Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/046—Salts
• • 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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
• • 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
  • C11D1/37—Mixtures of compounds all of which are anionic
• • 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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
  • C11D17/065—High-density particulate detergent compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/10—Carbonates ; Bicarbonates
• • 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
  • C11D1/29—Sulfates of polyoxyalkylene ethers

Definitions

• the present invention relates to granular detergent compositions having surfactant particles with reduced electrolyte concentrations, and m particular to detergent compositions with surfactant particles of reduced carbonate levels
• liquid detergent compositions granular products retain numerous advantages. These advantages include performance, formulation capability, lower-cost packaging and higher product stability.
• the advantages of product stability and formulation capability are derived in large part from the nature of granular admixtures where components can be individually stabilized and isolated into particles before being admixed with other particles. This physical separation m the final detergent composition allows the use of materials that are potentially unstable in a composition such as bleaches, enzymes, etc.
• performance of granular detergent compositions depends on depends on both dispersion of the granules in the wash water and the dissolution of the individual granules. In general, there is an optimal balance between the two properties. Particles that dissolve well typically have poor dissolution while particle that disperse well are often slow to dissolve. While slow dissolution impacts cleaning performance by limiting the amount of cleaning agent available in the wash, it is poor dissolution that may have the greatest consumer noticeable impact is non- soluble residues on fabrics
• One way to minimize these electrolyte-surfactant interactions is to simply reduce the amount of electrolyte m the formulation.
• a reduction of the typically alkaline electrolytes, for example sodium carbonate will result in a reduction the wash water pH and as a result a reduction m cleaning peiformance of the detergent composition Therefore, it is desirable to maintain, if not increase, the level of electrolyte m the formulation.
• the need remains to impro ⁇ 'e the dissolution issues surrounding granular detergent compositions to maintain formulation flexibility over liquid detergent compositions, particularly dissolution m cold water conditions.
• the present invention involves the formulation of a fully formulated detergent composition which comprises a surfactant system having an electrolyte rich surfactant zone and an electrolyte poor surfactant zone.
• the composition may be m the form of a single particle with separate discrete surfactant zones or may be in the form of multiple particles wherein each surfactant zone is represented by a separate particle
• the electrolyte poor zone is an agglomerated detergent particle and the electrolyte rich zone is a spray-dried detergent particle.
• the composition also includes other detergent adjunct ingredients.
• the electrolyte poor surfactant zone comprises less than about 20%, more preferably less than about 10%, even more preferably less than about 2% and most preferably about 0% electrolyte m conjunction with a surfactant or blend of surfactants selected from the class of alkyl sulfate surfactants.
• the electrolyte rich surfactant zone comprises more than about 20%, more preferably more than about 35% and most preferably more than about 45% electrolyte m conjunction with a surfactant or blend of surfactants selected from an anionic surfactant which is not an alkyl sulfate suifactants, preferably alkyl benzene sulfonates
• a surfactant or blend of surfactants selected from an anionic surfactant which is not an alkyl sulfate suifactants, preferably alkyl benzene sulfonates
• an object of the present invention to provide a superior performing granular detergent composition which has the solubility profile on par with liquid detergents.
• this solubility via zone separation of electrolytes and certain surfactant ingredients.
• particles means the entire size range of a detergent final product or component or the entire size range of discrete particles, agglomerates, or granules in a final detergent product or component admixture. It specifically does not refer to a size fraction (i.e., representing less than 100% of the entire size range) of any of these types of particles unless the size fraction represents 100% of a discrete particle in an admixture of particles. For each type of particle component in an admixture, the entire size range of discrete particles of that type have the same or substantially similar composition regardless of whether the particles are in contact with other particles.
• the agglomerates themselves are considered as discrete particles and each discrete particle may be comprised of a composite of smaller primary particles and binder compositions.
• geometric mean particle diameter means the geometric mass median diameter of a set of discrete particles as measured by any standard mass-based particle size measurement technique, preferably by dry sie ⁇ 'ing.
• the phrase "geometric standard deviation" or “span” of a particle size distribution means the geometric breadth of the best-fitted log-normal function to the above-mentioned particle size data which can be accomplished by the ratio of the diameter of the 84.13 percentile divided by the diameter of the 50 th percentile of the cumulative distribution (D S .13 /D 5 o); See Gotoh et al, Powder Technology ⁇ Handbook, pp. 6-11, Meral Dekker 1997. .
• the phrase “builder” means any inorganic material having “builder” performance in the detergency context, and specifically, organic or inorganic material capable of removing water hardness from washing solutions
• the term “bulk density” refers to the uncompressed, untapped powder bulk density, as measured by pouring an excess of powder sample through a funnel into a smooth metal vessel (e.g., a 500 ml volume cylinder), scraping off the excess from the heap above the nm of the vessel, measuring the remaining mass of powder and dividing the mass by the volume of the vessel.
• the present invention involves the design of a granular detergent composition having superior solubility via the separation of selected detergent ingredients that have increased tendency to form gels of lower solubility during the dispersion and dissolution of a granular detergent when in proximity to each other.
• the detergent ingredients which have been identified as having the increased tendency to form lump-gel residues are alkyl sulfate surfactants and electrolytes. Electrolytes are commonly present in detergent compositions to provide such benefits as alkalinity, building etc. and are typically present as alkali metal salts such as carbonate, chloride and sulfate salts. Most typical is sodium carbonate and is the most pieferred electrolyte according to the present invention.
• the granular detergents are divided into electrolyte poor and electrolyte rich zones.
• the electrolyte poor zone contains lower levels of electrolyte than that present m the electrolyte rich zone.
• the alkyl sulfate surfactants are concentrated m the electrolyte poor zone thereby minimizing their interaction with the electrolytes prior to complete solubility of the surfactants
• the electrolyte poor zone contains less than about 20% by weight of the particle of electrolyte, preferably less than about 10% by weight and most preferably less than about 2% by weight of the particle of the electrolyte with levels around 0 being the most preferred.
• the electrolyte poor zone also preferably includes at least about 2%, more preferably about 5% and most preferably about 10% by weight of the particle of the alkyl sulfate surfactant.
• the electrolyte rich zone contains higher levels of the electrolyte than that present in the electrolyte poor zone. Accordingly, anionic surfactants other than the alkyl sulfates may be formulated into this electrolyte rich zone.
• the anionic surfactant in this zone is an alkyl benzene sulfonate surfactant.
• the electrolyte rich zone contains more than about 20% by weight of the particle of electrolyte, preferably more than about 30%, and more preferably more than about 35% by weight of the particle of electrolyte In addition, the electrolyte rich zone contains more than about 0% by weight of the particle of anionic surfactant, more preferably more than about 2% and most preferably more than 5% by weight of the particle.
• the electrolyte poor zone and the electrolyte nch zone comprise separate particles diffe ⁇ ng composition as formulated into the granular detergent.
• the particles may be selected from spray-dried, agglomeration, extrusion, pelletization, compaction and various other particle making processes as well known in the art.
• one particle may be a spray-dried particle while the other particle is agglomerated
• the electrolyte rich zone is a spray-dried particle while the preferred electrolyte poor zone is an agglomerated particle
• the preferred electrolyte poor zone is an agglomerated particle
• the electrolyte rich zone and the electrolyte poor zone are separate and distinct zones of the same particle.
• two separate sub-particles of differing composition may be agglomerated together to form single particle having the distinct zones as described herein.
• the anionic surfactants useful in the present invention are split into the alkyl sulfate surfactants which according to the present invention are separated from the electrolytes m the detergent composition and the remaining anionic surfactants which may be formulated m either particle.
• the alkyl sulfates are defined as alkyl sulfates, alkyl alkoxy sulfate, alkyl sulfonates, alkyl alkoxy carboxylate, alkyl alkoxylated sulfates with the remaining amomc surfactant being selected from the group consisting of alkylbenzene sulfonate, alpha olefin sulfonate, paraffin sulfonates, alkyl ester sulfonates, , sarcosinates, taurmates, and mixtures thereof.
• amomc surfactant When present, amomc surfactant will be present typically m an effective amount m the overall detergent composition. More preferably, the composition may contain at least about 0.5%, more preferably at least about 5%, even more preferably still, at least about 10% by weight of said composition of anionic surfactant. The composition will also preferably contain no more than about 90%, more preferably no more than about 50%, even more preferably, no more than about 30%o by weight of said composition of amomc surfactant.
• Alkyl sulfate surfactants providing excellent overall cleaning ability alone and particularly when used in combination with polyhydroxy fatty acid amides (see below), including good grease/oil cleaning over a wide range of temperatures, wash concentrations, and wash times, dissolution of alkyl sulfates can be obtained, as well as improved formulabihty liquid detergent formulations are water soluble salts or acids of the formula ROS03M wherein R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydioxyalkyl having a C10-C20 alkyl component, more preferably a C12-C18 alkyl or hydroxyalkyl, and M is H or a cation, e g , an alkali (Group IA) metal cation (e.g , sodium, potassium, lithium), substituted or unsubstituted ammonium cations such as methyl-, dimethyl-, and t ⁇ methyl ammonium and quaternary ammonium
• alkyl sulfate surfactant preferably is the secondary (2.3) alkyl sulfates. These surfactants preferably are of the formula:
• these surfactants contain from 10 to 18 carbon atoms. Suitable examples of these amomc surfactants are disclosed m U.S. 3,234,258 Morris, issued February 8, 1966; U.S. 5,075,041 Lutz, issued December 24, 1991 ; U.S. 5,349,101 Lutz et al., issued September 20, 1994; and U.S. 5,389,277 P ⁇ eto, issued February 14, 1995 each incorporated herein by reference;
• alkyl sulfate surfactant are the alkyl alkoxylated sulfate.
• These surfactants are water soluble salts or acids typically of the formula RO(A)mS03M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably C12-C18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, etc.), ammonium or substituted-ammomum cation.
• R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10-C24
• Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein Specific examples of substituted ammonium cations include methyl-, dimethyl-, t ⁇ methyl-ammomum and quaternary ammonium cations, such as tetramethyl-ammomum, dimethyl pipe ⁇ dinium and cations derived from alkanolammes, e.g monoethanolamme, diethanolamme, and t ⁇ ethanolamine, and mixtures thereof
• Exemplary surfactants are C12-C18 alkyl polyethoxylate (1.0) sulfate, C12-C18 alkyl polyethoxylate (2.25) sulfate, C12-C18 alkyl polyethoxylate (3 0) sulfate, and C12-C18 alkyl polyethoxylate (4.0) sulfate wherein M is conveniently selected from sodium and potassium.
• Surfactants for use herein can be made from natural or synthetic alcohol feedstocks
• Cham lengths represent average hydrocarbon distributions, including branching
• the amomc surfactant component may comprise alkyl sulfates and alkyl ether sulfates derived from conventional alcohol sources, e g , natural alcohols, synthetic alcohols such as those sold under the trade name of NEODOLTM, ALFOLTM, LIALTM, LUTENSOLTM and the like.
• Alkyl ether sulfates are also known as alkyl polyethoxylate sulfates.
• alkyl sulfate surfactant are one or more (preferably a mixture of two or more) mid-cham branched surfactants, preferably mid-cham branched alkyl alkoxy alcohols having the formula:
• M is a water soluble cation and may comprises more than one type of cation, for example, a mixture of sodium and potassium.
• the index w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; z is an integer of at least 1; provided w + x + y + z is from 8 to 14.
• EO and PO represent ethyleneoxy units and propyleneoxy units having the formula:
• the mid-chain branched surfactants are preferably mixtures which comprise a surfactant system Therefore, when the surfactant system comprises an alkoxylated surfactant, the index m indicates the average degree of alkoxylation withm the mixture of surfactants. As such, the index m is at least about 0.01 , preferably with the range of from about 0.1, more preferably from about 0.5, most preferably from about 1 to about 30. preferably to about 10. more preferably to about 5.
• the value of the index m lepresents a distribution of the average degree of alkoxylation corresponding to m, or it may be a single specific chain with alkoxylation (e.g., ethoxylation and/or propoxylation) of exactly the number of units corresponding to m.
• the preferred mid-cham branched surfactants of the present invention which are suitable for use in the surfactant systems of the present invention have the formula:
• the surfactant systems of the present invention which comprise mid-cham branched surfactants are preferably formulated m two embodiments.
• a first preferred embodiment comprises mid-chain branched surfactants which are formed from a feedstock which comprises 25% or less of mid-cham branched alkyl units. Therefore, prior to admixture with any other conventional surfactants, the mid-cham branched surfactant component will comprise 25% or less of surfactant molecules which are non-lmear surfactants
• a second preferred embodiment comprises mid-cham branched surfactants which are formed from a feedstock which comprises from about 25% to about 70% of mid-cham branched alkyl units. Therefore, prior to admixture with any other conventional surfactants, the mid-cham branched surfactant component will comprise from about 25% to about 70% surfactant molecules which are non-lmear surfactants.
• anionic surfactant which are not included in the alkyl sulfates according to the present invention
• one type of anionic surfactant which can be utilized encompasses alkyl ester sulfonates. These are desirable because they can be made with renewable, non-petroleum resources.
• Preparation of the alkyl ester sulfonate surfactant component can be effected according to known methods disclosed in the technical literature. For instance, linear esters of C8-C20 carboxylic acids can be sulfonated with gaseous S03 according to "The Journal of the American Oil Chemists Society," 52 (1975), pp. 323-329. Suitable starting materials would include natural fatty substances as derived from tallow, palm, and coconut oils, etc.
• the preferred alkyl ester sulfonate surfactant especially for laundry applications, comprises alkyl ester sulfonate surfactants of the structural formula:
• R3 is a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof
• R4 is a C1-C6 hydrocarbyl, preferably an alkyl, or combination thereof
• M is a soluble salt-forming cation.
• Suitable salts include metal salts such as sodium, potassium, and lithium salts, and substituted or unsubstituted ammonium salts, such as methyl-, dimethyl, -trimethyl, and quaternary ammonium cations, e.g. tetramethyl-ammonium and dimethyl piperdinium, and cations derived from alkanolammes, e.g. monoethanol-amine, diethanolamme, and triethanolamine.
• R3 is C10-C16 alkyl
• R4 is methyl, ethyl or isopropyl.
• methyl ester sulfonates wherein R3 is C14-C16 alkyl.
• alkylbenzenesulphonates include the hard (ABS, TPBS), linear types, also known as LAS, and made by known process such as various HF or solid HF e.g., DETAL® (UOP) process, or made by using other Lewis Acid catalysts e.g., A1C1 3 . or made using acidic silica/alumina or made from chlorinated hydrocarbons, such as C9-C20 linear alkylbenzene sulfonates, particularly sodium linear alkyl C10-C15 benzene sulfonate.
• surfactants are water soluble salts or acids typically of the formula RAS03M wherein R is a branched or linear C10-C24 alkyl group, preferably a C10-C20 alkyl, more preferably C10-C18 alkyl, A is an aryl group , preferably benzene, or toluene, more preferably benzene unit, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, etc.), ammonium or substituted- ammonium cation.
• RAS03M wherein R is a branched or linear C10-C24 alkyl group, preferably a C10-C20 alkyl, more preferably C10-C18 alkyl, A is an aryl group , preferably benzene, or toluene, more preferably benzene unit, and M is H or a cation which can be, for example, a metal
• the surfactant systems of the laundry detergent compositions of the present invention can also comprise from about 0.001%, preferably from about 1%, more preferably from about 5%, most preferably from about 10% to about 100%, preferably to about 60%, more preferably to about 30% by weight, of the surfactant system, of one or more (preferably a mixture of two or more) modified alkyl arylsulfonate surfactants, or MLAS preferably surfactants wherein the aiyl unit is a benzene ring having the formula:
• L is an acyclic hydrocarbyl moiety comprising from 6 to 18 carbon atoms
• R 1 , R 2 , and R 3 are each independently hydrogen or C C 3 alkyl, provided R 1 and R 2 are not attached at the terminus of the L unit
• M is a water soluble cation having charge q wherein a and b are taken together to satisfy charge neutrality.
• amomc surfactants useful for detersive purposes can also be included in the compositions hereof These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamme salts) of soap, C8-C22 primary or secondary alkanesulphonates, C8-C24 olefinsulphonates, sulphonated polycarboxyhc acids prepared by sulphonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in Bntish patent specification No.
• salts including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamme salts
• soap C8-C22 primary or secondary alkanesulphonates
• C8-C24 olefinsulphonates C8-C24 olefinsulphonates
• sulphonated polycarboxyhc acids prepared by sul
• alkyl glycerol sulfonates 1,082,179, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isothionates such as the acyl isothionates, N-acyl taurates, fatty acid amides of methyl tau ⁇ de, alkyl succmamates and sulfosuccmates, monoesters of sulfosuccmate (especially saturated and unsaturated C12-C18 monoesters) diesters of sulfosuccmate (especially saturated and unsaturated C6-C14 diesters), N-acyl sarcosmates, sulfates of alkylpolysaccha ⁇ des such as the sulfates of alkylpoly
• Resm acids and hydrogenated resin acids are also suitable, such as rosm, hydrogenated rosm. and resin acids and hydrogenated res acids present in or derived from tall oil Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch) A vanety of such surfactants are also generally disclosed m U.S. Patent 3,929,678, issued December 30, 1975 to Laughlm, et al. at Column 23, line 58 through Column 29, line 23.
• Another type of useful anionic surfactant are the so-called diamonics. These are surfactants which have at least two amomc groups present on the surfactant molecule. Some suitable dianiomc surfactants are further described m copendmg U.S. Serial No. 60/020,503 (Docket No. 6160P), 60/020,772 (Docket No. 6161P), 60/020,928 (Docket No. 6158P), 60/020,832 (Docket No 6159P) and 60/020,773 (Docket No 6162P) all filed on June 28.
• the detergent composition can, and preferably does, include a detergent builder Builders are generally selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, polyhydroxy sulfonates, polyacetates, carboxylates, and polycarboxylates.
• a detergent builder Builders are generally selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, polyhydroxy sulfonates, polyacetates, carboxylates, and polycarboxylates.
• the alkali metal especially sodium, salts of the above.
• Preferred for use herein are the phosphates, carbonates, silicates, C. hopefully , careful fatty acids, polycarboxylates, and
• sodium tripolyphosphate More preferred are sodium tripolyphosphate, tetrasodium pyrophosphate, citrate, tartrate mono- and di-succinates, sodium silicate, and mixtures thereof (see below).
• inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from about 6 to 21, and orthophosphates.
• polyphosphonate builders are the sodium and potassium salts of ethylene diphosphomc acid, the sodium and potassium salts of ethane 1-hydroxy-l, 1 -diphosphomc acid and the sodium and potassium salts of ethane, 1 , 1 ,2-t ⁇ phosphomc acid.
• Other phosphorus builder compounds are disclosed m U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148, all of which are incorporated herein by reference.
• nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicates having a weight ratio of SiO ⁇ to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4.
• Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates.
• polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diamme tetraacetic acid, nitrilot ⁇ acetic acid, oxydisuccimc acid, melhtic acid, benzene polycarboxyhc acids, and citnc acid.
• Polymenc polycarboxylate builders are set forth in U.S. Patent 3,308,067, Diehl, issued March 7, 1967, the disclosure of which is incorporated herein by reference.
• Such materials include the water-soluble salts of homo- and copolymers of aliphatic carboxyhc acids such as maleic acid, ltaco c acid, mesaco c acid, fuma ⁇ c acid, acomtic acid, citracomc acid and methylenemalonic acid.
• Some of these materials aie useful as the water-soluble amomc polymer as hereinafter described, but only if m intimate admixture with the nonsoap amomc surfactant.
• polycarboxylates for use herein are the polyacetal carboxylates described in U.S. Patent 4,144,226, issued March 13, 1979 to Crutchfield et al., and U S. Patent 4,246,495, issued March 27, 1979 to Crutchfield et al., both of which are incorporated herein by reference. These polyacetal carboxylates can be prepared by bringing together under polymerization conditions an ester of glyoxyhc acid and a polymerization initiator.
• polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolyme ⁇ zation m alkaline solution, converted to the corresponding salt, and added to a detergent composition
• Particularly preferred polycarboxylate builders are the ether carboxylate builder compositions comprising a combination of tartrate monosuccmate and tartrate disuccmate described m U.S. Patent 4,663,071, Bush et al , issued May 5, 1987, the disclosure of which is incorporated herein by reference.
• M being an alkali metal, and having a S ⁇ O ⁇ :M ⁇ 0 weight ratio of from about 0.5 to about 4.0, are useful salts in the detergent granules of the invention at levels of from about 2% to about 15% on an anhydrous weight basis, preferably from about 3% to about 8%.
• Anhydrous or hydrated particulate silicate can be utilized, as well.
• any number of additional ingredients can also be included as components in the granular detergent composition.
• these include other detergency builders, bleaches, bleach activators, suds boosters or suds suppressors, anti-tarnish and anti-corrosion agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, nonbuilder alkalinity sources, chelating agents, smectite clays, enzymes, enzyme-stabihzmg agents and perfumes. See U.S. Patent 3,936,537, issued February 3, 1976 to Baskerville, Jr. et al., incorporated herein by reference.
• Bleaching agents and activators are described in U.S. Patent 4,412,934, Chung et al., issued November 1, 1983, and in U.S Patent 4,483,781, Hartman, issued November 20, 1984, both of which are incorporated herein by reference.
• Chelatmg agents are also described in U.S. Patent 4,663,071, Bush et al., from Column 17, line 54 through Column 18, line 68, incorporated herein by reference.
• Suds modifiers are also optional ingredients and are described m U.S. Patents 3,933,672, issued January 20, 1976 to Bartoletta et al., and 4,136,045, issued January 23, 1979 to Gault et al., both incorporated herein by reference.
• Suitable smectite clays for use herein are described in U.S. Patent 4,762,645, Tucker et al., issued August 9, 1988, Column 6, line 3 through Column 7, line 24, incorporated herein by reference.
• Suitable additional detergency builders for use herein are enumerated in the Baskerville patent, Column 13, line 54 through Column 16, line 16, and in U S Patent 4,663,071 , Bush et al., issued May 5, 1987, both incorporated herein by reference.
• Nal2(A102S ⁇ 02)12.27H20 having a primary particle size m the range from 0 1 to 10 micrometers (weight expressed on an anhydrous basis)
• Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between
• Amylase Amylolytic enzyme having 1.6% by weight of active enzyme, sold by
• Lipase Lipolytic enzyme having 2 0% by weight of active enzyme, sold by
• NAC-OBS (6-nonam ⁇ docaproyl) oxybenzene sulfonate
• HEDP 1 , 1 -hydroxyethane diphospho c acid PEGx Polyethylene glycol, with a molecular weight of x (typically 4,000) QEA b ⁇ s((C2H50)(C2H40)n)(CH3) -N+-C6H12-N+-(CH3) b ⁇ s((C2H50)-
• Sihcone antifoam Polydimethylsiloxane 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
• compositions exemplified above have at least 90% by weight of particles having a geometric mean particle diameter of from about 850 microns with a geometric standard deviation of from about 1.2. Unexpectedly, the compositions have improved aesthetics, fiowability and solubility.

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• 2000
  • 2000-08-07 AU AU66236/00A patent/AU777235B2/en not_active Ceased
  • 2000-08-07 CN CNB008116032A patent/CN1230520C/zh not_active Expired - Fee Related
  • 2000-08-07 WO PCT/US2000/021484 patent/WO2001011005A1/en not_active Application Discontinuation
  • 2000-08-07 BR BR0013082-6A patent/BR0013082A/pt not_active Application Discontinuation
  • 2000-08-07 KR KR10-2002-7001751A patent/KR100462265B1/ko not_active IP Right Cessation
  • 2000-08-07 HU HU0202875A patent/HUP0202875A3/hu not_active Application Discontinuation
  • 2000-08-07 CZ CZ2002451A patent/CZ2002451A3/cs unknown
  • 2000-08-07 MX MXPA02001515A patent/MXPA02001515A/es unknown
  • 2000-08-07 JP JP2001515794A patent/JP2003506564A/ja not_active Withdrawn
  • 2000-08-07 EP EP00953859A patent/EP1204736A1/en not_active Withdrawn
  • 2000-08-07 CA CA002380327A patent/CA2380327A1/en not_active Abandoned
  • 2000-08-07 TR TR2002/00329T patent/TR200200329T2/xx unknown
  • 2000-08-09 AR ARP000104109A patent/AR025083A1/es unknown
  • 2000-08-12 EG EG20001049A patent/EG22449A/xx active
• 2002
  • 2002-02-08 MA MA26517A patent/MA25541A1/fr unknown

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