Supramolecular protein organic silicon compound as well as preparation method and application thereof

Abstract

The invention provides a supramolecular protein organic silicon compound as well as a preparation method and application thereof. The supramolecular protein organic silicon compound is prepared from the following raw materials: a cationic organic silicon compound, hydrolyzed protein and an amino-containing silane compound. The supramolecular protein organic silicon compound is used for hair washing and caring products, has the functions of cleaning, caring and repairing damaged hair and the like, effectively improves the elasticity, glossiness, combability and antistatic property of hair and keeps scalp healthy, and the product stability is good.

Description

Technical Field

[0001] The invention belongs to the technical field of hair care products, and specifically relates to a supramolecular protein organosilicon complex and a preparation method and application thereof. Background Art

[0002] As an important part of the human body, hair has many functions, such as warmth retention, protection, sensory function, health monitoring, and beauty. Daily hair care usually requires the use of shampoo and conditioner. Shampoo can keep the scalp and hair clean and beautiful, while conditioner can improve, restore and maintain hair conditioning.

[0003] However, with the improvement of living standards, people pay more attention to the beauty of their hair, and usually dye or perm their hair. However, dyeing and perming hair use chemical substances, which can cause dry, frizzy, and inelastic hair, affecting the health of the scalp. In addition, the fast pace of life and the pressure from work and life can also cause malnutrition of hair follicles and excessive oil secretion, resulting in dry, split, fragile, dull, and hair loss. Therefore, higher requirements are placed on the functions of hair care products. Although traditional hair care products can clean hair, they can hardly meet consumers' requirements for healthy, shiny, and elastic hair.

[0004] CN105395401A discloses a shampoo with a hair care function. The shampoo comprises the following components by weight: a surfactant, a foaming agent, a conditioning agent, an essence, a preservative, water and a Chinese medicine extract. The Chinese medicine extract is prepared from the following raw materials: mulberry bark, Chinese toon bark, vitex rotundifolia, moutan bark, eclipta prostrata, cnidium monnieri, orientalis, amygdalus dulcis, and scutellaria baicalensis. The shampoo also has a hair care function. However, the elasticity, glossiness and antistatic properties of the shampoo on hair need to be further improved.

[0005] Therefore, it is an urgent problem to be solved in the art to develop a product that can simultaneously clean, care for and repair damaged hair, improve the elasticity, glossiness, combing properties and antistatic properties of hair, and maintain scalp health. Summary of the invention

[0006] In view of the shortcomings of the prior art, the present invention aims to provide a supramolecular protein organosilicon composite and its preparation method and application. The supramolecular protein organosilicon composite is used in hair care products, which can have the functions of cleaning, caring for and repairing damaged hair, improve the elasticity, glossiness, combing properties and antistatic properties of hair, and keep the scalp healthy.

[0007] To achieve this object, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides a supramolecular protein organosilicon composite, wherein raw materials for preparing the supramolecular protein organosilicon composite include cationic organosilicon compounds, hydrolyzed proteins and amino-containing silane compounds.

[0009] In the present invention, the hydrolyzed protein has affinity for damaged hair protein, can assemble with the damaged protein to form a supramolecular structure, repair damaged hair, and improve the gloss and elasticity of the hair; the cationic organic silicon compound and the aminosilane compound have adsorption, softness and antistatic properties; the cationic organic silicon compound, the hydrolyzed protein and the aminosilane compound form a supramolecular structure, which can form an organic silicon protective film on the surface of the hair and penetrate into the inside of the hair to protect the hair, improve the gloss and elasticity of the hair, repair damaged hair, improve the antistatic property and combing performance of the hair, and reduce heat damage and perm and dyeing damage to the hair; in addition, the formation of the supramolecular structure can also enable the originally water-insoluble dialkyl-terminated aminosilicone oil to combine with water, thereby increasing the stability in the hair care product and greatly improving the performance of the hair care product.

[0010] Preferably, the raw materials for preparing the supramolecular protein organosilicon composite include, by weight, 38.5 to 46 parts of cationic organosilicon compounds, for example, 38.5, 39, 39.5, 40, 40.5, 41, 41.5, 42, 42.5, 43, 43.5, 44, 44.5, 45, 5.5, 46, etc.; 3 to 18 parts of hydrolyzed protein, for example, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, etc.; 5 to 1 5 parts of aminosilane compounds can be, for example, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts, 10 parts, 10.5 parts, 11 parts, 11.5 parts, 12 parts, 12.5 parts, 13 parts, 13.5 parts, 14 parts, 14.5 parts, 15 parts, etc.; and 38.6-46 parts of solvents can be, for example, 38.5 parts, 39 parts, 39.5 parts, 40 parts, 40.5 parts, 41 parts, 41.5 parts, 42 parts, 42.5 parts, 43 parts, 43.5 parts, 44 parts, 44.5 parts, 45 parts, 45.5 parts, 46 parts, etc.

[0011] Preferably, the cationic silicone compound includes at least one of N-cyclohexyl-γ-aminopropyl polydimethylsiloxane, quaternary ammonium salt-80, polysilicone quaternary ammonium salt-16, polysilicone quaternary ammonium salt-8 or polysilicone quaternary ammonium salt-18, and more preferably quaternary ammonium salt-80.

[0012] Preferably, the hydrolyzed protein comprises hydrolyzed silk fibroin and / or hydrolyzed vegetable protein.

[0013] Preferably, the relative molecular mass of the hydrolyzed silk fibroin is 1000-12000, for example, 5000-8000; the relative molecular mass of the hydrolyzed plant protein is 1000-5000, for example, 1500-3000.

[0014] Preferably, the hydrolyzed vegetable protein comprises at least one of hydrolyzed soy protein, hydrolyzed wheat protein, hydrolyzed pea protein, hydrolyzed barley protein or hydrolyzed corn protein; more preferably, hydrolyzed wheat protein.

[0015] Preferably, the hydrolyzed protein includes hydrolyzed silk fibroin and hydrolyzed wheat protein, and the mass ratio of the hydrolyzed silk fibroin to the hydrolyzed wheat protein is (10-15):(4-6), wherein the specific values ​​in (10-15) can be, for example, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, etc.; the specific values ​​in (4-6) can be, for example, 4, 4.2, 4.4, 4.6, 4.8, 5, 5.2, 5.4, 5.6, 5.8, 6, etc.

[0016] In the present invention, the hydrolyzed proteins of different molecular weights can be purchased from the market, or prepared by conventional methods, including but not limited to enzymatic hydrolysis, acid hydrolysis or alkaline hydrolysis.

[0017] Preferably, the aminosilane compound includes at least one of dialkyl-terminated aminosilicone oil, amino-terminated aminosilicone oil or bis-aminopropyl polydimethylsiloxane.

[0018] Preferably, the number average molecular weight of the aminosilane compound is 300-8000, for example, 300, 500, 600, 800, 1000, 1200, 1400, 1600, 2000, 3000, 4000, 5000, 6000, 7000, 8000, etc.; more preferably 300-1500.

[0019] In a second aspect, the present invention provides a method for preparing the supramolecular protein organosilicon composite according to the first aspect, the preparation method comprising:

[0020] Under the condition that the pH value of the system is greater than the isoelectric point of the hydrolyzed protein, the cationic organosilicon compound, the hydrolyzed protein and the aminosilane compound are mixed to obtain the supramolecular protein organosilicon complex.

[0021] In the present invention, the cationic organosilicon compound has weak hydrophilicity, and the aminosilane compound is insoluble in water; when the pH value is above the isoelectric point, the protein is hydrolyzed into anionic properties, and through electrostatic adsorption, it combines with the cationic organosilicon compound and the aminosilane compound to form a supramolecular structure.

[0022] Preferably, the mixing temperature is 45-60°C, for example, 45°C, 46°C, 48°C, 50°C, 52°C, 54°C, 56°C, 58°C, 60°C, etc.

[0023] Preferably, the pH value of the system is 5.3-6.6, for example, it can be 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, etc.

[0024] Preferably, the preparation method comprises: premixing the cationic organosilicon compound with the hydrolyzed protein, adjusting the pH value to 5.3-6.6, heating to 45-60° C., adding an aminosilane compound thereto and mixing, to obtain the supramolecular protein organosilicon complex.

[0025] In the present invention, cationic organosilicon compounds and hydrolyzed proteins are pre-assembled at a molecular level at a specific pH value, and then amino-containing silane compounds are added to further perform supramolecular bonding to form a supramolecular protein organosilicon complex with a triple structure.

[0026] In a third aspect, the present invention provides a hair care product, comprising the supramolecular protein organosilicon complex according to the first aspect.

[0027] Preferably, in the hair care product, the mass percentage of the supramolecular protein silicone complex is 1-5%, for example, it can be 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.6%, 2.8%, 3%, 3.2%, 3.4%, 3.6%, 3.8%, 4%, 4.2%, 4.4%, 4.6%, 4.8%, 5% and the like.

[0028] Preferably, the hair care product further comprises, by mass percentage, 1-5% surfactant (for example, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.5%, 2.8%, 3%, 3.2%, 3.5%, 3.8%, 4%, 4.5%, etc.), 0.1-2% D-panthenol (for example, 0.1%, 0.2%, 0.4%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, etc.) and 73-89% water (for example, 73%, 74%, 75%, 76%, 77%, 78%, 80%, 82%, 84%, 86%, 88%, etc.).

[0029] The numerical range described in the present invention not only includes the point values ​​listed above, but also includes any point values ​​between the above numerical ranges that are not listed. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] The supramolecular protein organosilicon composite provided by the present invention is compounded with a cationic organosilicon compound, a hydrolyzed protein and an aminosilane compound, and the three form a supramolecular structure, so that the supramolecular protein organosilicon composite is used in hair care products, and can have the functions of cleaning, caring for and repairing damaged hair, and can effectively improve the elasticity, glossiness, combing properties and antistatic properties of the hair, keep the scalp healthy, and at the same time the product has good stability. DETAILED DESCRIPTION

[0032] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0033] Unless otherwise specified, the materials used in the present invention are as follows:

[0034] Quaternary ammonium salt-80: SiCare 2496F3 from Hunan Siluoke Silicone Co., Ltd.;

[0035] Dialkyl-terminated amino silicone oil: Hunan Siluoke Organic Silicone Co., Ltd. 2416;

[0036] Hydrolyzed wheat protein: Shenzhen Ruijit Biotechnology Co., Ltd., CAS No. 70084-87-6.

[0037] Hydrolyzed silk fibroin: Shenzhen Ruijit Biotechnology Co., Ltd., CAS No. 100085-35-1.

[0038] Example 1

[0039] The present embodiment provides a supramolecular protein organosilicon composite, wherein raw materials for preparing the supramolecular protein organosilicon composite include 40 parts of quaternary ammonium salt-80, 10 parts of hydrolyzed silk fibroin, 10 parts of dialkyl-terminated amino silicone oil and 40 parts of solvent 1,3-butanediol.

[0040] This embodiment provides a method for preparing a supramolecular protein organosilicon composite, which specifically comprises the following steps:

[0041] Quaternary ammonium salt-80, hydrolyzed silk fibroin and solvent are premixed, the pH value is adjusted to 5.5 with citric acid, the temperature is raised to 50° C., dialkyl-terminated amino silicone oil is added thereto and mixed for 1 hour to obtain the supramolecular protein organosilicon composite.

[0042] Example 2

[0043] The present embodiment provides a supramolecular protein organosilicon composite, wherein raw materials for preparing the supramolecular protein organosilicon composite include 39 parts of quaternary ammonium salt-80, 15 parts of hydrolyzed wheat protein, 13 parts of dialkyl-terminated amino silicone oil and 33 parts of solvent 1,3-butanediol.

[0044] This embodiment provides a method for preparing a supramolecular protein organosilicon composite, and the specific steps are the same as those in Embodiment 1.

[0045] Example 3

[0046] The present embodiment provides a supramolecular protein organosilicon composite, wherein raw materials for preparing the supramolecular protein organosilicon composite include 45 parts of quaternary ammonium salt-80, 6 parts of hydrolyzed silk fibroin, 6 parts of dialkyl-terminated amino silicone oil and 43 parts of solvent 1,3-butanediol.

[0047] This embodiment provides a method for preparing a supramolecular protein organosilicon composite, and the specific steps are the same as those in Embodiment 1.

[0048] Example 4

[0049] This embodiment provides a supramolecular protein silicone composite, which differs from Embodiment 1 only in that the raw materials include 57 parts of quaternary ammonium salt-80, 2 parts of hydrolyzed silk fibroin and 1 part of dialkyl-terminated amino silicone oil, and the types of raw materials and the preparation method are the same as those in Embodiment 1.

[0050] Example 5

[0051] This embodiment provides a supramolecular protein silicone composite, which differs from Embodiment 1 only in that the raw materials include 15 parts of quaternary ammonium salt-80, 25 parts of hydrolyzed silk fibroin and 20 parts of dialkyl-terminated amino silicone oil, and the types of raw materials and the preparation method are the same as those in Embodiment 1.

[0052] Example 6

[0053] This embodiment provides a supramolecular protein organosilicon composite, which differs from Embodiment 1 only in that quaternary ammonium salt-80 is replaced by polysiloxane quaternary ammonium salt-16 of equal mass, and other raw materials, dosages and preparation methods are the same as those in Embodiment 1.

[0054] Example 7

[0055] This embodiment provides a supramolecular protein silicone composite, which differs from Embodiment 1 only in that the total mass of the hydrolyzed protein remains unchanged, and includes hydrolyzed silk fibroin and hydrolyzed wheat protein in a mass ratio of 14:5, and the types of raw materials and preparation methods are the same as those in Embodiment 1.

[0056] Example 8

[0057] This embodiment provides a supramolecular protein silicone composite, which differs from Embodiment 1 only in that the total mass of the hydrolyzed protein remains unchanged, and includes hydrolyzed silk fibroin and hydrolyzed wheat protein in a mass ratio of 10:4, and the types of raw materials and preparation methods are the same as those in Embodiment 1.

[0058] Example 9

[0059] This embodiment provides a supramolecular protein organosilicon composite, which differs from Embodiment 7 only in that the total mass of the hydrolyzed protein remains unchanged, including hydrolyzed silk fibroin and hydrolyzed wheat protein in a mass ratio of 8:8, and other raw materials, amounts and preparation methods are the same as those in Embodiment 7.

[0060] Example 10

[0061] This embodiment provides a supramolecular protein silicone composite, which differs from Embodiment 7 only in that the total mass of the hydrolyzed protein remains unchanged, and includes hydrolyzed silk fibroin and hydrolyzed wheat protein in a mass ratio of 16:3, and other raw materials, amounts and preparation methods are the same as those in Embodiment 7.

[0062] Comparative Example 1

[0063] This comparative example provides a supramolecular protein organosilicon composite, which differs from Example 1 only in that quaternary ammonium salt-80 is replaced by polyquaternary ammonium salt-10 of equal mass, and other raw materials, dosages and preparation methods are the same as those in Example 1.

[0064] Comparative Example 2

[0065] This comparative example provides a protein-organic silicon composite, which is different from Example 1 only in that the preparation method does not adjust the pH value to 5.5, and other raw materials, amounts and preparation methods are the same as those in Example 1.

[0066] Comparative Example 3

[0067] This comparative example provides a supramolecular protein organosilicon composite, which is different from Example 1 only in that, among the raw materials for preparing the supramolecular protein organosilicon composite, the total mass of dialkyl-terminated amino silicone oil, quaternary ammonium salt-80 and hydrolyzed protein remains unchanged, the mass ratio of quaternary ammonium salt-80 and hydrolyzed protein remains unchanged, there is no dialkyl-terminated amino silicone oil, and other raw materials, amounts and preparation methods are the same as those in Example 1.

[0068] Comparative Example 4

[0069] This comparative example provides a supramolecular protein organosilicon composite, which is different from Example 1 only in that, among the raw materials for preparing the supramolecular protein organosilicon composite, the total mass of dialkyl-terminated amino silicone oil, quaternary ammonium salt-80 and hydrolyzed protein remains unchanged, the mass ratio of dialkyl-terminated amino silicone oil and hydrolyzed protein remains unchanged, there is no quaternary ammonium salt-80, and other raw materials, dosages and preparation methods are the same as those in Example 1.

[0070] Application Examples

[0071] This application example provides a hair conditioner, which includes, by mass percentage, 2.5% supramolecular protein organosilicon complex, 1% surfactant (French Seppic 305 emulsifier), 0.5% D-panthenol, and the balance is water; the supramolecular protein organosilicon complex is the supramolecular protein organosilicon complex or protein organosilicon complex provided in Examples 1 to 10 and Comparative Examples 1 to 4.

[0072] Performance Testing

[0073] (1) Hair tensile force: Natural black hair (length 30 cm, weight 10 g) was treated with the hair conditioner of the present invention in an amount of 10 g, and then the treated black hair was hot-ironed at 140° C. for 10 min, and the breaking force of the hair was tested using a hair tensile force tester;

[0074] (2) Glossiness: Natural black hair (length 30 cm, weight 10 g) was treated with the hair conditioner of the present invention in an amount of 10 g, then rinsed, blow-dried, combed with a comb, and arranged into flat plates with a width of 2 cm. The flat plates were fixed in a standard light source color matching light box, and the glossiness of the hair was evaluated by trained assessors according to a 5-point scoring rule, with 1 point indicating the worst glossiness and 5 points indicating the best glossiness;

[0075] (3) Combability: Natural black hair (length 30 cm, weight 10 g) was moistened with water and then treated with the hair conditioner of the present invention in an amount of 10 g. The hair was then rinsed and placed at 45°C.

[0076] The hair was dried in an oven, and then the hair temperature was lowered to room temperature. The combing force was tested using a hair combing tester, and the change in combing force before and after hair care was calculated, recorded as ΔF; ΔF = combing force before hair care - combing force after hair care.

[0077] The specific test results are shown in Table 1.

[0078] Table 1

[0079]

[0080]

[0081] As can be seen from Table 1, the supramolecular protein organosilicon composite provided by the present invention is compounded with a cationic organosilicon compound, a hydrolyzed protein and an aminosilane compound, and the three form a supramolecular structure, so that the supramolecular protein organosilicon composite is used in hair care products, which can have the functions of cleaning, caring for and repairing damaged hair, and can effectively improve the elasticity, glossiness, combing properties and antistatic properties of the hair, keep the scalp healthy, and at the same time the product has good stability.

[0082] The specific embodiments described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A supramolecular protein organosilicon composite, characterized in that: The raw materials for preparing the supramolecular protein organosilicon complex include cationic organosilicon compounds, hydrolyzed proteins and amino-containing silane compounds.

2. The supramolecular protein organosilicon composite according to claim 1, characterized in that: In parts by weight, the raw materials for preparing the supramolecular protein organosilicon complex include 38.5-46 parts of cationic organosilicon compounds, 3-18 parts of hydrolyzed protein, 5-15 parts of aminosilane compounds and 38.6-46 parts of solvents.

3. The supramolecular protein organosilicon composite according to claim 1 or 2, characterized in that: The cationic silicone compound includes at least one of N-cyclohexyl-γ-aminopropyl polydimethylsiloxane, quaternary ammonium salt-80, polysilicone quaternary ammonium salt-16, polysilicone quaternary ammonium salt-8 or polysilicone quaternary ammonium salt-18; more preferably, quaternary ammonium salt-80.

4. The supramolecular protein organosilicon composite according to any one of claims 1 to 3, characterized in that: The hydrolyzed protein includes hydrolyzed silk fibroin and / or hydrolyzed vegetable protein; Preferably, the relative molecular mass of the hydrolyzed silk fibroin is 1000-12000; the relative molecular mass of the hydrolyzed plant protein is 1000-5000.

5. The supramolecular protein organosilicon composite according to claim 4, characterized in that: The hydrolyzed vegetable protein comprises at least one of hydrolyzed soy protein, hydrolyzed wheat protein, hydrolyzed pea protein, hydrolyzed barley protein or hydrolyzed corn protein; preferably, hydrolyzed wheat protein.

6. The supramolecular protein organosilicon composite according to any one of claims 1 to 5, characterized in that: The hydrolyzed protein includes hydrolyzed silk fibroin and hydrolyzed wheat protein, and the mass ratio of the hydrolyzed silk fibroin to the hydrolyzed wheat protein is (10-15):(4-6).

7. The supramolecular protein organosilicon composite according to any one of claims 1 to 6, characterized in that: The aminosilane compound includes at least one of dialkyl-terminated aminosilicone oil, amino-terminated aminosilicone oil or bis-aminopropyl polydimethylsiloxane; Preferably, the number average molecular weight of the amino-containing silane compound is 300-8000, more preferably 300-1500.

8. A method for preparing a supramolecular protein organosilicon composite according to any one of claims 1 to 7, characterized in that: The preparation method comprises: Under the condition that the pH value of the system is greater than the isoelectric point of the hydrolyzed protein, the cationic organosilicon compound, the hydrolyzed protein and the aminosilane compound are mixed to obtain the supramolecular protein organosilicon complex.

9. The preparation method according to claim 8, characterized in that: The mixing temperature is 45-60°C; Preferably, the pH value of the system is 5.3 to 6.6; Preferably, the preparation method comprises: premixing the cationic organosilicon compound with the hydrolyzed protein, adjusting the pH value to 5.3-6.6, heating to 45-60° C., adding an aminosilane compound thereto and mixing, to obtain the supramolecular protein organosilicon complex.

10. A hair care product, characterized in that: The hair care product comprises the supramolecular protein organosilicon complex according to any one of claims 1 to 7; Preferably, in the hair care product, the mass percentage of the supramolecular protein organosilicon complex is 1 to 5%; Preferably, the hair care product further comprises, by weight percentage, 1-5% surfactant, 0.1-2% D-panthenol and 73-89% water.

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