WO1994004639A1 - Compositions liquides - Google Patents

Compositions liquides Download PDF

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Publication number
WO1994004639A1
WO1994004639A1 PCT/EP1993/002060 EP9302060W WO9404639A1 WO 1994004639 A1 WO1994004639 A1 WO 1994004639A1 EP 9302060 W EP9302060 W EP 9302060W WO 9404639 A1 WO9404639 A1 WO 9404639A1
Authority
WO
WIPO (PCT)
Prior art keywords
surfactant
composition according
primary alcohol
range
solvent
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.)
Ceased
Application number
PCT/EP1993/002060
Other languages
English (en)
Inventor
Francesco Maria Puerari
David Roscoe
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 NV
Original Assignee
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 NV filed Critical Unilever NV
Priority to AU47061/93A priority Critical patent/AU4706193A/en
Publication of WO1994004639A1 publication Critical patent/WO1994004639A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents
    • 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
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating 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
    • 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
    • C11D3/16—Organic compounds
    • C11D3/18—Hydrocarbons
    • 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
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • 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

  • the present invention relates to surfactant containing, liquid compositions which show improved storage stability, and in particular to carbonate containing compositions which are stable at low temperatures.
  • Powdered cleaning compositions consist mainly of builder or buffering salts such as phosphates, carbonates, silicates etc.
  • Such compositions display good inorganic soil removal, but they can be deficient in cleaning ability on organic soils such as the calcium and/or magnesium salts of fatty acids and fatty/greasy soils typically found in the domestic environment.
  • Liquid cleaning compositions generally comprise an organic solvent and have the great advantage that they can be applied to hard surfaces in neat or concentrated form so that a relatively high level of surfactant material and organic solvent is directly delivered onto the soil.
  • the surfactants used in commercial general purpose cleaners include one or both of linear alkyl benzene sulphonates and secondary alkane sulphonates.
  • liquid compositions are of particular utility in the cleaning of hard surfaces such as floors and walls and kitchen or bathroom surfaces as mentioned above and in cleaning soft furnishings such as upholstery, carpets, curtains etc.
  • cleaning soft furnishings such as upholstery, carpets, curtains etc.
  • Mixtures of linear alkyl benzene sulphonates with alcohol ethoxylates and optionally small amounts of fatty soaps comprise the surfactant system used in a number of successful commercial products.
  • the aforementioned surfactants are known to form stable systems. This stability is important on storage of the product, particularly at low temperatures, as phase separation of components, particularly relative separation of two or more of builders, solvent and surfactant is prevented.
  • the presence of sodium carbonate also buffers the pH of the product towards the alkaline, helping to saponify fats and oils and converting fatty acids into soaps while maintaining the pH in a region which is not particularly harmful to the skin providing that contact is not prolonged.
  • PAS primary alcohol sulphate
  • EP 107946 (P&G: 1982) which relates to liquid detergent compositions comprising Mg-PAS, a water soluble C 13 -C 18 alkane or alkene sulphonate and a water soluble alkyl ether sulphate.
  • EP 039110 (P&G: 1980) also relates to compositions comprising Mg-PAS, alkylbenzene sulphonate and alkyl ether sulphate.
  • a liquid, cleaning composition comprising:
  • surfactant comprising primary alcohol sulphate (i) and optionally one or more nonionic surfactant (ii) wherein at least 50%wt of the surfactant present is primary alcohol sulphate,
  • the potassium carbonate will be present as such at a level of l-20wt% on product. It should be noted that some or all of the potassium can be the potassium salt of the primary alcohol sulphate. Other sources of potassium ions can be employed: as a further alternative at least a part of the potassium may be supplied as potassium hydroxide: this has the advantage that the pH of the composition may be adjusted thereby.
  • a characteristic functional definition of the present invention is that it provides, isotropic, liquid cleaning composition comprising surfactant, and a carbonate salt, wherein at least 50%wt of the surfactant is a primary alcohol sulphate and wherein the carbonate salt does not precipitate out when the product is cooled to zero Celsius and stored for 24 hours at that temperature.
  • the preferred primary alcohol sulphate comprises a mixture of materials of the general formulation:
  • R is a C 8 to C 18 primary alkyl group and X is a solubilising cation. Suitable cations include sodium, magnesium, potassium, ammonium and mixtures thereof. Particularly preferred PAS molecules are those with a major proportion of C 10 -C 14 alkyl residues. These can be obtained by forming the PAS from fatty acids obtained from coconut oil although they can also be obtained from synthetic sources.
  • the final composition is such that the molar ratio of potassium ions to primary alcohol sulphate ions falls in the range 1:5 to 1:1 and is preferably around 1:2.
  • potassium carbonate ratios fall in the range 30:1 to 2:1, preferably 15:1 to 6:1.
  • Typical potassium carbonate contents are l-10%wt, preferably 2-5%wt.
  • compositions comprise 15-30% primary alkyl sulphate and 5-15% non-ionic surfactant.
  • the preferred ratio of the PAS to the non-ionic is in the range 3:1 to 1:1 and is preferably around 2:1.
  • the preferred nonionic surfactant is selected from the group comprising ethoxylated alcohols of the general -formula:
  • R 2 is straight or branched, C 8 to C 18 alkyl and the average degree of ethoxylation m is 1-14, preferably 3-8.
  • the starting materials for the synthesis of these ethoxylated alcohols, a minor component of the surfactant system, ' are available from both natural and synthetic sources.
  • the composition further comprises a solvent other than water.
  • Typical solvent contents are l-30%wt of the composition, preferably 5-20% of the composition.
  • Preferred ranges for the surfactant:solvent ratios fall in the range 1:1 to 10:1, preferably 2:1 to 5:1.
  • the presence of solvent is optional.
  • the solvent is selected from: propylene glycol mono n-butyl ether, dipropylene glycol mono n-butyl ether, propylene glycol mono t-butyl ether, dipropylene glycol mono t-butyl ether, diethylene glycol hexyl ether, ethyl acetate, methanol, ethanol, isopropyl alcohol, ethylene glycol monobutyl ether, di-ethylene glycol monobutyl ether and mixtures thereof.
  • Preferred solvents are selected from the group comprising ethanol (preferably as industrial methylated spirits), propylene glycol mono n-butyl ether (available as 'Dowanol PnB' [RTM] ) and di-ethylene glycol monobutyl ether
  • compositions of the invention can further comprise other components selected from the group comprising: perfumes, colours and dyes, hygiene agents, foam-control agents, viscosity modifying agents and mixtures thereof.
  • foam control agents comprise calcium sensitive soaps in combination with hydrocarbons.
  • compositions according to the present invention are isotropic.
  • An advantage of isotropic compositions, is that they need not be shaken vigorously before use.
  • compositions according to the present invention are transparent.
  • compositions form a clear solution when diluted with water.
  • compositions according to the present invention can contain a hydrophobic oil in combination with a calcium sensitive soap as a foam control system.
  • the hydrophobic oil is a linear or branched chain hydrocarbon, a terpene or a silicone oil. More preferably, the hydrophobic oil is a paraffin: most preferably having a 50%wt loss boiling point in the range 170-300, Celsius. The term 50% loss boiling point being intended to indicate that 50% of the weight of the paraffin can be distilled off at a temperature within this range. In general the limits of boiling points of paraffin suitable for use in the composition of the present invention lie between 171 and 250 Celsius. We have found that the isoparaffins, i.e. branched chain paraffins, are particularly effective when compared with other hydrophobic oils such as n-decane and n-tetradecane.
  • solubilised hydrophobic oil content of embodiments of the present invention is typically in the range 0.2-5wt%, preferably 1.0-2.0wt%.
  • the insoluble calcium salt-forming surfactant content of embodiments of the invention is 0.2-5%wt: the upper levels of this range being used for more highly concentrated compositions.
  • the insoluble calcium salt-forming surfactant content is in the range 1.0-2.0%wt.
  • Surfactants which form insoluble calcium salts include fatty acids and soluble salts of fatty acids (true 'soaps') with a suitable cation, preferably derived from fatty acids having an average carbon chain length in the range 8-24.
  • Alternative surfactants include surfactant sulphates and sulphonates: in general, anionic surfactants of which the calcium salt has a Krafft temperature above product use temperature.
  • the preferred ratio of insoluble calcium salt forming surfactant to hydrophobic oil is in the range 0.5-1:1-0.5, preferably about 1:1.
  • ISOPAR-L (RTM, ex Exxon), a branched hydrocarbon with a boiling point range of
  • PAS LIAL-123S (RTM ex. Eniche ) , a sodium salt of primary alcohol sulphate having an average alkyl chain length in the range C 12 -C 13 ;
  • BIODAC L5-S52 RTM: ex DAC
  • nonionic, ethoxylated alcohol surfactant having an average alkyl chain length in the range C12- C16 and average EO of 5.5-6.0.
  • CFA Coconut fatty acid (available commercially) ;
  • the quantity of metal hydroxide added was sufficient to bring the pH of the composition to pH 11 in all cases, rather than being exactly 0.2.
  • the precise quantity required is determined by experiment and is influenced by the free alkali level in the other components, particularly the PAS raw material .
  • the comparative examples Ex(2-5) were all found to form a precipitate identified by X-ray crystallography as sodium carbonate decahydrate after prolonged storage (more than 24 hours) at zero Celcius or after repeated (daily) freeze thaw cycles.
  • Example 2 shows that sodium carbonate leads to an unstable product and it can be seen from Example 3 that mere reduction in the level of carbonate has no effect .
  • Examples 4 and 5 demonstrate that use of potassium hydroxide to neutralise the fatty acid in the composition provides insufficient potassium ions.
  • Example 2 After freezing and subsequent re-heating to room temperature, a phase separation was observed and a lower layer of concentrated sodium carbonate solution formed. The separation of this layer was found to be irreversible without violent shaking of the product.
  • Example Ex(l) formed a semi-liquid slurry when stored under the same conditions as the control. When re-heated to room temperature the slurry became liquid without any phase separation. Even after multiple freeze/thaw cycles or prolonged storage at -15 Celsius there was no irreversible phase separation.

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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)

Abstract

L'invention décrit une composition nettoyante liquide comportant: a) 2-40 % en poids d'un tensioactif contenant du sulfate d'alcool primaire (i) et éventuellement un ou plusieurs tensioactifs non ioniques (ii) où au moins 50 % en poids du tensioactif présent est du sulfate d'alcool primaire, b) 1-30 % en poids d'un carbonate de potassium en phase aqueuse. Dans des formulations typiques selon la présente invention, la composition renferme également un solvant autre que de l'eau.
PCT/EP1993/002060 1992-08-11 1993-07-31 Compositions liquides Ceased WO1994004639A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU47061/93A AU4706193A (en) 1992-08-11 1993-07-31 Liquid compositions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9217001.8 1992-08-11
GB929217001A GB9217001D0 (en) 1992-08-11 1992-08-11 Liquid compositions

Publications (1)

Publication Number Publication Date
WO1994004639A1 true WO1994004639A1 (fr) 1994-03-03

Family

ID=10720158

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1993/002060 Ceased WO1994004639A1 (fr) 1992-08-11 1993-07-31 Compositions liquides

Country Status (3)

Country Link
AU (1) AU4706193A (fr)
GB (1) GB9217001D0 (fr)
WO (1) WO1994004639A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10947480B2 (en) 2016-05-17 2021-03-16 Conopeo, Inc. Liquid laundry detergent compositions

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100260693B1 (ko) * 1992-08-25 2000-07-01 알 브이 테이트 (로드니 비버스 테이트), 에이치 드로이. 씨. 지. 오닌크, 이. 에디, 산드라 웨드워즈 (에스 제이 에드워즈) 일차 알킬 술페이트 및 비이온계 계면활성제를 함유하는 액상 세정 조성물

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE573012A (fr) *
DE2038308A1 (de) * 1969-08-07 1971-03-25 Colgate Palmolive Co Herd- und Ofen-Reinigungsmittel
JPS60139262A (ja) * 1983-12-27 1985-07-24 ホーチキ株式会社 洗浄兼用消火薬剤
AU560848B2 (en) * 1982-09-09 1987-04-16 R & C Assets Pty Limited Oven cleaner
EP0295021A2 (fr) * 1987-06-10 1988-12-14 Albright & Wilson Limited Compositions détergentes liquides
EP0354010A2 (fr) * 1988-08-05 1990-02-07 Albright & Wilson Limited Compositions de nettoyage liquides
WO1991000901A1 (fr) * 1989-07-10 1991-01-24 Henkel Kommanditgesellschaft Auf Aktien Agents de lavage et de nettoyage liquides exempts de phosphates
WO1991016409A1 (fr) * 1990-04-25 1991-10-31 Unilever N.V. Compositions pour detergents liquides
EP0530708A2 (fr) * 1991-08-30 1993-03-10 ALBRIGHT & WILSON UK LIMITED Détergent liquide pour le linge

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE573012A (fr) *
DE2038308A1 (de) * 1969-08-07 1971-03-25 Colgate Palmolive Co Herd- und Ofen-Reinigungsmittel
AU560848B2 (en) * 1982-09-09 1987-04-16 R & C Assets Pty Limited Oven cleaner
JPS60139262A (ja) * 1983-12-27 1985-07-24 ホーチキ株式会社 洗浄兼用消火薬剤
EP0295021A2 (fr) * 1987-06-10 1988-12-14 Albright & Wilson Limited Compositions détergentes liquides
EP0354010A2 (fr) * 1988-08-05 1990-02-07 Albright & Wilson Limited Compositions de nettoyage liquides
WO1991000901A1 (fr) * 1989-07-10 1991-01-24 Henkel Kommanditgesellschaft Auf Aktien Agents de lavage et de nettoyage liquides exempts de phosphates
WO1991016409A1 (fr) * 1990-04-25 1991-10-31 Unilever N.V. Compositions pour detergents liquides
EP0530708A2 (fr) * 1991-08-30 1993-03-10 ALBRIGHT & WILSON UK LIMITED Détergent liquide pour le linge

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Derwent World Patents Index; Class D25, AN 85-219319 [36] *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10947480B2 (en) 2016-05-17 2021-03-16 Conopeo, Inc. Liquid laundry detergent compositions
US11572529B2 (en) 2016-05-17 2023-02-07 Conopeo, Inc. Liquid laundry detergent compositions

Also Published As

Publication number Publication date
GB9217001D0 (en) 1992-09-23
AU4706193A (en) 1994-03-15

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