KR20080007202A - Technology of vitamins onto porous chitosan beaols - Google Patents

Abstract

A chitosan gel suitable for the nutrient component of a composite feed for animals, its preparation method, a chitosan nutrient suitable for the nutrient component of a composite feed for animals, and its preparation method are provided to allow vitamin C and vitamin E to be added to a feed. A method for a chitosan gel suitable for the nutrient component of a composite feed for animals comprises the steps of making a powder from chitosan flake, mixing the obtained chitosan powder with a weak acidic aqueous solution to react them, thereby preparing a chitosan colloid having a low molecular weight; injecting the chitosan colloid into an alkali aqueous solution to react them, thereby gelling it; and washing the gelled chitosan with water several times.

Description

Immobilization of Vitamins Using Chitosan Beads {Technology of vitamins onto Porous chitosan Beaols}

 The present invention relates to a chitosan gel suitable for animal feed by processing chitosan flakes, and a chitosan nutrient suitable for animal feed having improved functionality by combining nutrients such as mineral vitamins to the chitosan gel, and a method for producing the same.

        In general, animal feed can be divided into animal feed as terrestrial animal and fish feed as marine animal, but these are all added with various feed additives to promote the growth of the carcass and improve the efficiency of the feed. have. As a nutritional supplement for feed, the main components are various kinds of vitamins and chitosan.

        Vitamins are important nutrients for fish, showing effects such as prevention of scurvy, fertilization rate, hatching rate, survival rate, upbringing improvement, prevention and reduction of various stresses from the environment, strengthening of immune function (anti-medical history), antioxidant activity, and liver protection. However, vitamins are easily destroyed under conditions such as heat, light, air, and moisture, and there is a problem that 50 -90% is lost when preparing a compound feed, and thus a supplemental vitamin is required.

       On the other hand, chitosan was obtained by deacetylating chitin contained in crabs, crayfish, and shrimp shells.In 1811, French historian Bracono discovered the unknown chitin contained in mushrooms. The chitin was newly obtained by chemist Rage acetylating in 1859, which is the chitosan commonly known today. These properties of chitosan are well known for activating depleted cells, inhibiting aging, strengthening immunity, preventing diseases, and regulating biorhythms along with the functions of activating the natural healing ability of living organisms. .

       In the case of applying such chitosan to fish, chitosan is effective in increasing fish body length and weight, promoting the growth rate, activating liver function, inhibiting the growth of pathogenic bacteria (antibacterial), regenerating damaged tissues and increasing the history of disease and digestion. It has been reported to show many effects such as enhanced function and cholesterol removal.

      Therefore, the feed for fish that is commonly used today is focused on producing a compound feed containing the vitamin and chitosan as essential nutrients.

      Conventional feeds currently commercially available are three types, injection pellet type, wet pellet type and simple pellet type, and are commercially available by adding various vitamin components thereto. It is becoming.

       In general, a method of administering various vitamins to fish is dissolved in water at a desired concentration (about 300 ppm), and then the vitamin is attached to the feed and administered. However, vitamin components are classified into water-soluble vitamins and fat-soluble vitamins based on their solubility, and they have heterogeneous properties with respect to their solubility.

       For example, in the case of a conventional injection pellet compound feed, the outer surface is coated with a fat-soluble component so that the compound feed does not easily loosen in water. Therefore, vitamin C or vitamin E dissolved in water does not adhere well to the surface of the blended feed and inevitably use a binder in order to overcome this situation. However, when the binder is added to attach the vitamin component to the surface of the blended feed, the cost must be paid additionally, which adds to the economic burden of fishermen, and the resulting efficiency is not high.

       In contrast, the wet pellet-type or simple pellet-type blended feed is manufactured without coating the outer surface thereof. Therefore, there is an advantage that can easily attach vitamin C and vitamin E to the outer surface of the blended feed. However, this type of compound feed has a low adhesion amount of vitamin C or vitamin E, and the compound feed is easily dissolved in water when the vitamin compound is attached to its outer surface and then administered to the fish. Since it is discarded, the economic loss is enormous, and there is a disadvantage in that the water quality is contaminated by the dissolved compound feed.

       On the other hand, looking at the formulations developed based on such a conventional method, Korean Patent Laid-Open No. 1999-24835 "chitosan oligosaccharides containing a feed additive composition"; Korean Patent Publication No. 1999-40962 "Aquaculture feed and aquaculture method for improving the immunity of fry"; Korean Patent Application Laid-Open No. 2000-24835 "Feeding nutritional composition for feed containing chitosan oligosaccharides"; In addition, Korean Patent Registration No. 171246 “chitin, chitosan and chitosan oligosaccharide-containing feed composition for fish” can be found.

       Among them, the Republic of Korea Patent Publication No. 1999-15681 "anti-pathological feed of fish farming" is converted to a low molecular weight chitosan by treating a high molecular weight chitosan having an molecular weight of about 100,000 with an organic acid, such low-molecular chitosan and diatom extract and Lecithin is added to the feed. However, this method is considered to be the focus of the invention simply to convert high molecular weight chitosan into organic acid and increase its absorption rate, and there is no mention of vitamin component.

       Patent Publication No. 1999-40962 "Aquaculture feed and fish farming method for improving the immunity of fry" is pre-mixed by adding 0.005 ~ 0.015% by weight of vitamin B1 and B2 to 1-5% by weight of chitosan solution, It discloses a method of adding 0.5 to 2% by weight to the existing fry feed. However, although this method is described as pre-mixing the vitamin component to the chitosan solution, it does not disclose a specific method and appears to be mixed in a conventional manner as in the prior art.

       On the other hand, the above-mentioned Patent Publication No. 2000-24835 "chitosan oligosaccharide-containing dietary nutritional supplement composition" by adding chitosan oligosaccharides to the general vitamin agent useful effect of the vitamin agent and antimicrobial action, immune enhancing action and anti-potentiation effect of chitosan oligosaccharides Various vitamin components are enumerated, insisting that synergistic effects such as promoting the growth of animals, improving feed efficiency, improving weight gain, and enhancing immunity can be achieved. However, the specification does not mention at all how the chitosan oligosaccharides and various vitamin components are combined or reacted with each other.

       On the other hand, the Republic of Korea Patent Registration No. 171246 "chitin and chitosan oligosaccharide-containing feed composition for livestock, fisheries" is to decompose chitin or chitosan by enzymatic method, so that the water-soluble degree of polymerization as a physical property of 2 to 10 chitin, chitosan oligosaccharides Introduced in liquid or powder form and added to feed or drinking water. However, this method also aims to improve the absorption rate of chitosan by treating chitosan in an enzymatic manner, and there is a disadvantage that the vitamin component is not mentioned at all.

   As described above, the conventionally used animal feed or fish feed for animal husbandry is a mixture of chitosan and vitamin components independently, or they are simply mixed with each other in a conventional manner. This water-soluble component and a fat-soluble component has a disadvantage that does not overcome the fact that they have opposite properties.

       Accordingly, it is an object of the present invention to convert to high molecular weight chitosan and to prepare insoluble chitosan in gelled form. When the chitosan is converted to low molecular weight, there is an advantage that the carcasses such as fish can easily digest it.

       It is also an object of the present invention to provide a chitosan nutrient which is particularly suitable for an animal feed containing a vitamin component and a chitosan component by physicochemically reacting the gelated chitosan with a water-soluble vitamin and a fat-soluble vitamin.

 The present invention relates to a chitosan gel suitable for animal feed by processing chitosan flakes, and a chitosan nutrient suitable for animal feed having improved functionality by combining nutrients such as mineral vitamins to the chitosan gel, and a method for producing the same.

       The present invention comprises the steps of pulverizing chitosan flakes and mixing them in a weakly acidic aqueous solution and reacting them with each other to produce a low molecular weight chitosan colloid; Adding the chitosan colloid to an alkaline aqueous solution and reacting and gelling the same; Washing the gelled chitosan by washing with water several times; It provides a chitosan gel prepared by the above method and a method for producing a chitosan gel particularly suitable as a nutritional component of the animal feed containing.

 Chitosan gel according to the present invention not only has a large number of functional groups on the surface, but also has a number of fine pores, various mineral components and vitamin components can be combined by physical and chemical methods. Therefore, according to the production method of the present invention and the chitosan gel produced by the method, there is an advantage that the water-soluble substance and the fat-soluble substance which can not be combined with the conventional method can be combined at the same time.

       Moreover, according to the functional chitosan gel which concerns on this invention, various mineral components and various vitamin components can be combined simultaneously efficiently. Therefore, it is possible to efficiently combine minerals to be added according to the characteristics of the various subjects.

       In addition, according to the chitosan gel according to the present invention, since they are insoluble in water, it is possible to prevent them from being easily released in water, which is particularly advantageous as a nutritional ingredient for fish feed.

In the present invention, the chitosan colloid is subjected to injection molding in the gelation step in order to use it as a feed for fish, so that the chitosan gel is preferably manufactured in a bead shape.

       In addition, the present invention comprises the steps of preparing chitosan beads prepared by the above production method; Dissolving the mineral component and the vitamin component in water to form a nutrient solution, and adding the bead-type chitosan gel to the nutrient solution to physically couple the nutrient component to the chitosan gel; It provides a chitosan nutrients particularly suitable for animal feed including, and a method of manufacturing the same.

       Hereinafter, the method for producing chitosan according to the present invention will be described in more detail and in detail for each step.

       One). Preparation of Chitosan Colloids:

       This is a step of preparing a low molecular weight chitosan colloid by powdering a conventional chitosan flake, mixing the powdered chitosan in a weakly acidic aqueous solution, and then reacting it for a predetermined time. Chitosan is a polysaccharide composed of acetylglucosamine and glucosamine, which is insoluble in water, and is a major component of cell walls and shells such as shellfish, shellfish, etc., and is produced annually by the biological system. In the present invention, the flake form of chitosan is finely powdered. Various types of mills can be used in the chitosan powdering process, and it is preferable to use a powder of about 100 mesh or less in consideration of homogenization and reactivity of the product. In the present invention, an acid solution containing 0.5 to 5 parts by weight of an acidic substance is prepared based on 100 parts by weight of water. In the preparation of the acidic solution, the acidic component does not need to be particularly limited, and the acidic solution can be prepared by adding an organic acid or an inorganic acid. More preferred forms use acetic acid or hydrochloric acid, which is the most readily available on the market.

       In the present invention, 1 to 10 parts by weight of chitosan powder is added to 100 parts by weight of the acidic solution, followed by stirring at room temperature to dissolve the chitosan powder. At this time, when the molecular weight of the chitosan powder is high, the concentration of the acidic component of the acid solution should be increased, and the amount of chitosan powder should be reduced. This is because a viscous chitosan colloidal solution can be prepared under these conditions.

       2). Gelation step of chitosan:

       This is a step in which the chitosan colloid prepared in the above step is added to the alkaline aqueous solution in a predetermined manner, and then reacted with each other for a predetermined time to gel the chitosan. Unlike the conventional method for preparing a conventional feed nutrient, the present invention gelatinizes the low molecular weight chitosan by dipping the low molecular weight chitosan once again in an alkaline aqueous solution. The alkaline aqueous solution used in the present invention can be prepared using a substance having hydroxide ions (-OH). The most preferred hydroxide ion materials are sodium hydroxide (NaOH) and potassium hydroxide (KOH), which are also readily available on the market and commonly used. The hydroxide ion material in the alkaline solution functions as a gelling agent by gelling chitosan in the colloidal form. At this time, the reaction temperature does not need to be particularly limited, but usually 10 to 50 ℃ degree is preferred, it is more preferable to react at a constant temperature. This is because, when reacted at a constant temperature, a more homogenized chitosan gel can be obtained. In addition, it is preferable to stir slowly to promote the reaction of the reactant chitosan and the gelling agent in the reaction process. In addition, the gelation reaction tends to proceed faster as the concentration of the gelling agent increases, and as the reaction temperature increases.

       3). Recovery stage of chitosan:

       When the gelling step is completed, the aqueous solution is discarded to recover the gelled chitosan, and the residue is washed several times with washing water. At this time, the washing water is preferably used purified water or distilled water. This is because the chitosan produced through the gelation step has many micropores in the gelation process. The chitosan gel according to the present invention has a specific surface area of about 250 to 300 m 2 / g from the wet state when it is prepared in a bead shape, and dried to dry it, and its specific surface area is about 3 to 10 m 2 / It was found to form g.

       Since the chitosan reaction product of the above-mentioned various steps is insoluble in water, it is preferable to keep it in distilled water.

The chitosan recovered through these various steps can be easily combined with other functional materials by the functional group (NH ₂ , OH) on the surface of the chitosan and the microbubbles of chitosan, so it is particularly suitable as a nutrient added to animal feed. In addition, it can be used variously as a functional nutritional agent by combining other functional substances. In particular, when the chitosan is prepared from small grains of chitosan beads, the chitosan can be particularly suitably used as a nutrient added to a feed compound of fish.

       In addition, the present invention provides a chitosan nutrient containing vitamins which is particularly suitable for the compounded feed of fish by physically chemically binding the vitamin component to the gelled chitosan. It is manufactured through the following process.

       One). Preparation of Gelled Chitosan Beads:

       It can be prepared in the same manner as the chitosan production method. Therefore, iii). Preparing a chitosan colloid, and ii). Gelation step of chitosan, i). The gelation chitosan beads are prepared by sequentially recovering the chitosan. However, ii) above. In the chitosan i-gelation step, the injection molding method is performed among various molding methods. In the injection molding method, the size of the final chitosan beads can be controlled by the diameter of the nozzle. For the compound feed of fish, the diameter of the chitosan beads is preferably about 0.1 to 0.3 cm. In this case, in order to manufacture chitosan beads, it is preferable to use an injection molding method, and by selecting the injection molding method, the diameter of the beads, the distribution of fine bubble pores in the particles, and the chitosan density inside the beads can be controlled. .

       2). Combined steps of vitamin components:

This is the step of binding the various vitamin components to the chitosan beads by the physical chemical method once the chitosan beads are manufactured through the above steps. To this end, 0.05 to 5 g of various additives are first administered to 1 liter of water, and this is well dispersed. At this time, the above additive contains various mineral components and vitamin components, and the vitamin component is an essential component. In addition, the present invention may include both a water-soluble vitamin and a fat-soluble vitamin. In particular, vitamin-C is preferable as the water-soluble vitamin, and vitamin-E is preferable as the fat-soluble vitamin. In the present invention, the reason why the vitamins having opposite properties can be used simultaneously is that the chitosan prepared in the previous step forms a plurality of functional groups (NH ₂ , OH) and fine bubble pores on the surface thereof in the gelling step. Because there is. The same applies to the use of mineral components.

In the present invention, the mineral component and the vitamin component dissolved in the aqueous solution form chemical bonds by the functional groups (NH ₂ , OH) on the surface of the chitosan gel administered therein, whereas the mineral component and the vitamin component are formed on the chitosan gel. The microbubble holes are physically coupled.

       The chitosan compound completed through such various steps may be particularly useful as a nutrient component suitable for animal feed. Such chitosan compounds may be blended into animal feed by conventional methods to form blended feeds.

       Hereinafter, the most preferred embodiment of the present invention will be described in detail. However, the following examples are only intended to describe the technical spirit of the present invention in more detail, and the technical spirit of the present invention is not limited thereto.

       <Example 1: Preparation of lem type chitosan gel >>

Chitosan powder was prepared by pulverizing a chitosan flake, which is an amine biopolymer having an average molecular weight of 5.2 × 10 ⁵ and a deacetylation degree of about 85%, by passing through a self mill. At this time, the used chitosan flake (flake) was in the shape as shown in Figure 1, this is a photograph taken by magnification 500 times with an electron microscope [Model: JSN 5400 (Jeol)].

       Meanwhile, 2 ml of acetic acid was mixed with 100 ml of distilled water, and then 3 g of the chitosan powder was added thereto, followed by stirring at room temperature to prepare a dissolved chitosan solution. Subsequently, 2 ml of hydrochloric acid at 2 mol concentration was mixed in distilled water to make an alkaline solution, and the colloidal chitosan solution was added dropwise to the alkaline solution. In this case, in order to prepare the gelated chitosan in the form of beads, injection molding method was used, and more specifically, 23GX disposable syringe nozzle manufactured by Korea Vaccine Co., Ltd. was used, while uniformly stirring the loaded chitosan and the alkaline solution. It lasted about a day. Thereafter, the alkaline solvent was discarded and washed 5 or 6 times with distilled water to obtain chitosan beads. The resulting chitosan beads were measured about 0.23 cm in diameter. FIG. 2 is a photograph taken at 300 times magnification with an electron microscope [Model: JSN 5400 (Jeol)] in the lyophilized state of the chitosan beads. FIG. According to the attached enlarged photograph (FIG. 2), it can be seen that a large number of fine bubble holes are formed inside the chitosan beads. The chitosan beads thus prepared were stored in distilled water. This is because when the chitosan beads are allowed to dry at room temperature without being stored in distilled water, the porous structure formed in the chitosan beads collapses and is very hardly changed by shrinking the chitosan beads.

       <Example 2: Preparation of vitamin-containing chitosan beads >>

       A water solution of 300 ppm was prepared by dissolving 0.2 g of vitamin-C and 0.1 g of vitamin-E in 1 L of water. 16 g of chitosan beads (wet state) prepared in Example 1 was added to the aqueous vitamin solution, and stirred uniformly at 25 ° C. at 200 rpm. As shown in FIG. 4, when about 1 hour after stirring, almost all of the vitamin-C was bound to chitosan beads, and the vitamin-E was bound to about 60%. After this procedure, functional chitosan beads were recovered. 3 is a photograph of the functional chitosan beads. It was stored in distilled water for use as a nutritional component of animal feed.

       The chitosan gel according to the present invention and a functional chitosan gel in which various mineral and vitamin components are combined using the same have been specifically described. However, these are only the most preferred embodiments of the present invention, and the present invention is limited thereto. It is not intended to be exhaustive or to be limited to the scope of the appended claims. In addition, anyone of ordinary skill in the art will be able to make various modifications and imitations according to the description of the specification of the present invention, but it will be apparent that this is also outside the scope of the present invention.

 Chitosan (X 500) Model: JSN 5400 (Jeol)

 2. SEM image of freeze dried chitosan beads (X 500) Model: JSN 5400 (Jeol)

 3. Functional Chitosan Feed Combined with Vitamin

 4. Combined experiment of vitamins

Claims (4)

  Method for preparing chitosan gel suitable as nutritional ingredient for animal feed        a). Powdering the chitosan flakes and mixing them in a weakly acidic aqueous solution and reacting them with each other to produce a low molecular weight chitosan colloid;        b). Adding the chitosan colloid to an alkaline aqueous solution and reacting and gelling the same;        c). Recovering the gelled chitosan by washing with water several times; Method for producing a chitosan gel suitable as a nutritional component of the animal feed compound comprising a A chitosan gel suitable as a nutrient for animal feeds, which is prepared according to claim 1.  Method for preparing chitosan nutrients suitable for animal feed,        a). Powdering the chitosan flakes and mixing them in a weakly acidic aqueous solution and reacting with each other to produce a low molecular weight chitosan colloid;        b). Injecting the chitosan colloid into an alkaline aqueous solution by injection molding and reacting the same to gel the beads;        c). Recovering the gelled chitosan by washing with washing water several times;        d). Dissolving the mineral component and the vitamin component in water to form a nutrient solution, and adding the bead-type chitosan gel to the nutrient solution, thereby physically chemically binding the nutrient component to the chitosan gel; Method for producing a chitosan nutrient suitable as a nutritional component of the animal feed formula comprising a. A chitosan nutrient suitable for animal feeds prepared by the method of claim 3 above

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