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WO2025238047A1 - Acétate de cellulose à faible degré de substitution - Google Patents

Acétate de cellulose à faible degré de substitution

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Publication number
WO2025238047A1
WO2025238047A1 PCT/EP2025/063150 EP2025063150W WO2025238047A1 WO 2025238047 A1 WO2025238047 A1 WO 2025238047A1 EP 2025063150 W EP2025063150 W EP 2025063150W WO 2025238047 A1 WO2025238047 A1 WO 2025238047A1
Authority
WO
WIPO (PCT)
Prior art keywords
cellulose acetate
composition
liquid
cleaning
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2025/063150
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English (en)
Inventor
Thomas Weiss
Roland Ettl
Erik BARTHEL
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of WO2025238047A1 publication Critical patent/WO2025238047A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/06—Cellulose acetate, e.g. mono-acetate, di-acetate or tri-acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/12—Cellulose acetate
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/226—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin esterified

Definitions

  • the present invention relates to a cellulose acetate, a process for producing cellulose acetate, the use of the cellulose acetate in cleaning compositions, as well as cleaning compositions comprising the cellulose acetate.
  • film-forming water-soluble polymers which may be dissolved in, e.g., mixtures of alcohol and water and which dry as non-sticky films, e.g., polyvinylpyrrolidones.
  • Such polymers are however typically not biodegradable.
  • Cellulose acetate is an organic ester of cellulose. Hydroxy groups are present at the 2-, 3- and 6-posi tion of glucose moieties comprised in cellulose. It is understood that the term "cellulose acetate” refers to partially acetylated cellulose, in which the acetyl content ranges from about 29% to 45%, corresponding to mono-, di-, and triacetate. Cellulose acetate is one of the most important cellulose derivatives and finds application, e.g., in textile fibers, plastics, films and paints.
  • the solubility of cellulose acetate in mixtures of alcohol and water, as well as the degree of biodegradability, are influenced by the degree of substitution.
  • triacetates are generally less soluble than diacetates, which are in turn generally less soluble than monoacetates.
  • Cellulose acetates with reduced degrees of substitution may be obtained by deacetylation, in particular by solvolysis.
  • Solvolysis is understood as a type of nucleophilic substitution or elimination wherein a solvent molecule acts as the nucleophile.
  • a specific example of solvolysis is alcoholysis.
  • a production process where the cellulose acetate can be obtained as a precipitate from solvolysis is particularly efficient.
  • EP 0 822 201 A2 describes a cellulose acetate propionate having an amorphous index of not more than 0.4.
  • cellulose esterified with acetic acid and propionic acid is treated with acetic acid and water to adjust the degree of substitution.
  • US 4,415,734 A describes a process for the preparation of cellulose acetate via alcoholysis.
  • acetic acid and methanol were used in the course alcoholysis.
  • EP 3 995 177 A1 describes a method for obtaining a cellulose acetate with a total degree of acetyl substitution in the range of 0.4 to 0.9.
  • the cellulose acetate is produced by solvolysis in the presence of an acid catalyst.
  • Methanol is preferably used as the solvent for solvolysis.
  • the cellulose acetate should be available through an efficient process.
  • the present invention provides a cellulose acetate having
  • the amorphous index (Am) is preferably in the range of 0.20 to 0.95, more preferably 0.40 to 0.85.
  • a cellulose acetate in accordance with the invention exhibits high solubility in mixtures of alcohol and water and moreover exhibits sufficiently high biodegradability.
  • the degree of substitution (DS, also referred to as the "degree of acetyl substitution”) relates to the total degree of substitution at the 2-postion, 3-position and 6-position of the glucose rings comprised in the cellulose acetate.
  • the degree of substitution can be determined via the following equation:
  • DS 162.14 x AV x 0.01 1 60.052 - 42.037 x AV x 0.01
  • DS is the total degree of acetyl substitution
  • AV is the acetyl value (%).
  • the acetyl value may be determined via a titrimetric method, for example in accordance with ASTM D817-96.
  • the amorphous index is considered indicative of the proportion of crystalline to amorphous components of the cellulose acetate.
  • a high proportion of amorphous components is believed to be indicative of transparent films being obtainable from the cellulose acetate.
  • the cellulose acetate has a number average molecular weight M n in the range of 1 ,000 to 100,000 g/mol, more preferably 1 ,000 to 50,000 g/mol, most preferably 1 ,000 to 10,000 g/mol.
  • M n number average molecular weight of the cellulose acetate increases the degree of biodegradability.
  • the molecular weight may be determined as described below in the experimental part.
  • the biodegradation of the cellulose acetate is at least 30 wt.-% by solids, preferably at least 60 wt.-% by solids, within 28 days according to OECD 301 F.
  • the present invention moreover relates to a process for producing cellulose acetate, in particular a cellulose acetate as described above, comprising
  • the solution comprises a solvent mixture of an aliphatic alcohol and an further organic solvent, the solvent mixture having a vapor pressure at 80 °C below 1.2 bar, preferably below 1.0 bar, and a Hansen solubility parameter 5d of at least 15.5 MPa 1/2 , preferably at least 15.7 MPa 1/2 , more preferably at least 15.9 MPa 1/2 ’ most preferably at least 16.1 or at least 16.2 MPa 1/2 .
  • Alcoholysis is carried out at a pressure in the range of 1 to 10 bar, preferably 1 to 9 bar, more preferably 1 to 6 bar, even more preferably 1 to 4 bar, especially 1 to 2 bar. It is particularly preferred that alcoholysis is carried out at 1 bar, i.e. , atmospheric pressure. All pressures herein are understood as absolute pressures, unless noted otherwise.
  • Alcoholysis is carried out at a temperature in the range of 80 to 170 °C, preferably 80 to 150 °C, more preferably 80 to 135 °C, even more preferably 80 to 110 °C, in particular 80 to 95 °C, especially 80 to 90 °C or 80 to 85 °C.
  • cellulose acetate decomposes.
  • the solvent mixture has a vapor pressure at 80 °C below 1 .2 bar, preferably below 1 .0 bar. Such a relatively low vapor pressure allows for carrying out the present process at temperatures of 80 °C and above without the need for applying significant overpressure so as to avoid excessive evaporation of the solvent mixture.
  • solubility parameters in the three dimensional Hansen solubility space are described in C. M. Hansen: "The Three Dimensional Solubility parameter and Solvent Diffusion Coefficient - Their Importance in Surface Coating Formulation”, Danish Technical Press, Copenhagen, 1967.
  • the Hansen solubility parameter 5d indicates the energy from dispersion forces between molecules, while 5 P denotes the energy from dipolar intermolecular force between molecules, and 5h denotes the energy from hydrogen bonds between molecules.
  • the unit of the Hansen solubility parameters of the parameters is MPa 1/2 .
  • Hansen solubility parameters for many compounds are tabulated in standard works, such as "Hansen Solubility Parameters: A User's Handbook”, C. M. Hansen, 2007, 2nd Edition, CRC.
  • Well-known modeling software, such as HSPIP 3.1.25 (3rd Edition), developed and distributed by C. M. Hansen, or COSMOquick 2021 can also be used to calculate Hansen solubility parameters based on the chemical structure of the compound.
  • the Hansen solubility parameters are calculated assuming room temperature, approximately 25 °C.
  • the Hansen solubility parameters, in particular 5d are calculated according to the method described for the working examples below.
  • the present invention also relates to a cellulose acetate obtained by the process of the invention. It is understood that the embodiments discussed herein apply to all aspects of the invention, unless noted otherwise. For example, the embodiments relating to the cellulose acetate of the invention also concern the process of the invention and the cellulose acetate obtainable by the process of the invention, as far as applicable.
  • the reaction parameters under which the cellulose acetate is obtained influence the substitution pattern at the 2-postion, 3-position and 6-position of the glucose rings comprised in the cellulose acetate.
  • the different positions are each substituted in varying degrees.
  • statistical deviations in the average degree of substitution can occur along the chain. It is believed that the most influential reaction parameters are time, temperature and catalysts used.
  • the present process allows for obtaining cellulose acetate under comparatively mild reaction conditions.
  • a heterogeneous reaction in solvent mixtures, from which the reaction products precipitate can lead to completely different product properties.
  • a heterogeneous reaction is envisaged in the process of the invention.
  • low reaction temperature may induce more strongly varying substitution patterns at the 2-postion, 3-position and 6-position of the glucose rings.
  • Specific reaction parameters may further result in a superposition with a different distribution of the degree of substitution along the main chain.
  • the substitution pattern of the cellulose acetate is associated with certain properties for a given degree of substitution.
  • the substitution pattern may affect the formation of intermolecular and intramolecular hydrogen bonds.
  • a regular formation of hydrogen bonds of the free OH valences can lead to a lower solubility due to altered self-aggregation and vice versa.
  • the col ligative property of the substance as a whole (in solution) may be affected. Deviations in the substitution pattern of the cellulose acetate may therefore lead to significantly altered physicochemical properties.
  • Gradient polymers of low-substituted cellulose acetates are particularly affected by such deviations in the substitution pattern.
  • a cellulose acetate can have the terminal properties of cellulose with selfaggregation, and at the same time have proportions of more highly substituted cellulose acetate with hydrophobic-associative properties.
  • the transitions may be fluid.
  • the aliphatic alcohol is selected from
  • Ci-Ce-monohydric alcohols such as methanol, ethanol, propanol and butanol
  • Ci-Ce-polyhydric alcohols such as ethylene glycol and propylene glycol.
  • the aliphatic alcohol is selected from Ci-Ce-monohydric alcohols, such as methanol, ethanol, propanol and butanol, more preferably from methanol and ethanol, especially methanol.
  • the further organic solvent is selected from
  • alkylene carbonates such as ethylene carbonate and propylene carbonate
  • glycol ethers such as 2-methoxyethanol and 2 -ethoxyethanol
  • dialkyl ketones such as methyl ethyl ketone and diethyl ketone.
  • the further organic solvent is selected from alkylene carbonates, such as ethylene carbonate and propylene carbonate, especially propylene carbonate.
  • the weight ratio of the aliphatic alcohol to the further organic solvent in the solvent mixture is in the range of 10 : 1 to 1 : 10, preferably in the range of 8 : 1 to 1 : 8, more preferably 6 : 1 to 1 : 6.
  • the weight of the solvent mixture is in the range of 50 to 90 wt.-%, preferably 60 to 90 wt.-%, more preferably 70 to 80 wt.-%, based on the weight of the solution of raw cellulose acetate.
  • the aliphatic alcohol primarily serves as the reactive nucleophile in the alcoholysis of raw cellulose acetate, whereas the presence of the further organic solvent allows for precipitation of cellulose acetate from the reaction mixture. Since the cellulose acetate precipitates from the reaction mixture in the presence of the further organic solvent, an additional precipitation medium such as an additional further organic solvent is not necessarily required, resulting in a more efficient process.
  • the content of water in the solvent mixture is preferably 2 parts by weight or less, more preferably 1 part by weight or less, and even more preferably 0.5 parts by weight or less, relative to 1 part by weight of the raw cellulose acetate.
  • water originally contained in the raw cellulose acetate may be removed in advance or not removed.
  • the water content percentage of the raw cellulose acetate may be, for example, 5 wt.% or less, 4 wt.% or less or 3 wt.% or less, and 1 wt.% or greater, in the raw cellulose acetate.
  • the water content of the raw cellulose acetate can be measured by the following method using a Kett moisture meter (METTLER TOLEDO HB43). Approximately 2.0 g of a sample in a water-containing state is placed on an aluminum sample pan of the Kett moisture meter and heated at 120°C until the weight does not change, and the water content percentage (wt.%) in the sample can be calculated from the weight change before and after the heating.
  • a Kett moisture meter MENU HB43
  • the raw cellulose acetate having a degree of substitution of at least 2.0 is not particularly limited and may for example be any such cellulose acetate commercially available.
  • the raw cellulose acetate is comprised in the solution in an amount of 5 to 30 wt.-%, preferably 10 to 25 wt.-%, more preferably 15 to 25 wt.-%, based on the weight of the solution of raw cellulose acetate.
  • the solution of raw cellulose acetate may be obtained in a straightforward manner by mixing the raw cellulose acetate, the aliphatic alcohol and the further organic solvent.
  • the alcoholysis is performed in the presence of an acidic catalyst.
  • Suitable acidic catalysts include inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid; and organic acids such as sulfonic acids, carboxylic acids and/or salts thereof, including methane sulfonic acid, trifluoroacetic acid and formic acid.
  • the acidic catalyst is preferably methane sulfonic acid.
  • the acidic catalyst preferably has an acid dissociation constant pKa in water at 25°C of 0 or less, more preferably -0.5 or less, and even more preferably -1.0 or less.
  • the acid dissociation constant pKa may be -6.0 or greater.
  • the acidic catalyst is typically used in an amount of 0.5 to 20 wt.-%, preferably 1 to 10 wt.-%, more preferably 2 to 4 wt.-%, based on the weight of raw cellulose acetate.
  • amount of the catalyst is too small, the time of the alcoholysis becomes excessively long.
  • amount of the catalyst is too large, the degree of change in depolymerization rate with respect to the alcoholysis temperature becomes greater, the control of the reaction end becomes difficult, and the cellulose acetate having the total degree of substitution according to the present disclosure is less likely to be obtained. Furthermore, nonuniform cellulose acetate having an uneven degree of acetyl substitution tends to be formed.
  • the time of alcoholysis is in the range of 20 to 300 min, for example 30 to 240 min, 60 to 200 min or 60 to 150 min. By setting the time to this range, the desired degree of substitution is typically achievable.
  • additional further organic solvent may be added at the end of the alcoholysis reaction to achieve a higher degree of precipitation of the cellulose acetate.
  • the additional further organic solvent may be the same or different than the one used in the solvent mixture.
  • the amount of additional further organic solvent is typically in the range of 5 to 500 wt.-%, preferably 10 to 200 wt.-%, more preferably 20 to 50 wt.-%, such as 20 to 30 wt.-%, based on the weight of the solvent mixture.
  • the solution may be subjected to cooling at the end of the alcoholysis to achieve a higher degree of precipitation of the cellulose acetate.
  • the solution is cooled to 10 to 100 °C, more preferably 20 to 80 °C, most preferably 20 to 40 °C.
  • the precipitated cellulose acetate is separated from the solution. Any suitable means may be used for this purpose, in particular mechanical separation. For example, the precipitated cellulose acetate may be filtered off.
  • the separated precipitated cellulose acetate may be washed, in particular with an organic solvent in which the cellulose acetate has poor solubility.
  • the cellulose acetate is washed with the additional further organic solvent used for achieving a higher degree of precipitation as described above.
  • the cellulose acetate may be subjected to further purification, such as precipitation fractionation (fractional precipitation) and/or dissolution fractionation (fractional dissolution).
  • Dissolution fractionation may be performed by forming a water-based solution by dissolving the precipitated cellulose acetate in water or a mixed solvent of water and a hydrophilic organic solvent such as acetone, and removing insoluble residues.
  • a hydrophilic organic solvent such as acetone
  • the dissolution of the precipitated cellulose acetate may be performed under stirring at 20 to 80°C, preferably 25 to 60°C.
  • the concentration of the cellulose acetate in the water-based solution is preferably in the range of 2 to 10 wt.-%, more preferably from 3 to 8 wt.-%, based on the weight of the water-based solution.
  • the concentration of the organic solvent in the mixed solvent is typically in the range of 5 to 50 wt.-%, preferably 10 to 40 wt.-%, based on the weight of the mixed solvent.
  • Suitable deposition methods include reprecipitation, e.g., using the additional further organic solvent used for achieving a higher degree of precipitation as described above, and spray drying.
  • a stabilizer may be added to the precipitated cellulose acetate.
  • the stabilizer suitably enhances the thermal stability of the cellulose acetate.
  • Suitable stabilizers include alkali metal compounds, alkaline earth metal compounds and transition metal oxides.
  • Preferred stabilizers include calcium compounds such as calcium hydroxide or magnesium oxide, sodium compounds such as sodium bicarbonate, and zink oxide.
  • Addition of the stabilizer is preferably performed in a volume ratio of a reaction mixture containing cellulose acetate to an aqueous solution of, e.g., calcium hydroxide (0.2 to 1.0 wt.-%) of 100:1 to 10:1.
  • the separated precipitated cellulose acetate is typically dried, optionally after washing and/or purification.
  • the method of drying is not particularly limited. Suitable methods include air drying such as hot-air drying, drying under reduced pressure, and vacuum drying.
  • the obtained cellulose acetate is dried may be pulverized.
  • the pulverization can be performed by using a known pulverizer, such as a sample mill, hammer mill, turbo mill, atomizer, cutter mill, bead mill, ball mill, roll mill, jet mill, and pin mill. Furthermore, freezing and crushing, dry crushing at room temperature, or wet crushing may be performed.
  • any reference to "the cellulose acetate” or “cellulose acetate of the invention” refers to a cellulose acetate of the invention as well as to a cellulose acetate obtained according to the process of the invention.
  • compositions of the present disclosure can "comprise” (i.e. contain other ingredients), “consist essentially of” (comprise mainly or almost only the mentioned ingredients and other ingredients in only very minor amounts, mainly only as impurities), or “consist of' (i.e. contain only the mentioned ingredients and in addition may contain only impurities not avoidable in an technical environment, preferably only the ingredients) the components of the present disclosure.
  • the terms "substantially free of ...” or” substantially free from ...” or “(containing/comprising) essentially no ...” may be used herein; this means that the indicated material is at the very minimum not deliberately added to the composition to form part of it, or, preferably, is not present at analytically detectable levels. It is meant to include compositions whereby the indicated material is present only as an impurity in one of the other materials deliberately included. The indicated material may be present, if at all, at a level of less than 1 %, or even less than 0.1%, or even more less than 0.01%, or even 0%, by weight of the composition.
  • the term "obtainable by” means that corresponding products do not necessarily have to be produced (i.e. obtained) by the corresponding method or process de-scribed in the respective specific context, but also products are comprised which exhibit all features of a product produced (obtained) by said corresponding method or process, wherein said products were actually not produced (obtained) by such method or process.
  • the term “obtainable by” also comprises the more limiting term “obtained by”, i.e. products which were actually produced (obtained) by a method or process described in the respective specific context.
  • number of carbon atoms refers to the total number of carbon atoms in said compound or substituent of a compound.
  • alkyl ether with at least 8 carbon atoms comprising alkylene oxide groups the total number of at least 8 carbon atoms needs to be the sum of the number of carbon atoms of the alkyl moiety and the number of carbon atoms of the alkylene oxide moieties.
  • containing one hydroxy group means that only one group -OH is present. Any functionalized group derived from a hydroxy group such as an ether group is not considered to be an -OH group.
  • containing at least two hydroxy groups means that two or more -OH groups are present.
  • hydroxy group is equal to the term "hydroxyl group” or "-OH group”.
  • Alcohols/compounds having only one hydroxy group such as methanol or ethanol, do, by consequence, not fall under the definition of an alcohol containing at least two hydroxy groups according to compound (A) of the present invention.
  • Any functionalized group derived from a hydroxy group such as an ether group is not considered to be an -OH group.
  • free of water means that the composition contains no more than 5 wt.-% of water based on the total amount of solvent, in another embodiment no more than 1 wt.-% of water based on the total amount of solvent, in a further embodiment the solvent contains no water at all.
  • component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.
  • the present invention moreover provides the use of a cellulose acetate of the invention in a cleaning composition.
  • the cleaning composition may comprise one or more cellulose acetates of the invention.
  • the present invention further provides a cleaning composition, comprising a cellulose acetate of the invention.
  • the cleaning compositions may be used in fabric and home care products, in particular cleaning compositions for improved oily and fatty stain removal, removal of solid dirt such as clay, prevention of greying of fabric surfaces, and/or anti-scale agents.
  • the cleaning composition is a laundry detergent composition and/or a dish wash detergent composition.
  • cleaning composition includes compositions and formulations designed for cleaning soiled material.
  • Such compositions include but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions, laundry prewash, laundry pretreat, laundry additives, spray products, dry cleaning agent or composition, laundry rinse additive, wash additive, post-rinse fabric treatment, ironing aid, dish washing compositions, hard surface cleaning compositions, unit dose formulation, delayed delivery formulation, detergent contained on or in a porous substrate or nonwoven sheet, and other suitable forms known to the person skilled in the art.
  • Such compositions may be used as a pre-laundering treatment, a post-laundering treatment, or may be added during the rinse or wash cycle of the laundering operation.
  • the cleaning compositions may be in any suitable form, including a liquid; a solid such as a powder, granules, agglomerate, paste, tablet, pouches, bar, gel; an emulsion; types delivered in dual- or multicompartment containers; single-phase or multi-phase unit dose; a spray or foam detergent; premoistened wipes (i.e., the cleaning composition in combination with a nonwoven material such as that discussed in US 6,121 , 165, Mackey, et al.); dry wipes (i.e., the cleaning composition in combination with a nonwoven materials, such as that discussed in US 5,980,931 , Fowler, et al.) activated with water by a user or consumer; and other homogeneous, non-homogeneous or single-phase or multiphase cleaning product forms.
  • the cleaning composition is a liquid or solid laundry detergent composition, preferably a liquid laundry detergent composition.
  • the cleaning composition is a liquid or solid, e.g., powder or tab/unit dose, detergent composition for manual or automatic dish wash, preferably a liquid manual dish wash detergent composition.
  • the cleaning composition is a hard surface cleaning composition that may be used for cleaning various surfaces such as hard wood, tile, ceramic, plastic, leather, carpet, metal, lacquered surfaces and glass.
  • a detergent formulation for washing dishes and cutlery i.e. a "hand dish detergent”.
  • a spray cleaner which is typically to be sprayed on a hard surface and then wiped away thereby removing soil and grease etc.
  • the cleaning compositions generally comprise the cellulose acetate in an amount of 0.05 to 50 wt.-%, preferably 0.1 to 15 wt.-%, more preferably 0.25 to 10 wt.-%, even more preferably 0.5 to 5 wt.-%, and most preferably in an amount of up to 3 wt.-%, based on the weight of the cleaning composition.
  • the cleaning composition is a liquid laundry detergent composition and comprises the cellulose acetate in a concentration of 0.1 to 6 wt.-%, preferably 0.5 to 3 wt.-%, more preferably 1 .0 to 2.5 wt.-%, based on the weight of the liquid laundry detergent composition.
  • the cleaning composition is a solid laundry detergent composition and comprises the cellulose acetate in a concentration of 0.1 to 5 wt.-%, preferably 0.3 to 2.5 wt.-%, more preferably 0.5 to 1 .5 wt.-% based on the weight of the solid laundry detergent composition.
  • the cleaning composition may further comprise 1 to 70 wt.-% of a surfactant system, in particular 2 to 60 wt.-% or 5 to 30 wt.-%.
  • the surfactant system may comprise a detersive surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, ampholytic surfactants, and mixtures thereof.
  • detersive surfactant encompasses any surfactant or mixture of surfactants that provide cleaning, stain removing, or laundering benefit to soiled material.
  • the cleaning composition When the cleaning composition is a liquid hand dishwashing or spray detergent cleaning composition, it typically comprises 0.1 to 50 wt.-%, preferably 1 to 35 wt.-%, more preferably 3 to 30 wt.-%, based on the weight of the cleaning composition, of a surfactant system.
  • the surfactant system preferably comprises 60 to 90 wt.-%, more preferably from 70 to 80 wt.-% of an anionic surfactant, based on the weight of the surfactant system.
  • the surfactant system comprises C10-C15 alkyl benzene sulfonates (LAS) and one or more additional surfactants selected from non-ionic, cationic, amphoteric, zwitterionic or other anionic surfactants, or mixtures thereof.
  • LAS alkyl benzene sulfonates
  • additional surfactants selected from non-ionic, cationic, amphoteric, zwitterionic or other anionic surfactants, or mixtures thereof.
  • the cleaning composition is a laundry detergent composition, in particular a liquid laundry detergent composition
  • the surfactant system comprises C12-C18 linear or branched alkyl ethoxylate surfactants with 5 to 10 ethoxy units and one or more additional surfactants selected from anionic, cationic, amphoteric, zwitterionic or other non-ionic surfactants, or mixtures thereof.
  • the cleaning composition is a laundry detergent composition, in particular a liquid laundry detergent composition
  • the surfactant system comprises Cs-C linear or branched alkyl ether sulfates with 1 to 5 ethoxy units and one or more additional surfactants selected from non-ionic, cationic, amphoteric, zwitterionic or other anionic surfactants, or mixtures thereof.
  • the cleaning composition additionally comprises at least one enzyme.
  • Suitable enzymes include lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases, pectate lyases, cutinases, DNases, xylanases, oxicoreductases, dispersins, mannanases and peroxidases, and combinations thereof.
  • the at least one enzyme is selected from lipases, hydrolases, amylases, proteases, cellulases, in particular from lipases.
  • the cleaning composition additionally comprises at least one antimicrobial agent. Suitable antimicrobial agents include 2-phenoxyethanol.
  • the cleaning composition preferably comprises the antimicrobial agent in an amount of 2 ppm to 5 wt.-% based on the weight of the composition, more preferably 0.1 to 2 wt.-%. This embodiment is preferred when the cleaning composition is a cleaning composition in liquid, solid or semi-solid form, preferably a concentrated liquid detergent formulation, single mono doses laundry detergent formulation, liquid hand dish washing detergent formulation or solid automatic dish washing formulation, more preferably a laundry detergent formulation.
  • the present invention provides a method of preserving an aqueous composition against microbial contamination or growth, such composition, specifically a cleaning composition, more preferably a cleaning composition in liquid, solid or semi-solid form, preferably being a concentrated liquid detergent formulation, single mono doses laundry detergent formulation, liquid hand dish washing detergent formulation or solid automatic dish washing formulation, more preferably a laundry detergent formulation, comprising the cellulose acetate, such method comprising adding at least one antimicrobial agent selected from the disclosed antimicrobial agents as disclosed hereinafter, such antimicrobial agent preferably being 2-phenoxyethanol.
  • the cleaning composition comprises 4,4'-dichloro 2-hydroxydiphenylether in an amount of 0.001 to 3 wt.-%, preferably 0.002 to 1 wt.-%, more preferably 0.01 to 0.6 wt.-%, based on the weight of the composition.
  • the cleaning composition is a liquid laundry detergent composition or a liquid hand dish composition, in particular a liquid laundry detergent composition or a liquid softener composition.
  • Liquid cleaning compositions preferably have a viscosity of from 50 to 10,000 mPa*s.
  • liquid manual dish wash cleaning compositions also “liquid manual dish wash compositions”
  • liquid manual dish wash compositions have a viscosity of preferably from 100 to 10,000 mPa*s, more preferably from 200 to 5,000 mPa*s and most preferably from 500 to 3,000 mPa*s at 20 °C
  • liquid laundry cleaning compositions have a viscosity of preferably from 50 to 3,000 mPa*s, more preferably from 100 to 1 ,500 mPa*s and most preferably from 200 to 1 ,000 mPa*s at 20 °C.
  • the cleaning compositions preferably comprise adjunct cleaning additives (also abbreviated herein as "adjuncts”), such adjuncts being preferably present additionally to a surfactant system as defined before.
  • adjunct cleaning additives also abbreviated herein as "adjuncts”
  • Suitable adjunct cleaning additives include builders, cobuilders, structurants or thickeners, clay soil removal/anti-redeposition agents, polymeric soil release agents, dispersants such as polymeric dispersing agents, polymeric grease cleaning agents, solubilizing agents, chelating agents, enzymes, enzyme stabilizing systems, bleaching compounds, bleaching agents, bleach activators, bleach catalysts, brighteners, malodor control agents, pigments, dyes, opacifiers, hueing agents, dye transfer inhibiting agents, chelating agents, suds boosters, suds suppressors (antifoams), color speckles, silver care, antitarnish and/or anti-corrosion agents, alkalinity sources, pH adjusters, pH-buffer agents, hydrotropes, scrubbing particles, antibacterial agents, anti-oxidants, softeners, carriers, processing aids, pro-perfumes, and perfumes.
  • dispersants such as polymeric dispersing agents, polymeric grease cleaning agents, solubilizing agents, chelating agents
  • Liquid cleaning compositions preferably additionally comprise at least one of rheology control/modifying agents, emollients, humectants, skin rejuvenating actives, and solvents.
  • Solid compositions preferably additionally comprise at least one of fillers, bleaches, bleach activators and catalytic materials.
  • Liquid cleaning compositions of the present invention may have any suitable pH-value.
  • the pH of the composition is adjusted to between 4 and 14. More preferably the composition has a pH of from 6 to 13, even more preferably from 6 to 10, most preferably from 7 to 9.
  • the pH of the composition can be adjusted using pH modifying ingredients known in the art and is measured as a 10% product concentration in demineralized water at 25°C. For example, NaOH may be used and the actual weight% of NaOH may be varied and trimmed up to the desired pH such as pH 8.0.
  • a pH >7 is adjusted by using amines, preferably alkanolamines, more preferably triethanolamine.
  • the term "inventive compound(s)” is understood to mean at least one cellulose acetate according to the invention or obtained according to a process of the invention.
  • compositions such as fabric and home care products and formulations for industrial and institutional cleaning, more specifically such as laundry and manual dish wash detergents, are known to a person skilled in the art.
  • Any composition known to the person skilled in the art, in connection with the respective use, can be employed within the context of the present invention by including at least one inventive cellulose acetate or cellulose acetate obtained according to the inventive process, preferably at least one such cellulose acetate in amounts suitable for expressing a certain property within such a composition, especially when such a composition is used in its area of use.
  • the cleaning compositions and formulations of the invention may - and preferably do - contain adjunct cleaning additives (also abbreviated herein as "adjuncts”), such adjuncts being preferably in addition to a surfactant system as defined before.
  • adjunct cleaning additives also abbreviated herein as "adjuncts”
  • Suitable adjunct cleaning additives include builders, cobuilders, structurants or thickeners, clay soil removal/anti-redeposition agents, polymeric soil release agents, dispersants such as polymeric dispersing agents, polymeric grease cleaning agents, solubilizing agents, chelating agents, enzymes, enzyme stabilizing systems, bleaching compounds, bleaching agents, bleach activators, bleach catalysts, brighteners, malodor control agents, pigments, dyes, opacifiers, hueing agents, dye transfer inhibiting agents, chelating agents, suds boosters, suds suppressors (antifoams), color speckles, silver care, antitarnish and/or anti-corrosion agents, alkalinity sources, pH adjusters, pH-buffer agents, hydrotropes, scrubbing particles, antibacterial agents, anti-oxidants, softeners, carriers, processing aids, pro-perfumes, and perfumes. All such adjuncts are detailed and exemplified further below.
  • Liquid cleaning compositions additionally may comprise - and preferably do comprise at least one of - rheology control/modifying agents, emollients, humectants, skin rejuvenating actives, and solvents.
  • Solid compositions additionally may comprise - and preferably do comprise at least one of - fillers, bleaches, bleach activators and catalytic materials.
  • a detersive surfactant encompasses any surfactant or mixture of surfactants that provide cleaning, stain removing, or laundering benefit to soiled material.
  • the cleaning compositions of the invention such as fabric and home care products, and formulations for industrial and institutional cleaning, more specifically such as laundry and manual dish wash detergents, preferably additionally comprise a surfactant system and, more preferably, also further adjuncts, as the one described above and below in more detail.
  • the surfactant system may be composed from one surfactant or from a combination of surfactants selected from anionic surfactants, non-ionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof.
  • a surfactant system for detergents encompasses any surfactant or mixture of surfactants that provide cleaning, stain removing, or laundering benefit to soiled material.
  • the cleaning compositions of the invention preferably comprise a surfactant system in an amount sufficient to provide desired cleaning properties.
  • the surfactant system may comprise a detersive surfactant selected from anionic surfactants, non-ionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof.
  • Wash composition may be any composition, formulation or product which is intended for use in laundry including laundry care, laundry cleaning etc.; hence this term will be used in the following denoting any composition, formulation or product.
  • anionic surfactants contribute usually by far the largest share of surfactants within such formulation.
  • inventive cleaning compositions for use in laundry comprise at least one anionic surfactant and optionally further surfactants selected from any of the surfactant classes described herein, preferably from non-ionic surfactants and/or amphoteric surfactants and/or zwitterionic surfactants and/or cationic surfactants.
  • Cleaning compositions may - and preferably do - also contain anionic surfactants - which may be employed also in combinations of more than one other surfactant.
  • Nonlimiting examples of anionic surfactants - which may be employed also in combinations of more than one surfactant - useful herein include C9-C20 linear alkylbenzenesulfonates (LAS), C10-C20 primary, branched chain and random alkyl sulfates (AS); C10-C18 secondary (2,3) alkyl sulfates; C10-C18 alkyl alkoxy sulfates (AExS) wherein x is from 1 to 30; C10-C18 alkyl alkoxy carboxylates comprising 1 to 5 ethoxy units; mid-chain branched alkyl sulfates as discussed in US 6,020,303 and US 6,060,443; mid-chain branched alkyl alkoxy sulfates as discussed in US 6,008,181 and US 6,020,303; modified alkylbenzene sulfonate (MLAS) as discussed in WO 99/05243, WO 99/05242 and WO 99
  • suitable anionic surfactants are alkali metal and ammonium salts of C8-Ci2-alkyl sulfates, of Ci2-Ci8-fatty alcohol ether sulfates, of Ci2-Ci8-fatty alcohol polyether sulfates, of sulfuric acid half-esters of ethoxylated C4-Ci2-alkylphenols (ethoxylation: 3 to 50 mol of ethylene oxide/mol), of C12-C18- alkylsulfonic acids, of C12-C18 sulfo fatty acid alkyl esters, for example of C12-C18 sulfo fatty acid methyl esters, of Cio-Cis-alkylarylsulfonic acids, preferably of n-Cio-Cis-alkylbenzene sulfonic acids, of C10-C18 alkyl alkoxy carboxylates and of soaps such as for example C8-C24-carboxylic acids.
  • Preference is given
  • anionic surfactants are selected from n-Cio-Cis-alkylbenzene sulfonic acids and from fatty alcohol polyether sulfates, which, within the context of the present invention, are in particular sulfuric acid half-esters of ethoxylated Ci2-Ci8-alkanols (ethoxylation: 1 to 50 mol of ethylene oxide/mol), preferably of n-Ci2-Ci8-alkanols.
  • alcohol polyether sulfates derived from branched (i.e., synthetic) Cn-Ci8-alkanols (ethoxylation: 1 to 50 mol of ethylene oxide/mol) may be employed.
  • the alkoxy lation group of both types of alkoxylated alkyl sulfates is an ethoxylation group and an average ethoxylation degree of any of the alkoxylated alkyl sulfates is 1 to 5, preferably 1 to 3.
  • the laundry detergent formulation of the present invention comprises from at least 1 wt. % to 50 wt. %, preferably in the range from greater than or equal to about 2 wt. % to equal to or less than about 30 wt. %, more preferably in the range from greater than or equal to 3 wt. % to less than or equal to 25 wt. %, and most preferably in the range from greater than or equal to 5 wt. % to less than or equal to 25 wt. % of one or more anionic surfactants as described above, based on the particular overall composition, including other components and water and/or solvents.
  • anionic surfactants are selected from C10-C15 linear alkylbenzenesulfonates, C10-C18 alkylethersulfates with 1-5 ethoxy units and C10-C18 alkylsulfates.
  • Cleaning compositions may also contain non-ionic surfactants - which may be employed also in combinations of more than one other surfactant.
  • Non-limiting examples of non-ionic surfactants - which may be employed also in combinations of more than one other surfactant - include: Cs-C alkyl ethoxylates, such as, NEODOL® non-ionic surfactants from Shell; ethylenoxide/propylenoxide block alkoxylates as PLURONIC® from BASF; C14-C22 mid-chain branched alkyl alkoxylates, BAEx, wherein x is from 1 to 30, as discussed in US 6,153,577, US 6,020,303 and US 6,093,856; alkylpolysaccharides as discussed in U.S.
  • Cs-C alkyl ethoxylates such as, NEODOL® non-ionic surfactants from Shell
  • ethylenoxide/propylenoxide block alkoxylates as PLURONIC® from BASF
  • C14-C22 mid-chain branched alkyl alkoxylates BA
  • non-ionic surfactants are in particular alkoxylated alcohols and alkoxylated fatty alcohols, di- and multiblock copolymers of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, furthermore alkylphenol ethoxylates, alkyl glycosides, polyhydroxy fatty acid amides (glucamides).
  • Examples of (additional) amphoteric surfactants are so-called amine oxides.
  • alkoxy lated alcohols and alkoxy lated fatty alcohols are, for example, compounds of the general formula (A)
  • R 1 is selected from linear Ci-Cio-alkyl, preferably ethyl and particularly preferably methyl,
  • R 2 is selected from C8-C22-alkyl, for example n-CsH , n-CioH2i, n-Ci2H25, n-Ci4H29, n-C Hss or n-CisHsz,
  • R 3 is selected from Ci-Cio-alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1 ,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n- heptyl, n-octyl, 2 -ethylhexyl, n-nonyl, n-decyl or isodecyl, m and n are in the range from zero to 300, where the sum of n and m is at least one.
  • m is in the range from 1 to 100 and n is in the range from 0 to 30.
  • compounds of the general formula (A) may be block copolymers or random copolymers, preference being given to block copolymers.
  • alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (B)
  • R 1 is identical or different and selected from linear Ci-C4-alkyl, preferably identical in each case and ethyl and particularly preferably methyl,
  • R 4 is selected from C6-C2o-alkyl, in particular n-CsH , n-C H2i, n-Ci2H25, n-Ci4H29, n-C Hss, n-CisHsz, a is a number in the range from zero to 6, preferably 1 to 6, b is a number in the range from zero to 20, preferably 4 to 20, d is a number in the range from 4 to 25.
  • At least one of a and b is greater than zero.
  • compounds of the general formula (B) may be block copolymers or random copolymers, preference being given to block copolymers.
  • non-ionic surfactants are selected from di- and multiblock copolymers, composed of ethylene oxide and propylene oxide. Further suitable non-ionic surfactants are selected from ethoxylated or propoxylated sorbitan esters. Alkylphenol ethoxylates or alkyl polyglycosides or polyhydroxy fatty acid amides (glucamides) are likewise suitable. An overview of suitable further non-ionic surfactants can be found in EP A 0 851 023 and in DE-A 198 19 187.
  • Mixtures of two or more different non-ionic surfactants may of course also be present.
  • non-ionic surfactants are selected from C12/14 and C16/18 fatty alkoholalkoxylates, C13/15 oxoalkoholalkoxylates, C13-alkoholalkoxylates, and 2-propyl- heptylalcoholalkoxylates, each of them with 3 - 15 ethoxy units, preferably 5-10 ethoxy units, or with 1-3 propoxy- and 2-15 ethoxy units.
  • Cleaning compositions may also contain amphoteric surfactants - which may be employed also in combinations of more than one other surfactant.
  • Non-limiting examples of amphoteric surfactants - which may be employed also in combinations of more than one other surfactant - include: water-soluble amine oxides containing one alkyl moiety of from about 8 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl moieties and hydroxyalkyl moieties containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl moieties and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms. See WO 01/32816, US 4,681 ,704, and US 4, 133,779. Suitable surfactants include thus so-called amine oxides, such as lauryl dimethyl amine oxide (“lauramine oxide”).
  • amphoteric surfactants are amine oxides.
  • Preferred amine oxides are alkyl dimethyl amine oxides or alkyl amido propyl dimethyl amine oxides, more preferably alkyl dimethyl amine oxides and especially coco dimethyl amino oxides.
  • Amine oxides may have a linear or mid-branched alkyl moiety.
  • the amine oxide is characterized by the formula
  • R 1 -N(R 2 )(R 3 )-O wherein R 1 is a Cs-C alkyl and R 2 and R 3 are selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxethyl, 2-hydroxypropyl and 3-hydroxypropyl.
  • the linear amine oxide surfactants in particular may include linear C10-C18 alkyl dimethyl amine oxides and linear C8-C12 alkoxy ethyl dihydroxy ethyl amine oxides.
  • Preferred amine oxides include linear C10, linear C10-C12, and linear C12-C14 alkyl dimethyl amine oxides.
  • mid-branched means that the amine oxide has one alkyl moiety having n1 carbon atoms with one alkyl branch on the alkyl moiety having n2 carbon atoms.
  • the alkyl branch is located on the alpha carbon from the nitrogen on the alkyl moiety.
  • This type of branching for the amine oxide is also known in the art as an internal amine oxide.
  • the total sum of n1 and n2 is from 10 to 24 carbon atoms, preferably from 12 to 20, and more preferably from 10 to 16.
  • the number of carbon atoms for the one alkyl moiety (n1) should be approximately the same number of carbon atoms as the one alkyl branch (n2) such that the one alkyl moiety and the one alkyl branch are symmetric.
  • symmetric means that (n1-n2) is less than or equal to 5, preferably 4, most preferably from 0 to 4 carbon atoms in at least 50 wt. %, more preferably at least 75 wt. % to 100 wt. % of the mid-branched amine oxides for use herein.
  • the amine oxide further comprises two moieties, independently selected from a C1-C3 alkyl, a C1-C3 hydroxyalkyl group, or a polyethylene oxide group containing an average of from about 1 to about 3 ethylene oxide groups.
  • the two moieties are selected from a C1-C3 alkyl, more preferably both are selected as a Ci alkyl.
  • amphoteric surfactants are selected from Cs-Cis alkyldimethyl aminoxides and Cs-C alkyl-di(hydroxyethyl)aminoxide.
  • amphoteric surfactants can - besides their typical action as surfactant - promote corrosion inhibition, such as compounds having one or two carboxylic groups and one or more amine groups, and optionally further containing also amide-groups and/or hydroxy-groups; such compounds for example being N-(2- carboxyethyl)-N-dodecyl-beta-alaninate (also named N-lauryl-beta-iminodipropionate metal salt, cocoamphodiacetate di-metal salt, cocoamphoacetate metal salt (the metal typically being sodium).
  • such amphoteric surfactants arte preferred when corrosion inhibition is of importance, such as in cleaning applications which typically have a high pH, e.g. automatic dish washing.
  • Cleaning compositions may also contain zwitterionic surfactants - which may be employed also in combinations of more than one other surfactant.
  • Suitable zwitterionic surfactants include betaines, such as alkyl betaines, alkylamidobetaine, amidazoliniumbetaine, sulfobetaine (INCI Sultaines) as well as the phosphobetaines.
  • betaines and sulfobetaines are the following (designated in accordance with INCI): Almond amidopropyl of betaines, Apricotamidopropyl betaines, Avocadamidopropyl of betaines, Babassuamidopropyl of betaines, Behenamidopropyl betaines, Behenyl of betaines, Canol amidopropyl betaines, Capryl/Capramidopropyl betaines, Carnitine, Cetyl of betaines, Cocamidoethyl of betaines, Cocamidopropyl betaines, Cocamidopropyl Hydroxysultaine, Coco betaines, Coco Hydroxysultaine, Coco/Oleam idopropyl betaines, Coco Sultaine, Decyl of betaines, Dihydroxyethyl Oleyl Glycinate, Dihydroxyethyl Soy Glycinate, Dihydroxyethyl Stearyl G
  • Preferred betaines are, for example, Ci2-Ci8-alkylbetaines and sulfobetaines.
  • the zwitterionic surfactant preferably is a betaine surfactant, more preferable a Cocoamidopropylbetaine surfactant.
  • Non-limiting examples of cationic surfactants - which may be employed also in combinations of more than one other surfactant - include: the quaternary ammonium surfactants, which can have up to 26 carbon atoms include: alkoxylated quaternary ammonium (AQA) surfactants as discussed in US 6, 136,769; dimethyl hydroxyethyl quaternary ammonium as discussed in US 6,004,922; dimethyl hydroxyethyl lauryl ammonium chloride; polyamine cationic surfactants as discussed in WO 98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006; cationic ester surfactants as discussed in US patents Nos. 4,228,042, 4,239,660 4,260,529 and US 6,022,844; and amino surfactants as discussed in US 6,221 ,825 and WO 00/47708, specifically amido propyldimethyl amine (APA
  • compositions according to the invention may comprise at least one builder.
  • builders In the context of the present invention, no distinction will be made between builders and such components elsewhere called “co-builders”. Examples of builders are complexing agents, hereinafter also referred to as complexing agents, ion exchange compounds, and precipitating agents. Builders are selected from citrate, phosphates, silicates, carbonates, phosphonates, amino carboxylates and polycarboxylates.
  • citrate includes the mono- and the dialkali metal salts and in particular the mono- and preferably the trisodium salt of citric acid, ammonium or substituted ammonium salts of citric acid as well as citric acid.
  • Citrate can be used as the anhydrous compound or as the hydrate, for example as sodium citrate dihydrate. Quantities of citrate are calculated referring to anhydrous trisodium citrate.
  • phosphate includes sodium metaphosphate, sodium orthophosphate, sodium hydrogenphosphate, sodium pyrophosphate and polyphosphates such as sodium tripolyphosphate.
  • the composition according to the invention is free from phosphates and polyphosphates, with hydrogenphosphates being subsumed, for example free from trisodium phosphate, pentasodium tripolyphosphate and hexasodium metaphosphate ("phosphate-free”).
  • phosphate-free should be understood within the context of the present invention as meaning that the content of phosphate and polyphosphate is in total in the range from 10 ppm to 0.2% by weight of the respective composition, determined by gravimetry.
  • carbonates includes alkali metal carbonates and alkali metal hydrogen carbonates, preferred are the sodium salts. Particularly preferred is Na2CO3.
  • phosphonates are hydroxyalkanephosphonates and aminoalkane _ 'phosphonates.
  • the hydroxyalkanephosphonates the 1-hydroxyethane-1 ,1 -diphosphonate (HEDP) is of particular importance as builder. It is preferably used as sodium salt, the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9).
  • Suitable aminoalkanephosphonates are preferably ethylene diamine tetra methylene _ 'phosphonate (EDTMP), diethylenetriaminepenta methylene _ 'phosphonate (DTPMP), and also their higher homologues. They are preferably used in the form of the neutrally reacting sodium salts, e.g. as hexasodium salt of EDTMP or as hepta- and octa-sodium salts of DTPMP.
  • amino carboxylates and polycarboxylates are nitrilotriacetates, ethylene diamine tetraacetate, diethylene triamine pentaacetate, triethylene tetraamine hexaacetate, propylene diamines tetraacetic acid, ethanol-diglycines, methylglycine diacetate, and glutamine diacetate.
  • amino carboxylates and polycarboxylates also include their respective non-substituted or substituted ammonium salts and the alkali metal salts such as the sodium salts, in particular of the respective fully neutralized compound.
  • Silicates in the context of the present invention include in particular sodium disilicate and sodium metasilicate, alumosilicates such as for example zeolites and sheet silicates, in particular those of the formula o-Na2Si2O5, p-Na2Si2O5, and 6-Na2Si2C>5.
  • compositions according to the invention may contain one or more builder selected from materials not being mentioned above.
  • builders are a-hydroxypropionic acid and oxidized starch.
  • builder is selected from polycarboxylates.
  • polycarboxylates includes non-polymeric polycarboxylates such as succinic acid, C2-Ci6-alkyl disuccinates, C2-Ci6-alkenyl disuccinates, ethylene diamine N,N'-disuccinic acid, tartaric acid diacetate, alkali metal malonates, tartaric acid monoacetate, propanetricarboxylic acid, butanetetracarboxylic acid and cyclopentanetetracarboxylic acid.
  • Oligomeric or polymeric polycarboxylates are for example polyaspartic acid or in particular alkali metal salts of (meth)acrylic acid homopolymers or (meth)acrylic acid copolymers.
  • Suitable co-monomers are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid.
  • a suitable polymer is in particular polyacrylic acid, which preferably has a weight-average molecular weight Mw in the range from 2000 to 40 000 g/mol, preferably 2000 to 10 000 g/mol, in particular 3000 to 8000 g/mol.
  • Further suitable copolymeric polycarboxylates are in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and/or fumaric acid.
  • Suitable hydrophobic co-monomers are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene, olefins with ten or more carbon atoms or mixtures thereof, such as, for example, 1 -decene, 1- dodecene, 1 -tetradecene, 1 -hexadecene, 1 -octadecene, 1-eicosene, 1-docosene, 1 -tetracosene and 1 -hexacosene, C22-a-olefin, a mixture of C2o-C24-a-olefins and polyisobutene having on average 12 to 100 carbon atoms per molecule.
  • Suitable hydrophilic co-monomers are monomers with sulfonate or phosphonate groups, and also non-ionic monomers with hydroxyl function or alkylene oxide groups.
  • allyl alcohol isoprenol, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, methoxypolybutylene glycol (meth)acrylate, methoxypoly(propylene oxide-co-ethylene oxide) (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, ethoxypolypropylene glycol (meth)acrylate, ethoxypolybutylene glycol (meth)acrylate and ethoxypoly(propylene oxide-co-ethylene oxide) (meth)acrylate.
  • Polyalkylene glycols here can comprise 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units per molecule.
  • Particularly preferred sulfonic-acid-group-containing monomers here are 1 -acryl amido- 1 -propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido- 2-methylpropanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2 -hydroxy-3- (2- propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1 -sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide,
  • Particularly preferred phosphonate-group-containing monomers are vinylphosphonic acid and its salts.
  • amphoteric polymers can also be used as builders.
  • compositions according to the invention can comprise, for example, in the range from in total 0.1 to 70% by weight, preferably 10 to 50% by weight, preferably up to 20% by weight, of builder(s), especially in the case of solid formulations.
  • Liquid formulations according to the invention preferably comprise in the range of from 0.1 to 8% by weight of builder.
  • Formulations according to the invention can comprise one or more alkali carriers.
  • Alkali carriers ensure, for example, a pH of at least 9 if an alkaline pH is desired.
  • a preferred alkali metal is in each case potassium, particular preference being given to sodium.
  • a pH >7 is adjusted by using amines, preferably alkanolamines, more preferably triethanolamine.
  • the laundry formulation or composition according to the invention comprises additionally at least one enzyme.
  • Useful enzymes are, for example, one or more hydrolases selected from lipases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases and peroxidases, and combinations of at least two of the foregoing types.
  • composition according to the present invention comprises additionally at least one enzyme.
  • the at least one enzyme is a detergent enzyme.
  • the enzyme is classified as an oxidoreductase (EC 1), a transferase (EC 2), a hydrolase (EC 3), a lyase (EC 4), an isomerase (EC 5), or a ligase (EC 6) (the EC-numbering is according to Enzyme Nomenclature, Recommendations (1992) of the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology including its supplements published 1993-1999).
  • the enzyme is a hydrolase (EC 3).
  • the enzyme is selected from the group consisting of proteases, amylases, lipases, cellulases, mannanases, hemicellulases, phospholipases, esterases, pectinases, lactases, peroxidases, xylanases, cutinases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, beta-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccases, nucleases, DNase, phosphodiesterases, phytases, carbohydrases, galactanases, xanthanases, xyloglucanases, oxidoreductase, perhydrolases, amino
  • the enzyme is selected from the group consisting of proteases, amylases, lipases, cellulases, mannanases, xylanases, DNases, disperses, pectinases, oxidoreductases, and cutinases, and combinations of at least two of the foregoing types.
  • the enzyme is a protease, preferably, a serine protease, more preferably, a subtilisin protease.
  • Such enzyme(s) can be incorporated into the composition at levels sufficient to provide an effective amount for achieving a beneficial effect, preferably for primary washing effects and/or secondary washing effects, like anti-greying or anti-pilling effects (e.g., in case of cellulases).
  • the enzyme is present in the composition at levels from about 0.00001 % to about 5%, preferably from about 0.00001 % to about 2%, more preferably from about 0.0001 % to about 1%, or even more preferably from about 0.001 % to about 0.5% enzyme protein by weight of the composition.
  • the enzyme-containing composition further comprises an enzyme stabilizing system.
  • the enzyme-containing composition described herein comprises from about 0.001 % to about 10%, from about 0.005% to about 8%, or from about 0.01% to about 6%, by weight of the composition, of an enzyme stabilizing system.
  • the enzyme stabilizing system can be any stabilizing system which is compatible with the enzyme.
  • the enzyme stabilizing system comprises at least one compound selected from the group consisting of polyols (preferably, 1 ,3-propanediol, ethylene glycol, glycerol, 1 ,2-propanediol, or sorbitol), salts (preferably, CaCI2, MgCI2, or NaCI), short chain (preferably, Ci-Ce) carboxylic acids (preferably, formic acid, formate (preferably, sodium formate), acetic acid, acetate, or lactate), borate, boric acid, boronic acids (preferably, 4-formyl phenylboronic acid (4-FPBA)), peptide aldehydes, peptide acetals, and peptide aldehyde hydrosulfite adducts.
  • polyols preferably, 1 ,3-propanediol, ethylene glycol, glycerol, 1 ,2-propanediol, or sorbitol
  • salts preferably, CaCI
  • the enzyme stabilizing system comprises a combination of at least two of the compounds selected from the group consisting of salts, polyols, and short chain carboxylic acids and preferably one or more of the compounds selected from the group consisting of borate, boric acid, boronic acids (preferably, 4-formyl phenylboronic acid (4-FPBA)), peptide aldehydes, peptide acetals, and peptide aldehyde hydrosulfite adducts.
  • the compounds selected from the group consisting of salts, polyols, and short chain carboxylic acids preferably one or more of the compounds selected from the group consisting of borate, boric acid, boronic acids (preferably, 4-formyl phenylboronic acid (4-FPBA)), peptide aldehydes, peptide acetals, and peptide aldehyde hydrosulfite adducts.
  • boronic acids preferably, 4-formyl phenylboronic acid (4-FP
  • protease inhibitors may be added, preferably selected from borate, boric acid, boronic acids (preferably, 4-FPBA), peptide aldehydes (preferably, peptide aldehydes like Z-VAL-H or Z-GAY-H), peptide acetals, and peptide aldehyde hydrosulfite adducts.
  • Compositions according to the invention may comprise one or more bleaching agent (bleaches).
  • Preferred bleaches are selected from sodium perborate, anhydrous or, for example, as the monohydrate or as the tetrahydrate or so-called dihydrate, sodium percarbonate, anhydrous or, for example, as the monohydrate, and sodium persulfate, where the term "persulfate” in each case includes the salt of the peracid H2SO5 and also the peroxodisulfate.
  • the alkali metal salts can in each case also be alkali metal hydrogen carbonate, alkali metal hydrogen perborate and alkali metal hydrogen persulfate.
  • the dialkali metal salts are preferred in each case.
  • Formulations according to the invention can comprise one or more bleach catalysts.
  • Bleach catalysts can be selected from oxaziridinium-based bleach catalysts, bleach-boosting transition metal salts or transition metal complexes such as, for example, manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen complexes or carbonyl complexes.
  • Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and also cobalt-, iron-, copper- and rutheniumamine complexes can also be used as bleach catalysts.
  • Formulations according to the invention can comprise one or more bleach activators, for example tetraacetyl ethylene diamine, tetraacetylmethylene diamine, tetra _
  • bleach activators for example tetra
  • Formulations according to the invention can comprise one or more corrosion inhibitors.
  • corrosion inhibitors include triazoles, in particular benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, also phenol derivatives such as, for example, hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol.
  • formulations according to the invention comprise in total in the range from 0.1 to 1 .5% by weight of corrosion inhibitor.
  • amphoteric surfactants can promote corrosion inhibition, such as compounds having one or two carboxylic groups and one or more amine groups, and optionally further containing also amide-groups and/or hydroxy-groups; such compounds for example being N-(2- carboxyethyl)-N-dodecyl-beta-alaninate (also named N-lauryl-beta-iminodipropionate metal salt, cocoamphodiacetate di-metal salt, cocoamphoacetate metal salt (the metal typically being sodium).
  • Formulations according to the invention may also comprise further cleaning polymers and/or soil release polymers.
  • the additional cleaning polymers may include, without limitation, "multifunctional polyethylene imines” (for example BASF's Sokalan® HP20) and/or “multifunctional diamines” (for example BASF's Sokalan® HP96), and also those disclosed and claimed in WO2021/254828, WO2022/136408A1 , WO2022/136409A1 , WO2021/165468, W02023/021103, W02023/021104, W02023/021105 and WO2023/117494.
  • multifunctional polyethylene imines for example BASF's Sokalan® HP20
  • multifunctional diamines for example BASF's Sokalan® HP96
  • Ethoxylated polyethylene imines are typically based on a polyethylene imine core and a polyethylene oxide shell.
  • Suitable polyethylene imine core molecules are polyethylene imines with a weight-average molecular weight Mw in the range of 500 to 5000 g/mol.
  • Mw weight-average molecular weight
  • Preferably employed is a molecular weight from 500 to 1000 g/mol, even more preferred is a Mw of 600 to 800 g/mol.
  • the ethoxylated polymer then has on average 5 to 50, preferably 10 to 35 and even more preferably 20 to 35 ethylene oxide (EO) units per NH-functional group.
  • EO ethylene oxide
  • Suitable multifunctional diamines are typically ethoxylated C2 to C12 alkylene diamines, preferably hexamethylene diamine, which are further quaternized and optionally sulfated.
  • Typical multifunctional diamines have a weight-average molecular weight Mw in the range from 2000 to 10000, more preferably 3000 to 8000, and most preferably 4000 to 6000 g/mol.
  • ethoxylated hexamethylene diamine may be employed, which contains on average 10 to 50, preferably 15 to 40 and even more preferably 20 to 30 ethylene oxide (EO) groups per NH-functional group, and which preferably bears two cationic ammonium groups and two anionic sulfate groups.
  • EO ethylene oxide
  • the cleaning compositions may contain at least one multifunctional polyethylene imine and/or at least one multifunctional diamine to improve the cleaning performance, such as preferably improve the stain removal ability, especially the primary detergency of particulate stains on polyester fabrics of laundry detergents.
  • the multifunctional polyethylene imines or multifunctional diamines or mixtures thereof according to the descriptions above may be added to the laundry detergents and cleaning compositions in amounts of generally from 0.05 to 15 wt. %, preferably from 0.1 to 10 wt. % and more preferably from 0.25 to 5 wt. % and even as low as up to 2 wt.%, based on the particular overall composition, including other components and water and/or solvents.
  • the cleaning compositions may contain at least one multifunctional polyethylene imine and/or at least one multifunctional di- and/or oligoamine, specifically any of the claimed polymers from WO2021/254828, WO2022/136408A1 , WO2022/136409A1 , WO2021/165468, W02023/021103, W02023/021104, W02023/021105 and/or WO2023/117494, to improve the cleaning performance, such as preferably improve the stain removal ability, especially the primary detergency of particulate stains on polyester fabrics of laundry detergents.
  • the multifunctional polyethylene imines or multifunctional di- or oligomines or mixtures thereof according to the descriptions above may be added to the laundry detergents and cleaning compositions in amounts of generally from 0.05 to 15 wt%, preferably from 0.1 to 10 wt% and more preferably from 0.25 to 5 wt% and even as low as up to 2 wt.%, based on the particular overall composition, including other components and water and/or solvents.
  • one aspect of the present invention is a laundry detergent composition, in particular a liquid laundry detergent, comprising (i) at least one inventive compound and (ii) at least one compound selected from multifunctional polyethylene imines and multifunctional diamines and mixtures thereof.
  • the ratio of the at least one inventive compound and (ii) the at least one compound selected from multifunctional polyethylene imines and multifunctional diamines and mixtures thereof is from 10: 1 to 1 : 10, preferably from 5: 1 to 1 :5 and more preferably from 3:1 to 1 :3.
  • Cleaning compositions, fabric and home care products and specifically the laundry formulations comprising the inventive cellulose acetate or cellulose acetate obtained according to the inventive process may also comprise at least one antimicrobial agent (named also "preservative”).
  • An antimicrobial agent is a chemical compound that kills microorganisms or inhibits their growth or reproduction.
  • Microorganisms can be bacteria, yeasts or molds.
  • a preservative is an antimicrobial agent which may be added to aqueous products and compositions to maintain the original performance, characteristics and integrity of the products and compositions by killing contaminating microorganisms or inhibiting their growth.
  • composition/formulation may contain one or more antimicrobial agents and/or preservatives as listed in patent WO2021/115912 A1 ("Formulations comprising a hydrophobically modified polyethyleneimine and one or more enzymes”) on pages 35 to 39.
  • Especially of interest for the cleaning compositions and fabric and home care products and specifically in the laundry formulations are any of the following antimicrobial agents and/or preservatives:
  • 4,4'-dichloro 2-hydroxydiphenyl ether further names: 5-chloro-2-(4-chlorophenoxy) phenol, Diclosan, DCPP), Tinosan® HP 100 (commercial product of BASF SE containing 30% of the antimicrobial active 4,4'- dichoro 2-hydroxydiphenylether); 2-Phenoxyethanol (further names: Phenoxyethanol, Methylphenylglycol, Phenoxetyethanol, ethylene glycol phenyl ether, Ethylene glycol monophenyl ether, 2-(phenoxy) ethanol, 2- phenoxy-1 -ethanol); 2-bromo-2-nitropropane-1,3-diol (further names: 2-bromo-2-nitro-1,3-propanediol, Bronopol); Glutaraldehyde (further names: 1-5-pentandial, pentane-1, 5-dial, glutaral, glutar-dialdehyde); G
  • CIT or “CMIT”
  • CMIT Mixture of 5-chloro-2-methyl-2H- isothiazol-3-one (“CMIT”) and 2-methyl-2H- isothiazol-3-one (“MIT”) (Mixture of CMIT/MIT); 1,2-benzisothiazol-3(2H)-one ("BIT”); Hexa-2,4-dienoic acid (trivial name "sorbic acid”) and its salts, e.g., calcium sorb-ate, sodium sorbate; potassium (E,E)-hexa-2,4- dienoate (Potassium Sorbate); Lactic acid and its salts; L-(+)-lactic acid; especially sodium lactate; Benzoic acid and salts of benzoic acid, e.g., sodium benzoate, ammonium benzo-ate, calcium benzoate, magnesium benzoate, MEA-benzoate, potassium benzoate; Salicylic acid and its salts, e.g., calcium salicylate, magnesium salicy
  • At least one antimicrobial agent or preservative may be added to the inventive composition in a concentration of 0.001 to 10% relative to the total weight of the composition.
  • the composition contains 2-phenoxyethanol in a concentration of 0.1 to 2% or 4,4'-dichloro 2- hydroxydiphenyl ether (DCPP) in a concentration of 0.005 to 0.6%.
  • DCPP 4,4'-dichloro 2- hydroxydiphenyl ether
  • the invention also encompasses a method of preserving an aqueous composition according to the invention against microbial contamination or growth, which method comprises addition of at least one antimicrobial agent or preservative, preferably 2-phenoxyethanol.
  • the invention also encompasses a method of providing an antimicrobial effect on textiles after treatment with a solid laundry detergent (e.g. powders, granulates, capsules, tablets, bars etc.), a liquid laundry detergent, a softener or an after-rinse containing 4, 4' -dichloro 2-hydroxydiphenyl ether (DCPP).
  • a solid laundry detergent e.g. powders, granulates, capsules, tablets, bars etc.
  • DCPP 4, 4' -dichloro 2-hydroxydiphenyl ether
  • Formulations according to the invention may also comprise water and/or additional organic solvents, e.g., ethanol or propylene glycol.
  • additional organic solvents e.g., ethanol or propylene glycol.
  • Further optional ingredients may be but are not limited to viscosity modifiers, cationic surfactants, foam boosting or foam reducing agents, perfumes, dyes, optical brighteners, and dye transfer inhibiting agents.
  • Another aspect of the present invention is also a dish wash composition, comprising at least one inventive compound(s) as described above.
  • an aspect of the present invention is also the use of the inventive compound(s) as described above, in dish wash applications, such as manual or automated dish wash applications.
  • Dish wash compositions according to the invention can be in the form of a liquid, semi-liquid, cream, lotion, gel, or solid composition, solid embodiments encompassing, for example, powders and tablets.
  • Liquid compositions are typically preferred for manual dish wash applications, whereas solid formulations and pouch formulations (where the pouches may contain also solids in addition to liquid ingredients) are typically preferred for automated dish washing compositions; however, in some areas of the world also liquid automated dish wash compositions are used and are thus of course also encompassed by the term "dish wash composition”.
  • the dish wash compositions are intended for direct or indirect application onto dishware and metal and glass surfaces, such as drinking and other glasses, beakers, dish and cooking ware like pots and pans, and cutlery such as forks, spoons, knives and the like.
  • the inventive method of cleaning dishware, metal and/or glass surfaces comprises the step of applying the dish wash cleaning composition, preferably in liquid form, onto the surface, either directly or by means of a cleaning implement, i.e., in neat form.
  • the composition is applied directly onto the surface to be treated and/or onto a cleaning device or implement such as a dish cloth, a sponge or a dish brush and the like without undergoing major dilution (immediately) prior to the application.
  • the cleaning device or implement is preferably wet before or after the composition is delivered to it.
  • the composition can also be applied in diluted form.
  • both neat and dilute application give rise to superior cleaning performance, i.e. the formulations of the invention containing at least one inventive compound, i.e. at least one inventive cellulose acetate or cellulose acetate obtained by the inventive process, exhibit excellent degreasing properties.
  • the effort of removing fat and/or oily soils from the dishware, metal and/or glass surfaces is decreased due to the presence of the inventive compound(s), even when the level of surfactant used is lower than in conventional compositions.
  • the composition is formulated to provide superior grease cleaning (degreasing) properties, long- lasting suds and/or improved viscosity control at decreased temperature exposures; preferably at least two, more preferably all three properties are present in the inventive dish wash composition.
  • Optional - preferably present - further benefits of the inventive manual dish wash composition include soil removal, shine, and/or hand care; more preferably at least two and most preferably all three further benefits are present in the inventive dish wash composition.
  • the inventive compound(s) is one component of a manual dish wash formulation that additionally comprises at least one surfactant, preferably at least one anionic surfactant.
  • the inventive compound(s) is one component of a manual dish wash formulation that additionally comprises at least one anionic surfactant and at least one other surfactant, preferably selected from amphoteric surfactants and/or zwitterionic surfactants.
  • the manual dish wash formulations contain at least one amphoteric surfactant, preferably an amine oxide, or at least one zwitterionic surfactant, preferably a betaine, or mixtures thereof, to aid in the foaming, detergency, and/or mildness of the detergent composition.
  • Preferred anionic surfactants for dish wash compositions are selected from C10-C15 linear alkylbenzenesulfonates, C10-C18 alkylethersulfates with 1-5 ethoxy units and C10-C18 alkylsulfates.
  • the manual dish wash detergent formulation of the present invention comprises from at least 1 wt% to 50 wt%, preferably in the range from greater than or equal to about 3 wt% to equal to or less than about 35 wt%, more preferably in the range from greater than or equal to 5 wt% to less than or equal to 30 wt%, and most preferably in the range from greater than or equal to 5 wt% to less than or equal to 20 wt% of one or more anionic surfactants as described above, based on the particular overall composition, including other components and water and/or solvents.
  • Dish wash compositions according to the invention may comprise at least one amphoteric surfactant.
  • amphoteric surfactants for dish wash compositions are already mentioned above for laundry compositions.
  • Preferred amphoteric surfactants for dish wash compositions are selected from Cs-Cis alkyl-dimethyl aminoxides and Cs-C alkyl-di(hydroxyethyl)aminoxide.
  • the manual dish wash detergent composition of the invention preferably comprises from 1 wt% to 15 wt%, preferably from 2 wt% to 12 wt%, more preferably from 3 wt% to 10 wt% of the composition of an amphoteric surfactant, preferably an amine oxide surfactant.
  • an amphoteric surfactant preferably an amine oxide surfactant.
  • the composition of the invention comprises a mixture of the anionic surfactants and alkyl dimethyl amine oxides in a weight ratio of less than about 10:1 , more preferably less than about 8:1 , more preferably from about 5:1 to about 2:1.
  • amphoteric surfactant provides good foaming properties in the dish wash composition.
  • amphoteric surfactants can - besides their typical action as surfactant - promote corrosion inhibition, such as compounds having one or two carboxylic groups and one or more amine groups, and optionally further containing also amide-groups and/or hydroxy-groups; such compounds for example being N-(2-carboxyethyl)-N-dodecyl-beta-alaninate (also named N-lauryl-beta-iminodipropionate metal salt, cocoamphodi acetate di-metal salt, cocoamphoacetate metal salt (the metal typically being sodium).
  • such amphoteric surfactants are preferred when corrosion inhibition is of importance, such as in cleaning applications which typically have a high pH, e.g. automatic dish washing.
  • Dish wash compositions according to the invention may comprise at least one zwitterionic surfactant.
  • Suitable zwitterionic surfactants for dish wash compositions are already mentioned above for laundry compositions.
  • Preferred zwitterionic surfactants for dish wash compositions are selected from betaine surfactants, more preferable from Cocoamidopropylbetaine surfactants.
  • the zwitterionic surfactant is Cocamidopropylbetaine.
  • the manual dish wash detergent composition of the invention optionally comprises from 1 wt% to 15 wt%, preferably from 2 wt% to 12 wt%, more preferably from 3 wt% to 10 wt% of the composition of a zwitterionic surfactant, preferably a betaine surfactant.
  • Dish wash compositions according to the invention may comprise at least one cationic surfactant.
  • Cationic surfactants when present in the composition, are present in an effective amount, more preferably from 0.1 wt% to 5 wt%, preferably 0.2 wt% to 2 wt% of the composition.
  • Dish wash compositions according to the invention may comprise at least one non-ionic surfactant.
  • non-ionic surfactants for dish wash compositions are already mentioned above for laundry compositions.
  • Preferred non-ionic surfactants are the condensation products of Guerbet alcohols with from 2 to 18 moles, preferably 2 to 15, more preferably 5-12 of ethylene oxide per mole of alcohol.
  • Other preferred non-ionic surfactants for use herein include fatty alcohol polyglycol ethers, alkylpolyglucosides and fatty acid glucamides.
  • the manual hand dish detergent composition of the present invention may comprise from 0.1 wt% to 10 wt%, preferably from 0.3 wt% to 5 wt%, more preferably from 0.4 wt% to 2 wt% of the composition, of a linear or branched C alkoxylated non-ionic surfactant having an average degree of alkoxylation of from
  • the linear or branched Cw alkoxylated non-ionic surfactant is a branched Cw ethoxylated non-ionic surfactant having an average degree of ethoxylation of from 2 to 6, preferably of from 3 to 5.
  • the composition comprises from 60 wt% to 100 wt%, preferably from 80 wt% to 100 wt%, more preferably 100 wt% of the total linear or branched Cw alkoxylated non-ionic surfactant of the branched Cw ethoxylated non-ionic surfactant.
  • the linear or branched Cw alkoxylated non- ionic surfactant preferably is a 2-propy lhepty I ethoxylated non-ionic surfactant having an average degree of ethoxylation of from 3 to 5.
  • a suitable 2-propy lheptyl ethoxylated non-ionic surfactant having an average degree of ethoxylation of 4 is Lutensol® XP40, commercially available from BASF SE, Ludwigshafen, Germany.
  • the use of a 2-propylheptyl ethoxylated non-ionic surfactant having an average degree of ethoxylation of from 3 to 5 leads to improved foam levels and long-lasting suds.
  • one aspect of the present invention is a manual dish wash detergent composition, in particular a liquid manual dish wash detergent composition, comprising (I) at least one inventive compound, and (II) at least one further 2-propylheptyl ethoxylated non-ionic surfactant having an average degree of ethoxylation of from
  • Dish wash compositions according to the invention may comprise at least one hydrotrope in an effective amount, to ensure the compatibility of the liquid manual dish wash detergent compositions with water.
  • Suitable hydrotropes for use herein include anionic hydrotropes, particularly sodium, potassium, and ammonium xylene sulfonate, sodium, potassium and ammonium toluene sulfonate, sodium, potassium, and ammonium cumene sulfonate, and mixtures thereof, and related compounds, as disclosed in U.S. Patent 3,915,903.
  • the liquid manual dish wash detergent compositions of the present invention typically comprise from 0.1 wt% to 15 wt% of the total liquid detergent composition of a hydrotrope, or mixtures thereof, preferably from 1 wt% to 10 wt%, most preferably from 2 wt% to 5 wt% of the total liquid manual dish wash composition.
  • Dish wash compositions according to the invention may comprise at least one organic solvent.
  • organic solvents examples include C4-C14 ethers and diethers, glycols, alkoxylated glycols, C6-C16 glycol ethers, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated linear C1-C5 alcohols, linear C1-C5 alcohols, amines, Cs-Cu alkyl and cycloalkyl hydrocarbons and halohydrocarbons, and mixtures thereof.
  • the liquid dish wash compositions will contain from 0.01 wt% to 20 wt%, preferably from 0.5 wt% to 15 wt%, more preferably from 1 wt% to 10 wt%, most preferably from 1 wt% to 5 wt% of the liquid detergent composition of a solvent.
  • solvents may be used in conjunction with an aqueous liquid carrier, such as water, or they may be used without any aqueous liquid carrier being present.
  • the absolute values of the viscosity may drop but there is a local maximum point in the viscosity profile.
  • the dish wash compositions herein may further comprise from 30 wt% to 90 wt% of an aqueous liquid carrier, comprising water, in which the other essential and optional ingredients are dissolved, dispersed or suspended. More preferably the compositions of the present invention comprise from 45 wt% to 85 wt%, even more preferably from 60 wt% to 80 wt% of the aqueous liquid carrier.
  • the aqueous liquid carrier may contain other materials which are liquid, or which dissolve in the liquid carrier, at room temperature (25 °C) and which may also serve some other function besides that of an inert filler.
  • Dish wash compositions according to the invention may comprise at least one electrolyte.
  • Suitable electrolytes are preferably selected from inorganic salts, even more preferably selected from monovalent salts, most preferably sodium chloride.
  • the liquid manual dish wash compositions according to the invention may comprise from 0.1 wt% to 5 wt%, preferably from 0.2 wt% to 2 wt% of the composition of an electrolyte.
  • Manual dish wash formulations comprising the inventive compound(s) may also comprise at least one antimicrobial agent.
  • the antimicrobial agent may be added to the inventive hand dish wash composition in a concentration of 0.0001 wt% to 10 wt% relative to the total weight of composition.
  • the formulation contains 2-phenoxyethanol in a concentration of 0.01 wt% to 5 wt%, more preferably 0.1 wt% to 2 wt% and/or 4, 4' -dichloro 2-hydroxydiphenyl ether in a concentration of 0.001 wt% to 1 wt%, more preferably 0.002 wt% to 0.6 wt% (in all cases relative to the total weight of the composition).
  • Further additional ingredients are such as but not limited to conditioning polymers, cleaning polymers, surface modifying polymers, soil flocculating polymers, rheology modifying polymers, enzymes, structurants, builders, chelating agents, cyclic diamines, emollients, humectants, skin rejuvenating actives, carboxylic acids, scrubbing particles, bleach and bleach activators, perfumes, malodor control agents, pigments, dyes, opacifiers, beads, pearlescent particles, microcapsules, antibacterial agents, pH adjusters including NaOH and alkanolamines such as mono-ethanolamines and buffering means.
  • the disclosed liquid formulations in this chapter may and preferably do comprise 0 to 2% 2-phenoxyethanol, preferably about 1 %, in addition to all other mentioned ingredients.
  • the disclosed liquid formulations in this chapter may and preferably do comprise 0-0.2% 4,4'-dichoro 2- hydroxydiphenylether, preferably about 0.15 %, in addition to all other mentioned ingredients.
  • the bleach-free solid laundry compositions may comprise 0-0.2% 4,4'-dichoro 2-hydroxydiphenylethe, preferably about 0.15 %, in addition to all other mentioned ingredients.
  • the disclosed formulations in this chapter may and preferably do comprise one or more enzymes selected from those disclosed herein above, more preferably a protease and/or an amylase, wherein even more preferably the protease is a protease with at least 90% sequence identity to SEQ ID NO: 22 of EP1921147B1 and having the amino acid substitution R101 E (according to BPN' numbering) and wherein the amylase is an amylase with at least 90% sequence identity to SEQ ID NO: 54 of WO2021032881A1, such enzyme(s) preferably being present in the formulations at levels from about 0.00001 % to about 5%, preferably from about 0.00001 % to about 2%, more preferably from about 0.0001 % to about 1 %, or even more preferably from about 0.001 % to about 0.5% enzyme protein by weight of the composition.
  • enzymes selected from those disclosed herein above, more preferably a protease and/or an amylase, wherein even more preferably the proteas
  • the invention provides a use of at least one cellulose acetate according to the invention or as obtained in the process according the invention in cleaning compositions and/or in fabric and home care products, preferably being a fabric detergent formulation or a hard surface cleaning formulation, more preferably laundry detergent or dish wash detergent, such composition or product preferably being in liquid or semi-liquid form, such composition or product even more preferably being a concentrated liquid detergent formulation, single mono doses laundry detergent formulation, liquid hand dish washing detergent formulation, most preferably a liquid laundry detergent formulation or a liquid hand dish wash detergent formulation, wherein the at least one cellulose acetate is present at a concentration of from about 0.01% to about 10% in weight % (based on the solid content of the cellulose acetate) in relation to the total weight of such composition or product, preferably the compositions or products further fulfilling at least one of the following requirements: a.
  • an enzyme preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, mannanases, hemicellulases, phospholipases, esterases, xylanases, DNases, dispersins, pectinases, oxidoreductases, cutinases, lactases and peroxidases, more preferably at least two of the aforementioned types, and in case an enzyme is comprised preferably also containing at least one enzyme-stabilizing system; b. comprising about 1 % to about 70% by weight of a surfactant system; c. comprising at least one further cleaning adjunct in effective amounts; d.
  • an improved washing performance preferably in primary cleaning
  • e. comprising an antimicrobial agent selected from the group consisting of 2-phenoxyethanol
  • f. comprising said antimicrobial agent in an amount ranging from 2 ppm to 5% by weight of the composition; more preferably comprising 0.1 to 2% of phenoxyethanol
  • g. comprising 4,4'-dichoro 2-hydroxydiphenylether in a concentration from 0.001 to 3%, preferably 0.002 to 1%, more preferably 0.01 to 0.6%, each by weight of the composition.
  • the invention provides composition comprising at least one cellulose acetate according to the invention or as obtained in the process according the invention, preferably being a cleaning composition or fabric and home care product, more preferably being a fabric detergent formulation or a hard surface cleaning formulation, more preferably laundry detergent or dish wash detergent, such composition or product preferably being in liquid or semi-liquid form, such composition or product even more preferably being a concentrated liquid detergent formulation, single mono doses laundry detergent formulation, liquid hand dish washing detergent formulation, most preferably a liquid laundry detergent formulation or a liquid hand dish wash detergent formulation, wherein the at least one cellulose acetate is present at a concentration of from about 0.01% to about 10% in weight % (based on the solid content of the cellulose acetate) in relation to the total weight of such composition or product, preferably the compositions or products further fulfilling at least one of the following requirements: a.
  • an enzyme preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, mannanases, hemicellulases, phospholipases, esterases, xylanases, DNases, dispersins, pectinases, oxidoreductases, cutinases, lactases and peroxidases, more preferably at least two of the aforementioned types, and in case an enzyme is comprised preferably also containing at least one enzyme-stabilizing system; b. comprising about 1 % to about 70% by weight of a surfactant system; c. comprising at least one further cleaning adjunct in effective amounts; d.
  • an improved washing performance preferably in primary cleaning
  • e. comprising an antimicrobial agent selected from the group consisting of 2-phenoxyethanol
  • f. comprising said antimicrobial agent in an amount ranging from 2 ppm to 5% by weight of the composition; more preferably comprising 0.1 to 2% of phenoxyethanol
  • g. comprising 4,4'-dichoro 2-hydroxydiphenylether in a concentration from 0.001 to 3%, preferably 0.002 to 1%, more preferably 0.01 to 0.6%, each by weight of the composition.
  • the invention provides a method for preserving a composition as described above against microbial contamination or growth, which method comprises addition of an antimicrobial agent selected from the group consisting of 2-phenoxyethanol to the composition which is an aqueous composition comprising water as solvent.
  • the invention provides a method of laundering fabric or of cleaning hard surfaces, which method comprises treating a fabric or a hard surface with a composition as described above, wherein the composition comprises 4,4'-dichloro 2-hydroxydiphenylether, preferably comprising 4,4'-dichloro 2- hydroxydiphenylether in a concentration from 0.001 to 3%, preferably 0.002 to 1%, more preferably 0.01 to 0.6%, each by weight of the composition.
  • a shown formulation is a "comparative formulation”; when the amount chosen is in the general range as disclosed herein and specifically within ranges disclosed herein as preferred amounts for the various ingredients and the inventive compound, the formulation is a formulation according to the invention.
  • Ingredients (other than the inventive compound) listed with amounts including “zero%” in the mentioned range may be present but not necessarily have to be present, in both the inventive and the comparative formulations.
  • each number encompassed by a given range is meant to be included in the formulations shown in this chapter, and all variations and permutations possible are likewise meant to be included.
  • the inventive compound is used in a laundry detergent.
  • Liquid laundry detergents according to the present invention are preferably composed of:
  • Preferred liquid laundry detergents according to the present invention are composed of:
  • anionic surfactants selected from C10-C15- LAS and C10-C18 alkyl ethersulfates containing 1-5 ethoxy-units
  • nonioic surfactants selected from Cio-Ci8-alkyl ethoxylates containing 3 - 10 ethoxy-units
  • soluble organic builders/ cobuilders selected from C10-C18 fatty acids, di- and tricarboxylic acids, hydroxy-di- and hydroxytricaboxylic acids, aminopolycarboxylates and polycarboxylic acids
  • an enzyme system containing at least one enzyme suitable for detergent use and preferably also an enzyme stabilizing system
  • Solid laundry detergents (like e.g. powders, granules or tablets) according to the present invention are preferably composed of:
  • Preferred solid laundry detergents according to the present invention are composed of:
  • anionic surfactants selected from C10-C15- LAS, C10-C18 alkylsulfates and C10-C18 alkyl ethersulfates containing 1-5 ethoxy-units
  • non-ionic surfactants selected from Cio-C -alkyl ethoxylates containing 3 - 10 ethoxy-units
  • inorganic builders and fillers selected from sodium carbonate, sodium bicarbonate, zeolites, soluble silicates, sodium sulfate
  • cobuilders selected from C10-C18 fatty acids, di- and tricarboxylic acids, hydroxydi- and hydroxytricarboxylic acids, aminopolycarboxylates and polycarboxylic acids
  • an enzyme system containing at least one enzyme suitable for detergent use and preferably also an enzyme stabilizing system
  • At least one compound according to the present invention is used in a manual dish wash detergent.
  • Liquid manual dish wash detergents according to the present invention are composed of:
  • liquid manual dish wash detergents are composed of:
  • a co-surfactant preferably selected from the group consisting of an amphoteric surfactant, a zwitterionic surfactant, and mixtures thereof;
  • an enzyme preferably also including an enzyme stabilizing system
  • Alternative preferred liquid manual dish wash detergents according to the present invention are composed of:
  • anionic surfactants selected from C10-C15- LAS, C10-C18 alkyl ethersulfates containing 1-5 ethoxy-units, and C10-C18 alkylsulfate
  • a non-ionic surfactant preferably a C -Guerbet alcohol alkoxylate
  • an enzyme preferably Amylase, and preferably also an enzyme stabilizing system
  • the term "inventive Compound(s)” is understood to mean at least one cellulose acetate according to the invention or obtained according to a process of the invention.
  • Liquid laundry frame formulations according to the invention are Liquid laundry frame formulations according to the invention:
  • Liquid laundry frame formulations according to the invention - continued Laundry powder frame formulations according to the invention: Laundry powder frame formulations according to the invention - continued: Further typical liquid detergent formulations LD1, LD2 and LD3 are shown in the following three tables: (numbers: wt.% active)
  • graft polymer (polyethylene glycol of Mn 6000 g/mol as graft base, grafted with 40 weight-% vinyl acetate (based on total polymer weight; produced following general disclosure of W02007138054A1 )
  • Liquid manual dish wash frame formulations according to the invention are Liquid manual dish wash frame formulations according to the invention:
  • the at least one compound as described in this invention is present at a concentration of from about 0.1 % to about 10%, preferably from about 0.2% to 5%, more preferably from about 0.5% to about 5%, all in relation to the total weight of such composition or product in relation to the total weight of such composition or product, and all numbers in between, and including all ranges resulting from selecting any of the lower limits mentioned and including further 0.2, 0.3, 0.4, 1 , 1.5, 2, 2.5, 3, 3.5 and 4, and combing with any of the upper limits mentioned and including 19, 18, 17, 16, 14, 13, 12, 11 , 9, 8, 7, and 6.
  • the at least one compound as described in this invention is present at a concentration of from about between 0.1 and 50%, preferably between 1 % and 30%, by weight of the detergent composition.
  • the invention provides a liquid composition, in particular a liquid laundry detergent composition, comprising a cellulose acetate and having a turbidity of less than 100 NTU, preferably less than 90 NTU, more preferably less than 80 NTU, as determined by nephelometric measurement relative to a formazine scale. Further details regarding the turbidity measurement may be found in the experimental section below. The above general discussion of liquid compositions likewise applies for this aspect, as well as the suitable amounts of cellulose acetate.
  • the liquid composition comprises the cellulose acetate in a concentration of 0.1 to 6 wt.-%, preferably 0.5 to 3 wt.-%, more preferably 1.0 to 2.5 wt.-%, based on the weight of the liquid composition.
  • the cellulose acetate is a cellulose acetate as discussed above or as obtained according to a process as discussed above.
  • Figure 1 shows an exemplary X-ray diffraction of different cellulose acetates.
  • the degree of substitution (DS, also referred to as the "degree of acetyl substitution”) relates to the total degree of substitution at the 2-postion, 3-position and 6-position of the glucose rings comprised in the cellulose acetate.
  • the degree of substitution can be determined via the following equation:
  • DS 162.14 x AV x 0.01 1 60.052 - 42.037 x AV x 0.01
  • DS is the total degree of acetyl substitution
  • AV is the acetyl value (%).
  • the acetyl value may be determined via a titrimetric method, for example in accordance with ASTM D817-96.
  • the amorphous index (Am) is defined in the following formula:
  • the X-ray scattering intensities are obtained via X-ray powder diffraction (XRD).
  • amorphous index powder samples were placed into a standard sample holder and flattened using a glass slide. Data was collected using a Bruker D8 Advance Series II Diffractometer with multiple sample changer; using Cu-Ka radiation. The voltage and current were set to 40kV and 40mA respectively. Primary side: Cu anode, divergence aperture: 0.1 ° with ASS; secondary side: scattered beam aperture: 8 mm with Ni 0.5 mm, Seller 4° + Lynx-Eye (3° aperture). Data was collected from 2° to 80° (2q), with a step size of 0.02° (2q). The integrated data collection time per step over all the channels of the utilized LynxEye detector 691 .2 seconds.
  • the most prominent features are tabulated and were determined in the following manner.
  • the background was estimated using the Bruker software DIFFRAC.EVA v5.
  • the background function parameters were set to the minimum values of zero for both curvature and threshold.
  • the position and intensity at maximum elevation was chosen to report. Due to the broad signals the error is estimated at 2°.
  • the reported lattice spacing is given for convenience only.
  • the reported intensity is the peak height over the computed background.
  • the relative intensities are pertinent, the absolute values are reported as well.
  • Fig. 1 An exemplary obtained X-ray diffraction is shown in Fig. 1.
  • the ordinate represents the X-ray scattering intensity (Kcps) and the abscissa represents the Bragg angle (29).
  • Kcps X-ray scattering intensity
  • abscissa represents the Bragg angle (29).
  • a major peak was observed for different cellulose acetates at the Bragg angle (29) of 17°.
  • the amorphous index (Am) was calculated according to the formula above.
  • the number average molecular weight (M n ) of cellulose acetate was determined by gel permeation chromatography in DMSO with 9.5 wt.-% LiBr.
  • the mobile phase (eluent) used was DMSO + 9.5 wt.-% LiBr.
  • the concentration of cellulose acetate in DMSO with 9.5 wt.-% LiBr was 1.5 mg per mL.
  • PolarGelM from Agilent was used as columns.
  • the GPC system was operated at a flow rate of 9.5 mL per min.
  • a DRI Agilent G1362A was used as the detection system.
  • Polystyrene standards (from Polymer Laboratories) having a molecular weight M n from 589 to 2,467,999 g/mol were used for the calibration.
  • the nephelometric turbidity was determined using a HI88793 device from Hanna with high accuracy ( ⁇ 2% plus 9.92 NTU) at 525 nm in a 1 cm cuvette, at a temperature of 25 °C.
  • the nephelometric turbidity measurement is relative to a formazine scale (NTU, nephelometric turbidity units) and is indicative of solubility of the components in a composition, in this case of the examined cellulose acetates.
  • NTU formazine scale
  • the vapor pressure of the mixtures was calculated using the extended Raoult's law.
  • the NRTL model was used as the gE model for interpolation.
  • the parameterization of the NRTL model was based on experimental data (exp. vapour-liquid phase equilibrium) as far as these were available and otherwise via the group contribution method UNI FAC (version 2023).
  • the Hansen parameters for dispersion (5d), hydrogen bonding (5h) and polarity (5 P ) were calculated using a Quantitative Structure Property Relationship (QSPR) from COSMOquick from 2008.
  • the Hansen parameters of the mixture were obtained by weighting with the volume fractions (Hansen Solubility
  • Cellulose acetates were obtained from raw cellulose acetate as described in the following.
  • the properties of the obtained cellulose acetates, including the armophous index (Am), the degree of substitution (DS), the number average molecular weight (Mn), and the weight average molecular weight (Mw) are shown in Table 1 below.
  • Acetic acid (720 g) and demineralized water (260 g) were mixed and heated to 40 °C.
  • Raw cellulose acetate (240 g; degree of substitution: 2.45; Mn: 30,000 g/mol; Aldrich) was dissolved therein while stirring.
  • methane sulfonic acid 100%, 24 g was added under stirring. The reaction mixture was subsequently stirred for approximately 55 h. Water was added stepwise: 250 mL after 8 h, 100 mL after 24 h, 200 mL after 30 h.
  • Acetic acid (400 g) and demineralized water (300) were mixed and heated to 100 °C.
  • Raw cellulose acetate (250 g; degree of substitution: 2.45; Mn: 30,000 g/mol; Aldrich) was dissolved therein while stirring.
  • the obtained cellulose acetate was precipitated in 2,000 mL of 2-propanol.
  • the thus obtained white precipitate was collected by filtration and with washed a mixture of 50 mL of 2-propanol and 5 mL 5% aqueous solution of NaHCOa.
  • Acetic acid (600 g) and demineralized water (216 g) were mixed and heated to 40 °C.
  • Raw cellulose acetate (200 g; degree of substitution: 2.45; Mn: 30,000 g/mol; Aldrich) was dissolved therein while stirring.
  • hydrochloric acid 37 wt.-%, 21.6 g was added under stirring.
  • the reaction mixture was subsequently stirred for approximately 50 h.
  • Water was added stepwise to avoid precipitation: 40 mL after 8 h, 20 mL after 24 h, 20 mL after 30 h.
  • the obtained cellulose acetate was precipitated in 2,000 mL of 2-propanol.
  • the thus obtained white precipitate was collected by filtration and washed with a mixture of 50 mL of 2-propanol and 5 mL 5% aqueous solution of NaHCOa.
  • raw cellulose acetate 200 g; degree of substitution: 2.45; Mn: 30,000 g/mol; Aldrich
  • Methane sulfonic acid 100%, 2 g
  • the reaction mixture was subsequently stirred at 100 °C for 4 h.
  • raw cellulose acetate 200 g; degree of substitution: 2.45; Mn: 30,000 g/mol; Aldrich
  • Methane sulfonic acid 100%, 2 g
  • the reaction mixture was subsequently stirred at 90 °C for 8 h.
  • the reaction mixture was allowed to cool to 25 °C, and the product precipitated from the reaction mixture.
  • the obtained cellulose acetate was filtered and washed with a solution of sodium acetate isopropanol (1 % sodium acetate: 2 x 200 mL). Subsequently, the product was dried in a vacuum oven (40 °C, 10 mbar) for 24 h.
  • the stirrer was started at low speed at room temperature.
  • the mixture was heated to a temperature of 80 °C over the course of about 30 min, and the stirring speed was increased to 200 rpm over the same time.
  • Methane sulfonic acid (100%) was added over the course of 10 min.
  • the reaction mixture was stirred for the time indicated in Table 1 below and maintained at about 80 °C. After cooling to 25 °C, the reaction mixture was filtered to obtain a white powder. The white powder was washed 3 times with 50 mL of methanol and finally with a 50 mL of NaHCOa saturated aqueous solution in 95% methanol.
  • the anti-greying performance of aqueous compositions was tested by preparing wash solutions using water of 14°dH hardness (2.5 mmol/L; Ca:Mg:HCO3 4:1 :8) containing 3 g/L of the test detergent TD (see Table 2 below) and 1.0 or 1 .5% b.w., with respect to the detergent dosage, of cellulose acetates obtained according to Table 1 above.
  • test fabrics were 10 cm x 10 cm squares of different cotton fabrics (wfk10A as standard cotton, wfK12A as cotton terry cloth, wfk80A as cotton knit, EMPA 221 as cotton fabric, cretonne, bleached without optical brightener, T-shirt from Brantic, Kapart brand) and different synthetic fabrics (wfk20A, wfk30A, EMPA406).
  • the test was performed in a launder-O-meter with beakers of 1 L size.
  • Greying material was 2.5 g EMPA 101 (purchased at EMPA Testmaterials, St Gallen, Switzerland), 2.5 g SBL 2004; red clay (purchased from wfk Testgewebe GmbH, Bruggen, Germany), 2.5 g SBL 2004; clay slurry (purchased from wfk Testgewebe GmbH, Bruggen, Germany), or carbon black (PentaCarbon GmbH, Germany).
  • the first cycle was run using the launder-O-meter beakers containing the test wash solution (0.25 L) plus test fabrics and ballast soil at 30 °C for 20 min (fabric to liquor ratio of 1 :10). After the wash, the test fabrics and ballast soil were separated. The process was repeated using the washed test fabrics and effectuating 5 cycles in total. New ballast soil was used for each cycle. After the 5 cycles, the test fabrics were rinsed in water, followed by drying at ambient room temperature overnight.
  • the greying of the cotton and synthetic test fabrics was measured by determining the degree of whiteness (reflectance values) after washing using a sphere reflectance spectrometer (SF 500 type from Datacolor, USA, wavelength range 360 to 700 nm, optical geometry d/8°) with a UV cut- off filter at 460 nm.
  • SF 500 type from Datacolor, USA, wavelength range 360 to 700 nm, optical geometry d/8°
  • the anti-greying properties of the detergents tested were then quantified after addition of 1.0 or 1.5% b.w. of the respective aqueous composition. Reflectance values decrease with the visible greying of the fabrics. Thus, the higher the reflectance value, the better the anti-greying performance of the detergent. Fabrics DR values represent the difference between the reflectance after wash of the test detergent T containing the corresponding polymer and the reflectance after the wash of the test detergent without the polymer for the summation of the 8 different test fabrics. The results are shown in Table 3 below.
  • Liquid detergent formulation TD as described above was mixed with different cellulose acetates at a concentration of 3 wt.-%.
  • the turbidity was determined by nephelometric measurement relative to a formazine scale (NTU). The results are shown in Table 4 below. Table 4

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Abstract

Un acétate de cellulose a un degré de substitution dans la plage de 0,3 à 1,5, de préférence de 0,5 à 1,0 ; et un indice amorphe (Am) tel que déterminé par diffraction des rayons X sur poudre de 0,10 à 1,10. L'invention concerne en outre un procédé de production d'acétate de cellulose, l'utilisation de l'acétate de cellulose dans une composition de nettoyage, un produit d'entretien textile et ménager, un produit de nettoyage industriel et institutionnel, un produit de soin cosmétique ou personnel, une composition comprenant l'acétate de cellulose, et une composition liquide comprenant un acétate de cellulose et ayant une turbidité inférieure à 100 NTU.
PCT/EP2025/063150 2024-05-14 2025-05-14 Acétate de cellulose à faible degré de substitution Pending WO2025238047A1 (fr)

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WO2021254828A1 (fr) 2020-06-17 2021-12-23 Basf Se Copolymères amphiphiles, alcoxylés, de polyéthylène/-propylène imine destinés à des formulations de détergent offrant de multiples avantages
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WO2023021103A1 (fr) 2021-08-19 2023-02-23 Basf Se Oligoalkylèneimines alcoxylées modifiées et oligoamines alcoxylées modifiées
WO2023021105A1 (fr) 2021-08-19 2023-02-23 Basf Se Polyalkylène imines alcoxylées modifiées ou polyamines alcoxylées modifiées
WO2023021104A1 (fr) 2021-08-19 2023-02-23 Basf Se Polyalkylène imines alcoxylées modifiées et polyamines alcoxylées modifiées pouvant être obtenues par un procédé comprenant les étapes a) à d)
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