CN109620743B

CN109620743B - Mouthwash containing acidic bactericide and preparation method thereof

Info

Publication number: CN109620743B
Application number: CN201910046403.2A
Authority: CN
Inventors: 郭伊妮; 王静
Original assignee: Weilai (guangzhou) Commodity Co Ltd
Current assignee: Weilai (guangzhou) Commodity Co Ltd
Priority date: 2019-01-17
Filing date: 2019-01-17
Publication date: 2019-12-20
Anticipated expiration: 2039-01-17
Also published as: CN109620743A

Abstract

The invention belongs to the technical field of daily chemical articles, and particularly relates to mouthwash containing an acidic bactericide and a preparation method thereof. The mouthwash containing the acidic bactericide comprises the following preparation raw materials in parts by weight: 75-86 parts of hypochlorous acid aqueous solution, 0.5-3.0 parts of edible ethanol, 0.5-2.5 parts of humectant, 0.5-3.0 parts of surfactant, 2.0-3.0 parts of sweetener, 1-5 parts of pullulan, 0.1-0.5 part of edible pigment and 6-10 parts of water. The mouthwash contains chloric acid aqueous solution which is an acidic bactericide, has excellent bactericidal performance, can kill pathogenic bacteria such as escherichia coli, candida albicans and the like, keeps the oral cavity clean and sanitary, is nontoxic and non-irritant, is stable and safe in system, and can be used for a long time.

Description

Mouthwash containing acidic bactericide and preparation method thereof

Technical Field

The invention belongs to the technical field of daily chemical articles, and particularly relates to mouthwash containing an acidic bactericide and a preparation method thereof.

Background

The hypochlorous acid aqueous solution is also called hypochlorous acid electrolyzed water, is developed and developed by Japan in 90 s of the 20 th century, is an acidic aqueous solution taking hypochlorous acid as a main sterilization component, and has the characteristics of strong sterilization capability, wide sterilization range, no pollution, no residue, safety, reliability, no toxicity or harm to human bodies, no skin irritation, convenient preparation, low price and the like. In 1997, researchers studied the bactericidal effect and safety, and in 2002, hypochlorous acid electrolyzed water was designated as a food bactericide in japan, and then it was put into use in the fields of food, livestock, agriculture, and the like.

The principle of hypochlorous acid electrolysis water generation is that a proper amount of dilute hydrochloric acid with low concentration and/or sodium chloride solution are added into an electrolysis tank with or without a diaphragm, chlorine and hydrogen ions are generated at an anode through electrolysis, the hydrogen ions are dissolved in water to enable the water to be acidic, the chlorine reacts with the water to generate hydrochloric acid and hypochlorous acid, and hydrogen is generated at a cathode. The chloric acid electrolyzed water is divided into strong-acid hypochlorous acid electrolyzed water (the pH value is 2.0-3.0) and slightly-acid hypochlorous acid electrolyzed water (the pH value is 5.0-6.5) according to the pH value. The strong acid hypochlorous acid electrolyzed water has excellent sterilization performance, has small influence on people and environment, can be used for sterilizing surgical instruments and endoscopes, has a corrosion effect on metals and can demineralize hard tissues in the oral cavity due to the strong acidity, and limits the application of the strong acid hypochlorous acid electrolyzed water in the oral cavity field. The pH value of the slightly acidic hypochlorous acid electrolyzed water is close to neutral, so that the method has high safety, small load on the environment and good application prospect in the field of oral cavity.

At present, the oral cavity cleaning of the dental patients is carried out by using the slightly acidic hypochlorous acid electrolyzed water, and the bactericidal rate of pathogenic bacteria such as enterococcus faecalis, streptococcus mutans and the like of the oral cavity of the dental patients is obviously improved after the oral cavity cleaning is found. On one hand, the slightly acidic hypochlorous acid electrolyzed water has poor stability, is easily influenced by illumination, air, time, contact impurities and the like, and causes the reduction of the sterilization effect or difficult persistence, so a container made of a light-proof and closed rigid polyvinyl chloride material is required to be used for storage, and the opening times are required to be reduced in the using process; on the other hand, the slightly acidic hypochlorous acid electrolyzed water has certain corrosivity to metals such as aluminum, copper and the like, and brings trouble to daily use of people. Therefore, the slightly acidic hypochlorous acid electrolyzed water is mainly focused on clinical application at present, and is rarely converted into oral cleaning products such as mouthwash and the like to circulate in the market, so that the application and popularization of the slightly acidic hypochlorous acid electrolyzed water oral care product are greatly restricted.

Therefore, in order to promote the application and popularization of the slightly acidic hypochlorous acid electrolyzed water oral care product, a proper mouth wash system needs to be prepared, so that the stability of the slightly acidic hypochlorous acid electrolyzed water is improved, the excellent sterilization effect is maintained, the corrosivity is reduced, and the daily use of people is facilitated.

Transparent packaging bottles are commonly used and color is added to the mouthwash in order to provide the mouthwash with a good appearance and to enhance human consumption. The existing food-grade pigments comprise synthetic pigments and natural pigments, the natural pigments are high in safety and have the defects of poor stability and sensitivity to light and heat, and the mouthwash is basically packaged by transparent plastic bottles, so that the natural edible pigments are rarely applied to the mouthwash. Gardenia yellow pigment (CAS number 94238-00-3) is a natural edible pigment prepared from Gardenia fruits as raw materials by extracting, separating, concentrating and drying, and is mainly used as a food colorant with good dyeability and bright color. Through retrieval, no research that gardenia yellow pigment is applied to mouthwash as a pigment is found.

Disclosure of Invention

In order to solve the problems in the prior art (such as poor stability of a hypochlorous acid aqueous solution, no mouthwash product containing the hypochlorous acid aqueous solution and the like), the invention provides the mouthwash, which contains an acidic bactericide of a chloric acid aqueous solution, remarkably improves the light and heat stability of the chloric acid aqueous solution, maintains the sterilization effect of the chloric acid aqueous solution on oral pathogenic bacteria, and has bright appearance and color and stable and safe system.

The mouthwash containing the acidic bactericide provided by the invention comprises the following preparation raw materials in parts by weight: 75-86 parts of hypochlorous acid aqueous solution, 0.5-3.0 parts of edible ethanol, 0.5-2.5 parts of humectant, 0.5-3.0 parts of surfactant, 2.0-3.0 parts of sweetener, 1-5 parts of pullulan, 0.1-0.5 part of edible pigment and 6-10 parts of water.

Preferably, the mouthwash of the invention further comprises the following preparation raw materials in parts by weight: 0.05-0.15 part of sodium fluoride.

Preferably, the mouthwash of the invention further comprises the following preparation raw materials in parts by weight: 0.5-1.0 part of edible essence.

Preferably, the humectant is glycerin.

Preferably, the surfactant is tween-20.

Preferably, the sweetener is xylitol.

Preferably, the edible pigment is gardenia yellow pigment.

Preferably, the hypochlorous acid aqueous solution is subacid hypochlorous acid electrolyzed water, the effective chlorine concentration is 40-200 mg/L, the pH value is 4.5-6.5, and the oxidation-reduction potential is not less than 600 mV.

Correspondingly, the invention also provides a preparation method of the mouthwash containing the acidic bactericide, which comprises the following steps:

s1, adding the humectant, the surfactant and the sweetener according to the formula amount into the ethanol according to the formula amount, and uniformly stirring to obtain a solution A;

s2, adding pullulan and edible pigment in formula amount into water in formula amount, and stirring uniformly to obtain solution B;

s3, mixing the hypochlorous acid aqueous solution with the solution A and the solution B according to the formula amount, and uniformly stirring to prepare the mouthwash containing the acidic bactericide.

Further, the step S1 includes adding 0.05 to 0.15 parts by weight of sodium fluoride.

Further, 0.5-1.0 part by weight of flavoring essence is added in the step S1.

In order to improve the stability of the hypochlorous acid aqueous solution and convert the hypochlorous acid aqueous solution into a mouth wash product, the inventor introduces pullulan into a mouth wash basic formula, and unexpectedly finds that the pullulan can obviously improve the stability of the chloric acid aqueous solution, so that the pullulan is suitable for being distributed on the market as an oral cleaning product. The reason is presumed that the pullulan polysaccharide has a highly ordered long-chain macromolecular structure, and is matched with molecules such as a humectant, a surfactant and the like to form a cross network structure, so that hypochlorous acid micromolecules can be kept stable in the network structure, the electrolysis and decomposition reaction is slowed down, the sterilization effect is maintained, and the corrosion to metal is reduced. However, the pullulan should not be added too much, otherwise the mouth wash system is sticky and not easy to pour out for use.

However, in the light test, the mouthwash product is unstable to light, needs to be stored in a shading mode or packaged by using a colored plastic bottle, greatly influences the purchasing desire of consumers, and is not favorable for daily use. The aqueous solution of gardenia yellow pigment is yellow, the color tone of the aqueous solution is hardly influenced by the change of the pH value of the environment, the light stability and the heat stability are better under neutral and alkaline conditions, but the light stability and the heat stability are poor under acidic conditions, and the aqueous solution is easy to brown. The inventor adds the pullulan into a basic formula of the mouthwash, adds a hypochlorous acid aqueous solution, and under the condition of illumination, the mouthwash is browned and turbid, and after the pullulan is added, the light stability and the heat stability of the mouthwash are obviously improved. Therefore, the pullulan and the gardenia yellow pigment are cooperated to improve the stability of the mouth wash containing the hypochlorous acid aqueous solution and ensure that the mouth wash obtains bright yellow color.

Therefore, compared with the prior art, the invention has the advantages that:

(1) the invention provides a novel mouthwash product, which contains a chloric acid aqueous solution which is an acidic bactericide, has excellent bactericidal performance, can kill pathogenic bacteria such as escherichia coli, candida albicans, staphylococcus aureus, pseudomonas aeruginosa and the like, keeps the oral cavity clean and sanitary, is nontoxic and non-irritant, and can be used for a long time.

(2) The mouthwash containing the acidic bactericide has the advantages of stable formula system, convenience in storage and transportation, bright appearance and color, simple preparation method, stable process, low cost, greenness, environmental protection and good market prospect.

Detailed Description

The invention is further illustrated by the following description of specific embodiments.

Example, the mouthwash containing an acidic bactericide of the present invention and the method of preparing the same

The formula of the mouthwash containing the acidic bactericide in embodiments 1 to 5 of the present invention is shown in table 1 below.

TABLE 1

The hypochlorous acid aqueous solution is slightly acidic hypochlorous acid electrolyzed water, the effective chlorine concentration is 40-200 mg/L, the pH value is 4.5-6.5, and the oxidation-reduction potential is not less than 600 mV.

The preparation method of the mouthwash containing the acidic bactericide in the embodiments 1-5 of the invention comprises the following steps:

s1, adding glycerol, tween-20, xylitol, sodium fluoride and edible essence into ethanol according to the formula amount, and uniformly stirring to obtain a solution A;

s2, adding pullulan polysaccharide and gardenia yellow pigment in the formula amount into water in the formula amount, and uniformly stirring to obtain a solution B;

Examples 1 to 5 the effective chlorine concentration and pH of the aqueous rinse containing the acidic bactericide are shown in Table 2 below.

TABLE 2

Item	Example 1	Example 2	Example 3	Example 4	Example 5
						Concentration of available chlorine	80mg/L	40mg/L	100mg/L	140mg/L	120mg/L
pH value	5.5	6.5	6.0	5.0	6.0

The formulation of the mouthwashes of comparative examples 1-4 is shown in table 3 below.

TABLE 3

Raw materials	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4
					Aqueous hypochlorous acid solution	81.4kg	80.4kg	81.1kg	80.1kg
Edible ethanol	2.0kg	2.0kg	2.0kg	5.0kg
					Glycerol	2.0kg	2.0kg	2.0kg	4.0kg
Tween-20	1.5kg	1.5kg	1.5kg	1.5kg
					Xylitol, its preparation method and use	2.5kg	2.5kg	2.5kg	2.5kg
Pullulan polysaccharide	/	3kg	/	3kg
					Gardenia yellow pigment	/	/	0.3kg	0.3kg
Water (W)	10kg	8kg	10kg	3kg
					Edible essence	0.6kg	0.6kg	0.6kg	0.6kg
Concentration of available chlorine	100mg/L	100mg/L	100mg/L	100mg/L
					pH value	6.0	6.0	6.0	6.0

Comparative example preparation of mouthwash the process is according to the examples.

Test example one, test of the bactericidal effect of the mouthwash containing an acidic bactericide of the present invention

1. Testing materials: escherichia coli (8099), Candida albicans (ATCC 10231), Staphylococcus aureus (ATCC6538), Pseudomonas aeruginosa (ATCC 15442), Bacillus subtilis var niger (ATCC 9372), a neutralizing agent (0.1% Tween in physiological saline), a phosphate buffer (0.03mol/L, pH 7.2), Bovine Serum Albumin (BSA), a tryptose old soybean agar medium, a Sabouraud medium, a nutrient agar medium, and the like.

2. The test method comprises the following steps: the mouth rinses of examples 3 and 5 and the aqueous hypochlorous acid solution were tested for their bactericidal effect according to the suspension method of the Disinfection Specification using an aqueous hypochlorous acid solution (effective chlorine concentration of 100mg/L, pH value of 6.0) as a control.

3. The results are shown in Table 4 below.

TABLE 4

As can be seen from the above table 4, the mouthwash containing the acidic bactericide has an ideal killing effect on pathogenic bacteria such as escherichia coli, candida albicans, staphylococcus aureus, pseudomonas aeruginosa, bacillus subtilis var niger and the like, and the sterilizing effect of the mouthwash is equivalent to that of a hypochlorous acid aqueous solution with the same effective chlorine concentration, which indicates that the auxiliary material of the mouthwash has no influence on the sterilizing effect of hypochlorous acid.

Test example two, toxicological test of mouthwash containing an acidic bactericide according to the present invention

The mouth rinses of examples 1 to 5 were tested according to the "disinfection technical specification" acute oral toxicity test and skin irritation test, and the toxicity was observed by comprehensive evaluation of the test animal LD50 and one-time complete skin irritation test.

Toxicological tests show that:

the results of the acute oral toxicity test of the mouthwash of examples 1-5 are as follows: actual nontoxic grade, LD50 is more than or equal to 5000 mg/kg;

examples 1-5 mouthwash one-time complete skin irritation test results: the skin irritation index is 0 to less than 0.5, and the skin irritation index is non-irritant level.

Therefore, the mouthwash containing the acidic bactericide is non-toxic and non-irritant, and is suitable for various people.

Test example three, corrosiveness test of mouthwash containing acidic bactericide of the present invention

1. The material is as follows: circular, 24.0mm in diameter and 1.0mm in thickness, and has a total surface area of about 9.80cm²(including upper, lower, peripheral surfaces and aperture sides) with a finish of 6. The raw materials are as follows: carbon steel (specification is GB/T700-65); aluminium (specification see GB/T1173-74).

2. The test method comprises the following steps: soaking in detergent with surface activity for 10min according to metal corrosion test of Disinfection technical Specification, removing oil sufficiently, and cleaning; test samples (mouth rinses of examples 1 to 4 and comparative examples 3 to 4, hypochlorous acid aqueous solution with an effective chlorine concentration of 100mg/L, pH value of 6.0) were prepared at the highest use concentration to soak the test pieces. During soaking, each metal sheet needs to be soaked in 200ml of a sample, oxide layers on two sides and the peripheral surface of the metal sheet are ground by 120-mesh-size water sand paper, and then tap water is used for cleaning. The diameter, thickness, pore size (to the nearest 0.1mm) of the tablets were measured. Degreasing again by using anhydrous acetone or anhydrous ethanol. Drying in a 50 ℃ constant temperature oven for 1h, weighing after the temperature is reduced to room temperature, weighing each metal sheet for 3 times after the balance returns to zero, and accurately weighing to 0.1mg, wherein the average value is taken as the weight before the test. When weighing, the user should wear clean gloves without touching the sample wafer directly.

3. The test results are shown in table 5 below.

TABLE 5

From table 5 above, it can be seen that: compared with a hypochlorous acid aqueous solution and a comparative example 3 (without pullulan), the mouthwash containing the acidic bactericide has obviously reduced corrosivity on aluminum sheets and carbon steel sheets, and the pullulan is prompted to slow down the corrosion of hypochlorous acid on metals such as aluminum, carbon steel and the like to a certain extent. Comparative example 4 changes the content of partial raw materials, so that the corrosivity of the raw materials on aluminum sheets and carbon steel sheets is improved, and the corrosion inhibition effect of the pullulan is influenced by other raw materials and contents.

Test example four stability test of mouth rinse containing acidic antiseptic according to the present invention

Accelerated thermal stability test: referring to an accelerated test method in disinfection product stability determination in disinfection technical Specification, commercially packaged samples (mouth washes of examples 1 to 5 and comparative examples 1 to 4) were placed in a 37 ℃ incubator in a dark place for 3 months. The content of available chlorine was measured before and after standing. The samples were tested in triplicate for three batches each time, and the average value was taken 2 times.

Accelerated photostability test: commercially packaged samples (mouthwash of examples 1 to 5 and comparative examples 1 to 4) were placed in an illumination box under the conditions of an illumination of 4500lx and a temperature of 20 ℃ for 10 days, sampled every 2 days for observation, and the appearance change was recorded, and the content of available chlorine was measured on the 10 th day.

The available chlorine test method is in accordance with Disinfection Specification 4.3.4.2.1. The decrease rate of the available chlorine content ═ effective chlorine content at the start of the test-effective chlorine content at the end of the test)/effective chlorine content at the start of the test ] × 100%. The results are shown in Table 6 below.

TABLE 6

From table 6 above, it can be seen that:

(1) the mouthwash containing the acidic bactericide in the embodiments 1 to 5 of the invention shows excellent stability through the thermal stability and light stability accelerated tests, the reduction rate of the hypochlorous acid content of the bactericidal active ingredient is lower than 10%, the appearance is normal, the adverse phenomena such as layering, precipitation and turbidity do not exist, the fresh yellow color is kept, and the quality guarantee period can be estimated to be 2 years.

(2) In comparison with example 3, comparative example 1, which did not contain pullulan and gardenia yellow pigment, was a colorless transparent liquid, and as a result, the hypochlorous acid content was greatly reduced and the system became a white turbid solution after the heat and light acceleration test. Compared with the comparative example 1, the pullulan is added in the comparative example 2, so that the thermal stability is obviously improved, but the light stability is poor; the gardenia yellow pigment is added in the comparative example 3, and the stability of the gardenia yellow pigment is not different from that of the comparative example 1 under the condition of not adding the pullulan; comparative example 4 changes the content of part of the raw materials, and then the chloric acid content is obviously reduced, and the system is browned yellow; the stability of the hypochlorous acid and the stability of the gardenia yellow pigment can be improved by the pullulan in the formula system, so that the light stability of the mouthwash is enhanced.

The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.

Claims

1. The mouthwash containing the acidic bactericide is characterized by comprising the following preparation raw materials in parts by weight: 75-86 parts of hypochlorous acid aqueous solution, 0.5-3.0 parts of edible ethanol, 0.5-2.5 parts of humectant, 0.5-3.0 parts of surfactant, 2.0-3.0 parts of sweetener, 1-5 parts of pullulan, 0.1-0.5 part of edible pigment and 6-10 parts of water;

the hypochlorous acid aqueous solution is subacid hypochlorous acid electrolyzed water, the effective chlorine concentration is 40-200 mg/L, the pH value is 4.5-6.5, and the oxidation-reduction potential is not less than 600 mV.

2. The mouthwash containing the acidic bactericide as claimed in claim 1, further comprising the following raw materials for preparation in parts by weight: 0.05-0.15 part of sodium fluoride.

3. The mouthwash containing the acidic bactericide as claimed in claim 1, further comprising the following raw materials for preparation in parts by weight: 0.5-1.0 part of edible essence.

4. The acidic antiseptic-containing mouthwash according to claim 1, wherein the humectant is glycerin.

5. The acidic bactericide-containing mouthwash according to claim 1, wherein the surfactant is tween-20.

6. The acidic bactericide-containing mouthwash according to claim 1, wherein the sweetener is xylitol.

7. The acidic bactericide-containing mouthwash according to claim 1, wherein the food color is gardenia yellow.

8. A process for preparing a mouthwash containing an acidic antiseptic according to claim 1, characterized in that it comprises the following steps:

s1, adding the humectant, the surfactant and the sweetener according to the formula amount into the edible ethanol according to the formula amount, and uniformly stirring to obtain a solution A;

9. The method for preparing the mouthwash containing the acidic disinfectant according to claim 8, wherein the step S1 further comprises adding 0.05 to 0.15 parts by weight of sodium fluoride and 0.5 to 1.0 parts by weight of flavoring essence.