EP0021830B1 - Low sudsing detergent compositions - Google Patents

Low sudsing detergent compositions Download PDF

Info

Publication number
EP0021830B1
EP0021830B1 EP80302130A EP80302130A EP0021830B1 EP 0021830 B1 EP0021830 B1 EP 0021830B1 EP 80302130 A EP80302130 A EP 80302130A EP 80302130 A EP80302130 A EP 80302130A EP 0021830 B1 EP0021830 B1 EP 0021830B1
Authority
EP
European Patent Office
Prior art keywords
detergent composition
composition according
foam
surfactant
mixture
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
Application number
EP80302130A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0021830A1 (en
Inventor
Derek Nicholls
William Buckley Temple
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
Priority to AT80302130T priority Critical patent/ATE3779T1/de
Publication of EP0021830A1 publication Critical patent/EP0021830A1/en
Application granted granted Critical
Publication of EP0021830B1 publication Critical patent/EP0021830B1/en
Expired legal-status Critical Current

Links

Images

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
    • C11D1/02—Anionic compounds
    • C11D1/34—Derivatives of acids of phosphorus
    • C11D1/345—Phosphates or phosphites
    • 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
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions

Definitions

  • This invention relates to detergent compositions intended for fabric washing.
  • low-sudsing compositions are the so-called "ternary" products, i.e. those based on mixtures of anionic surfactants, most commonly long chain alkyl benzene sulphonates and nonionic surfactants in which the sudsing capacity is controlled by the use of a calcium soap, formed in situ by the reaction of sodium salts of fatty acids and calcium ions forming part of the water hardness.
  • the nonionic surfactant also exerts an effect in controlling foam in these formulations as well as contributing to the detergency properties of the system.
  • the detergencies obtained from the compositions outlined above, which are embodied in consumer products such as "Persil Automatic” and “Bold Automatic” (registered Trade Marks) are quite acceptable.
  • a detergent composition comprising a primary or secondary alkyl sulphate surfactant or mixture of such surfactants and a non-soap anti-foam, characterized In that:
  • DE-A-2 544 707 discloses detergent compositions containing anionic sulphate surfactants and non-soap anti-foams in general, although the invention is mainly concerned with capped nonionic surfactants and their use.
  • the non-soap anti-foams which are disclosed do not include the mixtures of phosphate esters with waxes and oils which are claimed in the present application.
  • DE-A-2 650 971 discloses detergent compositions containing phosphate esters, but in the case the ' compositions are designed to be high foaming and the ester is present as a draining aid rather than a foam depressant.
  • the critical micelle concentration determines the point at which a substance attains maximum surface activity.
  • both the solubility product and the critical micelle concentration are measured at 60°C in the presence of 0.05 moles/litre of sodium chloride.
  • mixtures of different detergent active sulphates can be used, providing that the solubility product and critical micelle concentration of the mixture lies in the required range.
  • the anionic surfactant may be present in the mixture in an amount of from 5 to 35%, preferably, for economic reasons, from 5 to 25% by weight of the composition.
  • the specified anionic surfactants are sulphates rather than sulphonates, since in general the sulphates are much more biodegradable than the sulphonates.
  • sulphate class primary and secondary alkyl sulphates are preferred.
  • the high crystalline fraction secondary alkyl sulphates i.e. those in which a high percentage of the material has the sulphate group attached at the 2 or 3 position
  • the C ie-18 sulphates and the C 15-16 primary alcohol sulphates are particularly preferred.
  • the second essential component of the compositions of this invention is a non-soap anti-foam compound in the form of a phosphate ester or salt thereof, used in conjunction with waxes or oils such as mineral and vegetable oils.
  • non-soap anti-foam compounds of this invention may be present in the compositions in amounts from 0.05%, which would be the minimum amount which could possibly be effective, to 5%, which would be the practical maximum having regard to the extreme efficacy of the majority of non-soap anti-foam compounds, to their expense and to the necessity for keeping as much room in the composition as possible for other compounds.
  • the phosphate esters which may be used, optionally in salt form, having the following general formula: where A is -OH or R 2 O(EO) m ⁇ , R 1 and R 2 are the same or different C 12 ⁇ C 24 , preferably C 16 ⁇ C 22 , straight or branched chain, saturated or unsaturated alkyl groups, especially C 16 ⁇ C 18 linear saturated groups and m and n are the same or different and are 0 or an integer of from 1 to 6.
  • A is -OH and n is 0, so that the compounds are the monoalkyl phosphoric acids, preferably with linear alkyl groups. If any ethylene oxide (EO) groups are present in the alkyl phosphoric acids, they should not be too long in relation to the alkyl chain length to make the calcium or magnesium salts soluble in water during use.
  • EO ethylene oxide
  • the alkyl phosphate compounds are commonly mixtures of both mono- and di-alkyl phosphoric acids, with a range of alkyl chain lengths.
  • Predominantly monoalkyl phosphates are usually made by phosphorylation of alcohols or ethoxylated alcohols, when n or m is 1 to 6, using a polyphosphoric acid. Phosphorylation may alternatively be accomplished using phosphorus peroxide, in which case the mixed mono- and di-alkyl phosphates are produced. Under optimum reaction conditions only small quantities of unreacted materials or by-products are produced, and the reaction products can advantageously be used directly in the detergent compositions.
  • the wax may be of synthetic, mineral, vegetable or animal origin.
  • the waxes should normally melt at a temperature between 20°C and 120°C, preferably not more than 90°C and especially in the range of 30°C to 70°C (melting or softening point), i.e. lower than the maximum Intended wash temperatures for the detergent compositions.
  • waxes having melting points above the maximum intended wash temperatures they should be adequately dispersed In the wash liquor by suitable incorporation in the original detergent compositions.
  • the preferred waxes are of mineral origin, especially those derived from petroleum, including microcrystalline and oxidised microcrystalline petroleum waxes, petroleum jelly ("Vaseline”) and paraffin waxes.
  • Petroleum jelly is correctly a semi-solid wax, usually having a melting point of from, 30-40°C, but is for convenience here grouped with other solid waxes.
  • Synthetic waxes such as Fischer-Tropsch and oxidised Fischer-Tropsch waxes, or Montan waxes, or natural waxes such as beeswax, candelilla and carnauba waxes may be used if desired. Any of the waxes described may be used alone or in admixture with other waxes.
  • the waxes should be readily dispersible in the detergent liquor but not soluble therein and, preferably, they should not have very high saponification values, e.g. not in excess of about 100. It is advantageous to include emulsifying or stabilising agents for the waxes in the detergent compositions.
  • oils which may be used if desired are vegetable oils such as sesame oil, cotton seed oil, corn oil, sweet almond oil, olive oil, wheat germ oil, rice bran oil, or peanut oil, or animal oils such as lanolin, neat's foot oil, bone oil, sperm oil or cod liver oil. Any such oils used should of course not be highly coloured, of strong odour or otherwise unacceptable for use in a detergent composition.
  • Sodium ortho-, pyro- and tripolyphosphates are amongst several suitable detergency builders which are well known and commercially available, whilst many more have been described in the literature, especially in recent patent specifications on replacements for these phosphate based materials.
  • Other detergency builders which may be mentioned by way of example are alkali metal carbonates, especially sodium carbonate, alkali metal polyphosphonates, e.g.
  • sodium ethane-1-hydroxy-1,1-diphosphonate alkali metal amine carboxylates, such as sodium nitrilotriacetate and sodium ethylenediamine tetraacetate, alkali metal ether carboxylates, such as sodium oxydiacetate, sodium carboxymethyloxysuccinate, sodium carboxymethyloxymalonate and homologues thereof, alkali metal citrates, alkali metal mellitates and salts of polymeric carboxylic acids, such as sodium polymaleate, copolyethylenemaleate, polyitaconate and polyacrylate.
  • sodium carbonate Is used as a detergency builder it is advantageous to have present some calcium carbonate having a surface area of at least 10 m 2 /g, as described in GB-A-1,437,950.
  • detergency builder which can be used, either alone or in admixture with other builders, is a cation exchange material, especially a sodium aluminosilicate such as described in GB-A-1,429,143 or in NL-A-7403381.
  • Preferred materials of this type have the formula: and may be amorphous or crystalline, with some bound water usually in an amount of 10 ⁇ 30% depending on the drying conditions used.
  • Such sodium aluminosilicate materials should, of course, be very finely divided so as to minimise deposition on the fabrics during washing.
  • the amount of the detergency builder which is used is normally from 5% up to 80% by weight of the composition, preferably 10% to 60%, and the ratio by weight of the detergency builders to the detergent active compounds which are used is generally from 10:1 to 1:5 parts by weight.
  • the detergent compositions of the invention may take any of the usual physical forms, preferably as solid compositions, for example as powders, granules, flakes, ribbons, noodles or tablets, or they may be in liquid or paste form.
  • the detergent compositions may also be made by any of the conventional processes for making detergent compositions, especially by the technique of slurry making and spray-drying in the case of the preferred powder detergent compositions.
  • the detergent compositions of the invention may also include any of the conventional optional additives in the amounts usually employed in detergent compositions.
  • these additives include powder flow aids such as finely divided silicas and aluminosilicates, other lather controllers, anti-redeposition agen;a such as sodium carboxymethylcellulose, oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate, per-acid bleach precursors such as tetraacetyl- ethylenediamine, chlorine-releasing bleaching agents such as trichloroisocyanuric acid and alkali metal salts of dichloroisocyanuric acid, fabric softening agents such as clays of the smectite and illite types, anti-ashing aids, starches, slurry stabilisers such as copolyethylenemaleic anhydride and copolyvinyl- methylether-maleic anhydride, usually in salt form, inorganic salts such as sodium silicates and sodium sulphate, and usually present
  • the detergent compositions usually have an alkaline pH, generally in the region of pH 9-11, which is achieved by the presence of alkaline salts, especially sodium silicates such as the meta-, neutral or alkaline silicates, preferably at levels up to about 15% by weight.
  • alkaline salts especially sodium silicates such as the meta-, neutral or alkaline silicates
  • a series of fabric washing powders having the following formulation were prepared by spray-drying and post-dosing techniques.
  • the anionic detergent in each formulation is shown in Table 3.
  • the non-soap anti-foam was a 90:20 mixture of (i) petroleum jelly and (ii) Alf 5 (registered trade mark) which is a mixture of the sodium salts of mono- and di- C 16 alkyl phosphates.
  • the powders were used to wash polyester cotton test cloths soiled with a soil consisting of a mixture of inorganic materials and a synthetic sebum.
  • the detergent efficiency was followed by determining the reflectance of the washed cloth and expressing this as a percentage of the reflectance of the unsoiled cloth.
  • the washing procedures were carried out in Tergotometers (registered Trade Mark) using water of 40° French hardness, a temperature of 60°C, a product concentration of 0.15% and a 50 cpm agitation rate.
  • Two detergent powders according to the following formulation were prepared by spray-drying and post-dosing techniques.
  • the anionic detergent was the sodium salt of C 16 ⁇ C 18 high crystalline fraction secondary alkyl sulphate (SALS) and in the other it was the sodium salt of C 12.5 alkyl benzene sulphonate (DOBS-055) prepared by sulphonation of dodecylbenzene obtained from Shell Chemicals Limited as DOBS-055.
  • SALS secondary alkyl sulphate
  • DOBS-055 C 12.5 alkyl benzene sulphonate
  • test pieces were assessed by a panel of trained assessors. The results are shown in Table 4.
  • Lather heights were measured every 3 minutes using an arbitrary scale on the window of the machine.

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)
  • Detergent Compositions (AREA)
EP80302130A 1979-06-27 1980-06-25 Low sudsing detergent compositions Expired EP0021830B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80302130T ATE3779T1 (de) 1979-06-27 1980-06-25 Schwach schaeumende reinig ungsmittelzusammensetzungen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB7922438 1979-06-27
GB7922438 1979-06-27

Publications (2)

Publication Number Publication Date
EP0021830A1 EP0021830A1 (en) 1981-01-07
EP0021830B1 true EP0021830B1 (en) 1983-06-15

Family

ID=10506148

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80302130A Expired EP0021830B1 (en) 1979-06-27 1980-06-25 Low sudsing detergent compositions

Country Status (6)

Country Link
EP (1) EP0021830B1 (nl)
JP (1) JPS5611996A (nl)
AT (1) ATE3779T1 (nl)
DE (1) DE3063761D1 (nl)
MY (1) MY8600602A (nl)
ZA (1) ZA803843B (nl)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4363740A (en) * 1980-07-29 1982-12-14 Lever Brothers Company Process for making controlled sudsing detergent powder
ATE23560T1 (de) * 1982-02-04 1986-11-15 Unilever Nv Verfahren zur herstellung von schwach schaeumenden detergenszusammensetzungen.
EP0693109A1 (en) * 1993-04-08 1996-01-24 The Procter & Gamble Company Calcium-containing detergent compositions in stable liquid, gel or other forms with secondary (2,3) alkylsulfate surfactants
DE69408532D1 (de) * 1993-04-08 1998-03-19 Procter & Gamble Magnesium enthaltende reinigungsmittel in stabilen flüssigen, gelförmigen oder anderen formen mit sekundären (2,3) alkylsulfat tensiden
CA2160106A1 (en) * 1993-04-08 1994-10-27 Bruce Prentiss Murch Secondary (2,3) alkyl sulfate surfactants in mixed surfactant particles
CA2169090C (en) * 1993-08-17 2000-06-20 Todd Edmund Wichmann Granular detergent composition containing secondary (2,3) alkyl sulfate surfactant and a bleach/bleach activator system

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3010907A (en) * 1957-04-09 1961-11-28 Pennsalt Chemicals Corp Alkaline cleaning compositions
GB1518670A (en) * 1974-10-14 1978-07-19 Procter & Gamble Ltd Low-sudsing detergent compositions
GB1562793A (en) * 1975-11-07 1980-03-19 Unilever Ltd Cleaning composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Chemische Technologie Bd. 4, pp. 449-450 *

Also Published As

Publication number Publication date
JPH031359B2 (nl) 1991-01-10
ZA803843B (en) 1982-01-27
ATE3779T1 (de) 1983-06-15
MY8600602A (en) 1986-12-31
EP0021830A1 (en) 1981-01-07
JPS5611996A (en) 1981-02-05
DE3063761D1 (en) 1983-07-21

Similar Documents

Publication Publication Date Title
EP0046342B1 (en) Detergent compositions and processes of making thereof
US4223163A (en) Process for making ethoxylated fatty alcohols with narrow polyethoxy chain distribution
US4888119A (en) Cationic/anionic surfactant complex antistatic and fabric softening emulsion for wash cycle laundry applications
US5332513A (en) Particulate fabric softening and detergent compositions
US4465613A (en) Alkyl phosphoric salt-hydrocarbon wax lather controlled detergent compositions
DK158521B (da) Detergentsammensaetning indeholdende peroxygenblegeforbindelser og blegeaktivatorer af carboxylsyreestertypen
US7354892B2 (en) Low suds laundry detergents with enhanced whiteness retention
JPH0332598B2 (nl)
US5204010A (en) Cationic/anionic surfactant complex antistatic and fabric softening emulsion for wash cycle laundry applications
US4362642A (en) Alkyl phosphoric acid polyvalent salts-mineral oil lather controlled detergent compositions
JPS6356600A (ja) 消泡成分
EP0008829A1 (en) Controlled sudsing detergent compositions
EP0021830B1 (en) Low sudsing detergent compositions
US4009114A (en) Non-phosphate detergent composition
IE51245B1 (en) Granular detergent compositions
CA1180970A (en) Process for making controlled sudsing detergent powder
EP0030859B1 (en) Process for making detergent compositions
EP0054436B2 (en) Controlled-sudsing detergent compositions
US4832863A (en) Low-foam phosphate-free detergent
EP0095904B1 (en) Detergent liquors and compositions for use therein
EP0131393A1 (en) Glyceryl monoester emulsifier systems for improved oily soil removal in detergent compositions
EP0182411B1 (en) Detergent compositions containing polymers
US3332874A (en) Detergent composition
CA1100382A (en) Liquid detergent compositions
CA1101753A (en) Low-phosphorus detergent compositions built with high- orthophosphate/low-pyrophosphate mixtures

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB IT NL SE

17P Request for examination filed

Effective date: 19810402

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: UNILEVER NV

Owner name: UNILEVER PLC

ITF It: translation for a ep patent filed

Owner name: JACOBACCI & PERANI S.P.A.

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB IT LI NL SE

REF Corresponds to:

Ref document number: 3779

Country of ref document: AT

Date of ref document: 19830615

Kind code of ref document: T

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: UNILEVER NV

Owner name: UNILEVER PLC

REF Corresponds to:

Ref document number: 3063761

Country of ref document: DE

Date of ref document: 19830721

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19840630

Year of fee payment: 5

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19860616

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Effective date: 19870625

BERE Be: lapsed

Owner name: UNILEVER N.V.

Effective date: 19870630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19890630

ITTA It: last paid annual fee
EAL Se: european patent in force in sweden

Ref document number: 80302130.2

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19960604

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19970510

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19970520

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19970523

Year of fee payment: 18

Ref country code: DE

Payment date: 19970523

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19970619

Year of fee payment: 18

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970630

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970630

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980625

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980626

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990101

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19980625

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990226

EUG Se: european patent has lapsed

Ref document number: 80302130.2

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19990101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990401

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST