cleaning bar

Abstract

A cleaning bar is provided that includes a cleaning surfactant, water, and a crosslinked cellulose ether that contains 0.1 to 0.6 weight percent polyether groups, based on the weight of the crosslinked cellulose ether, wherein the cleaning bar is a solid.

Description

[Technical Field]

[0001] The present invention relates to a cleaning bar, specifically a cleaning bar comprising a cleaning surfactant, water, and a crosslinked cellulose containing 0.1 to 0.6 wt. % polyether groups, based on the weight of the crosslinked cellulose ether, wherein the cleaning bar is solid.

[0002] Cleaning bars remain popular with consumers for cleaning laundry, hard surfaces, skin, and hair.

[0003] Finished milled cleaning bars are traditionally prepared from non-soap surfactant or soap noodles having a total fatty matter (TFM) content of over 70% by weight, 10-14% by weight water, and other ingredients (e.g., titanium dioxide, surfactants, and fragrances). Currently, milled bars have a typical water content of about 8-15% by weight, while non-milled bars have a water content of 20-25% by weight.

[0004] Cleaning bars of various compositions are known. Conventional cleaning bars are formulated with various additives to provide the inherent benefits of cleaning burps. Conventional cleaning bars contain at least one surfactant (e.g., monovalent sodium, potassium, ammonium, and alkanolammonium salts of monocarboxylic fatty acids) and, optionally, one or more adjuvants, such as moisturizing creams, humectants, antimicrobial agents, water, fillers, polymers, processing aids, dyes, and fragrances, to enhance the cleaning and conditioning properties of the cleaning bar.

[0005] It is desirable to create cleaning bars with high water content for ease of formulation and process efficiency. Nevertheless, maintaining the high water content of the formulation after processing to form the finished cleaning bar has been difficult.

[0006] Therefore, there remains a need for new cleaning bar formulations that allow for high water content in the finished cleaning bar while retaining other desirable cleaning bar properties such as wear rate.

[0007] The present invention provides a cleaning bar comprising 5 to <78.99 wt. % cleaning surfactant, based on the weight of the cleaning bar; >21 to 50 wt. % water, based on the weight of the cleaning bar; 0.01 to 5 wt. % crosslinked cellulose ether, based on the weight of the cleaning bar, containing 0.1 to 0.6 wt. % polyether groups, based on the weight of the crosslinked cellulose ether; 0 to 3 wt. % processing aid, based on the weight of the cleaning bar; 0 to 3 wt. % optional ingredient selected from the group consisting of fragrance, colorant / dye, or combinations thereof, based on the weight of the cleaning bar; and 0 to 15 wt. % filler, based on the weight of the cleaning bar, wherein the cleaning bar is solid.

[0008] The present invention provides a cleaning bar comprising 5 to <78.99 wt. % cleaning surfactant, based on the weight of the cleaning bar; >21 to 50 wt. % water, based on the weight of the cleaning bar; 0.01 to 5 wt. % irreversibly crosslinked cellulose ether, based on the weight of the cleaning bar, containing 0.1 to 0.6 wt. % polyether groups, based on the weight of the irreversibly crosslinked cellulose ether; 0 to 3 wt. % processing aid, based on the weight of the cleaning bar; 0 to 3 wt. % optional ingredient selected from the group consisting of fragrance, colorant / dye, or combinations thereof, based on the weight of the cleaning bar; and 0 to 15 wt. % filler, based on the weight of the cleaning bar, wherein the cleaning bar is solid.

[0009] The present invention provides a method of making a cleaning bar, comprising: providing a cleaning surfactant; providing water; providing a crosslinked cellulose ether containing 0.1 to 0.6 weight percent polyether groups, based on the weight of the crosslinked cellulose ether; mixing the cleaning surfactant, the crosslinked cellulose ether, and the water to form a combination; milling the combination; extruding the milled combination; and die-cutting the extruded material to provide a cleaning bar.

[0010] The present invention provides a method of making a cleaning bar comprising: providing a cleaning surfactant; providing water; providing a crosslinked cellulose ether containing 0.1 to 0.6 weight percent polyether groups, based on the weight of the crosslinked cellulose ether; providing a fragrance; and providing a processing aid; the method comprising: mixing the cleaning surfactant, the crosslinked cellulose ether, the fragrance, the processing aid, and the water to form a combination; milling the combination; extruding the milled combination; and die-cutting the extruded material to provide a cleaning bar. DETAILED DESCRIPTION OF THE INVENTION

[0011] Surprisingly, it has been found that cleaning bars containing crosslinked cellulose ethers containing polyether groups in the crosslinker (preferably cellulose ethers containing alkyl ether groups and hydroxyalkyl ether groups) facilitate high water content (>21 wt%) in the finished cleaning bar while maintaining acceptable abrasion resistance.

[0012] Unless otherwise indicated, ratios, percentages, parts, etc. are by weight.

[0013] As used herein and in the appended claims, the term "DS" means the number of alkyl-substituted OH groups per anhydroglucose unit in a cellulose ether as determined by the Zeisel method.

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

[0015] As used herein and in the appended claims, the term "MS" 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.

[0016] As used herein and in the appended claims, the term "MS(hydroxyethyl)" or "MS(HE)" refers to 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.

[0017] As used herein and in the appended claims, the term "MS(hydroxypropyl)" or "MS(HP)" refers to 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.

[0018] 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.

[0019] Preferably, the cleaning bar of the present invention is selected from the group consisting of a laundry detergent bar, a personal care cleansing bar, a shampoo bar, a hard surface cleaning bar, a toilet block, and a dishwashing bar. More preferably, the cleaning bar of the present invention is selected from the group consisting of a laundry detergent bar, a personal care cleansing bar, and a shampoo bar. Most preferably, the cleaning bar of the present invention is a laundry detergent bar.

[0020] Preferably, the cleaning bar of the present invention comprises 5 to <78.99 wt. % (preferably 7 to 70 wt. %, more preferably 8 to 60 wt. %, and most preferably 10 to 55 wt. %) of cleaning surfactant, based on the weight of the cleaning bar; >21 to 50 wt. % (preferably >23 to 45 wt. %, more preferably 25 to 40 wt. %, and most preferably 30 to 37.5 wt. %) of water, based on the weight of the cleaning bar; and 0.01 to 5 wt. % (preferably 0.05 to 3 wt. %, more preferably 0.1 to 2.5 wt. %, even more preferably 0.15 to 2 wt. %, and most preferably 0.2 to 1.5 wt. %) of crosslinked cellulose ether, based on the weight of the cleaning bar, containing 0.1 to 0.6 wt. % of polyether groups, based on the weight of the crosslinked cellulose ether. and 0 to 3 wt. % (preferably 0.01 to 3 wt. %) of a processing aid, based on the weight of the cleaning bar; 0 to 3 wt. % (preferably 0.01 to 3 wt. %) of an optional ingredient selected from the group consisting of a fragrance, a colorant / dye, or a combination thereof, based on the weight of the cleaning bar; and 0 to 70 wt. % (preferably 2 to 65 wt. %, more preferably 2.5 to 60 wt. %, and most preferably 3 to 55 wt. %) of a filler, based on the weight of the cleaning bar, wherein the cleaning bar is solid (i.e., the cleaning bar does not appreciably change shape when placed on a rigid surface and left undisturbed at room temperature of 22°C and a pressure of 101.4 kPa for 24 hours).

[0021] Preferably, the cleaning bar of the present invention comprises 5 to <78.99 wt. % (preferably 7 to 70 wt. %, more preferably 8 to 60 wt. %, and most preferably 10 to 55 wt. %) of a cleaning surfactant based on the weight of the cleaning bar. More preferably, the cleaning bar of the present invention comprises 5 to <78.99 wt. % (preferably 7 to 70 wt. %, more preferably 8 to 60 wt. %, and most preferably 10 to 55 wt. %) of a cleaning surfactant based on the weight of the cleaning bar, the cleaning surfactant being selected from the group consisting of non-soap surfactants, soaps, and mixtures thereof. Most preferably, the cleaning bar of the present invention comprises 35 to <78.99 wt. % (preferably 37 to 70 wt. %, more preferably 40 to 60 wt. %, and most preferably 45 to 55 wt. %) of a cleaning surfactant based on the weight of the cleaning bar, the cleaning surfactant comprising a soap.

[0022] Preferably, the cleaning bar of the present invention contains 5 to 30% by weight (preferably 7 to 25% by weight, more preferably 8 to 20% by weight, most preferably 10 to 15% by weight) of a non-soap surfactant based on the weight of the cleaning bar. More preferably, the cleaning bar of the present invention contains 5 to 30% by weight (preferably 7 to 25% by weight, more preferably 8 to 20% by weight, most preferably 10 to 15% by weight) of a non-soap surfactant based on the weight of the cleaning bar. The non-soap surfactant may be selected from the group consisting of alkyl sulfonic acids, alkyl sulfates, alkyl sulfonates, alkyl sulfosuccinates, alkyl benzene sulfonic acids, alkyl benzene sulfates, alkyl benzene sulfonates, alkyl ether sulfonic acids, alkyl ether sulfates, alkyl ether sulfonates, paraffin sulfonic acids, paraffin sulfates, paraffin sulfonates, olefin sulfonic acids, olefins ... Preferably, the surfactant is selected from the group consisting of alkyl glyceryl ether sulfates, olefin sulfonates, alpha-sulfocarboxylates, esters of alpha-sulfocarboxylates, alkyl glyceryl ether sulfonates, alkyl glyceryl ether sulfates, alkyl glyceryl ether sulfonates, fatty acid sulfates, fatty acid sulfonates, sulfonates of fatty acid esters, alkylphenol polyethoxy ether sulfates, 2-acryloxy-alkane-1-sulfonic acids, 2-acryloxy-alkane-1-sulfonates, beta-alkyloxyalkane sulfonic acids, beta-alkyloxyalkane sulfonates, salts thereof, and mixtures thereof. Even more preferably, the cleaning bar of the present invention comprises 5 to 30 wt. % (preferably, 7 to 25 wt. %, more preferably, 8 to 20 wt. %, and most preferably, 10 to 15 wt. %) of a non-soap surfactant, based on the weight of the cleaning bar, the non-soap surfactant being selected from the group consisting of C 8~20 Alkylbenzene sulfonic acid, C 8~20 Alkylbenzene sulfate, C 8~20 Alkylbenzene sulfonate, C 8~20 Alkyl ether sulfonic acid, C 8~20 Alkyl ether sulfate, C 8~20Preferably, the cleaning bar comprises 5 to <30 wt. % (preferably 7 to 25 wt. %, more preferably 8 to 20 wt. %, and most preferably 10 to 15 wt. %) of a non-soap surfactant, based on the weight of the cleaning bar, and the non-soap surfactant is selected from the group consisting of alkyl ether sulfonates, paraffin sulfonic acids, paraffin sulfates, paraffin sulfonates, alpha-olefin sulfonic acids, alpha-olefin sulfates, alpha-olefin sulfonates, sulfonates of fatty acids, sulfonates of fatty acid esters, salts thereof, and mixtures thereof. Even more preferably, the cleaning bar comprises 5 to <30 wt. % (preferably 7 to 25 wt. %, more preferably 8 to 20 wt. %, and most preferably 10 to 15 wt. %) of a non-soap surfactant, based on the weight of the cleaning bar, the non-soap surfactant being selected from the group consisting of C 10~16 Alkylbenzene sulfonic acid, C 10~16 Alkylbenzene sulfonate, C 10~16 Alkylpolyethoxysulfonic acid, C 10~16 Alkyl polyethoxy sulfate, C 10~16 Even more preferably, the cleaning bar of the present invention comprises 5 to 30 wt. % (preferably, 7 to 25 wt. %, more preferably, 8 to 20 wt. %, and most preferably, 10 to 15 wt. %) of a non-soap surfactant, based on the weight of the cleaning bar, the non-soap surfactant being selected from the group consisting of alkyl polyethoxy sulfonates, salts thereof, and mixtures thereof. 11~14 Alkylbenzene sulfonic acid, C 11~14 Alkylbenzene sulfonate, C 11~14 Alkylpolyethoxysulfonic acid, C 11~14 Alkyl polyethoxy sulfate, C 11~14 Most preferably, the cleaning bar of the present invention comprises 5 to 30 wt. % (preferably, 7 to 25 wt. %, more preferably, 8 to 20 wt. %, and most preferably, 10 to 15 wt. %) of a non-soap surfactant based on the weight of the cleaning bar, the non-soap surfactant being selected from the group consisting of alkyl polyethoxy sulfonates, salts thereof, and mixtures thereof. 11~14 alkylbenzene sulfonic acid (preferably C 11~14 alkylbenzene sulfonic acid).

[0023] Preferably, the cleaning bar of the present invention comprises 35 to <78.99 wt. % (preferably 37 to 70 wt. %, more preferably 40 to 60 wt. %, and most preferably 45 to 55 wt. %) of a cleaning surfactant based on the weight of the cleaning bar. More preferably, the cleaning bar of the present invention comprises 35 to <78.99 wt. % (preferably 37 to 70 wt. %, more preferably 40 to 60 wt. %, and most preferably 45 to 55 wt. %) of a cleaning surfactant based on the weight of the cleaning bar, the cleaning surfactant being a soap selected from the group consisting of monovalent salts of monocarboxylic fatty acids having a counterion selected from the group consisting of sodium, potassium, ammonium, and alkanolammonium ions. Even more preferably, the cleaning bar of the present invention comprises 35 to <78.99 wt. % (preferably 37 to 70 wt. %, more preferably 40 to 60 wt. %, and most preferably 45 to 55 wt. %) of a cleaning surfactant, based on the weight of the cleaning bar, wherein the cleaning surfactant is a soap, the soap being an alkali (preferably sodium) salt of a fatty acid from at least one of animal fats and vegetable oils. Even more preferably, the cleaning bar composition of the present invention comprises 35 to <78.99 wt. % (preferably 37 to 70 wt. %, more preferably 40 to 60 wt. %, and most preferably 45 to 55 wt. %) of a cleaning surfactant, based on the weight of the cleaning bar, wherein the cleaning surfactant is a soap, the soap being an alkali (preferably sodium) salt of a fatty acid from at least one of palm oil, palm kernel oil, castor oil, rice bran oil, sunflower oil, coconut oil, soybean oil, peanut oil, tallow, lard, fish oil, and blends thereof.Even more preferably, the cleaning bar of the present invention comprises 35 to <78.99 wt. % (preferably 37 to 70 wt. %, more preferably 40 to 60 wt. %, and most preferably 45 to 55 wt. %) of a cleaning surfactant based on the weight of the cleaning bar, wherein the cleaning surfactant is a soap, and the soap is an alkali (preferably sodium) salt of a fatty acid from a 40:60 to 97:3 blend of oils and fats (preferably the blend of oils and fats is selected from a blend of palm and palm kernel oils and a blend of palm and coconut kernel oils). Most preferably, the cleaning bars of the present invention comprise 35 to <78.99 wt. % (preferably 37 to 70 wt. %, more preferably 40 to 60 wt. %, and most preferably 45 to 55 wt. %) of a cleaning surfactant based on the weight of the cleaning bar, the cleaning surfactant being a soap, the soap being an alkali (preferably sodium) salt of a fatty acid from a 50:50, 60:40, 70:30, 80:20, or 90:10 (preferably 80:20) blend of palm oil and palm kernel oil.

[0024] Preferably, the cleaning bar of the present invention comprises >21 to 50 wt. % (preferably >23 to 45 wt. %, more preferably 25 to 40 wt. %, and most preferably 30 to 37.5 wt. %) water based on the weight of the cleaning bar. More preferably, the cleaning bar of the present invention comprises >21 to 50 wt. % (preferably >23 to 45 wt. %, more preferably 25 to 40 wt. %, and most preferably 30 to 37.5 wt. %) water based on the weight of the cleaning bar, the water being at least one of distilled water and deionized water. Most preferably, the cleaning bar of the present invention comprises >21 to 50 wt. % (preferably >23 to 45 wt. %, more preferably 25 to 40 wt. %, and most preferably 30 to 37.5 wt. %) water based on the weight of the cleaning bar, the water being deionized water.

[0025] Preferably, the cleaning bar of the present invention contains 0.01 to 5 wt. % (preferably 0.05 to 3 wt. %, more preferably 0.1 to 2.5 wt. %, even more preferably 0.15 to 2 wt. %, and most preferably 0.2 to 1.5 wt. %) of a crosslinked cellulose ether, based on the weight of the cleaning bar, which contains 0.1 to 0.6 wt. % of a polyether group, based on the weight of the crosslinked cellulose ether. More preferably, the cleaning bar of the present invention contains 0.01 to 5 wt. % (preferably 0.05 to 3 wt. %, more preferably 0.1 to 2.5 wt. %, even more preferably 0.15 to 2 wt. %, and most preferably 0.2 to 1.5 wt. %) of a crosslinked cellulose ether, based on the weight of the cleaning bar, which contains 0.1 to 0.6 wt. % of a polyether group, based on the weight of the crosslinked cellulose ether, the crosslinked cellulose ether comprising a base cellulose ether and a crosslinking bond, the crosslinking bond containing a polyether group, and the base cellulose ether is a mixed cellulose ether containing a hydroxyalkyl ether group and an alkyl ether group. Even more preferably, the cleaning bar of the present invention contains 0.1 to 0.6 wt. % of a crosslinked cellulose ether, based on the weight of the cleaning bar, which contains 0.01 to 5 wt. % (preferably 0.05 to 3 wt. %, more preferably 0.1 to 2.5 wt. %, even more preferably 0.15 to 2 wt. %, and most preferably 0.2 to 1.5 wt. %) of a crosslinked cellulose ether, based on the weight of the crosslinked cellulose ether, the crosslinked cellulose ether comprising a base cellulose ether and a crosslinking bond, the crosslinking bond containing a polyether group, and the base cellulose ether is selected from the group consisting of hydroxyethyl methylcellulose, hydroxypropyl methylcellulose, methylhydroxyethyl hydroxypropyl cellulose, ethylhydroxyethyl cellulose, and combinations thereof.Most preferably, the cleaning bar of the present invention contains 0.01 to 5 wt. % (preferably 0.05 to 3 wt. %, more preferably 0.1 to 2.5 wt. %, even more preferably 0.15 to 2 wt. %, and most preferably 0.2 to 1.5 wt. %) of a crosslinked cellulose ether based on the weight of the cleaning bar, which contains 0.1 to 0.6 wt. % of a polyether group, based on the weight of the crosslinked cellulose ether, the crosslinked cellulose ether comprising a base cellulose ether and a crosslinking bond, the crosslinking bond containing a polyether group, and the base cellulose ether is hydroxyethyl methyl cellulose.

[0026] Preferably, the cleaning bar of the present invention comprises 0.01 to 5 wt. % (preferably 0.05 to 3 wt. %, more preferably 0.1 to 2.5 wt. %, even more preferably 0.15 to 2 wt. %, and most preferably 0.2 to 1.5 wt. %) of crosslinked cellulose ether based on the weight of the cleaning bar, which contains 0.1 to 0.6 wt. % of polyether groups based on the weight of the crosslinked cellulose ether, and the crosslinked cellulose is also an irreversibly crosslinked cellulose ether. More preferably, the cleaning bar of the present invention contains 0.1 to 0.6 wt % of polyether groups based on the weight of the crosslinked cellulose ether, and 0.01 to 5 wt % (preferably 0.05 to 3 wt %, more preferably 0.1 to 2.5 wt %, even more preferably 0.15 to 2 wt %, and most preferably 0.2 to 1.5 wt %) of crosslinked cellulose ether based on the weight of the cleaning bar, the crosslinked cellulose ether comprising a base cellulose ether and a crosslinking bond, the crosslinking bond containing a polyether group, the base cellulose ether being a mixed cellulose ether containing a hydroxyalkyl ether group and an alkyl ether group, and the crosslinked cellulose is also an irreversibly crosslinked cellulose ether. Even more preferably, the cleaning bar of the present invention contains 0.01 to 5 wt. % (preferably 0.05 to 3 wt. %, more preferably 0.1 to 2.5 wt. %, even more preferably 0.15 to 2 wt. %, and most preferably 0.2 to 1.5 wt. %) of crosslinked cellulose ether based on the weight of the cleaning bar, which contains 0.1 to 0.6 wt. % of polyether groups, based on the weight of the crosslinked cellulose ether, the crosslinked cellulose ether comprising a base cellulose ether and a crosslinking bond, the crosslinking bond containing a polyether group, the base cellulose ether being selected from the group consisting of hydroxyethyl methylcellulose, hydroxypropyl methylcellulose, methylhydroxyethyl hydroxypropyl cellulose, ethylhydroxyethyl cellulose, and combinations thereof, and the crosslinked cellulose is also an irreversibly crosslinked cellulose ether.Most preferably, the cleaning bar of the present invention contains 0.01 to 5 wt. % (preferably 0.05 to 3 wt. %, more preferably 0.1 to 2.5 wt. %, even more preferably 0.15 to 2 wt. %, and most preferably 0.2 to 1.5 wt. %) of crosslinked cellulose ether based on the weight of the cleaning bar, which contains 0.1 to 0.6 wt. % of polyether groups, based on the weight of the crosslinked cellulose ether, the crosslinked cellulose ether comprising a base cellulose ether and crosslinking bonds, the crosslinking bonds containing polyether groups, the base cellulose ether being hydroxyethyl methylcellulose, and the crosslinked cellulose also being an irreversibly crosslinked cellulose ether.

[0027] Preferably, the crosslinked cellulose ether contains 0.1 to 0.6 wt % (preferably 0.12 to 0.6 wt %, more preferably 0.12 to 0.45 wt %, and most preferably 0.12 to 0.29 wt %) of polyether groups based on the weight of the crosslinked cellulose ether. More preferably, the crosslinked cellulose ether contains 0.1 to 0.6 wt % (preferably 0.12 to 0.6 wt %, more preferably 0.12 to 0.45 wt %, and most preferably 0.12 to 0.29 wt %) of polyether groups based on the weight of the crosslinked cellulose ether, and the polyether groups are polyoxyalkylene groups 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 wt % (preferably 0.12 to 0.6 wt %, more preferably 0.12 to 0.45 wt %, most preferably 0.12 to 0.29 wt %) of polyether groups based on the weight of the crosslinked cellulose ether, and the polyether groups are polyoxypropylene groups having 2 to 100 (preferably 2 to 20, more preferably 3 to 15) oxypropylene groups per crosslink.

[0028] Preferably, the crosslinked cellulose ether of the present invention comprises a crosslinked base cellulose ether containing 0.1 to 0.6 wt. % polyether groups 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 base cellulose ethers include 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).

[0029] 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).

[0030] Preferably, the base cellulose ether contains a methyl ether substitution, and 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).

[0031] 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 degree of hydroxyethyl ether substitution MS(HE) of 0.05 to 0.75 (preferably 0.15 to 0.45, more preferably 0.20 to 0.40) and 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).

[0032] Preferably, the base cellulose ether is a mixed cellulose ether containing hydroxyalkyl ether substitution and alkyl ether substitution, more preferably a mixed cellulose ether having a hydroxypropyl ether substitution degree MS(PE) 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).

[0033] Preferably, the crosslinked cellulose ether comprises a base cellulose ether having crosslinks containing 0.1 to 0.6 wt. % polyether groups based on the weight of the crosslinked cellulose ether, the base cellulose ether being hydroxyethyl methyl cellulose, and the crosslinks being polyoxypropylene dioxyethylene ether crosslinks, for example, those produced as a reaction product of hydroxyethyl methyl cellulose and polypropylene glycol (PPG) glycidyl ether.

[0034] Crosslinking agents used to crosslink the base cellulose ether to form a crosslinked cellulose ether include compounds having a polyoxyalkylene or polyalkylene glycol group and two or more (preferably two) crosslinking groups, such as halogen groups, glycidyl or epoxy groups, and ethylenically unsaturated groups (e.g., vinyl groups) that form ether bonds 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)alkoxy ethers, dichloropolyoxyethylenes, diglycidyl polyalkoxy ethers, diglycidyl phosphonates, and divinyl polyoxyalkylenes containing sulfonic groups. Crosslinking agents having two different types of functional groups can be used. Examples include diglycidyl polyoxypropylene and glycidyl (poly)oxyalkyl methacrylates. Preferably, the crosslinking agent contains 2 to 100 (preferably 2 to 20, more preferably 3 to 15) oxyalkylene groups per molecule.

[0035] 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.

[0036] Preferably, crosslinked cellulose ether is irreversibly crosslinked cellulose ether.That is, the crosslink in crosslinked cellulose ether does not decompose during the intended use of crosslinked cellulose ether under normal conditions.In contrast, reversible crosslink is decomposed during the intended use of crosslinked cellulose ether under normal conditions.An example of the reversible crosslink in the cellulose ether intended for use in cleaning bar is that which is produced by using an aldehyde crosslinking agent (for example, glyoxal), and this crosslink is decomposed when crosslinked material is dissolved in water.

[0037] Preferably, the cleaning bars 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 <detection limit) crosslinked carboxymethyl cellulose, based on the weight of the cleaning bar.

[0038] Preferably, the cleaning bars of the present invention are solid. As used herein and in the appended claims with respect to cleaning bars, the term "solid" means that the cleaning bar does not appreciably change shape when placed on a rigid surface and allowed to rest on the rigid surface at room temperature (22°C) and pressure (101.4 kPa) for 24 hours.

[0039] Preferably, the cleaning bars of the present invention have an abrasion rate of 0.5 to 11 wt. % (more preferably, 1 to 8 wt. %, and most preferably, 1 to 4 wt. %), where abrasion rate is the weight loss of the cleaning bar after 4 days of use, as described in the Examples.

[0040] Preferably, the cleaning bars of the present invention further comprise optional ingredients. More preferably, the cleaning bars of the present invention further comprise optional ingredients selected from the group consisting of builders, humectants, processing aids (e.g., titanium dioxide), preservatives (e.g., benzoic acid, sorbic acid, phenoxyethanol), antioxidants (e.g., butylated hydroxytoluene), viscosity modifiers, polymers, free fatty acids, foam stabilizers, foam boosters, fillers, chelating agents, antimicrobial agents (e.g., biocides), pH adjusters, pH buffers, fragrances / fragrances, salts, colorants (e.g., dyes), and mixtures thereof. Most preferably, the cleaning bars of the present invention further comprise optional ingredients selected from the group consisting of processing aids (e.g., titanium dioxide), fragrances, colorants, and mixtures thereof.

[0041] Preferably, the cleaning bar of the present invention optionally further comprises 0 to 50 wt % (preferably 8 to 40 wt %, more preferably 10 to 30 wt %, and most preferably 10.5 to 15 wt %) of a builder based on the weight of the cleaning bar. More preferably, the cleaning bar of the present invention optionally further comprises 0 to 50 wt % (preferably 8 to 40 wt %, more preferably 10 to 30 wt %, and most preferably 10.5 to 15 wt %) of a builder based on the weight of the cleaning bar, the builder being selected from the group consisting of hydrated alkali metal phosphates, alkalis (including carbonates and bicarbonates), zeolites, ethylenediaminetetraacetates, nitrilotriacetates, and mixtures thereof. More preferably, the cleaning bars of the present invention optionally further comprise 0 to 50 wt. % (preferably 8 to 40 wt. %, more preferably 10 to 30 wt. %, and most preferably 10.5 to 15 wt. %) of a builder, based on the weight of the cleaning bar, selected from the group consisting of zeolite, sodium citrate, sodium carbonate, calcium carbonate, sodium bicarbonate, calcium bicarbonate, and mixtures thereof. Most preferably, the cleaning bars of the present invention optionally further comprise 0 to 50 wt. % (preferably 8 to 40 wt. %, more preferably 10 to 30 wt. %, and most preferably 10.5 to 15 wt. %) of a builder, based on the weight of the cleaning bar, the builder comprising at least one of sodium carbonate and calcium carbonate.

[0042] Preferably, the cleaning bar of the present invention further comprises a humectant. More preferably, the cleaning bar of the present invention further comprises 0.1 to 5 wt % (preferably 0.25 to 2 wt %, more preferably 0.5 to 1.5 wt %, and most preferably 0.75 to 1.25 wt %) of a humectant based on the weight of the cleaning bar. Even more preferably, the cleaning bar of the present invention further comprises 0.1 to 5 wt % (preferably 0.25 to 2 wt %, more preferably 0.5 to 1.5 wt %, and most preferably 0.75 to 1.25 wt %) of a humectant based on the weight of the cleaning bar, the humectant being a polyhydric alcohol selected from the group consisting of glycerin, sorbitol, propylene glycol, butylene glycol, hexylene glycol, ethoxylated glucose, 1,2-hexanediol, hexanetriol, dipropylene glycol, erythritol, trehalose, diglycerin, xylitol, maltitol, maltose, glucose, fructose, and mixtures thereof. Even more preferably, the cleaning bar of the present invention further comprises 0.1 to 5 wt % (preferably 0.25 to 2 wt %, more preferably 0.5 to 1.5 wt %, and most preferably 0.75 to 1.25 wt %) of a humectant based on the weight of the cleaning bar, the humectant comprising glycerin. Most preferably, the cleaning bar of the present invention further comprises 0.1 to 5 wt % (preferably 0.25 to 2 wt %, more preferably 0.5 to 1.5 wt %, and most preferably 0.75 to 1.25 wt %) of a humectant based on the weight of the cleaning bar, the humectant being glycerin.

[0043] Preferably, the cleaning bar of the present invention further comprises a processing aid. More preferably, the cleaning bar of the present invention further comprises 0.01 to 3 wt % (preferably 0.1 to 1.5 wt %, more preferably 0.25 to 1.25 wt %, and most preferably 0.5 to 1 wt %) of a processing aid based on the weight of the cleaning bar. Even more preferably, the cleaning bar of the present invention further comprises 0.01 to 3 wt % (preferably 0.1 to 1.5 wt %, more preferably 0.25 to 1.25 wt %, and most preferably 0.5 to 1 wt %) of a processing aid based on the weight of the cleaning bar, the processing aid being an inorganic powder material selected from the group consisting of talc, calcite, kaolin, silicon dioxide, titanium dioxide, diatomaceous earth, and mixtures thereof. Even more preferably, the cleaning bar of the present invention further comprises 0.01 to 3 wt. % (preferably 0.1 to 1.5 wt. %, more preferably 0.25 to 1.25 wt. %, and most preferably 0.5 to 1 wt. %) of a processing aid based on the weight of the cleaning bar, the processing aid being selected from the group consisting of talc, calcite, titanium dioxide, and mixtures thereof. Most preferably, the cleaning bar of the present invention further comprises 0.01 to 3 wt. % (preferably 0.1 to 1.5 wt. %, more preferably 0.25 to 1.25 wt. %, and most preferably 0.5 to 1 wt. %) of a processing aid based on the weight of the cleaning bar, the processing aid comprising titanium dioxide.

[0044] Preferably, the cleaning bar of the present invention further comprises a chelating agent. More preferably, the cleaning bar of the present invention further comprises 0.01 to 0.5 wt % (preferably 0.05 to 0.3 wt %, more preferably 0.075 to 0.25 wt %, and most preferably 0.1 to 0.2 wt %) of the chelating agent based on the weight of the cleaning bar. Even more preferably, the cleaning bar of the present invention further comprises 0.01 to 0.5 wt % (preferably 0.05 to 0.3 wt %, more preferably 0.075 to 0.25 wt %, and most preferably 0.1 to 0.2 wt %) of the chelating agent based on the weight of the cleaning bar, the chelating agent being selected from the group consisting of diethylenetriaminepentaacetic acid, 1-hydroxyethane-1,1-diphosphonic acid, citric acid, ethylenediaminetetraacetic acid (EDTA), salts thereof, and mixtures thereof. Even more preferably, the cleaning bar of the present invention further comprises 0.01 to 0.5 wt % (preferably 0.05 to 0.3 wt %, more preferably 0.075 to 0.25 wt %, and most preferably 0.1 to 0.2 wt %) of a chelating agent, based on the weight of the cleaning bar, selected from the group consisting of diethylenetriaminepentaacetic acid pentasodium salt, 1-hydroxyethane-1,1-diphosphonic acid disodium salt, citric acid, ethylenediaminetetraacetic acid (EDTA), ethylenediaminetetraacetic acid tetrasodium salt, and mixtures thereof. Most preferably, the cleaning bar of the present invention further comprises 0.01 to 0.5 wt % (preferably 0.05 to 0.3 wt %, more preferably 0.075 to 0.25 wt %, and most preferably 0.1 to 0.2 wt %) of a chelating agent, based on the weight of the cleaning bar, the chelating agent being ethylenediaminetetraacetic acid tetrasodium salt.

[0045] Preferably, the cleaning bar of the present invention further comprises a fragrance. More preferably, the cleaning bar of the present invention further comprises 0.01 to 3 wt % (preferably 0.1 to 2 wt %, more preferably 0.5 to 1.75 wt %, and most preferably 0.75 to 1.25 wt %) of fragrance based on the weight of the cleaning bar.

[0046] Preferably, the cleaning bar of the present invention further comprises a colorant, and more preferably, the cleaning bar of the present invention further comprises 0.01 to 3 wt % (preferably 0.1 to 2 wt %, more preferably 0.5 to 1.75 wt %, and most preferably 0.75 to 1.25 wt %) of a colorant based on the weight of the cleaning bar.

[0047] Preferably, the cleaning bar of the present invention comprises 0 to 70 wt. % (preferably, 2 to 65 wt. %, more preferably, 2.5 to 60 wt. %, and most preferably, 3 to 55 wt. %) of filler based on the weight of the cleaning bar. More preferably, the cleaning bar of the present invention comprises 0 to 70 wt. % (preferably, 2 to 65 wt. %, more preferably, 2.5 to 60 wt. %, and most preferably, 3 to 55 wt. %) of filler based on the weight of the cleaning bar, the filler further comprising a material selected from the group consisting of sulfates (e.g., magnesium sulfate), chlorides (e.g., sodium chloride), calcite, silicates (e.g., sodium silicate, hydrous aluminum silicate), dolomite, and mixtures thereof. Most preferably, the cleaning bar of the present invention comprises 0 to 18 wt. % (preferably, 2 to 10 wt. %, more preferably, 2.5 to 7.5 wt. %, and most preferably, 3 to 5 wt. %) of filler based on the weight of the cleaning bar, the filler comprising sodium silicate.

[0048] The cleaning bars of the present invention can be produced using well-known techniques, including melt casting (also known as melting and pouring), stamping, extrusion, milling, plodding, and combinations thereof.

[0049] Preferably, the method of making the cleaning bar of the present invention includes providing a cleaning surfactant (preferably, the cleaning surfactant is a soap, more preferably, the cleaning surfactant is a soap presented as soap noodles, and most preferably, the cleaning surfactant is a soap presented as soap noodles comprising an aqueous mixture of at least 70% by weight total fatty materials (TFM) and 10-15% by weight water); providing water; providing a crosslinked cellulose ether containing 0.1-0.6% by weight polyether groups, based on the weight of the crosslinked cellulose ether; mixing the cleaning surfactant, crosslinked cellulose ether, and water to form a combination (preferably, heating the cleaning surfactant, crosslinked cellulose ether, and water while mixing to form the combination); milling the combination; extruding the milled combination; and die-cutting the extruded material to provide the cleaning bar. More preferably, the method of making the cleaning bar of the present invention further comprises providing a cleaning surfactant (preferably, the cleaning surfactant is a soap, more preferably, the cleaning surfactant is a soap presented as soap noodles, and most preferably, the cleaning surfactant is a soap presented as soap noodles comprising an aqueous mixture of at least 70% by weight total fatty materials (TFM) and 10-15% by weight water); providing water; providing a crosslinked cellulose ether containing 0.1-0.6% by weight polyether groups, based on the weight of the crosslinked cellulose ether; providing a fragrance; and providing a processing aid; and further comprises mixing the cleaning surfactant, crosslinked cellulose ether, fragrance, processing aid, and water to form a combination; milling the combination; extruding the milled combination; and die-cutting the extruded material to provide the cleaning bar.

[0050] Some embodiments of the present invention will now be described in detail in the following examples.

[0051] 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 approximately 400 daltons and the following formula:

[0052] [ka] where n is 5.7 to 6.7 (EPILOX™ M985 poly(propylene glycol) diglycidyl ether crosslinker available from Leuna-Harze GmbH, Leuna, DE).

[0053] Ground cellulose floc (1.5 mol) was added to a 5 L autoclave. After briefly purging the autoclave with nitrogen gas, the contents of the autoclave were heated to 40°C. Dimethyl ether (DME, 4.7 mol / mol anhydroglucose units (AGU)) and methyl chloride (MCl, 3.2 mol / mol AGU) were then injected into the autoclave. Caustic soda (NaOH, 50 wt% strength aqueous, 1.9 mol NaOH / mol AGU) was added to the autoclave in three portions over 2 minutes at a temperature of 40°C. The reaction mixture was held at 40°C for 30 minutes. Ethylene oxide (0.45 mol / mol AGU) was then added, and the reaction mixture was held 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 increments at 30-second intervals. The contents of the autoclave were then heated to 80°C within 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 increments over 30 minutes, followed by a 70-minute cook-off period at 80°C. Following this, the product crosslinked cellulose ether was washed with hot (>95°C) water, neutralized with formic acid, granulated, dried, and milled.

[0054] Comparative Example C1 and Examples 1 to 7: Cleaning Bar Cleaning bars were prepared for each of Comparative Example C1 and Examples 1-7, having the compositions listed in Table 1. Soap noodles were ground in a Sigma mixer and mixed in the Sigma mixer with the other ingredients in the amounts listed in Table 1. All ingredients were added sequentially, not in any particular order, except for the fragrance, which was added last. The entire mass was then transferred from the Sigma mixer to a triple roll mill, where the mixture was ground. The entire process was carried out under ambient laboratory conditions. The mass received from the roll mill was then placed in a screw masher and extruded at a temperature of 45-65°C. The extruded mass was then cut into small pieces and punched with a soap die to provide the final cleaning bar.

[0055] [Table 1]

[0056] Moisture content of cleaning bar The moisture content of cleaning bars prepared according to Comparative Example C1 and Examples 1-7 was measured using a Mettler Toledo HX204 Halogen Moisture Analyzer using a drying temperature set at 150° C. and a 0.5 g sample selected from a cross section of the cleaning bar. The moisture content is reported in Table 2.

[0057] [Table 2]

[0058] Cleaning bar wear rate Trained panelists evaluated each of the cleaning bars prepared according to Comparative Example C1 and Examples 1-7 to assess the wear rate as the percent weight loss from the cleaning bar after four days of use using the following test protocol: A 20 cm x 15 cm piece of water-soaked poplin cotton cloth was taken. The cleaning bar was first weighed (each cleaning bar composition was tested in triplicate). The top surface of the bar was placed on the surface of the cloth and rubbed 10 times. Each rub was one horizontal stroke. Using a similar method, the bottom surface of the bar was rubbed 10 times on a different cloth kept under the same conditions. A total of 20 rubs were made per cleaning bar. The cleaning bar was allowed to sit for 30 minutes, and then the procedure was repeated. This process was repeated five times per day for each cleaning bar (i.e., 100 rubs per cleaning bar per day). The cleaning bar was then kept in a Petri dish in a tray containing some water, covered overnight with paraffin film just to create moisture. The next day, repeat this process (i.e., 100 rubs per cleaning bar) and then store the cleaning bar as described. This continues for four consecutive days. On the fifth day, weigh the cleaning bar and report the average wear rate in Table 3.

[0059] [Table 3]

Claims

1. A cleaning bar, 5 to <78.99 wt. % cleaning surfactant, based on the weight of the cleaning bar; >21-50 wt. % water, based on the weight of the cleaning bar; 0.01 to 5 wt. % of a crosslinked cellulose ether, based on the weight of the cleaning bar, the crosslinked cellulose ether containing 0.1 to 0.6 wt. % of polyether groups, based on the weight of the crosslinked cellulose ether; 0 to 3 weight percent of a processing aid, based on the weight of the cleaning bar; 0-3% by weight, based on the weight of the cleaning bar, of an optional ingredient selected from the group consisting of fragrance, colorant / dye, or combinations thereof; 0 to 15 wt. % filler, based on the weight of the cleaning bar; A cleaning bar, wherein the cleaning bar is solid.

2. 10. The cleaning bar of claim 1, wherein the crosslinked cellulose ether is an irreversibly crosslinked cellulose ether.

3. 3. The cleaning bar of claim 2, wherein the polyether group in the irreversibly crosslinked cellulose ether is a polyoxyalkylene group having 2 to 100 oxyalkylene groups.

4. 4. The cleaning bar of claim 3, wherein the polyoxyalkylene group is selected from the group consisting of polyoxyethylene, polyoxypropylene, and combinations thereof.

5. 5. The cleaning bar of claim 4, 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.

6. 6. The cleaning bar of claim 5, wherein the base cellulose ether is selected from the group consisting of hydroxyethyl methylcellulose, hydroxypropyl methylcellulose, methylhydroxyethyl hydroxypropyl cellulose, ethylhydroxyethyl cellulose, and combinations thereof.

7. the cleaning surfactant is a soap, the cleaning bar comprises 35 to <78.99 wt. % of the soap, based on the weight of the cleaning bar; and the cleaning bar comprises: 0.01 to 3 wt. % of a processing aid, based on the weight of the cleaning bar; and 0.01 to 3% by weight, based on the weight of the cleaning bar, of an optional ingredient selected from the group consisting of at least one of a fragrance and a dye; 10. The cleaning bar of claim 1, wherein the cleaning bar is a laundry cleaning bar.

8. the cleaning surfactant is a soap, the cleaning bar comprises 35 to <78.99 wt. % of the soap, based on the weight of the cleaning bar; and the cleaning bar comprises: 0.01 to 3 wt. % of a processing aid, based on the weight of the cleaning bar; 0.01 to 3 wt. % of an optional ingredient selected from the group consisting of at least one of a fragrance and a dye, based on the weight of the cleaning bar; and 0.1 to 5 wt. % of a humectant, based on the weight of the cleaning bar; 10. The cleaning bar of claim 1, wherein the cleaning bar is a personal care cleansing bar.

9. 1. A method of making a cleaning bar, comprising: providing a cleaning surfactant; Providing water and providing a crosslinked cellulose ether containing 0.1 to 0.6 weight percent polyether groups, based on the weight of the crosslinked cellulose ether; mixing the cleaning surfactant, the crosslinked cellulose ether, and the water to form a combination; milling the combination; extruding the milled combination; and stamping the extruded material to provide the cleaning bar.

10. Providing a fragrance; providing a processing aid; 10. The method of claim 9, wherein the fragrance and the processing aid are mixed with the cleaning surfactant, the crosslinked cellulose ether, and the water to form the combination.

Images