EP0882121A1 - Compositions pour le lavage de la vaisselle en machine comprenant des mesopores et des macropores siliceux - Google Patents

Compositions pour le lavage de la vaisselle en machine comprenant des mesopores et des macropores siliceux

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Publication number
EP0882121A1
EP0882121A1 EP97905868A EP97905868A EP0882121A1 EP 0882121 A1 EP0882121 A1 EP 0882121A1 EP 97905868 A EP97905868 A EP 97905868A EP 97905868 A EP97905868 A EP 97905868A EP 0882121 A1 EP0882121 A1 EP 0882121A1
Authority
EP
European Patent Office
Prior art keywords
automatic dishwashing
compositions
synthetic
bleach
composition
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Withdrawn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
EP97905868A
Other languages
German (de)
English (en)
Inventor
Gregory Stephen Caravajal
William Michael Scheper
James Charles Burckett-St. Laurent
Robert Ya-Lin Pan
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 EP0882121A1 publication Critical patent/EP0882121A1/fr
Withdrawn legal-status Critical Current

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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions
    • 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
    • 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
    • C11D3/395—Bleaching agents
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the present invention is in the field of automatic dishwashing detergent compositions, especially granules, but also including liquids, pastes, gels and other nongranular solids, such as tablets.
  • the compositions are formulated with or without phosphates.
  • the compositions contain special types of siliceous porous materials. These were hitherto normally reserved for use in petroleum refining, for example as catalyst supports, rather than as detergency ingredients. Preferred methods for washing tableware are included.
  • Automatic dishwashing particularly in domestic appliances, is an art very different from fabric laundering.
  • Automatic dishwashing appliances generally have a spray-action while domestic fabric laundering is done in different purpose-built machines, having a tumbling action.
  • Automatic dishwashing spray-action tends to cause foam. Foam can easily overflow low sills domestic dishwasher sills and slow down the rotary arm ofthe appliance, in turn reducing dish-cleaning.
  • Formulators of laundry detergents have arrived at products quite successful in the marketplace using common zeolites, such as the zeolite A type, which are 4
  • Angstrom relatively Al-rich, microporous (not mesoporous or macroporous) crystalline aluminosilicates, to soften wash water by ion exchange.
  • Zeolite A Zeolite P and many other silicates, aluminosilicates or other siliceous porous materials having limited solubility in water, a common example being amorphous silica, have been tried out for use in dishwashing. Results have been unspectacular at best. Nonetheless some highly specialized silicas have been successfully used, especially in combination with viscous polydimethylsiloxanes, as low-level antifoams.
  • a further object is to provide fully-formulated ADD compositions with or without phosphate builder, wherein the specifically identified siliceous materials are combined with additional selected ingredients, especially low-foam surfactants, preferably the nonionic type, and suds suppressors or antifoams, ideally with the further addition of enzymes and/or catalyzed or uncatalyzed bleaches, so as to deliver superior cleaning, material protection, bleaching and spotlessness / lack of film on the consumer's ware, especially with minimized redeposition of soil and/or product ingredients.
  • additional selected ingredients especially low-foam surfactants, preferably the nonionic type, and suds suppressors or antifoams
  • mesopores prepared by known processes which utilize liquid- crystal templating with surfactant materials, as described, for example, in US Patent No. 5,102,643, Kresge et al., issued April 7, 1992; US Patent No. 5,098,684, Kresge et al., issued March 24, 1992; and US Patent No. 5,108,725, Beck et al., issued April 28, 1992; the disclosures of all these patents being inco ⁇ orated herein by reference in their entirety.
  • siliceous materials primarily of interest in petroleum refining, are useful in automatic dishwashing compositions.
  • synthetic siliceous materials are specific types of synthetic siliceous materials: (I) synthetic siliceous mesopores and synthetic siliceous macropores (either of which types are typically homogeneous with respect to the starting-material source of, and porous material distribution of, silicate, and may be substituted or unsubstituted as defined hereinafter), which materials are typically manufactured without need of layer silicates or clay; and (II) a more limited number of synthetic siliceous porous materials manufactured with the essential inclusion of clays or layer silicates as starting-ingredients.
  • typical manufacture of the porous material involves using a geometrically organized fluid organic phase, typically a hexagonal phase of an amine or quaternary surfactant, as a "template”; polymerizing thereon or therewith a low molecular weight silicate; and calcining to remove the templating phase.
  • a geometrically organized fluid organic phase typically a hexagonal phase of an amine or quaternary surfactant, as a "template”
  • polymerizing thereon or therewith a low molecular weight silicate and calcining to remove the templating phase.
  • automatic dishwashing detergent compositions comprising the selected synthetic siliceous porous material, special types of surfactant (different, for example, from quaternary, cationic types used in synthesizing certain mesopores); and the balance automatic dishwashing detergent adjunct materials.
  • automatic dishwashing detergent compositions of the present invention comprise:
  • a synthetic siliceous porous material selected from the group consisting of (i) unsubstituted synthetic siliceous mesopores; (ii) substituted synthetic siliceous mesopores; (iii) unsubstituted synthetic siliceous macropores; (iv) substituted synthetic siliceous macropores; each of (i)-(iv) having - linear symmetrical channels of diameter from about 16 to about 100 Angstrom, BET surface area of from about 400 m2/g to about 1500 m2/g, and, when substituted, any element contributing to the substitution is an element selected from metallic and metalloid elements other than silicon; (v) synthetic siliceous porous materials derived from layer silicates or clays having BET surface area of about 800m 2 /g or higher and having linear unsymmetrical channels of smallest diameter from about 10 Angstrom to about 40 Angstrom; and (vi) mixtures thereof;
  • components (i)-(iv) exemplify the hereinbefore referenced Class (I) materials and (v) exemplify the Class (II) materials.
  • a preferred automatic dishwashing detergent is one wherein said synthetic siliceous porous material is a mesopore selected from (i) and (ii) identified supra, possessing a hexagonal array of said linear channels and, when substituted, a ratio defined by: moles (Si):moles (E) > 5 wherein moles (E) is a sum of moles of all elements other than silicon and oxygen in said siliceous porous material.
  • said synthetic siliceous porous material is (ii) and has a Si:E ratio of from about 10:1 to about 200: 1 and wherein said substituent elements summed in E, are selected from the group consisting of Aluminum, Iron, Ruthenium, Manganese and mixtures thereof, especially Aluminum.
  • a preferred synthetic siliceous porous material herein is a material designated as M41 S.
  • M41 S is an inorganic, non-layered, porous crystalline phase material having pores with diameters of at least about 13 Angstroms and which exhibits, after calcination, an X-ray diffraction pattern with at least one d-spacing greater than about 18 Angstroms with a relative intensity of 100.
  • M41S is a mesoporous class of materials which are described in U.S. Pat. No. 5,102,643 incorporated herein by reference.
  • the present compositions comprise special types of surfactant developed for automatic dishwashing purposes. These are described more fully hereinafter and include in particular certain low- foaming nonionics, such as EO/PO block polymeric surfactants, the Pluronic or Tetronic types manufactured by BASF, or the SLF types manufactured by Olin.
  • certain low- foaming nonionics such as EO/PO block polymeric surfactants, the Pluronic or Tetronic types manufactured by BASF, or the SLF types manufactured by Olin.
  • adjuncts for automatic dishwashing are also present, such as at least one adjunct selected from antifoams, enzymes, bleaches, bleach catalysts, builders, alkalis, and mixtures thereof. Certain preferred embodiments are free from polyacrylate dispersants. Other preferred embodiments are automatic dishwashing compositions comprising the selected synthetic siliceous porous material, low- foaming nonionic surfactant, antifoam, sodium perborate or percarbonate, a water- soluble transition metal bleach catalyst, citrate and/or phosphate builder, amylase and protease.
  • compositions herein comprise mesopores of the M41S type, especially the MCM-41 family.
  • the instant ADD's have numerous advantages, for example, they improve spotlessness and reduce film on the consumer's ware. Especially when they are formulated at very high pH and are polyacrylate-free, the compositions produce lower amounts of Ca/Mg film than otherwise comparable compositions not having the special siliceous component. When the special siliceous materials are used in conjunction with colored or Mn-containing bleach catalysts, any tendency of the catalyst to discolor glassware is eliminated. Free-flowing, quick-dispersing automatic dishwashing detergent granules can be produced. Depending on the level ofthe siliceous material, compositions having improved hardness "building" are also afforded.
  • the instant invention also encompasses cleaning methods; more particularly, a method of washing tableware in a domestic automatic dishwashing appliance, comprising treating the soiled tableware in an automatic dishwasher with an aqueous alkaline bath comprising an ADD composition ofthe invention.
  • the present invention inco ⁇ orates specifically selected siliceous materials into automatic dishwashing detergents.
  • Any "synthetic siliceous porous material” herein is a material, preferably a compound or mixture of compounds, which is synthetic.
  • synthetic as used herein means that the material referred to differs from naturally occurring minerals in that it has undergone at least one step of chemical transformation by human intervention, as distinct from exclusively geological intervention. Natural materials, such as sand or clay, or synthetic materials, such as hydro thermally synthesized layer silicates, are however allowable starting-materials in making certain ofthe synthetic siliceous porous materials useful herein.
  • siceous indicates that the material referred to is is a silicate or a silicate which is substituted by other elements, for example Fe, B or Al.
  • porous indicates a material having a plurality of pores 10 Angstrom or larger in diameter if the pores are equidimensional in cross-section, or. if the pores are irregular, a material having a plurality of pores 10 Angstrom or larger in the smallest dimension. Other porosity characteristics, for example expressed in terms of pore size and/or BET surface area, are described as appropriate throughout the specification.
  • Class (I) (i) unsubstituted synthetic siliceous mesopores; (ii) substituted synthetic siliceous mesopores; (iii) unsubstituted synthetic siliceous macropores; (iv) substituted synthetic siliceous macropores; Class (II): (v) synthetic siliceous porous materials derived at least in part from preformed polysilicate materials selected from clays and layer silicates subject to additional requirements described hereinafter; and (vi) mixtures thereof. All preferred synthetic siliceous porous materials herein are crystalline, to the extent that crystallinity can be determined by known diffraction methods: in this respect, all such materials are easily distinguished from any known amo ⁇ hous silicate, regardless of its porosity.
  • mesopores and “macropores” herein include representatives of a recently discovered class of compounds described in more detail hereinafter having linear symmetrical channels of diameter from about 16 to about 100 Angstrom and BET surface areas of from about 400 m 2 /g to about 1500 m2/g. They may be unsubstituted, i.e., entirely siliceous, or substituted by other elements.
  • any element contributing to the substitution is an element selected from metallic and metalloid elements other than silicon; examples of such elements being B, Al, Fe, Ru, Mn or mixtures thereof.
  • the materials, (v), derived from clays or layer silicates, are synthetic siliceous porous materials, preferably also mesoporous, having - BET surface area of about 800m2/g or higher and having linear unsymmetrical channels of smallest diameter from about 10 Angstrom to about 40 Angstrom.
  • all the conventional zeolites such as A, Y, X and P including the so-called "MAP” or “Maximum Aluminum” P types are specifically excluded as the essential porous component ofthe invention, as are conventionally known amo ⁇ hous sodium silicates.
  • the synthetic siliceous porous materials herein may, on account of their synthesis or chemical treatment, comprise components other than a covIERly linked silicate framework or substituted silicate framework.
  • Such optional components include water, for example as absorbed from the air, metal ions such as sodium, calcium, magnesium or potassium, alkali ions such as hydroxide, and, when prepared by templating, varying proportions of templating surfactant.
  • metal ions such as sodium, calcium, magnesium or potassium
  • alkali ions such as hydroxide
  • templating surfactant varying proportions of templating surfactant.
  • the materials useful herein, as first formed into gelled mesopore precursors are best calcined as taught in the art, whereby especially the templating surfactant, but also moisture, are removed; preferably, moreover, the materials are not treated with calcium prior to inco ⁇ oration in the ADD compositions.
  • MCM- 41 A particular class of M41S materials is the class of materials designated as MCM- 41.
  • MCM-41 has a hexagonal electron diffraction pattern that can be indexed with a d 10 o value greater than about 18 Angstroms and a hexagonal arrangement of uniformly sized pores with a maximum pe ⁇ endicular cross-section of at least about 13 Angstroms.
  • MCM-41 materials are described in U.S. Pat. No. 5,098,684 inco ⁇ orated by reference.
  • an automatic dishwashing detergent wherein there are present in the synthetic siliceous porous material channels or pores having diameter in the range from about 20 to about 60 Angstroms and said synthetic siliceous porous material is a member of a family of silicate mesopores known as MCM-41.
  • the mesoporous MCM-41 materials include those found useful as catalyst supports in U.S. Pat. No. 5,475,178, Del Rossi et al, December 12, 1995, inco ⁇ orated by reference. They may be characterized by a substantially uniform hexagonal honeycomb microstructure with uniform pores having a cell diameter greater than 13 Angstroms and typically in the range of 20 to 100 Angstroms. Preferred MCM-41 type materials useful herein have pore or channel diameter in the range from about 20 to about 60 Angstroms, as noted. MCM-41 may be synthesized as a metallosilicate with Bronsted acid sites by incorporating a tetrahedrally coordinated trivalent element, E, such as Al, Ga, B or Fe within the silicate framework.
  • E tetrahedrally coordinated trivalent element
  • Another preferred automatic dishwashing detergent herein is one wherein said synthetic siliceous porous material has a monomodal size distribution of hexagonal linear channels and at least 0.95 mole fraction of said substituent elements are Aluminum.
  • an automatic dishwashing detergent wherein said synthetic siliceous porous material is substantially free from substitution by boron and transition metals.
  • the present invention permits the use of the synthetic siliceous porous materials as supports for known bleach catalysts (see hereinafter) but the primary pu ⁇ ose or benefit is not catalytic.
  • Preferred mesoporous or macroporous materials herein are those having a minimum of intrinsic catalytic activity. This attractively permits their concurrent use as delivery systems for redox-sensitive aesthetic components of the automatic dishwashing detergent while keeping them no less effective for other benefits, such as spotting/filming reduction at high pH, as determined in the present invention.
  • the present invention is not limited in terms of the modality of the pore size distribution of the synthetic siliceous porous material.
  • mesopores are available which have bimodal distribution of pore sizes.
  • the present invention encompasses automatic dishwashing detergents wherein said synthetic siliceous porous material has a bimodal or multimodal size distribution of pores or channels.
  • a synthetic siliceous porous material termed a "double- mesopore” is made by dissolving NaOH in distilled water and mixing with cetyltrimethylammonium chloride (CTAC1); stirring the resulting mixture until homogeneous; and adding dropwise tetraethylorthosilicate with stirring for about 4 hours to form a gel having the composition: CTAC1:0.14 Na 2 O:5.1SiO .360H 2 O without accounting for ethanol evolved from the Si source.
  • This gel precursor of the mesopore is calcined in air at 550 deg. C. to form the final bimodal mesopore having well-defined smaller pores being distributed at around 30 Angstrom in diameter and larger pores within the range 80 - 200 Angstrom.
  • the present invention also encompasses an automatic dishwashing detergent wherein said synthetic siliceous porous material has an improved long-range structural order and an improved textural uniformity, for example as is achievable by the use of pH adjustment in the synthesis.
  • said improved long-range structural order and textural uniformity are the result of use of acetic acid in synthesis of said synthetic siliceous porous material.
  • the invention includes automatic dishwashing detergents wherein said synthetic siliceous porous material is derived from one or more of kanemite, ilerite, magdaite and kenyaite by cationic surfactant intercalation, for example using octylamine, cetyltrimethylammonium chloride or the like in presence or absence of water, preferably the latter, and pillaring with a gellable silicate such as tetraethyl orthosilicate, and has BET surface area of about 900 m 2 /g or higher.
  • Suitable materials are, for example, described in J. Chem. Soc, Chem. Commun, 1993, 680-682. Preferred materials of this type are typically calcined in a manner similar to the preferred MCM-41 type mesopores.
  • the present invention contemplates use in automatic dishwashing compositions of any synthetic siliceous porous material equivalent to those specifically illustrated, without limitation as to synthesis method; for example, variations of conventional synthesis procedure which minimize the use or loss of quaternary surfactant, e.g., through the use of supercritical argon extraction at temperatures well below the current typical calcination temperatures are contemplated.
  • the regular porous structure is maintained and the material can even be other than a silicate, such as a zinc oxide: see, for example, Huo et al, Nature, Vol. 368, 1994, pages 317-321, incorporated by reference, entitled "generalized synthesis of periodic surfactant/inorganic composite materials".
  • the zinc derivatives can, for example, be useful material care agents in automatic dishwashing compositions.
  • the synthetic siliceous porous materials of the present invention can be processed in various ways before adding them to the automatic dishwashing detergent composition.
  • Raw material forms of the synthetic siliceous porous material may be reduced in size by grinding or flaking if necessary by techniques well known in the art.
  • they will have a primary particle size from about 0.1 micron to about 150 micron, preferably from about 0.1 to about 10 micron, although agglomerates or composite particles may desirably be formed by binding the primary particles with low-foaming waxy nonionic surfactants of types described hereinafter.
  • Agglomerates will have particle size distributions matched to minimize segregation in granular-form automatic dishwashing detergents.
  • Tablet forms of the ADD compositions are also envisaged in which the essential porous material can have a useful binding function.
  • the ADD When formulating the ADD as a liquid or gel, it is desirable to use known techniques of modifying product rheology, for example as disclosed in the art for suspended bleach in liquid laundry detergents, so as to stabilize primary particles from separating.
  • Coated or uncoated forms of the synthetic siliceous porous material may be used; for example, when formulating a mesopore having ultra-low Al content into a highly alkaline liquid automatic dishwashing detergent, it is desirable to coat the mesopore with a waxy surfactant having a melting point of about 45 deg. C.
  • the synthetic siliceous porous material is dry-added to complete the ADD composition.
  • an automatic dishwashing composition having granular form, wherein said synthetic silicate is dry-added rather than being exposed to spray-drying to make the composition, whereby the chemical identity of said synthetic silicate is not substantially disrupted by interaction with acidic or alkaline adjuncts.
  • Automatic dishwashing compositions of the present invention comprise the above-identified specifically selected synthetic siliceous porous materials in combination with automatic dishwasher-compatible detersive surfactants and other automatic dishwashing adjunct materials, especially antifoams or "suds suppressors". Amounts ofthe essential ingredients can vary within wide ranges.
  • Preferred fully-formulated compositions typically comprise bleaches, such as hydrogen peroxide, perborates, percarbonates, peroxymonosulfates or diacyl peroxides (these are especially useful for tea and/or carotenoid soil/stain removal from mugs and cups, dishware and/or plastic kitchen articles; bleaches herein may be complemented by so-called “activators” and/or by bleach catalysts and/or bleach stabilizers); enzymes, especially alkali-stable hydrolases such as proteases or amylases (these are especially useful for protein and starchy soil cleaning, though other enzyme types may be used); builders such as phosphate or citrate (which help control calcium and/or magnesium and may assist buffering action); and alkalis (to adjust pH).
  • the present compositions may, moreover, comprise one or more processing aids, fillers, perfumes, conventional enzyme particle-making materials including enzyme cores or "nonpareils", enzyme inhibitors, as well as pigments, and the like.
  • materials used for the production of Automatic Dishwashing Detergent (“ADD") compositions herein are preferably checked for compatibility with spotting/filming on glassware. Test methods for spotting/filming are generally described in the automatic dishwashing detergent literature, including ASTM and DIN test methods. Certain oily materials, especially at longer chain lengths, and certain insoluble materials such as underivatized clays, as well as long-chain fatty acids or soaps which form soap scum are therefore preferably limited or excluded from the instant compositions.
  • pH ofthe ADD Compositions Preferred automatic dishwashing detergent compositions herein have a 1% aqueous solution pH of from about 7 to about 13, more preferably from about 8.5 to about 12.5, and most preferably of from greater than about 10.5 to about 12.0.
  • Highly preferred ADD compositions herein combine the above-identified preferred high-pH range on one hand, for example a pH of greater than about 1 1 , with relatively low total alkalinity on the other, having, for example, an alkalinity no higher than about 9 grams NaOH, or NaOH equivalent, per 100 grams of automatic dishwashing detergent product.
  • Surfactants Specially selected surfactants are useful in Automatic Dishwashing to assist cleaning, help defoam food soil foams, especially from proteins, and to help control spotting/filming and are desirably included in the present detergent compositions at levels of from about 0.01% to about 20% of the composition. In general, bleach- stable surfactants are preferred.
  • Low-Foaming Nonionic Surfactant - ADD compositions of the present invention preferably comprise low foaming nonionic surfactants (LFNIs).
  • LFNI low foaming nonionic surfactants
  • LFNI are typically present in amounts from 0.01 to about 10% by weight, preferably from about 0.25% to about 4%.
  • LFNIs are most typically used in ADDs on account of the improved water-sheeting action (especially from glass) which they confer to the ADD product. They also encompass non-silicone, nonphosphate polymeric materials further illustrated hereinafter which are known to defoam food soils encountered in automatic dishwashing.
  • Preferred LFNIs include nonionic alkoxylated surfactants, especially ethoxy ⁇ lates derived from primary alcohols, and blends thereof with more sophisticated surfactants, such as the polyoxypropylene/polyoxyethylene/polyoxypropylene (PO EO PO) reverse block polymers.
  • the PO/EO PO polymer-type surfactants are well-known to have foam suppressing or defoaming action, especially in relation to common food soil ingredients such as egg.
  • the invention encompasses preferred embodiments wherein LFNI is present, and wherein this component is solid at about 95°F (35°C), more preferably solid at about 77°F (25°C).
  • a preferred LFNI has a melting point between about 77°F (25°C) and about 140°F (60°C), more preferably between about 80°F (26.6°C) and 1 10°F (43.3°C).
  • the LFNI is an ethoxylated surfactant derived from the reaction of a monohydroxy alcohol or alkylphenol containing from about 8 to about 20 carbon atoms, with from about 6 to about 15 moles of ethylene oxide per mole of alcohol or alkyl phenol on an average basis.
  • a particularly preferred LFNI is derived from a straight chain fatty alcohol containing from about 16 to about 20 carbon atoms (Ci 6* ⁇ 20 alcohol), preferably a C]g alcohol, condensed with an average of from about 6 to about 15 moles, preferably from about 7 to about 12 moles, and most preferably from about 7 to about 9 moles of ethylene oxide per mole of alcohol.
  • the ethoxylated nonionic surfactant so derived has a narrow ethoxylate distribution relative to the average.
  • the LFNI can optionally contain propylene oxide in an amount up to about 15% by weight.
  • Other preferred LFNI surfactants can be prepared by the processes described in U.S. Patent 4,223,163, issued September 16, 1980, Builloty, inco ⁇ orated herein by reference.
  • Highly preferred ADDs herein wherein the LFNI is present make use of ethoxylated monohydroxy alcohol or alkyl phenol and additionally comprise a polyoxyethylene, polyoxypropylene block polymeric compound; the ethoxylated monohydroxy alcohol or alkyl phenol fraction of the LFNI comprising from about 20% to about 100%, preferably from about 30% to about 70%, of the total LFNI.
  • Suitable block polyoxyethylene-polyoxypropylene polymeric compounds that meet the requirements described hereinbefore include those based on ethylene glycol, propylene glycol, glycerol, trimethylolpropane and ethylenediamine as initiator reactive hydrogen compound.
  • Certain of the block polymer surfactant compounds designated PLURONIC® and TETRONIC® by the BASF- Wyandotte Co ⁇ ., Wyandotte, Michigan, are suitable in ADD compositions of the invention.
  • a particularly preferred LFNI contains from about 40% to about 70% of a polyoxypropylene/polyoxyethylene/polyoxypropylene block polymer blend comprising about 75%, by weight of the blend, of a reverse block co-polymer of polyoxyethylene and polyoxypropylene containing 17 moles of ethylene oxide and 44 moles of propylene oxide; and about 25%, by weight of the blend, of a block co ⁇ polymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 99 moles of propylene oxide and 24 moles of ethylene oxide per mole of trimethylolpropane.
  • LFNI LFNI having relatively low cloud points and high hydrophilic-lipophilic balance (HLB). Cloud points of 1% solutions in water are typically below about 32°C and preferably lower, e.g., 0°C, for optimum control of sudsing throughout a full range of water temperatures.
  • LFNIs which may also be used include a C ⁇ g alcohol polyethoxylate, having a degree of ethoxylation of about 8, commercially available as SLF18 from Olin Co ⁇ ., and any biodegradable LFNI having the melting point properties discussed hereinabove.
  • the automatic dishwashing detergent compositions herein are substantially free from cationic, zwitterionic and even anionic surfactants.
  • Certain anionic co-surfactants particularly fatty carboxylic acids, can cause unsightly films on dishware, as can many cationic surfactants having two long chains.
  • Conventional cationic surfactants such as cetyltrimethylammonium chloride frequently used in making synthetic siliceous mesopores, are found to produce high levels of foam which results in problematic overflows of domestic dishwashing applicances.
  • anionic surfactants are unacceptably high foaming. However certain anionic surfactant types are useful herein.
  • an anionic co-surfactant forming part of the surfactant component, (b), of the invention is typically of a type having good solubility in the presence of calcium alternately describable as a low Krafft temperature of the corresponding calcium salt, and has a relatively high critical micelle concentration (cmc).
  • preferred anionic cosurfactants herein have relatively short, e.g, about C8 hydrophobic chains, especially when said chains are linear. Branched-chain anionics, for example those having a total of from 6 to about 16 carbon atoms in the hydrophobe, can also be useful.
  • Such anionic co ⁇ surfactants are further illustrated by C6-C10 sulfobetaines, C6-C10 alkyl(polyethoxy)sulfates (AES), C6-C10 alkyl (polyethoxy)carboxylates, and Cfr CJO alkyl sulfates and sulfonates.
  • said essential component (b), the surfactant component is selected from low-foaming anionic surfactants, low-foaming nonionic surfactants, and mixtures thereof at levels of from about 0.05% to about 10% by weight. Additional Preferred ADD Embodiments
  • Preferred ADD compositions herein are also those wherein there is present: from about 0.001% to about 50% by weight of the synthetic siliceous porous material described hereinabove; from about 0.01% to about 20% by weight of the selected automatic dishwasher-compatible detersive surfactants described hereinabove, and the balance to 100% automatic dishwashing detergent adjuncts.
  • phosphate builder from about 0.1% to about 70%, preferably from about 0.5% to about 30%, of a source of
  • Such fully-formulated embodiments typically further comprise from about 0.1% to about 15% of a polymeric dispersant, although in certain preferred embodiments this ingredient is completely eliminated, from about 0.01% to about 10% of a chelant, and from about 0.00001% to about 10% of a detersive enzyme, though further additional or adjunct ingredients may be present.
  • ADD compositions herein in granular form typically limit water content, for example to less than about 7% free water, for best storage stability.
  • Certain preferred ADD compositions of this invention are substantially free of chlorine bleach.
  • substantially free of chlorine bleach is meant that the formulator does not deliberately add a chlorine-containing bleach additive, such as a chloroisocyanurate, to the preferred ADD composition.
  • a chlorine-containing bleach additive such as a chloroisocyanurate
  • the term “substantially free” can be similarly constructed with reference to preferred limitation of other ingredients.
  • an effective amount herein is meant an amount which is sufficient, under whatever comparative test conditions are employed, to enhance cleaning or spot/film results of a soiled surface.
  • the term “catalytically effective amount” refers to an amount of metal -containing bleach catalyst which is sufficient under whatever comparative test conditions are employed, to enhance cleaning of the soiled surface.
  • the soiled surface may be, for example, a porcelain cup with tea stain, dishes soiled with simple starches or more complex food soils, or a plastic spatula stained with tomato soup.
  • the test conditions will vary, depending on the type of washing appliance used and the habits of the user. Some machines have considerably longer wash cycles than others.
  • the present invention includes automatic dishwashing detergent compositions wherein said adjunct ingredients, (c), comprise a suds suppressor, sometimes termed an antifoam.
  • said suds suppressor is selected from silicone suds suppressors, fatty acid suds suppressors, fatty carboxylate salt suds suppressors, phosphate ester suds suppressors, hydrocarbon suds suppressors, fatty alcohol suds suppressors, fatty ester suds suppressors, and mixtures thereof.
  • said suds suppressor is substantially free from said phosphate ester suds suppressors, said fatty acid suds suppressors, and said fatty carboxylate suds suppressors.
  • Suitable levels of suds suppressor herein are in the range from about 0.001% to about 5%, preferably from about 0.01% to about 3% of the automatic dishwashing detergent composition.
  • said components (b) (the automatic dishwashing surfactant described supra) and (c) (the adjuncts including suds suppressor) are selected such that said composition produces a suds height of less than 2 inches in a domestic automatic dishwasher under normal use conditions.
  • Silicone suds suppressor technology and other defoaming agents useful herein are extensively documented in "Defoaming, Theory and Industrial Applications", Ed., P.R. Garrett, Marcel Dekker, N.Y., 1973, ISBN 0-8247-8770-6, inco ⁇ orated herein by reference. See especially the chapters entitled “Foam control in Detergent Products” (Ferch et al) and “Surfactant Antifoams” (Blease et al). See also U.S. Patents 3,933,672 and 4,136,045.
  • Highly preferred silicone suds suppressors are the compounded types known for use in laundry detergents such as heavy-duty granules, although types hitherto used only in heavy-duty liquid detergents may also be inco ⁇ orated in the instant compositions.
  • polydimethylsiloxanes having trimethylsilyl or alternate endblocking units may be used as the silicone.
  • These may be compounded with silica and/or with surface-active nonsilicon components, as illustrated by a suds suppressor comprising 12% silicone/silica, 18% stearyl alcohol and 70% starch in granular form.
  • a suitable commercial source of the silicone active compounds is Dow Corning Co ⁇ .
  • Levels of the suds suppressor depend to some extent on the sudsing tendency of the composition, for example, an ADD for use at 2000 ppm comprising 2% octadecyldimethylamine oxide may not require the presence of a suds suppressor. Indeed, it is an advantage of the present invention to select cleaning-effective amine oxides which are inherently much lower in foam-forming tendencies than the typical coco amine oxides. In contrast, formulations in which amine oxide is combined with a high-foaming anionic cosurfactant, e.g., alkyl ethoxy sulfate, benefit greatly from the presence of suds suppressor.
  • a high-foaming anionic cosurfactant e.g., alkyl ethoxy sulfate
  • Phosphate esters have also been asserted to provide some protection of silver and silver-plated utensil surfaces; however, the instant compositions can have excellent silvercare without a phosphate ester component. Without being limited by theory, it is believed that lower pH formulations, e.g., those having pH of 9.5 and below, plus the presence of the low level amine oxide, both contribute to improved silver care.
  • Preferred alkyl phosphate esters contain from 16- 20 carbon atoms.
  • Highly preferred alkyl phosphate esters are monostearyl acid phosphate or monooleyl acid phosphate, or salts thereof, particularly alkali metal salts, or mixtures thereof.
  • adjunct ingredients, (c) comprise one or more alkalis, buffers, fillers, bleaches, bleach catalysts, bleach activators, enzymes, enzyme adjuncts, builders, chelating agents, material protectants, pigments, and mixtures thereof.
  • adjuncts are now more fully described.
  • Adjunct Materials Detersive ingredients or adjuncts optionally included in the instant compositions can include one or more materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or designed to improve the aesthetics of the compositions.
  • adjunct materials comprise, in total, from about 30% to about 99.9%, preferably from about 70% to about 95%, by weight of the compositions), include other active ingredients such as builders, chelants, enzymes, suds suppressors, dispersant polymers (e.g., from BASF Co ⁇ .
  • ADD composition which is particularly appreciated by the consumer is that which contains bleach.
  • a granular automatic dishwashing composition comprising, in said component (c), an oxygen or chlorine bleach.
  • an oxygen or chlorine bleach is a chlorine bleach
  • suitable types include sodium dichloroisocyanurate or its hydrate, though more generally, any suitable chlorine or bromine bleach may be used.
  • oxygen bleach types typically a hydrogen peroxide source, preferably accompanied by a bleach catalyst or bleach activator.
  • nonphosphated or phosphated granular automatic dishwashing composition in one particular embodiment a phosphated granular automatic dishwashing composition, wherein said bleach is an oxygen bleach; said composition further comprising in said component (c), one or more detersive enzymes.
  • Hydrogen peroxide sources are described in detail in Kirk Othmer's Encyclopedia of Chemical Technology, 4th Ed (1992, John Wiley & Sons), Vol. 4, pp. 271-300 "Bleaching Agents (Survey)", and include the various forms of sodium perborate and sodium percarbonate, including various coated and modified forms.
  • An "effective amount" of a source of hydrogen peroxide is any amount capable of measurably improving stain removal (especially of tea stains) from soiled dishware compared to a hydrogen peroxide source-free composition when the soiled dishware is washed by the consumer in a domestic automatic dishwasher in the presence of alkali.
  • a source of hydrogen peroxide herein is any convenient compound or mixture which under consumer use conditions provides an effective amount of hydrogen peroxide. Levels may vary widely and are usually in the range from about 0.1% to about 70%, more typically from about 0.5% to about 30%, by weight ofthe ADD compositions herein.
  • the preferred source of hydrogen peroxide used herein can be any convenient source, including hydrogen peroxide itself.
  • perborate e.g., sodium perborate (any hydrate but preferably the mono- or tetra-hydrate), sodium carbonate peroxyhydrate or equivalent percarbonate salts, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, or sodium peroxide
  • sources of available oxygen such as persulfate bleach (e.g., OXONE ® monopersulfate, manufactured by DuPont).
  • Sodium perborate monohydrate and sodium percarbonate are particularly preferred. Mixtures of any convenient hydrogen peroxide sources can also be used.
  • a preferred percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1.000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers.
  • the percarbonate can be coated with a silicate, borate or water-soluble surfactants.
  • Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.
  • compositions herein may comprise only the essential components preferably complemented by a source of hydrogen peroxide
  • fully- formulated ADD compositions herein typically will also comprise other automatic dishwashing detergent adjunct materials to improve or modify performance. These materials are selected as appropriate for the properties required of an automatic dishwashing composition.
  • low spotting and filming is desired - preferred compositions have spotting and filming grades of 3 or less, preferably less than 2, and most preferably less than 1 , as measured by the standard test of The American Society for Testing and Materials (“ASTM”) D3556-85 (Reapproved 1989) "Standard Test Method for Deposition on Glassware During Mechanical Dishwashing".
  • low sudsing is desired — preferred compositions produce less than 2 inches, more preferably less than 1 inch, of suds in the bottom of the dishwashing machine during normal use conditions (as determined using known methods such as, for example, that described in U.S. Patent 5,294,365, to Welch et al., issued March 15, 1994).
  • Metal-containing Bleach Catalysts are examples of metal-containing Bleach Catalysts.
  • the present invention compositions and methods utilize metal- containing bleach catalysts that are effective for use in ADD compositions.
  • Preferred are manganese and cobalt-containing bleach catalysts.
  • One type of metal-containing bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity, such as copper, iron, titanium, ruthenium tungsten, molybdenum, or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrate having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and water-soluble salts thereof.
  • a transition metal cation of defined bleach catalytic activity such as copper, iron, titanium, ruthenium tungsten, molybdenum, or manganese cations
  • an auxiliary metal cation having little or no bleach catalytic activity such as zinc or aluminum cations
  • a sequestrate having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid
  • Preferred examples of theses catalysts include MnIV ( u -O)3(l,4,7-trimethyl-l,4,7-triazacyclononane)2- (PF 6 ) 2 ("MnTACN"), Mn ⁇ I 2 (u-O) j (u-OAc) 2 ( 1 ,4,7-trimethyl- 1 ,4.7-triazacycIono- nane)2-(C104)2, Mn IV 4(u-O) 6 (l,4,7-triazacyclononane)4-(ClO4)2.
  • ligands suitable for use herein include l,5,9-trimethyl-l,5,9-triazacyclododecane, 2- methyl-l,4,7-triazacyclononane, 2-methyl- 1,4,7-triazacyclononane, and mixtures thereof.
  • bleach catalysts useful in automatic dishwashing compositions and concentrated powder detergent compositions may also be selected as appropriate for the present invention.
  • Still another type of bleach catalyst is a water-soluble complex of manganese (II), (III), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups.
  • Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylitol, arabitol, adonitol, meso-erythritol, meso-inositol. lactose, and mixtures thereof.
  • U.S. Pat. 5,114,611 teaches another useful bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with an non-(macro)- cyclic ligand.
  • Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings.
  • said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro.
  • substituents such as alkyl, aryl, alkoxy, halide, and nitro.
  • Particularly preferred is the ligand 2,2'-bispyridylamine.
  • Preferred bleach catalysts include Co-, Cu-, Mn-, or Fe- bispyridylmethane and bispyridylamine complexes.
  • Highly preferred catalysts include Co(2,2'-bispyridylamine)Cl2, Di(isothiocyanato)bispyridylamine- cobalt (II), trisdipyridylamine-cobalt(II) perchlorate, Co(2,2- bispyridylamine)2 ⁇ 2G ⁇ 4, Bis-(2,2'-bispyridylamine) copper(II) perchlorate, tris(di-2-pyridyIamine) iron(II) perchlorate, and mixtures thereof.
  • bleach catalyst examples include Mn gluconate, Mn(CF3SO3)2 ⁇ Co( H3)5Cl, and the binuclear Mn complexed with tetra-N-dentate and bi-N- dentate ligands, including N4Mn III (u-O)2Mn IV N4) + and [Bipy2Mn III (u- O)2Mn Iv bipy 2 ]-(ClO4)3-
  • the bleach catalysts may also be prepared by combining a water-soluble ligand with a water-soluble manganese salt in aqueous media and concentrating the resulting mixture by evaporation. Any convenient water-soluble salt of manganese can be used herein.
  • Manganese (II), (III), (IV) and/or (V) is readily available on a commercial scale. In some instances, sufficient manganese may be present in the wash liquor, but, in general, it is preferred to detergent composition Mn cations in the compositions to ensure its presence in catalytically-effective amounts.
  • the sodium salt of the ligand and a member selected from the group consisting of MnSO4, Mn(ClO4)2 or MnCl2 (least preferred) are dissolved in water at molar ratios of ligand:Mn salt in the range of about 1 :4 to 4: 1 at neutral or slightly alkaline pH.
  • the water may first be de-oxygenated by boiling and cooled by spraying with nitrogen. The resulting solution is evaporated (under N2, if desired) and the resulting solids are used in the bleaching and detergent compositions herein without further purification.
  • the water-soluble manganese source such as MnSO4
  • MnSO4 is added to the bleach cleaning composition or to the aqueous bleaching/cleaning bath which comprises the ligand.
  • Some type of complex is apparently formed in situ, and improved bleach performance is secured. In such an in situ process, it is convenient to use a considerable molar excess of the ligand over the manganese, and mole ratios of ligand:Mn typically are 3:1 to 15:1.
  • the additional ligand also serves to scavenge vagrant metal ions such as iron and copper, thereby protecting the bleach from decomposition.
  • vagrant metal ions such as iron and copper
  • the bleach-catalyzing manganese complexes have not been elucidated, it may be speculated that they comprise chelates or other hydrated coordination complexes which result from the interaction of the carboxyl and nitrogen atoms of the ligand with the manganese cation.
  • the oxidation state of the manganese cation during the catalytic process is not known with certainty, and may be the (+11), (+III), (+IV) or (+V) valence state. Due to the ligands' possible six points of attachment to the manganese cation, it may be reasonably speculated that multi-nuclear species and/or "cage" structures may exist in the aqueous bleaching media. Whatever the fo ⁇ n of the active Mn ligand species which actually exists, it functions in an apparently catalytic manner to provide improved bleaching performances on stubborn stains such as tea. ketchup, coffee, wine, juice, and the like.
  • bleach catalysts are described, for example, in European patent application, publication no. 408,131 (cobalt complex catalysts), European patent applications, publication nos. 384,503, and 306,089 (metal lo-po ⁇ hy rin catalysts), U.S. 4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,71 1 ,748 and European patent application, publication no. 224,952, (absorbed manganese on aluminosilicate catalyst), U.S. 4,601 ,845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4,1 19,557 (ferric complex catalyst), German Pat.
  • the preferred cobalt catalyst of this type useful herein are cobalt pentaamine chloride salts having the formula [Co(NH3)5Cl] Y y , and especially [Co(NH 3 ) 5 Cl]Cl 2 .
  • T are selected from the group consisting of chloride, iodide, I3", formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PFg", BF4", B(Ph)4", phosphate, phosphite, silicate, tosylate, methanesulfonate, and combinations thereof.
  • T can be protonated if more than one anionic group exists in T, e.g., HPO42-, HCO3", H2PO4", etc.
  • T may be selected from the group consisting of non-traditional inorganic anions such as anionic surfactants (e.g., linear alkyl benzene sulfonates (LAS), alkyl sulfates (AS), alkylethoxysulfonates (AES), etc.) and/or anionic polymers (e.g., polyacrylates, polymethacrylates, etc.).
  • anionic surfactants e.g., linear alkyl benzene sulfonates (LAS), alkyl sulfates (AS), alkylethoxysulfonates (AES), etc.
  • anionic polymers e.g., polyacrylates, polymethacrylates, etc.
  • the M moieties include, but are not limited to, for example, F", SO4-2, NCS", SCN", S2 ⁇ 3"2, NH3, PO43-, and carboxylates (which preferably are mono- carboxylates, but more than one carboxylate may be present in the moiety as long as the binding to the cobalt is by only one carboxylate per moiety, in which case the other carboxylate in the M moiety may be protonated or in its salt form).
  • M can be protonated if more than one anionic group exists in M (e.g..
  • M moieties are substituted and unsubstituted C 1 -C30 carboxylic acids having the formulas:
  • R is preferably selected from the group consisting of hydrogen and C1-C30 (preferably C ⁇ -C ⁇ ⁇ ) unsubstituted and substituted alkyl, C6-C30 (preferably Cg-Cjg) unsubstituted and substituted aryl, and C3-C30 (preferably C5- Cjg) unsubstituted and substituted heteroaryl, wherein substituents are selected from the group consisting of -NR' 3 , -NR'4 + , -C(O)OR ⁇ -OR', -C(O)NR'2, wherein R* is selected from the group consisting of hydrogen and Cj-Cg moieties.
  • Such substituted R therefore include the moieties -(CH2) n OH and -(CH2) n R'4 + , wherein n is an integer from 1 to about 16, preferably from about 2 to about 10, and most preferably from about 2 to about 5.
  • M are carboxylic acids having the formula above wherein R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, straight or branched C4-C12 alkyl, and benzyl. Most preferred R is methyl.
  • Preferred carboxylic acid M moieties include formic, benzoic, octanoic, nonanoic, decanoic, dodecanoic, malonic, maleic, succinic, adipic, phthalic, 2-ethylhexanoic, naphthenoic, oleic, palmitic, triflate, tartrate, stearic, butyric, citric, acrylic, aspartic, fumaric, lauric, linoleic, lactic, malic, and especially acetic acid.
  • the B moieties include carbonate, di- and higher carboxylates (e.g., oxalate, malonate, malic, succinate, maleate), picolinic acid, and alpha and beta amino acids (e.g., glycine, alanine, beta-alanine, phenyialanine).
  • carboxylates e.g., oxalate, malonate, malic, succinate, maleate
  • picolinic acid e.g., glycine, alanine, beta-alanine, phenyialanine.
  • Cobalt bleach catalysts useful herein are known, being described for example along with their base hydrolysis rates, in M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg. Mech.. (1983), 2, pages 1-94.
  • the most preferred cobalt catalyst useful herein are cobalt pentaamine acetate salts having the formula [Co(NH3)5OAc] Ty, wherein OAc represents an acetate moiety, .9
  • catalysts may be coprocessed with adjunct materials so as to reduce the color impact if desired for the aesthetics of the product, or to be included in enzyme-containing particles as exemplified hereinafter, or the compositions may be manufactured to contain catalyst "speckles".
  • the cleaning compositions and cleaning processes herein can be adjusted to provide on the order of at least one part per hundred million of the active bleach catalyst species in the aqueous washing medium, and will preferably provide from about 0.01 ppm to about 25 ppm, more preferably from about 0.05 ppm to about 10 ppm, and most preferably from about 0.1 ppm to about 5 ppm, of the bleach catalyst species in the wash liquor.
  • typical automatic dishwashing compositions herein will comprise from about 0.0005% to about 0.2%, more preferably from about 0.004% to about 0.08%, of bleach catalyst by weight of the cleaning compositions.
  • the present fully-formulated ADD compositions desirably include particular kinds of enzyme.
  • "Detersive enzyme”, as used herein, means any enzyme having a cleaning, stain removing or otherwise beneficial effect in an ADD composition.
  • Preferred detersive enzymes are hydrolases such as proteases, amylases and lipases.
  • Highly preferred for automatic dishwashing are amylases and/or proteases, including both current commercially available types and improved types which, though more bleach compatible, have a remaining degree of bleach deactivation susceptibility. If only one enzyme is used, it is preferably an amyolytic enzyme when the composition is for automatic dishwashing use. Highly preferred for automatic dishwashing is a mixture of proteolytic enzymes and amyloytic enzymes.
  • the enzymes to be inco ⁇ orated include proteases, amylases, lipases, 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, thermostability, stability versus active detergents, builders, etc. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
  • Enzymes are normally inco ⁇ orated in the instant detergent compositions at levels sufficient to provide a "cleaning-effective amount".
  • cleaning- effective amount refers to any amount capable of producing a cleaning, stain removal or soil removal effect on substrates such as fabrics, dishware and the like. Since enzymes are catalytic materials, such amounts may be very small. In practical terms for current commercial preparations, typical amounts are 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 6%, 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.
  • AU Anson units
  • proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis. Another suitable 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 as ESPERASE®. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No. 1,243,784 of Novo.
  • protealytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the tradenames ALCALASE® and SAVINASE® by Novo Industries A/S (Denmark) and MAXATASE® by International Bio-Synthetics, Inc. (The Netherlands).
  • 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).
  • protease D is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, + 195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in the patent applications of A.
  • Amylases suitable herein include, for example, ⁇ -amylases described in British Patent Specification No. 1,296,839 (Novo), RAPIDASE®, International Bio- Synthetics, Inc. and TERMAMYL®, Novo Industries.
  • the present invention in certain preferred embodiments, can makes use of amylases having improved stability in detergents, especially improved oxidative stability.
  • a convenient absolute stability reference-point against which amylases used in these preferred embodiments of the instant invention represent a measurable improvement is the stability of TERMAMYL® in commercial use in 1993 and available from Novo Nordisk A/S.
  • This TERMAMYL® amylase is a "reference amylase". and is itself well-suited for use in the ADD (Automatic Dishwashing Detergent) compositions of the invention.
  • amylases herein share the characteristic of being "stability-enhanced" amylases, characterized, at a minimum, by a measurable improvement in one or more of: oxidative stability, e.g., to hydrogen peroxide/tetraacetylethylenediamine in buffered solution at pH 9-10; thermal stability, e.g., at common wash temperatures such as about 60°C; or alkaline stability, e.g., at a pH from about 8 to about 1 1, all measured versus the above- identified reference-amylase.
  • oxidative stability e.g., to hydrogen peroxide/tetraacetylethylenediamine in buffered solution at pH 9-10
  • thermal stability e.g., at common wash temperatures such as about 60°C
  • alkaline stability e.g., at a pH from about 8 to about 1 1, all measured versus the above- identified reference-amylase.
  • Prefe ⁇ ed amylases herein can demonstrate further improvement versus more challenging reference amylases, the latter reference amylases being illustrated by any of the precursor amylases of which preferred amylases within the invention are variants. Such precursor amylases may themselves be natural or be the product of genetic engineering. Stability can be measured using any of the art-disclosed technical tests. See references disclosed in WO 94/02597, itself and documents therein referred to being inco ⁇ orated by reference.
  • stability-enhanced amylases respecting the preferred embodiments of the invention can be obtained from Novo Nordisk A S, or from Genencor International.
  • Preferred amylases herein have the commonality of being derived using site- directed mutagenesis from one or more of the Baccillus amylases, especialy the Bacillus alpha-amylases, regardless of whether one, two or multiple amylase strains are the immediate precursors.
  • amylases are preferred for use herein despite the fact that the invention makes them “optional but preferred” materials rather than essential.
  • amylases are non-limitingly illustrated by the following: (a) An amylase according to the hereinbefore inco ⁇ orated WO/94/02597,
  • Met was substituted, one at a time, in positions 8,15,197,256,304,366 and 438 leading to specific mutants, particularly important being M197L and M197T with the M197T variant being the most stable expressed variant. Stability was measured in CASCADE® and SUNLIGHT®;
  • amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S.
  • amylases include those commercially marketed as DURAMYL by NOVO; bleach- stable amylases are also commercially available from Genencor.
  • 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.
  • Cellulases usable in, but not preferred, for the present invention include both bacterial or fungal cellulases. Typically, 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 DSM 1800 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.
  • Suitable lipase enzymes for detergent use 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 lipases 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 lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
  • lipolyticum NRRLB 3673 commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S. Biochemical Co ⁇ ., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
  • the LIPOLASE® enzyme derived from Humicola lanuginosa and commercially available from Novo is a preferred lipase for use herein.
  • Another prefe ⁇ ed lipase enzyme is the D96L variant of the native Humicola lanuginosa lipase, as described in WO 92/05249 and Research Disclosure No. 35944, March 10, 1994, both published by Novo.
  • lipolytic enzymes are less preferred than amylases and/or proteases for automatic dishwashing embodiments ofthe present invention.
  • Peroxidase enzymes can be used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are typically 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 O. Kirk. assigned to Novo Industries A/S.
  • the present invention encompasses peroxidase- free automatic dishwashing composition embodiments.
  • Enzyme-containing compositions herein, especially liquid compositions, herein may comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system.
  • the enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme.
  • Such stabilizing systems can comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boronic acid, and mixtures thereof.
  • the stabilizing system of the ADDs herein may further comprise from 0 to about 10%, preferably from about 0.01% to about 6% by weight, of chlorine bleach scavengers, added to prevent chlorine bleach species present in many water supplies from attacking and inactivating the enzymes, especially under alkaline conditions. While chlorine levels in water may be small, typically in the range from about 0.5 ppm to about 1.75 ppm, the available chlorine in the total volume of water that comes in contact with the enzyme during dishwashing is relatively large; accordingly, enzyme stability in-use can be problematic.
  • Suitable chlorine scavenger anions are widely known and readily available, and are illustrated by salts containing ammonium cations with sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc.
  • Antioxidants such as carbamate, ascorbate, etc., organic amines such as ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof, monoethanolamine (MEA), and mixtures thereof can likewise be used.
  • EDTA ethylenediaminetetracetic acid
  • MEA monoethanolamine
  • scavengers such as bisulfate, nitrate, chloride, sources of hydrogen peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, malate, tartrate, salicylate, etc., and mixtures thereof can be used if desired.
  • the chlorine scavenger function can be performed by several of the ingredients separately listed under better recognized functions, (e.g., other components of the invention such as sodium perborate), there is no requirement to add a separate chlorine scavenger unless a compound performing that function to the desired extent is absent from an enzyme- containing embodiment of the invention; even then, the scavenger is added only for optimum results.
  • the formulator will exercise a chemist's normal skill in avoiding the use of any scavenger which is majorly incompatible with other ingredients, if used.
  • ammonium salts can be simply admixed with the detergent composition but are prone to adsorb water and/or liberate ammonia during storage. Accordingly, such materials, if present, are desirably protected in a particle such as that described in U.S. Patent 4,652,392, Baginski et al.
  • the peroxygen bleach component in the composition is formulated with a bleach catalyst as described supra, or with an activator (peracid precursor), or with a combination of the two.
  • Suitable activator levels are in the range from about 0.01% to about 15%, preferably from about 1% to about 10%, more preferably from about 1% to about 8%, by weight of the composition.
  • Prefe ⁇ ed activators are selected from the group consisting of tetraacetyl ethylene diamin (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3- chlorobenzoylcaprolactam, benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate (NOBS), phenyl benzoate (PhBz), decanoyloxybenzenesulphonate (C I Q-OBS), benzoylvalerolactam (BZVL), octanoyloxybenzenesulphonate (Cg-OBS), perhydrolyzable esters and mixtures thereof, most preferably benzoylcaprolactam and benzoylvalerolactam.
  • Particularly prefe ⁇ ed bleach activators in the pH range from about 8 to about 9.5 are those selected having an OBS or VL leaving group.
  • Preferred bleach activators are those described in U.S. Patent 5,130,045, Mitchell et al, and 4.412,934, Chung et al, and copending patent applications U. S. Serial Nos. 08/064,624, 08/064,623, 08/064,621 , 08/064,562, 08/064,564, 08/082.270 and copending application to M. Burns, A. D. Willey, R. T. Hartshorn, C. K. Ghosh, entitled "Bleaching Compounds Comprising Peroxyacid Activators Used With Enzymes" and having U.S. Serial No. 08/133,691 (P&G Case 4890R). all of which are inco ⁇ orated herein by reference.
  • the mole ratio of peroxygen bleaching compound (as AvO) to bleach activator in the present invention generally ranges from at least 1 :1, preferably from about 20:1 to about 1 :1, more preferably from about 10: 1 to about 3:1.
  • Quaternary substituted bleach activators may also be included.
  • the present detergent compositions preferably comprise a quaternary substituted bleach activator (QSBA) or a quaternary substituted peracid (QSP); more preferably, the former.
  • QSBA quaternary substituted bleach activator
  • QSP quaternary substituted peracid
  • pH and Buffering Variation Prefe ⁇ ed ADD compositions herein will have pH ranges in accordance with the description hereinabove. It has been found, su ⁇ risingly, that one suitable approach to the provision of suitable pH ranges is through the use, as a source of alkalinity in said saisct component (c), an alkali metal oxide or alkaline earth oxide. A preferred oxide is Calcium Oxide.
  • Such an automatic dishwashing detergent composition can be made in a form substantially free from, or having, phosphate builders.
  • ADD compositions herein will be buffered, i.e., they are relatively resistant to pH drop in the presence of acidic soils.
  • other compositions herein may have exceptionally low buffering capacity, or may be substantially unbuffered.
  • Techniques for controlling or varying pH at recommended usage levels more generally include the use of not only buffers, but also additional alkalis, acids, pH-jump systems, dual compartment containers, etc., and are well known to those skilled in the art.
  • the preferred ADD compositions herein comprise a pH-adjusting component selected from water-soluble alkaline inorganic salts and water-soluble organic or inorganic builders.
  • the pH-adjusting components are selected so that when the ADD is dissolved in water at a concentration of 1,000 - 5,000 ppm, the pH remains in the range stated hereinabove.
  • One preferred nonphosphate pH-adjusting component ofthe invention is selected from the group consisting of:
  • - sodium silicate preferably hydrous sodium silicate having Si ⁇ 2:Na2 ⁇ ratio of from about 1 :1 to about 2: 1, and mixtures thereof with limited quantites of sodium metasilicate; - sodium citrate;
  • Preferred embodiments contain low levels of silicate other than the silicate included in the essential synthetic siliceous porous material. Suitable levels are from about 3% to about 10% Si ⁇ 2 by wight ofthe ADD composition.
  • Suitable levels are from about 3% to about 10% Si ⁇ 2 by wight ofthe ADD composition.
  • - Illustrative of highly preferred pH-adjusting component systems are binary mixtures of granular sodium citrate with anhydrous sodium carbonate, and three- component mixtures of granular sodium citrate trihydrate. citric acid monohydrate and anhydrous sodium carbonate.
  • the amount of the pH adjusting component in the instant ADD compositions is preferably from about 1% to about 50%, by weight of the composition. In a prefe ⁇ ed embodiment, the pH-adjusting component is present in the ADD composition in an amount from about 5% to about 40%, preferably from about 10% to about 30%, by weight.
  • compositions herein having a pH between about 9.5 and about 1 1 of the initial wash solution particularly preferred ADD embodiments comprise, by weight of ADD, from about 5% to about 40%, preferably from about 10% to about 30%, most preferably from about 15% to about 20%, of sodium citrate with from about 5% to about 30%, preferably from about 7% to 25%, most preferably from about 8% to about 20% sodium carbonate.
  • the essential pH-adjusting system can be complemented (i.e. for improved sequestration in hard water) by other optional detergency builder salts selected from nonphosphate detergency builders known in the art, which include the various water-soluble, alkali metal, ammonium or substituted ammonium borates, hydroxysulfonates, polyacetates, and polycarboxylates. Prefe ⁇ ed are the alkali metal, especially sodium, salts of such materials. Alternate water-soluble, non- phosphorus organic builders can be used for their sequestering properties.
  • polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid; nitrilotriacetic acid, tartrate monosuccinic acid, tartrate disuccinic acid, oxydisuccinic acid, carboxymethoxysuccinic acid, mellitic acid, and sodium benzene polycarboxylate salts.
  • the present automatic dishwashing detergent compositions may further comprise water-soluble silicates.
  • Water-soluble silicates herein are any silicates other than the essential synthetic siliceous porous material which are soluble to the extent that they do not adveresely affect spotting/filming characteristics of the ADD composition. Examples of such silicates are sodium metasilicate and. more generally, the alkali metal silicates, particularly those having a SiO2:Na2O 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 a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, Na SKS-6 and other water-soluble silicates usefule herein do not contain aluminum. NaSKS-6 is the ⁇ -Na2Si ⁇ 5 form of layered silicate and can be prepared by methods such as those described in German DE-A-3,417,649 and DE-A-3, 742,043.
  • SKS-6 is a preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi x ⁇ 2 x + j 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.
  • Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the ⁇ -, ⁇ - and ⁇ - forms.
  • 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.
  • Silicates particularly useful in automatic dishwashing (ADD) applications include granular hydrous 2-ratio silicates such as BRITESIL® H20 from PQ Co ⁇ ., and the commonly sourced BRITESIL® H24 though liquid grades of various silicates can be used when the ADD composition has liquid form. Within safe limits, sodium metasilicate or sodium hydroxide alone or in combination with other silicates may be used in an ADD context to boost wash pH to a desired level. Builders
  • an automatic dishwashing detergent composition wherein said component (c) comprises a builder selected from phosphates, citrates, NTA, noncitrate polycarboxylates having molecular weight below about 1000, and mixtures thereof; and wherein said detergent composition is substantially free from polymeric precipitation inhibitors, said polymeric precipitation inhibitors including polyacrylates having molecular weight above about 1000.
  • said phosphate builder comprises sodium tripolyphosphate.
  • detergent builders other than silicates 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 automatic dishwashing and fabric laundering compositions, for example to assist in the removal of particulate soils.
  • the level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least about 1% builder. High performance compositions typically comprise 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, however, are not excluded. Phosphate detergent builders for use in ADD compositions are well known.
  • Phosphate builder sources are described in detail in Kirk Othmer, 3rd Edition, Vol. 17, pp. 426-472 and in "Advanced Inorganic Chemistry” by Cotton and Wilkinson, pp. 394-400 (John Wiley and Sons, Inc.; 1972).
  • Prefe ⁇ ed levels of phosphate builders herein are from about 10% to about 75%, preferably from about 15% to about 40%, of phosphate builder.
  • inorganic, organic, P-containing or non-phosphate detergent builders include, but are not limited to, phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates, citrate, and layered silicate.
  • Conventional aluminosilicates such as zeolite A are preferably excluded from the instant compositions on account of their abrasiveness.
  • 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.
  • Various grades and types of sodium carbonate and sodium sesquicarbonate may be used, certain of which are particularly useful as carriers for o ⁇ her ingredients, especially detersive surfactants.
  • Organic detergent builders suitable for the pu ⁇ oses of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds.
  • polycarboxylate 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 or "overbased". When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
  • polycarboxylate builders include a variety of categories of useful materials.
  • One important category of polycarboxylate 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 hydroxypolycarboxylates copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5- trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid
  • various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid
  • polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic 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 laundry detergent and automatic dishwashing formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in combination with the aforementioned BRITESIL types, and or layered silicate builders. Oxydisuccinates are also useful in such compositions and combinations. Also suitable in the detergent compositions of the present invention are the
  • succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof.
  • a particularly preferred compound of this type is dodecenylsuccinic acid.
  • succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2- dodecenylsuccinate (prefe ⁇ ed), 2-pentadecenylsuccinate, and the like.
  • Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
  • Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226, Crutchfield et al, issued March 13, 1979 and in U.S. Patent 3,308.067. Diehi, issued March 7, 1967. See also U.S. Patent 3,723,322.
  • Fatty acids e.g., C ⁇ -Cj monocarboxylic acids
  • Fatty acids or their salts are undesirable in Automatic Dishwashing (ADD) embodiments in situations wherein soap scums can form and be deposited on dishware.
  • ADD Automatic Dishwashing
  • the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
  • Phosphonate builders such as ethane- 1 -hydroxy- 1 , 1 -diphosphonate and other known phosphonates (see. for example, U.S. Patents 3,159,581 ; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used though such materials are more commonly used in a low-level mode as chelants or stabilizers.
  • Chelating Agents such as ethane- 1 -hydroxy- 1 , 1 -diphosphonate and other known phosphonates
  • compositions herein may also optionally contain one or more transition- metal selective sequestrants, "chelants” or “chelating agents”, e.g., iron and/or copper and/or manganese chelating agents.
  • chelants e.g., iron and/or copper and/or manganese chelating agents.
  • Chelating agents suitable for use herein can be selected from the group consisting of aminocarboxylates, phosphonates (especially the aminophosphonates), polyfunctionally-substituted aromatic chelating agents, and mixtures thereof. 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 control iron, copper and manganese in washing solutions which are known to decompose hydrogen peroxide and/or bleach activators; other benefits include inorganic film prevention or scale inhibition.
  • chelating agents for use herein include the DEQUEST® series, and chelants from Monsanto, DuPont, and Nalco, Inc.
  • Aminocarboxylates useful as optional chelating agents are further illustrated by ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilo- triacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, diethylenetriamine-pentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts thereof.
  • chelant mixtures may be used for a combination of functions, such as multiple transition-metal control, long- term product stabilization, and/or control of precipitated transition metal oxides and/or hydroxides.
  • 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 l,2-dihydroxy-3,5-disulfobenzene.
  • a highly preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially (but not limited to) the [S,S] isomer as described in U.S. Patent 4,704.233, November 3, 1987, to Hartman and Perkins.
  • EDDS ethylenediamine disuccinate
  • the trisodium salt is prefe ⁇ ed though other forms, such as magnesium salts, may also be useful.
  • Aminophosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are acceptable in detergent compositions, and include the ethylenediaminetetrakis (methyl enephosphonates) and the diethylenetriaminepentakis (methylene phosphonates). Preferably, these aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • chelating agents or transition-metal-selective sequestrants will preferably comprise from about 0.001% to about 10%, more preferably from about 0.05% to about 1% by weight ofthe compositions herein. Dispersant Polymer
  • Certain ADD compositions herein may additionally contain a dispersant polymer.
  • a dispersant polymer in the instant ADD compositions is typically at levels in the range from 0 to about 25%, preferably from about 0.5% to about 20%, more preferably from about 1% to about 8% by weight of the ADD composition.
  • Dispersant polymers are useful for improved filming performance of the present ADD compositions, especially in higher pH embodiments, such as those in which wash pH exceeds about 9.5.
  • Particularly preferred are polymers which inhibit the deposition of calcium carbonate or magnesium silicate on dishware.
  • Dispersant polymers suitable for use herein are further illustrated by the film- forming polymers described in U.S. Pat. No. 4,379,080 (Mu ⁇ hy), issued Apr. 5, 1983.
  • Suitable polymers are preferably at least partially neutralized or alkali metal, ammonium or substituted ammonium (e.g., mono-, di- or triethanolammonium) salts of polycarboxylic acids.
  • the alkali metal, especially sodium salts are most preferred.
  • the molecular weight ofthe polymer can vary over a wide range, it preferably is from about 1,000 to about 500,000, more preferably is from about 1.000 to about 250,000, and most preferably, especially if the ADD is for use in North American automatic dishwashing appliances, is from about 1,000 to about 5,000.
  • suitable dispersant polymers include those disclosed in U.S. Patent No. 3,308,067 issued March 7, 1967, to Diehl.
  • Unsaturated monomeric acids that can be polymerized to form suitable dispersant polymers include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
  • monomeric segments containing no carboxylate radicals such as methyl vinyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 50% by weight ofthe dispersant polymer.
  • Copolymers of acrylamide and acrylate having a molecular weight of from about 3,000 to about 100,000, preferably from about 4,000 to about 20,000, and an acrylamide content of less than about 50%, preferably less than about 20%, by weight of the dispersant polymer can also be used. Most preferably, such dispersant polymer has a molecular weight of from about 4,000 to about 20,000 and an acrylamide content of from about 0% to about 15%, by weight ofthe polymer.
  • Particularly preferred dispersant polymers are low molecular weight modified polyacrylate copolymers.
  • Such copolymers contain as monomer units: a) from about 90% to about 10%, preferably from about 80% to about 20% by weight acrylic acid or its salts and b) from about 10% to about 90%, preferably from about 20% to about 80% by weight of a substituted acrylic monomer or its salt and have the general formula: -[(C(R 2 )C(R 1 )(C(O)OR 3 )] wherein the apparently unfilled valencies are in fact occupied by hydrogen and at least one of the substituents Rl, R2, or R3, preferably R' or R 2 , is a 1 to 4 carbon alkyl or hydroxyalkyl group; Rl or R can be a hydrogen and R 3 can be a hydrogen or alkali metal salt.
  • Suitable low molecular weight polyacrylate dispersant polymer preferably has a molecular weight of less than about 15,000, preferably from about 500 to about 10.000, most preferably from about 1,000 to about 5,000.
  • the most preferred polyacrylate copolymer for use herein has a molecular weight of about 3,500 and is the fully neutralized form of the polymer comprising about 70% by weight acrylic acid and about 30% by weight methacrylic acid.
  • Suitable modified polyacrylate copolymers include the low molecular weight copolymers of unsaturated aliphatic carboxylic acids disclosed in U.S. Patents 4,530,766, and 5,084,535.
  • Agglomerated forms of the present ADD compositions may employ aqueous solutions of polymer dispersants as liquid binders for making the agglomerate (particularly when the composition consists of a mixture of sodium citrate and sodium carbonate).
  • polyacrylates with an average molecular weight of from about 1,000 to about 10,000
  • acrylate/maleate or acrylate/flimarate copolymers with an average molecular weight of from about 2,000 to about 80,000 and a ratio of acrylate to maleate or fumarate segments of from about 30: 1 to about 1 :2.
  • examples of such copolymers based on a mixture of unsaturated mono- and dicarboxylate monomers are disclosed in European Patent Application No. 66,915, published December 15, 1982.
  • Other dispersant polymers useful herein include the polyethylene glycols and polypropylene glycols having a molecular weight of from about 950 to about 30,000 which can be obtained from the Dow Chemical Company of Midland, Michigan.
  • Such compounds for example, having a melting point within the range of from about 30°C to about 100°C, can be obtained at molecular weights of 1,450, 3,400, 4,500, 6,000, 7,400, 9,500, and 20,000.
  • Such compounds are formed by the polymerization of ethylene glycol or propylene glycol with the requisite number of moles of ethylene or propylene oxide to provide the desired molecular weight and melting point of the respective polyethylene glycol and polypropylene glycol.
  • the polyethylene, polypropylene and mixed glycols are referred to using the formula: HO(CH2CH 2 O) m (CH 2 CH(CH3)O) n (CH(CH3)CH2O) 0 OH wherein m, n, and o are integers satisfying the molecular weight and temperature requirements given above.
  • dispersant polymers useful herein include the cellulose sulfate esters such as cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose sulfate, methylcellulose sulfate, and hydroxypropylcellulose sulfate.
  • cellulose sulfate esters such as cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose sulfate, methylcellulose sulfate, and hydroxypropylcellulose sulfate.
  • Sodium cellulose sulfate is the most prefe ⁇ ed polymer of this group.
  • Suitable dispersant polymers are the carboxylated polysaccharides. particularly starches, celluloses and alginates, described in U.S. Pat. No. 3,723.322, Diehl, issued Mar. 27, 1973; the dextrin esters of polycarboxylic acids disclosed in U.S. Pat. No. 3,929,107, Thompson, issued Nov. 1 1 , 1975; the hydroxyalkyl starch ethers, starch esters, oxidized starches, dextrins and starch hydrolysates described in U.S. Pat No. 3,803,285, Jensen, issued Apr. 9, 1974; the carboxylated starches described in U.S. Pat. No. 3,629,121, Eldib, issued Dec. 21, 1971; and the dextrin starches described in U.S. Pat. No. 4,141,841, McDonald, issued Feb. 27, 1979.
  • Prefe ⁇ ed cellulose-derived dispersant polymers are the carboxymethyl celluloses.
  • the present ADD compositions may contain one or more material care agents which are effective as corrosion inhibitors and/or anti-tarnish aids.
  • material care agents include metasilicate, silicate, bismuth salts, manganese salts, paraffin, triazoles, pyrazoles, thiols, mercaptans, aluminium fatty acid salts, and mixtures thereof.
  • Suitable conosion inhibitors include paraffin oil, typically a predominantly branched aliphatic hydrocarbon having a number of carbon atoms in the range of from about 20 to about 50; prefe ⁇ ed paraffin oil is selected from predominantly branched C25- 45 species with a ratio of cyclic to noncyclic hydrocarbons of about 32:68.
  • a paraffin oil meeting those characteristics is sold by Wintershall, Salzbergen, Germany, under the trade name WINOG 70.
  • the addition of low levels of bismuth nitrate i.e., Bi(NO3)3 is also preferred.
  • conosion inhibitor compounds include benzotriazole and comparable compounds; mercaptans or thiols including thionaphtol and thioanthranol; and finely divided Aluminium fatty acid salts, such as aluminium tristearate.
  • the formulator will recognize that such materials will generally be used judiciously and in limited quantities so as to avoid any tendency to produce spots or films on glassware or to compromise the bleaching action of the compositions. For this reason, mercaptan anti-tarnishes which are quite strongly bleach-reactive and common fatty carboxylic acids which precipitate with calcium in particular are preferably avoided.
  • Other Optional Adjuncts are particularly benzotriazole and comparable compounds.
  • filler materials can also be present in the instant ADDs. These include sucrose, sucrose esters, sodium sulfate, potassium sulfate, etc., in amounts up to about 70%, preferably from 0% to about 40% of the ADD composition. Prefened filler is sodium sulfate, especially in good grades having at most low levels of trace impurities.
  • Sodium sulfate used herein preferably has a purity sufficient to ensure it is non-reactive with bleach; it may also be treated with low levels of sequestrants, such as phosphonates or EDDS in magnesium-salt form. Note that preferences, in terms of purity sufficient to avoid decomposing bleach, applies also to pH-adjusting component ingredients, specifically including any silicates used herein.
  • the present invention encompasses embodiments which are substantially free from sodium chloride or potassium chloride.
  • Hydrotrope materials such as sodium benzene sulfonate, sodium toluene sulfonate, sodium cumene sulfonate, etc., can be present, e.g., for better dispersing surfactant.
  • Bleach-stable perfumes (stable as to odor); and bleach-stable dyes such as those disclosed in U.S. Patent 4,714,562, Roselle et al, issued December 22, 1987 can also be added to the present compositions in appropriate amounts.
  • Other common detergent ingredients consistent with the spirit and scope of the present invention are not excluded.
  • ADD compositions herein can contain water-sensitive ingredients or ingredients which can co-react when brought together in an aqueous environment, it is desirable to keep the free moisture content ofthe ADDs at a minimum, e.g., 7% or less, preferably 4% or less of the ADD; and to provide packaging which is substantially impermeable to water and carbon dioxide. Coating measures have been described herein to illustrate a way to protect the ingredients from each other and from air and moisture. Plastic bottles, including refillable or recyclable types, as well as conventional banier cartons or boxes are another helpful means of assuring maximum shelf-storage stability. As noted, when ingredients are not highly compatible, it may further be desirable to coat at least one such ingredient with a low-foaming nonionic surfactant for protection.
  • substantially chlorine bleach-free granular automatic dishwashing compositions of the invention are as follows: a substantially chlorine- bleach free automatic dishwashing composition comprising amylase (e.g., TERMAMYL®) and/or a bleach stable amylase and a bleach system comprising a source of hydrogen peroxide selected from sodium perborate and sodium percarbonate and a cobalt catalyst as defined herein.
  • amylase e.g., TERMAMYL®
  • a bleach stable amylase e.g., a bleach stable amylase
  • a bleach system comprising a source of hydrogen peroxide selected from sodium perborate and sodium percarbonate and a cobalt catalyst as defined herein.
  • substantially chlorine-bleach free automatic dishwashing composition comprising an oxidative stability-enhanced amylase and a bleach system comprising a source of hydrogen peroxide selected from sodium perborate and sodium percarbonate, a cobalt catalyst, and TAED or NOBS.
  • the present invention also encompasses a method for cleaning soiled tableware comprising contacting said tableware with an aqueous medium comprising the hereinbefore-described mesoporous siliceous materials having a pore size from 15 to 100 angstroms present at concentrations of from about 2 ppm to about 100 ppm, preferably from about 2 ppm to about 30 ppm, more preferably from 2 ppm to about 10 ppm, and low sudsing nonionic surfactant at hereinbefore- referenced levels, in a domestic automatic dishwashing appliance,
  • said method suitably encompasses:
  • dispensing water and an alkaline automatic dishwashing detergent comprising a synthetic silicate selected from at least partially alkali-soluble mesopores and macropores into said dishwasher; - treating said soiled tableware for a period of at least about 2 minutes with the alkaline bath produced by said water and said detergent, and
  • the synthetic silicate is believed to be at least partially dissolved to provide silicate as a glass protectant and at least partially acts as a collector or scavenger of precipitating alkaline earth salts, improving the cleaning and/or material protection of said ware.
  • an automatic dishwashing composition comprising:
  • the prefened cobalt bleach catalysts having carboxylate ligands may further be made by the following synthesis methods which are illustrated for the preferred catalysts [Co(NH 3 ) 5 OAc] CI 2 ; [Co(NH 3 ) 5 OAc] (OAc) 2 ; [Co(NH 3 ) 5 OAc](PF 6 )2, and [Co(NH 3 ) 5 OAc](NO3)2.
  • Synthesis 1 [Co(NH3)5Cl]Cl 2 (26.4 g, 0.10 mol) is added to distilled water (800 mL). NH4OH (23.4 mL, 0.600 mol) is slowly added with stirring. The solution is then heated to 75°C and the solid dissolves with stirring.
  • Synthesis 3 Ammonium hydroxide (4498.0 mL, 32.3 mol, 28%) and ammonium chloride (749.8 g, 14.0 mol) are combined in a 12 L three-necked round-bottomed flask fitted with a condenser, internal thermometer, mechanical sti ⁇ er, and addition funnel. Once the mixture becomes homogeneous, cobalt(II) chloride hexahydrate (1500.0 g, 6.3 mol) is added in portions over 5 min forming a slurry. The reaction mixture warms to 50 °C and takes on a muddy color. H2O2 (429.0 g, 6.3 mol, 50%) is added over 30 min.
  • Ammonium acetate (67.83 g, 0.880 mol) and ammonium hydroxide (256.62, 2.050 mol, 28%) are combined in a 1000 ml three-necked round-bottomed flask fitted with a condenser, mechanical stirrer, and internal thermometer.
  • Cobalt(II) acetate tetrahydrate (1 10.00 g, 0.400 mol) is added to the clear solution that becomes brown-black once addition of the metal salt is complete.
  • the mixture warms briefly to 40 °C.
  • Hydrogen peroxide (27.21 g, 0.400 mol, 50%) is added dropwise over 20 min. The reaction warms to 60-65 °C and turns red as the peroxide is added to the reaction mixture.
  • the red mixture is treated with a solution of sodium nitrate (74.86 g, 0.880 mol) dissolved in 50 ml of water. As the mixture stands at room temperature, red crystals form. The solid is collected by filtration and washed with cold water and isopropanol to give 6.38 g (4.9%) of the complex as a red solid.
  • the combined filtrates are concentrated by rotary evaporation (50-55 °C, 15 mm Hg (water aspirator vacuum)) to a slurry. The slurry is filtered and the red solid remaining is washed with cold water and isopropanol to give 89.38 g (68.3%) of the complex. Total yield: 95.76 g (73.1%). Analysis by HPLC, UV-Vis, and combustion are consistent with the proposed structure.
  • Amylase (0.8% active) 0.5
  • Te ⁇ olymer selected from either 60% acrylic acid/20% maleic acid/20% ethyl acrylate, or 70% acrylic acid/10% maleic acid/20% ethyl acrylate. 2 ⁇ h e AvO level ofthe above formula is 2.2%.
  • Pentaammineacetatocobalt(III) nitrate prepared as described hereinbefore; may be replaced by MnTACN.
  • the ADD's of the above dishwashing detergent composition examples are used to wash tea-stained cups, starch-soiled and spaghetti-soiled dishes, milk-soiled glasses, and starch, cheese, egg or babyfood- soiled flatware by loading the soiled dishes in a domestic automatic dishwashing appliance and washing using either cold fill, 60°C peak, or uniformly 45-50°C wash cycles with a product concentration of the exemplary compositions of from about 1,000 to about 5,000 ppm, with excellent results.
  • the following examples further illustrate phosphate built ADD compositions which contain a bleach/enzyme particle, but are not intended to be limiting thereof.
  • Pentaammineacetatocobalt (III) nitrate may be replaced by MnTACN. May be replaced by 0.45 Protease D. Polyacrylate or Acusol 480N.
  • the catalyst and enzymes are introduced into the compositions as 200-2400 micron composite particles which are prepared by spray coating, fluidized bed granulation, marumarizing, prilling or flaking/grinding operations. If desired, the protease and amylase enzymes may be separately formed into their respective catalyst/enzyme composite particles, for reasons of stability, and these separate composites added to the compositions.
  • catalyst/enzyme particles prepared by drum granulation
  • the catalyst is incorporated as part of the granule core, and for example 4 the catalyst is post added as a coating.
  • the mean particle size is in the range from about 200 to
  • Amylase commercial 0.4 0.4
  • Example 4 is a Compact product and Example 5 is a Regular/Fluffy product are as follows:
  • compositions herein are as follows:
  • Nonionic Surfactant 4 2.0 1.5 1.2
  • Pentaamineacetatocobalt (III) nitrate may be replaced by MnTACN.
  • the catalyst and enzymes are introduced into the final compositions as 200-2400 micron catalyst/enzyme composite particles which are prepared by spray coating, marumarizing, prilling or flaking/grinding operations.
  • the protease and amylase enzymes may be separately formed into their respective catalyst/enzyme composite particles, for reasons of stability, and these separate composites added to the compositions.
  • the ADD's of the dishwashing detergent composition examples in 6-8 are used to wash tea-stained cups, starch-soiled and spaghetti-soiled dishes, milk-soiled glasses, starch, cheese, egg or babyfood- soiled flatware and tomato stained plastic dishes by loading the soiled items in a domestic automatic dishwashing appliance and washing using either cold fill, 60°C peak, or uniformly 45-50°C wash cycles with a product concentration of the exemplary compositions of from about 1 ,000 to about 5,000 ppm, with excellent results.
  • Synthetic siliceous porous material (equal ratio of each pore size) 26. 32, 46 angstrom pore mixture 1.2
  • Dispersant Polymer (See Note 1) 6.0 6.0 6.0 6.0
  • Nonionic Surfactant SPF18, Olin 2.0 2.0 2.0
  • Dispersant Polymer One or more of: Sokolan PA30, BASF Co ⁇ ., Accusol 480N, Rohm & Haas.
  • Amylase (Termamyl® 60T, Novo) 1 0
  • Protease 2 (Protease D, as 4% active protein ) 0 2.5
  • HEDP Hydroxyethyldiphosphonate
  • Nonionic Surfactant SPF18, Olin Corp. or LF404, BASF 2 2
  • Dispersant Polymer One or more of: Sokolan PA30, BASF Corp., Accusol 480N, Rohm & Haas.
  • Note 2 [Co NH3)5CI]Ci2 supplied by Dixon Fine Chemicals.
  • Example 13 The following fully-formulated solid-form automatic dishwashing detergents
  • Protease 2 (Protease D. as 4% active protein ) 0 2.5
  • HEDP Hydroxyethyldiphosphonate
  • Nonionic Surfactant SPF18, Olin Co ⁇ . or LF404. BASF 2 2
  • Dispersant Polymer One or more of: Sokolan PA30, BASF Co ⁇ ., Accusol 480N,

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Abstract

L'invention concerne des compositions détergentes pour le lavage de la vaisselle en machine comprenant des types spécifiques de matériaux poreux siliceux, notamment ceux connus en tant que mésopores tels que ceux de la famille MCM-41 utilisés dans l'industrie à des fins non détergentes, par exemple pour le raffinage du pétrole. Ces compositions ont notamment un faible pouvoir moussant et sont conçues pour être utilisées dans des lave-vaisselles domestiques à action de pulvérisation, et comprennent des tensioactifs spécifiques à faible pouvoir moussant et un agent antimousse formulé de façon à être compatible avec les matériaux poreux siliceux. Ces compositions peuvent être comprendre des phosphates ou être exemptes de phosphates, et sont généralement alcalines.
EP97905868A 1996-02-09 1997-02-07 Compositions pour le lavage de la vaisselle en machine comprenant des mesopores et des macropores siliceux Withdrawn EP0882121A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US1142696P 1996-02-09 1996-02-09
US11426P 1996-02-09
PCT/US1997/002046 WO1997029172A1 (fr) 1996-02-09 1997-02-07 Compositions pour le lavage de la vaisselle en machine comprenant des mesopores et des macropores siliceux

Publications (1)

Publication Number Publication Date
EP0882121A1 true EP0882121A1 (fr) 1998-12-09

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Application Number Title Priority Date Filing Date
EP97905868A Withdrawn EP0882121A1 (fr) 1996-02-09 1997-02-07 Compositions pour le lavage de la vaisselle en machine comprenant des mesopores et des macropores siliceux

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Country Link
EP (1) EP0882121A1 (fr)
JP (1) JPH11504069A (fr)
BR (1) BR9707378A (fr)
WO (1) WO1997029172A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9138393B2 (en) 2013-02-08 2015-09-22 The Procter & Gamble Company Cosmetic compositions containing substituted azole and methods for improving the appearance of aging skin
US9144538B2 (en) 2013-02-08 2015-09-29 The Procter & Gamble Company Cosmetic compositions containing substituted azole and methods for alleviating the signs of photoaged skin

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9904485D0 (en) * 1999-02-27 1999-04-21 Procter & Gamble Method for protecting and/or controlled release of active ingredient
US8093200B2 (en) 2007-02-15 2012-01-10 Ecolab Usa Inc. Fast dissolving solid detergent
MX395198B (es) * 2013-10-24 2025-03-25 Ecolab Usa Inc Composiciones y metodos para eliminar suciedades de las superficies.

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5227353A (en) * 1991-07-24 1993-07-13 Mobil Oil Corporation Hydroprocessing catalyst composition
AU4326193A (en) * 1992-06-25 1994-01-24 Unilever Plc Machine dishwashing composition
DE4223545A1 (de) * 1992-07-17 1994-01-20 Hoechst Ag Verfahren zur Herstellung von Natriumsilikaten mit Schichtstruktur sowie ihre Verwendung
CA2189865A1 (fr) * 1994-05-10 1995-11-16 Hermanus Jongkind Procede de preparation d'un tamis moleculaire a larges pores

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9729172A1 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9138393B2 (en) 2013-02-08 2015-09-22 The Procter & Gamble Company Cosmetic compositions containing substituted azole and methods for improving the appearance of aging skin
US9144538B2 (en) 2013-02-08 2015-09-29 The Procter & Gamble Company Cosmetic compositions containing substituted azole and methods for alleviating the signs of photoaged skin

Also Published As

Publication number Publication date
WO1997029172A1 (fr) 1997-08-14
JPH11504069A (ja) 1999-04-06
BR9707378A (pt) 1999-07-20

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