KR20000053238A - Aqueous alkaline peroxygen bleach-containing compositions - Google Patents

Abstract

PURPOSE: Provided is aqueous alkaline peroxygen bleach-containing compositions, and more particularly, stabilized and buffered compositions. CONSTITUTION: A stable liquid aqueous cleaning composition has a pH above 8, and comprises a peroxygen bleach, a radical scavenger, a chelating agent and a pH buffer. In a preferred embodiment, the composition further comprises an antimicrobial compound like an antimicrobial essential oil and/or an active thereof. In another preferred embodiment, the composition further comprises a solvent and/or a surfactant.

Description

Composition containing alkaline aqueous peroxygen bleach {AQUEOUS ALKALINE PEROXYGEN BLEACH-CONTAINING COMPOSITIONS}

Aqueous detergent compositions for household goods have been used for years as bleach to bleach and / or disinfect hard surfaces and / or fabrics. Hypochlorite bleach has been used most widely for this purpose because it is very effective and inexpensive. A disadvantage associated with hypochlorite is that consumers are perceived as not completely satisfied in terms of safety profiles.

Aqueous compositions comprising peroxygen bleach have generally not been used in the market for household goods, but they provide effective bleaching and / or disinfecting properties and have been recognized by consumers as being less coarse than hypochlorite-based compositions. For example, hydrogen peroxide has generally been recognized as environmentally acceptable because the decomposition products are oxygen and water. The lack of use in household goods is thought to be due in part to the instability of the compositions containing aqueous peroxygen bleach. This instability is especially pronounced in alkaline media, which are mainly caused by contamination of metal ions occurring in the composition itself and / or wash liquor after the composition is diluted with water.

In addition, compositions containing these aqueous peroxygen bleaches provide effective bleaching and / or disinfecting properties, but they do not effectively remove oily contaminants. Thus, there is still room to further improve the oily contaminant removal capability of compositions containing liquid aqueous peroxygen bleach.

It is therefore an object of the present invention to provide a composition containing a liquid aqueous peroxygen bleach which is effective in removing oily contaminants and which is chemically more stable and provides effective disinfecting capacity.

It is recently known that this object can be achieved by formulating a liquid alkaline aqueous composition comprising a peroxygen bleach, a radical scavenger, a chelating agent and a pH buffer and having a pH greater than 8.

Indeed, surprisingly chelating agents, preferably phosphonate / amino phosphonate chelating agents, radical scavengers, preferably di-tert-butyl hydroxy toluene (BHT) and / or butyl hydroxyanisole (BHA) It has been found that the combination of, and pH buffers, preferably borate pH buffers, in compositions containing alkaline aqueous peroxygen bleach can maintain both pH and peroxygen bleach stability over long term storage. It has also recently been found that compositions containing aqueous peroxygen bleach, including chelating agents, radical scavengers and pH buffers, are formulated at pHs higher than 8 to provide improved oily contaminant removal while providing effective disinfection.

The compositions according to the invention are suitable for use on all types of surfaces, including hard surfaces, inanimate surfaces such as fabrics, fabrics, carpets and the like, as well as biological surfaces such as human skin, oral cavity and the like. Preferred uses of the compositions of the invention are the use of hard surfaces and / or laundry applications such as laundry detergents, laundry additives or even laundry pretreatments. More specifically, the advantage of the compositions according to the invention is that they are suitable for use on delicate surfaces. Indeed, when the composition according to the invention is used in laundry applications, fabric damage and / or color damage is reduced when compared to the same composition without chelating agents and / or radical scavengers.

The aqueous compositions of the present invention may comprise antimicrobial compounds, preferably antimicrobial essential oils and / or antimicrobial active essential oils, which further contribute to the disinfectability of the composition. The advantage of such compositions is that they disinfect effectively against a wide range of strains, including gram positive and gram negative strains, as well as more resistant microorganisms (eg fungi), even at high dilution concentrations, for example, below dilution concentrations of 1: 100 (composition: water). Is to provide.

The aqueous compositions herein can include one or more surfactants and / or one or more solvents that further contribute to their overall decontamination ability.

EP 209 228B has a pH of 1 to 8 and has a peroxygen component (eg hydrogen peroxide), a metal chelating agent (eg amino phosphonate) and a radical scavenger (eg di-tert-butyl hydride). Stabilized peroxide compositions comprising oxytoluene).

Summary of the Invention

The present invention includes a stable liquid aqueous cleaning composition having a pH greater than 8 and comprising peroxygen bleach, radical scavenger, chelating agent and pH buffer.

In a preferred embodiment of the invention, the composition further comprises an antimicrobial compound, such as an antimicrobial essential oil and / or an antimicrobial active essential oil.

In another preferred embodiment of the invention, the composition further comprises a solvent and / or a surfactant.

The present invention relates to compositions containing alkaline aqueous peroxygen bleach, more particularly to stabilized and buffered compositions.

The composition according to the invention comprises as the first essential component a peroxygen bleach or mixtures thereof. Preferred peroxygen bleach is hydrogen peroxide or its water-soluble source or mixtures thereof. Hydrogen peroxide is most preferred for use in the compositions according to the invention.

The presence of peroxygen bleach, in particular hydrogen peroxide, in the composition according to the invention is believed to assist in the disinfection and / or bleaching of the composition.

Hydrogen peroxide source, as used herein, refers to any compound that generates perhydroxyl ions when the compound is in contact with water. Suitable water soluble sources of hydrogen peroxide for use herein include percarbonates, persilicates, persulfates (such as monopersulfates), perborates, peroxy acids (such as diperoxydodecanedioic acid (DPDA)), magnesium perphthalic acid, Dialkylperoxides, diacylperoxides, preformed percarboxylic acids, organic and inorganic peroxides and / or hydroperoxides or mixtures thereof.

Typically the compositions herein comprise 0.01 to 15% by weight, preferably 0.1 to 10% by weight, more preferably 0.5 to 8% by weight, most preferably based on the weight of the total composition of the peroxygen bleach or mixture thereof 0.3 to 5% by weight.

The composition according to the invention comprises as a second essential component a chelating agent or a mixture thereof. Chelating agents suitable for use herein are selected from the group consisting of phosphonate chelating agents, aminophosphonate chelating agents, substituted heteroaromatic chelating agents, and mixtures thereof.

Phosphonate chelating agents suitable for use herein include etidronic acid (1-hydroxyethylene-diphosphonic acid (HEDP)) and / or alkali metal ethane 1-hydroxydiphosphonate.

Suitable amino phosphonate chelating agents for use herein are amino alkylene poly (alkylene phosphonates), nitrilotris (methylene) triphosphonates, ethylene diamine tetra methylene phosphonates and / or diethylene triamine Penta methylene phosphonate.

These phosphonate / amino phosphonate chelating agents may be present in all or part of the acid functionality in acid form or in the form of salts of different cations. Such phosphonate / amino phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST.

As used herein, substituted heteroaromatic chelating agents include hydroxypyridine-N-oxides or derivatives thereof.

Suitable hydroxy pyridine N-oxides and derivatives thereof used according to the invention are In which X is nitrogen, Y is oxygen, -CHO, -OH, (CH ₂ ) _n -COOH group, n is 0 to 20, preferably 0 to 10, more preferably Is an integer of 0, and Y is preferably oxygen. Thus, particularly preferred hydroxy pyridine N-oxides and derivatives thereof for use herein are 2-hydroxy pyridine N-oxides.

Hydroxy pyridine N-oxides and derivatives thereof can be purchased from Sigma.

These chelating agents, in particular phosphonate chelating agents such as 1-hydroxyethylene diphosphonic acid, have been found to not only contribute to the chemical stability of the compositions of the present invention comprising peroxygen bleach (eg hydrogen peroxide) but also to disinfectability of such compositions. Particular preference is given to the compositions according to the invention.

Typically, the chelating agent or mixtures thereof are present in the composition of the present invention in an amount of 0.001 to 10% by weight, preferably 0.005 to 5% by weight, more preferably 0.01 to 2% by weight, based on the weight of the total composition. do.

The composition according to the invention comprises as a third essential component a radical scavenger or a mixture thereof. Suitable radical scavengers for use herein include well known substituted mono and dihydroxy benzenes and derivatives thereof, alkyl- and aryl carboxylates and mixtures thereof. Preferred radical scavengers for use herein are di-tert-butyl hydroxy toluene (BHT), p-hydroxy-toluene, hydroquinone (HQ), di-tert-butyl hydroquinone (DTBHQ), mono- Tert-butyl hydroquinone (MTBHQ), tert-butyl-hydroxy anisole (BHA), p-hydroxy-anisole, benzoic acid, 2,5-dihydroxy benzoic acid, 2,5-dihydroxyterephthalic acid , Toluic acid, catechol, tert-butyl catechol, 4-allyl catechol, 4-acetyl catechol, 2-methoxy-phenol, 2-ethoxy-phenol, 2-methoxy-4- (2- Propenyl) phenol, 3,4-dihydroxy benzaldehyde, 2,3-dihydroxy benzaldehyde, benzylamine, 1,1,3-tris (2-methyl-4-hydroxy-5-tertiary- Butylphenyl) butane, tert-butyl-hydroxy-aniline, p-hydroxy aniline, as well as n-propyl-gallate. Di-tert-butyl hydroxy toluene and / or tert-butyl-hydroxy anisole sold by SHELL as IONOL CP® is highly preferred for use herein. These radical scavengers also contribute to the stability of the compositions containing the peroxygen bleach herein.

Typically, the composition according to the invention comprises 0.0005 to 5% by weight, preferably 0.005 to 1.5% by weight, more preferably 0.01 to 1% by weight of radical scavengers or mixtures thereof, based on the weight of the total composition. .

The composition according to the invention comprises as a fourth component a pH buffer or a mixture thereof.

As used herein, "pH buffer" refers to a system consisting of a compound or combination of compounds that only slightly changes in pH when a strong acid or strong base is added. Thus, the inclusion of a pH buffer in the composition of the present invention can maintain the pH of the composition higher than 8 even during long term storage over the lifetime of the composition as compared to the same composition without the pH buffer.

Suitable pH buffers for use herein include borate pH buffers, phosphonates, silicates and mixtures thereof.

Borate pH buffers suitable for use herein include alkali metal salts of borate, alkyl borate, and mixtures thereof. Borate pH buffers suitable for use herein include borate, metaborate, tetraborate, octoborate, pentaborate, dodecarborate, borontrifluoride and / or alkyl borate having 1 to 12 carbon atoms, preferably 1 to 4 carbon atoms. Alkali metal salts. Suitable alkyl borates include methyl borate, ethyl borate and propyl borate. Alkali metal salts of metaborate (eg sodium metaborate), tetraborate (eg sodium tetraborate decahydrate) or mixtures thereof are particularly preferred herein.

Boron salts, such as sodium metaborate and sodium tetraborate, are trademarks of sodium metaborate® and Borax® under the trade names Borax and Societa Chimica Raderello (Borax and Societa Chimica). Larderello).

Typically, the compositions according to the invention are 0.001 to 15% by weight, preferably 0.01 to 10% by weight, more preferably 0.01 to 5% by weight, most preferably based on the weight of the total composition Comprises 0.1 to 3% by weight.

The composition according to the invention is aqueous. The composition preferably comprises 55 to 99% by weight, preferably 80 to 99% by weight, more preferably 85 to 98% by weight, based on the weight of the total composition.

The aqueous composition according to the invention has a pH of greater than 8, preferably of 8.1 to 10, more preferably of 8.2 to 9.5, more preferably of 8.2 to 8.8. The pH of the composition can be adjusted using an alkalizing agent. Examples of alkalizing agents are alkali metal hydroxides such as potassium hydroxide and / or sodium hydroxide, or alkali metal oxides such as sodium and / or potassium oxide.

As used herein, "effective disinfection" means that the alkaline aqueous compositions of the present invention, including peroxygen bleach, radical scavengers, chelates, and pH buffers, can significantly reduce the amount of bacteria on contaminated surfaces. Indeed, effective disinfecting properties include Candida albicans present on contaminated surfaces, as well as Gram-negative bacteria such as Staphylococcus aureus and Gram-negative bacteria such as Pseudomonas aeruginosa. It is obtained on a variety of microorganisms, including fungi, for example.

The antiseptic ability of the composition can be measured by the bactericidal activity of the composition. Suitable test methods for evaluating the bactericidal activity of the composition on clean surfaces are described in the European Standard for Standardization, published in November 1995 by the European Committee for Standardisation (European Standard, prEN 1040, CEN / TC 216 N 78). It is. The European Standard, prEN 1040, CEN / TC 216 N 78, specifies the test method and the requirements for the minimal bactericidal activity of the disinfectant composition. If bacterial colony forming units (cfu) were reduced from 10 ⁷ cfu (initial level) to 10 ² cfu (final level after contact with the disinfection product), the test passed, i.e. a reduction in viability of 10 ⁵ need. The composition according to the invention passes this test even when used in a very diluted state.

As used herein, the term "effective chemical stability" means that the alkaline aqueous compositions of the present invention, including peroxygen bleach, radical scavengers, chelating agents and pH buffers, are increased compared to the same composition that does not contain, for example, radical scavengers. It provides chemical stability.

The chemical stability of the composition can be assessed by measuring the concentration of available oxygen (often abbreviated as AvO ₂ ) at a given storage period after the composition has been prepared. The concentration of the effective oxygen can be measured by chemical titration methods known in the art, such as iodine titration, thiosulfamic acid titration, permanganese titration, and cerium sulfate titration. Criteria for selection of such and appropriate methods are described, for example, in WCSchumb, CNSatterfield and Wentworth ("Hydrogen Peroxide", Reinhold Publishing Corporation, New York, 1955) and Swon ( Daniel Swern, "Organic Peroxides", Editor Wiley Int. Science, 1970.

By “increased removal capacity of oily contaminants” as used herein is meant that the alkaline aqueous compositions of the present invention comprising peroxygen bleach, radical scavengers, chelating agents and pH buffers do not comprise such pH buffers but have the same composition with the same pH. Compared with, it provides increased removal capacity for oily contaminants.

The oily contaminant removal ability of certain compositions on contaminated surfaces can be assessed by the following test methods. For example, typical contaminated tiles to be used for decontamination are contaminated with a thin layer of oil, such as dirty car oils or household oils (eg olive oil / rapeseed oil), and then fired in an oven for 1 to 2 hours to adhere oil to the tiles. It may be a white magnetic tile reinforced. The composition according to the invention and the reference composition, such as the same composition, which does not contain the pH buffer, are applied to two identical portions of the contaminated tile undiluted for 1 minute, then removed with tap water and lightly brushed dry with a paper cloth. Serve

Contaminant removal can be assessed by comparing two parts of the tile treated as described above side by side. Visual grading scales (eg, 0-4) can be used to differentiate the panel score unit (psu).

The aqueous composition of the present invention may comprise an antimicrobial compound or mixtures thereof as an optional component.

Antimicrobial compounds suitable for use herein include antimicrobial essential oils or antimicrobial active essential oils, parabens, glutaraldehyde or mixtures thereof.

Preferred antimicrobial compounds for use herein are antimicrobial essential oils or active essential oils thereof. Antimicrobial essential oils suitable for use in the compositions are essential oils exhibiting antimicrobial activity. By “active essential oil” is meant herein any component of the essential oil that exhibits antimicrobial activity. Antimicrobial essential oils and their active essential oils are expected to act as protein denaturants. In addition, antimicrobial essential oils and their active essential oils are natural compounds that, when used to disinfect any surface, contribute to the safety profile of the compositions of the present invention. Another advantage of antimicrobial essential oils and their active essential oils is that they give a pleasant odor to the alkaline aqueous compositions of the present invention without the need to add flavorings. Thus, the advantage of the alkaline aqueous composition according to the present invention is that it provides a pleasant fragrance as well as excellent oily contaminant removal and effective disinfection.

These essential oils include thyme, lemongrass, citrus, lemon, orange, anise, clove, anise fruit, broiler, geranium, rose, mint, lavender, citronella, eucalyptus, peppermint, camphor, sandalwood, cedar and mixtures thereof. Including but not limited to these. The active essential oils to be used herein include thymol (eg present in thyme), jugenol (eg present in broilers and cloves), menthol (eg present in mints), geraniol (eg present in geraniums and roses) Verbenone (e.g., in Verbain), eucalyptol and pinocarbon (in eucalyptus), cedrol (e.g. in sandalwood), anetitol (e.g. in anise), cabarcrol , Hinokithiol, berberine and mixtures thereof. Preferred active essential oils for use herein are thymol, eugenol, verbenone, eucalyptol and / or geraniol.

Timol can be purchased, for example, from Aldrich and jugenol can be purchased from Sigma, Systems-Bioindustries-Manheimer Inc. (Sigma).

Suitable parabens for use in the compositions herein include ethyl parabens, methyl parabens, propyl parabens or mixtures thereof.

Glutaraldehyde can be purchased from Union Carbide or BASF.

Typically, the compositions comprise up to 5% by weight, preferably 0.006 to 4% by weight, more preferably 0.05 to 2% by weight, of antimicrobial compounds or mixtures thereof, based on the weight of the total composition.

The compositions of the present invention may further comprise any surfactant known to those skilled in the art, including nonionic, anionic, cationic, zwitterionic and / or zwitterionic surfactants. Such surfactants are preferred herein because they can contribute more to the cleaning ability of the present compositions.

Typically the compositions according to the invention comprise up to 50% by weight, preferably 0.1 to 30% by weight, more preferably 0.2 to 25% by weight, of surfactants or mixtures thereof, based on the weight of the total composition.

Particularly suitable anionic surfactants for use herein include water soluble salts or acids of the formula ROSO ₃ M, wherein R preferably consists of hydrocarbyl having 6 to 24 carbon atoms, preferably alkyl having 8 to 20 carbon atoms. Alkyl or hydroxyalkyl with urea, more preferably alkyl or hydroxyalkyl having 8 to 18 carbon atoms, M is H or a cation such as an alkali metal cation (eg sodium, potassium, lithium) or ammonium or substituted ammonium Derived from alkylamines such as, for example, methyl-, dimethyl- and trimethyl ammonium cations and quaternary ammonium cations such as tetramethylammonium, dimethyl pipedinium cations, and ethylamine, diethylamine, triethylamine and mixtures thereof Quaternary ammonium cation).

Other anionic surfactants suitable for use herein include alkyl-diphenyl-ether-sulfonates and alkyl-carboxylates. Other anionic surfactants include salts of soap (e.g., sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts), linear alkylbenzenesulfonates with 9 to 20 carbon atoms Sulfonated polycarboxylic acid salts prepared by sulfonating pyrolysis products of primary or secondary alkanesulfonates of 8 to 22 carbon atoms, olefinsulfonates of 8 to 24 carbon atoms, alkaline earth metal citrate as described in British Patent No. 1,082,179 Alkyl polyglycol ether sulfate having 8 to 24 carbon atoms (containing 10 mol or less of ethylene oxide); Alkyl ester sulfonates such as methyl ester sulfonate having 14 to 16 carbon atoms; Acyl glycerol sulfonate, fatty oleyl glycerol sulfate, alkyl phenol ethylene oxide ether sulfate, paraffin sulfonate, alkyl phosphate, isethionate (e.g. acyl isethionate), N-acyl taurate, alkyl succinamate and sulfosuccinate Sinates, monoesters of sulfosuccinates (particularly saturated and unsaturated monoesters having 12 to 18 carbon atoms), diesters of sulfosuccinates (in particular diesters having saturated and unsaturated carbon atoms of 6 to 14), acyl Sarcosinates, sulfates of alkylpolysaccharides (e.g. sulfates of alkylpolyglucosides, nonionic nonsulfated compounds are described below), branched primary alkyl sulfates, alkyl polyethoxy carboxylates (e.g. (CH ₂ CH ₂ O) _k CH ₂ COO ^- M ⁺ A compound wherein R is alkyl having 8 to 22 carbon atoms and k is 0 to 1 Integer is 0 and M is a soluble salt-forming cation). Resin acids and hydrogenated resin acids are also suitable, such as rosin and hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Schwartz, Perry and Berch, "Surface Active Agents and Detergents", Vol. I and II] is another example. These various surfactants are also described in US Pat. No. 3,929,678, line 23, line 58 to line 29, line 23, issued December 30, 1975 to Laughlin et al., Which is incorporated herein by reference. Is cited.

Preferred anionic surfactants for use in the compositions are alkyl benzene sulfonates, alkyl sulfates, alkyl alkoxylated sulfates, paraffin sulfonates and mixtures thereof. Zwitterionic surfactants suitable for use herein include amine oxides of the formula R1R2R3NO, wherein each of R1, R2 and R3 is independently a substituted or unsubstituted linear or branched saturated hydrocarbon chain of 1 to 30 carbon atoms. . Preferred amine oxide surfactants for use according to the invention are amine oxides of the formula R 1 R 2 R 3 NO, wherein R 1 is 1 to 30 carbon atoms, preferably 6 to 20, more preferably 8 to 16, most preferably 8 to 10 carbon atoms. R 2 and R 3 are independently substituted or unsubstituted linear or branched hydrocarbon chains having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, more preferably a methyl group. R 1 may be a substituted or unsubstituted linear or branched saturated hydrocarbon chain.

Suitable amine oxides for use herein are, for example, natural blends of amine oxides having 8 to 10 carbon atoms and amine oxides having 12 to 16 carbon atoms available from Hoechst.

Zwitterionic surfactants suitable for use herein contain both cationic and anionic hydrophilic groups on the same molecule at relatively broad pH. Typical cationic groups are quaternary ammonium groups, but groups charged in amounts such as phosphonium, imidazolium and sulfonium groups may be used. Typical anionic hydrophilic groups include carboxylates and sulfonates, but other groups such as sulfates, phosphonates, and the like can be used. Formula for some zwitterionic surfactants to be used herein is ^{_{R 1 -N + (R 2)}} (R 3) R 4 X - , and, R ₁ is a hydrophobic group, R ₂ and R ₃ are each of 1 to 4 carbon atoms Alkyl, hydroxy alkyl, or other substituted alkyl group which may be linked to N to form a ring structure, R ₄ is a moiety that connects a cationic nitrogen atom to a hydrophilic group, typically alkyl having 1 to 10 carbon atoms Ylene, hydroxy alkylene or polyalkoxy group, X is a hydrophilic group which is preferably a carboxylate or sulfonate group. R _{1, which} is a preferred hydrophobic group, is an alkyl group having 1 to 24 carbon atoms, preferably less than 18 carbon atoms, more preferably less than 16 carbon atoms. Hydrophobic groups may contain unsaturated and / or substituents and / or linking groups (eg, aryl groups, amido groups, ester groups, etc.). In general, simple alkyl groups are preferred for reasons of cost and stability.

Highly preferred zwitterionic surfactants include betaine and sulfobetaine surfactants, derivatives thereof, or mixtures thereof. Betaine or sulfobetaine surfactants are preferred herein because they increase the permeability of the fungal cell wall and thereby contribute to disinfection by allowing other active ingredients to enter the cell.

In addition, due to the mild action profile of the betaine or sulfobetaine surfactants, the surfactants are particularly suitable for cleaning sensitive surfaces, such as sensitive laundry or surfaces in contact with food and / or babies. In addition, betaine and sulfobetaine surfactants are extremely mild to the skin and / or surface to be treated.

Betaine and sulfobetaine surfactants suitable for use herein include beta containing both basic and acidic groups, which molecules provide both molecules of cationic and anionic hydrophilic groups over a wide pH range and form internal salts. Phosphorus / sulfobetaine and betaine detergents. Some common examples of such detergents are described in US Pat. No. 2,082,275, US Pat. No. 2,702,279, and US Pat. No. 2,255,082, which are incorporated herein by reference. Preferred betaines and sulfobetaines herein Wherein R1 is a hydrocarbon chain having 1 to 24 carbon atoms, preferably 8 to 18 carbon atoms, more preferably 12 to 14 carbon atoms, and R2 and R3 are hydrocarbon chains having 1 to 3 carbon atoms, preferably 1 to 3 carbon atoms. N is 1 to 10, preferably 1 to 6, more preferably an integer of 1, Y is selected from the group consisting of carboxyl and sulfonyl radicals, and R 1, R 2 and R 3 hydrocarbon chains or mixtures thereof The sum is 14 to 24 carbon atoms.

Examples of particularly suitable betaine surfactants include alkyl dimethyl betaines with 12 to 18 carbon atoms (eg coconut betaine) and alkyl dimethyl betaines with 10 to 16 carbon atoms (eg laurylbetaine). Coconut betaine is available from Seppic under the trade name Amonyl 265®. Laurylbetaine is commercially available from Albright & Wilson under the tradename Empigen BB / L®.

Other specific zwitterionic surfactants include the formula R ₁ -C (O) -N (R ₂ )-(C (R ₃ ) ₂ ) _n -N (R ₂ ) ₂ ⁽⁺⁾ -(C (R ₃ ) ₂ ) _n -SO ₃ ^(-) or R ₁ -C (O) -N (R ₂ )-(C (R ₃ ) ₂ ) _n -N (R ₂ ) ₂ ⁽⁺⁾ -(C (R ₃ ) ₂ ) _n -COO ^(-) , wherein each R ₁ is a hydrocarbon group such as an alkyl group having 8 to 20 carbon atoms, preferably 18 or less, more preferably 16 or less, and each of R ₂ is hydrogen (amido Attached to nitrogen), short chain alkyl or substituted alkyl of 1 to 4 carbon atoms, preferably methyl, ethyl, propyl, hydroxy, substituted ethyl or propyl and mixtures thereof, preferably methyl, and R Each ₃ is selected from the group consisting of hydrogen and hydroxy groups, each n is an integer from 1 to 4, preferably 2 or 3, more preferably 3, and optionally (C (R ₃ ) ₂ ) Having no more than one hydroxy group of residues. R ₁ groups may be branched and / or unsaturated. R ₂ groups may also be linked to form a ring structure. This type of surfactant is a fatty acylamidopropylene (hydroxypropylene) sulfobetaine having from 10 to 14 carbon atoms available under the trade name "Varion CAS sulfobetaine" from the Serex Company. .

In one preferred embodiment of the invention in which the present compositions are particularly suitable for disinfecting hard surfaces, the surfactants preferably comprise amine oxides and betaine or sulfobetaine surfactants, preferably 1: 1 to 100: 1, more preferably 6: Surfactant systems that typically comprise a weight ratio of 1 to 100: 1, most preferably 10: 1 to 50: 1, are typical. The use of such surfactants in the compositions for cleaning hard surfaces herein provides a cleaned surface with a gloss effect such that the degree of filming / bleaching remaining on the cleaned surface treated with the composition is minimized.

Suitable nonionic surfactants for use herein are commercial fatty alcohol ethoxylates and / or propoxylates having various fatty alcohol chain lengths and varying degrees of ethoxylation. Indeed the HLB value of such alkoxylated nonionic surfactants depends essentially on the chain length of the fatty alcohol, the nature of the alkoxylation and the degree of alkoxylation. A number of surfactants, including nonionic surfactants, can be purchased with a list of surfactants listed with their respective HLB values.

Hydrophobic nonionic surfactants having an HLB (hydrophilic lipophilic equilibrium) of less than 16, preferably less than 15, more preferably less than 12, most preferably less than 10 are particularly suitable herein as nonionic surfactants. These hydrophobic nonionic surfactants have been found to provide good oily cleavage.

Preferred hydrophobic nonionic surfactants for use in the compositions according to the invention are surfactants having a HLB of less than 16, according to the formula RO- (C ₂ H ₄ O) _n (C ₃ H ₆ O) _m H, wherein R is an alkyl chain having 6 to 22 carbon atoms or an alkyl benzene chain having 6 to 28 carbon atoms, n + m is 0 to 20, n is 0 to 15, m is 0 to 20, preferably n + m Is 1 to 15, n and m are 0.5 to 15, more preferably n + m is 1 to 10, and n and m are 0 to 10. Preferred R for use herein is an alkyl chain having 8 to 22 carbon atoms. Accordingly, hydrophobic nonionic surfactants suitable for use herein include Dobanol® 91-2.5 (HLB = 8.1; R is a mixture of alkyl chains of 9 and 11 carbon atoms, n is 2.5 and m is 0), Lutensol® TO3 (HLB = 8; R is an alkyl chain of 13 carbon atoms, n is 3, m is 0), Lutensol AO3 (HLB = 8; R is 13 carbon atoms) Is a mixture of an alkyl chain and an alkyl chain of 15 carbon atoms, n is 3 and m is 0), Tergitol® 25L3 (HLB = 7.7; R is an alkyl chain length of 12 to 15 carbon atoms, n Is 3, m is 0), dovanol 23-3 (HLB = 8.1; R is a mixture of an alkyl chain having 12 carbon atoms and an alkyl chain having 13 carbon atoms, n is 3, m is 0), dobanol 23-2 (HLB = 6.2; R is a mixture of an alkyl chain of 12 carbon atoms and an alkyl chain of 13 carbon atoms, n is 2, m is 0), dovanol 45-7 (HLB = 11.6; R is 14 carbon atoms) Is a mixture of an alkyl chain of and an alkyl chain of 15 carbon atoms, and n is 7, m is 0), dovanol 23-6.5 (HLB = 11.9; R is a mixture of an alkyl chain of 12 carbon atoms and an alkyl chain of 13 carbon atoms, n is 7 and m is 0), dobanol 25 -7 (HLB = 12; R is a mixture of an alkyl chain of 12 carbon atoms and an alkyl chain of 13 carbon atoms, n is 7 and m is 0), dovanol 91-5 (HLB = 11.6; R is 9 carbon atoms) A mixture of an alkyl chain and an alkyl chain of 11 carbon atoms, n is 5, m is 0, dobanol 91-6 (HLB = 12.5; R is a mixture of an alkyl chain of 9 carbon atoms and an alkyl chain of 11 carbon atoms, n is 6, m is 0), dovanol 91-8 (HLB = 13.7; R is a mixture of alkyl chains of 9 carbon atoms and alkyl chains of 11 carbon atoms, n is 8, m is 0), Dovanol Or 91-10 (HLB = 14.2; R is a mixture of alkyl chains having 9 to 11 carbon atoms, n is 10 and m is 0) or a mixture thereof. Preference is given here to dobanol 91-2.5, lutensol TO3, lutensol AO3, tergitol 25L3, dobanol 23-3, dobanol 23-2, dobanol 23-10 or mixtures thereof. The dobanol surfactants are commercially available from SHELL. The lutensol surfactant is commercially available from BASF and the tertitol surfactant is commercially available from UNION CARBIE.

The aqueous composition herein may comprise a solvent or mixture thereof as an optional component. When a solvent is used, the solvent advantageously provides enhanced cleaning ability to the compositions herein. Suitable solvents for incorporation into the compositions according to the invention include propylene glycol derivatives such as n-butoxypropanol or n-butoxypropoxypropanol, water soluble Carbitol® solvents or water soluble cellosolves (CELLOSOLVE). Solvent. The water-soluble carbitol solvent is a compound of 2- (2-alkoxyethoxy) ethanol in which the alkoxy group is derived from ethyl, propyl or butyl. Preferred water-soluble carbitols are 2- (2-butoxyethoxy) ethanol, also known as butyl carbitol. The water-soluble cellosolve solvent is a compound of 2-alkoxyethoxyethanols, and 2-butoxyethoxyethanol is preferable. Other suitable solvents are benzyl alcohol, methanol, ethanol, isopropyl alcohol, diols such as 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol and mixtures thereof . Preferred solvents for use herein are n-butoxypropoxypropanol, butyl carbitol and mixtures thereof. Most preferred solvent for use herein is butyl carbitol.

The solvent may typically be present in the composition of the present invention in an amount of up to 10% by weight, preferably from 0.1 to 8% by weight, more preferably from 0.5 to 6% by weight, based on the weight of the total composition.

The composition according to the invention may comprise a shear thinning polymeric thickener or mixtures thereof as an optional component.

Such shear-tackifying polymer thickeners are suitable because they perform a dual function when incorporated into the liquid composition according to the present invention, which functions as a user of the mist / steam of the peroxygen bleach when sprayed onto the surface to be disinfected. Not only prevents or reduces inhalation, but also increases the time that the composition is in contact with the vertical surface, thereby reducing the likelihood of the composition dropping.

Shear viscosity polymer thickeners suitable for use herein include synthetic and natural polymers. Shear viscosity polymer thickeners suitable for use herein are polyurethane polymers, polyacrylamide polymers, polycarboxylate polymers such as polyacrylic acid and sodium salts thereof, xanthan gum or derivatives thereof, alginates or derivatives thereof , Polysaccharide polymers such as ethoxylated cellulose, carboxymethyl cellulose, hydroxymethylcellulose, hydroxypropyl cellulose, hydroxyethyl cellulose and mixtures thereof.

Preferred shear-tackifying polymer thickeners for use in the compositions of the present invention are the Kelkel Division (KELTROL®), the KELZAN AR®, Kelzan Di35 (Kelco Division of Merck). Xanthan gum or derivatives thereof sold under trade names such as registered trademark), Kelzan S (registered trademark), Kelzan Xjet (registered trademark), and the like.

Xanthan gum is a special cellular polysaccharide of Xanthomonas campestras. Xanthan gum contains corn sugar or other corn sweetener by-product and is produced by fermentation. Xanthan gum contains a poly β- (1 → 4) -D-glucopyranosyl backbone similar to that found in cellulose. Aqueous dispersions of xanthan gum and derivatives thereof exhibit significant fluidity. Xanthan gum exhibits high pseudoplasticity over very wide concentrations and results in rapid shearing decay, which is generally understood to be reversible. Preferred xanthan materials include crosslinked xanthan materials. Xanthan polymers can be crosslinked with various known covalent reactive crosslinkers that react with the hydroxy functional groups of large polysaccharide molecules and can be crosslinked using divalent, trivalent or polyvalent metal ions. Such crosslinked xanthan gels are described in US Pat. No. 4,782,901, which is incorporated herein by reference. Suitable crosslinkers for the xanthan material include metal ions such as Al ⁺³ , Fe ⁺³ , Sb ⁺³ , Zr ⁺⁴ and other transition metals. Known organic crosslinkers can also be used. Preferred crosslinked xanthans of the present invention are Kelzan AL, a product of Kelco Division of Merck.

The molecular weight of the polycarboxylate polymers for use herein is between 500,000 and 4,500,000, preferably between 1,000,000 and 4,000,000. Most preferred polymers for use herein contain from 0.5% to 4% by weight crosslinker, wherein the crosslinker tends to interconnect with the linear strands of the polymer, resulting in crosslinking products. Suitable crosslinkers include polyalkenyl polyethers. Polycarboxylate polymers include polyacrylate polymers. Other monomers other than acrylic acid can be used to form such polymers comprising monomers such as maleic anhydride that serve as a source of additional carboxyl groups. The molecular weight per carboxylate group of the monomer containing carboxylate groups is typically 25 to 200, preferably 50 to 150, more preferably 75 to 125. In addition, other monomers, such as ethylene and propylene, may be present in the monomer mixture, if desired, as a diluent.

Preferred polycarboxylate polymers for use herein are polyacrylate polymers. Commercially available polymers in the form of polyacrylates are commercially available from Carbopol®, Acrysol® ICS-1, Polygel® and Sokalan® The polymer which is being used is mentioned. Most preferred polyacrylate polymers are copolymers of acrylic acid with alkyl (C ₅ -C ₁₀ ) acrylates (commercially available from Carbopol 1623 and Carbopol 695 at BF Goodrich) and air of acrylic acid and maleic anhydride. Coalescence (commercially available under the trade name Polygel DB from 3V Chemical Company). Mixtures of any of the polycarboxylate polymers described herein may be used.

The composition according to the present invention is 10% by weight or less, preferably 0.02 to 5% by weight, more preferably 0.02 to 2% by weight, most preferably 0.02 to 1% by weight, based on the weight of the total composition. May contain%. The aqueous compositions herein further comprise a variety of other optional ingredients such as enhancers, stabilizers, bleach activators, contaminant suspensions, dye transfer agents, brighteners, anti-dust agents, enzymes, dispersants, dye transfer inhibitors, pigments, perfumes and It may also include dyes.

The aqueous compositions according to the invention formulated in liquid form may be applied undiluted or diluted. Accordingly, the present invention includes a method of cleaning a surface by applying a composition as described herein to the surface.

"Surface" as used herein means any surface including human skin, oral cavity, biologic surfaces such as teeth and non-living surfaces. Inanimate surfaces include, but are not limited to, hard surfaces such as tiles, walls, floors, chrome, glass, soft vinyl, any plastics, plasticized, found in dwellings or car decorations such as kitchens and bathrooms. Wood, table tops, sinks, counter tops, dishes, sanitary appliances (e.g. sinks), showers, shower curtains, washbasins, toilets, etc. as well as textiles, for example clothing, curtains, drape, bed linen, bathroom Linens, tablecloths, sleeping bags, tents, upholstered furniture and carpets. The non-living surface may include, but is not limited to, household products such as refrigerators, freezers, dishwashers, automatic dryers, ovens, electronic ovens, dishwashers, and the like. The compositions of the present invention have been found to be particularly suitable for cleaning and / or disinfecting non-horizontal hard surfaces.

Preferably the composition according to the invention is applied to the surface to be cleaned in diluted form.

By "diluted form" herein is meant that the composition according to the invention in liquid or solid form may be diluted by the user with a liquid, typically water. The composition may be diluted by the user with water up to 100 times its own weight, preferably 80 to 40 times, more preferably 60 to 30 times.

Thus, the present invention also encompasses diluted compositions obtainable by dilution of the compositions according to the invention with water.

The aqueous composition according to the present invention may be packaged by various suitable detergent packaging techniques known to those skilled in the art. The aqueous composition herein may preferably be packaged in a dispenser for manual spraying, which is generally composed of synthetic organic polymeric plastic material. Accordingly, the present invention also includes the aqueous cleaning composition described herein packaged in a spray dispenser, preferably a triggered spray dispenser or a pumped spray dispenser.

For example, the spray dispenser evenly sprays the aqueous composition of the present invention onto a relatively wide surface to be cleaned, contributing to the washability of the composition. Such spray dispensers are particularly suitable for treating vertical surfaces.

Suitable spray dispensers used in accordance with the present invention are, for example, passive types commercially available from Specialty Packaging Products, Inc. or Continental Sprayers, Inc. And foam trigger dispensers. Dispensers of this type are described, for example, in US Pat. No. 4,701,311 to Dunning et al., US Pat. No. 4,646,973 to Focalarcci and US Pat. No. 4,538,745. Particularly preferred for use herein are the T8500® or T8900® available from Continental Sprayers International, or the T8100® available from Canyon, Northern Ireland. Can be mentioned. In such dispensers, the liquid composition is dispensed into fine droplets and sprayed towards the surface to be treated. Indeed, in such spray dispensers, the composition contained in the body of the dispenser is sprayed through the head of the spray dispenser by the energy associated with the pumping mechanism by the user when the user activates the pumping mechanism. More specifically, in the head portion of the sprayable dispenser, the composition is forced against a blockage (such as a grid or cone, etc.) to provide an impact that assists in subdividing the liquid composition, Help to form an enemy.

The composition of the present invention may be made in the form of a "wipe". By “wipe” is meant herein a disposable towel impregnated with the liquid composition according to the invention. Preferably the wipe is packaged in a plastic box. Thus, the present invention also includes a wipe, for example a disposable paper towel impregnated / impregnated with the liquid composition as described above. The advantage of such a product is that the user can use the cleaning composition more quickly, even in places other than at home, i.e. it is not necessary to pour the liquid composition according to the invention onto the surface to be cleaned and dry it completely with a cloth. In other words, the wipe allows the surface to be cleaned in a single step.

The invention will be further illustrated by the following examples.

The following compositions were prepared comprising the components described in the proportions described (in weight percent unless otherwise indicated).

This aqueous composition passed the prEN 1040 test of the European Standardization Association. Such compositions are used in undiluted or diluted form, eg, diluted 1: 100, 1:25, 1:50 and provide the ability to remove oily contaminants.

In addition, these compositions exhibited good chemical stability even under prolonged storage and / or stress conditions. In other words, such compositions showed less than 7% effective oxygen loss after 10 days at 50 ° C.

Claims (18)

A stable liquid aqueous cleaning composition having a pH greater than 8 and comprising a peroxygen bleach, a radical scavenger, a chelating agent and a pH buffer. The method of claim 1, Peroxide bleach is hydrogen peroxide; Percarbonate, persilicate, persulfate, perborate, peroxy acid, dialkylperoxide, diacylperoxide, preformed percarboxylic acid, organic peroxide, inorganic peroxide, organic hydroperoxide, inorganic hydroperoxide and their An aqueous source of hydrogen peroxide selected from the group consisting of mixtures; Or a water-soluble source of hydrogen peroxide and hydrogen peroxide as described above, preferably hydrogen peroxide. The method according to claim 1 or 2, A composition comprising peroxygen bleach or a mixture thereof from 0.01% to 15% by weight, preferably from 0.1% to 10% by weight, more preferably from 0.5% to 8% by weight, based on the weight of the total composition. The method according to any one of claims 1 to 3, Radical scavengers are substituted mono- or di-hydroxy benzenes or derivatives thereof, alkyl carboxylates, aryl carboxylates or mixtures thereof, preferably di-tert-butyl hydroxy toluene, p-hydroxy-toluene , Hydroquinone, di-tert-butyl hydroquinone, mono-tert-butyl hydroquinone, tert-butyl-hydroxy anisole, p-hydroxy-anisole, benzoic acid, 2,5-dihydroxy benzoic acid , 2,5-dihydroxyterephthalic acid, toluic acid, catechol, tert-butyl catechol, 4-allyl-catechol, 4-acetyl catechol, 2-methoxy-phenol, 2-ethoxy-phenol, 2-methoxy-4- (2-propenyl) phenol, 3,4-dihydroxy benzaldehyde, 2,3-dihydroxy benzaldehyde, benzylamine, 1,1,3-tris (2-methyl- 4-hydroxy-5-tert-butylphenyl) butane, tert-butyl-hydroxy-aniline, p-hydroxy aniline, n-propyl-gallate or mixtures thereof, It is preferably di-tert-butyl-hydroxytoluene, 3-tert-butyl-hydroxy anisole, or di-tert-butyl hydroxy toluene, and t-butyl-hydroxy anisole composition. The method according to any one of claims 1 to 4, A composition comprising from 0.0005% to 5% by weight, preferably from 0.005% to 1.5% by weight, more preferably from 0.01% to 1% by weight, based on the weight of the total composition of the radical scavenger. The method according to any one of claims 1 to 5, The chelating agent is selected from the group consisting of phosphonate chelating agents, aminophosphonate chelating agents, substituted heteroaromatic chelating agents, and mixtures thereof, more preferably 1-hydroxyethylene-diphosphonic acid, alkali metal ethane 1 -Hydroxy diphosphonate, nitrilo trimethylene phosphonate, ethylene diamine tetra methylene phosphonate, diethylene triamine pentamethylene phosphonate, 2-hydroxypyridine-N-oxide or mixtures thereof. The method according to any one of claims 1 to 6, A composition comprising a chelating agent or a mixture thereof from 0.001% to 10% by weight, preferably from 0.005% to 5% by weight, more preferably from 0.01% to 2% by weight, based on the weight of the total composition. The method according to any one of claims 1 to 7, The pH buffer is a borate pH buffer, phosphonate, silicate or mixtures thereof, preferably borate, metaborate, tetraborate, octoborate, pentaborate, dodecaronone, borontrifluoride, alkyl having 1 to 12 carbon atoms The composition is an alkali metal salt of a borate or mixture thereof, more preferably an alkali metal salt of metaborate, tetraborate or a mixture thereof. The method according to any one of claims 1 to 8, The pH buffer or a mixture thereof is 0.001% to 15% by weight, preferably 0.01% to 10% by weight, more preferably 0.01% to 5% by weight, most preferably 0.1 based on the weight of the total composition Wt% to 3 wt% composition. The method according to any one of claims 1 to 9, Antimicrobial compounds, preferably a) thyme, lemongrass, citrus, lemon, orange, anise, clove, anise fruit, broiler, geranium, rose, lavender, citronella, eucalyptus, peppermint, camphor, Antimicrobial essential oils typically obtained from the group consisting of sandalwood, cedar and mixtures thereof, b) thymol, eugenol, menthol, carbacrol, verbenone, eucalyptol, cedrol, anetol, pinocarbon, geraniol , An antimicrobial active essential oil typically selected from the group consisting of hinokithiol, berberine, and mixtures thereof, or c) the antimicrobial essential oil and b) the antimicrobial active essential oil. The method of claim 10, A composition comprising an antimicrobial compound at most 5% by weight, preferably 0.006% to 4% by weight, more preferably 0.05% to 2% by weight based on the weight of the total composition. The method according to any one of claims 1 to 11, The composition further comprises up to 50% by weight, preferably from 0.1% to 30% by weight, more preferably from 0.2% to 25% by weight, based on the weight of the total composition. The method of claim 12, Surfactants, a) chemical formula (Wherein R 1 is a hydrocarbon chain having 1 to 24 carbon atoms, preferably 8 to 18, more preferably 12 to 14 carbon atoms, R 2 and R 3 are hydrocarbon chains having 1 to 3 carbon atoms, preferably 1 carbon atom, n Is an integer from 1 to 10, preferably an integer from 1 to 6, more preferably 1, Y is selected from the group consisting of carboxyl and sulfonyl radicals, and the sum of the carbon numbers of the R1, R2 and R3 hydrocarbon chains is about Zwitterionic surfactants or mixtures thereof, preferably betaine or sulfobetaine surfactants, derivatives thereof, or mixtures thereof, b) zwitterionic surfactants or mixtures thereof, preferably of the formula R 1 R 2 R 3 NO, wherein each R 1, R 2 and R 3 are independently substituted or unsubstituted linear or branched saturated hydrocarbon chains having 1 to 30 carbon atoms, Preferably R 1 is a substituted or unsubstituted linear or branched saturated hydrocarbon chain having 6 to 20, preferably 8 to 16, more preferably 8 to 10 carbon atoms, and R2 and R3 are independently substituted or unsubstituted Amine oxides or mixtures thereof of linear or branched hydrocarbon chains having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, more preferably methyl groups), or c) said a) zwitterionic surfactant and b) zwitterionic surfactant. The method according to any one of claims 1 to 13, A composition comprising up to 10 wt%, preferably 0.1 wt% to 8 wt%, more preferably 0.5 wt% to 6 wt% of the solvent or mixture thereof, based on the weight of the total composition. The method of claim 14, The solvent is selected from the group consisting of propylene glycol derivatives, 2- (2-alkoxyethoxy) ethanols, 2-alkoxyethoxyethanols, benzyl alcohol, methanol, ethanol, isopropyl alcohol, diols and mixtures thereof, preferably Preferably a propylene glycol derivative, 2- (2-alkoxyethoxy) ethanol and mixtures thereof. The method according to any one of claims 1 to 15, The composition has a pH of 8.1 to 10, preferably 8.2 to 9.5, more preferably 8.2 to 8.8. The method according to any one of claims 1 to 16, A composition packaged in a spray dispenser. Wipe containing a composition according to any one of claims 1 to 16.