JPH0215527B2 - - Google Patents

Description

Detailed Description of the Invention The present invention relates to the production of a sorbic acid-potassium sorbate adduct (hereinafter abbreviated as "adduct") represented by the formula C ₆ H ₈ O ₂・C ₆ H ₇ O ₂ K. For more details regarding the method, please refer to sorbic acid (hereinafter abbreviated as "SA")
When producing adducts with potassium sorbate (hereinafter abbreviated as "KSA"), most of the
This invention relates to a method in which SA and KSA are forced into contact with each other in the presence of a small amount of water that does not dissolve them.

It is known that SA and KSA form an equimolar adduct, and it has already been shown that this adduct can be used as a food preservative in the same way as SA or KSA. However, there are few examples that have been clarified regarding the manufacturing method, and there seems to be only one example specifically described in JP-A-51-11707. And the known method is
This method is characterized by dissolving SA in a KSA aqueous solution by heating, and then cooling the solution to room temperature to crystallize the adduct. The solubility of SA is relatively small, less than 10g per 100g of KSA aqueous solution up to a temperature of around 60℃, so the dissolution of SA must be carried out at a fairly high temperature to avoid deterioration of KSA or adducts. I couldn't do anything. In particular, when the mother liquor was recycled in consideration of efficiency, significant deterioration was observed and coloration was observed that was difficult to decolorize with activated carbon, and as a result, the quality of the obtained adduct was not satisfactory.

The present inventor discovered that in the previously filed SA formulation and its manufacturing method (Japanese Patent Application Laid-Open No. 62-87045), if a certain amount of water is present, most of the SA remains undissolved at relatively low temperatures. It was also revealed that adducts are formed in the contact area by sufficient contact, but as a result of intensive research based on this fact, it was found that most of SA and KSA do not dissolve. When SA and KSA are forcibly mixed using a kneader or a mixer in the presence of a small amount of water, adducts are formed on the SA surface, and these adducts are ground up. The SA crystal falls off from the surface of the SA crystal, and the exposed SA reacts with KSA to form an adduct, which is then ground up and falls off from the SA crystal surface. miniaturized,
The present invention was achieved by discovering the completely unexpected fact that in the end it becomes almost completely an adduct.

In other words, SA and KSA are mixed and kneaded in the presence of a small amount of water that does not dissolve most of the SA and KSA, such as at a weight ratio of 0.03 to 0.3 to Mixture 1, which has approximately equal moles of SA and KSA. Or, by performing summation, the adduct is generally obtained as fine crystals of 10μ or less.

The temperature during mixing etc. in the present invention is 0~
50°C, preferably 15°C or more and less than 45°C.

The above-mentioned Japanese Patent Application Publication No. 11707/1970 or Japanese Patent Publication No. 1977-
The method described in No. 29520 involves heating and dissolving SA and KSA in a solvent and then cooling to crystallize the adduct, whereas the method of the present invention involves converting the reaction mixture into a homogeneous solution when producing the adduct. It is not necessary to do so. Therefore, there is no need to forcibly raise the temperature by external heating in order to make a homogeneous solution, and it can be carried out at room temperature, and in terms of preventing coloration, it does not require a large amount of thermal energy. This is very advantageous in this respect. Furthermore, the method of the present invention does not generate mother liquor, and therefore there is no need to consider recycling the mother liquor, compared to the method of JP-A-51-11707 or JP-B-45-29520. This is a very advantageous point.

Hereinafter, specific implementation conditions of the present invention will be explained in detail.

In the method of the present invention, adsorption treatment using activated carbon or the like or purification operations such as recrystallization are not performed, so it is preferable to use raw materials such as SA, KSA or water that have all been purified in advance.

The particle size of the SA and KSA to be used basically does not matter, but considering the time required for mixing, kneading, and sintering, it is generally desirable to use SA with a fine particle size. Preferably, SA that passes through a 60 mesh sieve is used.

Also, there is no problem whether the SA and KSA used are dry products or water-containing products, but in reality, the general production method for SA and KSA is using water or some organic solvents. It is advantageous in terms of the energy cost required for drying to use a water-containing product that has been dehydrated using a Centor or other solid-liquid separator.

The ratio of SA and KSA in the method of the present invention is 1:1 in molar ratio by weight to SA1, as the composition of the adduct is represented by the formula C ₆ H ₈ O ₂・C ₆ H ₇ O ₂ K.
Mixed targeting a ratio of KSA 1.34. Therefore, the preferred molar ratio is KSA 0.95 to 1.05 to SA1.
It is. The ratio of water to the mixture of SA and KSA is 0.03 to 0.3, preferably 0.05 to 0.15, based on the weight of the mixture.

If the ratio of water to the mixture of SA and KSA is less than 0.03 in terms of weight ratio, a problem arises in that the reaction between SA and KSA is difficult to occur, and therefore adducts are difficult to form. On the other hand, when the weight ratio of water to the mixture of SA and KSA is greater than 0.3, although some adducts are formed, they tend to be adducts with low purity, that is, adducts containing unreacted SA and KSA. A problem arises.

In addition, if the ratio of water to the equimolar mixture of SA and KSA is 0.15 to 0.30 by weight, there will be no problem with the formation of adducts, but when mixing, kneading, or sintering, The problem arises that it becomes sticky and difficult to handle. Therefore, if the ratio of water to the equimolar mixture of SA and KSA is 0.15 or more by weight, dry SA or KSA
It is preferable to adjust the value to 0.15 or less by adding water or scattering water by concentrating it. If the ratio of water to the mixture of SA and KSA is small, such as 0.03 or less in terms of weight ratio, water may be added to adjust the ratio to 0.03 or more.

Mixing, kneading, or summing in the method of the present invention may be performed using a commercially available device such as a kneader, simmering machine, mixing agitator, mixing/dispersing machine, or granulating machine.
This can be carried out using equipment that has capabilities such as grinding. Since the additive is softer and easier to grind than SA, special equipment is not required.
The adduct can be easily produced by mixing, kneading or sintering using equipment commercially available under the above names.

The reaction rate of SA and KSA can be determined by adding the adduct produced by mixing, kneading, or summing to toluene or other solvent that dissolves SA well but does not dissolve the adduct, stirs it, and then extracts SA into the solvent layer. After that, it is confirmed by analyzing the solvent layer by neutralization titration or gas chromatography. In other words, if unreacted SA and KSA are present in the adduct produced by mixing approximately equimolar amounts of SA and KSA, they will react to a solvent such as toluene.
The reaction rate is calculated by extracting SA and quantifying it by neutralization titration or gas chromatography. Therefore, if there is SA to be extracted, a highly pure adduct from which almost no SA is extracted can be obtained by further continuing mixing, kneading, or summing.

A simple confirmation method when producing a high-purity adduct is to measure the particle size of the adduct produced by mixing, kneading, or sintering using a magnifying glass or microscope. Can be done. In other words, if the particle size of the largest particle in the adduct is 10 μ or less, it can be considered that the desired adduct has been produced. If it is determined that reactants are present, further mixing, kneading, or summing is performed.

The production of adducts in the method of the present invention includes SA,
Mix, knead or mix a mixture of KSA and water.
SA,
Even if known antioxidants and hydrophilic surfactants are simultaneously added to the mixture consisting of KSA and water, no particular problem will occur. It is preferable to add a hydrophilic surfactant, such as a sucrose fatty acid ester, because it facilitates mixing, kneading, or massaging.

As mentioned above, the adduct produced by the method of the present invention has a very small particle size (the particle size of the adduct produced by the conventional method is approximately
Only those over 50μ can be obtained. ), which are fine particles with a particle size of 10μ or less, and have very advantageous physical properties when considering uniform dispersion in foods when used as a food preservative.

Further, since the fine particulate adducts produced by the method of the present invention are fine grains, they easily stick together and can be made into larger grains very easily. This is a very advantageous physical property when considering the advantages of granular products, such as convenience in drying and ease of handling as a product. In addition, the basic particles are fine particles with a particle size of 10 μm or less, and have suitable physical properties as a raw material for various SA-containing suspensions.

In the following examples, parts refer to parts by weight.

Example 1 A mixture consisting of 50 parts of SA, 67 parts of KSA, and 10 parts of water was repeatedly mixed, kneaded, or sludged in an EXDF type pre-extrusion granulator manufactured by Fuji Paudal Co., Ltd.
The mixture was dried under vacuum at 0.degree. C. to obtain 115 parts of a cylindrical adduct with a diameter of about 3 mm and a length of 5 to 10 mm. The maximum temperature during mixing, kneading, or mixing was 41°C. 2 g of the resulting adduct
was poured into 200 g of toluene, stirred vigorously for 15 minutes, filtered, and the SA extracted into the toluene layer was analyzed by neutralization titration and found to be 0.002 g of SA.
The response rate for SA and KSA was over 99.5%.

Example 2 50 parts of SA, 70 parts of KSA and sucrose fatty acid ester
Add 0.5 parts to a New Speed Kneader (trademark) manufactured by Okada Seiko Co., Ltd., and add approximately 30 parts by weight of water while mixing.
Spray for 60 minutes and mix, knead or simmer for an additional 30 minutes to form a paste-like water-containing adduct.
Obtained 145 copies. The temperature of the mixture was approximately 38°C when the amount of water was low, and approximately 28°C when the amount of water was increased.
2.5 g of the obtained water-containing adduct (2.0 g as adduct)
g) was added to 200 g of toluene, stirred vigorously for 30 minutes, left to stand, and analyzed the upper toluene layer by gas chromatography. It was found that SA was 0.007 g, and the SA reaction rate was over 99.5%. .

Example 3 0.5 part of sugar fatty acid ester was added to a mixture of 50 parts of SA, 67 parts of KSA, and 5 parts of water, and Okada Seiko
After mixing, kneading, or sintering for approximately 60 minutes using a New Speed Kneader (trademark) manufactured by Co., Ltd., the pellets are granulated using a crushing type granulator (New Speed Mill (trademark) manufactured by Okada Seiko Co., Ltd.). Approximately 12Kg of 0.5-1mm granular water-containing adduct
I got it. The maximum temperature from mixing to the end of granulation is approximately
It was 40℃. 2.1g of the obtained water-containing adduct (2.0g as adduct) was added to 200g of toluene.
After stirring vigorously for 30 minutes, the mixture was stopped and the upper toluene layer was analyzed using gas chromatography.
The amount of SA was 0.001 g, and the reaction rate of the adduct of SA and KSA was 99.5% or more.

Example 4 A mixture consisting of 50 parts of SA, 67 parts of KSA, and 15 parts of water was repeatedly mixed, kneaded, or tempered using a continuous kneader CKD model manufactured by Fuji Paudal Co., Ltd.
Fuji Paudal Co., Ltd. equipped with a screen with a hole diameter of 1 mm
It was granulated using a manufactured EXD type granulator. The resulting diameter of approx.
A cylindrical adduct with a length of 3 to 4 mm was fluidized at 40°C to 50°C, and then 2g of it was taken and SA was extracted with 200g of toluene, and 0.001g of SA was extracted. Therefore, the reaction rate of SA and KSA is over 99.5%.

Comparative Example 1 A mixture consisting of 50 parts of SA, 67 parts of KSA, and 0.6 parts of water was heated in a New Speed Kneader (trademark) manufactured by Okada Seiko Co., Ltd.
After mixing, kneading, or summing for about 30 minutes, the mixture was discharged. 2 g of the mixture was added to 200 g of toluene, stirred vigorously for 30 minutes, filtered, and the SA extracted into the toluene layer was analyzed by neutralization titration, and it was found to be about 0.8 g as SA, indicating a reaction between SA and KSA. The rate is below 10%.

Claims (1)

[Claims] 1. A mixture of sorbic acid, potassium sorbate, and water is mixed, kneaded, or summed, and at this time, the molar ratio of sorbic acid and potassium sorbate is adjusted to 1:1 to 1:1 potassium sorbate. 0.95～
1.05, and when the total amount of sorbic acid and potassium sorbate is 1, the proportion of water is 0.03 to 0.03 by weight.
0.3. A method for producing an adduct of sorbic acid and potassium sorbate. 2. The method according to claim 1, characterized in that the proportion of water is 0.03 to 0.15.