EP0195127B1 - Waschmittelbuilder - Google Patents

Waschmittelbuilder Download PDF

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Publication number
EP0195127B1
EP0195127B1 EP85115964A EP85115964A EP0195127B1 EP 0195127 B1 EP0195127 B1 EP 0195127B1 EP 85115964 A EP85115964 A EP 85115964A EP 85115964 A EP85115964 A EP 85115964A EP 0195127 B1 EP0195127 B1 EP 0195127B1
Authority
EP
European Patent Office
Prior art keywords
water
detergent builder
denotes
calcium
zeolite
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
Application number
EP85115964A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0195127A2 (de
EP0195127A3 (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
Priority to AT85115964T priority Critical patent/ATE53064T1/de
Publication of EP0195127A2 publication Critical patent/EP0195127A2/de
Publication of EP0195127A3 publication Critical patent/EP0195127A3/de
Application granted granted Critical
Publication of EP0195127B1 publication Critical patent/EP0195127B1/de
Anticipated expiration legal-status Critical
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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
    • C11D3/04—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
    • 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. This is aggravated by the fact that the finished mixture tends to segregate again.
  • zeolite granules are added to the already spray-dried detergent components. These zeolite granules are produced by spray drying an aqueous suspension of the zeolite powder with the addition of further detergent components.
  • a spray-dried powder component is known from European published patent application EP-OS 0114308, which consists of 60 to 80% by weight of aluminosilicate, 2 to 10% by weight of sodium sulfate, 1 to 5% by weight of a nonionic surfactant, 0 to 8% by weight. -% of a polyphosphonic acid and 10 to 25 wt .-% water.
  • an insoluble detergent builder which is characterized in that it contains easily disintegrating agglomerates of finely divided zeolite particles with ion exchange properties, which are held together by a binder, the particle size of the agglomerates being in a range corresponding to a mesh number from 4 to 180.
  • Carboxymethyl cellulose and methyl cellulose can be used as binders.
  • the invention relates to a granulated detergent builder consisting of:
  • the component according to formula I can be crystalline.
  • the component of the formula (an aluminum silicate can preferably be used.
  • y can be a number from 1.3 to 4.
  • the crystalline component according to formula 1 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 preparation kkann example by - carried by water reaction of water-soluble silicates with water-soluble aluminates in the presence.
  • 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 produced from Al (OH) 2 , Al 2 0 3 or Si0 2 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:
  • This molecular formula comprises two types of different crystal structures (or their non-crystalline precursors), which also differ in their molecular formulas. They are:
  • 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 e.g. are in the range between 0.1 ⁇ m and 0.1 mm. This refers to the primary particle size, i.e. 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.
  • the use of the aluminum silicates which are still moist from their production for the production of the detergent builders according to the invention has proven particularly useful since it has been found that the formation of secondary particles is practically completely prevented when these still moist products are used.
  • 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 adducts 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 C atoms, and with mono- or dialkylphenols with 6-14 C atoms in are particularly important the alkyl residues.
  • the adduct of 5 moles of ethylene oxide with tallow fatty alcohol is of particular interest.
  • non-or not completely water-soluble polyglycol ethers with 1-4 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble nonionic or anionic surfactants.
  • the water-soluble adducts of ethylene oxide with polypropylene glycol, alkylenediamine-polypropylene glycol and alkylpolypropylene glycols with 1-10 C atoms in the alkyl chain, in which the polypropylene glycol chain functions, are useful as nonionic surfactants, the addition products containing 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.
  • nonionic surfactant is a mixture of at least two different fatty alcohol ethoxylates based on isotridecyl alcohol or an aliphatic C 13 alcohol and ethylene oxide.
  • 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, --C 2 H 5 , 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.
  • 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 tempered to 45 ° C. in a 50 liter 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 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 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
  • the cover plate is provided in the middle with a circular opening (diameter: 3 cm) for receiving the filler pipe.
  • 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.
  • 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.
  • 100 g of the sample are brought into the shaking channel (2) via the feed funnel (1).
  • the frequency of the shaking trough should be 50 Hz and the opening gap should be set so that the substance has passed through the shaking trough in 1 minute.
  • the powder falls through a funnel (3) and a filler tube (4) into the inner cylinder of the test apparatus (5) underneath, while the dust outside this vessel collects on the base plate (6) of the outer cylinder (7).
  • any remaining powder in the funnel is transferred into the apparatus by gently tapping the funnel.
  • the dust deposited on the polished base 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 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Glass Compositions (AREA)
  • Fodder In General (AREA)
  • Glanulating (AREA)
EP85115964A 1985-02-09 1985-12-13 Waschmittelbuilder Expired - Lifetime EP0195127B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85115964T ATE53064T1 (de) 1985-02-09 1985-12-13 Waschmittelbuilder.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3504450 1985-02-09
DE19853504450 DE3504450A1 (de) 1985-02-09 1985-02-09 Waschmittelbuilder

Publications (3)

Publication Number Publication Date
EP0195127A2 EP0195127A2 (de) 1986-09-24
EP0195127A3 EP0195127A3 (en) 1987-09-30
EP0195127B1 true EP0195127B1 (de) 1990-05-23

Family

ID=6262087

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85115964A Expired - Lifetime EP0195127B1 (de) 1985-02-09 1985-12-13 Waschmittelbuilder

Country Status (13)

Country Link
US (1) US4683073A (no)
EP (1) EP0195127B1 (no)
JP (1) JPS61183397A (no)
KR (1) KR900000879B1 (no)
AT (1) ATE53064T1 (no)
AU (1) AU571766B2 (no)
DE (2) DE3504450A1 (no)
ES (1) ES8702483A1 (no)
FI (1) FI860555A (no)
NO (1) NO163017C (no)
PH (1) PH23310A (no)
PT (1) PT81979B (no)
YU (1) YU44539B (no)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3702111A1 (de) * 1987-01-24 1988-08-04 Henkel Kgaa Poroeses schichtsilikat/natriumsulfat-agglomerat
DE3702764A1 (de) * 1987-01-30 1988-08-11 Degussa Waschmittelbuilder
DE3735617A1 (de) * 1987-01-30 1988-08-11 Degussa Waschmittelbuilder
DE3735618A1 (de) * 1987-01-30 1988-08-11 Degussa Waschmittelbuilder
DE3715051A1 (de) * 1987-05-06 1988-11-17 Degussa Phosphatfreier waschmittelbuilder
US5174918A (en) * 1987-06-06 1992-12-29 Degussa Ag Stable aqueous suspensions of detergent zeolites and four oxo-alcohol ethoxylates
DE3818829A1 (de) * 1988-06-03 1989-12-14 Henkel Kgaa Koerniges adsorptionsmittel mit verbessertem einspuelverhalten
EP0425149A3 (en) * 1989-10-23 1992-03-25 Imperial Chemical Industries Plc Detergent compositions and processes of making them
US8151759B2 (en) * 2006-08-24 2012-04-10 Wright Innovations, Llc Orbital engine
EP3175844A1 (en) 2010-04-09 2017-06-07 Pacira Pharmaceuticals, Inc. Large diameter synthetic membrane vesicles
WO2012022034A1 (en) 2010-08-18 2012-02-23 Unilever Plc Improvements relating to fabric treatment compositions comprising targeted benefit agents
CN103747772B (zh) * 2011-08-24 2016-03-16 荷兰联合利华有限公司 包含非离子多糖的有益剂递送颗粒
CN103781460B (zh) 2011-08-24 2016-05-18 荷兰联合利华有限公司 包含右旋糖酐的有益剂递送颗粒
WO2013026657A1 (en) * 2011-08-24 2013-02-28 Unilever Plc Benefit agent delivery particles comprising non-ionic polysaccharides

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT334489B (de) * 1974-07-04 1976-01-25 Henkel & Cie Gmbh Verfahren zur herstellung phosphatarmer bzw. phosphatfreier wasch- und reinigungsmittel
AT375393B (de) * 1974-10-04 1984-07-25 Henkel Kgaa Verfahren zum waschen bzw. bleichen von textilien sowie mittel dazu
US4169075A (en) * 1974-10-10 1979-09-25 Henkel Kommanditgesellschaft Auf Aktien Process for the production of powdery washing agents by spray-drying
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
ZA774818B (en) * 1976-08-17 1979-03-28 Colgate Palmolive Co Disintegrable detergent builder agglomerates
DE2900063A1 (de) * 1979-01-02 1980-07-17 Henkel Kgaa Waschmittel mit einem gehalt an schaumdaempfend wirkendem polydimethylsiloxan und verfahren zu dessen herstellung
JPS5916596A (ja) * 1982-07-16 1984-01-27 Toshiba Corp 余剰汚泥引抜装置
DE3248022A1 (de) * 1982-12-24 1984-06-28 Henkel KGaA, 4000 Düsseldorf Spruehgetrocknetes mehrkomponenten-waschmittel

Also Published As

Publication number Publication date
PT81979A (de) 1986-03-01
NO860049L (no) 1986-08-11
ES551729A0 (es) 1987-01-01
YU44539B (en) 1990-08-31
YU5386A (en) 1988-04-30
NO163017C (no) 1990-03-21
JPH0357160B2 (no) 1991-08-30
JPS61183397A (ja) 1986-08-16
EP0195127A2 (de) 1986-09-24
FI860555A (fi) 1986-08-10
PH23310A (en) 1989-06-30
AU571766B2 (en) 1988-04-21
KR860006537A (ko) 1986-09-11
EP0195127A3 (en) 1987-09-30
NO163017B (no) 1989-12-11
DE3504450A1 (de) 1986-08-14
PT81979B (pt) 1987-12-30
DE3577877D1 (de) 1990-06-28
AU5218286A (en) 1986-08-14
FI860555A0 (fi) 1986-02-07
US4683073A (en) 1987-07-28
ATE53064T1 (de) 1990-06-15
ES8702483A1 (es) 1987-01-01
KR900000879B1 (ko) 1990-02-17

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