EP0050897B1 - Agglomérates d'aluminosilicates et compositions détergentes les contenant - Google Patents

Agglomérates d'aluminosilicates et compositions détergentes les contenant Download PDF

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Publication number
EP0050897B1
EP0050897B1 EP19810201157 EP81201157A EP0050897B1 EP 0050897 B1 EP0050897 B1 EP 0050897B1 EP 19810201157 EP19810201157 EP 19810201157 EP 81201157 A EP81201157 A EP 81201157A EP 0050897 B1 EP0050897 B1 EP 0050897B1
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Prior art keywords
agglomerate
weight
carbon atoms
aluminosilicate
zeolite
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EP19810201157
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German (de)
English (en)
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EP0050897A1 (fr
Inventor
Rodney Mahlon Wise
James Michael Vander Meer
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Procter and Gamble Co
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Procter and Gamble Co
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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

Definitions

  • the present invention relates to compositions of matter which are useful for water softening or as detergent builders.
  • Aluminosilicates which have high calcium and magnesium exchange rates and capacity have been added to water softening and detergent products to remove water hardness. Effective removal of calcium and magnesium ions from water when considered in the context of detergent products is important in that those ions can precipitate anionic surfactants rendering the former less effective in fabric cleaning. Moreover, if the calcium and magnesium ions are not removed from water used for washing, these ions will interact with soils on the fabrics thus interfering with soil removal.
  • aluminosilcates are to be admixed into the composition as a dry material, a considerable quantity of dust can be generated by improper handling of the finely divided aluminosilicate. Moreover, the aluminosilicates per se are not free flowing. It is also noted that if the aluminosilicate materials with which the present invention is concerned are admixed dry with the remainder of a composition, that segregation of the fine aluminosilicate materials will occur during packing and transportation of the finished product. The segregation is extremely undesirable in that when the consumer uses the product the lack of uniformity may result in over-usage or under-usage.
  • the present invention is an improvement on U.S. Patent 4.096.081, Phenicie et al, issued June 20, 1978.
  • This patent teaches agglomeration of the aluminosilicate particles using an organic agglomerating agent and an inorganic salt.
  • This agglomerate can be admixed with conventional spray-dried detergent granules.
  • a free-flowing particulate water softening composition comprising an intimate mixture of:
  • the aluminosilicate detergency builder of this invention comprise both amorphous and crystalline aluminosilicates as is well known in the art.
  • U.S. Patent 4.096.081 contains a description of such builders. Zeolites A, X, and P are preferred, with Zeolite A being most preferred.
  • ion-exchange builder materials herein are in a hydrated form, i.e., contain at least 10% by weight of water.
  • Highly preferred Zeolite A aluminosilicates herein contain the theoretical maximum of from 18% to 22% (wt.) water in their crystal matrix. It has been found, for example, that less highly hydrated Zeolite A aluminosilicates, e.g., those with about 6% water, do not function effectively as ion exchange builders when employed in the context of a laundry detergent composition.
  • a second essential feature of the ion exchange builder materials herein is their particle size range.
  • the amorphous aluminosilicates inherently have a small particle size (ca. 0.01-5 11 m diameter).
  • the crystalline aluminosilicates must have a small particle size in the range disclosed herein. Proper selection of small particle sizes results in fast, highly efficient builder materials.
  • the small particle size of the preferred aluminosilicates herein ⁇ 10 ⁇ m
  • amorphous aluminosilicate ion exchange builder/water softening materials herein can be prepared according to the following procedure:
  • the filter cake prepared by the foregoing process comprises a mixture of crystalline aluminosilicate and amorphous aluminosilicate in a 1:1 (wt.) ratio.
  • the material from the filter cake exhibits a rapid and efficient uptake of both Ca ++ and Mg ++ ions.
  • the filter cake is useful per se as an ion exchange material.
  • the drying is performed at 100°C to 105°C.
  • the amorphous aluminosilicate of this invention can, if desired, be separated from the amorphous-crystalline mixture prepared in the foregoing manner by simply suspending the filter cake mixture in water. When thus suspended, the crystalline portion of the mix settles out (over a period of 1-6 hours), whereas the amorphous material remains suspended in the aqueous medium.
  • the amorphous material can be separated by decantation or other physical means. Of course, low speed centrifugation can be employed to more rapidly separate the amorphous component from the crystalline component of the mixtures herein.
  • Both the crystalline and amorphous aluminosilicate ion exchangers herein are further characterized by their calcium ion exchange capacity which is at least 200 mg of CaC0 3 hardness/gram of aluminosilicate, calculated on an anhydrous basis, and which preferably lies within the range of 300 to about 352 mg CaCO/g.
  • the ion exchange materials herein are further characterized by their calcium ion exchange rate which is at least 0.034 g CaCO 3 /I/min/g of aluminosilicate (anhydrous basis).
  • Optimum aluminosilicates for builder purposes exhibit a calcium exchange rate of at least 0.068 g CaC0 3/ I/min/g.
  • amorphous aluminosilicate ion exchanges herein are further characterized by their magnesium exchange capacity, which is at least 42 mg of MgC0 3 hardness/gram of aluminosilicate, calculated on an anhydrous basis, and which generally lies within the range of 42 to 126 mg/g or greater.
  • the amorphous ion exchange materials herein are still further characterized by their magnesium ion exchange rate which is at least 0.004 g (Mg ++ )/I/min/g of aluminosilicate (anhydrous basis).
  • Optimum aluminosilicates for builder purposes exhibit a magnesium exchange rate of at least 0.008 g (Mg ++ )/I/min/g.
  • the ion exchange properties of the aluminosilicates herein can conveniently be determined by means of a calcium ion electrode and a divalent ion electrode.
  • the rate and capacity of Ca ++ and Mg ++ uptake from an aqueous solution containing a known quantity of Ca ++ and Mg ++ ions are determined as a function of the amount of aluminosilicate ion exchange material added to the solution.
  • the ion exchange rates of the amorphous and mixed amorphous-crystalline aluminosilicates herein are determined as follows.
  • the aluminosilicate prepared in the foregoing manner is added in the sodium form to 150 ml of aqueous solution containing 0.080 g/I Ca ++ and 0.041 g/I Mg ++ (measured as CaC0 3 ) at a concentration of 0.06% (wt.), pH of 10.0, and with gentle stirring of the solution.
  • the rate of calcium depletion is measured using the calcium electrode (commercially available; Orion@) and the rate of total calcium and magnesium depletion is determinea using the general divalent cation electrode. Magnesium ion removal is thereafter determined by the difference in readings. The rate of depletion is determined for each cation by taking measurements at appropriate time intervals.
  • Rate curves for calcium depletion, magnesium depletion and mixed calcium and magnesium depletion can be plotted as g/I v. time.
  • Calcium exchange capacity of the aluminosilicates herein can be determined by a simple titration method. In practice the aluminosilicate sample is equilibrated with a known excess of Ca ++. After equilibration and uptake of the calcium ion, the excess calcium ion remaining in solution is determined by a standard titration with EDTA, using a standard Eriochrome@ Black T Indicator. Magnesium ion capacity is determined titrimetrically, in similar fashion.
  • both the crystalline and amorphous aluminosilicates herein exhibit excellent rates of exchange and capacities for calcium ions.
  • the amorphous material herein additionally provides rapid and efficient uptake of magnesium ions. Accordingly, a mixture of crystalline and amorphous material can provide mixed Ca ++ /Mg ++ hardness control.
  • compositions of this invention are essentially free of the organic agglomerating agents of U.S. Patent 4,096,081.
  • the surfactant agglomerating agents of this invention include the following.
  • the detergent component of the present invention is a water-soluble salt of: an alcohol polyethoxylate sulfate with an average degree of ethoxylation of 1 to 10 and an alkyl chain length of from 8 to 20; an alkyl benzene sulfonate with an average alkyl chain length between 9 and 15, preferably from 11 to 13, and most preferably 11.8 carbon atoms; a C 6 -G ZO alpha-sulfocarboxylic acid or ester thereof having 1 to 14 carbon atoms in the alcohol radical; a C 8 ⁇ C 18 secondary paraffin sulfonate; a C 10 ⁇ C 18 olefin sulfonate or mixtures thereof; or other hardness insensitive anionic surfactant.
  • Such preferred detergents are discussed below. Blends of surfactants which exhibit hardness resistance (insensitivity) can be used as well.
  • An especially preferred alkyl ether sulfate detergent component of the present invention is a mixture of alkyl ether sulfates, said mixture having an average (arithmetic mean) carbon chain length within the range of 12 to 16 carbon atoms, preferably from 14 to 15 carbon atoms, and an average (arithmetic mean) degree of ethoxylation of from 1 to 4 moles of ethylene oxide, preferably from 2 to 3 moles of ethylene oxide.
  • such preferred mixtures comprise from 0 to 10% by weight of mixture of C 12-13 compounds, from 50 to 100% by weight of mixture of C 14-11 compounds, and from 0 to 45% by weight of mixture of C 16-17 compounds, and from 0 to 10% by weight of a mixture of C 18-19 compounds.
  • such preferred alkyl ether sulfate mixtures comprise from 0 to 30% by weight of mixture of compounds having a degree of ethoxylation of 0, from 45 to 95% by weight of mixture of compounds having a degree of ethoxylation from 1 to 4, from 5 to 25% by weight of mixture of compounds having a degree of ethoxylation from 5 to 8, and from 0 to 15% by weight of mixture of compounds having a degree of ethoxylation greater than 8.
  • the sulfated condensation products of ethoxylated alcohols of 8 to 24 alkyl carbons and with from 1 to 30, preferably 1 to 4 moles of ethylene oxide may be used in place of the preferred alkyl ether sulfates discussed above.
  • Preferred water-soluble organic detergent compounds herein also include alkyl benzene sulfonates (preferably essentially linear, although "hard” ABS may be used) containing from 9 to 15 carbon atoms in the alkyl group.
  • alkyl benzene sulfonates preferably essentially linear, although "hard” ABS may be used
  • Examples of the above are sodium and potassium alkyl benzene sulfonates in which the alkyl group contains from 11 to 13 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S. Pat. Nos. 2,220,099 and 2,477,383.
  • Especially valuable are straight chain alkyl benzene sulfonates in which the average of the alkyl groups is 11.8 carbon atoms, abbreviated as C 11.2 LAS.
  • Another useful detergent compound herein includes the water-soluble salts of esters of alpha- sulfonated fatty acids containing from 6 to 20 carbon atoms in the fatty acid group and their esters with alcohols containing from 1 to 14, preferably 1 to 2, carbon atoms.
  • olefin sulfonate detergent mixtures utilizable herein comprise olefin sulfonates containing from 10 to 18 carbon atoms. Such materials can be produced by sulfonation of olefins by means of uncomplexed sulfur trioxide followed by neutralization under conditions such that any sultones present are hydrolyzed to the corresponding hydroxy-alkane sulfonates.
  • the alpha-olefin starting materials preferably have from 14 to 16 carbon atoms. Said preferred alpha-olefin sulfonates are described in U.S. Pat. No. 3,332,880.
  • the secondary paraffin sulfonates embraced in the present invention are essentially linear and contain from 8 to 18 carbon atoms, preferably from 12 to 16 and more preferably from 14 to 15 carbon atoms in the alkyl radical.
  • anionic detergent compounds herein include the sodium alkyl glyceryl ether sulfates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; and sodium or potassium salts of alkyl phenol ethylene oxide ether sulfate containing 1 to 10 units of ethylene oxide per molecule and wherein the alkyl groups contain 8 to 12 carbon atoms.
  • Other useful detergents include water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from 2 to 9 carbon atoms in the acyl group and from 9 to 18 carbon atoms in the alkane moiety; beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from 8 to 18 carbon atoms in the alkane moiety; alkylmethylammoniopropane sulfonates and alkyl- methylammoniohydroxypropane sulfonates wherein the alkyl group in both types contains from 14 to 18 carbon atoms: and alkyl glycerol ether sulfates with from 10 to 18 carbon atoms in the alkyl radical.
  • compositions comprise from 1 to 4%, preferably from 2% to 3% of hardness insensitive anionic surfactant. Higher levels of surfactant simply dilute the zeolite without any benefit and can give undesirable physical properties to the agglomerate.
  • the surfactant improves dispersion of the zeolite as shown hereinafter thus minimizing unacceptable deposits, e.g. on fabrics, and increasing the rate of ion exchange.
  • the inorganic salts are water soluble and form ions. They promote dispersion of the aluminosilicate as shown to rapidly control the water hardness.
  • examples of such inorganic salts include those having alkali metal cations such as sodium, or potassium, and having as anions thereof sulfates, chlorides, carbonates, bicarbonates, aluminates and phosphates, and mixtures thereof.
  • Preferred inorganic salts include sodium sulfate, sodium carbonate, sodium orthophosphate, sodium pyrophosphate, sodium tripolyphosphate, and sodium hexametaphosphate. Especially preferred are sodium sulfate and sodium carbonate. Alkali metal silicates should not be present because of their ability to polymerize the aluminosilicate leading to deposits upon washed fabrics.
  • additional surface active agent (detergent surfactant) will be included as a portion of the overall detergent composition since the level of surfactant herein is insufficient to form a complete detergent product.
  • detergent components which may be used in the present invention are those described in U.S. Patent 3,852,211 to Ohren, issued December 3, 1974.
  • sulfuric acid is added to the synthesis liquor of the aluminosilicate to neutralize excess caustic (while staying above pH 9) and form Na 2 S0 4 .
  • the surfactant is then dispersed in the slurry and the product is spray or flash dried.
  • Another preferred method of preparing the agglomerate of the present invention is to spray the mixture of the aluminosilicate, the inorganic salt and the detergent surfactant to form granules of the size compatible with normal detergent particles. It is to be understood, however, that the product can take several forms, e.g. cakes, flakes, prills, or granules which are reduced by conventional methods to the appropriate size.
  • the preferred method of preparing the agglomerate of the present invention is by spray-drying or spray cooling the mass to form the agglomerate. It is essential when spray-drying is employed that the aluminosilicate should not be dehydrated beyond the point where its ion exchange capacity is adversely affected. Also, certain of the surfactants which are heat sensitive should not be heated to the extent at which they begin to decompose.
  • the apparatus for conducting the drying operating may be a multilevel spray-drying tower such as that described in U.S. Patent 3,629,950 and 3,629,955 issued to Davis et al.
  • the detergent surfactant will be present at from 0.5% to 4%, preferably from 1.5% to 2.5% by weight while the aluminosilicate will be present at from 60% to 95%, preferably from 70% to 80% by weight.
  • the inorganic salts which promote lessened friability are used at a level of from 0.5% to 10%, preferably from 2% to 4%. Larger amounts of the inorganic salts may be utilized in the particulate, however, the benefit reaches a maximum at 5% and additional amounts merely take up more formula room.
  • the agglomerate of the present invention When the agglomerate of the present invention is utilized as a water softener for laundering purposes, it is simply added to the wash tub or washing machine, preferably before the fabrics and the detergent composition are introduced and after the water has been introduced into the container.
  • the overall product is desirably added to the wash tub or the washing machine before the fabrics and after the water has been added.
  • the amount of the agglomerate utilized as a water softening pretreatment is simply an amount sufficient to remove most of the calcium and magnesium ions present in the wash water.
  • the product of the present invention normally has a density of from 0.45 gram per cc to 0.65 gram per cc, sufficient usage of the product will, under most United States conditions, be satisfied by the use of from 1/4 cup to 1 cup. Under continental European washing conditions where the water hardness is somewhat greater, the product will normally be used at a level of from 1/2 cup to 3 cups.
  • Laundry detergent products of the present invention are used under U.S. washing conditions at from 1/2 to 1-1/2 cups and from 1 cup to 3 cups under European washing conditions.
  • the agglomerate of this invention when added to a spray-dried detergent granule containing a surfactant to give an agglomerate level of from 5% to 80%, preferably from 10% to 60% by weight of the total composition, provides a complete detergent composition with little or no apparent formation of insolubles. This is especially important when the spray-dried detergent granule contains large amounts of silicates.
  • the agglomerate should have a size that is compatible with the detergent granule, e.g., not less than 100 ⁇ m in diameter, preferably not less than 150 ⁇ m in diameter.
  • the agglomerates of this invention do not break down unacceptably under ordinary handling and shipping.
  • Particle size can be adjusted by sieving and recycling or by adjusting spray drying pressure and nozzle size.
  • the agglomerates of this invention are completely free of the agglomerating compounds of U.S. Patent 4,096,081, and especially free of the polyethylene glycol of said patent.
  • Detergent compositions were made with the intent of increasing the thoroughness of zeolite builder dispersion in wash water.
  • the expected benefits of increased dispersion are (1) reduced incidence of insoluble aggregates on washed fabrics, and (2) increased rate of zeolite availability for complexation of water hardness.
  • NTU Nephelometer® Turbidity Unit
  • Both of the surfactants in E-H are acceptably hardness insensitive.
  • a tallow alkyl sulfate, for example, would be precipitated by free hardness and rendered ineffective as a zeolite dispersant. It is noted that the higher sustained dispersion at 30 minutes with samples E and F reflect the greater degree of hardness insensitivity of the alkyl polyethoxy sulfate vs. the alkylbenzene sulfonate of G and H.
  • the zeolite was dried from an aqueous slurry of 50-60% total water to which the other ingredients had been added.
  • the slurry was heated to 60°C and mixed thoroughly. This mixture was then dried in a thin film in a 70°C oven until only 18-20% H 2 0 remained.
  • the water of hydration in the Zeolite A is generally not removed under these conditions.
  • the dried cake was granulated arid screened through a 1.19 mm screen.
  • the resultant density was 0.58 g/cc.
  • the particle size was mostly greater than 1 50 II m.
  • Zeolite delivered to the wash water was controlled at 0.3 g/I and other components (except in B) were used as: sodium sulfate at 0.01 to 0.03 g/I, PEG 8000 at 0.01 to 0.015 g/I, and synthetic surfactants at 0.008 g/I.
  • Example II Composition of Example II was made using powdered zeolite (as received) admixed to the base granule composition.
  • the resulting detergent product was excessively dusty and free flow was unacceptable due to bridging and surging. Segregation is a further potential problem with this approach.
  • the zeolite composition of Example II is metered into a fluidized bed along with other dry ingredients and nonionic surfactant, minors, and perfume are sprayed on.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (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)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Claims (8)

1. Aggloméré d'adjuvant de détergence et de zéolite, stable et rapidement dispersable, consistant essentiellement en un mélange intime de:
(a) de 60% à 95% en poids d'un adjuvant de détergence de type aluminosilicate, choisi dans l'ensemble constitué par:
(i) un aluminosilicate amorphe;
(ii) une zéolite cristalline hydratée, choisie dans l'ensemble comprenant les zéolites A, X, P et leurs mélanges, contenant au moins 10% d'eau et ayant une granulométrie se situant entre 0,1 et 25 micromètres; et
(iii) des mélanges de l'espèce amorphe et de l'espèce cristalline;

lesdits aluminosilicates ayant une capacité d'échange de l'ion calcium d'au moins 200 mg de CaCOg/g; et une vitesse d'échange de l'ion calcium d'au moins 0,034 g de CaC03/I/min/g;
(b) de 1% à 4% en poids d'un tensioactif détergent anionique synthétique qui est relativement insensible à la dureté;
(c) de 0,5% à 10% en poids d'un sel minéral essentiellement exempt de silicates; et
(d) le reste étant de l'eau.
2. Composition selon la revendication 1, dans laquelle la dimension des agglomérés n'est pas inférieure à un diamètre de 100 micromètres.
3. Aggloméré selon la revendication 1, dans lequel l'aluminosilicate représente de 70% à 80% en poids, de tensioactif représente de 1,5% à 2,5% en poids, et le sel minéral représente de 2% à 4% en poids.
4. Aggloméré selon la revendication 2, dans lequel le tensioactif est choisi dans l'ensemble constitué par les sels hydrosolubles de:
(a) des (alcool polyéthoxylé)-sulfates dans lesquels l'alcool contient de 8 à 20 atomes de carbone et le degré moyen d'éthoxylation est de 1 à 10;
(b) des alkylbenzène sulfonates dont les groupes alkyles contiennent de 9 à 15 atomes de carbone;
(c) des acides alpha-sulfocarboxyliques contenant de 6 à 20 atomes de carbone;
(d) les esters de (a) avec des alcools contenant jusqu'à 14 atomes de carbone;
(e) des paraffine (secondaire) sulfonates contenant de 8 à 18 atomes de carbone;
(f) des oléfine sulfonates contenant de 8 à 18 atomes de carbone; et
(g) leurs mélanges.
5. Aggloméré selon la revendication 1, dans lequel la zéolite est la zéolite A.
6. Aggloméré selon les revendications 1, 3, 4 ou 5, dans lequel le sel minéral est choisi dans l'ensemble constitué par les sulfates, chlorures, carbonates, bicarbonates, aluminates, phosphates de sodium et de potassium, et leurs mélanges.
7. Aggloméré selon les revendications 1, 3, 4 ou 5, dans lequel le sel minéral est le carbonate de sodium ou le sulfate de sodium.
8. Composition détergente comprenant de 5% à 80% en poids de l'aggloméré de la revendication 1 et de 20% à 95% en poids d'un granule, séché par atomisation et contenant un tensioactif.
EP19810201157 1980-10-29 1981-10-20 Agglomérates d'aluminosilicates et compositions détergentes les contenant Expired EP0050897B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US20203380A 1980-10-29 1980-10-29
US202033 1988-06-03

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EP0050897A1 EP0050897A1 (fr) 1982-05-05
EP0050897B1 true EP0050897B1 (fr) 1985-03-06

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JP (1) JPS57131296A (fr)
CA (1) CA1160135A (fr)
DE (1) DE3169193D1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3301577A1 (de) * 1983-01-19 1984-07-19 Henkel KGaA, 4000 Düsseldorf Wasch- und reinigungsmittel
DE3827895A1 (de) * 1988-08-17 1990-02-22 Henkel Kgaa Verfahren zur herstellung phosphatreduzierter waschmitteltabletten
GB9113675D0 (en) * 1991-06-25 1991-08-14 Unilever Plc Particulate detergent composition or component
FR2696734B1 (fr) * 1992-10-09 1995-03-10 Rhone Poulenc Chimie Silico-aluminate de métal alcalin solide et amorphe.
DE4314885A1 (de) * 1993-05-05 1994-11-10 Sued Chemie Ag Verfahren zur Neutralisation der Säureform von anionischen Tensiden, danach erhaltene Agglomerate und Waschmittel
US6387873B1 (en) 2000-04-05 2002-05-14 The Procter & Gamble Company Detergent composition with improved calcium sequestration capacity
CN105886137A (zh) * 2014-12-15 2016-08-24 上海和黄白猫有限公司 高密度低温速溶洗衣粉及其制备方法
CN111032842A (zh) 2017-09-06 2020-04-17 花王株式会社 纤维制品用清洁剂组合物

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3985669A (en) * 1974-06-17 1976-10-12 The Procter & Gamble Company Detergent compositions
US4096081A (en) * 1976-02-06 1978-06-20 The Procter & Gamble Company Detergent compositions containing aluminosilicate agglomerates
CA1107349A (fr) * 1977-10-06 1981-08-18 Akio Koizumi Circuit protecteur sur regulateur de commutation
IT1160682B (it) * 1977-10-14 1987-03-11 Po Corp. Composizioni detergenti con coadiuvante di silano-zeolite
DE2903058A1 (de) * 1978-02-01 1979-08-09 Unilever Nv Verfahren zur herstellung von waschmittelpulver

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CA1160135A (fr) 1984-01-10
DE3169193D1 (en) 1985-04-11
EP0050897A1 (fr) 1982-05-05
JPS57131296A (en) 1982-08-14

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