Dishwashing detergent composition with enhanced degreasing effect and preparation method thereof

Abstract

The present invention relates to a dishwashing detergent composition with enhanced oil removal performance, comprising the following components by mass: a polyester polyether copolymer, a cationic surfactant, other surfactants, an adjuvant, and water. The dishwashing detergent composition with enhanced oil-dispersing performance is a formulation system that does not contain dodecylbenzenesulfonic acid and whose main component is a surfactant with a higher content of natural plant-based carbon chains. The composition is a weakly acidic to neutral formulation system with a controlled pH of 6-7. The polyester polyether copolymer of the present invention is combined with hydroxyethyl alkyl dimethyl ammonium chloride as a preferred composite system, exhibiting excellent oil removal performance and significantly and synergistically improving the oil-dispersing performance.

Description

Technical Field

[0001] The present invention relates to the technical field of detergents, in particular to a dishwashing detergent composition with enhanced degreasing effect and a preparation method thereof. Background Art

[0002] Currently, the dishwashing liquid industry is highly homogenized, with similar products and a lack of innovation, hindering its development. As a common household product, dishwashing liquid development should be guided by consumer demand and incorporate innovation. Economic development has led to improved literacy and a higher quality of life. Furthermore, consumers are demanding higher standards for dishwashing liquids, requiring them to be highly effective in removing dirt and oil, while also being mild and easy to use. Therefore, developing convenient usage methods, identifying suitable surfactants, and researching mild formulations for efficient oil removal are essential.

[0003] As we all know, sodium dodecylbenzene sulfonate (LAS) is a commonly used surfactant in detergents. It has good oil removal capabilities, is inexpensive, and is used in large quantities in detergent formulations. However, the carbon chain of dodecylbenzene is derived from petrochemicals, making it less environmentally friendly than other surfactants. Furthermore, the raw material has a dark color, which often affects the product's appearance. Formulations containing LAS surfactants are relatively traditional.

[0004] There are many products in the prior art that aim to improve degreasing effects. For example, the degreasing effect is enhanced by compounding fatty alcohol polyoxyethylene ether sodium sulfate, other sulfate surfactants, and amphoteric surfactant alkyl betaine; the composition is formed by compounding lipophilic polymers and hydrophobic polymers with adsorption carrier substances, which has significant selective adsorption for oily substances and can be compounded with surfactants to improve degreasing effects; and the mixing of polyester polyether copolymers and hydrophobically modified maleic acid copolymers can fundamentally improve the wettability and water absorption of fabrics, achieving better degreasing effects. However, none of the above technical solutions solves the problem of how to better improve the oil dispersion effect of the formulation system without adding dodecylbenzenesulfonic acid.

[0005] In summary, there is an urgent need to research and develop a dishwashing detergent that is sulfonic acid-free, has a mild formula and can enhance the oil dispersion effect, so as to solve the problems existing in the existing technology and meet the development needs of the current market. Summary of the Invention

[0006] Based on this, the present invention provides a dishwashing detergent composition with enhanced degreasing effect to overcome the deficiencies of the prior art.

[0007] One object of the present invention is to provide a dishwashing detergent composition with enhanced degreasing effect, wherein the dishwashing detergent composition with enhanced degreasing effect comprises the following components in mass fractions:

[0008] Polyester polyether copolymer 0.2-1.5%

[0009] Cationic surfactant 0.5-3%

[0010] Other surfactants 5-20%

[0011] Additives 0.1-2%

[0012] Water balance;

[0013] in,

[0014] The polyester polyether copolymer has the following general structural formula:

[0015] ;

[0016] The range of n is 6-100; the range of m is 1-15;

[0017] The cationic surfactant has the following general structural formula:

[0018] [ RN + (CH3)2-CH2-CH2-OH]Cl -

[0019] The R is selected from an alkyl group having 12 to 14 carbon atoms.

[0020] Preferably, R is an alkyl group having 12 carbon atoms.

[0021] The dishwashing detergent composition of the present invention, which has enhanced grease dispersibility, is a formulation system that does not contain dodecylbenzenesulfonic acid and whose main component is a surfactant with a higher content of natural plant-based carbon chains. The composition is a weakly acidic to neutral formulation system with a pH controlled at 6-7.

[0022] Furthermore, the molecular weight of the polyester polyether copolymer is 1000-15000.

[0023] Furthermore, the other surfactant is selected from one or more of anionic surfactants, nonionic surfactants and zwitterionic surfactants.

[0024] Furthermore, the anionic surfactant is selected from one or more of alkyl sulfates, fatty alcohol polyoxyethylene ether sulfates, fatty alcohol polyoxyethylene ether carboxylates, and secondary alkyl sulfonates;

[0025] Specifically, the secondary alkyl sulfonate, the alkyl group is preferably C12-C14, and the sodium salt is preferred. The secondary alkyl sulfonate has extremely strong penetration under strong alkaline and high temperature conditions, and has emulsification, degreasing and washing functions.

[0026] Specifically, the fatty acid methyl ester sulfonate preferably has an alkyl group of C12-C14, has good water solubility, and has good cleaning ability even in high-hardness environments, and has balanced cleaning, foaming, surface wetting, and penetration properties.

[0027] Specifically, the fatty alcohol polyoxyethylene ether sulfate preferably has an alkyl group of C12-C14, polyoxyethylene represents the average degree of ethoxylation, and the EO number is preferably 0.5-3.

[0028] Specifically, the fatty alcohol polyoxyethylene ether carboxylate preferably has an alkyl group of C12-C14, which is a linear alkyl group or a branched alkyl group. Polyoxyethylene represents the average degree of ethoxylation, and the EO number is preferably 2-10.

[0029] Furthermore, the nonionic surfactant is selected from one or more of alkyl glycosides, fatty alcohol polyoxyethylene ethers, secondary alcohol polyoxyethylene ethers, fatty alcohol EO-PO block polyethers, and fatty acid ester ethoxylates.

[0030] Specifically, the alkyl polyglycoside preferably has an alkyl group of C12-14, and the alkyl polyglycoside has excellent foaming, emulsifying, dispersing and detergency abilities.

[0031] Specifically, the nonionic surfactant fatty alcohol polyoxyethylene ether is a synthetic product of natural fatty alcohol and ethylene oxide, the fatty alcohol is preferably a fatty alcohol with a carbon number of C12-15, the fatty alcohol is a straight-chain alcohol or an isomerized alcohol, polyoxyethylene represents the average degree of ethoxylation, and the EO number is preferably 3-10.

[0032] Specifically, the secondary alcohol polyoxyethylene ether preferably has an alkyl group of C12-C14, polyoxyethylene represents the average degree of ethoxylation, and the EO number is preferably 9-15. Compared with AEO9, it has better wettability and permeability and can resist gelation in a concentrated system.

[0033] Specifically, the fatty alcohol EO-PO block polyether is preferably a C12-C15 linear alkyl or branched alkyl group, polyoxyethylene represents the average ethoxylation degree, and the EO number is preferably 2-10; polyoxypropylene represents the average propoxylation degree, and the PO number is preferably 2-5.

[0034] Specifically, the fatty acid ester ethoxylate preferably has a C12-C14 alkyl group, polyoxyethylene represents the average ethoxylation degree, and the EO number is preferably 6-15.

[0035] Furthermore, the zwitterionic surfactant is selected from one or more of amino acid surfactants, amine oxide surfactants, betaine surfactants, and imidazoline surfactants.

[0036] Furthermore, the auxiliary agent is selected from one or more of preservatives, solvents, enzyme preparations, anti-redeposition agents, pH regulators, flavors and salts.

[0037] Furthermore, the preservative is selected from one or more of phenoxyethanol, sodium benzoate, methylchloroisothiazolinone, benzisothiazolinone, isothiazolinone and derivatives thereof.

[0038] Furthermore, the anti-redeposition agent is selected from one or more of sodium polyacrylate, maleic acid acrylic acid copolymer, carboxymethyl cellulose, and homopolymer and copolymer of vinyl pyrrolidone.

[0039] Furthermore, the enzyme preparation is selected from one or more of protease, lipase and amylase.

[0040] Furthermore, the solvent is selected from one or more of glycerol, propylene glycol, ethanol, and polyethylene glycol.

[0041] Specifically, the inorganic salt is selected from one or more of halides, carbonates, bicarbonates, formates, acetates, sulfates, nitrates, and citrates.

[0042] Preferably, the inorganic salt is one or more of sodium chloride, sodium citrate, and sodium sulfate.

[0043] Another object of the present invention is to provide a method for preparing the above-mentioned dishwashing detergent composition with enhanced degreasing effect, characterized in that it comprises the following steps:

[0044] S1. Add water to a container, add anionic surfactant under heating conditions, and stir until dissolved;

[0045] S2. Stop heating, then add a nonionic surfactant, a zwitterionic surfactant and a cationic surfactant, and stir until dissolved;

[0046] S3. Add the remaining amount of water, adjust the pH after cooling, then add the polyester polyether copolymer and other additives, stir until dissolved, and obtain the dishwashing detergent composition with enhanced degreasing effect.

[0047] Furthermore, in step S1, the heating temperature is 25-40°C.

[0048] Furthermore, in step S3, the pH is 6-7.

[0049] The present invention has the following beneficial effects:

[0050] The dishwashing detergent composition of the present invention, which enhances oil-dispersibility, is formulated without dodecylbenzenesulfonic acid and primarily comprises a surfactant with a higher concentration of natural plant-based carbon chains. The composition is weakly acidic to neutral, with a pH controlled between 6 and 7.

[0051] 2. The dishwashing detergent of the present invention can be well compatible with anionic surfactants by adding a specific cationic surfactant hydroxyethyl alkyl dimethyl ammonium chloride, so that the dishwashing detergent composition can be stably present; at the same time, hydroxyethyl alkyl dimethyl ammonium chloride can reduce the negative charge repulsion of the hydrophilic end of the anionic mixed micelle, making it easier to form critical micelles with the anionic surfactant, having a lower CMC, reducing surface tension, making it easier for oil stains to curl into oil droplets and detach from the surface under preferential wetting, thereby having the effect of lowering the concentration required for decontamination and higher detergent activity of the surfactant.

[0052] 3. The polyester-polyether copolymer of the present invention is combined with hydroxyethyl alkyl dimethyl ammonium chloride to synergistically and significantly disperse oil stains, improving stain removal capabilities. Based on the principle of like dissolves like, the hydrophobic segments of the polyester-polyether copolymer easily come into contact with oil stains. Combined with the special hydrophobic carbon chains of the cationic surfactant, the oil stains are wrapped around and adsorbed and emulsified on the surface of the oil molecules. The polyester-polyether copolymer contains hydrophilic groups, and the polyether hydrophilic groups of the copolymer tend to face outward toward the water phase, thereby reducing the adsorption of oil stains on hard surfaces, making it easier for the oil stains to fall off the hard surfaces, achieving a good degreasing effect. In the present invention, hydroxyethyl alkyl dimethyl ammonium chloride and polyester-polyether copolymer, as a preferred composite system, demonstrate excellent degreasing capabilities. DETAILED DESCRIPTION

[0053] In order to more clearly illustrate the technical solutions of the present invention, the following examples are given. Unless otherwise stated, the raw materials, reactions and post-processing methods mentioned in the examples are common raw materials on the market and technical methods well known to those skilled in the art.

[0054] The terms "preferred," "preferably," "more preferred," and the like, used herein, refer to embodiments of the invention that may provide certain benefits under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.

[0055] It should be understood that, except in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending upon the desired properties to be obtained by the present invention.

[0056] Citric acid, a pH regulator, in the examples of the present invention was purchased from Guangzhou Reagent Factory.

[0057] The AES in the embodiment of the present invention is fatty alcohol polyoxyethylene ether sulfate, the fatty alcohol has 12-14 carbon atoms, an average degree of ethoxylation is 2, and is an anionic surfactant purchased from Anhui Jintong.

[0058] AEO9 in the examples of the present invention is a fatty alcohol polyoxyethylene ether, a fatty alcohol having 12-14 carbon atoms and an average degree of ethoxylation of 9, a nonionic surfactant, purchased from BASF.

[0059] CAB, cocamidopropyl betaine, and zwitterionic surfactants in the embodiments of the present invention were purchased from Guangzhou Tianci.

[0060] APG, alkyl polyglycoside and nonionic surfactant in the examples of the present invention were purchased from Shanghai Fakai.

[0061] MES in the embodiment of the present invention, fatty acid methyl ester polyoxyethylene sulfonate sodium, an anionic surfactant, was purchased from Petronas HC501.

[0062] The preservative in the embodiment of the present invention is a mixture of methylisothiazolinone and chloromethylisothiazolinone.

[0063] The polyester polyether copolymer in the embodiment of the present invention is purchased from Clariant SRN series products, which has the following general structural formula:

[0064] .

[0065] The hydroxyethyl lauryl dimethyl ammonium chloride and cationic surfactant in the embodiments of the present invention are purchased from Clariant PRAEPAGEN HY products.

[0066] The sodium polyacrylate in the comparative example of the present invention was purchased from Shanghai Myrrel Biochemical Technology Co., Ltd. with the brand name M87494.

[0067] The ingredients and corresponding mass fractions of the dishwashing detergent compositions with enhanced degreasing effects of Examples 1-4 are shown in Table 1.

[0068] Table 1 Components and their mass fractions in Examples 1-4

[0069]

[0070] The preparation method of the dishwashing detergent composition with enhanced degreasing effect of Examples 1-4 comprises the following steps:

[0071] S1. Add water to a container, add anionic surfactant under heating conditions, and stir until dissolved;

[0072] S2. Stop heating, then add a nonionic surfactant, a zwitterionic surfactant, and a cationic surfactant, and stir until dissolved;

[0073] S3. Add the remaining amount of water, adjust the pH after cooling, then add the polyester polyether copolymer and other additives, stir until dissolved, and obtain the dishwashing detergent composition with enhanced degreasing effect.

[0074] Furthermore, in step S1, the heating temperature is about 30°C.

[0075] Furthermore, in step S3, the pH is about 6.5.

[0076] Comparative Example

[0077] The difference between the comparative example and embodiment 1 is:

[0078] In Comparative Example 1, the polyether polyester copolymer was replaced with sodium polyacrylate, and the other ingredients and preparation methods were the same.

[0079] In Comparative Example 2, hydroxyethyl lauryl dimethyl ammonium chloride was replaced with benzalkonium chloride, and the other ingredients and preparation methods were the same.

[0080] In Comparative Example 3, the polyether polyester copolymer and hydroxyethyl lauryl dimethyl ammonium chloride were removed, and the other ingredients and preparation methods were the same.

[0081] The ingredients and corresponding mass fractions of the dishwashing detergent compositions with enhanced degreasing effects of Comparative Examples 1-3 are shown in Table 2.

[0082] Table 2 Components and mass fractions of the dishwashing detergent compositions of Comparative Examples 1-3

[0083]

[0084] Test Example 1

[0085] Product Decontamination Ability Test

[0086] The dishwashing detergent compositions of Examples 1-4 and Comparative Examples 1-2 were selected to perform a decontamination ability test. The specific test method and evaluation criteria are as follows:

[0087] The detergency test was carried out according to the foam position method in Appendix A.2 of GB / T 9985-2022. The test results are shown in Table 3.

[0088] Table 3 Results of national standard dishwashing number determination of dishwashing detergent compositions of Examples 1-4 and Comparative Examples 1-2

[0089]

[0090] According to Table 3, it can be seen that the detergency of Examples 1-4 is better than that of Comparative Examples 1-2. However, in Comparative Example 1, since the polyether polyester copolymer is replaced with sodium polyacrylate, it is unable to exert a synergistic effect with hydroxyethyl lauryl dimethyl ammonium chloride, resulting in a decrease in detergency; in Comparative Example 2, since benzalkonium chloride is used to replace hydroxyethyl lauryl dimethyl ammonium chloride, it is incompatible with anionic surfactants and is likely to produce negative effects, resulting in a decrease in detergency.

[0091] Test Example 2

[0092] Product oil removal rate test

[0093] Test method:

[0094] Wash the glass slide, dry it, and weigh it. The weight is recorded as M0. Add 0.2000g of artificial oil and evenly spread the oil on a 25mm*75mm glass slide. The total weight is recorded as M1. The artificial oil is prepared by mixing hot pot oil and vegetable oil in a mass ratio of 1:1.

[0095] The glass piece was placed at 0°C for 1 hour for accelerated aging, and then taken out and returned to room temperature. 30 mL of the dishwashing detergent composition of Example 1 and Comparative Examples 1-2 were respectively added to 50 mL fixed-volume plastic tubes, and the glass piece was placed in the tube. After standing for 5 minutes, the tube was taken out and rinsed with 500 mL of 250 ppm hard water. The tube was dried and weighed, which was recorded as M2.

[0096] Among them, the oil removal rate calculation formula is: oil removal rate = (M1-M2) / (M1-M0)×100%;

[0097] The test results are shown in Table 4.

[0098] Table 4 Degreasing rate measurement results of dishwashing detergent compositions of Examples 1-4 and Comparative Examples 1-3

[0099]

[0100] According to the results in Table 4, the dishwashing detergent compositions of Examples 1-4 have a better effect of improving the oil removal rate due to the introduction of the polyether polyester copolymer and hydroxyethyl lauryl dimethyl ammonium chloride. However, in Comparative Example 1, since the polyether polyester copolymer is replaced with polyacrylic acid, sodium polyacrylate is incompatible with hydroxyethyl lauryl dimethyl ammonium chloride. In Comparative Example 2, since benzalkonium chloride is used instead of hydroxyethyl lauryl dimethyl ammonium chloride, the cationic surfactant of benzalkonium chloride is incompatible with the system, not only does the oil removal ability not improve, but decreases, so the oil removal rate of the dishwashing detergent composition is worse. Comparative Example 3 does not add the two raw materials of polyether polyester copolymer and hydroxyethyl lauryl dimethyl ammonium chloride, and the oil removal ability of the detergent composition obtained is significantly weaker than that of the examples.

[0101] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations that come within the meaning and range of equivalents of the claims be embraced therein.

[0102] In addition, it should be understood that although this specification is described in terms of implementation methods, not every implementation method contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

Claims

1. A dishwashing detergent composition with enhanced degreasing effect, characterized in that: The dishwashing detergent composition with enhanced degreasing effect is composed of the following components by mass fraction: Polyester polyether copolymer 0.5-1.5% Cationic surfactant 2-3% Other surfactants 5-20% Additives 0.1-2% Water balance; in, The polyester polyether copolymer has the following general structural formula: ； The range of n is 6-100; the range of m is 1-15; The cationic surfactant is hydroxyethyl lauryl dimethyl ammonium chloride; The molecular weight of the polyester polyether copolymer is 1000-15000; The other surfactants are anionic surfactants, nonionic surfactants and zwitterionic surfactants; The anionic surfactant is selected from one or more of alkyl sulfates, fatty alcohol polyoxyethylene ether sulfates, fatty alcohol polyoxyethylene ether carboxylates, and secondary alkyl sulfonates; The nonionic surfactant is selected from one or more of alkyl glycosides, fatty alcohol polyoxyethylene ethers, fatty alcohol EO-PO block polyethers, and fatty acid ester ethoxylates; The auxiliary agent is a mixture of methylisothiazolinone and chloromethylisothiazolinone, a pH regulator, essence and sodium citrate.

2. The dishwashing detergent composition with enhanced degreasing effect according to claim 1, characterized in that: The zwitterionic surfactant is selected from one or more of an amino acid surfactant, an amine oxide surfactant, a betaine surfactant, and an imidazoline surfactant.

3. The method for preparing the dishwashing detergent composition with enhanced degreasing effect according to any one of claims 1 to 2, characterized in that: The steps include: S1. Add water to a container, add anionic surfactant under heating conditions, and stir until dissolved; S2. Stop heating, then add a nonionic surfactant, a zwitterionic surfactant and a cationic surfactant, and stir until dissolved; S3. Add the remaining amount of water, adjust the pH after cooling, then add the polyester polyether copolymer and other additives, stir until dissolved, and obtain the dishwashing detergent composition with enhanced degreasing effect.

4. The method for preparing the dishwashing detergent composition with enhanced degreasing effect according to claim 3, characterized in that: In step S1, the heating temperature is 25-40°C.

5. The method for preparing the dishwashing detergent composition with enhanced degreasing effect according to claim 3, characterized in that: In step S3, the pH is 6-7.

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