WO2022008732A1 - Amélioration de l'activité de conservateurs antimicrobiens - Google Patents

Amélioration de l'activité de conservateurs antimicrobiens Download PDF

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WO2022008732A1
WO2022008732A1 PCT/EP2021/069201 EP2021069201W WO2022008732A1 WO 2022008732 A1 WO2022008732 A1 WO 2022008732A1 EP 2021069201 W EP2021069201 W EP 2021069201W WO 2022008732 A1 WO2022008732 A1 WO 2022008732A1
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composition
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acid
group
compound
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PCT/EP2021/069201
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Hauke Rohwer
Menno Hazenkamp
Juergen Wiethan
Gabriele BOENEMANN
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Basf Se
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants

Definitions

  • the present invention relates to compositions with improved protection against micro bial attack, especially against degradation by bacteria, yeasts and molds, by certain antimicrobial agents in combination with a specific amphoteric surfactant.
  • the present invention further relates to a method for enhancing the preserving activity of such anti microbial agents by combining them with said amphoteric surfactant, and the corre sponding use of such surfactants as boosters for the antimicrobial, and especially pre serving, activity of antimicrobial agents, especially of 2-phenoxyethanol.
  • Preservatives are antimicrobial agents which may be added to products such as food products, beverages, pharmaceuticals, paints, biological samples, cosmetic and per sonal care products, household products, industrial products, wood, and many other products to prevent decomposition by microbial growth.
  • products such as food products, beverages, pharmaceuticals, paints, biological samples, cosmetic and per sonal care products, household products, industrial products, wood, and many other products to prevent decomposition by microbial growth.
  • the function of antimicrobial agents used as preservatives is the growth control of bacteria, yeasts and molds in the product during the entire shelf-life of the product in order to prevent proliferation of mi croorganisms resulting in damaging the quality and/or functionality of the preserved product.
  • the remaining antimicrobials which are not or at least less hazardous, like 2- phenoxyethanol, are often not very effective and need to be used in rather high concentrations to achieve an acceptable antimicrobial effect.
  • high concentrations are however not acceptable; for instance because of formulation issues or malodour or because beyond a certain concentration these products become hazardous, too.
  • high concentrations fail to give the desired effect.
  • WO2013/124784 recommends addition of a polyamine for improving antimicrobial ac- tivity of a number of antimicrobial agents including phenoxyethanol. There is still need to improve the activity of environmentally safe antimicrobial agents.
  • CN 104997659 relates to a cleansing gel for the skin containing 40-60 parts of water, 3-8 parts of potassium cocoyl glycinate, 2-5 parts of disodium laurylamphoacetate, 0.2- 0.8 parts of lemon essential oil, 0.2-0.8 parts of thyme essential oil and 0.1-0.6 parts of phenoxyethanol.
  • Floralys® moist toilet tissue for sensitive skin contains inter alia phenoxyethanol and disodium lauriminodipropionate. Their amounts are not indicated on the consumer information sheet or label.
  • Bryt® Night Cream is a skin cream commercialized by The London Skincare Co. and contains inter alia phenoxyethanol and disodium lauriminodipropionate. Their amounts are not indicated on the consumer information sheet or label.
  • the object of the present invention is to improve the effect of certain antimicrobials.
  • a more specific object is to provide a composition with an improved preservative and/or biocidal effect.
  • the present invention thus primarily pertains to the use of a compound (in the following also recalled as booster compound or component (b) comprising an anion of the formu wherein each n is independently in the range of from 1 to 8, m is in the range of from 1 to 21 , especially from 5 to 17, and cations compensating the negative charge of the anion are selected from the group consisting of alkaline, ammonium, and hydrogen cations, for enhancing the antimicrobial, and especially preserving, effect of an antimicrobial agent, typically in aqueous compositions.
  • a compound in the following also recalled as booster compound or component (b) comprising an anion of the formu wherein each n is independently in the range of from 1 to 8, m is in the range of from 1 to 21 , especially from 5 to 17, and cations compensating the negative charge of the anion are selected from the group consisting of alkaline, ammonium, and hydrogen cations, for enhancing the antimicrobial, and especially preserving, effect of an antimicrobial agent,
  • the antimicrobial agent is generally selected from agents showing an antimicrobial effect and/or used for preservation purposes; typically from the group consisting of 2- phenoxyethanol, 4,4’-dichloro 2’-hydroxydiphenylether, 2-bromo-2-nitropropane-1 ,3- diol, glutaraldehyde, 2,4-dichlorobenzylalcohol, 1 ,3, 5-tris-(2-hydroxyethyl)-1 ,3,5- hexahydrotriazine, formic acid and salts thereof, benzoic acid and salts thereof, sorbic acid and salts thereof, lactic acid and salts thereof, 3-iodo-2-propynylbutylcarbamate, sodium pyrithione, and isothiazolinones such as 1 ,2-benzisothiazol-3(2H)-one.
  • agents showing an antimicrobial effect and/or used for preservation purposes typically from the group consisting of 2- phenoxyethanol, 4,4’-dichlor
  • the antimicrobial agent is selected from 2-phenoxyethanol, 4,4’-dichloro 2’- hydroxydiphenylether, 2-bromo-2-nitropropane-1 ,3-diol, glutaraldehyde, 2,4- dichlorobenzylalcohol, 1 ,3,5-tris-(2-hydroxyethyl)-1 ,3,5-hexahydrotriazine, formic acid and salts thereof, benzoic acid and salts thereof, sorbic acid and salts thereof, lactic acid and salts thereof, and isothiazolinones such as 1 ,2-benzisothiazol-3(2H)-one, more preferably from the group consisting of 2-phenoxyethanol, 4,4’-dichloro 2’- hydroxydiphenylether, 2-bromo-2-nitropropane-1 ,3-diol, glutaraldehyde, formic acid, formic acid salts, and 1 ,2-benzisothiazol-3
  • agents showing an antimicrobial effect are agents showing an antimicrobial effect and typically used for preservation purposes; such as agents from the group consisting of 2-phenoxyethanol, 2-bromo-2-nitropropane-1 ,3-diol, glutaraldehyde, formic acid, formic acid salts, benzyl alcohol, 3 -iodo-2-propynylbutylcarbamate, sodium pyrithione, benzoic acid and its salts, sorbic acid and its salts, lactic acid and its salts, and isothiazolinones such as 1 ,2-benzisothiazol-3(2H)-one.
  • Salts are typically alkaline salts like sodium salts, or calcium salts or ammonium salts. Salts showing a good water solubility are preferred; specifically preferred salts of those components (a) having an acid functionality are noted below.
  • the antimicrobial agent is selected from the group consisting of 2-phenoxyethanol, 4,4’-dichloro 2’-hydroxydiphenylether, 2-bromo-2- nitropropane-1 ,3-diol, glutaraldehyde, formic acid, formic acid salts, and isothiazoli nones such as 1 ,2-benzisothiazol-3(2H)-one More preferred therein are 2- phenoxyethanol, 4,4’-dichloro 2’-hydroxydiphenylether, 1 ,2-benzisothiazol-3(2H)-one; most preferred is 2-phenoxyethanol.
  • compositions which compositions com prise the components: a) an antimicrobial agent selected from the group consisting of 2-phenoxyethanol, 4,4’- dichloro 2’-hydroxydiphenylether, 2-bromo-2-nitropropane-1,3-diol, glutaraldehyde, 2,4- dichlorobenzylalcohol, 1 ,3,5-tris-(2-hydroxyethyl)-1 ,3,5-hexahydrotriazine, formic acid and salts thereof, benzoic acid and salts thereof, sorbic acid and salts thereof, lactic acid and salts thereof, and isothiazolinones such as 1 ,2-benzisothiazol-3(2H)-one, and b) a compound comprising an anion of the formula (1A) wherein each n is independently in the range of from 1 to 8, m is in the range of from 1 to 21 , especially from 5 to 17, and cations compensating the negative charge of the formula (1A) wherein each
  • the compound of component (b) is alternatively expressed as a com pound of the formula (1) or an alkali metal salt thereof, earth alkaline metal salt thereof or ammonium salt there of.
  • the present invention relates to a composition
  • a composition comprising (a) at least one antimicrobial agent selected from the group consisting of 2- phenoxyethanol and 4,4’-dichloro 2’-hydroxydiphenylether; and (b) at least one compound of the formula (1 ) or an alkali metal, earth alkaline metal or ammonium salt thereof wherein each n is independently in the range of from 1 to 8; and m is in the range of from 1 to 21 ; where in case that the composition is a personal care composition and the antimicrobi al agent (a) comprises 2-phenoxyethanol, the overall weight ratio of 2-phenoxyethanol and the compound of the formula (1) or the salt thereof is preferably in the range of from 1:1 to 20:1; and where in all other cases, the overall weight ratio of the antimicrobial agent (a) and the compound of the formula (1) or the salt thereof is preferably in the range of from 1:10,000 to 20:1; provided that the composition does not contain a tocopheryl phosphate, does not contain a peroxide
  • the invention relates moreover to the use of a compound of the formula (1) or a salt thereof as defined above for enhancing the antimicrobial effect of the anti microbial agent (a) as defined above (i.e. of 2-phenoxyethanol or 4,4’-dichloro 2’- hydroxydiphenylether or a mixture of the two aforementioned antimicrobials).
  • the invention relates in particular also to the use of a compound of the formula (1) or a salt thereof as defined above in combination with said antimicrobial agent (a), for en hancing the preserving effect of said combination.
  • the invention relates in particular moreover to a method for enhancing the antimicrobi al effect of an antimicrobial agent selected from the group consisting of 2- phenoxyethanol and 4,4’-dichloro 2’-hydroxydiphenylether, especially of 2- phenoxyethanol, in a formulation, which method comprises incorporation of a com pound of the formula (1) or a salt thereof as defined into said formulation; where in case that the formulation is a personal care composition and the antimicrobial agent comprises 2-phenoxyethanol, the compound of the formula (1) or the salt thereof is incorporated into said formulation in such an amount that the resulting overall weight ratio of 2-phenoxyethanol and the compound of the formula (1 ) or the salt thereof in the formulation is preferably in the range of from 1:1 to 20:1; and where in all other cases, the compound of the formula (1) or the salt thereof is in corporated into said formulation in such an amount that the resulting overall weight ratio of the antimicrobial agent and the compound of the formula (1) or the salt thereof n the formulation is preferably in the range of from 1:10,000 to 20
  • an antimicrobial agent or short antimicrobial is an agent that combats or controls mi- crobes.
  • the expressions “microbicide” and “biocide” are used as synonyms for antimicrobials.
  • An antimicrobial effect encompasses a preservative as well as a biocidal effect.
  • Pre servative or preserving effect in terms of the present invention means that the material or product as such comprising an antimicrobial agent is protected against deterioration by microbial attack. As a consequence, the thusly protected material or product has for example a longer storage stability.
  • an antimicrobial is used in a laundry detergent composition as a preservative to keep the composition storage- stable by avoiding or reducing the proliferation or growth of microbes present therein and thus avoiding or reducing the deterioration of the properties of the composition, such as the formation of malodours, a change in viscosity or pH, a phase separation etc.
  • Biocidal effect in terms of the present invention means that the composition com- prising an antimicrobial agent exerts its antimicrobial effect on a product or material treated with and different from this composition.
  • this composition exerts a biocidal effect in terms of the present invention if microorganisms on or in laundry treated therewith are killed or hampered in their proliferation or growth by the application of said composition.
  • Another example of a biocidal application is a disinfectant or sanitizer composition which exerts its biocidal effect on materials or products treated therewith.
  • the biocidal effect has to be fast, since microbes on or in the treated materials or prod ucts have to be eliminated or reduced within seconds or minutes, whereas the preserv- ative effect is a long-term effect, since it has to prevail throughout the shelf-life of the product, which can be years.
  • Many antimicrobials have both a preservative and a bio cidal effect, the prevalence depending mainly on the concentration of the antimicrobial in the composition.
  • either both carboxyl groups are neutral ized (i.e. both carboxyl groups are present as C(0)OM + groups, where M + is a cation equivalent), or just one of the carboxyl groups is neutralized (i.e.
  • M + in this context stands for an alkali metal cation (e.g. Li + , Na + , K + ), an earth alkaline metal cation equivalent (e.g. (Mg 2+ ) 1 ⁇ 2 , (Ca 2+ ) 1 ⁇ 2 ) or an ammonium cation NH 4 + .
  • Suitable alkali metal salts are the lithium, sodium, potassium or caesium salts.
  • Suitable earth alkaline metal salts are the magnesium and calcium salts.
  • Embodiments (E.x) of the invention Embodiments (E.x) of the invention
  • the composition is a personal care composition and the anti microbial agent (a) comprises 2-phenoxyethanol, the overall weight ratio of 2- phenoxyethanol and the compound of the formula (1) or the salt thereof is prefer ably in the range of from 1:1 to 20: 1 ; and where in all other cases, the overall weight ratio of the antimicrobial agent (a) and the compound of the formula (1) or the salt thereof is preferably in the range of from 1 : 10,000 to 20: 1 ; provided that the composition does not contain a tocopheryl phosphate, does not contain a peroxide, and does not contain a permanently quaternized nitrogen compound, each in amounts larger than 0.01 % by weight of the total composition.
  • composition according to embodiment E.1 wherein the antimicrobial agent (a) is 2-phenoxyethanol.
  • composition according to embodiment E.14 where in all other cases (i.e. either the composition is not a personal care composition or the antimicrobial agent (a) does not comprise 2-phenoxyethanol or both), the overall weight ratio of the antimicrobial agent (a) and the compound of the formula (1) or the salt thereof is in the range of from 20:1 to 1:100.
  • composition according to embodiment E.15 where in all other cases (i.e. either the composition is not a personal care composition or the antimicrobial agent (a) does not comprise 2-phenoxyethanol or both), the overall weight ratio of the antimicrobial agent (a) and the compound of the formula (1) or the salt thereof is in the range of from 10:1 to 1:50.
  • composition according to embodiment E.16 where in all other cases (i.e. either the composition is not a personal care composition or the antimicrobial agent (a) does not comprise 2-phenoxyethanol or both), the overall weight ratio of the antimicrobial agent (a) and the compound of the formula (1) or the salt thereof is in the range of from 1:2 to 1:10.
  • E.19 The composition according to embodiment E.18, where, independently of the type of composition and antimicrobial agent (a), the overall weight ratio of the an- timicrobial agent (a) and the compound of the formula (1) or the salt thereof is in the range of from 2:1 to 20:1.
  • E.20 The composition according to embodiment E.19, where, independently of the type of composition and antimicrobial agent (a), the overall weight ratio of the an timicrobial agent (a) and the compound of the formula (1) or the salt thereof is in the range of from 5:1 to 15:1.
  • E.21 The composition according to any of the preceding embodiments, further com prising 10% by weight or more of water, relative to the total weight of the compo sition.
  • composition according to embodiment E.21 further comprising water in an amount of 40 to 99% by weight, relative to the total weight of the composition, which composition is under normal conditions (25°C, 1013 mbar) a liquid compo sition.
  • composition according to any of the preceding embodiments whose compo nent (a) comprises 2-phenoxyethanol as the only constituent of component (a) (i.e. 4,4’-dichloro 2’-hydroxydiphenylether is not present in the composition) and which composition has a pH in the range of from 2 to 11.
  • composition according to embodiment E.23 which has a pH of from 3 to 10.
  • E.28 The composition according to any of the preceding embodiments, comprising an alcohol.
  • E.29 The composition according to embodiment E.28, where the alcohol is a glycol.
  • composition according to any of the preceding embodiments which contains the antimicrobial agent (a) in a concentration ranging from 1 ppm to 7% by weight, and component (b) in a concentration of 0.001 to 7 % by weight, relative to the total weight of the composition.
  • composition according to any of the preceding embodiments, which compo sition contains components (a) and (b) as the only components with antimicrobial and/or preserving activity.
  • composition comprising at least one further component selected from the group consisting of surface active agents different from present component (b), hydrotropic agents, further additives and agents that stabilize the composition.
  • composition according to embodiment E.36 comprising at least one surfac tant different from present component (b).
  • composition according to any of embodiment E.37 to E.39, which composi tion contains 0.001 to 80% b.w. of a surfactant, relative to the total weight of the composition.
  • composition according to any of embodiment E.36 to E.40, which composi tion contains 0.001 to 10 parts by weight of a polyethylenimine per one part by weight of present component (a).
  • composition according to any of the preceding embodiments selected from the group consisting of process waters; metal working fluids; water based raw materials, polymer solutions, polymer dispersions, polymer emulsions, inorganic slurries, organic slurries, surfactants; animal hide; leather; crop protection prod ucts; household or technical products, preferably selected from the group consisting of paints, glues, adhesives, sealants, dyes, pigments and dispersions thereof, inks, wet wipes, liquid detergents, fabric softeners, liquid hard surface cleaners and liquid dishwashing compositions which are preferably selected from dish wash liquids and dish wash gels; and personal care products which are in par ticular selected from the group consisting of water-in-oil emulsions, oil-in-water emulsions, creams, lotions, liquid soaps, shampoo, make-up, hair dyes, sun pro tection products and wet wipes.
  • E.44 The composition according to any of the preceding embodiments, which is not a personal care composition.
  • E.45 The composition according to any of embodiments E.43 or E.44, selected from the group consisting of homecare compositions and compositions for cleaning or disinfecting on an industrial scale.
  • composition according to embodiment E.45, where the homecare composi tions and the compositions for cleaning or disinfecting on an industrial scale are selected from the group consisting of liquid laundry detergents, fabric softeners, liquid rug shampoos, liquid hard surface cleaners and liquid dishwashing compo sitions.
  • composition according to any of the preceding embodiments which is a laundry detergent composition further comprising an enzyme, or is an antimicrobial cleaning composition comprising, as component (a), 2- phenoxyethanol and 4,4’-dichloro 2’-hydroxydiphenylether as an additional anti microbial agent, each antimicrobial agent preferably in a concentration as defined in any of embodiments E.31 to E.33.
  • composition selected from the group consisting of liquid dishwashing compositions, liquid laundry detergent compositions, fabric softeners, liquid surface cleaning compositions and liquid rug shampoos, where the composition comprises
  • composition according to any of embodiments E.45 to E.48, where the over all weight ratio of the antimicrobial agent (a) and the compound of the formula (1) or the salt thereof (b) is in the range of from 20:1 to 1 :100.
  • composition according to embodiment E.49, where the overall weight ratio of the antimicrobial agent (a) and the compound of the formula (1) or the salt there of (b) is in the range of from 10:1 to 1 :50.
  • composition according to embodiment E.50, where the overall weight ratio of the antimicrobial agent (a) and the compound of the formula (1) or the salt there of (b) is in the range of from 1 : 1 to 1 :20.
  • Kit of parts comprising at least two parts, where the first part comprises at least one antimicrobial agent as defined in any of embodiments E.1 or E.2; the second part comprises at least one compound of the formula (I) or a salt thereof as de fined in any of embodiments E.1 or E.3 to E.10 and optionally at least one organ ic solvent; and an optional third part comprises at least one organic solvent; where the first part does not comprise a compound of the formula (i) or a salt thereof as defined in any of embodiments E.1 or E.3 to E.10; where the second part does not comprise any antimicrobial agent as defined in any of embodiments E.1 or E.2; where the optional third part does not comprise any antimicrobial agent as de fined in any of embodiments E.1 or E.2 nor the compound of the formula (I) or a salt thereof as defined in any of embodiments E.1 or E.3 to E.10; and where the first and second parts contain the at least one antimicrobial agent as defined in any of embodiments
  • E.54 Use of a compound of the formula (1) or a salt thereof as defined in any of em bodiments E.1 or E.3 to E.10, for enhancing the antimicrobial effect of the antimi crobial agent (a) as defined in embodiment E.1 or E.2, or, in combination with said antimicrobial agent, for enhancing the preserving ef- feet of said combination.
  • a method for enhancing the antimicrobial effect of an antimicrobial agent select ed from the group consisting of 2-phenoxyethanol and 4,4’-dichloro 2’- hydroxydiphenylether, especially of 2-phenoxyethanol, in a formulation which method comprises incorporation of a compound of the formula (1) or a salt thereof as defined in any of embodiments E.1 and E.3 to E.10 and optionally one or more further components as defined in embodiments E.21 , E.28, E.29, E.36, E.37, E.38 or E.39 into said formulation; where in case that the formulation is a personal care composition and the antimi crobial agent comprises 2-phenoxyethanol, the compound of the formula (1) or the salt thereof is incorporated into said formulation in such an amount that the resulting overall weight ratio of 2-phenoxyethanol and the compound of the for mula (1 ) or the salt thereof is preferably in the range of from 1:1 to 20: 1 ; and where in all other cases, the compound of the formula (1) or the salt thereof is
  • compositions typically are aqueous compositions as explained further be low.
  • the antimicrobial agent of component (a) in the compositions of the inven tion is or comprises, especially is 2-phenoxyethanol.
  • composition typically does not contain tocopherol or vitamin E compounds including salts or complexes thereof like phos phates, acetates etc.; a preferred composition is free from phosphates in general.
  • composition comprising components (a) and (b), and further optional com ponents as explained further below, further does not contain (y) a peroxide, and does not contain (z) a permanently quaternized nitrogen compound.
  • Absence of such components (x), (y) and/or (z) generally means that their amounts are equal or lower than 0.01% by weight of the total composition for each such component.
  • a preferred composition according to the invention contains present components (a) and (b), while it does not contain a compound com prising permanently quaternized nitrogen; such functional group is often present in an timicrobial agents and preservatives, but may show incompatibilities with anionic for mulation components. Due to the enhanced activity of the antimicrobial agent (a) and its superior preserving effect in aqueous products of the invention, there is no necessity to add any further antimicrobial agent other than present component (a).
  • the invention thus further provides the use of present components (a) and (b) as sole components providing antimicrobial, in particular preserving activity in an aqueous composition, and does provide the opportunity to formulate correspondingly preserved aqueous compo sitions.
  • Components (z) containing permanently quaternized nitrogen are compounds contain ing one or more nitrogen atoms with four chemical bonds to atoms other than hydro- gen; the nitrogen atom thusly quaternized permanently carries a net positive charge.
  • Many compounds comprising such permanently quaternized nitrogen are known as antimicrobials, such as benzalkonium chloride, or the homopolymer of dimethyl diallyl ammonium chloride available as Merquat ® 100.
  • Such excluded components stand in contrast to other nitrogen compounds not permanently quaternized, such as polyethyl- enimines noted further below, which may carry positive charges due to protonization of the nitrogen at lower pH.
  • the term permanently quaternized nitrogen compounds thus refers to compounds containing one or more quaternized nitrogen atoms, where none of the four bonds of at least one of these nitrogen atoms is an N-H bond.
  • 2-Phenoxyethanol is a compound of the formula:
  • 4,4’-Dichloro 2-hydroxydiphenyl ether is a compound of the formula:
  • 2-Bromo-2-nitropropane-1 ,3-diol (Bronopol®) is a compound of the formula: Glutaraldehyde, also known as 1 ,5-pentanedial, is of the formula OHC(CH ) CHO.
  • 2,4-Dichlorobenzyl alcohol is a compound of the formula: 1 ,3,5-T ris-(2-hydroxyethyl)-hexahydro-1 ,3,5-triazine is a compound of the formula
  • Formic acid of the formula H(CO)OH typically is present in combination with a salt of formic acid, such as an alkaline (e.g. sodium) salt, or possibly ammonium salt.
  • a salt of formic acid such as an alkaline (e.g. sodium) salt, or possibly ammonium salt.
  • R2 and R3 independently are hydrogen or chloro, or together with the carbon atoms they are attached to form an annellated benzene ring, such as in the compound 1 ,2- benzisothiazol-3(2H)-one.
  • 1 ,2-Benzisothiazol-3(2H)-one is a compound of the formula:
  • the compound of the formula (1) or its salt is used for en hancing the antimicrobial effect of the antimicrobial agent in an aqueous composition.
  • an aqueous composition is charac terized by containing 10 % b.w or more of water.
  • An especially preferred aqueous composition is a liquid composition which contains water in an amount of 30 to 99 %, or even 40 to 99 %, each b.w. of the total composition.
  • the composition of the invention typically is an aqueous composition
  • present component (b) is typical ly used according to the invention in an aqueous composition, which composition com prises 10 % b.w. or more of water, and preferably water in an amount of 30 to 99 % b.w. of the total composition, and preferably is, under normal conditions, a liquid com position.
  • Normal conditions means 25°C and 1013 mbar (1013 hPa)
  • Typical use according to the invention, and compositions of the invention comprises combining 0.001 to 1000, preferably 0.001 to 20, more preferably 0.01 to 10 parts by weight of the compound of the formula (1) or a salt thereof with 1 part by weight of said antimicrobial agent.
  • 0.05 to 0.5 parts by weight of the compound comprising an anion of the formula 1 is combined with 1 part by weight of said antimicrobial agent.
  • n is 1 or 2 and m is in the range of from 7 to 11.
  • the compound of the formula (1) or its salt is sodium n-octylimino-diacetate or sodium dodecylimino-diproprionate.
  • the compound of the formula (1) or its salt is typically used for enhancing the antimi crobial effect of said antimicrobial agent in a composition selected from home care for mulations, household formulations, personal care formulations; or technical formula tions, especially selected from the group consisting of process waters additives, metal working fluids, water based and typically liquid raw materials, polymer solutions, poly mer dispersions, polymer emulsions, inorganic slurries, organic slurries, surfactants, rheology modifiers, cosmetic raw materials such as dyes, emulsifiers, polymers, UV filters, antioxidants, UV protectants, vitamins, emollients, solvents; animal hide; leather; crop protection products; household or technical products like paints, glues, adhesives, sealants, dyes, pigments and dispersions thereof, inks, wet wipes, liquid detergents, fabric softeners, hard surface cleaners, dish wash liquids, dish wash gels; personal care products like water-in-oil emulsion
  • the invention also pertains to a composition
  • a composition comprising a) 2-phenoxyethanol, and b) a compound of the formula (T) CH 3 -(CH 2 ) m -N[(CH 2 ) n -COO- M + ] 2 (1') wherein n independently is from the range 1 to 8, m is from the range 1 to 21, especially 5 to 17, and
  • M + is a cation selected from alkali metal cations, earth alkaline metal cation equiva lents, hydrogen and the ammonium cation.
  • the present invention further pertains to the use of a compound of the for mula (1) or a salt thereof, as defined above, for enhancing the biocidal and/or preservative effect of 2-phenoxyethanol.
  • Salts or partial salts of the present compound of the formula (1) or (1'), wherein one or both carboxyl groups are neutralized typically dissociate in aqueous compositions.
  • the compound thus may be present with 2 groups COOH, one COOH and one COO, or two groups COO-; the compound thus further may be used as a buffer, which stabi lizes the pH of present composition.
  • the present composition typically does not contain vitamin E or to- copherol or derivatives thereof such as tocopherol esters, like a phosphate or acetate thereof.
  • Aqueous compositions of the invention generally have a pH from the range 2 to 11, e.g. 2 to 10; preferably 3 to 10, e.g 3 to 8 or 4 to 9; and especially 3 to 7
  • compo- nent a) comprises 4,4’-dichloro 2’-hydroxydiphenylether
  • such composition typically has a pH from the range 3 to 10, preferably 4 to 9.
  • Aqueous compositions of the invention whose component a) comprises 2-phenoxyethanol as the only constituent of compo nent a) generally may have a pH from the range 2 to 11, preferably 3 to 10.
  • compositions of the invention having a pH from the range 2 to 8, espe- daily 3 to 8, more specifically 3 to 7.
  • a further embodiment of certain technical interest is a composition further comprising an alcohol, for example a glycol, typically in an amount of 0.01 to 59 % b.w. of the total composition
  • composition according to the invention preferably contains the antimicrobial agent in compositions in a concentration ranging preferably from 1 ppm to 7% by weight, more preferably from 0.001 to 7% by weight, in particular from 0.01 to 7% by weight, relative to the total weight of the composition.
  • 2-phenoxyethanol is present in in a concentration of 0.01 to 2 %, especially 0.1 to 2 %, relative to the total weight of the composition.
  • 4,4’-dichloro 2’-hydroxydiphenylether is present in a concentra tion from 1 to 2000 ppm, relative to the total weight of the composition..
  • the present composition may contain only one of the above antimicrobial agents or a combination thereof, each in the specified concentration.
  • Component (b) is preferably present in a concentration of 0.001 to 7% by weight, in particular 0.01 to 5% by weight, relative to the total weight of the composition. Each of the concentrations/percentages given is by weight of the total composition.
  • the composition contains more than one antimicrobial agent of present component (a); i.e. it contains both 2-phenoxyethanol and 4,4’-dichloro 2’- hydroxydiphenylether; e.g. 2-phenoxyethanol in a concentration of for example 0.1 to 2% by weight and 4,4’-dichloro 2’-hydroxydiphenylether in a concentration of for exam ple from 1 to 2000 ppm.
  • the composition contains 2-phenoxyethanol in a con centration of for example 0.1 to 2% by weight and as further antimicrobial agent e.g.; bronopol in a concentration of for example 20 ppm to 1000 ppm; glutaraldehyde in a concentration of for example 10 ppm to 2000 ppm and/or formic acid (as an acid and/or its salt) in a concentration of for example 0.05 to 0.50% by weight (in all cases relative to the total weight of the composition).
  • bronopol in a concentration of for example 20 ppm to 1000 ppm
  • glutaraldehyde in a concentration of for example 10 ppm to 2000 ppm
  • formic acid as an acid and/or its salt
  • Combinations of present components (a) and (b) provide good preservation and stabili zation against microbial attack for a wide number of products as noted above, especial ly aqueous compositions. As noted above, there is generally no need to add any further antimicrobial agent or preserving agent to a composition preserved in accordance with the present invention.
  • the composition comprises only 2-phenoxyethanol and/or 4,4’- dichloro 2’-hydroxydiphenylether and the compound (1) or a salt thereof as antimicro bial agent, such as listed according to Art. 95 of EU Regulation 528/2012 (product types 1-13). Especially, it does not contain any of bronopol, glutaraldehyde or triclosan
  • the invention thus further includes a composition containing present components (a) and (b), but do not contain any further antimicrobial agent, such as listed according to Art. 95 of EU Regulation 528/2012 (product types 1-13), e.g. an compound noted be low, except for those compounds which are part of present component a) or used ac- cording to present invention in combination with the compound comprising the anion of present formula 1.
  • any further antimicrobial agent such as listed according to Art. 95 of EU Regulation 528/2012 (product types 1-13), e.g. an compound noted be low, except for those compounds which are part of present component a) or used ac- cording to present invention in combination with the compound comprising the anion of present formula 1.
  • present components (a) and (b) nevertheless may be combined with a fur ther antimicrobial agent, which is typically selected from the list according to Art 95 of EU Regulation 528/2012 (product types 1-13, especially its product types 6-13); pre ferred being one or more components of the following list:
  • Biphenyl -2-ol, and its salts o-phenylphenol, MEA-o-phenylphenate, potassium phenylphenate, sodium phenylphenate;
  • Hexa-2,4-dienoic acid (Sorbic acid, CAS No 110-44-1) and its salts, e.g. calci um sorbate, sodium sorbate
  • Hydrogen peroxide (CAS No. 7722-84-1) (the latter if present at all, is prefera bly contained in amounts of at most 0 01 % by weight of the total composition; preference being given to its total absence);
  • N,N'-methylenebismorpholine (MBM, CAS No 5625-90-1);
  • polyhexamethylene biguanide hydrochloride (PHMB, CAS No 1802181-67-4), polyhexamethylene biguanide hydrochloride (PHMB, CAS No. 27083-27-8), e.g. poly(iminoimidocarbonyl)iminohexamethylene hydrochloride, poly(iminocarbonimidoyliminocarbonimidoylimino -1 ,6-hexanediyl), polyam- inopropyl biguanide;
  • Salts of benzoic acid e.g ammonium benzoate, calcium benzoate, magnesium benzoate, MEA-benzoate, potassium benzoate;
  • Esters of benzoic acid e.g butyl benzoate, ethyl benzoate, isobutyl benzoate, isopropyl benzoate, methyl benzoate, phenyl benzoate, propyl benzoate;
  • Propionic acid and its salts e.g. ammonium propionate, calcium propionate, magnesium propionate, potassium propionate, sodium propionate
  • Salicylic acid and its salts e.g. calcium salicylate, magnesium salicylate, MEA salicylate, sodium salicylate, potassium salicylate, TEA salicylate;
  • Inorganic sulphites and hydrogensulphites e.g. sodium sulfite, ammonium sul fite, ammonium bisulfite, potassium sulfite, potassium hydrogene sulfite, sodium bisulfite, sodium metasulfite, potassium metasulfite, potassium metabisulfite;
  • butyl 4 -hydroxybenzoate and its salts e.g. butylparaben, sodium butyl paraben, potassium butyl paraben;
  • Propyl 4-hydroxybenzoate and its salts e.g. propyl paraben, sodium propyl paraben, potassium propyl paraben;
  • 59)4 -Hydroxybenzoic acid and its salts and esters e.g. methyl paraben, ethyl paraben, potassium ethyl paraben, potassium paraben, potassium methyl para ben, sodium methyl paraben, sodium ethyl paraben, sodium paraben, calcium paraben, calcium methyl paraben, calcium ethyl paraben;
  • Phenylmercuric salts including borate, e.g. phenyl mercuric acetate, phenyl mercuric benzoate (CAS Nos. 62-38-4 and 94-43-9);
  • Undec -10-enoic acid and its salts e.g. undecylenic acid, potassium un- decylenic acid, sodium undecylenic acid, calcium undecylenic acid, MEA- undecylenic acid, TEA-undecylenic acid;
  • Chlorocresol e,g, p-chloro-m-cresol (CAS No. 59-50-7);
  • Chloroxylenol (CAS Nos 88-04-0, 1321-23-9);
  • Methenamine (CAS No. 100-97-0);
  • Methenamine 3 -chloroallylochloride synonym: Quaternium 15 (CAS No 4080- 31-3) (the latter, if present at all, is preferably contained in amounts of at most 0.01% by weight of the total composition; preference being given to its total ab sence), 1 -(4-Chlorophenoxy)-1 -(imidazol-1 -yl)-3,3-dimethylbutan-2-one, synonym: Climbazole (CAS No 38083-17-9);
  • bromochorophene (CAS No 15435-29-7);
  • N,N' -bis(4-chlorophenyl)-3,12-diimino-2,4,11,13-tetraazatetradecanediamidine and its digluconate, diacetate and dihydrochloride e.g chlorohexidine, chlorhexidine digluconate, chlorohexidine diacetate, chlorhexidine dihydro chloride (CAS Nos 55-56-1 , 56-95-1 , 18472-51-0, 3697-42-5);
  • Alkyl (C12 -C22) trimethyl ammonium bromide and chloride e.g. behentrimoni- um chloriode, cetrimonium bromide, cetrimonium chloride, laurtrimonium bro mide, laurtrimonium chloride, steartrimonium bromide, steartrimonium chloride (CAS Nos 17301-53-0, 57-09-0, 112-02-7, 1119-94-4, 112-00-5, 1120-02-1, 112-03-8);
  • Benzalkonium chloride, bromide and saccharinate e.g. benzalkonium chloride, benzalkonium bromide, benzalkonium saccharinate (CAS Nos 8001-54-5, 63449-41-2, 91080-29-4, 68989-01-5, 68424-85-1 , 68391-01-5, 61789-71-7, 85409-22-9);
  • Phenoxypropanol (CAS-No. 770-35-4, CAS No 4169-04-4, propylene glycol phenyl ether, phenoxyisopropanol 1-phenoxy-2-propanol, 2-phenoxy-1- propanol);
  • Glucoprotamine (CAS-No. 164907-72-6, chemical description: reaction product of glutamic acid and alkylpropylenediamine, further names: Glucopro tamine 50);
  • Cyclohexyl hydroxyl diazenium-1 -oxide, potassium salt (CAS No. 66603- 10-9, further names: N-cyclohexyl-diazenium dioxide, Potassium HDO, Xyli- gene, Protectol® KD);
  • Formic acid (CAS-No. 64-18-6, further names: methanoic acid, Protectol® FM, Protectol® FM 75, Protectol® FM 85, Protectol® FM 99, Lutensol® FM) and its salts, e.g. sodium formiate (CAS No 141-53-7);
  • anorganic silver complexes such as silver zeolites and silver glass com pounds (e.g. Irgaguard® B5000, Irgaguard® B6000, Irgaguard® B7000) and others described in WO-A-99/18790, EP1041879B1; 107) 1 ,3,5-T ris-(2-hydroxyethyl)-hexahydro-1 ,3,5-triazin (CAS-No.
  • Hexyhydrotriazine Tris(hydroethyl)-hexyhydrotriazin, hexyhydro- 1 ,3-5-tris(2-hydroxyethyl)-s-triazine, 2,2',2"-(hexahydro-1 ,3,5-triazine-1 ,3,5- tri- yl)triethanol, Protectol® HT).
  • the one or more further antimicrobial agents if added to the present composition, typi cally is present in a concentration of 0.0005 to 10 %, e.g. 0.0005 to 0.5 %, relative to the total weight of the composition.
  • the present composition preferably comprises such further antimicrobial agent selected from the above list, especially one of the following:
  • the further antimicrobial agent is selected from biocides containing halogen atoms and/or containing phenolic moieties, formic acid, chlorine dioxide or chlorine dioxide generating compounds, or dialdehydes; especially 2-bromo- 2-nitropropane-1 ,3-diol, 4,4’-dichloro-2’-hydroxy-diphenylether, 2,4,4'-trichloro-2'- hydroxy-diphenyl ether, glutaraldehyde, formic acid, 1,2-ethanedial, 2,4-dichlorobenzyl alcohol, 3,5-dimethyl-1 ,3-5-thiadiazinane-2-thione, 1 ,3,5-tris-(2-hydroxyethyl)- hexahydro-1 ,3,5-triazine, 2-methylthio-4-tert-butylamino cyclopropylamino-6-(1 ,3,5- triazine), silver-glass, silver zeolite.
  • the invention is also directed to the use of the present composition for the manufacture of
  • a home care formulation such as a disinfectant, all purpose cleaner, dishwashing liquid, descaling agent, a bath room cleaner, a toilet bowl cleaner, and/or
  • a disinfectant and/or sanitary detergent of hard and/or soft surfaces such as a floor cleaner, a glass cleaner, a kitchen cleaner, a bath room cleaner, a sanitary clean er, a toilet bowl cleaner, a furniture cleaner, and/or
  • the invention is also directed to a product selected from the group consisting of home care formulation, a disinfectant of hard and/or soft surfaces, sanitary detergent of hard and/or soft surfaces, and product for clean in place (CIP), wherein said article contains the composition as described herein.
  • the present invention is es pecially directed to a product selected from the group consisting of disinfectant, all pur pose cleaner, dishwashing liquid, laundry detergent, fabric conditioner, descaling agent, bath room cleaner, toilet bowl cleaner, floor cleaner, glass cleaner, kitchen cleaner, sanitary cleaner, furniture cleaner and product for clean in place (CIP), where in said product comprises the aqueous composition as described herein.
  • the products containing the present composition may be in the form of a con- centrate that has to be diluted with water prior to use or are ready-to-use products, which are used as such, e.g. without dilution.
  • a disinfectant is a substance that is applied to non-living (i.e. inanimate) objects to destroy microorgan isms that are living on said objects.
  • the clean in place is a method of cleaning and/or disinfecting the interior surfaces of pipes, vessels, process equipment, filters and associated fittings without disassembly.
  • the clean in place prod uct according to this invention is especially used for removing soils and disinfection in facilities for processing typically liquid product streams such as beverages, milk, juices, etc.
  • the formulation of the invention can be used for disinfection of the interior surfaces in CIP after a separate cleaning step.
  • the cleaning step is performed with a cleaning formulation that is not biocidal or disinfecting. It may however also be the case that the formulation of the invention is used for CIP-cleaning and CIP disinfection in one single step.
  • the present composition typically comprises at least one further component selected from the group consisting of surface active agents different from present component (b), hydrotropic agents (of course also different from component (b)); especially select- ed from surfactants such as the group consisting of anionic surfactants, cationic surfac tants, nonionic surfactants, amphoteric surfactants.
  • the present composition may comprise one or more further additives improving the antimicrobial effect; one type of such additives is the class of polyethylenimines.
  • the present composition may further contain agents for stabilizing present component (a) and/or present component (b) in the formulation.
  • the further component comprises permanently quaternized nitrogen compounds (as may be the case for cationic and amphoteric surfactants), these are preferably contained in an overall amount of at most 0 01 by weight of the total compo sition; preference being given to their total absence
  • the present invention thus includes formulations comprising 0.01-10% of a combi nation of present components (a) and (b) as noted above, and at least one of the fol lowing components (c) 1-80% of one or more surface active agents
  • the present invention also includes formulations comprising 0.01-10% of a combina tion of present components (a) and (b) as noted above, and at least one of the follow ing components (c) 0-80% of one or more surface active agents
  • the present invention also includes formulations comprising 0.01-10% of a combina tion of present components (a) and (b) as noted above, and at least one of the follow ing components
  • surfactants will normally comprise at least one surfactant which may be anionic, cationic, nonionic or amphoteric.
  • the surfactant is anionic or non-ionic.
  • the cationic and amphoteric surfactants comprise permanently quater- nized nitrogen compounds, these are preferably contained in an overall amount of at most 0.01 by weight of the total composition; preference being given to their total ab sence.
  • the anionic surfactant can be, for example, a sulfate, sulfonate or carboxylate surfac tant or a mixture thereof. Often used are alkylbenzenesulfonates, alkyl sulfates, alkyl ether sulfates, olefin sulfonates, fatty acid salts, alkyl and alkenyl ether carboxylates or to an alpha-sulphonic fatty acid salt or an ester thereof.
  • sulfonates are, for example, alkylbenzenesulfonates having from 10 to 20 carbon atoms in the alkyl radical, alkyl sulfates having from 8 to 18 carbon atoms in the alkyl radical, alkyl ether sulfates having from 8 to 18 carbon atoms in the alkyl radical, and fatty acid salts derived from palm oil or tallow and having from 8 to 18 carbon at oms in the alkyl moiety.
  • the average molar number of ethylene oxide units added to the alkyl ether sulfates is from 1 to 20, preferably from 1 to 10.
  • the cation in the anionic surfactants is preferably an alkaline metal cation, especially sodium or potassium, more especially sodium.
  • Preferred carboxylates are alkali metal sarcosinates of formula R 19 ’- CON(R 20 ’)CH 2 COOM1 wherein R 19 ’ is C 9 -Ci 7 -alkyl or C 9 -Ci 7 -alkenyl, R 20 ’ is Ci-C 4 -alkyl and M1 is an alkali metal, especially sodium.
  • the non-ionic surfactant may be, for example, a primary or secondary alcohol ethox- ylate, especially a C8-C20 aliphatic alcohol ethoxylated with an average of from 1 to 20 mol of ethylene oxide per alcohol group. Preference is given to primary and secondary C10-C15 aliphatic alcohols ethoxylated with an average of from 1 to 10 mol of ethylene oxide per alcohol group.
  • Non-ethoxylated non-ionic surfactants for example alkylpoly- glycosides, glycerol monoethers and polyhydroxyamides (glucamide), may likewise be used.
  • composition may contain cationic surfactants.
  • cationic surfactants include all common cationic surface-active compounds, especially surfactants having a textile softening effect.
  • Cationic surfactants are, for example, ammonium salts such as Cs-Ci 6 - dialkyldimethylammonium halides, dialkoxydimethylammonium halides or imidazolini- um salts with a long-chain alkyl radical.
  • Amphoteric surfactants are, for example, derivatives of secondary or tertiary amines, for example C 6 -Cis-alkyl betaines (e.g cocoamidopropyl betaine; disodium cocoam- phodiacetate (DSCADA)) or C6-Ci5-alkyl sulfobetaines, or amine oxides such as alkyl- dimethylamine oxides.
  • Hydrotropic agents are compounds which solubilizes hydrophobic compounds in aque ous solution by means other than micellar solubilization. Similar to surfactants, hy drotropes often (but not necessarily) consist of a hydrophilic part and a hydrophobic part, but in contrast to surfactants the hydrophobic part is generally too small to cause spontaneous self-aggregation.
  • the hydrotropic agents comprise for example: ethoxylated or non ethoxylated mono alcohols, diols or polyols with a low number of carbon atoms or their ethers (e.g. etha nol, isopropanol, 1 ,2-dipropanediol, propyleneglycol, glyerin, ethylene glycol, ethylene glycol monoethylether, ethylene glycol monobutylether, propylene glycol monometh- ylether, propylene glycol monoethylether, propylene glycol monobutylether, diethylene glycol monomethylether; diethylene glycol monoethylether, diethylene glycol mono butylether and similar products).
  • ethoxylated or non ethoxylated mono alcohols e.g. etha nol, isopropanol, 1 ,2-dipropanediol, propyleneglycol, glyerin,
  • the polyols that come into consideration for that pur pose have preferably from 2 to 15 carbon atoms and at least two hydroxy groups.
  • the polyols may also contain further functional groups, especially amino groups, and/or may be modified with nitrogen.
  • Typical examples are as follows: glycerol, alkylene gly cols, for example ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and also polyethylene glycols having an average molecular weight of from 100 to 1000 Dalton; technical oligoglycerol mixtures having an intrinsic degree of condensation of from 1.5 to 10, for example technical diglycerol mixtures having a di glycerol content of from 40 to 50 % by weight; methylol compounds, such as, especial ly, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipen- taerythritol; lower alkyl-gluco
  • hydrotropic agents (d) comprise for example those mentioned in WO02/48298 A1 from page 7, 4th paragraph to page 8 under the “components (b)” and more specifi cally cumene sulfonate, ammonium cumene sulfonate, ammonium xylene sulfonate, potassium toluene sulfonate, sodium toluene sulfonate, sodium xylene sulfonate, tolu ene sulforic acid and xylene sulfonic acid.
  • components (e) Further additives
  • Examples for the other components (e) are organic acids (typically present in amounts from 0.1 to 10% b.w , preferably 0.2 to 5 %) like simple C1-C6 linear or branched mono- and di- and tri-carboxylic acids like formic acid, acetic acid, propanoic acid, oxalic acid and further organic acids like lactic acid, citric acid, tartric acid, mandelic acid, benzoic acid, salicylic acid, glutaric acid, sorbic acid and succinic acid.
  • organic acids typically present in amounts from 0.1 to 10% b.w , preferably 0.2 to 5 %
  • simple C1-C6 linear or branched mono- and di- and tri-carboxylic acids like formic acid, acetic acid, propanoic acid, oxalic acid and further organic acids like lactic acid, citric acid, tartric acid, mandelic acid, benzoic acid, salicylic acid, glutaric acid, sorbic acid and succinic acid.
  • additives comprise metal chelating and -complexing agents (also termed sequestrants, builders, structural substances, framework substances, chelators or sof teners) (typically present in amounts from 0.1 to 10% b.w., preferably 0.1 to 7 %), for example, EDTA, NTA, alaninediacetic acid or phosphonic acids, ethylene di-amine tetra acetic acid (EDTA), beta-alanine diacetic acid (EDETA), phosphonomethyl chi- tosan, carboxymethyl chitosan, hydroxyethylene di-amino tetraacetic acid, nitrilotri- acetic acid (NTA) and ethylenediamine disuccinic acid (S,S-EDDS, R,R-EDDS or S,R- EDDS), alkali metal phosphates, like tripolyphosphates, polycarboxylates, polycarbox- ylic acids, organic phosphonates, aminoalkylene
  • polycarboxylates are polyhydroxycarboxylates (typically present in amounts from 0.1 to 10 % b.w., preferably 0.2 to 7 %), like citrates, and acrylates, and copolymers thereof with maleic anhydride.
  • polycarboxylic acids are nitrilo- triacetic acid, ethylenediaminetetraacetic acid and ethylenediamine disuccinate either in racemic form or in the enantiomerically pure (S,S) form.
  • examples of phosphonates or aminoalkylenepoly(alkylenephosphonates) are alkali metal salts of 1-hydroxyethane-1,1-diphosphonic acid, nitrilotris(methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepenta- methylenephosphonic acid, and also salts thereof.
  • polyphosphonates are those having have the following formula wherein
  • Ri 8 is CH2PO3H2 or a water soluble salt thereof and d is an integer of the value 0, 1 , 2 or 3.
  • PEIs are polymers of ethylenediamine and can be characterized by repeating groups of the empirical for- mula -[CH 2 -CH 2 -NH] n - wherein n ranges from approximately from 10 to 100,000, e.g. from 10 to 15000.
  • PEI can be linear or branched (branched forms are not correctly re flected in the above formula; nevertheless the formula should also symbolize branched forms), where branching can result in dendrimers, star-like polymers, hyperbranched polymers and other branched forms.
  • the present composition contains a polyethylenimine (PEI) grafted with ethylene oxide and/or propyleneoxide, but no further polyamine or cationic polymer.
  • PEI polyethylenimine
  • such a composition contains a polyethylenimine grafted with ethylene oxide and/or propyleneoxide as the only cationic nitrogen com pound.
  • Such preferred polycationic polyethylenimines typically have a charge density from the range 5 to 25 meq/g as measured at a pH from the range 4 to 5.
  • the polyeth ylenimine preferably has a weight-average molecular weight (M w ) of 500 g/mol to 125 000 g/mol, and more preferably 750 g/mol to 100 000 g/mol (as determined by gel permeation chromatography (GPC), in particular with PEG or PMMA standard; specifi cally with multi angle light scattering (MALS) detector of the intermediate respective polyalkylenimine, with 1.5% by weight aqueous formic acid as eluent and cross-linked poly-hydroxyethyl methacrylate as stationary phase).
  • M w weight-average molecular weight
  • the PEI may be in linear or branched form or in the form of what are called den drimers; preferably they are present in the form of dendrimers. Particular preference is given to using polyethylenimine in dendrimer form.
  • dendrimer relates to a series of branched molecular structures, inter alia including dendrimers, star-like poly mers and hyperbranched polymers.
  • Polyethylenimines of this kind are available, for example, under the trade name Lupa- sol ® from BASF SE. A more precise description of such polyimines is found, for exam ple, in Macromolecules vol. 2, H.-G. Elias, 2007 Vol. 2, pages 447 to 456.
  • One particularly preferred embodiment of the invention uses as said at least one poly ethylenimine having a weight-average molecular weight of 500 g/mol to 125 000 g/mol, preferably of 750 g/mol to 100 000 g/mol, in dendrimer form. Mixtures of two, three or more of such PEIs may be combined with present components (a) and (b).
  • An important embodiment of the invention relates to a composition
  • a composition comprising e) at least one ethylenimine polymer (also recalled as polyethylenimine e) grafted with ethyleneoxide and/or propyleneoxide.
  • the polyethylenimine (e) has a mean molecular weight M w in the range of from 500 to 1000000 g/mol, especially 600 to 75000 g/mol, more especially 800 to 25000 g/mol, as detectable by gel permeation chromatography (GPC).
  • Highly branched polyethylenimines are characterized by their degree of branching (DB).
  • DB may be determined, for example, by 13 C-NMR spectrometry, preferably in D2O.
  • DB D +T/D+T+L wherein D stands for the fraction of tertiary amino groups, L (linear) stands for the frac tion of secondary amino groups, and T (terminal) stands for the fraction of primary ami no groups.
  • Highly branched polyethylenimines are those polyethylenimines whose DB ranges from 0.1 to 095, preferably 025 to 0.90, more preferably 030 to 0.80, amost preferably is 0.5 or higher, e.g 0.5-0.8.
  • the PEI backbone is usually branched, i.e. cer- tain N-hydrogen atoms in the above formula are replaced by CH2-CH2-NH2 or by a fur ther polyethylenimine chain, which again may be branched, thus leaving the above empirical formula unchanged.
  • PEIs are, under normal application conditions, e.g. in contact with water of pH close to the neutral such as pH 4-9 or pH 5-8, usually present in charged form as polycationic polymers or oligomers.
  • An example is an ethoxylated polyethylenimine comprising 5 parts by weight of a branched polyethylenimine core of molecular weight 600-800 (GPC) and 95 parts by weight of moieties of formula -CH2- CH2-O-.
  • GPC molecular weight 600-800
  • the present composition may, for example, contain 0001 to 10, parts by weight of a polyethylenimine, such as a branched polyethylenimine polymer, whose uncharged form conforms to the empirical formula -(CH2-CH2-NH) n - wherein n ranges from approx imately 10 to 100000, which polyethylenimine is grafted with ethylene oxide and/or propyleneoxide.
  • a polyethylenimine such as a branched polyethylenimine polymer, whose uncharged form conforms to the empirical formula -(CH2-CH2-NH) n - wherein n ranges from approx imately 10 to 100000, which polyethylenimine is grafted with ethylene oxide and/or propyleneoxide.
  • further additives are the following additional functional ingredi ents:
  • the compositions will comprise fatty acid esters.
  • ester oils are isopropylmyristate, isopropylpalmitate, isopropylstea- rate, isopropyl isostearate, isopropyloleate, n-butylstearate, n-hexyllaurate, n- decyloleate, isooctylstearate, iso-nonylstearate, isononyl isononanoate, 2- ethylhexylpalmitate, 2-hexyllaurate, 2-hexyldecylstearate, 2-octyldodecylpalmitate, oleyloleate, oleylerucate, erucyloleate, erucylerucate, cetearyl octanoate, cetyl palmi- tate, cetyl stearate, cetyl oleate, cetyl behenate, cetyl acetate, my
  • C10-C22 ethylene glycol fatty acid esters are desirably combined with the polymeric thickeners (described below).
  • the ester is preferably a diester, more preferably a C14-C18 diester, most preferably ethylene glycol distearate.
  • C10-C22 ethylene glycol fatty acid esters are utilized as the stabilizer, they will be present in a concentration range of: from about 3% to about 10%, preferably from about 5% to about 8%, more preferably from about 6% to about 8% of the personal cleansing compositions.
  • the enzyme is generally selected from the group of hydrolases (EC.3), which may be part of a liquid enzyme concentrate.
  • “Liquid enzyme concentrate” herein means any liquid enzyme-comprising product comprising at least one enzyme.
  • “Liquid” in the con text of enzyme concentrate is related to the physical appearance at 20°C and 101.3 kPa.
  • the liquid enzyme concentrate may result from dissolution of solid enzyme in solvent.
  • the solvent may be selected from water and an organic solvent
  • a liquid enzyme con centrate resulting from dissolution of solid enzyme in solvent may comprise amounts of enzyme up to the saturation concentration.
  • Dissolution herein means, that solid compounds are liquified by contact with at least one solvent. Dissolution means complete dissolution of a solid compound until the sat uration concentration is achieved in a specified solvent, wherein no phase-separation occurs
  • Liquid enzyme concentrates may comprise amounts of enzyme in the range of 0.1% to 40% by weight, or 05% to 30% by weight, or 1 % to 25% by weight, or 3% to 25% by weight, or 5% to 25% by weight, all relative to the total weight of the enzyme concen trate
  • liquid enzyme concentrates are resulting from fermentation and are aqueous.
  • Fermentation means the process of cultivating recombinant cells which express the desired enzyme in a suitable nutrient medium allowing the recombinant host cells to grow (this process may be called fermentation) and express the desired protein.
  • fermentation broth usually is collected and further processed, wherein the fermentation broth comprises a liquid fraction and a solid fraction.
  • the desired protein or enzyme may be recovered from the liquid fraction of the fermentation broth or from cell lysates. Recovery of the desired enzyme uses methods known to those skilled in the art. Suitable methods for recovery of proteins or enzymes from fermenta tion broth include but are not limited to collection, centrifugation, filtration, extraction, and precipitation.
  • Aqueous enzyme concentrates resulting from fermentation may comprise water in amounts of more than about 50% by weight, more than about 60% by weight, more than about 70% by weight, or more than about 80% by weight, all relative to the total weight of the enzyme concentrate.
  • Aqueous enzyme concentrates which result from fermentation may comprise residual components such as salts originating from the fermentation medium, cell debris originating from the production host cells, metabolites produced by the production host cells during fermentation.
  • residual components may be comprised in liquid enzyme concentrates in amounts less than 30% by weight, less than 20% by weight less, than 10% by weight, or less than 5% by weight, all relative to the total weight of the aqueous enzyme concentrate.
  • Hydrolases in the context of the present invention are identified by polypeptide se quences (also called amino acid sequences herein).
  • the polypeptide sequence speci fies the three-dimensional structure including the “active site” of an enzyme which in turn determines the catalytic activity of the same.
  • Polypeptide sequences may be iden tified by a SEQ ID NO. According to the World Intellectual Property Office (WIPO) Standard ST.25 (1998) the amino acids herein are represented using three-letter code with the first letter as a capital or the corresponding one letter.
  • the hydrolase according to the invention relates to parent enzymes and/or variant en zymes, both having enzymatic activity.
  • Hydrolases having enzymatic activity are enzy matically active or exert enzymatic conversion, meaning that enzymes act on sub strates and convert these into products.
  • Preferred hydrolases are selected from the group of enzymes acting on ester bond (E.C. 3.1), glycosylases (E.C. 3.2), and pepti dases (E.C. 3.4).
  • Enzymes acting on ester bond (E.C. 3.1) are hereinafter also re ferred to as lipases, and DNAses.
  • Glycosylases (E.C. 3.2) are hereinafter also referred to as either amylases, cellulases, and mannanases.
  • Peptidases are hereinafter also referred to as proteases.
  • enzyme herein excludes inactive variants of an enzyme.
  • a “parent” sequence (of a parent protein or enzyme, also called “parent enzyme”) is the starting sequence for introduction of changes (e.g. by introducing one or more amino acid substitutions, insertions, deletions, or a combination thereof) to the sequence, re sulting in “variants” of the parent sequences.
  • the term parent enzyme (or parent se quence) includes wild-type enzymes (sequences) and synthetically generated se quences (enzymes) which are used as starting sequences for introduction of (further) changes.
  • enzyme variant or “sequence variant” or “variant enzyme” refers to an en zyme that differs from its parent enzyme in its amino acid sequence to a certain extent. If not indicated otherwise, variant enzyme “having enzymatic activity” means that this variant enzyme has the same type of enzymatic activity as the respective parent en zyme.
  • Amino acid substitutions are described by providing the original amino acid of the par ent enzyme followed by the number of the position within the amino acid sequence, followed by the substituted amino acid.
  • Amino acid deletions are described by providing the original amino acid of the parent enzyme followed by the number of the position within the amino acid sequence, fol lowed by * .
  • Amino acid insertions are described by providing the original amino acid of the parent enzyme followed by the number of the position within the amino acid sequence, fol lowed by the original amino acid and the additional amino acid.
  • an inser tion at position 180 of lysine next to glycine is designated as “Gly180Glyl_ys” or “G180GK”
  • Arg170Tyr, Glu represents a substitution of arginine at position 170 with tyrosine or glutamic acid.
  • Arg170Tyr, Glu represents a substitution of arginine at position 170 with tyrosine or glutamic acid.
  • different alterations or optional substitutions may be indicated in brackets e.g. Arg170[Tyr, Gly] or Arg170 ⁇ Tyr, Gly ⁇ ; or in short R170 [Y,G] or R170 ⁇ Y, G ⁇ ; or in long R170Y, R170G.
  • Enzyme variants may be defined by their sequence identity when compared to a parent enzyme. Sequence identity usually is provided as “% sequence identity” or “% identity”. For calculation of sequence identities, in a first step a sequence alignment has to be produced. According to this invention, a pairwise global alignment has to be produced, meaning that two sequences have to be aligned over their complete length, which is usually produced by using a mathematical approach, called alignment algorithm.
  • the alignment is generated by using the algorithm of Needleman and Wunsch (J. Mol. Biol. (1979) 48, p. 443-453).
  • the program “NEEDLE” The European Molecular Biology Open Software Suite (EMBOSS)
  • EMBOSS European Molecular Biology Open Software Suite
  • %-identity (identical residues / length of the alignment region which is showing the respective se quence of this invention over its complete length) * 100.
  • enzyme variants may be described as an amino acid se quence which is at least n% identical to the amino acid sequence of the respective parent enzyme with “n” being an integer between 10 and 100.
  • var iant enzymes are at least 70%, at least 75%, at least 80%, at least 81%, at least 82%, at least 83%, at least 84%, at least 85%, at least 86%, at least 87%, at least 88%, at least 89%, at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98%, or at least 99% identical when com- pared to the full length amino acid sequence of the parent enzyme, wherein the en zyme variant has enzymatic activity.
  • Enzyme variants may be defined by their sequence similarity when compared to a par- ent enzyme. Sequence similarity usually is provided as “% sequence similarity” or “%- similarity”. % sequence similarity takes into account that defined sets of amino acids share similar properties, e.g by their size, by their hydrophobicity, by their charge, or by other characteristics. Herein, the exchange of one amino acid with a similar amino acid may be called “conservative mutation”.
  • ami no acid A is similar to amino acids S; amino acid D is similar to amino acids E and N; amino acid E is similar to amino acids D and K and Q; amino acid F is similar to amino acids W and Y; amino acid H is similar to amino acids N and Y; amino acid I is similar to amino acids L and M and V; amino acid K is similar to amino acids E and Q and R; amino acid L is similar to amino acids I and M and V; amino acid M is similar to amino acids I and L and V; amino acid N is similar to amino acids D and H and S; amino acid Q is similar to amino acids E and K and R; amino acid R is similar to amino acids K and Q; amino acid S is similar to amino acids A and N and T; amino acid T is similar to amino acids S; amino acid V is similar to amino acids I and L and M; amino acid W is similar to amino acids F and Y; amino acid Y is similar to amino acids F and H and W
  • Conservative amino acid substitutions may occur over the full length of the sequence of a polypeptide sequence of a functional protein such as an enzyme. In one embodi- ment, such mutations are not pertaining the functional domains of an enzyme. In one embodiment, conservative mutations are not pertaining the catalytic centers of an en zyme.
  • a value for sequence similarity of two amino acid sequences may be calculated from the same alignment, which is used to calculate %-identity.
  • %-similarity [ (identical residues + similar residues) / length of the alignment region which is showing the respective sequence(s) of this invention over its complete length ] * 100.
  • enzyme variants may be described as an amino acid se quence which is at least m% similar to the respective parent sequences with “m” being an integer between 10 and 100.
  • variant enzymes are at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98%, or at least 99% similar when compared to the full length polypeptide sequence of the parent enzyme, wherein the variant enzyme has enzymatic activity.
  • Enzymatic activity means the catalytic effect exerted by an enzyme, which usually is expressed as units per milligram of enzyme (specific activity) which relates to mole cules of substrate transformed per minute per molecule of enzyme (molecular activity).
  • Variant enzymes may have enzymatic activity according to the present invention when said enzyme variants exhibit at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at 10 least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or 100% of the enzymatic activity of the respective parent enzyme.
  • component (e) comprises at least one protease and/or at least one lipase and/or at least one amylase and/or at least one cellulase and/or at least one mannanase and/or at least one DNase.
  • inventive enzyme preparations comprise at least one protease (component (e)).
  • Proteases are members of class EC 3.4.
  • Proteases include ami- nopeptidases (EC 3.4.11), dipeptidases (EC 3.4.13), dipeptidyl-peptidases and tripep- tidyl-peptidases (EC 3.4.14), peptidyl-dipeptidases (EC 3.4.15), serine-type carboxy- peptidases (EC 3.4.16), metallocarboxypeptidases (EC 3.4.17), cysteine-type carboxy- peptidases (EC 3.4.18), omega peptidases (EC 3.4.19), serine endopeptidases (EC 3.4.11), ami- nopeptidases (EC 3.4.11), dipeptidases (EC 3.4.13), dipeptidyl-peptidases and tripep- tidyl-peptidases (EC 3.4.14), peptidyl-dipeptidases (EC 3.4.15
  • At least one protease is selected from serine proteases (EC 3.4.21), cysteine endopeptidases (EC 3.4.22), aspartic endopeptidases (EC 3.4.23), metallo-endopeptidases (EC 3.4.24), threonine endopeptidases (EC 3.4.25), or endo peptidases of unknown catalytic mechanism (EC 3.4.99).
  • at least one protease is selected from serine proteases (EC
  • Serine proteases or serine peptidases are characterized by having a serine in the catalytically active site, which forms a covalent adduct with the substrate during the catalytic reaction.
  • a serine protease in the context of the present invention is selected from the group consisting of chymotrypsin (e.g., EC 3.4.21.1), elastase (e.g., EC 3.4.21.36), elastase (e.g., EC 3.4.21.37 or EC 3.4.21.71), granzyme (e.g., EC
  • subtilisin is also known as subtilopeptidase, e.g., EC 3.4.21.62, the latter hereinafter also being referred to as “subtilisin”.
  • subtilases A sub-group of the serine proteases tentatively designated as subtilases has been pro posed by Siezen et al. (1991), Protein Eng. 4:719-737 and Siezen et al. (1997), Protein Science 6:501-523.
  • Subtilases includes the subtilisin family, thermitase family, the pro teinase K family, the lantibiotic peptidase family, the kexin family and the pyrolysin family.
  • subtilases A subgroup of the subtilases are the subtilisins which are serine proteases from the family S8 as defined by the MEROPS database (http://merops.sanger.ac.uk).
  • subtilisin related class of serine proteases shares a common amino acid sequence defining a catalytic triad which distinguishes them from the chymotrypsin related class of serine proteases.
  • subtilisins as described in WO 89/06276 and EP 0283075, WO 89/06279, WO 89/09830, WO 89/09819, WO 91/06637 and WO 91/02792.
  • Proteases are active proteins exerting “protease activity” or “proteolytic activity”. Prote olytic activity is related to the rate of degradation of protein by a protease or proteolytic enzyme in a defined course of time.
  • Proteolytic activity may be provided in units per gram enzyme.
  • 1 U prote ase may correspond to the amount of protease which sets free 1 pmol folin-positive amino acids and peptides (as tyrosine) per minute at pH 8.0 and 37°C (casein as sub strate).
  • Proteases of the subtilisin type may be bacterial proteases originating from a microorganism selected from Bacillus, Clostridium, Enterococcus, Geobacillus, Lactobacillus, Lactococcus, Oceanobacillus, Staphylococcus, Streptococcus, or Strep- tomyces protease, or a Gram-negative bacterial polypeptide such as a Campylobacter, E. coH, Flavobacterium, Fusobacterium, Helicobacter, Hyobacter, Neisseria, Pseudo monas, Salmonella, and Ureaplasma.
  • At least one protease is selected from Bacillus a /- calophilus, Bacillus amyloliquefaciens, Bacillus brevis, Bacillus circulans, Bacillus dau- sii, Bacillus coagulans, Bacillus firmus, Bacillus gibsonii, Bacillus lautus, Bacillus lentus, Bacillus Hcheniformis, Bacillus megaterium, Bacillus pumHus, Bacillus sphaericus, Ba cillus stearothermophi/us, Bacillus subtiHs, or Bacillus thuringiensis protease.
  • At least one protease is selected from the following: subtilisin from Bacillus amyloliquefaciens BPN' (described by Vasantha et al. (1984) J. Bacteriol. Volume 159, p 811-819 and JA Wells et al. (1983) in Nucleic Acids Research, Volume 11, p. 7911-7925); subtilisin from Bacillus Hcheniformis (subtilisin Carlsberg; disclosed in EL Smith et al. (1968) in J. Biol Chem, Volume 243, pp. 2184- 2191, and Jacobs et al. (1985) in Nucl. Acids Res, Vol 13, p.
  • subtilisin PB92 original sequence of the alkaline protease PB92 is described in EP 283075 A2; subtilisin 147 and/or 309 (Esperase®, Savinase®, respectively) as disclosed in WO 89/06279; subtilisin from Bacillus lentus as disclosed in WO 91/02792, such as from Bacillus lentus DSM 5483 or the variants of Bacillus lentus DSM 5483 as described in WO 95/23221; subtilisin from Bacillus a/ca/ophi/us ⁇ DSM 11233) disclosed in DE 10064983; subtilisin from Bacillus gibsonii ⁇ DSM 14391) as disclosed in WO 2003/054184; subtilisin from Bacillus sp.
  • subtilisin having SEQ ID NO: 1 (DSM 14390) disclosed in WO 2003/056017; subtilisin from Bacillus sp. (DSM 14392) disclosed in WO 2003/055974; subtilisin from Bacillus gibsonii (DSM 14393) disclosed in WO 2003/054184; subtilisin having SEQ ID NO: 1 (DSM 14390) disclosed in WO 2003/056017; subtilisin from Bacillus sp. (DSM 14392) disclosed in WO 2003/055974; subtilisin from Bacillus gibsonii (DSM 14393) disclosed in WO 2003/054184; subtilisin having SEQ ID NO: 1 (DSM 14392) disclosed in WO 2003/055974; subtilisin from Bacillus gibsonii (DSM 14393) disclosed in WO 2003/054184; subtilisin having SEQ ID NO: 1 (DSM 14392) disclosed in WO 2003/055974; subtilisin from Bacillus gibsonii (DS
  • component (e) comprises at least subtilisin 309 (which might be called Savinase herein) as disclosed as sequence a) in Table I of WO 89/06279 or a variant which is at least 80% identical thereto and has proteolytic activity.
  • subtilisin 309 which might be called Savinase herein
  • Examples of useful proteases in accordance with the present invention comprise the variants described in: WO 92/19729, WO 95/23221, WO 96/34946, WO 98/20115, WO 98/20116, WO 99/11768, WO 01/44452, WO 02/088340, WO 03/006602, WO 2004/03186, WO 2004/041979, WO 2007/006305, WO 2011/036263, WO 2011/036264, and WO 2011/072099.
  • Suitable examples comprise especially variants of subtilisin protease derived from SEQ ID NO:22 as described in EP 1921147 (which is the sequence of mature alkaline protease from Bacillus lentus DSM 5483) with ami no acid substitutions in one or more of the following positions: 3, 4, 9, 15, 24, 27, 33,
  • Suitable proteases include protease variants having proteolytic activity which are at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98% or at least 99% similar when compared to the full length polypeptide sequence of the parent enzyme.
  • At least one protease has SEQ ID NO:22 as described in EP 1921147, or a protease which is at least 80% identical thereto and has proteolytic activ ity.
  • said protease is characterized by having amino acid glutamic acid (E), or aspartic acid (D), or asparagine (N), or glutamine (Q), or alanine (A), or glycine (G), or serine (S) at position 101 (according to BPN’ numbering) and has prote olytic activity.
  • said protease comprises one or more further substi tutions: (a) threonine at position 3 (3T), (b) isoleucine at position 4 (4I), (c) alanine, threonine or arginine at position 63 (63A, 63T, or 63R), (d) aspartic acid or glutamic acid at position 156 (156D or 156E), (e) proline at position 194 (194P), (f) methionine at position 199 (199M), (g) isoleucine at position 205 (205I), (h) aspartic acid, glutamic acid or glycine at position 217 (217D, 217E or 217G), (i) combinations of two or more amino acids according to (a) to (h).
  • At least one protease may be at least 80% identical to SEQ ID NO:22 as described in EP 1921147 and is characterized by comprising one amino acid (according to (a)-(h)) or combinations according to (i) together with the ami no acid 101 E, 101D, 101N, 101Q, 101A, 101G, or 101S (according to BPN’ numbering) and having proteolytic activity.
  • said protease is characterized by comprising the mutation (according to BPN’ numbering) R101E, or S3T + V4I + V205I, or R101E and S3T, V4I, and V205I, or S3T + V4I + V199M + V205I + L217D, and hav ing proteolytic activity.
  • the protease having a polypeptide sequence according to SEQ ID NO:22 as described in EP 1921147 with R101E substitution may be called Lavergy Pro 104 LS herein, and is preferred in some embodiments.
  • protease according to SEQ ID NO:22 as described in EP 1921147 is characterized by comprising the mutation (according to BPN’ numbering) S3T + V4I + S9R + A15T + V68A + D99S + R101S + A103S + 1104V + N218D, and having prote olytic activity.
  • a combination of at least two proteases may be used.
  • inventive enzyme preparations comprise at least one lipase (com ponent (e)).
  • lipase means active protein having lipase activity (or lipolytic activity; triacylglycerol lipase, EC 3.1.1.3), cutinase activity (EC 3.1.1.74; enzymes having cutinase activity may be called cutinase herein), sterol ester ase activity (EC 3.1.1.13) and/or wax-ester hydrolase activity (EC 3.1.1.50).
  • lipase activity may be measured by ester bond hydrolysis in the substrate para-nitrophenyl palmitate (pNP-Palmitate, C:16) and releases pNP which is yellow and can be detected at 405 nm.
  • Lipolytic activity means the catalytic effect exerted by a lipase, which may be provided in lipolytic units (LU).
  • Lipases include those of bacterial or fungal origin.
  • a suitable lipase is selected from the following: lipases from Humicola (synonym Ther- momyces), e.g. from H. lanuginosa ⁇ T lanuginosus) as described in EP 258068, EP 305216, WO 92/05249 and WO 2009/109500 or from H. inso/ens as described in WO 96/13580; lipases derived from Rhizomucor miehei as described in WO 92/05249; li- pase from strains of Pseudomonas (some of these now renamed to Burkholderia ), e.g. from P. alcaligenes or P.
  • pseudoalcaligenes EP 218272, WO 94/25578, WO 95/30744, WO 95/35381, WO 96/00292
  • P. cepacia EP 3313766
  • P. stutzeri ⁇ GB 1372034 P. fiuorescens
  • Pseudomonas sp. strain SD705 WO 95/06720 and WO 96/27002
  • P. wisconsinensis WO 96/12012
  • Pseudomonas mendocina /WO 95/14783 P. giumae (WO 95/35381 , WO 96/00292)
  • lipase from Streptomyces griseus WO 2011/150157
  • stearothermophiius JP S64-074992 or B. pumiius (WO 91/16422); lipase from Candida antarctica as disclosed in WO 94/01541 ; cutinase from Pseudomonas mendocina (US 5389536, WO 88/09367); cutinase from Magnaporthe grisea (WO 2010/107560); cutinase from Fusarum soiani pisi as disclosed in WO 90/09446, WO 00/34450 and WO 01/92502; and cutinase from Humicoia lanuginosa as disclosed in WO 00/34450 and WO 01/92502.
  • Suitable lipases also include those referred to as acyltransferases or perhydrolases, e.g. acyltransferases with homology to Candida antarctica lipase A (WO 2010/111143), acyltransferase from Mycobacterium smegmatis (WO 2005/056782), perhydrolases from the CE7 family (WO 2009/67279), and variants of the M. smegmatis perhydrolase in particular the S54V variant (WO 2010/100028)
  • Suitable lipases include also those which are variants of the above described lipases which have lipolytic activity. Such suitable lipase variants are e.g. those which are de veloped by methods as disclosed in WO 95/22615, WO 97/04079, WO 97/07202, WO 00/60063, WO 2007/087508, EP 407225 and EP 260105.
  • Suitable lipases include lipase variants having lipolytic activity which are at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98% or at least
  • Suitable lipases include lipase variants having lipolytic activity which are at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98% or at least 99% similar when compared to the full length polypeptide sequence of the parent en zyme.
  • lipase is selected from fungal triacylglycerol lipase (EC class 3.1.1.3).
  • Fungal triacylglycerol lipase may be selected from lipases of Thermomyces lanuginosa.
  • at least one Thermomyces lanuginosa lipase is se lected from triacylglycerol lipase according to amino acids 1-269 of SEQ ID NO:2 of US 5869438 and variants thereof having lipolytic activity.
  • Triacylglycerol lipase accord ing to amino acids 1-269 of SEQ ID NO:2 of US 5869438 may be called Lipolase here in.
  • Thermomyces lanuginosa lipase may be selected from variants having lipolytic activity which are at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98% or at least 99% identical when compared to the full length polypeptide sequence of amino acids 1-269 of SEQ ID NO:2 of US 5869438.
  • Thermomyces lanuginosa lipase may be selected from variants having lipolytic activity comprising conservative mutations only, which do however not pertain the functional domain of amino acids 1-269 of SEQ ID NO:2 of US 5869438.
  • Lipase variants of this embodiment having lipolytic activity may be at least 95%, at least 96%, at least 97%, at least 98% or at least 99% similar when compared to the full length polypeptide se quence of amino acids 1-269 of SEQ ID NO:2 of US 5869438.
  • At least one Thermomyces lanuginosa lipase may be at least 80% identical to SEQ ID NO:2 of US 5869438 characterized by having amino acid T231R and N233R.
  • Said Thermomyces lanuginosa lipase may further comprise one or more of the following amino acid exchanges: Q4V, V60S, A150G, L227G, P256K. According to the present invention, a combination of at least two lipases may be used.
  • inventive enzyme preparations comprise at least one amylase (component (e)) “Amylases” according to the invention (alpha and/or beta) include those of bacterial or fungal origin (EC 3.2.1.1 and 3.2.1.2, respectively). Chemically modified or protein engineered mutants are included.
  • Amylases according to the invention have “amylolytic activity” or “amylase activity” in- volving (endo)hydrolysis of glucosidic linkages in polysaccharides a-amylase activity may be determined by assays for measurement of a-amylase activity which are known to those skilled in the art. Examples for assays measuring a-amylase activity are: a-amylase activity can be determined by a method employing Phadebas tablets as substrate (Phadebas Amylase Test, supplied by Magle Life Science). Starch is hydro- lyzed by the a-amylase giving soluble blue fragments.
  • the absorbance of the resulting blue solution, measured spectrophotometrically at 620 nm, is a function of the a- amylase activity.
  • the measured absorbance is directly proportional to the specific activ ity (activity/mg of pure a-amylase protein) of the a-amylase in question under the given set of conditions.
  • a-amylase activity can also be determined by a method employing the Ethyliden-4- nitrophenyl-a-D-maltoheptaosid (EPS).
  • EPS Ethyliden-4- nitrophenyl-a-D-maltoheptaosid
  • D-maltoheptaoside is a blocked oligosaccha ride which can be cleaved by an endo-arnylase.
  • the slope of the time dependent absorption- curve is directly proportional to the specific activity (activity per mg enzyme) of the a- amylase in question under the given set of conditions.
  • Amylolytic activity may be provided in units per gram enzyme.
  • 1 unit a- amylase may liberate 1.0 mg of maltose from starch in 3 min at pH 6.9 at 20°C.
  • At least one amylase may be selected from the following: amylases from Bacillus Hcheniformis having SEQ ID NO:2 as described in WO 95/10603 Suitable variants are described in WO 95/10603 comprising one or more substitutions in the following positions: 15, 23, 105, 106, 124, 128, 133,
  • Suitable variants of SEQ ID NO:6 include those comprising a deletion in positions 181 and/or 182 and/or a substitution in position 193.
  • Preferred variants of SEQ NO: 6 are those having a substitution, a de letion or an insertion in one or more of the following positions: R181, G182,
  • amylases having SEQ ID NO:1 as described in WO 2013/001078 or amylase variants comprising an alteration at two or more (several) positions corresponding to positions G304, W140, W189, D134, E260, F262, W284, W347, W439, W469, G476, and G477 within said SEQ ID NO:1.
  • amylases having SEQ ID NO:2 as described in WO 2013/001087 or amylase variants comprising a deletion of positions 181+182, or 182+183, or 183+184, within said SEQ ID NO:2, optionally comprising one or two or more modifications in any of positions corresponding to W140, W159, W167, Q169, W189, E194, N260, F262, W284, F289, G304, G305, R320, W347, W439, W469, G476 and G477 within said SEQ ID NO:2.
  • amylases which are hybrid alpha-amylases from above mentioned amylases as for example as described in WO 2006/066594;
  • hybrid amylases according to WO 2014/183920 with A and B domains having at least 90% identity to SEQ ID NO:2 of WO 2014/183920 and a C domain having at least 90% identity to SEQ ID NO:6 of WO 2014/183920, wherein the hybrid amylase has amylolytic activity; preferably the hybrid alpha-amylase is at least 95% identical to SEQ ID NO: 23 of WO 2014/183920 and having amylolytic activ ity;
  • hybrid amylase according to WO 2014/183921 with A and B domains having at least 75% identity to SEQ ID NO: 2, SEQ ID NO: 15, SEQ ID NO: 20, SEQ ID NO: 23, SEQ ID NO: 29, SEQ ID NO: 26, SEQ ID NO: 32, and SEQ ID NO: 39 as disclosed in WO 2014/183921 and a C domain having at least 90% identity to SEQ ID NO: 6 of WO 2014/183921 , wherein the hybrid amylase has amylolytic activity; preferably, the hybrid alpha-amylase is at least 95% identical to SEQ ID NO: 30 as disclosed in WO 2014/183921 and having amylolytic activity.
  • Suitable amylases comprised in component (e) include amylase variants of the amyl ases disclosed herein having amylase activity which are at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98% or at least 99% identical when compared to the full-length polypeptide sequence of the parent enzyme as disclosed above.
  • Suitable amylases comprised in component (e) include amylase variants of the amyl ases disclosed herein having amylase activity which are at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98% or at least 99% similar when compared to the full-length polypeptide sequence of the parent enzyme.
  • a combination of at least two amylases may be used.
  • At least one enzyme comprised in component (e) may be selected from the group of cellulases.
  • At least one cellulase may be selected from cellobiohydrolase (1 ,4-P-D- glucan cellobiohydrolase, EC 3.2 1.91), endo-ss-1 ,4-glucanase (endo-1 ,4-P-D-glucan 4-glucanohydrolase, EC 3.2.1.4) and ss-glucosidase (EC 3.2.1.21).
  • compo nent (e) comprises at least one cellulase of the glycosyl hydrolase family 7 (GH7, pfam00840), preferably selected from endoglucanases (EC 3.2.1.4).
  • Cellulases are enzymes involved in hydrolysis of cellulose. Assays for measurement of “cellulase activity” or “cellulolytic activity” are known to those skilled in the art. For example, cellulolytic activity may be determined by virtue of the fact that cellulase hydrolyses carboxymethyl cellulose to reducing carbohydrates, the reducing ability of which is determined colorimetrically by means of the ferricyanide reaction, according to Hoffman, W S., J. Biol. Chem. 120, 51 (1937).
  • component (e) comprises at least one cellulase 80% identical to a polypeptide sequence according to SEQ ID NO:2 of WO 95/02675. In one embodi ment, component (e) comprises at least one cellulase 80% identical to a polypeptide sequence according to SEQ ID NO:4 of WO 2004/053039. In one embodiment, com ponent (e) comprises at least one cellulase 80% identical to a polypeptide sequence according to SEQ ID NO:2 of WO 2002/99091.
  • Cellulolytic activity may be provided in units per gram enzyme. For example, 1 unit may liberate 1.0 pmole of glucose from cellulose in one hour at pH 5.0 at 37 °C (2 hour in cubation time).
  • Cellulases according to the invention include those of bacterial or fungal origin. In one embodiment, at least one cellulase is selected from cellulases comprising a cellulose binding domain. In one embodiment, at least one cellulase is selected from cellulases comprising a catalytic domain only, meaning that the cellulase lacks cellulose binding domain. According to the present invention, component (e) may comprise a combination of at least two cellulases, preferably selected from endoglucanases (EC 3.2.1.4) as dis closed above.
  • At least one enzyme comprised in component (e) may be selected from the group of mannan degrading enzymes.
  • At least one mannan degrading enzyme may be selected from b-mannosidase (EC 3.2.1.25), endo-1 ,4-0-mannosidase (EC 3.2.1.78), and 1,4-b- mannobiosidase (EC 3.2.1.100).
  • at least one mannan degrading enzyme is selected from the group of endo-1 ,4-0-mannosidase (EC 3.2.1.78), a group of enzymes which may be called endo-0-1,4-D-mannanase, b-mannanase, or mannanase herein.
  • a polypeptide having mannanase activity may be tested for mannanase activity accord ing to standard test procedures known in the art, such as by applying a solution to be tested to 4 mm diameter holes punched out in agar plates containing 0.2% AZCL gal- actomannan (carob), i. e. substrate for the assay of endo-1 ,4-beta-D-mannanase avail able as CatNo l-AZGMAfrom the company Megazyme (Megazyme's Internet address: http://www.megazyme.com/Purchase/indlex.html).
  • Component (e) may comprise at least one mannanase selected from alkaline man nanase of Family 5 or 26.
  • alkaline mannanase is meant to encompass mannanases having an enzymatic activity of at least 40% of its maximum activity at a given pH ranging from 7 to 12, preferably 7.5 to105.
  • At least one mannanase comprised in component (e) may be selected from man nanases originating from Bacillus organisms, such as described in JP-0304706 [beta- mannanase from Bacillus spi ⁇ , JP-63056289 [alkaline, thermostable beta-mannanase], JP-63036774 [ Bacillus microorganism FEERM P-8856 producing beta-mannanase and beta-mannosidase at an alkaline pH], JP-08051975 [alkaline beta-mannanases from alkalophilic Bacillus sp.
  • At least one mannanase comprised in component (e) is a polypep tide 80% identical to SEQ ID NO: 2 in US6566114. At least one mannanase comprised in component (e) may be selected from mannanases originating from Trichoderma or- ganisms, such as disclosed in WO 93/24622 or in WO 2011/085747.
  • component (e) may comprise a combination of at least two mannan-degrading enzymes, preferably selected from endo-1 ,4-b- mannosidase (EC 3.2.1.78) as disclosed above
  • DNAse activity may be determined on DNAse Test Agar with Methyl Green (BD, Frank lin Lakes, NJ, USA), which should be prepared according to the manual from supplier. Briefly, 21 g of agar is dissolved in 500 ml water and then autoclaved for 15 min at 121 °C. Autoclaved agar is temperated 10 to 48°C in water bath, and 20 ml of agar is to be poured into petridishes with and allowed to solidify by incubation o/n at room tempera ture. On solidified agar plates, 5 pi of enzyme solution is added and DNAse activity is observed as colorless zones around the spotted enzyme solutions.
  • BD Methyl Green
  • At least one DNAse comprised in component (e) may be selected from DNAses origi- nating from Bacillus such as from Bacillus cibi, Bacillus horikoshii, Bacillus horneckiae, Bacillus idriensis, Bacillus algicola, Bacillus vietnamensis, Bacillus hwajinpoensis , Pae- ni bad Hus mucHanginosus, Bacillus indicus, Bacillus luciferensis, Bacillus marisflavi, and variants thereof.
  • at least one DNAse in component (e) is se lected from polypeptides 80% identical to SEQ ID NO: 1 of WO 2019/081724.
  • Said polypeptide may comprise one or more substitutions at positions selected from T 1 , G4, S7, K8, S9, S13, N16, T22, S25, S27, D32, L33, S39, G41, S42, D45, Q48, S57, S59, N61, T65, S66, V76, F78, P91, S101, S106, Q109, A112, S116, T127, S130, T138, Q140, S144, A147, C148, W154, T157, Y159, G162, S167, Q174, G175, L177, S179, and C180 - all as disclosed in Wo2019/081724 and WO 2019/081721.
  • Component (e) may comprise DNAse variants having DNA degrading activity which are at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98% or at least 99% similar when compared to the full-length polypeptide sequence of the corresponding parent enzyme as disclosed above.
  • component (e) may comprise a combination of at least two DNAses.
  • the liquid enzyme preparation of the invention may comprise at least one enzyme sta bilizer.
  • Said enzyme stabilizer may be selected from boron-containing compounds, polyols, peptide aldehydes, other stabilizers, and mixtures thereof.
  • Boron-containing compounds may be selected from boric acid or its derivatives and from boronic acid or its derivatives such as aryl boronic acids or its derivatives, from salts thereof, and from mixtures thereof. Boric acid herein may be called orthoboric acid.
  • boron-containing compound is selected from the group consisting of aryl boronic acids and its derivatives.
  • boron-containing com pound is selected from the group consisting of benzene boronic acid (BBA) which is also called phenyl boronic acid (PBA), derivatives thereof, and mixtures thereof.
  • BBA benzene boronic acid
  • PBA phenyl boronic acid
  • phenyl boronic acid derivatives are selected from the group consisting of the derivatives of formula (1a) and (1b) formula: wherein
  • R1 is selected from the group consisting of hydrogen, hydroxy, non-substituted or sub stituted Ci-C 6 alkyl, and non-substituted or substituted C1-C6 alkenyl; in a preferred embodiment, R is selected from the group consisting of hydroxy, and non-substituted Ci alkyl;
  • R2 is selected from the group consisting of hydrogen, hydroxy, non-substituted or sub stituted Ci-C 6 alkyl, and non-substituted or substituted C1-C6 alkenyl; in a preferred embodiment, R is selected from the group consisting of H, hydroxy, and substituted Ci alkyl.
  • phenyl-boronic acid derivatives are selected from the group con sisting of 4-formyl phenyl boronic acid (4-FPBA), 4-carboxy phenyl boronic acid (4- CPBA), 4-(hydroxymethyl) phenyl boronic acid (4-HMPBA), and p-tolylboronic acid (p- TBA).
  • Suitable derivatives include: 2-thienyl boronic acid, 3-thienyl boronic acid, (2- acetamidophenyl) boronic acid, 2-benzofuranyl boronic acid, 1 -naphthyl boronic acid, 2-naphthyl boronic acid, 2-FPBA, 3-FBPA, 1-thianthrenyl boronic acid, 4-dibenzofuran boronic acid, 5-methyl-2-thienyl boronic acid, 1-benzothiophene-2 boronic acid, 2- furanyl boronic acid, 3-furanyl boronic acid, 4,4 biphenyl-diboronic acid, 6-hydroxy-2- naphthaleneboronic acid, 4-(methylthio) phenyl boronic acid, 4-(trimethylsilyl) phenyl boronic acid, 3-bromothiophene boronic acid, 4-methylthiophene boronic acid, 2- naphthyl boronic acid, 5-brom
  • Polyols may be selected from polyols containing from 2 to 6 hydroxyl groups. Suitable examples include glycol, propylene glycol, 1,2-propane diol, 1,2-butane diol, 1,2- pentane diol, ethylene glycol, hexylene glycol, glycerol, sorbitol, mannitol, erythriol, glucose, fructose, and lactose.
  • RASI RASI
  • BASI WASI (bifunctional alpha- amylase/subtilisin inhibitors
  • At least one peptide stabilizer may be selected from a compound of formula (2a) or a salt thereof or from a compound of formula (2b):
  • R 1 , R 2 , R 3 , R 4 , R 5 and Z within formulae (2a) and (2b) are defined as follows:
  • R 1 , R 2 and R 3 are each independently selected from the group consisting of hydrogen, optionally substituted C1-8 alkyl, optionally substituted C2-6 alkenyl, optionally substituted Ci-salkoxy, optionally substituted 3- to 12-membered cycloalkyl, and optionally substi tuted 6- to 10-membered aryl; or wherein each R 1 , R 2 and R 3 is independently selected as -(CH2)3- which is also attached to the nitrogen atom of-NH-C(H)- so that -N- C(H)R 1 ⁇ 2 or 3 - forms a 5-membered heterocyclic ring;
  • R 4 and R 5 are each independently selected from the group consisting of hydrogen, op tionally substituted Ci-s alkyl, optionally substituted C2-6 alkenyl, optionally substituted Ci-salkoxy, optionally substituted C- M acyl, optionally substituted Ci-s alkyl phenyl (e.g benzyl), and optionally substituted 6- to 10-membered aryl; or wherein R 4 and R 5 are joined to form an optionally substituted 5- or 6-membered ring;
  • Z is selected from hydrogen, an N-terminal protection group, and one or more amino acid residues optionally comprising an N-terminal protection group.
  • R 2 is a group such that NH-CHR 2 -CO is an L or D-amino acid residue of Gly, Ala, Val, Leu, lie, Met, Pro, Phe, Trp, Ser, Thr, Asp, Gin, Tyr, Cys, Lys, Arg, His, Asn, Glu, m-tyrosine, 3,4-dihydroxyphenylalanine, Nva, or Nle. More preferably, R 2 is a group such that NH-CHR 2 -CO is an L or D-amino acid residue of Ala, Cys, Gly, Pro, Ser, Thr, Val, Nva or Nle. Even more preferably, R 2 is a group such that NH-CHR 2 -CO is an L or D-amino acid residue of Ala, Gly, Pro or Val.
  • R 1 is a group such that NH-CHR 1 -CO is an L or D-amino acid resi due of Ala, Val, Gly, Arg, Leu, lie or His and R 2 is a group such that NH-CHR 2 -CO is an L or D-amino acid residue of Ala.
  • R 1 is a group such that NH- CHR 1 -CO is an L or D-amino acid residue of Ala, Val, Gly, Arg, Leu, lie or His and R 2 is a group such that NH-CHR 2 -CO is an L or D-amino acid residue of Gly.
  • R 1 is a group such that NH-CHR 1 -CO is an L or D-amino acid residue of Ala, Val, Gly, Arg, Leu, lie or His and R 2 is a group such that NH-CHR 2 -CO is an L or D-amino acid residue of Pro.
  • R 1 is a group such that NH-CHR 1 -CO is an L or D-amino acid residue of Ala, Val, Gly, Arg, Leu, lie or His and R 2 is a group such that NH-CHR 2 -CO is an L or D-amino acid residue of Val.
  • R 1 is a group such that NH-CHR 1 -CO is an L or D-amino acid resi due of Ala and R 2 is a group such that NH-CHR 2 -CO is an L or D-amino acid residue of Ala, Gly, Pro or Val.
  • R 1 is a group such that NH-CHR 1 -CO is an L or D-amino acid residue of Val and R 2 is a group such that NH-CHR 2 -CO is an L or D- amino acid residue of Ala, Gly, Pro or Val.
  • R 1 is a group such that NH-CHR 1 -CO is an L or D-amino acid residue of Gly and R 2 is a group such that NH- CHR 2 -CO is an L or D-amino acid residue of Ala, Gly, Pro or Val.
  • R 1 is a group such that NH-CHR 1 -CO is an L or D-amino acid residue of Arg and R 2 is a group such that NH-CHR 2 -CO is an L or D-amino acid residue of Ala, Gly, Pro or Val.
  • R 1 is a group such that NH-CHR 1 -CO is an L or D-amino acid resi due of Leu and R 2 is a group such that NH-CHR 2 -CO is an L or D-amino acid residue of Ala, Gly, Pro or Val.
  • R 1 is a group such that NH-CHR 1 -CO is an L or D-amino acid residue of lie and R 2 is a group such that NH-CHR 2 -CO is an L or D- amino acid residue of Ala, Gly, Pro or Val.
  • R 1 is a group such that NH-CHR 1 -CO is an L or D-amino acid residue of His and R 2 is a group such that NH- CHR 2 -CO is an L or D-amino acid residue of Ala, Gly, Pro or Val.
  • R 3 is a group selected from optionally substituted Ci-s alkyl, such as CH2Si(CH3)3, Ci-salkylphosphates such as (CH2) n PO(OR)2, Ci-s alkylnitriles such as CH 2 CN,
  • C-i-salkylsulfones such as CH2SO2R, Ci-salkylethers such as (CH2) n OR, C-i-salkylesters such as CH2CO2R, and Ci-salkylamides; optionally substituted C-i-salkoxy, optionally substituted 3- to 12-membered cycloalkyl, such as cyclohexylmethyl; and optionally substituted 6- to 10-membered aryl, wherein R is independently selected from the group consisting of hydrogen, optionally substituted Ci-s alkyl, optionally substituted Ci-s alkoxy, optionally substituted 3- to 12-membered cycloalkyl, optionally substituted 6- to 10-membered aryl, and optionally substituted 6- to 10-membered heteroaryl and n is an integer from 1 to 8, i.e. 1, 2, 3, 4, 5, 6, 7 or 8.
  • R 3 is a group such that NH-CHR 3 -CO is an L or D-amino acid residue of Tyr, m-tyrosine, 3,4-dihydroxyphenylalanine, Phe, Val, Ala, Met, Nva, Leu, lie or Nle or other non-natural amino acids carrying alkyl groups. More preferably, R 3 is a group such that NH-CHR 3 -CO is an L or D-amino acid residue of Tyr, Phe, Val, Ala or Leu.
  • R 1 and R 2 is a group such that NH-CHR 1 -CO and NH-CHR 2 -CO each is an L or D-amino acid residue of Ala, Cys, Gly, Pro, Ser, Thr, Val, Nva or Nle, and R 3 is a group such that NH-CHR 3 -CO is an L or D-amino acid residue of Tyr, m- tyrosine, 3,4-dihydroxyphenyl-alanine, Phe, Val, Ala, Met, Nva, Leu, lie or Nle.
  • R 1 is a group such that NH-CHR 1 -CO is an L or D-amino acid resi- due of Gly or Val
  • R 2 is a group such that NH-CHR 2 -CO is an L or D-amino acid residue of Ala
  • R 3 is a group such that NH-CHR 3 -CO is an L or D-amino acid residue of Tyr, Ala, or Leu.
  • R 1 is a group such that NH-CHR 1 -CO is an L or D-amino acid resi due of Val
  • R 2 is a group such that NH-CHR 2 -CO is an L or D-amino acid residue of Ala
  • R 3 is a group such that NH-CHR 3 -CO is an L or D-amino acid residue of Leu.
  • R 1 is a group such that NH-CHR 1 -CO is an L or D-amino acid resi due of Gly
  • R 2 is a group such that NH-CHR 2 -CO is an L or D-amino acid residue of Ala
  • R 3 is a group such that NH-CHR 3 -CO is an L or D-amino acid residue of Tyr.
  • R 1 is a group such that NH-CHR 1 -CO is an L or D-amino acid resi- due of Val
  • R 2 is a group such that NH-CHR 2 -CO is an L or D-amino acid residue of Ala
  • R 3 is a group such that NH-CHR 3 -CO is an L or D-amino acid residue of Ala.
  • R 1 is a group such that NH-CHR 1 -CO is an L or D-amino acid resi due of Val
  • R 2 is a group such that NH-CHR 2 -CO is an L or D-amino acid residue of Ala
  • R 3 is a group such that NH-CHR 3 -CO is an L or D-amino acid residue of Nor- leucine.
  • R 1 is a group such that NH-CHR 1 -CO is an L or D-amino acid resi due of Val
  • R 2 is a group such that NH-CHR 2 -CO is an L or D-amino acid residue of Ala
  • R 3 is a group such that NH-CHR 3 -CO is an L or D-amino acid residue of Nor- valine.
  • R 4 and R 5 are each independently selected from hydrogen, methyl, ethyl, i-propyl, n-propyl, i-butyl, s-butyl, n-butyl, i-pentyl, 2-pentyl, 3-pentyl, neopentyl, cyclopentyl, cyclohexyl, and benzyl.
  • R 4 and R 5 may each independently be selected from methyl, ethyl, isopropyl, 2-butyl or 3-pentyl. More preferably, R 4 and R 5 are both methyl, ethyl, isopropyl, 2-butyl or 3- pentyl.
  • Z is selected from hydrogen, an N-terminal protection group, and one or more amino acid residues optionally comprising an N-terminal protection group.
  • Z is an N-terminal protection group.
  • the N-terminal protection group is preferably a small aliphatic group, e.g., formyl, ace tyl, fluorenylmethyloxycarbonyl (Fmoc), fevf-butyloxycarbonyl (Boc), methoxycarbonyl (Moc); methoxyacetyl (Mac); methyl carbamate or a methylamino carbonyl/methyl urea group.
  • a small aliphatic group e.g., formyl, ace tyl, fluorenylmethyloxycarbonyl (Fmoc), fevf-butyloxycarbonyl (Boc), methoxycarbonyl (Moc); methoxyacetyl (Mac); methyl carbamate or a methylamino carbonyl/methyl urea group.
  • the N-terminal protection group is preferably a bulky aromatic group such as benzoyl (Bz), benzyloxycarbonyl (Cbz), jO -methoxybenzyl car bonyl (MOZ), benzyl (Bn), p-methoxybenzyl (PMB) or p-methoxyphenyl (PMP).
  • Bz benzoyl
  • Cbz benzyloxycarbonyl
  • MOZ jO -methoxybenzyl car bonyl
  • Bn benzyl
  • PMB p-methoxybenzyl
  • PMP p-methoxyphenyl
  • N-terminal protection groups are described in Greene’s Protective Groups in Organic Synthesis, Fifth Edition by Peter G. M. Wuts, published in 2014 by John Wiley & Sons, Inc and in Isidro-Llobet et al., Amino Acid-Protecting Groups, Chem. Rev. 2009 109(6), 2455-2504.
  • the N-terminal protection group is selected from benzyloxycarbonyl (Cbz),O-metho-xybenzyl carbonyl (MOZ), benzyl (Bn), benzoyl (Bz), yo-methoxybenzyl (PMB), yO-methoxyphenyl (PMP), formyl, acetyl (Ac), methyloxy, alkoxycarbonyl, methoxycar- bonyl, fluorenylmethyloxycarbonyl (Fmoc), or te/f-butyloxycarbonyl (Boc).
  • the N-terminal protection group is benzyloxycarbonyl (Cbz).
  • the peptide stabilizer is selected from compounds accord ing to formula (2b), wherein
  • R 1 and R 2 is a group such that NFI-CHR 1 -CO and NH-CHR 2 -CO each is an L or D-amino acid residue selected from Ala, Cys, Gly, Pro, Ser, Thr, Val, Nva or Nle, and R 3 is a group such that NH-CHR 3 -CO is an L or D-amino acid residue select ed from Tyr, m-tyrosine, 3,4-dihydroxyphenylalanine, Phe, Val, Ala, Met, Nva, Leu, lie or Nle; and ⁇ the N-terminal protection group Z is selected from benzyloxycarbonyl (Cbz), p- methoxybenzyl carbonyl (MOZ), benzyl (Bn), benzoyl (Bz), /7-methoxybenzyl (PMB), yO-methoxyphenyl (PMP), formyl, acetyl (Ac), methyloxy, alkoxycarbonyl
  • R 1 is a group such that NFI-CHR 1 -CO is an L or D-amino acid residue of Val
  • R 2 is a group such that NFI-CHR 2 -CO is an L or D-amino acid residue of Ala
  • R 3 is a group such that NH-CHR 3 -CO is an L or D-amino acid residue of Leu;
  • the N-terminal protection group Z is selected from benzyloxycarbonyl (Cbz), p- methoxybenzyl carbonyl (MOZ), benzyl (Bn), benzoyl (Bz), /7-methoxybenzyl (PMB), o-methoxyphenyl (PMP), formyl, acetyl (Ac), methyloxy, alkoxycarbonyl, methoxycarbonyl, fluorenylmethyloxycarbonyl (Fmoc), or te/7-butyloxycarbonyl (Boc); preferably, the N-terminal protection group Z is benzyloxycarbonyl (Cbz).
  • the enzyme preparation comprises about 0.1-2% by weight rela- tive to the total weight of the enzyme preparation of at least one peptide stabilizer.
  • the enzyme preparation comprises about 0.15-1%, or 0.2-0.5%, or about 0.3% by weight relative to the total weight of the enzyme preparation of at least one peptide stabilizer. More preferably, the enzyme preparation comprises about 0.3% by weight relative to the total weight of the enzyme preparation of a peptide stabilizer ac- cording to formula (2b) characterized in
  • R 1 is a group such that NH-CHR 1 -CO is an L or D-amino acid residue of Val
  • R 2 is a group such that NH-CHR 2 -CO is an L or D-amino acid residue of Ala
  • R 3 is a group such that NH-CHR 3 -CO is an L or D-amino acid residue of Leu;
  • N-terminal protection group Z is benzyloxycarbonyl (Cbz).
  • Components (f) are for example reducing agents, anti-oxidants and metal complex- ing/chelating agents.
  • Metal chelating and -complexing agents may also act as stabilizing agents; these op tional components, however, are mentioned under further additives (i.e. component (e), see above).
  • Reducing agents and anti-oxidants are for example the reducing agents mentioned in German patent DE2020968, page 3.
  • stabilizing agents (f) are for example the acids, acid generating substances, anti-oxidants, mild reducing agents and sequestering agents mentioned in Research Disclosure (1982), 213 471-2
  • anti-oxidants are those from the BASF Tinogard range, like Tinogard L01, Tinogard MD1, Tinogard NO, Tinogard Q, Tinogard TS, Tinogard TT.
  • Another class of stabilizer which will be employed in some embodiments of composi tions of the present disclosure comprises dispersed amorphous silica: i.e. fumed silica, precipitated silica and mixtures thereof.
  • dispersed amorphous silica refers to small, finely divided non-crystalline silica having a mean agglomerate particle size of less than about 100 microns.
  • amorphous silicas are usedas the stabilizer, they will be included in the compositions at levels ranging from about 0.1% to about 10%, prefera bly from about 0.25% to about 8%, more preferably from about 0.5% to about 5%.
  • Another class of stabilizer which will be employed in embodiments of the compositions of the present disclosure comprises dispersed smectite clay selected from the group consisting of bentonite and hectorite and mixtures thereof.
  • Bentonite is a colloidal alu minum clay sulfate (see Merck Index, Eleventh Edition, 1989, entry 1062, p. 164, which is incorporated by reference).
  • Hectorite is a clay containing sodium, magnesium, lithi um, silicon, oxygen, hydrogen and flouririe (See Merck Index, eleventh Edition, 1989, entry 4538, p.
  • smectite clay When smectite clay is employed as the stabilizer in some embodiments of the cleansing compositions of the present disclosure, it will be constitute about 0.1% to about 10%, preferably from about 025% to about 8%, more preferably from about 0.5% to about 5% of the composition.
  • passivating agents might be used for sta- bilization especially from the group of hectorite, bentonite, montmorillonit, nontronit, saponit, sauconit, beidellit, allevardit, illit, halloysit, attapulgit, sepiolit and/or talcum.
  • Other known stabilizers such as fatty acids and fatty alcohols, are also employed in some embodiment of the inventive compositions.
  • palmitic acid and lauric acid are especially preferred.
  • the present composition may contain 0001 to 80 % b.w of surfactant different from present component (b), relative to the total weight of the composition.
  • the present composition does not con tain cationic nitrogen compounds, especially in amounts larger than 0.01% of such component by weight of the total composition;
  • examples of such cationic nitrogen com pounds are cationic polyamines like cationic polyethylenimine; preferred compositions according to this embodiment thus are of high pH such as 8-10.
  • Antimicrobial compounds like those of present component (a) can be formulated into cleaning and disinfecting products. These may be cleaning products for hard surfaces, laundry detergents, fabric conditioners, hand dishwash products, products for disinfec tion and sanitization of hard surfaces, all purpose cleaners, floor cleaners, glass clean ers, kitchen cleaners, bath cleaners, sanitary cleaners, hygiene rinse products for fab rics, carpet cleaners, furniture cleaners, but also products for conditioning, sealing, caring or treating hard and soft surfaces.
  • the cleaning and disinfecting products can be solids, powders, granules, cakes, bars, tablets, but typically are liquids, pastes or gels. They may be ready to use products, or concentrates which are diluted before or during the cleaning, washing, treating or conditioning process.
  • Home care formulations such as products for cleaning and disinfecting typically contain one or more of components (c) to (f) noted above.
  • such home care formulations may further contain one or more fragrances, thickening agents and/or emulsifier systems, e.g. as noted below for personal care preparations.
  • a typical home care composition according to the invention contains the present com ponents (a) and (b), and optionally at least one further microbicidal compound, and at least one further component selected from non-ionic surfactants, anionic surfactants, amphoteric surfactants, water, alcohols and a combination thereof.
  • the home care compositions can include additional components such as enzymes, bleach es, whiteners, color care agents, fabric softeners, suds suppressors, dispersants, dye transfer inhibitors, chelating agents, aerosol propellants, gelling agents, thickening agents and a combination thereof.
  • the further component comprises permanently quaternized nitrogen compounds, these are preferably contained in amounts of at most 0.01 % by weight of the total composition; preference being given to their total absence.
  • the home care composition according to the invention can be formulated in a variety of ways and may include a hydrophilic phase, a hydrophobic phase and optionally at least one emulsifying agent.
  • the home care composition may be in the form of a liquids, semi-solid, paste, gel, bar, tablet, spray, foam, powder or granules.
  • the term "home care composition” means a composition for use in the general environment of human beings arid is further described in the following.
  • Home care compositions are generally nontoxic when applied in the vicinity of human beings, for example to fabrics and other items used by humans, when applied to surfaces used by, or in the vicinity of, humans, or when applied to spaces occupied by humans.
  • a further aspect of the invention is a method of using a home care composition, as de fined above and in the following, by applying the composition to an article, surface or space.
  • exemplary articles, surfaces and spaces include clothes, furniture fabrics, rugs and carpets, draperies, dishes and cooking utensils, grills, ovens, and other items used by humans.
  • surface includes hard surfaces in the human environment, such as floors, glass surfaces (such as glass windows, doors and countertops), other coun ter surfaces, bath, toilet bowl, sink and other bathroom surfaces.
  • space in cludes the interior portion of buildings occupied by humans, including the air contained therein.
  • a home care composition comprising present components (a) and (b) possesses effective antimicrobial preservative properties.
  • Home care compositions according to the invention include:
  • - surface cleaning compositions for example, glass, floor, counter, bath, toilet bowl, sink, appliance and furniture cleaning compositions
  • - deodorants for example, solid, liquid and spray deodorants air and/or surface deo dorants
  • - disinfectants for example, spray and solid air disinfectants (including gel); and spray, solid, liquid and paste surface disinfectants
  • laundry compositions for example detergents, fabric softeners and whiteners
  • Typical products comprising the present composition in the Home Care area include for example hard surface cleaners, floor cleaners, hard surface or floor disinfectants, all purpose cleaner, dish washing agents, bathroom cleaners or hand disinfectants.
  • the compositions and products of the invention may advantageously be used also for in dustrial or institutional (i.e. I&l) or hospital disinfection, cleaning and sanitation including Health Care, Building Care, Food service & kitchen hygiene, Food and beverage pro cessing or Laundry Care including hard surface cleaners and disinfectants, floor clean ers and disinfectants, hand disinfectants and soaps, CIP-cleaning products or fabric softeners.
  • dishwashing compositions preference is given to dishwashing compositions, laundry compositions, surface cleaning compositions, and rug shampoos.
  • the composition of the invention is selected from the group consisting of dishwashing compositions, laundry compositions, surface cleaning compositions, and rug shampoos.
  • Such compositions preferably comprise:
  • Suitable and preferred components (a) and (b) and suitable and preferred weight ratios thereof are those mentioned above.
  • the overall weight ratio of the antimicrobial agent (a) and the compound of the formula (1 ) or the salt thereof (b) is in the range of from 20: 1 to 1:100, more particularly from 10:1 to 1:50, even more particularly from 1:1 to 1:20, and specifically from 1 :2 to 1 :10.
  • Suitable and preferred surfactants (or surface-active compounds) of component (c) are listed above.
  • Suitable organic solvents of component (d) are for example Ci-Cs-alkanols, C2-C8- alkanediols, Ci-Cs-alkylmonoethers of CjrCs-alkanediols, polyetherpolyols, C-i-Cs- alkylmonoethers of polyetherpolyols, 5-, 6- or 7-membered lactones which may be substituted by one or more Ci-Ci2-alkyl groups; 5-, 6- or 7-membered cyclic carbonates which may be substituted by one or more Ci-Ci2-alkyl groups; aliphatic esters, carbox amides different from component (b), aliphatic, alicyclic or heterocyclic amine-N-oxides and mixtures of the afore-mentioned solvents.
  • organic solvents in this context are not restricted to “typical” solvents, i.e. to organic compounds with solvating properties which are liquid at 25°C, but encompass compounds with solvating properties having a higher melting point of at most 50°C, and also compounds which exert their solvating properties only when mixed with water, such as the above-mentioned aliphatic, alicyclic or heterocyclic amine-N-oxides, which would more correctly be termed solubilizers
  • C-i-Cs-alkanols are compounds R-OH, where R is linear or branched Ci-Cs-alkyl.
  • R is linear or branched Ci-Cs-alkyl.
  • C2-Cs-alkanediols are compounds HO-A-OH, where A is linear or branched C2-C8- alkanediyl (or C2-Cs-alkylene), where the two OH groups are not geminally bound (i.e. are not bound to the same carbon atom).
  • Examples are ethylene glycol (1 ,2- ethanediol), propylene glycol (1 ,2-propanediol), 1 ,3-propanediol, 1 ,2-butanediol, 1 ,4- butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,2- heptanediol, 1 ,2-octanediol and the like.
  • C-i-Cs-Alkylmonoethers of C2-Cs-alkanediols are compounds RO-A-OH, where A is as defined for the alkanediols above and R is Ci-Cs-alkyl.
  • Examples are ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether (butyl glycol), ethylene glycol mono-sec-butyl ether, ethylene glycol mono-isobutyl ether, eth ylene glycol mono-tert-butyl ether, ethylene glycol monopentyl ether, ethylene glycol monohexyl ether, ethylene glycol monoheptyl ether, ethylene glycol monooctyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol mono-n- butyl ether (butyl glycol), propylene glycol mono-sec-butyl ether,
  • Polyetherpolyols are formally the etherification products of alkanediols and thus com pounds HO-A-[0-A] n -OH, where each A is independently an alkylene group, generally a C2-C3-alkylene group, such as 1 ,2-ethylene, 1 ,2-propylene or 1 ,3-propylene, and n is from 1 to 100.
  • A is independently an alkylene group, generally a C2-C3-alkylene group, such as 1 ,2-ethylene, 1 ,2-propylene or 1 ,3-propylene
  • n is from 1 to 100.
  • Examples are polyethylene glycol, generally with a molecular weight of from 106 to ca. 4500, and polypropyleneglycol, generally with a molecular weight of from 134 to ca. 6000.
  • Ci-Cs-Alkylmonoethers of polyetherpolyols are compounds RO-A-[0-A] n -OH, where A and n are as defined for the polyetherpolyols above and R is Ci-Cs-alkyl.
  • Examples are polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polyeth- ylene glycol mono-n-propyl ether, polyethylene glycol mono-n-butyl ether, and the like.
  • Examples for 5-, 6- or 7-membered lactones which may be substituted by one or more Ci-Ci2-alkyl groups are g-butyrolactone, g-valerolactone, d-valorolactone, 5- decanolactone, 5-dodecanolactone and e-caprolactone which may carry one or more Ci-Ci2-alkyl substituents.
  • Examples for 5-, 6- or 7-membered cyclic carbonates which may be substituted by one or more Ci-Ci2-alkyl groups are ethylene carbonate, propylene carbonate and butylene carbonate which may carry one or more Ci-Ci2-alkyl substituents.
  • Suitable aliphatic esters are ethyl acetate, propyl acetate, butyl acetate, methylpropionate and ethyl propionate.
  • suitable carboxamides different from component (b) are N,N- dimethylformamide, N,N-diethylformamide and N,N-dimethylacetamide.
  • Suitable aliphatic, alicyclic or heterocyclic amine-N-oxides are N,N- dimethyl-N-ethylamine N-oxide, N,N,N-triethylamine N-oxide, N,N-dimethyl-N- cyclohexylamine N-oxide, N,N-dimethyl-N-ethanolamine N-oxide (DMEAO) and N- methylmorpholine N-oxide.
  • the solvent is selected from Ci-Cs-alkylmonoethers of C2-Cs-alkanediols (among which preference is given to Ci-C4-alkylmonoethers of a C2-C3-alkanediol, such as the Ci-C4-alkylmonoethers of ethylene glycol or propylene glycol, specific ex amples being ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether (also termed butylglyol), propylene glycol mono-n-propyl ether, propylene glycol mono- n-butyl ether and mixtures thereof, and 5-, 6- or 7-membered lactones which may carry one or more Ci-Ci2-alkyl groups; in particular from 5-, 6- or 7-membered lactones which may carry one or more Ci-Ci2-alkyl groups; specifically from g-butyrolactone, g- valerolact
  • the solvent is a C2-Cs-alkanediol, more preferably a C2-C4-alkanediol, in particular a C2-C3-alkanediol, such as ethylene glycol, 1,2- propanediol and 1 ,3-propanediol, and specifically 1 ,2-propanediol (propylene glycol).
  • a C2-Cs-alkanediol more preferably a C2-C4-alkanediol, in particular a C2-C3-alkanediol, such as ethylene glycol, 1,2- propanediol and 1 ,3-propanediol, and specifically 1 ,2-propanediol (propylene glycol).
  • the enzymes of component (e) are those typically used in laundry, dishwashing or cleaning compositions. Suitable and preferred enzymes are listed above
  • Sequestrants (f) also termed builders, structural substances, framework substances, complexing agents, chelators, chelating agents or softeners, bind alkaline earth metals and other water-soluble metal salts without precipitating. They help to break up soil, disperse soil components, help to detach soil and in some cases themselves have a washing effect. Suitable and preferred sequestrants are listed above (termed there as chelating or complexing agents).
  • Defoamer and/or foam stabilizer (g) are for example soaps, paraffins and silicone oils.
  • Further additives (h) are for example hydrotropic agents, acids, bases, buffering agents, enzyme stabilizers, bleaching agents, corrosion inhibitors, dyes, fragrances, thickeners, activity enhancers different from component (b) and inorganic salts.
  • the acids can be inorganic or organic. Suitable inorganic acids are for example sulfuric acid, hydrochloric acd and phosphoric acid, where sulfuric acid is generally preferred. Suitable organic acids are for example aliphatic, saturated non-substituted C1-C6- mono-, di- and tri-carboxylic acids such as formic acid, acetic acid, propanoic acid, ox alic acid, succinic acid and glutaric acid; aliphatic, saturated Ci-C 6 -mono-, di- and tri carboxylic acids carrying one or more OH groups, such as lactic acid, tartric acid and citric acid; aliphatic, unsaturated C-i-Ce-mono-, di- and tri-carboxylic acids such as sorb ic acid; aromatic carboxylic acids, such as benzoic acid, salicylic acid and mandelic acid; and sulfonic acids, such as methanesulf
  • Suitable bases are in particular inorganic bases, such as the carbonates mentioned in context with the sequestrant, e.g. sodium or potassium carbonate; further alkali metal and earth alkaline metal hydroxides, such as NaOH or KOH.
  • Suitable buffering agents are the typical systems, such as hydrogenphos- phate/dihydrogenphosphate buffer, carbonate/hydrogencarbonate buffer, acetic ac- id/acetate buffer or Tris buffer. Moreover, most of the above acids which are weak and the anion of which is not a strong salt also have buffering capacity.
  • a suitable bleaching agent is hydrogen peroxide (the latter if present at all, is however preferably contained in amounts of at most 0.01 % by weight of the total composition; preference being given to its total absence).
  • some enzymes have bleaching properties.
  • Dyes can be added to obtain a specific aesthetic appearance, but also be used as shading dyes for reducing or avoiding (auto-)oxidation of components of the composi tion, especially of unsaturated organic compounds, triggered by UV or visible light (e.g. if the container in which the composition is kept allows transmission of UV or visible light) and/or transition metal ion catalysis (if present). If used as shading dyes, these impart generally a violet or blue color. Shading dyes are particularly useful in laundry compositions, such as laundry detergents or textile softening compositions, where they can help avoiding yellowing of the textiles.
  • shading dyes are direct dyes (also known as substantive dyes; water soluble dyes with an affinity for fibres and which are taken up directly; generally azo dyes), e.g. violet 7, direct violet 9, direct violet 11 , direct violet 26, direct violet 31 , direct violet 35, direct violet 40, direct violet 41, direct violet 51, and direct violet 99; moreover direct violet 66; acid dyes, such as azine dyes, e.g. acid blue 98, acid violet 50, and acid blue 59, more preferably acid violet 50 and acid blue 98; or non-azine dyes, e.g.
  • hydrophobic dyes dyes which do not con tain any charged water solubilising group; generally selected from the groups of dis perse and solvent dyes, in particular blue and violet anthraquinone and mono-azo dyes, e.g. solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77; basic dyes (organic dyes which carry a net positive charge and deposit onto cotton), e.g.
  • triarylmethane basic dyes methane basic dye, anthraquinone basic dyes, basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71 , basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48; basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141; reactive dyes (dyes which contain an organic group capable of reacting with cellulose and linking the dye to cellulose with a covalent bond, and deposit onto cotton), e.g. reactive blue 19, reactive blue 163, reactive blue 182 and reactive blue, reactive blue 96; and dye conjugates (formed by binding direct, acid or basic dyes to polymers or particles via physical forces).
  • Fragrances can be of natural or synthetic origin; their nature is in general not critical.
  • natural aromatic substances are, for instance, extracts from blossom (lilies, lavender, roses, jasmine, neroli, ylang-ylang), from stems and leaves (geranium, patchouli, petitgrain), from fruit (aniseed, coriander, carraway, juniper), from fruit peel (bergamot, lemons, oranges), from roots (mace, angelica, celery, cardamom, costus, iris, calmus), from wood (pinewood, sandalwood, guaiacum wood, cedarwood, rosewood), from herbs and grasses (tarragon, lemon grass, sage, thyme), from nee dles and twigs (spruce, pine, Scots pine, mountain pine), from resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax).
  • Aromatic substance compounds of the es ter type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert- butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and ben ⁇ zyl salicylate.
  • the ethers include, for example, benzyl ethyl ether;
  • the aldehydes include, for example, the linear alkanals having from 8 to 18 hydrocarbon atoms, citral, citronellal, citronellyl oxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal;
  • the ketones include, for example, the ionones, isomethylionone and methyl cedryl ketone;
  • the alcohols include, for ex ample, anethol, citronellol, eugenol, isoeugenol, geraniol, linalool, phenyl ethyl alcohol and terpinol; and
  • the hydrocarbons include mainly the terpenes and balsams.
  • Ethereal oils of relatively low volatility which are chiefly used as aroma components, are also suitable as perfume oils, e.g. sage oil, chamomile oil, clove oil, melissa oil, oil of cinnamon leaves, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, labolanum oil and lavandin oil.
  • alpha-hexylcinnamaldehyde 2-phenoxyethyl isobutyrate (Pheni- rat 1 ), dihydromyrcenol (2,6-dimethyl-7-octen-2-ol), methyl dihydrojasmonate (preferably having a cis-isomer content of more than 60 wt.%) (Hedione 9 , Hedione HC 9 ), 4,6,6,7,8,8-hexamethyM ,3, 4, 6, 7, 8- hexahydrocyclopenta[g]benzopyran (Galaxolide 3 ), tetrahydrolinalool (3,7-dimethyloctan-3-ol), ethyl linalool, benzyl salicylate, 2-methyl-3- (4-tertbutylphenyl)propanal (Lilial 2 ), cinnamyl alcohol, 4,7-methano-3a,4,5,6,7,
  • the fragrances may optionally be incorporated in encapsulated form.
  • the thickeners serve to impart the desired viscosity to the composition of the invention.
  • any known thickener rheology modifier
  • Suitable thickeners may either be of natural origin or of synthetic nature.
  • Thickeners of natural origin are mostly derived from polysaccharides. Examples are xanthan, carob flour, guar flour, carrageenan, agar, tragacanth, gum arabic, alginates, modified starches such as hydroxyethyl starch, starch phosphate esters or starch ace tates, dextrins, pectins and cellulose derivatives, such as carboxymethylcellulose, hy- droxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellu- lose and the like.
  • Thickeners of natural origin are also inorganic thickeners, such as polysilicic acids and clay minerals, for example sheet silicates, and also the silicates mentioned for the builders. More specific examples are listed in the following table. Most are derived from smectite clays and silica derivatives.
  • synthetic thickeners are polyacrylic and polymethacrylic compounds, such as (partly) crosslinked homopolymers of acrylic acid, for example homopolymers of acrylic acid which have been crosslinked with an allyl ether of sucrose or pentaery- thritol, or with propylene (carbomers), for example the Carbopol® brands from BF Goodrich (e.g. Carbopol® 676, 940, 941 , 934 and the like) or the Polygel® brands from 3V Sigma (e.g.
  • Polygel® DA copolymers of ethylenically unsaturated mono- or dicar- boxylic acids, for example terpolymers of acrylic acid, methacrylic acid or maleic acid with methyl acrylate or ethyl acrylate and a (meth)acrylate which derives from long- chain ethoxylated alcohols, for example the Acusol® brands from Rohm & Haas (e.g.
  • Acusol® 820 or 1206A copolymers of two or more monomers which are selected from acrylic acid, methacrylic acid and the Ci-C4-alkyl esters thereof, for example copoly mers of methacrylic acid, butyl acrylate and methyl methacrylate or of butyl acrylate and methyl methacrylate, for example the Aculyn® and Acusol® brands from Rohm & Haas (e.g.
  • Aculyn® 22, 28 or 33 and Acusol® 810, 823 and 830), or crosslinked high molecular weight acrylic acid copolymers for example copolymers of Cio-C3o-alkyl acrylates with one or more comonomers selected from acrylic acid, methacrylic acid and the Ci-C4-alkyl esters thereof, said copolymers having been crosslinked with an allyl ether of sucrose or pentaerythritol (e.g. Carbopol® ETD 2623, Carbopol® 1382 or Carbopol® AQUA 30 from Rohm & Haas).
  • Suitable thickeners are moreover phospholipids, such as alkylated phosphatidyl cho line, phosphobetaines or alkyl phosphate quaternary compounds.
  • Examples of synthetic thickeners are also reaction products of maleic acid polymers with ethoxylated long-chain alcohols, for example the Surfonic L series from Texaco Chemical Co. or Gantrez AN-119 from ISP; polyethylene glycols, polyamides, polyi- mines and polycarboxylic acids.
  • Suitable activity enhancers different from component (b) are in particular PEI Suitable PEIs are defined above
  • Suitable inorganic salts are for example sodium chloride and calcium chloride.
  • the composition of the invention is a dishwashing composi tion Dishwashing compositions preferably comprise: (a) 0.001 to 7% by weight, relative to the total weight of the composition, of an anti microbial agent as defined above;
  • dishwashing compositions are in liquid or gel form and are suitable both for ma chine washing as well as for manual dishwashing.
  • manual dish- washing compositions have to be adapted so as not to present any hazard for the user.
  • the amount of optionally present acids and/or bases is such that the re sulting pH does not harm the user’s skin.
  • Suitable and preferred components (a) to (h) are those listed above.
  • the overall weight ratio of the antimicrobial agent (a) and the compound of the formula (1) or the salt thereof (b) is in the range of from 20:1 to 1:100, more particularly from 10:1 to 1:50, even more par ticularly from 1:1 to 1:20, and specifically from 1:2 to 1:10.
  • Dishwashing compositions may further comprise as component (h) anti-greying poly mers and scale inhibitor or scale dispersing agents.
  • composition of the invention is a laundry compo sition.
  • Laundry compositions preferably comprise:
  • Such laundry compositions are in liquid or gel form and are suitable both for machine washing as well as for manual laundry washing.
  • manual laundry compositions have to be adapted so as not to present any hazard for the user.
  • the amount of optionally present acids and/or bases is such that the resulting pH does not harm the user’s skin.
  • the overall weight ratio of the antimicrobial agent (a) and the compound of the formula (1) or the salt thereof (b) is in the range of from 20:1 to 1:100, more particularly from 10:1 to 1:50, even more particularly from 1:1 to 1:20, and specifically from 1 :2 to 1 :10.
  • Suitable and preferred components (a) to (h) are those listed above.
  • laundry compositions are laundry detergents, fabric softeners, rinsing compositions, bleacher compositions, and stain remover compositions. Preference is given to laundry detergents.
  • Laundry detergents may further comprise as component (h) dye transfer inhibitors, anti-greying polymers, soil release polymers, scale inhibitor or scale dispersing agents, anti-redeposition agents, anti-shrinking agents, anti-wrinkle agents, ironing aids, skin benefit agents, antistatic agents, processing aids, such as electrolyts, pearlisers, opaci- fiers, sunscreens, and/or antioxidants.
  • component (h) dye transfer inhibitors such as component (h) dye transfer inhibitors, anti-greying polymers, soil release polymers, scale inhibitor or scale dispersing agents, anti-redeposition agents, anti-shrinking agents, anti-wrinkle agents, ironing aids, skin benefit agents, antistatic agents, processing aids, such as electrolyts, pearlisers, opaci- fiers, sunscreens, and/or antioxidants.
  • Suitable softening agents are quaternary ammonium salts, especially quats or ester quats.
  • Quats are compounds [NR 1 R 2 R 3 R 4 ] + X-, wherein R 1 , R 2 , R 3 and R 4 are alkyl groups, where at least one, generally two is/are long-chained alkyl and the others are generally methyl or ethyl, and X- is a counter anion, such as chloride.
  • DSDMAC disearyl dimethyl ammonium chloride, also termed DODMAC (dioctadecyl dimethyl ammonium chloride)
  • TDMAC disitallow di-methyl ammonium chloride
  • DHTDMAC dehydrogenated tallow alkyl dimethyl ammonium chloride
  • DDAC- C10 dehydrogenated tallow alkyldimethylammonium chloride.
  • Esterquats are derived from alkanolamines in which at least one alkanol group is esterified with a fatty acid.
  • esterquats are derived from methyl-triethanol-ammmonium salts, where 1 , 2 or 3 of the OH groups are esterified with a fatty acid, and from dimethyl-diethanol-ammonium salts, where 1 or 2 OH groups are esterified with a fatty acid.
  • composition of the invention is a surface cleaning com position.
  • Surface cleaning compositions preferably comprise:
  • Such surface cleaning compositions are in liquid or gel form and are suitable for manu al use.
  • surface cleaning compositions for household use have to be adapted so as not to present any hazard for the user.
  • the amount of optionally present acids and/or bases is such that the resulting pH does not harm the user’s skin.
  • the overall weight ratio of the antimicrobial agent (a) and the compound of the formula (1) or the salt thereof (b) is in the range of from 20:1 to 1:100, more particularly from 10:1 to 1:50, even more particularly from 1:1 to 1:20, and specifically from 1 :2 to 1 :10
  • Suitable and preferred components (a) to (h) are those listed above.
  • Surface cleaning compositions may further comprise as component (h) anti-greying polymers and scale inhibitor or scale dispersing agents.
  • compositions containing present components (a) and (b) in combination with non-ionic surfactants and/or anionic surfactant and/or cationic sur factants and/or amphoteric surfactants (preference being given to anionic and non-ionic surfactants) present at a concentration effective to preserve the composition against microbes and/or to confer an antimicrobial effect on a person to whom it is applied.
  • Such compositions are non-toxic, cost-effective and shelf-stable over prolonged peri ods.
  • the further surfactants comprise permanently quaternized nitrogen compounds, these are preferably contained in amounts of at most 0.01 % by weight of the total com position; preference being given to their total absence.
  • compositions of the invention are contained in a wide variety of cosmetic preparations.
  • skin-care preparations e.g. skin-washing and cleansing preparations in the form of tablet-form or liquid soaps, soapless detergents or washing pastes
  • bath preparations e.g. liquid (foam baths, milks, shower preparations) or solid bath preparations, e.g. bath cubes and bath salts
  • skin-care preparations e.g. skin emulsions, multi-emulsions or skin oils
  • cosmetic personal care preparations e.g.
  • foot baths foot powders, foot creams or foot balsams, spe cial deodorants and antiperspirants or callus-removing preparations
  • light-protective preparations such as sun milks, lotions, creams or oils, sunblocks or tropicals, pre-tanning preparations or after-sun preparations
  • skin-tanning preparations e.g. self-tanning creams
  • depigmenting preparations e.g. preparations for bleaching the skin or skin-lightening preparations
  • insect-repellents e.g.
  • insect-repellent oils, lotions, sprays or sticks deodorants, such as deodorant sprays, deodorant aerosols, pump-action sprays, deo dorant gels, sticks or roll-ons, also waterfree-deodorant aersols or sticks; antiperspirants, e.g. antiperspirant sticks, creams or roll-ons, also waterfree- antiperspirant aerosols and waterfree antiperspirant sticks; preparations for cleansing and caring for blemished skin, e.g. synthetic detergents (sol id or liquid), peeling or scrub preparations or peeling masks; hair-removal preparations in chemical form (depilation), e.g.
  • deodorants such as deodorant sprays, deodorant aerosols, pump-action sprays, deo dorant gels, sticks or roll-ons, also waterfree-deodorant aersols or sticks
  • antiperspirants e.g. antiperspirant sticks, creams or roll-ons, also
  • hair-removing powders liquid hair-removing preparations, cream- or paste-form hair-removing preparations, hair-removing preparations in gel form or aerosol foams
  • shaving preparations e.g. shaving soap, foaming shaving creams, non-foaming shav ing creams, foams and gels, preshave preparations for dry shaving, aftershaves or aftershave lotions
  • fragrance preparations e.g. fragrances (eau de Cologne, eau de toilette, eau de par- fum, perfume de toilette, perfume), perfume oils or perfume creams
  • cosmetic hair-treatment preparations e.g. hair-washing preparations in the form of shampoos and conditioners, hair-care preparations, e.g.
  • pretreatment preparations hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, inten sive hair treatments, hair-structuring preparations, e.g. hair-waving preparations for permanent waves (hot wave, mild wave, cold wave), hair-straightening preparations, liquid hair-setting preparations, hair foams, hairsprays, bleaching preparations, e.g.
  • hydrogen peroxide solutions (the latter if present at all, it is preferably contained in amounts of at most 0.01 % by weight of the total composition; preference being given to its total absence), lightening shampoos, bleaching creams, bleaching powders, bleach ing pastes or oils, temporary, semi-permanent or permanent hair colourants, prepara tions containing self-oxidising dyes, or natural hair colourants, such as henna or cam omile.
  • Antidandruff preparations in the form of shampoos, conditioners, hair tonics, styling creams or gels or treatments packs
  • Some appropriate personal care compositions include deodorants, antiperspirants, skin care products for facial, foot, hand and whole body uses, sun protection products, per sonal cleaning products, hair care products, feminine hygiene products, oral care prod ucts and decorative cosmetics such as lipsticks, mascara, facial makeup cremes and rouge.
  • Suitable cosmetic preparation may exist in a wide variety of forms, for example: in the form of liquid preparations as a W/O, O/W, O/W/O, W/O/W or PIT emulsion and all kinds of microemulsions, in the form of a gel, in the form of an oil, a cream, milk or lotion, in the form of a powder, a lacquer, a tablet or make-up, in the form of a stick, in the form of a spray (spray with propellent gas or pump-action spray) or an aerosol, in the form of a foam, or in the form of a paste.
  • liquid preparations as a W/O, O/W, O/W/O, W/O/W or PIT emulsion and all kinds of microemulsions
  • a gel in the form of an oil, a cream, milk or lotion
  • a powder in the form of a powder, a lacquer, a tablet or make-up
  • a stick in the
  • the cosmetic or pharmaceutical preparations may be, for example, creams, gels, lo tions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders or ointments.
  • hair-washing preparations in the form of shampoos, hair conditioners, hair-care preparations, e.g pretreatment preparations, hair tonics, styling creams, styl ing gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair straightening preparations, liquid hair-setting preparations, hair foams and hairsprays.
  • hair-washing preparations in the form of shampoos.
  • Typical personal care preparations of the invention generally comprise 0 to 80% of one or more surface active agents (surfactants)
  • the present disclosure further provides methods of using the present personal care compositions.
  • the methods include contacting the inventive personal care composi tions with a part of the human body.
  • the method comprises applying the personal care composition to a body surface or part to be treated.
  • applying includes an appropriate action on the part of the user to contact the personal care composition to the body part. Applying includes, in some embodiments, spreading, spraying, squirting, wiping and brushing. The particular type of application depends on the body part to which the personal care composition is to be applied.
  • Body part means a part of body including the mouth and other epithelial surfaces of the body.
  • body part includes hair, skin and mouth, anus, urethra and vagina
  • the body part is often more specific.
  • the body part is the skin of the face, hand or foot.
  • the body part is the whole body.
  • the personal care compositions are deodorants or antiperspirants
  • body part can be the underarms.
  • the disclosure further provides a cleansing composition that comprises an anionic sur factant
  • the anionic surfactant is constituted from about 0 05% to about 10%, preferably from about 0 1% to about 2%, and more preferably from about 02% to about 1 %, by weight of the cleansing composition.
  • Non-limiting examples of anionic lathering surfactants useful in embodiments of the compositions of the present disclosure are disclosed in McCutcheon's, Detergents and Emulsifiers, North American edition (1990), published by The Manufacturing Confec- tion-er Publishing Co ; McCutcheon's, Functional Materials, North American Edition (1992); and U.S Pat No 3,929,678, to Laughlin et al., issued Dec 30, 1975, all of which are incorporated herein by reference.
  • Anionic surfactants for use in inventive cleansing compositions include alkyl and alkyl ether sulfates. These materials have the respective formulae R11 0-S03 M and R11 (CH2H4 0)x O S03 M, wherein R11 is a saturated or unsaturated, branched or un branched alkyl group from about 8 to about 24 carbon atoms, x is 1 to 10, and M is a water-soluble cation such as ammonium, sodium, potassium, magnesium, triethanola mine, diethanolamine and monoethanolamine.
  • the alkyl sulfates are typically made by the sulfation of monohydric alcohols (having from about 8 to about 24 carbon atoms) using sulfur trioxide or other known sulfation technique.
  • alkyl ether sulfates are typi-cally made as condensation products of ethylene oxide and monohydric alcohols (having from about 8 to about 24 carbon atoms) and then sulfated. These alcohols can be de-rived from fats, for example, coconut oil or tallow, or can be synthetic.
  • Specific examples of alkyl sulfates which are useful in some embodiments of inventive cleanser composi-tions are sodium, ammonium, potassium, magnesium, or TEA salts of lauryl or myristyl sulfate.
  • alkyl ether sulfates include ammonium, sodium, mag- nesium, or TEA laureth-3 sulfate.
  • sulfated monoglycerides of the formula R12 CO O CH2 C(OH)H CH2 O S03 M, wherein R12 is a saturated or unsatu- rat-ed, branched or unbranched alkyl group from about 8 to about 24 carbon atoms, and M is a water-soluble cation such as ammonium, sodium, potassium, magnesium, triethano-lamine, diethanolamine and monoethanolamine.
  • R12 is a saturated or unsatu- rat-ed, branched or unbranched alkyl group from about 8 to about 24 carbon atoms
  • M is a water-soluble cation such as ammonium, sodium, potassium, magnesium, triethano-lamine, diethanolamine and monoethanolamine.
  • fatty acids having from about 8 to about 24 carbon atoms
  • An example of a sulfated monoglyceride is sodium cocomonoglyceride sulfate.
  • Suitable anionic surfactants include olefin sulfonates of the form R13S03 M, wherein R13 is a mono-olefin having from about 12 to about 24 carbon atoms, and M is a water-soluble cation such as ammonium, sodium, potassium, magnesium, triethano- la-mine, diethanolamine and monoethanolamine.
  • R13 is a mono-olefin having from about 12 to about 24 carbon atoms
  • M is a water-soluble cation such as ammonium, sodium, potassium, magnesium, triethano- la-mine, diethanolamine and monoethanolamine.
  • These compounds can be produced by the sulfonation of olefins by means of uncomplexed sulfur trioxide, followed by neu- trali-zation of the acid reaction mixture in conditions such that any sulfones which have been formed in the reaction are hydrolyzed to give the corresponding hydroxyal- kanesulfonate.
  • anionic surfactants are the linear alkylbenzene sulfonates of the form R14 C6H4 S03 M, wherein R14 is a saturated or unsaturated, branched or un branched alkyl group from about 8 to about 24 carbon atoms, and M is a water-soluble cation such as ammonium, sodium, potassium, magnesium, triethanolamine, diethano lamine and mono ethanolamine. These are formed by the sulfonation of linear alkyl benzene with sulfur trioxide.
  • An example of this anionic surfactant is sodium do- decylbenzene sul-fonate.
  • Still other anionic surfactants suitable for embodiments of inventive the cleansing com position include the primary or secondary alkane sulfonates of the form R15 S03 M, wherein R15 is a saturated or unsaturated, branched or unbranched alkyl chain from about 8 to about 24 carbon atoms, and M is a water-soluble cation such as ammonium, sodium, potassium, magnesium, triethanolamine, diethanolamine and monoethanola mine.
  • R15 is a saturated or unsaturated, branched or unbranched alkyl chain from about 8 to about 24 carbon atoms
  • M is a water-soluble cation such as ammonium, sodium, potassium, magnesium, triethanolamine, diethanolamine and monoethanola mine.
  • R15 is a saturated or unsaturated, branched or unbranched alkyl chain from about 8 to about 24 carbon atoms
  • M is a water-soluble cation such as ammonium, sodium, potassium, magnesium, triethanolamine, diethanolamine and monoethanola mine.
  • alkane sulfonate useful herein is alkali metal or ammonium C13-C17 paraf-fin sulfonates.
  • taurates which are based on taurine, which is also known as 2-aminoethane->sulfonic acid.
  • taurates include N- alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethio- nate, according to the teaching of U.S. Pat. No. 2,658,072, which is incorporated herein by reference in its entirety.
  • Other examples of taurine derivatives that are useful in em bodiments of the disclosure include the acyl taurines formed by the reaction of n-methyl taurine with fatty acids (having from about 8 to about 24 carbon atoms).
  • alkylglyceryl ether sulfonates of the form R17 OCH2 C(OH)H CH2 S03 M, wherein R17 is a saturated or unsaturated, branched or unbranched alkyl group from about 8 to about 24 carbon atoms, and M is a water- soluble cation such as ammonium, sodium, potassium, magnesium, triethanolamine, diethano-lamine and monoethanolamine.
  • R17 is a saturated or unsaturated, branched or unbranched alkyl group from about 8 to about 24 carbon atoms
  • M is a water- soluble cation such as ammonium, sodium, potassium, magnesium, triethanolamine, diethano-lamine and monoethanolamine.
  • R17 is a saturated or unsaturated, branched or unbranched alkyl group from about 8 to about 24 carbon atoms
  • M is a water- soluble cation such as ammonium, sodium, potassium, magnesium, triethanolamine, diethano-lamine and monoethanol
  • Suitable anionic surfactants include the sulfonated fatty acids of the form R18 CH(S04) COOH and sulfonated methyl esters of the from R18 CH(S04) CO 0--CH3, where R18 is a saturated or unsaturated, branched or unbranched alkyl group from about 8 to about 24 carbon atoms.
  • These surfactants are generally formed by the sul- fonation of fatty acids or alkyl methyl esters (having from about 8 to about 24 carbon atoms) with sulfur trioxide or by other known sulfonation techniques. Examples include alpha sul-fonated coconut fatty acid and lauryl methyl ester.
  • Suitable anionic materials include acyl glutamates corresponding to the formula R19 CO N(COOH) CH2CH2 C02 M wherein R19 is a saturated or unsaturated, branched or unbranched alkyl or alkenyl group of about 8 to about 24 carbon atoms, and M is a water-soluble cation.
  • R19 is a saturated or unsaturated, branched or unbranched alkyl or alkenyl group of about 8 to about 24 carbon atoms
  • M is a water-soluble cation.
  • anionic materials include alkanoyl sarcosinates corresponding to the formula R20 CON(CH3) CH2CH2 C02 M wherein R20 is a saturated or unsaturated, branched or unbranched alkyl or alkenyl group of about 10 to about 20 carbon atoms, and M is a wa-ter-soluble cation.
  • alkanoyl sarcosinates corresponding to the formula R20 CON(CH3) CH2CH2 C02 M wherein R20 is a saturated or unsaturated, branched or unbranched alkyl or alkenyl group of about 10 to about 20 carbon atoms, and M is a wa-ter-soluble cation.
  • Nonlimiting examples of which include sodium lauroyl sar- cosinate, sodium cocoyl sarcosinate, and ammonium lauroyl sarcosinate.
  • anionic materials include alkyl ether carboxylates corresponding to the formula R21 (OCH2CH2)X OCH2 C02 M wherein R21 is a saturated or unsaturated, branched or unbranched alkyl or alkenyl group of about 8 to about 24 carbon atoms, x is 1 to 10, and M is a water-soluble cation.
  • R21 is a saturated or unsaturated, branched or unbranched alkyl or alkenyl group of about 8 to about 24 carbon atoms, x is 1 to 10, and M is a water-soluble cation.
  • anionic materials include acyl lactylates corresponding to the formula R22 CO [O CH(CH3) CO]X C02 M wherein R22 is a saturated or unsaturated, branched or un branched alkyl or alkenyl group of about 8 to about 24 carbon atoms, x is 3, and M is a water-soluble cation, nonlimiting examples of which include sodium cocoyl lactylate.
  • anionic materials include the carboxylates, nonlimiting examples of which include sodium lauroyl carboxylate, sodium cocoyl carboxylate, and ammonium lauroyl carbox- ylate.
  • Anionic flourosurfactants can also be used.
  • a counter cation, M counterbalances the negative charge of the anionic surfactant.
  • Some especially suitable counter cations are sodium, potassium, ammonium, mo- noeth-anolamine, diethanolamine, and triethanolamine.
  • An especially suitable counter cation is ammonium.
  • the disclosure further provides personal care and home care compositions that com prise one or more non-ionic surfactants.
  • Some nonionic surfactants are condensation prod-ucts of ethylene oxide with various reactive hydrogen-containing compounds re active therewith having long hydrophobic chains (for example aliphatic chains of about 12-20 carbon atoms), which condensation products (“ethoxamers”) contain hydrophilic polyox-yethylene moieties, such as condensation products of poly(ethyleneoxide) with fatty ac-ids, fatty alcohols, fatty amides, polyhydric alcohols (for example sorbitan monostearate) and polypropylene oxide (for example Pluronic materials).
  • Polyoxa- mers include for example block copolymers of polyoxyethylene and polyoxypropylene having an average molecular weight from about 3000 to 5000 and a preferred average molecular weight from about 3500 to 4000 and containing about 10-80% hydrophilic polyoxyethylene groups, by weight, of the block copolymer (for example Pluronic F127).
  • Other non-ionic surfactants are for example alkyl polyglucosids, alcanolamides, ethers of e.g fatty acids with ethylene oxid or polyethylenglycol, amine oxids e.g co- camidopropyla amine oxid.
  • amphoteric surfactants are secondary or thir aliphatic amine derivatives where aliphatic chain, linear or branched, contains at least 8 to 22 carbon atoms and one anionic group such as carbox-ylate, sulfonate, sulfate, phosphate or phosphonate, acyl/dialkyl ethylenediamines
  • acylamphoacetate, disodium acylamphodipropi- onate, sodium acylamphohydroxypro-pylsulfonate, disodium acylamphodiacetate, so dium acylamphopropionate where the acyl represents either an alkyl or alkenyl, mon- or polyunsaturated containing 5 to 29 carbon atoms, N-alkyl amino acids or imino acids Such as aminopropyl alkylglutamide, alkyla-
  • Furter examples are C8-C18-betains, C8-C18-sulfobetains, C8-C24-alkylamido-C1-C4- alkylene betains, imid-azoline carboxylates, alkylamphocarboxycarbonic acids, al- kylamphocarbonic acid (for example lauroamphoglycinate) and N-alkyl- ⁇ - aminopropionate or -iminodipropionate.
  • the amphoteric sur factant comprises C10-C20-alkylamidoC1-C4-alkylenbetaine and/or coco fatty acid amide propylbetaine.
  • the disclosure further provides personal care and home care compositions comprising a combination of anionic, non-ionic and amphoteric surfactants.
  • anionic, non-ionic and amphoteric surfactants are set forth above. Fragrances
  • compositions that comprise one or more fragrances.
  • fragrances particularly those containing plant derived oils
  • Some embodiments of the antimicrobial compositions of the present disclosure com prise suitable perfume oils mixtures of natural and/or synthetic aromatic substances.
  • Natural aromatic substances are, for example, extracts from blossom (lilies, lavender, roses, jasmine, neroli, ylang-ylang), from stems and leaves (geranium, patchouli, petitgrain), from fruit (aniseed, coriander, carraway, juniper), from fruit peel (bergamot, lemons, or-anges), from roots (mace, angelica, celery, cardamom, costus, iris, calmus), from wood (pinewood, sandalwood, guaiacum wood, cedarwood, rosewood), from herbs and grass-es (tarragon, lemon grass, sage, thyme), from needles and twigs (spruce, pine, Scots pine, mountain pine), from resins and balsams (galbanum, elemi, benzoin, myrrh, oliba-
  • Typical synthetic aromatic substances are, for example, products of the ester, ether, aldehyde, ketone, alcohol or hydrocarbon type.
  • Aromatic substance corn-pounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylben- zylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylme- thylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and ben ⁇ zyl salicy late.
  • the ethers include, for example, benzyl ethyl ether;
  • the aldehydes include, for example, the linear alkanals having from 8 to 18 hydrocarbon atoms, citral, citronellal, citronellyl oxyacetaldehyde, cyclamen alde-hyde, hydroxycitronellal, lilial and bour- geonal;
  • the ketones include, for example, the io-nones, isomethylionone and methyl cedryl ketone;
  • the alcohols include, for example, anethol, citronellol, eugenol, isoeuge- nol, geraniol, linalool, phenyl ethyl alcohol and terpi-nol; and
  • the hydrocarbons include mainly the terpenes and balsams.
  • Ethereal oils of rela tively low volatility which are chiefly used as aroma components, are also suitable as perfume oils, e.g. sage oil, camomile oil, clove oil, melissa oil, oil of cinnamon leaves, lime blossom oil, juniper berry oil, vetiver oil, oliba-num oil, galbanum oil, labolanum oil and lavandin oil.
  • the fragrances may optionally be incorporated in encapsulated form. Mildness-enhancing agents and moisturizing agents
  • the disclosure further provides personal care and home care compositions having “mildness-enhancing agents” added thereto.
  • These “mildness-enhancing ingredients” include cationic and nonionic polymers, co-surfactants, moisturizers and mixtures thereof.
  • Polymers used in some embodiments include: polyethylene glycols; polypro pylene glycols; hydrolyzed silk proteins; hydrolyzed milk proteins; hydrolyzed keratin proteins; guar hydroxypropyltrimonium chloride; polyquats; silicone polymers and mix- tures thereof.
  • Suitable cationic polymers are also, for example, cationic cellulose deriv atives, for example a quaternised hydroxymethyl cellulose obtainable under the name Polymer JR 400 from Amerchol (the latter, if present at all, is preferably contained in amounts of at most 0.01 % by weight of the total composition; preference being given to its total absence), cationic starches, copolymers of diallylammonium salts and acryla- mides, quarternised vinylpyrrolidone/vinyl imidazole polymers, for example Luviquat ® (BASF), condensation products of polyglycols and amines, quaternised collagen poly peptides, for example lauryldimonium hydroxypropyl hydrolyzed collagen (Lame- quat ® L/Gmnau), quaternised wheat polypeptides, polyethyleneimine (quaternised poly- petides, if present at all, are preferably contained in amounts of at most 0.01% by weight of the total composition
  • the mildness enhancing poly- mers comprise from about 0.1% to about 1%, preferably from about 0.2% to about 1.0%, and more preferably from about 0.2% to about 0.6%, by weight of the antimicro bial composition.
  • Co-surfactants used in some embodiments include: nonionic surfac tants such as the Genapol24 ® series of ethoxylated alcohols; POE(20) sorbitan monooleate (Tween ® 80); polyethylene glycol cocoate and Pluronic ® propylene ox- ide/ethylene oxide block polymers; and amphoteric surfactants such as alkyl betaines; alkyl sultaines; alkyl amphoacetates; alkyl amphodiacetates; alkyl amphopropionates; and alkyl amphodipropionates.
  • anionic, zwitterionic, amphoteric and non-ionic polymers come into consideration, for example, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl ma- leate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and esters thereof, uncrosslinked polyacrylic acids and polyacrylic acids crosslinked with polyols, acrylamidopropyl-trimethylammonium chloride /acrylate copolymers, octyl acrylamide/methyl methacrylatetertbutylaminoethyl methacrylate/2-hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copoly mers, vinylpyrrolidone/dimethylaminoethyl methacrylate/vin
  • the mildness enhancing co-surfactants comprise from about 20% to about 70%, preferably from about 20% to about 50%, by weight of the anionic surfactant, of the cleansing composition.
  • the disclosure further provides compositions comprising one or more lipid skin moisturizing agents, which provide a moisturizing benefit to the user when deposited to the user's skin.
  • lipophilic skin moisturizing agents are constitute about 0.1% to about 30%, preferably from about 02% to about 10%, most preferably from about 0.5% to about 5% by weight of the composition.
  • the lipophilic skin moisturizing agent is characterized by its solubility parameter, as defined by Vaughan in Cosmetics and Toiletries, Vol. 103, p.
  • a lipophilic skin-moisturizing agent having a Vaughan solubility Parameter (VSP) from 5 to 10, preferably from 55 to 9 is suitable for use in antimicrobial cleansing embodiments of the inventive antimicrobial composi- tions.
  • VSP Vaughan solubility Parameter
  • Lipid-type materials means lipophilic compounds, and include lipophilic skin conditioning agents.
  • Some such skin conditioning agents are: hydrocarbon oils and waxes; silicones; fatty acid derivatives; cholesterol; cholesterol derivatives; di- and tri-glycerides; vegetable oils; vegetable oil derivatives; liquid nondigestible oils (such as those described in U.S. Pat. No. 3,600,186 to Mattson, issued Aug. 17, 1971 and U.S. Pat. Nos. 4,005,195 and 4,005,196 to Jandacek et al., both issued Jan.
  • Blends of pet rolatum and hydrogenated and nonhydrogenated high molecular weight polybutenes, wherein the ratio of petrolatum to polybutene ranges from about 90:10 to about 40:60, are also suitable for use in some embodiments as the lipid skin moisturizing agent in the compositions herein.
  • Some additional examples of lipid-type materials are: dimethicone copolyol; dime- thylpolysiloxane; diethylpolysiloxane; high molecular weight dimethicone; mixed C1-C30 alkyl polysiloxane; phenyl dimethicone; dimethiconol, and mixtures of any two or more of the foregoing.
  • non-volatile silicones se lected from dimethicone; dimethiconol; mixed C1-C30 alkyl polysiloxane; and mixtures of any two or more thereof.
  • Nonlimiting examples of silicones useful in some embodi ments are described in U.S. Pat. No. 5,011,681, to Ciotti et al., issued Apr. 30, 1991, which is incorporated by reference.
  • Silicones or siloxanes are also components covered by the group of mildness-enhancing agents and moisturizing agents:
  • silicones any organosilicon polymers or oligo mers having a linear or cyclic, branched or crossl inked structure, of variable molecular weight, and essentially based of recurring structural units in which the silicone atoms are linked to each other by oxygen atoms (siloxane bond SiOSi), optionally substituted hydrocarbon radicals being directly linked via a carbon atom to the silicone atoms.
  • Cyclic siloxane polymers Cyclomethicones of the general formula such as cyclopentasiloxane, cyclohexasiloxane low viscous, volatile fluid
  • the INCI names for labeling specific cyclic dimethyl polysiloxane compounds are: Cy- clotrisiloxane (q.v.) when n is equal to 3, Cyclotetrasiloxane (q.v.) when n is equal to 4, Cyclopentasiloxane (q.v.) when n is equal to 5, Cyclohexasiloxane (q.v.) when n is equal to 6, and Cycloheptasiloxane when n is equal to 7 (q.v.).
  • Elastomer medium crosslinking with a density that allows elongation/distorsion of the molecule. We have to exclude PEG-modified Dimethicone Crosspolymers. Resin: high crosslinking with a density that provides some rigidity to the molecule
  • Resin silicones Dispersing agents such as KP-545 (Shin-Etsu); Acrylates/Dimethicone copolymer in Cyclopentasiloxane copolymer of dimethicone and one or more monomers of acrylic acid, methacrylic acid or one of their simple esters Siloxysilicates such as T rimethylsiloxysilicates T-resins; branched polymer of T-Units Q-resins; branched polymer of Q-Units:
  • Film-forming and water-resistant agents such as T rimethylsiloxysilicate; SR 399 (GE Silicones) or Wacker-Belsil TMS803 (Wacker Chemie); mixtures from Dow Corning such as DC 749 cosmetic fluid (T rimethylsiloxysilicate in Cyclopentasiloxane) or DC 593 fluid (T rimethylsiloxysilicate in Dimethicone)
  • AMS improve spreadability and wash-off resistance. For inorganic sunscreens, it improves particle dispersion, reduce the re-agglomeration and better long-lasting effect on skin.
  • simethicones which are mixtures of dimethicones having an average chain length of from 200 to 300 dimethylsiloxane units with hydrogenated silicates.
  • a detailed survey by Todd et al of suitable volatile silicones may in addition be found in Cosm. Toil. 91, 27 (1976).
  • lipid-type materials are: di- or tri-glycerides, based on C6-C18 fatty acids, modified by reaction with other alcohols (caprylic/capric triglycer ide, wheat germ glycerides, etc.). Fatty acid esters of polyglycerin (polyglyceryl-n such as polyglyceryl-4 caprate, polyglyceryl-2 isostearate, etc. or
  • Waxes including esters of long-chain acids and alcohols as well as compounds having wax-like properties, e.g., carnauba wax, beeswax (white or yellow), lanolin wax, candellila wax, ozokerite, japan wax, paraffin wax, microcrystalline wax, ceresin, ce- tearyl esters wax, synthetic beeswax, etc. Also, hydrophilic waxes as Cetearyl Alcohol or partial glycerides.
  • castor oil hydrogenated castor oil, sweet almond oil, wheat germ oil, corn oil, shea butter, cocoa butter, mink oil, sunflower oil, macadamia nut oil, hydrogenated tallow, apricot kernel oil, hazelnut oil, borago oil, soy bean oil; derivatized soybean oils such as maleated soy bean oil; safflower oil; cotton seed oil; corn oil; walnut oil; peanut oil; olive oil; cod liver oil; avocado oil; palm oil and sesame oil; vegetable oils and vegeta ble oil derivatives; coconut oil and derivatized coconut oil; cottonseed oil and derivat ized cottonseed oil; jojoba oil; cocoa butter; and the like, as well as mixtures of any two or more thereof.
  • Acetoglyceride esters are useful in some embodiments; and an exam ple is acetylated monoglyceride.
  • Lanolin and its derivatives are preferred in some em bodiments; and some examples are: lanolin, lanolin oil, lanolin wax, lanolin alcohols, lanolin fatty acids, isopropyl lanolate, acetylated lanolin, acetylated lanolin alcohols, lanolin alcohol linoleate and lanolin alcohol riconoleate.
  • Some embodiments might con- tain esters of long-chain acids and alcohols as well as compounds having wax-like properties, e.g., carnauba wax, beeswax (white or yellow), candellila wax, ozokerite, japan wax, paraffin wax, microcrystalline wax, ceresin, cetearyl esters wax, synthetic beeswax etc. Also, hydrophilic waxes as Cetearyl Alcohol or partial glycerides. Other components covered by the group of mildness-enhancing agents and moisturiz ing agents are Pearlescent waxes:
  • Alkylene glycol esters especially ethylene glycol distearate; fatty acid alkanolamides, especially coco fatty acid diethanolamide; partial glycerides, especially stearic acid monoglyceride; esters of polyvalent, unsubstituted or hydroxy-substituted carboxylic acids with fatty alcohols having from 6 to 22 carbon atoms, especially long-chained esters of tartaric acid; fatty substances, for example fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which in total have at least 24 carbon at oms, especially laurone and distearyl ether; fatty acids, such as stearic acid, hydroxys- tearic acid or behenic acid, ring-opening products of olefin epoxides having from 12 to 22 carbon atoms with fatty alcohols having from 12 to 22 carbon atoms and/or polyols having from 2 to 15 carbon atoms and from
  • the lipophilic skin condi tioning agent consists of lipids selected from the group consisting of: petrolatum; blends of petrolatum and high molecular weight polybutene; mineral oil; liquid nondi- gestible oils (for example liquid cottonseed sucrose octaesters); or blends of liquid di gestible or nondigestible oils with solid polyol polyesters (for example sucrose oc taesters prepared from C22 fatty acids), wherein the ratio of liquid digestible or nondi gestible oil to solid polyol polyester ranges from about 96:4 to about 80:20; hydrogen ated or nonhydrogenated polybutene; microcrystalline wax; polyalkene; paraffin; cerasin; ozokerite; polyethylene; perhydrosqualene; dimethicones; alkyl siloxane; polymethylsiloxane; methylphenylpolysiloxane; and mixtures of any two or more
  • a stabilizer will be in cluded at a level ranging from about 0.1% to about 10%, preferably from about 0.1% to about 8%, more preferably from about 0.1% to about 5% by weight of the antimicrobial composition.
  • a “stabilizer” is a compound or mixture that forms a crystalline stabilizing network in the liquid composition that prevents the lipophilic skin moisturizer agent droplets from coalescing and phase splitting in the product. The network exhibits time-dependent recovery of viscosity after shearing (for example, thixotropy).
  • the stabilizer employed in the present compositions comprises a polymeric thickener
  • a “thickener” is a compound capable of increasing the viscosity of a liquid composition, but which don’t necessarily form the aforementioned cross- linked matrix.
  • Particular thickeners are described in more detail in the following. Thick eners can be divided into at least 2 general categories: those that show the best per formance in water, and those that show the best performance in oils. In addition, it is also possible to differentiate them according to their nature, for example synthetic pol ymers, natural polymers and their derivatives, mineral polymers etc , but also according to their ionic character such as anionic, cationic, nonionic or amphoteric.
  • Phospholipid derivatives (permanently quaternized nitrogen compounds be ing preferably contained in amounts of at most 0.01% by weight of the total composi tion; preference being given to their total absence)
  • polymeric thickeners When polymeric thickeners are used as stabilizers in embodiments of the present compositions, they are typically included in an amount ranging from about 0 01% to about 5%, preferably from about 0.3% to about 3%, by weight of the composition.
  • the polymeric thickener is preferably an anionic, nonionic, cationic or hydrophobically modified polymer selected from the group consisting of: cationic polysaccharides of the cationic guar gum class with molecular weights of 1,000 to 3,000,000; anionic, cationic, and nonionic homopolymers derived from acrylic and/or methacrylic acid; anionic, cationic, and nonionic cellulose resins; cationic polyalkylene and ethoxypolyalkylene imines; polyethylene glycol of molecular weight from 100,000 to 4,000,000; and mixtures of two or moire thereof.
  • the polymer is preferably selected from the group consisting of sodium polyacrylate, hydroxy ethyl cellulose, cetyl hydroxy ethyl cellulose, and polyquaternium 10.
  • UV absorbers In some embodiments also one or more UV absorbers might be included in personal care applications (Table 3).
  • Table 3 Suitable UV filter substances and adjuvants which can be additionally used with the UV absorbers according to the present disclosure
  • Emulsi bomb systems may comprise for example: carboxylic acids and their salts: alkaline soap of sodium, potassium and ammonium, metallic soap of calcium or magnesium, organic basis soap such as Why, palmitic, stearic and oleic acid etc.. Alkyl phosphates or phosphoric acid esters, acid phosphate, diethanolamine phosphate, potassium cetyl phosphate. Ethoxylated carboxylic acids or polyethyleneglycol esters, PEG-n acylates.
  • Linear fatty alcohols having from 8 to 22 carbon atoms, branched from 2 to 30 mol of ethylene oxide and/or from 0 to 5 mol propylene oxide with with fatty acids having from 12 to 22 carbon atoms and with alkylphenols having from 8 to 15 carbon atoms in the alkyl group.
  • Fatty alcohol polyglycolether such as laureth-n, ceteareth-n, steareth-n, oleth-n.
  • Fatty acid polyglycolether such as PEG-n stearate, PEG-n oleate, PEG-n co- coate.
  • Monoglycerides and polyol esters Monoglycerides and polyol esters.
  • Fatty acid and polyglycerol ester such as monostearate glycerol, diisostearoyl polyglyceryl-3- diisostearates, polyglyceryl-3-diisostearates, triglyceryl diisostearates, polyglyceryl-2- sesquiisostearates or polyglyceryl dimerates. Mixtures of compounds from a plurality of those substance classes are also suitable.
  • Fatty acid polyglycolesters such as monos tearate diethylene glycol, fatty acid and polyethylene glycol esters, fatty acid and sac charose esters such as sucro esters, glycerol and saccharose esters such as sucro glycerides.
  • Sorbitol and sorbitan sorbitan mono- and di-esters of saturated and unsatu rated fatty acids having from 6 to 22 carbon atoms and ethylene oxide addition prod ucts.
  • Polysorbate-n series, sorbitan esters such as sesquiisostearate, sorbitan, PEG- (6)-isostearate sorbitan, PEG-(10)-sorbitan laurate, PEG-17- dioleate sorbitan.
  • O/W emulsifiers such as methyl gluceth-20 sesquistearate, sorbitan stearate/sucrose cocoate, methyl glucose ses- quistearate, cetearyl alcohol/cetearyl glucoside.
  • W/O emulsifiers such as methyl glu cose dioleate/ methyl glucose isostearate.
  • Sulfates and sulfonated derivatives dialkyl- sulfosuccinates, dioctyl succinate, alkyl lauryl sulfonate, linear sulfonated parafins, sul fonated tetraproplyne sulfonate, sodium lauryl sulfates, amonium and ethanolamine lauryl sulfates, lauyl ether sulfates, sodium laureth sulfates, sulfosuccinates, aceyl isothionates, alkanolamide sulfates, taurines, methyl taurines, imidazole sulfates.
  • Amine derivatives, amine salts, ethoxylated amines, oxide amine with chains contain- ing an heterocycle such as alkyl imidazolines, pyridine derivatives, isoquinoteines, cetyl pyridinium chlorure, cetyl pyridinium bromide, quaternary ammonium such as cetyltri- methylbroide amonium broide (CTBA), stearylalkonium.
  • an heterocycle such as alkyl imidazolines, pyridine derivatives, isoquinoteines, cetyl pyridinium chlorure, cetyl pyridinium bromide, quaternary ammonium such as cetyltri- methylbroide amonium broide (CTBA), stearylalkonium.
  • CTBA cetyltri- methylbroide amonium broide
  • Amide derivatives alkanola- mides such as acylamide DEA, ethoxylated amides such as PEG-n acylamide, oxyde- amide Polysiloxane/polyalkyl/polyether copolymers and derivatives, dimethicone, copolyols, silicone polyethylene oxide copolymer, silicone glycol copolymer.
  • Propox- ylated or POE-n ethers (Meroxapols), Polaxamers or poly(oxyethylene)m-block- poly(oxypropylene)n-block(oxyethylene) Zwitterionic surfactants that carry at least one quaternary ammonium group and at least one carboxylate and/or sulfonate group in the molecule
  • Zwitterionic surfactants that are especially suitable are betaines, such as N-alkyl-N,N-dimethylammonium glycinates, cocoalkyldimethylammonium glycinate,
  • N-acylaminopropyl-N,N-dimethylammonium glycinates cocoacylaminopropyldime- thylammonium glycinate and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines each having from 8 to 18 carbon atoms in the alkyl or acyl group and also cocoacylami- noethylhydroxyethylcarboxymethylglycinate, N-alkylbetaine, N-alkylaminobetaines.
  • Non ionic emulsifiers such as PEG-6 beeswax (and) PEG-6 stearate (and) pol- yglyceryl-2-isostearate [Apifac], glyceryl stearate ( and) PEG-100 stearate. [Arlacel 165], PEG-5 glyceryl stearate [arlatone 983 S], sorbitan oleate (and) polyglyceryl-3 ricinoleate.
  • Silicone emulsifiers particularly suitable for W/Si emulsions are those corresponding to the following formula: wherein m is a number from 1 to 20 n is a number from 0 to 500 p is a number from 0 to 50
  • R1 is linear or branched C1- C30 Alkyl radical or phenyl radical
  • R2 is - C c H2 c (-O- C2H4) a - ( -0-C3H6) b - ( -0-C4H8) d -
  • R3 R3 is - H, -OH; linear or branched alkyl C1 - C12; linear or branched alkoxy C1- C6; linear or branched acyloxy C2- C12;- NHCH2CH2COOM; aminoalkyl radical op tionally substituted on the amine function; - NHCO(CH2) d - COOM, C1-C30 carboxyacyl radical; where M is H, Na, K, Li, NH4 or organic amine; optionally substituted phos- phono group;
  • a is a number from 0 to 100
  • b is a number from 0 to 50
  • c is a number from 0 to 5
  • d is a number from 0 to 10.
  • Preferred silicone emulsifiers which are particularly recommended correspond to for mula wherein n is a number from 1 to 500
  • R is linear or branched C1- C30 Alkyl radical or phenyl radical
  • R2 is - CcH2c (-0- C2H4) a - ( -0-C3H6) b - 0(-C4H8) d - R3 R3, a, b, c & d have the same meaning as previously described.
  • Anionic emulsifiers such as PEG-2 stearate SE, glyceryl stearate SE [Monelgine, Cuti- na KD], propylene glycol stearate [Tegin P], cetearyl Alcohol and Sodium cetearyl sul fate [Lanette N, Cutina LE, Crodacol GP], cetearyl alcohol and sodium lauryl sulfate [Lanette W], trilaneth-4 phopshate and glycol stearate and PEG-2 stearate [Sedefos 75], glyceryl stearate and sodium lauryl Sulfate [Teginacid Special] Cationic acid ba ses such as cetearyl alcohol and cetrimonium bromide.
  • the emulsifiers may be used in an amount of, for example, from 1 to 30 % by weight, especially from 4 to 20 % by weight and preferably from 5 to 10 % by weight, based on the total weight of
  • the preferably amount of such emulsifier system could represent 5% to 20% of the oil phase.
  • the lipid phase will advantageously be selected from mineral oils; mineral waxes; oils (such as triglycerides of capric and caprylic acid); natural oils (such as castor oil); fats; waxes and other natural and syn thetic fats (for example esters of fatty acids with short chain alcohols, such as isopro panol, propylene glycol or glycerine) or esters of fatty alcohols with fatty acids or car boxylic acids with low number of carbon atoms; alkylbenzoate; silicone oils (such as dimethylpolysiloxane, diethylpolysiloxane, diphenylpolysiloxane); and/or mixtures of two or more thereofln various embodiments of the present disclosure, the oil phase of the emulsion, oleogel, hydrodispersion or lipodispersion is advantageously selected from saturated and/or unsaturated, branched and/or linear alkane carbonic
  • fatty acid triglycerides they will be selected from synthetic, semi-synthetic and natural oils, such as: olive oil, sunflower oil, soy oil, pea nut oil, rape-seed oil, palm oil, almond oil, coconut oil and similar oils.
  • the oil phase comprises other preferred ingredients, such as: 2- ethylhexylisostearate; octyldodecanol; isotridecylisononanoate; isoeicosane; 2- ethylhexylcocoate; C12-C15 alkyl benzoate; caprylic-caprinic acid-triglycerides and di- caprylic ether or mixtures of those ingredients (such as mixtures of 2- ethylhexylisostearate with C12-C15 alkylbenzoate); mixtures of C12-C15 alkylbenozoate and isotridecylisononanoate and mixtures of C12-C15 alkylbenzoate with 2- ethylhexylisostearate and isotridecylisononanoate.
  • other preferred ingredients such as: 2- ethylhexylisostearate; octyldode
  • cyclic or linear silicone oils can be used and are in some cases the only ingredient in the oil phase.
  • preferred silicone oils include: cyclomethicone (octamethylcyclotetra- siloxane), hexamethylcyclotrisiloxane, polydimethylsiloxane and poly(methylphenylsiloxane).
  • preferred hydrocarbons include: paraffin oil, squalane and squalene.
  • the aqueous phase contains for example ingredients such as: alcohols, diols or polyols with a low number of C-atoms or their ethers (for example ethanol, isopropanol, propyleneglycol, glycerin, ethylene glycol, ethylene glycol mo- noethylether, ethylene glycol monobutylether, propylene glycol monomethylether, pro pylene glycol monoethylether, propylene glycol monobutylether, diethylene glycol monomethylether; diethylene glycol monoethylether, diethylene glycol monobutylether and similar products); lower homologs of alcohols (such as ethanol, isopropanol, 1,2- dipropandiol and glycerin), as well as one or more thickeners for example: silicium di oxide, aluminum silicates, polysaccharides or derivatives thereof (for example hyalu ronic acid, xanthan gum, hydroxypropy
  • the present compositions will comprise fatty acid esters as noted further above under further additives (e).
  • the present compositions comprise dispersed amorphous silica, dispersed smectite clay, passivating agents, fatty acids and/or fatty alcohols as noted further above under stabilizing agent (f).
  • compositions comprise suitable skin lightening agents or skin bleaching ingredients, including kojic acid, arbutin, tranexamic acid, ascorbic acid and derivatives thereof, e.g., magnesium ascorbyl phosphate or sodium ascorbyl phosphateor other salts of ascorbyl phosphate. Also those ingredient dis played in the PCT application N° US 95/07432, filed on Feb.24,1995 and PCT applica tion N°US 95/02809, filed on Jan.3, 1995.
  • compositions comprise suitable anti-wrinkle agents including sulfur-containing D and L amino acids and their derivatives and salts, particu larly the N-acetyl derivatives, a preferred example of which is N-acetyl-L-cyteine; thiols; hydroxy acids (salicylic acid, glycolic acid), keto acids (pyruvic acid), phytic acid, lipoic acid; lysophophatidic acid, skin peel agents, flavonoids, stilbenes, cinnamates, resvera- trol, kijnetin, zeatin, dimethylaminoethanol, peptides from natural and synthetic sources, salts of sugar acids (Mn gluconate), terpene alcohols, vitamin B compounds such as vitamin B3, vitamin B1 (Thiamine), vitamin B2 (riboflavin), vitamin B5 (Panto thenic acid), vitamin Bt (carnitine), Vitamin B12 (cobalamine), vitamin B15 (pangamic acid
  • compositions comprise substances suitable for use as adjuvants for example alpha glucosylrutin (CAS No. 130603-71-3), 2-butyloctyl o- hydroxybenzoate (CAS No. 190085-41-7), vitamin E (CAS No.
  • vitamin E acetate (CAS No 58-95-7), diethylhexyl 2,6- naphthalate, di-n-butyl adipate, di(2- ethylhexyl)-adipate, di(2-ethylhexyl)-succinate and diisotridecylvestat, and also diol esters, such as ethylene glycol dioleate, ethylene glycol diisotridecanoate, propylene glycol di(2-ethylhexanoate), propylene glycol diisostearate, propylene glycol dipelar- gonate, butanediol diisostearate and neopentyl glycol dicaprylate.
  • diol esters such as ethylene glycol dioleate, ethylene glycol diisotridecanoate, propylene glycol di(2-ethylhexanoate), propylene glycol diisostearate, propylene glycol
  • the present cosmetic preparations to contain, as adjuvants, anti-foams, such as silicones, structurants, such as maleic acid, solubilisers, such as ethylene glycol, propylene glycol, butylene glycol, PEG40 hydrogenated castor oil, glycerol or diethylene glycol, opacifiers, such as latex, styrene/PVP or sty rene/acrylamide copolymers, complexing agents, such as EDTA, NTA, alaninediacetic acid or phosphonic acids, propellants, such as propane/butane mixtures, N2O, dimethyl ether, CO2, N2 or air, so-called coupler and developer components as oxidation dye precursors, reducing agents, such as thioglycolic acid and derivatives thereof, thiolactic acid, cysteamine, thiomalic acid or mercaptoethanesulfonic acid, or oxidising agents, such
  • compositions may further contain a colorant, i.e. any compound or mixture capable of imparting a color to the composition.
  • a colorant i.e. any compound or mixture capable of imparting a color to the composition.
  • compositions may further contain an emollient, i.e. a compound or mixture capable of making the skin more soft or supple.
  • an emollient i.e. a compound or mixture capable of making the skin more soft or supple.
  • Some embodiments comprise one or more antioxidants.
  • ami no acids or amino acid derivatives are e.g. ami no acids or amino acid derivatives; imidazoles and their derivatives; peptides such as D,L-carnosin; carotinoids; carotines and their derivatives; liponic acid; metal chelating agents (such as alpha-hydroxy fatty acids, palmitinic acid, phytinic acid, lactoferrine); alpha-hydroxyacids (for example lactic acid, maleic acid); humic acid; gallate; EDTA, EGTA and their derivatives; unsaturated fatty acids and their derivatives; vitamin C (ascorbic acid) and its derivatives (such as acetylated derivatives); rutinic acid and its derivatives; alpha-glycosyl rutin, ferulic acid, butylhydroxytoluol, butylhydroxyanisol and suitable derivatives; and/or mixtures of two or more of these substances.
  • antioxidants are for example:
  • - tocotrienol (a, b, g, d isomers), containing one unsaturated fatty chain, and its esters of acids ascorbic acid and its esters of acids such as phosphoric acid and also sodium, potassium, lithium and magnesium salts, Ascorbyl Tetraisopalmitate, further es ter with pyrrolidoncarboxylic acid and esters of acids with general formulas H(CH2)n(CHR)COOH (3)
  • CH3(CH2)mCH CH(CH2)nCOOH (4)
  • R is hydrogen atom or OH group
  • m, n are integral numbers from 0 to 20 where m+n sum is maximally 21.
  • Retinoids include all natural and/or synthetic analogs of vitamin A or retinal-like compounds which possess the biological activity of vitamin A in the skin as well as the geometric isomers and stereoisomers of these compounds.
  • Preferred compounds are retinal, retinol esters (e.g., C2-C22 alkyl esters (saturated or unsaturated alkyl chains) of retinal, including retinyl palmitate, retinyl acetate, retinyl propionate), retinal, and/or retinoic acid (including all trans retinoic acid and/or 13-cis-retinoic acid) or derivatives ...Other retinoids which are useful herein are described in U.S.
  • Suitable retinoids are tocopheryl-retinoate [tocopherol ester of retinoic ac id (trans or cis)], adapalene [6-(3-(1-adamantyl)-4-methoxyphenyl)-2-naphtoic acid] and tazarotene (ethyl 6-[2-(4,4-dimethylthiochroman-6-yl)- ethynyljnicotinate) carotenoids such as a-, b-, g-, and d-carotene, lutein, xanthophylls, zeaxan- thine, violaxanthine, cryptoxanthine, fukoxanthine, antheraxanthine, lycopene, didehydrolycopene and tetradehydrolycopene carotenoids enzymatic antioxidants such as Glutathione peroxidase, Cata
  • Lipoic acid and its derivatives such as alpha-lipoic acid...
  • Rutinic acid and its derivatives such as a-glucosylrutin, a water soluble flavo- noid, rutin hydrate (vitamin P)
  • Botanical extracts such as white and green tea extracts, chicory leaf extract (Cichorium intubybus), Passionflower extract (Passiflora incarnata), Aspalathus linearis extract, rosmary extract, red leaf extract of Aceraceae Maple tree or of Rosaceae Cherry tree, Curcuma longa L (curcuminoids active ingredients), Le- ontopodium alpinum extract, Emblica officinalis (phyllanthus emblica) tree ex tract.
  • white and green tea extracts chicory leaf extract (Cichorium intubybus), Passionflower extract (Passiflora incarnata), Aspalathus linearis extract, rosmary extract, red leaf extract of Aceraceae Maple tree or of Rosaceae Cherry tree, Curcuma longa L (curcuminoids active ingredients), Le- ontopodium alpinum extract, Emblica officinalis (phyllanthus emblica) tree ex tract.
  • Phenolic acids such as caffeic acid, 3,4-dihydroxyphenyl acetic acid, 3,4- dihydroxybenzoic acid.
  • Flavonoids and polyphenols such as flavanones selected from the group con sisting of unsubstituted flavanones, mono-substituted flavanones, and mixtures thereof; chalcones selected from the group consisting of unsubstituted Chal- cones, mono-substituted chalcones, di-substituted chalcones, tri-substituted chalcones, and miture therof; flavones selected from the group consisting of unsubstituted flavones, mono-substituted flavones, di-substituted flavones, and mixtures thereof; oe or more isoflavones; coumarins selected from the group consisting of unsubstituted coumarins, mono-substituted coumarins, di- substituted coumarins, and mixtures thereof; flavonols , anthocyanins, cate- chins, proanthocyani
  • Flavonoids which are broadly disclosed in US patents 5,686,082 and 5,686, 367 can also be used. Chlorogenic acid and ferulic acid. Further antimicrobia!!y active molecules, which are typically selected from the list of known biocides according to Art 95 of EU Regulation 528/2012 given further above.
  • the total amount of these further biocides and the antimicrobial agent of present component (a) generally remains within the limits specified for present component (a) alone, i.e. 1 part by weight of the biocide (a and optionally k) on 0.001 to 1000, especially 0.001 to 10, parts by weight of component (b); and 0.001 to 5 % b.w. of the biocide (sum of a and optionally k), relative to the total weight of the composition.
  • the invention further provides personal care compositions, which are oral care compositions, which include at least one ingredient other than present components (a) and (b) such as a non-ionic or anionic surfactant, an alcohol, a detergent or combinations thereof, which ingredient is of the type that is tolerated by teeth and buccal tissues, such as the gums and inner cheek.
  • Such orally acceptable compositions need not be ingestible (as most fluoride-containing toothpastes are not considered ingestible due their fluoride content), are non-toxic when applied to the mouth and then removed from the mouth.
  • the disclosure provides oral care compositions that are mouth rinses, mouth washes, tooth pastes, tooth gels, denture pastes, denture gels, chewing gums, solid lozenges and oral sprays, which are described in more detail herein.
  • the oral care compositions contain one or more additional oral care ingredients for treating the mouth, including the teeth, gums, tongue, or buccal skin surfaces.
  • additional ingredients include cleaning agents, abrasives, fluoridat ing agents, malodor treating agents, tooth whitening agents, anti-carries agents, gelling agents, antibacterial agents (other than the inventive antimicrobial agent), flavorings, colorants and combinations of two or more of the foregoing.
  • Such oral compositions may be used in a conventional manner commensurate with the physical form of the compositions, which may be liquid, paste, semi-solid or solid.
  • the compositions are pastes or gels
  • they are applied to a mouth surface (for example teeth and/or gums) with brushing.
  • the compositions are liquids, they are applied to the mouth surface with gargling or swishing. They may be removed from the mouth by expectorating and optionally rinsing with water or a mouth rinse.
  • compositions that possess antimicrobial activity against oral bacteria, and thus exhibit antibacterial effects in oral care applications.
  • inventive compositions fight plaque; reduce, slow the retard sion of, or prevent gingivitis; reduce, slow the progression of, or prevent periodontitis and/or reduce mouth malodor.
  • Such oral care compositions with antimicrobial activity further contain antimicrobial, anti-plaque, anti-gingivitis and/or anti-periodontitis agents such as chlorhexidine salts, quaternary compounds (such as cetrimonium bromide, benzalkonium chloride and cetyl pyridinium chloride) and/or phenolic substances ⁇ such as 2,4,4’-trichloro-2’-hydroxydiphenylether; 4A-dichloro-2-hydroxydiphenylether, thy mol, and other phenolic compounds having the following generic formula
  • R22, R23 and R24 are independently from each other alkyl (branched, cyclo or linear), aryl, O-aryl, o-alkyl (linear, cyclo, or branched) ⁇ .
  • the oral care compositions are, for example, mouth rinses, semi-solids such as toothpastes or gel dentifrices, chewing gums or solid lozenge or the like.
  • inventive oral compositions contain, for example: polishing agents (such as silica gels, colloidal silica or complex amorphous alkali metal aluminosilicate, sodium bicarbonate, sodium metaphosphate, potassium metaphosphate, tricalcium phosphate, dehydrated dicalcium phosphate, anhy drous dicalcium phosphate, calcium pyrophosphate, calcium carbonate, alumi num silicate, hydrated alumina, silica, bentonite and mixtures of any two or more thereof); humectants (such as glycerin, sorbitol, an alkylene glycol such as polyethylene glycol or propylene glycol, butylene glycol, PEG 40 hydrogenated castor oil and/or mixtures of any two or more thereof); water (for example as hereinbefore described); natural or synthetic thickener or gelling agent (such as Irish moss, iota- carragenan, kappa-carrageenan, gum traga
  • whitening agents for example peroxides, such as urea peroxide, carbamide per oxide and/or hydrogen peroxide
  • peroxides if present at all, are preferably contained in amounts of at most 0.01% by weight of the total composition; prefer ence being given to their total absence;
  • preservatives such as sodium benzoate
  • substances that release fluoride ions to protect against caries such as inorganic fluoride salts, for example sodium, potassium, ammonium or calcium fluoride or organic fluorides such as amine fluoride);
  • Another category of skin care formulations are water in silicone systems (w/silicone emulsions).
  • Silicones or siloxanes organosubstituted polysiloxanes
  • Dimethylpolysiloxanes methylphenylpolysiloxanes
  • cyclic silicones and also amino-, fatty acid-, alcohol-, poly- ether-, epoxy-, fluorine-, glycoside- and/or alkyl-modified silicone compounds, which at room temperature may be in either liquid or resinous form.
  • Linear polysiloxanes dime- thicone (Dow Corning 200 fluid, Rhodia Mirasil DM), dimethiconol, cyclic silicone fluids, cyclopentasiloxanes, volatiles (Dow Corning 345 fluid), phenyltrimethicone (Dow Corn ing 556 fluid).
  • simethicones are mixtures of dimethicones hav ing an average chain length of from 200 to 300 dimethylsiloxane units with hydrogenat ed silicates.
  • a concentration of those silicone emulsifiers ranging from 0.1% to 20% relative to the total weight of the emulsion, and more particularly from 0.5% to 10%, is recommended to develop stable emulsions.
  • the compound of formula 1 (b) is disodi- um-laurylimino-dipropionate (alternative name sodium dodecylimino-diproprionate; i.e. the active ingredient of Deriphat 160 C from BASF SE, Germany)
  • the invention relates moreover to a kit of parts comprising at least two parts, where the first part comprises at least one antimicrobial agent (a) as defined above; the second part comprises at least one compound of the formula (1) or a salt thereof as defined above and optionally at least one organic solvent, preferably as defined above; and an optional third part comprises at least one organic solvent, preferably as defined above; where the first part does not comprise any compound of the formula (1) or salt thereof; where the second part does not comprise any antimicrobial agent as defined above; where the optional third part does not comprise any antimicrobial agent as defined above nor any compound of the formula (1) or salt thereof; and where the first and second parts contain the at least one antimicrobial agent as defined above and the at least one compound of the formula (1) or salt thereof in such amounts that when the first and the second part are mixed the resulting overall weight ratio is as defined above.
  • the first part comprises at least one antimicrobial agent (a) as defined above
  • the second part comprises at least one compound of the formula (1) or a salt thereof as defined above and optionally at least one
  • the first and second parts contain the at least one antimi crobial agent as defined above and the at least one compound of the formula (1) or salt thereof in such amounts that when the first and the second part are mixed the resulting overall weight ratio is in the range of from 1:1 to 20:1 , more preferably from 2:1 to 20:1 , in particular from 5:1 to 15:1.
  • components (a) and (b) are present as a physical mixture, in a kit of parts they are formulated separately, but provided in such a form that they nevertheless form a functional unity. They form thus a true combination through a purpose-directed application.
  • the functional unity is expressed for example in the fact that the parts contain the antimicrobial agent and the compound (1) or salt thereof in such amounts that when mixed, they result in the desired weight ratio.
  • An other way to express functional unity may be a use instruction explaining the combined use of the two or more parts of the kit.
  • Yet another way to express functional unity may be a physical connection.
  • the different parts of the kit may be bound to each other via an adhesive tape or strap or any other type of tie, or may be assembled in a common container, such as a box, package, basket etc. or packed together in a plastic foil.
  • the kit of parts is a kit of two parts, where the first part comprises at least one antimicrobial agent as above; and the second part comprises at least one compound of the formula (1) or salt thereof as defined above and at least one organic, where the organic solvent has preferably one of the above preferred mean ings.
  • the kit of parts is a kit of three parts, where the first part comprises at least one antimicrobial agent as defined above; the second part comprises at least one compound of the formula (1) or salt thereof as defined above; and the third part comprises at least one organic, where the organic solvent has preferably one of the above preferred meanings.
  • the invention relates moreover to the use of a carboxamide compound of the formula (1) or salt thereof as defined above for enhancing the antimicrobial, in particular the preserving, activity of the antimicrobial agent as defined above.
  • room temperature depicts a temperature from the range 22-25°C; over night means a period of 12 to 15 hours; percentages are given by weight of the total composition, if not indicated otherwise. Normal conditions stand for atmospheric pressure and room temperature.
  • the compound of the formula (1) or (T) may be present as acid, salt (e.g. disodium-laurylimino-dipropionate) and/or partial salt (e.g. sodium dodecylimino- diproprionate), independent from the form originally added to the formulation.
  • salt e.g. disodium-laurylimino-dipropionate
  • partial salt e.g. sodium dodecylimino- diproprionate
  • the samples are inoculated with a bacterial mix consisting of: Escherichia coii DSM 1576
  • A/ca/igenes faeca/isOSM 13644 Pseudomonas aeruginosa ATCC 15442 Staphylococcus aureus ATCC 6538 Burkhoideria cepacia DSM 7288 Pseudomonas put id a DSM 12735
  • Samples are stored at 25°C for 14 days (series A) or 21 days (series B). After 7 days, the samples of series B are re-inoculated with the same bacterial mix.
  • Results Series A Results Series B (re-inoculation at day 7) Addition of present amphoteric surfactant to 2-phenoxyethanol results in a surprisingly enhanced antimicrobial activity.
  • Example 2 Preservation of a neutral aqueous 10% propylene glycol solution
  • Example 3 Preservation of a neutral aqueous 10% propylene glycol solution

Abstract

La présente invention concerne une composition comprenant un agent antimicrobien spécifique et un composé de formule (1) ou un sel de celui-ci (1), n étant indépendamment dans la plage allant de 1 à 8 et m étant dans la plage allant de 1 à 21 ; et l'utilisation du composé de formule (1) ou un sel de celui-ci pour améliorer l'activité de certains agents antimicrobiens, en particulier lorsqu'il est utilisé en tant que conservateur pour des préparations aqueuses.
PCT/EP2021/069201 2020-07-10 2021-07-09 Amélioration de l'activité de conservateurs antimicrobiens WO2022008732A1 (fr)

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CN114767560A (zh) * 2022-05-20 2022-07-22 常州瑞昊环保科技有限公司 一种抗菌组合物及其应用

Citations (139)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US367A (en) 1837-08-31 hotchkiss
US5686A (en) 1848-08-01 Powder-proof lock
US2658072A (en) 1951-05-17 1953-11-03 Monsanto Chemicals Process of preparing amine sulfonates and products obtained thereof
US3600186A (en) 1968-04-23 1971-08-17 Procter & Gamble Low calorie fat-containing food compositions
DE2020968A1 (de) 1970-04-29 1971-11-18 Henkel & Cie Gmbh Bactericide Seife
GB1372034A (en) 1970-12-31 1974-10-30 Unilever Ltd Detergent compositions
FR2252840A1 (fr) 1973-11-30 1975-06-27 Oreal
US3929678A (en) 1974-08-01 1975-12-30 Procter & Gamble Detergent composition having enhanced particulate soil removal performance
US4005195A (en) 1976-02-12 1977-01-25 The Procter & Gamble Company Compositions for treating hypercholesterolemia
US4005196A (en) 1976-02-12 1977-01-25 The Procter & Gamble Company Vitaminized compositions for treating hypercholesterolemia
JPS55102699A (en) * 1979-02-01 1980-08-06 Nitsupon Teiipooru Kk Detergent composition for disinfection
EP0218272A1 (fr) 1985-08-09 1987-04-15 Gist-Brocades N.V. Enzymes lipolytiques et leur usage dans des compositions détergentes
US4677120A (en) 1985-07-31 1987-06-30 Molecular Design International Topical prodrugs for treatment of acne and skin diseases
EP0258068A2 (fr) 1986-08-29 1988-03-02 Novo Nordisk A/S Additif enzymatique pour détergent
EP0260105A2 (fr) 1986-09-09 1988-03-16 Genencor, Inc. Préparation d'enzymes à activité modifiée
JPS6336774B2 (fr) 1979-05-25 1988-07-21 Tokyo Shibaura Electric Co
EP0283075A2 (fr) 1987-02-27 1988-09-21 Gist-Brocades N.V. Clonage moléculaire et expression de gènes codant pour des enzymes protéolytiques
JPS6356289B2 (fr) 1979-11-15 1988-11-08 Kansai Denryoku Kk
WO1988009367A1 (fr) 1987-05-29 1988-12-01 Genencor, Inc. Compositions de nettoyage a base de cutinase
US4797300A (en) 1987-04-10 1989-01-10 The Procter & Gamble Company Compositions containing novel solid, nondigestible, fat-like compounds
EP0305216A1 (fr) 1987-08-28 1989-03-01 Novo Nordisk A/S Lipase recombinante de humicola et procédé de production de lipases recombinantes de humicola
JPS6474992A (en) 1987-09-16 1989-03-20 Fuji Oil Co Ltd Dna sequence, plasmid and production of lipase
WO1989006279A1 (fr) 1988-01-07 1989-07-13 Novo-Nordisk A/S Genes de subtilisine mutes
WO1989006276A2 (fr) 1988-01-08 1989-07-13 Dpz Deutsches Primatenzentrum Gesellschaft Mbh Retrovirus de primates du type hiv-2, vaccins, compositions diagnostiques et pharmaceutiques
EP0331376A2 (fr) 1988-02-28 1989-09-06 Amano Pharmaceutical Co., Ltd. ADN recombinant, bactérie du genre pseudomonas le contenant et son utilisation dans un procédé de production de lipase
WO1989009819A1 (fr) 1988-04-12 1989-10-19 Genex Corporation Mutations combinantes de stabilisation de subtilisine
WO1989009830A1 (fr) 1988-04-12 1989-10-19 Genex Corporation Mutations de subtilisine
US4885311A (en) 1987-06-29 1989-12-05 Molecular Design International Topical transretinoids for treatment of acne and skin diseases
WO1990009446A1 (fr) 1989-02-17 1990-08-23 Plant Genetic Systems N.V. Cutinase
EP0407225A1 (fr) 1989-07-07 1991-01-09 Unilever Plc Enzymes et compositions détergentes enzymatiques
JPH034706A (ja) 1989-05-31 1991-01-10 Kubota Corp 人工種子作成方法
WO1991002792A1 (fr) 1989-08-25 1991-03-07 Henkel Research Corporation Enzyme proteolytique alcaline et procede de production
US5011681A (en) 1989-10-11 1991-04-30 Richardson-Vicks, Inc. Facial cleansing compositions
WO1991006637A1 (fr) 1989-10-31 1991-05-16 Genencor International, Inc. Mutants de subtilisine
US5049584A (en) 1988-12-14 1991-09-17 Molecular Design International Dermal uses of cis-retinoids for the treatment of cancer
WO1991016422A1 (fr) 1990-04-14 1991-10-31 Kali-Chemie Aktiengesellschaft Lipases bacillaires alcalines, sequences d'adn de codage pour celles-ci et bacilles produisant ces lipases
WO1991018974A1 (fr) 1990-05-29 1991-12-12 Chemgen Corporation HEMICELLULASE ACTIVE A DES VALEURS EXTREMES DE pH ET DE TEMPERATURE AINSI QUE SES MOYENS DE PRODUCTION
WO1992005249A1 (fr) 1990-09-13 1992-04-02 Novo Nordisk A/S Variantes lipasiques
US5124356A (en) 1987-06-29 1992-06-23 Molecular Design International, Inc. Dermal uses of trans-retinoids for the treatment of photoaging
WO1992019729A1 (fr) 1991-05-01 1992-11-12 Novo Nordisk A/S Enzymes stabilisees et compositions detergentes
WO1993024622A1 (fr) 1992-05-22 1993-12-09 Alko Ltd. Mannanases, genes les codant, procede d'isolement de ces genes, et procedes de blanchiment de pates de lignocellulose
WO1994001541A1 (fr) 1992-07-06 1994-01-20 Novo Nordisk A/S Lipase de c. antarctica et variantes lipasiques
WO1994002597A1 (fr) 1992-07-23 1994-02-03 Novo Nordisk A/S Alpha-amylase mutante, detergent, agent de lavage de vaisselle et de liquefaction
US5306514A (en) 1990-04-26 1994-04-26 The Procter & Gamble Company Solid, nondigestible, fat-like compounds and food compositions containing same
US5306515A (en) 1990-04-26 1994-04-26 The Procter & Gamble Company Reduced calorie pourable shortening, cooking oils, salad oils or like compositions
US5306516A (en) 1990-04-26 1994-04-26 The Procter & Gamble Company Shortening compositions containing polyol fatty acid polyesters
WO1994018314A1 (fr) 1993-02-11 1994-08-18 Genencor International, Inc. Alpha-amylase stable a l'oxydation
WO1994025578A1 (fr) 1993-04-27 1994-11-10 Gist-Brocades N.V. Nouveaux variants de lipase utilises dans des detergents
WO1995002675A1 (fr) 1993-07-12 1995-01-26 Novo Nordisk A/S Composition detersive comprenant deux cellulases
US5389536A (en) 1986-11-19 1995-02-14 Genencor, Inc. Lipase from Pseudomonas mendocina having cutinase activity
WO1995006720A1 (fr) 1993-08-30 1995-03-09 Showa Denko K.K. Nouvelle lipase, micro-organisme la produisant, procede de production de cette lipase, et utilisation de ladite lipase
WO1995010603A1 (fr) 1993-10-08 1995-04-20 Novo Nordisk A/S Variants d'amylase
WO1995014783A1 (fr) 1993-11-24 1995-06-01 Showa Denko K.K. Gene de lipase et lipase variante
WO1995022615A1 (fr) 1994-02-22 1995-08-24 Novo Nordisk A/S Procede pour preparer un variant d'une enzyme lipolytique
WO1995023221A1 (fr) 1994-02-24 1995-08-31 Cognis, Inc. Enzymes ameliorees et detergents les contenant
WO1995030744A2 (fr) 1994-05-04 1995-11-16 Genencor International Inc. Lipases a resistance aux tensioactifs amelioree
WO1995035381A1 (fr) 1994-06-20 1995-12-28 Unilever N.V. Lipases modifiees provenant de pseudomonas et leur utilisation
WO1996000292A1 (fr) 1994-06-23 1996-01-04 Unilever N.V. Pseudomonas lipases modifiees et leur utilisation
JPH0851975A (ja) 1991-10-09 1996-02-27 Res Dev Corp Of Japan 新規なβ−マンナナーゼとその製造方法
WO1996012012A1 (fr) 1994-10-14 1996-04-25 Solvay S.A. Lipase, micro-organisme la produisant, procede de preparation de cette lipase et utilisation de celle-ci
WO1996013580A1 (fr) 1994-10-26 1996-05-09 Novo Nordisk A/S Enzyme a activite lipolytique
WO1996023872A1 (fr) 1995-02-02 1996-08-08 Stichting Centraal Laboratorium Van De Bloedtransfusiedienst Van Het Nederlandse Rode Kruis Enrichissement de cellules souches hematopoietiques provenant du sang ou de la moelle osseuse
WO1996027002A1 (fr) 1995-02-27 1996-09-06 Novo Nordisk A/S Nouveau gene de lipase et procede de production de lipase a l'aide de celui-ci
WO1996034946A1 (fr) 1995-05-05 1996-11-07 Novo Nordisk A/S Variantes du type protease et compositions
WO1997003296A1 (fr) 1995-07-08 1997-01-30 Hohmann Joerg Dispositif de mesure de l'allongement d'un boulon filete ou d'une vis
WO1997004079A1 (fr) 1995-07-14 1997-02-06 Novo Nordisk A/S Enzyme modifiee a activite lipolytique
WO1997007202A1 (fr) 1995-08-11 1997-02-27 Novo Nordisk A/S Nouvelles enzymes lipolytiques
WO1997011164A1 (fr) 1995-09-20 1997-03-27 Genencor International, Inc. Mannanase purifiee provenant de bacillus amyloliquefaciens et procede de preparation
US5686082A (en) 1992-12-24 1997-11-11 L'oreal Cosmetic or pharmaceutical composition containing a combination of a polyphenol and a ginkgo extract
WO1997043424A1 (fr) 1996-05-14 1997-11-20 Genencor International, Inc. α-AMYLASES MODIFIEES POSSEDANT DES PROPRIETES MODIFIEES DE FIXATION DU CALCIUM
WO1998013459A1 (fr) 1996-09-24 1998-04-02 The Procter & Gamble Company Detergents liquides contenant un enzyme proteolytique, un aldehyde peptidique et des ions calcium
WO1998020115A1 (fr) 1996-11-04 1998-05-14 Novo Nordisk A/S Variants et compositions de subtilase
WO1998020116A1 (fr) 1996-11-04 1998-05-14 Novo Nordisk A/S Variants de subtilase et compositions
US5869438A (en) 1990-09-13 1999-02-09 Novo Nordisk A/S Lipase variants
WO1999011768A1 (fr) 1997-08-29 1999-03-11 Novo Nordisk A/S Variants de la protease et compositions
WO1999019467A1 (fr) 1997-10-13 1999-04-22 Novo Nordisk A/S MUTANTS D'α-AMYLASE
WO1999018790A1 (fr) 1997-10-10 1999-04-22 Nvid International, Inc. Desinfectant et procede de fabrication associe
WO1999064619A2 (fr) 1998-06-10 1999-12-16 Novozymes A/S Nouvelles mannanases
WO2000022103A1 (fr) 1998-10-13 2000-04-20 Novozymes A/S Polypeptide modifie a reponse immunitaire reduite
WO2000034450A1 (fr) 1998-12-04 2000-06-15 Novozymes A/S Variantes de cutinase
WO2000060063A1 (fr) 1999-03-31 2000-10-12 Novozymes A/S Variante genetique de lipase
WO2000060060A2 (fr) 1999-03-31 2000-10-12 Novozymes A/S Polypeptides presentant une activite alcaline alpha-amylase et acides nucleiques les codant
EP1093796A1 (fr) 1999-10-22 2001-04-25 L'oreal Emulsions contenant au moins un filtre uv organique insoluble et un polymere associatif
WO2001044452A1 (fr) 1999-12-15 2001-06-21 Novozymes A/S Variants de subtilase a performance de nettoyage amelioree sur des taches d'oeuf
WO2001092502A1 (fr) 2000-06-02 2001-12-06 Novozymes A/S Variants de cutinase
WO2002010355A2 (fr) 2000-08-01 2002-02-07 Novozymes A/S Mutants d'alpha-amylase a proprietes modifiees
WO2002039974A1 (fr) 2000-11-17 2002-05-23 Natural Environment Research Council Compositions de soins personnels
WO2002048298A1 (fr) 2000-12-14 2002-06-20 Ciba Specialty Chemicals Holding Inc. Compositions tensioactives
DE10064983A1 (de) 2000-12-23 2002-07-18 Henkel Kgaa Neue Alkalische Protease aus Bacillus alcalophilus (DSM 11233)
WO2002088340A2 (fr) 2001-05-02 2002-11-07 Henkel Kommanditgesellschaft Auf Aktien Nouvelles variantes de proteases alcalines et detergents contenant ces nouvelles variantes
WO2002099091A2 (fr) 2001-06-06 2002-12-12 Novozymes A/S Endo-beta-1,4-glucanase
WO2003006602A2 (fr) 2001-07-12 2003-01-23 Novozymes A/S Variants de subtilase
WO2003041675A2 (fr) 2001-11-12 2003-05-22 Skinlab Gmbh Utilisation de sterols et de leurs derives dans des preparations cosmetiques et dermatologiques de protection contre les uva
WO2003041676A1 (fr) 2001-11-14 2003-05-22 Cognis Deutschland Gmbh 6 Co. Kg Preparation cosmetique renfermant des polycarbonates
WO2003054184A1 (fr) 2001-12-20 2003-07-03 Henkel Kommanditgesellschaft Auf Aktien Nouvelle protease alcaline extraite de bacillus gibsonii (dsm 14393) et agents de lavage et de nettoyage contenant cette nouvelle protease alcaline
WO2003055974A2 (fr) 2001-12-22 2003-07-10 Henkel Kommanditgesellschaft Auf Aktien Nouvelle protease alcaline obtenue a partir de bacillus sp. (dsm 14392) et agents de lavage et de nettoyage contenant cette protease alcaline
WO2003056017A2 (fr) 2001-12-22 2003-07-10 Henkel Kommanditgesellschaft Auf Aktien Nouvelle protease alcaline obtenue a partir de bacillus sp (dsm 14390) et agents de lavage et de nettoyage contenant cette protease alcaline
US6616935B1 (en) 1998-12-28 2003-09-09 Celanese Ventures Gmbh Method of filtering UV- light
WO2004003186A2 (fr) 2002-06-26 2004-01-08 Novozymes A/S Subtilases et variants de la subtilase presentant une immunogenicite modifiee
WO2004041979A2 (fr) 2002-11-06 2004-05-21 Novozymes A/S Variantes de subtilase
WO2004053039A2 (fr) 2002-12-11 2004-06-24 Novozymes A/S Composition detergente
WO2005056782A2 (fr) 2003-12-03 2005-06-23 Genencor International, Inc. Perhydrolase
WO2005063974A1 (fr) 2003-12-23 2005-07-14 Henkel Kommanditgesellschaft Auf Aktien Nouvelle protease alcaline et produits detergents et nettoyants contenant cette nouvelle protease alcaline
WO2005103244A1 (fr) 2004-04-23 2005-11-03 Henkel Kommanditgesellschaft Auf Aktien Nouvelles proteases alcalines et agents de lavage et detergents renfermant celles-ci
WO2006002643A2 (fr) 2004-07-05 2006-01-12 Novozymes A/S Variants d'alpha-amylases presentant des proprietes modifiees
WO2006066594A2 (fr) 2004-12-23 2006-06-29 Novozymes A/S Variantes de l'alpha-amylase
WO2007006305A1 (fr) 2005-07-08 2007-01-18 Novozymes A/S Variants de subtilase
WO2007087508A2 (fr) 2006-01-23 2007-08-02 Novozymes A/S Variantes de lipase
WO2009061380A2 (fr) 2007-11-05 2009-05-14 Danisco Us Inc., Genencor Division Variants de bacillus sp. ts-23 alpha-amylase à propriétés modifiées
WO2009067279A1 (fr) 2007-11-21 2009-05-28 E.I. Du Pont De Nemours And Company Production de peracides employant une enzyme ayant une activité de perhydrolyse
WO2009109500A1 (fr) 2008-02-29 2009-09-11 Novozymes A/S Polypeptides à activité lipase et polynucléotides codant ces polypeptides
WO2009118375A2 (fr) 2008-03-26 2009-10-01 Novozymes A/S Compositions stabilisées d’enzymes liquides
WO2010065455A2 (fr) 2008-12-01 2010-06-10 Danisco Us Inc. Enzymes ayant une activité lipase
WO2010100028A2 (fr) 2009-03-06 2010-09-10 Huntsman Advanced Materials (Switzerland) Gmbh Procédés enzymatiques de blanchissement-azurage des textiles
WO2010104675A1 (fr) 2009-03-10 2010-09-16 Danisco Us Inc. Alpha-amylases associées à la souche bacillus megaterium dsm90, et leurs procédés d'utilisation
WO2010107560A2 (fr) 2009-03-18 2010-09-23 Danisco Us Inc. Cutinase fongique de magnaporthe grisea
WO2010111143A2 (fr) 2009-03-23 2010-09-30 Danisco Us Inc. Acyltransférases associées à cal a et leurs procédés d'utilisation
WO2011036264A1 (fr) 2009-09-25 2011-03-31 Novozymes A/S Utilisation de variants de protéase
WO2011036263A1 (fr) 2009-09-25 2011-03-31 Novozymes A/S Variants de subtilase
WO2011072099A2 (fr) 2009-12-09 2011-06-16 Danisco Us Inc. Compositions et procédés comprenant des variants de protéase
WO2011084412A1 (fr) 2009-12-21 2011-07-14 Danisco Us Inc. Compositions détergentes contenant une lipase issue de thermobifida fusca et leurs procédés d'utilisation
WO2011084599A1 (fr) 2009-12-21 2011-07-14 Danisco Us Inc. Compositions détergentes contenant une lipase de bacillus subtilis et procédés d'utilisation associés
WO2011084417A1 (fr) 2009-12-21 2011-07-14 Danisco Us Inc. Compositions détergentes contenant une lipase issue de geobacillus stearothermophilus et leurs procédés d'utilisation
WO2011085747A1 (fr) 2010-01-13 2011-07-21 Direvo Industrial Biotechnology Gmbh Nouveaux variants de la mannanase
WO2011098531A1 (fr) 2010-02-10 2011-08-18 Novozymes A/S Variants et compositions contenant des variants à stabilité élevée en présence d'un agent chélateur
WO2011150157A2 (fr) 2010-05-28 2011-12-01 Danisco Us Inc. Compositions de détergent contenant une lipase de streptomyces griseus et leurs procédés d'utilisation
WO2012137147A1 (fr) 2011-04-08 2012-10-11 Danisco Us, Inc. Compositions
WO2013001087A2 (fr) 2011-06-30 2013-01-03 Novozymes A/S Procédé de criblage d'alpha-amylases
WO2013001078A1 (fr) 2011-06-30 2013-01-03 Novozymes A/S Variants d'alpha-amylase
WO2013124784A1 (fr) 2012-02-20 2013-08-29 Basf Se Amélioration de l'activité antimicrobienne de biocides par des polymères
WO2013184577A1 (fr) 2012-06-08 2013-12-12 Danisco Us Inc. Variants d'alpha-amylase dérivés de l'alpha-amylase de cytophaga sp. amylase/ (cspamy2)
WO2014100018A1 (fr) 2012-12-19 2014-06-26 Danisco Us Inc. Nouvelle mannanase, compositions et procédés pour les utiliser
WO2014183920A1 (fr) 2013-05-17 2014-11-20 Novozymes A/S Polypeptides présentant une activité alpha-amylase
WO2014183921A1 (fr) 2013-05-17 2014-11-20 Novozymes A/S Polypeptides présentant une activité alpha-amylase
CN104997659A (zh) 2015-08-12 2015-10-28 江苏绿科生物技术有限公司 一种柔滑洁面啫喱
WO2016092009A1 (fr) 2014-12-10 2016-06-16 Henkel Ag & Co. Kgaa Agent de lavage et de nettoyage solide comprenant de l'amylase
US9502809B2 (en) 2014-04-11 2016-11-22 Tyco Electronics Japan G.K. Surface mount connector
US9507432B2 (en) 2008-02-27 2016-11-29 Qualcomm Incorporated Enhanced input using recognized gestures
WO2019081721A1 (fr) 2017-10-27 2019-05-02 Novozymes A/S Variants de la dnase

Patent Citations (144)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US367A (en) 1837-08-31 hotchkiss
US5686A (en) 1848-08-01 Powder-proof lock
US2658072A (en) 1951-05-17 1953-11-03 Monsanto Chemicals Process of preparing amine sulfonates and products obtained thereof
US3600186A (en) 1968-04-23 1971-08-17 Procter & Gamble Low calorie fat-containing food compositions
DE2020968A1 (de) 1970-04-29 1971-11-18 Henkel & Cie Gmbh Bactericide Seife
GB1372034A (en) 1970-12-31 1974-10-30 Unilever Ltd Detergent compositions
FR2252840A1 (fr) 1973-11-30 1975-06-27 Oreal
US3929678A (en) 1974-08-01 1975-12-30 Procter & Gamble Detergent composition having enhanced particulate soil removal performance
US4005195A (en) 1976-02-12 1977-01-25 The Procter & Gamble Company Compositions for treating hypercholesterolemia
US4005196A (en) 1976-02-12 1977-01-25 The Procter & Gamble Company Vitaminized compositions for treating hypercholesterolemia
JPS55102699A (en) * 1979-02-01 1980-08-06 Nitsupon Teiipooru Kk Detergent composition for disinfection
JPS6336774B2 (fr) 1979-05-25 1988-07-21 Tokyo Shibaura Electric Co
JPS6356289B2 (fr) 1979-11-15 1988-11-08 Kansai Denryoku Kk
US4677120A (en) 1985-07-31 1987-06-30 Molecular Design International Topical prodrugs for treatment of acne and skin diseases
EP0218272A1 (fr) 1985-08-09 1987-04-15 Gist-Brocades N.V. Enzymes lipolytiques et leur usage dans des compositions détergentes
EP0258068A2 (fr) 1986-08-29 1988-03-02 Novo Nordisk A/S Additif enzymatique pour détergent
EP0260105A2 (fr) 1986-09-09 1988-03-16 Genencor, Inc. Préparation d'enzymes à activité modifiée
US5389536A (en) 1986-11-19 1995-02-14 Genencor, Inc. Lipase from Pseudomonas mendocina having cutinase activity
EP0283075A2 (fr) 1987-02-27 1988-09-21 Gist-Brocades N.V. Clonage moléculaire et expression de gènes codant pour des enzymes protéolytiques
US4797300A (en) 1987-04-10 1989-01-10 The Procter & Gamble Company Compositions containing novel solid, nondigestible, fat-like compounds
WO1988009367A1 (fr) 1987-05-29 1988-12-01 Genencor, Inc. Compositions de nettoyage a base de cutinase
US4885311A (en) 1987-06-29 1989-12-05 Molecular Design International Topical transretinoids for treatment of acne and skin diseases
US5124356A (en) 1987-06-29 1992-06-23 Molecular Design International, Inc. Dermal uses of trans-retinoids for the treatment of photoaging
EP0305216A1 (fr) 1987-08-28 1989-03-01 Novo Nordisk A/S Lipase recombinante de humicola et procédé de production de lipases recombinantes de humicola
JPS6474992A (en) 1987-09-16 1989-03-20 Fuji Oil Co Ltd Dna sequence, plasmid and production of lipase
WO1989006279A1 (fr) 1988-01-07 1989-07-13 Novo-Nordisk A/S Genes de subtilisine mutes
WO1989006276A2 (fr) 1988-01-08 1989-07-13 Dpz Deutsches Primatenzentrum Gesellschaft Mbh Retrovirus de primates du type hiv-2, vaccins, compositions diagnostiques et pharmaceutiques
EP0331376A2 (fr) 1988-02-28 1989-09-06 Amano Pharmaceutical Co., Ltd. ADN recombinant, bactérie du genre pseudomonas le contenant et son utilisation dans un procédé de production de lipase
WO1989009819A1 (fr) 1988-04-12 1989-10-19 Genex Corporation Mutations combinantes de stabilisation de subtilisine
WO1989009830A1 (fr) 1988-04-12 1989-10-19 Genex Corporation Mutations de subtilisine
US5049584A (en) 1988-12-14 1991-09-17 Molecular Design International Dermal uses of cis-retinoids for the treatment of cancer
WO1990009446A1 (fr) 1989-02-17 1990-08-23 Plant Genetic Systems N.V. Cutinase
JPH034706A (ja) 1989-05-31 1991-01-10 Kubota Corp 人工種子作成方法
EP0407225A1 (fr) 1989-07-07 1991-01-09 Unilever Plc Enzymes et compositions détergentes enzymatiques
WO1991002792A1 (fr) 1989-08-25 1991-03-07 Henkel Research Corporation Enzyme proteolytique alcaline et procede de production
US5011681A (en) 1989-10-11 1991-04-30 Richardson-Vicks, Inc. Facial cleansing compositions
WO1991006637A1 (fr) 1989-10-31 1991-05-16 Genencor International, Inc. Mutants de subtilisine
WO1991016422A1 (fr) 1990-04-14 1991-10-31 Kali-Chemie Aktiengesellschaft Lipases bacillaires alcalines, sequences d'adn de codage pour celles-ci et bacilles produisant ces lipases
US5306514A (en) 1990-04-26 1994-04-26 The Procter & Gamble Company Solid, nondigestible, fat-like compounds and food compositions containing same
US5306516A (en) 1990-04-26 1994-04-26 The Procter & Gamble Company Shortening compositions containing polyol fatty acid polyesters
US5306515A (en) 1990-04-26 1994-04-26 The Procter & Gamble Company Reduced calorie pourable shortening, cooking oils, salad oils or like compositions
WO1991018974A1 (fr) 1990-05-29 1991-12-12 Chemgen Corporation HEMICELLULASE ACTIVE A DES VALEURS EXTREMES DE pH ET DE TEMPERATURE AINSI QUE SES MOYENS DE PRODUCTION
US5476775A (en) 1990-05-29 1995-12-19 Chemgen Corporation Hemicellulase active at PH and temperature extremes
US5869438A (en) 1990-09-13 1999-02-09 Novo Nordisk A/S Lipase variants
WO1992005249A1 (fr) 1990-09-13 1992-04-02 Novo Nordisk A/S Variantes lipasiques
WO1992019729A1 (fr) 1991-05-01 1992-11-12 Novo Nordisk A/S Enzymes stabilisees et compositions detergentes
JPH0851975A (ja) 1991-10-09 1996-02-27 Res Dev Corp Of Japan 新規なβ−マンナナーゼとその製造方法
WO1993024622A1 (fr) 1992-05-22 1993-12-09 Alko Ltd. Mannanases, genes les codant, procede d'isolement de ces genes, et procedes de blanchiment de pates de lignocellulose
WO1994001541A1 (fr) 1992-07-06 1994-01-20 Novo Nordisk A/S Lipase de c. antarctica et variantes lipasiques
WO1994002597A1 (fr) 1992-07-23 1994-02-03 Novo Nordisk A/S Alpha-amylase mutante, detergent, agent de lavage de vaisselle et de liquefaction
US5686082A (en) 1992-12-24 1997-11-11 L'oreal Cosmetic or pharmaceutical composition containing a combination of a polyphenol and a ginkgo extract
WO1994018314A1 (fr) 1993-02-11 1994-08-18 Genencor International, Inc. Alpha-amylase stable a l'oxydation
WO1994025578A1 (fr) 1993-04-27 1994-11-10 Gist-Brocades N.V. Nouveaux variants de lipase utilises dans des detergents
WO1995002675A1 (fr) 1993-07-12 1995-01-26 Novo Nordisk A/S Composition detersive comprenant deux cellulases
WO1995006720A1 (fr) 1993-08-30 1995-03-09 Showa Denko K.K. Nouvelle lipase, micro-organisme la produisant, procede de production de cette lipase, et utilisation de ladite lipase
WO1995010603A1 (fr) 1993-10-08 1995-04-20 Novo Nordisk A/S Variants d'amylase
WO1995014783A1 (fr) 1993-11-24 1995-06-01 Showa Denko K.K. Gene de lipase et lipase variante
WO1995022615A1 (fr) 1994-02-22 1995-08-24 Novo Nordisk A/S Procede pour preparer un variant d'une enzyme lipolytique
WO1995023221A1 (fr) 1994-02-24 1995-08-31 Cognis, Inc. Enzymes ameliorees et detergents les contenant
EP1921147A2 (fr) 1994-02-24 2008-05-14 Henkel Kommanditgesellschaft auf Aktien Enzymes améliorées et détergents les contenant
WO1995030744A2 (fr) 1994-05-04 1995-11-16 Genencor International Inc. Lipases a resistance aux tensioactifs amelioree
WO1995035381A1 (fr) 1994-06-20 1995-12-28 Unilever N.V. Lipases modifiees provenant de pseudomonas et leur utilisation
WO1996000292A1 (fr) 1994-06-23 1996-01-04 Unilever N.V. Pseudomonas lipases modifiees et leur utilisation
WO1996012012A1 (fr) 1994-10-14 1996-04-25 Solvay S.A. Lipase, micro-organisme la produisant, procede de preparation de cette lipase et utilisation de celle-ci
WO1996013580A1 (fr) 1994-10-26 1996-05-09 Novo Nordisk A/S Enzyme a activite lipolytique
WO1996023872A1 (fr) 1995-02-02 1996-08-08 Stichting Centraal Laboratorium Van De Bloedtransfusiedienst Van Het Nederlandse Rode Kruis Enrichissement de cellules souches hematopoietiques provenant du sang ou de la moelle osseuse
WO1996027002A1 (fr) 1995-02-27 1996-09-06 Novo Nordisk A/S Nouveau gene de lipase et procede de production de lipase a l'aide de celui-ci
WO1996034946A1 (fr) 1995-05-05 1996-11-07 Novo Nordisk A/S Variantes du type protease et compositions
WO1997003296A1 (fr) 1995-07-08 1997-01-30 Hohmann Joerg Dispositif de mesure de l'allongement d'un boulon filete ou d'une vis
WO1997004079A1 (fr) 1995-07-14 1997-02-06 Novo Nordisk A/S Enzyme modifiee a activite lipolytique
WO1997007202A1 (fr) 1995-08-11 1997-02-27 Novo Nordisk A/S Nouvelles enzymes lipolytiques
WO1997011164A1 (fr) 1995-09-20 1997-03-27 Genencor International, Inc. Mannanase purifiee provenant de bacillus amyloliquefaciens et procede de preparation
WO1997043424A1 (fr) 1996-05-14 1997-11-20 Genencor International, Inc. α-AMYLASES MODIFIEES POSSEDANT DES PROPRIETES MODIFIEES DE FIXATION DU CALCIUM
WO1998013459A1 (fr) 1996-09-24 1998-04-02 The Procter & Gamble Company Detergents liquides contenant un enzyme proteolytique, un aldehyde peptidique et des ions calcium
WO1998020115A1 (fr) 1996-11-04 1998-05-14 Novo Nordisk A/S Variants et compositions de subtilase
WO1998020116A1 (fr) 1996-11-04 1998-05-14 Novo Nordisk A/S Variants de subtilase et compositions
WO1999011768A1 (fr) 1997-08-29 1999-03-11 Novo Nordisk A/S Variants de la protease et compositions
WO1999018790A1 (fr) 1997-10-10 1999-04-22 Nvid International, Inc. Desinfectant et procede de fabrication associe
EP1041879B1 (fr) 1997-10-10 2007-12-05 Pure Bioscience Desinfectant et procede de fabrication associe
WO1999019467A1 (fr) 1997-10-13 1999-04-22 Novo Nordisk A/S MUTANTS D'α-AMYLASE
US6566114B1 (en) 1998-06-10 2003-05-20 Novozymes, A/S Mannanases
WO1999064619A2 (fr) 1998-06-10 1999-12-16 Novozymes A/S Nouvelles mannanases
WO2000022103A1 (fr) 1998-10-13 2000-04-20 Novozymes A/S Polypeptide modifie a reponse immunitaire reduite
WO2000034450A1 (fr) 1998-12-04 2000-06-15 Novozymes A/S Variantes de cutinase
US6616935B1 (en) 1998-12-28 2003-09-09 Celanese Ventures Gmbh Method of filtering UV- light
WO2000060063A1 (fr) 1999-03-31 2000-10-12 Novozymes A/S Variante genetique de lipase
WO2000060060A2 (fr) 1999-03-31 2000-10-12 Novozymes A/S Polypeptides presentant une activite alcaline alpha-amylase et acides nucleiques les codant
EP1093796A1 (fr) 1999-10-22 2001-04-25 L'oreal Emulsions contenant au moins un filtre uv organique insoluble et un polymere associatif
WO2001044452A1 (fr) 1999-12-15 2001-06-21 Novozymes A/S Variants de subtilase a performance de nettoyage amelioree sur des taches d'oeuf
WO2001092502A1 (fr) 2000-06-02 2001-12-06 Novozymes A/S Variants de cutinase
WO2002010355A2 (fr) 2000-08-01 2002-02-07 Novozymes A/S Mutants d'alpha-amylase a proprietes modifiees
WO2002039974A1 (fr) 2000-11-17 2002-05-23 Natural Environment Research Council Compositions de soins personnels
WO2002048298A1 (fr) 2000-12-14 2002-06-20 Ciba Specialty Chemicals Holding Inc. Compositions tensioactives
DE10064983A1 (de) 2000-12-23 2002-07-18 Henkel Kgaa Neue Alkalische Protease aus Bacillus alcalophilus (DSM 11233)
WO2002088340A2 (fr) 2001-05-02 2002-11-07 Henkel Kommanditgesellschaft Auf Aktien Nouvelles variantes de proteases alcalines et detergents contenant ces nouvelles variantes
WO2002099091A2 (fr) 2001-06-06 2002-12-12 Novozymes A/S Endo-beta-1,4-glucanase
WO2003006602A2 (fr) 2001-07-12 2003-01-23 Novozymes A/S Variants de subtilase
WO2003041675A2 (fr) 2001-11-12 2003-05-22 Skinlab Gmbh Utilisation de sterols et de leurs derives dans des preparations cosmetiques et dermatologiques de protection contre les uva
WO2003041676A1 (fr) 2001-11-14 2003-05-22 Cognis Deutschland Gmbh 6 Co. Kg Preparation cosmetique renfermant des polycarbonates
WO2003054184A1 (fr) 2001-12-20 2003-07-03 Henkel Kommanditgesellschaft Auf Aktien Nouvelle protease alcaline extraite de bacillus gibsonii (dsm 14393) et agents de lavage et de nettoyage contenant cette nouvelle protease alcaline
WO2003056017A2 (fr) 2001-12-22 2003-07-10 Henkel Kommanditgesellschaft Auf Aktien Nouvelle protease alcaline obtenue a partir de bacillus sp (dsm 14390) et agents de lavage et de nettoyage contenant cette protease alcaline
WO2003055974A2 (fr) 2001-12-22 2003-07-10 Henkel Kommanditgesellschaft Auf Aktien Nouvelle protease alcaline obtenue a partir de bacillus sp. (dsm 14392) et agents de lavage et de nettoyage contenant cette protease alcaline
WO2004003186A2 (fr) 2002-06-26 2004-01-08 Novozymes A/S Subtilases et variants de la subtilase presentant une immunogenicite modifiee
WO2004041979A2 (fr) 2002-11-06 2004-05-21 Novozymes A/S Variantes de subtilase
WO2004053039A2 (fr) 2002-12-11 2004-06-24 Novozymes A/S Composition detergente
WO2005056782A2 (fr) 2003-12-03 2005-06-23 Genencor International, Inc. Perhydrolase
WO2005063974A1 (fr) 2003-12-23 2005-07-14 Henkel Kommanditgesellschaft Auf Aktien Nouvelle protease alcaline et produits detergents et nettoyants contenant cette nouvelle protease alcaline
WO2005103244A1 (fr) 2004-04-23 2005-11-03 Henkel Kommanditgesellschaft Auf Aktien Nouvelles proteases alcalines et agents de lavage et detergents renfermant celles-ci
WO2006002643A2 (fr) 2004-07-05 2006-01-12 Novozymes A/S Variants d'alpha-amylases presentant des proprietes modifiees
WO2006066594A2 (fr) 2004-12-23 2006-06-29 Novozymes A/S Variantes de l'alpha-amylase
WO2007006305A1 (fr) 2005-07-08 2007-01-18 Novozymes A/S Variants de subtilase
WO2007087508A2 (fr) 2006-01-23 2007-08-02 Novozymes A/S Variantes de lipase
WO2009061380A2 (fr) 2007-11-05 2009-05-14 Danisco Us Inc., Genencor Division Variants de bacillus sp. ts-23 alpha-amylase à propriétés modifiées
WO2009067279A1 (fr) 2007-11-21 2009-05-28 E.I. Du Pont De Nemours And Company Production de peracides employant une enzyme ayant une activité de perhydrolyse
US9507432B2 (en) 2008-02-27 2016-11-29 Qualcomm Incorporated Enhanced input using recognized gestures
WO2009109500A1 (fr) 2008-02-29 2009-09-11 Novozymes A/S Polypeptides à activité lipase et polynucléotides codant ces polypeptides
WO2009118375A2 (fr) 2008-03-26 2009-10-01 Novozymes A/S Compositions stabilisées d’enzymes liquides
WO2010065455A2 (fr) 2008-12-01 2010-06-10 Danisco Us Inc. Enzymes ayant une activité lipase
WO2010100028A2 (fr) 2009-03-06 2010-09-10 Huntsman Advanced Materials (Switzerland) Gmbh Procédés enzymatiques de blanchissement-azurage des textiles
WO2010104675A1 (fr) 2009-03-10 2010-09-16 Danisco Us Inc. Alpha-amylases associées à la souche bacillus megaterium dsm90, et leurs procédés d'utilisation
WO2010107560A2 (fr) 2009-03-18 2010-09-23 Danisco Us Inc. Cutinase fongique de magnaporthe grisea
WO2010111143A2 (fr) 2009-03-23 2010-09-30 Danisco Us Inc. Acyltransférases associées à cal a et leurs procédés d'utilisation
WO2011036264A1 (fr) 2009-09-25 2011-03-31 Novozymes A/S Utilisation de variants de protéase
WO2011036263A1 (fr) 2009-09-25 2011-03-31 Novozymes A/S Variants de subtilase
WO2011072099A2 (fr) 2009-12-09 2011-06-16 Danisco Us Inc. Compositions et procédés comprenant des variants de protéase
WO2011084412A1 (fr) 2009-12-21 2011-07-14 Danisco Us Inc. Compositions détergentes contenant une lipase issue de thermobifida fusca et leurs procédés d'utilisation
WO2011084599A1 (fr) 2009-12-21 2011-07-14 Danisco Us Inc. Compositions détergentes contenant une lipase de bacillus subtilis et procédés d'utilisation associés
WO2011084417A1 (fr) 2009-12-21 2011-07-14 Danisco Us Inc. Compositions détergentes contenant une lipase issue de geobacillus stearothermophilus et leurs procédés d'utilisation
WO2011085747A1 (fr) 2010-01-13 2011-07-21 Direvo Industrial Biotechnology Gmbh Nouveaux variants de la mannanase
WO2011098531A1 (fr) 2010-02-10 2011-08-18 Novozymes A/S Variants et compositions contenant des variants à stabilité élevée en présence d'un agent chélateur
WO2011150157A2 (fr) 2010-05-28 2011-12-01 Danisco Us Inc. Compositions de détergent contenant une lipase de streptomyces griseus et leurs procédés d'utilisation
WO2012137147A1 (fr) 2011-04-08 2012-10-11 Danisco Us, Inc. Compositions
WO2013001087A2 (fr) 2011-06-30 2013-01-03 Novozymes A/S Procédé de criblage d'alpha-amylases
WO2013001078A1 (fr) 2011-06-30 2013-01-03 Novozymes A/S Variants d'alpha-amylase
WO2013124784A1 (fr) 2012-02-20 2013-08-29 Basf Se Amélioration de l'activité antimicrobienne de biocides par des polymères
WO2013184577A1 (fr) 2012-06-08 2013-12-12 Danisco Us Inc. Variants d'alpha-amylase dérivés de l'alpha-amylase de cytophaga sp. amylase/ (cspamy2)
WO2014100018A1 (fr) 2012-12-19 2014-06-26 Danisco Us Inc. Nouvelle mannanase, compositions et procédés pour les utiliser
WO2014183921A1 (fr) 2013-05-17 2014-11-20 Novozymes A/S Polypeptides présentant une activité alpha-amylase
WO2014183920A1 (fr) 2013-05-17 2014-11-20 Novozymes A/S Polypeptides présentant une activité alpha-amylase
US9502809B2 (en) 2014-04-11 2016-11-22 Tyco Electronics Japan G.K. Surface mount connector
WO2016092009A1 (fr) 2014-12-10 2016-06-16 Henkel Ag & Co. Kgaa Agent de lavage et de nettoyage solide comprenant de l'amylase
CN104997659A (zh) 2015-08-12 2015-10-28 江苏绿科生物技术有限公司 一种柔滑洁面啫喱
WO2019081721A1 (fr) 2017-10-27 2019-05-02 Novozymes A/S Variants de la dnase
WO2019081724A1 (fr) 2017-10-27 2019-05-02 Novozymes A/S Variants de dnase

Non-Patent Citations (28)

* Cited by examiner, † Cited by third party
Title
"McCutcheon's, Detergents and Emulsifiers", 1990, THE MANUFACTURING CONFECTION-ER PUBLISHING
"McCutcheon's, Functional Materials", 1992
"Merck Index", 1989, pages: 729
ANNA HERMAN: "Antimicrobial Ingredients as Preservative Booster and Components of Self-Preserving Cosmetic Products", CURRENT MICROBIOLOGY, vol. 76, no. 6, 12 April 2018 (2018-04-12), New York, pages 744 - 754, XP055619588, ISSN: 0343-8651, DOI: 10.1007/s00284-018-1492-2 *
CAS , no. 520-45-6
CAS , no. 60372-77-2
CAS, no. 1802181-67-4
COSM. TOIL., vol. 91, 1976, pages 27
DARTOIS ET AL., BIOCHEMICA ET BIOPHYSICA ACTA, vol. 1131, 1992, pages 253 - 360
DATABASE GNPD [online] MINTEL; 28 September 2017 (2017-09-28), ANONYMOUS: "Moist Toilet Tissue for Sensitive Skin", XP055760995, Database accession no. 5127731 *
DATABASE GNPD [online] MINTEL; 8 January 2015 (2015-01-08), ANONYMOUS: "Night Cream", XP055761002, Database accession no. 2753513 *
DELMAR ET AL., ANALYTICAL BIOCHEM, vol. 99, 1979, pages 316 - 320
EL SMITH ET AL., J. BIOL CHEM, vol. 243, 1968, pages 2184 - 2191
GUPTA ET AL., APPL. MICROBIOL. BIOTECHNOL., vol. 60, 2002, pages 381 - 395
GUPTA ET AL., BIOTECHNOL. APPL. BIOCHEM., vol. 37, 2003, pages 63 - 71
H.-G. ELIAS, MACROMOLECULES, vol. 2, 2007, pages 447 - 456
HOFFMAN, W. S., J. BIOL. CHEM., vol. 120, 1937, pages 51
ISIDRO-LLOBET ET AL.: "Amino Acid-Protecting Groups", CHEM. REV., vol. 109, no. 6, 2009, pages 2455 - 2504, XP055559012, DOI: 10.1021/cr800323s
JA WELLS ET AL., NUCLEIC ACIDS RESEARCH, vol. 11, 1983, pages 7911 - 7925
JACOBS ET AL., NUCL. ACIDS RES, vol. 13, 1985, pages 8913 - 8926
K.F.DEPOLO: "Farbstoffkommission der Deutschen Forschungsgemeinschaft", 1984, VERLAG CHEMIE, article "Kosmetische Farbemittel", pages: 250 - 106
NEEDLEMANWUNSCH, J. MOL. BIOL., vol. 48, 1979, pages 443 - 453
PETER G. M. WUTS: "Greene's Protective Groups in Organic Synthesis", 2014, JOHN WILEY & SONS
RESEARCH DISCLOSURE, vol. 213, 1982, pages 471 - 2
SIEZEN ET AL., PROTEIN ENG., vol. 4, 1991, pages 719 - 737
SIEZEN ET AL., PROTEIN SCIENCE, vol. 6, 1997, pages 501 - 523
VASANTHA ET AL., J. BACTERIOL., vol. 159, 1984, pages 811 - 819
VAUGHAN, COSMETICS AND TOILETRIES, vol. 103, October 1988 (1988-10-01), pages 47 - 69

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114767560A (zh) * 2022-05-20 2022-07-22 常州瑞昊环保科技有限公司 一种抗菌组合物及其应用
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