CN1145094A

CN1145094A - Laundry detergent bars containing fabric softening clay and cellulase enzyme

Info

Publication number: CN1145094A
Application number: CN 95192355
Authority: CN
Inventors: E·P·发库卡吉斯; M·A·G·米拉索尔; G·V·拉马南
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1994-03-30
Filing date: 1995-03-30
Publication date: 1997-03-12
Also published as: WO1995027036A1; MA23492A1; MX9604431A

Abstract

A laundry bar containing from about 10 % to about 60 % by weight anionic surfactant, from about 5 % to about 60 % by weight detergent builder, and from about 0.02 % to about 2 % by weight of cellulase enzymes is disclosed. In a preferred embodiment, a laundry bar further comprises from about 0.5 % to about 30 % of a smectite-type softening clay, and optionally a polymeric clay flocculating agent at a level of about 0.001 % to about 30 % by weight of the fabric softening clay. A preferred clay flocculating agent is a poly(ethylene oxide) having an average molecular weight of 100,000 to about 10 million. An optionally-added detergent chelant is preferably alkali metal, alkali earth metal, and heavy metal salts of diethylenetriamine penta (methylene phosphonic acid), diethylenetriamine penta (acetic acid), ethylenediamine tetra (methylene phosphonic acid), ethylenediamine tetra (acetic acid), and mixtures thereof.

Description

Laundry detergent bar comprising fabric softening clay and cellulase

Background

The present invention relates to an improved laundry detergent bar. More particularly, the present invention relates to laundry detergent bars comprising anionic detergent surfactant, detergent builder, cellulase and fabric softening clay. Preferred compositions also include an effective amount of a clay flocculating agent.

Detergent compositions in the form of synthetic granular and liquid detergents are used in most applications for washing clothes, particularly those commonly used in mechanical washing machines. In some of these applications, laundry detergent bars containing synthetic organic surfactants and detergency builders are used to wash clothes, more often in applications where mechanical washing machines are not commonly used.

Technical developments in the field of laundry detergent bars have involved the efficient formulation of detergent bars in the cleaning of garments; it has acceptable foaming properties in both hot and cold water as well as in hard and soft water; it has acceptable practical wear rate, hardness, durability and hand feel; it has low smear (quantity); and it has a pleasant smell and appearance. Examples of laundry bars include those described in the following patents and publications: U.S. patent 3,178,370 (issued to Okenfuss on 13.4.1965, incorporated herein by reference) describes laundry detergent bars containing sodium Alkyl Benzene Sulphate (ABS), sodium tripolyphosphate, sodium bicarbonate, trisodium orthophosphate and water, and a process for producing these; philippine patent 13,778 (Anderson, 9/23.1980) describes a synthetic detergent laundry bar comprising a surfactant, an alkali metal pyrophosphate, from about 18% to about 60% alkaline earth metal carbonate, and from about 1% to about 20% water; U.S. patent 4,543,204 (issued to Gervasio 24.9.1985) discloses laundry detergent bars comprising 10-35% higher fatty alkyl sulfates, and 1-10% higher fatty acids, which make the bars more resistant to breakage during use and storage; united states patent 5,089,174 to Kaw et al, 2.18.1992, discloses an improved laundry bar comprising an anionic surfactant mixture comprising an alkyl sulfate and an alkyl benzene sulfonate to which a fatty alcohol is added to beneficially reduce the rate of attrition and improve solubility of the bar. The surfactant ratio disclosed is an alkyl sulfate/alkyl benzene sulfonate ratio of 90/10-10/90 (by weight); and philippine patent 26,860 (issued to Unilever on 11/16 1982) discloses a laundry bar. It comprises at least 1/3 a surfactant which is a primary alkyl sulphate and 12-60% of a builder consisting of at least two alkali metal phosphates selected from orthophosphates, pyrophosphates and tripolyphosphates.

Processes for producing laundry detergent bars are well known in the art. Examples of methods and processes for producing laundry bars include those described in the following patents and publications: philippines patent 23,689 (issued to Unilever on 27.9.1989) discloses a process for the manufacture of detergent bars containing 7-45% detergent surfactant which comprises neutralising the acid precursor of the detergent surfactant with an alkaline material (such as a carbonate) in the presence of a desiccant/adsorbent material such as oleum, sulphuric acid and anhydrous sulphate, followed by the addition of other ingredients and then forming the bar; and Philippines 24,551 (Unilever, 8.3.1990) disclose a process for the production of detergent bars containing 7-45% detergent surfactant and 0-60% builder which comprises neutralising the acid precursor of the detergent surfactant with an alkaline material (such as a carbonate) in the presence of 0.25-50% by weight of a siliceous material such as crystalline aluminosilicate, silica gel and amorphous silica, followed by the addition of other ingredients and then forming the detergent bar.

Examples of laundry bars containing clay as filler material include those described in Philippine patent 17712 (issued to Unilever on 11/19 1984) disclosing a bar containing detergent surfactant, builder and from 0.5 to 45% of a layered aluminosilicate filler such as bentonite and from 2.5 to 57% of a substantially water-insoluble particulate non-layered aluminosilicate filler, wherein both fillers comprise from 10 to 60% by weight of the total weight of the bar, Philippine patent 18,128 (issued to Unilever on 3/22 1985) disclosing a bar containing detergent surfactant, builder, from 0.5 to 45% of a layered aluminosilicate filler and from 10 to 60% of a non-builder, substantially water-soluble filler, wherein both fillers comprise from 10.5 to 60.5% by weight of the bar, and Philippine patent 27,321 (issued on 6/8/1993) disclosing a mixture of calcium carbonate with at least one of alkyl sulphate, a mixture of alkyl sulphate and from alkyl sulphate, the remainder of which consists of alkyl sulphate, from 70 to 60% of alkyl sulphate, from alkyl sulphate α to 52% and from the balance of the total weight of the bar.

Laundry bars containing softening clays improve the softness of garments laundered by the bars by using such clays. Examples of laundry bars comprising softening clays include those described in the following patents and publications: philippines 22,589 (Firmenich & Cie, 10.17.1988) discloses a laundry bar comprising anionic surfactant, builder and 5-50% softener, which may include up to 40% of a smectite-type clay having an ion exchange capacity higher than 50mgq/100gm, such as bentonite.

In areas where granular detergent compositions are used, particulate softening clays are often used, alone or in combination with other softening ingredients, either as part of the granular detergent composition itself or as a separate laundry additive to the water used to rinse the clothes. Clay flocculants are known to be used in conjunction with such particulate softening clays in granular detergent compositions to improve the deposition of such clays, and hence the softness of their garments. Examples of granular detergent compositions containing softening clay and clay flocculating agent include those described in the following patents and publications: european patent publication EP0,299,575-Al (The Procter & gamble company) published on 18.1.1989 discloses detergent compositions containing fabric softening smectite-type clays and a polymeric clay flocculating agent; and European patent publication EP0,313,146-Al (The Procter & Gamble Company), published 26/4/1989, discloses detergent compositions containing fabric softening smectite-type clays treated with an organic wetting agent to enhance their softening benefits, and optionally a polymeric clay flocculating agent.

Enzymes are commonly incorporated into detergent compositions. Preferred enzyme materials include commercially available amylases, neutral and alkaline proteases, lipases, peroxidases and esterases. Suitable proteases are described for example in GB-A-1243784, EP-A-0130756 and U.S. Pat. Nos. 5,185,250 and 5,204,015. Suitable amylases are disclosed in GB-A-1296839. Lipases for use in detergent compositions are disclosed in GB-A-1372034 and EP-A-0341947. WO89/099813 discloses a suitable peroxidase. Detergent compositions comprising in particular cellulases are also known. Such compositions are disclosed, for example, in U.S. patent application Ser. No. 08/119922(The Procter & Gamble Company), U.S. Pat. No. 4,435,307 and GB-A-2075028 and GB-A-2095275, filed 9/10/1993.

It is an object of the present invention to improve the color recovery and retention benefits of laundry bars containing cellulase and softening clay as well as the fabric softening benefits.

It is another object of the present invention to improve the garment softness, color recovery and retention of laundry bars containing cellulase and softening clay while providing good surfactant benefits, cleaning benefits, abrasion rate, solubility and other bar aesthetics.

Summary of The Invention

The laundry detergent bar of the present invention comprises a detergent surfactant, a detergency builder, an effective amount of a fabric softening clay and a cellulase. Preferably, the bar further comprises an effective amount of a clay flocculating agent to improve the garment softening effect of the clay and the color recovery and retention of the cellulase.

Detailed Description

While the specification concludes with claims particularly pointing out and distinctly claiming the subject matter of the present invention, it is believed that the invention will be better understood from a consideration of the following detailed description of the invention. In this specification, all percentages are by weight, all temperatures are in degrees celsius, and molecular weights are weight average and decimal, unless otherwise indicated.

Preferably, the bar comprises from about 10% to about 60% by weight anionic surfactant, from about 5% to about 60% by weight detergent builder, from 0.5% to about 30% smectite-type softening clay and from about 0.02% to about 2.0% cellulase. More preferably, the bar further comprises a polymeric clay flocculating agent in an amount of from about 0.001 to about 30% by weight of the softening clay.

Preferably, the polymeric clay flocculating agent is selected from the group consisting of polyethylene oxides, polyacrylamides, and polyacrylates having a molecular weight of about 100,000 to about 1 million. Detergent surfactant

The wash bars of the present invention typically contain from 10% to about 60% anionic surfactant. One preferred anionic surfactant for use is Alkyl Sulfate (AS) having an alkyl chain of 10 to 20 carbon atoms, branched Alkyl Benzene Sulfonate (ABS) having an alkyl chain of 10 to 22 carbon atoms, linear alkyl benzene sulfonate (LAS) having an alkyl chain of 10 to 22 carbon atoms, and mixtures thereof. Preferred bars comprise from about 15% to about 40%, more preferably from about 18% to about 32% of such anionic surfactants.

The alkyl moiety of said ABS or LAS surfactants preferably contains 10 to 16 carbon atoms, more preferably 10 to 14 carbon atoms. The most preferred alkylbenzene sulfonate surfactant is LAS.

The alkyl portion of the AS surfactant preferably contains from 10 to 18 carbon atoms, more preferably from 12 to 16 carbon atoms. The AS surfactant may comprise a mixture of a longer chain AS, such AS an AS having 16 to 18 carbon atoms, and a shorter chain alkyl group, such AS an alkyl group having 11 to 13 carbon atoms. Preferred AS surfactants include coconut alkyl sulfates, tallow alkyl sulfates, and mixtures thereof; coconut alkyl sulfates are most preferred.

The cation of ABS, LAS and AS is preferably sodium, although other useful cations include triethanolamine, potassium, ammonium, magnesium and calcium or mixtures thereof.

One preferred anionic surfactant comprises a mixture of AS and alkyl benzene sulphonate. The mixture of AS and alkylbenzene sulphonate surfactants preferably comprises AS surfactant to alkylbenzene sulphonate (weight ratio) in the range 10: 90 to 95: 5, more preferably 40: 60 to 95: 5, most preferably 75: 25 to about 90: 10. In a preferred embodiment, the detergent bar comprises a mixture of anionic surfactants comprising AS and LAS in a molar ratio of from 80: 20 to about 90: 10, more preferably from about 82: 18 to about 88: 12, most preferably from about 84: 16 to about 87: 13. Such a wash bar is disclosed in copending philippine patent application 47165-a, filed on 29/10/1993, assigned to The Procter & Gamble Company by Rodney m.wise and Belal u.siddique. Detergent builder

The detergent bars of the present invention contain from about 5% to about 60% by weight of detergent builder. Preferred wash bars contain from about 5% to about 30% builder, more preferably from about 5% to about 20%, by weight of the bar. These detergent builders can be, for example, the water-soluble alkali metal salts of phosphoric acid, pyrophosphoric acid, orthophosphoric acid, tripolyphosphoric acid, higher polyphosphoric acids and mixtures thereof. One preferred builder is a water soluble alkali metal salt of tripolyphosphate, and a mixture of tripolyphosphate and pyrophosphate. The builder may also be a non-phosphate detergent builder. Specific examples of non-phosphorus, inorganic detergency builders include the water-soluble inorganic carbonates and bicarbonates. Particularly useful herein are alkali metal (e.g., sodium and potassium) carbonates, bicarbonates, and silicates.

Sodium carbonate is a particularly preferred ingredient in detergent bars because, in addition to its use as a builder, it can also provide alkalinity to the detergent bar to improve detergency and can also act as a neutralising agent for acidic components added in bar processing, sodium carbonate being particularly preferred as an inorganic salt for neutralising acid precursors of anionic surfactants such as alkyl sulphuric acid and alkyl benzene sulphonic acid used in such detergent bars.

Aluminosilicate ion exchange materials are also useful. These aluminosilicates may be crystalline or amorphous in structure, either naturally occurring or synthetically derived. Preferred synthetic crystalline aluminosilicate ion exchange materials herein are those commercially available under the names zeolite a, zeolite B and zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material is zeolite a, having the formula:

Na₁₂[(AlO₂)₁₂·(SiO₂)1₂]·_xH₂o wherein x is from about 20 to about 30, especially about 27.

Water-soluble organic detergency builders, such as alkali metal, ammonium and substituted ammonium polycarboxylates, are also useful herein. Specific examples of useful polycarboxylate builders include the sodium, potassium, ammonium and substituted ammonium salts of the following acids: ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acid, polyacrylic acid, polymaleic acid, acrylic acid-maleic acid copolymer, polyaspartic acid, and citric acid, or these acids themselves. These polymers typically have an average molecular weight of less than about 100,000, more preferably about 1000-10,000, and other useful polycarboxylate detergency builders are those materials set forth in U.S. Pat. No.3,308,067 to Diehl, 3.7.1967, which is incorporated herein by reference. Mixtures of detergent builders may be used in the present invention.

Copolymers of acrylic acid and maleic acid are preferred as co-builders since their use in combination with fabric softening clays and clay flocculants has been found to further stabilize and improve clay deposition and fabric softening performance.

Examples of particularly preferred builders include tripolyphosphate (STPP) and sodium pyrophosphate (TSPP), and mixtures thereof. Other examples of particularly preferred builders include zeolites and polycarboxylates. Cellulase enzymes

The incorporation of cellulase improves the color retention and recovery and softening effect of the laundry bar. Without being limited by theory, cellulases hydrolyze glycosidic linkages in cellulose to small molecule monosaccharides. Washing fabrics produces microfibers and pilling on cotton fabrics, which causes the fabrics to scatter, fade and become worn. Under mechanical agitation, cellulase removes these microfibers and globules, giving the fabric a new and lighter color. Particularly preferred enzymes are Carezyme supplied by Novo Nordisk in particulate form^®A cellulase. Preferred cellulases are from 5.0T to 5,000 Cevu/g and from 1.0T to 1,000 Cevu/g.

Cellulase may be added to the bars to provide from about 0.02% to about 2%, more preferably from about 0.05% to about 0.5% by weight of the bars. Fabric softening clay

When an effective amount of fabric softening clay is incorporated with the cellulase, improvements in color retention recovery and fabric softening are observed.

The fabric softening clay is preferably a smectite type clay. Smectite-type clays can be described as swellable three-layer clays; i.e., aluminosilicates and magnesium silicates having an ion exchange capacity of at least about 50meq per 100 grams of clay. The clay particles are preferably of a size such that they are not tactilely perceptible so as to not have a gritty feel on the treated garment fabric.

There are two different classes of smectite-type clays; first, alumina is present in the silicate lattice; second, magnesium oxide exists in the silicate lattice. These smectites have the formula Al₂(Si₂O₅)₂(OH)₂And Mg₃(Si₂O₅)₂(OH)₂Corresponding to the alumina and magnesia type clays, respectively. It should be recognized that the range of water of hydration in the above formula may vary with the processing to which the clay is subjected. Furthermore, atomic substitution by iron and magnesium may occur in the smectite lattice when a metal cation such as Na⁺、Ca⁺⁺And H⁺Can coexist in the water of hydration to provide electrical neutrality. This is in addition to what is explained belowSuch cationic substitution is not important for the use of these clays, since the desired physical properties of the clay are not changed at all as a result.

The tri-layer aluminosilicates useful herein are also characterized by a dioctahedral lattice, whereas the tri-layer magnesium silicate has a trioctahedral lattice.

As explained above, the clay used in the composition of the invention comprises a cationic counterion. Such as protons, sodium ions, potassium ions, calcium ions, magnesium ions, and the like. The habit between clays is to distinguish on the basis of one cation adsorbed mainly or exclusively. For example, a sodium clay is a clay in which the adsorbed cation is predominantly sodium. Such adsorbed cations may undergo an exchange reaction with cations present in the aqueous solution. A typical exchange reaction involving a smectite-type clay is represented by the following equation:

since one equivalent weight of ammonium ion replaces one equivalent weight of sodium in the above equilibrium reaction, it is customary to measure the cation exchange capacity (sometimes referred to as "base exchange capacity") in terms of milliequivalents per 100g of clay (meq/100 g).

The cation exchange capacity of clay is a well-known parameter for determining the effectiveness of clay as a fabric softener. The cation exchange capacity can be determined by well-established analytical techniques. See, for example, H van Olphen, "Clay Colloid Chemistry," Interscience Publishers, 1963 and related references cited herein. Preferably, the clay particles used in the present invention have an ion exchange capacity of at least about 50meq/100 g.

The smectite-type clays useful in the compositions of the invention are well known and most are commercially available. Such clays include, for example, montmorillonite, chromite (volchouskoite), nontronite, bentonite, hectorite, saponite, sauconite, and vermiculite. The clays used in the present invention are available under various trade names, such as Thixogel No.1 (also "Thixo-Jell") and Gelwhite GP from Georgia Kaolin Co., Elizabeth, New Jersey; volcalay BC and volcalay No.325 from American Colloid co, Skokie, Illinois; black Hills BentoniteBH450 from International Minerals and Chemicals; and Veegum Pro and Veegum F from r.t.vanderbilt. It will be appreciated that this smectite-type mineral achieves a mixture of various expected metal entities in their entirety. Such mixtures of smectite minerals are suitable for use in the present invention.

Although any of the smectite-type clays described herein can be used in the present invention, certain clays are preferred, for example Gelwhite GP is a very white smectite-type clay and is therefore preferred when formulating white granular detergent compositions. Volclay BC is a lattice containing at least 3% iron (expressed asFe₂O₃) Of smectite type clay mineralAnd has a very high ion exchange capacity, volcalay BC is one of the most effective clays for current compositions from the viewpoint of product performance. On the other hand, certain smectite-type clays that are sufficiently contaminated with silicate minerals have ion exchange capacities below the desired range and cannot be used in current compositions.

Suitable clay minerals for use herein may be selected by virtue of the fact that: the smectite showed a true 14 AX-ray diffraction pattern. This characteristic pattern, in combination with the exchange capacity measurement performed as described above, provides a basis for selecting a particular smectite-type mineral for use in the disclosed composition.

Acid-treated bentonite or other softening clays, such as those disclosed in philippine patent 18,297 issued on 20.5.1985 and assigned to Unilever, can also be used as fabric softening clays.

Fabric softening clays may be added to the bars to provide from about 0.5% to about 30%, more preferably from about 0.5% to about 25%, even more preferably from about 5% to about 20%, and most preferably from about 5% to about 14% by weight of the bar. Clay flocculating agent

The polymeric clay flocculating agent is selected to provide improved deposition of fabric softening clay, the effect of which is to improve the garment softening effect of the clay and to improve the color recovery and retention benefits of the cellulase. Typically such materials have a high molecular weight greater than about 100,000. Examples of such materials may include long chain polymers and copolymers derived from monomers such as ethylene oxide, acrylamide, acrylic acid, dimethylaminoethyl methacrylate, vinyl alcohol, vinyl pyrrolidone, and aziridine. Gums like guar gum are also suitable.

One preferred clay flocculating agent is selected from the group consisting of high molecular weight polyethylene oxides, polyacrylamides, and polyacrylates having a molecular weight of from about 100,000 to about 1 million. It has been found that the use of a clay flocculating agent for laundry bars containing softening clay provides unexpectedly improved softening clay deposition and garment softening on garments compared to laundry bars containing softening clay alone. The amount of clay flocculating agent used in the laundry bar is preferably an effective amount to provide significantly improved fabric softening. The amount of clay flocculating agent used may vary with the type of clay flocculating agent used in the laundry bar, the type of fabric softening clay and the type and amount of other detergent adjuncts. The amount of clay flocculating agent is conveniently expressed as a weight percentage of the amount of fabric softening clay in the wash bar. The strip typically comprises, based on the weight of the fabric softening clay, from about 0.001% to about 30% clay flocculating agent, more preferably from about 0.01% to about 15%, most preferably from about 0.2% to about 5%.

The effectiveness of clay flocculants generally increases as the molecular weight of the flocculant increases. The polymers generally have an average molecular weight of from about 100,000 to about 1 million, more preferably from about 150,000 to about 5 million. As with the amount of clay flocculant, the selection of an appropriate polymer molecular weight depends on the type of clay and type of flocculant as well as the other ingredients of the composition.

Preferred clay flocculants are poly (ethylene oxide) polymers.

Optional Components

The detergent bars of the invention may contain up to about 70% by weight of optional ingredients commonly used in detergent products. A typical classification and assortment of optional surfactants, optional builders and other ingredients for use in the present invention occurs in EP550,652 published on 5/23 1972 to Norris, U.S. Pat. No.3,664, 96l and 4/16 1992, which are incorporated herein by reference. The following are representative of such substances, but are not limited thereto. Optional detergent surfactant: optional detergent surfactants may be included at levels up to about 10%, more preferably from about 0.1% to about 5% by weight of the composition. Types of detergent surfactants that may be used as optional surfactants include anionic, cationic, nonionic, amphoteric and zwitterionic surfactants and mixtures thereof.

Optional anionic surfactants useful herein as co-surfactants include: sodium alkyl glyceryl ether sulfates, particularly those derived from the higher alcohols of tallow and coconut oil;

sodium coconut oil fatty acid monoglyceride sulfonates and sulfates;

alkylphenol ethylene oxide ether sulfuric acidAnd methyl ester R-CH (SO)₃M)-COOR¹Wherein R is C₈-C₂₂Alkyl or alkenyl, R¹Is C₁-C₄Alkyl, and M is a counterion, preferably Na or K, such as those disclosed in WO-93-05013, published 3/18 1992; a sulfonate salt;

secondary alkyl sulfates having alkyl chains of 10 to 20 carbon atoms; higher fatty acids (i.e., "soaps") such as the sodium, potassium, ammonium, and alkanolammonium salts of higher fatty acids. Soaps can be prepared by direct saponification of fats and oils or by neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of fatty acid mixtures derived from coconut oil and tallow, i.e., sodium or potassium soaps of tallow and coconut oil;

the alkyl alkoxy sulfates comprise alkyl moieties of 6 to 18 carbon atoms and alkoxy moieties comprising an average of about 0.5 to about 20 moles of alkoxy, preferably ethoxy units, more preferably about 0.5 to about 5 moles of ethoxy units; and

formula RO (CH)₂CH₂O)_xCH₂COO^-M⁺Wherein R is C₆-C₁₈An alkyl group; x is from 0 to 10, and the ethoxylate distribution is such thatCalculated, the amount of material with x being 0 is less than 20%, the amount of material with x being greater than 7 is less than 25%, and wherein when the R average is C₁₃Or less x is 2 to 4 on average, and when R is greater than C₁₃The average value of x is 3-6; and M is an alkali metal, an alkaline earth metal, ammonium, mono-, di-and triethanolammonium.

Other optional surfactants may be nonionic and may include:

alkyl polysaccharides, alkyl polyglycosides, such as described in U.S. Pat. No. 4,565,647 to lleado;

of the formula R-C (O) -N (R)¹) Polyhydroxy fatty acid amides of-Z, wherein R is C₅-C₃₁Hydrocarbyl, preferably C₁₁-C₁₇Alkyl or alkenyl, R¹Is H, C₁-C₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or mixtures thereof, preferably methyl, and Z is a group having at least 3 direct linkagesPolyhydroxy (straight chain) hydrocarbyl chains to hydroxy groups in the chain, preferably-CH₂-(CHOH)₄-CH₂OH, such as described in EP550,652;

semi-polar nonionic surfactants such as water-soluble amine oxide, water-soluble phosphine oxide and water-soluble sulfoxide surfactants; and

water-soluble nonionic synthetic surfactants, which are broadly defined as compounds prepared by the condensation of an oxirane group (hydrophilic in nature) with an organic hydrophobic compound which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyethylene group condensed with any individual hydrophobic group can be easily adjusted to give a water-soluble compound having a desired degree of balance between hydrophilic and hydrophobic portions.

Cationic surfactants may also be used in the detergent compositions of the present invention, suitable quaternary ammonium surfactants being selected from mono-C₆-C₁₆Preferably C₆-C₁₀N-alkyl or alkenyl ammonium surfactants in which the remaining N moiety is substituted with methyl, hydroxyethyl or hydroxypropyl groups.

Optional surfactants also include amphoteric surfactants including aliphatic derivatives of heterocyclic secondary and tertiary amines, zwitterionic surfactants including derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, water-soluble α -sulfonated fatty acid ester salts, alkyl ether sulfates, water-soluble salts of olefin sulfonates, β -alkoxy alkane sulfonates, surfactants having the formula R (R)¹)₂N⁺R²COO^-Wherein R is C₆-C₁₈A hydrocarbyl radical, preferably C₁₀-C₁₆Alkyl radicals or C₁₀-C₁₆An amidoalkyl group, each R¹Is generally C₁-C₃Alkyl, preferably methyl and R₂Is C₁-C₅A hydrocarbyl radical, preferably C₁-C₃Alkylene group, more preferably C₁-C₂An alkylene group. Examples of suitable betaines include cocoamidopropyl dimethyl betaine; cetyl dimethyl betaine; c_12-14Amidopropyl betaine; c_8-14Amide compoundHexyl diethylbetaine; 4[ C ]_14-16Methylamino diethylamino]-1-carboxybutane; c_16-18Amido dimethyl betaine; c_12-16Amidopentane diethylbetaine; and C_12-16Acyl methylamino dimethyl betaine.The preferred betaine is C_12-18Dimethyl-aminocaproate salt and C_10-18Amidopropane (or ethane) dimethyl (or diethyl) betaine; and has the formula (R)¹)₂N⁺R²SO₃ ^-Wherein R is C₆-C₁₈A hydrocarbyl radical, preferably C₁₀-C₁₆Alkyl radical, more preferably C₁₂-C₁₃Alkyl radical, each R¹Is generally C₁-C₃Alkyl, preferably methyl, and R²Is C₁-C₆A hydrocarbyl radical, preferably C₁-C₃Alkylene or preferably hydroxyalkylene groups. Examples of suitable sulfobetaines include C₁₂-C₁₄Dimethylamino-2-hydroxypropyl sulfonate, C₁₂-C₁₄Amidopropylamino-2-hydroxypropyl sulfobetaine, C₁₂-C₁₄Dihydroxyethyl aminopropane sulfonate, and C_16-18Dimethylaminohexane sulfonate, preferably C_12-14Amidopropylamino-2-hydroxypropyl sulfobetaine.

In addition to the above co-surfactants, a hydrotrope or mixture of hydrotropes may be used in laundry detergent bars. Preferred hydrotropes include alkali metal salts of toluene sulfonic acid, xylene sulfonic acid, cumene sulfonic acid, sulfosuccinic acid and mixtures thereof, preferably the sodium salt thereof. Preferably, a hydrotrope, present in acid or salt form and substantially anhydrous, is added to the linear alkyl benzene sulphonic acid and then neutralised. The hydrotrope is preferably present in an amount of from about 0.5% to about 5% of the laundry detergent bar. Detergent sequestrant: a particularly preferred optional component of the present invention is a detergent sequestrant. Such chelating agents are capable of sequestering and chelating alkali metal cations (such as sodium, lithium and potassium), alkaline earth metal cations (such as magnesium and calcium) and most preferably heavy metal cations such as iron, manganese, zinc and aluminum. Preferred cations include: sodium, magnesium, zinc and mixtures thereof. Detergent sequestrants are particularly beneficial in maintaining good cleaning and improved surfactant benefits despite the presence of softening clays and clay flocculants. Without being bound by any theory, it is believed that the soft clay structure comprises iron (Fe) and other transition metal ions. During the washing process, the transition metal ions can be displaced into the wash solution by calcium and magnesium substitution in the wash water and in the scale of iron or other transition metal ions. These metal ions are known to cause yellowing and graying of fabrics. Detergent sequestrants can significantly reduce these effects.

The detergent chelant is preferably a phosphate chelant, specifically a chelant selected from the group consisting of diethylenetriamine pentamethylenephosphonic acid, ethylenediamine tetramethylene phosphonic acid and mixtures, salts and complexes thereof, and an acetate chelant, specifically a chelant selected from the group consisting of diethylenetriamine pentaacetic acid, ethylenediamine tetraacetic acid and mixtures, salts and complexes thereof. Particularly preferred are the sodium, zinc, magnesium and aluminum salts of diethylenetriamine pentamethylenephosphonic acid, diethylenetriamine pentaacetic acid, and mixtures and complexes thereof. Preferably such salts or complexes have a molar ratio of metal ion to chelator molecules of at least 1: 1, preferably at least 2: 1.

The detergent chelant may be included in the laundry bar in an amount up to about 5%, preferably from about 0.1% to about 3%, more preferably from about 0.2% to about 2%, most preferably from about 0.5% to about 1.0%. Such a detergent chelant component may be used to beneficially improve the surfactant benefit of the laundry bar of the present invention by implying that for a given amount of anionic surfactant and a given amount of detergent chelant, comparable sudsing and cleaning results are achieved compared to a similar laundry bar containing a higher amount of anionic surfactant without detergent chelant.

The detergent sequestrant may be applied in particulate or granular form, or as a water or solvent solution. Methods for preparing these salts and complexes are well known, as described in U.S. Pat. No. 4,259,200 issued to 3/31/81, the disclosure of which is incorporated herein by reference. One preferred form is fine or granular. The granules and particles of the detergent sequestrant may be formed from an organic or inorganic binding material. One suitable organic binding material is, for example, a nonionic surfactant. Suitable inorganic binder materials include sodium tripolyphosphate, sodium carbonate, magnesium sulfate, and the like. Any granulation technique known in the art may be used, for example by spraying molten nonionic surfactant onto a moving bed of metal complex to be dried, fluid bed drying, etc.

In addition to cellulases, another particularly preferred component is a detergent enzyme. Non-limiting types of enzymes include cellulases, lipases, amylases, lipolytic enzymes (Lipolase), maleases, proteases, catalases, maltases and phosphatases. Especially preferred are cellulases, lipases, proteases, amylases, and mixtures thereof. The enzyme is advantageously used in an amount of up to 5%.

Another useful optional component of the laundry detergent bars of the present invention is a silicate, especially sodium or magnesium silicate. Sodium silicate, which may be used in an amount up to about 15% silicate solids, may have a weight ratio of SiO₂∶Na₂O is from about 1.0: 1 to about 3.4: 1.

Another preferred additional component is a layered crystalline alkali silicate. One preferred commercially available layered silicate is referred to as "SKS-6" (Na)₂Si₂O₅) From Hoechst and disclosed in us patent 4,664,839 issued on 12.5.1987. Another preferred layered silicate is disclosed in EP publication 550,048(Kao), 7.7.1993, which discloses a synthetic crystalline material having a chain structure and a composition in anhydrous form of the formula:

_xM₂O·_ySiO₂·_zM¹o, wherein M represents Na and/or K; m¹Represents Ca and/or Mg; y/x is 0.5-2.0; andz/x is 0.005-1.0, and the chain structure is 900-1200cm in Raman spectrum^-1Within a range of at least 970 + -20 cm^-1A major dispersion peak appears. Such a layered silicate material is particularly preferred, since it may beProviding alkalinity and calcium sequestering or builder functionality.

Another preferred adjunct ingredient to the laundry bar is a fatty alcohol having an alkyl chain of from 8 to 22 carbon atoms, more preferably from 12 to 18 carbon atoms. Fatty alcohols are effective in reducing the bar wear rate and rub-off (mushiness) of current laundry bars. One preferred fatty alcohol has alkyl chains containing predominantly 16-18 carbon atoms, so-called "high cut fatty alcohols," which may exhibit a lower fatty alcohol-based odor relative to wide cut fatty alcohols. Typically the fatty alcohol is included in the laundry bar in an amount up to 10%, more preferably from about 0.75% to about 6%, most preferably from about 2% to about 5%. Fatty alcohols are typically added to the formulations of the present invention as free fatty alcohols. However, small amounts of fatty alcohol may be added to the bars as impurities or as unreacted starting material. For example, laundry bars based on coconut fatty alkyl sulphate may contain as unreacted starting material from 0.1% to 3.5%, more typically from 2% to 3%, by weight of free coconut fatty alcohol calculated on the basis of coconut fatty alkyl sulphate.

The free fatty alcohol may also act as a foam booster to enhance and extend foam formation and durability. For the foam booster, a preferred fatty alcohol has an alkyl chain containing primarily 12-14 carbon atoms and is used in the composition in an amount of about 0.5% to 3%. Preferably, the narrow fraction C₁₂The alkanol is used in an amount of 0.5% to 2%.

Another preferred laundry component may comprise a soil release polymer. Such soil release polymers may be used in amounts up to 5%, preferably from about 0.05% to about 3%, more preferably from about 0.2% to about 1.0%. Soil release polymers can improve the multi-cycle cleaning of garments laundered with laundry bars. Preferred soil release polymeric materials include those disclosed in U.S. patent 4,877,896 issued at 31.10.1989 and U.S. patent 5,182,043 issued at 26.1.1993, the disclosures of which are incorporated herein by reference.

Preferred soil release polymers are substantially linear esters having a sulfoaroyl end-capping unit molecular weight of from about 500 to about 20,000, wherein said esters comprise, on a molar basis:

(i) about 1 to about 2 moles of sulfobenzoyl end-cappedFormula (MO)₃S)(C₆H₄) -units of CO-, wherein M is a salt-forming cation;

(ii) from about 2 to about 50 moles of oxy-1, 2-propenyloxy units or mixtures thereof with oxyethylene oxy units, provided that the molar ratio of oxy-1, 2-propenyloxy to oxyethylene oxy is from about 1: 10 to about 1: 1; and

(iii) (iv) about 1 to about 40 moles of terephthaloyl units, provided that said units defined by (ii) and (iii) are present in a molar ratio of about 2: 1 to about 1: 24; and, for each mole of said ester, may also contain:

(iv)0 to about 30 moles of a compound of the formula- (O) C (C)₆H₃)(SO₃M) 5-sulfoisophthaloyl units of C (O) -wherein M is a salt-forming cation; or

(v)0 to about 25 moles of a compound of the formula- (OCH)₂CH₂)_nPoly (oxyethylene) oxy units of O-, wherein the average degree of ethoxylation, n, is from 2 to about 100; or

(vi) (vi)0 to about 30 moles of said mixture of units (iv) and (v) in a molar ratio of about 29: 1 to about 1: 29.

Preferably, said substantially linear, sulfoaroyl end-capped ester comprises, on a molar basis:

(i) about 2 moles of formula (MO)₃S)(C₆H₄) A sulfoaroyl end-capping unit of-C (O) -wherein M is sodium;

(ii) about 14 moles of oxy-1, 2-propenyloxy units or mixtures thereof with oxyethylene oxy units, having oxy-1, 2-propenyloxy groups; an oxyethylene oxy molar ratio of about 1: 0 to about 1: 7; and

(iii) about 11 moles of terephthaloyl units; and

(iv) about 2 moles of a compound of the formula- (O) C (C)₆H₃)(SO₃M) 5-sulfoisophthaloyl units of C (O) -wherein M is sodium,

and wherein at least 20% of the esters are esters having a molecular weight of about 800-20,000.

Another preferred soil release polymer is a sulfonated polyethoxy/propoxy end-capped ester oligomer comprising: (i) about 1 to about 2 moles of formula ((MO)₃S)CH₂)_m(CH₂)_m(CH₂CH₂O)(RO)_n-sulfonated polyethoxy/propoxy end-capping units wherein M is a salt-forming cation selected from sodium and tetraalkylammonium, M is 0 or 1, R is ethylene, propylene or mixtures thereof, and n is 0-2; (ii) from about 0.5 to about 66 moles of units selected from: a) an oxyethylene oxy unit; b) a mixture of oxyethylene oxy and oxy-1, 2-propyleneoxy units wherein said oxyethylene oxy units are present in a molar ratio of oxyethylene oxy to oxy-1, 2-propyleneoxy of from 0.5: 1 to about 10: 1; and c) a mixture of a) or b) with poly (oxyethylene) oxy units, wherein said poly (oxyethylene) oxy units have a degree of polymerization of 2 to 4; with the proviso that when the degree of polymerization of said poly (oxyethylene) oxy units is 2, the molar ratio of poly (oxyethylene) oxy units to units in total ii) is from 0: 1 to about 0.33: 1, and when the degree of polymerization of said poly (oxyethylene) oxy units is 3, the molar ratio of poly (oxyethylene) oxy units to units in total ii) is from 0: 1 to about 0.22: 1; and when the degree of polymerization of said poly (oxyethylene) oxy units is 4, the molar ratio of poly (oxyethylene) oxy units to units in ii) as a whole is from 0: 1 to about 0.14: 1; iii) about 1.5 to about 40 moles of terephthaloyl units;and (iv)0 to about 26 moles of a compound of the formula- (O) C (C)₆H₃)(SO₃M) 5-sulfoisophthaloyl units of C (O) -wherein M is a salt-forming cation. Preferably, such ester oligomers have a molecular weight of from about 500 to about 20,000, more preferably from about 500 to about 5,000.

One particularly preferred ester oligomer polymer has the formula: NaO₃S(CH₂CH₂O)₂-C(O)-(C₆H₄)-C(O)O-[-CH₂CRH-O-C(O)-(C₆H₄)-C(O)O-]₄--[-CH₂CRH-O-C(O)-(C₆H₄)SO₃Na-C(O)O-]₁-CH₂CH₂OCH₂CH₂SO₃Na wherein R is H or CH in a molar ratio of about 1.8: 1₃。

The soil release polymer may be added to the bar composition during manufacture in liquid or granular form. In a preferred embodiment, the soil release polymer is in the form of low density, porous particles. Such porous soil release polymer forms may be manufactured by spray drying soil release polymers in liquid form, alone or with one or more carrier materials, to remove substantially all of the free water or other solvent liquid, by spray drying methods well known in the art.

Another preferred optional component in the laundry bar is a Dye Transfer Inhibition (DTI) ingredient to prevent a reduction in fabric color fastness and strength. A preferred DTI component may comprise a polymeric DTI material capable of binding fade dyes to prevent their deposition onto fabrics, and a decolorizing DTI material capable of decolorizing fade dyes by oxidation. An example of decolorizing DTI is hydrogen peroxide or a source of hydrogen peroxide, such as percarbonate or perborate. Non-limiting examples of polymeric DTI materials include polyvinylpyridine N-oxide, polyvinylpyrrolidone (PVP), PVP-polyvinylimidazole copolymer, and mixtures thereof.

More specifically, the polyamine N-oxides preferred for use herein comprise units having the following structural formula: R-A_x-P; wherein P is a polymerizable unit to which an N-O group may be attached or an N-O group may form part of a polymerizable unit, or an N-O group may be attached to both units; a is one of the following structures: -nc (O) -, -c (O) O-, -S-, -O-, -N ═ O; x is 0 or 1; and R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group or any combination thereof to which the N of the N-O group may be attached or which is part of these groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.

The N-O group can be represented by the following general formula:

wherein R is₁、R₂、R₃Is aliphatic, aromatic, heterocyclic or alicyclic group or combinations thereof; x, y and z are 0 or 1; and the N of the N-O group may be linked to or form part of any of the above groups. The amine oxide units of the polyamine N-oxides have a pKa of < 10, preferably a pKa of < 7, more preferably a pKa of < 6.

Any polymer backbone can be used so long as the amine oxide polymer formed is water soluble and has dye transfer inhibiting properties. Examples of suitable polymer backbones are polyvinyl, polyalkylene, polyester, polyether, polyamide, polyimide, polyacrylate, and mixtures thereof. The polymer may comprise random or block copolymers wherein one monomer type is an amine N-oxide and the other monomer type is an N-oxide. Amine N-oxides generally have a ratio of amine to amine N-oxide of from 10: 1 to 1: 1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can vary with the appropriate copolymerization or with the appropriate degree of N-oxidation. Polyamine oxides of almost any degree of polymerization can be obtained. Generally, the average molecular weight is 500-; more preferably 1,000-500,000; most preferably 5,000 and 100,000.

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (known as "PVPI") are also preferred for use in the present invention. Preferably, the PVPI has an average molecular weight of 5,000-1,000,000, more preferably 5,000-200,000, and most preferably 10,000-20,000. (the average molecular weight range is determined by light scattering as described by Barth et al, Chemical Analysis, Vol 113, "modern methods of Polymer Characterization. the disclosure is incorporated herein by reference.) the PVPI copolymer typically has a molar ratio of N-vinylimidazole to N-vinylpyrrolidone of 1: 1 to 0.2: 1, more preferably 0.8: 1 to 0.3: 1, most preferably 0.6: 1 to 0.4: 1. These polymers may be linear or branched.

The compositions of the present invention may also contain polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000. Examples of PVP are disclosed in, for example, EP-A-262,897 and EP-A-256,696, which are incorporated herein by reference. Compositions containing PVP may also contain polyethylene glycol ("PEG") having an average molecular weight of from about 500 to about 100,000, preferably from about 1,000 to about 10,000. Preferably, the weight ratio of PEG to PVP is from about 2: 1 to about 50: 1, more preferably from about 3: 1 to about 10: 1.

One or more polymeric DTI materials may also be combined with one or more decolorizing DTI materials. The DTI material is advantageously used in the strip in an amount of up to about 10%, preferably from about 0.05% to about 5%, more preferably from about 0.2% to about 2%.

In addition to the softening clay, another preferred optional component of the laundry bar is a secondary fabric softening component. Such materials may be used in amounts of about 0.1% to 5%, more preferably 0.3% to 3%, and do not include: formula R₄R₅R₆Amine of N, wherein R₄Is C₅-C₂₂Hydrocarbyl radical, R₅And R₆Independently of C₁-C₁₀A hydrocarbyl group. One preferred amine is ditallow methyl amine; these amines are reacted with a compound of the formula R₇Complexes of COOH fatty acids, in which R₇Is C₉-C₂₂Hydrocarbyl, as disclosed in Ep No.0,133,804; these amines are reacted with a compound of the formula R₈-O-P(O)(OH)-OR₉And HO-P (O) (OH) -OR₉Of phosphoric acid esters of (a) wherein R₈And R₉Independently of the formula-alkyl- (OCH)₂CH₂) C of alkyl ethoxylates₁-C₂₀An alkyl group; cyclic amines such as imidazolines of the general formula 1- (higher alkyl) amido (lower alkyl) -2- (higher alkyl) imidazolines, wherein the higher alkyl group contains 12-22 carbons and the lower alkyl group contains 1-4 carbons, such as described in british patent application GB2,173,827; and formula R₁₀R₁₁R₁₂R₁₃N⁺X^-Wherein R is₁₀Is an alkyl group having 8 to 20 carbons, R₁₁Is an alkyl group having 1 to 10 carbons, R₁₂And R₁₃Alkyl having 1-4 carbons, preferably methyl, and X is an anion, preferably CI^-Or Br^-E.g. C_12-13Alkyl trimethyl ammonium chloride.

And another optional component in the laundry bar is a bleaching component. The bleaching component may be^-OOH-based sources such as sodium perborate monohydrate, sodium perborate tetrahydrate, and sodium percarbonate. Sodium percarbonate (2 Na)₂CO₃·3H₂O₂) Is preferred because it has the dual function of a source of HOOH and a source of sodium carbonate.

Another optional bleaching component is the peracid itself, formula:

CH₃(CH₂)_w-NH-C(O)-(CH₂)_zCO₃h wherein Z is 2-4 and W is 4-10. (the latter compound in which Z is 4-and W is 8 is hereinafter referred to as NAPAA). The bleach component may comprise bleach component stabilisers, polyaminocarboxylic acid sequestrants, polyaminocarboxylic acids such as ethylenediaminotetraacetic acid, triethylenetriaminepentaacetic acid and ethylenediaminodisuccinic acid and water soluble alkali metal salts thereof, and may be added to the strip in an amount of up to 20%, preferably from about 1% to about 10%, more preferably from about 2% to about 6%.

Sodium sulfate is a well known filler that is compatible with the compositions of the present invention. Sodium sulfate may be a by-product of the surfactant sulfation and sulfonation processes, or may be added separately.

Calcium carbonate (also known as Calcarb) is also well known and is often used as a component of laundry bars. Such materials are generally used in amounts up to 40%, preferably from about 5% to about 25%.

Adhesives that hold the strips together in a cohesive, soluble form may also be used and include natural and synthetic starches, gums, thickeners and mixtures thereof.

Soil suspending agents may be used. In the present invention, their use is balanced with a fabric softening clay/clay flocculant system to provide optimum cleaning and fabric softening benefits. Soil suspending agents may also include carboxymethyl cellulose and water soluble salts of carboxymethyl cellulose. A preferred soil suspending agent is an acrylic acid/maleic acid copolymer, commercially available under the name Sokolan^®Commercially available from BASF corp. Other soil suspending agents include polyethylene glycols having a molecular weight of about 400-10,000, ethoxylated mono-and polyamines, and quaternary salts thereof.

Optical brighteners are also preferred optional ingredients in the laundry bars of the present invention. Preferred optical brighteners are diaminostilbene and stilbene-biphenyl type optical brighteners. Examples of preferred such optical brighteners are 4,4 ' -bis { [ 4-anilino-6-bis (2-hydroxyethyl) amino-1, 3, 5-triazin-2-yl ] amino } stilbene-2, 2 ' -disulfonic acid disodium salt, 4,4 ' -bis (2-sulfostyryl) biphenyl and 4,4 ' -bis [ (4-anilino-6-morpholino-1, 3, 5-triazin-2-yl) amino ] stilbene-2, 2 ' -disulfonic acid disodium salt. Such optical brighteners or mixtures thereof may be used in the wash bar in amounts of about 0.05% to 1.0%.

Dyes, pigments, bactericides, and perfumes may also be added to the wash bar composition. Processing:

the detergent laundry bars of the invention may be processed using conventional soap or detergent bar manufacturing equipment with some or all of the following major equipment: blender/mixer, mill or refining plodder, two-stage vacuum plodder, edge-printing lettering device/cutter, cooling tunnel, and packaging machine.

In a typical process, cellulase enzymes, fabric softening clay and optionally clay flocculating agents are typically mixed with other materials in a blender. Alkyl benzene sulphonic acid (when used) is added to a mixture of basic inorganic salts (preferably including sodium carbonate) and the resulting partially neutralised mixture is mechanically treated to achieve homogeneity and complete neutralisation of the mixture. Once the neutralization reaction is complete, the alkyl sulfate surfactant is added, followed by the addition of the other ingredient materials. Mixing may be carried out for 1 minute to 1 hour, with conventional mixing times of 2 to 20 minutes. The blender mixture was discharged to the surge tank. The product is transferred from the surge tank to a mill or refiner-plodder via a multi-work transfer conveyor.

The alkylbenzenesulfonic acids (HLAS) can be prepared by well-known methods, such as with SO₃Or oleum. It may preferably include an excess of inorganic sulfuric acid (H) in the HLAS material₂SO₄) This helps to raise the temperature of the product through neutralization due to the heat of neutralization of the inorganic sulfuric acid.

Additionally, the cellulase, fabric softening clay and clay flocculant may be added independently at other times or locations in the process, depending on the type of equipment and type of formulation being made.

After grinding or preliminary pressing, the product is then conveyed to a secondary vacuum plodder operating at high vacuum, for example 600-. The product is extruded and cut into the desired lengths and then printed with the product brand name. The printed strips can be cooled, for example in a cooling tunnel, and then packaged, boxed and stored.

Examples of the inventive strip are listed below by way of illustration, but not by way of limitation.

Examples

Various bar compositions can be made by the above-described methods.

Example number

1 2 3 4 5 6

(weight percent) alkyl sulfate 25.5025.5025.5025.5025.5025.50 Na (C)_12-18)LAS 4.50 4.50 4.50 4.50 4.50 4.50Na₂CO₃3.003.003.003.003.003.00 calcium carbonate 42.2142.1642.0632.2132.1632.06 cellulase¹0.050.10.20.050.10.2 Bentonite Clay 101010 fluorescent whitening agent 0.200.200.200.200.200.20 acrylate 0.440.440.440.440.440.44 organic Polymer 2.002.002.002.002.002.00 TiO₂ 1.00 1.00 1.00 1.00 1.00 1.00

… … … … … … … residual ingredient 2 … … … … … … … … …

1. Carezyme supplied by Novo Nordisk having an activity of 5000Cevu/gm starting material^®A cellulase.

2. The remaining ingredients include water (about 2% -8%, including water of hydration), sodium sulfate, calcium carbonate, and other minor ingredients. Various bar compositions may be prepared by the methods described above.

Example number

7 8 9 10 11 12 13 14 15 16

(weight percent) NaCFAS (C)_12-18) 19.13 16.88 25.50 22.50 22.50 13.50 13.50 25.50Na(C_12-18)LAS 3.38 5.63 4.50 20.00 25.00 4.50Na₂CO₃ 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00DTPP¹ 0.70 0.70 0.70 0.70 0.70 0.70 0.70 0.70 0.70 1.50PEO-300M²0.300.300.300.300.300.15 PEO-600M 0.200.200.20 PEO-1.2MM 0.15 Bentonite Clay 10.010.010.010.012.012.012.010.012.010.0 Sokolan CP-5³0.700.700.700.700.700.701.000.700.700.70 TSPP 5.005.00 STPP 15.0015.005.015.0010.0010.0015.0015.005.00 Zeolite 1.251.251.251.251.251.2525.002.502.502.00 sodium laurate 9.009.00 SRP-A⁴ 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.300.15 protease⁵0.100.100.100.100.10 Amylase⁶0.750.750.750.75 Lipase 0.100.10 cellulase⁷ 0.15 0.15 0.15 0.15

The remaining ingredients⁸

1. Sodium diethylenetriamine pentaphosphonic acid.

2. PEO is a poly (ethylene oxide) with the indicated molecular weight.

3. Sokolan CP-5 is a maleic acid-acrylic acid copolymer.

4. SRP-A is

NaO₃S(CH₂CH₂O)₂-C(O)-(C₆H₄)-C(O)O-[-CH₂CRH-O-C(O)-(C₆H₄)-C(O)O-]₄-

-[-CH₂CRH-O-C(O)-(C₆H₄)SO₃Na-C(O)O-]₁-CH₂CH₂OCH₂CH₂SO₃Na，

Wherein R is H or CH in a ratio of about 1.8: 1₃。

5. Protease activity was 1Au/gm of starting material.

6. The amylase activity was 100,000amu/gm of starting material.

7. Carezyme supplied by NovoNordisk having an activity of 5000Cevu/gm starting material^®A cellulase.

8. The remaining ingredients include water (about 2% -8% including water of hydration), sodium sulfate, calcium carbonate and other minor ingredients.

Claims

1. A laundry detergent bar comprising:

(a) from about 10% to about 60% by weight of an anionic surfactant,

(b) from about 5% to about 60%, by weight, of a detergent builder, and

(c) from about 0.02% to about 2%, by weight, of cellulase enzyme, and

(d) from about 0.5% to about 30% by weight of fabric softening clay to improve the color restoration and retention effects of the cellulase.

2. A laundry detergent bar according to claim 1 further comprising from about 0.001% to about 30%, by weight of the fabric softening clay, of a polymeric clay flocculating agent to improve the garment softening effect of the fabric softening clay and the color restoration and maintenance effect of the cellulase enzymes.

3. A laundry detergent bar according to claim 1 comprising from about 0.5% to about 30% smectite-type fabric softening clay.

4. A laundry bar according to claim 1 wherein said anionic surfactant is selected from the group consisting of alkyl sulfates having an alkyl chain of from 10 to 20 carbon atoms, linear alkyl benzene sulfonates (LAS) having an alkyl chain of from 10 to 22 carbon atoms, branched Alkyl Benzene Sulfonates (ABS) having an alkyl chain of from 10 to 22 carbon atoms, and mixtures thereof.

5. The laundry bar of claim 4 wherein the surfactant comprises a mixture of Alkyl Sulphate (AS) and linear alkyl benzene sulphonate (LAS) in a molar ratio AS: LAS of from 50: 50 to 100: 0.

6. The laundry bar of claim 1 wherein the detergent builder comprises sodium tripolyphosphate, tetrasodium pyrophosphate, or mixtures thereof.

7. A laundry bar according to claim 6 wherein the builder is 5% to 20% sodium tripolyphosphate.

8. A laundry detergent bar comprising:

(a) from about 15% to about 30% of an anionic surfactant selected from the group consisting of alkyl sulfates, alkyl benzene sulfonates, and mixtures thereof.

(b) From about 5% to about 20% of a phosphate builder selected from the group consisting of tripolyphosphates, pyrophosphates, and mixtures thereof,

(c) from about 0.02% to about 2.0% cellulase, and

(d) from about 5% to about 14% smectite-type fabric softening clay.

9. A laundry bar according to claim 8 comprising from about 0.05% to about 0.50% cellulase.

10. A laundry bar according to claim 8 further comprising polymerized polyethylene oxide as a clay flocculating agent in an amount of from about 0.2% to about 5% by weight of the fabric softening clay and having a molecular weight of from 150,000 to 3 million.