EP0617733B1 - Detergent de blanchissage en poudre et adjuvant de detergent - Google Patents

Detergent de blanchissage en poudre et adjuvant de detergent Download PDF

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Publication number
EP0617733B1
EP0617733B1 EP92925246A EP92925246A EP0617733B1 EP 0617733 B1 EP0617733 B1 EP 0617733B1 EP 92925246 A EP92925246 A EP 92925246A EP 92925246 A EP92925246 A EP 92925246A EP 0617733 B1 EP0617733 B1 EP 0617733B1
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EP
European Patent Office
Prior art keywords
weight
mixture
sodium
zeolite
carbons
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP92925246A
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German (de)
English (en)
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EP0617733A1 (fr
Inventor
Terry Crutcher
Joe D. Sauer
Kim R. Smith
James E. Borland
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Albemarle Corp
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Albemarle Corp
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Priority claimed from US07/810,197 external-priority patent/US5238595A/en
Application filed by Albemarle Corp filed Critical Albemarle Corp
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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
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • 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
    • C11D1/02—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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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 phosphate-free granular laundry detergents and more particularly to such detergents having improved cleaning power.
  • Granular laundry detergents, or laundry powders typically comprise (A) one or more surfactants, such as alkyl sulfates, alkyl ether sulfates, alkylbenzene sulfonates, ethoxylated alkylphenols, ethoxylated alcohols, or amine oxides, and (B) one or more detergent builders, such as sodium tripolyphosphate, sodium nitrilotriacetate, or a sodium aluminum silicate.
  • surfactants such as alkyl sulfates, alkyl ether sulfates, alkylbenzene sulfonates, ethoxylated alkylphenols, ethoxylated alcohols, or amine oxides
  • detergent builders such as sodium tripolyphosphate, sodium nitrilotriacetate, or a sodium aluminum silicate.
  • the amine oxide is one in which R' and R" are independently selected from methyl, ethyl, and 2-hydroxyethyl, and it is blended with the zeolite so as to provide 2.3-7.0 mmols of amine oxide per gram of zeolite, it increases the divalent ion sequestration rate of the zeolite; and the use of the blend in the laundry detergent minimizes premature precipitation of the anionic surfactant from solution when the laundry detergent is used.
  • the surfactant which comprises 1-30% by weight of the laundry detergent is preferably employed in an amount such as to constitute 10-20% of the total detergent weight, and its components are preferably proportionated so that the surfactant consists of at least 80% by weight of the ethoxylated fatty alcohol and up to 10% by weight of each of the other components when the anionic surfactant is an alkylbenzene sulfonate and at least 90% by weight of the ethoxylate and up to 5% by weight of each of the other components when the anionic surfactant is a fatty acid soap.
  • Ethoxylated fatty alcohols which may be used in the practice of the invention are ordinarily compounds corresponding to the formula Z(OCH 2 CH 2 ) n OH in which Z is an alkyl group containing 4-30 carbons, preferably 10-18 carbons, and n is an integer of 1-50, preferably 2-15.
  • Particularly preferred ethoxylated fatty alcohols are apt to be (1) the ethoxylate of a mixture of C 6 and C 10 alcohols in which n is 3, (2) the ethoxylate of a mixture of C 12 and C 14 alcohols in which n is 3, and (3) the ethoxylate of a mixture of C 12 and C 14 alcohols in which n is 6.
  • ethoxylates corresponding to the formula such as those formed from one or more alcohols such as butanol, isobutanol, hexanol, octanol, decanol, dodecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol, eicosanol, docosanol, tetracosanol, and triacontanol, are also utilizable.
  • alcohols such as butanol, isobutanol, hexanol, octanol, decanol, dodecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol, eicosanol, docosanol, tetracosanol, and triacontanol
  • the alkylbenzene sulfonate component of the laundry detergent may be any alkali metal or ammonium salt of an alkylbenzene sulfonate in which the alkyl group contains 10-18 carbons, but it is preferably sodium dodecylbenzene sulfonate.
  • the fatty acid soap may be any of the fatty acid salts, usually sodium salts, known as soaps - usually a salt of a fatty acid containing 12-20 carbons, such as oleic, ricinoleic, and stearic acids, tallow fatty acid mixtures, and coco fatty acid.
  • the C 12 coco soaps are preferred however.
  • the amine oxide component may be one containing one or two long-chain alkyl groups, although - to permit increasing the divalent ion sequestration rate of the zeolite - it is preferred for the amine oxide to contain only one long-chain alkyl group, most preferably such a group containing 10-18 carbons and having a straight chain in at least most of the molecules, generally at least 70%, preferably at least 90% of the molecules. Especially preferred are the amine oxides in which both R' and R" are methyl.
  • the utilizable amine oxides include, e.g., N-octyldimethylamine oxide, N,N-didecylmethylamine oxide, N-decyl-N-dodecylethylamine oxide, N-dodecyldimethylamine oxide, N-tetradecyldimethylamine oxide, N-tetradecyl-N-ethylmethylamine oxide, N-tetradecyl-N-ethyl-2-hydroxyethylamine oxide, N,N-ditetradecyl-2-hydroxyethylamine oxide, N-hexadecyldimethylamine oxide, N-hexadecyldi-2-hydroxyethylamine oxide, N-octadecyldimethylamine oxide, N,N-dieicosylethylamine oxide, N-docosyl-N-2-hydroxyethylmethylamine oxide, N-tetracosyldimethylamine oxide, and mixture
  • the amine oxide used in the practice of the invention may be a conventional amine oxide (i.e., one prepared as a dilute aqueous solution), it is preferable for the amine oxide to be one that has been prepared in solid form, such as the amine oxide dihydrates and dihydrate-containing materials of U.S. Patent 5,071,594 (Borland et al.). Dilute aqueous solutions have to be dried in the production of a laundry powder. Moreover, when the amine oxide is blended with the zeolite so as to increase its divalent ion sequestration rate, it is important for the resulting mixture to contain 0-30% by weight of water so that it will be a powder rather than a paste.
  • the detergent builder which is employed together with the aforementioned surfactant mixture is a sodium aluminum silicate, and it is used in an amount such as to constitute 1-50%, preferably 20-40%, of the total weight of the laundry detergent.
  • Any suitable zeolite e.g., zeolite A, X, or Y, may be utilized as the sodium aluminum silicate; but zeolite A is ordinarily preferred.
  • the remaining essential components of the laundry detergent are (1) sodium silicate, which makes up 1-20%, preferably 5-15%, of the total weight of the detergent, (2) an anti-redeposition agent, such as sodium polyacrylate or sodium carboxymethylcellulose, which constitutes 0.1-5%, preferably 0.1-1%, of that total weight, and (3) one or more inorganic fillers, or processing aids, such as sodium sulfate, carbonate, or bicarbonate, which make up 10-80% of the weight of the detergent.
  • the detergent may also contain optional ingredients, e.g., one or more bleaching agents, such as sodium percarbonate or perborate, and one or more of the fabric softeners, such as quaternary ammonium salts, sometimes used in laundry detergents.
  • the components of the laundry detergent may be combined in any suitable manner, it is frequently preferred to preblend the zeolite and the amine oxide, especially when the amine oxide is contains only one long chain and is to be mixed with the zeolite in such proportions as to increase the divalent ion sequestration rate, i.e., so as to provide 2.3-7, preferably 3.1-5.4, more preferably 3.5-4.7, and most preferably about 3.9 mmols of the amine oxide per gram of the zeolite.
  • amine oxide/zeolite builder systems may be incorporated into the laundry detergents of the invention or other anionic surfactant-containing cleaning compositions in the same manner as conventional detergent builders to produce formulations from which the anionic surfactants are less apt to precipitate prematurely.
  • cleaning compositions include:
  • the laundry detergents of the invention are advantageous in that they match premium phosphate-containing detergents in performance while being free of (1) the phosphates that are already of environmental concern and (2) any unusual ingredients that would require new environmental or toxicological testing. Moreover, they are effective over a wide range of soils and conditions; impart softening to laundered fabrics even without the inclusion of additional fabric softeners, such as the quaternary ammonium salts mentioned above; and can actually be less costly to make than premium phosphate-containing and phosphate-free laundry detergents that are already commercially available.
  • Blends A and B phosphate-free laundry detergents of the invention
  • Blend C a phosphate-free control laundry detergent
  • Blend D a phosphate-containing control laundry detergent
  • Blends A B C* D* N-tetradecyldimethylamine oxide 1 1 -- -- Sodium dodecylbenzene sulfonate 1 -- 13 10 C 12 coco soap -- 1 -- -- 6-EO ethoxylate of a mixture of C 12 and C 14 alcohols 18 18 -- -- Soda ash 41.6 41.6 22 24 Sodium sulfate -- -- 25 25 25 Sodium silicate 8 8 2 5 Sodium carboxymethylcellulose -- -- 1 1 1 Sodium polyacrylate 0.4 0.4 -- -- Sodium tripolyphosphate -- -- -- 30 Zeolite A 30 30 30 -- Tridecyl sulfate -- -- 7 5 * comparative blends
  • Example 2 Test the cleaning performance of laundry detergents A, C, and D of Example 2 by (1) placing six standard dust-sebum soiled cotton/polyester swatches in a vessel containing one liter of 200 ppm hard water (Ca ++ /Mg ++ ratio of 3/2), (2) adding 1.5g of the detergent to be tested, (3) agitating the contents of the vessel for ten minutes at 100 rpm, (3) rinsing the swatches with the hard water for five minutes at the same temperature used for the washing, (4) drying the rinsed swatches on a flat bed press for ten minutes, (5) measuring the reflectance of each of the swatches in a tergotometer, (6) averaging the results, and (7) calculating the difference between the average reflectance and the reflectance of a zero control as the detergency (L).
  • L detergency
  • Blend B The test results obtained with Blend B are similar to those obtained with Blend A, which, as demonstrated above, compares very favorably with premium commercial laundry detergents in cleaning performance when used in water having a hardness of 200 ppm Ca and in an amount comparable to one cup of detergent in a normal washing machine.
  • the following examples show that a favorable comparison in its performance is also found when the water used for the test has different degrees of hardness or when different amounts of detergent are utilized.
  • Example 3 test at 38°C on dust-sebum soiled swatches except for (1) using polyester/cotton swatches provided by a different manufacturer and having a higher loading of soil and (2) varying the amount of detergent employed as shown in Table IV, which also shows the increases in reflectance determined by the tests.
  • Table IV Increase in Reflectance g Detergent per L Water Blend A Blend C Blend D 0.5 11.0 5.9 6.5 1.0 15.0 13.0 11.5 1.5 19.9 15.0 20.0 2.0 20.5 16.0 22.0 2.5 22.0 21.0 22.0 3.0 22.5 21.5 22.6 3.5 23.0 21.5 23.0

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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)
  • Inorganic Chemistry (AREA)
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Abstract

Un détergent de blanchissage en poudre sans phosphate ayant une capacité de nettoyage comparable à celle d'un détergent contenant un super phosphate comprend: (A) 1 à 30 % en poids d'un tensioactif, (B) 1 à 50 % en poids d'un adjuvant de détergent à base de silicate d'aluminium de sodium, (C) 1 à 20 % en poids de silicate de sodium, (D) 0,1 à 5 % en poids d'un agent anti-redéposition, et (E) 10 à 80 % en poids d'une charge inorganique, le tensioactif se composant (1) d'un mélange de 20 à 98 % en poids d'un alcool gras éthoxylé, de 1 à 75 % en poids d'un métal alcalin ou de sel d'ammonium d'un sulfonate de benzène d'alkyle dans lequel le groupe alkyle contient 10 à 18 atomes de carbone, et 1 à 20 % en poids d'un oxyde d'amine correspondant à la formule RR'R''NO où R est un groupe alkyle primaire contenant 8 à 24 atomes de carbone; R' est méthyle, éthyle ou 2-hydroxy-éthyle; et R'' est sélectionné indépendamment dans les groupes méthyle, éthyle, 2-hydroxyéthyle, et alkyle primaire contenant 8 à 24 atomes de carbone, ou (2) d'u un mélange de 85 à 98 % en poids d'éthoxylate, 1 à 12 % en poids d'un savon d'acide gras, et 1 à 6 % en poids d'oxyde d'amine.

Claims (12)

  1. Détergent pour lessive granulaire exempt de phosphate comprenant (A) 1 à 30 % en poids d'un mélange d'agents tensioactifs alcool gras éthoxylé/agent tensioactif anionique/oxyde d'amine dans lequel l'oxyde d'amine répond à la formule RR'R"NO dans laquelle R est un groupe alkyle primaire en C8-C24 ; R' est un groupe méthyle, éthyle ou 2-hydroxyéthyle ; et R" est choisi indépendamment parmi les groupes méthyle, éthyle, 2-hydroxyéthyle et alkyle primaire en C8-C24, (B) 1 à 50 % en poids d'un adjuvant de détergence de silicate de sodium et d'aluminium, (C) 1 à 20 % en poids de silicate de sodium, (D) 0,1 à 5 % en poids d'un agent antiredéposition, et (E) 10 à 80 % en poids d'une charge minérale, le mélange d'agents tensioactifs étant constitué (1) d'un mélange de 20 à 98 % en poids de l'éthoxylate, 1 à 75 % en poids d'un sel de métal alcalin ou d'ammonium d'un alkylbenzènesulfonate dans lequel le groupe alkyle est en C10 à C18, et 1 à 20 % en poids de l'oxyde d'amine ou (2) un mélange de 85 à 98 % en poids de l'éthoxylate, 1 à 12 % en poids d'un savon d'acide gras et 1 à 6 % en poids de l'oxyde d'amine.
  2. Détergent pour lessive selon la revendication 1, comprenant 10 à 20 % en poids de l'agent tensioactif, 20 à 40 % en poids de l'adjuvant, 5 à 15 % en poids du silicate de sodium et 0,1 à 1 % en poids de l'agent antiredéposition.
  3. Détergent pour lessive selon la revendication 2, dans lequel (A) l'agent tensioactif est constitué d'un mélange contenant au moins 80 % en poids d'un alcool gras éthoxylé répondant à la formule Z(OCH2CH2)nOH dans laquelle Z et un groupe alkyle en C10 à C18 et n est un entier de 2 à 15, jusqu'à 10 % en poids de dodécylbenzènesulfonate de sodium et jusqu'à 10 % en poids d'un oxyde d'amine répondant à la formule RR'R"NO dans laquelle R est un groupe alkyle primaire en C8 à C24, et R' et R" sont choisis indépendamment parmi les groupes méthyle, éthyle et 2-hydroxyéthyle, (B) l'adjuvant de détergence est une zéolite A, (C) l'agent antiredéposition est choisi parmi le polyacrylate de sodium, la carboxyméthylcellulose sodique et leurs mélanges, et (D) la charge minérale est un ou plusieurs composés choisis parmi le sulfate de sodium, le carbonate de sodium et le bicarbonate de sodium.
  4. Détergent pour lessive selon la revendication 3, dans lequel (A) l'agent tensioactif est constitué d'un mélange de 90 % en poids de l'éthoxylate d'un mélange d'alcools en C12 et C14 dans lesquels n est 6, 5 % en poids de dodécylbenzènesulfonate de sodium et 5 % en poids d'oxyde de N-tétradécyldiméthylamine, (B) l'agent antiredéposition est le polyacrylate de sodium, et (C) la charge minérale est le carbonate de sodium.
  5. Détergent pour lessive selon la revendication 4, constitué de 20 % en poids du mélange d'agents tensioactifs, 30 % en poids de zéolite A, 8 % en poids de silicate de sodium, 0,4 % en poids de polyacrylate de sodium et 41,6 % en poids de carbonate de sodium.
  6. Détergent pour lessive selon la revendication 2, dans lequel (A) l'agent tensioactif est constitué d'un mélange contenant au moins 90 % en poids d'un alcool gras éthoxylé répondant à la formule Z(OCH2CH2)nOH dans laquelle Z et un groupe alkyle en C10 à C18 et n est un entier de 2 à 15, jusqu'à 5 % en poids d'un savon de coprah en C12, et jusqu'à 5 % en poids d'un oxyde d'amine répondant à la formule RR'R"NO dans laquelle R est un groupe alkyle primaire en C8 à C24, et R' et R" sont choisis indépendamment parmi les groupes méthyle, éthyle et 2-hydroxyéthyle, (B) l'adjuvant de détergence est la zéolite A, (C) l'agent antiredéposition est choisi parmi le polyacrylate de sodium, la carboxyméthylcellulose sodique et leurs mélanges, et (D) la charge minérale est un ou plusieurs composés choisis parmi le sulfate de sodium, le carbonate de sodium et le bicarbonate de sodium.
  7. Détergent pour lessive selon la revendication 6, dans lequel (A) l'agent tensioactif est constitué d'un mélange de 90 % en poids de l'éthoxylate d'un mélange d'alcools en C12 à C14 dans lesquels n est 6, 5 % en poids du savon et 5 % en poids de l'oxyde de N-tétradécyldiméthylamine, (B) l'agent antiredéposition est le polyacrylate de sodium, et (C) la charge minérale est le carbonate de sodium.
  8. Détergent pour lessive selon la revendication 7, constitué de 20 % en poids du mélange d'agents tensioactifs, 30 % en poids de zéolite A, 8 % en poids de silicate de sodium, 0,4 % en poids de polyacrylate de sodium et 41,6 % en poids de carbonate de sodium.
  9. Mélange convenant pour l'utilisation comme adjuvant de détergence et constitué (A) d'une zéolite, (B) de 2,3 à 7,0 mmoles par gramme de zéolite d'un oxyde d'amine répondant à la formule RR'R"NO dans laquelle R est un groupe alkyle primaire en C6 à C24, et R' et R" sont choisis indépendamment dans le groupe constitué des groupes méthyle, éthyle et 2-hydroxyéthyle, et (C) de 0 à 30 % d'eau par rapport au poids du mélange.
  10. Mélange selon la revendication 9, dans lequel R est un groupe alkyle primaire en C10 à C18, R' et R" sont des groupes méthyle et la quantité d'oxyde d'amine est de 3,1 à 5,4 mmoles par gramme de zéolite.
  11. Mélange selon la revendication 10, dans lequel la quantité d'oxyde d'amine est de 3,5 à 4,7 mmoles par gramme de zéolite.
  12. Mélange selon la revendication 11, dans lequel l'oxyde d'amine est l'oxyde de N-tétradécyldiméthylamine et la zéolite est la zéolite A.
EP92925246A 1991-12-19 1992-11-17 Detergent de blanchissage en poudre et adjuvant de detergent Expired - Lifetime EP0617733B1 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
US810197 1991-12-19
US07/810,197 US5238595A (en) 1991-12-19 1991-12-19 Detergent builder
US85160092A 1992-03-16 1992-03-16
US851600 1992-03-16
US87828192A 1992-05-04 1992-05-04
US878281 1992-05-04
PCT/US1992/009854 WO1993012217A1 (fr) 1991-12-19 1992-11-17 Detergent de blanchissage en poudre et adjuvant de detergent

Publications (2)

Publication Number Publication Date
EP0617733A1 EP0617733A1 (fr) 1994-10-05
EP0617733B1 true EP0617733B1 (fr) 1997-04-23

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EP92925246A Expired - Lifetime EP0617733B1 (fr) 1991-12-19 1992-11-17 Detergent de blanchissage en poudre et adjuvant de detergent

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EP (1) EP0617733B1 (fr)
JP (1) JPH07509501A (fr)
CA (1) CA2126238A1 (fr)
DE (1) DE69219358T2 (fr)
WO (1) WO1993012217A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7226899B2 (en) 2003-12-23 2007-06-05 Kimberly - Clark Worldwide, Inc. Fibrous matrix of synthetic detergents

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Publication number Priority date Publication date Assignee Title
WO1995014072A1 (fr) * 1993-11-19 1995-05-26 The Procter & Gamble Company Composition detergente contenant des tensioactifs oxyde d'amine et sulfonate
MA23390A1 (fr) * 1993-12-07 1995-07-01 Procter & Gamble Composition detergente contenant un tensioactif d'oxyde-amine sous forme d'agglomerats
JPH09512850A (ja) * 1994-05-10 1997-12-22 ザ、プロクター、エンド、ギャンブル、カンパニー 陰イオン界面活性剤とアミンオキシド界面活性剤と脂肪酸とを含有するヘビーデューティー液体洗濯洗剤組成物
JP3513313B2 (ja) * 1996-03-13 2004-03-31 花王株式会社 衣料用高密度粒状洗剤組成物

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US4276205A (en) * 1980-02-04 1981-06-30 The Procter & Gamble Company Detergent compositions containing amine oxide and nonionic surfactants and polyethylene glycol
JPS5919597B2 (ja) * 1980-04-23 1984-05-07 ライオン株式会社 ゼオライト含有無燐粒状洗剤組成物
US5071594A (en) * 1989-10-02 1991-12-10 Ethyl Corporation Free flowing granular laundry detergent comprising tert-amine oxide dihydrate
CA2025973A1 (fr) * 1989-10-02 1991-04-03 Albemarle Corporation Detergent a lessive surpuissant

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7226899B2 (en) 2003-12-23 2007-06-05 Kimberly - Clark Worldwide, Inc. Fibrous matrix of synthetic detergents

Also Published As

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CA2126238A1 (fr) 1993-06-24
WO1993012217A1 (fr) 1993-06-24
DE69219358D1 (de) 1997-05-28
DE69219358T2 (de) 1997-08-07
JPH07509501A (ja) 1995-10-19
EP0617733A1 (fr) 1994-10-05

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