Detergent composition

Abstract

The present invention relates to a stable liquid detergent composition comprising - 10 wt% to 14 wt% of hydrogen peroxide, - 0.005 wt% to 1 wt% phthalimidoperoxycaproic acid or a salt thereof, - 0.0005 wt% to 1 wt% of at least one chelating stabilizer, and - 0.1 wt% to 40 wt% of at least one surfactant, and optionally water to 100 wt%.

Description

[0001] DETERGENT COMPOSITION

[0002] FIELD OF THE INVENTION

[0003] The present invention relates to the field of detergent compositions and uses thereof .

[0004] BACKGROUND OF THE INVENTION

[0005] Detergents are an indispensable part of everyday li fe and are essential in routinely cleaning and washing processes . Examples of commercially available detergent products include laundry and fabric softeners , all-purpose cleaners , and mixtures intended for soaking (pre-washing) , rinsing or bleaching . Detergent formulations , in particular for fabric washing, must remove a wide variety of stains and soils from di f ferent fabric types under a broad range of wash conditions . Principal components of detergent formulations include surfactants , builders , and enzymes to remove primarily oily, greasy, particulate , and proteinaceous soils and stains .

[0006] Many detergents still cannot remove some stains ef fectively without the aid of other solutions such as hydrogen peroxide (H2O2 ) • Hydrogen peroxide is well known in the art and used as a bleaching agent , antiseptic, or as a component in detergent formulations . Since hydrogen peroxide breaks down into innocuous products such as oxygen and water, it also represents a safe environmental cleaning component . However, hydrogen peroxide is also known for its challenges in stability, especially in environments containing various other substances . For instance , hydrogen peroxide is highly susceptible to decomposition by the presence of transition metal cations that are typically contained in the additional ingredients of the formulation ( i . e . surfactants , builders , etc . ) . Furthermore , an alkaline environment is typically required to optimi ze the cleaning and bleaching ef ficiency of peroxide-containing cleaning agents . However, under alkaline conditions , hydrogen peroxide tends to decompose during storage , reducing its concentration and, consequently, its cleaning and bleaching ef ficiency over time .

[0007] US 2021 / 130736 discloses a process for the manufacture of an aqueous composition suitable for disinfecting and cleansing . The composition described therein comprises hydrogen peroxide, at least one fatty acid, at least one amine oxide, and peroxyacetic acid, and may include stabilizers for peroxyacids and / or hydrogen peroxide such as ethylenediaminetetraacetic acid (EDTA) , diethylenetriaminepentaacetic acid (DTPA) , quinolinic acid, picolinic acid, dipicolinic acid, and 1-hydroxyethylidene- 1 , 1-diphosphonic acid (HEDP) .

[0008] US 2021 / 400961 describes a composition for sterilization and cleaning comprising 0.001 wt% to 30 wt% of peroxyacetic acid, 0.001 wt% to 30 wt% of hydrogen peroxide, 1 wt% to 70 wt% of acetic acid and / or a salt thereof, 0.001 wt% to 5 wt% of polyoxyethylene lauryl ether acetic acid or a salt thereof as surfactant and water.

[0009] US 11,713,436 discloses a method of bleaching and disinfecting laundry articles by using a composition comprising peroxycarboxylic acids and disinfectants. The composition comprises 0.1 wt% to 40 wt% of peroxycarboxylic acid, 0.5 wt% to 10 wt% of a stabilizing agent, and an acid-stable surfactant.

[0010] It is imperative achieving a stable detergent formulation to ensure proper efficiency and shelf life of detergents comprising hydrogen peroxide.

[0011] It is, therefore, an object of the present invention to provide a stable and efficient detergent formulation.

[0012] SUMMARY OF THE INVENTION

[0013] Thus, the present invention relates to a stable liquid detergent composition comprising

[0014] - 10 wt% to 14 wt% of hydrogen peroxide,

[0015] - 0.005 wt% to 1 wt% phthalimidoperoxycaproic acid (PAP) or a salt thereof,

[0016] 0.0005 wt% to 1 wt% of at least one chelating stabilizer, and

[0017] - 0.1 wt% to 40 wt% of at least one surfactant, and optionally water to 100 wt%.

[0018] It surprisingly turned out that the composition of the present invention is a highly storage stable liquid detergent, so that the hydrogen peroxide present in the composition remains stable over time under storage conditions. The composition of the present invention addresses also the challenge of efficiently cleaning materials, such as removing stains from textiles or porous materials, preferably when diluted with water in a ratio from 1:0.1 to 1:500, preferably 1:10 to 1:500, more preferably from 1:50 to 1:400, more preferably 1:50 to 1:300, more preferably 1:50 to 1:200. The composition of the present invention and in particular the hydrogen peroxide present therein is stable for up to two years of storage and shows exceptional cleaning properties during shelf-life. In addition, it has been found that the composition according to the present invention shows an effective biocidal activity. Hence, the composition of the present invention surprisingly combines both detergent and disinfectant properties while maintaining stability against hydrogen peroxide decomposition over time.

[0019] The composition of the present invention is a stable cleaning agent as well as an effective disinfectant of various materials or surfaces, also when diluted with water in a ratio from 1:0.1 to 1:500, preferably 1:10 to 1:500, more preferably from 1:50 to 1:400, more preferably 1:50 to 1:300, more preferably 1:50 to 1:200, to give a ready-to-use formulation. For instance, the composition of the present invention and the composition diluted with water in a ratio to up to 1:500 show the ability to disinfect different materials (e.g. textiles) and / or washing machines. Although laundering mainly aims to remove visible soil and stains, the removal of microorganisms and viruses is also an important step in the reconditioning of textiles. Furthermore, disinfecting the washing machine regularly is not only crucial for maintaining cleanliness, preventing mold and bacteria growth, and ensuring optimal appliance longevity, but also plays a role in preventing the contamination of textiles. This, in turn, is important for safeguarding human health, as contaminated textiles can serve as a medium for the transmission of infectious agents, further emphasizing the importance of a comprehensive approach to laundry hygiene. It could be also shown that the compositions of the present invention reduce and even prevent the formation of biofilms in washing machines. The present invention provides stable compositions with cleaning and biocidal properties, wherein stability of the compositions is not only pivotal for maintaining biocidal properties but also crucial for ensuring consistent cleaning performance.

[0020] In addition, the compositions of the present invention are particularly effective in the cold washing zone (18 to 40 °C) during laundering. The strive for energy efficiency led to a rising need to lower washing temperatures in laundering processes. It has been found that the present compositions show also good cleaning performance at lower washing temperatures, demonstrating their ability to remove stains and maintain biocidal activity while ensuring an energy-efficient washing process.

[0021] Another aspect of the present invention relates to the use of the stable liquid detergent composition of the present invention as a washing product and / or biocidal product, in particular as a laundry detergent or as a dishwashing liquid.

[0022] A further aspect of the present invention relates to a ready-to-use formulation comprising a composition as defined above and water in a ratio from 1:0.1 to 1:500, preferably 1:10 to 1:500, more preferably from 1:50 to 1:400, more preferably 1:50 to 1:300, more preferably 1:50 to 1:200.

[0023] The compositions of the present invention are useful for households (B2C) and also for professional (B2B) users, such as shared laundries, hotels, hospitals, nursing homes, and kindergartens. The compositions of the present invention are also useful as a household and commercial disinfectant, bactericide, sporicide, fungicide and / or virucide, sanitizer, and cleaner. Adding to the versatility and applications of the compositions according to the present invention, the compositions are not only useful for a wide range of cleaning and biocidal applications but also specifically applicable for Clean-In-Place (CIP) and Clean-Out-of-Place (COP) methods. These methods are particularly valuable in various industries for ensuring thorough sanitation of equipment and surfaces without disassembly, further highlighting the compositions broad utility in maintaining hygiene standards across numerous settings.

[0024] Yet another aspect of the present invention relates to a method for preparing a stable liquid detergent composition comprising the step of mixing - 10 wt% to 14 wt% hydrogen peroxide,

[0025] - 0.005 wt% to 1 wt% phthalimidoperoxycaproic acid or a salt thereof,

[0026] 0.0005 wt% to 1 wt% of at least one chelating stabilizer, and

[0027] - 0.1 wt% to 40 wt% of at least one surfactant, and optionally water to 100 wt%.

[0028] Another aspect of the present invention relates to a method for cleaning a surface or textile comprising a) the step of contacting the surface or textile with a composition according to the invention, or b) the steps of mixing a composition of the invention with water in a ratio from 1:0.1 to 1:500, preferably 1:10 to 1:500, more preferably from 1:50 to 1:400, more preferably 1:50 to 1:300, more preferably 1:50 to 1:200, and contacting the surface or textile with said mixture.

[0029] DETAILED DESCRIPTION OF THE INVENTION

[0030] As used herein, the term "liquid detergent composition" refers to a composition capable to remove soil from a substrate. The substrate can be, for instance, a fabric, a metallic substrate, a plastic substrate, or a ceramic substrate. The composition can be used, for instance, as laundry pre-treatment , laundry post-treatment, or can be added during the rinse cycle or wash cycle of a laundry operation. The liquid detergent composition can be in a form selected from the group consisting of pourable liquids, foamable liquids, gels, creams, and combinations thereof. The liquid detergent composition can be aqueous or non-aqueous, and can be anisotropic, isotropic, or a combination thereof.

[0031] The term "stable liquid detergent composition", as used herein, means that the relative decay of the hydrogen peroxide concentration of the liquid detergent composition is less than 15 %, preferably less than 12 %, preferably less than 10 %, preferably less than 5 %, during a period of two years. To determine the relative decay of the hydrogen peroxide concentration, an accelerated aging protocol, as outlined by the Biocidal Products Regulation (BPR, Regulation (EU) 528 / 2012) , can be used for simulating long-term stability. This method involves exposing the product to a temperature of 54 °C for 14 days, a process designed to mimic the effects of two years of shelf life in a condensed timeframe. A further accelerated aging protocol that can be employed is the Peroxide Industry Standard Method for accelerated aging, a test that exposes the product to 60 °C for up to 144 hours. This approach is designed to simulate the effects of two years of shelf life within a significantly shorter period. The insights gained from these observations are crucial in predicting detergent's long-term stability and ensuring its effectiveness, even under extreme conditions. Surprisingly, the present composition shows limited diminution in hydrogen peroxide concentration under accelerated aging conditions, as specified above. This degree of diminution also aligns with other operational exigencies of the composition, such as biocidal activity as well as washing efficacy.

[0032] The term "biocidal activity", as used herein, refers to the ability of the composition according to the invention to reduce the concentration of a contaminant composition that is harmful to human or animal health or that causes damage to natural or manufactured products. Preferably, the contaminant is a microorganism, such as a bacterium, yeast, virus, fungus, protozoa, or pests, such as insects, algae, or mites. Exemplarily the composition of the present invention is able to eliminate or inhibit the growth of bacteria like Escherichia coli, Staphylococcus aureus, Salmonella enterica, Listeria monocytogenes , Pseudomonas aeruginosa , Bacillus cereus, Clostridium perfringens , Methicillin-resistant Staphylococcus aureus (MRSA) , Streptococcus pyogenes, Mycobacterium tuberculosis, Helicobacter pylori, Clostridium difficile, Neisseria gonorrhoeae, Legionella pneumophila, Shigella spp . , Enterococcus faecium, Klebsiella pneumoniae . The composition of the present invention can also eliminate or inhibit the growth of yeasts or fungi like Candida albicans , Saccharomyces cerevisiae, Aspergillus niger, Fusarium oxysporum, Exophiala dermatitidis, Exophiala phaeomu- riformis, Candida parapsilosis, Rhodotorula mucilaginosa, Aure- obasidium spp., Exophiala spp., Fusarium oxysporum, Fusarium solani , Peni cilli um crustosum, Debaryomyces hansenii , Meyerozyma guilli ermondii , Candida Parapsil osi s , or Sporothrix clava te . Also , the activity of viruses such as Norovirus , Rotavirus , Influenza virus , Adeno viruses , Corona viruses or Human papillomavirus (HPV) can be reduced by the composition of the present invention .

[0033] As used herein, the term "reduction" means that 90 % , preferably 95 % , more preferably 99 % , from the original concentration of viable microorganisms and viruses is killed and inactivated, respectively . The concentration of the contaminant composition can be reduced by at least 4-log, preferably at least 5-log, preferably at least 6-log, preferably at least 7-log, after application of the composition according to the present invention . The biocidal activity can be assessed according to the biocidal regulation (BPR, Regulation (EU) 528 / 2012 ) , which requires testing of biocidal products in accordance with the overarching standard EN 14885 for biocidal ef ficacy . In particular, the ef ficacy for non-medical area on bacteria can be carried out according to EN 1276 , and ef ficacy for non-medical area on yeasts and fungi according to EN 1650 , while ef ficacy for medical area requires standards carried out according to EN 13727 for bacteria, and EN 13624 for yeasts and fungi . In addition, a carrier test according to EN 16616 for medical area and EN 17658 for non-medical area can be performed to determine the ef fectiveness in reducing microorganism levels under practical cleaning conditions . Furthermore , EN 13697 can be utili zed for quantitatively assessing bactericidal and fungicidal activity on non-porous surfaces , EN 14476 for determining virucidal activity in the medical area, and EN 16777 to test virucidal activity in the non-medical area, ensuring a broad-spectrum biocidal assessment .

[0034] The term "washing ef ficacy" , as used herein, refers to the cleaning performance of the composition of the present invention in regard to the ability to remove stains and maintain textile integrity of laundry . The washing ef ficacy can be determined following the guidelines set by the International Association for Soaps , Detergents , and Maintenance Products (AISE ) . The composition of the present invention shows good washing efficacy while maintaining the stability over time.

[0035] "At least one", as used herein, refers to one or more, preferably to two or more, three or more, four or more, or five or more.

[0036] According to a preferred embodiment of the present invention, the pH of the composition of the present invention is 4 or less, more preferably 3 or less, more preferably 2.5 or less, more preferably 1 or less.

[0037] According to another preferred embodiment of the present invention, the pH of the composition of the present invention is between 0.2 and 4, preferably between 0.2 and 3, more preferably between 0.2 and 2, more preferably between 0.2 and 1.5, more preferably between 0.2 and 1.

[0038] It has been turned out that the composition of the present invention can be stable at pH 4 or less. It has been found that the composition might also be stable at more neutral or acidic conditions to achieve good cleaning efficiency while maintaining hydrogen peroxide stability over time.

[0039] According to another preferred embodiment of the present invention, the stable liquid detergent composition comprises 10 wt% to 12 wt%, preferably 11 wt% to 12 wt%, hydrogen peroxide.

[0040] According to another preferred embodiment of the present invention, the composition comprises 0.05 wt% to 1 wt%, preferably 0.05 wt% to 0.75 wt%, phthalimidoperoxycaproic acid or a salt thereof.

[0041] The presence of phthalimidoperoxycaproic acid in the composition of the present invention results in a particular stable composition, in particular in regard to the degradation of hydrogen peroxide. Furthermore, it was surprisingly found that the presence of phthalimidoperoxycaproic acid in the composition of the present invention has a beneficial impact on the compositions' biocidal activity, in particular if diluted with water at the ratios disclosed herein.

[0042] The composition according to the present invention also comprises at least one chelating stabilizer.

[0043] The term "chelating stabilizer", as used herein, refers to a molecule that is capable to bind metal ions to create stable complexes. These complexes can sequester and scavenge trace metal impurities that may accelerate the decomposition of hydrogen peroxide.

[0044] According to a preferred embodiment of the present invention, the at least one chelating stabilizer is a phosphonic stabilizer, an aromatic stabilizer, or a combination thereof. Thus, the composition of the present invention may comprise at least one phosphonic stabilizer and / or at least one aromatic stabilizer.

[0045] A "phosphonic stabilizer", as used herein, relates to compounds comprising or being phosphonates containing R1-PO (OM1 / 2) 2 groups. A preferred phosphonate / phosphonic stabilizer according to the invention may have the general formula wherein R1is an organic moiety, X1is OH or OMi and X2is OH or OM2, wherein Mi and M2 represent an alkali metal ion or ammonium ion. The organic moiety R1may be a substituted or unsubstituted C1-C12 alkyl moiety, C3-C10 cycloalkyl moiety or Ce- Ci4 aryl moiety. One or more of the carbon atoms of said moieties may be substituted with a nitrogen atom. The organic moiety may be attached to 1 to 10 further phosphonate groups of the general formula ( I ) .

[0046] According to another preferred embodiment of the present invention, the composition comprises 0.0005 wt% to 1 wt%, preferably 0.0005 wt% to 0.5 wt%, more preferably 0.005 wt% to 0.5 wt%, of the at least one phosphonic stabilizer. The composition, therefore, meets the limits Regulation (EC) No 648 / 2004 of the European Parliament and of the Council on detergents regarding the upper phosphorous content limit of 0.5 g compared to the recommended detergent volume for standard washing machine filling .

[0047] According to another preferred embodiment of the present invention, the at least one phosphonic stabilizer is selected from the group consisting of 1-hydroxyethylidene-l , 1- diphosphonic acid (HEDP) , aminotris (methylenephosphonic acid) (ATMP) , diethylenetriamine penta (methylenephosphonic acid) (DTPMP) , hexamethylenediamine tetra (methylenephosphonic acid) (HMDTMP) , ethylenediamine tetra (methylenephosphonic acid) (EDTMP) , 2-phosphonobutane-l , 2 , 4-tricarboxylic acid (PBTC) , bis (hexamethylenetriamine penta (methylenephosphonic acid) ) , and mixtures thereof.

[0048] According to another preferred embodiment of the present invention, the composition comprises 0.0005 wt% to 1 wt%, preferably 0.0005 wt% to 0.5 wt%, more preferably 0.005 wt% to 0.1 wt%, of the at least one aromatic stabilizer.

[0049] As used herein, the term "aromatic stabilizer" refers to a chelating stabilizer characterized by one or more planar rings of atoms joined by covalent bonds. Preferably, the aromatic stabilizer includes carbocyclic aromatic rings, such as benzene or naphthalene rings, as well as heteroaromatic rings, such as pyridine and quinoline. According to another preferred embodiment of the present invention, at least one aromatic stabilizer is selected from the group consisting of dipicolinic acid, picolinic acid, salicylic acid, and mixtures thereof.

[0050] According to another preferred embodiment of the present invention, the composition comprises further at least one inorganic stabilizer selected from the group consisting of phosphoric acid, nitric acid, pyrophosphoric acid salts, and mixtures thereof. Preferably, pyrophosphoric acid salts are potassium pyrophosphate or disodium pyrophosphate.

[0051] The composition of the present invention may also comprise carboxylic acids and / or salts thereof. However, it turned out that carboxylic acids and / or salts thereof may have a negative influence on the stability of hydrogen peroxide at higher concentrations. Hence, if carboxylic acids and / or salts thereof are added to the composition of the present invention it is preferred that the composition comprises 1 wt% or less, preferably 0.5 wt% or less, of at least one carboxylic acid.

[0052] According to another preferred embodiment of the present invention, the at least one carboxylic acid is selected from the group consisting of citric acid, sulfosalicylic acid, sulfosuccinic acid, glycolic acid, oxalic acid, propionic acid, maleic acid, ascorbic acid, neopentanoic acid, nitrilotriacetic acid, tartaric acid, ethylenediaminetetraacetic acid (EDTA) , malonic acid, succinic acid, and glutaric acid, preferably citric acid.

[0053] It is preferred to keep the amount of citric acid in the composition according to the present invention as low as possible .

[0054] According to another preferred embodiment of the present invention, the composition comprises 0.05 wt% or less, preferably 0.005 wt% to 0.05 wt%, more preferably 0.005 wt% to 0.01 wt%, of at least one stannate stabilizer, preferably sodium stannate .

[0055] Stannates are known to be highly effective stabilizers against the decomposition of hydrogen peroxide. Surprisingly, it has been found that stannate stabilizers, when used in concentrations exceeding 0.01 wt%, adversely affects the stability of hydrogen peroxide in the composition of the present invention.

[0056] According to a preferred embodiment of the present invention, the composition comprises 0.1 wt% to 30 wt%, preferably 0.1 wt% to 25 wt%, more preferably 1 wt% to 20 wt%, even more preferably 1 wt% to 15 wt%, of the at least one surfactant.

[0057] The composition of the present invention comprises at least one surfactant. Surfactants are known in the art and relate to chemical compounds that decrease the surface tension or interfacial tension between two liquids. Surfactants usually have a chemical structure with two different functional groups with different affinity, namely a hydrophobic tail and a hydrophilic head. Surfactants can be classified into ionic surfactants and nonionic surfactants. Ionic surfactants can be subclassified into anionic surfactants, where the hydrophilic group dissociates into anions in aqueous solutions, cationic surfactants that dissociate into cations, and amphoteric surfactants that dissociate into anions and cations. Nonionic surfactants are surfactants that do not dissociate into ions in aqueous solutions. Thus, according to another preferred embodiment of the present invention, at least one surfactant is an anionic, cationic, nonionic, amphoteric surfactant, or a combination thereof.

[0058] According to another preferred embodiment of the present invention, the anionic surfactant is selected from the group consisting of alkylbenzene sulfonate, alkylbenzene sulfonate acid, alcohol ethoxylate or a copolymer thereof, alcohol ethoxylate propoxylate or a copolymer thereof, alkyl carboxylate, alkyl carboxylate salts, alkyl ether sulfates, alkyl ether sulfate salts, lauryl ether sulfate, lauryl ether sulfate salts, and mixtures thereof.

[0059] According to a preferred embodiment of the present invention, the alkylbenzene sulfonate acid is dodecyl benzene sulfonic acid (ABS) .

[0060] According to a further preferred embodiment of the present invention, alcohol ethoxylate is lauryl alcohol or an ether thereof .

[0061] As mentioned above, the stability of hydrogen peroxide can be negatively influenced by metal ions present in other components, such as surfactants. According to another preferred embodiment of the present invention, the composition comprises less than 0.01 wt%, more preferably less than 0.005 wt% of at least one metal ion. The concentration of metal ions in the composition can be determined by known methods in the art, such as TCP (inductively coupled plasma) spectroscopy and / or ETAAS (electro thermal atomic absorption spectroscopy) . By keeping the metal ion content low, the stability of the composition according to the present invention can be further enhanced. Preferably, the metal ions are transition or alkaline earth metal ions.

[0062] According to another preferred embodiment of the present invention, the composition further comprises at least one ingredient selected from the group consisting of brightening agents, dyes, fragrances, defoaming agents, antifoamers, builders, buffering agents, skin conditioning agents, rheology modifiers, emulsifiers, softening agents, anti-static agents, color protection agents, odor removal agents, odor capturing agents, ultraviolet light protection agents, water repellency agents and plasticizers . Brightening agents, also called "fluorescent whitening agents" (FWAs) and "fluorescent brightening agents" (FBAs) , improve the appearance of whiteness on the fabrics. In particular, brightening agents absorb ultraviolet light. The reflection in the blue region results in an effect of improved whiteness . According to a preferred embodiment of the present invention, the composition comprises 0.005 wt% to 1 wt%, preferably 0.005 wt% to 0.5 wt%, more preferably 0.005 wt% to 0.25 wt%, even more preferably 0.005 wt% to 0.15 wt%, even more preferably 0 wt% to 0.15 wt%, of the at least one brightening agent.

[0063] According to a further preferred embodiment of the present invention, the composition comprises 0.005 wt% to 0.5 wt%, preferably 0.005 wt% to 0.2 wt%, more preferably less than 0.2 wt%, of the at least one dye.

[0064] According to another preferred embodiment of the present invention, the composition comprises 0.005 wt% to 1 wt%, preferably 0.005 wt% to 0.5 wt%, more preferably less than 0.5 wt%, of the at least one fragrance.

[0065] In a number of cleaning operations, foam negatively affects good cleaning practice in that it may clog lines, reduces the pressure of cleaning, and slows down the proper agitation and mechanical operation of the cleaning devices. Hence, according to a preferred embodiment of the present invention, the composition comprises 0.005 wt% to 10 wt%, preferably 0.005 wt% to 5 wt%, more preferably 0.1 wt% to 3 wt%, of the at least one antifoamer .

[0066] According to another preferred embodiment of the present invention, at least one antifoamer is selected from the group consisting of aliphatic acids, aliphatic acids esters, alcohols, vegetable oils, waxes, mineral oils, mineral oil derivatives, dimethyl silicone, siloxanes, alkyl silanes, and hydrophobic silica antifoamer, whereby antifoamers from the group of siloxanes are most preferred.

[0067] According to another preferred embodiment of the present invention, the composition of the present invention comprises 0.001 wt% to 5 wt%, preferably 0.001 wt% to 2 wt%, of the at least one builder.

[0068] Builders can be added to the compound according to the invention to increase and protect the cleaning efficiency of the surfactants. Builders can have a number of functions, including softening, buffering, and emulsifying.

[0069] According to another preferred embodiment of the present invention, the at least one builder is selected from the group consisting of carboxylic acid salts, gluconates, and combinations thereof.

[0070] As discussed above, the composition of the present invention is useful as a washing product and / or biocidal product. Preferably, the composition of the present invention can be used as washing product for cleaning fabrics, dishware, cookware, and / or cutlery. The composition of the present invention can be added to washing machines or dish washing machines. The composition is also useful as cleaning and biocidal product in many different applications, such as in hospitals, clinics, laboratories, dental offices, home care, and chronic care facilities. In particular, the composition of the present invention can also be used in food and beverage processing and preparation, animal husbandry, the hospitality industry, and for general sanitation, e.g. janitorial services.

[0071] The composition can be used in a concentrated or diluted form. In particular, the composition of the present invention can be used at a dilution ranging from 1 to 500 times, preferably 1 to 400 times. "Dilution ranging from 1 to 500 times", as used herein, means that the liquid composition of the present invention can be diluted in the range from 1:0.1 to 1:500, preferably 1:1 to 1:400, more preferably 1:50 to 1:300, more preferably 1:50 to 1:200, with water. A composition of the present invention is particularly preferred mixed with water in a ratio from 1:0.1 to 1:500, preferably 1:10 to 1:500, more preferably from 1:50 to 1:400, more preferably 1:50 to 1:300, more preferably 1:50 to 1 : 200.

[0072] The effectiveness of the composition at these dilution rates indicates its suitability for industry use, addressing the challenge of removing stains from textiles and porous materials while maintaining disinfectant qualities. The composition according to the present invention may consistently demonstrate high efficacy in stain removal and microbial reduction across dilutions between 1 and 500 times. It has been found that the composition of the present invention keeps its unique properties even after dilution. The composition can maintain or enhance its microbiological effectiveness at more concentrated dilutions. Such efficacy is particularly pertinent in scenarios where more intense cleaning and disinfection might be necessary, such as in heavily soiled textiles or environments with stringent hygiene requirements .

[0073] A further aspect of the present invention relates to a method for preparing the stable liquid detergent composition by mixing hydrogen peroxide, the at least one peroxyacid or salts thereof, the at least one chelating stabilizer, and the at least one surfactant, as defined herein. The components of the composition can be mixed simultaneously or successively. The mixture can also be heated to a temperature of between 15 °C and 50 °C, preferably between 25 °C and 40 °C.

[0074] According to another preferred embodiment of the present invention, the pH of the mixture is adjusted to 4 or less, more preferably 2.5 or less, more preferably 1 or less, even more preferably between 0.2 and 1.

[0075] Another aspect of the present invention relates to a method for cleaning a surface or textile comprising a) the step of contacting the surface or textile with a composition according to the invention, or b) the steps of mixing a composition of the invention with water in a ratio from 1:0.1 to 1:500, preferably 1:10 to 1:500, more preferably from 1:50 to 1:400, more preferably 1:50 to 1:300, more preferably 1:50 to 1:200, and contacting the surface or textile with said mixture.

[0076] The present invention is further illustrated by the following examples, however, without being restricted thereto.

[0077] EXAMPLES

[0078] Example 1: Stability of hydrogen peroxide I

[0079] In this example the longevity and consistency of each formulation was evaluated, ensuring that the active ingredients, particularly hydrogen peroxide, maintained their efficacy over time .

[0080] Compositions of various formulations were prepared by mixing the components of each composition at defined ratios, as indicated in Tables 1 and 2. The pH of the compositions was properly adjusted by adding NaOH. The relative decay of hydrogen peroxide of each composition was tested as an indicator of stability over time . The stability testing was conducted in accordance with the standard procedures for sample aging, as outlined in the Biocidal Products Regulation (BPR, Regulation (EU) 528 / 2012 ) . Speci fically, the testing included :

[0081] - Exposure of the formulati ons to 54 °C for 14 days (accel era ted aging test) :

[0082] To simulate long-term stability, an accelerated aging protocol as outlined by the Biocidal Products Regulation (BPR) was utili zed . This method involves exposing the samples to a temperature of 54 ° C for 14 days , a process designed to mimic the effects of two years of shel f li fe in a condensed timeframe .

[0083] - Exposure of the formulati ons to 60 °C for 144 hours (Peroxide Industry Standard Method) :

[0084] The second accelerated aging protocol employed was the Peroxide Industry Standard Method for accelerated aging, a more intensive test that exposes the product to 60 ° C for 144 hours ( 6 days ) . This approach was designed to s imulate the ef fects of two years of shel f li fe within a signi ficantly shorter period . Crucially, the samples were tested every 24 hours during this period . This frequent testing allows us to closely monitor and understand the changes and degradation patterns of hydrogen peroxide in the formulation over time . The insights gained from these observations were invaluable in predicting the composition ' s long-term stability and ensuring its ef fectiveness , even under extreme conditions .

[0085] - Determina ti on of hydrogen peroxide :

[0086] Hydrogen peroxide concentration was determined by titration with 0 . 1 M KMnCt in sul furic acid medium .

[0087] The stability of the compositions of the present invention is a very important indicator of product viability and ef fectiveness over time . Stability is primarily assessed by monitoring the concentration of hydrogen peroxide , the active component known for its ef ficacy in cleaning and disinfection . To ensure a comprehensive understanding of stability, two distinct accelerated aging methods of evaluation were employed. Samples were deemed stable if the relative decay of hydrogen peroxide remained below 10 %, preferably below 5 %.

[0088] Table 1 shows the formulations of the tested compositions according to the invention. The compositions comprised sodium citrate (SC) , citric acid (CA) , dodecyl benzene sulfonic acid (ABS) , anionic surfactants including lauryl alcohol (LA; such as ROKAnol® L7A, ROKAnol® L3A, and / or ROKAnol® L10A) , alcohol ethoxylate propoxylate copolymers (AEPC; such as Rokamer®2000 and / or Rokamer®2600 ) , antifoamer (AF) , and phthalimidoperoxycaproic acid (PAP) . The formulations further contained next to the above- mentioned components 0.01 wt% 1-hydroxyethylidene-l , 1-diphos- phonic acid (HEDP) , 0.08 wt% dipicolinic acid (DA) , and 12 wt% hydrogen peroxide (H2O2) .

[0089] Table 1: Stability of hydrogen peroxide in formulations I.

[0090]

[0091] The compositions in Table 2 comprised citric acid (CA) , dodecyl benzene sulfonic acid (ABS) , anionic surfactants including lauryl alcohol (LA; such as ROKAnol® L7A, ROKAnol® L3A, ROKA- nol® L5A and / or ROKAnol® L10A) , alcohol ethoxylate propoxylate copolymers (AEPC; such as Rokamer®2000 and / or Rokamer®2600 ) , and phthalimidoperoxycaproic acid (PAP) . The formulations further contained next to the above-mentioned components 0.01 wt% 1- hydroxyethylidene-1 , 1-diphosphonic acid (HEDP) , 0.08 wt% dipicolinic acid (DA) , and 12 wt% hydrogen peroxide (H2O2 ) .

[0092] Table 2: Stability of hydrogen peroxide in formulations II.

[0093] The results in Table 1 show that samples 1 to 29 according to the invention exhibited a relative decay in hydrogen peroxide concentration of less than 10 %, most samples even less than 5 %, under the conditions mentioned above. As shown in Table 2, the samples 30 to 36 show a significant increase in hydrogen peroxide decay compared to samples 1 to 29. These results demonstrate the superior storage stability of the composition of the present invention.

[0094] Example 2: Stability of hydrogen peroxide II

[0095] Similarly, like in Example 1, stability of each formulation was evaluated by accelerated aging tests at 54 °C and 60 °C (as described above) .

[0096] Table 3 shows the influence of phthalimidoperoxycaproic acid (PAP) on hydrogen peroxide stability in formulations. The compositions comprised sodium citrate (SC) , potassium citrate (PC) , dodecyl benzene sulfonic acid (ABS) , anionic surfactants including lauryl alcohol (LA; such as ROKAnol® L7A, ROKAnol® L3A, and / or ROKAnol® L10A) , alcohol ethoxylate propoxylate copolymers (AEPC; such as Rokamer®2000 and / or Rokamer®2600 ) , antifoamer (AF) , and phthalimidoperoxycaproic acid (PAP) . The formulations further contained next to the above-mentioned components 0.01 wt% 1-hydroxyethylidene-l , 1-diphosphonic acid (HEDP) , 0.08 wt% dipicolinic acid (DA) , and 12 wt% hydrogen peroxide (H2O2) .

[0097] Table 3: Effect of different phthalimidoperoxycaproic acid

[0098] (PAP) concentrations on relative decay of hydrogen peroxide.

[0099] The data presented in Table 3 demonstrate that the stabil ity of hydrogen peroxide is influenced by the concentration of phthalimidoperoxycaproic acid . Speci fically, samples with phthalimidoperoxycaproic acid concentrations exceeding 1 wt% exhibit reduced hydrogen peroxide stability, as evidenced by a relative decay greater than 10 % . In contrast , samples with phthalimidoperoxycaproic acid concentrations of 1 wt% or less display superior stability, with a relative decay below 10 % .

[0100] Additionally, samples containing more than 1 wt% phthalimidoperoxycaproic acid were observed to lack homogeneity, with visible white precipitation of undissolved phthalimidoperoxycaproic acid noted ( refer to samples 14 and 15 in Table 3 ) . Sample homogeneity is a critical parameter in detergent formulations , as it ensures consistent washing performance and mitigates potential issues during application . Uni form distribution of components — active ingredients , surfactants , and builders — across the mixture is essential to guarantee that each dose delivers a consistent composition, thereby ensuring reliable efficacy with every use . Moreover, achieving a homogeneous mixture enhances the structural stability of the detergent , contributing to improved product integrity . Conversely, non-homogeneous formulations are prone to phase separation, aggregation, or degradation over time , which can compromise shel f li fe and usability . Thus , maintaining homogeneity is paramount for both performance and longevity of the product .

[0101] Exampl e 3 : Stabili ty of hydrogen peroxide III

[0102] To assess the influence of stabili zers on hydrogen peroxide decomposition in more detail , compositions comprising di f ferent amounts of dipicolinic acid ( DA) , 1-hydroxyethylidene- l , 1-di- phosphonic acid (HEDP ) , sodium stannate ( SSn) , and aminotris (methylenephosphonic acid) (ATMP ) were tested . Table 4 shows the results of relative decay for nine di f ferent compositions. The compositions comprised anionic surfactants including lauryl alcohol (LA; such as ROKAnol® L7A, ROKAnol® L3A, and / or ROKAnol® L10A) , alcohol ethoxylate propoxylate copolymers (AEPC; such as Rokamer®2000 and / or Rokamer®2600 ) , 1-hydroxyethyl- idene-1 , 1-diphosphonic acid (HEDP) , aminotris (meth- ylenephosphonic acid) (ATMP) , sodium stannate (SSn) , and dipicolinic acid (DA) . The formulations further contained next to the above-mentioned components 0.5 wt% potassium citrate (PC) , 12 wt% dodecyl benzene sulfonic acid (ABS) , 12 wt% hydrogen peroxide (H2O2) , 0.5 wt% antifoamer, and 0.05 wt% phthalimidoperoxycaproic acid (PAP) .

[0103] Table 4: Influence of stabilizers on hydrogen peroxide sta- bility .

[0104] As shown in Table 4, it was found that various combinations of phosphonic, aromatic, and stannate stabilizers ascertain their collective impact on stability.

[0105] Example 4: Peroxyacids

[0106] As previously noted, the stability of active components serves as a critical indicator of a product's viability and efficacy over time. Peroxyacids, akin to hydrogen peroxide, are regarded as active constituents. Consequently, their stability is an integral aspect of the overall product stability.

[0107] To evaluate the impact of various peroxyacids on the formulation, samples containing differing concentrations of phthalimidoperoxycaproic acid (PAP) or peroxyacetic acid (PAA) were prepared. The stability of both peroxyacids was assessed by measuring their relative decomposition following two previously mentioned accelerated aging tests (conducted at 54 °C and 60 °C) . The methodologies employed for the determination of phthalimidoperoxycaproic acid and peroxyacetic acid concentrations are elaborated below.

[0108] - Determination of phthalimidoperoxycaproic acid:

[0109] Phthalimidoperoxycaproic acid was determined spectrophoto- metrically with UV-Vis spectrophotometer. Samples were diluted 100-times. Absorbance was measured at wavelength of 299 nm .

[0110] - Determination of peroxyacetic acid:

[0111] Peroxyacetic acid was determined iodometrically. Samples were diluted in cold sulfuric acid medium. In the first phase, hydrogen peroxide was titrated with 0.1 M KMnCh . In the second phase, peroxyacetic acid was determined with 0.05 M Na2S2O3.

[0112] Table 5 shows the comparison of phthalimidoperoxycaproic acid (PAP) and peroxyacetic acid (PAA) stability in formulations. The compositions comprised anionic surfactants including lauryl alcohol (LA; such as ROKAnol® L7A, ROKAnol® L3A, and / or ROKAnol® L10A) , alcohol ethoxylate propoxylate copolymers (AEPC; such as Rokamer®2000 and / or Rokamer2600, and phthalimidoperoxycaproic acid (PAP) or peroxyacetic acid (PAA) . The formulations further contained next to the above-mentioned components 0.01 wt% 1-hydroxyethylidene-l , 1-diphosphonic acid (HEDP) , 0.25 wt% sodium citrate (SC) , 0.08 wt% dipicolinic acid (DA) , 12 wt% dodecyl benzene sulfonic acid (ABS) , 0.75 wt% antifoamer, and 12 wt% hydrogen peroxide (H2O2) .

[0113] Table 5: Stability of peroxyacetic acid in formulations after accelerated aging tests.

[0114] Table 6: Stability of phthalimidoperoxycaproic acid in for- mulations after accelerated aging tests.

[0115] The data presented in Tables 5 and 6 indicate that the stability of phthalimidoperoxycaproic acid (PAP) surpasses that of peroxyacetic acid (PAA) within the formulation. The superior stability of phthalimidoperoxycaproic acid is evidenced by its consistently low relative decay across all samples, with values remaining below 10 % following both accelerated aging tests. In contrast, peroxyacetic acid exhibits significantly lower stability, with a relative decay exceeding 45 % in all tested samples.

[0116] Example 5: Biocidal activity

[0117] In compliance with the Biocidal Products Regulation (BPR, Regulation (EU) 528 / 2012) , the formulations of the present invention have been subjected to stringent testing to confirm their biocidal efficacy against a range of microorganisms, with a focus on challenging pathogens such as Candida albicans. The evaluation emphasized the performance of the composition at various dilutions, particularly targeting efficacy at a 100-times dilution (1 % concentration in solution) . This specific concentration is critical as it simulates the dilution occurring in a washing machine during the main wash cycle, making it a realistic and practical test of the composition's efficacy in typical usage scenarios .

[0118] To comprehensively evaluate the biocidal performance of the composition according to the present invention, different formulations were prepared and tested, as shown in Tables 7 to 9. The compositions comprised potassium citrate (PC) , dodecyl benzene sulfonic acid (ABS) , and anionic surfactants including lauryl alcohol (LA; such as ROKAnol® L7A, ROKAnol® L3A, and / or ROKA- nol® LIO) and alcohol ethoxylate propoxylate copolymers (AEPC; such as Rokamer®2000 and / or Rokamer®2600 ) , hydrogen peroxide (H2O2) , antifoamer (AF) , and phthalimidoperoxycaproic acid (PAP) . The formulations further contained next to the above-mentioned components 0.01 wt% 1-hydroxyethylidene-l , 1-diphosphonic acid (HEDP) , and 0.08 wt% dipicolinic acid (DA) .

[0119] The compositions were further diluted 100-times to prepare a solution comprising 1 % of each composition (Table 7) . The biocidal activity against Candida albicans was tested following protocols of EN 1650 under simulated dirty conditions. The criterion for passing the test stipulates a 4-log reduction.

[0120] Table 7: Samples exhibiting high disinfection efficacy at 1 % sample dilution. Table 8: Samples exhibiting high disinfection efficacy at 0.5 % sample dilution.

[0121] Some of the samples demonstrated effective biocidal action even at a 0.5 % (200-times dilution) concentration (Table 8) . This accomplishment is particularly significant as it indicates the high potency of the composition of the present invention, even at minimal concentration levels.

[0122] Table 9: Samples demonstrating inadequate disinfection efficacy at 1 % sample dilution.

[0123] This targeted methodology underscores the product's potent biocidal capabilities, particularly in settings demanding the highest disinfection standards. Data highlighting instances of unsuccessful outcomes are detailed in Table 9.

[0124] Results from Tables 7 and 9 demonstrate that achieving the requisite 4-log reduction at a 1 % sample concentration (100-times dilution) necessitates a minimum of 10 wt% hydrogen peroxide in the formulation. Notably, samples containing 10 wt% hydrogen peroxide alone (samples 32 and 33) failed to meet this threshold. In contrast, formulations combining 10 wt% hydrogen peroxide with the addition of phthalimidoperoxycaproic acid (PAP) consistently achieved the required 4-log reduction. These findings highlight the critical role of phthalimidoperoxycaproic acid in enhancing the biocidal efficacy necessary for meeting stringent performance criteria.

[0125] Example 6: Foaming test

[0126] When utilized in washing machines, the product must maintain foam levels below a specified threshold to prevent residual foam in the machine or on garments post-cycle. Extensive testing in washing machines has established that this foaming limit corresponds to a maximum of 6 mL of foam as measured by the Bartsch test, employed to assess the foaming propensity of the samples.

[0127] Bartsch test (0. Bartsch, Kolloidchem. Beih., 20 (1) , 1924, as reported by J. J. Bickerman, Foams, Springer-Verlag, New York, 1973) is a shaking test that can be used to determine foaming and foam stability. This is achieved by measuring the initial foam height and the height of the disintegrating foam after a certain time. In the Bartsch test, foam is created with a predetermined number of manual shakes. The foam height is measured using a measuring cylinder.

[0128] Prior to conducting the Bartsch test, samples were diluted 100-times. The test was carried out using 50 mL measuring cylinders, with the diluted sample filled to the 5 mL mark. Following 20 manual shakes, the initial foam height was recorded (Vt = o) • A subsequent measurement was taken after 15 minutes (Vt= 15 min) . Foaming was then calculated as the geometric mean of the initial foam volume and the foam volume after 15 minutes.

[0129] The formulations evaluated in this example contained, in addition to hydrogen peroxide as specified in the following table, 0.01 wt% 1-hydroxyethylidene-l , 1-diphosphonic acid (HEDP) , 0.25 wt% sodium citrate (SC) , 0.08 wt% dipicolinic acid (DA) , 12 wt% dodecyl benzene sulfonic acid (ABS) , 6 wt% anionic surfactants including lauryl alcohol (LA; such as ROKAnol® L7A, ROKAnol® L3A, and / or ROKAnol® L10) , 5 wt% alcohol ethoxylate propoxylate copolymers (AEPC; such as Rokamer®2000 and / or Roka- mer®2600) , 0.05 wt% phthalimidoperoxycaproic acid (PAP) , and 0.75 wt% antifoamer.

[0130] Table 10: Foaming properties of samples with different hydrogen peroxide concentrations.

[0131] According to results in Table 10, optimal foaming is observed in samples with a hydrogen peroxide concentration of 14 wt% or less (samples 1 to 6) , resulting in foam volumes below 6 mL . Conversely, samples exceeding 14 wt% hydrogen peroxide (samples 7 to 11) exhibit diminished foaming performance, with foam volumes surpassing 6 mL .

Claims

CLAIMS1. A stable liquid detergent composition comprising- 10 wt% to 14 wt% hydrogen peroxide,- 0.005 wt% to 1 wt% phthalimidoperoxycaproic acid or a salt thereof,0.0005 wt% to 1 wt% of at least one chelating stabilizer, and- 0.1 wt% to 40 wt% of at least one surfactant, and optionally water to 100 wt%.

2. The composition of claim 1, wherein the pH of said composition is 4 or less.

3. The composition of claim 1 or 2, wherein the pH of said composition is between 0.2 and 4.

4. The composition of any one of claims 1 to 3, wherein the composition comprises 10 wt% to 12 wt% hydrogen peroxide.

5. The composition of any one of claims 1 to 4, wherein the composition comprises 0.05 wt% to 1 wt% phthalimidoperoxycaproic acid or a salt thereof.

6. The composition of any one of claims 1 to 5, wherein the at least one chelating stabilizer is a phosphonic stabilizer, an aromatic stabilizer or a combination thereof.

7. The composition of claim 6, wherein the composition comprises0.0005 wt% to 1 wt% of the at least one phosphonic stabilizer.

8. The composition of claim 6 or 7, wherein the at least one phosphonic stabilizer is selected from the group consisting of 1-hydroxyethylidene-l , 1-diphosphonic acid (HEDP) , aminotris (methylenephosphonic acid) (ATMP) , diethylenetriamine penta (methylenephosphonic acid) (DTPMP) , hexamethylenediamine tetra (methylenephosphonic acid) (HMDTMP) , ethylenediamine tetra (methylenephosphonic acid) (EDTMP) , 2-phosphonobutane-1 , 2 , 4-tricarboxylic acid (PBTC) , bis (hexamethylenetriamine penta (methylenephosphonic acid) ) , and mixtures thereof.

9. The composition of any one of claims 6 to 8, wherein the composition comprises 0.0005 wt% to 1 wt%, preferably 0.0005 wt% to 0.5 wt%, of the at least one aromatic stabilizer.

10. The composition of any one of claims 6 to 9, wherein the at least one aromatic stabilizer is selected from the group consisting of dipicolinic acid, picolinic acid, and salicylic acid.

11. The composition of any one of claims 1 to 10, wherein the composition comprises further at least one inorganic stabilizer preferably selected from the group consisting of phosphoric acid, nitric acid, pyrophosphoric acid salts, and mixtures thereof .

12. The composition of any one of claims 1 to 11, wherein the composition comprises further 0.05 wt% or less of at least one stannate stabilizer, preferably of sodium stannate.

13. The composition of any one of claims 1 to 12, wherein the composition comprises 0.1 wt% to 30 wt% of the at least one surfactant .

14. The composition of any one of claims 1 to 13, wherein the at least one surfactant is an anionic, cationic, nonionic, amphoteric surfactant, or a combination thereof.

15. Use of the composition of any one of claims 1 to 14 as a washing product and / or a biocidal product.

16. Method for cleaning a surface or textile comprising a) the step of contacting the surface or textile with a composition according to any one of claims 1 to 14, or b) the steps of mixing a composition of any one of claims1 to 14 with water in a ratio from 1:0.1 to 1:500, preferably1:10 to 1:500, more preferably from 1:50 to 1:400, and contacting the surface or textile with said mixture.

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