CN113698998A

CN113698998A - Stable detergent composition with antibacterial effect

Info

Publication number: CN113698998A
Application number: CN202111132531.2A
Authority: CN
Inventors: 江丹; 李淑钰; 钟美; 刘艳珍; 邱振名; 黄亮; 张利萍; 沈兵兵
Original assignee: Guangzhou Liby Enterprise Group Co Ltd
Current assignee: Guangzhou Liby Enterprise Group Co Ltd
Priority date: 2021-09-26
Filing date: 2021-09-26
Publication date: 2021-11-26
Anticipated expiration: 2041-09-26
Also published as: CN113698998B

Abstract

The invention relates to a stable detergent composition with antibacterial effect, and relates to the technical field of daily chemical industry. The stable detergent composition with antibacterial efficacy comprises 0.3 to 1.1 percent of a stability promoting system by mass percent, wherein the stability promoting system has the following characteristics: the stabilization promoting system is a mixture of component A1 and component A2; the component A1 is selected from a complexone type complexing agent; component A2 is selected from compounds containing boron element; the detergent composition contains 0.05-0.15% of component A1 and 0.2-1% of component A2. The stable and antibacterial detergent composition provided by the invention can ensure that the detergent composition has good capability of resisting microbial contamination, greatly reduces risks caused by microbial contamination, maintains good protease stability and preservative stability of the detergent composition, and maintains good appearance stability and odor stability of the detergent composition.

Description

Stable detergent composition with antibacterial effect

Technical Field

The invention relates to the technical field of daily chemical industry, in particular to a stable detergent composition with antibacterial effect.

Background

The liquid detergent contains a large amount of water and organic substances, so that a good nutrient source is provided for the growth of microorganisms; meanwhile, the products are neutral and non-oxidation-reduction products, so that the products are easily polluted by microorganisms. The production process of the daily chemical liquid detergent product is simple, the daily chemical liquid detergent product is generally not subjected to a sterilization or degerming process like the production of food and medicines, and the daily chemical liquid detergent product is a commodity which is repeatedly used for many times, so that the risk of deterioration caused by microbial contamination is higher. Currently, there are many detergent products on the market that claim to have antibacterial and bacteriostatic efficacy. Although these products are added with antibacterial components, the products often have antibacterial spectrum, and the antibacterial spectrum is single, so the products are also polluted by microorganisms to cause the risk of deterioration.

In order to ensure the stability of the efficiency of the detergent in different scenes such as production, transportation, sale and use, the daily chemical industry adopts a corrosion resistance challenge test to evaluate the tolerance capability of a liquid detergent product to microbial pollution. Currently, there is no standardized test method available internationally for laundry products. Preservative challenge tests are most used internationally to screen preservative systems. This method is primarily evaluated for the resistance of the wash product to contamination by free bacteria and fungi.

It is mentioned in patent CN111304281A that the contamination of liquid detergent products is mainly caused by bacteria, and therefore the preservative efficacy of liquid detergent products against bacteria is particularly important. Lilongjie et al isolated and screened a bacterium from a putrefactive sample containing an isothiazolinone preservative and found that the bacterium has a biofilm-producing property. Isolation and identification of biofilm-producing strains and analysis of its biofilm-producing properties [ J ] china journal of bioengineering, 2013, 33 (11): 38-43 Bridier et al reviewed the results of others and indicated that biofilms were significantly more resistant to disinfectants than free bacteria. [ Bridier A, Briandet R, Thomas V, et a1. Resistence of bacterial biolofils to pathogens: a review [ J ]. Biofaulng, 2014, 27 (9): 1017-1032] on one hand, because the bactericide is generally a molecule with high chemical reaction, the existence of organic substances such as protein, nucleic acid, polysaccharide and the like can greatly weaken the efficacy of the bactericide; on the other hand, the bactericide is effective only when it comes into direct contact with bacteria, and extracellular polymers in the biofilm become a transport-limiting factor of the bactericide. Cationic biocides such as quats have difficulty penetrating negatively charged biofilms due to charge attraction. In the biofilm of pseudomonas aeruginosa, the longer the carbon chain length of benzalkonium chloride, the more resistant the biofilm is. Hydrogen peroxide also only penetrates and partially kills cells in biofilms formed by the absence of catalase. At the same time, diffusion-limited penetration of the antimicrobial agent by the biofilm may also result in lower levels of antimicrobial agent exposure in deeper regions of the biofilm, and thus adaptation of cells within the biofilm to sub-lethal concentrations of the antimicrobial agent. In a third aspect, the growth of biofilms is associated with the physiological adaptation of cells, which may also lead to increased resistance to antiseptics, from the development of cell attachment to three-dimensional structures. US20150342848a1 also mentions that bacterial cells in biofilms are up to 500 times more resistant to certain antimicrobial agents than planktonic cells.

The bacteria are present in the biofilm in an aggregated form which imparts a physiological characteristic that distinguishes them from free states. The bacteria in the aggregation state can resist harsh environment, have higher drug resistance and activity, and have certain difference with the free state microorganisms in metabolic behavior. Once the bacteria live and multiply in the liquid product in an aggregated state, the bacteria can cause obvious changes in the efficacy of the liquid product in a short time; for example, odor changes produce off-flavors, appearance changes produce turbidity, and preservatives are depleted.

In summary, the evaluation test of the resistance of liquid products to microbial contamination should take account of both free and aggregated bacteria. Although patent CN111304281A provides an evaluation method for evaluating the biofilm inhibition efficacy of liquid detergent products using biofilm, no idea and direction for developing biofilm-resistant liquid detergents are given.

The chelating agent and the boron-containing compound have a decomposing and inhibiting effect on the biofilm. US20150342848a1 discloses the use of chelating agents and transport enhancers (MSM or DMSO) to inhibit biofilm formation in vivo. CN108774600B discloses an endoscope cleaning humectant, wherein a biological hydrolase is used for hydrolyzing substances such as protein and extracellular polysaccharide in a biological membrane, the biological membrane is disintegrated together under the action of a cationic bactericide, and a boric acid ester compound in the humectant is used for stabilizing the hydrolase and promoting the decomposition of protease on protein pollutants. US20200296971a1 discloses a method of inhibiting and/or dispersing biofilm by applying boric acid dissolved in a solvent to the biofilm. WO2012137166a1 discloses oxoborane compounds which reduce or prevent the formation of and/or damage of biofilms in or on substrates.

It is noted that the above patents use chelating agents and boron-containing compounds alone without considering the effect of their combination, and on the other hand, the patents report the use of these materials to produce a transient biofilm-disrupting or biofilm-inhibiting effect, whether they be chelating agents or boron-containing compounds. And the object of the action is a living organism or a hard surface in vitro. The application environments of the above-mentioned subject of action and liquid detergent products are very different, and the latter is a need for an effect of continuously suppressing decomposition or inhibition of biofilm. For the shelf life of liquid detergent products, which can last for 2 to 3 years, and the service life of several months, it is critical to ensure that the odor, appearance and microbial count of the product are not significantly changed during storage and use.

It must be noted that the use of chelating agents has both advantages and disadvantages on the impact of liquid detergents. Detergent ingredients, such as proteases, preservatives often require divalent metals for stability. US8691743 reports the use of calcium ions to stabilize proteases in liquid detergents. US3870795B, US4067878B report the use of divalent metal ions to stabilize isothiazolinone compounds in preservatives. The inventor also found in previous work that, in a specific concentration range, calcium ions and magnesium ions in the sulfonic acid type surfactant and the washing water can form a complex, and the complex has a good killing or inhibiting effect on certain bacteria. Chelation of divalent cations by chelating agents in detergent compositions may lead to degradation of enzyme preparations, preservatives, and other performance degradations. Thus, improper use of the chelating agent may cause serious problems in compatibility of the components. The low temperature solubility of boron-containing compounds is also a concern and if such materials do not dissolve well in the composition, they can precipitate out resulting in an unpleasant appearance change.

Therefore, there is a need to develop a stable detergent composition with antibacterial effect, which can resist the contamination of microorganisms and maintain the stability of its properties (appearance, odor, component content), and has good antibacterial and detergency performance.

Disclosure of Invention

In order to solve the above technical problems, the present invention provides a stable detergent composition having antibacterial efficacy.

It is another object of the present invention to provide a detergent composition having good enzyme preparation stability, good preservative stability and good antibacterial effect.

It is another object of the present invention to provide a method for imparting good stability to detergent compositions.

In order to achieve the purpose, the invention adopts the following technical scheme:

the invention provides a stable detergent composition with antibacterial effect, which comprises the following components in percentage by weight:

(1)0.3 to 1.1% of a stabilization promoting system, said stabilization promoting system having the following characteristics;

(1-1) the stabilization promoting system is a mixture of component A1 and component A2;

(1-2) component A1 is selected from a complexone type complexing agent;

(1-3) component a2 is selected from compounds containing boron element;

(1-4) the content of the component A1 in the detergent composition is 0.05-0.15%, and the content of the component A2 is 0.2-1%;

(2)4 to 15 percent of sulfonic acid type surfactant;

(3) 10-20% of other surfactant;

(4)0.01 to 5 percent of enzyme preparation;

(5)0.001 to 2 percent of preservative;

(6)0.01 to 15 percent of auxiliary agent;

(7) the balance being solvent.

Ammonia carboxylic complexing agent (A1) selected from one or more of ethylenediamine tetraacetate, cyclohexanediamine tetraacetate, ethylene glycol diethyl diamine tetraacetate, ethylenediamine tetrapropionate, diethylenetriamine pentaacetate, triethylenetetramine hexaacetate or 2-hydroxyethyl ethylenediamine triacetate; the cationic portion of the salt is selected from the group consisting of sodium ions, potassium ions, ammonium ions, and ammonium ions formed from organic amines.

The compound (A2) containing boron, characterized in that:

(1) the content of boron element is 10% or more of the molecular weight of the compound (A2) containing boron element,

(2) the solubility of the compound (A2) containing boron element in 100g of pure water at 25 ℃ was more than 5 g.

The further technical proposal is that the compound (A2) containing boron element is selected from metaborate, orthoborate and polyborate; the cation part of the salt is selected from sodium ions, potassium ions, ammonium ions and ammonium ions formed by organic amine, or a mixture of one or more of the following chemical formulas (1);

R_x: a group consisting of C, H and one or more of O, N, S;

M⁺: sodium ions, potassium ions, ammonium ions, and ammonium ions formed from organic amines.

A sulfonic acid type surfactant selected from the group consisting of alkyl sulfonates, alkyl benzene sulfonates, fatty acid alkyl ester sulfonates, succinate sulfonates, alkyl alcohol polyoxyethylene ether sulfonates, sulfoalkyl esters of fatty acids, sulfoalkyl amides of fatty acids; the carbon number of the alkyl group of the sulfonic acid type surfactant is 6 to 24, and the sulfonic acid type surfactant is selected from linear alkyl and branched alkyl, and is saturated alkyl or alkyl containing one or more unsaturated double bonds; the cationic portion of the salt is selected from the group consisting of sodium ions, potassium ions, ammonium ions, and ammonium ions formed from organic amines.

Other surfactants selected from the group consisting of alkyl sulfates of C8 to C18, ethoxylated fatty alcohol sulfates of C8 to C18, fatty acid salts of C8 to C18, ethoxylated fatty alcohol ether carboxylates, fatty alcohol alkoxylates, alkyl glycosides, fatty acid alkoxylates, fatty acid alkylolamides, fatty acid methyl ester ethoxylates, mixtures of one or more of polyether surfactants.

The enzyme preparation comprises one or more of protease and amylase; the enzyme preparation further comprises a mixture of one or more of cellulase, lipase, pectinase or mannanase.

A preservative selected from the group consisting of isothiazolone derivatives including methylisothiazolinone, methylchloroisothiazolinone, benzisothiazolinone, and one or more mixtures of phenoxyl, sodium benzoate, parabens.

The auxiliary agent is selected from one or a mixture of more of polymers, inorganic salts, viscosity regulators, antibacterial agents, coloring agents, essences and pH regulators;

the solvent is water and organic solvent, and the organic solvent is selected from polyalcohol or polyalcohol ether.

The stable detergent composition with antibacterial effect is characterized in that:

(1) the antibacterial rate of the detergent composition is more than 99.9%;

(2) after undergoing an aging test, the detergent composition has an enzyme formulation retention greater than 80% after aging for 4 weeks and greater than 65% after aging for 8 weeks; the detergent composition has a preservative retention of greater than 80%; the odor, appearance of the detergent composition is not significantly changed;

(3) the detergent composition does not undergo significant changes in odor, appearance, preservative content after undergoing the microbial contamination test.

The stable and antibacterial detergent composition provided by the invention can ensure that the detergent composition has good capability of resisting microbial contamination, greatly reduces risks caused by microbial contamination, maintains good protease stability and preservative stability of the detergent composition, and maintains good appearance stability and odor stability of the detergent composition.

Detailed Description

In order to more fully understand the technical contents of the present invention, the technical solutions of the present invention will be further described and illustrated with reference to the following specific embodiments.

All percentages, parts and ratios are based on the total weight of the composition of the present invention, unless otherwise specified. All weights as they pertain to listed ingredients are assigned to levels of active material and, therefore, do not include solvents or by-products that may be included in commercially available materials, unless otherwise specified. The term "percent by weight content" may be referred to herein by the symbol "%".

All molecular weights herein are weight average molecular weights expressed in daltons, unless otherwise indicated.

All formulations and tests herein occur at 25 ℃ environment, unless otherwise indicated.

The use of "including," "comprising," "containing," "having," or other variations thereof herein, is meant to encompass the non-exclusive inclusion, as such terms are not to be construed. The term "comprising" means that other steps and ingredients can be added that do not affect the end result. The term "comprising" also includes the terms "consisting of and" consisting essentially of. The compositions and methods/processes of the present invention comprise, consist of, and consist essentially of the essential elements and limitations described herein, as well as any of the additional or optional ingredients, components, steps, or limitations described herein. The terms "potency", "performance", "effect" and "efficacy" are not distinguished from one another herein. The terms "change" and "variation" do not distinguish between them. The terms "chelating" and "complexing" do not distinguish between them. The terms "chelating agent" and "complexing agent" do not distinguish between them. The term "free" as used herein means that the additive is not added by man, and specifically means that the content is 0.01% by weight or less.

Liquid detergent composition

The liquid detergent composition of the present invention is contacted with a substrate (such as fabric articles, tableware, etc.) to be contacted in water, thereby removing stains from the surface of the substrate and achieving the purpose of cleaning the surface of the substrate.

Liquid detergent compositions typically comprise a surfactant system and other adjuncts including, but not limited to, viscosity modifiers, polymers, anti-redeposition agents, water softeners, enzyme preparations, colorants, preservatives, perfumes, pigments and the like. The detergent, liquid detergent, composition and liquid composition in the present invention are all liquid detergent compositions. Liquid detergents include, but are not limited to, the following products: laundry detergents, laundry care agents, laundry fragrances, laundry softeners, hand dishwashing detergents, fruit and vegetable detergents, range hood detergents, laundry beads, automatic dishwasher dishwashing detergents, kitchen detergents and the like and other homogeneous or multiphase cleaning product forms.

Stabilization promoting system

The stabilization promoting system of the present invention imparts the following benefits to the detergent composition: (1) resistance to microbial contamination, absence of odor from the composition due to microbial contamination, appearance, and significant changes in preservative content. (2) The antibacterial efficacy and the comprehensive stability of the composition are maintained. After the stabilizer is added to the accelerating system, the antibacterial efficiency and the comprehensive stable efficiency of the composition can still maintain the equivalent level before the addition, and the efficiency is not obviously reduced.

The stability promoting system is a mixture of a component A1 and a component A2, wherein the component A1 is selected from an ammonia carboxylic complexing agent; component a2 is selected from compounds containing elemental boron. The weight percentage content of the stabilization promoting system is 0.3 to 1.1 percent, the weight percentage content of the component A1 is 0.05 to 0.15 percent, and the weight percentage content of the component A2 is 0.2 to 1 percent.

Aminocarboxylic complexing agents

It is known in the art that the role of complexing agents is to bind metal ions and thereby reduce the concentration of free metal ions in aqueous systems. The aminocarboxylic complexing agent disclosed by the invention conforms to the following chemical general formula:

r is a group consisting of C, H, O, S, N and the like,

n is a positive integer such as 1, 2, 3.. eta.. etc.,

m + is the cationic portion of a salt selected from the group consisting of sodium, potassium, ammonium, and ammonium formed from organic amines.

In previous studies by the inventors, it was found that not all aminocarboxylic complexing agents can be used as component A1 of the stabilization promoting system. Only those complexing agents of the aminocarboxylic type which have a stability constant (log K) with respect to calcium ions of more than 8.0 and less than 15.0 can be used as component A1 of the stability-promoting system. Table 1 shows stability constants of the aminocarboxylic type complexing agent and calcium ion previously tested by the present inventors. The test conditions were 25 ℃, the ionic strength was 0.1mol/L, the metal ion was calcium ion, and the stability constant was expressed as logK.

TABLE 1 stability constants logK of chelating agents for calcium ions

The aminocarboxylic complexing agent satisfying the above conditions is component a1 of the stabilization promoting system, specifically one or a mixture of more of ethylenediaminetetraacetic acid (EDTA), cyclohexanediaminetetraacetate (DCTA), ethylenediethylenetriaminetetraacetic acid (EGTA), Ethylenediaminetetrapropionate (EDTP), Diethylenetriaminepentaacetate (DTPA), triethylenetetraminehexaacetate (TTHA), or 2-hydroxyethylethylenediaminetriacetic acid (HEDTA).

Compound containing boron element

Component a2, which is a stabilization promoting system, refers to a boron-containing compound that satisfies the following conditions:

(1) the content of boron element is 10% or more of the molecular weight of the component A2,

(2) component A2 has a solubility in 100g of pure water of greater than 5g at 25 ℃.

The molecular weight of the component A2 was calculated from the molecular weight of the compound after removal of the water of crystallization.

Further, component a2 is selected from the group consisting of metaborate, orthoborate, polyborate, the cationic portion of said salts being selected from the group consisting of sodium ions, potassium ions, ammonium ions, and ammonium ions formed from organic amines; or a mixture of one or more of the following formulae;

R_x: a group consisting of C, H and one or more of O, N, S;

Suitable examples of component A2 are sodium metaborate (boron content of 13.22%, calculated as crystal-water-free compound; solubility of 18g/100g pure water), sodium tetraborate (boron content of 21.49%, calculated as crystal-water-free compound; solubility of 26g/100g pure water), ammonium pentaborate (boron content of 27.01%, calculated as crystal-water-free compound; solubility of 10g/100g pure water).

Phenylboronic acid (boron content 8.87%, calculated as a compound without water of crystallization; solubility 10g/100g pure water), 4-formylphenylboronic acid (boron content 7.21%, calculated as a compound without water of crystallization; solubility less than 5g/100g pure water) did not meet the requirements of component A2 and could not be used as component A2.

In previous studies by the inventors it was found that there is a large correlation between the dissolution properties of the boron-containing compound and the stability of the appearance of the detergent composition. The solubility of the boron-containing compound used in the solution of the present invention needs to be greater than 5g/100g pure water. In addition, the compound with lower boron element content does not obviously improve the capability of resisting microbial contamination of the detergent composition, so the boron content of the boron-containing compound adopted in the technical scheme of the invention is more than 10%.

Sulfonic acid type surfactant

The sulfonic acid type surfactant is selected from alkyl sulfonate, alkyl benzene sulfonate, fatty acid alkyl ester sulfonate, succinate sulfonate, alkyl alcohol polyoxyethylene ether sulfonate, fatty acid sulfoalkyl ester or fatty acid sulfoalkyl amide; the carbon number of the alkyl group of the sulfonic acid type surfactant is 6 to 24, and the sulfonic acid type surfactant is selected from linear alkyl and branched alkyl, saturated alkyl or alkyl containing one or more unsaturated double bonds; the cationic portion of the salt is selected from the group consisting of sodium ions, potassium ions, ammonium ions, and ammonium ions formed from organic amines.

The present inventors have found in previous work that the loose combination of a sulfonic acid type surfactant and a divalent hard water ion such as calcium ion, magnesium ion, etc. can impart good antibacterial efficacy to a detergent composition. Hard water ions are not specially added, and the hard water ions can play a role only by enabling the hardness of the washing water of the washing system to be more than 50 ppm. The sulfonic acid type surfactant is present in the detergent composition at a level of from 4% to 15% by weight.

The alkylbenzene sulfonate satisfies the following formula:

R₁is alkyl with 6 to 24 carbon atoms, M⁺Is a cationic moiety. A suitable example is sodium dodecylbenzenesulfonate.

The alkyl chain segment of the alkyl sulfonate is a straight chain or a branched chain; is a saturated alkyl group, or an alkyl group containing one or more unsaturated double bonds. The alkyl sulfate having 6 to 24 carbon atoms in the alkyl group is preferable, and the alkyl sulfate having 8 to 18 carbon atoms is more preferable. Suitable examples are sodium dodecyl sulphate, sodium alpha-alkenyl sulphonate.

The alkyl sulfonate satisfies the following formula:

R₂-SO₃ ^-M⁺

R₂a saturated or unsaturated alkyl group having 12 to 20 carbon atoms, preferably a saturated or unsaturated alkyl group having 13 to 17 carbon atoms, M⁺Is a cationic moiety. A suitable example is sodium hexadecyl sulfonate.

The alkyl alcohol polyoxyethylene ether sulfonate satisfies the following formula:

the fatty acid alkyl ester sulfonate satisfies the following formula:

r4 is methyl, ethyl, propyl, butyl and other short chain alkyl. n is a positive integer such as 1, 2, 3. n is preferably a positive integer of 10 to 24, and more preferably 16, 18. Suitable examples are sodium methyl hexadecanoate sulphonate, sodium methyl octadecanoate sulphonate.

The sulfoalkyl ester of a fatty acid satisfies the formula:

R₅a saturated or unsaturated alkyl group having a carbon number of 10 to 20, preferably 16 to 18, M⁺Is a cationic moiety. n is a positive integer such as 1, 2, 3. n is preferably 2. A suitable example is the ester of oleic acid and sodium isethionate, i.e. sodium oleoyloxyethylsulphonate.

The sulfoalkyl amide of the fatty acid satisfies the following formula:

R₆a saturated or unsaturated alkyl group having a carbon number of 10 to 20, preferably 16 to 18, M⁺Is a cationic moiety. n is a positive integer such as 1, 2, 3. n is preferably 2. R₇The alkyl group is a short chain alkyl group such as methyl, ethyl, propyl, butyl, etc., preferably methyl. Suitable examples are amides of oleic acid and sodium N-methylsulphonate, i.e. sodium N-oleoyl-N-methyltaurate.

The succinate sulfonate satisfies the following formula

R₈A saturated or unsaturated alkyl group having a carbon number of 10 to 20, preferably a saturated or unsaturated alkyl group having a carbon number of 12 to 18, M⁺Is a cationic moiety. A suitable example is the sodium salt of lauryl sulfosuccinate.

Other surfactants

Other surfactants selected from the group consisting of alkyl sulfates of C8 to C18, ethoxylated fatty alcohol sulfates of C8 to C18, fatty acid salts of C8 to C18, ethoxylated fatty alcohol ether carboxylates, fatty alcohol alkoxylates, alkyl glycosides, fatty acid alkoxylates, fatty acid alkylolamides, fatty acid methyl ester ethoxylates, mixtures of one or more of polyether surfactants. Other surfactants may be present in the detergent composition at levels of from 10% to 20%.

The alkyl sulfate can be a linear chain or a branched chain in the alkyl chain segment, and can be a saturated alkyl or an alkyl containing one or more unsaturated double bonds. Alkyl sulfates having an alkyl carbon number of 8 to 18. A suitable example is sodium lauryl sulphate.

The ethoxylated fatty alcohol sulfate is a derivative of an ethoxylated fatty alcohol satisfying the following formula:

r9 is alkyl having 6 to 24 carbon atoms; x is 0.5 to 30; wherein M is⁺As cations, for example, potassium ions, sodium ions, ammonium ions, and the like. R1 may be a linear or branched alkyl group; it may be a saturated alkyl group or an alkyl group having one or more unsaturated double bonds. A suitable example is Texapon N70 from BASF.

The fatty acid salt is a fatty acid salt with 8 to 18 carbon atoms. The alkyl chain segment of the fatty acid may be a straight chain or a branched chain, and may be a saturated alkyl group or an alkyl group having one or more unsaturated double bonds. The fatty acid salt may be a single composition or a mixture of multiple fatty acid compositions. Suitable examples are sodium oleate, sodium laurate. The fatty acid salt further comprises an ethoxylated fatty alcohol ether carboxylate, the fatty alcohol preferably having a carbon number of from 8 to 18 and an average degree of ethoxylation of from 2.0 to 5.0.

The fatty alcohol alkoxylates have the general formula:

n is 6 to 24; x is 0.5 to 30 and y is 0 to 10. The fatty alcohol alkoxylate is a product of ring opening polymerization of fatty alcohol and alkylene oxide under the action of an alkaline catalyst, and is basically a mixture. The fatty alcohol includes a straight chain alcohol or a branched chain isomeric alcohol. Alkoxy groups include ethoxy and propoxy groups. The fatty alcohol is preferably a fatty alcohol having a carbon number of 8 to 18, and the preferred alcohols include, but are not limited to, one of hexanol, octanol, decanol, 2-ethylhexanol, 3-propylheptanol, lauryl alcohol, isotridecyl alcohol, tridecyl alcohol, tetradecyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, and mixtures thereof. The average degree of ethoxylation x is preferably from 2 to 12. Preferred examples are the NEODOL series of linear fatty alcohol ethoxylates products from SHELL, the ECOSURF EH series of ethoxylated and propoxylated 2-ethylhexanols products from DOW, the Lutensol XL series of ethoxylated and propoxylated 3-propylheptanols products from BASF and the Lutensol XP series of ethoxylated 3-propylheptanols products from BASF.

The alkyl glycoside has the following general formula:

n is 6 to 24 and p is 1.1 to 3. Preferably n is 8 to 16. Suitable alkyl glycosides are, for example, the Glucopon series of alkyl glycosides from BASF.

The fatty acid alkoxylates, preferably from ethoxylated C8 to C18 fatty acid esters, have an average degree of ethoxylation of from 2 to 10. May contain an ethoxylated alkyl sorbitan ester having an alkyl carbon number of from 6 to 18 and an average degree of ethoxylation of from 4 to 20; a suitable example is the Corda Tween series of products.

The fatty acid alkylolamide has fatty acid with carbon number of 6-24, and can be linear fatty acid, branched fatty acid, saturated fatty acid or unsaturated fatty acid; the alkyl alcohol number is 0 to 2. Monoethanolamide, diethanolamide, isopropanolamide of fatty acids having a carbon number of 8 to 18 are preferred, a suitable example being coconut diethanolamide.

The fatty acid methyl ester ethoxylate has the following formula:

n is 6 to 24; x is 2 to 20. Preferably, n is 8 to 18 and x is 0.5 to 30. Preferably x is 4 to 10. A suitable example is the LION company MEE product.

The polyether surfactant. The polyether surfactant is a polymer, a nonionic surfactant containing ethylene oxide and/or propylene oxide repeating units, suitable examples being the Pluronic series from BASF.

Enzyme preparation

The enzyme preparation is a mixture of one or more of protease and amylase, and can also contain one or more of lipase, cellulase, mannanase and pectinase. The enzyme preparation may be present in an amount of from 0.01% to 5%, or preferably from 0.1% to 2% by weight of the detergent composition. Examples of suitable proteases are the commercial proteases from Novin (Savinase series proteases, Progress Uno series proteases), or from Dupont (Effectenz series proteases, Preferenz series proteases), or from Pasteur (Lavergy series proteases).

Preservative

The preservative of the present invention is used to provide preservative performance to a detergent composition at a level of from 0.001% to 2%, preferably from 0.001% to 0.05% by weight of the detergent composition. One or more selected from methylisothiazolinone, methylchloroisothiazolinone, benzisothiazolinone, phenoxyl, sodium benzoate, and p-hydroxybenzoate.

Auxiliary agent

The auxiliary agent is selected from one or a mixture of more of polymers, inorganic salts, viscosity regulators, antibacterial agents, coloring agents, essences and pH regulators.

Antibacterial agent

The detergent compositions of the present invention may further comprise an anti-bacterial agent. The anti-bacterial agent is selected from, but not limited to: hypochlorous acid and salts thereof, p-chloro-m-xylenol, p-chloro-m-cresol, hydroxy-dichloro-diphenyl ether, hydroxy-trichloro-diphenyl ether, triclocarban, o-phenylphenol, dodecyl dimethyl benzyl ammonium chloride, dodecyl trimethyl ammonium chloride, tetradecyl dimethyl benzyl ammonium chloride, tetradecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, didecyl dimethyl ammonium chloride, polyhexamethylene biguanide hydrochloride, 1-hexadecyl pyridine chloride, zinc pyrithione, and pyridone ethanolamine salt.

Acid-base regulator

The pH regulator comprises an acidity regulator and an alkalinity regulator. Wherein the acidity regulator is selected from organic acid, inorganic acid and strong acid and weak base salt which are well known in the daily chemical product industry, preferably selected from citric acid, succinic acid and boric acid, and more preferably selected from citric acid. The alkalinity regulator is selected from organic alkali, inorganic alkali and strong alkali and weak acid salt which are well known in the daily chemical product industry, and is preferably selected from organic amine, alkali metal hydroxide and alkali metal carbonate. Suitable examples are sodium hydroxide, potassium hydroxide, triethanolamine.

Polymer and method of making same

Polymers of the present invention include, but are not limited to: salts of homopolymers of acrylic acid, salts of copolymers of acrylic acid; cellulose derivatives such as carboxymethyl cellulose, ethyl hydroxyethyl cellulose, methyl cellulose; homopolymers and copolymers of vinylpyrrolidone, such as copolymers of linear polyvinylpyrrolidone, N-vinylpyrrolidone and vinyl acetate; polyethyleneimine derivatives, for example ethoxylated polyethyleneimine, polyethylene terephthalate and derivatives thereof, polyethylene glycol and derivatives thereof. The polymers impart soil redeposition resistance to the detergent composition, or promote soil release from the surface of the substrate, or enhance the appearance of the detergent composition.

The term "solvent" in the present invention means water and an organic solvent. The organic solvent is selected from polyhydric alcohol and polyhydric alcohol ether; suitable examples are propylene glycol, glycerol. In addition to the above ingredients, the detergent compositions of the present invention may contain various conventional and customary additives such as cosolvents, solubilizers, structurants, suds boosters, suds suppressors, fabric softeners, bleach systems, anti-wrinkle agents, and the like. These additives and the associated methods of use are well known to those skilled in the art, and the particular type and amount of such additives can be selected and adjusted to the particular needs.

Efficacy and deterioration against microbial contamination

The terms "efficacy against microbial contamination", "ability to withstand microbial challenge", "preservative efficacy", "preservative performance" of the present invention are not distinguished from each other. By "efficacy against microbial contamination" is meant the ability of the composition to resist microbial infection without producing significant changes in odor, appearance, and preservative content. The phenomenon that the composition generates obvious odor change, appearance change and preservative content change after being infected by microorganisms is called 'deterioration'.

Evaluation method and evaluation grade of microbial contamination resistance

The microorganism involved in the method for evaluating the efficacy against microbial contamination of the present invention is a bacterium. In particular to bacteria in an aggregated state. The invention adopts a 'microorganism aggregation method', carries out microorganism infection on the composition by using bacterial lawn, and evaluates the capability of a sample to resist microorganism infection by means of appearance change, odor change, preservative content change and the like of the composition.

The appearance change of the sample caused by intolerance of microbial contamination refers to the phenomenon that bacterial lawn serves as a microbial infection source, after the sample is infected, the size of the bacterial lawn is increased after the sample is cultured for a plurality of times at a certain temperature, the color of the sample in a container is changed, a biological film is formed on the inner wall of the container, and the like.

The odor change caused by the sample intolerance to microbial contamination means that bacterial lawn is used as a microbial infection source, and after the sample is infected, the sample is cultured for a plurality of times at a certain temperature to generate odor which is perceptible and unpleasant and has obvious odor difference with the odor of the sample before infection.

The change of the content of the preservative caused by the sample intolerance to microbial contamination means that the content of the preservative is obviously changed after the sample is cultured for a plurality of times at a certain temperature after the sample is infected by bacterial lawn serving as a microbial infection source.

The microorganism aggregation method is to collect and fix bacterial lawn by using a lawn sampler and use the collected and fixed bacterial lawn as a microorganism infection source to infect a sample. The lawn sampler is a hollow cone with an upper through opening and a lower through opening, and the upper opening is provided with a diagonal plane. The upper opening of the lawn sampler is used for collecting lawns and fixing the lawns to propagate the lawns; the lower opening is communicated with the upper opening to ensure that the sampler floats on the surface of the liquid in the liquid, and the lawn can obtain enough oxygen for growth and propagation. The oblique section of the opening on the lawn sampler is S1, and S1 is an ellipse; the lower opening is circular; the difference between the diameters of the upper inner wall and the outer wall of the lawn sampler is 1-2 mm.

The method for evaluating the microbial contamination resistance comprises the following specific steps:

step 1: coating bacteria on Tryptone Soy Agar (TSA) plate, and culturing at 36 deg.C for 24 hr to obtain thallus Porphyrae plate;

step 2: selecting a lawn plate which is freshly cultured or stored in a refrigerator at 4 ℃ for no more than 7 days, scraping the lawn on the plate by using a lawn sampler, and covering the upper inclined plane of the sampler with the lawn S1; the number of the live bacteria of the lawn collected on each sampler is 5 multiplied by 10⁹CFU/one to 5X 10¹⁰CFU/one;

and step 3: placing the sample in a sterile container, adding the sampler with the lawn in the step (2), sealing the sterile container, culturing at 36 ℃ for 28 days, and keeping the container to stand as much as possible in the process;

and 4, step 4: the efficacy of the samples against microbial contamination was evaluated as follows.

(1) Visual method

The procedure for determining the results of the visual method was as follows: if the lawn in the sterile container grows obviously or the size is increased, the color of the sample in the container is changed, and the inner wall of the container has the phenomena of biomembrane and the like, the sample is judged to be not passed through by visual judgment; and if the lawn in the sterile container is not obviously grown or the size is reduced, the color is not changed, and the inner wall has no biofilm, judging that the visual judgment is passed. Each sample was tested in 5 replicates. The total visual determination pass rate a (%) of the sample was calculated by the following formula.

(2) Olfaction method

The result judgment steps of the olfaction method are as follows: the odor in the containers containing the samples after incubation was evaluated organoleptically using a panel of experts. The expert panel is a sensory evaluation panel which is composed of at least 3 persons and at most 7 persons and has the capability of obviously distinguishing the concentration of the peculiar smell after training. The sensory evaluation means that the odor intensity was scored by a panel (from 3 to 7 persons) according to the following table 2. Finally, the scores of all members of the expert group are summed, the average value is calculated according to the number of people, and 1 decimal is reserved for the result. Higher scores indicate more intense off-notes.

Each sample was tested in 5 replicates and only the single replicate with the greatest odor intensity was retained.

TABLE 2 evaluation of odor intensity

(3) Changes in preservative content caused by microbial infection

The changes in preservative content due to microbial infection were tested as follows: the preservative content of the sample before and after microbial infection is detected by using chromatography, and the change degree of the component content is evaluated by using the preservative retention rate Rm. The subscript m represents the change in preservative content caused by the microorganism. And Rm is less than or equal to 80%, judging that the preservative content is obviously changed. And if Rm is more than 80%, judging that the preservative content is not obviously changed.

R_i: preservative content of the sample before being subjected to microbial infection, expressed as a weight percentage;

R_ii: preservative content of the sample after being subjected to microbial infection, expressed as a weight percentage;

rm: preservative retention,%.

When more than one preservative is present in the composition, the preservative retention Rm is calculated as follows.

Ra_i: preservative a content of the sample before being subjected to microbial infection, expressed as a weight percentage;

Rb_i: preservative b content of the sample before being subjected to microbial infection, expressed as a weight percentage;

......

Rn_i: preservative n content of the sample before being subjected to microbial infection, expressed as a weight percentage;

Ra_ii: preservative a content of the sample after being subjected to microbial infection, expressed as a weight percentage;

Rb_ii: preservative b content of the sample after being subjected to microbial infection, expressed as a weight percentage;

......

Rn_ii: preservative n content of the sample after being subjected to microbial infection, expressed as a weight percentage;

rm: preservative retention,%.

The efficacy of the samples against microbial contamination was evaluated in combination with the results of visual, olfactory and preservative retention, as shown in table 3.

TABLE 3 evaluation criteria for efficacy against microbial contamination

Antibacterial performance test method and evaluation grade

The terms "antibacterial", "bactericidal" and "degerming" in the present invention are not distinguished from each other. The terms "antibacterial property", "bactericidal property" and "bactericidal efficacy" are not to be distinguished from each other. The antibacterial rate, the sterilization rate and the degerming rate are not distinguished.

The antibacterial performance refers to the capability of the fabric detergent composition in killing microorganisms, and is carried out according to QB/T2738-2012 evaluation method for antibacterial and bacteriostatic effects of daily chemical products. The action concentration is 1 percent; the acting time is 20 minutes; acting on strains: staphylococcus aureus ATCC 6538. The antibacterial performance is described in terms of bactericidal activity in the present invention.

Evaluation criteria for antibacterial Properties

Calculating the sterilization rate of the sample according to the following formula:

the sterilization ratio (%) - (viable cell count of control sample-viable cell count of test sample)/viable cell count of control sample × 100%

When the sterilization rate is less than 90%, the evaluation grade is 'no antibacterial property'; when the sterilization rate is more than or equal to 90 percent, the evaluation grade is 'antibacterial property'. When the sterilization rate is more than 99.9%, the evaluation grade is 'good antibacterial performance'. The higher the bactericidal rate, the stronger the antibacterial action.

Comprehensive stability performance

The term "overall stability" as used herein refers to the ability of a sample to undergo aging testing without significant changes in odor, appearance, and component content. The invention refers to the condition that the product generates obvious odor change, appearance change and component content change after aging test as unstable. Conversely, it is said to be "stable" or "having good stability properties".

The term "overall stability properties" in the context of the present invention includes both "component stability properties" and "organoleptic stability properties".

Component stability Properties

The component stability performance specifically refers to the change of the content of the enzyme preparation and the content of the preservative after the sample is subjected to aging test. The less variation in enzyme formulation and preservative levels indicates the better stable performance of the components of the sample.

Stability of the enzyme preparation: and the enzyme activity retention rate E is used for quantitatively characterizing the stability of the enzyme preparation in the components before and after aging test. The aging test of the enzyme preparation specifically refers to the ratio of the residual enzyme activity (U1) to the initial enzyme activity (U0) which is not stored under the specific conditions, after the sample is placed in a closed container and stored at the constant temperature of 37 +/-1 ℃ for a period of 4 weeks and 8 weeks. The enzyme activity test method is adopted for testing. The enzyme activity is tested by adopting a colorimetric method, a stable colored compound is generated according to the reaction of a product of the enzyme reaction and a specific chemical reagent, and the color depth of the compound and the concentration of the product are in a linear relation in a certain range, so that the enzyme activity is measured. The enzyme activity retention rate E was calculated as follows. The enzyme activity retention rate is more than 80% after aging for 4 weeks and more than 65% after aging for 8 weeks, and the enzyme preparation is judged to have no obvious change. The enzyme activity retention rate is more than 80% after aging for 4 weeks and less than or equal to 65% after aging for 8 weeks, and the enzyme preparation is judged to be obviously changed. The enzyme activity retention rate is less than or equal to 80 percent after aging for 4 weeks, and the enzyme preparation is judged to be obviously changed. The fact that the enzyme preparation has no obvious change indicates that the enzyme preparation has good stability.

E(％)＝(U1/U0)*100％

U0: initial enzyme activity of the sample prior to being subjected to the enzyme preparation aging test;

u1: residual enzyme activity of the sample after aging test of the enzyme preparation;

e: retention rate of enzyme activity,%.

When more than one enzyme preparation is contained in the composition, E is calculated for each enzyme preparation, and the result of E of only one enzyme preparation with the lowest retention rate is taken as the enzyme activity retention rate of the total enzyme preparation.

Stability of the preservative: the content of the preservative before and after the sample was subjected to the aging test was measured by chromatography, and the degree of change in the content of the component was evaluated by the preservative retention ratio Ra. The subscript a represents the change in preservative content caused by aging testing. The aging test of the preservative means that a sample is placed in a closed container, placed in an environment with the temperature of 45 +/-2 ℃, and is restored to the room temperature of 25 +/-5 ℃ after being kept at the constant temperature for 4 weeks. When Ra is more than 80%, it is judged that "the content of the preservative is not significantly changed". When Ra is 80% or less, it is judged that "the content of the preservative is significantly changed". "no significant change in preservative content" indicates good preservative stability.

R_iii: preservative content of the sample before being subjected to aging test for preservatives;

R_iv: preservative content of the sample after being subjected to an aging test for preservatives;

ra: preservative retention after aging test,%.

When more than one preservative is present in the composition, the preservative retention Ra is calculated as follows.

Ra_iii: preservative a content of the sample before being subjected to microbial infection, expressed as a weight percentage;

Rb_iii: preservative b content of the sample before being subjected to microbial infection, expressed as a weight percentage;

......

Rn_iii: preservative n content of the sample before being subjected to microbial infection, expressed as a weight percentage;

Ra_iv: preservative a content of the sample after being subjected to microbial infection, expressed as a weight percentage;

Rb_iv: preservative b content of the sample after being subjected to microbial infection, expressed as a weight percentage;

.......

Rn_iv: preservative n content of the sample after being subjected to microbial infection, expressed as a weight percentage;

ra: preservative retention after aging test,%.

Sensory stability Properties

The sensory stability properties, specifically the change in appearance and the change in odor after the samples were subjected to aging tests. The less change in appearance and odor indicates the better organoleptic stability of the sample.

Aging test method for sensory stability performance:

high-temperature stability: placing the sample in a closed container, keeping the temperature at 45 +/-2 ℃ for one month, returning to the room temperature of 25 +/-5 ℃, observing the appearance, uncovering the container to evaluate the smell. The control was a sample that was not aged.

Low-temperature stability: placing the sample in a closed container, keeping the temperature at 0 +/-2 ℃ for one month, returning to the room temperature of 25 +/-5 ℃, observing the appearance, uncovering the container to evaluate the smell. The control was a sample that was not aged.

And (3) normal temperature stability: after bottling and sealing, the composition is placed at 25 + -5 deg.C for one month, and the appearance is directly observed, and the odor is evaluated by uncapping. The control was a sample that was not aged.

Sensory stability evaluation criteria

With "-" there is no significant difference in appearance and odor of the samples after aging test; compared with the control sample. "-" indicates that the sample had good organoleptic stability properties.

The slight change in appearance or odor is indicated by "+" as compared to the control. The "+ +" indicates a significant change in appearance or odor, as compared to the control. The strong change in appearance or odor is indicated by "+++" as compared to the control. "+", "+ + + + +", which indicates that the sample was unstable.

Evaluation criteria for comprehensive stability Performance

The overall stability performance of the samples was evaluated as per table 4. Only the samples satisfying the following conditions at the same time were judged to have "good" overall stability. The properties include:

enzyme activity retention rate E: greater than 80% after 4 weeks of aging and greater than 65% after 8 weeks of aging.

Preservative retention ratio Ra: greater than 80% after 4 weeks of aging.

High temperature stability, odor and appearance were all "no significant changes".

Low temperature stability, odor and appearance were all "no significant changes".

The stability at normal temperature, the smell and the appearance are all 'no obvious change'.

TABLE 4 evaluation criteria for comprehensive stability Performance

Method for testing detergency performance of washing machine

The washing decontamination performance test is carried out according to GB/T13174-2008. Three dirty cloths, namely sebum, protein and carbon black, are adopted, and the whiteness W1 of the three dirty cloths before washing is measured by using a WSD-3U fluorescence whiteness meter of Beijing Kangguan optical instruments Limited. The washing water with the hardness of 250ppm is prepared according to GB/T13174-2008, wherein the molar ratio of calcium ions to magnesium ions is 3: 2.

The detergent composition was formulated into a 0.2% solution with 250ppm of wash water to meet the standard laundry detergent as per GB/T13174-2008. Washing for 1 time by using a RHL Q type vertical decontamination machine of China institute of daily chemical industry, wherein the washing time is 20min, the washing temperature is 30 ℃, the stirring speed is 120 r/min, three kinds of dirty cloth are rinsed and dried, and the whiteness W2 of the three kinds of dirty cloth after washing is measured by using a WSD-3U fluorescence whiteness meter. The difference in whiteness Δ W is calculated as follows:

ΔW＝W2-W1

w2: the whiteness of the dirty cloth after washing is improved,

w1: whiteness of the stained cloth before washing.

The smaller the Δ W value, the smaller the difference in whiteness after washing before washing of stained cloth, and the poorer the washing performance of the detergent composition.

The detergency ratio P of the detergent composition was calculated by the following formula based on the aw value of the control, and two decimal places were retained.

P＝ΔW i/ΔWI

Δ W i: difference in whiteness of detergent composition;

Δ WI: difference in whiteness of control.

A P value of less than 1 indicates that the detergent composition has a lower detergency than the control and a P value of greater than 1 indicates that the detergent composition has a higher detergency than the control. The larger the P value, the stronger the detergency of the detergent composition. When the P value is more than or equal to 1.10, the detergent composition has good washing and stain removal performance.

Methods of formulation and use

The detergent compositions of the present invention are useful in a manner well known to those skilled in the art, and typically are used by contacting the particular detergent composition embodiment with the surface of the article to be cleaned, either undiluted or diluted in water, and then rinsing the surface of the article to be cleaned. Preferably, the articles to be washed are subjected to a washing step between the above-mentioned contacting step and the rinsing step. The washing step includes, but is not limited to, scrubbing and mechanical agitation. The washed objects comprise fabrics and tableware. The detergent composition has a concentration of from about 500ppm to 10000ppm in water, preferably from 5 ℃ to about 60 ℃. The ratio of water to items to be washed is preferably from about 1: 1 to about 20: 1.

Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The following examples are intended to further describe and demonstrate embodiments within the scope of the present invention. The examples are therefore to be understood as merely illustrative of the invention in more detail and not as limiting the content of the invention in any way.

In the following examples, all amounts are by weight unless otherwise indicated, and the amounts of the listed ingredients are converted to active material amounts.

EDTA: ethylenediaminetetraacetate, belonging to the class of component A1,

DTPA: diethylene triamine pentaacetate, which belongs to the class of component A1,

DCTA: cyclohexanediaminetetraacetic acid salts, which belong to the class of component A1,

EDDHA, ethylenediamine di-o-phenyl acetate, which does not conform to the complexing agent of the technical proposal,

MGDA: the methylglycine diacetate does not conform to the complexing agent of the technical scheme,

GLDA: glutamic acid diacetate, a complexing agent not conforming to the technical scheme,

sodium metaborate, which belongs to the class of component A2,

sodium tetraborate, of the class of component a2,

ammonium pentaborate, said class being component a 2.

Phenylboronic acid, a boron-containing compound not in accordance with the present technical solution,

4-formylphenylboronic acid, boron-containing compounds not in accordance with the present invention

And (3) LAS: C10-C13 sodium linear alkyl benzene sulfonate belongs to the category of sulfonic acid surfactants,

MES: C16-C18 fatty acid methyl ester sodium sulfonate belongs to the category of sulfonic acid surfactants,

AEO: ethoxylated fatty alcohols, with an average degree of ethoxylation of 7 to 9, belong to the class of other surfactants.

APG: C8-C14 alkyl glycosides, belonging to the class of other surfactants,

CAB: cocamidopropyl betaine belongs to the class of other surfactants.

Protease: commercially available from Novozymes corporation.

Amylase: commercially available from Novozymes corporation.

And (3) preservative A: a mixture of methylisothiazolinone and chloromethylisothiazolinone.

And (3) preservative B: a mixture of methylisothiazolinone and phenoxyethanol.

Organic solvent: mixture of glycerol and propylene glycol

Process for the preparation of a liquid detergent composition:

(1) adding part of deionized water into the preparation tank;

(2) starting stirring, heating to 50-60 ℃, converting the sulfonic acid surfactant in an acid form into corresponding salt under an alkaline condition, and stirring until the sulfonic acid surfactant is completely dissolved;

(3) adding other surfactants, and stirring until the surfactant is completely dissolved;

(4) stopping heating, adding the rest deionized water into the preparation tank, and accelerating the temperature reduction;

(5) cooling to below 40 deg.C, adding component A1 and component A2 of stabilization promoting system, enzyme preparation, essence, antiseptic, polymer and other components, stirring to dissolve completely;

(6) adding a viscosity regulator, stirring until the viscosity regulator is completely dissolved, regulating the pH value and the viscosity, and discharging after the detection is qualified.

Examples 1 to 4, and comparative example 1 were prepared according to the above-described preparation method. The specific compositions are shown in Table 5 below.

Table 5 compositions of examples 1 to 4, comparative example 1

Examples 5 to 7 and comparative examples 2 to 9 were prepared according to the above preparation method 1. Table 6 identifies the points of distinction.

TABLE 6 similarities and differences between examples 5 and 7 and between comparative examples 2 and 9

Microbial contamination resistance efficacy of examples 1 to 7 and comparative examples 1 to 9

Examples 1 to 7 and comparative examples 1 to 9 were tested according to the evaluation method of the efficacy against microbial contamination described above, and the results are shown in Table 7.

TABLE 7 microbial contamination resistance efficacy of examples 1 to 7, comparative examples 1 to 9

As can be seen from the data, examples 1 to 7 of the present invention all had good efficacy against microbial contamination. Whereas none of comparative examples 1 to 9 passed the efficacy test for resistance to microbial contamination, producing a visual appearance change and a very strong off-flavor. Analysis revealed that the amount of preservative used in comparative example 1 (150ppm) was 15 times the preservative content in example 3 (10ppm), but completely failed the contamination resistance test. All the parallel test samples of comparative example 1 deteriorated without exception, the preservative was completely decomposed by the microorganisms, and a strong odor was generated. This is due to the fact that the microorganisms used in the efficacy test for tolerant microorganisms are present in the aggregated form and are effective against the action of preservatives. The stable promoting system provided by the technical scheme of the invention can effectively break down the microorganisms in an aggregated state, thereby endowing the detergent composition with the effects of resisting microbial contamination without deterioration and keeping stable appearance, smell and preservative content.

Comparative examples 2 and 3 used MGDA and GLDA, two aminocarboxylic complexing agents that did not meet the requirements of the present invention. The stability constants logK of MGDA and GLDA to calcium ions are less than 8.0. Comparative examples 4 and 5 use two boron-containing compounds that do not meet the requirements of the present invention, phenylboronic acid and 4-formylphenylboronic acid. The boron content of the phenylboronic acid and the 4-formylphenylboronic acid is less than 10%. None of comparative examples 2 to 5 passed the efficacy test for resistance to microbial contamination, produced visual appearance changes and a very strong off-flavor, and resulted in microbial degradation of the preservative. The stable promoting system provided by the invention adopts a proper aminocarboxylic complexing agent and a proper boron-containing compound, can effectively resist the pollution of microorganisms, and passes the test with excellent performance.

Comparative example 6 and comparative example 7, component a1 and component a2 used alone, respectively, are technical solutions not in accordance with the present invention. Comparative examples 8 and 9 are compositions of component a1 and component a2, but at lower levels than the present invention. None of comparative examples 6 to 9 passed the efficacy test for resistance to microbial contamination. The stable promotion system provided by the invention provides reasonable components and proportions, can effectively resist the pollution of microorganisms, and passes the test with excellent performance.

Antibacterial efficacy of examples 1 to 7 and comparative example 10

Comparative example 10 was prepared in the same manner. Table 8 identifies the points of distinction.

TABLE 8 heterology of comparative example 10

Examples 1 to 7 and comparative example 10 were tested according to the evaluation method of microbial contamination resistance and the evaluation method of antibacterial effectiveness described above, and the results are shown in Table 9.

Table 9 microbial contamination resistance efficacy and antibacterial efficacy of examples 1 to 7, comparative example 10

As can be seen from the data, the evaluation scale was "good antibacterial property" when the antibacterial ratio of examples 1 to 7 of the present invention was > 99.9%.

Comparative example 10 had good efficacy against microbial contamination, but the antibacterial rate was < 90%, and the rating was "no antibacterial property". In comparative example 10, the amount of the sulfonic acid type surfactant used was lower than the requirement of the technical solution of the present invention, and the antibacterial efficacy thereof could not satisfy the technical effect of the present invention.

The overall stability performance of examples 1 to 7 and comparative examples 11 to 13

Comparative examples 11 to 13 were prepared in the same manner. Table 10 identifies the points of distinction.

TABLE 10 heterology of comparative examples 11 to 13

Examples 1 to 7 and comparative examples 11 to 13 were tested according to the evaluation method of the comprehensive stability performance described above, and the results are shown in Table 11.

TABLE 11 Overall stability Performance for examples 1 to 7, comparative examples 11 to 13

As can be seen from the data, the overall stability performance rating for examples 1 through 7 of the present invention is "good". The examples of the present invention have good component stability and sensory stability. After undergoing different aging tests, the enzyme activity retention rate E, the preservative retention rate Ra, and the appearance and the smell of the composition can be kept stable.

The overall stability performance rating of comparative examples 11 to 13 is "unstable". Specifically, comparative example 11 showed cloudiness in appearance after the aging test, failing to pass the sensory stability test; this may be the result of the boron containing compound being present in an amount higher than required by the present invention. Comparative example 12 after 8 weeks of aging test, the enzyme activity retention rate E was reduced to 65% or less; the requirements of the detergent composition of the present invention are not satisfied. It is possible that the EDDHA used in comparative example 12 does not meet the performance requirements of the present invention for component a1 because of its too large calcium ion chelating constant. Comparative example 13 after 8 weeks of aging test, the enzyme activity retention rate E was reduced to 65% or less; the requirements of the detergent composition of the present invention are not satisfied. It is possible to cause the component A1 used in comparative example 13 to exceed the range required by the present invention.

Cleaning and stain removal Performance of examples 1 to 7

Examples 1 to 7 were tested according to the evaluation method of detergency and detergency performance in washing described above, and the results are shown in Table 12.

Table 12 detergency performance for washing of examples 1 to 7

Technical scheme	Sebum P1 value	Protein P2 value	Carbon black P3 value
				Example 1	1.15	2.10	1.16
Example 2	1.20	2.00	1.13
				Example 3	1.12	2.15	1.15
Example 4	1.19	2.30	1.12
				Example 5	1.13	2.50	1.15
Example 6	1.17	2.07	1.18
				Example 7	1.14	2.00	1.14

As can be seen from the data, examples 1 to 7 of the present invention all had P values greater than 1.10 for all three soils rated "having good cleaning performance.

The technical contents of the present invention are further illustrated by the examples, so as to facilitate the understanding of the reader, but the embodiments of the present invention are not limited thereto, and any technical extension or re-creation based on the present invention is protected by the present invention.

Claims

1. A stable detergent composition having antibacterial efficacy, characterized by comprising, in mass percent, from 0.3% to 1.1% of a stability promoting system having the following characteristics:

the stabilization promoting system is a mixture of component A1 and component A2;

the component A1 is selected from a complexone type complexing agent;

component A2 is selected from compounds containing boron element;

the detergent composition contains 0.05-0.15% of component A1 and 0.2-1% of component A2.

2. The stable and antibacterial detergent composition according to claim 1, wherein said aminocarboxylic complexing agent is selected from the group consisting of one or more of ethylenediaminetetraacetate, cyclohexanediaminetetraacetate, diethyleneglycoldiethyleneglycolethylendiaminetetraacetate, ethylenediaminetetrapropionate, diethylenetriaminepentaacetate, triethylenetetraminehexaacetate, and 2-hydroxyethylethylenediaminetriacetate; the cationic portion of the salt is selected from the group consisting of sodium ions, potassium ions, ammonium ions, and ammonium ions formed from organic amines.

3. The stable detergent composition with antibacterial effect of claim 1, wherein said compound containing boron element,

(1) the content of boron element is 10% or more of the molecular weight of the compound containing boron element,

(2) the solubility of the compound containing boron element in 100g of pure water at 25 ℃ is more than 5 g.

4. The stable, antimicrobially effective detergent composition as recited in claim 3, wherein said boron containing compound is selected from the group consisting of metaborate, orthoborate, and polyborate, wherein said salts have a cationic moiety selected from the group consisting of sodium, potassium, ammonium, and ammonium formed from organic amines; or a mixture of one or more satisfying chemical formula (1);

R_x: a group consisting of one or more of element C, H and element O, N, S;

5. The stable detergent composition with antibacterial effect according to claim 1, characterized by further comprising the following components by mass percent:

4 to 15 percent of sulfonic acid type surfactant;

10-20% of other surfactant;

0.01 to 5 percent of enzyme preparation;

0.001 to 2 percent of preservative;

0.01 to 15 percent of auxiliary agent;

the balance being solvent.

6. The stable detergent composition having antibacterial effect according to claim 5, wherein said sulfonic acid type surfactant is selected from the group consisting of alkyl sulfonate, alkyl benzene sulfonate, fatty acid alkyl ester sulfonate, succinate sulfonate, alkyl alcohol polyoxyethylene ether sulfonate, sulfoalkyl ester of fatty acid or sulfoalkyl amide of fatty acid; the carbon number of the alkyl group of the sulfonic acid type surfactant is 6 to 24, and the sulfonic acid type surfactant is selected from linear alkyl and branched alkyl, and is saturated alkyl or alkyl containing one or more unsaturated double bonds; the cationic portion of the salt is selected from the group consisting of sodium ions, potassium ions, ammonium ions, and ammonium ions formed from organic amines.

7. The stable, antimicrobially effective detergent composition as claimed in claim 5, wherein said additional surfactant is selected from the group consisting of C8-C18 alkyl sulfate, C8-C18 ethoxylated fatty alcohol sulfate, C8-C18 fatty acid salt, ethoxylated fatty alcohol ether carboxylate, fatty alcohol alkoxylate, alkyl glycoside, fatty acid alkoxylate, fatty acid alkylolamide, fatty acid methyl ester ethoxylate, and mixtures of one or more polyether surfactants.

8. The stable, antimicrobially effective detergent composition as recited in claim 5, wherein said enzyme preparation comprises one or a mixture of more of a protease and an amylase.

9. The stable, antimicrobially effective detergent composition as recited in claim 8, wherein said enzyme preparation further comprises a mixture of one or more of cellulase, lipase, pectinase, or mannanase enzymes.

10. The stable and antibacterial detergent composition according to claim 5, wherein said preservative is selected from the group consisting of isothiazolone derivatives including methylisothiazolinone, methylchloroisothiazolinone, benzisothiazolinone, and one or more of phenoxyalcohol, sodium benzoate, and parabens.

11. The stable and antibacterial detergent composition according to claim 5, wherein said adjunct is selected from the group consisting of polymers, inorganic salts, viscosity modifiers, anti-bacterial agents, colorants, perfumes, and pH modifiers; the solvent is water and/or organic solvent, and the organic solvent is selected from polyalcohol or polyalcohol ether.

12. The stable, antibacterial detergent composition according to claim 1, characterized by:

(1) the antibacterial rate of the detergent composition is more than 99.9%;

(3) the odor, appearance, preservative content of the detergent composition did not change significantly after being subjected to the microbial contamination test.