BACKGROUND In societies where mechanical washing machines are not common, laundry detergent bars comprising synthetic organic surfactants and detergency builders are used in the laundering of clothes. Technical developments in the field of laundry detergent bars have concerned formulating bars which are effective in cleaning clothes ; which have acceptable sudsing characteristics in warm and cool water and in hard and soft water; which have acceptable in-use wear rates, hardness, durability, and feel ; which have low smear; and which have a leasing odor and appearance.

Laundry bar compositions typically contain peroxygen bleach, such as perborate and percarbonate bleach. Peroxygen bleach compounds have been used commercially as a source of active oxygen in bleaching, detergent, cleaning, rinsing, and scouring formulations. Although not wanting to be limited by theory, their effectiveness is believed to result from an oxidative process which decolorizes or removes impurities or foreign matter from the material being treated.

Based on the foregoing, there is a continuing desire to provide laundry bar compositions with peroxygen bleach having improved physical properties. In addition, there is a need for peroxygen containing bleach bars with a lower evolution of oxygen gas so that the bar composition has improved physical properties.

None of the existing art provides all of the advantages and benefits of the present invention.

SUMMARY The present invention is directed to a laundry detergent bar composition having calcium peroxide.

A preferred bar composition contains from about 0.1% to about 30% of calcium peroxide.

These and other features, aspects, and advantages of the present invention will become evident to those skilled in the art from a reading of the present disclosure.

DETAILED DESCRIPTION While the specification concludes with claims particularly pointing out and distinctly claiming the invention, it is believed the present invention will be better understood from the following description.

All percentages are by weight of total composition unless specifically stated otherwise.

All ratios are weight ratios unless specifically stated otherwise.

As used herein,"comprising"means that other steps and other ingredients which do not affect the end result can be added. This term encompasses the terms"consisting of"and"consisting essentially of'.

All cited references are incorporated herein by reference in their entireties.

Citation of any reference is not an admission regarding any determination as to its availability as prior art to the claimed invention.

Laundry bars which contain perborate bleach may have less than acceptable physical properties, after the bars have been exposed to water during consumer use. Although not wanting to be limited by theory, it is believed that as

the perborate bleach is exposed to the wash water, the perborate dissolves and releases hydrogen peroxide, a source of a high evolution of oxygen gas. Due to the high evolution of oxygen gas within the laundry bar, layering of the bar may result. Laundry bars that have layering is undesirable, as the bar may easily break, become crumbly when handled by the consumer during the wash, and dissolve rapidly during use. The word"layering"in this document means "cracking"or"to be cracked"on the side of the bar.

Calcium Peroxide The composition of the present invention contains calcium peroxide.

Although not wanting to be limited by theory, as compared to perborate bleach, it is believed that calcium peroxide results in less evolution of oxygen gas when exposed to the wash water. Therefore the physical property of the bar is improved if the peroxygen bleach used in the bar composition is replace with calcium peroxide wholly or in part.

Calcium peroxide is described in The Merck Index, 11 Ih Edition. Calcium peroxide's chemical formula is described as Ca02. Hydrates of CaO2 and mixtures of hydrates and CaO2 can also be used. One example of a calcium peroxide hydrates is CaO28H2O. Calcium peroxide is commercially available by FMC, L'Air Liquide, Nippon Peroxide (Japan), Shimakyo Chemical (Japan), Solvay Deutschland, Solvay Interox (United Kingdom), and Tomita Seiyaku (Japan) but any other commercially available material also can be used for the present invention. Example of calcium peroxide include CaO2 (non hydrate), Ca028H20 or any hydrates. A preferred calcium peroxide is Ca02.

Commercial calcium peroxide is usually a mixture made by the reaction of calcium hydroxide and hydrogen perxide. Commercially available materials usually contain about 60-75% CaO2, with the remainder being a mixture of calcium oxide, calcium hydroxide, and calcium carbonate.

In a preferred calcium peroxide of the present invention, the AVO (Available oxygen) should be from about 5 ppm to 44 ppm, preferably from about 10 ppm to 44 ppm, more preferably from about 20 ppm to 44 ppm. The calcium peroxide in the detergent composition is preferably at a level from about 0.10 % to about 30 % by weight; more preferably, from about 1% to about 10%; most preferably, from about 3% to about 6%.

Oxygen bleaches deliver"available oxygen" (AvO) or"active oxygen" which is typically measurable by standard methods such as iodide/thiosulfate

and/or ceric sulfate titration. See the well-known work by Swern, or Kirk Othmer's Encyclopedia of Chemical Technology under"Bleaching Agents".

When the oxygen bleach is a peroxygen compound, it contains-O-O-linkages with one O in each such linkage being"active". AvO content of such an oxygen bleach compound, usually expressed as a percent, is equal to 100 * the number of active oxygen atoms * (16/molecular weight of the oxygen bleach compound).

ADDITIONAL COMPONENTS Surfactant The laundry bars of the present invention may further include surfactants.

Surfactants useful in the present invention include anionic, nonionic, cationic, and zwitterionic (e. g. amphoteric).

The bar composition of the present invention preferably contains from about 0.5% to about 60% surfactant by weight of the total bar composition.

Preferably, the bar composition contains from about 10% to about 50%, more preferably, from about 15% to about 30% surfactant, by weight of the total bar composition.

Anionic surfactants are preferably selected from the group consisting of linear alkyl benzene sulfonate, alkyl sulfate, alkyl ethoxylate sulfate and mixtures thereof.

Anionic synthetic detergent surfactants which are suitable for use herein include the water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl"is the alkyl portion of acyl groups.) Examples of this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcools (Cg 18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil ; and the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e. g., those of the type described in U. S. Patents 2,220,099 and 2,477,383.

Especially valable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as Cl 13 LAS. The alkali metal salts, particularly the sodium salts

of these surfactants are preferred. Alkylbenzene sulfonates and processes for making them are disclosed in U. S. Patent Nos. 2,220,099 and 2,477,383.

Mixtures of the above types of anionic surfactants are preferred.

Specifically, preferred anionic surfactants are C10-18 linear alkyl benzene sulfonates, C10 1 g alkyl sulfates, and mixtures thereof. C10 1 g alkyl sulfates can be in many physical forms, such as paste or flakes ; the flake form is preferred.

One preferred composition contains a mixture of LAS: Alkyl sulfate in a ratio of from about 10: 90 to about 100: 1, preferably from about 20: 80 to about 40: 60.

Other synthetic anionic surfactants suitable for use herein as surfactants are alkyl ethoxylate sulfates, the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcools derived from tallow and coconut oil ; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates. Preparation of alkyl glyceryl ether sulfonates are described in detail in U. S. Pat. 3,024,273, Whyte et al., issued March 6,1962.

In addition, optional synthetic anionic surfactants include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxyalkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin and paraffin sulfonates containing from about 12 to 20 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.

A typical listing of the classes and species of other surfactants, (e. g. nonionic, zwitterionic and amphoteric surfactants) useful herein appears in U. S.

Pat. No. 3,664,961, issued to Norris on May 23,1972, and EP 550,652, published on April 16,1992. Cationic surfactant is another optional surfactant.

Amine Oxides are excellent cosurfactants that may be used in conjunction with the present invention. Preferred types are C12-C1 g amine oxides, preferably C14. If included, the level of amine oxide in the final bar composition is from about 1 % to about 10%, preferably, from about 2% to about 5%.

Builder The bar composition may further contain builders. Builders are mainly divided as phosphate builder and non-phosphate builder.

The bar composition may further contain at least about 2% phosphate builder, by weight of the total bar composition. Preferably, the bar composition comprises from about 5% to about 40%, more preferably, from about 10% to about 25% phosphate builder, by weight of the total bar composition. The phosphate builder is selected from the group consisting of phosphates, pyrophosphates, orthophosphates, tripolyphosphates, higher polyphosphates, and mixtures thereof. Polyphosphates include both cyclic or linear polyphosphates.

The phosphate builders are preferably water-soluble alkali-metal salts of phosphate, including pyrophosphates, orthophosphates, tripolyphosphates, higher polyphosphates, and mixtures thereof. Preferred phosphate builders are a water-soluble alkali-metal salt of tripolyphosphate, and a mixture of tripolyphosphate and pyrophosphate. Specific preferred examples of phosphate builders include sodium tripolyphosphates (STPP) and tetra sodium pyrophosphates (TSPP), and mixtures thereof.

The builder can optionally contain in addition to the phosphate builder, a non-phosphate detergent builder. Specific examples of non-phosphate, inorganic detergency builders include water-soluble inorganic carbonate and bicarbonate salts. The alkali metal (e. g., sodium and potassium) carbonates and bicarbonates are particularly useful herein. Other specifically preferred examples of builders include polycarboxylates, zeolite, and layered silicates.

Sodium carbonate or sodium hydroxide, another optional ingredient, is particularly preferred as a neutralizing inorganic salt for an acid precursor of an anionic surfactant used in such compositions, such as the alkyl ether sulfuric acid and alkylbenzene sulfonic acid. Co-polymers of acrylic acid and maleic acid are preferred in the subject compositions as auxiliary builders.

Other Bleaching Agent The bar composition may further contain other bleaching agents in addition to calcium peroxide. It is also possible to substitute magnesium peroxide for a portion or the calcium peroxide used in the detergent bar formulation. Other bleaching agents also useful herein can be any of the peroxygen bleach agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known. Mixtures of bleach agents can also be used. The preferred ratio of calcium peroxide versus other peroxygen bleach is from about 100: 0 to about

10: 90, preferably from about 25: 75 to about 50: 50, more preferably from about 60: 40 to about 75 to 25.

A preferred composition of the present invention contains from about 0.1% to about 30% peroxygen bleach (calcium peroxide and other peroxygen bleach), by weight of the total bar composition. Preferably, the bar composition comprises from about 1% to about 10%, more preferably, from about 2% to about 5% peroxygen bleach, by weight of the total bar composition.

Preferred peroxygen bleaching agents include those peroxygen bleaching compounds which are capable of yielding hydrogen peroxide in an aqueous solution. These compounds are well known in the art and include hydrogen peroxide and the alkali metal peroxides, organic peroxide bleaching compounds such as urea peroxide, and inorganic persalt bleaching compounds, such as the alkali metal perborates, percarbonates, perphosphates, and the like.

Preferred peroxygen bleaching agents include peroxygen bleach selected from the group consisting of perborates, percarbonates, peroxyhydrates, peroxides, persulfates, and mixtures thereof. Specific preferred examples include : sodium perborate, commercially available in the form of mono-and tetra-hydrates, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Particular preferred are sodium perborate tetrahydrate, and especially, sodium perborate monohydrate. Sodium perborate monohydrate is especially preferred because it is very stable during storage and yet still dissolves very quickly in the bleaching solution. If used, peroxygen bleach is preferably contained from about 0% to about 1 % by weight of the laundry bar composition.

Persulfate bleach (e. g., OXONE, manufactured commercially by DuPont) can also be used.

Percarbonate bleach can also be used. Such preferred percarbonate bleach are dry particles having an average particle size in the range from about 500 micrometers to about 1,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers. Optionally, the percarbonate can be coated with silicate, borate or water-soluble surfactants. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.

Bleach activator

The bar compositions herein may optionally contain one or more bleach activators. If present, the amount of bleach activators will typically be from about 0.05% to about 10%; more typically, from about 0.05% to about 5% by weight.

Peroxygen bleach agents, the perborates, the percarbonates, etc., are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i. e., during the washing process) of the peroxy acid corresponding to the bleach activator. Various nonlimiting examples of activators are disclosed in U. S. Patent 4,915,854, issued April 10,1990 to Mao et al, and U. S. Patent 4,412,934. The nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used. See also U. S. 4,634,551 for other typical bleaches and activators useful herein.

Highly preferred amido-derived bleach activators are those of the formulae: Rl (R5) C (O) R2C (O) L or R1C (O) N (R5) R2C (O) L wherein R1 is an alkyl group containing from about 6 to about 12 carbon atoms, R2 is an alkylene containing from 1 to about 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group. A leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred leaving group is phenyl sulfonate.

Preferred examples of bleach activators of the above formulae include (6- octanamido-caproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamidocaproyl) oxybenzenesulfonate, and mixtures thereof as described in U. S. Patent 4,634,551.

Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U. S. Patent 4,966,723, issued October 30, 1990. A highly preferred activator of the benzoxazin-type is: Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae :

wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U. S. Patent 4,545,784, issued to Sanderson, October 8,1985, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.

Bleach catalyst The laundry bar composition of the present invention optionally comprises a bleach catalyst. The catalyst is included in the laundry bar at a level from about 0.002% to about 14%, and preferably from about 0.02% to about 10%.

If desired, the bleach compounds can be catalyzed by means of a manganese compound. Such compounds are well known in the art and include, for example, the manganese-based catalysts disclosed in U. S. Pat. 5,246,621, U. S. Pat. 5,244,594; U. S. Pat. 5,194,416; U. S. Pat. 5,114,606; and European Pat. App. Pub. Nos. 549, 271A1, 549, 272A1, 544, 440A2, and 544, 490A1 ; Preferred examples of these catalysts include Mniv2 (u-0) 3 (1, 4, 7-trimethyl-1, 4, 7- triazacyclononane) 2 (PF6) 2, MnII12 (u-O) i (u-OAc) 2 (1,4,7-trimethyl-1,4,7- triazacyclononane) 2 (C104) 2, Mnv4 (u-0) 6 (1,4,7-triazacyclononane) 4 (Cl04) 4, Mnl (u-0) 1 (u-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (CI04) 3, Mniv (1, 4,7-trimethyl-1,4,7-triazacyclononane)- (OCH3) 3 (PF6), and mixtures thereof. Other metal-based bleach catalysts include those disclosed in U. S. Pat.

4,430,243 and U. S. Pat. 5,114,611. The use of manganese with various complex ligands to enhance bleaching is also reported in the following United States Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084. The bleach compounds may also be

catalyzed by organic bleach boosters as described in U. S. Pat. 5,576,282 and 5,710,116.

As a practical matter, and not by way of limitation, the compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 0.1 ppm to about 700 ppm, more preferably from about 1 ppm to about 500 ppm, of the catalyst species in the laundry liquor.

Enzyme The amount of enzyme in the detergent composition is preferably at a level from about 0.0011 mg to about 2.2 mg of active enzyme per gram of the detergent composition; more preferably, from about 0.0011 mg to about 1.1 mg; and most preferably, from about 0.0011 mg to about 0.55 mg per gram of the composition. Enzymes to be incorporated include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof.

A wide range of enzyme materials and means for their incorporation into synthetic detergent compositions are also disclosed in U. S. Patent 3,553,139, issued January 5,1971 to McCarty et al. Enzymes are further disclosed in U. S.

Patent 4,101,457, Place et al, issued July 18,1978, and in U. S. Patent 4,507,219, Hughes, issued March 26,1985, both. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U. S. Patent 4,261,868, Hora et al, issued April 14,1981. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in U. S. Patent 3,600,319, issued August 17,1971 to Gedge, et al, and European Patent Application Publication No. 0 199 405, Application No. 86200586.5, published October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U. S. Patent 3,519,570.

Suitable examples of proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis. One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE by Novo Industries A/S of Denmark, hereinafter"Novo". The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo. Other suitable proteases include ALCALASE and SAVINASE from Novo and MAXATASE Tll from

International Bio-Synthetics, Inc., The Netherlands ; as well as Protease A as disclosed in EP 130,756 A, January 9,1985 and Protease B as disclosed in EP 303,761 A, April 28,1987 and EP 130,756 A, January 9,1985. See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 9203529 A to Novo.

Other preferred proteases include those of WO 9510591 A to Procter & Gamble.

When desired, a protease having decreased adsorption and increased hydrolysis is available as described in WO 9507791 to Procter & Gamble. A recombinant trypsin-like protease for detergents suitable herein is described in WO 9425583 to Novo.

In more detail, an especially preferred protease, referred to as"Protease D"is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in the patent applications of A. Baeck, et al, entitled"Protease-Containing Cleaning Compositions"having US Serial No.

08/322,676, and C. Ghosh, et al,"Bleaching Compositions Comprising Protease Enzymes"having US Serial No. 08/322,677, both filed October 13,1994.

Protease enzymes are usually present in an amount that ranges from about 0.0055 mg to about 0.022 mg of active enzyme per gram of the composition. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.

Cellulase enzymes usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U. S. Patent 4,435,307, Barbesgoard et al, issued March 6,1984, which discloses fungal cellulase produced from Humicola insolens and Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the

hepatopancreas of a marine mollusk (Dolabella Auricula Solander). Suitable cellulases are also disclosed in GB-A-2,075,028; GB-A-2,095,275 and DE-OS- 2,247,832. CAREZYME TM (Novo) is especially useful.

Cellulase enzymes are usually present in an amount that ranges from about 0.002 mg to about 0.04 mg of active enzyme per gram of the composition.

Preferable is Carezymew having an activity of 5000 CEVU per gram. Most preferable is Carezymew having an activity of 1000 CEVU per gram.

A preferred bar composition comprises a mixture of enzymes: (1) from about 0.0055 mg to about 0.022 mg of protease enzyme per gram of the composition; and (2) from about 0.002 mg to about 0.04 mg of cellulase enzyme per gram of the composition.

Amylases suitable herein, especially for, but not limited to automatic dishwashing purposes, include, for example,-amylases described in GB 1,296,839 to Novo; RAPIDASE TM, International Bio-Synthetics, Inc. and TERMAMYL TM, Novo. FUNGAMYLT" from Novo is especially useful.

Engineering of enzymes for improved stability, e. g., oxidative stability, is known.

See, for example J. Biological Chem., Vol. 260, No. 11, June 1985, pp. 6518- 6521. Certain preferred embodiments of the present compositions can make use of amylases having improved stability in detergents such as automatic dishwashing types, especially improved oxidative stability as measured against a reference-point of TERMAMYLT" in commercial use in 1993. These preferred amylases herein share the characteristic of being"stability-enhanced"amylases, characterized, at a minimum, by a mesurable improvement in one or more of: oxidative stability, e. g., to hydrogen peroxide/tetraacetylethylenediamine in buffered solution at pH 9-10; thermal stability, e. g., at common wash temperatures such as about 60°C ; or alkaline stability, e. g., at a pH from about 8 to about 11, measured versus the above-identified reference-point amylase.

Stability can be measured using any of the art-disclosed technical tests. See, for example, references disclosed in WO 9402597. Stability-enhanced amylases can be obtained from Novo or from Genencor International. One class of highly preferred amylases herein have the commonality of being derived using site- directed mutagenesis from one or more of the Bacillus amylases, especially the Bacillus-amylases, regardless of whether one, two or multiple amylase strains are the immediate precursors. Oxidative stability-enhanced amylases vs. the

above-identified reference amylase are preferred for use, especially in bleaching, more preferably oxygen bleaching, as distinct from chlorine bleaching, detergent compositions herein. Such preferred amylases include (a) an amylase according to the hereinbefore incorporated WO 9402597, Novo, Feb. 3,1994, as further illustrated by a mutant in which substitution is made, using alanine or threonine, preferably threonine, of the methionine residue located in position 197 of the B. licheniformis alpha-amylase, known as TERMAMYL, or the homologous position variation of a similar parent amylase, such as B. amyloliquefaciens, B. subtilis, or B. stearothermophilus ; (b) stability-enhanced amylases as described by Genencor International in a paper entitled"Oxidatively Resistant alpha- Amylases"presented at the 207th American Chemical Society National Meeting, March 13-17 1994, by C. Mitchinson. Therein it was noted that bleaches in automatic dishwashing detergents inactivate alpha-amylases but that improved oxidative stability amylases have been made by Genencor from B licheniformis NCIB8061. Methionine (Met) was identified as the most likely residue to be modified. Met was substituted, one at a time, in positions 8,15,197,256,304, 366 and 438 leading to specific mutants, particularly important being M197L and M197T with the M197T variant being the most stable expressed variant. Stability was measured in CASCADE and SUNLiGHT ; (c) particularly preferred amylases herein include amylase variants having additional modification in the immediate parent as described in WO 9510603 A and are available from the assignee, Novo, as DURAMYL. Other particularly preferred oxidative stability enhanced amylase include those described in WO 9418314 to Genencor International and WO 9402597 to Novo. Any other oxidative stability-enhanced amylase can be used, for example as derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant parent forms of available amylases.

Other preferred enzyme modifications are accessible. See WO 9509909 A to Novo.

Other amylase enzymes include those described in WO 95/26397 and in co-pending application by Novo Nordisk PCT/DK96/00056. Specific amylase enzymes for use in the detergent compositions of the present invention include- amylases characterized by having a specific activity at least 25% higher than the specific activity of TermamylT" at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 10, measured by the PhadebasT""-amylase activity assay. (Such PhadebasT""-amylase activity assay is described at pages 9-10,

WO 95/26397.) Also included herein are-amylases which are at least 80% homologous with the amino acid sequences shown in the SEQ ID listings in the references.

Amylase enzymes are usually present in an amount that ranges from about 0.0045 mg to about 0.45 mg of active enzyme per gram of the composition.

Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB 1,372,034. See also lipases in Japanese Patent Application 53,20487, laid open Feb. 24,1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P"Amano,"or"Amano-P."Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e. g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U. S. Biochemical Corp., U. S. A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. LIPOLASE"enzyme derived from Humicola lanuginosa and commercially available from Novo, see also EP 341,947, is a preferred lipase for use herein. Lipase and amylase variants stabilized against peroxidase enzymes are described in WO 9414951 A to Novo.

See also WO 9205249 and RD 94359044.

Lipase activity is expressed in Lipase Unit (LU) which is the amount of lipase which produces 1 umol of titratable fatty acid per minute in a pH stat. under the following conditions: temperature of 30°C ; pH of 9.0; substrate is an mulsion of 3.3 wt% of olive oil and 3.3% gum arabic, in the presence of 13mmol/I Ca2+ mmol/l NaCI in 5 mmo)/t Tris buffer.

Lipase enzymes are usually present in an amount that ranges from about 0.0022 mg to about 1.1 mg of active enzyme per gram of the composition.

Peroxidase enzymes are used in combination with oxygen sources, e. g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching,"i. e. to prevent the transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.

Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro-and bromo- peroxidase. Peroxidase-containing detergent compositions are disclosed, for

example, in PCT International Application WO 89/099813, published October 19, 1989, by O. Kirk, assigned to Novo Industries A/S.

Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin.

However, their choice is governed by several factors such as pH-activity and/or stability optima, thermostability, stability versus active detergents, builders and so on. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.

Moisture The bar composition preferably has a total moisture content from about 0.1% to about 10%, by weight of the final bar composition. Preferably, the bar composition has a total moisture content from about 1% to about 5%, more preferably, from about 2.5% to about 4.5%, by weight of the total bar composition. The total moisture level of the final bar composition can be determined by any methods known in the art by one skilled in the area of laundry bar compositions. One common method is the Bidwell Sterling Distillation method. Another known method is the Karl Fischer Moisture Titration Method.

See AOCS official method Dd2a-59 issue 93 and AOCS official method Dd2b-59 issue 89.

In addition, a hydrotrope, or mixture of hydrotropes, may be present in the laundry detergent bar. Preferred hydrotropes include the alkali metal, preferably sodium, salts of toluene sulfonate, xylene sulfonate, cumene sulfonate, sulfosuccinate, and mixtures thereof. Preferably, the hydrotrope is added to the linear alkyl benzene sulfonic acid prior to its neutralization. The hydrotrope, if present, will preferably be present at from about 0.5% to about 5% of the laundry detergent bar.

OTHER ADDITIONAL COMPONENTS The bar composition of the present invention may further contain additional components, which are optional for the bar composition of the present invention.

Sodium carbonate or sodium hydroxide, another optional ingredient, is particularly preferred as a neutralizing inorganic salt for an acid precursor of an anionic surfactant used in such compositions, such as the alkyl ether sulfuric acid and alkylbenzene sulfonic acid. Co-polymers of acrylic acid and maleic acid are preferred in the subject compositions as auxiliary builders.

Binding agents is particularly preferred to give the bar composition good binding and a good rate of hardening during the manufacture of the bar compositions. Preferably the addition of magnesium sulfate to the bar composition gives such benefits. When used, the bar composition comprises from about 1.5% to about 10%, more preferably, from about 2% to about 5% magnesium sulfate, by weight of the final bar composition. When magnesium sulfate is used, it must be added in the manufacturing process after the addition of both the calcium salt and siliceous material.

Soil suspending agents can be used. Soil suspending agents can also include water-soluble salts of carboxymethylcellulose and carboxyhydroxymethylcellulose. A preferred soil suspending agent is an acrylic/maleic copolymer, commercially available as Sokolan0§), from BASF Corp.

Other soil suspending agents include polyethylene glycols having a molecular weight of about 400 to 10,000, and ethoxylated mono-and polyamines, and quaternary salts thereof. If included, it can be at levels up to about 5%, preferably about 0.1 to 1%.

A preferred component of the present invention is a chelating agent.

Such chelating agents are able to sequester and chelate alkali cations (such as sodium, lithium and potassium), alkali metal earth cations (such as magnesium and calcium), and most importantly, heavy metal cations such as iron, manganese, zinc and aluminum. Preferred cations include sodium, magnesium, zinc, and mixtures thereof.

The chelating agent is preferably selected from a group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof.

One preferred chelating agent is a phosphonate chelating agent, particularly one selected from the group consisting of diethylenetriamine penta (methylene phosphonic acid), ethylene diamine tetra (methylene phosphonic acid), and mixtures and salts and complexes thereof, and an acetate chelating agent, particularly one selected from the group consisting of diethylenetriamine penta (acetic acid), ethylene diamine tetra (acetic acid), and mixtures and salts and complexes thereof. The dry form of the phosphonate chelating agent is particularly preferred, although the liquid form is also an option. Particularly preferred are sodium, zinc, magnesium, and aluminum salts

and complexes of diethylenetriamine penta (methylene phosphonate) diethylenetriamine penta (acetate), and mixtures thereof.

Preferably such salts or complexes have a molar ratio of metal ion to chelating agent molecule of at least 1: 1, preferably at least 2: 1. The detergent chelating agent can be included in the laundry bar at a level up to about 5%, preferably from about 0.1% to about 5%, more preferably from about 0.2% to about 2%, most preferably from about 0.5% to about 1.0%.

Another optional component of the laundry bar is fatty alcohol having an alkyl chain of 8 to 22 carbon atoms, more preferably from 12 to 18 carbon atoms.

A preferred fatty alcohol has an alkyl chain predominantly containing from 16 to 18 carbon atoms, so-called"high-cut fatty alcohol,"which can exhibit less base odor of fatty alcohol relative to broad cut fatty alcools. Typically fatty alcool, if any, is present in the laundry bar at up to a level of 10%, more preferably from about 0.75% to about 6%, most preferably from about 2% to about 5%. The fatty alcohol is generally added to a laundry bar as free fatty alcool. However, low levels of fatty alcohol can be introduced into the bars as impurities or as unreacted starting material. For example, laundry bars based on coconut fatty alkyl sulfate can contain, as unreacted starting material, from 0.1% to 3.5%, more typically from 2% to 3%, by weight of free coconut fatty alcohol on a coconut fatty alkyl sulfate basis.

Another optional component in the laundry bar is a dye transfer inhibiting (DTI) ingredient to prevent diminishing of color fidelity and intensity in fabrics. A preferred DTI ingredient can include polymeric DTI materials capable of binding fugitive dyes to prevent them from depositing on the fabrics, and decolorization DTI materials capable of decolorizing the fugitives dye by oxidation. An example of a decolorization DTI is hydrogen peroxide or a source of hydrogen peroxide, such as percarbonate or perborate. Non-limiting examples of polymeric DTI materials include polyvinylpyrridine N-oxide, polyvinylpyrrolidone (PVP), PVP- polyvinylimidazole copolymer, and mixtures thereof. Copolymers of N- vinylpyrrolidone and N-vinylimidazole polymers (referred to as"PVPI") are also preferred for use herein. The amount of DTI included in the subject compositions, if any, is about 0.05-5%, preferably about 0.2-2%.

Another optional component in the laundry bar is a fabric softener component. Such materials can be used, if any, at levels of about 0.1% to 5%, more preferably from 0.3% to 3%, and can include: amines of the formula

R4R5R6N, wherein R4 is C5 to C22 hydrocarbyl, R5 and R6 are independently Cl to C10 hydrocarbyl. One preferred amine is ditallowmethyl amine; complexes of such amines with fatty acid of the formula R7COOH, wherein R7 is Cg to C22 hydrocarbyl, as disclosed in EP No. 0,133,804; complexes of such amines with phosphate esters of the formula R80-P (O) (OH)-ORg and HO-P (O) (OH)-ORg, wherein R8 and Rg are independently Cl to C20 alkyl of alkyl ethoxylate of the formula-alkyl- (OCH2CH2) ; cyclic amines such as imidazolines of the general formula 1- (higher alkyl) amido (lower alkyl)-2- (higher alkyl) imidazoline, where higher alkyl is from 12 to 22 carbons and lower alkyl is from 1 to 4 carbons, such as described in UK Patent Application GB 2,173,827; and quaternary ammonium compounds of the formula RloRllRl2Rl3N+X-, wherein Rlo is alkyl having 8 to 20 carbons, Ri is alkyl having 1 to 10 carbons, Ri2 and Ri3 are alkyl having 1 to 4 carbons, preferably methyl, and X is an anion, preferably Cl-or Br, such as C12 13 alkyl trimethyl ammonium chloride.

Sodium sulfate is a well-known filler that is compatible with the compositions of this invention. It can be a by-product of the surfactant sulfation and sulfonation processes, or it can be added separately. Calcium carbonate (also known as Calcarb) is also a well known and often used filler component of laundry bars. Talc is another optional filler material. Filler materials are typically used, if included, at levels up to 40%, preferably from about 5% to about 25%.

The fabric softening clay is preferably a smectite-type clay that is compatible with the compositions of this invention. The smectite-type clays can be described as expandable, three-layer clays ; i. e., alumino-silicates and magnesium silicates, having an ion exchange capacity of at least about 50 meq/100 g. of clay. Preferably the clay particles are of a size that they can not be perceived tactilely, so as not to have a gritty feel on the treated fabric of the clothes. The fabric softening clay can be added to the bar to provide about 1% to about 50% by weight of the bar, more preferably from about 2% to about 20%, and most preferably about 3% to 14%.

While any of the smectite-type clays described herein are useful in the present invention, certain clays are preferred. For example, Gelwhite GP is an extremely white form of smectite-type clay and is therefore preferred when formulating white granular detergent compositions. Volclay BC, which is a smectite-type clay mineral containing at least 3% iron (expressed as Fe203) in the crystal lattice, and which has a very high ion exchange capacity, is one of the

most efficient and effective clays for use in the instant compositions from the standpoint of product performance. On the other hand, certain smectite-type clays are sufficiently contaminated by other silicate minerals that their ion exchange capacities fall below the requisite range; such clays are of no use in the instant compositions.

It has been found that the use of a clay flocculating agent in a laundry bar containing softening clay provides surprisingly improved softening clay deposition onto the clothes and clothes softening performance, compared to that of laundry bars comprising softening clay alone. The polymeric clay flocculating agent is selected to provide improved deposition of the fabric softening clay.

Typically such materials have a high molecular weight, greater than about 100,000. Examples of such materials can include long chain polymers and copolymers derived from monomers such as ethylene oxide, acrylamide, acrylic acid, dimethylamino ethyl methacrylate, vinyl alcohol, vinyl pyrrolidone, and ethylene imine. Gums, like guar gums, are suitable as well. The preferred clay flocculating agent is a poly (ethylene oxide) polymer. The amount of clay flocculating agent, if any, is about 0.2-2%, preferably about 0.5-1 %.

Optical brighteners are also optional ingredients in laundry bars of the present invention. Preferred optical brighteners are diamino stilbene, distyrilbiphenyl-type optical brighteners. Preferred as examples of such brighteners are 4,4'-bis { [4-anilino-6-bis (2-hydoxyethyl) amino-1,3,5-trizin-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, can be used at levels in the bar of from about 0.05% to about 1.0%.

Dyes, pigments, germicides, and perfumes can also be added to the bar composition. If included, they are typically at levels up to about 0.5%.

Another optional component of the subject invention composition is a photobleach material, particularly phthalocyanine photobleaches which are described in U. S. Patent 4,033,718 issued July 5,1977, incorporated herein by reference. Preferred photobleaches are metal phthalocyanine compounds, the metal preferably having a valance of +2 or +3; zinc and aluminum are preferred metals. Such photobleaches are available, for example, under the tradename TINOLUS or as zinc phthalocyanine sulfonate. The photobleach components, if included, are typically in the subject compositions at levels up to about 0.02%,

preferably from about 0.001% to about 0.015%, more preferably from about 0.002% to about 0.01%.

Titanium dioxide is another optional component. It can be a preferred ingredient for aesthetics of the bar composition, e. g. whiteness.

Bar Physical Properties The bars of the present invention have improved physical properties, including improved in-process and aged hardness of the bar as well as reduced solubility in water during washing. In addition, the bars of the present invention have improved cleaning benefits as well as mildness benefits.

The bars of the present invention are sufficiently hard. A preferred test method measures bar hardness after three weeks of aging. Bars are aged for three weeks at 80°F/80 relative humidity (RH). To measure the bar hardness, a needle with a point angle of 43° attached to a force gauge (Control International, Lincolnwood, IL, USA) was forced onto the plane of the bar surface to a depth of 5.8 mm. A preferred bar hardness reading of laundry bar compositions using this test method is about 55-70 Ibs. Bars of the present invention fall within the range. Another method to measure bar hardness is to measure the penetration of a needle through the bar surface under a standard weight for 5 seconds using a cone penetrometer. One such penetrometer is made by Associated Instrument Manufacturers India Pvt. Ltd. (Model number AIM 512). The weight of the rod and the cone is 149 grams and an additional 50 gram weight is placed on the cone. The penetration reading of a fresh bar made as per the present invention will typically be about 20-30 (1/10 mm) and 15-20 (1/10 mm) after 40 minutes.

Bars aged about 3 days at ambient conditions will typically have a bar penetration reading of about 5-12 (1/10 mm).

Processing The detergent laundry bars of the present invention can be processed in conventional soap or detergent bar making equipment with some or all of the following key equipment: blender/mixer, mill or refining plodder, two-stage vacuum plodder, logo printer/cutter, cooling tunnel and wrapper.

In a typical process the raw materials are mixed in the blender. Alkyl benzene sulfonic acid is reacted with alkaline inorganic satts to complete neutralization, the amount of alkaline inorganic salt being at least sufficient to completely neutralize the acid. At least 5% of the phosphate builder must be present during the neutralization reaction. Preferably at least 10% can be

present. Then other optional surfactants followed by any additional optional components such as chelating agents are added. The mixing can take from one minute to one hour, with the usual mixing time being from about two to twenty minutes. The blender mix is charged to a surge tank. The product is conveyed from the surge tank to the mill or refining plodder via a multi-worm conveyor.

After milling or preliminary plodding, the product is then conveyed to a two-stage vacuum plodder, operating at high vacuum, e. g. 600 to 740 mm of mercury vacuum, so that entrapped air/gas is removed. The product is extruded and cut to the desired bar length, and printed with the product brand name. The printed bar is preferably cooled, for example in a cooling tunnel, before it is wrapped, cased, and sent to storage. It is preferred that the packed cases of bars be stored at a temperature of 20-30°C immediately after packing. Without intending to be limited by theory, this step allows the bars to reach a stable state, physically as well as chemically. After this stabilizing stage, storing the bars at a high temperature and humidity condition should not affect the bar's physical properties and aesthetics.

A preferred laundry bar composition is made by the following method: The raw materials are first mixed in a blender. STPP, sodium carbonate and pre- neutralized CFAS (if a mixture of CFAS/LAS is used as surfactant system) are mixed for about 1-2 minutes This is followed by the addition of linear alkyl benzene sulfonic acid and sulfuric acid (if present in the formulation). The acids are then completely neutralized by the sodium carbonate in the seat of the blender. (The amount of sodium carbonate should be at least an amount sufficient to neutralize the acids.) Then, a chelating agent, if present is added, followed by other optional surfactants (if present), and any other additional optional components. The total mixing time can take up to about one hour, with the usual mixing time being from about five to twenty minutes. As one of the last ingredients, calcium peroxide and optionally, other peroxygen bleaching agents and enzymes can be added to the mixture and then mixed, preferably, for an additional 2 minutes. It is preferred that the calcium peroxide is added as one of the last ingredients, the temperature of the blender mixture is about 45 to 65°C.

The blender mix is charged to a surge tank. The product is conveyed from the surge tank to the mill or refining plodder via a multi-worm conveyor.

After milling or preliminary plodding, the product is then conveyed to a two-stage vacuum plodder, operating at high vacuum, e. g. 600 to 740 mm of mercury vacuum, so that entrapped air is removed. The product is extruded and cut to the desired bar length, and printed with the product brand name. The printed bar is cooled, for example in a cooling tunnel, before it is wrapped, cased, and sent to storage as described above.

EXAMPLES The following examples further describe and demonstrate the preferred embodiments within the scope of the present invention. The examples are given solely for the purpose of illustration, and are not to be construed as limitations of the present invention since many variations thereof are possible without departing from its spirit and scope.

1 2 3 4 5 (weight percent) NaLAS 20 6.45 6.45 6.45-- NaCFAS 20 15.05 15.05 15.05-- Na2CO3 15.00 15.00 15.00 10.00 10.00 STPP 14.00 10.00 10.00 15.00 15.00 Na2S04--5. 00 5.00---- CaS04--5. 00 5.00---- Ca02 5.00 4.00 4.00 4.00 4.00 PB1--0. 50--0. 25-- PB4----0. 50 0.25-- PC--------0. 50 Protease 0.08 0.08 0.08 0.08-- Cellulase------0. 10 0.10 Moisture 3.00 3.00 3.00 6.00 4.00 Brightener 0.20 0.20 0.20 0.20 0.20 Chelent 0.40 0.40 0.40 0.40 0.40 CaCO3 20.00 20.00 20.00 20.00 20.00 Others balance balance balance balance balance 100.00 100.00 100.00 100.00 100.00 STPP: Anhydrous sodium tripolyphosphate PB1 : Anhydrous sodium perborate bleach of nominal formula NaBO2. H202 PB4: Sodium perborate tetrahydrate of nominal formula NaB02. 3H20. H202 LAS: Sodium linear C11-13 alkyl benzene sulfonate CFAS: Coconut Fatty Alcohol Sulfate

PC: Percarbonate It is understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to one skilled in the art without departing from the scope of the present invention.