Title of Invention

"LAUNDRY DETERGENT BAR COMPOSITION".

Abstract The present invention is directed to a laundry detergent bar composition having both perborate and percarbonate in a specific ratio. A preferred bar composition contains perborate and percarbonate in a ratio from about 85:15 to about 30:70, more preferably, from about 35:15 to about 50:50, even more preferably, from about 80:20 to about 50:50. The bars of the present invention have improved bleaching benefit and is effective for a wide variety of stafn removal.
Full Text FIELD
The present Invention relates to a laundry detergent bar composition containing a peroxygen bleach. More specifically, the present invention relates to a laundry detergent bar containing both percarbonate and perborate.
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 pleasing 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 oxidatlve process which decolorizes or removes impurities or foreign matter from the material being treated. Two examples of peroxygen compounds that have been used as a source of active oxygen in these formulations are perborate and percarbonate.
It has now been found that a laundry detergent bar composition containing perborate and percarbonate bleach in a specific ratio has Improved bleaching benefit and is effective for a wide variety of stain removal.
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 both perborate and percarbonate in a specific ratio of from about 85:15 to about 30:70.
A preferred bar composition contains perborate and percarbonate at a more specific ratio, wherein the ratio of the perborate and the percarbonate is from about 65:15 to about 50:50, more preferably, from about 80:20 to about 50:50,
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 wrth 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.
Although not wanting to be limited by theory, it Is believed that the bleach performance on stains is dependent upon the type of peroxygen bleach used in the bar composition. A specific peroxygen bleach may be effective for one type of stain removed, but less effective for another type of stain removal. For example, perborate Is effective for bleaching/decolorizing polyphenollc stains such as tea and coffee but not as effective for bleaching stains containing guar
gums such as chocolate stains. On the other hand, percarbonate is more effective on chocolate stains but not as effective as perborate on other types of stains, So a laundry detergent bar composition containing both perborate and percarbonate bleach at a specific ratio has improved bleaching benefit and is effective for a wide variety of stain removal. Perborate and Percarfoongfe
The laundry bars of the present invention contain perborate and percarbonate ata ratio of from about 90:10 to about 10;90.
Perborate also known as peroxoborate, and/or salts of perborate may be used in the present invention. Examples Include sodium perborate, lithium perborate, potassium perborate, rubidium perborate, cesium perborate, ammonium perborate, barium perborate are known. Potassium perborate and sodium perborate are preferable; sodium perborate is more preferable. Sodium perborate's chemical formula is described as NaBC^HjO or Na2B4.0$10H20. Particularly 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. Perborate Is commercially available by Solvay-intenox, but any other commercially available material can also be used for the present invention,
Percarbonate, also Known as peroxocarbonate, and/or salts of percarbonate, may also be used. Examples include sodium .percarbonate, ammonium percarbonate, potassium percarbonate or rubidium percarbonate are known. Potassium percarbonate or sodium percarbonate is preferable; sodium percarbonate is more preferable. Sodium percarbonate's chemical formula Is described as Na2CO,.nHaOz , where n can range from Y*. to 5. Preferable percarbonate is where n - !4 to 3. Percarbonate Is commercially available by Sclvay-lnterox and Degussa, but any other commercially available material can also be used for the present invention. Percarbonate bleach contains dry particles having an average particle size in the range from about 500 micrometers to about 1,000 micrometers, wherein not more than about 10% by weight of the particles are smaller than about 200 micrometers and wherein not more than about 10% by weight of the particles are larger than about 1,250 micrometers. Optionally, the percarbonate can be coated with silicate, borate or water-soluble surfactants.
A preferred bar composition contains perborate and percarbonate at a more specific ratio, wherein the ratio of the perborate and the percarbonate is from about 85:15 to about 30:70, more preferably, from about 80:20 to about 50:50.
The composition of the present invention preferably contains from about 0;1% to about 20% the mixture of perborate and percarbonate, by weight of the total bar composition. Preferably, the bar composition contains from about 1 % to about 10% peroxygen bleach, by weight of the total bar composition. Surfactant
The laundry bars of the present invention may further include surfactants.
Surfactants useful In the present invention include aniontc, nonlonlc,
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, alky! sulfate, alkyi 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 aikyloiammonium salts of organic sulfuric reaction products having In their molecular structure an aikyl 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 alcohols (03.13 carton atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium aikylbenzene suifonates 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 valuable are linear straight chain aikylbenzene suifonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as Ci 1-13 LAS. The alkali metal salts, particularly the sodium salts of these surfactants are preferred. Aikylbenzene suifonates and processes for
making them are disclosed in U,S. Patent Nos. 2,220,093 and 2,477,383.
Mixtures of the above types of anionlc surfactants are preferred. Specifically, preferred anlonic surfactants are C-to-18 linear alkvl benzene sulfonates, CIQ.-JQ aikyl sulfates, and mixtures thereof, C-jQ-18 alW 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 anlonic surfactants suitable for use herein as surfactants are alkyl ethoxylate sulfates, the sodium aikyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monogfyceride sulfonates and sulfates. Preparation of alkyi glyceryl ether suifonates are described In detail In U.S. Pat. 3,024,273, Whyte et at., issued March 6,1962.
In addition, optional synthetic anlonic surfactants include the water-soluble salts of esters of alpha-suifonated 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-sulfonlc 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-alkyioxy 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, zwitterionlc and amphoteric surfactants) useful herein appears in U.S, Pat. No. 3.664,961, issued to Morris on May 23, 1972, and EP 550,652, published on April 16,1992. Cationic surfactant Is another optional surfactant.
Amine Oxides are excellent eosurfactants that may be used in conjunction with the present invention. Preferred types are C-|2-Cl8 amin* oxides, preferably C-|4. 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%.
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. A. Builder
The composition of the present invention may further contain at least about 5% phosphate builder, by weight of the total bar composition. Preferably, the bar composition contains from about 7% to about 35%, more preferably, from about 14% to about 25% phosphate builder, by weight of the total bar composition. The phosphate bulider Is selected from the group consisting of phosphates, pyrophoephates, 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 pyropnospnates, orthophosphates, tripolyphosphates, higher polyphosphates, and mixtures thereof. Preferred phosphate builders are a water-soluble alkali-metal salt of tripolyphosphate, and a mixture of tripolyphoephate 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 alkyi ether sulfurlc acid and aikyibenzene sulfonic acid. Co-polymers of acrylic acid and malelc acid are preferred in the subject compositions as auxiliary builders. B, Other bleach agents
The present invention composition contains a mixture of perborate and percarbonate at a specific ratio as a bleach agent. Other bleach agents can also be used herein in addition to perborate and percarbonate. Any of the known bleach agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes may be used,
Other bleach agents include hydrogen peroxide and the alkali metal peroxides, the alkali earth metal peroxide, organic peroxide bleaching compounds such as urea peroxide, and Inorganic persalt bleaching compounds,
such as the alkali metal perphosphates, and the like. Mixtures of two or more such bleaching compounds can also be used, if desired.
Preferred other bleach agents are selected from the group consisting of peroxyhydrates, peroxides, persulfates, and mixtures thereof.
Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used. C. 8leach activators
The detergent compositions herein may 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 c* the formulae;
R1N(R5)C(0)R2C(0)L or RlC(0)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 alkaryi 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 nucleophlllc attack on the bleach activator by the perhydrolysis anion. A preferred leaving group i& phenyl sulfonate.
Preferred examples of bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesuifonate, {6-nonanamidocaproyl)oxybenzenesulfonati,
(6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as described In U.S. Patent 4,634,551.
Another class of bleach activators contains 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 benzoxazirt-type is:
(Figure Removed)
Still another class of preferred bleach activators Includes the acyl lactam activators, especially acyl caprolaetams and acyl valerolactams of the formulae:
(Formula Removed)
wherein R6 is H or an alkyl, aryl, afkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms. Highly preferred lactam activators Include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caproladam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl vaierolactam, octanoyl valerolactam, decanoyf valerolactam, undacenoyl vaieroiactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1935, which discloses acyl caprolactams, Including benzoyl caprolactam, adsorbed into sodium perborate. D. Bleach catalyst
The laundry bar composition of the present invention may also contain 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 bo 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. 549,271 A1, 549.272A1, 544.440A2, and 544.490A1;
Preferred examples of these catalysts Include Mn'V2(u-°)3('.4,7-trlmethyl-l14,7.
triazacycJononane)2(PF6)2- Mn"(2(u-0)i{U-OAc)2(1,4,7-trimethyl-1l4,7-
triazacyclononane)2.(CI04)2, Mn'v4(u*0)g(l ,4,7-triazacyciononane)4{CIO4)4, MnlHMnlv4(u-0)i (u-OAc)2-(1,4,7-trimethyl-1,4,7-triazacyctononana)2(Ci04)3, Mn'v(1,4,7.trimethyl-1,4,7-triazacyclononaneHOCH3)3(PFe), 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.
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. E. Enzymes
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. Upases, cellulases, and peraxidases, as well as mixtures thereof.
A wide range of enzyme materials and means for their incorporation fnto synthetic detergent compositions are also disclosed In U.S. Patent 3,553,129. 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, 1965, both. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. Patent 4,261,868, Mora etal, 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. 86200536.5, 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 3. subtilis and B. lichenifomis, One suitable protease is Obtained from a strain of Bacillus, having maximum activity throughout the pH ranga 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 G8 1,243,784 to Novo, Other suitable proteases
include ALCAUSE™ and SAVINASE™ from Novo and MAXATASE™ from International Bio-Synthetics, Inc., The Netherlands; as well as Protease A as disclosed in EP 130.756 A, January 9, 1985 and Protease & 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 rocombinant trypsln-like protease for detergents suitable herein Is described in WO 9425563 to Novo.
In more detail, an especially preferred protease, referred to as "Protease D" Is a carbonyl hydrolase variant having an amino add 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, +208, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyicliquefaciens subtilisln, as described in the patent applications of A. Baeck, et ai, entitled "Pratease-Containlng Cleaning Compositions' having US Serial No. 08/322,676, and C. Ghosh, et a!, "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 commorcial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composftion.
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 US, Patent 4,435,307, Barbesgoard et al, issued March 6, 1984, which discloses fungal cellulase produced from Humlcola insolens and Humlcola 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™ (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 Csrezyme™ having an activity of 5000 CEVU per gram. Most preferable Is Carezyme™ having an activity of 1000 CEVU per gram.
A preferred bar composition contains 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™, International Bio-Synthetics, Inc. and TERMAMYL™, Novo. FUNGAMYL™ from Novo is especially useful. Engineering of enzymes for improved stability, e.g., oxldative 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 TERMAMYL™ in commercial use in 1993, These preferred amylases herein share the characteristic of being "stability-enhanced" amylases, characterized, at a minimum, by a measurable improvement in one or more of: oxjdative stability, e.g., to hydrogen peroxide / tetraacetylethyienedlamtne in buffered solution at pH 9-10; thermal stability, e.g., at common wash temperatures such as about 60^0; or alkaline stability, e.g., at a pH from about 6 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 Badilus -amylases, regardless of whether one, two or multiple amylase strains are the Immediate precursors. Oxldative 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 alanin* or threonine, preferably threonine, of trie 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. amylollquefaciens, B, subtilis, or 8, steanthermophflus; (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. Mltchinson. 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 lichenifotmis NCIB60G1. 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 433 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 9309909 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 fnclude -amytases characterized by having a specific activity at least 25% higher than the specific activity of Termamyl™ at a temperature range of 25eC to 55*C and at a pH value in the range of 8 to 10, measured by the Phadebas™ -amylase activity assay. (Such Phadebas™ -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 SEC ID listings in the references.
Amylase enzymes are usually present in an amount that ranges from about 0,0046 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 Pseudcmonas stutzeri ATCC 19,154, as disclosed in GB 1,372,034, See also tipases 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 CAromooacter viscosum, e.g. C/iromobacfer viscosum ver. HpQlyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobictef vIscQsum 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 RO 94359044.
Lipase activity Is expressed in Lipase Unit (LU) which is the amount of lipase which produces 1umol 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 emulsion of 3.3 wt% of olive oil and 3.3% gum arable, in the presence of 13mmoVi Ca2+ mmol/l NaCI In 5 mmol/l Trls 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, ilgnlnase, and haloperoxldase such as chloro- and brcmo-peroxidase. Peroxidase-contalning 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, thermostabllity, 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 ceilulases.
F. Moisture
The composition of the present Invention preferably has a total moisture content from about 0,1% to about 6%, by weight of the final bar composition. Preferably, the bar composition has a total moisture content from about 1% to about 5*/c, more preferably, from about 2.5% to about 4.S%, 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 Bldwell 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.
G. Hydrotropes
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 sultanate, cumane sulfonate, sulfosuccinate, and mixtures thereof. Preferably, the hydrotrope is added to the linear alky! benzene suffonic acid prior to its neutralization. The hydrotrope, ff present, will preferably be present at from about 0.5% to about 5% of the laundry detergent bar. H. Binding agents
Binding agents are 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 contains 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. Other useful binding agents are solid non-thixotropic binding agents such as cocomonoethanolamide (CMEA). I, Soil suspending agents
Soil suspending agents can also be used. Soil suspending agents can also include water-soluble salts of carboxymethyicelluiose and carboxyhydroxymethylcellulose. A preferred soil suspending agent is an acrylic/malelc copolymer, commercially available as Sokolan®, from BASF Corp, Other soiJ 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 0.1-1%. J. Crtelatlng agents
A preferred component of the present invention is a chelating agent. Such chela ting agents are able to sequester and cheiate 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 cheating 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 cheating agent, particularly one selected from the group consisting of diethylenetriamlne penta(methy)ene phosphonic acid), ethylene diamEne tetra(methylene phosphonic acid), and mixtures and salts and complexes thereof, and an acetate chelating agent, particularly one selected from the group consisting of diethylenetriamlne penta(acetlc acid), ethylene diamine tetra(acetlc 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, sine, magnesium, and aluminum salts and complexes of dlethylenetn'amine penta(methylene phosphonate) diethylenetriamlne penta (acetate), and mixtures thereof.
Preferably such salts or complexes have & 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%. K. Other additional components
Other additional components of the laundry bars include 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 exhibrt less base odor of fatty alcohol relative to broad cut fatty alcohols. Typically fatty alcohol, 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 alcohol. However, low levels of fatty alcohol can be introduced into the bans 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.
Other additional components In the laundry bars include a dye transfer inhibiting (DTI) ingredient to prevent diminishing of color fidelity and intensity in fabrics. A preferred DTI ingredient can include polymeric OTI materials capable of binding fugitive dyes to prevent them from depositing on the fabrics, and decolortzation 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 percarfconate or pert orate. Non-limiting examples of polymeric DTI materials include polyvinylpym'dine N-oxide, polyvlnylpyrrolWone (PVP), PVP-polyv!nylim!dazole copolymer, and mixtures thereof. Copolymers of N-vinylpyrrolidone and N-vinylimidazol© 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%.
Other additional components in the laundry bar include 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 Cg to C22 nydrocarbyl, RS and Re are Independently Ci to Cio hydrocarbyl. One preferred amine is dltallowmethyl amine; complexes of such amines with fatty acid of the formula R7COOH, wherein R? Is Cg to 022 hydrocarbyl, as disclosed In EP No, 0,133,804; complexes of such amines with phosphate esters of the formula R8Q-P(O)(QH)-OR and HO-P(0)(OH)ORQ, wherein RS and Rg are independently C1 to C20 alkyl of alkyl ethoxyiate of the formula -alkyl-(OCH2CH2); cyclic amines such as imfdazolines of the general formula 1-(higher alkyl) amino (lower alkyl)-2-higher alkyljlmldazollne, where higher alkyl is from 12 to 22 carbons and lower alkyl Is from 1 io 4 carbons, such as described in UK Patent Application GB 2,173,827; and quaternary ammonium compounds of the formula R10R11R12R13N*X-, wherein R10 is alkyl having 8 to 20 carbons, RII is alkyl having 1 to 10 carbons, R12 and R18 are alkyl having 1 to 4 carbons, preferably methyl, and X Is an anlon, preferably CC or Br, such as C12-13 alkyl trimethy! 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-sllicates 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 day can be added to the bar to provide about 1% to about 60% 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 am 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 Pe203) In the crystal lattice, and which had a very high ion exchange capacity, Is one of the most efficient and effective days 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 fait below the requisite range; such clays are of no use in the Instant compositions.
A day flocculating agent In a laundry bar is also be an additional component. 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 ethyiene oxide, acrylamide, acrylic add, dimethylamino ethyl methacrylate, vinyl alcohol, vinyl pyrrolldone, and ethyiene imfne. Gums, like guar gums, are suitable as well. The preferred clay flocculating agent is a polyethylene oxide) polymer. The amount of clay flocculating agent, If any, is about 0,2-2%, preferably about O.S-1%.
Optical brlghteners can also be additional ingredients In laundry bars of the present Invention, Preferred optical brighteners are diamino stilbene, distyriiblphenyl-type optical brlghteners. Preferred as examples of such brighteners are 4,4'-b!s{[4-anilino-6-bis(2-hydoxyethyO amine~1,3,5-trizin-2-yl]amlno}stiibene-212'.disulfonic acid dlsodium salt, 4-4'-bls(2-sulfostyryi) biphenyt and 4l41-bis((4-anilino-6-rnorpholino-1,3,5-triazln-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% -1.0%.
Other additional components are a photobleach material, particularly phthaiocyanlne photobleaches which are described in U.S. Patent 4,033,713 issued July 5,1977, incorporated herein by reference. Preferred photobleaches are metal phthaiocyanine 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 TIN OLDS or as zinc phthaiocyanine 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%.
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%.
Titanium dioxide is another additional component, (t can be a preferred ingredient for aesthetics of the bar composition, e.g. whiteness. Process
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 alKatlne inorganic salts 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 can 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 ft is wrapped, cased, and sent to storage. It la 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 maten'als 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 adds.) 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, sodium perborate and sodium percarboante at a specific ratio and optionally, enzymes can be added to the mixture and then mixed, preferably, for an additional 2 minutes. It is preferred that when the peroxygen bleaches are 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 oar 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.
(weight percent)
(Table Removed)
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.




WHAT IS CLAIMED IS:
1. A laundry detergent bar composition comprising perborate and
percarbonate at a specific ratio, wherein the ratio of the perborate and the
percarbonate is from about 65:15 to about 30:70.
2. The detergent bar composition according to claim 1, wherein the ratio of
the perborate and the percarbonate ,s from about 85:15 to about 50:50.
3. The detergent bar composition according to Claim 1, comprising from
about 0.1% to about 20% of a mixture of perborate and percartsonats, by weight
of the total bar.
4. A laundry detergent bar composition comprising:

(a) a mixture of perborate and percarbonate wherein the ratio of the perborate
and the percarbonate is from about 85:15 to about 30:70;
(b) a detersive surfactant; and
(c) a detergent builder.

5. The detergent bar composition according to Claim 4, wherein the bar
composition comprises from about 10% to about 60% by weight of surfactant and
from about 5% to about 60% by weight of detergent builder,
6. The detergent bar composition according to Claim 4, wherein the
detersive surfactant Is selected from the group consisting of anionic, catlonic,
amphoteric, nonlonic surfactant, and mixtures thereof; and wherein the detergent
builder is selected from the group consisting of phosphates, pyrophospnates,
orthophosphates, trlpolyphosphates, higher phosphates, alkali metal carbonates
and bicarbonates, alkali silicates, aluminosilicates, poly car boxyIa tes, and
mixtures thereof.
7. The detergent bar composition according to Claim 4, wherein the bar
composition further comprises an enzyme selected from the group consisting of
protease, cellulase, amylase, lipase, peroxidase and mixtures thereof.
8. The detergent bar composition according to Claim 4, wherein the
perborate is selected from the group consisting of sodium perborate
monohydrate, sodium perborate tetrahydrate and mixtures thereof and the
percarbonate is selected from the group consisting of sodium percarbonate,
potassium percarbonate and mixtures thereof.
9. The detergent bar composition according to Claim 6, wherein the anionic
surfactant is selected from the group consisting of linear alkyl benzene sulfbnate,
alkyl sulfate, alkyl ethoxylate suffate and mixtures thereof.
10. The detergent bar composition according to Claim 6, wherein the anionic
surfactant Is a mixture of CFAS (Coconut Fatty Alcohol Sulfate} and LAS (Linear
Alkyl Sulfate} at a ratio of from about 0:100 to about 100:0.
11. A laundry detergent bar substantially as hereinbefore described
in any one of the examples.

Documents:

1274-del-1999-abstract.pdf

1274-del-1999-assignment.pdf

1274-del-1999-claims.pdf

1274-del-1999-correspondence-others.pdf

1274-del-1999-correspondence-po.pdf

1274-del-1999-description (complete).pdf

1274-del-1999-form-1.pdf

1274-del-1999-form-19.pdf

1274-del-1999-form-2.pdf

1274-del-1999-form-26.pdf

1274-del-1999-form-5.pdf

1274-del-1999-petition-138.pdf


Patent Number 213223
Indian Patent Application Number 1274/DEL/1999
PG Journal Number 01/2008
Publication Date 04-Jan-2008
Grant Date 24-Dec-2007
Date of Filing 22-Sep-1999
Name of Patentee THE PROCTER & GAMBLE COMPANY
Applicant Address ONE PROCTER & GAMBLE PLAZA, CINCINNATI, OHIO 45202 UNITED STATES OF AMERICA.
Inventors:
# Inventor's Name Inventor's Address
1 TRAJANO, TRACE WENDELL DE GUZMAN 1632 A. MACEDA ST. SAMPALOC MANILA 1015 PHILIPPINES.
2 MIRASOL, MA AMELITA GONZALES 30 P STA. AGUEDA DRIVE, CITIHOMES REGENCY PARANAQUE METRO, PHILIPPINES.
3 AUGUSTIN , JOSIELY GONZAGA BLK LOT 13 CORTEZ ST., PARKVIEW HOME SUNVALLEY PARANAQUE 1700 PHILIPPINES.
PCT International Classification Number C11D 3/39
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 US98/19914 1998-09-23 U.S.A.