GB2406574A - Extruded fabric cleaning bar - Google Patents

Abstract

A low water containing extruded bar (preferably a synthetic soap bar or stick) contains a moisture sensitive source of active oxygen. The use of such a bar for laundry and carpet cleaning is also disclosed. The bar may include alkylbenzene sulfonic acid, alkyl sulfate, nonionic alcohol ethoxylate, silicone surfactant, coated sodium percarbonate, calcium peroxide, TAED, HEDP, and enzyme.

Description

EXTRUDED FABRIC CLEANING BAR

The invention relates to new low water containing extruded bar (preferably a synthetic soap bar or stick) containing a moisture sensitive source of active oxygen and the use of such a bar for laundry and carpet cleaning.

Synthetic soap bars, typically having a holder, are popular in many countries as laundry aids or for cleaning carpet. The area to be cleaned is wetted and the bar is rubbed over the area where some of the bar is rubbed off and deposited on to the stain. The use of the term fabric cleaning bar denotes the absence of natural soap (although a minor amount of up to 10% w/w may be present), su-ch products are not suitable for personal use, such as hand washing, as they are too harsh.

Natural standard soap bars for personal care cannot be adapted to be fabric cleaning bars and include a moisture sensitive source of active oxygen, such as sodium percarbonate or sodium perforate which are common oxygen bleach actives, due to their high water content causing the quick degradation of these actives with consequential oxygen evolving and the bar cracking.

In prior patent applications WO 97/44434, WO 99/20731, WO 00/17308, WO 00/17312, WO 99/20734, WO 00/17308 and US 4,911, 860 the stability of moisture sensitive sources of active oxygen is improved in 3s synthetic soap bars by limiting the level of water, in the range between o.s and 10% w/w and using chelating agents, known to reduce the level of metals into the formula. Metals can act as catalysts for oxygen bleach degradation.

Both the reduction in the water level and the use of chelating agents have not been found to be enough to provide an acceptably stable soap bar matrix. In particular problems arise in the manufacture of such products where elevated temperatures are needed in order to manufacture the product.

The present invention is related to the usage of glycol ethers and solvents in general to provide a low temperature extrusion process for synthetic soap bar manufacturing, thus enabling the inclusion of such temperature sensitive agents.

Therefore, we present as a feature of the invention an extruded fabric cleaning bar comprising: at least one anionic surfactant; at least one organic solvent, preferably a glycol ether; at least one builder; a solid water-soluble source of active oxygen; optionally, at least one chelating agent; optionally up to 10% w/w of a nonionic surfactant; optionally up to 10% w/w of minor ingredients selected from one or more of the following fragrance, bleach activator, enzyme, bleach catalyst and colour (pigment or dye).

Glycol ethers have been in particular found to allow a low temperature extrusion, in the range between 10 40 C, whereas standard manufacturing conditions are in the range 40-80 C. Glycol ethers are able to provide a mixture sufficiently soft and workable for the extrusion process even at low temperature. This unexpected property is in addition more interesting considering the low level of glycol ethers necessary to achieve a low temperature extrusion are from 0.01 to 10% w/w and ideally is between 0.1-5% w/w.

The manufacturing process for the extruded cleaning bar is simple and can be divided into four different steps. Therefore we present as a feature of the invention a method of manufacturing a fabric cleaning bar comprising; a) neutralization of at least one anionic acid surfactant with an alkaline source to form a solid; b) adding and mixing of all remaining solid and/or liquid raw materials in any order (preferably the source of active oxygen is added last); c) extruding at low temperature the resultant mixture, preferably in the range of 10 to 40 C, ideally 25 to 40 C)i and d) cutting the extrudate.

We present a further feature of the invention a method of cleaning fabric comprising the steps of (a) rubbing a fabric cleaning bar, as defined herein, on to the fabric; and either (b) adding an additional cleaning composition dissolved in water to the fabric; or (c) rinsing deposited fabric cleaning bar from the fabric with water.

As an additional step the cut extrudate can optionally be stamped into a different shape. The stamping may optionally include the provision of words or designs into the surface of the bar.

The extruded bars described in this invention have a weight in the range 50-600g, preferred range is 100-300g.

Preferably the alkaline source is an alkali metal salt, such as sodium carbonate.

Points of advantage found in this invention: Good oxygen bleach storage stability, obtained by limiting the water content and the low temperature extrusion process through the use of solvents, i.e. glycol ethers, in the formula.

Use of glycol ethers as the main solvent has been found to provide formula workability even at low solvent concentration.

Good oxidisable stain removal performance that is not present in current soap bar products.

Granular bleach has been found to give good stain removal due to the higher mechanical action obtained with the granular bleach.

Low fibre/colour damage of washed fabric.

Source of Active Oxygen An essential ingredient is a source of active oxygen. A preferred source according to the present invention is hydrogen peroxide or sources thereof. As used herein a hydrogen peroxide source refers to any water-soluble source of hydrogen peroxide. Suitable watersoluble sources of hydrogen peroxide for use herein include percarbonates, organic or inorganic peroxides and perforates.

Hydrogen peroxide or sources thereof provide from 0.1% to 40% w/w, preferably from 0.5% to 30% w/w, most preferably from 1% to 15% w/w of the total composition.

As used herein active oxygen concentration refers to the percentage concentration of elemental oxygen, with an oxidation number zero, that being reduced to water would be stoichiometrically equivalent to a given percentage concentration of a given peroxide compound, when the peroxide functionality of the peroxide compound is completely reduced to oxides. The active oxygen sources according to the present invention increase the ability of the compositions to remove oxidizable stains, to destroy malodorous molecules and to kill germs.

The concentration of available oxygen can be determined by methods known in the art, such as the iodimetric method, the permanganometric method and the cerimetric method. Said methods and the criteria for the choice of the appropriate method are described for example in "Hydrogen Peroxide", W. C. Schumo, C. N. Satterfield and R. L. Wentworth, Reinhold Publishing Corporation, New York, 1955 and "Organic Peroxides", 3s Daniel Swern, Editor Wiley Int. Science, 1970.

Suitable organic and inorganic peroxides for use in the compositions according to the present invention include diacyl and dialkyl peroxides such as dibenzoyl peroxide, dilauroyl peroxide, dicumyl peroxide, persulphuric acid and mixtures thereof.

Suitable preformed peroxyacids for use in the compositions according to the present invention include diperoxydodecandioic acid DPDA, magnesium perphthalatic acid, perlauric acid, perbenzoic acid, diperoxyazelaic acid and mixtures thereof.

Bleach Activator Optionally, the compositions may additionally comprise from 1% to 30% w/w, preferably from 2% to 20% w/w of peracid precursors, i.e. compounds that upon reaction with hydrogen peroxide product peroxyacids.

Examples of peracid precursors suitable for use in the present invention can be found among the classes of anhydrides, amides, imides and esters such as acetyl triethyl citrate (ATC) described for instance in EP 91 87 0207, tetra acetyl ethylene diamine (TAED), succinic or maleic anhydrides.

Water level The water level in the fabric cleaning bar has been limited by the use of raw materials that are water free or contain less than 5% w/w, and preferably below 1% w/w.

The water content is also kept low due to the water that is not evaporated during the neutralisation step. The total water content of the fabric cleaning bar is below 10% w/w and preferably below 5%w/w.

Solvent The solvent is found to be useful at levels of 0.01 to 10%w/w, preferred level is between 0.1-5% w/w. The solvent constituent may include one or more alcohol, glycol, acetate, ether acetate, glycerol, polyethylene glycol (with molecular weight ranging from 200 to 10000), silicones or glycol ethers. Exemplary alcohols useful in the compositions of the invention include C2-C8 primary and secondary alcohols which may be straight chained or branched, preferably pentanol and hexanol.

Preferred solvents for the invention are glycol ethers and examples include those glycol ethers having the general structure Ra-O-[CH2-CH(R)(CH2)m-O]n-H, wherein Ra is C1 to 20 alkyl or alkenyl, or a cyclic alkane of at least 6 carbon atoms, which may be fully or partially unsaturated or aromatic; n is an integer from 1 to 10; preferably from 1 to 5; each R is selected from H or CH3 and m is the integer 0 or 1.

Specific and preferred solvents are selected from propylene glycol methyl ether, n is from 1 to 5 and each R is selcted from H or CH3 dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol npropyl ether, ethylene glycol n-butyl ether, diethylene glycol n-butyl ether, diethylene glycol methyl ether, propylene glycol, ethylene glycol, isopropanol, ethanol, methanol, diethylene glycol monoethyl ether acetate, and particularly useful are, propylene glycol phenyl ether, ethylene glycol hexyl ether and diethylene glycol hexyl ether.

Surfactants Preferred total level of surfactant is in the range from 1 to 50% w/w, ideally 10 to 30% w/w and preferably to 25% w/w. Nonionic and anionic surfactants can be used.

The nonionic surfactant, when present, is preferably a surfactant having a formula RO(CH2CH20)nH wherein R is a mixture of linear, even carbonnumber hydrocarbon chains ranging from C12H25 to C16H33 and n represents the number of repeating units and is a number of from about 1 to about 12. Examples of other nonionic surfactants include higher aliphatic primary alcohol containing about twelve to about 16 carbon atoms which are condensed with about three to thirteen moles of ethylene oxide.

Other examples of nonionic surfactants include primary alcohol ethoxylates (available under the Neodol tradename from Shell Co.), such as Cll alkanol condensed with 9 moles of ethylene oxide (Neodol 1-9), C12- 13 alkanol condensed with 6.5 moles ethylene oxide (Neodol 23-6.5), C12-13 alkanol with 9 moles of ethylene oxide (Neodol 23-9), C12-15 alkanol condensed with 7 or 3 moles ethylene oxide (Neodol 25-7 or Neodol 25-3), C14-15 alkanol condensed with 13 moles ethylene oxide (Neodol 3s 45-13), C9-11 linear ethoxylated alcohol, averaging 2.5 moles of ethylene oxide per mole of alcohol (Neodol 91- 2.5), and the like.

Other examples of nonionic surfactants suitable for use in the present invention include ethylene oxide condensate products of secondary aliphatic alcohols containing 11 to 18 carbon atoms in a straight or branched chain configuration condensed with 5 to 30 moles of ethylene oxide. Examples of commercially available nonionic detergents of the foregoing type are C11-15 secondary alkanol condensed with either 9 moles of ethylene oxide (Tergitol 15-S-9) or 12 moles of ethylene oxide (Tergitol 15-S-12) marketed by Union Carbide, a subsidiary of Dow Chemical.

Octylphenoxy polyethoxyethanol type nonionic surfactants, for example, Triton X-100, as well as amine oxides can also be used as a non-ionic surfactant in the present invention.

Other examples of linear primary alcohol ethoxylates are available under the Tomadol tradename such as, for example, Tomadol 1-7, a C11 linear primary alcohol ethoxylate with 7 moles EO; Tomadol 25-7, a C12-C15 linear primary alcohol ethoxylate with 7 moles EO; Tomadol 45-7,a C14-C15 linear primary alcohol ethoxylate with 7 moles EO; and Tomadol 91-6, a C9- C11 linear alcohol ethoxylate with 6 moles EO.

A preferred surfactant is an anionic surfactant.

Such anionic surface-active agents are frequently provided in an acid for and salified during manufacturing s as alkali metal salts, ammonium salts, amine salts, aminoalcohol salts or magnesium salts. Contemplated as useful are one or more sulfate or sulfonate compounds including: alkyl benzene sulfates, alkyl sulfates, alkyl ether sulfates, alkylamidoether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkyleulfonates, alkylamide sulfonates, alkylaryleulfonates, olefinsulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfosuccinamate, alkyl sulfoacetates, alkyl phosphates, alkyl ether phosphates, acyl sarconsinates, acyl isethionates, and N-acyl taurates. Generally, the alkyl or acyl radical in these various compounds comprise a carbon chain containing 12 to 20 carbon atoms.

Other anionic surfactant considered in this invention are alkyl naphthalene sulfonate anionic surfactants of the formula:

R SO3M

wherein R is a straight chain or branched alkyl chain having from about 1 to about 25 carbon atoms, saturated or unsaturated, and the longest linear portion of the alkyl chain is 15 carbon atoms or less on the average, M is a cation which makes the compound water soluble especially an alkali metal such as sodium or magnesium, ammonium or substituted ammonium cation.

3s Super wetting agent A super wetting agent is capable of reducing the surface tension in water at values below 25 mN/m, in the range between 18 and 25 mN/m at concentrations of 0.0001 1%w/v, preferably between 0.001 and 0.1%w/w.

Preferred levels in the solid composition are between 0.01 and 10%w/w. Examples of super wetting agents of this invention are silicone glycol copolymers and flurosurfactants. The silicone glycol copolymers are described by the following formula: CH3 'CH3 ' 'CH3 CH3 CH3-Si-O- Si- O _ Si-O - Si-CH3 CH3 CH3 X R y CH3 (CH2CH2O)m (CH2CHO)n-R, CH3 Where x, y, m and n are whole number ranging from O to 25. X is preferred between 0-10 and y, m and n between 0 5. R and R' are straight chain or branched alkyl chain having from about 1 to about 25 carbon atoms, saturated or unsaturated, and the longest linear portion of the alkyl chain is 15 carbon atoms or less on the average.

The fluorinated surfactant is described in the following formulae: F(CF2) n-CH2CH2-S-CH2CH2-COOM F(CF2)nN(CH3)(CH2)3(CH2CHzO)x OSO2M 17 CF3(cF2cF2)n(cFcF)m-(cH2cH2o)x-opo3M2 Wherein n, m and x are integers having a value from 0 to 15; preferred values are between 1 and 12, M is a cation which is capable of making the compound water soluble especially an alkali metal such as sodium or magnesium, ammonium or substituted ammonium cation.

Builder The extruded cleaning bar composition can comprise of at least one builder or a combination of them from 1 to 80% w/w, preferably from 10 to 60% w/w and more preferably from 25 to 50% w/w.

Examples of sesquicarbonate, bicarbonate and carbonate builders are the alkaline earth and the alkali metal carbonates, including sodium and calcium carbonate and sesqui-carbonate and mixtures thereof. Other examples of carbonate type builders are the metal carboxy glycine and metal glycine carbonate.

Other builders useful for this invention are sodium chloride, bentonite, zeolites, citrates, talc and metal sulfate salts as sodium, calcium and aluminium sulfates.

Examples of chelating agents are described below: - the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures therefore with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.

- iminosuccinic acid metal salts - polyaspartic acid metal salts.

- ethylene diamino tetra acetic acid and salt forms.

- water-soluble phosphonate and phosphate builders are useful for this invention. Examples of phosphate budders are the alkali metal tripolyphosphates, sodium potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate sodium polymeta/phosphate in which the degree of polymerization ranges from 6 to 21, and salts of physic acid. Specific examples of watersoluble phosphate builders are the alkali metal tripolyphosphates, sodium potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from 6 to 21, and salts of physic acid. Such polymers include the polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.

Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivates such as the carboxymethloxysuccinates described in GB-A-1,379,241, lactoxysuccinates described in GB-A- 1,389,732, and aminosuccinates described in NL-A-7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3- propane tricarboxylates described in GB-A-1,387,447.

Polycarboxylate containing four carboxy groups include oxydisuccinates disclosed in GB-A-1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1, 1,2,3-propane tetracarobyxlates.

Polycarboxylates confining sulfa substituents include the sulfosuccinate derivatives disclosed in GB-A-1,398,421, GB-A-1,398,422 and US-A-3,936448, and the sulfonated pyrolsed citrates described in GB-A-1,439,000.

Alicylic and heterocyclic polycarboxylates include cyclopentane-cis,cis, cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5,6-hexane - hexacarboxylates and carboxymethyl derivates of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in GB-A-1,425,343.

Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups 2s per molecule, more particularly citrates.

Suitable polymer water-soluble compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two caroxylic radicals separated from each other by not more than two carbon atoms, carbonates, bicarbonates, borates, phosphates, and mixtures of any of thereof.

The carboxylate or polycarboxylate builder can be 3s monomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.

Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic lo acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the watersoluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, barbaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.

Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivates such as the carboxymethloxysuccinates described in GB-A-1,379, 241, lactoxysuccinates described in GB-A-1,389,732, and aminosuccinates described in NL-A-7205873, and the oxypolycarboxylate materials such as 2oxa-1,1,3-propane tricarboxylates described in GB-A-1,387,447.

Polycarboxylate containing four carboxy groups include oxydisuccinates disclosed in GB-A-1,261,829, 1,1,2,2 ethane tetracarboxylates, 1,1,3,3propane tetracarboxylates and 1,1,2,3-propane tetracarobyxlates.

Polycarboxylates confining sulfo suibstituents include the sulfosuccinate derivatives disclosed in GB-A 1,398,421, GB-A-1,398,422 and US-A-3,936448, and the sulfonated pyrolsed citrates described in GB-A-1,439,000.

Alicylic and heterocyclic polycarboxylates include cyclopentane-cis,cis, cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5,6hexane hexacarboxylates and carboxymethyl derivates of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in GB-A-1,425,343.

Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.

More preferred polymers are homo-polymers, copolymers and multiple polymers of acrylic, flourinated acrylic, sulfonated styrene, maleic anhydride, metacrylic, iso- butylene, styrene and ester monomers.

Examples of these polymers are Acusol supplied from Rohm & Haas, Syntran supplied from Interpolymer and Versa and Alcosperse series supplied from Alco Chemical, a National Starch & Chemical Company.

- The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures therefore with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.

Chelating Agent In the context of the present application it will be appreciate that builders are compounds that sequester metal ions associated with the hardness of water, e.g. calcium and magnesium, whereas chelating agents are compounds that sequester transition metal ions capable of catalyzing the degradation of oxygen bleach systems.

s However, certain compounds may have the ability to do perform both functions.

Suitable chelating agents to be used herein include chelating agents selected from the group of phosphonate chelating agents, amino carboxylate chelating agents, polyfunctionally-substituted aromatic chelating agents, and further chelating agents like glycine, salicylic acid, aspartic acid, glutamic acid, malonic acid, or mixtures thereof. Chelating agents when used, are typically present herein in amounts ranging from 0.01% to 15%w/w of the total composition and preferably from 0.05% to 5%w/w.

Suitable phosphonate chelating agents to be used herein may include ethydronic acid as well as amino phosphonate compounds, including amino alkylene poly (alkylene phosphonate), alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates, and diethylene triamine penta methylene phosphonates. The phosphonate compounds may be present either in their acid form or as salts of different cations on some or all of their acid functionalities. Preferred phosphonate chelating agents to be used herein are diethylene triamine penta methylene phosphonates. Such phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST TM.

Polyfunctionally-substituted aromatic chelating agents may also be useful in the compositions herein. See U.S. patent 3,812,044, issued May 21, 1974, to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy -3,5- disulfobenzene.

A preferred biodegradable chelating agent for use herein is ethylene diamine N,N'-disuccinic acid, or alkali metal, or alkaline earth, ammonium or substitutes ammonium salts thereof or mixtures thereof.

Ethylenediamine N,N'-disuccinic acids, especially the (S,S) isomer have been extensively described in US patent 4, 704, 233, November 3, 1987, to Hartman and Perkins.

Ethylenediamine N,N'-disuccinic acids is, for instance, commercially available under the tradename ssEDDS TM from Palmer Research Laboratories.

Suitable amino carboxylates to be used herein include ethylene diamine tetra acetates, diethylene triamine pentaacetates, diethylene triamine pentaacetate (DTPA) ,N- hydroxyethylethylenediamine triacetates, nitrilotri- acetates, ethylenediamine tetrapropionates, triethylenetetraaminehexa- acetates, ethanol-diglycines, propylene diamine tetracetic acid (PDTA) and methyl glycine diacetic acid (MGDA), both in their acid form, or in their alkali metal, ammonium, and substituted ammonium salt forms. Particularly suitable amino carboxylates to be used herein are diethylene triamine penta acetic acid, propylene diamine tetracetic acid (PDTA) which is, for instance, commercially available from BASF under the trade name Trilon FS TM and methyl glycine all-acetic acid (MGDA).

Additional, optional, ingredients, such as fragrances, dyes and enzymes, are present at levels of up to 10% w/w, preferably less then 2% w/w.

RES LTS: The extruded cleaning bar formulations of this invention have been tested in terms of storage stability, stain removal and colour damage damage.

STORAGE STABILITY TEST: The extruded bar formulations have been put in stability in polypropylene/polyethylene flow pack that is a standard packaging used for soap bars. Room temperature, 20 C/90%RH, 30 C/70%RH, 40 C/75%RH and 50 C conditions have been used. The extruded bar has also been tested in the same conditions without any packaging protection to do a disaster check on the product stability.

A storage rating has been assigned to the formulations for appearance quality identification. The percarbonate level and product weight percentage increase have been also considered important parameters for storage stability evaluation.

The storage stability situation has been monitored after 2 weeks and 6 weeks and compared with the starting s values. A recording data table with the corresponding storage rating is reported below: Storage Synthetic Soap Sodium rating Synthetic Soap bar weight % percarbonate bar appearance (SR) increase level* (%) 0 As initial 0 from 9 to 10% 1 As initial Less than 5% from 9 to 10% 2 As initial Less than 10% from 9 to 10% 3 As initial Less than 10% from 8 to 9% 4 As initial Less than 10% from 7 to 8% Start blowing and cracking From 10 and 20% from 5 to 7% effects Evident blowing 6 and cracking More than 20% from 3 to 5% effects 7 Start soap bar More than 20% from 0 to 3% dlssolutlon *10 % is the starting sodium percarbon. ate level.

The higher the rating number, the worse the storage performance.

STAIN REMOVAL TEST: The stain removal evaluation of standard soils has been done considering the Soil Removal Index (SRI). The L*a*b* scale has been used with a spectrophotometer with the W-filter at 460 nm. SRI is described as: SRI=100-[(Lc*-Lw*)2 + (a*c-a*w)2 + (bc*-bw*)2]1/2 Where: L* = reflectance a* = redness/greeness b* = yellowness/blueness c = unstained white fabric w = washed stain SRI = 100 means a complete stain removal.

Standard prepared stains have been used for the test.

Standard stains (aged stain):

- L

Blood Proteolytic Cotton Empa 111 Empa Institute Grass Prot./oxid. Cotton Empa 164 Empa Institute Wine Oxidisable Cotton WFK 10L WFK Institute Blueb Cotton CFT CS-15 CFT Institute Lipst Greasy Cotton Empa 141 Empa Institute *Empa Test Materials in Switzerland WFK Testgewebe GmbH in Germany C.F.T.Center For Test materials B.V. in The Netherlands The cleaning procedure is done by wetting the stain with water, scrubbing the stain swatches from top to bottom 15 times. After 5 minutes the swatches are rinsed with warm water (T=40 C) and then left to dry.

COLOUR DAMAGE TEST: Three multiple washing cycles, the same previously described in the stain removal test, have been done onto blue and red, direct and reactive cotton swatches to check any potential damage of the formulations of this invention. Rin Supreme, Unilever market leader soap bars in India has been used as a reference of a very well known and established product in the market.

The cleaning procedure is done by wetting the stain with water, scrubbing the stain swatches from top to bottom 15 times. After 5 minutes the swatches are rinsed with warm water (T=40 C) and then left to dry. The cleaning procedure has been repeated twice more time in the same swatch area.

*WOK Testgewebe GmbH in Germ any The colour safety has been measured by instrumental readings after 3 washing cycles. The instrumental analysis has been carried out considering delta E values

between the unwashed and the washed fabric swatches.

The L*a*b* scale has been used with a spectrophotometer with the W-filter at 460 nm. AE is defined as per each coloured fabric considered as: LE=[(LC*-LW*) 2 + (a*C-a*w) + (bc*-bw*) ] / Where: L* = reflectance a* = redness/greenness b* = yellowness/blueness c = unwashed coloured fabric w = washed coloured fabric HE equals O means no colour damage and in general the lower the value the lower the colour damage.

EXAMPLES:

The extruded bar formulations are typically prepared by doing a neutralization step of the anionic surfactants, followed by mixing each solid ingredient together in a suitable container and spraying on top the liquids ingredients as solvents non ionic surfactants, fragrances. Examples of compositions forming a part of the present invention are set below in Tab 1, 2 and 3 with the various components identified in Tab 4.

In the examples where glycol ethers are present, the extrusion step has been done at 25 C, whereas in their absence the extrusion has been done at 60 C.

Table 1

Components Ex 1 Ex 2 Ex 3 Ex 4 Ex 5 Ex 6 Ex 7 Ex a %W/W %W/W %W/W %W/W %W/W %W/W %W/W %W/W LAS-M 20.0 15.0 15.0 15.0 15.0 15. 0 15.0 15.0 Alkyl sulfate = = = 10.0 10.0 10.0 10.0 Nonionic alcohol 5.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Ethoxylate __ Silicone Surfactant 1.0 1.5 1.5 Coated sodium percarbonate 10.0 10.0 10.0 10.0 10.0 10.0 10.0 Calcium 10. 0 10.0 10.0 10.0 peroxide TAED 3.0 3.0 3.0 3.0 HEDP 4Na 0.2 0.2 0.2 0.2 0. 2 0.2 0.2 0.2 Dowanol DPM 0.5 1.0 1.0 1.0 1.0 1.0 1.0 1.0 sulfate 14.3 20. 3 19.9 11.4 12.9 10.3 12.9 carbonate 22.0 22.0 22.0 22.0 22.0 22.0 29. 0 22.0 Calcium 27.5 27.5 27.5 27.5 25.9 27.5 27.5 27.5 carbonate Enzyme Blend 0.4 0.4 0.4 0.4 0.4 s

Table 2

Components I Ex 9 Ex 10 Ex 11 Ex 12 Ex 13 Ex 14 Ex 15 %w/w %w/w %w/w %w/w %w/w %w/w %w/w LAS-M 20.0 20.0 20.0 20.0 15.0 10.5 15. 0 Alkyl sulfate 2.0 2.0 2.0 Non-ionic alcohol 2.0 2.0 2.0 3.0 2.0 2.0 2.0 EthoxYolate Silicone 0.5 1.0 1.5 1.5 1.5 1.5 1 5 surfactant.

Coated sodium 10.0 10.0 10.0 10.0 8.0 8.0 8.0 percarbonate TAED 3.0 3.0 1. 5 Dowanol DPM 1.0 1.0 1.0 PEG 6000 6.0 HEDP 4Na 0.2 0.2 0.2 0.2 0.2 0.2 0. 2 sulfate 17.8 17.3 16.8 15.8 19.3 19.8 22.8 Sodium 22.0 22.0 22.0 22. 0 22.0 22.0 22.0 carbonate Calcium 5 1 27.5 1 27.5 1 275 27.5 1 27.5 1 27.5 1 27.

I carbonate I I I II l I l s

Table 3

Components Ex 16 Ex 17 Ex 18 Ex 19 %w/w %w/w %w/w %w/w LAS-M 18.0 18.0 18.0 18.0 Alkyl sulfate Nonionic Alcohol 2.0 2.0 2.0 2.0 ethoxylate Coated sodium 10.0 10.0 10.0 percarbonate Uncoated sodium 10.0 percarbonate

TAED

Dowanol DPM 1.0 1.0 1.0 1.0 HEDP 4Na 0.2 0.2 0.2 0.2 Sodium sulfate 19. 3 19.3 carbonate 22.0 41.3 42.3 22.0 carbonate 27.5 27.5 27.5 27.5

Table 4

Component Description of component

LAS-M Alkyl benzene sulfonic acid Alkyl sulfate Sulfopon 1218-G from Cognis Dowanol DPM Dipropylene glycol methyl ether from Dow chem.

EXAMPLE RESULTS:

The stain removal and colour safety performances have been compared with Rin Supreme, synthetic soap bar, produced by Unilever and Sole Gran Bucato, natural soap bar, produced by Reckitt Benckiser.

Results for storage stability test: In the table below are reported the storage rating values (SR) per each storage condition. SR values below or equal 3 are considered as good storage stability.

Stability test rating (SR) Product2 weeks 6 weeks 1 _ 40 C 50 C 20 C 40C 50 C Ex 9 1 2 1 2 1 2 3 3 4 2 Ex 17 0 0 0 0 0 0 0 0 1 1 Ex 18 1 2 3 1 2 4 4 2 Ex 19 0 0 0 0 0 1 0 1 1 Results for stain removal and wicking test: Rin Supreme and Sole Gran Bucato have been used as references. Per each product/stain 4 replicates have been considered and the values reported in the table below are averaged.

Stain removal Index = Sebum|Lipstick|Make up|DMO|Blueberry|Grass|Blood|Wine| Tea Ref 1* 25. 1 12.5 49.9 0.0 9.8 5.0 19.0 10.3 5.5 Ref 2* 23.4 17.2 57.0 0.0 13.2 3. 0 22.0 s.a 4.7 Ex 1 50.9 26.5 70.8 5.2 _ _ _ Ex 2 38.1 _ _ 33.4 18.4 32.9 22.2 30.0 Ex 3 39.0 _ _ 27.3 16.4 30.1 20.6 20.3 Ex 4 32.5 _ _ 30.4 11. 2 31.7 20.6 13.7 Ex 5 32.5 _ _ 29.3 13.0 30.7 16.5 10.4 Ex 6 33.3 _ _ 21. 3 8.9 27.7 11.3 9.9 Ex 7 33.5 _ _ 30.7 13.5 32.1 17.3 14.6 Ex 8 29. 9 _ _ 32.3 10.7 30.8 14.0 13.5 Ex 9 47.8 21.3 64.3 23. _ _ _ _ Ex 10 47.8 23.2 66.6 23. _ _ _ _ Ex 11 38.2 21.9 65.2 22. _ _ _ _ Ex 12 37.9 20.8 63. 7 20. _ _ _ _ Ex 13 37.6 _ _ 30.2 17.8 _ _ 25.0 Ex 14 35.7 _ _ 29.0 16. 5 _ _ 29.2 Ex 15 33.5 _ _ 24.8 15.3 _ _ 20.9 Ex 16 30.1 _ _ 37.9 21. 1 _ _ 30.3 Ex 17 32.3 _ _ 37.2 20.6 _ _ 29.6 Ex 19 30.1 _ 39.7 20. 6 _ _ 24.6 s * Ref 1 = Rin Supreme; Ref 2 = Sole Gran Bucato.

Results for colour safety: Rin Supreme synthetic soap bar has been used as a reference. Four replicates have been considered per each product/colour type and the values reported in the table below are averaged. s

Damage test Product Direct blue Reactive Direct red Reactive red

BE LE HE ME

Ref 1 1.2 1.9 3.9 7.4 Ref 2 1.5 1.3 3.7 2.4 Ex 13 1.0 2.3 4.4 6.2 Ex 16 1. 6 1.5 3.3 6.2 Ex 17 1.2 1.1 3.4 6.1 Ex 19 1.5 0.5 4.0 7.8 * Ref 1 = Rin Supreme; Ref 2 = Sole Gran Bucato

Claims (3)

1. Claims 1. An extruded fabric cleaning bar comprising: at least one anionic

   surfactant; at least one organic solvent, preferably a glycol ether; at least one builder; a solid water-soluble source of active oxygen; optionally, at least one chelating agent; optionally up to 10% w/w of a nonionic surfactant; optionally up to 10% w/w of minor ingredients selected from one or more of the following fragrance, bleach activator, enzyme, bleach catalyst and colour (pigment or dye).
2. 2. A method of manufacturing an extruded cleaning bar as described in claim 1, comprising; a) neutralization of at least one anionic acid surfactant with an alkaline source to form a solid; b) adding and mixing of all remaining solid and/or liquid raw materials, in any order; c) extruding at low temperature the resultant mixture, preferably in the range of from 10 to 40 C, preferably between 25 and 40 C; and d) cutting the extrudate.
3. 3. A method of cleaning fabric comprising the steps of (a)rubbing a fabric cleaning bar, as defined in claim 1, onto the fabric; and either (b) adding an additional cleaning composition

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   s dissolved in water to the fabric, or (c) rinsing the deposited fabric cleaning bar from the fabric with water.