A liquid detergent composition comprising a fabric conditioner

Abstract

The application discloses a liquid detergent composition, which is composed of the following components in mass fraction: 0.5-2% of fabric finishing agent, 2-50% of non-ionic surfactant, 0.1-10% of auxiliary agent, and the rest is solvent; the fabric finishing agent is a fluorine-containing acrylate polymer. The fabric finishing agent provided by the application is applied in the liquid detergent composition, and can endow the polyester fabric after washing with excellent waterproof performance, washing stain removal performance and good appearance stability.

Description

Technical Field

[0001] This invention relates to the field of daily chemical technology, and in particular to a liquid detergent composition that imparts excellent waterproof properties to polyester fabrics after washing. Background Technology

[0002] In modern society, people are increasingly focused on health and exercise, and outdoor activities have become an indispensable part of life. Therefore, outdoor sportswear needs unique functions to meet the needs of different sports scenarios, with waterproofing being the most popular feature. When engaging in outdoor activities in damp or rainy environments, waterproof clothing effectively prevents rain or dew from penetrating the garment, keeping the body dry. This is crucial for maintaining body temperature, preventing colds, and avoiding discomfort caused by dampness. Furthermore, waterproof clothing not only protects the body but also the equipment and belongings carried. For example, waterproof backpacks or bags effectively prevent items from getting damp or damaged by water. These advantages make waterproof outdoor clothing essential equipment for outdoor enthusiasts.

[0003] Polyester, as the most common material for outdoor sportswear, typically undergoes waterproofing treatments concentrated in the fabric finishing stage. For example, patent CN 110983796B uses a coating process to bond an organosilicon coating to the fabric surface, while patent CN114941244B emulsifies organosilicon and organofluorine waterproofing agents at high temperatures to obtain a waterproof finishing liquid, which is then applied to the fabric surface through padding and drying to form a waterproof film. However, the effectiveness of these waterproofing treatments gradually decreases during daily washing and air drying, thus reducing the lifespan of outdoor sportswear. When the fabric's waterproofing function significantly declines, waterproofing sprays are generally used for remediation, such as patent CN 109763345B. However, these products require large amounts of volatile organic solvents in their formulations, resulting in a pungent odor and potential harm to humans. Therefore, the industry hopes to develop a detergent that simultaneously enhances the waterproofing performance of clothing during the stain removal process, enabling waterproofing of the fabric surface through a simple wash and dry process at room temperature. This would help consumers extend the lifespan of outdoor sportswear and prevent accidents. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides a fabric finishing agent that imparts excellent water-repellent properties to polyester fabrics after washing. Another objective of this invention is to provide a detergent composition that imparts excellent water-repellent properties to polyester fabrics after washing.

[0005] To achieve the above objectives, the present invention adopts the following technical solution: A liquid detergent composition comprising the following components by mass fraction: 0.5% to 2% fabric finishing agent, 2% to 50% nonionic surfactants, 0.1% to 10% adjuvants, The remainder is solvent; The fabric finishing agent is a fluorinated acrylate polymer, composed of monomer unit a and monomer unit b, wherein monomer unit a has the following general chemical formula (1): (1) Wherein, R1: H or C6H5 or C n H 2n+1 n is a positive integer from 1 to 4; R2: C m F 2m+1 m is a positive integer from 4 to 10; The monomer unit b has the following general chemical formula (2): (2) Wherein, R1: H or C6H5 or C n H 2n+1 n is a positive integer from 1 to 4; R3: C p H 2p+1 p is a positive integer from 12 to 26.

[0006] The fluorinated acrylate polymer has a weight-average molecular weight of 60,000 to 200,000, a fluorine content of 4% to 15%, and a monomer unit a to monomer unit b ratio of 1:2 to 1:20.

[0007] The liquid detergent composition further contains anionic surfactants at a content of 0.1% to 15%, wherein the content of alkylbenzene sulfonate in the liquid detergent composition is less than 2%.

[0008] The sum of the mass fractions of nonionic surfactants and anionic surfactants in the liquid detergent composition is ≥15%.

[0009] The anionic surfactant is selected from one or more mixtures of alkylbenzene sulfonates, C8 to C18 alkyl sulfates, C8 to C18 ethoxylated fatty alcohol sulfates, C8 to C18 fatty acid salts, and ethoxylated fatty alcohol ether carboxylates; the alkylbenzene sulfonate has 6 to 24 alkyl carbons and is selected from straight-chain alkyl and branched alkyl, and may be a saturated alkyl or an alkyl containing one or more unsaturated double bonds.

[0010] The nonionic surfactant is selected from one or more of the following: fatty alcohol alkoxylates, alkyl polysaccharides, fatty acid ester alkoxylates, fatty acid alkylolamides, fatty acid methyl ester ethoxylates, and polyether surfactants.

[0011] The additives are selected from one or more of the following: acid-base regulators, enzyme preparations, preservatives, polymers, inorganic salts, viscosity modifiers, antibacterial agents, colorants, fragrances, and chelating agents.

[0012] The solvent is a mixture of water and an organic solvent; the organic solvent is selected from polyols and / or polyol ethers.

[0013] The liquid detergent composition imparts excellent water-repellent properties to polyester fabrics. Excellent water-repellent properties are defined as a water permeability time of ≥90s and a water stain rating of ≥4 after washing, according to the water-repellent performance evaluation method.

[0014] The liquid detergent composition exhibits excellent detergency and good appearance stability. Excellent detergency means the liquid detergent composition achieves a detergency ratio (P) ≥ 1.03 for soiled cloths containing sebum, protein, and carbon black. Good appearance stability means that after aging treatment, the liquid detergent composition remains a homogeneous system with essentially no change in color.

[0015] The technical solution described in this invention has the following beneficial effects: 1. The fabric finishing agent provided by the present invention, when applied in a liquid detergent composition, can impart excellent waterproof properties to polyester fabrics after washing.

[0016] 2. The liquid detergent composition provided by the present invention has excellent washing and stain removal performance and good appearance stability.

[0017] 3. The liquid detergent composition provided by the present invention can complete the waterproofing treatment of polyester fabrics during the room temperature washing process, which is simple and easy and does not require additional steps. Attached Figure Description

[0018] To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the following description of the embodiments will be briefly introduced. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0019] Figure 1 This is an image showing the appearance of the detergent composition sample from Example 2 after aging.

[0020] Figure 2 This is a diagram showing the appearance of the detergent composition sample of Comparative Example 3 after aging.

[0021] Figure 3 This is a partial view of the appearance of the detergent composition sample of Comparative Example 3 after aging.

[0022] Figure 4This is a diagram showing the appearance of the detergent composition sample of Comparative Example 7 after aging.

[0023] Figure 5 This is a partial view of the appearance of the detergent composition sample of Comparative Example 7 after aging.

[0024] Figure 6 This is a diagram showing the appearance of the detergent composition sample of Comparative Example 9 after aging.

[0025] Figure 7 This is a partial view of the appearance of the detergent composition sample of Comparative Example 9 after aging.

[0026] Figure 8 This is a diagram showing the water-retention phenomenon of the fabric sample in Example 2.

[0027] Figure 9 This is a diagram showing the water-soaking phenomenon of the fabric sample in Comparative Example 1.

[0028] Figure 10 This is a diagram showing the water-retention phenomenon of fabric sample 4 in Comparative Example 4.

[0029] Figure 11 This is a diagram showing the water-retention phenomenon of fabric sample 8 in comparison. Detailed Implementation

[0030] To better understand the technical content of the present invention, the technical solution of the present invention will be further introduced and explained below in conjunction with specific embodiments.

[0031] For those skilled in the art, the features, beneficial effects, and advantages of the present invention will become clearer upon reading the contents disclosed in this specification.

[0032] In this invention, unless otherwise specified, all percentages, fractions, and ratios are calculated based on the total mass of the compositions of this invention. Unless otherwise specified, the mass fractions of listed components refer to the content of active substances, i.e., the listed components do not include diluents, byproducts, or other components that may be present in raw materials obtained through purchase. The term "mass fraction" is represented by the symbol "%".

[0033] Unless otherwise specified, the preparation and testing environment for the compositions of this invention is 25°C.

[0034] The dimensions and numerical values ​​disclosed in this invention should not be construed as strict limitations on the precise values ​​stated therein. Unless otherwise specified, each such dimension is intended to represent the value and a range of functionally equivalent values ​​around that value. For example, a dimension disclosed as “45°C” is intended to represent “about 45°C”.

[0035] The terms "comprising," "including," "containing," "containing," "having," or other variations thereof in this invention are intended to cover non-closed inclusion, and no distinction is made between these terms. The term "comprising" also includes the terms "consisting of" and "essentially composed of," meaning that other components or preparation steps may be added without significantly altering the final result, depending on the specific circumstances. The detergent compositions of this invention may comprise those consisting of and substantially consisting of the essential elements and limitations described herein, as well as any additional or optional ingredients, components, steps, or limitations described herein.

[0036] In this invention, there is no distinction between "performance" and "efficiency". Similarly, there is no distinction between "waterproofness" and "waterproof performance".

[0037] Liquid detergent composition This invention relates to a liquid detergent composition, the term "liquid" encompassing forms in which a solid component is present within a liquid composition such as a dispersion, gel, or slurry. The liquid composition also includes capsule-type detergents prepared using the liquid composition of this invention.

[0038] The term "liquid detergent composition" refers to any fabric detergent composition that includes a liquid capable of wetting and treating fabrics. Wetting and treating fabrics can be achieved through methods such as pre-treatment with the undiluted composition, hand washing after dilution with tap water, or machine washing. Liquid detergent compositions can provide fabric care benefits including stain removal and water resistance.

[0039] The liquid detergent composition of the present invention comprises a surfactant, a fabric finishing agent, an auxiliary agent, and the balance being a solvent.

[0040] The liquid detergent composition contains 2% to 50% nonionic surfactant. It may also contain anionic surfactant at a content of 0.1% to 15%, wherein the alkylbenzene sulfonate content of the anionic surfactant in the liquid detergent composition is less than 2%. The sum of the mass fractions of the nonionic surfactant and the anionic surfactant is ≥15%.

[0041] The additives include one or more of the following: acid-base regulators, enzyme preparations, preservatives, polymers, inorganic salts, viscosity modifiers, antibacterial agents, colorants, fragrances, and chelating agents.

[0042] Fabric finishing agents The liquid detergent composition of the present invention contains 0.5% to 2% of a fabric finishing agent selected from fluorinated acrylate polymers, and is composed of monomer unit a and monomer unit b, wherein monomer unit a has the following general chemical formula (1): (1) Wherein, R1: H or C6H5 or C n H 2n+1 n is a positive integer from 1 to 4, R2:C m F 2m+1 m is a positive integer from 4 to 10; The monomer unit b has the following general chemical formula (2): (2) Wherein, R1: H or C6H5 or C n H 2n+1 n is a positive integer from 1 to 4, R3:C p H 2p+1 p is a positive integer from 12 to 26.

[0043] The fluorine content in fluorinated acrylate polymers is expressed as fluorine content (F%) and is calculated using the following formula: In the above formula: M F This refers to the atomic weight of fluorine. 2m+1 is C in single unit a m F 2m+1 The number of fluorine atoms in a unit cell, where m is a positive integer from 4 to 10. M a denoted as molecular weight of monomer unit a; N a The number of repeats of monomer unit a in the polymer; M b is the molecular weight of monomer unit b; N b The number of repeats of monomer unit b in the polymer.

[0044] The fluorine content of the fluorinated acrylate polymer is 4% to 15%.

[0045] The weight-average molecular weight of the fluorinated acrylate polymer is 60,000 to 200,000, and the ratio of monomer unit a to monomer unit b is 1:2 to 1:20.

[0046] Anionic surfactants The liquid detergent composition of the present invention contains an anionic surfactant at a mass fraction of 0.1% to 15%, and the content of alkylbenzene sulfonate in the liquid detergent composition is less than 2%. The anionic surfactant is selected from one or more mixtures of alkylbenzene sulfonates, C8 to C18 alkyl sulfates, C8 to C18 ethoxylated fatty alcohol sulfates, C8 to C18 fatty acid salts, and ethoxylated fatty alcohol ether carboxylates; the alkylbenzene sulfonate has an alkyl carbon number of 6 to 24, is selected from straight-chain alkyl and branched alkyl, and can be a saturated alkyl or an alkyl containing one or more unsaturated double bonds.

[0047] The cationic portion of the anionic surfactant is selected from sodium ions, potassium ions, ammonium ions, and ammonium ions formed from organic amines. Among the ammonium ions formed from organic amines, the organic amines are selected from ethanolamine, ethylenediamine and its byproducts, and tetraalkylammonium hydroxide; ethanolamines include monoethanolamine, diethanolamine, triethanolamine, N-alkyldiethanolamine, etc.; ethylenediamine and its byproducts include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc.; and tetraalkylammonium hydroxides include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, etc.

[0048] The alkylbenzene sulfonate of the present invention has an alkyl group having 6 to 24 carbon atoms, selected from straight-chain alkyl groups and branched alkyl groups; it may be a saturated alkyl group or an alkyl group containing one or more unsaturated double bonds.

[0049] The alkylbenzene sulfonate satisfies the following formula: R a That is, alkyl groups with 6 to 24 carbon atoms, where M+ is a cationic moiety. A suitable example is dodecylbenzene sulfonate.

[0050] The ethoxylated fatty alcohol sulfate of the present invention is a derivative of ethoxylated fatty alcohols and has the following general formula: R b It is an alkyl group having 6 to 24 carbon atoms; x is 0.5 to 15; wherein M + The moiety is cationic. R1 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. R1 is preferred. b It is a straight-chain alkyl group having 8 to 18 carbon atoms. x represents the average degree of ethoxylation, which is 0.5 to 15, preferably 0.5 to 10, and more preferably 0.5 to 3. A suitable example is Texapon N70 from BASF.

[0051] The alkyl sulfates of the present invention may have straight-chain or branched alkyl segments, and may be saturated alkyl groups or alkyl groups containing one or more unsaturated double bonds. Alkyl sulfates with 6 to 24 carbon atoms are preferred, and alkyl sulfates with 8 to 18 carbon atoms are more preferred. A suitable example is dodecyl sulfate.

[0052] In some embodiments, an α-olefin sulfonate is contained, having the following general formula: a is between 0 and 2, R c It is an alkyl group having 6 to 24 carbon atoms, preferably R. c It is an alkyl group having 8 to 18 carbon atoms.

[0053] In some embodiments, the mixture of anionic surfactants contains a fatty acid salt, preferably a fatty acid salt with 8 to 18 carbon atoms. The alkyl segment of the fatty acid can be straight-chain or branched, and can be a saturated alkyl group or an alkyl group containing one or more unsaturated double bonds. The fatty acid salt can be a single component or a mixture of multiple fatty acids. Suitable examples are oleate and laurate. The fatty acid salt also contains an ethoxylated fatty alcohol ether carboxylate, wherein the fatty alcohol preferably has 8 to 18 carbon atoms and an average degree of ethoxylation preferably of 2.0 to 10.

[0054] The anionic surfactant mixture may also contain one or more mixtures of alkyl disulfonates or their derivatives, preferably alkyl diphenyl ether disulfonates, a suitable example being sodium dodecyl diphenyl ether disulfonate, a product of Dow Company's Dowfax series. It may also contain sulfosuccinates, preferably disodium salt of fatty alcohol polyoxyethylene ether sulfosuccinate monoester, wherein the fatty alcohol preferably has 8 to 18 carbon atoms and an average degree of ethoxylation preferably of 2.0.

[0055] Nonionic surfactants The liquid detergent composition of the present invention contains 2% to 50% of a nonionic surfactant, wherein the surfactant is selected from one or more of fatty alcohol alkoxylates, alkyl polyglycosides, fatty acid ester alkoxylates, fatty acid alkylolamides, fatty acid methyl ester ethoxylates, and polyether surfactants.

[0056] The fatty alcohol alkoxylates have the following general formula: n is 6 to 24; x is 5 to 30; and y is 0 to 10. The fatty alcohol alkoxylates are products of ring-opening polymerization of fatty alcohols and epoxides under a basic catalyst, and are essentially mixtures. Fatty alcohols include straight-chain alcohols or branched isomeric alcohols. Alkoxy groups include ethoxy groups and propoxy groups. The fatty alcohols are preferably fatty alcohols with 8 to 18 carbon atoms, and preferred alcohols include, but are not limited to, one or mixtures of octanol, decanol, 2-ethylhexanol, 3-propylheptanol, lauryl alcohol, isotrimethylene glycol, tridecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, palmitol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, linoleyl alcohol, and linolenic acid alcohol. The average degree of ethoxylation x is preferably 2 to 12. Preferred examples include SHELL's NEODOL series of straight-chain fatty alcohol ethoxylated 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, and BASF's Lutensol XP series of ethoxylated 3-propylheptanol products.

[0057] The alkyl polysaccharide has the following general formula: n is 6 to 24, and p is 1.1 to 3. Preferably, n is 8 to 16. Suitable alkyl polyglycosides include BASF's Glucopon series of alkyl glycosides.

[0058] The fatty acid ester alkoxylate is preferably an ethoxylated C8 to C18 fatty acid ester with an average degree of ethoxylation of 2 to 10. It may contain an ethoxylated sorbitol alkyl ester with 6 to 18 alkyl carbons and an average degree of ethoxylation of 4 to 20; a suitable example is the Tween series products from Corda.

[0059] The fatty acid alkylolamide has a fatty acid with 6 to 24 carbon atoms, and can be a straight-chain fatty acid or a branched fatty acid, and can be a saturated fatty acid or an unsaturated fatty acid; the number of alkyl alcohols is 0 to 2. Preferred fatty acid alkylolamides are monoethanolamides, diethanolamides, or isopropanolamides with 8 to 18 carbon atoms; a suitable example is coconut oil diethanolamide.

[0060] The fatty acid methyl ester ethoxylate has the following formula: n is 6 to 24; x is 2 to 20. Preferably, n is 8 to 18 and x is 0.5 to 30, more preferably x is 4 to 10. A suitable example is LION's MEE product.

[0061] The polyether surfactant. A polyether surfactant is a polymer containing repeating ethylene oxide and / or propylene oxide units, a suitable example being the Pluronic series products from BASF.

[0062] Amphoteric surfactants Furthermore, the liquid detergent composition of the present invention may also contain an amphoteric surfactant in a mass fraction of 0.01% to 15%. There is no distinction between the amphoteric surfactant and the amphoteric surfactant-type surfactant. The amphoteric surfactant includes betaine-type surfactants, imidazoline-type surfactants, amino acid-type surfactants, and amine oxide-type surfactants, including but not limited to: alkyl betaine, fatty amide betaine, fatty amide propyl betaine, fatty amide propyl hydroxypropyl sulfonated betaine, sodium alkyl acetate imidazoline, fatty acid imidazoline, sulfonic acid imidazoline, aminopropionic acid derivatives, glycine derivatives, alkyl dimethyl amine oxide, fatty amide propyl dimethyl amine oxide, etc. Suitable examples include dodecyl amine oxide, cocamidopropyl amine oxide, cocamidopropyl betaine, etc.

[0063] cationic surfactants Furthermore, the liquid detergent composition of the present invention may also contain a cationic surfactant in a mass fraction of 0.01% to 15%. The cationic surfactant includes quaternary ammonium salt surfactants, heterocyclic surfactants, and polymeric cationic surfactants, including: mono-long linear chain quaternary ammonium salts, bis-long linear chain quaternary ammonium salts, benzyl quaternary ammonium salts, hydroxyalkyl quaternary ammonium salts, fatty amide propyl hydroxyalkyl quaternary ammonium salts, and polyquaternary ammonium salts copolymerized with vinylpyrrolidone and unsaturated amides or unsaturated quaternary ammonium salts.

[0064] Additives The liquid detergent composition of the present invention contains 0.1 to 10% of an adjuvant, wherein the adjuvant is selected from one or more of acid-base regulators, enzyme preparations, preservatives, polymers, inorganic salts, viscosity modifiers, antibacterial agents, colorants, fragrances, and chelating agents.

[0065] acid-base regulators The acid-base regulators of this invention include acidity regulators and alkalinity regulators. The acidity regulator is selected from organic acids, inorganic acids, and strong acid-weak base salts well-known in the daily chemical industry, preferably citric acid, succinic acid, and boric acid, and more preferably citric acid. The alkalinity regulator, also known as an alkaline agent, refers to inorganic bases and organic amines; the preferred inorganic base is a metal hydroxide such as sodium hydroxide; the organic amine is selected from ethanolamine, ethylenediamine and its byproducts, and tetraalkylammonium hydroxide; ethanolamines include monoethanolamine, diethanolamine, triethanolamine, N-alkyldiethanolamine, etc.; ethylenediamine and its byproducts include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc.; and tetraalkylammonium hydroxides include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, etc.

[0066] enzyme preparations The enzyme preparation described in this invention is one or a mixture of protease and amylase, and may also contain one or more of lipase, cellulase, mannanase, and pectinase. The enzyme preparation has a weight percentage of 0.01% to 5% of the detergent composition, or preferably 0.1% to 2%.

[0067] Antibacterial agents The detergent composition of the present invention may further comprise an antibacterial agent. The antibacterial agent is selected from, but not limited to, hypochlorous acid and its salts, p-chloro-resorcinol, p-chloro-resorcinol, hydroxydichlorodiphenyl ether, hydroxytrichlorodiphenyl ether, triclocarban, o-phenylphenol, dodecyl dimethyl benzyl ammonium chloride, dodecyl trimethyl ammonium chloride, tetradecyl dimethyl benzyl ammonium chloride, tetradecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, didecyl dimethyl ammonium chloride, polyhexamethylene biguanide hydrochloride, 1-hexadecylpyridine chloride, zinc pyridinium thione, and pyridone ethanolamine salt.

[0068] polymer The polymers described in this invention include, but are not limited to: salts of homopolymers of acrylic acid, salts of copolymers of acrylic acid; cellulose derivatives, such as carboxymethyl cellulose, ethyl hydroxyethyl cellulose, and methyl cellulose; homopolymers and copolymers of vinylpyrrolidone, such as copolymers of linear polyvinylpyrrolidone, N-vinylpyrrolidone, and vinyl acetate; and polyvinylimide derivatives, such as ethoxylated polyvinylimide, polyethylene terephthalate and its derivatives, and polyethylene glycol and its derivatives. These polymers impart beneficial effects to detergent compositions, such as resistance to redeposition of dirt, promotion of dirt dissociation from substrate surfaces, or improvement of the appearance of the detergent composition.

[0069] solvent The term "solvent" in this invention refers to water and organic solvents, which are selected from polyols and / or polyol ethers; suitable examples include propylene glycol, glycerol, ethylene glycol, diethylene glycol, and sorbitol.

[0070] In addition to the above-mentioned components, the detergent compositions of the present invention may also contain various common and conventional additives such as cosolvents, solubilizers, structuring agents, foaming agents, defoaming agents, fabric softeners, bleaching systems, and anti-wrinkle agents. These additives and related methods of use are well known to those skilled in the art, and their specific types and dosages can be adjusted according to actual needs.

[0071] polyester fabric The term "polyester fabric" in this invention refers to a fabric in which the fiber content, by weight percentage, is 60% or more polyester. Other fibers constituting the fabric include, but are not limited to, cotton, spandex, and nylon.

[0072] Waterproof performance test method The waterproof performance described in this invention includes the following aspects: (1) water permeability time; (2) water immersion test. The sample for the waterproof performance test is a polyester fabric sample (100% polyester fiber content), with a weight of 220 g / m². 2 .

[0073] Water permeability time test method The polyester fabric sample was cut into a circle with a diameter of 8 cm. It was washed and rinsed three times and dried in accordance with GB / T 13174-2021 Determination of detergency and recycle performance of detergents for clothing. This sample was used as the test sample for water permeability time.

[0074] Under an environment of (20±1)℃ and (65±2)% humidity, place a 6cm diameter funnel in a 100mL conical flask, then lay the sample flat on top of the funnel. Measure 3ml of deionized water using a graduated cylinder and pour it into the center of the sample. Start timing until all the water has permeated the sample, and record the permeation time (s). The longer the permeation time, the better the waterproofness of the fabric sample. The evaluation level is determined according to Table 1.

[0075] Table 1 Evaluation Level of Permeability Time Water test method The polyester fabric sample was cut into a 200mm*200mm square, washed according to GB / T 13174-2021 Determination of detergency and recycle performance of detergents for clothing, rinsed three times and dried to serve as the wet test sample.

[0076] Under an environment of (20±1)℃ and (65±2)% humidity, the water-repellent test samples were placed for at least 4 hours and then tested according to GB / T 4745-2012 "Test and Evaluation of Water Repellency of Textiles - Water Repellency Method". The water repellency rating of each sample was determined according to the description of the water repellency phenomenon in Table 2. The higher the water repellency rating, the better the waterproof performance of the fabric sample.

[0077] Table 2 Water Repellency Rating Excellent waterproof performance The liquid detergent composition of this invention can impart excellent waterproof properties to polyester fabrics, namely, the water permeability time of the polyester fabric after washing is ≥90s, and the water stain rating is ≥4. The waterproof performance rating criteria are shown in Table 3.

[0078] Table 3 Waterproof Performance Evaluation Levels Washing and stain removal performance test method The detergency testing of the aged liquid detergent composition was conducted according to GB / T 13174-2021, "Determination of Detergency and Recycled Washing Performance of Detergents for Clothing". Three types of soiled fabrics—sebum, protein, and carbon black—were used, and their pre-wash whiteness (W1) was measured using a WSD-3U fluorescence whiteness meter from Beijing Kangguang Optical Instrument Co., Ltd. Washing water with a hardness of 250 ppm was prepared according to GB / T 13174-2021, with a calcium-to-magnesium ion molar ratio of 3:2.

[0079] The liquid detergent composition was prepared into a 0.2% solution using 250 ppm of washing water. A standard laundry detergent conforming to GB / T13174-2021 "Determination of detergency and recycle performance of detergents for clothing" was used as a reference, and a 0.2% solution was prepared using 250 ppm of washing water.

[0080] A single wash was performed using an RHLQ vertical stain remover from the China Daily Chemical Industry Research Institute. The wash time was 20 minutes, the wash temperature was 30℃, and the agitation speed was 120 rpm. The three types of soiled cloths were rinsed, dried, and their whiteness (W2) after washing was measured using a WSD-3U fluorescent whiteness meter. The whiteness difference (ΔW) was calculated as follows: △W = W2 - W1.

[0081] W2: Whiteness of the soiled cloth after washing. W1: Whiteness of the soiled cloth before washing.

[0082] The smaller the △W value, the smaller the difference in whiteness of the soiled cloth before and after washing, and the worse the washing performance of the detergent composition.

[0083] Using the control value △W as a benchmark, calculate the detergency ratio P of the detergent composition according to the following formula, and keep the result to two decimal places.

[0084] P=△W i / △W I , △W i Whiteness difference of the detergent composition △W I : Whiteness difference compared to the control group.

[0085] Excellent washing and stain removal performance The term "excellent washing and detergency performance" in this invention refers to a liquid detergent composition having a detergency ratio P of 1.03 or greater for all three types of soiled fabrics: sebum, protein, and carbon black, according to the test method in GB / T 13174-2021 "Determination of detergency and recycle performance of detergents for clothing".

[0086] Test methods for appearance stability The appearance of the liquid detergent composition after aging treatment was evaluated visually, using the liquid detergent composition before aging treatment as a control. Appearance stability was graded as "good," "fair," and "poor." The aging treatment described in this invention refers to placing the detergent composition in a sealed PE (polyethylene) bottle and storing it for four weeks at 45°C and 70% to 80% relative humidity. The terms aging treatment, aging test, and accelerated aging treatment are not distinguished. Appearance stability was evaluated according to Table 4.

[0087] Table 4 Evaluation levels of appearance stability performance Good appearance stability The term "good appearance stability" in this invention means that the liquid detergent composition remains a homogeneous system in appearance and its color remains essentially unchanged after aging treatment.

[0088] Preparation and usage instructions The liquid detergent composition of the present invention is prepared using various methods well known to those skilled in the art, ensuring that the components constituting the liquid detergent composition are uniformly mixed. The composition can be formulated using conventional methods, and specific formulation parameters, such as formulation temperature, stirring time, and heating / cooling rates, should be selected based on the physicochemical properties and stability of the components.

[0089] The method of using the liquid detergent composition involved in this invention is well known to those skilled in the art. A more conventional method of use is to bring the detergent composition into contact with the item to be washed, either as a undiluted solution or diluted in water, and then wash it by wiping, mechanical stirring or other means, and finally rinse it off the surface of the item. The item to be washed is a polyester fabric.

[0090] Example Without further detailed explanation, it is believed that those skilled in the art can fully utilize the present invention based on the above description. The following embodiments are intended to further illustrate and demonstrate specific implementations within the scope of the present invention. Therefore, the embodiments should be understood as being used only to illustrate the present invention in more detail, and not to limit the scope of the present invention in any way.

[0091] In the following examples, unless otherwise specified, all contents are percentages by mass, and the contents of the listed ingredients are converted contents of active substances.

[0092] The following compounds are used in the following embodiments.

[0093] Fluorinated acrylate polymer-1, R1 is CH3, R2 is C6F 13 R3 is C 18 H 37 The weight-average molecular weight is 100,000, the ratio of monomer unit a to monomer unit b is approximately 1:7.9, the fluorine content is 8%, and it belongs to the category of fabric finishing agent, which meets the requirements of the technical solution of this invention. Fluorinated acrylate polymer-2, R1 is CH3, R2 is C6F 13 R3 is C 18 H 37 It has a weight-average molecular weight of 75,000, a monomer unit a to monomer unit b ratio of approximately 1:17, a fluorine content of 4%, and belongs to the category of fabric finishing agent, which meets the requirements of the technical solution of this invention. Fluorinated acrylate polymer-3, R1 is CH3, R2 is C6F 13 R3 is C 18 H 37 The weight-average molecular weight is 150,000, the ratio of monomer unit a to monomer unit b is approximately 1:3.7, the fluorine content is 15%, and it belongs to the category of fabric finishing agent, which meets the requirements of the technical solution of this invention. Fluorinated acrylate polymer-4, R1 is CH3, R2 is C2F5, R3 is C 18 H 37 The weight-average molecular weight is 80,000, the ratio of monomer unit a to monomer unit b is approximately 1:2.1, the fluorine content is 10%, and it belongs to the category of fabric finishing agent, which does not meet the requirements of the technical solution of this invention. Fluorinated acrylate polymer-5, R1 is CH3, R2 is C 12 F 25 R3 is C 18 H 37 The weight-average molecular weight is 130,000, the ratio of monomer unit a to monomer unit b is approximately 1:11.9, the fluorine content is 10%, and it belongs to the category of fabric finishing agent, which does not meet the requirements of the technical solution of this invention. Fluorinated acrylate polymer-6, R1 is CH3, R2 is C6F 13 R3 is C 18 H 37 The weight-average molecular weight is 115,000, the ratio of monomer unit a to monomer unit b is approximately 1:23, the fluorine content is 3%, and it belongs to the category of fabric finishing agent, which does not meet the requirements of the technical solution of this invention. Fluorinated acrylate polymer-7, R1 is CH3, R2 is C6F 13 R3 is C 18 H 37 The weight-average molecular weight is 170,000, the ratio of monomer unit a to monomer unit b is approximately 1:3.3, the fluorine content is 16%, and it belongs to the category of fabric finishing agent, which does not meet the requirements of the technical solution of this invention. Fluorinated acrylate polymer-8, R1 is H, R2 is C4F9, R3 is C 12 H 25 The weight-average molecular weight is 60,000, the ratio of monomer unit a to monomer unit b is approximately 1:5.8, the fluorine content is 10%, and it belongs to the category of fabric finishing agent, which meets the requirements of the technical solution of this invention. Fluorinated acrylate polymer-9, R1 is C6H5, R2 is C 10 F 21 R3 is C 26 H 53 The weight-average molecular weight is 195,000, the ratio of monomer unit a to monomer unit b is approximately 1:6.4, the fluorine content is 10%, and it belongs to the category of fabric finishing agent, which meets the requirements of the technical solution of this invention. Fluorinated acrylate polymer-10, R1 is C4H9, R2 is C8F 17 R3 is C 18 H 37 The weight-average molecular weight is 150,000, the ratio of monomer unit a to monomer unit b is approximately 1:7.0, the fluorine content is 10%, and it belongs to the category of fabric finishing agent, which meets the requirements of the technical solution of this invention. Linear alkylbenzene sulfonic acid, abbreviated as LAH, belongs to the category of anionic surfactant precursors.

[0094] Linear alkylbenzene sulfonates, abbreviated as LAS, belong to the category of anionic surfactants.

[0095] Ethoxylated fatty alcohol sulfates, abbreviated as AES, belong to the category of anionic surfactants.

[0096] Dodecanoic acid belongs to the category of anionic surfactant precursors, fatty acids.

[0097] Tetradecanoic acid belongs to the category of anionic surfactant precursors, fatty acids.

[0098] Oleic acid belongs to the category of anionic surfactant precursors and fatty acids.

[0099] Fatty alcohol polyoxyethylene ether (9), abbreviated as AEO9. It belongs to the category of nonionic surfactants.

[0100] Sodium hydroxide belongs to the category of acid-base regulators.

[0101] Citric acid belongs to the category of acid-base regulators.

[0102] Sodium citrate, which is classified as a chelating agent.

[0103] Glycerin belongs to the category of organic solvents.

[0104] Propylene glycol belongs to the category of organic solvents.

[0105] Deionized water belongs to the solvent category.

[0106] Protease: It belongs to the category of enzyme preparations.

[0107] Sodium polyacrylate: It belongs to the category of polymers.

[0108] A mixture of methylisothiazolinone and chloromethylisothiazolinone: the category is preservative.

[0109] The following examples and comparative methods for preparing liquid detergent compositions 1) First, add deionized water to the mixing pot; 2) Heat to 50 to 60°C and under alkaline conditions, convert straight-chain alkylbenzene sulfonic acid and fatty acids into their corresponding salts, stirring until completely dissolved; 3) Remove the heat source and wait for the temperature to drop below 50°C. Then, add other surfactants, fabric finishing agents, polymers, and chelating agents in sequence and stir until dissolved. 4) Add fragrance, coloring, and other additives, disperse thoroughly, and then add acid-base adjuster to adjust the pH value; 5) Add preservatives, disperse thoroughly, and discharge after passing the test.

[0110] Examples 1 to 4 were prepared according to the above preparation method, and their specific compositions are shown in Table 5.

[0111] Table 5 Composition of Examples 1 to 4 Note: In the mixture of sodium salts of dodecanoic acid, tetradecanoic acid, and oleic acid, the mass ratio of the precursors dodecanoic acid, tetradecanoic acid, and oleic acid is 1:1:1.

[0112] Examples 5 to 12, and Comparative Examples 1 to 9 were prepared according to the above-described liquid detergent composition preparation method. Table 6 clearly indicates the differences.

[0113] Table 6. Similarities and differences between Examples 5 to 12 and Comparative Examples 1 to 9 Waterproof performance tests were conducted on Examples 1 to 12 and Comparative Examples 1 to 9, using the methods described above. The results are shown in Table 7.

[0114] Table 7. Waterproofing performance test results of Examples 1 to 12 and Comparative Examples 1 to 9 As shown in Table 7, Examples 1 to 12 all impart excellent waterproof performance to the fabric, specifically, the water permeability time after washing is ≥90s, and the water staining rating is ≥4. For example, the water staining phenomenon of the fabric sample in Example 2 is as follows: Figure 8 As shown in Table 7, this is because fluoropolymers can reduce the surface tension of the treated fabric to 10 to 15 mN / m, far lower than the surface tension of water (approximately 70 mN / m), thus exhibiting excellent waterproof performance. The data in Table 7 illustrate that the technical solution of this invention enables the fabric finishing agent to be effectively deposited on the fabric surface during washing, thereby reducing the fabric's surface energy and enhancing its waterproof performance. Clothing with excellent waterproof properties can prevent water and moisture from penetrating the body, especially outdoors or in humid environments, helping to keep the body dry and comfortable.

[0115] The fabrics treated with Comparative Examples 1, 2, 4, 5, and 6 had a water permeability time of less than 90 seconds and a water staining rating of less than 4, thus failing to achieve the effect of the technical solution of this invention. For example, the water staining phenomenon of the fabric sample in Comparative Example 1 was as follows: Figure 9 As shown. The water permeability time of the fabric treated in Comparative Example 8 reached 98s, but the water staining rating was 3.5 (less than 4), and it could not achieve the effect of the technical solution of this invention. The water staining phenomenon of the fabric sample in Comparative Example 8 is as follows. Figure 11 As shown.

[0116] Comparative Example 1 did not contain any fluorinated acrylate polymer, i.e., it did not contain the fabric finishing agent required by the technical solution of this invention. Comparative Example 2 contained 0.4% fluorinated acrylate polymer, and the amount of fabric finishing agent used was lower than the lower limit required by the technical solution of this invention. This indicates that the content of finishing agent deposited on the fabric after washing is 0 or too low, which cannot effectively reduce the surface energy of the fabric to meet the waterproof requirements.

[0117] Comparative Example 4 contains 3% sodium linear alkylbenzene sulfonate, which exceeds the upper limit of sodium linear alkylbenzene sulfonate usage in the technical solution of this invention. This affects the effective deposition of the fabric finishing agent on the fabric, thus failing to meet the waterproofing requirements. The water staining phenomenon of the fabric sample in Comparative Example 4 is as follows: Figure 10 As shown in the diagram, Comparative Example 5 does not contain LAS, but its AES content is 14%, and the total anionic surfactant content is 16%, exceeding the upper limit of anionic surfactant content in the technical solution of this invention, and therefore cannot achieve the effect of the technical solution of this invention. This illustrates that the content and strength of anions in the detergent system will affect the effective deposition of the fabric finishing agent on the fabric. Excessively high anionic content or strength will greatly reduce the bonding degree between the fluorinated acrylate polymer and the fabric surface, thereby affecting the waterproof performance.

[0118] Comparative Example 6 uses a fluorinated acrylate polymer-4 with R2 being C2F5, where the carbon chain length of the fluoroalkyl group is lower than the carbon chain length required by the technical solution of this invention. Comparative Example 8 uses a fluorinated acrylate polymer-6 with a fluorine content of 3%, where the fluorine content of the polymer is lower than the lower limit of the fluorine content required by the technical solution of this invention. This indicates that if the carbon chain length of the fluoroalkyl group in the fluorinated acrylate polymer is too short or the fluorine content is insufficient, it will affect the degree of reduction of the surface energy of the fabric, thereby affecting the waterproof performance.

[0119] The waterproof performance of the fabrics after washing in Comparative Examples 3, 7, and 9 was rated as excellent, and their performance was comparable to that of the Example.

[0120] The appearance stability performance was evaluated according to the aforementioned evaluation method. Examples 1 to 12, Comparative Example 3, Comparative Example 7 and Comparative Example 9 were evaluated, and the results are shown in Table 8.

[0121] Table 8. Results of appearance stability tests for Examples 1 to 12, and Comparative Examples 3, 7, and 9. As shown in Table 8, the detergent compositions prepared in Examples 1 to 12 exhibited a homogeneous appearance after aging, with essentially no change in color, and were rated as good. The appearance of the liquid detergent composition sample from Example 2 after aging was as follows: Figure 1 As shown.

[0122] The appearance of the liquid detergent composition sample prepared in Comparative Example 3 after aging is as follows: Figure 2 , Figure 3As shown, the sample exhibited a white precipitate, resulting in a poor evaluation grade. The appearance of the detergent composition prepared in Comparative Example 7 after aging is as follows. Figure 4 , Figure 5 As shown, the sample also showed a white precipitate, and the evaluation grade was poor. Comparative Example 3 contained 3% fluorinated acrylate polymer, which exceeded the upper limit of the dosage in the technical solution of this invention. The precipitation of the fluorinated acrylate polymer caused changes in appearance. Comparative Example 7 used R2 as C 12 F 25 The fluorinated acrylate polymers, whose fluoroalkyl carbon chain length exceeds the upper limit of the carbon chain length required by the technical solution of this invention, will also precipitate white sediment and cause changes in appearance in the aged detergent composition. Comparative Example 9 uses a fluorinated acrylate polymer with a fluorine content of 16%, which exceeds the upper limit of the fluorine content required by the technical solution of this invention. Its appearance after aging is as follows: Figure 6 , Figure 7 As shown, the sample exhibits a small white precipitate, and its appearance is rated as average.

[0123] The detergency performance of Examples 1 to 12 was tested, and the results are shown in Table 9.

[0124] Table 9. Decontamination performance of Examples 1 to 7 As shown in Table 9, the stain removal ratio P of Examples 1 to 12 for the three types of soiled cloths containing sebum, protein, and carbon black is ≥1.03, and the evaluation level is "having excellent washing and stain removal performance".

[0125] In summary, the detergent compositions of Examples 1 to 12 can impart excellent water resistance to washed fabrics, and also have excellent washing and stain removal performance as well as good appearance stability.

[0126] The above description is merely an example to further illustrate the technical content of the present invention, so as to facilitate the reader's understanding. However, it does not mean that the implementation of the present invention is limited to this. Any technical extension or re-creation made in accordance with the present invention is protected by the present invention.

Claims

1. A liquid detergent composition, characterized in that, It consists of the following components by mass fraction: 0.5% to 2% fabric finishing agent, 2% to 50% nonionic surfactants, 0.1% to 10% adjuvants, 0.1% to 15% anionic surfactants, The remainder is solvent; The fabric finishing agent is a fluorinated acrylate polymer, composed of monomer unit a and monomer unit b, wherein monomer unit a has the following general chemical formula (1): (1) Wherein, R1: H or C6H5 or C n H 2n+1 n is a positive integer from 1 to 4; R2: C m F 2m+1 m is a positive integer from 4 to 10; The monomer unit b has the following general chemical formula (2): (2) Wherein, R1: H or C6H5 or C n H 2n+1 n is a positive integer from 1 to 4; R3: C p H 2p+1 p is a positive integer from 12 to 26; The fluorinated acrylate polymer has a weight-average molecular weight of 60,000 to 200,000, a fluorine content of 4% to 15%, and a ratio of monomer unit a to monomer unit b of 1:2 to 1:

20. The alkylbenzene sulfonate in the anionic surfactant is present in a concentration of less than 2% in the liquid detergent composition.

2. The liquid detergent composition according to claim 1, characterized in that, The sum of the mass fractions of the nonionic surfactant and the anionic surfactant is ≥15%.

3. The liquid detergent composition according to claim 2, characterized in that, The anionic surfactant is selected from one or more of the following: alkylbenzene sulfonates, C8 to C18 alkyl sulfates, C8 to C18 ethoxylated fatty alcohol sulfates, C8 to C18 fatty acid salts, and ethoxylated fatty alcohol ether carboxylates.

4. The liquid detergent composition according to claim 1, characterized in that, The nonionic surfactant is selected from one or more of the following: fatty alcohol alkoxylates, alkyl polysaccharides, fatty acid ester alkoxylates, fatty acid alkylolamides, fatty acid methyl ester ethoxylates, and polyether surfactants.

5. The liquid detergent composition according to claim 1, characterized in that, The additives are selected from one or more of the following: acid-base regulators, enzyme preparations, preservatives, polymers, inorganic salts, viscosity modifiers, antibacterial agents, colorants, fragrances, and chelating agents.

6. The liquid detergent composition according to claim 1, characterized in that, The solvent is water and / or an organic solvent; the organic solvent is selected from polyols and / or polyol ethers.

7. The liquid detergent composition according to any one of claims 1-6, characterized in that, The stain removal ratio P for three types of soiled cloths (sebum, protein, and carbon black) is ≥1.

03.

8. The liquid detergent composition according to any one of claims 1-6, characterized in that, When placed in a sealed PE bottle and stored at 45℃ and 70% to 80% relative humidity for four weeks, the appearance remains a homogeneous system and the color does not change.

9. The liquid detergent composition according to any one of claims 1-6, characterized in that, After washing polyester fabrics, the water permeability time of the polyester fabrics is ≥90s, and the water repellency rating is ≥4.

10. The application of a fabric finishing agent in a liquid detergent composition for improving the water resistance of polyester fabrics, characterized in that, The liquid detergent composition comprises the following components by mass fraction: 0.5% to 2% fabric finishing agent, 2% to 50% nonionic surfactants, 0.1% to 10% adjuvants, 0.1% to 15% anionic surfactants, The remainder is solvent; The fabric finishing agent is a fluorinated acrylate polymer, composed of monomer unit a and monomer unit b, wherein monomer unit a has the following general chemical formula (1): (1) in, R1: H or C6H5 or C n H 2n+1 n is a positive integer from 1 to 4; R2: C m F 2m+1 m is a positive integer from 4 to 10; The monomer unit b has the following general chemical formula (2): (2) Wherein, R1: H or C6H5 or C n H 2n+1 n is a positive integer from 1 to 4; R3: C p H 2p+1 p is a positive integer from 12 to 26; The fluorinated acrylate polymer has a weight-average molecular weight of 60,000 to 200,000, a fluorine content of 4% to 15%, and a ratio of monomer unit a to monomer unit b of 1:2 to 1:

20. The alkylbenzene sulfonate in the anionic surfactant is present in a concentration of less than 2% in the liquid detergent composition.

Images