ascorbic acids, L-
It was confirmed that ascorbic acid-2-pyrophosphate tetrasodium salt exhibits extremely high stability in extruder granulated feed.

(Example 3) The following experiment was conducted to confirm whether each of the animals shown in Table 3 retained the enzyme activity to decompose AP into L-ascorbic acid in the body.

2cc of blood or lymph from each animal shown in Table-3
Collect it and put it in a Lace test tube, and add 002 to this test tube.
Add 2 cc of physiological saline containing ascorbic acid-2 pyrophosphate tetrasodium salt at a concentration of 4%.
It was set as cc.

20 μQ of this solution was taken and subjected to high performance liquid chromatography to quantify mono-ascorbic acid-2-pyrophosphate, and this value was designated as C.

Next, this solution was left at 37°C for 1 hour, and then 20μ
Q was taken and similarly L-ascorbic acid-2-pyrophosphate was determined by high performance liquid chromatography, and this value was designated as D.

If this D is organically reduced compared to C, it is thought that L-ascorbic acid-2-pyrophosphate ester has been degraded by an enzyme, and therefore there is enzyme activity that decomposes AP into L-ascorbic acid. Assuming that Table 3 shows (+
). If there is no change in C and D, set AP to L-
Assuming that there is no enzyme activity to decompose it into ascorbic acid (
−).

From the results shown in Table 3, it was confirmed that the enzyme activity that decomposes L-ascorbic acid-2-pyrophosphate into 7-ascorbic acid exists in a wide range of animals.

〔Effect of the invention 〕

As explained above, the extruder granulated feed according to the present invention contains A P (L-ascorbic acid-2) in the feed.
-Pyrophosphate ester or its salts), and this AP has extremely high thermal stability compared to ascorbic acid-2=sulfuric acid esters and ascorbic acid 2-phosphate esters, and It is not decomposed even under high temperature and high pressure inside the granulator, and can remain in the feed after granulation at a high residual rate.It is also taken into the living body along with the feed, and when absorbed, it is quickly converted to mono-ascorbic acid. It can be converted and exhibit its activity as vitamin C. Therefore, the extruder granulated feed according to the present invention can sufficiently retain the activity of vitamin C in the feed and inorganic phosphoric The amount of released can be extremely reduced.

In other words, it is possible to contain AP in a mixed state with other feed ingredients before granulation in the extruder, which greatly simplifies the manufacturing process compared to feed made by adsorbing L-ascorbic acid after granulation. can do.

Furthermore, AP is extremely stable against air oxidation compared to ascorbic acid, and can prevent the disadvantage that the activity of vitamin C in feed decreases over time during the distribution process.

In addition, since AP can be uniformly dispersed in granulated feed, losses caused by ascorbic acid on the surface of the feed decomposing or eluting into water when added to water can be greatly reduced. It is possible to improve the activity efficiency of L-ascorbic acid in feed.

Claims (1)

[Claims] An extruder granulated feed characterized by containing L-ascorbic acid-2-pyrophosphate or its salts.