EP0430328B1 - Verfahren zur Herstellung von Ton enthaltenden Reinigungspulvern hoher Dichte - Google Patents

Verfahren zur Herstellung von Ton enthaltenden Reinigungspulvern hoher Dichte Download PDF

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Publication number
EP0430328B1
EP0430328B1 EP90203012A EP90203012A EP0430328B1 EP 0430328 B1 EP0430328 B1 EP 0430328B1 EP 90203012 A EP90203012 A EP 90203012A EP 90203012 A EP90203012 A EP 90203012A EP 0430328 B1 EP0430328 B1 EP 0430328B1
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EP
European Patent Office
Prior art keywords
weight
detergent
clay
process according
sodium
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
EP90203012A
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English (en)
French (fr)
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EP0430328A2 (de
EP0430328A3 (en
Inventor
Graem Douglas Armstrong
Donal Gerard Cronin
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.)
Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Publication date
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0430328A2 publication Critical patent/EP0430328A2/de
Publication of EP0430328A3 publication Critical patent/EP0430328A3/en
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Publication of EP0430328B1 publication Critical patent/EP0430328B1/de
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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • 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
    • 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
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions

Definitions

  • the present invention relates to a process for preparing a granular detergent composition or component having a high bulk density and good powder properties. More in particular, it relates to a process for the preparation of a granular detergent composition having good powder dissolution properties and a good softening in the wash performance.
  • the first type of process involves spray-drying an aqueous detergent slurry in a spray-drying tower.
  • the various components are dry-mixed and optionally agglomerated with liquids, e.g. nonionics.
  • the most important factor that governs the bulk density of a detergent powder is the bulk density of the starting materials in the case of a dry-mixing process, or the chemical composition of the slurry in the case of a spray-drying process. Both factors can only be varied within a limited range. For example, the bulk density of a dry-mixed powder can be increased by increasing its content of relatively dense sodium sulphate, but the latter does not contribute to the detergency of the powder, so that its overall properties as a washing powder will generally be adversely affected.
  • the Japanese patent application 61 069897 discloses a process in which a spray-dried detergent powder containing a high level of anionic surfactant and a low level of builder (zeolite) is subjected successively to a pulverizing and a granulating treatment in a high-speed mixer/granulator.
  • the granulation is carried out in the presence of an "agent for improving surface properties" and optionally a binder.
  • the present invention provides a process for the preparation of a granular detergent composition or component having a bulk density of at least 550 g/l, which comprises the steps of adding up to 35% by weight of a swelling clay to a particulate starting material comprising:
  • a particulate starting material is admixed with a swelling clay and treated in a high-speed mixer/granulator.
  • the starting material for the process according to the invention comprises (a) from 10 to 70% by weight of non-soap detergent active material, and (b) at least 15% by weight of water-soluble crystalline inorganic salts, including sodium tripolyphosphate and/or sodium carbonate, the weight ratio of
  • the starting material comprises the compounds usually found in detergent compositions such as detergent active materials, builders, and so forth, all well known in the art.
  • the detergent active material may be selected from non-soap anionic, ampholytic, zwitterionic or nonionic detergent active materials or mixtures thereof. Particularly preferred are all anionic or mixtures with nonionic detergent active materials such as a mixture of an alkali metal salt of an alkyl benzene sulphonate together with an alkoxylated alcohol.
  • the preferred detergent compounds which can be used are synthetic anionic and nonionic compounds.
  • the former are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from 8 to 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals.
  • suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C8-C18) alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl (C9-C20) benzene sulphonates, particularly sodium linear secondary alkyl (C10-C15) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty monoglyceride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C8-C18) fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralized with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurine; alkane mono
  • Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
  • Specific nonionic detergent coompounds are alkyl (C6-C22) phenols-ethylene oxide condensates, generally 5 to 25 EO, i.e.
  • nonionic detergent compounds include long-chain tertiary amine oxides, long-chain tertiary phosphine oxides and dialkyl sulphoxides.
  • detergent compounds for example, mixed anionic or mixed anionic and nonionic compounds
  • Amounts of amphoteric or zwitterionic detergent compounds can also be used in the compositions of the invention but this in not normally desired owing to their relatively high cost. If any amphoteric or zwitterionic detergent compounds are used, it is generally in small amounts in compositions based on the much more commonly used synthetic anionic and/or nonionic detergent compounds.
  • the detergency builder may be any material capable of reducing the level of free calcium ions in the wash liquor and will preferably provide the composition with other beneficial properties such as the generation of an alkaline pH, the suspension of soil removed from the fabric and the suspension of the fabric-softening clay material.
  • the level of the detergency builder may be from 10% to 70% by weight, most preferably from 25% to 50% by weight.
  • detergency builders include precipitating builders such as the alkali metal carbonates, bicarbonates, orthophosphates, sequestering builders such as the alkali metal tripolyphosphates or nitrilotriacetates, or ion exchange builders such as the amorphous alkali metal aluminosilicates or the zeolites.
  • the starting material may be prepared by any suitable method, such as spray-drying or dry mixing.
  • a suitable particulate material may also be prepared by a dry neutralization process in which a liquid acid anionic surfactant precursor is reacted with a solid alkaline inorganic component, such as carbonate.
  • dry neutralization processes are for example disclosed in the British Patents 2 166 452 (Kao), 1 404 317 (Bell) or 1 369 269 (Colgate).
  • the starting material is fed into a high-speed mixer/granulator having both a stirring action and a cutting action.
  • the preferred type of high-speed mixer/granulator for use in the process of the invention is bowl-shaped and has a substantially vertical stirrer axis. It is especially preferred when the mixer/granulator additionally has cutter means positioned on a side wall. These stirrer and cutter means may advantageously be operated independently of one another, and at separately variable speeds. It is also preferred if the vessel of the mixer is equipped with a jacket for cooling or heating purposes. If necessary, cooling may be effected by means of a cryogenic unit.
  • Examples of preferred mixers are the Fukae (Trade Mark) FS-G series manufactured by Fukae Powtech Kogyo Co., Japan, e.g. the Fukae FS30.
  • This apparatus is essentially in the form of a bowl-shaped vessel accessible via a top port, provided near its base with a stirrer having a substantially vertical axis, and a cutter on a side wall.
  • a similar mixer manufactured in India is the Sapphire (Trade Mark) RMG series of rapid mixer/granulators, which, like the Fukae mixer, is available in a range of different sizes.
  • This apparatus is essentially in the form of a bowl-shaped vessel raised up pneumatically to seal against a fixed lid.
  • a three-bladed stirrer and a four-bladed shutter share a single substantially vertical axis of rotation mounted on the lid.
  • the stirrer and cutter may be operated independently of one another, the stirrer at speeds of 75 rpm or 150 rpm, and the cutter at speeds of 1440 rpm or 2880 rpm.
  • the vessel can be fitted with a water jacket which may be used to cool or heat the content of the vessel.
  • the Sapphire RMG-100 mixer which is suitable for handling a 60 kg batch of detergent powder, has a bowl of about 1 meter diameter and 0.3 meters deep; the working capacity is 200 liters.
  • the stirrer blades are of 1 meter diameter and the cutter blades are of 0.1 meter diameter.
  • mixers found to be suitable for use in the process of the invention include the Diosna (Trade Mark) V series ex Dierks and Söhne, Germany; and the Pharma Matrix (Trade Mark) ex T.K. Fielder Ltd, England.
  • Other mixers believed to be suitable for use in the process of the invention are the Fuji (Trade Mark) VG-C series ex Fuji Sangyo Co., Japan; and the Roto (Trade Mark) ex Zanchetta & Co. srl, Italy.
  • These apparatus (which may be continuous or batch fed) essentially consist of a large, static hollow cylinder and a rotating shaft in the middle.
  • the shaft has several different types of blades mounted thereon.
  • the rotation speed which may be variable, will depend on the degree of densification and the particle size desired.
  • the blades on the shaft provide a thorough mixing action of the solids and the liquids which may be admixed at this stage.
  • the mean residence time is somewhat dependent on the rotational speed of the shaft and the position of the blades with continuous plant.
  • High-speed cutter blades, independently driven, may also be incorporated in this type of mixer operating normally to the main agitator, e.g. Lodige (Trade Mark) KM series or Drais (Trade Mark) KT series.
  • a pretreatment may be carried out, for example a pulverization step. Whether this is necessary is dependent, amongst other things, on the method of preparing of the starting material, its particle size and moisture content. For example, spray-dried powders are more likely to require a pulverization pretreatment than dry-mixed powders.
  • a suitable stirring/cutting regime must be chosen which will generally be characterized by relatively high speeds for both the stirrer and the cutter and a relatively short residence time, for example of 1 to 4 minutes.
  • the granulation step is similarly carried out by running the stirrer and the cutter at a relatively high speed, but here the presence of a liquid binder is necessary.
  • the preferred binder is water.
  • the amount of binder added should preferably not exceed about 6 % by weight, because higher levels may adversely affect the flow properties of the final product.
  • the liquid binder may be added before or during granulation, preferably by spraying it in while the apparatus is running.
  • the starting material may also already contain sufficient moisture, such that addition of further liquid binder is not necessary. In this case, pulverization and granulation may be carried out as a single operation.
  • the granulation is carried out at a temperature above ambient, such as a temperature above 30 or 45 °C.
  • a spray-dried detergent base powder leaving the tower at a temperature of approximately 45°C or above may be fed directly into the process of the present invention.
  • the spray-dried powder may be cooled first, e.g. by means of an airlift.
  • a swelling clay is added to the mixer/granulator in an amount of up to 35% by weight of the starting material.
  • the swelling clay material may be any such material capable of providing a fabric-softening benefit.
  • these materials will be of natural origin containing a three-layer swellable smectite clay.
  • the clay is of the calcium and/or sodium montmorillonite type.
  • a clay-containing material as a fabric softener will depend amongst other things on the level of smectite clay. Impurities such as calcite, feldspar and silica will often be present. Relatively impure clays can be used, provided that such impurities are tolerable in the composition.
  • the level of the fabric-softening clay material in the composition should be sufficient to provide a softening benefit. Amounts from 1.5% to 35% by weight, preferably from 4% to 20% by weight, calculated on the basis of the clay mineral per se were found to be effective.
  • the compositions according to the invention optionally may contain other ingredients usually found in detergent compositions, in the amounts in which such additives are normally employed in fabric-washing detergent compositions.
  • additives include the lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, lather depressants, oxygen releasing bleaching agents such as sodium perborate and sodium percarbonate, peracid bleach precursors, chlorine releasing bleaching agents such as trichloroisocyanuric acid, fillers such as sodium sulphate, and, usually present in very minor amounts, fluorescent agents, perfumes, enzymes such as proteases, lipases and amylases, germicides and colorants.
  • the process of the present invention enables the preparation of detergent compositions having a high bulk density of at least 550 g/l. It is a surprising advantage of the process of the invention that the bulk density of the obtained powders is higher than when the clay is admixed to the crutcher slurry prior to spray-drying of the starting material.
  • a further advantage of the process of the invention is that the softening action of the final detergent powder is improved relative to when the clay is admixed to the crutcher slurry followed by spray-drying. This effect of the present process can be established by methods used for assessment of softening delivery as they have previously been described in the art.
  • the following detergent powders were prepared by spray-drying aqueous slurries.
  • the compositions (in % by weight) of the powders thus obtained are given below.
  • Example 2 contained a Ca-clay (Prassa ex Colin Stewart Minerals, U.K.) which was added to the crutcher slurry and spray-dried. Sodium carbonate was in this case omitted from the slurry to maintain it at a sufficiently low viscosity to aid in spray-drying.
  • Example 3 was a spray-dried powder without clay but including carbonate.
  • compositions of Examples 2 and 3 had a higher percentage by weight of LAS, STP and silicate than the composition of Example 1 to allow for dilution on post-dosing of either carbonate or clay, respectively, during the densification/granulation step.
  • the powders were added (10 kg - Example 1; 9.2 kg - Example 2; 9.0 kg - Example 3) to a Fukae FS-30 high-speed mixer/granulator.
  • the powders were pulverized for 2 minutes at 70°C with a stirrer rotation of 300 rpm and a cutter rotation of 3000 rpm.
  • 0.8 kg sodium carbonate and 1.0 kg Ca-clay were added to the densified powders of Examples 2 and 3.
  • Granulation was then effected by addition of about 150 ml water over a time period of one minute at a stirrer rotation speed of 275 rpm and a cutter rotation speed of 3000 rpm.
  • the resulting powders were sieved for oversize (>1700 »m).
  • the composition (in % by weight) of the powders was as follows:
  • Table 4 Also shown in Table 4 are the softening properties of the various compositions.
  • the softening delivery of concentrated powders of Examples 1-3 was measured on terry toweling fabric. Tergotometer washes at a powder concentration of 3.6 g/l were performed for 30 minutes with a cloth to liquor weight ratio of 1:20.
  • the relative softening delivery was measured according to standard practice by a trained panel of ten people, as described in the art.
  • Example 3 The superior softening delivery of the composition of Example 3 according to the invention (in which the clay was post-dosed during granulation) may also be illustrated by a further comparative experiment whereby the clay powder was added to Example 1 during the wash at concentrations equivalent to Example 3.
  • Example 2 When the clay was added separately to the wash using the composition of Example 1, a softness value of 97.5 was found. Comparison of this value with the softness value of 99.5 found for Example 3 indicates that essentially the full softening performance is delivered by the process of the invention. However, when the clay was added to the crutcher slurry prior to spray-drying as in Example 2, a much lower softness value of 75.3 was found.

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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)
  • Detergent Compositions (AREA)

Claims (7)

  1. Verfahren zur Herstellung einer körnchenförmigen Waschmittelzusammensetzung oder -komponente mit einer Schüttdichte von mindestens 550 g/l, umfassend die Schritte der Zugabe von bis zu 35 Gew.-% eines quellbaren Tons zu einem teilchenförmigen Ausgangsmaterial, umfassend:
    (a) 10 bis 70 Gew.-% eines nicht-seifenartigen Waschmittelaktivstoffs, und
    (b) mindestens 10 Gew.-% wasserlösliche kristalline anorganische Salze, einschließlich Natriumtripolyphosphat und/oder Natriumcarbonat,
       wobei das Gewichtsverhältnis von (a) zu (b) höchstens 2,5 beträgt und Behandeln des Gemisches in einem Hochgeschwindigkeitsmischer/Granulator mit sowohl einer Rührwirkung als auch einer Schneidwirkung.
  2. Verfahren nach Anspruch 1, wobei das Gewichtsverhältnis von (a) zu (b) 0,1 bis 2,0 und vorzugsweise 0,1 bis 1,0 beträgt.
  3. Verfahren nach einem der vorangehenden Ansprüche, wobei der quellbare Ton ein Ton vom Calcium- und/oder Natriummontmorillonittyp ist.
  4. Verfahren nach einem der vorangehenden Ansprüche, wobei der Hochgeschwindigkeitsmischer/Granulator ein Hochgeschwindigkeitsmischer/Granulator vom Schalentyp mit einer im wesentlichen vertikalen Rührerachse ist.
  5. Verfahren nach einem der vorangehenden Ansprüche, wobei das teilchenförmige Ausgangsmaterial sprühgetrocknetes Waschmittelpulver umfaßt.
  6. Verfahren nach einem der vorangehenden Ansprüche, wobei das teilchenförmige Ausgangsmaterial 15 bis 50 Gew.-% Natriumtripolyphosphat umfaßt.
  7. Verfahren nach einem der vorangehenden Ansprüche, wobei die Granulierung bei einer Temperatur von mindestens 45°C ausgeführt wird.
EP90203012A 1989-11-27 1990-11-14 Verfahren zur Herstellung von Ton enthaltenden Reinigungspulvern hoher Dichte Expired - Lifetime EP0430328B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8926718 1989-11-27
GB898926718A GB8926718D0 (en) 1989-11-27 1989-11-27 Process for the preparation of detergent compositions

Publications (3)

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EP0430328A2 EP0430328A2 (de) 1991-06-05
EP0430328A3 EP0430328A3 (en) 1991-07-31
EP0430328B1 true EP0430328B1 (de) 1995-02-15

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EP90203012A Expired - Lifetime EP0430328B1 (de) 1989-11-27 1990-11-14 Verfahren zur Herstellung von Ton enthaltenden Reinigungspulvern hoher Dichte

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EP (1) EP0430328B1 (de)
JP (1) JPH0762160B2 (de)
KR (1) KR950001687B1 (de)
AU (1) AU627958B2 (de)
BR (1) BR9005981A (de)
CA (1) CA2030451C (de)
DE (1) DE69016945T2 (de)
ES (1) ES2067658T3 (de)
GB (1) GB8926718D0 (de)
IN (1) IN172032B (de)
MY (1) MY104539A (de)
ZA (1) ZA909477B (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2615165C2 (ru) * 2012-06-08 2017-04-04 Дзе Проктер Энд Гэмбл Компани Визуально контрастные частицы с эстетическими свойствами, характеризующиеся повышенной растворимостью в воде, особенно эффективные в комбинации с порошковыми или гранулированными композициями

Families Citing this family (8)

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Publication number Priority date Publication date Assignee Title
US5563673A (en) * 1991-09-06 1996-10-08 Canon Kabushiki Kaisha Camera
GB9513327D0 (en) * 1995-06-30 1995-09-06 Uniliver Plc Process for the production of a detergent composition
GB9711359D0 (en) 1997-05-30 1997-07-30 Unilever Plc Detergent powder composition
GB9711356D0 (en) 1997-05-30 1997-07-30 Unilever Plc Particulate detergent composition
ID29296A (id) 1997-05-30 2001-08-16 Unilever Nv Komposisi deterjen butiran lembut yang bebas mengalir
GB9711350D0 (en) * 1997-05-30 1997-07-30 Unilever Plc Granular detergent compositions and their production
ATE260331T1 (de) * 1999-04-30 2004-03-15 Procter & Gamble Waschmittelzusammensetzungen in tablettenform
KR20040029501A (ko) * 2002-10-01 2004-04-08 김철홍 콜로이드성 은 입자 수용액을 이용한 무공해 콩나물재배방법

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54149707A (en) * 1978-05-17 1979-11-24 Lion Corp Detergent composition
GB2063289B (en) * 1979-11-13 1984-02-22 Unilever Ltd Low phosphate spray-dried powders
JPH0680160B2 (ja) * 1984-09-14 1994-10-12 花王株式会社 流動性の改良された高密度の粒状洗剤の製法
JPS6169897A (ja) * 1984-09-14 1986-04-10 花王株式会社 流動性の改良された高密度の粒状洗剤の製法
EP0229671B1 (de) * 1986-01-17 1991-03-13 Kao Corporation Granuliertes Reinigungsmittel von hoher Dichte
GB8817386D0 (en) * 1988-07-21 1988-08-24 Unilever Plc Detergent compositions & process for preparing them
CA1323277C (en) * 1988-04-29 1993-10-19 Robert Donaldson Process for preparing detergent compositions
GB8810193D0 (en) * 1988-04-29 1988-06-02 Unilever Plc Detergent compositions & process for preparing them

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2615165C2 (ru) * 2012-06-08 2017-04-04 Дзе Проктер Энд Гэмбл Компани Визуально контрастные частицы с эстетическими свойствами, характеризующиеся повышенной растворимостью в воде, особенно эффективные в комбинации с порошковыми или гранулированными композициями

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Publication number Publication date
ES2067658T3 (es) 1995-04-01
JPH03210398A (ja) 1991-09-13
JPH0762160B2 (ja) 1995-07-05
ZA909477B (en) 1992-07-29
BR9005981A (pt) 1991-09-24
KR950001687B1 (ko) 1995-02-28
IN172032B (de) 1993-03-20
KR910009910A (ko) 1991-06-28
CA2030451A1 (en) 1991-05-28
GB8926718D0 (en) 1990-01-17
MY104539A (en) 1994-04-30
CA2030451C (en) 1999-07-27
EP0430328A2 (de) 1991-06-05
AU6690690A (en) 1991-05-30
EP0430328A3 (en) 1991-07-31
DE69016945D1 (de) 1995-03-23
DE69016945T2 (de) 1995-06-14
AU627958B2 (en) 1992-09-03

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