CN113854295B - Antibacterial composition - Google Patents
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- CN113854295B CN113854295B CN202111296891.6A CN202111296891A CN113854295B CN 113854295 B CN113854295 B CN 113854295B CN 202111296891 A CN202111296891 A CN 202111296891A CN 113854295 B CN113854295 B CN 113854295B
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/12—Quaternary ammonium compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
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- A—HUMAN NECESSITIES
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- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
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- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/30—Amines; Substituted amines ; Quaternized amines
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- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3723—Polyamines or polyalkyleneimines
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- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38618—Protease or amylase in liquid compositions only
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- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
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Abstract
The invention discloses an antibacterial composition, which consists of a quaternary ammonium salt bactericide A and a bactericide B, wherein the bactericide B comprises a repeating unit with a structure shown in the following formula:wherein R and R' are alkyl groups having 1 to 3 carbon atoms, X ‑ Is CH 3 SO 4 ‑ 、CH 3 CH 2 SO 4 ‑ Or halogen ions, the weight percentage of the molecular weight of the repeating unit in the total molecular weight of the bactericide B is more than 70, the weight average molecular weight of the bactericide B is 2000-400000, and the weight ratio of the bactericide A to the bactericide B is 1: 10-5: 1. The invention also discloses a liquid detergent with antibacterial effect, which comprises the following components: 0.1 to 5 percent of bactericide A,0.1 to 5 percent of bactericide B,0.5 to 65 percent of surfactant, 0.2 to 30 percent of washing assistant and the balance of water. The invention has excellent sterilization effect under low concentration and strong anti-interference capability to hard water and surfactant.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to an antibacterial composition with hard water resistance and surfactant interference resistance.
Background
Along with the improvement of living standard of people, the sanitary requirement on living environment is higher and higher, so in the daily chemical cleaning field, besides the conventional detergent product, the product with the sterilization function on the fabric and the hard surface is more and more valued by consumers. The quaternary ammonium salt bactericide belongs to a cationic surfactant bactericide, has an action mechanism that positive charges are carried by the bactericide, the bactericide can be adsorbed on the surface of bacteria to form micelles, and a hydrophobic group is inserted into a bacterial lipid layer to change the permeability of a cell membrane, destroy the cell structure, influence the metabolism of the bacteria and finally cause the death of the bacteria. The quaternary ammonium salt bactericide has low bactericidal concentration, stable chemical performance, no corrosive bleaching effect and low irritation to skin and tissues, and is suitable for use in household environment. However, the quaternary ammonium salt bactericide belongs to a cationic surfactant, and the compatibility of the components and the use conditions of the bactericide have many limitations, such as the incompatibility with an anionic surfactant (most of the existing liquid detergent formula systems mainly use the anionic surfactant), the bactericidal effect is reduced under the condition of hard water, and the application of the quaternary ammonium salt bactericide in household sterilization functional products is greatly limited. For example, CN201610307397.8 discloses an antibacterial fabric detergent and a preparation method thereof, quaternary ammonium salt bactericide, nonionic surfactant, zwitterionic surfactant and other components are compounded to prepare the detergent with dual effects of decontamination and sterilization, and the detergent does not contain anionic surfactant.
Disclosure of Invention
The invention aims to provide an antibacterial composition with hard water resistance and surfactant interference resistance, and also provides a liquid detergent based on the antibacterial composition, so that the liquid detergent has excellent antibacterial effect while maintaining the dirt-removing capacity.
The antibacterial composition provided by the invention consists of a bactericide A and a bactericide B, wherein the bactericide A is a quaternary ammonium salt bactericide, and the bactericide B comprises a repeating unit with a structure shown in the following formula:
wherein R and R' are alkyl groups having 1 to 3 carbon atoms, X - Is CH 3 SO 4 - 、CH 3 CH 2 SO 4 - Or halide ions, the percentage of the molecular weight of the recurring units in the total molecular weight of fungicide B is greater than 70, preferably 80. The weight average molecular weight of the bactericide B is 2000-400000, preferably 5000-200000; the weight ratio of the bactericide A to the bactericide B is 1: 10-5: 1.
The bactericide A can be a mono-quaternary ammonium salt or a di-quaternary ammonium salt bactericide, and can be one or more of dodecyl dimethyl benzyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide, di-decyl dimethyl ammonium chloride, di-decyl dimethyl ammonium bromide, cetyl pyridine chloride, ethylene (didodecyl dimethyl ammonium bromide) and ethylene (ditetradecyl dimethyl ammonium bromide).
The liquid detergent based on the antibacterial composition comprises the following components: 0.1 to 5 percent of antibacterial composition, 0.5 to 65 percent of surfactant, 0.2 to 30 percent of washing assistant and the balance of water.
The surfactant is one or more of nonionic surfactant, cationic surfactant, anionic surfactant and zwitterionic surfactant, wherein the anionic surfactant is non-soap anionic surfactant, and the mass content of the anionic surfactant is less than 80ppm multiplied by the using dilution factor.
The washing auxiliary agent comprises one or more of fillers, excipients, binders, anti-redeposition agents, chelating agents, enzyme preparations, alkaline agents, pH regulators, viscosity regulators, preservatives, pigments, fluorescent whitening agents and essences.
For a better understanding of the present disclosure, the following detailed description constitutes a key part of the present invention. All percentages, ratios, and proportions used herein are by weight percent of the composition, unless otherwise specified. All average values are by weight of the composition or components thereof, unless expressly stated otherwise.
In the field of daily chemical cleaning, in addition to conventional detergent products, products having a sterilizing function for fabrics and hard surfaces are increasingly gaining attention, and products having both a cleaning and sterilizing function are certainly more popular with consumers. The quaternary ammonium salt bactericide belongs to a cationic surfactant bactericide, has an action mechanism that positive charges are carried by the bactericide, the bactericide can be adsorbed on the surface of bacteria to form micelles, and a hydrophobic group is inserted into a bacterial lipid layer to change the permeability of a cell membrane, destroy the cell structure, influence the metabolism of the bacteria and finally cause the death of the bacteria. The quaternary ammonium salt bactericide has low bactericidal concentration, stable chemical performance, no corrosive bleaching effect and low irritation to skin and tissues, and is suitable for use in household environment. However, the quaternary ammonium salt bactericide belongs to a cationic surfactant, and the compatibility of the components and the use conditions of the bactericide have a plurality of limitations, if the bactericide cannot be compatible with an anionic surfactant, the bactericidal effect is obviously reduced under the condition of hard water, so that the application of the quaternary ammonium salt bactericide in household degerming functional products is greatly limited. As is known in the art, quaternary ammonium salt bactericides cannot be compatible with anions, so that the compounding of nonionic or/and zwitterionic surfactants and quaternary ammonium salt bactericides is an easily-conceived technical scheme, however, the inventor finds that even nonionic surfactants can obviously reduce the bactericidal effect of quaternary ammonium salt bactericides. The inventor further researches and invents that the quaternary ammonium salt bactericide and the specific polyquaternium bactericide can achieve synergistic effect, and can solve the problem that a single quaternary ammonium salt bactericide is easily influenced by hard water and a surfactant.
Fungicide A
The bactericide A is a quaternary ammonium salt bactericide, further, the quaternary ammonium salt bactericide is divided into a single-quaternary ammonium salt bactericide or a double-quaternary ammonium salt bactericide according to the number of ammonium salt structures contained in a molecule, and is divided into a single-chain quaternary ammonium salt and a double-chain quaternary ammonium salt according to the number of long-chain alkyl groups in the molecule, wherein the long-chain alkyl groups are generally 8-18 carbon, and although the double-chain quaternary ammonium salt can reduce the adverse effects of an anionic surfactant and hard water to a certain extent, the combination with the anionic surfactant is still required to be avoided. Examples of the single-chain quaternary ammonium salts include dodecyldimethylbenzyl ammonium chloride (benzalkonium chloride), dodecyldimethylbenzyl ammonium bromide (benzalkonium bromide), and cetylpyridinium chloride (cetylpyridinium chloride). Examples of the double-chain quaternary ammonium salt include bisoctyl dimethyl ammonium chloride, bisoctyl dimethyl ammonium bromide, bisdecyl dimethyl ammonium chloride, bisdecyl dimethyl ammonium bromide and the like. The biquaternary ammonium salt is formed by connecting two single quaternary ammonium salt molecules at or close to a hydrophilic head group of the quaternary ammonium salt through a connecting group, but the biquaternary ammonium salt is still small molecular quaternary ammonium salt and cannot radically change the defects of the quaternary ammonium salt bactericide, and the biquaternary ammonium salt can be ethylene base (didodecyldimethylammonium bromide) and ethylene base (ditetradecyldimethylammonium bromide).
Fungicide B
The bactericide B is a quaternary ammonium salt type cationic polymer, and comprises a repeating unit shown in the following formula (1), R and R' are alkyl with 1-3 carbon atoms, and X - Is CH 3 SO 4 - 、CH 3 CH 2 SO 4 - Or halide ions, the molecular weight of the recurring units of formula (1) is more than 70% of the total molecular weight, preferably the molecular weight of the recurring units of formula (1) is more than 80% of the total molecular weight;
the weight average molecular weight of the fungicide B is 2000 to 400000, and preferably 5000 to 200000.
The cationic polymer is conventionally poly-hydroxypropyl dimethyl ammonium chloride, is a copolymer of epichlorohydrin and dimethylamine, further can contain other alkylamine polymerization monomers, such as ethylamine, diethylamine, ethylenediamine and the like, and further comprises a block copolymer of poly-hydroxypropyl dimethyl ammonium chloride and other polymer structural segments.
For quaternary ammonium salt type cationic polymers, the cationic charge density can be measured by Kjeldahl methodThe nitrogen content value is calculated, but the influence factor is more, and the larger deviation can be caused with the actual situation. For water-soluble quaternary ammonium cationic polymers, the charge density can be expressed in terms of cationic degree, and the test method is to formulate the polymer into an aqueous solution and use K 2 CrO 4 Indicator, the end point is when the brick red color is titrated by silver nitrate standard solution, and the cationic degree DC% = [ M multiplied by N x (V-V) 0 )]V (1000 × W × polymer feedstock solids content) × 100%; v-volume of silver nitrate standard solution consumed by sample (mL); w-sample mass (g); v 0 Blank consumption silver nitrate standard solution volume (mL); m-the molecular weight of the recurring unit of formula (1); concentration of N-silver nitrate standard solution (mol/L). The cationic charge density of the polymer is characterized by the cationic degree, preferably the cationic degree is more than 70, and more preferably the cationic degree is more than 80.
Antibacterial composition
Compared with a single bactericide A or a single bactericide B, the bactericide A and the bactericide B composition have a better bactericidal effect, show a synergistic effect, and simultaneously remarkably improve the anti-interference capability on hard water and a surfactant. The mass ratio of the bactericide A to the bactericide B in the invention is 1: 10-5: 1, the preferred mass ratio is 1: 5-3: 1, and the further preferred mass ratio is 1: 3-2: 1. Preferably, the total mass content of the bactericide A and the bactericide B is more than 8ppm multiplied by the use dilution factor, namely, the antibacterial composition has a remarkable bactericidal effect when the concentration of the bactericide after dilution is more than 8 ppm.
Surface active agent
As described above, the antibacterial composition of the present invention has significantly improved hard water and surfactant interference resistance compared to conventional single quaternary ammonium salt bactericides, and thus, in the present invention, the antibacterial composition may further comprise a surfactant, and the amount of the surfactant may be set according to the concentration degree of the detergent. The surfactant in the invention is one or more of anionic surfactant, nonionic surfactant and amphoteric surfactant. The antibacterial composition still has a bactericidal effect when containing a proper amount of anionic surfactant, wherein the anionic surfactant is a non-soap anionic surfactant, and the mass content of the anionic surfactant is less than 80ppm multiplied by the use dilution factor, preferably less than 60ppm multiplied by the use dilution factor. Washing according to GB/T13174 method for measuring detergency and circulation washing performance of detergent for clothing, for common (non-concentrated) detergent, including washing powder and washing liquid, the washing concentration is 0.2%, namely diluting 500 times for use, the anionic surface active mass content is less than 4%, preferably less than 3%. According to QB/T1224 concentrated detergent marking product technical Specification, the concentration of the concentrated laundry detergent sample with total active matter more than 30% is 0.1%, and the concentration of the concentrated laundry detergent sample with total active matter more than 45% is 0.07%.
Further, the anionic surface activity comprises one or more of linear alkylbenzene sulfonate, fatty alcohol-polyoxyethylene ether sulfate, fatty alcohol-polyoxyethylene ether carboxylate, alpha-olefin sulfonate and fatty acid methyl ester sulfonate.
Further, the anionic surfactant is preferably fatty alcohol-polyoxyethylene ether sulfate or fatty alcohol-polyoxyethylene ether carboxylate, wherein the fatty alcohol-polyoxyethylene ether sulfate contains 2 or 3 EO chains; the fatty alcohol polyoxyethylene ether carboxylate contains 7 or 9 EO chains.
The nonionic surfactant is selected from one or more of fatty alcohol ethoxylate, fatty acid methyl ester ethoxylate, alkyl polyglycoside, alkyl alcohol amide, and ethoxylated sorbitan fatty acid ester.
The zwitterionic surfactant comprises one or more of betaine type surfactant, imidazoline type surfactant, amino acid type surfactant, and amine oxide type surfactant, including but not limited to: alkyl betaines, fatty amidobetaines, fatty amidopropyl betaines, fatty amidopropyl hydroxypropyl sulfobetaines, including sodium alkyl acetate type imidazolines, fatty acid type imidazolines, sulfonic acid type imidazolines; aminopropionic acid derivatives, glycine derivatives; alkyl dimethyl amine oxide, fatty amidopropyl dimethyl amine oxide, and the like.
Washing assistant
When the antibacterial composition of the present invention contains a surfactant, it further contains a relevant detergent builder, and the term "detergent builder" broadly refers to other auxiliary materials in the detergent, in addition to the surfactant and water, including the following optional detergent builders: one or more of fillers, excipients, binders, anti-redeposition agents, chelating agents, enzyme preparations, alkaline agents, pH adjusting agents, viscosity adjusting agents, preservatives, pigments, optical brighteners and perfumes. The choice of detergent auxiliaries can vary widely among different types of detergents, and these are well known to those skilled in the art and can be suitably formulated by conventional means.
Compared with the prior art, the invention has the beneficial effects that:
1) The synergistic effect is achieved by compounding the bactericide A and the bactericide B.
2) The antibacterial composition has excellent bactericidal effect under low concentration and strong anti-interference capability to hard water and surfactant.
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 particular embodiments and benefits within the scope of the present invention. The examples are to be construed as merely illustrative of the present invention in more detail and not limitative thereof in any way whatsoever.
Detailed Description
In the following examples, all contents are weight percentages unless otherwise indicated, and the contents of the listed ingredients are converted contents of active substances.
In the examples, the following abbreviations will be used and have the indicated functions.
AE09: ethoxylated fatty alcohol, average degree of ethoxylation 9, nonionic surfactant.
AES: ethoxylated fatty alcohol sulfate with fatty alcohol carbon number of 12-14 and average ethoxylation degree of 2, and anionic surfactant.
And (3) LAS: linear alkyl benzene sulfonic acid sodium, carbon atom number is 10-13, anion surface active agent.
LAB: lauramidopropyl betaine, zwitterionic surfactant.
Benzalkonium chloride: dodecyl dimethyl benzyl ammonium chloride.
Cetylpyridinium chloride: cetyl pyridinium chloride.
Protease: alkaline protease, a product of Novozymes corporation.
Preservative: a mixture of methylisothiazolinone and chloromethylisothiazolinone.
In all examples, the cationic polymers were purchased from Demet Fine chemical group, inc., and are detailed in Table 1.
TABLE 1 cationic Polymer feed information
Examples and comparative examples
Comparative and examples were prepared according to the compositions of tables 2 and 3 below
Table 2 comparative and example antimicrobial compositions
Table 3 comparative and example antimicrobial compositions and examples composition two
Test example 1 Sterilization Effect test
The antibacterial and bacteriostatic performance test is carried out according to QB/T2738-2012 'evaluation method for antibacterial and bacteriostatic effects of daily chemical products'. The action concentration is 0.2%; the acting time is 20 minutes; acting on strains: escherichia coli (ATCC 25922) or Staphylococcus aureus (ATCC 6538). In the present invention, for comparison, a test was conducted under a pure water condition and a standard hard water condition with a hardness of 342mg/L, respectively.
The antibacterial performance is expressed by the bactericidal rate, and the bactericidal rate of the sample is calculated according to the following formula:
sterilization (%) = (viable cell count of control sample-viable cell count of test sample)/viable cell count of control sample × 100%
TABLE 4 comparative and example antimicrobial compositions and examples for antimicrobial effectiveness
As can be seen from the results of table 4, comparative example 1, which uses benzalkonium chloride alone as the bactericide, showed a significant decrease in the bactericidal effect under hard water conditions. Comparative example 2 shows that the bactericidal effect of benzalkonium chloride is remarkably reduced in the presence of nonionic surfactant, while example 2 shows that the benzalkonium chloride compounded with 2521 still has a good bactericidal effect under hard water conditions. The comparative example 3 is a single polyquaternium bactericide DM-2521, and shows that the polyquaternium bactericide DM-2521 has good hard water resistance, but the embodiment 1 adopts benzalkonium chloride and DM-2521 to compound to achieve better bactericidal effect, and the bactericidal rate of the polyquaternium bactericide is obviously superior to that of the comparative examples 1 and 3 which adopt a single bactericide. Comparative example 4 is the compound of benzalkonium chloride and polyquaternium DM-2518, and the result shows that the sterilization effect is not ideal.
TABLE 5 comparative and example antimicrobial compositions and effectiveness of examples (342 mg/L hard water condition)
As can be seen from the results in Table 5, comparative examples 5 and 6, which employ a quaternary ammonium salt bactericide alone, exhibited a very low bactericidal ratio when further comprising a zwitterionic surfactant and an anionic surfactant, whereas examples 3 to 6, which employ a quaternary ammonium salt bactericide compounded with a DM-2521 bactericide, exhibited a higher bactericidal ratio at a use concentration of 0.2% in the presence of a small amount of an anionic surfactant. The results of example 3 show that the antibacterial composition of the present invention has a good bactericidal effect against both staphylococcus aureus (gram-positive bacteria) and escherichia coli (gram-positive bacteria).
Test example 2 Long-term bacteriostatic test
The term "long-lasting bacteriostasis test method" of the present invention specifically comprises the following test steps.
1. Preparation of test bacterial suspension: taking staphylococcus aureus which is freshly cultured on a slant, sucking 5.0mL of bacterial suspension preparation liquid into the slant test tube, repeatedly blowing and sucking, and washing off lawn. Subsequently, the wash solution was transferred in its entirety to another sterile tube and mixed with an electric mixer for 20s or shaken 80 times on the palm to homogenize the bacterial suspension. The bacterial suspension is prepared to bacterial liquid concentration of 1 × 105CFU/mL to 3 × 105CFU/mL.
2. Washing the cloth piece: cutting the specified cloth sample into cloth pieces with specified size, autoclaving, oven drying, washing the cloth pieces with detergent composition according to specified steps, and using hard water with specified hardness as reference. The specified cloth sample refers to cotton fabric conforming to GB/T7568.2-2008 and polyester fabric conforming to GB/T7568.4-2008. The specified size means that each piece of cloth is a circular piece having a diameter of 4.5cm to 5 cm.
A hard water solution of 100g detergent composition at 0.3% concentration was prepared in a 250ml long neck beaker. The hard water solution has a hardness of 50ppm to 500ppm (calculated as CaC03, and a molar ratio of calcium ions to magnesium ions of 3: 2), and is autoclaved at 121 ℃ for 20min before use. 100g of hard water having a hardness of 350ppm (calculated as CaCO3 and having a molar ratio of calcium ions to magnesium ions of 3: 2) was used as a control. Hard water was autoclaved at 121 ℃ for 20min before use.
A magnetic stirring rotor having a diameter of 6cm was added to each of the liquid-filled long-necked beakers, and a cloth piece having a prescribed size was put in. Putting 15-17 pieces of cloth into each bottle, enabling the weight ratio of the cloth pieces to the liquid in each long-neck beaker to be 3: 100-3.5: 100, and stirring and washing the long-neck beaker on a magnetic stirrer at 300rpm for 20min; the liquid was decanted.
The cloth pieces of each long-neck beaker were then removed and transferred to a 2L beaker. One for each 2L beaker. Adding 1L of sterile distilled water into each beaker, and squeezing water on the cloth pieces after the cloth pieces are grabbed and washed for 1min by hands; the number of rinses was 2. After rinsing, the rinsed cloth pieces in each flask were removed and placed in a sterile plate. And each beaker corresponds to 1 sterile plate, and each sterile plate is opened in the biological safety cabinet and is ventilated and dried.
3. Inoculation of the samples: in each group, 2 cloth samples treated with the same detergent composition and 2 cloth samples treated with a control were stacked in 2 empty sterile petri dishes, and 0.2mL of the above-mentioned bacterial suspension was added dropwise, requiring the bacterial suspension to spread as uniformly as possible over the sample. Each test group contained two parallel test subgroups, each test subgroup comprising 1 group of detergent composition treated pieces of cloth (hereinafter referred to as test sample) and 1 group of control treated pieces of cloth (hereinafter referred to as control sample), for immediate elution and testing after inoculation and bacterial elution and testing after continued incubation, respectively.
4. Elution immediately after inoculation: clamping 1 group of test samples and 1 group of control samples which are just inoculated with bacteria by using sterile tweezers, respectively putting into 2 homogeneous bags containing 10g of sterile bacteria eluent, beating for 1min in a beating homogenizer machine, and eluting the bacteria from the test samples.
5. Inoculating cloth pieces, continuously culturing and eluting: 2 sterile culture dishes (1 containing a test sample after inoculation and 1 containing a control sample after inoculation) placed with the inoculated bacteria suspension cloth pieces are covered with a culture dish cover, and the culture dish cover is sealed by a preservative film to prevent the liquid on the carrier from evaporating. Co-culturing at 36 deg.C for 24 hr, and controlling relative humidity to above 85%. After the culture time is up, putting each test sample and the control sample into a homogenizing bag containing 10g of sterile bacteria eluent respectively, beating for 1min in a beating homogenizer, and eluting the bacteria from the samples.
6. And (3) measuring the viable count: 1mL of the eluate was pipetted (step 4 and step 5), transferred into a test tube containing 9mL of phosphate buffered saline (hereinafter referred to as PBS), and sufficiently shaken. 1mL of the sample solution was aspirated from the tube, and the sample solution was sufficiently shaken in another tube containing 9 mLPBS. And in the same way, the eluates in the step 4 and the step 5) are respectively diluted by 10 times in a gradient manner. The suction head is replaced once every time the suction head is moved.
1mL of the sample solution is respectively sucked from each test tube of the serial dilution by a pipette and injected into a plate, 15mL to 20mL of tryptone soy agar medium (TSA) at the temperature of 45 ℃ to 46 ℃ is poured into the plate, a cover is covered on the plate, the plate is placed at room temperature until the mixture is solidified, the plate is inverted and cultured for 48 hours at the temperature of 36 ℃, and the colony count is counted.
The above steps 3 to 6 are tested at least 3 times in parallel.
7. And (3) evaluating the experimental effectiveness: the average number of colonies of the control bacteria eluted immediately after inoculation should be 1X 105CFU/mL to 9X 105CFU/mL, and the bacterial growth value F is counted according to formula (3), and when F is greater than or equal to 1.5, the test is judged to be effective.
F = lgCt-lgC0 … … … … … … … … … … … … … … … formula (3)
F-bacterial growth value for the control;
ct: number of bacteria after a period of time of inoculation and incubation of the control;
c0: number of bacteria measured immediately after inoculation of the control.
8. Calculating the bacteriostatic rate: the bacteriostasis rate is calculated according to the formula (4), and two decimal places are reserved in the result. And taking the calculated value of the bacteriostasis rate as the long-acting antibacterial test result. When the calculated value of the inhibition rate is negative, the expression is 0.00, and when the calculated value of the inhibition rate is more than 99.99%, the expression is more than 99.99%. When the bacteriostatic rate is more than or equal to 90.00 percent in 3 times of tests, the test sample has long-acting antibacterial effect.
Bacteriostasis rate (%) = (C _ T-T _ T)/C _ T × 100% … … … … … … … … … … … … … … … … formula (4)
Ct: the number of bacteria measured after inoculation and incubation of the control for a period of time;
tt: number of bacteria measured after the test sample was inoculated and incubated for a period of time.
TABLE 6 Long-term bacteriostatic test results
As can be seen from the results of table 6, the antibacterial composition of the present invention can impart a long-lasting bacteriostatic effect to fabrics after the washing treatment of the fabrics.
Test example 3 stain removal Performance test
The test method comprises the following steps: the whiteness of the black cloth JB01, the protein cloth JB02 and the sebum cloth JB03 before and after washing is compared with that of the black cloth in the national standard by using the method of GB/T13174 determination of detergency and circular washing performance of detergents for clothing.
And (3) testing conditions are as follows: the washing solution is made of 250ppm hard water, the sample washing concentration is 2g/L, the washing time is 20 minutes, the washing temperature is 30 ℃, and the stirring speed is 60r/min.
Comparative sample: prepared according to standard laundry detergent in QB/T1224 liquid detergent for clothing.
TABLE 7 stain removal Performance test results
From the results of the tests in Table 7, it can be seen that the decontamination effect of the example 3 on the JB-01, JB-02 and JB-03 soiled cloths is equivalent to or better than that of the standard laundry detergent, which indicates that the antibacterial composition and the surfactant of the present invention have good compatibility, bactericidal effect and decontamination performance.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, so that any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (6)
1. An antibacterial composition, characterized in that, the antibacterial composition comprises a bactericide A and a bactericide B, wherein the bactericide A is a quaternary ammonium salt bactericide, and the bactericide B comprises a repeating unit with the following formula structure:
wherein R and R' are alkyl groups having 1 to 3 carbon atoms, X - Is CH 3 SO 4 - 、CH 3 CH 2 SO 4 - Or halogen ions, the weight percentage of the molecular weight of the repeating unit in the total molecular weight of the bactericide B is more than 70 percent, and the weight average molecular weight of the bactericide B is 2000-400000; the weight ratio of the bactericide A to the bactericide B is 1:3 to 2:1;
the bactericide A is one or more of dodecyl dimethyl benzyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide, bis-decyl dimethyl ammonium chloride, bis-decyl dimethyl ammonium bromide, cetyl pyridine chloride, ethylene-based bis (dodecyl dimethyl ammonium bromide) and ethylene-based bis (tetradecyl dimethyl ammonium bromide).
2. The antimicrobial composition of claim 1, wherein said biocide B comprises recurring units having a molecular weight greater than 80% of the total molecular weight of biocide B, and biocide B has a weight average molecular weight of from 5000 to 200000.
3. A liquid detergent comprising an antimicrobial composition, wherein the components of the liquid detergent comprise: 0.1-5% by weight of the antibacterial composition of claim 1, 0.5-65% by weight of a surfactant, 0.2-30% by weight of a washing aid, and the balance of water.
4. The liquid detergent according to claim 3, wherein the surfactant is one or more of a nonionic surfactant, an anionic surfactant and a zwitterionic surfactant, wherein the anionic surfactant is a non-soap anionic surfactant and has a mass content of less than 80ppm x dilution factor in use.
5. The liquid detergent according to claim 4, wherein the non-soap anionic surfactant is a fatty alcohol-polyoxyethylene ether sulfate or a fatty alcohol-polyoxyethylene ether carboxylate.
6. The liquid detergent according to claim 3, wherein the detergent adjunct comprises one or more of fillers, binders, anti-redeposition agents, chelating agents, enzyme preparations, pH adjusting agents, viscosity adjusting agents, preservatives, pigments, optical brighteners and perfume.
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