EP0249474A2 - Cleaning compositions - Google Patents
Cleaning compositions Download PDFInfo
- Publication number
- EP0249474A2 EP0249474A2 EP19870305170 EP87305170A EP0249474A2 EP 0249474 A2 EP0249474 A2 EP 0249474A2 EP 19870305170 EP19870305170 EP 19870305170 EP 87305170 A EP87305170 A EP 87305170A EP 0249474 A2 EP0249474 A2 EP 0249474A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- antioxidant
- fatty acyl
- process according
- weight
- 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.)
- Granted
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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0084—Antioxidants; Free-radical scavengers
-
- 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
- C11D1/126—Acylisethionates
-
- 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
- C11D10/042—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on anionic surface-active 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/006—Detergents in the form of bars or tablets containing mainly surfactants, but no builders, e.g. syndet bar
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2006—Monohydric alcohols
- C11D3/2034—Monohydric alcohols aromatic
Definitions
- This invention relates to cleaning compositions containing fatty acyl isethionate as at least part of detergent active present.
- the compositions may in particular be in the form of bars for personal washing.
- Bars containing fatty acyl isethionate as the main detergent active have been marketed commercially for a number of years, and have achieved considerable acceptance in North America.
- Bars containing substantial amounts of isethionate have a distinctive odour, and it is known that the quality of the fatty acid used in production of the isethionate needs to be controlled in order to control the odour of the freshly-made product. Provided that this quality control is done, the fresh product can have an acceptable odour despite being subjected to high temperatures during the process of manufacture.
- the commercially made product with an acceptable odour when freshly made, has a shelf life which is generally satisfactory. Such a requirement must be the case for a product which has been accepted by consumers.
- the present invention resides in a finding that the shelf life of products containing fatty acyl isethionate can be improved by the incorporation into such products of small quantities of each of an antioxidant, a sequestrant for iron and a sequestrant for copper. It is essential to this invention that all three of these items are present.
- GB patent specification 1169551 (Unilever Limited) teaches the use of 0.02% EHDP and 0.02% EDTA by weight in soap bars.
- the specification suggests that fatty acyl isethionate can be present but does not take the matter further and in particular does not tackle the particular problem addressed in the present invention.
- the present invention provides a cleaning composition containing detergent active which includes at least some fatty acyl isethionate wherein the composition also contains at least 0.002% by weight of the composition of each of an antioxidant, a sequestering agent for iron, and a sequestering agent for copper.
- the invention provides a process of producing a cleaning composition which contains detergent active including at least some fatty acyl isethionate, which comprises incorporating into the composition at least 0.002% by weight of the composition of each of an antioxidant, a sequestering agent for iron and a sequestering agent for copper.
- a fatty acyl compound used to manufacture the isethionate is sparged with nitrogen or some other gas which does not react with it, prior to reaction to form the fatty acyl isethionate. It should then be maintained under an atmosphere of such gas until the isethionate formation step has been carried out. Accordingly a preferred process includes flushing a fatty acyl-containing precursor under an atmosphere of such gas.
- a preferred composition of this invention has its fatty acyl isethionate made in this way.
- Sparging with nitrogen will generally consist in bubbling the nitrogen through the fatty acyl-containing precursor compound while the latter is in a liquid form.
- the fatty acyl compound normally used is coconut fatty acid.
- the antioxidant used should be a compound able to suppress reactions proceeding via a free radical mechanism, and will generally be a free radical scavenging agent. Many such compounds are available.
- a compound is chosen which is able to survive the conditions under which a fatty acyl-containing precursor compound is reacted to form fatty acyl isethionate, and is added to the precursor compound before that reaction. Notably it may be added to coconut fatty acid as the precursor compound.
- the antioxidant is added after the fatty acyl isethionate has been formed and any other high temperature steps have been carried out. Suitably it is incorporated in the composition and maintained at a temperature below 170°C.
- a preferred antioxidant is 2,6-di-t-butyl-4-methylphenol referred to hereinafter as BHT.
- a preferred level of addition of this compound is 200 ppm (0.02% by weight) based on the fatty acyl-containing precursor.
- a preferred sequestering agent for copper is ethylene diamine tetra acetic acid (EDTA) or a soluble salt thereof such as its tetra sodium salt or mixtures thereof.
- EDTA ethylene diamine tetra acetic acid
- Such agents are known to enhance the activity of iron in accelerating autoxidation, but can be used successfully provided there is a satisfactory sequestering agent for iron present. The two sequestering agents are then acting synergistically.
- the preferred sequestering agent for iron is 1-hydroxyethane-1,1-diphosphonic acid (EHDP) or a soluble salt thereof or mixtures thereof. This sequestering agent can be used successfully even when the cleaning composition is superfatted. If the composition does not contain free fatty acid then an alternative possibility for the sequestering agent for iron is magnesium trisilicate.
- sequestering agents will generally be added after the fatty acyl isethionate has been formed and any other high temperature processing steps have been carried out.
- the sequestering agents are incorporated in the composition and maintained at a temperature below 170°C.
- the present process includes preparing the fatty acyl isethionate from isethionate and free fatty acid and flashcooling the product, and thereafter adding sequestering agents and also preferably the antioxidant.
- the quantity of the antioxidant, and of each sequestering agent should be sufficient to be effective. As indicated above, the amount should be at least 0.002% by weight of the composition and it is preferred to use a greater amount so that the composition contains at least 0.005% or at least 0.01% of each sequestering agent.
- the stoichiometric equivalent of 0.02% tetrasodium EDTA is 33 ppm copper.
- the stoichiometric equivalent of 0.02% EHDP (as pure acid) is 54 ppm iron. These quantities are well above the amounts of contaminating copper and iron which we have been able to detect in fatty acyl isethionate-containing bars as currently marketed.
- the total quantity of antioxidant plus sequestering agents will normally be below 1% by weight of the composition and indeed normally less than 0.1% by weight.
- Fatty acyl isethionates normally used in cleaning compositions have 8 to 18 carbon atoms in the fatty acyl group. Particularly preferred is coconut fatty acyl.
- the coconut fatty acyl may have been hardened, that is to say the amount of olefinic unsaturation reduced, in well known manner.
- the detergent actives present in a cleaning composition bar may consist exclusively or substantially exclusively of fatty acyl isethionate and soap. For example the amount of any other detergent active may be less than 2% of all detergent active present.
- Weight ratios of soap to fatty acyl isethionate may range from 10:90 to 95:5, preferably 15:85 to 60:40, and may be in the range 10:90 to 35:65 or 25:75.
- fatty acyl isethionate may provide at least 40%, preferably from 48%, up to 53% by weight of the composition.
- acyl isethionate and soap are not the only detergent actives present they may nevertheless constitute most of the detergent active present, e.g. more than three quarters of it with the weight ratio of soap to acyl isethionate still being within the range as indicated above.
- This invention is particularly applicable when fatty acyl isethionate constitutes at least the majority of detergent active present.
- a superfatted composition may contain more than 5% free fatty acid.
- the amount of superfatting acid may be more than equivalent to the amount of soap, so that soap is converted into its acid form to a substantial degree.
- the soap used may contain some additive to prevent deterioration of its own odour, but of course the amount will be diluted on mixing with fatty acyl isethionate. Generally a separate addition of the antioxidant and sequestrants of this invention will be required.
- the present invention may in particular be applied when the fatty acyl isethionate has been prepared by reaction of C8-C18 fatty acyl compound, usually the fatty acid itself with an isethionate at temperatures in excess of 100°C.
- BHT can be added to individual batches of coconut fatty acid and allowed to mix into the acid as that acid is sparged with nitrogen.
- EDTA and EHDP can conveniently be carried out by periodically dosing a small quantity of each of these materials into a tank where the fatty acyl isethionate is mixed with other ingredients of a cleaning composition. Both materials can be added in the form of aqueous solution and since the amounts which are added are small the increased water content of the composition is not significant.
- the two sequestering agents need to be added to the fatty acyl isethionate through separate pipework because if solutions of them are allowed to mix together before mixing with other material, there is a tendency for solids to crystallise out from the mixed solution.
- composition suitably admixed with for example soap and any other conventional additive e.g. dye, perfume, free fatty acid, sodium isethionate is suitably worked and formed into for example bars.
- any other conventional additive e.g. dye, perfume, free fatty acid, sodium isethionate is suitably worked and formed into for example bars.
- coconut fatty acid was reacted to form sodium fatty isethionate by the process described in US patent specification No. 3320292.
- the process comprises reacting a concentrated solution of sodium isethionate with coconut fatty acid in the presence of zinc oxide acting as catalyst.
- the reaction mixture is maintained at a temperature of about 232°C under a nitrogen blanket in order to remove water and allow the reaction to proceed.
- the resulting product is stripped to remove residual free coconut fatty acid.
- Stearic acid can be added at this stage in order to retain fluidity.
- the stripped product is then flash cooled, suitably by admixing with for example sodium isethionate solution.
- Other ingredients, in particular soap can then be admixed. For bars the mixture can then be rolled, milled, plodded and stamped.
- coconut fatty acid was reacted to form sodium fatty isethionate by the process of patent specification US 3320292.
- the process was carried out in slightly different ways to provide experimental and control products.
- the coconut fatty acid was sparged with nitrogen before reaction and the sparged material thereafter kept under a nitrogen atmosphere throughout all the reaction process steps carried out at elevated temperatures.
- BHT was included in the coconut fatty acid used for the experimental material, so as to provide 200 ppm BHT in the fatty acid. After flashcooling tetrasodium EDTA and EHDP were added to the experimental material to provide 0.02% by weight of each in the mixture.
- control material was prepared in the same way from the same batch of fatty acid but without nitrogen sparging, and without the additions of BHT, EDTA salt and EHDP.
- the experimental and control product materials were both processed into unperfumed and perfumed bars which were subjected to storage tests.
- the tester was provided with reference samples which were stored under refrigerated conditions so that these reference samples should undergo minimal change in odour. Even so, it should be appreciated that any ratings of 1, 2 or 3 are not truly absolute but rather are comparative between the experimental and control materials at the time of the test.
- Example 1 The preparation of sodium fatty acyl isethionate, processing of the product into bars and storage testing of those bars was carried out in the same way as for Example 1.
- the control bars are prepared without nitrogen sparging and without any BHT, EDTA or EHDP.
- a first experimental material was prepared while employing nitrogen sparging and adding the BHT to the coconut fatty acid.
- a second experimental material was also prepared while employing nitrogen sparging and the addition of BHT to the fatty acid before reaction: additionally tetra sodium EDTA and EHDP were added to this second experimental material after the reaction had been carried out.
- the products were prepared from the same coconut and stearic fatty acid production (ex Emery Chemicals Toronto) in order to ensure equivalence in the initial odour and chemical composition of the raw materials. All batches were produced with nitrogen sparging during the heat-up and reaction stages and during the stripping and flash cooling stages.
- the chromatographs for the control (ie unpreserved) product E indicate significant peaks of low molecular weight aldehydes and hydrocarbons, which are attributable to the result of oxidative degeneration (ie autoxidation) of unsaturated fatty acids.
- the two principal contributors to the malodour are isopentanal/pentanal and hexanal.
- sample C is less stable than sample D.
- sample D is less stable than sample D.
- the most stable product was that which was prepared with Na4EDTA, EHDP and BHT added after flash cooling as virtually all the identifiable low molecular weight aldehydes and hydrocarbons were eliminated.
Abstract
Description
- This invention relates to cleaning compositions containing fatty acyl isethionate as at least part of detergent active present. The compositions may in particular be in the form of bars for personal washing.
- Bars containing fatty acyl isethionate as the main detergent active have been marketed commercially for a number of years, and have achieved considerable acceptance in North America.
- There have also been numerous proposals for bars in which fatty acyl isethionate is used in admixture with other detergent active(s) which may be soap.
- Bars containing substantial amounts of isethionate have a distinctive odour, and it is known that the quality of the fatty acid used in production of the isethionate needs to be controlled in order to control the odour of the freshly-made product. Provided that this quality control is done, the fresh product can have an acceptable odour despite being subjected to high temperatures during the process of manufacture.
- The commercially made product, with an acceptable odour when freshly made, has a shelf life which is generally satisfactory. Such a requirement must be the case for a product which has been accepted by consumers.
- We have now appreciated however that products containing fatty acyl isethionate, and having an acceptable odour when produced, nevertheless can have a tendency to develop an undesirable odour on prolonged storage at ambient temperature. We consider that it would be desirable to ameliorate this tendency, so as to enhance the shelf life of such products.
- We believe that the cause of this hitherto unrecognised defect is a process of autoxidation after production. Without being bound by this belief as to the cause, the present invention resides in a finding that the shelf life of products containing fatty acyl isethionate can be improved by the incorporation into such products of small quantities of each of an antioxidant, a sequestrant for iron and a sequestrant for copper. It is essential to this invention that all three of these items are present.
- GB patent specification 1169551 (Unilever Limited) teaches the use of 0.02% EHDP and 0.02% EDTA by weight in soap bars. The specification suggests that fatty acyl isethionate can be present but does not take the matter further and in particular does not tackle the particular problem addressed in the present invention.
- In one aspect the present invention provides a cleaning composition containing detergent active which includes at least some fatty acyl isethionate wherein the composition also contains at least 0.002% by weight of the composition of each of an antioxidant, a sequestering agent for iron, and a sequestering agent for copper.
- In a second aspect the invention provides a process of producing a cleaning composition which contains detergent active including at least some fatty acyl isethionate, which comprises incorporating into the composition at least 0.002% by weight of the composition of each of an antioxidant, a sequestering agent for iron and a sequestering agent for copper.
- It is strongly preferred that a fatty acyl compound used to manufacture the isethionate is sparged with nitrogen or some other gas which does not react with it, prior to reaction to form the fatty acyl isethionate. It should then be maintained under an atmosphere of such gas until the isethionate formation step has been carried out. Accordingly a preferred process includes flushing a fatty acyl-containing precursor under an atmosphere of such gas. A preferred composition of this invention has its fatty acyl isethionate made in this way.
- Sparging with nitrogen will generally consist in bubbling the nitrogen through the fatty acyl-containing precursor compound while the latter is in a liquid form. The fatty acyl compound normally used is coconut fatty acid.
- The antioxidant used should be a compound able to suppress reactions proceeding via a free radical mechanism, and will generally be a free radical scavenging agent. Many such compounds are available. Preferably a compound is chosen which is able to survive the conditions under which a fatty acyl-containing precursor compound is reacted to form fatty acyl isethionate, and is added to the precursor compound before that reaction. Notably it may be added to coconut fatty acid as the precursor compound. Preferably however the antioxidant is added after the fatty acyl isethionate has been formed and any other high temperature steps have been carried out. Suitably it is incorporated in the composition and maintained at a temperature below 170°C.
- A preferred antioxidant is 2,6-di-t-butyl-4-methylphenol referred to hereinafter as BHT.
- A preferred level of addition of this compound is 200 ppm (0.02% by weight) based on the fatty acyl-containing precursor.
- A preferred sequestering agent for copper is ethylene diamine tetra acetic acid (EDTA) or a soluble salt thereof such as its tetra sodium salt or mixtures thereof. Such agents are known to enhance the activity of iron in accelerating autoxidation, but can be used successfully provided there is a satisfactory sequestering agent for iron present. The two sequestering agents are then acting synergistically.
- The preferred sequestering agent for iron is 1-hydroxyethane-1,1-diphosphonic acid (EHDP) or a soluble salt thereof or mixtures thereof. This sequestering agent can be used successfully even when the cleaning composition is superfatted. If the composition does not contain free fatty acid then an alternative possibility for the sequestering agent for iron is magnesium trisilicate.
- These preferred sequestering agents will generally be added after the fatty acyl isethionate has been formed and any other high temperature processing steps have been carried out. Suitably the sequestering agents are incorporated in the composition and maintained at a temperature below 170°C.
- Thus preferably the present process includes preparing the fatty acyl isethionate from isethionate and free fatty acid and flashcooling the product, and thereafter adding sequestering agents and also preferably the antioxidant.
- The quantity of the antioxidant, and of each sequestering agent should be sufficient to be effective. As indicated above, the amount should be at least 0.002% by weight of the composition and it is preferred to use a greater amount so that the composition contains at least 0.005% or at least 0.01% of each sequestering agent.
- The stoichiometric equivalent of 0.02% tetrasodium EDTA is 33 ppm copper. The stoichiometric equivalent of 0.02% EHDP (as pure acid) is 54 ppm iron. These quantities are well above the amounts of contaminating copper and iron which we have been able to detect in fatty acyl isethionate-containing bars as currently marketed. The total quantity of antioxidant plus sequestering agents will normally be below 1% by weight of the composition and indeed normally less than 0.1% by weight.
- Fatty acyl isethionates normally used in cleaning compositions have 8 to 18 carbon atoms in the fatty acyl group. Particularly preferred is coconut fatty acyl. The coconut fatty acyl may have been hardened, that is to say the amount of olefinic unsaturation reduced, in well known manner. The detergent actives present in a cleaning composition bar may consist exclusively or substantially exclusively of fatty acyl isethionate and soap. For example the amount of any other detergent active may be less than 2% of all detergent active present. Weight ratios of soap to fatty acyl isethionate may range from 10:90 to 95:5, preferably 15:85 to 60:40, and may be in the range 10:90 to 35:65 or 25:75.
- As taught in US Patent 2894912 (Geitz) fatty acyl isethionate may provide at least 40%, preferably from 48%, up to 53% by weight of the composition.
- If acyl isethionate and soap are not the only detergent actives present they may nevertheless constitute most of the detergent active present, e.g. more than three quarters of it with the weight ratio of soap to acyl isethionate still being within the range as indicated above. This invention is particularly applicable when fatty acyl isethionate constitutes at least the majority of detergent active present.
- A superfatted composition may contain more than 5% free fatty acid. In a composition which is preponderantly fatty acyl isethionate, together with some soap, the amount of superfatting acid may be more than equivalent to the amount of soap, so that soap is converted into its acid form to a substantial degree.
- In a composition which contains a small amount of soap, the soap used may contain some additive to prevent deterioration of its own odour, but of course the amount will be diluted on mixing with fatty acyl isethionate. Generally a separate addition of the antioxidant and sequestrants of this invention will be required.
- The present invention may in particular be applied when the fatty acyl isethionate has been prepared by reaction of C₈-C₁₈ fatty acyl compound, usually the fatty acid itself with an isethionate at temperatures in excess of 100°C.
- BHT can be added to individual batches of coconut fatty acid and allowed to mix into the acid as that acid is sparged with nitrogen.
- The addition of EDTA and EHDP to fatty acyl isethionate can conveniently be carried out by periodically dosing a small quantity of each of these materials into a tank where the fatty acyl isethionate is mixed with other ingredients of a cleaning composition. Both materials can be added in the form of aqueous solution and since the amounts which are added are small the increased water content of the composition is not significant.
- However, the two sequestering agents need to be added to the fatty acyl isethionate through separate pipework because if solutions of them are allowed to mix together before mixing with other material, there is a tendency for solids to crystallise out from the mixed solution.
- The composition suitably admixed with for example soap and any other conventional additive e.g. dye, perfume, free fatty acid, sodium isethionate is suitably worked and formed into for example bars.
- Embodiments of the present invention will now be described by way of example only with reference to the following Examples.
- In each of the examples coconut fatty acid was reacted to form sodium fatty isethionate by the process described in US patent specification No. 3320292. In outline the process comprises reacting a concentrated solution of sodium isethionate with coconut fatty acid in the presence of zinc oxide acting as catalyst. The reaction mixture is maintained at a temperature of about 232°C under a nitrogen blanket in order to remove water and allow the reaction to proceed. The resulting product is stripped to remove residual free coconut fatty acid. Stearic acid can be added at this stage in order to retain fluidity. The stripped product is then flash cooled, suitably by admixing with for example sodium isethionate solution. Other ingredients, in particular soap, can then be admixed. For bars the mixture can then be rolled, milled, plodded and stamped.
- Coconut fatty acid was reacted to form sodium fatty isethionate by the process of patent specification US 3320292. The process was carried out in slightly different ways to provide experimental and control products. For the experimental material the coconut fatty acid was sparged with nitrogen before reaction and the sparged material thereafter kept under a nitrogen atmosphere throughout all the reaction process steps carried out at elevated temperatures. BHT was included in the coconut fatty acid used for the experimental material, so as to provide 200 ppm BHT in the fatty acid. After flashcooling tetrasodium EDTA and EHDP were added to the experimental material to provide 0.02% by weight of each in the mixture. The control material was prepared in the same way from the same batch of fatty acid but without nitrogen sparging, and without the additions of BHT, EDTA salt and EHDP. The experimental and control product materials were both processed into unperfumed and perfumed bars which were subjected to storage tests.
- To assess storage stability, the bars were wrapped in a conventional wrapping used for bars for personal washing, and stored for twelve weeks at room temperature (20°C), 28°C and 38°C. Odour was assessed by a human tester and rated on a scale as follows:
- 1. Excellent
- 2. Good ie standard for a commercial product
- 3. Fair
- 4. Poor
- 5. Unsatisfactory
- All bars were rated 1 or 2 prior to storage. The general condition of the bars was also noted.
- To assist in standardising the results observed at one time with the results at another time e.g. after storage, the tester was provided with reference samples which were stored under refrigerated conditions so that these reference samples should undergo minimal change in odour. Even so, it should be appreciated that any ratings of 1, 2 or 3 are not truly absolute but rather are comparative between the experimental and control materials at the time of the test.
-
- The preparation of sodium fatty acyl isethionate, processing of the product into bars and storage testing of those bars was carried out in the same way as for Example 1. As in Example 1 the control bars are prepared without nitrogen sparging and without any BHT, EDTA or EHDP. A first experimental material was prepared while employing nitrogen sparging and adding the BHT to the coconut fatty acid. A second experimental material was also prepared while employing nitrogen sparging and the addition of BHT to the fatty acid before reaction: additionally tetra sodium EDTA and EHDP were added to this second experimental material after the reaction had been carried out.
- The bars were wrapped, subjected to storage under various conditions, and tested in the same manner as for Example 1.
- The experiment was then repeated but with no control material (lacking nitrogen sparging and all of BHT, EDTA and EHDP), and making perfumed bars only. The storage tests were used to compare the materials with and without EDTA and EHDP.
-
-
- 1. Excellent
- 2. Good = Standard
- 3. Fair All bars rated 1 or 2 bofore storage
- 4. Poor
- 5. Unsatisfactory
- F = fatty
- ox = oxidized
- ran. = rancid
- sl. ox. = slightly oxidized
- PW = perfume weak
- It can be seen from the Tables that the provision of nitrogen sparging prior to reaction and addition of BHT to the coconut fatty acid before reaction produced only a marginal improvement in the odour rating whereas if this was combined with addition of EDTA and EHDP, there was a clearly observable improvement.
- The preparation of sodium fatty acyl isethionate and processing of the product into bars was carried out in the same way as for Example 1. In the present example five different processing regimes were followed with regard to the use of the sequestering and antioxidant agents in order to compare the effect of the presence of the sequestering agents and the antioxidant when used separately and when used together and the point of addition of the antioxidant.
- The products were prepared from the same coconut and stearic fatty acid production (ex Emery Chemicals Toronto) in order to ensure equivalence in the initial odour and chemical composition of the raw materials. All batches were produced with nitrogen sparging during the heat-up and reaction stages and during the stripping and flash cooling stages.
- The five different regimes followed were:
- A. 200 ppm BHT added to the coconut fatty acid raw material (equivalent to 75 ppm BHT on a finished product basis).
- B. 0.02% Na₄EDTA and 0.02% EHDP added to the flashed cooled sodium fatty isethionate base.
- C. A combination of A. and B.
- D. 0.02% Na₄EDTA, 0.02% EHDP and 0.0075% BHT (75 ppm BHT on a finished product basis) added to the flash cooled sodium fatty isethionate base.
- E. A control product, with no initiation or propagation inhibitors, except 15 ppm of BHT normally contained in the stearic acid.
- All the regimes were absent of the standard 30 ppm BHT which had been added in the previous examples. When produced each bar was packaged in standard cartons and wraps. For the product of each regime some bars were stored at room temperature and some at a raised temperature (38 degrees C). After one month the bars stored at 38 degrees C were analysed by gas chromatography and mass spectroscopy.
-
- The chromatographs for the control (ie unpreserved) product E indicate significant peaks of low molecular weight aldehydes and hydrocarbons, which are attributable to the result of oxidative degeneration (ie autoxidation) of unsaturated fatty acids. The two principal contributors to the malodour are isopentanal/pentanal and hexanal.
- The addition of 200 ppm of BHT alone to the coconut fatty acids (sample A) offered little improvement, as significant levels of isopentanal and hexanal were still present. However methyl pentenes and hexane were substantially eliminated.
- The products (samples B, C and D) prepared with the two chelating agents were significantly more stable than the control product or the product with BHT only. The low molcular weight hydrocarbons, isopentanal/pentanal, and the methyl pentenes were all minimised or eliminated from all bars containing Na₄EDTA and EHDP.
- A comparison of samples C and D, which each contain all three agents but differ in their point of addition of BHT, shows that sample C is less stable than sample D. Thus the most stable product was that which was prepared with Na₄EDTA, EHDP and BHT added after flash cooling as virtually all the identifiable low molecular weight aldehydes and hydrocarbons were eliminated.
Claims (20)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB868614462A GB8614462D0 (en) | 1986-06-13 | 1986-06-13 | Cleaning composition |
GB8614462 | 1986-06-13 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0249474A2 true EP0249474A2 (en) | 1987-12-16 |
EP0249474A3 EP0249474A3 (en) | 1989-08-16 |
EP0249474B1 EP0249474B1 (en) | 1993-06-09 |
Family
ID=10599431
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19870305170 Revoked EP0249474B1 (en) | 1986-06-13 | 1987-06-11 | Cleaning compositions |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0249474B1 (en) |
CA (1) | CA1311399C (en) |
DE (1) | DE3786113T2 (en) |
ES (1) | ES2054671T3 (en) |
GB (1) | GB8614462D0 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5132037A (en) * | 1989-05-05 | 1992-07-21 | Lever Brothers Company, Division Of Conopco, Inc. | Aqueous based personal washing cleanser |
US5234619A (en) * | 1989-05-05 | 1993-08-10 | Lever Brothers Company, Division Of Conopco, Inc. | Aqueous based personal washing cleanser |
WO1994026866A1 (en) * | 1993-05-19 | 1994-11-24 | Unilever Plc | Improvememts relating to soap bars |
US5500155A (en) * | 1994-03-18 | 1996-03-19 | Henkel Kommanditgesellschaft Auf Aktien | Detergent mixtures of fatty acid isethionate salts and fatty alcohols |
US5691287A (en) * | 1995-12-21 | 1997-11-25 | S. C. Johnson & Son, Inc. | Low irritation cleansing bar |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8129327B2 (en) | 2006-12-01 | 2012-03-06 | The Procter & Gamble Company | Packaging for high moisture bar soap |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1081233A (en) * | 1965-02-19 | 1967-08-31 | Maurice Bierre | Stabiliser for antioxidant in soaps, oils and like products |
GB1169551A (en) * | 1966-03-11 | 1969-11-05 | Unilever Ltd | Detergent Bar |
FR2154048A5 (en) * | 1971-09-17 | 1973-05-04 | Ici Ltd | |
EP0189332A2 (en) * | 1985-01-25 | 1986-07-30 | Unilever Plc | Toilet bars |
-
1986
- 1986-06-13 GB GB868614462A patent/GB8614462D0/en active Pending
-
1987
- 1987-06-08 CA CA000539133A patent/CA1311399C/en not_active Expired - Fee Related
- 1987-06-11 DE DE19873786113 patent/DE3786113T2/en not_active Revoked
- 1987-06-11 ES ES87305170T patent/ES2054671T3/en not_active Expired - Lifetime
- 1987-06-11 EP EP19870305170 patent/EP0249474B1/en not_active Revoked
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1081233A (en) * | 1965-02-19 | 1967-08-31 | Maurice Bierre | Stabiliser for antioxidant in soaps, oils and like products |
GB1169551A (en) * | 1966-03-11 | 1969-11-05 | Unilever Ltd | Detergent Bar |
FR2154048A5 (en) * | 1971-09-17 | 1973-05-04 | Ici Ltd | |
EP0189332A2 (en) * | 1985-01-25 | 1986-07-30 | Unilever Plc | Toilet bars |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5132037A (en) * | 1989-05-05 | 1992-07-21 | Lever Brothers Company, Division Of Conopco, Inc. | Aqueous based personal washing cleanser |
US5234619A (en) * | 1989-05-05 | 1993-08-10 | Lever Brothers Company, Division Of Conopco, Inc. | Aqueous based personal washing cleanser |
US5290471A (en) * | 1989-05-05 | 1994-03-01 | Lever Brothers Company, Division Of Conopco, Inc. | Aqueous based personal washing cleanser |
WO1994026866A1 (en) * | 1993-05-19 | 1994-11-24 | Unilever Plc | Improvememts relating to soap bars |
US5482643A (en) * | 1993-05-19 | 1996-01-09 | Lever Brothers Company, Division Of Conopco, Inc. | Soap bars made with ternary system of fatty isethionate ester, fatty acid, and water |
CN1049452C (en) * | 1993-05-19 | 2000-02-16 | 尤尼利弗公司 | Improvements relating to soap bars |
US5500155A (en) * | 1994-03-18 | 1996-03-19 | Henkel Kommanditgesellschaft Auf Aktien | Detergent mixtures of fatty acid isethionate salts and fatty alcohols |
US5691287A (en) * | 1995-12-21 | 1997-11-25 | S. C. Johnson & Son, Inc. | Low irritation cleansing bar |
Also Published As
Publication number | Publication date |
---|---|
GB8614462D0 (en) | 1986-07-16 |
EP0249474A3 (en) | 1989-08-16 |
DE3786113D1 (en) | 1993-07-15 |
CA1311399C (en) | 1992-12-15 |
DE3786113T2 (en) | 1993-09-16 |
ES2054671T3 (en) | 1994-08-16 |
EP0249474B1 (en) | 1993-06-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4180470A (en) | Method for improved acyl isethionate detergent bars | |
FR2479256A1 (en) | AQUEOUS WHITENING COMPOSITION | |
KR870007271A (en) | Ether carboxylate detergent enhancer and preparation method thereof | |
JPH0214960B2 (en) | ||
EP0842257A1 (en) | Dish washer product in tablet form | |
EP0312278A2 (en) | Detergent composition | |
EP0249474B1 (en) | Cleaning compositions | |
EP0147207B2 (en) | Disinfectants | |
DE102007003885A1 (en) | Use of a builder system comprising alkali metal tripolyphosphate and iminodisuccinic acid to produce automatic dishwasher formulations | |
EP0239606B1 (en) | Detergent compositions | |
US4239662A (en) | Liquid detergent compositions | |
JP2007517944A (en) | Fatty soap / fatty acid soap that is processed and foamed well | |
CA2011316A1 (en) | Prevailingly liquid detergent and/or bleaching compositions containing low molecular weight tertiary amines in the form of n-oxide | |
US7662761B2 (en) | Soap bars comprising insoluble multivalent ion soap complexes | |
GB2083490A (en) | Built detergent bars | |
EP0045208B1 (en) | Process for making controlled sudsing detergent powder | |
PT99511A (en) | Process for the preparation of a bleach or granular detergent composition comprising a amidoparoxyacidic bleach and perfum | |
US5759982A (en) | Laundry bars with polyethylene glycol as a processing aid | |
RU2290431C2 (en) | Easily extrudable soap blocks containing alpha-hydroxyacid salts | |
EP0433257B1 (en) | A process for enhancing the bleaching effect at washing and use of certain amphoteric compounds in a detergent composition for enhancing the bleaching effect | |
US3518201A (en) | Chlorine release detergent composition with improved defoamer stability | |
US5441663A (en) | Composition | |
JPS6041117B2 (en) | Method for reducing wear rate of acyl isethionate solid detergent and acyl isethionate cosmetic detergent | |
GB2083491A (en) | Built detergent bars | |
US3723329A (en) | Soap tablet production |
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 |
Kind code of ref document: A2 Designated state(s): CH DE ES FR GB IT LI NL SE |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): CH DE ES FR GB IT LI NL SE |
|
17P | Request for examination filed |
Effective date: 19890726 |
|
17Q | First examination report despatched |
Effective date: 19901210 |
|
RAP3 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: UNILEVER N.V. Owner name: UNILEVER PLC |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): CH DE ES FR GB IT LI NL SE |
|
REF | Corresponds to: |
Ref document number: 3786113 Country of ref document: DE Date of ref document: 19930715 |
|
ET | Fr: translation filed | ||
ITF | It: translation for a ep patent filed |
Owner name: JACOBACCI CASETTA & PERANI S.P.A. |
|
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
26 | Opposition filed |
Opponent name: COLGATE-PALMOLIVE COMPANY Effective date: 19940309 |
|
NLR1 | Nl: opposition has been filed with the epo |
Opponent name: COLGATE-PALMOLIVE COMPANY. |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2054671 Country of ref document: ES Kind code of ref document: T3 |
|
EAL | Se: european patent in force in sweden |
Ref document number: 87305170.0 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19950510 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 19950515 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19950524 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19950526 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19950529 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 19950607 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19950629 Year of fee payment: 9 |
|
RDAG | Patent revoked |
Free format text: ORIGINAL CODE: 0009271 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: PATENT REVOKED |
|
27W | Patent revoked |
Effective date: 19950719 |
|
GBPR | Gb: patent revoked under art. 102 of the ep convention designating the uk as contracting state |
Free format text: 950719 |
|
NLR2 | Nl: decision of opposition | ||
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |