A silanolized derivative of hydrolyzed animal and plant proteins, its preparation method and application

Abstract

This invention discloses a silanolized derivative of hydrolyzed animal and plant proteins, its preparation method, and its application. The method involves pretreating a complex of animal and plant proteins with β-mercaptoethanol, followed by enzymatic hydrolysis with two proteases. After hydrolysis, post-treatment yields hydrolyzed protein powder. A silanol derivatizing agent is pretreated to obtain a silanol derivative. The hydrolyzed protein powder is then added to the silanol derivatizing agent for a silanol derivatization reaction. After the reaction, desaturation is applied to remove the alcohol, yielding silanolized hydrolyzed protein, which is the aforementioned silanolized derivative of hydrolyzed animal and plant proteins. The silanolized derivative of hydrolyzed animal and plant proteins obtained in this invention has applications in the preparation of hair care products such as smoothing agents, hair care product breakage prevention agents, hair care product moisturizers, and hair care product repair agents. When applied to hair, the product exhibits increased extensibility and smoothness, enhancing its penetration into damaged hair, resulting in better and faster-acting effects.

Description

Technical Field

[0001] This invention relates to a silanolized derivative, specifically to a silanolized derivative of hydrolyzed animal and plant proteins, its preparation method, and its application, belonging to the field of biopharmaceutical technology. Background Technology

[0002] In daily life, sunlight, ultraviolet radiation, hair dyes, hot perms, and blow-drying can cause changes in hair structure and photodegradation. This can lead to the lifting and even peeling of the hair cuticle, resulting in easy loss of hair protein, decreased strength, elasticity, and cleanliness. Hair may appear rough to the touch, yellowish, dull, inelastic, and brittle. Other signs of hair damage include complete cuticle loss, exposed cortex, split ends, breakage, and split ends. In short, hair damage severely affects appearance, causes distress, and can even directly impact mental health. Therefore, various active compounds are used in daily chemical products to improve hair quality and repair damaged hair.

[0003] Organosilicon compounds (such as silicone oil and emulsified silicone oil) are widely added to hair care products due to their excellent spreadability and smoothness, while peptides are widely added due to their nourishing, adsorption, penetration, and moisturizing effects. Using such products can repair frizzy and damaged hair, making it smoother and shinier. However, silicone oil is usually suitable for oil-soluble systems, while peptides are used in water-soluble systems. The two systems are incompatible and easily separate when they form an emulsion. To solve the above problems, a lot of research has been conducted to combine organosilicon compounds with peptides through chemical reactions. As a result, a class of compounds that have both the nourishing, adsorption, and penetrating properties of peptides and the spreadability and smoothness of organosilicon compounds have been developed. These compounds are often named silanolized peptides or silanolized hydrolyzed proteins. Due to their effects, these compounds are widely used in daily chemical products.

[0004] Research on the preparation of silanolized hydrolyzed protein has been conducted before. Japanese Patent JP2007277195A mentions that after hydrolyzing a silane coupling agent in water-soluble alcohol, it is reacted with the side chain amino groups of hydrolyzed peptides with an average molecular weight of 200-3,000 Da under alkaline conditions and at a temperature of 40-55 degrees Celsius to obtain silanolized hydrolyzed peptides. Chinese Patent CN 116287076 B discloses a silanolized hydrolyzed protein product, its preparation method, and its application. Plant protein raw materials are pretreated with alkaline water to obtain a protein alkaline-treated clear liquid; a complex protease is added to the obtained protein alkaline-treated clear liquid for hydrolysis, and the liquid is filtered to obtain a hydrolyzed protein solution; a polyhydroxysilane and a catalyst are added to the obtained hydrolyzed protein solution, and a crude product is obtained through reaction; the obtained crude product is then neutralized, decolorized, and deodorized to prepare a safe, effective, highly utilized, and strongly adsorbed silanolized hydrolyzed protein product.

[0005] Analysis of previous literature and patents reveals that most studies involve the reaction of silane derivatizers containing epoxy groups with the amino groups of peptides. The bonding or grafting process between peptides and silane derivatizers falls into two categories: amino reactions (the amino groups carried by the terminal amino groups and lysine residues of the peptide react with the silane epoxy groups), and thiol reactions (the thiol groups of cysteine ​​residues in the peptide react with the silane epoxy groups). In peptide molecules treated with common acids, bases, and enzymes, the number of amino and thiol groups exposed that can react with silane compounds is limited, resulting in poor silane incorporation rates and unsatisfactory silane peptide compounds. Summary of the Invention

[0006] The technical problem to be solved by this invention is to address the shortcomings of existing technologies by providing a silanolized derivative of hydrolyzed animal and plant proteins, its preparation method, and its application. The method of this invention increases the contact between silane and polypeptide, making the reaction more complete, shortening the reaction time, increasing the silane compound introduction rate, and enhancing the performance of the final product. When the product of this invention is applied to hair, its extensibility and smoothness are increased, which increases its penetration into damaged hair, resulting in better and faster effects.

[0007] To achieve the above objectives, the present invention adopts the following technical solution:

[0008] One objective of this invention is to provide a method for preparing silanolized derivatives of hydrolyzed animal and plant proteins, comprising the following steps:

[0009] (1) Preparation of hydrolyzed proteins or peptides:

[0010] Animal and plant proteins are combined to obtain a composite animal-plant protein. β-mercaptoethanol is added to the composite animal-plant protein for pretreatment to break the dithiol bonds in the composite animal-plant protein. After pretreatment, protease is added to the system for enzymatic hydrolysis to degrade the proteins in the composite animal-plant protein and expose the amino groups in the proteins. After enzymatic hydrolysis, the protein is sequentially subjected to activated carbon adsorption, dialysis, and pH adjustment to obtain a crude hydrolyzed protein solution. The crude hydrolyzed protein solution is then sequentially concentrated, ultrafiltered, and dried to obtain hydrolyzed protein powder.

[0011] (2) Pretreatment of silanol derivatives:

[0012] After adjusting the pH of water to acidic using organic acids, a silanol derivatizing agent is added and stirred to hydrolyze the epoxy groups into hydroxyl groups, thus obtaining the silanol derivatizing agent.

[0013] (3) Preparation of proteins by silanolization hydrolysis:

[0014] Prepare a hydrolyzed protein solution with a solid content of 20-25% by preparing the hydrolyzed protein powder obtained in step (1). Add the silanol derivatizer obtained in step (2) to the hydrolyzed protein solution, control the pH to 8.5-9.5, and stir while adding. The hydrolyzed protein and silanol derivatizer undergo silanol derivatization reaction under stirring conditions. After the reaction is completed, de-alcoholization under reduced pressure is performed to obtain silanolized hydrolyzed protein, which is the silanolized derivative of the animal and plant hydrolyzed protein.

[0015] In the above technical solution, in step (1), the animal protein is any one of collagen, silk protein, keratin, elastin, etc.; the plant protein is any one of wheat protein, corn protein, soybean protein, oat protein, rice protein, etc. Both animal and plant proteins are chosen as protein sources. Natural proteins are diverse, and the proportions of amino acids in various animal and plant proteins vary greatly. Different natural proteins often exhibit different functional emphases due to their different amino acid compositions. For example, soybean protein and yeast protein are rich in glutathione (glutamic acid, cysteine, glycine) and exhibit good antioxidant properties. Therefore, during use, we can control the types and proportions of amino acids to improve the overall use value of the product through synergistic effects.

[0016] In the above technical solution, in step (1), the animal protein is preferably keratin; the plant protein is preferably soybean protein; the mass ratio of soybean protein and keratin when compounded is 2:1. There are two types of reactions between peptides and silane derivatives during bonding or grafting: one is an amino reaction (the terminal amino group and the amino group carried by lysine in the peptide react with the silane epoxy group), and the other is a thiol reaction (the thiol group of cysteine ​​in the peptide reacts with the silane epoxy group). Therefore, we choose keratin from animal proteins and soybean protein from plant proteins as protein sources because keratin in wool and feathers has a very high cysteine ​​content, accounting for 10%-14%, which is close to the cysteine ​​content in hair. After hydrolysis by special means, the exposed thiol content is high, which is more conducive to the later reaction with silane derivatives and effectively increases yield. Soybean protein, a plant protein, has a high lysine content, accounting for 6.0%-7.5%, and the cysteine ​​content in soybean protein is also higher than that of other plant proteins.

[0017] In the above technical solution, in step (1), the pretreatment involves a treatment time of 30 minutes to 2 hours, a treatment temperature of 45°C, and a pH of 8-9 in the system. The mass ratio of the composite animal and plant protein to β-mercaptoethanol is 1:60 to 1:40, and the concentration of β-mercaptoethanol in the mixed system is controlled at 10-18 mmol / L. Because the composite protein has a large molecular weight, ranging from hundreds of thousands to millions of Daltons, the protein composite powder undergoes further degradation treatment. To ensure more complete degradation of the composite protein and expose more amino and thiol groups, β-mercaptoethanol, alkaline protease, and alkaline aminopeptidase are selected to treat the composite animal and plant protein together. The purpose of β-mercaptoethanol is to expose the thiol groups in the protein and break disulfide bonds.

[0018] In the above technical solution, in step (1), the protease includes alkaline protease and alkaline aminopeptidase, with a mass ratio of alkaline protease to alkaline aminopeptidase of (1-4):1, and an enzyme activity of 200,000 u / g; during enzymatic hydrolysis, the substrate concentration is 20-40 wt%, and the enzyme dosage is 1 wt%; during enzymatic hydrolysis, the pH of the system is 8-9, the hydrolysis temperature is 50℃, and the hydrolysis time is 3-6 h. Two proteases are added for enzymatic hydrolysis, wherein the purpose of alkaline protease is to degrade the protein, thereby reducing the overall protein molecular weight, and the purpose of alkaline aminopeptidase is to expose the amino groups in the protein.

[0019] In the above technical solution, in step (1), after the enzymatic hydrolysis is completed, the enzyme is inactivated and the system is adsorbed by the porous activated carbon to perform decolorization and deodorization treatment; after dialysis to remove mercaptoethanol, the pH of the system is adjusted to 7.0 to obtain hydrolyzed protein crude liquid; at this time, the liquid contains a wide molecular weight distribution of polypeptides, ranging from tens of Daltons to hundreds of thousands of Daltons, and contains free amino acids, small short peptides, medium peptide chains and long peptide chains. After the hydrolyzed protein crude liquid is concentrated, it is subjected to ultrafiltration. The hydrolyzed protein crude liquid is treated with a 3kDa ultrafiltration membrane and dried to obtain hydrolyzed protein powder with an average molecular weight range of 200-3000 Da.

[0020] In the above technical solution, in step (2), the silanol derivative is selected from any one of 3-(2,3-epoxypropoxy)propylmethyldimethoxysilane, 3-(2,3-epoxypropoxy)propylmethyldiethoxysilane, 3-(2,3-epoxypropoxy)propylmethyldipropoxysilane, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, and 3-(2,3-epoxypropoxy)propyltriethoxysilane; however, the silanol derivative is not limited to the above types, and any silane coupling agent containing an epoxy group is applicable.

[0021] In the above technical solution, in step (2), the organic acid is formic acid or acetic acid. After adjusting the pH of water to 4.5-5.0 with organic acid, silanol derivatizing agent is added and stirred for 30 minutes to hydrolyze the epoxy group into hydroxyl group, which is then hydrolyzed into 3-(2,3-epoxypropoxy)propylmethyldihydroxysilane or 3-(2,3-epoxypropoxy)propyltrihydroxysilane, thus obtaining the silanol derivatizing agent.

[0022] In the above technical solution, in step (3), the silanol derivatizer is added to the hydrolyzed protein solution under stirring at 45°C. The mass ratio of the solute in the hydrolyzed protein solution to the silanol derivatizer is 5:1 (calculated based on molecular weight). After the silanol derivatizer is added, stirring continues, the temperature is maintained at 45°C, the pH of the system is controlled at 8.5-9.5, the reaction is stopped after stirring for 3 hours, and the silanolized hydrolyzed protein is obtained after de-alcoholization under reduced pressure, which is the silanolized derivative of the animal and plant hydrolyzed protein.

[0023] In the above technical solution, in step (3), the hydrolyzed protein and the silanol derivatizing agent undergo a silanol derivatization reaction under stirring conditions, wherein: the reaction formula of the amino group (-NH2) of the hydrolyzed protein with the epoxy group (-C2H3O-) in the silanol derivatizing agent is shown in Formula I:

[0024] I;

[0025] In the formula, R represents the remaining part of the polypeptide, and R' represents the remaining organic part of the silane.

[0026] In the above technical solution, in step (3), the reaction formula for the reaction between the thiol group (-SH) of the hydrolyzed protein and the epoxy group (-C2H3O-) in the silanol derivatizer is shown in Formula II:

[0027] II;

[0028] In the formula, R represents the remainder of the polypeptide. R' represents the remainder of the silane.

[0029] The second objective of this invention is to provide a silanolized derivative of hydrolyzed animal and plant proteins obtained by the above-described preparation method.

[0030] A third objective of this invention is to provide an application of the above-mentioned silanolized derivatives of hydrolyzed animal and plant proteins in the preparation of hair care product smoothing agents, hair care product anti-breakage agents, hair care product moisturizers, and hair care product repair agents.

[0031] Compared with existing technologies, it has the following characteristics:

[0032] (1) The present invention enables the polypeptide groups of hydrolyzed protein to expose more amino (terminal amino) and thiol groups through specific means, thereby obtaining hydrolyzed protein, which can enrich more amino and thiol groups, increase the contact between silane and hydrolyzed protein, make the reaction more complete, shorten the reaction time, and increase the number of silane compounds attached to hydrolyzed protein by multiples, thereby improving the introduction rate and enhancing the performance of the final product.

[0033] (2) The product of the present invention maintains the nutritional and adsorption properties of hydrolyzed protein while improving the grafting rate and yield, thereby increasing the extensibility and smoothness of silanized hydrolyzed protein on hair and increasing its permeability to damaged hair. In practical applications, it has better effects and faster results. Attached Figure Description

[0034] Figure 1 To verify the effect of different silanized hydrolyzed protein solutions in Example 1 on improving the combing properties of hair strand friction, the diagram shows: Represents the friction force of wet combing. Represents the friction force of dry combing;

[0035] Figure 2 To verify the combing improvement effect of different silanized hydrolyzed protein solutions on the reduction rate of hair bundle friction in Example 1, the diagram shows: This represents the rate of reduction in wet combing friction. Represents the friction force of dry combing;

[0036] Figure 3 To verify the effect of different silanized hydrolyzed protein solutions on improving the longevity of hair follicle moisturizing in Example 4, the diagram shows: ■ represents Example 1, ● represents Example 2, ▲ represents Example 3, ▼ represents Example 4, and ◆ represents Example 5. Representative Comparative Example 1, This represents the blank control group;

[0037] Figure 4-a SEM image to verify the effect of the silanized hydrolyzed protein solution from Example 1 in Example 5 on the nutritional repair of hair cuticles;

[0038] Figure 4-b SEM image to verify the effect of the silanized hydrolyzed protein solution from Example 2 in Example 5 on the nutritional repair of hair cuticles;

[0039] Figure 4-c SEM image to verify the effect of the silanized hydrolyzed protein solution from Example 3 in Example 5 on the nutritional repair of hair cuticles;

[0040] Figure 4-d SEM image to verify the effect of the silanized hydrolyzed protein solution from Example 4 in Example 5 on the nutritional repair of hair cuticles;

[0041] Figure 4-e SEM image to verify the effect of the silanized hydrolyzed protein solution of Example 5 on the nutritional repair of hair cuticles in Example 5;

[0042] Figure 4-f SEM image to verify the effect of the hydrolyzed protein solution of Comparative Example 1 in Example 5 on the nutritional repair of hair cuticles;

[0043] Figure 4-g SEM images were used to verify the effect of the blank control group in Example 5 on the nutritional repair of hair cuticles. Detailed Implementation

[0044] The following describes in detail the specific embodiments of the technical solution of the present invention, but the present invention is not limited to the following description:

[0045] To better illustrate the purpose, technical solution, and advantages of this invention, the invention will be further described below with reference to specific embodiments. Unless otherwise specified, the experimental methods used in the embodiments are conventional methods, and the materials and reagents used are commercially available unless otherwise specified.

[0046] The technical solution of the present invention will be described below with reference to specific embodiments:

[0047] Example 1:

[0048] A method for preparing silanolized derivatives of hydrolyzed animal and plant proteins includes the following steps:

[0049] (1) Preparation of hydrolyzed proteins or peptides:

[0050] The selected plant and animal proteins, soybean protein and keratin, were compounded at a mass ratio of 2:1. The compounded plant and animal proteins were then pretreated with β-mercaptoethanol for 1 hour at a pH of 8.0 and a temperature of 45°C. The mass ratio of the compounded protein to β-mercaptoethanol was 1:40, and the concentration of β-mercaptoethanol in the mixture was controlled at 18 mmol / L. Next, two proteases were added to the system: an alkaline protease and an alkaline aminopeptidase at a mass ratio of 1:1, with an enzyme activity of 200,000 u / g, a substrate concentration of 30 wt%, and an enzyme dosage of 1 wt%. Enzymatic hydrolysis was performed at a pH of 8.5, a temperature of 50°C, and a time of 3 hours. After enzymatic hydrolysis, the enzymes were inactivated, and the mixture was decolorized and deodorized using activated carbon porous adsorption. After dialysis to remove β-mercaptoethanol, the pH was adjusted to 7.0, yielding a crude hydrolyzed protein solution. This solution was concentrated and then ultrafiltered using a 3 kDa ultrafiltration membrane. After drying, hydrolyzed protein powder with an average molecular weight range of 200-3000 Da was obtained.

[0051] (2) Pretreatment of silanol derivatives:

[0052] The silanol derivatizing agent used is 3-(2,3-epoxypropoxy)propylmethyldiethoxysilane. After adjusting the pH of water to 4.5 with acetic acid, 3-(2,3-epoxypropoxy)propylmethyldiethoxysilane is added and stirred for 30 minutes to hydrolyze the diethoxy group of the alkoxy group into two hydroxyl groups, which in turn hydrolyzes into 3-(2,3-epoxypropoxy)propylmethyldihydroxysilane, thus obtaining the silanol derivatizing agent.

[0053] (3) Preparation of proteins by silanolization hydrolysis:

[0054] The hydrolyzed protein powder obtained in step (1) was prepared into a hydrolyzed protein solution with a solid content of 25%. Under stirring conditions at 45°C and pH 8.5-9.5, a silanol derivatizing agent was added to the hydrolyzed protein solution. The mass ratio of the solute to the silanol derivatizing agent in the hydrolyzed protein solution was 5:1 (calculated based on molecular weight). The hydrolyzed protein and silanol derivatizing agent under stirring conditions underwent a silanol derivatization reaction. The reaction was stopped after maintaining the temperature and stirring for 3 hours (the epoxy value was monitored during this period to determine the reaction progress). After the reaction was completed, the hydrolyzed protein was de-alcoholized under reduced pressure to obtain silanolized hydrolyzed protein, which is the aforementioned silanolized derivative of animal and plant hydrolyzed protein. The obtained silanolized hydrolyzed protein was diluted with water to prepare a solution with a solid content of 30%, which is the silanolized hydrolyzed protein solution, for later use.

[0055] Example 2:

[0056] A method for preparing silanolized derivatives of hydrolyzed animal and plant proteins is basically the same as that in Example 1, except that the mass ratio of the two proteases is different from that in Example 1. The ratio of alkaline protease to alkaline aminopeptidase is 4:1. After obtaining the silanolized hydrolyzed protein, water is added to prepare a solution with a solid content of 30%, which is a silanolized hydrolyzed protein solution for later use.

[0057] Example 3:

[0058] A method for preparing silanolized derivatives of hydrolyzed animal and plant proteins is basically the same as that in Example 1, except that 3-(2,3-epoxypropoxy)propyltriethoxysilane is used as the silanol derivative agent. After obtaining the silanolized hydrolyzed protein, water is added to prepare a solution with a solid content of 30%, which is a silanol hydrolyzed protein solution for later use.

[0059] Example 4:

[0060] A method for preparing silanolized derivatives of hydrolyzed animal and plant proteins is basically the same as that in Example 1, except that: in step (1), β-mercaptoethanol is not used for pretreatment, but only two proteases are used for enzymatic hydrolysis. Only alkaline protease and alkaline aminopeptidase are used to degrade the complex animal and plant proteins to obtain silanolized hydrolyzed proteins. Water is then added to prepare a solution with a solid content of 30%, which is a silanolized hydrolyzed protein solution for later use.

[0061] Example 5:

[0062] A method for preparing silanolized derivatives of hydrolyzed animal and plant proteins is basically the same as that in Example 1, except that: in step (1), after pretreatment with β-mercaptoethanol, only one protease is used for enzymatic hydrolysis, and only alkaline protease is used to degrade the complex protein to obtain silanolized hydrolyzed protein. After adding water, a solution with a solid content of 30% is prepared, which is a silanolized hydrolyzed protein solution for later use.

[0063] Comparative Example 1:

[0064] A method for preparing a silanolized derivative of hydrolyzed animal and plant protein is basically the same as step (1) in Example 1. After obtaining hydrolyzed protein powder, water is added to prepare a solution with a solid content of 30%, which is a hydrolyzed protein solution.

[0065] Verification Example 1:

[0066] The physicochemical properties of the products from the above embodiments and comparative examples were tested, including the following tests:

[0067] (1) Sensory indicators

[0068] Color determination is based on Gardner colorimetry, referencing GB / T 22295-2008.

[0069] (2) Determination of total nitrogen

[0070] The Kjeldahl method was used for nitrogen determination, and the method was based on GB 5009.5-2016.

[0071] (3) Determination of average molecular weight

[0072] The detection was performed using gel permeation chromatography, following the method specified in GB / T 31816-2015.

[0073] (4) Determination of silicon content

[0074] The detection was performed using spectrophotometry, following the method specified in GB / T 17518-2012.

[0075] (5) Determination of introduction rate

[0076] The introduction rate was calculated by comparing the amino terminus (Sanger method) and thiol terminus (Ellman method) before and after silanol derivatization. Introduction rate = [1 - (sum of amino and thiol terminus after derivatization) / (amino and thiol terminus before derivatization)] * 100%.

[0077] The test results are shown in Table 1:

[0078] Table 1: Results of Physicochemical Properties Test

[0079] project Senses Total nitrogen content Average molecular weight Silicon content Introduction rate Example 1 Gardner10 ≥3.84% 1232 Da 3.50% 91% Example 2 Gardner 10 ≥3.68% 1755 Da 2.90% 85% Example 3 Gardner 11 ≥3.80% 1251 Da 3.40% 87% Example 4 Gardner 9 ≥3.20% 2520 Da 1.53% 65% Example 5 Gardner 10 ≥3.35% 2379 Da 1.87% 75% Comparative Example 1 Gardner 9 ≥3.85% 1104 Da 0 % --

[0080] Verification Example 2:

[0081] Samples A, B, C, D, and E were prepared by dispersing the silanized hydrolyzed protein solutions from Examples 1-5 and deionized water at a mass ratio of 5:95. Sample F was prepared by dispersing Comparative Example 1 and deionized water at a mass ratio of 5:95. A blank control sample G was also set up. The effect of the samples on improving the combability of hair strands was tested. The test steps are as follows:

[0082] Hair strands were washed using sample AF. First, the hair was wetted, then the sample was evenly applied to the strands and rubbed for 1 minute. The water flow was kept constant, and the strands were rinsed for 2 minutes. After washing, the strands were fixed on a testing platform to maintain tautness. A multi-functional hair tester was used to test the friction of the hair strands, measuring wet combing friction (a1) and dry combing friction (a2) after the hair strands were dried with a hairdryer. Sample G was tested using deionized water for wet combing friction (b1) and dry combing friction (b2). The formula for calculating the friction reduction rate is: (Friction of blank control sample G - Friction of target sample) / Friction of blank control sample G × 100%. A higher value indicates a more significant improvement in combability. The effects of different silanized hydrolyzed protein solutions on the combability improvement of hair strand friction are shown in the figure. Figure 1 , 2 As shown.

[0083] The experimental results show that silane-modified hydrolyzed protein is far superior to the unmodified group (Comparative Example 1) in improving hair combability. When wet-combing, the unmodified group showed an improvement rate of only 8.6%, while the silane-modified group showed an improvement rate 3.5-4.9 times higher. When dry-combing, the unmodified group showed an improvement rate of 10.3%, while the silane-modified group showed an improvement rate 3.2-4.4 times higher. This is because the silanized groups possess both strong hydrophobicity and smoothness, enabling them to firmly bind to the hair surface and form a durable adsorption film, reducing cuticle friction. Unmodified hydrolyzed protein, relying only on weak polarity for adhesion, is easily rinsed out, resulting in limited effectiveness.

[0084] Of all the samples, Example 1 performed best, exhibiting the lowest friction (46.8g / 33.2g) in wet / dry combing and the highest improvement rate (42.1% / 45.3%). Its silane substitution rate and molecular chain length showed the best compatibility with hair structure, making it a suitable benchmark process. In summary, silanized hydrolyzed protein (especially the product from Example 1) is the preferred choice as a smoothing agent in hair care products, replacing traditional unmodified protein, and significantly improving combability. Unmodified protein is more suitable for moisturizing and repairing; silanization modification can be performed when improved combability is required.

[0085] Verification Example 3:

[0086] Samples A, B, C, D, and E were prepared by dispersing the silanized hydrolyzed protein solutions from Examples 1-5 and deionized water at a mass ratio of 5:95. Sample F was prepared by dispersing the hydrolyzed protein solution from Comparative Example 1 and deionized water at a mass ratio of 5:95. A blank control sample G was also set up. The effect of the samples on improving the hair strand's elasticity was tested. The test steps are as follows:

[0087] Select healthy human hair (from the same person and the same area, avoiding perming and dyeing), cut it into 5cm long bundles, each bundle containing 50 hairs (ensuring uniform thickness and length), wash with deionized water, and air dry. Place all hair bundles in a constant temperature and humidity chamber for 24 hours to equilibrate and eliminate the influence of environmental humidity on hair moisture content.

[0088] Immerse the hair strand completely into the corresponding sample, let it stand for 5 minutes, remove the hair strand, remove excess liquid from the surface, and then place it in a constant temperature and humidity chamber for 1 hour to equilibrate (allowing the sample to fully absorb and stabilize).

[0089] The blank control (sample G) was immersed in deionized water, and a tensile test was started until the hair broke, at which point the instrument automatically recorded the results. The effects of different silanized hydrolyzed protein solutions on improving hair strand extensibility are shown in Table 2.

[0090] Table 2. Test data on the effect of silanized hydrolyzed protein solution on improving hair strand elasticity.

[0091] Sample number Initial clamping length (mm) Average elongation at break (mm) Average elongation at break (%) Improvement rate in extensibility (%) A (Example 1) 50 5.63±0.15 11.3±0.10 41.3 B (Example 2) 50 5.30±0.22 10.5±0.17 31.3 C (Example 3) 50 5.17±0.32 10.3±0.28 28.8 D (Example 4) 50 4.77±0.13 9.5±0.66 18.8 E (Example 5) 50 4.97±0.19 9.9±0.29 23.8 F (Comparative Example 1) 50 4.17±0.27 8.3±0.29 3.8 G (Blank control) 50 4.00±0.44 8.0±0.38 --

[0092] Experimental results showed that silanized hydrolyzed protein significantly improved hair elongation. It improved hair stretchability by 5-11 times, with the stretchability improvement rate of the silanized group being 18.8%-41.3%, which is 5-11 times that of Comparative Example 1 (3.8%). Among them, the improvement rate of Example 1 (41.3%) was 10.9 times that of Comparative Example 1.

[0093] This demonstrates that silanized hydrolyzed protein does not simply enhance the function of hydrolyzed protein, but rather achieves this through molecular structure optimization (introducing silane chains). Small molecule peptides penetrate the gaps in the hair shaft, while silane chains form a film on the surface, creating a "filling + reinforcement" effect. Furthermore, the low-friction properties of silane chains reduce friction between hair shaft fibers, allowing tensile force to be transmitted evenly, ultimately improving hair breakage elongation.

[0094] Verification Example 4:

[0095] Samples A, B, C, D, and E were prepared by dispersing the silanized hydrolyzed protein solutions from Examples 1-5 and deionized water at a mass ratio of 5:95. Sample F was prepared by dispersing the hydrolyzed protein solution from Comparative Example 1 and deionized water at a mass ratio of 5:95. A blank control sample G was also set up. The effects of the samples on improving the moisturizing and lasting properties of hair strands were tested. The test steps are as follows:

[0096] Select a healthy person's hair strand, wash it twice with neutral shampoo, rinse thoroughly with deionized water, and let it sit.

[0097] Then air-dry to constant weight (weight change ≤0.1%). Sample AF was immersed at 30℃ with constant temperature shaking for 30 minutes, while the blank group was treated with deionized water. After removal, excess liquid was absorbed with filter paper, and the samples were dried in a 40℃ oven for 1 hour for later use. Hair moisture absorption stage: Samples were placed in a high-humidity environment and left to stand for 2 hours to allow the hair to fully absorb moisture and reach moisture balance. Moisture loss tracking: Samples were transferred to a low-humidity environment, and timing was started. Sample weight was measured every hour using a thermogravimetric analyzer (recorded as m2, m3...m6), continuously tracking for 6 hours (covering the main time dimensions of a typical day). Moisture retention rate (%) = (sample weight at a certain time point - constant weight of sample) / (initial weight after moisture absorption - constant weight of sample) × 100%. Different silanized hydrolyzed protein solutions showed effects on improving the durability of hair strand moisturizing. Figure 3 As shown.

[0098] This experiment tested the moisturizing and long-lasting effects on hair by comparing silanized hydrolyzed protein samples (AE), a group of unsilanized hydrolyzed protein samples (F), and a blank control (G). The following conclusions were drawn: Silanization modification significantly improves the hair moisturizing effect of hydrolyzed protein. At 6 hours, the moisture retention rate of AE was 58.2%-71.2%, far exceeding that of F (39.5%) and G (28.5%), and the advantage became more pronounced over time. Differences in the effects among the AE groups were observed, ranked as A > B > C > E > D, which is related to the protein degradation process and molecular structure. In summary, silanized hydrolyzed protein can form a stable protective film on the hair surface, reducing moisture loss, and can be used as a long-lasting moisturizing hair care ingredient, with the formulation in Example 1 being the optimal one.

[0099] Verification Example 5:

[0100] Hair cuticle SEM test

[0101] Samples A, B, C, D, and E were prepared by dispersing the silanized hydrolyzed protein solution from Examples 1-5 and deionized water at a mass ratio of 5:95. Sample F was prepared by dispersing the hydrolyzed protein solution from Comparative Example 1 and deionized water at a mass ratio of 5:95. A blank control sample G was also set up. The effects of the samples on the nutritional repair of hair cuticles were tested. The test steps are as follows.

[0102] The collected hair samples were washed with deionized water to remove surface dirt and grease, and then air-dried or blow-dried using a low-temperature hair dryer. The dried hair samples were divided into several groups, each containing a certain number of hairs. The experimental group hair samples were immersed in the sample AG for a period of time to promote the penetration and effect of the sample on the hair. They were then thoroughly rinsed with deionized water. The washed hair samples were then air-dried or dried at a low temperature (e.g., 30-40℃) to avoid affecting the hair structure. The soaking, washing, and drying steps were repeated 10 times. Scanning electron microscopy (SEM) images were then taken. The SEM images of the cuticle nutrition repair effects of different embodiments on hair bundles are shown in Figures 4a-g.

[0103] This experiment, through 10 cycles of soaking-washing-drying and scanning electron microscopy observation, yielded the following conclusions: the nutritional repair effect of silanized hydrolyzed protein (sample AE) on hair cuticles is significantly better than that of unmodified hydrolyzed protein (sample F) and blank control (sample G).

[0104] In the blank group G, the hair cuticles were severely open and damaged; sample F showed only slight improvement, as the unmodified protein was easily washed away, limiting its repair effect. Sample AE, however, showed significantly improved cuticle closure and integrity, providing lasting protection. Among these, sample A, corresponding to Example 1, showed the best effect, with cuticle closure approaching that of healthy hair, with only a very small number slightly open, due to its optimal compatibility between silane substitution rate, molecular chain length, and hair structure. While samples B and C showed better repair effects than D and E, they were slightly inferior to A due to differences in compatibility. In conclusion, prioritizing the use of silanized hydrolyzed proteins with superior compatibility (especially products using the process of sample A) can enhance the hair care product's ability to repair and protect the hair cuticles.

[0105] The above examples are merely illustrative of the technical concept and features of the present invention and should not be construed as limiting the scope of protection of the present invention. All equivalent transformations or modifications made in accordance with the essence of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing silanolized derivatives of hydrolyzed animal and plant proteins, characterized in that, The steps include the following: (1) Preparation of hydrolyzed proteins or peptides: Animal and plant proteins are combined to obtain a composite animal and plant protein. β-mercaptoethanol is added to the composite animal and plant protein for pretreatment to destroy the dithiol bonds in the composite animal and plant protein. After the pretreatment, protease is added to the system for enzymatic hydrolysis to degrade the proteins in the composite animal and plant protein and expose the amino groups in the proteins. After the enzymatic hydrolysis, the protein is successively adsorbed by activated carbon, dialyzed, and the pH is adjusted to obtain a crude hydrolysate. The crude hydrolyzed protein solution was successively concentrated, ultrafiltered, and dried to obtain hydrolyzed protein powder. (2) Pretreatment of silanol derivatives: After adjusting the pH of water to acidic using organic acids, a silanol derivatizing agent is added and stirred to hydrolyze the epoxy groups into hydroxyl groups, thus obtaining the silanol derivatizing agent. (3) Preparation of proteins by silanolization hydrolysis: Prepare a hydrolyzed protein solution with a solid content of 20-25% by preparing the hydrolyzed protein powder obtained in step (1). Add the silanol derivatizer obtained in step (2) to the hydrolyzed protein solution, control the pH to 8.5-9.5, and stir while adding. The hydrolyzed protein and silanol derivatizer undergo silanol derivatization reaction under stirring conditions. After the reaction is completed, de-alcoholization under reduced pressure is performed to obtain silanolized hydrolyzed protein, which is the silanolized derivative of the animal and plant hydrolyzed protein.

2. The method for preparing silanolized derivatives of hydrolyzed animal and plant proteins according to claim 1, characterized in that: In step (1), the animal protein is any one of collagen, silk protein, keratin, elastin, etc.; the plant protein is any one of wheat protein, corn protein, soybean protein, oat protein, rice protein, etc.

3. The method for preparing silanolized derivatives of hydrolyzed animal and plant proteins according to claim 2, characterized in that: In step (1), the animal protein is keratin; the plant protein is soybean protein; and the mass ratio of soybean protein and keratin when compounded is 2:

1.

4. The method for preparing silanolized derivatives of hydrolyzed animal and plant proteins according to claim 1, characterized in that: In step (1), the pretreatment is as follows: the treatment time is 30 minutes to 2 hours, the treatment temperature is 45℃, the pH of the system during treatment is 8-9, the mass ratio of the compound animal and plant protein to β-mercaptoethanol is 1:60 to 1:40, and the concentration of β-mercaptoethanol in the mixed system is controlled at 10-18 mmol / L; the protease includes alkaline protease and alkaline aminopeptidase, the mass ratio of alkaline protease to alkaline aminopeptidase is (1-4):1, and the enzyme activity is 200,000 u / g; during enzymatic hydrolysis, the substrate concentration is 20-40 wt%, and the enzyme dosage is 1 wt%; during enzymatic hydrolysis, the pH of the system is 8-9, the hydrolysis temperature is 50℃, and the hydrolysis time is 3-6 h.

5. The method for preparing silanolized derivatives of hydrolyzed animal and plant proteins according to claim 1, characterized in that: In step (1), after the enzymatic hydrolysis is completed, the enzyme is inactivated and the system is adsorbed by the porous activated carbon, thereby performing decolorization and deodorization treatment. After removing mercaptoethanol by dialysis, the pH of the system was adjusted to 7.0 to obtain crude hydrolyzed protein solution. The crude hydrolyzed protein solution was concentrated and then subjected to ultrafiltration. The crude hydrolyzed protein solution was treated with a 3kDa ultrafiltration membrane and dried to obtain hydrolyzed protein powder with an average molecular weight range of 200-3000 Da.

6. The method for preparing silanolized derivatives of hydrolyzed animal and plant proteins according to claim 1, characterized in that: In step (2), the silanol derivative is selected from any one of 3-(2,3-epoxypropoxy)propylmethyldimethoxysilane, 3-(2,3-epoxypropoxy)propylmethyldiethoxysilane, 3-(2,3-epoxypropoxy)propylmethyldipropoxysilane, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, and 3-(2,3-epoxypropoxy)propyltriethoxysilane.

7. The method for preparing silanolized derivatives of hydrolyzed animal and plant proteins according to claim 1, characterized in that: In step (2), the organic acid is formic acid or acetic acid. After adjusting the pH of water to 4.5-5.0 with the organic acid, the silanol derivatizing agent is added and stirred for 30 minutes to hydrolyze the epoxy group into the hydroxyl group, which is then hydrolyzed into 3-(2,3-epoxypropoxy)propylmethyldihydroxysilane or 3-(2,3-epoxypropoxy)propyltrihydroxysilane, thus obtaining the silanol derivatizing agent.

8. The method for preparing silanolized derivatives of hydrolyzed animal and plant proteins according to claim 1, characterized in that: In step (3), the silanol derivatizer is added to the hydrolyzed protein solution under stirring at 45°C. The mass ratio of the solute to the silanol derivatizer in the hydrolyzed protein solution is 5:1 (calculated based on molecular weight). After the silanol derivatizer is added, stirring continues, the temperature is maintained at 45°C, the pH of the system is controlled at 8.5-9.5, and the reaction is stopped after stirring for 3 hours. After de-alcoholization under reduced pressure, silanolized hydrolyzed protein is obtained, which is the silanolized derivative of the animal and plant hydrolyzed protein.

9. A silanolized derivative of hydrolyzed animal or plant protein obtained by the preparation method according to any one of claims 1 to 8.

10. The use of the silanolized derivative of hydrolyzed animal and plant proteins according to claim 9 in the preparation of hair care product smoothing conditioner, hair care product extension and breakage prevention agent, hair care product moisturizer, and hair care product repair agent.

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