CN114053162B

CN114053162B - Color-stable preservative composition containing sorbic acid and application thereof

Info

Publication number: CN114053162B
Application number: CN202111593482.2A
Authority: CN
Inventors: 于跃; 冯士清; 赵华
Original assignee: Beijing Meike Xingye Biotechnology Co ltd
Current assignee: Beijing Meike Xingye Biotechnology Co ltd
Priority date: 2021-12-23
Filing date: 2021-12-23
Publication date: 2023-10-20
Anticipated expiration: 2041-12-23
Also published as: CN114053162A

Abstract

The invention discloses a color-stable preservative composition containing sorbic acid and application thereof. The preservative composition consists of organic acid accounting for 5-35% of the total weight of the composition, stabilizing agent accounting for 0.05-2%, solubilizer accounting for 10-40%, synergistic agent accounting for 1-20% and solvent accounting for 20-80%. The composition overcomes the defects of easy discoloration and poor water solubility of sorbic acid, ensures that the composition containing sorbic acid can keep stable color under the conditions of high temperature, illumination and oxygen contact through the synergistic effect of the components, has good water solubility and good anti-corrosion effect, and can be widely applied to products such as cosmetics, household washing articles, wet tissues and the like.

Description

Color-stable preservative composition containing sorbic acid and application thereof

Technical Field

The invention relates to a color-stable preservative composition containing sorbic acid and application thereof, in particular to a preservative composition containing sorbic acid with good water solubility and capable of keeping color stability under the conditions of high temperature, illumination and oxygen contact and application thereof.

Background

Sorbic acid has the chemical name of 2, 4-hexadienoic acid and the structural formula of CH ₃ Ch=chch=chcooh. Pure sorbic acid is colorless needle-like crystals or white crystalline powder, odorless or slightly special odor. Melting point 132-135 deg.C, boiling point 228 deg.C (decomposition temperature). The pure product is stable in a sealed state, and is easy to oxidize and color when placed in air. Is easily dissolved in organic solvents such as alcohol, ether and the like, and is slightly dissolved in water. The solubility in water (g/100 g) is 0.16 at 20 ℃ and only 3.8 at 100 ℃, so that the water-based paint is not easy to add and use.

Sorbic acid and potassium sorbate are internationally recognized, broad-spectrum, efficient and safe food preservative agents recommended by the national grain and agricultural organization and the world health organization. Sorbic acid and salts thereof are also cosmetic preservatives allowed to be used in various countries in the world, and are also recorded by pharmacopoeias of various countries as bacteriostatic agents. The molecular structure of sorbic acid contains carboxyl and conjugated double bond, and the carboxyl makes sorbic acid acidic and inhibits the growth of microorganisms; the conjugated double bond can be combined with sulfhydryl of microbial enzyme (under the condition of pH less than 6), so that the structure of enzyme system is destroyed, the enzyme is deactivated, and the microorganism propagation is finally inhibited, so that the aims of corrosion prevention and fresh preservation are achieved. Sorbic acid needs to pass through the cell membrane to inhibit the enzyme system and undissociated sorbic acid molecules can act. Sorbic acid has inhibitory effect on all mold, yeast and aerobic bacteria under acidic conditions (pH < 6), but is hardly effective on anaerobic spore forming bacteria and Lactobacillus acidophilus. Recent studies have shown that sorbic acid has higher antibacterial activity than saturated carboxylic acids of the same carbon number and also prevents the growth of botulinum, staphylococcus aureus, salmonella, etc. Unsaturated fatty acids are intermediates of the assimilation of saturated fatty acids, and can normally participate in metabolism in vivo and be assimilated to produce carbon dioxide and water, so sorbic acid can be regarded as a component of food and is harmless to the human body.

At present, sorbic acid and salts thereof are widely applied to industries such as food, beverage, pickle, can, tobacco, medicine, cosmetics, agricultural products, feed and the like. In cosmetics and personal care products, the chinese, european union, has regulated its maximum allowable use concentration of 0.6% (in terms of acid); the Japanese regulation of the maximum use concentration of 0.5% (total); the U.S. CIR gave the conclusion that it was safe to use sorbic acid at a concentration of not more than 5% and potassium sorbate at a concentration of not more than 1%.

Sorbic acid is slightly soluble in water and is not easy to add and use. The salts of sorbic acid are soluble in alcohols, glycols and are very soluble in water, for example potassium sorbate with a solubility in water of 138g/100g at 20 ℃. Sorbate is easy to add, but still needs to be converted into non-dissociative sorbic acid molecules under acidic conditions (pH < 6) to exert an antibacterial effect, so that sorbate added to the formulation also has the risk of precipitating out due to sorbic acid molecule formation. Because of the characteristics of molecular structures, sorbic acid and salts thereof are easy to oxidize to cause color change, and especially the color change is more obvious in a solution formula. The characteristic of easy color change not only can influence the appearance of products, particularly cosmetics, but also seriously can influence the smell, the flavor and the antibacterial effect of the products.

In the prior art, in order to prevent sorbic acid and salts thereof from being discolored, metal ions, allantoin, complexing agents or antioxidants and the like are generally added to achieve a certain effect.

Chinese patent publication No. CN1175899a, entitled "method for inhibiting brown discoloration caused by sorbate in food and cosmetic compositions", discloses a method for stabilizing food and cosmetic compositions preserved with sorbate in visual and sensory sense, achieving the inventive effect by using allantoin or allantoin and citrate as brown discoloration inhibitor, which has synergistic effect, and which has less color change within 6 months of sorbate in aqueous solution, but does not involve long-term color stabilization of cosmetics (generally for 2 to 3 years) having a long shelf life, nor does it involve solving the problem of poor solubility of sorbic acid in aqueous solution.

U.S. patent publication No. US966246, entitled "stabilized sorbic acid or salts thereof", reduces brown discoloration and odor change caused by sorbate by the addition of metal ions (e.g., manganese, copper, zinc, cobalt, etc.). However, the addition of these heavy metal ions to foods and cosmetics to stabilize color is generally inadequate and unsuitable due to physiological inadequacies.

Furthermore, there are also documents [ Domsch, a. (1994): die Kosmetischen Praparate, volume 2; wassrige und tensidhaltige Formulierungen,4th edition,page 329,Augsburg; verlg fur die chemische Industrie it is reported that sorbate is still subject to discoloration problems in cosmetics that are stored for relatively long periods of time, subject to oxidation. The most commonly employed protection to date is the use of complexing agents (EDTA or citrate) which retard the color change caused by sorbate. However, in transparent plastic bottles, the above-mentioned discoloration problems still remain, especially at high temperatures. Methods for preventing discoloration by adding complexing agents are described and remain limited by the packaging and environment of use.

Disclosure of Invention

The invention provides a color-stable preservative composition containing sorbic acid, which overcomes the defects of easy discoloration and poor water solubility of sorbic acid, and can keep the color stability of the composition containing sorbic acid under the conditions of high temperature, illumination and oxygen contact through the synergistic effect of the components, and has good water solubility and good preservative effect.

The preservative composition consists of 5-35% of organic acid, 0.05-2% of stabilizer, 10-40% of solubilizer, 1-20% of synergistic agent and 20-80% of solvent, wherein the total weight of the composition is 5-35%; the sum of the contents of the components is 100 percent.

The organic acid content of the preservative composition is preferably 10 to 30%.

The stabilizer content in the preservative composition is preferably 0.2 to 1%.

The content of the solubilizer in the preservative composition is preferably 20-30%.

The synergistic agent content in the preservative composition is preferably 5-15%.

The solvent content in the preservative composition is preferably 40 to 65%.

The organic acid in the preservative composition is sorbic acid or a mixture of sorbic acid and at least one of benzoic acid, dehydroacetic acid and salicylic acid.

The stabilizer in the preservative composition is a mixture of citric acid (salt) and one of vitamin C, sodium vitamin C phosphate, butyl hydroxy anisole, 2, 6-di-tert-butyl-p-cresol, propyl gallate, vitamin E acetate and dilauryl 3,3' -thiodipropionate, and the ratio (weight ratio) of the citric acid (salt) to the antioxidant in the mixture is 1:1-2. The mixture has a more pronounced effect on preventing sorbic acid discoloration than citric acid (salt) or an antioxidant alone.

The solubilizer in the preservative composition is polyoxyethylene (n) ₁ ) Castor oil, polyoxyethylene (n) ₂ ) Hydrogenated castor oil, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, or a mixture of two thereof. Selecting polyoxyethylene (n) ₁ ) Castor oil or polyoxyethylene (n) ₂ ) Polymerization degree n of polyoxyethylene in molecule when castor oil is hydrogenated ₁ Or n ₂ Typically 35 to 60; the fatty alcohol polyoxyethylene ether is generally AEO9; the alkylphenol ethoxylates are generally NP-10 or OP-10.

The synergistic agent in the preservative composition is one or a mixture of two of 1, 2-pentanediol, 1, 2-hexanediol, 1, 2-octanediol, 1, 2-decanediol, ethylhexyl glycerol, octanoyl hydroxamic acid, glycerol caprylate, octanoyl glycine and polylysine.

The solvent in the preservative composition is one or a mixture of at least two of 1, 2-propylene glycol, 1, 3-propylene glycol, methyl propylene glycol, dipropylene glycol, 1, 3-butanediol, 2, 3-butanediol, polyethylene glycol 200, polyethylene glycol 400, propylene carbonate, phenoxyethanol and benzyl alcohol.

The preservative composition provided by the invention is easy to prepare, and organic acid, a stabilizer, a solubilizer, a synergistic agent and a solvent are stirred and mixed according to a specified proportion to form a homogeneous solution at a certain temperature (30-60 ℃) by using a method known by a person skilled in the art.

The preservative composition disclosed by the invention can keep stable color under the conditions of high temperature, illumination and oxygen contact.

The preservative composition can keep stable color at 60 ℃ (200 hours) and 90 ℃ (80 hours).

The preservative composition can keep stable color in the illumination intensity of 6000Lux and the illumination time of 10 days.

The preservative composition can keep stable color under the condition of continuously introducing oxygen for 1-8 hours.

The preservative composition provided by the invention can be completely water-soluble under the use concentration, and is free from turbidity and precipitation under normal temperature and low temperature.

The preservative composition of the invention greatly improves the color stability and water solubility of sorbic acid and the corrosion resistance due to the synergistic effect of the components, and can be widely applied to the fields of cosmetics, household washing products, wet tissues and other products.

Detailed Description

The examples described below illustrate the invention in detail, see Table 1. In these examples, all amounts and proportions are by weight.

Example 1

TABLE 1 content of the components of the composition (%)

In a 200mL three-mouth bottle with a stirrer and a thermometer, adding a solvent, a synergistic agent, a solubilizer, an organic acid and a stabilizer according to the feeding amount calculated according to the content of each component in table 1, heating to about 50 ℃ under stirring to completely dissolve the solid, clarifying and transparentizing the solution, and cooling to room temperature to obtain the preservative composition containing sorbic acid with stable color. The obtained composition can keep stable color under the conditions of high temperature, illumination and oxygen contact, has good water solubility and has good anti-corrosion effect.

Example 2

The compositions 3# and 6# and 9# of example 1 were replaced with solvents without the addition of stabilizers to give the corresponding control compositions 3-0# and 6-0# and 9-0# and the control compositions, the corresponding compositions of example 1 and the other compositions were placed in a constant temperature and humidity cabinet for investigation of color stability at high temperatures. The results are shown in tables 2 and 3.

TABLE 2 color stability of the compositions at high temperature (60 ℃ C.)

The results in Table 2 show that the composition containing the stabilizer is more stable in color and has more excellent color stability than the composition without the stabilizer at 60℃for 200 hours.

TABLE 3 color stability of the compositions at high temperature (90 ℃ C.)

The results in Table 3 show that the composition containing the stabilizer is more stable in color and has more excellent color stability than the composition without the stabilizer at 90℃for 80 hours.

Example 3

The compositions 3#, 6# and 9# of example 1 were replaced with solvents without the addition of stabilizers to give the corresponding control compositions 3-0#, 6-0# and 9-0#, and the control compositions, the corresponding compositions of example 1 and the other compositions were placed in a light incubator for investigation of color stability under light conditions. The results are shown in Table 4.

TABLE 4 color stability of the compositions under light (intensity 6000 Lux)

The results in Table 4 show that the composition containing the stabilizer was more stable in color and more excellent in color stability than the composition without the stabilizer under the conditions of an illumination intensity of 6000Lux for 10 days.

Example 4

The compositions 3#, 6# and 7# of example 1 were each adjusted for the stabilizer ratio, replaced with solvent without stabilizer and only one stabilizer was added to give the corresponding control compositions, see table 5. 100mL of the control composition, 100mL of the corresponding composition in example 1 and 100mL of the other compositions in example 1 are respectively put into 200mL triangular flasks, water bath is carried out at 45-50 ℃, oxygen is introduced into the flasks at an air inflow of 1L/min, the color change of each composition under the condition of introducing oxygen in the same time is recorded, and the color stability is examined. The results are shown in Table 6.

TABLE 5 content of the components of the composition (%)

TABLE 6 color stability of the compositions under oxygen-fed conditions

As can be seen from the results in Table 6, the composition without the stabilizer was easily discolored and had poor color stability under the condition of introducing oxygen; the single antioxidants or citric acid (salt) have certain discoloration prevention effect of the composition; but the binary stabilizer of the antioxidant and the citric acid (salt) has better anti-discoloration effect, and the stabilizer with the proportion (weight ratio) of the citric acid (salt) and the antioxidant of 1:1-2 has better effect and the synergistic effect of the two is optimal. The composition of the present invention is demonstrated to have excellent color stability under oxygen exposure.

Example 5

Sorbic acid was simply dissolved in a solvent at a concentration of 10% and 20% to prepare solutions, and control samples # 2-0 and # 4-0 were obtained as shown in Table 7. The control sample and the composition of example 1 were added to water at an amount of 1.5%, and the dissolution in water was observed under stirring at room temperature (20 ℃). The results are shown in Table 8.

TABLE 7 control sample component content (%)

TABLE 8 dissolution of the compositions in water

The results in Table 8 show that the composition of the present invention can greatly improve the actual solubility of organic acids such as sorbic acid in water, and the dissolution performance of sorbic acid in water cannot be significantly improved by only dissolving with a simple solvent. The composition can completely meet the actual application requirement of sorbic acid under the normal addition amount.

Example 6

The sorbic acid pure product, the control sample in example 5 and part of the related composition in example 1 were subjected to a minimum inhibitory concentration (MIC value) test by a plate coating method (for mold, yeast) and a dilution culture method (for bacteria), and the results are shown in table 9.

TABLE 9 MIC values for each composition

The results in table 9 show that the actual bacteriostatic ability of the compositions of the invention is superior to the pure sorbic acid alone or the simple solvent-dissolved control samples at equivalent sorbic acid active concentrations as compared to the control samples. The composition has better synergistic effect and better anti-corrosion effect.

Example 7

The preservative composition of the present invention can be used in various cosmetics, including rinse-off products (such as facial cleanser, shampoo, body wash, hand cleanser, toothpaste, etc.) and leave-on products (such as cream, emulsion, toner, mask, etc.); can also be used for household washing articles (such as tableware detergent, laundry liquid, kitchen and toilet cleaners, etc.); can also be used in various wet tissues. Table 10 shows the amounts of the compositions of example 1 added to various types of products.

TABLE 10 additive amount of the compositions of the invention applied to various products

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Claims

1. A color stable sorbic acid-containing preservative composition characterized in that: consists of organic acid accounting for 5 to 35 percent of the total weight of the composition, stabilizing agent accounting for 0.05 to 2 percent, solubilizer accounting for 10 to 40 percent, synergistic agent accounting for 1 to 20 percent and solvent accounting for 20 to 80 percent;

the organic acid is sorbic acid or a mixture of sorbic acid and at least one of benzoic acid, dehydroacetic acid and salicylic acid;

the stabilizer is a mixture of one of vitamin C, sodium ascorbyl phosphate, butyl hydroxy anisole, 2, 6-di-tert-butyl-p-cresol, propyl gallate, vitamin E acetate and dilauryl 3,3' -thiodipropionate and citric acid or citrate;

the weight ratio of the citric acid or the citrate to the other stabilizer in the stabilizer mixture is 1:1-2;

the solubilizer is one or two of polyoxyethylene (n 1) castor oil, polyoxyethylene (n 2) hydrogenated castor oil, fatty alcohol polyoxyethylene ether and alkylphenol polyoxyethylene ether;

the synergistic agent is one or two of 1, 2-pentanediol, 1, 2-hexanediol, 1, 2-octanediol, 1, 2-decanediol, ethylhexyl glycerol, octanoyl hydroxamic acid, glycerol octanoate, octanoyl glycine and polylysine;

the solvent is one or a mixture of at least two of 1, 2-propylene glycol, 1, 3-propylene glycol, methyl propylene glycol, dipropylene glycol, 1, 3-butanediol, 2, 3-butanediol, polyethylene glycol 200, polyethylene glycol 400, propylene carbonate, phenoxyethanol and benzyl alcohol.

2. A preservative composition according to claim 1, characterized in that: the polyoxyethylene (n 1) castor oil or polyoxyethylene (n 2) hydrogenated castor oil has a polyoxyethylene polymerization degree n1 or n2 of 35 to 60; the fatty alcohol polyoxyethylene ether is AEO9; the alkylphenol ethoxylates are NP-10 or OP-10.

3. Preservative composition according to claim 1 or 2, characterized in that: the organic acid accounts for 10-30% of the total weight of the composition.

4. Preservative composition according to claim 1 or 2, characterized in that: the stabilizer accounts for 0.2-1% of the total weight of the composition.

5. Preservative composition according to claim 1 or 2, characterized in that: the solubilizer accounts for 20-30% of the total weight of the composition.

6. Preservative composition according to claim 1 or 2, characterized in that: the synergistic agent accounts for 5-15% of the total weight of the composition.

7. Preservative composition according to claim 1 or 2, characterized in that: the solvent accounts for 40-65% of the total weight of the composition.

8. Use of the preservative composition according to any one of claims 1 to 7 in cosmetics, household washing products, wet wipes.