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
  • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
  • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
  • C11D11/02—Preparation in the form of powder by spray drying
• • 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

Definitions

• the present invention generally relates to processes for producing a granular detergent composition. More particularly, the invention is directed to processes during which a high density detergent composition is produced from starting detergent materials, one of which is a mid-chain branched surfactant.
• the mid-chain branched surfactants are mid-chain branched primary alkyl sulfate surfactants and mid-chain branched primary alkyl alkoxylated sulfate surfactants having an average of greater than 14.5 carbon atoms.
• the process produces a free flowing, granular detergent composition which can be commercially sold as a modern compact detergent product.
• the first type of process involves spray-drying an aqueous detergent slurry in a spray-drying tower to produce highly porous detergent granules.
• the various detergent components are dry mixed after which they are agglomerated with a binder such as a nonionic or anionic surfactant.
• a binder such as a nonionic or anionic surfactant.
• surfactants and combinations thereof in detergent compositions.
• various anionic surfactants especially the alkyl benzene sulfonates, alkyl sulfates, alkyl alkoxy sulfates and various nonionic surfactants, such as alkyl ethoxylates and alkylphenol ethoxylates are commonly used in detergent formulations.
• Surfactants have found use as detergent components capable of the removal of a wide variety of soils and stains. A consistent effort, however, is made by detergent manufacturers to improve detersive properties of detergent compositions by providing new and improved surfactants.
• a problem commonly associated with anionic surfactants is their sensitivity to cold water and/or hard water.
• R'CH CH 2 OSO 3 X wherein the total number of carbon atoms ranges from 12 to 20 and Rl is a straight chain alkyl radical containing 9 to 17 carbon atoms and R2 is a straight chain alkyl radical containing 1 to 9 carbon atoms (67% 2-methyl and 33% 2-ethyl branching is exemplified).
• EP 342,917 A Unilever, published Nov. 23, 1989 describes laundry detergents containing a surfactant system in which the major anionic surfactant is an alkyl sulfate having an assertedly "wide range" of alkyl chain lengths (the experimental appears to involve mixing coconut and tallow chain length surfactants).
• Methyl- substituted sulfates include the known "isostearyl" sulfates; these are typically mixtures of isomeric sulfates having a total of 18 carbon atoms.
• isostearyl sulfates
• EP 401,462 A assigned to Henkel, published December 12, 1990, describes certain isostearyl alcohols and ethoxylated isostearyl alcohols and their sulfation to produce the corresponding alkyl sulfates such as sodium isostearyl sulfate. See also K.R. Wormuth and S. Zushma, Langmuir, Vol.
• pp 31-34 relating to foaming data for surfactants which include C12 and C 13 alkyl sulfates containing 3 and 4 methyl branches, respectively
• Varadaraj et al. Langmuir, Vol. 6 (1990)
• pp 1376- 1378 which describes the micropolarity of aqueous micellar solutions of surfactants including branched alkyl sulfates.
• Linear Guerbet alcohols are available from Henkel, e.g., EUTANOL G-16.
• the present invention meets the aforementioned needs in the art by providing a process which produces a compact granular detergent composition directly from mid-chain branched surfactants and other starting detergent ingredients.
• the mid-chain branched surfactants are mid-chain branched primary alkyl sulfate surfactants and mid-chain branched primary alkyl alkoxoxylated sulfate surfactants having an average of greater than 14.5 carbon atoms.
• the process involves mixing a surfactant paste and drying detergent ingredients, spray drying the resulting slurry, compacting the spray dried granules, grinding and coating the granules to form the finished detergent product.
• the detergent compositions resulting from the processes of the invention have acceptable flow properties, a narrow particle size distribution, and exhibit improved cleaning performance over a wide variety of stains and/or soils, even under relatively high water hardness and low temperature wash water conditions.
• a process for preparing a crisp, free flowing, high density detergent composition comprises the steps of: (A) continuously mixing a detergent surfactant paste and dry starting detergent material into a mixer to obtain a slurry, the surfactant paste containing mid-chain branched surfactant compounds of the formula:
• A" is a hydrophobic C9 to C22, total carbons in the moiety, preferably from about C12 to about C18, mid-chain branched alkyl moiety having: (1) a longest linear carbon chain attached to the - X - B moiety in the range of from 8 to 21 carbon atoms; (2) one or more Ci - C3 alkyl moieties branching from this longest linear carbon chain; (3) at least one of the branching alkyl moieties is attached directly to a carbon of the longest linear carbon chain at a position within the range of position 2 carbon, counting from carbon #1 which is attached to the - X - B moiety, to position ⁇ - 2 carbon, the terminal carbon minus 2 carbons; and (4) the surfactant composition has an average total number of carbon atoms in the A ⁇ -X moiety in the above formula within the range of greater than 14.5 to about 18, preferably from about 15 to about 17; (b) B is a hydophilic moiety selected from sulfates,
• FIG. 1 is a flow chart illustrating a preferred process in which the various steps of the process are serially positioned in accordance with the invention.
• the present process is used in the production of a compact granular detergent composition using starting detergent ingredients including a mid-chain branched surfactant by way of a series of processing steps including a spray drying step and additional "post- tower” steps.
• post-tower detergent granules it is meant those detergent granules which have been processed through a conventional spray-drying tower or similar apparatus.
• the invention entails continuously mixing into a mixer or crutcher starting detergent ingredients including a surfactant paste which includes the mid-chain branched surfactant and a dry starting detergent materials, together which form a slurry 10.
• the surfactant paste preferably comprises water and from about 25% to about 75%, preferably from about 35% to about 65% and, most preferably from about 38% to about 55%, of the surfactants one of which is the mid-chain branched surfactant which is described in detail hereinafter.
• the dry starting detergent material comprises from about 10% to about 50%, preferably from about 15% to about 45% and, most preferably from about 20% to about 40% of an aluminosilicate or zeolite builder and from about 10% to about 40%, preferably from about 15% to about 30% and, most preferably from about 15% to about 25% of a sodium carbonate.
• additional starting detergent ingredients several of which are described hereinafter may be mixed into the mixer or crutcher without departing from the scope of the invention.
• the next step of the process involves spray drying 12 the slurry 10 by inputted or spraying the slurry into a spray drying tower or equivalent apparatus to form spray dried granules 14.
• the spray dried 14 granules have a density of from about 350 g/1 to about 550 g/1 as they exiting the spray drying step 12.
• One or more spray-drying towers may be employed to manufacture granular laundry detergents which often have a density of about 500 g 1 or less.
• an aqueous slurry of various heat-stable ingredients in the final detergent composition are formed into homogeneous granules by passage through a spray-drying tower, using conventional techniques, at temperatures of about 175°C to about 225°C.
• the spray dried granules 14 are sent to compacting apparatus for the compaction step 16 of the process.
• the spray dried granules are compacted to form compacted granules 18 which have a density of from about 1000 g/1 to about 1700 g/1.
• the compacted granules 18 are sent to grinding apparatus for the grinding step 20 of the process. Any known conventional compacting and grinding apparatus can be used herein In the grinding step 20, ground detergent particles 22 are formed.
• oversized ground particles 24, typically having a median particle size greater than about 1 150 microns, can be recycled back to the grinding step 20 for additional grinding to the desired particle size.
• the next step of the process entails a coating step 26 in which the ground detergent particles 22 are coated with a coating agent.
• the coating agent is preferably selected from the group consisting of aluminosilicates, silicates, carbonates and mixtures thereof.
• the coating agent not only enhances the free fiowability of the resulting detergent composition which is desirable by consumers in that it permits easy scooping of detergent during use. It is preferable to conduct the coating step in a moderate speed mixer such as a Lodige KM (Ploughshare) mixer, Drais® K-T 160 mixer or similar brand mixer.
• the main centrally rotating shaft speed is from about 30 to about 160 rpm, more preferably from about 50 to about 100 rpm.
• the mean residence time in the moderate speed mixer is preferably from about 0.1 minutes to about 10 minutes, most preferably the residence time is about 0.5 minutes to about 6 minutes.
• the mean residence time can be conveniently and accurately measured by dividing the tear weight of the mixer/densifier at steady state by the throughput (e.g., kg/hr).
• a liquid such as a nonionic surfactant can be inputted to the moderate speed mixer.
• the binder is preferably selected from the group consisting of water, anionic surfactants, nonionic surfactants, polyethylene glycol, polyvinyl pyrrolidone polyacrylates, citric acid and mixtures thereof. Other suitable binder materials including those listed herein are described in Beerse et al, U.S. Patent No. 5,108,646 (Procter & Gamble Co.).
• the liquid distribution is accomplished by cutters, generally smaller in size than the rotating shaft, which preferably operate at about 3600 rpm.
• the coating step 26 occurs in one ore more, preferably four, serially positioned mixers as described previously.
• the resulting high density detergent composition 28 exiting the coating step 26 has a density of from about 650 g/1 to about 950 g/1, more preferably from about 700 g/1 to about 900 g/1.
• the last step of the process can be an admixing step 30 in which admixing adjunct detergent ingredients to the high density detergent composition 28.
• the adjunct detergent ingredients are selected from the group consisting of enzymes, detergent builders, bleaching agents, bleach activators, dyes, soil release agents, and mixtures thereof.
• the surfactant paste includes surfactant mixtures comprising mid-chain branched surfactant compounds as described herein before.
• certain points of branching e.g., the location along the chain of the R, R 1 , and/or RX moieties in the above formula
• the formula below illustrates the mid-chain branching range (i.e., where points of branching occur), preferred mid-chain branching range, and more preferred mid-chain branching range for mono-methyl branched alkyl A° moieties useful according to the present invention.
• the present invention branched surfactant compositions may comprise two or more mid-chain branched primary alkyl sulfate surfactants having the formula
• the surfactant mixtures of the present invention comprise molecules having a linear primary alkyl sulfate chain backbone (i.e., the longest linear carbon chain which includes the sulfated carbon atom). These alkyl chain backbones comprise from 12 to 19 carbon atoms; and further the molecules comprise a branched primary alkyl moiety having at least a total of 14, but not more than 20, carbon atoms.
• the surfactant mixture has an average total number of carbon atoms for the branched primary alkyl moieties within the range of from greater than 14.5 to about 17.5.
• the present invention mixtures comprise at least one branched primary alkyl sulfate surfactant compound having a longest linear carbon chain of not less than 12 carbon atoms or more than 19 carbon atoms, and the total number of carbon atoms including branching must be at least 14, and further the average total number of carbon atoms for the branched primary alkyl chains is within the range of greater than 14.5 to about 17.5.
• a C16 total carbon primary alkyl sulfate surfactant having 13 carbon atoms in the backbone must have 1, 2, or 3 branching units (i.e., R, R? and or R ⁇ ) whereby total number of carbon atoms in the molecule is at least 16.
• the C16 total carbon requirement may be satisfied equally by having, for example, one propyl branching unit or three methyl branching units.
• R, R 1 , and R ⁇ are each independently selected from hydrogen and C1 -C3 alkyl (preferably hydrogen or C1 -C2 alkyl, more preferably hydrogen or methyl, and most preferably methyl), provided R, R ⁇ and R ⁇ are not all hydrogen. Further, when z is 1, at least R or Rl is not hydrogen.
• surfactant compositions the above formula does not include molecules wherein the units R, R 1 , and R ⁇ are all hydrogen (i.e., linear non-branched primary alkyl sulfates), it is to be recognized that the present invention compositions may still further comprise some amount of linear, non-branched primary alkyl sulfate.
• this linear non-branched primary alkyl sulfate surfactant may be present as the result of the process used to manufacture the surfactant mixture having the requisite one or more mid-chain branched primary alkyl sulfates according to the present invention, or for purposes of formulating detergent compositions some amount of linear non-branched primary alkyl sulfate may be admixed into the final product formulation.
• non-sulfated mid-chain branched alcohol may comprise some amount of the present invention compositions. Such materials may be present as the result of incomplete sulfation of the alcohol used to prepare the alkyl sulfate surfactant, or these alcohols may be separately added to the present invention detergent compositions along with a mid-chain branched alkyl sulfate surfactant according to the present invention.
• M is hydrogen or a salt forming cation depending upon the method of synthesis.
• salt forming cations are lithium, sodium, potassium, calcium, magnesium, quaternary alkyl amines having the formula
• R , R , R- > and R" are independently hydrogen, C1-C22 alkylene, C4-C22 branched alkylene, Cj-C6 alkanol, C1-C22 alkenylene, C4-C22 branched alkenylene, and mixtures thereof.
• Preferred cations are ammonium (R ⁇ , R4, R5 ar j R6 equal hydrogen), sodium, potassium, mono-, di-, and trialkanol ammonium, and mixtures thereof.
• the monoalkanol ammonium compounds of the present invention have R ⁇ equal to Cj-Cg alkanol, Ry, R5 and R" equal to hydrogen; dialkanol ammonium compounds of the present invention have R?
• alkanol ammonium salts of the present invention are the mono-, di- and tri- quaternary ammonium compounds having the formulas:
• M is sodium, potassium and the C2 alkanol ammonium salts listed above; most preferred is sodium.
• 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; and w + x + y + z is an integer from 8 to 14.
• the preferred surfactant mixtures of the present invention have at least 0.001%, more preferably at least 5%, most preferably at least 20% by weight, of the mixture one or more branched primary alkyl sulfates having the formula
• the mixtures of surfactant comprise at least 5% of a mid chain branched primary alkyl sulfate having Rl and R ⁇ independently hydrogen, methyl, provided Rl and R2 are not both hydrogen; x + y is equal to 8, 9, or 10 and z is at least 2. More preferably the mixtures of surfactant comprise at least 20% of a mid chain branched primary alkyl sulfate having Rl and R ⁇ independently hydrogen, methyl, provided Rl and R ⁇ are not both hydrogen; x + y is equal to 8,9, or 10 and z is at least 2.
• Preferred detergent compositions according to the present invention for example one useful for laundering fabrics, comprise from about 0.001% to about 99% of a mixture of mid-chain branched primary alkyl sulfate surfactants, said mixture comprising at least about 5 % by weight of two or more mid-chain branched alkyl sulfates having the formula:
• the present invention surfactant composition may comprise a mixture of branched primary alkyl sulfates having the formula
• surfactant compositions when R ⁇ is a C1-C3 alkyl, comprising less than about 20%, preferably less than 10%, more preferably less than 5%, most preferably less than 1%, of branched primary alkyl sulfates having the above formula wherein z equals 1.
• Preferred mono-methyl branched primary alkyl sulfates are selected from the group consisting of: 3 -methyl pentadecanol sulfate, 4-methyl pentadecanol sulfate, 5-methyl pentadecanol sulfate, 6-methyl pentadecanol sulfate, 7-methyl pentadecanol sulfate, 8- methyl pentadecanol sulfate, 9-methyl pentadecanol sulfate, 10-methyl pentadecanol sulfate, 11 -methyl pentadecanol sulfate, 12-methyl pentadecanol sulfate, 13-methyl pentadecanol sulfate, 3-methyl hexadecanol sulfate, 4-methyl hexadecanol sulfate, 5- methyl hexadecanol sulfate, 6-methyl hex
• Preferred di-methyl branched primary alkyl sulfates are selected from the group consisting of: 2,3-methyl tetradecanol sulfate, 2,4-methyl tetradecanol sulfate, 2,5-methyl tetradecanol sulfate, 2,6-methyl tetradecanol sulfate, 2,7-methyl tetradecanol sulfate, 2,8- methyl tetradecanol sulfate, 2,9-methyl tetradecanol sulfate, 2, 10-methyl tetradecanol sulfate, 2,11 -methyl tetradecanol sulfate, 2, 12-methyl tetradecanol sulfate, 2,3-methyl pentadecanol sulfate, 2,4-methyl pentadecanol sulfate, 2,5-methyl pentadecanol sulfate, 2,6-methyl penta
• branched primary alkyl sulfates comprising 16 carbon atoms and having one branching unit are examples of preferred branched surfactants useful in the present invention compositions:
• M is preferably sodium
• branched primary alkyl sulfates comprising 17 carbon atoms and having two branching units are examples of preferred branched surfactants according to the present invention:
• M is preferably sodium
• the present invention branched surfactant compositions may comprise one or more mid-chain branched primary alkyl polyoxyalkylene surfactants having the formula
• the surfactant mixtures of the present invention comprise molecules having a linear primary polyoxyalkylene chain backbone (i.e., the longest linear carbon chain which includes the alkoxylated carbon atom). These alkyl chain backbones comprise from 12 to 19 carbon atoms; and further the molecules comprise a branched primary alkyl moiety having at least a total of 14, but not more than 20, carbon atoms.
• the surfactant mixture has an average total number of carbon atoms for the branched primary alkyl moieties within the range of from greater than 14.5 to about 17.5.
• the present invention mixtures comprise at least one polyoxyalkylene compound having a longest linear carbon chain of not less than 12 carbon atoms or more than 19 carbon atoms, and the total number of carbon atoms including branching must be at least 14, and further the average total number of carbon atoms for the branched primary alkyl chains is within the range of greater than 14.5 to about 17.5.
• a C16 total carbon (in the alkyl chain) primary polyoxyalkylene surfactant having 15 carbon atoms in the backbone must have a methyl branching unit (either R, Rl or R ⁇ is methyl) whereby the total number of carbon atoms in the molecule is 16.
• R, Rl, and R ⁇ are each independently selected from hydrogen and C1-C3 alkyl (preferably hydrogen or Cj-C2 alkyl, more preferably hydrogen or methyl, and most preferably methyl), provided R, Rl, and R?- are not all hydrogen. Further, when z is 1, at least R or Rl is not hydrogen.
• surfactant compositions the above formula does not include molecules wherein the units R, Rl, and R ⁇ are all hydrogen (i.e., linear non-branched primary polyoxyalkylenes), it is to be recognized that the present invention compositions may still further comprise some amount of linear, non-branched primary polyoxyalkylene. Further, this linear non-branched primary polyoxyalkylene surfactant may be present as the result of the process used to manufacture the surfactant mixture having the requisite mid-chain branched primary polyoxyalkylenes according to the present invention, or for purposes of formulating detergent compositions some amount of linear non-branched primary polyoxyalkylene may be admixed into the final product formulation.
• non-alkoxylated mid-chain branched alcohol may comprise some amount of the present invention polyoxyalkylene-containing compositions. Such materials may be present as the result of incomplete alkoxylation of the alcohol used to prepare the polyoxyalkylene surfactant, or these alcohols may be separately added to the present invention detergent compositions along with a mid-chain branched polyoxyalkylene surfactant according to the present invention.
• EO/PO are alkoxy moieties, preferably selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups, more preferably ethoxy, wherein m is at least about 1 , preferably within the range of from about 3 to about 30, more preferably from about 5 to about 20, and most preferably from about 5 to about 15.
• the (EO/PO) m moiety may be either a distribution with average degree of alkoxylation (e.g., ethoxylation and/or propoxylation) 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 surfactant mixtures of the present invention have at least 0.001%, more preferably at least 5%, most preferably at least 20% by weight, of the mixture one or more mid-chain branched primary alkyl polyoxyalkylenes having the formula
• the mixtures of surfactant comprise at least 5%, preferably at least about 20%, of a mid chain branched primary alkyl polyoxyalkylene having Rl and R ⁇ independently hydrogen or methyl, provided R and R ⁇ are not both hydrogen; x + y is equal to 8, 9 or 10 and z is at least 2.
• Preferred detergent compositions according to the present invention for example one useful for laundering fabrics, comprise from about 0.001% to about 99% of a mixture of mid-chain branched primary alkyl polyoxyalkylene surfactants, said mixture comprising at least about 5 % by weight of one or more mid-chain branched alkyl polyoxyalkylenes having the formula:
• the present invention surfactant composition may comprise a mixture of branched primary alkyl polyoxyalkylenes having the formula
• EO/PO are alkoxy moieties, preferably selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein m is at least about 1, preferably within the range of from about 3 to about 30, more preferably from about 5 to about 20, and most preferably from about 5 to about 15; provided that when R ⁇ is C1-C3 alkyl the ratio of surfactants having z equal to 2 or greater to surfactants having z of 1 is at least about 1 : 1, preferably at least about 1.5: 1, more preferably at least about 3: 1, and most preferably at least about 4: 1.
• R ⁇ is C1-C3 alkyl comprising less than about 50%, preferably less than about 40%, more preferably less than about 25%, most preferably less than about 20%, of branched primary alkyl polyoxyalkylene having the above formula wherein z equals 1.
• Preferred mono-methyl branched primary alkyl ethoxylates are selected from the group consisting of: 3-methyl pentadecanol ethoxylate, 4-methyl pentadecanol ethoxylate, 5-methyl pentadecanol ethoxylate, 6-methyl pentadecanol ethoxylate, 7-methyl pentadecanol ethoxylate, 8-methyl pentadecanol ethoxylate, 9-methyl pentadecanol ethoxylate, 10-methyl pentadecanol ethoxylate, 1 1 -methyl pentadecanol ethoxylate, 12- methyl pentadecanol ethoxylate, 13-methyl pentadecanol ethoxylate, 3-methyl hexadecanol ethoxylate, 4-methyl hexadecanol ethoxylate, 5-methyl hexadecanol ethoxylate, 6-methyl hexa
• Preferred di-methyl branched primary alkyl ethoxylates selected from the group consisting of: 2,3-methyl tetradecanol ethoxylate, 2,4-methyl tetradecanol ethoxylate, 2,5- methyl tetradecanol ethoxylate, 2,6-methyl tetradecanol ethoxylate, 2,7-methyl tetradecanol ethoxylate, 2,8-methyl tetradecanol ethoxylate, 2,9-methyl tetradecanol ethoxylate, 2, 10- methyl tetradecanol ethoxylate, 2,11 -methyl tetradecanol ethoxylate, 2, 12-methyl tetradecanol ethoxylate, 2,3-methyl pentadecanol ethoxylate, 2,4-methyl pentadecanol ethoxylate, 2,5-methyl pentadecanol ethoxylate, 2,6-methyl pent
• branched surfactant compositions may comprise one or more (preferably a mixture of two or more) mid-chain branched primary alkyl alkoxylated sulfates having the formula:
• the surfactant mixtures of the present invention comprise molecules having a linear primary alkoxylated sulfate chain backbone (i.e., the longest linear carbon chain which includes the alkoxy-sulfated carbon atom). These alkyl chain backbones comprise from 12 to 19 carbon atoms; and further the molecules comprise a branched primary alkyl moiety having at least a total of 14, but not more than 20, carbon atoms.
• the surfactant mixture has an average total number of carbon atoms for the branched primary alkyl moieties within the range of from greater than 14.5 to about 17.5.
• the present invention mixtures comprise at least one alkoxylated sulfate compound having a longest linear carbon chain of not less than 12 carbon atoms or more than 19 carbon atoms, and the total number of carbon atoms including branching must be at least 14, and further the average total number of carbon atoms for the branched primary alkyl chains is within the range of greater than 14.5 to about 17.5.
• a C 16 total carbon (in the alkyl chain) primary alkyl alkoxylated sulfate surfactant having 15 carbon atoms in the backbone must have a methyl branching unit (either R, Rl or R ⁇ is methyl) whereby the total number of carbon atoms in the primary alkyl moiety of the molecule is 16.
• R, R , and R ⁇ are each independently selected from hydrogen and C1-C3 alkyl (preferably hydrogen or C1-C2 alkyl, more preferably hydrogen or methyl, and most preferably methyl), provided R, R , and R ⁇ are not all hydrogen. Further, when z is 1, at least R or Rl is not hydrogen.
• surfactant compositions the above formula does not include molecules wherein the units R, R , and R ⁇ are all hydrogen (i.e., linear non-branched primary alkoxylated sulfates), it is to be recognized that the present invention compositions may still further comprise some amount of linear, non- branched primary alkoxylated sulfate.
• this linear non-branched primary alkoxylated sulfate surfactant may be present as the result of the process used to manufacture the surfactant mixture having the requisite mid-chain branched primary alkoxylated sulfates according to the present invention, or for purposes of formulating detergent compositions some amount of linear non-branched primary alkoxylated sulfate may be admixed into the final product formulation.
• mid-chain branched alkyl sulfate may be present in the compositions. This is typically the result of sulfation of non- alkoxylated alcohol remaining following incomplete alkoxylation of the mid-chain branched alcohol used to prepare the alkoxylated sulfate useful herein. It is to be recognized, however, that separate addition of such mid-chain branched alkyl sulfates is also contemplated by the present invention compositions.
• non-sulfated mid-chain branched alcohol may comprise some amount of the present invention alkoxylated sulfate-containing compositions.
• Such materials may be present as the result of incomplete sulfation of the alcohol (alkoxylated or non-alkoxylated) used to prepare the alkoxylated sulfate surfactant, or these alcohols may be separately added to the present invention detergent compositions along with a mid-chain branched alkoxylated sulfate surfactant according to the present invention.
• EO/PO are alkoxy moieties, preferably selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein m is at least about 0.01, preferably within the range of from about 0.1 to about 30, more preferably from about 0.5 to about 10, and most preferably from about 1 to about 5.
• the (EO/PO) m moiety may be either a distribution with average degree of alkoxylation (e.g., ethoxylation and/or propoxylation) 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 surfactant mixtures of the present invention have at least 0.001%, more preferably at least 5%, most preferably at least 20% by weight, of the mixture one or more mid-chain branched primary alkyl alkoxylated sulfates having the formula
• the mixtures of surfactant comprise at least 5%, preferably at least about 20%, of a mid chain branched primary alkyl alkoxylated sulfate having Rl and R ⁇ independently hydrogen or methyl, provided Rl and R ⁇ are not both hydrogen; x + y is equal to 8, 9 or 10 and z is at least 2.
• Preferred detergent compositions according to the present invention for example one useful for laundering fabrics, comprise from about 0.001% to about 99% of a mixture of mid-chain branched primary alkyl alkoxylated sulfate surfactants, said mixture comprising at least about 5 % by weight of one or more mid-chain branched alkyl alkoxylated sulfates having the formula:
• the present invention surfactant composition may comprise a mixture of branched primary alkyl alkoxylated sulfates having the formula
• R ⁇ is C1-C3 alkyl comprising less than about 50%, preferably less than about 40%, more preferably less than about 25%, most preferably less than about 20%, of branched primary alkyl alkoxylated sulfate having the above formula wherein z equals 1.
• Preferred mono-methyl branched primary alkyl ethoxylated sulfates are selected from the group consisting of: 3-methyl pentadecanol ethoxylated sulfate, 4-methyl pentadecanol ethoxylated sulfate, 5-methyl pentadecanol ethoxylated sulfate, 6-methyl pentadecanol ethoxylated sulfate, 7-methyl pentadecanol ethoxylated sulfate, 8-methyl pentadecanol ethoxylated sulfate, 9-methyl pentadecanol ethoxylated sulfate, 10-methyl pentadecanol ethoxylated sulfate, 11 -methyl pentadecanol ethoxylated sulfate, 12-methyl pentadecanol ethoxylated sulfate, 13-methyl pentade
• Preferred di-methyl branched primary alkyl ethoxylated sulfates selected from the group consisting of: 2,3-methyl tetradecanol ethoxylated sulfate, 2,4-methyl tetradecanol ethoxylated sulfate, 2,5-methyl tetradecanol ethoxylated sulfate, 2,6-methyl tetradecanol ethoxylated sulfate, 2,7-methyl tetradecanol ethoxylated sulfate, 2,8-methyl tetradecanol ethoxylated sulfate, 2,9-methyl tetradecanol ethoxylated sulfate, 2, 10-methyl tetradecanol ethoxylated sulfate, 2,1 1-methyl tetradecanol ethoxylated sulfate, 2, 12-methyl tetradecanol ethoxylated
• the paste can include adjunct surfactants such as those selected from anionics other than BAS, nonionic, zwitterionic, ampholytic and cationic classes and compatible mixtures thereof.
• adjunct surfactants such as those selected from anionics other than BAS, nonionic, zwitterionic, ampholytic and cationic classes and compatible mixtures thereof.
• Detergent surfactants useful herein are described in U.S. Patent 3,664,961, Norris, issued May 23, 1972, and in U.S. Patent 3,919,678, Laughlin et al., issued December 30, 1975, both of which are incorporated herein by reference.
• Useful cationic surfactants also include those described in U.S. Patent 4,222,905, Cockrell, issued September 16, 1980, and in U.S. Patent 4,239,659, Murphy, issued December 16, 1980, both of which are also incorporated herein by reference.
• adjunct detergent surfactants useful in the present surfactant paste.
• Water-soluble salts of the higher fatty acids i.e., "soaps" are useful anionic surfactants in the compositions herein.
• Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids.
• Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
• Additional anionic surfactants which suitable for use herein include the water- soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure a straight-chain alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
• alkyl is the alkyl portion of acyl groups.
• Examples of this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C Intel .
• anionic surfactants suitable for use herein are the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium of ethylene oxide per molecule and wherein the alkyl groups contain from about 8 to about 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl group contains from about 10 to about 20 carbon atoms.
• suitable anionic surfactants include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxyalkane- 1 -sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; water-soluble salts of olefin and paraffin sulfonates containing from about 12 to 20 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
• Preferred adjunct anionic surfactants are C. _ 1 classroom linear alkylbenzene sulfonate and C, n , deliberately alkyl sulfate.
• low moisture (less than about 25% water) alkyl sulfate paste can be the sole ingredient in the surfactant paste.
• Most preferred are C . chief . touching alkyl sulfates, linear or branched, and any of primary, secondary or tertiary.
• a preferred embodiment of the present invention is wherein the surfactant paste comprises from about 20% to about 40% of a mixture of sodium C. disturb . , linear alkylbenzene sulfonate and sodium C . _ .
• alkyl sulfate in a weight ratio of about 2: 1 to 1 :2.
• Another preferred embodiment of the detergent composition includes a mixture of Cj ⁇ -18 alkyl sulfate and C J O- 18 alkyl ethoxy sulfate in a weight ratio of about 80:20.
• Water-soluble nonionic surfactants are also useful in the instant invention.
• Such nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature.
• the length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
• Suitable nonionic surfactants include the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 15 carbon atoms, in either a straight chain or branched chain configuration, with from about 3 to 12 moles of ethylene oxide per mole of alkyl phenol. Included are the water-soluble and water-dispersible condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with from 3 to 12 moles of ethylene oxide per mole of alcohol.
• nonionics suitable for use herein are semi-polar nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from abut 10 to 18 carbon atoms and two moieties selected from the group of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of about 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon atoms.
• Preferred nonionic surfactants are of the formula R (OC-H .) OH, wherein R is a C, 0 -C, , alkyl group or a C Pain-C. ⁇ alkyl phenyl group, and n is from 3 to about 80.
• Particularly preferred are condensation products of C ⁇ -C, - alcohols with from about 5 to about 20 moles of ethylene oxide per mole of alcohol, e.g., C . ⁇ -C . _ alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol.
• Nonionic surfactants include polyhydroxy fatty acid amides. Examples are N-methyl N- 1 -deoxyglucityl cocoamide and N-methyl N- 1 -deoxyglucityl oleamide. Processes for making polyhydroxy fatty acid amides are known and can be found in Wilson, U.S. Patent No. 2,965,576 and Schwartz, U.S. Patent No. 2,703,798, the disclosures of which are incorporated herein by reference.
• Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
• Zwitterionic surfactants include derivatives of aliphatic, quaternary, ammonium, phosphonium, and sulfonium compounds in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms.
• Cationic surfactants can also be included in the present invention.
• Cationic surfactants comprise a wide variety of compounds characterized by one or more organic hydrophobic groups in the cation and generally by a quaternary nitrogen associated with an acid radical. Pentavalent nitrogen ring compounds are also considered quaternary nitrogen compounds. Suitable anions are halides, methyl sulfate and hydroxide. Tertiary amines can have characteristics similar to cationic surfactants at washing solution pH values less than about 8.5. A more complete disclosure of these and other cationic surfactants useful herein can be found in U.S. Patent 4,228,044, Cambre, issued October 14, 1980, incorporated herein by reference.
• Cationic surfactants are often used in detergent compositions to provide fabric softening and/or antistatic benefits.
• Antistatic agents which provide some softening benefit and which are preferred herein are the quaternary ammonium salts described in U.S. Patent 3,936,537, Baskerville, Jr. et al., issued February 3, 1976, the disclosure of which is incorporated herein by reference.
• compositions of the invention can contain all manner of organic, water-soluble detergent compounds, inasmuch as the builder material are compatible with all such materials.
• at least one suitable adjunct detergent ingredient is preferably included in the detergent composition.
• the adjunct detergent ingredient is preferably selected from the group consisting of builders, enzymes, bleaching agents, bleach activators, suds suppressors, soil release agents, brighteners, perfumes, hydrotropes, dyes, pigments, polymeric dispersing agents, pH controlling agents, chelants, processing aids, crystallization aids, and mixtures thereof.
• the following list of detergent ingredients and mixtures thereof which can be used in the compositions herein is representative of the detergent ingredients, but is not intended to be limiting.
• One or more builders can be used in conjunction with the builder material described herein to further improve the performance of the compositions described herein.
• the builder can be selected from the group consisting of aluminosilicates, crystalline layered silicates, MAP zeolites, citrates, amorphous silicates, polycarboxylates, sodium carbonates and mixtures thereof.
• the sodium carbonate ingredient can serve as the inorganic alkaline material when a liquid acid precursor of the mid-chain branched surfactant is used.
• Other suitable auxiliary builders are described hereinafter.
• Preferred builders include aluminosilicate ion exchange materials and sodium carbonate.
• the aluminosilicate ion exchange materials used herein as a detergent builder preferably have both a high calcium ion exchange capacity and a high exchange rate. Without intending to be limited by theory, it is believed that such high calcium ion exchange rate and capacity are a function of several interrelated factors which derive from the method by which the aluminosilicate ion exchange material is produced.
• the aluminosilicate ion exchange materials used herein are preferably produced in accordance with Corkill et al, U.S. Patent No. 4,605,509 (Procter & Gamble), the disclosure of which is incorporated herein by reference.
• the aluminosilicate ion exchange material is in "sodium" form since the potassium and hydrogen forms of the instant aluminosilicate do not exhibit the as high of an exchange rate and capacity as provided by the sodium form.
• the aluminosilicate ion exchange material preferably is in over dried form so as to facilitate production of crisp detergent agglomerates as described herein.
• the aluminosilicate ion exchange materials used herein preferably have particle size diameters which optimize their effectiveness as detergent builders.
• particle size diameter represents the average particle size diameter of a given aluminosilicate ion exchange material as determined by conventional analytical techniques, such as microscopic determination and scanning electron microscope (SEM).
• the preferred particle size diameter of the aluminosilicate is from about 0.1 micron to about 10 microns, more preferably from about 0.5 microns to about 9 microns. Most preferably, the particle size diameter is from about 1 microns to about 8 microns.
• the aluminosilicate ion exchange material has the formula Na z [(A10 2 ) z .(Si ⁇ 2)y]xH 2 0 wherein z and y are integers of at least 6, the molar ratio of z to y is from about 1 to about 5 and x is from about 10 to about 264. More preferably, the aluminosilicate has the formula
• These preferred aluminosilicates are available commercially, for example under designations Zeolite A, Zeolite B and Zeolite X.
• Naturally-occurring or synthetically derived aluminosilicate ion exchange materials suitable for use herein can be made as described in Krummel et al, U.S. Patent No. 3,985,669, the disclosure of which is incorporated herein by reference.
• the aluminosilicates used herein are further characterized by their ion exchange capacity which is at least about 200 mg equivalent of CaC ⁇ 3 hardness/gram, calculated on an anhydrous basis, and which is preferably in a range from about 300 to 352 mg equivalent of CaC ⁇ 3 hardness/gram. Additionally, the instant aluminosilicate ion exchange materials are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca "H 7gallon/minute/-gram/gallon, and more preferably in a range from about 2 grains Ca "H 7gallon/minute/-gram/gallon to about 6 grains Ca "H 7gallon/minute/-gram/gallon .
• This Example illustrates the process of the invention which produces free flowing, crisp, high density detergent composition.
• Two feed streams of various detergent starting ingredients including a surfactant paste containing the mid-chain branched surfactant and water and the other stream containing starting dry detergent material containing aluminosilicate and sodium carbonate are fed to a crutcher for continuous mixing, thus forming a slurry.
• the slurry is fed to a conventional spray drying process in which the slurry is passed though a spray drying tower having a counter current stream of hot air (200-300°C) resulting in the formation of porous spray dried granules having a density of about 250 g/1.
• the spray dried granules are sent to a compactor (commercially available from the Sahut Company) which form compacted granules having a density of about 1300 g/1. Subsequently and continuously, the compacted granules are sent to a grinder to form ground detergent particles having a density of about 700 g/1.
• the ground detergent particles excluding oversized ground particles which recycled back to the grinder, are fed to the first of four serially positioned moderate speed mixers.
• Each of the moderate speed mixers are Lodige KM-600 mixers in which aluminosilicate is added to coat the ground detergent particles resulting in a high density detergent composition having a density of 800 g/1.
• Admixed ingredients are added as the high density detergent composition is passed through a vertical mixer such as a Fukae mixer.
• the final composition of the high density detergent composition produced by the process is given below:

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