Detergent for cleaning and washing delicate fabrics

Abstract

FIELD: household chemicals.SUBSTANCE: invention relates to the composition of a detergent for treating woven products made from protein fibers. A detergent for cleaning and washing delicate fabrics in an aqueous medium includes ethoxylated fatty alcohols of unbranched and branched structure with a carbon chain length from C6 to C18 and a degree of ethoxylation from 5 to 15, potassium and sodium salts of saturated and unsaturated fatty acids with the presence of double bonds in the chemical structure from zero to two, alkyl polyglucosides with a number of carbohydrate residues of 2–4 and a hydrocarbon chain length of C6–C14, glycols, polycarboxylates with a polymer structure, where the monomer has the formula -(CH2CHCOOX)-, where X = Na, K, CH3, and a functional protective component of an alkaline nature at a certain ratio of components.EFFECT: reliable detergent for cleaning and washing delicate fabrics in water.1cl, 2 tbl, 3 ex

Description

[0001] Technical field

[0002] The present invention relates to a detergent composition for treating woven products made from protein fibers, primarily under gentle washing conditions (wet cleaning).

[0003] The treatment of items made from natural protein fibers—such as silk, wool, cashmere, angora, and casein-based fibers—is an important and relevant area in textile chemistry and professional cleaning. In recent years, wet cleaning technologies (aquacleaning) have steadily grown in popularity as an alternative to traditional dry cleaning, especially for delicate and premium fabrics. Wet cleaning requires new solutions that combine high stain removal efficiency with maximum fiber care.

[0004] It is known from literature that natural protein fibers, by their chemical nature, are susceptible to the effects of alkaline environments. It is believed that at pH levels above 8–9, destructive processes occur in the structure of keratin and fibroin: hydrolysis of amide bonds, swelling and disintegration of interchain bonds, and leaching of low-molecular components, leading to a loss of strength and changes in the appearance and color of the fabric. This is why all professional regulations (e.g., RAL-GZ 992, EN ISO 3175) recommend the use of neutral or slightly acidic detergents when working with wool and silk.

[0005] However, there is a contradiction between the requirements for fiber preservation and the need to effectively remove stains. Most stubborn stains (including grease, pigment, and others) are much more effectively broken down and dispersed in an environment with a higher pH. This environment not only promotes chemical degradation but also enhances electrostatic effects, increases the negative charge on the fiber surface, and promotes the formation of surfactant micelles. This leads to increased penetration of detergents and emulsification of stains. Consequently, detergents with a low or neutral pH, used today for washing protein fabrics, are often insufficiently effective in removing complex stains, especially at low temperatures (up to 30-40°C) or with limited mechanical action (typical of wet cleaning).

[0006] The professional laundry and wet cleaning industry currently faces a dual challenge: on the one hand, preserving the structure and color of protein fibers; on the other, ensuring a high degree of stain removal comparable to that achieved in a standard alkaline environment. The problem is compounded by the fact that modern specialized detergents lack components capable of simultaneously raising the pH of the solution and preserving the structure of protein fibers. This creates a barrier to technological progress in wet cleaning and limits the introduction of more powerful yet safe formulations for premium fabrics.

[0007] Therefore, there is an objective need to develop new detergent formulations that effectively remove stains in a moderately alkaline environment while preserving protein fibers from chemical degradation. This challenge requires innovative approaches and research into agents capable of acting as "alkaline but non-aggressive" agents that exhibit electrostatic compatibility with protein structures. Solving this challenge is crucial for the entire professional cleaning, wet cleaning, and industrial textile finishing industries.

[0008] Technology Level

[0009] Detergents for wool and silk intended for delicate washing are known, such as the compositions described in patent CN101985584B (published January 23, 2013). This invention uses EDTA (Trilon B) as a component for gentle soil removal. However, the product is designed for a neutral or slightly acidic pH and is not sufficiently effective in removing complex protein or fatty stains. Furthermore, it lacks a fiber protection mechanism in alkaline environments.

[0010] Patent application CN104830562A (published August 12, 2015) discloses a liquid formula with 7-11% EDTA, suitable for washing woolen items. Despite the high concentration of chelating agent, the composition is also designed for neutral or slightly alkaline conditions and does not actively raise the pH to 8.5-11. The protective effect of this component on fiber under alkaline conditions is not described.

[0011] Russian patent RU2308480C1 (published October 20, 2007) proposes a detergent based on whey and EDTA. While it emphasizes naturalness and gentleness, its effectiveness in removing stains is achieved in a mild environment, and acidic stabilizers limit its effectiveness in removing grease and protein stains.

[0012] The use of polyethyleneimines, amine derivatives, and cationic polymers as wool protectors in dyeing or chemical treatment formulations is also known (see, for example, patent application US3632295A, published on 04.01.1972, and patent DE19533713C1, published on 23.01.2015). However, these solutions relate to high-temperature or chemically aggressive environments and are not applicable to low-temperature cleaning in an aqueous environment.

[0013] The disadvantage of the solutions known from the prior art is the inability to be used in an environment with an elevated pH (8.5–11.5), the absence of components in the composition of detergents that increase the cleaning ability without an aggressive effect on protein fibers, as well as the inability to stabilize the color and structure of fabrics through electrostatic shielding and inhibition of degradation.

[0014] All the analogs considered are either limited in the pH level of the washing solution, or do not provide a protective effect on the fibers, or do not have sufficient cleaning activity in the fatty and protein range of contaminants.

[0015] Despite the availability of a wide range of detergents designed for protein fibers, an analysis of the most recent technical solutions shows that they do not provide comprehensive fabric protection at high pH levels. The closest in essence are formulations containing chelating agents; however, in these solutions, the components serve solely as water softeners or stabilizers, without any targeted action to protect the fiber structure and color. Furthermore, such formulations are still limited to a neutral or slightly acidic reaction and are not suitable for conditions requiring enhanced cleaning performance by raising the pH.

[0016] Compositions containing polyethyleneimine or amine derivatives used to protect fibers in dyeing require high temperatures, a chemically active environment, and cannot be adapted to the low-temperature wet washing conditions typical of wet cleaning.

[0017] Thus, no known solution combines the ability to maintain an alkaline pH of 8.5–11.5 without damaging protein fibers, stabilize fabric color and structure through adsorption of active components, and enhance the cleaning effect through electrostatically increasing the ζ-potential and combined emulsifying activity with surfactants. This confirms the lack of technically feasible solutions with a similar mechanism of action, necessitating the development of new formulations focused on safe alkaline cleaning of natural protein fibers while simultaneously protecting them and effectively removing stains.

[0018] Disclosure of invention

[0019] The problem that the claimed invention is aimed at solving is to develop a detergent for delicate and effective cleaning and washing of delicate fabrics in an aqueous environment at elevated pH values ​​(from 8.5 to 11) without destructive effects on the fiber structure and coloring, providing a complex action of amine-containing weak nucleophiles that have the ability to electrostatically stabilize the surface and simultaneously increase the alkalinity of the environment without aggressive effects on protein fibers.

[0020] The technical result achieved by implementing the present invention consists in increasing the efficiency of a detergent for cleaning and washing delicate fabrics in an aqueous medium, namely, increasing the efficiency of removing contaminants, including protein, fat and pigment components, at a pH of 8.5–11.5, while simultaneously ensuring the stability of the properties of protein fibers during their processing, namely, ensuring the protection of protein fibers (wool, silk, casein fibers) from chemical destruction during alkaline processing; ensuring the stabilization of the color of the fibers, a low value of the ΔEab2000 indicator (less than 1) before and after processing, as well as a comparison during processing at a pH of 5.5–7 and a pH of 10–11.5; preventing shrinkage of woolen fabrics during aqueous processing.Additional technical results include the following: ensuring compatibility with wet cleaning conditions, including low temperatures and limited mechanical impact; simultaneous implementation of a cleaning and protective effect in a single composition without the need for neutralizing additives; ensuring the possibility of use in both professional environments (dry cleaning) and at home.

[0021] The specified technical result is achieved by using a detergent for cleaning and washing delicate fabrics in an aqueous environment, including:

[0022] - (i) non-ionic surfactants (surfactants), in the form of ethoxylated fatty alcohols of unbranched structure with a carbon chain length from C6 to C18 and a degree of ethoxylation from 5 to 15, wherein the content of the mixture by weight of the detergent is 10-25%,

[0023] - (ii) non-ionic surfactants (surfactants), in the form of ethoxylated branched fatty alcohols with a carbon chain length from C6 to C18 and a degree of ethoxylation from 5 to 15, wherein the content of the mixture by weight of the detergent is 3-10%,

[0024] - (iii) soaps in the form of potassium and sodium salts of fatty saturated and unsaturated acids of various structures with the presence of double bonds in the chemical structure from zero to two inclusive, and the content of the mixture by weight of the detergent is 2-7%,

[0025] - (iv) alkyl polyglucosides with a number of carbohydrate residues from 2 to 4 and a hydrocarbon chain length from C6 to C14, wherein the content of the mixture by weight of the detergent is 2-5%,

[0026] - (v) glycol components selected from butyl cellosolve or propylene glycol, or butyl diglycol, or propoxylated butanol or methanol with a number of propoxy groups from 1 to 3, wherein the content of the mixture by weight of the detergent is 2-10%,

[0027] - (vi) polycarboxylates with a polymeric structure, where the monomer has the formula –(CH2СHСOOX)-, where X=Na, K, CH 3, where the content of the mixture by weight of the detergent is 0.5-3%

[0028] - (vii) a functional protective component of alkaline nature with a structure selected from the following group:

[0029]

[0030] or

[0031]

[0032] or

[0033]

[0034] where R' is selected from H, CH3, C2H5, iso-C3H9, CH2COOX. X is selected from H + , Na + , K + , NH4 +. Where R'' is selected from H, CH3, C2H5, iso-C3H9, CH2COOX. X is selected from H + , Na + , K + , NH4 + . Where R''' is selected from H, CH3, C2H5, iso-C3H9, CH2COOX. X is selected from H + , Na + , K + , NH4 + , where Y is selected from H, CH3.

[0035] The content of the functional protective component mixture by weight of the detergent is 2-15%. The rest is water.

[0036] Definitions of terms

[0037] Below, the terms and their definitions used in the description of the technical solution will be discussed in detail.

[0038] Protein fibers are natural polymers built on amino acid chains, including wool, silk, casein fibers, and similar materials. They are sensitive to alkaline environments and tend to hydrolyze at elevated pH values.

[0039] Nucleophilicity is a chemical property that determines a molecule's ability to attack electrophilic centers. Weak nucleophiles are characterized by reduced reactivity and a lower probability of breaking sensitive structures (e.g., peptide bonds).

[0040] ζ-potential (zeta potential) is an electrokinetic parameter that reflects the surface charge of a material in a liquid medium. Increasing ζ-potential leads to increased particle repulsion and contaminant dispersion.

[0041] Surfactant micelles are aggregates of surface-active substances that form at concentrations above the CMC (critical micelle concentration) and are capable of encapsulating fats, oils and other non-polar contaminants.

[0042] Aqua cleaning is a technology for gentle water cleaning of delicate fabrics using specialized programs and limited mechanical impact.

[0043] Implementation of the invention

[0044] A key feature of the invention is the use of a functional protective component with an amine group, which is a weak nucleophile with a high affinity for the negatively charged surface of protein fibers. This component performs two functions: increasing the alkalinity of the medium, which improves cleaning ability, and stabilizing the fiber surface through electrostatic interaction of nitrogen atoms and partial adsorption, preventing swelling, pigment leaching, and structural degradation.

[0045] The functional protective component interacts with the fiber through electrostatic affinity and weak nucleophilicity, preventing aggressive reactions with protein bonds. This product thus provides enhanced stain removal while preserving the color and structure of the fibers. Furthermore, it can be used not only in wet cleaning but also in industrial textile processing.

[0046] The key features of the claimed detergent are:

[0047] • Use of a functional protective component of an alkaline nature (for example, weak amine nucleophiles) that does not damage protein fibers, while creating a pH of the environment of 8.5–11.

[0048] • Increased cleaning ability of the composition due to electrostatic and solubilizing effects without increasing aggressiveness.

[0049] • Electrostatic adsorption of active molecules on the fiber surface and stabilization of its color.

[0050] • Compatible with existing wet cleaning technologies and minimizes shrinkage and color loss.

[0051] • Possibility of selling the composition as a ready-made product or in the form of a concentrate.

[0052] The detergent according to the invention is obtained by sequentially or simultaneously mixing the components with stirring in an aqueous medium at a temperature of 20 to 50°C. The process is carried out in a standard container with a stirrer (laboratory or industrial), ensuring a homogeneous mixture. No chemical transformations occur. The procedure includes the following steps:

[0053] 1. Adding the main volume of water and dissolving in it polycarboxylates with a polymer structure, where the monomer has the formula -(CH2СHСOOX)- (where X=Na, K, CH3), with stirring until completely dissolved in an amount of 0.5-3% by weight of the detergent.

[0054] 2. Non-ionic surfactants, glycols, soaps, and alkyl polyglycosides are added sequentially, ensuring their dispersion. Non-ionic surfactants are ethoxylated straight-chain fatty alcohols with a carbon chain length from C6 to C18 and a degree of ethoxylation from 5 to 15 in an amount of 10-25% by weight of the detergent, and ethoxylated branched fatty alcohols with a carbon chain length from C6 to C18 and a degree of ethoxylation from 5 to 15 in an amount of 3-10% by weight of the detergent. Glycol components (glycols) are selected from the following: butyl cellosolve, propylene glycol, butyl diglycol, propoxylated butanol or methanol with a number of propoxy groups from 1 to 3. The amount of glycols by weight of the detergent is 2-10%.Soaps are added in the form of potassium and sodium salts of saturated and unsaturated fatty acids, the structure of which does not affect the technical result, while containing from zero to two double bonds in the chemical structure. The amount of soap added is 2-7% by weight of the detergent. Alkyl polyglucosides with a number of carbohydrate residues from 2 to 4 and a hydrocarbon chain length from C6 to C14 are used in an amount of 2-5% by weight of the detergent.

[0055] 3. A functional protective component of an alkaline nature (e.g., an amine-containing nucleophile) is introduced into the mixture at the final stage. When adding it, focus on a structure selected from the following group:

[0056] or or ,

[0057] where R' is selected from H, CH3, C2H5, iso-C3H9, CH2COOX. X is selected from H + , Na + , K + , NH4 + , R'' is selected from H, CH3, C2H5, iso-C3H9, CH2COOX. X is selected from H + , Na +, K + , NH4 + , R''' is selected from H, CH3, C2H5, iso-C3H9, CH2COOX. X is selected from H + , Na + , K + , NH4 + , and Y is selected from H, CH3. The amount of added functional protective component by weight of the detergent is 2-15%.

[0058] 4. The mixture is homogenized until a stable transparent liquid without visible phase separation is obtained.

[0059] If necessary, functional additives (preservatives, flavors, colorants) are added to the composition without affecting the stability of the main action.

[0060] The finished product can be packaged in containers. The composition is stable when stored for at least 24 months at temperatures from +5 to +30°C.

[0061] The production process is easily scalable and does not require special conditions or catalysts, making it suitable for both laboratory production and industrial implementation.

[0062] The invention is implemented primarily in professional dry cleaners equipped with wet cleaning equipment. Detergents based on the claimed composition are dispensed manually or using automatic dosing systems into the first bath of the wash cycle.

[0063] The processing temperature is selected based on the product's composition and ranges from 25 to 40°C. Neutralization of the composition after use is not required. Residues of the product are easily removed by rinsing.

[0064] This method is a single-bath process: for delicate fabrics, a second wash stage or additional rinsing is not used. The fiber treatment (mechanical agitation) meets industry standards for delicate fabrics (low G-factor up to 0.45, shortened cycles).

[0065] The product can also be used in household conditions - for hand or machine washing - with the same temperature and safety parameters.

[0066] Thus, the invention provides an industrially suitable and universal solution for treating delicate protein fiber products without damage under high alkalinity of the washing solution.

[0067] To evaluate the protective properties, color stabilization effect, and the absence of shrinkage, delicate fabrics (natural wool and silk without fibers of a different chemical nature) with an exact size of 100 mm by 100 mm were tested by immersing them in the corresponding solvents with a volume of 200 ml for 10 minutes while stirring with a magnetic anchor at a speed of 200 rpm. The temperature of the solvents was 25 ° C, and the temperature of the control experiment with water as a solvent was 25 ° C. Then, the fabric pieces were dried in air for 2 hours. To calculate shrinkage, the linear dimensions (length and width) were measured, and the deviation from the norm in % was calculated (see Table 1). To measure the color change, a 3NH TS8500S reflectance spectrophotometer was used (measurement conditions D65 / 10 °, aperture 25.4 mm without using a UV LED). The color change was calculated in comparison with the original samples using the standardized value ΔE ab 2000 (see table 1).

[0068] The detergent under study includes: a non-ionic surfactant (Sintanol ALM-7) with a concentration of 20% by weight, ethoxylated (3EO) isotridecyl alcohol - 5% by weight, potassium soap based on stearic and lauric acids in a molar ratio of 2 to 1 - 4% by weight, alkyl polyglucosyl with a chain length of C0810 - 2%, butyl diglycol - 4%, polyacrylate 1% and a functional protective component - 10%. A washing solution with a concentration of 10% is prepared from the detergent. Thus, the mass concentration of the functional protective component in the test solution is 1%.

[0069] Table 1. Study of color retention and shrinkage of natural wool and silk when using the claimed detergent with different contents of one of the presented functional protective components

[0070] Concentration (mass) pH of 1% solution Silk sample size (after processing)* ∆E 2000 Size of wool sample (after processing) ∆E 2000 Water - 6,26 100*92 0 100*99 0 Alkaline components causing destruction: Sodium hydroxide 0,30% 13,2 100*86 5,53 98*91 4,9 Sodium carbonate 1,0% 11,76 100*87 3,2 98*92 3,76 Sodium bicarbonate 1,0% 9,51 100*88 2,1 98*95 2,2 Tetrasodium glutamate diacetate 1,0% 11,12 100*88 1,63 100*97 1,52 Components of the invention that do not cause destruction: Tetranatium salt of ethylenediaminetetraacetic acid 1,0% 11,34 100*92 0,39 100*99 0,56 Monoethanolamine 1,0% 11,35 100*92 0,45 100*99 0,48 N-Dimethylmonoethanolamine 1,0% 11,54 100*92 0,70 100*99 0,51 trisodium salt of nitrilotriacetic acid 1,0% 11,44 100*92 0,41 100*99 0,62

[0071] A change in linear dimensions of up to 1-1.5% is normal for woolen products and does not result in damage. Furthermore, the fabric regains its dimensions during finishing (for example, when using wet-heat treatment). ΔE change ab 2000 should be less than 1, which indicates that the color change cannot be seen with the naked eye.

[0072] The experimental data show that at a pH of 10 to 11.5, the detergent with these active nitrogen-containing components does not affect the color of the materials, and according to microscopy, there is no destruction of the fibers, which is fundamentally different from the use of sodium hydroxide, sodium carbonate and sodium bicarbonate solutions, even at a similar and lower pH level.

[0073] Silk shrinks by up to 10% in one dimension upon contact with water, regardless of the pH of the environment. However, such items are processed during the wet cleaning process by fixing them to a fabric backing, and the primary purpose is to protect the color and structure of the fiber, which, as noted above, does occur.

[0074] To confirm the increased washing ability in relation to natural wool, experiments were conducted on the treatment of standard contamination EMPA 107 (olive oil - wool - soot) from Swissatest (Switzerland) with a detergent according to the described formula and with various examples of the functional protective component indicated in Table 2.

[0075] Table 2. Testing the cleaning ability of the tested detergent depending on the selected functional protective component on EMPA107 contamination

[0076] Functional component type pH of 1% solution ∆E 2000 Absent 7,5 0 (standard) Tetranatium salt of ethylenediaminetetraacetic acid 11,44 3,28 Monoethanolamine 11,35 3,55 Trisodium nitrite triacetic acid 11,34 3,89

[0077] As can be seen from Table 2, olive oil removal is significantly better at an alkaline pH than at a neutral pH. Thus, the detergent according to the invention demonstrates both high cleaning performance and safety against protein fibers.

[0078] Examples of the detergent of the invention:

[0079] Example 1.

[0080] The ratio of components, mass% is as follows:

[0081] 1. Non-ionic surfactant (Sintanol ALM-7) 20%,

[0082] 2. Ethoxylated (3EO) isotridecyl alcohol 5%

[0083] 3. Potassium soap based on stearic and lauric acids in a molar ratio of 2 to 1 - 4%, alkyl polyglucosyl with a chain length of C8-10 - 2%

[0084] 4. Butyl diglycol – 4%,

[0085] 5. Polyacrylate (aqueous solution 50%) 1% of the active substance

[0086] 6. Tetrasodium salt of ethylenediaminetetraacetic acid component - 10%

[0087] As a result of the study of the ability to remove oleophilic contaminants (olive oil-soot) from wool according to Example 1, the following values ​​of the parameter ∆E were established 2000 – 3.28. By the change in color of natural silk ∆E 2000 = 0.39.

[0088] Therefore, the composition according to example 1 at an alkaline pH level (10.5-11.5) has high cleaning ability and a gentle effect on natural protein fibers.

[0089] Example 2.

[0090] The ratio of components, mass% is as follows:

[0091] 1. Non-ionic surfactant (Sintanol DS-10) 15%,

[0092] 2. Ethoxylated (3EO) isotridecyl alcohol 3%

[0093] 3. Potassium soap based on stearic and lauric acids in a molar ratio of 2 to 1 - 4%, alkyl polyglucosyl with a chain length of C12-14 - 7%

[0094] 4. Propylene glycol – 8%,

[0095] 5. Polyacrylate (aqueous solution 50%) 0.5% of the active substance

[0096] 6. Trisodium nitrilotriacetic acid component – ​​15%

[0097] As a result of the study of the ability to remove oleophilic contaminants (olive oil-soot) from wool according to example 2, the following values ​​of the parameter ∆E were established 2000 – 3.9. By the change in color of natural silk ∆E 2000 = 0.41.

[0098] Therefore, the composition according to example 2 at an alkaline pH level (10.5-11.5) has high cleaning ability and a gentle effect on natural protein fibers.

[0099] Example 3.

[0100] The ratio of components, mass% is as follows:

[0101] 1. Non-ionic surfactant (ethoxylated alcohol-Guerbet C10 with a degree of ethoxylation of 5 EO - Rokanol GA5) 15%,

[0102] 2. Ethoxylated (5EO) isotridecyl alcohol 10%

[0103] 3. Potassium soap based on stearic and lauric acids in a molar ratio of 2 to 1 - 4%, alkyl polyglucosyl with a chain length of C12-14 - 10%

[0104] 4. Dowanol PnB – 2%,

[0105] 5. Polyacrylate (aqueous solution 50%) 3% of the active substance

[0106] 6. Monoethanolamine – 5%

[0107] As a result of the study of the ability to remove oleophilic contaminants (olive oil-soot) from wool according to Example 3, the following values ​​of the parameter ∆E were established 2000 – 3.65. By the change in color of natural silk ∆E 2000 = 0.51.

[0108] Therefore, the composition according to example 3 at an alkaline pH level (10.5-11.5) has high cleaning ability and a gentle effect on natural protein fibers.

[0109] The compositions of examples 1-3, in terms of cleaning ability and delicate action on natural protein fibers, meet the requirements for professional wet cleaning in an aquatic environment.

[0110] The proposed invention addresses the pressing need to simultaneously improve the effectiveness of detergents while protecting the structure and color of protein fibers at elevated pH. By using a functional alkaline protective component (e.g., selected amine-containing components)—weak nucleophiles with high electrostatic compatibility with protein substrates—a previously unattainable combination is achieved: high cleaning power and color retention in alkaline environments.

[0111] This development meets the modern needs of the textile laundry and care industry, particularly wet cleaning, where the proportion of delicate and composite materials requiring aqueous treatment is increasing. The invention is technologically simple to implement, does not require expensive or toxic components, is stable, easily scalable, and can be used in both professional and domestic environments. Compositions based on it are affordable, do not require aggressive stabilizers, provide stable storage, and are compatible with standard dosing systems.

[0112] Although the invention is described with reference to specific embodiments and examples, it will be obvious to those skilled in the art that these descriptions serve only to illustrate the essence of the invention and do not limit its scope. Various modifications, the selection of equivalent components, or the implementation of compositions in different proportions are possible without deviating from the essence and spirit of this technical solution.

[0113] The invention opens up a new category of alkaline, yet safe, detergents that can effectively and gently treat protein fibers and mixed-composition fabrics, improving both the quality of cleaning and the durability of products.

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