EP0246896B1 - Detergenszusammensetzungen - Google Patents

Detergenszusammensetzungen Download PDF

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Publication number
EP0246896B1
EP0246896B1 EP87304524A EP87304524A EP0246896B1 EP 0246896 B1 EP0246896 B1 EP 0246896B1 EP 87304524 A EP87304524 A EP 87304524A EP 87304524 A EP87304524 A EP 87304524A EP 0246896 B1 EP0246896 B1 EP 0246896B1
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EP
European Patent Office
Prior art keywords
detergent
detergent composition
calcite
sodium
weight
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
EP87304524A
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English (en)
French (fr)
Other versions
EP0246896A1 (de
Inventor
Cornelis Gerhard Van Kralingen
Robert Ernst Niemantsverdriet
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
Original Assignee
Unilever PLC
Unilever NV
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Publication date
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to AT87304524T priority Critical patent/ATE52535T1/de
Publication of EP0246896A1 publication Critical patent/EP0246896A1/de
Application granted granted Critical
Publication of EP0246896B1 publication Critical patent/EP0246896B1/de
Anticipated expiration legal-status Critical
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates

Definitions

  • This invention relates to detergent compositions, in particular built detergent compositions with low or zero levels of phosphate.
  • Detergent compositions conventionally include, in addition to a detergent ac- five material, a phosphate detergency builder, such as sodium tripolyphosphate.
  • a phosphate detergency builder such as sodium tripolyphosphate.
  • Belgium Patent 861 435 discloses a phosphate-free particulate detergent composition comprising both an alkali metal carbonate and bicarbonate, zeolite and a nonionic detergent.
  • a detergent composition which can be substantially free of phosphate builders, and which includes an alkali metal carbonate and an aluminosilicate material, by the addition of a seed crystal.
  • a detergent composition comprising at least one synthetic detergent active material, an alkali metal carbonate and a water-insoluble aluminosilicate, ion-exchange builder, characterised in that it further comprises at least 1% by weight of a calcium carbonate seed crystal having a surface area of at least 2 m2/g.
  • the detergent composition according to the invention necessarily includes a synthetic detergent active material otherwise referred to herein simply as a detergent compound.
  • the detergent compound may be selected from anionic, nonionic, zwitterionic and amphoteric synthetic detergent active materials and mixtures thereof. Many suitable detergent compounds are commercially available and are fully described in the literature, for example in "Surface Active Agents and Detergents", Volumes I and li, by Schwartz, Perry and Berch.
  • a suitable level of the detergent compound in the composition is from 5% to 40%, preferably from 10% to 25% by weight.
  • 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 about 8 to about 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 (C s - d e ) alcohols produced for example from tallow or coconut oil, sodium and potassium alkyl (C 9 ⁇ C 20 ) benzene sulphonates, particularly sodium linear secondary alkyl (C 10 -C 15 ) 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 (Ce-C1e) 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 neutralised with sodium hydroxide; sodium and potassium salts of fatty acid amides of
  • 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.
  • nonionic detergent compounds are alkyl (C 6 -C 22 ) phenols-ethylene oxide condensates, generally up to 25 EO, ie up to 25 units of ethylene oxide per molecule, the condensation products of aliphatic (C 8 -C 18 ) primary or secondary linear or branched alcohols with ethylene oxide, generally up to 40 EO, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine.
  • Other so-called 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 may be used in the detergent compositions, particularly in the latter case to provide controlled low sudsing properties. This is beneficial for compositions intended for use in suds-intolerant automatic washing machines.
  • Amounts of amphoteric or zwitterionic detergent compounds can also be used in the compositions of the invention but this is not normally desired due 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.
  • mixtures of amine oxides and ethoxylated nonionic detergent compounds can be used.
  • Soaps may also be present in the detergent compositions of the invention:
  • the soaps are particularly useful at low levels in binary and ternary mixtures, together with nonionic or mixed synthetic anionic and nonionic detergent compounds, which have low sudsing properties.
  • the soaps which are used are the water-soluble salts of C 10 -C 20 fatty acids in particular with inorganic cations such as sodium and potassium. It is particularly preferred that the soaps should be based mainly on the longer chain fatty acids within this range, that is with at least half of the soaps having a carbon chain length of 16 or over.
  • soaps from natural sources such as tallow, palm oil or rapeseed oil, which can be hardened if desired, with lesser amounts of other shorter chain soaps, prepared from nut oils such as coconut oil or palm kernel oil.
  • the amount of such soaps can be up to about 20% by weight, with lower amounts of 0.5% to about 5% being generally sufficient for lather control. Amounts of soap between 2% and 20%, especially between 5% and 15%, can advantageously be used to give a beneficial effect on detergency and reduced levels of incrustation.
  • the alkali metal carbonate and water insoluble aluminosilicate are used as detergency builder materials in the present invention.
  • the alkali metal carbonate is preferably selected from carbonates and sesquicarbonates of sodium and potassium and is most preferably sodium carbonate.
  • the alkali metal carbonate is preferably present in the detergent composition at a level of 5% to 50% by weight, most preferably from 10% to 40% by weight of the composition.
  • the aluminosilicate builder is preferably crystalline or amorphous material having the general formula: Naz (AIC ⁇ )z (Si0 2 ) Y x H 2 0 wherein Z and Y are integers of at least 6, the molar ratio of Z to Y is in the range from 1.0 to 0.5, and x is an integer from 15 to 264 such that the moisture content is from 10% to 28% by weight.
  • the alumino-silicate preferably has a particle size of from 0.1 to 100 microns, ideally between 0.1 and 10 microns and a calcium ion exchange capacity of at least 200 mg.calcium carbonate/g.
  • the water-insoluble aluminosilicate ion exchange material has the formula Nai2(Al 02SiO2)12XH20 wherein x is an integer of from 20 to 30, preferably about 27. This material is available commercially as Zeolite A.
  • the aluminosilicate material is preferably present in the detergent composition at a level within the range from 1% to 40%, based on the anhydrous material, by weight of the composition.
  • the essential alkali metal carbonate and aluminosilicate material it is possible to include minor amounts of other precipitating builder materials, other ion-exchange builder materials and sequestering builder materials.
  • the further builder material is a non-phosphate material.
  • the calcium carbonate seed crystal is any crystalline form of calcium carbonate, such as calcite, aragonite or travertine or a mixture thereof.
  • the seed crystal is calcite.
  • the calcium carbonate seed crystal preferably has a surface area of at least 30m 2 /g. A level from at least 1% to a preferred upper limit of 10% by weight of the seed crystal in the detergent composition is used. Below a level of 1% the addition of calcite has no effect on the detergency of the detergent composition. No further improvement in detergency is found if more than 10% by weight of calcite is added to the detergent composition.
  • a detergent composition according to the invention may contain any of the conventional additives in the amounts in which such materials are normally employed in fabric washing detergent compositions.
  • these additives include lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, lather depressants, antiredeposition agents, such as sodium carboxymethyl cellulose and cellulose ethers, oxygen- releasing bleaching agents such as sodium perborate and sodium percarbonate, peracid bleach precursors, chlorine-releasing bleaching agents, fabric softening agents, inorganic salts, such as sodium sulphate, and usually present in very minor amounts fluorescent agents, perfumes, germicides and colourants.
  • lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids
  • lather depressants such as sodium carboxymethyl cellulose and cellulose ethers
  • antiredeposition agents such as sodium carboxymethyl cellulose and cellulose ethers
  • an amount of an alkali metal silicate particularly sodium ortho-, meta- or preferably neutral or alkaline silicate.
  • alkali metal silicates at levels of at least 1%, and preferably from 3% to 15%, by weight of the composition, is advantageous in decreasing the corrosion of metal parts in washing machines, besides giving processing benefits and generally improved powder properties.
  • the more highly alkaline ortho- and metasilicates would normally only be used at lower amounts within this range, in admixture with the neutral or alkaline silicates.
  • detergent compositions of the invention it is generally also desirable to include a structurant material, such as succinic acid, and/or other dicarboxylic acids, sucrose and polymers, in detergent compositions of the invention, to provide a powder having excellent physical properties.
  • a structurant material such as succinic acid, and/or other dicarboxylic acids, sucrose and polymers
  • succinic acid this can react with the alkali metal carbonate present to give an alkali-metal bicarbonate, or sesquicarbonate.
  • Detergent compositions according to the invention may be produced by any of the techniques commonly employed in the manufacture of fabric washing detergent compositions, including particularly slurry- making and spray-drying processes.
  • the calcium carbonate seed crystal and the following optional components, the silicate material, enzyme, bleach and perfume may be post-dosed to a spray-dried powder comprising the detergent active, the detergency builders and any other optional materials.
  • the water softening capacity of a number of co-builders when added to zeolite A was examined. Two grams of zeolite were added to a litre of 40 ° FH water. (The water hardness was adjusted using stock solutions of calcium chloride). After one minute, 1g (occasionally 2g) of a co- builder was added. Experiments were carried out at ambient temperature and at 40 ° C. Values of pCa for each solution were determined using conventional methods.
  • the detergent composition comprised 20% zeolite A, 20% sodium carbonate, 9% alkyl benzene sulphonate (DOBS JN) and 4% of an alkoxylated alcohol (Synperonic A7) and was present at a level of 5g/l.
  • Figure 1 shows graphically the variation of pCa with the concentration of calcite, where the level of calcite is based on the weight of sodium carbonate present in the composition.
  • Calcite Socal U3
  • sodium perborate monohydrate and alkaline sodium silicate were post-dosed to a spray-dried powder detergent composition
  • a spray-dried powder detergent composition comprising 8.1% alkyl benzene sulphonate (Sirene X12L, ex SIR), 3.6% of an alkoxylated alcohol (Lutensol AO-7, ex BASF), 3.7% soap, 27.7% sodium carbonate, 18% zeolite A, 6.5% sodium sulphate, 2% succinic acid, and minor quantities of other conventional detergent additives.
  • the sodium perborate monohydrate and alkaline sodium silicate were present at levels of 9% and 5% respectively in the detergent composition.
  • a composition was prepared in which the calcite was replaced by an equivalent amount of sodium sulphate.
  • the compositions were added to water of varying hardness and pCa values were measured. The following results were obtained.
  • test cloths were washed in a laboratory apparatus with a detergent composition (X) comprising 9% alkyl benzene sulphonate (DOBS JN), 4% of an alkoxylated alcohol (Synperonic A7), 20% zeolite A, 20% sodium carbonate, 2% calcite (Socal U3), 10% sodium sulphate, 5% alkaline sodium silicate and 0.5% sodium carboxylmethyl cellulose.
  • X alkyl benzene sulphonate
  • Synperonic A7 an alkoxylated alcohol
  • zeolite A 20% sodium carbonate
  • 2% calcite Socal U3
  • 10% sodium sulphate 5% alkaline sodium silicate
  • 0.5% sodium carboxylmethyl cellulose a detergent composition
  • Test cloths were also washed in the same detergent composition except that it contained no calcite (Detergent composition Y ).
  • test cloths were then dried and the value of A R at 460 nm was determined using a "Zeiss Elrepho" reflectometer fitted with a UV filter ( A R represents the difference in the value of the reflectance of the test cloth compared to the untreated cloth). Triplicate experiments were performed and the following results were obtained.
  • Test cloths were washed at 40 ° C with the detergent composition present at a level of 4g/l.
  • Test cloths were washed at 40 ° C with the detergent composition present at a level of 8g/l.
  • Calcite sodium perborate monohydrate and alkaline sodium silicate were as post-dosed to a spray-dried powder detergent composition
  • a spray-dried powder detergent composition comprising 8.1% alkyl benzene sulphonate (Sirene X12L, ex SIR), 3.6% of an alkoxylated alcohol (Lutensol AO-7, ex BASF), 3.7% soap, 27.7% sodium carbonate, 18% zeolite A, 6.5% sodium sulphate, 2% succinic acid, and minor quantities of other conventional detergent additives.
  • the sodium perborate monhydrate and alkaline sodium silicate were present at levels of 9% and 5% respectively in the detergent composition.
  • Test cloths were washed in a laboratory apparatus with each of the above detergent compositions. The experiments were carried out in 40 ° FH water at a temperature of 60 ° C with a concentration of the detergent composition of 5g/l, the duration of the wash cycle was 20 minutes. The test cloths were then dried and the value of A R at 460nm was determined using a "Zeiss Elrepho" reflectometer fitted with a UV filter. ( A R is defined as in Example 4).
  • ° FH with respect to water hardness is the molar concentration of free hard water ions x 10-4.
  • pCa is the negative logarithm of the free calcium ion concentration.

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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 (6)

1. Detergenszusammensetzung enthaltend mindestens ein synthetisches detergensaktives Material, ein Alkalimetallcarbonat und einen wasserunlöslichen Aluminiumsilikat-lonenaustausch-Builder, dadurch gekennzeichnet, daß sie zusätzlich mindestens 1 Gew.-% eines Calciumcarbonatkristallkeims mit einer Oberfläche von mindestens 2 m2/g enthält.
2. Detergenszusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß sie etwa 5 bis etwa 40 Gew.-% synthetisches detergensaktives Material, etwa 1 bis etwa 40 Gew.-% eines wasserunlöslichen Aluminiumsilikats auf Basis von wasserfreiem Material, 5 bis 50 Gew-.% eines Alkalimetallcarbonats und 1 bis 10 Gew.-% eines Calciumcarbonatkristallkeims enthält.
3. Detergenszusammensetzung nach den Ansprüchen 1 oder 2, dadurch gekennzeichnet, daß das synthetische detergensaktive Material ausgewählt ist aus synthetischen anionischen, nichtionischen, amphoteren oder zwitterionischen Detergensverbindungen oder Mischungen davon.
4. Detergenszusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß der Calciumcarbonatkristallkeim Calcit ist.
5. Detergenszusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß der Calciumcarbonatkristallkeim eine Oberfläche von mindestens 30 m2/g aufweist.
6. Detergenszusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß der wasserunlösliche Aluminiumsilikat-Builder ein Zeolith ist.
EP87304524A 1986-05-23 1987-05-21 Detergenszusammensetzungen Expired - Lifetime EP0246896B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87304524T ATE52535T1 (de) 1986-05-23 1987-05-21 Detergenszusammensetzungen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB868612705A GB8612705D0 (en) 1986-05-23 1986-05-23 Detergent compositions
GB8612705 1986-05-23

Publications (2)

Publication Number Publication Date
EP0246896A1 EP0246896A1 (de) 1987-11-25
EP0246896B1 true EP0246896B1 (de) 1990-05-09

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ID=10598406

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Application Number Title Priority Date Filing Date
EP87304524A Expired - Lifetime EP0246896B1 (de) 1986-05-23 1987-05-21 Detergenszusammensetzungen

Country Status (13)

Country Link
EP (1) EP0246896B1 (de)
JP (1) JPS62288695A (de)
KR (1) KR900004537B1 (de)
AT (1) ATE52535T1 (de)
AU (1) AU579513B2 (de)
BR (1) BR8702650A (de)
CA (1) CA1314189C (de)
DE (1) DE3762628D1 (de)
ES (1) ES2015576B3 (de)
GB (1) GB8612705D0 (de)
IN (1) IN166763B (de)
TR (1) TR24555A (de)
ZA (1) ZA873657B (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2238315A (en) * 1989-11-24 1991-05-29 Unilever Plc Detergent composition
WO1998040457A1 (en) * 1997-03-11 1998-09-17 The Procter & Gamble Company Builder mixture containing crystalline calcium carbonate builder for use in detergent compositions
GB2415964B (en) * 2004-07-03 2008-04-16 Appaya Raghunath Naik Detergent formulations based on soap and fatty acid N-methyl glucamides
WO2007017619A1 (en) * 2005-08-10 2007-02-15 Appaya Raghunath Naik Detergent formulations based on soap and fatty acid n-methyl glucamide
CN112500936B (zh) * 2020-12-11 2024-03-19 纳爱斯集团有限公司 洗衣粉及其生产工艺、造粒粉和造粒粉的造粒工艺

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1471278A (en) * 1973-07-06 1977-04-21 Colgate Palmolive Co Liquid abrasive compositions
US4347152A (en) * 1976-12-02 1982-08-31 Colgate-Palmolive Company Phosphate-free concentrated particulate heavy duty laundry detergent
US4399048A (en) * 1977-10-06 1983-08-16 Colgate-Palmolive Company High bulk density particulate heavy duty laundry detergent
PH17712A (en) * 1979-10-12 1984-11-19 Unilever Nv Detergent bars
DE3534888A1 (de) * 1984-10-02 1986-04-10 Toyo Soda Manufacturing Co., Ltd., Shinnanyo, Yamaguchi Koernige zeolith-zusammensetzung als builder und sie enthaltendes waschmittel

Also Published As

Publication number Publication date
BR8702650A (pt) 1988-02-23
ES2015576B3 (es) 1990-09-01
TR24555A (tr) 1991-11-21
GB8612705D0 (en) 1986-07-02
EP0246896A1 (de) 1987-11-25
AU7321187A (en) 1987-11-26
ZA873657B (en) 1989-01-25
KR900004537B1 (ko) 1990-06-29
IN166763B (de) 1990-07-14
DE3762628D1 (de) 1990-06-13
AU579513B2 (en) 1988-11-24
CA1314189C (en) 1993-03-09
JPS62288695A (ja) 1987-12-15
ATE52535T1 (de) 1990-05-15
KR870011238A (ko) 1987-12-22

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