Detergent and preparation method and application thereof

Abstract

The invention belongs to the technical field of detergents, and discloses a detergent and a preparation method and application thereof. The detergent disclosed by the invention is prepared from the following components in parts by weight: 0.1 to 5 parts of fatty acid amide propyl dimethyl tertiary amine, 0.1 to 8 parts of sulfonic acid group or sulfuric acid group surfactant and 5 to 25 parts of fatty alcohol polyether nonionic surfactant, the ratio of the anion to the non-anion of the detergent is 5%-50%. The detergent provided by the invention can maintain viscosity and appearance stability in a wider pH range.

Description

Technical Field

[0001] This invention relates to the field of detergent technology, specifically to a detergent, its preparation method, and its application. Background Technology

[0002] Market research indicates that consumers prefer detergent products with good viscosity. Therefore, best-selling ordinary liquid detergents on the market generally need to maintain a certain viscosity to ensure a pleasant sensory experience during use.

[0003] Fatty alcohol polyoxyethylene ether (AEO9) is currently the most produced nonionic surfactant and an important component of liquid detergents. It offers advantages such as low irritation, good detergency, solubilization, and rinsing properties in formulations. However, its dosage and relative proportion significantly affect the product's viscosity. Most existing detergent products are anionic-nonionic systems, with anionic surfactants accounting for a relatively higher proportion than nonionic surfactants (i.e., an anionic-to-nonionic ratio greater than 50%). This is primarily due to the viscosity-reducing effect of polyether-type nonionic surfactants.

[0004] Fatty alcohol polyether nonionic surfactants have a viscosity-reducing effect in detergent formulations, especially isomeric alcohol ethers or special polyether nonionic surfactants containing PO segments, which have a more pronounced viscosity-reducing effect and make viscosity adjustment more difficult. In existing technologies, for liquid detergent formulations with low anion-to-nonionic ratios, the following two types of thickening methods exist:

[0005] One approach is to construct the viscosity system using a network system formed independently by high-molecular polymers, such as polyacrylate copolymers, modified acrylate copolymers, cellulose ethers, xanthan gum, carrageenan, polyvinyl alcohol, and polyoxyethylene, among other natural or synthetic polymer raw materials. Compared to surfactant self-thickening systems, polymeric thickeners are not only more expensive, but also produce products with different viscosity characteristics, potentially exhibiting poor shear resistance, shear thinning, and stringing during flow.

[0006] Another approach is for formulations with a relatively high anionic-to-nonionic ratio, such as 30%–50%. In this case, a small amount of anionic surfactant combined with a relatively high surfactant thickener can be used under specific pH and ingredient ratio conditions to construct a viscosity system. Common surfactants of this type include alkanolamide surfactants, amine oxide surfactants, betaine-type surfactants, and glycerol polyether fatty acid esters. However, for laundry detergent products, the drawback of this approach is that, besides achieving the thickening goal, surfactant thickeners can lead to excessive foaming, resulting in a difficult-to-rinse feel for consumers. Furthermore, this approach has very limited cleaning effectiveness for detergent formulations with even lower anionic-to-nonionic ratios. Summary of the Invention

[0007] The purpose of this invention is to overcome the shortcomings of the prior art and provide a detergent, its preparation method, and its application.

[0008] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0009] In a first aspect, the present invention provides a detergent comprising, by weight, the following components: 0.1 to 5 parts of fatty acid propyl dimethyl tertiary amine, 0.1 to 8 parts of sulfonic acid or sulfuric acid surfactant, and 5 to 25 parts of fatty alcohol polyether nonionic surfactant.

[0010] The detergent has an anionic-to-nonionic surfactant ratio of 5% to 50%. This ratio refers to the proportion of anionic surfactant to the sum of anionic and nonionic surfactants.

[0011] In the detergent composition system of this invention, a viscosity system is constructed by utilizing the self-assembly of a weak cation formed by fatty amide propyl dimethyl tertiary amine under acidic conditions and a pseudo-polymeric anionic-cationic surfactant formed by long-chain sulfonate or sulfate anionic surfactants. Through a special high-addition amount of polyether nonionic surfactant (low anionic-to-nonionic ratio), and utilizing the good electrostatic shielding effect of nonionic surfactants, viscosity and appearance stability can be maintained over a wider pH range. Even with a high polyether nonionic addition amount (i.e., low anionic-to-nonionic ratio), this system can still maintain transparency and stability, maintain good appearance viscosity, and produce moderate foam that is easy to rinse.

[0012] Preferably, the detergent contains 1.5 to 4 parts of fatty acid amide propyl dimethyl tertiary amine, 1 to 8 parts of sulfonic acid or sulfuric acid surfactant, and 5 to 20 parts of fatty alcohol polyether nonionic surfactant; the ratio of anionic to nonionic surfactant in the detergent is 10% to 42.9%.

[0013] More preferably, the anion-to-non-anion ratio of the detergent is any one or a combination of 10%, 15%, 16.7%, 20%, 25%, 30%, 37.5%, 40%, and 42.9%.

[0014] As a preferred embodiment of the detergent of the present invention, the chemical formula of the fatty amide propyl dimethyl tertiary amine is R-CONH-CH2CH2CH2N(CH3)2, wherein R is an alkyl group of C12 to C22.

[0015] Preferably, the R is an alkyl group within the range of any one or both of C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, and C22.

[0016] In a preferred embodiment of the detergent of the present invention, the fatty alcohol polyether nonionic surfactant is a compound formed by reacting a fatty alcohol with at least one of ethylene oxide, propylene oxide, and butane oxide; preferably, the fatty alcohol polyether nonionic surfactant is a compound formed by the addition reaction of a fatty alcohol with at least one of ethylene oxide, propylene oxide, and butane oxide.

[0017] As a further preferred embodiment of the detergent described in this invention, the fatty alcohol polyether nonionic surfactant is at least one of linear alcohol polyoxyethylene ether, linear alcohol polyoxypropylene polyoxyethylene ether, isomeric alcohol polyoxyethylene ether, and isomeric alcohol polyoxypropylene polyoxyethylene ether.

[0018] In a preferred embodiment of the detergent described in this invention, the detergent has a pH value of 3.0 to 7.0; preferably, the detergent has a pH value of 3.2 to 6.8.

[0019] More preferably, the pH value of the detergent is within the range of any one or both of 3.2, 3.5, 4.0, 4.6, 4.7, 4.8, 5.0, 5.5, 6.0, 6.5, and 6.8.

[0020] In a preferred embodiment of the detergent of the present invention, the mass ratio of the sulfonic acid-based or sulfuric acid-based surfactant to the fatty acid amide propyl dimethyl tertiary amine is (0.5-20):1; preferably, the mass ratio is (1.5-10):1.

[0021] Preferably, the mass ratio of the sulfonic acid-based or sulfuric acid-based surfactant to the fatty acid amide propyl dimethyl tertiary amine is any one or a combination of 0.5:1, 1:1, 1.5:1, 2:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, and 9:1.

[0022] As a preferred embodiment of the detergent of the present invention, it further includes 0 to 5 parts of additives; the additives include acid additives, salts, preservatives, enzyme preparations, fragrances, color protectants, whitening agents and anti-redeposition agents.

[0023] Preferably, it also includes 0 to 5 parts of fragrance; more preferably, it also includes any one or a combination of 0.001, 0.01, 0.1, 0.2, 0.3, 0.4, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, and 5 parts of fragrance.

[0024] As a further preferred embodiment of the detergent described in this invention, the acid additive includes at least one selected from hydrochloric acid, sulfuric acid, phosphoric acid, citric acid, acetic acid, and lactic acid.

[0025] Secondly, the present invention provides a method for preparing the detergent described in the first aspect, comprising the following steps:

[0026] Take the components according to the specified weight parts, mix them evenly, and the product is ready.

[0027] Thirdly, the present invention applies the detergent described in the first aspect to daily chemical products.

[0028] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0029] 1. This invention utilizes a polyanionic-cationic surfactant formed by a long-chain sulfonate or sulfate surfactant and a long-chain amide tertiary amine, containing a structure similar to a gemini surfactant. Since sulfonic acid and sulfate are both strong acids compared to carboxylic acids, they can maintain their ionized form over a lower and wider pH range. In a special high-addition polyether nonionic (low anionic-to-nonionic ratio) formulation, the excellent electrostatic shielding effect of the nonionic surfactant enables the maintenance of viscosity and appearance stability over a wider pH range, with moderate foaming and easy rinsing. This overcomes the problems of poor compatibility of anionic-cationic surfactants under conventional conditions (such as using organic polyacids (citric acid, phthalic acid) and acidic amide tertiary amines to form viscoelastic fluids within a narrow weak acid pH range), which easily leads to phase separation and excessive foaming that is difficult to rinse.

[0030] 2. This invention provides a new approach for thickening detergent formulations containing isomeric alcohol polyoxyethylene ethers with strong viscosity-reducing effects, and expands the applications of related special nonionic polyethers. Detailed Implementation

[0031] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below with reference to specific embodiments. Those skilled in the art should understand that the specific embodiments described herein are only for explaining the present invention and are not intended to limit the present invention. In the present invention, the technical features described in an open-ended manner include both closed-ended technical solutions composed of the listed features and open-ended technical solutions that include the listed features.

[0032] Unless otherwise specified, in the following examples and comparative examples, lactic acid and fragrance were obtained from commercially available industrial-grade raw materials, and the same lactic acid and fragrance were used in parallel experiments. The lactic acid was industrial lactic acid with a purity of 80%. The anionic / nonionic ratio refers to the proportion of anionic surfactant to the sum of anionic and nonionic surfactants, expressed as a percentage. " / " indicates a dosage of 0; "-" indicates that data was not measured. The dosages of all components are purified by mass fractions.

[0033] In the following examples and comparative examples, after adjusting the pH of the detergent to a specific value with 5% dilute sulfuric acid, the performance of the detergent composition was tested using the following method:

[0034] (1) Viscosity was measured at 25°C using a rotor viscometer;

[0035] (2) The method for determining the stability at -5℃ is as follows: place the sample in a constant temperature bath at -5℃ for 24 hours and observe whether the sample precipitates. √ indicates that the stability test is qualified.

[0036] (3) The concentration of Roche foam was measured at 40°C using a Roche foam apparatus. The concentration was 2.5 g / L for 150 ppm hard water.

[0037] The compounds used in the following examples and comparative examples are described below, but are not limited to these compounds:

[0038] Stearamide propyl dimethylamine (S-18) was purchased from Guangzhou Dongxiong Chemical Co., Ltd.

[0039] Lauroamide propyl dimethylamine (PKO-12), purchased from Zanyu Technology Group Co., Ltd.;

[0040] Myristamidopropyl dimethylamine (PKO-14) was purchased from Zanyu Technology Group Co., Ltd.

[0041] Palmitamide propyl dimethylamine (PKO-16), purchased from Zanyu Technology Group Co., Ltd.;

[0042] Oleamide propyl dimethylamine (PKO-O) was purchased from Zanyu Technology Group Co., Ltd.

[0043] Erucamide propyl dimethylamine (PKO-22) was purchased from Guangzhou Huayu Fine Chemical Co., Ltd.

[0044] AEO9, fatty alcohol polyoxyethylene ether, purchased from BASF AG;

[0045] Lutensol XL-80, isomeric C10 alcohol POEO alkoxylate, purchased from BASF;

[0046] Lutensol TO-7, an isomeric C13 alcohol ethoxylate, was purchased from BASF.

[0047] Sodium alkylbenzene sulfonate (LAS), sodium α-olefin sulfonate (AOS), and sodium lauryl sulfate (K12) are all commercially available.

[0048] The composition of the detergents in Examples 1-17 and Comparative Examples 1-5 is shown in Tables 1-4.

[0049] The preparation methods of the detergents in Examples 1-17 and Comparative Examples 1-5 are as follows:

[0050] The detergent is obtained by mixing the components according to their mass proportions.

[0051] Table 1: Components (parts by mass) of the detergents in Examples 1-4 and Comparative Examples 1 and 2 and their test results

[0052]

[0053] Comparing the test results of the detergents in Examples 1-4 and Comparative Examples 1-2 in Table 1, it can be seen that the stability of the formulation of alkylbenzene sulfonic acid and stearamide propyl dimethylamine (S-18) under weakly acidic conditions is related to the ratio of anions to nonionic surfactants in the detergent composition system. When the proportion of nonionic surfactants in the composition system is relatively low, such as in Comparative Examples 1 and 2, the detergent samples appear cloudy and the liquid separates into layers. However, when the relative content of AEO9 in the composition system is increased, the detergent samples become transparent. This indicates that the nonionic surfactants in the composition system play a good electrostatic shielding role, thus making it possible to combine tertiary amines and sulfonic acid anionic surfactants under acidic conditions. Comparing the viscosity values ​​of the detergents in Examples 1-3, it can be seen that increasing the relative content of AEO9 in the composition system slightly decreases the viscosity value of the detergent samples, but still maintains a certain viscosity, avoiding the problem of a sharp drop in viscosity that occurs when increasing the proportion of AEO9 in the detergent system in the prior art. From the Roche foam data of the detergents in Examples 1-4, the amount of foam in the detergent samples is moderate, and the foam is relatively stable.

[0054] Table 2: Components (parts by mass) of the detergents in Examples 5, 6 and Comparative Example 3 and their test results

[0055] Components Example 5 Example 6 Comparative Example 3 LAS 2 1 0.5 <![CDATA[AEO9]]> 18 19 19.5 S-18 2 2 2 Lactic acid (80%) 1 1 1 essence 0.3 0.3 0.3 Adjust the pH to a specific value using 5% dilute sulfuric acid. 5.8 6.0 4.6 Anion ratio / % 10.0 5.0 2.5 Appearance transparent transparent transparent Viscosity / mPa.s 305 235 52 -5℃ stability √ √ √ <![CDATA[Roche foam (H0 / H5, mm)]]> 140 / 138 135 / 134 130 / 128

[0056] Comparing the test results of the detergents in Examples 5 and 6 and Comparative Example 3 in Table 2, it can be seen that by keeping the amount of S-18 constant and gradually reducing the alkylbenzene sulfonic acid content in the composition system, the viscosity of the detergent decreases. These results indicate that the viscosity system of the detergent relies on the interaction between anions and cations, and that when cations are in excess, the detergent also exhibits low viscosity. Since the anionic-to-nonionic ratio of the composition system reacts with the content of anionic surfactants in the formulation, it can be concluded that the lower limit of the anionic-to-nonionic ratio that can thicken the detergent composition system is approximately 5%.

[0057] Table 3: Components (parts by mass) and test results of detergents in Examples 7-9 and Comparative Examples 4 and 5

[0058]

[0059]

[0060] By keeping the component ratios of the detergent composition system constant and only adjusting the pH value, a comparison of the test results of Examples 7-9 and Comparative Examples 4 and 5 in Table 3 shows that the viscosity of the detergent exhibits a bell-shaped trend with pH, ​​maintaining good viscosity within the pH range of 3.2 to 6.8. This may be because the sulfonate ion is selected as a tertiary amine cation in the composition system, maintaining a similar ionization form over a wider acidic pH range. Therefore, from a macroscopic perspective, the detergent maintains a certain viscosity across a wide pH range, especially at pH 3.2.

[0061] Table 4: Components (parts by mass) of the detergents in Examples 10-17 and their test results

[0062]

[0063]

[0064] The use of anionic surfactants in detergent compositions was expanded. Comparing the test results of detergents in Examples 10-12 of Table 4, it can be seen that surfactants with sulfonate or sulfate structures in the composition system, under specific anionic / nonionic ratio conditions, can produce detergent products with similar good viscosity. Similarly, polyether-type nonionic surfactants in the same formulation can also be appropriately expanded; for example, using isomeric alcohol ethers such as XL-80 and TO7 can also exhibit viscosity properties similar to AEO9. This indicates that the present invention provides a new method for thickening detergent compositions containing isomeric alcohol polyoxyethylene ethers with strong viscosity-reducing effects. Comparing the test results of detergents in Examples 13-17 of Table 4, it can be seen that tertiary amide propylamines with different alkyl chain lengths exhibit similar properties, and the thickening effect of the system slightly improves with increasing alkyl carbon chain length.

[0065] In theory, under acidic conditions, without altering the charge properties of the anionic and cationic surfactants in the detergent composition system, the acidic additives used in this invention can also be extended to other organic or inorganic acids, which will not be listed in detail here.

[0066] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A detergent, characterized in that, By weight, it includes the following components: 0.1 to 5 parts of fatty acid propyl dimethyl tertiary amine, 0.1 to 8 parts of sulfonic acid or sulfuric acid surfactant, and 5 to 25 parts of fatty alcohol polyether nonionic surfactant. The ratio of anion to non-anion in the detergent is 5% to 50%.

2. The detergent according to claim 1, characterized in that, The chemical formula of the fatty amide propyl dimethyl tertiary amine is R-CONH-CH2CH2CH2N(CH3)2, wherein R is an alkyl group of C12 to C22.

3. The detergent according to claim 1, characterized in that, The fatty alcohol polyether nonionic surfactant is a compound formed by reacting fatty alcohol with at least one of ethylene oxide, propylene oxide, and butane oxide.

4. The detergent according to claim 3, characterized in that, The fatty alcohol polyether nonionic surfactant is at least one of linear alcohol polyoxyethylene ether, linear alcohol polyoxypropylene polyoxyethylene ether, isomeric alcohol polyoxyethylene ether, and isomeric alcohol polyoxypropylene polyoxyethylene ether.

5. The detergent according to claim 1, characterized in that, The detergent has a pH value of 3.0 to 7.

0.

6. The detergent according to claim 1, characterized in that, The mass ratio of the sulfonic acid-based or sulfuric acid-based surfactant to the fatty acid amide propyl dimethyl tertiary amine is (0.5–20):

1.

7. The detergent according to claim 1, characterized in that, It also includes additives; the additives include acid additives, salts, preservatives, enzyme preparations, fragrances, color protectants, whitening agents and anti-redeposition agents.

8. The detergent according to claim 7, characterized in that, The acid additive includes at least one of hydrochloric acid, sulfuric acid, phosphoric acid, citric acid, acetic acid, and lactic acid.

9. A method for preparing the detergent according to any one of claims 1 to 8, characterized in that, Includes the following steps: Take the components according to the specified weight parts, mix them evenly, and the product is ready.

10. The use of the detergent according to any one of claims 1 to 8 in daily chemical products.

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