CN111971018A

CN111971018A - Dandruff-removing itching-relieving hair-washing and hair-nourishing composition containing fibroin component and preparation method thereof

Info

Publication number: CN111971018A
Application number: CN201980014295.9A
Authority: CN
Inventors: 张向阳
Original assignee: Guangzhou Qiyuan Biotechnology Co ltd
Current assignee: Guangzhou Qiyuan Biotechnology Co ltd
Priority date: 2018-10-15
Filing date: 2019-03-29
Publication date: 2020-11-20
Also published as: WO2020077956A1; CN108992357A

Abstract

The scurf-removing itching-relieving hair washing and nourishing composition comprises the following components in parts by weight: 70-85 parts of deionized water, 0.1-03 parts of disodium ethylene diamine tetraacetate, 0.2-0.4 part of citric acid, 1-3 parts of glycerol, 10-15 parts of AESA surfactant, 1-3 parts of imidazoline, 1-3 parts of olefin sodium sulfonate, 1-3 parts of diethanolamide, 2-4 parts of cellulose acetate butyrate, 1-8 parts of fibroin hydrolysate, 0.1-0.3 part of Kathon, 0.1-0.3 part of essence and a proper amount of sodium chloride.

Description

Dandruff-removing itching-relieving hair-washing and hair-nourishing composition containing fibroin component and preparation method thereof

Technical Field

The invention relates to a hair washing and nourishing composition, belongs to the technical field of chemical nursing products, and particularly relates to a scurf removing, itching relieving, hair washing and nourishing composition containing a fibroin component and a preparation method thereof.

Background

Dandruff is a common physiological phenomenon in humans and is a repetitive and multiple skin problem. The increase of dandruff not only brings discomfort to people along with scalp itching, but also very affects the beauty of the head. The traditional theory of removing dandruff and relieving itching is considered as follows: dandruff is produced by fungi such as malassezia furfur. Much research has focused on how to inhibit or kill these microorganisms with better biocides.

Therefore, the dandruff removing and itching relieving components with various shapes and various types and with the bactericidal effect are applied to the dandruff removing and itching relieving shampoo products. To these shampoo formulations are added ingredients such as: synthetic bactericides such as ganbaosu, ZPT, OTC and the like, or plant bactericides such as honeysuckle, citronella, tea tree oil, radix sophorae flavescentis and the like, but even if the synthetic bactericides, the ZPT, the OTC and the like are adopted, no product can better solve the problem of dandruff and scalp pruritus. Because, another key factor in scalp formation-dandruff and scalp itching caused by dry skin-is overlooked.

In fact, researches show that the surface of human scalp has an ecological balance microecological environment consisting of physiological lipid, natural moisturizing factors, microbial populations and the like, and the scalp can be kept healthy by maintaining the microecological environment balance of the scalp.

Therefore, to maintain our scalp micro-ecological balance, we have started from maintaining physiological lipid balance, scalp moisturization, maintaining scalp microbial population stability, etc. when we design anti-dandruff product formulations. Shampoo products in the prior art do not consider the product formula for removing dandruff from the aspects of maintaining scalp micro-ecological balance, and solve the technical problems of scalp dryness, water shortage and the like from the aspects of solving physiological factors generated by dandruff from the source.

As is known, silk is composed of an outer layer of sericin and an inner layer of fibroin. The sericin is silkworm sericin and the fibroin is keratin, and is a superior natural skin care material. However, since silk is mainly used in textile industry today, there is no silkworm dedicated to the development and cultivation of cosmetics, and thus, many problems such as too many impurities in raw materials of products, high allergic rate, etc. are caused.

However, reports of using hydrolyzed fibroin materials as the main component of anti-dandruff have not been made.

Disclosure of Invention

In view of the problems of the prior art, the present invention aims to provide an anti-dandruff itching-relieving hair-washing and hair-nourishing composition containing a fibroin component, which solves the problem of dandruff caused by excessive proliferation of microorganisms by comprehensively considering two factors of enhancing the moisture retention of the scalp and properly inhibiting the normal level of the microbial population of the scalp on the basis of the theory of improving and maintaining the micro-ecological environment of the scalp by using a shampoo containing a fibroin component.

The invention also aims to provide a preparation method of the anti-dandruff itching-relieving hair washing and nourishing composition containing the fibroin component.

The technical scheme adopted by the invention is as follows:

a preparation method of fibroin hydrolysate comprises the following steps:

1) selecting silkworm cocoons of high-quality breeding silkworms with large shell thickness, removing silkworm chrysalis, silkworm clothing and impurities in the silkworm cocoons, and mincing for later use;

2) using 0.1-1% sodium carbonate or sodium bicarbonate solution as degumming agent with cocoon content of 0.4-10%, controlling hydrolysis temperature at 50-100 deg.C water bath temperature for degumming for 2-4 hr, filtering to obtain hydrolyzed silk fibroin (filtrate) and silk fibroin fiber (filter residue); desalting the obtained filtrate by an electrodialysis device to obtain desalted hydrolyzed sericin for use, wherein the desalted solution can be used for next hydrolysis, so that the discharge, the cost and the pollution are reduced;

3) dissolving the silk fibroin fiber filter residue in a neutral salt solution with the mass ratio concentration of 30-50%, and controlling the temperature to be 80-100 ℃; the hydrolysis end point is judged by comparing and testing the light transmittance of the hydrolysate through an ultraviolet visible spectrophotometer;

4) performing electrodialysis on the hydrolyzed silk fibroin liquid to remove the impurity ions in the solution, and circulating the solution until the conductivity of the solution is 100-500us/cm to obtain a light yellow silk fibroin pure solution; the separated electrolyte solution can be used for the next hydrolysis production;

5) and finally, mixing the fibroin protein solution with the mass concentration of 1-5% and the sericin protein solution with the mass concentration of 1-5% to obtain the whole silk hydrolysate with the protein molecular weight of 2-20 ten thousand daltons.

Further, in step 1), the method for breeding silkworm cocoons comprises:

1) selecting the mulberry field:

the mulberry is planted in the Yunnan mountain area with sufficient sunlight and large day-and-night temperature difference, the mulberry leaves have high sugar content and are beneficial to the healthy growth of silkworm babies, so that high-quality cocoon shells with thick shells are obtained, in addition, a natural barrier is formed by the unique small basin structure in the Yunnan mountain area, so that the pesticide in the non-silkworm rearing area is reduced from scattering to the silkworm rearing area, and the pesticide residue of a final product is guaranteed;

2) selection of breeding silkworms:

the breeding silkworm is a second generation silkworm obtained from a silkworm industry technical station, and the breeding silkworm is adopted for the purpose of stable content of the obtained sericin protein and the silk fibroin protein, so that a hydrolysis final product with a stable ratio of the hydrolyzed sericin protein to the hydrolyzed silk fibroin protein is obtained;

3) a culture environment:

the culture environment of the silkworm is related to the microbial control of the later-stage product and silkworm leaf disease; in the invention, the silkworm breeding environment adopts aseptic, ventilated and dry silkworm indoor breeding to reduce the risks of germs, microorganisms and the like of the final product;

4) storage conditions were as follows:

silk is an active protein and needs to be stored in a cool, dry, ventilated place.

Further, in the step 3), the neutral salt solution is selected from anhydrous CaCl with the mass ratio concentration of 30-50%₂、CaCl ₂-H ₂O、CaCl ₂-2H ₂O or LiBr solution.

Further, in the step 3), the control of the hydrolysis end point is to ensure that the molecular weight of the fibroin of the final product obtained in the step 5) is controlled within an interval range of 2 ten thousand to 20 ten thousand daltons, mainly concentrated within the interval range of 10 ten thousand to 20 ten thousand daltons, and the hydrolysate obtained by other patents or processes is the silk peptide or the amino acid; the control of the molecular weight of the final product is a guarantee of the efficacy of the product obtained by the product of the invention.

In addition, the dandruff removing, itching relieving, hair washing and nourishing composition containing the fibroin component comprises the following components in percentage by weight:

70-85 parts of deionized water, 0.1-0.3 part of disodium ethylene diamine tetraacetate, 0.2-0.4 part of citric acid, 1-3 parts of glycerol, 10-15 parts of AESA surfactant, 1-3 parts of imidazoline, 1-3 parts of olefin sodium sulfonate, 1-3 parts of diethanolamide, 2-4 parts of cellulose acetate butyrate, 1-8 parts of fibroin hydrolysate, 0.1-0.3 part of Kathon, 0.1-0.3 part of essence and a proper amount of sodium chloride.

The scurf-removing itching-relieving hair washing and nourishing composition containing the fibroin component is prepared from the fibroin hydrolysate by the following process:

1) degumming the silkworm cocoons by using a weak alkaline aqueous solution as a degumming agent according to a conventional method, wherein the degumming agent is used for degumming the silkworm cocoons under the conditions that the mass percent of the solution of the degumming agent is 0.4-6%, the pH value is 8-11, and the hydrolysis temperature is 50-100 ℃;

2) filtering the solution in the step 1) to form degumming hydrolysate and silk fibroin fibers;

3) separating the degumming hydrolyzed solution filtered out in the step 2) into sericin hydrolyzed solution and dialysis ionic solution through electrodialysis, retaining the sericin hydrolyzed solution, and transferring the dialysis ionic solution to next sericin hydrolysis; the hydrolysis end point is judged by comparing and testing the light transmittance of the hydrolysate through an ultraviolet visible spectrophotometer;

4) dissolving the silk fibroin fibers obtained by filtering in the step 2) in a neutral salt solution with the temperature of 60-100 ℃ and the mass percent of 30-60% to form silk fibroin liquid;

5) performing electrodialysis on the hydrolyzed silk fibroin solution obtained in the step 4) to remove ions in the solution, and circulating until the conductivity of the solution is reduced to 10-500us/cm to obtain a light yellow silk fibroin pure solution, wherein the ion solution after electrodialysis can be circularly used as a neutral solution in the step 4);

6) and (3) uniformly mixing the sericin hydrolysate obtained in the step 3) and the fibroin pure solution obtained in the step 5) to obtain the novel fibroin hydrolysate with the characteristics of the surfactant.

Further, in the step 1), the degumming agent adopts sodium carbonate or sodium bicarbonate water solution; the hydrolysis temperature is 50-80 ℃, and the hydrolysis time is 2-4 hours;

further, the hydrolysis end point control of the fibroin in the step 3) is to determine the hydrolysis end point by testing the light transmittance of the hydrolysate with an ultraviolet-visible spectrophotometer so as to obtain the fibroin with the molecular weight of 1 ten thousand-20 ten thousand daltons and the optimal molecular weight of 10 ten thousand-20 ten thousand daltons, so that the final product has the optimal effects of foamability, foam stability, moisture retention, scalp repair and the like.

Further, the neutral salt solution in the step 4) is CaCl_2、CaCl _2-H ₂O、CaCl _2-2H ₂O or LiBr solution.

In addition, the invention also provides a preparation method of the dandruff removing, itching relieving, hair washing and nourishing composition containing the fibroin component, which comprises the following steps:

1) mixing the raw materials of the components at room temperature, adding water and disodium ethylene diamine tetraacetate into a pot, stirring and dissolving;

2) sequentially adding AESA, imidazoline, olefin sodium sulfonate, diethanol amide, glycerol and cellulose acetate butyrate for dissolving and completely transparent;

3) sequentially adding the kasong and the essence to dissolve and completely transparent;

4) finally, adding fibroin hydrolysate silk, stirring uniformly, adding salt to adjust viscosity (25 ℃): 5000, adding citric acid to adjust the pH value to 5.8-6.5.

Furthermore, the dandruff removing, itching relieving, hair washing and nourishing composition used in hair washing has the scalp micro-ecological environment consisting of physiological lipid, natural moisturizing factors and scalp microorganism population which are improved.

By means of the technical scheme, the invention has the following advantages and beneficial technical effects:

1) the fibroin hydrolysate obtained by the fibroin hydrolysis process is based on the theory of how to maintain the scalp micro-ecological environment, and the special moisture retention and repair functions of the fibroin hydrolysate are utilized, so that the problems of scalp dryness, water shortage, easy breakage of hair and the like are solved, and the physiological reason of dandruff generation is solved fundamentally.

2) In addition, the inhibition effect of the silk hydrolysate on the main microorganism commonly recognized to influence dandruff is tested by adopting the silk hydrolysate with different concentrations, and the silk hydrolysate with different concentrations of 3 percent and 4 percent obtained by adopting the silk protein hydrolysis process described by the invention respectively has 14 percent and 24 percent inhibition rate on the malassezia furfur.

Therefore, the two mechanisms are applied simultaneously, and the synergistic effect is achieved on better inhibition of dandruff; the scalp care product can improve the skin moisturizing performance, improve the scalp micro-ecological environment consisting of physiological lipid, natural moisturizing factors and scalp microbial population, maintain the scalp health, and achieve the effects of removing dandruff and relieving itching.

3) The dandruff removing, itching relieving, hair washing and hair nourishing composition containing the fibroin component can achieve the effect of removing dandruff without adding any Chinese herbal medicine or synthetic bactericide; as can be seen from the results of multiple tests, the shampoo prepared by the formula without any dandruff removing and itching relieving component also has the dandruff removing and itching relieving effects.

Moreover, the clean scalp can be maintained for 3-4 days, in the actual production formula, a proper Chinese herbal medicine bactericide or a synthetic bactericide is matched in the formula, so that the dandruff problem caused by excessive reproduction of microorganisms is solved, the two mechanisms are simultaneously applied, the synergistic effect on better inhibiting the dandruff is achieved, and the scalp care liquid has the characteristics of simple formula and excellent use effect.

Drawings

FIG. 1 is a schematic diagram showing the distribution range of the main molecular weight of the silk hydrolysate of the present invention ranging from 2 ten thousand to 20 ten thousand daltons.

FIG. 2 is a graph showing the effect of the test of the compatibility of the silk hydrolysate and other surfactants according to the present invention.

Fig. 3 is a graph showing the scalp effects of the anti-dandruff, anti-itching hair washing and caring composition of the present invention before and after use, respectively.

Detailed Description

The technical solutions of the present invention are described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, 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.

We have found that the ecological environment of the scalp surface is constructed by physiological lipids, dandruff, moisturizing factors, microbial populations, and the like. Microorganisms are not necessarily the primary factor in the acceleration of scalp exfoliation. The lack of moisturizing components such as physiological lipids and fibroin is an important cause of dandruff generation and accelerated exfoliation. The aim of removing dandruff and relieving itching can be achieved by constructing or protecting a healthy ecological environment on the surface of the scalp:

1) physiological lipid and filaggrin cooperate to construct a barrier of scalp epidermis;

2) moisturizing factors such as fibroin and degradation products thereof keep the water content of the horny layer, maintain the pH weak acid environment of the horny surface layer, strengthen the adhesion effect of intercellular substance, and further maintain the flora balance on the skin surface; normal proliferation of scalp microbial populations and breakdown of dandruff may be converted to partial moisturizing factors.

3) The hydrolyzed fibroin has a large amount of hydrophilic groups on the decomposed side chain, so that good hygroscopicity is obtained, and the moisture retention of scalp can be enhanced. The sericin and the micromolecular keratin obtained by the fibroin hydrolysis process can form a 'mud' cell adhesion substance on the surface of the scalp, and can repair epidermal cells to be peeled off and delay the falling off of the scalp. Meanwhile, the hair shaft can be repaired, and the hair breakage can be prevented or reduced.

4) The fibroin hydrolysate obtained by the fibroin hydrolysis process has a certain inhibiting effect on malassezia furfur.

5) The irritability of conventional surfactants used in shampoo is one of the factors of dandruff formation, and a part of foaming agent in shampoo stimulates scalp to accelerate and increase the production of dandruff. The sericin hydrolysate obtained by the fibroin hydrolysis process can effectively prevent or reduce the irritation of the foaming agent to the scalp, thereby further reducing dandruff.

In summary, the main principle of the present invention is: the skin moisturizing performance is improved, the scalp micro-ecological environment of the scalp consisting of physiological lipid, natural moisturizing factors and scalp microbial population is improved, the scalp health is maintained, the fibroin hydrolysate obtained by the adopted fibroin hydrolysis process has a certain inhibiting effect on malassezia furfur, and the irritation of a foaming agent to the scalp can be effectively prevented or reduced, so that the effects of removing dandruff and relieving itching are achieved.

The invention provides a dandruff-removing itching-relieving hair washing and nourishing composition containing a fibroin component, which comprises the following components in parts by weight:

The fibroin hydrolysate added into the dandruff-removing itching-relieving hair washing and nourishing composition containing the fibroin component enhances the moisture retention of the scalp, repairs and improves the adhesion among scalp keratinocytes, and improves the scalp micro-ecological environment consisting of physiological lipid, natural moisture retention factors and scalp microbial population of the scalp, thereby achieving the technical effect of slowing or reducing the generation of dandruff.

The key point of the technology of the invention and the difference with other patent applications is that a retention type skin moisturizing component which is not easy to wash is added in the formula, and especially, fibroin hydrolysate obtained by a special process is preferably added. As is well known, silk is mainly composed of two components: sericin and silk fibroin. Wherein the sericin is mainly collagen, and the fibroin is keratin. Silk contains 18 kinds of amino acids, and 10 kinds of amino acids essential or semi-essential for human body. Since sericin and fibroin need to be hydrolyzed under different hydrolysis conditions, we adopt a two-step hydrolysis method to obtain a fibroin hydrolysate containing both sericin and keratin.

The raw material source of silk and the preparation process of the fibroin hydrolysate will be described below.

Raw material source of silk

The invention selects special silk for cosmetics, which needs to meet the following conditions:

1. selection of mulberry field

2. selection of breeding silkworms

The breeding silkworm is the second generation silkworm obtained from the silkworm industry technical station, and the breeding silkworm is adopted for the purpose of obtaining the stable content of the sericin and the silk fibroin, thereby obtaining a hydrolysis final product with the stable proportion of the hydrolyzed sericin and the hydrolyzed silk fibroin.

3. Cultivation environment

The culture environment of the silkworm is related to the microbial control of the later-stage product and silkworm leaf disease. In the invention, the silkworm breeding environment adopts sterile, ventilated and dry silkworm breeding indoors to reduce the risks of germs, microorganisms and the like of the final product.

4. Storage conditions

Secondly, the production process and quality control of the fibroin hydrolysate:

a silk raw material with good quality needs to be subjected to quality control of each link. Selecting breeding silkworms; from mulberry leaf planting to silkworm feeding; from mature silkworms to cocoons; from storage to transport; especially, the hydrolysis process control of the silk can be realized through different process control, so that the activity of the silk protein can be well kept, and the hydrolyzed silk protein with different molecular weights and different functions can be obtained.

Example 1 (preparation of Silk protein hydrolysate)

A preparation process of fibroin hydrolysate comprises the following steps:

1) selecting 10g of high-quality silkworm cocoons with large shells, removing silkworm pupas in the silkworm cocoons, removing silkworm coats from the silkworm cocoons, cleaning impurities, and mincing for later use;

2) using 90 g of 1% sodium carbonate solution as a degumming agent, controlling the hydrolysis temperature at 50-80 ℃ for degumming for 4h, and filtering to obtain hydrolysis filtrate and silk fibroin fiber (filter residue);

3) dissolving the silk fibroin fiber filter residue in 30% anhydrous CaCl by mass₂In the solution, the temperature is 60-100 ℃; when the light transmittance reaches about 40%, stopping hydrolysis;

4) performing electrodialysis on the hydrolyzed silk fibroin liquid in a semi-permeable membrane permeation bag to remove the impurity ions in the solution, and circulating the solution until the conductivity of the solution is 100us/cm to obtain a light yellow silk fibroin pure solution;

5) simultaneously carrying out electrodialysis on the degumming water solution obtained by degumming until the conductivity is reduced to 100us/cm of the sericin solution, thus obtaining a light yellow sericin solution;

6) and finally, mixing the fibroin protein solution and the sericin protein solution to obtain the whole silk hydrolysate which has the molecular weight range of 2-20 ten thousand daltons, smooth hand feeling and good water-retaining property.

The whole silk hydrolysate of this example was used to prepare a novel silk protein hydrolysate with surfactant properties.

As shown in FIG. 1, the light yellow whole silk hydrolysate of this example has a main molecular weight range of 2 ten thousand to 20 ten thousand daltons. The product has smooth hand feeling and good water retention, has certain foamability and has good foam increasing and stabilizing effects when being compounded with other surfactants.

Example 2 (preparation of fibroin hydrolysate)

A preparation process of fibroin hydrolysate comprises the following steps:

1) selecting 20g of high-quality silkworm cocoons with large shells, removing silkworm pupas in the silkworm cocoons, removing the silkworm cocoons, cleaning impurities, and mincing for later use;

2) using 150 g of 0.5% sodium bicarbonate solution as degumming agent, controlling the hydrolysis temperature at 50-80 ℃ for degumming for 3h, and filtering to obtain hydrolysis filtrate and silk fibroin fiber (filter residue);

3) dissolving the silk fibroin fiber filter residue in anhydrous CaCl with the mass ratio concentration of 50%₂In the solution, the temperature is 60-100 ℃; when the light transmittance reaches about 35%, stopping hydrolysis;

4) performing electrodialysis on the hydrolyzed silk fibroin liquid in a semi-permeable membrane permeation bag to remove the impurity ions in the solution, and circulating until the conductivity of the solution is 500us/cm to obtain a light yellow silk fibroin pure solution;

5) simultaneously carrying out electrodialysis on the degumming water solution obtained by degumming until the conductivity is reduced to 500us/cm of the sericin solution, thus obtaining a light yellow sericin solution;

6) finally, mixing the silk fibroin solution and the sericin solution to obtain the product with the molecular weight of 5-20 kilodalton; the whole silk hydrolysate has smooth hand feeling and good water retention property.

The main molecular weight range of the light yellow whole silk hydrolysate is 5-20 ten thousand daltons; the product has smooth hand feeling and good water retention, has certain foamability and has good foam increasing and stabilizing effects when being compounded with other surfactants.

Example 3 (preparation of fibroin hydrolysate)

A preparation process of fibroin hydrolysate comprises the following steps:

1) selecting 30g of high-quality silkworm cocoons with large shells, removing silkworm pupas in the silkworm cocoons, removing the silkworm cocoons, cleaning impurities, and mincing for later use;

2) using 200 g of 5% sodium bicarbonate solution as a degumming agent, controlling the hydrolysis temperature at 50 ℃ for degumming for 4h, and filtering to obtain hydrolysis filtrate and silk fibroin fiber (filter residue);

3) dissolving the silk fibroin fiber filter residue in anhydrous CaCl with the mass ratio concentration of 60%₂In the solution, the temperature is 100 ℃; when the light transmittance reaches about 50%, stopping hydrolysis;

4) performing electrodialysis on the hydrolyzed silk fibroin liquid in a semi-permeable membrane permeation bag to remove the impurity ions in the solution, and circulating until the conductivity of the solution is 400us/cm to obtain a light yellow silk fibroin pure solution;

5) simultaneously carrying out electrodialysis on the degumming water solution obtained by degumming until the conductivity is reduced to 400us/cm of the sericin solution, thus obtaining a light yellow sericin solution;

6) finally, mixing the silk fibroin solution and the sericin solution to obtain the product with the molecular weight of 10-20 kilodalton; functional whole silk hydrolysate.

The main molecular weight range of the light yellow whole silk hydrolysate is 10-20 ten thousand daltons; the product has smooth hand feeling and good water retention, has certain foamability, and has good foam increasing and stabilizing effects when being compounded with other surfactants (such as coco glucoside, sodium lauryl glucoside carboxylate, lauryl glucoside and fatty alcohol-polyoxyethylene ether).

Effect test example 1 (skin irritation)

1. Multiple skin irritation tests (test report provided by the Guangdong provincial insurance testing center).

2. The detection basis is as follows: method for skin irritation test in 2015 edition, technical Specification for cosmetic safety.

3. Test method

3.1 contamination method:

4 common-grade New Zealand rabbits, each half of the female rabbit and the male rabbit. Before the test, the two sides of the spine of the experimental animal are cut off, and the hair removing range is about 3cm by 3cm respectively at the left side and the right side. Applying about 0.5ml of the test substance on the left skin of the animal, applying the area of about 2.5cm, applying for 1 time per day, continuously applying for 14 days, and using the other side as blank control. Shearing hair before each smearing from the next day, removing residual test substance with purified water, and treating the control area. The results were observed for one hour. The test results are shown in table 1 below.

TABLE 1 results of multiple skin irritation tests on New Zealand rabbits with the products of examples 1-3 of the present invention

The results of table 1 above show: the test article is non-irritating to the repeated skin irritations of New Zealand rabbits.

3. And (3) detection results: no erythema or edema skin irritation was observed on the skin of the new zealand rabbits during the observation period, and the score of each animal was 0 point per day for the sample group (the results of the multiple skin irritation tests of the product of example 1 on new zealand rabbits are shown in Table 1 below).

4. And (4) evaluating the results: according to the judgment standard of skin irritation in 2015 edition of technical Specification for cosmetic safety, the products submitted to inspection in examples 1-3 of the invention have no irritation after being subjected to skin for several times.

Effect test example 2 (foam-increasing and foam-stabilizing action)

The test method comprises the following steps:

1) 5 g of surfactant to be detected and the silk hydrolysate related to the invention are diluted into 5 percent solution by purified water, 20ml of the solution is taken, the oscillation is carried out for the same time with the same force, the height of the foam after the oscillation is measured, and the density of the foam is visually observed. And left for 4 hours, and the residual amount of foam was observed;

2) adding purified water to 100ml of 2.5 g of surfactant to be detected and 2.5 g of fibroin hydrolysate related to the invention, and taking 20ml of solution. And (5) oscillating the mixture with the same strength for the same time, measuring the height of the foam after oscillation, visually observing the density of the foam, standing for 6 hours, and observing the residual amount of the foam.

As a result, it was found that: compared with the solution without the compound, the solution compounded with the silk hydrolysate has the advantages that the foam amount is increased after the equal-force and equal-time vibration, the compactness of the foam is obviously enhanced, and the foam residual amount after the solution is placed for 6 hours is equal to or more than the foam residual amount after the solution is placed for 4 hours by using the surfactant alone.

As shown in fig. 2, at the same concentration, the same volume and the same shaking force, the complex formulation test results: the silk hydrolysate has good foam increasing and stabilizing effects when being compounded with other surfactants.

Effect test example 3 (bacteriostasis test)

Through tests, the fibroin hydrolysate obtained by the fibroin hydrolysis process has a certain inhibiting effect on malassezia furfur.

As shown in table 2 below, it was found that the fibroin hydrolysate obtained by the fibroin hydrolysis process described in the present invention has 14% and 24% inhibition rate for malassezia furfur at two different concentrations of 3% and 4%, respectively.

Detection unit: guangdong province microorganism analysis and detection center

TABLE 2 inhibition of Malassezia furfur by fibroin hydrolysates

By testing the inhibition effect of the silk hydrolysate on malassezia furfur, which is a main microorganism generally recognized to influence dandruff, by using the silk hydrolysate with different concentrations, the silk hydrolysate with different concentrations of 3% and 4% obtained by using the silk protein hydrolysis process described by the invention has 14% and 24% inhibition rate on malassezia furfur respectively.

In addition, as can be seen from the results of the following tests, the shampoo prepared by the formula without any dandruff removing and itching relieving components has the same dandruff removing and itching relieving effects, and the clean scalp can be maintained for 3-4 days. From this, it can be concluded that: dandruff formation, drying of the scalp, is directly related to scalp care.

In the actual production formula, if a proper Chinese herbal medicine bactericide or a proper synthetic bactericide is matched in the formula to solve the problem of dandruff caused by excessive reproduction of microorganisms, the two mechanisms are simultaneously applied, and the synergistic effect on inhibiting the generation of dandruff is better.

The technical scheme of the dandruff-removing itching-relieving hair-washing and hair-nourishing composition has the advantages that the fact that the dandruff-removing itching-relieving bactericide is not added and the product can achieve the dandruff-removing itching-relieving effect is verified through the verification formula of only adding the silk hydrolysate, which is not available in the existing products.

All the following raw material components are commercially available products.

Wherein, deionized water in the raw material components is a solvent; disodium ethylene diamine tetraacetate is a metal chelating agent stabilizing system; a citric acid-based pH adjuster; glycerin common humectant; the AESA surfactant is a main foaming agent; imidazoline is taken as a foam booster; olefin sodium sulfonate is used as a foam-increasing and foam-stabilizing agent; diethanolamide is used as a foam-increasing and foam-stabilizing agent; cellulose acetate butyrate is used as a thickening stabilizer; the silk hydrolysate is a moisturizing conditioner, and can improve the micro-ecological environment of the scalp by enhancing the moisturizing property of the scalp, so that the aim of inhibiting dandruff generation is fulfilled; the kasong is a preservative; the essence is an aromatizer; sodium chloride is a thickening stabilizer.

The silk hydrolysate obtained by the production process is added into the formula, and is mainly characterized in that most molecules of the silk hydrolyzed protein are concentrated in the range of 2-20 ten thousand daltons and belong to middle and small molecular proteins.

Example 4 preparation of dandruff-removing, itching-relieving shampoo-nourishing composition

A dandruff-removing itching-relieving hair washing and nourishing composition containing a fibroin component comprises the following components in parts by weight:

78 g of deionized water, 0.1 g of disodium ethylene diamine tetraacetate, 0.2 g of citric acid, 2 g of glycerol, 10g of AESA surfactant, 2 g of imidazoline, 1 g of olefin sodium sulfonate, 1 g of diethanolamide, 2 g of cellulose acetate butyrate, 5 g of the silk hydrolysate of the embodiment 1, 0.1 g of kason, 0.1 g of essence and a proper amount of sodium chloride;

when in preparation, the raw materials of the components are mixed at room temperature, and water and disodium ethylene diamine tetraacetate are added into a pot to be stirred and dissolved; sequentially adding AESA, imidazoline, olefin sodium sulfonate, diethanol amide, glycerol and cellulose acetate butyrate for dissolving and completely transparent; sequentially adding the kasong and the essence to dissolve and completely transparent; and finally, adding the silk hydrolysate silk, uniformly stirring, and adding salt to adjust the viscosity (25 ℃): 5000, adding citric acid to adjust the pH value to 5.8-6.5.

Example 5 preparation of dandruff-removing, antipruritic, hair-washing and hair-caring composition

85 g of deionized water, 0.1 g of ethylene diamine tetraacetic acid (EDTA-2Na), 0.2 g of citric acid, 3 g of glycerol, 15 g of AESA surfactant, 3 g of imidazoline, 3 g of olefin sodium sulfonate (AOS), 3 g of diethanol amide (6501), 3 g of Cellulose Acetate Butyrate (CAB), 7 g of the silk hydrolysate of example 2, 0.1 g of cason, 0.1 g of essence and a proper amount of sodium chloride.

Example 6 (preparation of anti-dandruff antipruritic shampoo and hair tonic composition)

82 g of deionized water, 0.1 g of disodium ethylene diamine tetraacetate, 0.2 g of citric acid, 1.5 g of glycerol, 12 g of AESA surfactant, 1 g of imidazoline, 2.5 g of olefin sodium sulfonate, 2 g of diethanolamide, 4 g of cellulose acetate butyrate, 8 g of the silk hydrolysate of the embodiment 3, 0.1 g of Kathon, 0.1 g of essence and a proper amount of sodium chloride;

The invention adds the silk hydrolysate in the formula, belongs to a detention type skin moisturizing component which is not easy to wash, utilizes the effects of two main components of silk glue and silk fibroin of the silk, wherein the silk glue is mainly collagen, the silk fibroin is keratin, 18 amino acids contained in the silk, and 10 necessary or semi-necessary amino acids of a human body are contained in the silk glue and the silk fibroin.

Any shampoo sold in the existing market can be added into the formula of the embodiment of the invention and mixed to form the shampoo; the invention also can add proper Chinese herbal medicine bactericide or synthetic bactericide into the formula, solves the problem of dandruff caused by excessive reproduction of microorganisms, and has synergistic effect on better inhibiting the generation of dandruff by applying the two mechanisms simultaneously.

The contents of the effect test examples of the anti-dandruff, anti-itching hair washing and nourishing composition are as follows.

Effect test example 4

The dandruff removing, itching relieving, hair washing and hair nourishing compositions of examples 4 to 6 of the present invention were subjected to the examination of microorganisms and sanitary chemistry according to the technical Specification for safety of cosmetics 2015.

And (3) displaying a detection result: three samples (products of examples 4-6) submitted for inspection were tested for hygienic safety according to the technical specifications for cosmetic safety 2015, as follows:

1. and (3) microbial detection: the total number of colonies, the total number of moulds and yeasts, the detection results of heat-resistant coliform bacteria, staphylococcus aureus and pseudomonas aeruginosa all meet the requirements;

2. and (3) sanitary chemical inspection: the detection results of mercury, arsenic, cadmium and the antidandruff agent (including salicylic acid, ketoconazole, climbazole, zinc pyrithione and piroctone olamine) all meet the requirements.

TABLE 3 sanitary chemistry test results

Conclusion of table 4: sanitary chemical examination results (without Pb, Hg and As, without anti-dandruff agent)

TABLE 4 microbiological test results

Inspection item	Test results	Limit value
Total number of colonies (CFT/g)	<10	≤1000
Total number of mold and yeast (CFT/g)	<10	≤100
Thermotolerant coliform bacteria/g	Not detected out	Cannot be detected
Staphylococcus aureus/g	Not detected out	Cannot be detected
Pseudomonas aeruginosa/g	Not detected out	Cannot be detected

Conclusion of table 4: the total number of colonies was satisfactory and no bacterial infection was detected.

Effect test example 5

In order to achieve the test effect, 100 volunteers with symptoms of dandruff and scalp itch are selected for testing, and the shampoo of the embodiment 4-6 is used for cleaning for 20 days every 3 days and is used according to the normal hair washing step, and the effective rate is up to 98.6% according to the test.

The anti-dandruff effect test results of the silk anti-dandruff shampoo and hair care composition are shown in table 5 below.

Wherein the hair quality types are classified into oily, dry, neutral and damaged hair; which are described separately below.

Oiliness: greasy hair, sticky feeling to the touch, much dandruff and lack of luster;

drying: dry hair, rough to the touch, not smooth, lack gloss, changeability after styling;

and (3) neutrality: glossy, supple, healthy hair quality; the product is neither greasy nor dry, has moderate hardness, rich and soft, and has natural luster;

damaged hair: the hair was dry, rough to the touch, lackluster, and yellow-dark.

TABLE 5 Dedandruff shampoo Hair Conditioning compositions of fibroin antidandruff tests examples 4-6

Description of the anti-dandruff Effect:

is very good: the scalp is clean after washing, no scurf can be seen, and the scalp can be maintained for 2 to 3 days; the effect is general: after washing, the scalp is clean and can not see dandruff, but the dandruff can be seen again the next day; ③ no effect: after washing, the hair is dried and dandruff is visible.

In addition, as shown in fig. 3, the sample prepared by the verification formula of the present invention was used by randomly selecting 12 volunteers, and both dandruff and scalp pruritus were improved to some extent.

Based on the theory of how to maintain the scalp micro-ecological environment, the invention achieves the effects of removing dandruff and relieving itching by improving the skin moisturizing performance, improving the scalp micro-ecological environment consisting of physiological lipid, natural moisturizing factors and scalp microbial population of the scalp and maintaining the scalp health.

The results of a plurality of tests show that the shampoo prepared by the formula without any dandruff removing and itching relieving component has the same dandruff removing and itching relieving effects, the clean scalp can be maintained for 3-4 days, and the shampoo has the characteristics of simple formula and good using effect.

The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, so that any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention will still fall within the scope of the technical solution of the present invention without departing from the content of the technical solution of the present invention.

Claims

The preparation method of the fibroin hydrolysate is characterized by comprising the following steps:

1) selecting silkworm cocoons of high-quality breeding silkworms with large shell thickness, removing silkworm chrysalis, silkworm clothing and impurities in the silkworm cocoons, and mincing for later use;

2) using 0.1-1% sodium carbonate or sodium bicarbonate solution as degumming agent with cocoon content of 0.4-10%, controlling hydrolysis temperature at 50-100 deg.C water bath temperature for degumming for 2-4 hr, filtering to obtain hydrolyzed silk fibroin (filtrate) and silk fibroin fiber (filter residue); desalting the filtrate by an electrodialysis device to obtain desalted hydrolyzed sericin for use, wherein the desalted solution can be used for next hydrolysis;

3) dissolving the silk fibroin fiber filter residue in a neutral salt solution with the mass ratio concentration of 30-50%, and controlling the temperature to be 80-100 ℃; the hydrolysis end point is judged by comparing and testing the light transmittance of the hydrolysate through an ultraviolet visible spectrophotometer;

4) performing electrodialysis on the hydrolyzed silk fibroin liquid to remove the impurity ions in the solution, and circulating the solution until the conductivity of the solution is 100-500us/cm to obtain a light yellow silk fibroin pure solution; the separated electrolyte solution can be used for the next hydrolysis production;

5) and finally, mixing the fibroin protein solution with the mass concentration of 1-5% and the sericin protein solution with the mass concentration of 1-5% to obtain the whole silk hydrolysate with the protein molecular weight of 2-20 ten thousand daltons.
The method for preparing fibroin hydrolysate according to claim 1, characterized in that: in the step 1), the silkworm cocoon cultivation method comprises the following steps:

1) selecting the mulberry field:

the mulberry is planted in the Yunnan mountain area with sufficient sunlight and large day-and-night temperature difference, the mulberry leaves have high sugar content and are beneficial to the healthy growth of silkworm babies, so that high-quality cocoon shells with thick shells are obtained, in addition, a natural barrier is formed by the unique small basin structure in the Yunnan mountain area, so that the pesticide in the non-silkworm rearing area is reduced from scattering to the silkworm rearing area, and the pesticide residue of a final product is guaranteed;

2) selection of breeding silkworms:

the breeding silkworm is a second generation silkworm obtained from a silkworm industry technical station, and the breeding silkworm is adopted for the purpose of stable content of the obtained sericin protein and the silk fibroin protein, so that a hydrolysis final product with a stable ratio of the hydrolyzed sericin protein to the hydrolyzed silk fibroin protein is obtained;

3) a culture environment:

the culture environment of the silkworm is related to the microbial control of the later-stage product and silkworm leaf disease; the silkworm breeding environment adopts aseptic, ventilated and dry silkworm breeding in a room so as to reduce the risks of germs, microorganisms and the like of a final product;

4) storage conditions were as follows:

silk is an active protein and needs to be stored in a cool, dry, ventilated place.
The method for preparing fibroin hydrolysate according to claim 1, characterized in that: in the step 3), the neutral salt solution is selected from anhydrous CaCl with the mass ratio concentration of 30-50%₂、CaCl ₂-H ₂O、CaCl ₂-2H ₂O or LiBr solution.
The method for preparing fibroin hydrolysate according to claim 1, characterized in that: in the step 3), the control of the hydrolysis end point is to ensure that the molecular weight of the fibroin of the final product obtained in the step 5) is controlled within the range of 2-20 ten thousand daltons, and is mainly centralized within the range of 10-20 ten thousand daltons.
A dandruff-removing itching-relieving hair-washing and hair-nourishing composition containing a fibroin component is characterized in that: comprises the following components in percentage by weight:

70-85 parts of deionized water, 0.1-03 parts of disodium ethylene diamine tetraacetate, 0.2-0.4 part of citric acid, 1-3 parts of glycerol, 10-15 parts of AESA surfactant, 1-3 parts of imidazoline, 1-3 parts of olefin sodium sulfonate, 1-3 parts of diethanolamide, 2-4 parts of cellulose acetate butyrate, 1-8 parts of fibroin hydrolysate, 0.1-0.3 part of Kathon, 0.1-0.3 part of essence and a proper amount of sodium chloride.
The dandruff-removing itching-relieving hair cleansing and conditioning composition containing a fibroin component according to claim 5, characterized in that: the fibroin hydrolysate is prepared by the following process:

1) degumming the silkworm cocoons by using a weak alkaline aqueous solution as a degumming agent according to a conventional method, wherein the degumming agent is used for degumming the silkworm cocoons under the conditions that the mass percent of the solution of the degumming agent is 0.4-6%, the pH value is 8-11, and the hydrolysis temperature is 50-100 ℃;

2) filtering the solution in the step 1) to form degumming hydrolysate and silk fibroin fibers;

3) separating the degumming hydrolyzed solution filtered out in the step 2) into sericin hydrolyzed solution and dialysis ionic solution through electrodialysis, retaining the sericin hydrolyzed solution, and transferring the dialysis ionic solution to next sericin hydrolysis; the hydrolysis end point is judged by comparing and testing the light transmittance of the hydrolysate through an ultraviolet visible spectrophotometer;

4) dissolving the silk fibroin fibers obtained by filtering in the step 2) in a neutral salt solution with the temperature of 60-100 ℃ and the mass percent of 30-60% to form silk fibroin liquid;

5) performing electrodialysis on the hydrolyzed silk fibroin solution obtained in the step 4) to remove ions in the solution, and circulating until the conductivity of the solution is reduced to 100-;

6) and (3) uniformly mixing the sericin hydrolysate obtained in the step 3) and the fibroin pure solution obtained in the step 5) to obtain the novel fibroin hydrolysate with the characteristics of the surfactant.
The dandruff-removing itching-relieving hair cleansing and conditioning composition containing a fibroin component according to claim 4, characterized in that:

in the step 1), the degumming agent adopts sodium carbonate or sodium bicarbonate water solution; the hydrolysis temperature is 50-80 ℃, and the hydrolysis time is 2-4 hours;

step 4) the neutral salt solution is CaCl₂、CaCl _2-H ₂O、CaCl _2-2H ₂O or LiBr solution.
The method for preparing the dandruff-removing itching-relieving hair washing and caring composition containing fibroin component according to any one of claims 4 to 7, characterized in that: the manufacturing process comprises the following steps:

1) mixing the raw materials of the components at room temperature, adding water and disodium ethylene diamine tetraacetate into a pot, stirring and dissolving;

2) sequentially adding AESA, imidazoline, olefin sodium sulfonate, diethanol amide, glycerol and cellulose acetate butyrate for dissolving and completely transparent;

3) sequentially adding the kasong and the essence to dissolve and completely transparent;

4) finally, adding the silk hydrolysate silk, stirring uniformly, adding salt to adjust the viscosity (25 ℃): 5000, adding citric acid to adjust the pH value to 5.8-6.5.
A method for removing dandruff and relieving itching of scalp, wherein the dandruff-removing, itching-relieving, hair-washing and hair-nourishing composition used in hair washing is the dandruff-removing, itching-relieving, hair-washing and hair-nourishing composition prepared by the preparation method of the dandruff-removing, itching-relieving, hair-washing and hair-nourishing composition containing fibroin component according to claim 6, and has the function of improving scalp micro-ecological environment consisting of physiological lipid, natural moisturizing factor and scalp microbial population of scalp.