EP0328190A2 - Particulate laundry detergent composition - Google Patents
Particulate laundry detergent composition Download PDFInfo
- Publication number
- EP0328190A2 EP0328190A2 EP19890200221 EP89200221A EP0328190A2 EP 0328190 A2 EP0328190 A2 EP 0328190A2 EP 19890200221 EP19890200221 EP 19890200221 EP 89200221 A EP89200221 A EP 89200221A EP 0328190 A2 EP0328190 A2 EP 0328190A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- particulate
- mixture
- fatty acids
- laundry detergent
- mole
- 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
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D9/00—Compositions of detergents based essentially on soap
- C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
- C11D9/06—Inorganic compounds
- C11D9/08—Water-soluble compounds
- C11D9/10—Salts
-
- 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
- C11D9/00—Compositions of detergents based essentially on soap
- C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
- C11D9/06—Inorganic compounds
- C11D9/08—Water-soluble compounds
- C11D9/10—Salts
- C11D9/12—Carbonates
-
- 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
- C11D9/00—Compositions of detergents based essentially on soap
- C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
- C11D9/22—Organic compounds, e.g. vitamins
- C11D9/26—Organic compounds, e.g. vitamins containing oxygen
- C11D9/267—Organic compounds, e.g. vitamins containing oxygen containing free fatty acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
Definitions
- the present invention relates to a novel, particulate laundry detergent composition which contains no, or reduced levels of inorganic phosphate compounds. Furthermore, it relates to a particulate base material suitable for use in such detergent compositions and to a method of manufacturing this particulate base material.
- Conventional laundry detergent compositions contain phosphate compounds, especially sodium tripolyphosphate (STP), as building agents. Owing to the negative effects of phosphates on the environment, there has been an increasing interest in developing new laundry detergent compositions which have a low or zero phosphate content. However, it has proved to be difficult to match the excellent builder properties of the phosphate-containing compositions.
- STP sodium tripolyphosphate
- zeolites As builder in zero-P laundry detergent formulations.
- the application of zeolites in laundry detergent formulations has a number of drawbacks.
- zeolites In the first place, zeolites have a tendency to cause a bad powder structure. Further more, they tend to interact with silicates which are usually present in the composition as anti-corrosion agents, and they can cause dispensing problems in the washing machine and incrustation on the washed fabrics.
- compositions of the invention utilise acid soap both as a powder base and as a builder:
- the composition according to the invention comprises as a first particulate material a fatty acid mixture in which up to 35 mole% may be unsaturated fatty acids, which mixture has been neutralised to an extent of 25-60 mole %, and as a second particulate material a base in an amount sufficient to render the pH of the composition at a 0.5 wt% concentration in water higher than 8.
- detergent additives may be present, such as a bleach system, proteolytic enzymes, anti-foaming agents, optical brighteners, perfumes, anti-corrosion additives, etc.
- the composition according to the invention exhibits very satisfactory wash performance without the need for phosphate or zeolite builders, although the presence of low levels of these materials is not prohibited and may be beneficial. Powder properties such as flow and compressibility are also excellent.
- the particulate laundry detergent composition according to the invention preferably contains 30-80 wt.% of granular acid soap particles.
- the acid soap is a mixture of free fatty acids and soap, or a partially neutralized mixture of fatty acids.
- a wide range of saturated and/or unsaturated fatty acids may be used, but it was found that the powder properties of the particulate composition become less favourable at a content of unsaturated fatty acids of more than 35 mole%. More specifically, such powders tend to be sticky and are barely free-flowing.
- the mixture of fatty acid consists essentially of 5 - 20 mole% C16-C18 unsaturated fatty acids, and 95 - 80 mole% of a mixture of C8-C14 saturated fatty acids and C16-C18 saturated fatty acids in a ratio of 3:1-1:2.
- C8-C14 saturated fatty acids will also be referred to as laurics
- C14-C16 saturated fatty acids as stearics
- C16-C18 unsaturated fatty acids as oleics.
- the C16-C18 saturated fatty acids or stearics are mainly responsible for the builder properties, while they contribute little to detergency.
- the C16-C18 unsaturated fatty acids or oleics are important for their builder properties but especially for detergency.
- the C8-C14 saturated fatty acids or laurics contribute both to the building and to the detergency, but their main function is to facilitate processing of the soap/fatty acid mixture, and to ensure adequate dissolution properties.
- the laundry detergent compositions according to the present invention can be prepared by dry-mixing the various ingredients into a suitable mixture.
- the acid soap is used in the form of a particulate material, for example, prills or noodles.
- Particle size and shape may be chosen at will and are discussed in more detail below.
- These acid soap particles can be prepared by dissolving a suitable amount of soap in a mixture of fatty acid in the molten state, followed by solidification and processing of the solid mass. Alternatively, they can be prepared by partial in situ saponification or neutralization of a mixture of fatty acids. In this process, a solid base material is gradually admixed with the molten fatty acid mixture.
- Suitable basic compounds are, for example, soda ash (sodium carbonate), sodium disilicate or metasilicate, or sodium hydroxide.
- the operating temperature required to process these mixtures increases with the fatty acid chain length and degree of neutralization, and is preferably within the range of 70-140 C.
- the detergent composition of the present invention contains a particulate base in an amount sufficient to render the pH of the composition, at a 0.5 wt.% concentration in water, higher than 8.
- a base material in principle any base can be used which can be prepared in a particulate form and which readily dissolves in water without forming precipitates with the soap fatty acid particles.
- the same base is used as for the partial neutralization of the fatty acid mixture.
- the laundry detergent composition according to the invention may additionally contain other detergent compounds, such as anionic and/or nonionic non-soap detergent-active compounds. These may be incorporated in the particulate acid soap base, or present as a separate ingredient.
- the acid soap particles may contain up to 10% by weight of anionic and/or nonionic surfactant: higher levels can be detrimental to powder properties.
- anionic or nonionic surfactants may be carried on a porous inorganic material which is admixed with the acid soap particles.
- An example of such an adjunct is a liquid ethoxylated C13-C15 alcohol sprayed on to a Burkeite carrier. If the inorganic carrier is a basic material, the adjunct may serve as the basic component (second particulate material) of the composition.
- a particularly preferred method of preparing acid soap particles was found to be spray-cooling. It was found thereby that particles or prills are obtained with excellent properties with regard to the dissolution rate, stability and to wash performance of the complete detergent composition.
- prills of any desired size and bulk density can be obtained by manipulation of the process conditions. Prills of average particle size 250-1000 m and buk density 400-750 g/e are preferred for compatibility with the other solid ingredients of the compsition, so that segregation in the pack is minimised.
- soaps as well as fatty acids may form various eutectic complexes; such complexes may also be formed between soaps and fatty acids, resulting in highly' complicated phase diagrams for such mixtures.
- This aspect is particularly relevant to the question of meeting the 35-40 ° C target for the solidification temperature.
- the relative amounts of laurics and stearics should not exceed a 1:1 ratio; nevertheless, some liquefaction at the eutectic temperature of about 33 C cannot be avoided.
- the presence of some low melting laurics/stearics complex may be expected to have a favourable effect on the low temperature solubility.
- a number of fatty acid mixtures were prepared, having the compositions shown in Table A. The mixtures were then heated and at approximately 65. C they began to melt. Heating was continued and after complete melting at a temperature of about 80 C soda ash (sodium carbonate) was gradually added in an amount of 0.1 kg/min to control the C02-evolution until the desired degree of neutralization had been reached. At the same time, the temperature was gradually raised to approximately 140 ⁇ C.
- soda ash sodium carbonate
- the solubility was measured as follows: The rate of dissolution of the soap/fatty acid noodles was determined by monitoring the increase in conductivity resulting from dissolution of the soap part of the noodles. In this method, 3 g/I of the sample is added to 1 I demineralized water at 25 . C with continuous stirring, using a magnetic stirrer. The rate of dissolution is expressed as the time required to dissolve 50% of the soluble part of the soap/fatty acid blend (t1 ⁇ 2) . The maximum conductivity is measured after heating to above the melting temperature of the fatty acids, followed by cooling down to ambient temperature.
- Examples 1-3 were repeated, but instead the molten acid/soap mixtures were spray-cooled in a spray tower to form prills.
- the spray-cooling conditions are shown in Table B.
- the powder properties of the prills obtained are given in Table C.
- a mixture of fatty acids was prepared, having thefollowing composition :
- Example 7 The procedure of Example 7 was repeated, using a fatty acid mixture of the following composition :
- the acid soap prills obtained according to Example 7 were used to formulate a complete laundry detergent composition by dry-mixing various other ingredients to the prills, such as a nonionic detergent on a Burkeite carrier, a bleach system and an enzyme.
- composition of the complete detergent powder is given in Table E. Also shown are two commercially available laundry detergent compositions, composition B being a low-P and composition A a zero P composition, both based on zeolites.
- the wash performance of these three compositions was established in a Zanussi ZF 822W top loading drum washing machine, using the normal 40* C cotton cycleprogramme "C".
- 2.5 kg clean mixed wash load of clean cotton pieces and standard soiled test cloths was processed at a liquor/cloth ratio of approximately 6.
- the water temperature was 20 ° C at a pressure of 2.0 kg/cm2.
- the water hardness was 9 or 25 GH.
- the wash powder was added in a dosage of 7.5 g/I. The differences in reflectance of the test clothes before and after the wash ( R * 460) were recorded.
Abstract
Description
- The present invention relates to a novel, particulate laundry detergent composition which contains no, or reduced levels of inorganic phosphate compounds. Furthermore, it relates to a particulate base material suitable for use in such detergent compositions and to a method of manufacturing this particulate base material.
- Conventional laundry detergent compositions contain phosphate compounds, especially sodium tripolyphosphate (STP), as building agents. Owing to the negative effects of phosphates on the environment, there has been an increasing interest in developing new laundry detergent compositions which have a low or zero phosphate content. However, it has proved to be difficult to match the excellent builder properties of the phosphate-containing compositions.
- It is known to use zeolites as builder in zero-P laundry detergent formulations. However, the application of zeolites in laundry detergent formulations has a number of drawbacks. In the first place, zeolites have a tendency to cause a bad powder structure. Further more, they tend to interact with silicates which are usually present in the composition as anti-corrosion agents, and they can cause dispensing problems in the washing machine and incrustation on the washed fabrics.
- We have now found that in accordance with the present invention a new low- or zero-P particulate laundry detergent composition can be provided, without the need for zeolites. The compositions of the invention utilise acid soap both as a powder base and as a builder:
- The composition according to the invention comprises as a first particulate material a fatty acid mixture in which up to 35 mole% may be unsaturated fatty acids, which mixture has been neutralised to an extent of 25-60 mole %, and as a second particulate material a base in an amount sufficient to render the pH of the composition at a 0.5 wt% concentration in water higher than 8.
- Optionally conventional detergent additives may be present, such as a bleach system, proteolytic enzymes, anti-foaming agents, optical brighteners, perfumes, anti-corrosion additives, etc.
- The composition according to the invention exhibits very satisfactory wash performance without the need for phosphate or zeolite builders, although the presence of low levels of these materials is not prohibited and may be beneficial. Powder properties such as flow and compressibility are also excellent. The particulate laundry detergent composition according to the invention preferably contains 30-80 wt.% of granular acid soap particles.
- The acid soap is a mixture of free fatty acids and soap, or a partially neutralized mixture of fatty acids. In principle, a wide range of saturated and/or unsaturated fatty acids may be used, but it was found that the powder properties of the particulate composition become less favourable at a content of unsaturated fatty acids of more than 35 mole%. More specifically, such powders tend to be sticky and are barely free-flowing. The lower the proportion of saturated fatty acid of chain length <C14 present, the greater the proportion of unsaturated fatty acids that can be tolerated.
- Preferably, the mixture of fatty acid consists essentially of 5 - 20 mole% C16-C18 unsaturated fatty acids, and 95 - 80 mole% of a mixture of C8-C14 saturated fatty acids and C16-C18 saturated fatty acids in a ratio of 3:1-1:2.
- For the purpose of this invention, the following definitions will be used: C8-C14 saturated fatty acids will also be referred to as laurics, C14-C16 saturated fatty acids as stearics and C16-C18 unsaturated fatty acids as oleics.
- In the mixture of fatty acids, the C16-C18 saturated fatty acids or stearics are mainly responsible for the builder properties, while they contribute little to detergency. The C16-C18 unsaturated fatty acids or oleics are important for their builder properties but especially for detergency. The C8-C14 saturated fatty acids or laurics contribute both to the building and to the detergency, but their main function is to facilitate processing of the soap/fatty acid mixture, and to ensure adequate dissolution properties.
- The laundry detergent compositions according to the present invention can be prepared by dry-mixing the various ingredients into a suitable mixture.
- According to the invention, the acid soap is used in the form of a particulate material, for example, prills or noodles. Particle size and shape may be chosen at will and are discussed in more detail below. These acid soap particles can be prepared by dissolving a suitable amount of soap in a mixture of fatty acid in the molten state, followed by solidification and processing of the solid mass. Alternatively, they can be prepared by partial in situ saponification or neutralization of a mixture of fatty acids. In this process, a solid base material is gradually admixed with the molten fatty acid mixture. Suitable basic compounds are, for example, soda ash (sodium carbonate), sodium disilicate or metasilicate, or sodium hydroxide. When soda ash is used, only C02 is formed as a by-product, which is easily removed from the reaction mixture. When using sodium alkaline silicates, the formation of insoluble silicates may lead to a higher viscosity of the molten soap/fatty acid mixture. On the other hand, incorporation of silicates directly in the soap/fatty acid matrix is advantageous for the powder structure, and problems associated with the dry mixing of silicates as such are avoided. The operating temperature required to process these mixtures increases with the fatty acid chain length and degree of neutralization, and is preferably within the range of 70-140 C.
- Furthermore, the detergent composition of the present invention contains a particulate base in an amount sufficient to render the pH of the composition, at a 0.5 wt.% concentration in water, higher than 8. As a base material, in principle any base can be used which can be prepared in a particulate form and which readily dissolves in water without forming precipitates with the soap fatty acid particles. Preferably, the same base is used as for the partial neutralization of the fatty acid mixture.
- The laundry detergent composition according to the invention may additionally contain other detergent compounds, such as anionic and/or nonionic non-soap detergent-active compounds. These may be incorporated in the particulate acid soap base, or present as a separate ingredient. The acid soap particles may contain up to 10% by weight of anionic and/or nonionic surfactant: higher levels can be detrimental to powder properties.
- Alternatively or additionally, anionic or nonionic surfactants, but especially nonionic surfactants, may be carried on a porous inorganic material which is admixed with the acid soap particles. An example of such an adjunct is a liquid ethoxylated C13-C15 alcohol sprayed on to a Burkeite carrier. If the inorganic carrier is a basic material, the adjunct may serve as the basic component (second particulate material) of the composition.
- A particularly preferred method of preparing acid soap particles was found to be spray-cooling. It was found thereby that particles or prills are obtained with excellent properties with regard to the dissolution rate, stability and to wash performance of the complete detergent composition.
- Using the spray-cooling process, prills of any desired size and bulk density can be obtained by manipulation of the process conditions. Prills of average particle size 250-1000 m and buk density 400-750 g/e are preferred for compatibility with the other solid ingredients of the compsition, so that segregation in the pack is minimised.
- When following the soap/fatty acid spray-cooling route, apart from the builder/active and solubility requirements, a number of additional factors should be considered:
- 1. To ensure adequate handling and storage properties, the soap/fatty acid-mixture should be sufficiently solid at temperatures below 35-40 C.
- 2. For processing reasons, complete liquefaction should preferably be possible below 100°C. In practice, this means a maximum mixing temperature <150 C. It was found that meeting this requirement means that the soap content of the mixture should be limited to 25-60 mole%, depending on the fatty acid composition.
- 3. The composition of the mixture, in terms of fatty acid types and degree of neutralization, should be such as to ensure adequate solubility at low wash peratures, i.e. in the 20-40° C region.
- It will be clear to the man skilled in the art that these requirements are not easy to fulfil at the same time. A number of characteristics of soap/fatty acid mixtures have to be considered.
- Firstly, soaps as well as fatty acids may form various eutectic complexes; such complexes may also be formed between soaps and fatty acids, resulting in highly' complicated phase diagrams for such mixtures. This aspect is particularly relevant to the question of meeting the 35-40 ° C target for the solidification temperature. In addition, it was found that preferably the relative amounts of laurics and stearics should not exceed a 1:1 ratio; nevertheless, some liquefaction at the eutectic temperature of about 33 C cannot be avoided. Although not ideal from a handling/stability point of view, the presence of some low melting laurics/stearics complex may be expected to have a favourable effect on the low temperature solubility.
- Secondly, a further complication arises from the phenomenon of metathesis; addition of soap to a fatty acid mixture will lead to equilibration reactions, resulting in the presence of soap and free acids for all chain length homologues in a specific ratio, depending on the reactivity of the individual acids. Fortunately, the reactivities of unsaturated and saturated acids differ to such an extent that in a practical situation in these mixtures, the oleics will be preferentially converted into soap. Significant amounts of lauric soap and stearic soap can only present when the proportion of soap exceeds that of oleate.
- The invention will now be illustrated by the following Examples.
- A number of fatty acid mixtures were prepared, having the compositions shown in Table A. The mixtures were then heated and at approximately 65. C they began to melt. Heating was continued and after complete melting at a temperature of about 80 C soda ash (sodium carbonate) was gradually added in an amount of 0.1 kg/min to control the C02-evolution until the desired degree of neutralization had been reached. At the same time, the temperature was gradually raised to approximately 140` C.
- Subsequently, the partially neutralized fatty acid mixture was allowed to cool until solidification had occurred. The solid mass was noodled, using a sodium press. Noodles having a diameter of 1 mm and a length of about 5 mm were obtained. The properties of the noodles and the handling properties are shown in Table A. The solubility was measured as follows: The rate of dissolution of the soap/fatty acid noodles was determined by monitoring the increase in conductivity resulting from dissolution of the soap part of the noodles. In this method, 3 g/I of the sample is added to 1 I demineralized water at 25. C with continuous stirring, using a magnetic stirrer. The rate of dissolution is expressed as the time required to dissolve 50% of the soluble part of the soap/fatty acid blend (t½) . The maximum conductivity is measured after heating to above the melting temperature of the fatty acids, followed by cooling down to ambient temperature.
-
-
- From comparison of Examples 1-3 with 4-6 it follows that by spray-cooling the partially neutralized fatty acid mixtures, prills are obtained having particularly advantageous solubility and powder properties.
- A mixture of fatty acids was prepared, having thefollowing composition :
- 20 wt.% oleics
- 45 wt.% C12-C14 fatty acids
- 35 wt.% stearics
-
- The procedure of Example 7 was repeated, using a fatty acid mixture of the following composition :
- 30 wt.% oleics
- 40 wt.% C12-C14 fatty acids
- 30 wt.% stearics
- The acid soap prills obtained according to Example 7 were used to formulate a complete laundry detergent composition by dry-mixing various other ingredients to the prills, such as a nonionic detergent on a Burkeite carrier, a bleach system and an enzyme.
- The composition of the complete detergent powder is given in Table E. Also shown are two commercially available laundry detergent compositions, composition B being a low-P and composition A a zero P composition, both based on zeolites.
- The wash performance of these three compositions was established in a Zanussi ZF 822W top loading drum washing machine, using the normal 40* C cotton cycleprogramme "C". 2.5 kg clean mixed wash load of clean cotton pieces and standard soiled test cloths was processed at a liquor/cloth ratio of approximately 6. The water temperature was 20 ° C at a pressure of 2.0 kg/cm2. The water hardness was 9 or 25 GH. The wash powder was added in a dosage of 7.5 g/I. The differences in reflectance of the test clothes before and after the wash ( R*460) were recorded.
- The results of the tests at the two different degrees of water hardness using four different test cloths, including the standard EMPA-101 and WFK-10C cloths, are shown in Table F. From these results it is clear that, even at a high water hardness, a very satisfactory washing performance was observed, despite the fact that no phosphate or zeolite builder was present.
The mixture was heated to 65 C and, under continuous heating, solid sodium carbonate was added until a degree of saponification of 33% was reached. The molten soap/fatty acid mixture was subsequently spray-cooled at a temperature of 110 °C, using the conditions given in Table B.
The molten fatty acid mixture was partially neutralized, using solid sodium disilicate, and subsequently spray-cooled. The properties of the prills obtained are given in Table D above and indicate highly satisfactory handling properties.
Claims (15)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8803263 | 1988-02-12 | ||
GB888803263A GB8803263D0 (en) | 1988-02-12 | 1988-02-12 | Particulate laundry detergent composition |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0328190A2 true EP0328190A2 (en) | 1989-08-16 |
EP0328190A3 EP0328190A3 (en) | 1990-10-24 |
EP0328190B1 EP0328190B1 (en) | 1994-05-04 |
Family
ID=10631597
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19890200221 Expired - Lifetime EP0328190B1 (en) | 1988-02-12 | 1989-02-02 | Particulate laundry detergent composition |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0328190B1 (en) |
JP (1) | JPH0668120B2 (en) |
DE (1) | DE68915015T2 (en) |
ES (1) | ES2051983T3 (en) |
GB (1) | GB8803263D0 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0350189A2 (en) * | 1988-07-07 | 1990-01-10 | City Of Hope National Medical Center | Multi-specimen slides for immunohistologic procedures |
US5935923A (en) * | 1996-09-10 | 1999-08-10 | Lever Brothers Company, Division Of Conopco, Inc. | Process for preparing high bulk density detergent compositions |
US20150017311A1 (en) * | 2013-07-02 | 2015-01-15 | Milk Specialties Global | Partial neutralization of free fatty acid mixtures with potassium, livestock feed compositions including them, and methods of making same |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011246682A (en) * | 2010-05-24 | 2011-12-08 | Touki Corp | Powdered detergent |
EP3963037A1 (en) * | 2019-04-29 | 2022-03-09 | The Procter & Gamble Company | A process for making a laundry detergent composition |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB989007A (en) * | 1961-01-23 | 1965-04-14 | Procter & Gamble | Detergent bar |
GB1287625A (en) * | 1969-08-25 | 1972-09-06 | Procter & Gamble Ltd | Improved toilet soap |
GB2010894A (en) * | 1977-12-26 | 1979-07-04 | Kao Corp | Soap for scouring pad |
EP0042647A1 (en) * | 1980-06-20 | 1981-12-30 | Unilever N.V. | Particulate, soap-containing detergent composition |
EP0470033A2 (en) * | 1990-08-01 | 1992-02-05 | Asturiana De Zinc, S.A. | Installation for removing the zinc deposited by electrolysis on aluminium plates |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5230962B2 (en) * | 1972-12-12 | 1977-08-11 | ||
JPS5231202B2 (en) * | 1973-11-01 | 1977-08-13 |
-
1988
- 1988-02-12 GB GB888803263A patent/GB8803263D0/en active Pending
-
1989
- 1989-02-02 ES ES89200221T patent/ES2051983T3/en not_active Expired - Lifetime
- 1989-02-02 DE DE1989615015 patent/DE68915015T2/en not_active Expired - Fee Related
- 1989-02-02 EP EP19890200221 patent/EP0328190B1/en not_active Expired - Lifetime
- 1989-02-10 JP JP1032558A patent/JPH0668120B2/en not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB989007A (en) * | 1961-01-23 | 1965-04-14 | Procter & Gamble | Detergent bar |
GB1287625A (en) * | 1969-08-25 | 1972-09-06 | Procter & Gamble Ltd | Improved toilet soap |
GB2010894A (en) * | 1977-12-26 | 1979-07-04 | Kao Corp | Soap for scouring pad |
EP0042647A1 (en) * | 1980-06-20 | 1981-12-30 | Unilever N.V. | Particulate, soap-containing detergent composition |
EP0470033A2 (en) * | 1990-08-01 | 1992-02-05 | Asturiana De Zinc, S.A. | Installation for removing the zinc deposited by electrolysis on aluminium plates |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0350189A2 (en) * | 1988-07-07 | 1990-01-10 | City Of Hope National Medical Center | Multi-specimen slides for immunohistologic procedures |
EP0350189A3 (en) * | 1988-07-07 | 1991-05-29 | City Of Hope National Medical Center | Multi-specimen slides for immunohistologic procedures |
US5935923A (en) * | 1996-09-10 | 1999-08-10 | Lever Brothers Company, Division Of Conopco, Inc. | Process for preparing high bulk density detergent compositions |
US20150017311A1 (en) * | 2013-07-02 | 2015-01-15 | Milk Specialties Global | Partial neutralization of free fatty acid mixtures with potassium, livestock feed compositions including them, and methods of making same |
Also Published As
Publication number | Publication date |
---|---|
JPH0668120B2 (en) | 1994-08-31 |
DE68915015T2 (en) | 1994-08-18 |
DE68915015D1 (en) | 1994-06-09 |
EP0328190A3 (en) | 1990-10-24 |
EP0328190B1 (en) | 1994-05-04 |
GB8803263D0 (en) | 1988-03-09 |
ES2051983T3 (en) | 1994-07-01 |
JPH01268799A (en) | 1989-10-26 |
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