WO1995016016A1 - Composition detergente contenant un tensioactif a l'oxyde d'amine sous forme d'agglomerats - Google Patents

Composition detergente contenant un tensioactif a l'oxyde d'amine sous forme d'agglomerats Download PDF

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Publication number
WO1995016016A1
WO1995016016A1 PCT/US1994/014274 US9414274W WO9516016A1 WO 1995016016 A1 WO1995016016 A1 WO 1995016016A1 US 9414274 W US9414274 W US 9414274W WO 9516016 A1 WO9516016 A1 WO 9516016A1
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WIPO (PCT)
Prior art keywords
detergent composition
surfactant
amine oxide
detergent
surfactants
Prior art date
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PCT/US1994/014274
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English (en)
Inventor
Ronald Allen Swift
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The Procter & Gamble Company
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Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to JP7516385A priority Critical patent/JPH09506389A/ja
Priority to BR9408264A priority patent/BR9408264A/pt
Priority to AU13393/95A priority patent/AU1339395A/en
Priority to EP95904882A priority patent/EP0733095A1/fr
Publication of WO1995016016A1 publication Critical patent/WO1995016016A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides

Definitions

  • the present invention is generally directed to a detergent composition in the form of agglomerates having improved biodegradability and cleaning, especially in cold temperature laundering solutions. More particularly, the invention is directed to an agglomerated, nil-phosphate detergent composition containing an amine oxide surfactant as the principle surfactant and reduced levels of linear alkylbenzene sulfonate surfactant (also referenced herein as "LAS") so as to improve the overall biodegradability of the detergent composition.
  • the detergent composition also achieves improved cleaning by increasing the solubility of the amine oxide surfactant and LAS. especially in cold temperature washing solutions (e.g. 5°C to 30°C) and high water hardness conditions (e.g. 7 grains/gallon).
  • the detergent of the invention is in the form of detergent agglomerates rather than spray dried granules.
  • conventional detergent compositions contain mixtures of various surfactants in order to remove a wide variety of soils and stains from surfaces.
  • various anionic surfactants especially the alkyl benzene sulfonates, are useful for removing particulate soils
  • various nonionic surfactants such as the alkyl ethoxylates and alkylphenol ethoxylates, are useful for removing greasy soils.
  • Another class of surfactants which has found use in various compositions where emulsification is desired comprises the secondary alkyl sulfates (also referenced herein as "SAS").
  • the conventional secondary alkyl sulfate surfactants are available as generally pasty, random mixtures of sulfated linear and/or partially branched alkanes.
  • Rossall et al. U.S. Patent No. 4,235,752 disclose a detergent surfactant which is a C j o_ j g secondary alkyl sulfate containing 50% of 2/3 sulfate isomers and 40% of various other effective isomers.
  • the surfactant materials disclosed by Rossall et al is for use primarily in dishwashing operations.
  • Tosaka et al also exemplifies only "liquid" dishwashing detergent compositions and hard surface cleaning compositions, although powdered forms of such compositions are also contemplated.
  • the Tosaka et al patent does not incorporate amine oxide surfactants directly into detergent agglomerates for increased solubility in cold temperature washing solutions. Rather. Tosaka et al combine discrete amine oxide particles with spray dried granules to form their detergent composition.
  • the Tosaka et al patent does not speak to the solubility problem associated with cold temperature laundering solutions, a problem particularly prevalent when using detergents having sulfate-based (i.e. AS, SAS. AES, etc.) surfactant systems comprising less than about 30% of LAS.
  • alkyl sulfate surfactants including both primary and secondary alkyl sulfates
  • cold temperature e.g. 5°C to 30°C
  • compact detergent products For the consumer, the smaller package size attendant with compact detergent products provides for easy storage and handling. For the manufacturer, unit storage costs, shipping costs and packaging costs are lowered.
  • compact detergents have its difficulties.
  • in a typical compact detergent formulation the so-called "inert" ingredients such as sodium sulfate are substantially eliminated.
  • such ingredients do play a role in enhancing solubility of conventional detergents.
  • compact detergents often suffer from solubility problems, especially in cold temperature laundering solutions.
  • conventional compact or low density detergent granules are usually prepared by spray drying processes which result in extremely porous detergent particles that are quite amenable to being dissolved in aqueous washing solutions.
  • compact detergents are typically comprised of less porous, high density detergent particles which are less soluble.
  • the compact form of granular detergents typically comprise particles or granules which contain high levels of detersive ingredients with little or no room for solubilizing agents, and since such particles are intentionally manufactured at high bulk densities, the net result can be a substantial problem with regard to in- use solubility. Accordingly, despite the disclosures in the art, there remains a need for a detergent composition which has improved cleaning performance, especially in cold temperature washing solutions. This need is especially prevalent in the art of compact or high density detergents currently being used by consumers. There is also a need for such a detergent composition which achieves these benefits by way of exhibiting improved solubility of the surfactants in the composition under high hardness and cold temperature water conditions. Also, there is a need for such a detergent composition which exhibits improved biodegradability.
  • the present invention meets the needs identified above by providing a detergent composition in the form of agglomerates which exhibit improved solubility or dissolution of the surfactants in cold temperature washing solutions as well as under high water hardness conditions.
  • the detergent composition comprises a surfactant system having a high level of an amine oxide surfactant in combination with a low level of linear alkylbenzene sulfonate surfactant.
  • the low level i.e. less than about 30% of the surfactant system, and the omission of phosphates in the detergent composition is maintained for purposes of achieving improved biodegradability.
  • Other adjunct detergent ingredients may also be included in the agglomerates which form the detergent composition.
  • high active (high surfactant levels) particles e.g. SAS and AS
  • the phrase "improved solubility" means that the solubility of the surfactants of the detergent composition is enhanced by at least 5% in the laundering solution when employed in the manner of this invention, as compared to the solubility of the same surfactants per se, under the same test conditions (i.e. water temperature and pH, stirring speed and time, particle size, water hardness, and the like).
  • agglomerates refers to particles formed by agglomerating particles which typically have a smaller mean particle size than the formed agglomerates. All percentages, ratios and proportions used herein are by weight, unless otherwise specified. All documents including patents and publications cited herein are incorporated herein by reference.
  • a detergent composition in form of agglomerates comprises from about 1% to 50% by weight of a detersive surfactant system.
  • the surfactant system itself comprises, by weight of the surfactant system, (i) at least about 50% of an amine oxide surfactant, and (ii) less than about 30% of a linear alkylbenzene sulfonate surfactant.
  • the detergent composition includes at least about 1% by weight of a detergency builder to enhance cleaning.
  • the surfactant system and the builder are agglomerated to form detergent agglomerates which are substantially free of phosphates.
  • the surfactants in the detergent composition have improved solubility in an aqueous laundering solution.
  • solubility of the amine oxide surfactant, the LAS surfactant and other surfactants, if included, is enhanced by at least 5%. preferably 10 to 50%, over those same surfactants alone under the same test conditions in aqueous washing solutions at cold temperatures, i.e. 5°C to 30°C.
  • a method for laundering soiled fabrics comprises the step of contacting soiled fabrics with an effective amount of a detergent composition as described herein in an aqueous laundering solution.
  • An effective amount is typically on the order of 1000 to 1500 ppm.
  • the invention is directed to a detergent composition having improved solubility in cold temperature laundering solutions.
  • a multitude of consumers around the world launder soiled clothes in conventional washing machines unique to their particular geographic location.
  • these conventional washing machines launder the soiled clothes in water supplied at relatively cold temperatures, for example in range of 5°C to 30°C, and at high hardness concentrations, e.g. 7 grains/gallon (rich with Ca and Mg ions).
  • Most of the modern day consumers also use compact or condensed laundry detergents to accomplish their laundering needs. Under the aforementioned conditions, solubility of current detergents in aqueous laundering solutions has been a problem.
  • the solubility of a detergent composition can be increased by incorporating amine oxide surfactant with a minimal amount (less than 30% of the surfactant system) of linear alkylbenzene sulfonate surfactant directly into the detergent by way of agglomeration.
  • the detergent composition in the form of agglomerates, the solubility of the overall surfactant system in the laundering solution is improved, especially those solutions kept at cold temperatures (e.g. 5°C to 30°C).
  • the preferred detergent composition of the invention comprises from about 1% to about 50%, preferably from about 15% to about 40%, by weight a surfactant system of which at least 50%, preferably from about 50% to about 100%.
  • the surfactant system may include nonionic surfactants and/or anionic surfactants such as those selected from the group consisting of alkyl sulfates, alkyl ethoxy sulfates, secondary alkyl sulfates and mixtures thereof While the level of these adjunct surfactants can vary, generally they comprise from about 0.01% to about 50% of the surfactant system.
  • the detergent composition of the invention also comprises at least about 1%, preferably from about 10% to about 40%. of a detergency builder.
  • the detergent composition may also include one or more of adjunct detergent ingredients.
  • adjunct detergent ingredients Nonlimiting examples of the detergency builder and such adjunct ingredients are described in detail hereinafter.
  • the detergent composition herein is formulated and processed to achieve a density of at least 650 g/1 for purposes of producing a "compact" detergent product.
  • the detergent agglomerates which form the detergent composition of the invention preferably do not contain phosphates and contain little or no LAS. Further, it is important for the detergent composition to be in the form of "agglomerates" as opposed to spray dried granules. This is particularly important since most amine oxide surfactants cannot be readily subjected to spray drying processes without causing or creating extremely adverse plumes from the spray drying towers. The same is true for alkyl sulfate and alkyl ethoxy sulfate surfactants. As a consequence, past as well as current detergents only incorporate amine oxide surfactants as a "separate" adjunct ingredient. This, however, does not provide the detergent composition with satisfactory solubility characteristics.
  • the detergent composition of the present invention incorporates the amine oxide directly "into" the individual agglomerates by way of an agglomeration process technique as described hereinafter. While not intending to be limited by theory, it is believed that the amine oxide is brought into the aqueous laundering solution more rapidly and more completely as a result of being intimately bound within the agglomerates. In agglomerated form, the amine oxide apparently is extremely hygroscopic and has very little crystallinity tendencies so as to be very soluble, especially in cold temperature washing solutions. Furthermore, by utilizing an amine oxide surfactant along with other adjunct surfactants such as AS, AES and SAS, the overall solubility of the detergent agglomerates in cold washing solutions and high hardness conditions is improved, thereby resulting in improved cleaning performance.
  • the "improved solubility" achieved by the detergent composition is concerned with enhanced solubility of the surfactant system of which at least 50% is an amine oxide surfactant.
  • the improvement represents at least a 5% increase in solubility of the surfactant system in the wash solution over the solubility of the same surfactants if they were dissolved alone or without being contained in a detergent composition as defined herein. More preferably, the solubility improvement is from about 10% to about 50%.
  • any comparison of the surfactant system solubility should be completed under the same laundering conditions, e.g. water temperature, hardness and pH, stirring speed and time, and particle size. Typical surfactant system solubility improvements are set forth in the Examples hereinafter.
  • the amount of the surfactant system in the washing solution can be determined.
  • the amount of amine oxide surfactant dissolved can be determine by way of a titration technique during which samples of the aqueous laundering solution containing the detergent composition are taken after one minute and filtered with 0.45 mm nylon filter paper, after which a cationic titrant, which can be commercially purchased, e.g. from Sigma Chemical Company under the trade name Hyamine. is added to the filtered solution. The filtered solution is then titrated with an anionic titrant such as sodium dodecyl sulfate. From the foregoing, the amount of cationic surfactant, i.e.
  • amine oxide which was dissolved in the washing solution can be determined.
  • the solubility of the other optional surfactants contained in the surfactant system can be determined by well known techniques such as the so-called "catSO ⁇ " titration technique.
  • the Examples presented hereinafter illustrate the improved solubility of the amine oxide surfactant as well as the aforementioned titration technique.
  • the agglomerated detergent composition contains a surfactant system including at least 50% of an amine oxide surfactant and less than about 30% of LAS.
  • the surfactant system may include additional surfactants, nonlimiting examples of which are provided hereinafter.
  • amine oxide surfactants suitable for used herein have the general formula
  • R j is a Cg_24 alkyl group or a substituted C _24 alkyl group.
  • R2 and R3 are H, a C1.3 alkyl group or a substituted C ] _3 alkyl group, and n is from 0 to about 10.
  • Nonlimiting examples of the amine oxide surfactant include C j o-i8 amine oxides, secondary amine oxides, and tertiary amine oxides.
  • the tertiary amine oxide surfactant may be in hydrated form and have the general formula R1R2R3NO n ⁇ O wherein Ri , R2 and R3 are the same as above and n is 1 or 2.
  • tertiary amines suitable for use herein include those containing one or two short-chain groups independently selected from methyl, ethyl, and 2- hydroxyethyl groups, with the remaining valences of the amino nitrogen being satisfied with long- chain groups independently selected from primary alkyl groups containing 8-24 carbons, e.g., octyl. decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, and tetracosyl groups.
  • the primary alkyl groups may be branched-chain groups, but the preferred amines are those in which at least most of the primary alkyl groups have a straight chain.
  • tert-amines are N-octyldimethylamine, N,N-didecylmethylamine, N- decyl-N-dodecylethylamine.
  • SUBSTltUTE SHEET (RULE 26) octadecyldimethylamine. N.N-dieicosylethylamine, N-docosyl-N-2-hydroxyethylmethylamine. N- tetracosyldimethylamine, etc.
  • tertiary as well as secondary amine oxides suitable for use herein include dimethyldodecylamine oxide, dimethyltetradecylamine oxide, ethylmethyltetradecylamine oxide, cetyldimethylamine oxide, dimethylstearylamine oxide, cetylethylpropylamine oxide, diethyldodecylamine oxide, diethyltetradecylamine oxide, dipropyldodecylamine oxide. bis-(2- hydroxyethyl) dodecylamine oxide, bis(2-hydroxyethyl)-3-dodecoxy-2-hydroxypropylamine oxide.
  • amine oxide surfactants for use herein include C12-14 dimethylamine oxides. Most preferred is dimethyldodecylamine oxide.
  • the surfactant system can include conventional Ci j -C j g alkyl benzene sulfonates (also referenced herein as "LAS) as long as the level does not exceed about 30% of the surfactant system. While the biodegradability of the so-called "LAS" surfactants have been the subject of some concern, the surfactant system herein may include a small amount of (i.e. less than 30%) LAS for purposes of improving the overall solubility of the detergent composition without substantially decreasing the overall biodegradability of the present detergent composition.
  • LAS alkyl benzene sulfonates
  • Adjunct Surfactants The surfactant system may also include a variety of adjunct surfactants wherein the aggregate amount of the adjuncts do not exceed 50% of the surfactant system.
  • adjunct surfactants Nonlimiting examples are presented herein and include conventional primary alkyl sulfate surfactants have the general formula
  • ROS03-M+ wherein R is typically a linear C 10 -C20 hydrocarbyl group and M is a water-solubilizing cation.
  • Branched-chain primary alkyl sulfate surfactants having 10-20 carbon atoms can also be used herein; see, for example, European Patent Application 439,316, Smith et al, filed 21.01.91, the disclosure of which is incorporated herein by reference (Included in the term "alkyl” is the alkyl portion of acyl groups). Included in the surfactant system are the C j o-C j alkyl alkoxy sulfates ("AE X S"; especially EO 1-7 ethoxy sulfates). Conventional secondary alkyl sulfate surfactants can also be used herein and include those materials which have the sulfate moiety distributed randomly along the hydrocarbyl "backbone" of the molecule. Such materials may be depicted by the structure
  • a selected secondary (2,3) alkyl sulfate surfactant is used herein which comprises structures of formulas A and B
  • x and (y+1) are, respectively, integers of at least about 6, and can range from about 7 to about 20, preferably about 10 to about 16.
  • M is a cation, such as an alkali metal, ammonium, alkanolammonium, alkaline earth metal, or the like.
  • Sodium is typical for use as M to prepare the water-soluble (2,3) alkyl sulfates, but ethanolammonium, diethanolammonium, triethanolammonium, potassium, ammonium, and the like, can also be used. It is preferred that the secondary (2,3) alkyl sulfates be substantially free (i.e., contain less than about 20%, more preferably less than about 10%, most preferably less than about 5%) of such random secondary alkyl sulfates.
  • the preparation of the secondary (2,3) alkyl sulfates of the type useful herein can be carried out by the addition of H2SO4 to olefms. A typical synthesis using -olefins and sulfuric acid is disclosed in U.S.
  • 2,3-disulfates may also be present, but generally comprise no more than 5% of the mixture of secondary (2,3) alkyl mono-sulfates.
  • Such materials are available as under the name "DAN”, e.g., "DAN 200" from Shell Oil Company.
  • solubility of the "crystalline" secondary (2,3) alkyl sulfate surfactants is desired, the formulator may wish to employ mixtures of such surfactants having a mixture of alkyl chain lengths.
  • a mixture of Ci 2-C1 g alkyl chains will provide an increase in solubility over a secondary (2,3) alkyl sulfate wherein the alkyl chain' is, say. entirely C j g.
  • the solubility of the secondary (2,3) alkyl sulfates can also be enhanced by the addition thereto of other surfactants such as the material which decreases the crystallinity of the secondary (2,3) alkyl sulfates.
  • Such crystallinity-interrupting materials are typically effective at levels of 20%, or less, of the secondary (2,3) alkyl sulfate.
  • surfactants useful in conjunction with the surfactants described herein are the Ci ⁇ -C j alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the Ci . j glycerol ethers, the C jQ -Cig alkyl polyglycosides and their corresponding sulfated polyglycosides, and C j 2-C j g alpha-sulfonated fatty acid esters.
  • the conventional nonionic and amphoteric surfactants such as the alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C -C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C j ⁇ -C j g betaines and sulfobetaines ("sultaines"), can also be included in the overall compositions.
  • the CJ Q -C j N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C ⁇ -C j N-methylglucamides. See WO 9,206.154.
  • N-propyl through N-hexyl C j ⁇ -C j g glucamides can be used for low sudsing.
  • C1Q-C20 conventional soaps may also be used. If high sudsing is desired, the branched- chain C j o-Ci6 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.
  • the detergent composition of the invention also includes a detergency builder material to assist in controlling mineral hardness.
  • Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of paniculate soils.
  • Inorganic detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates). sulphates, and aluminosilicates.
  • silicate builders are the alkali metal silicates, particularly those having a Si ⁇ 2-Na2 ⁇ ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck.
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6").
  • Hoechst commonly abbreviated herein as "SKS-6”
  • the Na SKS-6 silicate builder does not contain aluminum.
  • NaSKS-6 has the delta-Na2Si ⁇ 5 morphology form of layered silicate.
  • SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi x ⁇ 2 X + ⁇ yH2 ⁇ wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20. preferably 0 can be used herein.
  • Various other layered silicates from Hoechst include NaSKS-5. NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms.
  • delta-Na2Si ⁇ 5 (NaSKS-6 form) is most preferred for use herein.
  • Other silicates may also be useful such as for example magnesium silicate, which can serve as a crisping agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
  • Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15. 1973.
  • Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations.
  • Aluminosilicate builders include those having the empirical formula:
  • aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3.985.669. Krummel. et al, issued October 12. 1976.
  • Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X.
  • the crystalline aluminosilicate ion exchange material has the formula:
  • This material is known as Zeolite A.
  • the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
  • Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds.
  • poly- carboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
  • polycarboxylate builders include a variety of categories of useful materials.
  • One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4.663.071. issued to Bush et al. on May 5. 1987.
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120.874 and 4.102,903.
  • ether hydroxypolycarboxylates copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6- trisulphonic acid, and carboxymethyloxysuccinic acid
  • various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid
  • polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • Citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used, however, in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.
  • succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof.
  • a particularly preferred compound of this type is dodecenylsuccinic acid.
  • succinate builders include: laurylsuccinate. myristylsuccinate, palmitylsuccinate. 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent
  • Fatty acids e.g., Ci2-C j g monocarboxylic acids
  • Ci2-C j g monocarboxylic acids can also be incorporated into the compositions alone, or in combination with the aforesaid builders, especially citrate and/or the succinate builders, to provide additional builder activity.
  • Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
  • the detergent composition can also include any number of additional ingredients in an amount from 0% to about 75% by weight of the detergent composition.
  • additional ingredients include bleaches, bleach activators, suds boosters or suds suppressers, anti-tarnish and anticorrosion agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, non-builder alkalinity sources, chelating agents, smectite clays, enzymes, enzyme-stabilizing agents and perfumes. See U.S. Patent 3,936,537, issued February 3, 1976 to Baskerville, Jr. et al., incorporated herein by reference. Bleaching agents and activators are described in U.S. Patent 4,412,934, Chung et al., issued
  • Enzymes can be included in the formulations herein for a wide variety of fabric laundering purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and for the prevention of refugee dye transfer, and for fabric restoration.
  • the enzymes to be incorporated include proteases, amylases, Upases, cellulases. and peroxidases, as well as mixtures thereof.
  • Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH-activity and/or stability optima, thermostability, stability versus active detergents, builders and so on.
  • bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
  • proteases are the subtilisins which are obtained from particular strains of B. sub tilts and B.lichenifo ms.
  • Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trade name ESPERASE. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No. 1,243,784 of Novo.
  • Proteolytic enzymes suitable for removing protein-based stains include those sold under the trade names ALCALASE and SAVINASE by Novo Industries A S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (The Netherlands).
  • Other proteases include Protease A (see European Patent Application 130,756, published January 9, 1985) and Protease B (see European Patent Application Serial No. 87303761.8, filed April 28, 1987, and European Patent Application 130.756, Bott et al, published January 9, 1985).
  • Amylases include, for example, ⁇ -amylases described in British Patent Specification No. 1,296,839 (Novo). RAPID ASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo Industries.
  • the cellulase usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5.
  • Suitable cellulases are disclosed in U.S. Patent 4.435.307, Barbesgoard et al, issued March 6, 1984. which discloses fungal cellulase produced from Humicola insolens and Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas. and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander).
  • suitable cellulases are also disclosed in GB-A- 2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372.034. See also Upases in Japanese Patent Application 53.20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P.” Other commercial Upases include Amano-CES, Upases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
  • lipolyticum NRRLB 3673 commercially available from Toyo Jozo Co.. Tagata. Japan; and further Chromobacter viscosum Upases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and Upases ex Pseudomonas gladioli.
  • the LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo is a preferred lipase for use herein.
  • Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate. perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching.” i.e.
  • Peroxidase enzymes are known in the art. and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase.
  • Peroxidase- containing detergent compositions are disclosed, for example, in PCT Intemational Application WO 89/099813, published October 19, 1989, by O. Kirk, assigned to Novo Industries A/S.
  • dye transfer inhibiting agents may also be included, for example, polyvinylpyrrolidone, polyamine N-oxide, copolymers of N-vinylpyrrolidone and N-vinylimidazole are a suitable dye transfer inhibiting polymers for use in the present detergent composition.
  • the level of such additional dye transfer inhibiting agents may vary, but typically will be from about 0.01% to about 10% by weight of the detergent composition.
  • Step A Preparation of Surfactant Paste -
  • the objective is to combine the surfactants including the amine oxide surfactant and liquids in the compositions into a common mix in order to aid in surfactant solubilization and agglomeration.
  • the surfactants and other liquid components in the composition are mixed together in a Sigma Mixer at 140°F (60°C) at about 40 rpm to about 75 rpm for a period of from 15 minutes to about 30 minutes to provide a paste having the general consistency of 20.000-40,000 centipoise.
  • the paste is stored at 140°F (60°C) until agglomeration Step (B) is ready to be conducted.
  • Step B Agglomeration of Powders with Surfactant Paste -
  • the purpose of this Step is to transform the base formula ingredients into flowable detergent agglomerates having a mean particle size range of from about 800 microns to about 1600 microns.
  • the powders including materials such as zeolite, citrate, citric acid builder, layered silicate builder (as SKS-6), sodium carbonate, ethylenediaminedisuccinate, magnesium sulfate and optical brightener
  • the Eirich Mixer R-Series
  • mixed briefly ca. 5 seconds - 10 seconds
  • the surfactant paste from Step A is then charged into the mixer and the mixing is continued at about 1500 rpm to about 3000 rpm for a period from about 1 minute to about 10 minutes, preferably 1-3 minutes, at ambient temperature.
  • the mixing is stopped when course agglomerates (average particle size 800-1600 microns) are formed.
  • Step C The purpose of this Step is to reduce the agglomerates' stickiness by removing/drying moisture and to aid in particle size reduction to the target particle size (in the mean particle size range from about 800 to about 1600 microns, as measured by sieve analysis).
  • the wet agglomerates are charged into a fluidized bed at an air stream temperature of from about 41°C to about 60°C and dried to a final moisture content of the particles from about 4% to about 10%.
  • Step D Coat Agglomerates and Add Free-Flow Aids -
  • the objective in this Step is to achieve the final target agglomerate size range of from about 800 microns to about 1600 microns, and to admix materials which coat the agglomerates, reduce the caking/lumping tendency of the particles and help maintain acceptable flowability.
  • the dried agglomerates from Step C are charged into the Eirich Mixer (R-Series) and mixed at a rate of about 1500 rpm to about 3000 rpm while adding 2-6% Zeolite A (median particle size 2-5 ⁇ m) during the mixing.
  • the mixing is continued until the desired median particle size is achieved (typically from about 5 seconds to about 45 seconds). At this point, from about 0.1% to about 1.5% by weight of precipitated silica (average particle size 1-3 microns) is added as a flow aid and the mixing is stopped.
  • compositions A-E are made in accordance with the agglomeration process described above.
  • Compositions A. B and C are within the scope of the invention and compositions D and E are outside of the invention and are presented for purposes of comparison as described in Example II hereinafter.
  • the relative proportions of compositions A-E, in agglomerate form, are listed in Table I below.
  • Neodol nonionic surfactant commercially available from Shell Chemical Company under the trade name Neodol
  • compositions A-E 1170 ppm are dissolved in an aqueous laundering solution having a water temperature of 10°C and a water hardness of 7 grains/gallon (Ca:Mg ratio of 3: 1).
  • the laundering solution is continuously agitated at a rate of 75 rpm and samples of the wash solution were taken at various time intervals as shown in Table I below.
  • the amount of surfactant in the laundering solution is determined by conducting the titration technique described previously wherein samples are taken from individual wash solutions containing one of the compositions A-E and titrated to determine the cationic surfactant concentration. More specifically, the amount of cationic surfactant dissolved in the laundering solution is determined by filtering the aforementioned samples through 0.45 nylon filter paper to remove the insolubles and thereafter, adding a cationic titrant. such as HyamineTM which is commercially available from Sigma Chemical Company, to the filtered solution. The filtered solution is then titrated with an anionic titrant to determine the cationic concentration.
  • a cationic titrant such as HyamineTM which is commercially available from Sigma Chemical Company
  • the relative amount of surfactant dissolved in the wash solution can be determined. This technique is well known and others may be used if desired, especially if concentrations of anionic and nonionic surfactants are desired. The results are shown in Table II below. TABLE ⁇
  • compositions A, B and C which are within the scope of the invention surprisingly have improved solubility over compositions D and E which are outside the scope of the invention.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

Cette invention se rapporte à une composition détergente sous forme d'agglomérats, qui contient environ 1 à 50 % en poids d'un système de tensioactifs détersifs. Ce système de tensioactifs comprend lui-même, en poids par rapport au système de tensioactifs, (i) au moins 50 % environ d'un tensionactif à l'oxyde d'amine, et (ii) moins de 30 % environ d'un tensioactif aux sulfonates d'alkylbenzène linéaires (LAS). Cette composition détergente contient également au moins 1 % environ en poids d'un adjuvant de détergent, destiné à accroître le pouvoir nettoyant. Le système de tensioactifs et l'adjuvant sont agglomérés pour former des agglomérats détergents essentiellement exempts de phosphates. Les tensioactifs de cette composition détergente présentent une meilleure solubilité dans les solutions de blanchissage aqueuses. Ainsi, la solubilité du tensioactif à l'oxyde d'amine, du tensioactif LAS et, le cas échéant, d'autres tensioactifs, est améliorée, dans les mêmes conditions de test, d'au moins 5 % par rapport à celle observée avec des tensioactifs identiques mais non combinés de cette même façon.
PCT/US1994/014274 1993-12-07 1994-12-07 Composition detergente contenant un tensioactif a l'oxyde d'amine sous forme d'agglomerats WO1995016016A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP7516385A JPH09506389A (ja) 1993-12-07 1994-12-07 凝集体の形態のアミンオキシド界面活性剤含有洗剤組成物
BR9408264A BR9408264A (pt) 1993-12-07 1994-12-07 Composição detergente contendo tensoativo xido de amina na forma de aglomerados
AU13393/95A AU1339395A (en) 1993-12-07 1994-12-07 Detergent composition containing amine oxide surfactant in the form of agglomerates
EP95904882A EP0733095A1 (fr) 1993-12-07 1994-12-07 Composition detergente contenant un tensioactif a l'oxyde d'amine sous forme d'agglomerats

Applications Claiming Priority (2)

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US16345093A 1993-12-07 1993-12-07
US08/163,450 1993-12-07

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WO1995016016A1 true WO1995016016A1 (fr) 1995-06-15

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CA (1) CA2177678A1 (fr)
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0863973A1 (fr) * 1995-09-26 1998-09-16 The Procter & Gamble Company Composition detergente comprenant un melange d'adjuvant bicarbonate-zeolite
US5958871A (en) * 1995-09-26 1999-09-28 The Procter & Gamble Company Detergent composition based on zeolite-bicarbonate builder mixture
WO2008071519A1 (fr) * 2006-12-13 2008-06-19 Henkel Ag & Co. Kgaa Préparation de granulats d'oxyde d'amine et leur mise en œuvre
WO2015191434A2 (fr) 2014-06-09 2015-12-17 Stepan Company Détergents pour nettoyage à l'eau froide
WO2016111884A2 (fr) 2015-01-08 2016-07-14 Stepan Company Détergents textiles à l'eau froide

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108441337B (zh) * 2018-02-12 2021-03-16 广州蓝月亮实业有限公司 一种表面活性剂组合物

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US3234139A (en) * 1961-12-21 1966-02-08 Procter & Gamble Diamine dioxide detergent compositions
US3281368A (en) * 1961-12-04 1966-10-25 Procter & Gamble Built tertiary amine oxide detergents
JPS5754159A (ja) * 1980-09-18 1982-03-31 Nippon Oil & Fats Co Ltd Aminokishidonofuntaikamataharyukahoho
JPH02178399A (ja) * 1988-12-29 1990-07-11 Lion Corp 粒状洗剤組成物
EP0421327A1 (fr) * 1989-10-02 1991-04-10 Albemarle Corporation Détergent universel pour le linge
US5071594A (en) * 1989-10-02 1991-12-10 Ethyl Corporation Free flowing granular laundry detergent comprising tert-amine oxide dihydrate
WO1993012217A1 (fr) * 1991-12-19 1993-06-24 Ethyl Corporation Detergent de blanchissage en poudre et adjuvant de detergent

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US3281368A (en) * 1961-12-04 1966-10-25 Procter & Gamble Built tertiary amine oxide detergents
US3234139A (en) * 1961-12-21 1966-02-08 Procter & Gamble Diamine dioxide detergent compositions
BE664371A (fr) * 1964-05-25 1965-11-24
US3341459A (en) * 1964-05-25 1967-09-12 Procter & Gamble Detergent compositions
JPS5754159A (ja) * 1980-09-18 1982-03-31 Nippon Oil & Fats Co Ltd Aminokishidonofuntaikamataharyukahoho
JPH02178399A (ja) * 1988-12-29 1990-07-11 Lion Corp 粒状洗剤組成物
EP0421327A1 (fr) * 1989-10-02 1991-04-10 Albemarle Corporation Détergent universel pour le linge
US5071594A (en) * 1989-10-02 1991-12-10 Ethyl Corporation Free flowing granular laundry detergent comprising tert-amine oxide dihydrate
WO1993012217A1 (fr) * 1991-12-19 1993-06-24 Ethyl Corporation Detergent de blanchissage en poudre et adjuvant de detergent

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PATENT ABSTRACTS OF JAPAN vol. 6, no. 127 (C - 113) 13 July 1982 (1982-07-13) *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0863973A1 (fr) * 1995-09-26 1998-09-16 The Procter & Gamble Company Composition detergente comprenant un melange d'adjuvant bicarbonate-zeolite
EP0863973A4 (fr) * 1995-09-26 1999-02-10 Procter & Gamble Composition detergente comprenant un melange d'adjuvant bicarbonate-zeolite
US5958871A (en) * 1995-09-26 1999-09-28 The Procter & Gamble Company Detergent composition based on zeolite-bicarbonate builder mixture
WO2008071519A1 (fr) * 2006-12-13 2008-06-19 Henkel Ag & Co. Kgaa Préparation de granulats d'oxyde d'amine et leur mise en œuvre
WO2015191434A2 (fr) 2014-06-09 2015-12-17 Stepan Company Détergents pour nettoyage à l'eau froide
US10421930B2 (en) 2014-06-09 2019-09-24 Stephan Company Detergents for cold-water cleaning
WO2016111884A2 (fr) 2015-01-08 2016-07-14 Stepan Company Détergents textiles à l'eau froide
US10570352B2 (en) 2015-01-08 2020-02-25 Stepan Company Cold-water laundry detergents

Also Published As

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MA23390A1 (fr) 1995-07-01
BR9408264A (pt) 1996-12-10
AU1339395A (en) 1995-06-27
JPH09506389A (ja) 1997-06-24
CA2177678A1 (fr) 1995-06-15
CN1142848A (zh) 1997-02-12
EP0733095A1 (fr) 1996-09-25

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