CN114796018A - Silicon-free shampoo and preparation method thereof - Google Patents

Abstract

The invention relates to silicon-free shampoo and a preparation method thereof, and relates to the technical field of daily chemical industry. The silicon-free shampoo comprises, by mass, 0.1-0.4% of amphiphilic copolymer, 0.1-0.8% of polyquaternary ammonium salt, 1.0-6.0% of cocamidopropyl betaine, 4-10% of alkyl glycoside, 5-40% of amino acid surfactant, 0.5-1% of foam stabilizer and the balance of water. The silicon-free shampoo disclosed by the invention adopts the amphiphilic copolymer, so that the comb performance is more excellent. The compound solution formed after the amphiphilic copolymer and the polyquaternium are reacted has higher viscosity. The silicon-free shampoo disclosed by the invention has excellent combing performance, and the wet combing performance of the shampoo is obviously superior to that of a silicon-containing shampoo sold in the market.

Description

Silicon-free shampoo and preparation method thereof

Technical Field

The invention relates to the technical field of daily chemical industry, in particular to silicon-free shampoo and a preparation method thereof.

Background

In recent years, silicone oil-free washing and protecting products gradually come into the visual field of people, researchers mostly search substitutes of silicone oil from natural products at present, soapnut saponin, tea saponin and the like are applied, but the irritation is large, the using effect of silicon-containing products cannot be achieved, and meanwhile, the natural products are complex in extraction process, long in time consumption and high in cost, so that the silicone oil-free washing and protecting products are difficult to popularize due to the limitations. Therefore, it is necessary to research and prepare a silicone oil substitute which is simple and quick, low in cost and good in carding property.

The cationic surfactant has electrostatic interaction with negatively charged hair and can be combined with the amphiphilic polymer with benzene rings, which provides a theoretical basis for the amphiphilic polymer to stay on the hair. At present, researchers have shown that amphiphilic polymers can be combined with small molecule cationic surfactants (such as BTAC and the like) and applied to hair conditioners, and have good wet combing effect. However, the small-molecule cationic surfactant is strong in irritation, easily causes problems of itching, inflammation and the like of the scalp, and is difficult to apply to shampoo. Therefore, the existing system is difficult to effectively realize the high-value product of the small-molecular cationic surfactant in the shampoo, and a macromolecular cationic polymer substitute is needed to be found to solve the problems of low viscosity and poor combing property of the shampoo.

Disclosure of Invention

Therefore, the invention aims to solve the technical problem of overcoming the problems of low viscosity and poor combing property of the shampoo without silicone oil in the prior art.

In order to solve the technical problems, the invention provides silicon-free shampoo and a preparation method thereof. The invention adopts macromolecular cationic compounds, such as polyquaternium, cationic guar gum and the like, and can be compounded with macromolecular cations through the amphiphilic random polymer to be combined, thereby improving the combing performance of hair.

The invention provides silicon-free shampoo which comprises, by mass, 0.1-0.4% of amphiphilic copolymer, 0.1-0.8% of polyquaternary ammonium salt, 1.0-6.0% of cocamidopropyl betaine, 4-10% of alkyl glycoside, 5-40% of amino acid surfactant, 0.5-1% of foam stabilizer and the balance of water.

In one embodiment of the present invention, the amphiphilic copolymer is prepared from hydrophobic monomers styrene and hydrophilic monomers according to a molar ratio of 4: 6-7: 3, mixing, and copolymerizing by a solution free radical polymerization method under the action of an initiator.

In one embodiment of the present invention, the hydrophilic monomer is acrylic acid and/or methacrylic acid.

In one embodiment of the invention, the initiator is azobisisobutyronitrile and/or dimethyl azobisisobutyrate.

In one embodiment of the invention, the nitrogen content of the polyquaternium is 0.8-2.2%.

In one embodiment of the present invention, the polyquaternium is one or more of polyquaternium (JR-125), polyquaternium (JR-400), polyquaternium (JR-30M), polyquaternium (SL-60), polyquaternium (LR-30M), and polyquaternium (SL-30).

In one embodiment of the invention, the thickener is a mixed system of amphiphilic copolymer and polyquaternium.

In one embodiment of the invention, the conditioning agent is a mixed system of amphiphilic copolymer and polyquaternium.

In one embodiment of the invention, the carbon chain length of the alkyl glycoside is from 8 to 16.

In one embodiment of the invention, the carbon chain length of the alkyl glycoside is from 12 to 16. The alkyl glycoside APG has the best foamability and foam stability when the carbon chain length is 12-16, and the longer the carbon chain length, the less irritating.

In one embodiment of the invention, the amino acid surfactant is one or more of sodium cocoyl glycinate, potassium cocoyl glycinate, sodium lauroyl glutamate, sodium lauroyl sarcosinate and sodium cocoamidopropionate.

In one embodiment of the invention, the foam stabilizer is one or more of coconut fatty acid monoethanolamide, lauramide DEA (ninal), and coconut fatty acid diethanolamide.

The second purpose of the invention is to provide a preparation method of the silicon-free shampoo, which comprises the following steps,

(1) dissolving cocamidopropyl betaine, alkyl glycoside and amino acid surfactant in water, mixing, and heating to 75-85 deg.C;

(2) sequentially adding polyquaternium water solution and amphiphilic copolymer solution, uniformly mixing and cooling to 50-60 ℃;

(3) adding the water solution of the foam stabilizer, uniformly mixing, and cooling to 20-30 ℃ to obtain the silicon-free shampoo.

Compared with the prior art, the technical scheme of the invention has the following advantages:

(1) the amphiphilic copolymer (St-co-MAA) adopted by the silicon-free shampoo has more excellent combing performance. A compound solution formed by the action of the amphiphilic copolymer (St-co-MAA) and the polyquaternium has higher viscosity, and six polyquaterniums have the maximum acting force and the highest apparent viscosity when r is about 1.0.

(2) The silicon-free shampoo disclosed by the invention has different weighting scores on foamability, foam stability, transparency and viscosity, has excellent combing performance, the wet combing performance of the shampoo is obviously superior to that of the silicon-containing shampoo sold in the market, and the addition of the amphiphilic copolymer can obviously improve the wet combing performance of the shampoo.

(3) The silicon-free shampoo disclosed by the invention has better temperature resistance and shear rate resistance, and when the temperature is 70 ℃, the shear rate is 1s ^-1 Still has higher viscosity.

Drawings

In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the present disclosure taken in conjunction with the accompanying drawings, in which:

FIG. 1 is a graph showing the combing properties of P (St-co-MAA) and P (St-co-AA) in test example 1 of the present invention.

FIG. 2 is a graph showing the viscosity titration curves of six polyquaterniums and amphiphilic copolymer P (St-co-MAA) of test example 2 of the present invention.

FIG. 3 is a graph showing the viscosity of the system of test example 3 of the present invention as the shear rate becomes higher.

FIG. 4 is a graph showing the viscosity of the system according to test example 3 of the present invention as it increases from 20 ℃ to 80 ℃.

FIG. 5 is a graph showing the effect of amphiphilic copolymers of test example 5 of the present invention on shampoo flocculation.

Fig. 6 shows a shampoo combing test according to test example 5 of the present invention; wherein (a) is a wet combing test and (b) is a dry combing test, representing significant differences.

Detailed Description

The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.

For a further understanding of the present invention, reference will now be made in detail to the following examples. The details of the reagents used in the description are shown in table 1:

TABLE 1

For a further understanding of the present invention, reference will now be made in detail to the present invention with reference to the following examples. The details of the apparatus used in the description are shown in table 2:

TABLE 2

1. Shampoo compounded by P (St-co-MAA) and different polyquaterniums

Table 3 shows the formulations (in 30 g) of the shampoos of examples 1-6:

TABLE 3

(1) Synthesis of P (St-co-MAA)

Styrene (St) and methacrylic acid (MAA) (molar ratio 6: 4, total molar amount 0.1mol) monomers were charged into a 250mL reaction flask, 30mL of isopropanol was added, and at the same time, Azobisisobutyronitrile (AIBN) (3% of the total molar amount of St and AA monomers) as an initiator was added, nitrogen was introduced to remove oxygen for about 30min, and the flask was sealed. The reaction bottle is placed in an oil bath pot and reacts for 24 hours at a constant temperature of 65 ℃. After the reaction is finished and the reaction product is naturally cooled, washing and precipitating by using petroleum ether, repeatedly washing for three times, and drying for 24 hours in a constant-temperature oven at the temperature of 45 ℃ to obtain the product.

(2) Preparation of shampoo (30 g, unless otherwise specified, all dissolved in deionized water)

1) Dissolving 0.15g of polyquaternium in deionized water, stirring until the polyquaternium is uniformly dissolved, and obtaining a polyquaternium water solution which is transparent and uniform;

2) adding 2g of amphiphilic copolymer (St-co-MAA) into deionized water, adding NaOH to dissolve, and preparing 100mL of amphiphilic copolymer standard solution;

3) dissolving 0.54g of cocamidopropyl betaine, 2.4g of alkyl glycoside and 2.4g of amino acid surfactant in the remaining water, mixing well and heating to 80 ℃; then adding the polyquaternary ammonium salt aqueous solution and 1.8mL of amphiphilic copolymer standard solution, uniformly mixing and cooling to 55 ℃;

4) and finally, adding 0.24g of foam stabilizer, uniformly mixing and cooling to room temperature to obtain the silicon-free shampoo.

2. Shampoo prepared from cocamidopropyl betaine, alkyl glycoside, polyquaternary ammonium salt or potassium cocoyl glycinate with different dosages

Substantially as in example 1, table 4 shows a table of the levels of factors for the shampoos of examples 7-15:

TABLE 4

Table 5 shows a partial stock orthographic table for shampoos of examples 7-15:

TABLE 5

Comparative example 1

The same as example 1 except that P (St-co-MAA) was changed to P (St-co-AA).

Comparative example 2

Essentially the same as example 1, except that P (St-co-MAA) was not added.

Comparative example 3

Commercially available silicon containing shampoos.

Comparative example 4

Commercially available silicon-free shampoos.

Test example 1

The combing Performance test was carried out for P of example 1 (St-co-MAA) and P of comparative example 1 (St-co-AA):

weighing 2g of dried P (St-co-MAA) or P (St-co-AA) into a beaker, adding 22mL of 1% NaOH solution (the molar ratio of NaOH to MAA or AA is 1: 1), stirring and dissolving for 24h, adjusting the pH value to 9.0, and then adding a 100mL volumetric flask to a constant volume to prepare 20g/L of polymer mother liquor.

Beauverine Trimethyl Ammonium Chloride (BTAC) with certain effective mass (namely mass multiplied by 0.85) is weighed and added with deionized water to be dissolved at 80 ℃. A certain volume of the polymer solution is measured and mixed with a BTAC solution at 80 ℃ (the concentration of BTAC is 2%) to prepare a compound solution with a molar ratio (r) of 1.2, r is the ratio of St to BTAC in the polymer, and a wet carding performance test is carried out on the compound solution, and the structure is shown in figure 1.

FIG. 1 is a graph of combing performance in the wet condition of P (St-co-MAA) and P (St-co-AA) after exposure to BTAC. As can be seen from the figure, P (St-co-MAA) is reduced by 33.9% compared to the original by 23.6% compared to the original by 23.9%, the former has more excellent combing performance due to the hydrophobicity provided by methyl group in MAA, and although one methyl group in small molecule provides less hydrophobicity, the two have larger difference in hydrophilicity and hydrophobicity in polymer.

Test example 2

Viscosity performance tests were performed on the P (St-co-MAA) and polyquaternium compounded solutions of examples 1-6:

the rheometer test fixture adopts a standard ETC circular steel plate fixture with the diameter of 40mm, the Gap value of 53mm and the cone angle of 1 degree. Before testing, firstly, the fixture is calibrated and zeroed, experimental parameters are set, a Flow Sweep mode is selected to measure the steady-state rheology of the solution, and the shear rate is 10 ^-3 -10 ³ s ^-1 The equilibration time was 30s and the test required to ensure even fill and no air bubbles between the fixture and the sample. Before the dynamic rheological test, the linear viscoelastic region of the sample is determined by amplification, and the modulus change of the solution is measured by frequency mode on strain in a selected parallel region, and the result is shown in FIG. 2.

FIG. 2 is a graph of the viscosity titration curves for six polyquaterniums (10mL, 1%) and amphiphilic copolymer P (St-co-MAA). As can be seen from the data, the titration limits for SL-60, SL-30 and LR-30M are 0.6mL, and for JR-30M, JR-400 and JR-125 are 1.0mL, above which a floc is formed, with turbidity. Among them, SL-60 has the highest viscosity of 3623.45pa.s, and JR-125 has the lowest viscosity of only 170.67pa.s, but is equivalent to 2% BTAC, r ═ 1.2 viscosity (187pa.s), so it can be seen that the apparent viscosity of the solution after the action of the macromolecular polyquaternium and the amphiphilic copolymer is much greater than the viscosity of the small molecule and the amphiphilic copolymer, which is attributed to more binding sites in the macromolecular chain and the chain entanglement of the macromolecular and the amphiphilic copolymer.

Table 6 shows the performance parameters of six polyquaterniums, wherein the higher the solution viscosity, the higher the molecular weight of the polyquaternium. As can be seen from FIG. 2, the titration limits of SL-60, SL-30 and LR-30M are the same, and the nitrogen contents of the three are also the same; this relationship also exists for JR-30M, JR-400 and JR-125, and to verify whether the molar ratio (r) of polyquaternium to amphiphilic copolymer is also calculated as follows:

for 10mL of 1% SL-60 (nitrogen content 0.8-1.1);

m _SL–60 ＝10×0.01＝0.1g；

m _N ＝0.1×(0.8％～1.1％)＝0.0008～0.0011g；

at this point, 2% 6: the limit of 4P (St-co-MAA) was 0.6 mL;

and for polyquaterniums having a nitrogen content of from 1.5 to 2.2, n _N ＝1.07×10 ^-4 ～1.57×10 ^-4 mol，n _St ＝1.24×10 ^-4 mol, r is 1.16 to 0.79. It can be seen that the cation-pi electron relationship of the polyquaternium and the amphiphilic copolymer also conforms to the rule of small molecule cations, namely that the acting force is the maximum and the apparent viscosity is the highest when the molar ratio is about 1.0. As can be seen from a comparison of Table 6, when the nitrogen content is 1.5 to 2.2%, the higher the molecular weight of the polyquaternium, the higher the apparent viscosity of the solution, indicating that the force with the amphiphilic copolymer is greater; when the nitrogen content is 0.8-1.1%, the molecular weights of LR-30M, SL-30 and SL-60 are equivalent, but the viscosity of LR-30M after being reacted with the amphiphilic copolymer is far less than that of SL-30 and SL-60, because the modified substituent group of LR-30M is different from that of SL-30 and SL-60, and the apparent viscosity caused by the modified substituent group is different.

TABLE 6

Test example 3

Shampoo generally affects the residual amount of amphiphilic copolymer on hair due to the interaction of amphiphilic copolymer and polyquaternium JR-30M (example 4) influenced by two factors, shear rate and temperature.

(1) Influence of shear Rate

The dynamic viscosity was measured by a DHR-2 dynamic shear rheometer, as shown in FIG. 3, where the viscosity of the system decreased with increasing shear rate, i.e., the entire process was shear thinning. The characteristics of Newtonian fluid do not appear in the process of increasing the shear rate, so that the P (St-co-MAA) and JR-30M mixed system is not typical of Newtonian fluid.

(2) Influence of temperature on viscosity

The viscosity change trend of the P (St-co-MAA) and JR-30M mixed system along with the temperature rise from 20 ℃ to 80 ℃ is measured by a DHR-2 dynamic shear rheometer, a small amount of deionized water is dripped around a die during measurement, an anti-volatilization device is additionally arranged, the measurement result is shown in figure 4, and the overall trend is that the viscosity of the system is reduced along with the temperature rise. At a temperature of 70 ℃, the system is still viscous, but somewhat reduced from the initial viscosity. The system has certain temperature resistance and can be applied to different temperature environments.

Test example 4

Foam test method: measuring the foam property of a sample by adopting a measuring cylinder oscillation method, measuring 30mL of solution to be measured in a 100mL measuring cylinder with a plug at normal temperature, shaking up and down for 20 times at 180 degrees, and recording the foam height (H) at different times _0min ，H _30min ) The average value was obtained by repeating the experiment three times.

And (3) transparency test: and measuring the transparency of the shampoo by using a double-beam ultraviolet-visible spectrophotometer, wherein the measurement wavelength is set to be 600nm, and deionized water is used as a blank background. The shampoo was slowly poured into a quartz cuvette to prevent air bubbles from forming, and each sample was measured three times and the average value was taken.

Sequencing each index, respectively giving 10-2 points from high to low, wherein the viscosity of the shampoo is difficult to adjust and is an important parameter in the shampoo, and the important parameter is taken as a main factor and accounts for 40%; the formula is silicone oil-free shampoo, and has higher requirement on transparency, so that the transparency accounts for 30%; the foaming properties and the foam reduction rate were 20% and 10%, respectively, and the overall score was viscosity × 0.4+ transparency × 0.3+ foaming properties × 0.2+ foam reduction rate × 0.1, and the results of the experiment are shown in table 7. According to the data, under the evaluation criteria, the scores are in the order of example 12 > 7 ═ 10 > 15 > 8 > 11 > 9 > 11 > 10, the factors are in the order of APG12-16 > JR-400 > CAB-35 > AK-302, and the concentration of the polyquaternium of examples 7 and 12 is 0.8%, the concentration is relatively high, and the irritation is greater, so the shampoo of example 10 is selected for the next study.

TABLE 7

Test example 5

(1) Flocculation experiment

Flocculation is an important mechanism for depositing effective substances in the shampoo on hair, partial shampoo has no flocculation phenomenon, in order to investigate the influence of the addition of the amphiphilic copolymer on the flocculation effect of the shampoo, the shampoos of example 10 and comparative example 2 are respectively diluted by 1-20 times, and the absorbance at 600nm under different dilution times is measured by an ultraviolet spectrophotometer, and the result is shown in fig. 5.

According to a flocculation dynamic curve, the shampoo has obvious flocculation, when the dilution multiple is low, the higher the dilution multiple is, the larger the flocculation amount is, the flocculation peak value is reached after the dilution is performed by a certain multiple, and then the flocculation amount is reduced along with the continuous increase of the dilution multiple until the flocculation amount completely disappears. This is because at high concentrations (> CMC) of surfactant, micelles formed by the anions and cations can "dissolve" in solution; as the concentration of the surfactant decreases, the cationic polymer and the anionic surfactant are electrostatically bonded to form a coagulated complex, and the coagulated complex appears as a flocculent gel in appearance; with further increase of dilution factor, the surfactant concentration is much lower than CMC, a uniform and stable liquid is formed, and flocculation disappears. In addition, the addition of the amphiphilic copolymer can generate flocculation at a lower dilution factor, and can increase the flocculation amount, which is probably due to the influence of cation-pi electron interaction on the surfactant micelle, and the amphiphilic copolymer can consume a part of cations, so that the surfactant micelle can be separated out to generate flocculation at a lower dilution factor.

(2) Combing experiments

The shampoos of example 10 and comparative examples 2-4 were comb tested and the results are shown in fig. 6.

As can be seen from fig. 6(a), for wet combing performance, the combing work of the shampoo prepared by the optimization experiment is that the commercial silicon-free shampoo > commercial silicon-containing shampoo > non-polymer shampoo > the shampoo of example 10, which shows that the shampoo formula prepared by the optimization experiment has excellent wet combing performance, the combing work of the shampoo of example 10 is significantly lower than that of other products (P is less than 0.01), and the amphiphilic copolymer is proved to be capable of obviously improving the wet combing performance of hair. As can be seen in fig. 6(b), the dry combing performance measures example 10 shampoo > no added polymer shampoo > commercial silicon free shampoo > commercial silicon containing shampoo.

It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.

Claims (10)

1. The silicon-free shampoo is characterized by comprising, by mass, 0.1-0.4% of an amphiphilic copolymer, 0.1-0.8% of polyquaternary ammonium salt, 1.0-6.0% of cocamidopropyl betaine, 4-10% of alkyl glycoside, 5-40% of an amino acid surfactant, 0.5-1% of a foam stabilizer and the balance of water.

2. The silicon-free shampoo of claim 1, wherein the amphiphilic copolymer is prepared from styrene, a hydrophobic monomer, and a hydrophilic monomer in a molar ratio of 4: 6-7: 3, mixing, and copolymerizing by a solution free radical polymerization method under the action of an initiator.

3. The silicon-free shampoo of claim 2 wherein the hydrophilic monomer is acrylic acid and/or methacrylic acid.

4. The silicon-free shampoo of claim 2 wherein the initiator is azobisisobutyronitrile and/or dimethyl azobisisobutyrate.

5. The silicon-free shampoo as defined in claim 1 wherein the polyquaternium has a nitrogen content of 0.8-2.2%.

6. The silicon-free shampoo of claim 1 wherein the alkyl glycoside has a carbon chain length of from 8 to 16.

7. The silicon-free shampoo of claim 1 wherein the alkyl glycoside has a carbon chain length of 12 to 16.

8. The silicon-free shampoo of claim 1 wherein the amino acid surfactant is one or more of sodium cocoyl glycinate, potassium cocoyl glycinate, sodium lauroyl glutamate, sodium lauroyl sarcosinate and sodium cocoamidopropionate.

9. The silicon-free shampoo of claim 1 wherein the foam stabilizer is one or more of coconut fatty acid monoethanolamide, lauramide DEA, and coconut fatty acid diethanolamide.

10. The method for preparing a silicon-free shampoo according to any one of claims 1-9, comprising the steps of,

(1) dissolving cocamidopropyl betaine, alkyl glycoside and amino acid surfactant in water, mixing, and heating to 75-85 deg.C;

(2) adding polyquaternium water solution and amphiphilic copolymer solution, mixing uniformly and cooling to 50-60 ℃;

(3) adding a foam stabilizer, uniformly mixing, cooling to 20-30 ℃ and obtaining the silicon-free shampoo.

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