JPS6165802A - Preservative - Google Patents

Abstract

PURPOSE:To obtain a water-soluble preservative having excellent stability and giving a transparent and stable solution only by adding to a liquid object, etc., and lightly stirring the mixture, by dissolving a p-hydroxybenzoic acid ester and quillaja saponin in a hydrated hydrophilic organic solvent. CONSTITUTION:A p-hydroxybenzoic acid ester having excellent preservative and fungicidal effect and high safety, especially butyl ester, etc. is used as an active component, and is compound with a solubilizing agent consisting of a quillaja saponin which is a natural surfactant used in food industry. The composition is dissolved in a hydrophilic organic solvent such as hydrated ethyl alcohol, acetic acid, etc., stirred under heating until the whole mixture turns transparent, and cooled to obtain the objective preservative. EFFECT:There is no lowering of the commercial value of the preservative caused by the isolation of p-hydroxybenzoic acid. The quillaja saponin is tasteless and odorless at the normal dose, and is inert to the taste and flavor of the food and drink to be treated. The solubilization effect is maintained even in acidic state. The agent can be used in foods, drinks, cosmetics, pharmaceuticals, etc. without troubles.

Description

[Detailed Description of the Invention] Field of Industrial Application The present invention relates to preservation methods for improving the function and quality of various foods and beverages, cosmetics, pharmaceuticals, etc. and preventing the growth of mold. Furthermore, the present invention relates to a water-based preservative containing paraoxybenzoic acid ester as a ti-active ingredient.

Lower alkyl esters of paraoxic acid, especially 7-tyl ester, isobutyl ester, propyl ester,
Isopropyl esters and ethyl esters have been widely used in foods, vinegar, soft drinks [1 water, fruit sauces, fruits and vegetables] as a preservative for fruits and vegetables, and have also been used in cosmetics and pharmaceuticals (added here). 9 However, paraoxybenzoic acid esters are difficult to dissolve in water;
For this reason, various bath-dissolving or dispersion methods are used for heavy use. - As an example, among the paraoquin anadani acid esters, butyl is the most commonly used for food and beverages. In the case of ester (hereinafter referred to as POBB), POBB is first dissolved in a 5% aqueous sodium hydroxide solution, propylene glycol, ethanol, or acetic acid, and this solution is dropped into heated food and drinks to disperse it. When using this method, POBB does not completely dissolve in the final product after addition, but is dispersed in the form of fine particles. It may damage the value of Song Dynasty products.
Dispersed and emulsified by adding molasses and chill, eutectic with baraoquin benzoic acid ester, IX, and compound as oil-in-water type 2L punishment (also historical method). In some cases, POBB dispersed in water may become cloudy or produce particles.
Soy sauce made of OIIB in a solubilized state 1.
1j mouthwash (!1.+f Publication No. 19599, 1972) is also known, but the ingredient clicyrrhizin has a strong II taste, and the acidic aqueous solution Precipitation occurs in the inside, so the second type of anti-erosion is -membrane-like.
11, 1” Suitable r+T't8jI other than grass extract
1. The agent has not yet been found, and therefore, there is no example of solubilizing Baraoki/Onsori Aku Matachiru and preserving it.

Roseoxyam 7Q is used for cosmetics, pharmaceuticals, and other items other than food and drink.

When using hexaacid esters, in the case of food and drink;
Since the use of single solvents and surfactants is not regulated, it is common practice to use nonionic surfactants such as 1Uleen and Span as a single agent to create a town. ing.

Problems to be Solved by the Invention The present invention solves the following problems: Despite its excellent antiseptic and antifungal properties and safety, the present invention has the above-mentioned problems, which make it difficult to use. In view of the fact that it can be used only within a limited range, paraoxybenzoin can easily form a stable solubilized state with a wide range of additives and exhibit excellent antiseptic and antifungal effects. This paper attempts to improve the preservation of acid esters using highly safe natural product-based solubilizers.

Means for Solving the Problems The preservative provided by the present invention is prepared by dissolving roseoxybenzoic acid ester and Quillaja saponin in a hydrophilic solvent.

Quillaya Saboni/ is a Quillaja tree (tlt) used in South American braziers.
A natural surfactant extracted from 1° of skin,
It has been confirmed that it has better biodegradability than synthetic surfactants and is highly safe, so it has recently come to be used in the food field.

However, Juki focused on its strong foaming effect,
It is used as a foaming agent for non-alcoholic beverages and as a foaming agent for fresh drinks, and of course, this surfactant or oxybenzoic acid ester may be used as a preservative. There are no examples of it being used as an emulsifying agent like a mulching agent.

In the preservative of the present invention, the rosewood/benzoic acid ester and the rosewood sabonin are completely dissolved in the hydrophilic tE1jB medium to form a stable transparent solution. When the preservative of the present invention containing this preservative is used and added to each station, Quillaya Saboni/ is able to solubilize the roseoxybenzoic acid ester, which would otherwise precipitate immediately, into a dissolved state. keep.

It should be noted that the solubilizing effect of Quillaja saponin is thought to be helpful in keeping the il liquid state of Baraoki/benzoic acid ester stable, depending on the state of the preservative used, and the degree of its contribution depends on each component. It seems that it varies depending on the blending ratio.

The solubilizer/Quillaya saponin used in the present invention includes saponin extracted and purified from Quillaya skin, as well as saponin obtained by chemically processing it, and like Quillaya saponin, rose oxybenzoin. Those capable of solubilizing acid esters are also included.

There are many hydrophilic solvents that can be used chemically for the water-containing hydrophilic trtI8 medium. (According to current regulations, the solvents that can be used are ethyl alcohol, propylene glycol, and acetic acid.) If the additive is a cosmetic or pharmaceutical product, isopropyl alcohol, glycerifol, etc. Each of the preservatives of the present invention (IVI
rIi, the suitable ratio of components is determined by the solvent used and the
In addition to the type of benzoic acid ester, it differs depending on the storage conditions, usage conditions t+ determined depending on the use of L, etc.
The point is that the shape of the preservative (stable and transparent when there is one island, and that it can maintain three states), and the use of the preservative 11
．． 9 may be anything that can realize the above-mentioned state of being closed (, 17).

However, in many cases, Quillaja saponin is required in an amount of about 1(20%) to 200% by weight based on Balaaki/benzoic acid ester. In addition, good results can be obtained when the water content of the hydrophilic solvable solvent is within the following range, for example, when POBB is used as the rosewood/benzoic acid ester and a preservative containing about 10% of POBB is to be produced. It will be done.

Hydrophilic (Solvent Water Content (v, v%)) Ethyl Alcohol 20-70 Isopropyl Alcohol 30-70 Propylene Glyfur 20-60 Acetic Acid 20-60 Water Containing Hydrophilic is when the water content of the solvent is high. roseoxyan, 12,
It is difficult to dissolve in acid or chill, and only a thin preservative of this ingredient can be obtained. On the other hand, water-containing hydrophilic (note: 8 medium water content! (゛ is 11y. It becomes 211 L.

The preservative of the present invention is prepared by adding Paraoquin Ankyu Pr Acidic Matachiru and Gukillayasabonin into a hydrophilic solvent containing water,
Continue stirring under heating until the whole becomes transparent, then cool] J
By doing? : In that case, to the extent that it does not interfere with the solubilization of Quillaja saponin, surfactants other than Quillaja saponin or surfactants other than Quillaja saponin may be used.
111 ester, glycerin fatty acid ester, quacum, etc. may be added.

Effects of the Invention The preservative of the present invention is produced by Quillaya Saponin Town, 1i-11-
Depending on the application, it not only has excellent stability in the preservative state, but also when added to liquid or tape-like objects, it can be made into a transparent and stable preservative by simply stirring. The δ state is expressed as χ. When using the preservative of the present invention, there is no fear that balaoquin benzoate will be released and the commercial value will be impaired. Furthermore, Quillaya saponin is tasteless and odorless in normal doses, and does not have any adverse effect on the taste or aroma of foods and beverages to which it is added. Because I don't
The f-preservative of the present invention can be used in a wide range of food and drink products, cosmetics,
It can be used in medicines, etc. without any problems. Therefore, the present invention takes advantage of the excellent antiseptic and antifungal effects of paraoxyammonium, Q, and hexaacid esters (but can also be used in fields where it was difficult to use them for various reasons).
1.

1 turn The present invention will be explained below with reference to Test Examples and Examples.

The Quillaja saponin used in each test example was as described in Examples below.

Test example 1 Propylene glycol ・↓()% water, ;; P O in the liquid
[3B was concentrated so that 1 part was 1%, and the sample SO+nl was added to 30' (:, 7 crystals, POBB was solved, and then 2S'C was added. !!, When cooled, P OB B was precipitated and the limb became internally warm. While stirring this precept ISk, Quillaya saponin was added little by little and yp <, and when 2.8 g = Quillaya saponin was added. The POBEI residue was made into a liquid, and the whole became transparent and in the form of a solution.

A similar test was conducted on pond rose oxybenzoate ester, and the results were as follows.

Rose oxybenzoic acid ester Quillaja saponin addition g (
g) Ethyl ester 1.5 Propyl ester 2.1 Isopropyl ester 2.0 In Butyl ester
2.7 methyl ester
1.0 Test Example 2 POBB, Quillaja saponin (or glycyrrhizin),
Butypyrene glycol and water were combined in the weight ratio shown in the table below and heated and stirred at 40-60'C to obtain a clear solution.

Example of the present invention Control example 1 ΔPlate V POBB H) H)
It) Quillaya Saponin 4
- - Grinarritin - -10 Propylene glycol 40, to
40 water 46 50
40 For each of the above examples, 0.1 part by weight was adjusted to pH
The mixture was added dropwise to 1 part of 100yl' of No. 3,3 buffer solution (temperature: 80°C) with stirring, and after the addition was completed, the mixture was stirred for an additional 5 minutes and then subjected to a cooling test. In this case, in Control Example 1, precipitates were observed from the time of dropping, and even more precipitates were formed after cooling. Although Control Example 2 is not the same as Control Example 11, I wonder if precipitates will gradually form after cooling! , was missed. In contrast, in the case of the example of the present invention, no precipitate was observed after cooling.

Example 1 Perform RF boiling extraction on 1kS of shredded Kiraya rice bark with about 10 times the amount of water, and concentrate the extract to dryness91; (After crushing the solid matter, += of ethanol is added, warmed to dissolve the liquid, allowed to cool, and the precipitate is collected.This is *dried to obtain EIY Fl' Quillaya Saponi/120g of one color powder.

Quillaya saponin 40g 1:P obtained as described above
OBBloog, propylene glycol (50 t) ml, and water (360 ml) were added and heated while pouring, and then cooled to obtain a yellow-brown transparent preservative.

When 1 ml of the above preservative was added to 10 ml of water, heated to 40"C and stirred, a pale yellow and transparent mixture was immediately formed, and this state remained stable even after being left to cool for a long time. Ta.

Separately, a soy sauce anti-scaling test was conducted using the above preservative. In other words, raw soy sauce (TN: 1.L
Salt:) 7.3%, specific gravity: Bo 721 degrees + nH: 4
．． 3) was fired to 80'C, a preservative was added, the mixture was cooled, and the precipitated soil was removed.
Transfer 51) ml to a wide-mouthed bottle, inoculate it with +lli membranous yeast (separated and cultured from the above-mentioned yeast in pasteurization 11; i), and place in a 30' incubator. ,
9. Check the status of the issue. I did it. The addition rate of the additive is 0 to 0.
．． God within 20%]? After 1 hour of history of wheat, the result was exactly as the dog said.

0 - Shishishi + 100 H4m m fl, (i5 - '---f1.H1--
1111110.20 −−−−−−−−− [dyu 1−: Kahi or recognized h linai±: It looks like something moldy or floating 10~++I: It looks moldy or floating Example 2 10g of the Quillaja saponin obtained in Example 1 was added with 2% paraoki/methyl benzoate (10g, 50% sucrose fatty acid ester)
g, ethanol 5] 0+lIl and water 20t3m
After heating with stirring, cool and transfer the entire amount to IC.
A yellow-brown transparent preservative was obtained.

Add the above stored n l + n l to 100 ml of water, 4 (
When heated to 1'C and stirred, a pale yellow and transparent layer was formed;
A dank liquid was formed, and this state remained stable even after cooling and leaving for a long period of time.

In addition, when the lotion containing the above preservative was formulated with the following formulation, there was no turbidity, and after storage for 6 () days at room temperature, there was no turbidity or peel rI1. T, I didn't recognize it.

Probile/Glycol 5?6 Ex/-le 5?5 Fragrance (Dou), Pigment iM iI7 Preservation +-1 (+, 5% Water Residual oxidation ) % propylene glycol aqueous solution 80 () Place 8 in the mouth 11.Separately, P C1B B15 hair; Milky white liquid obtained by dispersing eutectic propyl 20 parts by weight in 50 parts by weight of water] t) I) m
Prepare 1 liter of Quillaja saponin solution and add 1 liter of water to it.
111 ml of the mixture was added, heated while stirring, and then cooled to obtain a yellow transparent preservative with a total amount of IC.

Add the above stored fLtm+ to 1 t) Oml of water, ↓O”C
When the mixture was heated to a temperature of 15°C and stirred for 15 minutes, a pale yellow transparent layer was immediately formed, and this state remained stable after being allowed to cool and stand for a long period of time.

Implementation f 11. 1 Using the Quillaja saponin obtained in Example 1, Preservation 11 with the same composition as the Quillaja saponin except that it did not contain the Quillaja saponin was manufactured as a Umaji Kogesho product prepared with the preservative of the present invention. .And its composition is as follows.

Tenka Reisho Presentation POBr3 11'1% 1
0% Quillaya Saponin 20 Propylene Glycol 4; S.

water 40
40 The above two types of preservatives - A dog-like abuse test was conducted to investigate the stability of these two preservatives when added to Shiroura. First, 0.1% preservative is added to '7fL product 1-Shi-nai-shoura. *o'c by l'+' method
Pasteurize it, leave it to cool, drain it, remove it, and add 511+nl of Tsukonomi human test fluid to make the five-type test tube. wide (-1
Hi/; Kotori blows 1 (゛'s sky:be) every minute for 5 minutes.

As a result of the above test, it was found that using the Nljjjj product, it was red.
Colored dots, ゛? , Is it a plaything, it increases 14 times and 1 ヽ on a considerable shore, and that jt is ``) (stop + h k 1-1' on the wall of the hin: ?'i L. To this, λ-f In fact, when I used 1 x 1 product, no floating matter was generated, and I was able to confirm that there were some particles in the PO13B coconut oil.

Deputy K Ben J Satoko Itai-You

Claims (2)

[Claims] (1) A preservative prepared by dissolving paraoxybenzoic acid ester and Quillaja saponin in a water-containing hydrophilic organic solvent. (2) The preservative according to claim 1, wherein the hydrophilic organic solvent is ethyl alcohol, propylene glycol, or acetic acid.