CA2006531C - Bleaching composition - Google Patents
Bleaching compositionInfo
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- CA2006531C CA2006531C CA002006531A CA2006531A CA2006531C CA 2006531 C CA2006531 C CA 2006531C CA 002006531 A CA002006531 A CA 002006531A CA 2006531 A CA2006531 A CA 2006531A CA 2006531 C CA2006531 C CA 2006531C
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- surfactant
- hydrogen peroxide
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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
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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)
Abstract
Solutions of hydrogen peroxide which are alkaline, can be thickened with a combination of surfactant and electrolyte without unacceptable loss of stability.
Surfactant may be alkyl ether sulphate:
R(OC2H4)n OSO3M
or a combination of amine oxide R(CH3)2NO with alkane sulphonate RSO3M or alcohol sulphate ROSO3M where any R is C8 to C20 alkyl and any M is a solubilising cation and n is 0.5 to 5. Stabiliser is present and may be colloidal hydrous stannic oxide or may be a phosphonate as specified in EP-B-9839.
Surfactant may be alkyl ether sulphate:
R(OC2H4)n OSO3M
or a combination of amine oxide R(CH3)2NO with alkane sulphonate RSO3M or alcohol sulphate ROSO3M where any R is C8 to C20 alkyl and any M is a solubilising cation and n is 0.5 to 5. Stabiliser is present and may be colloidal hydrous stannic oxide or may be a phosphonate as specified in EP-B-9839.
Description
2006531.
BLEACHING COMPOSITION
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.
It is well known that hydrogen peroxide is unstable unless stabilising agents are present. These counteract decomposition catalysed by transition metal ions. Hydrogen peroxide gives better bleaching action if used under alkaline conditions. However, stabilisation of hydrogen peroxide under alkaline conditions is difficult and in consequence commercial solutions of hydrogen peroxide 2006531.
have generally been acidic for the sake of stability.
Certain phosphonates able to stabilise hydrogen peroxide in alkaline solution are disclosed in EP-B-9839 (Unilever).
The presence of electrolyte tends to cause decomposition of alkaline hydrogen peroxide solution. For instance, we have found that a 4% by weight solution of hydrogen peroxide, made alkaline to pH 10 and containing 0.25% of ethylene diamine tetramethylene phosphonic acid as stabiliser (which is not as effective as the phosphonates in accordance with EP-B-9839) was found to retain 95% of its hydrogen peroxide after two weeks storage at 37C. By contrast, 85% or less of the hydrogen peroxide was retained if the solution also contained 1% by weight of sodium chloride, while only about 50% of the hydrogen peroxide was retained if the solution contained 10% by weight of sodium chloride. Similar results were observed using sodium tripolyphosphate rather than sodium chloride as the added electrolyte. Doubling the quantity of the phosphonate stabiliser had little effect on the rate of decomposition.
Thus, 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.
We have now found, however, that it is possible to formulate an aqueous alkaline solution of hydrogen peroxide 3 20~6531 which is thickened with surfactant and electrolyte yet does have sufficient stability to be useful as a commercial product.
According to the present invention there is provided a liquid bleaching composition comprising an aqueous alkaline solution of pH 8.0-10.5, containing:
a) 1-15% by weight hydrogen peroxide, b) a stabilizer for hydrogen peroxide, c) 0.05-0.30 Molar electrolyte other than surfactant, and, d) 0.75-3% by weight of a combination of:
i) an amphoteric surfactant, and, ii) an anionic surfactant which is either a Cg-C20 alkane sulphonate or a Cg-C20 alcohol sulphate.
We have found that use of 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 15 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.
When the surfactant is a combination, in accordance with the alternative 2 0 (b) above, a preferred B
4 2006~31 possibllity for the nonionic/amphoteric surfactant is an amine oxide surfactant, preferably 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. Then, if primary alcohol sulphate is the anionic surfactant 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.
The electrolyte concentration in a composition of this invention may be such that the total amount of salts other than surfactant is not more than 7~ by weight, better not more than 5~ or 3~. The electrolyte level may be such as to give a concentration of electrolyte in the range 0.05 to 0.30 molar, preferably 0.1 to 0.2 molar. Once again , , ..~, .
2006~31 higher concentrations may be used but are less preferred.
Stabiliser for the hydrogen peroxide may be a phosphonate sequestrant in accordance with EP-B-9839, which defines the phosphonate compounds as of the general formula:
(P03 X2 )CH2~ /CH2 ( P03 X2 ) N-CH2 -CH2 ~ ( N~CH2 -CH2 )n -N
( P03 X2 )CH2 CH2 (P03 X2 ) CH2 ( P03 X2 ) wherein n = 1-4; and X is H or a water-soluble cation selected from the group consisting of alkali metals, ammonium, substituted ammonium and alkaline earth metals.
Such 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.
These compounds are effective to counter decomposition catalysed by iron but are less effective against manganese. We have found that it may be possible to prevent contamination by traces of manganese (e.g. by use of sufficiently pure raw materials) so that a separate stabiliser against manganese may not be required. However, if required 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.
Another possible stabilising agent which we have found to be effective in alkaline solution against 200~53~
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 lO- 2 molar, preferably 3 x lO- 3 to 6 x lO- 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.
Since the 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 8.0 to 10.5, better 8.5 to 9.8 or 10Ø 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, reckoned as pure H2 2 ' desirably lies in the range from 1 to 15% by weight preferably 2 to 10% by weight.
Example 1 Formulations were prepared containing the constituents set out in Table 1 below. The compositions were stored in plastic bottles at 37C. At intervals aliquots were removed and titrated with potassium permanganate to determine the level of hydrogen peroxide remaining. Results are included in Table 1.
The viscosity of these formulations was measured using a Ubbelohde capillary viscometer and found to be approximately lOOcS.
% by weight 5 Constituent A B C
Hydrogen peroxide 5 5 5 (reckoned as anhydrous) Tallow dimethylamine oxide 1.0 1.0 1.0 Sodium alkane sulphonate 0.5 0.5 0.5 Perfume 1.0 1.0 1.0 15 Tetrasodium pyrophosphate 1.8 - -(reckoned as anhydrous) Phosphonate stabiliser 0.15 according to EP 9839 Borax (reckoned as anhydrous) - 1.6 1.6 Sodium stannate trihydrate - 0.5 0.1 Sodium hydroxide to give: pH 9.6pH 9.6 pH 9.0 Water ----- balance to 100% -----H202 remaining after 50 days: 85% 79%
H202 remaining after 100 days: 96%
Example 2 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:-2(:)~)653~.
SnCl2 with borax 68%
Na2SnO3 with borax 47%
SnS0~ with borax 45%
Na2SnO3 without borax 96%
SnCl4 without borax 68%
Example 3 A range of formulations were prepared, all containing:
Hydrogen peroxide 5.0% reckoned as anhydrous Tetrasodium pyrophosphate 3.0% (approx 1.8% reckoned as decahydrateanhydrous) Phosphonate stabiliser according to EP 9839 0.3%
Perfume 0.1%
Sodium hydroxideto pH 9.6 25 Thickening systemvariable Water --- balance to 100% ---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 (A0) together with sodium lauryl sulphate (SLS), or sodium alkane sulphonate (SAS), which was a secondary alkane sulphonate derived from an n-alkane 10 201~6~1 mixture which i8 principally Cl 3 to Cl fl .
Vlscosities of the formulations were measured using a Ubbelohde capillary viscometer. The results obtained are shown in the accompanying Figures.
Figure 1 shows variation ln viscosity with the proportion of SLS ln an A0/SLS mixture, while the total amount of A0 plus SLS is varied from 1.1% to 1.9% by weight of the composition.
Figure 2 shows variation in viscosity for A0/SAS
mixtures while the total of A0 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 A0 plus SAS. For instance in Figure 1 the concentration of surfactant to give a viscosity of lOOcS is 1.2%, and an increase from this of 0.2%, up to 1.4%, would double the viscosity to 200cS. In Figure 2 1.4% total surfactant gives a viscosity of lOOcS. Increasing by 0.2% increases the viscosity to 150cS and a larger increase, to 1.8%, is required to achieve 200cS.
~3 '' 2~06531 Example 4 An alkaline solution of hydrogen peroxide was 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, reckoned as anhydrous, 1 0 was 4% by weight. The solution was 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 Cl2-Cl4 alkyl dimethyl amine oxide and 4.5% by weight sodium lauryl sulphate. This was used with a sodium chloride concentration of 9% by weight.
The solution was 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 was between 80 and 85%.
B
.
BLEACHING COMPOSITION
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.
It is well known that hydrogen peroxide is unstable unless stabilising agents are present. These counteract decomposition catalysed by transition metal ions. Hydrogen peroxide gives better bleaching action if used under alkaline conditions. However, stabilisation of hydrogen peroxide under alkaline conditions is difficult and in consequence commercial solutions of hydrogen peroxide 2006531.
have generally been acidic for the sake of stability.
Certain phosphonates able to stabilise hydrogen peroxide in alkaline solution are disclosed in EP-B-9839 (Unilever).
The presence of electrolyte tends to cause decomposition of alkaline hydrogen peroxide solution. For instance, we have found that a 4% by weight solution of hydrogen peroxide, made alkaline to pH 10 and containing 0.25% of ethylene diamine tetramethylene phosphonic acid as stabiliser (which is not as effective as the phosphonates in accordance with EP-B-9839) was found to retain 95% of its hydrogen peroxide after two weeks storage at 37C. By contrast, 85% or less of the hydrogen peroxide was retained if the solution also contained 1% by weight of sodium chloride, while only about 50% of the hydrogen peroxide was retained if the solution contained 10% by weight of sodium chloride. Similar results were observed using sodium tripolyphosphate rather than sodium chloride as the added electrolyte. Doubling the quantity of the phosphonate stabiliser had little effect on the rate of decomposition.
Thus, 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.
We have now found, however, that it is possible to formulate an aqueous alkaline solution of hydrogen peroxide 3 20~6531 which is thickened with surfactant and electrolyte yet does have sufficient stability to be useful as a commercial product.
According to the present invention there is provided a liquid bleaching composition comprising an aqueous alkaline solution of pH 8.0-10.5, containing:
a) 1-15% by weight hydrogen peroxide, b) a stabilizer for hydrogen peroxide, c) 0.05-0.30 Molar electrolyte other than surfactant, and, d) 0.75-3% by weight of a combination of:
i) an amphoteric surfactant, and, ii) an anionic surfactant which is either a Cg-C20 alkane sulphonate or a Cg-C20 alcohol sulphate.
We have found that use of 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 15 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.
When the surfactant is a combination, in accordance with the alternative 2 0 (b) above, a preferred B
4 2006~31 possibllity for the nonionic/amphoteric surfactant is an amine oxide surfactant, preferably 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. Then, if primary alcohol sulphate is the anionic surfactant 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.
The electrolyte concentration in a composition of this invention may be such that the total amount of salts other than surfactant is not more than 7~ by weight, better not more than 5~ or 3~. The electrolyte level may be such as to give a concentration of electrolyte in the range 0.05 to 0.30 molar, preferably 0.1 to 0.2 molar. Once again , , ..~, .
2006~31 higher concentrations may be used but are less preferred.
Stabiliser for the hydrogen peroxide may be a phosphonate sequestrant in accordance with EP-B-9839, which defines the phosphonate compounds as of the general formula:
(P03 X2 )CH2~ /CH2 ( P03 X2 ) N-CH2 -CH2 ~ ( N~CH2 -CH2 )n -N
( P03 X2 )CH2 CH2 (P03 X2 ) CH2 ( P03 X2 ) wherein n = 1-4; and X is H or a water-soluble cation selected from the group consisting of alkali metals, ammonium, substituted ammonium and alkaline earth metals.
Such 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.
These compounds are effective to counter decomposition catalysed by iron but are less effective against manganese. We have found that it may be possible to prevent contamination by traces of manganese (e.g. by use of sufficiently pure raw materials) so that a separate stabiliser against manganese may not be required. However, if required 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.
Another possible stabilising agent which we have found to be effective in alkaline solution against 200~53~
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 lO- 2 molar, preferably 3 x lO- 3 to 6 x lO- 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.
Since the 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 8.0 to 10.5, better 8.5 to 9.8 or 10Ø 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, reckoned as pure H2 2 ' desirably lies in the range from 1 to 15% by weight preferably 2 to 10% by weight.
Example 1 Formulations were prepared containing the constituents set out in Table 1 below. The compositions were stored in plastic bottles at 37C. At intervals aliquots were removed and titrated with potassium permanganate to determine the level of hydrogen peroxide remaining. Results are included in Table 1.
The viscosity of these formulations was measured using a Ubbelohde capillary viscometer and found to be approximately lOOcS.
% by weight 5 Constituent A B C
Hydrogen peroxide 5 5 5 (reckoned as anhydrous) Tallow dimethylamine oxide 1.0 1.0 1.0 Sodium alkane sulphonate 0.5 0.5 0.5 Perfume 1.0 1.0 1.0 15 Tetrasodium pyrophosphate 1.8 - -(reckoned as anhydrous) Phosphonate stabiliser 0.15 according to EP 9839 Borax (reckoned as anhydrous) - 1.6 1.6 Sodium stannate trihydrate - 0.5 0.1 Sodium hydroxide to give: pH 9.6pH 9.6 pH 9.0 Water ----- balance to 100% -----H202 remaining after 50 days: 85% 79%
H202 remaining after 100 days: 96%
Example 2 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:-2(:)~)653~.
SnCl2 with borax 68%
Na2SnO3 with borax 47%
SnS0~ with borax 45%
Na2SnO3 without borax 96%
SnCl4 without borax 68%
Example 3 A range of formulations were prepared, all containing:
Hydrogen peroxide 5.0% reckoned as anhydrous Tetrasodium pyrophosphate 3.0% (approx 1.8% reckoned as decahydrateanhydrous) Phosphonate stabiliser according to EP 9839 0.3%
Perfume 0.1%
Sodium hydroxideto pH 9.6 25 Thickening systemvariable Water --- balance to 100% ---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 (A0) together with sodium lauryl sulphate (SLS), or sodium alkane sulphonate (SAS), which was a secondary alkane sulphonate derived from an n-alkane 10 201~6~1 mixture which i8 principally Cl 3 to Cl fl .
Vlscosities of the formulations were measured using a Ubbelohde capillary viscometer. The results obtained are shown in the accompanying Figures.
Figure 1 shows variation ln viscosity with the proportion of SLS ln an A0/SLS mixture, while the total amount of A0 plus SLS is varied from 1.1% to 1.9% by weight of the composition.
Figure 2 shows variation in viscosity for A0/SAS
mixtures while the total of A0 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 A0 plus SAS. For instance in Figure 1 the concentration of surfactant to give a viscosity of lOOcS is 1.2%, and an increase from this of 0.2%, up to 1.4%, would double the viscosity to 200cS. In Figure 2 1.4% total surfactant gives a viscosity of lOOcS. Increasing by 0.2% increases the viscosity to 150cS and a larger increase, to 1.8%, is required to achieve 200cS.
~3 '' 2~06531 Example 4 An alkaline solution of hydrogen peroxide was 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, reckoned as anhydrous, 1 0 was 4% by weight. The solution was 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 Cl2-Cl4 alkyl dimethyl amine oxide and 4.5% by weight sodium lauryl sulphate. This was used with a sodium chloride concentration of 9% by weight.
The solution was 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 was between 80 and 85%.
B
.
Claims (7)
1. A liquid bleaching composition comprising an aqueous alkaline solution of pH 8.0-10.5, containing:
a) 1-15% by weight hydrogen peroxide, b) a stabilizer for hydrogen peroxide, c) 0.05-0.30 Molar electrolyte other than surfactant, and, d) 0.75-3% by weight of a combination of:
i) an amphoteric surfactant, and, ii) an anionic surfactant which is either a C8-C20 alkane sulphonate or a C8-C20 alcohol sulphate.
a) 1-15% by weight hydrogen peroxide, b) a stabilizer for hydrogen peroxide, c) 0.05-0.30 Molar electrolyte other than surfactant, and, d) 0.75-3% by weight of a combination of:
i) an amphoteric surfactant, and, ii) an anionic surfactant which is either a C8-C20 alkane sulphonate or a C8-C20 alcohol sulphate.
2. A composition according to claim 1 wherein the surfactant is a combination of (i) a trialkyl amine oxide having one C8-C20 alkyl group and two C1 to C4 alkyl groups and (ii) a said anionic surfactant.
3. A composition according to claim 1 wherein the amount of electrolyte in solution is such that the total quantity of salts other than surfactant in the composition does not exceed 5% by weight based on the whole composition.
4. A composition according to claim 1 wherein the surfactant is a said alkyl ether sulphate and the electrolyte concentration is in the range from 0.75 to 10%
by weight.
by weight.
5. A composition according to claim 1, claim 2 or claim 3 wherein the stabiliser is colloidal hydrous stannic oxide.
6. A composition according to claim 1, claim 2 or claim 3 wherein the stabiliser is a compound of the formula:
wherein n = 1-4; and X is H or a water-soluble cation selected from the group consisting of alkali metals, ammonium, substituted ammonium and alkaline earth metals.
wherein n = 1-4; and X is H or a water-soluble cation selected from the group consisting of alkali metals, ammonium, substituted ammonium and alkaline earth metals.
7. A composition according to claim 1, claim 2 or claim 3 having a pH in the range from 8.5 to 10.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8830296.3 | 1988-12-28 | ||
| GB888830296A GB8830296D0 (en) | 1988-12-28 | 1988-12-28 | Bleaching composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2006531A1 CA2006531A1 (en) | 1990-06-28 |
| CA2006531C true CA2006531C (en) | 1996-09-03 |
Family
ID=10649218
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002006531A Expired - Fee Related CA2006531C (en) | 1988-12-28 | 1989-12-22 | Bleaching composition |
| CA002006530A Expired - Fee Related CA2006530C (en) | 1988-12-28 | 1989-12-22 | Bleaching composition |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002006530A Expired - Fee Related CA2006530C (en) | 1988-12-28 | 1989-12-22 | Bleaching composition |
Country Status (11)
| Country | Link |
|---|---|
| EP (2) | EP0376704B1 (en) |
| JP (2) | JP2562064B2 (en) |
| AU (2) | AU623961B2 (en) |
| BR (2) | BR8906844A (en) |
| CA (2) | CA2006531C (en) |
| DE (2) | DE68921181T2 (en) |
| ES (2) | ES2067558T3 (en) |
| GB (1) | GB8830296D0 (en) |
| IN (2) | IN171127B (en) |
| NO (2) | NO173885C (en) |
| ZA (2) | ZA899842B (en) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8830296D0 (en) * | 1988-12-28 | 1989-02-22 | Unilever Plc | Bleaching composition |
| DE4123142A1 (en) * | 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 (en) * | 1994-04-18 | 1999-09-16 | Henkel Kgaa | Aqueous bleach |
| US5492540A (en) * | 1994-06-13 | 1996-02-20 | S. C. Johnson & Son, Inc. | Soft surface cleaning composition and method with hydrogen peroxide |
| WO1996001311A1 (en) * | 1994-07-01 | 1996-01-18 | Warwick International Group Limited | Bleaching compositions |
| US5736497A (en) * | 1995-05-05 | 1998-04-07 | Degussa Corporation | Phosphorus free stabilized alkaline peroxygen solutions |
| DE19623571C2 (en) * | 1996-06-13 | 2000-06-08 | Cognis Deutschland Gmbh | Thickener for aqueous hydrogen peroxide solutions |
| BR9704210A (en) * | 1997-07-31 | 1999-02-02 | Unilever Nv | Detergent composition and dish washing process |
| 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 |
| EP1123375B1 (en) * | 1998-10-22 | 2005-04-20 | Colgate-Palmolive Company | Thickened liquid hydrogen peroxide bleach compositions |
| 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 (en) * | 2003-07-28 | 2005-01-29 | De Nora Elettrodi Spa | ELECTRODE FOR ELECTROCHEMICAL PROCESSES AND METHOD FOR ITS ACHIEVEMENT |
| 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 (en) * | 2005-01-07 | 2007-08-30 | Henkel Kgaa | Liquid bleach composition |
| CN105925398B (en) * | 2016-05-17 | 2018-11-23 | 河南工程学院 | A kind of degerming liquid detergent composition and preparation method thereof |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL222456A (en) * | 1956-11-14 | |||
| BE580351A (en) * | 1958-07-10 | |||
| DE1271885B (en) * | 1964-01-04 | 1968-07-04 | Henkel & Cie Gmbh | Liquid, storage-stable detergents, bleaching agents and oxidizing agents |
| 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 (en) * | 1981-09-01 | 1983-03-07 | 三菱瓦斯化学株式会社 | Liquid detergent |
| DE3205318A1 (en) * | 1982-02-15 | 1983-08-18 | Henkel KGaA, 4000 Düsseldorf | DISINFECTANT CONCENTRATE |
| CA1205275A (en) * | 1982-06-14 | 1986-06-03 | Kenneth J. Radimer | Stabilization of high purity hydrogen peroxide |
| JPS593006A (en) * | 1982-06-14 | 1984-01-09 | エフ・エム・シ−・コ−ポレ−シヨン | Method of stabilizing high-purity hydrogen peroxide |
| FR2552124B1 (en) * | 1983-09-20 | 1986-09-12 | Ugine Kuhlmann | NOVEL FLUID FORMULATIONS FOR STORAGE-STABLE TEXTILE BLEACH BATHS AND PROCESS FOR OBTAINING SAME |
| JP2783999B2 (en) * | 1985-06-12 | 1998-08-06 | 花王株式会社 | Bleach composition |
| GB8830296D0 (en) * | 1988-12-28 | 1989-02-22 | Unilever Plc | Bleaching composition |
-
1988
- 1988-12-28 GB GB888830296A patent/GB8830296D0/en active Pending
-
1989
- 1989-12-21 ZA ZA899842A patent/ZA899842B/en unknown
- 1989-12-21 ZA ZA899843A patent/ZA899843B/en unknown
- 1989-12-22 CA CA002006531A patent/CA2006531C/en not_active Expired - Fee Related
- 1989-12-22 AU AU47271/89A patent/AU623961B2/en not_active Ceased
- 1989-12-22 CA CA002006530A patent/CA2006530C/en not_active Expired - Fee Related
- 1989-12-22 AU AU47272/89A patent/AU624209B2/en not_active Ceased
- 1989-12-27 NO NO895260A patent/NO173885C/en not_active IP Right Cessation
- 1989-12-27 NO NO895261A patent/NO172354C/en not_active IP Right Cessation
- 1989-12-27 DE DE68921181T patent/DE68921181T2/en not_active Expired - Fee Related
- 1989-12-27 DE DE68921182T patent/DE68921182T2/en not_active Expired - Fee Related
- 1989-12-27 ES ES89313623T patent/ES2067558T3/en not_active Expired - Lifetime
- 1989-12-27 ES ES89313625T patent/ES2067559T3/en not_active Expired - Lifetime
- 1989-12-27 EP EP89313623A patent/EP0376704B1/en not_active Expired - Lifetime
- 1989-12-27 EP EP89313625A patent/EP0376706B1/en not_active Expired - Lifetime
- 1989-12-27 IN IN354/BOM/89A patent/IN171127B/en unknown
- 1989-12-27 IN IN355/BOM/89A patent/IN170708B/en unknown
- 1989-12-28 BR BR898906844A patent/BR8906844A/en not_active IP Right Cessation
- 1989-12-28 JP JP1345128A patent/JP2562064B2/en not_active Expired - Fee Related
- 1989-12-28 BR BR898906843A patent/BR8906843A/en not_active IP Right Cessation
- 1989-12-28 JP JP1345129A patent/JPH0735520B2/en not_active Expired - Lifetime
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