JPH04171035A - Formation of waterproof film and waterproof substance - Google Patents

Abstract

PURPOSE:To provide waterproofness to a substance susceptible to the change of properties in response to the reaction of a water system by adding a specific mixture B to a specific mixture A, reacting components of the mixture B to seal the substance with a fatty acid metal salt powder of the mixture A and coating the particle surface of the sealed substance. CONSTITUTION:A mixture A is prepared by adding 0.01 to 100 pts.wt. of a fatty acid metal salt powder to 1 pt.wt. of a substance and separately a mixture B is prepared by adding 0.5 to 2 equivalents of a metal compound to 1 equivalent of a fatty acid. 0.01 to 1 pt.wt. of the mixture B is slowly added to 1 pt.wt. of the mixture A and they are mixed at 40 deg.C to 120 deg.C. Simultaneously, components of the mixture B are reacted to form a fatty acid metal salt anew, permitting the substance to be sealed with a fatty acid metal salt powder of the mixture A and the particle surface of the sealed substance to be coated to form a waterproof film. A waterproof substance can be obtained according to this procedure.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides a method for forming a water-resistant film on a substance useful in various fields such as livestock, fisheries, agriculture, food, medicine, and household products, and a method thereof. Relating to a water-resistant material obtained by the method.

[Conventional technology]

There are many cases where substances are not soluble in aqueous media until they are placed in the conditions for which they are intended to be used, and require water resistance or water insolubility, particularly in areas such as livestock, fisheries, agriculture, food, medicine, and household products. There are many demands.

For example, in livestock farming, it is widely practiced to orally administer various water-soluble physiologically active substances and allow them to be absorbed in the digestive tract so that the substances can exert their own physiological effects. In fact, for livestock such as pigs, protein and simple amino acids are added to feed to shorten fattening time and improve meat quality. However, in animals such as cattle, when these water-soluble physiologically active substances are orally administered as they are, they are denatured and degraded by the microorganisms that coexist in the rumen, and the abomasum where amino acids and other substances should be absorbed. Not only does it not reach the subsequent digestive organs, but a large amount of harmful substances such as ammonia are generated, which harms the health of the animals, making it impossible to achieve the original purpose.

In order to solve this problem, water-soluble physiologically active substances are dispersed in the protective substance in order to reach the digestive organs after the abomasum without being decomposed in the rumen, that is, to provide rumen bypass properties. A method of administering granular materials has been adopted.

On the other hand, in aquaculture fisheries, it is necessary to prevent aquaculture feed such as oil and protein from dissolving or diffusing into the water, reducing the feeding rate of fish and shellfish, and at the same time, to prevent aquaculture water from being contaminated or spoiled. Efforts have been made to impart appropriate water resistance to bait.

In addition, in fields such as agriculture, food, medicine, and household products, useful water-soluble substances gradually dissolve in aqueous media or dissolve at certain pH levels.
Appropriate water resistance is imparted so that water-soluble substances are released into the aqueous medium only when the area is out of range.

Japanese Patent Publication No. 43-11362 proposes hardened vegetable fats and bran wax as protective substances; for example, DL-methionine, kaolin, and stearic acid are slurried,
This is coated with hydrogenated vegetable fat using a centrifugal extrusion device. Furthermore, JP-A No. 47-38467 proposes coating proteins such as methionine, glucose, physiologically active substances such as fats and oils with fatty acids having 14 or more carbon atoms or their salts, and JP-A No. 53-127819 proposes The publication describes a method of mixing L-ascorbic acid with a melt of fats and oils with a melting point of 50°C to 80°C, lecithin, and glycerin fatty acid monoester, and cooling and powdering the mixture, as described in JP-A-56-1.
No. 54956 discloses a method in which a fatty acid having 14 to 22 carbon atoms, ricinoleic acid, or a salt thereof (sodium salt, potassium salt, calcium salt) and a physiologically active substance (for example, methionine) are melt-mixed, and the mixture is cooled and granulated. is proposed. In addition to these, Japanese Patent Application Laid-Open Nos. 59-66843, 59-198946, and 63-29550
Publication No. 7, Publication No. 63-294747, Publication No. 63-31
No. 3546, No. 63-313547, No. 63
-317050 publication, 63-317052 publication,
63-317053, etc., but most methods involve melt-mixing physiologically active substances with various high-melting-point oils and fats, fatty acids, or fatty acid salts, cooling them, and then granulating them.

(Problem to be Solved by the Invention) However, with the method according to the above-mentioned prior art, it is possible to achieve most of the objectives in the case of relatively hydrophobic substances;
In the case of highly water-soluble substances such as lysine hydrochloride, cracks occur due to shrinkage when the molten mixture is cooled and solidified, and water-soluble substances elute through these cracks, and furthermore, water penetrates and the internal pressure of the particles increases. This has the disadvantage that the coating particles are destroyed.

As a result of repeated research on this problem, the present inventors previously proposed in Japanese Patent Application No. 1-178040 that a water-soluble substance is coated with a fatty acid and a metal oxide powder, and then water is added to produce a fatty acid metal salt. We proposed a coating method using

However, in order to impart sufficient hydrophobicity to a water-soluble substance, it is necessary to form a very large amount of coating layer, and there is a drawback that it takes an extremely long time to obtain a water-resistant substance. In other words, if you try to coat with a large amount of fatty acid metal salt at one time, the whole will stick firmly and form a huge lump, and if you reduce the amount of fatty acid metal salt used in one operation, it will not be enough. It was found that in order to form a protective film, it is necessary to repeat the coating operation many times. [Means for solving the problem] The present inventors conducted further research to solve the above problem. As a result, we have arrived at the present invention.

That is, the present invention provides a method for imparting water resistance to a substance by coating the substance with a fatty acid metal salt, in which (1) fatty acid metal salt powder is added at a ratio of 0.01 to 100 parts by weight per 1 part by weight of the substance; In addition, a mixture A is prepared, and separately (2) fatty acid 1
Mixture B is prepared by adding the metal compound at a ratio of 0.5 to 2 equivalents, and (3) 80.01 to 1 part by weight of the mixture is gradually added to 1 part by weight of mixture A at 40°C to 120°C. At the same time, the substance and the powder of the fatty acid metal salt of Mixture A are fixed together by reacting the components of Mixture B to newly generate a fatty acid metal salt, and at the same time coating the surface of the particles of the fixed substance. A method for forming a water-resistant film characterized by the following, and a water-resistant substance obtained by the method for forming a water-resistant film.

The method for forming a water-resistant film of the present invention can be applied to any substance to be coated, and can be applied for the purpose of protecting substances that are decomposed and altered by reaction in an aqueous system.

Substances targeted by the present invention include not only substances with low water solubility or hydrophobicity, but also substances with high hydrophobicity, regardless of whether they are organic or inorganic.

The method for forming a water-resistant film of the present invention is particularly applicable to physiologically active substances, such as physiologically active substances that are easily altered and decomposed by microorganisms living symbiotically in the rumen when orally administered to a ruminant animal.

These physiologically active substances include feed such as protein, amino acids and derivatives thereof such as methionine, lysine, tryptophan, threonine, glutamic acid, and aspartic acid, fatty acid salts such as vitamin A and vitamin A acetate,
Vitamin B, vitamin C, vitamin D2, vitamin D3
, vitamin E, nicotinic acid and other vitamins and their derivatives.

In addition to antibiotics such as penicillin, there are substances containing physiologically useful elements such as calcium, iron, and phosphorus.

The method of the present invention can be applied to a solid substance as it is, or can be applied to a liquid substance after being impregnated with another solid substance or powder.

In the method of the present invention, the fatty acids constituting the fatty acid metal salt used in the mixture A and the fatty acids used in the mixture B are saturated or unsaturated fatty acids having 4 to 30 carbon atoms, or mixed fatty acids thereof, including animal oils and vegetable oils. These include fatty acids obtained from natural oils and fats such as beef tallow fatty acid, palm oil fatty acid, rapeseed oil fatty acid, coconut oil fatty acid, fish oil fatty acid, and fatty acids obtained from these fatty acids through physical and chemical operations such as distillation, fractionation, and hydrogenation. and so on. The fatty acids constituting the fatty acid metal salt used in mixture A and the fatty acids used in mixture B may be the same fatty acid, or may be different fatty acids.

The metals constituting the fatty acid metal salt used in mixture A and the metals constituting the metal compound used in mixture B are metals that exhibit water-insolubility or hydrophobicity when converted into salts of the fatty acids described above, and include calcium, magnesium, lithium, Metals include barium, cadmium, zinc, lead, copper, mercury, iron, chromium, nickel, and aluminum.

The metal compound for obtaining the fatty acid metal salt used in the mixture A of the present invention and the metal compound used in the mixture B are organic or inorganic compounds of these metals, and oxides, hydroxides, etc. are particularly preferred. The metal compound for obtaining the fatty acid metal salt and the metal compound used in mixture B may be the same metal compound or may be different metal compounds.

The fatty acid metal salt used in the mixture A of the present invention is a compound in which the above-mentioned fatty acid and the above-mentioned metal form a salt.The fatty acid metal salt used in the mixture A of the present invention is a compound in which the above-mentioned fatty acid and the above-mentioned metal form a salt. metathesis method, which generates and liberates hydrophobic fatty acid metal salts by adding
It is obtained by a manufacturing method such as a wet method in which a fatty acid and a metal compound are reacted in an aqueous medium. Further, in order to carry out the present invention more effectively, it is preferable that the fatty acid metal salt used in mixture A is in a powder state.

In the reaction of producing a fatty acid metal salt from the mixture B of the present invention, water, a catalyst, etc. that are absolutely necessary for carrying out the reaction may be added. For example, when a metal oxide is reacted, a small amount of water is added to convert it into a metal hydroxide, which is then reacted with a fatty acid, but once a fatty acid metal salt is produced, water is produced again and the reaction proceeds further.

In order to remove volatile components such as water from the water-resistant material obtained in this way, heating operation, depressurization operation, etc. can be added to remove volatile components.

The obtained water-resistant material is often more elastic than the original material and becomes larger particles, so if fine particles are required, the obtained water-resistant material is pulverized. Furthermore, if large particles are required, the large particles can be sorted out using a filter, and the remaining fine particles can be made into large particles by a method such as reprocessing using the method of the present invention.

〔Effect of the invention〕

By the method of the present invention, water resistance can be imparted to substances that are susceptible to deterioration in aqueous reactions, and the obtained water-resistant substances can be effectively utilized because they are stable in aqueous systems.

〔Example〕

Examples of the present invention will be described below to explain the present invention more specifically.

Example 1 This experiment was carried out using highly water-soluble lysine hydrochloride (manufactured by Ajinomoto ■).

Mixture A having the composition shown in Table 1 was placed in a fluidized mixing type granulator (high speed mixer LFS-GS-IJ manufactured by Fukae Kogyo N).
Mixture B with the composition shown in Table 1 heated to 80°C and water were gradually added and reacted, and the resulting product was put in a granulator to form a sample. No
, 1 to No. 12 were obtained.

As the fatty acid calcium fatty acid of mixture A and the fatty acid of mixture B, palm oil fatty acids were used.

The water resistance of the obtained sample was evaluated based on the elution rate of lysine hydrochloride with respect to water.

Measurement of elution rate Add 200ml of distilled water and 8g of sample to an eggplant flask.
After heating at 39°C for 10 minutes at an amplitude of 7 cm and 90 cycles per minute, it was filtered through a 200 mesh filter, and lysine in the filtrate was colored with ninhydrin.
The dissolution rate of lysine hydrochloride contained in the sample was determined by visible light absorption colorimetry of m.

Table 1 shows the particle size and dissolution rate of the sample.

Samples No. 1 to No. 004 of the present invention all have a low elution rate and are provided with excellent water resistance.

Comparative samples No. 005 to No. 12 showed no granules, or even if granules were obtained, a high dissolution rate was obtained, and water resistance was not imparted.

Example 2 The test was carried out using DL-methionine (manufactured by Nippon Soda ■).

Mixture A and mixture B having the compositions shown in Table 2 and water were heated to 80°C.
The mixture was kneaded in a double-arm kneader (manufactured by Irie Shokai Co., Ltd.) whose temperature was raised to obtain a lump. After cooling this lump to room temperature, it was passed through a sieving machine (Crushing and grading machine MG-205 manufactured by Fukae Kogyo ■) to obtain sample No. 5 with an average particle size of 5 mm.

13 to No. 17 were obtained.

Measurement of dissolution rate The dissolution rate was determined in the same manner as in Example 1, except that the shaking time was 1 hour.

Table 2 shows the elution rate, and samples No. 13 to No. 1 of the present invention,
No. 15 shows a low dissolution rate and is endowed with excellent water resistance. Comparative samples No. 16 and No. 17 showed a high elution rate and were not provided with water resistance.

Table 2 Note 1) Fatty acid is palm oil fatty acid.

Example 3 The test was carried out using powdered silica (manufactured by Nippon Silikani Gyogyo ■).

Using mixture A and mixture B having the compositions shown in Table 3, the treatment was carried out in the same manner as in Example 1. Sample No. 18
~ No. 21 was obtained.

Hydrophobicity Evaluation Put 100ml of water and 5g of the sample in a beaker, stir gently several times with a spa chiller, and then check the dispersion state. The results were evaluated based on the following criteria.

Condition evaluation 0: All floating, excellent Δ: Partially suspended, inferior ×: All suspended Very poor The evaluation results are shown in Table 3. Sample No. of the present invention.

Samples No. 18, No. 19, and No. 19 are suspended in water and have excellent hydrophobicity, but comparative samples No. 20, No. 21, and No. 19 are suspended in water and have excellent hydrophobicity.
is not given hydrophobicity.

Table 3 Patent applicant: NOF Corporation

Claims (1)

[Claims] 1. A method for imparting water resistance to a substance by coating the substance with a fatty acid metal salt, in which (1) 0.01 to 100 parts by weight of fatty acid metal salt powder is applied to 1 part by weight of the substance; Separately, (2) a metal compound was added at a ratio of 0.5 to 2 equivalents to 1 equivalent of fatty acid to prepare a mixture B, and (3) at 40°C to 120°C. 0.01 to 1 part by weight of Mixture B is gradually added and mixed to 1 part by weight of Mixture A, and the components of Mixture B are reacted to newly generate a fatty acid metal salt, thereby forming the substance and the fatty acid metal salt of Mixture A. A method for forming a water-resistant film, the method comprising fixing the powder and simultaneously coating the surface of the particles of the fixed substance. 2. A water-resistant substance obtained by the method for forming a water-resistant film according to claim 1.