Detergent formulations

Abstract

There is provided a detergent formulation comprising a detergent surfactant and a crosslinked cellulose ether, the crosslinked cellulose ether containing 0.1 to 0.6 wt. % polyether groups, based on the weight of the crosslinked cellulose ether.

Description

[Technical field]

[0001] The present invention relates to detergent formulations, in particular detergent formulations incorporating a detergent surfactant and a crosslinked cellulose ether, the crosslinked cellulose ether containing 0.1 to 0.6% by weight of polyether groups based on the weight of the crosslinked cellulose ether.

[0002] Detergent formulations in tablet form offer several advantages over formulations provided in granular form, such as ease of administration, storage, transportation and handling.

[0003] Detergent formulations in tablet form are typically prepared by premixing the components of the detergent formulation and then forming the premixed components into tablets using a suitable device, such as a tablet press. Detergent tablets are typically formed using compression of the components to provide a tablet that is robust enough to facilitate transportation and handling without damage. In addition to being robust, detergent tablets must dissolve quickly enough so that the detergent components can be released into the wash water as soon as possible at the start of the wash cycle.

[0004] A dichotomy persists in conventional formulations: higher compression forces used in preparing detergent tablets generally correlate with improved robustness; whereas lower compression forces used in preparing detergent tablets generally correlate with improved (faster) dissolution in the wash water. This dichotomy is exacerbated by the fact that conventional detergent tablet formulations tend to exhibit relatively poor long-term storage stability, which has historically been compensated for by using higher compression specifications during manufacturing.

[0005] One detergent tablet composition is described by Whitaker et al. in U.S. Patent No. 6,974,789. Whitaker et al. disclose a detergent tablet for use in a washing machine, the tablet having two or more phases, at least one of which comprises one or more of the following: a) a polymeric disintegrant having a particle size distribution such that at least 90% by weight has a particle size less than about 0.3 mm and at least 30% by weight has a particle size less than about 0.2 mm, or b) a water-soluble hydrated salt having a solubility in distilled water of at least about 25 g / 100 g at 25° C., the salt being selected from sodium acetate, sodium metaborate, sodium orthophosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium potassium tartrate, potassium aluminum sulfate, calcium bromide, calcium nitrate, sodium citrate, potassium citrate, and hydrates of mixtures thereof, the detergent tablet comprising: i) a first phase in the form of a shaped body having at least one mold therein, the shaped body having a compressible force of at least 250 kg / cm 2 and ii) a second phase in the form of a compressed particulate solid fixed within said mould, said compressed particulate solid being compressed at a pressure of about 350 kg / cm. 2 and a second phase, compressed at a pressure less than 1000 nm.

[0006] Nonetheless, there remains a need for new detergent tablet formulations, particularly those that exhibit robustness for shipping and handling, while dissolving rapidly when introduced into water.

[0007] The present invention provides a detergent formulation comprising a detergent surfactant and a crosslinked cellulose ether, the crosslinked cellulose ether containing 0.1 to 0.6% by weight of polyether groups, based on the weight of the crosslinked cellulose ether.

[0008] The present invention provides a detergent formulation comprising a detergent, a crosslinked cellulose ether, the crosslinked cellulose ether containing 0.1-0.6% by weight of polyether groups based on the weight of the crosslinked cellulose ether, a solvent and a binder, wherein the crosslinked cellulose ether is an irreversibly crosslinked cellulose ether, and the detergent formulation is a detergent tablet.

[0009] The present invention provides a method for cleaning soiled fabric articles, comprising providing soiled fabric articles, providing a detergent formulation according to the present invention, providing wash water, providing rinse water, applying the wash water and the detergent formulation to the soiled fabric articles to provide cleaned fabric articles, and rinsing the cleaned fabric articles with rinse water. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Surprisingly, detergent tablet formulations of the present invention comprising crosslinked cellulose ethers containing 0.1-0.6 wt. % polyether groups based on the weight of the crosslinked cellulose ether exhibit significantly higher tensile properties compared to conventional binder / structurant components while at the same time exhibiting good dissolution properties with comparable first wash performance. Furthermore, the incorporation of crosslinked cellulose ethers containing 0.1-0.6 wt. % based on the weight of the crosslinked cellulose ether allows the use of water in place of propylene glycol traditionally used in detergent tablet formulations, significantly reducing the cost of the formulation and improving the environmental profile of the detergent tablet formulation while maintaining comparable first wash performance.

[0011] Unless otherwise indicated, ratios, percentages, parts, etc. are by weight. Weight percentages (or wt%) in a composition are percentages of dry weight, i.e., excluding any water that may be present in the composition. Percentages of monomer units in a polymer are percentages of solids weight, i.e., excluding any water present in a polymer emulsion.

[0012] As used herein, unless otherwise indicated, the terms "weight average molecular weight" and "Mw" are used interchangeably to refer to weight average molecular weight when measured in the conventional manner using gel permeation chromatography (GPC) and conventional standards such as polystyrene standards. The technique of GPC is discussed in detail in Modem Size Exclusion Chromatography, WW Yau, JJ Kirkland, DDBly; Wiley-Interscience, 1979, and A Guide to Materials Characterization and Chemical Analysis, JP Sibilia; VCH, 1988, p.81-84. Weight average molecular weight is reported herein in units of Daltons.

[0013] The term "phosphate-free" as used in this specification and the appended claims means a composition containing ≦1 wt.% (preferably, ≦0.5 wt.%, more preferably, ≦0.2 wt.%, even more preferably, ≦0.01 wt.%, even more preferably, ≦0.001 wt.%, and most preferably below the detection limit) phosphate (measured as elemental phosphorus).

[0014] As used herein and in the appended claims, the term "DS" refers to the number of alkyl-substituted OH groups per anhydroglucose unit in a cellulose ether, as determined by the Zeisel method.

[0015] The term "DS(methyl)" or "DS(M)" as used herein and in the appended claims means the number of methyl-substituted OH groups per anhydroglucose unit in a cellulose ether as determined by the Zeisel method.

[0016] The term "MS" as used herein and in the appended claims means the number of moles of etherifying reagent bound as an ether per mole of anhydroglucose unit as a hydroxyalkyl substituent in a cellulose ether, as determined by the Zeisel method.

[0017] The term "MS(hydroxyethyl)" or "MS(HE)" as used herein and in the appended claims means the number of moles of etherifying reagent bound as an ether per mole of anhydroglucose unit as a hydroxyethyl substituent in a cellulose ether as determined by the Zeisel method.

[0018] The term "MS(hydroxypropyl)" or "MS(HP)" as used herein and in the appended claims means the number of moles of etherifying reagent bound as an ether per mole of anhydroglucose unit as a hydroxypropyl substituent in a cellulose ether as determined by the Zeisel method.

[0019] The term "Zeisel method" refers to the Zeisel cleavage procedure for determining MS and DS. See G. Bartelmus and R. Ketterer, Zeitschrift für Analytische Chemie, Vol. 286 (1977, Springer, Berlin, DE), pages 161-190.

[0020] Preferably, the detergent formulation of the present invention is selected from liquid detergents, detergent tablets, detergent granules and detergent powders. More preferably, the detergent formulation of the present invention is selected from the group consisting of at least one of liquid laundry detergent formulations, liquid dishwashing detergent formulations, laundry or dishcare detergent tablets (or pearls), toilet tablets, granular laundry detergent formulations, granular dishwashing detergent formulations, powder laundry detergent formulations and powder dishwashing detergent formulations. Most preferably, the detergent formulation of the present invention is a laundry or dishcare (preferably laundry) detergent tablet.

[0021] Preferably, the detergent formulation (preferably, detergent tablet formulation) of the present invention comprises a detergent surfactant (preferably 5 to 65 wt. % (preferably 10 to 60 wt. %, more preferably 20 to 55 wt. %, most preferably 40 to 50 wt. %) of detergent surfactant, based on the weight of the detergent formulation) and a crosslinked cellulose ether containing 0.1 to 0.6 wt. % of polyether groups, based on the weight of the crosslinked cellulose ether (preferably 0.1 to 25 wt. % (preferably 0.5 to 20 wt. %, more preferably 1 to 17.5 wt. %, most preferably 5 to 15 wt. %) of crosslinked cellulose ether, based on the weight of the detergent formulation).

[0022] Preferably, the detergent formulation of the present invention comprises a detergent surfactant. More preferably, the detergent formulation of the present invention comprises 5 to 65% by weight (more preferably, 10 to 60% by weight, even more preferably, 20 to 55% by weight, most preferably, 40 to 50% by weight) of detergent surfactant based on the weight of the detergent formulation. Even more preferably, the detergent formulation of the present invention comprises 5 to 65% by weight (more preferably, 10 to 60% by weight, even more preferably, 20 to 55% by weight, most preferably, 40 to 50% by weight) of detergent surfactant based on the weight of the detergent formulation, the detergent surfactant being selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and mixtures thereof. Most preferably, the detergent formulation of the present invention comprises 5 to 65% by weight (more preferably, 10 to 60% by weight, even more preferably, 20 to 55% by weight, most preferably, 40 to 50% by weight) of detergent surfactant based on the weight of the detergent formulation, the detergent surfactant being selected from the group consisting of mixtures comprising anionic surfactants and nonionic surfactants.

[0023] Anionic surfactants include alkyl sulfates, alkylbenzene sulfates, alkylbenzene sulfonic acids, alkylbenzene sulfonates, alkyl polyethoxy sulfates, alkoxylated alcohols, paraffin sulfonic acids, paraffin sulfonates, olefin sulfonic acids, olefin sulfonates, alpha-sulfocarboxylates, esters of alpha-sulfocarboxylates, alkyl glyceryl ether sulfonic acids, alkyl glyceryl ether sulfonates, sulfates of fatty acids, sulfonates of fatty acids, sulfonates of fatty acid esters, alkyl phenols, alkyl phenol polyethoxy ether sulfates, 2-acryloxy-alkane-1-sulfonic acids, 2-acryloxy-alkane-1-sulfonates, beta-alkyloxyalkane sulfonic acids, beta-alkyloxyalkane sulfonates, amine oxides, and mixtures thereof. Preferred anionic surfactants include C 8~20 Alkylbenzene sulfate, C 8~20 Alkylbenzene sulfonic acid, C 8~20 Alkylbenzene sulfonates, Paraffin sulfonic acids, Paraffin sulfonates, Alpha-olefin sulfonic acids, Alpha-olefin sulfonates, Alkoxylated alcohols, C 8~20 Alkylphenols, amine oxides, sulfonates of fatty acids, sulfonates of fatty acid esters, C 8~20 alkyl polyethoxy sulfates, and mixtures thereof. More preferred anionic surfactants include C 10~13 Alkylbenzene sulfonic acid, C 10~13 Alkylbenzene sulfonate, C 10~13 Paraffin sulfonic acid, C 10~13 Paraffin Sulfonate, C 10~13 The most preferred anionic surfactants include C 10~13 Alkylbenzene sulfonates are included.

[0024] Nonionic surfactants include alkoxylates, polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers, hydroxy mixed ethers, fatty acid polyglycol esters and mixtures thereof. Preferred nonionic surfactants include alkoxylates. More preferred nonionic surfactants are according to formula I:

[0025] [ka] In the formula, w is an average of 5 to 40 (preferably 7 to 27, more preferably 8 to 20, and most preferably 7 to 12), and R 3 is hydrogen and linear or branched C 1~20 Alkyl groups (preferably hydrogen and linear or branched C 1~15 Alkyl groups, more preferably linear C 1~15 alkyl groups), R 4 is linear or branched C 1~20 Alkyl groups and linear or branched C 1~4 Hydroxyalkyl groups (preferably linear or branched C 1~15 Alkyl groups and linear or branched C 1~4 Hydroxyalkyl groups, more preferably linear C 1~15 Alkyl groups and linear or branched C 1~3 Hydroxyalkyl groups, most preferably linear C 1~15 alkyl groups), each R 5 are independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl, and 2-methyl-2-butyl (preferably hydrogen, methyl, and ethyl, more preferably hydrogen and methyl, and most preferably hydrogen), with the proviso that R 3 and R 4The total number of carbon atoms in R is 5 to 21 (preferably 6 to 20 carbon atoms, more preferably 7 to 18 carbon atoms, and most preferably 11 to 15 carbon atoms). Even more preferred nonionic surfactants are according to formula I, where w is an average of 8 to 16, and R 3 is hydrogen and linear C 1~15 alkyl groups; R 4 is linear or branched C 1~15 Alkyl groups and linear or branched C 1~4 hydroxyalkyl groups; R 5 is selected from the group consisting of hydrogen, methyl and ethyl groups, where R 3 and R 4 The total number of carbon atoms in R is 6 to 20. The most preferred nonionic surfactants are according to formula I, where w is an average of 7 to 12, and R 3 is hydrogen and linear C 1~15 alkyl groups; R 4 is a linear C 1~15 Alkyl groups and linear or branched C 1~3 hydroxyalkyl groups; R 5 is hydrogen, with the exception that R 3 and R 4 The total number of carbon atoms is 7 to 18.

[0026] Cationic surfactants include quaternary surface active compounds. Preferred cationic surfactants include quaternary surface active compounds having at least one of ammonium, sulfonium, phosphonium, iodonium, and arsonium groups. More preferred cationic surfactants include at least one of dialkyldimethylammonium chloride and alkyldimethylbenzylammonium chloride. Even more preferred cationic surfactants include C 16~18 Dialkyldimethylammonium chloride, C 8~18At least one of alkyl dimethyl benzyl ammonium chloride, ditallow dimethyl ammonium chloride, and ditallow dimethyl ammonium chloride is included. The most preferred cationic surfactant is ditallow dimethyl ammonium chloride.

[0027] Examples of amphoteric surfactants include betaines, amine oxides, alkylamidoalkylamines, alkyl-substituted amine oxides, acylated amino acids, derivatives of aliphatic quaternary ammonium compounds, and mixtures thereof. Preferred amphoteric surfactants include derivatives of aliphatic quaternary ammonium compounds. More preferred amphoteric surfactants include derivatives of aliphatic quaternary ammonium compounds having a long chain group with 8 to 18 carbon atoms. Even more preferred amphoteric surfactants include C 12~14 At least one of alkyl dimethylamine oxide, 3-(N,N-dimethyl-N-hexadecyl-ammonio)propane-1-sulfonate, and 3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate is included. The most preferred amphoteric surfactants include C 12~14 At least one of alkyl dimethyl amine oxides may be mentioned.

[0028] Preferably, the detergent formulation of the present invention comprises 0.1 to 25% by weight (preferably 0.5 to 20% by weight, more preferably 1 to 17.5% by weight, most preferably 5 to 15% by weight) of a crosslinked cellulose ether containing 0.1 to 0.6% by weight of a polyether group based on the weight of the crosslinked cellulose ether, based on the weight of the detergent formulation. More preferably, the detergent formulation of the present invention comprises 0.1 to 25% by weight (preferably 0.5 to 20% by weight, more preferably 1 to 17.5% by weight, most preferably 5 to 15% by weight) of a crosslinked cellulose ether containing 0.1 to 0.6% by weight of a polyether group based on the weight of the crosslinked cellulose ether, the crosslinked cellulose ether comprising a base cellulose ether and a crosslink, the crosslink containing a polyether group, the base cellulose ether being a mixed cellulose ether containing a hydroxyalkyl ether group and an alkyl ether group. Even more preferably, the detergent formulation of the present invention comprises 0.1 to 25 wt. % (more preferably 0.5 to 20 wt. %, more preferably 1 to 17.5 wt. %, most preferably 5 to 15 wt. %) of a crosslinked cellulose ether containing 0.1 to 0.6 wt. % polyether groups based on the weight of the crosslinked cellulose ether, the crosslinked cellulose ether comprising a base cellulose ether and a crosslink, the crosslink containing a polyether group, the base cellulose ether being selected from the group consisting of hydroxyethyl methylcellulose, hydroxypropyl methylcellulose, methyl hydroxyethyl hydroxypropyl cellulose, ethyl hydroxyethyl cellulose, and combinations thereof. Most preferably, the detergent formulation of the present invention comprises 0.1 to 25% by weight (preferably 0.5 to 20% by weight, more preferably 1 to 17.5% by weight, most preferably 5 to 15% by weight) of a crosslinked cellulose ether containing 0.1 to 0.6% by weight of polyether groups based on the weight of the crosslinked cellulose ether, the crosslinked cellulose ether comprising a base cellulose ether and a crosslink, the crosslink containing a polyether group and the base cellulose ether is hydroxyethyl methyl cellulose.

[0029] Preferably, the detergent formulation of the present invention comprises 0.1 to 25% by weight (preferably 0.5 to 20% by weight, more preferably 1 to 17.5% by weight, most preferably 5 to 15% by weight) of a crosslinked cellulose ether, based on the weight of the detergent formulation, containing 0.1 to 0.6% by weight of a polyether group based on the weight of the crosslinked cellulose ether, the crosslinked cellulose ether being an irreversibly crosslinked cellulose ether. More preferably, the detergent formulation of the present invention comprises 0.1 to 25% by weight (preferably 0.5 to 20% by weight, more preferably 1 to 17.5% by weight, most preferably 5 to 15% by weight) of a crosslinked cellulose ether, based on the weight of the detergent formulation, containing 0.1 to 0.6% by weight of a polyether group based on the weight of the crosslinked cellulose ether, the crosslinked cellulose ether comprising a base cellulose ether and a crosslink, the crosslink containing a polyether group, the base cellulose ether being a mixed cellulose ether containing a hydroxyalkyl ether group and an alkyl ether group, the crosslinked cellulose ether being either an irreversibly crosslinked cellulose ether. Even more preferably, the detergent formulation of the present invention comprises 0.1 to 25 wt. % (more preferably 0.5 to 20 wt. %, more preferably 1 to 17.5 wt. %, most preferably 5 to 15 wt. %) of a crosslinked cellulose ether containing 0.1 to 0.6 wt. % polyether groups based on the weight of the crosslinked cellulose ether, the crosslinked cellulose ether comprising a base cellulose ether and a crosslink, the crosslink containing a polyether group, the base cellulose ether being selected from the group consisting of hydroxyethyl methylcellulose, hydroxypropyl methylcellulose, methyl hydroxyethyl hydroxypropyl cellulose, ethyl hydroxyethyl cellulose, and combinations thereof, and the crosslinked cellulose ether being an irreversibly crosslinked cellulose ether.Most preferably, the detergent formulation of the present invention comprises 0.1 to 25 wt. % (preferably 0.5 to 20 wt. %, more preferably 1 to 17.5 wt. %, most preferably 5 to 15 wt. %) of a crosslinked cellulose ether containing 0.1 to 0.6 wt. % polyether groups based on the weight of the crosslinked cellulose ether, the crosslinked cellulose ether comprising a base cellulose ether and a crosslink, the crosslink containing a polyether group, the base cellulose ether being hydroxyethyl methylcellulose and the crosslinked cellulose ether being an irreversibly crosslinked cellulose ether.

[0030] Preferably, the crosslinked cellulose ether contains 0.1 to 0.6% by weight (preferably 0.12 to 0.6% by weight, more preferably 0.12 to 0.45% by weight, most preferably 0.12 to 0.29% by weight) of a polyether group based on the weight of the crosslinked cellulose ether. More preferably, the crosslinked cellulose ether contains 0.1 to 0.6% by weight (preferably 0.12 to 0.6% by weight, more preferably 0.12 to 0.45% by weight, most preferably 0.12 to 0.29% by weight) of a polyether group based on the weight of the crosslinked cellulose ether, and the polyether group is a polyoxyalkylene group having 2 to 100 (preferably 2 to 20, more preferably 3 to 15) oxyalkylene groups per crosslink. Most preferably, the crosslinked cellulose ether contains 0.1 to 0.6% by weight (preferably 0.12 to 0.6% by weight, more preferably 0.12 to 0.45% by weight, and most preferably 0.12 to 0.29% by weight) of a polyether group based on the weight of the crosslinked cellulose ether, and the polyether group is a polyoxypropylene group having 2 to 100 (preferably 2 to 20, more preferably 3 to 15) oxypropylene groups per crosslink.

[0031] Preferably, the crosslinked cellulose ether comprises a base cellulose ether having crosslinks, containing 0.1-0.6 wt.% polyether group based on the weight of the crosslinked cellulose ether. Preferably, the base cellulose ether is selected from hydroxyalkyl cellulose ethers, alkyl cellulose ethers, and combinations thereof. Examples of the base cellulose ether include, for example, methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, methyl ethyl hydroxyethyl cellulose, hydrophobically modified ethyl hydroxyethyl cellulose, hydrophobically modified hydroxyethyl cellulose, sulfoethyl methyl hydroxyethyl cellulose, sulfoethyl methyl hydroxypropyl cellulose, and sulfoethyl hydroxyethyl cellulose. Preferably, the base cellulose ether is a mixed cellulose ether containing both hydroxyalkyl ether groups and alkyl ether groups, such as alkyl hydroxyethyl cellulose and hydroxyalkyl methyl cellulose (e.g., hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, methyl hydroxyethyl hydroxypropyl cellulose, and ethyl hydroxyethyl cellulose).

[0032] Preferably, the base cellulose ether contains a hydroxyalkyl ether substitution. More preferably, the base cellulose ether has a degree of hydroxyethyl ether substitution MS(HE) or hydroxypropyl ether substitution MS(HP) of 1.5 to 4.5 (preferably, 2.0 to 3.0).

[0033] Preferably, the base cellulose ether contains a methyl ether substitution. More preferably, the base cellulose ether has a degree of methyl ether substitution DS(M) of 1.2 to 2.1 (preferably, 1.3 to 1.7, more preferably, 1.35 to 1.60).

[0034] Preferably, the base cellulose ether is a mixed cellulose ether containing hydroxyalkyl ether substitution and alkyl ether substitution, and more preferably, the base cellulose ether is a mixed cellulose ether having a hydroxyethyl ether substitution degree MS(HE) of 0.05 to 0.75 (preferably, 0.15 to 0.45, more preferably, 0.20 to 0.40) and a methyl ether substitution degree DS(M) of 1.2 to 2.1 (preferably, 1.3 to 1.7, more preferably, 1.35 to 1.60).

[0035] Preferably, the base cellulose ether is a mixed cellulose ether containing hydroxyalkyl ether substitution and alkyl ether substitution. More preferably, the base cellulose ether is a mixed cellulose ether having a hydroxypropyl ether substitution degree MS (HP) of 0.1 to 1.5 (preferably, 0.2 to 1.2) and a methyl ether substitution degree DS (M) of 1.2 to 2.1 (preferably, 1.3 to 2.0).

[0036] Preferably, the crosslinked cellulose ether comprises a base cellulose ether having crosslinks containing 0.1 to 0.6 weight percent polyether groups based on the weight of the crosslinked cellulose ether, the base cellulose ether being a hydroxyethyl methylcellulose and the crosslinks being polyoxypropylene dioxyethylene ether crosslinks, for example, those produced as the reaction product of hydroxyethyl methylcellulose with polypropylene glycol (PPG) glycidyl ether.

[0037] The crosslinking agent used to crosslink the base cellulose ether to form the crosslinked cellulose ether may include a compound having a polyoxyalkylene or polyalkylene glycol group, two or more (preferably two) crosslinking groups such as halogen, glycidyl or epoxy groups, and an ethylenically unsaturated group (e.g., vinyl group) that forms an ether bond with the base cellulose ether to form the crosslinked cellulose ether. Preferably, the crosslinking agent is selected from the group consisting of 1,2-dichloro(poly)alkoxyether, dichloropolyoxyethylene, diglycidyl polyalkoxyether, diglycidyl phosphonate, and divinyl polyoxyalkylene containing sulfone group. Crosslinking agents having two different types of functional groups can be used. Examples include diglycidyl polyoxypropylene and glycidyl (poly)oxyalkyl methacrylate. Preferably, the crosslinking agent contains 2 to 100 (preferably 2 to 20, more preferably 3 to 15) oxyalkylene groups per molecule.

[0038] Preferably, the amount of crosslinking agent contained in the crosslinked cellulose ether is in the range of 0.0001 to 0.05 equivalents (preferably, 0.0005 to 0.01 equivalents, more preferably, 0.001 to 0.005 equivalents), where 1 "equivalent" represents the molar ratio of the crosslinking agent to the number of moles of anhydroglucose units (AGU) in the base cellulose ether.

[0039] Preferably, crosslinked cellulose ether is irreversibly crosslinked cellulose ether.That is, the crosslink in crosslinked cellulose ether does not decompose during intended use of crosslinked cellulose ether under normal conditions.In contrast, reversible crosslink decomposes during intended use of crosslinked cellulose ether under normal conditions.An example of reversible crosslink in the cellulose ether intended for use in detergent formulations is that which is produced using aldehyde-based crosslinking agent (e.g. glyoxal), and this crosslink decomposes when crosslinked material dissolves in water.

[0040] Preferably, the detergent formulations of the present invention comprise <0.5 wt.% (preferably <0.01 wt.%, more preferably <0.001 wt.%, even more preferably <0.0001 wt.%, most preferably below the limit of detection) crosslinked carboxymethylcellulose based on the weight of the detergent formulation.

[0041] Preferably, the detergent formulation of the present invention further comprises at least one optional ingredient selected from the group consisting of solvents, binders, bleaches, bleach activators, stabilizers, foam control agents, enzymes, optical brighteners, fillers, processing aids and fragrances.

[0042] Preferably, the detergent formulation of the present invention optionally further comprises a solvent. More preferably, the detergent formulation of the present invention optionally further comprises 0-45 wt. % (preferably 0.1-40 wt. %, more preferably 5-35 wt. %, most preferably 15-30 wt. %) of a solvent based on the weight of the detergent formulation. Even more preferably, the detergent formulation of the present invention optionally further comprises 0-45 wt. % (preferably 0.1-40 wt. %, more preferably 5-35 wt. %, most preferably 15-30 wt. %) of a solvent based on the weight of the detergent formulation, the solvent being selected from the group consisting of water, an organic solvent, and mixtures thereof. Even more preferably, the detergent formulation of the present invention optionally further comprises 0-45 wt. % (preferably 0.1-40 wt. %, more preferably 5-35 wt. %, most preferably 15-30 wt. %) of a solvent based on the weight of the detergent formulation, the solvent being selected from the group consisting of water, an organic solvent, and mixtures thereof, the organic solvent being an aliphatic alcohol (e.g. C 1~6 Alkanol, C 1~6alkyl diols), monoalkylene glycol ethers (e.g., ethylene glycol propyl ether, ethylene glycol n-butyl ether, ethylene glycol t-butyl ether, propylene glycol propyl ether, propylene glycol n-butyl ether, propylene glycol t-butyl ether, propylene glycol methyl ether acetate, propylene glycol diacetate), polyalkylene glycol ethers (e.g., diethylene glycol ethyl ether, diethylene glycol propyl ether, diethylene glycol n-butyl ether, diethylene glycol t-butyl ether, diethylene glycol hexyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, dipropylene glycol n-butyl ether, dipropylene glycol t-butyl ether, dipropylene glycol phenyl ether, dipropylene glycol methyl ether acetate, tripropylene glycol methyl ether, tripropylene glycol ethyl ether, tripropylene glycol propyl ether, tripropylene glycol n-butyl ether, tripropylene glycol t-butyl ether), and mixtures thereof. Most preferably, the detergent formulation of the present invention optionally further comprises 0 to 45 wt. % (preferably 0.1 to 40 wt. %, more preferably 5 to 35 wt. %, most preferably 15 to 30 wt. %) of a solvent, based on the weight of the detergent formulation, selected from (i) a mixture of water and dipropylene glycol n-butyl ether, and (ii) a mixture of propylene glycol and dipropylene glycol n-butyl ether.

[0043] Preferably, the detergent formulation of the present invention optionally further comprises a binder. More preferably, the detergent formulation of the present invention optionally further comprises 0-30 wt. % (preferably 0.1-30 wt. %, more preferably 5-25 wt. %, most preferably 10-20 wt. %) of a binder based on the weight of the detergent formulation. Even more preferably, the detergent formulation of the present invention optionally further comprises 0-30 wt. % (preferably 0.1-30 wt. %, more preferably 5-25 wt. %, most preferably 10-20 wt. %) of a binder based on the weight of the detergent formulation, the binder being a C 2 hydroxypropyl ether having 5-100 moles of ethylene oxide per mole of alcohol. 10~20 Alcohol ethoxylates (preferably C containing 20 to 100 moles of ethylene oxide per mole of alcohol) 15~20 a primary alcohol ethoxylate), polyvinylpyrrolidone having an average molecular weight of 12,000 to 700,000 daltons, polypropylene glycol having an average molecular weight of 600 to 5,000,000 daltons (preferably 1,000 to 400,000 daltons, more preferably 1,000 to 10,000 daltons), polyethylene glycol having an average molecular weight of 600 to 5,000,000 daltons (preferably 1,000 to 400,000 daltons, more preferably 1,000 to 10,000 daltons), a copolymer of maleic anhydride and ethylene, methyl vinyl ether, or methacrylic acid, wherein the maleic anhydride comprises at least 20 mole percent of the copolymer, C 10~20 Mono- and diglycerol ethers, C 10~20The surfactant is selected from the group consisting of fatty acids, cellulose derivatives such as methylcellulose, carboxymethylcellulose, and hydroxyethylcellulose, homo- and copolymeric polycarboxylic acids and their salts, and mixtures thereof. Most preferably, the detergent formulation of the present invention optionally further comprises 0-30% by weight (preferably 0.1-30% by weight, more preferably 5-25% by weight, most preferably 10-20% by weight) of a binder based on the weight of the detergent formulation, the binder being a polyethylene glycol having an average molecular weight of 600-5,000,000 Daltons (preferably 1,000-400,000 Daltons, more preferably 1,000-10,000 Daltons).

[0044] Preferably, the detergent formulation of the present invention further comprises 0-10% by weight of a bleaching agent, based on the weight of the detergent formulation. Preferred bleaching agents include, for example, sodium perborate and sodium percarbonate.

[0045] Preferably, the detergent formulation of the present invention further comprises 0-10% by weight of a bleach activator, based on the weight of the detergent formulation. Preferred bleach activators include, for example, tetraacetyl ethylene diamine (TAED) and sodium nonanoyloxybenzene sulfonate (NOBS).

[0046] Preferably, the detergent formulation of the present invention further comprises 0-1 wt. % of a stabilizer, based on the weight of the detergent formulation. Preferred stabilizers include, for example, phosphonates.

[0047] Preferably, the detergent formulation of the present invention further comprises 0 to 2 wt. % (preferably 0.01 to 2 wt. %) of a fragrance, based on the weight of the detergent formulation.

[0048] Preferably, the detergent formulation of the present invention further comprises 0-2 wt. % (preferably 0.1-2 wt. %) of an enzyme based on the weight of the detergent formulation. More preferably, the detergent formulation of the present invention further comprises 0-2 wt. % (preferably 0.1-2 wt. %) of an enzyme based on the weight of the detergent formulation, the enzyme being selected from the group consisting of protease, cellulase, amylase, mannanase, lipase, and mixtures thereof. Most preferably, the detergent formulation of the present invention further comprises 0-2 wt. % (preferably 0.1-2 wt. %) of an enzyme based on the weight of the detergent formulation, the enzyme comprising a mixture of protease, amylase, and mannanase.

[0049] Preferably, the detergent formulation of the present invention further comprises 0 to 0.3 wt. % of an optical brightener, based on the weight of the detergent formulation. Preferred optical brighteners include, for example, fluorescent whitening agents.

[0050] Preferably, the detergent formulation of the present invention further comprises 0-74.09 wt. % (preferably, 0.1-74.09 wt. %, more preferably, 5-70 wt. %) of a filler based on the weight of the detergent formulation. More preferably, the detergent formulation of the present invention further comprises 0-74.09 wt. % (preferably, 0.1-74.09 wt. %, more preferably, 5-70 wt. %) of a filler based on the weight of the detergent formulation, the filler comprising at least one of sodium sulfate, sodium chloride, calcite, and dolomite. Most preferably, the detergent formulation of the present invention further comprises 0-74.09 wt. % (preferably, 0.1-74.09 wt. %, more preferably, 5-70 wt. %) of a filler based on the weight of the detergent formulation, the filler being selected from the group consisting of sodium sulfate, sodium chloride, calcite, dolomite, and mixtures thereof.

[0051] Preferably, the detergent formulation of the present invention further comprises a solvent and a binder, and the detergent formulation is a detergent tablet. More preferably, the detergent formulation of the present invention further comprises a solvent, a binder, a fragrance and an enzyme, and the detergent formulation is a detergent tablet. Most preferably, the detergent formulation of the present invention further comprises 0.1 to 40 wt % (preferably 5 to 35 wt %, more preferably 15 to 30 wt %) of a solvent based on the weight of the detergent formulation, 0.1 to 30 wt % (preferably 5 to 25 wt %, more preferably 10 to 20 wt %) of a binder based on the weight of the detergent formulation, 0.01 to 2 wt % of a fragrance based on the weight of the detergent formulation, and 0.05 to 2 wt % of an enzyme based on the weight of the detergent formulation, and the detergent formulation is a detergent tablet.

[0052] Preferably, the method of washing soiled fabric articles of the present invention comprises providing a soiled fabric article (preferably, the soiled fabric article comprises cotton, more preferably, the soiled fabric article is selected from cotton and polyester-cotton blends), providing wash water, providing rinse water, providing a detergent formulation of the present invention, applying the wash water and the detergent formulation to the soiled fabric article to provide a washed fabric article, and then rinsing the washed fabric article with rinse water. Preferably, the method of washing soiled fabric articles of the present invention comprises providing a soiled fabric article (preferably, the soiled fabric article comprises cotton, more preferably, the soiled fabric article is selected from cotton and polyester-cotton blends), providing wash water, providing rinse water, providing a detergent formulation of the present invention, applying the wash water and the detergent formulation to the soiled fabric article to provide a washed fabric article, and then rinsing the washed fabric article with rinse water, and the detergent formulation is a detergent tablet.

[0053] Preferably, in the method of cleaning soiled fabric articles of the present invention, the soiled fabric articles are treated with the detergent formulation and wash water using well-known techniques. Preferably, the detergent formulation is mixed with the wash water in a weight ratio of detergent formulation to wash water of 1:100 to 1:1,000.

[0054] Some embodiments of the present invention will now be described in detail in the following examples.

[0055] Synthesis 1: Crosslinked cellulose ether The crosslinker used in Synthesis 1 was a linear poly(propylene glycol) diglycidyl ether made from polypropylene glycol (PPG) having a molecular weight of about 400 Daltons and having the formula:

[0056] [ka] where n is 5.7 to 6.7 (EPILOX™ M985 poly(propylene glycol) diglycidyl ether crosslinker available from Leuna-Harze GmbH, Leuna, DE).

[0057] Milled cellulose floc (1.5 mol) was added to a 5 L autoclave. After purging the autoclave with nitrogen gas, the contents of the autoclave were heated to 40° C. Dimethyl ether (DME, 4.7 mol / mol of anhydroglucose units (AGU)) and methyl chloride (MCl, 3.2 mol / mol AGU) were then injected into the autoclave. Caustic soda (NaOH, 50% strength by weight in water, 1.9 mol NaOH / mol AGU) was added to the autoclave in three portions over a period of 2 minutes at a temperature of 40° C. The reaction mixture was maintained at 40° C. for 30 minutes. Ethylene oxide (0.45 mol / mol AGU) was then added and the reaction mixture was maintained at 40° C. for 10 minutes. The crosslinker (EPILOX™ M985 crosslinker, 0.0025 mol / mol AGU) was dissolved in 20 mL of isopropanol and added to the contents of the autoclave in six portions at 30 second intervals. The contents of the autoclave were then heated to 80° C. for 40 minutes. At 80° C., a water-soluble monovalent copper ligand (MCL2, 1.3 mol / mol AGU) was rapidly injected into the autoclave. NaOH (0.67 mol / mol AGU) was then added in seven portions over a period of 30 minutes, followed by a cook-off period of 70 minutes at 80° C. Following this, the product crosslinked cellulose ether was washed with hot (>95° C.) water, neutralized with formic acid, granulated, dried, and ground.

[0058] Comparative Example C1 and Examples 1-2: Detergent Tablets Detergent tablets having the compositions shown in Table 1 were prepared for each of Comparative Example C1 and Examples 1-2. Polyethylene glycol was added to a vessel heated and set at 80°C with stirring (4-blade propeller at 200 rpm). Solvent (propylene glycol, demineralized water, glycol ether solvent) was then added to the vessel contents with continued stirring. Surfactants (secondary alcohol ethoxylate, nonionic surfactant, C 10~13The container contents were then mixed with sodium alkylbenzene sulfonate (Na 2 O 4 ) and stirred until homogenous. ...

[0059] [Table 1]

[0060] Primary cleaning performance test The primary wash performance of the laundry tablets of Comparative Example C1 and Examples 1-2 was evaluated on a Miele W1614 with the program set to Cotton / 40°C / 1,000 rpm (124 min). Each load required 10-11 liters of wash water with 25° French hardness and 23 TAC. The soil used was 4 SBL 2004. Each load of laundry contained 6 pillowcases, 5 huckaback towels, and 1 bed sheet. Each load was pre-washed (3 cycles) before testing. The stained fabrics (11 stains - sebum with carbon black on cotton, sebum with carbon black on polyester / cotton blend, grass / mud on polyester / cotton blend, dirty motor oil, tomato puree, chocolate drink on cotton, standard clay on cotton, red china clay on cotton, dried ink on cotton, spaghetti sauce, and lard) (3 stains - grass, balsamic salad dressing, and potato starch) were sewn onto the monitor placed with the laundry load. Both stained monitors were dried overnight on a drying line. The stains were measured with a MACH5+ instrument (L, a, and b). The results are shown in Table 2, where ΔE * follows the formula: ΔE * = ΔE aw -ΔE bw In the formula, ΔEaw is measured from the fabric after washing, and ΔE bw is measured from the fabric before washing. The higher the ΔE * corresponds to better primary cleaning performance.

[0061] [Table 2]

[0062] hardness The indentation hardness of the detergent tablet materials prepared according to Comparative Example C1 and Examples 1-2 was measured using a Shore Instrument and Manufacturing Co. durometer according to ASTM D 2240. The average Shore A hardness of five separate measurements per detergent tablet material is shown in Table 3.

[0063] [Table 3]

Claims

1. 1. A detergent formulation comprising: A detergent surfactant; a crosslinked cellulose ether, the crosslinked cellulose ether containing 0.1 to 0.6 weight percent polyether groups based on the weight of the crosslinked cellulose ether.

2. 2. The detergent formulation of claim 1, wherein the crosslinked cellulose ether is an irreversibly crosslinked cellulose ether.

3. 3. The detergent formulation of claim 2, wherein the detergent formulation is selected from the group consisting of liquid detergents, detergent tablets and powder detergents.

4. A solvent; and a binder, 3. The detergent formulation of claim 2, wherein the detergent formulation is a detergent tablet.

5. 5. The detergent formulation of claim 4, wherein the polyether groups in the irreversibly crosslinked cellulose ether are polyoxyalkylene groups having from 2 to 100 oxyalkylene groups.

6. 6. The detergent formulation of claim 5, wherein the polyoxyalkylene group is selected from the group consisting of polyoxyethylene, polyoxypropylene, and combinations thereof.

7. 7. The detergent formulation of claim 6, wherein the irreversibly crosslinked cellulose ether comprises a base cellulose ether and a crosslink, the crosslink containing the polyether group, and the base cellulose ether containing a hydroxyalkyl ether group and an alkyl ether group.

8. 8. The detergent formulation of claim 7, wherein the base cellulose ether is selected from the group consisting of hydroxyethyl methylcellulose, hydroxypropyl methylcellulose, methyl hydroxyethyl hydroxypropyl cellulose, ethyl hydroxyethyl cellulose, and combinations thereof.

9. 9. The detergent formulation of claim 8 further comprising a fragrance and an enzyme.

10. 11. A method for cleaning soiled fabric articles, comprising: providing a soiled fabric article; providing the detergent formulation of claim 1; providing wash water; providing rinse water; applying the wash water and the detergent formulation to the soiled fabric article to provide a cleaned fabric article; and rinsing the cleaned fabric article with the rinse water.