EP1144581A1 - Improved detergent compositions comprising hybrid zeolite builders - Google Patents

Improved detergent compositions comprising hybrid zeolite builders

Info

Publication number
EP1144581A1
EP1144581A1 EP00906921A EP00906921A EP1144581A1 EP 1144581 A1 EP1144581 A1 EP 1144581A1 EP 00906921 A EP00906921 A EP 00906921A EP 00906921 A EP00906921 A EP 00906921A EP 1144581 A1 EP1144581 A1 EP 1144581A1
Authority
EP
European Patent Office
Prior art keywords
occluded
hybrid
cobuilder
builder
mixtures
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Withdrawn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
EP00906921A
Other languages
German (de)
French (fr)
Inventor
Robert Henry Rohrbaugh
Eugene Joseph Pancheri
James Charles T. Roger Burckett-St.Laurent
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 EP1144581A1 publication Critical patent/EP1144581A1/en
Withdrawn legal-status Critical Current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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/86—Mixtures of anionic, cationic, and non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/364—Organic compounds containing phosphorus containing nitrogen
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes

Definitions

  • compositions contain particular aluminosilicate builders, preferably hyb ⁇ ds of aluminosilicate and specific occluded mate ⁇ als such as silicate, carbonate, sulfate, phosphate, borate, nitrate, mt ⁇ te, Na ⁇ O, or mixtures thereof
  • the builder can be surface-modified or can be processed in a particular manner
  • the compositions further contain selected detergent adjuncts, such as certain surfactants, enzymes, polymers and/or bleaches Other adjuncts, e.g , conventional surfactants, enzymes, builders or bleaches can also be present
  • Zeolites hitherto formulated in detergents lack an ideal combination of low cost, ease of manufacture, high equilibrium binding of both Ca and Mg, rapid kinetics of binding for Ca and Mg, and ability to hold large amounts of surfactant Zeolites or aluminosi cates, when added to laundry detergents, can interact adversely with numerous laundry detergent adjuncts, e g bleaches, bleach catalysts, enzymes, b ⁇ ghteners and other additives, and/or produce unacceptable harshness and/or give other major problems, such as redeposition onto textiles
  • adjuncts or differently charged additives such as cationic surfactants, catalysts or enzymes to adsorb onto relatively large, aniomcally charged surfaces of insoluble inorganic builders Since such adjuncts are often expensive and tend to be used at relatively low levels in detergent compositions, their loss by any mechanism, such as interaction with the builder, can have dramatic effects on overall cleaning performance
  • improved detergent compositions beyond those desc ⁇ bed in WO 98/42622 can be formulated by combining the hyb ⁇ d zeolite-silicates of WO98/42622 with particular detergent ingredients
  • improved detergent compositions are formed by combining detergent ingredients with certain hyb ⁇ d zeolite- cobuilders not specifically described in WO98/42622 In these materials, the hvb ⁇ d builder has an occluded material other than silicate, such as sulfate, borate, nitrate, nitrite, phosphate, or Na-,0
  • improved detergent compositions are formed by combining detergent ingredients with combinations of hyb ⁇ d zeolite-silicate and hybrid zeohte-cobuilder systems wherein these combinations are not desc ⁇ bed in WO98/42622
  • the hyb ⁇ d builder has both occluded silicate and another occluded matenal other than silicate, especially an amon having charge greater than 1 , such as occluded sulfate, occluded borate, occluded phosphate, though occluded nitrate, occluded nit ⁇ te, or mixtures of any of the aforementioned cobuilders is possible
  • alkali metal oxides or hydroxides such as Na-,0 or NaOH, are present with excellent results
  • improved detergent compositions are formed by combining detergent ingredients with any of said hyb ⁇ d zeohte-silicate or hyb ⁇ d zeohte-cobuilder systems, wherein the hybnd zeolite-silicate or hyb ⁇ d zeohte-cobuilder occluded system is further modified by chemical or physical modification of the external surfaces Such modification can range quite widely, from a chemical approach, such as surface silylation or treatment with reactive ammosihcones, to a physical approach, such as such as direct contacting of the hybrid with PEG, e g , PEG 4000.
  • the surface treatment adjunct can improve one or more aspects of cleaning or fabric care when the treated hyb ⁇ d is included in a detergent formulation
  • the treated hyb ⁇ d when formulated with low- level cationic cosurfactants, enzymes, transition metal bleach catalysts, or the like, can be shown to have a reduced tendency to interfere with the cleaning performance of such desirable adjuncts
  • improved detergent compositions are formed by combining detergent ingredients with any of said hyb ⁇ d mate ⁇ als in the presence of innocuous fillers or common inorganic pigments, including in particular nonzeolitic alummosihcates such as hvdroxysodalite and or talc and/or whiteners such as titanium dioxide
  • nonzeolitic alummosihcates such as hvdroxysodalite and or talc
  • whiteners such as titanium dioxide
  • the hvdroxysodalite or other filler or whitener or mineral can be present in the hybrid, e g , through crystal imperfections, can be present in the builder system, or can be introduced along with other detergent ad]uncts
  • these filled detergent compositions might be expected to be significantly worse for cleaning than the unfilled types of compositions, they are surprisingly effective, for example in laundry bars
  • the present invention therefore, has numerous advantages, including improved laundry cleaning and/or anti-redeposition performance and/o r cost effectiveness as compared with the cleaning and/or antiredeposition performance offered bv WO98/42622 alone
  • Other significant advantages are improved compatibility of the formulated ingredients, for example, a reduced tendency of the hyb ⁇ d builder to interact negatively w ith coformulated detergent ingredients
  • the present invention includes a detergent composition
  • a detergent composition comprising (a) from about 0 1 % to about 99% of a builder system comp ⁇ sing. in part, a particulate inorganic ion-exchanging builder material, said builder material comp ⁇ sing a hybrid of crystalline zeohtic aluminosilicate and at least one occluded nonsihcate cobuilder, and (b) from about 0 1 % to about 99% of detergent adjuncts
  • said hyb ⁇ d compnses from about 0 01 to 1 0, more preferably 0 10 to 1 0 weight fraction of said builder system and said hyb ⁇ d is characte ⁇ zed by a capacity to sequester calcium in excess of the amount of charge inducing aluminum in the zeohtic aluminosilicate
  • said hyb ⁇ d is characte ⁇ zed by a calcium i
  • the occluded nonsihcate cobuilder can be selected from (I) the group consisting of occluded phosphate, occluded carbonate, occluded borate, occluded nitrate, occluded nit ⁇ te, occluded sulfate, occluded Na ⁇ O and mixtures thereof, and (n) mixtures of said occluded nonsihcate cobuilder and occluded silicate, provided that in anv of said mixtures of occluded nonsihcate and occluded silicate, the weight fraction of occluded silicate is no more than about 0 99, preferably no more than about 0 80
  • the invention also encompasses a detergent composition
  • a detergent composition comprising (a) from about 0 1 % to about 99% of a builder system comprising, in part, a particulate inorganic ion-exchanging builder mate ⁇ al, said builder mate ⁇ al comp ⁇ sing a hyb ⁇ d of crystalline aluminosilicate and an occluded cobuilder, said hyb ⁇ d further comp ⁇ sing at least one adsorbed or externally chemically bonded cobuilder or adjunct other than said occluded cobuilder, and (b) from about 0 1 % to about 99% of detergent adjuncts other than any adjunct of said builder system
  • the adsorbed or externally chemically bonded cobuilder or adjunct can be a builder adjunct or a nonbuilder adjunct
  • the externally chemicallv bonded cobuilder or adjunct is a nonbuilder adjunct, it preferably reduces the negative surface charge of the hybrid relative to the nontreated hybrid, whereby said component (a) has improved compatibility with cationically charged surfactants and/or enzymes
  • the detergent composition of the invention can readily accommodate a detergent adjunct comp ⁇ sing at least one cationic detersive surfactant
  • a detergent adjunct comp ⁇ sing at least one cationic detersive surfactant Other detergent adjuncts may be present, such as at least one anionic detersive surfactant, especially mid-chain branched types, in addition to said cationic detersive surfactant
  • said occluded cobuilder is selected from the group consisting of occluded silicate cobuilder, occluded nonsihcate cobuilder, and mixtures thereof
  • occluded cobuilder is an occluded silicate cobuilder
  • such embodiments include those wherein the hybrid is fully in accordance with the above-identified Engelhard patent publication
  • the invention also encompasses embodiments wherein said occluded cobuilder is selected from the group consisting of occluded nonsihcate cobuilder and mixtures of occluded nonsihcate cobuilder and occluded silicate cobuilder, and wherein said occluded nonsihcate cobuilder is selected from the group consisting of occluded nitrate, occluded phosphate, occluded carbonate, occluded borate, occluded nit ⁇ te, occluded sulfate, occluded Na 2 O and mixtures thereof
  • certain art-known occluded zeolites outside of the above-identified Engelhard publication, are useful herein such occluded zeolites are not known to the inventors as having been used in any laundry detergent, especially modern high-density granules or tablet form-detergents
  • the present invention encompasses a detergent composition comp ⁇ sing (a) from about 0
  • said hyb ⁇ d preferably comprises at least about 0 01 weight fraction of said builder system and wherein said occluded cobuilder is selected from group consisting of occluded silicate cobuilder, occluded nonsihcate cobuilder and mixtures of said occluded silicate cobuilder and said occluded silicate cobuilder, and w herein said occluded nonsihcate cobuilder, when present, is present at a weight ratio to occluded silicate cobuilder of from about 1 1000 to about 1000 1 and is selected from the group consisting of occluded nitrate, occluded phosphate, occluded carbonate, occluded borate, occluded nit ⁇ te, occluded sulfate, occluded a ⁇ O and mixtures thereof
  • the builder system itself can be varied
  • a detergent composition as defined hereinabov e wherein said hyb ⁇ d comprises at least about
  • ethercarboxylates preferably carboxymethyloxysuccinate, tartrate monosuccinate, tartrate disuccmate, oxydisuccmate or mixtures thereof
  • carbonates preferably sodium carbonate and/or sodium bicarbonate
  • polyacetal carboxylates and mixtures thereof
  • Aminofunctional variants of the ether carboxylates can also be used (Desirably for cost reasons at least 80% by weight of the soluble or exchangeable cations inherent in the builder system are sodium, however other soluble cations, especially potassium, can be included at varying levels and calcium and/or magnesium may also be present
  • Magnesium silicate in particular can be used as a cobuilder or as an adjunct desirable for processing reasons
  • Other highly desirable detergent compositions compnse the hybrid builder together with an additional specified builder material as described in more detail hereinafter As noted the invention
  • the detergent compositions incorporate biodegradably branched detersive surfactants
  • biodegradably branched detersive surfactants include detergent compositions wherein said detergent adjunct comp ⁇ ses at least one detersive surfactant having at least one biodegradably branched hydrophobe, said surfactant being selected from m ⁇ d-cha ⁇ n-C : -C -brancned C,-C
  • the invention includes detergent compositions wherein said hyb ⁇ d builder mate ⁇ al has a capacity to sequester calcium anywhere in excess of the amount of charge inducing aluminum in the crystals of the hyb ⁇ d builder matenal
  • said hybrid builder material comprises is characte ⁇ zed bv a calcium ion exchange capacity of at least 25% greater than the calcium ion exchange capacity of a reference matenal selected from non-hybndized zeolite A
  • the total SiO-, in said hyb ⁇ d builder mate ⁇ al can be from 1 02 to 1 50 times the framework SiO, as determined by compa ⁇ son of x-ray diffraction, x-ray fluorescence and " * S ⁇ NMR analysis
  • the invention includes a detergent composition
  • a detergent composition comprising (a) from about 0 1 % to about 99% of a builder system comp ⁇ sing, in part, a particulate inorganic ion-exchanging builder material compnsing a hyb ⁇ d of crystalline aluminosilicate and occluded silicate having a SiOJA O, ratio below 3 and formed by a process comp ⁇ sing the step of adding an aluminum source to a concentrated silicate solution having a pH above 12, said silicate solution having been at least partially depolyme ⁇ zed by heating prior to the addition of said aluminum source, and (b) from about 0 1% to about 99% of at least one detergent adjunct selected from the group consisting of (l) detersive surfactants having at least one biodegradably branched hydrophobe, (n) organic polymeric materials selected from the group consisting of end capped ohgome ⁇ c esters, hydrophobically modified polyacrylates te olymers compn
  • said step of depolymenzmg said sodium silicate solution preferably compnses heating at temperatures of from 50 °C to 85 °C for a pe ⁇ od of 10 minutes or longer
  • compositions compnses soluble silicate as a non-occluded cobuilder and wherein the total level of soluble silicate in said composition as a whole is limited, and is preferably no more than the equivalent of about 3% by weight of the composition of 2 Or sodium silicate
  • the hybnd has measurable hvdroxysodalite as evidenced by XRD powder pattern
  • compositions wherein said builder system comprises said particulate hybrid aluminosilicate mate ⁇ al in conjunction with at least one traditional builder mate ⁇ al, at a ratio of hybnd aluminosilicate to traditional builder material of from 5 1 to about to about 1 5, compositions which comp ⁇ se as an adjunct a low level of chelant (preferably less than about 2% by weight of the composition, more preferably from about 0 1 % to about 1 5%, highly prefe ⁇ ed chelants indlude DTPA, EDTA, S,S'-ED
  • the present invention has other embodiments and ramifications, such as a detergent composition comp ⁇ sing (a) from about 0 1% to about 99% of a builder system comp ⁇ sing, in part, a particulate inorganic ion-exchanging builder mate ⁇ al compnsing a hyb ⁇ d of crystalline aluminosilicate and occluded cobuilder, said hyb ⁇ d having a SiOJAKO ratio below 3 and formed by a process comprising the step of adding an aluminum source to a concentrated silicate solution having a pH above 12.
  • a detergent composition comp ⁇ sing (a) from about 0 1% to about 99% of a builder system comp ⁇ sing, in part, a particulate inorganic ion-exchanging builder mate ⁇ al compnsing a hyb ⁇ d of crystalline aluminosilicate and occluded cobuilder, said hyb ⁇ d having a SiOJAKO ratio below 3 and formed by
  • silicate solution having been at least partially depolyme ⁇ zed by heating prior to the addition of said aluminum source and further, optionally but preferably, at least one source of occludable nonsihcate cobuilder having been added in any step and/or further, optionally but preferably, at least one surface treating agent having been applied to the external surfaces of said hyb ⁇ d after formation thereof, subject to at least one of the following provisions with respect to the composition of said builder system
  • the builder system has measurable hydroxysodahte as evidenced by peaks at 14 0, 24 3 and 25 1 degrees 2 theta in the XRD powder pattern of the builder system taken as a whole and/or
  • the hybrid has measurable hydroxysodahte as evidenced by peaks at 14 0, 24 3 and 25 1 degrees 2 theta in the XRD powder pattern of the builder system taken on its own and/or
  • the hybnd has measurable occluded nonsihcate cobuilder as evidenced directly and/or indirectly by any combination of elemental analysis, XRD powder pattern, 29 S ⁇
  • the hybrid has measurably different wetting and/or surface charge as compared with a non-surface treated hybnd, and (b) from about 0 1 % to about 99% of at least one detergent adjunct
  • said hybnd compnses occluded silicate, wherein said hyb ⁇ d is characte ⁇ zed by 29 S ⁇ NMR peaks in the range -81 to -85 ppm
  • said detergent composition has the form of a laundry bar, tablet, low -density granule or powdei, high-density granule or powder (e g , > 600 g/hter), paste, or gel or liquid having dispersed solids, wherein said hybrid has a measurable improvement in the sum of Calcium binding and Magnesium binding as compared to Zeolite A, delta-layered silicates and mixtures thereof
  • the present invention encompasses a detergent composition compnsing (a) from about 0 1% to about 99% of a builder system comp ⁇ sing, in part, a particulate inorganic ion-exchanging builder mate ⁇ al comp ⁇ sing a hyb ⁇ d of crystalline aluminosilicate and occluded cobuilder.
  • said hybnd having a SiOVAKO, ratio below 3 and formed by a process comprising the step of adding an aluminum source to a concentrated silicate solution having a pH above 12, said silicate solution having been at least partially depolymenzed by heating prior to the addition of said aluminum source and further, optionally but preferably, at least one source of occludable nonsihcate cobuilder having been added in any step and/or further, optionally but preferably, at least one surface treating agent having been applied to the external surfaces of said hybrid after formation thereof, and (b) from about 0 1% to about 99% of at least one detersive adjunct, provided that said detergent composition has solid form and the process for prepa ⁇ ng the detergent composition comprises at least one step of combining said hyb ⁇ d mate ⁇ al with a film-formmg polymer
  • detergent compositions as generally desc ⁇ bed heremabove wherein the hyb ⁇ d matenal has measurably different wetting and/or surface charge as compared with a non-surface treated hybrid
  • the detergent composition wherein the hybnd matenal has measurably different wetting and/or surface charge as compared with a non-surface treated hybnd, and wherein said measurable difference is accomplished by a step of treating the hybrid mate ⁇ al with PEG or a film-forming polymer
  • the present invention includes detergent compositions having a builder system
  • a "builder system” as defined herein compnses one or more detergent ingredients known in the art as “builders”, provided that there is included at least one "hybrid” or “occluded” aluminosilicate builder as defined in more detail hereinafter
  • the builder system differs from builder systems disclosed in WO98/42622 in that the hybnd builder matenal is different from the hyb ⁇ ds of WO98/42622
  • the builder system can be identical with those disclosed in WO98/42622. however, in this circumstance, the present detergent compositions have additional improving features de ⁇ ving from the selection of adjuncts and/or the method of processing
  • a "builder system” as defined herein must have at least one ingredient which helps control water hardness
  • Water hardness includes uncomplexed calcium ansing from water and/or soils on dirty fabncs, more generally and typically, “water hardness” also includes other uncomplexed cations having the potential to precipitate under alkaline conditions, especially the alkaline earths, more particularly magnesium
  • Well-known conventional builders include sodium t ⁇ polyphosphate, a "soluble complexing builder” which has a range of functions and benefits beyond complexation of calcium, such functions include, for example, peptization of inorganic soils
  • Another well-known builder is zeolite A, especially 0.01-10 micron zeolite A m sodium form This builder is a relatively insoluble crystalline matenal, which functions by ion exchange and is sometimes termed an "ion exchanging builder”
  • Yet another well- known builder is sodium carbonate Sodium carbonate functions as a "precipitating builder” - it reduce
  • mate ⁇ als known as chelants. and/or organic polymers, such as sodium polyacrylate, which have a builder function, however for the purposes of unambiguously accounting for mate ⁇ als m the present formulations, the convention will be used of separately accounting for chelants and those organic polymers which have a builder function - they will be added up with separately added detergent adjuncts This is for purposes of formula accounting and does not exclude such mate ⁇ als, in practice, from being coprocessed with the "builder system", for example into high density agglomerated particles
  • a builder system comprising a hybrid as defined hereinafter, together with sodium carbonate and a member selected from the group consisting of sodium oxydisuccinate, sodium carboxymethyloxysuccinate, sodium nit ⁇ lot ⁇ acetate, sodium citrate, and mixtures thereof,
  • a builder system comp ⁇ sing a hyb ⁇ d as defined hereinafter having a film- forming polyme ⁇ c coating, optionally together with one or more of zeolite A, sodium carbonate, and sodium citrate (recall that in such a case, the level of polymer for formula accounting purposes is accounted into the detergent adjunct outside of the builder system)
  • the detergent compositions and builder systems herein are required to include at least one crystalline, particulate, inorganic ion exchanging builder matenal compnsing a hybrid of crystalline zeohtic aluminosilicate and at least one occluded cobuilder
  • the term "hybnd” indicates that the aluminosilicate and cobuilder are integrated into the same crystal, as distinct from a simple mixture of separate crystals of the components
  • the term “occluded” further particularizes the location of one mate ⁇ al relative to the other by specifying that the cobuilder is included into rather than simply externally onto the aluminosilicate crystals
  • the term “hybnd” may be used herein as a shorthand, when unqualified, it encompasses all suitable particulate crystalline alummosihcates. having whatever kind of occluded material which helps detergent performance
  • zeolite compositions comprising both a cobuilder and a zeolite useful as a builder, provided that the composition is the product of a process compnsing the step of adding an aluminum source to a concentrated silicate solution or silicate - cobuilder solution having a pH above 12, said silicate solution or si cate-cobuildei solution having been at least partially depolymenzed, preferably by heating, pnor to the addition of said aluminum source
  • the cobuilder may vary widely, and includes phosphate, carbonate, borate, nitrate, nit ⁇ te, sulfate, Na,O. NaOH and mixtures thereof This alternate definition emphasizes that the present invention is not limited to a particular theory of operation
  • hybnd builder matenals herein can be catego ⁇ zed into a number of distinct classes, depending on the matenal that is occluded into the aluminosilicate crystals
  • hybrids comprising both occluded silicate and occluded nonsihcate cobuilder
  • the hybrid builder materials can further vary depending on the crystal type, thus hybnds herein can in general be hyb ⁇ ds based on a zeolite A crystal type, a zeolite P or gismondine crystal type, AX type, or any other crystal type known to be associated with ion-exchanging aluminosilicate materials
  • Hyb ⁇ ds comp ⁇ sing occluded silicate include those of WO 98/42622, Engelhard, which are disclosed in detail hereinafter
  • Hybrids compnsing occluded nonsihcate cobuilder include the particulate crystalline alummosihcates having occluded matenal selected the group consisting of occluded phosphate, occluded carbonate, occluded borate, occluded nitrate, occluded nit ⁇ te, occluded sulfate, occluded Na : O, occluded NaOH and mixtures thereof
  • occluded is used to emphasize that not only is the selected matenal to be present, it must be located in the aluminosilicate crystals The precise location may vary, though in most instances, it is believed that at least a portion of the occluded matenal lies outside the smallest zeolite cages while lying at least in part inside the larger zeolite cages
  • Mixtures of hyb ⁇ ds can in general be used in any proportion Such mixtures include mixtures of a hyb ⁇ d according to WO 98
  • Hybrid matenals herein can have a range of particle sizes, primary crystals in the size range of from about 0 01 to about 20 microns being suitable, from about 1 micron to about 10 micron and having a good ability to diffract X-rays being prefe ⁇ ed Such pnmary crystals can be agglomerated into larger aggregates to minimize dusting and/or segregation in fully-formulated laundry detergents
  • All hyb ⁇ ds herein can in general vary in pnmary crystallite size and degree of crystal perfection
  • Hybnd materials herein can have a range of occluded cobuilder content, for example from about 0 001 to about 1 0 number fraction of available occlusion sites can be occupied by occluded cobuilder
  • Hybrids having combinations of occluded and adsorbed cobuilder are possible
  • Hybnd materials herein can have varying cation composition, for example including hydrogen or ammonium or even in part calcium or magnesium, though typically the prefe ⁇ ed cation is sodium Potassium or lithium, if present, will be in rather limited proportion, e.g , less than about 0 01% of available exchangeable sites Charge-balancing amounts of such cations can be present, or sub-charge balancing amounts, for example when the hybrid material is extensively washed in pure water
  • Hybrid matenals herein can optionally have adsorbed or occluded organic adjuncts, such as perfumes Wherever located in a manufactured formulation, perfumes, like organic polymeric builders or chelants, are added up, for formula accounting purposes, outside of the builder system
  • Hybrid mate ⁇ als herein can hav e varying degree of hydration, for example if used in detergent compositions which are aqueous suspensions, they can be fully hydrated In other nonhmiting examples, if the hyb ⁇ d material is incorporated in a nonaqueous liquid detergent, a high-density granular detergent comprising bleach or bleach precursor, or a composition comprising a hydrolytically labile perfume precursor or pro-perfume, the hybrid mate ⁇ al may be anhydrous or only pamally hydrated Prefe ⁇ ed hyb ⁇ d builders hav ing occluded nonsihcate cobuilder herein have occluded mate ⁇ als which are typically relatively small inorganic anions, e.g , occluded phosphate, occluded carbonate, occluded borate, occluded nitrate, occluded nit ⁇ te, occluded sulfate, and mixtures thereof
  • a prefe ⁇ ed group of hyb ⁇ d builders having occluded nonsihcate cobuilder have occluded mate ⁇ als which have an anionic charge greater than one, e g., occluded phosphate, occluded carbonate, occluded sulfate, and mixtures thereof
  • a prefe ⁇ ed group of hybrid builders having occluded nonsihcate cobuilder have occluded matenals which are phosphorus-free and boron-free, e g , occluded carbonate occluded nitrate, occluded nitnte, occluded sulfate, and mixtures thereof
  • a prefe ⁇ ed group of hybrid builders having occluded nonsihcate cobuilder have occluded mate ⁇ als which are nitnte-free, e g , occluded carbonate, occluded nitrate, occluded sulfate, and mixtures thereof
  • occluded matenals which are nitrate-free, nitnte-free, boron-free and phosphorus- free, e g occluded carbonate, occluded sulfate, occluded Na-,0, occluded NaOH and mixtures thereof
  • hyb ⁇ d builder herein is characterized by at least one of
  • said hvb ⁇ d is charactenzed by a 15-m ⁇ nute or equilibrium calcium ion exchange capacity of at least 15% greater, preferably at least 20%, more preferably at least 25% greater than the calcium ion exchange capacity of a reference material selected from non-hyb ⁇ dized zeolite A
  • a reference material selected from non-hyb ⁇ dized zeolite A
  • Such reference zeolite A in fully Na-exchanged form has a theoretical cation exchange capacity of about 7 meq/g, typically 5-7 meq/g e g 6 meq/g in practice wherein the abbreviation "meq/g" stands for milhequivalents per gram
  • Levels of builder system in the completed laundry detergent powder, syndet bar, gel, tablet or pouch can vary widely , for example from 0 1% to about 99% of a builder system comprising the essential hybrid matenal
  • the proportion of the hyb ⁇ d aluminosilicate builder material can likewise vary, compnsing from about 0 01 to 1 0, more preferably 0 10 to 1 0, weight fraction of the builder system
  • Hvb ⁇ d Aluminosilicate Not According to WO 98/42622 It is to be emphasized that the present invention includes embodiments in which, by way of hyb ⁇ d mate ⁇ al, onlv hybrid alummosihcates not according to WO 98/42622 are used as an essential component These hyb ⁇ ds in general can be selected in any proportion from
  • this cobuilder is selected from the group consisting of phosphate, carbonate, borate, nitrate, nitnte, sulfate, Na,O, NaOH and mixtures thereof
  • silicate-type hyb ⁇ ds as per WO 98/42622 and hyb ⁇ ds having nonsihcate cobuilder selected from the group consisting of phosphate, carbonate, borate, nitrate, nit ⁇ te, sulfate, Na O and mixtures thereof in all proportions are also encompassed
  • hybrids not according to WO 98/42622 herein generally include those known in the art of zeolite manufacture, see for example "Zeolite Chemistry and Catalysis", Ed J A Rabo. ACS Monograph Series, Vol 171 , Amencan Chemical Society, Washington D.C . 1976.
  • Such matenals include, for example, borate-occluded, hydroxide-occluded, or nitrate- or other nitrate salt-occluded zeolite A See, for example, the work by Ba ⁇ er, or by Liquornik and Marcus refe ⁇ ed to in the cited standard texts
  • the occluded salt molecules may , or may not penetrate the sodahte cages of the zeolite, and can be a ⁇ anged in the larger cages
  • the occlusion may be of the so-called reversible type, or may be non-reversible
  • Occlusion for the present purposes is best conducted with sodium as cation and without a transition-metal as the cation, though more generally, transition-metal or silver cation occluded variations are possible and can have beneficial effects, such as enhancement of antimicrobial activity of a detergent composition
  • the present invention also encompasses occlusion of Na,O in zeolites, such as Na : O-occluded zeolite A It is known that certain zeolites tend to decompose nitrate catalytically to NaNO : (chabazite and mordenite) and even to produce Na O
  • hybnd alummosihcates herein can be prepared by any known method, see for example the ACS monograph cited supra and references therein such methods can be aqueous-based, for example using the above-identified anions in a method otherwise similar to the Engelhard WO 98/42622 method or v ariations thereof, or can be non- aqueous or melt-based methods
  • Prefe ⁇ ed hyb ⁇ ds and combinations include those wherein the zeolite is zeolite A, B, P, X, AX or MAP, sodium is the sole cation, and the occluded cobuilder is selected from carbonate, hydroxide and NaO
  • Suitable levels are from about 0 1% to about 80%, preferably from about 0 5% to about 30%, by weight, of the hybrid aluminosilicate when it is used alone
  • Suitable levels of a builder system in the present detergent compositions are from about 0 1 % to about 85%, preferably from about 1% to about 40%, by w ⁇ ight Builders other than the hyb ⁇ d aluminosilicate are conventional and can.
  • water-soluble organic builders such as 2,2'-oxyd ⁇ succ ⁇ nate sodium salts, citric acid sodium salts, carboxymethyloxysuccinate sodium salts, nit ⁇ lot ⁇ acetic acid sodium salts and the like
  • water-insoluble inorganic builders such as zeolites A, P, B, X, or any ol their modifications
  • water-soluble organic builders such as various cellulosic polymers
  • water-soluble inorganic builders such as sodium carbonates, sodium phosphates, sodium tnpolyphosphates and the like, encompassing a wide range of calcium and/or magnesium binding capability and rate
  • the builder system can be complemented by one or more materials known as chelants, (chelants like, organic polymers, being added up separately in the formula accounting and being materials which generally have the capability to strongly bind transition metal ions or colloidal transition metal precipitates m aqueous alkaline media)
  • Chelants suitable for use herein include ethylenediamine disuccinate sodium salts, EDTA,
  • the present invention includes embodiments in which a particular hyb ⁇ d aluminosilicate according to WO 98/42622 is used as an essential component
  • This hyb ⁇ d matenal can be obtained from Engelhard Corp It is a crystalline zeohtic aluminosilicate having occluded silicate, and in WO 98/42622 it is termed a "hybnd zeolite/silica composition" (HZSC)
  • HZSC zeolite/silica composition
  • HZSC matenals may be prepared by-crystal zmg high aluminum zeolites in highly alkaline/high silica environments Chemical analysis indicates an excess of silica in the HZSC beyond that inherent to their crystalline frameworks Such matenals, at least in certain cases, demonstrate sequestration capacities for cations such as calcium which exceed the amount of zeohtic aluminum available foi ion-exchange and even exceed the theoretical limit possible for a zeolite Thus, HZSC materials and their properties are potentially different ooth in degree and in kind from those of a conventional zeolite According to the inventors of WO 98/42622, the "key mechanism ir the effectiveness of HZSC materials is denved from the ability of zeolite cages to isolate and stabilize small, highly charged silicate units " The inventors of the present invention remark that alternative theo ⁇ es can be advanced, for example it is known that small cobuilder polyanions (in this case silicate) can reduce electrostatic repulsion
  • WO 98/42622 discloses that silicate units are introduced du ⁇ ng synthesis of HZSC by providing an environment wherein silica in the reaction mixture is depolymenzed to highly charged predominantly monomenc units before crystallization begins
  • the occluded silicate units of the HZSC are visible in 29 S ⁇ NMR spectra
  • the HZSC as a whole is stated to be "more powerful" in complexmg multivalent cations than are existing zeolites, silicates or mixtures thereof
  • the zeolite framework and occluded silicate units are stated to "act in concert, as a new type of hybnd composition, showing properties neither zeolites, silicates nor physical blends of the two demonstrate"
  • the HZSC's demonstrate unusually rapid rates of sequestration, important in applications such as detergent building
  • the capacity for silicates to complex ions such as calcium and magnesium is inversely proportional to silicate chain length and directly proportional to the electronic charge on that chain fragment Silicates depolyme ⁇ ze with increasing alkalinity (See Fig 1 of WO 98/42622)
  • silicates are polymenc
  • pH's silica not only becomes predominantly monome ⁇ c, but also that monomer may possess multiple charges If such small, highly charged fragments could be exposed to solutions beanng multivalent cations, very powerful high capacity sequestration agents would result
  • the inventors of WO 98/42622 assert that they have created such a situation by isolating and stabilizing substantial concentrations of such species within zeolite cages where ions such as calcium and magnesium are free to enter from an aqueous environment (such as wash water) and react with these powerful sequestration agents
  • HZSC compositions can be prepared by reacting a finely divided aluminum source such as a d ⁇ ed aluminosilicate gel or powdered gibbsite and more preferably finely divided metakaohn with concentrated silicate solutions at pH values abov e 12 at temperatures ranging from about ambient to about 100°C and at atmospheric pressure It is crucial for the preparation of the HZSC compositions that the aluminum source must be added last to the reaction mixture Thus, if all the ingredients of the reaction mixture are added together and heated to crystallization temperature, a conventional zeolite of the pnor art will be formed, and the HZSC materials of WO 98/42622 will not be formed
  • HZSC compositions by heating the reaction mixture at temperatures of from 50°C to 85°C before the addition of the aluminum source for a pe ⁇ od of time of about 30 minutes or longer While not wishing to be bound by any theory of operation, it appears that heating the reaction mixture for about 30 minutes pnor to aluminum addition allows the silicate to depolyme ⁇ ze and form the predominantly occluded silicate units previously discussed According to WO 98/42622.
  • HZSC ' s can also be prepared by reacting finely divided metakaohn with concentrated sodium silicate solutions at pH values above 12 at temperatures ranging from about ambient to about 100°C and at atmosphe ⁇ c pressure
  • WO 98/42622 also states a preference to use high purity metakaohns, especially those low in iron and titania, w hen color is a consideration
  • metakaohn having an Fe ; O, content below 1 %, preferably below 0 5% by weight and a TiO, content below 2% by weight preferably below 1% bv weight are useful
  • the metakaohn should be in powder form These powders may be prepared by removing grit and coarse impurities from kaolin ores, usually fractionating the deg ⁇ tted crude, drying the resulting slurry of fractionated hydrous kaolin, pulverizing the dried matenal, calcining in conventional manner to produce metakaohn (see, for example, U S 3,1 12,176 (Haden et al )), and pulverizing the metakaohn by means of a hammer mill or the like
  • U S 3,014,836 Proctor et al is cross-referenced herein for its disclosure of producing calcined kaolin pigment
  • the particle sizes of the hydrous kaohnite precursor of the metakaohn starting mate ⁇ al affect the size of the HZSC product Since HZSC products having a fine particle size are usually prefe ⁇ ed, fine particle size metakaohns obtained from fine particle size hydrous kaolins are recommended These particle sizes are most frequently measured by kaolin producers as values obtained by sedimentation, typically using a Sedigraph® 5100 analyzer (supplied by Micromeretics Corporation) and the values are reported as "equivalent spherical diameter" (e s.d ) Use of other measunng instruments may give somewhat different values In Example 3 of WO 98/42622, reproduced below as "HZSC Synthesis Example 1", illustrative of the WO 98/42622 process, typical samples of the hydrous kaolm precursor of the metakaohn are about 90% by weight finer than 1 micron, e.s.d., as measured using the Sedigraph® 5100 instrument The
  • the zeolite crystals are washed thoroughly with water, preferably deionized water, to remov e sodium and spunous silica from the crystal surfaces In some cases, some replacement of sodium by hydrogen may take place du ⁇ ng washing
  • water preferably deionized water
  • the crystals can be washed w ith solutions other than those of pure water
  • about 5 to 40% of the silica content of the washed crystals is due to the occluded silicate species, usually to 20%
  • the total S ⁇ O 2 analysis as determined by conventional chemical analytical means will exceed that of the S ⁇ O : that would be expected based on the framework silica content as indicated by x-ray powder patterns and 9 S ⁇ NMR analysis of the HZSC composition
  • the occluded silicate portion of this silica is readily ascertained from the "S ⁇ NMR peaks at about -81 to -85 ppm
  • 29 S ⁇ NMR has become a standard technique in the analysis of zeolites
  • the utility of this technique is based on the fact that different frequencies co ⁇ espond to different electronic environments around the silicon, typically affected in zeolites by the chemistry of neighbonng atoms and/or Si-O bond angles 29 S ⁇ NMR detects all the Si, not just that which is associated with long-range crystallinity This makes it sensitive to species that may not be detected by XRD HZSC Synthesis Example 1 (see Example 3 of WO 98/42622)
  • Hybrid Zeohte-Sihca Composition based on a gismondine-type aluminosilicate.
  • HZSC Hybrid Zeohte-Sihca Composition
  • the following procedure is applied 1000 grams of fine particle size metakaohn obtained by calcining an ultrafme mechanically delaminated ground hydrous kaolin (90% by weight finer than 1 micron, e s d ), followed by pulvenzation is used
  • the powdered metakaohn is blended into an alkaline silicate solution containing 702 grams of N- Brand® sodium silicate solution and 1064 grams of NaOH in 4800 grams of deiomzed water which have been mixed and preheated to 72°C
  • the mixture is then reacted with vigorous stirnng at 72°C for eight hours at ambient pressure in an open stainless steel vessel
  • the crystalline product of the reaction is filtered and washed three times with 2000-ml lots of 72°C deiomzed water
  • the aluminum content of a zeolite is expected to equal its cationic content in that each framework aluminum induces one net negative framework charge which is counterbalanced by cations in order to maintain electroneutrahty Extra sodium is a characteristic of HZSC and is believed to be the result of sodium in association with the occluded silicate species
  • the average particle size (50% by weight finer than) of the crystalline product is 5 5 microns as determined by a Sedigraph® 5100
  • HZSC Synthesis Example 2 See (see Example 10 of WO 98/42622)
  • an HZSC mate ⁇ al is prepared by the following procedure
  • An alkaline silicate solution is prepared by dissolving 175 0 grams of NaOH and 99 0 grams of N-Brand® sodium silicate in 522 8 grams deiomzed water After mixing and preheating the mixture to 80°C, 109 5 grams Metamax® metakaohn are added and the mixture reacted by stimng for one hour at 80°C in a constant temperature bath The resultant product is filtered and washed three times with 1000-ml lots of deiomzed water The sample is then d ⁇ ed overnight in a forced air oven at 100°C The product of this example demonstrates a strong, clean XRD powder pattern characte ⁇ stic of Zeolite A This mate ⁇ al is then subjected to the hardness sequestration test of WO 98/42622 Example 7 The 15 second and 15 minute hardness removal readings are 43% and 51% respectively , showing that hardness sequestration is remarkably faster and substantially more thorough than that of unmodified Zeolite A The hyb ⁇ d composition offers
  • HZSC Synthesis Example 3 (see Example 13 of WO 98/42622) In order to prepare an improved builder, termed a HZSC, based on a gismondine- type structure, the following procedure is followed
  • Example 12 An identical synthesis mixture to that of WO 98/42622 Example 12 is prepared but in a different order of addition/reaction Thus, 74 97 pounds of deiomzed water, 42 7 pounds of 50% NaOH solution and 14 12 pounds of N-brand Sodium silicate are combined and heated under agitation to 72°C in a stainless steel reactor After an equilibration period of 30 minutes to allow silicate depolymenzation, 20 0 pounds of Luminex brand metakaohn are added and the-mixture reacted under vigorous agitation for 8 hours at 72° C After the reaction penod, the product is washed and filtered on several large pan filters including multiple reslumes and nnses with substantial excess of deiomzed water
  • the powder XRD pattern for this product is that of a highly crystalline mate ⁇ al of a gismondine-type structure, consistent with that of WO 98/42622 Example 12
  • 29 S ⁇ NMR shows a clear shoulder to the main peak at -81 to-85 ppm which is characte ⁇ stic of an HZSC
  • HZSC Synthesis Example 4 (see Example 14 of WO 98/42622) In order to prepare an improved builder, termed a HZSC, based on a gismondine- type structure, and to demonstrate that aluminum sources other than metakaohn may be employed in the formation of HZSC, the following procedure is followed
  • An aluminosilicate gel with gross composition approaching 1 1 Si/Al is prepared bv dissolving 2 95 kg of NaAlO-,, in 14 0 kg deiomzed water To this is added 7 45 kg N- Brand® sodium silicate The resultant gel is beaten with a high shear blade to a homogeneous appea ⁇ ng consistency The homogenized gel is poured into stainless steel pans and is dned in an oven overnight at 100° C A portion of this dned gel is pulvenzed and employed as dried aluminosilicate reactant Thus, 89 grams of NaOH and 88 grams of N-Brand® sodium silicate are dissolved in 600 grams of deiomzed water and brought to a temperature of 72° C under agitation After equilibrating, 160 grams of the dried gel aluminosilicate reactant are added to the mixture under agitation and crystallized at 72° C for 5 5 hours The sample is washed and vacuum filtered with an excess
  • Example 1 (WO 98/42622 Example 3) at pH 10 (typical of wash water) is established by exchanging 3 0 grams of the matenal twice with 6 0 grams of CaCU 2H,O dissolved in 400 ml deiomzed water The exchanges are each conducted for approximately 45 minutes at a temperature of 100°C The sample is filtered and washed six times with approximately 100 cc deiomzed water to remove any spunous CaCU The sample is then dned at 100°C for approximately 12 hours The sample is then subjected to conventional X-ray fluorescence chemical analysis techniques The analysis reveals 23 5 weight % CaO, 42 0 weight % S ⁇ Oont 31 9 weight % Nl 2 O 3 and approximately 1 0 % other mate ⁇ als on a dry weight basis Thus, the material contains 7 0 meq/g Si.
  • This test indicates that HZSC matenals at 15 seconds are more rapid than the reference mate ⁇ als (conventional zeolites) and, at least in the case of HZSC having gismondine-type structure, have improved 15-m ⁇ nute removal data than the reference mate ⁇ als Note, however, that if the HZSC materials have reduced crystal size relative to the reference matenals, an improvement in 15 sec hardness removal is expected Since, for the zeolite A-type HZSC, the 15-m ⁇ nute removal data is not substantially improved over the reference matenals, this leaves some question as to
  • Detergent compositions of the present invention include a builder svstem that comprises, at least in part, the hyb ⁇ d aluminosilicate as hereinbefore desc ⁇ bed. togetner w ith specified detergent adjuncts
  • the present inventive detergent compositions are required to constitute a combination of a WO 98/42622 hyb ⁇ d material and at least one selected detergent adjunct not disclosed or suggested in WO 98/42622
  • selected adjuncts especially advantageous in conjunction with hybnd builders, are desc ⁇ bed in detail hereinafter as "Class I detergent adjuncts"
  • the present inventive detergent compositions compnse at least the hyb ⁇ d builder mate ⁇ al and one or more broadly defined detergent adjuncts
  • these more broadly defined detergent adjuncts can include any detergent adjunct or adjunct class disclosed in WO 98/42622 and the associated literature references, as well as any Class I detergent adjunct
  • prefe ⁇ ed Class I adjuncts are included in all the prefened embodiments of all detergent compositions herein at levels of from about 0 0001% to about 99% of the detergent composition
  • the prefened detergent compositions preferably include at least two Class I detergent adjuncts, more preferably at least three such adjuncts
  • Prefened detergent compositions according to the invention may contain (a) from 2 to 60 wt % of one or more detergent surfactants, (b) from 10 to 80 wt % of one or more detergencv builders, including the hybrid aluminosilicate, (c) from 5 to 40 wt % of a bleach system, (d) from 0 05 to 10% of enzyme or mixtures thereof, and (e) optionally other detergent ingredients to 100 wt % Bleach-free embodiments are, of course, also contemplated
  • Highly prefened detergent compositions herein compnse in addition to (a) the hybnd builder, (b) from about 0 1% to about 99% of at least one detersive adjunct selected from the group consisting of (I) detersive surfactants having at least one branched, preferably mid-chain branched hydrophobe, (n) organic polymenc mate ⁇ als selected from polyacetal carboxylates hydrophobically modified polyacrylates, terpolymers comp ⁇ sing acrylate or maleate, polymenc soil release agents, polymenc dye transfer inhibitors, polyamines, polyimines, polymenc rheology modifiers, and mixtures thereof, (in) oxygen bleach promoting mate ⁇ als selected from hydrophobic bleach activators; organic bleach boosters; transition-metal bleach catalysts; photobleaches and mixtures thereof; (iv) faoric care promoting agents other than said organic polymeric materials; and (v) mixtures of (i) - (iv). Sources and examples of such materials have
  • the present invention includes important embodiments comprising at least one biodegradably branched and/or crystallinity disrupted and/or mid-chain branched surfactant or surfactant mixture.
  • biodegradably branched and/or crystallinity disrupted and/or mid-chain branched indicate that such surfactants or surfactant mixtures are characterized by the presence of surfactant molecules having a moderately non-linear hydrophobe; more particularly, wherein the surfactant hydrophobe is not completely linear, on one hand, nor is it branched to an extent that would result in unacceptable biodegradauon.
  • the prefened biodegradably branched surfactants are distinct from the known commercial LAS, ABS, Exxal, Lial, etc. types, whether branched or unbranched.
  • the biodegradably branched materials comprise particularly positioned light branching, for example from about one to about three methyl, and/or ethyl, and or propyl or and/or butyl branches in the hydrophobe, wherein the branching is located remotely from the surfactant headgroup, preferably toward the middle of the hydrophobe.
  • branching is located remotely from the surfactant headgroup, preferably toward the middle of the hydrophobe.
  • Typically from one to three such branches can be present on a single hydrophobe, preferably only one.
  • Such biodegradably branched surfactants can have exclusively linear aliphatic hydrophobes, or the hydrophobe- can include cycloaliphatic or aromatic substitution.
  • Highly prefened are MCB analogs of common linear alkyl sulfate, linear alkyl poly(alkoxylate) and linear alkylbenzenesulfonate surfactants, said surfactant suitably being selected from mid-chain-C,-C 4 -branched C 8 - C l i( -alkyl sulfates, mid-chain-C,-C 4 -branched C 8 -C 1 s -alkyl ethoxylated, propoxylaied or butoxylated alcohols, mid-chain-C,-C -branched -C ⁇ -alkyl ethoxysulfates, mid-chain- C r C 4 -branched C 8 -C, 6 -alkyl benzenesulfonates and mixtures thereof.
  • the surfactants can in general be in acid or salt, for example sodium, potassium, ammonium or substituted ammonium, form.
  • the biodegradably branched surfactants offer substantial improvements in cleaning performance and/or usefulness in cold water and/or resistance to water hardness and/or economy of utilization.
  • Such surfactants can, in general, belong to any known class of surfactants, e.g., anionic, nonionic, cationic, or zwitterionic.
  • the biodegradably branched surfactants are synthesized through processes of Procter & Gamble, Shell, and Sasol.
  • biodegradably branched surfactants herein in more detail include MCB surfactants as disclosed in the following references
  • MCB noniomc surfactants including MCB pnmary alkyl polyoxyalkylenes of formula (1) CH 3 CHJCH : ) tt C(R)H(CH 2 ) C(R')H(CH 2 ),C(R 2 )H(CH 2 ) z (EO/PO) m OH (1 ), where the total number of carbon atoms in the branched pnmary alkyl moiety of this formula, including the R, R' and R ' branching, but not including the carbon atoms in the EO/PO alkoxy moiety, is preferably 14-20, and wherein further for this surfactant mixture, the average total number of carbon atoms in the MCB pnmary alkyl hydrophobe moiety is preferably 14 5-17 5, more preferably 15-17, R, R 1 and R 2 are each independently selected from hydrogen and 1 -3C alkyl, preferably methyl, provided R, R, R 1 and R 2 are each independently selected from hydrogen and 1
  • R, R 1 3-7C linear alkyl
  • WO97/38957 A also discloses (l)
  • branched alkyl carboxylate surfactants by oxidising the alcohols or their aldehyde intermediates
  • the branched carboxylates formed can be used as a feedstock to prepare branched acyl taurate, acyl isethionate, acyl sarcosinate or acyl N-methylglucamide surfactants, etc
  • WO97'39091 A published 10/23/97 includes disclosure of a detergent surfactant composition comp ⁇ sing at least 0 5 (especially 5, more especially 10, most especially 20) wt% of longer alkyl chain, MCB surfactant of formula (I) A-X-B (I) wherein A is a 9-22 (especially 12-18) C MCB alkyl hydrophobe having (1) a longest linear C chain attached to the X-B moiety of 8-21 C atoms, (11) 1-3C alkyl mo ⁇ ety(s) branching from this longest linear chain, (111) at least one of the branching alkyl moieties attached directly to a C of the longest linear C chain at a position within the range of position 2 C, counting from C 1 which is attached to the Cr B moiety , to the omega-2 carbon (the terminal C minus 2C), and (iv) the surfactant composition has an average total number of C atoms in the A-X moiety of 14.5-17.5 (especially 15-17), and B is
  • (6) methyl branched primary alkyl sulphates selected from 3-, 4- 5-, 6-, 7-, 8-, 9-, 10-, 1 1 -, 12- or 13- methyl pentadecanol sulphate, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 1 1-, 12-, 13-, or 14- methyl hexadecanol sulphate, 2.3-, 2,4-, 2.5-. 2.6-.
  • WO97 / 39087 A published 10 / 23 97 includes disclosure of a surfactant composition
  • WO 98/23566 A Shell published 06/04/98 discloses branched pnmary alcohol compositions having 8-36 C atoms and an average number of branches per mol of 0 7-3 and compnsing ethyl and methyl branches Also disclosed are (1 ) a branched primary alkoxylate composition preparable by reacting a branched primary alcohol composition as above with an oxirane compound, (2) a branched pnmary alcohol sulphate preparable by sulphating a pnmary alcohol composition as above, (3) a branched alkoxylated pnmary alcohol sulphate preparable by alkoxylating and sulphating a branched alcohol composition as above, (4) a branched pnmary alcohol carboxylate preparable by oxidising a branched pnmary alcohol composition as above, (5) a detergent composition comp ⁇ sing (a) surfactant!
  • s) selected from branched primary alcohol alkoxylates as in (1 ), branched primary alcohol sulphates as in (2), and branched alkoxylated pnmary alcohol sulphates as in (3), (b) a builder, and (c) optionally add ⁇ t ⁇ ve(s) selected from foam control agents, enzymes, bleaching agents, bleach activators, optical bnghteners.
  • Biodegradably branched surfactants useful herein also include the modified alkylaromatic, especially modified alkylbenzenesulfonate surfactants described in copending commonly assigned patent applications [ INSERT MLAS Case REFERENCES mcl 7303P, 7304P and the earlier filed MLAS cases]
  • these surfactants include (P&G Case 6766P) alkylarylsulfonate surfactant systems comprising from about 10% to about 100% by weight of said surfactant system of two or more crystalhnity-disrupted alkylarylsulfonate surfactants of formula (B-Ar-D) a (M c l + ) b wherein D is SO3", M is a cation or
  • compositions also include (P&G Case 7303P) surfactant mixtures comp ⁇ sing (preferably, consisting essentially of) (a) from about 60% to about 95% bv weight (preferably from about 65% to about 90%, more preferably from about 70% to about 85%) of a mixture of branch rmula (1)
  • M is a cation or cation mixture (preferably selected from H, Na, K, Ca, Mg and mixtures thereof, more preferably selected from H, Na, K and mixtures thereof, more preferably still, selected from H, Na, and mixtures thereof) having a valence q (typically from 1 to 2, preferably 1)
  • a and b are integers selected such that said compounds are electroneutral (a is typically from 1 to 2, preferably 1 , b is 1 )
  • R 1 is C,-C, alkyl (preferably C,-C, alkyl, more preferably methyl)
  • R 2 is selected from H and C,-C, alkyl (preferably H and C,-C 2 alkyl, more preferably H
  • composition is further charactenzed by a 2/3-phenyl index of from about 350 to about 10,000 (preferably from about 400 to about 1200, more preferably from about 500 to about 700) (and also preferably wherein said surfactant mixture has a 2- methyl-2-phenyl index of less than about 0 3, preferably less than about 0 2, more preferably less than about 0 1, more preferably still, from 0 to 0 05)
  • surfactant mixtures comprising the product of a process comp ⁇ sing the steps of alkylating benzene with an alkvlating mixture, sulfonating the product of (I), and neutralizing the product of (II), wherein said alkylating mixture comprises (a) from about 1 % to about 99 9%, by weight of branched C--C 2( monoolefins, said branched monoolefins having structures identical with those of the branched monoolefins formed by dehydrogenating branched parafins of formula R'LR ° wherein L is an acyclic aliphatic moiety consisting of carbon and hydrogen and containing two terminal methyls, R 1 is C, to C, alkyl, and R ' is selected from H and C, to C, alkyl, and (b) from about 0 1 % to about 85%, by
  • Prefened detergent compositions herein also include those wherein the hybnd builder material of WO 98/42622, or a different hyb ⁇ d builder as disclosed herein, are combined with selected cationic surfactants
  • selected cationic surfactants include (1) cationic surfactants having one long chain and three relatively short chains in which one or more substituents attached to the nitrogen atom contain oxygen, as foi example in hydroxyethyl, and/or in which the relatively long chain is branched
  • Such surfactants include, foi example, compounds having the formula R'N ⁇ R'R" X wherein R' is C ⁇ -C 16 linear or branched alkyl (optionally including one or more aryl, ether or ester moieties) and wherein R 2 -R 4 can vary independently and can, for example, comprise methyl, ethyl, propyl, butyl, hydroxyethyl, hydroxypropyl and mixtures thereof provided that at least one of R 2 -R 4
  • X " is any compatible anion, for example one selected from halogen, (e.g chloride, bromide), acetate, citrate, lactate, glvcolate, phosphate nitrate, sulfate, and alkylsulfate Mixtures of these compounds and the conesponding anions can be used, and/or (n) cationic surfactants having the formula
  • R- is an alkyl or alkyl benzyl group having from 8 to 18 carbon atoms in the alkyl chain, each R J is selected from the group consisting of -CH2CH2-.
  • each R 4 is selected from the group consisting of C1 -C4 alkyl.
  • Rj , R 2 , R 3 , and R4 are independently selected from an aliphatic group of from 1 to about 22 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkylarmdo, hydroxyalkyl, aryl or alkylaryl group having up to about 22 carbon atoms; and
  • X is a salt- forming anion such as those selected from halogen, (e.g chlonde, bromide), acetate, citrate, lactate, glvcolate, phosphate nitrate, sulfate, and alkylsulfate radicals, wherein said compounds the aliphatic groups contain, in addition to carbon and hydrogen atoms, other linkages such as ether linkages, and/or other groups such as amino groups The longer chain aliphatic groups, e.g .
  • Prefened is when Rj , R 2 , R3, and R4 are independently selected from Cl to about C22 alkyl Especially prefened for some purposes are cationic mate ⁇ als containing two long alkyl chains and two short alkyl chains or those containing one long alkyl chain and three short alkyl chains other than methyl
  • the long alk l chains in the compounds described in the previous sentence have from about 8 to about 22 carbon atoms, preferably from about 10 to about 14 carbon atoms
  • bis- alkoxylated quaternary ammonium (bis-AQA) surfactants and combinations including same disclosed in WO9744433 Al WO9744431 Al , WO9744432 Al , WO9743394 A, WO9743393 A, WO9743391 A, WO9743390 A, WO9743389 A, WO9743371 A, WO9744420 A, WO9744419 A, WO9744418 A, WO9743388 A, WO9743387 A, WO9743365 A, WO9743364 A See also WO9738968 Al
  • the selected cationic surfactants can be used herein for one or more purposes, including net contribution to cleaning, especially of greasy soils, or for other purposes, such as softening through the wash and/or for antimicrobial purposes
  • Suitable levels of these cationic surfactants herein are from about 0 1% to about 20%, preferably from about 1 % to about 15%, although much higher levels, e.g , up to about 30% or more, may be useful especially in noniomc cationic (i.e . limited or anionic-free) formulations
  • Highly prefened compositions however combine the cationic surfactant at a very low level, e.g . from about 0 1 % to about 5%, preferably not more than about 2%, with the HZSC materials
  • the selected cationic surfactants, even at said low levels, are surpnsingly effective w ith the HZSC builder matenals
  • alkylt ⁇ methylammonium cationic surfactants can be used in conjunction with the selected cationic surfactant types if desired Selected Sugar-denved Surfactants
  • Prefened detergent compositions herein also include those wherein the hybnd builder matenal of WO 98/42622 or a different hybrid builder as disclosed herein is combined with selected sugar-denv ed surfactants
  • selected sugar-denved surfactants include particular the C.-C,,, alkyl N-methyl glucamides, for example as disclosed in WO 92/06070 A or WO 92/05071 A published 04/16/92, any of the known lactobionamide surfactants, and combinations of the glucosamides and/or lactobionamides with alkylpolyglucosides (APG's) Cationic-Aniomc Ion Pair
  • Surfactants US 5,472,455 discloses water-soluble complexes of anionic and cationic surfactants These are useful in conjunction with hybnd builders Bleach
  • Prefened detergent compositions of the invention include those combining HZSC or hybrid builders with selected bleach or bleach-forming mate ⁇ als Transition-metal bleach catalysts These selected mate ⁇ als include one or more transition-metal-containing bleach catalysts such as the mate ⁇ als descnbed in WO 98/39406 A, WO 98/39405 A.
  • WO 98/39335 A for example those more specifically illustrated hereinafter - see also WO 97/00937, WO 96/06155, EP 718398 A, US 5,720,897 and WO 97/48787
  • transition-metal bleach catalysts based on any ⁇ gid macropolycychc hgand, for example any mononuclear or dmuclear transition metal complex based on t ⁇ azacyclononane, more preferably monometallic catalysts wherein the ⁇ gid macropolycychc hgand is cross-bndged, as in Bcyclam or any of its homologs, for example those in which terminal alkyl moieties connected to nitrogen are selected from methyl, ethyl and mixtures thereof
  • a particularly useful transition-metal bleach catalyst wherein the terminal alkyl moieties connected to nitrogen are methyl is [Mn(Bcyclam)C12]
  • the selected bleach-promoting mate ⁇ als also include organic bleach catalysts or organic bleach boosters or so-called oxygen transfer agents, for example the N-acyhmine types desc ⁇ bed in WO98/07825 A or the phosphinoyl lmme types desc ⁇ bed in US 5,652,207
  • Such mate ⁇ als also include sulfommines
  • These matenals are organic catalysts for bleaching, as distinct from the so-called bleach activators or bleach precursors such as TAED, which are stoichiomet ⁇ c, and not catalytic
  • Organic bleach catalysts include the compounds themselves and/or any of their precursors, for example any suitable ketone for 5 production of dioxiranes and/or any of the hetero-atom containing analogs of dioxirane precursors or dioxiranes , such as sulfommines and or the lmmes descnbed in U S 5.576,282 and references descnbed therein
  • Organic bleach catalysts can, in general, include ani
  • Prefe ⁇ ed detergent compositions herein include, in addition to a hybrid builder mate ⁇ al, a hvdrophobic peracid or an activator capable of releasing such peracid.
  • 15 hvdrophobic types include those containing a chain of six or more carbon atoms, prefened hydrophobic types having a linear aliphatic C8-C14 chain optionally substituted by one or more ether oxygen atoms and/or one or more aromatic moieties, preferably positioned such that the peracid is an aliphatic peracid More generally , such optional substitution by ether oxygen atoms and/or aromatic moieties can be applied to any of the
  • peracids or bleach activators herein Branched-cham peracid types and aromatic peracids having one or more C3-C16 linear or branched long-chain substituents can also be useful
  • the peracids can be used in the acid form or as any suitable salt with a bleach-stable cation
  • R5 R5 or mixtures thereof wherein R' is alkyl, aryl, or alkaryl containing from about 1 to about 14 carbon atoms, R " is alkylene, arylene or alkarylene containing from about 1 to about 14 carbon atoms, and R" is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms
  • these peracids have a sum of carbon atoms in R 1 and R 2 30 together of about 6 or higher, preferably from about 8 to about 14, they are particularly suitable as hydrophobic peracids for bleaching a vanety of relatively hydrophobic or "hpophihc" stains, including so-called “dingy” types Calcium, magnesium, or substituted ammonium salts may also be useful
  • a bleach activator which yields the conesponding peracid under perhydrolysis conditions can desirably be used
  • the bleach activator will generally have a leaving group having any suitable p
  • the bleach activator or precursor is an acethylated diamme, such as tetracetylethylenediamine (TAED)
  • hydrophobic bleach activators or the conesponding peracids useful herein are acetylemc matenals such as undec-10-ynoyl-oxy-benzene sulphomc acid or related activators as disclosed in DE19616782 Al
  • Another useful bleach mate ⁇ al de ⁇ ves from phfhahmido- substituted matenals such as phfhahmido- percaproic acid or 6-phthahm ⁇ dohexaneperoxo ⁇ c acid (CAS Registry Number 128275-31 - 0), for example as disclosed in US 5,487,818, US 5,415,796, EP 852,259 A, and WO 98/39405 A though other phthahmido-substituted bleach promoting matenals, for example those of EP 780,374 A or EP 325,288 A, can also be used.
  • Yet another useful hydrophobic bleach activator and or the conesponding peracid are disclosed in US 5,061,807, DE 3823172 A, and Japanese Laid-open patent application (Kokai) No 4- 28799
  • the peracid is preferably 3-dodecyl-2.5-d ⁇ ox
  • More particularly prefened hydrophobic bleach activators include sodium nonanoyloxybenzene sulfonate (NOBS or SNOBS), substituted amide types, and the above-identified activators related to certain imidoperacid bleaches, for example as described in U.S 5,061,807
  • acyl lactam activators especially the acyl caprolactams (e.g WO 94-28102 A), acyl valerolactams (e.g U.S 5,503,639), and certain N(alkanoyl) ammo alkanoyloxybenzene sulfonates as descnbed in WO 98/27056 A
  • activators are compounds that, under perhydrolysis conditions, release (I) percarboxyhc acids and (n) labile groups that can act as a substrate for enzymes, especially redox-active enzymes See DE19713852 A
  • Combinations of the above-identified peracids and/or bleach activators are also especially useful Moreover, combinations of the above-identified peracids and/or activators with conventional bleach activators, especially TAED, can give very good combinations of dingy and hydrophihc stain removal
  • Bleach activators are suitably used m amounts of from 1 to 8 wt %, preferably Photobleaches
  • the present invention encompasses combinations of the hereinabove-defined hyb ⁇ d builder materials with photobleaches
  • any photobleach can be used, such as the fully or partially sulfonated zinc and/or aluminium phthalocyamnes, see for example BE-865371 A, GB 1408144 A, US 4,497,741, RD 182041 or EP 119,746
  • Other photobleaches suitable for use herein are any of those commercially available from CIBA
  • prefened photobleaches useful herein in particular include Si-phthalocyanmes as disclosed in WO 97/05202 A, low-hue photobleaches as desc ⁇ bed in WO 98/32832 A and US 5.679,661 , superoxide-generating photobleaches as described in WO 98/32829 A, singlet oxygen generating photobleaches as descnbed WO 98/32828 A, and other photobleaches as desc ⁇ bed in WO 98 '32827 A, WO 98328
  • bleach-promotmg enzymes in general include any enzymes having bleach-promoting action via oxidation or reduction of colored soils and/or stains
  • bleach-promoting enzymes includes live natural or genetic-engineered enzymes having a bleach-promotmg function with or without there being a requirement for addition of any other redox-active or bleaching matenal
  • bleach-promoting enzymes encompasses the enzymes themselves and any related polypeptides having similar effect Suitable bleach-promoting enzymes herein include oxidoreductases More particular bleach-promoting enzymes include oxidases or combination systems including same (DEI 9523389 Al ), mutant blue copper oxidases (WO9709431 Al ), peroxidases (see for example US 5,605,832, WO97/31090 Al ), mannanases (WO971 1 164 Al ), laccases, see WO
  • Oxidoreductases and or their associated antibodies can be used, for example with H,Oalthough as taught in WO 98/07816 A Depending on the type of detergent composition, other redox- active enzymes can be used, even, for example, catalases (see, for example JP09316490
  • the bleach-promoting enzymes can be coated (see for example WO9731088 Al ) oi uncoated
  • hybnd builder with any oxygenase of extracellular ongin, especially fungal oxygenase such as dioxygenase of extracellular origin
  • oxygenase of extracellular ongin especially fungal oxygenase such as dioxygenase of extracellular origin
  • the latter is most especially quercetinase, catechinase or an anthocyanase. optionally in combination with other suitable oxidase, peroxidase or hydrolytic enzymes.
  • Enzyme compositions herein can be solid or liquid, aqueous or non-aqueous and include a substantially water-free liquid composition comprising (A) an enzyme, (B) a substance selected from (I) substances which in aqueous medium are precursors for substrates for the enzyme, and (n) substances which are cofactors for the enzyme, and (C) a non-aqueous liquid phase as described in WO9741215 Al
  • Prefened bleach-promoting enzyme systems include systems which generate hydrogen peroxide m-situ, for example glucose oxidases or glucose oxidase-hke polypeptides as taught in WO9820136 Al , or an enzyme having aminoalcohol- or D- aminoacid-oxidase activity and a substrate for this enzyme as desc ⁇ bed in DEI 9545729
  • Still further useful detergent compositions herein are those one-part or multi-part compositions or wash media comprising the hybrid builder mate ⁇ als together with bleach-promoting enzyme systems comprising chloroperoxidase, a hydrogen peroxide source, chlonde and adhering agent, preferably formed at or near the site of use, as desc ⁇ bed in WO 98/42370 A
  • bleach-promoting enzyme related systems useful herein include those of
  • WO 9807824 A and WO9807816 Al which disclose a detergent composition comp ⁇ sing a source of hydrogen peroxide and a donor-hydrogen peroxide oxido-reductase-directed antibody
  • the present invention also encompasses combinations of the hereinabove-defined hybrid builder materials with specific inorganic builders, more particularly one or more of the following mate ⁇ als Crystalline silicates
  • Specific crystalline silicates especiallv useful herein include a foliated crystalline sodium silicate with high delta-phase fraction as disclosed m EP-860398 Al , DEI 9707449 Cl , particular layered or sheet silicates as disclosed m JP09025116, JP 10007416 A, WO9703018 Al , DE19613060 Al , EP-753568 A, EP-745559 Al , US5567404 A, EP- 731058 Al .
  • crystalline sodium silicate having delta, alpha, beta- and/or NS-phase as disclosed in WO9719156 Al other crystalline silicates as disclosed in WO9716525 Al , JP0831 1494 A, JP0831 1493 A.
  • JP08268708 A crystalline silicates made by sinte ⁇ ng amorphous silicates as disclosed in JP0918361 1 A, crystalline disihcates as disclosed in DE4439083 Al , crystalline silicate powders with RUB-18 structure and specified X-ray diffraction pattern as disclosed in EP-775670 Al , anhydrous crystalline silicates especially containing potassium as disclosed in WO 9831631 Al , JP09302384 A, and metasihcate pentahydrate as disclosed in CN1 131 125 A
  • Amorphous silicates Specific amorphous sodium silicates useful herein include sodium silicate -metal sulphate composite powders containing the metal sulphate as a solid solution as disclosed in EP- 728837 Al , amorphous ammonium and alkali silicate granules as disclosed IT1265262 B, X-ray amo ⁇ hous sodium silicate w ith low crystallisation temperatures prepared from amo ⁇ hous silicate with higher water content that can be converted to beta- and alpha- modifications by microwave drying in stages, as disclosed in DE19710383 Al , other specific amo ⁇ hous silicates as disclosed in DE19541755 Al , DE19525378 Al , WO96/28382 A, DE4446363 Al , DE4435632 Al , JP10007417 A, JP09309719 A, and crystal hne/amo ⁇ hous silicate combinations as disclosed in JP09087690 A, JP09067592 A Amorphous alummosihcate
  • zeolite compositions useful herein in conjunction with the hybnd builder matenals include P-type zeolites as disclosed in EP 758,626 Al , WO96/34828 Al , WO96/14270 Al , alkali metal silicates deposited onto P-type zeolites as disclosed in WO9734980 Al , gamma-madiated zeolites as disclosed in CN1 1 13263 A, or the equivalent material made without inadiation; alumino-silicates having primarily tetrahedrally coordinated aluminium, formed by the chemical modification of 2: 1 layer clay minerals as disclosed in WO9618576 Al ; zeolites prepared from aluminosilicate gels under pulsation as disclosed in RU2083493 Cl ; microporous zeolite A-LSX as disclosed in EP-816291 Al ; zeolites grown with the assistance of microwave energy as disclosed in DE19548742 Cl ; and mechanically crushed ze
  • Magnesiosilicates can be used in conjunction with the hybrid builders herein. These include the magnesiosihcate materials of WO 97/10179.
  • a highly prefened illustrative magnesiosihcate compound for use as a builder component with the hybrid builder materials herein is one having a calcium binding capacity (CBC) of at least 10 mg CaO per gram at room temperature, a magnesium binding capacity (MBC) of at least 10 mg MgO per gram at room temperature, and a calcium binding rate (CBR) of no more than 300 seconds at room temperature, being the time taken to remove half of the Ca2+ from a ⁇ 100 ppm Ca2+ solution at a loading of 3g per litre, and having either a stuffed silica polymo ⁇ h-related structure or a layered structure with a characteristic broad X-ray powder diffraction peak occurring at a d-spacing of between 1 1 and 17 A.
  • CBC calcium binding capacity
  • MLC magnesium binding
  • Seeded builder systems Various seeded builder can be used in conjunction with the hybrid builder materials herein. These include sodium carbonate in combination with a crystallization seed for calcium carbonate, see GB 1 437 950; tabular calcium carbonates as disclosed in WO9840458 Al ; rhombohedral calcium carbonates as disclosed in WO9840457 Al ; WO9840456 Al ; WO9840455 Al ; see also builders with crystalline microstructure comprising carbonate WO9638526 Al ; WO9733966 Al ; WO9638525 Al ; WO9638524 Al. Other inorganic builders
  • inorganic builders especially useful in conjunction with the hybrid builders herein are noncaking silicates treated with organic compounds as disclosed in JP09208218 A; other new silicates as disclosed in JP 10081509 A; compacted sodium silicates as disclosed in WO9717286 Al ; trisodium phosphate hydrate as disclosed in WO9715527 Al ; and an ion-capturing agent for alkaline earth metal ions which contains a precipitating agent for the ions within pores of a porous support.
  • the support is silica gel.
  • the pore diameter of the support is 0.3-15 nm.
  • the precipitating agents comprise alkali metal carbonates, bicarbonates, silicates, sulphates and organic acid salts.
  • JP09241680 A This latter builder is as disclosed in JP09241680 A.
  • Yet another useful inorganic builder contains alkaline retarding particles, surfactant and an ion blockade agent to elevate pH of washing water after lowenng its hardness, as disclosed in WO9709414 Al Non-bleaching enzymes
  • Enzymes other than gene ⁇ c proteases and amylases as refened to m WO 98/42622 can be used in conjunction with the hyb ⁇ d builders to unexpectedly great advantage
  • Such enzymes include non-gene ⁇ c proteases, non-generic amylases, non-bleaching enzymes other than proteases and/or amylases, bleaching enzymes, combinations thereof, combinations thereof with any suitable antibodies, inhibitors, stabilizers, or promoters, and combinations of any such non-genenc enzymes and/or enzyme-specific adjuncts with genenc proteases and/or amylases Bleaching enzymes and adjuncts specific for use therewith, for formula accounting pu ⁇ oses, are accounted with the bleach system, as desc ⁇ bed elsewhere herein
  • Prefened non-bleaching enzymes useful in conjunction with hybrid builder materials herein include enzymes derived from extremophiles, as well as hvdrolases other than protease and/or amylase
  • Prefened non-bleaching enzymes other than protease and/or amylase in particular can have low or even very high activity (EP 839,05 A), can include combinations of plant cell wall degrading enzymes and non-cell wall-degrading enzymes (WO 98/39403 A) and can.
  • pectinase (WO 98/06808 A, JP 10088472 A, JP 10088485 A), pectolyase (WO98/06805 Al ), pectin lyases free from other pectic enzymes (WO9806807 Al), chondnotinase ( EP 747,469 A), xylanase ( EP 709.452 A, WO 98/39404 A, WO98/39402 A) including those de ⁇ ved from microtetraspora flex osa (US 568391 1 ), isopeptidase (WO 98/16604 A), keratinase (EP 747,470 A.
  • pectinase (WO 98/06808 A, JP 10088472 A, JP 10088485 A)
  • pectolyase (WO98/06805 Al )
  • pectin lyases free from other pectic enzymes (WO
  • WO 98/40473 A hpase ( GB 2,297,979 A, WO 96/16153 A, WO 96/12004 A, EP 698,659 A, WO 96/16154 A), cellulase or endoglucanase (GB 2,294,269 A, WO 96/27649 A, GB 2,303,147 A, WO98/03640 A, see also neutral or alkaline cellulases denved from c n'sosporwm lucbwwense strain VKM F-3500D as disclosed in WO9815633 A), polygalacturonase (WO 98/06809 A), mycodextranase (WO 98/13457 A), thermitase (WO 96/28558 A), cholesterol esterase (WO 98 28394 A), or any combination thereof
  • Prefened proteases useful herein include certain vanants ( WO 96/28566 A, WO
  • proteases are multiply-substituted protease vanants comp ⁇ sing a substitution of an ammo acid residue with another naturally occur ⁇ ng ammo acid residue at an am o acid residue position conesponding to position 103 of Bacillus amvloliquefaciens subtihsin in combination with a substitution of an ammo acid residue with another naturally occur ⁇ ng amino acid residue at one or more amino acid residue positions conesponding to positions 1. 3. 4. 8, 9, 10, 12, 13, 16, 17, 18. 19, 20, 21 , 22, 24. 27, 33. 37, 38, 42, 43, 48, 55, 57, 58. 61, 62, 68, 72, 75, 76, 77, 78, 79, 86.
  • protease variant includes a substitution of amino acid residues at positions conesponding to positions 103 and 76, there is also a substitution of an amino acid residue at one or more amino acid residue positions other than amino acid residue positions conesponding to positions 27, 99, 101, 104, 107, 109, 123, 128.
  • Bacillus amvloliquefaciens subtihsin and/or multiply-substituted protease variants comprising a substitution of an amino acid residue with another naturally occurring amino acid residue at one or more amino acid residue positions conesponding to positions 62, 212, 230, 232, 252 and 257 of Bacillus amvloliquefaciens subtihsin as described in PCT Application Nos.
  • PCT/US98/22588, PCT/US98/22482 and PCT/US98/22486 all filed on October 23, 1998 from The Procter & Gamble Company (P&G Cases 7280&, 7281 & and 7282L, respectively). Bleach/amylase/protease combinations (EP 755,999 A; EP 756,001 A; EP
  • enzymes and their directly linked inhibitors are useful in conjunction with the present hybrid builders.
  • Enzymes and their non-linked inhibitors used in selected combinations herein include protease with protease inhibitors selected from proteins, peptides and peptide derivatives as described in WO 98/13461 A, WO 98/13460 A, WO 98/13458 A, WO 98/13387 A.
  • Amylases can be used with amylase antibodies as taught in WO 98/07818 A and WO 98/07822 A, lipases can be used in conjunction with lipase antibodies as taught in WO 98/07817 A and WO 98/06810 A, proteases can be used in conjunction with protease antibodies as taught in WO 98/07819 A and WO 98/06811 A, Cellulase can be combined with cellulase antibodies as taught in WO 98/07823 A and WO 98/07821 A. More generally, enzymes can be combined with similar or dissimilar enzyme directed antibodies, for example as taught in WO 98/07820 A or WO 98/06812 A.
  • the prefened enzymes herein can be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Prefe ⁇ ed selections are influenced by factors such as pH-activity and/or stability optima, thermostability. and stability to active detergents, builders and the like. In this respect bacterial or fungal enzymes are prefened, such as bacterial amylases and proteases, and fungal cellulases. Pro-perfume and/or enduring perfume
  • the present detergent compositions include those wherein a hybrid builder is combined with a pro-perfume, pro-accord and/or a particular, enduring perfume system.
  • Such selected ingredients are disclosed more fully in EP 864,642 Al ; EP 864,642 Al ; WO98/07809 A or WO98/07814 A or WO98/07812 A or WO98/07683 A or WO98/07407 A or WO98/27192 A or WO98/0781 1 A (beta keto-esters); WO97/34986 A or WO97/34989 A or WO97/34578 Al or WO98/27190 A or WO98/06803 A (pro- fragrant acetals and or ketals); WO9731094 Al or US 5,500,138 (enduring perfume system) WO96/29281 A (schiff bases and/or esters); US 5,668,102 (esters of non-allylic perfume alcohols); and ZA9610649 A (sulf
  • End-capped polymeric soil release agents are especially useful in conjunction with the present hybrid builder materials.
  • Suitable SRA's can have an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone as described in U.S. 4,968,451 ; nonionic end-capped 1,2-propylene/polyoxyethylene terephthalate polyesters as in U.S.
  • SRA is an oligomer having empirical formula (CAP)2(EG/PG)5(T)5(SIP)1 which compnses terephthaloyl (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-l ,2-propylene (EG/PG) units and which is preferably terminated with end-caps (CAP), preferably modified isethionates, as taught in U.S. 5,415,807.
  • CAP end-caps
  • prefened SRA's are oligomeric esters of empirical formula: ⁇ (CAP)x(EG/PG)y'(DEG)y"(PEG)y'"(T)z(SIP)z'(SEG)q(B)m ⁇
  • Prefened SEG and CAP monomers for these esters include Na-2-(2-,3- dihydroxypropoxy)ethanesulfonate (“SEG”), Na-2- ⁇ 2-(2-hydroxyethoxy) ethoxy ⁇ ethanesulfonate (“SE3”) and its homologues and mixtures thereof and the products of ethoxylating and sulfonating allvl alcohol
  • Prefened SRA esters in this class include the product of transeste ⁇ fying and ohgomenzing sodium 2- ⁇ 2-(2- hydroxyethoxy)ethoxy ⁇ ethanesulfonate and or sodium 2-[2- ⁇ 2-(2-hvdroxyefhoxy)- ethoxyjethoxyjethanes
  • builder systems and detergent compositions of the present inv ention can also contain from about 0 1% to about 10%, typically from about 0 3% to about %, preferably from about 0 3% to about 4%.
  • a film-forming polymer soluble in an aqueous slurrv comprising the organic surfactants, aluminosilicate mate ⁇ als, and neutral or alkaline salts herein
  • the polymer must be at least partially soluble in the slurry for it to dry to a film capable of cementing the granule walls together as the slurry is dned
  • the polymer should be substantially soluble in the slurry, and is preferably completely soluble in the slurry
  • the slurry will typically compnse a surfactant phase and the insoluble aluminosilicate matenal suspended in a solution (often saturated) of the neutral or alkaline salt, which preferably compnses sodium sulfate
  • the slurry w usually be alkaline in nature due to the presence of the aluminosilicate mate ⁇ al and either anionic surfactants or alkaline salts Since the
  • Prefened polymers of the above group are the carboxymethyl celluloses
  • Particularly prefened polymers for use herein are 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%, of the polymer
  • Most preferably the polymer has a molecular weight of from about 4,000 to about 10,000 and an acrylamide content of from about 5% to about 15%
  • Such a polymer acts to increase the percentage of a crutcher mix that is in the aqueous (lye) phase This improves the rate at which droplets of the crutcher mix will dry in a spray tower and can desirably increase the density of the resulting detergent granules when, for example, large amounts of sodium sulfate or other high-density inorganic salt is in the lye phase
  • the present detergent compositions also include those wherein a hybrid builder is combined with organic builders selected from - poiycarboxylates, more particularly those of JP 10147640 A denved from catalytic-oxidation of (a) OH-containing compounds selected from glyce ⁇ ne, glyce ⁇ c acid (GA) , glycerates, tartronic acid (TA) and tartronates in the presence of (b) metal salts selected from Fe salts and Zn salts as catalysts and polyme ⁇ sing (c) ketomalonic acid or its salts, - compositions compnsing alkali metal or ammonium borates and compounds having at least two OH groups in v icinal configuration as disclosed in WO96/38523 A,
  • the present detergent compositions also include those wherein a hybrid builder is combined with a functional polymer other than a soil release agent or film-fo ⁇ nmg polymer as defined heremabove
  • Prefened among such polymers are one or more members selected from the group consisting of
  • polymeric dye transfer inhibitors for example PVPNO, see for example EP-704523 Al or WO96/20996 Al or polymers of DEI 9621509 Al or WO96/37598 Al available from BASF,
  • polyimme de ⁇ vatives such as ethoxylated/propoxylated polyalkyleneamme polymers (see for example US 5,565, 145) or functionahzed backbone polyamines (see WO97/42286 Al ),
  • softemng-through-the wash detergents or additives can be prepared by combining the hybrid builders with cationic biodegradable softeners as disclosed EP 831,144 A, ZA9702461 A, WO97/34976 A, WO 97/36976 A, biodegradable di ester quaternary ammonium compounds as disclosed in WO 98/03619 A, softeners having hydrolyzable moieties as disclosed in WO97/34975 A, quats with mono-long chain softeners as disclosed in WO97/34972 A, unsaturated softeners as disclosed m WO98/17757 A, chelant/unsaturated softener combinations as disclosed in WO97/13828 A, esterquats and unsaturated fatty acids as disclosed in WO 97/1 1 142 A, low-odor softeners as disclosed in WO 98/47991 A, dryer-activated softeners
  • the present hybrid builder materials are usefully inco ⁇ orated into laundry bars or syndet bars, which can be made by any known technique
  • some prefe ⁇ ed combinations with the hyb ⁇ d builder are with fillers such as magnesium or calcium sulfates, kaolin, clays, hydroxysodahte, or the like, divalent metal sulfates as disclosed in WO98/20103 A, soap syndet/ starch combinations as disclosed m WO98/18896 A, in bars of enhanced firmness as disclosed in AU 9656053 A, with enzymes as disclosed in WO98/18897 A, with dihydnc alcohols as disclosed in WO98/1661 1 A, pour-molded with soap-based network structures as disclosed in WO98/1 1864 A, with anionic detergents, soaps, polyphosphates and specified poly hvdroxy fatty acid amides as disclosed in WO98/05752 A, with absorbent gelling materials as disclosed in US 5,703,026, as pour
  • the detergent compositions of the invention can contain one or more conventional detergent surfactants chosen from soap and non-soap anionic, cationic, noniomc, amphote ⁇ c and zwittenonic detergent-active compounds, and mixtures thereof
  • suitable surfactants are available and are descnbed in the literature, for example, in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch, in the well-known Mc Cutcheon's, and in the "Surfactant Science Series" of texts published by Marcel Dekker, New York
  • Prefened surfactants include synthetic non-soap anionic and noniomc types, though soaps, including those de ⁇ ved from vegetable sources, can also be used, especially in bars
  • Anionic surfactants are well-known and include alkylbenzene sulphonates, e g ,
  • Pnmary and secondary alkyl sulphates particularly C12-C15 pnmary alkyl sulphates, alkyl ether sulphates, olefin sulphonates, alkyl xylene sulphonates, dialkyl sulphosuccinates, and fatty acid ester sulphonates, such as methyl ester sulfonates, can be used Sodium salts are typically prefened
  • Noniomc surfactants that may be used include pnmary and secondary alcohol ethoxylates, especially C8-C20 pnmary and secondary aliphatic alcohols ethoxylated with from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially C9-C15 pnmarv aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethvlene oxide per mole of alcohol.
  • the conesponding denvatives of Guerbet, Exxal®, Isofol® or Lial® alcohols can also be useful
  • non-ethoxylated noniomc surfactants for example polyhvdroxyamides
  • surfactant detergent-active compound
  • amount will depend on the intended use of the composition different surfactant systems may be chosen for handwashing products and for products intended for use in different types of washing machine
  • the surfactant system can optionally be complemented by one or more cationic surfactants, such as fatty alkyl tnmethylammonium salts or variants thereof
  • cationic surfactants such as fatty alkyl tnmethylammonium salts or variants thereof
  • Suitable cationic surfactants are desc ⁇ bed in following documents, all of which are inco ⁇ orated by reference herein in their entirety M C Publishing Co , McCutcheon's, Detergents & Emulsifiers, (North American edition 1997), Schwartz, et al , Surface Active Agents. Their Chemistry and Technology. New York Interscience Publishers, 1949.
  • U S Patent 3,155,591 U S Patent 3,929,678, U S Patent 3,959,461 U S Patent 4,387.090 and U S Patent 4.228,044
  • special-pu ⁇ ose surfactants for example the linear or branched - C 20 fatty alkyldimefhylamine-N-oxides may be added for grease cleaning Cationic or amine oxide surfactants, when present, are typically used at levels below about 5%. More generally at levels in the range from about 0 1% to about 2% The total amount of surfactant system present will also depend on the intended end use, but suitably ranges from about 2% to about 60 wt %, preferably from 5% to 40 wt %
  • Detergent compositions suitable for use in most automatic fabnc washing machines generally contain anionic non-soap surfactant, or noniomc surfactant, or combinations of the two in any ratio, optionally together with soap Builders
  • the detergent compositions of the invention contain a hvbrid aluminosilicate as described in detail hereinbefore as a detergencv builder. This material may be complemented by one or more of the above-identified Class I adjuncts or any of the following detergency builders.
  • the total amount of detergency builder in the compositions, including the hybrid aluminosilicate and other builders, if present, will suitably range from 10 to 85 wt.%.
  • a suitable complementary builder is selected from zeolite A, zeolite P, zeolite X, zeolite NX (or any other co-crystallized zeolite having equivalent effect), maximum aluminum zeolite P, and mixtures thereof.
  • the amount of zeolite present may suitably range from 5 to 60 wt.%, more preferably from 15 to 40 wt.%, calculated on an anhydrous basis (equivalent to from 6 to 75 wt.%, preferably from 19 to 50 wt.%, calculated on a hydrated basis).
  • the zeolite may, if desired, be used in conjunction with other inorganic or organic builders.
  • Inorganic builders that may be present include sodium carbonate.
  • Organic builders that may be present include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymefhyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts though this list is not intended to be exhaustive.
  • organic builders useful herein include polyacetal carboxylates, for example polymers and copolymers having polyglyoxylate structural units; see, for example, US 4,146,495; US 4,140,676; EP 803,521 A: such materials are available from Monsanto, Nippon Shokubai, BASF and others.
  • Prefened supplementary builders for use in conjunction with the hybrid aluminosilicate include citric acid salts, more especially sodium citrate, suitably used in amounts of from 3 to 20 wt.%, more preferably from 5 to 15 wt.%.
  • Other supplementary builders are the water-soluble or partly water-soluble silicates, whether crystalline or amo ⁇ hous.
  • layer silicates such as SKS-6 from Hoechst/Clariant and/or common 2-ratio or 3-ratio soluble silicates.
  • layer silicates such as SKS-6 from Hoechst/Clariant and/or common 2-ratio or 3-ratio soluble silicates.
  • Such materials when present, are typically used at levels in the range from about 0.1% to about 20%) of the composition; more commonly, the level is below about 10%.
  • suitable silicate builders include water-soluble and hydrous solid types and including those having chain-, layer-, or three-dimensional- structure as well as amo ⁇ hous-solid silicates or other types.
  • Prefened are alkali metal silicates, particularly those liquids and solids having a SiO 2 :Na 2 O ratio in the range 1.6:1 to 3.2:1, including solid hydrous 2-rat ⁇ o silicates marketed by PQ Co ⁇ under the tradename BRITESIL®, e g , BRITESIL H2O, and layered silicates, e g , those desc ⁇ bed in U S 4.664,839, May 12.
  • H P Rieck NaSKS-6 or "SKS-6” is a crystalline layered aluminum-free ⁇ - Na-,S ⁇ O, silicate marketed bv Hoechst and is prefe ⁇ ed especially m granular laundry compositions
  • DE-A-3.417.649, DE-A-3,742,043 technical publications of Hoechst / Clanant, for example Surfactant Science Senes, Marcel Dekker, New York, see Vol 71 , Ed M S Showell, published 1998 See more particularly Chapter 3, "Builders The Backbone of Powdered Detergents" by Hans-Peter Rieck of Hoechst / Clanant
  • layered silicates such as those having the general formula NaMS ⁇ x O 2N , yH 2 O 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 also or alternately be used herein
  • Layered silicates from Hoechst also include NaSKS-5, NaSKS-7 and NaSKS-1 1, as the ⁇ , ⁇ and ⁇ layer-silicate forms
  • Other silicates may also be useful, e g magnesium silicate, for example for bleach stabilizing or process aid pu ⁇ oses
  • crystalline ion exchange mate ⁇ als or hydrates having chain structure and a composition represented by xM.,0 ySiO ⁇ zM'O as anhyd ⁇ de wherein M is Na and/or K, M' is Ca and/or Mg, y/x is 0 5 to 2 0 and z/x is 0 005 to 1 0 as taught in U S 5,
  • aluminosilicate builders or zeolites can be useful in certain embodiments These include materials having fo ⁇ nula [M ? (AlO2) z (S ⁇ O2) xH 2 O wherein z and v are integers of at least 6, the molar ratio of z to v is in the range from 1 0 to 0 5, and x is an integer from 15 to 264
  • Alummosihcates can be crystalline or amo ⁇ hous, naturally-occumng or synthetically denved
  • An aluminosilicate production method is in U S 3,985,669, Krummel, et al, October 12, 1976
  • Prefe ⁇ ed synthetic crystalline aluminosilicate ion exchange materials are available as Zeolite A, Zeolite P (B), Zeolite X and, to whatever extent this differs from Zeolite P, the so-called Zeolite MAP Natural types, including chnoptilohte, may be used Zeolite A has the formula Na
  • Suitable carbonate builders include alkaline earth and alkali metal carbonates as disclosed in German Patent Application No 2,321 ,001 published on November 15, 1973, although sodium bicarbonate, sodium carbonate, sodium sesquicarbonate, and other carbonate minerals such as trona
  • Other useful carbonate builders are those of U S 5,658,867 issued August 19, 1997, to Panchen et al inco ⁇ orated herein by reference or any convenient multiple salts of sodium carbonate and calcium carbonate such as those having the composition 2NaXO, CaCO when anhydrous, and even calcium carbonates including calcite, aragomte and vatente, especially forms having high surface areas relative to compact calcite may be useful, for example as seeds or for use in synthetic detergent bars
  • polycarboxylate polymers more especially acryhc/maleic copolymers, suitably used in amounts of from 0 5 to 15 wt %, especially from 1 to 10 wt %, of the detergent composition
  • the invention however includes embodiment
  • Detergent compositions of the invention can also include one or more components of a conventional bleach system
  • a bleach system may generally compnse any source of oxidative or reductive bleach, for example chlonne bleaches such as hyophahte, especially hypochlo ⁇ te, any hypohahte precursor, such as sodium dichloroisocyanurate, or any reductiv e bleach, for example sodium hydrosulphite or sodium bisulfite
  • Prefened bleach systems include those which are oxidative and compnse at least one source of bleaching oxygen Most generally, for example, when using a transition-metal bleach catalyst, there is no need for any source of bleaching oxygen other than oxygen from the air Quite typically, however, a source of bleaching oxygen is added into the formulation
  • sources of bleaching oxygen include hydrogen peroxide, sodium perborate monohydrate. sodium perborate tetrahydrate, sodium percarbonate, any other salt or adduct capable of releasing hydrogen peroxide in water, and mixtures thereof
  • bleach activators bleach precursors
  • TAED tetraacetylethylenediamme
  • peracetic acid Bleach stabilizers for example heavy metal sequestrants and/or free radical inhibitors
  • sodium percarbonate or other persalts may be present in an amount of from 5 to 30 wt %, preferably from 10 to 25 wt %
  • Bleach activators are suitably used in amounts of from 1 to 8 wt %, preferably from 2 to 5 wt %
  • Organic or inorganic peroxyacids can also be used These are normally in an amount within the range of from 2 to 10 wt %, preferably from 4 to 8 wt %
  • Enzymes Conventional proteases and/or amylases can be used in the present compositions, for example Savinase ®
  • Prefened SRA's can have hydrophihc segments and hydrophobic segments and can include charged, e.g., anionic or even cationic (see U.S 4,956,447), as well as noncharged monomer units Structures may be linear, branched or even star-shaped Prefened SRA's include ohgomenc terephthalate esters, e.g., made by transestenfication/oligomenzation with a suitable catalyst Such esters may mco ⁇ orate additional monomers binding through one. two, three, four or more positions, generally without heavy crosshnkmg
  • SRA's also include those w ith segments of ethylene terephthalate or propylene terephthalate with ethylene oxide or propylene oxide, see U.S 3,959.230 and U.S 3,893,929.
  • cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow , and the C1 -C4 alkylcelluloses and C4 hydroxyalkyl celluloses, see U.S 4,000,093
  • Suitable SRA's characterized by poly(v ⁇ nyl ester) hydrophobe segments include graft copolymers of poly(v ⁇ nyl ester), e.g., C ⁇ -C vinyl esters, preferably poly(v ⁇ nyl acetate), grafted onto polyalkylene oxide backbones See European Patent Application 0 219 048, published April 22, 1987 by Kud, et al
  • Commercially available SRA's include SOKALAN SRA's such as SOKALAN HP-22, available from
  • SRA's include (I) noniomc terephthalates using dnsocyanate coupling agents to link up polymenc ester structures, see U.S 4,201 ,824 and U.S 4,240,918, (II) SRA's with carboxylate terminal groups made by adding t ⁇ melhtic anhybnde to known SRA's to convert terminal hydroxyl groups to t ⁇ melhtate esters See also U.S 4,525,524, (III) anionic terephthalate-based SRA's of the urethane-lmked vanety, see U.S 4,201,824; (IV) poly(v ⁇ nyl caprolactam) and related co-polymers with monomers such as vinyl pynohdone and/or dimethylammoethyl me hacrylate, including both noniomc and cationic polymers, see U.S 4,579,681 , (V) graft copolymers, in
  • compositions of the present invention can also optionally contain water- soluble ethoxylated or acylated amines or polyamines having clay soil remov al and antiredeposition properties
  • Granular detergent compositions which contain these compounds typically contain from about 0 01% to about 10 0% by weight of the water- soluble ethoxylated amines, liquid detergent compositions typically contain about 0 01% to about 5%
  • a prefened soil release and anti-redeposition agent is ethoxylated tetraethylene pentamine See U S 4,597,898 See also European Patent Application 1 1 1,965, published June 27, 1984
  • Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 1 1 1 ,984, published June 27.
  • Another type of prefened antiredeposition agent includes the known cellulosic materials such as carboxy methyl cellulose (CMC) Polymenc Dispersing Agents Polymenc dispersing agents can be used herein at levels from about 0 1 % to about
  • Such agents include polymenc polycarboxylates and polyethylene glycols
  • Polymenc dispersing agents are believed to enhance detergent builder performance, by mechanisms such as crystal growth inhibition, particulate soil release, peptization, or anti-redeposition
  • Polymenc polycarboxylate matenals can be prepared by polymenzing or copolyme ⁇ zing suitable unsaturated monomers, preferably m their acid form
  • Unsaturated monome ⁇ c acids that can be polymenzed to form suitable polymenc polycarboxylates include acrylic acid, maleic acid (or maleic anhybnde), fumanc acid, itaconic acid, acomtic acid, mesaconic acid, citraconic acid and methylenemalonic acid
  • the presence in the polymeric polycarboxylates herein or monome ⁇ c segments, containing no carboxylate radicals such as vmylmethy l ether, styrene, ethylene, etc is suitable provided that such segments do not constitute more than about 40% by weight
  • Particularly suitable polymenc polycarboxylates can be denved from acrylic acid, as m water-soluble salts of polymerized acrylic acid
  • the average molecular weight of such polymers preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000
  • Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts See U S 3,308,067
  • Acryhc/maleic-based copolymers may also be used Such matenals include the water-soluble salts of copolymers of acrylic acid and maleic acid
  • the average molecular weight of such copolymers preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000
  • the ratio of acrylate to maleate segments will generally range from about 30 1 to about 1 1 , more preferably from about 10 1 to 2 1
  • Alkali metal, ammonium and substituted ammonium salts of the polymers can be used See European Patent Application No 66915, published December 15, 1982, as well as in EP 193,360, published September 3, 1986, which also descnbes such polymers comp ⁇ sing hydroxypropylacrylate
  • Still other useful dispersing agents include the maleic/acryhc/vinyl alcohol te ⁇ olymers
  • Such mate ⁇ als are also disclosed in EP 193,360, including, for example, the 45/45/10 t
  • PEG polyethylene glycol
  • PEG polyethylene glycol
  • Typical molecular weight ranges for these pu ⁇ oses range from about 500 to about 100,000, preferably from about 1 ,000 to about 50,000, more preferably from about 1 ,500 to about 10,000
  • Polyaspartate and polyglutamate dispersing agents may also be used A prefened average molecular weight is about 10,000
  • va ⁇ ous te ⁇ olymers and hydrophobically modified copolymers including those marketed by Rohm & Haas, BASF Co ⁇ , Nippon Shokubai and others for all manner of water-treatment, textile treatment, oi detergent applications Bnghtener
  • Suitable b ⁇ ghteners include those identified in U.S 4,790,856 These include PHORWHITE b ⁇ ghteners from Verona Other b ⁇ ghteners disclosed in '856 include Tmopal UNPA, Tinopal CBS and Tmopal 5BM, available from Ciba-Geigy.
  • compositions of the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabnc to another du ⁇ ng the cleaning process
  • dye transfer inhibiting agents include polyvmyl pyno done polymers, polyamine N-oxide polymers copolymers of N-vinylpynohdone and N- vinyhmidazole, and certain mate ⁇ als accounted for in the bleach system such as zmc, manganese, aluminum and silicon phthalocyamnes, peroxidases, and mixtures thereof
  • these agents typically compnse from about 0 01%> to about 10% by weight of the composition, preferably from about 0 01 % to about 5%, and more preferably from about 0 05% to about 2% Chelating Agents
  • Detergent compositions herein may also optionally contain one or more chelating agents for metals such as iron and or manganese in water-soluble, colloidal or particulate form or associated as oxides or hydroxides, or found in association with soils such as humic substances
  • chelating agents effectively control such transition metals, especially limiting deposition of such transition-metals or their compounds on fab ⁇ cs and/or controlling undesired redox reactions in the wash medium and or at fabnc or hard surface interfaces
  • Such chelating agents include those having low molecular weights as well as polymenc types, typically having at least one, preferably two or more donor heteroatoms such as O or N, capable of co-ordination to a transition-metal
  • Common chelating agents can be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof
  • Prefened chelating agents (chelants) include EDTA, S,S'-EDDS
  • chelating agents will generally comprise from about 0 001% to about 15% by weight of detergent composition More preferably , chelating agents will compnse from about 0 01 % to about 3 0%> by weight of the composition
  • Suds Suppressors - Suds suppressors useful herein may be single mate ⁇ als or may be mixed or compounded in known ways See, for example, Kirk Ofhmer Encyclopedia of Chemical Technology, 3rd. Ed., Vol. 7, ppg 430-447 (John Wiley & Sons, Inc., 1979).
  • Common suds suppressors include C10-C24, preferably C16-C18 monocarboxylic fatty acids and salts thereof. See U.S. Patent 2,954,347.
  • Suitable salts include Na, K, Li, Ca, Mg, Al, Zn, ammonium and alkanolammonium salts.
  • Stearic acid and aluminium tristearate are common examples.
  • Alternate suds suppressors include high molecular weight liquid or waxy linear, cyclic or mixed C12-C70 hydrocarbons (see U.S.
  • paraffins or haloparaffins such as paraffins or haloparaffins
  • fatty acid esters such as fatty acid triglycerides
  • fatty acid esters of monovalent alcohols such as stearone
  • N- alkylated aminotriazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines
  • hydrocarbyl especially stearyl, preferably monostearyl, phosphate esters such as monostearyl acid phosphate.
  • silicone suds suppressors including polyorganosiloxane oils, such as polydimefhylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica.
  • polyorganosiloxane oils such as polydimefhylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins
  • combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica See U.S. 4,265,779, EP 89307851.9, U.S. 3,455,839, and German Patent Application DOS 2,124,526. Silicone defoamers and suds controlling agents in granular detergent compositions are further disclosed in U.S. 3,
  • a solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (prefened), or polypropylene glycol.
  • the primary silicone suds suppressor is branched crosslinked.
  • Certain liquid laundry detergent compositions with controlled suds will comprise from about 0.001 to about 1.
  • silicone suds suppressor comprising (1 ) a nonaqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than about 2 weight %; and without polypropylene glycol.
  • a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of
  • the secondary alcohols include the Cg-Cjg alkyl alcohols having a C ⁇ -C ⁇ chain.
  • a prefened alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12.
  • Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem.
  • Mixed suds suppressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1 :5 to 5:1.
  • Suds suppressors when utilized, are preferably present in a "suds suppressing amount.
  • Suds suppressing amount is meant that the formulator of the composition can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines.
  • compositions herein A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including perfumes, enzyme stabilizers, softening clays such as bentonites, montmorillonites, hectorites, other clays such as laponite or kaolin, chlorine scavengers, such as ammonium sulfate; other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, fillers, especially for bar compositions, etc.
  • magnesium and/or calcium salts such as MgCl 2 , MgSO 4 , CaCl 2 , CaSO 4 , magnesium silicates and the like, can be added, for example as fillers for bar forms of the compositions.
  • detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating.
  • the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate.
  • the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.
  • the detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 1 1 , preferably between about 7.0 and 10.5, more preferably between about 7.0 to about 9.5.
  • Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
  • compositions herein can vary in physical form, as nonlimitingly illustrated by granular, tablet, bar, and pouch forms.
  • the compositions include the so-called concentrated granular detergent compositions adapted to be added to a washing machine by means of a dispensing device placed in the machine drum with the soiled fabric load.
  • the mean particle size of the components of granular detergent compositions herein is preferably be such that no more that 5% of particles are greater than 1 7mm in diameter and not more than 5% of particles are less than 0 15mm in diameter
  • Mean particle size herein can be determined by sieving a sample of mate ⁇ al to be sized into a number of fractions (typically 5) on a se ⁇ es of Tyler sieves Weights of fractions are plotted against the aperture size of the sieves The mean particle size is the aperture size through which 50% by weight of the sample would pass
  • Certain prefened granular detergent compositions in accordance herein are high- density types, now common in the marketplace, typically these have a bulk density of at least 600 g/htre, more preferably from 650 g/htre to 1200 g/litre Laundry washing method
  • Machine laundry methods herein typically compnse treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a detergent composition of the invention
  • an "effective amount” is here meant from 40g to 300g of product dissolved or dispersed a wash solution of volume from 5 to 65 litres
  • product "usage levels" can vary widely, depending not only on the type and seventy of soils and stains, but also on wash water temperatures and volumes and type of washing machine
  • a dispensing device is employed in the washing method
  • the dispensing device is charged with the detergent product, and is used to introduce the product directly into the drum of the washing machine before the start of the wash cycle Its capacity should be such as to be able to contain sufficient detergent product as would normally be used in the washing method
  • the dispensing device containing the detergent product is placed inside the drum At the commencement of the wash cycle of the washing machine, water is introduced into the drum and the drum penodically rotates
  • the design of the dispensing device should be such that it permits containment of the dry detergent product but then allows release of this product du ⁇ ng the wash cycle in response to its agitation as the drum rotates and also as a result of its contact with the wash water
  • the dispensing device may be a flexible container, such as a bag or pouch
  • the bag may be of fibrous construction coated with a water impermeable protective mate ⁇ al so as to retain the contents, such as is disclosed in European published Patent Application No 0018678
  • it may be formed of a water-msoluble synthetic polymenc matenal provided with an edge seal or closure designed to rupture m aqueous media as disclosed in European published Patent Application Nos 001 1500. 0011501 , 0011502, and 001 1968
  • a convenient form of water-frangible closure compnses a water soluble adhesive disposed along and sealing one edge of a pouch formed of a water impermeable polymenc film such as polyethylene or polypropylene Abbreviations used in Examples
  • Alkyl Sulfate CxyAS Alkyl sulfate typically sodium salt form, derived from fatty alcohol containing from x to y carbon atoms Examples include sodium tallow alkyl sulfate (TAS) and primary, guerbet, and mid-chain branched (WO
  • alkyl sulfates containing from 10 to 20 carbon atoms (more typically from 14 to 16 or from 16 to 18) or mixtures thereof
  • Noniomc linear or branched (WO 97/39091 ) noniomc surfactant typically CxyEz derived from fatty alcohol with chamlength of from x to v condensed with an average of z moles of ethylene oxide
  • Suitable examples include
  • Hyb ⁇ d builder Mate ⁇ al as disclosed in the Synthesis Examples hereinabove Zeolite system one or more of - Zeolite A Hydrated sodium aluminosilicate of formula Na j 2 (A10 2 S ⁇ O 2 ) ⁇ 27H 2 0 having a primary particle size in the range from 0 1 to 10 micrometers (weight expressed on an anhydrous basis) Zeolite P Zeolite P (may be maximum aluminum type) Zeolite X Zeolite X Zeolite AX Zeolite AX Zeolites A,X co-crystallized (Condea, EP 816291 Al ) Silicate system 2r or 3r sodium silicate; crystalline layered silicate of formula ⁇ - a 2 S ⁇ 2 ⁇ 5
  • TSPP Tetrasodium pyrophosphate non-polymer type polycarboxylate.
  • Carbonate Anhydrous sodium or potassium carbonate e.g., with particle size between
  • a preferred polymer-type polycarboxylate has polyglyoxylate structural units
  • Enzyme system one or more of -
  • Hydrophobic Bleach NOBS i.e.. nonanoyloxybenzene sulfonate in the form of the sodium salt
  • Activator NAC-OBS i.e . (6-nonam ⁇ docaproyl) oxybenzene sulfonate
  • mixtures or similar
  • Organic Bleach Booster e.g.. omega-(3.4-d ⁇ hydro ⁇ soqu ⁇ nohn ⁇ um alkane sulfonate(s) of U.S.
  • Transition-metal Bleach e.g., as desc ⁇ bed in WO 97/00937.
  • Chelant System one or more of:
  • DTPA Diethylene t ⁇ amine pentaacetic acid
  • DTPMP Diethylene t ⁇ amine penta (methvlene phosphonate). marketed by Monsanto under the Tradename Dequest 2060
  • Soil Release Agent one or more of SRP 1 Sulfobenzoyl and capped esters with oxyethylene oxy and terephthalovl backbone or SRP of US 5,415,807
  • PVNO Polyvmylpy ⁇ done N-oxide polymer with an average molecular weight of
  • Antifoam System e g polydimefhvlsiloxane foam controller with siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10 1 to 100 1 , may be complemented by fatty ac ⁇ d(s)
  • Bicarbonate Anhydrous sodium bicarbonate w ith a particle size distribution between 400 ⁇ m and 1200 ⁇ m
  • Stabilizers process aids, other minors e g , one or more of
  • Granular laundry detergents for use in domestic appliances or handvvashmg of laundry at from 100 to 10,000 ppm, depending on appliance and/or water and/or conditions, are re ared in accordance with the invention:
  • Granular laundry detergents for use in domestic appliances or handwashing of laundry at from 100 to 10,000 ppm, depending on appliance and/or water and/or conditions, are prepared in accordance with the invention:
  • Spray-drying towers can be used to make granular laundry detergents or base powders These often have a density less than about 500 g/1 Typically, an aqueous slurry of ingredients is passed through a spray-drymg tower at temperatures of about 175°C to about 225°C
  • Spray-dned granules can be densified by loading a liquid, often a noniomc surfactant, into the pores of the granules and/or passing them through one or more high speed mixer/densifiers such as a device sold as a "Lodige CB 30" or “Lodige CB 30 Recycler”
  • a high speed mixer/densifier such as a device sold as a "Lodige CB 30" or “Lodige CB 30 Recycler”
  • This comprises a static cyhnd ⁇ cal mixing drum having a central rotating shaft on which are mounted mixing/cutting blades Ingredients for the detergent composition are introduced into the drum and the shaft/blade assembly is rotated at speeds in the range of 100-2500 m to provide thorough mixing/densification See U.S 5,149,455 and 5,565,422
  • Other suitable commercial apparatus includes the "Shugi Granulator” and the "Drais K-TTP 80
  • Spray-dned granules can also be densified by treating them in a moderate speed mixer/densifier so as to obtain particles, for which the "Lodige KM" (Senes 300 or 600) or “Lodige Ploughshare” mixer/densifiers are suitable and are typically operated at 40-160 ⁇ m
  • Other useful equipment includes the "Drais K-T 160"
  • This process step using a moderate speed mixer/densifier e g Lodige KM
  • the aforementioned high speed mixer/densifier e g Lodige CB
  • Other types of granules manufactu ⁇ ng apparatus useful herein include the apparatus disclosed in U.S Patent 2,306,898, to G L Heller, December 29, 1942
  • the process may include one or more streams of undersized particles These can be recycled to the mixer/densifiers for further agglomeration or build-up Oversized particles can be sent to grinding apparatus, the product of which is fed back to the mixing/densifying equipment
  • Such recycles facilitate overall particle size control giving in finished compositions which hav ing a relatively uniform dist ⁇ bution of particle size (400-700 microns) and density (> 550 g 1) See U S 5,516,448 and U S 5,489,392
  • Other suitable processes which do not call for sprav-drymg are descnbed in U S 4,828,721, U S 5,108,646 and h S 5.178,798
  • the high density detergent compositions can be produced using a fluidized bed mixer in which the ingredients are combined as an aqueous slurry (typically 80% solids content) and sprayed into a fluidized bed to provide finished granules
  • a fluidized bed mixer in which the ingredients are combined as an aqueous slurry (typically 80% solids content) and sprayed into a fluidized bed to provide finished granules
  • pnor to fluid bed mixing the slurry can be treated using the aforementioned Lodige CB mixer/densifier or a "Flexomix 160" mixer/densifier, available from Shugi Fluidized bed or moving beds of the type available under the tradename "Escher Wyss" can also be used
  • Another alternate process involves feeding a liquid acid precursor of an anionic surfactant, an alkaline inorganic mate ⁇ al (e g sodium carbonate) and optionally other detergent ingredients into a high speed mixer/densifier (residence time 5-30 seconds) so as to form particles containing a partially or totally neutralized anionic surfactant salt and the other starting detergent ingredients
  • a high speed mixer/densifier e g Lodige KM
  • high density detergent compositions can be produced by blending conventional spray-dned detergent granules with detergent agglomerates m vanous proportions (e g a 60 40 weight ratio of granules to agglomerates) produced by one or a combination of the processes discussed herein
  • Additional adjunct ingredients such as enzymes, perfumes, b ⁇ ghteners and the like can be sprayed oi admixed with
  • PolyethyleneGlycol (MW 4000) 20 20 10
  • Termamyl amylase 60 KNU/g- 0.3 0.3 -

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Abstract

Built laundry detergent compositions, especially granules, powders, tablets or syndet bars for domestic use, wherein the builder comprises at least in part a hybrid crystalline aluminosilicate having occluded silicate, carbonate, sulfate, phosphate, borate, nitrate, nitrite, Na2O, or mixtures thereof; and wherein the hybrid can further be chemically or physically surface-modified, combined with other builders, or processed in particular ways; and wherein the hybrid is coformulated with detergent adjuncts selected to improve the compositions, especially certain surfactants, particularly mid-chain branched types; certain bleach systems, especially those having bleach catalysts; and certain enzymes or other adjuncts.

Description

IMPROVED DETERGENT COMPOSITIONS COMPRISING HYBRID
ZEOLITE BUILDERS
TECHNICAL FIELD
This invention relates to built detergents for domestic use, especially having granular, tablet or syndet bar form The compositions contain particular aluminosilicate builders, preferably hybπds of aluminosilicate and specific occluded mateπals such as silicate, carbonate, sulfate, phosphate, borate, nitrate, mtπte, Na^O, or mixtures thereof
The builder can be surface-modified or can be processed in a particular manner The compositions further contain selected detergent adjuncts, such as certain surfactants, enzymes, polymers and/or bleaches Other adjuncts, e.g , conventional surfactants, enzymes, builders or bleaches can also be present
BACKGROUND OF THE INVENTION The formulation of zeolite builders into detergents is technically difficult Zeolites hitherto formulated in detergents lack an ideal combination of low cost, ease of manufacture, high equilibrium binding of both Ca and Mg, rapid kinetics of binding for Ca and Mg, and ability to hold large amounts of surfactant Zeolites or aluminosi cates, when added to laundry detergents, can interact adversely with numerous laundry detergent adjuncts, e g bleaches, bleach catalysts, enzymes, bπghteners and other additives, and/or produce unacceptable harshness and/or give other major problems, such as redeposition onto textiles
Another significant technical problem is a strong tendency for low-level adjuncts or differently charged additives such as cationic surfactants, catalysts or enzymes to adsorb onto relatively large, aniomcally charged surfaces of insoluble inorganic builders Since such adjuncts are often expensive and tend to be used at relatively low levels in detergent compositions, their loss by any mechanism, such as interaction with the builder, can have dramatic effects on overall cleaning performance
Accordingly, substantial and costly research and expeπmentation are needed to integrate a synthetic inorganic builder mateπal with other detergent ingredients so as to benefit from its properties and at the same time avoid negating or reducing the desirable effect(s) of the adjuncts with which it is formulated Such expeπmentation often results in failure There is, therefore, an ongoing unmet need for fully formulated detergent compositions acceptably incorporating synthetic inorganic builders, especiallv certain types for which synthesis methods have only recently been descπbed
BACKGROUND ART WO 98/42622, to Englehard Corporation, published October 1 , 1998, provides processes for preparing certain hybrid zeolite-silicate compositions These materials do not contain hydroxysodahte, indeed a comparison is given to demonstrate the absence thereof Also descπbed are some detergent formulations using the hybrid alummosihcates Solving the problems of formulating these hybrid builders, especially with certain potentially interacting low-level, high cost ingredients, are not, however, specifically addressed It appears to be assumed that the hybπd zeolite-silicate can simph be formulated as a replacement for current zeolites, and the formulation teaching is to conventional zeolite detergents according to the theory of operation described in WO 98/42622, the hybrid mateπal has a higher charge Whether for this reason or due to some other theory of operation, it has now been discovered that the WO 98/42622 hybπd materials do not have the same properties for purposes of formulation into detergents as do the conventional detergent zeolite, zeolite A
While WO 98/42622 provides apparently useful synthesis methods, and the evidence provided in WO 98/42622 strongly suggests that the WO 98/42622 hybπd matenal is different from zeolite MAP, w hether this hybrid or silicate-occluded mateπal is in fact novel may, or may not, be the case There exists a substantial body of old pπor art on zeolite manufacture which is not in computer-readable form and as such is relatively difficult to find and/or search An accessible fraction of this art includes disclosure of occluded, or hybrid-type (to use the WO 98/42622 language) zeolites or hybπd alummosihcates having occluded salts of various kinds, and hints that occlusion is well-known to zeolite manufacturers For example, occluded zeolites are described in "Zeolite Chemistry and Catalysis", Ed J A Rabo, ACS Monograph Series, Vol 171 , American Chemical Society, Washington D C , 1976 See more particularly Chapter 5, "Salt Occlusion in Zeolite Crystals", pages 332 - 349 and references cited therein, see also Chapter 1 of the same reference Thus, such mateπals include, for example, sodium nitrate-occluded or other nitrate salt-occluded zeolite A, see the work referenced by Liquomik and Marcus See also Chapter 1, pages 58-63 of the same ACS monograph, which discloses, for example, NaAlO: occluded zeolite A, other occluded alummosihcates, such as borate-occluded sodahte, NaOH-occluded sodahte, Na O,- occluded cancπnite, halide- or nitrate-occluded zeolite Y, and yet other salt-occluded zeolites In Chapter 4 of the ACS monograph, it is noted "Another consequence of the Donnan equihbπum is tnat electrolyte invasion can occur In this process, anions from the aqueous phase enter into the zeolite phase with a correspondingly equivalent number of additional cations " See also Chapter 4 of the same ACS monograph at pages 310-1 1 1, foi example the statement "Modified \ aneties of many zeolites can be prepared by occluding extraneous species within the zeolite crystal either duπng or after synthesis " Reference is made to the work of Barrer and others In Chapter 5 at page 338, reference is made to borate-occluded zeolite A In shon, a wealth of occluded aluminosilicate mateπals appear to be disclosed in the art
Surpnsingly, in contrast, other than m WO 98/42622, there appears to be no specific disclosure whatever of the use of occluded or hybrid-type zeolites or other occluded alummosihcates in detergent compositions
It is therefore against a background of (a) an apparent plurality of occlusions in zeolites coupled with (b) a lack of teaching on how to formulate occluded or hybπd-type aluminosilicate materials in detergents other than as a mere substitute for zeolite A or P as taught in WO 98/42622, that the present invention is provided
Additionally by way of background on zeolites and occluded zeolites, the practitioner is refeπed to D W Breck, "Zeolite Molecular Sieves", Wiley, New York, 1974 and to Kirk Othmer's Encycopedia of Chemical Technology, 4th Edition, 1995, Wiley . New York, see Vol 16, "Molecular Sιe\ es" Builders in general are descπbed in many patents issued to Procter &. Gamble,
Unilever, Hoechst / Claπant, Kao, Lion, Crosfield, PQ Corp , and others One recent review in the context of detergents is in Surfactant Science Series, Marcel Dekker, New York, see Vol 71 , Ed M S Showell, published 1998 See more particularly Chapter 3, "Builders The Backbone of Powdered Detergents" by Hans-Peter Rieck of Hoechst Claπant
All percentages herein are weight of the detergent composition unless otherwise noted All references cited are incorporated by reference in their entirety Ratios and prooortions are by weight unless otherwise specifically indicated
SUMM ARY OF THE INVENTION
In a first aspect or embodiment of the invention, it has now been discovered that improved detergent compositions beyond those descπbed in WO 98/42622 can be formulated by combining the hybπd zeolite-silicates of WO98/42622 with particular detergent ingredients In a second aspect or embodiment of the invention, improved detergent compositions are formed by combining detergent ingredients with certain hybπd zeolite- cobuilders not specifically described in WO98/42622 In these materials, the hvbπd builder has an occluded material other than silicate, such as sulfate, borate, nitrate, nitrite, phosphate, or Na-,0
In a third aspect or embodiment of the invention, improved detergent compositions are formed by combining detergent ingredients with combinations of hybπd zeolite-silicate and hybrid zeohte-cobuilder systems wherein these combinations are not descπbed in WO98/42622 In these systems, the hybπd builder has both occluded silicate and another occluded matenal other than silicate, especially an amon having charge greater than 1 , such as occluded sulfate, occluded borate, occluded phosphate, though occluded nitrate, occluded nitπte, or mixtures of any of the aforementioned cobuilders is possible In other variations, alkali metal oxides or hydroxides, such as Na-,0 or NaOH, are present with excellent results
In a fourth aspect or embodiment of the invention, improved detergent compositions are formed by combining detergent ingredients with any of said hybπd zeohte-silicate or hybπd zeohte-cobuilder systems, wherein the hybnd zeolite-silicate or hybπd zeohte-cobuilder occluded system is further modified by chemical or physical modification of the external surfaces Such modification can range quite widely, from a chemical approach, such as surface silylation or treatment with reactive ammosihcones, to a physical approach, such as such as direct contacting of the hybrid with PEG, e g , PEG 4000. waxy nomonic surfactants, film-forming polymers as defined in detail hereinafter, or combinations of chemical and physical treatment The surface treatment adjunct can improve one or more aspects of cleaning or fabric care when the treated hybπd is included in a detergent formulation For example, the treated hybπd when formulated with low- level cationic cosurfactants, enzymes, transition metal bleach catalysts, or the like, can be shown to have a reduced tendency to interfere with the cleaning performance of such desirable adjuncts
In a fifth aspect or embodiment of the invention, improved detergent compositions are formed by combining detergent ingredients with any of said hybπd mateπals in the presence of innocuous fillers or common inorganic pigments, including in particular nonzeolitic alummosihcates such as hvdroxysodalite and or talc and/or whiteners such as titanium dioxide The hvdroxysodalite or other filler or whitener or mineral can be present in the hybrid, e g , through crystal imperfections, can be present in the builder system, or can be introduced along with other detergent ad]uncts While these filled detergent compositions might be expected to be significantly worse for cleaning than the unfilled types of compositions, they are surprisingly effective, for example in laundry bars Without being limited by theory, the absolute magnitude of the cation exchange capacity and even the rate of sequestration of Duilder mateπals are not the only factors to consider in arπvmg at excellent detergent compositions Wetting and dispersion rates, and processing characteπstics of the mateπals, for example, can also be important Thus, while the introduction of mateπals such as hydroxysodalite and the aforementioned surface treatments of the hybrid may not add to the technical measurable builder capacity , through these other factors, the filler and/or surface treatment mateπal may lead to improved detergent compositions This is particularly true when problems such as redeposition are properly addressed through coformulation of the hybrid builder with other selected detergent adjuncts
The present invention, therefore, has numerous advantages, including improved laundry cleaning and/or anti-redeposition performance and/or cost effectiveness as compared with the cleaning and/or antiredeposition performance offered bv WO98/42622 alone Other significant advantages are improved compatibility of the formulated ingredients, for example, a reduced tendency of the hybπd builder to interact negatively w ith coformulated detergent ingredients
DETAILED DESCRIPTION - PREFERRED EMBODIMENTS The present invention includes a detergent composition comprising (a) from about 0 1 % to about 99% of a builder system compπsing. in part, a particulate inorganic ion-exchanging builder material, said builder material compπsing a hybrid of crystalline zeohtic aluminosilicate and at least one occluded nonsihcate cobuilder, and (b) from about 0 1 % to about 99% of detergent adjuncts Preferably in said embodiment, said hybπd compnses from about 0 01 to 1 0, more preferably 0 10 to 1 0 weight fraction of said builder system and said hybπd is characteπzed by a capacity to sequester calcium in excess of the amount of charge inducing aluminum in the zeohtic aluminosilicate Alternately, said hybπd is characteπzed by a calcium ion exchange capacity of at least 15% greater, preferably at least 20%, more preferably at least 25% greater than the calcium ion exchange capacity of a reference material selected from non-hybridized zeolite A Such reference zeolite A in fully Na-exchanged form has a theoretical cation exchange capacity of about 7 meq/g, typically 5-7 meq/g, e g , 6 meq/g in practice Such mateπal for reference purposes suitably has a particle size of from about 1 micron to about 10 microns
The occluded nonsihcate cobuilder can be selected from (I) the group consisting of occluded phosphate, occluded carbonate, occluded borate, occluded nitrate, occluded nitπte, occluded sulfate, occluded Na^O and mixtures thereof, and (n) mixtures of said occluded nonsihcate cobuilder and occluded silicate, provided that in anv of said mixtures of occluded nonsihcate and occluded silicate, the weight fraction of occluded silicate is no more than about 0 99, preferably no more than about 0 80
The invention also encompasses a detergent composition comprising (a) from about 0 1 % to about 99% of a builder system comprising, in part, a particulate inorganic ion-exchanging builder mateπal, said builder mateπal compπsing a hybπd of crystalline aluminosilicate and an occluded cobuilder, said hybπd further compπsing at least one adsorbed or externally chemically bonded cobuilder or adjunct other than said occluded cobuilder, and (b) from about 0 1 % to about 99% of detergent adjuncts other than any adjunct of said builder system
The adsorbed or externally chemically bonded cobuilder or adjunct can be a builder adjunct or a nonbuilder adjunct When the externally chemicallv bonded cobuilder or adjunct is a nonbuilder adjunct, it preferably reduces the negative surface charge of the hybrid relative to the nontreated hybrid, whereby said component (a) has improved compatibility with cationically charged surfactants and/or enzymes
When such surface treatment of the hybrid is practiced, the detergent composition of the invention can readily accommodate a detergent adjunct compπsing at least one cationic detersive surfactant Other detergent adjuncts may be present, such as at least one anionic detersive surfactant, especially mid-chain branched types, in addition to said cationic detersive surfactant
In general, said occluded cobuilder is selected from the group consisting of occluded silicate cobuilder, occluded nonsihcate cobuilder, and mixtures thereof
Thus there are prefeπed embodiments wherein said occluded cobuilder is an occluded silicate cobuilder, such embodiments include those wherein the hybrid is fully in accordance with the above-identified Engelhard patent publication
However the invention also encompasses embodiments wherein said occluded cobuilder is selected from the group consisting of occluded nonsihcate cobuilder and mixtures of occluded nonsihcate cobuilder and occluded silicate cobuilder, and wherein said occluded nonsihcate cobuilder is selected from the group consisting of occluded nitrate, occluded phosphate, occluded carbonate, occluded borate, occluded nitπte, occluded sulfate, occluded Na2O and mixtures thereof In this case, certain art-known occluded zeolites, outside of the above-identified Engelhard publication, are useful herein such occluded zeolites are not known to the inventors as having been used in any laundry detergent, especially modern high-density granules or tablet form-detergents In another embodiment the present invention encompasses a detergent composition compπsing (a) from about 0 1% to about 99% of a builder system comprising in part, a particulate inorganic ion-exchanging builder material, said builder mateπal comprising a hvbπd of crystalline aluminosilicate and an occluded cobuilder, and (b) from about 0 1 % to about 99% of at least one detergent adjunct selected from the group consisting of (l) detersive surfactants having at least one biodegradably branched hydrophobe, (n) organic polymeric materials selected from the group consisting of end- capped oligomeπc esters, hydrophobically modified polyacrylates, terpolymers compπsing maleate or acrylate, polymeric dye transfer inhibitors, polyimme deπvatives, and mixtures thereof, (in) oxygen bleach promoting mateπals selected from the group consisting of organic bleach boosters, transition-metal bleach catalysts, photobleaches, bleach-promoting enzymes and mixtures thereof, (iv) fabπc care promoting agents other than softeners or said organic polymeric materials, and (v) mixtures of (l) - (iv)
In this latter embodiment, said hybπd preferably comprises at least about 0 01 weight fraction of said builder system and wherein said occluded cobuilder is selected from group consisting of occluded silicate cobuilder, occluded nonsihcate cobuilder and mixtures of said occluded silicate cobuilder and said occluded silicate cobuilder, and w herein said occluded nonsihcate cobuilder, when present, is present at a weight ratio to occluded silicate cobuilder of from about 1 1000 to about 1000 1 and is selected from the group consisting of occluded nitrate, occluded phosphate, occluded carbonate, occluded borate, occluded nitπte, occluded sulfate, occluded a^O and mixtures thereof The builder system itself can be varied Thus there is encompassed a detergent composition as defined hereinabov e wherein said hybπd comprises at least about 0 10 weight fraction of said builder system and wherein from about 0 10 to about 0 90 weight fraction of said builder system is selected from the group consisting of zeolite A, zeolite B, zeolite P, zeolite MAP. zeolite X, zeolite AX, clays, layer silicates, chain silicates, soluble silicates, citrates, nitπlotπacetates, ethercarboxylates (preferably carboxymethyloxysuccinate, tartrate monosuccinate, tartrate disuccmate, oxydisuccmate or mixtures thereof), carbonates (preferably sodium carbonate and/or sodium bicarbonate), polyacetal carboxylates, and mixtures thereof Aminofunctional variants of the ether carboxylates can also be used (Desirably for cost reasons at least 80% by weight of the soluble or exchangeable cations inherent in the builder system are sodium, however other soluble cations, especially potassium, can be included at varying levels and calcium and/or magnesium may also be present Magnesium silicate in particular can be used as a cobuilder or as an adjunct desirable for processing reasons) Other highly desirable detergent compositions compnse the hybrid builder together with an additional specified builder material as described in more detail hereinafter As noted the invention encompasses embodiments wherein the hybnd is in accordance with the above-identified Engelhard patent, and other embodiments wherein the hybπd is not in accordance with Engelhard Such embodiments include any detergent composition wherein the builder system has measurable hvdroxysodalite as evidenced by peaks at 14 0, 24 3 and 25 1 degrees 2 theta in the XRD powder pattern of the builder system taken as a whole, oi wherein the hybπd has measurable hvdroxysodalite as evidenced by peaks at 14 0, 24 3 and 25 1 degrees 2 theta in the XRD powder pattern of the hybrid examined on its own
In certain especially prefeπed embodiments the detergent compositions incorporate biodegradably branched detersive surfactants These embodiments include detergent compositions wherein said detergent adjunct compπses at least one detersive surfactant having at least one biodegradably branched hydrophobe, said surfactant being selected from mιd-chaιn-C:-C -brancned C,-C| g-alkyl sulfates. mιd-chaιn-CrC4-branched C -Ct -alkyl ethoxylated. propoxylated or butoxylated alcohols, mid-chain-C -C4- branched C3-C^-alkyl ethoxysulfates mιd-chaιn-C,-C,-branched -C^-alkyl benzenesulfonates and mixtures thereof, and wherein said detersive surfactant is present at a level of from about 0 1 % to about 30% by weight of said detergent composition
The invention is quite tolerant of variations in quality of the hybnd matenal Thus the invention includes detergent compositions wherein said hybπd builder mateπal has a capacity to sequester calcium anywhere in excess of the amount of charge inducing aluminum in the crystals of the hybπd builder matenal Preferably, however, said hybrid builder material comprises is characteπzed bv a calcium ion exchange capacity of at least 25% greater than the calcium ion exchange capacity of a reference matenal selected from non-hybndized zeolite A Also in preferred embodiments the total SiO-, in said hybπd builder mateπal can be from 1 02 to 1 50 times the framework SiO, as determined by compaπson of x-ray diffraction, x-ray fluorescence and "*Sι NMR analysis
In another prefeπed embodiment the invention includes a detergent composition comprising (a) from about 0 1 % to about 99% of a builder system compπsing, in part, a particulate inorganic ion-exchanging builder material compnsing a hybπd of crystalline aluminosilicate and occluded silicate having a SiOJA O, ratio below 3 and formed by a process compπsing the step of adding an aluminum source to a concentrated silicate solution having a pH above 12, said silicate solution having been at least partially depolymeπzed by heating prior to the addition of said aluminum source, and (b) from about 0 1% to about 99% of at least one detergent adjunct selected from the group consisting of (l) detersive surfactants having at least one biodegradably branched hydrophobe, (n) organic polymeric materials selected from the group consisting of end capped ohgomeπc esters, hydrophobically modified polyacrylates te olymers compnsing maleate or acrylate, polymeric dye transfer inhibitors, polyimine deπvatives, and mixtures thereof, (in) oxygen bleach promoting materials selected from the group consisting of organic bleach boosters transition-metal bleach catalysts, photobleaches, bleach-promoting enzymes and mixtures thereof, (iv) fabπc care promoting agents other than softeners or said organic polymeric matenals, and (v) mixtures of (1) - (iv)
In such embodiments said step of depolymenzmg said sodium silicate solution preferably compnses heating at temperatures of from 50 °C to 85 °C for a peπod of 10 minutes or longer
Such embodiments include those wherein said composition compnses soluble silicate as a non-occluded cobuilder and wherein the total level of soluble silicate in said composition as a whole is limited, and is preferably no more than the equivalent of about 3% by weight of the composition of 2 Or sodium silicate Also included are the compositions wherein the hybnd has measurable hvdroxysodalite as evidenced by XRD powder pattern, compositions wherein said builder system comprises said particulate hybrid aluminosilicate mateπal in conjunction with at least one traditional builder mateπal, at a ratio of hybnd aluminosilicate to traditional builder material of from 5 1 to about to about 1 5, compositions which compπse as an adjunct a low level of chelant (preferably less than about 2% by weight of the composition, more preferably from about 0 1 % to about 1 5%, highly prefeπed chelants indlude DTPA, EDTA, S,S'-EDDS and mixtures thereof ), compositions comprising as an adjunct a dual-chelant system hav ing at least one nonphosphonate aminofunctional chelant and at least one phosphonate-functional chelant, and compositions compπsing as an adjunct a low level of polycarboxylate polymer (preferably a Murphy-type system, low polymer levels, e.g.. less than about 2%)
The present invention has other embodiments and ramifications, such as a detergent composition compπsing (a) from about 0 1% to about 99% of a builder system compπsing, in part, a particulate inorganic ion-exchanging builder mateπal compnsing a hybπd of crystalline aluminosilicate and occluded cobuilder, said hybπd having a SiOJAKO ratio below 3 and formed by a process comprising the step of adding an aluminum source to a concentrated silicate solution having a pH above 12. said silicate solution having been at least partially depolymeπzed by heating prior to the addition of said aluminum source and further, optionally but preferably, at least one source of occludable nonsihcate cobuilder having been added in any step and/or further, optionally but preferably, at least one surface treating agent having been applied to the external surfaces of said hybπd after formation thereof, subject to at least one of the following provisions with respect to the composition of said builder system
- the builder system has measurable hydroxysodahte as evidenced by peaks at 14 0, 24 3 and 25 1 degrees 2 theta in the XRD powder pattern of the builder system taken as a whole and/or
- the hybrid has measurable hydroxysodahte as evidenced by peaks at 14 0, 24 3 and 25 1 degrees 2 theta in the XRD powder pattern of the builder system taken on its own and/or
- the hybnd has measurable occluded nonsihcate cobuilder as evidenced directly and/or indirectly by any combination of elemental analysis, XRD powder pattern, 29Sι
NMR or other known techniques and/or
- the hybrid has measurably different wetting and/or surface charge as compared with a non-surface treated hybnd, and (b) from about 0 1 % to about 99% of at least one detergent adjunct
In certain preferred examples of such compositions, said hybnd compnses occluded silicate, wherein said hybπd is characteπzed by 29Sι NMR peaks in the range -81 to -85 ppm
In other prefeπed examples of such compositions, said detergent composition has the form of a laundry bar, tablet, low -density granule or powdei, high-density granule or powder (e g , > 600 g/hter), paste, or gel or liquid having dispersed solids, wherein said hybrid has a measurable improvement in the sum of Calcium binding and Magnesium binding as compared to Zeolite A, delta-layered silicates and mixtures thereof
Moreover the present invention encompasses a detergent composition compnsing (a) from about 0 1% to about 99% of a builder system compπsing, in part, a particulate inorganic ion-exchanging builder mateπal compπsing a hybπd of crystalline aluminosilicate and occluded cobuilder. said hybnd having a SiOVAKO, ratio below 3 and formed by a process comprising the step of adding an aluminum source to a concentrated silicate solution having a pH above 12, said silicate solution having been at least partially depolymenzed by heating prior to the addition of said aluminum source and further, optionally but preferably, at least one source of occludable nonsihcate cobuilder having been added in any step and/or further, optionally but preferably, at least one surface treating agent having been applied to the external surfaces of said hybrid after formation thereof, and (b) from about 0 1% to about 99% of at least one detersive adjunct, provided that said detergent composition has solid form and the process for prepaπng the detergent composition comprises at least one step of combining said hybπd mateπal with a film-formmg polymer
Equally included in the invention are detergent compositions as generally descπbed heremabove wherein the hybπd matenal has measurably different wetting and/or surface charge as compared with a non-surface treated hybrid
In one prefeπed embodiment of such compositions, there is encompassed herein the detergent composition wherein the hybnd matenal has measurably different wetting and/or surface charge as compared with a non-surface treated hybnd, and wherein said measurable difference is accomplished by a step of treating the hybrid mateπal with PEG or a film-forming polymer
Builder system
In more detail, the present invention includes detergent compositions having a builder system A "builder system" as defined herein compnses one or more detergent ingredients known in the art as "builders", provided that there is included at least one "hybrid" or "occluded" aluminosilicate builder as defined in more detail hereinafter
In certain embodiments, the builder system differs from builder systems disclosed in WO98/42622 in that the hybnd builder matenal is different from the hybπds of WO98/42622
In other embodiments, the builder system can be identical with those disclosed in WO98/42622. however, in this circumstance, the present detergent compositions have additional improving features deπving from the selection of adjuncts and/or the method of processing
At a minimum, a "builder system" as defined herein must have at least one ingredient which helps control water hardness "Water hardness" includes uncomplexed calcium ansing from water and/or soils on dirty fabncs, more generally and typically, "water hardness" also includes other uncomplexed cations having the potential to precipitate under alkaline conditions, especially the alkaline earths, more particularly magnesium Well-known conventional builders include sodium tπpolyphosphate, a "soluble complexing builder" which has a range of functions and benefits beyond complexation of calcium, such functions include, for example, peptization of inorganic soils Another well-known builder is zeolite A, especially 0.01-10 micron zeolite A m sodium form This builder is a relatively insoluble crystalline matenal, which functions by ion exchange and is sometimes termed an "ion exchanging builder" Yet another well- known builder is sodium carbonate Sodium carbonate functions as a "precipitating builder" - it reduces water hardness by forming one or more types of insoluble complex, such as calcium carbonate Builder systems herein can in general include one or more water-soluble complexing builders and/or one or more ion-exchanging builders and/or one or more precipitating builders, provided that an essential hybrid component as defined hereinafter is present
Art-disclosed builder systems often also include transit! on-metal binding mateπals known as chelants. and/or organic polymers, such as sodium polyacrylate, which have a builder function, however for the purposes of unambiguously accounting for mateπals m the present formulations, the convention will be used of separately accounting for chelants and those organic polymers which have a builder function - they will be added up with separately added detergent adjuncts This is for purposes of formula accounting and does not exclude such mateπals, in practice, from being coprocessed with the "builder system", for example into high density agglomerated particles
Typical builder systems herein are further exemplified by
- a builder system compnsing a hybrid as defined hereinafter, together with a layered silicate and sodium carbonate, - a builder system compπsing a hybπd as defined hereinafter, together with sodium tnpolyphosphate,
- a builder system comprising a hybrid as defined hereinafter, together with sodium carbonate and a member selected from the group consisting of sodium oxydisuccinate, sodium carboxymethyloxysuccinate, sodium nitπlotπacetate, sodium citrate, and mixtures thereof,
- a builder system compπsing a hybπd as defined hereinafter, together with zeolite A and sodium carbonate, and
- a builder system compπsing a hybπd as defined hereinafter having a film- forming polymeπc coating, optionally together with one or more of zeolite A, sodium carbonate, and sodium citrate (recall that in such a case, the level of polymer for formula accounting purposes is accounted into the detergent adjunct outside of the builder system)
In terms of essential component, the detergent compositions and builder systems herein are required to include at least one crystalline, particulate, inorganic ion exchanging builder matenal compnsing a hybrid of crystalline zeohtic aluminosilicate and at least one occluded cobuilder The term "hybnd" indicates that the aluminosilicate and cobuilder are integrated into the same crystal, as distinct from a simple mixture of separate crystals of the components The term "occluded" further particularizes the location of one mateπal relative to the other by specifying that the cobuilder is included into rather than simply externally onto the aluminosilicate crystals The term "hybnd" may be used herein as a shorthand, when unqualified, it encompasses all suitable particulate crystalline alummosihcates. having whatever kind of occluded material which helps detergent performance
In alternate terms, "hybπd" or "occluded" builder materials herein also encompasses all those zeolite compositions comprising both a cobuilder and a zeolite useful as a builder, provided that the composition is the product of a process compnsing the step of adding an aluminum source to a concentrated silicate solution or silicate - cobuilder solution having a pH above 12, said silicate solution or si cate-cobuildei solution having been at least partially depolymenzed, preferably by heating, pnor to the addition of said aluminum source In such compositions, the cobuilder may vary widely, and includes phosphate, carbonate, borate, nitrate, nitπte, sulfate, Na,O. NaOH and mixtures thereof This alternate definition emphasizes that the present invention is not limited to a particular theory of operation
In general, the hybnd builder matenals herein can be categoπzed into a number of distinct classes, depending on the matenal that is occluded into the aluminosilicate crystals
(a) hybrids compnsing occluded silicate,
(b) hybrids comprising occluded nonsihcate cobuilder,
(c) hybrids comprising both occluded silicate and occluded nonsihcate cobuilder The hybrid builder materials can further vary depending on the crystal type, thus hybnds herein can in general be hybπds based on a zeolite A crystal type, a zeolite P or gismondine crystal type, AX type, or any other crystal type known to be associated with ion-exchanging aluminosilicate materials
Hybπds compπsing occluded silicate include those of WO 98/42622, Engelhard, which are disclosed in detail hereinafter
Hybrids compnsing occluded nonsihcate cobuilder include the particulate crystalline alummosihcates having occluded matenal selected the group consisting of occluded phosphate, occluded carbonate, occluded borate, occluded nitrate, occluded nitπte, occluded sulfate, occluded Na:O, occluded NaOH and mixtures thereof The adjective "occluded" is used to emphasize that not only is the selected matenal to be present, it must be located in the aluminosilicate crystals The precise location may vary, though in most instances, it is believed that at least a portion of the occluded matenal lies outside the smallest zeolite cages while lying at least in part inside the larger zeolite cages Mixtures of hybπds can in general be used in any proportion Such mixtures include mixtures of a hybπd according to WO 98/42622 with mixtures of a hybπd varying from WO 98/42622 through possession of at least one of (1) a different, nonsihcate occluded cobuilder or (n ) a distinct crystal type as compared with WO 98/42622
Hybrid matenals herein can have a range of particle sizes, primary crystals in the size range of from about 0 01 to about 20 microns being suitable, from about 1 micron to about 10 micron and having a good ability to diffract X-rays being prefeπed Such pnmary crystals can be agglomerated into larger aggregates to minimize dusting and/or segregation in fully-formulated laundry detergents All hybπds herein can in general vary in pnmary crystallite size and degree of crystal perfection Hybnd materials herein can have a range of occluded cobuilder content, for example from about 0 001 to about 1 0 number fraction of available occlusion sites can be occupied by occluded cobuilder Hybrids having combinations of occluded and adsorbed cobuilder are possible
Hybnd materials herein can have varying cation composition, for example including hydrogen or ammonium or even in part calcium or magnesium, though typically the prefeπed cation is sodium Potassium or lithium, if present, will be in rather limited proportion, e.g , less than about 0 01% of available exchangeable sites Charge-balancing amounts of such cations can be present, or sub-charge balancing amounts, for example when the hybrid material is extensively washed in pure water Hybrid matenals herein can optionally have adsorbed or occluded organic adjuncts, such as perfumes Wherever located in a manufactured formulation, perfumes, like organic polymeric builders or chelants, are added up, for formula accounting purposes, outside of the builder system
Hybrid mateπals herein can hav e varying degree of hydration, for example if used in detergent compositions which are aqueous suspensions, they can be fully hydrated In other nonhmiting examples, if the hybπd material is incorporated in a nonaqueous liquid detergent, a high-density granular detergent comprising bleach or bleach precursor, or a composition comprising a hydrolytically labile perfume precursor or pro-perfume, the hybrid mateπal may be anhydrous or only pamally hydrated Prefeπed hybπd builders hav ing occluded nonsihcate cobuilder herein have occluded mateπals which are typically relatively small inorganic anions, e.g , occluded phosphate, occluded carbonate, occluded borate, occluded nitrate, occluded nitπte, occluded sulfate, and mixtures thereof
A prefeπed group of hybπd builders having occluded nonsihcate cobuilder have occluded mateπals which have an anionic charge greater than one, e g., occluded phosphate, occluded carbonate, occluded sulfate, and mixtures thereof A prefeπed group of hybrid builders having occluded nonsihcate cobuilder have occluded matenals which are phosphorus-free and boron-free, e g , occluded carbonate occluded nitrate, occluded nitnte, occluded sulfate, and mixtures thereof
A prefeπed group of hybrid builders having occluded nonsihcate cobuilder have occluded mateπals which are nitnte-free, e g , occluded carbonate, occluded nitrate, occluded sulfate, and mixtures thereof
Another prefeπed group of hybrid builders having occluded nonsihcate cobuilder have occluded matenals which are nitrate-free, nitnte-free, boron-free and phosphorus- free, e g occluded carbonate, occluded sulfate, occluded Na-,0, occluded NaOH and mixtures thereof
Unless otherwise noted, hybπd builder herein is characterized by at least one of
(l) a 5-mιnute rate of calcium sequestration at least 15%, preferably at least 20%), more preferably at least 25% greater than that of zeolite A having comparable crystal size, and/or (n) a 15-mιnute or equilibrium capacity to sequester calcium in excess of the amount of charge inducing aluminum in the zeohtic aluminosilicate Alternately, said hvbπd is charactenzed by a 15-mιnute or equilibrium calcium ion exchange capacity of at least 15% greater, preferably at least 20%, more preferably at least 25% greater than the calcium ion exchange capacity of a reference material selected from non-hybπdized zeolite A Such reference zeolite A in fully Na-exchanged form has a theoretical cation exchange capacity of about 7 meq/g, typically 5-7 meq/g e g 6 meq/g in practice wherein the abbreviation "meq/g" stands for milhequivalents per gram Such matenal for reference purposes suitably has a panicle size of from about 1 micron to about 10 microns See, for example, the methods disclosed in WO 98/42622 and further detailed hereinafter, especially Table 1 and the discussion of percentage improvement following immediately thereafter which illustrate how the above-identified percentages are to be calculated
Levels of builder system in the completed laundry detergent powder, syndet bar, gel, tablet or pouch can vary widely , for example from 0 1% to about 99% of a builder system comprising the essential hybrid matenal The proportion of the hybπd aluminosilicate builder material can likewise vary, compnsing from about 0 01 to 1 0, more preferably 0 10 to 1 0, weight fraction of the builder system
Hvbπd Aluminosilicate Not According to WO 98/42622 It is to be emphasized that the present invention includes embodiments in which, by way of hybπd mateπal, onlv hybrid alummosihcates not according to WO 98/42622 are used as an essential component These hybπds in general can be selected in any proportion from
(1) silicate-containing hybnds of zeolites having crystal type which differs by X- ray diffraction from those disclosed in WO 98/42622 and (n) hybrids of a crystalline aluminosilicate and at least one non-silica or nonsihcate occluded cobuilder Preferably this cobuilder is selected from the group consisting of phosphate, carbonate, borate, nitrate, nitnte, sulfate, Na,O, NaOH and mixtures thereof
Of course, combinations of silicate-type hybπds as per WO 98/42622 and hybπds having nonsihcate cobuilder selected from the group consisting of phosphate, carbonate, borate, nitrate, nitπte, sulfate, Na O and mixtures thereof in all proportions are also encompassed
The hybrids not according to WO 98/42622 herein generally include those known in the art of zeolite manufacture, see for example "Zeolite Chemistry and Catalysis", Ed J A Rabo. ACS Monograph Series, Vol 171 , Amencan Chemical Society, Washington D.C . 1976. incorporated herein by reference See more particularly the same Volume, Chapter 5, "Salt Occlusion in Zeolite Crystals", pages 332 - 349 and references cited therein Such matenals include, for example, borate-occluded, hydroxide-occluded, or nitrate- or other nitrate salt-occluded zeolite A See, for example, the work by Baπer, or by Liquornik and Marcus refeπed to in the cited standard texts The occluded salt molecules may , or may not penetrate the sodahte cages of the zeolite, and can be aπanged in the larger cages In general, the occlusion may be of the so-called reversible type, or may be non-reversible
Occlusion for the present purposes is best conducted with sodium as cation and without a transition-metal as the cation, though more generally, transition-metal or silver cation occluded variations are possible and can have beneficial effects, such as enhancement of antimicrobial activity of a detergent composition In addition to occlusion of carbonate, nitrate, nitnte, sulfate, phosphate, borate, mixtures thereof, and mixtures thereof with silicate in any proportion, the present invention also encompasses occlusion of Na,O in zeolites, such as Na:O-occluded zeolite A It is known that certain zeolites tend to decompose nitrate catalytically to NaNO: (chabazite and mordenite) and even to produce Na O
The hybnd alummosihcates herein can be prepared by any known method, see for example the ACS monograph cited supra and references therein such methods can be aqueous-based, for example using the above-identified anions in a method otherwise similar to the Engelhard WO 98/42622 method or v ariations thereof, or can be non- aqueous or melt-based methods
Prefeπed hybπds and combinations include those wherein the zeolite is zeolite A, B, P, X, AX or MAP, sodium is the sole cation, and the occluded cobuilder is selected from carbonate, hydroxide and NaO
Suitable levels are from about 0 1% to about 80%, preferably from about 0 5% to about 30%, by weight, of the hybrid aluminosilicate when it is used alone
Suitable levels of a builder system in the present detergent compositions are from about 0 1 % to about 85%, preferably from about 1% to about 40%, by w≤ight Builders other than the hybπd aluminosilicate are conventional and can. for example, be selected from water-soluble organic builders such as 2,2'-oxydιsuccιnate sodium salts, citric acid sodium salts, carboxymethyloxysuccinate sodium salts, nitπlotπacetic acid sodium salts and the like, water-insoluble inorganic builders such as zeolites A, P, B, X, or any ol their modifications, water-soluble organic builders such as various cellulosic polymers, and water-soluble inorganic builders such as sodium carbonates, sodium phosphates, sodium tnpolyphosphates and the like, encompassing a wide range of calcium and/or magnesium binding capability and rate The builder system can be complemented by one or more materials known as chelants, (chelants like, organic polymers, being added up separately in the formula accounting and being materials which generally have the capability to strongly bind transition metal ions or colloidal transition metal precipitates m aqueous alkaline media) Chelants suitable for use herein include ethylenediamine disuccinate sodium salts, EDTA, HEDP, DTPA and mixtures thereof, typical levels are in the range of from about 1 ppm to about 2% by weight of the detergent composition Hvbπd Aluminosilicate Component according to WO 98/42622
The present invention includes embodiments in which a particular hybπd aluminosilicate according to WO 98/42622 is used as an essential component This hybπd matenal can be obtained from Engelhard Corp It is a crystalline zeohtic aluminosilicate having occluded silicate, and in WO 98/42622 it is termed a "hybnd zeolite/silica composition" (HZSC) The terms "aluminosilicate having occluded silica", "aluminosilicate having occluded silicate", "hybrid zeolite/silica composition", and the acronym "HZSC" are used interchangeably
According to WO 98/42622, HZSC matenals may be prepared by-crystal zmg high aluminum zeolites in highly alkaline/high silica environments Chemical analysis indicates an excess of silica in the HZSC beyond that inherent to their crystalline frameworks Such matenals, at least in certain cases, demonstrate sequestration capacities for cations such as calcium which exceed the amount of zeohtic aluminum available foi ion-exchange and even exceed the theoretical limit possible for a zeolite Thus, HZSC materials and their properties are potentially different ooth in degree and in kind from those of a conventional zeolite According to the inventors of WO 98/42622, the "key mechanism ir the effectiveness of HZSC materials is denved from the ability of zeolite cages to isolate and stabilize small, highly charged silicate units " The inventors of the present invention remark that alternative theoπes can be advanced, for example it is known that small cobuilder polyanions (in this case silicate) can reduce electrostatic repulsions between cations in alummosihcates This can stabilize both sodium-exchanged and calcium- exchanged occluded alummosihcates relative to the non-occluded alummosihcates Such theory would be broadly consistent with the compositional descnption of HZSC While less likely in view of the WO 98/42622 data, sodium metasihcate, if intimately mixed with zeolite could alternately provide compositions, effectively made by the processes of WO 98/42622, which act more effectively than builder compositions hitherto available, for example by an improved concerted action as a precipitating cobuilder. together with the zeolite Theory should therefore not be considered limiting of the present invention Rather, the value of WO 98/42622 as a source of builder for the present invention may he to a greater extent in the product of the descπbed processes than in the precise mode of descnption of the compositions
The above cautions notwithstanding, WO 98/42622 discloses that silicate units are introduced duπng synthesis of HZSC by providing an environment wherein silica in the reaction mixture is depolymenzed to highly charged predominantly monomenc units before crystallization begins The occluded silicate units of the HZSC are visible in 29Sι NMR spectra The HZSC as a whole is stated to be "more powerful" in complexmg multivalent cations than are existing zeolites, silicates or mixtures thereof The zeolite framework and occluded silicate units are stated to "act in concert, as a new type of hybnd composition, showing properties neither zeolites, silicates nor physical blends of the two demonstrate" In addition to high capacity for ion exchange, the HZSC's demonstrate unusually rapid rates of sequestration, important in applications such as detergent building
By way of technical background, but without being limited by theory, the sequestration properties of zeolites arises from their ability to ion-exchange The ion- exchange ability deπves from isomorphous substitution of Al(III) for Sι(IV) in classical zeolite frameworks which results in a net excess of negative charge in the aluminosilicate framework This requires counterbalancing by the inclusion of exchangeable cations Excess charge, and thus exchange capacity, is a function of aluminum content "Detergent" zeolites, according to WO 98/42622, have hitherto been restricted to the relatively short list of "high aluminum" zeolites By Lowenstem's Rule, the Si/Al ratio of a zeolite may not be lower than 1 0 and concomitantly, the aluminum content may not exceed 7 0 meq per gram for an anhydrous mateπal m the sodium form This capacity may alternatively be expressed as 197 mg CaO per gram zeolite (anhydrous) when water softening is the desired exchange reaction Zeolites demonstrating this maximum aluminum content include Zeolite A, high aluminum analogs of Zeolite X and high aluminum analogs of gismondine (often refeπed to as Zeolite B, P or MAP) Also according to WO 98/42622, while Zeolite A has been the "detergent zeolite" of choice for years, the possibility of employing a high aluminum version of gismondine- type mateπals in calcium sequestration has been known for more than a generation (USP 3.1 12,176 Haden et al ) and has recently found renewed interest (for example, USP 5,512.266 Brown, et al ) In addition to zeolites, the ability of silicates to complex ions such as calcium and especially magnesium has long been known and sodium silicate has long been employed as a cheap, low performance detergent builder More recently, complex silicates such as Hoechst SKS-6 have been developed which are claimed to be competitive with higher performance zeolites
Moreover, according to WO 98/42622, the capacity for silicates to complex ions such as calcium and magnesium is inversely proportional to silicate chain length and directly proportional to the electronic charge on that chain fragment Silicates depolymeπze with increasing alkalinity (See Fig 1 of WO 98/42622) At moderate pH (where wash cycles are conducted) silicates are polymenc However, at much higher pH's silica not only becomes predominantly monomeπc, but also that monomer may possess multiple charges If such small, highly charged fragments could be exposed to solutions beanng multivalent cations, very powerful high capacity sequestration agents would result The inventors of WO 98/42622 assert that they have created such a situation by isolating and stabilizing substantial concentrations of such species within zeolite cages where ions such as calcium and magnesium are free to enter from an aqueous environment (such as wash water) and react with these powerful sequestration agents
WO 98/42622 further discloses that HZSC compositions can be prepared by reacting a finely divided aluminum source such as a dπed aluminosilicate gel or powdered gibbsite and more preferably finely divided metakaohn with concentrated silicate solutions at pH values abov e 12 at temperatures ranging from about ambient to about 100°C and at atmospheric pressure It is crucial for the preparation of the HZSC compositions that the aluminum source must be added last to the reaction mixture Thus, if all the ingredients of the reaction mixture are added together and heated to crystallization temperature, a conventional zeolite of the pnor art will be formed, and the HZSC materials of WO 98/42622 will not be formed
According to WO 98/42622, it is even more desirable to prepare HZSC compositions by heating the reaction mixture at temperatures of from 50°C to 85°C before the addition of the aluminum source for a peπod of time of about 30 minutes or longer While not wishing to be bound by any theory of operation, it appears that heating the reaction mixture for about 30 minutes pnor to aluminum addition allows the silicate to depolymeπze and form the predominantly occluded silicate units previously discussed According to WO 98/42622. HZSC's can also be prepared by reacting finely divided metakaohn with concentrated sodium silicate solutions at pH values above 12 at temperatures ranging from about ambient to about 100°C and at atmospheπc pressure
WO 98/42622 also states a preference to use high purity metakaohns, especially those low in iron and titania, w hen color is a consideration For example, metakaohn having an Fe;O, content below 1 %, preferably below 0 5% by weight and a TiO, content below 2% by weight preferably below 1% bv weight are useful The metakaohn should be in powder form These powders may be prepared by removing grit and coarse impurities from kaolin ores, usually fractionating the degπtted crude, drying the resulting slurry of fractionated hydrous kaolin, pulverizing the dried matenal, calcining in conventional manner to produce metakaohn (see, for example, U S 3,1 12,176 (Haden et al )), and pulverizing the metakaohn by means of a hammer mill or the like U S 3,014,836 Proctor et al is cross-referenced herein for its disclosure of producing calcined kaolin pigments from an acidic (bleached) filter cake of kaolin by steps including drying, pulvenzmg, calcining and repulveπzing, in practice of this invention the procedures of Proctor et al must be modified by using lower calcination temperature to produce the desired metakaohn form of calcined clay The kaolin ore may be upgraded by means such as froth flotation, magnetic punfication. selectiv e flocculation, mechanical delammation, grinding or combinations thereof before drying, pulverization, calcination and repulvenzation In many commercial operations, a chemically dispersed slip of the kaolin is dried in a spray dryer, forming microspheres See, for example, U S Patent No 3,586,523 Fanselow et al The resulting microspheres of hydrous (uncalcined) kaolin are then pulveπzed, calcined and repulveπzed, as taught in the patent of Fanselow et al
Further according to WO 98/42622, the particle sizes of the hydrous kaohnite precursor of the metakaohn starting mateπal affect the size of the HZSC product Since HZSC products having a fine particle size are usually prefeπed, fine particle size metakaohns obtained from fine particle size hydrous kaolins are recommended These particle sizes are most frequently measured by kaolin producers as values obtained by sedimentation, typically using a Sedigraph® 5100 analyzer (supplied by Micromeretics Corporation) and the values are reported as "equivalent spherical diameter" (e s.d ) Use of other measunng instruments may give somewhat different values In Example 3 of WO 98/42622, reproduced below as "HZSC Synthesis Example 1", illustrative of the WO 98/42622 process, typical samples of the hydrous kaolm precursor of the metakaohn are about 90% by weight finer than 1 micron, e.s.d., as measured using the Sedigraph® 5100 instrument The high bπghtness hydrous kaolm used in this example can be prepared from a coarse white Georgia kaolm crude by steps compπsing degnttmg, froth flotation to remove colored impunties, mechanical delamination and fractionation The fractionated product, about 90% by weight finer than 1 micron e.s.d., can be recovered as a dispersed fluid aqueous slip that can be spray dried, pulveπzed, calcined to metakaohn condition and repulveπzed The particle size of the repulveπzed metakaohn is coarser than that of the hydrous kaolm HZSC compositions of WO 98 42622 can moreover be prepared by synthesizing those zeohtic molecular sieves that hav e a high Al:O,/SιO, molar ratio, e g., SiOJAUO, molar ratios in the range of 2 to 3 according to the teachings of the prior art, with the crucial exception that the aluminum source is added last to the reaction mixture. Species include type P (also refeπed to as type B), zeolite A. high alumina X types and chabazite analogs
After crystallization, the zeolite crystals are washed thoroughly with water, preferably deionized water, to remov e sodium and spunous silica from the crystal surfaces In some cases, some replacement of sodium by hydrogen may take place duπng washing The crystals can be washed w ith solutions other than those of pure water About 5 to 40% of the silica content of the washed crystals is due to the occluded silicate species, usually to 20% Thus, the total SιO2 analysis as determined by conventional chemical analytical means will exceed that of the SιO: that would be expected based on the framework silica content as indicated by x-ray powder patterns and 9Sι NMR analysis of the HZSC composition The occluded silicate portion of this silica is readily ascertained from the "Sι NMR peaks at about -81 to -85 ppm
29Sι NMR has become a standard technique in the analysis of zeolites The utility of this technique is based on the fact that different frequencies coπespond to different electronic environments around the silicon, typically affected in zeolites by the chemistry of neighbonng atoms and/or Si-O bond angles 29Sι NMR detects all the Si, not just that which is associated with long-range crystallinity This makes it sensitive to species that may not be detected by XRD HZSC Synthesis Example 1 (see Example 3 of WO 98/42622)
In order to prepare an improved builder, termed a Hybrid Zeohte-Sihca Composition (HZSC). based on a gismondine-type aluminosilicate. the following procedure is applied 1000 grams of fine particle size metakaohn obtained by calcining an ultrafme mechanically delaminated ground hydrous kaolin (90% by weight finer than 1 micron, e s d ), followed by pulvenzation is used The powdered metakaohn is blended into an alkaline silicate solution containing 702 grams of N- Brand® sodium silicate solution and 1064 grams of NaOH in 4800 grams of deiomzed water which have been mixed and preheated to 72°C The mixture is then reacted with vigorous stirnng at 72°C for eight hours at ambient pressure in an open stainless steel vessel The crystalline product of the reaction is filtered and washed three times with 2000-ml lots of 72°C deiomzed water The crystalline product is dried in a forced air oven at 100°C overnight The crystalline product is analyzed and found to have a gross chemical Si/Al molar ratio of approximately 1 15 (SiOVALO, = 2 30) An XRD powder pattern essentially identical to that of WO 98/42622 Example 1 and 2 (characteπstic of gismondine-type zeolites) is obtained This mateπal is a HZSC (Hybπd Zeohte-Sihca Composition) in accordance with WO 98/42622
Additionally, the sodium content of this material as synthesized is found to be essentially equal to that of the silica (Na/Si =1 01 ), and to be substantially above the aluminum content on a molar basis (Na/Al = 1 16) Generally, the aluminum content of a zeolite is expected to equal its cationic content in that each framework aluminum induces one net negative framework charge which is counterbalanced by cations in order to maintain electroneutrahty Extra sodium is a characteristic of HZSC and is believed to be the result of sodium in association with the occluded silicate species
The average particle size (50% by weight finer than) of the crystalline product is 5 5 microns as determined by a Sedigraph® 5100
HZSC Synthesis Example 2 - See (see Example 10 of WO 98/42622) In order to synthesize an improved builder, termed a Hybrid Zeohte-Sihca Composition, in this example based on a Zeolite A framework, an HZSC mateπal is prepared by the following procedure
An alkaline silicate solution is prepared by dissolving 175 0 grams of NaOH and 99 0 grams of N-Brand® sodium silicate in 522 8 grams deiomzed water After mixing and preheating the mixture to 80°C, 109 5 grams Metamax® metakaohn are added and the mixture reacted by stimng for one hour at 80°C in a constant temperature bath The resultant product is filtered and washed three times with 1000-ml lots of deiomzed water The sample is then dπed overnight in a forced air oven at 100°C The product of this example demonstrates a strong, clean XRD powder pattern characteπstic of Zeolite A This mateπal is then subjected to the hardness sequestration test of WO 98/42622 Example 7 The 15 second and 15 minute hardness removal readings are 43% and 51% respectively , showing that hardness sequestration is remarkably faster and substantially more thorough than that of unmodified Zeolite A The hybπd composition offers substantial advantages over comparable zeolites in both rate and amount of hardness removal
HZSC Synthesis Example 3 (see Example 13 of WO 98/42622) In order to prepare an improved builder, termed a HZSC, based on a gismondine- type structure, the following procedure is followed
An identical synthesis mixture to that of WO 98/42622 Example 12 is prepared but in a different order of addition/reaction Thus, 74 97 pounds of deiomzed water, 42 7 pounds of 50% NaOH solution and 14 12 pounds of N-brand Sodium silicate are combined and heated under agitation to 72°C in a stainless steel reactor After an equilibration period of 30 minutes to allow silicate depolymenzation, 20 0 pounds of Luminex brand metakaohn are added and the-mixture reacted under vigorous agitation for 8 hours at 72° C After the reaction penod, the product is washed and filtered on several large pan filters including multiple reslumes and nnses with substantial excess of deiomzed water
The powder XRD pattern for this product is that of a highly crystalline mateπal of a gismondine-type structure, consistent with that of WO 98/42622 Example 12 However, unlike Example 12 of WO 98/42622, 29Sι NMR shows a clear shoulder to the main peak at -81 to-85 ppm which is characteπstic of an HZSC Additionally, elemental analysis indicates the characteπstic elevated Si/Al ratio (Si/Al = 1 20) and sodium levels approaching molar silicon contents (Na Si - 1 01) and the charactenstic excess of sodium to aluminum on a molar basis (Na Al 1 21 )
With the NMR indication of occluded silicate, exhaustive calcium exchange is conducted as in WO 98/42622 Example 12 Analysis of the exhaustively exchanged sample yields 23 8% CaO, 43 2% SiO, and 31 4% Al,O3 on a dry weight basis Thus, the material contains approximately 7 20 meq/g Si, 6 16 meq/g Al and 8 49 meq/g Ca The Ca Al meq/g ratio approaching 1 4 is consistent with that of an HZSC and not consistent with that of a zeolite which is limited to 1 0 The calcium capacity approaching 8 5 meq/g is consistent with an HZSC and inconsistent with the 7 0 meq/g theoretical limit noted for zeolites The product of this example is an HZSC and not merely a high aluminum version of Zeolite P as prepared in WO 98/42622 Example 12 in spite of the fact that both are preparable using identical reactants, reaction times and temperatures and crystalhzation/washmg equipment It is therefore apparent that the order of reactant addition and probably full depolymeπzation of silicate are imperative in the formation of HZSC
HZSC Synthesis Example 4 (see Example 14 of WO 98/42622) In order to prepare an improved builder, termed a HZSC, based on a gismondine- type structure, and to demonstrate that aluminum sources other than metakaohn may be employed in the formation of HZSC, the following procedure is followed
An aluminosilicate gel with gross composition approaching 1 1 Si/Al is prepared bv dissolving 2 95 kg of NaAlO-,, in 14 0 kg deiomzed water To this is added 7 45 kg N- Brand® sodium silicate The resultant gel is beaten with a high shear blade to a homogeneous appeaπng consistency The homogenized gel is poured into stainless steel pans and is dned in an oven overnight at 100° C A portion of this dned gel is pulvenzed and employed as dried aluminosilicate reactant Thus, 89 grams of NaOH and 88 grams of N-Brand® sodium silicate are dissolved in 600 grams of deiomzed water and brought to a temperature of 72° C under agitation After equilibrating, 160 grams of the dried gel aluminosilicate reactant are added to the mixture under agitation and crystallized at 72° C for 5 5 hours The sample is washed and vacuum filtered with an excess of deiomzed water and dned at 100° C overnight The XRD powder pattern for this material is that of a highly crystalline gismondine-type structure The 29Sι NMR spectrum shows a clear shoulder to the main peak at -81 to -85 ppm, characteπstic of HZSC
The HZSC matenal produced in accordance with this example is tested in accordance with the procedure set forth in WO 98/42622 Example 7
The results obtained indicate that the matenal obtained by this example possess the same rapid cation exchange removal I e 48% in 15 seconds and 82% in 15 minutes as is possessed by the novel matenal of WO 98/42622 Example 3 (HZSC Synthesis
Example 1 supra) Thus, this example establishes that aluminum sources other than metakaohn may be employed the synthesis of HZSC matenals
Equilibrium ion exchange capacity of a HZSC (see WO 98/42622 Example 5)
The full sequestration capacity of the crystalline product of HZSC Synthesis
Example 1 (WO 98/42622 Example 3) at pH 10 (typical of wash water) is established by exchanging 3 0 grams of the matenal twice with 6 0 grams of CaCU 2H,O dissolved in 400 ml deiomzed water The exchanges are each conducted for approximately 45 minutes at a temperature of 100°C The sample is filtered and washed six times with approximately 100 cc deiomzed water to remove any spunous CaCU The sample is then dned at 100°C for approximately 12 hours The sample is then subjected to conventional X-ray fluorescence chemical analysis techniques The analysis reveals 23 5 weight % CaO, 42 0 weight % SιO„ 31 9 weight % Nl2O3 and approximately 1 0 % other mateπals on a dry weight basis Thus, the material contains 7 0 meq/g Si. 6 26 meq/g Al and 8 37 meq/g Ca Not only does this indicate 34% more calcium than can be accounted for by exchange with the available aluminum, it is nearly 20% greater than the 7 0 meq capacity theoretically possible for ion-exchange into a maximum aluminum zeolite In terms of mg CaO/g anhydrous zeolite (as in the Henkel test) this is a capacity of 236, well above the theoretical zeolite maximum of 197 Clearly, zeolite ion-exchange is not the only sequestration mechanism operating for the HZSC
The Synthesis Examples supra demonstrate the preparation of the WO 98/42622 materials denoted "HZSC" for Hybrid Zeohte-Sihca Compositions which demonstrate remarkable speed and thoroughness of multivalent cation complexation This is especially useful in water softening/detergent building applications These properties are asserted in WO 98/42622 to deπve from the ability of zeolite cages to occlude small, highly charged silicate species Whatever the theory with respect to the structure of these compositions, the zeolite and entrained or occluded silicate appear to act in concert as a hybπd composition showing properties that neither zeolites, specifically tested silicates, nor physical blends of the two demonstrate
In order to further demonstrate that the HZSC 29Sι NMR peaks at about -81 to -85 ppm are due to occluded silicate in HZSC compositions, samples of 2 MAP products marketed by Crosfield under the tradenames Zeocros 180 and Doucil A- 24 are obtained and tested as received XRD powder patterns for both samples indicate measurable hydroxysodahte as evidenced by peaks at 14 0, 24 3 and 25 1 degrees 2 theta, WO 98/42622 Figures 4a, b A sample of high aluminum zeolite P made in accordance with the method of Haden (U S Patent 3,1 12,176) is found to contain no discernible sodahte as determined by XRD Representative samples of HZSC, including those of WO 98/42622 Examples 3 and 13, are examined by XRD and in no case is measurable sodahte present
Pure zeolite MAP as prepared by the Haden method is subjected to 29Sι NMR analysis It is found free of the shoulder at -81 to -85 ppm characteristic of HZSC, WO 98/42622 Figure 5a
In a publication by Can, S W , Gore, B and Anderson, M W , Chem Mater 1997, Vol 9, pgs 1927- 1932, it has been noted that as-received Crosfield zeolite MAPs contain an NMR shoulder near that characteπstic of HZSC With no such shoulder present in the pure MAP of Haden, an alternativ e explanation to Can et al's claim of the shoulder being due to surface hvdroxyl groups was sought by the inventors of WO 98/42622 Thus, they obtained a sample of hydroxysodahte and found it to have 1 large NMR peak centered at about -85 0 ppm Published values for sodahte from about - 83 5 to -85 ppm. with the v anation largely due to the exact degree of hydration (see High Resolution Solid State NMR of Silicates and Zeolites. G Engelhardt and D Michel, John Wilev & Sons Chichester 1987) This hydroxysodahte was added by the WO 98/42622 inventors at a 1 % level to the pure MAP and resulted in an XRD pattern, WO 98/42622 Figure 4c, essentially identical to the sodahte-contaminated MAP of the commercial Crosfield products, WO 98/42622 Figures 4a, b The WO 98/42622 inventors subjected this mixture to 29Sι NMR analysis and contrasted it to the pure MAP of Haden, sodahte contaminated Crosfield MAP, and HZSC of WO 98/42622 Example 3 Pure MAP has no shoulder in the region of -83 ppm. noted by Can et al , (WO 98/42622 Figure 5a) Addition of 1% sodahte yielded a spectrum, WO 98/42622 Figure 5c, with the shoulder essentially identical (although weaker) to that of the sodahte-contaminated Crosfield product, WO 98/42622 Figure 5d Thus, the most reasonable explanation for Can et al's observations is sodahte contamination in the as-received Crosfield MAPs HZSC is free of these contaminants and yet still contains the characteristic NMR shoulder It is most reasonable to assign this shoulder to occluded silicates which are also expected in this regime as no sodahte is present
Hardness Sequestration Rate (See WO 98/42622 Example 7) In order to assess the relative performance of HZSC-type mateπals versus zeolite as water softening agents in mixtures resembling wash water, sequestration tests are conducted in mixed calcium/magnesium solutions at 35°C and pH 10 1 5 liter charges of 1 03 molar calcium plus magnesium solutions are buffered with glycme solutions to a pH of 10 The Ca Mg molar ratio is established at 3 1 The test hardness solutions are heated to 35°C in a constant temperature bath at which point 0 45 gram charges of air- equihbrated HZSC or reference builders are added and the test mixtures agitated by an overhead stiner at a rate of 200 rpm Total hardness concentration is monitored by an Orion Model 9332BN total hardness electrode connected to an Onon Model 720A pH meter Both the "instantaneous" and "equihbnum" hardness removal of a builder can be cntical parameters depending upon the particular environment in which they are employed Hardness removal at 15 seconds is taken as indicative of "instantaneous" hardness removal and readings at 15 minutes are taken as a measurement of "equihbnum" properties HZSC mateπals as well as reference materials are sub]ected to this test and the results are summanzed as Table 1
TABLE 1 Timed Hardness Removal by HZSC-type builders and some reference materials
Sample Hardness Removed Hardness Removed 15 seconds 15 Minutes
HZSC Mateπals Svnth Ex ϋ
HZSC1 * 48% 82% 1
HZSC2** 43% 51% 2
HZSC3* 48%, 82% 4 * gismondine-type hybnd with occluded silicate ** zeolite A-type hybπd with occluded silicate
Reference Materials (See WO 98/42622) Zeolite A 10% 41%
Zeolite MAP 18% 55%
COH 6% 48%
Note with respect to percentage improvement levels discussed heieinabove,
HZSC1 and HZSC3 have a 15-second hardness removal improvement, as compared with zeolite A, of ((48 - 10) / 10) x 100 = 380 0% HZSC1 and HZSC3 have a 15-mιnute hardness removal improvement, as compared w ith zeolite A, of ((82 - 41 ) / 41 ) x 100 = 100 0% This test indicates that HZSC matenals at 15 seconds are more rapid than the reference mateπals (conventional zeolites) and, at least in the case of HZSC having gismondine-type structure, have improved 15-mιnute removal data than the reference mateπals Note, however, that if the HZSC materials have reduced crystal size relative to the reference matenals, an improvement in 15 sec hardness removal is expected Since, for the zeolite A-type HZSC, the 15-mιnute removal data is not substantially improved over the reference matenals, this leaves some question as to the value of the overall water-softening improvement offered by the zeolite A-type HZSC Such overall value is, however, not only a function of water softening in a simple test as given above, but also is dependent on the effective cleaning performance in a fully-formulated laundry detergent This latter performance is affected by the presence of laundry detergent adjuncts In short, the manufacturer of builder matenals is in a position to suggest builder matenals to be evaluated by the detergent formulator. but is not well-placed to accurately predict through simple tests which mateπals are most effective m practice Detergent compositions
Detergent compositions of the present invention include a builder svstem that comprises, at least in part, the hybπd aluminosilicate as hereinbefore descπbed. togetner w ith specified detergent adjuncts
When the builder system does not differ from WO 98/42622, the present inventive detergent compositions are required to constitute a combination of a WO 98/42622 hybπd material and at least one selected detergent adjunct not disclosed or suggested in WO 98/42622 These selected adjuncts, especially advantageous in conjunction with hybnd builders, are descπbed in detail hereinafter as "Class I detergent adjuncts"
When the builder system differs from one disclosed in WO 98/42622. more particularly when the hybrid builder matenal is not one specifically disclosed in WO 98/42622, the present inventive detergent compositions compnse at least the hybπd builder mateπal and one or more broadly defined detergent adjuncts These more broadly defined detergent adjuncts can include any detergent adjunct or adjunct class disclosed in WO 98/42622 and the associated literature references, as well as any Class I detergent adjunct Of course, prefeπed Class I adjuncts are included in all the prefened embodiments of all detergent compositions herein at levels of from about 0 0001% to about 99% of the detergent composition Moreover, the prefened detergent compositions preferably include at least two Class I detergent adjuncts, more preferably at least three such adjuncts
Prefened detergent compositions according to the invention may contain (a) from 2 to 60 wt % of one or more detergent surfactants, (b) from 10 to 80 wt % of one or more detergencv builders, including the hybrid aluminosilicate, (c) from 5 to 40 wt % of a bleach system, (d) from 0 05 to 10% of enzyme or mixtures thereof, and (e) optionally other detergent ingredients to 100 wt % Bleach-free embodiments are, of course, also contemplated
Highly prefened detergent compositions herein compnse, in addition to (a) the hybnd builder, (b) from about 0 1% to about 99% of at least one detersive adjunct selected from the group consisting of (I) detersive surfactants having at least one branched, preferably mid-chain branched hydrophobe, (n) organic polymenc mateπals selected from polyacetal carboxylates hydrophobically modified polyacrylates, terpolymers compπsing acrylate or maleate, polymenc soil release agents, polymenc dye transfer inhibitors, polyamines, polyimines, polymenc rheology modifiers, and mixtures thereof, (in) oxygen bleach promoting mateπals selected from hydrophobic bleach activators; organic bleach boosters; transition-metal bleach catalysts; photobleaches and mixtures thereof; (iv) faoric care promoting agents other than said organic polymeric materials; and (v) mixtures of (i) - (iv). Sources and examples of such materials have been given in the summary hereinabove. Class I detergent adjuncts
Biodegradably branched surfactant
The present invention includes important embodiments comprising at least one biodegradably branched and/or crystallinity disrupted and/or mid-chain branched surfactant or surfactant mixture. The terms "biodegradably branched" and/or "crystallinity disrupted" and/or "mid-chain branched" (acronym "MCB" used hereinafter) indicate that such surfactants or surfactant mixtures are characterized by the presence of surfactant molecules having a moderately non-linear hydrophobe; more particularly, wherein the surfactant hydrophobe is not completely linear, on one hand, nor is it branched to an extent that would result in unacceptable biodegradauon. The prefened biodegradably branched surfactants are distinct from the known commercial LAS, ABS, Exxal, Lial, etc. types, whether branched or unbranched. The biodegradably branched materials comprise particularly positioned light branching, for example from about one to about three methyl, and/or ethyl, and or propyl or and/or butyl branches in the hydrophobe, wherein the branching is located remotely from the surfactant headgroup, preferably toward the middle of the hydrophobe. Typically from one to three such branches can be present on a single hydrophobe, preferably only one. Such biodegradably branched surfactants can have exclusively linear aliphatic hydrophobes, or the hydrophobe- can include cycloaliphatic or aromatic substitution. Highly prefened are MCB analogs of common linear alkyl sulfate, linear alkyl poly(alkoxylate) and linear alkylbenzenesulfonate surfactants, said surfactant suitably being selected from mid-chain-C,-C4-branched C8- Cl i(-alkyl sulfates, mid-chain-C,-C4-branched C8-C1 s-alkyl ethoxylated, propoxylaied or butoxylated alcohols, mid-chain-C,-C -branched -C^-alkyl ethoxysulfates, mid-chain- CrC4-branched C8-C,6-alkyl benzenesulfonates and mixtures thereof. When anionic, the surfactants can in general be in acid or salt, for example sodium, potassium, ammonium or substituted ammonium, form. The biodegradably branched surfactants offer substantial improvements in cleaning performance and/or usefulness in cold water and/or resistance to water hardness and/or economy of utilization. Such surfactants can, in general, belong to any known class of surfactants, e.g., anionic, nonionic, cationic, or zwitterionic. The biodegradably branched surfactants are synthesized through processes of Procter & Gamble, Shell, and Sasol. These surfactants are more fully disclosed in WO98/23712 A published 06/04/98; WO97/38957 A published 10/23/97; WO97/38956 A published 10/23/97, WO97/39091 A published 10/23/97. WO97/39089 A published 10 23/9 WO97/39088 A published 10/23/97, WO97O9087 Al published 10/23/97, WO97/38972 A published 1C23/97, WO 98/23566 A Shell, published 06/04/98, technical bulletins of Sasol, and the following pending patent applications assigned to Procter & Gamble [ add complete list of pending cases]
Prefeπed biodegradably branched surfactants herein in more detail include MCB surfactants as disclosed in the following references
WO98/23712 A published 06/04/98 includes disclosure of MCB noniomc surfactants including MCB pnmary alkyl polyoxyalkylenes of formula (1) CH3CHJCH:)ttC(R)H(CH2) C(R')H(CH2),C(R2)H(CH2)z(EO/PO)mOH (1 ), where the total number of carbon atoms in the branched pnmary alkyl moiety of this formula, including the R, R' and R' branching, but not including the carbon atoms in the EO/PO alkoxy moiety, is preferably 14-20, and wherein further for this surfactant mixture, the average total number of carbon atoms in the MCB pnmary alkyl hydrophobe moiety is preferably 14 5-17 5, more preferably 15-17, R, R1 and R2 are each independently selected from hydrogen and 1 -3C alkyl, preferably methyl, provided R, R1 and R: are not all hydrogen and, when z is 1 , at least R or R1 is not hydrogen, w is an integer of 0-13, x is an integer of 0-13, y is an integer of 0-13, z is an integer of at least 1 , w+x+y+z is 8-14, and EO/PO are alkoxy moieties preferably selected from ethoxy, propoxy and mixed ethoxy/propoxy groups, where m is at least 1 , preferably 3-30, more preferably 5-20, most preferably 5-15 Such MCB noniomcs can alternately include butylene oxide denved moieties, and the -OH moiety can be replaced by any of the well-known end-capping moieties used for conventional noniomc surfactants
WO97/38957 A published 10/23/97 includes disclosure of mid- to near-mid-chain branched alcohols of formulae R-CH2CH2CH(Me)CH-R'-CH2OH (I) and HOCH,-R-CH2- CH2-CH(Me)-R' (II) compπsing (A) dimeπsing alpha -olefins of formula RCH=CH, and R'CH=CH2 to form olefins of formula R(CH2),-C(R')=CH2 and R'(CH2)2-C(R)=CH2, (B) (0 lsomeπsing the olefins and then reacting them with carbon monoxide/hydrogen under Oxo conditions or (n) directly reacting the olefins from step (A) with CO/H2 under Oxo conditions In the above formulae, R, R1 = 3-7C linear alkyl WO97/38957 A also discloses (l) production of MCB alkyl sulphate surfactants by sulphating (I) or (II), (n) preparation of MCB alkylethoxy sulphates which compnses ethoxylating and then sulphating (I) or (II), (in) preparation of MCB alkyl carboxylate surfactants which compnses oxidising (I) or (II) or their aldehyde intermediates and (iv) preparation of MCB acyl taurate, MCB acyl isethionate, MCB acyl sarcosinate or MCB acyl N- methylglucamide surfactants using the branched alkyl carboxylates as feedstock WO97β8956 A published 10/23 '97 discloses the preparation of mid- to near mid- cham branched alpha olefins which is effected by (a) prepanng a mixture of carbon monoxide and hydrogen, (b) reacting this mixture in the presence of a catalyst under Fischer-Tropsch conditions to prepare a hydrocarbon mixture compπsing tne descπbed olefins, and (c) separating the olefins from the hydrocarbon mixture WO97 38956 A further discloses the preparation of mid- to near mid-chain branched alcohols by reacting the olefins described with CO/H, under Oxo conditions These alcohols can be used to prepare ( 1 ) MCB sulphate surfactants by sulphating the alcohols, (2) MCB alkyl ethoxy sulphates by ethoxylating, then sulphating. the alcohols, or (3) branched alkyl carboxylate surfactants by oxidising the alcohols or their aldehyde intermediates The branched carboxylates formed can be used as a feedstock to prepare branched acyl taurate, acyl isethionate, acyl sarcosinate or acyl N-methylglucamide surfactants, etc
WO97'39091 A published 10/23/97 includes disclosure of a detergent surfactant composition compπsing at least 0 5 ( especially 5, more especially 10, most especially 20) wt% of longer alkyl chain, MCB surfactant of formula (I) A-X-B (I) wherein A is a 9-22 (especially 12-18) C MCB alkyl hydrophobe having (1) a longest linear C chain attached to the X-B moiety of 8-21 C atoms, (11) 1-3C alkyl moιety(s) branching from this longest linear chain, (111) at least one of the branching alkyl moieties attached directly to a C of the longest linear C chain at a position within the range of position 2 C, counting from C 1 which is attached to the Cr B moiety , to the omega-2 carbon (the terminal C minus 2C), and (iv) the surfactant composition has an average total number of C atoms in the A-X moiety of 14.5-17.5 ( especially 15-17), and B is a hydrophihc (surfactant head- group) moiety preferably selected from sulfates, sulfonates, polyoxyalkylene ( especially polyoxyethylene or polyoxypropylene), alkoxylated sulphates, polyhydroxy moieties, phosphate esters, glycerol sulphonates, polygluconates, polyphosphate esters, phosphonates, sulphosuccinates, sulphosuccinates, polyalkoxylated carboxylates, glucamides, tauπnates, sarcosinates, glycinates, lsethionates, monoJdi-alkanol-amides, monoalkanolamide sulphates, diglycol-amide and their sulphates, glyceryl esters and their sulphates, glycerol ethers and their sulphates, polyglycerol ether and their sulphates, sorbitan esters, polyalkoxylated sorbitan esters, ammomo-alkane-sulphonates, amidopropyl betames, alkylated quat , alkylated/poly-hydroxyalkylated (oxypropyl) quat., lmidazohnes, 2-yl succinates, sulphonated alkyl esters and sulphonated fatty acids; and X- IS -CH2- or -C(O)- WO97β9091 A also discloses a laundry detergent or other cleaning composition compnsing (a) 0 001 -99% of detergent surfactant (I), and (b) 1 - 99 999% of adjunct ingredients WO97/39089 A published 10 23/97 includes disclosure of liquid cleaning compositions compπsing (a) as part of surfactant system 0 1 -50 (especially 1 -40) wt % of a mid-chain branched surfactant of formula (I), (b) as the other part of the surfactant system 0 1-50 wt% of co-surfactant(s), (c) 1 -99 7 wt% of a solvent, and (d) 0 1 -75 wt% of adjunct ingredients Formula (I ) is A-CH.-B wherein A = 9-22 (especially 12-18) C MCB alkyl hydrophobe having (1) a longest linear C chain attached to the X-B moiety of 8-21 C atoms, (n) 1-3C alkyl moιety(s) branching from this longest linear chain, (in) at least one of the branching alkyl moieties attached directly to a C of the longest linear C chain at a position within the range of position 2 C, counting from Carbon No 1 which is attached to the CH2B moiety, to the omega-2 carbon (the terminal C minus 2C), and (iv) the surfactant composition has an average total number of C atoms the A-λ moiety of 14 5-17 5 ( especially 15-17), and B is a hydrophihc moiety selected from sulphates, polyoxyalkylene (especially polyoxyethylene and polyoxypropylene) and alkoxylated sulphates WO97/39088 A published 10 23/97 includes disclosure of a surfactant composition comprising 0 001 -100% of MCB pnmary alkyl alkoxylated sulphate(s) of formula (I)
CH,CH2(CH) CHR(CH2) CHR'(CHNCHR2(CH )OSO3M (I) wherein the total number of C atoms in compound (I) including R. R1 and R , is preferably 14-20 and the total number of C atoms in the branched alkyl moieties preferably averages 14 5-17 5 (especially 15-17), R, R' and R: are selected from H and 1 -3C alkyl ( especially Me) provided R, R1 and R2 are not all H, w hen z = 1 at least R or R' is not H, M are cations especially selected from Na. K, Ca, Mg. quaternary alkyl ammonium of formula N^R R'R6 (II), M is especially Na and/or K, R\ R R\ R( are selected from H, 1-22C alkylene, 4-22C branched alkylene. 1 -6C alkanol, 1-22C alkenylene, and/or 4-22C branched alkenylene, w , x, y = 0-13, / is at least 1 , w +x+y+z = 8-14 WO97/39088 A also discloses (1 ) a surfactant composition compπsing a mixture of branched pnmary alkyl sulphates of formula (I) as above M is a w ater-soluble cation, When R"1 is 1 -3C alkyl, the ratio of surfactants having z = 1 to surfactants having z = 2 or greater is preferably at least 1 1 ( most especially 1 100), (2) a detergent composition compπsing (a) 0 001-99% of MCB pnmary alkyl alkoxylated sulphate of formula (III) and/or (IV) CHJCH2)aCH(CH3)(CH2)bCH >SO,M (III)
CH3(CH2)dCH(CH,)(CH2)cCH(CH1)CH2OSO,M (IV) wherein a, b, d, and e are integers, preferably a+b = 10-16, d+e = 8-14 and when a+b = 10, a = 2-9 and b = 1-8, when a+b = 1 1, a = 2-10 and b = 1 -9, when a+b = 12, a = 2-1 1 and b = 1 -10, when a+b = 13, a = 2-12 and b = 1 -1 1 , when a+b = 14, a = 2-13 and b = 1-12, when a+B = 15, a = 2- 14 and b = 1-13, when a+b = 16, a = 2-14 and b = 1 -14. when d+e = 8. d = 2-7 and e = 1 - 6, when d+e = 9, d = 2-8 and e = 1 -7, when d-^e = 10, d = 2-9 and e = 1 -8, when d+e = 1 1 , d = 2-10 and e = 1 -9, when d+e = 12, d = 2-1 1 and e = 1-10, when d+e = 13. d = 2-12 and e = 1 -1 1 , when d+e = 14, d = 2-13 and e = 1-12, and (b) 1 -99 99 wt% of detergent adjuncts, (3) a mid-chain branched primary alkyl sulphate surfactant of formula(V)
OLCH2(CHNCHR'(CH2) CHR2(CH_NOSO3M (V) wherein x, y = 0-12, z is at least 2, x+y+z = 1 1 -14, R1 and R' are not both H, when one of R' or R" is H, and the other is Me, x + y +z is not 12 or 13, and when R' is H and R2 is Me, x + y is not 1 1 when z = 3 and x + y is not 9 when z = 5, (4) Alkyl sulphates of formula (III) in which a and b are integers and a = b = 12 or 13, a = 2-1 1, b = 1 -10 and M is Na, K, and optionally substituted ammonium, (5) alkyl sulphates of formula (IV) in which d and e are integers and d = e is 10 or 1 1 and when d = e is 10. d = 2-9 and e = 1-8, when d = e = 1 1, d = 2-10 and e = 1 -9 and m is Na. K. optionally substituted ammonium ( especially Na), (6) methyl branched primary alkyl sulphates selected from 3-, 4- 5-, 6-, 7-, 8-, 9-, 10-, 1 1 -, 12- or 13- methyl pentadecanol sulphate, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 1 1-, 12-, 13-, or 14- methyl hexadecanol sulphate, 2.3-, 2,4-, 2.5-. 2.6-. 2,7-, 2,8-, 2,9-, 2,10-, 2,1 1 -, 2,12-mefhyl tetradecanol sulphate, 2.3-. 2,4-, 2.5-. 2.6-. 2,7-. 2,8-, 2,9-, 2,10-, 2,1 1 -, 2,12-, or 2,13- methyl pentadecanol sulphate and/or mixtures of these compounds
WO97/39087 A published 10/23 97 includes disclosure of a surfactant composition comprising 0 001 -100% of mid-chain branched pnmary alkyl alkoxylated sulphate(s) of formula (1) wherein that total number of C atoms in compound (I) including R, R' and R\ but not including C atoms of EO/PO alkoxy moieties is 14-20 and yhe total number of C atoms in branched alkyl moieties averages 14 5-17 5 (especially 15-17), R, Rl and R2 = H or 1-3C alkyl ( especially Me) and R, R' and R2 are not all H, when z = 1 at least R or R' is not H, M = cations especially selected from Na, K, Ca, Mg, quaternary alkyl amines of formula (II) ( M is especially Na and/or K) R3, R4, R\ R6 = H, 1-22C alkylene, 4-22C branched alkylene. 1 -6C alkanol, 1-22C alkenylene, and/or 4-22C branched alkenylene, w , x, y = 0-13, z is at least 1 , w+x+y+z = 8-14, EO/PO are alkoxy moieties, especially ethoxy and/or propoxy, m is at least 0 01. especially 0 1-30, more especially 0 5-10, most especially 1 -5 Also disclosed are (1 ) a surfactant composition compπsing a mixture of branched primary alkyl alkoxylated sulphates of formula (I) When R: = 1-3C alkyl, the ratio of surfactants having z = 2 or greater to surfactant having z = 1 is at least 1 1 , especially 1 5 1 , more especially 3 1, most especially 4 1 , (2) a detergent composition compπsing (a) 0 001 -99% of mid-cha branched pnmary alkyl alkoxylated sulphate of formula (III) and/or (IV) M is as above, a, b, d, and e are integers, a+b = 10-16. d+e = 8-14 and when a+b = 10, a = 2-9 and b = 1-8, when a+b = 1 1 , a = 2- 10 and b = 1-9, when a+b = 12. a = 2-1 1 and b = 1-10, when a+b = 13. a = 2-12 and b = 1-1 1 , when a+b = 14, a = 2-13 and b = 1 -12, when a+b = 15, a = 2-14 and b = 1 -13 when a+b = 16, a = 2-14 and b = 1-14, when d+e = 8, d = 2-7 and e = 1-6, when d+e = 9, d = 2- 8 and e = l -~. when d-re = 10, d = 2-9 and e = 1-8, when d+e = 1 1, d = 2-10 and e = 1 -9, when d+e = 12, d = 2-1 1 and e = 1 -10. when d+e = 13, d = 2-12 and e = 1-1 1 , when d+e = 14, d = 2-13 and e = 1 -12. and (b) 1 -99 99 wt% of detergent adjuncts, (3) a MCB pnmary alkyl alkoxylated sulphate surfactant of formula(V) Rl, R2, M, EO/PO, m as above, x,y = 0-12, z is at least 2, x+y+z = 1 1-14, (4) a mid-cham branched alkyl alkoxylated sulphate of formula (III) in which a = 2-1 1 , b = 1 -10, a+b = 12 or 13, M, EO/PO and m are as above, (5) a mid-chain branched alkyl alkoxylated sulphate compound of formula (IV) in which d+e = 10 or 1 1 , when d+e = 10, d = 2-9 and e = 1-8 and when d+e = 1 1 , d = 2-10 and e = 1 -9 M is as above ( especially Na), EO/PO and m are as above, and (6) methyl branched pnmary alkyl ethoxylated sulphates selected from 3-, 4- 5-, 6-, 7-, 8-, 9-, 10-, 1 1-, 12- or 13- methyl pentadecanol ethoxylated sulphate, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 1 1-, 12-, 13-. or 14- methyl hexadecanol ethoxylated sulphate, 2,3-, 2,4-, 2,5-, 2,6-, 2,7-, 2,8-, 2,9-, 2,10-, 2.1 1 -, 2.12-methyl tetradecanol ethoxylated sulphate, 2,3-, 2,4-, 2,5-, 2,6-, 2,7-, 2,8-, 2.9-, 2,10-, 2,1 1-, 2,12-, or 2,13- methyl pentadecanol ethoxylated sulphate and/or mixtures of these compounds The compounds are ethoxylated with average degree of ethoxylation of 0 1 -10 WO97 8972 A published 10 23/97 includes disclosure of a method for manufacturing longer chain alkyl sulphate surfactant mixture compositions compπsing (a) sulphating with SO,, preferably in a falling film reactor, a long chain aliphatic alcohol mixture having an average carbon chain length of at least 14 5-17 5, the alcohol mixture compπsing at least 10%, preferably at least 25%, more preferably at least 50% still more preferably at least 75%, most preferably at least 95% of a MCB aliphatic alcohol having formula (I), where R,R'.R2 = H or 1 -3C alkyl, preferably methyl, provided R, R1 and R are not all H. and when z = 1 , at least R or R' is not H, w,x,y = integers 0-13, z = integer of at least 1. and w+x+y+z = 8-14, where the total number of carbon atoms in the branched primary, alkyl moiety of formula (I), including the R, R1 and R2 branching, is 14-20, and where further for the alcohol mixture the average total number of carbon atoms in the branched pnmary alkyl moieties having formula (I) is > 14 5-17 5, preferably, >15-17, and (b) neutralising the alkyl sulphate acid produced by step (a), preferably using a base selected from KOH, NaOH, ammonia, monoethanolamine, tπethanolamine and mixtures of these Also disclosed is a method for manufactuπng longer chain alkyl alkoxylated sulphate surfactant mixture compositions, compnsing alkoxylating the specified long chain aliphatic alcohol mixture, sulphating the resulting polyoxyalkvlene alcohol with SO,, and neutralising the resulting alkyl alkoxvlate sulphate acid Alternatively, the alkyl alkoxylated sulphates may be produced directly from the polyoxyalkylene alcohol by sulphating with SO, and neutralising
WO 98/23566 A Shell, published 06/04/98 discloses branched pnmary alcohol compositions having 8-36 C atoms and an average number of branches per mol of 0 7-3 and compnsing ethyl and methyl branches Also disclosed are (1 ) a branched primary alkoxylate composition preparable by reacting a branched primary alcohol composition as above with an oxirane compound, (2) a branched pnmary alcohol sulphate preparable by sulphating a pnmary alcohol composition as above, (3) a branched alkoxylated pnmary alcohol sulphate preparable by alkoxylating and sulphating a branched alcohol composition as above, (4) a branched pnmary alcohol carboxylate preparable by oxidising a branched pnmary alcohol composition as above, (5) a detergent composition compπsing (a) surfactant! s) selected from branched primary alcohol alkoxylates as in (1 ), branched primary alcohol sulphates as in (2), and branched alkoxylated pnmary alcohol sulphates as in (3), (b) a builder, and (c) optionally addιtιve(s) selected from foam control agents, enzymes, bleaching agents, bleach activators, optical bnghteners. co-builders, hydrotropes and stabilisers The pnmary alcohol composition, and the sulphates, alkoxylates, alkoxy sulphates and carboxylates prepared from them exhibit good cold water detergency and biodegradabihty Biodegradably branched surfactants useful herein also include the modified alkylaromatic, especially modified alkylbenzenesulfonate surfactants described in copending commonly assigned patent applications [ INSERT MLAS Case REFERENCES mcl 7303P, 7304P and the earlier filed MLAS cases] In more detail, these surfactants include (P&G Case 6766P) alkylarylsulfonate surfactant systems comprising from about 10% to about 100% by weight of said surfactant system of two or more crystalhnity-disrupted alkylarylsulfonate surfactants of formula (B-Ar-D)a(Mcl+)b wherein D is SO3", M is a cation or cation mixture, q is the valence of said cation, a and b are numbers selected such that said composition is electroneutral, Ar is selected from benzene, toluene, and combinations thereof, and B compnses the sum of at least one pnmary hydrocarbyl moiety containing from 5 to 20 carbon atoms and one or more crystalhnity-disrupting moieties wherein said crystalhmty-disruptmg moieties interrupt or branch from said hydrocarbyl moiety, and wherein said alkylarylsulfonate surfactant system has crystallinity disruption to the extent that its Sodium Critical Solubility Temperature, as measured by the CST Test, is no more than about 40°C and wherein further said alkylarylsulfonate surfactant system has at least one of the following properties percentage biodegradation, as measured by the modified SCAS test, that exceeds tetrapropylene benzene sulfonate, and weight ratio of nonquaternarv to quaternary carbon atoms m B of at least about 5 1
Such compositions also include (P&G Case 7303P) surfactant mixtures compπsing (preferably, consisting essentially of) (a) from about 60% to about 95% bv weight (preferably from about 65% to about 90%, more preferably from about 70% to about 85%) of a mixture of branch rmula (1)
(I) wherein L is an acyclic aliphatic moiety consisting of carbon and hydrogen and having two methyl termini, and wherein said mixture of branched alkylbenzenesulfonates contains two or more (preferably at least three, optionally more) of said compounds differing in molecular weight of the anion of said formula (I) and wherein said mixture of branched alkylbenzenesulfonates is characterized by an average carbon content of from about 10 0 to about 14 0 carbon atoms (preferably from about 1 1 0 to about 13 0. more preferably from about 1 1 5 to about 12 5). wherein said average carbon content is based on the sum of carbon atoms in R', L and R\ (preferably said sum of carbon atoms in R', L and R" IS from 9 to 15, more preferably, 10 to 14) and further, wherein L has no substituents other than A, R1 and R:, M is a cation or cation mixture (preferably selected from H, Na, K, Ca, Mg and mixtures thereof, more preferably selected from H, Na, K and mixtures thereof, more preferably still, selected from H, Na, and mixtures thereof) having a valence q (typically from 1 to 2, preferably 1), a and b are integers selected such that said compounds are electroneutral (a is typically from 1 to 2, preferably 1 , b is 1 ), R1 is C,-C, alkyl (preferably C,-C, alkyl, more preferably methyl), R2 is selected from H and C,-C, alkyl (preferably H and C,-C2 alkyl, more preferably H and methyl, more preferably H and methyl provided that in at least about 0.5, more preferably 0 7, more preferably 0 9 to 1.0 mole fraction of said branched alkylbenzenesulfonates R2 is H), A is a benzene moiety (typically A is the moiety -C6H4- , with the SO3 moiety of Formula (I) in para- position to the L moiety, though in some proportion, usually no more than about 5%, preferably from 0 to 5% by weight, the SO, moiety is ortho- to L), and (b) from about 5% to about 60% by weight (preferably from about 10% to about 35%, more preferably from about 15% to about 30%) of a mixture of nonbranched alkylbenzenesulfonates having formula (II) (II) wherein a, b, M, A and q are as defined hereinbefore and Y is an unsubstituted hneai aliphatic moiety consisting of carbon and hydrogen having two methyl termini, and wherein Y has an average carbon content of from about 10 0 to about 14 0 (preferably from about 1 1 0 to about 13 0, more preferably 11 5 to 12 5 carbon atoms), (preferably said mixture of nonbranched alkylbenzenesulfonates is further characterized by a sum of carbon atoms in Y. of from 9 to 15, more preferably 10 to 14), and wherein said composition is further charactenzed by a 2/3-phenyl index of from about 350 to about 10,000 (preferably from about 400 to about 1200, more preferably from about 500 to about 700) (and also preferably wherein said surfactant mixture has a 2- methyl-2-phenyl index of less than about 0 3, preferably less than about 0 2, more preferably less than about 0 1, more preferably still, from 0 to 0 05)
Also encompassed by way of mid-chain branched surfactants of the alkylbenzene- deπved types are surfactant mixtures comprising the product of a process compπsing the steps of alkylating benzene with an alkvlating mixture, sulfonating the product of (I), and neutralizing the product of (II), wherein said alkylating mixture comprises (a) from about 1 % to about 99 9%, by weight of branched C--C2( monoolefins, said branched monoolefins having structures identical with those of the branched monoolefins formed by dehydrogenating branched parafins of formula R'LR° wherein L is an acyclic aliphatic moiety consisting of carbon and hydrogen and containing two terminal methyls, R1 is C, to C, alkyl, and R' is selected from H and C, to C, alkyl, and (b) from about 0 1 % to about 85%, by weight of C--C2I linear aliphatic olefins, wherein said alkylating mixture contains said branched C--C20 monoolefins having at least two different carbon numbers in said C--C20 range, and has a mean carbon content of from about 9 5 to about 14 5 carbon atoms, and wherein said components (a) and (b) are at a weight ratio of at least about 15 85 Selected cationic surfactants
Prefened detergent compositions herein also include those wherein the hybnd builder material of WO 98/42622, or a different hybπd builder as disclosed herein, are combined with selected cationic surfactants These selected cationic surfactants include (1) cationic surfactants having one long chain and three relatively short chains in which one or more substituents attached to the nitrogen atom contain oxygen, as foi example in hydroxyethyl, and/or in which the relatively long chain is branched Such surfactants include, foi example, compounds having the formula R'N^R'R" X wherein R' is Cς-C16 linear or branched alkyl (optionally including one or more aryl, ether or ester moieties) and wherein R2-R4 can vary independently and can, for example, comprise methyl, ethyl, propyl, butyl, hydroxyethyl, hydroxypropyl and mixtures thereof provided that at least one of R2-R4 is hydroxyalkyl, preferably hydroxyethyl. X" is any compatible anion, for example one selected from halogen, (e.g chloride, bromide), acetate, citrate, lactate, glvcolate, phosphate nitrate, sulfate, and alkylsulfate Mixtures of these compounds and the conesponding anions can be used, and/or (n) cationic surfactants having the formula
[R2(OR3 )y][R4(OR3)y]2R5N+X- vvherein R- is an alkyl or alkyl benzyl group having from 8 to 18 carbon atoms in the alkyl chain, each RJ is selected from the group consisting of -CH2CH2-.
CH2CH(CH3)-, -CH2CH(CH2OH)-, -CH2CH2CH2-. and mixtures thereof; each R4 is selected from the group consisting of C1 -C4 alkyl. C] -C4 hydroxyalkyl, benzyl nng structures formed by joining the two R4 groups, -CH2CHOH- CHOHCOR6CHOHCH2OH wherein R^ is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0, R^ is the same as R4 or is an alkyl chain wherein the total number of carbon atoms of R^ plus R^ is not more than about 18; each y is from 0 to about 10 and the sum of the y values is from 0 to about 15; and X is any compatible anion. for example chlonde and/or cationic surfactants other than the conventional alkyltnmethylammonium salts conesponding to the general formula:
wherein Rj , R2, R3, and R4 are independently selected from an aliphatic group of from 1 to about 22 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkylarmdo, hydroxyalkyl, aryl or alkylaryl group having up to about 22 carbon atoms; and X is a salt- forming anion such as those selected from halogen, (e.g chlonde, bromide), acetate, citrate, lactate, glvcolate, phosphate nitrate, sulfate, and alkylsulfate radicals, wherein said compounds the aliphatic groups contain, in addition to carbon and hydrogen atoms, other linkages such as ether linkages, and/or other groups such as amino groups The longer chain aliphatic groups, e.g . those of about 12 carbons, or highei, can be saturated or unsaturated Prefened is when Rj , R2, R3, and R4 are independently selected from Cl to about C22 alkyl Especially prefened for some purposes are cationic mateπals containing two long alkyl chains and two short alkyl chains or those containing one long alkyl chain and three short alkyl chains other than methyl The long alk l chains in the compounds described in the previous sentence have from about 8 to about 22 carbon atoms, preferably from about 10 to about 14 carbon atoms
Also useful herein are the bis- alkoxylated quaternary ammonium (bis-AQA) surfactants and combinations including same disclosed in WO9744433 Al WO9744431 Al , WO9744432 Al , WO9743394 A, WO9743393 A, WO9743391 A, WO9743390 A, WO9743389 A, WO9743371 A, WO9744420 A, WO9744419 A, WO9744418 A, WO9743388 A, WO9743387 A, WO9743365 A, WO9743364 A See also WO9738968 Al
The selected cationic surfactants can be used herein for one or more purposes, including net contribution to cleaning, especially of greasy soils, or for other purposes, such as softening through the wash and/or for antimicrobial purposes
Suitable levels of these cationic surfactants herein are from about 0 1% to about 20%, preferably from about 1 % to about 15%, although much higher levels, e.g , up to about 30% or more, may be useful especially in noniomc cationic (i.e . limited or anionic-free) formulations Highly prefened compositions however combine the cationic surfactant at a very low level, e.g . from about 0 1 % to about 5%, preferably not more than about 2%, with the HZSC materials The selected cationic surfactants, even at said low levels, are surpnsingly effective w ith the HZSC builder matenals
Conventional, especially alkyltπmethylammonium cationic surfactants can be used in conjunction with the selected cationic surfactant types if desired Selected Sugar-denved Surfactants
Prefened detergent compositions herein also include those wherein the hybnd builder matenal of WO 98/42622 or a different hybrid builder as disclosed herein is combined with selected sugar-denv ed surfactants These selected sugar-denved surfactants include particular the C.-C,,, alkyl N-methyl glucamides, for example as disclosed in WO 92/06070 A or WO 92/05071 A published 04/16/92, any of the known lactobionamide surfactants, and combinations of the glucosamides and/or lactobionamides with alkylpolyglucosides (APG's) Cationic-Aniomc Ion Pair Surfactants US 5,472,455 discloses water-soluble complexes of anionic and cationic surfactants These are useful in conjunction with hybnd builders Bleach
Prefened detergent compositions of the invention include those combining HZSC or hybrid builders with selected bleach or bleach-forming mateπals Transition-metal bleach catalysts These selected mateπals include one or more transition-metal-containing bleach catalysts such as the mateπals descnbed in WO 98/39406 A, WO 98/39405 A. WO 98/39335 A, for example those more specifically illustrated hereinafter - see also WO 97/00937, WO 96/06155, EP 718398 A, US 5,720,897 and WO 97/48787
Particularly prefened are iron- or manganese containing bleach catalysts Even more highly prefened are transition-metal bleach catalysts based on any πgid macropolycychc hgand, for example any mononuclear or dmuclear transition metal complex based on tπazacyclononane, more preferably monometallic catalysts wherein the πgid macropolycychc hgand is cross-bndged, as in Bcyclam or any of its homologs, for example those in which terminal alkyl moieties connected to nitrogen are selected from methyl, ethyl and mixtures thereof A particularly useful transition-metal bleach catalyst wherein the terminal alkyl moieties connected to nitrogen are methyl is [Mn(Bcyclam)C12]
"Bcyclam" (5,12-dιmethyl-l,5,8.12-tetraaza-bιcyclo[6 6 2]hexadecane) is prepared according to J Amer Chem Soc . ( 1990), 1 12. 8604 Bcyclam (1 00 g . 3 93 mmol) is dissolved in dry CH3CN (35 mL, distilled from CaH2) The solution is evacuated at 15 mm until the CH3CN1 begins to boil The flask is then brought to atmospheric pressure with Ar This degassing procedure is repeated 4 times Mn(pyπdιne)2Cl2 (1.12 g , 3 93 mmol), synthesized according to the literature procedure of J Inorg Nucl Chem , (1974), 36, 1535, is added under Ar and the mixture is stined overnight at room temperature The reaction solution is filtered with a 0.2μ filter The filtrate is evaporated 1.35 g of product is collected, 90% yield The amount of transition metal bleach catalyst when present in the detergent compositions of the invention is suitably from 0 0001 % to 1 wt.%, more typically from 0 001 % to about 0.1% Organic Bleach Catalysts
The selected bleach-promoting mateπals also include organic bleach catalysts or organic bleach boosters or so-called oxygen transfer agents, for example the N-acyhmine types descπbed in WO98/07825 A or the phosphinoyl lmme types descπbed in US 5,652,207 Such mateπals also include sulfommines These matenals are organic catalysts for bleaching, as distinct from the so-called bleach activators or bleach precursors such as TAED, which are stoichiometπc, and not catalytic Organic bleach catalysts include the compounds themselves and/or any of their precursors, for example any suitable ketone for 5 production of dioxiranes and/or any of the hetero-atom containing analogs of dioxirane precursors or dioxiranes , such as sulfommines and or the lmmes descnbed in U S 5.576,282 and references descnbed therein Organic bleach catalysts can, in general, include anionic, cationic, noniomc or zwittenomc types Zwitteπonic types are among the most prefened Prefened organic bleach catalysts more particularly include omega-(3,4-
10 dihydroisoquinohnium alkane sulfonates as in US 5,576,282 and oxazindmes as descnbed in US 5,710,1 16 Levels can be, for example, from about 0 01% to about 5% Hvdrophobic and other selected Bleach activators and/or precursors
Prefeπed detergent compositions herein include, in addition to a hybrid builder mateπal, a hvdrophobic peracid or an activator capable of releasing such peracid The
15 hvdrophobic types include those containing a chain of six or more carbon atoms, prefened hydrophobic types having a linear aliphatic C8-C14 chain optionally substituted by one or more ether oxygen atoms and/or one or more aromatic moieties, preferably positioned such that the peracid is an aliphatic peracid More generally , such optional substitution by ether oxygen atoms and/or aromatic moieties can be applied to any of the
20 peracids or bleach activators herein Branched-cham peracid types and aromatic peracids having one or more C3-C16 linear or branched long-chain substituents can also be useful The peracids can be used in the acid form or as any suitable salt with a bleach-stable cation
Especially useful herein are the organic percarboxyhc acids of formula
O O O O
II II II II
R1-C— N— R2-C-OOH , R1— N— C— R2-C-OOH
I I
? 5 R5 R5 or mixtures thereof wherein R' is alkyl, aryl, or alkaryl containing from about 1 to about 14 carbon atoms, R" is alkylene, arylene or alkarylene containing from about 1 to about 14 carbon atoms, and R" is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms When these peracids have a sum of carbon atoms in R1 and R2 30 together of about 6 or higher, preferably from about 8 to about 14, they are particularly suitable as hydrophobic peracids for bleaching a vanety of relatively hydrophobic or "hpophihc" stains, including so-called "dingy" types Calcium, magnesium, or substituted ammonium salts may also be useful With respect to any of these peracids, a bleach activator which yields the conesponding peracid under perhydrolysis conditions can desirably be used The bleach activator will generally have a leaving group having any suitable pKa for perhydrolysis m-use The pK, of the conjugate acid of the leaving group is a measure of suitability, and is typically from about 4 to about 10. or higher, preferably from about 6 to about 12, more preferably from about 8 to about 1 1 Common leaving groups include oxybenzenesulfonate Most commonly, when peracetic acid is the desired peracid, the bleach activator or precursor is an acethylated diamme, such as tetracetylethylenediamine (TAED)
Other useful hydrophobic bleach activators or the conesponding peracids useful herein are acetylemc matenals such as undec-10-ynoyl-oxy-benzene sulphomc acid or related activators as disclosed in DE19616782 Al
Another useful bleach mateπal, whether in the preacid, bleach activator, or diacyl peroxide form, deπves from phfhahmido- substituted matenals such as phfhahmido- percaproic acid or 6-phthahmιdohexaneperoxoιc acid (CAS Registry Number 128275-31 - 0), for example as disclosed in US 5,487,818, US 5,415,796, EP 852,259 A, and WO 98/39405 A though other phthahmido-substituted bleach promoting matenals, for example those of EP 780,374 A or EP 325,288 A, can also be used Yet another useful hydrophobic bleach activator and or the conesponding peracid are disclosed in US 5,061,807, DE 3823172 A, and Japanese Laid-open patent application (Kokai) No 4- 28799 The peracid is preferably 3-dodecyl-2.5-dιoxo-l -pynohdιne hexaneperoxoic acid Analogs v arying in length of the longest chain from C8-Cl6, as well as branched analogs, other related lmidoperoxycarboxylic acids as disclosed in US 5,061 ,807, and any of the conesponding activators with any known leaving-group are equally applicable herein
More particularly prefened hydrophobic bleach activators include sodium nonanoyloxybenzene sulfonate (NOBS or SNOBS), substituted amide types, and the above-identified activators related to certain imidoperacid bleaches, for example as described in U.S 5,061,807 Also useful are the acyl lactam activators especially the acyl caprolactams (e.g WO 94-28102 A), acyl valerolactams (e.g U.S 5,503,639), and certain N(alkanoyl) ammo alkanoyloxybenzene sulfonates as descnbed in WO 98/27056 A
The diacyl peroxides conesponding to any of the above-identified peracids and/or activators are also encompassed herein
Also useful herein as activators are compounds that, under perhydrolysis conditions, release (I) percarboxyhc acids and (n) labile groups that can act as a substrate for enzymes, especially redox-active enzymes See DE19713852 A
Combinations of the above-identified peracids and/or bleach activators are also especially useful Moreover, combinations of the above-identified peracids and/or activators with conventional bleach activators, especially TAED, can give very good combinations of dingy and hydrophihc stain removal
Bleach activators are suitably used m amounts of from 1 to 8 wt %, preferably Photobleaches
The present invention encompasses combinations of the hereinabove-defined hybπd builder materials with photobleaches In general, any photobleach can be used, such as the fully or partially sulfonated zinc and/or aluminium phthalocyamnes, see for example BE-865371 A, GB 1408144 A, US 4,497,741, RD 182041 or EP 119,746 Other photobleaches suitable for use herein are any of those commercially available from CIBA However prefened photobleaches useful herein in particular include Si-phthalocyanmes as disclosed in WO 97/05202 A, low-hue photobleaches as descπbed in WO 98/32832 A and US 5.679,661 , superoxide-generating photobleaches as described in WO 98/32829 A, singlet oxygen generating photobleaches as descnbed WO 98/32828 A, and other photobleaches as descπbed in WO 98 '32827 A, WO 9832826 A, WO 98/32825 A and WO 98/32824 A Photobleaches can be used singly or in combination Type and amount of hue can be adjusted according to the desires of the formulator Bleach-promoting enzymes
The present invention encompasses combinations of the hereinabove-defined hvbπd builder mateπals with bleach-promoting enzymes Bleach-promotmg enzymes in general include any enzymes having bleach-promoting action via oxidation or reduction of colored soils and/or stains The term "bleach-promoting enzymes" includes live natural or genetic-engineered enzymes having a bleach-promotmg function with or without there being a requirement for addition of any other redox-active or bleaching matenal Moreover the term "bleach-promoting enzymes" encompasses the enzymes themselves and any related polypeptides having similar effect Suitable bleach-promoting enzymes herein include oxidoreductases More particular bleach-promoting enzymes include oxidases or combination systems including same (DEI 9523389 Al ), mutant blue copper oxidases (WO9709431 Al ), peroxidases (see for example US 5,605,832, WO97/31090 Al ), mannanases (WO971 1 164 Al ), laccases, see WO9838287 Al or WO9838286 Al or for example, those laccase vanants having ammo acid changes m mvcehophthora or scvtalidium laccase(s) as descπbed in WO9827197 Al or mediated laccase systems as descπbed in DE19612193 Al ). or those deπved from coprinus strains (see, for example WO9810060 Al or WO9827198 Al ), phenol oxidase or polyphenol oxidase (JP10174583 A) or mediated phenol oxidase systems (WO971 1217 A), enhanced phenol oxidase systems (WO 9725468 A WO9725469 A), phenol oxidases fused to an ammoacid sequence having a cellulose binding domain (WO9740127 Al , WO9740229 Al ) or other phenol oxidases (WO9708325 A, WO9728257 Al ) or superoxide dismutases
Oxidoreductases and or their associated antibodies can be used, for example with H,O„ as taught in WO 98/07816 A Depending on the type of detergent composition, other redox- active enzymes can be used, even, for example, catalases (see, for example JP09316490
A) The bleach-promoting enzymes can be coated (see for example WO9731088 Al ) oi uncoated
Also useful herein are combinations of the hybnd builder with any oxygenase of extracellular ongin, especially fungal oxygenase such as dioxygenase of extracellular origin The latter is most especially quercetinase, catechinase or an anthocyanase. optionally in combination with other suitable oxidase, peroxidase or hydrolytic enzymes. all a taught WO9828400 A2
Enzyme compositions herein can be solid or liquid, aqueous or non-aqueous and include a substantially water-free liquid composition comprising (A) an enzyme, (B) a substance selected from (I) substances which in aqueous medium are precursors for substrates for the enzyme, and (n) substances which are cofactors for the enzyme, and (C) a non-aqueous liquid phase as described in WO9741215 Al
Prefened bleach-promoting enzyme systems include systems which generate hydrogen peroxide m-situ, for example glucose oxidases or glucose oxidase-hke polypeptides as taught in WO9820136 Al , or an enzyme having aminoalcohol- or D- aminoacid-oxidase activity and a substrate for this enzyme as descπbed in DEI 9545729
Al
Other useful bleach-promoting enzyme systems useful herein incorporate hpoxygenase enzyme, unsaturated acid and a transition metal ion as descπbed in DK9800352 A In a prefened mode, the hpogygenase or other suitable bleach-promoting enzyme is combined with the transition metal bleach catalysts taught elsewhere herein
Still further useful detergent compositions herein are those one-part or multi-part compositions or wash media comprising the hybrid builder mateπals together with bleach-promoting enzyme systems comprising chloroperoxidase, a hydrogen peroxide source, chlonde and adhering agent, preferably formed at or near the site of use, as descπbed in WO 98/42370 A
Other bleach-promoting enzyme related systems useful herein include those of
WO 9807824 A and WO9807816 Al which disclose a detergent composition compπsing a source of hydrogen peroxide and a donor-hydrogen peroxide oxido-reductase-directed antibody
Builder The present invention also encompasses combinations of the hereinabove-defined hybrid builder materials with specific inorganic builders, more particularly one or more of the following mateπals Crystalline silicates Specific crystalline silicates especiallv useful herein include a foliated crystalline sodium silicate with high delta-phase fraction as disclosed m EP-860398 Al , DEI 9707449 Cl , particular layered or sheet silicates as disclosed m JP09025116, JP 10007416 A, WO9703018 Al , DE19613060 Al , EP-753568 A, EP-745559 Al , US5567404 A, EP- 731058 Al . crystalline sodium silicate having delta, alpha, beta- and/or NS-phase as disclosed in WO9719156 Al other crystalline silicates as disclosed in WO9716525 Al , JP0831 1494 A, JP0831 1493 A. JP08268708 A, crystalline silicates made by sinteπng amorphous silicates as disclosed in JP0918361 1 A, crystalline disihcates as disclosed in DE4439083 Al , crystalline silicate powders with RUB-18 structure and specified X-ray diffraction pattern as disclosed in EP-775670 Al , anhydrous crystalline silicates especially containing potassium as disclosed in WO 9831631 Al , JP09302384 A, and metasihcate pentahydrate as disclosed in CN1 131 125 A
Amorphous silicates Specific amorphous sodium silicates useful herein include sodium silicate -metal sulphate composite powders containing the metal sulphate as a solid solution as disclosed in EP- 728837 Al , amorphous ammonium and alkali silicate granules as disclosed IT1265262 B, X-ray amoφhous sodium silicate w ith low crystallisation temperatures prepared from amoφhous silicate with higher water content that can be converted to beta- and alpha- modifications by microwave drying in stages, as disclosed in DE19710383 Al , other specific amoφhous silicates as disclosed in DE19541755 Al , DE19525378 Al , WO96/28382 A, DE4446363 Al , DE4435632 Al , JP10007417 A, JP09309719 A, and crystal hne/amoφhous silicate combinations as disclosed in JP09087690 A, JP09067592 A Amorphous alummosihcates Amoφhous alummosihcates useful herein include those of JP09202613 A, JP083331 13 A
Crystalline alummosihcates and/or zeolites
Specific zeolite compositions useful herein in conjunction with the hybnd builder matenals include P-type zeolites as disclosed in EP 758,626 Al , WO96/34828 Al , WO96/14270 Al , alkali metal silicates deposited onto P-type zeolites as disclosed in WO9734980 Al , gamma-madiated zeolites as disclosed in CN1 1 13263 A, or the equivalent material made without inadiation; alumino-silicates having primarily tetrahedrally coordinated aluminium, formed by the chemical modification of 2: 1 layer clay minerals as disclosed in WO9618576 Al ; zeolites prepared from aluminosilicate gels under pulsation as disclosed in RU2083493 Cl ; microporous zeolite A-LSX as disclosed in EP-816291 Al ; zeolites grown with the assistance of microwave energy as disclosed in DE19548742 Cl ; and mechanically crushed zeolite A having particle size below 1 micron as disclosed in JP09067117 A. Magnesiosilicates Magnesiosilicates can be used in conjunction with the hybrid builders herein. These include the magnesiosihcate materials of WO 97/10179. In more detail, a highly prefened illustrative magnesiosihcate compound for use as a builder component with the hybrid builder materials herein is one having a calcium binding capacity (CBC) of at least 10 mg CaO per gram at room temperature, a magnesium binding capacity (MBC) of at least 10 mg MgO per gram at room temperature, and a calcium binding rate (CBR) of no more than 300 seconds at room temperature, being the time taken to remove half of the Ca2+ from a ~ 100 ppm Ca2+ solution at a loading of 3g per litre, and having either a stuffed silica polymoφh-related structure or a layered structure with a characteristic broad X-ray powder diffraction peak occurring at a d-spacing of between 1 1 and 17 A. Seeded builder systems Various seeded builder can be used in conjunction with the hybrid builder materials herein. These include sodium carbonate in combination with a crystallization seed for calcium carbonate, see GB 1 437 950; tabular calcium carbonates as disclosed in WO9840458 Al ; rhombohedral calcium carbonates as disclosed in WO9840457 Al ; WO9840456 Al ; WO9840455 Al ; see also builders with crystalline microstructure comprising carbonate WO9638526 Al ; WO9733966 Al ; WO9638525 Al ; WO9638524 Al. Other inorganic builders
Other inorganic builders especially useful in conjunction with the hybrid builders herein are noncaking silicates treated with organic compounds as disclosed in JP09208218 A; other new silicates as disclosed in JP 10081509 A; compacted sodium silicates as disclosed in WO9717286 Al ; trisodium phosphate hydrate as disclosed in WO9715527 Al ; and an ion-capturing agent for alkaline earth metal ions which contains a precipitating agent for the ions within pores of a porous support. Preferably the support is silica gel. The pore diameter of the support is 0.3-15 nm. The precipitating agents comprise alkali metal carbonates, bicarbonates, silicates, sulphates and organic acid salts. This latter builder is as disclosed in JP09241680 A. Yet another useful inorganic builder contains alkaline retarding particles, surfactant and an ion blockade agent to elevate pH of washing water after lowenng its hardness, as disclosed in WO9709414 Al Non-bleaching enzymes
Enzymes other than geneπc proteases and amylases as refened to m WO 98/42622 can be used in conjunction with the hybπd builders to unexpectedly great advantage Such enzymes include non-geneπc proteases, non-generic amylases, non-bleaching enzymes other than proteases and/or amylases, bleaching enzymes, combinations thereof, combinations thereof with any suitable antibodies, inhibitors, stabilizers, or promoters, and combinations of any such non-genenc enzymes and/or enzyme-specific adjuncts with genenc proteases and/or amylases Bleaching enzymes and adjuncts specific for use therewith, for formula accounting puφoses, are accounted with the bleach system, as descπbed elsewhere herein
Prefened non-bleaching enzymes useful in conjunction with hybrid builder materials herein include enzymes derived from extremophiles, as well as hvdrolases other than protease and/or amylase
Prefened non-bleaching enzymes other than protease and/or amylase in particular can have low or even very high activity (EP 839,05 A), can include combinations of plant cell wall degrading enzymes and non-cell wall-degrading enzymes (WO 98/39403 A) and can. more specifically, include pectinase (WO 98/06808 A, JP 10088472 A, JP 10088485 A), pectolyase (WO98/06805 Al ), pectin lyases free from other pectic enzymes (WO9806807 Al), chondnotinase ( EP 747,469 A), xylanase ( EP 709.452 A, WO 98/39404 A, WO98/39402 A) including those deπved from microtetraspora flex osa (US 568391 1 ), isopeptidase (WO 98/16604 A), keratinase (EP 747,470 A. WO 98/40473 A), hpase ( GB 2,297,979 A, WO 96/16153 A, WO 96/12004 A, EP 698,659 A, WO 96/16154 A), cellulase or endoglucanase (GB 2,294,269 A, WO 96/27649 A, GB 2,303,147 A, WO98/03640 A, see also neutral or alkaline cellulases denved from c n'sosporwm lucbwwense strain VKM F-3500D as disclosed in WO9815633 A), polygalacturonase (WO 98/06809 A), mycodextranase (WO 98/13457 A), thermitase (WO 96/28558 A), cholesterol esterase (WO 98 28394 A), or any combination thereof Prefened proteases useful herein include certain vanants ( WO 96/28566 A, WO
96/28557 A, WO 96/28556 A, WO 96/25489 A)
Other particularly useful proteases are multiply-substituted protease vanants compπsing a substitution of an ammo acid residue with another naturally occurπng ammo acid residue at an am o acid residue position conesponding to position 103 of Bacillus amvloliquefaciens subtihsin in combination with a substitution of an ammo acid residue with another naturally occurπng amino acid residue at one or more amino acid residue positions conesponding to positions 1. 3. 4. 8, 9, 10, 12, 13, 16, 17, 18. 19, 20, 21 , 22, 24. 27, 33. 37, 38, 42, 43, 48, 55, 57, 58. 61, 62, 68, 72, 75, 76, 77, 78, 79, 86. 87, 89, 97, 98. 99, 101 , 102, 104, 106, 107, 109, 1 1 1 , 1 14, 1 16, 1 17. 1 19, 121, 123, 126. 128. 130. 131. 133, 134, 137, 140, 141 , 142, 146, 147, 158, 159, 160, 166, 167, 170, 173. 174. 177. 181 , 182, 183, 184. 185, 188, 192, 194, 198. 203, 204, 205, 206, 209. 210, 21 1, 212, 213, 214, 215, 216, 217, 218, 222, 224, 227, 228, 230, 232, 236. 237, 238, 240, 242. 243, 244, 245, 246, 247, 248, 249. 251 , 252, 253, 254, 255, 256, 257, 258, 259, 260, 261. 262. 263. 265. 268, 269, 270, 271 , 272, 274 and 275 of Bacillus amvloliquefaciens subtihsin; wherein when said protease variant includes a substitution of amino acid residues at positions conesponding to positions 103 and 76, there is also a substitution of an amino acid residue at one or more amino acid residue positions other than amino acid residue positions conesponding to positions 27, 99, 101, 104, 107, 109, 123, 128. 166, 204, 206, 210, 216, 217, 218, 222, 260, 265 or 274 of Bacillus amvloliquefaciens subtihsin and/or multiply-substituted protease variants comprising a substitution of an amino acid residue with another naturally occurring amino acid residue at one or more amino acid residue positions conesponding to positions 62, 212, 230, 232, 252 and 257 of Bacillus amvloliquefaciens subtihsin as described in PCT Application Nos. PCT/US98/22588, PCT/US98/22482 and PCT/US98/22486 all filed on October 23, 1998 from The Procter & Gamble Company (P&G Cases 7280&, 7281 & and 7282L, respectively). Bleach/amylase/protease combinations (EP 755,999 A; EP 756,001 A; EP
756.000 A) are also useful.
Also in relation to enzymes herein, enzymes and their directly linked inhibitors. e.g., protease and its inhibitor linked by a peptide chain as described in WO 98/13483 A, are useful in conjunction with the present hybrid builders. Enzymes and their non-linked inhibitors used in selected combinations herein include protease with protease inhibitors selected from proteins, peptides and peptide derivatives as described in WO 98/13461 A, WO 98/13460 A, WO 98/13458 A, WO 98/13387 A.
Amylases can be used with amylase antibodies as taught in WO 98/07818 A and WO 98/07822 A, lipases can be used in conjunction with lipase antibodies as taught in WO 98/07817 A and WO 98/06810 A, proteases can be used in conjunction with protease antibodies as taught in WO 98/07819 A and WO 98/06811 A, Cellulase can be combined with cellulase antibodies as taught in WO 98/07823 A and WO 98/07821 A. More generally, enzymes can be combined with similar or dissimilar enzyme directed antibodies, for example as taught in WO 98/07820 A or WO 98/06812 A. The prefened enzymes herein can be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Prefeπed selections are influenced by factors such as pH-activity and/or stability optima, thermostability. and stability to active detergents, builders and the like. In this respect bacterial or fungal enzymes are prefened, such as bacterial amylases and proteases, and fungal cellulases. Pro-perfume and/or enduring perfume
The present detergent compositions include those wherein a hybrid builder is combined with a pro-perfume, pro-accord and/or a particular, enduring perfume system. Such selected ingredients are disclosed more fully in EP 864,642 Al ; EP 864,642 Al ; WO98/07809 A or WO98/07814 A or WO98/07812 A or WO98/07683 A or WO98/07407 A or WO98/27192 A or WO98/0781 1 A (beta keto-esters); WO97/34986 A or WO97/34989 A or WO97/34578 Al or WO98/27190 A or WO98/06803 A (pro- fragrant acetals and or ketals); WO9731094 Al or US 5,500,138 (enduring perfume system) WO96/29281 A (schiff bases and/or esters); US 5,668,102 (esters of non-allylic perfume alcohols); and ZA9610649 A (sulfonates of perfume alcohols) End-capped soil release agents
End-capped polymeric soil release agents (see, for example, US 5,415,807, WO96/18715 A2, WO97/23542 Al and many other patents to Gosselink et al) are especially useful in conjunction with the present hybrid builder materials. Suitable SRA's can have an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone as described in U.S. 4,968,451 ; nonionic end-capped 1,2-propylene/polyoxyethylene terephthalate polyesters as in U.S. 4,71 1 ,730; partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721.580; the nonionic-capped block polyester oligomeric compounds of U.S. 4.702,857; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S. 4,877,896, the latter being typical of SRA's useful in both laundry and fabric conditioning products, an example being an ester composition made from m-sulfobenzoic acid monosodium salt, PG and DMT optionally but preferably further comprising added PEG, e.g., PEG 3400.
Another prefened SRA is an oligomer having empirical formula (CAP)2(EG/PG)5(T)5(SIP)1 which compnses terephthaloyl (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-l ,2-propylene (EG/PG) units and which is preferably terminated with end-caps (CAP), preferably modified isethionates, as taught in U.S. 5,415,807.
Yet another group of prefened SRA's are oligomeric esters of empirical formula: {(CAP)x(EG/PG)y'(DEG)y"(PEG)y'"(T)z(SIP)z'(SEG)q(B)m} Prefened SEG and CAP monomers for these esters include Na-2-(2-,3- dihydroxypropoxy)ethanesulfonate ("SEG"), Na-2- {2-(2-hydroxyethoxy) ethoxy} ethanesulfonate ("SE3") and its homologues and mixtures thereof and the products of ethoxylating and sulfonating allvl alcohol Prefened SRA esters in this class include the product of transesteπfying and ohgomenzing sodium 2-{2-(2- hydroxyethoxy)ethoxy} ethanesulfonate and or sodium 2-[2- {2-(2-hvdroxyefhoxy)- ethoxyjethoxyjethanesulfonate, DMT. sodium 2-(2.3-dιhydroxypropoxy) ethane sulfonate, EG, and PG using an appropriate Tι(IV) catalyst and can be designated as (CAP)2(T)5(FG/PG)1 4(SEG)2 5(B)0 13 wherein CAP is (Na+ -O3S[CH2CH2O]3 5)- and B is a unit from glycenn and the mole ratio EG/PG is about 1 7 1 as measured by conventional gas chromatography after complete hydrolysis Processing of Hybnd Builder with Film-forming Polymers
Certain embodiments of builder systems and detergent compositions of the present inv ention, especially those in granular or powder form, can also contain from about 0 1% to about 10%, typically from about 0 3% to about %, preferably from about 0 3% to about 4%. more preferably 0 5% to about 2 5% by weight of a film-forming polymer soluble in an aqueous slurrv comprising the organic surfactants, aluminosilicate mateπals, and neutral or alkaline salts herein The polymer must be at least partially soluble in the slurry for it to dry to a film capable of cementing the granule walls together as the slurry is dned For optimum granule physical properties, the polymer should be substantially soluble in the slurry, and is preferably completely soluble in the slurry The slurry will typically compnse a surfactant phase and the insoluble aluminosilicate matenal suspended in a solution (often saturated) of the neutral or alkaline salt, which preferably compnses sodium sulfate The slurry w ill usually be alkaline in nature due to the presence of the aluminosilicate mateπal and either anionic surfactants or alkaline salts Since the slurry will generally be a strong electrolyte solution, optimum solubility of the polymer is obtained when it is in the form of an at least partially neutralized or substituted alkali metal, ammonium or substituted ammonium (e g , mono-, di- or tnethanol ammonium) salt The alkali metal, especially sodium, salts are most prefened While the molecular weight of the polymer can vary over a ide range, it preferably is from about 1000 to about 500,000, more preferably is from about 2000 to about 250,000, and most preferably is from about 3000 to about 100.000 Suitable film-forming polymers herein include homopolymers and copolymers of unsaturated aliphatic mono- or polycarboxyhc acids Prefened carboxyhc acids are acrylic acid, hydroxyacryhc acid, mefhacryhc acid, maleic acid, fumaπc acid, itaconic acid, acomtic acid, crotonic acid, and citraco c acid The polycarboxyhc acids (e g maleic acid) can be polymensed in the form of their anhydrides and subsequently hydrolyzed The copolymers can be formed of mixtures of the unsaturated carboxyhc acids with or without other copolymensable monomers, or they can be formed from single unsaturated carboxyhc acids with other copolymeπsable monomers In either case, the percentage by weight of the polymer units denved from non-carboxyhc acids is preferably less than about 50% Suitable copolymeπsable monomers include, for example, vinyl chlonde, vinyl alcohol, furan, acrylonitnle, vinyl acetate, methyl acrylate, methyl methacrylate, styrene, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, acrylamide, ethylene, propylene and 3-butenoιc acid Prefeπed polymers of the above group are the homopolymers and copolymers of acrylic acid, hydroxyacrylic acid, or methacryhc acid, which in the case of the copolymers contain at least about 50%, and preferably at least about 80%o, by weight of units derived from the acid Particularly prefened polymers are sodium polyacrylate and sodium polyhydroxyacrylate Other specific prefened polymers are the homopolymers and copolymers of maleic anhydride, especially the copolymers with ethylene, styrene and vinyl methyl ether These polymers are commercially available under the trade names Versicol and Gantrez The polymerisation of acrylic acid homo- and copolymers can be accomplished using free-radical initiators, such as alkali metal persulphates, acyl and aryl peroxides, acyl and aryl peresters and aliphatic azocompounds The reaction can be earned out in situ or in aqueous or non-aqueous solutions or suspensions Cham- terminating agents can be added to control the molecular weight The copolymers of maleic anhydπde can be synthesised using any of the types of free-radical initiators mentioned above in suitable solvents such as benzene or acetone, or in the absence of a solvent, under an inert atmosphere These polymerisation techniques are well known in the art It will be appreciated that instead of using a single polymenc aliphatic carboxyhc acid, mixtures of two or more polymeric aliphatic carboxyhc acids can be used to prepare the above polymers Other film-forming polymers useful herein include the cellulose sulfate esters such as cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose sulfate, methylcellulose sulfate, and hydroxypropylcellulose sulfate Sodium cellulose sulfate is the most prefened polymer of this group Other suitable film-forming polymers are the carboxylated polysacchaπdes. particularly starches, celluloses and alginates, described in U.S. Pat No 3.723.322. Diehl. issued Mar. 27, 1973; the dextnn esters of polycarboxyhc acids disclosed in U.S Pat No. 3,919,107, Thompson, issued Nov. 1 1, 1975; the hydroxyalkyl starch ethers, starch esters, oxidized starches, dextπns and starch hydrolysates described in U S Pat No 3,803,285, Jensen, issued Apr 9, 1974, and the carboxylated starches descnbed in U.S Pat No 3,629,121 , Eldib, issued Dec. 21 , 1971 , all coφorated herein by reference Prefened polymers of the above group are the carboxymethyl celluloses Particularly prefened polymers for use herein are 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%, of the polymer Most preferably the polymer has a molecular weight of from about 4,000 to about 10,000 and an acrylamide content of from about 5% to about 15% Such a polymer acts to increase the percentage of a crutcher mix that is in the aqueous (lye) phase This improves the rate at which droplets of the crutcher mix will dry in a spray tower and can desirably increase the density of the resulting detergent granules when, for example, large amounts of sodium sulfate or other high-density inorganic salt is in the lye phase
US 4,379,080 issued Apnl 5, 1983 provides additional detail, in particular, descnption of useful spray drying processes which can be used to combine the present hybrid builders with film-forming polymers Organic builders
The present detergent compositions also include those wherein a hybrid builder is combined with organic builders selected from - poiycarboxylates, more particularly those of JP 10147640 A denved from catalytic-oxidation of (a) OH-containing compounds selected from glyceπne, glyceπc acid (GA) , glycerates, tartronic acid (TA) and tartronates in the presence of (b) metal salts selected from Fe salts and Zn salts as catalysts and polymeπsing (c) ketomalonic acid or its salts, - compositions compnsing alkali metal or ammonium borates and compounds having at least two OH groups in v icinal configuration as disclosed in WO96/38523 A,
- succimc acid denvatives of mono, di or tπ-pentaerythntol as disclosed in WO96/22961 A,
- improved types of polyacetal carboxylates as disclosed in EP 803,521 A, - tartronic acid prepared by catalytic oxidn of e g glycerine as disclosed in
JP08151345 A, JP08092156 A,
- di- or ohgotartaπc acids as disclosed in DE195231 16 Al ,
- sugar acid succinates as disclosed in DEI 9515899 Al ,
- dextπn, optionally oxidized as disclosed DE19613880 Al , WO97/20905 A, DE19545727 A1. DE19545723 Al ,
- oxidized starch and or polysacchaπdes and or maltodextπns as disclosed in WO96/29351 A, WO96/27618 A, DE4426443 A, WO98271 18 A, JP09249892 A, WO97/32903 A, JP09188704 A, EP 755,944 A, WO9638484 A,
- cysteic monosuccinates as disclosed in WO97/23450 A, - soluble aminoether carboxyhc acids as disclosed in JP10204045 A,
JP10204044 A, JP10088189 A, and - mixtures thereof
Functional Polymers other than Soil Release Agents and/or Film-forming Polymers
The present detergent compositions also include those wherein a hybrid builder is combined with a functional polymer other than a soil release agent or film-foπnmg polymer as defined heremabove
Prefened among such polymers are one or more members selected from the group consisting of
- hydrophobically modified polyacrylates (see, for example, EP 812,905 A2, EP 786,516 A2, such mateπals are available from Rohm & Haas, National Starch and others),
- teipolymers compnsing acrylate or maleate (see, for example, US 4,647,396, US 4,698,174, EP 608.845, such mateπals are available from Rohm & Haas and others),
- polymeric dye transfer inhibitors (for example PVPNO, see for example EP-704523 Al or WO96/20996 Al or polymers of DEI 9621509 Al or WO96/37598 Al available from BASF,
- polyamines (see, for example WO97/00936 Al , WO97/23546 Al , WO97/28207 Al , WO97/42285 Al and WO 97/35950 Al ),
- polyimme deπvatives such as ethoxylated/propoxylated polyalkyleneamme polymers (see for example US 5,565, 145) or functionahzed backbone polyamines (see WO97/42286 Al ),
- polymenc rheology modifiers (see, for example modified polysacchandes, known "deflocculating polymers" - see for example US 5,147,576, and mixtures thereof), and - mixtures of any of the foregoing polymers
Softeners
The present hybπd builders can be used with certain specific softeners with excellent results For example, softemng-through-the wash detergents or additives can be prepared by combining the hybrid builders with cationic biodegradable softeners as disclosed EP 831,144 A, ZA9702461 A, WO97/34976 A, WO 97/36976 A, biodegradable di ester quaternary ammonium compounds as disclosed in WO 98/03619 A, softeners having hydrolyzable moieties as disclosed in WO97/34975 A, quats with mono-long chain softeners as disclosed in WO97/34972 A, unsaturated softeners as disclosed m WO98/17757 A, chelant/unsaturated softener combinations as disclosed in WO97/13828 A, esterquats and unsaturated fatty acids as disclosed in WO 97/1 1 142 A, low-odor softeners as disclosed in WO 98/47991 A, dryer-activated softeners as disclosed in US 5,830,835, clear softeners as disclosed in WO98 17756 A, WO 97/03169 A, EP- 839899 Al , carboxyhc quaternary ammonium fabnc softener plus cationic nitrogen containing charge booster(s) combinations as disclosed in WO 98/12292 A, US 5.733.855 A, WO 98/12293 A, WO 98/08924 A, or dispersible polyolef s as disclosed WO97/46654 A
Fillers and bars especially svndet bars
The present hybrid builder materials are usefully incoφorated into laundry bars or syndet bars, which can be made by any known technique In such combinations, some prefeπed combinations with the hybπd builder are with fillers such as magnesium or calcium sulfates, kaolin, clays, hydroxysodahte, or the like, divalent metal sulfates as disclosed in WO98/20103 A, soap syndet/ starch combinations as disclosed m WO98/18896 A, in bars of enhanced firmness as disclosed in AU 9656053 A, with enzymes as disclosed in WO98/18897 A, with dihydnc alcohols as disclosed in WO98/1661 1 A, pour-molded with soap-based network structures as disclosed in WO98/1 1864 A, with anionic detergents, soaps, polyphosphates and specified poly hvdroxy fatty acid amides as disclosed in WO98/05752 A, with absorbent gelling materials as disclosed in US 5,703,026, as pour-molded bars made by alcohol-free processes as disclosed in US 5.703,025 or with paraffin wax, WO 97/22684 A, bars with anionic synthetic detergent surfactant, bleaching agent and non liquid thixotropic binding agents as disclosed m WO97/44434 A, in bars with soil-releasing agents as disclosed in WO97/42283 A, BR 9502489 A, in bars with cellulase as disclosed in WO 9706985 A, in bars with chelant as disclosed in CN 1 107884 A, or in bars with bleach and enzyme as disclosed in WO 97/08283 A Detergent adjuncts other than Class 1 adjuncts Detergent surfactants
The detergent compositions of the invention can contain one or more conventional detergent surfactants chosen from soap and non-soap anionic, cationic, noniomc, amphoteπc and zwittenonic detergent-active compounds, and mixtures thereof Many suitable surfactants are available and are descnbed in the literature, for example, in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch, in the well-known Mc Cutcheon's, and in the "Surfactant Science Series" of texts published by Marcel Dekker, New York Prefened surfactants include synthetic non-soap anionic and noniomc types, though soaps, including those deπved from vegetable sources, can also be used, especially in bars Anionic surfactants are well-known and include alkylbenzene sulphonates, e g ,
"linear" types having an alkyl chain length of C8-C15 or non-biodegradable "hard- branched" types though these latter types are relatively undesirable, especially where not permitted by legislation or where environmental considerations are paramount Pnmary and secondary alkyl sulphates, particularly C12-C15 pnmary alkyl sulphates, alkyl ether sulphates, olefin sulphonates, alkyl xylene sulphonates, dialkyl sulphosuccinates, and fatty acid ester sulphonates, such as methyl ester sulfonates, can be used Sodium salts are typically prefened
Noniomc surfactants that may be used include pnmary and secondary alcohol ethoxylates, especially C8-C20 pnmary and secondary aliphatic alcohols ethoxylated with from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially C9-C15 pnmarv aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethvlene oxide per mole of alcohol The conesponding denvatives of Guerbet, Exxal®, Isofol® or Lial® alcohols can also be useful
Also of interest are non-ethoxylated noniomc surfactants, for example polyhvdroxyamides The choice of detergent-active compound (surfactant), and the amount, will depend on the intended use of the composition different surfactant systems may be chosen for handwashing products and for products intended for use in different types of washing machine
The surfactant system can optionally be complemented by one or more cationic surfactants, such as fatty alkyl tnmethylammonium salts or variants thereof Examples of other suitable cationic surfactants are descπbed in following documents, all of which are incoφorated by reference herein in their entirety M C Publishing Co , McCutcheon's, Detergents & Emulsifiers, (North American edition 1997), Schwartz, et al , Surface Active Agents. Their Chemistry and Technology. New York Interscience Publishers, 1949. U S Patent 3,155,591 , U S Patent 3,929,678, U S Patent 3,959,461 U S Patent 4,387.090 and U S Patent 4.228,044
Additionally, special-puφose surfactants, for example the linear or branched - C20 fatty alkyldimefhylamine-N-oxides may be added for grease cleaning Cationic or amine oxide surfactants, when present, are typically used at levels below about 5%. more generally at levels in the range from about 0 1% to about 2% The total amount of surfactant system present will also depend on the intended end use, but suitably ranges from about 2% to about 60 wt %, preferably from 5% to 40 wt %
Detergent compositions suitable for use in most automatic fabnc washing machines generally contain anionic non-soap surfactant, or noniomc surfactant, or combinations of the two in any ratio, optionally together with soap Builders As noted, the detergent compositions of the invention contain a hvbrid aluminosilicate as described in detail hereinbefore as a detergencv builder. This material may be complemented by one or more of the above-identified Class I adjuncts or any of the following detergency builders. The total amount of detergency builder in the compositions, including the hybrid aluminosilicate and other builders, if present, will suitably range from 10 to 85 wt.%.
A suitable complementary builder is selected from zeolite A, zeolite P, zeolite X, zeolite NX (or any other co-crystallized zeolite having equivalent effect), maximum aluminum zeolite P, and mixtures thereof. The amount of zeolite present may suitably range from 5 to 60 wt.%, more preferably from 15 to 40 wt.%, calculated on an anhydrous basis (equivalent to from 6 to 75 wt.%, preferably from 19 to 50 wt.%, calculated on a hydrated basis).
The zeolite may, if desired, be used in conjunction with other inorganic or organic builders. Inorganic builders that may be present include sodium carbonate. Organic builders that may be present include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymefhyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts though this list is not intended to be exhaustive.
Other organic builders useful herein include polyacetal carboxylates, for example polymers and copolymers having polyglyoxylate structural units; see, for example, US 4,146,495; US 4,140,676; EP 803,521 A: such materials are available from Monsanto, Nippon Shokubai, BASF and others. Prefened supplementary builders for use in conjunction with the hybrid aluminosilicate include citric acid salts, more especially sodium citrate, suitably used in amounts of from 3 to 20 wt.%, more preferably from 5 to 15 wt.%. Other supplementary builders are the water-soluble or partly water-soluble silicates, whether crystalline or amoφhous. These include the so-called layer silicates such as SKS-6 from Hoechst/Clariant and/or common 2-ratio or 3-ratio soluble silicates. Such materials, when present, are typically used at levels in the range from about 0.1% to about 20%) of the composition; more commonly, the level is below about 10%.
In more detail, suitable silicate builders include water-soluble and hydrous solid types and including those having chain-, layer-, or three-dimensional- structure as well as amoφhous-solid silicates or other types. Prefened are alkali metal silicates, particularly those liquids and solids having a SiO2:Na2O ratio in the range 1.6:1 to 3.2:1, including solid hydrous 2-ratιo silicates marketed by PQ Coφ under the tradename BRITESIL®, e g , BRITESIL H2O, and layered silicates, e g , those descπbed in U S 4.664,839, May 12. 1987, H P Rieck NaSKS-6 or "SKS-6", is a crystalline layered aluminum-free δ- Na-,SιO, silicate marketed bv Hoechst and is prefeπed especially m granular laundry compositions See DE-A-3.417.649, DE-A-3,742,043 and technical publications of Hoechst / Clanant, for example Surfactant Science Senes, Marcel Dekker, New York, see Vol 71 , Ed M S Showell, published 1998 See more particularly Chapter 3, "Builders The Backbone of Powdered Detergents" by Hans-Peter Rieck of Hoechst / Clanant
Other layered silicates, such as those having the general formula NaMSιxO2N , yH2O 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 also or alternately be used herein Layered silicates from Hoechst also include NaSKS-5, NaSKS-7 and NaSKS-1 1, as the α, β and γ layer-silicate forms Other silicates may also be useful, e g magnesium silicate, for example for bleach stabilizing or process aid puφoses Also suitable herein are crystalline ion exchange mateπals or hydrates having chain structure and a composition represented by xM.,0 ySiO^ zM'O as anhydπde wherein M is Na and/or K, M' is Ca and/or Mg, y/x is 0 5 to 2 0 and z/x is 0 005 to 1 0 as taught in U S 5,427,71 1
Conventional aluminosilicate builders or zeolites can be useful in certain embodiments These include materials having foπnula [M?(AlO2)z(SιO2) xH2O wherein z and v are integers of at least 6, the molar ratio of z to v is in the range from 1 0 to 0 5, and x is an integer from 15 to 264 Alummosihcates can be crystalline or amoφhous, naturally-occumng or synthetically denved An aluminosilicate production method is in U S 3,985,669, Krummel, et al, October 12, 1976 Prefeπed synthetic crystalline aluminosilicate ion exchange materials are available as Zeolite A, Zeolite P (B), Zeolite X and, to whatever extent this differs from Zeolite P, the so-called Zeolite MAP Natural types, including chnoptilohte, may be used Zeolite A has the formula NaI2[(AlO2)12(SιO2)I2].xH2O wherein x is from 20 to 30, especially 27 Dehydrated zeolites (x = 0 - 10) may also be used Preferably, the aluminosilicate has a particle size of 0 1 - 10 microns in diameter
Suitable carbonate builders include alkaline earth and alkali metal carbonates as disclosed in German Patent Application No 2,321 ,001 published on November 15, 1973, although sodium bicarbonate, sodium carbonate, sodium sesquicarbonate, and other carbonate minerals such as trona Other useful carbonate builders are those of U S 5,658,867 issued August 19, 1997, to Panchen et al incoφorated herein by reference or any convenient multiple salts of sodium carbonate and calcium carbonate such as those having the composition 2NaXO, CaCO when anhydrous, and even calcium carbonates including calcite, aragomte and vatente, especially forms having high surface areas relative to compact calcite may be useful, for example as seeds or for use in synthetic detergent bars Also prefened to complement the builder in certain embodiments are polycarboxylate polymers, more especially acryhc/maleic copolymers, suitably used in amounts of from 0 5 to 15 wt %, especially from 1 to 10 wt %, of the detergent composition The invention however includes embodiments from which such conventional polycarboxylate polymers are substantially absent The term "substantially absent" means that no amount is deliberately added though adventitious amounts may be present, for example as a result of presence in a preformulated additive, such as a particulate enzyme additive Bleach
Detergent compositions of the invention can also include one or more components of a conventional bleach system Such a bleach system may generally compnse any source of oxidative or reductive bleach, for example chlonne bleaches such as hyophahte, especially hypochloπte, any hypohahte precursor, such as sodium dichloroisocyanurate, or any reductiv e bleach, for example sodium hydrosulphite or sodium bisulfite Prefened bleach systems include those which are oxidative and compnse at least one source of bleaching oxygen Most generally, for example, when using a transition-metal bleach catalyst, there is no need for any source of bleaching oxygen other than oxygen from the air Quite typically, however, a source of bleaching oxygen is added into the formulation Such sources of bleaching oxygen include hydrogen peroxide, sodium perborate monohydrate. sodium perborate tetrahydrate, sodium percarbonate, any other salt or adduct capable of releasing hydrogen peroxide in water, and mixtures thereof
Conventional bleach systems also often include hydrophihc bleach activators (bleach precursors) or the conesponding peracids, for example TAED (tetraacetylethylenediamme) or peracetic acid Bleach stabilizers, for example heavy metal sequestrants and/or free radical inhibitors, may also be present In certain instances, for example, low levels of tin compounds are used to stabilize bleach In detergent compositions herein, sodium percarbonate or other persalts may be present in an amount of from 5 to 30 wt %, preferably from 10 to 25 wt % Bleach activators are suitably used in amounts of from 1 to 8 wt %, preferably from 2 to 5 wt % Organic or inorganic peroxyacids can also be used These are normally in an amount within the range of from 2 to 10 wt %, preferably from 4 to 8 wt % Enzymes Conventional proteases and/or amylases can be used in the present compositions, for example Savinase ®, Termamyl® available from Novo or enzymes as taught in WO 98/42622, Engelhard Polymenc Soil Release Agent Polymeric soil release agents, hereinafter "SRA" or "SRP's", can be used herein
Levels include from 0.01 % to 10 0%, typically from 0.1% to 5%, preferably from 0.2% to 3 0% Prefened SRA's can have hydrophihc segments and hydrophobic segments and can include charged, e.g., anionic or even cationic (see U.S 4,956,447), as well as noncharged monomer units Structures may be linear, branched or even star-shaped Prefened SRA's include ohgomenc terephthalate esters, e.g., made by transestenfication/oligomenzation with a suitable catalyst Such esters may mcoφorate additional monomers binding through one. two, three, four or more positions, generally without heavy crosshnkmg
SRA's also include those w ith segments of ethylene terephthalate or propylene terephthalate with ethylene oxide or propylene oxide, see U.S 3,959.230 and U.S 3,893,929. cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow , and the C1 -C4 alkylcelluloses and C4 hydroxyalkyl celluloses, see U.S 4,000,093 Suitable SRA's characterized by poly(vιnyl ester) hydrophobe segments include graft copolymers of poly(vιnyl ester), e.g., C\-C vinyl esters, preferably poly(vιnyl acetate), grafted onto polyalkylene oxide backbones See European Patent Application 0 219 048, published April 22, 1987 by Kud, et al Commercially available SRA's include SOKALAN SRA's such as SOKALAN HP-22, available from BASF, Germany Other SRA's are polyesters with repeat units containing 10-15% by weight of ethylene terephthalate together with 90-80% by weight of polyoxyethylene terephthalate. deπved from a polyoxyethylene glycol of average molecular weight 300-5,000 Commercial examples include ZELCON 5126 from duPont and MILEASE T from ICI
Additional classes of SRA's include (I) noniomc terephthalates using dnsocyanate coupling agents to link up polymenc ester structures, see U.S 4,201 ,824 and U.S 4,240,918, (II) SRA's with carboxylate terminal groups made by adding tπmelhtic anhybnde to known SRA's to convert terminal hydroxyl groups to tπmelhtate esters See also U.S 4,525,524, (III) anionic terephthalate-based SRA's of the urethane-lmked vanety, see U.S 4,201,824; (IV) poly(vιnyl caprolactam) and related co-polymers with monomers such as vinyl pynohdone and/or dimethylammoethyl me hacrylate, including both noniomc and cationic polymers, see U.S 4,579,681 , (V) graft copolymers, in addition to the SOKALAN types from BASF made, by grafting acrylic monomers on to sulfonated polyesters, these SRA's assertedly have soil release and anti-redeposition activity similar to known cellulose ethers see EP 279,134 A, 1988, (VI) grafts of vinv l monomers such as acrylic acid and vinyl acetate on to proteins such as caseins, see EP 457,205 A, 1991 , (VII) polyester-polyamide SRA's prepared by condensing adipic acid, caprolactam, and polyethylene glycol, especially for treating polyamide fabπcs, see DE 2,335,044 1974 Other useful SRA's are descnbed in U S 4.240,918 4.787.989 4,525,524 and 4,877,896 Clav Soil Removal/Anti-redeposition Agents
The compositions of the present invention can also optionally contain water- soluble ethoxylated or acylated amines or polyamines having clay soil remov al and antiredeposition properties Granular detergent compositions which contain these compounds typically contain from about 0 01% to about 10 0% by weight of the water- soluble ethoxylated amines, liquid detergent compositions typically contain about 0 01% to about 5%
A prefened soil release and anti-redeposition agent is ethoxylated tetraethylene pentamine See U S 4,597,898 See also European Patent Application 1 1 1,965, published June 27, 1984 Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 1 1 1 ,984, published June 27. 1984, the zwittenomc polymers disclosed in European Patent Application 1 12,592, published July 4, 1984, and the amme oxides disclosed in U S 4,548,744 Other clay soil removal and/or anti redeposition agents are disclosed in U S 4,891,160, and WO 95/32272, published November 30, 1995 Another type of prefened antiredeposition agent includes the known cellulosic materials such as carboxy methyl cellulose (CMC) Polymenc Dispersing Agents Polymenc dispersing agents can be used herein at levels from about 0 1 % to about
7%, by weight, especially in the presence of hybnd alummosihcates, zeolite and/or layered silicate builders Such agents include polymenc polycarboxylates and polyethylene glycols Polymenc dispersing agents are believed to enhance detergent builder performance, by mechanisms such as crystal growth inhibition, particulate soil release, peptization, or anti-redeposition
Polymenc polycarboxylate matenals can be prepared by polymenzing or copolymeπzing suitable unsaturated monomers, preferably m their acid form Unsaturated monomeπc acids that can be polymenzed to form suitable polymenc polycarboxylates include acrylic acid, maleic acid (or maleic anhybnde), fumanc acid, itaconic acid, acomtic acid, mesaconic acid, citraconic acid and methylenemalonic acid The presence in the polymeric polycarboxylates herein or monomeπc segments, containing no carboxylate radicals such as vmylmethy l ether, styrene, ethylene, etc is suitable provided that such segments do not constitute more than about 40% by weight
Particularly suitable polymenc polycarboxylates can be denved from acrylic acid, as m water-soluble salts of polymerized acrylic acid The average molecular weight of such polymers preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000 Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts See U S 3,308,067
Acryhc/maleic-based copolymers may also be used Such matenals include the water-soluble salts of copolymers of acrylic acid and maleic acid The average molecular weight of such copolymers preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000 The ratio of acrylate to maleate segments will generally range from about 30 1 to about 1 1 , more preferably from about 10 1 to 2 1 Alkali metal, ammonium and substituted ammonium salts of the polymers can be used See European Patent Application No 66915, published December 15, 1982, as well as in EP 193,360, published September 3, 1986, which also descnbes such polymers compπsing hydroxypropylacrylate Still other useful dispersing agents include the maleic/acryhc/vinyl alcohol teφolymers Such mateπals are also disclosed in EP 193,360, including, for example, the 45/45/10 teφolymer of acryhc/maleic/vinyl alcohol
Another polymenc mateπal which can be included is polyethylene glycol (PEG) PEG can exhibit dispersing agent performance as well as act as a clay soil removal- antiredeposition agent Typical molecular weight ranges for these puφoses range from about 500 to about 100,000, preferably from about 1 ,000 to about 50,000, more preferably from about 1 ,500 to about 10,000
Polyaspartate and polyglutamate dispersing agents may also be used A prefened average molecular weight is about 10,000
Other polymer types which may be used include vaπous teφolymers and hydrophobically modified copolymers, including those marketed by Rohm & Haas, BASF Coφ , Nippon Shokubai and others for all manner of water-treatment, textile treatment, oi detergent applications Bnghtener
Any optical bπghteners or other bπghtening or whitening agents known m the art can be incoφorated at levels typically from about 0 01 % to about 1 2%, by weight, into the detergent compositions herein Suitable bπghteners include those identified in U.S 4,790,856 These include PHORWHITE bπghteners from Verona Other bπghteners disclosed in '856 include Tmopal UNPA, Tinopal CBS and Tmopal 5BM, available from Ciba-Geigy. Arctic White CC and Arctic White CWD, the 2-(4-styryl-phenyl)-2H- naptho[ 1 ,2-d]tπazoles, 4,4'-bιs-( 1.2,3-tnazol-2-yl)-stιlbenes, 4,4'-bιs(styryl)bιsphenyls, and the aminocoumaπns Specific examples of these bnghteners include 4-methyl-7- diethyl- amino coumann, l,2-bιs(benzιmιdazol-2-yl)ethylene, 1 ,3-dιphenyl-pyrazohnes, 2,5-bιs(benzoxazol-2-yl)thιophene, 2-styryl-naptho[l,2-d]oxazole, and 2-(stιlben-4-yl)- 2H-naphtho[l,2-d]tnazole See also U S 3,646,015 Dye Transfer Inhibiting Agents
The compositions of the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabnc to another duπng the cleaning process Generally, such dye transfer inhibiting agents include polyvmyl pyno done polymers, polyamine N-oxide polymers copolymers of N-vinylpynohdone and N- vinyhmidazole, and certain mateπals accounted for in the bleach system such as zmc, manganese, aluminum and silicon phthalocyamnes, peroxidases, and mixtures thereof If used, these agents typically compnse from about 0 01%> to about 10% by weight of the composition, preferably from about 0 01 % to about 5%, and more preferably from about 0 05% to about 2% Chelating Agents
Detergent compositions herein may also optionally contain one or more chelating agents for metals such as iron and or manganese in water-soluble, colloidal or particulate form or associated as oxides or hydroxides, or found in association with soils such as humic substances Prefened chelants effectively control such transition metals, especially limiting deposition of such transition-metals or their compounds on fabπcs and/or controlling undesired redox reactions in the wash medium and or at fabnc or hard surface interfaces Such chelating agents include those having low molecular weights as well as polymenc types, typically having at least one, preferably two or more donor heteroatoms such as O or N, capable of co-ordination to a transition-metal, Common chelating agents can be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof Prefened chelating agents (chelants) include EDTA, S,S'-EDDS, DTPA, phosphonate types such as HEDP and mixtures thereof
If utilized, chelating agents will generally comprise from about 0 001% to about 15% by weight of detergent composition More preferably , chelating agents will compnse from about 0 01 % to about 3 0%> by weight of the composition Suds Suppressors - Suds suppressors useful herein may be single mateπals or may be mixed or compounded in known ways See, for example, Kirk Ofhmer Encyclopedia of Chemical Technology, 3rd. Ed., Vol. 7, ppg 430-447 (John Wiley & Sons, Inc., 1979). Common suds suppressors include C10-C24, preferably C16-C18 monocarboxylic fatty acids and salts thereof. See U.S. Patent 2,954,347. Suitable salts include Na, K, Li, Ca, Mg, Al, Zn, ammonium and alkanolammonium salts. Stearic acid and aluminium tristearate are common examples. Alternate suds suppressors include high molecular weight liquid or waxy linear, cyclic or mixed C12-C70 hydrocarbons (see U.S. 4,265,779) such as paraffins or haloparaffins; fatty acid esters such as fatty acid triglycerides; fatty acid esters of monovalent alcohols; aliphatic Cι -C4o ketones such as stearone; N- alkylated aminotriazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines; and hydrocarbyl, especially stearyl, preferably monostearyl, phosphate esters such as monostearyl acid phosphate. Another prefened category of suds suppressors comprises silicone suds suppressors including polyorganosiloxane oils, such as polydimefhylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica. See U.S. 4,265,779, EP 89307851.9, U.S. 3,455,839, and German Patent Application DOS 2,124,526. Silicone defoamers and suds controlling agents in granular detergent compositions are further disclosed in U.S. 3,933,672 and U.S. 4,652,392. In certain prefened silicone suds suppressors useful herein, a solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (prefened), or polypropylene glycol. The primary silicone suds suppressor is branched crosslinked. Certain liquid laundry detergent compositions with controlled suds will comprise from about 0.001 to about 1. most preferably from about 0.05 to about 0.5, weight % of silicone suds suppressor comprising (1 ) a nonaqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than about 2 weight %; and without polypropylene glycol. Similar amounts can be used in granular compositions, gels, etc. See also U.S. Patents 4,978,471, Starch, issued December 18, 1990, and 4,983,316, Starch, issued January 8, 1991, 5,288,431, Huber et al., issued February 22, 1994, and U.S. Patents 4,639,489 and 4,749,740, Aizawa et al at column 1 , line 46 through column 4, line 35. Other suds suppressors useful herein comprise the secondary alcohols (e.g., 2- alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075,1 18 and EP 150,872. The secondary alcohols include the Cg-Cjg alkyl alcohols having a C\-C\ chain. A prefened alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12. Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem. Mixed suds suppressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1 :5 to 5:1.
Suds suppressors, when utilized, are preferably present in a "suds suppressing amount. By "suds suppressing amount" is meant that the formulator of the composition can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines. Other Ingredients
A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including perfumes, enzyme stabilizers, softening clays such as bentonites, montmorillonites, hectorites, other clays such as laponite or kaolin, chlorine scavengers, such as ammonium sulfate; other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, fillers, especially for bar compositions, etc. If desired, magnesium and/or calcium salts such as MgCl2, MgSO4, CaCl2, CaSO4, magnesium silicates and the like, can be added, for example as fillers for bar forms of the compositions.
Various detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating. Preferably, the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate. In use, the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.
The detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 1 1 , preferably between about 7.0 and 10.5, more preferably between about 7.0 to about 9.5. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art. Form of the compositions
Compositions herein can vary in physical form, as nonlimitingly illustrated by granular, tablet, bar, and pouch forms. The compositions include the so-called concentrated granular detergent compositions adapted to be added to a washing machine by means of a dispensing device placed in the machine drum with the soiled fabric load. The mean particle size of the components of granular detergent compositions herein is preferably be such that no more that 5% of particles are greater than 1 7mm in diameter and not more than 5% of particles are less than 0 15mm in diameter
"Mean particle size" herein can be determined by sieving a sample of mateπal to be sized into a number of fractions (typically 5) on a seπes of Tyler sieves Weights of fractions are plotted against the aperture size of the sieves The mean particle size is the aperture size through which 50% by weight of the sample would pass
Certain prefened granular detergent compositions in accordance herein are high- density types, now common in the marketplace, typically these have a bulk density of at least 600 g/htre, more preferably from 650 g/htre to 1200 g/litre Laundry washing method
Machine laundry methods herein typically compnse treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a detergent composition of the invention By an "effective amount" is here meant from 40g to 300g of product dissolved or dispersed a wash solution of volume from 5 to 65 litres
In the context of fabπc laundeπng, product "usage levels" can vary widely, depending not only on the type and seventy of soils and stains, but also on wash water temperatures and volumes and type of washing machine In a prefened use aspect a dispensing device is employed in the washing method
The dispensing device is charged with the detergent product, and is used to introduce the product directly into the drum of the washing machine before the start of the wash cycle Its capacity should be such as to be able to contain sufficient detergent product as would normally be used in the washing method Once the washing machine has been loaded with laundry, the dispensing device containing the detergent product is placed inside the drum At the commencement of the wash cycle of the washing machine, water is introduced into the drum and the drum penodically rotates The design of the dispensing device should be such that it permits containment of the dry detergent product but then allows release of this product duπng the wash cycle in response to its agitation as the drum rotates and also as a result of its contact with the wash water
Alternatively, the dispensing device may be a flexible container, such as a bag or pouch The bag may be of fibrous construction coated with a water impermeable protective mateπal so as to retain the contents, such as is disclosed in European published Patent Application No 0018678 Alternatively it may be formed of a water-msoluble synthetic polymenc matenal provided with an edge seal or closure designed to rupture m aqueous media as disclosed in European published Patent Application Nos 001 1500. 0011501 , 0011502, and 001 1968 A convenient form of water-frangible closure compnses a water soluble adhesive disposed along and sealing one edge of a pouch formed of a water impermeable polymenc film such as polyethylene or polypropylene Abbreviations used in Examples
LAS Sodium Ci ι _i 3 alkyl benzene sulfonate (linear, branched or mixed)
Alkyl Sulfate CxyAS Alkyl sulfate, typically sodium salt form, derived from fatty alcohol containing from x to y carbon atoms Examples include sodium tallow alkyl sulfate (TAS) and primary, guerbet, and mid-chain branched (WO
97;39088) alkyl sulfates containing from 10 to 20 carbon atoms (more typically from 14 to 16 or from 16 to 18) or mixtures thereof
Alkvl Alkoxv Sulfate Sodium salt of linear or branched (WO 97/39087) fatty alcohol condensed with one or more moles of ethylene oxide, propylene oxide, esp sodium
Cj -Cjy alkyl sulfate condensed with z moles of ethylene oxide, e g ,
C15E1 S
Noniomc linear or branched (WO 97/39091 ) noniomc surfactant, typically CxyEz derived from fatty alcohol with chamlength of from x to v condensed with an average of z moles of ethylene oxide Suitable examples include
C25E3, C24E5, C45E7
Glucamide Cj2-C ]4 (coco) alkyl N-methyl glucamide or
Cj 6-C] g alkyl N-methyl glucamide
Amine Oxide linear or branched (WO 97/39091 ) C12-C18 Alkyldimethylamme N-Oxide QAS Quaternary ammonium surfactant, e.g , dodecyltπmethylammonium chloride or
R2 N+(CH3)2(C2H4OH) X" with R2 = C12 - C14 and x " = Cf
Fatty Acid Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallov. and coconut fatty acids (longer-chain soaps may be dual-functional and contribute to suds suppression), Cι 2-Cj4 topped whole cut fatty acids, mixtures
Hybπd builder Mateπal as disclosed in the Synthesis Examples hereinabove Zeolite system one or more of - Zeolite A Hydrated sodium aluminosilicate of formula Naj 2(A102SιO2)^ 27H20 having a primary particle size in the range from 0 1 to 10 micrometers (weight expressed on an anhydrous basis) Zeolite P Zeolite P (may be maximum aluminum type) Zeolite X Zeolite X Zeolite AX Zeolites A,X co-crystallized (Condea, EP 816291 Al ) Silicate system 2r or 3r sodium silicate; crystalline layered silicate of formula δ- a2Sι2θ5
.(Hoechst/Claπant) Amorphous sodium silicate (Sι02:Na20 = 2.0; 1 ). mixtures thereof
(hydration of any zeolite may vary)
Phosphates - one or more of
STPP Anhydrous sodium tπpolyphosphate
TSPP Tetrasodium pyrophosphate non-polymer type polycarboxylate. one or more of :- Citrate Anhydrous citric acid; tπ-sodium citrate dihydrate of activity 86.4% with a particle size distribution between 425μm and 850μm, mixtures thereof
TMSOOS Tartrate Monosuccinate / Tartrate Disuccmate, Sodium Salts
ODS 2,2'-oxydιsuccmate, Sodium Salts
CMOS Carboxymethyloxysuccinate, Sodium Salts
NTA Nitπlotπacetic Acid, Sodium Salts
Carbonate Anhydrous sodium or potassium carbonate, e.g., with particle size between
200μm and 900μm for admix; or lower, e.g., below lOOμm. if to be further agglomerated.
Polymer-type any polycarboxylate of m.w. above about 1 ,000, especially sodium salt of polycarboxylate copolymer of 1 4 maleic/acryhc acid, average molecular weight about
70,000. sodium salt. Sodium polyacrylate of average molecular weight
4,500; mixtures thereof; or mixtures of said polymers with any PEG. A preferred polymer-type polycarboxylate has polyglyoxylate structural units
(see, for example, US 4,146,495; US 4, 140,676; EP 803,521 A)
Carbohydrate Sodium carboxymethyl cellulose; methyl cellulose ether with a degree of antiredeposition agent polymerization of 650 available from Shin Etsu Chemicals ; starch-derived, sugar-derived, sorbitol-deπved or any other carbohydrate-deπved antiredeposition agent or ash buildup prevention agent, or mixtures thereof. Enzyme system; one or more of -
Protease Proteolytic enzyme of activity 4KNPU'g sold by NOVO Industries A/S under the tradename Savmase
Alcalase Proteolytic enzyme of activity 3AU/g sold by NOVO Industries A/S Cellulase Cellulolytic enzyme of activity 1000 CEVU/g sold by NOVO Industries A/S under the tradename Carezyme
Amylase Amylolytic enzyme of activity 120KNU/g sold by NOVO Industries A/S under the tradename Termamyl 120T
Lipase Lipolytic enzyme of activity lOOKLU/g sold by NOVO Industries A/S under the tradename Lipolase
Endolase Endoglucanase enzyme of activity 3000 CEVU/g sold by NOVO Industries
A/S
Primary Oxygen Bleach Sodium perborate tetrahydrate of nominal formula NaB02.3H7O.H207
(abbre\ . PB4). anhydrous sodium perborate bleach of nominal formula
NaB02.H202 (abbre\ PB 1 ); sodium percarbonate of nominal formula
2Na2C0^.3H 02 (abbre\ PC); any of these in coated or uncoated forms; or mixtures thereof
Hydrophi c Bleach any water-soluble acylated di- or lower poly-amine, esp Activator tetraacetylethylenediamine
Hydrophobic Bleach NOBS. i.e.. nonanoyloxybenzene sulfonate in the form of the sodium salt, Activator NAC-OBS. i.e . (6-nonamιdocaproyl) oxybenzene sulfonate; mixtures; or similar
Hydrophobic preformed e.g., EP 778342 A 1 peroxyacid
Organic Bleach Booster e.g.. omega-(3.4-dιhydroιsoquιnohnιum alkane sulfonate(s) of U.S.
5,576,282
Transition-metal Bleach e.g., as descπbed in WO 97/00937. WO 96/06155, EP 718,398 A Catalyst
Photobleach Sulfonated zinc phthlocyanine encapsulated m bleach dextrin soluble polymer; or low-hue photobleach - see, for example, Si phthalocyamne derivatives of WO 97/05202
Chelant System, one or more of:
DTPA Diethylene tπamine pentaacetic acid DTPMP Diethylene tπamine penta (methvlene phosphonate). marketed by Monsanto under the Tradename Dequest 2060
EDDS Ethylenediamine-N.N'-disuccimc acid, (S,S) isomer in the form of its sodium salt
HEDP l . l -hvdro\yethane diphosphonic acid Bπghtener Disodium 4 4'-bιs(2-sulphostyryl)bιphenyl, Disodium 4,4'-bιs(4-anιlιno-6- morpholιno- 1 3 5-tπazιn-2-yl)amιno) stιlbene-2 2'-dιsulfonate, mixtures
Soil Release Agent one or more of SRP 1 Sulfobenzoyl and capped esters with oxyethylene oxy and terephthalovl backbone or SRP of US 5,415,807
SRP 2 Diethoxylated poly ( 1 , 2 propylene terephthalate) short block polymer
Cotton Soil Release Agent e g . as descπbed in WO 97/42285
TEPAE Tetraefhylenepentaamine ethoxylate
PVP Polyvinylpyrrolidine polymer, with an average molecular weight of 60,000
PVNO Polyvmylpyπdone N-oxide polymer, with an average molecular weight of
50.000
PVPVI Copolymer of polyunylpyrohdone and vinyhmidazole with an average molecular weight of 20,000
Antifoam System e g , polydimefhvlsiloxane foam controller with siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10 1 to 100 1 , may be complemented by fatty acιd(s)
Other materials Bicarbonate Anhydrous sodium bicarbonate w ith a particle size distribution between 400μm and 1200μm
Sulfate Anhydrous sodium sulfate
Stabilizers, process aids, other minors e g , one or more of
Borate Sodium borate
Wax Paraffin wax
PEGx Polyethylene glycol, with a molecular weight of x
PEO Polyethylene oxide, with an average molecular weight of 50.000
Perfume Any perfume or pro-perfume, see, for example, "blooming perfume" m WO
97 34987 In the following examples all levels are quoted as % by weight of the composition'
Example 1
Granular laundry detergents for use in domestic appliances or handvvashmg of laundry at from 100 to 10,000 ppm, depending on appliance and/or water and/or conditions, are re ared in accordance with the invention:
Example 2
Granular laundry detergents for use in domestic appliances or handwashing of laundry at from 100 to 10,000 ppm, depending on appliance and/or water and/or conditions, are prepared in accordance with the invention:
High Density Detergent Composition Processes
Spray-drying towers can be used to make granular laundry detergents or base powders These often have a density less than about 500 g/1 Typically, an aqueous slurry of ingredients is passed through a spray-drymg tower at temperatures of about 175°C to about 225°C
Additional process steps must be used to obtain high density, low dosage detergents "High density" means greater than about 550, typically greater than about 650, grams/liter or "g/1") Thus spray-dned granules can be densified by loading a liquid, often a noniomc surfactant, into the pores of the granules and/or passing them through one or more high speed mixer/densifiers such as a device sold as a "Lodige CB 30" or "Lodige CB 30 Recycler" This comprises a static cyhndπcal mixing drum having a central rotating shaft on which are mounted mixing/cutting blades Ingredients for the detergent composition are introduced into the drum and the shaft/blade assembly is rotated at speeds in the range of 100-2500 m to provide thorough mixing/densification See U.S 5,149,455 and 5,565,422 Other suitable commercial apparatus includes the "Shugi Granulator" and the "Drais K-TTP 80
Spray-dned granules can also be densified by treating them in a moderate speed mixer/densifier so as to obtain particles, for which the "Lodige KM" (Senes 300 or 600) or "Lodige Ploughshare" mixer/densifiers are suitable and are typically operated at 40-160 φm Other useful equipment includes the "Drais K-T 160" This process step using a moderate speed mixer/densifier (e g Lodige KM) can be used alone or sequentially with the aforementioned high speed mixer/densifier (e g Lodige CB) to achieve the desired density Other types of granules manufactuπng apparatus useful herein include the apparatus disclosed in U.S Patent 2,306,898, to G L Heller, December 29, 1942
While it may be more suitable to use the high speed mixer/densifier followed by the low speed mixer/densifier, the reverse sequential mixer/densifier configuration can also be used One or a combination of various parameters including residence times m the mixer/densifiers, operating temperatures of the equipment, temperature and/or composition of the granules, the use of adjunct ingredients such as liquid binders and flow aids, can be used to optimize densification of the spray-dned granules By way of example, see the processes in U S 5,133,924, U S 4,637.891 , (granulating spray-dned granules with a liquid binder and aluminosilicate), U S 4,726,908, (granulating spray - dned granules with a liquid binder and aluminosilicate;, and U S 5,160,657, (coating densified granules with aluminosilicate) Heat sensitive or highly volatile detergent ingredients are preferably incoφorated into the detergent composition without resorting to spray drying, for example, by feeding thermally sensitive or volatile ingredients continuously or batchwise into mixing/densifying equipment One prefened embodiment involves charging a surfactant paste and an anhydrous mateπal into a high speed mixer/densifier (e g Lodige CB) followed by a moderate speed mixer/densifier (e g Lodige KM) to form high density agglomerates See U S 5,366,652 and U S 5,486,303 The liquid/solids ratio of ingredients can be selected to obtain high density agglomerates that are more free flowing and crisp See U S 5,565,137
Optionally , the process may include one or more streams of undersized particles These can be recycled to the mixer/densifiers for further agglomeration or build-up Oversized particles can be sent to grinding apparatus, the product of which is fed back to the mixing/densifying equipment Such recycles facilitate overall particle size control giving in finished compositions which hav ing a relatively uniform distπbution of particle size (400-700 microns) and density (> 550 g 1) See U S 5,516,448 and U S 5,489,392 Other suitable processes which do not call for sprav-drymg are descnbed in U S 4,828,721, U S 5,108,646 and h S 5.178,798
In yet another embodiment, the high density detergent compositions can be produced using a fluidized bed mixer in which the ingredients are combined as an aqueous slurry (typically 80% solids content) and sprayed into a fluidized bed to provide finished granules Optionally pnor to fluid bed mixing the slurry can be treated using the aforementioned Lodige CB mixer/densifier or a "Flexomix 160" mixer/densifier, available from Shugi Fluidized bed or moving beds of the type available under the tradename "Escher Wyss" can also be used
Another alternate process involves feeding a liquid acid precursor of an anionic surfactant, an alkaline inorganic mateπal (e g sodium carbonate) and optionally other detergent ingredients into a high speed mixer/densifier (residence time 5-30 seconds) so as to form particles containing a partially or totally neutralized anionic surfactant salt and the other starting detergent ingredients Optionally, the contents in the high speed mixer/densifier can be sent to a moderate speed mixer/densifier (e g Lodige KM) for further mixing resulting in the finished high density detergent composition See U S 5.164,108 Optionally, high density detergent compositions can be produced by blending conventional spray-dned detergent granules with detergent agglomerates m vanous proportions (e g a 60 40 weight ratio of granules to agglomerates) produced by one or a combination of the processes discussed herein Additional adjunct ingredients such as enzymes, perfumes, bπghteners and the like can be sprayed oi admixed with the agglomerates, granules or mixtures thereof produced by the processes discussed herein For example, see US 5,569,645 EXAMPLES 4-6 Several detergent compositions made in accordance with the invention and specifically for top-loading washing machines are exemplified below The base granule is prepared by a conventional spray drying process in which the starting ingredients are formed into a slurry and passed though a spray drying tower having a countercunent stream of hot air (200-300°C) resulting in the formation of porous granules The admixed agglomerates are formed from two feed streams of detergent ingredients which are continuously fed, at a rate of 1400 kg/hr, into a Lodige CB-30 mixer/densifier, one of which compnses a surfactant paste containing surfactant and water and the other stream containing starting dry detergent matenal containing sodium carbonate and insoluble inorganic builder such as hybrid aluminosilicate or combinations thereof with zeolite The rotational speed of the shaft in the Lodige CB-30 mixer/densifier is about 1400 The contents from the Lodige CB-30 mixer/densifier are continuously fed into a Lodige KM- 600 mixer/densifier for further build-up agglomeration The resulting detergent agglomerates are then fed to a fluid bed dryer and to a fluid bed cooler before being admixed with the spray dned granules The remaining adjunct detergent ingredients are sprayed on or dry added to the blend of agglomerates and granules Alternately the magnseiosihcate can be dry-added, in hole or in part, to the composition
Base Granule
Aluminosilicate 180 0 170
Sodium sulfate 100 80 190 Sodium polyacrylate polvmer 30 30 20
PolyethyleneGlycol (MW=4000) 20 20 10
C j 2- 13 lmear alkylbenzene 60 60 70 sulfonate, Na
Cj4_i6 secondary alkyl sulfate, Na 30 30 30 14.15 alkyl ethoxvlated sulfate, Na 30 30 90
Sodium silicate 10 10 20 Bπghtener 24^ 0.3 0.3 0.3
Sodium carbonate 7.0 7.0 25 *7
DTPA ] 0.5 0.5 -
Admixed Agglomerates
C]4_j ς alkyl sulfate, Na 5.0 5.0 -
C j 2- 13 linear alkylbenzene 2.0 2.0 - sulfonate, Na
Sodium Carbonate 4.0 1 1.0 -
PolyethyleneGlycol (MW=4000) 1.0 1.0 -
Admix
Hybrid aluminosilicate - 20.0 5.0
C12-i5 alkyl ethoxylate (EO = 7) 2.0 2.0 0.5
Perfume 0.3 0.3 1.0
Polyvinylpyrπ done 0.5 0.5 -
Polyvinylpyπdine N-oxide 0.5 0.5 -
Polyvinylpyrrolidone-polyvinyhmidazole 0.5 0.5 -
Distearylamine & Cumene sulfonic acid 2.0 2.0 -
Soil Release Polymer - 0.5 0.5 -
Lipolase Lipase ( 100.000 LU/1)4 0.5 0.5 -
Termamyl amylase (60 KNU/g)- 0.3 0.3 -
CAREZYME® ( 1000 CEVU/g)4 0.3 0.3 -
Protease (40mg/g)-s 0.5 0.5 0 5
NOBS 3 5.0 5.0 -
Sodium Percarbonate 12.0 12.0 -
Polydimethylsiloxane 0.3 0.3 -
Miscellaneous (water, etc.) balance balance balance
Total 100 100 100
' Diethylene Tπamine Pentaacetic Acid
2Made according to U.S. Patent 5.415,807. issued May 16, 1995
3 Nonanoyloxybenzenesulfonate
4 Purchased from Novo Nordisk A/S ^ Purchased from Genencor
" Purchased from Ciba-Geigy Aluminosilicate = 1 - 10 A Zeolite A

Claims

WHAT IS CLAIMED IS:
1. A detergent composition comprising:
(a) from 0.1 % to 99% of a builder system comprising, in part, a particulate inorganic ion-exchanging builder material, said builder material comprising:
(i) a hybrid of crystalline aluminosilicate, preferably a hybrid of crystalline zeolitic aluminosilicate; and
(ii) at least one occluded cobuilder, preferably selected from the group consisting of occluded silicate cobuilder, occluded nonsihcate cobuilder, and mixtures thereof, more preferably an occluded silicate cobuilder,
(iii) optionally, at least one cobuilder or adjunct other than said occluded cobuilder adsorbed on or externally chemically bonded to said fiydrid; wherein preferably said hybrid has a SiOJALO, ratio below 3 and is formed by a process comprising the step of adding an aluminum source to a concentrated silicate solution having a pH above 12, said silicate solution having been at least partially depolymerized by heating prior to the addition of said aluminum source; and
(b) from 0.1% to 99% of at least one detergent adjunct, preferably selected from adjuncts other than any adjunct of said builder system, more preferably selected from the group consisting of:
(i) detersive surfactants, preferably from 0.1 % to 30% by weight of said detergent composition, preferably selected from the group consisting of: cationic surfactants, anionic surfactants, surfactants having at least one biodegrabably branched hydrophobe and mixtures thereof, wherein the surfactant having at least one biodegradably branched hydrophobe is preferably selected from mid-chain-
C,-C4-branched C8-C,8-alkyl sulfates, mid-chain-C,-C4-branched C8-C18-alkyl ethoxylated, propoxylated or butoxylated alcohols, mid-chain-C,-C -branched C8- CI8-alkyl ethoxysulfates, mid-chain-C,-C4-branched C8-C1()-alkyl benzenesulfonates and mixtures thereof; (ii) organic polymeric materials selected from the group consisting of end capped oligomeric esters, hydrophobically modified polyacrylates, teφolymers comprising maleate or acrylate, polymeric dye transfer inhibitors, polyimine derivatives, and mixtures thereof;
(iii) oxygen bleach promoting materials selected from the group consisting of organic bleach boosters, transition-metal bleach catalysts, photobleaches, bleach-promoting enzymes and mixtures thereof; (iv) fabric care promoting agents other than softeners or said organic polymeric materials; and
(v) optionally, a chelant or a dual-chelant system having at least one nonphosphonate aminofunctional chelant and at least one phosphonate-functional chelant; and
(vi) optionally, a polycarboxylate polymer, preferably a Muφhy-type polycarboxylate polymer system; wherein said polycarboxylate polymer, when present, is present in said detergent composition at a level less than 2% by weight of the composition; and (vii) mixtures of (i) - (vi).
2. A detergent composition according to Claim 1 wherein said hybrid of crystalline zeohtic aluminosilicate comprises from 0.01 to 1.0 weight fraction of said builder system and said hybrid of crystalline zeolitic aluminosilicate is characterized by a capacity to sequester calcium in excess of the amount of charge inducing aluminum in the zeolitic aluminosilicate and/or said hybrid of crystalline zeolitic aluminosilicate is characterized by a calcium ion exchange capacity of at least 15% greater than the calcium ion exchange capacity of a reference material selected from non-hybridized zeolite A.
3. A detergent composition according to any of the preceding Claims wherein said occluded nonsihcate cobuilder is selected from (i) the group consisting of occluded phosphate, occluded carbonate, occluded borate, occluded nitrate, occluded nitrite, occluded sulfate, occluded Na;O and mixtures thereof; and (ii) mixtures of said occluded nonsihcate cobuilder and occluded silicate; provided that in any of said mixtures of occluded nonsihcate cobuilder and occluded silicate, the weight fraction of occluded silicate is no more than 0.99, preferably no more than 0.80.
4. A detergent composition according to any of the preceding Claims wherein said adsorbed or externally chemically bonded cobuilder or adjunct is a nonbuilder adjunct and wherein said nonbuilder adjunct reduces the negative surface charge of the hybrid relative to the nontreated hybrid, whereby said component (a) has improved compatibility with cationically charged surfactants and/or enzymes.
5. A detergent composition according to any of the preceding Claims wherein said occluded cobuilder is selected from the group consisting of occluded nonsihcate cobuilder and mixtures of occluded nonsihcate cobuilder and occluded silicate cobuilder; and wherein said occluded nonsihcate cobuilder is selected from the group consisting of occluded nitrate, occluded phosphate, occluded carbonate, occluded borate, occluded nitnte, occluded sulfate, occluded N ,O and mixtures thereof
6 A detergent composition according to any of the preceding Claims wherein said hybπd compnses at least 0 01 weight fraction of said builder system and wherein said occluded cobuilder is selected from the group consisting of occluded silicate cobuilder, occluded nonsihcate cobuilder and mixtures of said occluded silicate cobuilder and said occluded silicate cobuilder, and wherein said occluded nonsihcate cobuilder, when present, is present at a weight ratio to occluded silicate cobuilder of from 1 1000 to
1000 1 and is selected from the group consisting of occluded nitrate, occluded phosphate, occluded carbonate, occluded borate, occluded nitnte, occluded sulfate, occluded Na,O and mixtures thereof
7 A detergent composition according to any of the preceding Claims wherein said hybrid comprises at least 0 10 weight fraction of said builder system and wherein from 0 10 to 0 90 weight fraction of said builder system is selected from the group consisting of zeolite A, zeolite B, zeolite P, zeolite MAP, zeolite X, zeolite AX, clays, layer silicates, chain silicates, soluble silicates, citrates, nitπlotπacetates, ethercarboxylates, carbonates, polyacetal carboxylates. and mixtures thereof, wherein said ethercarboxylates are preferably selected from the group consisting of carboxymethyloxysuccinate, tartrate monosuccinate, tartrate disuccinate, oxydisuccinate and mixtures thereof and wherein said carbonates are preferably selected from the group consisting of sodium carbonate, sodium bicarbonate and mixtures thereof
8 A detergent composition according to any of the preceding Claims wherein the builder system has measurable hydroxysodahte as evidenced by XRD powder pattern, preferably as evidenced by peaks at 14 0, 24 3 and 25 1 degrees 2 theta in the XRD powder pattern of the builder system taken as a whole, more preferably wherein the hybπd has measurable hydroxysodahte as evidenced by peaks at 14 0, 24 3 and 25 1 degrees 2 theta in the XRD powder pattern of the hybπd examined on its own
9 The detergent composition according to any of the preceding Claims wherein said hybπd builder material has a capacity to sequester calcium in excess of the amount of charge inducing aluminum in the crystals of the hybπd builder mateπal
10 The detergent composition according to any of the preceding Claims wherein said hybrid builder mateπal comprises is characterized by a calcium ion exchange capacity of at least 25% greater than the calcium ion exchange capacity of a reference mateπal selected from non-hybridized zeolite A
1 1 The detergent composition according to any of the preceding Claims wherein the total SiO, in said hybrid builder mateπal is from 1 02 to 1 50 times the framework SiO-, as determined by compaπson of x-ray diffraction, x-ray fluorescence and 29Sι NMR analysis
12 The detergent composition according to any of the preceding Claims wherein said step of depolymenzmg said sodium silicate solution compnses heating at temperatures of from 50 °C to 85 °C for a period of 10 minutes or longer
13 The detergent composition according to any of the preceding Claims wherein said composition compnses soluble silicate as a non-occluded cobuilder and wherein the total level of soluble silicate in said composition as a whole is limited, and is preferably no more than the equivalent of 3% by weight of the composition of 2 Or sodium silicate
14 The detergent composition according to any of the preceding Claims wherein said builder system compnses said particulate hybrid aluminosilicate material in conjunction with at least one traditional builder material, at a ratio of hybnd aluminosilicate to traditional builder mateπal of from 5 1 to 1 5
15 A detergent composition according to any of the preceding Claims wherein said hybπd has a SiOJAKO, ratio below 3 and formed by a process compπsing the step of adding an aluminum source to a concentrated silicate solution having a pH above 12, said silicate solution having been at least partially depolymenzed by heating pnor to the addition of said aluminum source and further, optionally but preferably, at least one source of occludable nonsihcate cobuilder having been added m any step and/or further, optionally but preferably, at least one surface treating agent having been applied to the external surfaces of said hybπd after formation thereof, subject to at least one of the following provisions with respect to the composition of said builder system - the builder system has measurable hydroxysodahte as evidenced by peaks at 14 0, 24.3 and 25 1 degrees 2 theta in the XRD powder pattern of the builder system taken as a whole and/or - the hybrid has measurable hydroxysodahte as evidenced by peaks at 14.0, 24.3 and 25.1 degrees 2 theta in the XRD powder pattern of the builder system taken on its own and/or
- the hybrid has measurable occluded nonsihcate cobuilder as evidenced directly and/or indirectly by any combination of elemental analysis, XRD powder pattern, 29Si NMR or other known techniques and/or
- the hybrid has measurably different wetting and/or surface charge as compared with a non-surface treated hybrid.
16. A detergent composition according to any of the preceding Claims wherein said hybrid comprises occluded silicate; wherein said hybrid is characterized by 9Si NMR peaks in the range -81 to -85 ppm.
17. A detergent composition according to any of the preceding Claims wherein said detergent composition has the form of a laundry bar, tablet, low-density granule or powder, high-density granule or powder (e.g., > 600 g/liter), paste, or gel, wherein said hybrid has a measurable improvement in the sum of Calcium binding and Magnesium binding as compared to Zeolite A, delta-layer silicates and mixtures thereof.
18. A detergent composition according to any of the preceding Claims wherein said detergent composition is in solid form and the process for preparing the detergent composition comprises at least one step of combining said hybrid material with a film- forming polymer.
19. A detergent composition according to any of the preceding Claims wherein the hybrid material has measurably different wetting and/or surface charge as compared with a non-surface treated hybrid, and preferably wherein said measurable difference is accomplished by a step of treating the hybrid material with PEG or a film-forming polymer.
20. A detergent composition according to any of the preceding Claims wherein said chelant, when present, is present in said detergent composition at a level less than 2%> by weight of the composition; preferably from 0.1% to 1.5% by weight of the composition; wherein said chelant is preferably selected from the group consisting of: DTPA; EDTA;
S,S'-EDDS and mixtures thereof.
EP00906921A 1999-01-21 2000-01-14 Improved detergent compositions comprising hybrid zeolite builders Withdrawn EP1144581A1 (en)

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WO2002046346A1 (en) * 2000-12-05 2002-06-13 Unilever Plc Improved detergent bar composition
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CN100353157C (en) * 2005-05-24 2007-12-05 周大宁 Liquid for testing effect of washing hands
JP5133083B2 (en) * 2008-02-08 2013-01-30 花王株式会社 Liquid detergent composition
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JP6238451B2 (en) * 2014-04-16 2017-11-29 ライオン株式会社 Liquid detergent for textile products
WO2018124092A1 (en) * 2016-12-27 2018-07-05 花王株式会社 Powder detergent composition for textile products
CN109135936A (en) * 2017-06-27 2019-01-04 海门市彼维知识产权服务有限公司 A kind of strong dirt-removing detergent
CN107699398A (en) * 2017-10-19 2018-02-16 杨忠华 A kind of special liquid detergent of bafta
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