EP0042188B2 - Reinigungsmittelzusammensetzung mit einem niedrigen Gehalt an Aminoxiden - Google Patents

Reinigungsmittelzusammensetzung mit einem niedrigen Gehalt an Aminoxiden Download PDF

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Publication number
EP0042188B2
EP0042188B2 EP19810200601 EP81200601A EP0042188B2 EP 0042188 B2 EP0042188 B2 EP 0042188B2 EP 19810200601 EP19810200601 EP 19810200601 EP 81200601 A EP81200601 A EP 81200601A EP 0042188 B2 EP0042188 B2 EP 0042188B2
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Prior art keywords
alkyl
detergent
water
weight
builder
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French (fr)
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EP0042188B1 (de
EP0042188A1 (de
Inventor
Robertus Johannes Cornelis Koster
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Procter and Gamble European Technical Center
Procter and Gamble Co
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Procter and Gamble European Technical Center
Procter and Gamble Co
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Priority to AT81200601T priority Critical patent/ATE9714T1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides

Definitions

  • This invention relates to detergent compositions containing low levels of amine oxides.
  • These amine oxides are substituted by at least one long chain alkyl or alkenyl group.
  • Preferred amine oxides have at least two alkyl, especially methyl, or two alkylene oxide, especially ethylene oxide, groups attached to the nitrogen atom(s).
  • These compositions produce an alkaline laundry liquor pH.
  • These compositions exhibit a breed range of remarkable textile treatment benefits, particularly enhanced soil release and cleaning properties.
  • U.S. Patent 3 985 923, Basadur, issued October 12, 1976, relates to the application of renewable soil release finish during the rinsing step from a dilute aqueous acidic solution.
  • the release agent is a copolymer based on a dibasic carboxylic acid and a glycolic compound.
  • U.S. Patent 3 962 152 Nicol, Hays, issued June 8, 1976 pertains to the laundry treatment deposition of renewable soil release finish to synthetic treatment fabrics treated therewith.
  • the soil release finish consists of ethylene terephthalate and polyethylene oxide terephthalate.
  • the performance benefits derived from the utilization of the like additives are premised on the deposition of a releasable coating onto the fiber from the laundry/rinsing step.
  • the coating will be rinsed off during the next laundry cycle, inclusive of the total soil accumulated thereon, to thus provide a "non-alterated" degree of cleaning.
  • the total prior art refers to the utilization of mostly monoamine oxides in a conventional detergent functionality. It is widely recognized that such aminoxides are good surfactants and indeed have been utilized in commercial detergent executions. However, the art is not suggestive of incidental textile benefits derivable from utilizing unexpectedly low levels of the very components in a non-surfactant functionality.
  • the present invention comprises particulate built detergent compositions having enhanced soil release and cleaning properties containing:
  • compositions herein have an alkaline pH in the range from 8.5 - 11 (1 % aqueous solution 20°C).
  • the detergent compositions of the present invention are defined in five essential parameters:
  • Optional ingredients can be added to provide various performance and aesthetic benefits.
  • the detergent compositions herein comprise as a first essential component, anionic surface-active agent.
  • the anionic surface-active agent represents from 5 % to 25 %, preferably from 5 % to 20 %.
  • Suitable anionic detergents include ordinary alkali metal soaps of higher fatty acids containing from about eight to 24 carbon atoms and preferably from 10 to 20 carbon atoms.
  • sodium alkyl glyceryl ether sulfonates especially those ethers of higher alcohols derived from tallow and coconut oil
  • sodium coconut oil fatty acid monoglyceride sulfonates and sulfates also represent a class of very useful anionic surface-active agents.
  • Useful in this invention are also salts of 2-acyloxyalkane-1-sulfonic acids.
  • 0-alkoxy alkane sulphonates can also be used.
  • Specific examples of ⁇ -alkyloxy alkane sulfonates having low hardness (calcium ion) sensitivity useful herein to provide superior cleaning levels under household washing conditions include: potassium-S-methoxydecanesulfonate, sodium 2-methoxytridecanesulfonate, potassium 2-ethoxyte- tradecylsulfonate, and sodium 2-isopropoxyhexadecylsulfonate.
  • Paraffin sulfonates containing a straight or branched chain, saturated aliphatic hydrocarbon radical having from 8 to 24, preferably 12 to 18, carbon atoms can also be used.
  • alkyl ether sulfates alkyl ether sulfates. These materials have the formula wherein
  • alkyl ether sulfates are those comprising a mixture of individual compounds, said mixture having an average alkyl chain length of from 12 to 16 carbon atoms and an average degree of ethoxylation of from 1 to 4 moles of ethylene oxide.
  • Such a mixture also comprises from 0 to 20 % by weight C 12 - 13 compounds; from 60 to 100 % by weight of C 14 - 15 - 16 compounds; form 0 to 20 % by weight of C 17 - 18 - 19 compounds; from 3 to 30 % by weight of compounds having a degree of ethoxylation of 0; from 45 to 90 % by weight of compounds having a degree of ethoxylation of from 1 to 4; from 10 to 25 % by weight of compounds having a degree of ethoxylation of from 4 to 8; and from 0.1 to 15 % by weight of compounds having a degree of ethoxylation greater than 8.
  • a second essential component in the compositions herein is represented by an amine oxide having the formula wherein
  • This amine oxide component is used in a level from 0.25 % to 0.75 %. Utilizing less than the minimum levels will not provide anymore the inventive benefits, whereas levels above the specified definition will not yield anymore performance advantages but rather unexpectedly causes noticeable cleaning performance negatives, particularly whiteness deficiencies.
  • Suitable species of the amine oxide component for use herein correspond to the general formula above wherein the individual substituents can be varied as follows:
  • One particularly preferred class of amine oxide species is represented by mono-amine oxides having the following substituents.
  • a specific example of this preferred class of mono-amine oxides is: N-C 12 -C 14 coconut alkyl-N,N-dimethyl amine oxide.
  • Another particularly preferred class of amine oxide species is represented by bisamine oxides having the following substituents.
  • a specific example of this preferred class of bis-amine oxides is: N-hydrogenated C 16 -C l8 tallow alkyl-N,N',N'-tri-(. droxyethyl)-propylene-1,3-diamine oxide.
  • compositions herein shall yield upon dissolution in water an alkaline laundry liquor.
  • a 1 % aqueous solution of granular detergent compositions shall have an alkaline pH in the range from 8.5 to 11, measured at 20°C.
  • the pH can be adjusted by known means inclusive of alkaline buffer substances such as alkali hydroxides, ammonium hydroxide, amines and substituted amines, such as mono-, di- and triethanolamines; alkaline builder substances such as alkalimetal carbonates, alkalimetal phosphates and polyphosphates, citric acid and alkalimetal silicates.
  • alkaline buffer substances such as alkali hydroxides, ammonium hydroxide, amines and substituted amines, such as mono-, di- and triethanolamines
  • alkaline builder substances such as alkalimetal carbonates, alkalimetal phosphates and polyphosphates, citric acid and alkalimetal silicates.
  • suitable pH adjusting agents shall of course take into
  • the detergent compositions of this invention further contain a detergent builder in a level from 10 % to 45 %.
  • the builder component can be represented by all known water-soluble and water-insoluble detergent builder ingredients.
  • Non-limiting examples of suitable water-soluble, inorganic alkaline builder salts include the alkali metal carbonates, borates, phosphates, polyphosphates, tripolyphosphates, bicarbonates, silicates, and sulfates.
  • Specific examples of such salts include the sodium and potassium tetraborates, bicarbonates, carbonates, tripolyphosphates, pyrophosphates, and hexametaphosphates.
  • Suitable organic alkaline detergency builder salts are:
  • alkali metal salts of the foregoing inorganic and organic polyvalent anionic builder salts are preferred for use herein from an economic standpoint, the ammonium, alkanolammonium (e.g. triethanolammonium, diethanolammonium and monoethanolammonium) and other water-soluble salts of any of the foregoing builder anions can be used.
  • alkanolammonium e.g. triethanolammonium, diethanolammonium and monoethanolammonium
  • other water-soluble salts of any of the foregoing builder anions can be used.
  • Mixtures of organic and/or inorganic builders can be used herein.
  • One such mixture of builders is disclosed in Canadian Patent No. 755 038, e.g., a ternary mixture of sodium tripolyphosphate, trisodium nitrilotriacetate, and trisodium ethane-1-hydroxy-1,1-diphosphonate.
  • detergency builder material useful in the present invention comprises a water-soluble material capable of forming a water-insoluble reaction product with water hardness cations, preferably in combination with a crystallization seed which is capable of providing growth sites for said reaction product.
  • materials capable of forming the water-insoluble reaction product include the water-soluble salts of carbonates, bicarbonates, sesquicarbonates, silicates, aluminates and oxalates.
  • the alkali metal, especially sodium, salts of the foregoing materials are preferred for convenience and economy.
  • Preferred crystallization seed materials are calcium carbonate, calcium oxide and calcium hydroxide. Such "seeded builder" compositions are fully disclosed in British Patent Specification No. 1 424 406.
  • Non-seeded precipitating builder systems employing pyrophosphates or mixtures thereof with orthophosphates are also useful herein.
  • Precipitating pyrophosphate and orthopyrophosphate builder systems are disclosed in DE-A-2 542 704 and 2 605 052 published April 15 and August 16, 1976, respectively.
  • Suitable examples of water-insoluble detergent builders are selected from the group consisting of zeolites A, X, or P(B), or mixtures thereof, having a particle size diameter of from 0.01 micrometer to 25 micrometers and containing at least 10 % water of hydration, and amorphous hydrate aluminosilicate material of the empirical formula: wherein
  • the preferred synthetic crystalline aluminosilicate materials for use herein commonly known as Zeolites A, X, and P(B) should contain at least 10 % water of hydration and should have a particle size diameter of from 0.5 micrometer to 30 micrometers, more preferably from 0.5 micrometer to 10 micrometers.
  • Aluminosilicate materials are more fully described in U.S. Patent 4 096 081, Phenicie et al., issued June 20, 1978, and German Patent No. 2 704 003, Ohren, published on August 18, 1977.
  • the amorphous alumininosilicate materials suitable for use herein are fully described in U.S. Patent No. 4 180 485, Llenado, published December 25, 1979.
  • the water-insoluble detergent builders are frequently and preferably utilized in the granular compositions herein in conjunction with a water-soluble detergent cobuilder ingredient in a weight ratio of aluminosilicate: water-soluble detergent cobuilder of from 4 : 1 to 1 : 4.
  • Suitable examples of preferred water-soluble co-builder ingredients are represented by the water-soluble salts of nitrilotriacetic acid, polyphosphates e.g. tripolyphosphates, and citrates.
  • the cations of these cobuilders can e.g. be represented by alkalimetal ions, sodium, potassium, lithium, and by organic ions such as amines, substituted amines (alkanolamines) and ammonium ions.
  • the detergent compositions contain a peroxybleach compound in an amount from 3 % to 50 %, preferably from 5 % to 35 %.
  • Suitable peroxybleach compounds are all those which are known to be adapted for use in or have already been used in detergent technology. Examples of such peroxybleaches include the water-soluble alkali salts of perborate mono-hydrate, perborate tetrahydrate, persulfates, persilicates, perphosphates, and percarbonates.
  • Organic oxygen-bleach activators can also advantageously be used in oxygen-bleach containing detergent executions of this invention.
  • activators examples include phthalic anhydride, tetra-acetyl ethylene diamine, tetra-acetyl methylene diamine and tetra-acetyl glycouril. Such activators are frequently used in levels from 0.2 % to 15 %, preferably from 1 % to 4 %. The weight ratios of the peroxybleach compound to the activator is frequently in the range from about 10 : 1 to 2 : 1.
  • compositions of this invention can comprise a series of supplementary components to perfect and complement the benefits derived from the compositions herein.
  • additional components include brighteners, dyes, perfumes, bactericides, processing aids, anti-oxidants, corrosion inhibitors, enzymes suds regulants and so on.
  • the copolymeric vinyl ingredient is normally used in an amount from 0.1 % to 6 %, preferably from 0.25 % to 4 %.
  • these copolymeric ingredients include a water-soluble acid, an alkali-metal salt of that acid, an ester, or a C 1 - 2 alkyl or alkylolamide of a maleic anhydridevinyl C 1 - 4 alkyl ether copolymer.
  • the specific viscosity of, for example, the maleic anhydride-vinyl Ci- 4 alkyl ether, preferably methylether, copolymer for use herein normally varies between 0.1 and 6, most preferably between 0.2 and 5.0.
  • the (molecular) monomer ratio (maleic : vinylalkylether) is preferably in the range from 2 : 1 to 1 : 2.
  • the specific viscosity is defined by measuring the viscosity of the solution of 1 g of the anhydride copolymer in 100 ml methylethylketone at 25°C in a series of 100 Cannon-Fenske® viscosity meter.
  • the copolymeric component can serve as slurry processing aid to thus provide a detergent product having improved physical properties including flowability.
  • Another optional ingredient is a mixture of alkoxylated mono- and diesters of phosphoric acid.
  • phosphoric esters are preferably represented by alkoxylated fatty alcohols having from 10 to 22 carbon atoms with 2 to 15 moles ethylene oxide or propylene oxide.
  • the weight ratio of monophosphoric esters to diphosphoric esters is usually in the range from 6 : 1 to 3 : 1, preferably 4 : 1.
  • anti-oxidant material is 4,4'-thiobis(6-tert-butyl-m-cresol).
  • the detergent compositions can additionally contain an enzymatic ingredient.
  • Proteases, amylases and lipases can be added in an amount from 0.001 % to 5 % to augment and aid in the cleaning activity of the detergent compositions herein.
  • Preferred proteolytic enzymes are disclosed in Belgian Patent 775 854, to EYMERY et al., granted May 26, 1972.
  • the detergent compositions of this invention frequently comprise a suds regulant in a level of 0.01 % - 10 %.
  • Suitable suds regulants are well-known in detergent technology and most of these can easily be used in combination with the claimed technology.
  • detergent suds regulants which can be used include saturated fatty acids especially those having 16 to 24 carbon atoms in the alkylchain, non-ionic suds regulants and mixtures thereof.
  • Another class of well-known suds regulants are silicones, preferably silanated silicones in admixture with microcrystalline waxes.
  • Preferred suds regulants containing a separately processed detergent additive on basis of a water-insoluble liquid hydrocarbon, an adjunct material preferable a solid hydrocarbon, and a hydrophobic silica are described in U.S. Patent 4 192 761, Peltre and Lafleur, issued March 11, 1980. These liquid hydrocarbon-containing regulants are preferably used in granular executions.
  • a detergent composition was prepared having the following formulation:
  • a series of spray-drying sensitive ingredients were added to the above base-powder by dry-mixing, namely: 0.35 % of N-hydrogenated tallow-N,N',N'-tri-(2-hydroxyethyl)-propylene-1,3-diamine-N-N'-dioxide was sprayed onto the mixture of the base-powder and the spray-drying sensitive ingredients.
  • the detergent compositions were used for comparative laundry tests in a Miele®W421 washing machine.
  • compositions of example I wherein the tallowdiaminediox- ide is substituted by an equivalent level of: N-C 12-14 -alkyl-N,N',N'-tri-(2-hydroxyethyl)-propylene-1,3-diamine-N,N'-di oxide; N-palmityl-N,N',N'-hepta-(2-hydroxyethyl)-ethylene-1,2-diamine-N,N'-dioxide; N-C 16-18- tallowalkyl-N,N-dimethyl-N-amine oxide; N-C 12-14 -coconut alkyl-N,N-di-(2-hydroxyethyl)-N-amine oxide; or N-C 16-18 -tallowalkyl-N,N-di-(2-hydroxyethyl)-N-amine oxide.
  • a detergent composition was prepared having the following composition:
  • the amine oxide was incorporated into the crutcher.
  • the spray-drying sensitive were added to the base-powder by dry-mixing.
  • Detergent compositions were prepared by using the di-aminedioxide of Example I in accordance with the technique set forth in that example:

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (4)

1. Teilchenförmige Reinigungsmittelzusammensetzung mit verbesserten Schmutzfreisetzungs- und Reinigungseigenschaften, enthaltend:
(a) 5 - 25 Gew.-% eines oberflächenaktiven Mittels;
(b) 0,25 - 0,75 Gew.-% eines Aminoxids mit der Formel
Figure imgb0013
worin
R eine Alkyl- oder Alkenylgruppe mit 10 bis 22 Kohlenstoffatomen ist, die Reste R1, die identisch oder voneinander verschieden sind, aus C1-4-Alkyl, Ethylenoxid und Propylenoxid ausgewählt sind,
n eine ganze Zahl von 1 bis 6 ist,
m eine ganze Zahl von 0 bis 6 ist,
p 0 oder 1 ist,
x, y und z für Alkylsubstituenten jeweils 1 sind und für Ethylenoxid-oder Propylenoxidsubstituenten solche ganze Zahlen im Bereich von 1 bis 10 sind, daß die Summe von (x+y+z) nicht größer als 25 ist,
(c) 3 - 50 Gew.-% einer Peroxybleichverbindung; und
(d) 10 - 45 Gew.-% eines Detergensgerüststoffes; wobei eine 1 %-ige wäßrige Lösung der Zusammensetzung gemessen bei 20° C, einen pH im Bereich von 8,5 bis 11 hat und wobei das oberflächenaktive Mittel ein anionisches oberflächenaktives Mittel ist.
2. Reinigungsmittelzusammensetzung gemäß Anspruch 1, welche zusätzlich 0,01 Gew.-% bis 10 Gew.-% eines Detergensschaumreglers enthält.
3. Reinigungsmittelzusammensetzung gemäß Anspruch 1, worin der Detergensgerüststoff ein Gemisch aus
(i) einem wasserlöslichen Detergensgerüststoff, ausgewählt aus der aus den wasserlöslichen Salzen von Nitrilotriessigsäure, Polyphosphaten und Citraten bestehenden Gruppe; und
(ii) einem synthetischen, kristallinen, wasserunlöslichen Aluminosilicatgerüststoffmaterial, das aus der aus Zeolith A, Zeolith X und Zeolith P(B) bestehenden Gruppe ausgewählt ist wobei das Aluminosilicatmaterial wenigstens 10 Gew.-% des Silicats an Hydratationswasser enthält und einen Teilchendurchmesser im Bereich von 0,5 bis 30 Mikrometer hat, ist;
wobei das Gewichtsverhältnis des wasserlöslichen Detergensgerüststoffes : wasserunlöslichem Aluminosilicatgerüststoff im Bereich von 4 : 1 bis 1 : 4 liegt.
4. Zusammensetzung gemäß Anspruch 1, worin das Aminoxid aus der Gruppe ausgewählt ist, die aus N-C12-14-Kokos- nußalkyl-N,N-dimethyl-N-aminoxid; N-Talg -C16-18-alkyl-N,N',N-tri-(2-hydroxyethyl)-propylen-1,3-diamin -N,N'-dioxid; N-C12-14-Alkyl-N,N',N'-tri-(2-hydroxyethyl) -propylen-1,3-diamin-N,N'-dioxid; N-C16-1a-Talgalkyl-N,N -dimethyl-N-aminoxid; N-C12-14-Kokosnu ßalkyl-N,N-di-(2 -hydroxyethyl)-N-aminoxid; und N-C16-18-Talgalkyl-N,N-di-(2-hydroxyethyl)-N-aminoxid besteht.
EP19810200601 1980-06-17 1981-06-03 Reinigungsmittelzusammensetzung mit einem niedrigen Gehalt an Aminoxiden Expired EP0042188B2 (de)

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Application Number Priority Date Filing Date Title
AT81200601T ATE9714T1 (de) 1980-06-17 1981-06-03 Reinigungsmittelzusammensetzung mit einem niedrigen gehalt an aminoxiden.

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GB8019680 1980-06-17
GB8019680 1980-06-17
GB8038306 1980-11-28
GB8038306 1980-11-28

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EP0042188A1 EP0042188A1 (de) 1981-12-23
EP0042188B1 EP0042188B1 (de) 1984-10-03
EP0042188B2 true EP0042188B2 (de) 1990-02-28

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Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0095205B1 (de) * 1982-05-24 1986-10-15 THE PROCTER & GAMBLE COMPANY Fettsäure enthaltende Detergenszusammensetzungen
US4548744A (en) * 1983-07-22 1985-10-22 Connor Daniel S Ethoxylated amine oxides having clay soil removal/anti-redeposition properties useful in detergent compositions
FR2556364B1 (fr) * 1983-12-10 1989-10-27 Sandoz Sa Compositions detergentes liquides exemptes de phosphate
EP0735131A3 (de) * 1995-03-27 1996-12-11 Procter & Gamble Verwendung von Aminoxid-Tensiden zur Verbesserung der Fleckentfernung
US5972875A (en) * 1997-04-23 1999-10-26 Crutcher; Terry Low-foaming amine oxide surfactant concentrate and method of manufacture
WO2001071062A1 (en) * 2000-03-21 2001-09-27 Holland Novochem Bv Corrosive preventive composition and method of using the same
US11130709B2 (en) 2015-05-19 2021-09-28 Gcp Applied Technologies Inc. Polyalkoxylated polyamine oxide defoaming compositions

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL286242A (de) * 1961-12-04
BE626346A (de) * 1961-12-21
ZA774818B (en) * 1976-08-17 1979-03-28 Colgate Palmolive Co Disintegrable detergent builder agglomerates
IT1160682B (it) * 1977-10-14 1987-03-11 Po Corp. Composizioni detergenti con coadiuvante di silano-zeolite

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DE3166434D1 (en) 1984-11-08
EP0042188A1 (de) 1981-12-23

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