JPH07119191B2 - Method for stabilizing menadione bisulfite and composition of menadione bisulfite - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for stabilizing menadione bisulfite and a menadione bisulfite composition. Menadione bisulfite has not only blood coagulation action, but also potentiating the effect of steroid hormones to enhance anti-inflammatory action, so it is not only used as a medicine for therapeutic purposes but also for vitamin K supplementation in livestock feed. It is a compound useful as an additive.

[Prior Art] 2-Methyl-1,4-naphthoquinone belonging to vitamin K is also called menadione or vitamin K ₃ and is one of the vitamins having a blood coagulating action and is used as a drug or a livestock feed additive. It is useful. However, menadione has low heat and light stability, and this tendency is remarkable especially when it is used in combination with other additives such as choline chloride. In addition, since it is insoluble in water, it has a drawback that it is difficult to mix it uniformly, for example, when it is mixed with feed. Therefore, usually, particularly when used as a feed additive, a compound obtained by adding bisulfite of an alkali metal or an alkaline earth metal to menadione,
For example, it is used in the form of menadione sodium bisulfite (MSB).

MSB has the same good blood coagulation action as menadione, is water-soluble, and has improved stability compared to menadione, but it is still not sufficiently stable against water, heat, and light. I can not say. Therefore, it has been attempted to react menadione bisulfite with an appropriate weakly basic compound to improve its stability. For example, menadione dimethylpyrimidinol bisulfite (MPB) obtained by the reaction of MSB and 2-hydroxy-4,6-dimethylpyrimidine is one example thereof, but MPB is found to have improved stability but is not soluble in water. It has a drawback that it becomes low and the compoundability becomes poor.

[Problems to be Solved by the Invention] Therefore, the present inventors have conducted various studies for the purpose of obtaining the same effect as improving the water solubility and further improving the stability thereof. That is, an object of the present invention is to provide a method for stabilizing menadione bisulfite while maintaining the distributability to feed and the like, and a stabilized composition.

[Means for Solving the Problems] A method for stabilizing menadione bisulfite according to the present invention, which has solved the above problems, is menadione bisulfite having a water absorption ratio of 1 g.
(Water) / g or more capacity, and pH of 5g (water) / g mixture
Water-absorbing polymer substance (hereinafter referred to as mixture pH) within the range of 6 or less and 1 or more (hereinafter referred to as water-absorbing polymer substance)
The main point is that the menadione bisulfite composition of the present invention is prepared by supporting menadione bisulfite salt on a water-absorbing polymer.

That is, according to the present invention, menadione bisulfite is
-Menadione bisulfite is supported on a water-absorbing polymer without the need to react with -hydroxy-4,6-dimethylpyrimidine, etc. to lead to a new derivative or to perform surface treatment such as coating with mineral oil. The stabilization of menadione bisulfite can be achieved only by such a simple operation. The details will be described below.

As the water-absorbing polymer substance used in the present invention,
Any polymer substance which is harmless to humans and animals and has a property of absorbing and swelling water or an aqueous solution or a vapor thereof to form a hydrogel and having a mixture pH of 6 or less and 1 or more may be used. As such a water-absorbing polymer substance,
For example, starch-acrylonitrile graft copolymer hydrolyzate, acrylic acid ester-vinyl acetate copolymer saponification product, acrylonitrile copolymer or acrylamide copolymer hydrolyzate, starch-acrylic acid graft polymer, self-polymerization Examples thereof include crosslinked polyacrylic acid, polyacrylic acid crosslinked products, crosslinked isobutylene-maleic anhydride copolymers, and partially neutralized products of these polymers. Among them, polyacrylic acid type polymer substances are preferable because they are easily available. The pH of the mixture of these macromolecular substances depends on the amount of protons that can be released from the carboxy groups present in the macromolecular substance, and this depends on the chemical structure of the monomer before polymerizing the macromolecular substance or the post-polymerization step. It can be adjusted by neutralizing an appropriate amount with a basic substance such as sodium hydroxide or by acid treatment. Mixture pH
If a water-absorbing polymer having a ratio of greater than 6 is used, the desired stability of menadione bisulfite cannot be obtained. Of course, it is effective to support menadione bisulfite in a state where the pH of the mixture, which is the requirement of the present invention, becomes 6 or less by heat-treating even a water-absorbing polymer substance having a mixture pH of more than 6. Also, when the pH of the mixture is lower than 1, the stability of menadione bisulfite is lowered.

For the unique properties of the water-absorbing polymer, see the mixture above.
In addition to pH, water absorption capacity can be mentioned.
It is preferable that it has a capacity of 1 g (water) / g or more. When the water absorption capacity is less than 1 g (water) / g, in the present invention, for example, a carrying method is performed in which a water-absorbing polymer substance is allowed to absorb an absorbable amount of menadione bisulfite aqueous solution or less and then dried. In such a case, a sufficient amount of menadione bisulfite is not supported by one-time loading, and a large amount of water-absorbing polymer substance is required to support a fixed amount of menadione bisulfite.

Furthermore, the water-absorbing polymer substance is preferably granular,
Specifically, it is desired that the particle size when dried is 10 μm or more and 1000 μm or less, and more preferably 50 μm or more and 500 μm or less. By using such a granular water-absorbing polymer substance, there is an advantage that grinding after menadione bisulfite absorption and drying is very easy or unnecessary, and a menadione bisulfite composition having a relatively uniform particle size is obtained. Not only the obtained operability in the stability improving treatment is improved, but also the stability of menadione bisulfite supported on the water-absorbing polymer is improved.

In the present invention, various additives may be added to the menadione bisulfite-supporting composition. For example, when the menadione bisulfite-supporting composition obtained by the present invention is used as an additive for poultry feed, it is possible to add a coloring agent, and poultry can be efficiently colored if the poultry prefers it. Has the effect of being ingested by. Further, in this case, since the light shielding effect is obtained by coloring, the effect of improving the stability of menadione bisulfite is also obtained. It is also possible to mix other vitamins and drugs together, and it is particularly effective to absorb a water-soluble drug or a liquid substance such as ethyl alcohol and use it as a feed additive.

Next, a method for supporting menadione bisulfite on an absorptive polymer will be described. The method of supporting is not particularly limited and may be simply mixing, but it is preferable to follow the method described below.

First, menadione sulfite is dissolved in water or an aqueous acid solution,
Make menadione bisulfite aqueous solution. The concentration of menadione bisulfite contained in the aqueous solution of menadione bisulfite is preferably not more than the solubility of menadione bisulfite. If it is used in a suspended state having a solubility or higher, uneven loading occurs when it is absorbed by a water-absorbing polymer substance, and sufficient stability cannot be obtained. In addition, the bisulfite aqueous solution 10
An organic or inorganic acid of about wt% may be added, in which case the stability of the menadione bisulfite aqueous solution is further improved.

Next, the water absorbent polymer substance is made to absorb the above menadione hydrogen sulfite aqueous solution.

The amount of the menadione bisulfite aqueous solution is determined by the concentration of menadione bisulfite contained therein, the water absorbable amount of the water-absorbing polymeric substance and the target carrying amount,
If the amount of the menadione bisulfite aqueous solution is too large, the utility cost for drying becomes high, and for example, if the amount of the water-absorbent polymer substance exceeds the absorbable amount, it is difficult to carry the target amount of menadione bisulfite. Becomes On the other hand, if the amount is too small as compared with the amount of the water-absorbing polymer substance, uneven loading of menadione bisulfite will occur. Usually, it is advisable to absorb a menadione bisulfite solution having a maximum water absorption amount or less, for example, 1 to 50 times by weight of the water-absorbing polymer substance.

The resulting water-absorbent polymer composition is dried if necessary. The drying method is carried out by a known method, but the drying temperature is preferably 60 ° C. or lower for the purpose of preventing the denaturation of menadione bisulfite during drying, and for example, vacuum drying is also effective. The dried composition may be ground to a desired particle size, if necessary.

The present invention will be described in more detail with reference to the following examples, but the following examples are not intended to limit the present invention, and any modification or implementation within the scope of the gist of the preceding and the following is included in the technical scope of the present invention. It

Example 1 Example 1 25 wt% MSB in 40 parts by weight of a water-absorbing polymer substance (sodium polyacrylate, pH value of mixture 2.5) having a particle size of 100 to 200 μm
The gel-like substance obtained by absorbing 400 parts by weight of the aqueous solution is
It was dried under reduced pressure at 20 ° C. and a pressure of 20 μmHg. The obtained substance was easily crushed into a white porous material to obtain white granules carrying 65% by weight of MSB.

Example 2 400 parts by weight of a 25 wt% MSB aqueous solution containing 0.01 part of a red colorant (Edible Red No. 2) was absorbed in 40 parts of the same water-absorbing polymer as in Example 1 to obtain a red gel-like substance. 40 ° C, pressure
It was dried under reduced pressure at 20 mmHg. The obtained red porous material was easily pulverized to obtain red granules carrying 64% by weight of MSB.

Stability test Test 1 The MSB-supported materials obtained in Example 1 and Example 2 and unstabilized commercially available MSBs were placed in open glass containers, respectively, and allowed to stand under the following conditions for comparative observation of changes with time of MSB. did.

Temperature: 35-45 ° C Relative humidity: 70-80% The results are shown in Fig. 1.

As shown in FIG. 1, Examples 1 and 2 showed a MSB residual rate of 98% or more after 20 days, but in the case of MSB alone, the residual rate decreased to 80% after 20 days. Was there.

Test 2 Mixed feed base material 1k consisting of corn flour / soybean flour / rice flour
In g, the following amounts of choline hydrochloride, vitamins and Example 1
Alternatively, the stability test was performed under the same conditions as in Test 1 for the MSB-supported material obtained in Example 2 or a mixture of unstabilized commercially available MSB.

Vitamin A 1,000,000 IU Vitamin D ₃ 2000,000 IU Vitamin E 1,000 IU Vitamin B ₁ 0.4 g Vitamin B ₂ 2 g Vitamin B ₆ 0.4 g Choline hydrochloride (50%, support SiO ₂ ) 300 g Example 1 or Example 2 FIG. 2 shows the results of 2 g of the MSB-supported material obtained in 1. or the unstabilized commercial MSB (converted to menadione).

As shown in FIG. 2, MSB compounded in the feed without being supported by the water-absorbing polymer showed a remarkable decrease in the residual rate as compared with the case of using it alone, but in Examples 1 and 2, 20 days passed. Even after
It showed an excellent residual rate of 95% or more.

[Advantages of the Invention] The present invention is configured as described above, and can impart excellent stability to menadione bisulfite by a simple method of supporting menadione bisulfite on a water-absorbing polymer. I can do it now. Moreover, the menadione bisulfite composition obtained by this method can be easily and uniformly dispersed in feed or the like.

[Brief description of drawings]

1 and 2 are graphs showing the relationship between the elapsed days and the MSB residual rate in stability tests 1 and 2, respectively.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Noriaki Ikeda No. 992, Nishikioki, Kamahama, Aboshi-ku, Himeji-shi, Hyogo Prefecture 1 Catalytic Research Laboratory, Nippon Catalysis Chemical Industry Co., Ltd. Address No. 1 inside Catalytic Research Institute of Nippon Catalysis Chemical Co., Ltd. (72) Inventor Akira Inoue No. 992 No. 1 Nishikioki, Okehama, Aboshi-ku, Himeji City, Hyogo Prefecture

Claims (2)

[Claims] 1. A water absorption capacity of 1 g of menadione bisulfite.
(Water) / g or more capacity, and pH of 5g (water) / g mixture
The method for stabilizing menadione bisulfite is characterized in that it is supported on a water-absorbing polymer substance having a ratio of 6 or less and 1 or more. 2. A water absorption capacity of 1 g of menadione bisulfite.
(Water) / g or more capacity, and pH of 5g (water) / g mixture
6. A menadione bisulfite composition, wherein the menadione bisulfite composition is supported on a water-absorbing polymer substance having a ratio of 6 or less and 1 or more.