US3726813A - Detersive particulate composition - Google Patents

Detersive particulate composition Download PDF

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US3726813A
US3726813A US00083601A US3726813DA US3726813A US 3726813 A US3726813 A US 3726813A US 00083601 A US00083601 A US 00083601A US 3726813D A US3726813D A US 3726813DA US 3726813 A US3726813 A US 3726813A
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water
composition
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salt
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G Borrello
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    • 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
    • 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
    • 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
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates

Definitions

  • a water-soluble, mechanically worked, substantially homogeneous, particulate detersive composition said composition being formed of discrete particles each comprising (a) to 40% by weight of water-soluble, higher alkyl aryl sulfonate detergent salt, having 9 to carbons in the alkyl group (b) 10% to 40% by Weight of a lower alkyl benzene sulfonate salt having one to three carbon atoms in the lower alkyl group, (0) 5% to 50% by weight of at least one water-soluble inorganic salt, and (d) 2 to by weight of water; the ratio of (a) to (b) being between 124 and 6:1; the major portion of said particles being organic; said particles being non-tacky, rigid, breakable, and non-friable, having a density of 0.5 to 0.9 gm./ cc., and having an average
  • the present invention relates to a non-tacky, rigid, breakable, non-friable, quickly water-soluble, extruded, particulate detersive composition containing a higher alkyl aryl sulfonate detergent salt. More particularly, the particulate composition will include, in addition to the alkyl aryl sulfonate detergent salt, a lower alkyl aryl sulfonate, an inorganic salt and water, said combination being effective to produce said product.
  • detergent compositions comprising a physical mixture of dry particles of alkyl aryl sulfonate with dry particles of xylene sulfonate.
  • such compositions are disclosed as being useful powdered detergents.
  • Such powdered detergents, formed from mixtures of dry materials are subject to various undesirable effects, such as non-uniformity of composition for any given sample, caking, segregation, flowability, and dusting problems.
  • the present invention provides a detersive composition which eliminates the disadvantages of prior art.
  • compositions of the invention are useful per se or in admixture with other particulate synthetic organic detergent materials and can be prepared in the desired form in a simple, economical, and facile manner by mechanically working, extruding and granulating a composition as described hereinbelow of 10 to parts by weight of a higher alkyl aryl sulfonate detergent salt, 10 to 40 parts of a lower alkyl aryl sulfonate salt, and 2 to 20 parts of a water-soluble, inorganic alklaline builder salt.
  • the mixture may also desirably contain 5 to parts of at least one highly water soluble, inorganic alkali metal salt such as the sulfate, halide, bicar- 3,726,813 Patented Apr. 10, 1973 bonate, or sesquicarbonate salts thereof.
  • the total amount of organic material in the composition will constitute a ma or proportion thereof and for this purpose the content of higher and lower alkyl aryl sulfonate salt may be supplemented with other organic materials such as the alkali and alkaline earth metal salts of alkyl sulfates, e.g.
  • alkyl aryl sulfonates shall fall within the ranges given above, and the ratio of higher to lower alkyl aryl sulfonate is 1:4 to 6:1, preferably 1:2 to 2:1, and most desirably the amount of higher alkyl aryl sulfonate should be approximately the same as the amount of the lower alkyl aryl sulfonate.
  • Some water will also be present in the final product, generally in an amount between about 2 and 20% by weight.
  • Such compositions consist of non-tacky, breakable, non-friable particles which dissolve or disperse in less than 120 seconds and preferably in less than seconds.
  • the rigid, breakable, non-friable detersive compositions are suitably prepared by admixing the higher alkyl aryl sulfonate detergent, the lower alkyl aryl sulfonate salt, the inorganic salt, and water to form a rheologically extrudable mixture, mechanically working the mixture to effect homogeneity by compacting and extruding said mixture at a temperature at the exit of the extruder of about 10 C. to 40 C. to form a plurality of thin strands having a cross sectional area of from 0.04 mm. to 0.8 mmF, contacting the strands immediately upon their extrusion with a jet of air at a temperature of between about 5 C. and 45 C.
  • the extruded strands are broken into lengths by passing them through a screen or other suitable equipment.
  • This process can be carried out in inexpensive, small-capacity equipment without the need for removing large quantities of water.
  • the size of the particles of the composition can be easily adjusted.
  • the non-tacky, rigid, breakable, water-soluble, particulate detersive composition of the invention is useful as a light duty detergent for clothes, dishes, or other similar functions. Because of the non-tacky characteristics of the discrete particles forming the composition of the instant invention, it will not segregate and is substantially free from caking. Such particles are extremely free flowing and quite useful as a substitute for the powdered hand cleansers normally dispensed from Washroom receptacles.
  • the present composition is also particularly useful as an additive to spray dried or other particulate detergent compositions or as a carrier for an adjuvant such as color, brightener, enzyme, or other material. Such material, carrying a brightener for example is useful as an after laundry whitener to be added to the second rinse.
  • each of the final particles formed from the strands has a substantially plastic nature. This is surprising because of the presence of crystalline materials such as the inorganic salt. The plastic nature is evident from a microscopic examination of the individual particles which discloses that each particle has a substantially smooth surface and a lack of crystalline structures therein. Further, despite their plastic nature, which facilitates extrusion, the strands are readily breakable and, at the same time, are substantially non-friable. Ready breakability is generally not characteristic of plastic materials and non-friability is usually not characteristic of breakable materials. Accordingly, the
  • the non-friable, breakable alkyl aryl sulfonate composition is prepared by using simple, small-capacity mechanical working equipment. Adequate mechanical working as well as the proper choice of the constituent salts and their relative proportions will provide particles having the desired physical properties.
  • the mechanical working operation imparts homogeneity in order to achieve a physical structure within the mixture that results in the desired surface and internal characteristics.
  • Mechanical working refers to plodding and extruding, i.e., compacting the plastic mixture under pressure and forcing it through one or more orifices of restricted size and preferably will also include shearing the composition as, for example, by passing the plastic mixture between a series of rolls rotating at different speeds and having varying clearances.
  • the mechanical working generally results in a rise in temperature which may be regulated by adding or removing heat during the operation.
  • the final product will be in the form of spaghetti-like noodles, the cross-sectional area of which will depend upon the size of the extrusion orifice and should be between 0.04 mm. and 0.8 mm. and preferably 0.06 to 0.3 mm.
  • the extruded noodles are subjected to a jet of air, and the air is maintained in contact with them for a short period of time. In this zone the temperature of the noodles is adjusted to between 15 C. and 25 C.
  • the air treatment of the extruded noodles causes free moisture, as for example from 1% to 5% by weight thereof to be removed and a hardened surface to be formed.
  • the material is then broken into short lengths by suitable means, such as by forcing them through a granulation screen having openings from 0.177 mm. to 10.0 mm., preferably from 0.25 mm. to 3.36 mm.
  • the resultant particulate material will be free-flowing, non-friable, and rigid.
  • the product is suitable for use per se or in admixture with particulate detergent compositions comprising a synthetic organic detergent.
  • particulate detergent compositions comprising a synthetic organic detergent.
  • the particles of the detersive composition can be blended with particulate spray-dried compositions having a major proportion of particles with a diameter from 0.3 mm. to 2.0 mm.
  • the resultant water-soluble, mechanically worked, substantially homogeneous detersive composition is formed of discrete particles each of which consists essentially of (a) to 40% by Weight of water-soluble, higher alkyl aryl sulfonate detergent salt having 9 to carbons in the alkyl group; (b) 10% to 40% by weight of a lower alkyl benzene sulfonate salt having one to three carbon atoms in the lower alkyl group; (c) 5% to 50% by weight of a water-soluble, alkali metal, inorganic salt of which 2% to by weight is an alkaline, hydratable, builder salt selected from the group consisting of orthophosphate, pyrophosphate, tripolyphosphate, silicate, carbonate, borate, and mixtures thereof and the balance includes a salt selected from the group consisting of sulfate, halide, bicarbonate and sesquicarbonate; and (d) 2% to 20% by weight of water; the ratio of (a) to (b) being between
  • the hard, non-friable detersive particles formed in the manner described herein will include at least one higher alkyl aryl sulfonate salt having 9 to 18, preferably 10 to 15, carbon atoms in the higher alkyl group.
  • the higher alkyl group may be in the form of a straight or branched chain.
  • These detergents are employed in the form of their water-soluble salts, such as the sodium, potassium, ammonium, alkylolammoniurn and magnesium salts.
  • Suitable detergents include higher alkyl benzene sulfonates, higher alkyl toluene sulfonates, higher alkyl phenol sulfonates, and higher alkyl napthalene sulfonates.
  • Preferred sulfonates are the dodecyl and tridecylbenzene sulfonates.
  • a particularly preferred sulfonate is the linear C C alkyl benzene sulfonate having a high content of 3- (or higher) phenyl isomers and a correspondingly low content less (than about 30%) of 2- (or lower phenyl isomers), i.e., wherein the benzene ring is preferably attached in large part at the 3 or higher (e.g., 4, 5, 6, or 7) position of the alkyl group and the content of isomers in which the benzene ring is attached at the 2 or 1 position is correspondingly low.
  • the particularly preferred sulfonates are disclosed in U.S. 3,320,174.
  • the higher alkyl aryl sulfonate detergents may be added in particulate form, such as that obtained by spray drying or drum drying.
  • the alkyl aryl sulfonate detergent may be formed in situ by being supplied in the mixing vessel in a liquid acid state, e.g., a liquid containing by weight 88% of alkyl aryl sulfonic acid, 7.5% of sulphuric acid, and 4.5% water, where it is neutralized with an alkali metal or alkaline earth metal hydroxide, carbonate, or bicarbonate.
  • the lower alkyl benzene sulfonate salts will have one to three carbon atoms in the alkyl group.
  • Suitable lower alkyl benzene sulfonate salts include the sodium and potassium salts of xylene, toluene, isopropyl benzene, and ethylbenzene sulfonates.
  • Commercial xylene and toluene sulfonates are mixtures of isomers.
  • analyses of commercial xylene sulfonates show by weight about 40 to 58% metaxylene sulfonate, 10 to 35% orthoxylene sulfonate, 15 to 30% paraxylene sulfonate, and 0 to 20% of ethylbenzene sulfonate; and analyses of commercial toluene sulfonates show about 70% to of paratoluene sulfonate and about 20% to 30% of orthotoluene sulfonate.
  • Other water-soluble sulfonated salts such as the ammonium, alkylolammonium, and magnesium salts, may also be used. These materials may be added in either solid or liquid form.
  • commercial sodium xylene sulfonate is available in the form of a 90% to active powder or as a 30% to 45% active aqueous liquid.
  • active aqueous liquid usually, where it is available as an aqueous liquid, the form in which it is added depends upon the form and water content of the other essential ingredients of the composition.
  • At least one water-soluble, inorganic salt is used in an amount not exceeding the amount of organic material in the composition.
  • Such salts will include a water-soluble, alkali metal, hydratable or hydrated, inorganic, alkaline builder salt.
  • the preferred material is sodium tripolyphosphate.
  • Such inorganic, hydratable, alkaline builder salts are well known in the art, and major proportions thereof are often used in combination with sulfonate or sulfate detergents to increase their detersive efficiency.
  • alkali metal pyrophosphates such as sodium carbonate, silicates such as sodium metasilicate, borates such as sodium tetraborate, and mixtures thereof.
  • Phase I and Phase II sodiium tripolyphosphate and mixtures thereof may be use
  • the foregoing builder salts will preferably be supplied in the form of anhydrous particles.
  • These builder salts in the environment of the invention and in the prescribed amounts are effective in hardening the extruded noodles so that they are non-tacky and retain their descrete form. This hardening effect also facilitates the extrusion in noodle form by altering the noodle surface to reduce the tendency of the noodles to stick together.
  • orthophosphates carbonates such as sodium carbonate
  • silicates such as sodium metasilicate
  • borates such as sodium tetraborate
  • Both Phase I and Phase II sodiium tripolyphosphate and mixtures thereof may be use
  • the foregoing builder salts will preferably be supplied in
  • such salts will be inorganic alkali metal sulfate salts which normally are present as the sodium or potassium salts.
  • Other salts which are highly water soluble can also be used. These include the bicarbonates such as sodium or potassium bicarbonate, sesquicarbonate's such as sodium sesquicarbonate, and halogen salts such as sodium chloride.
  • the anions mentioned above with relation to the sulfate salts may also be used With the cations referred to immediately above.
  • the detersive composition also contains generally 2% to 20% water.
  • the water aids in forming a rheologically extrudable mixture.
  • Water also helps to promote the neutralization reaction when the alkyl aryl sulfonate salt is formed in situ and may serve as a carrier for small amounts of adjuvant, e.g. color, brightener, germicide, etc. It should be recognized that the total amount of water present will be the sum of the amount of water added directly and the water added with the other ingredients.
  • spray-dried alkyl aryl sulfonate normally contains 1% to 3% water and can contain up to 10% Water.
  • adjuvants can be incorporated in the noodlelike compositions before the constituents thereof are mechanically worked.
  • Such adjuvants may include 0.01% to 2% of coloring materials, such as water-soluble dyes and water dispersable pigments; 0.01% to 2% of perfumes; 0.1 to 5% of activators for oxygen bleaches, such as the activators disclosed in the Italian patent application No. 35,409/69 filed Mar. 3, 1969 corresponding to U.S. application Ser. No. 726,571, filed May 3, 1968; 0.01% to of fluorescent brightening agents, such as the derivatives and analogues of coumarin, diaminiostilbene, diaminobensofuran, and the bleach-stable brighteners disclosed in U.S.
  • the amount and choice of higher alkyl aryl sulfonates in the mechanically worked, noodle-like composition is selected to yield a product having the desired physical and performance characteristics. It contributes to the foaming and cleansing action of the final detergent composition and, where an adjuvant is included as described above the noodle composition functions as a dispersing or stabilizing agent therefor.
  • the proportion of the higher alkyl aryl sulfonate detergent will usually be in the range of 10 to 40 parts by weight and, preferably 10 to 32 parts by weight, of the carrier.
  • the builder salt hardeners comprise a minor proportion and are usually present in an amount sufficient to impart the desired hardness, i.e., about 2% but not more than about 20% by weight, preferably from 5% to by Weight. It is preferred to have a tripolyphosphate hardener present in an amount such that the weight ratio of tripolyphosphate salt to organic sulfonate salt is in the range of 1:4 to 1:12.
  • the foregoing spaghetti-like noodles can advantageously be blended with a particulate detergent composition comprising a synthetic organic detergent (such as spray-dried hollow beads or spongeous low-density granules) to form a washing composition.
  • a synthetic organic detergent such as spray-dried hollow beads or spongeous low-density granules
  • the proportion of the spaghetti-like detersive composition in the ultimate washing composition will be from 0.01% to 50% by weight, and preferably from 0.5% to 20% by weight, of the total washing composition.
  • the ultimate washing composition will normally also contain inorganic alkaline or neutral builder salts which are well recognized in the art as detergency aids.
  • the synthetic detergent component of the particulate detergent composition used in the ultimate washing products may be an anionic, nonionic, or amphoteric surface active detergent or a mixture of two or more of the foregoing detergents.
  • the anionic detergents include those detergent compounds which contain an organic hydrophobic group and an anionic solubilizing group in their molecular structure.
  • Typical examples of anionic solubilizing groups are sulfonate, sulfate, carboxylate, phosphonate, and phosphate.
  • anion carboxylate detergents i.e., soaps, are generally used only in compositions designed for use in soft water because of the adverse effect of hard water thereon.
  • anionic detergents which fall within the scope of the anionic detergent class include the Water-soluble salts, e.g., the sodium, ammonium, and alkylolammonium salts of higher fatty acids or resin acids containing about 8 to 24 carbon atoms, preferably 10 to 20 carbon atoms.
  • Suitable fatty acids can be obtained from oils and Waxes of animal or vegetable origin, e.g., tallow, grease, coconut oil, tall oil, and mixtures thereof.
  • Particularly useful are the sodium and potassium salts of the fatty acid mixtures derived from coconut oil and tallow, e.g., sodium coconut soap and potassium tallow soap.
  • the anionic class of detergents also includes the watersoluble sulfated and sulfonated synthetic detergents having an alkyl radical of 8 to 26, preferably about 12 to 22 carbon atoms, in their molecular structure. (The term alkyl includes the alkyl portion of the higher acyl radicals.)
  • the sulfonated anionic detergents are the higher alkyl mononuclear aromatic sulfonates such as the higher alkyl benzene sulfonates containing from 10 to 16 carbon atoms in the alkyl group in a straight or branched chain, e.g., the sodium, potassium, and ammonium salts of higher alkyl benzene sulfonates, and higher alkyl toluene sulfonates, higher alkyl phenol sulfonates, and higher alkyl naphthalene sulfonates.
  • the higher alkyl mononuclear aromatic sulfonates such as the higher alkyl benzene sulfonates containing from 10 to 16 carbon atoms in the alkyl group in a straight or branched chain, e.g., the sodium, potassium, and ammonium salts of higher alkyl benzene sulfonates, and higher alkyl to
  • a preferred sulfonate is linear alkyl benzene having a high content of 3- (or higher) phenyl isomers and a correspondingly low content (well below 50%) of 2- (or lower) phenyl isomers, i.e., wherein the benzene ring is preferably attached in large part at the 3 or higher (e.g., 4, 5, 6, or 7) position of the alkyl group and the content of isomers in which the benzene ring is attached at the 2 or 1 position is correspondingly low.
  • Particularly preferred materials are set forth in U.S. Pat. 3,3 20,174.
  • Suitable anionic detergents are the olefin sulfonates, including long chain alkenes sulfonates, long chain hydroxyalkane sulfonates, or mixtures of alkene sulfonates and hydroxyalkane sulfonates.
  • olefin sulfonate detergents may be prepared in a known manner by the reaction of S0 with long chain olefins containing 8 to 25, preferably 11 to 21 carbon atoms and having the formula RCH-CHR where R is higher alkyl grou of 6 to 23 carbon atoms and R is an alkyl group of 1 to 17 carbons or hydrogen to form a mixture of sultones and alkenesulfonic acids which is then treated to convert the sultones to sulfonates.
  • sulfate or sulfonate detergents are paraffin sulfonates containing about 10 to 20, preferably about 15 to 20 carbon atoms, e.g., the primary parafiin sulfonates made by reacting long chain alpha olefins and bisulfites and paraffin sulfonates having sulfonate groups distributed along the parafiin chain as shown in U.S. Pat. 2,503,280; 2,507,088; 3,260,741; 3,372188; and German Pat.
  • the suitable anionic detergents include also the acyl sarcosinates (e.g., sodium lauroyl sarcosinate), sodium and potassium salts of the reaction product of higher fatty acids containing 8 to 18 carbon atoms in the molecule esterified with isethionic acid, and sodium and potassium salts of the higher fatty acid amide of methyl taurine, e.g., sodium cocoyl methyl taurate and sodium stearoyl methyl taurate.
  • acyl sarcosinates e.g., sodium lauroyl sarcosinate
  • sodium and potassium salts of the reaction product of higher fatty acids containing 8 to 18 carbon atoms in the molecule esterified with isethionic acid e.g., sodium cocoyl methyl taurate and sodium stearoyl methyl taurate.
  • Anionic phosphate surfactants in which the anionic solubilizing group attached to the hydrophobic group is an oxyacid of phosphorous are also helpful in the detergent compositions.
  • Suitable phosphate surfactants are the sodium, potassium, and ammonium alkyl phosphate esters such as (RO) PO M and ROPO M in which R represents an alkyl chain containing from about 8 to about 20 carbon atoms or an alkyl phenyl group having 8 to 20 carbon atoms and M represents a soluble cation.
  • R represents an alkyl chain containing from about 8 to about 20 carbon atoms or an alkyl phenyl group having 8 to 20 carbon atoms and M represents a soluble cation.
  • the particular anionic detergent salt will be suitably selected depending upon the particular formulation and the proportions therein.
  • Preferred salts include the ammonium, substituted ammonium (mono-, diand triethanol-ammonium), alkali metal (such as sodium and potassium) and alkaline earth metal (such as calcium and magnesium) saits of the higher alkyl benzene sulfonates, the higher alkyl sulfates, the higher fatty acid monoglyceride sulfates, the higher acyl sarcosinates, the described isethionates, and the described taurates.
  • the nonionic detergents which are used as the organic surface active component of the washing compositions are generally the condensation product of an organic aliphatic or alkyl aromatic hydrophobic compound and hydrophilic ethylene oxide groups or, with the polyhydration product thereof, polyethylene glycol. Practically any hydrophobic compound having a carboxy, hydroxy amide, or amino group with a free hydrogen attached to the nitrogen can be condensed with ethylene oxide to form a nonionic detergent. Further, the length of the polyetheneoxy chain can be adjusted to achieve the desired balance between the hydrophobic and hydrophilic elements.
  • the nonionic detergents include the polyethylene oxide condensate of one mole of alkyl phenol containing from about 6 to about 12 carbon atoms in a straight or branched chain alkyl configuration with about 5 to moles of ethylene oxide, e.g., nonyl phenol condensed with 9 moles of ethylene oxide, dodecyl phenol condensed with 15 moles of ethylene oxide, and dinonyl phenol condensed with 15 moles of ethylene oxide. Condensation products of the corresponding alkyl thiophenol with 5 to 30 moles of ethylene oxide are also suitable.
  • nonionic detergent class also included in the nonionic detergent class are the condensation products of a higher alcohol containing about 8 to 22 carbon atoms in a straightor branchedchain configuration condensed with about 5 to 3() moles of ethylene oxide, e.g., lauryl myristyl alcohol condensed with 16 moles of ethylene oxide.
  • Nonionic detergents are the condensation product of ethylene oxide on a hydrophobic base formed by the condensation of propylene oxide and propylene glycol. These materials are sold under the trade name Pluronic.
  • the molecular weight of the hydrophobe ranges from about 1,500 to 1,800, and the polyethylene oxide content may comprise up to of the total weight of the condensate.
  • nonionic detergents include the ethylene oxide addends of monoesters of hexahydric alcohols and inner ethers thereof with higher fatty acids containing about 10 to 20 carbon atoms, e.g., sorbitan monolaurate, sorbitan mono-oleate, and mannitan monopalmitate.
  • the water-soluble ampholytic or amphoteric detergents which can be used in the compositions of this invention generally contain a hydrophobic alkyl group of about 8 to 18 carbon atoms, at least one anionic watersolubilizing group, e.g., carboxy, sulfo, sulfate, phosphate, or phosphono, and at least one cationic group, e.g., nonquaternary nitrogen, quaternary ammonium, or quaternary phosphonium group, in their molecular structure.
  • the alkyl group may be straight chain or branched and the specific cationic atom may be part of a heterocyclic ring.
  • ampholytic detergents include the alkyl beta-aminopropionates, RN(H)C H 'COOM; the alkyl beta-iminodipropionates, RN(C II )COOM and the long chain imidazole derivatives having the following formula:
  • R is an alkyl group of about 8 to 18 carbon atoms
  • W is selected from the group of R OH, R OM and R OR COOM
  • Y is selected from the group consisting of 01-11 R S0; and 12 080
  • R is an alkylene or hydroxyalkylene group containing 1 to 4 carbon atoms
  • R is selected from the group consisting of alkyl, alkyl aryl and fatty acyl glyceride groups having 6 to 18 carbon atoms in the alkyl or acyl group
  • M is a watersoluble cation, e.g., alkali metal, ammonium or alkylolammonium.
  • Preferred detergents are sodium N-lauryl beta-aminopropionate, disodium N-lauryl iminodipropionate, and the disodium salt of 2-laurylcycloimidium-1- hydroxyl, l-ethoxyethanoic acid, l-ethanoic acid.
  • Other imidazole detergents are described in US. 2,773,068; US. 2,781,354 and 11.8. 2,781,357.
  • amphoteric detergents are the sultaine and betaine types having the following general structure:
  • Preferred compounds are l-(myristyl dimethylammonio) acetate and 1- (myristyl dimethylammonio -2-hydroxypropane-3sulfonate.
  • amphoteric imidazole detergents have the following structure:
  • R is a higher acyclic group of 7 to 17 carbon atoms and M is a water-soluble cation, e.g., sodium, potassium, ammonium and mono-dior trialkyloarnmonium.
  • the acyclic groups may be derived from coconut oil fatty acids (a mixture of fatty acids containing 8 to 18 carbon atoms), lauric fatty acid, and oleic fatty acid, and alkyl groups of 7 to 17 carbons are preferred acyclic groups.
  • any of the above described anionic, cationic, nonionic, ampholytic, or amphoteric detergents may also be used as a portion of the organic part of the spaghettilike composition although as described hereinabove the mixture of lower and higher alkyl aryl sulfonate detergent salts must comprise at least about of the total noodle composition.
  • Suitable builder salts are the phosphates, condensed phosphates (e.g., pyrophosphates or tripolyphosphates), silicates, borates, and carbonates (including bicarbonates), as well as organic builders such as salts of nitrilotriacetic acid or ethylene diamine tetraacetic acid.
  • Sodium and potassium salts are preferred.
  • sodium tripolyphosphate potassium pyrophosphate, sodium hexametaphosphate, sodium carbonate, sodium bicarbonate, sodium sesquibicarbonate, sodium tetraborate, sodium silicate, salts (e.g., Na salt) of methylene diphosphonic acid, disodium diglycollate, trisodium nitrilotriacetate, or mixtures of such builders, including mixtures of pentasodium tripolyphosphate and trisodium nitrilotriacetate in a ratio, of these two builders, of 1:10 to 10:1, e.g., 1:1. Generally, one to five parts of builder salt will be used for each part of synthetic organic detergent in a heavy-duty washing composition.
  • salts e.g., Na salt
  • methylene diphosphonic acid disodium diglycollate
  • trisodium nitrilotriacetate or mixtures of such builders, including mixtures of pentasodium tripolyphosphate and triso
  • 'Other materials may be present in the washing products.
  • materials such as the higher fatty acid amides may be added to improve detergency and to modify the foaming properties in a desirable manner.
  • materials such as the higher fatty acid alkanolamides preferably having 2-3 carbons in each alkanol group attached to a fatty acyl radical containing 10l 8 carbons (preferably 110 14 carbons), such as lauric or myristic monoethanolamides, diethanolamides and isopropanolamides.
  • foam builders are the tertiary amine oxides of the general formula R R R N O wherein R is an alkyl radical of about 10 to 18 carbon atoms, R and R are alkyl or hydroxyalkyl groups containing 1 to 3 carbon atoms, and the arrow represents a semipolar bond. Included among the satisfactory amine oxides are lauryl dimethyl amine oxide and myristyl dimethyl amine oxide.
  • Fatty alcohols of 10-18 carbon atoms such as lauryl or coconut fatty alcohols or cetyl alcohol, are suitable additives also.
  • these materials and the foregoing foam builders are added in minor amounts, usually from about /2% to 10%, preferably 1% to 6%, based on the total solids.
  • the composition may include specific chelating agents, such as salts of ethylene diamine tetraacetic acid.
  • Other conventional auxiliary materials include soil suspending agents, e.g., sodium carboxymethyl cellulose, tarnish inhibitors, e.g., melamine, fluorescent brightening agents, coloring materials, germicides, skin conditioning agents, e.g. lanolin, etc. These materials will generally be admixed with the aqueous synthetic organic detergent and the other ingredients of the composition prior to the heat-drying step when one is employed.
  • a green-colored, fast-dissolving, particulate laundry component is prepared having the following composition:
  • Viscofil green 2 GL which is a phthalocyanlne pigment.
  • Viscofil green 2 GL powder is dispersed in water in the presence of minor amounts of sodium tripolyphosphate and sodium toluene sulfonate to form a color dispersion having the following composition.
  • Green colorant 1.14 Sodium toluene sulfonate 1.00 Sodium tripolyphosphate 1.00 Water 96.86
  • color dispersion facilitates the rate at which a homogeneously colored detergent mixture can be obtained.
  • toluene sulfonate and the inorganic salts are blended in a powder mixer and passed through a grinding mill to eliminate all particles larger than 60 mesh (US. Standard Sieve size).
  • the ground mixture and the formula amount of sodium tridecylbenzene sulfonate are charged into a ribbon-type amalgamator. Twelve parts by weight of the foregoing color dispersion are admixed with eighty-eight parts by weight of the foregoing powder mixture, and mixing is continued for about eight minutes to form substantially uniformly colored paste.
  • the resultant paste is milled on a standard 3-roll mill having a clearance of 0.5 mm. between the rolls.
  • the temperature of the rolls is maintained at about 20 C. and the product is removed from the mill in the form of homogeneous, green-colored ribbons.
  • These ribbons are discharged onto an endless belt which feeds the hopper of a standard screw extruder-type plodder.
  • the plodder is equipped with a wire net having openings of 0.5 mm. and a perforated plate having a series of tapered holes therein. These holes have a diameter which varies from 12-16 mm. with the largest diameter at the exit.
  • the milled material is continuously conglomerated and extruded through the perforated plate by action of the rotating screw.
  • the final product is extruded onto an endless belt as threads of spaghettilike noodles.
  • the extrusion temperature in the extruder barrel is maintained at 20 C. by circulating water through a jacket which surrounds the barrel and the temperature at the exit is maintained at 40 C.
  • the noodles are immediately cooled by a jet of air as they emerge from the plodder.
  • the noodles are then placed on an endless belt where they remam while air at 20 C. is passed thereover until they become non-tacky, hard, and breakable, at which time they are discharged into a granulator apparatus equipped with an 8-mesh screen where they are broken as they are forced through the screen.
  • the resultant product is formed of particles, each having a cross-sectional area of about 0.25 mm. and a length of 34 mm.
  • the specific gravity of the product is 1.45 gm./cc.
  • the bulk density of the product is about 0.75 gm./ cc.
  • the solubility of the particulate product was determined by measuring the time in seconds required to dissolve 1 gm. of product in 300 ml. of 20 C. water under agitation by a 50 mm. diameter propeller rotating at 180 rpm. All of the green-colored particles dissolved within 40 seconds.
  • Such a particulate product is characterized as fast dissolving or rapidly soluble because the usual solubility rate for spray-dried detergent in this test is from to 600 seconds.
  • the freshly extruded noodles contain about 12.9% water, and the resultant particle green-colored product contains 11.5% by weight of water.
  • EXAMPLE 2 One part by weight of the noodles formed in Example 1 is admixed with 99 parts by weight of an uncolored,
  • Example 3 The composition of Example 1 is reproduced with the exception that sodium xylene sulfonate is substituted for sodium toluene sulfonate.
  • the resulting green-colored, particulate product dissolved in 40 seconds using the solubility test of Example 1 and had a bulk density of 0.7 gm./ cc. and a specific gravity of 1.42.
  • EXAMPLE 4 The following composition is prepared using the process and equipment set forth in Example 1.
  • the resulting product has a homogeneous green color
  • EXAMPLE 5 The following composition is prepared in accordance with the process of Example 1 with the exception that the mixture from the amalgamation is mechanically worked using a 5-roll mill having a clearance of 0.5 mm. between rolls prior to being extruded at a temperature of 40-45 C.
  • the resulting homogeneously green-colored particles dissolve in eighty seconds using the test of Example 1 and have a bulk density of 0.67 gm./cc. and a specific gravity of 1.48 gm./cc. Addition of 0.4 part by weight of the product to 99.6 parts by weight of the white noncolored composition used in Example 1 yields a greenspeckled product having a very distinctive appearance.
  • EXAMPLE 6 A green-colored, particulate product having the following composition is prepared.
  • the foregoing composition is prepared by adding 0.5 kg. of tap water and 0.7 kg. of sodium carbonate anhydrous powder to 3.0 kg. of dodecyl benzene sulfonic acid in a leak-proof amalgamator with agitation.
  • Dodecylbenzene sulfonic acid analyzes 88% sulfonic acid, 7.5% sulphuric acid, and 4.5% water.
  • the sodium carbonate powder is added in small increment to facilitate neutralization of the sulfonic acid.
  • mixing is continued until a homogeneous appearing mixture is obtained. Then, 0.9 kg.
  • the resulting green-colored, homogeneous paste is mechanically worked on a 3 roll mill having a clearance of 0.5 mm. between the rolls, and the product is removed from the mill in the form of flakes which are are discharged into the hopper of the plodder used in Example 1.
  • the paste is extruded at a temperature in the range of 20 C. to C. in the form of noodles having a thickness of 0.5 mm. After further cooling, the noodles are passed through an 8-mesh screen to form a product having a length of 3-4 mm.
  • the resultant green-colored product dissolves in thirty seconds in the solubility test and has a specific gravity of 1.5 gm./cc. and a bulk density of 0.65 gm./cc.
  • a distinctively colored product having an aesthetic appearance is produced.
  • Example 7 The composition of Example 1 is reproduced with the exception that the commercial enzyme material Alcalase in an amount of 20% based on the weight of the total composition is added thereto before it is milled.
  • the re sulting noodle composition is especially effective to remove protein stains in addition to its normal cleansing ability.
  • a water-soluble, mechanically worked, substantially homogeneous, particulate detersive composition said composition being formed of discrete particles each of which consists essentially of (a) 10% to 40% by weight of Water-soluble, higher alkyl aryl sulfonate detergent salt having a 9 to 15 carbons in the alkyl group; (b) 10% to 40% by weight of a lower alkyl benzene sulfonate salt having one to three carbon atoms in the lower alkyl group; (c) 5% to by weight of a water-soluble, alkali metal, inorganic salt of which 2% to 20% by weight is an alkaline, hydratable, builder salt selected from the group consisting of orthophosphate, pyrophosphate, tripolyphosphate, silicate, carbonate borate, and mixtures thereof and the balance includes a salt selected from the group consisting of sulfate, halide, bicarbonate and sesquicarbonate; and (d) 2% to 20% by weight of water; the ratio of (a
  • composition of claim 1 wherein said higher alkyl aryl sulfonate is sodium or potassium alkyl benzene sulfonate containing an average of 12 to 14 carbon atoms in the higher alkyl group.
  • composition of claim 1 wherein said lower alkyl aryl sulfonate is a sodium or potassium lower alkyl benzene sulfonate.
  • composition of claim 1 wherein said discrete particles have an average cross sectional area of from 0.06 mm. to 0.3 mm.
  • composition of claim 1 wherein said mechanically worked, breakable, non-friable detersive composition contains in addition a colorant.
  • composition of claim 1 which further includes /2% to 10% by weight of a detergent foam booster selected from the group consisting of C -C fatty acid alkanolamides having 2 to 3 carbon atoms in each alkanol group, tertiary amine oxides of the formula R R R N O wherein R is an alkyl radical of 10 to 18 carbon atoms and R and R are each alkyl or hydroxy alkyl groups containing 1 to 3 carbon atoms, and C -C fatty alcohols.
  • a detergent foam booster selected from the group consisting of C -C fatty acid alkanolamides having 2 to 3 carbon atoms in each alkanol group, tertiary amine oxides of the formula R R R N O wherein R is an alkyl radical of 10 to 18 carbon atoms and R and R are each alkyl or hydroxy alkyl groups containing 1 to 3 carbon atoms, and C -C fatty alcohols.
  • a washing composition consisting essentially of 0.01% to 50% by weight of the water-soluble, mechanically worked, nontacky, rigid, breakable, non-friable and substantially homogeneous particulate detersive compositionof claim 1 and 50% to 99.99% by weight of a second particulate detergent composition comprising a synthetic Organic detergent selected from the group consisting of anionic, nonionic, and amphoteric detergents, and mixtures thereof.
  • said second particulate detergent composition includes, in ad dition a water-soluble, inorganic, alkaline builder salt.
  • washing composition of claim 7 wherein said second particulate detergent composition is a spray-dried composition.
  • a process for preparing a water-soluble mechanically worked, non-tacky, rigid, breakable, non-friable, homogeneous particulate detergent composition each particle consisting essentially of (a) 10% to 40% by weight of water-soluble, higher alkyl aryl sulfonate detergent salt having 9 to 15 carbons in the alkyl group; (b) 10% to 40% by Weight of a lower alkyl benzene sulfonate salt having one to three carbon atoms in the lower alkyl group; (c) to 50% by weight of a water-soluble alkali metal, inorganic salt of which 2% to 20% by weight is an alkaline, hydratable, builder salt selected from the group consisting of orthophosphate, pyrophosphate, tripolyphosphate, silicate, carbonate, borate and mixtures thereof and the balance includes a salt selected from the group consisting of sulfate, halide, bicarbonate and sesquicarbonate; and (d) 2% to 20% by weight of
  • a process as set forth in claim 10 wherein said mechanical working step includes milling said composition prior to the compacting and extruding step.

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CA (1) CA929439A (zh)
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DE (1) DE2050560B2 (zh)
DK (2) DK132898C (zh)
ES (1) ES384188A1 (zh)
FR (1) FR2066255A5 (zh)
GB (1) GB1303479A (zh)
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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4759867A (en) * 1983-07-07 1988-07-26 The Clorox Company Hard surface acid cleaner
US4925585A (en) * 1988-06-29 1990-05-15 The Procter & Gamble Company Detergent granules from cold dough using fine dispersion granulation
US4933100A (en) * 1988-01-19 1990-06-12 Colgate-Palmolive Co. Built synthetic organic detergent composition patties and processes for washing laundry therewith
US5034147A (en) * 1988-01-19 1991-07-23 Colgate-Palmolive Company Process for manufacture of built synthetic organic detergent composition patties
US5045238A (en) * 1989-06-09 1991-09-03 The Procter & Gamble Company High active detergent particles which are dispersible in cold water
US5496486A (en) * 1994-06-30 1996-03-05 Amway Corporation Process for increasing liquid surfactant loading in free flowing powder detergents
WO1997033961A1 (en) * 1996-03-15 1997-09-18 Amway Corporation Powder detergent composition and method of making
US5714456A (en) * 1996-03-15 1998-02-03 Amway Corporation Process for making discrete whitening agent particles
US5714452A (en) * 1996-03-15 1998-02-03 Amway Corporation Whitening agent particle composition
US5714450A (en) * 1996-03-15 1998-02-03 Amway Corporation Detergent composition containing discrete whitening agent particles
US5998351A (en) * 1996-03-15 1999-12-07 Amway Corporation Discrete whitening agent particles method of making, and powder detergent containing same
EP1043387A2 (de) * 1999-03-27 2000-10-11 Cognis Deutschland GmbH Alkylbenzolsulfonat-Granulate
WO2001029162A1 (de) * 1999-10-21 2001-04-26 Henkel Kommanditgesellschaft Auf Aktien Abriebverbesserte wasch- oder reinigungsmittelformkörper
WO2002006432A1 (en) * 2000-07-13 2002-01-24 The Procter & Gamble Company Granular detergent composition having an improved solubility
US6589931B2 (en) 2000-07-13 2003-07-08 The Procter & Gamble Company Granular detergent composition having an improved solubility

Families Citing this family (15)

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Publication number Priority date Publication date Assignee Title
US4289640A (en) * 1974-01-21 1981-09-15 Colgate-Palmolive Company Cleaning compositions
US4399049A (en) 1981-04-08 1983-08-16 The Procter & Gamble Company Detergent additive compositions
CA1217690A (en) * 1983-07-07 1987-02-10 Clement K. Choy Hard surface acid cleaner
DE3617756C2 (de) * 1985-05-29 1995-01-19 Lion Corp Verfahren zum Herstellen einer granularen Detergentien-Zusammensetzung mit hoher Schüttdichte
GB2231579A (en) * 1989-05-09 1990-11-21 Unilever Plc Spray-dried detergent
ATE107352T1 (de) * 1989-08-09 1994-07-15 Henkel Kgaa Herstellung verdichteter granulate für waschmittel.
DE4007601A1 (de) * 1990-03-09 1991-09-12 Henkel Kgaa Verfahren zum herstellen von granulaten eines wasch- oder reinigungsmittels
DE19531690A1 (de) * 1995-08-29 1997-03-06 Henkel Kgaa Figurenhaft ausgestaltete feste und verdichtete Mehrkomponentengemische aus dem Bereich der Wasch- und Reinigungsmittel sowie Verfahren zu ihrer Herstellung
GB9711350D0 (en) * 1997-05-30 1997-07-30 Unilever Plc Granular detergent compositions and their production
DE69817811T2 (de) 1997-05-30 2004-04-01 Unilever N.V. Rieselfähige körnige waschmittelzusammensetzungen
GB9711356D0 (en) 1997-05-30 1997-07-30 Unilever Plc Particulate detergent composition
GB9711359D0 (en) 1997-05-30 1997-07-30 Unilever Plc Detergent powder composition
DE19848024A1 (de) * 1998-10-17 2000-04-20 Henkel Kgaa Verfahren zur Herstellung extrudierter Formkörper
WO2010122050A2 (en) 2009-04-24 2010-10-28 Unilever Plc Manufacture of high active detergent particles
EP2243822A1 (en) 2009-04-24 2010-10-27 Unilever PLC Detergent powder with high active detergent particles

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US2634240A (en) * 1949-07-09 1953-04-07 Standard Oil Dev Co Alkyl aryl sulfonate detergent composition
US2773833A (en) * 1951-09-14 1956-12-11 California Research Corp Non-caking alkyl aryl sulfonate detergent compositions
NL131792C (zh) * 1964-07-17
US3515672A (en) * 1965-06-24 1970-06-02 Colgate Palmolive Co Apparatus and process for the preparation of detergent compositions

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4759867A (en) * 1983-07-07 1988-07-26 The Clorox Company Hard surface acid cleaner
US4933100A (en) * 1988-01-19 1990-06-12 Colgate-Palmolive Co. Built synthetic organic detergent composition patties and processes for washing laundry therewith
US5034147A (en) * 1988-01-19 1991-07-23 Colgate-Palmolive Company Process for manufacture of built synthetic organic detergent composition patties
US4925585A (en) * 1988-06-29 1990-05-15 The Procter & Gamble Company Detergent granules from cold dough using fine dispersion granulation
US5045238A (en) * 1989-06-09 1991-09-03 The Procter & Gamble Company High active detergent particles which are dispersible in cold water
US5496486A (en) * 1994-06-30 1996-03-05 Amway Corporation Process for increasing liquid surfactant loading in free flowing powder detergents
US5635467A (en) * 1994-06-30 1997-06-03 Amway Corporation Powdered composition exhibiting increased liquid surfactant loading for free flowing powder detergents
US5714456A (en) * 1996-03-15 1998-02-03 Amway Corporation Process for making discrete whitening agent particles
WO1997033961A1 (en) * 1996-03-15 1997-09-18 Amway Corporation Powder detergent composition and method of making
US5714452A (en) * 1996-03-15 1998-02-03 Amway Corporation Whitening agent particle composition
US5714450A (en) * 1996-03-15 1998-02-03 Amway Corporation Detergent composition containing discrete whitening agent particles
US5714451A (en) * 1996-03-15 1998-02-03 Amway Corporation Powder detergent composition and method of making
US5998351A (en) * 1996-03-15 1999-12-07 Amway Corporation Discrete whitening agent particles method of making, and powder detergent containing same
US6080711A (en) * 1996-03-15 2000-06-27 Amway Corporation Powder detergent composition and method of making
EP1043387A2 (de) * 1999-03-27 2000-10-11 Cognis Deutschland GmbH Alkylbenzolsulfonat-Granulate
EP1043387A3 (de) * 1999-03-27 2003-03-26 Cognis Deutschland GmbH & Co. KG Alkylbenzolsulfonat-Granulate
WO2001029162A1 (de) * 1999-10-21 2001-04-26 Henkel Kommanditgesellschaft Auf Aktien Abriebverbesserte wasch- oder reinigungsmittelformkörper
WO2002006432A1 (en) * 2000-07-13 2002-01-24 The Procter & Gamble Company Granular detergent composition having an improved solubility
US6589931B2 (en) 2000-07-13 2003-07-08 The Procter & Gamble Company Granular detergent composition having an improved solubility

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FR2066255A5 (zh) 1971-08-06
BE757913A (fr) 1971-04-01
DE2050560A1 (de) 1971-04-29
ZA706664B (en) 1972-05-31
GB1303479A (zh) 1973-01-17
ZM11170A1 (en) 1972-10-23
DK132898A (zh)
ES384188A1 (es) 1973-01-01
DE2050560B2 (de) 1978-09-21
NO134914C (zh) 1977-01-05
DK132898B (da) 1976-02-23
CH561773A5 (zh) 1975-05-15
DE2050560C3 (zh) 1979-05-17
NL7015681A (zh) 1971-04-27
NO134914B (zh) 1976-09-27
CA929439A (en) 1973-07-03
SE354671B (zh) 1973-03-19
DK132898C (da) 1976-07-26

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