EP0368364A2 - Adjuvant actif pour agents de lavage - Google Patents

Adjuvant actif pour agents de lavage Download PDF

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Publication number
EP0368364A2
EP0368364A2 EP89123122A EP89123122A EP0368364A2 EP 0368364 A2 EP0368364 A2 EP 0368364A2 EP 89123122 A EP89123122 A EP 89123122A EP 89123122 A EP89123122 A EP 89123122A EP 0368364 A2 EP0368364 A2 EP 0368364A2
Authority
EP
European Patent Office
Prior art keywords
water
weight
cat
calcium
insoluble
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.)
Granted
Application number
EP89123122A
Other languages
German (de)
English (en)
Other versions
EP0368364B1 (fr
EP0368364A3 (en
Inventor
Manfred Dr. Diehl
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Degussa GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Degussa GmbH filed Critical Degussa GmbH
Publication of EP0368364A2 publication Critical patent/EP0368364A2/fr
Publication of EP0368364A3 publication Critical patent/EP0368364A3/de
Application granted granted Critical
Publication of EP0368364B1 publication Critical patent/EP0368364B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC

Definitions

  • Powdered zeolite type A which can be used as a phosphate substitute in detergents, is a lumpy powder which tends to agglomerate due to its small particle size. It is difficult to mix this zeolite powder with the other detergent components to form a homogeneous powder. The fact that the finished mixture tends to segregate again makes it difficult.
  • zeolite granules are added to the already spray-dried detergent components. These zeolite granules are u. a. produced by spray drying an aqueous suspension of the zeolite powder with the addition of further detergent components.
  • x is a number from 0.7 to 1.5 Me boron or aluminum and y is a number from 0.8 to 6, 4 to 5% by weight sodium sulfate 2 to 3% by weight of nonionic surfactant 0 to 1 wt% alkali 0.5 to 1 wt .-% carboxymethyl cellulose and / or methyl cellulose Rest of water to be used for the production of phosphate-free detergents (DE-OS 35 04 450).
  • the invention relates to a granulated detergent builder consisting of: 67.7% by weight of a water-insoluble silicate capable of binding calcium in the form of a finely divided, bound water-containing, synthetically produced, water-insoluble, crystalline compound of the general formula (Cat 2 / n O) x . Me2O3.
  • x is a number from 0.7 to 1.5 Me boron or aluminum and y is a number from 0.8 to 6 2 to 3% by weight of nonionic surfactant 2.5% by weight sodium sulfate 1.1 to 5 wt .-% carboxymethyl cellulose and / or methyl cellulose Rest of water
  • the component of the formula I can be crystalline.
  • An aluminum silicate can preferably be used as the component according to formula I.
  • y can be a number from 1.3 to 4.
  • the crystalline component according to formula I can be a type A zeolite.
  • the aluminum silicates according to formula I can be naturally occurring or synthetically produced products, with the synthetically produced products being preferred.
  • the production can e.g. B. by reaction of water-soluble silicates with water-soluble aluminates in the presence of water.
  • aqueous solutions of the starting materials can be mixed with one another or a component present in the solid state can be reacted with the other component present as an aqueous solution.
  • the desired aluminum silicates are also obtained by mixing both components in the solid state in the presence of water.
  • Aluminum silicates can also be prepared from Al (OH) 2, Al2O3 or SiO2 by reaction with alkali silicate or alkali aluminate solutions.
  • the production can also be carried out by other known processes.
  • the invention relates to aluminum silicates which have a three-dimensional space lattice structure.
  • the preferred calcium binding capacity which is approximately in the range from 100 to 200 mg CaO / g AS, usually around 100 to 180 mg CaO / g AS, is found above all in compounds of the composition: 0.7 - 1.1 Na2O. Al2O3. 1.3-3.3 SiO2.
  • the crystalline aluminum silicate present in aqueous suspension can be separated from the remaining aqueous solution by filtration and dried. Depending on the drying conditions, the product contains more or less bound water.
  • the aluminum silicates do not need to be dried at all after their preparation in order to prepare the detergent builders according to the invention; rather, an aluminum silicate that is still moist from manufacture can be used, and this is particularly advantageous.
  • the particle size of the individual aluminum silicate particles can be different and z. B. are in the range between 0.1 and 0.1 mm. This refers to the primary particle size, i.e. H. the size of the particles obtained during the precipitation and, if appropriate, the subsequent crystallization. It is particularly advantageous to use aluminum silicates which consist of at least 80% by weight of particles with a size of 10 to 0.01 ⁇ m, in particular 8 to 0.1 ⁇ m.
  • These aluminum silicates preferably no longer contain primary or secondary particles with diameters above 45 ⁇ m.
  • Secondary particles are particles that are formed by agglomeration of the primary particles into larger structures.
  • powdered zeolite of type A with a particularly defined particle spectrum is used as component A.
  • Such zeolite powder can according to DE-AS 24 47 021, DE-AS 25 17 218, DE-OS 26 52 419, DE-OS 26 51 420, DE-OS 26 51 436, DE-OS 26 51 437; DE-OS 26 51 445 or DE-OS 26 51 485 can be produced. They then have the particle distribution curves given there.
  • a powdery zeolite of type A can be used, which has the particle size distribution described in DE-OS 26 51 485.
  • Addition products of 4 to 40, preferably 4 to 20 moles of ethylene oxide with 1 mole of fatty alcohol, alkylphenol, fatty acid, fatty amine, fatty acid amide or alkanesulfonamide can be used as nonionic surfactants.
  • the addition products of 5-16 mol of ethylene oxide with coconut oil or tallow fatty alcohols, with oleyl alcohol or with secondary alcohols with 8-18, preferably 12-18, carbon atoms, and with mono- or dialkylphenols with 6-14 carbon atoms in, are particularly important the alkyl residues.
  • the adduct of 5 moles of ethylene oxide with tallow fatty alcohol is of particular interest.
  • water-soluble nonionic surfactants but also not or not completely water-soluble polyglycol ethers with 1-4 ethylene glycol ether residues in the molecule of interest, especially if they are used together with water-soluble nonionic or anionic surfactants.
  • the water-soluble adducts of ethylene oxide with polypropylene glycol, alkylene diamine polypropylene glycol and alkyl polypropylene glycols with 1-10 carbon atoms in the alkyl chain, in which the polypropylene glycol chain is hydrophobic are usable as nonionic surfactants which contain 20-250 ethylene glycol ether groups and 10-100 propylene glycol ether groups.
  • Nonionic surfactants of the amine oxide or sulfoxide type can also be used.
  • fatty alcohol ethoxylates based on isotridecyl alcohol or an aliphatic C13 alcohol and ethylene oxide for use as a nonionic Tenisd.
  • This mixture can preferably consist of fatty alcohol ethoxylates with 4.5 to 5.5 EO and fatty alcohol ethoxylates with 6 to 8 EO.
  • a mixture of at least two different alkylphenol ethoxylates of the formula can also be used as the nonionic surfactant be used.
  • R can be an aliphatic radical with 1 to 15, for example -CH3, -C2H5, propyl, butyl, pentyl, hexyl, heptyl, octyl and nonyl preferably with 9 C atoms such as nonyl.
  • the radical R can be substituted in the ortho, meta and / or para position.
  • Mixtures can also be used in which, in addition to p-substituted aryl ring, o-substituted benzene ring is also present. Mixtures are used in which there is 90% p-substitution and 10% ortho-substitution.
  • n can mean 2 to 7, preferably 4 to 6, in particular 5 in the case of one alkylphenol ethoxylate used in the mixture and 8 to 15, preferably 8 to 12, in particular 9 or 10 in the other alkylphenol ethoxylate.
  • n can also mean mixtures of the alkylphenolates in each case 7 or 9 or 12.
  • alkylphenol ethoxylates and the isotridecyl alcohol ethoxylates can each be used in any mixture, preferably in a ratio of 1: 9 to 9: 1, preferably 2: 3 to 3: 2, in particular 0.9: 1.1 to 1.1: 0.9 will.
  • the proportion of carboxymethyl cellulose and / or methyl cellulose can be 2.4 to 5.0% by weight in a preferred embodiment of the invention.
  • NaOH and / or KOH can be used as alkali.
  • the granular detergent builder according to the invention can be prepared by mixing the individual components with one another, setting a consistency suitable for spray drying by measuring the amount of water and spray-drying the suspension thus obtained by known methods.
  • the granulated detergent builder according to the invention is stable in transportation, easy to redisperse and extremely low in dust.
  • the product according to the invention has an extremely high absorption capacity for water and surfactants.
  • the granular detergent builder according to the invention can be processed into a detergent simply by mixing it with the other granular detergent constituents. The mixture does not separate.
  • a zeolite A filter cake according to DE-OS 26 51 485 is produced.
  • the powdery zeolite of type A obtained in this way has the particle spectrum given there.
  • the zeolite A filter cake is stirred up with a dissolver and then heated to 45 ° C. in a 50 l vessel.
  • the nonionic surfactant is stirred in at 75-76 rpm with a MIG stirrer 15 ', the temperature of the slurry rising to 50 ° C.
  • the following surfactant is used as the only component or in mixtures as a stabilizer: Tallow alcohol ethoxylate 5 EO
  • the suspension obtained is mixed with the other constituents listed in the tables and then spray-dried (nozzle dryer inlet temperature 180 ° C., exhaust air temperature 75 ° C.).
  • the funding tests were carried out on a power tube conveyor screw. The samples were subjected to one or two conveyance. See Table 2 for results.
  • test products 1, 2 and 3 have the best stability despite the very coarse grain. These three samples show only a slight deterioration in the flow behavior in the bulk cone even after being pumped twice and are therefore to be assessed better than the comparison sample 4 according to the prior art.
  • the powder falling into a cylinder via a shaking trough is collected in a vessel under the shaking point, while the dust particles outside this vessel settle on the base plate of the cylinder and can be determined gravimetrically.
  • the following devices are used:
  • Apparatus for determining the dust consisting of a shaking channel Manufacturer: AEG, type DR 50 220 V 50 Hz, 0.15 A. Outer cylinder Height: 70 cm, diameter 40 cm closed at the top, open at the bottom
  • the cover plate is provided in the middle with a circular opening (diameter: 3 cm) for receiving the filler pipe.
  • Inner cylinder Height 10 cm, diameter: 18 cm closed at the bottom, open at the top.
  • Base plate Shape round Diameter: 48 cm
  • Filler pipe Length 30 cm, diameter: 2.5 cm Immersion depth of the tube in the outer cylinder: 20 cm.
  • the immersion depth is kept constant by a brass disc (diameter: 15 cm, thickness: 1 mm) soldered to the outer wall of the filler pipe.
  • funnel upper diameter 15 cm Spout diameter: 1.8 cm
  • the apparatus is shown in the drawing. According to the figure, the shaking channel is set up on a laboratory table. The rest of the apparatus should be arranged in such a way that the outlet of the shaking channel lies directly above the center of the funnel (3) and its distance from the top edge of the funnel is 5.5 cm.
  • the frequency of the shaking channel should be 50 Hz and the opening gap should be set so that the substance has passed through the shaking channel in 1 minute.
  • the powder falls through a funnel (3) and a filler pipe (4) into the inner cylinder of the test apparatus (5) below, while the dust outside this vessel accumulates on the base plate (6) of the outer cylinder (7).
  • any remaining powder in the funnel is transferred to the apparatus by gently tapping the funnel.
  • the dust deposited on the polished floor plate is collected in a small bowl with a metal spatula and weighed out.
  • the dust content is given in percent based on the weight.
  • the pneumatic or mechanical conveying properties were tested with the spray-dried detergent builder according to the invention, which contains the non-ionic surfactant tallow alcohol 5EO (example 3): the changes in the bulk density and the flow behavior were measured to assess the conveyed goods.
  • the spray-dried detergent builder according to the invention which contains the non-ionic surfactant tallow alcohol 5EO (example 3): the changes in the bulk density and the flow behavior were measured to assess the conveyed goods.
  • the sample was fed into a material separator via a rising screw conveyor.
  • the adjustable drive motor was set to a low rotation of 300 rpm.

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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)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
EP89123122A 1987-01-30 1987-11-26 Adjuvant actif pour agents de lavage Expired - Lifetime EP0368364B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE3702763 1987-01-30
DE3702763 1987-01-30
DE19873735618 DE3735618A1 (de) 1987-01-30 1987-10-21 Waschmittelbuilder
DE3735618 1987-10-21
EP87117460A EP0279038B1 (fr) 1987-01-30 1987-11-26 Adjuvant actif pour agents de lavage

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
EP87117460.3 Division 1987-11-26

Publications (3)

Publication Number Publication Date
EP0368364A2 true EP0368364A2 (fr) 1990-05-16
EP0368364A3 EP0368364A3 (en) 1990-06-06
EP0368364B1 EP0368364B1 (fr) 1994-06-01

Family

ID=25852033

Family Applications (2)

Application Number Title Priority Date Filing Date
EP87117460A Expired - Lifetime EP0279038B1 (fr) 1987-01-30 1987-11-26 Adjuvant actif pour agents de lavage
EP89123122A Expired - Lifetime EP0368364B1 (fr) 1987-01-30 1987-11-26 Adjuvant actif pour agents de lavage

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP87117460A Expired - Lifetime EP0279038B1 (fr) 1987-01-30 1987-11-26 Adjuvant actif pour agents de lavage

Country Status (7)

Country Link
US (1) US4883607A (fr)
EP (2) EP0279038B1 (fr)
JP (1) JPH0660319B2 (fr)
AT (1) ATE106443T1 (fr)
DE (3) DE3735618A1 (fr)
DK (2) DK170031B1 (fr)
ES (2) ES2053935T3 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3715051A1 (de) * 1987-05-06 1988-11-17 Degussa Phosphatfreier waschmittelbuilder
DE4109501A1 (de) * 1991-03-22 1992-09-24 Degussa Waessrige stabile suspension wasserunloeslicher, zum binden von calciumionen befaehigter silikate und deren verwendung zur herstellung von wasch- und reinigungsmitteln
DE19525870A1 (de) * 1995-07-15 1997-01-16 Grueter Hans Jochen Verfahren zur Herstellung einer Polysaccharid-Suspension
JP2000500799A (ja) * 1995-11-29 2000-01-25 ユニリーバー・ナームローゼ・ベンノートシヤープ 顆粒状洗剤ビルダー

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT335035B (de) * 1974-10-10 1977-02-25 Henkel & Cie Gmbh Stabile suspensionen wasserunloslicher, zum binden von calciumionen befahigter silikate und deren verwendung zur herstellung von wasch- und reinigungsmitteln
US4379080A (en) * 1981-04-22 1983-04-05 The Procter & Gamble Company Granular detergent compositions containing film-forming polymers
GB8415302D0 (en) * 1984-06-15 1984-07-18 Unilever Plc Fabric washing process
DE3504451A1 (de) * 1985-02-09 1986-08-14 Degussa Ag, 6000 Frankfurt Waschmittelbuilder
DE3504450A1 (de) * 1985-02-09 1986-08-14 Degussa Ag, 6000 Frankfurt Waschmittelbuilder

Also Published As

Publication number Publication date
DK29588D0 (da) 1988-01-22
DE3766950D1 (de) 1991-02-07
ATE106443T1 (de) 1994-06-15
ES2053935T3 (es) 1994-08-01
ES2020253B3 (es) 1991-08-01
DE3789971D1 (de) 1994-07-07
JPH0660319B2 (ja) 1994-08-10
EP0368364B1 (fr) 1994-06-01
US4883607A (en) 1989-11-28
DK170031B1 (da) 1995-05-01
DK19995A (da) 1995-02-24
DK170716B1 (da) 1995-12-18
EP0279038A1 (fr) 1988-08-24
DE3735618A1 (de) 1988-08-11
EP0368364A3 (en) 1990-06-06
DK29588A (da) 1988-07-31
JPS63193996A (ja) 1988-08-11
EP0279038B1 (fr) 1991-01-02

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