A high efficiency bacteriostatic tableware detergent composition and its preparation method

Abstract

The application discloses a high-efficiency bacteriostatic tableware detergent composition, which comprises the following components in mass fraction: modified organosilicon 0.2-2%, cationic surfactant 0.2-2%, dodecyl benzene sulfonic acid 7-12%, other surfactants 8-15.5%, auxiliary agent 0.1-2%, and water in remainder; wherein the modified organosilicon is obtained by reaction of octamethylcyclotetrasiloxane with KH550 and polyethylene glycol glycidyl ether. The modified organosilicon is compounded with specific cationic surfactants, dodecyl benzene sulfonic acid and other components, has higher permeability to bacterial cells, can more efficiently destroy the shell, protein and other structures in the cells, and inhibit the growth and reproduction of the cells. The synergistic effect of the various components in the application complements each other, so that the detergency, bacteriostasis and stability of the detergent composition are obviously improved, the cost is relatively low, and the application prospect is good.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of detergent. It mainly relates to a high-efficiency bacteriostatic tableware detergent composition and a preparation method thereof. BACKGROUND

[0002] At present, the tableware detergent industry has a high degree of homogeneity, and the products are basically the same. The development of tableware detergents should be guided by the requirements of consumers and innovative in products. According to the survey data, the regular tableware detergent products on the market basically have good oil stain removal effect. In order to further win the favor of consumers, in addition to maintaining the washing capacity and washing feel, the antibacterial function of the detergent is gradually concerned by people. However, considering the requirements of the daily chemical industry on toxicity, cost and other factors, the antibacterial agents such as triclosan, triclocarban, p-chloro-m-cresol and chlorine dioxide are mainly used in the detergents with antibacterial performance. The advantages of such traditional antibacterial / antibacterial agents are strong effect and low dosage, but most of them have low toxicity. Therefore, it has certain market prospect to develop a tableware detergent with high-efficiency bacteriostatic effect, safety, stability and low cost.

[0003] Prior art, such as CN1142994C, discloses a bactericidal type of washing-up liquid and its production method. The bactericidal type of washing-up liquid is prepared by proportioning chlorine dioxide, fatty alcohol polyoxyethylene ether sodium sulfate, fatty acyl diethanolamine, sodium dodecyl benzene sulfonate, ethylenediaminetetraacetic acid, sodium tetraborate and deionized water. The bactericidal agent chlorine dioxide used in the bactericidal type of washing-up liquid has strong antibacterial ability, but it is not stable, volatile and irritating. However, the composition of the above technical solution has limited bacteriostatic effect, the product is not stable, and the cost is high, which does not meet the demand for high-efficiency bacteriostatic, safe, stable and low-cost tableware detergent.

[0004] In view of the above, it is urgent to develop a new technical solution to solve the problems in the prior art. SUMMARY

[0005] Based on this, the present application provides a high-efficiency bacteriostatic tableware detergent composition and a preparation method thereof. The detergent has high-efficiency bacteriostatic effect, is safe, non-toxic and low in cost.

[0006] One object of the present application is to provide a high-efficiency bacteriostatic tableware detergent composition, which comprises the following components by mass fraction:

[0007]

[0008]

[0009] The modified organosilicon is obtained by reacting octamethylcyclotetrasiloxane with KH550 and polyethylene glycol glycidyl ether.

[0010] Further, the preparation method of the modified organosilicon comprises the following steps:

[0011] S1. Blending octamethylcyclotetrasiloxane, KH550 and a catalyst, heating and reacting, adjusting pH to obtain an intermediate product;

[0012] S2. Blending polyethylene glycol glycidyl ether with the intermediate product, heating and reacting to obtain the modified organosilicon.

[0013] Further, in step S1, the heating and reacting is performed at a temperature of 50-80℃ for 10-20h.

[0014] Further, in step S2, the heating and reacting is performed at a temperature of 50-70℃ for 1-2h.

[0015] Further, the catalyst is dodecylbenzenesulfonic acid.

[0016] In the modified organosilicon, first, octamethylcyclotetrasiloxane (D4) is reacted with amino silane coupling agent KH550 to make D4 and KH550 polymerize by ring opening to obtain an intermediate product with introduced amino groups, then the amino groups in the intermediate product are reacted with polyethylene glycol glycidyl ether containing epoxy groups to realize the grafting of alkoxy polyether segments, the present application introduces a large number of amino groups and alkoxy long chains into the hydrophobic D4, realizes hydrophilic modification, and at the same time makes it have weak cationicity, thereby greatly improving the emulsification and dispersion effect of the composition, improving the product stability, making the product less likely to separate and precipitate, and having better decontamination effect. At the same time, the modified organosilicon is compounded with specific cationic surfactants, dodecylbenzenesulfonic acid and other ingredients, has higher penetration force on bacterial cells, can more efficiently destroy the shell, protein and other structures in the cells, and inhibit the growth and reproduction of the cells.

[0017] Further, the cationic surfactant has the following general structure:

[0018] [R-N + (CH3)2-CH2-CH2-OH]Cl-;

[0019] The R is selected from alkyl groups with 12-14 carbon atoms.

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

[0021] Further, the other surfactants are selected from one or more of anionic surfactants, nonionic surfactants and zwitterionic surfactants.

[0022] Further, the anionic surfactant is selected from one or more of fatty alcohol polyoxyethylene sulfate, fatty alcohol polyoxyethylene carboxylate, secondary alkyl sulfonate, fatty acid ester polyoxyethylene sulfonate.

[0023] Specifically, the secondary alkyl sulfonate, alkyl preferably C12-C14, preferably sodium salt, has strong penetration under strong alkali and high temperature conditions, and has emulsifying, deoiling and washing functions.

[0024] Specifically, the fatty acid methyl ester sulfonate, alkyl preferably C12-C14, has good water solubility and good cleaning ability in high hardness environment, and has balanced decontamination, foaming, surface wetting and penetration performance.

[0025] Specifically, the fatty alcohol polyoxyethylene sulfate, alkyl preferably C12-C14, polyoxyethylene represents the average degree of ethoxylation, and the EO number is preferably 0.5-3.

[0026] Specifically, the fatty alcohol polyoxyethylene carboxylate, alkyl preferably C12-C14 alkyl, the alkyl is linear alkyl or branched alkyl, polyoxyethylene represents the average degree of ethoxylation, and the EO number is preferably 2-10.

[0027] Further, the nonionic surfactant is selected from one or more of alkyl glycoside, fatty alcohol polyoxyethylene ether, secondary alcohol polyoxyethylene ether, fatty alcohol EO-PO block polyether, fatty acid ester ethoxylate.

[0028] Specifically, the alkyl glycoside, alkyl preferably C12-14, has excellent foaming, emulsifying, dispersing and decontamination ability.

[0029] 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 carbon number C12-15, the fatty alcohol is linear alcohol or isomeric alcohol, polyoxyethylene represents the average degree of ethoxylation, and the EO number is preferably 3-10.

[0030] Specifically, the secondary alcohol polyoxyethylene ether, alkyl preferably C12-C14, polyoxyethylene represents the average degree of ethoxylation, and the EO number is preferably 9-15, which has better wetting and penetration than AEO9, and can resist gel in concentrated system.

[0031] Specifically, the fatty alcohol EO-PO block polyether, preferably C12-C15 linear alkyl or branched alkyl, polyoxyethylene represents the average degree of ethoxylation, and the EO number is preferably 2-10; polyoxypropylene represents the average degree of propoxylation, and the PO number is preferably 2-5.

[0032] Specifically, the fatty acid ester ethoxylate, preferably C12-C14 alkyl, polyoxyethylene represents the average degree of ethoxylation, the number of EOs is preferably 6-15.

[0033] Further, the zwitterionic surfactant is selected from one or more of an amino acid type surfactant, an amine oxide type surfactant, a betaine type surfactant, an imidazoline surfactant.

[0034] Further, the auxiliary agent is selected from one or more of a preservative, a solvent, an enzyme preparation, an anti-redeposition agent, a neutralizing agent, a pH adjusting agent, a fragrance, and a salt.

[0035] Further, the enzyme preparation is selected from one or more of a protease, a lipase, an amylase.

[0036] Further, the preservative is selected from one or more of phenoxyethanol, sodium benzoate, methyl chloroisothiazolinone, benzisothiazolinone, isothiazolinone and its derivatives.

[0037] Further, the anti-redeposition agent is selected from one or more of sodium polyacrylate, maleic acid-acrylic acid copolymer, carboxymethyl cellulose, homopolymers and copolymers of vinylpyrrolidone.

[0038] Further, the solvent is selected from one or more of glycerol, propylene glycol, ethanol, polyethylene glycol.

[0039] Further, the neutralizing agent is selected from one or more of sodium hydroxide, potassium hydroxide.

[0040] Specifically, the salt is selected from one or more of halide salt, carbonate salt, bicarbonate salt, formate salt, acetate salt, sulfate salt, nitrate salt, citrate salt.

[0041] Preferably, the salt is one or more of sodium chloride, sodium citrate, sodium sulfate.

[0042] Another object of the present application is to provide a preparation method of the above-mentioned high-efficiency bacteriostatic tableware detergent composition, comprising the following steps:

[0043] L1. Add deionized water to the container according to the mass fraction, then add sodium hydroxide, and then add dodecylbenzenesulfonic acid, and stir until dissolved;

[0044] L2. Add AES, AEO9, APG, sodium cocoyl glutamate, and stir until dissolved;

[0045] L3. Add modified silicone and hydroxyethyl lauryl dimethyl ammonium chloride, and stir until dissolved;

[0046] L4. Add the essence, preservative, sodium citrate, stir until uniform, after cooling to room temperature, add citric acid, adjust the pH to 6.5-7.5, to obtain the high-efficiency bacteriostatic tableware detergent composition.

[0047] The present application has the following beneficial effects:

[0048] 1. The high-efficiency bacteriostatic tableware detergent composition provided by the present application takes dodecylbenzenesulfonic acid, cationic surfactant, and modified silicone as main components, and has a weakly acidic to neutral formula system with a pH controlled at 6.5-7.5. The prepared composition has a high-efficiency bacteriostatic effect, with a bacteriostatic rate on Staphylococcus aureus of greater than 90%, excellent detergency, lower raw material cost, and stability under various conditions.

[0049] 2. The tableware detergent of the present application contains a high content of dodecylbenzenesulfonic acid, which is neutralized by sodium hydroxide to obtain the corresponding anionic surfactant dodecylbenzenesulfonate. After compounding with specific cationic surfactant hydroxyethyl alkyl dimethyl ammonium chloride, modified silicone, and other components, the cationic charge in the composition can interact with the negative charge on the bacterial cell membrane, destroy the integrity of the bacterial cell wall, and make the bacteria lose protection. The modified silicone has certain cationic properties and also has a hydrophilic functional group, so it has higher affinity and permeability to the bacterial cell wall; its cationic property can reduce the repulsion between the negative charge of dodecylbenzenesulfonate and the negative charge of the bacterial cell membrane through a cationic bridge, so that the hydrophobic carbon chain of a large amount of dodecylbenzenesulfonate can more easily enter the cytoplasm of the bacteria through the cationic charge bridge across the cell membrane, and the benzene ring in the dodecylbenzenesulfonate has good degreasing power and can destroy the protein structure in the cell, ultimately leading to the death of the bacteria, thereby achieving the effect of inhibiting the growth and reproduction of bacteria. DETAILED DESCRIPTION

[0050] In order to more clearly illustrate the technical solutions of the present application, the following examples are listed. The raw materials, reactions, and post-treatment means appearing in the examples are all common raw materials on the market and technical means well known to those skilled in the art, unless otherwise stated.

[0051] The words "preferred", "preferably", "more preferred" and the like in the present application refer to the embodiments of the present application that can provide certain beneficial effects in certain cases. However, other embodiments can also be preferred in the same or other cases. In addition, the description of one or more preferred embodiments does not imply that other embodiments are not usable, nor is it intended to exclude other embodiments from the scope of the present application.

[0052] It should be understood, that, except in any operating examples, or otherwise indicated herein and that the statement of amounts of ingredients or of all numbers in the specification and claims, are understood as being preceded by the word "about". It is also to be understood that the numerical parameters set forth in the following description and attached claims are approximations that can vary depending upon the desired properties sought to be obtained in accordance with the present application.

[0053] The temperature in the embodiments of the present application, if not specifically stated, refers to room temperature.

[0054] The hydroxyethyl lauryl dimethyl ammonium chloride in the embodiments of the present application is a cationic surfactant, and the brand is Clariant PRAEPAGEN HY with a content of 50%.

[0055] The dodecyl benzene sulfonic acid in the embodiments of the present application is purchased from Anhui Jintong.

[0056] The AES in the embodiments of the present application is a fatty alcohol polyoxyethylene sulfate with a content of 70%, a fatty alcohol carbon atom number of 12-14, and an average ethoxylation degree of 2, and is an anionic surfactant, which is purchased from Anhui Jintong.

[0057] The sodium cocoyl glutamate in the embodiments of the present application is an amphoteric surfactant with a content of 30%, which is purchased from Guangzhou Tianci.

[0058] The APG in the embodiments of the present application is an alkyl glycoside with a content of 50%, which is a non-ionic surfactant, and is purchased from Shanghai Fuke.

[0059] The AEO9 in the embodiments of the present application is a fatty alcohol polyoxyethylene ether with a fatty alcohol carbon atom number of 12-14 and an average ethoxylation degree of 9, which is a non-ionic surfactant, and is purchased from BASF.

[0060] The preservative in the embodiments of the present application is a mixture of methyl isothiazolinone and chloromethyl isothiazolinone, which is purchased from DuPont HG Kathon series.

[0061] The citric acid in the embodiments of the present application is a pH regulator, which is purchased from Guangzhou Reagent Factory.

[0062] The sodium hydroxide in the embodiments of the present application is a neutralizing agent, which is purchased from Guangzhou Reagent Factory.

[0063] The methoxy polyethylene glycol glycidyl ether in the embodiments of the present application has an average molecular weight of 1000.

[0064] In the embodiments of the present application, the preparation method of the modified organosilicon includes the following steps:

[0065] S1. 60 g octamethylcyclotetrasiloxane was added to 150 g water, heated to 70℃, then 10 g KH550 and 2 wt% of dodecylbenzenesulfonic acid of the reaction system, as well as a trace amount of emulsifier OP-10, 70℃ for 12 h, after cooling, adjust the pH to 7 with 25% ammonia, centrifugal, remove the solvent to obtain the intermediate product;

[0066] S2. 10 g of methoxy polyethylene glycol glycidyl ether was added to the intermediate product, and reacted at 60℃ for 1 h to obtain the modified silicone.

[0067] The ingredients and corresponding mass fractions in the high-efficiency bacteriostatic dishwashing detergent compositions of Examples 1-4 are shown in Table 1.

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

[0069]

[0070]

[0071] The preparation method of the high-efficiency bacteriostatic dishwashing detergent compositions of Examples 1-4 includes the following steps:

[0072] L1. According to the above mass fraction, deionized water was added to a container, then sodium hydroxide was added, followed by dodecylbenzenesulfonic acid, and stirred until dissolved;

[0073] L2. Add AES, AEO9, APG, sodium cocoyl glutamate, and stir until dissolved;

[0074] L3. Add modified silicone and hydroxyethyl lauryl dimethyl ammonium chloride, and stir until dissolved;

[0075] L4. Add fragrance, preservative, sodium citrate, stir until uniform, then add citric acid after cooling to room temperature, adjust the pH to 6.5-7.5 to obtain the high-efficiency bacteriostatic dishwashing detergent composition.

[0076] Based on the example setting, Comparative Examples 1-3, the ingredients and corresponding mass fractions in the dishwashing detergent compositions of Comparative Examples 1-3 are shown in Table 2.

[0077] Table 2 Ingredients and their mass fractions in Comparative Examples 1-3

[0078]

[0079] The difference between Comparative Examples 1-3 and the examples is that Comparative Example 1 removes the modified silicone and the hydroxyethyl lauryl dimethyl ammonium chloride; Comparative Example 2 reduces the content of dodecyl benzene sulfonic acid; Comparative Example 3 removes the modified silicone and replaces the hydroxyethyl lauryl dimethyl ammonium chloride with benzalkonium chloride of the same mass, and the other ingredients and preparation methods are the same as in the examples.

[0080] Test Example 1

[0081] The detergent compositions obtained in the examples and comparative examples were subjected to antibacterial testing.

[0082] The antibacterial effect test was carried out according to the suspension quantitative method in QB / T 2738-2005, and Staphylococcus aureus was used as a representative of the bacteria.

[0083] The test results are shown in Table 3.

[0084] Table 3 Antibacterial test results

[0085] sample Antibacterial rate (%) Example 1 95.3 Example 2 >99 Example 3 >99 Example 4 >99 Comparative Example 1 66.5 Comparative Example 2 57.9 Comparative Example 3 30.8

[0086] According to Table 3, the antibacterial rates of Examples 1-4 are all greater than 90%, which meet the requirements of strong antibacterial. However, Comparative Example 1 does not add the two raw materials of modified silicone and hydroxyethyl lauryl dimethyl ammonium chloride, so that the antibacterial rate is less than 90%, and the effect is not ideal; Comparative Example 2 has a low dosage of dodecyl benzene sulfonic acid, which cannot effectively play a synergistic effect with the two raw materials of modified silicone and hydroxyethyl lauryl dimethyl ammonium chloride, and the antibacterial effect is poor; Comparative Example 3 uses benzalkonium chloride to replace hydroxyethyl lauryl dimethyl ammonium chloride, which is not compatible with anionic surfactants and can easily produce negative effects, resulting in a significant decrease in antibacterial effect.

[0087] Test Example 2

[0088] The detergent compositions obtained in the examples and comparative examples were subjected to soil removal capacity testing.

[0089] The soil removal capacity test was carried out according to the foam position method in Appendix A.2 of GB / T 9985-2022.

[0090] The test results are shown in Table 4.

[0091] Table 4 Soil removal test results

[0092]

[0093]

[0094] According to Table 4, it can be concluded that the high-efficiency bacteriostatic tableware detergent compositions of Examples 1-4 have better detergency than Comparative Examples 1-3. The Examples have excellent detergency by compounding a high content of dodecylbenzenesulfonic acid with a cationic surfactant and a modified silicone. The detergency of Comparative Examples 1-3 is relatively poor due to the reduced amount of dodecylbenzenesulfonic acid. In particular, Comparative Example 3 has a significantly reduced detergency because the strong cationic surfactant benzalkonium chloride is used to replace hydroxyethyl lauryl dimethyl ammonium chloride, which is incompatible with anionic surfactants.

[0095] Test Example 3

[0096] The detergent compositions obtained in the Examples and Comparative Examples were subjected to stability tests.

[0097] The specific indicators for testing the stability of the detergent are as follows:

[0098] Normal temperature stability: The sample was placed at room temperature for 4 weeks, and the appearance was observed.

[0099] Low temperature stability: The sample was placed in a refrigerator at 0°C for 4 weeks, and the appearance was observed after recovery to room temperature.

[0100] High temperature stability: The sample was placed in an oven at 45°C for 4 weeks, and the appearance was observed after recovery to room temperature.

[0101] The test results are shown in Table 5.

[0102] Table 5: Stability test results

[0103]

[0104] According to Table 5, it can be concluded that the high-efficiency bacteriostatic tableware detergent compositions of Examples 1-4 have good stability, while Comparative Example 3 has a precipitation and stratification phenomenon. This is because benzalkonium chloride is used to replace hydroxyethyl lauryl dimethyl ammonium chloride, which is incompatible with anionic surfactants.

[0105] It is apparent to those skilled in the art that the present application is not limited to the details of the foregoing exemplary embodiments, and that the present application can be implemented in other specific forms without departing from the spirit or essential characteristics of the present application. Therefore, the embodiments should be considered in all respects as illustrative and not restrictive, and the scope of the present application should be defined by the appended claims rather than the above description, and all changes coming within the meaning and range of equivalency of the claims are intended to be embraced therein.

[0106] Furthermore, it should be understood that although the specification is described in terms of embodiments, not every embodiment includes every feature described. The specification can include implicit combinations of explicitly mentioned features and / or explicit combinations of implicitely mentioned features. Each embodiment depends on the explicit combinations of features and / or the implicit combinations of features made specifically within that embodiment, and each such embodiment can be combined with every other such embodiment to create further embodiments.

Claims

1. A high performance bacteriostatic dishwashing detergent composition characterized in that, The high-efficiency bacteriostatic tableware detergent composition comprises the following components by mass fraction: Modified silicone 0.2-2% Cationic surfactant 0.2-2% Dodecyl benzene sulfonic acid 7-12% Other surfactants 8-15.5% Auxiliary agent 0.1-2% Water balance; The modified silicone is obtained by the reaction of octamethylcyclotetrasiloxane, KH550 and polyethylene glycol glycidyl ether; The preparation method of the modified silicone comprises the following steps: S1. Blending octamethylcyclotetrasiloxane, KH550 and a catalyst, heating and reacting, adjusting pH to obtain an intermediate product; S2. Blending polyethylene glycol glycidyl ether with the intermediate product, heating and reacting to obtain the modified silicone; In step S1, the temperature of the heating and reaction is 50-80℃, and the time is 10-20 h; In step S2, the temperature of the heating and reaction is 50-70℃, and the time is 1-2 h; The cationic surfactant is hydroxyethyl lauryl dimethyl ammonium chloride; The other surfactants are a mixture of AES, AEO9, APG and sodium cocoyl glutamate; The auxiliary agent is selected from a mixture of preservatives, neutralizing agents, pH adjusting agents and salts.

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