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EP0693105A1 - Compositions detergentes - Google Patents

Compositions detergentes

Info

Publication number
EP0693105A1
EP0693105A1 EP94914042A EP94914042A EP0693105A1 EP 0693105 A1 EP0693105 A1 EP 0693105A1 EP 94914042 A EP94914042 A EP 94914042A EP 94914042 A EP94914042 A EP 94914042A EP 0693105 A1 EP0693105 A1 EP 0693105A1
Authority
EP
European Patent Office
Prior art keywords
builder
weight
zeolite
alkyl
composition according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP94914042A
Other languages
German (de)
English (en)
Other versions
EP0693105A4 (fr
Inventor
Gerald Marcel Baillely
Susan Eleanor Stewart
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0693105A1 publication Critical patent/EP0693105A1/fr
Publication of EP0693105A4 publication Critical patent/EP0693105A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds

Definitions

  • Layered silicate builders are used in combination with secondary (2,3) alkyl sulfate surfactants in laundry detergent compositions.
  • the compositions minimize the deposition of inor ⁇ ganic matter onto fabrics, which helps to maintain the soft "hand" of fabrics laundered therewith.
  • Detergent formulators are faced with a variety of diffi ⁇ culties when preparing laundry detergent compositions. In general, such compositions must be safe with respect to the user and with respect to the fabrics being laundered. On the other hand, such compositions must be sufficiently robust that they will remove a wide variety of tenacious soils and stains from fabrics under usage conditions which range from cold water washing tem ⁇ peratures up to boil washes.
  • Phosphate builders were once highly important to detergent formulators, since they safely and economically enhance the cleaning performance of synthetic detersive surfactants. However, phosphate builders are not now in use in many regions of the world, and detergent formulators have turned to nonphosphorus builder materials, Including various polycarboxylate builders. However, polycarboxylate builders are not as effective as phos ⁇ phates and must often be used in combination with other ingredi ⁇ ents to enhance detergency performance.
  • zeolites Since the mid-1970's, zeolites have become the builders of choice, especially for the formulation of heavy-duty granular laundry detergents. Unfortunately, minuscule amounts of the zeolites can deposit onto fabric surfaces each time fabrics are laundered with zeolite-built detergents. As the fabrics undergo multiple washes, the zeolite buildup (also sometimes referred to as "ash” or "inorganics”) can reach sufficient levels that the original soft feel, or "hand", of the fabrics is substantially diminished.
  • the proper selection of surfactants Ue., the secondary (2,3) alkyl sulfates ("SAS"), used in combination with layered silicate builders, provides detergent compositions which minimize much of the aforesaid undesirable build-up of inorganic deposits onto fabrics.
  • the secondary (2,3) alkyl sulfates are mild to skin.
  • the secondary alkyl (2,3) sulfates are more soluble in aqueous media than their counterpart primary alkyl sulfates of comparable chain lengths. Accordingly, they can be formulated as readily-soluble, high-surfactant (i.e., "high-active”) concen ⁇ trated granular laundry detergents.
  • the secondary (2,3) alkyl sulfates can be made available in solid, particulate form, they can be dry-mixed into granular detergent compositions without the need for passage through spray drying towers.
  • the secondary (2,3) alkyl sulfates when used in the manner disclosed herein, it has now been determined that they are both aerobically and anaerobically degradable, which assists in their disposal in the environment.
  • Preferred detergent compositions which comprise biodegradable or otherwise ecologically acceptable ingredients can thus be provided.
  • the present invention relates to detergent compositions especially adapted to laundering fabrics with minimized build-up of inorganic residues, especially zeolite builder residues, on said fabrics, characterized by: i) a builder system which comprises a layered silicate builder and optional adjunct builders; and ii) a detersive surfactant system which comprises secondary
  • the minimum amount of layered silicate builder in the finished product is at least 4%, by weight, and preferably ranges from about 10% to about 50% by weight of the compositions.
  • zeolites can optionally be used as adjunct builders in the present compositions.
  • the amount of zeolite builder should be no more than 22%, prefer- ably no more than 16%, by weight of said compositions.
  • the amount of zeolite builder should be no more than 30%, preferably no more than 22%, by weight of said compositions.
  • the compositions can also comprise polycarboxylate adjunct builders, especially citrate, and thus include mixtures of such carboxylate builders plus the layered silicate, optionally with zeolites.
  • the polycarboxylate builders will typically comprise from about 5% to about 20% by weight of the compositions. Mixtures of layered silicate/citrate and layered silicate/cit ⁇ rate/zeolite builders within the compositional ranges noted above are preferred builders herein.
  • compositions can optionally comprise nonionic adjunct surfactants as well as optional anionic adjunct surfactants such as members selected from the group consisting of alkylbenzene suifonates, alkylether sulfates, alpha-sulfonated fatty acid esters, branched-chain and linear primary alkyl sulfates, and mixtures thereof.
  • nonionic adjunct surfactants such as members selected from the group consisting of alkylbenzene suifonates, alkylether sulfates, alpha-sulfonated fatty acid esters, branched-chain and linear primary alkyl sulfates, and mixtures thereof.
  • anionic adjunct surfactants such as members selected from the group consisting of alkylbenzene suifonates, alkylether sulfates, alpha-sulfonated fatty acid esters, branched-chain and linear primary alkyl sulfates, and mixtures thereof.
  • compositions herein can also optionally contain various adjunct cationic surfactants, and mixtures of such cationic and nonionic adjunct surfactants.
  • Useful cationics include the io-Ci ⁇ alkyl trimethylammonium halides, the Cio-Ci ⁇ alkyl dimethyl (Ci-C ⁇ ) hydroxyalkylammonium halides, Cio-Ci ⁇ choline esters, and the like. If used, such cationic surfactants can comprise from 1% to 15% by weight of the compositions herein.
  • compositions herein can additionally comprise a dispers- ing agent, which further assists in the diminution of inorganic residues on fabrics.
  • Preferred compositions comprise said layered silicate builder, said secondary (2,3) alkyl sulfate surfactant, from 0% to 22% by weight of zeolite adjunct builder and a dispers ⁇ ing agent, especially polyaspartate, at levels of dispersing agent preferably in the range from about 0.1% to about 7% by weight.
  • compositions herein can additionally comprise one or more auxiliary cleaning or fabric conditioning agents selected from the group consisting of enzymes, soil release agents, bleach and bleach activators, clay fabric softeners, optical brighteners, and mixtures thereof.
  • auxiliary cleaning or fabric conditioning agents selected from the group consisting of enzymes, soil release agents, bleach and bleach activators, clay fabric softeners, optical brighteners, and mixtures thereof.
  • Such agents typically comprise from about 0.1% to about 45% by weight of the compositions.
  • a highly preferred granular detergent composition herein comprises nonphosphate ingredients, characterized in that at least 60% of the ingredients therein comprise a mixture of: i) an anionic surfactant, typically 10%-30% by weight, which is a secondary (2,3) alkyl sulfate; ii) optionally, a nonionic surfactant which is a polyhydroxy fatty acid amide, an alkyl polyglycoside, or mixtures thereof, typically 5%-30% by weight; iii) optionally, an anionic surfactant which is a member selected from the group consisting of linear primary alkyl sulfates, alkyl ether sulfates, or mixtures thereof; iv) at least 4%, preferably from about 4% to about 35% by weight, of a layered silicate builder; v) optionally, a polycarboxylate builder; vi) optionally, a zeolite builder which comprises no more than 22% by weight, preferably no more than 16% by weight, of the
  • the invention also encompasses a method for cleaning fabrics while minimizing zeolite builder residues on said fabrics, characterized in that it comprises contacting said fabrics, preferably with agitation, with an aqueous bath which contains at least about 100 ppm (typically 100 ppm-5000 ppm) of a laundry detergent which comprises a secondary (2,3) alkyl sulfate surfactant, and a layered silicate builder, said detergent composition containing no more than 22% by weight of zeolite builder.
  • a laundry detergent which comprises a secondary (2,3) alkyl sulfate surfactant, and a layered silicate builder, said detergent composition containing no more than 22% by weight of zeolite builder.
  • the C10-C20 secondary (2,3) alkyl sulfates can conveni ⁇ ently be employed herein.
  • the C14-C18 compounds are preferred for laundry cleaning operations. All percentages, ratios and proportions herein are by weight, unless otherwise specified. All
  • Alkyl Sulfate Surfactants For the conveni ⁇ ence of the formulator, the following identifies and illustrates the differences between the sulfated surfactants employed herein and otherwise conventional alkyl sulfate surfactants. Conventional primary alkyl sulfate surfactants have the general formula
  • R0S03"M+ wherein R is typically a linear C10-C20 hydrocarbyl group and M is a water-solubilizing cation.
  • Branched-chain primary alkyl sulfate surfactants i.e., branched-chain "PAS" having 10-20 carbon atoms are also known; see, for example, European Patent Application 439,316, Smith et al , filed 21.01.91.
  • Secondary alkyl sulfate surfactants are those materials which have the sulfate moiety distributed randomly along the hydrocarbyl "backbone" of the molecule. Such materials may be depicted by the structure
  • x and (y+1) are, respectively, integers of at least about 6, and can range from about 7 to about 20, preferably about 10 to about 16.
  • M is a cation, such as an alkali metal, ammonium, alkanolammonium, alkaline earth metal, or the like.
  • Sodium is typical for use as M to prepare the water-soluble (2,3) alkyl sulfates, but ethanolam- monium, diethanolammonium, triethanolammonium, potassium, ammonium, and the like, can also be used.
  • the physical/chemical properties of the foregoing types of alkyl sulfate surfactants are unexpectedly different, one from another, in several aspects which are important to formulators of various types of detergent compositions.
  • the primary alkyl sulfates can disadvantageously interact with, and even be precipi ⁇ tated by, metal cations such as calcium and magnesium.
  • the primary alkyl sulfates can be problematic due to such interactions with calcium or magnesium cations.
  • the solubility of the primary alkyl sulfates is not as great as the secondary (2,3) alkyl sulfates.
  • the formulation of high-active surfactant particles has now been found to be simpler and more effective with the secondary (2,3) alkyl sulfates than with the primary alkyl sulfates.
  • the secondary (2,3) alkyl sulfates are exceptionally easy to formulate as heavy-duty laundry detergents.
  • the random secondary alkyl sulfates i.e., secondary alkyl sulfates with the sulfate group at positions such as the 4, 5, 6, 7, etc. secondary carbon atoms
  • such materials tend to be tacky solids or, more generally, pastes.
  • the random alkyl sulfates do not afford the processing advantages associated with the solid secondary (2,3) alkyl sulfates when formulating detergent granules, bars, or tablets.
  • the secondary (2,3) alkyl sulfates herein provide better sudsing than the random mixtures.
  • the secondary (2,3) alkyl sulfates be substantially free (i.e., contain less than about 20%, more preferably less than about 10%, most preferably less than about 5%) of such random secondary alkyl sulfates.
  • One additional advantage of the secondary (2,3) alkyl sulfate surfactants herein over other positional or "random" alkyl sulfate isomers is in regard to the improved benefits afforded by said secondary (2,3) alkyl sulfates with respect to soil redeposition in the context of fabric laundering operations. As is well-known to users, laundry detergents loosen soils from fabrics being washed and suspend the soils in the aqueous laundry liquor.
  • the secondary (2,3) alkyl sulfates used herein are quite different in several important properties from the secondary olefin suifonates (e.g., U.S. Patent 4,064,076, Klisch et al, 12/20/77); accordingly, the secondary suifonates are not the focus of the present invention.
  • the preparation of the secondary (2,3) alkyl sulfates of the type useful herein can be carried out by the addition of H2SO4 to olefins.
  • a typical synthesis using o-olefins and sulfuric acid is disclosed in U.S. Patent 3,234,258, Morris, or in U.S. Patent 5,075,041, Lutz, granted December 24, 1991.
  • solubility of the "crystalline" secondary (2,3) alkyl sulfate surfactants is desired, the formulator may wish to employ mixtures of such surfactants having a mixture of alkyl chain lengths.
  • a mixture of C12-C18 alkyl chains will provide an increase in solubility over a secondary (2,3) alkyl sulfate wherein the alkyl chain is, say, entirely Ci6-
  • the solubility of the secondary (2,3) alkyl sulfates can also be enhanced by the addition thereto of other surfactants such as the alkyl ethoxylates or other nonionic surfactants, or by any other material which decreases the crystallinity of the secondary (2,3) alkyl sulfates.
  • Such crystalUnity-interrupting materials are typically effective at levels of 20%, or less, of the secondary (2,3) alkyl sulfate.
  • the layered silicate builders used herein include various alkali metal silicates, particularly those having a Si ⁇ 2: a2 ⁇ ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck.
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6").
  • the Na SKS-6 silicate builder does not contain aluminum.
  • NaSKS-6 has the delta- a2Si ⁇ 5 morphology form of layered silicate.
  • SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi ⁇ 2 ⁇ +i*yH2 ⁇ wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein.
  • Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms.
  • delta-Na2Si0s (NaSKS-6 form) is most preferred for use herein.
  • Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
  • Adjunct Ingredients can optionally be included in the compositions herein to assist in controlling mineral hardness.
  • Inorganic as well as organic builders can be used.
  • Builders are typically used in fabric laundering composi ⁇ tions to assist in the removal of particulate soils.
  • adjunct builder can vary widely depending upon the end use of the composition and its desired physical form.
  • the compositions will typically comprise at least about 1% adjunct builder.
  • Granular formulations typically com ⁇ prise from about 10% to about 80%, more typically from about 15% to about 50% by weight, of the detergent builder.
  • Lower or higher levels of builder are not meant to be excluded, so long as the relative total amounts of the layered silicate builder and the zeolite adjunct builder set forth hereinabove are followed.
  • Aluminosilicate builders i.e., zeolites
  • Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations.
  • Aluminosilicate builders include those having the empirical formula:
  • Preferred aluminosilicates are zeolite builders which have the formula:
  • aluminosilicate ion exchange materials are commer ⁇ cially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosili ⁇ cates or synthetically derived. A method for producing alumino- silicate ion exchange materials is disclosed in U.S.
  • Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), and Zeolite X.
  • the crystalline aluminosilicate ion exchange material has the formula:
  • This material is known as Zeolite A.
  • the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
  • Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds.
  • polycar ⁇ boxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred. Included among the polycarboxylate builders are a variety of categories of useful materials.
  • poly ⁇ carboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al , on May 5, 1987.
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
  • ether hydroxy- polycarboxylates copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisul- phonic acid, and carboxymethyloxysuccinic acid
  • various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid
  • polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricar- boxylic acid, carboxy ethyloxysuccinic acid, and soluble salts thereof.
  • Citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular composi ⁇ tions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations. Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-l,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986.
  • succinic acid builders include the C5-C20 alkyl and alkenyl succinic adds and salts thereof.
  • a particularly preferred compound of this type is dodecenylsuccinic acid.
  • succinate builders include: laurylsuc ⁇ cinate, yristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccin- ates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
  • Fatty acids e.g., C1 -C18 monocarboxylic acids
  • the aforesaid builders especially citrate and/or the succinate builders, to provide additional builder activity.
  • Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
  • Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
  • Phosphate builders may be used in regions of the world where they are acceptable, but are not preferred herein.
  • Enzymes - Detersive enzymes may optionally, but preferably, be included in the detergent formulations herein for a wide variety of fabric laundering purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, for the prevention of refugee dye transfer and for fabric restoration.
  • the enzymes to be incorporated include proteases, amylases, Upases, cellulases, and peroxidases, as well as mixtures thereof. 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, ther ostability, 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.
  • Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically about 0.01 mg to about 3 mg, of active enzyme per gram of the composition. Stated otherwise, the compositions herein will typically comprise from about 0.001% to about 5%, preferably 0.01%-1%, by weight of a commercial enzyme preparation. 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. Suitable examples of proteases are the subtilisins which are obtained from particular strains of B.subtilis and B.licheniforms.
  • protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trade name ESPERASE. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No. 1,243,784 of Novo.
  • Proteolytic enzymes suitable for removing protein-based stains include those sold under the tradenames ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (The Netherlands).
  • Other proteases include Protease A (see European Patent Application 130,756, published January 9, 1985) and Protease B (see European Patent Application Serial No. 87303761.8, filed April 28, 1987, and European Patent Application 130,756, Bott et al, published January 9, 1985).
  • Amylases include, for example, ⁇ -amylases described in British Patent Specification No. 1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo Industries.
  • the cellulases 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-0S-2.247.832.
  • 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 British Patent 1,372,034. See also Upases in Japanese Patent Application 53-20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P.” Other commercial Upases include Amano-CES, Upases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
  • 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 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 0. Kirk, assigned to Novo Industries A/S.
  • Enzvme Stabilizers The enzymes employed herein are stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes. (Calcium ions are generally somewhat more effective than magnesium ions and are preferred herein if only one type of cation is being used.) Additional stability can be provided by the presence of various other art-disclosed stabil ⁇ izers, especially borate species: see Severson, U.S. 4,537,706, cited above.
  • Typical detergents, especially liquids will com ⁇ prise from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 5 to about 15, and most preferably from about 8 to about 12, millimoles of calcium ion per liter of finished composition. This can vary somewhat, depending on the amount of enzyme present and its response to the calcium or magnesium ions.
  • the level of calcium or magnesium ions should be selected so that there is always some minimum level available for the enzyme, after allowing for complexation with builders, fatty acids, etc., in the composition.
  • any water-soluble calcium or magnesium salt can be used as the source of calcium or magnesium ions, including, but not limited to, calcium chloride, calcium sulfate, calcium malate, calcium maleate, calcium hydroxide, calcium formate, and calcium acetate, and the corresponding magnesium salts.
  • a small amount of calcium ion generally from about 0.05 to about 0.4 millimoles per liter, is often also present in the composition due to calcium in the enzyme slurry and formula water.
  • the formulation may include a sufficient quantity of a water-soluble calcium ion source to provide such amounts in the laundry liquor. In the alternative, natural water hardness may suffice.
  • compositions herein will typically comprise from about 0.1% to about 2% by weight of a water-soluble source of calcium or magnesium ions, or both. The amount can vary, of course, with the amount and type of enzyme employed in the composition.
  • compositions herein may also optionally, but preferably, contain various additional stabilizers, especially borate-type stabilizers.
  • additional stabilizers especially borate-type stabilizers.
  • such stabilizers will be used at levels in the compositions from about 0.25% to about 10%, preferably from about 0.5% to about 5%, more preferably from about 0.75% to about 3%, by weight of boric acid or other borate compound capable of forming boric acid in the composition (calculated on the basis of boric acid).
  • Boric acid is preferred, although other compounds such as boric oxide, borax and other alkali metal borates (e.g., sodium ortho-, meta- and pyroborate, and sodium pentaborate) are suitable.
  • Substituted boric acids e.g., phenylboronic acid, butane boronic acid, and p-bromo phenylboronic acid
  • bleaching agents may be at levels of from about 1% to about 30%, more typically from about 5% to about 20%, of the detergent composition, especially for fabric laundering. If present, the amount of bleach activators will typically be from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.
  • the bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents.
  • Perborate bleaches e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.
  • One category of bleaching agent that can be used without restriction encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
  • Such bleaching agents are dis ⁇ closed in U.S. Patent 4,483,781, Hartman, issued November 20,
  • Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al .
  • Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxy- hydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used. Mixtures of bleaching agents can also be used. Peroxygen bleaching agents, the perborates, the percarbon- ates, 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.
  • the nonanoyloxybenzene sulfon- ate (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.
  • Bleaching agents other than oxygen bleaching agents are also known 1n the art and can be utilized herein.
  • One type of non- oxygen bleaching agent of particular interest includes photo- activated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. See U.S.
  • detergent compositions will typically contain from about 0.025% to about 1.25%, by weight, of such bleaches, especially sulfonated zinc phthalocyanine.
  • Polymeric Soil Release Agent Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions and processes of this invention.
  • Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
  • the polymeric soil release agents useful herein especially include those soil release agents having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to about 30 oxypropylene units wherein said mixture con ⁇ tains a sufficient amount of oxyethylene units such that the hydrophile component has hydrophilicity great enough to increase the hydrophilicity of conventional polyester synthetic fiber surfaces upon deposit of the soil release agent on such surface, said hydrophile segments preferably comprising at least about 25% oxyethylene units and more preferably, especially for such compon ⁇ ents having about 20 to 30 oxypropylene units, at
  • the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from 2 to about 200, although higher levels can be used, preferably from 3 to about 150, more prefer- ably from 6 to about 100.
  • Suitable oxy C4-C6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as M ⁇ 3S(CH2)nOCH2CH2 ⁇ -, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink.
  • Polymeric soil release agents useful in the present invention also include cellulosic derivatives such as hydroxyether cellu- losic polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of Cj-C4 alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al .
  • Soil release agents characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., Ci-C ⁇ vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones.
  • poly(vinyl ester) e.g., Ci-C ⁇ vinyl esters
  • poly(vinyl acetate) grafted onto polyalkylene oxide backbones such as polyethylene oxide backbones.
  • Commercially available soil release agents of this kind include the S0KALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany).
  • One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate.
  • This polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur issued July 8, 1975.
  • Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units containing 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000.
  • this polymer include the commercially available material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
  • Another preferred polymeric soil release agent is a sulfon ⁇ ated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone.
  • These soil release agents are described fully in U.S. Patent 4,968,451, issued November 6, 1990 to J. J. Scheibel and E. P. Gosselink.
  • Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al , the anionic end-capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
  • Preferred polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al, which discloses anionic, especially sulfo- aroyl, end-capped terephthalate esters.
  • soil release agents will generally comprise from about 0.01% to about 10.0%, by weight, of the detergent composi ⁇ tions herein, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0%.
  • Chelatinq Agents may also optionally contain one or more iron and/or manganese chelating agents.
  • Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
  • Amino carboxylates useful as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyethylethylenedi- aminetriacetates, nitrilotriacetates, ethylenediamine tetrapropri- onates, triethylenetetraaminehexaacetates, diethylenetriamine- pentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
  • Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent composi ⁇ tions, and include ethylenediaminetetrakis (methylenephosphon- ates), nitrilotris (methylenephosphonates) and diethylenetriamine- pentakis (methylenephosphonates).
  • these amino phos ⁇ phonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al .
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy -3,5-disulfobenzene.
  • EDDS ethylenediamine disuccinate
  • these chelating agents will generally comprise from about 0.1% to about 10% by weight of the detergent composi ⁇ tions herein. More preferably, if utilized, the chelating agents will comprise from about 0.1% to about 3.0% by weight of such compositions.
  • compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and anti-redeposition properties.
  • Granular detergent compositions which contain these compounds typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylated amines; liquid detergent compositions typically contain about 0.01% to about 5%.
  • the most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986.
  • Another group of preferred clay soil removal/antiredeposition agents are the cationic compounds dis ⁇ closed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984.
  • Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S.
  • Other clay soil removal and/or antiredeposition agents known in the art can also be utilized in the compositions herein.
  • Another type of preferred anti- redeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.
  • CMC carboxy methyl cellulose
  • Polymeric Dispersing Agents can advantageously be utilized at levels from about 0.1% to about 7%, by weight, in the compositions herein, especially in the presence of zeolite and/or layered silicate builders. Suitable polymeric dispersing agents include polymeric polycarboxylates and poly ⁇ ethylene glycols, although others known in the art can also be used.
  • polymeric dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release peptization, and anti-redeposition.
  • Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form.
  • Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylene alonic acid.
  • the presence in the polymeric polycarboxylates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.
  • Particularly suitable polymeric polycarboxylates can be derived from acrylic acid.
  • acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid.
  • the average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000.
  • Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued March 7, 1967.
  • Acrylic/maleic-based copolymers may also be used as a pre ⁇ ferred component of the dispersing/anti-redeposition agent.
  • Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid.
  • the average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most prefer ⁇ ably from about 7,000 to 65,000.
  • the ratio of acrylate to aleate segments in such copolymers will generally range from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1.
  • Water- soluble " salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Appli ⁇ cation No. 66915, published December 15, 1982.
  • PEG poly ⁇ ethylene glycol
  • PEG can exhibit dispersing agent perform ⁇ ance as well as act as a clay soil removal/antiredeposition agent.
  • Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.
  • Polyaspartate and polyglutamate dispersing agents are especially preferred for use herein, especially in conjunction with zeolite adjunct builders.
  • Brightener Any optical brighteners or other brightening or whitening agents known in the art can be incorporated at levels typically from about 0.05% to about 1.2%, by weight, into the detergent compositions herein.
  • Commercial optical brighteners which may be useful in the present invention can be classified into subgroups which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982).
  • optical brighteners which are useful in the present compositions are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988. These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba- Geigy; Arctic White CC and Artie White CWD, available from Hilton- Davis, located in Italy; the 2-(4-styryl-phenyl)-2H- naphthol[l,2- d]triazoles; 4,4'-bis- (l,2,3-triazol-2-yl)-stil- benes; 4,4'-bis- (styryl)bisphenyls; and the aminocoumarins.
  • these brighteners include 4-methyl-7-diethyl- amino coumarin; l,2-bis(-benzimidazol-2-yl)ethylene; 1,3-diphenylphrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-naphth-[l,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho- [l,2-d]triazole. See also U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton.
  • Suds Suppressors - Compounds for reducing or suppressing the formation of suds can be incorporated into the compositions of the present invention. Suds suppression can be of particular import ⁇ ance under conditions such as those found in European-style front loading laundry washing machines, or in the concentrated deter- gency process of U.S. Patents 4,489,455 and 4,489,574, or when the detergent compositions herein optionally include a relatively high sudsing adjunct surfactant.
  • suds suppressors A wide variety of materials may be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979).
  • One category of suds suppressor of particular interest encompasses monocarboxylic fatty acids and soluble salts therein. See U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
  • the monocarboxylic fatty acids and salts thereof used as suds suppressor typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms.
  • Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
  • the detergent compositions herein may also contain non- surfactant suds suppressors.
  • non- surfactant suds suppressors include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C18-C40 ketones (e.g. stearone), etc.
  • suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g. K, Na, and Li) phosphates and phosphate esters.
  • the hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form.
  • the liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of about -40 * C and about 5 * C, and a minimum boiling point not less than about 110 * C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferrably having a melting point below about lOO'C.
  • the hydrocarbons constitute a preferred category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al .
  • the hydrocarbons thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms.
  • paraffin as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
  • Another preferred category of non-surfactant suds suppressors comprises silicone suds suppressors. This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed of fused onto the silica. Silicone suds suppressors are well known in the art and are, for example, disclosed in U.S.
  • Patent 4,265,779 issued May 5, 1981 to Gandolfo et al and European Patent Application No. 89307851.9, published February 7, 1990, by Starch, M. S.
  • Other silicone suds suppressors are disclosed in U.S. Patent 3,455,839 which relates to compositions and processes for defoaming aqueous solutions by incorporating therein small amounts of polydimethylsiloxane fluids.
  • silicone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526.
  • Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al, and in U.S. Patent 4,652,392, Baginski et al , issued March 24, 1987.
  • An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:
  • polydimethylsiloxane fluid having a viscosity of from about 20 cs. to about 1500 cs. at 25 * C; (ii) from about 5 to about 50 parts per 100 parts by weight of (i) of siloxane resin composed of (CH3)3 SiO ⁇ /2 units of Si ⁇ 2 units in a ratio of from (CH3)3 SiO ⁇ /2 units and to Si ⁇ 2 units of from about 0.6:1 to about 1.2:1; and
  • the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), and not polypropylene glycol.
  • the primary silicone suds suppressor is branched/cross!inked and not linear.
  • typical liquid laundry detergent compositions with controlled suds will optionally comprise from about 0.001 to about 1, preferably from about 0.01 to about 0.7, most preferably from abut 0.05 to about 0.5, weight
  • said silicone suds suppressor which comprises (1) a nonaqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than about 2 weight %; and without polypropylene glycol. Similar amounts can be used in granular compositions, gels, etc. See also U.S. Patents 4,978,471, Starch, issued December 18, 1990, and 4,983,316,
  • the silicone suds suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/poly- propylene glycol, all having an average molecular weight of less than about 1,000, preferably between about 100 and 800.
  • the polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room temperature of more than about 2 weight %, preferably more than about 5 weight %.
  • the preferred solvent herein is polyethylene glycol having an average molecular weight of less than about 1,000, more preferably between about 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300. Preferred is a weight ratio of between about 1:1 and 1:10, most preferably between 1:3 and 1:6, of polyethylene glycol :copolymer of polyethylene-polypropylene glycol .
  • the preferred silicone suds suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, like PLUR0NIC L101.
  • Other suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872.
  • the secondary alcohols include the C6 ⁇ Ci6 alkyl alcohols having a C ⁇ -Ci6 chain.
  • a preferred alcohol is 2-butyl octanol , which is available from Condea under the trademark IS0F0L 12.
  • Suds suppressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1:5 to 5:1.
  • suds should not form to the extent that they overflow the washing machine.
  • Suds suppressors, when utilized, are preferably present in a "suds suppressing amount.”
  • Suds suppressing amount is meant that the formulator of the composition can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines.
  • the compositions herein will generally comprise from 0% to about 5% of suds suppressor.
  • monocarboxylic fatty acids, and salts therein When utilized as suds suppressors, monocarboxylic fatty acids, and salts therein, will be present typically in amounts up to about 5%, by weight, of the detergent composition. Preferably, from about 0.5% to about 3% of fatty monocarboxylate suds suppressor is utilized. Silicone suds suppressors are typically utilized in amounts up to about 2.0%, by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarly to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing. Preferably from about 0.01% to about 1% of silicone suds suppressor is used, more preferably from about 0.25% to about 0.5%.
  • these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjunct materials that may be utilized.
  • Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from about 0.1% to about 2%, by weight, of the composition.
  • Hydrocarbon suds suppressors are typically utilized in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used.
  • the alcohol suds suppressors are typically used at 0.2%-3% by weight of the finished compositions
  • compositions herein can also be used with a variety of other adjunct ingredi- ents which provide still other benefits in various compositions within the scope of this invention.
  • the following illustrates a variety of such adjunct ingredients, but is not intended to be limiting therein.
  • Fabric Softeners Various through-the-wash fabric softeners, especially the impalpable smectite clays of U.S. Patent 4,062,647, Storm and Nirschl, issued December 13, 1977, as well as other softener clays known in the art, can optionally be used typically at levels of from about 0.5% to about 10% by weight in the present compositions to provide fabric softener benefits concurrently with fabric cleaning.
  • Clay softeners can be used in combination with amine and cationic softeners, as disclosed, for example, in U.S. Patent 4,375,416, Crisp et al , March 1, 1983 and U.S. Patent 4,291,071, Harris et al , issued September 22, 1981.
  • Adjunct Surfactants can optionally contain various anionic, nonionic, cationic, zwitterionic, etc. surfactants. If used, such adjunct surfactants can be present at levels of from about 5% to about 35% of the compositions. However, it is to be understood that the incorporation of adjunct anionic surfactants is entirely optional herein, inasmuch as the cleaning performance of the secondary (2,3) alkyl sulfates is excellent and these materials can be used to entirely replace such surfactants as the alkyl benzene suifonates in fully-formulated detergent compositions.
  • Nonlimiting examples of optional surfactants useful herein include the conventional Cn-Ci ⁇ alkyl benzene suifonates and primary and random alkyl sulfates, the Cio-Ci ⁇ alkyl alkoxy sulfates (especially EO 1-5 ethoxy sulfates), Cio-Ci ⁇ alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the Cio-Ci ⁇ alkyl polyglycosides and their corresponding sulfated polyglycosides, C12-C18 alpha-sulfonated fatty acid esters, C12-C18 alkyl and alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C12-C18 betaines and sulfobetaines ("sultaines”), Cio-Ci ⁇ amine oxides, and the like. Other conven ⁇ tional useful surfactants are listed in standard texts.
  • adjunct nonionic surfactants especially useful herein comprises the polyhydroxy fatty acid amides of the formula: 0 Rl
  • R2 - (f - N - Z wherein: R is H, Ci-C ⁇ hydrocarbyl, 2-hydroxyethyl , 2-hydroxy- propyl, or a mixture thereof, preferably C1-C4 alkyl, more prefer ⁇ ably Ci or C2 alkyl, most preferably Ci alkyl (i.e., methyl); and R2 is a C5-C32 hydrocarbyl moiety, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most preferably straight chain C11-C19 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least 2 (in the case of glyceraldehyde) or at least 3 hydroxyls (in the case of other reducing sugars) directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or prop
  • Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl moiety.
  • Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose, as well as glyceraldehyde.
  • high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials.
  • Z preferably will be selected from the group consisting of -CH2-(CHOH) n -CH2 ⁇ H, -CH(CH20H)-(CH0H) n _ ⁇ - CH2OH, -CH2-(CHOH)2(CHOR')(CHOH)-CH2 ⁇ H, where n is an integer from 1 to 5, inclusive, and R' is H or a cyclic mono- or poly- saccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH2 ⁇ H.
  • R can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-isobutyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.
  • R is preferably methyl or hydroxyalkyl.
  • R is preferably C2-C8 alkyl, especially n-propyl, iso-propyl, n-butyl, iso-butyl, pentyl , hexyl and 2-ethyl hexyl .
  • R2-C0-N ⁇ can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
  • the methods comprise reacting N-alkylamino polyols with, preferably, fatty acid methyl esters in a solvent using an alkoxide catalyst at temperatures of about 85'C to provide high yields (90-98%) of polyhydroxy fatty acid amides having desirable low levels (typically, less than about 1.0%) of sub-optimally degradable cyclized by-products and also with improved color and improved color stability, e.g., Gardner Colors below about 4, preferably between 0 and 2.
  • any unreacted N-alkylamino polyol remaining in the product can be acylated with an acid anhydride, e.g., acetic anhydride, maleic anhydride, or the like, to minimize the overall level of such residual amines in the product.
  • an acid anhydride e.g., acetic anhydride, maleic anhydride, or the like.
  • Resi ⁇ dual sources of classical fatty acids, which can suppress suds can be depleted by reaction with, for example, triethanolamine.
  • cyclized by-products herein is meant the undesirable reaction by-products of the primary reaction wherein it appears that the multiple hydroxyl groups in the polyhydroxy fatty acid amides can form ring structures which are, in the main, not readily biodegradable. It will be appreciated by those skilled in the chemical arts that the preparation of the polyhydroxy fatty acid amides herein using the di- and higher saccharides such as maltose will result in the formation of polyhydroxy fatty acid amides wherein linear substituent Z (which contains multiple hydroxy substituents) is naturally "capped” by a polyhydroxy ring structure. Such materials are not cyclized by-products, as defined herein.
  • the foregoing polyhydroxy fatty acid amides can also be sulfated, e.g., by reaction with S03/pyridine, and the resulting sulfated material used as an adjunct anionic surfactant herein.
  • SAS secondary (2,3) alkyl sulfates
  • PFAS polyhydroxy fatty acid amide surfactants
  • AE alkyl ethoxylate surfactants
  • AS primary alkyl sulfate surfactants
  • the improved solubility is of substantial benefit under cold water conditions (e.g., at tempera ⁇ tures in the range of 5'C to about 30 * C) where the rate of solubility of detergent granules in an aqueous washing liquor can be problematic.
  • the improved solubility achieved herein is also of substantial benefit when preparing the modern compact or dense detergent granules where solubility can be problematic.
  • Other Ingredients A wide variety of other ingredients useful in detergent compositions can be included in the composi ⁇ tions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, etc.
  • suds boosters such as the C10-C16 alkanol mides can be incorporated into the compositions, typically at 1%-10% levels.
  • the C10-C1 monoethanol and diethanol amides illustrate a typical class of such suds boosters.
  • Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous.
  • soluble magnesium salts such as MgCl2, MgS04, and the like, can be added at levels of, typically, 0.1%-2%, to provide additional sudsing.
  • Various detersive ingredients employed in the present compo- sitions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating.
  • the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate.
  • the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.
  • a porous hydro ⁇ phobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5% of C13-15 ethoxylated alcohol E0(7) nonionic surfactant.
  • the enzyme/surfact ⁇ ant solution is 2.5 X the weight of silica.
  • the resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be used).
  • silicone oil various silicone oil viscosities in the range of 500-12,500 can be used.
  • the result ⁇ ing silicone oil dispersion is emulsified or otherwise added to the final detergent matrix.
  • ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected” for use in deter ⁇ gents, including liquid laundry detergent compositions.
  • Liquid detergent compositions can contain water and other solvents as carriers. Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol , and isopro- panol are suitable.
  • Monohydric alcohols are preferred for solu- bilizing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol , ethylene glycol, glycerine, and 1,2- propanediol) can also be used.
  • the compositions may contain from 5% to 90%, typically 10% to 50% of such carriers.
  • the detergent compositions herein will preferably be formu ⁇ lated such that, during use in aqueous cleaning operations, the wash water will have a pH of between about 7.5 and about 11, preferably pH 9-11. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
  • particulate detergents herein comprising the secondary (2,3) alkyl sulfate surfactants can be prepared using a variety of well-known processes. For example, particles can be formed by agglomeration, wherein solids (including the secondary (2,3) alkyl sulfates) are forced/hurled together by physical mixing and held together by a binder. Suitable apparatus for agglomeration includes dry powder mixers, fluid beds and turbilizers, available from manufacturers such as L ⁇ dige, Eric, Bepex and Aeromatic.
  • particles can be formed by extrusion.
  • solids such as the secondary (2,3) alkyl sulfates are forced together by pumping a damp powder at relatively high pressures and high energy inputs through small holes in a die plate.
  • This process results in rod like particles which can be divided into any desired particle size.
  • Apparatus includes axial or radial extruders such as those available from Fuji, Bepex and Teledyne/Readco.
  • particles can be formed by prilling.
  • a liquid mixture containing the desired ingredients i.e., one of them being secondary (2,3) alkyl sulfate particles
  • the desired ingredients i.e., one of them being secondary (2,3) alkyl sulfate particles
  • the liquid droplets cool they become more solid and thus the particles are formed.
  • the solidification can occur due to the phase change of a molten binder to a solid or through hydration of free mois ⁇ ture into crystalline bound moisture by some hydratable material in the original liquid mixture.
  • particles can be formed by compaction. This method is similar to tablet formation processes, wherein solids (i.e., secondary [2,3] alkyl sulfate particles) are forced together by compressing the powder feed into a die/mold on rollers or flat sheets.
  • solids i.e., secondary [2,3] alkyl sulfate particles
  • particles can be formed by melt/solidifica ⁇ tion.
  • particles are formed by melting the second- ary (2,3) alkyl sulfate with any desired additional ingredient and allowing the melt to cool, e.g., in a mold or as droplets.
  • Binders can optionally be used in the foregoing methods to enhance particle integrity and strength.
  • Water alone, is an operative binder with secondary (2,3) alkyl sulfates, since it will dissolve some of the secondary (2,3) alkyl sulfate to provide a binding function.
  • Other binders include, for example, starches, polyacrylates, carboxymethylcellulose and the like. Binders are well-known in the particle making literature. If used, binders are typically employed at levels of 0.1%-5% by weight of the finished particles.
  • fillers such as hydratable and nonhydratable salts, crystalline and glassy solids, various detersive ingredi ⁇ ents such as zeolites and the like, can be incorporated in the particles. If used, such fillers typically comprise up to about 20% by weight of the particles.
  • Particles prepared in the foregoing manner can be subse ⁇ quently dried or cooled to adjust their strength, physical proper ⁇ ties and final moisture content, according to the desires of the formulator.
  • the preferred overall making process for particulate products herein involves three distinct Steps: (1) agglomeration of the ingredients to form the base formula, followed by; (2) admixing various ingredients with the agglomerates formed in Step (1) (e.g., percarbonate bleach, bleach activators, and the like); and optionally, but preferably, (3) spraying materials such as perfume onto the final mix.
  • the base formula is agglomerated as opposed to spray dried in order to prevent degradation of some of the heat sensitive surfactants.
  • the resulting product is a high density (ranging from 600 g/liter - 800 g/liter) free flowing detergent mix that can be used in place of current spray dried laundry detergents.
  • Aeromatic fluidized bed or a continuous type static or vibrating fluidized bed (NIRO, Bepex or Carrier Companies); and (D) coating the agglomerates using a mixer such as an Eirich Mixer, R-Series.
  • Step A Preparation of Surfactant Paste -
  • the objective is to combine the surfactants and liquids in the compositions into a common mix in order to aid in surfactant solubilization and agglomeration.
  • the surfactants and other liquid components in the composition are mixed together in a Sigma Mixer at 140'F (60 * C) at about 40 rpm to about 75 rpm for a period of from 15 minutes to about 30 minutes to provide a paste having the general consistency of 20,000-40,000 centipoise.
  • the paste is stored at 140 * F (60 * C) until agglomeration Step (B) is ready to be conducted.
  • the ingredients used in this Step include surfactants, acrylate/maleic polymer (m.w.
  • Step B Agglomeration of Powders with Surfactant Paste -
  • the purpose of this Step is to transform the base formula ingredients into flowable detergent particles having a medium particle size range of from about 300 microns to about 600 microns.
  • the powders including the layered silicate builder (as SKS-6), optional citrate and zeolite adjunct builders, sodium carbonate, ethylenediaminedisuccinate, magnesium sulfate and optical brightener) are charged into the Eirich Mixer (R-Series) and mixed briefly ⁇ ca. 5 seconds - 10 seconds) at about 1500 rpm to about 3000 rpm in order to mix the various dry powders fully.
  • the surfactant paste from Step A is then charged into the mixer and the mixing is continued at about 1500 rpm to about 3000 rpm for a period from about 1 minute to about 10 minutes, preferably 1-3 minutes, at ambient temperature.
  • the mixing is stopped when coarse agglomerates (average particle size 800-1600 microns) are formed.
  • Step C The purpose of this Step is to reduce the agglomer ⁇ ates' stickiness by removing/drying moisture and to aid in particle size reduction to the target particle size (in the median particle size range from about 300 to about 600 microns, as measured by sieve analysis).
  • the wet agglomerates are charged into a fluidized bed at an air stream temperature of from about 41 * C to about 60 * C and dried off to a final moisture content of the particles from about 4% to about 10%.
  • Step D Coat Agglomerates and Add Free-Flow Aids -
  • the objective in this Step is to achieve the final target particle size range of from about 300 microns to about 600 microns, and to admix materials which coat the agglomerates, reduce the caking/ lumping tendency of the particles and help maintain acceptable flowability.
  • the dried agglomerates from Step C are charged into the Eirich Mixer (R-Series) and mixed at a rate of about 1500 rpm to about 3000 rpm while adding 2-6% Zeolite A (median particle size 2-5 ⁇ m) during the mixing. The mixing is continued until the desired median particle size of from about 1200 to about 400 microns is achieved (typically from about 5 seconds to about 45 seconds).
  • a laundry bar suitable for hand-washing soiled fabrics is prepared by standard extrusion processes and comprises the following: Ingredient % (wt.)
  • a granular detergent herein comprises the following. Ingredient % (wt.) Secondary (2,3) alkyl sulfate* 5.0
  • Example VII The compositions of Example I and II are modified by including 0.5% of a commercial amylase preparation (TERMAMYL) therein.
  • EXAMPLE VIII Additional examples of particulate laundry detergents with mixed surfactants especially suitable for use in front-loading washing machines such as those commonly used in Europe are as follows.
  • Ci6 secondary (2,3) alkyl sulfate Na 6.92 9.00 7.60 c 16/18 primary alkyl sulfate 2.05 3.00 1.30 c 12"Cl5 alkyl ethoxy (1-3) sulfate 0.17 0.40 0.10
  • a nonphosphate granular laundry detergent composition herein which comprises biodegradable or biologically inert ingredients is as follows. Ingredient % (wt.) Ci6 secondary (2,3) alkyl sulfate, Na 20.0 c 12-14 N-methyl gluca ide 10.0
  • compositions herein comprising the layered sili- cate builder/secondary (2,3) alkyl sulfate vs. more conventional compositions which contain, for example, zeolite/primary alkyl sulfate ingredients.
  • Test Methodology Performance of the above compositions is tested in a Launderometer with stain tracer swatches using 3.3 g of test product in 400 ml water pots. Water hardness is 25 * German (3:1 Ca:Mg ratio). Four replicates per product are used. The wash cycle is 30'C for 45 minutes. At the end of the cycle, the stain tracer swatches (dirty motor oil; shoe polish; cosmetics on polyester/cotton swatches; clay soil on cotton swatch) are manually rinsed in clean water and visually graded. In such tests the results are as follows. Formulation A vs. B

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Abstract

L'invention concerne des compositions détergentes qui comprennent comme adjuvant, du silicate en couches et, comme tensioactifs, des sulfates secondaires d'alkyle (2,3) ayant des quantités réduites de zéolites comme adjuvants. Les compositions permettent un excellent nettoyage du tissu tout en minimisant le dépôt de résidus inorganiques sur les surfaces du tissu.
EP94914042A 1993-04-08 1994-04-05 Compositions detergentes Withdrawn EP0693105A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB939307493A GB9307493D0 (en) 1993-04-08 1993-04-08 Detergent compositions
GB9307493 1993-04-08
PCT/US1994/003728 WO1994024238A1 (fr) 1993-04-08 1994-04-05 Compositions detergentes

Publications (2)

Publication Number Publication Date
EP0693105A1 true EP0693105A1 (fr) 1996-01-24
EP0693105A4 EP0693105A4 (fr) 1996-05-15

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EP94914042A Withdrawn EP0693105A4 (fr) 1993-04-08 1994-04-05 Compositions detergentes

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EP (1) EP0693105A4 (fr)
JP (1) JPH08511042A (fr)
CN (1) CN1124975A (fr)
CA (1) CA2160108A1 (fr)
GB (1) GB9307493D0 (fr)
WO (1) WO1994024238A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2294704A (en) * 1994-11-05 1996-05-08 Procter & Gamble Bleaching composition
ES2216025T3 (es) * 1995-04-20 2004-10-16 Kao Corporation Compuesto detergente blanqueante.
WO1997032952A1 (fr) * 1996-03-08 1997-09-12 The Procter & Gamble Company Preparation de particules de sulfate alkyle secondaire possedant une meilleure solubilite
US5955418A (en) * 1997-02-26 1999-09-21 The Procter & Gamble Company Secondary alkyl sulfate surfactant with improved solubility by kneading/extruding process
US7638474B1 (en) 2008-08-05 2009-12-29 The Clorox Company Natural laundry detergent compositions
BR112022018106A2 (pt) * 2020-03-11 2022-10-25 Unilever Ip Holdings B V Composição sólida de limpeza, método para redução do número de enxágues e uso de uma combinação

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Publication number Priority date Publication date Assignee Title
US3234258A (en) * 1963-06-20 1966-02-08 Procter & Gamble Sulfation of alpha olefins
DE3413571A1 (de) * 1984-04-11 1985-10-24 Hoechst Ag, 6230 Frankfurt Verwendung von kristallinen schichtfoermigen natriumsilikaten zur wasserenthaertung und verfahren zur wasserenthaertung
DE3416472A1 (de) * 1984-05-04 1985-11-07 Hoechst Ag, 6230 Frankfurt Weichmacher enthaltende waschmittel
DE3416669A1 (de) * 1984-05-05 1985-11-07 Hoechst Ag, 6230 Frankfurt Weichmachendes waschmittel
DE3812556A1 (de) * 1988-04-15 1989-10-26 Hoechst Ag Waschmittel mit lagerstabilisiertem bleichsystem
US5075041A (en) * 1990-06-28 1991-12-24 Shell Oil Company Process for the preparation of secondary alcohol sulfate-containing surfactant compositions

Non-Patent Citations (2)

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Title
No further relevant documents disclosed *
See also references of WO9424238A1 *

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WO1994024238A1 (fr) 1994-10-27
GB9307493D0 (en) 1993-06-02
CN1124975A (zh) 1996-06-19
CA2160108A1 (fr) 1994-10-27
JPH08511042A (ja) 1996-11-19
EP0693105A4 (fr) 1996-05-15

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