JPS58113143A - Novel compounded material and its use - Google Patents

Abstract

PURPOSE:A novel compounded material containing propionic acid in a stable form, useful for fungusproofing of feed or food, obtained by blending three components of liquid volatile propionic acid, sodium propionate having high moisture absorbing properties, and calcium propionate having low antifungal properties. CONSTITUTION:(1mol) Propionic acid is blended with (0.1-10mol, preferably 0.25-6.25mol) sodium propionate and (0.1-5mol, preferably 0.5-2.5mol) calcium propionate, heated at 50-140 deg.C, dissolved, and the prepared solution is gradually cooled, solidified, to give a novel compounded material. The compounded material has hardly a pungent odor of propionic acid of its own, no high moisture absorbing properties of sodium propionate, and much more improved antifungal effect than sodium propionate and calcium propionate. The amount of the compounded material used is 0.01-1wt%, preferably 0.05-0.7wt% based on feed or food.

Description

[Detailed description of the invention] The present invention relates to novel composites and their uses.

Propionic acid is an organic acid with antibacterial properties and is useful for preventing mold in feed and food. However, this acid is liquid and volatile, and is extremely irritating and inconvenient to handle, so its salts, sodium propionate and calcium propionate, are actually used. By the way, propionic acid is an acid-type antibacterial agent like nruvic acid, so its antibacterial properties depend on the pH of the feed and food to which it is added.
It is influenced by H, and the lower the pH, the stronger it becomes. Sodium propionate and calcium propionate are neutral or slightly alkaline and have no ability to lower pH. Furthermore, since it is the propionic acid molecule itself that has antibacterial activity, it is natural that propionic acid exhibits the strongest antibacterial activity compared to its sodium salt or calcium salt when added in the same amount. Therefore, it would be of great industrial significance if the above-mentioned drawbacks of propionic acid could be overcome and propionic acid could be directly powdered and made into a stable form. Furthermore, since sodium propionate has strong hygroscopicity and calcium propionate has weak antibacterial properties, improvements in this respect are also desirable. The present inventors have arrived at the present invention as a result of intensive research to achieve such an objective.

The present invention is a novel complex consisting of propionic acid, sodium propionate and calcium propionate, and containing propionic acid in a stable form.

The ratio of the three components in the composite of the present invention may be arbitrary as long as it contains propionic acid in a stable form, but usually 0.1 to 10 mol of sodium propionate and 0.1 mol of calcium propionate per mol of propionic acid. ~5 mol, especially 0.25 to 6.25 mol of sodium propionate and 0.5 to 2.5 mol of calcium propionate.

To prepare the composite of the present invention, sodium propionate and calcium propionate are first added and mixed to propionic acid. In this case, the amount of the three components used is preferably such that propionic acid is in excess of the above composition ratio. This mixture is then heated to dissolve it. A compound can be obtained at a heating temperature. As a method for removing propionic acid, conventional drying methods such as gout drying, vacuum drying, spray drying, drum drying, etc. are used.

The composite of the present invention can also be prepared by adding inorganic calcium and inorganic sodium compounds to propionic acid and allowing it to act, and then removing the produced water and excess propionic acid.

Examples of inorganic calcium compounds include calcium hydroxide, calcium carbonate, and calcium oxide, and examples of inorganic sodium compounds include sodium hydroxide, sodium carbonate, and sodium hydrogen carbonate. The reaction can also be carried out in the presence of an organic solvent. It is believed that the product has a certain composition and is not just a mixture.

Feed for poultry, feed for pets such as dogs and cats, feed for laboratory animals such as rabbits and rats, feed for farmed fish, especially 0.0%
It is preferable to use it in a proportion of 5 to 0.7% by weight.

The fact that the composite of the present invention is not just a mixture of three components is that
There is almost no propionic acid odor (the amount of propionic acid hardly decreases with normal drying, there is almost no hygroscopicity even though it contains sodium propionate, and
This is clear from the line diffraction image. Although it is possible to form some composites by simply mixing the three components, the composition is unspecified and the properties for use are unsatisfactory.

Although the composite of the present invention contains a large amount of propionic acid, it has almost no stimulants peculiar to propionic acid, and does not have the strong hygroscopicity of sodium propionate. And Gropio Ru.

The existence of a double salt of propionic acid and sodium propionate is known, but this salt easily releases propionic acid and disappears when heated. In addition, a compound of propionic acid and calcium propionate can contain propionic acid in a stable form and has almost no stinging or hygroscopic properties, but it has a mildewproofing effect on feed compared to sodium propionate and calcium propionate. low.

For these reasons, the composite of the present invention is recognized as a novel composition, and exhibits excellent effects that cannot be obtained with each component alone, a composite of two components, or a mere mixture of three components.

Example 1 0 sodium propionate per mol of propionic acid
．． 11-0.24 mol and calcium propionate 0.
Add 0.095 to 0.22 mol and heat to 140° C. while stirring to dissolve. After dissolution, the solution was allowed to cool and solidify, and the resulting transparent solidified product was crushed to form a slurry, and excess propionic acid was removed at 20 Torr and 50 to 60°C.

The slightly moist pellet was spread on a enamel dish and dried under ventilation at 50-60° C. for about 6 hours with occasional crushing, to obtain a white, free-flowing powder.

This powder has almost no propionic acid odor.

Furthermore, the X-ray diffraction image did not have any diffraction peaks seen in the mixture of thorium propionate and calcium propionate, and diffraction peaks not seen in this mixture were observed. Table 1 shows the component composition, odor, and moisture absorption state of the composite of the present invention and of sodium propionate alone and a double salt of sodium propionate as a comparison. The mixing ratio (mol) of the other two components to 1 mol of propionic acid is as follows.

Composite 10, 11 0.22 2 0.17 0.17 3 0.2 0.13 4 0.22 0.11 5 0.24 0.095^ 1' 8- Note 1): Each composite is Determine the amount of sodium using atomic absorption spectrometry.
The composition of each was analyzed by determining the amount of calcium by chelate titration using F and DTA solutions, and the amount of propionic acid using normal sodium hydroxide solution.

Note 2): The moisture absorption state of each composite was investigated as follows.

(1) Moisture absorption rate: Accurately weigh about 1 g of each sample into a glass petri dish with an inner diameter of 5.5 cm, and use a desiccator adjusted to a relative humidity of 81.1% at 30°C (using a saturated aqueous solution containing ammonium sulfate crystals). - Place it inside and leave it in a constant temperature room at 60°C for 24 hours. The weight increase of each sample was measured, and the moisture absorption rate was calculated from the following formula.

Moisture absorption rate = (weight increase / weighed sample weight) x 10'D (2
) State of sample after test: Changes in state due to moisture absorption of the sample after moisture absorption rate measurement were observed and described.

Example 2 Calcium hydroxide 37 g (0.5 mol), water 59 m
E and 229.4 g (3.1 mol) of propionic acid were charged into a reaction kolben and heated at 80 to 100° C. for 30 minutes with stirring. Then 50% sodium hydroxide 809
(1 mol of NaOH) was gradually added dropwise, and after the completion of dropping,
The mixture was heated and stirred at 0 to 120°C for 60 minutes. Next, the contents were allowed to cool and solidify, crushed finely and spread in a glass petri dish, and dried with ventilation at 50-60℃ for 8 hours while occasionally crushing in a mortar.A white, free-flowing powder was obtained, with almost no odor of propionic acid. There was no. The water content of this composite (6) is 0.9%, and the molar ratio of propionic acid, sodium propionate, and calcium propionate is 2. '0
: 1.9 : 1.0, and showed the same X-ray diffraction pattern as Composites 1 to 5 (Example 1).

Example 3 A feed mold-proofing test was conducted using the composites prepared in Examples 1 and 2. The test method is as follows.

0.1% and 0.2% of each test drug was added to a commercially available compound feed for dairy cows (moisture content 16.4%) and mixed to prepare the test feed. The sample was placed in a desiccator adjusted to 60°C and a relative humidity of 92.6% (using a saturated aqueous solution containing potassium nitrate crystals), then stored in a former greenhouse at 30°C and observed orally. The effective number of days of storage before mold growth was investigated.The test was repeated twice and the average number of effective storage days was determined.The pH of the feed was determined by dipping the feed into 10 times the volume of deionized water before starting the storage test. When it was suspended in and measured, it was 6.86,
The effective storage period was 12 days. The test results are shown in Table 2.

It is clear that all of the composites of the present invention have better preservative effects than sodium propionate or calcium propionate.

Example 4 Wheat flour (strong flour) 400.9, water 248ml, sugar 16
g, yeast 8g, shortening 16g, salt 7.2g
．． A dough was prepared by kneading 0.9 g of fermentation accelerator and 0.9 g of calcium propionate with or without adding 0.2% of calcium propionate or the compound of the present invention as shown in Table 4. I made bread. After baking, 6 slices of bread were sliced from the - test group, placed 2 slices each in a polyethylene bag, and placed in a thermostat at 30°C for a storage test.

The results are shown in Table 3.

Note in Table 6: Number of slices of bread on which mold growth was observed out of six slices of bread The composite of the present invention had a better preservative effect than calcium propionate, and mold growth was suppressed.

Applicant: Ueno Pharmaceutical Application Research Institute Co., Ltd. Agent: Patent Attorney Masao Kobayashi 15- Procedural amendment (voluntary) February 14, 1982 Mr. Kazuo Wakasugi, Commissioner of the Patent Office Display of 1 incident Patent Application No. 189071/1983 2. Name of the invention Novel composites and their uses 3. Person who makes corrections Relationship to the incident: Patent applicant address 4. Deputy manager 5 Date of amendment order , -6, Number of inventions increased by amendment 8. Contents of amendment As per the attached correction sheet.

16- The following corrections are made in the specification of the written amendment (Japanese Patent Application No. 189071/1982).

1. On page 4, line 2, "gout dryness" is changed to "ventilation dryness."

2. “Propionic acid” IJ on page 7, lines 4-3 from the bottom
IJium alone and a mixture of sodium propionate and calcium propionate, as well as propionic acid.

3. Add "〃" to the fourth column (blank area) of Comparative Examples 1 and 2 in the table on page 10.

4. Change "Compounds 1 to 5 (Example 1)" in lines 6 to 5 from the bottom of page 12 to "Composite 4 of Example 1" 35. No. 15
Delete "as shown in Table 4" on pages 7-8 lines.

Applicant: Ueno Pharmaceutical Application Research Institute Co., Ltd.

Claims (1)

[Claims] 1. A novel composite consisting of propionic acid, sodium propionate and calcium propionate, and containing propionic acid in a stable form. 2. Consists of propionic acid, sodium propionate and calcium propionate;