CN117821177A - High-efficiency antibacterial tableware detergent composition and preparation method thereof - Google Patents

Abstract

The invention discloses a high-efficiency antibacterial tableware detergent composition, which comprises the following components in parts by mass: 0.2-2% of modified organosilicon, 0.2-2% of cationic surfactant, 7-12% of dodecylbenzene sulfonic acid, 8-15.5% of other surfactants, 0.1-2% of auxiliary agent and the balance of water; wherein the modified organosilicon is obtained by reacting octamethyl cyclotetrasiloxane with KH550 and polyethylene glycol glycidyl ether. The modified organosilicon of the invention is compounded with specific cationic surfactant, dodecyl benzene sulfonic acid and other components, has higher penetrability to bacterial cells, can destroy the structures of shells, proteins and the like in the cells more efficiently, and inhibits the growth and propagation of the cells. The invention complements each other through the synergistic effect among a plurality of components, so that the decontamination, bacteriostasis and stability of the detergent composition are obviously improved, and the cost is lower at the same time, thereby having good application prospect.

Description

High-efficiency antibacterial tableware detergent composition and preparation method thereof

Technical Field

The invention belongs to the technical field of detergents. Mainly relates to a high-efficiency antibacterial tableware detergent composition and a preparation method thereof.

Background

At present, the tableware detergent industry has the phenomenon of high homogenization, and the products are different in size. The development of dishwashing detergents should be guided by consumer demands and innovations should be made in the product. The research data show that the conventional dish detergent products on the market have good degreasing effect basically, and the products are further favored by consumers, so that the antibacterial/bacteriostatic functions of the detergent are gradually focused on besides the washing capability and the washing hand feeling. However, considering the requirements of the daily chemical industry on factors such as toxicity and cost, currently, antibacterial agents such as triclosan, triclocarban, parachlorometaxylenol, chlorine dioxide and the like are mainly used in the detergent with antibacterial performance. The traditional antibacterial/bacteriostatic agent has the advantages of strong effect and low dosage, but most of the traditional antibacterial/bacteriostatic agents have low toxicity. Therefore, the development of the tableware detergent with high-efficiency antibacterial effect, safety, stability and low cost has a certain market prospect.

The prior art, such as CN1142994C, discloses a sterilizing detergent and a production method thereof, wherein the sterilizing detergent is prepared from chlorine dioxide, fatty alcohol polyoxyethylene ether sodium sulfate, fatty acyl diethanol amine, sodium dodecyl benzene sulfonate, ethylenediamine tetraacetic acid, sodium tetraborate and deionized water according to a proportion, and the sterilizing agent used by the sterilizing detergent has strong chlorine dioxide antibacterial capability, but is not stable enough, is easy to volatilize and has irritation. However, the composition of the technical scheme has the advantages of limited antibacterial effect, unstable product, high cost and unsatisfied high-efficiency antibacterial effect, and is safe, stable and low-cost.

In view of the foregoing, there is a need to develop a new technical solution to solve the problems in the prior art.

Disclosure of Invention

Based on the above, the invention provides a high-efficiency antibacterial tableware detergent composition and a preparation method thereof, and the detergent has high-efficiency antibacterial effect, is safe to organisms, is nontoxic and has low cost.

An object of the present invention is to provide a highly effective bacteriostatic dishwashing detergent composition comprising the following ingredients in mass fraction:

wherein the modified organosilicon is obtained by reacting octamethyl cyclotetrasiloxane with KH550 and polyethylene glycol glycidyl ether.

Further, the preparation method of the modified organic silicon comprises the following steps:

s1, mixing octamethyl cyclotetrasiloxane, KH550 and a catalyst, heating for reaction, and regulating pH to obtain an intermediate product;

s2, blending polyethylene glycol glycidyl ether with the intermediate product, and heating for reaction to obtain the modified organosilicon.

Further, in the step S1, the temperature of the heating reaction is 50-80 ℃ and the time is 10-20h.

Further, in the step S2, the temperature of the heating reaction is 50-70 ℃ and the time is 1-2h.

Further, the catalyst is dodecylbenzene sulfonic acid.

In the modified organosilicon, octamethyl cyclotetrasiloxane (D4) and an aminosilane coupling agent KH550 are reacted at first, so that D4 and KH550 are subjected to ring-opening polymerization to obtain an intermediate product with amino groups introduced, and then the amino groups in the intermediate product are reacted with polyethylene glycol glycidyl ether containing epoxy groups to realize grafting of alkoxy polyether chain segments, and a large amount of amino groups and alkoxy long chains are introduced into hydrophobic D4 to realize hydrophilic modification, and meanwhile, the modified organosilicon has weak cationic property, thereby greatly improving the emulsification and dispersion effects of the composition, improving the stability of the product, ensuring that the product is not easy to delaminate and precipitate and has better decontamination effect. Meanwhile, the modified organosilicon is compounded with components such as a specific cationic surfactant, dodecylbenzene sulfonic acid and the like, has higher penetrability to bacterial cells, can damage structures such as shells, proteins and the like in the cells more efficiently, and inhibits growth and propagation of the cells.

Further, the cationic surfactant has the following structural formula:

[R-N ⁺ (CH ₃ ) ₂ -CH ₂ -CH ₂ -OH]Cl-；

the R is selected from alkyl with 12-14 carbon atoms.

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

Further, the other surfactant is selected from one or more of anionic surfactant, nonionic surfactant and zwitterionic surfactant.

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

In particular, the alkyl of the secondary alkyl sulfonate is preferably C12-C14, preferably sodium salt, and the secondary alkyl sulfonate has extremely strong penetrability under the conditions of strong alkali and high temperature and has the functions of emulsification, deoiling and washing.

Specifically, the fatty acid methyl ester sulfonate is preferably C12-C14, has good water solubility, has better cleaning capability in a high-hardness environment, and has balanced decontamination, foaming, surface wetting and permeability.

In particular, the fatty alcohol polyoxyethylene sulfate, alkyl is preferably C12-C14, polyoxyethylene represents the average degree of ethoxylation, and EO number is preferably 0.5-3.

In particular, the fatty alcohol-polyoxyethylene carboxylate is an alkyl group, preferably a C12-C14 alkyl group, wherein the alkyl group is a linear alkyl group or a branched alkyl group, polyoxyethylene represents an average ethoxylation degree, and EO number is preferably 2-10.

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 and fatty acid ester ethoxylate.

In particular, the alkyl glycoside, the alkyl of which is preferably C12-14, has excellent foaming, emulsifying, dispersing and detergency.

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 C12-15 carbon number, the fatty alcohol is a straight-chain alcohol or an isomeric alcohol, polyoxyethylene represents the average ethoxylation degree, and EO number is preferably 3-10.

In particular, the secondary alcohol polyoxyethylene ether, the alkyl of which is preferably C12-C14, polyoxyethylene represents the average ethoxylation degree, the EO number is preferably 9-15, has better wettability and permeability than AEO9, and can resist gel in a concentrated system.

In particular, said fatty alcohol EO-PO block polyether, preferably a C12-C15 linear or branched alkyl, polyoxyethylene representing the average degree of ethoxylation, the EO number preferably being from 2 to 10; the polyoxypropylene represents an average degree of propoxylation, and the PO number is preferably 2 to 5.

In particular, the fatty acid ester ethoxylates, preferably C12-C14 alkyl groups, polyoxyethylene represents the average degree of ethoxylation, and EO numbers are preferably from 6 to 15.

Further, the zwitterionic surfactant is selected from one or more of amino acid type surfactant, amine oxide type surfactant, betaine type surfactant and imidazoline surfactant.

Further, the auxiliary agent is selected from one or more of preservative, solvent, enzyme preparation, anti-redeposition agent, neutralizing agent, pH regulator, essence and salt.

Further, the enzyme preparation is selected from one or more of protease, lipase and amylase.

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

Further, the anti-redeposition agent is selected from one or more of sodium polyacrylate, maleic acid acrylic acid copolymer, carboxymethyl cellulose, homo-and copolymers of vinyl pyrrolidone.

Further, the solvent is one or more selected from glycerol, propylene glycol, ethanol and polyethylene glycol.

Further, the neutralizer is selected from one or more of sodium hydroxide and potassium hydride.

Specifically, the salt is selected from one or more of halogen salt, carbonate, bicarbonate, formate, acetate, sulfate, nitrate and citrate.

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

Another object of the present invention is to provide a process for preparing the above-mentioned high-efficiency bacteriostatic dishwashing detergent composition comprising the steps of:

l1, adding deionized water into a container according to the mass fraction, then adding sodium hydroxide, then adding dodecylbenzene sulfonic acid, and stirring until the mixture is dissolved;

l2, adding AES, AEO9, APG and sodium cocoyl glutamate, and stirring to dissolve;

l3, adding modified organic silicon and hydroxyethyl lauryl dimethyl ammonium chloride, and stirring until the mixture is dissolved;

and L4, adding essence, preservative and sodium citrate, stirring uniformly, cooling to room temperature, adding citric acid, and regulating pH to 6.5-7.5 to obtain the efficient antibacterial tableware detergent composition.

The invention has the following beneficial effects:

1. the invention provides a high-efficiency antibacterial tableware detergent composition, which takes dodecylbenzene sulfonic acid, cationic surfactant and modified organosilicon as main components, and is a weakly acidic to neutral formula system, and the pH is controlled to be 6.5-7.5. The prepared composition has high-efficiency antibacterial effect, the antibacterial rate to staphylococcus aureus is more than 90%, the detergency is excellent, the raw material cost is low, and the composition is stable under various conditions.

2. The tableware detergent contains high-content corresponding anionic surface active dodecyl benzene sulfonate obtained by neutralizing dodecyl benzene sulfonic acid with sodium hydroxide, and after the high-content dodecyl benzene sulfonate is compounded with specific cationic surface active hydroxyethyl alkyl dimethyl ammonium chloride, modified organic silicon and other components, the cationic charge in the composition can interact with negative charges on bacterial cell membranes to damage the integrity of bacterial cell walls and ensure that bacteria are not protected. The modified organosilicon has certain cationic property and hydrophilic functional groups, so that the modified organosilicon has higher affinity and penetrability to bacterial cell walls; the attached cationic property of the dodecyl benzene sulfonate can reduce the repulsive property of the negative charge of the dodecyl benzene sulfonate and the negative charge of a bacterial cell membrane through a cationic bridge, so that a large number of hydrophobic carbon chains of the dodecyl benzene sulfonate enter the cytoplasm of bacteria through the cell membrane more easily through the cationic charge bridge, and benzene rings in the dodecyl benzene sulfonate have better degreasing force, can damage protein structures in the cells, and finally lead to bacterial death, thereby realizing the effect of inhibiting bacterial growth and reproduction.

Detailed Description

In order to more clearly illustrate the technical solution of the present invention, the following examples are set forth. The starting materials, reactions and workup procedures used in the examples are those commonly practiced in the market and known to those skilled in the art unless otherwise indicated.

The words "preferred," "more preferred," and the like in the present disclosure refer to embodiments of the present disclosure that may provide certain benefits in some instances. However, other embodiments may 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.

It should be understood that, except in any operating examples, or where otherwise indicated, quantities or 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 attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention.

The temperatures in the examples of the present invention, unless otherwise specified, refer to room temperature.

The hydroxyethyl lauryl dimethyl ammonium chloride in the embodiment of the invention is a cationic surfactant, and the brand of the hydroxyethyl lauryl dimethyl ammonium chloride is the chemical PRAEPAGEN HY of the Clariant, and the content of the hydroxyethyl lauryl dimethyl ammonium chloride is 50%.

Dodecylbenzene sulfonic acid in the examples of the present invention was purchased from jatropha curcas.

The AES, the fatty alcohol polyoxyethylene sulfate, the 70% content, the fatty alcohol carbon number of 12-14, the average degree of ethoxylation of 2 and the anionic surfactant are purchased from the Mallotus japonicus.

The sodium cocoyl glutamate of the present examples, 30% content, zwitterionic surfactant, was purchased from the canthus.

APG, alkyl glycoside, 50% content, nonionic surfactant in the examples of the present invention were purchased from Shanghai makinje.

AEO9, fatty alcohol polyoxyethylene ether, fatty alcohol with 12-14 carbon atoms, average ethoxylation degree of 9, nonionic surfactant, and the like are purchased from Basoff company.

The preservative in the examples of the present invention is a mixture of methylisothiazolinone and chloromethyl isothiazolinone, available from Dupont HG kathon series.

Citric acid, a pH adjuster, in the examples of the present invention was purchased from guangzhou reagent factories.

The sodium hydroxide in the examples of the present invention is a neutralizing agent, purchased from guangzhou reagent plant.

The average molecular weight of the methoxypolyethylene glycol glycidyl ether in the embodiment of the invention is 1000.

In the embodiment of the invention, the preparation method of the modified organic silicon comprises the following steps:

s1, adding 60g of octamethyl cyclotetrasiloxane into 150g of water, heating to 70 ℃, then adding 10g of KH550, 2wt% of dodecylbenzene sulfonic acid of a reaction system, and a micro-emulsifier OP-10, reacting for 12 hours at 70 ℃, cooling, adjusting the pH to 7 by using 25% ammonia water, centrifuging, and removing a solvent to obtain an intermediate product;

s2, adding 10g of methoxy polyethylene glycol glycidyl ether into the intermediate product, and reacting at 60 ℃ for 1h to obtain the modified organosilicon.

The ingredients and corresponding mass fractions of the high-potency bacteriostatic dishwashing detergent compositions of examples 1-4 are shown in table 1.

TABLE 1 Components and mass fractions of examples 1-4

The process for preparing the high-performance bacteriostatic dishwashing detergent compositions of examples 1-4 comprises the steps of:

l1, adding deionized water into a container according to the mass fraction, then adding sodium hydroxide, then adding dodecylbenzene sulfonic acid, and stirring until the mixture is dissolved;

l2, adding AES, AEO9, APG and sodium cocoyl glutamate, and stirring to dissolve;

l3, adding modified organic silicon and hydroxyethyl lauryl dimethyl ammonium chloride, and stirring until the mixture is dissolved;

and L4, adding essence, preservative and sodium citrate, stirring uniformly, cooling to room temperature, adding citric acid, and regulating pH to 6.5-7.5 to obtain the efficient antibacterial tableware detergent composition.

Comparative examples 1-3 were set based on the examples, and the ingredients and corresponding mass fractions in the dishwashing detergent compositions of comparative examples 1-3 are shown in table 2.

TABLE 2 Components and mass fractions of comparative examples 1-3

Comparative examples 1 to 3 differ from the examples in that: comparative example 1 modified silicone and hydroxyethyllauryldimethyl ammonium chloride were removed; comparative example 2 reduced dodecylbenzenesulfonic acid content; comparative example 3 modified silicone was removed and hydroxyethyllauryldimethyl ammonium chloride was replaced with equal mass of benzalkonium chloride, and the other ingredients and preparation methods were the same as in the example.

Test example 1

The detergent compositions obtained in the examples and comparative examples were subjected to antibacterial tests.

Antibacterial effect test was performed according to the suspension quantification method in QB/T2738-2005, and Staphylococcus aureus was used as a representative strain.

The test results are shown in Table 3.

TABLE 3 antibacterial test results

Sample of	Bacteriostasis 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

As can be seen from Table 3, the bacteriostasis rates of examples 1-4 are all greater than 90%, and all meet the requirements of strong bacteriostasis. In the comparative example 1, as modified organic silicon and hydroxyethyl lauryl dimethyl ammonium chloride are not added, the antibacterial rate is less than 90%, and the effect is not ideal; in the comparative example 2, the dosage of the dodecylbenzene sulfonic acid is low, so that the synergistic effect cannot be effectively exerted on two raw materials of the modified organic silicon and the hydroxyethyl lauryl dimethyl ammonium chloride, and the antibacterial effect is poor; comparative example 3 because of the replacement of hydroxyethyl lauryl dimethyl ammonium chloride with benzalkonium chloride, which is incompatible with anionic surfactants, antagonism was easily negative, resulting in a greatly reduced bacteriostatic effect.

Test example 2

The detergent compositions obtained in examples and comparative examples were subjected to detergency tests.

Detergency tests were carried out according to the foam level method of appendix A.2 in GB/T9985-2022.

The test results are shown in Table 4.

Table 4 decontamination test results

As can be seen from Table 4, the high-performance bacteriostatic dishwashing detergent compositions of examples 1-4 have better detergency than comparative examples 1-3, and the examples impart excellent detergency to the products by compounding high levels of dodecylbenzenesulfonic acid with cationic surfactant, modified silicone. While comparative examples 1 to 3 were also relatively poor in detergency due to the reduced amount of dodecylbenzenesulfonic acid, especially comparative example 3, because the use of the strong cationic surfactant benzalkonium chloride instead of hydroxyethyllauryl dimethyl ammonium chloride was incompatible with the anionic surfactant, resulting in a significant decrease in detergency.

Test example 3

The detergent compositions obtained in the examples and comparative examples were subjected to stability test.

The specific investigation indexes of the detergent stability are as follows:

stability at normal temperature: the samples were left at room temperature for 4 weeks to observe appearance;

low temperature stability: placing the sample in a refrigerator at 0 ℃ for 4 weeks, recovering the room temperature, and observing the appearance;

high temperature stability: the sample was placed in an oven at 45 ℃ for 4 weeks, allowed to return to room temperature, and observed for appearance.

The test results are shown in Table 5.

TABLE 5 stability test results

As can be seen from Table 5, the highly bacteriostatic dishwashing detergent compositions of examples 1-4 of the present invention have good stability, while comparative example 3 shows precipitation delamination due to the replacement of hydroxyethyllauryl dimethyl ammonium chloride with benzalkonium chloride, which is incompatible with anionic surfactants.

It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.

Claims (9)

1. The efficient antibacterial tableware detergent composition is characterized by comprising the following components in parts by mass:

wherein the modified organosilicon is obtained by reacting octamethyl cyclotetrasiloxane with KH550 and polyethylene glycol glycidyl ether.

2. A highly effective bacteriostatic dishwashing detergent composition according to claim 1, characterized in that said modified silicone is prepared by a process comprising the steps of:

s1, mixing octamethyl cyclotetrasiloxane, KH550 and a catalyst, heating for reaction, and regulating pH to obtain an intermediate product;

s2, blending polyethylene glycol glycidyl ether with the intermediate product, and heating for reaction to obtain the modified organosilicon.

3. A highly bacteriostatic dishwashing detergent composition according to claim 2, wherein in step S1, said heating reaction is carried out at a temperature of 50-80 ℃ for a period of 10-20 hours.

4. A highly bacteriostatic dishwashing detergent composition according to claim 2, wherein in step S2, the heating reaction is carried out at a temperature of 50-70 ℃ for a period of 1-2 hours.

5. A highly effective bacteriostatic dishwashing detergent composition according to claim 1, wherein said cationic surfactant has the following structural formula:

[R-N ⁺ (CH ₃ ) ₂ -CH ₂ -CH ₂ -OH]Cl ^- ；

the R is selected from alkyl with 12-14 carbon atoms.

6. A high-performance bacteriostatic dishwashing detergent composition according to claim 1, wherein said other surfactant is selected from one or more of anionic, nonionic and zwitterionic surfactants.

7. A high-efficiency bacteriostatic dishwashing detergent composition according to claim 1, wherein said adjunct is selected from one or more of preservatives, solvents, enzyme preparations, anti-redeposition agents, neutralising agents, pH-adjusting agents, fragrances and salts.

8. A highly bacteriostatic dishwashing detergent composition according to claim 7, wherein said enzyme preparation is selected from one or more of proteases, lipases and amylases.

9. A process for preparing a highly effective bacteriostatic dishwashing detergent composition according to any one of claims 1-8, characterized in that said process for preparing a highly effective bacteriostatic dishwashing detergent composition comprises the steps of:

l1, adding deionized water into a container according to the mass fraction, then adding sodium hydroxide, then adding dodecylbenzene sulfonic acid, and stirring until the mixture is dissolved;

l2, adding AES, AEO9, APG and sodium cocoyl glutamate, and stirring to dissolve;

l3, adding modified organic silicon and hydroxyethyl lauryl dimethyl ammonium chloride, and stirring until the mixture is dissolved;

and L4, adding other auxiliary agents, stirring uniformly, cooling to room temperature, adding citric acid, and regulating the pH to 6.5-7.5 to obtain the efficient antibacterial tableware detergent composition.