CN112080350A - Efficient powder cleaning agent and preparation method thereof - Google Patents

Efficient powder cleaning agent and preparation method thereof Download PDF

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Publication number
CN112080350A
CN112080350A CN202011181091.5A CN202011181091A CN112080350A CN 112080350 A CN112080350 A CN 112080350A CN 202011181091 A CN202011181091 A CN 202011181091A CN 112080350 A CN112080350 A CN 112080350A
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Prior art keywords
polyoxyethylene ether
parts
alcohol polyoxyethylene
sodium
surfactant
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严敬华
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Zhejiang Shiweikang Biomedical Materials Co ltd
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Zhejiang Shiweikang Biomedical Materials Co ltd
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Priority to CN202011181091.5A priority Critical patent/CN112080350A/en
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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
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/32—Amides; Substituted amides
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • 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
    • C11D1/008—Polymeric surface-active agents
    • 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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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

The invention relates to the technical field of cleaning agents, in particular to a high-efficiency powder cleaning agent and a preparation method thereof, wherein the high-efficiency powder cleaning agent comprises, by weight, 40-70 parts of a builder, 25-35 parts of an oxidant, 1-5 parts of an active agent and 3-10 parts of a surfactant; the oxidant is selected from one or more of sodium percarbonate, sodium perborate, sodium persulfate, potassium percarbonate, potassium perborate and potassium persulfate. The efficient powder cleaning agent provided by the invention has strong dirt removing capability which is not limited by low temperature, has an obvious sterilization effect, and simultaneously has strong stability in a high-humidity environment, can maintain the powder structure of the cleaning agent for a long time, and avoids influence on application of the cleaning agent due to premature moisture absorption and agglomeration.

Description

Efficient powder cleaning agent and preparation method thereof
Technical Field
The invention relates to the technical field of cleaning agents, in particular to a high-efficiency powder cleaning agent and a preparation method thereof.
Background
In daily household cleaning, liquid cleaning agents such as liquid detergents and laundry detergents are mostly used by people, but the liquid cleaning agents contain more water, are heavy in weight, are inconvenient to carry and are difficult to transport. The existing solid cleaning particles, such as washing powder, have strong alkalinity, great irritation and damage to skin when in use, certain corrosivity, insufficient environmental protection and poor storage stability. For example, Chinese patent CN1477184A mentions that chlorine dioxide is applied to washing powder to achieve good sterilization effect, but the stability of chlorine dioxide is poor in the product storage process; hydrogen peroxide and peracetic acid, as broad-spectrum, quick-acting, high-efficient bactericides, are widely used in washing powder, Chinese patent CN106906062A adds sodium percarbonate into washing powder, under the action of tetraacetylethylenediamine activator, peroxyacetic acid is produced, which has strong bactericidal action on fabrics, and simultaneously has brightening and brightening effects on fabrics, but the sodium percarbonate has poor stability and is easy to decompose in the storage process of the product, and the water temperature above 40 ℃ is required in the washing process, so that the bactericidal action of peroxide can be fully exerted.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a high-efficiency powder cleaning agent, which comprises 40-70 parts of builder, 25-35 parts of oxidant, 1-5 parts of active agent and 3-10 parts of surfactant in parts by weight; the oxidant is selected from one or more of sodium percarbonate, sodium perborate, sodium persulfate, potassium percarbonate, potassium perborate and potassium persulfate.
As a preferable technical scheme of the invention, the sodium percarbonate is coated sodium percarbonate with the particle size of 20-40 meshes.
As a preferable technical solution of the present invention, the surfactant is fatty alcohol polyether.
As a preferable technical solution of the present invention, the fatty alcohol polyether includes an isomeric alcohol polyoxyethylene ether.
As a preferable technical scheme of the invention, the hydroxyl value of the isomeric alcohol polyoxyethylene ether is 25-31 mgKOH/g.
As a preferable technical scheme of the present invention, the fatty alcohol polyether further includes fatty alcohol polyoxyethylene ether polyoxypropylene ether, and the weight ratio of the fatty alcohol polyoxyethylene ether polyoxypropylene ether to the isomeric alcohol polyoxyethylene ether is 1: (1.5-2.5).
As a preferable technical scheme of the invention, the carbon number of the fatty alcohol in the fatty alcohol polyoxyethylene ether polyoxypropylene ether is 4-13.
As a preferable technical scheme of the invention, the builder is selected from one or more of sodium carbonate, potassium carbonate and sodium bicarbonate.
As a preferable technical scheme of the invention, the bulk density of the sodium carbonate is 0.45-0.7g/cm3。
The second aspect of the present invention provides a method for preparing the high efficiency powder detergent, which comprises: uniformly mixing the builder, the oxidant, the active agent and the surfactant at 40-50 ℃, putting into a granulator, granulating, cooling and drying to obtain the detergent.
Compared with the prior art, the invention has the following beneficial effects:
the efficient powder cleaning agent provided by the invention has strong dirt removing capability which is not limited by low temperature, has an obvious sterilization effect, and simultaneously has strong stability in a high-humidity environment, can maintain the powder structure of the cleaning agent for a long time, and avoids influence on application of the cleaning agent due to premature moisture absorption and agglomeration.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the number clearly indicates the singular.
The invention provides a high-efficiency powder cleaning agent, which comprises, by weight, 40-70 parts of a builder, 25-35 parts of an oxidant, 1-5 parts of an active agent and 3-10 parts of a surfactant.
In one embodiment, the high efficiency powder detergent comprises 59.3 parts of builder, 30.1 parts of oxidant, 3.9 parts of active agent and 6.7 parts of surfactant by weight.
Oxidizing agent
In one embodiment, the oxidizing agent is selected from one or more of sodium percarbonate, sodium perborate, sodium persulfate, potassium percarbonate, potassium perborate, potassium persulfate.
Preferably, the sodium percarbonate is coated sodium percarbonate.
Preferably, the particle size of the sodium percarbonate is 20 to 40 mesh.
In a preferred embodiment, the oxidizing agent is sodium percarbonate.
Sodium percarbonate is an inorganic substance, belongs to a strong oxidant, and has a molecular formula of 2Na2CO3·3H2O2Or Na2CO3·1.5H2O2. The appearance is white crystal or crystalline powder, and oxygen can be released when the powder is wet. Sodium percarbonate is an addition compound of hydrogen peroxide and sodium carbonate, and is mainly used as a bleaching agent and an oxidizing agent, and a detergent, a cleaning agent and a bactericide in chemical industry, papermaking, textile, dyeing and finishing, food, medicine, health and other departments. Other applications are similar to sodium perborate and can replace sodium perborate to save boron salts.
Preferably, the sodium percarbonate is coated sodium percarbonate.
Preferably, the particle size of the sodium percarbonate is 20 to 40 mesh.
The coated sodium percarbonate with the particle size of 20-40 meshes guarantees the shelf life to a certain extent.
Active agent
In one embodiment, the active agent is selected from one or more of tetraacetylethylenediamine, nonanoylphenyl ester sulfonate, decanoylphenyl ester sulfonate, tetrasodium iminodisuccinate.
Preferably, the active agent is tetraacetylethylenediamine.
The tetraacetylethylenediamine is used as a peroxide activator, so that the washing effect and the disinfection and sterilization functions of the peroxide in low-temperature water are improved.
Bleaching agent is an important auxiliary agent in detergent, and mainly comprises two main classes of oxygen-containing bleaching agent and chlorine-containing bleaching agent. Among many washing products, bleaching detergents have been widely favored since the 70 s since their appearance because of their high whitening, brightening, disinfecting, sterilizing and detergent-removing effects on fabrics. Oxygen-containing bleaching agents are added to more than 90% of detergents in European markets, and the sales of such oxygen-containing bleaching detergents in the U.S. market are also increasing at an annual growth rate of 20% to 25%.
Among bleaching agents, oxygen-containing bleaching agents, especially peroxide bleaching agents, have been much more promising than conventional chlorine-containing bleaching agents. The oxygen-containing bleaching agent has no toxicity and chlorine smell, is suitable for all fibers and colored fabrics, has a series of advantages of good compatibility with various surfactants and enzymes and the like, and is popular among consumers. Oxygen-containing bleaching agents are most commonly used Sodium Perborate (SPB), accounting for about 75% of the total used. Because of high stability of sodium perborate, only when the service temperature exceeds 70qC and releases nascent oxygen, can exert its bleaching effect effectively, and a large amount of synthetic fibers and wool fabrics can not adapt to this temperature. There is a need to develop activators that can promote bleaching effectiveness at low temperatures.
Tetraacetylethylenediamine (TAED) is a bleach activator meeting such a requirement, and it has excellent bleaching performance at low temperatures, good environmental protection and a suitable price, and the TAED/sodium perborate system has become a european standard bleach activator system, and 75% to 80% of bleach detergents used in europe use the TAED/sodium perborate system. There are studies showing that: in the formula of the detergent, when the content of the tetraacetylethylenediamine reaches 1.5-5.0%, the sodium perborate can exert the bleaching effect at normal temperature.
Surface active agent
In one embodiment, the surfactant is a fatty alcohol polyether.
Preferably, the fatty alcohol polyether comprises the isomeric alcohol polyoxyethylene ethers.
The chemical products using isomeric alcohol polyoxyethylene ether as a surfactant are mainly classified into isomeric dodecyl alcohol polyoxyethylene ether, isomeric undecyl alcohol polyoxyethylene ether, isomeric tridecyl alcohol polyoxyethylene ether and the like.
Preferably, the hydroxyl value of the isomeric alcohol polyoxyethylene ether is 25-40 mgKOH/g; more preferably, the isomeric alcohol polyoxyethylene ether has a hydroxyl value of 25 to 31 mgKOH/g.
Preferably, the isomeric alcohol polyoxyethylene ether is selected from one or more of isomeric dodecyl alcohol polyoxyethylene ether, isomeric undecyl alcohol polyoxyethylene ether and isomeric tridecyl alcohol polyoxyethylene ether; more preferably, the isomeric alcohol polyoxyethylene ether is isomeric tridecanol polyoxyethylene ether.
The applicant has found that when sodium percarbonate is coated sodium percarbonate and the particle size is 20-40 meshes, the detergency is poor by using a conventional surfactant of a detergent, such as sodium linear alkylbenzene sulfonate, sodium dodecyl sulfate, sodium olefin sulfonate, sodium fatty acid polyoxyethylene ether sulfate and alkylolamide, however, the applicant has surprisingly found that when the surfactant is fatty alcohol polyether, especially fatty alcohol polyether including isomeric alcohol polyoxyethylene ether, and the isomeric alcohol polyoxyethylene ether is isomeric tridecanol polyoxyethylene ether, especially isomeric tridecanol polyoxyethylene ether having a hydroxyl value of 25-40mgKOH/g, the detergency can be improved for a short time, the applicant believes that a possible reason is that the isomeric alcohol polyoxyethylene ether, especially isomeric tridecanol polyoxyethylene ether having a hydroxyl value of 25-40mgKOH/g, has a strong action force between coated sodium percarbonate molecules in an aqueous solution, meanwhile, the isomeric tridecanol polyoxyethylene ether serving as the isomeric alcohol polyoxyethylene ether is fully spread on the coated sodium percarbonate protective film, so that the coated sodium percarbonate protective film is promoted to be decomposed, and sodium percarbonate molecules can quickly release active oxygen under the action of tetraacetylethylenediamine within a specified time to play a role in decontamination capability.
In one embodiment, the fatty alcohol polyether further comprises fatty alcohol polyoxyethylene ether polyoxypropylene ether, wherein the weight ratio of the fatty alcohol polyoxyethylene ether to the isomeric alcohol polyoxyethylene ether is 1: (1.5-2.5).
Preferably, the weight ratio of the fatty alcohol-polyoxyethylene ether polyoxypropylene ether to the isomeric alcohol-polyoxyethylene ether is 1: 1.8.
preferably, the carbon number of the fatty alcohol in the fatty alcohol polyoxyethylene ether polyoxypropylene ether is 4-13; more preferably, the carbon number of the fatty alcohol in the fatty alcohol polyoxyethylene ether polyoxypropylene ether is 12.
Preferably, the weight average molecular weight of the fatty alcohol polyoxyethylene polyoxypropylene ether is 1200-2000; more preferably, the fatty alcohol polyoxyethylene polyoxypropylene ether has a weight average molecular weight of 1500.
The applicant finds that when the isomeric tridecanol polyoxyethylene ether exists and the powder detergent is placed in an environment with the humidity of 80%, the powder detergent can accelerate the phenomenon of moisture absorption and agglomeration, and the stability of the powder detergent is influenced, and the applicant surprisingly finds that when the fatty alcohol polyoxyethylene ether is added, the carbon number of the fatty alcohol is 4-13, especially 12, and the weight-average molecular weight is 1500, the phenomenon of moisture absorption and agglomeration of the powder detergent in the environment with the humidity of 80% can be effectively reduced, and the applicant considers that under the condition, the possible reason is that sodium carbonate, potassium carbonate and isomeric tridecanol polyoxyethylene ether molecules in a builder in the powder detergent are not directly contacted with water molecules in the air due to the longer fatty chain and random polyether in the fatty alcohol polyoxyethylene ether molecules, so that the compactness of the protective film on the surface of the powder detergent molecules is improved, the hygroscopicity of the powder detergent is hindered, however, the applicant unexpectedly finds that if the content of the fatty alcohol polyoxyethylene ether polyoxypropylene ether is too large, the adhesion between the powder in the powder detergent is promoted, and the stability is reduced.
Builder
In one embodiment, the builder is selected from one or more of sodium carbonate, potassium carbonate, sodium bicarbonate.
Preferably, the sodium carbonate has a bulk density of 0.45 to 0.7g/cm3。
Bulk density is the mass per unit volume measured immediately after filling of a container into which dust or powder is freely filled.
Preferably, the builders are sodium carbonate, potassium carbonate and sodium bicarbonate; further preferably, the weight ratio of the sodium carbonate, the potassium carbonate and the sodium bicarbonate is (3-8): 1: (0.5-1); more preferably, the weight ratio of sodium carbonate, potassium carbonate and sodium bicarbonate is 5.6: 1: 0.75.
preferably, the sodium carbonate has a bulk density of 0.45 to 0.7g/cm3。
The applicants have unexpectedly found that when the builder comprises sodium carbonate, potassium carbonate and sodium bicarbonate, and the bulk density of the sodium carbonate is in the range of from 0.45 to 0.7g/cm3The applicant believes that the possible reason for the accelerated dissolution time of the powder detergent is that it spreads in an aqueous solution at a bulk density of 0.45 to 0.7g/cm3Fatty alcohol poly (ester of sodium and potassium carbonate) sThe polyoxyethylene polyoxypropylene ether can be easily separated from the water, and can be diffused in the water solution to accelerate the emulsifying capacity of the fatty alcohol polyoxyethylene ether polyoxypropylene ether, and the bulk density is 0.45-0.7g/cm3The sodium carbonate and the potassium carbonate absorb water and swell in time to be dissolved.
The second aspect of the present invention provides a method for preparing the high efficiency powder detergent, which comprises: uniformly mixing the builder, the oxidant, the active agent and the surfactant at 40-50 ℃, putting into a granulator, granulating, cooling and drying to obtain the detergent.
In one embodiment, the method for preparing the high-efficiency powder cleaning agent comprises the following steps: uniformly mixing the builder, the oxidant, the active agent and the surfactant at 45 ℃, putting into a granulator, granulating, cooling and drying to obtain the detergent.
Examples
Hereinafter, the present invention will be described in more detail by way of examples, but it should be understood that these examples are merely illustrative and not restrictive. The starting materials used in the examples which follow are all commercially available unless otherwise stated.
Example 1
Embodiment 1 of the present invention provides an efficient powder detergent, which comprises the following components: 40 parts of a builder, 25 parts of an oxidant, 1 part of an active agent and 3 parts of a surfactant.
The oxidant is coated sodium percarbonate with a particle size of 20-40 meshes, and is purchased from Zhejiang gold peroxide GmbH.
The active agent is tetraacetylethylenediamine.
The surfactant is isomeric alcohol polyoxyethylene ether and fatty alcohol polyoxyethylene ether polyoxypropylene ether, and the weight ratio of the surfactant to the surfactant is 1.5: 1; the isomeric alcohol polyoxyethylene ether is isomeric tridecanol polyoxyethylene ether, the hydroxyl value is 25-31mgKOH/g, and the isomeric alcohol polyoxyethylene ether is purchased from the chemical industry Co., Ltd. of Wujiang, and the model is E-1340; the fatty alcohol polyoxyethylene ether polyoxypropylene ether has the fatty alcohol carbon number of 12 and the weight-average molecular weight of 1500, is purchased from Heian petrochemical plants of Jiangsu province and has the model of CPE-1500.
The builderSodium carbonate, potassium carbonate and sodium bicarbonate, and the weight ratio of the sodium carbonate to the potassium carbonate to the sodium bicarbonate is 3: 1: 0.5, the bulk density of the sodium carbonate is 0.45-0.7g/cm3From Zibo, Shang Co., Ltd.
The preparation method of the high-efficiency powder cleaning agent comprises the following steps: uniformly mixing the builder, the oxidant, the active agent and the surfactant at 45 ℃, putting into a granulator, granulating, cooling and drying to obtain the detergent.
Example 2
Embodiment 2 of the present invention provides an efficient powder detergent, which comprises the following components: 70 parts of builder, 35 parts of oxidant, 5 parts of active agent and 10 parts of surfactant.
The oxidant is coated sodium percarbonate with a particle size of 20-40 meshes, and is purchased from Zhejiang gold peroxide GmbH.
The active agent is tetraacetylethylenediamine.
The surfactant is isomeric alcohol polyoxyethylene ether and fatty alcohol polyoxyethylene ether polyoxypropylene ether, and the weight ratio of the surfactant to the surfactant is 2.5: 1; the isomeric alcohol polyoxyethylene ether is isomeric tridecanol polyoxyethylene ether, the hydroxyl value is 25-31mgKOH/g, and the isomeric alcohol polyoxyethylene ether is purchased from the chemical industry Co., Ltd. of Wujiang, and the model is E-1340; the fatty alcohol polyoxyethylene ether polyoxypropylene ether has the fatty alcohol carbon number of 12 and the weight-average molecular weight of 1500, is purchased from Heian petrochemical plants of Jiangsu province and has the model of CPE-1500.
The builder is sodium carbonate, potassium carbonate and sodium bicarbonate, and the weight ratio of the builder is 8: 1: 1, the bulk density of the sodium carbonate is 0.45-0.7g/cm3From Zibo, Shang Co., Ltd.
The preparation method of the high-efficiency powder cleaning agent comprises the following steps: uniformly mixing the builder, the oxidant, the active agent and the surfactant at 45 ℃, putting into a granulator, granulating, cooling and drying to obtain the detergent.
Example 3
Embodiment 3 of the present invention provides an efficient powder detergent, which comprises the following components: 59.3 parts of builder, 30.1 parts of oxidant, 3.9 parts of active agent and 6.7 parts of surfactant.
The oxidant is coated sodium percarbonate with a particle size of 20-40 meshes, and is purchased from Zhejiang gold peroxide GmbH.
The active agent is tetraacetylethylenediamine.
The surfactant is isomeric alcohol polyoxyethylene ether and fatty alcohol polyoxyethylene ether polyoxypropylene ether, and the weight ratio of the surfactant to the surfactant is 1.8: 1; the isomeric alcohol polyoxyethylene ether is isomeric tridecanol polyoxyethylene ether, the hydroxyl value is 25-31mgKOH/g, and the isomeric alcohol polyoxyethylene ether is purchased from the chemical industry Co., Ltd. of Wujiang, and the model is E-1340; the fatty alcohol polyoxyethylene ether polyoxypropylene ether has the fatty alcohol carbon number of 12 and the weight-average molecular weight of 1500, is purchased from Heian petrochemical plants of Jiangsu province and has the model of CPE-1500.
The builder is sodium carbonate, potassium carbonate and sodium bicarbonate, and the weight ratio of the builder is 5.6: 1: 0.75, the bulk density of the sodium carbonate is 0.45-0.7g/cm3From Zibo, Shang Co., Ltd.
The preparation method of the high-efficiency powder cleaning agent comprises the following steps: uniformly mixing the builder, the oxidant, the active agent and the surfactant at 45 ℃, putting into a granulator, granulating, cooling and drying to obtain the detergent.
Example 4
Embodiment 4 of the present invention provides an efficient powder detergent, which comprises the following components: 59.3 parts of builder, 30.1 parts of oxidant, 3.9 parts of active agent and 6.7 parts of surfactant.
The oxidant is coated sodium percarbonate with a particle size of 20-40 meshes, and is purchased from Zhejiang gold peroxide GmbH.
The active agent is tetraacetylethylenediamine.
The surfactant is isomeric alcohol polyoxyethylene ether and fatty alcohol polyoxyethylene ether polyoxypropylene ether, and the weight ratio of the surfactant to the surfactant is 1.8: 1; the isomeric alcohol polyoxyethylene ether is isomeric tridecanol polyoxyethylene ether, the hydroxyl value is 18-21mgKOH/g, and the isomeric alcohol polyoxyethylene ether is purchased from Nantong Yongle chemical Co., Ltd, and the model is E-1360; the fatty alcohol polyoxyethylene ether polyoxypropylene ether has the fatty alcohol carbon number of 12 and the weight-average molecular weight of 1500, is purchased from Heian petrochemical plants of Jiangsu province and has the model of CPE-1500.
The builder is sodium carbonate, potassium carbonate and sodium bicarbonate, and the weight ratio of the builder is 5.6: 1: 0.75, the bulk density of the sodium carbonate is 0.45-0.7g/cm3From Zibo, Shang Co., Ltd.
The preparation method of the high-efficiency powder cleaning agent comprises the following steps: uniformly mixing the builder, the oxidant, the active agent and the surfactant at 45 ℃, putting into a granulator, granulating, cooling and drying to obtain the detergent.
Example 5
Embodiment 5 of the present invention provides an efficient powder detergent, which comprises the following components: 59.3 parts of builder, 30.1 parts of oxidant, 3.9 parts of active agent and 6.7 parts of surfactant.
The oxidant is coated sodium percarbonate with a particle size of 20-40 meshes, and is purchased from Zhejiang gold peroxide GmbH.
The active agent is tetraacetylethylenediamine.
The surfactant is isomeric alcohol polyoxyethylene ether and fatty alcohol polyoxyethylene ether polyoxypropylene ether, and the weight ratio of the surfactant to the surfactant is 1.8: 1; the isomeric alcohol polyoxyethylene ether is isomeric tridecanol polyoxyethylene ether, the hydroxyl value is 18-21mgKOH/g, and the isomeric alcohol polyoxyethylene ether is purchased from Nantong Yongle chemical Co., Ltd, and the model is E-1360; the fatty alcohol polyoxyethylene ether polyoxypropylene ether has the fatty alcohol carbon number of 4 and the weight-average molecular weight of 1000, is purchased from Heian petrochemical plants of Jiangsu province and has the model of BPE-1000.
The builder is sodium carbonate, potassium carbonate and sodium bicarbonate, and the weight ratio of the builder is 5.6: 1: 0.75, the bulk density of the sodium carbonate is 0.45-0.7g/cm3From Zibo, Shang Co., Ltd.
The preparation method of the high-efficiency powder cleaning agent comprises the following steps: uniformly mixing the builder, the oxidant, the active agent and the surfactant at 45 ℃, putting into a granulator, granulating, cooling and drying to obtain the detergent.
Example 6
Embodiment 6 of the present invention provides an efficient powder detergent, which comprises the following components: 59.3 parts of builder, 30.1 parts of oxidant, 3.9 parts of active agent and 6.7 parts of surfactant.
The oxidant is coated sodium percarbonate with a particle size of 20-40 meshes, and is purchased from Zhejiang gold peroxide GmbH.
The active agent is tetraacetylethylenediamine.
The surfactant is isomeric alcohol polyoxyethylene ether and fatty alcohol polyoxyethylene ether polyoxypropylene ether, and the weight ratio of the surfactant to the surfactant is 1.8: 1; the isomeric alcohol polyoxyethylene ether is isomeric tridecanol polyoxyethylene ether, the hydroxyl value is 18-21mgKOH/g, and the isomeric alcohol polyoxyethylene ether is purchased from Nantong Yongle chemical Co., Ltd, and the model is E-1360; the fatty alcohol polyoxyethylene ether polyoxypropylene ether has the fatty alcohol carbon number of 4 and the weight-average molecular weight of 1500, is purchased from Heian petrochemical plants of Jiangsu province and has the model of BPE-1500.
The builder is sodium carbonate, potassium carbonate and sodium bicarbonate, and the weight ratio of the builder is 5.6: 1: 0.75, the bulk density of the sodium carbonate is 0.45-0.7g/cm3From Zibo, Shang Co., Ltd.
The preparation method of the high-efficiency powder cleaning agent comprises the following steps: uniformly mixing the builder, the oxidant, the active agent and the surfactant at 45 ℃, putting into a granulator, granulating, cooling and drying to obtain the detergent.
Example 7
Embodiment 7 of the present invention provides an efficient powder detergent, which comprises the following components: 59.3 parts of builder, 30.1 parts of oxidant, 3.9 parts of active agent and 6.7 parts of surfactant.
The oxidant is coated sodium percarbonate with a particle size of 20-40 meshes, and is purchased from Zhejiang gold peroxide GmbH.
The active agent is tetraacetylethylenediamine.
The surfactant is isomeric alcohol polyoxyethylene ether; the isomeric alcohol polyoxyethylene ether is isomeric tridecanol polyoxyethylene ether, the hydroxyl value is 25-31mgKOH/g, and the isomeric alcohol polyoxyethylene ether is purchased from the chemical industry Co., Ltd. in Wujiang, and the model is E-1340.
The builder is sodium carbonate, potassium carbonate and sodium bicarbonate in a weight ratioIs 5.6: 1: 0.75, the bulk density of the sodium carbonate is 0.45-0.7g/cm3From Zibo, Shang Co., Ltd.
The preparation method of the high-efficiency powder cleaning agent comprises the following steps: uniformly mixing the builder, the oxidant, the active agent and the surfactant at 45 ℃, putting into a granulator, granulating, cooling and drying to obtain the detergent.
Example 8
Embodiment 8 of the present invention provides an efficient powder detergent, which comprises the following components: 59.3 parts of builder, 30.1 parts of oxidant, 3.9 parts of active agent and 6.7 parts of surfactant.
The oxidant is coated sodium percarbonate with a particle size of 20-40 meshes, and is purchased from Zhejiang gold peroxide GmbH.
The active agent is tetraacetylethylenediamine.
The surfactant is fatty alcohol polyoxyethylene ether polyoxypropylene ether; the fatty alcohol polyoxyethylene ether polyoxypropylene ether has the fatty alcohol carbon number of 12 and the weight-average molecular weight of 1500, is purchased from Heian petrochemical plants of Jiangsu province and has the model of CPE-1500.
The builder is sodium carbonate, potassium carbonate and sodium bicarbonate, and the weight ratio of the builder is 5.6: 1: 0.75, the bulk density of the sodium carbonate is 0.45-0.7g/cm3From Zibo, Shang Co., Ltd.
The preparation method of the high-efficiency powder cleaning agent comprises the following steps: uniformly mixing the builder, the oxidant, the active agent and the surfactant at 45 ℃, putting into a granulator, granulating, cooling and drying to obtain the detergent.
Example 9
Embodiment 9 of the present invention provides an efficient powder detergent, which comprises the following components: 59.3 parts of builder, 30.1 parts of oxidant, 3.9 parts of active agent and 6.7 parts of surfactant.
The oxidant is coated sodium percarbonate with a particle size of 20-40 meshes, and is purchased from Zhejiang gold peroxide GmbH.
The active agent is tetraacetylethylenediamine.
The surfactant is isomeric alcohol polyoxyethylene ether and fatty alcohol polyoxyethylene ether polyoxypropylene ether, and the weight ratio of the surfactant to the surfactant is 1.8: 1; the isomeric alcohol polyoxyethylene ether is isomeric tridecanol polyoxyethylene ether, the hydroxyl value is 25-31mgKOH/g, and the isomeric alcohol polyoxyethylene ether is purchased from the chemical industry Co., Ltd. of Wujiang, and the model is E-1340; the fatty alcohol polyoxyethylene ether polyoxypropylene ether has the fatty alcohol carbon number of 12 and the weight-average molecular weight of 1500, is purchased from Heian petrochemical plants of Jiangsu province and has the model of CPE-1500.
The builder is potassium carbonate and sodium bicarbonate, and the weight ratio of the builder to the builder is 1: 0.75.
the preparation method of the high-efficiency powder cleaning agent comprises the following steps: uniformly mixing the builder, the oxidant, the active agent and the surfactant at 45 ℃, putting into a granulator, granulating, cooling and drying to obtain the detergent.
Example 10
Embodiment 10 of the present invention provides an efficient powder detergent, which comprises the following components: 59.3 parts of builder, 30.1 parts of oxidant, 3.9 parts of active agent and 6.7 parts of surfactant.
The oxidant is coated sodium percarbonate with a particle size of 20-40 meshes, and is purchased from Zhejiang gold peroxide GmbH.
The active agent is tetraacetylethylenediamine.
The surfactant is isomeric alcohol polyoxyethylene ether and fatty alcohol polyoxyethylene ether polyoxypropylene ether, and the weight ratio of the surfactant to the surfactant is 1.8: 1; the isomeric alcohol polyoxyethylene ether is isomeric tridecanol polyoxyethylene ether, the hydroxyl value is 25-31mgKOH/g, and the isomeric alcohol polyoxyethylene ether is purchased from the chemical industry Co., Ltd. of Wujiang, and the model is E-1340; the fatty alcohol polyoxyethylene ether polyoxypropylene ether has the fatty alcohol carbon number of 12 and the weight-average molecular weight of 1500, is purchased from Heian petrochemical plants of Jiangsu province and has the model of CPE-1500.
The builder is sodium carbonate and sodium bicarbonate, and the weight ratio of the builder to the builder is 5.6: 0.75, the bulk density of the sodium carbonate is 0.45-0.7g/cm3From Zibo, Shang Co., Ltd.
The preparation method of the high-efficiency powder cleaning agent comprises the following steps: uniformly mixing the builder, the oxidant, the active agent and the surfactant at 45 ℃, putting into a granulator, granulating, cooling and drying to obtain the detergent.
Example 11
Embodiment 11 of the present invention provides an efficient powder detergent, which comprises the following components: 59.3 parts of builder, 30.1 parts of oxidant, 3.9 parts of active agent and 6.7 parts of surfactant.
The oxidant is coated sodium percarbonate with a particle size of 20-40 meshes, and is purchased from Zhejiang gold peroxide GmbH.
The active agent is tetraacetylethylenediamine.
The surfactant is isomeric alcohol polyoxyethylene ether and fatty alcohol polyoxyethylene ether polyoxypropylene ether, and the weight ratio of the surfactant to the surfactant is 1.8: 1; the isomeric alcohol polyoxyethylene ether is isomeric tridecanol polyoxyethylene ether, the hydroxyl value is 25-31mgKOH/g, and the isomeric alcohol polyoxyethylene ether is purchased from the chemical industry Co., Ltd. of Wujiang, and the model is E-1340; the fatty alcohol polyoxyethylene ether polyoxypropylene ether has the fatty alcohol carbon number of 12 and the weight-average molecular weight of 1500, is purchased from Heian petrochemical plants of Jiangsu province and has the model of CPE-1500.
The builder is sodium carbonate, potassium carbonate and sodium bicarbonate, and the weight ratio of the builder is 5.6: 1: 0.75, the bulk density of the sodium carbonate is more than 0.9g/cm3Purchased from Longsheng chemical industry.
The preparation method of the high-efficiency powder cleaning agent comprises the following steps: uniformly mixing the builder, the oxidant, the active agent and the surfactant at 45 ℃, putting into a granulator, granulating, cooling and drying to obtain the detergent.
Performance evaluation
1. Decontamination capability: the soil removal capability of the high-efficiency powder cleaning agent obtained in the embodiments 1 to 11 is respectively tested according to the GB/T13174-2008 standard, wherein three types of dirty cloth, namely JB-02 protein dirty cloth, JB-03 sebum dirty cloth and JB-04 edible oil dirty cloth, are used for testing, the soil removal ratio is respectively measured, the soil removal ratio is superior when being greater than 1.05, and is inferior when being 1-1.05.
2. High humidity stability: the high performance powder cleaners obtained in examples 1 to 11 were placed in an environment of 80% humidity for one month to observe whether or not the caking phenomenon occurred.
3. Dissolving time: respectively placing the high-efficiency powder cleaning agents obtained in the embodiments 1-11 into water with a certain temperature of 10 ℃ to ensure that the mass concentration of the high-efficiency powder cleaning agents is 0.2%, stirring at a rotating speed of 60 r/min, recording the time for completely dissolving the cleaning agents, respectively accurately dissolving the cleaning agents until the tested dissolving time is unequal, sequencing the dissolving time from low to high, sequentially numbering the cleaning agents as 1-11, and numbering the cleaning agents as 1-3 as a first level; the numbers of the two stages are 4-8, and the numbers of the three stages are 9-11.
TABLE 1
Figure BDA0002750203270000121
Figure BDA0002750203270000131
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.

Claims (10)

1. The efficient powder cleaning agent is characterized by comprising, by weight, 40-70 parts of a builder, 25-35 parts of an oxidant, 1-5 parts of an active agent and 3-10 parts of a surfactant; the oxidant is selected from one or more of sodium percarbonate, sodium perborate, sodium persulfate, potassium percarbonate, potassium perborate and potassium persulfate.
2. The efficient powder detergent as claimed in claim 1, wherein the sodium percarbonate is coated sodium percarbonate with a particle size of 20-40 mesh.
3. The efficient powder detergent as claimed in claim 2, wherein the surfactant is fatty alcohol polyether.
4. The efficient powder detergent as claimed in claim 3, wherein the fatty alcohol polyether comprises an isomeric alcohol polyoxyethylene ether.
5. The efficient powder detergent according to claim 4, wherein the isomeric alcohol polyoxyethylene ether has a hydroxyl value of 25-31 mgKOH/g.
6. The efficient powder cleaning agent as claimed in claim 4, wherein the fatty alcohol polyether further comprises fatty alcohol polyoxyethylene ether polyoxypropylene ether, and the weight ratio of the fatty alcohol polyoxyethylene ether polyoxypropylene ether to the isomeric alcohol polyoxyethylene ether is 1: (1.5-2.5).
7. The efficient powder detergent as claimed in claim 6, wherein the carbon number of fatty alcohol in the fatty alcohol polyoxyethylene ether polyoxypropylene ether is 4-13.
8. A high efficiency powder detergent as claimed in any one of claims 1-7, wherein the builder is selected from one or more of sodium carbonate, potassium carbonate and sodium bicarbonate.
9. The high efficiency powder detergent according to claim 8, wherein the bulk density of the sodium carbonate is 0.45-0.7g/cm3。
10. A method for preparing a high efficiency powder detergent according to any one of claims 1-9, comprising: uniformly mixing the builder, the oxidant, the active agent and the surfactant at 40-50 ℃, putting into a granulator, granulating, cooling and drying to obtain the detergent.
CN202011181091.5A 2020-10-29 2020-10-29 Efficient powder cleaning agent and preparation method thereof Pending CN112080350A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113512476A (en) * 2021-08-09 2021-10-19 浙江家至洁科技有限公司 Multifunctional clothes, kitchen and household cleaning agent and preparation method thereof
CN114806742A (en) * 2022-05-25 2022-07-29 晋江市佐净日用品有限责任公司 Oxygen-increasing phosphorus-free cleaning paste and preparation method thereof
CN115651770A (en) * 2022-11-02 2023-01-31 浙江华诺化工有限公司 Powdery foaming cleaning agent containing catalase and preparation method thereof
CN114806742B (en) * 2022-05-25 2024-06-04 晋江市佐净日用品有限责任公司 Preparation method of oxygen-increasing phosphorus-free cleaning paste

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6641866B2 (en) * 2000-04-26 2003-11-04 Oriental Chemical Industries Co., Ltd. Process for manufacturing granular coated sodium percarbonate for detergent
EP2326704A4 (en) * 2008-09-24 2014-07-09 Ecolab Inc Granular cleaning and disinfecting composition
JP2017008318A (en) * 2015-06-16 2017-01-12 シーバイエス株式会社 Sterilization detergent composition
CN111304016A (en) * 2020-03-24 2020-06-19 广州立白企业集团有限公司 Sterilizing washing powder
CN111778115A (en) * 2020-08-17 2020-10-16 重庆迈捷实业有限公司 Cleaning agent and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6641866B2 (en) * 2000-04-26 2003-11-04 Oriental Chemical Industries Co., Ltd. Process for manufacturing granular coated sodium percarbonate for detergent
EP2326704A4 (en) * 2008-09-24 2014-07-09 Ecolab Inc Granular cleaning and disinfecting composition
JP2017008318A (en) * 2015-06-16 2017-01-12 シーバイエス株式会社 Sterilization detergent composition
CN111304016A (en) * 2020-03-24 2020-06-19 广州立白企业集团有限公司 Sterilizing washing powder
CN111778115A (en) * 2020-08-17 2020-10-16 重庆迈捷实业有限公司 Cleaning agent and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113512476A (en) * 2021-08-09 2021-10-19 浙江家至洁科技有限公司 Multifunctional clothes, kitchen and household cleaning agent and preparation method thereof
CN114806742A (en) * 2022-05-25 2022-07-29 晋江市佐净日用品有限责任公司 Oxygen-increasing phosphorus-free cleaning paste and preparation method thereof
CN114806742B (en) * 2022-05-25 2024-06-04 晋江市佐净日用品有限责任公司 Preparation method of oxygen-increasing phosphorus-free cleaning paste
CN115651770A (en) * 2022-11-02 2023-01-31 浙江华诺化工有限公司 Powdery foaming cleaning agent containing catalase and preparation method thereof

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