EP0376704B1 - Bleaching composition - Google Patents

Bleaching composition Download PDF

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Publication number
EP0376704B1
EP0376704B1 EP89313623A EP89313623A EP0376704B1 EP 0376704 B1 EP0376704 B1 EP 0376704B1 EP 89313623 A EP89313623 A EP 89313623A EP 89313623 A EP89313623 A EP 89313623A EP 0376704 B1 EP0376704 B1 EP 0376704B1
Authority
EP
European Patent Office
Prior art keywords
hydrogen peroxide
surfactant
weight
stabiliser
viscosity
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
EP89313623A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0376704A1 (en
Inventor
David Ellis Clarke
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 EP0376704A1 publication Critical patent/EP0376704A1/en
Application granted granted Critical
Publication of EP0376704B1 publication Critical patent/EP0376704B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3937—Stabilising agents
    • C11D3/394—Organic 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid 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
    • 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
    • C11D1/143—Sulfonic 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
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides

Definitions

  • This invention relates to thickened liquid bleach compositions which may be suitable for sale and use as a domestic bleach.
  • Pourable domestic bleach is frequently thickened by including one or more surfactants which, in the presence of electrolyte, act to thicken the solution rendering it more viscous than water. Thickening of a pourable domestic bleach helps the user to control dispensing of the composition and retards drainage from surfaces to which it is applied.
  • This invention relates to such compositions which include surfactant and electrolyte to increase the viscosity.
  • the compositions of the invention may be pourable or may be even more viscous so as not to be poured easily.
  • a domestic bleach needs to be adequately stable so that a substantial proportion of the bleaching agent survives during storage between manufacture and use.
  • Prior to this invention commercial liquid bleach products have frequently utilised hypochlorite as bleaching agent.
  • US 3388069 discloses peroxide based compositions which have surface active properties due to the presence of C10-C24 amine oxides.
  • Amine oxides are amphoteric surfactants and are said to have some stabilizing effect on peroxides at a pH of up to 8.0 (see Lindner col. 2 line 69). It is believed that the compositions will not thicken in the absence of the anionic surfactant.
  • the compositions of Lindner do not have storage stability at higher pH: the compositions of Lindner are often stored at a rather lower pH than they are intended for use at, and an alkali is added before use.
  • any attempt to make a surfactant-thickened, alkaline domestic liquid bleach product using hydrogen peroxide as the bleaching agent would encounter the potential problem that the thickening of the solution would require the presence of some electrolyte but that this electrolyte would serve to accelerate decomposition of the peroxide.
  • a liquid, bleaching composition comprising an aqueous alkaline solution of pH 8.0-10.5, containing:
  • a surfactant as specified above is advantageous in achieving thickening with a fairly low electrolyte concentration. This may make it possible for the electrolyte to be provided by ions which are in the composition for other reasons, without deliberate addition of salt for the sole purpose of enhancing ionic strength. Apart from considerations of peroxide stability, a benefit of a low electrolyte concentration is a reduced tendency for the product to leave streaks on a surface which is cleaned with it.
  • a preferred possibility for the amphoteric surfactant is a trialkyl amine oxide with one long chain alkyl of 8 to 20 carbon atoms and two alkyl groups of 1 to 4 carbon atoms.
  • the weight ratio of amine oxide:alcohol sulphate is preferably in the range from 82:18 to 65:35, better 80:20 to 65:35, even better 80:20 to 70:30.
  • Alkane sulphonate is preferred over alcohol sulphate because the viscosity is less sensitive to changes in the composition, so making it easier to produce an end product with repeatable viscosity.
  • the weight ratio of amine oxide to alkane sulphonate (when this is used) is preferably in the range from 80:20 to 50:50 or better 65:35, and preferably in the narrower range from 70:30 to 65:35.
  • One or more further surfactants may also be included, within the scope of this invention.
  • a sequestering agent may be used in an amount from 0,01 to 1% by weight. This is approximately 1.5 x 10 ⁇ 4 to 2 x 10 ⁇ 2 molar.
  • a separate stabilising agent to counteract manganese may be a phosphate salt used in an amount from 0.5% up to 4% by weight, preferably 1 to 3% (reckoned as anhydrous salt). Tetrasodium pyrophosphate may be used as such a salt.
  • colloidal hydrous stannic oxide Another possible stabilising agent which we have found to be effective in alkaline solution against decomposition caused by transition metals including both iron and manganese, is colloidal hydrous stannic oxide.
  • This stabilising agent is preferably formed in-situ in the solution as the product of hydrolysis of a soluble tin compound.
  • Various tin compounds can be added to the solution to undergo hydrolysis to form the stannic oxide, including tin sulphate, sodium stannate, tin dichloride and tin tetrachloride.
  • Suitable concentrations of tin compound in the composition may lie in the range from 10 ⁇ 4 molar to 10 ⁇ 2 molar, preferably 3 x 10 ⁇ 3 to 6 x 10 ⁇ 3 molar.
  • the quantity of tin compound should not be substantially greater than necessary, since excess of it can itself cause peroxide decomposition.
  • An optimum concentration of the tin compound (or any stabiliser) can be determined by making test solutions with various concentrations of the stabiliser and analytically determining the amount of hydrogen peroxide remaining after a period of storage.
  • An appropriate viscosity for a pourable composition having the appearance of a thick liquid is a dynamic viscosity in the range from 40 to 250 centipoise (0.05 to 0.25 Pa.sec), preferably about 100 centipoise (0.1 Pa.sec). More viscous liquids for example with viscosity in the range from 250 to 1000 centipoise or more are also within the scope of the invention.
  • compositions of this invention are generally aqueous, they will usually have specific gravity close to unity. Consequently values of kinematic viscosities (in stokes) will be numerically approximately the same as values of dynamic viscosity (in poise). Dynamic viscosities expressed in Pascal.sec will be approximately 1000 times kinetic viscosities expressed in m2 .sec ⁇ 1.
  • the pH of the solution is preferably in the range from 8.5 to 9.8 or 10.0. With a phosphonate stabiliser it is further preferred that the pH is in the narrower range from 9.2 to 9.8, while with colloidal stannic oxide as stabiliser it is preferable to use a slightly lower pH in the range from 8.7 to 9.3.
  • a buffer may be included to maintain pH at the desired value, but this may not be necessary.
  • a phosphate, if present, will give a buffering action.
  • Another compound which may be used for this purpose is borax.
  • the concentration of hydrogen peroxide in compositions of this invention desirably lies in the range from 2 to 10% by weight.
  • Formulations were prepared containing the constituents set out in Table 1 below. The compositions were stored in plastic bottles at 37°C. At intervals aliquots were removed and titrated with potassium permanganate to determine the level of hydrogen peroxide remaining. Results are included in Table 1.
  • Example 1 The procedure of Example 1 was repeated, using formulations with the same amounts of hydrogen peroxide, surfactant, perfume and dye.
  • Various tin compounds were used at a concentration of 6 x 10 ⁇ 3 molar, both with and without 3.0% borax decahydrate. Glass bottles were used, which are somewhat detrimental to stability. In every case pH was 9.6 initially. Proportions of hydrogen peroxide remaining after 28 days were:- SnCl2 with borax 68% Na2SnO3 with borax 47% SnSO4 with borax 45% Na2SnO3 without borax 96% SnCl4 without borax 68%
  • the thickening systems used various constituents and varied both in the properties and total amounts of materials employed.
  • the thickening systems contained tallow dimethylamine oxide (AO) together with sodium lauryl sulphate (SLS), or sodium alkane sulphonate (SAS), which was a secondary alkane sulphonate derived from an n-alkane mixture which is principally C13 to C18.
  • AO tallow dimethylamine oxide
  • SLS sodium lauryl sulphate
  • SAS sodium alkane sulphonate
  • Viscosities of the formulations were measured using a Ubbelohde capillary viscometer. The results obtained are shown in the accompanying Figures.
  • Figure 1 shows variation in viscosity with the proportion of SLS in an AO/SLS mixture, while the total amount of AO plus SLS is varied from 1.1% to 1.9% by weight of the composition.
  • Figure 2 shows variation in viscosity for AO/SAS mixtures while the total of AO plus SAS is varied from 1.2% to 2.6% of the composition. It can be seen that the viscosity maxima are broader peaks, while the maximum viscosity is less sensitive to variation in the total amount of AO plus SAS.
  • concentration of surfactant to give a viscosity of 100cS is 1.2%, and an increase from this of 0.2%, up to 1.4%, would double the viscosity to 200cS.
  • 1.4% total surfactant gives a viscosity of 100cS. Increasing by 0.2% increases the viscosity to 150cS and a larger increase, to 1.8%, is required to achieve 200cS.
  • Alkaline solutions of hydrogen peroxide were prepared containing surfactant, sodium chloride and stannic chloride which hydrolysed to colloidal hydrous stannic oxide.
  • the quantities of surfactant and sodium chloride were such as to give viscosities well in excess of that preferred for a pourable "thick liquid” type of bleach product. Smaller quantities could be used to give a "thick liquid” type of bleach product.
  • the initial concentration of hydrogen peroxide was 4% by weight.
  • the solutions were made alkaline to pH 10 with sodium hydroxide.
  • Stannic chloride was used at a concentration of 2.3 x 10 ⁇ 3 molar.
  • the surfactant system consisted of 4.5% by weight of C12-C14 alkyl dimethyl amine oxide and 4.5% by weight sodium lauryl sulphate. This was used with a sodium chloride concentration of 95 by weight.
  • the solutions were stored at 40°C and the amount of hydrogen peroxide remaining was determined at intervals. It was found that the amounts of hydrogen peroxide remaining were between 80 and 85%.

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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)
  • Cosmetics (AREA)
EP89313623A 1988-12-28 1989-12-27 Bleaching composition Expired - Lifetime EP0376704B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB888830296A GB8830296D0 (en) 1988-12-28 1988-12-28 Bleaching composition
GB8830296 1988-12-28

Publications (2)

Publication Number Publication Date
EP0376704A1 EP0376704A1 (en) 1990-07-04
EP0376704B1 true EP0376704B1 (en) 1995-02-15

Family

ID=10649218

Family Applications (2)

Application Number Title Priority Date Filing Date
EP89313625A Expired - Lifetime EP0376706B1 (en) 1988-12-28 1989-12-27 Bleaching composition
EP89313623A Expired - Lifetime EP0376704B1 (en) 1988-12-28 1989-12-27 Bleaching composition

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP89313625A Expired - Lifetime EP0376706B1 (en) 1988-12-28 1989-12-27 Bleaching composition

Country Status (11)

Country Link
EP (2) EP0376706B1 (enrdf_load_stackoverflow)
JP (2) JPH0735520B2 (enrdf_load_stackoverflow)
AU (2) AU623961B2 (enrdf_load_stackoverflow)
BR (2) BR8906843A (enrdf_load_stackoverflow)
CA (2) CA2006531C (enrdf_load_stackoverflow)
DE (2) DE68921181T2 (enrdf_load_stackoverflow)
ES (2) ES2067559T3 (enrdf_load_stackoverflow)
GB (1) GB8830296D0 (enrdf_load_stackoverflow)
IN (2) IN171127B (enrdf_load_stackoverflow)
NO (2) NO173885C (enrdf_load_stackoverflow)
ZA (2) ZA899842B (enrdf_load_stackoverflow)

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8830296D0 (en) * 1988-12-28 1989-02-22 Unilever Plc Bleaching composition
DE4123142A1 (de) * 1991-07-12 1993-01-14 Henkel Kgaa Fluessigwaschmittel
US5217710A (en) * 1992-03-05 1993-06-08 Chesebrough-Pond's Usa Co. Stabilized peroxide gels containing fluoride
GB9319943D0 (en) * 1993-09-28 1993-11-17 Solvay Interox Ltd Thickened compositions
GB2286603B (en) * 1994-02-14 1998-03-25 Jeyes Group Plc Bleach compositions
DE4413433C2 (de) * 1994-04-18 1999-09-16 Henkel Kgaa Wäßrige Bleichmittel
US5492540A (en) * 1994-06-13 1996-02-20 S. C. Johnson & Son, Inc. Soft surface cleaning composition and method with hydrogen peroxide
AU2801395A (en) * 1994-07-01 1996-01-25 Warwick International Group Limited Bleaching compositions
US5736497A (en) * 1995-05-05 1998-04-07 Degussa Corporation Phosphorus free stabilized alkaline peroxygen solutions
DE19623571C2 (de) * 1996-06-13 2000-06-08 Cognis Deutschland Gmbh Verdickungsmittel für wäßrige Wasserstoffperoxidlösungen
BR9704210A (pt) * 1997-07-31 1999-02-02 Unilever Nv Composição detergente e processo de lavagem de pratos
GB9812457D0 (en) * 1998-06-10 1998-08-05 Secr Defence Surface coatings
AU741580B2 (en) * 1998-06-23 2001-12-06 Saban Ventures Pty Limited Improved disinfection
BR9914702A (pt) * 1998-10-22 2001-07-10 Colgate Palmolive Co Composição de branqueamento lìquida espessada alcalina, e, processo de branqueamento de tecidos
GB2349892A (en) * 1999-05-13 2000-11-15 Warwick Internat Group Ltd Metal cleaning
GB2397823A (en) * 2003-01-31 2004-08-04 Reckitt Benckiser Nv Aqueous cleaning compositions
GB2401875A (en) * 2003-05-22 2004-11-24 Reckitt Benckiser Nv Aqueous cleaning compositions
ITMI20031543A1 (it) * 2003-07-28 2005-01-29 De Nora Elettrodi Spa Elettrodo per processi elettrochimici e metodo per il suo ottenimento
US7169237B2 (en) 2004-04-08 2007-01-30 Arkema Inc. Stabilization of alkaline hydrogen peroxide
US7431775B2 (en) * 2004-04-08 2008-10-07 Arkema Inc. Liquid detergent formulation with hydrogen peroxide
US7045493B2 (en) 2004-07-09 2006-05-16 Arkema Inc. Stabilized thickened hydrogen peroxide containing compositions
DE102005000955B4 (de) * 2005-01-07 2007-08-30 Henkel Kgaa Flüssige Bleichmittelzusammensetzung
CN105925398B (zh) * 2016-05-17 2018-11-23 河南工程学院 一种除菌液体洗涤剂组合物及其制备方法

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Publication number Priority date Publication date Assignee Title
BE562380A (enrdf_load_stackoverflow) * 1956-11-14
NL113683C (enrdf_load_stackoverflow) * 1958-07-10
DE1271885B (de) * 1964-01-04 1968-07-04 Henkel & Cie Gmbh Fluessige, lagerbestaendige Wasch-, Bleich- und Oxydationsmittel
US3701825A (en) * 1970-10-23 1972-10-31 Fmc Corp Stabilization of hydrogen peroxide with ethylenediamine tetra (methylenephosphonic acid)
FR2140822A5 (en) * 1971-06-09 1973-01-19 Air Liquide Bleaching liquids - contg hydrogen peroxide or persalts in alkaline medium with stabilisers
US4304762A (en) * 1978-09-27 1981-12-08 Lever Brothers Company Stabilization of hydrogen peroxide
US4299802A (en) * 1980-03-31 1981-11-10 Union Carbide Corporation Process for removing carbonyl sulfide from gaseous streams
DE3168426D1 (en) * 1980-04-01 1985-03-07 Interox Chemicals Ltd Liquid detergent compositions, their manufacture and their use in washing processes
JPS56151798A (en) * 1980-04-01 1981-11-24 Interox Chemicals Ltd Liquid detergent composition
JPS5838800A (ja) * 1981-09-01 1983-03-07 三菱瓦斯化学株式会社 液体洗浄剤
DE3205318A1 (de) * 1982-02-15 1983-08-18 Henkel KGaA, 4000 Düsseldorf Desinfektionsmittelkonzentrat
CA1205275A (en) * 1982-06-14 1986-06-03 Kenneth J. Radimer Stabilization of high purity hydrogen peroxide
JPS593006A (ja) * 1982-06-14 1984-01-09 エフ・エム・シ−・コ−ポレ−シヨン 安定化された過酸化水素水溶液
FR2552124B1 (fr) * 1983-09-20 1986-09-12 Ugine Kuhlmann Nouvelles formulations fluides pour bains alcalins de blanchiment textile stables au stockage et leur procede d'obtention
JP2783999B2 (ja) * 1985-06-12 1998-08-06 花王株式会社 漂白剤組成物
GB8830296D0 (en) * 1988-12-28 1989-02-22 Unilever Plc Bleaching composition

Also Published As

Publication number Publication date
EP0376706B1 (en) 1995-02-15
CA2006530A1 (en) 1990-06-28
ES2067559T3 (es) 1995-04-01
IN170708B (enrdf_load_stackoverflow) 1992-05-09
EP0376706A1 (en) 1990-07-04
NO895260L (no) 1990-06-29
NO173885B (no) 1993-11-08
NO895261L (no) 1990-06-29
DE68921181D1 (de) 1995-03-23
JPH02227499A (ja) 1990-09-10
JP2562064B2 (ja) 1996-12-11
DE68921182D1 (de) 1995-03-23
AU4727289A (en) 1990-07-05
NO173885C (no) 1994-02-16
ZA899843B (en) 1991-08-28
CA2006531C (en) 1996-09-03
NO172354B (no) 1993-03-29
NO172354C (no) 1993-07-07
NO895260D0 (no) 1989-12-27
ES2067558T3 (es) 1995-04-01
JPH0735520B2 (ja) 1995-04-19
BR8906843A (pt) 1990-09-18
JPH02227498A (ja) 1990-09-10
DE68921181T2 (de) 1995-06-14
DE68921182T2 (de) 1995-06-14
AU4727189A (en) 1990-07-05
BR8906844A (pt) 1990-09-25
ZA899842B (en) 1991-08-28
NO895261D0 (no) 1989-12-27
CA2006530C (en) 1996-10-15
AU624209B2 (en) 1992-06-04
IN171127B (enrdf_load_stackoverflow) 1992-07-25
GB8830296D0 (en) 1989-02-22
AU623961B2 (en) 1992-05-28
EP0376704A1 (en) 1990-07-04
CA2006531A1 (en) 1990-06-28

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