CN111893006B - Detergent composition - Google Patents
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- CN111893006B CN111893006B CN202010680821.XA CN202010680821A CN111893006B CN 111893006 B CN111893006 B CN 111893006B CN 202010680821 A CN202010680821 A CN 202010680821A CN 111893006 B CN111893006 B CN 111893006B
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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
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
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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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
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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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
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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
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
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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
- C11D1/66—Non-ionic compounds
- C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
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Abstract
The invention discloses a detergent composition. The detergent composition comprises the following components in percentage by mass: 3-30% of fatty alcohol-polyoxyethylene ether; 0.5 to 14 percent of C6 to C8 fatty alcohol EO/PO block polyether; 0.5 to 10 percent of fatty acid salt; 0-10% of an anionic surfactant; wherein the anionic surfactant does not include a fatty acid salt. The detergent composition provided by the invention has the characteristics of excellent low-foam performance, clear and transparent appearance, good fluidity, excellent detergency and the like. The detergent composition disclosed by the invention is good in formula stability, safe and environment-friendly, and has a wide application prospect.
Description
Technical Field
The invention relates to the technical field of daily-use chemistry, in particular to a detergent composition.
Background
In the process of washing fabrics, especially in the process of machine washing, too much foam can bring many negative effects, such as reducing the decontamination effect of a detergent, increasing the water consumption for rinsing and the rinsing times, weakening the treatment effect of a care agent in the rinsing stage and the like, and in severe cases, the foam can overflow in the washing process, damage a washing machine and other adverse effects can also occur. Whether household fabric cleaning or industrial fabric cleaning, how to effectively control the foaming amount and reduce the using amount of rinsing water and rinsing times is a technical problem which is concerned by the formula of the detergent.
At present, two ideas are mainly adopted in the washing industry to solve the problems of high foam and difficult rinsing in the machine washing process:
firstly, the addition of fatty acid salt, especially saturated fatty acid salt, in the detergent can reduce the foaming of the laundry detergent to a great extent and can improve the bleaching performance to a certain extent. The fatty acid salt mainly forms slightly soluble calcium fatty acid with calcium ions in water, destroys a liquid film and plays a defoaming role, so that a good defoaming effect can be achieved in hard water generally, the defoaming performance in soft water is reduced to some extent, and the defoaming performance has a retarding effect. In addition, the short-carbon-chain fatty acid salt has a poor defoaming effect, and the medium-and long-carbon-chain fatty acid salt has a high Krafft point and is likely to precipitate at low temperature, which affects the appearance of the liquid detergent. Therefore, the use of high levels of fatty acid salts in detergent formulations with a clear and transparent appearance is undesirable.
The second is to incorporate silicone antifoam agents, such as organopolysiloxanes, into the detergent. High viscosity silicone defoamer compositions can deliver significant foam control benefits during washing. However, suds suppressing systems such as silicones are difficult to disperse effectively in liquid detergent compositions and require emulsification by various means prior to addition of the detergent. At present, a plurality of commercial organic silicon defoaming agents are products emulsified by various diluents, the defoaming effect is greatly reduced, and a higher dosage is usually required to achieve a certain foam control effect. Compared with fatty acid salts, the organic silicon defoaming agent is obviously insensitive to water hardness response and can play a role in controlling foam in soft and hard water. However, because of the density difference between silicone antifoam emulsions and liquid detergents, stable dispersion in ordinary laundry detergents over long periods of time is difficult and it is necessary to construct special structuring systems for them. In addition, the dispersion of the silicone antifoaming agent in the laundry detergent can cause the transparency of the laundry detergent to be remarkably reduced. Therefore, the use of silicone antifoams in liquid detergents remains very limited.
There is a continuing need in the laundering art for detergent compositions with better suds control which are consistently in a very low sudsing state during the 4 stages of initial wash, mid-wash, before the end of wash, and final rinse. Even if the detergent is used excessively by consumers, negative performances such as foam overflowing, bleaching and the like can not occur. In addition, the detergent composition should have the following characteristics: the appearance is clear and transparent, still has fine mobility under the low temperature condition, can satisfy the requirement of the different climatic conditions in each area, and bulk viscosity is low, matches the requirement of getting liquid of intelligent washing machines such as automatic liquid feeding, accords with the specialization demand of market high-quality product. How to develop a detergent composition with such effects becomes a technical problem which workers in the field need to solve urgently.
Disclosure of Invention
In order to overcome the problems of the prior art detergent compositions described above, it is an object of the present invention to provide a detergent composition having excellent low foaming performance, clear and transparent appearance, good fluidity, and good foam control performance in various water hardness and washing machine models. It is a further object of the present invention to provide a process for the preparation of such detergent compositions. It is a further object of the present invention to provide the use of such detergent compositions.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a detergent composition, which comprises the following components in percentage by mass:
3-30% of fatty alcohol-polyoxyethylene ether;
0.5 to 14 percent of C6 to C8 fatty alcohol EO/PO block polyether;
0.5 to 10 percent of fatty acid salt;
0-10% of an anionic surfactant;
the anionic surfactant does not include a fatty acid salt.
In the detergent composition provided by the invention, fatty alcohol polyoxyethylene ether and C6-C8 fatty alcohol EO/PO block polyether belong to nonionic surfactants. The anionic surfactants used in the present invention include anionic surfactants other than fatty acid salts (non-soap) as well as fatty acid salts (soap).
Preferably, in the detergent composition of the present invention, the fatty alcohol-polyoxyethylene ether includes at least one of C12-C18 fatty alcohol-polyoxyethylene ether and C8-C20 branched alcohol-polyoxyethylene ether; more preferably, the fatty alcohol-polyoxyethylene ether comprises at least one of C12-C14 fatty alcohol-polyoxyethylene ether and C12-C15 branched alcohol-polyoxyethylene ether; still more preferably, the fatty alcohol-polyoxyethylene ether comprises at least one of AEO3, AEO5, AEO7, AEO9 and isomeric tridecanol polyoxyethylene ether.
Preferably, in the detergent composition, the fatty alcohol-polyoxyethylene ether accounts for 3-25% by mass; further preferably, the mass percent of the fatty alcohol-polyoxyethylene ether is 3-20%; further preferably, the mass percent of the fatty alcohol-polyoxyethylene ether is 4-18%; more preferably, the mass percent of the fatty alcohol-polyoxyethylene ether is 4-15%.
Preferably, in the detergent composition, the percentage of the anionic surfactant to the total mass of the fatty alcohol-polyoxyethylene ether, the anionic surfactant and the C6-C8 fatty alcohol EO/PO block polyether is less than 55%; further preferably, the percentage of the anionic surfactant in the total mass of the fatty alcohol-polyoxyethylene ether, the anionic surfactant and the EO/PO block polyether of the C6-C8 fatty alcohol is 2-54%; still further preferably, the percentage of the anionic surfactant in the total mass of the fatty alcohol-polyoxyethylene ether, the anionic surfactant and the EO/PO block polyether of the C6-C8 fatty alcohol is 4-54%; more preferably, the percentage of the anionic surfactant in the total mass of the fatty alcohol-polyoxyethylene ether, the anionic surfactant and the C6-C8 fatty alcohol EO/PO block polyether is 6-54%.
Preferably, in the detergent composition of the present invention, the anionic surfactant accounts for 0.5% to 10% by mass of the detergent composition; more preferably, the anionic surfactant is 1 to 10% by mass of the detergent composition.
The anionic surfactant referred to in the detergent compositions of the present invention is a non-fatty acid salt (non-soap) anionic surfactant. Preferably, in the detergent composition, the anionic surfactant comprises at least one of an organic sulfonic acid surfactant and an organic sulfuric acid surfactant; further preferably, the anionic surfactant comprises at least one of alkyl benzene sulfonate, alkyl sulfonate, alpha-olefin sulfonate, fatty acid methyl ester sulfonate, succinate sulfonate, alkyl sulfate and fatty alcohol-polyoxyethylene ether sulfate; the sulfonate is preferably an alkali metal sulfonate; the sulfate is preferably an alkali metal sulfate. Still further preferably, the anionic surfactant is selected from one or a combination of sodium linear alkylbenzene sulfonate (LASNa), sodium fatty alcohol-polyoxyethylene ether sulfate (AES).
In the detergent composition, EO in the C6-C8 fatty alcohol EO/PO block polyether represents a polyoxyethylene group, and PO represents a polyoxypropylene group.
Preferably, in the detergent compositions of the present invention, the C6-C8 fatty alcohol EO/PO block polyether has a cloud point of less than 60 ℃; more preferably, the cloud point of the EO/PO block polyether of the C6-C8 fatty alcohol is lower than 40 ℃; still more preferably, the cloud point of the EO/PO block polyether of the C6-C8 fatty alcohol is lower than 39 ℃; more preferably, the C6-C8 fatty alcohol EO/PO block polyether has a cloud point of 29 ℃ or less.
Preferably, in the detergent composition, the mass percent of the EO/PO block polyether of the C6-C8 fatty alcohol is 1-12%; more preferably, the mass percent of the EO/PO block polyether of the C6-C8 fatty alcohol is 3-10%; still more preferably, the mass percent of the EO/PO block polyether of the C6-C8 fatty alcohol is 5-8%.
The fatty acid salts described in the detergent compositions of the invention may be referred to as soaps, i.e. higher fatty acid salts. Preferably, in the detergent composition, the fatty acid salt includes at least one of an alkali metal salt of a fatty acid having from C10 to C20, an alkali metal salt of coconut oil fatty acid, and an alkali metal salt of palm kernel oil fatty acid. The fatty acid alkali metal salt of C10-C20 can be saturated fatty acid alkali metal salt of C10-C20 or unsaturated fatty acid alkali metal salt of C10-C20. Further preferably, the fatty acid salt comprises at least one of coconut oil sodium fatty acid, sodium stearate, sodium palmitate, sodium myristate and sodium laurate; still more preferably, the fatty acid salt is selected from one or a combination of coconut oil sodium fatty acid and sodium stearate.
Preferably, in the detergent composition of the present invention, the fatty acid salt is 1% to 10% by mass.
Preferably, in the detergent composition, the total mass percentage of all the surfactants, namely fatty alcohol-polyoxyethylene ether, C6-C8 fatty alcohol EO/PO block polyether, fatty acid salt and anionic surfactant, is less than or equal to 50%; further preferably, the total mass percent of the fatty alcohol-polyoxyethylene ether, the EO/PO block polyether of the C6-C8 fatty alcohol, the fatty acid salt and the anionic surfactant is less than or equal to 30 percent; still further preferably, the total mass percent of the fatty alcohol-polyoxyethylene ether, the EO/PO block polyether of the fatty alcohol C6-C8, the fatty acid salt and the anionic surfactant is 15-30%; more preferably, the total mass percent of the fatty alcohol-polyoxyethylene ether, the EO/PO block polyether of the fatty alcohol with the carbon number of 6-8, the fatty acid salt and the anionic surfactant is 20-29%.
Preferably, such detergent compositions of the present invention further comprise an adjunct.
In the detergent composition of the present invention, the amount of the auxiliary may be added as needed. When the auxiliary agent is added to the detergent composition, the mass percentage of the auxiliary agent in the detergent composition is preferably 0 to 30%, more preferably 0.01 to 20%, and still more preferably 0.1 to 10%.
Preferably, in the detergent composition of the present invention, the auxiliary agent comprises at least one of a thickening agent, an acid-base regulator, an enzyme, a chelating agent, a stabilizer, a colorant, a preservative, an essence, and a cosolvent; further preferably, the auxiliary agent comprises at least one of a thickening agent, an acidity and alkalinity regulator, an enzyme, a chelating agent and a preservative.
Preferably, the detergent composition of the present invention further comprises water.
Preferably, the detergent composition of the present invention further comprises water in balance. Namely, in the detergent composition, water is the rest of the components except the above components (including fatty alcohol polyoxyethylene ether, C6-C8 fatty alcohol EO/PO block polyether, fatty acid salt, anionic surfactant and auxiliary agent).
In a second aspect, the present invention provides a process for the preparation of the above detergent composition.
A preparation method of the detergent composition comprises the following steps: mixing the components to obtain the detergent composition.
Preferably, the process for preparing the detergent composition of the present invention comprises the steps of: mixing fatty alcohol-polyoxyethylene ether, C6-C8 fatty alcohol EO/PO block polyether, fatty acid salt, anionic surfactant and water, and adding an auxiliary agent to obtain the detergent composition.
In some preferred embodiments of the present invention, the detergent composition is prepared by a process comprising the steps of: mixing fatty alcohol-polyoxyethylene ether, C6-C8 fatty alcohol EO/PO block polyether, fatty acid salt, anionic surfactant and water, adding a chelating agent, a thickening agent or a stabilizing agent, mixing, adding an acid-base regulator to adjust the pH value of the solution, adding an enzyme, a coloring agent or a preservative, mixing, and mixing with water to obtain the detergent composition.
The pH value of the detergent composition is preferably 5-11; further preferably 7 to 10; more preferably 7.5 to 9.
In a third aspect the invention provides the use of a detergent composition as described above.
A fabric detergent comprises the detergent composition.
Preferably, the fabric detergent of the present invention is a fabric washing liquor; further preferably, the fabric detergent of the present invention is a laundry detergent. The fabric detergent of the invention is a standard laundry detergent which can be suitable for being used as a reference washing machine and is used for evaluating the performance of the washing machine.
The invention has the beneficial effects that:
the detergent composition provided by the invention has the characteristics of excellent low-foam performance, clear and transparent appearance, good fluidity, excellent detergency and the like. The detergent composition has good formula stability, and is safe and environment-friendly.
Specifically, compared with the prior art, the invention has the following advantages:
1. when the detergent composition is applied to washing, the detergent composition is always in a very low-foam state in 4 stages such as initial washing, middle washing, before washing, final rinsing and the like. The detergent composition has excellent foam control performance in various water hardness and washing machine types.
2. When the detergent composition is used in an excessive amount, no negative effects such as foaming and bleaching occur.
3. The detergent composition has good detergency, can be used for commercial laundry detergent products and evaluating the performance of washing machines, and has wide application prospect.
Drawings
FIG. 1 is a graph of the amount of suds washed in a drum washing machine by a detergent sample;
FIG. 2 is a graph showing the amount of bubbles washed in a drum washing machine under various conditions in example 1.
Detailed Description
The detergent composition provided by the embodiment of the invention comprises the following components: fatty alcohol-polyoxyethylene ether, EO/PO block polyether of C6-C8 fatty alcohol, fatty acid salt and anionic surfactant; wherein the anionic surfactant does not include a fatty acid salt.
The components of the detergent compositions of the examples of the present invention are described in further detail below:
fatty alcohol polyoxyethylene ether
Fatty alcohol polyoxyethylene ether (AEO), also known as polyoxyethylene fatty alcohol ether, belongs to a nonionic surfactant.
The type of the fatty alcohol-polyoxyethylene ether used in the detergent composition of the embodiment of the present invention is not limited, and specifically, the fatty alcohol-polyoxyethylene ether may be at least one selected from the group consisting of fatty alcohol-polyoxyethylene ethers having C12-C18, and branched alcohol-polyoxyethylene ethers having C8-C20. In some specific implementations of the invention, the fatty alcohol-polyoxyethylene ether is selected from at least one of AEO3, AEO5, AEO7, AEO9, and isomeric tridecanol polyoxyethylene ethers. The numbers 3, 5, 7 and 9 of AEO3, AEO5, AEO7 and AEO9 indicate the average number of EO segments in AEO. The isomeric tridecanol polyoxyethylene ether can be selected from isomeric tridecanol polyoxyethylene ethers with EO numbers of 5, 7 or 9.
In the detergent composition of the embodiment of the invention, the mass percent of the fatty alcohol-polyoxyethylene ether is 3% -30%, preferably 3% -25%, more preferably 3% -20%, still more preferably 4% -18%, and more preferably 4% -15%.
Di, C6-C8 fatty alcohol EO/PO block polyether
The C6-C8 fatty alcohol EO/PO block polyether is a fatty alcohol (the carbon chain length is C6-C8) EO/PO block polyether, and belongs to a nonionic surfactant. The polyether is composed of polyoxyethylene (EO) and Polyoxypropylene (PO), and is usually made by copolymerizing EO and PO.
The C6-C8 fatty alcohol EO/PO block polyether used in the detergent composition of the embodiments of the present invention may be at least one selected from the group consisting of hexanol EO/PO block polyether, heptanol EO/PO block polyether, and octanol EO/PO block polyether. The C6-C8 fatty alcohol EO/PO block polyether can be in a branched chain structure or a linear chain structure.
In the detergent compositions of the embodiments of the present invention, the cloud point of the C6-C8 fatty alcohol EO/PO block polyether is less than 60 ℃, preferably, the cloud point of the C6-C8 fatty alcohol EO/PO block polyether is less than 40 ℃, more preferably, the cloud point of the C6-C8 fatty alcohol EO/PO block polyether is less than 39 ℃. Cloud point can be determined according to method D in GB/T5559-2010(ISO 1065:1991) determination of cloud points of nonionic surfactants of the ethylene oxide type and ethylene oxide-propylene oxide block polymerization type.
In the detergent composition of the embodiment of the invention, the mass percentage of the C6-C8 fatty alcohol EO/PO block polyether is 0.5-14%, preferably 1-12%, more preferably 3-10%, and even more preferably 5-8%.
Salts of fatty acids
Fatty acid salts are also an anionic surfactant. In particular, the fatty acid salts employed in the detergent compositions of the present invention are higher fatty acid salts, also known as soaps.
The type of the fatty acid salt used in the detergent composition of the embodiment of the present invention is not limited, and specifically, the fatty acid salt may be at least one selected from the group consisting of alkali metal salts of fatty acids C10 to C20, alkali metal salts of coconut oil fatty acids, and alkali metal salts of fatty acids of palm kernel oil; more preferably, the fatty acid salt is at least one selected from coconut oil sodium fatty acid, sodium stearate, sodium palmitate, sodium myristate and sodium laurate; still more preferably, the fatty acid salt is selected from one or a combination of coconut oil sodium fatty acid and sodium stearate.
In the detergent composition, when the content of the fatty acid salt, i.e., soap is too high, problems of deterioration in fluidity and stability of the detergent composition are caused. Therefore, in the detergent composition of the embodiment of the present invention, the mass percentage of the fatty acid salt is preferably 0.5% to 10%, and more preferably 1% to 10%.
Tetra, anionic surfactant
The anionic surfactants employed in the detergent compositions of the present embodiments do not include fatty acid salts, i.e., anionic surfactants that are non-fatty acid salts (non-soap).
The anionic surfactant used in the detergent composition of the embodiment of the present invention may be at least one selected from the group consisting of an organic sulfonic acid surfactant and an organic sulfuric acid surfactant; further preferably, the anionic surfactant is at least one selected from alkyl benzene sulfonate, alkyl sulfonate, alpha-olefin sulfonate, fatty acid methyl ester sulfonate, succinate sulfonate, alkyl sulfate and fatty alcohol-polyoxyethylene ether sulfate; still further preferably, the anionic surfactant is selected from one or a combination of sodium linear alkylbenzene sulfonate (LASNa), sodium fatty alcohol-polyoxyethylene ether sulfate (AES).
The detergent composition of the embodiment of the present invention may or may not contain an anionic surfactant. The anionic surfactant is contained in the detergent composition in an amount of 0 to 10% by mass, preferably 0.5 to 10% by mass, more preferably 1 to 10% by mass, and still more preferably 4 to 10% by mass.
Fifth, auxiliary agent
The detergent compositions of the embodiments of the present invention also include an adjunct. The auxiliary agent can comprise thickening agent, acid-base regulator, enzyme, chelating agent, stabilizer, colorant, preservative, essence and cosolvent.
5.1 thickening Agents
The detergent compositions of the embodiments of the present invention may be optionally added or not added with a thickener to adjust viscosity according to the application requirements. The thickening agent is at least one selected from fatty alcohol-polyoxyethylene ether acrylic acid copolymer, fatty acid alkanolamide, ethoxylated fatty acid polyglycerol ester, alkali-swellable emulsion polymer, N-dodecyl-2-pyrrolidone and polyethylene glycol distearate.
When the thickener is used, the content of the thickener is usually 0 to 5% by mass, preferably 0.1 to 5% by mass, and more preferably 0.5 to 2% by mass of the detergent composition.
5.2 acid-base regulators
The pH adjusting agent, also called pH adjusting agent, can be used inorganic and/or organic alkalinity sources as well as acidifying agents.
In some embodiments of the present invention, the source of inorganic alkalinity may be selected from one or a combination of sodium hydroxide, potassium hydroxide; the organic alkalinity source can be selected from one or the combination of monoethanolamine and triethanolamine; the inorganic acidifying agent can be at least one selected from HF, HCl, HBr, HI, boric acid, phosphoric acid, phosphonic acid, sulfuric acid and sulfonic acid; the organic acidulant may be selected from at least one of citric acid, C1 to C30 carboxylic acids.
The pH of the detergent compositions of the examples of the present invention was adjusted by the addition of an acid base modifier. Preferably, the pH value of the detergent composition is adjusted to 5-11 by adding an acid-base regulator; preferably, the pH value of the detergent composition is adjusted to 7-10 by adding an acid-base regulator; further preferably, the pH value of the detergent composition is adjusted to 7.5-9 by adding an acid-base regulator.
5.3 enzymes
In some embodiments of the invention, the enzyme is selected from one or more of protease, cellulase, lipase, amylase, pectinase, xylanase, oxidase, reductase, peroxidase; further preferably one or a combination of protease, cellulase, amylase and lipase. If an enzyme is used, the content of the enzyme is usually 0.01 to 10% by mass, preferably 0.1 to 5% by mass of the detergent composition.
5.4 chelating agents
In some embodiments of the present invention, the chelating agent is at least one selected from the group consisting of aminocarboxylic acid compounds, organic aminophosphonic acid compounds, and sodium citrate. Such aminocarboxylic acid compounds include, but are not limited to: ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylenediaminetetraacetic acid, nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DEPTA); such organo aminophosphonic acid compounds include, but are not limited to: ethylenediaminetetra (methylenephosphonic acid), 1-hydroxyethane 1, 1-diphosphonic acid (HEDP) and aminotri (methylenephosphonic acid). If a chelating agent is used, the content of the chelating agent is usually 0.1 to 10% by mass, preferably 1 to 5% by mass of the detergent composition.
5.5 stabilizers
In some embodiments of the invention, the stabilizer is selected from a polymer of microbial fermentation origin, natural plant origin, natural extract origin, or mixtures thereof, i.e., at least one of reduced gum, locust bean gum, guar gum, gellan gum, xanthan gum, carrageenan, xanthan gum, cellulose gum, gelatin, pectin. If a stabilizer is used, the content of the stabilizer is usually 0.02 to 5% by mass, preferably 0.5 to 3% by mass of the detergent composition.
5.6 colorants
In some embodiments of the present invention, the colorant may be selected from pigments and/or dyes, and may include colorants commonly used in laundry detergents or fabric softeners.
If a colorant is used, the content of the colorant is usually 0.0001 to 0.5% by mass, preferably 0.01 to 0.1% by mass of the detergent composition.
5.7 preservatives
In some embodiments of the invention, the preservative is selected from at least one of cason (a mixture of 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one), 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one. If a preservative is used, the content of the preservative is usually 0.001 to 1% by mass, preferably 0.01 to 0.2% by mass of the detergent composition.
5.8 essence
In some embodiments of the present invention, the perfume is selected from at least one of the following: herbal fragrances such as peppermint, spearmint, rosemary, thyme; fruit scents such as apple, almond, grape, cherry, pineapple, pear, honey peach, mango, orange, strawberry, blueberry, citrus; floral scents, such as rose-like, lavender-like, carnation-like; and vanilla, gardenia, hawthorn, vegetarian cabbage, honeysuckle, cyclamen, hyacinth, bracken, clove, jasmine, lily, mimosa, magnolia, orchid, narcissus, orange blossom, licorice, reseda green, clover, violet, sweet pea, and wallflower. If essence is used, the content of the essence is usually 0.01-5% by mass, preferably 0.05-2% by mass of the detergent composition.
5.9 Co-solvent
In some embodiments of the present invention, the cosolvent is selected from one or more of ethanol, propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, propylene glycol, glycerol, diethylene glycol, dipropylene glycol, and polyethylene glycol. By adding the cosolvent, the surfactant and water can be uniformly mixed to play a stabilizing role.
The detergent composition of the present invention comprises, in addition to the above components, the balance of water.
The detergent composition of the present invention can be prepared by merely mixing the components. In some embodiments of the invention, the detergent composition may be prepared by first mixing the surfactants with water and then adding the adjunct.
The detergent composition provided by the invention can be applied to the preparation of fabric detergents, such as laundry detergents.
The present invention will be described in further detail with reference to specific examples. The starting materials, reagents or apparatus used in the examples and comparative examples were obtained from conventional commercial sources or can be obtained by a method of the prior art, unless otherwise specified. Unless otherwise indicated, the testing or testing methods are conventional in the art.
The components used in the following examples are illustrated below:
the types and characteristics of the fatty alcohol EO/PO surfactants are shown in Table 1. The cloud point test method in Table 1 was as described in GB/T5559-2010(ISO 1065:1991) method D in determination of the cloud point of ethylene oxide-type and ethylene oxide-propylene oxide block-polymerized nonionic surfactants. For fatty alcohol EO/PO surfactants with cloud points below 10 ℃, the method can only detect the cloud point below 10 ℃ and cannot detect specific cloud point data.
TABLE 1 fatty alcohol EO/PO surfactant types and characteristics
| Numbering | DPH-1 | DHP-2 | DPH-3 | DPH-4 |
| Carbon chain distribution | Isooctyl alcohol | C6 | C10 | Isooctyl alcohol |
| Cloud Point (. degree.C., aqueous solution) | <10.0 | 29.0 | 39.1 | 64.0 |
AES: the fatty alcohol-polyoxyethylene ether sodium sulfate has the fatty alcohol carbon number of 12-14 and the EO number of 2.
LASNa: the linear alkyl benzene sulfonic acid sodium salt has 10-13 carbon atoms.
AEO 9: C12-C14 fatty alcohol polyoxyethylene ether with EO number of 9.
AEO 7: C12-C14 fatty alcohol polyoxyethylene ether with EO number of 7.
Isomeric tridecanol polyoxyethylene ether (9): isomeric tridecanol polyoxyethylene ether with EO number of 9.
The rest components are all common detergent raw materials sold in the market.
Hard water used in the examples is referred to GB/T13174-2008' determination of detergency and circular washing performance of detergent for clothingChapter 7, section 1. To prepare 250ppm (as CaCO)3Expressed) hard water, the formulation method is as follows: weighing 16.70g of CaCl2And 20.37gMgCl2Adding 10.0L of deionized water, stirring well, and using 1.0L to 10.0L to obtain 250mg/kg (ppm) of hard water.
Examples 1 to 10
The compositions of examples 1 to 10 of the detergent composition are shown in Table 2.
TABLE 2 composition of detergent compositions of the examples
The preparation method of the detergent composition in examples 1 to 10 is as follows: according to the composition shown in the table 2, surfactants such as AES, LASNa, AEO9, AEO7, isotridecanol polyoxyethylene ether (9), DPH-1, DPH-2 and coconut oil soap are added into a certain amount of water, sodium citrate is added, stirring is carried out for dissolving (heating if necessary), a thickening agent is added, sodium hydroxide is used for adjusting the pH value of the solution to 7.5-9.0, protease and preservative are finally added, and the water is added after uniform stirring and water replenishing. The prepared detergent composition is stored in a sealed and light-proof way for later use.
Comparative examples 1 to 11
The compositions of comparative examples 1 to 11 of the detergent composition are shown in Table 3.
Table 3 composition of comparative example detergent composition
The preparation methods of the detergent compositions of comparative examples 1 to 9 were the same as those of the detergent composition examples, except that the raw materials were added in the compositions shown in Table 3.
The detergent compositions of the examples and comparative examples were subjected to performance tests while taking a standard laundry detergent for comparative analysis. The standard laundry detergent is a laundry detergent modified according to national standard No. 1 of GB/T13174-2008 'determination of detergency and circulating washing performance of detergent for clothing'.
The test indexes and methods are respectively illustrated as follows:
1. active content
Active content test method: GB/T13173 + 2008 & surfactant detergents test methods chapter 7.
2. Anion proportion (except soap)
Method for calculating anion ratio (excluding soap): the mass content of non-soap anionic surfactant in the detergent composition formulation is summed and divided by the sum of the mass content of non-soap anionic surfactant and non-ionic surfactant. Taking example 1 as an example, as shown in table 2, the formulation was 2% AES and 2% LASNa for non-soap anionic surfactants and 10% AEO9 and 5% DPH-1 for non-ionic surfactants, so that the anion proportion of example 1 (excluding soap) ═ 2% + 2%/(2% + 2% + 10% + 5%) × 100% ═ 21%.
3. pH (stock solution)
pH (stock solution) test method: GB/T6368-2008-potentiometric method for measuring pH value of surfactant aqueous solution, the test temperature is 25 ℃.
4. Viscosity of the oil
Viscosity test method: GB/T5561-2012 method for determining the viscosity and flow properties of surfactants by means of a rotational viscometer, test temperature 5 ℃.
5. Stability of
The stability test method comprises the following steps: QB/T1224-. And (3) judging the stability to be qualified if uniform liquid without layering, obvious suspended matters (except products added with uniform suspended particle components) or precipitates and mechanical impurities appears through a stability test, and representing the stability by the square root. In the stability test, problems such as delamination, suspended matter, precipitation, mechanical impurities and the like were found, and the stability was judged to be unsatisfactory, and indicated by "x".
6. Amount of foam
The foam quantity testing method comprises the following steps: the detergents of the examples and comparative examples were evaluated using a drum washing machine of the same brand and model (capacity 9kg), a standard program was selected, water (tap water) was automatically fed in 10g per sample, and the washing machine tub was rotated once counterclockwise and once more clockwise during washing, and recorded as one cycle. From the start of the wash, the foam level scale (indicated by the marked water scale line) was recorded every 3 cycles.
A total of 11 recorded levels were summed to reflect the foam height throughout the wash. The foam level was 200mL and below, representing an average foam level during the process of 1/3 below the roller window, indicating that the formulation had a very low wash foam level, i.e., the "low foam" effect described in the present invention.
7. National standard detergency test
The detergency of the standard laundry detergent and the detergency of the comparative examples and examples were tested in accordance with GBT 13174-2008 "determination of detergency and circulating washing performance of detergents for clothing".
8. IEC detergency test
The detergency performance of different samples in washing machines was tested according to IEC60456-2010 "Methods washing machines for using the water by the method for measuring the performance.
9. Foam amount of different washing stages of drum washing machine
According to the test conditions of IEC60456-2010 "cleaning machines for cleaning uses-Methods for measuring the performance", the foams in 4 stages of initial washing (washing 10min), middle washing (washing 20min), before washing (washing 28min), and after final rinsing (program end) were recorded in the washing machine.
10. Thickening performance
The fluidity of the samples was evaluated by testing the viscosity at 5 ℃ and 23 ℃ of the samples by introducing a thickener and examining the thickening behavior.
The results of the tests on the active content, anion ratio (excluding soap), pH (stock), viscosity (5 ℃), stability, foam level of the detergent composition examples and standard laundry detergents are shown in table 4. The "/" in table 4 indicates no test.
Table 4 detergent composition examples and standard laundry detergent test results
The detergent compositions of examples 1 to 10 were all clear and transparent in appearance.
The results of the tests of the active content, anion ratio (excluding soap), pH (stock solution), viscosity (5 ℃), stability, and foam amount of the comparative examples of the detergent compositions are shown in table 5. The "/" in table 5 indicates no test.
Table 5 comparative example test results for detergent compositions
Comparative examples 2 and 6 showed delamination in the stability test and the viscosity at 5 c could not be measured. The detergent compositions of the remaining comparative examples were clear and transparent in appearance.
The results of the suds level test for specific wash cycles for the detergent composition examples, comparative examples and standard laundry detergent can be seen in table 6.
Table 6 foam amount test results
From the above test results, the following conclusions can be drawn:
(1) the foam of the formula is greatly influenced by different anion ratios, the anion ratio of the example 1 is 21%, and the foam is low in the washing process; the anion ratio of comparative example 1 was 57%, the foam was high during washing (> 200 mL); the anion ratio of example 4 was 54%, and the foam reached a critical state during washing.
(2) The increased amount of DPH-1 was found to be beneficial for foam control (higher amounts of DPH-1 in example 2 than in example 1 and lower wash foam). However, when the amount of DPH-1 was too high (comparative example 2), the appearance of the formulation was unstable and phase separation was easy.
(3) For EO/PO surfactants with the same carbon chain composition (e.g., C8 alcohol EO/PO surfactants), the lower the cloud point, the better the defoaming action. For example, example 1 and comparative example 3, where the carbon chains of the EO/PO surfactants were isooctanols, the cloud point of DPH-1 in aqueous solution was < 10 ℃ and the cloud point of DPH-4 in aqueous solution was 64 ℃. The foam of example 1 is significantly lower than that of comparative example 3.
(4) The formulation using C10 EO/PO surfactant DPH-3 (comparative example 4) had a significantly higher foam level than the formulation using C8 alcohol EO/PO surfactant DPH-1 (example 1) and than the formulation using C6 alcohol EO/PO surfactant DPH-2 (example 10).
(5) A certain level of soap is required in the detergent composition formulation otherwise suds are significantly enhanced (examples 3-5 compared to comparative example 5). However, the soap content exceeding a certain amount results in an unacceptable stability of the detergent composition (comparative example 6).
(6) When the active matter content of the detergent composition is too high, the foam is rapidly increased and the viscosity of the formula is rapidly increased during the washing process, and the fluidity is deteriorated (example 1 and comparative examples 7 to 9).
(7) Nonionic surfactants of various structures are suitable for use in the detergent compositions of the present invention, for example, polyoxyethylene ether (9) of natural alcohol (C12-C14) in example 1, polyoxyethylene ether (9) of isotridecanol in example 6, and polyoxyethylene ether (7) of natural alcohol (C12-C14) in example 7. However, too high a total amount of nonionic surfactant (other than EO/PO nonionic surfactant) leads to detergent compositions with unacceptable stability and rapidly increasing viscosity, such as in comparative example 7.
The detergent composition examples, comparative examples and standard laundry detergent samples were subjected to the national standard detergency test, and the test results are shown in table 7. In table 7, the stain removal value indicates the difference before and after washing, and a higher numerical value indicates better washing effect; r1 and R2 show that two parallel experiments were performed. The stain release ratio refers to the stain release value of the detergent sample (average of R1 and R2) divided by the stain release value of the standard laundry detergent (average of R1 and R2).
TABLE 7 results of the national Standard detergency test
As can be seen from the results of the national standard detergency test in table 7, the detergency of the sample of this example is significantly better than that of the standard laundry detergent. In addition, the samples of this example had good stain removal performance while being low foaming.
IEC detergency tests were performed on detergent composition examples, comparative examples, and standard laundry detergent samples, and the test results are shown in table 8. In Table 8, the Y value indicates detergency, and a higher value indicates better detergency.
TABLE 8 IEC detergency test results
As can be seen from the IEC detergency test results of table 8, the detergency of the sample of this example is significantly better than that of the standard laundry detergent. In addition, the sample of this example exhibited good detergency while having low foam.
The detergent composition examples, comparative examples and standard laundry detergent samples were tested for the amount of suds at different washing stages of a drum washing machine. Photographs were recorded in the washing machine for 10 minutes of washing (wash phase), 20 minutes of washing (wash phase), 28 minutes of washing (before the end of wash phase) and 4 phases of program end according to the test conditions of IEC 60456-2010. FIG. 1 shows a graph of the amount of foam washed in a drum washing machine with a sample of detergent, the wash water being tap water. From the pictures of the windows of the drum washing machine (diameter of the circular window is 30cm) in fig. 1, the amount of foam of the present example is very small, and there is almost no foam at each stage of washing and rinsing, which is significantly better than the standard laundry detergent and the comparative example. Example 1 was also tested for the amount of suds washed in a drum washing machine under different conditions, as can be seen in figure 2. FIG. 2 shows the foam amount of example 1 in the case of tap water washing (standard), hard water washing at 250ppm (standard), and 2 times the standard (tap water washing). As can be seen from FIG. 2, the detergent of this example can be washed in water with various hardness and has good foam control effect; when the detergent is used in an excessive amount, negative performances such as foam overflowing, bleaching and the like do not occur.
The thickening performance of the different detergent samples was analyzed. Table 9 shows the results of the viscosity tests for example 3, example 8 and example 9.
Table 9 viscosity test results
| Example 3 | Example 8 | Example 9 | |
| Thickener mass content (%) | 0 | 1.0 | 2.0 |
| Viscosity (cp, 5 ℃ C.) | 65 | 104 | 311 |
| Viscosity (cp, 23 ℃ C.) | 51 | 95 | 231 |
The detergent composition provided by the invention can realize controllable tackifying of a formula by introducing the thickening agent. From the test results in table 9, it can be seen that the samples of the examples have good fluidity, and the viscosities under different temperature conditions are all lower than 500cp, so that the liquid taking requirements of the washing machine can be well met, and the washing machine is particularly suitable for automatic liquid adding washing machines.
The detergent provided by the invention is suitable for various washing machine models, including commercial washing machines and reference washing machines for evaluating the washing machines. The detergent can be used as a standard laundry detergent for evaluating the performance of a washing machine.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (7)
1. A detergent composition characterized by: the composite material comprises the following components in percentage by mass:
3% -30% of fatty alcohol-polyoxyethylene ether;
0.5% -14% of C6-C8 fatty alcohol EO/PO block polyether;
0.5% -10% of fatty acid salt;
0.5-10% of an anionic surfactant;
the anionic surfactant does not include a fatty acid salt;
the cloud point of the C6-C8 fatty alcohol EO/PO block polyether is lower than 40 ℃;
the percentage of the anionic surfactant in the total mass of the fatty alcohol-polyoxyethylene ether, the anionic surfactant and the C6-C8 fatty alcohol EO/PO block polyether is less than 55%;
the anionic surfactant comprises at least one of an organic sulfonic acid surfactant and an organic sulfuric acid surfactant.
2. A detergent composition according to claim 1, characterized in that: the fatty alcohol-polyoxyethylene ether comprises at least one of C12-C18 fatty alcohol-polyoxyethylene ether and C8-C20 branched alcohol-polyoxyethylene ether.
3. A detergent composition according to claim 1, characterized in that: the fatty acid salt comprises C10-C20 fatty acid alkali metal salt.
4. A detergent composition according to claim 1, characterized in that: the detergent composition further comprises an adjunct; the auxiliary agent comprises at least one of thickening agent, acid-base regulator, enzyme, chelating agent, stabilizer, colorant, preservative, essence and cosolvent.
5. A detergent composition as claimed in claim 1, 2, 3 or 4, characterised in that: the detergent composition further comprises water.
6. A process for preparing a detergent composition as claimed in any one of claims 1 to 5, characterized in that: the method comprises the following steps: mixing the components to obtain the detergent composition.
7. A fabric washing detergent characterized by: comprising the detergent composition of any of claims 1 to 5.
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| CN112646166B (en) * | 2020-12-22 | 2023-08-01 | 赞宇科技集团股份有限公司 | Method for rapidly improving solubility of fatty alcohol polyoxyethylene ether sodium sulfate |
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