Glycoprotein and polyquaternium-51 synergistic color-fixing and repairing silicon-free cleaning composition and preparation method thereof

Abstract

The invention discloses a silicon-free washing and care composition with glycoprotein and polyquaternium-51 synergistic color fixation and repair and a preparation method of the silicon-free washing and care composition with glycoprotein and polyquaternium-51 synergistic color fixation and repair. The composition is prepared from the following components in parts by weight: 1 to 5 parts of glycoprotein grafted and modified by epoxy butyl sulfonate, 0.5 to 3 parts of polyquaternium-51, 0.2 to 2 parts of 2, 5-dihydroxy terephthalamide, glycerol, sodium lauroyl sarcosinate, cocamidopropyl betaine, citric acid, a preservative, essence and deionized water. The glycoprotein grafted and modified by the epoxy butyl sulfonate is prepared by reacting glycoprotein, the epoxy butyl sulfonate, sodium bicarbonate, ethanol and deionized water. Through the synergistic effect of the modified glycoprotein and the polyquaternium-51, the color fixing performance and the repairing effect of hair are effectively improved, the hair surface friction coefficient is reduced, meanwhile, the system is kept stable in long-term storage, the color fixing agent is remarkably superior to a contrast sample which is not modified or lacks key components, and the color fixing agent has a good application prospect.

Description

Technical Field

[0001] This invention relates to the field of daily chemical industry, specifically to a silicone-free washing and care composition for synergistic color fixing and repair by glycoprotein and polyquaternium-51, and its preparation method. Background Technology

[0002] In existing hair care compositions, silicone oils are widely used as smoothing and repairing ingredients. These materials can form a hydrophobic film on the hair surface, improving feel and shine in the short term. However, silicone oils have the following drawbacks: First, they are difficult to rinse thoroughly, easily accumulating on the hair and scalp, leading to increased burden on the scalp barrier and even clogging of hair follicles; second, the density of the silicone oil film affects hair breathability, and long-term use is detrimental to scalp health; third, when applied after hair dyeing, silicone oil's role is mainly focused on surface lubrication, offering limited help in stabilizing the binding of pigment molecules to hair fibers, thus the problem of color fading after dyeing remains prominent. To address the issues of color fixation and repair in hair dyeing, existing technologies attempt to introduce proteins, polysaccharides, or cationic polymers. For example, whey protein hydrolysate, soy protein, and gelatin peptides, due to their amino acid residues, can bind to keratin on the hair surface to some extent, but their water solubility and structural stability are insufficient, easily lost during rinsing, resulting in limited repair effects. Glycoproteins, as natural macromolecules, possess both hydrophilicity and a certain degree of biocompatibility. However, the loose structure of natural glycoproteins and the lack of sufficient hydrophobic interaction sites make it difficult to achieve a strong binding to dye molecules.

[0003] Therefore, existing hair care compositions still have significant shortcomings in terms of silicone-free alternatives, hair color fixing effects, and multi-component synergistic repair. There is an urgent need to develop a synergistic system based on modified glycoproteins, polyquaternium-51, and novel small molecules to improve color fixing, repair, and smoothness performance. Summary of the Invention

[0004] To overcome the shortcomings of the aforementioned background technology, the present invention aims to provide a silicone-free shampoo and conditioner composition and its preparation method that synergistically fixes and repairs hair color with glycoprotein and polyquaternium-51. The present invention uses epoxy butyl sulfonate-grafted modified glycoprotein, polyquaternium-51, and 2,5-dihydroxyterephthalamide, an organic small molecule not previously used in this field, as the main components, combined with glycerin, surfactants, acidity regulators, preservatives, and fragrance additives to form a silicone-free system. Through this combination design, the synergistic effect of epoxy butyl sulfonate-grafted modified glycoprotein and polyquaternium-51 is achieved, while introducing novel small molecules to enhance the system's stability and adhesion, thereby constructing a shampoo and conditioner formula that combines color fixing and repair effects. The formula is silicone-free and environmentally friendly, reducing residue; improving hair color fixing effect; enhancing hair repair properties; and significantly improving smoothness.

[0005] The objective of this invention can be achieved through the following technical solutions:

[0006] A silicone-free shampoo and conditioner composition for synergistic color-fixing and repair with glycoprotein and polyquaternium-51, comprising the following raw materials in parts by weight: 1-5 parts of glycoprotein grafted with epoxy butyl sulfonate; 0.5-3 parts of polyquaternium-51; 0.2-2 parts of 2,5-dihydroxyterephthalamide; 2-5 parts of glycerin; 5-15 parts of sodium lauroyl sarcosinate; 2-8 parts of cocamidopropyl betaine; 0.05-0.5 parts of citric acid; 0.1-0.5 parts of preservative; 0.1-0.3 parts of fragrance; and 60-85 parts of deionized water.

[0007] Optionally, the glycoprotein grafted with epoxybutyl sulfonate comprises the following raw materials in parts by weight: 10-30 parts glycoprotein; 2-10 parts epoxybutyl sulfonate; 0.5-2 parts sodium bicarbonate; 20-50 parts ethanol; and 50-100 parts deionized water.

[0008] Optionally, the method for preparing glycoproteins modified by epoxy butyl sulfonate grafting includes the following steps:

[0009] (1) Add the glycoprotein to deionized water and dissolve it under stirring to form a glycoprotein solution;

[0010] (2) Add an alkaline regulator to the glycoprotein solution to adjust the pH to alkaline, and add ethanol to obtain a stable premix;

[0011] (3) Slowly add the epoxy butyl sulfonate solution to the premixed solution and carry out the grafting reaction under stirring to obtain the modified reaction solution;

[0012] (4) The modified reaction solution was dialyzed to remove unreacted monomers and small molecule impurities. After concentration, it was spray-dried to obtain epoxy butyl sulfonate grafted modified glycoprotein solid.

[0013] Optionally, the concentration of the glycoprotein solution in step (1) is 0.5% to 2.0%; the pH range of step (2) is 8.2 to 8.8, and the amount of ethanol added is 30% to 60% of the volume of the glycoprotein solution; the drop time of the epoxy butyl sulfonate solution in step (3) is 30 to 60 min, the reaction temperature is 25 to 35 °C, and the reaction time is 2 to 4 h; the dialysis time in step (4) is 24 to 48 h, and the molecular weight cutoff of the dialysis bag is 3.5 to 10 kDa.

[0014] Optionally, 2,5-dihydroxyterephthalamide is a terephthalamide derivative with a hydroxyl group attached to the 2 and 5 positions of the benzene ring.

[0015] Alternatively, the preservative is a mixture of phenoxyethanol and ethylhexylglycerin in a mass ratio of 3:1.

[0016] Optionally, a method for preparing a silicone-free shampoo and conditioner composition for synergistic color-fixing and repair by glycoprotein and polyquaternium-51 includes the following steps:

[0017] S1, Dissolve the glycoprotein grafted with epoxy butyl sulfonate in deionized water to obtain a glycoprotein solution;

[0018] S2, add sodium lauroyl sarcosinate and cocamidopropyl betaine to the glycoprotein solution in sequence and mix well;

[0019] S3, add polyquaternium-51 and 2,5-dihydroxyterephthalamide, stir until homogeneous to obtain a mixture;

[0020] S4. After cooling the mixture, add glycerin, preservatives, fragrance and citric acid, adjust the pH to obtain the target shampoo and conditioner composition.

[0021] Optionally, the reaction conditions for step S1 are: glycoprotein solution concentration of 0.5% to 2.0%; the reaction conditions for step S2 are: stirring rate of 200 to 400 rpm; the reaction conditions for step S3 are: stirring at 40°C for 30 to 60 min; and the reaction conditions for step S4 are: final pH of 5.0 to 5.5.

[0022] The beneficial effects of this invention are:

[0023] This invention utilizes epoxy butyl sulfonate grafted modified glycoprotein, simultaneously introducing sulfonate groups and covalent binding sites formed by epoxy ring opening onto its molecules. This allows it to more firmly adsorb onto the keratin structure on the hair surface, reducing loss during washing and thus significantly improving the stability of pigment retention after dyeing. Simultaneously, it introduces 2,5-dihydroxyterephthalamide, a small molecule not previously used in hair care, which forms a hydrogen-bonded cross-linking network with the modified glycoprotein and polyquaternium-51 on the hair surface. This further enhances the synergistic effect between the components, resulting in excellent performance in colorfastness and repair of damaged hair cuticles. Attached Figure Description

[0024] The invention will now be further described with reference to the accompanying drawings.

[0025] Figure 1 Infrared spectra of glycoproteins modified by epoxy butyl sulfonate grafting and glycoproteins;

[0026] Figure 2 A bar chart comparing the color-fixing performance of samples with different ratios;

[0027] Figure 3 A bar chart comparing the tensile strength improvement rate of samples with different ratios;

[0028] Figure 4A bar chart comparing the elongation at break recovery rates of samples with different ratios;

[0029] Figure 5 A bar chart comparing the friction coefficients of samples with different ratios. Detailed Implementation

[0030] The present invention will be further described below with reference to specific embodiments. However, the present invention is not limited to the following embodiments. Equivalent adjustments made without departing from the spirit and essence of the present invention should also be considered to fall within the protection scope of the present invention.

[0031] Example 1

[0032] The purpose of this embodiment is to verify the color-fixing performance and repairing effect of the prepared shampoo and conditioner composition when each component is taken at the upper limit of the defined range.

[0033] S1. Add 10 parts of glycoprotein to 50 parts of deionized water and dissolve it under stirring at 500 rpm to obtain a glycoprotein solution; add 2 parts of sodium bicarbonate to adjust the pH of the solution to 8.5, and then add 50 parts of ethanol to obtain a homogeneous premix.

[0034] S2, 10 parts of epoxy butyl sulfonate were dissolved in 20 parts of ethanol to prepare a solution. The solution was added dropwise to the premixed solution at a rate of 0.2 mL per minute over 60 minutes at 30°C. The reaction was continued with stirring for 4 hours to obtain an epoxy butyl sulfonate-grafted modified glycoprotein solution. The solution was placed in a dialysis bag with a molecular weight cutoff of 10 kDa and dialyzed in deionized water for 48 hours, with the water changed every 6 hours. The solution was then concentrated and spray-dried to obtain 5 parts of epoxy butyl sulfonate-grafted modified glycoprotein.

[0035] S3, take 5 parts of epoxy butyl sulfonate grafted modified glycoprotein, add 85 parts of deionized water, dissolve at a stirring speed of 300 rpm, then add 15 parts of sodium lauroyl sarcosinate, 8 parts of cocamidopropyl betaine, 3 parts of polyquaternium-513 salt and 2 parts of 2,5-dihydroxyterephthalamide in sequence, stir for 30 minutes and cool to 25°C, then add 5 parts of glycerin and 0.5 parts of preservative, wherein the preservative is prepared by phenoxyethanol and ethylhexylglycerin in a mass ratio of 3:1, add 0.3 parts of fragrance and 0.5 parts of citric acid, adjust the pH to 5.5, and the final shampoo and conditioner composition is obtained.

[0036] Example 2

[0037] The purpose of this embodiment is to verify the overall balance of color-fixing and repairing properties of the prepared shampoo and conditioner composition when each component takes the middle value of a limited range.

[0038] S1. Add 20 parts of glycoprotein to 75 parts of deionized water and dissolve it under stirring at 500 rpm to obtain a glycoprotein solution; add 1 part of sodium bicarbonate to adjust the pH of the solution to 8.4, and then add 35 parts of ethanol to obtain a homogeneous premix.

[0039] S2, dissolve 6 parts of epoxy butyl sulfonate in 15 parts of ethanol to prepare a solution. Add the solution dropwise to the premixed solution at a rate of 0.15 mL per minute over 45 minutes at 28°C, and continue stirring for 3 hours to obtain an epoxy butyl sulfonate-grafted modified glycoprotein solution. Place this solution in a dialysis bag with a molecular weight cutoff of 6 kDa and dialyze it in deionized water for 36 hours, changing the water every 6 hours. Then concentrate and spray dry to obtain 3 parts of epoxy butyl sulfonate-grafted modified glycoprotein. According to... Figure 1 The infrared spectroscopy results show that the N–H and O–H stretching vibration peaks at 3400 cm⁻¹ are still prominent in the glycoprotein. However, in the glycoprotein grafted with epoxy butyl sulfonate, a new S=O stretching vibration peak at 1050 cm⁻¹ and an S–O stretching vibration peak at 830 cm⁻¹ are added. At the same time, characteristic peaks of C–N and O=S=O appear near 1230 cm⁻¹. These features indicate that the sulfonate group was successfully introduced into the glycoprotein molecular structure, and the intermolecular hydrogen bonding was enhanced, proving that the modification process was effectively completed and providing a structural basis for improving its color-fixing and repair properties.

[0040] S3, take 3 parts of epoxy butyl sulfonate grafted modified glycoprotein, add 72 parts of deionized water, dissolve at a stirring speed of 300 rpm, then add 10 parts of sodium lauroyl sarcosinate, 5 parts of cocamidopropyl betaine, 1.5 parts of polyquaternium-511, and 1 part of 2,5-dihydroxyterephthalamide, stir for 30 minutes and cool to 25°C, then add 3.5 parts of glycerin and 0.3 parts of preservative, wherein the preservative is prepared by mixing phenoxyethanol and ethylhexylglycerin in a mass ratio of 3:1, add 0.2 parts of fragrance and 0.25 parts of citric acid, and adjust the pH to 5.2 to obtain the final shampoo and conditioner composition.

[0041] Example 3

[0042] The purpose of this embodiment is to verify the color-fixing performance and repairing effect of the prepared shampoo and conditioner composition when each component is taken at the lower limit of a defined range.

[0043] S1. Add 10 parts of glycoprotein to 100 parts of deionized water and dissolve it under a stirring speed of 500 rpm to obtain a glycoprotein solution; add 0.5 parts of sodium bicarbonate to adjust the pH of the solution to 8.2, and then add 20 parts of ethanol to obtain a homogeneous premix.

[0044] S2, dissolve 2 parts of epoxy butyl sulfonate in 10 parts of ethanol to prepare a solution, and add it dropwise to the premixed solution at a rate of 0.1 mL per minute over 30 minutes at 25°C. Continue stirring and react for 2 hours to obtain an epoxy butyl sulfonate-grafted modified glycoprotein solution. Place the solution into a dialysis bag with a molecular weight cutoff of 3.5 kDa, dialyze it in deionized water for 24 hours, changing the water every 4 hours, then concentrate and spray dry to obtain 1 part of epoxy butyl sulfonate-grafted modified glycoprotein.

[0045] S3, take 1 part of epoxy butyl sulfonate grafted modified glycoprotein, add 60 parts of deionized water, dissolve at a stirring speed of 300 rpm, then add 5 parts of sodium lauroyl sarcosinate, 2 parts of cocamidopropyl betaine, 0.5 parts of polyquaternium-51 and 0.2 parts of 2,5-dihydroxyterephthalamide, stir for 30 minutes and cool to 25°C, then add 2 parts of glycerin and 0.1 parts of preservative, wherein the preservative is prepared by mixing phenoxyethanol and ethylhexylglycerin in a mass ratio of 3:1, add 0.1 parts of fragrance and 0.05 parts of citric acid, adjust the pH to 5.0, and the final shampoo and conditioner composition is obtained.

[0046] Comparative Example 1

[0047] The purpose of this comparative example is to verify the effect of unmodified glycoprotein on formulation performance when no epoxide butyl sulfonate grafting modification is performed.

[0048] S1. Add 20 parts of glycoprotein to 75 parts of deionized water and dissolve it under stirring at 500 rpm to obtain a glycoprotein solution; add 1 part of sodium bicarbonate to adjust the pH of the solution to 8.4, and then add 35 parts of ethanol to obtain a homogeneous premix.

[0049] S2, without adding epoxybutyl sulfonate, the solution was stirred at 28°C for 3 hours to obtain an unmodified glycoprotein solution; the solution was placed in a dialysis bag with a molecular weight cutoff of 6 kDa, dialyzed in deionized water for 36 hours, with the water changed every 6 hours, then concentrated and spray-dried to obtain 3 portions of unmodified glycoprotein.

[0050] S3, take 3 parts of unmodified glycoprotein, add 72 parts of deionized water, dissolve at a stirring speed of 300 rpm, then add 10 parts of sodium lauroyl sarcosinate, 5 parts of cocamidopropyl betaine, 1.5 parts of polyquaternium-511, and 1 part of 2,5-dihydroxyterephthalamide in sequence, stir for 30 minutes and cool to 25°C, then add 3.5 parts of glycerol and 0.3 parts of preservative, wherein the preservative is prepared by mixing phenoxyethanol and ethylhexylglycerol in a mass ratio of 3:1, add 0.2 parts of fragrance and 0.25 parts of citric acid, and adjust the pH to 5.2 to obtain the comparative example 1 sample.

[0051] Comparative Example 2

[0052] The purpose of this comparative example is to verify the changes in formulation performance without the addition of 2,5-dihydroxyterephthalamide.

[0053] S1. Add 20 parts of glycoprotein to 75 parts of deionized water and dissolve it under stirring at 500 rpm to obtain a glycoprotein solution; add 1 part of sodium bicarbonate to adjust the pH of the solution to 8.4, and then add 35 parts of ethanol to obtain a homogeneous premix.

[0054] S2, dissolve 6 parts of epoxy butyl sulfonate in 15 parts of ethanol to prepare a solution, and add it dropwise to the premixed solution at a rate of 0.15 mL per minute over 45 minutes at 28°C. Continue stirring and react for 3 hours to obtain an epoxy butyl sulfonate-grafted modified glycoprotein solution. Place the solution into a dialysis bag with a molecular weight cutoff of 6 kDa, dialyze it in deionized water for 36 hours, changing the water every 6 hours, then concentrate and spray dry to obtain 3 parts of epoxy butyl sulfonate-grafted modified glycoprotein.

[0055] S3, take 3 parts of epoxy butyl sulfonate grafted modified glycoprotein, add 73 parts of deionized water, dissolve at a stirring speed of 300 rpm, then add 10 parts of sodium lauroyl sarcosinate, 5 parts of cocamidopropyl betaine and 11.5 parts of polyquaternium-5, without adding 2,5-dihydroxyterephthalamide, stir for 30 minutes and cool to 25℃, then add 3.5 parts of glycerol and 0.3 parts of preservative, wherein the preservative is prepared by phenoxyethanol and ethylhexylglycerol in a mass ratio of 3:1, add 0.2 parts of fragrance and 0.25 parts of citric acid, adjust the pH to 5.2, and obtain the comparative example 2 sample.

[0056] Performance testing

[0057] 1. Colorfastness test

[0058] Samples obtained from Examples 1-3 and Comparative Examples 1-2 were used to wash and condition standard human hair strands that had undergone hair dyeing treatment. Each sample was washed 10 times in a 40°C water bath for 3 minutes each time, rinsed thoroughly with deionized water, and air-dried. The L*a*b* color difference values ​​were measured before and after washing using a spectrophotometer, and the color difference ΔE was calculated. The smaller the ΔE, the better the color fixation performance.

[0059] 2. Repair performance test

[0060] Damaged human hair strands that had undergone chemical bleaching were selected and treated with samples obtained in Examples 1-3 and Comparative Examples 1-2, respectively. Tensile strength and elongation at break were measured using a universal testing machine at 20°C. Repair performance was evaluated by the increase in strength and recovery of elongation at break after treatment relative to untreated damaged hair strands.

[0061] 3. Surface smoothness test

[0062] Human hair strands treated with the samples obtained in Examples 1-3 and Comparative Examples 1-2 were used to measure the friction force on the hair surface using a coefficient of friction tester. A standard probe was slid along the hair surface at a speed of 2 cm / min under a fixed load, and the coefficient of friction was recorded. A lower coefficient of friction indicates better smoothness.

[0063] 4. Storage stability test

[0064] The samples obtained in Examples 1-3 and Comparative Examples 1-2 were aliquoted into sealed containers and stored at 4°C and 40°C, respectively, for 30 days. Samples were taken every 5 days to check for stratification or flocculation, and the pH value and viscosity change rate were measured. Samples without stratification or precipitation, with a pH drift of less than 0.3 and a viscosity change rate of less than 10%, were considered stable.

[0065] Table 1 Performance Test Results

[0066] Sample number Color fixation performance ΔE Tensile strength improvement rate (%) Recovery rate of elongation at break (%) coefficient of friction Storage stability (30 days) Example 1 2.5 28 35 0.38 Stable, pH drift 0.2, viscosity change rate -4%. Example 2 1.8 35 42 0.32 Stable, pH drift 0.1, viscosity change rate -3%. Example 3 2.9 25 30 0.40 Stable, pH drift 0.2, viscosity change rate -5%. Comparative Example 1 5.6 12 15 0.55 Unstable, exhibiting slight stratification, pH shift of 0.6, and viscosity change rate of -12%. Comparative Example 2 6.1 10 12 0.58 Unstable, exhibiting flocculation, pH drift of 0.7, and viscosity change rate of -15%.

[0067] As shown in Table 1, in the comprehensive performance comparison, Examples 1 to 3 all showed significantly better performance than Comparative Examples 1 and 2, indicating that the synergistic design of the epoxy butyl sulfonate-grafted modified glycoprotein and 2,5-dihydroxyterephthalamide used in this invention has significant advantages in terms of color fixation, repair, smoothness, and stability. Among them, Example 2 performed the best in all indicators, becoming the optimal solution and fully demonstrating the contribution of the innovative components.

[0068] Figure 2 Regarding color-fixing performance, the ΔE values ​​of the examples were all less than 3, while those of the comparative examples were all greater than 5, showing a significant difference. In particular, the ΔE value of Example 2 was only 1.8, indicating that it had the best color retention effect after dyeing and could significantly reduce fading during the washing process. In contrast, the ΔE values ​​of Comparative Example 1 and Comparative Example 2 were 5.6 and 6.1, respectively, indicating that the color-fixing effect was significantly insufficient when the glycoprotein was not modified or when 2,5-dihydroxyterephthalamide was lacking.

[0069] Figure 3 as well as Figure 4 The results show that in terms of repair performance, Example 2 exhibits a 35% increase in tensile strength and a 42% recovery rate in elongation at break, both significantly higher than the 28% and 35% of Example 1 and the 25% and 30% of Example 3, while the comparative examples show only a 10% to 15% increase and recovery rate. This result demonstrates that the two-component synergistic system employed in this invention can effectively repair damaged keratin structures in hair, improving hair toughness and flexibility.

[0070] like Figure 5As shown, in terms of surface smoothness, the coefficients of friction for the sample examples were all below 0.40, with Example 2 having the lowest coefficient at 0.32, exhibiting the best hair smoothness. The coefficients of friction for Comparative Examples 1 and 2 were 0.55 and 0.58, respectively, which were significantly higher, indicating that the hair surface of the comparative examples was still rough and lacked sufficient smoothness.

[0071] Regarding storage stability, Examples 1 to 3 maintained a uniform appearance without stratification or flocculation under 30-day storage conditions at 4°C and 40°C, with pH drift controlled within 0.2 and viscosity change rate not exceeding 5%, demonstrating high stability. In contrast, Comparative Example 1 showed slight stratification within 30 days, with a pH drift of 0.6 and a viscosity change rate of -12%; Comparative Example 2 showed significant flocculation, with a pH drift of 0.7 and a viscosity change rate of -15%, indicating significantly insufficient stability.

[0072] In summary, as shown in Table 1, the embodiments, especially Embodiment 2, performed best in all four aspects of color fixation, repair, smoothing, and storage stability, far superior to the comparative examples, thus verifying the significant advantages and inventiveness of the innovative technical solution of this invention.

Claims

1. A silicon-free wash-and-condition composition for the simultaneous color care repair of glycoproteins and polyquaternium-51, characterized in that it comprises: The raw materials include the following components by weight: 1-5 parts of glycoprotein grafted with epoxy butyl sulfonate; 10.5-3 parts of polyquaternium-5; 0.2-2 parts of 2,5-dihydroxyterephthalamide; 2-5 parts of glycerin; 5-15 parts of sodium lauroylmethylamino acetate; 2-8 parts of cocamidopropyl betaine; 0.05-0.5 parts of citric acid; 0.1-0.5 parts of preservative; 0.1-0.3 parts of essence; and 60-85 parts of deionized water.

2. A silicon-free wash-and-condition composition for the synergistic color care of a glycoprotein with Polyquatemium-51 according to claim 1, characterized in that, The glycoprotein grafted with epoxy butyl sulfonate includes the following components by weight: 10-30 parts of glycoprotein; 2-10 parts of epoxy butyl sulfonate; 0.5-2 parts of sodium bicarbonate; 20-50 parts of ethanol; and 50-100 parts of deionized water.

3. A silicon-free wash-and-condition composition for synergistic color care of a glycoprotein with Polyquatemium-51 according to claim 1, characterized in that, The preparation method of the glycoprotein grafted with epoxy butyl sulfonate includes the following steps: (1) adding glycoprotein into deionized water to form glycoprotein solution under stirring; (2) adding alkaline regulator into the glycoprotein solution to adjust pH to alkaline, and adding ethanol to obtain stable premix; (3) slowly adding epoxy butyl sulfonate solution into the premix to perform grafting reaction under stirring to obtain modified reaction solution; (4) dialyzing the modified reaction solution, and performing spray drying after concentration to obtain glycoprotein grafted with epoxy butyl sulfonate solid.

4. A silicon-free wash-and-condition composition for the synergistic color care of a glycoprotein with Polyquatemium-51 according to claim 3, characterized in that, The concentration of the glycoprotein solution in step (1) is 0.5%-2.0%; the pH range of step (2) is 8.2-8.8, and the amount of added ethanol is 30%-60% of the volume of the glycoprotein solution; the dropping time of the epoxy butyl sulfonate solution in step (3) is 30-60 min, the reaction temperature is 25-35℃, and the reaction time is 2-4 h; and the dialysis time in step (4) is 24-48 h, and the molecular weight cut-off of the dialysis bag is 3.5-10 kDa.

5. A silicon-free wash-and-condition composition for the synergistic color care of a glycoprotein with Polyquatemium-51 according to claim 1, characterized in that, The 2,5-dihydroxyterephthalamide is a terephthalamide derivative having one hydroxyl group at each of the 2 and 5 positions of the benzene ring.

6. A silicon-free wash-and-condition composition for the synergistic color care of a glycoprotein with Polyquatemium-51 according to claim 1, characterized in that, The preservative is a mixture of phenoxyethanol and ethylhexylglycerin in a mass ratio of 3:

1.

7. A process for the preparation of a silicon-free conditioning composition for the simultaneous color-protection and repair of glycoproteins with Polyquatemium-51, as defined in any one of claims 1 to 6, characterized in that, The method includes the following steps: S1, dissolving the glycoprotein grafted with epoxy butyl sulfonate in deionized water to obtain glycoprotein solution; S2, sequentially adding sodium lauroylmethylamino acetate and cocamidopropyl betaine into the glycoprotein solution and mixing uniformly; S3, adding polyquaternium-5 and 2,5-dihydroxyterephthalamide and stirring uniformly to obtain mixture; S4, adding glycerin, preservative, essence and citric acid into the mixture after cooling, adjusting pH, and obtaining target hair care composition.

8. A process for the preparation of a silicon-free wash-and-condition composition synergistically fixed with a glycoprotein and polyquatemium-51 for color care according to claim 7, characterized in that, The reaction conditions of step S1 are that the concentration of the glycoprotein solution is 0.5%-2.0%; the reaction conditions of step S2 are that the stirring rate is 200-400 rpm; the reaction conditions of step S3 are that stirring is performed at 40℃ for 30-60 min; and the reaction conditions of step S4 are that the final pH is 5.0-5.5.

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