CN110903918B - Antibacterial fabric detergent composition - Google Patents

Antibacterial fabric detergent composition Download PDF

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CN110903918B
CN110903918B CN201911171544.3A CN201911171544A CN110903918B CN 110903918 B CN110903918 B CN 110903918B CN 201911171544 A CN201911171544 A CN 201911171544A CN 110903918 B CN110903918 B CN 110903918B
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antibacterial
detergent composition
composition
biguanide
fabric detergent
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CN110903918A (en
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钟敏贤
邱振名
黄亮
林焕容
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Guangzhou Liby Enterprise Group Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88Ampholytes; Electroneutral compounds
    • C11D1/94Mixtures with anionic, cationic or non-ionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/046Salts
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    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • C11D3/2079Monocarboxylic acids-salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • C11D3/2086Hydroxy carboxylic acids-salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/30Amines; Substituted amines ; Quaternized amines
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    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/33Amino carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723Polyamines or polyalkyleneimines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50Perfumes
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/62Quaternary ammonium compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/662Carbohydrates or derivatives
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88Ampholytes; Electroneutral compounds
    • C11D1/90Betaines

Abstract

The invention relates to the technical field of fabric detergents, in particular to a stable antibacterial fabric detergent composition containing a chelating agent and a biguanide type antibacterial agent simultaneously. The stability promoter consisting of the electrolyte A and the ethoxylated polyethyleneimine in a certain proportion is added into the composition, so that the compatibility problem of the biguanide antibacterial agent and the chelating agent is solved, the biguanide antibacterial agent and the chelating agent can stably coexist in the composition for a long time, and the stability problems of turbidity, precipitation and the like caused by coexistence of the biguanide antibacterial agent and the chelating agent in the fabric detergent are solved; the composition has an obvious synergistic promotion effect on the antibacterial effect of the biguanide antibacterial agent, so that the biguanide antibacterial agent in the composition can achieve a good antibacterial effect at a low dosage, and the product cost is greatly saved; in addition, the chelating agent can stably coexist in the composition for a long time, so that the decontamination performance of the composition is ensured and improved, and the problems of yellowing and the like caused by long-term and multiple times of washing of clothes are solved.

Description

Antibacterial fabric detergent composition
Technical Field
The invention relates to the technical field of fabric detergents, in particular to a stable antibacterial fabric detergent composition containing a chelating agent and a biguanide type antibacterial agent.
Background
At present, anion and nonionic surfactants are commonly compounded in the formula of the laundry detergent, and most of antibacterial laundry detergents are added with bactericides to achieve the antibacterial effect, but after the laundry detergent is diluted in water in a large amount, the action concentration of the contained antibacterial agent can be greatly reduced, and the antibacterial effect is directly influenced.
The biguanide antibacterial agent is a novel cationic amphiphilic molecule antibacterial agent, and has high efficiency, broad spectrum, no irritation, and no odorAnd the like, and is particularly effective to fungi such as candida albicans and the like which are easy to cause gynecological diseases. The major contributor to biguanide antimicrobials is the (═ NH) reactive group, which is accessible to H+Combined to form (═ NH)+) A cation. The negatively charged bacteria are attracted by cations, so that the bacteria cannot divide and reproduce, lose activity, inhibit the respiratory function and cause 'contact death'. Biguanide based antibacterial agents are more commonly used in professional disinfection and household products, but are less commonly used in laundry detergents. Active groups in the biguanide antibacterial agent are positively charged and are easily neutralized by components with negative charges (such as anionic activity and the like) in a laundry detergent to form turbidity or precipitation, so that the stability and the antibacterial effect of a product are influenced, so a nonionic or zwitterionic surfactant system is mostly adopted, the detergency of the formula is generally poor, and the biguanide antibacterial agent is added in the formula in a large amount to easily cause skin irritation and has high cost.
Most areas in China are hard water and contain various metal ions, wherein magnesium ions, calcium ions and the like can reduce the washing effect of the surfactant. The metal ions also cause the fabric to turn yellow, turn gray, feel hard, etc. Therefore, the laundry detergent is usually added with a chelating agent, so that the water hardness can be reduced, dirt is easy to dissociate, disperse and remove, and meanwhile, the chelating agent plays an important role in promoting the washing effect of the surfactant.
Sodium citrate and the like have good chelating ability and low price due to the fact that molecules contain a plurality of carboxylate radicals, and are commonly used as chelating agents in laundry detergents. However, such chelating agents are negatively charged because they contain multiple carboxylate groups and are incompatible with the positively charged biguanide reactive groups. The biguanide group has high activity, electropositivity formed by polymerization, linear long molecular structure and larger relative molecular mass, and generates flocculation effect when being mutually adsorbed with a chelating agent with negative charge, so that the mixture is highly turbid. This is because the adsorption effect of the negatively charged chelating agent changes the interface charge of the biguanide antibacterial agent dispersion system, and causes coagulation and sedimentation phenomena, which affects the stability and greatly reduces the bactericidal effect.
Chinese patent CN200710179670 discloses an antibacterial laundry detergent capable of simultaneously sterilizing and decontaminating, chinese patent CN201280020640 discloses a sterilizing composition and a sterilizing detergent composition, chinese patent CN201010177957 discloses a sterilizing detergent, chinese patent CN201710980949 discloses a non-toxic floor furniture cleaning agent with sterilizing function, chinese patent CN201110276751 discloses a textile antimicrobial washing finishing agent, chinese patent CN200980115520 discloses a cleaning, sterilizing and disinfecting preparation, chinese patent CN200910195827 discloses a compound polyhexamethylene guanidine antibacterial hand washing solution, chinese patent CN201310613452 discloses a computer sterilizing detergent and a preparation method thereof, biguanide antibacterial agents are all used in the patent documents, but chelating agents are not added, and the compatibility contraindication between the biguanide antibacterial agents and the chelating agents can affect coagulation and sedimentation phenomena, has great influence on the stability of the formula and the sterilization effect.
At present, some patents use chelating agents in the formulation containing biguanide antibacterial agents, but most of them require addition of a large amount of fatty alcohol compounds, short-chain fatty alcohol ethers or other organic solvents for solubilization and penetration promotion. For example, chinese patent CN201610307397 discloses an antibacterial fabric detergent, which adopts a biguanide antibacterial agent, adds a chelating agent, and simultaneously adds a relatively high amount of C1-6 alkyl alcohol for solubilization. Chinese patent CN201610720405 discloses an antibacterial high-efficiency laundry detergent, which comprises biguanides as antibacterial components, chelating agent, and organic solvents such as ethanol, 2-methyl-2, 4-pentanediol and diethylene glycol monobutyl ether. Chinese patent CN200410101068 discloses a multifunctional disinfecting and sterilizing detergent composition and a preparation method thereof, wherein a guanidine bactericide is adopted, a chelating agent is added, and a large amount of fatty alcohol compounds are added for solubilization. The large amount of fatty alcohol compounds, short-chain fatty alcohol ethers or other organic solvents leads to high formulation cost and is not favorable for the use safety of skin.
Disclosure of Invention
The present invention has been made in view of the above problems occurring in the prior art, and an object of the present invention is to provide a stable antibacterial fabric detergent composition containing both a chelating agent and a biguanide-type antibacterial agent, and having high detergency and antibacterial properties.
In order to achieve the purpose, the invention adopts the following technical scheme.
An antibacterial fabric detergent composition comprises the following components in percentage by mass:
Figure BDA0002287294050000021
the electrolyte A is selected from at least one of hydrochloride, acetate, carbonate, bicarbonate, nitrate, hydrogen phosphate, dihydrogen phosphate, oxalate, sulfate and sulfite.
Preferably, the electrolyte A is a sodium salt, a potassium salt or an ammonium salt.
More preferably, the electrolyte a is selected from at least one of sodium chloride, potassium chloride, sodium sulfate and ammonium chloride.
Preferably, the weight average molecular weight of the polyethyleneimine backbone in the ethoxylated polyethyleneimine is 300-2000, and the average degree of ethoxylation is 2-50.
More preferably, the weight average molecular weight of the polyethyleneimine backbone in the ethoxylated polyethyleneimine is from 500 to 2000, and the average degree of ethoxylation of the ethoxylated polyethyleneimine is from 5 to 50.
Preferably, the biguanide antibacterial agent is at least one selected from the group consisting of chlorhexidine, polyhexamethylene biguanide, polyaminopropyl biguanide, hydrochloride, acetate and gluconate of chitosan biguanide.
Preferably, the chelating agent is at least one selected from the group consisting of citrate, α -glucoheptonate, methylglycine diacetate, glutamic acid diacetate, N-dicarboxylic acid amino-2-hydroxypropane sulfonate, and 3-hydroxy-2, 2' -iminodisuccinate.
More preferably, the chelating agent is a lithium salt, potassium salt or sodium salt.
More preferably, the chelating agent is sodium citrate, sodium glutamate diacetate (GLDA) or glycine diacetic acid (MGDA).
Preferably, the other auxiliary agents comprise at least one of an enzyme preparation, an acid-base regulator, a essence and a preservative.
Preferably, the surfactant consists of a cationic surfactant, a nonionic surfactant and a zwitterionic surfactant; and the mass percent of each surfactant in the antibacterial fabric detergent composition is as follows:
0.5 to 10 percent of cationic surfactant,
5 to 30 percent of nonionic surfactant,
1-30% of zwitterionic surfactant.
More preferably, the cationic surfactant is at least one selected from the group consisting of quaternary ammonium salt surfactants, heterocyclic surfactants, and polymeric cationic surfactants.
More preferably, the nonionic surfactant is selected from at least one of fatty alcohol alkoxylates, alkyl polyglycosides, fatty acid alkoxylates, fatty acid ethoxylates, fatty acid alkylolamides, ethoxylated sorbitan esters.
More preferably, the zwitterionic surfactant is at least one selected from the group consisting of an amino acid type surfactant, an amine oxide type surfactant, a betaine type surfactant and an imidazoline type surfactant.
Preferably, in the antibacterial fabric detergent composition, the weight percentage of the biguanide antibacterial agent is preferably 0.05-3%; the mass percent of the electrolyte A is preferably 2-4%; the mass percentage of the ethoxylated polyethyleneimine is preferably 0.5 to 3%.
Preferably, in the antibacterial fabric detergent composition, the weight ratio of the electrolyte A to the ethoxylated polyethyleneimine is preferably 0.3 to 25, more preferably 0.5 to 8.
Preferably, the above-mentioned antibacterial fabric detergent composition has a pH of 4.0 to 7.0.
The pH of the antibacterial fabric detergent composition is adjusted to 4.0 to 7.0(25 ℃) with an acid-base adjusting agent, preferably 5.0 to 6.5(25 ℃).
The pH regulator comprises an acidity regulator and an alkalinity regulator.
Preferably, the acidity regulator is selected from citric acid, succinic acid, hydrochloric acid; the alkalinity regulator is selected from organic amine, alkali metal hydroxide and alkali metal carbonate.
More preferably, the acidity regulator is citric acid and the alkalinity regulator is sodium hydroxide.
Compared with the prior art, the invention has the beneficial effects that:
the stability promoter consisting of the electrolyte A and the ethoxylated polyethyleneimine in a certain proportion is added into the composition, so that the compatibility problem of the biguanide antibacterial agent and the chelating agent is solved, the biguanide antibacterial agent and the chelating agent can stably coexist in the composition for a long time, and the stability problems of turbidity, precipitation and the like caused by coexistence of the biguanide antibacterial agent and the chelating agent in the fabric detergent are solved; in addition, the stabilizing accelerator consisting of the electrolyte A and the ethoxylated polyethyleneimine in the proportion has an obvious synergistic accelerating effect on the antibacterial effect of the biguanide antibacterial agent, so that the biguanide antibacterial agent in the composition can achieve a good antibacterial effect at a low dosage, the product cost is greatly saved, and the stabilizing accelerator has a high-efficiency antibacterial effect on pathogenic bacteria such as staphylococcus aureus, escherichia coli, candida albicans and the like; in addition, the chelating agent can stably coexist in the composition for a long time, so that the decontamination performance of the composition is ensured and improved, and the problems of yellowing and the like caused by long-term and multiple times of washing of clothes are solved.
The composition disclosed by the invention is weakly acidic, has good washing performance without adding an anionic surfactant, reduces the irritation of the composition to the skin, and is mild and skin-friendly.
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 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.
Fabric detergent composition
The fabric detergent composition of the present invention is contacted with a substrate (i.e., fabric article) to be contacted in water, thereby removing stains from the surface of the substrate and cleaning the surface of the substrate. The fabric detergent compositions of the present invention include, but are not limited to, liquid fabric detergent compositions and solid fabric detergent compositions.
Liquid fabric detergent compositions typically comprise a surfactant system and other common adjuvants including viscosity modifiers, anti-redeposition agents, water softeners, optical brighteners, enzyme preparations, colorants, preservatives, perfumes and the like.
Antibacterial agent
The term "antibacterial agent" as referred to in the present invention means a compound whose main action is to kill or prevent the growth or reproduction of bacteria and fungi. Conventional antibacterial agents include phenol-containing antibacterial agents (e.g., p-chloroxylenol), oxygen-containing antibacterial agents, and the like, and the preferred antibacterial agent of the present invention is a biguanide antibacterial agent.
Biguanide antibacterial agent
The content of the biguanide antibacterial agent in the detergent composition is 0.01-5% by weight, preferably 0.05-3% by weight.
The cation of the biguanide antibacterial agent is selected from at least 1 of chlorhexidine, polyhexamethylene biguanide, polyaminopropyl biguanide and chitosan biguanide, and polyhexamethylene biguanide is preferred. The anion is selected from 1 of hydrochloric acid, acetic acid and gluconic acid, preferably hydrochloric acid. Namely, the biguanide antibacterial agent is at least one selected from chlorhexidine, polyhexamethylene biguanide, polyaminopropyl biguanide, hydrochloride, acetate and gluconate of chitosan biguanide.
Chelating agents
The chelating agent is present in the detergent composition in an amount of from 1% to 5% by weight.
The chelating agent may be at least 1 selected from citrate, α -glucoheptonate, methylglycine diacetate, glutamic acid diacetate, N-dicarboxamide-2-hydroxypropane sulfonate, and 3-hydroxy-2, 2' -iminodisuccinate, preferably 1 or more selected from citrate, glutamic acid diacetate (GLDA), and glycine diacetate (MGDA). The salt may be selected from lithium, sodium and potassium salts, preferably sodium, potassium and more preferably sodium.
Electrolyte A
The content of the electrolyte A in the detergent composition is 1.5-5% by weight, preferably 2-4% by weight.
The positive ions of the electrolyte A are selected from one or more of sodium ions, potassium ions and ammonium ions, and the negative ions are selected from one or more of chloride ions, acetate ions, carbonate ions, bicarbonate ions, nitrate ions, hydrogen phosphate ions, dihydrogen phosphate ions, oxalate ions, sulfate ions and sulfite ions; preferably any one or a mixture of two or more of sodium chloride, potassium chloride, sodium sulfate and ammonium chloride. Namely, the electrolyte A is at least one selected from hydrochloride, acetate, carbonate, bicarbonate, nitrate, hydrogen phosphate, dihydrogen phosphate, oxalate, sulfate and sulfite, and the electrolyte A is sodium salt, potassium salt or ammonium salt.
Ethoxylated polyethyleneimine
The weight average molecular weight of the main chain of the polyethyleneimine in the ethoxylated polyethyleneimine of the present invention is 300 to 2000, and the average degree of ethoxylation is 2 to 50. Preferably, the weight average molecular weight of the polyethyleneimine backbone in the ethoxylated polyethyleneimine is from 500 to 2000. Preferably, the ethoxylated polyethyleneimine has an average degree of ethoxylation of from 5 to 50. The content of the ethoxylated polyethyleneimine is 0.1-5 wt% of the detergent composition, and preferably 0.5-3 wt%.
Ratio of electrolyte A to ethoxylated polyethyleneimine
It has been found that the positive charges of the active groups of biguanide antibacterial agents are easily adsorbed by negatively charged chelating agents, so that the repulsive force between particles is weakened or disappeared, and the particles are aggregated to form polymers to precipitate, thereby greatly reducing the sterilization effect while affecting the stability.
We have surprisingly found that the combination of electrolyte a and ethoxylated polyethyleneimine in a specific ratio allows for stable co-presence of chelating agent and biguanide antibacterial agent, while promoting the antibacterial action of the biguanide antibacterial agent at low levels. Since the mechanism of stably promoting the antibacterial action has not been clearly studied, it is presumed that the possible mechanism is: the electrolyte A and the ethoxylated polyethyleneimine with proper proportion can change the charge distribution of the polymer more easily, and on one hand, the biguanide antibacterial agent can be recovered again by the interface charge changed by the chelating agent, the repulsion among particles is increased, and the biguanide antibacterial agent is not easy to aggregate with each other and settle; on the other hand, a certain synergistic effect may exist between the active groups of the biguanide antibacterial agent and the active groups of the biguanide antibacterial agent, so that the bactericidal effect of the biguanide antibacterial agent is enhanced, and even the biguanide antibacterial agent with low dosage can achieve better antibacterial performance.
From the viewpoint of enhancing the antibacterial effect of the biguanide antibacterial agent, the weight ratio of the electrolyte a to the ethoxylated polyethyleneimine in the stabilization accelerator is 0.3 to 50, preferably 0.3 to 25, and more preferably 0.5 to 8.
Cationic surfactant
The detergent compositions according to the examples herein comprise cationic surfactants in an amount of from 0.5 to 10% by weight. The cationic surfactant is selected from at least one of quaternary ammonium salt surfactants, heterocyclic surfactants and polymer cationic surfactants; including but not limited to: mono-long linear quaternary ammonium salts, bi-long linear quaternary ammonium salts, benzyl quaternary ammonium salts, hydroxyalkyl quaternary ammonium salts, fatty amidopropyl hydroxyalkyl quaternary ammonium salts, polyquaternary ammonium salts obtained by copolymerization of vinyl pyrrolidone with unsaturated amides or unsaturated quaternary ammonium salts.
Nonionic surfactant
In the examples herein, the total weight of the mixture of nonionic surfactants is from 5 to 30% of the total weight of the liquid detergent composition.
The nonionic surfactant is selected from at least one of fatty alcohol alkoxylates, alkyl polyglycosides, fatty acid alkoxylates, fatty acid ethoxylates, fatty acid alkylolamides and ethoxylated sorbitan esters.
In some embodiments, the nonionic surfactant mixture preferably contains a fatty alcohol alkoxylate having the general formula:
Figure BDA0002287294050000071
wherein n is 6 to 24; x is 0.5 to 30 and y is 0 to 10.
It should be noted that the fatty alcohol alkoxylate is a product of ring-opening polymerization of a fatty alcohol and an alkylene oxide in the presence of an alkaline catalyst, and thus is 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 ECOSURFEH 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 from BASF.
In some embodiments, the nonionic surfactant mixture preferably comprises an alkyl polyglycoside having the general formula:
Figure BDA0002287294050000072
wherein n is 6 to 24, p is 1.1 to 3, preferably n is 8 to 16. In one embodiment, alkyl polyglycosides such as the Glucopon series of alkyl glycosides from BASF are selected.
The nonionic surfactant mixture may contain fatty acid alkoxylates, preferably from ethoxylated C8 to C18 fatty acid esters, with 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 nonionic surfactant mixture may contain fatty acid alkylolamides, the fatty acid having 6 to 24 carbon atoms, may be a linear fatty acid, may be a branched fatty acid, may be a saturated fatty acid, and may be an 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 nonionic surfactant mixture may contain fatty acid methyl ester ethoxylates of the general formula:
Figure BDA0002287294050000081
wherein n is 6 to 24; x is 2 to 20, preferably n is 8 to 18, x is 0.5 to 30. Preferably x is 4 to 10.
The nonionic surfactant mixture may also contain a polyether surfactant. The polyether surfactant is a polymer, a nonionic surfactant containing ethoxy and/or propoxy repeating units, suitable examples being the Pluronic series from BASF.
Zwitterionic surfactants
The detergent composition of the present invention comprises 1-30 wt% of a cationic surfactant.
The zwitterionic surfactant is selected from at least one of betaine surfactant, imidazoline surfactant, amino acid surfactant and amine oxide surfactant; including but not limited to: alkyl betaines, fatty amidobetaines, fatty amidopropyl betaines, fatty amidopropyl hydroxypropyl sulfobetaines, sodium alkyl acetate type imidazolines, fatty acid type imidazolines, sulfonic acid type imidazolines, aminopropionic acid derivatives, glycine derivatives, alkyl dimethyl amine oxides, fatty amidopropyl dimethyl amine oxides, and the like.
Other auxiliaries
The other auxiliary agents comprise any one or a combination of more of an enzyme preparation, an acid-base regulator, a viscosity regulator, an anti-redeposition agent, essence and a preservative.
Enzyme preparation
One or more enzyme preparations may be included in the detergent compositions of the present invention to enhance the soil release properties of the product and to provide other benefits to fabric care. The enzyme preparation is selected from the following enzymes: proteases, alpha-amylases, cellulases, hemicellulases, phospholipases, esterases, lipases, peroxidases/oxidases, pectinases, lyases, mannanases, cutinases, reductases, xylanases, pullulanases, tannases, pentosanases, maltoglucanases, arabinases, beta-glucanases, preferably proteases. Suitable proteases include, but are not limited to, Savinase16L from Novin, Savinase Ultra16XL, Savinase event 16L, Progress Uno 101L, Progress Uno 100L, Effect P150 from DuPont, preferenzP200, preferenzP300, and Lavergy 104L, 104LS from Bassfer. The enzyme preparation is contained in an amount of 0.001-5%, preferably 0.01-2% by weight based on the total weight of the detergent composition.
Acid-base regulator
The detergent composition of the present invention has a weakly acidic solution, and the pH of the solution is 4.0 to 7.0, preferably 5.0 to 6.5. The pH is controlled by adding an acidity or alkalinity adjusting agent, which includes acidity and alkalinity adjusting agents. 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 weak acid salt which are well known in the daily chemical product industry, preferably selected from organic amine, alkali metal hydroxide and alkali metal carbonate, more preferably sodium hydroxide.
Essence
The detergent compositions to which the present invention relates may contain perfume which comprises all perfume ingredients suitable for use in cleaning products.
Preservative
The detergent compositions according to the invention may comprise a preservative in an amount to provide preservative properties to the liquid formulation, the preservative being present in an amount of from 10ppm to 500ppm and being selected from the group consisting of 1, 2-benzisothiazolin-3-one, 2-methylisothiazolin-3-one, 5-chloro-2-methylisothiazolin-3-one, phenoxyethanol, DMDMH, and mixtures thereof.
Antibacterial power testing method
The antibacterial power refers to the killing capability of the fabric detergent composition on different bacteria and fungi, 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: escherichia coli ATCC 25922, Staphylococcus aureus ATCC 6538, Candida albicans ATCC 10231.
Evaluation criteria for antibacterial power
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 antibacterial property is not achieved; has antibacterial effect when the bactericidal rate is more than or equal to 90%. The higher the bactericidal rate, the stronger the antibacterial action.
Stability testing method
High-temperature stability: after the composition is bottled and sealed, the mixture is placed at 45 +/-2 ℃ and is kept at the constant temperature for one month, and the appearance is observed under the environment of returning to the room temperature of 25 +/-5 ℃.
Low-temperature stability: the composition is bottled and sealed, then is placed at 0 +/-2 ℃ for a month at constant temperature, and is restored to the room temperature of 25 +/-5 ℃ for observation of appearance.
And (3) normal temperature stability: the composition is bottled, sealed, kept at 25 + -5 deg.C for one month, and directly observed.
Stability evaluation criteria
The sample is uniform liquid, is not layered, has no precipitate and is qualified in stability;
the sample is represented by "+" as turbid liquid, demixing or precipitation and unqualified stability, and the number of "+" represents the turbid demixing degree, and the more the turbid or precipitation phenomenon is obvious, the more unstable the sample is.
Detergency testing method
Detergency in the present invention refers to the ability of a fabric detergent composition to remove various stains. The test is carried out according to the method of the national standard GB/T13174-2008. Three dirty cloths of carbon black, protein and sebum are adopted, and a WSD-3U fluorescence whiteness meter is used for measuring the whiteness W1 of the three dirty cloths before washing. Hard water with the hardness of 250ppm is prepared according to GB/T13174-2008 standard, and one-time washing is completed by adopting an RHLQ type vertical decontamination machine, wherein the addition amount of a detergent is 2g/L in a common type, and the concentration type is 0.7 g/L. Washing time is 20min, washing temperature is 30 ℃, stirring speed is 120r/min, the washed dirty cloth is rinsed and dried, whiteness W2 of the washed cloth piece is tested by a whiteness meter, and a whiteness difference delta W calculation method is as follows:
Δ W ═ W2-W1; wherein W2 is the whiteness after washing, and W1 is the whiteness before washing.
The detergency of the sample detergent is compared with that of the national standard detergent to calculate a P value,
p ═ Δ W sample/Δ W standard; the delta W sample is the whiteness difference of the soiled cloth before and after cleaning with the sample detergent, and the delta W standard is the whiteness difference of the soiled cloth before and after cleaning with the national standard detergent.
Evaluation criteria for detergency
Higher P values indicate better detergency. If P is more than or equal to 1, the product is qualified, and if P is less than 1, the product is judged to be unqualified.
Skin safety evaluation test method
The skin safety evaluation test of the invention refers to the seventh part of the cosmetic safety technical specification 2015 edition, namely the repeated open type smearing experiment in the human skin patch test method. The method comprises the steps of selecting 30 volunteers, taking hands as test parts, diluting a detergent sample to be tested into 0.2% concentration by using pure water, taking the pure water as a control during testing, enabling the test subjects to completely soak the left hands into the diluent of the detergent to be tested, completely soak the right hands into the pure water for 1 minute, evaluating hand feeling after soaking is finished, and cleaning the hands by using clear water after evaluation is finished. From the start of the test, the skin reactions were observed 1 time per day for 7 consecutive days.
Skin safety evaluation criteria
The skin grade of the volunteers after each product use was judged and determined according to the skin reaction judgment standard in the repeated open smearing test for human skin in the cosmetic hygiene Specification (2015 edition) (see Table 1).
TABLE 1 grading Standard of skin response for repetitive open-type skin painting test
Figure BDA0002287294050000101
The safety of the test samples on human skin was evaluated according to the following criteria, using the number of cases in which each skin reaction of volunteers was graded after 7 days:
if the test sample is 0-level reaction, judging that the safety of the test sample to the human skin is good;
if there are grade 1 adverse skin reactions below 3 cases (including 3 cases) and grade 2 adverse skin reactions below 1 case (including 1 case), the test sample is judged to have general safety to human skin.
If more than 3 skin adverse reactions with grade 1 exist and more than 1 skin adverse reaction with grade 2 exist, the test sample is judged to have poor safety to human skin.
Methods of formulation and use
The fabric detergent compositions of the present invention are prepared by various methods well known to those skilled in the art. The formulation of the composition may be carried out by conventional means, and the appropriate processing temperature and processing time will be selected with reference to the state and effect of the components in solution, and the stability of the components.
The fabric detergent composition of the present invention is used in a manner well known to those skilled in the art, and is typically used by bringing a specific detergent composition into contact with the surface of a laundry in an undiluted manner or in a diluted manner in water (a contact step), and then rinsing the surface of the laundry (a rinsing step). 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.
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.
In the examples below, the following abbreviations will be used and have the indicated functions.
AEO 7: ethoxylated fatty alcohol, average degree of ethoxylation 7, nonionic surfactant.
AEO 9: ethoxylated fatty alcohol, average degree of ethoxylation 9, nonionic surfactant.
APG: alkyl glucoside, wherein the number of carbon atoms of the alkyl is 8-16, the average polymerization degree is 1.1-3, and the nonionic surfactant is used as a surfactant.
LAB: lauramidopropyl betaine, zwitterionic surfactant.
1227: dodecyl dimethyl benzyl ammonium chloride and cationic surfactant.
1631: cetyl trimethyl ammonium chloride and cationic surfactant.
PHMB: polyhexamethylene biguanide hydrochloride and biguanide antibacterial agent.
EPEI: ethoxylated polyethyleneimine, abbreviated to PEIm(EO)nM represents the weight average molecular weight of the polyethyleneimine backbone in the ethoxylated polyethyleneimine and n represents the average degree of ethoxylation, polymer.
GLDA: glutamic acid, sodium diacetate, and a chelating agent.
MGDA: sodium methylglycinate diacetate and a chelating agent.
Process for preparing liquid detergent composition
1) Adding part of deionized water into the preparation tank;
2) starting heating, adding a surfactant, and stirring until the surfactant is completely dissolved;
3) stopping heating, adding the rest deionized water into the preparation tank, and accelerating the temperature reduction;
4) cooling to below 40 deg.C, adding biguanide antibacterial agent, electrolyte A, ethoxylated polyethyleneimine, enzyme preparation, essence, antiseptic and other components, and stirring to dissolve completely;
5) adding a viscosity regulator and an acid-base regulator, stirring until the mixture is completely dissolved, regulating the pH value and the viscosity, and discharging after the detection is qualified.
First, antibacterial test
The detergent compositions prepared in examples 1 to 10 and comparative examples 1 to 18 were respectively composed of the following components in tables 2 to 4, which were uniformly mixed, and then the viscosity and pH thereof were adjusted to product design requirements by adding a viscosity modifier and an acid-base modifier. The pH of the detergent compositions prepared in the following examples and comparative examples was controlled to be between 5.0 and 6.5. The detergent compositions prepared in each example and comparative example were respectively subjected to antibacterial tests according to the test methods described previously, and the test results are shown in tables 2 to 5.
TABLE 2 results of antibacterial tests of examples 1-3 and comparative examples 1-6
Figure BDA0002287294050000121
In comparative example 1, no biguanide antibacterial agent was added, and no antibacterial effect was exhibited. Comparative example 2 with a lower amount of PHMB, but without the addition of the stabilization promoters (electrolyte a and ethoxylated polyethyleneimine) and chelating agent, there was no antibacterial effect against staphylococcus aureus, escherichia coli, and candida albicans. Comparative example 3 added lower amounts of PHMB and sodium citrate, but no stabilization promoter, had no antimicrobial effect against staphylococcus aureus, escherichia coli, and candida albicans. Comparative example 4 with electrolyte a alone and no ethoxylated polyethyleneimine has no antimicrobial effect against staphylococcus aureus, escherichia coli and candida albicans. Comparative example 5, with only ethoxylated polyethyleneimine and no electrolyte a, had no antimicrobial effect against staphylococcus aureus, escherichia coli and candida albicans. In comparative example 6, although the electrolyte a and the ethoxylated polyethyleneimine were added, there was no antibacterial effect against staphylococcus aureus, escherichia coli, and candida albicans due to improper mixing ratio of the electrolyte a and the ethoxylated polyethyleneimine.
As can be seen from the results of the tests of the detergent compositions prepared in the above examples and comparative examples, when PHMB and sodium citrate were present, potassium chloride or PEI was added separately500(EO)20No antibacterial effect; when potassium chloride and PEI500(EO)20When the weight ratio of the components is 1: 6, the antibacterial effect is not generated; in examples 1 to 3, potassium chloride and PEI500(EO)20The weight ratio of the components is 1: 2, 8: 1 and 50: 1 respectively, the sterilizing rate of the detergent composition on staphylococcus aureus and escherichia coli reaches 99.9%, the detergent composition has an antibacterial effect on candida albicans, and the antibacterial effect is obviously promoted when the electrolyte A and the ethoxylated polyethyleneimine are used together in a proper ratio.
Table 3 results of antibacterial test of example 4 and comparative examples 7 to 12
Figure BDA0002287294050000131
In example 4, sodium acetate and PEI2000(EO)50The weight ratio of the components is 3: 1, the antibacterial agent has strong antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans, and the sterilization rate reaches 99.9%. Comparative example 7 the detergent composition had no antibacterial effect against staphylococcus aureus, escherichia coli and candida albicans, since PHMB was not added. Comparative example 8, in which 5% of PHMB was added but electrolyte a, ethoxylated polyethyleneimine and chelating agent were not added, the detergent composition had antibacterial effects against staphylococcus aureus and escherichia coli, but no antibacterial effect against candida albicans. In comparative example 9, after adding GLDA, the antibacterial effect of PHMB is obviously reduced due to the compatibility problem of PHMB and GLDA, and no antibacterial effect is exerted on staphylococcus aureus, escherichia coli and candida albicans, and in comparative example 10 and comparative example 11, sodium acetate and PEI are respectively and independently added2000(EO)50The antibacterial effect of the detergent composition is not obviously improved. As can be seen from comparative example 12,when sodium acetate and PEI2000(EO)50At a weight ratio of 100: 1, the detergent composition also has no antibacterial effect.
Table 4 results of antibacterial tests of example 5 and comparative examples 13 to 18
Figure BDA0002287294050000141
In example 5, ammonium sulfate and PEI2000(EO)50The weight ratio of the components is 2: 5, the antibacterial agent has strong antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans, and the sterilization rate reaches 99.9%. In comparative example 13, since chlorhexidine hydrochloride was not added, the detergent composition had no antibacterial effect against staphylococcus aureus, escherichia coli, and candida albicans. Comparative example 14, in which 0.5% of chlorhexidine hydrochloride was added but electrolyte a, ethoxylated polyethyleneimine and chelating agent were not added, the detergent composition had an antibacterial effect against staphylococcus aureus but no antibacterial effect against escherichia coli and candida albicans. In comparative example 15, after the addition of MGDA, the antibacterial effect of chlorhexidine hydrochloride was significantly reduced due to the compatibility problem between chlorhexidine hydrochloride and MGDA, and no antibacterial effect was observed against staphylococcus aureus, escherichia coli, and candida albicans, in comparative example 16 and comparative example 17, ammonium sulfate and PEI were separately added300(EO)2The antibacterial effect of the detergent composition is not obviously improved. As can be seen from comparative example 18, when ammonium sulfate and PEI300(EO)2At a weight ratio of 1: 16, the detergent composition also has no antibacterial effect.
TABLE 5 results of antibacterial tests of examples 6-10
Figure BDA0002287294050000151
The compositions of examples 6-10 were supplemented with appropriate proportions of sodium acetate and PEI500(EO)5The sterilizing rate of the detergent composition on staphylococcus aureus and escherichia coli reaches 99.9%, and the sterilizing rate on candida albicans is more than 98.3%.
Second, stability test
The detergent compositions prepared in the above examples 1 to 10 and comparative examples 1 to 18 were subjected to stability tests according to the test methods described previously, and the test results are shown in tables 6 to 9.
TABLE 6 stability test results for examples 1-3 and comparative examples 1-6
Figure BDA0002287294050000152
Figure BDA0002287294050000161
The detergent compositions of comparative examples 1 and 2 were both clear and transparent with only the biguanide antibacterial agent PHMB or sodium citrate added. In comparative example 3, turbidity immediately occurred due to the simultaneous addition of PHMB and sodium citrate to the composition, and white precipitates occurred during the high and low temperature accelerated stability examination. As can be seen from comparative examples 4 and 5, when PHMB and sodium citrate were present in the composition, even though potassium chloride or PEI was added separately to the composition500(EO)20The composition still has turbidity, precipitation and unqualified stability. As can be seen from comparative example 6, when PHMB and sodium citrate were present in the composition, even though potassium chloride and PEI were added simultaneously to the composition500(EO)20If potassium chloride and PEI500(EO)20The addition ratio of (A) is not proper, the composition still has turbidity, and the stability is not qualified.
When PHMB and sodium citrate coexist in the composition, if potassium chloride and PEI are added in proper proportion500(EO)20Compositions as in examples 1-3 wherein potassium chloride and PEI500(EO)20The weight ratio of PHMB to sodium citrate is 1: 2, 8: 1 and 50: 1 respectively, so that PHMB and sodium citrate can stably coexist in the composition, the composition is a clear and transparent liquid, and the stability is qualified in the high-low temperature accelerated stability test.
Table 7 stability test results of example 4 and comparative examples 7 to 12
Figure BDA0002287294050000162
As can be seen from comparative example 7 and comparative example 8, the compositions were clear and transparent when only the biguanide antibacterial agent PHMB or GLDA was present in the compositions, while as shown in comparative example 9, when PHMB and GLDA were added simultaneously to the compositions, the compositions immediately became cloudy and white precipitates appeared as stability was high and low temperature accelerated stability. As can be seen from comparative examples 10 and 11, when PHMB and GLDA were present in the composition, even though sodium acetate or PEI was added separately to the composition500(EO)50The composition still has turbidity, precipitation and unqualified stability. As can be seen from comparative example 12, when PHMB and GLDA were present in the composition, even though sodium acetate and PEI were added simultaneously to the composition500(EO)50Sodium acetate and PEI500(EO)50The addition ratio of (A) is not proper, the composition still has turbidity, and the stability is not qualified.
When PHMB and GLDA coexist in the composition, if sodium acetate and PEI are added in appropriate proportion2000(EO)50The composition of example 4, wherein the sodium acetate and PEI2000(EO)50The weight ratio of PHMB to GLDA is 3: 1 respectively, PHMB and GLDA can stably coexist in the composition, the composition is clear and transparent liquid, and the stability is qualified in high-low temperature accelerated stability investigation.
Table 8 stability test results of example 5 and comparative examples 13 to 18
Figure BDA0002287294050000171
As can be seen from comparative example 13 and comparative example 14, only chlorhexidine hydrochloride and MGDA, which are biguanide antibacterial agents, were present in the composition, and the composition was clear and transparent, while as shown in comparative example 15, when chlorhexidine hydrochloride and MGDA were added simultaneously to the composition, the composition immediately appeared cloudy, and white precipitation appeared as the stability was high and low and accelerated stability was examined.On the other hand, as can be seen from comparative examples 16 and 17, when chlorhexidine hydrochloride and MGDA coexist in the composition, even if ammonium sulfate or PEI is added separately in the composition300(EO)2The composition still has turbidity, precipitation and unqualified stability. As can be seen from comparative example 12, when chlorhexidine hydrochloride and MGDA coexist in the composition, even if ammonium sulfate and PEI are added simultaneously to the composition300(EO)2If ammonium sulfate and PEI300(EO)2The addition ratio of (A) is not proper, the composition still has turbidity, and the stability is not qualified.
When chlorhexidine hydrochloride and MGDA coexist in the composition, if ammonium sulfate and PEI are added in proper proportion300(EO)2The composition of example 5, wherein ammonium sulfate and PEI300(EO)2The weight ratio of the chlorhexidine hydrochloride to the MGDA is 2: 5, so that the chlorhexidine hydrochloride and the MGDA stably coexist in the composition, the composition is a clear and transparent liquid, and the stability is qualified in high-temperature and low-temperature accelerated stability investigation.
TABLE 9 stability test results for examples 6-10
Example 6 Example 7 Example 8 Example 9 Example 10
Stability at Normal temperature - - - - -
High temperature stability - - - - -
Stability at Low temperature - - - - -
When PHMB and GLDA coexist in the composition, if sodium acetate and PEI are added in appropriate proportion500(EO)5As in the compositions of examples 6 to 10, PHMB and GLDA were allowed to coexist stably in the composition, and the composition was a clear and transparent liquid, and the stability was acceptable in the high and low temperature accelerated stability test.
Third, detergency test
The above examples 1, 4 and 5 and comparative examples 2, 8 and 14 were subjected to national standard soil removal tests as described, and the results are shown in Table 10.
TABLE 10 results of the soil release test at the national Standard
Figure BDA0002287294050000181
As can be seen from the comparison of the results of the national standard soil removal tests of the examples and the comparative examples in Table 10, the addition of the chelating agent significantly improves the soil removal performance of the JB-01, JB-02 and JB-03 national standard soil removal cloths in comparison with the samples (examples 1, 4 and 5) to which the chelating agent is added and the samples (comparative examples 2, 8 and 14) to which the chelating agent is not added.
Fourth, human skin safety test
The results of the human skin safety tests performed on examples 1, 4 and 5 above were shown in Table 11, according to the methods described above.
TABLE 11 skin response statistics
Figure BDA0002287294050000182
As can be seen from the data in Table 11, after the volunteers used the samples of examples 1, 4 and 5 of the present invention for 7 days, the skin reaction grades are all 0 grade, and no obvious adverse reaction phenomenon occurs, which indicates that the laundry detergent sample of the present invention has good safety to human skin.
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 (10)

1. The antibacterial fabric detergent composition is characterized by comprising the following components in percentage by mass:
Figure FDA0002836113080000011
the electrolyte A is selected from at least one of hydrochloride, acetate, carbonate, bicarbonate, nitrate, hydrogen phosphate, dihydrogen phosphate, oxalate, sulfate and sulfite.
2. The antibacterial fabric detergent composition according to claim 1, wherein the surfactant is composed of a cationic surfactant, a nonionic surfactant and a zwitterionic surfactant; and the mass percent of each surfactant in the antibacterial fabric detergent composition is as follows:
0.5 to 10 percent of cationic surfactant,
5 to 30 percent of nonionic surfactant,
1-30% of zwitterionic surfactant.
3. The antibacterial fabric detergent composition as claimed in claim 1, wherein the weight average molecular weight of the polyethyleneimine backbone in the ethoxylated polyethyleneimine is 300-2000, and the average degree of ethoxylation is 2-50.
4. The antibacterial fabric detergent composition according to claim 1, wherein the biguanide antibacterial agent is selected from at least one of chlorhexidine, polyhexamethylene biguanide, polyaminopropyl biguanide, chitosan biguanide hydrochloride, acetate and gluconate.
5. An antibacterial fabric detergent composition as claimed in claim 1, wherein the chelating agent is selected from at least one of citrate, α -glucoheptonate, methylglycine diacetate, glutamate diacetate, N-dicarboxylic acid amino-2-hydroxypropane sulfonate and 3-hydroxy-2, 2' -iminodisuccinate.
6. The antibacterial fabric detergent composition according to claim 2, wherein the cationic surfactant is at least one selected from quaternary ammonium salt-based surfactants, heterocyclic-based surfactants, and polymeric cationic surfactants.
7. The antimicrobial fabric detergent composition of claim 2, wherein the nonionic surfactant is selected from at least one of fatty alcohol alkoxylates, alkyl polyglycosides, fatty acid alkoxylates, fatty acid alkylolamides, ethoxylated sorbitan esters.
8. The antibacterial fabric detergent composition according to claim 2, wherein the zwitterionic surfactant is at least one selected from the group consisting of amino acid type surfactants, amine oxide type surfactants, betaine type surfactants, and imidazoline type surfactants.
9. The antibacterial fabric detergent composition according to claim 1, wherein the other auxiliary agents comprise at least one of an enzyme preparation, an acid-base modifier, a perfume, and a preservative.
10. The antibacterial fabric detergent composition according to any one of claims 1 to 9, wherein the pH of the antibacterial fabric detergent composition is 4.0 to 7.0.
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