Collagen, preparation method and application thereof, and hair product for repairing and / or fluffing hair

Abstract

The invention relates to a collagen preparation and hair care technology, and discloses collagen, a preparation method and application thereof, and a hair product for repairing and / or fluffing hair. The weight-average molecular weight of the collagen is 2500-10000 Da, and the content of components with the molecular weight larger than or equal to 2000 and smaller than 5000 Da is 17-28 w / w%. The raw material of the collagen is non-fish-source gelatin with the following components: 18-31w / w% of a component with a molecular weight greater than or equal to 150000 and less than or equal to 2000000 Da, 10-22w / w% of a component with a molecular weight greater than or equal to 100000 and less than 150000 Da, 28-33w / w% of a component with a molecular weight greater than or equal to 50000 and less than 100000 Da, and the balance of water. The content of components with the molecular weight larger than or equal to 10000 and smaller than 50000 Da is 13-38 w / w%, and the content of components with the molecular weight smaller than 10000 Da is 2-5 w / w%. The collagen can play a role in repairing and fluffing hair at the same time.

Description

Technical Field

[0001] The invention relates to collagen preparation and hair care technology, and in particular to collagen and a preparation method and application thereof, as well as a hair product for repairing and / or making hair fluffy. Background Art

[0002] Hair is a long-chain polymer aggregate of keratin, and its main component is keratin. Keratin is composed of a variety of amino acids, among which cystine has the highest content, generally up to 14% or more. Hair is composed of hair follicles and hair shafts. Among them, the hair shaft is composed of the medulla layer, cortex layer, and stratum corneum from the inside to the outside. The stratum corneum is the outermost layer of the hair shaft, which is a scale-like structure (hair scales) formed by the folding of multiple layers of hair cuticle cells.

[0003] As people pursue beauty, more and more people begin to change their appearance by dyeing and perming their hair. However, the chemical ingredients used in dyeing and perming hair can cause varying degrees of damage to hair fibers. In addition, other external factors such as daily combing, sunlight exposure, and the use of poor quality hair care products can cause damage to the hair cuticle, ultimately leading to problems such as frizziness, dullness, curliness, and split ends.

[0004] At present, most of the hair care products on the market use silicone oil, silicone oil substitutes or natural oils to repair hair scales. For example, the silicone oil in silicone oil-containing hair care products can adhere to the gaps in the hair scales, repair the hair and make the hair smooth, but long-term use will cause silicone oil to accumulate on the hair, making the hair unnatural, thick and collapsed. In silicone-free hair care products, natural oils or silicone oil substitutes (such as alcohol ethers and glyceride conditioners, etc.) are often used to repair the hair, but there are also problems of thickness and collapse after washing, and there is a certain irritation to the scalp.

[0005] In order to improve the volume of hair, hair care products generally add cationic conditioning agents. For example: guar hydroxypropyltrimonium chloride, polyquaternium-10, polyquaternium-11, etc. However, cationic conditioning agents are generally chemically synthesized and have a certain degree of irritation to the scalp. For example, polyquaternium-10 can cause skin irritation.

[0006] Some hair care products add protein ingredients, generally to increase the effectiveness of the product and sales promotion content, but the effect of protein ingredients is often limited and the added content is low. It needs to be combined with chemical synthetic reagents, and it is not possible to truly use only bio-based protein ingredients to repair and fluff hair. The role of collagen in shampoo products reported in related literature is mostly to repair hair and protect hair. There is no collagen that can simultaneously repair and fluff hair. Summary of the invention

[0007] The purpose of the present invention is to overcome the problems of thick hair, collapse of hair and the like caused by silicone oil or natural oil or silicone oil substitutes (such as alcohol ether and glyceride conditioning agents, etc.) in the prior art hair care products when repairing hair scales, and to provide a collagen protein and a preparation method and application thereof, as well as a hair product for repairing and / or fluffing hair. The collagen protein can simultaneously play the role of repairing and fluffing hair, and can be used to prepare hair products without silicone oil, grease or cationic conditioning agents, thereby effectively improving the safety of the hair products.

[0008] In order to achieve the above-mentioned purpose, the first aspect of the present invention provides a collagen, the weight average molecular weight of the collagen is 2500-10000Da, and the content of the component with a molecular weight greater than or equal to 2000 and less than 5000Da in the collagen is 17-28w / w%; the raw material of the collagen is non-fish source gelatin with the following composition: the content of the component with a molecular weight greater than or equal to 150000 and less than or equal to 2000000Da is 18-31w / w%, the content of the component with a molecular weight greater than or equal to 100000 and less than 150000Da is 10-22w / w%, the content of the component with a molecular weight greater than or equal to 50000 and less than 100000Da is 28-33w / w%, the content of the component with a molecular weight greater than or equal to 10000 and less than 50000Da is 13-38w / w%, and the content of the component with a molecular weight less than 10000Da is 2-5w / w%.

[0009] Preferably, the raw material of the collagen is non-fish gelatin having the following composition: the content of components with a molecular weight greater than or equal to 150,000 and less than or equal to 2,000,000 Da is 18-23 w / w%, the content of components with a molecular weight greater than or equal to 100,000 and less than 150,000 Da is 10-14 w / w%, the content of components with a molecular weight greater than or equal to 50,000 and less than 100,000 Da is 28-32 w / w%, the content of components with a molecular weight greater than or equal to 10,000 and less than 50,000 Da is 30-38 w / w%, and the content of components with a molecular weight less than 10,000 Da is 2-5 w / w%.

[0010] Preferably, the weight average molecular weight of the collagen is 3000-7000Da, and the content of the component with a molecular weight greater than or equal to 2000 and less than 5000Da in the collagen is 22-27w / w%.

[0011] Preferably, the weight average molecular weight of the non-fish source gelatin is 80,000-160,000 Da, preferably 80,000-119,000 Da.

[0012] The second aspect of the present invention provides a method for preparing collagen, the method comprising: mixing non-fish-derived gelatin with a protease and performing enzymolysis to obtain collagen with a weight average molecular weight of 2500-10000Da;

[0013] The non-fish source gelatin has the following composition: the content of components with a molecular weight greater than or equal to 150,000 and less than or equal to 2,000,000 Da is 18-31 w / w%, the content of components with a molecular weight greater than or equal to 100,000 and less than 150,000 Da is 10-22 w / w%, the content of components with a molecular weight greater than or equal to 50,000 and less than 100,000 Da is 28-33 w / w%, the content of components with a molecular weight greater than or equal to 10,000 and less than 50,000 Da is 13-38 w / w%, and the content of components with a molecular weight less than 10,000 Da is 2-5 w / w%;

[0014] The protease is selected from at least one of neutral protease, trypsin, papain and bromelain.

[0015] Preferably, the non-fish source gelatin has the following composition: the content of components with a molecular weight greater than or equal to 150,000 and less than or equal to 2,000,000 Da is 18-23 w / w%, the content of components with a molecular weight greater than or equal to 100,000 and less than 150,000 Da is 10-14 w / w%, the content of components with a molecular weight greater than or equal to 50,000 and less than 100,000 Da is 28-32 w / w%, the content of components with a molecular weight greater than or equal to 10,000 and less than 50,000 Da is 30-38 w / w%, and the content of components with a molecular weight less than 10,000 Da is 2-5 w / w%;

[0016] Preferably, the weight average molecular weight of the collagen is 3000-7000Da, and the content of the component with a molecular weight greater than or equal to 2000 and less than 5000Da in the collagen is 22-27w / w%;

[0017] Preferably, the weight average molecular weight of the non-fish source gelatin is 80,000-160,000 Da, preferably 80,000-119,000 Da.

[0018] Preferably, relative to 1g of the non-fish-derived gelatin, the amount of enzyme used in the enzymatic hydrolysis is 200-1800U.

[0019] Preferably, the conditions for the enzymatic hydrolysis include at least: a temperature of 45-60° C., a pH of 6.5-7, and a time of 1-3 h.

[0020] Preferably, the method comprises: mixing and dissolving the non-fish-derived gelatin with a solvent and then performing the enzymatic hydrolysis.

[0021] Preferably, the weight ratio of the non-fish source gelatin to the solvent is 1:4-6, and the temperature of the mixed dissolution is 48-63°C.

[0022] Preferably, the method further comprises: concentrating and drying the enzymatic hydrolysis product.

[0023] The third aspect of the present invention provides collagen prepared by the method as described above.

[0024] The fourth aspect of the present invention provides the use of the collagen as described above in hair products.

[0025] Preferably, the hair product uses the collagen as the only active ingredient for repairing and / or loosening hair.

[0026] Preferably, the hair product is selected from at least one of shampoo, hair care and hair shampoo and hair care products, more preferably a hair shampoo and hair care product.

[0027] A fifth aspect of the present invention provides a hair product for repairing and / or loosening hair, wherein the hair product contains the collagen as described above.

[0028] Preferably, the hair product uses the collagen as the only active ingredient for repairing and / or loosening hair.

[0029] Preferably, the content of collagen in the hair product is 0.5-7w / w%, more preferably 1-5w / w%.

[0030] Preferably, the hair product further contains a surfactant, a moisturizer, a thickener, an acidity regulator, a fragrance, a preservative and water.

[0031] Through the above technical scheme, the collagen provided by the present invention can be adsorbed on the surface of hair, repair hair scales, and make hair fluffy. It can be used as the only bio-based hair care raw material with repairing and fluffing effects, and added to hair care products without silicone oil, grease (natural or chemically synthesized), and cationic conditioning agents, to play a role in fluffing hair while repairing and protecting hair. The collagen can truly achieve the use of pure bio-based protein to repair and fluff hair, reduce the use of chemically synthesized hair care raw materials such as cationic conditioning agents that have a fluffing effect, reduce the irritation of chemical synthetic reagents to the scalp, and improve the safety of hair products. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 This is an electron micrograph of damaged hair that has not been repaired;

[0033] Figure 2 This is an electron microscope image of collagen prepared in comparative example 1 repairing damaged hair;

[0034] Figure 3is an electron microscope image of collagen prepared in Example 1 repairing damaged hair;

[0035] Figure 4 This is a comparison chart of the fluffiness of in vitro damaged real human hair bundles of the same mass after using shampoos of different formulas: No. 1 is the hair after washing with the basic formula shampoo, No. 2 is the hair after washing with the shampoo obtained by adding the collagen prepared in Comparative Example 1 to the basic formula shampoo, and No. 3 is the hair after washing with the shampoo obtained by adding the collagen prepared in Example 1 to the basic formula shampoo. DETAILED DESCRIPTION

[0036] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0037] The first aspect of the present invention provides a collagen having a weight average molecular weight of 2500-10000Da, wherein the content of components with a molecular weight greater than or equal to 2000 and less than 5000Da in the collagen is 17-28w / w%; the raw material of the collagen is non-fish-derived gelatin having the following composition: the content of components with a molecular weight greater than or equal to 150000 and less than or equal to 2000000Da is 18-31w / w%, the content of components with a molecular weight greater than or equal to 100000 and less than 150000Da is 10-22w / w%, the content of components with a molecular weight greater than or equal to 50000 and less than 100000Da is 28-33w / w%, the content of components with a molecular weight greater than or equal to 10000 and less than 50000Da is 13-38w / w%, and the content of components with a molecular weight less than 10000Da is 2-5w / w%.

[0038] During the research and development process, the inventor of the present invention unexpectedly discovered that collagen with a weight average molecular weight of 2500-10000Da can be prepared by using collagen partial hydrolyzate with a specific molecular weight distribution, namely non-fish-derived gelatin, as a raw material and enzymatic hydrolysis with a specific protease, and can be adsorbed on the surface of hair to repair hair scales and make hair fluffy. It can be added to hair care products without silicone oil, oil (natural or chemically synthesized), or cationic conditioning agents as the only bio-based hair care raw material with repairing and fluffing effects, and can play a role in fluffing hair while repairing and protecting hair. The collagen can truly realize the use of pure bio-based protein to repair and fluff hair, reduce the use of chemically synthesized hair care raw materials such as cationic conditioning agents that have a fluffing effect, reduce the irritation of chemical synthetic reagents to the scalp, and improve the safety of hair products.

[0039] In the present invention, non-fish-derived gelatin refers to gelatin extracted from bones, skins, tendons, tendons, etc. of animals other than fish (such as cattle, sheep, pigs, etc.). Fish-derived gelatin refers to gelatin extracted from fish skin, fish scales, fish bones, etc.

[0040] In the present invention, the raw material of the collagen is a non-fish-derived gelatin having the following composition: the content of the component with a molecular weight greater than or equal to 150,000 and less than or equal to 2,000,000 Da is 18-31 w / w%, specifically 18 w / w%, 20 w / w%, 22 w / w%, 24 w / w%, 26 w / w%, 28 w / w%, 30 w / w%, 31 w / w%, or any value between the foregoing two values, preferably 18-23 w / w%; the content of the component with a molecular weight greater than or equal to 100,000 and less than 150,000 Da is 10-22 w / w%, specifically 10 w / w%, 12 w / w%, 14 w / w%, 16 w / w%, 18 w / w%, 20 w / w%, 22 w / w%, or any value between the foregoing two values, preferably 10-14 w / w%; the content of the component with a molecular weight greater than or equal to 100,000 and less than 150,000 Da is 10-22 w / w%, specifically 10 w / w%, 12 w / w%, 14 w / w%, 16 w / w%, 18 w / w%, 20 w / w%, 22 w / w%, or any value between the foregoing two values, preferably 10-14 w / w%; The content of the component with a molecular weight greater than or equal to 10000 and less than 50000Da is 13-38w / w%, specifically 13w / w%, 18w / w%, 23w / w%, 28w / w%, 33w / w%, 38w / w%, or any value between the two values, preferably 30-38w / w%; the content of the component with a molecular weight less than 10000Da is 2-5w / w%, specifically 2w / w%, 3w / w%, 4w / w%, 5w / w%, or any value between the two values. By controlling the non-fish-derived gelatin raw materials to an optimal molecular weight composition, the collagen obtained has a better repair effect on damaged hair and a better fluffy effect on hair.

[0041] In the present invention, the weight average molecular weight of the collagen is 2500-10000Da, specifically 2500Da, 3500Da, 4500Da, 5500Da, 6500Da, 7500Da, 8500Da, 9500Da, 10000Da, or any value between the foregoing two values. In order to further enhance the repair effect of collagen on damaged hair and the fluffy effect on hair, preferably, the weight average molecular weight of the collagen is 3000-7000Da.

[0042] In the present invention, in order to further enhance the repairing effect of collagen on damaged hair and the fluffy effect on hair, preferably, the weight average molecular weight of the non-fish source gelatin is 80,000-160,000 Da, specifically 80,000 Da, 90,000 Da, 100,000 Da, 110,000 Da, 120,000 Da, 130,000 Da, 140,000 Da, 150,000 Da, 160,000 Da, or any value between the foregoing two values, more preferably 80,000-119,000 Da.

[0043] The non-fish-derived gelatin raw material used in the present invention can be obtained by screening with a gel permeation chromatography (GPC) to have the specific molecular weight and content distribution.

[0044] In the present invention, the weight-average molecular weight is measured by high-performance size exclusion chromatography, the molecular weight determination method of non-fish-derived gelatin raw materials is based on General Chapter 0514 (Molecular Exclusion Chromatography) of the 2020 edition of the "Pharmacopoeia of the People's Republic of China", and the molecular weight determination method of collagen obtained after enzymatic hydrolysis is based on Appendix A of GB 31645-2018 "National Food Safety Standard Collagen Peptide".

[0045] The second aspect of the present invention provides a method for preparing collagen, the method comprising: mixing non-fish-derived gelatin with a protease for enzymatic hydrolysis to obtain collagen with a weight average molecular weight of 2500-10000Da, wherein the content of the component with a molecular weight greater than or equal to 2000 and less than 5000Da in the collagen is 17-28w / w%;

[0046] The non-fish source gelatin has the following composition: the content of components with a molecular weight greater than or equal to 150,000 and less than or equal to 2,000,000 Da is 18-31 w / w%, the content of components with a molecular weight greater than or equal to 100,000 and less than 150,000 Da is 10-22 w / w%, the content of components with a molecular weight greater than or equal to 50,000 and less than 100,000 Da is 28-33 w / w%, the content of components with a molecular weight greater than or equal to 10,000 and less than 50,000 Da is 13-38 w / w%, and the content of components with a molecular weight less than 10,000 Da is 2-5 w / w%;

[0047] The protease is selected from at least one of neutral protease, trypsin, papain and bromelain.

[0048] The preparation method of the present invention uses the collagen partial hydrolyzate - non-fish-derived gelatin as a raw material, and prepares collagen with repairing and fluffy functions through gelatin screening with a specific molecular weight distribution and enzymatic hydrolysis technology. The process is simple and easy to operate, which is conducive to the industrial production of collagen.

[0049] The protease used in the present invention is commercially available.

[0050] According to the present invention, preferably, the non-fish source gelatin has the following components: the content of the component with a molecular weight greater than or equal to 150000 and less than or equal to 2000000Da is 18-23w / w%, the content of the component with a molecular weight greater than or equal to 100000 and less than 150000Da is 10-14w / w%, the content of the component with a molecular weight greater than or equal to 50000 and less than 100000Da is 28-32w / w%, the content of the component with a molecular weight greater than or equal to 10000 and less than 50000Da is 30-38w / w%, and the content of the component with a molecular weight less than 10000Da is 2-5w / w%;

[0051] According to the present invention, preferably, the weight average molecular weight of the collagen is 3000-7000Da, and the content of the component with a molecular weight greater than or equal to 2000 and less than 5000Da in the collagen is 22-27w / w%.

[0052] According to the present invention, preferably, the weight average molecular weight of the non-fish source gelatin is 80,000-160,000 Da, preferably 80,000-119,000 Da.

[0053] According to the present invention, preferably, relative to 1g of the non-fish-derived gelatin, the amount of enzyme used in the enzymatic hydrolysis is 200-1800U, specifically 200U, 400U, 600U, 800U, 1000U, 1200U, 1400U, 1600U, 1800U, or any value between the two aforementioned values; more preferably 600-1800U. The inventors have found that under this preferred embodiment, it is beneficial to further enhance the repair effect of collagen on damaged hair and the fluffy effect on hair.

[0054] According to the present invention, preferably, the conditions for the enzymolysis include at least: a temperature of 45-60°C, specifically 45°C, 48°C, 51°C, 54°C, 57°C, 60°C, or any value between the two values; a pH of 6.5-7, specifically 6.5, 6.6, 6.7, 6.8, 6.9, 7, or any value between the two values; a time of 1-3h, specifically 1h, 1.5h, 2h, 2.5h, 3h, or any value between the two values. The inventors have found that under this preferred embodiment, it is beneficial to improve the efficiency of enzymolysis and further enhance the repair effect of collagen on damaged hair and the fluffy effect on hair.

[0055] According to the present invention, preferably, the method comprises: mixing and dissolving the non-fish-derived gelatin with a solvent and then performing the enzymatic hydrolysis. Exemplarily, the solvent is pure water.

[0056] Further preferably, the weight ratio of the non-fish source gelatin to the solvent is 1:4-6, and the temperature of the mixed dissolution is 48-63°C.

[0057] In the present invention, after the enzymatic hydrolysis reaction is completed, the enzyme is generally inactivated at above 90°C for 15-25 minutes, and the enzymatic hydrolysis product is subsequently treated after the enzymatic hydrolysis solution is cooled. Preferably, the method further comprises: concentrating and drying the enzymatic hydrolysis product to obtain a pure collagen product. The concentration can concentrate the enzymatic hydrolysis solution to a collagen concentration of 25-35w / w% in the feed liquid, and then drying, wherein the drying method can be conventional drying, freeze drying, vacuum drying, spray drying, etc., preferably spray drying.

[0058] The third aspect of the present invention provides collagen prepared by the method as described above.

[0059] The fourth aspect of the present invention provides the use of the collagen as described above in hair products.

[0060] The collagen provided by the present invention can be adsorbed on the surface of hair to repair hair scales and make hair fluffy. Preferably, the hair product uses the collagen as the only active ingredient that has the effect of repairing and / or making hair fluffy.

[0061] In the present invention, the hair product is selected from at least one of shampoo, hair care and hair shampoo and hair care products, more preferably a hair shampoo and hair care product. The hair product may further contain a carrier acceptable to the hair product.

[0062] A fifth aspect of the present invention provides a hair product for repairing and / or loosening hair, wherein the hair product contains the collagen as described above.

[0063] According to the present invention, preferably, the hair product uses the collagen as the only active ingredient having the effect of repairing and / or loosening hair.

[0064] According to the present invention, preferably, the content of collagen in the hair product is 0.5-7w / w%, specifically 0.5w / w%, 1w / w%, 2w / w%, 3w / w%, 4w / w%, 5w / w%, 6w / w%, 7w / w%, or any value between the aforementioned two values; more preferably 1-5w / w%.

[0065] According to the present invention, the hair product may contain other carriers required for forming the product. Preferably, the hair product further contains a surfactant, a moisturizer, a thickener, an acidity regulator, a fragrance, a preservative and water.

[0066] Among them, the surfactant can be one or more of sodium laureth sulfate, cocamidopropyl betaine, sodium lauryl sulfate, cocamide MEA, ammonium laureth sulfate, ammonium lauryl sulfate, sodium lauroyl sarcosinate, and sodium cocoyl methyl taurate;

[0067] The humectant may be one or more of glycerol, hydrolyzed corn starch, propylene glycol, and 1,3-butylene glycol;

[0068] The thickener may be one or more of sodium chloride, potassium chloride, ammonium chloride, hydroxypropyl methylcellulose, and guar gum;

[0069] The acidity regulator can be one or more of sodium hydroxide, potassium hydroxide, citric acid, and hydrochloric acid;

[0070] The preservative may be one or more of potassium sorbate, sodium benzoate, phenoxyethanol, and parabens.

[0071] The above raw materials are all commercially available.

[0072] According to the present invention, preferably, based on the total weight of the hair product, the content of each raw material in the hair product is: the content of the above-mentioned collagen is 0.5-7w / w%, the content of the surfactant is 8-30w / w%, the content of the humectant is 1.0-4.0w / w%, the content of the thickener is 1.0-3.0w / w%, the acidity regulator adjusts the pH value to a range of 5.5-6.5, the content of the fragrance is 0.1-1.0w / w%, the content of the preservative is 0.05-0.5w / w%, and the balance is water.

[0073] According to a particularly preferred embodiment of the present invention, the method for preparing collagen comprises:

[0074] Screening non-fish-derived gelatin with a specific molecular weight and distribution by gel permeation chromatography (GPC), wherein the non-fish-derived gelatin has the following composition: a component content of a molecular weight greater than or equal to 150,000 and less than or equal to 2,000,000 Da is 18-31 w / w%, a component content of a molecular weight greater than or equal to 100,000 and less than 150,000 Da is 10-22 w / w%, a component content of a molecular weight greater than or equal to 50,000 and less than 100,000 Da is 28-33 w / w%, a component content of a molecular weight greater than or equal to 10,000 and less than 50,000 Da is 13-38 w / w%, and a component content of a molecular weight less than 10,000 Da is 2-5 w / w%;

[0075] Weigh a certain amount of non-fish-derived gelatin, mix and dissolve the non-fish-derived gelatin and water at a weight ratio of 1:4-6 at a temperature of 48-63° C. to obtain a solution;

[0076] The solution is adjusted to pH 6.5-7.0 with an inorganic base, mixed with a protease, and subjected to enzymatic hydrolysis at a temperature of 45-60° C. for 1-3 hours, wherein the protease is selected from at least one of neutral protease, trypsin, papain and bromelain, and the amount of the protease is 200-1800 U relative to 1 g of the non-fish-derived gelatin;

[0077] After the enzymatic hydrolysis is completed, the enzyme is inactivated at above 90°C for 15-25 minutes, and the enzymatic hydrolyzate is cooled and concentrated to a collagen concentration of 25-35w / w% in the feed liquid, and then spray-dried to obtain collagen with a weight average molecular weight of 2500-10000Da.

[0078] The present invention will be described in detail below through examples.

[0079] In the following examples, non-fish-derived gelatin and fish-derived gelatin were both from Baotou Dongbao Biotechnology Co., Ltd.;

[0080] Sodium laureth sulfate, cocamidopropyl betaine, glycerin, sodium chloride, sodium benzoate, sodium hydroxide, and flavors are all commercially available daily chemical or food grade raw materials;

[0081] Unless otherwise specified, other raw materials or reagents involved, such as isolated human hair bundles and proteases, are commercially available products.

[0082] In the following examples, non-fish gelatin raw materials with specific molecular weight and molecular weight distribution were screened by gel permeation chromatography (GPC), and the method was based on General Rule 0514 (size exclusion chromatography) of the 2020 edition of the Pharmacopoeia of the People's Republic of China. The method for determining the molecular weight of collagen after enzymatic hydrolysis was based on Appendix A of GB 31645-2018 National Food Safety Standard Collagen Peptide.

[0083] Example 1

[0084] Screening non-fish-derived gelatin with a specific molecular weight and molecular weight distribution by gel permeation chromatography (GPC), as shown in Table 1; Weighing a certain mass of gelatin, adding it into 53° C. pure water at a ratio of gelatin: water = 1:4 (w / w) to dissolve it to obtain a solution;

[0085] The pH value of the solution was adjusted to 7 with an inorganic base (sodium hydroxide), and 1800U / g of gelatin neutral protease was added, and enzymolysis was carried out at 50°C for 2.5h. After the enzymolysis was completed, the enzyme was inactivated at above 90°C for 20min, and the enzymolysis solution was cooled and concentrated to a collagen concentration of 30w / w% in the feed liquid, and then spray-dried to obtain collagen with a weight-average molecular weight of 4200Da, in which the content of components with a molecular weight greater than or equal to 2000 and less than 5000Da was 26w / w%.

[0086] Example 2

[0087] Screening non-fish-derived gelatin with a specific molecular weight and molecular weight distribution by gel permeation chromatography (GPC), as shown in Table 1; Weighing a certain mass of gelatin, adding it into 58° C. pure water at a ratio of gelatin: water = 1:5 (w / w) to dissolve it to obtain a solution;

[0088] The pH value of the solution was adjusted to 6.5 with an inorganic base (sodium hydroxide), and 400U / g of papain was added to gelatin, and enzymolysis was carried out at 55°C for 2h. After the enzymolysis was completed, the enzyme was inactivated at above 90°C for 25min, and the enzymolysis solution was cooled and concentrated to a collagen concentration of 25w / w% in the feed liquid, and then spray-dried to obtain collagen with a weight-average molecular weight of 10000Da, in which the content of components with a molecular weight greater than or equal to 2000 and less than 5000Da was 17w / w%.

[0089] Example 3

[0090] Screening non-fish-derived gelatin with a specific molecular weight and molecular weight distribution by gel permeation chromatography (GPC), as shown in Table 1; Weighing a certain mass of gelatin, adding it into 63° C. pure water at a ratio of gelatin: water = 1:6 (w / w) to dissolve it to obtain a solution;

[0091] The pH value of the solution was adjusted to 7.0 with an inorganic base (sodium hydroxide), and 1750U / g of bromelain was added to gelatin, and enzymolysis was carried out at 60°C for 1.5h. After the enzymolysis was completed, the enzyme was inactivated at above 90°C for 15min, and the enzymolysis solution was cooled and concentrated to a collagen concentration of 30w / w% in the feed liquid, and then spray-dried to obtain collagen with a weight-average molecular weight of 7000Da, in which the content of components with a molecular weight greater than or equal to 2000 and less than 5000Da was 22w / w%.

[0092] Example 4

[0093] Collagen was prepared according to the raw materials and method of Example 1, except that pure water at 48°C was added to dissolve the obtained solution, and the added protease was replaced with trypsin at 600 U / g gelatin, and the enzymatic hydrolysis was carried out at 45°C for 3 h;

[0094] The weight average molecular weight of the collagen prepared in Example 4 is 3000 Da, and the content of the component with a molecular weight greater than or equal to 2000 and less than 5000 Da in the collagen is 27 w / w%.

[0095] Example 5

[0096] Using the gelatin in Example 3 as a raw material, a certain amount of gelatin was weighed and added into 58° C. pure water at a ratio of gelatin: water = 1:5 (w / w) to dissolve the obtained solution;

[0097] The pH value of the solution was adjusted to 6.8 with an inorganic base (sodium hydroxide), and 1000U / g gelatin neutral protease and 200U / g gelatin papain were added, and enzymolysis was carried out at 55°C for 2h. After the enzymolysis was completed, the enzyme was inactivated at above 90°C for 25min, and the enzymolysis solution was cooled and concentrated to a collagen concentration of 30w / w% in the feed liquid, and then spray-dried to obtain collagen with a weight-average molecular weight of 5100Da, in which the content of components with a molecular weight greater than or equal to 2000 and less than 5000Da was 24w / w%.

[0098] Example 6

[0099] Using the gelatin in Example 2 as a raw material, a certain amount of gelatin was weighed and added into 58° C. pure water at a ratio of gelatin: water = 1:6 (w / w) to dissolve to obtain a solution;

[0100] The pH value of the dissolved solution was adjusted to 7 with an inorganic base (sodium hydroxide), and 1200U / g gelatin neutral protease and 500U / g gelatin bromelain were added, and enzymolysis was carried out at 55°C for 1 hour. After the enzymolysis was completed, the enzyme was inactivated at above 90°C for 20 minutes, and the enzymolysis solution was cooled and concentrated to a collagen concentration of 25w / w% in the feed liquid, and then spray-dried to obtain collagen with a weight-average molecular weight of 8500Da, in which the content of components with a molecular weight greater than or equal to 2000Da and less than 5000Da was 20w / w%.

[0101] Example 7

[0102] Using the gelatin in Example 3 as a raw material, a certain amount of gelatin was weighed and added into 48° C. pure water at a ratio of gelatin: water = 1:5 (w / w) to dissolve the gelatin to obtain a solution;

[0103] The pH value of the solution was adjusted to 7 with an inorganic base (sodium hydroxide), and 600U / g gelatin neutral protease and 300U / g gelatin trypsin were added, and enzymolysis was carried out at 45°C for 2h. After the enzymolysis was completed, the enzyme was inactivated at above 90°C for 20min, and the enzymolysis solution was cooled and concentrated to a collagen concentration of 35w / w% in the feed liquid, and then spray-dried to obtain collagen with a weight-average molecular weight of 2500Da, in which the content of components with a molecular weight greater than or equal to 2000Da and less than 5000Da was 28w / w%.

[0104] Example 8

[0105] Collagen was prepared according to the method of Example 6, except that the gelatin used in Example 8 was shown in Table 1, and the added protease was replaced by 1000 U / g gelatin neutral protease and 400 U / g gelatin bromelain, and the enzymatic hydrolysis was carried out at 55° C. for 1 h;

[0106] The weight average molecular weight of the collagen prepared in Example 8 is 9300 Da, and the content of the component with a molecular weight greater than or equal to 2000 Da and less than 5000 Da in the collagen is 18 w / w%.

[0107] Comparative Example 1

[0108] Collagen was prepared according to the method of Example 1, except that the gelatin raw material was replaced with non-fish-derived gelatin having a molecular weight and molecular weight distribution shown in Table 1.

[0109] The weight average molecular weight of the collagen prepared in Comparative Example 1 is 4100 Da, and the content of the component with a molecular weight greater than or equal to 2000 and less than 5000 Da in the collagen is 24 w / w%.

[0110] Comparative Example 2

[0111] Collagen was prepared according to the method of Example 1, except that the gelatin raw material was replaced with fish-derived gelatin having the molecular weight and molecular weight distribution shown in Table 1.

[0112] The weight average molecular weight of the collagen prepared in Comparative Example 2 is 5000 Da, and the content of the component with a molecular weight greater than or equal to 2000 and less than 5000 Da in the collagen is 22 w / w%.

[0113] Comparative Example 3

[0114] Collagen was prepared according to the materials and method of Example 1, except that the added protease was replaced by 1800 U / g gelatin alkaline protease.

[0115] The weight average molecular weight of the collagen prepared in Comparative Example 3 is 7600 Da, and the content of the component with a molecular weight greater than or equal to 2000 and less than 5000 Da in the collagen is 16 w / w%.

[0116] Table 1 Molecular weight and molecular weight distribution of gelatin used in the examples and comparative examples

[0117]

[0118] Test Case

[0119] 1. Electron microscope test

[0120] Referring to the damaged hair procedure in T / GDCA017-2023 "Hair Care Product Efficacy Evaluation Method", isolated damaged human hair was prepared. The collagen prepared in Example 1 and the collagen prepared in Comparative Example 1 were respectively prepared into a collagen aqueous solution with a concentration of 3w / w%, which was used to treat isolated damaged human hair and then the hair was subjected to electron microscopy testing. Specifically, the isolated damaged human hair was immersed in the collagen aqueous solution, taken out after soaking for 30 minutes, rinsed with running water for 1 minute, and dried naturally. For details of the electron microscopy test results, see Figures 1 to 3 .

[0121] from Figures 1 to 3 It can be seen that the hair scales of the unrepaired damaged hair are curled and fall off; after the damaged hair is repaired with the collagen prepared in Comparative Example 1, the hair scales are partially closed, but still curled to a certain extent; after the damaged hair is repaired with the collagen prepared in Example 1, the hair scales are completely closed. It can be seen that the damaged hair repair effect of the collagen prepared in Example 1 is significantly better than that of the collagen prepared in Comparative Example 1.

[0122] 2. Combing performance test

[0123] Prepare in vitro damaged human hair according to the damaged hair procedure in T / GDCA017-2023 "Hair Care Product Efficacy Evaluation Method". Comb the treated in vitro damaged human hair evenly and pack it into bundles, each bundle weighing 5g.

[0124] A basic formula shampoo without silicone oil, grease (natural or chemically synthesized), or cationic conditioning agent for all-in-one hair washing and conditioning is prepared. The basic formula shampoo (100 g) comprises the following components: 15.0 g of sodium laureth sulfate (concentration of 70 w / w%), 5.0 g of cocamidopropyl betaine (concentration of 30 w / w%), 1 g of glycerin, 2 g of sodium chloride, 1 g of essence, 0.08 g of sodium benzoate, sodium hydroxide for adjusting the pH value to 6.5, and the remainder being water.

[0125] In the basic formula shampoo, the collagen prepared in Examples 1 to 8 and Comparative Examples 1 to 3 (the addition amount is 3 g / 100 g of the basic formula shampoo) is added respectively to form the test shampoo. After testing the original combing force of the hair bundle, 1 g of each test shampoo is used to wash the damaged human hair (5 g per bundle) for 3 minutes, and the combing force of the hair bundle is measured after the human hair bundle is naturally dried. The results are shown in Table 2. The smaller the combing force, the easier the hair bundle is to comb and the smoother the surface of the hair bundle.

[0126] Table 2 Test results of combing performance of hair bundles of Examples and Comparative Examples

[0127] serial number Original combing force (N) Combing force after treatment (N) Example 1 0.109 0.051 Example 2 0.115 0.079 Example 3 0.113 0.066 Example 4 0.112 0.060 Example 5 0.116 0.061 Example 6 0.110 0.070 Example 7 0.114 0.076 Example 8 0.112 0.073 Comparative Example 1 0.110 0.108 Comparative Example 2 0.117 0.116 Comparative Example 3 0.114 0.111

[0128] 3. Fluffiness test

[0129] Prepare in vitro damaged human hair according to the damaged hair procedure in T / GDCA017-2023 "Hair Care Product Efficacy Evaluation Method". Comb the treated in vitro damaged human hair evenly and pack it into bundles, each bundle weighing 5g.

[0130] A basic formula shampoo without silicone oil, grease (natural or chemically synthesized), or cationic conditioning agent for all-in-one hair washing and conditioning is prepared. The basic formula shampoo (100 g) comprises the following components: 15.0 g of sodium laureth sulfate (concentration of 70 w / w%), 5.0 g of cocamidopropyl betaine (concentration of 30 w / w%), 1 g of glycerin, 2 g of sodium chloride, 1 g of essence, 0.08 g of sodium benzoate, sodium hydroxide for adjusting the pH value to 6.5, and the remainder being water.

[0131] In the basic formula shampoo, the collagen prepared in Examples 1 to 8 and Comparative Examples 1 to 3 was added respectively (the added amount was 3 g / 100 g of basic formula shampoo) to form test shampoos corresponding to Examples 1 to 8 and Comparative Examples 1 to 3.

[0132] Weigh 1g of the above basic formula shampoo and test shampoo respectively, wash the in vitro human hair bundles (5g per bundle) for 3 minutes, and hang them to dry naturally for 24 hours before measuring. Comb each hair bundle 10 times with an antistatic comb and take a picture. Import the picture into the computer, fix the starting position with CAD software, draw points on the edge of the hair bundle, connect the lines into a closed curve, calculate the area of ​​the hair bundle, and compare the size of the hair bundle area under the same shooting conditions. The results are shown in Table 3; the larger the hair bundle area, the better the hair fluffiness. Comparative pictures of the hair fluffiness test of the collagen prepared in Example 1 and Comparative Example 1 are shown in Figure 4 .

[0133] Table 3 Hair bundle fluffiness test results of the embodiment and comparative example

[0134] serial number <![CDATA[Area (mm 2 )]]> Example 1 72324 Example 2 66997 Example 3 68754 Example 4 69543 Example 5 70122 Example 6 67566 Example 7 68005 Example 8 67213 Comparative Example 1 60230 Comparative Example 2 60115 Comparative Example 3 60303

[0135] Figure 4 No. 1 is the hair washed with the basic formula shampoo; No. 2 is the hair washed with the shampoo obtained by adding the collagen prepared in Comparative Example 1 to the basic formula shampoo; No. 3 is the hair washed with the shampoo obtained by adding the collagen prepared in Example 1 to the basic formula shampoo. Figure 4 It can be seen that compared with the basic formula shampoo, the fluffiness of the hair after washing with the collagen shampoo prepared in Comparative Example 1 did not change significantly, while the hair after washing with the collagen shampoo prepared in Example 1 was significantly more fluffi.

[0136] In the basic formula shampoo, the collagen prepared in Example 1 and Comparative Example 1 was added according to the collagen concentration in Table 4 (based on the total mass of the shampoo, the concentration of collagen was 0.5w / w%, 1w / w%, 2w / w%, 3w / w%, 4w / w%, 5w / w%, 6w / w%, 7w / w%), respectively, to form test shampoos with different protein concentrations. Weigh 1g of each of the above test shampoos, wash the in vitro human hair bundles (5g per bundle) for 3 minutes, and hang them to dry naturally for 24 hours before measuring. Each hair bundle was combed 10 times with an antistatic comb and then photographed. The picture was imported into the computer, the starting position was fixed by CAD software, the edge of the hair bundle was plotted, and the lines were connected into a closed curve to calculate the hair bundle area. The hair bundle area was compared under the same shooting conditions. The results are shown in Table 4; the larger the hair bundle area, the better the hair fluffiness.

[0137] Table 4 Hair volume test results of collagen shampoo with different concentrations prepared in Example 1 and Comparative Example 1

[0138]

[0139] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A collagen protein, characterized in that The weight average molecular weight of the collagen is 2500-10000Da, and the content of the component with a molecular weight greater than or equal to 2000 and less than 5000Da in the collagen is 17-28w / w%; The raw material of the collagen is non-fish-derived gelatin with the following composition: the content of components with a molecular weight greater than or equal to 150,000 and less than or equal to 2,000,000 Da is 18-31 w / w%, the content of components with a molecular weight greater than or equal to 100,000 and less than 150,000 Da is 10-22 w / w%, the content of components with a molecular weight greater than or equal to 50,000 and less than 100,000 Da is 28-33 w / w%, the content of components with a molecular weight greater than or equal to 10,000 and less than 50,000 Da is 13-38 w / w%, and the content of components with a molecular weight less than 10,000 Da is 2-5 w / w%.

2. The collagen according to claim 1, characterized in that The raw material of the collagen is non-fish-derived gelatin with the following composition: the content of components with a molecular weight greater than or equal to 150,000 and less than or equal to 2,000,000 Da is 18-23 w / w%, the content of components with a molecular weight greater than or equal to 100,000 and less than 150,000 Da is 10-14 w / w%, the content of components with a molecular weight greater than or equal to 50,000 and less than 100,000 Da is 28-32 w / w%, the content of components with a molecular weight greater than or equal to 10,000 and less than 50,000 Da is 30-38 w / w%, and the content of components with a molecular weight less than 10,000 Da is 2-5 w / w%.

3. The collagen according to claim 1 or 2, characterized in that The weight average molecular weight of the collagen is 3000-7000Da, and the content of the component with a molecular weight greater than or equal to 2000 and less than 5000Da in the collagen is 22-27w / w%; Preferably, the weight average molecular weight of the non-fish source gelatin is 80,000-160,000 Da, more preferably 80,000-119,000 Da.

4. A method for preparing collagen, characterized in that: The method comprises: mixing non-fish-derived gelatin with protease for enzymolysis to obtain collagen with a weight average molecular weight of 2500-10000Da, wherein the content of components with a molecular weight greater than or equal to 2000 and less than 5000Da in the collagen is 17-28w / w%; The non-fish source gelatin has the following composition: the content of components with a molecular weight greater than or equal to 150,000 and less than or equal to 2,000,000 Da is 18-31 w / w%, the content of components with a molecular weight greater than or equal to 100,000 and less than 150,000 Da is 10-22 w / w%, the content of components with a molecular weight greater than or equal to 50,000 and less than 100,000 Da is 28-33 w / w%, the content of components with a molecular weight greater than or equal to 10,000 and less than 50,000 Da is 13-38 w / w%, and the content of components with a molecular weight less than 10,000 Da is 2-5 w / w%; The protease is selected from at least one of neutral protease, trypsin, papain and bromelain.

5. The method according to claim 4, characterized in that The non-fish source gelatin has the following components: the content of the component with a molecular weight greater than or equal to 150,000 and less than or equal to 2,000,000 Da is 18-23 w / w%, the content of the component with a molecular weight greater than or equal to 100,000 and less than 150,000 Da is 10-14 w / w%, the content of the component with a molecular weight greater than or equal to 50,000 and less than 100,000 Da is 28-32 w / w%, the content of the component with a molecular weight greater than or equal to 10,000 and less than 50,000 Da is 30-38 w / w%, and the content of the component with a molecular weight less than 10,000 Da is 2-5 w / w%; Preferably, the weight average molecular weight of the collagen is 3000-7000Da, and the content of the component with a molecular weight greater than or equal to 2000 and less than 5000Da in the collagen is 22-27w / w%; Preferably, the weight average molecular weight of the non-fish source gelatin is 80,000-160,000 Da, preferably 80,000-119,000 Da.

6. The method according to claim 4 or 5, characterized in that: Relative to 1g of the non-fish-derived gelatin, the amount of enzyme used in the enzymatic hydrolysis is 200-1800U.

7. The method according to claim 4 or 5, characterized in that: The conditions of the enzymatic hydrolysis at least include: a temperature of 45-60°C, a pH of 6.5-7, and a time of 1-3h; Preferably, the method comprises: mixing and dissolving the non-fish-derived gelatin with a solvent and then performing the enzymatic hydrolysis; Preferably, the weight ratio of the non-fish-derived gelatin to the solvent is 1:4-6, and the temperature of the mixed dissolution is 48-63°C; Preferably, the method further comprises: concentrating and drying the enzymatic hydrolysis product.

8. Collagen obtained according to the method according to any one of claims 4 to 7.

9. Use of the collagen according to any one of claims 1 to 3 and 8 in hair products; Preferably, the hair product uses the collagen as the only active ingredient for repairing and / or loosening hair; Preferably, the hair product is selected from at least one of shampoo, hair care and hair shampoo and hair care products, more preferably a hair shampoo and hair care product.

10. A hair product for repairing and / or loosening hair, characterized in that: The hair product contains the collagen according to any one of claims 1 to 3 and 8; Preferably, the hair product uses the collagen as the only active ingredient for repairing and / or loosening hair; Preferably, the content of collagen in the hair product is 0.5-7w / w%, more preferably 1-5w / w%; Preferably, the hair product further contains a surfactant, a moisturizer, a thickener, an acidity regulator, a fragrance, a preservative and water.

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