CN115975739A - Detergent composition and stable laundry beads for use therein - Google Patents

Abstract

The invention discloses a detergent composition and a stable washing coagulated bead applied by the detergent composition, and relates to the technical field of daily chemical industry. The detergent composition comprises the following components in percentage by weight: 11-30% of high boiling point solvent A, 3-10% of low boiling point solvent B, 2-10% of organic amine neutralizer, 0-8% of fatty acid salt, 0.1-1% of reducing agent, 15-30% of nonionic surfactant, 15-40% of anionic surfactant and the balance of water. The stable laundry beads are made from a water-soluble film encapsulating a detergent composition. According to the invention, through effective compounding of the organic solvent and the fatty acid salt, the problem of color change of the high-content sulfonate surfactant after the washing condensation bead is aged can be effectively improved, and the content of the polyoxyethylene ether sulfate is increased in the presence of a reducing agent, so that solid particles can not be separated out from the surface of the washing condensation bead, and the washing condensation bead has excellent storage stability and decontamination performance.

Description

A detergent composition and stable laundry beads used therein

Technical Field

The invention belongs to the field of daily chemical industry, and particularly relates to a liquid detergent composition suitable for water-soluble film encapsulation and containing an organic amine neutralizer, and stable laundry beads using the same.

Background Art

As people's pace of life accelerates, laundry detergent beads are becoming more and more popular among consumers due to their ultra-concentrated contents, single-bead precise quantitative delivery design, convenience of use, energy saving and environmental protection, and the market share of detergent beads is also growing.

Laundry detergent beads are made of a colorless and transparent water-soluble film that encapsulates the contents. Consumers are more directly aware of the appearance and smell than traditional bottled detergent products. Changes in the appearance of laundry detergent beads will give consumers a bad sensory experience, so maintaining the storage stability of laundry detergent beads over a long shelf life has always been a special concern of the industry.

In traditional liquid detergent products, water is usually the main solvent. Therefore, when selecting raw materials, the main considerations are their solubility and dispersibility in water. For laundry beads, low water content limits the application of many original conventional raw materials, among which the most typical raw material is the neutralizer. In traditional liquid detergent formulas, the main neutralizers used are sodium hydroxide or potassium hydroxide. The ionic salts formed by the neutralization of commonly used anionic surfactants have low solubility in systems with low water content, and the final formulated composition has poor stability and is prone to turbidity, precipitation and other problems. Although this problem can be solved to a certain extent by partially or completely replacing anionic surfactants with non-ionic surfactants, zwitterionic surfactants, etc., from the perspective of maintaining the detergency of detergents and other properties, the method of improving the neutralizer to retain the anionic surfactant is obviously more in line with long-term needs, so laundry beads usually use organic bases instead of inorganic bases.

However, the addition of organic amines will react with aldehydes in the detergent composition or polyethylene water-soluble film to produce Schiff base reaction, thereby causing the composition to change color, especially in the system with high content of sulfonate surfactants. At present, the main method of slowing down the discoloration is to add a reducing agent to the composition. However, the reducing agent will generate sulfate after oxidation. When the sulfate reaches saturation, it will precipitate from the water-soluble film and recrystallize on the outer surface of the laundry beads, which seriously affects the appearance of the product, thereby limiting the use of polyoxyethylene ether sulfate surfactants in the composition.

Patent US20210309948A discloses a technical solution using diallyldimethylammonium chloride copolymers and reducing agents such as sulfites, which can reduce the discoloration of the liquid detergent composition, but it still causes the problem of precipitation outside the film. Moreover, the addition of cationic polymer diallyldimethylammonium chloride copolymers will lead to a decrease in the solubility of the water-soluble film. Patent CN113980749A discloses a stable water-soluble film-encapsulated liquid detergent composition, which also uses nitrogen-containing compounds and reducing agents such as sulfites. Although it can effectively improve the overall stability of the washing composition, the nitrogen-containing compounds introduced at the same time require sufficient water to dissolve, which will also increase the cost of the composition.

Summary of the invention

In order to solve the problems existing in the above-mentioned prior art, the purpose of the present invention is to provide a stable laundry beads, which are made of a water-soluble film-encapsulated detergent composition, wherein the detergent composition can effectively improve the color change problem of laundry beads with a high content of sulfonate surfactants after aging through the effective compounding of organic solvents and fatty acid salts, and increasing the content of polyoxyethylene ether sulfate in the presence of a reducing agent will not cause solid particles to precipitate on the surface of the laundry beads, and has excellent storage stability and detergency performance.

To achieve the above object, the present invention adopts the following technical solutions:

A detergent composition comprises the following components in weight percentage: 11-30% of a high boiling point solvent A, 3-10% of a low boiling point solvent B, 2-10% of an organic amine neutralizer, 0-8% of a fatty acid salt, 0.1-1% of a reducing agent, 15-30% of a nonionic surfactant, 15-40% of anionic surfactant, and the balance is water.

Furthermore, the high boiling point solvent A is selected from one or more combinations of glycerol, diethylene glycol, dipropylene glycol, polyethylene glycol, and sorbitol. The weight percentage content of the high boiling point solvent A in the detergent composition is 11-30%, preferably 14-25%.

Furthermore, the low boiling point solvent B is selected from one or more combinations of propylene glycol, ethylene glycol, and dipropylene glycol methyl ether. The weight percentage content of the low boiling point solvent B in the detergent composition is 3-10%, preferably 5-8%.

Furthermore, the organic amine neutralizer is selected from a combination of one or more of ethanolamine, ethylenediamine and its co-products and tetraalkylammonium hydroxide; the ethanolamine is selected from at least one of monoethanolamine, diethanolamine, triethanolamine and N-alkyldiethanolamine; the ethylenediamine and its co-products are selected from at least one of diethylenetriamine, triethylenetetramine and tetraethylenepentamine; the tetraalkylammonium hydroxide is selected from at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide and tetrabutylammonium hydroxide.

Preferably, the organic amine neutralizer is selected from one or more mixtures of monoethanolamine, diethanolamine, triethanolamine, and N-alkyldiethanolamine.

More preferably, the organic amine neutralizer is selected from a mixture of one or more of monoethanolamine and triethanolamine.

Furthermore, the weight percentage of the organic amine neutralizer in the liquid detergent composition is 2-10%. The organic amine neutralizer can adjust the pH of the composition to 7-8.

Furthermore, the reducing agent is selected from a mixture of one or more of thiosulfate, pyrosulfite, sulfite and bisulfite.

Preferably, the reducing agent is selected from a mixture of one or more of pyrosulfite, bisulfite and sodium sulfite.

Furthermore, the weight percentage of the reducing agent in the liquid detergent composition is 0.1-1%.

Furthermore, the fatty acid salt is selected from a mixture of one or more fatty acid salts of C8-C18.

Preferably, the fatty acid salt is selected from a mixture of one or more of oleate, laurate, cocoate and ethoxylated fatty alcohol ether carboxylate.

Furthermore, the weight percentage content of the fatty acid salt in the liquid detergent composition is 0-8%, preferably 2-6%.

Furthermore, the nonionic surfactant is selected from a mixture of one or more of fatty alcohol alkoxylates, alkyl polysaccharides, fatty acid ester alkoxylates, fatty acid alkylolamides, fatty acid methyl ester ethoxylates, and polyether surfactants.

Furthermore, the weight percentage of the nonionic surfactant in the detergent composition is 15-30%.

Furthermore, the anionic surfactant is selected from a mixture of one or more of C6-C24 alkylbenzene sulfonates, C8-C18 alkyl sulfates, and C8-C18 ethoxylated fatty alcohol sulfates; wherein the alkylbenzene sulfonates are linear alkyl groups and branched alkyl groups, which may be saturated alkyl groups or alkyl groups containing one or more unsaturated double bonds.

Preferably, the alkylbenzene sulfonate is dodecylbenzene sulfonate; the alkyl sulfate is dodecyl sulfate; and the ethoxylated fatty alcohol sulfate is Texapon N70 from BASF.

Furthermore, the weight percentage of the anionic surfactant in the liquid detergent composition is 10-40%.

Furthermore, the detergent composition also contains 0-5% of other auxiliary agents; the other auxiliary agents are selected from at least one of chelating agents, enzyme preparations, preservatives, polymers, inorganic salts, viscosity regulators, antibacterial agents, colorants, flavors, and acid-base regulators.

Furthermore, the detergent composition can be encapsulated with a water-soluble film to prepare laundry beads.

A stable laundry bead comprises a water-soluble film and the above-mentioned detergent composition; the water-soluble film encapsulates the detergent composition; the water-soluble film is a mixture of one or more polyvinyl alcohol homopolymers and polyvinyl alcohol copolymers; the polyvinyl alcohol homopolymer is a hydrolysis product of a homopolymer of vinyl acetate; the polyvinyl alcohol copolymer is a hydrolysis product of a copolymer of vinyl acetate and a second monomer, the second monomer is an acrylic monomer, and the molar percentage of the second monomer in the polyvinyl alcohol copolymer is 2%-9%.

Furthermore, the viscosity of the aqueous solution of the film with a mass percentage of 4% is 10 centipoise to 25 centipoise.

The technical solution described in the present invention has the following beneficial effects:

1. The present invention unexpectedly discovered that, by simply adding a single reducing agent, the laundry beads prepared from a high content of sulfonate surfactant can have stable color after aging, and have a higher cost-effectiveness, better storage stability and detergency performance.

2. The characteristic of the present invention is that the laundry beads are prepared from high-content sulfate-type surfactants by effectively compounding organic solvents and fatty acid salts, and have no precipitation outside the membrane after aging and have good storage stability.

DETAILED DESCRIPTION

For those skilled in the art, the features, benefits and advantages of the present invention will become apparent by reading the contents disclosed in this specification.

Unless otherwise indicated, all percentages, fractions and ratios are calculated based on the total weight of the composition of the present invention. Unless otherwise indicated, all weights of listed ingredients are given as active ingredients, so they do not include solvents or by-products that may be included in commercially available materials. The term "weight percentage content" herein may be represented by the symbol "%".

Unless otherwise indicated, all molecular weights herein are weight average molecular weight expressed in Daltons.

Unless otherwise specified, all formulations and tests herein took place at 25°C.

As used herein, "includes," "comprising," "including," "containing," "having," or other variations are intended to encompass non-closed inclusions, and no distinction is made between these terms. The term "comprising" means that other steps and ingredients that do not affect the end result may be added. The term "comprising" also includes the terms "consisting of" and "consisting essentially of." The compositions and methods/processes of the present invention comprise, consist of, and consist essentially of the essential elements and limitations described herein, as well as any additional or optional ingredients, components, steps, or limitations described herein. "Not containing" herein means that it is not considered to be added, specifically referring to a weight percentage of less than 0.01%.

Laundry Pods

The laundry pod comprises a water soluble film which encloses a liquid composition in at least one compartment.Multi-compartment laundry pods can separate chemically incompatible ingredients or where it is desirable to release a portion of the ingredients earlier or later.

The laundry condensate composition refers to a detergent composition in a liquid state. The composition can be encapsulated by a water-soluble film to form a laundry condensate product. The laundry condensate composition is diluted according to a certain ratio, or directly contacted with a substrate (i.e., a fabric product, a hard surface, etc.) to be contacted, thereby removing stains on the substrate surface and achieving the purpose of cleaning the substrate surface. The liquid laundry condensate composition generally also contains a solvent, a surfactant system and other common detergent aids such as a viscosity regulator, an enzyme preparation, a fragrance, etc.

Water soluble film

The water-soluble film of the present invention is a water-soluble polymer prepared from monomers, and then obtained by film-making equipment. The water-soluble polymer refers to a mixture of one or more polyvinyl alcohol homopolymers and copolymers. The term water-soluble film of the present invention is not distinguished from water-soluble film. The thickness of the water-soluble film is 65 microns to 90 microns.

The polyvinyl alcohol homopolymer is a hydrolysis product of a homopolymer of vinyl acetate, and the polyvinyl alcohol copolymer is a hydrolysis product of a copolymer of vinyl acetate and a second monomer. The second monomer is selected from a mixture of one or more of acrylic acid, acrylic esters, methacrylic acid, and methacrylic esters. The polyvinyl alcohol homopolymer or copolymer refers to a hydrolysis product of a homopolymer or copolymer of vinyl acetate, and the degree of hydrolysis is 86%-99%. The test method for the degree of hydrolysis is described in detail in "GB/T12010.2-2010 Plastic Polyvinyl Alcohol Material (PVAL) Part 2: Performance Determination". In this standard, the degree of hydrolysis is called the degree of alcoholysis, and the two have the same meaning.

Method for preparing laundry beads

The laundry beads disclosed herein include at least one sealed cavity. Thus, the laundry beads may include a single cavity or multiple cavities. In embodiments including multiple cavities, each cavity may contain the same and/or different compositions. In turn, the composition may take any suitable form, including but not limited to liquids, solids, and combinations thereof (e.g., solids suspended in liquids). The cavities of multi-cavity beads may have the same or different sizes and/or volumes.

The laundry beads of the present invention can be processed in three ways: vertical filling, horizontal filling and drum filling. Drum filling is preferred, which has the highest production efficiency and can be produced continuously. Each row of the drum can contain a plurality of mold cavities of the same shape, and the transition between the bottom inner wall and the side wall of the mold is designed to have a curvature radius of 9.525 mm. The curvature radius enables the mold to give the membrane package rounded corners, thereby forming a generally rectangular package shape and a rounded transition to the bottom membrane surface. Holes are set for the cavity along the bottom surface to suck the vacuum on the membrane and pull the membrane into the mold.

Before vacuuming, the bottom film needs to be heated by a heating roller or infrared light to soften the water-soluble film, which is beneficial for the next step of vacuuming. The heating temperature is 60-90°C. Vacuuming requires a negative pressure in the range of 100 mbar to 600 mbar for about 0.5 to 1.5 seconds, so that the bottom film is completely attached to the bottom surface of the mold.

The mask needs to pass through a wetting roller. The wetting agent can be water, film composition or plasticizer. It is very important to control the speed of the wetting roller, which will affect the amount of water applied and the sealing strength in the later stage. Apply appropriate pressure in the sealing area to seal the upper and lower films to form a completely closed cavity. Next, use a cutting knife to cut the edges of the film to prepare unit dose products.

High boiling point solvent A

The weight percentage content of the high boiling point solvent A in the liquid detergent composition is 11-30%, preferably 14-25%.

The high boiling point solvent A is selected from one or more combinations of glycerol, diethylene glycol, dipropylene glycol, polyethylene glycol, and sorbitol. A suitable example of the polyethylene glycol is PEG400.

The high boiling point solvent A is a solvent with a boiling point of ≥200°C (101.3 kPa), and this type of solvent is not very volatile in the gel beads product.

Low boiling point solvent B

The weight percentage content of the low boiling point solvent B in the liquid detergent composition is 3-10%, preferably 5-8%.

The low boiling point solvent B is a solvent with a boiling point of less than 200° C. (101.3 kPa). The low boiling point solvent B is selected from one or more combinations of propylene glycol, ethylene glycol, and dipropylene glycol methyl ether.

PVA membrane has a certain degree of permeability, and water, solvents and oxygen can easily pass through the membrane layer, affecting the stability of the contents. During the long-term storage of gel beads, some solvents and water will gradually evaporate, and the composition ratio of the contents will change significantly. After losing some solvents and water, the contents may precipitate sulfate particles or gel stratification. The yellowing of gel beads is mainly caused by the oxidation of organic amines. Oxygen can easily pass through the membrane, exacerbating the oxidation of organic amines.

We unexpectedly discovered that controlling organic solvents with different boiling points within an appropriate dosage range can alleviate the oxidation of organic amines to a certain extent, and also has a good inhibitory effect on the precipitation of low-solubility sulfates. Since the mechanism of the effect of different boiling point organic solvents on relieving discoloration and improving particle precipitation has not been clearly studied, it is speculated that the possible mechanism is: compared with low-boiling point solvents, high-boiling point solvents are less likely to volatilize through the PVA film during long-term storage and aging, and the oxidation of organic amines reacts more slowly within a specific high- and low-boiling point solvent combination range, thereby having a certain improvement effect on discoloration; and high- and low-boiling point solvents within a specific dosage range have a better ability to bind free water, which can make the free water in the content less volatile to a certain extent, thereby preventing the precipitation or precipitation of low-solubility sulfate particulate matter.

Organic amine neutralizer

The weight percentage content of the organic amine neutralizer in the liquid detergent composition is 2-10%.

The organic amine neutralizer is selected from a combination of one or more of ethanolamine, ethylenediamine and its co-products and tetraalkylammonium hydroxide. The ethanolamine is selected from at least one of monoethanolamine, diethanolamine, triethanolamine and N-alkyldiethanolamine; the ethylenediamine and its co-products are selected from at least one of diethylenetriamine, triethylenetetramine and tetraethylenepentamine; the tetraalkylammonium hydroxide is selected from at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide and tetrabutylammonium hydroxide.

Preferably, the organic amine neutralizer is selected from one or more mixtures of monoethanolamine, diethanolamine, triethanolamine or N-alkyldiethanolamine.

More preferably, the organic amine neutralizer is selected from one or more mixtures of monoethanolamine or triethanolamine.

reducing agent

The weight percentage content of the reducing agent in the liquid detergent composition of the present invention is 0.1-1%, preferably 0.2-0.6%.

The reducing agent is selected from a mixture of one or more of thiosulfate, pyrosulfite, sulfite and bisulfite. Preferably, the reducing agent is selected from a mixture of one or more of pyrosulfite, bisulfite and sodium sulfite.

The cation part of the sulfite, thiosulfate, pyrosulfite and bisulfite is selected from at least one of sodium ion, potassium ion, ammonium ion and ammonium ion formed by organic amine. Among the ammonium ions formed by organic amine, the organic amine is selected from one or more combinations of ethanolamine, ethylenediamine and its co-products and tetraalkylammonium hydroxide. The ethanolamine is selected from at least one of monoethanolamine, diethanolamine, triethanolamine and N-alkyldiethanolamine; the ethylenediamine and its co-products are selected from at least one of diethylenetriamine, triethylenetetramine and tetraethylenepentamine; the tetraalkylammonium hydroxide is selected from at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide and tetrabutylammonium hydroxide.

We have found that only a mixture of one or more of the above-mentioned sulfites, thiosulfates, pyrosulfites, and bisulfites can impart enhanced stability to the liquid detergent composition. Certain sulfur-containing molecules other than those disclosed in the technical solution of the present invention, such as dithionites, thiourea dioxide, etc., not only fail to stabilize the liquid detergent composition, but also may bring negative effects such as odor.

Fatty acid salts

The weight percentage of the fatty acid salt in the liquid detergent composition of the present invention is 0-8%, preferably 2-6%.

The fatty acid salt is selected from a mixture of one or more fatty acid salts of C8-C18. The alkyl chain segment can be straight chain or branched, and can be a saturated alkyl or an alkyl containing one or more unsaturated double bonds. The fatty acid salt can be a single composition or a mixture of multiple fatty acid salts. Preferably, the fatty acid salt is selected from a mixture of one or more of oleate, laurate, cocoate, and ethoxylated fatty alcohol ether carboxylate. In the ethoxylated fatty alcohol ether carboxylate, the carbon number of the fatty alcohol is preferably 8-18, and the average degree of ethoxylation is preferably 2.0-10.

Anionic surfactants

The weight percentage of the anionic surfactant in the liquid detergent composition of the present invention is 15-40%.

The anionic surfactant is selected from one or more of C6-C24 alkylbenzene sulfonates, C8-C18 alkyl sulfates, C8-C18 ethoxylated fatty alcohol sulfates, and ethoxylated fatty alcohol ether carboxylates; the alkyl group may be a linear alkyl group or a branched alkyl group; the alkyl group may be a saturated alkyl group or an alkyl group containing one or more unsaturated double bonds.

The cationic part of the anionic surfactant is selected from at least one of sodium ions, potassium ions, ammonium ions, and ammonium ions formed by organic amines. Among the ammonium ions formed by organic amines, the organic amines are selected from a combination of one or more of ethanolamine, ethylenediamine and its co-products, and tetraalkylammonium hydroxide. Ethanolamine is selected from at least one of monoethanolamine, diethanolamine, triethanolamine, and N-alkyldiethanolamine; ethylenediamine and its co-products are selected from at least one of diethylenetriamine, triethylenetetramine, and tetraethylenepentamine; and tetraalkylammonium hydroxide is selected from at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide.

The alkylbenzene sulfonate of the present invention has an alkyl carbon number of 6-24, and is selected from at least one of a straight-chain alkyl group and a branched-chain alkyl group; it can be a saturated alkyl group or an alkyl group containing one or more unsaturated double bonds. In the technical solution of the present invention, the content of the alkylbenzene sulfonate is 10%-28%. The content of the alkylbenzene sulfonate is calculated based on the content of alkylbenzene sulfonic acid.

The alkylbenzene sulfonate satisfies the following formula:

Ra is an alkyl group having 6 to 24 carbon atoms, and M ⁺ is a cationic moiety. A suitable example is dodecylbenzenesulfonate.

The ethoxylated fatty alcohol sulfates of the present invention are derivatives of ethoxylated fatty alcohols and have the following general formula:

R _b is an alkyl group with a carbon number of 6-24; x is 0.5-15; wherein M ⁺ is a cationic moiety. R ₁ can be a straight-chain alkyl group or a branched alkyl group; it can be a saturated alkyl group or an alkyl group containing one or more unsaturated double bonds. Preferably, R _b is a straight-chain alkyl group with a carbon number of 8-18. x represents the average degree of ethoxylation, which is 0.5-15, preferably 0.5-10, and more preferably 0.5-3. A suitable example is Texapon N70 from BASF.

The alkyl sulfate of the present invention may have a straight chain or a branched chain alkyl segment, and may be a saturated alkyl or an alkyl containing one or more unsaturated double bonds. Alkyl sulfates having an alkyl carbon number of 6 to 24 are preferred, and alkyl sulfates having an alkyl carbon number of 8 to 18 are further preferred. A suitable example is dodecyl sulfate.

In some embodiments, an alpha olefin sulfonate is contained, having the following general formula:

a is 0-2, Rc is an alkyl group having 6-24 carbon atoms, and preferably Rc is an alkyl group having 8-18 carbon atoms.

The anionic surfactant mixture may also include one or more mixtures of alkyl disulfonates or their derivatives, preferably alkyl diphenyl oxide disulfonates, a suitable example being dodecyl diphenyl oxide disulfonates, Dowfax series products of DOW. It may also include sulfosuccinates, preferably disodium salt of fatty alcohol polyoxyethylene ether sulfosuccinic acid monoester, the carbon number of the fatty alcohol is preferably 8-18, and the average degree of ethoxylation is preferably 2.0.

Nonionic surfactants

The nonionic surfactant of the present invention contains 15-30% by weight in the liquid detergent composition.

The nonionic surfactant is selected from a mixture of one or more of fatty alcohol alkoxylates, alkyl polysaccharides, fatty acid ester alkoxylates, fatty acid alkyl alcohol amides, fatty acid methyl ester ethoxylates, and polyether surfactants.

The fatty alcohol alkoxylate has the following general formula:

Among them, n is 6-24; x is 0.5-30, and y is 0-10.

n is 6-24; x is 0.5-30, and y is 0-10. The fatty alcohol alkoxylate is a product of ring-opening polymerization of fatty alcohol and alkylene oxide under the action of an alkaline catalyst, and is basically a mixture. Fatty alcohols include straight-chain alcohols or branched isomeric alcohols. Alkoxy groups include ethoxy groups and propoxy groups. Fatty alcohols are preferably fatty alcohols with a carbon number of 8-18, and preferred alcohols include but are not limited to hexanol, octanol, decanol, 2-ethylhexanol, 3-propylheptanol, lauryl alcohol, isodecanol, tridecanol, tetradecanol, hexadecanol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, linoleyl alcohol, linoleyl alcohol, and linoleyl alcohol, and mixtures thereof. The average ethoxylation degree x is preferably 2-12. Suitable examples include: fatty alcohol polyoxyethylene ether (9), i.e. AEO9; SHELL's NEODOL series of straight-chain fatty alcohol ethoxylate products; DOW's ECOSURF EH series of ethoxylated and propoxylated 2-ethylhexanol products; BASF's Lutensol XL series of ethoxylated and propoxylated 3-propylheptanol products; BASF's Lutensol XP series of ethoxylated 3-propylheptanol products, etc.

The alkyl polyglycoside has the following general formula:

Wherein, n is 6-24, and p is 1.1-3. Preferably, n is 8-16. Suitable alkyl glycosides include the Glucopon series alkyl glycoside products of BASF.

The fatty acid ester alkoxylate is selected from one or more compositions of ethoxylated C8-C18 fatty acid esters with an average ethoxylation degree of 2-10. It may contain ethoxylated sorbitan alkyl esters with an alkyl carbon number of 6-18 and an average ethoxylation degree of 4-20; a suitable example is the Tween series products of Corda Company.

The fatty acid alkyl alcohol amides are provided, wherein the carbon number of the fatty acid is 6-24, and the fatty acid may be a straight-chain fatty acid or a branched-chain fatty acid, and may be a saturated fatty acid or an unsaturated fatty acid; and the number of alkyl alcohols is 0-2. Preferably, the fatty acid carbon number is 8-18, and the monoethanolamide, diethanolamide, and isopropanolamide are used, and a suitable example is coconut oil diethanolamide.

The fatty acid methyl ester ethoxylate has the following general formula:

Wherein, n is 6-24; x is 0.5-30. Preferably n is 8-18, and x is 2-20. More preferably, x is 4-10. A suitable example is MEE product of LION Company.

The polyether surfactant refers to a block polymer with surface activity, and refers to a non-ionic surfactant obtained by adding polyethylene oxide or propylene oxide to an initiator. Suitable examples include the Pluronic series products of BASF.

Other additives

Other auxiliary agents involved in the present invention include one or more combinations of enzyme preparations, acid-base regulators, flavors, preservatives, antibacterial agents, polymers, and chelating agents.

Enzyme preparations

The detergent composition of the present invention may include one or more enzyme preparations to improve the decontamination performance of the product and bring other effects that are beneficial to fabric care. The enzyme preparation is selected from at least one of protease, α-amylase, cellulase, hemicellulase, phospholipase, esterase, lipase, peroxidase/oxidase, pectinase, lyase, mannanase, cutinase, reductase, xylanase, pullulanase, tannase, pentosanase, maltose, arabinase, and β-glucanase, preferably protease. Suitable proteases include, but are not limited to, Savinase 16L, Savinase Ultra 16XL, Savinase Evity 16L, Progress Uno 101L, and Progress Uno 100L from Novozymes, Effectenz P150, Preferenz P200, and Preferenz P300 from DuPont, and Lavergy 104L and 104LS from BASF. The enzyme preparation content is 0.001%-5%, preferably 0.01%-2% by weight of the total weight of the detergent composition.

Acid-base regulator

The acid-base regulator of the present invention includes an acidity regulator and an alkalinity regulator. Among them, the acidity regulator is selected from organic acids, inorganic acids and strong acid and weak base salts well known in the daily chemical products industry, preferably citric acid, succinic acid, boric acid, and more preferably citric acid. Alkalinity regulator, i.e., organic amine. Organic amine is selected from at least one of ethanolamine, ethylenediamine and its co-products, and tetraalkylammonium hydroxide. Ethanolamine is selected from at least one of monoethanolamine, diethanolamine, triethanolamine, and N-alkyldiethanolamine; ethylenediamine and its co-products are selected from at least one of diethylenetriamine, triethylenetetramine, and tetraethylenepentamine; tetraalkylammonium hydroxide is selected from at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide.

essence

The detergent composition of the present invention may contain fragrance, and the fragrance includes all fragrance ingredients suitable for washing products.

preservative

The detergent composition involved in the present invention may contain a preservative for providing the liquid formula with preservative performance. The amount of the preservative involved is 10ppm-500ppm, and the preservative is selected from one or a mixture of more than one of 1,2-benzisothiazolin-3-one, 2-methylisothiazolin-3-one, 5-chloro-2-methylisothiazolin-3-one, phenoxyethanol, and DMDMH.

Antibacterial Agents

The detergent composition of the present invention may further contain an antibacterial agent. The antibacterial agent is selected from at least one of hypochlorous acid and its salts, p-chlororesorcinol, p-chlororesorcinol, hydroxydichlorodiphenyl ether, hydroxytrichlorodiphenyl ether, triclocarban, o-phenylphenol, dodecyldimethylbenzylammonium chloride, dodecyltrimethylammonium chloride, tetradecyldimethylbenzylammonium chloride, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, didecyldimethylammonium chloride, polyhexamethylene biguanide hydrochloride, 1-hexadecylpyridinium chloride, pyrithione zinc, and pyridone ethanolamine salt.

polymer

The polymers described in the present invention include: salts of homopolymers of acrylic acid; salts of copolymers of acrylic acid; cellulose derivatives, such as carboxymethyl cellulose, ethyl hydroxyethyl cellulose, methyl cellulose; homopolymers and copolymers of vinyl pyrrolidone, such as linear polyvinyl pyrrolidone, copolymers of N-vinyl pyrrolidone and vinyl acetate; polyethylene imine derivatives, such as ethoxylated polyethylene imine, polyethylene terephthalate and its derivatives, polyethylene glycol and its derivatives. The polymers impart the detergent composition with the beneficial effects of anti-soil redeposition and/or promoting the dissociation of dirt from the substrate surface and/or improving the appearance of the detergent composition.

Chelating agents

The chelating agent of the present invention is selected from a mixture of one or more of citrate, glutamic acid diacetate, methylglycine diacetate, ethylenediaminetetraacetate, cyclohexanediaminetetraacetate, ethylene glycol diethyl ether diaminetetraacetate, ethylenediaminetetrapropionate, diethylenetriaminepentaacetate, triethylenetetraaminehexaacetate, and 2-hydroxyethylethylenediaminetriacetate. The cation of the salt of the chelating agent can be selected from sodium ions, lithium ions, and ammonium ions formed by organic amines.

In addition to the above ingredients, the detergent composition of the present invention may also contain various common and conventional additives such as cosolvents, solubilizers, structurants, foaming agents, defoamers, fabric softeners, bleaching systems, anti-wrinkle agents, etc. These additives and related use methods are well known to those skilled in the art, and the specific types and amounts thereof can be adjusted according to actual needs.

Method for preparing detergent composition

The laundry condensate composition of the present invention is prepared by various methods known to those skilled in the art. The composition can be prepared by conventional means, and the appropriate processing temperature and processing time should be selected according to the state and function of the components in the solution and the stability of the components.

Without further elaboration, it is believed that those skilled in the art can use the above to the greatest extent possible the present invention. The following examples are intended to further introduce and demonstrate specific embodiments within the scope of the present invention. Therefore, the examples are to be understood as being only used to illustrate the present invention in more detail, and are not intended to limit the present invention in any way.

A method for preparing a detergent composition comprises the following steps:

1) mixing water, a high boiling point solvent A, a low boiling point solvent B and an organic amine neutralizer;

2) adding anionic surfactant, mixing until the solution is clear, and cooling with chilled water;

3) When the temperature drops to 40-50°C, add nonionic surfactant and mix until completely dissolved;

4) Adjust the pH to 7-8;

6) Add other additives and stir until completely dissolved;

7) Add the remaining amount of deionized water and stir evenly.

Storage stability of detergent compositions

High temperature stability: After the composition is bottled and sealed, it is placed in an environment of 45℃±1℃. After being kept at a constant temperature for 4 weeks, it is restored to room temperature of 25℃±5℃. The composition has no stratification or precipitation, and the high temperature stability is qualified.

Low temperature stability: After the composition is sealed in a bottle, it is placed in an environment of 0℃±2℃ and kept at a constant temperature for 4 weeks, then taken out and observed immediately. If there is no stratification or precipitation in the composition, it is qualified for low temperature stability.

Freeze-thaw cycle stability: Place in -15℃--20℃ environment, keep constant temperature for 24 hours, then take out, and place in room temperature 25℃±5℃ environment for 24 hours as one cycle, repeat four cycles, and observe the state of the composition each time. The composition has no stratification or precipitation, and the freeze-thaw cycle stability is qualified.

Room temperature stability: After the composition is bottled and sealed, it is placed in a room temperature environment (20°C-30°C). After 4 weeks, the composition has no stratification or precipitation, and the room temperature stability is qualified.

Storage stability of laundry pods

High-temperature precipitation stability: The laundry beads were placed open in a constant temperature blast oven at 45±1℃ for 2 weeks. No particles or powder were precipitated outside the membrane and no leakage occurred, indicating that the high-temperature precipitation stability was qualified.

High temperature and high humidity stability: The laundry beads were sealed in a high-density polyethylene (HDEP) bag and stored at 45±1°C and 70%-80% relative humidity for 8 weeks. They were then taken out of the constant temperature and humidity chamber to test color change, precipitation outside the film, and solubility.

Laundry Pod Color Change Test and Color Change Rate Rating

The outer membrane of the laundry beads was cut open and the contents were taken out. The color change of the contents before and after high temperature and high humidity treatment was tested using a colorimeter. The color change rate (Y) of the contents was calculated according to the following formula (1).

Y＝Db2-Db1 (1), Y: content color change rate;

Db1: Db value (yellow-blue value) of a unit dose of the liquid detergent composition before high-temperature and high-humidity aging treatment;

Db2: Db value (yellow-blue value) of a unit dose of liquid detergent composition after high temperature and high humidity aging treatment;

High temperature and high humidity aging treatment: Place the laundry beads in a high-density polyethylene (HDEP) bag, seal it, and store it at 45±1°C and 70%-80% relative humidity for 8 weeks.

Table 1 Color change rate of the condensed beads after high temperature and high humidity aging treatment

Laundry beads dissolution performance test

The solubility performance referred to in the present invention refers to the dissolution of laundry beads in 1 liter of water. One laundry bead is placed in a beaker, and the bead is stirred and dissolved in the beaker for a period of time, and then the stirring is stopped. All the solution and residue in the beaker are immediately filtered through a 60-mesh gauze sieve, and the solubility performance is rated within 1 minute based on the filter residue on the gauze sieve.

The time for the beads to be stirred and dissolved in the beaker is referred to as the dissolution time. For beads that have not been aged, the dissolution time is 5 minutes. For bags that have been aged, the dissolution time is 10 minutes.

The solubility ratings are shown in Table 4. The solubility was determined visually, with rating 1 representing complete solubility and rating 4 representing no solubility.

Table 2 Evaluation level of dissolution performance

Detergency Test Method

Detergent power in the present invention refers to the ability of a fabric detergent composition to remove different stains. The test is conducted according to the method of national standard GB/T 13174-2008. Three types of dirty cloth, carbon black, protein, and sebum, are used, and the WSD-3U fluorescent whiteness meter measures the whiteness W1 of the three types of dirty cloth before washing. Hard water with a hardness of 250ppm is prepared according to GB/T 13174-2008 standard, and a RHLQ vertical detergent is used to complete one washing. The amount of detergent added is 2g/L for ordinary type and 0.7g/L for concentrated type. The washing time is 20min, the washing temperature is 30°C, the stirring speed is 120r/min, the washed dirty cloth is rinsed and dried, and the whiteness W2 of the washed cloth is tested by a whiteness meter. The calculation method of the whiteness difference △W is as follows:

ΔW=W2-W1 (2), where W2 is the whiteness after washing and W1 is the whiteness before washing.

The detergency of the sample detergent is compared with the detergency of the national standard detergent to calculate the P value, as shown in formula (3):

P = △W sample / △W standard (3), where △W sample is the whiteness difference of the dirty cloth before and after washing with the sample detergent, and △W standard is the whiteness difference of the dirty cloth before and after washing with the national standard detergent.

Detergency Evaluation Standard

A P value of <1 indicates that the detergent composition has a lower decontamination ability than the control, and a P value of >1 indicates that the detergent composition has a higher decontamination ability than the control. The larger the P value, the stronger the decontamination ability of the detergent composition. When the P value is ≥1.10, the detergent composition has good decontamination performance.

Without further elaboration, it is believed that those skilled in the art can use the above to the greatest extent possible the present invention. The following examples are intended to further introduce and demonstrate specific embodiments within the scope of the present invention. Therefore, the examples are to be understood as being only used to illustrate the present invention in more detail, and are not intended to limit the present invention in any way.

In the following examples, unless otherwise specified, all contents are expressed in weight percentage, and the contents of the listed components are the converted active substance contents.

In the following examples, the following components were used.

Glycerol belongs to the category of high boiling point solvent A.

Polyethylene glycol 400 belongs to the category of high boiling point solvent A.

Dipropylene glycol, belongs to the category of high boiling point solvent A.

Propylene glycol, belongs to the category of low boiling point solvent B.

Ethylene glycol, belongs to the category of low boiling point solvent B.

Sodium metabisulfite belongs to the category of reducing agents.

Sodium bisulfite, belongs to the category of reducing agents.

Sodium sulfite belongs to the category of reducing agents.

Linear alkylbenzene sulfonic acid, referred to as LAH, belongs to the category of anionic surfactant precursors.

Ethoxylated alcohol sulfate, referred to as AES, belongs to the category of anionic surfactants.

Dodecanoic acid belongs to the category of fatty acid salt precursors.

Myristic acid, belongs to the category of fatty acid salt precursors.

Oleic acid, belongs to the category of fatty acid salt precursors.

Fatty alcohol polyoxyethylene ether (9), referred to as AEO9, belongs to the category of nonionic surfactants, fatty alcohol alkoxylates. Ethoxylated and propoxylated 3-propylheptanol, referred to as Lutensol XL, belongs to the category of nonionic surfactants, fatty alcohol alkoxylates.

Ethoxylated 3-propylheptanol, referred to as Lutensol XP, belongs to the category of nonionic surfactants, fatty alcohol alkoxylates.

Monoethanolamine belongs to the category of organic amine neutralizers.

Triethanolamine belongs to the category of organic amine neutralizer.

Deionized water, which belongs to the category of solvents.

Sodium citrate, belongs to the category of other additives.

Protease: It belongs to the category of other auxiliary agents.

Fragrance: It belongs to the category of other additives.

Pigments: belong to the category of other additives.

Examples and Comparative Examples

The following examples are provided for illustration and comparison of the present invention and are not intended to limit the present invention.

The corresponding weight percentages of the components in Examples 1-6 and Comparative Examples 1-20 were used to prepare detergent compositions according to the above-mentioned preparation method of detergent compositions, and the detergent compositions were encapsulated according to the preparation method of laundry beads to prepare laundry beads, and the storage stability of the detergent compositions and laundry beads was tested according to the method described above. Table 3, Table 5, and Table 7 show the weight percentage content of the components in the detergent compositions of Examples 1-6 and Comparative Examples 1-20. Table 4, Table 5, and Table 6 show the storage stability test results of the detergent compositions and laundry beads prepared from Examples 1-6 and Comparative Examples 1-20.

Table 3 Compositions of detergent compositions A to J

Table 4 Storage stability of detergent compositions A to J and laundry beads

From the above Tables 3 to 4, the stability test results of Examples 1, 2, 5, and 6 are compared with those of Comparative Examples 1-4. It is found that when the fatty acid salt content is within the range described in the technical solution of the present invention, but the organic solvent is not within the range, such as the high boiling point solvent A is lower than the range value of the technical solution of the present invention, and the amount of the low boiling point solvent B is higher than the range value of the technical solution of the present invention (Comparative Examples 1-4), although the storage stability of the detergent compositions G-J is qualified, the corresponding laundry beads all have particle precipitation at high temperature, that is, the high temperature precipitation stability fails. At the same time, the color change rate of the content after high temperature and high humidity aging is significantly deteriorated, especially for the composition G-I corresponding to the high sulfonic acid content (>20%), the color change rate Db value of the beads is>15, and the color change phenomenon is serious, and it cannot pass the high temperature and high humidity stability test. And the results of Comparative Examples 2 and 3 show that for the detergent compositions H and I with high AES content, it will further cause the sulfate in the AES to precipitate particles outside the membrane, and the high temperature and high humidity stability cannot pass.

Table 5 Composition of detergent compositions K to Q

Table 6 Storage stability of detergent compositions K to Q and laundry beads

Compared with Example 5, although the content of fatty acid salt in the detergent composition of Comparative Example 5 is within the range described in the present invention, the content of high boiling point solvent A exceeds the range described in the present invention, while the content of low boiling point solvent B is lower than the range described in the present invention, and its low temperature and freeze-thaw cycle stability both show stratification, and the storage stability of the detergent composition is unqualified. At the same time, after high temperature and high humidity aging, the color change rate of the contents deteriorates, the contents leak outside the bead membrane, and the membrane does not dissolve, that is, the high temperature and high humidity stability also fails.

Compared with Example 5, the content of fatty acid salt in Comparative Example 6 is within the range described in the present invention, but the content of high boiling point solvent A exceeds the range described in the present invention, and when the content of low boiling point solvent B is higher than the range described in the present invention, although the storage stability of the detergent composition and the high temperature precipitation stability of the laundry beads can pass, the high temperature stability of the beads cannot pass, and the color change rate of the contents deteriorates and the film does not dissolve.

Compared with Example 1, the results of Comparative Example 7 show that when the contents of the high-boiling point solvent A and the low-boiling point solvent B are both lower than the range described in the present invention, even if the fatty acid salt content is within the range described in the present invention, the storage stability of the detergent composition and the storage stability of the laundry beads cannot be passed.

The analysis results of the above comparative examples 1-7 indicate that when the fatty acid salt content is within the range described in the present invention, and the amounts of the high-boiling point solvent A and the low-boiling point solvent B exceed the range of the technical solution of the present invention, they will respectively cause different degrees of adverse effects on the storage stability of the detergent composition and the storage stability of the laundry beads.

Comparative Examples 8 and 9 were compared with Examples 1 and 5 respectively, and it was found that the fatty acid salt and the low boiling point solvent B were both within the range of the present invention, but when the high boiling point solvent A was higher or lower than the range value, although it could pass the storage stability test of the detergent composition, it still could not pass the storage stability test of the laundry beads, and the color change rate Db value of its contents after high temperature and high humidity aging was significantly increased, and the discoloration was more serious. When the high boiling point solvent A was lower than the range value, it would lead to the phenomenon of high temperature precipitation of particles, and when it was higher than the range value, it would also lead to the phenomenon of precipitation outside the film and obvious deterioration of the film solubility.

A comparative analysis of the stability test results of Comparative Examples 10-11 and Examples 2 and 5 shows that the fatty acid salt and the high boiling point solvent A are both within the range of the present invention. When the low boiling point solvent B is lower than the range value (Comparative Example 10), both the storage stability of the detergent composition and the storage stability of the laundry beads cannot pass; when the low boiling point solvent is higher than the range value (Comparative Example 11), although the storage stability of the detergent composition can pass, it will also cause the laundry beads to discolor and become unqualified after high temperature and high humidity aging and the water solubility of the membrane will deteriorate.

Table 7 Compositions of detergent compositions R to Z

Table 8 Storage stability of detergent compositions R to Z and laundry beads

The stability test results of Comparative Examples 12-14 show that when the high boiling point solvent A and the low boiling point solvent B are both within the range of the present invention, and the amount of fatty acid salt exceeds the range, the color change rate Db value of the laundry beads after high temperature and high humidity aging will be significantly increased compared with Example 6, Example 1, and Example 5, respectively, and the color change is serious, that is, it cannot pass the high temperature and high humidity stability test. In particular, for Comparative Example 12 with high sulfonic acid and high AES content, compared with Example 6, it also causes the phenomenon of precipitation of extra-membrane particles during high temperature and high temperature and high humidity aging, and the low temperature stability test of the washing composition cannot be passed.

The above comparative examples illustrate that the dosage of fatty acid salt has a significant impact on the storage stability of the detergent composition and the storage stability of the laundry beads, and needs to be controlled within the scope of the technical solution of the present invention to achieve good high temperature and high humidity storage stability of the laundry beads.

Compared with Examples 1, 4 and 5, the stability results of Comparative Examples 15-17 show that when any one of the high boiling point solvent A, the low boiling point solvent B and the fatty acid salt is not within the scope of the present invention, the storage stability of the detergent composition and the storage stability of the laundry beads cannot pass the test.

Comparison of the stability performance results of the above embodiments and comparative examples shows that the organic solvents and fatty acid salts described in the present invention can effectively improve the storage stability of the detergent composition and the laundry beads by compounding them within a specific dosage range; in particular, the problem of color change after aging of laundry beads with a high content of sulfonate surfactants can be effectively solved; and the content of polyoxyethylene ether sulfate in the laundry beads can be increased without causing the precipitation of solid particles on the surface of the laundry beads.

Compared with Example 6, the stability test results of Comparative Example 18 show that the color change rate Db value of the content without reducing agent is 23.4, and the color change rate of the content is poor, which is not conducive to high temperature stability. The stability test results of Comparative Examples 19-20 show that when the reducing agent of the present invention is not used, and the same weight percentage of sodium dithionite and thiourea dioxide are used instead, the contents have a strong pungent odor, and thiourea dioxide also causes the precipitation of particles, and the storage stability cannot pass.

The stability performance results of the above comparative examples indicate that a single reducing agent can stabilize the color of laundry beads prepared from a high content of sulfonate-type surfactants after aging, and that increasing the content of polyoxyethylene ether sulfate in the presence of the reducing agent of the present invention will not lead to the precipitation of solid particles on the surface of the laundry beads, and that when the reducing agent of the present invention is not used, the liquid detergent composition and the laundry beads cannot be given enhanced stability.

(2) Detergency test

The above Examples 1-6 were tested according to the aforementioned detergency test method, and the results are shown in Table 9.

Table 9 Detergency test results of Examples 1-6

Sample No. Carbon black dirty cloth P value Protein stain P value Sebum-stained cloth P value Example 1 1.10 2.42 1.29 Example 2 1.13 3.61 1.16 Example 3 1.15 3.06 1.26 Example 4 1.18 3.54 1.39 Example 5 1.16 3.47 1.35 Example 6 1.13 3.58 1.27

From the comparison of the detergency test results in Table 9, it can be seen that Examples 1-6 provided by the present invention not only have long-term storage stability, but also have good washing and detergency performance, and can pass the detergency test.

The above description is only used to further illustrate the technical content of the present invention by examples, so as to facilitate readers to understand more easily, but it does not mean that the implementation mode of the present invention is limited to this. Any technical extension or re-creation made according to the present invention is protected by the present invention.

Claims (10)

1. A detergent composition, characterized in that it comprises the following components in weight percentage: 11-30% high boiling point solvent A, 3-10% low boiling point solvent B, 2-10% organic amine neutralizer, 0-8% fatty acid salt, 0.1-1% reducing agent, 15-30% nonionic surfactant, 15-40% anionic surfactant, and the balance is water; the high boiling point solvent A is selected from a combination of one or more of glycerol, dipropylene glycol, polyethylene glycol, and sorbitol; the low boiling point solvent B is selected from a combination of one or more of propylene glycol, ethylene glycol, and dipropylene glycol methyl ether. 2. The detergent composition according to claim 1, characterized in that the fatty acid salt is selected from a combination of one or more fatty acid salts of C8-C18. 3. The detergent composition according to claim 1, characterized in that the organic amine neutralizer is selected from a combination of one or more of ethanolamine, ethylenediamine and its co-products and tetraalkylammonium hydroxide. 4. The detergent composition according to claim 3, characterized in that the ethanolamine is selected from at least one of monoethanolamine, diethanolamine, triethanolamine, and N-alkyldiethanolamine; the ethylenediamine and its co-products are selected from at least one of diethylenetriamine, triethylenetetramine, and tetraethylenepentamine; and the tetraalkylammonium hydroxide is selected from at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide. 5. The detergent composition according to claim 1, characterized in that the reducing agent is selected from a combination of one or more of thiosulfates, pyrosulfites, sulfites and bisulfites. 6. The detergent composition according to claim 1, characterized in that the nonionic surfactant is selected from a combination of one or more of fatty alcohol alkoxylates, alkyl polysaccharides, fatty acid ester alkoxylates, fatty acid alkylolamides, fatty acid methyl ester ethoxylates, and polyether surfactants. 7. The detergent composition according to claim 1, characterized in that the anionic surfactant is selected from a combination of one or more of C6-C24 alkylbenzene sulfonates, C8-C18 alkyl sulfates, and C8-C18 ethoxylated fatty alcohol sulfates. 8. The detergent composition according to claim 1, characterized in that it also comprises 0-5% of other auxiliary agents; the other auxiliary agents are selected from at least one of chelating agents, enzyme preparations, preservatives, polymers, inorganic salts, viscosity modifiers, antibacterial agents, colorants, flavors, and acid-base regulators. 9. A stable laundry detergent bead, characterized in that it comprises a water-soluble film and a detergent composition as described in any one of claims 1 to 8; the water-soluble film encapsulates the detergent composition; the water-soluble film is a mixture of one or more polyvinyl alcohol homopolymers and polyvinyl alcohol copolymers; the polyvinyl alcohol homopolymer is a hydrolysis product of a homopolymer of vinyl acetate; the polyvinyl alcohol copolymer is a hydrolysis product of a copolymer of vinyl acetate and a second monomer, the second monomer is an acrylic monomer, and the molar percentage of the second monomer in the polyvinyl alcohol copolymer is 2%-9%. 10. The stable laundry beads according to claim 9, characterized in that the mass percentage of the water-soluble film is 4%; and the viscosity of the aqueous solution is 10 centipoise to 25 centipoise.