EP0234818B1 - Detergent compositions - Google Patents

Detergent compositions Download PDF

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Publication number
EP0234818B1
EP0234818B1 EP87301227A EP87301227A EP0234818B1 EP 0234818 B1 EP0234818 B1 EP 0234818B1 EP 87301227 A EP87301227 A EP 87301227A EP 87301227 A EP87301227 A EP 87301227A EP 0234818 B1 EP0234818 B1 EP 0234818B1
Authority
EP
European Patent Office
Prior art keywords
composition according
water
composition
weight
detergent active
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
EP87301227A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0234818A2 (en
EP0234818A3 (en
Inventor
Ian Eric Niven
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
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 Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0234818A2 publication Critical patent/EP0234818A2/en
Publication of EP0234818A3 publication Critical patent/EP0234818A3/en
Application granted granted Critical
Publication of EP0234818B1 publication Critical patent/EP0234818B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C11D1/83—Mixtures of non-ionic with anionic 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • 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
    • 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
    • C11D3/1233—Carbonates, e.g. calcite or dolomite
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/42—Amino alcohols or amino ethers
    • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
    • 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
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • This invention relates to detergent compositions, in particular to detergent compositions intended to be used for washing fabrics in an automatic washing machine, and more especially to such compositions which contain little or no phosphorus containing materials.
  • Detergent compositions usually contain, in addition to a detergent active material, a detergency builder whose role, inter alia , is to remove hardness ions from the wash liquor which would otherwise reduce the efficiency of the detergent active material.
  • a detergency builder whose role, inter alia , is to remove hardness ions from the wash liquor which would otherwise reduce the efficiency of the detergent active material.
  • Water-soluble phosphate materials have been extensively used as detergency builders. However for a number of reasons, including eutrofication allegedly caused by phosphates and cost, there has been a desire to use alkali metal carbonates especially sodium carbonate instead. Alkali metal carbonate detergency builders suffer however from a number of disadvantages.
  • the reaction between the alkali metal carbonate and calcium ions which are present in hard water results in the formation of water-insoluble calcium carbonate which, depending on the conditions, may be in such a form as to become deposited on the washed fabrics.
  • the reaction between the alkali metal carbonate and the calcium ions of the water is slow, especially at low temperatures and is readily inhibited by materials which act as calcium carbonate precipitate growth inhibitors, referred to herein as poisons.
  • poisons materials which act as calcium carbonate precipitate growth inhibitors
  • the detergent active material may be chosen from a number of classes of materials but it is preferred to use a mixture of an anionic non-soap detergent active, a nonionic detergent active and soap.
  • detergent compositions containing such a ternary active system together with an alkali metal carbonate and calcite suffer from poor dispensability from automatic washing machines.
  • the user places an appropriate amount of detergent powder in a dispenser where it is retained until needed by the machine.
  • water enters the dispenser and washes the powder into a feed pipe leading to the washing compartment of the machine. If the powder is not substantially washed out of the dispenser by the process, not only is it wasted but after repeated use it will build up and eventually block the dispenser and/or the feed pipe. Alternatively, it requires the user to clean out the dispenser after each wash cycle.
  • UK Patent Specification GB 2 104 912 A describes at Example 8, a calcite/carbonate built composition having a ternary active system wherein the proportions of anionic, nonionic and soap within that system, fall within the ranges specified above. However, the composition does not fall within the above definition as a whole because the soap content is stated to be 12%. Moreover, the prior UK Specification contains no teaching, explicit or implicit, as to how one may obtain improved dispensing properties with calcite/carbonate built ternary systems.
  • soap content not to exceed 10% by weight of the total composition, it is preferred for this figure to be no more than 8%.
  • composition contains from 5% to 40% by weight of the detergent active system, preferably not more than 25%.
  • the detergent active mixture contains from about 35% to about 60% anionic active; from about 21% to about 26% nonionic active; and from about 15% to about 35% soap.
  • the non-soap (synthetic) anionic detergent active compound is usually the water-soluble alkali metal salt of an organic sulphate and sulphonate 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 (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 neutralised with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurine; alkane mono
  • Suitable nonionic detergent compounds 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 compounds are alkyl (C6-C22) phenols-ethylene oxide condensates, generally 5 to 25 EO, ie 5 to 25 units of ethylene oxide per molecule, the condensation products of aliphatic (C8-C18) primary or secondary linear or branched alcohols with ethylene oxide, generally 5 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.
  • the term "soap" includes not only the usual alkali metal and alkaline earth metal salts of fatty acids, but also the organic salts which can be formed by complexing fatty acids with organic nitrogen-containing materials such as amines and derivatives thereof.
  • the soap comprises salts of higher fatty acids containing from 8 to 24 carbon atoms, preferably from 10 to 20 carbon atoms in the molecule, or mixtures thereof.
  • soaps include sodium stearate, sodium palmitate, sodium salts of tallow, coconut oil and palm oil fatty acids and complexes between stearic and/or palmitic fatty acid and/or tallow and/or coconut oil and/or palm oil fatty acids with water-soluble alkanolamines such as ethanolamine, di- or triethanolamine, N-methylethanol- amine, N-ethylethanolamine, 2-methylethanolamine and 2,2-dimethyl ethanolamine and N-containing ring compounds such as morpholine, 2′-pyrrolidone and their methyl derivatives.
  • water-soluble alkanolamines such as ethanolamine, di- or triethanolamine, N-methylethanol- amine, N-ethylethanolamine, 2-methylethanolamine and 2,2-dimethyl ethanolamine and N-containing ring compounds such as morpholine, 2′-pyrrolidone and their methyl derivatives.
  • An essential ingredient of the composition is a water-soluble carbonate material as a builder.
  • This is preferably sodium or potassium carbonate or a mixture thereof, for reasons of cost and efficiency.
  • the carbonate salt is preferably fully neutralised but it may be partially neutralised, for example a sesquicarbonate may be used in partial replacement of the normal carbonate salt; the partial salts tend to be less alkaline and therefore less efficient.
  • the amount of water-soluble carbonate material in the detergent composition can be varied widely, but the amount should be at least 5% by weight, such as from 10% to 40%, preferably 10% to 35% by weight, though an amount of up to 75% could possibly be used if desired in special products
  • the amount of the water-soluble carbonate material is determined on an anhydrous basis, though the salts may be hydrated either before or when incorporated into the detergent composition. It should be noted that it may also be desirable to limit the carbonate content to a lower level within the range mentioned, so as to decrease the risk of internal damage following any accidental ingestion, for example by children.
  • the composition necessarily contains a water-insoluble particulate carbonate material.
  • This material must be capable of acting as a seed crystal for the precipitate which results from the reaction between the calcium hardness ions of the water and the water-soluble carbonate.
  • this water-insoluble particulate material is a seed crystal for calcium carbonate, such as calcium carbonate itself.
  • the water-insoluble particulate carbonate material should be finely divided, and should have a surface area of at least 10 m2/g, and preferably at least 15 m2/g.
  • the particularly preferred material has surface area from 30-100 m2/g. Insoluble carbonate material with surface areas in excess of 100 m2/g may be used, if such materials are economically available.
  • BET Brunauer, Emmet & Teller
  • the high surface area material be prepared in the absence of poisons, so as to retain its seed activity.
  • the insoluble carbonate material will usually have an average particle size of less than 10 ⁇ m, as measured by sieve analysis, but may be granulated for ease of handling.
  • any crystalline form thereof may be used or a mixture thereof, but calcite is preferred as aragonite and vaterite are less readily available commercially, and calcite is a little less soluble than aragonite or vaterite at most usual wash temperatures.
  • any aragonite or vaterite is used it is generally in admixture with calcite.
  • the term 'calcite' is used to mean either calcite itself or any other suitable water-insoluble calcium carbonate seed material.
  • the selected level of calcite in the overall composition depends on the specific surface area as described above.
  • the amount of calcite used in the compositions should be from 5% to 60%, more preferably from 5% to 30%.
  • the detergent active material and the water-soluble carbonate material it is possible to include minor amounts of other detergency builders, provided that the total amount of the detergency builders does not exceed 85% by weight, so as to leave room in the detergent composition for other desirable ingredients.
  • the detergent composition can optionally contain any of the conventional ingredients in the amounts in which such ingredients are normally employed in fabric washing detergent compositions.
  • One such optional ingredient is an alkali metal silicate, particularly sodium neutral, alkaline, meta- or orthosilicate.
  • a low level of silicate for example 5-10% by weight, is usually advantageous in decreasing the corrosion of metal parts in fabric washing machines, and it may give processing benefits. If higher levels of silicate are used up to a practical maximum of 30%, for example from 10% to 20% by weight, there can be a more noticeable improvement in detergency, which may permit some decrease in the water- soluble carbonate material content. This effect appears to be particularly beneficial when the wash liquor are used in water with appreciable levels of magnesium hardness.
  • the amount of silicate can also be used to some extent to control the equilibrium pH of the wash liquor, which is generally within the range of 9-11, preferably 10-11 for an aqueous solution of the composition at the recommended concentration. It should be noted that a higher pH (ie over pH 10.5) tends to be more efficient as regards detergency, but it may be less desirable for domestic safety.
  • Sodium silicate is commonly supplied in concentrated aqueous solution, but the amounts are calculated on an anhydrous basis.
  • 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, fabric softening agents, inorganic salts such as sodium sulphate, and, usually present in very minor amounts, fluorescent agents, perfumes, enzymes such as proteases and amylases, germicides and colourants.
  • 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, fabric softening agents, inorganic salts such as sodium sulphate, and, usually present in very minor
  • the detergent compositions 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 for the manufacture of detergent powders.
  • compositions were prepared according to the following formulations. Each composition was made in the form of a powder by spray drying a slurry of the stated components, with the exception of the sodium silicate, sodium perborate and TAED (when used), which were added separately to the spray dried base powder. The powders were sprayed to a target moisture content of 3-4%.
  • each example 150g of powder was placed in the dispenser of a HOOVER (Trade Mark) automatic washing machine.
  • Cold water was allowed to enter the dispenser at a rate of 2 litres per minute for 2 minutes.
  • the water had a hardness of 24°FH (ie a free calcium ion concentration of 24 x 10 ⁇ 4 molar).
  • the water pressure was 34.5 kPa (5 psi). After allowing the water to drain naturally out of the dispenser the weight of the powder residue therein was measured.
  • compositions according to the invention leave significantly less residue in the residue than the comparison compositions A to D.

Landscapes

  • 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)
EP87301227A 1986-02-14 1987-02-12 Detergent compositions Expired - Lifetime EP0234818B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB868603667A GB8603667D0 (en) 1986-02-14 1986-02-14 Detergent composition
GB8603667 1986-02-14

Publications (3)

Publication Number Publication Date
EP0234818A2 EP0234818A2 (en) 1987-09-02
EP0234818A3 EP0234818A3 (en) 1990-03-14
EP0234818B1 true EP0234818B1 (en) 1993-05-19

Family

ID=10593064

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87301227A Expired - Lifetime EP0234818B1 (en) 1986-02-14 1987-02-12 Detergent compositions

Country Status (12)

Country Link
EP (1) EP0234818B1 (cs)
JP (1) JPH0198700A (cs)
KR (1) KR900004494B1 (cs)
AU (1) AU581805B2 (cs)
BR (1) BR8700608A (cs)
DE (1) DE3785863T2 (cs)
ES (1) ES2054662T3 (cs)
GB (1) GB8603667D0 (cs)
IN (1) IN166157B (cs)
NO (1) NO168488C (cs)
TR (1) TR23702A (cs)
ZA (1) ZA871068B (cs)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8711423D0 (en) * 1987-05-14 1987-06-17 Unilever Plc Detergent composition
GB9008013D0 (en) * 1990-04-09 1990-06-06 Unilever Plc High bulk density granular detergent compositions and process for preparing them
KR100461096B1 (ko) * 1997-05-02 2005-04-06 주식회사 엘지생활건강 초고농축분말세제의제조방법
EP2366006B1 (en) * 2008-12-16 2013-08-14 Unilever NV Solid builder composition

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4076653A (en) * 1973-08-08 1978-02-28 Lever Brothers Company Detergent compositions
GB1481685A (en) * 1973-08-15 1977-08-03 Unilever Ltd Detergent ingredient
GB1515273A (en) * 1974-09-06 1978-06-21 Unilever Ltd Production of detergent compositions
US4407722A (en) * 1981-06-18 1983-10-04 Lever Brothers Company Fabric washing process and detergent composition for use therein
US4436637A (en) * 1982-12-13 1984-03-13 Colgate-Palmolive Company Fabric softening heavy duty liquid detergent containing a mixture of water insoluble soap and clay
GB8334017D0 (en) * 1983-12-21 1984-02-01 Unilever Plc Detergent composition

Also Published As

Publication number Publication date
NO870581L (no) 1987-08-17
AU581805B2 (en) 1989-03-02
EP0234818A2 (en) 1987-09-02
ZA871068B (en) 1988-10-26
JPH0198700A (ja) 1989-04-17
IN166157B (cs) 1990-03-24
KR900004494B1 (ko) 1990-06-28
NO168488B (no) 1991-11-18
NO168488C (no) 1992-02-26
DE3785863T2 (de) 1993-08-26
NO870581D0 (no) 1987-02-13
EP0234818A3 (en) 1990-03-14
JPH0545639B2 (cs) 1993-07-09
BR8700608A (pt) 1987-12-15
KR870008017A (ko) 1987-09-23
TR23702A (tr) 1990-06-29
AU6867387A (en) 1987-08-20
GB8603667D0 (en) 1986-03-19
DE3785863D1 (de) 1993-06-24
ES2054662T3 (es) 1994-08-16

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