阅读说明：本技术 一种温和型防腐体系及其制备方法和应用 (Mild anticorrosion system and preparation method and application thereof ) 是由 汪垠明 田伟兰 卢正美 于 2021-08-26 设计创作，主要内容包括：本发明公开了一种温和型防腐体系及其制备方法和应用,所述防腐体系包括：聚氨丙基双胍1～3wt％,西吡氯铵0.5～2wt％,对羟基苯乙酮0.3～0.8wt％,二元醇10～30wt％,余量为水。本发明针对现有的防腐体系对眼睛具有刺激作用,无法实现真正的无泪配方的缺陷,通过对多种具有防腐功能的防腐剂进行筛选和复配,使组分间发挥协同增效作用,制备得到了一种温和型防腐体系,不仅拓展了抗菌谱,显著提高防腐效果,同时还有效增强了防腐剂的温和保湿性,使其具有良好肤感并且不会对眼睛产生刺激作用,几乎不会导致眼睛发红、干涩或疼痛等问题,实现了真正的无泪配方。(The invention discloses a mild anticorrosion system, a preparation method and application thereof, wherein the anticorrosion system comprises the following components: 1-3 wt% of poly aminopropyl biguanide, 0.5-2 wt% of cetylpyridinium chloride, 0.3-0.8 wt% of p-hydroxyacetophenone, 10-30 wt% of dihydric alcohol and the balance of water. Aiming at the defects that the existing antiseptic system has an irritation effect on eyes and cannot realize a real lacrimation-free formula, the mild antiseptic system is prepared by screening and compounding a plurality of antiseptic agents with antiseptic functions to enable the components to exert a synergistic interaction effect, so that the antiseptic system not only expands the antimicrobial spectrum and obviously improves the antiseptic effect, but also effectively enhances the mild moisture retention of the antiseptic agent, enables the antiseptic agent to have good skin feel, cannot generate an irritation effect on eyes, hardly causes the problems of redness, dryness, pain and the like of the eyes, and realizes the real lacrimation-free formula.)

1. A mild preservative system characterized in that said preservative system comprises: 1-3 wt% of poly aminopropyl biguanide, 0.5-2 wt% of cetylpyridinium chloride, 0.3-0.8 wt% of p-hydroxyacetophenone, 10-30 wt% of dihydric alcohol and the balance of water.

2. A mild preservative system according to claim 1 wherein said glycol is selected from the group consisting of: any one or more of propylene glycol, 1, 2-butanediol, 1, 3-butanediol, 1, 2-pentanediol and 1, 2-hexanediol.

3. A mild preservative system according to claim 1, wherein said preservative system comprises: 2 wt% of polyaminopropyl biguanide, 1 wt% of cetylpyridinium chloride, 0.5 wt% of p-hydroxyacetophenone, 20 wt% of propylene glycol and the balance of water.

4. A process for the preparation of a mild preservative system according to any one of claims 1 to 3, comprising: dissolving p-hydroxyacetophenone in polyol at 50-60 ℃, then sequentially adding polyaminopropyl biguanide and cetylpyridinium chloride, and fully dissolving and mixing to obtain the antiseptic system.

5. Use of a mild preservative system according to any one of claims 1 to 3 in cosmetics.

6. Use according to claim 5, characterized in that said cosmetic product comprises: moisturizing lotion, cosmetic water, lotion, cream, shampoo, facial cleanser, and makeup remover.

7. The use according to claim 5, wherein the preservative system is added in an amount of 3 to 6 wt%.

8. A rose hydrosol comprising the mild preservative system of any one of claims 1 to 3.

9. The rose hydrosol of claim 8, wherein the method of making the rose hydrosol comprises:

step 1, mixing rose petals and water, and then placing the mixture into a distillation kettle for distillation and extraction;

step 2, introducing the mixture generated by distillation into a condenser, and condensing to obtain distillate;

step 3, introducing the distillate obtained in the step 2 into an oil-water separator, and separating the lower layer of the hydrolat from the upper layer of the essential oil to obtain hydrolat;

and 4, filling the hydrosol, and adding the antiseptic system to obtain the rose hydrosol.

10. The rose hydrosol according to claim 9, wherein in the step 4, when the temperature of the hydrosol is 10-15 ℃, the antiseptic system is added in an amount of 4 wt% of the total mass of the hydrosol.

Technical Field

The invention relates to the technical field of cosmetics, in particular to a mild anticorrosion system and a preparation method and application thereof.

Background

The preservative is an essential component in cosmetics and daily chemical care products, and has the main function of protecting products from being polluted by microorganisms in the production or use process. The existing antiseptic systems are very many, and the commonly used antiseptic system is phenoxyethanol, which has specific bacteriostasis to pseudomonas aeruginosa, has certain bacteriostasis to gram-positive bacteria and gram-negative bacteria, has the characteristics of solubility, low toxicity, no hypersensitive stimulation and the like in water, white mineral oil, palmitic acid isopropyl acetate and other cosmetic components, and is widely applied. In recent years, with the increasing demands of consumers for "no additive" and "no preservative", the research in the field of preservative systems has been receiving wide attention.

In order to improve the antiseptic effect, a plurality of substances with antiseptic effect need to be compounded to prepare an antiseptic system so as to expand the antibacterial range and enhance the antibacterial effect. Polyaminopropylbiguanide, a cationic surfactant whose terminal guanidino groups can interact with groups or elements in the organism, destroying its normal substance and energy metabolism, and is therefore widely used in disinfection and preservative systems. Cetylpyridinium chloride, a nitrogen-containing cationic surfactant, acts to inhibit and kill pathogenic bacteria, primarily by lowering surface tension. P-hydroxyacetophenone, hexanediol, pentanediol, caprylic glycol, glyceryl caprylate monoester and the like are also non-traditional preservatives which are widely applied in the market at present. The literature 'study on bacteriostatic performance of polyaminopropyl biguanide and cetylpyridinium chloride in cosmetic water' discloses a technical scheme for compounding two cationic bacteriostatic agents, namely polyaminopropyl biguanide and cetylpyridinium chloride to improve the preservative effect. P-hydroxyacetophenone is also often blended with pentanediol, hexanediol, etc. to avoid bacterial invasion and infection, and is mild in nature. However, the preservative system still has irritation to eyes during use, and the eyes can feel stabbing pain or dry and astringent. With the high standard requirements for products, how to improve the irritation of preservatives to the eyes, achieving a true "tear-free formulation" is an important research and development direction in the field at present.

Disclosure of Invention

Aiming at the defects that an antiseptic system in the prior art has an irritation effect on eyes and cannot realize a real tear-free formula, the invention provides a mild antiseptic system and a preparation method and application thereof.

In order to achieve the purpose, the invention adopts the technical scheme that:

the invention provides a mild corrosion protection system, which comprises: 1-3 wt% of poly aminopropyl biguanide, 0.5-2 wt% of cetylpyridinium chloride, 0.3-0.8 wt% of p-hydroxyacetophenone, 10-30 wt% of dihydric alcohol and the balance of water.

Further, the diol is selected from: any one or more of propylene glycol, 1, 2-butanediol, 1, 3-butanediol, 1, 2-pentanediol and 1, 2-hexanediol.

Further, the preservative system comprises: 2 wt% of polyaminopropyl biguanide, 1 wt% of cetylpyridinium chloride, 0.5 wt% of p-hydroxyacetophenone, 20 wt% of propylene glycol and the balance of water.

Further, the method comprises: dissolving p-hydroxyacetophenone in polyol at 50-60 ℃, then sequentially adding polyaminopropyl biguanide and cetylpyridinium chloride, and fully dissolving and mixing to obtain the antiseptic system.

The invention also provides application of the mild preservative system in cosmetics.

Further, the cosmetic comprises: moisturizing lotion, cosmetic water, lotion, cream, shampoo, facial cleanser, and makeup remover.

Furthermore, the addition amount of the anticorrosion system is 3-6 wt%.

The invention also provides rose hydrosol which contains the mild anticorrosion system.

Further, the preparation method of the rose hydrosol comprises the following steps:

step 1, mixing rose petals and water, and then placing the mixture into a distillation kettle for distillation and extraction;

step 2, introducing the mixture generated by distillation into a condenser, and condensing to obtain distillate;

step 3, introducing the distillate obtained in the step 2 into an oil-water separator, and separating the lower layer of the hydrolat from the upper layer of the essential oil to obtain hydrolat;

and 4, filling the hydrosol, and adding the antiseptic system to obtain the rose hydrosol.

Further, in the step 4, when the temperature of the hydrolat is 10-15 ℃, the anticorrosion system accounting for 4 wt% of the total mass of the hydrolat is added.

Compared with the prior art, the invention has the beneficial effects that: aiming at the defects that the antiseptic system in the prior art has stimulation to eyes and causes stabbing pain and dryness after entering eyes, the antiseptic substances in the antiseptic system are analyzed, screened, matched and combined to enable the components to have synergistic effect, so that the antibacterial spectrum of the antiseptic system is widened, the antiseptic and sterilization effects are obviously improved, the moisturizing effect and the skin feel are improved, meanwhile, the stimulation to the eyes by the antiseptic is obviously reduced, when the pure dew containing the antiseptic system enters the eyes, stimulation can not be basically felt, the eyes hardly have red lacrimation and dryness and pain, a real 'lacrimation-free formula' is realized, the antiseptic system can be widely applied to various cosmetics or daily care products, and the antiseptic system has high production and application values.

Detailed Description

The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

This example provides a rose hydrosol comprising a preservative system, wherein the preservative system comprises: 2 wt% of polyaminopropyl biguanide, 1 wt% of cetylpyridinium chloride, 0.5 wt% of p-hydroxyacetophenone, 20 wt% of propylene glycol and the balance of water.

The preparation method of the anticorrosion system comprises the following steps: dissolving p-hydroxyacetophenone in propylene glycol at 50-60 ℃, then sequentially adding polyaminopropyl biguanide and cetylpyridinium chloride, and fully dissolving and mixing to obtain the antiseptic system.

The preparation method of the rose hydrosol comprises the following steps:

step 1, mixing rose petals and water, placing the mixture into a distillation kettle, and distilling and extracting the mixture at 50-70 ℃;

step 2, introducing the mixture generated by distillation into a condenser, and condensing to obtain distillate;

step 3, introducing the distillate obtained in the step 2 into an oil-water separator, and separating the lower layer of the hydrolat from the upper layer of the essential oil to obtain hydrolat;

and 4, sterilizing and filling the hydrolat, and adding the preservative system accounting for 4 wt% of the total mass of the hydrolat when the temperature of the hydrolat is 10-15 ℃ to obtain the rose hydrolat.

Example 2

The present embodiment is different from embodiment 1 in that:

(1) the preservative system comprises: 1 wt% of polyaminopropyl biguanide, 0.5 wt% of cetylpyridinium chloride, 0.3 wt% of p-hydroxyacetophenone, 10 wt% of 1, 2-butanediol and the balance of water.

(2) When the temperature of the hydrolat is 10-15 ℃, the anticorrosion system accounting for 6 wt% of the total mass of the hydrolat is added.

Example 3

The present embodiment is different from embodiment 1 in that:

(1) the preservative system comprises: 3 wt% of polyaminopropyl biguanide, 2 wt% of cetylpyridinium chloride, 0.8 wt% of p-hydroxyacetophenone, 30 wt% of 1, 2-pentanediol and the balance of water.

(2) When the temperature of the hydrolat is 10-15 ℃, the anticorrosion system accounting for 3 wt% of the total mass of the hydrolat is added.

Comparative example 1

This comparative example differs from example 1 in that: the preservative system comprises: 2 wt% of polyaminopropyl biguanide, 1 wt% of cetylpyridinium chloride and the balance of water.

Comparative example 2

This comparative example differs from example 1 in that: the preservative system comprises: 0.5 wt% of p-hydroxyacetophenone, 20 wt% of propylene glycol and the balance of water.

Comparative example 3

This comparative example differs from example 1 in that: the preservative system comprises: 0.5 wt% of p-hydroxyacetophenone, 20 wt% of 1, 2-hexanediol and the balance of water.

Comparative example 4

This comparative example differs from example 1 in that: the preservative system comprises: 0.5 wt% of p-hydroxyacetophenone, 20 wt% of 1, 2-pentanediol and the balance of water.

Comparative example 5

This comparative example differs from example 1 in that: the preservative system comprises: 0.5 wt% of poly-aminopropyl biguanide, 0.3 wt% of cetylpyridinium chloride, 0.2 wt% of p-hydroxyacetophenone, 8 wt% of propylene glycol and the balance of water.

Comparative example 6

This comparative example differs from example 1 in that: the preservative system comprises: 4 wt% of polyaminopropyl biguanide, 3 wt% of cetylpyridinium chloride, 1 wt% of p-hydroxyacetophenone, 35 wt% of propylene glycol and the balance of water.

Evaluation protocol

1. Corrosion challenge test

The antiseptic efficacy of each sample was verified by taking the rose hydrosol samples prepared in examples 1 to 3 and comparative examples 1 to 6, respectively, in accordance with the united states pharmacopoeia (USP 41 to NF 36), chapter 51 antiseptic efficacy test.

The test method comprises the following steps: separately formulating bacterial and fungal suspensions comprising: escherichia coli (ATCC 8739), Pseudomonas aeruginosa (ATCC 9027), Staphylococcus aureus (ATCC 6538), Candida albicans (ATCC 10231) and Aspergillus Brazilian (ATCC 16404), wherein the concentration of the bacteria is 5X 10⁷CFU/mL, fungal concentration 3X 10⁶CFU/mL, mixed and inoculated in the rose hydrosol sample, and the survival number of the mixed bacteria is checked on 0, 7, 14, 21 and 28 days after inoculation, wherein the lower the survival number, the better the antiseptic effect. The measurement results are shown in table 1.

Table 1 corrosion protection challenge test results

2. Eye irritation test

The rose hydrosol samples prepared in examples 1-3 and comparative examples 1-4 were taken, and the eye reaction scores and the eye irritation reaction grading of the products were performed on different samples according to the acute eye irritation/corrosion test in chapter six of the technical safety standards for cosmetics (2015 edition), and the operation process was as follows:

1.8-2.2 kg of 24 healthy adult white rabbits are taken and divided into 7 groups of 3 rabbits each. Healthy adult white rabbits were acclimatized in the laboratory animal room for 3 days before the experiment. Both eyes of the test animals were examined (including examination with sodium fluorescein) within 24h before the start of the test. Animals with eye irritation symptoms, corneal defects, and conjunctival damage were not used for the test. The experimental animals and the experimental animal rooms meet the national regulations. And can be used for feeding standard compound feed without limitation of drinking water

In the actual test, the lower eyelid of one side of the eye of the rabbit is slightly pulled open, 0.1mL of the test object is dropped into the conjunctival sac, and the upper eyelid and the lower eyelid are passively closed for 1s to prevent the test object from being lost. The other eye was not treated for self-control. Eyes are not washed within 24 hours after the test object is dripped. If the tested object is proved to have irritation, 3 rabbits are selected for carrying out the washing effect test, namely, 30 seconds after the tested object is dripped into the eyes of the rabbits, and at least 30 seconds of water flow which is enough and has a fast flow speed and can not cause the eyes of the animals to be damaged is used for washing.

The eyes of the animals were examined after instillation of the test substance and the score of eye irritation response was recorded according to the scoring criteria for eye damage in table 2. The eye irritation effect of the different samples was graded according to the product eye irritation response grading of table 3 according to the integral.

TABLE 2 Scoring criteria for ocular lesions

TABLE 3 grading of the eye irritation response of the products

Note: when the cornea, iris and conjunctiva are 0, it is judged to be non-irritant.

The results of testing the samples of examples 1 to 3 and comparative examples 1 to 4 for eye irritation are shown in Table 4.

TABLE 4 eye irritation test results

Combining the test results of tables 1 and 4, the rose hydrosol samples of examples 1-3 not only have excellent preservative effect due to the mild preservative system of the present invention, but also have killing effect on various bacteria and fungi, and simultaneously the irritation to eyes is significantly reduced through the synergistic effect of the components, and after the test, the rose hydrosol shows no irritation or micro-irritation to eyes, so that the rose hydrosol can be made into or approach to the tear-free formula infinitely, wherein the combined effect of example 1 is the best. Compared with the examples 1-3, when any component in the preservative system is omitted, the preservative effect is obviously deteriorated, and the irritation effect on eyes is stronger; when the content of each substance in the components is reduced, although the irritation to eyes is reduced, the antiseptic and antibacterial effects are obviously reduced; when the content of each substance in the components is increased, the stimulation effect on eyes is obviously enhanced, but the antiseptic effect is not obviously improved. In summary, only when the preservative system of the invention is adopted, the irritation to eyes can be reduced while the preservative and bactericidal effects are improved, thereby realizing or approaching a lacrimless formula infinitely.

3. Chick embryo chorioallantoic membrane vascular stimulation test (CAMVA)

The rose hydrosol samples prepared in the examples 1-3 of the invention were subjected to a chick embryo chorioallantoic membrane vascular stimulation test to further verify the low irritation effect of the preservative system of the invention.

(1) Test materials and methods

The method selects the fertilized chick embryo of SPF-level White Lai Hangzhou chicken (White egg chicken), the supplier has the qualification of' fixed-point manufacturing enterprises for producing and inspecting the SPF chick (egg) approved by the scientific and technological department, and the quality of the chick embryo is in accordance with the requirement of the national standard.

At room temperature of 20-25 deg.c and relative humidity of 45-70%. The hatching temperature is 37.5 +/-0.5 ℃, and the relative humidity is 50-60%. The purchased 0-day-old embryos were surface-cleaned with 70% alcohol and placed in an incubator (37. + -. 1 ℃ C.) for incubation.

(2) CAM preparation

Chick embryos were checked daily for survival and any abnormal chick embryos were discarded. Hatching 14d, peeling off the egg shell at the end of the air chamber by using dental zigzag forceps, exposing the white egg membrane, dripping a few mL0.9% NaCl solution by using a suction pipe to moisten the egg membrane, and pouring out the 0.9% NaCl solution. Carefully remove the intima with forceps to ensure the vascular membrane is not damaged. Teflon rings were placed on the CAM of each chick embryo as the area of action for dripping the diluted sample.

(3) Procedure of the test

Day 14 chick embryos were selected and 40. mu.l of the sample from examples 1-3 was added to the built-in ring of each chick embryo with pure water as the blank and 0.05M SLS as the positive control. After the dropping is finished, the chick embryos are placed in an incubator environment for 30 +/-5 min, then the chick embryos are taken out of the incubator to be scored, the closed preservative film is removed, the eggshells are stripped to increase the CAM visual field, the change of the CAM blood vessels inside the ring and the change of the CAM blood vessels outside the ring are observed and compared by means of a stereoscopic microscope under auxiliary illumination, and the damage of the blood vessels inside the ring is evaluated. The observations from each chick embryo were recorded.

(4) Evaluation criteria

And (3) classifying vascular effects:

ghost blood vessel ghost vessel: refers to a vessel with no blood perfusion in the blood vessel;

② hyperemia: refers to the phenomenon of blood engorgement caused by the blood failing to flow in blood vessels or by the blood vessels inflating.

③ hemorrhage: blood flows from the blood vessel into the blood vessel and then flows out of the blood vessel, and may be manifested in various forms such as punctate hemorrhage or flocculent diffuse hemorrhage.

The scoring criteria were:

NC value: the irritation level of the test subjects was compared according to the average score size (i.e., NC value) of the vascular injury score. "0 < NC ≦ 2" indicates a stressful stimulus, i.e. a non-traumatic stimulus. The capillary vessels have no bleeding injury; 2< NC < 3, showing slight stimulation, namely slight traumatic stimulation is generated at the moment, and capillary blood vessels have slight bleeding injury at the moment; NC is more than or equal to 3 and less than or equal to 5, and the blood capillary shows moderate stimulation, namely, serious traumatic stimulation is generated at the moment, and the blood capillary shows serious bleeding injury which may be irreversible injury; NC is more than 5, which is marked by severe stimulation, namely extremely severe traumatic stimulation is generated at the moment, and capillaries bleed in a large area, and the bleeding amount is large, which is irreversible damage.

(5) Results of the experiment

The results show that the rose hydrosol samples of the embodiments 1 to 3 of the invention have extremely low irritation and almost no irritation to chick embryos, namely the samples of the invention are lacrimation-free formulas, can be widely applied to various cosmetics or daily washing products, fully meet the high standard and high requirement of consumers on products, and have extremely high production and application values.

The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.