Thickening suspension polymer with wide pH value and transparency, preparation method, cleaning agent composition containing same, preparation method and application

Abstract

The present invention discloses a thickening suspension polymer with wide pH transparency, a preparation method, and a cleaning agent composition containing the same, a preparation method, and applications. The thickening suspension polymer is made of raw material components and deionized water, and the raw material components include the following components in percentage by mass: 10.0-75.5% of a hydrophilic monomer, 15.0-85.0% of a hydrophobic monomer, 0-3.0% of a cross-linking monomer, 0.5-16.0% of an amino acid containing a double bond, 0.5-5.0% of an emulsifier, and 0.1-1.0% of an initiator. The present invention uses a double-bond amino acid to react on a polymer chain of an acrylic thickener, so that amino acid surfactants can be linked to form micelles in the formula system, thereby achieving effective thickening of the formula and solving the difficulty of thickening the amino acid surfactant system. The composition containing the same has the characteristics of a wide transparency pH range, high thickening viscosity, good conditioning, stable performance, and is suitable for use as a shampoo.

Description

Technical Field

[0001] The present invention belongs to the field of cleaning and washing, and in particular relates to a thickening suspension polymer with a wide pH value and transparency, a preparation method, and a cleaning agent composition containing the same, as well as a preparation method and application. Background Art

[0002] As consumers become increasingly concerned about the safety of toiletries, sulfate surfactants are considered to have excessive degreasing capabilities and are highly irritating. Consequently, more consumers are opting for milder amino acid surfactants as the primary surfactant in shampoos and body washes. However, amino acid surfactant micelles are relatively fragmented, making them difficult to thicken in formulas. Furthermore, when using amphoteric surfactants such as amino acids as the primary surfactant, their solubility changes with pH changes due to their isoelectric points. This can cause some previously compatible hydrophobic small molecules (such as fragrances) and charged macromolecules (such as cationic conditioners and carboxylate thickeners) to precipitate, compromising the clarity of the formula and the conditioning properties of the product during use, significantly limiting the product's practical use.

[0003] Consumers are increasingly focused not only on cleansing functions like shampooing, but also on the cosmetic experience. For example, a more glamorous appearance requires the addition of pearlescent powder, flower petals, soft beads, and walnut particles. This often requires the addition of acrylic (ester) emulsion thickeners to provide sufficient suspending properties in addition to thickening.

[0004] Some thickeners used in the daily chemical industry have issues with aqueous solution clarity, compounded clarity, conditioning properties, suspension performance, and emulsion stability. For example, patent CN103772625B discloses a product that eliminates high yield values ​​by compounding an emulsifier and a neutralizing monomer. However, the monomer structure of the product itself is not specifically designed. When used in shampoo formulations, the anionic acrylic emulsion and cationic conditioning agent produce electrostatic complexation, reducing the amount of deposition during shampoo use. Consumers experience this as insufficient conditioning.

[0005] To address the difficulty in thickening shampoo formulas using amino acid surfactants, patent CN201710992510.5 discloses an amino acid thickening shampoo composed of three surfactants: amino acid surfactant, sodium olefin sulfonate, and betaine. However, this formulation requires a very high surfactant concentration, generally above 35%, resulting in strong degreasing ability and increased scalp irritation. Furthermore, as the amount of amphoteric surfactants such as betaine and amino acid surfactants increases, the transparency of the formula becomes increasingly demanding due to the presence of both cationic and anionic ions, which exhibit an isoelectric point. When the isoelectric point is exceeded, charge reversal occurs, and the micelle structure changes. This poses significant limitations on downstream applications.

[0006] Therefore, there is still a need for a thickening suspension polymer with a wide pH value and high transparency and a cleaning agent composition containing the same that is suitable for use in daily chemical products such as shampoo. Summary of the Invention

[0007] The technical problem to be solved by the present invention is to provide a thickening suspension polymer with a wide pH value transparency range, wherein the thickening suspension polymer has high transparency in a wide pH value range.

[0008] Another object of the present invention is to provide a method for preparing the aforementioned thickening suspension polymer having a wide pH transparency range.

[0009] Another object of the present invention is to provide a cleaning composition containing the aforementioned thickening suspending polymer with a wide pH transparency range, wherein the cleaning composition has excellent high transparency and conditioning properties within a wide pH range, and the product has the characteristics of low odor and low irritation.

[0010] Another object of the present invention is to provide a method for preparing the cleaning composition.

[0011] Another object of the present invention is to provide applications of the cleaning composition.

[0012] In order to achieve the above object of the invention, the present invention adopts the following technical solutions:

[0013] A thickening suspension polymer with a wide pH value and transparency, comprising, by weight percentage, 20%-35% of raw material components and 65%-80% of deionized water;

[0014] The raw material components include the following components in percentage by mass: 10-75.5% of hydrophilic monomer, 15-85% of hydrophobic monomer, 0-3% of cross-linking monomer, 0.5-16% of amino acid containing double bonds, 0.5-5% of emulsifier, and 0.1-1% of initiator.

[0015] In a specific embodiment, the double bond-containing amino acid is selected from at least one of histidine and tryptophan.

[0016] In a specific embodiment, the hydrophilic monomer is selected from at least one of maleic anhydride, itaconic acid, itaconate, acrylic acid, acrylate, methacrylic acid, methacrylate, citraconic acid, citraconic acid, fumaric acid, fumarate, crotonic acid, crotonate, aconitic acid or aconitate.

[0017] In a specific embodiment, the hydrophobic monomer is selected from at least one of styrene, monobutyl itaconate, vinyl acetate, methyl acrylate, ethyl acrylate, butyl acrylate, isopropyl acrylate, isooctyl acrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isopropyl methacrylate, isooctyl methacrylate or hydroxyethyl methacrylate.

[0018] In a specific embodiment, the crosslinking monomer is selected from olefins containing two unsaturated double bonds, more preferably at least one of N,N'-methylenebisacrylamide, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate or diallyl phthalate.

[0019] In a specific embodiment, the emulsifier is prepared by compounding a nonionic emulsifier and an anionic emulsifier, wherein the anionic emulsifier is selected from at least one of sodium succinate sulfonate, sodium diisobutylnaphthalene sulfonate, sodium dodecylbenzene sulfonate or sodium lauryl sulfate; and the nonionic emulsifier is selected from at least one of Span-80, Tween, alkylphenol polyoxyethylene ether or isomeric alcohol polyoxyethylene ether.

[0020] In a specific embodiment, the initiator is a water-soluble persulfate initiator, more preferably at least one of ammonium persulfate, sodium persulfate or potassium persulfate.

[0021] On the other hand, a method for preparing the aforementioned thickening suspension polymer with wide pH value transparency comprises the following steps:

[0022] 1) dissolving 17-90% of the total weight of the emulsifier in water accounting for 38.5%-70% of the total water added, then adding a hydrophobic monomer, a hydrophilic monomer, and a crosslinking monomer, and stirring in an emulsifier to form a pre-emulsion S1;

[0023] 2) dissolving 5-50% of the total weight of the emulsifier in water accounting for 2-33.5% of the total water added, then adding an amino acid containing a double bond and a hydrophilic monomer, wherein the weight ratio of the amino acid containing a double bond to the hydrophilic monomer is 1:5 to 1:1, and stirring in an emulsifier to form a pre-emulsion S2;

[0024] 3) dissolving 5-33% of the total weight of the emulsifier in 28%-59.5% of the total water added, and adding the solution to the reactor; adding the pre-emulsion S1 obtained in step 1) dropwise to the reactor, adding 50-90% of the total weight of the initiator at a reaction temperature of 80-90° C. to initiate polymerization, and keeping the temperature for 1-1.5 hours after the addition is completed;

[0025] 4) The pre-emulsion S2 obtained in step 2) is then added dropwise to the reactor described in step 3), and polymerization is initiated by adding 10-50% of the total weight of the initiator at a reaction temperature of 80-90° C. After the addition is completed, the mixture is kept warm for 0.5-3 hours to obtain the thickened suspension polymer.

[0026] In another aspect, a cleaning composition comprises the following components, based on the total weight of the composition:

[0027] (a) 0.01 to 15% of the aforementioned or prepared by the aforementioned method, thickening suspension polymer with wide pH value transparency, preferably 0.5 to 8%;

[0028] (b) 10-30% of a mild surfactant, preferably 15-25%;

[0029] (c) 0.01 to 5% of a conditioning agent, preferably 0.1 to 2%;

[0030] (d) The balance is aqueous carrier.

[0031] In a specific embodiment, the mild surfactant of component (b) is selected from at least one of sodium lauryl sarcosinate, sodium lauryl glutamate, sodium lauryl alanine, alkyl amino oxides, alkyl betaines, cocamidopropyl betaine, disodium cocoamphodiacetate, alkyl sulfobetaines, alkyl glycinates, alkyl carboxyglycinates, acyl taurates and acyl glutamates, C12-C16 alkyl glucoside or sodium lauroyl glutamate; preferably, the alkyl and / or acyl groups have 8 to 19 carbon atoms.

[0032] In a specific embodiment, the conditioning agent of component (c) is selected from at least any one of polyquaternium salts, quaternized proteins, cationic guar gums or water-soluble silicone oils; preferably, the conditioning agent is selected from at least any one of guar hydroxypropyltrimonium chloride, polyquaternium-10 or polydimethylsiloxane.

[0033] In a specific embodiment, the aqueous carrier of component (d) is selected from water and a mixture of one or more of sodium chloride, a pH adjuster, an antidandruff agent, a fragrance, an emulsifier, a chelating agent, a sunscreen, a preservative, and a pearlescent agent; preferably, the aqueous carrier comprises the following components in percentage by weight, based on the total weight of the aqueous carrier:

[0034] 0-1% pH adjuster;

[0035] 0-3% anti-dandruff agent;

[0036] 0-3% fragrance;

[0037] 0-3% emulsifier;

[0038] 0-0.5% chelating agent;

[0039] 0-1% sunscreen;

[0040] 0-1% preservatives;

[0041] 0-1% pearlescent agent;

[0042] 0-1% petal or particle suspension;

[0043] 0-1% sodium chloride;

[0044] The rest is water.

[0045] In a specific embodiment, the anti-dandruff agent is selected from at least any one of climbazole, pyrithione zinc, piroctone olamine salt or triclosan;

[0046] The preservative is selected from at least one of kasone, paraben, sodium benzoate, salicylic acid, DMDM ​​hydantoin or phenoxyethanol;

[0047] The fragrance is selected from artificial synthesis or natural essences;

[0048] The emulsifier is selected from at least one of cocamide MIPA, cocoyl monoethanolamide, and PEG-150 distearate;

[0049] The chelating agent is selected from at least one of disodium EDTA, tetrasodium EDTA, and methylglycine diacetic acid (MGDA);

[0050] The petals are selected from at least any one of natural petals and agar petals, and the particles are selected from agar particles;

[0051] The pH regulator is selected from at least one of citric acid, sodium citrate, potassium hydroxide, sodium hydroxide, and triethanolamine.

[0052] In another aspect, a method for preparing the aforementioned cleaning composition comprises the step of stirring and mixing the components (a) to (d) in proportion until they are uniform.

[0053] In another aspect, the above-mentioned cleaning composition or the cleaning composition prepared by the preparation method according to claim 9 is used in shampoo.

[0054] Compared with the prior art, the present invention has the following beneficial effects:

[0055] The present invention uses double-bond amino acids to react with the polymer chain of the acrylic thickener. Due to their similar structures, the amino acid surfactants can be linked to form micelles in the formula system, thereby achieving effective thickening of the formula and solving the difficulty of thickening the amino acid surfactant system.

[0056] Because the amphoteric surfactant (abbreviated as "surfactant") system has a clear isoelectric point, when the pH value exceeds the isoelectric point, its apparent charge will be reversed, resulting in a decrease in the solubility of the system and a decrease in transparency. The present invention can increase the compatibility with the amphoteric surfactant by adding amino acids to the polymer chain segments. Furthermore, when the pH value increases, when the positive and negative charges of amphoteric surfactants such as betaine and amino acid surfactant systems change, the compatibility of the polymer with the amphoteric surfactant is significantly increased, thereby making the formula have good formula transparency. Since the amino acid group is added in the second step of the reaction, it is mainly polymerized on the periphery of the polymer chain. This ensures that after the polymer is neutralized with alkali in the formula, the chain segments can fully stretch when they swell and open, further enhancing the formula compatibility of the polymer; at the same time, the introduction of amino acid ingredients reduces the complexation of the product with cationic conditioners during use, thereby increasing the conditioning ability.

[0057] Because the polymer of the present invention utilizes a two-step polymerization process, with odor-prone monomers polymerized in the first step, followed by thermal insulation, and then the second polymerization step, the finished emulsion can reduce residual monomers such as ethyl acrylate, thereby reducing product odor. Furthermore, amino acid surfactant systems are difficult to thicken due to their broken micelles. The present invention utilizes a second step to add amino acid polymerization, dispersing the amino acid surfactants at the periphery of the system. This significantly enhances the interaction between the polymer and the amino acid surfactant system, thereby thickening the amino acid surfactant system. DETAILED DESCRIPTION

[0058] The present invention will be further described below through specific examples. The examples of the present invention are only for illustration of the present invention and do not limit the scope of the present invention.

[0059] The main raw materials and sources of the embodiments are shown in Table 1:

[0060] Table 1. Main raw materials and sources

[0061] Abbreviation Compound Manufacturer HEMA Hydroxyethyl acrylate Wanhua Chemical Group Co., Ltd. EA Ethyl acrylate Shanghai Dongtu Chemical Co., Ltd. EHA 2-Ethylhexyl acrylate Wanhua Chemical Group Co., Ltd. HTD Histidine Xi'an Musen Bioengineering Co., Ltd. TPH Tryptophan Shandong Fuhe Biotechnology Co., Ltd. DLM Methionine Shandong Fuhe Biotechnology Co., Ltd. AA acrylic acid Wanhua Chemical Group Co., Ltd. MAA Methacrylic acid Wanhua Chemical Group Co., Ltd. IA Itaconic acid Shanghai Aladdin Biochemical Technology Co., Ltd. TA Citraconic acid Shanghai Aladdin Biochemical Technology Co., Ltd. ACA Aconitic acid Shanghai Aladdin Biochemical Technology Co., Ltd. APS Ammonium persulfate Jinan Fengle Chemical Co., Ltd. SDS Sodium lauryl sulfate Shanghai Youyang Industrial Co., Ltd. APE Pentaerythritol triallyl ether Japan Tosoh MMA Methyl methacrylate BASF China Co., Ltd. TMPTE Trimethylolpropane triallyl ether Evonik Specialty Chemicals

[0062] Unless otherwise specified, other raw materials can be obtained through commercial channels.

[0063] The suspension thickening performance of acrylic emulsion in shampoo is mainly characterized by the viscosity and yield value of the shampoo. The test methods are:

[0064] ①Use Brookfield viscometer and 64# rotor to measure the viscosity at 0.5r, 1r, and 20r respectively;

[0065] ② The yield value is represented by subtracting the viscosity value measured at 1r from the viscosity value measured at 0.5r and then dividing by 100. The larger the yield value, the better the suspension.

[0066] [Example 1]

[0067] (1) 3.6 g SDS, 200 g water, 110 g EA, 10 g HEMA, 40 g EHA, 80 g MAA, 5 g AA, 1 g TMPTE and 1 g APE were sequentially added into a container for pre-emulsification to obtain pre-emulsion solution 1.

[0068] 2.16 g of SDS, 30 g of water, 30 g of MAA and 15 g of HTD were sequentially added into a container for pre-emulsification to obtain pre-emulsion solution 2.

[0069] (2) 0.9 g of SDS and 180 g of water were added to the reactor, and stirring and heating were started. When the temperature in the reactor reached 85°C, the pre-emulsion 1 and 225 g of a 1 wt% APS aqueous solution were added dropwise for a total of 1.5 hours. After the addition was completed, the mixture was kept warm for 1 hour. Then, the pre-emulsion 2 and 75 g of a 1 wt% APS aqueous solution were added dropwise for a total of 1 hour. After the addition was completed, the mixture was kept warm for 1 hour.

[0070] (3) Cooling to 30° C., adding water to adjust the final solid content to 30%, filtering the material to obtain the final acrylic acid thickened suspension polymer emulsion.

[0071] [Example 2-10]

[0072] According to the method in Example 1, and using the raw materials in the amounts shown in Table 2, the acrylic acid thickened suspension polymer emulsions of Examples 2-10 were prepared.

[0073] [Comparative Examples 1-7 and Comparative Examples 9-10]

[0074] Referring to the method in Example 1, acrylic emulsions of Comparative Examples 1-7 and Comparative Example 9 were prepared using the raw materials in the amounts shown in Table 2.

[0075] [Comparative Example 8]

[0076] (1) Refer to the pre-emulsion configuration amount in the table to obtain pre-emulsion 1 and pre-emulsion 2.

[0077] (2) Add 0.6 g SDS and 180 g water to the reactor, start stirring and heating, wait until the temperature in the reactor rises to 85 ° C, and simultaneously add pre-emulsion 1, emulsion 2 and 300 g 1 wt% APS aqueous solution dropwise for a total of 2.5 hours. After the addition is completed, keep warm for 2 hours.

[0078] (3) Cooling to 30° C., adding water to adjust the final solid content to 30%, filtering the material to obtain the final acrylic emulsion.

[0079] Table 2, the amount of each raw material in the examples and comparative examples / g

[0080]

[0081] A Emulsion Performance

[0082] Stability test: Place the emulsion in a 50-degree oven for one month, then take it out and observe whether there is any stratification or oil floating. Filter it and observe the change in the residue content. If the residue content exceeds 500, it is unqualified.

[0083] Odor evaluation: Ten odor evaluation panel members were recruited to rate the odor of the lotion (1-5 points), with 1 being the worst odor and 5 being the best odor.

[0084] After the stability and odor meet the requirements, the water phase performance and formulation performance are evaluated.

[0085] B water phase performance evaluation

[0086] Preparation of aqueous phase sample: 3.3 g of acrylic emulsion was added to 96.7 g of water, and then neutralized with 18% NaOH aqueous solution to pH = 6.5. The transparency and viscosity at this time were tested.

[0087] Transparency test: After the transparency instrument has completed its self-test, preheat it for 20 minutes. Determine the wavelength of 420nm, perform zero calibration based on pure water, insert the sample, and read the transparency value.

[0088] Viscosity Test: After the system self-check is complete, place the container containing the sample on the container holder. Select 20 rpm and immerse the rotor in the sample until the mark on the stirring blade shaft is flush with the liquid surface. The instrument will automatically start running. After a few seconds, when the data stabilizes, read the viscosity value.

[0089] C formula performance test

[0090] The mild shampoo formula was prepared by using the acrylic emulsion obtained in the above examples and comparative examples. The formula is shown in Table 3:

[0091] Table 3. Mild shampoo formula

[0092] Recipe 1 Recipe 2 Comparative formula 1 Comparative Formula 2 name Mass / g Mass / g Mass / g Mass / g Function / Manufacturer Deionized water to 100 to 100 to 100 to 100 Acrylic emulsion 8.3 8.3 - - Histidine - 1 - 1 Lauroyl Sarcosine 14 - 14 - Surfactants / Clariant Sodium lauroyl glutamate - 9 - 9 Surfactants / Clariant Sodium Lauroyl Alanine - 4 - 4 Surfactants / Clariant 18% NaOH aqueous solution 1.0 2.0 1.0 2.0 Neutralizer Cocamidopropyl Betaine 3.3 4.3 3.3 4.3 Surfactants / BASF Polyquaternium-10 0.3 0.3 0.3 0.3 Cationic / Dow PHCG 0.5 0.5 0.5 0.5 Preservatives / Dow essence 0.5 0.5 0.5 0.5 Spices / Man's

[0093] Note: Raw materials without manufacturer's name can be used interchangeably as long as they are of the same type.

[0094] The specific preparation method is:

[0095] The prepared acrylic emulsion was added to deionized water, stirring was initiated, and sodium laureth sulfate was added at 300 rpm. The mixture was then neutralized to a pH of 6.5 with an 18% aqueous NaOH solution, and the speed was gradually increased to 800 rpm. After stirring for 10 minutes, cocamidopropyl betaine, polyquaternium-10, PHCG, and fragrance were added all at once. Stirring was continued for 30 minutes to produce the shampoo. To verify the thickening effect of the acrylic emulsion at high pH, ​​different amounts of the aforementioned aqueous NaOH solution were added to Formulations 1 and 2, and subsequent performance testing of the formulations was performed. To further verify the specific application effects of the thickener of the present invention, a basic formulation performance test was conducted, followed by subsequent shampoo application evaluation. The pH value of Formulation 1 and Comparative Formulation 1 was adjusted to 6.5, while the pH value of Formulation 2 and Comparative Formulation 2 was adjusted to 8.

[0096] The shampoos prepared from the acrylic emulsions of the examples and comparative examples were tested for their suspension and thickening properties.

[0097] Shampoo Viscosity Test: After the system self-test completes, place the container containing the sample on the container holder. Select 0.5 rpm, 1 rpm, or 20 rpm, and immerse the rotor in the sample until the mark on the stirring blade shaft is flush with the liquid surface. The instrument automatically starts running. After a few seconds, when the data stabilizes, record the viscosity value at 20 rpm.

[0098] Shampoo yield value test: According to the previous viscosity values ​​of 0.5rpm and 1rpm, calculate the yield value = (η 0.5r -η 1r ) / 100.

[0099] Further performance testing on the hair comb:

[0100] Hair tress smoothness test: 15 wt% sodium laureth sulfate solution was used to clean two sets of unused hair tresses. The combing work was obtained using the MTT175 hair tester as the initial combing work, and recorded as W. initial1 、W initial2 ; The hair bundles were washed with a twenty-fold diluted test shampoo (containing a polymer) and a blank shampoo (without any conditioner), and the test combing work and blank combing work were obtained by the above test steps and recorded as W test and W blank The combing smoothness index can be recorded as:

[0101] Smoothness index = (W blank / W initial2 -W test / W initial1 )*100%.

[0102] The odor stability and water phase performance of the acrylic emulsions in the examples and comparative examples, as well as the prepared mild shampoo, were tested for transparency and suspension thickening performance at different pH values. The performance evaluation results are shown in Table 4:

[0103] Table 4. Comparison of viscosity and suspension properties of mild shampoo formulas

[0104]

[0105]

[0106] It can be seen from Examples 1-10 that with appropriate emulsifier ratios and monomer combinations, stable emulsions can be obtained, and they have good viscosity and transparency in water. They have high transparency and viscosity in two difficult-to-thicken amino acid shampoo formulas, and have a yield value (generally, the yield value of products that are difficult to suspend should be >180), and have good conditioning properties after use.

[0107] By comparing Examples 1-2 with Comparative Examples 1-2, it can be found that when the ratio of the thickening acid to the amphoteric amino acid in the pre-emulsion S2 added in the second step is too high, the reaction process is unstable and the emulsion produces more slag; when this ratio is too low, the proportion of amphoteric amino acids is too high and is located on the periphery of the latex particles, so that when alkali is added for neutralization, the proportion of acid monomers is too small, and the molecular chain cannot be effectively unfolded, resulting in lower viscosity and lower transparency.

[0108] By comparing Example 2 with Comparative Example 3, it can be found that the reactive amino acid added in the first step of polymerization reacts in large quantities on the polymer main chain. Since a relatively large number of acid monomers are introduced in the second step of polymerization, the amino acid cannot be effectively expanded on the periphery of the polymer after neutralization, and thus cannot play an effective role in linking micelles in the surfactant system. The formula viscosity is relatively low and the conditioning ability is poor.

[0109] By comparing Example 3 with Comparative Example 4, it can be found that since methionine cannot participate in the reaction process, there is no obvious improvement in the use effect of the polymer.

[0110] By comparing Examples 2-3 with Comparative Examples 5-6, it can be found that when the emulsifier ratio is too small, the reaction polymerization process is unstable and the product is prone to slag; when the emulsifier ratio is too high, the micelle ratio in the polymerization process is relatively high, and the molecular weight of the obtained emulsion is too low. Although the transparency of the obtained product is good, the low molecular weight makes the viscosity of the product in the aqueous phase and the formulation too low, and the yield value is insufficient, which cannot meet the actual use process.

[0111] By comparing the results of Example 4 with Comparative Example 7, it can be found that the introduction of ester monomers into the second-step pre-emulsion S2 not only results in an insufficient monomer elimination process, resulting in a strong product odor, but also reduces the proportion of external acid and amphoteric amino acids in the molecular chain, resulting in insufficient product performance in both the aqueous phase and the formulation. By comparing the results of Example 4 with Comparative Example 8, it can be found that the direct dropwise addition of monomers without separate steps results in a strong product odor. Moreover, since the monomers are added dropwise together, a reasonable distribution of amphoteric amino acids and hydrophilic acids is not achieved, resulting in poor thickening, transparency, and conditioning properties.

[0112] By comparing the results of Example 1 with those of Comparative Example 9, it can be found that when the acid monomer ratio is too low, the polymer chain segments cannot be opened after adding alkali, which manifests as emulsion demulsification.

[0113] Comparison of the results of Example 1 with Comparative Example 10, and Comparative Examples 1 and 2, reveals that the addition of amino acid monomers to the system during the polymerization stage enables better interaction with the amino acid system in the final formulation. This not only ensures high system transparency and increases system viscosity and yield value, but also effectively mitigates the effects of isoelectric point changes on system solubility when the pH value increases and the positive and negative charge shifts occur. This significantly increases the compatibility of the polymer with the amphoteric surfactant, resulting in formulation transparency across a wide pH range. Furthermore, it reduces complexation with cationic conditioning agents during use, thereby enhancing conditioning properties.

[0114] Although the present invention has been described in detail through the above preferred embodiments, it should be understood that the above description is not intended to limit the present invention. Those skilled in the art will appreciate that, based on the teachings of this specification, modifications or adjustments may be made to the present invention. Such modifications or adjustments should also be within the scope defined by the claims of the present invention.

Claims

1. A cleaning composition, characterized in that Based on the total weight of the composition, the following components are included: (a) 0.01-15% thickening suspension polymer with wide pH transparency; (b) 10-30% mild surfactant; (c) 0.01 to 5% of a conditioning agent; (d) the balance being an aqueous carrier; The thickening suspension polymer with wide pH value and transparency comprises, by weight percentage, 20%-35% of raw material components and 65%-80% of deionized water; The raw material components include the following components in percentage by weight: 10-75.5% of a hydrophilic monomer, 15-85% of a hydrophobic monomer, 0-3% of a cross-linking monomer, 0.5-16% of an amino acid containing a double bond, 0.5-5% of an emulsifier, and 0.1-1% of an initiator; wherein the amino acid containing a double bond is selected from at least one of histidine and tryptophan; The method for preparing the thickening suspension polymer with wide pH value and transparency comprises the following steps: 1) dissolving 17-90% of the total weight of the emulsifier in water accounting for 38.5%-70% of the total water added, then adding a hydrophobic monomer, a hydrophilic monomer, and an optional crosslinking monomer, and stirring in an emulsifier to form a pre-emulsion S1; 2) dissolving 5-50% of the total weight of the emulsifier in water accounting for 2-33.5% of the total water added, then adding an amino acid containing a double bond and a hydrophilic monomer, wherein the weight ratio of the amino acid containing a double bond to the hydrophilic monomer is 1:5 to 1:1, and stirring in an emulsifier to form a pre-emulsion S2; 3) dissolving 5-33% of the total weight of the emulsifier in 28%-59.5% of the total water added, and adding the solution to the reactor; adding the pre-emulsion S1 obtained in step 1) dropwise to the reactor, adding 50-90% of the total weight of the initiator at a reaction temperature of 80-90° C. to initiate polymerization, and keeping the temperature for 1-1.5 hours after the addition is completed; 4) adding the pre-emulsion S2 obtained in step 2) dropwise to the reaction kettle described in step 3), adding 10-50% of the total weight of the initiator at a reaction temperature of 80-90° C. to initiate polymerization, and keeping the temperature for 0.5-3 hours after the addition is completed to obtain the thickened suspension polymer; The hydrophilic monomer is selected from at least one of maleic anhydride, itaconic acid, itaconate, acrylic acid, acrylate, methacrylic acid, methacrylate, citraconic acid, citraconic acid, fumaric acid, fumarate, crotonic acid, crotonate, aconitic acid or aconitate; The hydrophobic monomer is selected from at least one of styrene, monobutyl itaconate, vinyl acetate, methyl acrylate, ethyl acrylate, butyl acrylate, isopropyl acrylate, isooctyl acrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isopropyl methacrylate, isooctyl methacrylate or hydroxyethyl methacrylate; The mild surfactant of component (b) is selected from at least one of sodium lauryl sarcosinate, sodium lauryl glutamate, sodium lauryl alanine, alkyl amino oxides, alkyl betaines, cocamidopropyl betaine, disodium cocoamphodiacetate, alkyl sulfobetaines, alkyl glycinates, alkyl carboxyglycinates, acyl taurates and acyl glutamates.

2. The cleaning composition according to claim 1, wherein Includes the following components: (a) 0.5-8% thickening suspension polymer with wide pH transparency; (b) 15-25% mild surfactant; (c) 0.1-2% conditioning agent; (d) The balance is aqueous carrier.

3. The cleaning composition according to claim 1 or 2, characterized in that The crosslinking monomer is selected from olefins containing two unsaturated double bonds.

4. The cleaning composition according to claim 3, wherein The cross-linking monomer is at least one of N,N'-methylenebisacrylamide, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate or diallyl phthalate.

5. The cleaning composition according to claim 1 or 2, characterized in that The emulsifier is prepared by compounding a nonionic emulsifier and an anionic emulsifier, wherein the anionic emulsifier is selected from at least one of sodium sulfosuccinate, sodium diisobutylnaphthalene sulfonate, sodium dodecylbenzene sulfonate or sodium lauryl sulfate; and the nonionic emulsifier is selected from at least one of Span-80, Tween, alkylphenol polyoxyethylene ether or isomeric alcohol polyoxyethylene ether.

6. The cleaning composition according to claim 1 or 2, characterized in that The initiator is a water-soluble persulfate initiator.

7. The cleaning composition according to claim 6, characterized in that The initiator is at least one of ammonium persulfate, sodium persulfate or potassium persulfate.

8. The cleaning composition according to claim 1, wherein Acyl glutamates include sodium lauroyl glutamate.

9. The cleaning composition according to claim 1, wherein The alkyl group and / or acyl group has 8 to 19 carbon atoms.

10. The cleaning composition according to claim 1 or 2, characterized in that The conditioning agent of component (c) is selected from at least any one of polyquaternium salts, quaternized proteins or water-soluble silicone oils.

11. The cleaning composition according to claim 10, characterized in that The polyquaternium salts include cationic guar gums.

12. The cleaning composition according to claim 10, characterized in that The conditioning agent is selected from at least any one of guar hydroxypropyltrimonium chloride, polyquaternium-10 or polydimethylsiloxane.

13. The cleaning composition according to claim 1 or 2, characterized in that The aqueous carrier of the component (d) is selected from water and one or a mixture of sodium chloride, pH regulator, anti-dandruff agent, essence, emulsifier, chelating agent, sunscreen, preservative, and pearlescent agent.

14. The cleaning composition according to claim 13, characterized in that The aqueous carrier comprises the following components in percentage by weight, based on the total weight of the aqueous carrier: 0-1% pH adjuster; 0-3% anti-dandruff agent; 0-3% fragrance; 0-3% emulsifier; 0-0.5% chelating agent; 0-1% sunscreen; 0-1% preservatives; 0-1% pearlescent agent; 0-1% petal or particle suspension; 0-1% sodium chloride; The rest is water.

15. The cleaning composition according to claim 14, characterized in that The anti-dandruff agent is selected from at least one of climbazole, pyrithione zinc, piroctone olamine salt or triclosan; The preservative is selected from at least one of kasone, paraben, sodium benzoate, salicylic acid, DMDM ​​hydantoin or phenoxyethanol; The fragrance is selected from artificial synthesis or natural essences; The emulsifier is selected from at least one of cocamide MIPA, cocoyl monoethanolamide, and PEG-150 distearate; The chelating agent is selected from at least one of disodium EDTA, tetrasodium EDTA, and MGDA; The petals are selected from at least any one of natural petals and agar petals, and the particles are agar particles; The pH regulator is selected from at least any one of citric acid, sodium citrate, potassium hydroxide, sodium hydroxide, and triethanolamine.

16. The method for preparing the cleaning composition according to any one of claims 1 to 15, characterized in that: The method comprises the steps of stirring and mixing the components (a) to (d) in proportion until they are uniform.

17. Use of the cleaning composition according to any one of claims 1 to 15 or the cleaning composition prepared by the preparation method according to claim 16 in the preparation of shampoo.

Images